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10
Applied Ceramic Technology
10
Applied
Ceramic
Technology
Volume I
Copyright 2005 SACMI IMOLA
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ISBN 88-88108-48-3
To the reader................................................................................................................................. 9
Introduction ................................................................................................................................ 11
The production process ........................................................................................................... 22
Chapter V Physical and structural properties of ceramic raw materials .... 175
Particle size distribution ....................................................................................................... 176
How water influences ceramic systems............................................................................. 186
8
Introduction
TO THE READER
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Applied Ceramic Technology
10
Introduction
INTRODUCTION
Just what is a ceramic material? While dozens of definitions are possible, it can
effectively be described as any product, having a form, made up of non-metallic inor-
ganic raw materials (whether mineral or artificial), which, from an incoherent powdery
state, are transformed, via various processes, into a semi-finished item, which, through fir-
ing, becomes a solid object of partially crystalline and partially vitreous structure.
Virtually all the transformations and/or mixings become permanent after firing.
When speaking of inorganic raw materials it is necessary to bear in mind the level
of abundance of the most common elements in the earths crust, as it will obviously
be convenient and advantageous to manufacture ceramic items using the most widely
available and economic raw materials.
Fig. 1 (below) shows that these essentially include silicon and aluminium oxides
Fig. 1. The most common elements in the earths crust (from Kingery: Introduction to Ceramics - Wi-
ley).
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having different Fe, Ca, Mg, Na and K contents: these are, effectively, the 7 most
common elements in nature and are always present in a ceramic body.
PERIODIC TABLE
INERT
GASES
Atomic number
Chemical symbol
Atomic weight
it can be seen just how few ceramic-relevant elements there are (Al, Si, Ca, Mg, Fe,
Ti, Na e K). Even when the main constituents of glazes (e.g. Pb, Zn, Sn, Zr, Cr, Ni,
Cr, V, B etc.) are taken into account it is evident that the assortment of elements
characterising a TRADITIONAL CERAMIC material is a restricted one.
In keeping with the general, introductory nature of this chapter, it can be said
that, where these materials are concerned, the field of study is limited to products
normally made up of natural oxides such as:
TILES.
SANITARYWARE.
TABLEWARE.
BRICK.
CERTAIN REFRACTORY ITEMS.
12
Introduction
Despite this description of the ceramic characteristics that the chemical compo-
sition confers on the bodies, it is a well known fact that chemical analysis of a
ceramic body or raw material is not in itself the most important aspect of product
characterisation: it can easily be demonstrated that products with greatly differing
performance and fields of use, such as low water-absorption floor tiles, sanitary-
ware items, bricks etc. all have very similar chemical composition.
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14
Introduction
[Remember that, for a system in equilibrium, tertiary diagrams illustrate the composi-
tion of systems consisting of 3 components. They display the relative percentages account-
ed for by each component as shown in the diagram below (Fig. 2b): any point within the
triangular area of the diagram is effectively an intersection of the lines running parallel
to the sides of the triangle and the point at which these lines converge gives the percentage
values of the components in the system. The percentage content of component A is read
off on the left-hand side of the triangle, component B on its base and component C on its
right-hand side.
For example, in fig. 2b point P represents a system where component A accounts for 30%
of the material (point E), B accounts for 20% (point F) and C the remaining 50% (point
G)].
Fig. 2b. How to read off composition percentages on the axes of a tertiary diagram.
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Fig. 3. SiO2/Al2O3/Fe2O3 tertiary diagram showing the compositional fields for majolica, cottoforte
and red gres bodies (Vincenzini and Fiori, 1977, vol. 2).
G = red gres
C = cottoforte
M = majolica
Fig. 4. Fe2O3/Na2O + K2O/MgO + CaO tertiary diagram showing the compositional fields for ma-
jolica, cottoforte and red gres bodies (Vincenzini and Fiori, 1977, vol. 2).
16
Introduction
GR = red gres
Fig. 5. SiO2/Al2O3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O diagram showing the composition-
al fields for red gres and potassium and sodium white gres bodies (Fabbri and Fiori, 1983, vol. 1).
GR = red gres
Fig. 6. Al2O3/Na2O/K2 tertiary diagram showing the compositional fields for potassium and sodium
white gres and red gres (Fabbri and Fiori, 1983, vol. 1).
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GR = red gres
Fig. 7. Al2O3/Na2O + K2O/TiO2 + Fe2O3 + MgO + CaO2 tertiary diagram showing the composi-
tional fields for red gres and potassium and sodium white gres bodies (Fabbri and Fiori, 1983, vol. 1).
Fig. 8. SiO2/Al2O3 + TiO/Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram showing the compo-
sitional fields for majolica, cottoforte and red gres clays (Sandrolini and Palmonari, 1974, vol. 2).
18
Introduction
Oxygen
Silicon
Silicon
Oxygen
Fig. 9. Phyllosilicate repetition units: SiO4-4 tet- Fig. 10. Two-dimensional projection of oc-
rahedrons and Al(OH)63- octahedrons. tahedral structural units.
These form two-dimensional particles, the distance between two identical struc-
tural repetition units varying as a function of the type of material, as illustrated in
Fig. 11.
The interlayer space between two particles, micelles or two strings of particles
etc. may, by way of this repetition unit arrangement, vary from a minimum of 2.7
(in kaolinite) to a maximum of 8 (in chlorites) or more Angstroms [1Å = 10-8 cm],
thus determining whether or not extraneous molecules or ions can infiltrate the
structure.
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(A) Na-montmorillonite
(B) Ca-montmorillonite
(A) Vermiculite
(B) Tri-octahedral chlorite
Fig. 11. Examples of the different inter-lattice spacings that characterise clayey raw materials.
20
Introduction
Where water lies between the particles they are able to slide against each other
more easily (i.e. thus conferring plasticity).
Such spaces may also be occupied by fluxing ions such as Na+ and K+, which
modify the technological properties of the raw material.
For this reason it is highly important that the mineralogical nature of the clayey
contents of a body be known so that the advantages and disadvantages of their
employment can be identified: this information is obtained using X-ray diffractom-
etry (XRD) techniques.
Particle size distribution is another key factor: it is obvious that the purpose of
forming and firing a semi-finished ceramic item is to obtain a product in which
solid-solid reactions have been activated and completed as far as possible. In this
regard results are greatly influenced by the contact surface area of the particles: a
greater contact surface area is more conducive to the heat-induced passage from
sintering to reaction to fusion (see Fig. 12).
While the clayey particles are themselves small, they need to be mixed with
particles of other appropriately sized materials so as to plug as many gaps as possi-
ble and thus obtain maximum density: this is achieved via proper combination of
several grain sizes.
Therefore, proper control of body particle size distribution cannot be achieved
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via simple sieve residue alone: checks should be run using appropriate instrumenta-
tion (X-ray or laser etc.) that takes into account the interaction principles between
the individual particles (diffraction, scattering etc.).
Whatever the employed ceramic body raw material selection method, the subse-
quent production process will invariably be as follows:
IN-QUARRY selection, mining and quality control.
PREPARATION of raw materials for mixing.
BODY preparation via GRINDING.
FORMING.
DRYING.
Additional procedures to add AESTHETIC value to the product.
FIRING.
SORTING, PACKAGING and STORAGE.
Each of these stages requires attention and must be planned and executed care-
fully: constant quality control is essential.
There follows a stage-by-stage summary of the most common tile manufactur-
ing processes:
BODY PREPARATION
CRUSHER dry Hammer mill
Pendulum mill
wet Alsing (ball) mill
Continuous mill
Fast agitating disperser
22
Introduction
The following flow-charts (Tab. 3-4) summarise the most common production
processes.
raw material
storage
raw material
storage ê
ê batching
batching
ê
ê
wet grinding
wet or dry grinding
í î
ê
spray drying continuous mill discontinuous mill
or wetting
ê î í
pressing
spray drying
ê
drying ê
pressing
ê
biscuit firing ê
ê drying
glazing ê
ê glazing
glaze firing
ê
ê firing
sorting
ê
sorting
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If every stage of the production process has been well planned, properly-made
tiles will exit the plant: yet the aesthetic and performance requisites required of
tiles in airport halls differ enormously from those intended for use in apartment
bathrooms or on industrial flooring. Hence the concept of tile classification, summed
up as follows.
24
Introduction
Chapter I
Many properties of clays and other ceramic raw materials depend on the type
and quantity of the various minerals that constitute them. The identification of
such minerals is therefore of primary importance. Yet clear-cut identification is
made difficult by the fact that ceramic raw materials rarely consist of pure, well
crystallised minerals: instead, several minerals are generally present in appreciable
quantities together with many other minor constituents. Given these circumstanc-
es, identification of the main phases can be difficult, especially where they are all
rather similar.
Sometimes, and this is often the case with clays, a mineral cannot be identified
without prior purification and separation. Furthermore, a single clay may contain
various minerals and is nearly always associated with significant quantities of quartz,
calcareous materials, micas and others.
Also, clayey minerals are made up of very small particles (dimensions as small as
100 Å, that is 10-6 cm, are frequent), making identification even more problematic.
Moreover, clayey raw materials are often characterised by isomorphic substitution,
created by the genesis conditions described in the following chapter.
In general, then, analysis methods used for the study of these raw materials
must allow for recognition of minerals of non-constant, often intermingled com-
position sometimes made up of extremely small particles. Since identification of a
mineral depends on its key characteristics, which must necessarily always be the
same independently of mine attitude and the surrounding environment, analytical
methods which make use of the univocal properties of the individual raw material
classes must be employed.
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tics of the predominant mineral in the mix, they do not identify its individual com-
ponents.
Sampling
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Identification and characterisation of ceramic raw materials
Chemical analysis
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28
Identification and characterisation of ceramic raw materials
The main methods used in quantitative ceramic material chemical analysis are
based on interaction (of the fluorescent emittance, absorption or emission type) of
the sample with electromagnetic radiation. The main methods are:
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Other chemical analysis methods pertinent to the search for specific elements
(e.g. FLAME PHOTOMETRY in tracking down alkaline elements) do, of course,
exist, but a detailed account of these is beyond the scope of this book.
It is, instead, worthwhile pointing out that specific chemical tests can be used to
check for the presence of specific elements (carbon, sulphur, fluorine...) or anions
(CO32- carbonates, SO42- sulphates
): these employ analytical techniques that are
generally simple and efficacious and provide extremely important information for
evaluating the applicability of a raw material in a ceramic process.
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Identification and characterisation of ceramic raw materials
Fig. 13a.
Optical Systems
Torch
Generator
(ICP)
Pump/
Nebuliser
SPECTROMERC
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This type of analysis allows the technician to check for the presence of individ-
ual crystal phases in a sample and thus trace its mineral composition, the evaluation
of which is of primary importance in defining the technological characteristics of
a raw material or the contribution it will make to a body.
A preliminary form of such mineralogical information is provided first by na-
ked-eye and then microscopic inspection under reflected, polarised and transmitted
light (on naked samples included in the resin): by combining the cited observations
with other optical properties (e.g. refractive index) it is possible to obtain good
discrimination and recognition results. In the mineralogical analysis of ceramic
materials the entire science of optical microscopy should be viewed as a branch in
its own respect consisting of numerous techniques (as illustrated by the abundant
literature) that achieved maximum diffusion between the 1940s and 60s.The most
widespread mineralogical analysis technique now in use is X-RAY DIFFRACTO-
METRY (XRD). This can be effected on individual crystals or, more commonly, on
powders (Fig. 16).
The incident X-radiation falling on the sample, properly filtered so as to confer
monochromaticity, interacts with the crystal lattice, giving rise to related diffrac-
tion images, via the equation Bragg nλ = 2dsinϑ, at the inter-lattice distance d of the
crystal as a function of the diffraction angle. Since a wide range of X-ray sources
can be used (the most common is provided by Ni-filtered Cu anticathodes emitting
CuKα = 1.541 Å only) it is correct to list every interaction set of a particular crystal
lattice with the list of the active lattice distances expressed in Angstroms (Å).
Indexes and data bases are available for all crystalline substances (PDF, see the
examples in tables 5 and 6). These are updated by an international controlling body.
This reference material allows recognition of crystal types in natural and artificial
samples, while recent software improvements now provide more modal manage-
ment of diffractometry data, providing quantitative evaluations with regard to the
presence of individual minerals.
Of course, when working with powders it is essential that the sample be high-
ly representative of the whole. There should be no preferential orientation, easily
caused by bi-directionally developed crystals: this is why preparation and laying
out of the sample are so important. Milling must be carried out as efficiently as
possible, taking care not to alter the structural characteristics of the sample, es-
pecially where clayey, so as to aid homogenisation of all the phases and ensure
casual orientation of all crystalline faces; where analysis with a spinning sample
holder is excluded (such equipment is usually unavailable), one must be reason-
ably certain that a strongly non-oriented sample has been prepared, even in the
concomitant presence of phases having different density and inappropriate crys-
tallographic habit, such as clays and micaceous materials having micelles of a
well-developed bi-directional form.
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Identification and characterisation of ceramic raw materials
and simple and, on sufficiently simple matrices, leads to fairly easy interpretation of
the gathered data, allowing moreover through combination with the verified pres-
ence of certain crystal phases, attribution of a chemical formula and combination
with quantitative chemical analysis so-called rational analysis of a raw material or
body (i.e. approximation of its composition expressed in standard minerals). It will
therefore be possible to evaluate a ceramic body not only in terms of its oxide-based
chemical composition, but also its mineralogical composition, expressed in Quartz,
Kaolinite, Illite, Calcite, Dolomite, Albite (Sodium feldspar), Microcline (Potassium
feldspar) etc. (see Fig. 17 for example).
Thermal analyses
As the heading suggests, there is more than one way of analysing samples via
the parameter variations that occur as a function of an increase (or decrease) in
temperature. Variations in weight, temperature, heat evolved or absorbed, dimen-
sions, gaseous substances emitted etc. can all be registered as a function of a partic-
ular temperature gradient. Each of these techniques has a corresponding type of
analysis, as listed below:
TGA (ThermoGravimetricAnalysis),
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34
Identification and characterisation of ceramic raw materials
Fig. 17. Example of body chart with rational XRF + XRD analysis.
DTA (DifferentialThermalAnalysis),
DSC (DifferentialScanningCalorimetry),
TMA (ThermoMechanicalAnalysis) or DIL (Dilatometry),
EGA (EvolvedGasAnalysis).
These types of analysis are not only an obvious method for observing and pre-
dicting the behaviour of an individual raw material or a body during drying, firing
or cooling: they are also an excellent aid in determining the mineralogical composi-
tion of a material, as the observed effects closely correlate with the crystalline struc-
ture and the phase transformations of various minerals. Since the presence of min-
erals and salts such as dolomite, carbonates, sulphates, sulphides and fluorides etc.
(Figs. 18-22) can be recognised, such analyses can also help identify chemical pa-
rameters.
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Fig. 18. Comparison between the most significant (appropriately schematised) DTA curves represent-
ing clayey minerals: A = kaolinite; B = metahalloysite; C = Na-montmorillonite; D = Ca-montmo-
rillonite; E = vermiculite; F = sepiolite; G = polygorskite.
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Identification and characterisation of ceramic raw materials
Fig. 20. Examples of dilatometric curves. Unfired samples undergo irreversible transformation (curve
a) and fired ones, in cooling, essentially return along the curve followed during heating (curve b).
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Fig. 21. Dilatation-Shrinkage (DS) and Differential Thermal Analysis (DTA) of secondary minerals
(by G. Peco 1970) Ca = limestone; Q = quartz; Cr = cristobalite; F = feldspar.
Fig. 22. Dilatation-Shrinkage (DS) and Differential Thermal Analysis (DTA) of standard clayey
minerals (by G. Peco 1970). C = kaolinite; H = halloysite; M = montmorillonite; Mi = mica.
38
Identification and characterisation of ceramic raw materials
where α is the linear thermal expansion coefficient between T1 and T2, L0 is the
initial length of the sample and ∆L is the difference between LT1 and LT2. It is,
however, consolidated practice in a factory to use, instead, the cubic coefficient. This
is obtained by multiplying the linear coefficient obtained from dilatometric mea-
surements by 3, on the arbitrary assumption that the propensity towards dimen-
sional variation is the same in all directions.
This data is extremely important in evaluating compatibility between different
materials during heating and, more importantly, during cooling, where any tension
that has built up as a result of dilatometric incompatibility becomes permanent.
Firing of a glaze that has been applied to a ceramic body is a classic example (Fig.
23).
In the light of the above it is clear that there exists the opportunity or, rather,
the need, to effect a series of fine analytical checks on raw materials used in the
ceramic production process: most companies do not have the relevant instruments
and thus checks are generally outsourced to laboratories or external bodies with
the equipment for accurate examination.
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Fig. 23. Opposing effects of dilatometric incompatibility between glaze and body in the cooling part of
the cycle: case A αglaze > αbiscuit - case B αglaze < αbiscuit.
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Identification and characterisation of ceramic raw materials
For these reasons, manufacturers would be advised to carry out the following
checks.
Moisture content
Size and appearance
Residue
Carbonates
Reducing agents
Pu - Ps
u% = _______ x 100
Pu
Sieve residues
One hundred grams of dry sample is weighed and treated in a laboratory agita-
tor for about 30 minutes with 300 ml of de-ionised water to which 1g of sodium
tripolyphosphate or sodium polyacrylate is added so that the particles are complete-
ly broken up and dispersed.
The slip is sieved at 1,000, 2,500 and 10,000 mesh/cm2 (180, 125 and 60 µm
screens).
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Fig. 25. Apparatus for determination of the various particle size distribution bands.
The residue obtained in the various sieves is dried to constant weight and then
weighed. The resulting values directly provide residue percentages for the various
mesh sizes.
With non-plastic raw materials it may be interesting to carry out dry measure-
ment by sieving about 200 g of dried material through a sieve column of appropri-
ate mesh sizes [e.g. 11(2,000) - 35(1,000) - 140(500) - 590(250) - 1,600(150) - 4,700(90)
and 9,500(63) mesh/cm2 (mm)].
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Identification and characterisation of ceramic raw materials
Fig. 26. Apparatus for the determination of carbonate minerals (calcite and dolomite).
Assuming that CO2 has been generated by CaCO3 only: % CaCO3 =% CO2 . 2.273.
Formula:
ml of reduced K2Cr2O7 × 0.69 (stoichiometric factor)
___________________________________________ = total reducers %
sample weight (g)
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Example:
Blank control test: 10.0 ml of K2Cr2O7 added, 21.5 ml of FeSO4 necessary for
end point without clay: correction factor = 0.465 (10/21.5).
Measurement test: 2.125 g of sample + 10 ml K2Cr2O7, 19.25 ml of FeSO4 nec-
essary for end point: 10 - (19.25 x 0.465) × 0.69 /2.125 = 0.34% total reducers.
This measurement essentially detects the organic substances in the sample, but
is also influenced by the presence of any reducing substance, especially mineral
sulphides such as Pyrite, Marcasite etc.
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Identification and characterisation of ceramic raw materials
Chapter II
ROCKS
The term rock refers to a natural aggregate of one or more minerals. The term
mineral refers to a homogeneous natural solid with a well defined chemical com-
position and its own crystalline structure. The interconnected processes that lead
to rock formation constitute what is known as the rock cycle. The earth is essen-
tially made up of a series of concentric layers - the Crust, the Mantle and the Core.
Crust
Mantle
Molten
outer core
Solid
inner core
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A part of the mantle (the external part) is molten as a result of the high temper-
atures and pressures at such depths; if this part of the mantle shifts to areas where
temperature and pressure are lower (i.e. towards the earths crust) it may solidify,
thus giving rise to intrusive rock. Where the molten mass (MAGMA) reaches the
surface, it cools much more rapidly, giving rise to extrusive rocks.
Intrusive rocks may subsequently be brought to the surface by forces of tectonic
origin.
Degradation processes effected by both atmosphere and hydrosphere continu-
ally alter the surface of the earths crust: for example, erosion may dismantle
existing igneous rock of both intrusive and extrusive origin. Such surface deg-
radation gives rise to sedimentary rocks. Aqueous solutions can lead to precipi-
tation of salts or supply materials to organisms. allowing them to form shells or
skeletons. Granules produced by the erosion of pre-existing rock, salts separated
from solutions by the activity of organisms and salts which precipitate directly
from the solutions themselves give rise to an accumulation of sediments. The
latter are compressed and permeated by other layers forming above them and
thus undergo that transformation (DIAGENESIS) which leads to the formation
of sedimentary rocks. These continue to be buried by later deposits and are con-
sequently shifted to greater and greater depths. However, tectonic forces may
bring them back to the surface where they are again exposed to degradation. Al-
ternatively, movements in the earths crust may bury rocks (sedimentary, extru-
sive, intrusive) even deeper; beyond certain depths, the changes in pressure and
temperature cause profound modifications. This is where metamorphic rocks are
formed. Like the others, metamorphic rocks too can be brought to the surface and
subject to degradation, thus resulting in new layers of sedimentary rock. Alter-
natively, rocks may be carried to extreme depths (or close to very high tempera-
ture zones) where they melt and give rise to new magma of a composition differ-
ent from that of the original magma.
Volcano
Atmosphere
Sea
Plutons
Metamorphic Rocks
46
Rocks
The mantle-fed magma can arrive at the surface rapidly via volcanoes (2) or
consolidate within the earths crust (1). In this case tectonic forces (3) may brings
plutons (igneous intrusions) to the surface where the atmosphere and hydrosphere
cause degradation (4). The eroded materials are carried away by rivers and streams
into depository basins (5). This is where accumulation begins (6), transforming the
sediments into sedimentary rock (7). These may be returned to the surface (8) where
the destruction-accumulation pattern begins anew, or may sink deeper (9) where
they are transformed into metamorphic rocks. Similarly, intrusive rocks (1) can be
transformed into metamorphic rocks (9) by variations in temperature and pressure.
If pressure and temperature conditions are particularly intense the metamorphic
rocks will fuse and give rise to new magma (11).
The black arrows indicate tectonic forces.
Magma
Clays, materials of prime importance to the ceramic industry, are extremely var-
iable rocks made up of different minerals, generally of a silicate nature, sedimented
in the form of platelets, fibres, belts etc., and are, for the most part, associated with
other minerals of detrital origin that often play a key role.
Variety is vast, since the combinations of initial rock types, morphological and
climatic conditions, types of erosion and alteration, transport and sedimentation
conditions, state and duration of attitude are virtually incalculable.
To render the concept of genesis clearer, consider a rise or any zone exposed to
atmospheric agents: erosion is caused by the combined action of rain, wind and the
freeze-thaw cycle, resulting in material that accumulates in the form of soil or is
washed far away by surface waters, giving rise to sedimentary basins.
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Primary rocks
Sedimentary rocks
Produced by the consolidation of sediments, solid particles suspended in fluids
(usually water) that transport them considerable distances from the site of erosion.
These particles settle from the fluid owing to their greater density. The complete
formation process, then, involves the alteration phase of the original materials fol-
lowed by erosion, transport and, finally, depositing, the final result of which is greatly
influenced by the size of the particles and the pressures/temperatures exerted on
the sedimentary layer by subsequent geological events in the zone, any intervening
chemical reaction etc.
Among the sedimentary rocks, the most common minerals are clays, quartz and
calcite; it is important to distinguish:
a) Detrital rocks (argillites, pelites, conglomerates
)
48
Rocks
It is also important to point out that further classification is often effected ac-
cording to dimensional criteria. Such criteria give rise to different classifications of
well defined terminology such as those illustrated in the table below:
ROCKS CONSTITUENTS mm
Coherent Incoherent
Metamorphic rocks
These are formed by chemical-physical solid state reactions caused by shifts in
the earths crust, such as, for example, in the sinking of surface rock masses.
In general, the crystals of rocks formed in this way point in the direction of the
tensions and loads acting on them (e.g. schist); the temperature increase associated
with the geothermal gradient originating from increased proximity with the earths
mantle leads to dehydration of the original minerals (e.g. formation of potassium
feldspars from micas).
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the sedimentation basin so as to better understand the mechanisms that form clayey
rocks.
At present the earths crust, on average, is thought to be as follows:
The minerals representative of this composition are not very numerous, and are
those that generally give rise to clays.
50
Rocks
PYROXINES 9%
AMPHIBOLES 6%
MUSCOVITE KAl2[AlSi3O10](OH,F)2 3%
FELDSPATHOIDS <1%
Leucite K[AlSi2O6]
Nepheline KNa3[AlSiO4]4
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Sorosilicates, with two, three, four or six tetrahedrons, possibly in a closed loop
configuration.
52
Rocks
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Bearing in mind the ionic radius of oxygen and silicon (the second most wide-
spread element) it can be seen how this has the bulk to be at the centre of a compact,
regular polyhedron of minimum potential energy, with a coordination number of 4
(i.e. the tetrahedron [SiO4]4-).
The octahedral configuration with a coordination number of 6 is given by the
regular arrangement of the oxygen ions or, more commonly, hydroxyls (OH-),
which have the same radius around an Al3+ ion of a size suitable for containment
at the centre of such a structure.
Both silicon-based tetrahedrons and aluminium-based octahedrons can combine
together to form repetition units via apex-apex, edge-edge or face-face bonds, giv-
ing rise to different structural repetition units of various shape.
The combination of tetrahedral and octahedral structural units, arranged in reg-
ularly overlain layers with well-defined inter-layer distances, is also possible: those
distances are extremely important in determining the macroscopic characteristics
of individual clayey minerals.
The simplest configuration is the two-layer one, with alternation of units made
up of tetrahedral linked 2-by-2 by an apex (Si2O5)2- and octahedral layers (Fig-
ures 29 a and b show grouping of the kaolinite and montmorillonite).
(A) Halloysite
(B) Kaolinite
54
Rocks
(A) Na-montmorillonite
(B) Ca-montmorillonite
This can be described by the rough formula (OH)3Al2(OH)Si2O5, or, more appro-
priately, Al2O32SiO22H2O, which corresponds better with the chemical analysis, ex-
pressed in oxides. This molecule is electrically neutral (6 positive charges from the
aluminum + 8 positive silicon charges = 14 positive charges, saturated by the 4
negative charges of the OH- groups and 10 negative charges from the remaining 5
oxygens = 14 negative charges) and consists of particles around 1 µ thick, although
the finest may be smaller than 0.005 µ (i.e. the equivalent of 7 elementary sheets),
thus forming ionic crystals of varying size.
Clayey minerals of greater complexity may have octahedral layers interspersed
between tetrahedral layers, in 3-layer arrangements as is seen with talc and pyro-
phyllite; this structure is also seen in Illite (mica group), where the triple tetrahe-
dral/octahedral/tetrahedral layer is associated with another octahedral layer etc.
(Figs. 30-31).
(A) Vermiculite
(B) Tri-octahedral Chlorite
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(A) Muscovite
(B) Illite
This way of organising different types of clayey sheet constitutes the most use-
ful distinctive criteria in classifying clayey mineral groups. The fact that there is,
between the sheets, a space large enough to allow the introduction of one or more
water molecules (inter-sheet or inter-layer water) gives rise to a further classifica-
tion, this time a technological one, as the presence of such water greatly influences
the capacity of these various layers to slide against each other and thus ultimately
determine the plasticity of the material.
It is thus possible to formulate a simplified classification of the main clayey ma-
terials:
Non-crystalline ALLOPHANES
Within such groups, the nature and position of the substitutive cations consti-
tute a further classification criteria.
56
Rocks
which means that the calcium ion can replace the sodium ion more easily than
the reverse. This compensatory exchange effect may vary as a function of the ionic
charge of the solutions.
An enormous variety of exchanges can take place, even including in-tetrahedron
substitution of silicon with aluminum; thus, as a function of the ionic charge, com-
pensation processes are activated, mainly through the participation of K+ and Na+
ions that position themselves, via electrostatic attraction, on the basal faces of the
micelles. In the case of Illite, for example, substitution of aluminum with silicon
may take place in the octahedron and this weakens the total ionic charge of the
clayey micelle in which there was a charge imbalance of a sign opposite to that at
tetrahedral level: the K+ cations, then, are fixed less stably on the surfaces, but tend
to position themselves laterally, largely where there are discontinuities or fractures,
and this alters the characteristics of this clayey material even further.
The process occurs, in the same way, and especially as regards substitutions in
the octahedral layers, in smectite-type minerals. In these cases there is a general
decrease in ion-sheet and sheet-sheet binding forces, thus leading to a variable lat-
tice distance that consequently allows insertion of whole water molecules, with all
the resulting consequences.
Similar phenomena occur in the chlorites, but the inter-layer water is often re-
placed by Al(OH)3, Fe(OH)3 and, above all, Mg(OH)2.
Cationic exchange capacity (CEC), easily established using routine analytical tech-
niques, is an intensive measurement which provides a realistic image of just how
much these phenomena are present in a clayey mineral. It gives a measure of the
ease of cationic exchange in the structure of the mineral, via the introduction of
Na+ ions. Observing that:
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From the above it can be seen that it is possible to effect a more or less complete
characterisation of clays in general via the description of a few clayey minerals
(kaolinite, illite, montmorillonite and chlorites), although it should be born in mind
that polyphyllitic mixed layers often occur (e.g. Bravaisite, consistent in a mix of
Illite and Montmorillonite).
58
Rocks
Chapter III
Kaolinite
Mineralogical structure
The base element consists of a tetrahedral sheet in which each tetrahedron
consists of four oxygen atoms (each with two negative charges), positioned at its
apexes, and a silicon atom (with four positive charges) at its centre. This is associat-
ed with an octahedral sheet in which each octahedron consists of six OH- hydrox-
yl units (each carrying a negative charge) located at its apexes and a cation (usually
trivalent but also bivalent) at its centre. This base element is illustrated in Fig. 32.
Structure of kaolinite
according to Gruner
Elementary
kaolinite cell
Fig. 32.
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The tetrahedral unit thus has four non-saturated negative charges; the octahe-
dral unit is negative too with three (if the cation is trivalent) or four (if bivalent)
non-saturated charges.
In the kaolinitic base element the two sheets bind by substituting an OH hy-
droxyl on each octahedron with the sharing of an oxygen atom (at the tetrahedron
apex) which had a free charge.
This anion is thus shared by a tetrahedron and two octahedrons in that each OH
hydroxyl unit is balanced by the aluminum cations of two adjoining octahedrons.
With this coupling the kaolinite structure is electrically neutral. This structure can
be repeated (vertically) a great many times while maintaining the same distance
between equal, adjoining levels.
It is this structural rigidity that explains the non-expandability of the pre-
served lattice despite the weakness of the forces on which maintenance of the struc-
ture depends (Van der Waals and hydrogen links).
Chemical composition
Al2(X2O5)(OH)4
Where x is the element in the tetrahedral position (Si4+ and, as vicariant, Al3+
and Fe3+, which lead the structure to be deficient by one positive charge).
Theoretical composition
SiO2 = 46.54%; Al2O3 = 39.50%; H2O= 13.96%
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Raw materials for ceramic bodies
and the addition of plasticizing materials (vegetable and carbonaceous parts) that
sometimes blacken the raw material.
The presence of certain chlorites can mask the presence of kaolinite owing to
coincidence of basal reflections at 12.50° (corresponding to 7.18 Å).
In this case any splitting that occurs in the reflection on the 002 plane must be
checked for, given that there exists a small difference between the lattice distance of
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disordered
kaolinite
kaolinite (3.47Å) and chlorite (3.54Å) to which positioning of the peaks at 24.90
and 25.20 correspond respectively.
The DTA (Differential Thermal Analysis) diagram for kaolinite (Fig. 34) shows
a net endothermic peak at 580-600 °C, associated with the transformation of ka-
olinite in meta-kaolin with crystallisation water loss; at around 980 °C there is,
instead, a marked exothermic peak that is probably connected with the crystallisa-
tion of mullite or alumina (Fig. 35).
Thermogravimetric (TG) analysis shows a sharp weight loss at around 520~580
°C (i.e. when the crystallisation water is lost); no variations, instead, are observed
towards 980 °C, in that this particular exothermic reaction is caused by the libera-
tion of bond energy and not the removal of material.
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Raw materials for ceramic bodies
Fig. 34. DTA curves for several minerals in the kaolinite group.
Fig. 35. Mullite crystals formed by heating of kaolinite in a siliceous matrix (magnification x 37,000)
(by Kingery: Introduction to Ceramics - Wiley).
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Temperature °C
Fig. 36. Dilatometric curve for a high-purity kaolin sample, showing two abrupt contractions corre-
sponding to the dehydroxylation phase and the recrystallization reaction.
Fig. 37. Dilatometric curves for kaolins of increasing quartz content (from curve a to curve c); the
effect of the quartz gradually prevails over that of the kaolinite.
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Raw materials for ceramic bodies
Fig. 38. Dilation-Shrinkage of kaolinite-quartz mixes (by G. Peco 1970). (0, 12, 24, 36, 48% of
quartz).
The table below gives standard mineralogical analysis for some common kaoli-
nitic raw materials:
BALL CLAY 1 2 3 5 6
Kaolinitic Minerals 50 48 76 27 36
Micaceous Minerals 21 19 11 25 32
Montmorillonite Minerals 4
Quartz 22 28 7 37 28
Feldspars 5 4
Others 1 1 3 2
CHINA CLAY 7 8 9 11 12
Kaolinitic Minerals 85 80 79 92 87
Micaceous Minerals 14 16 15 2
Montmorillonite Minerals
Quartz 3 4 1 2
Feldspars ~ 5 8
Others 2 1 1
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Raw materials for ceramic bodies
In the field of frits and glazes kaolinitic materials, purified using wet techniques,
are used as components in mixes to be fritted (melted) and as a plasticizing addi-
tive during the grinding of frits.
Kaolins of lesser purity are employed in the manufacture of alumina refracto-
ries where they act as alumina carriers.
For some such products untreated kaolins contaminated by the presence of iron
may sometimes be used.
However, only a small percentage of the worlds total kaolin output is actually
employed in the ceramic industry: almost 90%, in fact, is channelled into the paper
industry where it is used as a filler or surface coating.
It is also used in minor quantities as:
a filler for tyres and rubber
a filler for paints
a pharmaceutical support (pills)
a cosmetic and toothpaste support
a powdery insecticide support
a fertiliser support.
Illite
Mineralogical structure
Similar to that of the micas. The basic structural unit consists of two tetrahe-
dral sheets sandwiching an octahedral one (of trioctahedral form), as illustrated
in Fig. 39. It is virtually the same as the montmorillonite structure except that some
silicon cations are always substituted by aluminum to which potassium is added,
thus maintaining the electrical balance of the structure.
However, the potassium cation is attached securely and is not easily replaced as
happens with montmorillonite.
The structural differences between illite and mica lie in lesser substitution of
silicon with aluminum and, therefore, less potassium aggregation. Furthermore,
illite may contain interlayered water molecules.
In addition to the trioctahedral illites, others of dioctahedral form (a sheet of
tetrahedrons with a sheet of octahedrons) exist.
Alteration causes the latter types to turn into montmorillonite while the former
are transformed into vermiculite. The SiO2/Al2O3 ratio (taking into account substi-
tutions in the octahedral sheet) varies from 2 to 4; it is frequently 3. Glauconite
(ferroan illite), an illite of particular interest, is generated by alteration of the bi-
otite.
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Chemical composition
Illite is represented by the following formula:
Yet it is not completely definable; aluminum substitutes the silicon less frequent-
ly and, as a consequence, less potassium is required.
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Raw materials for ceramic bodies
Illite-chlorite clays
Illite-kaolinite materials
German
English
French
Fig. 40. Al2O3/Na2O + K2O/TiO2 + Fe2O3 + MgO + CaO tertiary diagram showing composition-
al fields for red gres clays and the imported kaolinitic materials used in white gres (Fabbri & Fiori,
1985/7).
Illite-chlorite clays
Illite-kaolinite materials
German
English
French
Fig. 41. Na2O + K2O/Fe2O3 + TiO2 /MgO + CaO tertiary diagram showing compositional fields for
red gres clays and the imported kaolinitic materials used in white gres (Fabbri & Fiori, 1985/7).
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Illite-chlorite clays
Illite-kaolinite materials
German
English
French
Fig. 42. SiO2 /AlO3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram showing com-
positional fields for red gres clays and the imported kaolinitic materials used in white gres (Fabbri
& Fiori, 1985/7).
nepheline
Feldspars syenite
Feldspathic rocks
Quartz-feldspathic sands
Quartz sands
Fig. 43. SiO2/Al2O3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram illustrating the
compositional fields for complementary raw materials used in the production of gres (Fabbri & Fiori,
1985/7).
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Raw materials for ceramic bodies
Yet Italy is not Europes only source of illite: of particular renown are the Hun-
garian deposits of white illite associated with montmorillonite, the plastic Miocene
clay of Czechoslovakia, and the vast Ukrainian deposits of kaolinitic illite that pro-
ducers of porcelain tiles (also known as vitrified stoneware or referred to by its
Italian name gres porcellanato) have recently begun using. In the United States (Illi-
nois), the illite deposits for the production of expanded clay have been in use for
some time.
Extraction techniques in hilly areas consist of successive ripping and scraping
operations on terraces (usually more than 20 m wide and some tens of metres long).
These continue until deposits are exhausted. Alternatively, on slopes, high-power
bulldozers are used.
In semi-flat areas where the extraction zone provides more room for manoeuvre,
scrapers are preferred to bulldozers. This vehicle, as the name implies, scrapes
wide strips of terrain, funnelling the material inwards towards the machine: this
system provides excellent homogenisation of the raw material, a process aided by
the vehicle loading system.
Ripping and scraping has several points in its favour. Firstly, it allows work to
be carried out over a vast surface area, with large-scale transportation of material
resulting in low unit costs. Secondly, there is the advantage of flexibility: unsuit-
able extraction zones can be isolated and the same machines can be used for both
handling and treatment of the extracted clay (crumbling, homogenisation, dry-
ing).
This last sequence takes place in the quarry itself: a 15-20 cm thick layer of the
material is spread out and left in the sun for a full day, occasionally being churned
over to ensure proper uniformity of exposure to the suns rays.
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Temperature °C
Fig. 44. The DTA curve for illite is characterised by weak endothermic effects at temperatures which, in
other clayey minerals, cause much more intense reactions.
Temperature °C
Fig. 45. A typical DTA curve for muscovite and dioctahedral micas in general.
As can be seen, the mineralogical picture is a fairly constant one and, on the
whole the only significant differences concern carbonate content which swings
from a maximum of 20-23% in Pliocene and Pleistocene grey-blue clays to 13-
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Raw materials for ceramic bodies
Fig. 46. Dilatation-Shrinkage of illite-quartz mixes (by G. Peco 1970). (0, 12, 24, 36, 48% of quartz).
16% in those of the Antognola series and just 0-6% in the red-beds.
With regard to red-beds it should be pointed out that these sometimes have a
very high carbonate content (sometimes higher than 16%!).
A final observation concerns natural plasticity (i.e. that of the unground raw
material); clays of the Antognola series and especially red-beds have undergone
diagenesis processes which have partially or completely inhibited this typical prop-
erty of clayey materials.
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On the whole tiles obtained from these raw materials are readily vitrified. Car-
bonate-free tiles achieve complete vitrification at 1050-1080 °C, within very tight
palliers (ranges); carbonitic ones are slightly more refractory and become vitreous
beyond 1100 °C, collapsing suddenly with a total absence of pallier (a characteristic
of carbonates).
Where clays are rich in carbonates fired product colouring varies from salmon
pink to yellowy and greeny-yellow (at vitrification); other clays, instead, become
bright red at lower temperatures, switching to dark brown when liquid-state reac-
tions gain the upper hand.
Montmorillonite (smectite)
Mineralogical structure
The (trioctahedral) base structure is made up of two tetrahedral sheets enclos-
ing an octahedral one (see Fig. 47). Specifically, this is the structure of pyrophyllite.
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Raw materials for ceramic bodies
The mineral crystals of this group are bound by particularly weak forces. There
are no hydrogen bonds (as in kaolinite) in that there is no possibility of contact
between the octahedral and tetrahedral layers belonging to different base struc-
tures, because the former are prisoners inside the latter. The only links are the
Van der Waals weak forces: consequently, the insertion of water molecules is ex-
tremely easy, resulting in the crystalline structure expanding to nearly six times
its original volume. The greater reactivity of the montmorillonite family (with re-
spect to, for example, the kaolinite family) derives from the suitability of the inter-
nal faces that mark the boundary of each base structure, in that these elements are
easily separable. The property known as isomorphic substitution (i.e. the capacity
for replacement of a cation with another of a different charge) is also much evident.
If, for example, a trivalent (aluminum) ion replaces the (tetravalent) silicon of the
tetrahedrons, electrical equilibrium is only achieved following absorption of an ex-
ternal (mono or bivalent) cation; in this second case the number will be equal to
half the negative charges released by the isomorphic substitution.
The peculiar behaviour of montmorillonite is partly explained by the extremely
small size of its particles.
Then there is the significant diversity between the sodium and calcic montmo-
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rillonites: the former are much more plastic with a much higher ionic exchange
capacity.
It is also fairly common to encounter mixed structures created by the association
of montmorillonite and illite (interlayers). These are formed owing to the similari-
ty of the two different mineral sheets.
Chemical composition
X2Y4O10 (OH)2
Theoretical composition
SiO2 = 66.7%; Al2O3 = 28.3%; H2O = 5%
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Raw materials for ceramic bodies
-
-
1
1
-
1 1
Temperature °C
Fig. 49. DTA curve for montmorillonite; the low temperature dehydration peak (100-250 °C) is the
most intense and characteristic and its form varies greatly as a function of the interlayer cation: a) Ca-
montmorillonite; b) Na-montmorillonite. The other dioctahedral smectites (beidellite and montronite)
have curves similar to those of montmorillonite.
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Temperature °C
Fig. 50. Typical DTA curve for trioctahedral smectite minerals such as saponite.
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Raw materials for ceramic bodies
a first contraction towards 180 °C followed by further expansion (which reaches its
maximum towards 573 °C should the raw material also contain free quartz).
Towards 900 °C further contraction is induced by sample sintering reactions
and softening.
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Ceramic uses
While the use of clayey raw materials containing montmorillonite in layers mixed
with illite is quite common (especially in the manufacture of tiles, bricks and pot-
tery), utilisation of almost exclusively montmorillonite materials is extremely lim-
ited owing to the characteristics listed in the preceding paragraph. It should be
pointed out that montmorillonite has a markedly negative effect on the rheological
properties of slips. Bentonite, when hydrated, swells enormously and takes on the
aspect of a colloidal gel.
Chlorite
Mineralogical structure
These are lamellar minerals having an aspect similar to that of mica.
The classic chlorite structure consists of an alternating association of a mica-
ceous-like sheet (where an Al3+ or Mg2+ octahedral plane is enclosed by two
hexagonal planes of silica tetrahedrons) with a brucite one (characterised by a
flat hexagonal lattice of silica tetrahedrons with a central cation) as illustrated in
Fig. 52.
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Raw materials for ceramic bodies
Chemical composition
The mineralogical structure is not original, but derives, rather, from those of the
two associated micaceous and brucite sheets.
Composition of the micaceous sheets is as follows:
X8Y6O10 (OH)4
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X6 (OH)12
When, in the micaceous structure, an Si4+ replaces an Al3+, the resultant electri-
cal charge difference is balanced by an excess charge in the brucite sheet generated
by the replacement of Al3+ with Mg2+.
The theoretic formula of true chlorite (or leptochlorite) is as follows:
Oscillation of the x value (which can vary from 1 to 2) and the nature of the
substituents lead to the formation of different varieties, such as bavalite (ferrous
chlorite), clinocore, penninite, prochlorite, etc.
Mining techniques in hilly areas see the application of ripping and scraping
techniques on terraces which continues until the material is exhausted (such ter-
races are generally more than 20 m wide and some tens of metres long). On slopes
high-power bulldozers are generally used.
In semi-flat areas where the extraction zone is of considerable size, scrapers are
preferred to bulldozers.
This vehicle, as the name implies, scrapes long, wide strips of terrain, funnel-
ling the material inwards for collection.
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Raw materials for ceramic bodies
This last sequence takes place in a clearing within the quarry grounds; a 15-20
cm thick layer of the material is spread out and left in the sun for a full day,
occasionally being turned to ensure proper uniformity of exposure to the suns
rays.
The 12.5° diffraction corresponds to that of the 001 kaolinite plane which can
cause errors in interpretation. To prevent this inconvenience the analysis is repeat-
ed by preheating the sample to 550-600 °C. In this case the detected basal reflec-
tions are cancelled while those at 6.2° are reinforced.
DTA analysis (Fig. 54) of different chlorite types gives widely varying results; a
first endothermic peak is generally noted towards 400 °C when the hydroxyls of
the brucite sheet are removed. A second peak is seen between 600 and 800 °C: this
corresponds to removal of the hydroxyls from the micaceous sheet.
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10 15
Fig. 53. X-ray diffraction patterns for two different, randomly-oriented chlorite polytypes: a) and b)
illustrate how the two samples have significant, yet differentiated peaks with respect to the 001 basal
plane and illustrate evident variations as regards the diffraction planes marked 1, 2, 3, 4 and 5.
Temperature °C
Fig. 54. DTA curves for the chlorites group show evident endothermic and exothermic peaks (curve a);
as iron content increases (curve b) there is a gradual lowering of the temperature at which the exother-
mic reaction takes place.
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Raw materials for ceramic bodies
On the whole the tiles obtained from these raw materials are quite fusible. Those
without carbonates vitrify completely at 1050-1080 °C within a very tight range.
Carbonate ones are slightly more refractory and become vitreous beyond 1100
°C, shrinking suddenly (a characteristic of carbonates).
Post-firing colour ranges from salmon pink to yellowy to greenish-yellow (on
vitrification) where clays are carbonate-rich; others have much deeper hues of red
(at lower temperatures) and turn dark brown once liquid-state reactions gain the
upper hand.
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Ceramic uses
Once again, Italian clayey raw materials of a predominantly illite-chlorite
nature are considered. They are mainly applied in the ceramic industry as fol-
lows:
grey-blue Pliocene-Pleistocene clays in high-porosity coloured bodies (majolica)
for glazed wall tiling
grey clays of the Antognola series for medium-porosity coloured bodies (cot-
toforte) for glazed floor and wall tiles; unglazed Tuscan cotto type bodies
red-beds for frost-proof or low-porosity (single firing) glazed/unglazed (red gres)
for residential, industrial and outdoor flooring.
Pliocene grey-blue clays (i.e. those with a higher degree of natural plasticity)
are widely used in the manufacture of rustic pottery (majolica), ornaments and in
the production of large extruded bricks (lug bricks and ceiling bricks).
Talc
Mineralogical structure
Mineral of mica-like structure with an elementary sheet made up of two
hexagonal planes of silica tetrahedrons containing an Mg2+ octahedral plane (Fig.
55).
Chemical composition
Talc is a magnesium acid metasilicate having the following formula:
Mg3Si4O10 (OH)2
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Raw materials for ceramic bodies
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Differential thermal analysis (DTA) of a pure talc shows just one endothermic
peak between 900 and 1000 °C, which marks the point at which the OH hydroxyls
are removed.
In certain cases, the presence of chlorite and the loss of zeolite water are high-
lighted.
The corresponding TG analysis indicates marked weight loss. Dilatometry too
is often influenced by the presence of other minerals, especially chlorite, which causes
a net increase in dilatation between 600 and 800 °C.
4
4
9.36
3.11
4
4.68
4 4
4
4.57
2.48
4
2.63
28.62
18.86
34.5
34.0
9.44
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Raw materials for ceramic bodies
Mass %
Temperaturs difference
Temperature °C
Temperature °C
Given this behaviour, even small in-body percentages (2-5%) can make a use-
ful contribution by forming, with the alkali in the feldspars, eutectic mixes with
particularly low melting points. Such effects are often desirable in the manufac-
ture of compact materials with extremely low water absorption (e.g. porcelain
tiles).
Ceramic uses
The introduction of talc into ceramic bodies allows manufacturers to control
thermal expansion.
This dilatometric aspect is especially important in the manufacture of tiles.
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Raw materials for ceramic bodies
Talc is also used in the production of certain magnesium glazes, while in sani-
taryware manufacture it is sprinkled in the mould cavities to aid release (especial-
ly in the manufacture of large items).
Many of the above-cited uses require high-purity talc, except where used in
coloured tile body mixes.
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“NON-PLASTIC” MATERIALS
Silica
Mineralogical structure
The base structure of silica consists of a tetrahedron with oxygen anions at its
apexes and a centrally-positioned silicon atom. A complete tetrahedron, then, has
four negative ions (Figs. 59-60-61).
Anhydrous silicon has three crystalline forms: quartz, trydimite and cristobalite
and a glassy amorphous (i.e. non-crystalline) one. Each main type has varieties that
are stable in particular temperature ranges.
Fig. 59. Structural arrangement of silica tetrahedrons in quartz (British Ceramic Society).
Fig. 60. Crystalline structure (A) and vitreous structure (B) (according to W.H. Zachariasen and B.E.
Warren).
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Raw materials for ceramic bodies
Fig. 61. Trydimite (a) and cristobalite (b) structures (Worral, Clays and Ceramic Raw Materials -
Elsevier).
Fig. 62. Equilibrium diagram for silica, including the metastable portions (from Kingery, Introduction
to Ceramics - Wiley).
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Chemical formula
SiO2
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Raw materials for ceramic bodies
Note, though, that the term quartzites also refers to high-purity sedimentary
quartz deposits with an extremely high degree of cementation and to metamorphic
deposits characterised by recrystallization of the original granules.
A last, more specific type of silica deposit concerns the diatomites. These are
sedimentary rocks mainly consisting of the siliceous shells of diatoms (tiny marine
algae), and are characterised by high porosity and friability.
Such deposits, where in fresh water, are known as fossil flours while sedimentary
deposits in marine environments are known as tripoli.
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3.34
1
4.26
1
1 1
1.81
1
1
2.45
1
2.28
2.12
2.23
1.98
39.46
26.63
42.45
36.54
20.84
50.1
45.7
heating cooling
Temperature °C
Fig. 64. Endothermic effect (during heating) and exothermic effect (during cooling) in a quartz sam-
ple; the thermal inertia of the system provokes a delay in the appearance of maximum intensity, both in
cooling and heating.
Dilatometry (Fig. 65) shows, during heating, a sharp increase at 573 °C. This
corresponds to the switch from quartz α to quartz β , which, as is known, is accom-
panied by a sharp increase in volume.
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Raw materials for ceramic bodies
The same phenomenon occurs even more markedly just beyond 220 °C, when
cristobalite (rarely present) passes from the α to the β form.
If, during cooling, not all the free silica has been bound by the neo-formation
of more complexly-structured minerals (e.g. wollastonite or mullite), the passage
from quartz α to quartz β is signalled by marked dimensional contraction.
This is a particularly critical moment in ceramic manufacturing as excessively
fast cooling can cause certain types of damage to the tile.
Fig. 65. Dilatometric behaviour in various structural forms of silica (from: Worral, Clays and Ceramic
Raw Materials - Elsevier).
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With quartzites the main (and most costly) task is grinding of the rocky frag-
ments; this is followed by granulometric classification.
Magnetic separation systems can be used to remove some impurities. However,
the efficacy of these methods is frequently undermined by electrostatic charging of
the dust: as a result, the use of powerful magnetic fields may cause the loss of a
substantial portion of output.
Companies often mine crystalline deposits containing both quartz and feldspars.
In these cases treatment becomes a somewhat more complex affair, being designed
to separate the two mineralogical components as efficaciously as possible.
Note that some users of silica such as the glass industry demand materials of
highly specific particle size distribution.
Glass makers, in fact, require that all particles fall within the 0.1 - 0.8 mm
range.
Ceramic uses
Single fired tiles, whether white or red body, use only small quantities of sand
(maximum 10-15%).
With coloured bodies even low-purity sands (e.g. those with a substantial iron
content) can be used without any particular problems.
Often, compositions for white single firing products do not include the direct
introduction of siliceous sands: the same effect is attained by employing natural
mixes of feldspar, clay and quartz known as partially kaolinized feldspars.
Some porcelain tile formulas also make use of minimum percentages of siliceous
materials. The addition of silica to vitreous-china and porcelain bodies serves the
purpose of balancing the presence of SiO2 and alumina, thus providing the stoichi-
ometric ratios, which, in firing, lead to the formation of mullite.
In the tile industry the main aim is to open up the mixes to aid degassing of
any impurities (organic substances) in the raw materials and removal of water dur-
ing the drying process: a further positive effect is reduced contraction and deforma-
tion (during firing).
Another important aspect concerns particle size distribution and the (crystalline
or amorphous) state of the quartz particles. Ceramic companies tend to use already
ground powders so as to reduce body grinding times.
While natural silica deposits already consisting of very fine particles do exist
(pyroclastic and diatomite deposits), these materials, unfortunately, have extreme-
ly negative effects on the rheological properties of ceramic slips and cannot be
used.
Manufacturers of vitreous-china and porcelain sanitaryware require especially
pure siliceous materials.
Proportions used are generally in the order of 20-25%. Earthenware pottery
requires about 10-15%, while glazed white body wall tiles employ quantities in the
order of 10-20%.
Silica is also used in the production of acid refractories. Siliceous bricks are
manufactured starting with quartzites: these are ground to the required particle
size distribution, with just small percentages of binder being added.
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Raw materials for ceramic bodies
Semi-silicates require the introduction of about 10% alumina; fireclays are 30-
40% alumina, the remaining part consisting of quartz.
Diatomites are used for insulating bricks.
Silica is also used in the preparation of frits where it is introduced in quantities
of 20-40%; for the most part it is air classified, although certain formulations re-
quire (sometimes significant) quantities in fine sand form.
Feldspathic minerals
Mineralogical structure
The basic feldspar structure consists of a ring of four tetrahedral units (Fig.
66); potassic and sodium feldspars have three silicon tetrahedrons and one alumi-
num one while in calcic feldspars half the four tetrahedral units are silicon-based
and half aluminium-based.
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K
Fig. 66. Elementary feldspar cell.
The crystals appear as flattened hexagonal prisms and are stable at low temper-
atures.
Carnegieite is an allotrope form of nepheline, stable at high temperatures; it
derives, by way of a process analogous to that illustrated above, from cristobalite
(another allotrope form of silica). Note that nepheline is found together with alka-
line feldspars in rocks called nepheline syenites, characterised by a silica content
deficiency.
Chemical composition
The general chemical formula for feldspars is as follows:
X Y4 O8
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Raw materials for ceramic bodies
Note, however, that solid solutions between these three feldspars are frequent; in
particular, albite and anorthite form, at high temperature, a continuous series of
crystalline solutions that remain intact even after cooling (plagioclases). These go
by the following names (the albite/anorthite ratio is indicated in brackets):
oligoclase (7/1)
andesine (2/1)
labradorite (1/2)
bytownite (1/7).
X4 (Al4Si4O16)
where X mostly consists of Na, with K accounting for no more than 1/3.
Theoretical nepheline is made up of: 41.5% SiO2, 35.2% Al2O3 , 17.5% Na2O and
5.8% K2O.
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102
Raw materials for ceramic bodies
generally requires the use of explosives. In the event of partial kaolinization explo-
sives may be limited to a pre-mining role, being used to shatter the deposit before
machinery is moved in to extract it.
However, machinery can sometimes be used to extract the material from such
deposits directly.
The tout-venant is sorted manually (e.g. as it passes along on a conveyor belt),
although more recently, automatic sorting systems using optical recognition tech-
nology have been employed.
After crushing, it is then sub-divided by particle size. Magnetic separators are
sometimes used: these easily retain the metallic particles that stem from wear on the
machinery itself, but have little effect on weakly magnetic materials such as biotite,
a common contaminant.
In this case, getting results means applying a more intense magnetic field, yet in
doing so there is a real risk of attracting useful rocky particles that were electrically
charged during grinding. Such contaminants can sometimes render the deposits
unusable; a well-known case regards the above-cited Cornish Stone, where deeper
and deeper extraction has transferred operations into less kaolinized areas that are
decidedly richer in fluorine minerals. As is known, fluorine is a source of severe
environmental pollution, so the rock cannot be used unless it is put through floata-
tion treatment.
This is so costly that the material has effectively been priced out of the market,
explaining why mining in this still-important deposit has been brought to a halt.
Concentration of alkali content via floatation is a widespread practice in the
USA.
This technique allows the quartz to be separated from the feldspar using various
chemical reagents, creating special foams that remove, in suspension, one of the
two minerals.
With sedimentary deposits (feldspathic sands and sandstones) the most common
treatment consists of washing (which removes the mainly clayey fine particles) fol-
lowed by drying in a rotary kiln.
Where the deposit is poorly cemented earth-moving machinery (bulldozers and
scrapers) can be used to extract it without any need for grinding. If not, explosives
are used in the mine, then crushers break up the fragments.
Albite:
Angular position of peaks = 27.86 - 23.52 - 13.84 - 24.16 - 22.04° 2ϑ
Lattice distances = 3.20 - 3.78 - 6.39 - 3.68 - 4.03 Å
Orthoclase:
Angular position of peaks = 27.70 - 29.94 - 26.82 - 23.54 - 21.14° 2ϑ
Lattice distances = 3.21 - 2.98 - 3.32 - 3.77 - 4.20 Å
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Nepheline
Angular position of peaks = 29.46 - 22.96 - 27.08 - 21.08 - 30.68° 2ϑ
Lattice distances = 3.03 - 3.87 - 3.29 - 4.21 - 2.91 Å
Leucite:
Angular position of peaks = 27.24 - 25.86 - 16.43 - 30.60 - 31.48° 2ϑ
Lattice distances = 3.27 - 3.44 - 5.39 - 2.92 - 2.84 Å
For albite, DTA readings give endothermic peaks between 820 and 900 °C, indi-
cating its allotropic transformation.
Analysis of oligoclase and labradorite gives analogous peaks between 780 and
820 °C.
With nepheline, thermal activity is observed towards 1250 °C as a result of the
minerals allotropic transformation. Since there are no matter-removing reactions,
TG analysis provides us with no information at all.
Dilatometry shows an absence of variation up to 1050 -1100 °C, after which the
start of contraction which reaches its peak after 1100 °C is observed.
Ceramic uses
Feldspathic materials are used extensively wherever manufacturers intend to
achieve a high degree of vitrification: for example, in porcelain tiles and light co-
loured low porosity products 25 to 55% is used.
In vitreous-china sanitaryware and porcelain feldspathic materials are introduced
in quantities ranging from 20 to 30% and from 17 to 37% respectively.
Such percentages, of course, not only change from composition to composi-
tion but also as a function of the alkali content of the feldspathic material being
added.
Producers select potassium or sodium feldspar according to the desired specifi-
cations of the final product: bear in mind that potassium feldspar is a less powerful
flux than sodium feldspar but provides manufacturers with a wider vitrification range
(Figs. 67-68).
Fig. 67. Fusibility test sequence for the Alavus feldspar as revealed by a Leitz heating microscope
(softening point 1240 °C, melting point 1400 °C).
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Raw materials for ceramic bodies
Fig. 68. Softening range of feldspathic fluxers identified by heating microscope (A softening point, B
melting point).
Feldspar is sometimes added to lower the expansion coefficient when other raw
materials tend to produce a biscuit with an excessively high coefficient that can,
after glazing, take on the convexity caused by excessive glaze compression.
Large quantities of (sodium or potassium) feldspar are also used in the produc-
tion of frits: here, percentages vary from 20 to 40%.
Nepheline can be used instead of feldspar, however, because of its expense (es-
pecially where consumers are far from its source) its application is limited to cir-
cumstances where its high fluxing properties are essential.
Pyrophyllite
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Mineralogical structure
A clayey mineral with a mica-like base structure consisting of two hexagonal
layers of silica tetrahedrons containing an octahedral layer of Al3+ (see Fig. 69).
Like talc, the external surfaces of the particles are covered with the oxygen atoms
of the SiO4 sheet, while the hydroxyls are always in the interior, protected by the
two tetrahedral layers. This condition gives structural neutrality, considerable sta-
bility and chemical inertia.
Chemical composition
Al2Si4O10(OH)2
O
OH
AI
8.13Å
SI
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Raw materials for ceramic bodies
1
3.34
0
0
3.03
9.19
0
-
4.59
1
9.97
- + -
4.25
1 1+ 0 +
4.98
1
1.99
2.45
2.55
2.12
7.16
35.12
20.85
12.35
19.31
45.4
42.4
36.5
29.1
26.6
17.7
9.61
8.86
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Ceramic uses
The highly refractory nature of pyrophyllite limits its range of applications.
There are few examples of it being used in the manufacture of white body wall tiles
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Raw materials for ceramic bodies
or glazed floor tiles (as in Brazil, etc.). In such cases, it is used in extremely low
percentages.
Generally speaking, pyrophyllite lowers the expansion coefficient and limits fir-
ing shrinkage: it might, therefore, be used in the production of bodies that vitrify at
high temperature (floor tiles) yet show reduced shrinkage where fired at low tem-
peratures (wall tiles).
It is also used to produce tableware, as it gives the fired product a glossy appear-
ance. Its main use, however, is in the manufacture of refractories, insulation ceram-
ics and refractory crucibles.
Wollastonite
Mineralogical structure
Wollastonite has a sorosilicate structure where two silicon tetrahedrons connect
to form a pair sharing an oxygen ion (Fig. 73).
Usually of fibrous appearance (the crystals are needle-shaped or, sometimes,
tabular), this mineral has a specific weight of 2.9, scores 4.5-5 on the Mohs hard-
ness scale and is white in colour.
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Chemical composition
A calcium metasilicate with the following formula:
Ca SiO3
Synthetic wollastonite
Made from limestone and siliceous fireclay (a kaolinitic clay of disordered struc-
ture).
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Raw materials for ceramic bodies
Ceramic uses
Mainly used in the manufacture of floor and wall tiles.
7
1
3.83
3.31
7
7
3.51
7
2.97
7 7 7
3.08
2.55
7
2.30
7 7
2.72
77
2.34
1.91
2.16
2.18
41.69
47.4
41.3
39.1
38.4
35.1
32.9
30.0
29.5
26.9
25.3
23.2
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Used extensively in the USA and Scandinavia where this mineral is available
cheaply.
In single firing products the addition of wollastonite improves the bending
strength of the bodies, reduces firing shrinkage and speeds up kiln cycle times due
to the smoother thermal expansion characteristics of the body. In porcelain tiles it
is used as a bleaching agent.
On unfired items wollastonite acts (like sands) as a lean raw material while dur-
ing firing (beyond 980-1050 °C) it acts as a flux.
Cooling can be faster as the beta to alpha quartz inversion at around 570 °C is
much reduced.
The introduction of this mineral in ceramic compositions also gives dimension-
al uniformity and aids glaze-body match.
Further characteristics of ceramic bodies based on wollastonite include: low ther-
mal expansion, lustre, a smooth surface and minimum swelling.
Wollastonite is also an important component in frits (being used in quantities
ranging from 5 to 20%), particularly in those used to produce sanitaryware and fine
ceramics where it provides an improved melting range and increases lustre.
It is also introduced, albeit in very limited percentages, into certain refractory
compositions (e.g. saggers) where it is thought to improve thermal shock and im-
pact resistance.
Carbonates
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Raw materials for ceramic bodies
Crystalline structure
Different carbonate minerals crystallise into the following systems:
Limestones:
Calcite rhombohedral
Aragonite orthorhombic
Dolomite: rhombohedral
Magnesite: rhombohedral
Aragonite is irreversibly transformed into calcite at around 500 °C.
Dolomites
Similar to that of limestone; however, during diagenesis about half the Ca2+
cations are replaced by Mg2+ (present in the saturating marine solutions) giving rise
to regular stratification between the two carbonates.
The increased pressure that accompanies accumulation aids substitution in that
magnesium is smaller than calcium and is embedded more easily.
Magnesites
Genesis is identical to that of dolomite, the two minerals often being found to-
gether.
It can be said that magnesite represents the final stage in the substitution of
calcium with magnesium.
Both a crystalline and cryptocristalline type can be distinguished.
In the latter, genesis is thought to have its origins in the reactions between car-
bonate-rich water and magnesium-rich silicate rock.
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tion of important parts of some of the continents mountain chains (Alps, Apen-
nines, Carpathians etc.).
Some of the more recent deposits, such as those concentrated in North Africa
(Tuf) and the Caribbean (caliza arrecifal) have not undergone diagenesis and are
found in a semi-coherent state.
Although calcareous rocks are not particularly hard their extraction does re-
quire the use of explosives; the above-cited semi-coherent deposits can be extracted
with the aid of earth-moving machinery.
Dolomites
Dolomite deposits (which take their name from the famous Alpine chain, itself
named after the French scientist Dolomieu) are also common, their origins dating
back to the Silurian, Devonian, Triassic and Jurassic eras.
Like limestone, the extraction of dolomites requires the use of explosives.
Magnesites
The main big-crystal deposits are located in Austria, ex-USSR, Czechoslovakia,
Spain, Brazil, China, the USA, Canada and Australia.
Cryptocrystalline deposits are of stromatolith form and are contained in ser-
pentines and ultrabasic rocks.
Key deposits of this type are found in Greece (Macedonia), the ex-Yugoslavian
nations (Balkan region), Austria (Steinmarck), Turkey (Eskisehir), India, the USA,
countries formerly part of the USSR and Canada.
Dolomites
Diffractometric analysis (using Cu Ka radiation ) highlights the characteristic
peaks corresponding to lattice distances of 2.88, 2.67, 2.53, 2.40, 2.19 and 1.80 rel-
ative to the following angular values: 30.97, 33.51, 35.34, 37.39, 41.14, 50.57. 2ϑ.
DTA clearly shows how, as in the case of dolomite, dissociation takes place in
two separate stages, at 780 and 920 °C respectively.
Thermogravimetric (TG) analysis also highlights the removal of the carbon
dioxide at those temperatures. The mineral behaves as if it were a mix of calcium
carbonates and magnesium.
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Raw materials for ceramic bodies
2.88
#
3.04
$ ## #
#
$$ #
2.29
2.19
1.91
$$$
1.87
2.09
1.80
$
1.78
2.50
#
2.40
$
2.53
#
2.67
2.85
44.93
30.97
29.33
50.57
41.16
37.39
35.34
33.51
49.42
47.42
43.08
39.34
51.1
35.9
31.3
Fig. 75. X-ray diffractometry analysis of dolomite (left.) and calcite (right).
(D = dolomite, C = calcite).
Temperature (°C)
Fig. 76. Differential thermal analysis curves for calcite (curve a) and dolomite (curve b) with in-air
decomposition.
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Magnesite
Differential thermal analysis (DTA) reveals an endothermic peak connected with
decomposition of the mineral and removal of the CO2 at a temperature ranging
from 400 to 650 °C. Correspondingly, thermogravimetric (TG) analysis reveals a
steep gradient in that zone.
A B
Shrink. Water. Abs. Shrink. Water. Abs.
1095° 4.8 7.3 7.3 0
1055° 1.2 16.6 7.8 1.3
1010° 0.9 17.8 4.1 8.7
960° 0.9 18.0 2.2 11.4
910° 0.9 18.0 1.4 13.8
CaCO3 tot.% 15.0 2.0
Ceramic uses
Limestones and dolomites are essential raw materials in the manufacture of low-
porosity, low-shrinkage ceramic items such as porous wall tiles and glazed single
fired tiles intended for both wall and floor (monoporosa).
Their inclusion (limited, though, to 20/22 and 14/16% respectively) allows bod-
ies of suitable absorption values (especially for glazing purposes) and almost zero
shrinkage (or with a maximum shrinkage of 0.5~0.6%) to be produced. This last
characteristic has, in the past, allowed high-stack firing technology to be used in
situations that would not be feasible if shrinkage were too high.
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Raw materials for ceramic bodies
In single firing wall tiles limestone and dolomite are used (as a natural calcare-
ous clay corrective) in CaCO3 percentages of up to 12-15%, giving the tiles, thanks
to the formation of calcium silicates and magnesium, low firing shrinkage (< 1%).
Their presence, however, complicates firing (especially pre-heating) of the glazes,
as heat-induced dissociation of the carbonates causes CO2 emissions which must
pass through the glaze without hindrance so as not to alter it and cause pin hole
defects (called de-gassing effects).
In this sense it is also possible to make modifications to porcelain tile bodies by
adding carbonates of pre-fixed particle size distribution to the slip or the powder,
thus obtaining a new body suitable for the production of quality wall tiles.
The presence of carbonates, then, generally leads to an increase in the expan-
sion coefficient, thus improving compatibility with the majority of commercially
available glazes.
Consequently, carbonates are used extensively in the manufacture of majolica
and earthenware.
Dolomite and magnesite are also used in the manufacture of basic refractory
items.
Carbonate-rich clays are usually used in the manufacture of extruded products.
At this point it is important to point out the importance of the so-called coquinas.
These are calcareous fragments sometimes larger than 1 cm. They derive from de-
posits of chemical origin, or sometimes originate from the shell fragments of long-
dead marine animals (bivalves, gastropods, brachiopods, etc.). In both cases, when-
ever raw materials containing these elements are extruded or dry-ground, prob-
lems can arise. With tiles, dimpled white-yellow spots appear on the body, leading
to pin-holing of the glaze.
In the case of bricks the coquina fragments, partially dehydrated after firing,
can re-expand as a result of re-hydration or re-absorption of atmospheric CO2: if
this happens after the product has been laid flaking and breakage will result, with
easily imaginable effects on the appearance of walls.
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ACCESSORY MINERALS
PRESENT IN CERAMIC RAW MATERIALS
Halloysite
Mineralogical structure
A mineral from the kaolinite family, it associates a tetrahedral sheet with an
octahedral one that has the quality of being hydrous (dioctahedral) (Fig. 77).
The intervening layer of water molecules gives the sheets a certain mobility.
They thus tend to roll up into cylinders, as examination under an electron micro-
scope clearly shows.
This characteristic behaviour can be explained by examination of the differen-
tial tensions between the tetrahedral sheet and the octahedral one.
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Raw materials for ceramic bodies
However, the attraction between the sheets is evidently higher than the differen-
tial tension: if the contrary were true the lattice itself would be destroyed.
The cylinders can, however, unroll and flatten out, turning into metalloysite,
characterised by lower water content and a lattice distance of 7.4 Å (against the
10.1 Å of halloysite).
Metalloysite loses its entire water layer at around 200 °C and irreversibly chang-
es into a kaolinite-like structure.
In passing from kaolinite to metalloysite to halloysite a progressive increase in
hydration is observed, accompanied by an increased degree of disorder of the lat-
tice.
It is interesting to note how crystal size in the various kaolinite-family minerals
depends on the degree of stability (and disorder) of the structure.
Note that the smaller particles belong to halloysite while the larger ones are
seen in kaolinite.
Chemical composition
Al2 (X2 O5) (OH)4 2H2O
X = element in a tetrahedral position (to all intents and purpose this is Si4+ only,
in that substitutions with vicariants such as Al3+ or Fe3+ are almost never observed:
as is known, the latter result in the structure lacking a positive charge).
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Some American States (Utah, Nevada, Idaho, North Carolina and Georgia) have
particularly extensive extraction sites.
The most important European deposits are found in France (Dordoigne) while
minor deposits exist in Czechoslovakia and ex-Yugoslavia.
Quarries are generally of the open-cast type and employ standard earth-moving
machinery (bulldozers, scrapers, hydraulic excavators, etc.).
HALLOYSITE
METALLOYSITE
Fig. 78. Diffractogram pattern for halloysite, characterised by an intense reflection at about 4.4 Å, often
stronger than the basal ones at 7.2-7.4 Å and about 3.6 Å, which are broad and asymmetric towards
lower angles.
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Raw materials for ceramic bodies
The differential thermal analysis (DTA) diagram for halloysite reveals a charac-
teristic endothermic peak just before 200 °C associated with the loss of interlayer
water; at higher temperatures behaviour is similar to that of kaolinite. A new en-
dothermic peak starts at 450 °C as a consequence of removal of the OH- hydroxyls
while at around 980 °C, in connection with the crystallisation of mullite or alumina,
a distinct exothermic peak is observed.
Correspondingly, thermogravimetric (TG) analysis reveals a sharp weight loss
just before 200 °C and towards 450 °C, connected with removal of the inter-layer
water and the OH hydroxyls respectively.
No variation, of course, is noted at 980 °C as this exothermic reaction does not
involve the removal of material, just the freeing of bond energy.
Dilatometry analysis shows initial, weak dilatation balanced by evident shrink-
age just beyond 150 °C: this is caused by the removal of interlayer water.
Once this phase is complete shrinkage continues, albeit on a much shallower
gradient, until just beyond 450 °C when a new, marked contraction occurs (loss of
the OH- hydroxyls); that contraction persists towards 880 °C at which point sinter-
ing reactions take hold and steeper-gradient shrinkage is observed, with conse-
quent softening of the sample.
Note that intense drying shrinkage makes removal of the water a real problem
and that this operation often leads to the fracture of a substantial number of
pieces.
Ceramic uses
In practice, halloysite is rarely used in the manufacture of tiles whatever their
colour (usually a coarse halloysite is used in combination with other raw materi-
als); it is, in fact, best avoided as there are considerable complications at the dry-
ing stage.
It is sometimes employed in the manufacture of bricks (especially in the USA),
fire-bricks and refractories (bear in mind that this is, in any case, a raw material of
high alumina content).
The use of halloysite in these products is justified when the plasticity of the mix
needs to be increased.
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Finally, note that this material has rather peculiar rheological properties: conse-
quently, its use in products involving wet grinding of raw materials leads to poor
deflocculation of the body.
On the whole, then, utilisation of a halloysite raw material must be well con-
tained (within 5-20%): such percentages will allow for fairly generalised use (pot-
tery, porous and vitrified tiles).
Mineralogical structure
Attapulgite: this is a silicon inosilicate. The tetrahedron apexes alternately point
in opposing directions; this distribution is coordinated between the two chains in
the sense that apexes pointing towards the other chain will find, on the latter, a
specular situation.
Octahedrally coordinated Al3+ and Mg2+ cations lie between the apexes of the
tetrahedrons of these two chains.
The structure is completed by the introduction of OH- hydroxyls at the extrem-
ity of the octahedrally-arranged cations while the interstices are filled with water
molecules.
Sepiolite: again an inosilicate, very similar in structure to attapulgite, yet differs
in terms of the size of the platelets and the minimum possibility of cation substitu-
tion. Sepiolite platelets are 50% larger than attapulgite ones.
Vermiculite: a phyllosilicate, the structure of which consists of overlaying mica-
like silicon units; on the whole the construction has a well-defined negative charge
(as observed in chlorite minerals) balanced by the (hydrous) Mg ions inserted be-
tween the silicate layers. The magnesium may be substituted by other cations. Dio-
ctahedral and trioctahedral forms also exist. This mineral has the characteristic,
when heated rapidly, of swelling up to 50 times its initial size and giving rise to
worm-like elements.
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Raw materials for ceramic bodies
Chemical composition
Attapulgite: (Mg, Al)2 Si4O10(OH) . 4H2O
The substitutions that lead to a deficit of valence are balanced by the insertion
of alkaline-earth cations.
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being examined. Nevertheless, above 100 °C, there is a distinct endothermic peak
associated with the removal of zeolite water. This is followed by a second peak
(towards 600 °C) associated with evaporation of the OH- hydroxyls. Since these are
effectively weight losses they are also show up in TG analysis as the customary on-
diagram gradient increases.
Sepiolite
The DTA curve shows a first endothermic peak at around 150 °C (loss of inter-
layer water) and a second at 800 °C (removal of the OH- hydroxyls), while towards
850 °C a net endothermic peak caused by neo-crystallisation of enstatite (SiO2 .MgO)
and cristobalite (SiO2) is observed.
Vermiculite
Differential thermal analysis gives a marked endothermic peak at around 150 °C
with a lower endothermic effect at 180 °C; both refer to the removal of water mol-
ecules. At 550 °C, and more markedly at 850 °C, endothermic peaks associated with
hydroxyl removal are clearly observed (Fig. 81-82).
All the reactions involve removal of material and consequently show up on the
TG curve too.
Ceramic uses
Use in the ceramic industry is extremely limited. Attapulgite and sepiolite (min-
erals rich in magnesium) can be employed in the production of magnesium glazes.
The attapulgite of Argenteuil has been used in the manufacture of Sèvres porce-
lain. Sepiolite is introduced into compositions for porous tiles, insulation porcelains,
pottery and sanitaryware. Thanks to the noted porosity of its structure it may also
be used in the production of insulating refractory bricks.
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Raw materials for ceramic bodies
sepiolite
quartz
potassium feldspar
Fig. 80. Example of a diffractogram for a sepiolite sample containing quartz and potassic feldspar
impurities.
Temperature °C
Fig. 81. DTA curves for vermiculite. The overall configuration of the endothermic effect at 100-250
°C is modelled mainly by the type of interlayer cation: A = magnesium; B = calcium, C = sodium.
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Micas
126
Raw materials for ceramic bodies
The structure of these minerals is similar to that of illite; they consist, in fact,
of two layers of silicon tetrahedrons enclosing a layer of aluminum octahedrons.
Numerous substitutions come into play, creating electrical imbalances that are ad-
justed by the introduction of new ions.
Biotite (or ferroan mica) has a brown-blackish, shiny appearance and is a prime
constituent of granites, rocks related to feldspars: consequently, it is often en-
countered as a contaminant in mined feldspar deposits.
The presence of biotite, within certain limits, correlates with that of anorthite
(calcium feldspar). During alteration of the source rocks (weathering, contact meta-
morphism etc.) it can easily alter into sericite, and is thus found only rarely in sedi-
mentary rocks. Muscovite (or potassic mica) appears in the form of metallic-like,
hexagonally-shaped, shiny, flexible platelets that flake easily. These platelets can
become enormous (even over 1 metre), as seen in Indian deposits. Like biotite, it is
present in certain types of granite, alteration transforming it into illite; neverthe-
less, it is frequently found in sedimentary rocks (clays and sands), sometimes in
significant percentages (even over 10%).
Sericite appears as long flat greenish fragments or needles. In certain sedimenta-
ry rocks its lithoid, non-carbonate nature (as in certain sandstones) constitutes, to-
gether with the ferrous hydroxides, the cement that binds the various components.
Diffractometry analysis of biotite (using Cu Kα radiation) highlights the character-
istic lattice distances (10.1 Å, 3.37 Å, 2.66 Å, 2.45 Å, 2.18 Å) with corresponding
peaks at the following angles: 8.70, 26.42, 33.66 and 41.40° 2ϑ.
A similar analysis of muscovite gives peaks at 26.80, 8.86, 34, 88, 45, 50 and
29.82° corresponding to lattice distances of 3.32, 9.95, 2.57, 1.99 and 2.99 Å.
DTA of biotite yields a completely flat line up to 1000 °C, while the same test on
muscovite shows an endothermic peak between 800 and 950 °C corresponding to
removal of the OH- hydroxyls (Fig. 83).
Biotite constitutes a significant problem in certain feldspar deposits, where only
high-intensity magnetic separators can remove it. However, it is not uncommon for
the separators to attract feldspar and quartz particles that were electrically charged
during grinding. In such cases a choice usually has to be made between somewhat
partial separation of the biotite (resulting in commercialisation of a product that,
after firing, varies in colour from grey to blackish and is blemished by black dots) or
a consistent loss of useful material which the magnetic separators inevitably re-
move together with the mica.
When present in substantial percentages, muscovite too can cause serious diffi-
culties.
A well-known example of this problem is Cornish Stone, extraction of which
ceased because the deposit was steadily becoming more and more muscovite-rich.
While muscovite can be split from the other components by winnowing and
floatation, such processes are very expensive, thus pricing the material out of the
market, which automatically selects products unaffected by this problem that do
not necessitate separation systems.
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Mineral hydroxides
128
Raw materials for ceramic bodies
DTA and TGA analysis of the various minerals give the following dehydration
temperatures:
gibbsite: from 240 to 380 °C
diaspore: from 410 to 570 °C
bohemite: from 450 to 580 °C
goethite: starting from 250 °C.
Soluble salts
The geological history of the earth shows that the formation of sedimentary
ceramic raw material deposits is closely linked to that of soluble salt minerals. The
presence of these minerals is caused by precipitation conditions in sea water at the
same time as fine particles from suspensions of continental origin are deposited.
Hence the presence of such mineral contaminants in clayey deposits of sedi-
mentary origin. Nevertheless it should not be forgotten that the (mostly lacustrine)
continental deposits also derive from the break-up of pre-existing rocks that may,
in turn, have been of sedimentary origin, thus allowing transfer of soluble salts
from one generation of rocks to the next.
Soluble salts show up in a variety of ways.
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Fig. 84. List of the main aluminum, manganese, and titanium oxide and/or ferrous hydroxide reflec-
tions in decreasing interplanar spacing order.
130
Raw materials for ceramic bodies
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They assume many different forms, ranging from thinly-spread films of varying
consistency and hardness to protruding crystallisations, soft and fragile or compact
and tough.
As usual, differential thermal analysis (DTA) provides useful information as to
the exo and endothermic reactions that take place during heating. Gypsum (dihy-
drate calcium sulphate) shows a first endothermic peak at 140 °C (transformation
into a hemi-hydrate), a second, smaller one at 150 °C (transformation in anhydride)
and a tiny exothermic one at 350 °C indicating the change from soluble anhydride
to insoluble anhydride.
At 1125 °C the anhydride changes from type α to type β (small endothermic
peak) and dissociation of CaO from SO3 begins.
Pyrolysis of the chlorides, instead, is complete by 700 °C; the magnesium sul-
phate begins to disassociate towards 900 °C, while in the case of sodium sulphate
such reactions may persist beyond 1000 °C. It thus follows that neo-genesis of
alkaline sulphates and alkaline-earths is almost completely annulled in ceramic bodies
that sinter at temperatures above 1000 °C.
Finally, in the case of ferric sulphate, pyrolysis begins towards 170 °C, while in
magnesium sulphate it is only seen above 400 °C.
As regards its influence on slip rheology it can be stated that the presence of
dissociated sodium and potassium soluble salts aids deflocculation while calcium,
magnesium and even iron ones cause flocculation.
Thixotropy too depends on the surface properties of the colloidal particles of
clay and is significantly influenced by the electrolytes that act on alterations be-
tween the particles.
It is known that the quantity of alkaline chlorides is directly proportional to the
tendency towards formation of kaolinitic clay suspension gels and inversely pro-
portional in the case of slips consisting of montmorillonites. The presence of sol-
uble salts can thus produce opposing effects which depend on the clayey minerals
present.
The firing behaviour of the main soluble salts is characterised by pyrolysis, with
consequent elimination of the gaseous phase and dehydration phenomena. For ex-
ample, the loss of the gypsum water molecules occurs at low temperature, overlap-
ping water loss in expandable-lattice clayey minerals, thus contributing to total
shrinkage of the piece at the drying and preheating stage.
The consequences of the above-cited phenomena increase in significance as fir-
ing cycle times shorten.
Certain reactions, almost insignificant in traditional tunnel kiln cycles, cause
huge problems in the rapid and ultra-rapid cycles of single firing items, difficulties
that can often only be resolved by eliminating certain raw materials.
Where rapid cycles are employed a further complication is posed by the re-
sistance of the glaze, as it covers a body that has not been stabilised by a first
firing.
Pyrolysis reactions involving the removal of gas when the glaze has high fluid-
ity, or the employment of unsuitable glazes, give rise to small craters on the face
of the tile that damage the finished item irreparably.
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Raw materials for ceramic bodies
Single firing glazes will only let gas bubbles pass through where fusibility is
extremely high or extremely low; in the former case low-temperature fusibility al-
lows re-closure of craters opened up by bubbles breaking the surface.
In the latter, the glaze only fuses at high temperature and thus preserves an
earth-like porosity well into the firing process, allowing gas bubbles to pass through
without hindrance.
Some authors claim that soluble salts cause black core problems, yet the source
of such defects is actually the presence of non-mineral carbon and iron.
The main effect of soluble salts on unglazed fired pieces is the appearance of
efflorescence.
This term refers to deposits that settle on the surface of the biscuit (sometimes
on the dried product too) by way of the mineral salt precipitation that occurs under
saturation conditions.
This phenomenon, generally seen on bricks, but also on both pressed and ex-
truded tiles, only occurs when the ceramic body is porous enough to allow, within
its interior, migration of salt solutions.
On reaching the surface, these give rise to rapid water evaporation. The raw
material must, of course, have a relatively high content of such salts (and alkaline
oxides and lime) or they must form during firing by way of pyrolysis of the pyrite
or the presence of sulphur in the kiln fuel. The phenomenon is perceptible as soon
as fired products contain more than 0.5%.
Efflorescence is, in order of frequency (on dried and fired products), caused by
sodium sulphates, calcium, potassium and magnesium, the carbonates of these met-
als and chlorides and alkaline nitrates. On fired items sulpho-aluminates and alka-
line carbonates are also observed.
The formation of efflorescence is greatly influenced by factors affecting the move-
ment of saline solutions inside the fired bodies (dimensions and distribution of
pores) and the way in which water evaporation occurs: bear in mind that, under
certain circumstances, this takes place not on the surface but in the interior of the
ceramic body.
Where salts migrate to the surface of pressed tiles (generally seen on double
firing wall tiles) there may be an accumulation of alkali-containing salts in those
zones subject to greater heating during drying (i.e. tile edges).
The extreme consequence of this phenomenon, also caused by re-wetting of the
biscuit during glazing, is the alteration of the chemical composition of the glazes at
the edges of the tile via increased contribution of fusible salts; it makes this part of
the tile, already subject to greater interaction with the heat of the kiln, even more
sensitive to temperature variations and, on average, more fusible. This can lead to
the side of the tile having an overly-fused, clearer-coloured appearance generated
by air bubbles in the glaze.
A similar phenomenon generated by salt migration is seen on porcelain tiles.
This defect is generated by salts building up at the tile support points during dry-
ing, thus giving rise to zones with a greater post-firing vitreous phase content of
shinier appearance.
In both cases the problem can be resolved in addition to attempting to elimi-
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nate salt-carrying raw materials by making drastic changes to the drying cycle,
accelerating it to the limits of piece bending strength so as to aid high-speed water
evaporation and thus prevent migration and accumulation of salts on certain parts
of the tile.
Vegetable substances (some examples are given in Fig. 86) found in clayey raw
materials can be divided into two main groups: non-carbonized and carbonized
materials.
The former include roots, wood fragments, leaves and humic acids; these ele-
ments are largely present in recent deposits or those connected with the pedolith
layer, or occur simply as a result of incomplete clearing of vegetation prior to ex-
traction.
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Raw materials for ceramic bodies
These vegetable substances are normally eliminated during the firing process,
sometimes with the aid of oxidising substances specially added to the body: they
start combusting at around 250 °C and stop at approximately 450 °C.
The latter group consisting of various types of carbon and generally found in
older geological formations is considerably more stable. Normally immune to treat-
ment with oxidants, these materials will, during firing, burn away in the 300 to 600
°C range.
The presence of vegetable substances causes various difficulties in the produc-
tion of both single and double firing items.
In fast single firing especially where cycles are less than an hour, iron minerals
are present (red body) and manufacturers aim to produce low-absorption bodies
centrally-placed, black ellipsoidal stains (black core) can form and, in the most
serious cases, there is intense swelling. These result from incomplete combustion
of the organic substances, giving rise to graphitic carbon which blackens the ce-
ramic body, while the CO2 from the burnt part, unable to pass through the piece,
causes swelling.
Furthermore, where inorganic salts are present, Na2SO4 salts also form: these
contribute to the formation of vitreous phases, blackened or darkened by the pres-
ence of chromophore cations (e.g. Fe, Cu, Cr etc.).
Where mineral sulphides (e.g. iron or copper sulphides) are present complex
reactions take place, giving rise to combinations between the silica and sulphide
decomposition products (Fig. 87) and resulting in a black, highly fusible glaze.
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The actual appearance of such phenomena will also depend on other factors
such as powder grain size and moisture content, pressing force, firing curves and
in-kiln atmosphere. Negative effects can be reduced by:
introducing lean (non-plastic) raw materials into the composition (sands, lapilli,
chamotte)
adding oxidants to the composition (MnO2, various nitrates)
increasing the particle size of components and powders
reducing the moisture content of the powders (but taking care not to unduly
lower the dry bending strength)
lowering pressing pressure
applying a more appropriate firing curve that makes the 250-600 °C interval last
as long as possible
establishing an in-kiln atmosphere that is as oxidising as possible.
This mineral is generated under hydrothermal conditions that often lead to the
kaolinization of feldspathic veins. Thats why it is usually found together with ka-
olin, as seen in the famous kaolinitic deposit of Djebel Debar (Algeria). Observation
136
Raw materials for ceramic bodies
of a DTA chart for this material shows a first endothermic peak at 550 °C (water
loss) while a second (at 850 °C) indicates the removal of a good part of the sulphur
dioxide that accompanies the formation of alumina and potassium sulphate.
The exothermic peak visible just after 700 °C has yet to be fully understood. The
freeing of sulphur trioxide involves problems cited previously.
Vitreous materials
Found in clayey or sandy deposits when, during genesis, volcanic materials are
introduced at the same time as sedimentation of the water-suspended particles.
When small, such products may be transported (by wind) a long way from the
point of origin (i.e. from the volcanoes). The characteristic vitreous state of these
materials is unstable and tends to evolve towards the crystalline; however, it is a
transformation that requires an extremely long time to develop and reach comple-
tion. This explains why vitreous particles of this type are still found in sediments
that are not particularly recent (as with certain red-beds of the Emilia Apennines).
The presence of these materials gives rise to melting dark dots on the biscuit
surface; with certain glaze types, this problem can become more marked and lead to
production problems.
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138
Raw materials for ceramic bodies
Chapter IV
In selecting raw materials for the production of ceramic frits the following crite-
ria must be taken into consideration:
consistency of chemical composition over time
consistency of particle size distribution over time
low Fe and Cr content
absence of difficult-to-melt minerals (kyanite and sillimanite) that, remaining in
the frit as unmolten elements, compromise its quality
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last but not least, materials should be economically viable and readily avail-
able.
The most important and thus the most commonly used materials are:
quartzes and sands
sodium feldspars
potassium feldspars
boric acid
pentahydrate borax
colemanite (calcium borate)
anhydrous borax (sodium borate)
ulexite (sodium and calcium borate)
calcium carbonate
zirconium silicate
zinc oxide
barium carbonate
dolomite
kaolin.
Such a variety of raw materials means there is a need to make basic choices in
terms of storage and handling solutions. It should be noted, in fact, that some of
the above-cited raw materials cannot be stored in silos (or, rather, not in a way that
is straightforward).
Moreover, materials such as barium carbonate, titanium dioxide and potassium
nitrate are not available in bulk.
Zinc oxide differs from other materials in that, in its light form, it cannot be
stored in, or, rather, extracted from, silos: consequently, it is now common practice
to employ so-called heavy zinc oxide, a material without any particular handling
problems.
Given the above difficulties and the simple fact that they are often utilised in
small quantities these raw materials are, then, generally stored in sacks rather than
silos, while others may be delivered in bulk by truck.
Information regarding the type of minerals from which these materials are ex-
tracted, refining processes and chemical/particle size distribution limits that make
these compounds suitable/unsuitable for fusion is given below (see p. 145).
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Raw materials for frits and glazes
Final ceramic surface coatings are, then, made up of thin vitreous layers. They
are applied in aqueous suspensions obtained by water grinding the frit and any
other raw components in the composition onto fired or dried unfired ceramic
bodies.
A certain glass type, known as cristallina, is, on some wall tiles, applied on
already glazed and decorated tiles to obtain brighter and deeper colour effects.
Another characteristic glaze is maiolica, highly opaque, usually applied thickly
to give a rich white and glossy tile surface. The glaze get its opacity from the frit
opacifier, usually, zirconium silicate.
There are also frits for specific, finely-targeted use, such as those employed in
monoporosa. In addition to opacity and brilliance, these must also have very high
softening points (1020-1050 °C) so as to favour emission of the gas (CO2) emitted
from the body during firing.
With glazes, instead, the diffusion of vitreous single firing products has meant
that, in addition to the concept of opacity other factors such as surface appearance
(matt, semi-matt) should be considered.
This chapter will deal first with the theoretical aspects of the nature of the
glass, and then provide a review of the different types of frit and, finally, glaze
compounds.
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Tab. 8.
The key physical characteristic of glasses is that they are isotropic while crys-
talline-structured solid bodies are known to be anisotropic.
In the past, this led to the belief that glasses were amorphous substances; how-
ever, recent studies by Zachariasen and Warren have established that the character-
istic tetrahedral coordination of silicon is maintained in glass too.
While these tetrahedrons are, in crystals, arranged as a strictly regular geomet-
ric construction, in glasses they are arranged chaotically, without periodicity or
symmetry.
So while we can speak of a glass lattice, it must be born in mind that this is a
disordered, contorted lattice essentially made up of silicon and oxygen.
Two-dimensional illustrations of the tetrahedral arrangement in crystal-type
silica and molten silica are shown in figures 88 and 89 respectively.
Like silica glass, common glass also features this irregular arrangement of tet-
rahedrons; moreover, in the latter the ions of the other constituent elements fill the
gaps left by the silicon and oxygen.
The bonds in the glass lattice are not all equivalent as they are in crystalline
lattices; consequently, the energy needed to break them apart is differentiated.
Thus, as temperature rises the level of thermo-agitation energy increases until a
level sufficient to break the weakest bonds is reached.
Continued raising of the temperature results in the gradual breakdown of the
lattice and the corresponding, progressive liquefaction of the glass.
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Raw materials for frits and glazes
For every temperature, then, there is a corresponding glass structure that char-
acterises it. During solidification, as the temperature gradually falls, the glass re-
establishes the bonds and tends to take on the structural state associated with lower
energy levels. However, as the increase in viscosity around the transition point is
somewhat rapid, the internal state of the solidified glass corresponds to that of
higher temperatures. Consequently, structural instability arises: while this instabil-
ity necessarily tends to evolve it does so over a very long time interval (Tab. 9).
Anorhtite
Gehlenite
Sphene
Gahnite
Willemite
Cristobalite
Tridymite
Spodumene
Magnesium titanate
Wollastonite
Rutile
Cordierite
Forsterite
Enstatite
Diopside
Zirconium silicate
Zirconium oxide
Celsian
Leucite
Tab. 9. Some crystalline components in de-vitrified frits.
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The cations, which, in the oxide state, can be obtained in the vitreous state sim-
ply by heating and are thus known as lattice-forming cations are Si4+ and B3+.
While silicon forms apex-linked tetrahedrons, the coordination 3 boron forms
equilateral triangles at the centre of which lies the B3+ ion.
Since the silicon ion has four bonds, while the boron ion has just three, it can be
seen how boric glass is less viscous and thus more fusible.
The fluxing cations, also known as lattice modifiers, split the links between the
tetrahedrons once they are added in the oxide state:
O O O O
O Si O Si O by introduction of Na2O O Si O O Si O
O O O Na Na O
These ions generally take up positions in the interstices between the siliceous
polyhedrons.
The greater the number of sodium ions introduced, the greater the number of
splits, and so on, thus diminishing the viscosity of the glass. Furthermore, the high
number of splits between the tetrahedrons ends up compromising the existence of
the vitreous state itself because the more freedom the tetrahedrons gain, the more
marked is their tendency to take on the regular structure of crystals and, conse-
quently, of devitrified glass (Tab. 9).
O O O O
O Si O Si O by introduction of CaO O Si O O Si O
O O O Ca O
Stabilising cations are lattice modifiers too: unlike alkaline cations, which, be-
cause of their weak ionic potential are only loosely linked to the lattice and thus
easily removed, resulting in alteration of the glass, alkaline-earth cations have twice
as much ionic potential and therefore reinforce the lattice structure of the glass and
act as stabilisers.
The replacement of a modifier ion (Na) with another of higher electrical charge
(Ca), having more or less the same dimensions, causes:
an increase in density, because the greater attractive force exerted on the adja-
cent oxygen ions gives rise to greater compactness
an increased refractive index as a result of the increased density
a reduction in electrical conductivity stemming from reduced mobility of the
cations, in turn caused by increased bond energy
increased viscosity for the same above-cited reason.
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Raw materials for frits and glazes
1 - Silica (SiO2)
Introduced in the form of quartz, quartz sands, feldspathic sands and feld-
spars.
Silica is the prime component of vitreous compositions as it has the property of
vitrifying under the effect of the fluxes within a very broad temperature range. The
fluxes or modifiers are: PbO, B2O3 , K2O, Na2O and Li2O. Glazes rich in silica are
highly resistant to chemical agents and are extremely hard. The higher the silica
content in a glaze the higher its firing temperature.
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LATTICE FORMERS
INTERMEDIATES
MODIFIERS
146
Raw materials for frits and glazes
high toxicity, proportional to lead content and as a function of the form in which
the glass is bound
high sensitivity to acid attack where oxide content exceeds a certain propor-
tion.
6 - Alumina (Al2O3)
Introduced as calcined alumina or alumina hydrate, feldspars, kaolin, corun-
dum.
In glazes in appropriate proportions (4-8%) it confers, in the case of low-temper-
ature glazes, the following:
increased viscosity
reduced tendency to de-vitrify (crystallization)
increased bending strength
reduced expansion coefficient
increased resistance to acids
improved opacity (introduced in high percentages in concordance with the glaze
firing temperature).
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148
Raw materials for frits and glazes
Adding TiO2 colours the glass: even at just 2% yellowing is observed. Simulta-
neously the surface of the finishing glaze takes on a matt appearance, becoming
hard and coarse as oxide percentages increase.
It has opacifying properties that improve in the absence of B2O3 and especially
where the glass composition is rich in Al2O3 and added in the mill; under these
conditions the colour fades.
These characteristics are particularly evident if TiO2 is introduced into the glass
as anatase, while, where introduced as rutile, it loses its de-vitrifying characteristics
until, in high percentages at high firing temperatures, it gives rise to needle-shaped
crystals.
Crystallisation occurs mainly in high-fusibility glasses.
The most commonly used glaze opacifiers are micronized products, while pow-
ders are used in frit melting and sands are used as hardeners or fillers. Low firing
temperature glazes, opacifiers with zirconates, often have non-smooth surfaces, un-
doubtedly in relation to their highly viscous nature.
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Types of frit
Tab. 11.
150
Raw materials for frits and glazes
Tab. 12.
Frits are used as bases in finishing glazes and in low-temperature glazes to ren-
der the components insoluble.
The market offers a wide range of frits having different fusibility, glossing, opaci-
fication and matting performance specifications.
They can be grouped as follows:
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centage of SiO2 (50-60%) and a low percentage of fluxing elements (20-25%, in-
cluding Na2 O-K2 O-PbO-B2O3).
The rest of the composition consists of stabilisers (Al2O3-ZnO-CaO-BaO-MgO),
almost always accounting for only very limited percentages (max 7-9%).
These frits are mainly used in the preparation of transparent glazes although
they are occasionally employed in low percentages in certain glazes fired at low
temperature.
At temperatures above 1100 °C these are employed albeit in low percentages
in the preparation of almost all glazes so as to improve vitrification and confer
fusibility.
c - for monoporosa
For porous fast single firing technology, the frit will have a radically different
composition on account of specific needs of the bodies, which generally have a high
carbonate content (8-14%).
This has thus resulted in the development and fine-tuning of frits with high
melting points that soften above 950 °C so as to allow complete emission of the
carbon dioxide formed during decomposition of the calcite and/or dolomite.
Examination under a heating microscope must show such frits to have a very
high softening point together with a sphere point close to that of the previously
described frit.
To satisfy these requisites and aid/trigger this eutectic fusion it has been nec-
essary to increase CaO, ZnO, MgO and BaO oxide content (with respect to double
firing).
At the same time the percentage of fluxing oxides has been reduced. The
goal was to produce fast frits (i.e. capable of melting suddenly at high temper-
ature).
Opacification is achieved with the aid of zirconium silicate, introduced into the
composition in quantities ranging from 8 to 14%.
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Raw materials for frits and glazes
Na2O → decrease
N
K2O → increase
Na2O+K2O → decrease
CaO → increase
ZnO → increase
BaO → increase
MgO → increase
B2O3 → decrease
SiO2 → decrease
These frits are mainly used in the preparation of glossy white glazes of both the
high and low-temperature firing type.
Of course, in glazes fired at high temperature the percentage of frit diminishes
considerably in favour of the raw materials. In the preparation of glazes other than
glossy whites these frits are used only occasionally.
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The widespread use of these frits stems from their fusibility which favours in-
mill introduction of high quantities of raw material and devitrification of all the
154
Raw materials for frits and glazes
matting elements. In this way a range of glazes with significant technical and
aesthetic differences can be obtained simply by using just one frit and varying in-
mill addition.
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Cadmium and selenium frits are used on their own to obtain the respective glaz-
es, unable to be produced in any other form.
Coloured frits are only used to obtain certain coloured transparents or to intro-
duce colorants in a stabilised form in flame or disc applications.
Tables 13 and 14 show approximate compositions and key characteristics of the
most commonly used frits in traditional/fast double firing and monoporosa tech-
nology (i.e. transparent, glossy and matt white).
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Raw materials for frits and glazes
ELEMENTS A B C A B C A B C
alkali 8 6 4 8 7 5 1
MgO 1 1 2
CaO 3 8 12 3 6 9 5 40 40
BaO 3 3
ZnO 1 10 11 1 6 13 28
PbO 4 15 11 11
Al2O3 8 8 9 6 7 6 1
B2O3 19 6 3 15 11 5 10 6 6
SiO2 58 54 60 58 52 52 40 43 43
ZrO2 9 11 8
TiO2
Firing T 970 1040 1110 970 1040 1110 970 1040 1110
Softening T 890 950 1020 920 940 1040 750 1100 1100
Semi-sph. T 1160 1150 1120 1240 1210 1140 1000 1150 1150
Firing cycle 10h 40min. 50min. 10h 40min. 50min. 10h 40min. 50min.
Frit kiln T 1350 1450 1470 1350 1450 1520 1300 1350 1350
CT CR CM BT BR BM MT MR MM
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ELEMENTS A B C D E F G H I
BaO 0-2
ZrO2 0-5
TiO2 7-10
A bisilicate
B rocaille
C monosilicate
D leadfree flux
E monoboron
F lustre glaze
G ZnO matt
H CaO matt
I TiO2 matt
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Raw materials for frits and glazes
Õ engobe Ô
FAST DOUBLE-
FIRING
Õ matt Ô
POROUS SIGLE-
FIRING
glazes for silk-screen
Õ Ô
printing
particular glazes Ô
waxy glazes Ô
VITRIFIED
SINGLE-FIRING
majolica glazes Ô
cotto-like glazes Ô
crystalline glazes Ô
technical glazes Ô
These factors have given rise to the present-day situation where different tech-
nologies are used to produce commercially overlapping products. Such technologies
include:
traditional double firing
fast double firing
porous single firing (monoporosa)
vitrified single firing.
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Each of these technologies, which can themselves be split into sub-groups, re-
quires glazes of specific chemical-physical characteristics.
This technology virtually the only one up until the 1960s involved dry ground
and pressed bodies fired in tunnel kilns at around 1000-1150 °C in a 15-30 hr cycle.
The obtained ceramic biscuit, known as cottoforte, was characterised by high water
absorption and porosity.
This was sent on to the glazing line and then fired again at around 950 °C to
1050 °C in a further 12-hr cycle. Until just a few decades ago virtually all commer-
cially available tiles glossy, matt, rustic and surface-effects glaze were produced
this way.
To avoid giving an out-of-date classification of double firing glazes, note that
the glazes now employed in nearly all double firing operations are the following:
Transparent glaze
This product is normally used to manufacture tiles with a transparent, deep-
glaze look.
The application sequence usually involves a layer of engobe made up of frits of
the zirconium white and/or transparent alkaline type to which feldspar raw materi-
als, zirconium silicates (to improve covering), clays and kaolins (to adjust rheology)
may be added on top of which the glaze is applied.
In addition to these components, double firing engobes may also contain other
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Raw materials for frits and glazes
frits having specific functions: as fluxes to improve anchoring to the body, or special
frits to increase the expansion coefficient of the layer of glaze in order to prevent
excessive tile convexity.
After the engobe the transparent glaze may be applied directly or there may be
an intervening second layer of glaze which regulates the fusibility between them.
Then the film of true transparent glaze is applied.
Silk-screen printing can be before or after the transparent layer to obtain a deep
or surface effect.
Chemical-physical parameters are the same as those for zirconium whites, ex-
cept for the absence of zirconium silicate which gives the finishing glaze a transpar-
ent appearance.
Any introduction of additives is effected as with zirconium whites. In quantita-
tive terms it should be born in mind that the engobes and semi-glazes usually have
different viscosity characteristics from those of whites and transparents in that
they have a higher plastic raw material content (clays and kaolins).
Matt glazes
These cover a decidedly smaller wall tile market share (10-20%) than glossy
glazes. They are formulated as a function of devitrification with the development
of a matt surface.
Devitrification is generally caused by an excess of calcium or zinc. In this firing
technology both alumina and zirconia can also be used as they contribute to the
creation of a matt surface in addition to conferring their other typical characteris-
tics.
Zinc, titanium, calcium, barium and magnesium oxides matt by crystallisation
while aluminum oxide and sometimes zirconium silicate matt by hardening.
Glazes matted with zinc and titanium oxides normally consist of a fusible vitre-
ous base and tend to be leaded.
Aesthetically, they are an imperfect white, tending to grey where zinc is present
and yellow where titanium is included.
Glazes matted with alkaline-earth oxides are always white in colour and are nor-
mally highly viscous. Glazes matted by hardening always consist of fusible vitreous
bases (see frit group 4) thoroughly hardened with alumina, corundum and zirconi-
um silicate.
When the matting element is alumina or corundum, satin-finish glazes are ob-
tained while, with zirconium silicate as a matting element, stone-like glazes are
obtained.
Low-temperature matt glazes (ZnO-CaO) are directly made with the relative
frits (see frit group 6) in high percentages: at higher firing temperatures, raw mate-
rials added to the mill are used.
One of the most frequent problems is a varying degree of matt across the kiln
cross-section. In some cases partially glossy tiles are produced where in-kiln burn-
ers are too close to the product and create microclimates unfavourable for devitrifi-
cation.
Matt surfaces are also influenced by in-kiln cooling conditions. Gradual cooling,
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Engobes
These are applied before the glazes and have a wide range of functions.
For example, engobes can homogenise the degree of water absorption in subse-
quent applications.
They are thus able to reduce the dimples caused by inconstant absorption across
the surface of the body.
Engobes also have the function of slowing down water absorption, thus pre-
venting the formation of air bubbles in successive applications. Ceramic functions
include the slowing down and, above all, splitting up of the gas bubbles that rise up
from the body during firing because of pyrite, hematite or chalcopyrite (coquina)
clusters in impure bodies. A further function is that of isolating the colour of the
body, covering the base and thus making subsequent use of coloured transparent
glazes or coloured preparation bases possible without any interference with the
(often dark) body colour.
Note also that engobes aid adhesion to the body without there being any prob-
lems of aggression with the latter and they also modify the average expansion
coefficient of the vitreous state so as to avoid the problems cited earlier. Perfect
calibration of all these chemical and rheological parameters with the optimum use
of frits and raw materials is thus highly important.
Today, more knowledge and skill is required for proper formulation of engobes
than glazes themselves.
The normally-used frits belong to the category of glossy whites, alkaline trans-
parents, fluxes (used to a lesser extent) to aid adhesion and special high-expansion
frits (to modify the dilatometric characteristics of the system). Overall percentages
vary from 40% to 80%. Raw materials used to complete formulation all of which
must be high quality include: zirconium (for covering performance), good quality
feldspars and quartzes and plastic raw materials (for rheology) such as clays and
kaolins. In this case very good fluidisation is required to ensure a good on-product
spread during application.
Note that this technology was largely developed to reduce the high production
costs associated with traditional double firing; that goal was achieved by introduc-
ing a whole series of automation and firing technology changes that have since
gone on to characterise the entire ceramic industry.
Employment of new kiln construction materials with low thermal inertia and
the adoption of single layer roller systems (thus doing away with the need for sup-
ports) allowed manufacturers to develop firing cycles (min. 25 minutes ~ max. 60
minutes) according to product size without failure of the ceramic body. Costs thus
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Raw materials for frits and glazes
fell on all fronts but glaze suppliers were forced to reformulate their entire range
of products.
Zirconium whites
These glazes, even when used in a fast double firing context, continue to consist
of at least 90% frit. However, the base frit making up these glazes has been substan-
tially modified to adapt thermal characteristics to the much faster firing cycles. As
regards the other technological aspects it can be said that the concepts expressed in
the description of traditional double firing zirconium whites remain valid. Remem-
ber that it is, here, more difficult to attain high opacity owing to the difficulty in
achieving a good degree of glaze maturation. Applying an increased percentage of
zirconium and balancing out its refractory effect with increased boron and alkali
content fails to provide good results in that it can cause partial solubility of the frit.
Matt glazes
Like the above glazes, these too differ substantially from the corresponding tradi-
tional double firing products. Observations as to the required modifications largely
correspond to those given in previous sections.
There is no progression in passing from a glossy surface to a matt one: the switch
from satin-finish surfaces to gypsum-like ones takes place without any intermediate
values. Experience teaches us that the best way of obtaining devitrified surfaces is
to use calcium even in very high percentages introduced in the form of wollas-
tonite or to use specific frits.
Introducing calcium as a carbonate or as a dolomite is, instead, inadvisable, in
that CO2 bubbles produced by thermal decomposition may be trapped. Zinc is also
capable of giving very soft matt surfaces, but obtaining a glaze that remains inert in
the face of chemical aggression is virtually impossible where this oxide is present in
substantial percentages. Fluidity should be better than it is with traditional double
firing glazes. It is possible to have both opacified and transparent products although
control of crazing is more difficult on the latter. Application of an engobe is nor-
mally required.
Engobes
Fast double firing employs higher-expansion engobes to ensure flatness or slight
convexity of the tiles: therefore more use is made of special high-expansion frits.
The remaining parameters are similar to those of traditional double firing en-
gobes.
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Special glazes
A whole range of wall tile glazes that were extremely successful in the past have
now lost ground in terms of commercial potential to white and semi-transparent
glazed products. A brief list of these follows below (Fig. 92).
Waxy glazes
Semi-covering glazes of average fusibility. Normally formulated with semi-flux-
es to which small percentages of zirconium, zinc, etc. are added. These were used
with coloured preparation bases and applied using techniques that led to uneven
thickness.
They are now mainly used in single firing and are currently making a weak
comeback in both traditional and rapid double firing.
Consequently, their composition is generally as follows:
medium-fusibility vitreous base: type 4 frits or a mix of group 1 (A and B) and
group 5 frits
waxy glazes
streaked glazes
torn glazes
iridescent
GLAZES
PARTICULAR flaked glazes
FOR
DOUBLE-FIRING
pearled glazes
crystalized glazes
leather glazes
Fig. 92. Different types of glazes once used in double firing (from the 60s to the 80s).
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Raw materials for frits and glazes
Iridescent glazes
Glazes containing special components that give surface iridescence. Used rarely.
The iridescence was obtained from boric vapour fallout (using leaded frits with a
high percentage of boric oxide known as blue frits) or by using specific heavy
metal oxides such as V, Bi, Mo, W.
Flaked glazes
Highly fusible glazes made up of special oxides (such as that of cerium) which
tend to generate split-ups and produce an effect where white flakes are immersed in
the transparent glaze. Used rarely, as they tend to craze.
Rustic-effect glazes
These glazes are currently regaining ground in the wall tile business while in
the flooring sector they are already used extensively. They contain hard raw mate-
rials of large particle size such as zircon sands and corundums which give the tiles
a rustic appearance.
All those glazes having varyingly fusible vitreous bases strongly hardened with
coarse materials can be classified in this group. These materials (various sands and
corundums) are normally introduced into the composition at the end of grinding.
Pearled glazes
Glazes having a soft surface and slightly gloss-matt nuances that evoke the ap-
pearance of a pearl. These are normally leaded and opacified with oxides (e.g. stan-
nic oxide). Not used on todays market.
These could be categorized as matt glazes, but since they have rather unique
composition and reactivity characteristics they deserve a separate description.
A fusible vitreous base forms the necessary starting point for the production of
this glaze (see group 5 frits for low firing temperatures). This base is then opacified
with micronized zirconium silicate in medium-low percentages and then matted
with the oxide mix (ZnO-TiO2-SnO2).
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Leathery glazes
Glazes resembling worked leather in terms of texture and colour. Normally of
leaded formulation, they are rich in stannic oxide, zirconium silicate, and contain a
little titanium dioxide. Colouring is provided by an orange pigment, accompanied
by ferrous oxide. These were often applied on markedly leather-coloured bases and
used flame effects to improve the overall chromatic effect. Used extensively until
just a few years ago they have now all but disappeared, although they are still used
in specific niches of the wall tile industry.
Aventurines
Glasses characterised by minute crystals in suspension (Fe-Cr-Cu), made highly
fusible by a lead monoxide and/or alkaline-boric compound-based composition.
Crystallization occurs by saturation (during firing) of these finishing glazes on the
part of an oxide and relative separation of the latter during cooling.
Preparation bases
Made up of strongly-coloured, varyingly fusible finishing glazes. Never used on
their own but always beneath other glazes.
Zirconium whites
With respect to fast double firing formulations it became necessary to increase
percentages of oxides such as CaO, ZnO, MgO and BaO in order to promote and
trigger this eutectic fusion. At the same time percentages of fluxing oxides such
as alkalis and boric oxide were reduced.
The aim is to have rapid frits that melt suddenly at high temperatures. The
same concept is equally valid for the alkaline transparent frits. As regards other
characteristics the observations made for fast double firing apply.
Rheological aspects require, in addition to fluidisers, the introduction of 0.3% of
CMC (carboxymethyl cellulose) to help bind the unfired glaze to the body. Without
the CMC adhesion during preheating would be insufficient.
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Raw materials for frits and glazes
Matt glazes
Formulations differ little from those used in rapid double firing. The additives
used in the whites and transparents are applicable here too.
Engobes
In this case too, the observations made vis-à-vis fast double firing apply. Perhaps
more so than in other cases (i.e. fast and traditional double firing), much attention
needs to be paid to viscosity.
Appropriate percentages of fluidising materials (0.05-0.3%) are, in fact, added to
the engobes because they are formulated using percentages of clay and glaze weights
higher than those used in fast double firing.
Nearly all wall tiling products, whether they employ zirconium white, alkaline
transparent or matt glazes, employ silk-screen or rotary decorating techniques to
meet aesthetic demand. A specific series of glazes has thus been developed for this
purpose.
The glazes in question are dispersed with short or medium-chain polyglycols to
give pastes just the right viscosity and simultaneously ensure decomposition of the
polyglycols themselves in the first stage of preheating, thus avoiding interference
at the glaze softening phase. The most frequently used glazes are the following (see
Fig. 93).
Range of colours
These are coloured glazes and coloured transparent frits that can be applied
under various conditions.
To obtain neutral effects alkaline transparent bases are generally used.
For slightly deeper effects the use of semi-fluxing materials is preferred.
Subsequent definition of matrix parameters refers to the number of threads
per cm.
Silk-screen printing matrices are generally made with nylon, polyester or, in
special cases, steel fabric.
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range of colours
highly-covering white
glazes
lustre glazes
iridescent glazes
reactive glazes
Fig. 93. Glaze types most frequently used as screen printing bases (all production technologies).
Heavy glazes
Used for incision effects on zirconium white or transparent glazes. Formulated
with vanadium frits or bases with high PbO percentages. Printing is usually effect-
ed with matrices having 51-77 threads per cm2.
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Raw materials for frits and glazes
Lustre glazes
Formulated with alkaline bases to which tungstic oxide or metallic tungsten are
added. Can also be formulated with special cerium frits. Matrices with 45-100 threads
per cm2 are used.
Iridescent glazes
Formulated with boric bases or heavy metals such as molybdenum, bismuth,
vanadium. Matrices with 21-45 threads per cm are used.
Reactive glazes
Used under the glaze (not just in screen printing) to obtain a mixing effect with
the overlying glaze during firing. Of high fusibility and applied using matrices hav-
ing 18-45 threads per cm.
This is currently the most widespread floor tile production technology. In the
Sassuolo area this technology was largely based on the use of local dry or wet-
ground red clays for the higher quality products. Red bodies were then replaced by
wet-ground, spray-dried ones and, more recently, these have, in part, been replaced
by stoneware or porcelain.
Over the years the technology has been refined to provide products of ever-
more sophisticated aesthetics and ever-better quality. Glazing is effected on a hot
body after treatment in a drier (80-120 °C).
It is essential to glaze the tile while it is hot enough to evaporate the water in the
glaze suspension and thus aid drying.
The addition of carboxymethyl cellulose in the glaze suspension is indispens-
able in ensuring proper adhesion of the glaze-body interlayer during preheating.
Light coloured bodies are generally fired at a temperature of around 1160-1220
°C with cycles lasting 35-55 minutes.
Red bodies are generally fired at temperatures of around 1120-1130 °C with
cycle times similar to those cited above. Finally, high-porosity red bodies are fired at
1080-1100 °C with firing cycles of 30 to 50 minutes.
Descriptions of the most commonly used single firing floor tile glazes are given
below.
Waxy glazes
Refers to a category of glazes used extensively in single firing of a silky matt
appearance. Their covering capacity lies midway between that of a white and a
transparent.
Sometimes, completely transparent products are also defined as waxy (but only
in single firing).
Fusibility is always medium-to-high and under-glaze decorations or applications
may be applied. Above-glaze applications are generally limited to silk-screen deco-
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ration only. CMC is added to these glazes to improve on-body adhesion. Formula-
tion generally makes use of averagely leaded frits.
The added raw materials, which make up 10-30% of the glaze are: zirconium
silicates, zinc and stannic oxides, feldspars, wollastonite, clays and kaolins.
Rustic-effect glazes
In recent years this category has become extremely diversified. These glazes
generally have non-gloss surfaces, are soft to the touch and opaque to reflection of
light or rough and strongly satined. They may also be gypsum-like and markedly
opaque. Formulation varies widely. The employed frits are of the semi-fluxing type,
such as, for example, disilicates, accompanied by various other frits. Added raw ma-
terials too constitute a highly varied group, ranging from corundums and sands to
confer hardness and coarseness to zinc oxide, tin and wollastonite for softness (cal-
cium is also introduced as carbonate and/or dolomite). Feldspars and nephelines
are also employed to give the glazes glassiness and clays and kaolins to regulate
rheology.
Zirconium silicate is used in low percentages. Covering capacity is highly vari-
able and depends on the need to utilise highly elaborate (and often under-glaze)
applications. Items produced with these glazes are commercially referred to as rus-
tic. Such products may require up to 15 successive applications that involve disc
application, brushing, airbrushing, washing with water, air-jet blowing and dry ap-
plications. The resulting aesthetics are superbly sophisticated, especially when one
bears in mind that pre-structured bodies can extend decorative opportunities even
further.
Cotto glazes
These glazes were created to imitate classic, unglazed cotto. They have since
been diversified into a range of products to meet more specific aesthetic needs such
as rustic cottos etc.
Composition largely falls into line with that of the rustic glazes, yet a wider
range of colours is available. These products are normally off-shade and matched
with rustics to obtain floors that fall within the extensive rustic category. Applica-
tion is as described for rustics.
Crystallised glazes
Currently regaining lost ground after a prolonged absence from the market.
Formulated using fluxing frits and high percentages of titanium dioxide. The
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Raw materials for frits and glazes
above-cited oxide crystallizes during firing under the form of rutile. The use of
coloured bases gives rise to deep-colour effect products. The greatest inconve-
niences stem from the level of crystallization which is difficult to keep constant.
Modern fast firing processes should aid uniformity of firing across the entire kiln
cross-section.
Engobes
These serve the same purposes described for the other technologies. Formulated
with a high percentage of clayey raw materials and kaolins.
Coloured bases
May be formulated with fluxing frits coloured on fusion, mixes made with high
percentages of pigments and colorant oxides such as ferrous and manganese ox-
ide.
These coloured bases are used to obtain special under-glaze effects by way of
their reactivity with the overlying glazes.
The applied glaze layer can also be brushed to concentrate the colour in struc-
tured body cavities, thus creating highly interesting deep-colour effects.
Matt glazes
These glazes are formulated using frits of high calcium, zinc and/or magnesium
content. Semi-fluxing frits are sometimes used too, while zirconium silicate, wollas-
tonite and plastic materials are added in the mill.
Matt glazes are generally applied using the disc method.
Technical glazes
These glazes feature excellent abrasion resistance and porosity both on the
surface and inside the vitreous mass. Generally formulated using hard raw mate-
rials such as corundums. Special frits that give rise to devitrification-type crystal-
lisation during firing are sometimes used too (glass-ceramic). Application begins
with a specific white base followed by fairly thick (e.g. 12-thread) silk-screen print-
ing that provides the product with marked technical characteristics. Improvement
of on-product aesthetics is achieved via widespread utilisation of coloured silk-
screen printing products applied between the base and the thick technical glaze
layer.
Dry-application grains
Dry application techniques have come a long way over the last few years: these
were originally conceived to meet both the continually evolving aesthetic demand
and satisfy a pressing need within the ceramic industry to reduce the environmental
impact of glaze application and preparation.
It should be born in mind that the grinding and wet application of glazes
generates substantial quantities of by-products (i.e. ceramic sludge) which need
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172
Raw materials for frits and glazes
The final stage consists of particle size selection. These grains offer a series of
advantages with respect to frit grains. The first is the total absence of infusions in
that sintered grains are produced with ground glazes. A second advantage lies in the
possibility of using just about any type of composition, an alternative unavailable
where frits are used “as they come”.
The particle size range for these sintered grains spans from 0.18 to 1.5 mm. While
sintered grains cost much more than frit grains their use is justified by the excellent
aesthetic effects they produce.
The third mainline grain group takes the name of pelletized grains.
These are produced from ground, dried glazes that are pelletized and hardened
with chemical additives. Once again, proper particle sizing is essential, the typical
range spanning from 0.18 to 3 mm. Used on all tile types, these grains provide a
range of advantages with respect to their sintered cousins, not least of which is the
lower cost. The use of additives acting as binders may cause degassing problems
(especially where firing conditions are borderline and products are already loaded
with other organic substances that have to be decomposed).
Glossy white
Used on the market in all three above-described types. The frit grain is usually
produced in a less fusible form while sintered and pelletized grains use high-fusibility,
generally leaded white glazes opacified with zirconium, tin, zinc.
Transparent glaze
Here too, the most commonly used products are highly fusible. Suitable for types
that require the grains to melt until the product spreads completely. In other cases
tiles with only partial grain fusion are produced.
White matt
This product is difficult to use in pelletized form in that it is harder to eliminate
the adhesive degassing problems. As a frit grain there are often persistent infusion-
related problems.
Another generalized problem is that it is difficult to obtain flat surfaces without
using zinc (albeit in small percentages) as a devitrifying agent.
Remember that in these cases zinc often lays the tile surface open to attack by
acid.
Special grains
These include glazes with lustre effects (those obtained from the frit being es-
pecially effective), crystallized effects and deep-colour transparent effects (sintered
grains are in a league of their own here).
Note that it is also possible to mix different grain types (even where they belong
to different families) and production techniques, thus multiplying the range of ce-
ramic and chromatic effects. It should, however, be born in mind that particle size
differences must be limited otherwise separation and layering will occur during both
storage and application.
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Technical grains
Usually of very fine particle size, these are frit or pelletized grains. Applied on
specific base glazes in very thin layers. Made from frits belonging to the technical
family, they thus feature excellent abrasion resistance and good compactness even
inside the vitreous mass. Capable of passing even the ISO 10545/7 Class V test.
Fig. 94 provides an overview of grain types, showing how they split into the
three main production technologies.
LUSTRE
GLAZE
COLOURED
TRANSPARENT
FRIT
CRYSTALLIZED
GLAZE
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Raw materials for frits and glazes
Chapter V
Many properties of raw materials, whether fired or unfired, correlate with their
chemical or mineralogical composition.
Yet other parameters, such as size and shape of particles, their arrangement and
the way they come into contact with each other the very structure of the ceramic
body are equally important. Such factors strongly influence the chemical and physi-
cal changes that take place in the presence of the energy input associated with
firing.
For this reason, most ceramic materials need to be broken down to a size that
will optimise subsequent production processes: this goal can be achieved via a series
of methods, collectively known as COMMINUTION.
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The main problem is the sharp drop in grinding efficiency that occurs as the par-
ticles get smaller.
It is thus common practice to employ return-feed screening systems that filter
out already-ground material as soon as it forms.
A raw material made up of particles of different size and shape may be defined
as a particulate system: size distribution of the grains in such a system is enor-
mously important, yet very difficult to measure.
Were they perfectly spherical, it would be easy to sort them via dimensional or
gravimetric selection (assuming constant sphere density): yet with a clayey system
the matter is somewhat more complex, making it difficult to define exactly what is
meant by the word particle.
While it has already been described how a clay is made up of extremely small
particles (micelles), it is also a known fact that these micelles, in the ceramic bodies
and raw materials themselves, are aggregated and agglomerated, thus making them
difficult to isolate in their free form.
Particles produced by grinding clays, then, will essentially be made up of many
small agglomerates of irregular form and variable surface/peripheral charge, thus
influencing behaviour in aqueous suspensions and during firing.
The first problem, then, in attempting to measure the dimensions of ceramic
particles and their distribution, is to decide whether to concentrate on the dimen-
sions of the individual particles or, vice versa, the agglomerates.
Similarly, the choice of pre-analysis dispersion systems will be decisive, as these
could break down the agglomerates/particles or even cause further agglomeration:
particle size analysis on a material dispersed in water with rheological additives
gives results that differ substantially from measurements made on the same powder
in its dry state.
Further complications are found in the enormous variety of granulometric sizes
within a ceramic body, especially where it has been dry-ground: however, even wet-
ground materials contain particles ranging in size from just a few tenths of a µm, to
tens of mm, and there is no instrumentation capable of providing adequate accu-
racy over such a wide range.
Finally, the particles of a ground ceramic material, especially where clayey, are
far from spherical, often plate-like.
These particles are mixed in with other materials that break down to form par-
ticles that, while spherical, are of greatly differing density.
Nevertheless, use of statistical evaluation and particle shape correction equa-
tions, which give spherical-equivalent diameters, makes it possible to effect reliable
particle size distribution measurements of solids in a suspension (usually in an aque-
ous solution) so as to evaluate the behaviour of the combinations during grinding,
forming, drying and firing.
176
Physical and structural properties of ceramic raw materials
The main dimensional classification methods are listed in the following table,
which orders the methods according to minimum and maximum detectable particle
size.
Sieving > 50
Micro-sieving/filtration 0.2 - 50
Sedimentation 1 - 50
Elutriation 2 - 50
Centrifugation 0.05 - 5
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The above table highlights the limitations of sieving methods, their use being
confined to rather approximate discrimination: on the other hand, hydrodynamic
methods, long used for finer resolutions, are complex and lengthy (especially so for
very fine particles). The best compromise is to use short wavelength incident radia-
tion (X or laser) interaction instruments through the application of modifications
to Stokes law.
This is expressed by the following equation:
2 (ρ - ρ ) g r 2
1 2
V= ____________________
9η
where V, the speed of a falling particle in cm/sec, is obtained from the values:
η viscosity of the suspension medium [water = 0.013 (10 °C), 0.010 (20 °C), 0.008
(30 °C) poises].
ρ1 density of the particle
ρ2 density of the suspension medium
g gravitational acceleration (981 cm/sec)
r radius of the particle, assumed to be spherical (cm).
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Physical and structural properties of ceramic raw materials
At constant temperature, where all constant parameters are known and the sedi-
mentation speed of a set of particles is measured, it will be possible to calculate the
average dimensions of the particles themselves.
By applying Stokes equation values to a particle with a density of approximately
2.5 g/cm3 and a diameter of 1 mm, it can be deduced that it will drop through water
at 20 °C, in the absence of any interaction with the water itself, at just under 1.2
cm/hour. The appropriate practical modifications to the equation, as a function of a
real particle, reduces this speed to about 0.3 cm/hr, thus giving a clear idea of just
how long hydrometric particle size analysis can take where a sedimentation of at
least 20 cm (and thus a wait of some 64 hours) is required.
Fig. 95. Example of differential and cumulative particle size distribution curve.
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All this is essentially based on a no larger than
principle through use of
appropriate sieves.
At this point it is important to highlight, with particular reference to grinding
(and homogenisation), the influence of variations in particle size both throughout
the process and on final product characteristics and classification.
The understanding and control of particle size is essential to ensure optimum
body texture and homogeneity and the required porosity, specific weight, modulus
of rupture.
The texture of the material is strongly influenced by the type and degree of
grinding. This is because grinding alters the size and shape of the individual grains
and causes variations in the way in which they associate, thus influencing particle
packability and final density.
Various studies on maximum attainable packing density have been carried out
with regard to both spherical particle systems with no particle deformation and
for isomorph sphere systems: these studies have yielded an ideal distribution that
gives rise to two possible solutions: open packing with spheres arranged by
cubic symmetry, where empty gaps account for 48% of the entire occupied vol-
ume and closed tetrahedral-symmetry packing with gaps accounting for just
26% of total volume.
Of course, systems featuring mixtures of different, always-spherical grains will
give rise to ever-more complicated theoretical models which optimise use of space
enormously: for example, a tri-modal system based on appropriately calibrated
spheres (having an assumed diameter ratio of 50:8:1) of large (62% by volume),
medium (24%) and small (9%) size will, in theory, fill the space very efficiently,
leaving an air-gap residue of just 5% (62 + 24 + 9 + 5 = 100%).
While the individual particles in a ceramic body are generally angular rather
than spherical the above-explained general principle may be taken except where
particles are particularly elongated in one direction as being applicable, albeit
inexactly as there are many other inconveniences linked to the fact that the irregu-
lar shape of the particles stops them sliding against each other.
On the other hand, that irregularity will, statistically, give rise to the real possi-
bility of forming more extensive areas of tighter agglomeration and, all in all,
lowering average porosity.
In general, grinding processes that involve initial impact crushing followed by
abrasive comminution (as in an Alsing-type ball mill), give optimum yields in terms
of attainable density, especially where the treated materials are of different hard-
ness and density: this thus permits the co-presence of relatively coarse particles
(feldspars, quartz etc.) and others of smaller and smaller particle size distribution
(e.g. clays).
Clearly, a particle size control system consisting of just one simple sieving (so-
180
Physical and structural properties of ceramic raw materials
called sieve residue) serves only to establish whether production activities com-
pleted thus far have remained within operational parameters. Fig. 96 shows two
bodies (the particle size distribution curves of which are illustrated) with an identi-
cal residue of about 2% at 63 µm: yet they clearly differ substantially in terms of
particle size composition, with body A having a Gaussian distribution around 15
µm, and body B having bimodal distribution centred around 0.6 µm, with an aver-
age dimension of about 9 µm.
Fig. 96. Particle size distribution analysis of two bodies having same residue but different particle size
distribution.
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The technological behaviour of the two bodies, which seem identical in the light
of residue-only analysis will actually be radically different, as B is much more
compactable than A.
The unpackability of ground raw materials and the forces applied during the
forming process (pressing, extrusion
) make the production of a ceramic body
without any empty spaces at all virtually impossible, no matter how accurate selec-
tion and particle size distribution may be.
All ceramic materials, except for some glasses, have pores or empty spaces: the
porosity of a material is, then, defined by the quantity of air it contains. In scientific
literature there are six different kinds of porosity (see Fig. 97):
Fig. 97. Different types of porosity. From: Grimshaw, Chemistry and Physics of Clays-Benn.
a) closed pores
b) capillary canals connecting closed pores
c) blind pores
d) interconnected pores
e) open or ink bottle pores
f) micropores (so small they prevent entry of water or any other liquids).
There are two types of closed pore: those formed by pressing the semi-finished
item and those originating from open pores that are sealed by material that melts or
forms during firing.
In both cases, but mostly the latter, closed pores are full of air, water vapour,
SO2, CO2 or CO, or even O2.
When a ceramic body is heated, the pressure inside the pore increases and
exerts considerable force on the surrounding solid material: this can cause fissur-
ing, lamination and even explosions as long as the material remains rigid (low
temperature), but when the latter starts to soften at temperatures close to and
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Physical and structural properties of ceramic raw materials
beyond the vitrification point, the pressure exerted by the enclosed gas may cause
expansion of the material itself and create bubbles which, in turn, form new
macroscopic pores.
Dimples or pin-hole defects seen on fired glazes often stem from closed pores
too: these are formed by carbonates, sulphates and other pyrolysis-affected com-
pounds that emit gas at high temperatures: if this occurs when the glasses in the
glaze are about to become plastic the glaze will block the escape and elimination of
such gases.
Open pores (i.e. those connected to the exterior by capillary channels of varying
length and width) may be formed by the original particle packing configuration,
elimination of water vapour during drying or the initial stages of firing, elimina-
tion of gas during firing, micro-structural alterations in the pieces during drying
etc. The presence of such pores is closely tied to the size of the body particles and
how they are packed.
In general, since fluids (rainwater with regard to freezing resistance and inks,
oils etc. for staining and cleaning parameters) can enter and exit open pores, it is
preferable for a fired product to have open pores of either a very large average
diameter (>300 µm, to allow easy evacuation of water or introduction of deter-
gent solutions) or a very small one (<40 µm, the smaller the better) so as to make
fluid entry difficult and prevent any water contained therein from freezing as a
result of extremely strong capillary forces: it thus follows that materials with a
substantial amount of medium-size open pores (from 40 to 300 µm) remain at
risk.
Such a wide range of scenarios makes it possible to measure two different body
parameters: total porosity and apparent porosity.
The true (or real) porosity of a body is the ratio of all (open and closed) empty
space volumes to total volume, while the much more frequently-used apparent po-
rosity parameter is defined as the ratio between the volume of water the body can
absorb under certain conditions (during prolonged boiling or vacuum treatment)
and the total volume of the piece.
Such porosities will clearly be influenced by the dimensions, shape and packing
of the particles, the chemical nature of the materials making up the body, and the
technological treatment applied to materials during production: an often-underesti-
mated parameter is the intrinsic porosity of the individual particles.
As stated in the introduction, depending on their mineralogical formation, clays
possess widely differing structures with interlayer spaces ranging from 5 to 20 or
more Å; in this respect they differ greatly, of course, from quartz or other compact
material particles.
For this reason a clay-based body containing large quantities of sands and feld-
spars, especially where the latter are of suitable particle size, will be less porous
than that of a predominantly clayey body.
In addition to these morphological features, body texture and particle size distri-
bution will play an important role in physical and chemical reactivity during firing,
as will be illustrated further on.
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Any particle size variation, in fact, will have an influence on the specific surface
area of the powders and an immediate influence on the inter-particle surfaces, sharply
increasing that reactivity surface area, which, via solid-solid or solid-viscous liquid
reactions (high-temperature ceramic bodies), is of primary importance for proper
sintering.
The example in Fig. 98 shows a ceramic body matrix made up of relatively coarse
feldspar (F) and quartz (Q) particles contained in a brick-like framework of clayey
particles:
The sintering process begins at the particle contact points, where the fluxing
action of the feldspars first acts (the black dots in the far left drawing).
Following initial reactivity, which tends to involve the smaller particles in closer
contact with the fluxing agents, a liquid phase forms: this goes on to involve, par-
tially, the surrounding clayey structure.
During the process, and especially during cooling, crystalline neo-phases form
and reinforce the sintering phenomena in the mass.
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Physical and structural properties of ceramic raw materials
In both the former case (particle size distribution either natural or induced by
raw material grinding) and the latter (particle size distribution of semi-finished
items), it is essential to evaluate the relative amount of the different granule classes
so as to obtain the best possible mix and optimum compaction.
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Water plays a vital role in ceramics. Most ceramic raw materials are sedimentary
in nature and thus formed in an aqueous environment.
Many key minerals are of secondary origin, created by water-induced weather-
ing of primary rock.
Furthermore, water is added at most stages of the ceramic production process
to aid completion of shaped semi-finished items.
Although water has a significant effect on any type of raw material, it plays a
particularly important role in clays owing to the already-described structural char-
acteristics: these include inter-particle spaces and electrostatic charges that allow
intense interaction with the water molecules, which, because oxygen and hydrogen
have different electronic affinities, may be seen as small dipoles with a partial nega-
tive charge on the
Hδ+
O and a partial positive charge on the H δ-O < δ+.
H
When water is mixed in with the powders in quantities equal to approximately
one fifth the weight of the powder itself, plastic bodies are obtained. Where that
proportion rises to between a third and a half, suspensions of extremely differenti-
ated rheological characteristics result: given the dimensions of the clayey particles,
these may be considered and treated as colloidal suspensions.
Given the complex nature of water these basic interlayer electrostatic interac-
tions are accompanied by others dependent on structural or chemical irregularities,
generally influencing the surface of the particles:
a) distorted ionic groupings
b) broken surface bonds, unsaturated bonds, sliding or crumbling planes
c) cations of unsaturated charge, or cations which create charge defects in the crys-
tal lattice etc. If a basal plane of the crystal lattice is theoretically in electrical
equilibrium and the surface, vice versa, has a excess/insufficient charge (gener-
ally caused by the high number of oxygen2- atoms in the ceramic material), a
fracture will greatly disturb that equilibrium, causing different attraction/repul-
sion scenarios involving the water molecules (Fig. 99).
In-depth analysis of double layer interactions is outside the scope of this pub-
lication. Many experts interpret it as a sort of molecular condenser, the (zeta)
potential of which can be calculated by studying variations in the potential en-
ergy of the system (see Fig. 101). Here we shall simply examine the macroscopic
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Physical and structural properties of ceramic raw materials
Fig. 99. Kaolinite crystals with positive and negative edge charges (A and B respectively), defloccula-
tion (C), edge-to-face flocculation (D), face-to-face flocculation (E), flocculated Ca clay (F), deflocculat-
ed clay -Na (G).
free water
free water
bound
water
Fig. 100. Distribution of charges and water, free and bound, around clay particles in suspension. The
cross-hatched area in the middle is the clayey core.
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Zeta potential:
e = charge
D = dielectric constant
d = distance between rigid and diffuse layer
rigid diffuse
layer layer
potential
resultant
R = repulsion
distance
A = attraction
Fig. 101. Attraction and repulsion potentials in a radial direction starting from the surface of a grain
dispersed in a solution.
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Physical and structural properties of ceramic raw materials
As regards aqueous suspensions of ceramic bodies, the main events which need
to be controlled and guided are flocculation and its opposite, deflocculation. In the
former, rapid sedimentation of flaky particle aggregates of greater density easily
separated from the system are created from within a homogeneous in-water particle
suspension. In the latter attempts are made, vice versa, to aid dispersion of aggre-
gates using appropriate additives, thus obtaining particles that remain in suspen-
sion for long periods even in the absence of agitation. This last characteristic is, of
course, particularly sought after in the wet grinding of clayey bodies.
Both effects are the result of disturbing the solid-water electrical particle layers:
flocculation is usually caused by the introduction of small and therefore high
charge-density bi or tri-valent cations; these can seriously alter the electrostatic
equilibrium of the suspension. Deflocculation, instead, is generally achieved by adding
organic or inorganic polymeric molecules that isolate the particles from each other
by separating them on account of their structural characteristics. Here too, the
presence of appropriate cations (Na+, NH+) that alter the equilibrium of the double
layer aids the effectiveness of the additive.
Because ceramic particles are negatively charged, they easily attract positively
charged cations. The tendency of cations to be adsorbed has been shown, for the
most common, to be: H+ > Al3+ > Ba2+ > Sr2+ > Ca2+ > Mg2+ > NH4+ > K+ >Na+ >
Li+, so the useful cations, such as sodium and potassium, have little chance to act.
The effect (which will depend on the ratio of their charge and volume) may be used
to vary the electrical characteristics of a suspension or by adding excess to act on
the exchange equilibrium
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Physical and structural properties of ceramic raw materials
Chapter VI
One of the biggest challenges facing the ceramic technician is translating that
colourful jargon surrounding the practical aspects of rheological phenomena into
more rigorous terminology.
Remarks such as the glaze flows like oil, its bubbly, its settled and hard-
ened in the tank, its thinned out too much, the mills jammed and the slip
has frozen are all common factory floor comments. These empirical expressions
actually reflect considerable knowledge of how rheological factors affect the pro-
duction process. Yet it is a knowledge that has been built up on a trial and error
basis and which, to a large extent, has not been rationalised in a way that allows it
to be transmitted.
Nevertheless, the ceramic industry continued to rely on this rather uncertain
wealth of knowledge for years, and it has to be said that production processes
were, by and large, kept under control; when production cycles were slower and
product change-overs less frequent, this level of understanding was more than
good enough.
Now, though, with the advent of new technologies and the fast-changing flurry
of products and glazes there is no longer time to build up an empirical understand-
ing of events.
Instead, the glaze or body slip must comply with precise production standards,
defined according to standardised units of measure.
Let us begin by shedding some light on the concept of viscosity. This term has
become a part of everyday vocabulary and is now mentally associated with a greater
or lesser ease of flow.
To arrive at an exact definition it is first necessary to define the exact physical
measurement one is referring to.
A rather crude definition of viscosity might be the effort needed to make a fluid
attain a certain speed.
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The first thing is to clarify that one cannot refer to the speed of a moving fluid as
if it were a racing car.
If that were the case then all the fluid, like all the components of the car, would
be moving in exactly the same way.
For example, we can talk about the speed of a drop of water as it falls into an
empty glass: the entire drop moves with respect to the sides of the glass and thus its
speed is defined by the ratio between distance covered and time taken as with the
racing car.
Yet a fluid flowing in a tube is subject to quite a different set of conditions: the
part of the fluid in contact with the wall of the tube moves much more slowly than
the fluid in its middle. The absolute speed of a fluid molecule thus differs according
to its position inside the tube, reaching a maximum in the centre and a minimum up
against the walls.
In shifting from the wall to the centre, then, speed increases constantly; this is
because none of the molecules are free to move in the same way as a car on the race
track or the drop falling into the glass.
They are, instead, obstructed by the other molecules in the fluid as a result of
internal friction.
The wider the tube the easier it is for the fluid to flow because the particles in the
central zone are less affected by friction than those up against the walls. Or, in tubes
of equal diameter, the lower the friction between the molecules of the fluid the
higher the speed of the fluid in the central position.
Velocity gradient
To define viscosity we need to know all the parameters affecting it. One of these
is the velocity gradient. If, in a certain zone of a moving fluid mass we measure
maximum speed (vmax), and in another the minimum (Vmin) and then the distance
separating the two points at which the measurements were taken (l), we obtain a
gradient value valid for the moment of measurement. The difference between the
two speeds divided by the distance is defined as the velocity gradient and is indi-
cated by D:
As we have seen, this value is directly affected by the degree of friction within
the fluid. If, all conditions being equal, a fluid has a high velocity gradient this
indicates that its molecules generate low-level internal friction. The physical di-
mensions of D are:
v [LT -1]
D= ___ = _______ = [T 1] = reciprocal seconds
L [L]
This is the inverse of a time. Reference is always made to the velocity gradient
expressed in reciprocal seconds.
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Rheology: basic concepts
Shear stress
The second element affecting viscosity is the stress the fluid is subject to.
Let us go back to our example of the tube for a moment: tube diameter and in-
fluid friction remaining equal, it can intuitively be seen that increasing pressure
increases the velocity gradient (i.e. the fluid will flow faster).
However, the concept of pressure, as a description of the stress to which the
fluid is subject, is inadequate in that it is not necessarily connected with flow.
In a closed system there is no flow at all, whatever the applied pressure. This is
because pressure is the ratio between a force and a surface perpendicular to the force
itself and does not necessarily generate movement.
Example: a concrete block resting on a floor generates a pressure defined as
force per unit of surface area. Getting the block to move requires considerable force,
but such force must be applied parallel to the floor, not perpendicular to it. At a
certain point, once the applied force reaches a certain threshold, the block will start
moving along the surface of the floor.
The force needed to start the block moving will be considerable as cohesive forces
that bind two objects in contact when at standstill need to be overcome: such mo-
tion-opposing forces, which tend to stick two immobile objects together, are de-
fined as static friction.
In mechanics the ratio between the orthogonal forces acting on the two surfaces
in contact, when movement begins, is defined as the coefficient of static friction, µ
(mu).
Note that, since the coefficient of friction is an intrinsic characteristic of the two
surfaces in contact, surface area is non-influential: both forces act on the same sur-
face even though they are orthogonal.
When the body, still subject to the pressure of its own weight, finally starts
moving, a traction force needs to be applied: this will be proportional to speed and
surface roughness.
This applied stress, like the above-mentioned static friction, is needed to over-
come the forces generated by dynamic friction (generally lower than static fric-
tion).
Of course, one cannot speak of friction between two surfaces subject to orthogonal
forces where fluids in motion are concerned: the relevant concept in this case is
internal friction, and thus the only significant value when studying the flow of a
fluid is the force applied tangentially to the unit of surface.
This is defined as shear stress and is indicated by the Greek letter τ (tau) and is
measured as a pressure:
Ft [LMT-2]
τ= ___ = ________ = [L-1 MT-2] = N / m2 = Pascal
A [L ]
2
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Viscosity
Referring to the above measurements it can be said that applying a force to a
certain area of a fluid mass to keep it moving causes the fluid to respond by gener-
ating shear stresses that result in different zone-to-zone speeds.
Within the mass, then, a velocity gradient is created. Its value depends on the
internal friction of the fluid, a factor closely related to its viscosity.
Viscosity is defined as the ratio between the shear stress and the velocity gradi-
ent. It is indicated by the Greek letter η (eta) and has the dimensions of a pressure
over time:
τ [L-1MT-2]
η= ____ = _________ = [L-1 MT-1] = Ns/m2 = 10 Poises
[T ]
-1
[T ]
-1
This essential formula tells us that viscosity is directly proportional to the shear
stress needed to obtain a given velocity gradient in the fluid.
On the basis of the units of measure adopted for D and τ, viscosity is usually
defined as:
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Rheology: basic concepts
fully described by the value η as it remains constant whatever the flow speed and
depends on temperature only.
A graph showing τ (shear stress) values against variations in D (velocity gradi-
ent) gives us the line illustrated in Fig. 102.
Yield point
Experience teaches us that ceramic suspensions are decidedly non-Newtonian.
In attempting to define those divergences from ideal behaviour that significantly
affect the technological cycle, it should first be pointed out that one of the most
important aspects of such a suspension is that it will often start flowing only when
applied shear stress exceeds a certain threshold.
Similarly, if it is already moving, it will only stop doing so once shear stress
drops back below that threshold.
Returning momentarily to the example of the concrete block resting on a floor,
there is a clear analogy with the tangential force needed to shift the block. The level
of such force depends on friction.
Getting back to the flow of fluids (i.e. rheology), this threshold value is defined
as the yield-point. This is an initial shear stress indicated by τ0 (tau zero) and is
measured in pascals.
Where a fluid has a yield point and flow only begins at a threshold level of shear
stress, the velocity gradient remains zero until the τ0 level is reached as in the graph
in Fig. 103. This important characteristic is common in ceramic fluids where flow
stops though still subject to shear stress.
It is this parameter that determines the spread of disc-applied glazes, the form
of the droplets in the droplet method, the thickness of the dipped glaze or the
thickness of glaze applied to a vertical surface before it starts to run.
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Fig. 102. Standard rheogram for Newtonian-type fluid where the following relationship applies:
τ
η = _____ = tan α.
D
Fig. 103. Rheogram for a fluid with an initial yield point τ0 (Bingham plastic).
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Rheology: basic concepts
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Thixotropy
A third type of rheological behaviour frequently encountered in ceramics is thix-
otropy which, if excessive, can cause difficulties.
This is a tendency that leads some suspensions to change their rheological
behaviour as a function of the yield stress they have previously been subject to.
The most common scenario is that in which viscosity is lower where the fluid
comes from a situation of higher stress, and is often when a yield point exists.
In practice a graph illustrating τ and D for initially higher and then lower veloc-
ity gradients (D) yields a rheogram with hysteresis (Fig. 104).
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Rheology: basic concepts
Fig. 104. Rheograms showing hysteresis and corresponding definitions of the behaviour that produces
them.
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Rheology: basic concepts
Rheology of clays
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A water-clay system can also be controlled via the use of deflocculants: the
same ceramic material deflocculated with different percentages of sodium tripoly-
phosphate (STPP) will show significant system rheology differences, with the ap-
pearance of a yield point and accentuation of hysteresis.
Less favourable rheological conditions reign with higher tripolyphosphate per-
centages, indicative of an over-deflocculation that causes incorrect system fluidi-
zation.
Analogous situations arise when the type of deflocculant is changed.
Given our present level of understanding it can be said that the phosphates
(especially tripolyphosphates) tend to give good results right across the known
range of clays by providing sufficient control of system thixotropy. Silicates yield
good results with clays that are lean or of high kaolin content, but control of
thixotropy is more difficult than with phosphates.
Organic products are generally good dispersants and stabilizers but are less
efficient in controlling apparent viscosity. As regards the ratio between
deflocculants, the yield point and plastic viscosity in water-clay systems, little
information is available. This is particularly so in industrial-type systems, owing
to the difficulty of discriminating between the various factors that influence the
two parameters above.
The most common clayey minerals in clays used by the ceramic industry are
kaolin, illite, the smectites (montmorillonite, nontronite) and chlorites.
The rheological characteristics of a clay thus depend on the type and quantity
of clayey minerals it contains, though they cannot neatly be summed as a function
of their in-clay percentages. This is because of the already-cited presence of ac-
cessory minerals, which can be important in defining the rheological characteris-
tics of a clay.
There follows a brief description of the rheological characteristics of the above-
cited minerals: however these observations refer to the minerals in their pure
state, while for clays used in industry other parameters influence.
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Rheology: basic concepts
Illites: as illites of a purity comparable to that of kaolins do not exist, one can
only reason in terms of clayey systems containing varying percentages of illites.
This fact, taking into account that rheological characteristics cannot neatly
relate to the percentage of minerals present and the difficulties in determining
the percentages of such minerals with accuracy, shows how difficult it is to inter-
pret the rheological characteristics of an illite clay.
Let us evaluate, for example, an illite-kaolinitic clay in which other minerals
and impurities are assumed to be absent.
In this case, compared to a kaolin, all other conditions being equal, there is an
increase in the plastic behaviour of the system, with more accentuated thixotropy
and greater apparent viscosity.
On the other hand, comparing an illite-montmorillonite to a montmorillonite
clay, the apparent viscosity, yield point and thixotropy of the system will be lower,
but compared to an illite-kaolinite clay they will on average be higher.
All in all it can be said that illite is a clayey mineral having rheological charac-
teristics less desirable than those of kaolin as there is the appearance of a yield
point and thixotropy.
Certain grinding conditions emphasise these characteristics as illite is more
sensitive to grinding than kaolinite. The most effective deflocculants are tripoly-
phosphate and sodium metasilicate, while products that act on pH only, such as
carbonate and sodium hydrate, are of limited use. This is because the natural pH
of illite is less acid than kaolin.
The above observations will obviously require modification where minerals of
a different nature predominate in the illite clay system.
Both plastic and apparent viscosity are high even where the percentage of solids
is low. A certain differentiation in the behaviour of these clayey minerals is ob-
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served as a function of the type of cations in the layers. There are, roughly speak-
ing, three main types of montmorillonite: acid, sodium and calcium. The acids are
montmorillonites obtained by treating natural minerals generally extracted as so-
dium or calcium montmorillonite.
Generally speaking, the acids are extremely difficult to deflocculate, unless
deflocculants that raise pH sharply are used. On the other hand the sodiums are the
easiest to deflocculate and can be fluidized with STPP and polyacrylates.
Calcium montmorillonite is the mineral commonly found in clays for ceramic
use; it is more difficult to deflocculate than the sodium type and generally requires
phosphate or polyacrylate-based mixes. In any case, use of this mineral must be
tightly controlled and it is good practice to limit quantities to no more than 6% in
lean bodies and 4% in plastic bodies.
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Rheology: basic concepts
Lab tests using de-ionised water have confirmed that soluble ion slips prepared
with de-ionised water show much better viscosity than all the others prepared with
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potable or industrial water (other variables remaining equal) for reasons already
cited (presence of flocculating ions, high total ionic charge).
Furthermore, ceramic body grinding water is often the worst in the whole fac-
tory, containing runoff and waste from other departments (i.e. glazes, various or-
ganic substances and so on). However, even clean water recovered from waste
beneficiation can contain small quantities of flocculants (ferric chloride, aluminum
chloride, lime, polyacrylamides) and can have worse effects from a rheological
viewpoint than untreated waste water.
A further grinding water factor is pH: as already mentioned, there is an optimum
deflocculation pH range (normally 8 to 9). Water with pH values outside this range
will make the whole process more difficult.
From these observations it can be concluded that periodic inspection of the grind-
ing water may be useful, if not necessary. Rather than a true chemical analysis,
which would be difficult to carry out inside most ceramic production plants, it might
be preferable to run the following tests as they can be completed quickly and do not
require the use of costly equipment:
a) pH: using a pH-meter. The importance of pH is cited in the preceding para-
graphs.
b) electrical conductivity: using a conductimeter (simple hand-held versions are
available), giving an approximate idea of total ionic concentration.
c) total hardness: determined by titration, measures the quantity of flocculating
ions (Ca2+ and Mg2+).
d) COD (Chemical Oxygen Demand): a measure of the oxidizable organic substan-
ces in the water. This assessment, while more complex than the others, is done
by titration.
Periodic and frequent control of these parameters will provide sufficient (but
incomplete) grinding water quality data, allowing correlations to be drawn between
changes in such parameters and any worsening of the rheological characteristics
of the slips. It also allows, albeit in an entirely empirical fashion, the establishment
of a good water range outside which action needs to be taken (e.g. dilution with
non-recycled water).
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Rheology: basic concepts
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Grinding residue (curve A) decreases and finally stabilises: extending the grind-
ing time beyond this point yields no advantages whatsoever and merely wears the
grinding media. Viscosity, instead, initially declines sharply, stabilises during a sec-
ondary variable-duration phase and then recovers over the final phase as grinding
continues.
This behaviour can be explained as follows. The initial falloff in viscosity is
caused by the action of the deflocculant; the constant-viscosity phase is linked to
the fact that the clayey portion, which is more involved in the interactions with the
deflocculant, is already, at this point, in a homogeneous system of a particle size
distribution well below that set by the residue; the final increase is a result of vari-
ous factors:
Viscosity
Residue
time
Fig. 105. Changes in viscosity and residue during wet grinding.
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Rheology: basic concepts
At this stage of the process, where the system is subject to continuous and in-
tense shear stresses, viscosity is the most important factor: it must be low enough to
allow proper movement of the grinding media but not so low as to cause their rapid
wear, which would result in poor grinding efficiency. This is particularly true where
high-density grinding media are used.
Some examples of viscous grinding have, in fact, led to a reduction in overall
grinding times.
Unloading difficulties can effectively be resolved by adding small quantities of
deflocculant (generally 10-20% of the total quantity) a few minutes before the end
of grinding: this lowers the yield point and results in smooth slip outflow. High-
efficiency liquid deflocculants and automatic or semi-automatic dosing systems make
the task considerably easier.
Emptying or unloading the mills normally takes from 15 minutes to 1 hour; the
slip is subject to low shear stress and factors such as yield point and thixotropy
count for more than viscosity in itself.
It is at this stage that thixotropic slips with a high yield point tend to take on a
pseudo-solid structure (in jargon, they are said to ice or gel), forming a surface
crust and leaving significant quantities of residue on the grinding media and the
mill lining, thus making unloading tasks long and difficult.
It is interesting to note how this effect is never seen while the slip is kept mov-
ing, yet increases progressively under standstill or slow-flow conditions.
Systems which, at the end of grinding, reach and exceed 70-80 °C are a case
aside; in addition to having higher viscosity, these often form surface crusts because
of the increase in local density induced by water evaporation. Note also that exces-
sive end-of-grinding temperatures are not only useless (or detrimental) as regards
the rheological characteristics of the slip: they also imply wasteful use of energy
and may be indicative of problems or irregularities in grinding media size and/or
the ratio between the latter and the mill load.
Sieving is sometimes an integral part of unloading or is sometimes carried out
afterwards. It will be fast where yield points are low since an important trend is
towards finer mesh sizes to maximise the removal of potentially damaging impuri-
ties.
Sieving is often the slowest part of the entire production process. Consequently,
a number or series of sieves are used.
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At this point the body slip goes into holding tanks with low-speed agitation.
Holding times vary greatly depending on the size of the plant, ranging from 6-8
hours to 12-15 days.
Under these conditions (very low shear stresses and extended duration) time-
dependent phenomena such as thixotropy become crucial, especially where tanks
are full and there are nearly-still areas of slip.
Consequently, the formation of surface crusts often a tell-tale sign of im-
pending gelling or thickening of the entire mass are sometimes observed:
this event is known and feared by all ceramists, as it is the forerunner of a whole
series of difficulties. To recover from this problem pre-diluted liquid deflocculant
is added but it may take time to disperse throughout the tank.
Ceramic suspensions have inherently poor stability and should not be held for
prolonged periods unnecessarily.
Where unloading and sieving problems or thixotropy-related in-tank viscosity
increases occur continuously and frequently an in-depth rheological analysis and
review of the entire process may well be needed.
This chapter does not aspire to give a precise, exhaustive explanation of (or
easy solutions to) problems that often stem from a host of concurrent factors. It
does, however, intend to scrutinise the various factors contributing to the rheo-
logical characterisation of a body slip and provide guidelines that allow produc-
ers to predict (if not prevent) the phenomena and take effective countermea-
sures:
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Rheology: basic concepts
on the raw materials at the same time as the usual technological ones (absorp-
tion, shrinkage, firing colour, presence of carbonates etc.).
The same phenomena occurs when errors in formulation, weighing and so on
result in combinations overly-rich in plastic components being fed into the
mills.
3.B) Addition of sludge, glazes and recycled materials from glazing plants: once
again, laboratory testing is essential.
3.C) Addition (or increase) of exhausted lime from kiln filters. As calcium ions
cause flocculation in slips, dosing must be calibrated with care. With respect
to lime-free loads extra deflocculant must be added according to the quantity
of lime that has been introduced: in the most difficult cases this ranges from
50 to 100%, and has led some companies to abandon the use of recovered
lime in grinding altogether as it is anti-economic with respect to other solu-
tions (e.g. assistance from specialised companies).
4.B) Drop in percentage of deflocculant as the latter itself absorbs the water. A
fairly rare phenomenon that is usually easily visible to the naked eye.
5.A) Variation in particle size distribution in that there is an increase in the fine or
super-fine fraction owing to an extended grinding time (drop in residue). A
marked increase in grinding time generally leads to increased viscosity.
5.B) Like 5.A but brought about by the addition/increase of very fine recycled
dust or unfired scrap. In these cases too it is highly advisable to effect lab
tests before making any definitive changes.
The stocked and sieved slip is pumped to the spray drier at a pressure of a few
tens of atmospheres (on average about 30 Atm) using piston pumps.
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From a rheological viewpoint this is perhaps the least understood stage of the
entire process, as the physical stress the system is subject to is virtually impos-
sible to reproduce using laboratory instruments. On the whole though, it seems
safe to state that the system, where subject to very high yield stress, behaves in a
Newtonian manner in a laminar fluxing situation, at least as far as the nozzle
outlet where, aided mechanically, it rapidly transforms into a disordered cloud
to form the droplets that, following interaction with heat, will become spray-dried
grains.
If this fails to happen (or happens too late) the jets released from the nozzles
are projected and build up on the inner surface of the chamber, which if left can
seriously affect the performance of the drier.
Density, viscosity and other rheological parameters undoubtedly influence the
quality of the spray-dried product, but correlations between these parameters are
difficult and individual experiments are necessary in each case.
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Rheology: basic concepts
Rheological additives
Na5P3O10
A dispersant is that prevailing fluid phase into which the non-mixable solid or
liquid fractions are dispersed (such fractions thus represent the dispersed phase). In
most applications the dispersant is water.
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Deflocculation is that process in which the solid colloidal particles in the dispers-
ant fluid (e.g. a slip) move away from each other yet remain in suspension because of
the repelling electrostatic action that the deflocculant substance induces (by increas-
ing their zeta potential).
A fluidizer is a substance capable of making a fluid flow more smoothly (i.e.
lowering its viscosity). It is the exact opposite of a thickener, an agent that in-
creases the consistency of a fluid mass.
A deflocculant is a substance which, when added in small quantities to a fluid
mass, is capable of preventing agglomeration of the colloidal particles and thus
their precipitation. Since this effect can be achieved via dispersion (i.e. by addition
of the fluid phase) the two can easily be confused; while it is certainly true that a
deflocculant also acts as a fluidizer, it is not necessarily true that all fluidizers are
also deflocculants. The fundamental mechanisms that explain the deflocculating
action may be explained as follows:
l. shifting of the pH towards basic values by introducing OH- ions into the H2O-
solid system via an addition of monovalent bases or basic electrolytes which, by
hydrolysis, give OH- ions (an excess causes over-deflocculation).
2. substitution of other cations constituting the positive side of the diffused double
layer with Na+, K+, Li+, NH4+.
3. an increase in the negative charge on the clayey particles by adsorption of cer-
tain types of anion (adsorption is preferential for anions of higher valence with
a strong electric field).
4. increase in the total negative charge of the solid-liquid system, assuming a non-
ionic colloid carrying a negative charge.
5. addition of a shielding colloid that shields the suspended particles from the
action of flocculants.
6. elimination of any flocculants:
by precipitation of the flocculating ion
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Rheology: basic concepts
undesirable side effects, but also the effect they have on the dehydration rate, plas-
ticity and bending strength of the body.
The influence of the deflocculant on thixotropy and its effects during the down-
stream forming phase (adhesion to dies, chemical aggression on mould) must also
be evaluated.
Inorganic deflocculants are more sensitive to the nature and the quantity of ions
already present in the suspension, are not eliminated during the drying and firing
phase and do not generally have any thixotropic effects.
Concentrations being equal, organic deflocculants are more effective, less sensi-
tive to interference from other ions and have greater stabilising power. They volatilise
during firing, are usually thixotropic and are more expensive.
Choosing the right deflocculant is a case-by-case affair and will necessarily in-
volve practical tests.
The most complex problems can be resolved by using compatible mixes of or-
ganic and inorganic substances that provide good synergic performance.
Inorganic deflocculants
Na2CO3
The aggression of the salt Na2SO4 lowers deflocculating power and damages the
plaster.
Na2CO3 , which melts at 850 °C, increases plasticity and the dry bending strength
of bodies but reduces the drying rate.
Na2O - n SiO2
The sodium silicate, which hydrolyses easily with an alkaline reaction (pH > 11)
gives Na+ and OH- by separating the colloidal silica
The silicate is not as aggressive towards the plaster as the carbonate and has
binding properties. Where sulphates are present its deflocculating power is reduced.
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The mix:
Na2CO3 + Na2O - n SiO2
has the advantage of acting in a good four of the six ways described in the
preceding paragraph (namely 1, 2, 5 and 6). It thus has a higher deflocculating
power and results in fewer defects being caused by the aggression of Na2CO3. These
are stable solutions that let gelatinous silica separate. Additions usually fall in the
0.2-0.6% range (by weight).
Phosphates, Polyphosphates
Those with the most remarkable deflocculating power are sodium
hexamethaphosphate (NaPO3)6 and the polyphosphates, especially sodium tripoly-
phosphate (Na5P3O10).
The mechanism exploits the fact that the phosphoric anion is one of the anions
that is preferentially adsorbed by the clay particle, increasing its negative charge.
The consequent increase in the zeta potential makes a key contribution to a greater
dispersant effect. They are also capable of seizing flocculating ions to form coordi-
nation complexes.
An example is provided by hexamethaphosphoric acid (H6P6O18) which, with the
Ca2+, Mg2+, Fe3+ ions forms complex compounds of the following type:
[CaP6O18]4-, [Ca2P6O18]2-
BaCO3
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Rheology: basic concepts
the zeta potential) especially in the presence of the ideal flocculant Ca2+, Mg2+, Fe3+
etc.
This is because the SO4= anion (unlike other anions such as the phosphoric one)
is easily adsorbed by the clayey particle even in substitution of the OH- ions. This
happens even if SO4= is present in the form of a strong electrolyte (e.g. Na2SO4):
other strong electrolytes such as NaCl act similarly.
The ideal thing is thus to remove the SO4= groups.
As mentioned above Na2CO3 reacts with the sulphates (e.g. CaSO4) and CaCO3
precipitate forms, removing the Ca2+ flocculating cation, but failing to eliminate the
SO4= anions which always remain (like Na2SO4 soluble in H2O) even where silicates
or sodium phosphates are present:
Organic deflocculants
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The colloidal clay-humic acid mix is very stable and thus difficult to disperse. A
commercially available humate-based deflocculant has been obtained by treating
the lignite with soda.
Tannin compounds
Tannins of a colloidal nature and those of vegetable origin such as the humic
acids (used in tanning processes owing to their insolubility and because they pre-
vent the leather gelatine from rotting), have deflocculating properties.
The prototypes are tannic acid and gallatannic acid (a mix of glucose and gal-
lic acid esters), the latter belonging to the vast group of the phenolic acids, organic
compounds having a molecule that simultaneously houses more than one carboxylic
group and one or more phenolic hydroxyls.
From this compound for the elimination of CO2, pyrogallic acid is obtained. The
alkaline salts of such compounds (sodium tannate, sodium gallate, pyrogallates) are
all good deflocculants on a par with the humic derivatives. It has been hypothesized
that the tannin molecules are adsorbed at the surface of the dispersed particles with
the aromatic part protruding into the dispersant. This would alter the exterior of
the particles with variations in hydration and consequent lowering of viscosity.
Acrylic derivatives
Derived from acrylic acid CH2 = CHCOOH, with an acid force greater than that
of acetic acid, CH3 COOH.
Na+ ed NH4+ salts can easily be obtained via substitution of H+.
Acrylic acid gives rise to a wide range of polymers with which it is possible to
form acrylic resins, important groups of thermoplastic resins. Furthermore, the
double ethylenic bond is another point capable of reacting. Also of interest are
compounds of the CH2 = CHCOOR type where
R = metal, alkyl
If R = CH3 (acrylic ester)
If R = C2 H5 (polyester)
Others of importance are: CH2 = CHCH acrylonitrile
CH2 = CHNH, acrylamide
Acrylic acid and its derivatives polymerise easily under the action of heat, light
and peroxides (benzoyl), giving rise to (polyanionic) polyacrylic acids with the corre-
sponding polyelectrolytes, the polyacrylic derivatives, polyesters, polyacrylnitriles etc.
COOR CN
| |
- CH2- CH - CH2 - CH - CH - CH2 - CH - CH2 -
| |
COOR CN
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Rheology: basic concepts
Polyacrylic acid dissolves fairly slowly in water and its alkaline salts are easily
soluble. Polyesters and polyacrylnitriles are insoluble.
It should be noted how certain electrolytes obtained by way of a partial alkaline
hydrolysis of the polyacrylnitrile have considerable aggregating power. Others are
effective dispersants.
The length of the chain is fundamental. Those of greater molecular mass act as
flocculants.
Polyacrylates are electrolytes and perform their deflocculating action according
to the rules typical of the deflocculant; the polymer anion is easily adsorbable by the
clayey particles, thus guaranteeing an exceptional dispersant action and excellent
stability over time.
Acrylic deflocculants appear to be better than traditional ones (silicate, carbon-
ate, NaOH, polyphosphates), seeming less sensitive to overdeflocculation and inter-
fering cations.
Their thermo-plastic nature, however, can make their employment difficult. Fig.
106 compares acrylic deflocculants with other deflocculants such as silicate and
sodium tripolyphosphate which alter the viscosity of a slip as a function of the
quantity introduced.
Polypropylate Na
Brookfield viscosity (epoises)
Acrylic RLP/4
Acrylic R727/S
Acrylic R747
Percentage of deflocculant
Fig. 106. Comparison of how various deflocculants, applied in different percentages, affect the viscosity
of a white tile body (by G. Malandrino).
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Ammonium derivatives
Substituting NH3 (ammonia) with one or more organic radicals gives methy-
lamine (RNH4) and diethylamine etc. The amines are basic substances which disso-
ciate in water. Aliphatic amines are more dissociated in aqueous solutions than NH3
and are thus more basic. Aromatic amines are less basic.
Many substances such as ethyl amine, diethylamine, polyvinylammine and pip-
eridine are good deflocculants but are used only rarely.
Oxalates
COOH
These derive from oxalic acid | which is quite a strong acid and can form
COOH
complex salts. Sodium and ammonium oxalate are used little as deflocculants: these
are both soluble in water, unlike the other oxalates which are insoluble.
Sodium and ammonium oxalate have the property of making the Ca2+ precipi-
tate completely. The oxalate anion may also be adsorbed by the surface of the clay
particles. These compounds are also used together with others having a higher
deflocculating power.
Other substances
Other deflocculating substances worth remembering are the sodium salts of the
polymerised alchil-naphtalen-sulphonic (pH 8-10,5) acids, lithium citrate and the
sodium derivatives of carboxymethyl cellulose (CMC), an electrolyte with colloidal
anion (Fig. 107).
The CMC anion is irreversibly adsorbed at the surface of the mineral particles,
thus increasing their negative charge and dispersion capacity. The smaller the de-
gree of polymerisation, the greater the observed deflocculating effect.
CMC is used in ceramics as a binder while, however, bearing in minds its
deflocculating properties.
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Rheology: basic concepts
Cellulose
Caboxymethyl cellulose
aqueous suspension systems used in ceramics is of great importance and the main
operative mechanisms of rheological additives have been illustrated.
As seen, rheological additives are used because it is necessary to work with aque-
ous suspensions of a high solid content; yet we must be able to modify and/or
maintain precise characteristics of viscosity, plasticity, thixotropy etc. vis-à-vis the
manner in which the solution will subsequently be used.
For this reason various classes of rheological additives have been defined as a
function of the role they play in the preparation and control of clayey bodies and
glazes.
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Of coarse, the whole process also depends on other factors such as the grinding
time and the cost/performance ratio of the deflocculant.
Sodium bicarbonate used only rarely in spray drying bodies and only in those
bodies with very low plastic clayey fraction content (white body double firing) be-
cause of its low fluidizing effect.
Side effects
Common to all deflocculants not just those used in ceramic bodies is the
phenomenon of over-deflocculation. This is an increase in apparent viscosity caused
by an excess of deflocculant. Organic products, where introduced into bodies where
a situation of compromise or risk already exists, tend to emphasize those black
core reduction phenomena caused by poor permeability or problems connected
with a firing curve that is unsuitable for oxidation. This tendency is much less marked
in synthetic products.
Another effect (this time a positive one) sometimes observed, although not yet
fully understood, is a possible increase in the unfired strength of the pressed items.
This is mainly connected with silicates or sodium polyphosphates.
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Rheology: basic concepts
Ceramic glazes
As seen, in the ceramic industry the use of rheological additives is not so much
governed by economic-productive aspects as by the absolute need to work with
suspensions having certain chemical-physical properties that are suitable for on-tile
application and compatible with different application technologies which often in-
volve machines with extremely different operating principles.
In this case, rather than sub-dividing the most commonly employed additives on
the basis of characterisation, they have been classified according to the effects they
produce:
1) Deflocculants the main effect these have on a glaze slip is to lower its appar-
ent viscosity. These products can be added at the grinding stage or on the glazing
line (the latter being suitable for liquid or easily soluble products only).
The main product classes are the already-seen ones of the sodium polyphosphates
(tripoly, tetrapoly...), the sodium or ammonia derivatives of polyacrylic or
polymetacrylic acid or copolymers of more complex structure.
The advantages of high density grinding (i.e. with a high percentage of solid)
are as follows:
reduction of grinding times
greater uniformity of particle size distribution
better reproducibility
greater versatility in subsequent applications.
These additives are used in varying percentages, depending on the efficiency of the
product and the desired effect: generally, percentages range from 0.03% to 0.4%.
Additions along the production line are mainly to correct viscosity to the specifica-
tion required by the application machinery and the aesthetic effects instantaneously.
Another (positive) effect sometimes observed, the mechanism of which has yet
to be fully understood, is a possible increase in the unfired strength of the glaze,
largely connected with utilisation of silicates and sodium polyphosphates.
Side effects
Can be summed up as follows:
a) glaze dries more slowly
b) improved spreading, especially with disc application
c) slower short-term sedimentation rates
d) formation of extremely tenacious sediments (or cementing) in the medium and
long term
e) reduced plasticity and thixotropy in high-density glaze suspensions where bell
application systems are used.
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Overdosing effects
a) viscosity too low and flow excessive: may cause irregular application (e.g. accu-
mulation at sides)
b) overdeflocculation.
The final group of additives is the glues (binders). Certain glues are used in ceram-
ics as glaze adhesives. There are various types: methylcellulose, ether and ester
starches etc. Undoubtedly the most commonly used glues are the carboxymethyl
celluloses (CMC).
Use is made of their properties as binders, in that they improve the cohesion of
the unfired glaze particles and the adhesion of the latter to the tile body, as evapo-
ration regulators (they slow down evaporation of the liquid phase), and they im-
prove the spreading characteristics of the glazes.
Rheological effects strictly depend on the type of CMC used: a rough classifica-
tion, based on the viscosity of the solutions at 2%, can be made as follows:
low-viscosity CMC (between 5 and 50 mpa.s approx., where mpa.s = milli pascal ×
second)
medium-viscosity CMC (between 100 and 1000 mpa.s approx.)
high-viscosity CMC (between 1000 and 10,000 mpa.s and beyond)
The corresponding rheological effects, at standard usage percentages of 0.1-
0.6%, are:
low-viscosity CMC causes a slight drop in viscosity in the suspension and
tends to lead to cementing
medium-viscosity CMC limited effect on viscosity and a light suspending ef-
fect
high-viscosity CMC causes an increase in viscosity and has a high suspending
effect. Overdosing, of course, causes excessive increase in viscosity, extended
drying times, irregular absorption of the glaze by the body.
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Rheology: basic concepts
Fig. 108. Rheological behaviour of a bell-applied double firing glaze: high viscosity (indicated by
graph gradient), zero yield point. (Curve obtained after stressing the fluid at the maximum value of D
for 1 minute).
without additive
Fig. 109. Effect of adding small quantities of sodium tripolyphosphate (NaTPP) and carboxymethyl
cellulose (CMC) to a glaze with high yield point. (Curve obtained after stressing the fluid at the maxi-
mum value of D for 1 minute).
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without additive
Fig. 110. Effect of adding high molecular weight CMC to a low-viscosity glaze. (Curve obtained after
stressing the fluid at the maximum value of D for 1 minute).
Fig. 111. Rheological behaviour of a disc-applied glaze. (Curve obtained after stressing the fluid at the
maximum value of D for 1 minute).
Kaolin
Without additive
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Rheology: basic concepts
Fig. 113. Effects on rheological properties of increasing the apparent density of a glaze: as density
increases there is a marked increase of all parameters: viscosity (gradient), thixotropy (area of hyster-
esis), yield point (shift from origin).
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f) Organic substances decompose under the effects of heating, giving rise to gase-
ous substances which exit via the glazed surface. If there is poor compatibility
between the quantity and quality of the organic substances and the firing cycle
there may be degassing and black speck problems.
The presence of certain organic products (starches, CMC and other cellulose
derivatives) also causes biological decomposition via micro-organisms (moulds, bac-
teria). This mostly occurs in solution. The main effect in a glaze slip is loss of
adhesive power, which immediately translates into pin-holing, dimples right across
the surface, and then micro-fractures and fissures on the sides.
This problem occurs with glazes containing CMC applied some few days after
grinding.
In truth, though, it should be noted that the rheological additives form only a
tiny proportion of total chemical auxiliaries, represented by silk-screen printing
products. The latter, in fact, are the main cause of fume filter clogging and in-
creased COD in waste waters etc.
As far as the BODIES are concerned there is a widespread tendency for produc-
ers to use low-cost additives, even where they are less effective. Producers also tend
to invest little in new product research.
The most widely used product class is that of the fluidizer-deflocculant
polyphosphates. In particular, sodium tripolyphosphate is used extensively in quan-
tities of 0.2 - 0.4% (by dry raw material weight).
These are normally used in percentages of around 0.1%. Since they are perfectly
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Rheology: basic concepts
soluble (the products are commercialised in solution), their action is always well
distributed and stable over time.
The main disadvantages, though, are high costs and the fact that the polyacrylic
chain breaks up if added during grinding, thus reducing effectiveness. Further-
more, as they are organic compounds they are less suitable for addition to the body
as they produce, by pyrolysis, damaging reducer compounds and ammonia (or, gen-
erally, nitrogen-containing) salts which makes the lime in purification units mal-
odorous. If dosage is excessive their effects are irreversible but an increase of so-
dium and/or ammonium may create undesired effects.
Other additives which have been used or tested in a production context are hu-
mates etc., applied in percentages varying from 0.1 to 0.2%; while considered to be
highly active, they have very slow reaction times owing to their low solubility. This
can create serious problems at the mill before they are effective. While generally
inexpensive, these additives contain high percentages of carbon, with all its pos-
sible consequences.
Sodium silicate has the advantage of being very low cost, but its effectiveness is
not generalised and it does not exert a truly deflocculating action.
Overdosing can cause serious problems, and optimisation curves are very nar-
row indeed.
We shall now take a look at the additives used in the preparation of GLAZES. In
general it can be said that double firing glazes do not require any particular addi-
tives (sometimes suspension agents are used), single firing glazes always feature the
addition of glues and sometimes suspension agents, while monoporosa glazes gen-
erally require the addition of glue, fluidizer and sometimes a suspension agent.
Particle size distribution of the glaze itself (and thus mill load and grinding
media) plays a key role in glaze rheology as does solubility of the frits, which can
place cations of enormous rheological interference in the solution, with consequent
aging problems.
The fluidizers used in actual industrial production belong to the same categories
as those used in bodies.
There also exist specially produced combined-action salt mixtures with very
good storage properties.
Excessive dosing of these products results in excessive viscosity increases with
deleterious in-tank (ricotta) effects.
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Rheology: basic concepts
Chapter VII
Plasticity allows a ceramic body to be moulded into a shape that will subse-
quently be fixed during firing. This plastic state may be seen as an intermediate
condition in which the material is neither a solid nor a viscous liquid.
Applying pressure to a liquid causes it to flow according to the limitations and
specifications described in the preceding chapters, yet applying pressure to a solid
generates no appreciable changes until the ultimate load is exceeded and the piece
breaks.
A body with plastic properties behaves in an intermediate manner, as is evident
in the case of extruded materials prepared from bodies with a high water content:
outflow speed is proportional to applied pressure and continues as long as that pres-
sure is applied, yet the material maintains its shape and cannot therefore be consid-
ered a liquid.
With dry pressed ceramic materials (with a moisture content of about 3-6%)
the body does not have plastic properties as such; nevertheless the mineralogical
composition of the components and water content are essential for good pressing
results. The very structure of the clayey minerals crystallised strips separated
by well-defined gaps allows the lattice sheets to slide against each other when the
interlayer water acts as a lubricant.
Plasticity in these semi-plastic systems depends, then, on the formation of a
film of water around each individual grain of material. The thickness of that
layer is crucial: if it is excessive a second layer of free water which does not
interact with solid particles or cations in fracture zones forms, generating a
different type of flow that is actually detrimental to the plasticity of the system.
On the other hand, insufficient quantities of water will cause the particles to touch
each other, generating attrition and destroying any plastic properties. System plas-
ticity thus depends on a certain equilibrium which, in turn, depends on water
content and wettable surface area.
The thickness of the film of water enveloping the clayey particles when plastic-
ity is at its height, while difficult to calculate, has been defined (for an applied pres-
sure of 8 Kg/cm2) as:
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This ideal value can be significantly altered by innumerable factors, which, one
way or another, change the state of disturbance and electrostatic interaction be-
tween the water and the clayey particles. Such factors include:
water content
particle size distribution
size, shape and structure of particles
particle composition
aggregation
surface area and intermolecular attraction
the effects of additives (including natural additives such as salts dispersed in the
raw materials)
particle orientation.
Water added to raw materials for refinement (e.g. production of pure kaolins),
purification or grinding purposes must subsequently be reduced to allow moul-
ding.
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The removal of water
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Atm p 105 Pa
Temperature °C
Fig. 114. Saturated water vapour pressure at different temperatures.
For example:
80 g of clay from 100 to 1000 °C: m. Cs. ∆T = 80. 0.2. 900 = 14,400 calories
234
The removal of water
Drying rate
time
Fig. 115. Variation of drying speed against time (according to Y.H. Perry, from A.G. Verduch).
Drying rate
Moisture
Fig. 116. Variation of drying speed against moisture content (according to Y.H. Perry, from A.G.
Verduch).
the drying power of the work area, relative humidity, air speed
forces acting at capillary level
shrinkage caused by loss of moisture.
The drying process, then, involves transfer of heat from the surrounding envi-
ronment to the ceramic body and the simultaneous movement of water vapour in
the opposite direction. The heat (energy) needed for the former may reach the piece
via convection, radiation or conduction: normally, all three are involved.
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The most common effect of drying (by hot air convection) can be described by
the sequence:
transfer of heat from air to piece
transformation of water from liquid to vapour
removal of vapour from surface of piece
transport of liquid water from piece interior to the surface.
When surface evaporation speed exceeds internal capillary transfer capacity an-
other drying phase begins during which the evaporation front moves inside the
piece itself.
All this is usually represented by the classic description of a convection-type
drying process for porous and hygroscopic materials, according to a curve split into
at least three phases that are governed by different drying speed gradients at differ-
ent depths.
During the first drying phase water evaporation occurs as per the laws that gov-
ern evaporation from a body of water such as a lake, where a constant surface area
is in contact with an air flow of constant temperature and relative humidity: drying
speed is thus constant too.
During the second stage, drying speed decreases rapidly as the volume of water
evaporating from the surface has to be drawn from the interior of the piece by
capillary action: the rapidity with which this takes place will depend on the extent
to which the piece is heated and its dimensional variations (which influence the
vapour pressure of the fluid and thus its transfer speed).
As the evaporation front moves deeper and deeper into the piece, drying speed
falls as capillary resistance to diffusion increases: this resistance, of course, is in-
versely proportional to the size of the capillary ducts themselves. The smaller the
average diameter of the capillary the higher the resistance (according to the func-
tion x = k √ rt, where x is the speed of diffusion of the liquid, r is the capillary
radius, t is time and k is a constant that takes into account the surface tension and
viscosity of the liquid according to Poiseuilles law).
As a rough guide, vapour pressure values for water as a function of capillary
diameter are given in the following table:
236
The removal of water
According to Norton, the diffusion of water in the interior of the ceramic piece
is, then, a function of various parameters
dV k (U2 - U1) p
___ = ___________ dV/dt = flow rate of water through the piece
dt dη
U1-U2 = difference in moisture content between core
and surface
p = permeability of the ceramic body
d = distance from surface of interior point U2
η = water viscosity
in which the most representative variable of the choice of raw materials, techno-
logical process and characteristics of the ceramic piece is undoubtedly p (perme-
ability), greatly affected by particle size, plasticity and compaction etc.
Clays and ceramic bodies subject to drying, then, undergo consistent modifica-
tions in terms of shrinkage and weight loss caused by the evaporation of water.
Barellatographic analysis, employed to see just how these variations progress, yields
Bigot curves which illustrate the behaviour of the material in terms of shrinkage/
weight loss at a constant T, or other curves derived from these.
The drying process revealed by the barellatograph corresponds to theoretical
models put forward by Bourry (see Figs. 117 and 118). These diagrams represent
the percentages of body (by volume) occupied by clay, water and pores as a function
of drying time.
The ABC curve illustrates shrinkage: at time T1, for example, a body with an
initial volume of 100 consists of up of 56% clay + 15% water + 8% pores, and has
undergone a shrinkage of 21%.
Such curves, initially developed for extrusion technologies employing very slow
drying cycles (at ambient temperature and relative humidity), can also be traced
making the appropriate modifications for products of low water content subject
to extremely fast, high-temperature drying cycles.
As seen, one of the most significant factors affecting evaporation during the
drying of ceramic materials is the surface area of the material to be dried, which
influences the permeability of the material itself. Evaporation speed is also influ-
enced by hygrometric parameters in the drying area: a flow of dryer or completely
dry air is particularly effective in increasing evaporation during the first stage of
drying, while its influence will decrease at the capillary transfer stage as surface
evaporation comes to an end.
Once the critical humidity point is reached (point of inflection on Bigot curve),
the ceramic body assumes an almost-definitive consistency and rigidity and adapts
to tension less easily.
As shrinkage in the first stages of drying is much more marked than in subse-
quent stages, the resulting tension may lead to differential shrinkage, deformation
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Kaolin Montmorillonite
Shrinkage
Shrinkage
Water Pores
Volume (%)
Volume (%)
Water Pores
Clay
Clay
Hours Hours
Shrinkage
Water Pores
Volume (%)
Clay
Hours
238
The removal of water
or crazing when an excessive humidity gradient exists between the interior and
exterior of the ceramic body. The distribution of water around the particles and
the way in which the latter gather closer together as drying progresses are illus-
trated in the diagrams in Fig. 119.
The differing orientation of the clayey particles and the presence of differently
sized particles of other hard materials has, then, an enormous influence on dry-
ing. For example, clayey structures with a playing card castle configuration dry
faster than those arranged as a deck of cards. This is because the latter are more
compact and oppose greater resistance to evaporation.
Figure A Before the start of drying the indi- Figure B As soon as the surface water has evapo-
vidual particles are separated by a thin film of rated and water starts being drawn from the in-
water (grey area). terior by capillarity, the particles begin moving
and may start coming into contact with each other.
Figure C Even after the second drying stage Figure D In the final stages of drying tem-
significant quantities of water still remain be- peratures must exceed boiling point to remove any
tween the particles, in the pores. residue. At this point there is a partial collapse of
the particle structure.
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Illustrating, then, what happens during the removal of water in terms of its
interaction with solid particles as opposed to its position in the piece, it can be said
that drying removes the water in pores or interstices, water adsorbed on the surface
of the mineral (especially clayey) particles or water introduced into their structural
interlayer.
None of these types of water form part of the crystalline structure of the
clayey minerals.
The drying (and plastic) properties of clays are mainly determined by the size
and shape of particles, by composition and structure, ionic exchange capacity,
exchangeable types of ion and, finally, by their current state of hydration. To
these intrinsic qualities must be added extrinsic ones such as spatial relations
between the particles, pore size and interstice size distribution, degree of com-
paction etc.
The water surrendered at modest temperatures that which is neither part of
the crystalline structure nor attributable to the OH- hydroxyls in the composition
(the so-called chemical water expelled between 500 and 800 °C) can be divided
into three categories:
water in the pores, on the surface and at the edges of the particles
interlayer water, between elementary clayey sheets (e.g. in smectites)
water in structural channels (e.g. in zeolites).
Eliminating water of the first category requires low yet constant energy as seen
in Fig. 115 and thus relatively low temperatures (even ambient temperatures will do
where relative humidity is low). Temperatures in excess of 100 °C are used to accel-
erate the process and increase the thermal gradient between the interior and exte-
rior of the piece.
On the other hand, waters of the second and third category are eliminated with
lesser or greater difficulty as a function of various other parameters closely tied to
the texture and compaction of the materials. Interactions between clay and water
depend, in fact, on the physical and chemical reactivity of the surface of the clayey
mineral, where oxygen, hydroxyls and in the fracture zones other elements are
present; the distribution of these active sites determines the surface activity of the
clayey minerals (exchange capacity, ionic selectivity...); specific surface charge, sur-
face area and pH also play an important role.
Clayey minerals are not perfect crystals. On the one hand, they always have frac-
tured edges and consequent bond breaks that remain unsaturated. On the other
hand isomorphic atomic substitutions bring cations of different oxidation states
into play; these alter the natural electro-neutral structure of the crystal. These
factors, then, cause the solid particles to behave as if they were large, weakly (mostly
negatively) charged insoluble ions, as isomorph substitutions of insufficient charge
are more common.
These charged particles are, then, distributed in contact with and within the wa-
ter, which is, of course, impure (i.e. exempt from ionic charges due to saline
solubilisations).
240
The removal of water
Thus far, we have examined concepts that regard drying by convection. Drying
processes that use only conduction are few and have little relevance here owing to
the poor thermal conductivity of ceramic materials. Yet the drying possibilities
offered by radiation are, instead, certainly worth a brief look as they offer the op-
tion of a more selective kind of drying that acts almost only on the water actually
contained in the piece.
These systems can accelerate the drying process significantly and are extremely
energy-efficient, using electromagnetic radiation at the infrared (IR) and micro-
wave (MW) wavelengths (see Fig. 120).
In both cases, since the majority of water in the piece is contained in its inner-
most layers and ceramic materials are virtually radiation-transparent, heating takes
place from within.
This is because it is the water which first transforms the radiation energy into
heat energy.
Of course, this also aids evacuation of vapour because, unlike convection heat-
ing, surface porosity is unaffected by structural shrinkages (except, perhaps, at the
end of drying). Infrared driers exploit the fact that water has an almost unitary
absorbance factor (0.92) for radiation of wavelength λ = 2.8 µm, and a still-excel-
lent absorbance factor (0.91) at λ = 5.95 µm (see Fig. 121).
The main obstacles to its use, especially in Italy, lie in the high cost of electricity
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(such hyper-frequency radiation cannot be generated from any other source) and
the difficulty of controlling the drying process effectively, as it tends to be too
rapid, thus causing the pieces to break. Moreover, the working life of microwave
generators (magnetrons) is relatively limited and their maintenance is somewhat
costly.
A description of the most commonly used drying systems employed by the ce-
ramic industry is given in the relevant section of Volume II of this work, which
242
The removal of water
focuses more on the ceramic products themselves. That section will also examine
the most important technological parameters for proper control of the drying pro-
cess, namely:
temperature distribution
contact surface area
airflow
vapour extraction.
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244
Description of ceramic products
Chapter VIII
Although we have now clarified the main characteristics of the individual raw
materials and stated how they are selected, combined and prepared, we have yet to
provide information on the most suitable combinations and mixtures for the pro-
duction of ceramic tiles, which cover a wide range of technological characteristics.
In fact, depending on the context in which they are used, tiles must have good-to-
excellent load, abrasion and stain resistance (floor tiles) or, where they are to form
regular geometric patterns, need to be sized extremely accurately (wall tiles). Tiles
may sometimes be laid outdoors where they are subject to freeze/thaw cycles or
extremes of heat and humidity where different absorption and long term reactivity
to water or humidity are required.
These characteristics are listed in the International Standards contained in the
Appendices at the end of this volume.
Two of the most important final properties required of a tile, whether glazed or
unglazed, are bending strength and good dimensional characteristics (size and flat-
ness), as illustrated in Fig. 122. Yet these properties, with limits and tolerances that
depend on the intended type of product, are not in themselves sufficient to define
the formulation of a good body.
There are, in fact, plenty of other conditions that need to be satisfied, such as: a
plasticity sufficient for moulding and unfired handling purposes, the ability to dry
PRIME
OTHER NECESSARY GOALS
GOALS
FINAL TILE DURING FINAL TILE
PROPERTIES MANUFACTURING PROCESS PROPERTIES
Unfired bending
Ease of drying
of black core
Good glaze
Rapid firing
Sizing and
expansion
Absence
moisture
Bending
strength
strength
flatness
Limited
cycles
match
Composition
Grinding
Pressing
Firing
245
Applied Ceramic Technology
the material properly (and perhaps very rapidly), suitability for the firing process
etc.
Should manufacturers fail to meet these conditions the final product may suffer
from defects such as lamination, cracking, incompatibility with the glazed surface,
black core, post-expansion and so on.
Going back for a moment to bending strength, it should be pointed out that
products must meet minimum strengths as defined by relevant standards (Fig. 123);
to this end the ISO standard requires that not only Modulus of Rupture (MOR) but
also Breaking Strength be measured so as to ensure product bending strength inde-
pendent of thickness and size.
While, in fact, MOR is an intensive measurement that characterises the quality
of one material with respect to another, effective breaking strength indicates the
working behaviour of the specific piece.
To illustrate: a thin vitrified product has in any case a very high modulus, yet
the effective breaking load might actually be less than that of a standard-thick-
ness wall tile.
Another example that highlights the difference is the behaviour of unfired tiles
of identical thickness but differing sizes (e.g. 20 × 20 cm and 50 × 50 cm tiles): their
modulus will, of course, be the same, but the effective breaking load (and thus resis-
tance to stress on the production line) in the bending strength test will be much
lower for the larger tile.
This explains why finished product bending strength requisites set by Interna-
tional Standards establish minimum Modulus of Rupture from 15 N/mm2 (wall
tiles - class B III) up to 35 N/mm2 (stoneware - class B Ia), while minimum breaking
strength values range from 60 to 130 Kg.
MOR (kg/cm2)
Fig. 123. Bending strength requisites according to ISO standards (1 kg per cm2 ~ 0.1 N/mm2).
246
Description of ceramic products
Meeting these requisites is fairly easy, in that the same body can be used for more
than one product class; yet things become a little trickier when all the key proper-
ties of the tile are taken into consideration.
Above all, body behaviour during vitrification needs to be examined (Fig. 124):
vitrification curves (shrinkage and water absorption as a function of maximum fir-
ing temperature) for different product types [red (R) and white (B) body wall tile,
red (R) and white (B) body floor tile, porcelain tile (P)] show just how great the
differences can be.
% WA
wall red
wall white
floor red
floor white
porcelain tile
Wall tile bodies have high porosity within a fairly wide range at low-temperature
and then vitrify too rapidly to be used as flooring. A body intended for total vitrifi-
cation (water absorption = 0), such as stoneware, has, unlike standard glazed floor
tile bodies, wider stability at low porosities.
Such behaviour needs to be understood not only for production process
optimisation but can also be explained, forecast and modified as a function of the
chemical-physical characteristics of raw materials and body formulations.
As with porosity, shrinkage curves highlight an enormous diversity of behaviour
between the various bodies (Fig. 125).
The graph shows that white bodies are generally more stable than red, which are
more clayey and have a less balanced composition, in both vitreous and porous com-
positions.
As far as porous products (typical of wall tiling) are concerned, note the limited
shrinkage (< 1%) at low firing temperatures: this was once deemed necessary to
ensure maximum size uniformity.
Bending strength (Fig. 126) is, then, for the most part linked to processes that
take place during sintering.
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Shrinkage %
wall red
wall white
floor red
floor white
porcelain tile
wall red
wall white
floor red
floor white
porcelain tile
Consequently higher strengths are seen for the red bodies. which tend to be
more vitreous, except for porcelain tiles, the composition of which is specifically
intended to develop the glassy phases.
So far only those macroscopic factors that are usually monitored and controlled
during the production process have been considered. It is, though, possible to make
a more in-depth analysis of the structural modifications that take place in the mate-
248
Description of ceramic products
rials (especially during firing), thus allowing us to observe the root causes of the
phenomena illustrated above.
This more detailed examination highlights even sharper differences between the
compositional and behavioural differences of porous and vitrified bodies.
Starting with the former (Fig. 127), it can be seen how wall tile bodies are
characterised by an abundance of calcium and/or magnesium in the form of car-
bonates that decompose at temperatures above 800 °C, freeing the corresponding
oxides.
These oxides subsequently react with the rest of the ceramic matrix to form (at
relatively low temperatures) new crystalline compounds, Ca and Mg silica-alumi-
nates that provide a certain firing stability and develop bending strength before
giving rise to an uncontrollable fusion.
The numerous crystallines that can be created by a CaO - Al2 O3 - SiO2 system
are shown in the tertiary diagram in Fig. 128. Note the formation of gehlenite,
pseudo-wollastonite and anorthite, which, together, can lead to marked lowering
of melting points, thus fuelling further reactions via the formation of liquid
phases.
The following table (Fig. 129) shows some of the properties of the crystalline
compounds already in both the original compositions and the neo-formed composi-
% WA
Shrinkage
MOR
Decomposition
Degassing through glaze
of carbonates Presence
Tendency towards post-expansion
of free CaO
Increased bending strength
Dimensional stability
Increased shrinkage
Formation of Deformation
crystalline phases:
Gehlenite Uncontrolled
Uncontrolled
Diopside formation
formation of
of
Wollastonite glassy
glass phases
Anorthite phase
Fig. 127. Wall tiles: the symbols correspond to A.A. (water absorption), MOR (bending strength) and
shrinkage.
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Quartz
Albite
Orthoclase
Anorthite
Gehlenite
p-Wollastonite
Diopside
Forsterite
Spinel
Mullite
Fig. 129. Expansion coefficients and melting points for crystalline compounds existing or formed in the
bodies.
250
Description of ceramic products
tions (i.e. those formed during firing); these take part in the firing process and influ-
ence the final structural properties of the products. Note the generally high expan-
sion coefficients of the new compounds containing calcium and magnesium which
serve to inhibit shrinkage.
Theoretical melting points for pure compounds are, however, very high and their
formation from solid-solid or solid-liquid reactions is thus difficult: therefore the
percentages detected in fired products (especially where rapid firing cycles are used)
are generally low.
This is particularly true for mullite, which is unlikely to form even at very high
maximum firing temperatures. XRD analysis of fired wall tile powders (Fig. 130)
still show, however, significant traces of crystallinity of starting minerals, espe-
cially quartz, and partial formation of neo-phases (e.g. Diopside).
Fig. 130. X-ray diffraction analysis of wall tile body (Q= quartz, C= neo-formed comp.).
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The Na2O - K2O - Al2O3 - SiO2 tertiary diagram (Fig. 133) for sodium silicates,
potassium silicates and silica, shows how, in certain compositional fields, the devel-
opment of a liquid phase at decidedly low temperatures is possible (1118 °C for
sodium feldspar, 1150 °C for potassium feldspar). The tertiary diagrams refer, of
course, to systems in thermodynamic equilibrium and do not provide any informa-
tion on reaction speeds and necessary vitrification time which, especially in fast
firing cycles, must be brief.
252
Description of ceramic products
Absorption
Shrinkage
MOR
Phase transformations:
Metakaolin-spinel
Partial crystallite destruction Increased bending strength
(albite, orthoclase, quartz) Increased frost resistance,
Reduced permeability, shrinkage
Formation of
Deformation
glassy phase
Increased bending strength
Formation of new
crystallites (mullite)
Fig. 132. Totally vitrifiable bodies (for symbols Absorption and MOR see fig. 127).
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Applied Ceramic Technology
However, the reaction speeds of solid state compounds depends greatly on the
available surface area and, therefore, particle-size distribution. Completion of a crys-
talline solid particle reaction is unlikely inside a ceramic body. Yet it is possible for
reactions, mostly of the cementing type, to take place between the individual grains
aided by imperfections in the crystalline lattices and impurities, which, even in small
quantities can act as catalysts or give rise to low-fluxing eutectics (the same quan-
tity of material, at a density of, for example, 2.5 g/cm3, has a reaction area of 24
cm2/g where its average particle diameter is 1 mm; if this size is reduced to 50 µm,
the reaction area increases to 480 cm2/g).
Taking into consideration all the above factors and arguments and, most impor-
tantly, production needs, plant limitations, market demand, the availability of suit-
able raw materials and their cost, producers need to decide which type of ceramic
tile to manufacture. There are, in essence, three main product classes:
PORCELAIN TILES
254
Description of ceramic products
Chapter IX
WALL TILES
Introduction
Tiles were one of the earliest man-made technological materials.
From the very start they provided hygiene and fulfilled artistic and decorative
functions as well.
One of the oldest examples of glazed tiling is to be found on the Ishtar gate of
the Babylonian king Nebuchadnezzar II (575 B.C.), a restored version of which is
now on show in the Pergamon museum of Berlin.
Then there are the palaces of Nimroud and Khosabab, those of Cyrus, Darius,
Xerxes, several monuments in India, China and Turkey. The ceramic tile, then, has
been with us throughout nearly all human history.
In Italy, tiles were first manufactured during the Middle Ages, absorbing Arab
and other influences.
From these tentative beginnings came modern ceramics with its well-defined,
standardised products such as majolica, cottoforte, earthenware, gres, etc.
In Italy, the ceramics industry took off in the post-war reconstruction period of
the 1950s, with the manufacture of red gres and majolica and the advent of
cottoforte, a classic Italian product made using double firing techniques. It was
also during the 50s that ceramics was transformed from a network of small-scale
workshops into a true industry.
The technical dynamism of the industry proved decisive in promoting continu-
ous evolution of processes and materials.
The result was a shift from traditional double firing to fast double/single firing.
Tiles also became larger and their aesthetic/decorative effects were constantly up-
graded.
Most of these developments have taken place over the last twenty years, stem-
ming from experience in single fired floor tile products.
During the 70-80s the fast firing process, as far as wall tiles were concerned,
focussed almost entirely on glazed tiles and was initially a simplification of tradi-
tional tunnel firing systems using refractory saggers on cars.
Later, during the energy crisis at the beginning of the 80s the single firing
process was developed and adopted for porous body tiles too.
Single and double fast firing technology quickly became commonplace all over
the globe. Its spread has been (and is) dependent on a number of factors: local
levels of technical and professional skill, energy costs, labour costs and cultural
traits.
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Applied Ceramic Technology
The market
Figure 134 compares the evolution of the Italian market for double firing and
monoporosa wall tiles from 1990 to 1998. Note the slight fall off in double firing
output in 1993, followed by a more positive trend which lasted until 1998, stabilis-
ing at about 85 million m2 in the period 1996-97-98.
Monoporosa, however, showed a constant upward trend from 1991 onwards,
reaching a peak of 48 million m2 in 1995. The graph in Figure 135 shows percent-
ages of output accounted for by single and double firing respectively against the
total quantity of wall tiles.
Product classification
General wall tile classification includes products obtained by both double and
single firing.
International ISO UNI EN 13006 classifies ceramic tiles into several groups on
the basis of their forming method and finished product water absorption (see Fig.
137).
On the basis of current ISO 13006 standards, porous wall tiles are included in
the group
Fig. 134. Evolution of Italian monoporosa and double firing output from 1991 to 1998 (millions of
square metres source: Ceramic World Review n. 32/99).
256
Wall tiles
Water absorption
Shaping
GROUP
dry pressing BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
≤ 0.5% BIIa BIIb BIII
GROUP
BIb
Bib
0.5% - 3%
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Applied Ceramic Technology
Technical features
Wall tiles generally have the following characteristics:
high dimensional stability during firing, with almost no shrinkage (less than
1%)
porosity between 13% and 18% (expressed as percentage of water absorbed)
MOR between 200 and 250 kg/cm2.
These properties are only indicative, mainly helping us to classify the product
from a commercial viewpoint that takes into account its field of use.
The specifications provided for under ISO 10545.1 - 17, group BIII, include the
dimensional, physical and ceramic properties of the products.
Fig. 138 charts these last two, without taking size into account.
For more realistic comparison purposes the table shows, in addition to the values
defined by the standards, some characteristics of products actually available on the
market.
Any description of wall tiles must necessarily include the types and characteris-
tics of the glazes used in the new fast firing technologies. It should also be observed
that, as far as surface aesthetics (i.e. glazes) are concerned, the use of such technolo-
gies has neither modified nor materially improved the final results, since aesthetic
quality was already very high. Transparent (crystalline) glasses and opaque glazes
(mainly white), both of which are glossy, remain the most popular glaze bases to
this day.
While glazes have evolved to suit different firing technologies (traditional, dou-
ble fast, monoporosa), their technical performance in terms of resistance to stain-
ing, chemical agents and abrasion have remained largely unchanged. In the case of
white and crystalline glazes, the limitations and the potential provided by the
new technologies have required new frit and glaze formulations, with a shift from
viscous low-fluxing materials to high-fluxing compounds with eutectic melting.
This evolution in composition has affected both double fast firing and monoporosa
glazes.
Aesthetic features
Size
During the 60-70s, traditional firing processes mainly offered 15 × 15 and 20 ×
20 cm tiles. With the introduction of fast double firing and porous single firing
(monoporosa), tile size increased to 25 × 33, 33 × 45 and in certain cases 40 × 60 cm
and beyond.
The most common sizes, however, are those in the middle of the range: 20 × 20,
20 × 25, 25 × 33 cm etc.
Large tile production is much more limited but now increasing rapidly, such tiles
no longer being seen as just niche products. Such large tiles generally require sin-
258
Wall tiles
Standards 10545.1 and 10545.2 are not shown in the table owing to limited space. Nevertheless, the reader is reminded that they
contain sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (< 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving.
For more detailed information see UNI publications (Italy).
Fig. 138. Technical characteristics of porous wall tiles according to ISO standards.
gle-layer kilns and the advanced automation/ handling systems now available on
new fast-firing plants.
Trims
Special pieces, considered complementary to standard tile production, have gained
much ground in recent years. These pieces feature relief work obtained by pressing
(inserts, festoons, bull-nose pieces etc.). Production of such items is generally
outsourced to other companies and they are made using a glazing process followed
by decoration and third firing.
Moreover, there is also an increasing demand, especially in American and Asian
countries, for trims acting as a technical complement: these are used to finish
outside or inside corners or frame the perimeter of a tile-covered surface. Generally
speaking, these pieces are obtained using presses of limited power and special dies.
They are normally double-fired. In most cases, biscuit pieces are covered with stand-
ard glazes.
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Surface appearance
Traditionally, wall tiles have always been glossy. Consequently, glazes are gener-
ally transparent (crystalline) or opaque (basically white), rarely matt.
In the 60-70s, in traditional firing, frits with a high content of lead, boron and
cerium were used to obtain such decorative effects as torn, reactive, mother-of-
pearl, etc.
From a ceramic viewpoint, the effects were fascinating, yet their resistance to
abrasion and chemical aggression was very limited. The adoption of new formula-
tions and the partial replacement of lead with other fluxes has now provided manu-
facturers with crystallines and glazes on a par with their predecessors but better
suited to the new technologies.
Recently, the influence of developments in architecture and interior design has
given rise to new effects known as antiqued, which mimic aged plaster, chalky
surfaces, etc. and are sometimes highlighted by special elements built into the tile,
such as structured surfaces or intentional chipping around the edge.
The bulk of production, though, still uses glossy-effect glazes, enriched by decors
that take their cue from natural stones such as marble and breccia etc.
General features
In recent years wall tile compositions have evolved considerably, mainly to adapt
to fast firing cycles where body and glaze are fired together.
With monoporosa there may be interference between the degassing of certain
raw materials in the biscuit and the molten glass: this can lead to surface defects on
the glaze.
The key factors in the evolution of body compositions from those suited to
traditional firing, then fast double firing and finally porous single firing have
been:
reduction of clayey material percentages
introduction of higher percentages of fillers and complementary raw materials
(feldspars, feldspathic sands, quartz)
limitation of minerals which give off gaseous phases at high firing temperatures
(calcite and/or dolomite), especially in monoporosa.
In pursuing these goals it has been possible to employ tried and tested materials
by changing the quantitative composition.
In the case of monoporosa, it is preferable to use raw materials with a high
degree of purity and a fine particle size distribution.
Generally speaking, finished wall cladding products must have a high degree of
size stability.
260
Wall tiles
According to commercial classification, wall tiles can be divided into red and
white. In both cases, the raw materials are of two basic types:
clayey materials
complementary materials (feldspars, feldspathic sands, quartzes, calcites).
Figure 139 shows the chemical-physical features of the raw materials most com-
monly used in bodies for both fast double firing and monoporosa.
Some notes about the overall nature and mineralogical features of these materi-
als follow.
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1 1 2 3 4
3
4 2
3
1
2
3
1
2
3
PHYSICAL FEATURES A B C D
1
2 BREAKING LOAD BEFORE DRYING kg/cm2 6/8 8/10 10/15 4/6
4
BREAKING LOAD AFTER DRYING kg/cm2 15/20 20/30 25/40 10/15
3 4
1
FIRING AT 1100 °C A B C D
2
POROSITY % 8/12 2/6 5/10 15/20
12
SHRINKAGE % 2/3 4/6 3/5 2/4
Fig. 139. Chemical and physical characteristics of different raw materials suitable for the production
of porous products, especially monoporosa for indoor tiles.
262
Wall tiles
Feldspathic sands, feldspars and quartz: introduced into the composition as fillers
and/or sandy non-plastic materials to facilitate effusion of the volatile compounds
which escape during firing. Potassium feldspars are preferred as they are less reac-
tive than the sodium kind.
Feldspars also help lower the overall expansion coefficient of the ceramic body.
Quartz also plays a key role in adjusting the expansion coefficient (the latter in-
creases proportionally to the quantity present).
Given the rather coarse particle size distribution and the fast firing cycle, reac-
tivity of free quartz against alkaline-earth oxides (CaO and MgO) is thought to be
limited.
Calcite and/or dolomite: fundamental materials for wall tile bodies. In-body per-
centages range from 8% to 15%.
Their natural and post-grinding particle size distribution is particularly impor-
tant. In fact, very fine particle size distributions favour both decarbonation reac-
tions and, at a later stage, synthesis reactions with residuals of the clayey materi-
als (especially amorphous silica), thus allowing formation of transparent neo-formed
compounds (over 900 °C).
Of special importance are the kinetics of decarbonation and thus the kinetics of
gas (CO2) emission before softening of the surface glass (glaze) takes place.
The evolution and completion of synthesis reactions between silica, alkaline-
earth oxides and alumina play a key role in defining the physical and mechanical
features of the ceramic piece after firing (bending strength, expansion coefficient,
etc.).
It is evident that the quantitative ratio of clayey materials, calcite, feldspars,
quartz etc. depend on the intrinsic mineralogical nature and particle size distribu-
tion of the clays.
As a rough guide, Fig. 140 illustrates both a monoporosa (red and white fired
colour) and a fast double firing composition.
Body composition
As stated above, wall tiles can be obtained by double or single firing, and always
using fast cycles. Furthermore, body composition may aim to produce white or red
firing products. The latter mainly consist of varyingly carbonatic clays with a high
iron content. Other components may include feldspathic sands, feldspars, quartzites
and if necessary calcites and/or dolomites.
White firing bodies, on the other hand, use more balanced mixes of light col-
oured clays, calcite, feldspathic sands and quartz.
The most significant difference between white and red compositions lies in the
quantity and typology of clay used, whereas the most significant percentage differ-
ence between double and single-fired bodies is that the former may have high per-
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Applied Ceramic Technology
Fig. 140. Possible compositions for porous single firing (red and white) and double firing bodies.
centages of calcite and/or dolomite, even as high as 15-18% and, in certain cases,
raw materials with a slightly lower degree of purity may be used.
Figure 141 shows examples of different body compositions for porous single
firing and fast double firing, red and white firing respectively. In addition to com-
pound formulations (i.e. formulations obtained by mixing raw materials), the chart
also shows a clay-only body formulation.
This kind of composition is used more frequently in the case of fast red double
firing and is quite widespread in zones which have access to mixed clayey materi-
als which already include the various complementary minerals. Figure 141 also
shows the (CaO-MgO) - SiO2 - Al2O3 tertiary diagram for the formulations in the
previous figure. Three specific body compositions are highlighted; two of them are
264
Wall tiles
TIPOLOGIA - TYPOLOGY SiO2 Al2O3 TiO2 Fe2O3 CaO MgO K2O Na2O P.F.
Monoporosa 65.38 12.89 0.29 0.53 7.00 1.26 0.72 0.19 11.69
Monoporosa 61.42 14.08 1.18 1.22 7.40 0.99 2.06 0.17 10.96
Monoporosa rossa - Red monoporosa 56.10 15.12 0.91 3.79 7.80 1.40 1.25 0.90 12.89
Monoporosa rossa - Red monoporosa 54.76 15.98 0.90 4.88 8.10 0.77 2.37 0.99 11.31
Monoporosa rossa - Red monoporosa 65.99 18.9 0.70 3.04 0.80 0.56 1.72 4.67 3.62
Monoporosa 60.26 16.34 0.76 1.16 7.60 0.42 2.23 0.59 10.78
Monoporosa 69.36 12.30 0.50 0.59 5.70 0.29 3.47 0.23 7.37
Bicottura - double fired 60.31 13.40 0.57 1.95 9.35 0.31 1.17 0.25 12.82
Bicottura - double fired 61.29 11.45 0.68 2.85 5.92 2.61 2.39 2.03 10.76
Bicottura - double fired 59.37 11.58 0.63 4.56 5.78 3.13 2.49 2.04 10.44
Bicottura - double fired 63.12 12.68 0.52 4.51 6.06 0.79 2.71 0.42 8.51
Bicottura - double fired 65.80 13.77 0.89 1.56 5.82 0.6 1.41 1.86 8.29
CaO+MgO
Fast firing
Bicottura - Fast firing
Monoporosa
Monoporosa
Monoporosa rossa - Red monoporosa
Red monoporosa
SiO2 Al2O3
CD.0110
Fig. 141. Composition areas in the (CaO+MgO) - SiO2 - Al2O3 tertiary system relevant to the above-
described body composition for monoporosa and fast double firing.
for white and red monoporosa, whereas the third is a special combination obtained
only with double firing clayey material.
Product features
The final features of a ceramic wall tile are heavily influenced by newly formed
compounds which develop during firing.
These are created by the reactivity of calcium and magnesium oxides which
originate, respectively, from the destruction of the calcite and/or dolomite lattices
during firing, with the silica and alumina originating from the destruction of the
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clayey lattice. These newly formed compounds are gehlenite, diopside, anorthite
and wollastonite.
Features such as bending strength, expansion coefficient, moisture expansion
etc. depend on the quantity and quality of these compounds.
In fast firing cycles the tendency towards synthesis of new compounds, start-
ing with phases of varying reactivity, largely depends on the natural particle size
distribution of the materials and the degree of grinding that follows.
The pattern of decomposition and synthesis reactions which take place during
fast firing of a monoporosa body is shown in Figure 142: this diagram shows the
dynamics of original mineral decomposition and the formation of new compounds.
Figure 143 shows X-ray diffraction patterns for different firing temperatures.
Note that at 900 °C dolomite has almost entirely disappeared, yet the first crystal-
lisation embryos attributable to diopside and gehlenite have appeared. The
latter tend to increase up to a temperature of 1140 °C.
The most frequently used glazes are glossy, either transparent (crystalline) or
opaque (basically white).
These glazes use different frits depending on how they are to be used (i.e.
traditional or fast double firing or monoporosa).
Frits generally account for 90-95% of the glaze.
Small quantities (5-10%) of plastic materials such as china and ball clay, as
well as organic additives which adjust rheological features and adhesion to the
biscuit are used too.
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Wall tiles
*103
1.50 1.50
1140°C
1100°C
0.75 0.75
900°C
*103 650°C
3.50 0.00 0.00
22.00 32.00 42.00 52.00
2θ
1.75 1140°C
1100°C
900°C
0.00 650°C
2.00 22.00 42.00 62.00 2θ
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To achieve these goals, alkaline-boron fluxes are used in most cases. To further
optimise viscosity at peak firing temperature, the latest frits include high quanti-
ties of CaO and ZnO in their formulation, mainly at the expense of Na oxide.
Monoporosa
The need for carbonate minerals in wall tile body compounds (useful for intro-
ducing calcium and magnesium oxide) has resulted in considerable technological
problems in finding appropriate glazes for porous single firing.
Gas (CO2) emissions from the calcite and/or dolomite within a temperature
range of 750-950 °C (the maturing zone of traditional glazes) was one of the
main problems in perfecting this process.
The need for glaze softening temperatures higher than 950 °C made it neces-
sary to use new high-temperature fluxing formulations, based on eutectic melting
compounds.
This was made possible by reducing the quantity of oxides such as B2O3 and
Na2O and introducing CaO, MgO, ZnO and K2O as active elements in order to
bring about high temperature eutectic fusion.
To clarify this behaviour, Figure 144 shows heating microscope softening graphs
for two frit samples A and B. Sample A is a glaze for traditional double firing
which softens about 60-70 °C earlier than B. Sample A is clearly unsuited to
porous single firing because of its tendency to seal the surface too soon, trapping
gases in the body.
Figure 144 also shows the different chemical compositions for frits A and B,
used in traditional double firing and in porous single firing respectively.
Besides softening points, other important factors useful in defining the firing
behaviour of a monoporosa frit include: surface tension and hot viscosity of the
glaze.
Low surface tension helps to eliminate any gas bubbles in the glaze during
firing.
Low hot viscosity values, on the other hand, favour better glaze application
and also improve the smooth covering of the surfaces it comes into contact with
(engobe and/or body).
In addition to reactivity with the engobe and/or the body, glaze expansion
coefficient is also of great importance. A good expansion match with body and
engobe is essential to control tile curvature.
Engobes
An engobe is a partially glassy composition usually applied on the body. It is
virtually indispensable on monoporosa products and certainly advisable on dou-
ble firing ones and serves the following purposes:
inhibits any reactions of the glaze with chromophore impurities in the body
268
Wall tiles
A B
A
SiO2 55/56 53/55
Al2O3 7/8 8/9
20°C 840°C 960°C 1050°C 1260°C B 2O 3 12/13 8/9
CaO 2/3 7/9
MgO 0.5/1.5 2/4
Na2O 6.5/7.5 -
K2 O 2/3 3/5
B
ZnO 1/2 9/10
20°C 940°C 1020°C 1060°C 1210°C ZrO2 8/9 5/6
Fig. 144. Softening graphs under Leitz heating microscope: two frit samples of different softening
points.
The engobes normally used for monoporosa and double fast firing consist of a
percentage of frits (30-40%), ball-clays, zirconium silicate and sometimes feldspar
and quartz. The specific functions of each component may be summarised as fol-
lows:
the frits help to make the glassy matrix
the ball-clays provide the required plasticity
zirconium silicate improves the degree of whiteness
quartz and feldspar help control not only the fusibility of the mix, but also its
expansion coefficient.
Figure 145 shows two macro photographs which highlight how the engobe re-
duces contamination by any impurities present in the biscuit.
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Fig. 145. Macro photographs showing how the engobe reduces contamination by any impurities inside
the body.
The final properties and appearance of the product not only depend on the chemi-
cal and mineralogical nature of its raw material components but also on the practi-
cal as well as the technical requirements demanded by the various processes in the
production cycle.
a - Grinding
b - Spray drying
c - Pressing
d - Drying
e - Biscuit firing
f - Glazing
g - Monoporosa firing
h - Glaze firing
a - Grinding
The purpose of grinding is to reduce the size and homogenise the incoming raw
materials until a final, constant particle size distribution is attained.
With porous single firing bodies, the extent of raw material grinding, together
with other chemical and physical factors, may affect the extent to which carbonates
break down during firing and hence appreciably influence the temperature at which
gas (CO2) is emitted. The degree of grinding can also influence the reactivity of the
components being fired, and the degree to which newly formed compounds are
created.
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Wall tiles
Grinding residue
_____ Breaking load after firing (kg/cm2) .......... Calcite precentage in the grinding residue (%)
Fig. 146. Changes in fired breaking load (left scale) relative to the percentage of calcite in the grinding
residue (right scale).
illustrates variations in fired breaking load (kg/cm2) in fired materials made from
compositions with different residues after grinding.
The same graph also shows the percentage of CaCO3 in the residue, again for
the same compositions: post-grinding residue, in the case of compound bodies for
either monoporosa or double firing, is generally around 4-6% (at 63 microns - 230
mesh). In the case of red firing bodies, which mainly consist of clayey materials,
this value can be as low as 3-4%.
b - Spray drying
The purpose of this process is to evaporate a part of the water contained in the
slip while forming spheroid particles.
The particle size distribution of a wall tile body is not so different from that of
any other spray-dried body (i.e. single-fired floor tiles, porcelain etc.).
The graph in Figure 147 illustrates the similarity of the typical particle size
bands for monoporosa and double firing bodies.
Note that there is a concentration in both of around 70 to 80% in the 425-180
micron range.
c - Pressing
The purpose of pressing is to obtain the greatest possible green tile powder
density that is compatible with the black core or degassing problems which may
arise during firing.
Applying different pressing forces will, of course, result in pressed pieces of
different bulk densities and thus different shrinkage and porosity values too.
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Double firing
Microns
Fig. 147. Estimated variations in particle size distributions of monoporosa and fast double firing
bodies (spray-dried).
In the case of porous products, green bulk density variations do not involve
substantial shrinkage changes because shrinkage values for these products are in
any case very low (less than 1%).
High bulk density values (more than 2.1-2.2 g/cm3) can make the escape of gas
from the body more difficult during firing, and may cause boiling problems on the
glaze (monoporosa).
Bulk density differences within an individual pressed piece (e.g. powder loading
errors) can give rise to areas of porosity values that cause glaze application and
absorption problems.
The graph in Figure 148 shows the range of bulk dry density within which frits
having different softening points should not suffer from de-gassing problems.
The graphs also show the generally accepted production threshold values (shaded
area).
Specific moulding pressures for compound wall tile bodies are generally around
200-250 kg/cm2; for red firing bodies, which tend to be more plastic, pressure may
be less, even as low as 150 kg/cm2.
272
Wall tiles
Fig. 148. Relationship between dry bulk density ranges within which frits with different softening
points should not have degassing problems (shaded area).
d - Drying
This is an apparently simple stage, since the physical phenomena that accom-
pany the evaporation of residual humidity in the body (4-7%) are sufficiently un-
derstood and easily controlled.
During this phase, as residual moisture evaporates, the bending strength of the
ceramic piece increases because the particles move closer together and develop
stronger bonds.
In single firing products bending strength must be high: to withstand the me-
chanical stress of silk-screen printing. MOR must be no less than 25 kg/cm2.
With modern day drying cycles it is good practice to keep dimensional shifts
during drying within a shrinkage range of 0-0.3% so as to prevent cracking on the
faces or edges of the tiles.
e - Biscuit firing
Firing curves and kiln temperatures must permit and aid the development of
reactions between the various components so that the desired fired properties (po-
rosity, bending strength, expansion coefficient etc.) can be obtained.
It should be evident at this point that the sintering reactions of a ceramic mass
depend on the chemical and physical nature of the body, the degree of grinding, the
bulk density of the pressed material, and, finally, on the firing temperature (the
graph in Fig. 149 shows how unfired bulk density affects porosity and shrinkage
values.
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The graph in Figure 150 highlights the thermal expansion coefficient of sam-
ples fired at different temperatures. In both cases the data refers to a red firing body
composition.
f - Glazing
With wall tiles, the most commonly marketed products belong to the: transpar-
ent crystalline and opacified glossy white glazes.
Todays market demands a wide range of finishes, including rustic and antique
effects.
This trend, deeply rooted in the floor tile industry, is also beginning to take hold
in the wall tile market, though to a far lesser extent.
The most common glaze application devices are the bell units.
These allow producers to achieve smooth, mirror-like surfaces by passing the
unfired or fired tile through a continuous curtain of glaze of constant thickness
and flow rate.
In order to optimise application and prevent problems related to the glazing of
unfired tiles (monoporosa) there is now a tendency to reduce the quantity of water
in glaze slips as far as possible.
The rheological behaviour of such suspensions is often far from ideal and takes
on characteristics which tend towards a plastic and often thixotropic condition. In
the case of bell applications, optimum rheological performance in a traditional stand-
ard glaze will be provided by high density, very low yield point, constant viscosity
and very low thixotropy values.
Bulk
Bulkdensity
densityafter drying
after drying
(gr/cm ))
(gr/cm 33
0,00 20
Water absorption
0,20
absorption
Contrazione
15
Shrinkage
Shrinkage
0,40
0,60 10
Water
0,80
5
1,00
1,20 0
Fig. 149. Influence of post-drying bulk density on water absorption (porosity) and fired contrac-
tion.
274
Wall tiles
400
350
300
(30+400°C)
3 Alpha
250
200
150
100
CD.0106
50
0
650 750 850 950 1050 1100 1150
Firing
Temperatura di temperature
cottura - Firing (°C)
temperature (°C)
Fig. 150. Thermal expansion coefficients of body samples fired at different temperatures.
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τ [Pa]
Tau
300
NR 1 H2O 27.0%
200
100
NR 2 H2O 28.5%
0
0 100 200 300 D [1 / s]
Figure 151. Variations in the speed gradient D (1/s) as a function of shear stress t (Pa) for glaze
suspensions of different densities.
Another important aspect is screening and magneting of the glazes. Highly effi-
cient circular vibrating screens are now used almost universally.
There are three types of magnet but their efficiency depends on the flow rate
and density of the glaze:
cylindrical metal bars
beehive-shaped
rollers.
Tab. 13. Rheological characteristics such as viscosity, yield point and thixotropy for different glaze
suspensions (values indicative only).
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Wall tiles
g - Monoporosa firing
This is a very important stage of production, since all the reactions which deter-
mine the features of the final product take place here.
Monoporosa firing dynamics are special, since the body mass contains carbon-
ates and must be compatible with glaze characteristics.
The glaze must behave eutecticly, have certain refractory characteristics and
be fairly gas-permeable up to temperatures in the 950-1030 °C range after which it
must melt suddenly.
The critical parts of the firing curve and the technical explanations of them are
highlighted in Fig. 152.
The initial part of the curve up to 800 °C (A) coincides with the pre-heating
phase of the material and the destruction of the clayey materials.
In part (B), between 800 and 900 °C, the carbonates start to decompose and
CO2 escapes. It is essential that the glaze maintain a certain porosity during this
stage to aid gas emission.
In part (C), between 900 and 1100 °C, synthesis reactions between alkaline-
earth oxides (CaO, MgO), generated by decomposition of carbonates, take place
and residual amorphous phases appear due to the disintegration of the clays.
The development of these neo-formed compounds is essential in adjusting and
defining the physical and mechanical features of the product.
Monoporosa Temp.
Tile
Lower zone
Tile
Lower zone
Fig. 152. Simplified firing temperature graph illustrating basic firing aspects of monoporosa mate-
rials:
A: destruction of clayish minerals
B: total expulsion of gas (CO2)
C: neo-formed compounds begin to appear
D: stabilization of neo-formed crystalline compounds and complete melting of glaze
E: fast tile cooling.
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278
Wall tiles
DOUBLE FIRING
Fig. 153. Glazed tile and biscuit firing curves (double firing).
CD.0112
<
MOR modulus of rupture (kg/cm2)
>
=
Shrinkage (%)
Water Abs. (%)
Porosity
?
>
=
<
Fig. 154. Variations in MOR, shrinkage and porosity for bodies fired at different temperatures. The
significance of the different shaded areas is number-coded (4 refers to the most frequently used industri-
al firing temperatures for these materials).
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The dynamism of the ceramic industry has been decisive in the ongoing evolu-
tion of production processes.
The 70s saw significant technological-engineering developments, with a change-
over from traditional tunnel kilns to modern processes with roller kilns and fast
firing cycles.
Adoption of such technologies involved completely new layouts and the huge
increase in automation led to significant cuts in production costs. Significant devel-
opments in each stage of the production process continued to be made throughout
the 80s too.
These included:
widespread use of wet discontinuous grinding
introduction of spray drying
increased use of hydraulic presses
adoption of fast driers
increased use of roller kilns.
The introduction of fast firing processes for wall tiles was neither as immediate
nor as far-reaching as it was for floor tiles. Traditional firing technology, with the
plant engineering and automation solutions available at that time, not to mention
the aesthetic quality of the then-produced tiles, was still to some extent irreplace-
able.
However, the advent of so-called high-temperature fluxing eutectic glazes ac-
celerated technological developments, since the surfaces attainable with these glazes
were and still are of high aesthetic quality and comparable to, if not better than,
traditional ones.
The 90s thus saw a boom in monoporosa and fast double firing processes, result-
ing in manufacturing improvements and lower industrial costs.
Todays production plants offer various levels of sophistication, depending on
their degree of automation and type of control systems.
The factors influencing the degree of sophistication of a new plant are:
local levels of technology and general education
plant size
required plant flexibility.
Figure 155 shows flow diagrams for monoporosa and fast double firing, and
highlights the various processing phases (assuming use of continuous grinding,
increasingly popular even in small and medium-size plants).
Note that with monoporosa the material can be stored after glazing and firing
and can also be sent directly from the kiln outlet to the sorting area. In the case of
double firing, storage of the biscuit and the glazed tiles takes place in specially
designated areas.
280
Wall tiles
Fig. 155. Flow diagram for monoporosa and double firing processes with modern plants featuring
continuous grinding.
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Tiles are moulded in hydraulic presses, dried in fast automatic driers, put through
fast firing cycles in roller kilns and sorted using almost entirely automated machin-
ery.
Modern electronics has made it possible to automate the movement of green
and fired tile cars completely using wire and laser-guided systems.
The effects of such rapid technological-engineering developments are evident
and may be summarised as follows:
increased operator productivity
decrease in surface area occupied by plant
lower unit industrial costs.
Figure 156 shows the lay-out for a fast double firing wall tile plant.
1 2 4 6
3a 3b
CD.0109
Fig. 156. General plant lay-out for the fast double firing manufacture of about 8000 m3/day of wall
tiles.
Key: 1. Body batching and preparation - 2. Pressing - 3a. Body firing area -
3b. Glazed tile firing area - 4. Glazed and fired product storage -
5. Glazing department - 6. Sorting.
Machines
A brief description of the main machines used in a typical wall tile production
plant follows.
Other machines and production processes involving dry grinding and powder
re-granulation, which can also be used to produce wall tiles, will not be dealt with
here.
Dry preparation can be used in double firing where body compositions rich in
clayey materials (or materials with very similar morphological features) are avail-
able.
Production of monoporosa using dry grinding is less widespread and is gener-
ally more difficult.
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Wall tiles
Weighing systems
Mills
Wet grinding of the body may be performed using either a continuous or dis-
continuous process: selecting the most appropriate one depends on a number of
factors, such as:
plant size
professional qualifications of work force
characteristics of raw materials.
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required in the spray drier: this is because it is possible to work with slips having a
greater solid content than would be possible with discontinuous grinding.
To clarify, a brief description of the constructive and functional differences fol-
lows.
Discontinuous mills are cylinder-shaped and made of very thick sheet metal.
They have material loading-unloading ports and their interior is lined with various
materials, such as silica, alubit® (sintered alumina) or rubber; the grinding media
may be made of silica or alubit®.
The drive unit may be fitted with a static frequency converter and PLC control
logic so as to allow, where necessary, variations in mill rotation speed even during
the grinding cycle itself in order to optimise power consumption and productiv-
ity.
The continuous mill also consists of a cylindrical steel structure. The cylinder
interior is divided into two or three grinding chambers, separated by one or two
bulkheads. Hatches that open outwards are provided for inspection and mainte-
nance purposes.
The inside of the mill is lined with specially shaped wear-resistant rubber de-
signed to provide maximum grinding efficiency. Once again, grinding media may be
silica or alubit®.
In discontinuous grinding the properly batched load is introduced into the mill
together with the preset quantity of water and fluidizer.
Once grinding is over and the residue has been checked, the slip is screened and
unloaded into storage tanks.
In continuous grinding, instead, the mix is introduced into the mill without in-
terruption by various loading systems. The raw materials and the deflocculant are
pre-mixed with the watery suspension containing the screening residues.
At the mill outlet, the slip is classified first with a wide-mesh screen, then with a
battery of finer screens to sort the material more efficiently. The screen residue is
returned to the mill together with the pre-batched water, while the slip is delivered
to a holding tank equipped with an agitator from where it can be sent directly to the
spray drier.
Should the physical characteristics of the materials be satisfactory (naturally
low residue values), a part of the clays (and, if needed, the green scrap) can be
dissolved in a turbine mixer without being introduced into the mill.
Alternatively, the clayey raw materials may be put through a preliminary
disintegrator after which they are ground in the mill together with other body
components.
This option is especially appropriate where bodies have a high proportion of
very plastic clays with relatively high natural moisture content (above 15-20%).
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Wall tiles
Spray driers
Spray drying evaporates nearly all the water contained in the slip. Water con-
tent is reduced to percentages of around 4 to 7% by spray drying.
The slip is injected upwards from the bottom of the drier through variously
sized nozzles situated on a ring mounted at the centre of the cylinder: these noz-
zles are fed by high pressure pumps (25-30 bar).
Simultaneously, hot air flows downwards from the top of the cylinder and is
distributed tangentially, the counter-flow with the slip resulting in heat exchange.
The spray drier may be seen as the final digester of dirty wash water, sludge
and all the powders generated during the production process as it batches them
into the slip systematically.
To ensure compliance with environmental standards, the spray drier can also
be provided with dry or wet filters to capture particularly fine dust which would
otherwise be dispersed with the steam coming out of the chimney.
Where appropriate, the spray drier can be powered by co-generation systems
so as to reduce running costs.
The spray drier, then, transforms the slip into a powder of controlled parti-
cle size and humidity which is then conveyed, via conveyor belts, to the storage
silos.
Presses
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Hydraulic press.
This last requirement is met not only by the above-mentioned isostatic punches:
special feeding devices which ensure uniform powder distribution in the die are
also used.
Driers
Drying, which eliminates the residual moisture from the just-pressed tiles, is
performed on either vertical or horizontal driers.
The tiles exiting the presses are transferred on roller conveyors.
Vertical driers consist of a load-bearing structure made of steel sections with
insulation panelling.
The tiles are laid out on racks (consisting of revolving roller shelves) which are
hinged on the links of a chain system that supports them and moves them through
the drying channels.
Internal ducts feed hot air to the drying area and cold air to the cooling area via
a series of manually adjusted dampers. Heat is provided by air-flow (in-vein) burn-
ers which can run on liquid and/or gas fuels.
Horizontal driers consist of metal modules with insulating panels and insulated
exterior piping for air re-circulation.
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Wall tiles
The tiles run through the whole length of the drier on a speed-adjustable roller
conveyor. The machine consists of a series of identical modules, each one with its
own independent thermo-hygrometric and ventilation air flow characteristics. Each
zone has its own hot air generators too.
Normally, the final section of the machine is designed to stabilise the tempera-
ture of the outgoing pieces.
With vertical driers, the drying cycle lasts 35-70 minutes; with horizontal
driers, cycles can be speeded up to 6-20 minutes. In both cases, however, the dura-
tion of the cycle depends on the type of body and the size and thickness of the
pieces.
With monoporosa, a uniform tile temperature at the drier outlet is essential.
Since vertical driers have high thermal inertia, they keep the surface temperature of
the outgoing tiles within minimal tolerances even in the event of frequent produc-
tion line (glazing) stoppages.
Glazing machines
The glazing lines used for monoporosa and double firing products are essen-
tially the same, except for a few complementary devices such as the fettlers (the
type depends on whether the tiles are fired or dried). Monoporosa glazing lines are
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generally longer. As seen, the majority of wall tiles have smooth, mirror-like sur-
faces. The most suitable engobe/glaze application devices for this sort of finish are
bell units.
Special airless atomisation systems have also become increasingly widespread:
these provide even distribution of water, fixing agents and engobe. Where an-
tique or rustic effects are desired, repeated application tasks such as flashing, brush-
ing, dry application, etc. will be required in addition to the traditional disc or bell
curtain glazing systems.
Glazing machine manufacturers have responded to such requirements with ma-
chinery that provides high-quality aesthetics. Note also that in order to obtain a
proper degree of flexibility on glazing lines there should be numerous application
stations and all the relevant equipment useful for rapid product change-over. This
inevitably implies very long glazing lines which have, over the years, maintained
the same basic structural and functional features.
Moving on to decoration, the wide range of print types and patterns currently
in demand means that both flat and rotary screen machines are used. Rotary ma-
chines are increasingly used because they are fast and require little monitoring and
maintenance.
There are several kinds of rotary silk-screen printing machines, the main differ-
ences lying in the printing technique. Those deserving of special mention are the
tampo-print and lithographic decor machines and others employing more sophisti-
cated decor techniques, such as the incave-graphic method which uses hollowed
silicon rollers carrying the decor image.
Glazing line automation concepts are evolving steadily. This has led to the avail-
ability of: devices for dynamic applied glaze weight control, PLC units to manage
drive speed via inverters, etc.
However, the extreme automation now seen at just about every stage of the
production process has yet to appear in the glazing department as personnel still
play an essential, priority role.
Kilns
The 70s saw the industry start switching from slow to fast firing: hence all
stages of the firing process have been reviewed accordingly, as fast firing has cre-
ated new technological opportunities.
Today, an extensive knowledge of raw materials, the nature of the bodies, the
composition of engobes and glazes as well as the wealth of acquired experience
have all resulted in the simplification and standardisation of this phase too.
Ever-more complex, sophisticated kilns and equipment now make it possible to
achieve a degree of temperature adjustment and control which, even just a few
years ago, would have been unthinkable.
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Wall tiles
Kiln cross-sections have increased and combustion systems have been improved,
providing constant, uniform temperature over the entire kiln cross-section.
Burner lay-out and number, of course, differ in the double firing and monoporosa
kilns. The burners and their combustion chambers are normally sized so as to pro-
vide high combustion flame speeds and low per-unit thermal potential.
In addition to high speed burners, todays technology provides other burner
types which allow the user to fluctuate the flame over the kiln cross-section and
adjust flame power, cyclical flow and duration. This optimises the way in which
the heat is distributed over the tiles, especially at critical points of the firing
curve.
The burner unit generally constituting the combustion chamber may be made
either of refractory rammed material or silicon carbide. The latter gives better heat
resistance at maximum firing temperatures and also provides greater resistance to
thermal shock.
Tile conveyance rollers are a key feature on modern kilns. These may be made of
ceramic or metal; each kiln zone is fitted with specific roller types suited to that
particular stage of the firing cycle.
Adoption of rapid single or multi-layer firing has facilitated tile handling, fa-
voured production of large tiles and increased production flexibility.
A high degree of flexibility in determining and setting firing curves, together
with maintenance of firing conditions, is ensured by microprocessor control sys-
tems which keep temperatures within very narrow tolerances.
Computers provide high levels of kiln automation and also allow the user to
monitor and store the process data.
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Sorting
Although sorting does not affect product features, it is a delicate stage in the
production cycle.
Here too, automation is pervasive, covering everything up to boxing and
palletizing.
Tile geometry (flatness) can be checked by electronic and/or camera systems
which then send the product to specific outlet points.
The number of outlets depends on classification logic and product flatness/shad-
ing criteria.
Normally, there are seven outlet positions (two shades and three sorting classes).
In highly automated installations the operator need only analyse aesthetic defects
and code the tiles to define their class.
In addition to the traditional metal trolley tile handling and storage systems
where the trolleys are pushed along tracks by rigid push and transfer bars, handling
and storage installations with automatic drive vehicles are becoming increasingly
widespread.
In double firing, biscuit storage systems consist of wide racks. The tiles are then
picked up by devices provided with suction cups which transfer them to the glazing
line.
Other solutions feature tile stacking platforms. Tiles are then sent on to the
glazing lines via trolleys which move along flat trackless surfaces, guided by a floor-
embedded wire or laser beam system.
The same AGV (wire-guided) or LGV (laser-guided) systems can be used in
single firing to move the trolleys carrying both the green and fired tiles.
In both cases, a computerised control station monitors all transport system han-
dling, effecting real-time monitoring of production flows to and from the tile stor-
age area.
Conclusions
Porous single firing and fast double firing, following initial teething problems,
have undoubtedly resulted in technical and aesthetic achievements which are com-
parable and certainly superior to those of traditional double firing.
Today, monoporosa and fast double firing may be seen as two complementary
technologies, and only an in-depth assessment of the technical, economical, cul-
tural and environmental aspects facing the manufacturer will allow selection of the
most appropriate plant.
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Wall tiles
Although the decorative features achieved to date have been excellent (they would
have been unimaginable just 10 years ago), research both technical and graphic
is likely to result in even more exciting results.
Larger tiles and surface effects which realistically resemble marble and breccia
will allow ceramic products to compete with natural materials on an almost even
footing, as many now have technical properties superior to their natural equiva-
lents.
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292
Description of ceramic products
Chapter X
FLOOR TILES
Foreword
Simple brick-like cotto tiles have been used as paving for so many centuries that it
is impossible to establish exactly when they first appeared.
Painted and glazed natural-coloured terracotta, and decorated paving tiles are,
however, thought to have appeared in the 11th century AD. From then on, up to the
20th century, floor tile production in Italy was very limited, largely being under-
taken by craftsmen working for wealthy clients.
The acceleration of development that was to transform Italian ceramics into a
true industry took place at the beginning of the 1950s, when cottoforte first came on
the market; this classically Italian product was made using traditional double firing
techniques, and had features which made it ideal for paving.
Two other key technological developments were made during the 50s: the auto-
matic press and the tunnel kiln.
Increasing market demand combined with these two innovations transformed
craftsmens workshops into true industrial companies.
During the 60s fast firing plants appeared. These introduced single firing tech-
nology, thus paving the way for the use of highly automated continuous production
systems.
In simple terms single firing means a production system in which the tile body
and the on-tile glazes are fired together in a single operation. It became widely
established around the mid-70s.
The ceramic industry of the 70s and 80s was dominated by three highly impor-
tant factors:
Automation
Fast firing
The energy crisis.
The introduction of single firing, with the use of fast firing cycles, was to lead
to substantial changes, especially as regards firing technology and kiln construc-
tion.
Innovation was certainly not limited to firing: changes occurred throughout the
production cycle, especially in tile handling.
Tunnel kilns, which conveyed stacked tiles on wheeled cars, were abandoned in
favour of roller kilns where the tiles were supported by refractory plates. The latter
developed into present-day kiln versions where tiles are moved by rollers directly
without the need for an intervening support.
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The same period also saw modernisation of the kiln structure and improved
reliability, with greatly improved firing performance and much enhanced control of
thermodynamic parameters.
Thermodynamic notions vis-à-vis the new roller kilns were entirely different
from those applied to tunnel kilns.
New ideas concerning fast tile firing were based on the theoretical models devel-
oped by Prof. Korac, and with roller kilns these ideas were soon adopted on an
industrial scale.
These models identified the single layer kiln as the one with the lowest specific
consumption too.
In the context of the 70s energy crisis, then, this new technology was also to
spread fast on account of its economic benefits.
Yet the success of vitrified single firing products was not just related to energy
savings: there were other plus factors, such as simplification of the glazing system,
the opportunity to produce large tiles, the adoption of advanced automation sys-
tems.
The introduction onto the market of vitrified single firing products meant that
consumers could enjoy greatly improved physical and mechanical features but with-
out having to compromise on aesthetic content.
This combination of technical quality and aesthetic content plus lower manufac-
turing costs has, then, made floor tiles extremely popular.
The market
Figure 157 shows the evolution of vitrified single firing tile output in Italy from
1990 to 1998.
This data is compared with porcelain tile output over the same period.
Note that the slight fall off in output in 1991 and 1992 was followed by a con-
stantly upward trend that lasted until 1996.
Over the same period, porcelain tiles gained ground constantly.
The following graph (Fig. 158) shows changes in the percentages of output
accounted for by vitrified single firing tiles and porcelain tiles as from 1990. Fig.
159, however, shows annual output increases for these two products.
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Floor tiles
Fig. 157. Comparison of Italian vitrified single firing tile output and porcelain tile output from 1991
to 1998 (the porcelain tile figures for 1997-1998 include 27 and 70 million m2 of glazed porcelain
tiles respectively).
Fig. 159. Annual output variations for vitrified single firing tiles and porcelain tiles (variations on
1991 output levels).
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Product classification
The term vitrified single fired tile is self-explanatory. It refers to a tile body
with a compact mass (grès in Italian), although international standards define
different degrees of porosity, expressed as water absorption, for different classes of
materials (see Figure 160).
The classification below is based on ISO 13006 standards which distinguish prod-
ucts according to their degree of porosity:
Note that some products included in the BIb family are totally frost-proof.
Water absorption
Shaping
GROUP
dry pressing BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
≤ 0.5% BIIa BIIb BIII
GROUP
BIb
Bib
0.5% - 3%
Technical features
Table 14 summarises the main features of the materials belonging to the various
families (specifications required by UNI EN ISO 10545-1/17 standards).
296
B I b ( H2O = 0.5 - 3 %) B II a ( H2O = 3 - 6 %) B II b ( H2O = 6 - 10 % )
WATER ABSORPTION ISO 10545.3 > 0.5, < 3% (max. 3.3 %) > 3 , < 6 % (max. 6.5%) > 6, < 10 % (max. 11 %)
2 2
MODULUS OF RUPTURE (MOR)* ISO 10545.4 30 N/mm (min 27) > 22 N/mm (min. 20) > 18 N/mm2 (min. 16)
BREAKING STRENGTH* ISO 10545.4 min 1100 - min 700 N min 1000 - min 600 N min 800 - min 500 N
3 3
a) DEEP ABRASION RESISTANCE** ISO 10545.6 a) max. 175 mm a) 345 mm a) 540 mm3
b) SURFACE ABRASION RESISTANCE** ISO 10545.7 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
EXPANSION COEFFICIENT ISO 10545.8 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE
THERMAL SHOCK RESISTANCE ISO 10545.9 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE
MOISTURE EXPANSION ISO 10545.10 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE
297
CRAZING RESISTANCE ISO 10545.11 REQUIRED ** REQUIRED ** REQUIRED **
Floor tiles
FROST RESISTANCE ISO 10545.12 REQUIRED FOR SUB-ZERO EXTERNAL USE SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
RESISTANCE TO HOUSEHOLD CHEMICALS ISO 10545.13 CLASS GB min - UB min *** CLASS GB min - UB min *** CLASS GB min - UB min ***
RESISTANCE TO ACIDS AND ALKALIS ISO 10545.13 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
RESISTANCE TO STAINING I SO 10545.14 CLASS 3 min **** CLASS 3 min **** CLASS 3 min ****
FRICTION COEFFICIENT** ISO 10545.17 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
Standards 10545.1 and 10545.2 regard sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (≥ 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving
*** Unglazed products
**** Glazed products
For more detailed information see UNI publications (Italy).
Applied Ceramic Technology
The table clearly shows why these materials, capable of withstanding heavy wear
and mechanical stress, are especially suited for use as floor tiles.
In the context of single firing floor tiles, glazes assume enormous importance
and should be seen as an integral part of the tile itself.
Since the advent of vitrified single firing, glazes have gone through several stages
of development.
The first glazes repeated the features of products obtained by traditional firing.
Later, during the 80s and early 90s, marked changes in the technical characteristics
of the body led to the development of new glazes (grains, sintered and devitrified
materials).
These were generally applied using a mixture of dry and wet techniques. The
resulting products were of a rather simple appearance based on combination of
colours and sizes; technical aspects took precedence over aesthetic ones.
The trend over the last few years has been towards glazed surfaces with a
natural stone look.
Especially popular are surfaces with an aged (or antique) appearance. Sum-
ming up, it can be said that the evolution and optimisation of technical fea-
tures has made excellent aesthetic results available to all.
In terms of abrasion resistance most tiles of this kind are Class 4, with some
Class 5, as per test methods defined in ISO 10545-7.
With regard to body features, there is an increasing, though not generalised,
tendency for porosimetrical parameters to approach those of porcelain tiles (i.e.
water absorption values around 1%).
This trend towards emulation of porcelain tiles is slowly shifting single firing
products out of their traditional water absorption range (3% < WA < 6%) into
the BI UNI EN 176 class.
Aesthetic features
Size
Much of the production over the last few years has focussed on square, aver-
age-size tiles.
In 1996, Italian production of the 30 × 30 cm size accounted for about 40-45%
of total output.
Rectangular sizes took a far less significant share of the market.
Surface appearance
Recently, there has been an increasing trend, especially in Italy, towards tiles
with an antique or stone-like appearance (matt satined surfaces). Such finishes
are achieved through use of specifically developed glazes and structural-type mor-
phological operations on the tile surface and perimeter.
Attaining such results requires quite complicated glazing lines consisting of
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Floor tiles
General features
According to one kind of commercial classification, bodies suitable for the manu-
facture of vitrified single firing floor tiles can be divided into red and white.
In both cases, raw materials are of two basic types:
clayey materials
complementary materials (feldspars, feldspathic sands, quartzes, calcites).
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3 1 2 3
2 1
3
2 1
3
2 1
3
Key: A - plastic clay; B - semi-plastic white clays (china clay); C - red
2 1 vitrifiable clays; D - potassium feldspars; E - sodium feldspar; F - feld-
spathic sands; G - quartz.
3 PHYSICAL FEATURES A B C
3
2
1 FIRING AT 1100 °C A B C
1
BREAKING LOAD AFTER FIRING kg/cm2 180/250 80/120 200/300
Fig. 161. Vitrified single fired tiles: chemical-physical characteristics of various raw materials (single
firing technology). The lowest percentages (0.5-1.0%) are shown in the table only as they will not show
up on the graph.
Body composition
Unlike white, red bodies mainly consist of clays with a high iron content and
small percentages of complementary materials such as feldspars and quartzites.
White-firing bodies, on the other hand, are more diversified and feature a bet-
ter balance of raw materials that includes iron-free clays, feldspars, feldspathoids,
quartz.
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Floor tiles
Figure 162 shows, as an example, two compositions for white and red bodies
respectively.
White bodies, due to the inherent nature of their raw materials, have wider and
more stable size and absorption ranges than red ones because of their higher alumina
and lower ferric oxide content, and have very different vitrification characteristics
(see Fig. 163).
The increase in linear shrinkage and the decrease in water absorption develop
less gradually and at lower temperatures in red gres compared to white gres. The
red develops more liquid phase of lower viscosity from the illitic materials. This is
particularly true in the case of red bodies consisting mainly of clayey minerals (75-
80%).
Where red clays are mixed with feldspars and quartz, firing behaviour (varia-
tions in shrinkage and porosity) is closer to that of light-coloured bodies.
Figure 164 shows composition areas occupied by various formulations inside the
Al2O3 - SiO2 - Alkali tertiary diagram, while Figure 165 shows the areas which can
be derived from the same compositions (A = Feldspathoids, B = Quartzes, C = Clay
minerals).
In particular, the diagrams show six light-coloured body compositions of which
three have predominantly sodium fluxing agents (Ws) and three predominantly
potassium fluxing agents (Wp), together with four red vitrified single firing compo-
sitions.
Fig. 162. Body compositions for red and white vitrified tiles.
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<
<
= <
=
=
TYPE SiO2 Al2O3 TiO2 Fe2O3 CaO MgO K2O Na2O P.F.
Ws 67.93 18.70 1.15 1.51 1.35 0.35 1.20 3.44 4.49
Ws 66.80 18.09 1.50 1.96 1.42 0.38 1.50 3.36 5.46
Ws 66.35 21.33 0.76 1.22 0.68 0.40 1.76 3.18 4.50
R 68.00 15.85 0.53 4.56 0.36 0.46 3.00 1.91 4.81
R 66.37 16.00 1.07 4.79 0.98 0.96 2.91 1.52 5.70
R 68.30 17.15 0.53 3.04 0.54 0.54 2.80 1.73 5.65
R 65.35 15.60 0.76 4.25 1.15 1.55 3.33 1.63 6.15
Wp 66.75 19.95 0.48 1.71 0.57 0.51 5.00 1.80 3.66
Wp 67.03 18.00 0.54 1.52 0.67 0.95 4.00 1.55 5.78
Wp 66.18 18.80 0.54 1.52 0.67 0.95 4.37 1.30 5.78
Wp 67.54 18.76 0.71 1.06 0.57 0.48 4.37 1.30 5.50
SiO2 Al2O3
1 Wpp
GB
Ws = white
GB sbody with sodium
2 Wss
GB = gres grosso
R = red body grosso
Gr = gres
3 3 R
Gr 2
2 3 1
1 Wp =p white
GB = gresbodygrosso
with potassium
CD.0064
Alcali
Alkali Al2O3
Fig. 164. Composition areas for various body formulations within the Al2O3-SiO2-Alkali tertiary sys-
tem.
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Floor tiles
Fig. 165. Composition areas of red and white single firing bodies related to mineralogical components.
The physical properties of glazes, such as resistance to wear, acids and alkalis,
ultimately determine where such products can be used.
This is why research into new kinds of glass with innovative physical-mechani-
cal and chemical properties is ongoing.
Glaze properties basically depend on the raw materials used in their formulation
and on firing temperature.
Formulation is based on the use of different kinds of frit (medium and high
viscosity) in varying proportions; nowadays eutectic-melting frits (calcium and zinc)
are used too.
Other natural and synthetic materials are introduced into the glazes together
with the frits, depending on the exact texture and glaze properties the manufac-
turer is aiming at.
Some of these non-fritted components, such as feldspars, nepheline and zinc
oxide form, together with the frits, the vitreous matrix of the glaze.
Others, such as zirconium sand and corundum, are partly dissolved inside the
glass and help improve abrasion resistance, or else work as opacifiers (zirconium
silicate) or matting agents (alumina oxide).
Other glaze components include:
Anatase (titanium dioxide). Not only a matting agent: it also has positive effects
on the mechanical and chemical properties of the glass.
Wollastonite, calcium and magnesium carbonate. Minerals with an alkaline-ear-
th base which act as matting agents and help form the vitreous matrix.
One of the most important features of a glaze is its expansion coefficient, which
must match that of the body so as to control the final tile curvature.
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The final features of a product depend not only on the chemical and mineralogi-
cal nature of the raw materials, but on the technical conditions during the produc-
tion process and these two factors will be inter-related particularly in the following
areas:
a - Grinding
b - Spray drying
c - Pressing
d - Drying
e - Glazing
f - Firing
a - Grinding
The purpose of grinding is to reduce the size of the raw materials to a final,
constant required particle size.
With vitrified bodies, the degree of grinding of the raw material, together with
other chemical and physical factors, may affect the degree of vitrification and thus
influence shrinkage and porosity values.
The graph in Figure 166 shows variations in shrinkage of a given composition
against grinding residues over a range of temperatures.
Generally speaking, post-grinding residue, for compound vitrified bodies, is
around 7-10% (63 microns-230 mesh). In the case of red bodies, mainly consisting
of clayey materials, this value may drop to 4-6%.
b - Spray drying
The purpose of this process is to evaporate a part of the water contained in the
slip while forming spherical particles. Such particles are of a similar size in all types
of ceramic tile body.
Fig. 167 illustrates particle size distribution for a single-fired body. Note that
some 70-80% of particles are grouped in the 180-425 micron range.
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Floor tiles
Fig. 166. Fired shrinkage as a function of grinding residue variations (checked with a 63-micron
screen).
50%
40%
30%
20%
10%
0%
600 425 300 250 180 125 63
microns
Fig. 167. Particle size distribution of a spray-dried vitrified single firing tile powder.
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c - Pressing
Pressing aims to achieve the greatest possible green tile powder density that is
compatible with the black core or degassing problems which may arise during
firing.
Applying different pressing forces will, of course, result in pieces of different
bulk densities and thus different shrinkage and porosity values too.
The graphs in Figures 168-169 highlight variations in these two parameters
as a function of moulding pressure and firing temperature for a white body. In
white bodies specific moulding pressure is around 250-300 kg/cm2 (white). For
red bodies, which tend to be more plastic, pressure may be lower, around 200 Kg/
cm2.
d - Drying
This is an apparently simple operation, since the physical phenomena which take
place during the evaporation of residual body moisture (4-7%) are understood and
easily controlled.
Note, however, that extremely kaolinitic bodies do tend to expand after drying,
resulting in low unfired bending strength.
Where drying is too fast this may lead to cracks on the tiles. With todays cycles,
post-drying expansion should be a maximum of 0.3% or 0.4% and may even be
negative. Dried piece bending strength should be at least 25 kg/cm2.
e - Glazing
The catalogues of todays ceramic companies feature countless types of glazes.
Generally, however, they all belong to one of the following families:
glossy
matt (devitrified)
rustic.
These products are obtained by layering different glazes using dry and wet ap-
plication techniques.
Wet techniques require special devices such as discs, spray-guns and silk-screen
printing machines. With dry materials (grains and agglomerates) powder applica-
tors are used.
The use of so many kinds of glaze requires a very flexible production plant,
especially on the glazing lines themselves. Furthermore, each application and the
numerous kinds of glaze which overlap on the same product have very different
features, thus necessitating different know-how and skills for each product.
Some floor tiles require only simple disc applications where the glaze is ap-
plied in minimal quantities (up to 500 g/m2), while others require complex proce-
dures (up to 20 different applications) involving applied glaze weights of up to 3
kg/m2.
These glazes may be both wet (density of 1.2 - 2.0 kg/l) and dry applied (highly
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Floor tiles
Fig. 168. Fired shrinkage and water absorption as a function of specific moulding pressure.
Fig. 169. How green bulk density influences post-firing shrinkage and water absorption.
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variable particle size distribution). It is often necessary to apply binders and other
organic products.
The green body is therefore subject to considerable stress and must be able to
absorb considerable quantities of water without bending beyond a certain limit, as
this would compromise silk-screen printing operations.
f - Firing
Optimum firing curves allow fusion reactions and crystallisation to take place on
the various body and glaze components.
These reactions help produce the required absorption and shrinkage goals, while
improving the technical features and the finish of the glazed surface.
The vitrification conditions of a ceramic mass evidently depend not only on the
chemical and physical nature of body but also on the extent of grinding, the bulk
density of the pressed material and on maximum firing temperature.
Fig. 169 shows the influence of green tile bulk density on fired shrinkage and
porosity of a red vitreous body.
To evaluate the characteristics of a body, it is very important to define its size
stability and change in porosity (if any) where firing is performed using different
temperature cycles and/or gradients.
Figure 170 highlights variations in breaking load (MOR), shrinkage and water
absorption at different temperature intervals for a typical vitrified single firing body.
The same graph also identifies the physical-mechanical characteristics relative
to optimum firing temperature.
The dynamism of the ceramic industry has been decisive in the ongoing evolu-
tion of the production process.
The 70s saw significant technological-engineering developments, accompanied
by a shift from double firing to single firing production processes. Adoption of such
technology, which uses roller kilns and rapid firing cycles, involved completely new
layouts.
Shortened firing times and single/multi-layer roller kilns led to huge increases
in automation while cutting production costs significantly. Important developments
in each stage of the production process continued to be made throughout the 80s
too.
These included:
widespread use of wet discontinuous grinding with Alsing mills
introduction of spray drying
increased use of hydraulic presses
adoption of fast driers
increased use of roller kilns.
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Floor tiles
<
?
>
>
=
=
<
The flow chart in Figure 171 illustrates the various stages of the vitrified single
firing process.
Continuous grinding now becoming more widespread even in small and me-
dium-size plants is followed by pressing with high-tonnage hydraulic presses,
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Fig. 171. Vitrified single firing process block diagram for a modern plant (with continuous or discon-
tinuous grinding).
310
Floor tiles
drying with fast automatic (both vertical and horizontal) driers and fast firing using
roller kilns.
The sorting department uses almost entirely automated machinery.
Electronic control systems now allow full automation of green and fired tile
handling, with storage cars being wire or laser-guided.
The effects of such rapid technological-engineering developments are evident
and may be summarised as follows:
increased operator productivity
decrease in surface area occupied by plant
lower unit costs.
1a 1b 4 6
5
2
3
CD.0075
Fig. 172. Lay-out for production of vitrified single firing floor tiles. 1a. Body preparation; 1b. Glaze
preparation; 2. Pressing and drying dept.; 3. Glazing dept.; 4. Unfired/fired tile storage area; 5. Fir-
ing dept.; 6. Sorting dept.
Machines
A brief description of the main machines such as wet grinding mills and spray
driers used in a typical single firing production plant follows.
Although other machines and production processes (involving dry grinding and
powder re-granulation) can be used to produce floor tiles, they are much less com-
monplace and will not be dealt with here.
Weighing systems
Batching may be performed using machinery and equipment of varying levels
of automation.
With discontinuous grinding, batching of raw materials may be carried out
using traditional mechanical leverage systems, or more sophisticated systems
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Mills
Selecting either a continuous or discontinuous process depends on a number of
factors, such as:
plant size
professional qualifications of work force
characteristics of raw materials.
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Floor tiles
Even more modern continuous mills do not have dividing separation plates but
control the flow of material through them with spiral lifters built into the rubber
linings. Hatches that open outwards are provided for inspection and maintenance
purposes and for replenishing the grinding media.
The inside of the mill is lined with specially shaped wear-resistant rubber de-
signed to provide maximum grinding efficiency. Once again, grinding media may be
made of silica or alubit®.
In discontinuous grinding the properly batched load is introduced into the mill
together with the preset quantity of water and fluidizer.
Once grinding is over and the residue has been checked, the slip is screened and
unloaded into storage tanks.
In continuous grinding, instead, the mix is introduced into the mill by various
loading systems.
The raw materials and the deflocculant pre-mixed with the watery suspension
containing the screening residues are introduced together.
At the mill outlet, the slip is sieved first through a wide-mesh screen, then with
a battery of finer screens to classify the material more efficiently. The screening
residue is returned to the mill together with the pre-batched water, while the slip is
delivered to a holding tank equipped with an agitator from where it can be pumped
to the spray drier.
Should the physical characteristics of the materials be satisfactory (low residue
values), a part of the clays (and, if need be, the green scrap) can be dispersed in a
turbo-mixer without being introduced into the mill.
Alternatively, the clayey raw materials may be pre-dispersed after which they are
ground in the mill together with other body components.
This option is particularly appropriate where bodies have a considerably high
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proportion of very plastic clays with relatively high natural moisture content (above
15-20%).
Spray drying
Spray drying evaporates nearly all the water in the slip leaving a powder con-
taining just 4-7% moisture.
The slip is injected upwards from the bottom of the drier via nozzles of various
size situated on a ring placed at the centre of the cylinder: these nozzles are fed by
high pressure pumps (25-30 bar).
Simultaneously, hot air flows downwards from the top of the cylinder and is
distributed tangentially.
The counter-flow of the hot air and the atomised droplets of slip results in heat
exchange.
The spray drier may also be seen as the final consumer of dirty wash water,
sludge and all the powders generated during the production process.
To ensure compliance with environmental standards, the spray drier can also be
provided with dry or wet filters to separate and collect particularly fine dust which
would otherwise be dispersed with the steam coming out of the chimney.
Where appropriate, the spray drier can be powered by co-generation systems so
as to reduce running costs.
The spray drier, then, transforms the semi-finished slip into a powder of con-
trolled particle size and humidity which is then conveyed, via conveyor belts, to the
storage silos.
Presses
This stage of the process is a very important aspect of ceramic production tech-
nology. Normally, the aim is to obtain the highest green tile density that is compat-
ible with degassing and black core problems.
Moulding pressures used for these products generally fall within the 200 - 350
Kg/cm2 range or may be higher still.
Todays hydraulic presses are highly developed and given the available pressing
power, they are also ideal for the production of large tiles.
High mechanical/ceramic reliability and greatly reduced power absorption pro-
vide further benefits.
In addition to the actual press, accessories such as the die and powder filler box
play a key role.
Most of the dies used to form vitrified single fired tiles are of the entering
punch type and are normally rubber-lined so as to cut down the frequency with
which they need to be cleaned. Rubber is also used to obtain structured surface
effects.
The punch may be of the traditional rigid or more innovative isostatic type.
The latter allows optimisation of pressing homogeneity and thus ensures uniform
bulk density right across the tile.
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Floor tiles
Hydraulic press.
This is an important concept because, with vitrified single firing floor tiles, not
only pressing power but homogeneous loading of the powders inside the die cavity
is essential.
Proper loading is normally achieved by using alveolar grating (grid) as op-
posed to the more traditional slatted ones.
Imperfect loading can lead to incorrect tile geometry (orthogonality and square-
ness). Such problems can be resolved using special powder feeders or, as mentioned
above, isostatic punches, which have proved highly successful in reducing geom-
etry defects of the finished tiles subject to shrinkage.
Driers
Drying, which eliminates the residual moisture from the just-pressed tiles, is
performed on either vertical or horizontal driers.
The tiles exiting the presses are transferred on roller conveyors to the driers.
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Vertical driers consist of a load-bearing structure made of steel sections with insu-
lated panelling.
The tiles are laid out on racks (consisting of revolving roller shelves) which are
hinged on the links of a chain system that supports them and moves them through
the drying channels.
Internal ducts feed hot air to the drying area and cold air to the cooling area via
a series of manually adjusted dampers. Heat is provided by air-flow burners which
can run on liquid and/or gas fuels.
Horizontal driers consist of metal modules with insulating panels and insulated
exterior piping for air re-circulation.
The tiles run through the whole length of the drier on a speed-adjustable roller
conveyor having one or more levels.
The drier consists of a series of identical modules, each one with its own inde-
pendent thermo-hygrometric and ventilation air flow characteristics. Each zone has
its own hot air generators too.
Normally, the final section of the machine is designed to stabilise the tempera-
ture of the outgoing pieces.
With vertical driers, the drying cycle lasts 35-70 minutes; with horizontal
driers, cycles can be speeded up to 6-20 minutes. In both cases, however, the
duration of the cycle depends on the type of body and the size and thickness of
the pieces.
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Floor tiles
Glazing machines
The world tile market has become an increasingly sophisticated and diversified
one, requiring machines and equipment capable of producing a wide range of glaz-
ing and decoration applications.
Glazing machine manufacturers have responded to this demand with machinery
that provides superb aesthetic effects yet still relies to a large extent on the manual
skills inherent in all glazing operations.
Note also that in order to obtain a proper degree of flexibility on glazing lines
there should be numerous application stations and all the relevant equipment use-
ful for rapid product change-over. This inevitably implies very long glazing lines
which have, over the years, maintained the same basic structural and functional
features.
Where antique or rustic effects are desired, repeated application tasks such as
flashing, brushing, dry application, etc. will be required.
Where glossy finishes are required the engobe and glaze are best applied using
bell units.
There is also an increasing trend towards the use of spray-gun devices that
evenly distribute water, fixing agents and (airless) engobe over the tile surface.
Moving on to decoration, the wide range of print types and patterns currently
in demand means that both flat and rotary screen machines are used. Rotary ma-
chines are increasingly popular because they are fast and require little monitoring
and maintenance.
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Several kinds of rotary silk-screen printing machines exist, the main differences
lying in the printing technique. Those deserving of special mention are the tampo-
print and lithographic decor machines and others employing more sophisticated
techniques, such as the incave-graphic method which uses hollowed silicon rollers
carrying the decor image.
Glazing line automation concepts are also evolving steadily. This has led to the
availability of: devices for the dynamic control of the applied glaze weight, PLC
units to manage drive speed via inverters, etc.
However, the extreme automation now seen at just about every stage of the
production process has yet to appear in the glazing department as personnel still
play an essential, priority role.
Kilns
The 70s saw the industry start switching from slow to fast firing: hence all
stages of the firing process have been reviewed accordingly, as fast firing has led to
the development of new technologies.
Today, an extensive knowledge of raw materials, the nature of the bodies, the
composition of engobes and glazes as well as the wealth of acquired experience
have resulted in the simplification and standardisation of this phase too.
Ever-more complex, sophisticated kilns and equipment now make it possible to
achieve a degree of temperature adjustment and control which, even just a few
years ago, would have been unthinkable.
Kiln widths have increased and combustion systems have been improved, pro-
viding constant, uniform temperature over the entire kiln cross-section. The burn-
ers and their combustion chambers are normally sized so as to provide high com-
bustion flame speeds and low per-unit thermal potential. In addition to high speed
burners, todays technology provides other burners which allow the user to fluctu-
ate the flame over the kiln cross-section and adjust flame power, cyclical flow and
duration.
This optimises the way in which the heat is distributed over the materials to be
fired, especially at critical points of the firing curve.
The burner unit generally constituting the combustion chamber may be made
either of refractory rammed material or silicon carbide. The latter gives the unit
better heat resistance at maximum firing temperatures and also provides greater
resistance to thermal shock.
Tile conveyance rollers are a key feature on modern kilns. These may be made of
ceramic or metal; each kiln zone is fitted with specific roller types suited to that
particular stage of the firing cycle.
Adoption of rapid single or multi-layer firing has facilitated tile handling, fa-
voured production of large tiles and increased production flexibility.
Firing temperatures and cycles generally fall within the 1100-1200 °C and 35-
60' ranges respectively, depending on the nature of the ceramic materials and the
size of the tiles.
Fig. 173 shows two firing curves. The first is generally suitable for standard
318
Floor tiles
white bodies, while the second is designed for bodies sensitive to black core prob-
lems.
A high degree of flexibility in determining and setting firing curves, not to
mention maintenance of firing conditions, is ensured by microprocessor control
systems which keep temperatures within very narrow tolerances. Computers pro-
vide high levels of kiln automation and also allow the user to monitor and store the
process data.
Fig. 173. Typical firing curves for standard vitrified single firing floor tile bodies and those sensitive to
black core.
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Sorting
Although sorting does not affect product features, it is an important stage in the
production cycle. In this area too, automation is pervasive, covering everything up
to boxing and palletizing. Tile geometry (size and flatness) can be checked by elec-
tronic and/or camera systems which then send the product to specific outlet points.
In highly automated installations the operator need only analyse aesthetic defects
and code the tiles to define their class.
Conclusions
After twenty years of continuous technological development, todays single fired
floor tiles are products of superb technical and aesthetic quality.
However, research continues and there is still room for innovation and improve-
ment. Technical and structural tile properties already go far beyond the standards
required by the construction industry; tile finish and decor can also successfully
compete with anything offered by other natural or artificial materials. Last but not
least, ceramic floor tiles remain inexpensive and enjoy excellent market competi-
tiveness.
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Description of ceramic products
Chapter XI
PORCELAIN TILES
Foreword
Porcelain tiles (also known as fine porcelain tiles, fully vitrified stoneware or
sometimes referred to by the Italian gres porcellanato) have excellent technical char-
acteristics, featuring exceptionally good bending strength and water absorptions
often lower than 0.1%.
In the context of the ceramic tile industry, porcelain tiles have gained ground
rapidly, from a very small share of the market and a limited range of applications to
an ever-increasing level of demand and wider fields of use.
While, in the past, this product was of interest largely on account of its techni-
cal characteristics, its refined aesthetic potential has now ensured its success in more
sophisticated market segments, accompanied by a marked increase in output.
Yet porcelain tiles are not exactly new. While their origins lie in now-obsolete
production technologies, development can be attributed to the introduction of in-
novative chemical-mineralogical compositions suitable for use with modern tech-
nologies such as high pressure moulding, recently developed decoration techniques
and, of course, fast firing - even on large tiles.
This chapter provides a general overview of the porcelain tile market, techno-
logical aspects, the different stages of the production cycle and the outlook for the
future.
Market
Note that in the early 80s just 8 million m2 of porcelain tiles were produced,
accounting for just 2% of Italian ceramic tile output. By the year 2000 that figure
had jumped to 300 million m2, some 40% of all Italian output. Fig. 174 illustrates
this extraordinary escalation. The increase in output can be explained by the fact
that these tiles are appreciated not only in Italy and Europe but all over the world
(60% of Italian porcelain tiles are exported).
Global porcelain tile production capacity is currently estimated at around 700
million m2/year (accurate figures are difficult to obtain as there is a lack of informa-
tion with regard to China, which has a huge industry, and new producers are ap-
pearing all the time the world over). Production involves 265 companies, 100 of
which are Italian.
The key producer nations are China with about 80 plants, Spain with 22, Taiwan
with 20, France and Germany with 7, Malaysia with 7, Thailand, Indonesia and
India with 5.
Bringing up the rear are Portugal, Poland, the Czech and Slovak Republics, Tur-
key, South Korea, Japan, the Philippines, Sri Lanka, Argentina, the USA, Venezuela
and Morocco, each having just a few or only one production plant.
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Output
Fig.174. Production and sales data for Italian porcelain tiles from 1991 to 1998 (In 1997 and 1998
glazed porcelain tiles accounted for 24,750,000 and 70,322,000 m2 respectively).
Technical characteristics
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Porcelain tiles
Water absorption
Shaping
GROUP
B BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
dry pressing ≤ 0.5% BIIa BIIb BIII
GROUP
BIb
Bib
0.5% - 3%
Moreover, they are highly resistant to frost, chemicals and stains and have ex-
ceptional bending and compression strength etc.
Tab. 15 illustrates their main characteristics, comparing standard-permitted mini-
mum values with real values observed on marketed products.
Other aspects which should not be underrated are their antistatic and hy-
gienic properties, making them ideal for computer rooms, hospitals and operat-
ing rooms.
Commercial specifications
Size
Over the last ten years some 90% of Italian output has been accounted for by
medium size tiles.
More specifically, 60% can be attributed to the 30 × 30 cm and 33 × 33 cm sizes,
with 40 × 40 cm tiles accounting for just 10%.
In addition to these standard sizes, there are other products which range from
the very large (e.g. 60 × 120 up to 120 × 180 cm) to the very small (accessories and
trims).
Moreover, porcelain tile producers have recently begun to offer product ranges
which coordinate square and rectangular tiles, especially on rustic product
lines.
Categories of use
The combination of technical and aesthetic aspects determines the suitability of
the final product for a specific use.
Fig. 176 illustrates different fields of application for different types of glazed
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BREAKING STRENGTH* ISO 10545.4 min 1300 - min 700 N min 1500 - min 2000 N
b) SURFACE ABRASION RESISTANCE** ISO 10545.7 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
Standards 10545.1 and 10545.2 are not shown in the table owing to limited space. Nevertheless, the reader is reminded that they
refer to sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (< 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving
*** Unglazed products
For more detailed information see UNI publications (Italy).
Tab. 15. Porcelain tiles according to ISO BIa standards. Standard-required values and actual product
values are shown.
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Porcelain tiles
Aesthetical characteristics
Requisiti estetici Stoneware
Glossy Gres ceramico
Brillante
Klinker
Resistance Aesthetics
Resistenza Estetica
CD.0023
Fig. 176. Surface characteristics related to fields of application. Note that porcelain tiles, previously
confined to industrial uses, are now used extensively in the heavy commercial field and have gained a
foothold in the medium commercial field.
and unglazed tile, namely: light commercial, medium commercial, heavy commer-
cial and industrial.
The y-axis indicates technical and aesthetic values while the x-axis illustrates
the increasing bending strength and resistance to wear corresponding to a decrease
in aesthetic appearance.
Note that porcelain tiles, originally confined to an industrial context, now oc-
cupy a significant share of the heavy commercial field and, thanks to their much-
improved aesthetic properties, the medium commercial field too.
Research has led to the creation of new, innovative tile types which maintain the
above technical characteristics. This has resulted in marked product differentiation
and the spread of porcelain tiles into areas traditionally occupied by tiles of high
aesthetic value.
There follows a general overview of these relatively new commercial types, in-
cluding those which have been on the market for some time.
a) Plain tiles
The simplest products from an aesthetic viewpoint. Pastel shades dominate. Pol-
ished plain tiles are often used in shopping malls. Obtained from spray-dried pow-
ders of uniform colour.
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sulting in the so-called salt and pepper effect. The base body colour is often white
or another light colour.
d) Macro granito
Obtained from spray-dried powder mixes with a 10-50% of a large grain con-
tent. The latter are produced via dry or wet regranulation of spray-dried or mi-
cronized powders of single or multiple colour. The tile surface background colour
is similar to that of granito or marble effect products, thus highlighting the grains
to give a natural stone-like appearance. These products normally feature a polished
finish.
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Porcelain tiles
The raw materials used in porcelain tile body compositions can be divided into
several mineral groups, each with its own specific function: the clayey raw materials
confer plasticity, while complementary non-plastic materials include fluxing miner-
als or those with a structural function.
The former include minerals of illitic-kaolinitic or montmorillonitic origin. These
have plastic characteristics that vary as a function of mineralogical structure and
particle size distribution. Fluxing minerals include feldspars and feldspathoids, talc,
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Tinte
Plain Unite
colours
Event Tint
Granito
Granito
Granite
Marble effect
Variegato
Shaded
(veined)
Macrograniti
Macro granito
Macrogranite
Rustici
Rustics
Rustics
Decorati
Decorated
Decorated
0 5 10 15 20 25 30 35 40
Fig. 178. Expected development trends for different types of porcelain tile.
eurites, pegmatites, while quartz and generally quartzites the most refractory
ones have a structural function.
All components must have low concentrations of colouring oxides (e.g. Fe2O3
and TiO2) to prevent contamination of natural body colour.
Quantitative body component ratios depend on the mineralogical nature and
particle size distribution of the clays and, finally, on the reactivity of the latter with
the fluxing minerals.
Fig. 179 provides an overview of the chemical and physical characteristics of
porcelain tile compositions/products.
The PLASTIC CLAY (B) provides the green tile plastic properties needed dur-
ing pressing and confers the required post-drying bending strength.
The CHINA CLAY (A) complements the unfired properties of the plastic clay,
yet is also essential in increasing the alumina content of the body. Feldspar (or
possibly a small quantity of talc) acts as a flux at standard firing temperatures
(1200-1230 °C).
Quartz, where it participates in the melting of the feldspars, helps balance vis-
cosity and the vitreous flows; where it does not, it constitutes the base matrix of the
crystal phase in the finished product, together with a small quantity of mullite,
generated by decomposition of the china-clays.
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Porcelain tiles
3 1 2 3 4
1
2
4
1
3 2
3
1
4 2 Key: A - Semi plastic white clay; B - Plastic white clay; C - Sodium feldspar; D -
Quartz; E - Talc.
2 3
PHISICAL FEATURES A B
1
BREKING LOAD BEFORE DRYING Kg/cm2 4/6 8/10
1
3 2 FIRING TO 1100 °C A B
Fig. 179 - Chemical and physical characteristics of raw materials used in porcelain tile production.
The table indicates the Na feldspar, yet K feldspar or mixes of the two may also be used. The lowest
percentages (0.5-1.0%) are shown in the table only as they will not show up on the graph.
Compositions
Porcelain tiles have evolved from the material known as chemical stoneware.
This was once used to produce small (5 × 5 cm, 10 × 10 cm) tiles, using now-
obsolete technologies.
The adoption of modern compositions, roller kilns and modern, high power,
high precision hydraulic presses have resulted in progressive improvement of tech-
nological product characteristics and yielded the benefits of reliability provided by
fast firing.
Fig. 180 compares a traditional chemical stoneware composition (item 1: firing
temperature about 1200-1220 °C and firing cycles of 30-50 hours) and a present-
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day fast firing composition (item 2: temperature of 1200-1230 °C and cycles of 50-
70 min.).
The structures of the fired materials are similar in both, but in the slow firing
one there is high mullite content and no microporosities (closed or open pores),
thus conferring very high stain resistance.
Nearly zero porosity and the formation of mullite crystals can mainly be attrib-
uted to the extended firing time, which aids sintering and hardening.
The porcelain tile composition shown in fig. 180 (item 2) is typical of a so-called
base body.
For tiles decorated with soluble salts a very white (so-called superwhite) body is
preferred to bring out the intensity and nuances of the colours.
Other raw materials such as zirconium silicate, anhydrous alumina etc. are thus
used to augment whiteness; where these refractory raw materials are introduced
they partially replace quartz.
To clarify the above concepts Fig. 181 gives a chemical analysis of several base
and superwhite bodies as well as a ceramic stoneware body once used with tunnel
kilns.
The SiO2-Al2O3-(K2O+Na2O) tertiary diagram for these compositions is also
given.
These values should only be taken as a rough guide as there is a tolerance for
each in relation to the type of oxide in question.
Fig. 180. Possible porcelain tile compositions using the raw materials described above. 1) Standard
porcelain tile composition for traditional processing cycles (temperature of 1200-1220 °C and cycles of
30-50 hours). 2) Composition for fast cycles (temperature of 1200-1230 °C and cycles of 50-70 min-
utes).
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Porcelain tiles
40 0 Body components 1 2 3 4 5
SiO2 65 67 71 68 64
K2
Al2O3 24 21.0 18 18 21
O
30 10
3
2O
-N
1
Al
a2O
20 2 5 20
4
3 CaO + MgO 0.1 0.8 0.9 0.7 0.7
Fe2O3 + TiO2 0.3 0.8 0.9 0.6 1.0
10 30 ZrO2 - - - 4.4 3.1
90 80 70 60
P.F. 6.1 4.2 3.4 3.4 3.4
SiO2 CD.0027
Fig. 181. SiO2-Al2O3-(K2O + Na2O) tertiary diagram illustrating the following body compositions: 1.
Chemical stoneware (tunnel kiln firing) 2-3. Porcelain tile (base bodies) 4-5. Porcelain tile (superwhite
bodies).
a) Spray-dried powders
Spray-dried powder particle size distribution is largely the same as with other
tile types.
The table below shows particle size distribution for a standard body.
> 600 1%
600 - 425 9%
425 - 300 10%
300 - 250 42%
250 - 180 17%
180 - 125 14%
< 125 7%
b) Regranulated powders
Regranulation consists of increasing grain sizes from 0.1-0.8 mm (spray-dried
powders) to 2-8 mm, depending on the specific process:
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ture content is near to that of spray-dried powder. Specific weight is usually higher
than in spray-dried powders (1.15-1.30 g/cm3).
Whether dry or wet compacted, the percentage of grains added to the basic
spray-dried powders is generally lower than 25% to prevent the risk of subsequent
pressing problems.
The machines and techniques used to produce the grains will be described in
Plant engineering solutions further on.
c) Micronized powders
For certain tile types (e.g. marble effect tiles) it may be necessary to use superfine
(micronized) powders which generally have a particle size distribution of less than
200 µm.
These are obtained by crushing the spray-dried powders even further.
Despite the handling and storage problems associated with micronized powders,
where mixed with spray-dried powders they give tile finishes of superb aesthetic
quality.
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Porcelain tiles
Final product features depend not only on the chemical and mineralogical nature
of the raw materials, but on the technological parameters used during the produc-
tion process too.
a) Degree of grinding: to aid vitrification and hardening during firing, the ground
slip residue on 230 mesh must be very low, in the 0.5 - 1% range (average parti-
cle diameters of 15 - 20 microns). Such fineness helps to increase the specific
surface area of the particles in the ceramic mass and therefore their firing reac-
tivity.
b) Unfired density: the aim of pressing is to achieve the greatest possible green tile
density that is compatible with the black core or degassing problems which can
arise during firing. Standard moulding pressures (350-450 kg/cm2) give pressed
tile densities of 1.95-2.00 g/cm3.
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With macro granito higher pressing pressures (up to 600 kg/cm2) are needed to
compensate for the unavoidable variations in the bulk density of the grains.
c) Firing cycle and temperature: it is in this final phase that the results of grinding
and pressing are seen. Here, the key parameters are temperature and cycle time:
these must be carefully evaluated if the goal of a vitrified material of very low
porosity is to be achieved. On average, fast firing of porcelain tiles requires cycles
of 50-70 minutes and firing temperatures of about 1200-1230 °C.
Note that the above parameters must be evaluated as a whole because the inter-
action and combined effects of simultaneous variations in one or more of them
must be considered as illustrated in Fig. 182.
With coloured bodies it is very important to obtain a good vitrification curve
balance vis-à-vis the various compositions; added pigments, in fact, can modify
the tendency of the body to vitrify and shift the optimum firing point (see Fig. 183),
sometimes making it necessary to modify the composition.
Fig. 184, instead, shows changes in bending strength, firing shrinkage and water
absorption as a function of firing temperature.
Finished product properties (virtually zero water absorption, very high bending
strength, exceptional deep scratch resistance and excellent resistance to staining)
are influenced both by the choice of raw materials and the conditions prevailing at
the batching, grinding, pressing, drying and firing stages.
Pr
es
se
ure
dp
rat
rod
pe
uc
tem
td
en
ing
sit
Fir
yg
r/c
m
3
Residue %
Fig. 182. Diagram showing how the degree of grinding, unfired bulk density and firing temperature
influence tile vitrification.
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Porcelain tiles
Shrinkage
(%)
Fig. 183. Vitrification curves for bodies coloured with different pigments or colouring oxides. In this
example the balance of the different curves may be regarded as satisfactory.
<
>
=
= >
<
Fig. 184. Diagram illustrating changes in bending strength, shrinkage and water absorption for differ-
ent firing temperatures.
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Production technology
Compared to other kinds of ceramic tile, porcelain tiles involve some techno-
logical and engineering aspects that are unique:
the slip colouring process, common to all porcelain tile output
batching and mixing of the coloured powders needed for the granitos
production of grains and their combination with powders of different density
for the manufacture of macro granitos
distribution of the coloured powders directly in the press cavity (veined pro-
ducts)
formulation, application and drying of colouring solutions for decorated pro-
ducts.
The block diagram in Fig. 185 gives a general overview of the different stages
of the porcelain tile production process, while Fig. 186 illustrates how flows relate
to the different tile types.
Manufacturers of plain tiles will, of course, have the most straightforward pro-
duction plant set-ups.
Where granitos are manufactured the plant becomes more complex on account
of the batching and mixing of differently coloured and/or treated powders.
Macrogranitos require further changes to the powder granulation process and
also involve handling of separation phenomena which can appear when the grains
are mixed with the spray-dried powders.
Whilst the diagram shows the application of colour onto unfired tiles it could
also be applied to prefired or inertised tiles.
Fig. 187 gives an example of a versatile production plant lay out, arranged for
all the above products, glazed or decorated; each area identifies a department.
Batching
Depending on the degree of plant complexity and the type of grinding pro-
cess (discontinuous or continuous), batching may feature various levels of auto-
mation.
With discontinuous grinding, batching of raw materials may be carried out us-
ing traditional mechanical leverage systems, or more sophisticated systems involv-
ing individual weighing hoppers with load cells.
Continuous grinding generally features a microprocessor-controlled continuous
weighing system.
The batched mix is stored in a pre-loading silo, from where it is fed into the mill
continuously after mixing of the raw materials and the deflocculant with the aque-
ous suspension containing re-circulated sieve residue.
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Porcelain tiles
POWDER STORAGE
UNFIRED STORAGE
Fig. 185. Block diagram showing flows related to the production of different product types.
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Plain colour
Granito
Veined-shaded
Decorated
Rustics
Macrogranito
Fig. 186. Block diagram showing possible production flows for various porcelain tile types.
In certain cases, producers pre disperse part of the clayey materials (usually the
finer, more plastic part) and sometimes the unfired base body scrap too.
This gives a clayey suspension that can be added to the mill or sent further
downstream where it is mixed with the slip produced by the mill itself.
Grinding
Continuous mills, generally used to obtain the base slip (white body), are becom-
ing more and more common in porcelain tile production plants too.
A series of sieves are installed at the mill outlet. The first of these is designed to
separate any coarse solid particles (e.g. grinding media residue) while the others
have a more technological function, screening the slip to be spray-dried.
The sieving residue is recycled into the mill.
Body colouring
Base bodies can be coloured by the discontinuous addition of concentrated syr-
ups (the term syrup refers to a coloured slip with a high concentration of pig-
ments). These suspensions are ground in task-specific mills or by continuously
batching and mixing the syrups themselves using devices for the measurement and
regulation of flow (by volume or mass).
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Porcelain tiles
2
4 6
1 5
CD.0032
Fig. 187. Lay-out for manufacture of porcelain granito, macro granito and decorated tiles.
Key: 1. - Body preparation area; 2. - Pressing and drying dept.; 3. - Glazing dept.; 4. - Unfired/fired
tile storage; 5. - Firing dept.; 6. - Sorting dept.
Volumetric delivery systems batch concentrated syrups held in tanks (each con-
taining just one colour) and allow producers to adjust the delivery rate according to
the desired degree of concentration.
Massic batching units, instead, use density measurements to dose liquid semi-
finished products. Electronic batching control systems ensure accurate setting and
monitoring of the mixing process.
Spray drying
The size of a spray drying department largely depends on the tile type and the
number of spray-dried powder colours required.
Although spray drying is theoretically the same for all ceramic products, the
complexity of the powder mix (dependent on aesthetic and commercial goals) de-
termines the required number of tanks and silos and the number and production
potential of the spray driers.
Furthermore, where regranulation processes are required there will be a need
for extra grain storage silos.
Leaving aside micronized powders and grains (used in veined and macro granito
respectively), optimum particle size distribution for base bodies and colours used to
manufacture granitos is actually very similar to that seen in the manufacture of
other types of tile.
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Storage silos.
wet regranulation
Agglomeration is effected by spraying the slips (which may be differently coloured)
onto a mass of powder agitated by rotary stirrers. The process simultaneously gives
rise to agglomeration and colouring.
Pressing
Extreme compaction gives rise to a high density tile structure which limits shrink-
age and greatly reduces the porosity of the fired product. However, the specific
moulding pressure (normally in the order of 350-450 kg/cm2) must be such that
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Porcelain tiles
the resulting pressed tile density still allows oxidation of organic substances and
escape of the gases produced during firing.
Another essential factor is homogeneity of powder loading inside the press cavi-
ties. The physical nature of some mixtures, such as those consisting of both spray-
dried powders and grains, can vary substantially, thus making pressing somewhat
problematic.
To ensure optimum cavity filling press fillers can be fitted with an alveolar float-
ing grating. These devices allow manufacturers to limit in-cavity filling variations,
resulting in fewer surface defects (shaded lines, differences in colour tone etc.) and
dimensional variations. In recent years the resolution of such geometrical defects
has been significantly aided by the introduction of isostatic moulds.
Hydraulic press.
Drying
The drying of porcelain tiles does not involve any particular difficulties as drier
operating conditions and drying cycles are very similar to those used in the manu-
facture of other sorts of tile.
Where tiles are to be decorated with soluble salts it is essential that they have
bending strengths that support the pressure of silk-screen printing (25-30 kg/
cm2).
Driers may be vertical or horizontal: from a technological point of view these
are essentially the same. Drying cycles in vertical driers generally range from 45 to
65 minutes, depending on tile size and thickness (the bigger and thicker the tile, the
longer the cycle).
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On horizontal driers cycles fall within the 15-30 minute range, once again de-
pending on tile dimensions.
Where soluble salts are applied on glazing lines it is essential that the tem-
perature at the drier exit be stabilised so that the salt spreads uniformly through
the tile.
If this is not so problems of heterogeneous colour tone will probably arise,
becoming especially evident after the tile has been polished.
Decoration
The technology concerning the use of soluble salts is relatively new and some-
times complex.
Steady product evolution and increasing demand for ever-more sophisticated
tiles has seen the number of special glazing lines equipped for this purpose grow
rapidly.
Such lines vary in length from 30 to 80 m depending on the complexity of the
product, which in the simplest cases need just 1 or 2 silk-screen printings compared
to 3 or 4 silk-screen printings plus disc or spray-gun applications in the more com-
plex ones.
The key factors affecting the outcome of glazing are:
body temperature: affects the diffusion of the saline solution through the tile
application type and method: the quantities of colouring salts or glazes to be
used largely depend on the application method (disc, silk-screen printing,
spray-gun), as each one has its specific characteristics and properties. Note
that with silk-screen paste decoration the salt takes much longer to penetrate
the body
applied quantity: the amount of colouring salt determines the intensity of the
colour, as does the quantity of solvent, which affects the depth of impregna-
tion.
Firing
As already said, firing aims to achieve vitrification (nearly zero water absorp-
tion) of the mass and dimensional stability. The most important factors are:
reactivity among the body components
the degree of slip grinding
moulding pressure
firing temperature and cycle time.
342
Porcelain tiles
The complex destruction reaction of the clayey lattices, which starts with the
vitreous flows and continues until a compact structure is formed, is controlled by
the heat energy supplied during firing.
Other factors, such as slip grinding and pressed tile density, affect the kinetics of
the reaction (i.e. its rate).
The heat energy responsible for the inter-component reactions is defined by the
firing curve (fig. 188); this is designed to supply a quantity of energy that allows
reactions to take place gradually without affecting tile geometry.
Firing cycles currently used for porcelain tiles range from just 45 minutes for
the smallest, thinnest tiles (e.g. 20 × 20 cm, 7 mm thick) to 90 minutes for the
largest, thickest ones (e.g. 60 × 60 cm, 12 mm).
Cycles may stretch to 120-160 minutes where outsize tiles in the order of 100 ×
200 cm are produced.
Maximum firing temperatures range from 1180 to 1240 °C. The exact tempera-
ture will depend on body composition, the extent of slip grinding, the compactness
of the pressed powders etc.
Recently developed roller kilns specially designed for high temperatures em-
ploy sophisticated microprocessor control systems which allow manufacturers to
maintain accurate control over firing conditions and thus keep temperatures within
very narrow tolerances.
High power computers and dedicated software let the user display real-time pro-
duction data, firing conditions and work parameters: where required, these can be
printed.
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Sorting
Although sorting selection and sub-division of tiles according to the markets
quality requirements does not affect the characteristics of the finished product it
is an important part of the production process.
Tile sorting is an essential tool in defining company image: hence sorting crite-
ria must be evaluated with great care.
344
Porcelain tiles
surface levelling, this operation makes the tile as flat as possible and eliminates
any scratches or surface imperfections
polishing: this represents the first stage of finishing and involves progressive
reduction of surface roughness through the use of a series of abrasives of de-
creasing coarseness
finishing: the surface is treated with finer and finer abrasives to produce the final
mirror-like finish.
Once the above process has been completed, squaring and bevelling machines
can be used to finish the edges of the tiles.
Theoretical polishing line feed rates may be as high as 8 m/min, but in practice
work rates are conditioned by tile size and sorting methods: where sorting is manual,
speeds are unlikely to exceed 4 m/min.
Technical outlook
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be pointed out that even a multiphase ceramic material has intrinsic microporosity
owing to the impossibility of filling the empty gaps between the solid crystal par-
ticles and the surrounding glass phase, even after a long firing cycle.
Even porcelain tiles feature such microporosity, albeit at minimum levels: unless
controlled carefully, this could lead to problems of surface cleanliness.
In general, open porosity values are very low (about 0.1% in terms of water
absorption and 0.5% in terms of mercury porosimetry) and so the tile surface tends
to resist staining well.
Internal closed porosity, instead, is estimated at 6%, with pore sizes ranging
from 1 to 10 microns; this porosity is exposed during polishing where about 0.5-1
mm of surface material is removed.
There are several ways (some of which have already been widely adopted) to
reduce the effects, or the incidence of residual microporosity itself, on product per-
formance.
On the question of microporosity, it has been demonstrated that penetration of
staining agents and their removal are linked to pore size and diameter. Relatively
large open pores will obviously make the product easier to clean, but to the detri-
ment of the visual aspect of the surface.
Vice versa, very small pores solve the problem in advance, as they block any
intrusion of foreign matter; as part of their product enhancement efforts, manufac-
turers thus prefer this small pore approach.
Appropriate adjustments to work parameters can also provide significant in-
creases in tile density. For example:
by increasing the specific surface area of body components, particularly the har-
der ones (quartz and feldspars). Controlled via the milling process
by increasing powder compaction with higher moulding pressure
by using more reactive fluxes compatible with the chemical-physical stability of
the bodies and their tendency towards pyroplastic deformation.
Aesthetic outlook
In the light of current (2000) output trends, porcelain tile aesthetics will inevita-
bly continue to evolve, widening the range of decorative effects a key factor in the
success of the product even further.
New products playing a key role in this aesthetic diversification are the already-
cited macro granitos, tiles decorated with soluble salts, veined tiles, structured rus-
tic products decorated with soluble salt flashing and other techniques such as brush-
ing. Then there are those obtained using mixed application techniques (silk-screen
printing, pelletized glazes and the use of soluble salts on both structured and flat
surfaces).
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Porcelain tiles
With some product types, polishing provides surfaces that closely resemble marble
and natural granite.
This ongoing aesthetic progress can only raise the added value of porcelain
tiles even further, and is likely to lead to their use on the residential market and as
outdoor wall cladding through the application of tiles as large as or even larger
than 100 × 200 cm.
Conclusions
It is logical to assume that advances in decoration will also allow porcelain tiles
to capture a significant share of the high quality wall tile market (indoor and out-
door tiles for public buildings, shopping malls etc.).
From a technical viewpoint the results already obtained are excellent. Now, to-
gether with the evolution of decoration devices (on the press itself or along the
production line), the industry is steadily creating a well balanced product capable
of competing with natural materials.
Further improvements to productivity are likely to be achieved by making
organisational changes to body preparation departments, where the production of
high-quality, versatile base bodies will probably become more common, allowing
manufacturers to make modifications, using additives, to the bodies in the slip tanks
or the mills themselves.
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348
Description of ceramic products
Chapter XII
Accessories and Trims form a vast high added value product category that
consists of tiles decorated in second (single firing tiles), third and fourth firing,
mosaics, strip and border tiles and other elements that can be matched with both
wall and floor tiles.
The accessories and trims industry is, then, closely tied to standard tile manufac-
turing. It consists of companies that actually produce these complementary prod-
ucts and others that perform specific tasks separate from the actual ceramic side of
manufacturing (cutting, polishing, on-mesh gluing etc.).
Even today, accessories and trims are often referred to as third fired products.
This is because, back in the mid-70s when the industry largely consisted of small
family concerns, finished tiles were usually hand decorated (mostly with floral mo-
tifs); since the bulk of output consisted of double firing wall tiles this hand-painted
decoration was subsequently third fired.
Over the last twenty years things have changed somewhat: aesthetics have im-
proved immeasurably and output has rocketed. These changes have affected not only
decoration (trims included) but also accessories such as strip and skirting tiles.
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A continuously expanding market for wall and floor tiles now key elements in
furnishing has significantly accelerated growth in the accessories and trims in-
dustry, to the extent that some of the original third firing workshops are now
modern industrial concerns of key importance.
The market
The accessories and trims market is closely tied to the wall and floor tile market:
tile companies, in fact, usually offer customers a line of decorated items (borders,
strips, inserts and trims) specially made by external accessory manufacturers to
match their own plain tiles.
In recent years the main accessory producers have activated direct-to-market
distribution, providing the final user with a greatly increased selection of plain
and decorated items and thus allowing him to engage in true product personalisa-
tion.
Market potential is continually on the increase, as accessories and trims con-
sumption is to some extent dictated by fashion a concept once confined to the
clothing market.
In Italy alone some 120 companies employ over 3000 workers (late 90s), gener-
ating total sales of over e 250 million; 9% of companies (11) employ over 100
people and may thus be considered small-medium plants rather than just work-
shops.
Yet attaining reliable output figures for individual items is virtually impossible
owing to the vastness of the product range.
350
Accessories and trims
Different ceramic accessory and trim types (from Fashion tile, Gruppo Editoriale Faenza Editrice).
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At least 50% of output is accounted for by the first item on the list (i.e. tiles
produced in 2nd, 3rd and 4th firing).
Technology
In the mid 70s the accessories and trims industry essentially consisted of small
workshops: decoration in the form of hand painting of simple motifs or application
of decals was largely manual, with second-grade tiles often being recovered for
these purposes.
The decorated tiles were then fired in muffle kilns, which had limited holding
capacity and relatively long firing cycles.
Since then two key innovations have been introduced into the decorating depart-
ment, both regarding the initial phase of operations: automated silk-screen printers
have replaced the hand-held brush while roller kilns have greatly modified factory
layouts and increased cycle flexibility.
The whole decorating process has thus become very similar to the glazing/fir-
ing sequence used to produce the tiles themselves, although manual ability is still
important in ensuring accurate application.
Tile decorators may no longer need any particular drawing or painting skills,
but they must be able to position the printing screens, batch the colours and moni-
tor the process in general.
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Accessories and trims
Instruments for chromatic graphic settings (from Fashion Tile, Gruppo Editoriale Faenza Editrice).
Today, accessories and trims still involve a degree of craftsmanship, thus pre-
cluding the introduction of massive automation (which is not justified by the small
production runs).
Nevertheless, given the keenly competitive nature of the accessory and trim mar-
ket and the fact that both machinery and glaze/colour manufacturers dedicate sig-
nificant resources to it, it seems reasonable to expect further improvements in the
future.
Technologically, then, the industry has moved on from manual or carbon-dust-
ing techniques followed by hand painting, to the application of decals, ever-more
numerous and complex silk-screen printings and the dry application of pigment
grains, glazes or glasses.
Recent years have also seen the perfection of cutting and assembly techniques
for composite trims and huge improvements in polishing.
The current trend is towards personalised relief decoration: this effect, attain-
able via the employment of complex on-press systems, acquires particular aesthetic
value in 3rd firing by combining 2-3 silk-screen colour coatings with the application
of highly transparent grains (vetrosa).
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The latter are mixed with glues and starches, the low expansion coefficient
and chemical nature of which allow application of very thick layers, thus provid-
ing double firing, single firing and porcelain tiles with a substantial degree of
relief.
Vetrosa are generally layered: a first pressed layer is compacted onto the tile
and a second silk-screen layer and a third layer are sprinkled over the entire tile so
as to consolidate the decoration.
Second firing decoration is also increasingly used on porcelain tiles: silk-screen
machines apply powders on the fired tile which then has a fast re-firing cycle (960-
980 °C).
These decorations, often polished, are specially designed to provide not only
excellent aesthetic properties but also a high degree of hardness and abrasion
resistance. This is achieved by mixing compositions that, when combined with
industrial frits, lead to the formation of glass ceramics (partially recrystallised
glasses).
At this point a few words should be said about lapping, a technology often used
to enhance aesthetics. Lapping involves a technique that, even where glazes of a
particular hardness and gloss are applied on perfectly flat tiles, allows the user
(through use of carefully selected abrasives) to partially polish the glaze without
Products featuring polished relief glaze decoration (from Fashion tile, Gruppo Editoriale Faenza
Editrice).
354
Accessories and trims
actually removing any surface layers and therefore without exposing any closed
pores in the glaze itself.
The water jet technique, used extensively in the porcelain tile sector, allows manu-
facturers to produce myriad geometric forms, from the very simple to the very com-
plex: very high pressure water jets carrying abrasive sands have proved to be highly
effective in cutting the hard, compact ceramic while numerical control devices pro-
vide pinpoint accuracy.
Attractive, highly detailed compositions, pre-assembled on paper or mesh, some-
times using marble or cotto inserts shaped by diamond-tipped tools, can thus be
created. The resulting design opportunities are innumerable.
Another key development in the decoration of accessories and trims is the Four
Colour (or Quadro) system. This is essentially an evolution of silk-screen printing
in which four prime colours are overlapped to obtain any other desired colour: used
in conjunction with computerised graphics, manufacturers can produce high-defini-
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tion photographic quality images with excellent colour separation. Four colour print-
ing requires more precise alignment at the moment of application than with stand-
ard silk-screen printing: consequently, the latest machines feature electronic piece
alignment.
Materials
The decorative materials used with accessories and trims can be split into:
Ceramic colours and pigments.
Precious metals and lustres.
Ceramic glazes (relief and non-relief).
Vetrosa grains or glass pastes.
Metallic-like colours.
Solvents, suspending agents, printing and painting media.
The ceramic colours used to decorate accessories are similar to those used on
tiles: they largely consist of frits, ceramic pigments and various inorganic raw ma-
terials (mainly oxides) which are mixed and ground to obtain a fine powder (gener-
ally < 30 µm).
Depending on the decoration technique and the specific requisites of the final,
356
Accessories and trims
decorated, fired product, one of the following three kinds of ceramic colour will be
used:
On-glaze colours: applied on the already-glazed, fired tile; this is then re-fired
between 700 and 950 °C, the exact temperature depending on the firing cycle
which causes the colours to melt and combine with the glaze surface underne-
ath.
In-glaze colours: these penetrate the glaze during firing. Used extensively in
tableware and porcelain decoration, highly resistant to chemical aggression and
abrasion.
Under-glaze colours: normally applied beneath a layer of transparent or semi-
transparent glaze, diffusing into the latter during firing.
Ceramic colours are usually supplied in powder form and thus need to be sus-
pended in appropriate liquids so that they can be applied on the tile; such vehicles
generally consist of glycols or organic polyglycols that burn away during firing.
For porcelain tiles a decoration technique has been developed in which the ap-
plied metal organic pigments penetrate the dried unfired or fired tile. Their effects
can be further enhanced after firing by polishing.
Colours for third firing applications are normally pre-mixed by the supplier,
who may also provide the correct fluxes to suit the firing cycles. Where the sup-
plier provides the bases small quantities of pigments can be added to adjust their
shade.
Third firing decoration often makes use of precious metals and lustres. Lustres
are semi-finished items similar to lacquers, made up of organo-metallic compounds
with a precious metal base combined with resins that form a film once fired on glass,
majolica or porcelain.
Lustres produce very thin, intensely coloured films, often no thicker than the
wavelength of the incident light.
The resulting luminous interference and reflection phenomena produce attrac-
tive, highly glossy, iridescent effects. Lustres are classified according to tone, which
depends on precious metal content, and the type of effect (e.g. crackled, veined,
iridescent, pearl).
Metal preparations involve the use of organic compounds with a precious metal
base; these are combined with other organo-metallic fluxes to aid adhesion and with
resins to produce films.
When applied on a smooth substrate they form, after firing, a very thin yet highly
reflective metallic film.
The resulting colours depend on the combination of precious metals: bright
golds (red-yellows consisting of Au), yellow golds (yellow-green, consisting of
an Au/Ag alloy), platinums (white gold, Au/Pt alloy) or palladiums (white gold,
Au/Pd alloy).
Introducing small quantities of matting agent produces a similar effect but with
a matt finish. A whole series of intermediate burnished finishes can be obtained by
introducing special additives.
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There are also other products which can be sprinkled onto the piece: these are
obtained from gold leaf and precipitated gold powder. They are extensively used in
the production of high quality decals.
Organisation
Accessory and trim production enterprises must be flexible and capable of re-
sponding to the needs of their client companies (i.e. tile manufacturers) quickly, as
the market often forces the latter to operate on a just-in-time basis.
That flexibility has largely been attained thanks to the advent of roller kilns,
which, because they are much more compact and have much faster firing cycles than
traditional systems, are far better suited to the production of small lots.
Flexibility has also been enhanced by the increased number of small sub-suppli-
ers performing so-called intermediate processes (silk-screen printing) or comple-
mentary tasks (cutting, mesh mounting, decal application etc.).
In certain manufacturing areas these enterprises form an important part of the
local economy.
Another, equally important factor is logistics, an aspect that has changed consid-
erably over recent years: in an industry in which the handling of materials is cru-
cial, the refinement of logistics management techniques and the appearance of lo-
gistics specialists virtually unheard of in ceramics until just a few years ago has
proved inevitable.
It seems reasonable to assume that, in the near future, increasing market pres-
sures will make logistics a key aspect of every stage of the product life-cycle, from
the supply of raw materials to post-sales assistance.
Providing a realistic Italy-wide picture of the accessory-trim output situation is
virtually impossible. Accessories, trims etc. play an increasingly important auxil-
iary role in top-of-the-range tiles, and represent a fast-expanding area of strategic
importance (the last few years have seen consistent annual growth rates of around
12%).
Whats more, there is a whole host of small and very small businesses which are
difficult to categorise as they are often small workshops or even family concerns
focussing on tasks such as hand painting, silk-screen decoration, cutting, bevelling,
gluing and polishing.
Accessory manufacturers (who are in direct contact with big industrial clients
and thus play a key role in this market) now outsource an increasing amount of
work to these enterprises.
Trims
358
Accessories and trims
Use of trims is especially widespread in the United States and other Anglo-
Saxon countries; the relative narrowness of the overall tile market dictates rather
scant total output.
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edge. This explains why, despite the fact that there are over 160 different types of
trim, so few of them are produced in numbers that justify the installation of auto-
mated machinery.
For further information on the terminology, nomenclature and classification of
these products the reader should consult the relevant trim production standards
(see bibliography).
Production line
360
Accessories and trims
b) piece handling
Another key factor is the conveying system: while most pieces can be conveyed
normally along a standard production line there are many others which require the
use of refractory supports, racks and plates. However, as the latter generally in-
volve only a relatively small portion of output, an alternative to manual handling
especially on the glazing line is difficult to justify.
The main features of a trim production line are illustrated in the flow sheet in
Fig. 189 and the plant layout diagram in Fig. 190.
Body preparation
Generally the body is the same as that used for standard tile production (both
porous and vitrified products).
This does not, however, mean that bodies are always spray dried the same way:
with trims spray-drying should aim to produce coarser grains with as low a fine
content as possible (maximum 3% at < 200 micron). Moisture content will gener-
ally be higher too (up to 6.5-7%).
This coarser, wetter spray-dried product makes the powders more plastic, thus
reducing the density differences created in the piece during pressing.
Pressing
Regularly shaped pieces can be produced using the standard single firing proc-
ess. In this instance the presses are those used for the traditional formats, equipped
with normally-raised moulds or shaped dies.
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More geometrically complex pieces must be produced outside the main line us-
ing manual-ejection presses.
Keeping the moulds clean can sometimes be a problem on account of the
higher moisture content of the powders and the frequent use of fluidisers and
release agents (special sprays or even diesel fuel). Moulds are generally lined
with rubber.
PRESS
PRESSES
e.g. PH 690
e.g. PH 120
whit automatic collection,
fettling, brushing
Manual
Drier
fettling and
rack loading
on refractory
plate
Chamber
drier
Glazing
Firing
362
Accessories and trims
1 Feeder
2 - Brusher
FUME TREATMENT UNIT
3 - Blower
4 - Water spray
5 - Drive unit
6 - Silk-screen printing
7 - Double disc booth
STORAGE AREA
8 - Conveyor
9 - Bell unit
10 - Glaze stirrer
11 - Spray gun
12 - Scraper unit
13 - Turntable
14 - Single disc booth
15 - Aligner +
straightener
16 - Row former
17 - Aut. KPT4 line
unloader
18 - Aut. KPT5 line
unloader
19 - Press
20 - Aut. KPT2 line
loader
21 - Tile aligner
22 - Roller pre-kiln
drier
23 - Automatic roller
unit
24 - FL 29.4/1600 gas
kiln
25 - Bar cooler
26 - Modular roller unit
27 - Tunnel drier
28 - Glazing station
(optional)
29 - FL 14.7 kiln
(optional)
30 - Press with auto.
unload. (optional)
31 - Complete cutting
line (optional)
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Drying
A standard fast single layer drier is generally used.
Where geometry allows, the pieces are run through the machine directly on
the rollers; where more irregular they are conveyed in special containers or on
refractory or metal plates.
Where piece thickness varies considerably (with the accompanying risk of ex-
cessive stress) a shuttle drier may be more appropriate.
Glazing
Together with fettling this is the most delicate stage of the process and the list
of potential problems is a long one.
Most difficulties stem from the need to apply a similar thickness of glaze on
differently oriented surfaces.
Glazing may be single or double-row and use bell, waterfall or disc application
systems.
The piece is sometimes tilted (vertically and transversely) when under the ap-
plicator to optimise glazing of curved surfaces.
As at the press outlet, piece-specific scraping and deburring systems are in-
stalled.
Where pieces are of particularly complex geometry they are glazed manually
on lines characterised by versatility and flexibility.
The trims are normally placed on trays or directly on the conveyor belts. In
any case they must arrive at the glazing zone under pre set temperature condi-
tions so as to limit variations in shade.
Glazes should generally be of high thixotropy so that they freeze as soon as
they come into contact with the piece.
This reduces the risk of bare patches or glaze build-up on non-horizontal sur-
faces: it also helps stop lumps of glaze forming at the edges of inclined surfaces,
an inconvenience that requires fettling.
Storage
Given the highly discontinuous nature of production a loading-unloading stor-
age system should be installed at both the drier and glazing line outlets.
364
Accessories and trims
Firing
Regularly shaped pieces may be fired directly on the rollers using the same
firing cycles employed for standard production.
Others of more complex geometry will require separate piece-specific firing
sessions.
Kiln unloading and sorting are normally done manually, with a first quality
yield comparable to that of standard production for simple pieces and about 10-
15% less for more complex items.
Machines
While the manufacture of accessories and trims is still, to some extent, a craft-
like operation, industrial development has been rapid over recent years.
Although the introduction of modern technologies and materials have yielded
products with innovative aesthetic characteristics, this situation has obviously had
(and has) an effect on the originality and hand made nature of the individual
pieces.
The range of accessory and trim products is vast: some may be porous, others
partially or totally vitrified (e.g. porcelain tile accessories) and they may be pro-
duced using different technologies (e.g. double or single firing).
A perhaps even more important aspect concerns the configuration of the piece
(i.e. tile, border, bullnose tiles, pencil tiles etc.).
Such a heterogeneous range of products, then, clearly entails a wide range of
plant engineering solutions, an exhaustive description of which is beyond the
scope of this book.
The very nature of the materials (e.g. pieces pressed in a semi-plastic state to
obtain relief effects) calls for a high percentage of manual work and working
conditions are very different from those adopted for other, more standardised ce-
ramic accessories.
However, increased automation and, consequently, improved handling, has paved
the way for innovative plant layouts that reduce the need for manual labour. The
end result has been a huge fall in production costs.
The advent of fast firing has radically modified third firing (i.e. ceramic ac-
cessory) production criteria, yet it should be pointed out that its adoption was
neither immediate nor widespread and there are still items for which it cannot be
used (the appropriateness of fast firing ultimately depends on the configuration
and nature of the body).
The degree of sophistication of a third firing plant, then, essentially depends
on the characteristics and the individuality of the pieces.
Some manufacturing operations require hybrid layouts that feature a combina-
tion of both industrial and craft-like aspects (i.e. a high degree of automation and
a high degree of manual work).
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The flow diagram in Fig. 191 shows a typical production sequence for third
firing products. It is only intended as a rough guide in that it refers to one specific
product.
For example, flow charts illustrating the production scenario for bullnose tiles,
pencil tiles or pieces pressed in a semi-plastic state would be very different.
As illustrated in Fig. 190, the tiles, after being fired and unloaded from the
kiln, are stored on special racks (should further silk-screen applications or manual
decoration be required) and then re-introduced into the production cycle and re-
fired according to parameters compatible with the new decoration.
Fig. 192 shows a typical layout for the manufacture of tiles with third firing
technology.
The following section only deals with those processes peculiar to second, third
and fourth firing technology, leaving aside more global matters such as body grind-
ing, pressing, drying glazing and firing.
Decoration
While tile decoration in second, third and fourth firing processes can be done
manually, producers generally use, where possible, silk-screen printing machines:
their level of sophistication depends on the configuration of the piece and the
overall number of pieces to be decorated.
Manual decoration and silk-screen printing may be complemented by the ap-
plication of decals, for which a wide range of automatic machines is available.
Whatever the decorative task, it is preferable to brush the piece before starting.
The market offers a wide range of silk-screen machines, from traditional mod-
els to more modern ones that allow printing to be effected parallel or perpendicu-
lar to the conveyor.
Together, the above machines form decorating lines of varying complexity;
furthermore, the application of electronic logic can provide producers with accu-
rate line feed systems.
Relief effects can be obtained on tiles and multi-tile compositions with dry-
ground grains (Fig. 193) for which the market offers a wide range of application
machines. Production lines may also need to be equipped with compensers.
Depending on how much space is available for the various silk-screen print-
ing/glazing stages, the compenser may be equipped with an autonomous forced-
draught heating system.
Decorated pieces are generally stored on automatic rack systems which can
366
Accessories and trims
Line unloader
Sorting
Quality control
Fig. 191. Flow diagram illustrating tile production with third firing technology (standard production).
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Fig. 192. Generalised layout for production of tiles with third firing technology.
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Accessories and trims
Firing
Except for very thick pieces and trims with variable thickness, tiles decorated
in second, third and fourth firing are fired in single-layer kilns with cycles appro-
priate to the particular decoration (i.e. gold, platinum or glass grains). A complex
piece could therefore require several different cycles.
These successive firing cycles, even at lower temperatures, may alter the prod-
uct shade. It is therefore essential to inspect the tile for any such changes before
each successive firing: should this problem arise testing will be required to find
more suitable firing temperatures and cycles.
Fig. 193. Screen printing machines for the application of dry ground grains (Kemac).
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Fig. 194. Closed-circuit silk-screen printing machine for the production of trims in third firing (Kemac).
Sorting
Tiles are normally sorted at the kiln exit or stored on racks and sorted later.
These products are normally sorted manually.
Given the vast range of ceramic accessories and the relative production diffi-
culties, the spread of cutting technology already used extensively with stone
products has been rapid. Cutting machines allow manufacturers to reduce stand-
ard tiles to a whole range of sub-sizes which can then be used as borders or strips,
cornices, mosaic elements etc.
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Accessories and trims
These machines cut the ceramic material continuously and generally have tile
conveyance mechanisms featuring variable-speed drives. They also feature verti-
cal and transverse adjustment and allow fast change-over of the diamond-edged
cutting wheels.
Ceramic accessories and trims and the machines used to produce them play
a key role in todays ceramic industry. An exhaustive analysis of such a vast argu-
ment is beyond the scope of this book and this chapter, like the preceding ones on
wall, floor and porcelain tiles, is intended only as a basic introduction.
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Floor tiles
Appendix 1
STANDARDS
In July 2000 Italy adopted unified international ceramic tile standards, as drawn
up by ISO between August 1985 and July 1992.
To a large extent, these reflect the contents of the widely applied UNI-EN stan-
dards, yet it should be observed that substantial modifications have been made to
ceramic product classification and test methods. Furthermore, new technological
parameters have been introduced.
With regard to tile classification, the most important innovation is the sub-divi-
sion of the first water absorption class (≤ 3 %) for pressed products into two sub-
groups: the first of these is BIa, which includes tiles with water absorption of ≤
0.5%. This new system allows for easier, more accurate product classification.
VARIATIONS:
Moisture expansion and stain resistance (glazed and unglazed products)
Agents for resistance to chemical attacks at low and high concentration
Elimination of the Mohs hardness test (ex EN 101).
A complete version of the new ISO standards would amount to more than 100
pages. Owing to limited space and commercial copyright reasons there follows just
a brief summary of the various tile classes, the test methods and a table comparing
the old UNI-EN standards.
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Standards
ISO 10545.15 Leaching of Cadmium and Lead from glazed tiles New
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Crazing resistance 105 1 hour to reach 5 Atm 11 1 hour to reach 5 Atm and 2 hours
and 1 hour holding holding
Chemical resistance 106 immersion solutions and 13 immersion solutions and test times
(unglazed) times different from ISO different from EN
Abrasion resistance 154 classes from 1 to 4 7 classes from 1 to 5 with stain test
(glazed) compulsory for class 5
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Standards
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Description of ceramic products
Appendix 2
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Table 2. PERIODIC TABLE
INERT
GASES
Atomic number
Chemical symbol
Atomic weight
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Tables and figures
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Tables and figures
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Tables and figures
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Tables and figures
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Tables and figures
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Table 13/1. TABLE OF MATERIALS MOST COMMONLY EMPLOYED IN CERAMIC INDUSTRY
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Table 13/2.
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Tables and figures
Table 13/3.
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Table 13/4.
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Tables and figures
Table 13/5.
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Table 13/6.
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Tables and figures
Table 13/7.
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Table 13/8.
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Tables and figures
Table 13/9.
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Table 13/10.
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Tables and figures
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Tables and figures
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Tables and figures
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Tables and figures
A) BODY
1) For table 22A and 22D use the following formula:
Kg dry material to charge = 0.55 × Vu × d × y/100
2) For tables 22B and 22C use the following:
Kg dry material to charge = 0.67 × Vu × d × y/100
where:
Vu = working volume of the mill (with lining) in litres
d = slip density
y = % dry matter in the slip
0.55 – 0.67 = mill load coefficient with silica or alubit grinding media.
B) GLAZE
1) For porcelain grinding media use the following formula:
Kg dry glaze to charge = 0.345 × Vu × d × y/100
2) For table 22C use instead:
Kg dry glaze to charge = 0.455 × Vu × d × y/100
where:
Vu = working volume of the mill (with lining) in litres
d = glaze density at the outlet (generally l.7) in kg/l
y = % dry in the glaze (generally 67%)
0.455 = mill load coefficient with alubit grinding media.
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Table 22a. MILL LOADING
Lining: Silica - Grinding media: Silica
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Table 22b. MILL LOADING
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Tables and figures
B) Red body single firing vitrified tile 0.6-1 0.8-1.6 0.6-1.2 1.2-1.6
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Tables and figures
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Tables and figures
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Tables and figures
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Tables and figures
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Tables and figures
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Red Si-Zr-Fe
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Tables and figures
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Tables and figures
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The tertiary diagrams and graphs on the following pages illustrate the reactions between the various
oxides and compounds that take place during firing. The graphs are numbered 1-19 to make consulta-
tion easier.
Fig. 1.
Fig. 2.
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Fig. 3.
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Fig. 4.
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Tables and figures
Fig. 5.
Fig. 6.
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Fig. 7.
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Tables and figures
Fig. 8.
Fig. 9.
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Fig. 10.
Fig. 11.
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Fig. 12.
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Fig. 13.
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Tables and figures
Fig. 14.
Fig. 15.
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Fig. 16.
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Tables and figures
Fig. 17.
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Fig. 18.
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Tables and figures
Fig. 19.
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Standards
BIBLIOGRAPHY
For a greater understanding of ceramics and more detailed information the reader
is referred to the following works:
Grimshaw The Chemistry and Physics of Clays and Other related Materials
Benn Ltd (1981)
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Introduction
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Printed September 2002
by Tipografia Moderna of Ravenna
for Editrice La Mandragora of Imola