CN1374263A - Faraday rotation glass with high weld constant and its prepn - Google Patents

Faraday rotation glass with high weld constant and its prepn Download PDF

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CN1374263A
CN1374263A CN 02100399 CN02100399A CN1374263A CN 1374263 A CN1374263 A CN 1374263A CN 02100399 CN02100399 CN 02100399 CN 02100399 A CN02100399 A CN 02100399A CN 1374263 A CN1374263 A CN 1374263A
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faraday rotation
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CN1142111C (en
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聂春生
李宝璋
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TIANJIN SILICAT INST
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TIANJIN SILICAT INST
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc

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Abstract

The present invention is one Tb2O3-Al2O3-SiO2-B2O3 system Faraday rotation glass, which contains ZrO2, TiO2, ZnO, P2O5, Ga2O3 and other hybrid components, has large size and high performance and Veld optical rotation constant |V| not smaller than 0.33 min/A.cm (at 6328A). The glass has a percentage molecular composition of: Tb2O3 28.5-32, Al2O3 9-20, SiO2 24-40 and B2O3 18-25, total hybrid component less than 5; and has a Tb ion density not less than 11.7X10 to the power 21 each cu cm. The glass has excellent chemical homogeneity, low light absorption, controllable platinum particle number and practical technological performance.

Description

High Wilder constant Faraday rotation glass and preparation thereof
Technical field
The invention belongs to special glass, particularly a kind of high Wilder constant Faraday rotation glass and preparation thereof.
Background technology
Contain a large amount of paramagnetic rare-earth oxide compound Tb 2O 3Glass have big Wilder constant, as faraday's magnetic rotation material, for many years, come into one's own always.Since 1964, many scholars are with regard to Tb 3+The optically-active characteristic of ion in glass carried out the research aspect the physics.Know Tb according to the data introduction 3+It is because the configuration of its electronic structure is 4f that ion has paramagnetism 85s 25p 6, 6 parallel electronics of spin are arranged on f orbitals, it is non-vanishing to spin, and has permanent magnetic moment, in magnetic field, turn to along field direction, the magnetic of this paramagnetic material-light constant, promptly Wilder constant V is defined as negative value.The V constant formula of the paramagnetic glass that scholars propose is as follows: V = 4 π 2 μ Bv 2 3 chkT Np 2 g Σ n C n v 2 - v n 2 , p = g [ J ( J + 1 ) ] 1 2 .
μ B-Bohr magnetron in the formula, v-frequency, N-Tb 3+Ionic concn, the p-effective magneton number, the c-light velocity, the h-quantum of action, the k-Boltzmann constant, T-absolute temperature, g-Lang De divides the factor, C n-transition probability correlation, v n-jump frequency.According to formula as can be known, for obtaining height | V| value glass, Tb 3+The concentration N height of should trying one's best is introduced Tb as much as possible 2O 3, calculate according to the inventor, for making | V| 〉=0.33, should N 〉=11.7 * 10 21Individual/cm 3Simultaneously the molecular volume of other components in the glass is as far as possible little, so that receive more Tb in the regulation space content 3+
Domestic scholars is made | the glass of V|=0.33 (JiangYasi " SPIE ", Vol 1761, P268,1992) and | the glass of V|=0.238 (Nie Chunsheng " special glass ", Vol2, No2, P47,1985).
U.S. Pat P 3,420, and 601 propose Tb 2O 3-Al 2O 3-SiO 2-B 2O 3-ZnO system glass, its weight % compositing range is Tb 2O 340-75, Al 2O 30-10, SiO 20-5, B 2O 315-50, ZnO 0-10, such glass | the V| value is very high, it is said | and V| can reach 0.37, but because Al 2O 3And SiO 2Content is very low, and ZnO content is too high, is unfavorable for improving viscosity, and the pouring technology poor performance is difficult to make large-size glass.
U.S. Pat P 3,484, and 152 propose Tb 2O 3-Al 2O 3-SiO 2-R 2The O-RO system glass, its weight % compositing range is Tb 2O 330-70, Al 2O 310-20, SiO 220-46, R 2O 0.1-2.0, RO0.5-10.0, the temperature of fusion of such glass is 1600 ± 100 ℃, so high temperature of fusion must increase the weight of the platinum pollution, increases platinum grain quantity.
The Japan clear 51-46524 of special permission communique proposes Tb 2O 3-Al 2O 3-SiO 2-B 2O 3-ZrO 2System glass, its molecule % compositing range is Tb 2O 310-30, Al 2O 310-30, SiO 2〉=15, B 2O 3〉=10, ZrO 20-5, SiO 2+ B 2O 330-80, AlF 30-2, such glass has the better manufacturability energy, may make large-size glass, but Tb 2O 3Content is lower, is no more than 30%, | V| can not surpass 0.33, Tb in the example 2O 3Only be 25%, | V| is up to 0.312.
The Japan clear 57-43537 of special permission communique proposes a class borosilicate glass, and its weight % compositing range is Tb 2O 3+ La 2O 325-57, B 2O 310-42, SiO 20-12, R 2O 0-1, RO 8-24, ZrO 21-7, WO 30-7.Representative instance consists of SiO 25.5, B 2O 340.0 CaO 9.1, Tb 4O 741.5, ZrO 23.9.Because Tb 2O 3Content is lower, | the V| value can not surpass 0.30.
The clear 62-158135 of day disclosure special permission communique proposes Tb 2O 3-Al 2O 3-SiO 2-B 2O 3System glass is used to make the cladding and the core material of single-mode fiber, and its molecule % compositing range is Tb 2O 318-32, Al 2O 317-26, SiO 226-38, B 2O 318-34, ZrO 20-5, other are respectively the Ce of 0-5 2O 3, Pr 2O 3, Dy 2O 3And Ho 2O 3, it is the highest | and V| can reach 0.34.Because B 2O 3Content is higher, thereby cast viscosity is big inadequately, is difficult to make thick dimension glass.In addition, ZrO 2Though can improve viscosity, under the cooperation that lacks oxide compounds such as ZnO, when pouring into a mould thick blank cooling, ZrO 2Cause that easily glass inside separates out crystallization.
Chinese patent CN 1073927A proposes Tb 2O 3-Al 2O 3-SiO 2-B 2O 3System glass, its weight (%) compositing range is Tb 2O 356-69, Al 2O 33-12, SiO 26-24, B 2O 36-14, MgO 0-4, BaO0-8.Such glass Tb 2O 3High-content is 69%, | V| can not be very high, particularly adds alkaline-earth oxide, more is unfavorable for | the raising of V|.Because such glass needs secondary fusion, and temperature of fusion all surpasses 1450 ℃, thereby is unfavorable for the reduction of photoabsorption and alleviating of platinum pollution.
The flat 10-297933 of day disclosure special permission communique proposes Tb 2O 3-Ga 2O 3-SiO 2-B 2O 3System glass is used Ga 2O 3Replace the Al in the patent in early stage 2O 3, paramagnetic ion Tb as a result 3+And Ga 3+Total ion concentration N can be up to 14.3 * 10 21Individual/cm 3, thereby | V| is up to 0.49, but the poor stability of this class glass is difficult to make the large size blank.
Summary of the invention
In order to solve the problem of above-mentioned existence, the spy proposes a kind of good optical homogeneity that has, low photoabsorption, and the platinum pollution level is low, and temperature of fusion is low, and manufacturing dimension is thick, | the glass that the V| value is high.
To achieve these goals, the present invention implements by following scheme, and high Wilder constant Faraday rotation glass is Tb 2O 3-Al 2O 3-SiO 2-B 2O 3System glass, molecule % compositing range is:
Tb 2O 3????28.5-32％，?TiO 2????????0.5-3％，
Al 2O 3????9-20％，????ZnO??????????0.5-3％，
SiO 2??????24-40％，???P 2O 5???????0-3％，
B 2O 3?????18-25％，???Ga 2O 3??????0-5％，
ZrO 21-5%, Sb 2O 3And/or As 2O 30.3-1%.
ZrO wherein 2, TiO 2, ZnO, P 2O 5And Ga 2O 3Be the hydridization component, the Wilder constant | V| 〉=0.33 (6328 ), blank thickness 〉=30mm.
Above-mentioned Faraday rotation glass, its Al 2O 3, SiO 2And B 2O 3The average molecular per-cent of three components meets Al 2O 3, SiO 2And B 2O 3Numerical range in the zone that ABCD tetragon in the ternary relation graph is surrounded:
Above-mentioned Faraday rotation glass, the hydridization component ZrO that contains 2, TiO 2, ZnO, P 2O 5And Ga 2O 3, add a kind ofly at least, add total amount and must not surpass 5%.
Above-mentioned Faraday rotation glass, the Sb that it contains 2O 3And As 2O 3Be finings, also play the effect of hydridization component, add a kind ofly at least, the adding total amount is 0.3-1%.
Above-mentioned Faraday rotation glass, its preparation technology is identical with the preparation of special glass, but P among the present invention 2O 5The mode of introducing glass can directly add admixtion, or with containing PCl 3Oxygen and the nitrogen mixture vent method that is carrier gas introduce a part.
Above-mentioned Faraday rotation glass preparation, its temperature of fusion is lower than 1450 ℃.
Effect of the present invention is that manufacturing is a kind of | V| 〉=0.33, the large size Faraday rotation glass of thickness 〉=30mm, this glass has the excellent in chemical homogeneity, low photoabsorption, controlled platinum grain quantity has feasible processing performance simultaneously, be that temperature of fusion is no more than 1450 ℃, teeming temperature is no more than 1370 ℃, and ℃ (Tw is a teeming temperature, and the viscosity under this temperature is 10 in Tw-Tl＞50 4Pool; Tl is a liquidus temperature, i.e. the crystallization upper limit).
Description of drawings
Fig. 1 is Al 2O 3-SiO 2-B 2O 3Ternary relation graph.
Embodiment
The present invention will be further described below in conjunction with embodiment and principle:
Its molecule % compositing range is:
Tb 2O 3?????28.5-32％，?TiO 2????0.5-3％，
Al 2O 3?????9-20％，????ZnO??????0.5-3％，
SiO 2???????24-40％，???P 2O 5???0-3％，
B 2O 3??????18-25％，???Ga 2O 3??0-5％，
ZrO 21-5%, Sb 2O 3And/or As 2O 30.3-1%.
Its best molecule % compositing range is:
Tb 2O 3????29-31％，????TiO 2?????0.5-2％，
Al 2O 3????10-18％，????ZnO???????0.5-1.5％，
SiO 2??????25-39％，????P 2O 5????1.5-2.5％，
B 2O 3?????19-24％，????Ga 2O 3???1-3％，
ZrO 21-3%, Sb 2O 3And/or As 2O 30.3-0.8%.
1. preferably determine Al 2O 3, SiO 2And B 2O 3The relative percentage of three kinds of main glass ingredients.
Want | V| 〉=0.33, Tb 3+Concentration N must be greater than 11.7 * 10 21Individual/cm 3At Tb 2O 3-Al 2O 3-SiO 2-B 2In the O system glass, Tb 2O 3Should be for about 30 (molecule %), other hydridization component total amounts must not surpass 5%, like this, leave Al for 2O 3, SiO 2And B 2O 3Compositing range have only about 65%, what kind of rational proportion the three should just can make glass properties the best with, promptly near target of the present invention, this is epochmaking aspect.The present invention obtains a result through after the systematic study: as shown in Figure 1, and at Al 2O 3-SiO 2-B 2O 3(precondition is Tb in the three composition graphs of a relation 2O 3Be 30%, other hydridization compositions 4%, Al 2O 3, SiO 2And B 2O 3Summation is 66%), the relative percentage of representing with molecule % then meets the requirements in the zone that tetragon ABCD is surrounded, and the coordinate on four summits is as shown in table 1.
Table 1
Figure A0210039900071
2. introduce ZrO 2, TiO 2, ZnO, P 2O 5And Ga 2O 3The hydridization glass ingredient.
The quaternary system glass ingredient is simpler, is very easy to crystallization, and it is feasible introducing other rational hydridization compositions.Patent in advance is introduced separately into ZrO respectively 2And ZnO.The present invention finds, though ZrO 2Can improve viscosity, draw back the distance of Tw and Tl, restrain crystallization, but ZrO 2The oxide compound that belongs to high high field causes glass inner crystallization, particularly ZrO easily 2Greater than 5% o'clock, show very strong self tendency towards devitrification.For overcoming this shortcoming, introduce ZnO, the ZrO that ZnO can restrain 2Self crystallization.Though ZrO 2Can improve viscosity, and induce the glass body crystallization, but ZrO 2Nucleogenesis also disturbed the nucleation of glass itself, the two interferential result that the inner crystallization of glass is suppressed, and TiO 2The ZrO that helps of adding 2Nucleogenesis is again because TiO 2Also be intermediate oxide, help the expansion of glass formation range and stablizing of glass structure, so TiO 2Introducing be reasonably, but TiO 2Can cause that glass yellow, TiO 2The introducing amount should not surpass ZrO 2ZrO 2, TiO 2With ZnO three's effect glass inside is suppressed, crystallization only occurs in the surface.In addition, P 2O 5Also play and regulate viscosity and suppress the glass effect of nucleation automatically itself, Ga 2O 3Both having played the effect of hydridization component, itself is again paramagnetic substance, with Tb 2O 3Improve together | the V| value.
Below in conjunction with each concrete composition limited range (molecule %) of glass of the present invention and principle the present invention is described in further details:
1.Tb 2O 3?28.5-32％。Functional oxide Tb 2O 3The content height of should trying one's best will make | V| 〉=0.33, Tb 3+Concentration N must be greater than 11.7 * 10 21Individual/cm 3Being lower than 28.5% | V| does not reach requirement.If be higher than 32% then the processing performance of glass is poor, Tl raises, Tw-Tl even negative value occurs, the consequence that liquidus temperature Tl improves is to make cast very difficult, the large size heavy sheet glass can't be made, since the decline of anti-crystallization ability, its inner big area crystallization in the glass metal process of cooling after cast.Optimum range is 29-31%.
2.Al 2O 3?9-20％。Intermediate oxide Al 2O 3Can play the vital role of stabilized glass, it is not obvious to be lower than 9% effect, is higher than 20% anti-crystallization ability is descended, and also improves temperature of fusion simultaneously.Best compositing range is 10-18%.
3.SiO 2?24-40％。Glass generates body SiO 2Can guarantee the stability of glass, improve viscosity, reduce Tl, effectively suppress crystallization.Be lower than 24% easy crystallization, be higher than 40% and improve temperature of fusion, be difficult to fusing below 1450 ℃, cause fusing time, increase the weight of platinum and pollute, increase platinum grain by irrational prolongation.Best compositing range is 25-39%.
4.B 2O 3?18-25％。Glass generates body B 2O 3With SiO 2Act on identically, guarantee the stability of glass.B 2O 3Can reduce temperature of fusion significantly, reduce the favourable clarification of high temperature viscosity.B 2O 3Tw and Tl are descended simultaneously.Be lower than 18% glass melting temperature and surpass 1450 ℃, be higher than 25% viscosity degradation, Tw and Tl are approaching, easily crystallization.Best compositing range is 19-24%.
5.Al 2O 3, SiO 2And B 2O 3Three's relative percentage.So-called relative percentage is meant in 100% glass is formed, deducts Tb 2O 3About 34% with the shared ratio of hydridization oxide compound, remaining Al 2O 3, SiO 2And B 2O 3It is about 66% that the shared relative percentage ratio total amount of three should be, with it as 100%, every kind of shared relative percentage of oxide compound.
Use Al 2O 3, SiO 2And B 2O 3Ternary relation Fig. 1 illustrates three's relative percentage.A, B, 4 quadrilateral areas that surrounded of C, D are Al among Fig. 1 2O 3, SiO 2And B 2O 3Three's relative percentage scope, the coordinate on each summit are the listed data of table 1.
6.ZrO 2?1-5％。ZrO 2Be the high field intensity oxide compound, can improve viscosity, reduce Tl, suppress crystallization, it is not obvious to be lower than 1% effect, is higher than 5% and can causes the inner crystallization of glass and improve temperature of fusion.Best compositing range is 1-3%.
7.TiO 2?0.5-3％。Can regulate viscosity, the stabilized glass structure is with ZrO 2Suppress crystallization together, be higher than 3% glass and yellow, photoabsorption increases.Best compositing range is 0.5-2%.
8.Zn?0.5-3％。Energy stabilized glass structure is slowed down ZrO 2Negative impact, surpass 3% and make material property elongated, be unfavorable for controlling crystallization.Best compositing range is 0.5-1.5%
9.P 2O 5?0-3％。Generate body, P as glass 2O 5Can play the stabilized glass structure, suppress the effect of crystallization, surpass 3% and might cause phase-splitting.Best compositing range is 1.5-2.5%
10.Ga 2O 3?0-5％。Ga 2O 3Both being intermediate oxide, also is functional oxide, can effectively improve | V|, but Ga 2O 3Very expensive, should not use in a large number.Surpass 5% anti-crystallization ability and descend, the glass instability, best compositing range is 1-3%.
11.ZrO 2, TiO 2, ZnO, P 2O 5And Ga 2O 3Can be separately or optionally combination add, total amount must not surpass 5%.
12.Sb 2O 3And As 2O 3Add-on is 0.3-1% respectively, and resultant is lower than 1%, though be traditional finings, the two also plays the effect of hydridization component.
Below in conjunction with specific embodiment the present invention is described in further detail:
Table 2 provides the concrete composition of embodiment 1-8 and comparative example 9-11:
Table 2 (molecule %)
Embodiment Comparative example
????No ????1 ?????2 ?????3 ????4 ????5 ????6 ????7 ????8 ????9 ???10 ????11
????Tb 2O 3 ???32.0 ???30.94 ???31.54 ???31.0 ??30.5 ??30.8 ??30.6 ???30.0 ???31.0 ??32.0 ???31.0
????Al 2O 3 ???17.0 ???17.20 ???17.16 ???17.0 ??10.0 ??10.6 ??10.2 ???10.0 ???19.0 ??16.0 ???10.0
????SiO 2 ???24.5 ???25.34 ???25.04 ???25.0 ??37.0 ??36.6 ??36.7 ???37.0 ???26.0 ??23.5 ???38.0
????B 2O 3 ???22.5 ???22.84 ???22.73 ???23.0 ??19.5 ??19.0 ??19.5 ???19.0 ???24.0 ??21.5 ???18.0
????Zn ???- ???0.41 ???- ???1.5 ??1.0 ??1.0 ??- ???- ???- ??2.0 ???1.0
????TiO 2 ???2.0 ???1.61 ???1.72 ???0.9 ??0.5 ??0.5 ??- ???- ???- ??2.5 ???0.5
????ZrO 2 ???2.0 ???1.66 ???1.81 ???1.6 ??1.5 ??1.5 ??1.0 ???1.0 ???- ??2.5 ???1.5
????P 2O 5 ???- ???- ????- ???- ??- ??- ??2.0 ???- ???- ??- ???-
????Ga 2O 3 ???- ???- ????- ???- ??- ??- ??- ???3.0 ???- ??- ???-
????Sb 2O 3(adding) ???0.3 ???0.3 ????As 2O 3????0.3 ???As 2O 3???0.3 ??0.3 ??0.3 ??0.3 ???0.3 ???0.3 ??0.3 ???0.3
Table 3 provides the result of embodiment 1-8 and comparative example 9-11:
Table 3
Embodiment Comparative example
???1 ???2 ???3 ???4 ???5 ???6 ???7 ???8 ???9 ???10 ??11
Found scale (kilogram) ??5.0 ??5.0 ??5.0 ??6.5 ??5.4 ??11.5 ??11.5 ??5.0 ??5.0 ???5.0 ??5.5
Temperature of fusion (℃) ??1420 ??1420 ??1420 ??1420 ??1420 ??1420 ??1420 ??1420 ??1420 ??1420 ??1450
Clarifying temp (℃) ??1440 ??1440 ??1440 ??1440 ??1440 ??1440 ??1440 ??1440 ??1440 ??1440 ??1460
Teeming temperature (℃) ??1380 ??1380 ??1380 ??1370 ??1370 ??1340 ??1340 ??1340 ??1390 ??1380 ??1370
Blank dimension (mm) ??220×90 ??×30 ??205×90 ??×30 ??200×90 ??×30 ??210× ??105×35 ??165× ??105×40 ??210× ??135×40 ??210× ??135×40 ??210× ??105×30 ??200×90 ??×15 ??220×90 ??×30 ??165× ??105×40
The crystallization situation The surface On a small quantity On a small quantity On a small quantity On a small quantity On a small quantity On a small quantity On a small quantity On a small quantity On a small quantity More More
Inner Do not have Do not have Do not have Do not have Do not have Do not have Do not have Do not have Have Have Have
Tb 3N (×10 21Individual/cm 3) ??12.3 ??12.0 ??12.0 ??12.0 ??12.0 ??11.9 ??11.7 ??Tb 3+GA 3??12.4 ??11.7 ??12.4 ??12.0
| V| 〉=0.33 (branch/Austria centimetre, 6328A) ??0.35 ??0.34 ??0.34 ??0.34 ??0.34 ??0.34 ??0.33 ??0.35 ??0.33 ??0.35 ??0.34
Can find out a feature of glass of the present invention from the example of table 3, promptly a small amount of crystallization inevitably appears in the surface, but inner crystallization is controlled.
Embodiment 1～5:
Form as shown in table 2ly, raw material adopts Tb respectively 4O 7(speciality, Fe 2O 3＜5ppm), Al 2O 3(analytical pure), H 3BO 3(analytical pure), quartz sand (pickling, Fe 2O 3＜5ppm), ZrO 2(analytical pure), TiO 2(analytical pure), ZnO (analytical pure), P 2O 5(chemical pure), Ga 2O 3(spectroscopically pure), Sb 2O 3(analytical pure) and As 2O 3(analytical pure) mixes after the weighing, founds in 1.3 liter platinum crucibles.Preparation technology is identical with the preparation of special glass, and 1420 ℃ of temperature of fusion melted in about 4 hours, rises to 1440 ℃ of clarifications 3 hours, slowly reduces to the teeming temperature of coming out of the stove in about 5-7 hour, whole process usefulness platinum agitator agitation as appropriate homogenizing.540 ℃ of cast iron mould and die preheatings adopt the sliminess cast, anneal 760 ℃.Do not have crystallization at casting complete while glass metal, in the cooling solidification process, crystallization at first appears in air-glass surface, is easy to observe in mould.What is called " on a small quantity " is meant that crystallization individuality or druse are separated from each other in the table 3, does not form the full wafer big area, and thickness is no more than 0.5mm." more " is meant that xln is linked to be sheet, is scattered in band shape by the liquid flow path direction.So-called " nothing " is meant the no xln in 100 * 100mm surface area inside that the cast blank is being selected on inspection after annealing.The result reaches target of the present invention.
Embodiment 6:
In 2.4 liters of platinum crucibles, found, about 1 times of the scale of founding than the foregoing description, other conditions are same as the previously described embodiments, and the result reaches target of the present invention.
Embodiment 7:
Experiment condition is identical with embodiment 6, adds P when batching 2O 51.8%, 1380 ℃ of mixed gas that feeds with oxygen and nitrogen in glass metal is the PCl that contains of carrier gas 3Gas, PCl 3The dividing potential drop of gas is about the 200mm mercury column, and the feeding time is 4.5 hours, and chemical analysis results shows and contains 2.0% P in the glass 2O 5, prove to feed PCl 3Can introduce a certain amount of P 2O 5, deduction P that batching adds 2O 5Volatilization loss, P 2O 5Total amount reaches 2.0%.
Embodiment 8:
Experiment condition is identical with embodiment 1～5, introduces 3%Ga 2O 3After, not only help stabilization, no crystallization in the 30mm heavy sheet glass, and | the V| value is up to 0.35.
Comparative example 9:
Experiment condition is identical with embodiment 1～5, in nothing ZrO is arranged 2, TiO 2, under ZnO and other hydridization components situation about existing, crystallization appears in the cast blank inside of thickness 15mm.
Comparative example 10:
Experiment condition is identical with embodiment 1～5, at ZrO 2+ TiO 2+ ZnO total amount is that there is crystallization the cast blank inside of thickness 30mm under 7% the situation, shows that three's total amount surpasses 5% o'clock anti-crystallization ability and descends on the contrary.
Comparative example 11:
Experiment condition is identical with embodiment 1～5, but temperature of fusion is elevated to 1450 ℃, and clarifying temp is 1460 ℃, and glass surface has more crystallization as a result, and there is small amount of crystalline inside, shows when containing the hydridization composition Al 2O 3, SiO 2And B 2O 3ABCD quadrilateral area in the relative percentage slip chart 1 of three components is formed some Q and is positioned at outside this zone, and three composition relative percentages are Al 2O 315.2%, SiO 257.6%, B 2O 327.2%.Glass with this relative percentage does not reach target of the present invention.

Claims (6)

1. one kind high Wilder constant Faraday rotation glass is characterized in that Tb 2O 3-Al 2O 3-SiO 2-B 2O 3System glass, molecule % compositing range is:
Tb 2O 3????28.5-32％，?TiO 2????0.5-3％，
Al 2O 3????9-20％，????ZnO??????0.5-3％，
SiO 2??????24-40％，???P 2O 5???0-3％，
B 2O 3?????18-25％，???Ga 2O 3??0-5％，
ZrO 21-5%, Sb 2O 3And/or As 2O 30.3-1%.
ZrO wherein 2, TiO 2, ZnO, P 2O 5And Ga 2O 3Be the hydridization component, the Wilder constant | V| 〉=0.33 minute/centimetre (6328 ) difficult to understand, blank thickness 〉=30mm.
2. according to the described high Wilder constant Faraday rotation glass of claim 1, it is characterized in that its Al 2O 3, SiO 2And B 2O 3The average molecular per-cent of three components meets Al 2O 3, SiO 2And B 2O 3The zone that ABCD tetragon in the ternary relation graph is surrounded:
Figure A0210039900021
3. according to the described high Wilder constant Faraday rotation glass of claim 1, it is characterized in that the hydridization component ZrO that contains 2, TiO 2, ZnO, P 2O 5And Ga 2O 3, add a kind ofly at least, add total amount and must not surpass 5%.
4 according to the described high Wilder constant Faraday rotation glass of claim 1, it is characterized in that containing the Sb that equally also plays the hydridization component 2O 3And As 2O 3, add a kind ofly at least, the adding total amount is 0.3-1%.
5. one kind high Wilder constant Faraday rotation glass preparation is characterized in that P 2O 5The mode of introducing glass can directly add admixtion, or with containing PCl 3Oxygen and the nitrogen mixture vent method that is carrier gas introduce a part.
6. according to the described high Wilder constant Faraday rotation glass preparation of claim 5, it is characterized in that temperature of fusion is lower than 1450 ℃.
CNB021003998A 2002-01-23 2002-01-23 Faraday rotation glass with high weld constant and its prepn Expired - Fee Related CN1142111C (en)

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Cited By (9)

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CN100999384B (en) * 2006-01-11 2010-05-12 中国科学院西安光学精密机械研究所 Magnetic rotation glass and preparation process thereof
CN101328018B (en) * 2008-07-23 2010-12-08 祁学孟 Lead free and cadmium free diamagnetic magnetic rotation glass
CN101613183B (en) * 2009-04-07 2011-11-09 上海师范大学 Long-wave broadband ultraviolet excited multi-functional fluorescent glass and preparation method thereof
CN104479678A (en) * 2014-12-08 2015-04-01 陕西科技大学 Preparation method of fluorescent powder for wavelength conversion and solar battery assembly and preparation method thereof
CN107207321A (en) * 2015-01-28 2017-09-26 日本电气硝子株式会社 Glass material and its manufacture method
CN108706870A (en) * 2018-07-10 2018-10-26 齐鲁工业大学 A kind of high refractive index oxide glass of structure enhancing
CN110885188A (en) * 2019-11-12 2020-03-17 湖北戈碧迦光电科技股份有限公司 Paramagnetic optical glass and preparation method thereof
CN116348426A (en) * 2020-12-16 2023-06-27 日本电气硝子株式会社 Glass material
CN116444151A (en) * 2023-03-28 2023-07-18 长春理工大学 Terbium and holmium co-doped GBZT magneto-optical glass and preparation method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100999384B (en) * 2006-01-11 2010-05-12 中国科学院西安光学精密机械研究所 Magnetic rotation glass and preparation process thereof
CN101328018B (en) * 2008-07-23 2010-12-08 祁学孟 Lead free and cadmium free diamagnetic magnetic rotation glass
CN101613183B (en) * 2009-04-07 2011-11-09 上海师范大学 Long-wave broadband ultraviolet excited multi-functional fluorescent glass and preparation method thereof
CN104479678A (en) * 2014-12-08 2015-04-01 陕西科技大学 Preparation method of fluorescent powder for wavelength conversion and solar battery assembly and preparation method thereof
CN104479678B (en) * 2014-12-08 2016-08-24 陕西科技大学 The preparation method of a kind of wavelength convert fluorescent powder and solar module and manufacture method
CN107207321A (en) * 2015-01-28 2017-09-26 日本电气硝子株式会社 Glass material and its manufacture method
CN108706870A (en) * 2018-07-10 2018-10-26 齐鲁工业大学 A kind of high refractive index oxide glass of structure enhancing
CN108706870B (en) * 2018-07-10 2021-06-08 齐鲁工业大学 Structurally enhanced high-refractive-index oxide glass
CN110885188A (en) * 2019-11-12 2020-03-17 湖北戈碧迦光电科技股份有限公司 Paramagnetic optical glass and preparation method thereof
CN116348426A (en) * 2020-12-16 2023-06-27 日本电气硝子株式会社 Glass material
CN116444151A (en) * 2023-03-28 2023-07-18 长春理工大学 Terbium and holmium co-doped GBZT magneto-optical glass and preparation method thereof

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