CN1342617A - 低非线性折射率磷酸盐法拉第旋光玻璃 - Google Patents
低非线性折射率磷酸盐法拉第旋光玻璃 Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract 2
- 239000010452 phosphate Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000005304 optical glass Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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- 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
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Abstract
一种低非线性折射率磷酸盐法拉第旋光玻璃,主要用于法拉第旋转器。是含有大量Tb3+的旋光玻璃。是以Tb2O3和P2O5为基础的磷酸盐旋光玻璃。含有17-26mol%的Tb2O3,70-80mol%的P2O5,含有少量的Sb2O3,或少量的As2O3,或少量的Sb2O3+As2O3,还含有少量的Al2O3、B2O3、SiO2、R2O和RO。与在先技术比,本发明法拉第旋光玻璃具有较高的费尔德(Verdet)常数,低的非线性折射率n2,较高的V/n2值。在可见光区域及近红外是透明的,玻璃稳定性好,可以获得大尺寸均匀的旋光玻璃制品。
Description
技术领域:
本发明涉及一种用于法拉第旋转器的低非线性折射率磷酸盐法拉第旋光玻璃,特别是涉及高Tb2O3含量的旋光玻璃。而且是具有大的费尔德(Verdet)常数、小的非线性折射率(n2),能制成大尺寸高均匀制品的旋光玻璃。也就是涉及一种具有较大的法拉第效应,用于制造法拉第旋转器的玻璃材料。
背景技术:
作为法拉第旋转器的结构中通直流电流的线圈在旋光材料中产生一个纵向磁场、当线偏振光通过时,发生偏振面的旋转。旋转角为θ分(min)
θ=VLH其中,L为旋光材料的长度(cm),H为磁场强度,单位为奥斯特(Oe),V为旋光材料的固有常数,称费尔德(Verdet)常数。Verdet常数为旋光材料的一个基本性能。通过选择不同的磁场强度H和长度L,可实现不同的角度偏转,制成磁光开关、磁光隔离器。或通过改变电流进行磁场调制,实现光的调制,制成磁光调制器。若把旋光材料置于磁场附近,或有电流通过的导线附近时,通过测量偏振面的偏转角,可实现磁场强度或电流的测定。
当旋光材料用于激光领域时,强光的作用下,材料的折射率n随光强变化。式中n2为非线性折射率,E为光的电场强度。
n=n0+n2(E)2折射率变化将引起光束波面畸变和自聚焦现象,影响光束质量。希望降低旋光玻璃的n2值。上式中n0为普通光线下的折射率。
现有磁光材料包括玻璃和晶体二类。玻璃由于其光学均匀性好、透过波长范围广、吸收损耗低、易获得大尺寸成品而获得应用。如上述用这种玻璃制成的器件包括磁光开关、磁光调制器、磁光隔离器和各种磁光传感器。衡量法拉第旋光玻璃的性能费尔德(Verdet)常数是一个重要的指标,用V表示,即单位磁场强度下每单位光程所引起的偏振面旋转角度,单位为分/奥斯特.厘米(min/Oe.cm)或R/T.m。要求旋光玻璃具有大的Verdet常数,以产生较大的偏转,在一定的使用波长范围内具有高透过、低损耗。在先技术中的法拉第旋光玻璃都朝着增大Verdet常数的方向努力。如蒋亚丝等人提供的(参见“High Verdet constant Faraday rotator glasses”(高Verdet常数法拉第旋光玻璃),SPIE1761卷,268页,1992),在与激光相关的应用中,高强度激光可引起材料折射率的变化,出现光束质量劣化或自聚焦,降低n2可避免这些现象。因此要求法拉第旋光玻璃是高的费尔德(Verdet)常数、低的非线性折射率n2,或者是高的V/n2。
高费尔德(Verdet)常数法拉第旋光玻璃必需含有大量顺磁稀土离子,Ce3+、Pr3+、Tb3+或Dy3+离子均可产生大的Verdet常数。Pr3+和Dy3+在可见和红外区出现吸收带,具有实用意义的为含大量Ce3+和Tb3+的玻璃。含铈(Ce3+)的玻璃Verdet常数较小,而且在制造过程中出现价态变化,形成对Verdet没有贡献、短波长区域产生吸收的Ce4+。(参见S.Hirota等人,“法拉第旋转元件玻璃”,USP 4,168,176,Sep.18,1979)。
在先技术中含Tb3+玻璃是采用Tb2O3-SiO2系统(参见C.Robinson等人,“含稀土的铝硅酸盐法拉第旋光玻璃”,USP 3,484,152,Dec.16,1969;I.Tajima等人,“法拉第旋光玻璃”,USP 3,971,723,Jul.27,1976),这种玻璃的n2大。而且高Tb2O3含量玻璃的玻璃形成稳定性差,必须引入其它玻璃氧化物和中间体氧化物,少量SiO2、B2O3和Al2O3的引入是必要的。
高Tb2O3含量玻璃的熔化温度高,熔化困难;高温下P2O5挥发,产生熔体组成的不均匀,加入少量碱金属氧化物和碱土金属氧化物将使玻璃熔化、澄清温度下降。
发明内容:
本发明的目的为获得具有高V值,低n2和高V/n2的含大量三价铽离子(Tb3+)的磷酸盐法拉第旋光玻璃。将使本发明的旋光玻璃同时具有可见区和近红外透明,即可使用于520-1500nm波段。
本发明的法拉第旋光玻璃是以Tb2O3和P2O5为基础的磷酸盐旋光玻璃,组成中包含Tb2O3、P2O5、B2O3、Al2O3、R2O(碱金属化合物)、RO(碱土金属化合物)及SiO2,具体的组成按摩尔百分比(mol%)为:
Tb2O3 17-26% SiO2 0-6%
P2O5 70-80% R2O(Na2O+K2O) 0-6%
Al2O3 0-6% RO(BaO) 0-6%
B2O3 0-6% Sb2O3或As2O3 0.1-0.8%
或Sb2O3+As2O3
Tb2O3为玻璃的基本组成,其含量决定了玻璃Verdet常数的数值。Tb2O3含量少于17%时,玻璃的Verdet常数太低;Tb2O3含量大于26%时,玻璃不稳定,难以制成光学均匀的玻璃。
P2O5是玻璃的形成氧化物,当P2O5含量小于70%时,玻璃不稳定;大于80%时,玻璃的化学稳定性也变差,玻璃不具有实用价值。
少量引入Al2O3、B2O3、SiO2均能增加高Tb2O3玻璃的玻璃稳定性。超过6%时,将增加玻璃的n2。
R2O(Na2O+K2O)、RO(BaO+SrO)可降低玻璃的熔化温度。当Na2O+K2O大于6%或BaO+SrO大于6%时,玻璃形成的稳定性变差。
Tb离子在高温下大部分处于三价,要防止部分Tb离子形成四价而使玻璃变黄,影响短波区的透过。引入Sb2O3,或As2O3或Sb2O3+As2O3可使Tb4+还原为Tb3+,改善玻璃在近紫外区的透过率。Sb2O3、As2O3或Sb2O3+As2O3大于0.8%将增加玻璃的n2。
与在先技术比,本发明的旋光玻璃具有较高的Verdet常数、低的n2(本发明的n2小于1.44,比在先技术中最低的n2=1.59还要低)、具有较大的V/n2比值、在可见区及近红外(520~1500nm)透明、玻璃稳定性好、光学均匀性好、可获得大尺寸均匀制品等特点。
具体实施方式:
本发明的玻璃组成、Verdet常数和V/n2列于表1。
按照表1中所列的本发明的玻璃组成制备配合料,所用的原料分别为:Tb4O7、P2O5或H3PO3、Al(PO3)3或Al(OH)3、H3BO3、Sb2O3、As2O3,K2O、Na2O、BaO、SrO可用相应的硝酸盐或碳酸盐引入。原料经混合后加入石英坩埚中,在1300-1350℃温度下熔化、澄清,熔化或澄清时间取决于坩埚大小。熔化好的玻璃转入铂坩埚中,用陶瓷或铂搅拌器进行搅拌,逐渐降低温度,在1200-1300℃浇注入预热的模子中,玻璃硬化后转入退火炉中退火,获得光学均匀的旋光玻璃成品。
从表1中所列的11个实施例中,所获得具有较高的V常数、低的非线性折射率n2和较高的V/n2,充分证明了本发明的显著的进步。
表1:玻璃组成,Verdet常数、n2和V/n2
玻璃No. | 1 | 2 | 3 | 4 | 5 | 6 |
Tb2O3 (Mol%) | 19.94 | 19.87 | 19.88 | 19.88 | 19.87 | 24.23 |
P2O5 (Mol%) | 73.76 | 73.54 | 73.55 | 73.54 | 79 49 | 73.91 |
B2O3 (Mol%) | 5.96 | |||||
Al2O3 (Mol%) | 5.98 | |||||
BaO (Mol%) | ||||||
Na2O (Mol%) | 5.95 | 1.19 | ||||
SiO2 (Mol%) | 5.96 | |||||
Sb2O3 (Mol%) | 0.32 | 0.62 | 0.62 | 0.62 | 0.64 | 0.67 |
密度 (g/cm3) | 3 3 | 3.29 | 3.32 | 3.31 | 3.32 | 3.43 |
n2 (10-13esu) | 1.39 | 1.417 | 1.434 | 1.438 | 1.38 | 1.436 |
V632nm (min/Oe.cm) | 0 154 | 0.155 | 0 157 | 0.156 | 0.153 | 0.183 |
V/n2 (min/Oe.cm.10-12esu) | 1.108 | 1.094 | 1.095 | 1.085 | 1.111 | 1.274 |
V1064nm (min/Oe.cm) | 0.052 | 0.052 | 0.053 | 0.053 | 0.052 | 0.062 |
V/n2 (min/Oe.cm.10-12esu) | 0.374 | 0.367 | 0.37 | 0.369 | 0.377 | 0.434 |
玻璃No | 7 | 8 | 9 | 10 | 11 |
Tb2O3 (Mol%) | 17.95 | 17.9 | 19 58 | 19.88 | 19.87 |
P2O5 (Mol%) | 73.77 | 73.56 | 72.24 | 73.56 | 73.54 |
B2O3 (Mol%) | 1.98 | 1.99 | 1.99 | 1.98 | 1.99 |
Al2O3 (Mol%) | 3.99 | 1.99 | 1.69 | 3.97 | |
BaO (Mol%) | 1.98 | ||||
Na2O (Mol%) | 2 | 1.98 | 3.88 | 3.97 | |
SiO2 (Mol%) | |||||
Sb2O3 (Mol%) | 0.3 | 0.61 | 0.62 | 0.62 | 0.63 |
密度 (g/cm3) | 3.27 | 3.34 | 3.35 | 3.39 | 3.35 |
n2 (10-13esu) | 1.34 | 1.35 | 1.38 | 1.31 | 1.38 |
V632nm (min/Oe.cm) | 0.142 | 0.144 | 0.156 | 0.16 | 0.156 |
V/n2 (min/Oe.cm 10-12esu) | 1.059 | 1.067 | 1.133 | 1.221 | 1.133 |
V1064nm (min/Oe.cm) | 0.048 | 0.049 | 0.053 | 0.054 | 0.053 |
V/n2 (min/Oe.cm10-12esu) | 0.358 | 0.363 | 0.384 | 0.412 | 0.384 |
Claims (1)
1.一种低非线性折射率磷酸盐法拉第旋光玻璃,是含有Tb3+的旋光玻璃,其特征在于是以Tb2O3和P2O5为基础的磷酸盐旋光玻璃,具体的组成按摩尔百分比(mol%),含有17-26%的Tb2O3,70-80%的P2O5,0-6%的Al2O3,0-6%的B2O3,0-6%的SiO2,0-6%的Na2O加K2O,0-6%的BaO,0.1-0.8%的Sb2O3,或者0.1-0.8%的AS2O3,或者0.1-0.8%的Sb2O3加AS2O3。
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Cited By (5)
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CN100999384B (zh) * | 2006-01-11 | 2010-05-12 | 中国科学院西安光学精密机械研究所 | 一种磁旋光玻璃及其制备工艺 |
CN1927751B (zh) * | 2002-07-05 | 2010-06-23 | Hoya株式会社 | 近红外吸收玻璃、元件、滤光器及其制法和含铜玻璃 |
CN102627404A (zh) * | 2012-04-16 | 2012-08-08 | 陕西科技大学 | 一种含铋的顺磁性法拉第旋光玻璃的制备方法 |
CN102627403A (zh) * | 2012-04-16 | 2012-08-08 | 陕西科技大学 | 一种高掺量铒法拉第旋光玻璃的制备方法 |
CN106082684A (zh) * | 2016-06-11 | 2016-11-09 | 华南理工大学 | 一种高掺杂Tb3+磷酸盐玻璃芯复合材料光纤及其制备方法 |
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2001
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Cited By (7)
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---|---|---|---|---|
CN1927751B (zh) * | 2002-07-05 | 2010-06-23 | Hoya株式会社 | 近红外吸收玻璃、元件、滤光器及其制法和含铜玻璃 |
CN100999384B (zh) * | 2006-01-11 | 2010-05-12 | 中国科学院西安光学精密机械研究所 | 一种磁旋光玻璃及其制备工艺 |
CN102627404A (zh) * | 2012-04-16 | 2012-08-08 | 陕西科技大学 | 一种含铋的顺磁性法拉第旋光玻璃的制备方法 |
CN102627403A (zh) * | 2012-04-16 | 2012-08-08 | 陕西科技大学 | 一种高掺量铒法拉第旋光玻璃的制备方法 |
CN102627403B (zh) * | 2012-04-16 | 2014-03-12 | 陕西科技大学 | 一种高掺量铒法拉第旋光玻璃的制备方法 |
CN102627404B (zh) * | 2012-04-16 | 2014-04-16 | 陕西科技大学 | 一种含铋的顺磁性法拉第旋光玻璃的制备方法 |
CN106082684A (zh) * | 2016-06-11 | 2016-11-09 | 华南理工大学 | 一种高掺杂Tb3+磷酸盐玻璃芯复合材料光纤及其制备方法 |
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