CN101775661B - 一种蓝宝石掺杂剂的制备方法 - Google Patents
一种蓝宝石掺杂剂的制备方法 Download PDFInfo
- Publication number
- CN101775661B CN101775661B CN2009102516697A CN200910251669A CN101775661B CN 101775661 B CN101775661 B CN 101775661B CN 2009102516697 A CN2009102516697 A CN 2009102516697A CN 200910251669 A CN200910251669 A CN 200910251669A CN 101775661 B CN101775661 B CN 101775661B
- Authority
- CN
- China
- Prior art keywords
- sapphire
- ammonium
- doping agent
- powder
- content
- 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.)
- Active
Links
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 28
- 239000010980 sapphire Substances 0.000 title claims abstract description 28
- 239000002019 doping agent Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 8
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims abstract description 6
- 230000009615 deamination Effects 0.000 claims abstract description 5
- 238000006481 deamination reaction Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 3
- 230000023556 desulfurization Effects 0.000 claims abstract description 3
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 3
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010437 gem Substances 0.000 description 2
- 229910001751 gemstone Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- -1 photoelectron Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GLVPUAWFPNGKHO-UHFFFAOYSA-L N.[Fe+2].[O-]S([O-])(=O)=O Chemical compound N.[Fe+2].[O-]S([O-])(=O)=O GLVPUAWFPNGKHO-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明公开了一种蓝宝石掺杂剂的制备方法，其特征在于是将硫酸铁铵粉和氟钛酸铵粉分别加入到纯水中，制得溶液中的硫酸铁铵含量为0.005-0.01g/ml，氟钛酸铵含量为0.0005-0.001g/ml；按体积重量比14-15ml/Kg的比例将所述溶液与硫酸铝铵粉混合搅拌；然后，将混合后物料加热至200℃时，恒温60-90分钟进行脱水处理；再加热至900℃时，恒温100-120分钟进行脱氨、脱硫处理，得到目标产物。本发明适宜作为火焰法、提拉法等方法生长蓝宝石的原料，生长出的单晶体可用作优质窗口，高精密零部件等。
Description
技术领域
本发明涉及蓝宝石生产领域，具体是一种蓝宝石掺杂剂的制备方法。
背景技术
蓝宝石晶体(α-Al2O3单晶)是一种简单配位型氧化物晶体，属六方晶系，空间群D6 3 d2 R3 mc，其具有一系列独特的物理、机械和热特性，化学性能稳定。是一种熔点很高(2050℃)的难熔氧化物晶体，晶体硬度为9.0Mohs。Al2O3晶体从真空紫外、可见、近红外一直到中红外5.5μm均具有高的光学透过率，与许多其它光学窗口材料相比，有更好的机械性能和物理性能，如高硬度、高拉伸强度、抗冲刷性、热导性、机械稳定性和显著的抗热冲击性能等。一直广泛应用于红外军事装备、卫星和空间技术的仪表及高功率激光器的窗口材料，近来又成为重力波探测器中光学系统的首选材料。还是使用最广泛的氧化物衬底(主要用作半导体衬底和大规模集成电路衬底)材料之一。在军工、航天、LED衬底、光电子、半导体集成电路、特种零部件、高档奢侈品等领域被广泛应用，市场潜力十分巨大。为满足不同的理化性能需求，各种类型掺杂剂的作用就显得尤为重要。
作为窗口级蓝宝石，掺杂元素对蓝宝石的作用主要是指对其结构、颜色等方面的影响。蓝宝石属于刚玉类宝石，其主要化学成分为Al2O3，通常有铁、钛等类质同象替代铝。其中蓝宝石的颜色与主要致色元素的含量及其比值以及形成时的氧逸度有着密切的关系。如Fe3+、Si4+、Co2+是使蓝宝石呈现蓝色的主要离子，Cr3+离子可以使蓝宝石呈现出橙色和绿色，Mn4+离子可使蓝宝石呈现黄色。
晶体结构方面的变化直接导致蓝宝石的晶格完整度，硬度，抗热冲击性，导热性，机械稳定性、导电性、化学稳定性等理化性能发生改变，研究意义十分重大。为此在人工生长蓝宝石单晶体时，常常有意的掺杂大量元素进入到晶体中，以得到理想中的特性。
其中铁和钛的价间电荷转移是引起蓝宝石颜色变化的主因。在蓝宝石的生长过程中，由于环境中存在着Fe3+，六次配位态的Fe3+离子半径为0.063nm，与Al3+离子半径(0.061nm)接近。因而Fe3+与Al3+可以发生类质同象替代而进入晶格。但是，由于离子半径及电负性等的差异，这种替代发生后，Al2O3晶体结构中，金属阳离子与O2-的距离及作用力就会发生变化，即金属阳离子(Fe3+、Al3+)或O2-偏离原来的位置，这种变化导致了[AlO6]八面体位置对称性的降低，也导致了晶体场能量的变化，从而导致了Fe3+的轨道分裂，产生了蓝宝石对光波的选择性吸收。每种微量元素均对可见光的特定波段产生不同程度的吸收。Ti4+不产生晶体场光谱，在可见光区无吸收峰，但当它与其它低价过渡金属离子(如Fe2+)相邻时，可以产生吸收光谱，既是发生Ti3++O2→Ti4+的转变，位置在580nm左右。随着铁和钛含量的增高，蓝宝石的颜色逐渐加深；蓝宝石中由于铬、镍、锰杂质含量高，使宝石透明度变差，灰色调显著。掺杂元素越少晶体越纯净，晶格完整度越高，透光率越好。而由于铁、钛等元素进入到晶体的晶格之中，致使单晶蓝宝石的密度变大，并且进一步使晶格结构发生了改变，在冷凝过程中容易导致杂质分布不均形成色斑，对晶体的质量产生较大的影响。好处是可以增加晶体的抗热冲击性和提高晶体的硬度。所以为得到理想颜色和性质的蓝宝石，掺杂剂的选择、配比及其处理方法就成为了关键。
发明内容
本发明提供了一种蓝宝石掺杂剂的制备方法，适宜作为火焰法、提拉法等方法生长蓝宝石的原料，生长出的单晶体可用作优质窗口，高精密零部件等。
本发明的技术方案为：
一种蓝宝石掺杂剂的制备方法，其特征在于是将硫酸铁铵粉和氟钛酸铵粉分别加入到纯水中，制得溶液中的硫酸铁铵含量为0.005-0.01g/ml，氟钛酸铵含量为0.0005-0.001g/ml；按体积重量比14-15ml/Kg的比例将所述溶液与硫酸铝铵粉混合搅拌；然后，将混合后物料加热至200℃时，恒温60-90分钟进行脱水处理；再加热至900℃时，恒温100-120分钟进行脱氨、脱硫处理，得到目标产物。
本发明的方程式为：
1、所述溶液与硫酸铝铵粉混合后物料在加热至200℃时，恒温60-90min进行脱水处理：
2、脱水处理后的物料在加热至900℃时，恒温100-120分钟进行脱氨，脱硫反应：
本发明生产出的氧化铝粉料具有成本低、纯度高等明显优势，掺杂剂氧化铁中的Fe3+及氧化钛中的Ti4+离子嵌入到[AlO6]八面体，形成高分子聚合团，经过充分活化后，适宜作为火焰法、提拉法等方法生长蓝宝石的原料。所生长出的晶体颜色为蓝白色(接近透明)，平均透光率达到85％以上，硬度可达到莫氏9.2。可用作大尺寸优质窗口，高精密零部件等，具有广泛的市场和适用性。
具体实施方式
蓝宝石掺杂剂的制备方法：
将高纯硫酸铁铵粉和高纯氟钛酸铵粉加入到纯水中，混合溶解成溶液，溶液中硫酸铁铵的含量为0.005-0.01g/ml，氟钛酸铵的含量为0.0005-0.001g/ml，然后在溶液中加入硫酸铝铵粉混合搅拌，溶液与硫酸铝铵粉的比例为10-15ml∶1Kg，然后加热至200℃，恒温80-100min进行脱水反应，升温至900℃，恒温110-120min进行脱氨、脱硫反应，然后得产品。
Claims (1)
1.一种蓝宝石掺杂剂的制备方法，其特征在于是将硫酸铁铵粉和氟钛酸铵粉分别加入到纯水中，制得溶液中的硫酸铁铵含量为0.005-0.01g/ml，氟钛酸铵含量为0.0005-0.001g/ml；按体积重量比14-15ml/Kg的比例将所述溶液与硫酸铝铵粉混合搅拌；然后，将混合后物料加热至200℃时，恒温60-90分钟进行脱水处理；再加热至900℃时，恒温100-120分钟进行脱氨、脱硫处理，得到目标产物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102516697A CN101775661B (zh) | 2009-12-30 | 2009-12-30 | 一种蓝宝石掺杂剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102516697A CN101775661B (zh) | 2009-12-30 | 2009-12-30 | 一种蓝宝石掺杂剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101775661A CN101775661A (zh) | 2010-07-14 |
| CN101775661B true CN101775661B (zh) | 2011-06-15 |
Family
ID=42512242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102516697A Active CN101775661B (zh) | 2009-12-30 | 2009-12-30 | 一种蓝宝石掺杂剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101775661B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432268B (zh) * | 2011-09-04 | 2012-12-05 | 湖北菲利华石英玻璃股份有限公司 | 一种采用焰熔法将氧化铝粉末烧结成生产蓝宝石晶体用氧化铝块料的方法 |
| CN104562182B (zh) * | 2015-01-29 | 2017-04-19 | 常州焱晶科技有限公司 | 一种蓝宝石晶体的合成方法 |
| CN105568382B (zh) * | 2015-12-31 | 2018-02-09 | 同济大学 | 一种致色均匀的蓝色宝石晶体及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374251A (zh) * | 2002-04-08 | 2002-10-16 | 常耀辉 | 超纯纳米级氧化铝粉体的制备方法 |
| CN1631788A (zh) * | 2004-12-28 | 2005-06-29 | 中国铝业股份有限公司 | 一种球形高纯氧化铝的制备方法 |
| CN1769179A (zh) * | 2005-10-12 | 2006-05-10 | 中国铝业股份有限公司 | 一种生产单晶型氢氧化铝的方法 |
| JP2008100903A (ja) * | 2006-09-19 | 2008-05-01 | Sumitomo Chemical Co Ltd | αアルミナ粉末 |
| US20090098365A1 (en) * | 2005-07-16 | 2009-04-16 | Center For Abrasives And Refractories Research & Developement C.A.R.R.D. Gmbh | Nanocrystalline sintered bodies made from alpha aluminum oxide method for production and use thereof |
-
2009
- 2009-12-30 CN CN2009102516697A patent/CN101775661B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374251A (zh) * | 2002-04-08 | 2002-10-16 | 常耀辉 | 超纯纳米级氧化铝粉体的制备方法 |
| CN1631788A (zh) * | 2004-12-28 | 2005-06-29 | 中国铝业股份有限公司 | 一种球形高纯氧化铝的制备方法 |
| US20090098365A1 (en) * | 2005-07-16 | 2009-04-16 | Center For Abrasives And Refractories Research & Developement C.A.R.R.D. Gmbh | Nanocrystalline sintered bodies made from alpha aluminum oxide method for production and use thereof |
| CN1769179A (zh) * | 2005-10-12 | 2006-05-10 | 中国铝业股份有限公司 | 一种生产单晶型氢氧化铝的方法 |
| JP2008100903A (ja) * | 2006-09-19 | 2008-05-01 | Sumitomo Chemical Co Ltd | αアルミナ粉末 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101775661A (zh) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Synthesis of YAG powders by the co-precipitation method | |
| Rejisha et al. | Synthesis and characterization of strontium and barium bismuth borate glass-ceramics | |
| CN109402740B (zh) | 一种晶体材料、其制备方法及包含其的非线性光学晶体 | |
| Dai et al. | Fabrication of Tb3Al5O12 transparent ceramics using co-precipitated nanopowders: The influence of ammonium hydrogen carbonate to metal ions molar ratio | |
| Liu et al. | Fabrication and characterizations of (Tb1-xPrx) 3Al5O12 magneto-optical ceramics for Faraday isolators | |
| CN101775661B (zh) | 一种蓝宝石掺杂剂的制备方法 | |
| HUANG et al. | Fabrication and characterizations of Yb: YAG transparent ceramics using alcohol-water co-precipitation method | |
| Latha et al. | Effect of Li+ coodoping on the photoluminescence of novel green emitting BiOCl: Tb3+ nanophosphors for display, visualization of latent fingerprints and anticounterfeiting applications | |
| Lin et al. | Competitive crystallization of β-Zn2SiO4 and ZnO in an aluminosilicate glass | |
| CN102817072A (zh) | 一种用于导模法生长宝石单晶生长的掺杂原料的制备方法 | |
| Dai et al. | Synthesis of Tb4O7 nanopowders by the carbonate-precipitation method for Tb3Al5O12 magneto-optical ceramics | |
| CN101676449A (zh) | 一种非中心对称结构稀土硫化物的晶体生长方法 | |
| Shinde et al. | Structural and luminescence properties of Gd2Si2O7: Ce prepared by solution combustion followed by heat treatment | |
| Liu et al. | Two non-centrosymmetric mixed alkali metal and alkaline earth metal scandium borate nonlinear optical materials with short ultraviolet cutoff edges | |
| Zhang et al. | Synthesis and characteristics of fine crystalline LuAG: Ce phosphors by microwave-induced solution combustion method | |
| Ovanesyan et al. | Single crystal growth and characterization of LaLuO3 | |
| Li et al. | Effects of zirconium ions doping on the structural and thermochromic properties of VO 2 thin films | |
| Song et al. | Synthesis and characterization of CaF 2 nanoparticles with different doping concentrations of Er 3+ | |
| Eyassu et al. | Facile solvothermal synthesis of NIR absorbing CsxWO3 nanorods by benzyl alcohol route | |
| CN104005088A (zh) | 过渡族金属离子掺杂的镁铝尖晶石晶体的提拉法生长方法 | |
| Yan et al. | Solid-solid synthesis and structural phase transition process of SmF3 | |
| Yao et al. | Eu: Y2O3 nano-phosphor prepared by novel energy-saving solution combustion method | |
| Kang et al. | Hydrothermal syntheses and crystal structure of NH4Ln3F10 (Ln= Dy, Ho, Y, Er, Tm) | |
| Wang et al. | Crystal Growth and Characterization of a New Organometallic Nonlinear‐Optical Crystal Material: MnHg (SCN) 4 (C3H8O2) | |
| Zeng et al. | Novel NaFeTiO4 cool pigment with high-infrared reflectance and low thermal conductivity |
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 | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Nan Inventor after: Zhao Qing Inventor after: Jia Jianguo Inventor before: Luo Ping |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LUO PING TO: WANG NAN ZHAO QING JIA JIANGUO |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170718 Address after: Figure 028000 Town Industrial Park Tongliao city the Inner Mongolia Autonomous Region Muli Horqin district Patentee after: Bourne smile sapphire Co., Ltd. Address before: 237321, Hongshi Town, Jinzhai County, Anhui Province Patentee before: Homford Crystal Technology (Anhui) Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Figure 028000 Town Industrial Park Tongliao city the Inner Mongolia Autonomous Region Muli Horqin district Patentee after: Tongliao Seiko Sapphire Co., Ltd. Address before: Figure 028000 Town Industrial Park Tongliao city the Inner Mongolia Autonomous Region Muli Horqin district Patentee before: Bourne smile sapphire Co., Ltd. |