JPS6340799A - Production of titanium phosphate-potassium single crystal - Google Patents
Production of titanium phosphate-potassium single crystalInfo
- Publication number
- JPS6340799A JPS6340799A JP18318786A JP18318786A JPS6340799A JP S6340799 A JPS6340799 A JP S6340799A JP 18318786 A JP18318786 A JP 18318786A JP 18318786 A JP18318786 A JP 18318786A JP S6340799 A JPS6340799 A JP S6340799A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- ktipo5
- flux
- powder
- production
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ZBWBYBYOJRDPDE-UHFFFAOYSA-K potassium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[K+] ZBWBYBYOJRDPDE-UHFFFAOYSA-K 0.000 title description 2
- 230000004907 flux Effects 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000007716 flux method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 2
- 235000011009 potassium phosphates Nutrition 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000155 melt Substances 0.000 abstract 2
- 229910020494 K2WO4 Inorganic materials 0.000 abstract 1
- 238000000137 annealing Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract 1
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 241000080590 Niso Species 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、リン酸チタン・カリウム（ＫＴｉＰＯ５）単
結晶をフラックス法で育成することにより製造する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a titanium potassium phosphate (KTiPO5) single crystal by growing it by a flux method.
〔従来技術及び発明が解決しようとする問題点〕Ｋ Ｔ
ｉ Ｐ Ｏｓ単結晶は、近年非線形光学材料として注
目されている。その理由は、ＫＴｉＰＯ５単結晶を用い
ると赤外ＹＡＧレーザー光を緑色光に変調でき、しかも
この変換効率が極めて高いことにある。[Prior art and problems to be solved by the invention] K T
i P Os single crystal has recently attracted attention as a nonlinear optical material. The reason for this is that when KTiPO5 single crystal is used, infrared YAG laser light can be modulated into green light, and the conversion efficiency is extremely high.
ところで、上記用途に用いるＫ Ｔ ｉ Ｐ Ｏｓ単結
晶は、従来ＳＯＯ〜７００’ｃ、３０００気圧という過
酷な条件下で水熱合成法により育成されている。その理
由はＫＴｉＰＯｌをそのまま高温に熱するとＫ Ｔ ｉ
Ｐ Ｏ５のリン酸根が分解蒸散し、化学組成が変化す
るからである。このため得られるＫ Ｔ ｉ Ｐ Ｏｓ
単結晶は極めて高価となり、これが上記のように優れた
性能を有するにもかかわらず広く普及しない原因の一つ
になっている。By the way, the K Ti P Os single crystal used for the above purpose has conventionally been grown by hydrothermal synthesis under harsh conditions of SOO~700'c and 3000 atm. The reason is that when KTiPOl is heated to a high temperature, KTi
This is because the phosphate group of PO5 decomposes and transpires, changing the chemical composition. Therefore, the obtained K T i P Os
Single crystals are extremely expensive, which is one of the reasons why they are not widely used despite their excellent performance as described above.
本発明は、上記問題点に鑑み、ＫＴｉＰＯｓｌｌ結晶を
安価に製造すべく為されたものであり、ＫＴ ｉ Ｐ
Ｏｓ単結晶を大気圧で育成し得、低コストで製造し得る
方法を提供することを目的とする。In view of the above-mentioned problems, the present invention was devised to produce KTiPOsll crystal at low cost.
An object of the present invention is to provide a method that allows Os single crystals to be grown at atmospheric pressure and manufactured at low cost.
〔問題点を解決するための手段及び作用〕上記目的を達
成するため、本発明者等はフラ。[Means and effects for solving the problems] In order to achieve the above object, the inventors have completed the following steps.
ラス法によれば大気圧で育成できることに着目し、種々
のフラックスについて検討した結果、Ｋ、 ＭＯ，ＣＭ
はＷ、Ｍｏ、Ｃｒ及びＳから選ばれる少なくとも一種で
ある〕で表わされる化合物をフラノクスとして用いれば
よいことを見い出して本発明に到達した。Focusing on the fact that the lath method allows growth at atmospheric pressure, we investigated various fluxes and found that K, MO, CM
is at least one selected from W, Mo, Cr and S], and the present invention was achieved by discovering that a compound represented by the following formula may be used as a furanox.
本発明に用いるＫ Ｔ ｉ Ｐ Ｏｓ粉末はＫＰｏ、と
ＴｉＯ□の等モル混合物を焙焼して得られる。このＫ
Ｔ ｔ Ｐ Ｏｓ粉末のフラックスとしてＫｔ ＷＯ４
゜Ｋｔ ＭＯＯ４、に２ Ｃｒ０ａ及びに、ＳＯ，がら
選ばれる少くとも一種が用いられる。これらのフラック
スの中ではＫｔＷＯａが最も好ましい。The K Ti P Os powder used in the present invention is obtained by roasting an equimolar mixture of KPo and TiO□. This K
Kt WO4 as flux of T t P Os powder
At least one selected from ゜Kt MOO4, ni2Cr0a, and niSO is used. Among these fluxes, KtWOa is the most preferred.
上記ＫｚＭ○４フランクスにＭＯｚ、ＫＰＯ３を添加す
ることはＫ Ｔ ｉ’ Ｐ Ｏｓ単結晶を安定に育成す
る上で好ましい。即ち、Ｋ、ＭＯ，だけのフラックスの
場合、均一熔融するために１１００℃程度の温度に保持
する時間が長くなったり、この温度が幾分高くなると黒
色板状の結晶も析出することがあるが、Ｍ ０３ 、
Ｋ Ｐ ０３を添加すると、上記保持時間が長くなら
ないと共に、黒色板状結晶の析出を抑制できるからであ
る。この黒色板状結晶の組成は明らかではないが、Ｋ
Ｔ ｉ Ｐ Ｏｓ の部分分解生成物が核になって形成
されていると考えられる。従って、ＭＯ，はＫＴｉＰＯ
，のリン酸根の蒸散により過剰となるＫをに２ＭＯ，に
戻すように作用し、ＫＰｏ、３は不足したリン酸根を補
充するように作用するものと推測される。It is preferable to add MOz and KPO3 to the above-mentioned KzM○4 Franks in order to stably grow the KT i' P Os single crystal. In other words, in the case of a flux containing only K and MO, the time required to maintain the temperature at around 1100°C is longer in order to melt it uniformly, and if this temperature rises somewhat, black plate-like crystals may also precipitate. , M 03 ,
This is because when K P 03 is added, the above-mentioned retention time does not become long and the precipitation of black plate-like crystals can be suppressed. The composition of this black plate-like crystal is not clear, but K
It is thought that the partial decomposition products of T i P Os are formed as nuclei. Therefore, MO, is KTiPO
It is presumed that KPo,3 acts to restore the excess K to 2MO, due to transpiration of the phosphate radicals of , and KPo,3 acts to replenish the deficient phosphate radicals.
ＫＴｉＰ○５粉末とフラックスの混合割合は、Ｋ Ｔ
ｉ Ｐ Ｏｓを全体の１５モル％以上、好ましくは２０
モル％以上とするのが望ましい。ＫＴｉＰＯ２粉末の割
合が少な過ぎると単結晶の収率が低く、効率的でないか
らである。The mixing ratio of KTiP○5 powder and flux is KT
i P Os is 15 mol% or more of the total, preferably 20
It is desirable to set it to mol% or more. This is because if the proportion of KTiPO2 powder is too small, the yield of single crystals will be low and it will not be efficient.
Ｋ Ｔ ｉ Ｐ Ｏｓ粉末とフラックスを混合し、ルツ
ボ中で熔融し均熱にした後徐冷すれば、フラックス中に
Ｋ Ｔ ｉ Ｐ Ｏｓ単結晶が析出育成される。この処
理自体は通常のフラックス法による単結晶育成と同様で
ある。When K Ti POs powder and flux are mixed, melted in a crucible, soaked and then slowly cooled, a K Ti POs single crystal is precipitated and grown in the flux. This process itself is similar to single crystal growth using a normal flux method.
Ｋ Ｔ ｉ Ｐ Ｏｓ単結晶の育成を種々に条件を変え
て行った。育成容器には、５０ｍ１白金ルツボと、温度
プログラム設定器付の電気炉を用いた。昇温は何れも１
０℃／時とした。K Ti P Os single crystals were grown under various conditions. A 50 m1 platinum crucible and an electric furnace equipped with a temperature program setting device were used as the growth container. Temperature rise is 1
The temperature was set at 0°C/hour.
育成条件を下記の第１表に示す。The growth conditions are shown in Table 1 below.
」−一上一一及 第１表において停止温度は徐冷を停止した温度である。” - Ichikami In Table 1, the stop temperature is the temperature at which slow cooling was stopped.
この温度でルツボを電気炉から取り出し、放冷後フラッ
クスを温水で溶解し、析出結晶を分解回収した。At this temperature, the crucible was taken out from the electric furnace, and after being left to cool, the flux was dissolved in hot water, and the precipitated crystals were decomposed and recovered.
実験阻１〜３では針状のＫ Ｔ ｉ Ｐ Ｏｓ単結晶が
得られた。これはＫ Ｔ ｉ Ｐ Ｏ、の含有率が低く
、又徐冷停止温度が高過ぎたためと思われる。In Experiments 1 to 3, needle-shaped KTiPOs single crystals were obtained. This is probably because the content of K Ti PO was low and the slow cooling stop temperature was too high.
実験嵐４〜８では何れも透明結晶が得られ、寸法は１０
〜１５璽謳大の粒状であった。Transparent crystals were obtained in all experiments Arashi 4 to 8, and the size was 10.
The particles were about 15 cm in size.
尚、実験１１ｋ１４では黒色板状結晶がルツボ内壁に付
着していたが、実験隘７では黒色結晶の析出は殆んど認
められなかった。In addition, in Experiment 11k14, black plate-like crystals were attached to the inner wall of the crucible, but in Experiment No. 7, almost no black crystal precipitation was observed.
本発明法によれば、Ｋ Ｔ ｉ Ｐ Ｏｓ単結晶をフラ
ックス法により大気圧で育成できるようになり、これに
よってＫ Ｔ ｉ Ｐ Ｏｓ単結晶を低コストで製造し
得るようになった。According to the method of the present invention, it has become possible to grow a K Ti POs single crystal at atmospheric pressure by a flux method, thereby making it possible to manufacture a K Ti POs single crystal at low cost.
Claims (1)
ることにより製造する方法において、フラックスとしＫ
＿２ＭＯ＿４〔ＭはＷ、Ｍｏ、Ｃｒ及びＳから選ばれる
少なくとも一種である〕で表わされる化合物を用いるこ
とを特徴とするリン酸チタン・カリウム単結晶の製造方
法。[Claims] A method for producing a titanium/potassium phosphate single crystal by a flux method, in which K is used as the flux.
A method for producing a titanium/potassium phosphate single crystal, characterized by using a compound represented by _2MO_4 [M is at least one selected from W, Mo, Cr, and S].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18318786A JPS6340799A (en) | 1986-08-04 | 1986-08-04 | Production of titanium phosphate-potassium single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18318786A JPS6340799A (en) | 1986-08-04 | 1986-08-04 | Production of titanium phosphate-potassium single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6340799A true JPS6340799A (en) | 1988-02-22 |
| JPH037639B2 JPH037639B2 (en) | 1991-02-04 |
Family
ID=16131289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18318786A Granted JPS6340799A (en) | 1986-08-04 | 1986-08-04 | Production of titanium phosphate-potassium single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6340799A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997515A (en) * | 1988-12-12 | 1991-03-05 | Hamamatsu Photonics K.K. | Method of synthesizing single-crystal KTiOPO4 |
| US5084206A (en) * | 1990-02-02 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Doped crystalline compositions and a method for preparation thereof |
| EP2489708A1 (en) | 2011-02-16 | 2012-08-22 | Fujifilm Corporation | Inkjet ink composition and method for producing the same, and inkjet recording method |
| US10858527B2 (en) | 2017-07-19 | 2020-12-08 | Ricoh Company, Ltd. | Composition, cured product, image forming apparatus, and image forming method |
-
1986
- 1986-08-04 JP JP18318786A patent/JPS6340799A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997515A (en) * | 1988-12-12 | 1991-03-05 | Hamamatsu Photonics K.K. | Method of synthesizing single-crystal KTiOPO4 |
| US5084206A (en) * | 1990-02-02 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Doped crystalline compositions and a method for preparation thereof |
| EP2489708A1 (en) | 2011-02-16 | 2012-08-22 | Fujifilm Corporation | Inkjet ink composition and method for producing the same, and inkjet recording method |
| US10858527B2 (en) | 2017-07-19 | 2020-12-08 | Ricoh Company, Ltd. | Composition, cured product, image forming apparatus, and image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH037639B2 (en) | 1991-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0004974A2 (en) | Process for producing a single crystal of KTiOPO4 or its analogues | |
| US4305778A (en) | Hydrothermal process for growing a single crystal with an aqueous mineralizer | |
| JPS6340799A (en) | Production of titanium phosphate-potassium single crystal | |
| KR920007942A (en) | Dark blue transparent glass-ceramic products | |
| EP0410581B1 (en) | Process for preparing single crystal of potassium titanium arsonate | |
| EP0022193B1 (en) | Improved process for growing crystal of ktiopo4 and analogues thereof | |
| JPH02157193A (en) | Method for synthesizing ktiopo4 single crystal | |
| US4093502A (en) | Process for synthesizing and growing single crystalline beryl | |
| JP3041326B2 (en) | Method for producing KTiOPO4 single crystal | |
| JPH07507262A (en) | Single cesium titanyl arsenate type crystals and their production | |
| EP0148946B1 (en) | Method of producing a chrysoberyl single crystal | |
| US3431066A (en) | Method for producing yttrium aluminum oxide garnet crystals | |
| CN113668056B (en) | Compound molybdenum zinc potassium phosphate and molybdenum zinc potassium phosphate nonlinear optical crystal, preparation method and application | |
| US3091540A (en) | Garnet gemstones | |
| JPH0764668B2 (en) | Liquid fertilizer manufacturing method | |
| JPH0250080B2 (en) | ||
| JPS63215598A (en) | Production of barium borate single crystal having low temperature phase | |
| JPS6287495A (en) | Production of artificial beryl single crystal | |
| JPH03279298A (en) | Growth of beta-bab2o4 single crystal using nacl as flux | |
| JPH0640800A (en) | Production of potassium titanium phosphate single crystal | |
| JPH04275998A (en) | Production of single crystal | |
| JPH0933964A (en) | Nonlinear optical material and its production | |
| JPS6172638A (en) | Production of calcium phosphate-type crystallized glass | |
| US5102834A (en) | Vanadium garnet materials in the MnO-CaO-V2 O3 -SiO2 system | |
| GB1495800A (en) | Manufacture of monocrystalline gallium arsenide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |