Beruflich Dokumente
Kultur Dokumente
excellent technical properties of traditional bone china. The bodies were characterised for water absorption,
In a second step, we tried to develop a slip by analysing linear shrinkage (per calliper), geometrical density (in an
the rheology, viscosity and other factors to achieve analytical balance and calliper) and four-point flexural
optimal stabilisation to casting the pieces. strength tests.14 Deformation on firing test (also known
as pyroplastic deformation or sag test) was performed
with one piece for each test condition, as described in
Experimental Segadães.15 The microstructure was observed in an SEM
The waste glass used in this work was from the cleaning (Jeol JSM-5800) with microanalysis by an energy
and grinding of clear glass from pots and bottles, made dispersive spectrometer (Noran). Samples were prepared
with soda lime glass. It was then wet milled in a ball mill for SEM by polishing (with SiC abrasive paper in
with alumina media. decreasing particle size, ending with a suspension of
The basic body formulation of this study was 50% alumina in wool), sometimes followed by acid etching
calcined bone, 25% kaolin and 25% feldspar, in weight (20%HF, at different times) to remove glass phase.
percentage. The new formulation used 15% feldspar, 10% A casting slip was formulated with waste glass, and
waste glass, 50% calcined bone and 25% kaolin. The then, the density was adjusted to the proper value with
amount of waste glass was chosen based on preliminary addition of water. Ball clay (1%) was added to the batch.
tests. The slip was prepared with 70% of solid and 30% of
The chemical analysis of raw materials was carried deionised water with addition of 0?15% deflocculant
out by X-ray fluorescence (model Shimadzu-1800), and agent (ammonium polyacrylate).
crystalline phases were determined by X-ray diffraction The characterisation of the slip viscosity was made in
(Philips model X’Pert MPD) as shown in Table 1. a digital viscometer (model LVDV-II with small volume
Table 2 presents particle size distribution by laser device, spindle SC4-18, Brookfield, Stoughton, MA,
diffraction (model Cilas 1180). This analysis was USA). The deflocculant agent was added until the
performed after grinding the raw materials to sieve at minimum viscosity was reached.
325 mesh (opening of 45 mm).
The bone powder used here is from a company that Results
produces handmade items and is a waste from cutting and
polishing of bovine bones previously cleaned with caustic Characterisation, firing behaviour and
soda (NaOH). In laboratory, the bone powder was mechanical strength
calcined at 1000uC and milled until 90% of the particles Figure 1 and Table 3 show the results of technological
were ,14 mm, as recommended in the literature.12,13 characterisation tests. Figure 1 emphasises the difference
The body formulations of the raw materials were in firing behaviour between both body formulations.
mixed in the wet mill, dispersed with sodium silicate The firing ranges for each body are highlighted in
(solution in water) and passed through a sieve of 325 Fig. 1 informed by values of water absorption ,0?5%. It
mesh. Next, the body was dried (110uC) in an oven, can be observed that waste glass showed higher fluxing
moistened with water (8 wt-%) and granulated by strength compared to feldspar body, which reached
sieving mesh 20 (0?84 mm). The ceramic bodies were the desired vitrification only at 1260uC (Fig. 1). This
formed in hydraulic press, comminuted by a mortar, behaviour can be explained by the fact that a potassium
dried, mixed by hand and again moist (8 wt-%),
granulated (sieve 20 mesh) and pressed (at y30 MPa) Table 2 Raw materials particle size distribution after wet
to 8620660 mm dimensions. The pieces were naturally milling
dried for 48 h and in an oven at 110uC for at least 24 h.
Raw material particle size distribution/mm
The density (in kerosene) of the dry parts was
y1?90 g cm23. Tests were performed at least with eight Mean particle
specimens of each test body formulation. The firing Sample 10%,/mm 90%,/mm size/mm
temperatures investigated ranged from 1180 to 1280uC
in an electric muffle furnace. The bodies of both Calcined bone 0.52 11.21 4.16
formulations were fired simultaneously for each test Kaolin 2.35 14.26 7.89
Feldspar 2.03 41.49 22.5
temperature. The heating rate was 150uC h21, and the
Waste glass 2.18 32.3 19.82
dwell was 30 min at the maximum temperature.
1 Linear shrinkage and water absorption (WA) as function of firing temperature; feldspar and waste glass bodies
feldspar was used, which consists mainly of microcline the behaviour of vitrification is governed by the total
(KAlSi3O8). Alkali feldspar that has higher levels of amount of alkali ions and their distribution in the
albite (NaAlSi3O8) showed vitrification between 1220 microstructure. Therefore, the use of recycled materials
and 1240uC in another study performed by one of the such as glass waste was feasible, but it must provide a
authors.16 certain amount of fluxing oxides, for example, as shown
In Fig. 2, the microstructure of the parts of feldspar in Table 1 (established in preliminary tests, for the
and waste glass bodies can be observed. The difference present work), in order to reduce firing temperature.
of firing is evidenced by an amorphous phase covering Table 3 and Fig. 3 show that both formulations
the entire surface of the waste glass formulation, while achieved sufficiently high mechanical strength. There is
feldspar body shows large pores and open porosity. an almost direct relationship between pore size and
The addition of glass to the feldspar body (waste glass mechanical strength (Table 3). Considering what is
body) resulted in a lowering of 20uC in the onset shown in the microstructure (Fig. 2), the relationship
vitrification temperature, as shown in Table 3 and of pore size and the mechanical strength is clear. That is,
Fig. 1. In contrast, at 1280uC, the pieces have begun the larger the pore size and the amount of porosity, the
to show the expansion of porosity, even as a slight lower the mechanical strength. Porcelain mechanical
bloating, indicating that firing should not be perform- strength is mainly a function of its phases and
ed at temperatures above this temperature. Although porosity.18,19
waste glass is a strong flux, mainly due to the pre- In Fig. 4, using acid attack to remove glass phase, a
sence of sodium oxide (y14 wt-%), as previous studies fractured microstructure for both bodies can be seen. This
confirm,1,17 its mixture with feldspar provides a suffi- occurs as a consequence of the stress generated due to the
ciently broad range of firing. This allows commercial difference in thermal expansion between the matrix and
production of this body, since it is characteristic of bone the clusters of grains of b-tricalcium phosphate (linear
china’s short intervals of firing.10 Other studies, using thermal expansion coefficient of y12 1026 K21).11 As
conventional flux as alkali feldspar (richer in sodium cited before, the difference between bodies in pore size,
than the feldspar used in this work) and nepheline notably higher for the feldspar body, can be noted.
syenite, showed similar firing ranges and, in some cases, The size of clusters of b-tricalcium phosphate is also
lower ones.5,16 Thus, the presence of higher levels of different between the formulations (Fig. 4). These varia-
fluxing oxides in the glass body explains the lower tions in cluster size can be explained by many factors,
temperature of vitrification of this formulation. The such as the amount of glass phase, vitrification tempera-
mix of waste glass and potassium feldspar showed a ture and viscosity of the glass phase. These factors affect
vitrification behaviour similar to alkali feldspar. Thus, the capacity of accommodating the stresses generated by
Waste glass
1200 4.21¡0.51 10.49 2.10 46.5¡3.5
1220 0.67 12.30 2.24 61.7¡7.0
1240 0.05 13.55 2.27 54.3¡6.2
1260 0.00 14.62 2.33 56.5¡5.5
1280 0.18 13.53 2.24 63.5¡7.4
Feldspar
1240 1.22¡0.38 8.80 2.17 41.1¡4.3
1260 0.06 9.65 2.22 54.0¡4.1
1280 0.05 9.59 2.16 48.1¡4.7
2 Images (SEM): no chemical etching; a waste glass and 4 Images (SEM): chemical etching (20%HF, 20 s); a waste
b feldspar bodies fired at 1240uC; difference in vitrifica- glass and b feldspar bodies fired at 1240uC
tion is clear
bone china was observed in other studies, in which quartz
differential thermal expansion between the phases. was added as a raw material at levels of y6%.11,16
However, the main difference in Fig. 4 is the presence Usually, feldspar has quartz as a contaminant in the raw
of large and rounded pores in the feldspar body. material: on the other hand, waste glass does not have any
The difficulty to obtain higher firing ranges for bone quartz. However, a significant influence of quartz phase
china can be explained by the low amount of quartz. This on the firing behaviour of the bodies tested here is not
phase undergoes gradual dissolution during firing, expected. The microstructural analysis shows that the
increasing the amount of silica in the glass phase, which presence of quartz is small in the feldspar body (Fig. 4).
ensures higher viscosity and, consequently, higher dimen- Figure 5 shows the waste glass body microstructure at
sional stability of quartz porcelain pieces at elevated firing high magnification. During firing, it is very important
temperatures.16,20,21 The absence of quartz dissolution in that the viscosity and the amount of glass (amorphous)
phase are sufficient to make it possible to cover all the
microstructure. The glass phase must fill all the pores
and cracks to achieve a high mechanical strength of the
pieces.
To explain the lower firing temperatures of waste glass
body, it is proposed that the presence of waste glass acts
like a strong flux, i.e. it begins to melt (viscous flow
mechanism of sintering) at temperatures lower than those
of the conventional formulation (feldspar body) in order
to accelerate the sintering reactions. The contribution of
sodium ion provided by waste glass is considered the most
important factor reducing the sintering temperature and
leading to a condition close to vitrification of sodium
feldspar bodies.
7 Viscosity and shear stress in function of shear rate; waste glass and feldspar bodies
Conclusion
It was possible to produce bone china parts with 60 wt-
% of the batch sourced from recycled materials.
The use of recycled glass as a flux has reduced the firing
temperature, relative to potassium feldspar. However, the
range and firing temperature were similar to formulations
with sodium–potassium feldspar. This proves the pre-
dominance of the effect of sodium oxide over calcium
oxide, considering that this is present in smaller amounts
in the waste glass used for a viscous flow sintering
8 Viscosity in function of deflocculant amount; waste process.
glass and feldspar bodies Waste glass body reached lower firing temperatures
without pyroplastic deformation of parts occurring and
Slip casting characterisation with retention of similar technical properties to the
traditional body, such as mechanical strength and
Figure 7 illustrates the rheological curves of both for- thermal expansion. Its whiteness was superior, since
mulations tested. Note that the viscosity of the suspensions waste glass has no ferrous oxides.
decreases and shear stress increases, as shear rate increases. Feldspar and waste glass slip casting bodies showed
This is a typical behaviour of a Bingham curve.22 It can be similar rheological properties, with stabilised suspen-
inferred from Fig. 7 that the partial replacement of the sions, and typical Bingham curves, for the range of shear
feldspar flux decreased initial viscosity of the slip but did stress, shear rate and viscosity analysed. However, the
not change its behaviour (the same can be said about presence of waste glass was favourable to the defloccula-
Fig. 8). tion of the slips, since it provides the formation hydroxyl
Figure 8 and Table 4 exhibit the influence of defloccu- ion. This means cost savings associated with the
lant addition on the viscosity of the slips. Initially, it addition of additives.
reduces the viscosity of the suspension until a minimum
point. Feldspar slip needed more deflocculant to reach its Acknowledgements
minimum. However, for practical purposes, both slips
reached the same viscosity range for casting at y0?3 wt- The authors acknowledge CNPq for financial support;
% of deflocculant (as the slips had already been prepared Dr H. C. M. Lengler, geologist; and Professor Dr C. P.
with 0?15%, a total of 0?45 wt-% dispersant was used), Bergmann, head of Laboratory of Ceramic Materials/
according to Fig. 8. After this point, continuous addi- Universidade Federal do Rio Grande do Sul.
tions of deflocculant cause an increase in viscosity by
flocculating particles, as explained in literature.23 References
The shear rate of 0?7 s21 was used to obtain viscosity
data described in Table 4. It is observed that feldspar 1. S. R. Bragança and C. P. Bergmann: ‘Traditional and glass powder
porcelain: technical and microstructure analysis’, J. Eur. Ceram.
formulation showed a high viscosity with thicker wall Soc., 2004, 24, 2383–2388.
formation. According to Herrmann,24 the formation of 2. E. Bernardo, L. Esposito, E. Rambaldi and A. Tucci: ‘Glass based
walls depends on dispersion and/or thixotropy, and stoneware as a promising route for the recycling of waste glasses’,
thicker walls for short period of time is associated with Adv. Appl. Ceram., 2009, 108, (1), 2–8.
3. P. R. Jackson, P. Hancock and D. Cartlidge: ‘Recycled bottle glass as
higher viscosity. The density and minimum viscosity of a component of ceramic sanitaryware’, in ‘Proceedings of sustainable
both slips are suitable for porcelain production.25 It can waste management and recycling: glass waste’, (ed. M. C. Lymbachiya
be highlighted that waste glass had a lower dispersant and J. J. Roberts), 313–320; 2004, London, Thomas Telford.
consumption, as is desired for industrial purposes 4. T. Tarvornpanich, G. P. Souza and W. E. Lee: ‘Microstructural
evolution on firing soda–lime–silica glass fluxed whitewares,’
(,0?5 wt-%). The use of waste was also favourable for
J. Am. Ceram. Soc., 2005, 88, (5), 1302–1308.
deflocculation of hard porcelain, as shown in another 5. C. G. Portillo: ‘Influence of the type of melting on the properties of
study.9 Glass addition in a slip results in the formation bone porcelain,’ Bol. Soc. Céram. Vidrio, 1998, 38, (5), 397–402.
of hydroxide ion. This ion increased slip pH (waste glass 6. S. R. Bragança, H. C. M. Lengler and C. P. Bergmann:
slip pH 10, and feldspar slip pH 9). The adsorption of ‘Spodumene-bearing rock as flux for triaxial ceramic bodies’,
Adv. Appl. Ceram., 2011, 110, (5), 293–300.
OH2 on kaolinite particles promotes the deflocculation 7. A. Tucci, L. Esposito, L. Malmusi and E. Rambaldi: ‘New body
of the slip, by increasing the repulsion strength between mixes for porcelain stoneware tiles with improved mechanical
characteristics’, J. Eur. Ceram. Soc., 2007, 27, 1875–1881.
Table 4 Slip properties 8. Y. Iqbal, P. F. Messer and W. E. Lee: ‘Non-equilibrium micro-
structure of bone china’, Br. Ceram. Trans., 2000, 99, (3), 110–116.
Waste 9. S. R. Bragança and C. P. Bergmann: ‘Porcelain casting slips formulated
Bodies Feldspar glass with waste glass’, Int. J. Appl. Ceram. Technol., 2009, 6, (2), 264–269.
10. P. Rado: ‘Bone china’, in ‘Ceramics monographs – a handbook of
Slip density/g cm23 1.796 1.802 ceramics’, 1–10; 1981, Freiburg, Verlag Schmidt GmbH.
Surface area of the flux/m2 g21 3.98 3.82 11. Y. Iqbal, P. F. Messer and W. E. Lee: ‘Microstructural evolution in
Thickness wall forming in 1 min mm21 3.58 3.02 bone china’, Br. Ceram. Trans., 2000, 99, (5), 193–199.
12. D. Basnett and P. J. Cartwrigtht: ‘The effect of bone properties on
Initial viscosity/mPa s 11 584.0 8768.0
china casting’, Trans. J. Br. Ceram. Soc., 1989, 88, (5), 191–195.
Viscosity after deflocculation 704.0 576.0
13. J. J. Cooper: ‘Bone for bone china’, Br. Ceram. Trans., 1995, 94,
at 0.7 s21/mPa s
(4), 165–168.
14. ASTM C134-95 (2010) Standard Test Methods for Size, 20. W. M. Carty: ‘Observations on the glass phase composition in
Dimensional Measurements and Bulk Density of Refractory Brick porcelains’, Ceram. Eng. Sci. Proc., 2002, 23, (2), 79–94.
and Insulating Firebrick and ASTM C-133/97 (2008) Standard Test 21. K. H. Schüller: ‘Porcelain’, in ‘Ceramics monographs – a handbook
Methods for Cold Crushing Strength and Modulus of Rupture of of ceramics’, 1–6; 1979, Freiburg, Verlag Schmidt GmbH.
Refractories, ASTM, Philadelphia, PA, USA. 22. J. S. Reed: ‘Principles of ceramic processing’, 2nd edn, 281; 1995,
15. M. Segadães: ‘Refratários (Refractories)’, 40–41; 1997, Portugal, Oxford, John Wiley & Sons.
Universidade de Aveiro. 23. C. H. Schilling and I. A. Aksay: ‘Slip casting’, ‘ASTM engineered
16. S. R. Bragança and C. P. Bergmann: ‘A comparative study between materials handbook. Vol. 4: ceramics and glasses’, 153–158; 1991,
bone china and hard porcelain’, Ind. Ceram., 2008, 28, (3), 189–194. Cleveland, OH, ASTM International.
17. S. R. Bragança and C. P. Bergmann, ‘Waste glass in porcelain,’ 24. R. Herrmann: ‘Slip casting in practice’, in ‘Ceramics monographs –
Mater. Res., 2004, 8, (1), 01–07. a handbook of ceramics’, (ed. W. Bilke and D. Paetsch) 1–6; 1989,
18. C. S. Prasad and K. N. Maiti: ‘Thermo-mechanical properties of Freiburg, Verlag Schmidt GmbH.
bone china bodies’, Interceram, 1998, 47, (4), 221–227. 25. M. W. Carty and U. Senapati: ‘Porcelain – raw materials,
19. S. R. Bragança and C. P. Bergmann: ‘A view of whitewares mechanical processing, phase evolution, and mechanical behavior’, J. Am.
strength and microstructure’, Ceram. Int., 2003, 29, 801–806. Ceram. Soc., 1998, 81, (1), 3–20.