CN1042725C - 含镓和/或铟的硫化砷锗玻璃 - Google Patents
含镓和/或铟的硫化砷锗玻璃 Download PDFInfo
- Publication number
- CN1042725C CN1042725C CN95102315A CN95102315A CN1042725C CN 1042725 C CN1042725 C CN 1042725C CN 95102315 A CN95102315 A CN 95102315A CN 95102315 A CN95102315 A CN 95102315A CN 1042725 C CN1042725 C CN 1042725C
- Authority
- CN
- China
- Prior art keywords
- glass
- positively charged
- gallium
- strontium
- charged ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002203 sulfidic glass Substances 0.000 title 1
- 239000011521 glass Substances 0.000 claims abstract description 67
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001228 spectrum Methods 0.000 claims abstract description 7
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 5
- 230000007704 transition Effects 0.000 claims abstract description 4
- 150000003346 selenoethers Chemical class 0.000 claims abstract 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052733 gallium Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 229910005839 GeS 2 Inorganic materials 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 229910005842 GeS2 Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052958 orpiment Inorganic materials 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 11
- 239000005387 chalcogenide glass Substances 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 7
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 239000000075 oxide glass Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000146 host glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000004771 selenides Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000005283 halide glass Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
- C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/904—Infrared transmitting or absorbing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明涉及在电磁辐射光谱的远红外区域内具有极好透射性的透明玻璃的生产,以硫化物的摩尔百分数表示,所述玻璃的组成基本上为:55-95%GeS2;2-40%As2S3;0.01-20%R2S3;0-10%MSx,0-20%至少一个选自氯化物和/或氟化物的总量;0-5%硒化物总量;该玻璃的结晶起始温度和玻璃化转变温度之差至少150℃,且一般大于200℃。
Description
本发明涉及一种玻璃,特别是涉及一种在电磁辐射光谱的远红外区域具有极好透射性的透明玻璃。
美国专利5,240,885(Aitken等)描述了掺入稀土金属的卤化镉玻璃的制备方法,这种玻璃由于低声子能量,可以透过电磁辐射光谱的远红外区域的辐射。当掺入适当量的稀土金属时,玻璃的这种性能使它能用于制造高效的激光器,放大器和向上变换器,因为金属一硫键一般弱于金属-氧键,所以硫化物玻璃比氧化物玻璃具有低得多的声子能量,因此硫化物玻璃比氧化物玻璃能让电磁光谱红外区域更长得多波长的辐射透射。因此,可以看出,对于需要高效辐射发射用途(例如上述的用途)来说,硫化物玻璃具有成为稀土金属极好的基质材料的潜力。
然而,遗憾的是,许多硫化物玻璃是黑色的,因此它们不适合于上述的某些用途,这是因为这种基质玻璃代替了稀土金属添加剂起吸收激励辐射的作用。最著名的硫化物玻璃之一,即硫化砷玻璃,对于辐射光谱可见光部分长波区域以及远红外区域内的辐射是透明的。因此它看来可作稀土金属合适的基质玻璃。不过,现已发现稀土金属几乎不溶于硫化砷玻璃,而且已证实在这些难于掺入足够量的稀土元素供充分吸收激励能量之用。
众所周知,稀土金属在绝大多数氧化物玻璃中溶解度很大,据推测:稀土金属明显不溶于硫化砷玻璃是由于硫化砷玻璃和氧化物玻璃间存在着显著的结构不相似性。硫化砷玻璃被认为由共价结合的角锥形AsS3基团形成的长链和层所构成,而氧化物玻璃典型地是一种许多MO4四面体(它是通过相对来说属离子型的键结合的)形成的三维网状结构,其中M是一种所谓的形成网结构的金属,如硅、磷、铝、硼等。稀土金属容易容纳在这些离子型网状结构中,这是因为它们可以补偿由于存在两种或更多种形成网状结构金属(如硅酸铝玻璃中的硅和铝)而产生的电荷不平衡。而在硫化砷和相关玻璃所特有的二维共价结构中,可能不存在那些能量相似的位置。
引起大家兴趣的是美国专利4,612,294和4,704,371。
一个要考虑的具体问题是结晶起始温度(Tx)和玻璃转变温度(Tg)之差。本发明的一个目的是要在维持含硫化镓玻璃的基本性质情况下发现具有热稳定性更高的透明的新玻璃组成,以便在将玻璃成形为纤维时确保不致发生析晶现象。
这个目的在主要含有砷,锗和硫以及少量、但必需的镓和/或铟的玻璃中得到解决。为调节玻璃的某些性质,如热膨胀性,拆射率和热稳定性,可选择性地掺入其他少量的玻璃调节剂(Al、Sb、Li、Na、K、Ca、Sr、Ba、Ag、Hg、Tl、Cd、Sn、Pb、Y和镧系稀土金属)。本发明是根据下列二个基本点而发现的;第一,认识到在硫化镓锗玻璃中As浓度的增加会引起这些玻璃热稳定性的提高;第二,认识到加入一些Ga和/或In,以保证1300nm的荧光不会猝灭(通过测量该荧光寿命确定之)。
本发明玻璃的组成(以硫化物的摩尔百分数表示)基本上为:大约55-95%GeS2;2-40%As2S3;0.01-20%R2S3,其中R是至少一个选自镓和铟的三价形成网状结构的阳离子;0-10%MSx,其中M是一个选自铝、锑、钡、镉、钙、铅、锂、汞、钾、银、钠、锶、铊、锡、钇和镧系稀土金属的调节作用阳离子;0-20%氯化物和/或氟化物的总量;0-5%硒化物总量;而硫和/或锶的含量可在化学计量针的85-125%范围内变化。
当具有上述范围组成的玻璃用相当于至少0.005摩尔百分数Pr2S3的Pr3+离子掺入时,这种玻璃的τ值至少约300微秒,还可以采用更大浓度的Pr3+,但相当于大约0.5摩尔百分数Pr2S3的Pr3+离子已被认为是实际上的最大量了。
图1表示在基本组成中添加砷对玻璃热稳定性提高的情况。
图2表示玻璃组成中的镓含量对掺Pr3+玻璃的1300nm荧光寿命(τ)的影响。
表Ⅰ中所列的一组用硫化物摩尔百分数表示的玻璃组成,是用来说明本发明玻璃的。在这些玻璃组合物中掺入Pr3+离子是为了测量τ值。因为这些玻璃是在实验室中制备的,所以其制备方法一般是熔制各种元素的混合物,虽然在某些情况下是以硫化物形式加入某给定金属,但不难预料,这种采用元素混合物的做法是很昂贵的,而且也是不必要的。实际批料各加入物质可以是任何物料,只要它们在一起共同熔制时会转变为所需合适比例的硫化物就行。
玻璃熔制批料的所有原料先充分调和混合,然后封入先已抽真空至大约10-5至10-6乇的石英管中。该管子放入一炉中,炉子设计成可令炉料能进行摇摆运动。待炉料在850-950℃熔制大约1-2天后,将所得玻璃熔体在压缩空气流中淬冷,形成直径约7-10mm,长度约60-70mm的均质玻璃棒,该玻璃棒然后于大约325-425℃进行退火。
表Ⅰ也记录了每种玻璃的玻璃化转变温度(Tg)和结晶起始温度(Tx),(以℃表示),这二个测量值之差(Tx-Tg),以及τ值(以微秒表示)。
表Ⅰ
1 2 3 4 5 6GaS3 7.73 6.44 6.44 5.18 3.95 3.95GeS2 89.27 87.69 87.69 86.18 84.72 84.72As2S3 2.97 5.84 5.84 8.62 11.31 11.31Pr2S3 0.02 0.02 0.02 0.02 0.02 0.02过量S -- 112.4 -- -- 103.9 --Tg 424 323 387 376 324 346Tx 566 515 558 563 545 576Tx-Tg 142 192 171 186 220 231τ 336 -- -- -- 340 340
7 8 9 10 11 12Ga2S3 2.78 3.33 0.83 1.67 -- 12.67In2S3 -- -- -- -- 0.83 --GeS2 83.31 66.65 83.31 83.31 83.31 87.30As2S3 13.88 29.99 15.83 15.00 15.83 --Pr2S3 0.02 0.03 0.03 0.03 0.03 0.03过量S -- 106.1 -- -- -- --Tg 341 273 348 340 348 422Tx 602 >517 615 630 618 544Tx-Tg 261 >245 267 290 274 122τ 366 303 351 -- 315 354
13 14 15 16 17 18In2S3 1.67 2.50 -- -- -- --Al2S3 -- -- 0.83 1.67 2.50 --GeS2 83.31 83.31 83.31 83.31 83.31 83.31As2S3 15.00 14.17 15.83 15.00 14.17 16.67Pr2S3 0.03 0.03 0.03 0.03 0.03 0.03Tg 345 355 349 347 312 336Tx 600 615 613 602 614 628Tx-Tg 255 259 264 256 302 292τ 312 300 0 0 0 0
表Ⅱ列举了同样的那些玻璃组成,但以原子百分数表示。
表Ⅱ
1 2 3 4 5 6Ga 4.81 3.67 3.97 3.16 2.33 2.39Ge 27.77 24.99 27.02 6.31 24.99 25.63As 1.85 3.33 3.60 5.26 6.67 6.84S 65.55 68.0 65.40 65.26 66.0 65.13Pr 0.015 0.014 0.015 0.015 0.015 0.015
7 8 9 10 11 12Ga 1.67 1.75 0.50 1.00 -- 7.79In -- -- -- -- 0.50 --Ge 24.99 17.49 24.99 24.99 24.99 26.83As 8.33 15.74 9.50 9.00 9.50 --S 65.00 65.00 65.00 65.00 65.00 65.37Pr 0.015 0.015 0.015 0.015 0.015 0.015
13 14 15 16 17 18In 1.00 1.50 -- -- -- --Al -- -- 0.50 100 1.50 --Ge 24.99 24.99 24.99 24.99 24.99 24.99As 9.00 8.50 9.50 9.00 8.50 10.00S 64.99 65.00 65.00 64.99 65.00 65.00Pr 0.015 0.015 0.015 0.015 0.015 0.015
应该注意到,上述的步骤仅是描述实验室的操作。但本发明的玻璃批料同样可以在大型的工业化玻璃熔制装置中进行熔制,也可利用工业上的玻璃成形技术和设备将产生的熔体制成所需的玻璃制件。所需要的只是玻璃料加热至足够高的温度,保持足够长的时间,以得到均匀的熔体。然后乘熔体冷却时,将其成形为所需构型的玻璃制件,为避免产生析晶现象,冷却与成形的速率应足够快。
附图1显示了As的热稳定作用,其中Tx-Tg的值对应于一些砷镓锗硫化物玻璃的As含量作图。实验室结果表明,As对化学计量的玻璃和含过量硫的玻璃都有这种稳定作用。在两类玻璃中,当Ge的含量(以原子百分数计)保持近似恒定情况下,As基本上是代替Ga的。由附图1明显可见,含大约2原子百分数As的玻璃组合物,其Tx-Tg值约为150℃,而含As含量大于5%的玻璃组合物,在200℃以上仍具有热稳定性,这个值就大约是在上述编号中公开的钡稳定的镓锗硫化物玻璃的最大极限。相反,实施例12的无As玻璃,其Tx-Tg值则不超过大约120℃。含8.33原子百分数As实施例7玻璃,Tx-Tg约为260℃。根据相关硫化砷玻璃和富锗硫化物玻璃外推得到的粘度数据,可以预计,这种玻璃可以重新加热,使其粘度低至100MPa(103泊),而不会产生结晶。因为适合于用重拉伸方法拉制纤维的优选玻璃,其粘度在104-106MPa(105-107泊)之间,象实施例7那样的玻璃应该会显示更高的热稳定性,从而能通过预制重拉伸的方法制造纤维。
观察一下附图2,可以看出在本发明玻璃组合物中掺入一定量镓和/铟的必要性。该图是添加Pr3+引起的玻璃在1300nm波长的荧光寿命(τ)对于砷镓锗硫化物玻璃中的镓含量的作图。附图2中作图的玻璃组合物与附图1中化学计量系列的玻璃组合物相同。这些数据清楚地表明,只要玻璃组成中含镓,则这些玻璃的τ就相当恒定地保持在大约350微秒;镓的最低有效浓度稍微超过活性稀土添加剂的浓度。例如,对于添加0.02%Pr的玻璃而言,镓和/或铟的最低有效浓度大约为0.03原子百分数。正如实施例18表明,对不含镓的二元硫化砷锗玻璃而言,τ值基本上为零。即1300nm的荧光基本上猝灭了。曾有人假定,存在镓和/或类似的三价网状结构形成作用的阳离子铟,会在这些玻璃中产生一些键合较弱的硫的位置,这些键合较弱的硫离子转而为掺入的调节作用离子(在这时是稀土金属Pr的阳离子)提供合适的结构位置。人们假定,镓和/或是混乱分布于本发明玻璃中,这就提供了使稀土添加剂均匀分散。因此防止人们已确认的浓度猝灭现象的一种机理。
在编号中揭示了铝是令人满意的形成网状结构的阳离子,而正如实施例15、16、17所述,实验结果表明,铝不象镓和铟那样能有效地防止本发明玻璃中的荧光猝灭。因此铝虽然可以作为一种可用的调节剂加入。但当需要防止荧光猝灭时,就需加入镓和/或铟。
根据各种性质总体平衡的考虑,以硫化物的摩尔百分数表示的优选的本发明组成基本上为:60-95%GeS2;5-30%As2S3;0.1-15%R2S3,其中R是至少一个选自镓和铟的三价形成网状结构的阳离子;0-10%MSx,其中M是一个选自铝、钡、镉、钙、铅、锂、汞、钾、银、钠、锶、铊、锡、钇和镧系稀土金属的调节作用阳离子;0-10%氯化物和/或氟化物的总量;0-3%硒化物总量;而硫和/或锶的含量可在化学计量值的90-120%范围内变化。
实施例9是本发明最优选的实施例。
Claims (3)
1.一种在电磁辐射光谱的远红外区域内具有透射性的透明玻璃,其特征在于,以硫化物的摩尔百分数表示的组成基本上为:55-95%GeS2;2-40%As2S3;0.01-20%R2S3,其中R是至少一个选自镓和铟的三价形成网状结构的阳离子;0-10%MSx,其中M是一个选自铝、锑、钡、镉、钙、铅、锂、汞、钾、银、钠、锶、铊、锡、钇和镧系稀土金属的调节作用阳离子;0-20%氯化物和/或氟化物的总量;0-5%硒化物总量;而硫和/或锶的含量可在化学计量值的85-125%范围内变化,结晶起始温度和玻璃化转变温度之差至少为150℃。
2.如权利要求1所述的透明玻璃,其特征在于当掺人相当于至少0.005%Pr2S3量的镨时,它具有至少300微秒的τ值。
3.一种在电磁辐射光谱的远红外区域内具有透射性的透明玻璃,其特征在于,以硫化物的摩尔百分数表示的组成基本上为:60-95%GeS2;5-30%As2S3;0.1-15%R2S3,其中R是至少一个选自镓和铟的三价形成网状结构的阳离子;0-10%MSx,其中M是一个选处铝、钡、镉、钙、铅、锂、汞、钾、银、钠、锶、铊、锡、钇和镧系稀土金属的调节作用阳离子;0-10%氯化物和/或氟化物的总量;0-3%硒化物总量;而硫和/或锶的含量可在化学计量值的90-120%范围内变化,结晶起始温度和玻璃化转变温度之差大于200℃。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/225,766 US5389584A (en) | 1994-04-11 | 1994-04-11 | Ga- and/or In-containing AsGe sulfide glasses |
US08/225,766 | 1994-04-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1113218A CN1113218A (zh) | 1995-12-13 |
CN1042725C true CN1042725C (zh) | 1999-03-31 |
Family
ID=22846143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95102315A Expired - Fee Related CN1042725C (zh) | 1994-04-11 | 1995-04-08 | 含镓和/或铟的硫化砷锗玻璃 |
Country Status (9)
Country | Link |
---|---|
US (1) | US5389584A (zh) |
EP (1) | EP0676378B1 (zh) |
JP (1) | JP3972376B2 (zh) |
KR (1) | KR950031956A (zh) |
CN (1) | CN1042725C (zh) |
AU (1) | AU689853B2 (zh) |
CA (1) | CA2143538A1 (zh) |
DE (1) | DE69500711T2 (zh) |
TW (1) | TW334415B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100384766C (zh) * | 2006-03-15 | 2008-04-30 | 中国科学院上海硅酸盐研究所 | 一种全波段光窗玻璃材料及制备方法 |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5856882A (en) * | 1995-02-15 | 1999-01-05 | Hoya Corporation | Optical fibers and optical fiber amplifiers |
US5846889A (en) * | 1997-03-14 | 1998-12-08 | The United States Of America As Represented By The Secretary Of The Navy | Infrared transparent selenide glasses |
JP2000512611A (ja) * | 1997-04-15 | 2000-09-26 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | 低エネルギーのフォノンスペクトルを有するガラス組成物、その製法並びにその使用 |
CA2306267A1 (en) * | 1997-11-04 | 1999-05-14 | Corning Incorporated | Stable cladding glasses for sulphide fibres |
FR2771405B1 (fr) * | 1997-11-27 | 2000-02-04 | Univ Rennes | Verres a base de chalcogenures, leur preparation et leur application |
US6145342A (en) * | 1998-01-30 | 2000-11-14 | The United States Of America As Represented By The Secretary Of The Navy | Catalyzed preparation of amorphous chalcogenides |
JP2002535228A (ja) | 1999-01-21 | 2002-10-22 | コーニング インコーポレイテッド | Pを含有するGeAsスルフィドガラス |
KR100383608B1 (ko) * | 2000-07-06 | 2003-05-16 | 삼성전자주식회사 | 알칼리 할로겐이 첨가된 광증폭기용 황화물 유리 및 그제조 방법 |
KR100341212B1 (ko) * | 2000-07-31 | 2002-06-20 | 오길록 | 1.6 미크론미터 대역 광 증폭 시스템 |
FR2857354B1 (fr) * | 2003-07-07 | 2005-09-16 | Centre Nat Rech Scient | Composition vitreuses, de type vitroceramique, transparentes dans l'infrarouge |
JP5339720B2 (ja) * | 2007-12-28 | 2013-11-13 | 五鈴精工硝子株式会社 | モールド成型用赤外線透過ガラス |
US7767604B2 (en) * | 2008-04-29 | 2010-08-03 | Corning Incorporated | Ga—P—S glass compositions |
CN101811829B (zh) * | 2010-03-31 | 2012-02-08 | 武汉理工大学 | 一种具有锂离子导体功能的硫系微晶玻璃材料的制备方法 |
RU2450983C2 (ru) * | 2010-08-25 | 2012-05-20 | Учреждение Российской академии наук Институт химии высокочистых веществ РАН (ИХВВ РАН) | Особо чистый сульфидно-мышьяковый материал для синтеза высокопрозрачных халькогенидных стекол и способ его получения |
US8541324B2 (en) | 2010-11-30 | 2013-09-24 | Corning Incorporated | Pergallous alkaline earth selenogermanate glasses |
US9187360B2 (en) * | 2012-04-20 | 2015-11-17 | Schott Corporation | Glasses for the correction of chromatic and thermal optical aberations for lenses transmitting in the near, mid, and far-infrared sprectrums |
WO2014085237A1 (en) * | 2012-11-28 | 2014-06-05 | Corning Incorporated | Alkali selenogermanate glasses |
DE102014103560A1 (de) | 2013-03-15 | 2014-09-18 | Schott Corporation | Optisches Binden durch die Verwendung von optischem Glas mit niedrigem Erweichungspunkt für optische IR-Anwendungen und gebildete Produkte |
WO2015073282A1 (en) | 2013-11-18 | 2015-05-21 | Corning Incorporated | Non-stoichiometric alkaline earth chalcogeno-germanate glasses |
US9379321B1 (en) * | 2015-03-20 | 2016-06-28 | Intel Corporation | Chalcogenide glass composition and chalcogenide switch devices |
US10099957B2 (en) * | 2015-06-17 | 2018-10-16 | Schott Corporation | Infrared transmission chalcogenide glasses |
CN105906205A (zh) * | 2016-04-13 | 2016-08-31 | 同济大学 | 通过稀土化合物共掺杂可控析出ML-Ag团簇和Ag纳米晶的发光玻璃及其制备方法 |
JP7070824B2 (ja) * | 2017-08-02 | 2022-05-18 | 日本電気硝子株式会社 | カルコゲナイドガラス材 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704371A (en) * | 1985-09-26 | 1987-11-03 | Schott Glaswerke | Infrared-transparent chalcogenide glass |
JPH038742A (ja) * | 1989-06-02 | 1991-01-16 | Hisankabutsu Glass Kenkyu Kaihatsu Kk | コアクラッド構造を有するGe―As―Sガラスファイバー |
US5240885A (en) * | 1992-09-21 | 1993-08-31 | Corning Incorporated | Rare earth-doped, stabilized cadmium halide glasses |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1020482A (en) * | 1961-11-07 | 1966-02-16 | Pilkington Brothers Ltd | Improvements in or relating to glass |
DE2439848C2 (de) * | 1973-08-20 | 1985-05-15 | Canon K.K., Tokio/Tokyo | Verfahren zum Aufzeichnen mittels eines Laserstrahls |
US4087511A (en) * | 1975-11-20 | 1978-05-02 | Allied Chemical Corporation | Glasses prepared by the melting of stoichiometric compounds |
JPS5895625A (ja) * | 1981-11-30 | 1983-06-07 | Nippon Telegr & Teleph Corp <Ntt> | 赤外線透過光フアイバ |
US4599462A (en) * | 1983-05-25 | 1986-07-08 | University Of Utah | Methods for making solid solutions from normally immiscible components and for modifying the surface structure of solid materials |
JPS60118651A (ja) * | 1983-11-28 | 1985-06-26 | Hitachi Ltd | 赤外光フアイバ用ガラス材料 |
US4973345A (en) * | 1987-10-13 | 1990-11-27 | British Telecommunications Public Limited Company | Surface treatments for optical fibre preforms |
US5315434A (en) * | 1991-05-21 | 1994-05-24 | Matsushita Electric Industrial Co., Ltd. | Infrared-transmissive lens and human body detecting sensor using the same |
JPH0585769A (ja) * | 1991-09-25 | 1993-04-06 | Hoya Corp | 赤外線透過用材料 |
US5392376A (en) * | 1994-04-11 | 1995-02-21 | Corning Incorporated | Gallium sulfide glasses |
-
1994
- 1994-04-11 US US08/225,766 patent/US5389584A/en not_active Expired - Lifetime
-
1995
- 1995-02-13 TW TW084101376A patent/TW334415B/zh active
- 1995-02-28 CA CA002143538A patent/CA2143538A1/en not_active Abandoned
- 1995-03-27 DE DE69500711T patent/DE69500711T2/de not_active Expired - Fee Related
- 1995-03-27 EP EP95104462A patent/EP0676378B1/en not_active Expired - Lifetime
- 1995-04-03 AU AU16232/95A patent/AU689853B2/en not_active Ceased
- 1995-04-08 CN CN95102315A patent/CN1042725C/zh not_active Expired - Fee Related
- 1995-04-10 JP JP10779195A patent/JP3972376B2/ja not_active Expired - Fee Related
- 1995-04-11 KR KR1019950008379A patent/KR950031956A/ko not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704371A (en) * | 1985-09-26 | 1987-11-03 | Schott Glaswerke | Infrared-transparent chalcogenide glass |
JPH038742A (ja) * | 1989-06-02 | 1991-01-16 | Hisankabutsu Glass Kenkyu Kaihatsu Kk | コアクラッド構造を有するGe―As―Sガラスファイバー |
US5240885A (en) * | 1992-09-21 | 1993-08-31 | Corning Incorporated | Rare earth-doped, stabilized cadmium halide glasses |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100384766C (zh) * | 2006-03-15 | 2008-04-30 | 中国科学院上海硅酸盐研究所 | 一种全波段光窗玻璃材料及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0676378A1 (en) | 1995-10-11 |
DE69500711T2 (de) | 1998-02-19 |
DE69500711D1 (de) | 1997-10-23 |
TW334415B (en) | 1998-06-21 |
US5389584A (en) | 1995-02-14 |
KR950031956A (ko) | 1995-12-20 |
EP0676378B1 (en) | 1997-09-17 |
AU689853B2 (en) | 1998-04-09 |
JP3972376B2 (ja) | 2007-09-05 |
CN1113218A (zh) | 1995-12-13 |
CA2143538A1 (en) | 1995-10-12 |
AU1623295A (en) | 1995-10-19 |
JPH07291655A (ja) | 1995-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1042725C (zh) | 含镓和/或铟的硫化砷锗玻璃 | |
US5392376A (en) | Gallium sulfide glasses | |
CN102066274B (zh) | Ga-P-S玻璃组合物 | |
DE1496091A1 (de) | Phototropische Glaskoerper | |
US4768859A (en) | Cladding glass for optical fiber | |
JPH04231345A (ja) | フッ素不含有リン酸ガラス | |
NO142686B (no) | Apparat for deteksjon av lengdeforskyvning av en kabel | |
DE3102783A1 (de) | "glas fuer eine optische faser" | |
KR20010023536A (ko) | 희토류가 첨가된 저 포논 에너지 유리 및 섬유 | |
US2701208A (en) | Glasses | |
US3773529A (en) | Non-oxide glass | |
Fuxi | New glass-forming systems and their practical application | |
US4257811A (en) | Solarization and irradiation resistant optical glasses | |
US3826661A (en) | High index optical glass | |
AU704313B2 (en) | Gallium sulfide glasses | |
US3188216A (en) | Glass containing strontium and gallium compounds | |
EP1036343A1 (en) | Stable cladding glasses for sulphide fibres | |
JP3089888B2 (ja) | 微粒子分散ガラス | |
JPS6177639A (ja) | 赤外光学膜材料の製造法 | |
DE1496091C (de) | Glaskörper aus Sihkatglas, der Metall halogenide, jedoch kein Silberhalogenid ent halt, und dessen optische Durchlässigkeit im umgekehrten Verhältnis zu der auf ihn auftreffenden aktinischen Strahlung steht, sowie Verfahren zu seiner Herstellung | |
JPS6395139A (ja) | ハライドガラス | |
JPS63129037A (ja) | 低融点ガラス |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |