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Surface Tension, Density, Viscosity, and Electrical
Resistivity of Molten Binary Al kaline-Earth Borates
by LEO SHARTSIS and H. F. SHERMER
National Bureau of Standards, Washington, D. C.

Results of an investigation of some properties of Table 1. Surface Tension of Molten Binary Alkaline-Earth
the systems CaO-B203, SrO-BzOa, and BaO- Borates
BtOs are reported. The formation of two liquids Surface tension (dynes/cm.)
at low RO concentrations limited the range of r Y

Mole % 900“C. 1000°C. llOO°C. 1200DC. 1300OC.

compositions which could be measured. The
values of surface tension and temperature co- CaO
efficient of surface tension obtained for composi- 2.3* 81.4 84.4 87.6 91.4 95.8
tions where two immiscible liquids exist corre- 3.4* 81.5 85.8 89.3 94.0
sponded closely to those for pure BzOa. At RO 7.7* 80.7 83.5 87.3 91.1 95.1
concentrations above the two-liquid regions the 13.1* 81.5 83.8 87.8 92.2 95.7
20.3* 83.3 87.0 91.4 95.6
surface tension rose sharply with increasing RO
content. The densities in the liquid range as well 28.8 154.1 140.0 128.9 123.5 123.6
31.2 176.4 162.0 150.5 144.1 140.4
as at room temperature were in the order Ba > 31.2 160.2 -148.2 143.0 139.3
Sr > Ca. The introduction of RO into Bz03 34.7 186.2 179.4 173.0 170.2
caused contractions in the glass network; the 37.1 197.3 191.2 186.2
order of the contracting effect was Ca > Sr > 42.5 234.8 227.5 221.4
45.7 255.0 250.7 246.4
Ba. Neither the method of Huggins or of 50.3 274.8 272.2 270.0
Stevels was satisfactory for representing the 54.4 302$ 299.4 296.9
density behavior of these glasses. The viscosity
SrO
isotherms of barium borate liquids in the tem-
perature range 850” to 950OC. showed maxima 2.7* 82.4 86.0 88.6 93.2
at about 22 to 23 mole yo BaO; the other two 7.7* 80.0 83.0 86.7 91.0 95.0
systems were too fluid for the counterbalanced- 22.4 137.1 128.4 122.8 121.7 122.2
sphere apparatus used in this work. The equiv- 23.2 145.6 134.5 128.9 126.0 125.8
26.4 171.7 162.9 155.1 150.0 149.0
alent conductance increased with RO concen- 27.2 181.4 171.9 164.0 157.3 155.2
tration; the order for both specific and equiv- 29.5 194.2 185.8 178.3 172.1 165.6
alent conductance at corresponding concentra- 31.3 208.9 200.4 193.8 187.5 184.3
tions was Ba > Sr > Ca. 33.8
36.3
217.0
232.7
210.3
226.4
204.3
220.6
201.7
215.4
40.6 253.8 247.0 241.8 236.7
45.3 269.9 265 5 261.1 256.4
1. Introduction 50.6 286.0 281.4 276.2
STUDY of the surface tension, density, viscosity, and
55.1 302.8 298.3 292.5

A electrical resistivity of the systems Ca0-B203, SrO-

BsOa, and BaO-BzOa was undertaken as part of a com-
prehensive investigation of the various physical properties of
2.0*
2.3*
80.0 84.0
82.8
BaO
88.6
86.3
93.4
90.9
96.3
94.8
simple glassforming systems. These binary alkaline-earth 7.7* 79.4 82.4 87.2 ,91.8 96.3
borates are characterized by the formation of two-liquid re- 13.1* 88.1 89.9 92.1 99.8 106.3
gions a t low concentrations of alkaline-earth oxides. The 17.8 116.2 117.8 120.0 122.2
two-liquid region extends to 16 mole yoin the case of BaO,’ 20.2 145.7 141.0 137.5 137.6 135.4
20.8 150.5 145.8 142.1 140.7 139.7
to 21 mole % in the case of Sr0,2and to 27 mole % in the case 23.8t 171.4 165.8 161.1 167.9 ___ -
166.0
of CaO.3 The range of compositions that form homogeneous 24.71 174 7 170.4 166.6 163.8
glasses is therefore limited at the low-concentration end by 24.8t 177.0 172.4 168.9 163.5
this two-liquid formation. As the concentration of RO (al- 27.3 197 2 192 3 187.3 183.3 180.6
28.9t 201.2 195.6 192.0 189.3
kaline-earth oxide) is increased beyond the two-liquid region, 29.2 207.3 202.9 198.0 193.7 190.7
the liquids tend to crystallize with increasing ease on cooling 32.1 220.6 216.1 211.2 207
- _. .4
- -
203.5
and the glassy region is thus limited by the onset of devitrifi- 32.7t ~ 218.9 213.8 210.1 206.5
cation. In the present investigation it was found that the 33.3t 221.3 216.8 212.1 208.9
34.4t 226.9 221.2 216.6 212.5
36.3 239.0 233.7 228.9 224.8 220.7
36.9t 235.4 229.4 224.5 219.6
37.2f 238.3 232.0 227.0 221.1
Presented at the Fifty-Sixth Annual Meeting, The American 40.7t 249.6 242.8 237.5 232.5
Ceramic Society, Chicago, Ill., April 22, 1954 (Glass Division, 40.9 248.4 243.2 237.3 231.9
No. 16). Received December 16, 1953; revised copy received 45.9 263.4 257.4 251.1 242.9
April 6,1954. 51.6 275.1 269.0 261.7 252.4
The authors are, respectively, physical chemist and physicist, 56.6 288.9 282.4 274.0 263.4
National Bureau of Standards. 63.8 321.6 314.6 305.2 293.9
* E . M. Levin and H. F. McMurdie. “The Svstem BaO-
B&,” J. Am. (ham. Soc., 32 [3] 99-105 (1949); J. Research * Average composition, computed from batch, of both liquids
Nail. Bur. Standards, 42 [2] 131-38 (1949); RP 1956. in the two-liquid region. Only the surface tension of the upper
2 Marc Fo&, “Solubilities and Separations in Glasses,” Ann. liquid (low alkaline earth content) was measured.
chim., 11,359452 (1939); Ceram. Abstr., 19 [ l l ] 255 (1940). 1Glasses made from batch materials suitable for the manu-
a E. T.Carlson. “The System CaO-BpOa,” Bur. Standards J. facture of optical glasses.
Research, 9 [6] 825-32 (December 1932); RP 510. $ Extrapolated value.
544
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
November 1954 Molten Binary Alkaline-Earth Borates 545
3201 I I I I II. Preparation of Compositions and Methods of Test
The liquids investigated were made by melting the required
amounts of chemicals in platinum crucibles at approximately
13OO0C. The ingredients were chemically pure except for
those in the compositions marked with (t) in Table I; these
compositions were made from materials of practically equal
purity used in the production of optical glass. Alkaline-earth
oxides were introduced in the form of carbonates and boron
trioxide in the form of boric acid. The melts, which weighed
approximately 500 gm., were stirred with a platinum stirrer
until they appeared clear and then were poured into cold
iron molds.
Samples of the melted compositions were analyzed for RO
content before and after the surface-tension determinations by
a triple evaporation with HF and H2S04.* There was a gen-
eral tendency for the RO value to be a few tenths of a per cent
higher after the tests than before, indicating some loss of
Bz03 by volatilization during the determination of surface
tension. The reported compositions are the average of the
two determinations.
The method of measuring surface tension has been de-
scribed.4 It consists of determining the maximum pull exerted
on a thin-walled platinum cylinder when its lower edge is in
contact with the test liquid. In the present work the first
determination of the surface tension of any melt was made at
1300°C. Subsequent measurements were made a t intervals
of 100°C.; the temperature was decreased until the @ass was
Two Liquid Region too viscous to yield in a reasonable time or until crystallization
0 % (Surface Tension Is For Upper
40,Rich Liquid Only)
occurred. Density values used in the calculation of surface
tension were determined by weighing a platinum sphere im-
60 mersed in the molten test liquid.
0 10 20 30 40 50 60 70
The detailed procedure for measuring the viscosity and
R O (MOLE % )
density has been described.6 The motion of a platinum
Fig. 1. S\rrface tension of some binary alkaline-earth borotes a t 1 100°C. sphere suspended in the test liquid from one arm of a balance
Cimles, BOOliquids; rquares, SrO liquids; Mangles, COO liquids. Curves
are typical of those for the other test temperotures. is observed by measuring the velocity of the balance pointer.
The change of the velocity of the sphere with change in ap-
plied load is a measure of the viscosity of the liquid. Since
the load-versus-velocity curve a t any one viscosity is a

.L,, r Two
I
0
Liquid Re(
I I
1- straight line, the weight of the sphere in the test liquid is de-
termined by extrapolation to zero velocity. A t sufficiently
low viscosities the weight of the sphere in the test liquid may
z be determined by direct weighing. The density of the liquid
0 is calculated from the difference between the weight of the
(D
2
sphere in air and that in the test liquid together with the
1
W
I-
W +OD2 t. -I known volume and expansion of the sphere. Thermal ex-
pansivity (B) of any composition is calculated from the den-
z
0
sities a t any two temperatures by the equation
ln

- 0.02O I

- 0.04
t where dl and & are the two densities and Tl and T2are the
correspondingtemperatures.
Densities at room temperature (approximately 25 “C.)
were obtained from the difference in weight of annealed glass
samples in kerosene and in air. The samples were annealed
in an electric muffle furnace a t 590°C. for 2 hours. The cur-
rent was then shut off and the samples were allowed to cool in
-0.10 - the furnace.
I I I I The detailed procedure for measuring electrical resistance
0 10 20 30 40 50 60 70 has been described.6 The platinum viscosity crucible, a
R0 (MOLE X )
Fig. 2. Mean temperature coefflcient of surface tension of binary
alkaline-earth borates in the temperature range 11 00” to 1300°C.
Circles, BOOliquids; squares, SrO liquids; triangles, COO liquids. * The compositions were analyzed by J. R. Spann of the staff
of the National Bureau of Standards.
4 Leo Sharteis and A. W. Smock. “Surface Tensions of Some
Optical Glasses,” J . Am. Ceram. SOG.,30 [4] 130-36 (1947).
Leo Shartsis and Sa,m Spinner, “Viscosity and Density of
barium borates formed homogeneous glasses over a larger Molten Optical Glasses, J. Research Natl. Bur. Standards. 46
composition range (16 to 40 mole yo BaO) than did the stron- [3] 176-94 (1951); RP 2190; Ceram. Abstr., 1952, March, p.
tium h8)rates (21 to 36 mole yo SrO); the calcium borates 38c.
6L. Shartsis, W. Capps, and S. Spinner, “Viscosity and
showed the smdlest composition range of homogeneous Electrical Resistivity of Molten Alkali Borates,” J . Am. Ceram.
glasses (27 to 36 mole % CaO). SOC.,36 [lo] 319-26 (1953).
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
546 Journal of The American Ceramic Society-Shartsis and Shermer Vol. 37, No. 11
Table II. Densities of Binary Alkaline-Earth Borotes
___-____-_A
BaO
Temp.
__
Density
______ SrO
Temp. Density
- CaO
Temp.
_____
Density
Mole %
' ("C.) (gm./cc.) Mole % (OC.) (gm./cc.) Mole % ("C.) (gm./cc.)
17.8 1099 2.386 22.4 1117 2.378 28.8 25 2.483
1002 2.432 1015 2.431 25 2.475*
897 2.477 916 2.482
25 2.646
1104 2.385 25 2.637* 31.2 1102 2.231
1007 2.429 999 2.288
950 2.454 902 2.341
903 2.475 23.2 25 2.674 25 2.526
847 2.503 25 2.667* 25 2.519*
25 2.671

20.2 1104 2.526 26.4 1103 2.498 31.2 1204 2.174

1007 2.574 1050 2.526 1155 2.204
956 2.599 1002 2.555 1107 2.229
903 2.623 951 2.582 1061 2.254
854 2.644 25 2.800 1005 2.279
25 2.813 25 2.790* 956 2.304
25 2 804* 906 2.334
25 2.526
23.8 1004 2 739 27.2 1116 2.552 25 2.524*
950 2.777 1006 2.610
903 2.793 25 2.849
854 2.817 25 2.837* 34.7 1105 2.280
25 2.996 1056 2.309
25 2.986* 29.5 1100 2.604 25 8.590
1051 2.631 25 2.583'
27.3 1099 2.834 1010 2.657
999 2.896 954 2.687
949 2.925 25 2.928 37.1 1200 2.259
896 2.957 25 2.915* 1153 2.282
846 2.986 1105 2.306
25 8.186 31.3 1097 2.661 25 2.629
25 3.179* 997 2.723 25 2.622*
25 3.004
29.2 25 3.284 25 2.994*
42.5 1193 2.328
32.1 1100 3.016 33.8 I100 2.730 1145 2.349.
1001 3.082 1050 2.761
947 3.116 1001 2.790
898 3.151 958 2.819 45.7 1207 2.359
846 3.187 25 3.097 1156 2.379
25 3.423 1106 2.403
25 3.411*
36.3 1100 2.792
36.3 1101 3.160 1003 2.858 50.3 1199 2.398
1003 3.231 25 3.182 1156 2.417
956 3.265 25 3.168*
907 3.300
25 3.624 54.4 1197 2.430
25 3.611* 40.6 1223 2.825
1203 2.836
40.9 1100 3.306 1120 2.885
1004 3.377 Upper layer of 1107 1.496
two liquids 998 1.509
45.9 1211 3.377 900 1.521
1104 3.416 45.3 1205 2.953 802 1.536
1006 3.512 1154 2.976 700 1.559

51.6 1196 3.563

1100 3.624
996 3.688 Upper layer of 1106 1.532
two liquids 1002 1.538
56.6 1202 3.720 900 1.547
1103 3.743 805 1.563

63.8 1119 4.038

Upper layer of 1197 1.560

two liquids 1102 1.550
1007 1,557
900 1,569
800 1.584
692 1.610
* Chilled samples.

cylinder 2 in. in diameter and 3 in. high, acts as one of the output is amplified and fed into the verticarinput of a cathode-
electrodes of the conductance cell and the 0.6-in.-diameter ray oscillograph. The apparatus is calibrated at room tem-
platinum sphere (for measuring viscosity) is the other elec- perature by means of a series of RCl soWns.of known con-
bode. An 8.-c. signal is supplied to a resistance bridge whose ductivity.

November 1954 Molten Binary Alkaline-Earth Borates
4.0 I I I I
,BOO 25"~.
P dications are that above 56 mole % RO the order is reversed to
/
Y'
/
BaO l.lOO°C.
P Figure 2 shows a graph of the mean temperature coeffi-
,'SrO
,No 1100°C.
O
' . p C a O 25°C.
.-
I I I I
30 40 50 60
R O (mole %)
Fig. 3. Densities of alkaline-earth borates a t 25" and a t 1 1 00°C. Types
of liquids ond glasses are indicated adjacent to the curves. Crosses
represent densities a t 25°C. of barium borate glasses (which received
different annealing treatments) avoila ble from another investigation.
111. Results and Discussion
(I) Surfcrce Tension
Surface-tension data obtained for various compositions
over a considerable range of temperatures are given in Table
1. Data obtained at 1100°C. are shown graphically in Fig. 1
and are typical of the results obtained a t other temperatures.
The upper RO limit for each two-liquid region is indicated in
Fig. 1 by a short vertical bar on the horizontal line at 87
dynes per an. This line represents the surface tension at
1100°C. of the upper (less-dense) layer of all the compositions
in the two-liquid region, which extends to 16 mole % for
BaO, to 21 mole % for SrO, and to 27 mole % for CaO. The
liquid high in RO content sinks to the bottom whereas the one
rich in BzOa floats on top. When equilibrium is reached, the
composition of each layer is constant and independent of
the gross composition. In using the cylinder method, contact
is made with the upper BtOa-richliquid and the surface ten-
sions given in Table I and in Fig. I are those of the upper
layer.
The surface tensions of the upper layer for compositions in
the two-liquid region are practically identical with those for
pure B208. The greatest departure is shown by the 13.1
moIe % BaO liquid, the composition of which is close to the
upper limit of the two-liquid formation and may be unreliable
for that reason. Excluding the 13.1 mole yo BaO composi-
tion, the average d u e s for the surface tensions of the com-
positions in the two-liquid region a t QOOOC., 1000°C., and
llOO°C. are 80.5, 83.1, and 87.0 dynes per an. respectively.
The corresponding values for pure B20J are 80.5, 83.5, and
88.2 dynes per cm. Other investigators'* 21 a have noted that
the upper layer contains small amounts of RO (1 to 3%). The
finding that the presence of this small amount of RO does not
affect the surface tension may indicate a tendency for the
alkaline-earth ion to avoid the surface of the upper liquid.
7 Len Shartsis and Webster Capps, "Surface Tension of
M o h A I W Borates," J . A m . Ceram. SOC.,35 [7J IfXJ-7'2
(1962).
15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
547
Beyond the two-liquid region the surface tension rises
sharply with increasing RO concentration. Although the order
for surface tension a t 30 mole Yo RO is Ba > Sr > Ca, the in-
Ca > Sr > Ba. Thisreversal in order between low and high
RO concentrations is analogous to that encountered in the
alkali borate systems7 where the order is K > Na > Li in the
low alkali concentration range but inverts to Li > Na > K at
higher alkali concentrations.
cients of surface tension over the range 1100" to 1300°C.
In the two-liquid region the temperature coefficient of surface
tension is +0.041 dynes per an. per "C. Beyond the two-
liquid region the temperature coefficients decrease sharply at
first, then exhibit a transition region (30 to 40 moIe % RO)
where the decrease is not so sharp. In this transition region
there appears to be a small composition interval where the
order is Ba > Sr > Ca; however, the scatter of the points is
such that too much significance should not be attached to the
position of the curves as drawn. Beyond the transition re-
gion the curves assume the order Ca > Sr > Ba, analogous to
the behavior of alkali borates where the order Li > Na > R is
present a t high alkali concentrations.
(2) Density and Expunsivity
Table I1 presents values of density obtained a t room as well
as at elevated temperatures. Density values at room tempera-
ture are also shown for some samples (designated as chilled)
which were not annealed and serve to show the increases in
density found on annealing. Figure 3 shows a plot of density
data at 1100°C. and a t 25°C. as a function of RO content.
The crosses represent densities at 25°C. of barium borate
glasses available from another investigation in which different
and probably more effective annealing treatments were used.
Although the crosses appear a little higher, the agreement is
satisfactory. The density increases with RO content in all
cases; the rate of increase with concentration is in the order
Ba > Sr > Ca. At equal RO concentration and temperature
the order for density is also Ba > Sr > Ca. Figure 4 shows a
plot of the volume of liquid at 1000°C. containing 1 mole of
BzOa(69.64 gm.) as a function of cation concentration. Cor-
responding curves for alkali borate liquids8are shown for pur-
poses of comparison. The first additions of alkali oxide to
BzOs produce glasses whose volume is less than that of BzOa
alone. This contracting effect apparently diminishes with
increasing concentration of the alkali oxides and the volume
curves rise a t sufficiently high concentration. The apparent
contraction is greater for the smaller cations; thus the mini-
mum for the volume curve of the small lithium ion is below
that of the larger sodium ion, and the minimum in the
sodium curve is below that of the potassium curve. Similarly
the xolume m e s for the divalent borates show the order
Ba > Sr > Ca in agreement with the size order of the divalent
cations. At the very lowest concentrations of the divalent
cations the volume curves are below those of the alkali cat-
ions. Thus even the barium curve is below the lithium curve
at the very lowest concentration of Ba in spite of the much
greater ionic radius of Ba as compared with Li (1.43 vs. 0.78
a.u.).
This method of comparing the divalent cations with the
monovalent cations overlooks the fact that each divalent
cation brings one oxygen along with it into the glass whereas
each monovalent cation brings only one-half an oxygen with
it. Furthermore, the concentration variable used is a func-
tion of temperature. To minimize these difficulties, the
L. Shartsis, W. Capps, and S. Spinner, "Density and Ex-
prutsivity of Alkali Borates and Density Characteristics of Some
Other Binary Glasses,'.' J . Am. & e f m .Soc., 36 [a] 35-43 (1%3),
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Journal of The American Ceramic Society-Shartsis and Shermer Vol. 37, No. 11

13.0-

12.0.
0 0 38 0 16 0 24 0 32
I I I 1 Nhl ( g r a m a t o m M l g r a m a t o m 0)
8 16 24 32
C a t i o n concentration ( m o l e s / l i t e r ) Fig. 5. Vo. the volume (cc.) of liquid a t 1000°C. contoining 1 gm. atom
of oxygen (16 em.), vs. Nu, gram atoms of cations per gram atom of
Fig. 4. Volume of liquid at 1000°C. containing 1 mole (69.64 gm.) of oxygen. Types of liquids are indicated adjocent to the curves.
BlOs as a hnction of molar of cotion per liter of liquid. Types of liquids
are indicated adjacent to the curves.

manner of plotting shown in Fig. 5 was adopted. Figure 5 mental densities of alkali and alkaline-earth borates. For
shows a plot of VO,the volume of the liquid a t 1000°C. con- binary borates Huggins’ equations may be transformed to the
taining 1 gm. atom of oxygen, as a function of N M ,the gram following forms:
atoms of cations per gram atom of oxygen. The contractions
indicated in Fig. 4 are emphasized in Fig. 5. Minima such as Vo = NM Cm + NB CB (1)
are exhibited by the alkali borates are not obvious in the Ca, VO = volume of glass (cc.) containing 1 gm.atom of oxygen.
Sr, and Ba curves but can be inferred from the shapes of the NM = gram atoms of cations per gram atom of oxygen.
NB = gram atoms of boron per gram atom of oxygen.
curves at low concentrations together with the requirement = volume factor of cation (Na,Li, K, Ca, Sr, Ba).
CM
that they meet a t VO= 15.38 cc., the value for pure Bz03 a t CB = volume factor of boron.
1000°C. The curves for the divalent cations are incomplete
because of the formation of two liquids at low RO concentra- In the NBrange 0.50 to 0.67 the postulates of Huggins lead to
tions, but it takes no great stretch of the imagination to Visual- CB = ( 4 0 N ~- 1 4 ) / N ~ .Therefore
ize that at, for example, NM = 0.08 the order for the con- Vo = NM Cm + 40 NB - 14
tracting ef€ect would be Ca > Sr > Ba > Li > Na > K. At
high concentrations of cations the effect of cationic size per se For monovalent cations the condition for electroneutrality
becomes appreciable so that comparisons designed to show the +
requires that ~ N B NM= 2 or NB = (2 - N M ) / ~so , that
eflect of ionic potential should be confined to cations of ap- for monovalent cations
proximately equal sue. Na and Ca are nearly of equal size
(ionic radii 0.98 and 1.06 a.u., respectively) and Ca shows the
greater contracting effect, consistent with its greater electric
charge. Ba and K may also be compared (ionic radii 1.43
M Vo = NM(CM - 13.33) + 12.67 (2b)
and 1.33 a.u., respectively) and Ba shows the greater con- For divalent cations the condition for electroneutrality is
tracting effect, in line with its greater charge and in spite of 2Nx f ~ N = B2 or NB = 2(1 - Nm)/3; therefore
its somewhat larger size.
Figure 6 shows a plot of VOat room temperature as a func-
Vo i= + 80/3 - 8 0 N ~ / 3- 14
N M CM (30)
tion of N M . There are fewer data at room temperature be- M Vo = N M (CM - 26.67) + 12.67 (3b)
cause of crystallization of the alkaline-earth borates a t high Both (2b) and (3b) are equations of straight lines whose in-
concentrations of alkaline earth. The VOvalues are smaller tercepts are at 12.67 and slope (CM - 13.33) in the case of
in general, but the pattern shown a t 1000°C. is repeated a t alkali ions and (CM- 26.67) in the case of alkaline-earth ions.
lower temperatures. Some changes may be noted, such as
the rise of the Ba curve above that for Li and the flattening of
the minimum of the Na curve. e M. L. Huggins, “Density of Silicate Glasses as a Function of
It is of some interest to see how the results of Huggins’ Composition,” J . Opt. SOC.Amer., 30 191 42030 (1940); Cnam.
methodg of calculating densities compare with the expefi- Abstr., 20 [2]41 (1941).
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
November 1954 Molten Binary Alkaline-Earth Borates 549

I PK
14.01

1.61 1
. 1.62 1.66 L.70
R
1.74

Fig. 7. Stevels (footnote 10) X value versus R for binary alkaline-earth

1.78

borates. X = (12.16 - yd)/Rj y = moles of oxygen per 100 gm.of

glass; d = density; R = oxygen-to-boron ratio. Types of glasses are
indicated adjacent to the curves.

Table 111. Mean Volume Expansivity of Binary Alkaline-

Earth Borates Calculated from Change in Density with
Rg. 6. Vo, the volume (cc.) of glass a t room temperature containing 1
gm. atom of oxygen, vs. NM, gram atoms of cations per gram atom of
Temperature
oxygen. Types of glasses are indicated adjacent to the curves. Mean vol. Mean vol
expansivity expansivity
Temp. liquid range 25"-1100°C.
Mole % rance I o c . ) (D.D.m./'C.) (D.D.m./'C.)

BaO
The dashed lines in Fig. 6 show the calculated volume curves
for the alkalis. The displacement of Huggins' VO value for 17.8 847-1104 192
_- 111
pure BsOa from the experimental VO shown in Fig. 6 is caused
20.2 854-iio4 187 105
23.8 854-1004 190 105
by his use of a density value for BzOs smaller than the one em- 27 3 846-1099 212 116
ployed in this investigation. The volume factor for K 32.1 846-1100 223 126
(15.5) is greater than 13.33 and therefore its slope is positive. 36.3 907-1101 228 136
40.9 1004-1100 224
The volume factors, CM,for Na and Li are smaller than 13.33 45.9 1006-121 1 195
and therefore their lines have negative slopes. To simplify 51.6 996-1196 175
Fig. 6 the lines for Ba, Sr, and Ca are not shown, but they can
be calculated from equation (3b). The calculated curves sro
would be straight lines radiating from 12.67 with negative 22 4 91&1117 218 101
slopes having the values -10.67, -11.67, and -16.37, re- 26 4 951-1
. . ~~103 ~ . 22_
1 112
27.2 1006-1116 206 105
spectively. The straight-line requirements of Huggins' 29.5 954-1 100 218 116
method in the NB range 0.50 to 0.67 are not in accord with 31.3 997-1097 233 121
the experbentally observed minima. 33.8 958-1 100 230 125
Figure 7 shows a plot of the room-temperature data ac- 36.3 1003-1100 243 130
40.6 1120-1223 206
cording to the formula of Stevels'O: X = (12.16 -ya!)/R 45.3 1154-1205 1.52
(y = moles of oxygenions in 100 gm. of glass; d = density; R =
oxygen-to-boron ratio; X = a proportionality factor). CaO
According to Stevels, X should have a constant value of 2.3 31 2 906-1204 247 125
for R > 1.61. Inspection of Fig. 7 shows that X varies with 34 7 1056-1105 259 125
concentration and is a function of ionic size, the order of 37.1 1105-1200 219 129
42.5 1145-1193 188
values for the alkaline-earth borates being Ba > Sr > Ca. 15.7 1106-1207 185
This order is analogous to that observed with the alkalis,' 50.3 1156-1199 184
namely K > Na > Li. Stevels' designation of X as a "con-
traction-determining coefficient" derived from structural
considerations seems partly justified by experimental results.
The fact that X varies with concentration tends to limit its
usefulness.
Table III gives values of expansivity in the liquid range in density with temperature. The precision of such data is
and in the range 25' to llOO'C., both calculsLted~€romchange low, especially where the temperature range is small, and
caution should be used in drawing conclusions from them.
In the liquid range there seem to be maxima in expansivity
lo J. M. Stevels. Progress in Theory of Wyaicd Prapwtks
at ahout 36 mDLe % RO The over-all expansivity (25' to
of Glass. Elsevier Publishing Co., Inc., New Pork, 1948. 104 1lOO'C.) increases with increasing RO content over the con-
pp.; Ceram. Absir., 1949, March, p. 81b. centration ranges that were studied.
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
550 Journal of The American Ceramic Society-Shartsis and Shermer Vol. 37, No. 11
Table IV. Viscosity of Barium Borates
Wt.yo Mole yo Temp. (“(2.) Log 9

32.3 17.8 1002 1.062

897 1.866
898 1.848 2.5
804 3.008 - 850.C
1007 1.060
950 i.is9
903 1.851
35.8 20.2 1007 1.103
956 1.506
903 1.978
854 2.531
40.8 23.8 1004 1.096
950 1 573
903 1.978
854 2.547
45.3 27.3 949 1.501
896 1.935 1.0
846 2.552
51 .o 32.1 947 1.285
898 1.7ti9 I6 20 24 28
846 2.491
BOO (Mole % )
55.7 36.3 956 0.990
907 1.445 Fig. 8. log viscosity of some binary barium borates as a function
of BaO concentration.

L.8 r I I I 1
(3) v;acosity
With the exception of some of the barium compositions the
viscosities of the alkaline-earth borates were too low to be 1.6
measured with the available apparatus. Table I V gives the
viscosity results obtained with the barium borates and Fig. 8
shows a plot of the results at three temperatures. At each I.4
temperature there is evidence of a maximum at approxi-
mately 22 to 23 mole % BaO. A s i d a r maximum was ob-
served with the alkali borates.6 The viscosities of the barium a
1.2
borates are higher at 900OC. than those of the corresponding a
(mole per cent basis) alkali borates. It can be inferred that -I

the Sr and Ca borates are more fluid than the Ba borates be- I .o
cause they were too fluid to measure when not crystallized.
A t 916OC. a log TJ of 1.333 was found for a strontium borate of
22.4 mole % SrO. Inspection of Fig. 8 shows that the cor- t
responding barium borate has a higher viscosity.
0.8

0.6
\o
v1
(4) Ekctrical Resistivity 4 6 8 10 I2 14 16 18

Table V gives the electrical resistivity data obtained, and ALKALINE EARTH IONS, MOLES I LITER
Fig. 9 shows a plot of log R at llOO°C. (R = specific resist- Fig. 9. l o g R at 1 100aC. [R = specific resistance, ohms per cubic
ance, ohms per cubic centimeter) as a function of the con- centimeter) versus concentration of alkaline-earth ions. Types of liquids
centration of alkaline-earth cations. The resistivity de- are indicated adjacent to the curves.
creases with increasing concentration of alkaline earth. A t
corresponding RO concentrations the order Ca > Sr > Ba
exists for specific resistance. The resistance of the alkaline-
earth borates is much greater than that of the alkali borates of
comparable concentration.
Figure 10 shows a plot of the equivalent conductance at
1100OC. (the conductance of an amount of liquid containing
one electrochemical equivalent of alkaline-earth ions placed
between plane-parallel electrpdes 1 an.apart) as a function of
concentration at llOO°C. As is the case with the alkali
borates,a the equivalent conductance inueases with concentra-
tion, indicating that the mechanism of conduction does not
follow the Anhenius type, which consists of a dissociation of a
considerable portion of the electrolyte into positive and nega-
tive ions, but rather resembles a Grotthus type in which
conduction takes place by means of ion pairs that change
partners under the influence of an electric field. The ex-
change of partners of ion pairs can be expressed by the follow-
ing equation ; I I I I I I I

8 12 16 20 24 30 34
RoBeO4 + R++ -C Ro++ f RBzOd ALKALINE EARTH IONS,EQUIVALENTS PER LITER
Fig. 10. Equivalent conductance of molten binary alkaline-earth borates
where R = Ba, Sr, and Ca; ROis a particular R ion. at 1 1 OOOC. Types of liquids are indicated adjocent to the curve^.
 15512916, 1954, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1954.tb13987.x by Massachusetts Institute Of Technology, Wiley Online Library on [20/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
November 1954 Molten Binary Alkaline-Earth Borates 551
The explanation offered for Table V. Electrical Resistivities of Molten Binary Alkaline-Earth Borates
the behavior of alkaline-earth
borates under the influence of
an applied potential should be ~
Mole Yo
+
BaO
Temp. ("C.)
-
Log R
r
Mole %
SrO
Temp. ("C.)
7

Log R
.

Mole %
CaO
Temp. ("C.)
-
Loa R

taken with some reservation, 17.8 1313 0.993 22.4 1117 1.596 31.2 1204 0.982
1204 1.246 1015 2.185 1155 1.130
since the actual mechanism of 1099 1.568 916 3.066 1107 1.314
conduction may be much more 1002 2.058 1061 1.540
complicated than the one de- 597 2.764 1005 1 840
picted here. The values of 804 3.659 956 2.241
1104 1.596 906 2.784
equivalent conductance are 1007 2.083 26.4 1103 1.418
much lower for the alkaline- 950 2.386 1050 1.694
earth borates than for the 903 2.727 1002 2.077
alkali borates6 In spite of 847 3.288 951 2.350
796 3.887
the larger ionic size of Ba
20.2 1104 1.534 34.7 1105 1.196
and the higher viscosity of 1007 2.001 1056 1.439
barium borates, the equiva- 956 2.337 27.2 1116 1.487
lent conductance of barium 903 2.748 1006 2.123
borates is higher than that of 854 3.211
comparable strontium or cal- 23.8 1100 1.428
1004 1.902
cium borates. At compar- 950 2.246 29.5 1100 1.328 37.1 1200 0.832
able concentrations below 24 903 2.649 1051 I.766 1153 0.973
equivalents per liter the order 854 3.115 1010 1.868 1105 1.136
for equivalent conductance is 954 2.222 1050 1.354
Ba > Sr > Ca. 27.3 1099 1.288
999 1.774
949 2.064
IV. Summary and 896 2.509
846 3.018 31.3 1097 1.292
Conclusions 997 1.855
The surface tensions of a 32 1 1100 1.201 42.5 1193 0.724
1001 1.629 1145 0.845
series of calcium, strontium, 947 1.954
and barium borates were 898 2.344
measured. The values of 846 2.875 33.8 1100 1.209
surface tension obtained for 1050 1.425
36.3 1101 1.049 1001 1.710
the compositions which formed 1003 1.465 958 2.021
two liquids corresponded 956 1.712 45.7 1207 0.672
closely to those for pure B203. 907 2.077 1156 0.756
A t concentrations of RO above 854 2.592 1106 0.908
the two-liquid region, the 40.9 1100 0.924 36.3 1100 1.179
1004 I .272 1003 1.665
surface tension rose sharply.
45.9 1211 0.629
At 1100'C. the order for 1104 0.800
surface tension a t 30 mole yo 1006 1.107 50.3 1199 0.633
RO was Ba > Sr > Ca but 40.6 1223 0.724 1156 0.681
inverted to Ca > Sr > Ba at 51.6 1196 0.566 1203 0.819
1100 0.711 1120 0.986
56 mole %. The surface- 996 1 ,000
tension behavior of the alka- 45.3 1205 0.672 54.4 1197 0.531
line-earth borates showed 56.6 1202 0.629 1154 0.792
analogies to that of the alkali 1103 0.699
borates. 63.8 1119 0.582
A study of the densities of
binary alkaline-earth borates at
room and a t elevated tempera-
tures showed that large con-
tracting effects occurred upon the addition of alkaline-earth borates were considerably higher than those of the corre-
ions, especially a t the lower concentrations. These contracting sponding alkali borates.
effects were in the same order as the ionic potential, namely The specific conductance and the equivalent conductance
Ca > Sr > Ba. The methods of Stevels and Huggins for cal- were in the order Ba > Sr > Ca despite the fact that the
culating densities were not satisfactory when applied to the barium borates were the most viscous of the group and the
binary borates. The order for density was Ba > Sr > Ca. Ba ion was the largest. The equivalent conductance, as was
Only the barium borates were viscous enough to be meas- true with the alkali borates, increased with concentration.
ured with the counterbalanced-sphere apparatus used. The The range of concentrations of alkaline-earth oxides in
viscosity isotherms of the barium borate liquids in the tem- B ~ 0 3that form homogeneous glasses is limited by two-liquid
perature range 850' to 950'C. showed maxima around 22 to formation a t low concentrations and by crystallization a t high
23 mole % BaO. The viscosities observed for the barium concentrations. For this reason the data obtained are limited.

(See p. 558, this issue, for a discussion of Atcrest to those in the glass Jield)