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Arsenic-containing heavy-metal oxide glasses
Journal of Non-Crystalline North-Holland. Amsterdam
Solids
93 (1987)
ARSENIC-CONTAINING K. NASSAU, A T&T
HEAVY-METAL
D.L. CHADWICK
Bell Loborarories.
115-124
Murra.v
Received 27 February 1987 Revised manuscript received
Hill.
7 April
115
OXIDE
GLASSES
and A.E. MILLER NJ 07974,
USA
1987
A total of 68 binary through quinternary oxide arsenite glass compositions based on As,O, in combination with SbzO,. TlzO, PbO and/or Bi 2O3 were prepared. Glass and exothermic crystallization transition temperatures and thermal expansion coefficients were determined. Optical data were determined on the glass composition 40As0, 5~40Sb0,,~20TI0,,,, including the transparency range. refractive indexes, Sellmeier coefficients, Brillouin and Raman scattering data. and elastic constants.
1. Introduction This report is part of an extended study in infrared transmitting heavy-metal oxide glasses. Originally this study was intended to locate low-loss materials of interest as long distance optical transmission media; subsequently, such glasses were recognized as having exceptionally high Raman scattering coefficients; they have the potential of serving for active fiber Raman amplification. Initially glasses were studied using GeOz as the strong glass-forming agent combined with Bi *O,, Tl ,O, PbO, and/or Sb,O, [l-5]. The reason for avoiding SiO, is the infrared absorption expected for this relatively light cation oxide. Subsequently the study was extended to arsenite glasses based on As,O,, which is the only strong glass former besides GeO, having significant transmission potential farther into the infrared. This is illustrated by the calculated wavelength of he, the material dispersion crossover point, which is 1.3 pm for P,O,, B,O,, and SiO,, 1.7 pm for GeOz, and 1.9 pm for As,O, [6]. Arsenic oxide has long been used as a fining agent in glass [7], where it helps to remove bubbles and also tends to oxidize Fe0 to the less light-absorbing Fe,O,. Arsenic oxide also forms a pure vitreous phase by condensation from the vapor [8] or by quenching the melt in a sealed tube, used for various structural investigations [9,10]; these indicate the presence of rigid threemember rings with flexible connections between rings, quite unlike the arsenolite and claudetite forms of crystalline As,O, [lo]. There have been various reports on arsenite glasses containing arsenic oxide combined with alkalis and alkaline earths (e.g. ref. [ll]) or with GeO, and other oxides (e.g. ref. [12,13]) (the last of these [13] uses the designation
“arsenate” without any supporting data, however). heavy-metal oxide have been noted only rarely [14,15] and in patents [16.17].
Arsenite glasses containing in the technical literature
2. Experimental
The techniques of ball-milling. melting in heavy-walled platinum crucibles, water quenching in the crucible, and subsequent analyses have been described previously [2]. Reagents used were 99.8 + % AslO,, Bi,O,, PbO, Sb,O,, and TlzO, obtained from the Alpha Div.. Thiokol/Ventron Corp., Trenton. N.J. Loss of oxygen occurs in the change from Tl ,O, to Tl ,O: volatilization occurs with all but Bi?O, and PbO, but was kept to acceptable values by using the minimum temperatures necessary for melting and also by holding the melt only long enough for adequate mixing. Weight lossesof less than 0.5% were common; if the loss was over 30/o,then this is noted in the tables. The optical transmission and refractive index data were kindly taken by D.L. Wood as previously described [5,18], and the Raman and Brillouin data as described elsewhere[5,19].
3. Results
and discussion
The data obtained on binary, ternary, quaternary, and quinternary oxide compositions is presented in tables l-4, respectively. The presence of “bulk” glass as the only or dominant phase was based on visual examination, the absence of X-ray diffraction lines, the observation of a glass transition at Tg and an exothermic crystallization transformation at T,,, in differential thermal analysis (DTA) and Tg in thermomechanical analysis (TMA). For the determination of “some” or “trace” glass, visual examination was combined with an evaluation of the magnitude of the Tg and T,,, transformations in DTA. We continue to express compositions in cation percent as in our previous reports [l-5]. To obtain glasses with more than about 60% AsO,., it is necessary to use sealed tubes to prevent excessive vaporization; this region would undoubtedly have provided bulk glassin most or all of these systems in view of the strong glass-forming tendency of As,O,. Volatilization was lessof a problem with the increase in the number and amounts of other components and was almost totally absent in the 30-50%. AsO,,, quinternary compositions of table 4, where the lowest melting points were expected. There is extensive glass formation in the binary As,O,-Sb,O, system of table 1. Heaton and Moore [14] report a limit for glass formation of 67% SbO,.,; they also give an infrared absorption curve for the 50% composition. Much smaller glass-forming regions were noted for the other three binaries of table 1. Both Heaton and Moore [14] and Adams [15] report some glass up
Table 1 Binary oxide
glasses of As,O,
Composition
(cation
AsO, 10 20 30 40 50 60 70 20 30 40 50 60 20 40 50 60 30 40 50
s
SW 90
s
with
Sb,O,.
%) TI%
s
PbO
B%
80 70 60 50 40 30 80 70 60 50 40 80 60 50 40 70 60 50
T120.
PbO, or Bi,O,
Presence of glass
T ”
(Q,
Tc,,,, “’ (“0
a h’ (lo-” 23 23 23 24 23 26
trace
260
320
bulk bulk bulk ” bulk ‘I bulk ” bulk ” none” none L’ some trace ” some? ‘) none none bulk trace? none trace none ”
240 230 230 220 220 210 160? llO?
330 330 320 310? 280? 250? 180? 310. 380 280 -
230 250 220 360?
250 400?. 520?
K-‘)
24
I
”
rs is the glass transition temperature and T,,,, the initial exotherm (crystallization) temperature. both to the nearest loo;? indicates uncertainty about the interpretation of the data. h’ a is the linear thermal expansion coefficient. to the nearest 1 x lo-“. ” Significant volatization occurred. ‘) Opaque. probably two-phase glass.
to 60% PbO; a patent [17] includes 40 and 51% PbO compositions. There is increasingly extended occurrence of glass in the ternary, quaternary, and quinternary compositions of tables 2 and 3, as is so frequently observed in glass-forming systems. In this region there is a solder glass reported in a patent by Eubank and Beck [16], which at 40AsO,,, .40SbO,,, .20PbO has a softening point of 287°C and a thermal expansion coefficient (Y of 12.8 x lop6 K-‘; the Leitz patents [17] also list two glass-forming compositions: 33.3AsO,,, .44.2PbO. 22.5SbO,,, and 54.9AsO,,, . 41.8PbO. 3.3BiO,,. Overall, the glass-forming tendency of these oxides with AszO, in binary compositions can be given as Sb Z+ Pb > Ti > Bi. However, this order no longer applies in multi-component systems. In the quaternary compositions of table 3, for example, the best glass formation occurs in the absence of the intermediate-positioned Pb or Tl, while the absence of Bi, the poorest glassforming component in the binary compositions, here unexpectedly gives the least range of glasses. Extensive plotting of the occurrence of glass data of Tables 1 to 4 in multi-component diagrams, such as that shown in fig. 1. produced no additional insight in this question. If attention is focused only on average values for the 40-50s AsO,,, compositions of tables l-4, then several generalizations can be noted. The
Table 2 Ternary oxide Composition
glasses (cation
of As,O,
with
Sb,O,,
S) PbO
BiO 1.5
TI,Q.
PbQ,
and/or
Presence
T, "
T,,, "
a h'
of glass
(“C)
(“(3
(1O-6
360.480
17
340 350,460?
16 20
-
16 18
AsO,.,
SW,
T’0o.s
30 40
50 30
20 30
bulk bulk
280 270
40 40 50
40 45 40
20 I5 10
bulk bulk bulk
40 50 50
30 20 30
270 290 280 240
40 40 50
30
30 30 20 30 20
30 30
50 30
30 20
20
40 40
20 30
50 40
10
40 30
to table
Table 3 Quaternary
oxide
Composition
”
20 30
30 20
bulk trace
of AssO,
280 250
350 270
330
350 370,410 330
18 -
410
16
300 300 310
-
-
with
Sb,O,.
%)
AsO,.,
SW.,
T'%.s
PbO
25 30
25 20
25 30
25 20
30 40
30 20
10 20
30 20
50 25 30
10 25 20
10 25
30
350
270 290
15 -
BiO 1.5
25
TI,O,
PbO,
and/or
Presence of glass
(Q)
(T)
trace
200
trace trace trace
200 220 210
270 280,370 -
”
a’
Bi,O,
T
-
none some
260
T
30
30 15 20
30 20
15 20
bulk bulk
50 50
10 20
20 10
20
some
”
270
50 55 25
20 15
20 15
20 10
bulk ” some ”
270 260
25 10
15 25 30
bulk ” some ” some ”
270 340 320
20 10 25
bulk bulk
310 250
25
20 30 25
380,410 330 -
30 40
10 30 20
30 20 20
30 20 20
some some
300 220
360 290? 310,400
50 50
10 20
30 10
10 20
50 25 30
See footnotes
10
to table
1.
20 30
some
270 280 260 280
360, 420 350 320,430
some some
d’
250,270 260
some
”
260?
a h' (1O-6
380,460 410
40 40
25 30 20
"
260, 320 -
30 10
30 40
14 -
-
trace bulk”
360
300
”
40 30
-
230 230
”
trace trace bulk
30
320
K-‘)
1
glasses
(cation
” ”
bulk none trace
50
50 50 See footnotes
trace trace” trace 30
Bi,Q,
340
420? 330,340 380 380
310 330
390
18 16
19 18
16 15
K-‘)
K. Nassau et al. / Arsenic-containing Table
heavy-metal
oxide glasses
119
4
Quintemary
oxide
Composition
glasses
(cation
containing
As,O,,
I%)
TQs
Bi%
TI 2O, PbO,
Presence of glass
and
T =’
Bi 2O3
T
(Q)
(
r”” C)
”
a h’ (1O-6
A0.s
SW
30 30
10 20
20 10
20 20
20 20
trace
290?
350
some
30 40
25 10
10 10
25 20
10 20
bulk some
40 40 40
10 10 10
10 20 20
30 10
10 20
trace some
290 290 280 200?
380 370 340.370 260?
15 15
some bulk bulk
360 290
15 15 20
10 15 20
260 210
40 40 40
20 15 10
10 20 10
some bulk some
18 20 -
20 20
20 10 10
350 400.450 300
40 40
10 10 20
280 270 240 280 250
430,490 330,400
17 -
50 50 50
10 10 10
10 10
10 20 10
20 10 10
bulk d’ some
250. 330 220 220?
370,410 300 300
18.86 -
50
20
10
10
240
320
19
See
footnotes
.s
PbO
Sb,O,,
20 10 of table
some bulk
”
K-‘)
18 -
1.
values of Tg for the binary oxide systems are all about 225’ C, with T,,, being As . Sb - As. Pb - 310 o C > As . Bi - 250 o C. This combination of values gives A = T,,, - Tg, the temperature interval between the glass transition and the crystallization points, as the sequence As . Sb - As . Pb - 85 o C > As. Bi - 25OC.
50%
40%
AsOl
AsO,,~
‘v
“ill/)’ 0 BULK
GLASS
0
GLASS
SOME
B TRACE 30%
AsO,.~
GLASS
0 NO GLASS
3
SbOl.5 Fig.
1.
The
occurrence
of
glass
at three As,O, As,O,~Sb,O,~Tl,O~Bi,O~.
levels
in
the
quatemary
oxide
system
120
~OASO,,~
loSbO,,, I
Fig.
2. The differential
thermal transitions
,
1
400 (“C)
500
I
300 TEMPERATURE
200
analysis (Ts) and
of a quinternary double crystallization
oxide
arsenite exotherms
glass showing (r,,,).
double
glass
In the ternary oxide compositions of table 2. the equivalent Tg values range from a low of 230 o C for As. Sb . Pb to a high of 300 o C for As. Sb Bi and As. Tl . Bi. Values of T,,, range from 340 to 370 o C, and A from 60 to 80 o C. For the quaternaries of table 3, the equivalent values for T, and T,,,,, respectively, range from lows of 210” C and 260°C (with Bi absent) to highs of 31O’C and 380 o C (with Tl absent); A values range from 50 to 80 o C. The equivalent thermal expansion coefficients (X 10e6 K-‘) were 23 to 26 for all available binary compositions of As,O, with SbzO, or PbO but somewhat lower in the 14 to 18 range for more complex compositions. Double exotherms were observed in several compositions, presumably resulting from metastable transformations or multiple crystallizations; such phenomena are common in quenched oxide glasses [20]. Double glass transitions were also noted, particularly in the quinternary glasses of table 4. One of the compositions, namely 50AsO,., . lOSbO,,, . lOTlO,., . lOPb0. 20Bi0,,j, showed two glass transitions Tg’ and T,” and also T& and T& as can be seen in the DTA of fig. 2. This glass also showed the very unusual thermal expansion behavior of fig. 3, compared to the commonly-seen simple upper curve included for comparison. This was the only anomalous thermal expansion curve observed. This type of behavior has been previously reported in the GeOz-La,O, system [21]. Using the same approach, one can suggest an explanation for the anomalous thermal expansion behavior of fig. 2 on the basis of a phase-separated structure in which an interconnected or matrix phase has a low Tgf and a low (Y, while a second discontinuous phase has a higher T,” and a higher (Y. When the glass is heated, the discontinuous higher LY phase expands within the rigid matrix and builds up pressure. When the matrix Tg’ is approached, the result of this compressed second phase now dilating the matrix phase is an apparently anomalous very large thermal expansion as observed in fig. 3. The optical transparency of two of the arsenite glasses is given in fig. 4, where the curves for SiO, and GeO, are also included for comparison. The large absorptions in the 3.2 pm region are undoubtedly derived from hydroxyl
K. Nassau
et al. / Arsenic-containing
heavy-metal
oxide
glasses
121
1.2 TMA 5O/MIN
0.0
1.0 0.6
DTL
.l
0.2
0 0
100 TEMPERATURE
Fig.
3. The
anomalous
thermal
expansion .50SbO,,,
5DAso,.~
300
200 (“C)
curve of is included
the glass of fig. for comparison.
2; the normal
binary
present in the glass; the reaction of AszO, with water to form arsenious acid, As (OH), is well-known. This tendency to hydration is higher here than in the germanate glasses previously studied. For the quinternary oxide glass of fig. 4 , the refractive index no is 2.133, Tg = 270 ‘C, T,,, = 400 o C, and (Y = 20 x lo-” K-‘. An extended study was made of one of the two glasses of fig. 4, namely the ternary oxide glass 40AsO,,, .40SbO,,, . 20 TlO,,,. The refractive index data is
15T
0.2
0.4
0.6
5
loPbo
0.0
2.5 WAVELENGTH
Fig. 4. The optical
3.5
4.5
5.5
6.5
7.5
(pm)
transparency curves of two arsenite glasses compared to those of GeO, SiO,. Left section, w-visible, near ir; right section, farther ir.
and
K. Nassau et al. / Arsenic-containing
122
1.9oL
0.3
’
0.5
heavy-metal
I
I
I
I
1.0
1.5
2.0
2.5
WAVELENGTH
Fig. 5. The refractive
Table 5 Properties Sellmeier
index variation
of the glass 40AsO,.,
oxide glasses
with wavelength
.40SbO,
of the ternary
s .2OTlOo,s
coefjicienls:
Al A2 A3 B, B2 B3
1.41496 1.26444 2.04210 0.110100 0.222207 17.30334
Optical parameters: “0 “x0
Disp.=nr-nc Abbe number &I dM/dX High frequency acourric and elastic parameters: Longitudinal acoustic velocity Transverse acoustic velocity Shear modulus Young’s modulus Bulk modulus Poisson’s ratio Other parameters: Ts T exe a Density
3.0
+f-n)
2.002 1.921 0.049 20.45 2.314 pm 57.4 ps/nm.km.pm 2.78 1.55 13.0 33.3 24.9 0.277
km s-’ km s-’ GPa GPa GPa
27O’C 350°c 20~10-~ K-’ 5.45 g cmm3
oxide
arsenite
glass of fig. 4.
K. Nassau et al. / Arsenic-containing 50 50
I
heavy-metal
I
I
oxide glasses
123
I
40A~0~.5~4osbo,.5~20Tt00.5 40A~0~.5~4osbo,.5~20Tt0~.5
0' 0’
0
200
400 FREQUENCY
Fig. 6. The Raman
presented graphically formula,
scattering
600 SHIFT
curve
000
1000
(cm”) of the glass of fig. 5.
in fig. 5 and table 5 in the form of a three-term
Sellmeier
n2-l= iA;A’(x’-B,Z)-l, i=l
where A, and B, are constants and A is the wavelength at which the refractive index is n. Other parameters included in table 5 are those derived from the Sellmeier coefficients, including values of X a, the wavelength for zero material dispersion where d2n/dh2 = 0, d M/dh, the slope of the material dispersion at X,, the refractive indexes at the sodium D line and at h,, the dispersion the Abbe number (nb - l)/( nF - n,), as well as other materials nF-nc, parameters. Brillouin and Raman scattering data were also determined on this same glass. The Brillouin scattering, using 0.5145 pm excitation, shows frequency shifts Au = 15.3 and 8.5 for the longitudinal (uu or uh) and transverse (uh only) acoustic phonons, respectively. From these values the respective acoustic velocities are 2.78 x 10’ and 1.55 X lo5 cm s-r and lead to the high-frequency elastic constants given in table 5. The Raman scattering data for this same glass are shown in fig. 6. The strongest scattering occurs at 490 cm-’ and has a peak height of 37 times that
124
K. Nassau
el al. / Arsenic-conrarning
heaqv-meral
oxide
glasses
of the maximum peak of fused’silica. Two additional glasses were measured and gave peak heights of 16 times fused silica at 440 cm-’ and 36 times fused silica at 430 cm-’ in 50AsO,,, . 20Bi0,,5. 20SbO,,, . lOTlO,,, and 50AsO,., . a refractive index of 2.0 was assumed in the data 50SbO,,,. respectively; reduction for both these glasses in the absence of measurements. The high Raman scattering values here observed are as high or even higher than those in the germania-based heavy metal glasses previously studied [19]; against this must be considered the significant volatility of AszO, at the melting temperatures, which would make it very difficult to control the composition and therefore the refractive index profile of Raman active fibers. We wish to thank D.L. Wood for providing the transparency refractive index, J.W. Fleming for reducing the latter, and M.E. K.B. Lyons for helpful discussions.
data and Lines and
References [l] [2] [3] [4] [5] [6] [7] [S] [9] [IO] [ll] [12] [13] [14] [15] [16]
[17] [18] [19] [20]
[21]
K. Nassau and D.L. Chadwick. Mat. Res. Bull. 17 (1982) 715. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 65 (1982) 197. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 65 (1982) 486. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 66 (1983) 332. D.L. Wood. K. Nassau and D.L. Chadwick. Appl. Opt. 21 (1982) 4276. K. Nassau, Bell Syst. Tech. J. 60 (1981) 327. R. Kenworthy. Silicates Ind. 37 (1972) 245. W.A. Weyl and E C. Marboe, The Constitution of Glasses (Wiley-Interscience, New York, 1964) pp. 620-621. F.L. Galeener. G. Lucovsky and R.H. Geils. Phys. Rev. B19 (1979) 4251. M. Imaoka and H. Hasegawa, Phys. Chem. Glasses 21 (1980) 67. M. Imaoka. Glass-Formation Range and Glass Structure, Adv. in Glass Technol., Vol. 1 (Plenum. New York. 1962) pp. 149-163. N. Mochida and K. Takahashi, Proc. 10th Int. Congress on Glass. Vol. 13 (Ceramic Sot. of Japan. 1974) pp. 29-35. W.H. Grodkiewicz. H.M. O’Brian, L. Pressman. S. Singh, L.G. Van Uitert and G. Zydzik, J. Non-Cryst. Solids 44 (1981) 405; Mater. Res. Bull. 16 (1981) 373. H.M. Heaton and H. Moore, J. Sot. Glass Technol. 41 (1957) 3T-27T. R.V. Adams, Phys. Chem. Glasses 2 (1961) 101. W.R. Eubank and W.R. Beck, U.S. Patent 2.863.782 (1958). cited by T. Takamori. in: Treatise on Materials Science and Technology, Vol. 17, Glass II. eds. M. Tomozawa and R.H. Doremus (Academic Press, New York, 1979) 173. E. Leitz, German Patent 1,006,559 (April 26, 1967); French Patent 1,468,344 (Feb. 3, 1967). D.L. Wood and J.W. Fleming, Jr., Rev. Sci. Instr. 53 (1982) 43. A.E. Miller, K. Nassau, K.B. Lyons and M.E. Lines. to be published. K. Nassau, CA. Wang, and M. Grasso, J. Am. Ceram. Sot. 62 (1979) 74. K. Nassau, D.L. Chadwick, G.W. Kammlott and E.M. Rabinovich. Phys. Chem. Glasses 24 (1983) 150.
Solids
93 (1987)
ARSENIC-CONTAINING K. NASSAU, A T&T
HEAVY-METAL
D.L. CHADWICK
Bell Loborarories.
115-124
Murra.v
Received 27 February 1987 Revised manuscript received
Hill.
7 April
115
OXIDE
GLASSES
and A.E. MILLER NJ 07974,
USA
1987
A total of 68 binary through quinternary oxide arsenite glass compositions based on As,O, in combination with SbzO,. TlzO, PbO and/or Bi 2O3 were prepared. Glass and exothermic crystallization transition temperatures and thermal expansion coefficients were determined. Optical data were determined on the glass composition 40As0, 5~40Sb0,,~20TI0,,,, including the transparency range. refractive indexes, Sellmeier coefficients, Brillouin and Raman scattering data. and elastic constants.
1. Introduction This report is part of an extended study in infrared transmitting heavy-metal oxide glasses. Originally this study was intended to locate low-loss materials of interest as long distance optical transmission media; subsequently, such glasses were recognized as having exceptionally high Raman scattering coefficients; they have the potential of serving for active fiber Raman amplification. Initially glasses were studied using GeOz as the strong glass-forming agent combined with Bi *O,, Tl ,O, PbO, and/or Sb,O, [l-5]. The reason for avoiding SiO, is the infrared absorption expected for this relatively light cation oxide. Subsequently the study was extended to arsenite glasses based on As,O,, which is the only strong glass former besides GeO, having significant transmission potential farther into the infrared. This is illustrated by the calculated wavelength of he, the material dispersion crossover point, which is 1.3 pm for P,O,, B,O,, and SiO,, 1.7 pm for GeOz, and 1.9 pm for As,O, [6]. Arsenic oxide has long been used as a fining agent in glass [7], where it helps to remove bubbles and also tends to oxidize Fe0 to the less light-absorbing Fe,O,. Arsenic oxide also forms a pure vitreous phase by condensation from the vapor [8] or by quenching the melt in a sealed tube, used for various structural investigations [9,10]; these indicate the presence of rigid threemember rings with flexible connections between rings, quite unlike the arsenolite and claudetite forms of crystalline As,O, [lo]. There have been various reports on arsenite glasses containing arsenic oxide combined with alkalis and alkaline earths (e.g. ref. [ll]) or with GeO, and other oxides (e.g. ref. [12,13]) (the last of these [13] uses the designation
“arsenate” without any supporting data, however). heavy-metal oxide have been noted only rarely [14,15] and in patents [16.17].
Arsenite glasses containing in the technical literature
2. Experimental
The techniques of ball-milling. melting in heavy-walled platinum crucibles, water quenching in the crucible, and subsequent analyses have been described previously [2]. Reagents used were 99.8 + % AslO,, Bi,O,, PbO, Sb,O,, and TlzO, obtained from the Alpha Div.. Thiokol/Ventron Corp., Trenton. N.J. Loss of oxygen occurs in the change from Tl ,O, to Tl ,O: volatilization occurs with all but Bi?O, and PbO, but was kept to acceptable values by using the minimum temperatures necessary for melting and also by holding the melt only long enough for adequate mixing. Weight lossesof less than 0.5% were common; if the loss was over 30/o,then this is noted in the tables. The optical transmission and refractive index data were kindly taken by D.L. Wood as previously described [5,18], and the Raman and Brillouin data as described elsewhere[5,19].
3. Results
and discussion
The data obtained on binary, ternary, quaternary, and quinternary oxide compositions is presented in tables l-4, respectively. The presence of “bulk” glass as the only or dominant phase was based on visual examination, the absence of X-ray diffraction lines, the observation of a glass transition at Tg and an exothermic crystallization transformation at T,,, in differential thermal analysis (DTA) and Tg in thermomechanical analysis (TMA). For the determination of “some” or “trace” glass, visual examination was combined with an evaluation of the magnitude of the Tg and T,,, transformations in DTA. We continue to express compositions in cation percent as in our previous reports [l-5]. To obtain glasses with more than about 60% AsO,., it is necessary to use sealed tubes to prevent excessive vaporization; this region would undoubtedly have provided bulk glassin most or all of these systems in view of the strong glass-forming tendency of As,O,. Volatilization was lessof a problem with the increase in the number and amounts of other components and was almost totally absent in the 30-50%. AsO,,, quinternary compositions of table 4, where the lowest melting points were expected. There is extensive glass formation in the binary As,O,-Sb,O, system of table 1. Heaton and Moore [14] report a limit for glass formation of 67% SbO,.,; they also give an infrared absorption curve for the 50% composition. Much smaller glass-forming regions were noted for the other three binaries of table 1. Both Heaton and Moore [14] and Adams [15] report some glass up
Table 1 Binary oxide
glasses of As,O,
Composition
(cation
AsO, 10 20 30 40 50 60 70 20 30 40 50 60 20 40 50 60 30 40 50
s
SW 90
s
with
Sb,O,.
%) TI%
s
PbO
B%
80 70 60 50 40 30 80 70 60 50 40 80 60 50 40 70 60 50
T120.
PbO, or Bi,O,
Presence of glass
T ”
(Q,
Tc,,,, “’ (“0
a h’ (lo-” 23 23 23 24 23 26
trace
260
320
bulk bulk bulk ” bulk ‘I bulk ” bulk ” none” none L’ some trace ” some? ‘) none none bulk trace? none trace none ”
240 230 230 220 220 210 160? llO?
330 330 320 310? 280? 250? 180? 310. 380 280 -
230 250 220 360?
250 400?. 520?
K-‘)
24
I
”
rs is the glass transition temperature and T,,,, the initial exotherm (crystallization) temperature. both to the nearest loo;? indicates uncertainty about the interpretation of the data. h’ a is the linear thermal expansion coefficient. to the nearest 1 x lo-“. ” Significant volatization occurred. ‘) Opaque. probably two-phase glass.
to 60% PbO; a patent [17] includes 40 and 51% PbO compositions. There is increasingly extended occurrence of glass in the ternary, quaternary, and quinternary compositions of tables 2 and 3, as is so frequently observed in glass-forming systems. In this region there is a solder glass reported in a patent by Eubank and Beck [16], which at 40AsO,,, .40SbO,,, .20PbO has a softening point of 287°C and a thermal expansion coefficient (Y of 12.8 x lop6 K-‘; the Leitz patents [17] also list two glass-forming compositions: 33.3AsO,,, .44.2PbO. 22.5SbO,,, and 54.9AsO,,, . 41.8PbO. 3.3BiO,,. Overall, the glass-forming tendency of these oxides with AszO, in binary compositions can be given as Sb Z+ Pb > Ti > Bi. However, this order no longer applies in multi-component systems. In the quaternary compositions of table 3, for example, the best glass formation occurs in the absence of the intermediate-positioned Pb or Tl, while the absence of Bi, the poorest glassforming component in the binary compositions, here unexpectedly gives the least range of glasses. Extensive plotting of the occurrence of glass data of Tables 1 to 4 in multi-component diagrams, such as that shown in fig. 1. produced no additional insight in this question. If attention is focused only on average values for the 40-50s AsO,,, compositions of tables l-4, then several generalizations can be noted. The
Table 2 Ternary oxide Composition
glasses (cation
of As,O,
with
Sb,O,,
S) PbO
BiO 1.5
TI,Q.
PbQ,
and/or
Presence
T, "
T,,, "
a h'
of glass
(“C)
(“(3
(1O-6
360.480
17
340 350,460?
16 20
-
16 18
AsO,.,
SW,
T’0o.s
30 40
50 30
20 30
bulk bulk
280 270
40 40 50
40 45 40
20 I5 10
bulk bulk bulk
40 50 50
30 20 30
270 290 280 240
40 40 50
30
30 30 20 30 20
30 30
50 30
30 20
20
40 40
20 30
50 40
10
40 30
to table
Table 3 Quaternary
oxide
Composition
”
20 30
30 20
bulk trace
of AssO,
280 250
350 270
330
350 370,410 330
18 -
410
16
300 300 310
-
-
with
Sb,O,.
%)
AsO,.,
SW.,
T'%.s
PbO
25 30
25 20
25 30
25 20
30 40
30 20
10 20
30 20
50 25 30
10 25 20
10 25
30
350
270 290
15 -
BiO 1.5
25
TI,O,
PbO,
and/or
Presence of glass
(Q)
(T)
trace
200
trace trace trace
200 220 210
270 280,370 -
”
a’
Bi,O,
T
-
none some
260
T
30
30 15 20
30 20
15 20
bulk bulk
50 50
10 20
20 10
20
some
”
270
50 55 25
20 15
20 15
20 10
bulk ” some ”
270 260
25 10
15 25 30
bulk ” some ” some ”
270 340 320
20 10 25
bulk bulk
310 250
25
20 30 25
380,410 330 -
30 40
10 30 20
30 20 20
30 20 20
some some
300 220
360 290? 310,400
50 50
10 20
30 10
10 20
50 25 30
See footnotes
10
to table
1.
20 30
some
270 280 260 280
360, 420 350 320,430
some some
d’
250,270 260
some
”
260?
a h' (1O-6
380,460 410
40 40
25 30 20
"
260, 320 -
30 10
30 40
14 -
-
trace bulk”
360
300
”
40 30
-
230 230
”
trace trace bulk
30
320
K-‘)
1
glasses
(cation
” ”
bulk none trace
50
50 50 See footnotes
trace trace” trace 30
Bi,Q,
340
420? 330,340 380 380
310 330
390
18 16
19 18
16 15
K-‘)
K. Nassau et al. / Arsenic-containing Table
heavy-metal
oxide glasses
119
4
Quintemary
oxide
Composition
glasses
(cation
containing
As,O,,
I%)
TQs
Bi%
TI 2O, PbO,
Presence of glass
and
T =’
Bi 2O3
T
(Q)
(
r”” C)
”
a h’ (1O-6
A0.s
SW
30 30
10 20
20 10
20 20
20 20
trace
290?
350
some
30 40
25 10
10 10
25 20
10 20
bulk some
40 40 40
10 10 10
10 20 20
30 10
10 20
trace some
290 290 280 200?
380 370 340.370 260?
15 15
some bulk bulk
360 290
15 15 20
10 15 20
260 210
40 40 40
20 15 10
10 20 10
some bulk some
18 20 -
20 20
20 10 10
350 400.450 300
40 40
10 10 20
280 270 240 280 250
430,490 330,400
17 -
50 50 50
10 10 10
10 10
10 20 10
20 10 10
bulk d’ some
250. 330 220 220?
370,410 300 300
18.86 -
50
20
10
10
240
320
19
See
footnotes
.s
PbO
Sb,O,,
20 10 of table
some bulk
”
K-‘)
18 -
1.
values of Tg for the binary oxide systems are all about 225’ C, with T,,, being As . Sb - As. Pb - 310 o C > As . Bi - 250 o C. This combination of values gives A = T,,, - Tg, the temperature interval between the glass transition and the crystallization points, as the sequence As . Sb - As . Pb - 85 o C > As. Bi - 25OC.
50%
40%
AsOl
AsO,,~
‘v
“ill/)’ 0 BULK
GLASS
0
GLASS
SOME
B TRACE 30%
AsO,.~
GLASS
0 NO GLASS
3
SbOl.5 Fig.
1.
The
occurrence
of
glass
at three As,O, As,O,~Sb,O,~Tl,O~Bi,O~.
levels
in
the
quatemary
oxide
system
120
~OASO,,~
loSbO,,, I
Fig.
2. The differential
thermal transitions
,
1
400 (“C)
500
I
300 TEMPERATURE
200
analysis (Ts) and
of a quinternary double crystallization
oxide
arsenite exotherms
glass showing (r,,,).
double
glass
In the ternary oxide compositions of table 2. the equivalent Tg values range from a low of 230 o C for As. Sb . Pb to a high of 300 o C for As. Sb Bi and As. Tl . Bi. Values of T,,, range from 340 to 370 o C, and A from 60 to 80 o C. For the quaternaries of table 3, the equivalent values for T, and T,,,,, respectively, range from lows of 210” C and 260°C (with Bi absent) to highs of 31O’C and 380 o C (with Tl absent); A values range from 50 to 80 o C. The equivalent thermal expansion coefficients (X 10e6 K-‘) were 23 to 26 for all available binary compositions of As,O, with SbzO, or PbO but somewhat lower in the 14 to 18 range for more complex compositions. Double exotherms were observed in several compositions, presumably resulting from metastable transformations or multiple crystallizations; such phenomena are common in quenched oxide glasses [20]. Double glass transitions were also noted, particularly in the quinternary glasses of table 4. One of the compositions, namely 50AsO,., . lOSbO,,, . lOTlO,., . lOPb0. 20Bi0,,j, showed two glass transitions Tg’ and T,” and also T& and T& as can be seen in the DTA of fig. 2. This glass also showed the very unusual thermal expansion behavior of fig. 3, compared to the commonly-seen simple upper curve included for comparison. This was the only anomalous thermal expansion curve observed. This type of behavior has been previously reported in the GeOz-La,O, system [21]. Using the same approach, one can suggest an explanation for the anomalous thermal expansion behavior of fig. 2 on the basis of a phase-separated structure in which an interconnected or matrix phase has a low Tgf and a low (Y, while a second discontinuous phase has a higher T,” and a higher (Y. When the glass is heated, the discontinuous higher LY phase expands within the rigid matrix and builds up pressure. When the matrix Tg’ is approached, the result of this compressed second phase now dilating the matrix phase is an apparently anomalous very large thermal expansion as observed in fig. 3. The optical transparency of two of the arsenite glasses is given in fig. 4, where the curves for SiO, and GeO, are also included for comparison. The large absorptions in the 3.2 pm region are undoubtedly derived from hydroxyl
K. Nassau
et al. / Arsenic-containing
heavy-metal
oxide
glasses
121
1.2 TMA 5O/MIN
0.0
1.0 0.6
DTL
.l
0.2
0 0
100 TEMPERATURE
Fig.
3. The
anomalous
thermal
expansion .50SbO,,,
5DAso,.~
300
200 (“C)
curve of is included
the glass of fig. for comparison.
2; the normal
binary
present in the glass; the reaction of AszO, with water to form arsenious acid, As (OH), is well-known. This tendency to hydration is higher here than in the germanate glasses previously studied. For the quinternary oxide glass of fig. 4 , the refractive index no is 2.133, Tg = 270 ‘C, T,,, = 400 o C, and (Y = 20 x lo-” K-‘. An extended study was made of one of the two glasses of fig. 4, namely the ternary oxide glass 40AsO,,, .40SbO,,, . 20 TlO,,,. The refractive index data is
15T
0.2
0.4
0.6
5
loPbo
0.0
2.5 WAVELENGTH
Fig. 4. The optical
3.5
4.5
5.5
6.5
7.5
(pm)
transparency curves of two arsenite glasses compared to those of GeO, SiO,. Left section, w-visible, near ir; right section, farther ir.
and
K. Nassau et al. / Arsenic-containing
122
1.9oL
0.3
’
0.5
heavy-metal
I
I
I
I
1.0
1.5
2.0
2.5
WAVELENGTH
Fig. 5. The refractive
Table 5 Properties Sellmeier
index variation
of the glass 40AsO,.,
oxide glasses
with wavelength
.40SbO,
of the ternary
s .2OTlOo,s
coefjicienls:
Al A2 A3 B, B2 B3
1.41496 1.26444 2.04210 0.110100 0.222207 17.30334
Optical parameters: “0 “x0
Disp.=nr-nc Abbe number &I dM/dX High frequency acourric and elastic parameters: Longitudinal acoustic velocity Transverse acoustic velocity Shear modulus Young’s modulus Bulk modulus Poisson’s ratio Other parameters: Ts T exe a Density
3.0
+f-n)
2.002 1.921 0.049 20.45 2.314 pm 57.4 ps/nm.km.pm 2.78 1.55 13.0 33.3 24.9 0.277
km s-’ km s-’ GPa GPa GPa
27O’C 350°c 20~10-~ K-’ 5.45 g cmm3
oxide
arsenite
glass of fig. 4.
K. Nassau et al. / Arsenic-containing 50 50
I
heavy-metal
I
I
oxide glasses
123
I
40A~0~.5~4osbo,.5~20Tt00.5 40A~0~.5~4osbo,.5~20Tt0~.5
0' 0’
0
200
400 FREQUENCY
Fig. 6. The Raman
presented graphically formula,
scattering
600 SHIFT
curve
000
1000
(cm”) of the glass of fig. 5.
in fig. 5 and table 5 in the form of a three-term
Sellmeier
n2-l= iA;A’(x’-B,Z)-l, i=l
where A, and B, are constants and A is the wavelength at which the refractive index is n. Other parameters included in table 5 are those derived from the Sellmeier coefficients, including values of X a, the wavelength for zero material dispersion where d2n/dh2 = 0, d M/dh, the slope of the material dispersion at X,, the refractive indexes at the sodium D line and at h,, the dispersion the Abbe number (nb - l)/( nF - n,), as well as other materials nF-nc, parameters. Brillouin and Raman scattering data were also determined on this same glass. The Brillouin scattering, using 0.5145 pm excitation, shows frequency shifts Au = 15.3 and 8.5 for the longitudinal (uu or uh) and transverse (uh only) acoustic phonons, respectively. From these values the respective acoustic velocities are 2.78 x 10’ and 1.55 X lo5 cm s-r and lead to the high-frequency elastic constants given in table 5. The Raman scattering data for this same glass are shown in fig. 6. The strongest scattering occurs at 490 cm-’ and has a peak height of 37 times that
124
K. Nassau
el al. / Arsenic-conrarning
heaqv-meral
oxide
glasses
of the maximum peak of fused’silica. Two additional glasses were measured and gave peak heights of 16 times fused silica at 440 cm-’ and 36 times fused silica at 430 cm-’ in 50AsO,,, . 20Bi0,,5. 20SbO,,, . lOTlO,,, and 50AsO,., . a refractive index of 2.0 was assumed in the data 50SbO,,,. respectively; reduction for both these glasses in the absence of measurements. The high Raman scattering values here observed are as high or even higher than those in the germania-based heavy metal glasses previously studied [19]; against this must be considered the significant volatility of AszO, at the melting temperatures, which would make it very difficult to control the composition and therefore the refractive index profile of Raman active fibers. We wish to thank D.L. Wood for providing the transparency refractive index, J.W. Fleming for reducing the latter, and M.E. K.B. Lyons for helpful discussions.
data and Lines and
References [l] [2] [3] [4] [5] [6] [7] [S] [9] [IO] [ll] [12] [13] [14] [15] [16]
[17] [18] [19] [20]
[21]
K. Nassau and D.L. Chadwick. Mat. Res. Bull. 17 (1982) 715. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 65 (1982) 197. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 65 (1982) 486. K. Nassau and D.L. Chadwick, J. Am. Ceram. Sot. 66 (1983) 332. D.L. Wood. K. Nassau and D.L. Chadwick. Appl. Opt. 21 (1982) 4276. K. Nassau, Bell Syst. Tech. J. 60 (1981) 327. R. Kenworthy. Silicates Ind. 37 (1972) 245. W.A. Weyl and E C. Marboe, The Constitution of Glasses (Wiley-Interscience, New York, 1964) pp. 620-621. F.L. Galeener. G. Lucovsky and R.H. Geils. Phys. Rev. B19 (1979) 4251. M. Imaoka and H. Hasegawa, Phys. Chem. Glasses 21 (1980) 67. M. Imaoka. Glass-Formation Range and Glass Structure, Adv. in Glass Technol., Vol. 1 (Plenum. New York. 1962) pp. 149-163. N. Mochida and K. Takahashi, Proc. 10th Int. Congress on Glass. Vol. 13 (Ceramic Sot. of Japan. 1974) pp. 29-35. W.H. Grodkiewicz. H.M. O’Brian, L. Pressman. S. Singh, L.G. Van Uitert and G. Zydzik, J. Non-Cryst. Solids 44 (1981) 405; Mater. Res. Bull. 16 (1981) 373. H.M. Heaton and H. Moore, J. Sot. Glass Technol. 41 (1957) 3T-27T. R.V. Adams, Phys. Chem. Glasses 2 (1961) 101. W.R. Eubank and W.R. Beck, U.S. Patent 2.863.782 (1958). cited by T. Takamori. in: Treatise on Materials Science and Technology, Vol. 17, Glass II. eds. M. Tomozawa and R.H. Doremus (Academic Press, New York, 1979) 173. E. Leitz, German Patent 1,006,559 (April 26, 1967); French Patent 1,468,344 (Feb. 3, 1967). D.L. Wood and J.W. Fleming, Jr., Rev. Sci. Instr. 53 (1982) 43. A.E. Miller, K. Nassau, K.B. Lyons and M.E. Lines. to be published. K. Nassau, CA. Wang, and M. Grasso, J. Am. Ceram. Sot. 62 (1979) 74. K. Nassau, D.L. Chadwick, G.W. Kammlott and E.M. Rabinovich. Phys. Chem. Glasses 24 (1983) 150.