Basic and Applied Research: Section I

Thermodynamic Reassessment of the BaO-B2O3 System

H. Yu, Q. Chen, and Zh. Jin

(Submitted 21 November 1998; in revised form 29 May 1999) The BaO-B2O3 pseudobinary system is assessed. A two-sublattice ionic solution model, (Ba2+)P(O2, BO3, B4O2, B3O4.5)Q, is adopted to describe the liquid phase. All the solid phases are treated as 3 7 stoichiometric compounds. A set of parameters consistent with most of the available experimental data on both phase diagram and thermodynamic properties is obtained by using CALPHAD technique. A comparison between the calculated results and experimental data as well as a previous assessment is presented.

Introduction
Among alkali and alkaline earth borate systems, the BaOB2O3 system is well known because of the discovery of the BBO crystal (BaB2O4). It is important as an end-member of many higher-order borate systems, which may contain new favorable crystals. As with other borate systems, the knowledge of phase equilibria in this system is limited due to experimental restrictions. With the aid of the CALPHAD technique, thermodynamic assessment plays an important role in obtaining a precise phase diagram and reliable thermochemical information. Moreover, this work is also a vital part of setting up a database on functional crystals. The complicated structure of the borate amorphous phase results in numerous difficulties in the selection of a liquid model for borate systems. In previous assessments of CaOB2O3 and BaO-B2O3 by [95Che], a two-sublattice ionic solution model (Me2+)P(O2, BO3, B2O3)Q Me = Ca or Ba, was 3 adopted. Although the calculations in these systems can fit experimental data within reasonable deviations, this model still has some limitations and failed to produce an acceptable result in Li2O-B2O3 [97Yu1]. Hence, the authors modified this model into (Men+)P(O2, BO3, B4O2, B3O4.5)Q, where Men+ repre3 7 sents metal cation, and assessed Li2O-B2O3 successfully [97Yu1]. In order to both unify the liquid model and confirm its feasibility in alkaline earth borate systems, the authors reassessed CaO-B2O3 [97Yu2]. Although the results do not differ from the previous calculation significantly, which is natural because parameters can be adjusted to fit the experimental data to some extent, improvements are still noticed, especially in the calculated immiscibility region. In this article, the authors reassess BaO-B2O3 for the sake of unifying the liquid model in alkali and alkaline earth borate systems.

report a relatively complete phase diagram of BaO-B2O3; four compoundsBaO4B2O3, BaO2B2O3, BaOB2O3, and 3BaOB2O3were found. Temperature measurements were later repeated [53Lev]. Additionally, [58Ham] determined several liquidus points in this system; their results are generally in accordance with [53Lev]. Many researchers have contributed to the investigation of the liquid immiscibility region in BaO-B2O3 system, including [58Lev], [82Oht], [81Cle], [79Hag], and [87Hag]. Unfortunately, serious discrepancies among these data exist, and the determined critical temperatures vary within a temperature range of more than 200 K . This may be caused by experimental difficulties. [53Lev] initially reported that BaB2O4 (BaOB2O3), has an transformation at a temperature between 100 and 400 C. However, [69Hub] measured the temperature to be 925 5 C. This is supported by later studies, 920 10 C by [82Jin] and 925 C by [96Hik]. Thus, the authors adopted 925 C in the present work. Additionally, [96Hik] also determined the metastable melting point of BaB2O4 to be 1372 K. These data were also included in the optimization. This temperature is very close to that of BaB2O4, 1378 K, which indicates only a small difference in the thermodynamic properties between them. Thermodynamic data for the BaO-B2O3 system are very limited. [63Ste] determined heat capacities of glassy and crystalline BaO2B2O3 and BaO4B2O3. [89Mul] measured the mixing enthalpy of liquid at 1551 K. The authors included these data in the optimization.

Thermodynamic Model
The two-sublattice ionic solution model, (Men+)P(O2, BO3, B4O2, B3O4.5)Q, were adopted for this article. The value 3 7 of subscripts P and Q in the formulation are changeable: P = yi (i) = 2yO2 + 3yBO3 + 2yB O2
3 4 7

Experimental Data
The shortage and scatter of experimental data in BaO-B2O3 causes difficulties in the assessment. [49Lev] were the first to
H. Yu, Q. Chen, and Zh. Jin, Department of Materials Science and Engineering, Central South University of Technology, Changsha, Hunan 410083, P.R. China. Present address for Q. Chen: Department of Material Science and Engineering, Royal Institute of Technology, S-10044, Stockholm, Sweden. Contact e-mail: jin@mail.csut.edu.cn.

(Eq 1)

Q = yj j = yBa2+ = 2

(Eq 2)

where yi and i and yj and j represent the site fractions and charges of anion i and cation j, respectively. The Gibbs energy of the liquid is expressed as:

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479

Section I: Basic and Applied Research GL = yO2 0GBa2+:O2 + yBO3 0GBa2+:BO3 + yB O2 0GBa2+:B O2 m + 1.5 yB O
4 7

0G

+ yB O2 ln yB O2 + yB O ln yB O ) + Gex m
4 7 3 4.5 3 4.5

3 4.5

B2O3

+ R T(yO2 ln yO2 + yBO3 ln yBO3

3 3

4 7

Because heat capacity curves of glassy and crystalline BaO2B2O3 and BaO4B2O3 have been found to be similar [63Ste], 0GBa2+:B O2 is thus expressed as:
4 7

(Eq 3)
0G Ba2+:B4O2 7

= 2 0GS BaO2B O + C + D T
2 3

(Eq 5)

where 0GBa2+:O2 and 0GB O represent the Gibbs energy of the 2 3 pure liquid BaO and B2O3, which come from the SGTE substance 0G 2+ database. Ba :BO3 and 0GBa2+:B O2 are the Gibbs energy of 3 4 7 the associates Ba3(BO3)2 and Ba2(B4O7)2 in the liquid respectively. R is gas constant; T is temperature. 0GBa2+:BO3 is given 3 by Neumann-Kopps rule:

0G

Ba2+:BaO3 3

= 0GS 3BaOB O + A + B T
2 3

(Eq 4)

where 0GS BaO2B2O3 is the Gibbs energy of crystalline BaO2B2O3. In Eq 3, Gex is the excess Gibbs energy of liquid. For simplim fying this expression, one assumes that the same interactions exist between neutral and anionic species, weighted per negative charge. Additionally, another interaction parameter between BO3 and B4O2 is used to avoid unrealistic 3 7 immiscibility in the region between them. Therefore, Gex is dem scribed by:

Table 1 Parameters for the BaO-B2O3 system (J/mole of formula units)

Liquid
0G 2+ 2 = 2GBAOL Ba :O 0G B O = 1.5GB2O3L 0G 32+4.5 3 = 3GBAOL + GB2O3L 425,964.944 + 99.9297008 Ba :BO3 0G 2+ 0 Ba :B4O2 = 2 GBaO2B2O3 + 182,149.0308 9.660453 T 7 0L = 63,560.6090 60.6513205 T 1L 2L

= 74,213.2860 = 13,899.7384 0L 2+ Ba :BO3B O2 = 366,110.345 Solid B2O3

3 4 7

0GS B2O3 = GB2O3S BaO4B2O3 0G BaO4B2O3 =

5,880,719.74 + 1641.911415 T 290.953517 T ln T 0.111427633 T 2 + 2.65849867 106 T 1 3,316,249.845 + 975.6467177 T 172.663804 T ln T 0.0532353780 T 2 + 1.03216951 106 T 1

BaO2B2O3 0G BaO2B2O3 = BaOB2O3

0G BaO B2O3 = GBAOS + GB2O3S 168,651.488 BaOB2O3 0G BaO B2O3 = 0G 3BaO B2O3 =

GBAOS + GB2O3S 170,590.593 + 1.61868986 T 3GBAOS + GB2O3S 371,288.073 + 71.8050568 T

3BaOB2O3 Solid BaO

0GS BaO GBAOS Functions:

GB2O3L = 1,269,394.89 + 501,184.624 T 1 + 198.313176 T 35.6509435 T ln T 0.0739858812 T 2 + 1.10697483 105 T 3 (298.14 < T < 400.00) 1,272,805.86 + 732,599.572 T 1 + 256.720618 T 44.8913912 T ln T 0.0628129276 T 2 + 8.37141693 106 T 3 (400.00 < T < 723.00) 1,305,592.36 + 820.788302 T 129.704 T ln T (723.00 < T < 3000.00) GB2O3S = 1,293,465.45 + 501,184.624 T 1 + 231.605779 T 35.6509435 T ln T 0.0739858812 T 2 + 1.10697483 105 T 3 (298.14 < T < 400.00) 1,296,876.42 + 732,599.572 T 1 + 290.013221 T 44.8913912 T ln T 0.0628129276 T 2 + 8.37141693 106 T 3 (400.00 < T < 723.00) 1,329,662.91 + 854.080905 T 129.704 T ln T (723.00 < T < 3000.00) GBAOL = GBAOS + 58,576 26.623797 T GBAOS = 563,212.303 + 238.213889 T 45.367112 T ln T 0.0088301228 T 2 + 9.53812533 107T 3 + 126,373.536 T 1 (298.14 < T < 900.00) 566,075.47 + 277.305539 T 51.308392 T ln T 0.003335694 T 2 + 7.57304 109T 3 + 390,471.8 T 1 (900.00 < T < 2286.00) 584,226.131 + 398.668889 T 66.944 T ln T (2286.00 < T < 2400.00)

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Basic and Applied Research: Section I Gex = 2 yO2yB O [ 0L + 1L(yO2 yB O ) + 2L(yO2 yB O )2] m + 3 yBO3 yB O [
3 3 4.5 4 7 3 4.5 3 4.5

0L

+ 2 yB O2 yB O [
3 4 7

0L

1L(y 3 BO3

yB O ) +
3 4.5 3 4.5

3 4.5

2L(y

+ yBO3 yB O20LBa2+:BO3,B O2
3 4 7

1L(y B4O2 7

yB O ) +

BO3 3

yB O

3 4.5

Optimization and Calculation

All the optimizations and calculations are carried out within THERMO-CALC. The parameters are given in Table 1. The calculated BaO-B2O3 phase diagram is shown in Fig. 1, and detailed comparisons between the present and previous calculation are also presented in Fig. 2 and 3. As shown in Fig. 2, the calculated boundary of the miscibility gap at low temperature is in agreement with the previous work and fits most experimental data very well. Although the calculated critical point is about 80 K lower than the previous calculation and much closer to recent researches [87Hag], it does not indicate an improvement due to the scatter of experimental data. Such a difference can be eliminated by the adjustment of parameters; the calculation should be regarded as a compromise between those data and other information including thermochemical and phase equilibria data.

)2

2L(y B4O2 7

yB O )2]
3 4.5

3 4.5

(Eq 6)

All the compounds in BaO-B2O3 are stoichiometric. Since the heat capacities of BaO2B2O3 and BaO4B2O3 are available, their Gibbs energy functions can be written as:
0G

= a + bT + cT ln T + dT + eT 1

(Eq 7)

As to the other crystalline phases, the Gibbs energy is expressed according to Neumann-Kopps rule:
0GS xBaOyB2O3

= x 0GS + y 0GS O + A + BT BaO B

2 3

(Eq 8)

Table 2 Experimental and calculated invariant reactions in BaO-B2O3 system

Reactions L BaO + Ba3B L Ba3B L Ba3B + BaB L BaB L BaB + BaB2 L BaB2 L BaB2 + BaB4 L BaB4 L1 BaB4 + L2 [49Lev, 53Lev] T, K X(B2O3) 1643 1656 1188 1378 1177 1183 1142 1162 1151 0.127 0.221 0.443 0.594 0.980 0.700 [63Ste] T, K 1183 1162 T, K 1151 [82Oht] X(B2O3) 0.989 0.704 T, K 1619 1674 1191 1378 1166 1187 1144 1157 1154 [95Che] X(B2O3) 0.107 0.226 0.424 0.574 0.981 0.699 This work T, K X(B2O3) 1645 1654 1188 1378 1177 1183 1145 1161 1154 0.111 0.225 0.446 0.570 0.983 0.714

BaxBy represents crystalline phase xBaOyB2O3. X, mole fraction

Fig. 1 Calculated phase diagram of the BaO-B2O3 system

Fig. 2 Comparison between the present and previously (dashed line) calculated miscibility gap together with experimental data

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Section I: Basic and Applied Research There are also some differences between the calculated liquidus and that in the previous work; this is presented in Fig. 3. The calculated liquidus of BaOB2O3 is significantly improved, whereas that of 3BaOB2O3 becomes worse. According to the previous calculation, the temperature of the eutectic reaction L BaO + 3BaOB2O3 was low and the melting point of 3BaOB2O3 was high, deviating markedly from the experimental data. Sacrificing those data for invariant reactions, the previous calculation produced a very sharp liquidus for 3BaOB2O3 so that it would fit the data for the 3BaOB2O3 liquidus; this is believed to be unnecessary in the present work. Reasonably, the authors have paid more attention to temperatures of invariant reactions in the present assessment, as indicated in Table 2. The calculated mixing enthalpy of the liquid phase at 1551 K is presented in Fig. 4. The present assessment obtains nearly the same results as the previous work. A large difference between the experimental data near the B2O3 end still exists. Besides large experimental errors in this region, such deviation is also caused by the same factors as in the earlier CaOB2O3 assessment. The experimentally determined mixing enthalpy suggests a strong immiscibility tendency in the vicinity of B2O3. If so, the calculated miscibility gap is likely to extend to an extremely high temperature, which is obviously unrealistic. To some extent, the calculation could be regarded as a compromise between mixing enthalpy and miscibility gap. Figures 5 and 6 show the calculated heat content of BaO2B2O3 and BaO4B2O3 together with related experimental data from [63Ste]. Calculated thermodynamic properties including H298, S298, Hfus, and Sfus of crystalline phases are listed in Table 3 together with previous work. Without any experimental data, different results for BaOB2O3 and BaO3B2O3 are predicted by the two assessments.

Table 3 Calculated thermochemical properties of crystalline phases (standard reference state)

Phase BaO4B2O3 H298, J/mol 5,766,278 5,753,792 3,253,140 3,245,025 1,992,195 1,965,852 3,289,115 3,321,172 S298, J/mol K 402.979 433.230 224.050 252.884 124.369 166.213 198.568 264.995 Hfus, J/mol 115,183 115,389 115,583 85,719 87,054 85,726 72,294 43,838 183,488 201,244 Sfus, J/mol K 99.253 99.700 99.469 72.435 73.318 72.465 52.475 31.812 110.913 120.247 Reference This work [95Che] [63Ste] This work [95Che] [63Ste] This work [95Che] This work [95Che]

BaO2B2O3

BaOB2O3(a) 3BaOB2O3

(a) H298, S298 refer to BaOB2O3 and Hfus, Sfus refer to BaOB2O3

Fig. 3 Comparison between the present and previously (dashed line) calculated liquidus together with experimental data

Fig. 4 Calculated and experimentally determined [89Mul] mixing enthalpy of liquid at 1551 K (referred to liquid B2O3 and crystalline BaO)

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Journal of Phase Equilibria Vol. 20 No. 5 1999

Basic and Applied Research: Section I Figures 7 and 8 depict the calculated heat contents of liquid at the compositions of BaO2B2O3 and BaO4B2O3; they agree with the experimental data very well at high temperature. By extrapolating down to room temperature, they are also compared with the available information on glassy phases. The deviations at lower temperature are caused by the differences between glassy phase and supercooled liquid; as yet the glass transformations cannot be dealt with. denoted (Ba2+)P(O2, BO3, B4O2, B3O4.5)Q, is adopted to de3 7 scribe the liquid. All solid phases are treated as stoichiometric compounds. A set of parameters consistent with most of the available experimental data on both phase diagram and thermodynamic properties is obtained through optimization. Detailed comparison with previous work is also presented. Acknowledgment The authors wish to thank Prof. B. Sundman for providing the software Thermo-Calc. This work is financially supported by the National Advanced Materials Committee of China (NAMCC).

Conclusions
The BaO-B2O3 pseudobinary system is assessed thermodynamically in this work. A two-sublattice ionic solution model

Fig. 5 Heat content of crystalline BaO2B2O3

Fig. 6 Heat content of crystalline BaO4B2O3

Fig. 7 Heat content of glass and liquid at XBaO = 0.333 (referred to crystalline BaO2B2O3 at 298 K)

Fig. 8 Heat content of glass and liquid at XBaO = 0.2 (referred to crystalline BaO4B2O3 at 298 K

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Section I: Basic and Applied Research References

49Lev: E.M. Levin and H.F. McMurdie, The System BaO-B2O3, J. Res. Nat. Bur. Std., Vol 42 (No. 2), 1949, p 131-138 53Lev: E.M. Levin and G.M. Ugrinic, The System Barium Oxide-Boric Oxide-Silica, J. Res. Nat. Bur. Std., Vol 51 (No. 1), 1953, p 37-56 58Ham: E.H. Hamilton, G.W. Cleek, and O.H. Grauer, Some Properties of Glasses in the System Barium Oxide-Boric Oxide-Silica, J. Am. Ceram. Soc., Vol 41 (No. 6), 1958, p 209-215 58Lev: E.M. Levin and G.W. Cleak, Shape of Liquid Immiscibility Volume in the Barium Oxides-Boric Oxide-Silica, J. Am. Ceram. Soc., Vol 41 (No. 5), 1958, p 175-179 63Ste: D.R. Stewart and G.E. Rindone, High-Temperature Energy Relations in Borates: Alkaline-Earth and Lead Borate Compounds and Their Glasses, J. Am. Ceram. Soc., Vol 46 (No. 12), 1963, p 593-596 69Hub: K.H. Hubner, Neues Jahrb. Min. Monatsh., 1963, p 335 79Hag: V.B.M. Hageman and H.A.J. Oonk, The Region of Liquid Immiscibility in the System B2O3-BaO, Phys. Chem. Glasses, Vol 20 (No. 6), 1979, p 126-129 81Cle: K. Clemens, M. Yoshiyagawa, and M. Tomozawa, LiquidLiquid Immiscibility in BaO-B2O3, J. Am. Ceram. Soc., Vol 64 (No. 6)C, 1981, p 91-92 82Jin: J.-K. Liang, Y.-L. Zhang, and Q.-Z. Huang, The Kinetic Study of BaB2O4 Phase Transition, Acta Chim. Sin., Vol 40 (No. 11), 1982, p 994-1000 82Oht: Y. Ohta, K. Morinaga, and T. Yanagase, Liquid-Liquid Immiscibility in Several Binary Borate Systems, J. Ceram. Soc. Jpn., Vol 90 (No. 9), 1982, p 511-516 87Hag: V.B.M. Hageman and H.A.J. Oonk, Liquid Immiscibility in the system B2O3-MgO, B2O3-CaO, B2O3-SrO and B2O3-BaO Systems, Phys. Chem. Glasses, Vol 28 (No. 5), 1987, p 183-187 89Mul: F. Mller and S. Demirok, Thermochemical Study of the Liquid Systems BaO-B2O3 and CaO-B2O3, Glastech. Ber., Vol 62 (No. 4), 1989, p 142-149 95Che: Q. Chen, Ph.D. thesis, CSUT, Changsha, Hunan, P.R. China, 1995 96Hik: K. Hikaru, K. Yasuhiko, S. Katesumi, et al., High Temperature Powder X-Ray Diffraction Study of Barium Metaborate BaB2O4, Rep. Res. Lab. Eng. Mater., Tokyo Inst. Technol., Vol 19, 1994, p 9-17; Ceram. Abstr., Vol 75 (No. 3), 1996, p 382, 7506240A 97Yu1: H. Yu, Zh. Jin, Q. Chen, and M. Hillert, Thermodynamic Assessment of Li2O-B2O3 System, submitted for publication in J. Am. Ceram. Soc. 97Yu2: H. Yu, Q. Chen, and Zh. Jin, Thermodynamic Reassessment of CaO-B2O3 System, accepted for publication in Calphad

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