Beruflich Dokumente
Kultur Dokumente
1.Cement:
Concrete should not be confused with cement because the term cement refers
only to the dry powder substance used to bind the aggregate materials of
concrete. Upon the addition of water and/or additives the cement mixture
is referred to as concrete, especially if aggregates have been added.
Portland cement
2. History:
History of the origin of cement
Early uses
It is uncertain where it was first discovered that a combination of
hydrated non-hydraulic lime and a pozzolan produces a hydraulic mixture
(see also: Pozzolanic reaction), but concrete made from such mixtures was
first used on a large scale by Roman engineers.[1] They used both natural
pozzolans (trass or pumice)a local name of volcanic tuff. and (ground
brick or pottery) in these concretes. Many excellent examples of
structures made from these concretes are still standing, notably the huge
monolithic dome of the Pantheon in Rome and the massive Baths of
Caracalla.[2] The vast system of Roman aqueducts also made extensive use
of hydraulic cement.[3] The use disappeared in medieval Europe, although
weak pozzolanic concretes continued to be used as a core fill in stone
walls and columns.
Modern cement
All the above products could not compete with lime/pozzolan concretes
because of fast-setting (giving insufficient time for placement) and low
early strengths (requiring a delay of many weeks before formwork could
be removed). Hydraulic limes, "natural" cements and "artificial" cements
all rely upon their belite content for strength development. Belite
develops strength slowly. Because they were burned at temperatures below
1250 °C, they contained no alite, which is responsible for early strength
in modern cements. The first cement to consistently contain alite was made
by Joseph Aspdin's son William in the early 1840s. This was what we call
today "modern" Portland cement. Because of the air of mystery with which
William Aspdin surrounded his product, others (e.g. Vicat and I C Johnson)
have claimed precedence in this invention, but recent analysis[6] of both
his concrete and raw cement have shown that William Aspdin's product made
at Northfleet, Kent was a true alite-based cement. However, Aspdin's
methods were "rule-of-thumb": Vicat is responsible for establishing the
chemical basis of these cements, and Johnson established the importance
of sintering the mix in the kiln.
3. Production
There are three fundamental stages in the production of Portland cement:
(1) Preparation of the raw mixture
(2) Production of the clinler
(3) Cement grinding
Rawmix preparation
The raw materials for Portland cement production are a mixture (as fine
powder in the 'Dry process' or in the form of a slurry in the 'Wet process')
of minerals containing calcium oxide, silicon oxide, aluminium oxide,
ferric oxide, and magnesium oxide. The raw materials are usually quarried
from local rock, which in some places is already practically the desired
composition and in other places requires the addition of clay and
limestone, as well as iron ore, bauxite or recycled materials. The
individual raw materials are first crushed, typically to below 50 mm. In
many plants, some or all of the raw materials are then roughly blended
in a "prehomogenization pile." The raw materials are next ground together
in a rawmill. Silos of individual raw materials are arranged over the feed
conveyor belt. Accurately controlled proportions of each material are
delivered onto the belt by weigh-feeders. Passing into the rawmill, the
mixture is ground to rawmix. The fineness of rawmix is specified in terms
of the size of the largest particles, and is usually controlled so that
there are less than 5%-15% by mass of particles exceeding 90 μm in
diameter. It is important that the rawmix contains no large particles in
order to complete the chemical reactions in the kiln, and to ensure the
mix is chemically homogenous. In the case of a dry process, the rawmill
also dries the raw materials, usually by passing hot exhaust gases from
the kiln through the mill, so that the rawmix emerges as a fine powder.
This is conveyed to the blending system by conveyor belt or by a powder
pump. In the case of wet process, water is added to the rawmill feed, and
the mill product is a slurry with moisture content usually in the range
25-45% by mass. This slurry is conveyed to the blending system by
conventional liquid pumps.
Rawmix blending
Formation of clinker
Precalciner kiln
Typical clinker nodules
The raw mixture is heated in a cement kiln, a slowly rotating and sloped
cylinder, with temperatures increasing over the length of the cylinder
up to a peak temperature of 1400-1450 ℃. A complex succession of chemical
reactions take place (see cement kiln) as the temperature rises. The peak
temperature is regulated so that the product contains sintered but not
fused lumps. Sintering consists of the melting of 25-30% of the mass of
the material. The resulting liquid draws the remaining solid particles
together by surface tension, and acts as a solvent for the final chemical
reaction in which alite is formed. Too low a temperature causes
insufficient sintering and incomplete reaction, but too high a
temperature results in a molten mass or glass, destruction of the kiln
lining, and waste of fuel. When all goes to plan, the resulting material
is clinker. On cooling, it is conveyed to storage. Some effort is usually
made to blend the clinker, because although the chemistry of the rawmix
may have been tightly controlled, the kiln process potentially introduces
new sources of chemical variability. The clinker can be stored for a number
of years before use. Prolonged exposure to water decreases the reactivity
of cement produced from weathered clinker.
Cement grinding
A 10 MW cement mill, producing cement at 270 tonnes per hour
In order to achieve the desired setting qualities in the finished product,
a quantity (2-8%, but typically 5%) of calcium sulfate (usually gypsum
or anhydrite) is added to the clinker and the mixture is finely ground
to form the finished cement powder. This is achieved in a cement mill.
The grinding process is controlled to obtain a powder with a broad particle
size range, in which typically 15% by mass consists of particles below
5 μm diameter, and 5% of particles above 45 μm. The measure of fineness
usually used is the "specific surface", which is the total particle
surface area of a unit mass of cement. The rate of initial reaction (up
to 24 hours) of the cement on addition of water is directly proportional
to the specific surface. Typical values are 320-380 m2·kg−1 for general
purpose cements, and 450-650 m2·kg−1 for "rapid hardening" cements. The
cement is conveyed by belt or powder pump to a silo for storage. Cement
plants normally have sufficient silo space for 1–20 weeks production,
depending upon local demand cycles. The cement is delivered to end-users
either in bags or as bulk powder blown from a pressure vehicle into the
customer's silo. In developed countries, 80% or more of cement is
delivered in bulk, and many cement plants have no bag-packing facility.
In poor countries,bags are the normal mode of delivery.
4. Performance index
4.1 The main technical index of cement
(1)specific gravity and bulk density: The specific gravity of Portland cement
is 3:1, and the bulk density is usually 1300kg/M3 .
(2)fineness:Cement fineness refers to the granularity of cement particle. More
fine of the particle, the faster of the hardening, and the higher of early strength.
(3)setting time:the needed time for cement from mixing with water to starting
primary coagulation is called initial setting time. The needed time for cement
from mixing with water to finish coagulation is called final setting time. For
Portland cement, the initial time should not less than 45 min and final setting
time should not over 12 hours.
(4)strength:Strength of cement should match National Standard.
(5)volume stability: It refers to the equality of volume changing during cement
hardening, if there are more impurity in the cement, it will cause irregular
deformation.
(6)heat of hydration: Mix cement with water will cause exothermic reaction,
during hardening of cement, continuous release the heat is called heat of
hydration.
(7)standard consistency: It refers to the consistency of cement paste when it
has certain resistance to normal testing bar’s sinking inside of cement paste.
5. Basic knowledge of cement chemistry
Gelled material:——people use it since ancient times(e.g the pyramid, the
Colosseum 3000 years ago).There are mainly two kinds of building gelled materials:
non‐hydraulic gelled material—which cant get hardened in water(see the table
below) , and hydraulic gelled material.
Portland cement——was invented by Joseph Aspdin in the middle of 19th century.
It is the product of burned mixture of crumble limestone and fine clay, containing
65%—70% CaO, 18‐24% SiO2, 3‐8% Fe2O3, 3‐8% Al2O3,and a small quantity of
secondary oxide (e.g Na2O, K2O, MgO etc.) Much more effective manufacturing
process is used in modern cement plant.People can get that cement through
materials in a right proportion, which obtains prospective scale of intensity and
durability.
II、The formattion of clinker minerral
The key
k is efffective pu
ulverizing and
Raw materrial used in modern cement plantt enizing of raw mateerial. They get
homoge
limestone clayy dried and deh
hydrated iin suspen
nsion
chalk sch
hist preheatter and preecalcinator, after that the
sh
hell kao
olin mixture
e materiaal(raw matterial) will be
m
marlite oth
her silicate minerals burned in rottary kiln. When the
o
obtaining iro
on、aluminum temperrature comes up to 1500oC(at the
probably chalybeate
c correctivee materials firing zone
z of kiln ),materials have gone
g
thro on and sinttering. Viaa cooling prrocess we can get clinker
ough solid sstate reactio
and
d afterwardss it will be sent for pu with plaster.
ulverizing w
The formation of clinker mineral
1、Dehydration and decompose of raw material
With the dehydration, decomposition and activation of inserted water and clay
mineral:
Al 2O3 ⋅ 2 SiO2 ⎯
⎯→ Al 2O3 + 2 SiO2
2、Decomposition of carbonate
When the temperature is above 600℃, the carbonate of raw material begins to
decompose. When the temperature is around 750℃, MgCO3 decomposes
acutely and quickly ;Ca CO3 decomposes quickly at the temperature of 900℃,
and stops decomposing at1000℃.
MgCO 3 ⎯about
⎯⎯ ⎯→ MgO + CO 2 ↑
750℃
CaCO 3 ⎯about
⎯⎯ ⎯→ CaO + CO 2 ↑
910℃
3、Solid phase reaction
Due to the dehydration of clay、 decomposition of carbonate etc, SiO2、Al2O3、
Fe2O3、CaO come into being in the raw material, they are active and do exist
separately. They start the combination reaction with each other, and the reaction
speed gets faster gradually with the temperature increment. The solid phase
reaction, which occurs among the motes by mutual contact, is polystage
reaction, and it’s much complicated. The reacting process is as follows:
CaO + Al2O3 ⎯
⎯→ CaO ⋅ Al2O3
2CaO + SiO2 ⎯
⎯→ 2CaO ⋅ SiO2
(the formation reaction of C2S stops at about 1200℃)
4、The firing of clinker
When the temperature comes up to 1300℃, C3A and C4AF get fused, and
liquidoid appears in the materials. Absorbing CaO in the liquidoid, C2S becomes C3S:
This is called lime absorbing process. In real manufacturing process the
temperature of materials is controlled above 1300℃, usually between 1350~
1500℃, this scope is called “firing temperature”.
5. The cooling of clinker
Burned clinker needs to be cooled.the speed of cooling have much effect on the
quality of clinker. Fast cooling can prevent β − C2 S with good hydraulicity
turning into γ − C2 S that hardly has any hydraulicity. Fast cooling still can prevent
2、The Portland cement clinker mineral component
In the composition of Portland cement clinker,CaO、SiO2、AI2O3、Fe2O3 and so
on it is not only existence by the independent oxide compound ,but by two kinds or
two above oxide compounds responded that combines to plant the different oxide
compound the aggregate, namely existence shape by many kinds of chamotte
mineral . These chamotte mineral crystal is tiny.So, we may think that the Portland
cement chamotte is composed of a kind of mineral constituent, and the crystal tiny
man‐made rock..
In the Portland cement clinker ingredient's essential mineral has the following
four kinds:
calcium silicate : 3CaO·SiO2 , the abbreviation is C3S;
dicalcium silicate : 2CaO·SiO2, the abbreviation is C3S;
tricalcium aluminate ; 3CaO·Al2O3, the abbreviation is C3A
4CaO·Al2O3·Fe2O, the abbreviation is C4AF
Diffe C3S + C3A +
C3S C2S C3A C4AF
rentiates C2S C4AF
rota 42~ 15~ 4~ 10~ 72~ 20~
ry kiln 60 32 11 18 78 24
In addition, includes litter f‐CaO, crystallization magnesia(MgO),
cholinergic‐bearing mineral, vitreous body and so on..
The same as portland cement clinker, but there will be quite differents in the
main mineral content, because of the production clinker's technological conditions
are different or Clinker performance requirements of the different ingredients
chosen by the different programmes.
The four major minerals have their own characteristics, thus calcined clinker
and cement also affect the quality of a greater difference.
1、C3S is the most important mineral composition in Portland cement clinker. Its
content approximately composes the chamotte above 50%. In the C3S crystal often
includes few oxide compounds and so on MgO and Al2O3, these materials form the
solid solution, by named Alite, the abbreviation is A ore. Adding water to reconcile
C3S,The setting time is normal, The hydrated is quickly, early in the high‐intensity,
intensity progression rate is big. Its 28 days of intensities, 1 year intensity is highest in
4 kind of minerals,its volume air shrinkage is smally,and its frost resistance ie great.
Therefore, we hope have more C3S ingredients in the clinker togenerally. But it’s
hydration heat is highly,the water resisting property is badly, anti‐sulfate etching
power is badly too. Moreover, in calcine process, we needs the highly firing
temperature and the longly firing time can form the C3S, this causes the chamotte
the calcine operation becomes difficultly.So, in the actual production we has no
alternative but to cut pursues the C3S quantity, otherwise harmful ingredient f‐CaO
will be to increase, Causes to reduce the clinker quality.
2、When C2S function with water,the hydrated speed is slowly, intensity is lowly
in early time, but the intensity still faster growth after 28 days later,its may approach
C3S a year later. Its hydration heat is lowly,it dosen’t have volume air shrinkage, the
water resisting property and the anti‐sulfate etching power is strong. Its formation
temperature is low in generally, absolute C2S easy to have the multi‐crystal seed
transformation below in 1450 ℃,especially when is lower than 500℃,when β‐C2S
transforms intoγ‐ C2S, its density is more smaller, activeness is very low, and its
Volume expansion 10% , Lead to the clinker dusting, and causes the chamotte
intensity to reduce greatly. This kind of phenomenon happened comparatively much
in which vertical kiln production that bad ly ventilates,few liquid phase quantity, the
reducing atmosphere is more thicker and cool(ing) down is slowly. Firing at a higher
temperature, rapid cooling of the clinker, as C2S in the solution into a small amount
of Al2O3、Fe2O3、MgO,usually can be maintained β ‐. This is called β‐ C2S Belite,
the abbreviation is B ore.
C3S and C2S generic term is silicate mineral. The clinker mainly composed of
them, they occupy the clinker ingredient above 70%, Is the clinker intensity
important source. Portland cement. This is the Portland cement name origin.
3、C3A:After combined with water,hydration is more faster,the congealment
hardening is very quick,if does not add retarders and so on gypsum, easy to cause
the cement flash set. Its intensity is high in early times, however, little growth in the
latter part of intensity, even shrinks but actually.Its heat of hydration is high, the air
shrinkage distorts in a big way,the anti‐sulfate corrodes and the alkali resistance to be
bad..It's also brittle, poor wear resistance. In C3A may melt oxide compounds and so
on few SiO2, Fe2O3, MgO.
4、C4AF:the hydrated hardening speed is quickly, thus the early strength is high,
is only inferior to C3A.. Its long‐term strength is also high like C3S, different with C3A.
It's hydration heat low, the air shrinkage distortsu is small, the anti‐impact and the
anti‐sulfate corrodes to be good.
In fact, C4AF is the C2F—C8A3 continual solid solution, in general in Portland
cement clinker, this kind of continual solid solution's chemical composition
approaches in C4AF,so, represents in the chamotte by C4AF the hard aluminate
mineral, Is called only then Ritter (Celite), or C ore. In the mineral dissolves has few
oxide compounds and so on MgO、SiO2. The C ore assumes the white under the
emitting light, therefore is called the white intermediate phase.
C3A and C4AF and clinker in the composition of the vitreous and volatile
compounds, such as alkali,then Packing between C3S and C2S,are called for the
intermediate phase。Intermediate phase calcin to certain temperature in chamotte,
fuses the liquid phase。Liquid is the reaction of the necessary conditions for C3S。
Forms the essential mineral C3Sessential certain liquid phase quantity and the low
liquid phase viscosity。Therefore, in ordinary circumstances,we must have certain
quantity of C3Aand C4AF, thus guarantees certain liquid phase quantity;at the same
time,the C3A quantity cannot be excessively more,not only this considered that it
some bad characteristics which reveals in the hydrated process,it also lies in the
formation of large liquid viscosity,does not favor essential mineral C3S the
production。Of course, to the general technological conditions' cement kiln, has
certain amount C3A regarding the kiln skin (revolving furnace) is also necessary..
3、Clinker rate value and significance
Cement clinker is a collection of many fossils, But these minerals are also
combined from the main oxide compound chemical combinations.So, In production
control, we should not only to control the clinker in the oxide content,should also
control the oxide rate is the ratio between the value. Like this,may express between
the chemical composition and the mineral constituent relations quite conveniently,
its can express explicitly to cement clinker's performance and the calcine
influence.So,in production, the rate was as a production value of the control of a
target. The people were engaged in the cement production the experience to
summarize the chamotte rate the value for a long time. In the control of the clinker
production rate than the value of the absolute control of the oxide is more important,
but also more convenient. The rate of raw material is also the basis for the
ingredients. Various countries recognize several kind of commonly used rate value
formulas have four kinds.
In1868,german MishowEllis first proposed the hydraulic index (Hydraulic
Modulus) takes the control chamotte being suitable lime content a coefficient.
Calcium oxide and the acid oxide sum in chamotte mass percent ratio, indicated by
HM or m. Its formula is as follows:
CaO
HM =
SiO 2 + Al2 O 3 + Fe 2 O 3
In the formula: CaO, SiO2 、Al2O3 、Fe2O3 separately on behalf of chamotte in
various oxide compounds mass percent.
Usually hydraulic index fluctuation between 1.8~2.4. The above equation
supposes the calcium oxide quantity which various acid oxides unify is the same, in
fact when various acid oxides proportion has been changed,although the sum total
was invariable,but needs the calcium oxide quantity not to be the same..So, although
hydraulic index computation is simply,if only controls the similar hydraulic index, thus
has the disadvantageous influence to the chamotte quality and the calcine. Only then
simultaneously controls between various acid oxides the proportion, we can
guarantee the chamotte ingredient the stability
Afterward, keer proposed that in the chamotte between the acid oxide relates
rate the value, namely: Silicon rate, also calls the silica modulus, Indicated by SM or n:
aluminum rate, also calls the Iron Modulus or alumina rate, Indicated by IM or p.Its
formula is as follows:
SiO 2
SM(n ) =
Al 2 O 3 + Fe 2 O 3
Al 2 O3
IM ( p) =
Fe2 O3
In formula: CaO, SiO2 、Al2O3 、Fe2O3 separately on behalf of chamotte in various
oxide compounds mass percent.
Usually, portland cement clinker silicon rate between 1.7~2.7, aluminum rate
between 0.8~1.7. Some species silicon rate can be as high as about 4.0 such as white
Portland cement clinker, but the anti‐sulfate cement or cement of low heat of
hydration's aluminum rate may lower to 0.7.
The silicon rate is expresses in the clinker the silica content and the aluminum
oxide, the ferric oxide sum of mass ratio, also expressed the silicate mineral and the
melting agent mineral proportion in the clinker. When the aluminum rate is bigger
than 0.64,mathematics type which and the mineral constituent relates after between
the inferential reasoning silicon rate is:
C3S + 1.325C2S
SM =
1.434C3A +2.046C4AF
In formula: C3S 、C2S、C3A 、C4AF separately on behalf of chamotte in various
oxide compounds mass percent.
Obviously, the silicon rate of fluctuates ratio of along with the silicate mineral
and the melting agent mineral.. If the silicon rate is too higher in the clinker, when
calcine, because the liquid phase quantity obviously has reducesd, the chamotte
calcine is difficulties; Especially when the calcium oxide content to be lower, the
content of calcium silicate is higher, the clinker is easy to pulverize the silicon to lead
excessively lowly, the silicate mineral are too few in the clinker and affects the
strength of cement, because and the liquid phase content is excessively high, easy to
appear congeals the bulk, the knot accretions, the knot circle and so on, affects kiln's
operation.