ADDITIONAL THERMAL EXPANSION OF GYPSUM-BONDED INVESTMENT BY RAPID HEATING Farzaneh Aghajani (DDS Tehran University, Iran) Thesis submitted in fulfilment of the requirements for the degree of Master of Science in Dentistry Dental Materials Science Discipline Faculty of Dentistry The University of Sydney Australia March 1998Declaration This is to certify that the work presented in this thesis was carried out by the candidate in the Discipline of Dental Materials Science, Faculty of Dentistry, the University of Sydney and has not been submitted in any other university or institute for any higher degree, Farzaneh Aghajani, March 1998.Acknowledgment I wish to express my sincerest gratitude to Dr T. Mori, former Head of Biomaterial Research Unit, the University of Sydney, for her guidance, supervision and assistance in preparation of this thesis. Lam deeply indebted to Dr T. Sumi, Acting Head of Biomaterial Research Unit, the University of Sydney, for his supervision, encouragement and help. Special thanks go to Mr Ken Tyler whose expertise was essential in making and developing many devices to support my study. Grateful acknowledgment is extended to Dr R. Earnshaw for permitting the use of apparatus for some of my experiments. I would like to thank all my friends in Biomaterial Research Unit; Dr Danny Low, Dr Suchit Poolthong, Dr Napa Suansuwan, Dr Hungki Lee, Dr Peter Chung, and Mr Bill Higgs. Their friendship and kindnesses made my study easier.Dedication To my husband, Hamid, whose love and support helped and encouraged me through this study itiTable of Contents Declaration Acknowledgment Dedication Table of Contents List of Figures List of Tables Chapter 1 Background 1.1 Introduction 1.2 Development of gypsum-bonded investment 1.3 Gypsum and its dehydration 1.4 Calcium sulfate hemihydrate 1.4.1 Dry calcination 1.4.2 Wet calcination 1.4.3 Differences between o,- and B-calcium sulfate hemihydrate 1.5 Anhydrous calcium sulfate 1.5.1 H0-CaSOx 1.5.2 H-CaSOx 1.5.3 I-CaSOy Chapter 2 Purpose and Scope Chapter 3 Materials and Methods 3.1 Materials 3.2 Experimental methods 12 12 4 16 19 19 21 23 26 28 28 283.2.1 Analysis of the composition of investment powders 3.2.2 Thermal expansion measurement of investments (TMA) 3.2.3 Thermal expansion measurement of investments (rapid heating) 3.2.4 Mass changes of investment after heating 3.2.4.1 Slow heating of dry specimens 3.2.4.2 Rapid heating of dry specimens 3.2.4.3 Rapid heating of wet specimens Chapter 4 Results 4.1 Analysis of the composition of investment powders 4.2 Thermal expansion of investments (TMA) 4.3 Thermal expansion of investments (rapid heating) 4.4 Mass changes of investment after heating Chapter 5 Discussion Chapter 6 Summary and Conclusion Bibliography Appendix 28 30 31 34 34 35 35 36 36 40 42 46 53 65 68 79List of Figures Fig. 1-1a: Schematic position of calcium atoms, sulfate groups and water molecules in gypsum Fig. 1-1b: Schematic position of calcium, sulfur, and oxygen atoms, in gypsum in relation with water molecules Fig. 1-2: Coordination of ions in gypsum Fig. 1-3: DTA-TG curve of gypsum between room temperature and 800°C Fig. 1-4: Representative DTA-TG curves of two types of calcium sulfate hemihydrate Fig. 3-1: DTA-TG apparatus Fig. 3-2: TMA apparatus Fig. 3-3: Small and large specimens prepared for TMA and rapid heating technique, respectively Fig. 3-4: Apparatus used in measurement of thermal expansion in the rapid heating schedule Fig. 4-1a: Representative DTA-TG curves of three rapid heating gypsum- bonded investments Fig. 4-1b: Representative DTA-TG curves of two conventional gypsum- bonded investments Fig. 4-2: Representative thermal expansion curves of five investments Fig.4-3a & b: Representative thermal expansion curves of three investments under rapid heating Fig. 4-4: Mass changes occurring in dry specimens heated slowly Fig. 4-5: Mass changes occurring in dry specimens heated in the rapid heating conditions Fig. 4-6: Mass changes occurring in wet specimens heated in rapid heating conditions 18 29 30 32 33 38 39 41 43 48 50 52List of Tables Table 1-1: Effect of unreacted hemihydrate on the dehydration values of cast gypsum to hemihydrate and to anhydrite Table 3-1: Gypsum-bonded investments used in this study Table 4-1: DTA-TG results of five brands of gypsum-bonded investment powder Table 4-2: Mean thermal expansion value of five gypsum-bonded investments Table 4-3a: Results of thermal expansion measurement in rapid heating technique with consideration of time Table 4-3b: Results of thermal expansion measurement in rapid heating technique with consideration of temperature Table 4-4: Mass changes of dry specimens after slow heating Table 4-5: Mass changes of dry specimens after rapid heating Table 4-6: Mass changes of wet specimens after rapid heating 1 28 37 40 44 45 47 49 51 viiChapter One Background 1.1 Introduction We, in dentistry, all acknowlage that gypsum (calcium sulfate dihydrate) is heated to produce either plaster or stone, The two forms of the dehydrated product are often called B- and o:-hemihydrate, respectively. This most familiar dental product is used to make dental casts and dies. It is also combined with refractory material to make gypsum-bonded casting investment. In both cases plaster or stone returns to gypsum as a result of mixing with water. The gypsum binder in the investment is again subjected to the dehydration process, although the dehydration this time proceeds to the formation of calcium sulfate anhydrite as a temperature of typically 700°C is involved. It is assumed that B-hemihydrate or plaster is formed during the heating of the mould because the heating conditions are similar to those employed in the manufacture of plaster, the dry calcination or open kettle method. However, there has been no investigation that examined the conditions prevailing in the first step of dehydration in the mould and its effect on the thermal expansion behaviour. It is intended to critically review the development of gypsum-bonded investment and dehydration processes of gypsum to hemihydrate and to anhydrite. 1.2 Development of gypsum-bonded investment It has generally been accepted in dental casting that contraction of liquid metal in the mould can be compensated by adding more liquid metal from the crucible until the solidification temperature is reached (Price, 1908, 1911; Coleman, 1928; Earnshaw, 1958; Greenar et al, 1972; Phillips, 1991), Therefore, compensation of the contraction of the solidified metal, as it cools from the solidus to room temperature,Chapter 1: Background is the basis of dental precision casting theory. Finger and Jorgensen (1980) measured the thermal expansion of twelve dental gold alloys by push-rod dilatometery. Each specimen was annealed and heated to a temperature which was approximately 50°C below its solidus temperature. The mean thermal expansion between room temperature and solidus temperature was in the range of 1.68% to 1.80%, Coleman (1926, 1928) measured the thermal expansion of gold and a gold alloy from 25°C to 1041°C and 860°C, respectively. These were the highest temperatures at which the samples remained rigid. He gave thermal expansion values of 1.76% for gold and 1.62% for the alloy. This was followed by the measurement of “casting shrinkage” where the gold alloy was cast into an investment of known dimensions in a steel flask. He found the shrinkage of the gold alloy rod to be 1.25%. Since this value differed from that he had obtained before (1.62%), two possible explanations were given (Coleman, 1926, 1928; Souder, 1927); either the shrinkage was being restricted by fictional interlocking between the casting and the walls of the mould, “stretching” the casting as it cooled, or molten metal entered after the peripheral areas as the casting solidified. Hollenback and Skinner’s study (1946) has also shown “casting shrinkage” of 1.50+0.01% for a 22 carat dark gold alloy, Earnshaw (1960) cast rods (6.35 cm x 0.32 cm @) in a room temperature mould and measured the shrinkage of gold to be 1.74+0.03%. There has been a general acceptance of Coleman’s figure, 1.25% as a fixed entity. It was used as the value to be compensated in making small dental castings (Souder, 1927, 1930). At that time no single investment was available to fully compensate for the contraction of gold alloys and various methods of partial compensations were introduced. Van Horn (1920), while having much to say about the method of compensation, accepted this contraction value without question. Two patents for dental casting investments registered in 1933 on behalf of major American dentalChapter 1: Background companies contain statements that the expansion of an investment should be around 1.25% to offset the shrinkage of (gold alloy) castings during cooling (Moore, 1933; Van Allen, 1933). No references were given to the shrinkage value. Taggart introduced the casting process as we know today in 1907 and he marketed an investment under his own name which was regarded as one of the best investments of the day. It was expanding 0.88% (Price, 1908; Shell, 1960) at 538°C and contained 37.5 % plaster, 57.5% silica and 5% graphite (Shell, 1960). In 1929, Weinstein patented the use of boric acid to increase the thermal expansion of ‘gypsum-bonded investment and to increase its high temperature strength. In a patent on the use of sodium, potassium and lithium chlorides to increase thermal expansion of gypsum-bonded investment, Moore found that sodium chloride is the most effective of the three and suggested a concentration of 0.8% in investment powder (Moore, 1993). In 1930, Taylor e¢ al measured physical properties of thirty commercially available investments, They consisted of plaster, silica (quartz) and additives such as boric acid and graphite and were divided into three groups based on plaster content. The investments containing more than 40% plaster expanded about 0.1-0.2% when heated to 100°C -300°C but underwent marked contraction after this, The second group containing about 30-40% plaster showed an expansion of 0.2-0.8% at 700°C. ‘The third group which had less than 30% plaster, “high silica investment”, expanded more or less continuously to casting temperature and gave an expansion value of 0.9%. This study also gave data about an “experimental investment”; its setting expansion was 0.34% and had thermal expansion of 1.27% at 700°C, which was much higher than those of thirty eight investments available at the time. This investment contained 75% cristobalite and 25% plaster and was developed at the American National Bureau of Standards, The thermal expansion curve of the experimental investment was relatively flat in the range of 538°C -871°C, the range of temperatures at which excellent castings could be made (Volland & Paffenbarger, 1932). The first commercial investment (Kerr Cristobalite investment) appeared in aChapter 1: Background paper by Van Horn (1934). The investment had a thermal expansion of 1.35% at 649°C and MOD castings made were 0.3% undersized. Development of a wet-calcined (autoclaved) calcium sulphate hemihydrate, Hydrocal, was reported by Randel and Daily (1933). ‘This resulted in significant strength increases of the cast gypsum specimens (Earnshaw & Combe, 1981), but little has been documented of the use of wet-calcined calcium sulfate hemihydrate in gypsum- bonded investment. While investment manufacturers set a goal to reach 1.25% thermal expansion, several investigators have tried to find a method or an investment to increase thermal expansion. Earnshaw (1961, 1975) studied the effect of additives on thermal expansion of gypsum-bonded investment and developed an investment containing 0.2% NaCl. The investment, mixed with 10% glycerol solution, exhibited up to 1.7% thermal expansion at 700°C. He also found that boric acid had a similar effect as glycerol. Finger and Jorgensen (1980) also developed an experimental investment. It contained a high amount of cristobalite (40%) and quartz (35%). With a combination of glycerol and boric acid, the thermal expansion was increased. These investigators shared a common desire to reduce the setting expansion and Finger and Jorgensen used sodium and potassium citrate for this purpose. The investment was strong and was for use without a steel casting ring but is not commercially available. The attempt to suppress the setting expansion relates to the study of “hygroscopic expansion”. Scheu (1932) discovered the phenomenon of enhanced setting expansion of gypsum-bonded investment in the presence of water and named it “hygroscopic expansion”. It has been generally accepted that the hygroscopic technique causes considerable distortion of invested wax patterns (J@rgensen, 1953; Suffert & Mahler, 1955; Mumford & Phillips, 1958a; Fusayama, 1959a, 1959b; Van Aken, 1961; Mahler & Ady, 1963). This effect can be seen with wet liners, although to a much lesser expansion than achieved by immersing investments in water (Fusayama ef al, 1957; Fusayama, 1959a; Van Aken, 1961; Shell, 1969). Therefore,Chapter 1: Background many investigators have recommended reducing the setting expansion of investment (Skinner, 1933; Fusayama et al, 1957; Mumford & Phillips, 1958a; Fusayama, 1959; Van Aken, 1966; Earnshaw, 1969a; Finger & Jorgensen, 1980; Finger, 1980) Recently a new method to reduce the time required for mould heating has been introduced and several commercial products are now available. In this method, 30 minutes after the start of mixing investment, the mould is placed in an oven preheated to 700°C. After maintaining this temperature for 30 minutes casting is made. The total required time is one hour (rapid heating technique). In the development of dental casting investment, the use of cristobalite instead of quartz was a major step to attain higher thermal expansion in gypsum-bonded investment in the 1930s (Taylor et al., 1930). While it has been reported that these new investments contain quartz (Takahashi ef al., 1993), the manufacturers claim that they provide sufficient thermal expansion to compensate shrinkage of gold alloys. 1.3 Gypsum and its dehydration In the CaSO.-H,O system, three types of compounds have generally been recognised; gypsum or CaSO,.2H0, calcium sulfate hemihydrate or CaSO,.'/H,O (plaster or stone), and calcium sulfate anhydrite or CaSO,, Gypsum (CaSO«.2H0) is the most abundant sulfate mineral (Deer et al.,1963; Lehmann & Holland, 1966). It is a naturally occurring mineral mined in many parts of the world and has been used for many centuries, in one form or another (Winterbottom, 1917; Kelly et al., 1941; Phillips, 1991). It is supposed that the alabaster used in the building of King Solomon’s temple of biblical fame was a form of gypsum (Haddon, 1944; Phillips, 1991) and gypsum’s value as a commercial commodity has been known from time of the Egyptians (Winterbottom, 1917). History of scientific study of gypsum goes back to 1765 when Lavoisier (Davis 1907) described gypsum as a “salt formed by the union of the acid of vitriol with the earth of lime, containing water of crystallisation which can be driven off by a gentle heat,Chapter 1: Background the product being so called Plaster of Paris”. The term Plaster of Paris was given to this product because it was obtained by burning the gypsum from deposits near Paris, France. Deposits of gypsum, however, are found in most countries (Phillips, 1991, Craig, 1996). In North America and in Europe the plaster industry is based on massive deposits that are geologically old, while in Australia the raw gypsum is of recent geological origin and is often a loose granular material formed during the seasonal drying-up of salt lakes and concentrated naturally in wind-blown dunes Ridge, 1960). Gypsum usually occurs in nature as a fine grain, compact mass of small crystals. Among the various forms in which gypsum occurs are selenite, alabaster and satin- spar (Winterbottom, 1917; Kelly et al., 1941; Deer et al., 1963; Dietrich, 1983; Deer et al,, 1993). Selenite is generally colourless and transparent or translucent and shows pronounced cleavage planes, while alabaster is white and opaque and satin- spar has a pearly sheen appearance (Winterbottom, 1917; Deer ef al., 1963; Deer et al., 1993). Alll these varieties have the same energy content and probably the same crystalline form (Kelly et al., 1941). Gypsum (CaSOs.2H,0) is usually used as a blanket term covering all types of calcium sulfate dihydrate (Holdridge & Walker, 1967). Gypsum can also be prepared by precipitation from solutions of calcium salts and sulfates at room temperature or by allowing plaster to set in water. Gypsum crystal has been described as monoclinic in form with 4 or 8 molecules in the unit cell (Wooster, 1936; Kelly et al., 1941; Deer ef al., 1992) and is made up of layers of calcium atoms and sulfate groups, separated by sheets of water molecules (Figs. 1-1a & 1-1b). ‘The water molecules occupy important positions in the lattice and would be virtually impossible to remove without destroying the lattice. Therefore, any lower hydrate should have a different structure from that of dihydrate and this can be detected by x-ray diffraction (Feitknech, 1931; Wooster, 1936; Kelly, et al., 1941). CaSOx is formed by ionic bonding while the water layer is formed by hydrogen bonding. This structure provides the explanation why crystals of seleniteChapter 1: Background can be split in layers, because the plane of cleavage parallels the planes containing the water molecules (Kelly et al., 1941; Deer ef al., 1963; Ridge & Bertka, 1969; Arai & Yasue, 1979). Figure 1-2 shows that each calcium ion is coordinated by four oxygen atoms of a sulfate group and by two of water molecules. A three dimensional x-ray structural analysis conducted by Cole and Lancucki (1972a, 1972b, 1974) has revealed significant departure of the SO, ion from tetrahedral symmetry. This is because O; or y forms the bond with two water molecules, while there is no hydrogen bonding in On or On’ (Fig, 1-2) (Cole & Lancucki 1972a, 1974; Arai & Yasue, 1979). The tetrahedral symmetry increases after removal of the water molecules. The S-O distance becomes uniform in natural anhydrous calcium sulfate (Cheng & Zussman, 1963; Arai & Yasue, 1979). Fig.1-la: Schematic position of calcium atoms, sulfate groups and water molecules in gypsum (After Ridge & Bretka, 1969).Chapter 1: Background Sw Fig. 1-Ib: Schematic position of calcium, sulfur, and oxygen atoms,and water molecules in gypsum (after Arai & Yasue, 1979). Ca *S Fig. 1-2: Coordination of ions in gypsum showing O, , OY, Og and Oy’ bonding position (after AraiChapter 1: Background & Yasue, 1979) Gypsum, when exposed to air at ordinary temperature, is usually stable because the partial water vapour pressure of the atmosphere is greater than the dissociation pressure of gypsum. If gypsum is heated to a temperature at which its dissociation pressure becomes greater than the ambient water vapour pressure, it begins to dehydrate (Davis, 1907; Posnjak, 1938; Kelly ef al., 1941). This process is called calcination. The transition temperature (dehydration temperature) of gypsum to hemihydrate and water is between 70°C- 100°C (Randel & Daily, 1933; Holdridge & Walker, 1967; Boshouev et al,, 1983; Deer ef al., 1992). However, the speed of reaction at this low ‘temperature is so slow that calcination performed at this temperature is impractical. The rate at which gypsum loses water increases with an increase in heating temperature, but the temperature at which the reaction starts depends on the surrounding or partial water vapour pressure as well (Holdridge & Walker, 1967; Khalil ef al., 1971; Matsuya ef al., 1979). In the temperature range 20°C to 700°C, which is of importance in the dental uses of gypsum products, three phase transformations occur in the CaSOs.2H,0 system. The first two represent the two stages in the dehydration of gypsum, and the third transformation to anhydrous calcium sulfate (West & Sutton, 1954; Holdridge & Walker, 1967; Khalil & Gad, 1972; Matsuya et al., 1979; O’Brien 1997). These changes can be detected by differential thermal analysis. A pioneer investigation in differential thermal analysis was made by Le Chatelier who used a single thermocouple immersed in the sample (Pope & Judd, 1977; Wendlant, 1986). Le Chatelier heated powdered gypsum at a steady rate and noted two distinct breaks at about 128°C and 163°C on the time-temperature curve (Davis, 1907; Posnjak, 1938). A two thermocouple system is the basic feature of all modem differential thermal analysis methods (Pope & Judd, 1977). With a modern differential thermal analysis these breaks are shown as distinctive endothermic peaks occurring in the range 120°C-220°C, although the peaks temperature depends onChapter 1: Background conditions such as heating rate and atmosphere (Fig. 1-3). In fact two endothermic and one exothermic peaks are generally detected for the heating range of 20°C - 700°C (Grim & Rowland, 1944; West & Sutton, 1954; Fleck etal., 1960; Kuntz, 1962a; 1965; Holdridge, 1965; Lehmann & Holland, 1966; Holdridge & Walker, 1967; Clifton, 1971; Khalil & Gad, 1972; Matsuya ef al., 1978; Tasaki, 1979a; Mori, 1982, 1986). The first endothermic peak generally occurring between 120°C and 180°C, is associated with loss of 1'/, moles of water of crystallisation from dihydrate to hemihydrate. The second endothermic peak, occurring between 180°C and 220°C, is accompanied by loss of '/: mole water of hydration from hemihydrate to anhydrite (West & Sutton, 1954; Kuntze, 1965; Holdridge & Walker, 1967; Clifton, 1971; Khalil & Gad, 1972; Mori, 1986). The changes in mass are simultaneously recorded with modem thermograms (Fig. 1-3). % MASS DECREASE 2 i i 5 TEMPERATURE x 100°C Fig. 1-3: DTA-TG curve of gypsum between room temperature and 800°C (after Hasratiningsih, 1987)Chapter 1: Background The third peak indicates that the reaction is exothermic and generally occurs at 300°C- 360°C. No weight change takes place during this reaction which indicates anhydrite inversion (West & Sutton, 1954; Kuntze, 1965; Holdridge & Walker, 1967; Clifton, 1971; Khalil & Gad, 1972; Mori, 1986). The dehydration of gypsum to calcium sulfate hemihydrate leads to a mass decrease of 15.7% and further heating to anhydrite a total loss of all of its combined water of crystallisation of 20.9% (Khalil & Gad, 1972; Mori, 1986). These values are changed when cast gypsum specimens contain impurities or unreacted hemihydrate. Table 1-1 shows the effect of unreacted hemihydrate on the dehydration values of gypsum to hemihydrate and anhydrite Table 1-1: Effect of unreacted hemihydrate on the dehydration values of gypsum to hemihydrate and anhydrite (after Mori, 1986) Mass decreases due to Mass decreases due to Composition of cast dehydration to dehydration to anhydrite sum hemihydrate (%) (%e) 100% dihydrate 15.7 20.9 99% dihydrate 1% hemihydrate 15.5, 20.8 98% dihydrate 2% hemihydrate 15.4 20.6 97% dihydrate 3% hemihydrate 15.2 20.5 96% dihydrate 4% hemihydrate 15.1 20.3 95% dihydrate 5% hemihydrate 149 20.2 91% dihydrate 9% hemihydrate 143 19.6 84% dihydrate 16% hemihydrate 13.2 18.6 uChapter 1: Background 1.4 Calcium sulfate hemihydrate One of the important commercial uses of mineral gypsum is for manufacturing calcium sulfate hemihydrate (CaSO;.'/2H,0). Doubts were expressed as to whether calcium sulfate hemihydrate was a definite chemical species (Sodeau & Gibson, 1927; Ramsdell & Patridge, 1929), and many felt it would be better to regard it as hydrous calcium sulfate anhydrite (Holdridge, 1965). However, most of the evidence to date favours treating the hemihydrate as an individual species and it has been proven that calcium sulfate hemihydrate is a true hemihydrate not a zeolite’ (Weiser & Milligan, 1937; Weiser et al., 1936; Ridge, 1972 Matsuya ef al., 1979). The natural form of calcium sulfate hemihydrate is not readily available; while some support the existence of this form as the mineral bassanite (Deer ef al., 1963; Ridge & Beretka, 1969; Lager et al., 1984), the most commonly reported form is almost anhydrous (Dana, 1966; Arai & Yasue, 1979). The processes by which calcium sulfate hemihydrates are prepared are essentially dissociation reactions. In ordinary manufacturing operations, the dissociation takes place with the liberation of gaseous water. This process is called dry calcination and plaster is a well-known product. A number of processes involving dissociation with the formation of liquid water have been known as wet calcination. The result of this type of calcination is dental stone. 1.4.1 Dry calcination The most extensively used calcination method of this type is the kettle process, in which ground gypsum rocks are fed into large, flat vessels called kettles (Winterbottom, 1917; Worner,1942a). The kettles are fitted with stirring devices and means for the rapid discharge of the calcined products (Winterbottom, 1917; Worner,1942a). * Any of a large group of hydrous crystals characterised by a ready loss or gain of water of hydration without changing their crystals lattice.Chapter 1: Background In the traditional open kettle method, crushed gypsum rock is gradually heated to 110°C -120°C, at which temperature it takes on the appearance of an opaque white liquid in active ebullition. The powdered gypsum is agitated while being heated and the heating causes steam to be produced as a result of partial dehydration of gypsum. The steam evolved from the heating of the powder passes up through the mass of powders causing them to have the appearance of boiling (Winterbottom, 1917; Haddon, 1924; Randel & Dailey, 1933; Wormer, 1942a). This is called the “boil”. The “boiling” continues until the temperature reaches 130°C -135°C and the mass “settles down” (Winterbottom, 1917; Worner, 1942a). As more heat is supplied, the mass again commences to boil, and when the temperature reaches about 143°C, steam may again be seen rising freely from the kettle (Winterbottom, 1917; Worner,1942a). This is known as “second boil” in distinction to the first boil at about 110°C -120°C (Blair, 1966). In most plants the temperature is allowed to increase to 150°C -190°C (Worner, 1942a; Andrews, 1951). The product is actually anhydrous calcium sulfate (Haddon, 1924; Worner, 1942a; Holdridge, 1965; Blair, 1966) and is known as “second settle” plaster (Wiss ef al., 1930). It is practically impossible to produce pure hemihydrate by the kettle process of calcination (Randle & Daily, 1933). It requires a further important treatment known as “aging”; the product is matured by exposure to ambient air, during which time the anhydrous form is converted to hemihydrate by absorbing moisture from atmosphere (Winterbottom, 1917; Sekiya, 1957; Holdridge, 1965). Thermal effects of the first and second boils relate to the two endothermic peaks appearing below 200°C in the differential thermal analysis of gypsum (Section 1.3). By far the largest proportion of dry calcined plaster produced today is made in kettle type reactors (Ando, 1986; Karashina & Terada, 1986). In the traditional method, which is a batch process, both fuel and time are wasted; the kettles are successively charged with raw gypsum, heating each charge until the mass is completely calcined, then discharged and operation is repeated. Continues calcination using rotary calciners or kilns has been known for a long time (Winterbottom, 1917). In order to improve the efficiency of the batch process, attempts have been made to calcine rawChapter 1: Background gypsum not by the kettle method but by a continuous process (Blair, 1966; Conroy & Jorgenson, 1967; Conroy, 1967; Ando, 1986; Karashina & Terada, 1986). 1.4.2 Wet calcination The autoclaving process which was patented by Randle and Daily (1933) is a well known wet calcination method. Before this, however, there were other wet calcination methods by which some investigators prepared hemihydrate for their laboratory experiments. According to Winterbottom (1917), Armstrong in 1899 prepared the pure hemihydrate, CaSO. '/3H,0, by leaving powdered gypsum in contact with nitric acid for 18 hours at 40-50°C and obtained hemihydrate crystals in the form of fine needles. Davis (1907) also described the use of sodium chloride and magnesium chloride solutions. The transition of gypsum to hemihydrate in water should occur at a point where the vapour pressure of the water of crystallisation of gypsum becomes greater than the equilibrium vapour pressure of water. The temperature value, 97°C -98°C, has been reported by many investigators for this transition point (Ramsdel & Partridge, 1929; Toriumi & Hara, 1934; Posnjak,1938; Kelly ef al., 1941; Ridge & Beretka, 1969). If the vapour pressure of water surrounding gypsum becomes lower for some reason, analogous to dehydration in a vacuum, the transition point of gypsum is lowered. This can be done by placing gypsum in aqueous solutions having a lower vapour pressure than that of water. Ifa nonvolatile solute is added to a solvent, the vapour pressure of the solvent is decreased. At a given temperature, the average kinetic energy of all particles in the solution is the same. Essentially the same number of particles are at the surface in both the solution and pure solvent, However, in the case of a nonvolatile solute, only a fraction of these particles are volatile and have sufficient kinetic energy to escape from the solution. For example, the vapour pressure of water having a 20 % moleChapter 1: Background fraction of glucose becomes 14 mmHg, instead of 17.5 mmHg, at 20°C (Hunter e al, 1983; Brown & LeMay, 1985). Effective solutes such as CaCk, NaNOs and KI were described as “vapour pressure depressant” in Hoggat's patent (1952) which employed this principle for manufacturing hemihydrate. A saturated solution of sodium chloride converts gypsum into hemihydrate above TPC (Davis, 1907; Hoggat, 1952). Sekiya (1957) showed that the equilibrium temperatures for the dihydrate-hemihydrate transition were 92°C, 80°C and 60°C for CaCl, concentrations of 10%, 30% and 50%, respectively. Setoyama ef al. (1971), in their study on the phase equilibrium of calcium sulphate in nitric acid solutions, found that the equilibrium temperature for the dihydrate-hemihydrate transition was greatly affected by the concentration of the solution; the transition temperatures were 75°C, 59°C and 42°C for concentrations of 30%, 40% and 50%, respectively. Tt is clear from the above that these solution methods are a convenient way of obtaining hemihydrate crystals of the wet-calcined type in the laboratory. These solution methods were used by the investigators who studied the crystal structure of hemihydrate Florke, 1952a; Gay, 1965b, Lager ef al., 1984) Randel and Dailey (1933) in their patent for the autoclaving method state that “if the water of crystallisation is separated as a liquid from the gypsum molecule without explosively converting the water into steam, the gypsum crystals are not shattered into minute crystals of hemihydrate but the resulting product is in the form of rather large, definite, well-formed crystals and these crystals are probably recrystallised in the liquid water”. They found that the calcination could be completed within 5 to 7 hours under a pressure of about 1600 mmHg. The normal boiling point of a liquid is the temperature at which its equilibrium vapour pressure is that of the atmosphere, 760 mmHg. Therefore, the boiling point of a liquid depends on the surrounding air pressure. Increased pressure is often used in industry because most chemical reactions go faster as the temperature is increasedChapter 1: Background and pressure may be applied to prevent a liquid boiling away at a high temperature. The conditions given by Randel and Dailey (1933) in their patent for autoclaving of gypsum appear to be an application of this principle, since they gave a specific temperature of 123°C for a pressure of about 1600 mmHg. As they described, there is a strong chance for the hemihydrate to be recrystallised at this saturated vapour pressure where liquid water and water vapour coexist. Randel & Dailey (1933) also found that the autoclaved plaster required much less water to yield a workable viscosity than in the case of traditional dry-calcined plasters, and gave it the name “alpha-gypsum” to differentiate it from the traditional dry-calcined plasters. The name “alpha-gypsum” appears to be widely used in the USA to describe this high strength plaster (Sekiya, 1957). The product is marketed under the trade name "Hydrocal" (Eber! & Ingrain, 1949). Nagai and Sekiya (1948) also obtained an autoclaved hemihydrate under calcination conditions of 123°C and 2 atm (1520 mmHg). Another type of wet calcination, in which autoclaving and a solution method are combined, has also been reported (Haddon & Cafferata, 1944; Eber! & Ingrain, 1949; Combe & Smith, 1968). 1.4.3 Differences between dry- and wet-calcined calcium sulfate hemihydrate and their coexistence Calcium sulfate hemihydrate prepared by wet and dry calcination methods are often distinguished by the designations “* and “B". When Kelley et al, (1941) first established these prefixes, they used “ot for a hemihydrate made by autoclaving and “B* for a hemihydrate prepared by heating gypsum at 100°C in a vacuum (mmHg). Although these prefixes are normally used to indicate crystallographic differences, it is generally agreed that in this case no differences are found in their x-ray diffraction patterns (Weiser & Milligan, 1937; Mc Adie, 1964; Goto ef al., 1966; Bensted & Varma, 1972; Bushuev et al 1983). That is, the differences in the structures of o-Chapter 1: Background and - forms of hemihydrate are extremely slight, and there are no published sets of interplaner spacings for a and B-hemihydrate which might illustrate these differences and which could be used as reference material (Bushuev ef al., 1983). Based on heat of solution data, Kelley et al. (1941) introduced a theory that o:- hemihydrate is not only produced by solution processes or autoclaving but also at atmospheric pressure, if the atmosphere is saturated with water vapour. In the absence of water vapour the resulting hemihydrate is of the B-form and at intermediate water vapour pressures the heat of solution indicates a mixture of the ‘two modifications. The percentage of each modification depends on the degree of water vapour in the atmosphere. This theory raised a number of objections (Kuntz, 1962a, 1965) but Sukimoto and Mukaiyama (1984) found that the o-hemihydrate can be formed isothermally without autoclaving when gypsum is heated at 110°C -140°C under atmospheric pressure of water vapour. As Kelley et al. (1941) properly described, the a- and B-hemihydrate modifications are different in thermodynamic properties such as specific heat and heats of hydration, The difference initially noted by Powell (1958) in his differential thermal analysis demonstrates this unique thermodynamic property and the analysis has been generally accepted as a method of identifying c- and B-calcium sulfate hemihydrate (Powell, 1958; Fleck ef al., 1960; Kuntz, 1965; Holdridge, 1965; Miyazaki, 1966a, 1966b; Bell & Urie, 1970; Clifton, 1972; Bushuev & Borisov, 1982; Mori 1993). A simultaneous differential thermal analysis-thermogravimetry (DTA-TG) of calcium sulfate hemihydrate clearly demonstrates the difference by the position of the exothermic peak accompanying anhydrous inversion. Upon completion of the dehydration of hemihydrate to anhydrite which is accompanied by 6.2% weight loss (Clifton, 1971; Mori,1986, 1993), a rapid phase change in anhydrite showing a sharp exothermic peak between 200°C- 220°C, occurs with hemihydrates prepared by several wet calcination methods (autoclaving and dehydration in solutions) while the curve for a dry calcined hemihydrate (prepared in an air oven) indicates a gradual phase transition in temperatures between 300°C- 400°C (Powell, 1958; Fleck ef al.,Chapter 1: Background 1960; Kuntz, 1965; Holdridge, 1965; Miyazaki, 1966a, 1966b; Bell & Urie, 1970; Clifton, 1972; Bushuev & Borisov, 1982; Mori 1993). Therefore, identification by this method is possible only after the hemihydrate is heated at least to temperature up to 400°C. % MASS DECREASE ENDOTHERMIC ST EXOTHERMIC TEMPERATURE x 100°C Fig. 1-4: Representative DTA-TG curves of two types of calcium sulfate hemihydrate (after Mori, 1993). The exothermic peak in DTA curves of gypsum specimens generally appears in the same temperature range as that of B-hemihydrate, indicating that the heating conditions are similar to those prevailing in dry calcination and B-calcium sulfate hemihydrate is formed under common laboratory examinations. There are other differences between o.- and f-hemihydrate such as density and gauging water requirement which reflect the degree of crystal lattice perfection and surface characteristics. Wet calcined hemihydrates have lower bulk volumes and are dense regular particles, while dry calcined hemihydrates have high bulk volumes and are rough porous particles. The amount of water needed for a workable mix is lower in c-hemihydrate, and resulting cast gypsum specimens are stronger than thoseChapter 1: Background prepared from B-hemihydrate (Randel & Dailey, 1933; Kuntz, 1965; Enayetallah et, al., 1977; Bamshaw, 1986; Phillips,1991; Craig, 1996; O’Brien, 1997). 1.5 Anhydrous calcium sulfate Calcium sulphate anhydrite (CaSO,) is so named because in contrast to gypsum it is a sulfate of calcium which contains no water. Anhydrite exists in three forms. One form is hygroscopic, metastable or unstable anhydrite which is the main constituent of freshly prepared “second-settle” plaster (Section 1.4.1). A second form, which occurs in nature is known as natural or mineral anhydrite. Grahmann (1913, 1920) reported the existence of a third modification of anhydrite which was formed from natural anhydrite at about 1200°C. In 1938, Posnjak suggested the use of Greek prefixes, «CaSO, B-CaSO, and y-CaSO,, in the order of phases existing from highest to lowest temperature. This order is contrary to general mineralogical usage (Deer et al., 1963; Gay, 1965b). For example, these prefixes are used in the reverse order in the case of the high and low-temperature forms of the polymorphs of silica, and in the allotropic forms of metals such as iron and cobalt. It has been proposed, therefore, that the terms I-CaSOx, II-CaSOy, and II-CaSO, be used instead for the three polymorphic forms of calcium sulphate anhydrite, in descending order of temperature (Spath, 1951; Arai and Yasue, 1974; Mori, 1986). This terminology is used in the present study. 1.5.1 TI-CaS0, At about the beginning of this century, the name “soluble anhydrite” was given to this phase by van't Hoff and his associates to distinguish it from natural anhydrite; the substance they obtained had a greater solubility than natural anhydrite (Davis, 1907; Ramsédell & Partridge, 1929; Hammond & Withrow, 1933; Weiser et al., 1936; Posnjak, 1938; Newman & Wells, 1938). This name is, however, a misnomer as no data regarding its solubility exist. This is because the III-CaSOx phase is hygroscopic, and the measurement of its solubility is not practically possible (Davis,Chapter 1: Background 1907; Winterbottom, 1917; Posnjak, 1938; Kelley ef al, 1941). The formation of hemihydrate, when ITl-CaSO, makes contact with water vapour, invalidates van't Hoff and his associates, measurements of the vapour pressure of gypsum in equilibrium with “soluble anhydrite” (Davis, 1907; Ramsdell & Partridge, 1929; Posnjak, 1938). In water, rehydration of II-CaSO, proceeds to dihydrate through hemihydrate (Flérke, 1952a). According to Davis (1907), Cloze was the first to recognise the hygroscopic behaviour of III-CaSO,, although Davis himself reported this behaviour in detail. Davis found that anhydrite samples prepared in the laboratory gained weight under ambient conditions and reached constant value in about 12 hours. The resulting mass increases were from 7 to 7.5%, instead of 6.6% which is the theoretical value for the formation of hemihydrate (145.154 g/mole) from anhydrite (136.146 g/mole). Davis explained that the excess amount of weight gain was due to moisture mechanically retained by the newly-formed hemihydrate. Hammoad and Caferata (1933) showed that 10 gram samples of III-CaSO, reached constant weights in 1 to 2 days under ambient conditions (25°C, 50-65 % relative humidity). In a differential thermal analysis experiment of gypsum, Posnjak (1938) cooled the specimens just after the second endothermic peak and left them under ambient conditions over night. By heating those specimens again, he observed an endothermic peak at the same temperature range of the second endothermic peak of gypsum. He suggestéd that this is the proof of rehydration of “soluble anhydrite” to hemihydrate. It has been accepted that freshly prepared III-CaSO4 can be used as an effective desiccant (Winterbottom, 1917; Hammond & Caferata, 1933; Bower, 1934). It would be technically possible, in the dry calcination of gypsum, to find a temperature where the product is mostly hemihydrate. However the water requirement of such products is high and this can be reduced by dehydrating gypsum to III-CaSO, and aging it to hemihydrate (Sekiya, 1957). This is probably one of the reasons why the aging has been an essential process in the dry calcination of gypsum over many years (Wiss ef al., 1930; Gibson, 1932; Worner, 1942a; Holdridge, 1965). Some early investigators recognised that I-CaSO, was hygroscopic (Davis, 1907; 20Chapter 1: Background Haddon, 1924; Johnson, 1931; Gibson, 1932; Hammond and Withrow, 1933; Bower, 1934) and although hemihydrate and II-CaSO, resemble each other closely, significant structural differences between them were noted (Weiser ef al., 1936; Posnjak, 1938; Flérke, 1952a). Other workers, who were not aware of the hygroscopic behaviour of III-CaSO,, allowed samples of this phase, after preparation by calcination, to rehydrate to form hemihydrate (Linck & Jung, 1924; Caspari, 1936; Gregg & Willing, 1951). Because of this, they considered that III-CaSO, was structurally identical with hemihydrate, and they classed them both as zeolitic substances which lose and gain water without change in crystal structure. Even some investigators (Ramsdell & Partridge, 1929; Gardet et al., 1976) who were aware of ‘the hygroscopic nature of IIl-CaSO,, found no structural differences between it and hemihydrate in their X-ray diffraction studies, Today, however, it is generally accepted that III-CaSO, has a hexagonal crystal structure (Florke, 1952a; Arai & Yasue, 1979; Deer ef al., 1993). The precise temperature at which II]-CaSO, transforms to II-CaSO, depends on the calcination conditions. In a.-calcium sulfate hemihydrate it is much lower (200°C- 240°C) than B-calcium sulfate hemihydrate (320°C -370°C) and it can be detected by observing the exothermic peak in differential thermal analysis (Sections 1.3 and 1.4.3). When IlI-CaSO« is formed by dehydration of c.-calcium sulfate hemihydrate, it has a very ephemeral existence (Holdridge & Walker, 1967) and changes almost instantly to Il-CaSO,. 1.5.2 -CaSO, ‘When the calcination temperature of gypsum is high enough, the product is no longer hygroscopic. It is a stable form of calcium sulphate anhydrite and basically the same as natural anhydrite or I-CaSOy. There has been, however, abundant proof that the transition of III-CaSO, to II-CaSO, (hereafter, III-II transition) is sluggish. For example, Posnjak (1938) found that a gypsum sample was almost entirely I-CaSO4 only after heating at about 300°C for 20 hours. According to Kelley ef al, (1941), anChapter 1: Background the transition is easily noticeable at lower temperatures but the rate decreases to an inconveniently low level; therefore II-CaSO, is normally prepared by heating II- CaSO, or hydrous calcium sulphate for an hour at about 900°C. Ridge et al. (1964) reported that for the content of III-CaSO, to be reduced to less than 2 per cent in 4 hours, a temperature of about 400°C was required. It is not possible to produce perfectly ordered Il-CaSO, crystallites in reasonable laboratory times; the relatively sluggish nature of the III-II transition necessitates the supply of appreciable thermal energy to allow the reconstruction of the embryonic nuclei into reasonably ordered domains of a recognisable II-CaSO, structure (Gay, 1965a). Calcined gypsum can retain the hygroscopic nature of III-CaSO, to high temperatures, although it may not be an effective desiccant any more (Hammond & Caferata, 1933). These products, however, set when they contact with water (Haddon, 1924; Ramsdell & Partridge, 1929; Johnson, 1931; Gibson, 1932; FlOrke, 1952a: Arai ef al,, 1973). This property is utilised as “flooring plaster”, which is largely used in Germany under the name of Estrichgyps (Winterbottom, 1917; Andrews, 1951; Flérke, 1952a). Mineral anhydrite is used in the manufacture of ammonia and ammonium sulfate for sulfuric acid production (Deer ef al. 1963, 1993). The product which is practically inert in water is called “dead-burnt” plaster (Winterbottom, 1917 ; Gibson, 1932; Florke, 1952a). The II-II transition is observed as a small and gradual exotherm at temperatures between 300 and 500°C, when DTA is made on gypsum (West & Sutton, 1954; Fleck et al., 1960; Kuntze, 1962b; Khalil; 1972 Mori, 1985). The cause of this exothermic reaction was not known among early investigators (Grim & Rowland, 1944; Gruver, 1951), and West and Sutton (1954) appear to be the first to identify ‘the II-II transition with this exothermic effect. However, in wet-calcined hemihydrates this reaction is rapid and so a sharp, well-defined exothermic peak is obtained. The peak temperature in this case is much lower, 180°C -260°C (Powell, 1958; Fleck et al., 1960; Holdridge, 1965; Mori, 1986). This difference can be used to identify dry- and wet-calcined hemihydrate (Section 1.4.3). 2Chapter 1: Background Amounts of the II-CaSO, phase formed during calcination at high temperatures can be estimated by leaving the calcined sample under ambient conditions; III-CaSO, contained in the sample rehydrates to form hemihydrate since it is hygroscopic (Section 1.5.1). This results in a mass increase. Conversely, there is no mass change if the sample consists of stable II-CaSO, only. This method has been used to study the low and high temperature transformation of wet- and dry- calcined hemihydrates into I-CaSO, (Mitsuki & Kita, 1959; Powell, 1960; Powell & Way, 1962; Ridge et al,, 1964; Mori, 1986). Ridge et al. (1964) reported that estimates given by this method for the formation of II-CaSO4 were not very different from the values obtained by X-ray diffractometry. Details of the crystal structure of II-CaSOx were first investigated by Wasastjerna in 1925 and by Dickson and Binks in 1926 (Deer et al., 1963; Cheng & Zussman, 1963; Arai & Yasue, 1979). Although they found that natural anhydrite had an orthorhombic structure, the details reported were different. Cheng and Zussman (1963) redetermined the structure using Fourier and least-square refinements and supported the structure proposed by Wasastjerna. The tetrahedral symmetry of the SO, ion here is much higher than in gypsum (Deer et al., 1963, 1993; Cheng & Zussman, 1963; Arai & Yasue, 1979) 1.5.3 I-CaSO, Grahmann (1913, 1920) first reported the existence of this true form of calcium sulphate anhydrite. He studied natural anhydrite under a petrographic microscope equipped with a hot stage. Abrupt changes in interference colours and the appearance of the crystals served to identify the transition, which was at 196°C. He considered that the high-temperature modification had a monoclinic structure Masuda (1932) observed an endothermic and an exothermic reaction when II-CaSO, ‘was heated and then cooled at a rate of 5°C/min. The peak temperatures for the reactions were 1232°C and 1229°C, respectively. Newman (1941) obtained an intermediate temperature of about 1214°C in a heating experiment similar to that ofChapter 1: Background Masuda. Despite these early reports, the phase I-CaSO, has long been neglected. For example, Kelley ef al. (1941) described that virtually no data were extant on the physio-chemical properties of high-temperature CaSO,, if such a form existed; they considered that calcium sulphate itself would begin to dissociate at temperatures very much above 900°C. Deer et al, (1963) expressed their view that detailed evidence for this phase was lacking. Gay (1965a) concluded that I-CaSO, did not exist. Ridge (1960, 1969) first supported the existence of the three anhydrite phases but later referred to the two forms only, hexagonal and orthorhombic. Obviously, technical difficulties exist in the study of I-CaSO,. The Laue camera Florke (1952a) used was not suitable for investigating the structural changes occurring at temperatures near 1300°C. His specimens, either heated at 1450°C and then quenched or heated at 1100°C (1 hour) and then cooled slowly, were all II-CaSO, at room temperature. He made a farther high-temperature X-ray analysis and found that I-CaSO, had a cubic structure (Flérke, 1952b). DTA studies have been consistent in that the transition of II-CaSO, to I-CaSO4 ‘occurs at temperatures close to 1200°C (Gruver, 1951; West & Sutton, 1954; Gutt & Smith, 1967; Khalil & Gad, 1972; Mori, 1985). I-CaSO, melts at a temperature between 1450°C and 1500°C (Grahmann, 1913; Newman, 1941; Florke, 1952b; Gutt & Smith, 1967). Before this occurs, however, I-CaSO, can dissociate to form CaO and SO; gas at a temperature just after it has transformed from II-CaSO4 (Newman, 1941; Flérke, 1952b; West & Sutton, 1954; Khalil & Gad, 1972). The dissociation product CaO forms a eutectic mixture with the remaining CaSO,. This mixture melts at about 1350°C -1400°C and this is seen as an endothermic reaction (Newman, 1941; West & Sutton, 1954). Arai and Yasue (1974) supported the cubic structure determined for the I-CaSOx phase by Florke (1952b). However, they also stated that some of the X-ray 24Chapter 1: Background diffraction peaks reported by Flérke were not from I-CaSO4 but from CaO; the decomposition to CaO and SOs began before the transition of H-CaSO, to I-CaSOx occurred. They consider that I-CaSO, exists as a metastable phase before calcium sulphate decomposes. 25Chapter Two Purpose and Scope For many years gypsum-bonded investment has been used for gold casting in dentistry. Since Taggart (1907) introduced casting technique as we know it today, different types of gypsum-bonded investments have been developed (Section 1.2). Several heating procedures are commonly utilised. Moulds are usually placed in an coven 2-3 hours after the start of mixing the investment. By this time they possess a sufficiently high wet strength to be transferred to the oven (Craig, 1993). According to the Australian Standard for Gypsum-Bonded Casting Investment (AS 2795- 1985), after 2 hours from pouring the investment mix, moulds are placed in to a furnace at room temperature and the temperature is raised at a rate of 5 °C/min. This rate is maintained for the entire the heating cycle for investments which do not contain cristobalite. The total heating time is a little more than 2 hours. If an investment does contain cristobalite, a slower heating rate of 1°C/min over the temperature range of 200-300°C is recommended and thus the total heating time is about 3.5 hours. Typically about 4-6 hours is required between pouring the investment and making the casting. A new method to reduce the time required for mould heating has recently been introduced for gypsum bonded investment and several commercial products are now available. According to this method, 30 minutes after the start of mixing, the mould is placed in an oven preheated to 700°C. After maintaining the mould at this temperature for 30 minutes, the casting is made. The total time required before casting is only 1 hour. The new method is called rapid heating technique. The so-called wet calcination (autoclaving or solution method) of manufacturing calcium sulfate hemihydrate is a recrystallisation process that will produce well developed crystals and increase the size of crystals or expansion (Section 1.4.2). IfChapter 2: Purpose and Scope this mechanism can be brought in during the heating of moulds prepared from ‘gypsum-bonded investment, an additional increase in expansion to that from the refractory is attained. The aim of this study is to evaluate new investments marketed for the new casting technique and prove the hypothesis that in this type of heating a-calcium sulfate hemihydrate (dental stone) rather than 8- calcium sulfate hemihydrate (plaster) is formed and the recrystallisation process in the former adds extra expansion to those derived from the transformation of cristobalite and quartz. It is assumed that extra expansion is attained when conventional gypsum-bonded investment is heated quickly. The first part of the study is to quantify the composition of investment powders to investigate whether new investments for the rapid heating technique contain only ctistobalite or quartz or both. By doing so, compositional differences between the new investments and conventional cristobalite casting investment can be found. The second part of the study is to measure the thermal expansion of conventional and new investments under common laboratory measuring conditions to compare their expansion behaviour. Small specimens (5 x 20 mm) and a heating rate of 5°C/min will be employed. This will be followed by the measurement of thermal expansion of realistically large specimens (20 x 50 mm) under the rapid heating schedule. Two different methods of heating could produce some preliminary information about the hypothesis. The final part the study measures mass changes of the large investment specimens after heating under three different conditions; slow (5°C/min) and rapid heating of dry specimens and rapid heating of wet specimens. By measuring mass increases occurring in the specimens after heating, the degree of I-CaSO, rehydration and thus the formation of a- or B-calcium sulfate hemihydrate can be estimated (Section 1.5.1 & 1.5.2) 27Chapter 3: Materials and Methods Chapter Three Materials and Methods 3.1 Materials Five brands of gypsum-bonded casting investments were used. Three were new materials marketed as rapid heating investment and two were conventional cristobalite investments. Details of the investments are given together with code numbers in Table 3-1. ‘Table 3-1: Gypsum-bonded investments used Code] Type oflnvertment | Matera ‘WiP* | Manufsctrer Ri__| Rapidheating Crstouiek 033 | GE Comp, Tokyo, Japan 2 | Rapidbeating Crinobalte FF ‘035 | Shofa Ine, Koto, Japan ¥S_| Rapidbeating Crincbalte FF ‘035 | Noritake Co. Lid, Nagoya, Japan c Conventional ‘Griabale ay O58 | SybroalKer Products, OSA [= _[ coment Griabalte Miro | 033 | GC Corp, Tokye, Japan *:Water/Powder ratio recommended by manufacturer 3.2 Experimental Methods 3.2.1 Analysis of the composition of investment powders Differential thermal analysis (DTA) and thermogravimetry (TG) equipment (Thermoflex, Rigaku Co, Japan) was used in this experiment (Fig. 3-1). Each powder sample and c-alumina reference material were kept in a desiccator over silica gel for at least 24 hours before analysis. For each analysis a quantity of 200.00.1 mg was used for both sample and reference material. The test sample and reference material were placed in two separate compartments of a platinum sample holder. Each compartment had a recess at the base to accommodate the hot junction of a thermocouple. The powders were heated to 700°C at a rate of 10°C/min and a range 28Chapter 3: Materials and Methods of 225 WV was employed for DTA. TG analysis was set to display 20 mg mass change at full scale of the chart recorder. Alll five investments were used and five to seven analyses were made for each material. Peak temperature was determined for each exothermic and endothermic reaction appearing on the DTA curves and mass changes at various temperatures were calculated as percentage change from the TG curve for each sample. The accuracy of the DIA-TG equipment was 0.33% of fall scale for temperature (43.3°C for a full scale of 1000°C in DTA) and 0.2% for mass change in full scale (+ 0.04 mg for a full scale of 20 mg). Ambient laboratory conditions during measurement were 2121°C and 50+10% RH.Chapter 3: Materials and Methods 3.2.2 Thermal expansion measurement of investments (TMA) ‘Thermal expansion measurement was conducted on cylindrical specimens, 5 mm in diameter and 20 mm in height, using a thermo-mechanical analyser (TMA, Rigaku Denki Corp., Tokyo, Japan) shown in Fig, 3-2. Each investment was mixed in the water/powder ratio recommended by the manufacturer (Table 3-1). The investment powder and water were measured to an accuracy of 0.01g and a standardised mixing procedure was followed. The investment powder was sifted in to the water, the powder and the water then were mixed using 10 seconds hand spatulation at a rate of 3 turns/second. This was followed by 20 seconds mixing by a mechanical mixer under vacuum with a rotational speed of 425 r/min (Whip-Mix, Model B Power Mixer, USA). Investment mixes were poured into a three piece PTFE mould, which was lightly coated with a silicon release agent (P-R. silicone spray, Rocol, Australia) A glass plate was placed on top of the mould to form a flat surface. Specimens were aged in the closed mould for at least 2 hours and then dried under ambient conditions until they reached a constant mass Fig. 3-2: TMA apparatusChapter 3: Materials and Methods A cylindrical fused quartz with the same size as that of specimens was used as the reference material. Specimens and reference material were heated to 700°C at a rate of 5°C/min under a measuring load of 0.01 N (1g). Thermal expansion values were calculated as a percentage against original specimens height. Mass change after heating was also recorded (Mettler AE 163, Metter Instrument Corp., USA). All five investments were used and five specimens were examined for each material, Ambient laboratory conditions during measurement were 21 +1°C and 50:+10% RH. 3.2.3 Thermal expansion measurement of investments (rapid heating) This part of the expansion measurement attempted to simulate actual conditions of the rapid heating technique and used larger specimens, 25 mm in diameter and 50 mm in height (Fig. 3-3). Investments were mixed in the same way as described before (Section 3.2.2). A mould was designed to make an axial hole in the base of each specimen to accommodate the hot junction of a thermocouple. A round plate of Inconel (25mm in diameter, mass about 0.02 N) was placed on the top of each specimen during casting of the investment mix. This was to distribute the measuring force (about 0.14.N) over the specimens during thermal expansion measurement. ‘Two rapid heating investments (R1, R2) and a conventional investment (C1) were used in this part of experiment. Specimens were removed from the moulds 30 minutes after pouring the investment ‘mix, and then immediately transferred to a vertically disposed vitreous silica dilatometer (Fig. 3-4). The dilatometer contained a vitreous silica tube large enough ‘to accommodate the specimen. The base of the tube was flat and had an axial hole to accommodate a type K thermocouple for measuring specimen temperature. The thermocouple was connected to a data logger (Data Taker 500, Data Electronics, Australia) to record temperature every 5 seconds. The upper part of the silica tube was fixed to the upper part of the apparatus by a water-cooled clamp. The vitreous 31Chapter 3: Materials and Methods silica tube was provided with an exhaust system to prevent excessive accumulation of ‘water-vapour and other gases released from the specimen. A fused quartz push rod with a tapered tip was placed on the metal plate at the top of the specimen and moved relative to the silica tube as the specimen expanded. Movement of the rod was measured by means of a linear transducer which was fixed to the top of apparatus, The transducer was connected to a data logger (Data Taker 500, Data Electronics, Australia) to record the expansion every 5 seconds. A vertically moveable furnace had a type R thermocouple which was positioned between the silica tube and the inner wall of the furnace, This thermocouple was connected to a temperature controlling system (Type LVP/CC10, Eurotherm, Australia) to set and control furnace temperature. Preliminary measurements were made in order to monitor the accuracy of actual temperature achieved and temperature programmed. Fig, 3-3: Small (5@x20mm) and large specimens (25@x30mm) prepared for TMA and rapid heating experiment, respectively.Chapter 3: Materials and Methods The furnace was pre-heated to 700°C while it was in the lower position. After placing the specimen in the silica tube the furnace was pushed up by compressed air to expose the specimen to 700°C. Thermal expansion of the specimen was measured for 30 minutes and then the furnace was lowered to remove the specimen from the Linear transducer a Invar support Heat shield. fF 7 HK Water-cooled clamp Outer tube of x! fi ) Inner (moving) tube dilatometer of dilatometer rh |i Heat resisting ‘urnace alloy (Inconel) Vent Clamp tt A Refractory spacers Fig. 3-4: Apparatus used in measurement of thermal expansion in the rapid heating schedule. Dotted line shows furnace in upper position, 33Chapter 3: Materials and Methods silica tube. ‘The expansion was determined to the nearest 0.001 mm and expressed as a percentage of the original specimen length. Five measurements were made for each material. Ambient laboratory conditions during measurement were 21 -+1°C and 50:10% RH. The results were subjected to t-test to find any significant difference from those obtained by the TMA method (Section 3.2.2), 3.2.4 Mass changes of investment after heating The final part of the investigation measured mass increases of rapid heating investment after completion the heating cycle. The changes measured were due to rehydration of unstable or hygroscopic III-CaSO, to hemihydrate (Section 1.5.1). Rehydration will not be noticeable when o.-hemihydrate was pre-formed since in this form the IIl- I transition occurs rapidly at low temperatures and the stable II-CaSO, is the likely product. Noticeable rehydration (mass increase) implies the formation of B-hemihydrate (Section 1.5.2). In order to perform the calculation relating to the rehydration process accurately and also to reveal the situation taking place in the investment, three series of experiments were conducted, slow and rapid heating of dry specimens and rapid heating of wet specimens. Investments were prepared in the same way as described before and only the large specimens were used (Section 3.2.2). One rapid heating investment (R1) was used. Ambient laboratory conditions during measurement were 21 +1°C and $0410% RH. 3.2.4.1 Slow heating of dry specimens Specimens were aged in a closed mould for at least 2 hours and then dried under ambient conditions until they reached a constant mass. They were further dried in a desiccator over silica gel for at least 24 hours to attain a final equilibrium mass. Each dried specimen was placed in a room temperature furnace and then heated at a rate of 34Chapter 3: Materials and Methods 5°C/ min until the thermocouple inserted in the specimen showed a pre-determined temperature between 200°C-700°C. The specimen was removed from the furnace and weighed within less than a minute using a chemical balance (Mettler AE 163, ‘Mettler Instrument Corp., USA). All specimens were again left under ambient conditions until constant mass was reached and then stored in a desiccator over silica gel for at least 24 hours to attain a final equilibrium mass. The two equilibrium masses, before and after heating and the weight immediately after heating, were used to calculate the mass change. Five measurements were made for each temperature, 3.2.4.2 Rapid heating of dry specimens Dry specimens were prepared in the same way as above (Section 3.2.4.1). After recording the final equilibrium mass, each specimen was placed in the furnace pre~ heated to 700°C (Section 3.2.3) until the thermocouple inserted in the specimen showed a pre-determined temperature between 200°C-700°C. The specimen was removed from the furnace and weighed within less than a minute, All specimens were again left under ambient conditions until constant mass was reached, stored ina desiccator over silica gel for at least 24 hours to attain a final equilibrium mass. Five specimens were measured for each temperature. 3.2.4.3 Rapid heating of wet specimens Each specimen was removed from the mould 30 minutes after pouring the investment mix. It was weighed and placed in a furnace preheated to 700°C until the thermocouple inserted in the specimen showed a pre-determined temperature between. 200°C-700°C. The specimens were weighed before and twice after heating as before (Section 3.2.4.2). Five to seven specimens were measured for each temperature.Chapter 4; Results Chapter Four Results 4.1 Analysis of the composition of investment powders Representative DTA-TG curves obtained in this study are shown in Figure 4-1a & 4- 1b and the results are summarised in Table 4-1. Upon heating to 700°C four endothermic and one exothermic reactions were observed. The first endothermic reaction was observed only in R3 and C2 and had mean peak temperatures of 73°C and 76°C respectively. Mean mass decreases of only 0.19% (R3) and 0.27% (C2) were recorded at 100°C. There was no clear peak at this temperature range in other investments. The second endothermic peak appeared with all materials and had mean peak temperatures between 179°C and 185°C. The reaction was accompanied by larger mass decreases; 1.53% to 2.24% at 200°C. The third endothermic reaction occurred at about 250°C but a relatively large temperature range of 233°C-257°C was recorded for the peak temperature. The fourth endothermic peak was observed only in the rapid heating investments at about 570°C. There were no significant mass decreases during these third Oand fourth endothermic reactions. A small exothermic peak was noted at about 198°C - 200°C but this was not clear with C1. After the large mass decrease accompanied by the second endothermic reaction, only a small gradual decrease in mass of maximum 0.02% occurred between 200°C and 700°C in all investment powders except C1. This investment showed a further mass decrease of 0.22% between 200°C to 220°C after which there was no further mass decreases to 700°C. 36Le (sone.ap prepueys) oBeroAe axe UALOYS SenIEA, “QUOT AULOISHD OD = ZO ‘ABUT arTEGOISHD HOY = [9 ‘AA OHTEGOISH SYLON = € “Ad UIEAOISHD NYOUS = Ze “I Movs OO = TI e0'ze 0642 7'8e 860 00°92 Jopuig Jo aBequodseq (£0'0) 9% (€0'0) su" (Zo'0) 96° (S0'0) 981 (L0'0) 091 D004, (v0'0) 9¢°% (€0'0) SLT (Z0'0) 96° (p0'0) 98°T (80°0) 09°T 20009 (£0'0) 9¢% (£0'0) SLT (€0'0) 96° (S0'0) 98°1 (Lo'0) 091 0005 (Zoo) 977% (€0°0) SLT (£0'0) 96°L (p0'0) 98°T (L0°0) 091 ‘2000r (Zo0) 97% (€0°0) SLT (Zo'0) 96° (v0'0) s8°1 (£0°0) 09°L De00€ (£0'0) bez (00) €s'T (Zo'0) S61 (v0'0) s8°T (L0'0) 6s°1 20002 (00) £70 (Zo'0) 200 (10'0) 610 (00°0) 00°0 (00) 0'0 ‘20001 (%) sesvaxoap Sse ($0) 661 (1) 861 (b'0) 002 TD) 861 omMToOX (/'0) ozs (0'0) 69s (10) ozs ‘yutsoyropus Uy (WD sz 1) rz (SI) €&@ (L'0) osz (v0) ssz ‘omusoyjopus pig (G0) s8t @O 6LI (1) zat (8'0) p81 (8:0) 81 ‘oyueyyopue puz (8'0) 94 Od EL ‘quLOOPUD 38] (9) einqesoduray 3yeag (=) 7 @=9 10 (=u) eu (=wW ar O=) rt Tevoreyw synsay p sedey TopMod JUSUNSOAM popuog-UMsdAS Jo spuesg say Jo syNSeI HI -VL ‘I-h 1eL,ae suounsoaur pepuog-unsds8 Sunvay pides 2am Jo samo HI-V.LC eaneweseday -eT-p BY (Oo) amyeroda I, L 1 L L 009 = 00r 00z 008 009 = 00F_— «007 008 009 00r = 00 1 L 1 L 1 s ’ ‘yuerpopug : %) iv pL OL Tsasearoap sseWA, vid T vid mae ew wa Ta ° synsoy :p rerdey6 sjuaunsoaur pepuog-wnsd&S feuorusAtIoD Om) JO SaAINO HL-VLC eaneuosardoy :qI-p BL (Q.) exnperodure, 008 009 00r 007 008 009 00 007 ¥ squuetpopug, € | iv z ) oe oe sasearoop SSeIA, vid vid 1 ommompoxg, w TO 0 synsay p soideyDChapter 4: Results 4.2 Thermal expansion of investments (TMA) Representative thermal expansion curves of the five investments are shown in Figure 4-2 and the results are summarised in Table 4-2. Thermal expansion curves were highly reproducible up to 300°C in all investments. A.small gradual expansion of about 0.2% was observed up to 150°C in all investments. This was followed by a large expansion between 220°C-270°C. The rapid expansion was complete at about 325°C where a plateau was formed. The plateau was followed by a small shrinkage to 400°C. In the conventional investments (Cl & C2), a small expansion followed up to 700°C, while in the rapid heating investments (R1, R2, and R3) the small shrinkage was followed first by a gradual small expansion and then by a rapid and large expansion at 550°C-600°C. The remaining expansion was very small or a plateau. The final thermal expansion values at 700°C were very similar, 1.22 (R3) to 1.45 (C2). ‘Table 4-2: Mean thermal expansion values of five gypsum-bonded investments. R1= GC Cristoquick If; R2= Shofuu Cristobalite PF; R3= Noritake Cristobalite FF; C1= Kerr Cristobalite Inlay; C2= CG Cristobalite Micro ‘No. Thermal expansion % (Mean) 700°C Standard deviation 3 3.0 5 1.33 0.06 5 1.22 0.04 5 1.37 0.04 5 145 0.05 40It oxompy HENS 9D = 2D ‘Aoquy anTeqOISHS 119 = TD “A SHTEqOISHD OPEILON = CX ‘ald SHTEGOISHO NJONS = 7 APMbOISHD IO = TL ‘S]WOUNSOAUT BAY JO SeAIO UoIsUEdxe jeULIOy) oANMSaTdaY :z-p “BL (¢) exnyesoduray, 00L ' 0S9 009 OSS 00S OSF OOF OSE DOE OSZ 00T OST DOT OS O 1 1 1 f A , i A A + +—+ t + t t + t + 7Oo— TO cu— wh ta — SHNSOY “p Lorde aChapter 4: Results 4.3 Thermal expansion of investments (rapid heating) Representative thermal expansion curves of the three investments heated under the rapid heating program are shown in Figures 4-3a & 4-3b against time and temperature respectively. The results are summarised in the same way in Table 4-3a & 4-3b, The mean thermal expansion values obtained in this method of heating were 1.72% (RI), 1.93% (R2) and 1.84% (CI) at 700°C and after 30 minutes. They are significantly (p< 0.005) larger than those obtained from the small specimens by the TMA method (5°C/min). At 10 minutes from the start of heating, the mean expansion values were 0.68% (RI), 1.44% (R2) and 1.40% (C1). ‘These were already about 75% of the final expansion values at 30 minutes in R2 and Cl, while the expansion was about 40% of the final value in R1. Most of expansion(> 90%) occurred at 15 minutes but this was after 20 minutes in R1. The expansion curves were very different from those obtained from the TMA method in all three investments. After a small and slow expansion up to 200°C, the expansion was rapid until the end, although this was finished at around 500°C and a plateau was formed to 700°C in C1. The expansion rate of R2 was higher than R1. 42Chapter 4: Results Time (min.) Fig.4-3a: Representative thermal expansion curves of three investments under rapid heating, Thermal expansion (%) 0.5 7 —a eT nel +++ 0 200 400 600 800 Temperature CC) Fig.4-3b: Representative thermal expansion curves of three investments under rapid heating.oY (uonesep prepueig) aBeroav are uMOYS soneA (oro) 81 (O10) #8T (010) p8't (60°) 18" (60°0) OFT (400) seo ite} (80°0) €6°1 (80°0) 261 (80°0) 061 (Lo’0) 08" (s0'0) vet (90'0) sro aw (90'0) ZL1 (90'0) 89°1 (oo) ret Gro) 890 (€0'0) szo me um Og uw sz ‘uu ST ‘um OT (op) anyea worsuedysy yeusoy ‘|ulp Jo UoHBIOpIsuoS YAM onbruyoa} Supeoy pides uy quawomsvaus uo|sUEdxe yeUIEy) Jo SNSOY :E-p aq, sus sreesy (uonersep prepueyg) oBesone ose umoys sanpeA (O10) rs" (60'0) zs" (60'0) LoL (L0’0) of 1 (L0°0) £61 (90°0) ss'T (Lo'0) £91 (20'0) 9¢°1 (90°0) ZL: (400) 09°1 (40.0) 971 (50'0) 760 D600L 2.009 2000s 000% (0%) uorsuedxg yeunsoy, (Zo'0) 060 (so'0) szo 19 (s0'0) 001 (so'0) 6¢'0 wa (90°0) 0L'0 (S00) €z'0 a D2.00€ 00007, “amnyeroduray suourtoads Jo worresapisuos ym anbrnyoay Suryeay pides ur juowrounsvaus uorsuedxo [eULLOY} JO SINSOY :a€-p A148, sansa ip rodeChapter 4: Results 4-4 Mass changes of investment after heating Mass changes occurring in dry specimens heated slowly (S°C/min) are shown in Table 4-4 and illustrated in Figure 4-4. The maximum weight loss occurred at 700°C and had a mean value of 6.87%. More than 95% of this value was already reached when specimens were heated to 250°C. However the specimens heated to this ‘temperature were different from those heated to 700°C as their mass increases after equilibrium was reached. The lower target temperatures of 250°C-350°C produced larger mass increases. Weight recovery decreased with the increase in heating temperature. Mass changes occurring in dry specimens exposed to the rapid heating are shown in Table 4-5 and illustrated in Figure 4-5. The average maximum weight loss was again 6.85% but this occurred already at 500°C apparently due to the exposure to the high furnace temperature (700°C) from the beginning. The maximum weight loss was then constant up to 700°C. The maximum weight recovery also occurred at a lower target temperature of 200°C. At this maximum mass increase, however, it did not reach the full recovery to hemihydrate (upper horizontal line), indicating the formation of stable II-CaSO,. In this experiment also weight recovery decreased with increase of target temperature in specimens. Mass changes occurring in wet specimens heated in the rapid heating conditions are shown in Table 4-6 and illustrated in Figure 4-6. Maximum weight loss occurred at 700°C with the mean value of 6.58%. The maximum weight recovery occurred at 250°C and 300°C, the same as dry specimens heated in the rapid heating conditions. The difference was that weight recovery occurring in wet specimens was less than that in dry specimens. 46Chapter 4: Results Table 4-4: Mass changes of dry specimens (R) after slow heating. Temperature Weight loss after Weight loss after equilibrium Weight ec) heating (%) achieved (°%) recovery (%) 200) 5.83 0.17) 4.74 (0.04) 1.09 (0.19) 250 6.58 (0.04) 4,70 (0.11) 1.89 (0.08) 300 6.70 (0.08) 4.85 (0.17) 1.85 (0.10) 350 6.71 (0.04) 497 (0.14) 1.74 0.11) 400 6.74 (0.02) 5.72 (0.02) 1.02 (0.02) 450 6.79 (0.06) 5.97 (0.11) 0.82 (0.08) 500 6.79 (0.08) 6.05 (0.11) 0.74 (0.05) 550 6.81 (0.04) 6.13 (0..03) 0.68 (0.04) 600 6.81 (0.03) 6.17 (0.04) 0.64 (0.03) 650 6.84 0.02) 6.27 (0.01) 0.57 (0.01) 700 6.87 (0.04) 6.34 (0.03) 0.53 (0.05) Values are average (standard deviation) 478h aqespAyUroY 0} oapPAYuR oyyINs uMIOTEO Jo wonespAyax Jo onyea feonos09y) = au erUOZLOY reddy ‘omupAqu oreFINs waNIOTeO O1 uOREIPAYOP o40]dLU0o = [eIOz10Y EMO] ‘uMLIGHINbs Joye sosearoop sseUI = UY] pay ‘Bureay Joye sosearoap ssemI = OUT ONIEL ‘Aqmoys poreay (qf) suotmtoads Arp ut Surzano00 soBueyo sseyy :p-h “Bi Lg 2 ol's- | ge (%) 880] qBIOA 00L 009. 00s 00r 00€ 007 ool (Q.) aanyusaduray, simsoy :p radeChapter 4: Results Table 4-5: Mass changes of dry specimens (R) after rapid heating. Temperature Weight loss after Weight loss after equilibrium Weight ec) heating (%) achieved (°%) recovery (%) "3007 (@.07) 43 (0.07) "26 (0.05) 250 6.76 (0.03) 5.71 (0.02) 1.05 (0.03) 300 6.80 (0.04) 5.82 (0.08) 0.98 (0.05) 350 6.80 (0.07) 5.90 (0.13) 0.90 (0.07) 400 6.81 (0.05) 6.02 (0.11) 0.79 (0.07) 450 6.83 (0.02) 6.08 (0.03) 0.75 (0.04) 500 6.85 (0.04) 6.12 (0.04) 0.74 (0.01) 550 6.85 (0.06) 6.14 (0.07) 0.71 (0.04) 600 6.85 (0.09) 6.16 (0.05) 0.69 (0.07) 650 6.85 (0.04) 6.24 (0.03) 0.61 (0.01) 700 6.85 (0.02) 6.36 (0.02) 0.49 (0.04) Values are average (standard deviation) 49os syespAyueY 0} oypAqueE ‘oqRyINs wmNIDTRo Jo woHeIpAYos Jo onywA ToHosONTp = SUT TEUOZLOY Jody ‘owAPAyuE oyeyTNs umIDTeo 0} uOHTEIpAYap a19|dutoo = jeyOZHIOY JoMo7] ‘umLUgHINbe JOYE saseaioap sseUI = oUT] poy ‘SuNLoy Joye sasvaroop sseUI = OUT] On| ‘suommpuoo Supeay pidex oy ut poyeey (gf) suounoads Aup ut Suysnod0 soBueyo se :¢-p “St Le gg HF sus: s r e te 004 009 00s 00r 00€ 007 001 (9) emerodua synsoy :p soidey (%) sso] 181M,Chapter 4: Results Table 4-6; Mass changes of wet specimens (R) after rapid heating. Temperature Weight loss after Weight loss after equilibrium Weight ec) heating (%) ~=—"300 6.23 (0.06) 250 6.43 (0.23) 300 6.44 (0.02) 350 6.49 (0.03) 400 6.50 (0.03) 450 6.51 (0.12) 500 6.51 (0.03) 550 6.53 (0.08) 600 6.55 (0.08) 650 6.57 (0.07) 700 6.58 (0.10) achieved (%) 5.57 (0.08) 5.66 (0.24) 5.69 (0.01) 5.81 0.03) 5.86 (0.05) 5.87(0.11) 5.89 (0.03) 5.90 (0.07) 6.00 (0.07) 6.00 (0.04) 6.11 0.12) recovery (%) 0.65 (0.04) ~ 0.77 (0.03) 0.75 (0.02) 0.68 0.03) 0.64 (0.06) 0.64 (.03) 0.62(0.01) 0.63 (0.02) 0.55 (0.02) 0.57 (0.10) 0.47 (0.04) ‘Values are average (standard deviation) sloqBIpAYPUIY 0} IIPAYUR oFeyINS WANTOTLO FO ‘uoreapayps Jo anya jeoper03q = our] peruoztoy addr ‘D.00L 78 oTHpAYTE apagins WINIO]LO OF ‘worespAyap ara]duroo = yeywozyOy JeMorT ‘tuntaqymbe Joye soseasoop seu = our pay “Sunyvoy Joye sesvaoep sseur = avi OnkeL -suoripuoo Saneey pides ut pareoy (xf) suauajoads yom uy BuyLINOD SOBULYD SHIN 'S-h iq Lr 2 9 + 9 tt tt tH ° 004 009 oos oor os o0z oot F + + + + 0 (Do) emmeredute | (%) 8801 TBPChapter 5: Discussion Chapter Five Discussion Since Taggart (1907) introduced the casting process to dentistry as we know today, scientists have tried to find a way or an investment which compensates the shrinkage of gold alloys during dental casting. The amount to be compensated is, about 1.68%-1.80% (Section 1.2). Such a high expansions have never been reported during the heating of commercial gypsum-bonded investments and it is common to resort to the concept of total expansion where the setting expansion of an investment is combined with its thermal expansion. This study has shown that a ‘thermal expansion as high as 1.93% is occurring when newly released gypsum- bonded investments are heated according to the manufacturers’ rapid heating schedule (Section 4.3). Two questions then arise of these new investments, whether they have quite different composition from those of conventional gypsum- bonded investments, and secondly whether such high thermal expansions result solely from the rapid heating technique proposed. In anticipations of attaining these high thermal expansions by the rapid heating technique and encountering these questions, the present study started with the analysis of the investment compositions by means of simultaneous differential thermal analysis and thermogravimetry (DTA-TG). The first endothermic reaction, which was observed only in R3 (73°C) and C2 (76°C), was accompanied by small mass decreases of 0.19% (R3) and 0.27% (C2) at 100°C. This is most likely due to removal of moisture from investment powder (Mori 1993), since the endothermic reaction associated with the dehydration of dihydrate to hemihydrate usually occurs at about 120°C-150°C under dynamic heating conditions employed in DTA (Section 1.3). It appears the 24 hours drying over the silica gel was not enough to completely remove the moisture from these powders, 33Chapter 5: Discussion The large endothermic peak observed between 180°C- 185°C in all five investment powders indicates the change of calcium sulfate hemihydrate to anhydrite as it was accompanied by relatively large mass decreases of 1.53-2.2%. The dehydration ‘was complete at just below 300°C in all materials. The endothermic peak due to dehydration was immediately followed by an exothermic peak at about 200°C in all five investment powders. This exothermic peak at relatively low temperature, compare with that generally observed at a temperature of about 300°C, has been attributed to the almost instantaneous phase transition of calcium sulfate anhydrite from its unstable to stable phase that occurs with o.-calcium sulfate hemihydrate, in contrast to the sluggish transition in B- calcium sulfate hemihydrate (Powell, 1958; Fleck ef al., 1960; Kuntze, 1965; Holdridge, 1965; Miyazaki, 1966a, 1966b; Bell & Urie, 1970; Clifton, 1972; Bushuev & Borisov, 1982; Mori 1993). This unique exothermic peak was not quite clear in C1. Some additives such as sodium chloride can suppress the exothermic reaction in this temperature range (Mori, 1986). Ina similar DTA-TG study on investment powders, McAloon and Mori (1993) found that this investment powder (C1) contained o.- and B- calcium sulfate hemihydrate. There could have been some changes in the composition of this investment since their study. In fact, the thermal expansion of this investment has been increased as discussed later. The next endothermic peak which represents the phase change in cristobalite (a to B) took place around 250°C except in R3 (233°C). The a- 8 transition of cristobalite can occur in a wide temperature range of 120°C-275°C, depending upon the previous history of crystals, but it is generally around 225°C-275°C (Sosman 1965, Heaney et al., 1994). Two factors which affect this transition temperature are known, the temperature at which the cristobalite was originally formed and the kind of silica from which it was formed (Sosman 1965). 54Chapter 5: Discussion The final endothermic reaction at about 570°C was observed only in the rapid heating investments. This represents the change of quartz (ot to 8) (Sosman 1965, Heaney ef al., 1994), and reveals that the rapid heating investments investigated in the present study all contain both cristobalite and quartz. A reasonable estimate of the content of calcium sulfate hemihydrate in investment powders can be made by taking the mass decreases at 300°C as well as that at 100°C as moisture content and comparing with the theoretical value of dehydration of hemihydrate to anhydrite, 6.2% (Mori, 1993; McAloon & Mori, 1993). This calculation gives a range of 26%-32% by mass calcium sulfate hemihydrate in the original investment powders. This range has generally been agreed for its potential to produce a high thermal expansion (Skinner & Degni 1978, Phillips, 1993; Craig, 1997; O’Brien, 1997). Therefore, the only significant difference between the rapid heating and conventional gypsum-bonded investments appears to be the inclusion of quartz. The new investments may achieve similar thermal expansions generally obtained with the conventional investment containing cristobalite only. However, the use of cristobalite in place of quartz, was a major step to attain higher thermal expansion in gypsum-bonded investment in the 1930s, and a typical investment contained about 70%-75% cristobalite and 30%-25% calcium sulfate hemihydrate by weight (Coleman & Weinstein, 1933; Taylor et al, 1930; Van Allen, 1933). It is difficult therefore to expect that the new rapid heating gypsum-bonded investments, consisting of both quartz and cristobalite without much change in the content of calcium sulfate hemihydrate would achieve higher thermal expansion than those of the conventional cristobalite investments. The second part of study compared the thermal expansion behaviour of these investments under controlled laboratory conditions by means of thermomechanichal analysis (TMA). When a gypsum-bonded investment is heated, a number of dimensional changes take place. The changes occurring in the gypsum binder are mostly negative or contraction due to phase changes during dehydration (Earnshaw, 1975, 1978; Mori, 1986). This is because the density of gypsum is increased as it changes to 55Chapter 5: Discussion hemihydrate and to anhydrite (Mori, 1982, 1986). This is why, although the whole mould expands due to expansion of refractory, we observe a plateau or small shrinkage in the thermal expansion curve. In all materials tested in this study, the plateau occurred around 100°C -200°C, registering the first step of dehydration of gypsum binder to hemihydrate (Tasaki ef al., 1978; Tasaki, 1979; Mori, 1986). The plateau was followed by a large expansion between 220°C-270°C due to the 2-8 cristobalite conversion (Heaney et al., 1994). The high temperature phase is less dense than the low one (Sosman, 1965; ler, 1979). Slight differences in the position of the endothermic peak due to this inversion in the DTA-TG experiment coincided with the differences in the position of the large expansion. The onset of the TII-II transition at about 300°C results in a the formation of a plateau or rather distinct shrinkage between 300°C -350°C (Tasaki, 1978; Mori, 1982, 1986). In accordance with the last endothermic reaction in the DTA-TG experiment, another large expansion happened only in the rapid heating type of investments at around 550°C-600°C, reflecting conversion of a to B-quartz (Sosman, 1965, Heaney et al. 1994). The final thermal expansion values reached at 700°C were 1.32% (RI), 1.33% (R2), 1.22% (R3), 1.378 (CI), and 1.45 (C2). The highest value obtained from one of conventional investments (C2) and the lowest was from rapid heating (R3), which were expected. However, values from R1, R2, and C1 were quite close. There are several reports about thermal expansion values obtained by the rapid heating technique. Shibuya ef al. (1995) found no significant differences in thermal expansion between rapid heating and conventional heating, while Kobayashi ef al. (1995) reported that most rapid heating investments had higher ‘thermal expansion than conventional investments, Takahashi ef al. (1993) reported that there was no differences in thermal expansion between 20°C/min and 3°C/min, However, they found that gold plates cast by the rapid heating 56Chapter 5: Discussion technique were longer than those obtained from the conventional technique. They did not give an explanation for the difference, although the only logical explanation is that a higher thermal expansion was reached by the rapid heating technique. ‘During the heating of gypsum-bonded investments, two major contractions due to the dehydration of gypsum to hemihydrate at about 120°C and the III-II transition of anhydrite at about 300°C-350°C should be observed (Earnshaw, 1975, 1978; Mori 1986) since the contraction accompanied by the dehydration of hemihydrate to anhydrite is theoretically negligible (Mori, 1986). These contractions were easily noticed when the small investment specimens were heated at by a common laboratories measuring method. However, under the rapid heating conditions employed in this study, only the first contraction was noted at about 120°C and the thermal expansion curves exhibited more or less rapid expansion all the way up to 700°C, The start of this rapid expansion was always at about 200°C, indicating that the dehydration of gypsum was almost complete at this temperature. However, temperature is not distributed evenly in the mould under such a rapid heating method, and the outer part of the mould reaches the furnace temperature much faster than the inner part of the mould. Under these circumstances any phase transformation either in the binder or the refractory occurs over a prolonged period of time. Excess water and water released from gypsum crystals remain longer at the inner of the mould. Matsuya ef al. (1979) showed that increasing the vapour pressure around gypsum specimens increases the temperature at which dehydration occurs. The same would be expected in gypsum-bonded investment specimens. The expansion between 200°C and 700°C includes rapid or isothermal expansions due to a to B-cristobalite transformation and a- to B-quartz transformation. Because of these on going expansions the largest shrinkage occurring in the binder due to II-II phase change was masked and was noticeable at about 500°C only in the conventional cristobalite investment (C1). This is of course due to the non- 37Chapter 5: Discussion existence of the expansion accompanied by the o.- to B-quartz transformation, as the investment does not contain quartz (Section 5.1), The maximum expansion values obtained with the TMA measurement of the small specimens (1.32-1.37%) were already reached at 10 minutes after the furnace preheated to 700°C was raised. The temperature measured at the centre of the specimens was in the range of 400°C -550°C at this time and extra expansions were recorded for the remaining 20 minutes during which specimen temperature increased to 700 °C. ‘These expansion values were significantly higher than those of the same materials heated under typical laboratory measurement conditions (p<0.005). In a relatively old study Jones and Wilson (1968) found that Kerr Cristobalite Inlay investment (C1) gave higher thermal expansions when a faster heating rate of 20°C/min was used for both 1 and 24 hour aged specimens. They stated that “the coincidence of loss of absorbed water and dehydration of gypsum to anhydrite, combined with the inversion of cristobalite, could result in extra expansion”. This explanation suggests a combined effect of the binder and refractory. The hypothesis of the present study assumes the sole effect of binder on the increased thermal expansion. The final examination in this study was concentrated to prove this hypothesis using only one investment (R1). In order to perform the calculation relating to the rehydration process accurately and also to reveal the situation taking place in the investment, three series of experiments were conducted, slow and rapid heating of dry specimens and rapid heating of wet specimens. This material contained 26% of calcium sulfate hemihydrate (Section 4.1). When the investment powder is mixed with water to make cast investment specimens, calcium sulfate hemihydrate changes to form gypsum and the percentage ratio of gypsum will not be the same as that of hemihydrate in the original powder. If the cast specimen consists entirely of gypsum, its theoretical mass decreases to hemihydrate and anhydrite are 15.7% and 20.9% respectively. 58Chapter 5: Discussion Actual percentage of gypsum binder (G) in set investment specimens can be determined by the following formula G=(WL/ 209) x 100 (1) where WL is the final mass decrease at 700°C. Mass decreases reached at 700°C in dry specimens heated slowly and rapidly had mean values of 6.87% and 6.85% respectively, and they were not significantly different. The following discussion uses the average, 6.86%, which gives a value of 32.8% as the percentage content of gypsum binder in the set investment specimens prepared from this material. The final mass decreases was 6.58% in wet specimens heated rapidly, indicating that the dehydration was not complete at 700°C or 30 minutes after the start of heating. Presence of excess water in wet specimens can be the cause of this incomplete dehydration. ‘When metastable calcium sulfate anhydrite (I1I-CaSO,) is formed and subsequently exposed to ambient conditions, its rehydration to hemihydrate results in the theoretical weight recovery of 5.2% (20.9-15.7) in specimens originally consisting of 100% gypsum. Theoretical percentage of weight recovery (WRa) in investments can be determined by the formula WRa, (%) = (G x 5.2)/100 (2) In the investment used in this investigation, the theoretical WRa is 1.71% as the component of gypsum binder is 32.8%. The expected percentage weight recovery was reached in dry investment specimens heated both slowly (1.71%) and rapidly (1.70%), when the mould temperature was 300°C-350°C. The recovery was slightly lower (1.64%) in wet specimens heated to 300°C-350°C rapidly. The difference (WL-WR) is equivalent to the mass decrease from gypsum to hemihydrate and this is shown by the upper horizontal line in Figures 4-4, 4-5, and 4-6. 59Chapter 5: Discussion When dry specimens were heated slowly the dehydration was near completion at 350°C. However, the specimens subsequently showed large mass increases upon exposing to ambient conditions, and the final equilibrium attained coincided with the value calculated for the dehydration to hemihydrate (upper horizontal). This is because the phase formed at this temperature is metastable III-CaSO., which rapidly rehydrates to hemihydrate when exposed to atmospheric moisture (Section 1.5.1). This is a traditional way of manufacturing plaster where the freshly calcined material is allowed to mature in ordinary ambient storage conditions (aging), (Section 1.4.1). When gypsum is heated to a red heat, it becomes inert in water (dead burnt) or II-CaSO, (Wiss et al., 1930; Gibson 1932; Worner 1942) but the formation of this stable anhydrite occurs slowly even at a relatively high temperature range (Section 1.5). This means degree of Il-CaSO, to II-CaSO, conversion can be ascertained by examining the degree of III-CaSO, rehydration, This rehydration is not significant when a.-calcium sulfate hemihydrate is formed because the III-II transition is fast and occurs at a relatively low temperature range while in B-hemihydrate the conversion occurs slowly at a relatively high temperature range (Section 1.5). In a typical DTA, a rapid phase change in anhydrite showing a sharp exothermic peak between 200°C- 220°C occurs with hemihydrates prepared by several wet calcination methods (autoclaving and dehydration in solutions) while the curve for a dry calcined hemihydrate (prepared in an air oven) indicates a gradual phase transition in temperatures between 300°C- 400°C (Powell, 1958; Fleck et al., 1960; Kuntze, 1965; Holdridge, 1965; Miyazaki, 1966a, 1966b; Bell & Urie, 1970; Clifton, 1972; Bushuev & Borisov, 1982; Mori 1993). The inertness of the specimens was most pronounced when the specimens were wet and heated rapidly (Fig. 4-6). The expected full weight recovery of the dry specimens slowly heated to 350°C indicates that the stable II-CaSO, phase is not present and such a situation is possible through the formation of B-calcium sulfate hemihydrate. The result can be expected because the heating conditions were similar to those of dry calcination of gypsum. The weight recovery was in fact higher with the specimens heated toChapter 5: Discussion 300°C than those heated to 350°C (Table 4-4). Therefore, the maximum amount of metastable I1I-CaSO, considered to be formed at around 300°C. However at this temperature the dehydration is not complete, and hemihydrate coexists. The results from the dry specimens also indicate that the weight recovery takes place even after heated to 700°C, confirming the sluggish nature of the II-I transition under dry heating conditions. Then remaining III-CaSO, for the temperature range of 500°C to 700°C is similar and approximately a quarter (0.53%) the maximum at 300°C (1.89%). ‘When dry specimens were heated rapidly the dehydration was complete at 500°C (Table 4-5). This temperature is much higher (about 150°C) than that recorded with slow-heated dry specimens and thus shows that the specimen temperature increases rapidly before the water released from the gypsum crystals.are completely removed. In contrast to the almost full rehydration of metastable III- CaSO, to hemihydrate that was recorded with slow-heated dry specimens to 300°C, the rapidly heated dry specimens demonstrated the maximum but not full weight recovery in the specimens heated to 200°C. The lack of full dehydration at such a low temperature, at least in the vicinity of the thermocouple inserted in the specimens indicates the formation of stable II-CaSO, and this is possible only through the formation of c:-hemihydrate. The delayed water elimination will produced a favourable dehydration condition for the formation of a.-hemihydrate. According to DTA-TG analysis, the temperature at which III-II transition occurs is between 300°C-400°C in B-hemihydrate. Therefore, the highest weight recovery occurring in this temperature range means the highest production of B- hemihydrate at that temperature and can be used to estimate the percentage of its formation. In the specimens size and slow heating conditions employed in dry specimens, weight recovery was the highest at 300°C. In fact this agreed with the theoretical weight recovery (WRa), 1.71%, of the investment used. Actual percentage of B-calcium sulfate hemihydrate formed during the heating can be calculated by the following equation: 61Chapter 5: Discussion B-hemihydrate (%) = (WR/ WRa) x 100 (3) which WR is percentage of weight recovery occur in each temperature. After finding the percentage of B-calcium sulfate hemihydrate by weight recovery at 300°C, the amount of o.-calcium sulfate hemihydrate that has been formed can be given by a simple formula: ct-calcium sulfate hemihydrate (2%) = 100 ~ B-hemihydrate (%) The above formula estimates that the formation of about 33% cl-hemihydrate and 67% B-hemihydrate in the rapidly heated dry specimens and about 44% o- hemihydrate and 56% B-hemihydrate, in the rapidly heated wet specimens (Fig. 4- 6 and Table 4-6). This study supports the theory introduced by Kelley (1941) that c.-hemihydrate is produced not only by solution processes or autoclaving, but also at atmospheric pressure if the atmosphere is saturated with water vapour. In the absence of water vapour the resulting hemihydrate is of the B-form but at intermediate water vapour pressures the heats of solution indicates mixture of two modifications (Section 1.4.3). The percentage of each modification depends on the degree of water vapour in the atmosphere. Therefore even in dry specimens heated rapidly, water released from gypsum crystals creates conditions favourable for the formation of c-hemihydrate, when heated rapidly, as the temperature high enough to dehydrate gypsum to hemihydrate is quickly achieved without loosing the water released completed, in contrast to slow heating. The formation of a-calcium sulfate hemihydrate is further increased in wet specimens because of the presence of excess water. In the slow heating of dry specimens heat is distributed evenly in whole specimens and the accumulation of water or vapour is prevented, creating conditions similar to the production of B-calcium sulfate hemihydrate or plaster. An important difference between the a and B-hemihydrate modifications is the absence of superstructure in the former. This leads to greater mobility of the atoms of the crystal lattice of oz-modification and a greater increase in the size of 62Chapter 5: Discussion its crystals, compared with the crystals of the B-calcium sulfate hemihydrate. Dry calcination does not permit recrystallization and dehydration is a vigorous evaporation of water molecules from original gypsum crystals and results in poorly defined crystals which are porous with less volume than the original crystals (Kuntze, 1965; Bushuev et al, 1978). This explains the higher thermal expansion values obtained in the specimens having realistic size and heated by rapid heating technique compared with the values obtained from the conventional laboratory ‘measurement where specimens are usually small and the heating conditions tend to produce those of dry-calcination process even if the heating speed is high. This explains why we did not have a uniform view of the effect of rapid heating technique on the thermal expansion value (Kobayashi ef al, 1995; Shybuya et al, 1995; Takahashi et al, 1993). It is also noted that the extra thermal expansion attained by the rapid heating depends on the amount of the binder. Comparing the thermal expansion values of investments measured in TMA with those under the rapid heating, R1 which had the lowest percentage of binder (26%) gave the lowest increase in thermal expansion (1.72%). ‘The highest increase in thermal expansion value was observed with R2 which had the highest binder content (30%). Achieving a higher expansion with wet specimens is not a new phenomenon. Finger and Jargensen (1980) found that immersion of a mould prepared from a gypsum-bonded investment for three minutes in water before heating leads to 0.1% increase of thermal expansion. Whyte and Brockhurst (1996) found, in their experiment of sterilising dental casts by autoclaving (132°C for 5 minutes), that the casts increased in size after sterilisation. In heating moulds prepared from ‘gypsum-bonded investment, there is always the possibility of accumulating water or water vapour around gypsum crystals under the first step of dehydration, by immersing the mould in water before heating, by using water-absorbent ring liners and finally by placing moulds in a preheated oven. Therefore, the thermal expansion of a mould may have always been much higher than that measured under rather unrealistic laboratory conditions. Expansions comparable to that of gold alloy shrinkage (1.68%-1.80%) could have been occurring within the mould 63Chapter 5: Discussion without using any additives but by using a special laboratory technique developed empirically. 64Chapter 6: Summary and Conclusion Chapter Si Summary and Conclusions The aim of present study was to prove the hypothesis that the formation of c-calcium sulfate hemihydrate takes place and this is responsible for additional expansion attained in the recently introduced rapid heating technique of moulds prepared from gypsum-bonded investment. The technique exposes 30 minutes old moulds to furnace temperature of 700°C for 30 minutes before casting. Five brands of gypsum-bonded investment, three rapid heating and two conventional, were used. They had water/powder ratios of 0.33-0.38. Composition of the investment powders was initially quantified by simultaneous differential thermal analysis and thermogravimetry. Thermal expansion of small cast specimens prepared from these investments were then measured under common laboratory measuring conditions (5°C/min). This was followed by measurement of thermal expansion of large specimens under the rapid heating schedule. Expansion values obtained from the two heating methods were subjected to ¢-test to find any significant difference. The final experimental part measured mass changes of large specimens after heating under three different conditions; slow (5°C/min) and rapid heating of dry specimens and rapid heating of wet specimens. By these measurements formation of o- and B-calcium sulfate hemihydrate was detected and percentage of each modification was calculated for each heating schedule. After collecting the results of the above experiments the following conclusions were drawn: 65Chapter 6: Summary and Conclusion 1- The only difference found between the two types of investment was the type of refractory. The new investments contained both cristobalite and quartz while manufacturers claim they can achieve a similar thermal expansion that can be obtained from the conventional cristobalite investments. 2- Thermal expansion values obtained from the rapid heating technique were significantly higher than those obtained under common laboratory measuring conditions (p<0.005). The additional thermal expansion attained by the rapid heating depended on the amount of the binder. 3+ The full weight recovery of dry specimens slowly heated to 350°C, from the anhydrite to hemihydrate level, indicated that only B-calcium sulfate hemihydrate was formed in this heating method. 4-In both dry and wet specimens, o.-calcium sulfate hemihydrate was formed when the rapid heating technique was employed. Estimated amounts were 33% o.- hemihydrate (67% B-hemihydrate) in dry specimens and 44% o,-hemihydrate (56% B- hemihydrate) in wet specimens. The increased thermal expansions gained by the rapid heating technique are therefore due to the speed of heating and not due to the early start of heating. 5- Not only the excess water in moulds prepared from gypsum-bonded investment, but also the water released from the binder, produce conditions similar to those prevailing in wet methods of manufacturing calcium sulfate hemihydrate (dental stone). The accompaning recrystallisation process adds an extra expansion to that from refractory. The accumulation of water/water vapour favourable to recrystallisation did not occur in the conventional slow heating of dry specimens. 6- By using a method to produce t-calcium sulfate hemihydrate during heating of gypsum-bonded investments, thermal expansion to fully compensate the shrinkage of gold alloys can be reached without using any additives. 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BAppendix 1 Table 1.1: DTA-TG results of R1 (GC Cristoquik 11) [No. ‘MASS DECREASES UP TO_ ‘Endothermic Peaks [Exothermic Peal i006 [2006 _|300c_[4ooc [S00c_]e00C _]700c if 0.03] 1.61] 1.64] 1.64] 1.64] 1.64] 1.64] 185] 258) 571 200 2] 00s} 1.58 1.59] 157] 1.55[_ 15a sil 182|255| 570] 195] 3{___o|__1.5{_ 1.55] 155] 1s25|_1sil sil 182|255| 570] 1 4 009| 1.671 1.69] 1.69 1.69 1.69[ 1.67180] 254l 569] 195] 3{ 0.05] 1.64] 1.65] 1.65] 1.625] 1.62 1.6] 181255] 569] 198] 6|_0.06 1.64] 1.66] 1.66 1.65, 1.64] 1.63] _181| 255] _ 570] 198] of sil 1525{ sil 1s] us| 15] 18i|__255|__570) 198] Ix_|~ 004] 1.59[ 162|"1.61[ 1.60] 1.59] 158) 181.71] 255.29) 509. 198.14 sD |_ 0.03] 0.07] 0.06] 0.07] _0.07]_0.07]__0.07|__ 1. 1.25] 0.69] 157] Table 1.2: DTA-TG results of R2 (Shofu Cristobalite PF) [No. ‘MASS DECREASES UP TO [Endothermic peaks [Exothermic peal] ji00C [200 C [300 C J400c [5006 [600 [700C 1 1 oj] rsij 1s} 183] 1sil 181] 1.8| 183|__ 249] 569) 200) 2[ 0] 1.86] 1.88] 1.88] 1.86] 1.85] _1.85| _185| 250] 569) 200 3]___of 1.79] 1.8] 1.8] 1.79[ 1.78] 1.76] 184] 250] 569) 200 40] 1.88] 189{ 189] 189] 1.88] 186|_ 184| 250] 569] 201] S|_ooif 189] 19| 19| 19| 188] 1.87] 183] 251] 569 200 0.00} 1.85] 1.85] 1.86] 1.85] 1.84] _1.83] 183.80] 250.00] 569.00 200.20] [sD [_ 0.00} 0.04] 0.05] 0.04] 0.05] 0.04] 0.05] _0.84| _0.71| 0.00] 0.45 Table 1.3: DTA-TG results of R3 (Noritake Cristobalite FF) [No. MASS DECREASES UP TO. Endothermic peaks [Exothermic peal 100 C [200 C [300 C[400 [500 ¢ [6006 [700C. T]_ 0.19} 1.93] 1.93, 1.93] 1.97] 191] 1.9] 72179] 331] 569) 197 2! 0.2) 1.95] 1.96] 1.96] 1.95] 1.94 1.94] 73] _181| 232] 570] 198} 3] 0.19] 1.95] 1.951 1.95] 1.95) 1.94] 1.94] 68] 181] 232] 70] 193 4| 0.2] 1.95] 1.96] 1.96] 1.96 1.95| 1.94] 72 183] 232] 69] 197] 3] 0.18) 1.94] 1.95 1.93] 1.9119] 1.9! 75|__183|__235| 571 199 0.19} 1.98] 2| 2] 1.98] 1.95] 1.95] 75|__183|__234| 570] 200 | 0.19) 1.95] 1.96 1.96 1.94] 1.93] 1.93] 72.50] 181.67 232.67] 569.83] 198.1 [sD_| 0.01] 0.02 0.02] 0.03] 0.03] 0.02] 0.02] 2.59 1.63] 1.51] 0.75) LY 79Table 1.4: DTA-TG results of C1 (Kerr Cristobalite Inlay) Ss 0.035 | 0.04 | 1.291 | 1.46385 ‘Mass decreases up to [Endothermic Peaks|Exothermic peak] [600 C [700C 1 13] 188[ isi | 250 230 la 175 | 1.83 | 180" 250 228 3 175{_ 18[ 17s[ 249 227 la 168 | 1.75|" 180 |_250 229 5 173 [1.79 |" 178 |—_248 227 Is 174] 18[ 178[ 249 208 I7 174] ell 178 | 246 230 bx 1.741 | 1.809 | _179 | 248.857 | 298.4285714 SI 1272418021 Table 1.5: DTA-TG results of C2 (GC Cristobalite Micro) MASS DECREASES UP TO. [Endothennic Peaks [Exothermic Pea] (e000 _f700C 2224 23i| 73] 185] 233] 200) 229 2. 7__185|__257 200) 224 2275 75] 185] 257 195) 2204 2.2176] __184| 257 195) 2.24 220976184) 258) 199 225 2229 75.8 184.4 256, 199.4 ‘O04 0.03. 0.84) 0.55) LI 80Appendix 2 Table 2-1: Thermal expansion measurement of RI (TMA of GC Cristoquick II) |Temperature (°C) | TE 1%|TE2% |TE3% |TE4% |TE5%_|Average_|SD 0 0) 0 0 0) 0) 0 ol 50 0.05 0.04| 0.03) 0.05} 0.05 0.04] 0.01) 100 0.13 0.12] 0.11) 0.14! 0.13| 0.13] 0.01) 150 0.28 02 0.18 0.22! 02 0.22] 0.04! 200 04 0.33] 03 0.34] 031) 034] 0.04 250 0.54 0.46] 0.42 0.48| 0.43) 0.47] 0.05 300 09 0.83] 08! 0.85| 0.81) 0.84] 0.04 350 0.95 0.88] 0.84 0.87] 0.83) 0.87| 0.05 400 0.88 0.83] 0.77 0.83] 0.76 081] 0.05 450 0.89 0.86] 08} 0.86 0.81) 0.84] 0.04 500 0.96 0.94] 087 0.94) 0.89 0.92] 0.04 550 1.07| 1.05 0.98 1.05 1 1.03] 0.04] 600 1.29] 127] 12 127] 121 1.25| 0.04] 650 1.36] 1.32| 1.25 131) 1.26] 130 _ 0.05] 700 1.38 1.34] 1.27 133] 127] 132| 0.051 Table 2-2: Thermal expansion measurement of R2 (TMA of Shofu Cristobalite PF) Temperature CC] TE1%| 12% | TE3%| TE4% | TES % | Average] SD 0 0 0 0 0 0 a) 350 0.04 | 0.05 | 0.06 | 0.05 | 0.05 | 0.05 | 0.01 100 013 [014 [015 | 014 [014 | 014 | 001 150, 0.2 0.23 0.23 0.21 0.23 0.22 0.01 200) 034 | 038 | 038 | 036 | 039 | 037 | 0.02 250 074 {0.79 {0.77 [0.76 [079 {077 | 0.02 300 106 [is | a [i [6 [1.12 [0.04 ou 1.09 117 | 1.13 1.13 Lig | 114 0.04 400 0.99 [tir | 1.04 | 1.05 [1.13 | 1.06 | 0.06 450) or] 113 [1.05 [1.05 [1.15 [1.08 [0.06 500 1.05 [118 | Li [119 {1.12 | 0.06 550 Lu [124 [ie [116 [1.25 | 11s [0.06 600 nig [133 [125 | 2s 135127 [0.07 650 123 | 136 [128 | 128 | 137 [130 [0.06 700 125 | 138 13 13 14 133 0.06 81Table 2-3: Thermal expansion measurement of R3 (TMA of Noritake Cristobalite FF) [emperature CC) TEI % | TE2% | TES % | TE4% | TES % | Averag [SD 30, 005 {0.06 | 0.05 |_005 [0.05 [0.05 | 0.00 100 013 | 014 [013 | 0.13 [0.13 | 0.13 | 0.00 I 150) 022 | 021 | 021 | 019 [02 | 021 [001 200) 037 | 034 [035 [032 [035 | 035 [0.02 250 0.75 {0.69 | 071 | 068 [0.71 | 071 [0.03 300) 092 | 0.86 [oss | 084 | 089 | 08s [0.03 350 094 {089 [089 | 08s | 091 | 090 | 0.03 400 oss {os | osi | 076 | 084 | 082 | 0.04 450 o9 | 082 [083 [0.79 | 086 | 084 | 0.04 300 o97 | 08s | 089 | 086 | 0.93 [091 | 0.04 530 1.06 | 097 | 099 | 095 [1.02 | 1.00 | 0.04 600 123 [414 [nie [113 [as [17 [0.04 650 127 {tig [12 {ais [7122 [121 | 0.04 700) 12g [2 2r is J 24 [1.22 0.04 Table 2-4: Thermal expansion measurement of Cl (TMA of Kerr Cristobalite Inlay) Temperature (CQ) TE1% | TE2% | TE3% | TE4% | TES % | Average| SD 0 0 0 0 0 0 0 0 30 0.05 | 0.04 | 0.07 | 0.06 | 0.05 | 0.05 | 0.01 100) 015 [014 [016 [0.16 [015 [0.15 {0.01 150 022 [02 {022 | 022 | 022 | 022 | 0.01 200 0.32 | 0.29 | 031 | 032 | 031 | 031 [ 001 250 0.78 [0.72 | 0.76 | 08 | 0.78 [077 | 0.03 300 137, 1,32 135 133 133 1.34 0.02 350) 141 134 | 138 136 136, 137 | 0.03 400 134 [124 [129 | 126 [126 [128 | 0.04 450 1331.23 [127 [124 [124 [71.26 | 0.04 500 135_[ 125 [13 | 126 [126 [1.28 | 0.04 550 138 [127 [132 | 129 | 128 | 131 | 0.04 600 139 [129 [133 | 13 13 132 [0.04 650) a4ar_[ 131 [135 | 131 [132 [134 | 0.04 700 143 [134 [138 [133 [ 134 [136 | 0.04 82Table 2-5: Thermal expansion measurement of C2 (TMA of GC Cristobalite Micro) Temperature (C) | TE1% | 1E2% | 1H3% | Te4% | Te5% [AVERAGE | SD 0 o | 0 0 0 0 0 0 30 005] 005 | 005 | 005 | 0.06 (0.052 0.00 100 O14 [01s | 014 | 014 | 0.15 0.14 0.01 150 0.22 [0.23 | 022 | 02 | 0.23 0.22 (0.01 200 0.38 04 038 035_| 038 0.38 0.02 250) 0.52 | 054 | 052 | 048 | 051 051 0.02 300) 132_| 138 | 134 | 128 | 135 133) 0.04 350 137 | 145 [141 |_134 | 142 1.40 0.04 400) 131 14 135_|_127 | 136 1.34 0.05 450, 132_[ 141 136_|_127_[_137 135 0.05 500 135 [144 [139 13, 14 138 0.05 550 137_| 147 [iar [133 [1.43 1.40) 0.05 600) 139 [149 [a3 [135 | 145, Laz 0.05 650 Lar 15 144 | 136 [1.46 13 0.05 700 yas [sz [ae [138 [1.8 1.45 0.05 83Appendix 3 Table 3-1: Thermal expansion of R1 by rapid heating [Time (min.)| TE1 % | TE2% | TE3 % | TE4 % | TES % |Average| SD 0 0 0 0 0 0 0 0 0.5 0.07, 0.05 0.06 0.09 0.06, 0.07, 0.01 1 O11 0.13 0.14 0.15, 0.15 0.13 0.01 15 0.17, 0.18 0.17 0.18 0.19 0.18 0.01 2 0.20 | 0.21 | 017 | 018 | 020 | 019 | 0.02 25 0.21 0.20 0.17 0.18 0.21 0.20 0.02 3 0.22 | 0.22 | 017 | 019 | 021 | 020 | 0.02 3.5 0.22 0.23 0.17 0.19 0.22 0.21 0.03 4 0.23 | 0.23 | 017 | 0.20 | 023 | 021 | 0.03 4.5 0.25, 0.25 0.18 0.21 0.25 0.23 0.03 5 0.27 | 0.25 | 019 | 0.24 | 028 | 025 | 0.03 5.5 0.30 0.29 0.22 0.25 0.31 0.27 0.04 6 0.33, 0.31 0.24 0.29 0.34 0.30 0.04 6.5 0.38 0.34 0.26 0.32 0.34 0.33, 0.05 7 0.42 | 036 | 0.28 | 035 | 035 | 035 | 0.05 75 0.45 0.38 0.31 0.40, 0.37 0.38 0.05 8 048 | 041 | 034 | 048 | 041 | 042 | 0.06 8.5 0.52, 0.44 0.39. 0.54 0.47, 0.47, 0.06, 9 0.55 0.49 0.44 0.59 0.53 0.52 0.06 9.5 0.59 | 056 | 052 | 081 | 059 | 061 [ 011 10 0.62 0.62 0.61 0.86 0.66, 0.68 0.11 10.5 0.70. 0.67, 0.68 0.91 0.75 0.74 0.10 1 0.74 0.74 0.75, 0.97 0.84 0.81 0.10 1.5 0.79 0.79. 0.82 1.02 0.95 0.88 0.11 12 0.88 0.86, 0.89 1.09 1.04 0.95, 0.10 12.5 0.93 0.92 0.96 1.16 1 1.01 O11 13 1.04 | 098 | 111 [ 126 [ 117 | 111 | on 13.5 1.10 1.05 1.19 1,33 1.22 1.18 O11 14 125 [| 1.13 | 125 [| 139 | 126 | 126 | 0.09 14.5 1.29 1.19 130 1.42 130 1.30 0.08 15, 1,33 1.24 1.34 1.46 1.34 1.34 0.08 15.5 137 | 1.27 | 137 | 149 [| 137 [137 | 0.08 16 140 [130 | 140 | 1.52 [ 141 | 140 | 0.08 16.5 1.43 1.33 1.42 1.54 1.44 1.43 0.07 17, 144 [ 136 | 145 | 157 | 146 | 146 | 0.07 17.5 1.46 1.39 1.48 1.60 1.49 1.48 0.07 18 1.47 1.43 1.50 1.62 151 151 0.07 18.5 151 {1.44 [| 152 | 164 | 154 | 1.53 | 0.07 19 1,53 1.46 1.54 1.66 1.55 1.55 0.07 19.5 154 [| 148 | 156 | 1.67 [ 157 | 156 | 0.0720 1,55 1.49 1.58 1.69 1.59 1.58 0.07 20.5 | 157 | 1.51 _[ 1.59 | 1.70 | 1.61 | 1.60 | 0.07 21 158 1.52 1.60 171 1.62 1.61 0.07 21.5 1.59 1.53 161 1.72 1.63 1.62 0.07 22 1.60 1.55 1.63 1,73 1.64 1.63 0.07, 22.5 | 161 | 156 | 164 | 174 | 165 | 1.64 | 0.07 23 1.62_| 157 | 164 | 175 | 166 | 1.65 | 0.07 23.5 | 163 | 157 | 165 | 175 | 1.66 | 1.65 | 0.06 24 1.64 | 158 | 1.66 | 1.76 | 167 | 1.66 | 0.07 24.5 1.64 1.59 1.67 77 1.67 1.67 0.07 25 1.66 | 159 | 168 | 1.77 | 168 | 1.68 | 0.06 25.5 1.66 1.60 1.68 1.78 1.69 1.68 0.07 26 1.67 1.60 1.69 1.78 1.70 1.69 0.06 265 | 167 | 161 | 169 | 179 | 1.70 | 169 | 0.07 27 1.67 161 1.70 1.79 1,70 169 0.07, 275 | 168 | 162 | 171 | 179 | 1.71 | 1.70 | 006 28 1.68 1.62 L7L 1.80 171 1.70 ‘| 0,07 28.5 | 169 | 1.63 | 171 | 180 | 1.71 | 1.71 | 0.06 29 169 | 1.63 | 1.72 [| 181 | 1.71 | 1.71 | 0.06 29.5 1.69 1.63 1.73 181 171 171 0.06 30 1.70 | 1.6 | 1.73 [181 [1.71 [ 172 | 0.06 Table 3-2: Thermal expansion of R2 by rapid heating Time ] TE1% | TE2% | TE3% | TE4% | TES% | Average] SD (min.) 0 0 0 0 0 0 0 0.5 0.12 0.07 0.06 0.06 0.03 0.07 0.03 1 01s [013 | 013 | 014 | 010 | 013 | 0.02 15 0.17 0.17 0.18 0.19 0.16 0.17 0.01 2 0.19 0.18 0.20 0.23 0.20 0.20 0.02 25 021 | 020 | 022 | 0.24 | 022 | 022 | 001 3 0.25 | 022 | 025 | 026 | 024 | 024 | 0.01 3.5 0.30 0.25 0.27 0.28 0.26 0.27 0.02 4 0.36 0.28 0.31 0.32 0.29 0.31 0.03 4.5 0.44 0.33 0.37 0.37 0.33 0.37 0.04 5 0.53 0.40 0.44 0.43 0.38 0.44 0.06 5.5 0.63 0.47 0.51 0.51 0.45 0.51 0.07 6 073 | 055 | 059 | 061 | 052 | 060 | 0.08 65 083 | 066 | 067 | 071 | 060 | 069 | 0.09 7 0.93 0.78 0.76 0.81 0.69 0.79 0.09 75 1,02 0.87 0.86 0.93 0.78 0.89 0.09 8 1.12 1.04 0.97 1.04 0.88 1.01 0.09 858.5 1.20 1.14 1.07 1.15 0.97 1.10 0.09 9 1.30 1.29 117 1.27 1.07 1.22) 0.10 9.5 137 1.40 1.28 139 1.16 1.32) 0.10 10 1.46 1.47 1.36 147 1.25 1.40 0.10 10.5 1.52 1.53 1.43 1.55 1,33 147 0.09 ul 1.56 1.60 1.49 1.61 1.40 1.53 0.09 11.5 1.60 1.66 1.55 1.67 1.46 159 0.08 12 1.63 171 1.60 1,72 1.52 1.63 0.08 12.5 1.64 1.75 1.65 177 1.59 1.68 0.08 13 1.66 1.78 1.68 1.79 1.68 1,72 0.06 13.5 1.68 1.80 1.70 181 1.70 1.74 0.06 1.69 1.82 171 1.82 1.72 1,75 0.06 171 1.84 1.73 1.84 1.74 477 0.06, 1.72 1.85 1.75 1.86 1.76 1.79 0.06 1.73 1.87 1.77 1.88 1.78 1,80 0.06 1.75 1.88 1.78 1.87 1.80 1.81 0.06 1.76 1.90 1.79 1.90 181 1.83 0.06 177 1.91 1.80. 1.91 1.83 1.84 0.07 177 1.92 1.81 1.92. 1.84 1.85 0.07 1.78 1.93 1.82 1.93 1.85 1.86 0.07 1.79 1.94 1.83 1.94 1,86 1.87 0.07 1.79 1.95 1.84 1.95 1.87 1.88 0.07 1.80 1,95 1.85 1.96 1.88 1.89 0.07 1.81 1.96 1.85 1.96 1.89 1.89 0.07 1.81 1.97 1.86 1.97 1.90 1.90 0.07 181 1.97 1.86 1.97 191 1,90 0.07 1.82 1.98 1.87 1.97 191 191 0.07 1,82 1.98 1.87 1,98 1.92 191 0.07 1.82 1.98 1.87 1.98 1.93 1,92 0.07 1,82 1.99 1.88 1.98 1.93 1.92 0.07 1.82 1.99 1.88 1.98 1,93 1.92 0.07, 1.83 1.99 1.88 1.99 1.93 1,92 0.07 1.83 1.99 1.88 1.99 1.94 1.92 0.07 1.83 1.99 1.88 1.99 1,94 1,93 0.07 1.83 2.00 1.89 1.99 1,94 1.93 0.07 1.83 2.00 1.89 1.99 1.94 1.93 0.07 1.83 2.00 1.89 1.99 1.94 1.93 0.07 1.83 2.00 1.89 1.99 1.94 1.93 0.07 1.83 2.00 1.89 1.99. 1,94 1.93 0.07 1,83 2.00 1.89 1.99 1,94 1.93 0.07 1.83 2.00 1.89 1,99 1.94 1.93 0.07 1.83 2.00 1.88 1.99 1.94 1.93 0.07 1.84 2.00 1.88 1,99 1.94 1,93 0.07 1.84 2.00 1.88 2.00 1.94 1.93 0.07, 86Table 3-3: Thermal expansion of C1 by rapid heating Time TE1% | TE2% | TE3% | TE4% | TES% | Average sD (min) 0 0 0 0 0 0 0 0 0.5 0.07 0.04 -0.08 0.06, 0.06 0.03 0.06 1 0.13 0.11 0.02 0.12 0.11 0.09 0.06 15 0.17 0.15 0.02 0.16 0.14 0.13 0.06 2 0.20 0.17 0.05) 0.17 0.15 0.15 0.06 2.5 0.23 0.19 0.07, 0.19 0.16 0.17 0.06 3 0.26 0.21 0.09 0.22 0.18 0.19 0.06 3.5 0.28 0.23 0.12 0.25, 0.20 0.22 0.06 4 0.31 0.27 0.15 0.29 0.22 0.25 0.07 4S 0.35 0.31 0.19 0.34 0.26 0.29 0.07 5 0.40 0.36 0.24 0.39 0.30 0.34 0.07 5.5 0.46 0.42 0.30 0.45 0.35 0.40 0.07 6 0.54 0.48 0.38 0.53 0.41 0.47 0.07 6.5 0.62 0.55 0.46 0.63 0.47 0.55 0.08 7 0.71 0.66 0.55 0.73 0.54 0.64 0.09 75 0.84 0.79 0.69 0.83 0.66, 0.76. 0.08 8 0.96 0.95 0.81 0.95) 0.85 0.90 0.07 8.5 1,08 1.09 0.93 1,06 0.93 1.02 0.08 9 1.21 1.21 1.03 1.27 1.03 1.15 oul 9.5 1.34 1.33 1.13 1.35 1.16 1.26 0.11 10 1.47 1.44 1.26 1.42 1.29 1.37 0,09 10.5 1.59 1.52 141 1.48 1.39 1.48 0.08 ot 1.68 1.59 1.53 1.53 1.49 1.56 0.08 115 1.76 1.66 1.64 1.57 1.56 1.64 0.08 12 1.85 1,79 1.75 1.69 1.63 1.74 0.09 12.5 1.92 1.81 1.82 1,70 1.68 1.78 0.10 13 1.92 1.81 1.82 1.70 1.78 1.81 0.08 13.5 1,92 1.82 1.81 1.68 1.86 1.82 0.09 14 1.91 1.82 181 1.68 1.86 1.81 0.08 14.5 1.90 1.82 1.81 1.69 1.86 1.82 0.08 15 191 1,83 1.81 1.69 1,86 1,82 0.08 15.5 191 1.83 1.82 1.70 1.87 1,83 0.08 16 1,92 1.84 1.82) 1.70 1.87 1.83 0.08 16.5 1,92 1.84 1.83 1.71 1.87 1,83 0.08 17 1.93 1.84 1.83 171 1.88 1.84 0.08 17.5 1.93 1.85 1.83 1.71 1.88 1.84 0.08 18 1.94 1.85 1.84 171 1.88 1.84 0.08 18.5 1,94 1.85 1.84 1.71 1.88 1.85 0.08 19 1.94 1.85 1.84 171 1.89 1.85 0.08 19.5 1.95 1.86 1.84 171 1.88 1.85 0.09 20 1.95 1.86 1.84 1.72 1.89 1.85 0.09 E 20.5 1.96 1.86 1.84 1.72 1.89 1.85 0.09 87= 21 1,96 1.86 1.84 171 1.89) 1.85 0.09 21.5 1.96 1.86 1.84 1.72 1.89 1.85 0.09 22 1.96 1.86 1.84 1.72 1.89 1.85 0.09 22.5 1.96 1.86 1.84 1.72 1.89 1.85 0.09 23 1.96 1.86 1.84 171 1.89 1.85 0.09 23.5 1.96 1.86 1.84 171 1.89 1.85 0.09 24 1.96 1.86 1.84 171 1.89 1.85 0.09 24.5 1.96 1.86 1.84 171 1.89 1.85 0.09 25 1.96 1.86 1.84 17 1.89 1.85 0.09 25.5 1,96 1.86 1.84 171 1.89 1.85 0.09 26, 1.96 1.86 1.85 171 1.89 1.85 0.09 26.5 1.96 1.86 1.84 171 1.89 1.85 0.09 27 1.96 1.85 1.84 171 1,89 1.85 0.09 27.5 1.96 1.86 1.84 171 1.89 1.85 0.09 28 1.96 1.86 1.84 171 1.89 1.85 0.09 28.5 1.96 1.86 1.84 171 1.89 1.85 0.09 29 1.96 1.86 1.84 171 1:89 1.85 0.09 29.5 1.96 1.86 1.84 171 1.89 1.85 0.09 30 1.97 1.86 1.84 171 1.89 1.85 0.09 88Appendix 4 Mass changes of dry specimens after slow heatining [No] Target | W. before | W. after | Walter |WLAH]|WLAE] W temp. | Heating | Heating | Equilibrium | % | % | recovery% 200C | 35.3506 | 33.3625 | 33.6801 | 5.62 | 473 | 0.90 200C | 35.3534 | 33.2028 | 33.6977 | 6.08 | 468 | 1.40 200c_| 35.3492 | 33.3087 | 33.6666 | 5.77 | 4.76 | 1.01 200C_| 35.3502_| 33.2793 | 33.6697 | 5.86 | 4.75 | 1.10 200C 35.252 33.2093 33.5666 5.79 4.78 1.01 Average | 35.3311 33.2725 33.6561 5.83 474 1.09 SD 0.04 0.07 005 | 0.17 | 0.04 | 0.19 af a|oofro INo.| Target | W. before | W. after W. after |WLAH |WLAE W. temp. Heating Heating _| Equilibrium |_% %_|recovery%| [7 [2s0c [35.2569 | 32.9575 | 33.6417 | 652 | 4.58 1.94 2 | 250C 35.2722 32.9567 33.6603 6.56 | 4.57 1.99 3 | 250C 35.2614 32.9384 33.587 6.59 | 4.75 1.84 4 | 250C 35.4171 33.0741 33.7229 6.62 | 4.78 1.83 5_|_250C 35.3346 32.9957 33.6387 6.62 | 4.80 1.82 Average| 35.3084 32.9845 33.6501 6.58 | 4.70 1.89 SD 0.07 0.05 00s [004 [ou | 0.08 Target W.after | W.after [WLAH]WLAE| W. temy Heating | Equilibrium | _% | % _|recovery%| 300C 32,9925 | 33.5887 | 664 | 466 | 1.98 300C 32.8962 33.5118 6.80 5.05 1,74 300C 32,9929 33.6725, 6.62 4.69 1,92 300C 32,9354 | 33.5718 | 676 | 496 | 1.80 300C 33,0588 | 33.693 | 6.68 | 489 | 1.79 Average | 35,3218 32.95516 33.6076 6.70 4.85 1.85 SD. 0.07 0.07 0.07 0.08 [0.17 | 0.10 89Target | W. before | W. after | W.after |WLAH|WLAE | W. temp, | Heating | Heating | Equilibrium |_% | % _|recovery% 1 | 3s0c_| 35.2139 | 32.8705 | 33.5233 | 665 | 4.80 | 1.85 2 350c_| 35.2098 | 32.8489 | 33.4134 | 6.71 | 5.10 | 1.60 3 | 350c | 35.2351 | 32.8082 | 33.4914 | 6.72 | 495 |_1.77 4 3s0c_| 35.3411 | 32.9479 | 33.5286 | 6.77 | 5.13 | 1.64 3 | 350c [35.3254 | 32.9587 | 33.603 | 6.70 | 488 | 1.82 Average| 35,2651 32.8988 33.5119 6.71 497 1,74 SD 0.06 0.05 0.07 0.04 | 014 [O11 io] Target | W.befor | W.after | W.after |WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 1 400C 35,1263 32.7485 33.0922 6.77 5.79 0.98 2| 400C 35.2515 32.8699 33.2258 6.76 5.75 1.01 3 400C 35.2792 32.9134 33.2674 6.71 5.70 1.00 4 | 400C 35.3024 32.9242 33.2838 6.74 5.72 1.02 3 |_400c_| 35.3393 | 32.9507 | 33.3229 | 6.76 | 5.71 | 1.05 Average | 35.2931 | 32.9146 | 33.2750 | 6.74 | 5.72 | 1.02 SD 0.04 0.03 0.04 0.02 | 0.02 | 0.02 io] Target | W. befor | W.after | W.afer |WLAH|WLAE| Ww. temp. | Heating | Heating | Equilibrium | % | % [recovery % 1|_430c_| 35.3507 | 32.955 | 33.2726 | 678 | 5.88 | 0.90 2 | 4s0c_[35.2138 | 32.8283 | 33.1464 | 677 | 5.87 [| 0.90 3[ 450c_| "35.1869 | 32.8068 | 33.0588 | 6.76 | 6.05 | 0.72 4 450c_|~ 35.3255 | 32.9422 | 33.2332_| 675 | 5.92 | 082 5|_450c_|~ 35316 | 32.8808 | 33.1528 | 6.90 | 613 | 0.77 Average | 35.2786 | 32.8826 | 33.1728 | 6.79 | 5.97 | 0.82 SD 0.07 0.07 0.08 0.06 [ 0.11 | 0.08 90[No] Target | W. befor | W. after) W.after JWLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % [recovery % 1 500C 35.2967 32.9105 33.147 6.76 6.09 0.67 2 | sooc_| 35.1888 | 32.7899 | 33.0706 | 682 | 6.02 | 0.80 3 | sooc [35.2565 [329216 | 33.2026 | 662 | 5.83 | 0.80 4 | 500C 35.374 32.9687 33.2368 6.80 6.04 0.76 5 | 500C 35.3217 32.9228 33.1797 6.79 6.06 0.73 Average | 35.2875 32.9027 33.1673 6.76 6.01 0.75 SD 0.07 0.07 0.06 0.08 | 011 [ 0.05 io] Target | W. befor | W.after | W.after ]WLAH [WLAE _| temp. | Heating | Heating | Equilibrium | _% | % _|recovery% 1 s50c | ~35.1831 | 32.7709 | 33.0306 | 686 | 6.12 | 0.74 2| s50c_|_ 35.1509 | 32.7612 | 32.9805 | 680 | 617 | 0.62 3 [ 350c_|_35.0867_| 32.7071 [32.9425 | 678 | 6.11 | 0.67 4 | s50c_|_ 35.295 | 32.8634 | 33.1126 | 689 | 618 | 071 3 | s50c_ | 35.3471_[ 32.9355 | 33.1757 [| 6.82 | 614 | 068 Average [35.2126 | 32.8076 | 33.0484 | 683 | 615 | 068 SD oul 0.09 010 | 0.04 | 0.03 [ 0.04 [No] Target | W. befor | Wafer ] W.after |WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | _% | % _|recovery%| 1 | 600c | 35.2577 | 32.8417 | 33.0726 | 6.85 | 620 | 0.65 2 600c | 35.3485 | 32.9396 | 33.1791 | 681 | 6.14 | 0.68 3 | 600 | 35.3223 | 329287 | 33.1549 | 678 | 6.14 | 0.64 4 | 600C 35.3943 32.9926 33.209 6.79 | 6.17 0.61 5 600C 35,3559 32.9439 33.1577 6.82 | 6.22 0.60 Average | 35.3357 | 32.9293 | 33.1547 | 681 | 617 | 064 SD 0.05 0.05 0.05 | 0.03 | 0.04 | 0.03 91io] Target | W. befor | W. afer] W. after _| temp. | Heating | Heating | Equilibrium 1] 650c | 35.2473_[ 32.8439 | 33.0426 2 | 650C [~35.3228 [32.9129 | 33.1121 3 | 650 | 35.2747_| 32.8553 _| 33.0561 4 5 650C 35,3631 32.9371 33.1425 650C 35.36 32,9421 33.141 6.84 | 6.28 Average| 35.3136 [| 32.8983 | 33.0989 | 6.84 [ 6.27 sD 0.05 0.05 0.05 0.02 0.01 [No] Target W. after |W. after W. temp. Heating | Equilibrium | _% | %__|recovery% 1 [_700€ 32.9035 | 33.0657 | 6.83 | 637 | 0.46 2 700C 32,9658 33.1381 6.84 6.36 0.49 3 700C 32.9474 33.1364 6.86 6.33 0.53 4 700C 32.9961 33.2061 6.89 6.30 0.59 3 | 700C 32,8674 | 33.0654 | 6.92 | 636 | 0.56 Average | 35.3653 32,9360 33.1223 6.87 6.34 0.53 SD 0.05 0.05 0.06 0.04 | 0.03 | 0.05 Mass changes of dry specimens after rapid heating INo.| Target | W. befor | W. after WLAH |WLAE] W. temp. | Heating | Heating % _|_% _|recovery% 200 35.2619 32.8782 33.3402 6.76 5.45 131 200 35,3421 33.0003 33.4499 6.63 5.35 1.27 200 | 35383 | 33.0119 | 33.439 | 670 | 549 | 121 200_ | 35.28 | 329713 | 33.3298 | 654 | 553 | 1.02 200 | 35.2265 [329274 | 33301 | 653 | 547 | 1.06 Average| 35.329 | 32.96347 [33.4097 _| 6.70 | 5.43 |__1.26 sD 0.06 0.07 0.06 0.07 0.07 0.05 alafefo)a 92INo.] Target | W. befor | W.after | W.after |WLAH|WLAE] W. ‘temp. | Heating | Heating | Equilibrium | _% | % _|recovery% 1 250 35.4113 33.0239 33.3811 6.74 5.73 1.01 2 | 250 | 35.4526 [33.0487 | 33.4291 | 6.78 | 5.71 |_ 1.07 3 | 250 | 35.4927 [33.1068 | 33.4703 | 672 | 5.70 | 1.02 4 | 250 | 35.3367 | 32.9529 | 33.3264 | 675 | 5.69 | 1.06 5 250 35.3386 32.9398 33.3227 6.79 5.70 1.08 Average} 35.4064 33.0144 33.3859 6.76 5.71 1.05 sD 0.07 0.07 0.06 0.03 0.02 0.03 INo.| Target | W. befor | W.after | W.after [WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % [recovery % 1 |_300 | 353686 | 32.9855 | 333014 | 674 | 5.68 | 1.06 2 | 300 | 353218 | 329145 [ 33.2518 | 682 | 5.86 | 0.95 3 | 300 | 353699 | 32.9708 | 33.302 | 678 | 585 | 0.94 4] 300 | 35.324 | 32909 | 33.2438 | 684 | 5.89 | 0.95 S| 300 | 35.4122 [ 33.0005 | 33349 | 681 | 583 | 098 Average | 35.3593 32.9561 33.3016 6,80 5.82 0.98 SD 0.04 0.04 0.05 0.04 | 0.08 | 0.05 [No.[ Target | W. befor | W. after | W. after [WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % [recovery % 1 |_350__| 353743 | 33.0169 | 33.3528 | 6.66 | 5.71 | 0.95 2 [350 | 35.2903 | 329019 | 33.2491 | 677 | 578 | 098 3 350 35.4005 33.0062 33.3313 6.76 5.85 0.92 4 | 350_| 35.3954 [ 32.9827 | 33.3018 | 682 | 5.91 | 0.90 5 350 35.4346 33.0293 33.3352 6.79 5.92 0.86 6 350 35.2279 32.801 33.079 6.89 | 6.10 0.79 Average | 35.3538 | 32.9563 | 33.2749 | 678 | 588 | 0.90 SD 0.08 0.09 0 0.07 0.07 93No.) Target | W. befor | W.after | W.after |WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % recovery 1 | 400 [353691 | 32.9825 | 33.3073_| 6.75 | 5.83 2 | 400 [| 353473 | 32929 | 33.1965 | 684 | 6.08 | 0. 3 | 400 [ 353088 | 32.9052 | 33.175 | 681 | 604 | 0.76 4 {400 [35.3586 | 32.9557 | 33.2268 | 680 | 6.03 | 0.77 5 400 35.3036 32.8767 33.1515 6.87 6.10 0.78 Average| 35.3375 32.9298 33.21142 6.81 6.02 0.80 Lo sD 0.03 0.04 0.06 0.05 O11 0.07 [No.] Target | W.befor | W.afer | W. after JWLAH|WLAE] W. temp. | Heating } Heating | Equilibrium | % | % |recovery % 1 | 450 | 353916 | 32.9757 | 33.2245 | 683 | 612 | 0.70 2 450 35.3767 32.967 33.2279 6.81 6.07 0.74 3 | 450 [ 35.2945 | 32801 | 33.1548 | 681 | 6.06 | 0.75 4 | 450 [ 353498 | 329303 | 33.1957 | 684 | 6.09 | 0.75 5 450 35.3878 32.9598 33.2456 6.86 6.05 0.81 Average | 35.3601 32.9448 33.2097 6.83 6.08 0.75 sD. 0.04 0.03 0.04 0.02 0.03 0.04 [No.] Target | W. befor | W. after | W. after [WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 33.2088 6.84 | 6.10 0.74 32.8884 33.1538 6.94 6.18 0.75 32.9147 | 33.1781 | 684 | 610 | 0.75 32.9035 | 33.1625 | 685 | 612 | 0.73 32.9098 | 33.162__| 683 | 612 | 0.71 32.9126 | 33.1730 | 686 | 612 | 0.74 0.02 0:02 0.04 | 0.04 | 0.01INo.| Target | W. befor | W.after | W.after |WLAH]|WLAE| W. temp. | Heating | Heating | Equilibrium} % | % [recovery % 1 |_550_| 35.2874 | 32.8805 | 33.152 | 682 | 605 | 077 | 2] 550 | 35.2113 | 32.7754 | 33.0193 | 692 | 623 | 0.69 3 550 35.3497 32.9455 33.1869 6.80 | 6.12 0.68 4 550 35.3564 32.9484 33.1954 6.81 6.11 0.70 s[ 350_| 35.3943 | 32.9466 | 33.2051 | 692 | 619 | 0.73 Average | 35.3198 | 32.8993 | 33.1517 | 685 | 614 | O71 SD. 0.07 0.07 0.08 0.06 | 0.07 0.04 INo.| Target | W. befor | W.after | W. after [WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium |_% | % _|recovery%| 1 600 35.3089 32.8339 33.1142 7.01 6.22 0.79 2] 600 | 35.1946 | 32.7875 | 33.0423 | 684 | 612 | 0.72 3 | 600 [| 35.3494 | 32.9412 [33.1565 | 681 | 620 | 0.61 4 {600 [35.3359 | 32.9262 | 33.1573 | 682 | 617 | 0.65 3 [600 | 35.4022 | 32.9984 | 33.2346 | 679 | 612 | 0.67 Average | 35.3182 | 32.8974 | 33.1410 | 685 | 616 | 0.69 SD 0.08 0.09 0.07 0.09 | 0.05 | 0.07 INo.| Target | W. befor | W.after | W.after [WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % _|recovery%| 1 | 650 _| 35.4491 | 33.0307 | 33.2451 | 682 | 6.22 | 0.60 2] 650 | 35.2948 | 32.8833 | 33.0939 | 683 | 624 | 0.60 3 650 35.4186 33.0013 33.2189 6.82 6.21 0.61 4 [650__[35.4447_| 32.9989 [ 33.2179 | 690 | 628 | 0.62 S| 650 | 35.4183 | 32.9825 | 33.2035 | 688 | 625 [ 0.62 Average | _ 35,4051 32.9793 33.1959 6.85 6.24 0.61 sD 0.06 0.06 0.06 0.04 0.03 0.01 95[No] Target | W. befor | W.after | W.after ]WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 1 700 35.3264 32,8932 33.084 6.89 6.35 0.54 2 |_700 | 35.3307_| 32.9068 _| 33.0872 | 686 | 635 | 0.51 3 700 35.3726 32.9523 33.1108 6.84 6.39 0.45 4 [700 | 35.3434 [| 329298 | 33.0961 | 683 | 636 | 047 S| 700 | 35.2289 | 328132 | 32.9848 | 686 | 637 | 0.49 Average| 35.3204 | 32.8991 | 33.0726 | 6.86 | 636 | 0.49 SD 0.05 0.05 0.05 0.02 [ 0.02 | 0.04 Mass changes of wet specimens after rapid heating PNo.| Target ] W. befor] W.after | W.after |WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % recovery % 1 [200 [35.0689 [32.9202 | 33.1653 | 6.13 | 543 | 0.70 2 [200 | 35.0047 | 329199 | 33.131 | 6.20 | 5.60 | 0.60 3 | 200 | 35.1728 | 32.9645 [ 33.1894 | 6.28 | 5.64 | 0.64 4 200 35.1189 32.9145 33.1531 6.28 5.60 0.68 5 200 35.1489 32,9505 33.1765 6.25 5.61 0.64 ‘Average | 35.1208 SD 0.04 INo.| Target ] W. befor] W.after | W.after |WLAH]|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 35.2293 | 329118 | 33.1775 | 658 | 5.82 | 0.75 35.1377 32.812 33.084 6.62 5.84 0.77 35.189 | 32869 | 33.1356 | 659 | 584 | 0.76 35.1585 | 32.9915 | 33.2735 | 6.16 | 536 | 0.80 35.1267 | 32.9551 | 33.2098 | 618 | 5.46 | 0.73 35.1682 32.9079 33.1761 6.43 5.66 0.76 0.04 0.07 0.07 0.23 0.24 0.03 96[No] Target | W.befor | W.after | W.after |WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 35.1284 | 32.8585 | 33.1271 | 6.46 | 5.70 | 0.76 35.0971 | 32.8452 | 33.103 | 642 | 5.68 | 073 35.2078 32.9453 33.2055 6.43 5.69 0.74 35.1696 | 32.8976 | 33.1708 | 6.46 | 5.68 | 0.78 35.1589 | 32.9004 | 33.1588 | 642 | 5.69 | 0.73 | 35.1524_| 32.8894 | 33.1530 | 644 | 5.69 5 0.04 0.04 0.04 [0.02 | 0.01 2 [No] Target | W.befor | W.after | W.after JWLAH]|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 1 | 350_| 35.0793 | 32.7881 | 33.0269 | 653 | 5.85 | 0.68 2|_ 350 | 35.1054 | 328347 | 33.0738 | 647 | 5.79 | 0.68 3 | 350 | 35.0397 | 32.7722 | 33.0132 | 647 | 5.78 | 0.69 4 | 350 | _35.0963_|_32.8268 | 33.0535_| 6.47 | 5.82 | 0.65 5 350 35.0885 32.8042 33.0581 6.51 5.79 0.72 Average | 35.0818 | 32.8052 | 33.0451 | 649 | 5.81 | 0.08 ) 0.03 0.03 0.02 | 0.03 | 0.03 | 0.03 INo.] Target | W. befor | W.after | W.after [WLAH|WLAE] W. temp. | Heating | Heating | Equilibrium | % | % recovery % 1 | 400_| 35.0904 [32.795 | 33.0213 | 654 | 590 | 0.64 2 | 400 | 35191 | 32912 | 33.1348 | 648 | 5.84 | 0.63 3 | 400 | 35.081 | 32.7921 | 33.0215 | 652 | 5.87 | 0.65 4 | 400 | 35.1246 | 32.8443 [ 33.0898 | 649 | 5.79 | 0.70 3 | 400 | 35.1806 _[ 32.9069 | 33.0994 | 646 | 592 | 055 Average | 35.1335 | 32.8501 | 33.0734 | 650 | 5.86 | 0.64 sD 0.051 0.058 0.050 0.033 | 0.048 0.055 97No. é Target | W.befor | W.after | W. after [WLAH|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % |recovery 450 35.0138 | 32.7359 | 32.9571 _| 6.51 | 5.87 | 0.63 450 35.0865 32.7902 33.015 6.54 | 5.90 0.64 450 34.9224 | 32.7174 | 32.9425 | 631 | 5.67 | 0.64 450 35.0764 32.7774 32,9987 6.55 | 5.92 0.63 450 35.06892 | 32.7352 32,9797 6.65 | 5.96 0.70 Average| 35.0336 32.7512 32.9786 6.51 | 5.87 0.65 sD 0.068 0.031 0.030, 0.125 | 0.114 | 0.028 afafofof— W. befor | W.after | W.after JWLAH|WLAE] W. Heating | Heating | Equilibrium] % | % [recovery % 35.0127 | 32.7538 | 32.9682 | 645 | 5.84 | 0.61 35.0419 | 32.7568 | 32.9773 | 652 | 589 | 0.63 35.1262 32.8293 33.05 6.54 5.91 0.63 35.0876 | 32.7964 | 33.0112 | 653 | 592 | 0.61 35.0749 _| 32.7892 | 33,0006 | 6.52 | 591 | 0.60 Average | 35.0687 | 32.7851 | 33.0015 | 6.51 | 5.89 | 0.62 sD 0.04 0.03 0.03 0.03 [0.03 [0.01 W. befor | W.after | W. after [WLAH|WLAE] W. Heating | Heating | Equilibrium} % | % recovery 35.0547 _| 32.7933 | 33.0051 | 6.45 | 5.85 [| 0.60 35.0654 32.8098 33.0293 6.43 | 5.81 0.63 35.0863 32.7747 33.002 6.59 | 5.94 0.65, 35.0889 32.7798 33.0006 6.58 | 5.95 0.63 35.0794 32.7658 32.9974 6.60 | 5.94 0.66 35.0749 _| 32.7847 | 33.0069 | 6.53 | 5.90 | 0.63 0.01 0.02 0.01 0.08 | 0.07 0.02 98INo.] Target | W.befor | W.afier | W.after [WLAH]|WLAE| W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 1 | 600 | 35.1465 | 32.8476 | 33.0384 | 654 | 6.00 | 0.54 2 | 600 | 349912 | 32.7403 | 32927 | 6.43 | 5.90 | 053 3 | 600 | 35.0642 | 32.7289 | 329247 | 6.66 | 6.10 | 0.56 4 600 35.1124 32.8096 32,9976 6.56 6.02 0.54 3 | 600 | 35.0987 | 32.7905 | 32.9963 | 658 | 5.99 | 059 Average 35.083 32.783 32.977 6.55 6.00 0.55 sD 0.06 0.05 0.05 0.08 | 0.07 |_0.02 No.) Target | W. befor | W.after | W.after |WLAH]WLAE] W. temp. | Heating | Heating | Equilibrium | % | % |recovery % 1|_650_| 35.006 | 32.7106 [ 32.8847 | 656 | 606 | 0.50 2 | 650 | 35.1325 | 32.8517 | 33.024 | 649 | 6.00 | 0.49 3 | 650 | 35.1505 | 32.8056 | 33.0619 | 667 | 5.94 | 0.73 4{ 650 | 35.1237 | 32.8321 | 33.0145 | 652 | 601 | 052 5 | 650 | 35.1189 | 32.7996 | 33.0158 | 6.60 | 5.99 | 0.62 Average | _35.1063_| 32.7999 | 33.0002_| 6.57 | 6.00 | 0.57 SD 0.06 0.05 007 | 0.07 | 004 | 0.10 io] Target | W.befor | Wafer | Waller |WLAH |WLAE] W. temp. | Heating | Heating | Equilibrium | % | % _|recovery% 1 700 35.0837 32.8019 32.97 6.50 6.02 0.48 2 700 35.138 32.8535 33.0213 6.50 6.02 0.48 3 700 35.1735 32.8767 33.0377 6.53 6.07 0.46 4{ 700 | 35.1456 | 32.7894 | 32.9682 | 6.70 | 6.20 | 0.51 S| 700 | 35.1567 _| 32.8073 [ 32.9454 | 668 | 629 | 039 Average 35.140 32.826 32.989 6.58 6.12 0.46 2) 0.03 0.04 0.04 0.10 0.12 0.04 99