JPH04254585A - Formation of tungsten carbide film - Google Patents
Formation of tungsten carbide filmInfo
- Publication number
- JPH04254585A JPH04254585A JP3013527A JP1352791A JPH04254585A JP H04254585 A JPH04254585 A JP H04254585A JP 3013527 A JP3013527 A JP 3013527A JP 1352791 A JP1352791 A JP 1352791A JP H04254585 A JPH04254585 A JP H04254585A
- Authority
- JP
- Japan
- Prior art keywords
- tungsten
- film
- tungsten carbide
- hydrogen
- carbide film
- 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.)
- Pending
Links
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title 1
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000009877 rendering Methods 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052759 nickel Inorganic materials 0.000 description 13
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical group Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、機械部品、切削工具等
に耐摩耗性を与え、耐久性の大幅な向上が図れる硬質膜
、特に、このうちでも最も硬度および熱安定性等の物性
に優れているとされているタングステンカーバイト膜の
基材への形成方法に関する。[Industrial Application Field] The present invention is a hard film that imparts wear resistance to mechanical parts, cutting tools, etc. and can significantly improve durability. This invention relates to a method of forming a tungsten carbide film on a base material, which is said to be excellent.
【０００２】0002
【従来の技術】従来より切削工具等への硬質膜の形成方
法としては耐熱性金属、例えば、タングステン、モリブ
デンあるいはチタン等の炭化物膜をプラズマあるいは火
炎溶射により形成する方法が知られている。2. Description of the Related Art Conventionally, as a method of forming a hard film on a cutting tool or the like, a method is known in which a carbide film of a heat-resistant metal such as tungsten, molybdenum or titanium is formed by plasma or flame spraying.
【０００３】これらの方法では基材に稠密に密着させる
ことができず、所期の目的を十分に達成することは困難
であった。これに対して化学蒸着法（ＣＶＤ）によれば
高い密度（ほぼ理論密度）の膜が形成でき、しかも基材
に対する密着性が極めて優れており、種々検討されてい
る。このうち、耐摩耗性等の物性が特に優れているタン
グステンカーバイト膜のＣＶＤによる形成方法について
は、■６フッ化タングステン、水素およびベンゼンのよ
うな炭化水素からなるガス状混合物を４００〜１０００
℃の温度範囲で化学蒸着することにより、ＷＣあるいは
Ｗ２Ｃの形態のタングステンカーバイト膜の形成方法（
英国特許第１３２６７６９ 号）、あるいは、■６塩化
タングステン、水素およびメタンを１０００〜１２００
℃の範囲で化学蒸着させＷＣ膜を得る方法（Ｈ．Ｍａｎ
ｔｌｅら、Ｐｒｏｃｅｄｉｎｇｓ ｏｆ ｔｈｅ ５ｔ
ｈ Ｉｎｔ． Ｃｏｎｆ． ｏｎ ＣＶＤ （１９７５
） Ｐ．５４０ ）、あるいは、■６塩化タングステン
、水素およびベンゼンを９５０〜１４５０℃の範囲で化
学蒸着させＷＣあるいはＷ２Ｃの膜を得る方法（伊藤ら
、Ｊ．Ｃｒｙｓｔａｌ Ｇｒｏｗｔｈ，１２，２６５
（１９７２））等が知られている。[0003] These methods do not allow for dense adhesion to the substrate, making it difficult to sufficiently achieve the intended purpose. On the other hand, chemical vapor deposition (CVD) can form a film with a high density (approximately the theoretical density) and has extremely good adhesion to the substrate, and has been studied in various ways. Among these methods, the CVD method for forming tungsten carbide film, which has particularly excellent physical properties such as wear resistance, is as follows:
A method for forming tungsten carbide films in the form of WC or W2C by chemical vapor deposition in the temperature range of °C (
British Patent No. 1326769), or ■ 6 tungsten chloride, hydrogen and methane at 1000 to 1200
Method of obtaining WC film by chemical vapor deposition in the range of ℃ (H.Man
tle et al., Proceedings of the 5t
h Int. Conf. on CVD (1975
) P. 540), or (2) a method of chemical vapor deposition of tungsten hexachloride, hydrogen, and benzene in the range of 950 to 1450°C to obtain a WC or W2C film (Ito et al., J. Crystal Growth, 12, 265).
(1972)) are known.
【０００４】これらの方法においては、■の場合、これ
らの温度範囲ではＷ２Ｃ膜が主に生成され、ＷＣ膜を得
るためには■、■、■いずれの場合も反応温度を高くす
る必要があるため、基材の金属材料に好ましくない影響
を与え、得られる硬質膜形成金属材料は精密材料等への
使用が制限される等の問題があった。[0004] In these methods, in the case of (1), a W2C film is mainly produced in these temperature ranges, and in order to obtain a WC film, it is necessary to raise the reaction temperature in any of the cases of (2), (2), and (3). Therefore, there were problems such as having an undesirable effect on the metal material of the base material and restricting the use of the obtained hard film-forming metal material for precision materials and the like.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記した
従来法の問題点に鑑み、鋭意検討の結果、４００〜９０
０℃程度の反応温度においても種々の物性に優れたタン
グステンカーバイト膜を容易かつ効率的に基材に形成せ
しめることのできる方法を見いだし本発明に至った。[Means for Solving the Problems] In view of the problems of the conventional method described above, the present inventors have conducted extensive studies and found that the
The inventors have discovered a method that allows a tungsten carbide film with excellent various physical properties to be easily and efficiently formed on a substrate even at a reaction temperature of about 0° C., resulting in the present invention.
【０００６】すなわち本発明は、６フッ化タングステン
、一般式Ｒ３Ｎ（ただし、Ｒは水素またはアルキル基を
示す。）で表されるアミンおよび水素を含有するガスを
、４００〜９００℃の温度範囲において気相反応させる
ことを特徴とするタングステンカーバイトの製造方法、
および上記発明において、特に６フッ化タングステン、
一般式Ｒ３Ｎ（ただし、Ｒは水素またはアルキル基を示
す。）で表されるアミンおよび水素の混合比率をカーボ
ンのタングステンに対する原子比で１〜２０、水素のタ
ングステンに対する原子比で１〜１５の範囲とすること
を特徴とするタングステンカーバイト膜の形成方法を提
供するものである。That is, the present invention aims at treating tungsten hexafluoride, an amine represented by the general formula R3N (where R represents hydrogen or an alkyl group), and a hydrogen-containing gas at a temperature range of 400 to 900°C. A method for producing tungsten carbide characterized by a gas phase reaction,
And in the above invention, especially tungsten hexafluoride,
The mixing ratio of the amine represented by the general formula R3N (where R represents hydrogen or an alkyl group) and hydrogen is in the range of 1 to 20 in terms of the atomic ratio of carbon to tungsten and 1 to 15 in terms of the atomic ratio of hydrogen to tungsten. The present invention provides a method for forming a tungsten carbide film characterized by the following.
【０００７】本発明において用いるカーボン源としての
一般式Ｒ３Ｎ（ただし、Ｒは水素またはアルキル基を示
す。）で表されるアミンとしてはモノメチルアミン、ジ
メチルアミン、トリメチルアミン、モノエチルアミン、
ジエチルアミン、トリエチルアミン等の各種のアミン類
が挙げられるが、蒸気圧が高く供給の容易さ等の理由か
らトリメチルアミンが最も好ましい。これらアルキルア
ミンの使用量は、この分子中のカーボンと原料６フッ化
タングステンのタングステンとの比（Ｃ／Ｗ：原子比）
が１〜２０の範囲となるように選ばれる。アルキルアミ
ンの量がこの範囲よりも小さくなる場合には、タングス
テンカーバイト膜が得られにくく、タングステン（Ｗ）
との混合膜として得られ、タングステンカーバイト膜と
比較して光沢、耐摩耗性等の物性が劣り、好ましくない
。また、この範囲より大きくなっても特に不都合はない
が、原料のアルキルアミンがむだとなるためこの範囲以
下が好ましい。The amines represented by the general formula R3N (wherein R represents hydrogen or an alkyl group) used as a carbon source in the present invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Various amines such as diethylamine and triethylamine can be used, but trimethylamine is most preferred because of its high vapor pressure and ease of supply. The amount of these alkylamines used is determined by the ratio of carbon in this molecule to tungsten in the raw material tungsten hexafluoride (C/W: atomic ratio).
is selected so that it is in the range of 1 to 20. If the amount of alkylamine is smaller than this range, it is difficult to obtain a tungsten carbide film, and tungsten (W)
It is obtained as a mixed film with a tungsten carbide film, and its physical properties such as gloss and abrasion resistance are inferior to that of a tungsten carbide film, making it undesirable. Moreover, although there is no particular disadvantage if the amount is larger than this range, it is preferable that the amount is less than this range because the raw material alkylamine becomes wasteful.
【０００８】本発明においては、水素の量も限定される
ものである。すなわち水素のタングステンに対する比（
Ｈ／Ｗ：原子比）が１〜１５の範囲であることが必要で
あり、これより大きい場合には、タングステンとタング
ステンカーバイトとの混合膜が得られ、好ましくない。
また、この範囲より小さい場合、特に不都合はないが、
タングステンカーバイト膜の析出速度が遅くなり、原料
のアルキルアミンおよび６フッ化タングステンがむだと
なるため、好ましくない。In the present invention, the amount of hydrogen is also limited. That is, the ratio of hydrogen to tungsten (
H/W (atomic ratio) is required to be in the range of 1 to 15; if it is larger than this, a mixed film of tungsten and tungsten carbide will be obtained, which is not preferable. Also, if it is smaller than this range, there is no particular disadvantage, but
This is not preferable because the deposition rate of the tungsten carbide film becomes slow and the raw materials alkylamine and tungsten hexafluoride are wasted.
【０００９】本発明においては、反応温度は４００〜９
００℃の範囲が好ましく、より高温領域においてはタン
グステン膜が生成し、より低温領域においては析出速度
が小さくなる。特に、各種金属基材に適用して硬質膜を
得るようにする場合には、金属材料に対する好ましくな
い影響、すなわち、軟化、歪み等を回避し得る温度範囲
でタングステンカーバイト膜を形成し得る本発明方法は
極めて有益である。特に、その目的から、８００℃以下
が好ましい。In the present invention, the reaction temperature is 400 to 9
A range of 00° C. is preferable; a tungsten film is formed in a higher temperature region, and the precipitation rate becomes lower in a lower temperature region. In particular, when applying to various metal substrates to obtain a hard film, it is possible to form a tungsten carbide film within a temperature range that avoids undesirable effects on the metal material, such as softening and distortion. The invented method is extremely beneficial. In particular, for that purpose, the temperature is preferably 800°C or less.
【００１０】本発明においては、反応圧力は特に限定的
ではないが、大気圧でも十分に反応を行うことができる
ことは大きな特徴である。この場合には反応装置も特殊
なものを採用する必要はなく、操作も簡便となる。また
、窒素、アルゴンなどの不活性ガスを希釈ガスとして添
加しても何ら問題はない。[0010] In the present invention, the reaction pressure is not particularly limited, but a major feature is that the reaction can be carried out satisfactorily even at atmospheric pressure. In this case, there is no need to employ a special reactor, and the operation is simple. Further, there is no problem even if an inert gas such as nitrogen or argon is added as a diluent gas.
【００１１】[0011]
【実施例】以下、本発明を実施例により具体的に説明す
る。
実施例１
内径３．６ｃｍ、全長６０ｃｍ、均一温度領域長１０ｃ
ｍの反応器を具備した横型流通方式のＣＶＤ装置を用い
、原料ガスは反応器の一端の一つのノズルから導入し、
幅１．０ｃｍ、長さ１．５ｃｍ、厚さ０．４ｍｍのニッ
ケル基板を均一温度領域の中央に設置して反応を行った
。以下の実施例、比較例のいずれも同様にして反応を行
った。[Examples] The present invention will be specifically explained below using examples. Example 1 Inner diameter 3.6cm, total length 60cm, uniform temperature area length 10cm
Using a horizontal flow type CVD apparatus equipped with a reactor of
A nickel substrate with a width of 1.0 cm, a length of 1.5 cm, and a thickness of 0.4 mm was placed in the center of a uniform temperature region to conduct a reaction. Reactions were carried out in the same manner in both Examples and Comparative Examples below.
【００１２】６フッ化タングステン、トリメチルアミン
および水素のモル比を１：２：３（Ｃ／Ｗ原子比＝６．
０，Ｈ／Ｗ原子比＝６．０）とした混合ガスを大気圧下
、全流量１２０ｃｃ／ｍｉｎで８００℃に保たれた反応
器に導入し、この反応器に置かれたニッケル基板を３０
分間コーテイングした。ニッケル基板上には、７０μｍ
の膜が得られ、Ｘ線回折パターンからＷＣ膜であること
を確認した。The molar ratio of tungsten hexafluoride, trimethylamine and hydrogen was 1:2:3 (C/W atomic ratio = 6.
0, H/W atomic ratio = 6.0) was introduced into a reactor maintained at 800°C under atmospheric pressure at a total flow rate of 120 cc/min, and the nickel substrate placed in this reactor was
Coated for a minute. 70 μm on the nickel substrate
A film was obtained, and it was confirmed from the X-ray diffraction pattern that it was a WC film.
【００１３】実施例２
６フッ化タングステン、トリメチルアミンおよび水素の
モル比を１：１：１（Ｃ／Ｗ原子比＝３．０，Ｈ／Ｗ原
子比＝２．０）とした混合ガスを大気圧下、全流量１２
０ｃｃ／ｍｉｎで４００℃に保たれた反応器に導入し、
この反応器に置かれたニッケル基板を３０分間コーテイ
ングした。ニッケル基板上には、１０μｍの膜が得られ
、Ｘ線回折パターンからＷ３Ｃ膜であることを確認した
。Example 2 A mixed gas containing tungsten hexafluoride, trimethylamine and hydrogen in a molar ratio of 1:1:1 (C/W atomic ratio = 3.0, H/W atomic ratio = 2.0) was prepared in large quantities. Under atmospheric pressure, total flow rate 12
Introduced into a reactor maintained at 400°C at 0cc/min,
A nickel substrate placed in the reactor was coated for 30 minutes. A 10 μm film was obtained on the nickel substrate, and it was confirmed from the X-ray diffraction pattern that it was a W3C film.
【００１４】実施例３
６フッ化タングステン、トリエチルアミン、水素および
窒素のモル比を１：１：５：５（Ｃ／Ｗ原子比＝６．０
，Ｈ／Ｗ原子比＝１０．０）とした混合ガスを大気圧下
、全流量１２０ｃｃ／ｍｉｎで６００℃に保たれた反応
器に導入し、この反応器に置かれたニッケル基板を３０
分間コーテイングした。ニッケル基板上には、４０μｍ
の膜が得られ、Ｘ線回折パターンからＷ３Ｃ、Ｗ２Ｃ膜
であることを確認した。Example 3 The molar ratio of tungsten hexafluoride, triethylamine, hydrogen and nitrogen was 1:1:5:5 (C/W atomic ratio = 6.0
, H/W atomic ratio = 10.0) was introduced into a reactor maintained at 600°C at a total flow rate of 120 cc/min under atmospheric pressure, and a nickel substrate placed in this reactor was
Coated for a minute. 40 μm on the nickel substrate
A film was obtained, and it was confirmed from the X-ray diffraction pattern that it was a W3C or W2C film.
【００１５】比較例１
６フッ化タングステン、ベンゼンおよび水素のモル比を
１：１：３（Ｃ／Ｗ原子比＝６．０，Ｈ／Ｗ原子比＝６
．０）とした混合ガスを大気圧下、全流量１２０ｃｃ／
ｍｉｎで８００℃に保たれた反応器に導入し、この反応
器に置かれたニッケル基板を３０分間コーテイングした
。ニッケル基板上には、１５０μｍの膜が得られ、Ｘ線
回折パターンからＷ、Ｗ２Ｃ膜であることを確認した。Comparative Example 1 The molar ratio of tungsten hexafluoride, benzene and hydrogen was 1:1:3 (C/W atomic ratio = 6.0, H/W atomic ratio = 6).
．． 0) under atmospheric pressure with a total flow rate of 120cc/
The mixture was introduced into a reactor maintained at 800° C. for 30 minutes, and a nickel substrate placed in the reactor was coated for 30 minutes. A 150 μm film was obtained on the nickel substrate, and it was confirmed from the X-ray diffraction pattern that it was a W, W2C film.
【００１６】比較例２
６フッ化タングステン、トリメチルアミンおよび水素の
モル比を１：２：９（Ｃ／Ｗ原子比＝６．０，Ｈ／Ｗ原
子比＝１８．０）とした混合ガスを大気圧下、全流量１
２０ｃｃ／ｍｉｎで７００℃に保たれた反応器に導入し
、この反応器に置かれたニッケル基板を３０分間コーテ
イングした。ニッケル基板上には、１００μｍの膜が得
られ、Ｘ線回折パターンからＷ膜であることを確認した
。Comparative Example 2 A mixed gas containing tungsten hexafluoride, trimethylamine and hydrogen in a molar ratio of 1:2:9 (C/W atomic ratio = 6.0, H/W atomic ratio = 18.0) was At atmospheric pressure, total flow rate 1
The mixture was introduced into a reactor maintained at 700°C at a rate of 20 cc/min, and a nickel substrate placed in the reactor was coated for 30 minutes. A 100 μm film was obtained on the nickel substrate, and it was confirmed from the X-ray diffraction pattern that it was a W film.
【００１７】比較例３
６フッ化タングステン、トリメチルアミンおよび水素の
モル比を１：０．１：３（Ｃ／Ｗ原子比＝０．３，Ｈ／
Ｗ原子比＝６．０）とした混合ガスを大気圧下、全流量
１２０ｃｃ／ｍｉｎで７００℃に保たれた反応器に導入
し、この反応器に置かれたニッケル基板を３０分間コー
テイングした。ニッケル基板上には、６０μｍの膜が得
られ、Ｘ線回折パターンからＷ膜であることを確認した
。Comparative Example 3 The molar ratio of tungsten hexafluoride, trimethylamine and hydrogen was 1:0.1:3 (C/W atomic ratio = 0.3, H/
A mixed gas with a W atomic ratio of 6.0 was introduced into a reactor maintained at 700° C. under atmospheric pressure at a total flow rate of 120 cc/min, and a nickel substrate placed in the reactor was coated for 30 minutes. A 60 μm film was obtained on the nickel substrate, and it was confirmed from the X-ray diffraction pattern that it was a W film.
【００１８】[0018]
【発明の効果】本発明によれば、タングステンカーバイ
ト膜を効率よく基材に形成することができ、特に硬質膜
の形成においては均質、滑らかでかつ光沢のあるタング
ステンカーバイト膜を得ることができる。また、比較的
低温で膜形成できるため基材への悪影響を回避すること
ができ、各種精密機材としてひろく使用できるものであ
る。さらに本発明方法によれば大気圧下での膜形成が可
能であり、この場合には装置上の制約をほとんど受けず
、非常に工業的に有利な膜形成方法となるものである。[Effects of the Invention] According to the present invention, a tungsten carbide film can be efficiently formed on a base material, and in particular, when forming a hard film, a homogeneous, smooth, and glossy tungsten carbide film can be obtained. can. Furthermore, since the film can be formed at a relatively low temperature, it is possible to avoid adverse effects on the base material, and it can be widely used in various precision equipment. Furthermore, according to the method of the present invention, it is possible to form a film under atmospheric pressure, and in this case, there are almost no restrictions on equipment, making it a very industrially advantageous film forming method.
Claims (2)
だし、Ｒは水素またはアルキル基を示す。）で表される
アミンおよび水素を含有するガスを、４００〜９００℃
の温度範囲において気相反応させることを特徴とするタ
ングステンカーバイト膜の形成方法Claim 1: A gas containing tungsten hexafluoride, an amine represented by the general formula R3N (where R represents hydrogen or an alkyl group), and hydrogen is heated at 400 to 900°C.
A method for forming a tungsten carbide film characterized by carrying out a gas phase reaction in a temperature range of
の形成方法において、６フッ化タングステン、一般式Ｒ
３Ｎ（ただし、Ｒは水素またはアルキル基を示す。）で
表されるアミンおよび水素の混合比率をカーボンのタン
グステンに対する原子比で１〜２０、水素のタングステ
ンに対する原子比で１〜１５の範囲とすることを特徴と
する請求項１記載のタングステンカーバイト膜の形成方
法。2. The method for forming a tungsten carbide film according to claim 1, wherein tungsten hexafluoride, general formula R
The mixing ratio of the amine represented by 3N (where R represents hydrogen or an alkyl group) and hydrogen is in the range of 1 to 20 in terms of the atomic ratio of carbon to tungsten and 1 to 15 in terms of the atomic ratio of hydrogen to tungsten. 2. The method of forming a tungsten carbide film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3013527A JPH04254585A (en) | 1991-02-04 | 1991-02-04 | Formation of tungsten carbide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3013527A JPH04254585A (en) | 1991-02-04 | 1991-02-04 | Formation of tungsten carbide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04254585A true JPH04254585A (en) | 1992-09-09 |
Family
ID=11835630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3013527A Pending JPH04254585A (en) | 1991-02-04 | 1991-02-04 | Formation of tungsten carbide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04254585A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800383B1 (en) * | 1999-02-11 | 2004-10-05 | Hardide Limited | Tungsten carbide coating and method for producing the same |
| EP1899497A1 (en) * | 2005-06-29 | 2008-03-19 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Deposition method of ternary films |
| CN107130227A (en) * | 2017-07-06 | 2017-09-05 | 北京理工大学 | A kind of superfine nano-crystalline tungsten carbide coating and preparation method thereof |
-
1991
- 1991-02-04 JP JP3013527A patent/JPH04254585A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800383B1 (en) * | 1999-02-11 | 2004-10-05 | Hardide Limited | Tungsten carbide coating and method for producing the same |
| EP1899497A1 (en) * | 2005-06-29 | 2008-03-19 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Deposition method of ternary films |
| CN107130227A (en) * | 2017-07-06 | 2017-09-05 | 北京理工大学 | A kind of superfine nano-crystalline tungsten carbide coating and preparation method thereof |
| CN107130227B (en) * | 2017-07-06 | 2019-08-06 | 北京理工大学 | A kind of superfine nano-crystalline tungsten carbide coating and preparation method thereof |
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