JPH0427200B2 - - Google Patents
Info
- Publication number
- JPH0427200B2 JPH0427200B2 JP28652686A JP28652686A JPH0427200B2 JP H0427200 B2 JPH0427200 B2 JP H0427200B2 JP 28652686 A JP28652686 A JP 28652686A JP 28652686 A JP28652686 A JP 28652686A JP H0427200 B2 JPH0427200 B2 JP H0427200B2
- Authority
- JP
- Japan
- Prior art keywords
- alkali
- hexatitanate
- glass
- whisker
- firing
- 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
Links
- 239000003513 alkali Substances 0.000 claims description 46
- 238000010304 firing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007496 glass forming Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000012779 reinforcing material Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
〔産業上の利用分野〕
本発明は、複合材料の補強材として利用する六
チタン酸カリウムウイスカー、六チタン酸ナトリ
ウムウイスカー、その他六チタン酸アルカリウイ
スカー、およびこれらの混合物の製造方法に関す
る。
ここでウイスカーとは針状結晶であつて、その
アスペクト比が10以上のものをいう。
〔従来の技術〕
近年、技術の高度化は飛躍的に進行して新材料
としての複合材が種々開発されている。軽くて高
強度、高弾性、耐摩耗性等、配合される補強材も
各種多様化されているなかで、チタン酸アルカリ
繊維、特にウイスカー状の繊維が、その物性に着
目されつつある。
チタン酸アルカリでそのまま合成してウイスカ
ー状になるものとしては、二チタン酸アルカリお
よび四チタン酸アルカリが知られている。これま
で六チタン酸アルカリのウイスカーは直接製造す
ることができず、四チタン酸アルカリまたは二チ
タン酸アルカリからアルカリを溶脱して製造され
る。
四チタン酸アルカリウイスカーでも補強材とし
ての効果は発揮できるものの、使用状態でアルカ
リが溶脱しやすいため、水系での使用やアルカリ
が好まない材料への配合ができなかつた。そのた
め、化学的に安定な六チタン酸アルカリウイスカ
ーが有利である。
〔発明が解決しようとする問題点〕
六チタン酸アルカリを直接合成すると、特開昭
53−28100号公報に示されるように温度コントロ
ールを厳密に行うことが必要であり、六チタン酸
アルカリと同時に四チタン酸アルカリや、二チタ
ン酸アルカリも生成されてしまい、完全なものが
得にくかつた。完全なものを得る方法として従
来、特開昭53−26298号公報、特開昭60−34617号
公報、特開昭60−51615号公報に開示された技術
では、繊維状として得られた二チタン酸アルカ
リ、あるいは四チタン酸アルカリを水もしくは希
酸水溶液でアルカリを溶脱し、その組成を六チタ
ン酸アルカリと同程度にした後に、再び数百度の
温度で焼成する方法であるから、水温、スラリー
濃度等で溶脱程度が変わり、組成制御が難しく、
また水洗−乾燥−焼成の三重の工程をとるため、
エネルギコストが高いものであつた。
本発明はこのような三重の工程を経ずに、容易
に六チタン酸アルカリウイスカーを合成する方法
を提供することを目的とする。
〔問題点を解決するための手段〕
本発明は、ウイスカー状に生成された二チタン
酸アルカリあるいは四チタン酸アルカリにガラス
形成酸化物を混合して混合物を作る工程と、この
混合物をそのとき形成されるガラスの溶融する温
度であつて六チタン酸アルカリの溶融温度を越え
ない焼成温度で焼成する工程を備えたことを特徴
とする。
〔作用〕
二チタン酸アルカリあるいは四チタン酸アルカ
リのウイスカーを先行して合成する。ついで六チ
タン酸アルカリとするための余剰のアルカリとし
てガラス形成酸化物を添加混合し、焼成すること
よりアルカリ含有ガラス相を生成させ、ウイスカ
ー本体を六チタン酸アルカリにする。アルカリと
ガラス形成酸化物は高温で非常に結合しやすく、
ウイスカー表面にまぶされたガラス形成酸化物は
加熱により、アルカリを吸収してウイスカー表面
にアルカリ含有ガラスとしてコーテイングされ
る。反応式を代表的なケイ酸の場合で示すと、
６／４R2Ti4O9＋SiO2
→R2Ti6O13＋１／２R2Si2O5
3R2Ti2O5＋4SiO2
→R2Ti6O13＋2R2Si2O5
（Ｒはアルカリ金属）
である。
このときの温度はアルカリ含有ガラスが溶融す
る温度で、かつ六チタン酸アルカリが溶融しない
温度であり、なるべく高く設定する。実用的には
700〜1350℃が好ましい。
ウイスカー表面に生成されたアルカリ含有ガラ
スは補強材として用いる場合に、ウイスカー表面
の硬度が高くなるので剥離する必要はない。しか
し、特にしなやかさ、あるいは吸着性を求める場
合には熱水で洗うことにより、アルカリ−ケイ酸
系ガラス質を剥離することができる。この場合の
溶出液はいわゆる水ガラスとして利用できる。
添加混合するガラス形成酸化部物とは、代表的
なものとして、ケイ酸、ホウ酸、リン酸等であ
り、天然の物質としては、粘土、石英、長石、ホ
ウ砂等がある。また工業製品では石英、非晶質シ
リカ、ガラス屑等を使える。また添加する時点は
焼成途中でもよく、あるいあ一旦炉外に出して混
合して、再度焼成してもよい。エネルギーコスト
を考慮すれば焼成途中あるいは加熱中の700〜
1350℃で混合することが効率的である。
また、本本来ウイスカーは補強材に使われるも
のであるから、ガラス形成酸化物を混合して成形
し、内部に六チタン酸アルカリを充填したガラス
焼結体を直接製造することも可能とするものであ
る。
〔実施例〕
実施例 (1)
粉末状に焼成して得られた長さ80μｍの二チタ
ン酸カリウムあるいは四チタン酸カリウムのウイ
スカーと石英粉末あるいは酸化ホウ素を常温でヘ
ンシエルミキサーで１分間混合し、これを1100℃
で30分焼成した。その結果を表に示す。いずれも
ウイスカー表面がケイ酸カリウムガラスあるいは
ホウ酸カリウムガラスで覆われた六チタン酸カリ
ウムウイスカーを得た。
図にこの生成物の顕微鏡観察スケツチを示す。
[Industrial Application Field] The present invention relates to a method for producing potassium hexatitanate whiskers, sodium hexatitanate whiskers, other alkali hexatitanate whiskers, and mixtures thereof, which are used as reinforcing materials for composite materials. The whisker herein refers to a needle-shaped crystal with an aspect ratio of 10 or more. [Prior Art] In recent years, technological sophistication has progressed dramatically, and various composite materials have been developed as new materials. Amid diversification of reinforcing materials that are light, high strength, high elasticity, abrasion resistance, etc., alkali titanate fibers, especially whisker-like fibers, are attracting attention for their physical properties. Alkali dititanate and alkali tetratitanate are known as substances that can be synthesized directly into a whisker form using alkali titanate. Until now, it has not been possible to directly produce whiskers of alkali hexatitanate, but they are produced by leaching alkali from alkali tetratitanate or alkali dititanate. Alkaline tetratitanate whiskers can also be effective as a reinforcing material, but because alkali easily leaches out during use, they cannot be used in water systems or incorporated into materials that do not like alkalis. Therefore, chemically stable hexatitanate alkali whiskers are advantageous. [Problems to be solved by the invention] Direct synthesis of alkali hexatitanate
As shown in Publication No. 53-28100, it is necessary to strictly control the temperature, and alkali tetratitanate and alkali dititanate are also produced at the same time as alkali hexatitanate, making it difficult to obtain a complete product. It was boring. As a method for obtaining a complete product, the techniques disclosed in JP-A-53-26298, JP-A-60-34617, and JP-A-60-51615 have been used to obtain dititanium in the form of fibers. This method involves leaching the alkali of acid alkali or alkali tetratitanate with water or a dilute acid aqueous solution, making the composition similar to that of alkali hexatitanate, and then firing it again at a temperature of several hundred degrees. The degree of leaching changes depending on the concentration etc., making it difficult to control the composition.
In addition, because it takes a triple process of washing, drying, and firing,
Energy costs were high. An object of the present invention is to provide a method for easily synthesizing hexatitanate alkali whiskers without going through such triple steps. [Means for Solving the Problems] The present invention comprises a step of mixing a glass-forming oxide with a whisker-shaped alkali dititanate or alkali tetratitanate to form a mixture; The method is characterized by comprising a step of firing at a firing temperature that is the melting temperature of the glass to be used and does not exceed the melting temperature of the alkali hexatitanate. [Operation] Whiskers of alkali dititanate or alkali tetratitanate are synthesized in advance. Next, a glass-forming oxide is added and mixed as a surplus alkali to form an alkali hexatitanate, and an alkali-containing glass phase is generated by firing, thereby converting the whisker body into an alkali hexatitanate. Alkali and glass-forming oxides combine very easily at high temperatures;
The glass-forming oxide sprinkled on the whisker surface absorbs alkali by heating and is coated on the whisker surface as an alkali-containing glass. The reaction formula is shown in the case of a typical silicic acid: 6/4R 2 Ti 4 O 9 +SiO 2 →R 2 Ti 6 O 13 +1/2R 2 Si 2 O 5 3R 2 Ti 2 O 5 +4SiO 2 →R 2 Ti 6 O 13 +2R 2 Si 2 O 5 (R is an alkali metal). The temperature at this time is a temperature at which the alkali-containing glass melts and at which the alkali hexatitanate does not melt, and is set as high as possible. Practically speaking
700-1350°C is preferred. When the alkali-containing glass formed on the whisker surface is used as a reinforcing material, it is not necessary to peel it off because the whisker surface becomes hard. However, when particularly pliability or adsorption properties are desired, the alkali-silicate glass can be removed by washing with hot water. The eluate in this case can be used as so-called water glass. Typical glass-forming oxidized parts to be added and mixed are silicic acid, boric acid, phosphoric acid, etc., and natural substances include clay, quartz, feldspar, borax, etc. In addition, quartz, amorphous silica, glass scraps, etc. can be used for industrial products. Further, the addition may be done during the firing, or it may be taken out of the furnace, mixed, and fired again. Considering the energy cost, 700 ~ during firing or heating
Mixing at 1350°C is efficient. In addition, since whiskers are originally used as reinforcing materials, it is also possible to directly manufacture glass sintered bodies filled with alkali hexatitanate by mixing and molding glass-forming oxides. It is. [Example] Example (1) Whiskers of potassium dititanate or potassium tetratitanate with a length of 80 μm obtained by firing into powder and quartz powder or boron oxide were mixed for 1 minute in a Henschel mixer at room temperature. , this at 1100℃
Bake for 30 minutes. The results are shown in the table. In each case, potassium hexatitanate whiskers whose surfaces were covered with potassium silicate glass or potassium borate glass were obtained. The figure shows a microscopic observation sketch of this product.
以上説明したように、本発明によれば六チタン
酸アルカリウイスカーを簡単な工程で製造するこ
とができるから、工業的な利用価値が著しく向上
し、特に、混合物を作る工程を焼成中に行う場合
には、エネルギーの利用効率が高くなる。
また、ガラス質で表面が覆われた六チタン酸ア
ルカリウイスカーは、本発明の製造方法による生
成物であり、これをこのままの形態でガラス質と
調和する各種の機械部材、建築用材、電気材料、
その他物質の補強材として利用するときにきわめ
て有用である。
As explained above, according to the present invention, hexatitanate alkali whiskers can be produced in a simple process, so the industrial value is significantly improved, especially when the process of making the mixture is performed during firing. The efficiency of energy use increases. In addition, the hexatitanate alkali whisker whose surface is covered with glass is a product produced by the manufacturing method of the present invention, and it can be used in its original form to be used in various mechanical parts, construction materials, electrical materials, etc. that harmonize with glass.
It is extremely useful when used as a reinforcing material for other materials.
図は本発明実施例六チタン酸アルカリウイスカ
ーの顕微鏡観察スケツチ。
The figure is a microscopic observation sketch of an alkali hexatitanate whisker according to an example of the present invention.
Claims (1)
リあるいは四チタン酸アルカリにガラス形成酸化
物を混合して混合物を作る工程と、 この混合物をガラス相が溶融する温度であつて
六チタン酸アルカリの溶融温度を越えない焼成温
度で焼成する工程と を含む六チタン酸アルカリウイスカーの製造方
法。 ２ 混合物を作る工程は、常温で行う特許請求の
範囲第１項に記載の六チタン酸アルカリウイスカ
ーの製造方法。 ３ 混合物を得る工程は、焼成温度以下の加熱状
態で行う特許請求の範囲第１項に記載の六チタン
酸アルカリウイスカーの製造方法。 ４ 焼成温度は700〜1350℃の範囲に選ばれる特
許請求の範囲第１項に記載の六チタン酸アルカリ
ウイスカーの製造方法。[Scope of Claims] 1. A step of preparing a mixture by mixing a glass-forming oxide with an alkali dititanate or alkali tetratitanate produced in the form of a whisker; A method for producing an alkali hexatitanate whisker, comprising a step of firing at a firing temperature that does not exceed the melting temperature of the alkali titanate. 2. The method for producing an alkali hexatitanate whisker according to claim 1, wherein the step of preparing the mixture is carried out at room temperature. 3. The method for producing an alkali hexatitanate whisker according to claim 1, wherein the step of obtaining the mixture is performed in a heated state below the calcination temperature. 4. The method for producing an alkali hexatitanate whisker according to claim 1, wherein the firing temperature is selected in the range of 700 to 1350°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28652686A JPS63139099A (en) | 1986-12-01 | 1986-12-01 | Alkali hexatitanate whisker and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28652686A JPS63139099A (en) | 1986-12-01 | 1986-12-01 | Alkali hexatitanate whisker and its production |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3293277A Division JP2532012B2 (en) | 1991-11-08 | 1991-11-08 | Alkali hexatitanate whisker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63139099A JPS63139099A (en) | 1988-06-10 |
| JPH0427200B2 true JPH0427200B2 (en) | 1992-05-11 |
Family
ID=17705552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28652686A Granted JPS63139099A (en) | 1986-12-01 | 1986-12-01 | Alkali hexatitanate whisker and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63139099A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07106908B2 (en) * | 1988-10-12 | 1995-11-15 | チタン工業株式会社 | Potassium titanate fiber and thermoplastic resin composition containing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5627477A (en) * | 1979-08-10 | 1981-03-17 | Canon Inc | Original reader |
| JPS5636155A (en) * | 1979-08-31 | 1981-04-09 | Nec Corp | Logical circuit |
-
1986
- 1986-12-01 JP JP28652686A patent/JPS63139099A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63139099A (en) | 1988-06-10 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |