Characterization of Microstructure in Experimental Triaxial Ceramic Body

DOI : 10.2240/azojomo0270

Characterization of Microstructure in
Experimental Triaxial Ceramic Body
Jul 10 2008

Simón Y. Reyes López and Juan Serrato Rodríguez

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AZojomo (ISSN 1833-122X) Volume 4 July 2008

Topics Covered
Abstract
Introduction
Experimental Procedure
Results and Discussion
Phase Evolution and Densification of Triaxial Body
Conclusions
Acknowledgements
References
Contact Details

Abstract
The microstructural evolution in a triaxial body containing kaolin, quartz and anorthoclase
has been examined. DTA reveals that kaolin dehydroxylates at 4940°C and mullitization
starts at 990°C. Decreased intensity of the α-quartz peaks both in XRD and IR spectra up to
1300°C indicated the onset of partial dissolution of α-quartz at temperatures higher than
1200°C. Evidence of kaolinite relicts being engulfed and dissolved by liquid glass was seen
by SEM. Nanometric mullite formed on a pure clay relict was detected by XRD at 1050°C.
Apparent porosity and linear shrinkage data show the onset of densification at 1000°C and

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

the appearance of bloating at temperatures higher than 1250°C. During the last stage of
sintering at temperatures higher than 1100°C porosity is highly reduced and the body
densifies abruptly as feldspar melts.

Keywords
Triaxial Ceramics, Microstructure, Quartz Dissolution, Mullite, Bloating.

Introduction
Triaxial ceramics have been widely studied due to their diverse applications. Studies over
several decades, confirmed the need for a higher volume of data, particularly regarding
microstructural development to assist in the interpretation of triaxial systems [1, 2]. The
microstructure of a triaxial porcelain typically consists of residual quartz, and mullite in a
vitreous matrix [3, 4]. Lundin [5] and Schuller [6] reported the formation of two types of
mullite in porcelain bodies. Crystalline mullite in the form of clusters that show up in clay
residuals, are considered as primary mullite, while long needle habit mullite is referred to as
secondary mullite. Schuller [6] reports that to 1400°C as primary mullite transforms to
secondary mullite; the mullite forms in the presence of a silica-rich glass liquid phase
derived from the melting of feldspar.

Iqbal and Lee [2], reported the microstructural evolution in a model triaxial porcelain in
samples fired for 3 h at 600–1500°C. They found that the clay component dehydroxylated
to metakaolin at 550°C and metastable sanidine formed from decomposition of the feldspar
at about 600°C and dissolved at about 900°C. Liquid formation at 1000°C was associated
with melting of feldspar and silica discarded from metakaolin formation via the K2O–Al2O3–
SiO2 eutectic. Fine mullite and γ-alumina crystals precipitated in pure clay relicts and larger
mullite crystals in mixed clay-feldspar relicts at 1000°C.

Feldspars are low-melting mineral alkaline aluminosilicates and in triaxial bodies serve to
lower the temperature at which viscous liquid forms. The liquid phase reacts with other
body constituents and gradually permeates the microstructure, leading to its densification.
The group of feldspar minerals consists of three silicates: a potassium-aluminum silicate
(the orthoclase feldspars), a sodium-aluminium silicate, and a calcium-aluminium silicate
(the plagioclase feldspars) and their isomorphous mixtures. Typical final microstructures of
fired porcelain bodies consist of 10%–25% mullite, with composition ranging from
2Al2O3.SiO2 to 3Al2O3.2SiO2, 5 – 25% α-quartz (SiO2), and 0 –8% pores dispersed in 65 –
80% potassium aluminosilicate glass. Bodies with a high percentage of quartz also may
contain cristobalite [2].

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

A soda microcline named anorthoclase frequently used as a flux in triaxial body

compositions is an isomorphous mixture of KAlSi3O8 and NaAlSi3O8, the sodium-aluminium
silicate being in larger proportion. The purpose of this study is to investigate the
microstructure-densification relationships in an experimental stoneware obtained by slip
casting at temperatures up to 1300°C

Experimental Procedure
Homogeneous batches of powders, comprising kaolin (50 wt%), anorthoclase feldspar (40
wt%), and quartz sand (10 wt%) were made into a slurry by mixing in a porcelain jar in
which sodium silicate was added as deflocculating additive. Slips were cast into gypsum
moulds by the standard technique and dried at 1000C followed by firing up to 1300°C for
0.5 hr in an electrical furnace. Apparent density was measured via the Archimedes’s
method and water absorption according to ASTM Designation: C 373-88 (i.e. weight gain of
dried bulk samples after immersion in boiling water for 5 h and 24 h in cool water). Linear
shrinkage during sintering was calculated from the dimensions of the green and the
sintered samples. The shrinkage behaviour was also assessed by in-situ measurements in
a Theta thermodilatometer. Scanning electron microscopy, (Jeol JSM-6400, 25 kV
acceleration voltage), was done in secondary and backscattered electron modes in mirror-
polished surfaces etched by immersing in 2 vol% HF solution for 4 min. X-ray diffraction
analysis used a Siemens D5000 Cu Kα radiation 1.54 at 20 kV. DTA measurements were
done in a DSC (Model Q600 Instruments, New Castle, DE). Particle size measurements
were done in a Horiba Capa 300. Attenuated Total Reflection (ATR) (ZnSe crystal)
technique used an IR Spectrometer fitted with a Fourier transform (TENSOR™ 37 series
FT-IR, Bruker Optics Inc), while Raman spectra were obtained by a LabRam Analytical
Raman Microscope spectrometric (HORIBA Jobin Yvon).

Results and Discussion

Phase Evolution and Densification of Triaxial Body

DTA of triaxial composition (Figure 1) reveals endotherms with maxima at 31.71°C for
dehydration. The peak at 494.56°C, corresponds to dehydroxylation of kaolin to form
metakaolin. The exotherm at 990.36°C corresponds to the onset of crystallization of mullite.
TGA profile (Figure 1), shows mass loss of 5.9 wt%. Figures 2 and 3 show XRD and IR
phase evolution data for the triaxial body fired up to 1300°C.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 1. DTA and DTG Data of triaxial body. Dehydroxylation occurs at 494°C bringing
about a weight loss of 5.9 wt %. Note Mullitization at 990°C.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 2. X Ray Diffraction of triaxial body showing partial dissolution of quartz and the
appearance of mullite at about 1050°C.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 3.IR Spectra at various temperatures. Note dehydroxylation of Si-O-Al band at 3600
and 1000 cm-1 at 600°C.

XRD peaks show the absence of kaolinite at 600°C brought about from the loss of
hydroxylic groups from the structure at 494°C. Kaolinite and anorthoclase peaks are hardly
noticeable at 600°C. Decreased intensity of the α-quartz peaks both in XRD and IR spectra
up to 1300°C showed the onset of partial dissolution of α-quartz at temperatures higher
than about 1200°C.

SEM (Figure 4) shows crystalline quartz dissolving in a glassy matrix. Mullite was first
detected by XRD at 1050°C and its amount increased at higher temperatures. Such primary
mullite as disclosed by SEM (Figure 5) is a nanometric mullite formed on a pure clay relict.
On the other hand, Figure 6 shows the physical process of engulfing and dissolving clay
relicts, presumably feldspar initiated liquid is first formed and then dissolves clay relicts
from which mullite crystals may eventually crystallize. Figure 7 shows bubble formation
caused by gas elimination after heating to temperatures higher than 1200°C.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 4.SEM micrograph showing a large quartz crystal in glassy matrix in a sample
etched with HF.

Figure 5.SEM micrograph showing detail of primary mullite forming out of kaolinite.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 6. SEM micrograph depicting submicronic clay relicts being engulfed and dissolved
into the glass.

Figure 7. SEM micrograph showing large bubbles due to gas elimination.

Finally, apparent porosity and linear shrinkage were plotted at temperatures up to 1300°C,
in Figure 8. both curves show the onset of densification at 1000°C and the appearance of
bloating at temperatures higher than 1250°C.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Figure 8. In situ densification correlated to decreasing porosity.

Figure 9 shows DTA (a) and thermodilatometry (b) data, by comparing both curves it can be
seen that after dehydroxylation, the slope of the shrinkage curve changes as it does after
mullitization and again after feldspar melting during the last sintering stage. This suggests a
dependence of the aforementioned physical chemical changes and the sintering process.
Figure 10 correlates the shrinkage behaviour and the measured apparent porosity of the
body. As might be expected at temperatures higher than 1100°C the higher rate of
decreasing porosity brings about the abrupt last stage of shrinkage of the body.

Figure 9. In situ firing shrinkage of triaxial bodyfrom thermodilatometry (b) and DTA (a).
Note shrinkage changes coincident with dehydroxilation and mullitization temperature.

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Characterization of Microstructure in Experimental Triaxial Ceramic Body

Conclusions
A microstructure-densification relationship was found. Changes in the rate of shrinkage
from dilatometric in situ measurements were sensitive to phase transitions as detected by
DTA. The overriding rate of shrinkage took place after most of the liquid phase was formed
during the last stage of sintering within the 1100- 1200°C temperature range. Heating
beyond 1200°C led to body bloating.

Acknowledgements
Authors acknowledge financial support of the “Coordination de la Investigación Cientifica de
la Universidad Michoacana de San Nicolás de Hidalgo”. Assistance of Dr. Satoshi Sugita
Seuyoshi is gratefully appreciated.

References
1. Y. Iqbal and W. E. Lee, “Fired Porcelain Microstructure Revisited”, J. Am. Ceram. Soc., 82 [12] (1999) 3584–3590.

2. Y. Iqbal and W. E. Lee, “Microstructural Evolution in Triaxial Porcelain”, J. Am. Ceram. Soc., 83 [12] (2000) 3121–3127.

3. A. Klein, “Constitution and Microstructure of Porcelain”, Natl. Bur. Stand, Tech. Pap., 3-38 (1916-1917).

4. W. D. Kingery, Introduction to Ceramics, Second Edition. John Wiley & Sons, New York. 1976 pp.448-514.

5. S. T. Lundin, “Electron Microscopy of Whiteware Bodies”, Trans. Int. Ceram. Congr., 4, 383-390 (1954).

6. K. H. Schuller, “Reactions Between Mullite and Glassy Phase in Porcelains”, Trans. Br. Ceram. Soc., 63 [2] (1964) 103-117.

Contact Details
Simón Y. Reyes López and Juan Serrato Rodríguez

Universidad Michoacana de San Nicolás de Hidalgo

Instituto de Investigaciones Metalúrgicas,
Santiago Tapia 403, Morelia, Mich.
México. C.P. 58000
E-mail: yobannyr@yahoo.com.mx
E-mail: jserrato@zeus.umich.mx

This paper was also published in “Advances in Technology of Materials and Materials Processing Journal, 9[2] (2007) 173-178”.

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