JPH0643249B2 - Method for producing metal boride fiber - Google Patents
Method for producing metal boride fiberInfo
- Publication number
- JPH0643249B2 JPH0643249B2 JP21058088A JP21058088A JPH0643249B2 JP H0643249 B2 JPH0643249 B2 JP H0643249B2 JP 21058088 A JP21058088 A JP 21058088A JP 21058088 A JP21058088 A JP 21058088A JP H0643249 B2 JPH0643249 B2 JP H0643249B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- metal boride
- fiber
- catalyst
- producing
- 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 - Lifetime
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- Catalysts (AREA)
- Chemical Vapour Deposition (AREA)
- Inorganic Fibers (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は金属ほう化物繊維の製造法に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing metal boride fibers.
金属ほう化物繊維は、耐熱高強度材料、繊維分散強化耐
熱材料用繊維、導電材料として有用なものである。Metal boride fibers are useful as heat-resistant and high-strength materials, fibers for fiber dispersion-strengthened heat-resistant materials, and conductive materials.
従来技術 本出願人はさきに化学気相反応法による金属ほう化物繊
維の製造法において、触媒としてPt、Cu、Au及びPtから
選ばれた金属を用いる方法を発明した。（特願昭62-232
368号） この方法は例えば、ほう化チタン繊維を製造する場合、
気化し得るほう素化合物（例えば、ハロゲン化ほう素、
ジボラン、トリメチルボラン）と気化し得るチタン化合
物（例えば、ハロゲン化チタン、チタンカルボニル、チ
タンのメチル化合物、チタンアルコキシド）との気化ガ
スを水素ガスあるいはアルゴンガスで希釈し、600〜120
0℃に加熱した触媒を保持した反応管に通ずることによ
って製造する方法である。Prior Art The present applicant has previously invented a method of using a metal selected from Pt, Cu, Au and Pt as a catalyst in a method for producing a metal boride fiber by a chemical vapor reaction method. (Japanese Patent Application Sho 62-232
No. 368) This method, for example, when producing titanium boride fiber,
Boron compounds that can be vaporized (for example, boron halides,
Diborane, trimethylborane) and a vaporizable titanium compound (for example, titanium halide, titanium carbonyl, titanium methyl compound, titanium alkoxide) are diluted with hydrogen gas or argon gas to obtain 600 to 120
In this method, the catalyst heated to 0 ° C is passed through a reaction tube holding the catalyst.
しかし、この方法によると、使用触媒がPt、Cu、Au及び
Ptから選ばれたものであるから、これらの金属は微粉化
が困難である。そのため、これらの金属を耐熱耐蝕性の
板、例えばグラファイト板等の板上に真空蒸着法、スパ
ッター法、プラズマＣＶＤ法により微粒子状に付着させ
て用いることが必要であった。従って付着プロセスのた
めの高価な設備を必要とするばかりでなく、その処理も
煩雑であるため、コスト高となる欠点があった。また得
られる繊維も約１時間の反応で十数μｍ程度の長さであ
り、その数も少なく基板上にまばらに育成される程度で
あり、生産性が悪いという問題点があった。However, according to this method, the catalyst used is Pt, Cu, Au and
These metals are difficult to be pulverized because they are selected from Pt. Therefore, it has been necessary to adhere these metals to a heat and corrosion resistant plate such as a graphite plate in the form of fine particles by a vacuum deposition method, a sputtering method or a plasma CVD method. Therefore, there is a drawback that not only expensive equipment for the attachment process is required, but also the treatment is complicated, resulting in high cost. Further, the obtained fibers have a length of about a dozen μm or so in a reaction for about 1 hour, and the number thereof is small and they are sparsely grown on a substrate, which causes a problem of poor productivity.
発明の目的 本発明は前記方法における欠点及び問題点を解消しよう
とするもので、その目的は、触媒付着のための高価な設
備を必要とせず、簡便に長繊維のものも容易に、かつ高
効率で金属ほう化物繊維を製造する方法を提供するにあ
る。OBJECT OF THE INVENTION The present invention is intended to solve the drawbacks and problems in the above-mentioned method, and the object thereof is not to require expensive equipment for catalyst adhesion, and to easily and easily produce long fibers. An object is to provide a method for efficiently producing a metal boride fiber.
発明の構成 本発明者らは前記目的を達成すべく鋭意研究の結果、化
学気相反応による金属ほう化物繊維の製造法における触
媒として、Ni、Pd及びPtから選ばれた金属と得ようとす
る金属ほう化物の成分元素との二元あるいは三元合金を
用いると、これらの合金は微粉末とすることが容易で、
微粉末状で使用することが可能となり、これらの微粉末
状物を基板上あるいは容器中に置いたり、あるいは反応
雰囲気中に供給することにより効率よく、かつ長繊維の
ものも容易に得られる新知見を得た。この知見に基づい
て本発明を完成した。As a result of intensive research to achieve the above object, the present inventors intend to obtain a metal selected from Ni, Pd and Pt as a catalyst in the method for producing a metal boride fiber by a chemical vapor phase reaction. If binary or ternary alloys with metal boride constituent elements are used, these alloys can be easily made into fine powder,
It can be used in the form of fine powder, and by placing these fine powders on a substrate or in a container or supplying them to the reaction atmosphere, it is possible to obtain efficiently and easily long fibers. I got the knowledge. The present invention has been completed based on this finding.
本発明の要旨は、 １）化学気相反応法による金属ほう化物繊維の製造法に
おいてNi、Pd及びPtから選ばれた金属と得ようとする金
属ほう化物の成分元素との二元あるいは三元合金を触媒
として用いることを特徴とする金属ほう化物繊維の製造
法にある。The gist of the present invention is as follows: 1) Binary or ternary of a metal selected from Ni, Pd and Pt and a component element of the metal boride to be obtained in the method for producing a metal boride fiber by the chemical vapor reaction method. It is a method for producing a metal boride fiber characterized by using an alloy as a catalyst.
前記二元あるいは三元合金としては、Ni-B、Pd-B、Pt-
B、Ni-Ti、Pd-Ti、Ni-Ti-B、Pd-Ti-B、Pt-Ti-B、等が挙
げられる。As the binary or ternary alloy, Ni-B, Pd-B, Pt-
B, Ni-Ti, Pd-Ti, Ni-Ti-B, Pd-Ti-B, Pt-Ti-B and the like can be mentioned.
これらの合金の組成は合金塊が機械的にもろく、砕けや
すい性質をもち、粉砕法、研削法により容易に微粉末に
し得られる割合であることが好ましい。Ni-B合金は30〜
90原子％Ni-B、好ましくは50原子％Ni-B、Pd-B合金は３
〜90原子％Pb-B、好ましくは70原子％Pd-B、Pt-B合金は
20〜80原子％Pt-B、好ましくは60原子％Pt-B、Ni-Ti合
金は13〜92原子％Ni-Ti、好ましくは25原子％Ni-Ti、Pd
-Ti合金は10〜70原子％Pd-Ti、好ましくは33原子％Pb-T
i、Pt-Ti合金は10〜40原子％Pt-Ti、好ましくは16原子
％Pt-Ti、である。The composition of these alloys is preferably such that the alloy lumps are mechanically fragile and fragile, and can be easily made into fine powder by a grinding method or a grinding method. 30 for Ni-B alloy
90 atomic% Ni-B, preferably 50 atomic% Ni-B, Pd-B alloy 3
~ 90 atomic% Pb-B, preferably 70 atomic% Pd-B, Pt-B alloy
20-80 atomic% Pt-B, preferably 60 atomic% Pt-B, Ni-Ti alloy 13-92 atomic% Ni-Ti, preferably 25 atomic% Ni-Ti, Pd
-Ti alloy is 10-70 at% Pd-Ti, preferably 33 at% Pb-T
The i, Pt-Ti alloy is 10-40 atomic% Pt-Ti, preferably 16 atomic% Pt-Ti.
Ni-Ti-B、Pd-Ti-B、Pt-Ti-B等の三元合金は、前記の二
元合金を混合することにより得られる組成範囲のもので
あることが好ましい。The ternary alloy such as Ni-Ti-B, Pd-Ti-B, and Pt-Ti-B preferably has a composition range obtained by mixing the above binary alloys.
これらの合金は機械的にもろく、砕け易い性質を持つの
で、これを微粒子状、あるいは超微粒子状とし、反応管
中に設置した基板上または容器内に置くか、あるいは反
応ガスまたはキャリアーガスとともに、エアロゾルにし
て反応管内に供給してもよい。Since these alloys are mechanically fragile and have the property of being easily crushed, they are made into fine particles or ultrafine particles, and placed on a substrate or a container installed in a reaction tube, or together with a reaction gas or a carrier gas, It may be aerosolized and supplied into the reaction tube.
本発明の化学気相反応による金属ほう化物繊維の製法
は、前記したように、原料としての気化し得るほう素化
合物と気化し得る金属化合物との混合蒸気を、500〜140
0℃の温度、望ましくは1000℃の温度に加熱した反応管
に導き、反応管中の触媒により反応させることによって
得られる。この場合、両原料ガスはH2ガス、Heガス、Ar
ガス等で希釈して使用することが好ましい。The method for producing a metal boride fiber by the chemical vapor reaction of the present invention is, as described above, a mixed vapor of a vaporizable boron compound and a vaporizable metal compound as a raw material, 500 to 140.
It is obtained by introducing into a reaction tube heated to a temperature of 0 ° C., preferably 1000 ° C., and reacting with a catalyst in the reaction tube. In this case, both source gases are H 2 gas, He gas, Ar
It is preferable to use it after diluting it with a gas or the like.
本発明の方法によるTiB2繊維を製造する例を以下に挙げ
る。An example of producing TiB 2 fibers by the method of the present invention is given below.
実施例１． Ni、Ti及びＢの各粉末を石英管に真空封入し、1000℃で
２４時間加熱して24.5原子％Ni-TiB2の三元合金を作成
した。これを乳鉢により粉砕して粒径1000Å〜数μｍの
範囲に分散した微粒子とした。この微粒子触媒をグラフ
ァイト板上にふりかけ、これを透明石英製管状反応管内
に設置し、加熱炉により1000℃に加熱した。一方化学気
相反応の原料として、室温において液状のTiCl4及びBBr
3を用い、それぞれを蒸発器に入れ０℃に保持し、それ
ぞれ６０cc／分及び４０cc／分のH2ガスを通じて飽和し
たガスを生成し、これを１００cc／分のH2ガスで希釈し
て反応管内に導入した。反応時の全圧は大気圧で行っ
た。Example 1. Each powder of Ni, Ti and B was vacuum sealed in a quartz tube and heated at 1000 ° C. for 24 hours to prepare a ternary alloy of 24.5 atomic% Ni—TiB 2 . This was crushed in a mortar to obtain fine particles dispersed in a particle size range of 1000Å to several μm. The fine particle catalyst was sprinkled on a graphite plate, placed in a transparent quartz tubular reaction tube, and heated to 1000 ° C. in a heating furnace. On the other hand, as raw materials for the chemical vapor reaction, TiCl 4 and BBr, which are liquid at room temperature, are used.
3 , each was placed in an evaporator and kept at 0 ° C., and saturated gas was produced through H 2 gas of 60 cc / min and 40 cc / min, respectively, and diluted with 100 cc / min of H 2 gas to react. It was introduced into the pipe. The total pressure during the reaction was atmospheric pressure.
この条件で５０分間反応させた結果、グラファイト板上
に直径数百オングストロームから数ミクロンの長さ１〜
２mmのTiB2繊維が得られた。触媒を約１mg用いたとき、
得られる繊維の全量は約３００mgであった。As a result of reacting for 50 minutes under these conditions, a length of several hundred angstroms to several microns on a graphite plate having a diameter of 1 to 1
2 mm of TiB 2 fiber was obtained. When using about 1 mg of catalyst,
The total amount of fibers obtained was about 300 mg.
実施例２． 実施例1.と同様な方法により24.5原子％Ni-Ti合金から
なる微粒子触媒を作成し、これを用いて実施例1.と同様
な方法でTiB2繊維を製造した。その結果、実施例1.と同
様なTiB2繊維が得られた。Example 2. A fine particle catalyst made of a 24.5 atomic% Ni—Ti alloy was prepared by the same method as in Example 1. Using this, a TiB 2 fiber was produced by the same method as in Example 1. As a result, TiB 2 fibers similar to those of Example 1 were obtained.
実施例３． 50原子％Ni-B合金の微粒子触媒を用い、合成温度を800
℃とした以外は実施例1.と同様な方法でTiB2繊維を製造
した。この場合は菱面体構造を持つＢ繊維が混在した。Example 3. A synthesis temperature of 800 using a 50 atom% Ni-B alloy fine particle catalyst.
TiB 2 fibers were produced in the same manner as in Example 1 except that the temperature was changed to ° C. In this case, B fibers having a rhombohedral structure were mixed.
実施例4. 33原子％Pd-TiB2合金、33原子％Pd-Ti合金、70原子％Pd
-B合金の微粒子触媒をそれぞれ用いて実施例1.と同様な
方法でTiB繊維を製造した。得られた繊維の直径は数百
オングストロームと一様に細いものであった。Example 4. 33 atom% Pd-TiB 2 alloy, 33 atom% Pd-Ti alloy, 70 atom% Pd
A TiB fiber was produced in the same manner as in Example 1 using each of the -B alloy fine particle catalysts. The diameter of the obtained fiber was several hundred angstroms, which was uniformly thin.
実施例５． 16原子％Pt-TiB2合金、16原子％Pt-Ti合金、70原子％Pt
-B合金の微粒子触媒をそれぞれ用いて実施例1.と同様な
方法でTiB2繊維が得られた。Example 5. 16 atom% Pt-TiB 2 alloy, 16 atom% Pt-Ti alloy, 70 atom% Pt
TiB 2 fibers were obtained in the same manner as in Example 1 by using the -B alloy fine particle catalysts.
発明の効果 本発明の方法によると、触媒は粉砕により容易に微粒子
とすることができ、これを触媒支持基板上または容器内
に置くか、あるいは反応ガスまたはキャリアーガスとエ
アロゾルとして反応管内に供給することにより使用する
ことができる。従って、従来のように触媒を真空蒸着法
スパッター法、プラズマＣＶＤ法により基板上に付着さ
せることを必要としない。そのため高価な付着設備を必
要とせず、また煩雑な操作も必要としなく、コストを低
下し得られる。更に同時間で、従来法の数10μｍの長さ
より長い約１mmの長さでかつ繊度のそろったものが容易
に得られ、その収量も多くなる効果を有する。EFFECTS OF THE INVENTION According to the method of the present invention, the catalyst can be easily made into fine particles by pulverization, and the fine particles are placed on the catalyst supporting substrate or in the container, or supplied into the reaction tube as a reaction gas or carrier gas and an aerosol. It can be used by Therefore, it is not necessary to deposit the catalyst on the substrate by the vacuum vapor deposition method, the sputtering method, or the plasma CVD method as in the conventional case. Therefore, expensive adhesion equipment is not required and complicated operations are not required, and the cost can be reduced. Further, at the same time, a product having a length of about 1 mm, which is longer than the length of several tens of μm in the conventional method, and having a uniform fineness can be easily obtained, and the yield thereof can be increased.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０１Ｆ 9/08 Ｚ 7199−3Ｂ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location D01F 9/08 Z 7199-3B
Claims (2)
製造法においてNi、Pd及びPtから選ばれた金属と得よう
とする金属ほう化物の成分元素との二元あるいは三元合
金を触媒として用いることを特徴とする金属ほう化物繊
維の製造法。1. A catalyst for a binary or ternary alloy of a metal selected from Ni, Pd and Pt and a component element of a metal boride to be obtained in a method for producing a metal boride fiber by a chemical vapor reaction method. A method for producing a metal boride fiber, which is used as
製造法。2. The method according to claim 1, wherein the alloy catalyst is in the form of fine powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21058088A JPH0643249B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing metal boride fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21058088A JPH0643249B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing metal boride fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0259419A JPH0259419A (en) | 1990-02-28 |
| JPH0643249B2 true JPH0643249B2 (en) | 1994-06-08 |
Family
ID=16591667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21058088A Expired - Lifetime JPH0643249B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing metal boride fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643249B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4914977B2 (en) * | 2008-08-20 | 2012-04-11 | 和子 井川 | Tennis racket strike identification counter |
| JP2014046087A (en) | 2012-09-03 | 2014-03-17 | Seiko Instruments Inc | Electronic equipment and program |
| US10422809B2 (en) | 2012-09-03 | 2019-09-24 | Seiko Instruments Inc. | Electronic apparatus and program |
-
1988
- 1988-08-26 JP JP21058088A patent/JPH0643249B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259419A (en) | 1990-02-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |