HARMONIZATION OF VISCOSIMETRIC AND THERMODYNAMIC DATA FOR INDUSTRIAL MULTI-COMPONENT GLASSES AND GLASS MELTS Reinhard Conradt Aachen

University Institute of Mineral Engineering and Department of Glass and Ceramic Composites Mauerstrasse 5 52064 Aachen Germany

ABSTRACT A thermodynamic model used earlier with success for the prediction of glass properties is applied to nine industrial multi-component glasses, comprising E fibre, C fibre, stone wool, float, TV panel, and low expansion glasses. Data for the zero Kelvin entropy (vitrification entropy) Svit and the jump cP of the heat capacity at the glass transition temperature are derived. The same data are derived by an evaluation of the viscosity-temperature relation by means of the AdamGibbs equation. In general, the data derived by both approaches agree very well. However, in individual cases (Svit of the E fibre; cP of the float glass), larger deviations are found, which are exploited to identify shortcomings in the thermodynamic data base. INTRODUCTION Thermodynamic data of multi-component glass-forming systems have been successfully modeled in the past (see, e.g., [1-2] for geochemically relevant systems, and [3] for metallurgical slags). Calculated integral and partial molar properties, such as standard heats and Gibbs energies of formation, or chemical potentials of individual oxides agreed well with experimental data. By an own model which was designed for the composition of commercial glasses, the energy consumption of the batch-to-melt conversion or the hydrolytic stability of glasses was predicted in a reliable way [4-6]. However, experimental thermodynamic data for multi-component systems relevant to the glass industry are scant. Therefore, the verification and improvement of the model proceeds at a slow pace. The lack of thermodynamic data can be compensated, at least to a certain extent, by a systematic evaluation of viscosity data. This is the focus of the present paper. The scientific basis of this approach is not new. It dates back to the work by Adam and Gibbs [7] and has been applied with success to broaden the data base of one- and multi-component magmatic systems, see [8-9] and [10], respectively, and of nuclear waste glasses [11]. In the present paper, the approach is extended to viscosity data of industrial glasses, thereby exploiting the advantage that the glass industry possesses a host of reliable data of this type. The scope of this investigation comprises nine industrial glasses, among which are different man-made mineral fibre glasses, a float glass, a TV panel and a low expansion (Pyrex or Duran type) glass. THEORY Brief sketch of a thermodynamic model The model outlined below has been used with success to predict the properties of rigid glasses and glass melts from their chemical composition. The model consists of two parts, (1) an

appropriate thermodynamic description of glass-forming one-component systems, and (2) an extension of this description to multi-component systems. The thermodynamics of a one-component system in its stable liquid, metastable undercooled, glassy, and crystalline state at an ambient pressure of P = 1 bar is described by the following seven quantities in a comprehensive way. These are: H S Hfus Tliq cP(T) Hvit Svit cP Tg = = = = = the standard enthalpy at 298 K, for the crystalline solid, stable at T = Tg, the standard entropy at 298 K, for the crystalline solid, stable at T = Tg, the enthalpy of fusion, the liquidus temperature, the heat capacity of the crystalline solid as a function of temperature; represented by the polynomial cP(T) = A + BT + C/T2, the vitrification enthalpy, the vitrification entropy (zero Kelvin entropy of the glass), the jump of the heat capacity at the glass transition temperature, the glass transition temperature.

= = = =

In principle, all quantities referring to the glassy state depend on the cooling rate at which this state is reached. With the cooling rate defined, they assume unambiguous values. The details are not elaborated here. The set of quantities Hfus, Sfus, Tliq, Hvit, Svit, cP, and Tg is redundant. It is linked by the relations given in eqs. 1 to 3 a-c as specified in figure 1 a-b. Hc(T) and Sc(T) denote the configurational enthalpy and entropy, respectively.

S fus = H fus / Tliq

H C (T) = H
vit

(1)
T T liq

+ (c P ,liq c P ,cryst ) dT
Tg

=H

fus

(c P,liq c P,cryst ) dT

H vit + c P T Tg H H vit
and

fus

c P Tliq T

(2 a-c)

fus

c P Tliq Tg

)
Tliq

S C (T) = S vit +

Tg

c P ,liq c P ,cryst T Tg T Tliq Tg

dT

= S fus Tliq T

c P ,liq c P ,cryst T

dT

S vit c P ln

S fus c P ln

(3 a-c)

S vit

S fus c P ln

The knowledge of any four of the above redundant set of quantities is sufficient to derive the rest. As shown by a large number of calorimetric experiments [9], the error introduced by the approximation of the real shape of the cP jump by a constant value is insignificant; vitrification enthalpy values Hvit derived from the approximated cP(T) curves agree well with Hvit values directly measured. Thus HC(T) and SC(T) may be calculated as suggested by eqs. 2 c and 3 c.

undercooled melt

melt cryst., glass

area = heat capacity cP H

fus

-H

vit

area = S cryst. cP / T

fus

-S

vit

undercooled melt melt cryst.

cryst., glass 298 K Tg temperature T Tliq 298 K Tg temperature T Tliq

Fig. 1 a-b. Illustration of equations 2 a-c and 3 a-c; arbitrary units; the assumption that below Tg, cP(glass) cP(cryst), is valid in good approximation if the crystalline phase stable at Tg is taken into consideration The identification of the crystalline reference state of a one-component system is simple. It is usually polycrystalline but contains chemically identical phases. The crystalline reference state of a multi-component system, by contrast, is chemically heterogeneous. The thermodynamic description of a multi-component system in terms of crystalline reference states is a challenging task requiring strategies to identify the coexisting phases and to quantify their amounts. Once this problem is solved, a multi-component system is treated the very same way as outlined above, i.e., by assessing the enthalpy and entropy differences between the crystalline state and the corresponding glass or melt, respectively. An adequate strategy is developed by exploiting three fundamental principles found to be valid in the mineral world. These are: the principle of majority partition. By experience, even complicated multi-component systems, such as magmatic and igneous rock melts, metallurgical slags, commercial glasses, etc., can be represented by a predominant quaternary typically comprising more than 85 95 % of the oxides on a molar basis.

 the principle of parsimony. The very large number of combinatorial possibilities of compound formation is not exploited by nature. Rather, a quite limited set of binary and ternary compounds is found. The constitutional relations in a given multi-component system are therefore approximated in the following way: First, the minority oxides are allotted to a set of normative phases as suggested by the CIPW norm calculation (see e.g. [12]). The remaining four majority oxides are allotted to the respective constitutional sub-range in the predominant quaternary identified and reconstructed by the evaluation of existing phase diagrams. the principle of medium-range order mixing. Systems with a strong tendency to compound formation do not mix on a scale equivalent to 61023 per g-atom, not even in the liquid state way above Tliq. Therefore, when a system is expressed in terms of stoichiometric entities k with compositions identical to the co-existing mineral phases, then the contributions of mixing are minimized to an extent that they may be neglected. This has been formulated in detail before [13] and is well in line with experimental findings [14]. Consequently, a thermodynamic quantity Z, where Z may denote an enthalpy H, entropy S, or Gibbs energy G, of a multi-component system is obtained from the molar amounts nk and the quantities Zk of the pure compounds by a relation as simple as Z = nkZk . (4)

Eq. 4 is valid for the crystalline as well as for the liquid and glassy state if the k are taken in the respective state. Recently, the model was submitted to a stringent test: By own work, Gibbs energies of formation were calculated for four different mineral fibre glasses (alumina rich alkali + alkaline earth alumosilicate glasses containing iron oxide and further minor additions). The values were checked by calorimetry by an independent laboratory [15], yielding the following experimental vs. calculated values for the standard Gibbs energies of formation from the elements (in kJ per mol of oxides): -852.0 vs. -849.6; -865.0 vs. -867.2; -880.8 vs. -881.8; -855.4 vs. -852.7. The standard Gibbs energies of formation from the oxides read: -12.9 vs. -10.6; -35.4 vs. -37.7; -34.0 vs. -35.0; -44.1 vs. -41.4. Adam-Gibbs analysis of industrial glasses The model, as successful as it may have been in individual cases as above, suffers from a general lack of opportunities to be put to the test. This is simply because thermodynamic data, specifically, data for Svit, Hvit and cP, are rarely available for industrial products. Thus verification of the model and its data base proceeds very slowly. Therefore, use is made of the fact that glass producers need to have a good command of workability and cooling. In other words: They usually know the chemical composition and viscosity-temperature relation of their glasses well. Such data can be submitted to an analysis by the Adam-Gibbs equation [7], yielding information on Svit and cP. There is a host of data available for this approach, which have hardly ever been exploited. The method, however, has been used in the past to confirm thermodynamic data of glasses of predominantly scientific interest [9].

The Adam-Gibbs relation predicts a linear relationship between log and the reciprocal value of the product of configurational entropy SC(T) (see eq. 3 a-c) and absolute temperature: log = A + D Tg T S C (T ) . (5)

Employing eq. 3 b yields

log = A + D f (T ) with

(6)

f (T ) =

Tg T S vit

1 Tg c P 1 vit ln T S

(7)

For a set of experimentally determined viscosity data, eqs. 6-7 generate a linear relationship versus Tg/(TSC) for one distinct ratio of the so-called structure parameter a = cP/Svit only. After determining a by an incremental approach to optimal linearity (as, e.g., reflected by a maximum regression coefficient r2), optimal values for the intercept A and slope D in eq. 6 are obtained which are, in turn, converted to estimates of Svit and cP by

S vit =
and

D Lg A

(8)

c P = aS vit . In eq. (8), Lg denotes the decadic logarithm of the viscosity at Tg: Lg = log (T=Tg).

(9)

Thermodynamic modeling of vitrification entropies and jumps of the heat capacities In parallel to the above analysis, Svit and cP values are calculated from the glass composition by means of the constitutional model. The database used stems from various sources and is compiled in [16]. For glasses from the system Na2O-B2O3-SiO2, a revision of the database was implemented. The author has been noticing that for some reason, the constitutional model generated grossly erroneous results in the silica rich corner of the system. Existing phase diagrams do not seem to reflect the structural relations in the glasses well. Compounds of the type Na2OB2O3nSiO2 are often ignored, in spite of experimental and theoretical evidence [17, 18]. Polyakova [18] states that in lithium and sodium borosilicate systems, the structural groupings which exist in the vitreous state cannot form any corresponding crystalline structures for steric reasons. In the homologous sequence of potassium, rubidium, and cesium borosilicates, however, crystalline compounds isostructural to leucite, i.e., R2OB2O34SiO2, are formed, leading to the

suggestion [18] that lithium and sodium borosilicate glasses should be described in reference to such a compound as well. In order to implement a latent sodium boroleucite compound in the constitutional model, data for a hypothetical crystalline compound Na2OB2O34SiO2 are estimated from tabulated data for leucite Na2OAl2O34SiO2, NaBO2, NaAlO2, Al2O3, and B2O3. This is done under the assumption that H(Na2OB2O34SiO2) H(Na2OAl2O34SiO2) + 2H(NaBO2) 2H(NaAlO2), S(Na2OB2O34SiO2) S(Na2OAl2O34SiO2) + S(B2O3) S(Al2O3). The set of data thus obtained is refined against calorimetric data for the Gibbs energy of formation (from the oxides) of a glass with a composition (by wt.) of 14.21 Na2O, 20.21 B2O3, 65.58 SiO2, yielding -(45.300.81) kJ/mol [11]. The thermodynamic data obtained as described above are compiled in table 1. Figure 2 illustrates the constitutional relations allowing for the formation of a latent boroleucite compound. Tab. 1. Thermodynamic data for compounds k from the system Na2O-B2O3-SiO2; N = Na2O, B = B2O3, S = SiO2; M = molar mass in g/mol; H = enthalpy in kJ/mol, G = Gibbs energy in kJ/mol, T = temperature in in K; A, B, C = constants for the calculation of the heat capacity cP in J/(molK), by the polynomial cP = A + BT + C/T2; superscripts: = standard state at 298 K, 1 bar; = formation from the elements; vit = vitrification; tr = transition; data for the hypothetical compound NBS4: own estimates; the rest after data compiled in [16, 19]
M 340.455 201.217 131.598 371.934 -H S -G Hvit Svit Ttr Htr A 345.18 704.28 206.10 444.88 101.21 292.88 325.89 540.97 B10+3 C-5

k NB4

state

s liq NB2 s liq NB s liq NBS4 s liq

5902.8 276.1 3284.9 189.5 1958.1 147.1 5710.9 270.0

298 1085 130.4 3089.7 48.8 18.5 298 1016 81.2 1838.8 43.6 19.5 298 1239 72.5 5367.9 42.7 21.1 298 1123 71.1

5543.0 58.3 40.1

226.35 -95.81 77.11 -37.49 107.34 0.00

172.36 -63.47

RESULTS Table 2 shows the oxide compositions of six industrial glasses submitted to an Adam-Gibbs analysis. Experimental viscosity data are shown in figure 3 in terms of a Vogel-FulcherTammann plot. The glasses depicted cover a wide range of industrial products. In table 3, the same glasses are presented in terms of their constitutional compounds k. This presentation is the basis for the thermodynamic calculation of Svit and cP. The set of glasses is complemented by four stone wool type mineral fibre compositions, i.e., three recent ones and a former one melted from natural basaltic rock. The compositions of the latter glasses are given in terms of compounds k in table 4.

SiO2

NS2 NBS4 NS N 2S

B2O3
Fig. 2.

NB4 NB2

NB

N 2 B N3 B

Na2O

Constitutional relations in the ternary system Na2O-B2O3-SiO2; the open circle marks the composition of a glass investigated by calorimetry [11]

Tab. 2.

Composition of glasses DGG-1 [20], JM-753C [21], E fibre [22], low expansion (low ) [22], and TV panel [22], given as wt. % of oxides j float DGG-1 71.7 0.1 1.2 0.2 4.2 6.7 C fibre JM-753C 63.4 E fibre 55.15 0.57 14.42 6.86 0.44 4.22 17.73 low 80.99 TV panel 61.76 0.43 1.40 2.07 0.04 0.05 9.22 9.26 0.51 0.01 7.67 7.58

oxide j SiO2 TiO2 ZrO2 Al2O3 B2O3 Fe2O3 MgO CaO SrO BaO ZnO Li2O Na2O K2O SO3

5.1 4.8 3.1 6.2

2.19 12.60 0.04 0.01 0.02

15.0 0.4 0.4

15.6 1.0 0.2

0.61

0.01 4.09 0.05

Tab. 3.

Composition of five industrial glasses (see table 2), given in terms of normative compounds k in g per 100 g glass; for the C fibre glass (wool) and the low glass, the speciation using the compound Na2OB2O34SiO2 is shown; for DGG-1 (float glass), the thermodynamically correct speciation requiring the compound Na2OMgO4SiO2 [23] was approximated by a speciation using MgOSiO2 float [20] C fibre [21] E fibre [22] low [22] DGG 1 JM-753C 0.17 0.04 0.43 0.04 0.03 TV panel [22] 0.04 0.70 2.08 0.43 0.03 14.57 16.52 11.29 12.90

compound k

FeOFe2O3 FeOSiO2 ZnO2SiO2 ZrO2SiO2 TiO2 0.14 Li2OSiO2 SrOSiO2 BaO2SiO2 K2OAl2O36SiO2 2.26 5.95 K2O2SiO2 Na2OAl2O36SiO2 4.23 20.82 B2O3 Na2OB2O34SiO2 25.84 MgOSiO2 10.46 CaOAl2O32SiO2 CaOMgO2SiO2 16.78 Na2OMgO4SiO2 *) CaOSiO2 3.94 Na2O3CaO6SiO2 23.75 Na2O2SiO2 35.36 26.31 SiO2 23.61 *) no thermodynamic data available for this compound

0.57 0.03

0.32 5.19 6.86 10.96 9.46 16.77

36.59 22.67 9.30

0.04 0.02 0.10 22.54 18.80

18.39

62.38

For the stone wool type fibre glasses, viscosity data can be measured at temperatures above Tliq only. Due to their poor stability against crystallization, a major part of the viscosity temperature curve is hidden behind the crystallization curtain. Figure 4 shows that all industrial glasses yield straight lines in the Adam-Gibbs plot. For reasons of comparison, data for glassy anorthite are added. For anorthite glass, the following values have been measured [9]: cP = 34.1 J/(100 gK) and Svit = 13.1 1.4 J/(100 gK). The quality of the viscosity data analyzed in the present paper and the achieved linearity form an excellent basis to calculate cP and Svit. The high-T viscosity data of the stone wool type glasses (see figure 5) accumulate around the so-called fibrization level of log = 1.5 ( in dPas). For these glasses, the linear regression analysis was performed on the high-T data alone. As the resulting straight lines match the respective data points at Tg (for basalt less well than for the rest), they may be considered a sufficiently reliable basis for a determination of cP and Svit as well.

13 11
log , in dPas

E fibre glass low glass

9 7 5 3 glass wool JM-753C 1 400 600 800 1000 Tg/T 1200 1400 1600 TV panel glass

float glass DGG-1

Fig. 3.

Viscosity-temperature relation of five different industrial glasses; lines: calculated from eqs. 6-7; symbols: experimental data (float glass [20]; C glass wool [21]; E fibre, low , TV panel glass [22];)

Tab. 4.

Composition of four stone wool type fibre glasses, given in terms of normative compounds k in g per 100 g glass fibre 1 fibre 2 fibre 3 basalt 2.10 7.43 7.89 0.34 4.64 4.27 2.20 12.96 6.35 16.44 15.84 18.76

compound k P2O53CaO FeOFe2O3 FeOSiO2 MnOSiO2 CaOTiO2 K2OAl2O36SiO2 K2OAl2O32SiO2 Na2OAl2O36SiO2 Na2OAl2O32SiO2 MgOSiO2 CaOAl2O32SiO2 CaOMgO2SiO2 Na2O3CaO6SiO2 Na2O2SiO2 SiO2

2.88 0.55 0.28 0.34 2.37 5.51 2.24 41.58 40.70 3.40

5.67 1.08 0.31 0.58 1.78 7.61 3.82 41.86 28.71 8.32

6.98 1.33 0.37 0.58 1.60 8.56 19.40 41.70 7.05 12.10

16 E fibre glass 14 12
log , in dPas

low glass

10 8 6 4 2 0 -2 0

glassy anorthite TV panel glass

float glass DGG-1 glass wool JM-753C

10

12

14

Tg/(TSC) in (gK)/J

Fig. 4.

Adam-Gibbs plot for six different glasses; lines: calculated from eqs. 6-7; symbols: experimental viscosity data (float glass [20]; C glass wool [21]; E fibre, low , TV panel glass [22]; anorthite [9])
16 14 12
log , in dPas

fibre 3

fibre 2 fibre 1

10 8 6 4 2 0 -2 0

basalt wool from quarry "Westerwald" 2

2 2 4 6 8 10 12 Tg/(TSC) in (gK)/J

3 14

Fig. 5.

Adam-Gibbs plot for four different mineral wool glasses; lines: calculated from eqs. 6-7; symbols: experimental viscosity data

In table 5, the results obtained from the thermodynamic model and the Adam-Gibbs analysis are contrasted. In addition to the values for Svit and cP, the structure parameter a and the slope f (fragility slope) at which the viscosity value at Tg is approached in the Angell plot [24] are given, too. The fragility slope f is calculated from the first derivative (log ) / (Tg/T), eqs. 6-7, for T Tg. The precision of the data generated by the Adam-Gibbs analysis and by the constitutional model is 0.3 J per mol and 100 g glass. The precision is taken as the basis to assess the match of the two approaches. The accuracy of the data is much lower: Based on a previous comparison of experimental and modeled results [6], the error in cP is estimated as 5 %. The error of Svit typically amounts to 10 to 15 % [9]. Vitrification entropy Svit, jump of the heat capacity cP in the glass transition, structure parameter a = cP/Svit, and fragility slope f for different types of glass; AG: derived from an Adam-Gibbs analysis of viscosity data; MOD: calculated by the constitutional model Svit in J per mol and 100 g glass MOD 8.2 9.1 11.8 12.1 7.7 8.3 13.6 11.2 8.2 AG 8.3 9.0 11.8 12.1 7.9 8.3 18.1 12.0 7.4 cP in J per mol and 100 g glass MOD 30.2 29.5 29.6 19.9 18.8 18.5 24.3 14.5 12.4 AG 29.2 28.3 32.4 33.7 14.2 20.0 23.7 11.2 12.4 structure fragility slope parameter f= (Lg-A)(1-a) a = cP/Svit AG AG 3.5 64.6 3.1 59.3 2.8 56.7 2.8 63.5 1.8 38.9 2.4 46.7 1.3 37.7 0.9 26.7 1.7 36.7

Tab. 5.

glass

fibre 1 fibre 2 fibre 3 basalt DGG-1 glass wool E fibre low TV panel

DISCUSSION As a general result, vitrification entropies Svit from the thermodynamic model and the analysis of viscosity data match well. It is only in one case (E fibre glass) that a deviation is found which is worth being discussed. The deviation is attributed to the fact that no Ca borate phases were taken into account for the E fibre glass composition. With CaO being the only high-basicity oxide in the composition, the coexistence of wollastonite CaOSiO2 with pure B2O3 is most unlikely. Consequently, the data base for alkali free boron containing glasses has to be adjusted accordingly. As an especially appreciated result, the Svit value of the low glass is predicted well. It may be concluded that, with the introduction of the latent boroleucite compound in the database, the former problems encountered in modeling this type of glasses have been solved. This is expected to have an impact on the prediction of hydrolytic stability of pharmaceutical glasses and their theory-guided improvement. The modeling of cP is more difficult. This is due to the fact that the heat capacities of high-T liquids are often less well know than the formation properties of mineral compounds. Again, the

data match well for most glass types. The mismatch for the basalt should not be taken too serious, as the Adam-Gibbs evaluation is based on a relatively poor linear correlation of only three viscosity points (see figure 5). For some glasses (low ; glass wool), cP could be modeled successfully only if the latent boroleucite compound was taken into account. Here, the AdamGibbs analysis provided a most valuable incentive for a meanwhile accomplished improvement of the database. The obvious mismatch in cP for the float glass (DGG-1) comes as an unpleasant surprise. There is ample experimental proof that enthalpies, Gibbs energies and sodium oxide activities of typical float and container glasses can be modeled with satisfactory accuracy, which is obviously not the case for cP. The reason could not yet be identified in an unambiguous way. However, a comparison of the speciations of all glasses compiled in tables 3 and 4 shows that DGG-1 and fibre 3 are the only cases where Na2O2SiO2 and MgOSiO2 are supposed to coexist. According to the phase diagram [23], MgO should rather be allotted to a compound Na2OMgO4SiO2, thus allowing for the coexistence of Na2O2SiO2 and Na2OMgO4SiO2. As no data were available for this compound, a speciation using MgOSiO2 was adopted as an approximation. This approximation seems to have only a minor effect on the calculation of enthalpies etc., but it is unacceptable for the modeling of cP (even though the comparatively small amount of Na2O2SiO2 in the case of fibre 3 keeps the cP mismatch low). It is thus suggested that an improvement of the database for float and container glasses should focus on an assessment of data for Na2OMgO4SiO2. SUMMARY Viscosity data of glass forming systems have been exploited before with success to derive or confirm thermodynamic data of glass melts. Such work was, however, focused on melts with primarily scientific interest, or on melts relevant to geoscience. In the present paper, this approach was extended to industrial glasses of different compositional families. The study comprised the stone wool type fibre glasses which differ from natural systems in so far as they are atypically rich in MgO or alkali oxides. It also comprised traditional soda lime silicate glasses, different borosilicate systems (high silica; moderately high silica; alkali free) and systems with heavy alkali and alkaline earth elements (TV panel). The problem was tackled from two sides: Viscosity data were submitted to an Adam-Gibbs analysis, and data for the vitrification entropy Svit and the jump of the heat capacity cP were derived via a regression analysis. It is worth mentioning that the viscosity data of all glasses could be linearized. This confirms the assumption that the Adam-Gibbs analysis is a general tool applicable to multi-component glasses. In parallel to the Adam-Gibbs analysis, the quantities Svit and cP were calculated by the constitutional model. For this purpose, a new compound, i.e., the sodium boroleucite Na2OB2O34SiO2 was implemented in the database. The results of both approaches agree well. In a few individual cases, the comparison yields valuable incentives to improve the thermodynamic database. In order to improve the modeling of float and container glasses, the thermodynamic data of the compound Na2OMgO4SiO2 should be assessed.

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