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Glass Ceramics
HARSHAVARDHANA.N
Roll.No: 10411413
List of Figures i
List of Tables ii
Nomenclatures iii
Chapter 1. Introduction 1
1.1 Definition 1
1.2 Glass-ceramics 1
1.3 Machinability of Glass Ceramics 3
1.4 Advantages Machinable Glass ceramics 3
1.5 Application of machinable glass ceramics 4
Chapter 3 Summary 21
References 23
List of Figures
i
List of Tables
ii
Nomenclatures
Si Silicon
K Potassium
B Boron
Mg Magnesium
iii
Composition, Microstructure, Properties of Machinable Glass
Ceramics
Chapter-1: Introduction
1.1. Definition:
Machinable glass-ceramics is a white, opaque polycrystalline materials formed by the
controlled crystallization of glass. These glass ceramics can be easily machined into desired
shape using standard metalworking tools. [1]
Glass Ceramics + Machinability = Machinable glass-ceramics
1.2. Glass-ceramics:
The glass-ceramics are the polycrystalline materials formed by controlled
crystallization of glass It exhibits both the properties glasses and ceramics. These glass-
ceramics are produced by controlled crystallization process which results in exhibiting both
amorphous and crystalline phases.[1]
The production of glass-ceramics involves two main steps. .In the first stage of heat
treatment process, the batch is melted at 1700oC which results in formation of transparent
glass. During second stage of heat treatment, the glass-ceramics is produced by heating the
glass to a temperature range of 530oC to 760oC for the considerable period of time of about 8
hrs, which results in nucleation of crystals and followed by heat treatment to a temperature
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range of 850oC to 1100oC for about 3 hrs, which results in the formation of randomly
oriented glass-crystals.. Thus by the end of this process, partly crystallized glass ceramics
structure is formed which has the application in many field. [1]
A wide variety of glass-ceramic which are widely used are as follows [4]
2
1.3. Machinability of Glass Ceramics:
Machinability is defined as the ability of the material to machine easily with the
acceptable level of surface finish and depth of cut. Machinability is difficult to predict as it
involves many variables such as microstructure of the materials, grain size, heat treatment,
chemical composition, fabrication method, hardness, yield strength, of the materials, tensile
strength of the materials etc. Further it dependents on the physical conditions such as
modulus of elasticity, thermal conductivity, thermal expansion, and work hardening. [5]
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It has a very high strength, rigidity and creep limit.
It is radiation-resistant and is therefore used in nuclear engineering.
Machinable glass ceramics has a property to join or sealed to itself or other
materials in a number of ways through metallizing, brazing, fritting or using
epoxy resin.
It is white and can be bright-polished. Thus it is used in medical and optical
devices. [4,6,7]
4
Chapter-2 - Literature Survey
5
Saraswati et al (1992) have worked on glassed ceramics with K20-MgO-AI2O3-
MgF2-SiO2 composition through the sol-gel. Thus the resultant powder produced after heat
treatment is hot pressed into workable discs. Thus the glass-ceramic was found to be
machinable with conventional tools. Its physical and mechanical property is compare with
commercial macor and it is tabulated. Further the microstructure study is also made to
analyze the flexure strength of the given machinable glass ceramics.[15]
James et al (1987) have worked on preparation of mica based glass ceramics by using
the composition range as(in mole%): Al2O3 -1.5 to 15%, CaO - 22 to 55%, P2O5 - 28 to 65%,
SiO2 is upto 15.0%, Other Oxides is upto 15%. Two stages were used to prepare the
machinable glass ceramics. The first stage results in formation of glass and second stage is by
nucleating at elevated temperature to form a crystalline phase. [10]
George et al (1974) have worked on glass article wherein the predominant crystal
phase is synthetic fluromica. The composition are K2O - MgO –Al2O3- B2O3 - SiO2 - F with
microstructure consisting of very large 2D crystal having high aspect ratio. This feature is
easily cleavable in brittle matrix impart excellent machinability fracture energy.[20]
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2.2. Composition of machinable glass-ceramics
The general composition of machinable glass-ceramics are shown below [9,10, 11]
Further the addition of compound such as Na2O, K2O, Li2O, MgO, BaO and ZnO
to a small amount (0 to 5%) in glass ceramics results in reduction of liquidus temperature and
further modifying the viscosity of the melt.[11]
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is heating the glass to a temperature range of 560 oC to 760oC for 8 hrs, which results in
nucleation of crystals and followed by heated to a temperature range of 850 oC to 1100 oC for
3 hrs, which results in formation of ceramics crystals. Thus results in formation of randomly
oriented tetra silicic-mica crystals.[10,13]
After completion of first stage of heat treatment process, Differential Thermal Analysis
(DTA) is carried on the base glass at sufficient temperature range of 40o-1100oC inorder to
predict the nucleating and crystallization temperature of the glass-ceramics.[8]
8
The above mentioned raw materials Melting of batch at the sintering
is mixed together in ball mill using temperature of 1500 oC for 30Minutes
acetone medium for 24 hrs. Thus followed by quenching in air results in
results in formation of batch. formation of Glass.
Fig 5: Schematic flow diagram of heat treatment process for machinable glass-
ceramic[4,10,13]
9
b) When the temperature increased further, results in the increase in microstructure of
spherical mica to 0.2µm. and thus the material becomes opaque. The Variation of the size of
mica with respect temperature is clearly shown in fig 2.5 [11]
10
Thus in case of machinable glass-ceramics of variable microstructures, it is found that the
machinability is inversely proportional to the mechanical strength. Very fine-grained crystal
will have high-strength which is relatively more difficult to machine, where as coarse-grained
crystal will have low-strength which is relatively more easy to machine. Thus by heat
treatment process, coarse grained mica is obtained which can be easily machined to obtain
the desired shape.[12]
Porosity 0%
11
2.4.2. Thermal Properties [9]:
93 x 10-7 / °C (@ 25 to 300°C)
114 x 10 -7 / °C (@25 to 600°C)
126 x 10 -7 / °C (@25 to 800°C)
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2.5. Microstructure Study of Machinable Glass Ceramics
By X-ray diffraction study, it is revealed that the phases in machinable glass ceramics are
fluorophlogopite (KMg3AlSi3O10F2), mullite (3Al2O3 .2SiO2), magnesium fluoride (MgF2)
and a significant amount of glass.[11]
Scanning Electron Microscope image (SEM) clearly shows the morphology of the crystal
phases comprises of fluorophlogopite laths (~1-50 µm), elongated mullite (1-3 µm) and
spheroidal magnesium fluoride (~1 µm in diameter). Further the Energy Dispersed X-Ray
(EDX) analysis clearly confirms the presence of the mullite and MgF2 and also reveals glass
is a homogeneous composition potassium aluminosilicate [11]
(a) (b)
(c)
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X-ray diffraction study on the machinable glass-ceramics clearly reveals the crystallization
sequence at the various temperatures range. Thus after 1 h at 650oC, results in the formation
of chondrodite which can be identified by measuring the peak intensity. Further at 750oC
after 1 h, result in formation of norbergite and at 850oC after 1 h result in formation
fluorophlogopite and after 4 h at 950oC, there is a formation of only fluorophlogopite and
mullite remain [11]
14
Figure 12. X-ray diffraction pattern of machinable glass-ceramics subjected to heat
treatment at 4 h at 950oC and the two-step heat treatment (700oC for 2 h and 950 oC for
4 h) [11]
Energy Dispersed X-ray analysis (EDX) revealed the glass matrix (light contrast)
consist of potassium magnesium aluminosilicate and phase separated regions rich in Mg and
F with no K. The major component of the glass would be B2O3 and further it has K2O, Al2O3
and SiO2 thus results in producing potassium magnesium (boro)aluminosilicate glass [11]
(a) (b)
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(c) (d)
Figure 13: Microstructure of machinable glass-ceramics showing phase separation (a)
by SEM (b) TEM; (c) Energy Dispersed X-ray analysis (EDX) shows light contrast
continuous Mg, Al, Si, K,O-containing glass; (d)Energy Dispersed X-ray analysis (EDX)
shows the darker isolated regions rich with Mg and F with no K [11]
At 650 oC after 1 hr of heating crystals size is found to be less than 1 µm which results
in domination of microstructure presumably chondrodite, which is indicated by XRD pattern.
Thus the SEM image shows that there is a clustering of crystals taken place and these clusters
will act as a initial point of formation of the fluorophlogopite crystals [11].
At 750oC after 1 hr of heating the crystals of chondrodite was observed along with
formation of fluorophlogopite with a fan-like morphology. The morphology is due to the
formation of small cuboidal/spheroidal crystals with fluorophlogopite laths formation in
outwards direction. EDX analyses on this crystals revealed that they have the same
proportion as that of fully developed fluorophlogopite laths.[11]
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Figure 15: Microstructure at 750oC after 1 hr of heating [11]
The Complete fluorophlogopite laths is formed by heating the sample to 950oC for the period
of 4 hrs. Thus temperature gets increased, results in increase in crystal growth.[11]
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2.6. Machinability of Machinable Glass Ceramics
Two important factor that affects the degree of interlocking are [12]
Aspect ratio (plate diameter to the thickness)
Volume percentage of mica crystal.
Thus if the glass ceramics which containing 1/3 rd volume of mica, thus results in formation
of machinable glass ceramics. Thus, by making the volume percentage of mica crystal as a
constant, the aspect ratio of the crystal directly affects the machinability. Thus, the aspect
Figure 18: Microstructure of machinable glass ceramics with high aspect ratio [12]
Thus, the average mica plate diameter and thickness can be measured from the scanning
electron microscope. For extremely fine-grained mica glass-ceramics (plate diameters less
than 4.5 µm), the mechanical strength increases with the decrease in mica-plate diameter.
Thus, the resistance to the dislocation increases with the reduction in thickness value. [12]
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Most machinable glass-ceramics have mica plate diameters in the order of 20 µm with some
varieties having mica crystals as large as 250 µm. Over this range in crystal size, the strength
is found to be inversely proportional to the flake diameter. The decrease in strength with
increase in size. Further the strength controlling flaws are also increased as the mica grain
size increases.[12]
Machinable glass ceramics can be machined to make precision components but its machining
characteristics are different to metals and plastics. Machinable glass ceramics consists of
interlocking plate-like mica crystals in a glassy matrix. These crystals acts as a barrier for
stopping microscopic fractures, thus machinability is reduced. During machining, the tool
pulverizes and tears the surface to produce a fine powder of crystals and glass. The crystals
are so small (i.e less than 20 µm) that, which results in a good surface finish. After
machining, the component is cleaned and ready for use with no further treatment.[9]
The various machining operation that can be preformed on machinable Glass Ceramics are as
follows [9]
a) Sawing
Machinable glass ceramic can be sawed using carbide grit blade with a 30
m/min band speed, or a diamond or silicon carbide cut-off wheel.
B) Turning
Machinable glass ceramic can be machined using carbide tipped tools with the
suggested turning speeds is around 600 rpm for the diameter 5mm to 10mm rod.
Value of Feed rates will be around 20-30 mm/minute with a depth of cut value is 2-
4mm for roughing and less than 1mm for finishing.
Side and back rake angle, end and side relief angles should be around 5°. The
recommended side cutting edge angle is 15°-45° and the nose radius should be larger
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than 0.8mm.Thread cutting can also be done at low spindle speeds with the depth of
cut value as 0.025-0.040mm per pass.
Figure 19 – Tool wear vs Time of machining for machinable glass ceramics for turning
operation [12]
c) Milling
Machinable glass ceramic can be milled using typical head speeds of 1000–
1500 rpm with a chip load of 0.05mm per tooth. Depths of cut must be kept minimum
for the milling condition.
d) Drilling
Machinable glass ceramic can be grind using diamond grinding wheels for
obtaining the best results although silicon carbide and alumina wheels can be used.
Water is used as coolant.
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Chapter 3 - Summary
The microstructure study is done at the various phases for determining the
structure of machinable glass ceramics at various conditions. By X-ray diffraction study, it is
revealed that the phases in machinable glass ceramics are fluorophlogopite
(KMg3AlSi3O10F2), mullite (3Al2O3 .2SiO2), magnesium fluoride (MgF2) and a significant
amount of glass. Energy Dispersed X-ray analysis (EDX) studies clearly reveals that the glass
matrix (light contrast) consist of potassium magnesium aluminosilicate and phase separated
regions rich in Mg and F with no K. The major component of the glass would be B2O3 and
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further it has K2O, Al2O3 and SiO2 thus results in producing potassium magnesium
(boro)aluminosilicate glass. As the temperature increases from 650 oC to 950 oC, there is a
change of phase from chondrodite to fluorophlogopite crystals. Thus at 650oC after 1 hr of
heating crystals size is found to be less than 1 µm which results in domination of
microstructure presumably chondrodite, which is indicated by XRD pattern. At 950 oC after 1
hr of heating crystals size is found that the size of the mica increases to 20 µm which results
in domination of microstructure presumably fluorophlogopite crystals which are coarse in
nature which results in machinability of glass ceramics.
22
References:
[1] Kirk-Othmer, “Encyclopedia of Chemical Technology”, John Wiley & Sons, Inc, p
626-643.
[2] www.EuropTec.com
[3] http://www.pgo-online.com/intl/katalog/macor_machinable_glass_ceramic.html
[4] http://en.wikipedia.org/wiki/Glass-ceramic
[5] http://en.wikipedia.org/wiki/Machinability.
[6] http://www.ceramic-substrates.co.uk/macor_ceramic.html
[7] http://www.plasticsintl.com/datasheets/MACOR.pdf
[8] Shibayan Roy (2004) ‘Microstructure evaluation of machinable mica based glass
ceramics for dental application’, International Symposium of Research Students on
Material Science and Engineering, December 20, 2004, Chennai, India
[9] http://www.technicalglass.co.uk/pdf/macor_machinable_ceramics.pdf
[10] James, Peter, Finlay, ’Glass-ceramics’, Patent No – W087/ 07256, December 3, 2004
[11] Sazmal E. Arshad, William E. Lee and Peter F. James (2002) ‘Crystallization and
microstructural evolution of commercial fluosilicate glass-ceramic’, July 16, 2001,
Glass Technol., 43C, 69-80
[12] Grossman, D.G. (1972) ‘Machinable glass-ceramics based on tetrasilicic mica’, J.Am.
Ceram. Soc., 55(9), 446-449.
[14] http://www.twi.co.uk/jsp/Secure.jsp.
[15] Saraswati, Sarala Raoot. (1972) ‘Machinable mica based glass-ceramics’, Journal of
materials science., 27(1992), 429-432.
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[16] Denry, Lejus, Thery, and Masse. (1999) ‘Preparation and characterization of a new
lithium-containing glass-ceramic’, Elsevier Science Ltd., Vol. 34 (1999), Nos. 10/11,
pp. 1615–1627.
[17] Balk, No, Chun (1995) ‘A comparative evaluation method of machinability for mica-
based glass-ceramics’, Journal of materials science, Vol. 30, pp. 1801–1806.
[19] Toshio hamasaki, Katsuya eguchi, Yoshinori koyanagi, Akira matsumoto (1988)
‘Preparation and Characterization of Machinable Mica Glass-Ceramics by the Sol-Gel
Process’, Journal of the American Ceramic Society, 8 MAR 2005 Vol. 71,Issue-12,pp.
1120–1124.
[20] George H. Beall(1974) ‘Glass-ceramics for medicine and technology - Chain silicate
glass-ceramics’, Journal of Non-Crystalline Solids, Vol. 129, pp. 163-173.
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