JPH0637304B2 - Method for producing molybdenum disulfide fine particles - Google Patents
Method for producing molybdenum disulfide fine particlesInfo
- Publication number
- JPH0637304B2 JPH0637304B2 JP7751889A JP7751889A JPH0637304B2 JP H0637304 B2 JPH0637304 B2 JP H0637304B2 JP 7751889 A JP7751889 A JP 7751889A JP 7751889 A JP7751889 A JP 7751889A JP H0637304 B2 JPH0637304 B2 JP H0637304B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- laser
- gas
- molybdenum disulfide
- mos
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、レーザーによる二硫化モリブデン（MoS2）微
粒子の製造に関し、詳しくは、ガスブレークダウンを利
用したレーザーによる二硫化モリブデン微粒子の製造法
に関する。TECHNICAL FIELD The present invention relates to the production of molybdenum disulfide (MoS 2 ) fine particles by laser, and more specifically, a method for producing fine molybdenum disulfide fine particles by laser using gas breakdown. Regarding
（従来の技術） 一般に種々の材料となる物質は、原子の数が無限個の集
合体であり、その物質の大きさが極端に小さくなると、
特異な性質を示すようになる。物質の粒径が１μｍ（原
子数にして１０10個）以下のものは微粒子と呼ばれ、焼
結原料、触媒、生物工学等の種々の用途に用いられる新
素材として関心が持たれている。この場合、用いられる
微粒子に望ましい条件は、化学的純度が高いこと、球状
でありその粒径が小さいこと、粒径が均一であること等
である。このような微粒子の製造法としては、固相反応
法、液相反応法、気相反応法等があるが、上記の条件に
適合した微粒子の製造法としては気相反応法が最適であ
る。(Prior Art) In general, substances that are various materials are aggregates with an infinite number of atoms, and when the size of the substance becomes extremely small,
It shows unique properties. Particles having a particle diameter of 1 μm or less (10 10 in terms of the number of atoms) are called fine particles, and are attracting attention as new materials used for various purposes such as sintering raw materials, catalysts and biotechnology. In this case, desirable conditions for the fine particles to be used are that the chemical purity is high, that the particles are spherical and have a small particle size, and that the particle size is uniform. As a method for producing such fine particles, there are a solid-phase reaction method, a liquid-phase reaction method, a gas-phase reaction method and the like, and a gas-phase reaction method is most suitable as a method for producing fine particles which meet the above conditions.
他方、レーザー技術に関する進歩は目覚ましく、広い波
長領域で強力な光を発振するレーザーが開発されてい
る。とりわけ、典型的な赤外レーザーである炭酸ガスレ
ーザーは、その高効率、高出力のため、種々の用途が考
えられている。例えば、パルス発振ＴＥＡ−ＣＯ２レー
ザーの赤外多光子解離による同位体分離や連続発振CO2
レーザーの熱反応による微粒子製造等が研究されてお
り、すでに、第４図に示すような気相反応法とレーザー
誘起反応とを組合わせた微粒子生成法（セラミックス：
１９（１９８４）、No.６、ｐ４８２）が報告されてい
る。これは、反応ガスをCO2レーザーで加熱して、以下
に示す反応によって、Si、SiC、Si3N4の超微粒子を生成
するものである。On the other hand, progress in laser technology has been remarkable, and lasers that emit strong light in a wide wavelength range have been developed. In particular, carbon dioxide gas laser, which is a typical infrared laser, has been considered for various applications because of its high efficiency and high output. For example, isotope separation by infrared multiphoton dissociation of a pulse oscillation TEA-CO 2 laser or continuous oscillation CO 2
The production of fine particles by the thermal reaction of a laser has been studied, and a fine particle production method (ceramics: a combination of a gas phase reaction method and a laser-induced reaction as shown in FIG. 4) has already been conducted.
19 (1984), No. 6, p482). In this method, a reaction gas is heated by a CO 2 laser to generate ultrafine particles of Si, SiC, and Si 3 N 4 by the following reaction.
SiH4(g)→Si(s)＋2H2(g) 2SiH4(g)＋C2H4(g)→2SiC(s)＋6H2(g) 3SiH4(g)＋4NH3(g)→Si3N4(g)＋12H2(g) （発明が解決しようとする課題） 本発明者等は、レーザー応用技術を研究した過程で、前
述のCO2レーザーの熱反応法に代わって、気体の誘電破
壊（ガスブレークダウン）、すなわち、パルス発振レー
ザーを気体に照射するとレーザー光の時間的、空間的な
高輝度のために生じる現象を利用して、微粒子を生成す
ることができることを見い出した。このブレークダウン
を利用すると、原料気体にレーザーを照射して種々の反
応を誘起させ粒径の非常に小さい固体生成物を製造する
ことができる。この方法の特長は次のようなものであ
る。(1)照射光の波長領域に吸収帯を有しない物質も原
料として用いることができる。(2)光の吸収効率がよ
い。(3)操作圧が高く、反応は連鎖的なので収量が多
い。(4)器壁からの不純物の混入がない。(5)常温の反応
容器で高融点物質が得られる。(6)粒径分布が狭い微粒
子が得られる。(7)反応装置が単独で容易に行うことが
できる。本発明は、上記のような特長を有するレーザー
によるブレークダウンを利用したMoS2の微粒子を製造す
る方法を提供することを目的とする。SiH 4 (g) → Si (s) ＋ 2H 2 (g) 2SiH 4 (g) ＋ C 2 H 4 (g) → 2SiC (s) ＋ 6H 2 (g) 3SiH 4 (g) ＋ 4NH 3 (g) → Si 3 N 4 (g) + 12H 2 (g) (Problems to be solved by the invention) In the process of researching laser application technology, the present inventors have replaced the thermal reaction method of CO 2 laser described above with a dielectric of gas. It has been found that fine particles can be generated by utilizing the phenomenon of destruction (gas breakdown), that is, when a pulsed laser is applied to a gas, due to high temporal and spatial brightness of laser light. By utilizing this breakdown, it is possible to produce a solid product having a very small particle size by irradiating the raw material gas with a laser to induce various reactions. The features of this method are as follows. (1) A substance having no absorption band in the wavelength region of irradiation light can also be used as a raw material. (2) High light absorption efficiency. (3) The operating pressure is high and the reaction is chained, so the yield is high. (4) No impurities are mixed in from the vessel wall. (5) A high melting point substance can be obtained in a reaction vessel at room temperature. (6) Fine particles having a narrow particle size distribution can be obtained. (7) The reactor alone can be easily operated. It is an object of the present invention to provide a method for producing MoS 2 fine particles using the breakdown by a laser having the above characteristics.
（課題を解決するための手段） モリブデンカルボニル〔Mo(CO)6〕二硫化炭素（CS2）又
は硫化水素（H2S）を含む混合ガスにレーザー光を照射
して、ガスブレークダウン現象により二硫化モリブデン
（MoS2）の微粒子を生成することを特徴とする。(Means for Solving the Problems) By irradiating a mixed gas containing molybdenum carbonyl [Mo (CO) 6 ] carbon disulfide (CS 2 ) or hydrogen sulfide (H 2 S) with laser light, a gas breakdown phenomenon occurs. It is characterized by producing fine particles of molybdenum disulfide (MoS 2 ).
照射すべきレーザー光としてはパルス発振CO2レーザー
光を使用することができる。Pulsed CO 2 laser light can be used as the laser light to be irradiated.
（作 用） 以下本発明を詳しく説明する。(Operation) The present invention will be described in detail below.
粒径の揃った特性の良い微粒子の製法としては、気体原
料を用いる気相法が適しているが、MoS2の気体の原料と
して、モリブデンカルボニル〔Mo(CO)6〕と二硫化炭素
（CS2）又は硫化水素（H2S）の混合ガスを用いる。この
原料にCO2レーザー光を照射すると、レーザー光の単位
断面積当たりのエネルギー（フルエンス）が小さい場合
には、レーザー光のエネルギーはガスにほとんど吸収さ
れないが、ある程度以上の強さのレーザー光の場合、原
料ガス内でブレークダウンが起こって、照射されたレー
ザーエネルギーのほとんどが吸収される。これは原料ガ
ス分子の光エネルギーによるイオン化およびそれによっ
て生じた電子の光エネルギー吸収に続くイオン化の繰り
返しによって次ぎの反応が引き起こされる。The preparation of good uniform properties particle diameters microparticles, although vapor phase method using a gas material is suitable as a raw material gas of MoS 2, carbon disulfide and molybdenum carbonyl [Mo (CO) 6] (CS 2 ) or a mixed gas of hydrogen sulfide (H 2 S) is used. When this raw material is irradiated with CO 2 laser light, if the energy per unit cross-sectional area of the laser light (fluence) is small, the energy of the laser light is hardly absorbed by the gas, but the In this case, a breakdown occurs in the source gas, and most of the irradiated laser energy is absorbed. This is because the following reaction is caused by the ionization of the source gas molecules by the light energy and the absorption of the resulting light energy by the electrons, followed by the ionization.
Mo(CO6)＋CS2＝MoS2＋6CO＋Ｃ Mo(CO6)＋2H2S＝MoS2＋6CO＋2H2 この場合、照射に使用するレーザーの波長は、原料ガス
の吸収波長に関係なく、できるだけパルスエネルギーの
強い発振波長が良い。上記の反応によって得られるMoS2
は気相で均一核生成と成長によって生成した粒子状のも
ので、原理的に球状で粒径分布が狭く、粒径が０．１μ
ｍ以下の微粒子であり、生成条件の制御により得られる
微粒子の特性を変えることが可能である。Mo (CO 6 ) ＋ CS 2 ＝ MoS 2 ＋ 6CO ＋ C Mo (CO 6 ) ＋ 2H 2 S ＝ MoS 2 ＋ 6CO ＋ 2H 2 In this case, the wavelength of the laser used for irradiation is as strong as possible, regardless of the absorption wavelength of the source gas. Good oscillation wavelength. MoS 2 obtained by the above reaction
Are particles formed by uniform nucleation and growth in the gas phase, and are spherical in principle and have a narrow particle size distribution with a particle size of 0.1 μm.
Since the particles are m or less, the characteristics of the particles can be changed by controlling the production conditions.
実際の微粒子の製造には、回分式又は連続流通式の照射
セルを使用し、生成した微粒子はフィルターやその他の
補集装置で補集することができる。A batch type or continuous flow type irradiation cell is used for the actual production of the fine particles, and the produced fine particles can be collected by a filter or other collecting device.
（発明の効果） このように、本発明によって得られたMoS2微粒子は、粒
径が非常に小さくしかも均一であり、また、固体潤滑剤
として利用できる。現在、MoS2微粒子は粉砕法によって
製造されているが粒径が小さく均一な微粒子が得られに
くい。また、粉砕機からの不純物の混入も避けられな
い。本法では前述のように、生成原理も簡単なものであ
り、現行法よりも著しく有利である。(Effect of the Invention) As described above, the MoS 2 fine particles obtained by the present invention have a very small particle size and are uniform, and can be used as a solid lubricant. Currently, MoS 2 fine particles are manufactured by a pulverization method, but it is difficult to obtain fine particles having a small particle size. In addition, mixing of impurities from the crusher is inevitable. In this method, as described above, the principle of generation is also simple, which is a significant advantage over the current method.
（実施例） 本発明に使用した装置の概略を第１図に示す。CO2レー
ザー１１から発生された適切な波数のパルス状レーザー
光１２が絞り１６を通過した後、BaF2レンズ１３で集光
される。この集光されたレーザー光はKBr 窓１７を通し
て、照射反応容器１４内のMo(CO)6とCS2又はH2Sの混合
気体である試料気体１５を照射される。照射後、残留お
よび生成ガスを排気除去し、不活性ガスで容器内を充た
した後、補集容器１８に光反応により堆積した微粒子が
この容器から取り出される。(Example) An outline of an apparatus used in the present invention is shown in FIG. The pulsed laser light 12 having an appropriate wave number generated from the CO 2 laser 11 passes through the diaphragm 16 and then is condensed by the BaF 2 lens 13. The condensed laser light is irradiated through the KBr window 17 to the sample gas 15 which is a mixed gas of Mo (CO) 6 and CS 2 or H 2 S in the irradiation reaction container 14. After the irradiation, the residual gas and the generated gas are exhausted and removed, the inside of the container is filled with an inert gas, and then the fine particles deposited by the photoreaction in the collection container 18 are taken out from this container.
１２TorrのMo(CO)6と２００TorrのCS2の混合ガスにCO2
レーザーの９．６μｍ帯のＰ（２４）、すなわち１０４
３cm-1のパルス光を照射した、この時のパルスエネルギ
ーは約１Ｊ／pulse 、使用したレンズの焦点距離は７．
５cmである。CO 2 in a mixed gas of 12 Torr Mo (CO) 6 and 200 Torr CS 2.
P (24) of the 9.6 μm band of the laser, that is, 104
Irradiated with pulsed light of 3 cm −1 , the pulse energy at this time is about 1 J / pulse, and the focal length of the lens used is 7.
It is 5 cm.
第２図は生成した微粒子の粒径の分布を走査型電子顕微
鏡写真を用いて測定した結果のグラフである。本法によ
って得られた平均粒径が０．０７μｍの比較的均一な分
布を示すMoS2微粒子であることが確認できた。FIG. 2 is a graph showing the results of measuring the particle size distribution of the generated fine particles using a scanning electron microscope photograph. It was confirmed that the particles were MoS 2 fine particles having a mean particle size of 0.07 μm and a relatively uniform distribution obtained by this method.
また、生成した微粒子のＸ線回折の解析から得られた面
定数と元素分析の結果から、生成微粒子は非晶質のMoS2
であることを確認した。In addition, from the results of the surface constant and the elemental analysis obtained by the X-ray diffraction analysis of the produced fine particles, the produced fine particles are amorphous MoS 2
Was confirmed.
第１図は、本発明の実施例に用いた装置の概略図、 第２図は、本発明の実施例で得られたMo微粒子の粒径分
布を示すグラフ、 第３図は、従来の連続発振CO2レーザーを用いた気相法
による微粒子生成法の反応容器の概略図。 （符号の説明） １１……CO2レーザー、 １２……レーザー光、 １３……BaF2レンズ、 １４……照射反応容器、 １５……試料気体、 １６……絞り、 １７……KBr窓板、 １８……補集容器。FIG. 1 is a schematic view of an apparatus used in the examples of the present invention, FIG. 2 is a graph showing the particle size distribution of Mo fine particles obtained in the examples of the present invention, and FIG. Schematic diagram of a reaction vessel for a fine particle production method by a gas phase method using an oscillating CO 2 laser. (Explanation of symbols) 11 …… CO 2 laser, 12 …… Laser light, 13 …… BaF 2 lens, 14 …… Irradiation reaction vessel, 15 …… Sample gas, 16 …… Aperture, 17 …… KBr window plate, 18 ... Collection container.
Claims (1)
化炭素（CS2）又は硫化水素（H2S）とを含む混合ガスに
レーザー光を照射して二硫化モリブデン（MoS2）の微粒
子を製造する方法。1. A mixed gas containing molybdenum carbonyl [Mo (CO) 6 ] and carbon disulfide (CS 2 ) or hydrogen sulfide (H 2 S) is irradiated with laser light to produce molybdenum disulfide (MoS 2 ). Method for producing fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7751889A JPH0637304B2 (en) | 1989-03-29 | 1989-03-29 | Method for producing molybdenum disulfide fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7751889A JPH0637304B2 (en) | 1989-03-29 | 1989-03-29 | Method for producing molybdenum disulfide fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255537A JPH02255537A (en) | 1990-10-16 |
| JPH0637304B2 true JPH0637304B2 (en) | 1994-05-18 |
Family
ID=13636188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7751889A Expired - Lifetime JPH0637304B2 (en) | 1989-03-29 | 1989-03-29 | Method for producing molybdenum disulfide fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637304B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL133115A0 (en) * | 1999-11-24 | 2001-03-19 | Yeda Res & Dev | Method for micropatterning of surfaces |
-
1989
- 1989-03-29 JP JP7751889A patent/JPH0637304B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02255537A (en) | 1990-10-16 |
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