JP5860734B2 - Hard coating member and method for producing the same - Google Patents
Hard coating member and method for producing the same Download PDFInfo
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- JP5860734B2 JP5860734B2 JP2012056101A JP2012056101A JP5860734B2 JP 5860734 B2 JP5860734 B2 JP 5860734B2 JP 2012056101 A JP2012056101 A JP 2012056101A JP 2012056101 A JP2012056101 A JP 2012056101A JP 5860734 B2 JP5860734 B2 JP 5860734B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011248 coating agent Substances 0.000 title description 19
- 238000000576 coating method Methods 0.000 title description 19
- 239000000758 substrate Substances 0.000 claims description 25
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 21
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000007888 film coating Substances 0.000 claims description 10
- 238000009501 film coating Methods 0.000 claims description 10
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 9
- 239000010408 film Substances 0.000 description 81
- 239000007789 gas Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 29
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 13
- 229910052582 BN Inorganic materials 0.000 description 12
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- -1 diborane Chemical compound 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- Cutting Tools, Boring Holders, And Turrets (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
- Chemical Vapour Deposition (AREA)
Description
本発明は、硬質皮膜被覆部材およびその製造方法に関し、特に、窒素とホウ素を含む硬質皮膜が基材上に形成された硬質皮膜被覆部材およびその製造方法に関する。 The present invention relates to a hard coating member and a method for producing the same, and more particularly to a hard coating member having a hard coating containing nitrogen and boron formed on a substrate and a method for producing the same.
従来、耐摩耗性や耐焼き付き性が必要とされる自動車などの摺動部品や機械部材の他、高面圧下で使用される金型などの表面に、スパッタリングなどの物理的蒸着によって窒素含有クロム皮膜を形成して、耐摩耗性や耐焼き付き性を向上させる方法が知られている（例えば、特許文献１参照）。また、高硬度で耐摩耗性や摺動性に優れた立方晶窒化ホウ素（ＢＮ）により基材を被覆する方法も提案されている（例えば、特許文献２参照）。 Conventionally, nitrogen-containing chromium is produced by physical vapor deposition such as sputtering on the surfaces of sliding parts and machine parts such as automobiles that require wear resistance and seizure resistance, as well as dies used under high surface pressure. A method of forming a film to improve wear resistance and seizure resistance is known (see, for example, Patent Document 1). In addition, a method of coating a base material with cubic boron nitride (BN) having high hardness and excellent wear resistance and slidability has been proposed (see, for example, Patent Document 2).
しかし、特許文献１の方法のように、スパッタリングなどの物理的蒸着によって窒素含有クロム皮膜のような硬質皮膜を金属基材上に形成すると、皮膜自体の圧縮応力により皮膜を厚くするのが困難であり、皮膜の内部応力が大きくなって基材への密着性が悪くなるおそれがある。
However, when a hard film such as a nitrogen-containing chromium film is formed on a metal substrate by physical vapor deposition such as sputtering as in the method of
また、特許文献２の方法のように、ＢＮ皮膜で基材を被覆する場合、耐久性を高くするためには、ＢＮ皮膜を厚くする必要があるが、ＢＮ皮膜を１μｍ以上に厚くすると、ＢＮ皮膜の内部応力が大きくなって、基材との密着強度が悪くなるという問題がある。また、このようなＢＮ皮膜で金型などの基材の表面を被覆すると、ＢＮ皮膜の表面が相手部材と繰り返し接触することにより、温度の上昇および下降が繰り返されるので、耐熱衝撃性（相手部材との接触による熱サイクルに耐えること）が良好でなければＢＮ皮膜が容易に破壊される可能性があるため、耐熱衝撃性が良好であることが必要になる。また、耐熱衝撃性に優れたＢＮ皮膜で基材を被覆するためには、ＢＮ皮膜のヤング率（縦弾性係数）が低いことが必要になる。 Further, when the base material is coated with a BN film as in the method of Patent Document 2, it is necessary to increase the thickness of the BN film in order to increase the durability. However, if the BN film is increased to 1 μm or more, the BN film There is a problem that the internal stress of the film is increased and the adhesion strength with the substrate is deteriorated. Further, when the surface of a base material such as a mold is coated with such a BN film, the surface of the BN film repeatedly comes into contact with the mating member, so that the temperature rises and falls repeatedly. If it is not good), the BN film can be easily broken, so that it is necessary to have good thermal shock resistance. Moreover, in order to coat a base material with a BN film having excellent thermal shock resistance, the Young's modulus (longitudinal elastic modulus) of the BN film needs to be low.
したがって、本発明は、このような従来の問題点に鑑み、ヤング率（縦弾性係数）が低く、熱衝撃性に優れた硬質皮膜で基材が被覆された硬質皮膜被覆部材およびその製造方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention provides a hard film-coated member having a low Young's modulus (longitudinal elastic modulus) and a hard film excellent in thermal shock resistance and a method for producing the same. The purpose is to provide.
本発明者らは、上記課題を解決するために鋭意研究した結果、ＮとＣとＢとＳｉからなり、ビッカース硬さＨＶが８００以上であり且つ縦弾性係数が１００ＧＰａ以下である硬質皮膜を基材上に形成することにより、ヤング率（縦弾性係数）が低く、熱衝撃性に優れた硬質皮膜で基材が被覆された硬質皮膜被覆部材を製造することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are based on a hard coating composed of N, C, B, and Si, having a Vickers hardness HV of 800 or more and a longitudinal elastic modulus of 100 GPa or less. Found that by forming on a material, it is possible to produce a hard-coated member having a low Young's modulus (longitudinal elastic modulus) and a base material coated with a hard film excellent in thermal shock, and completed the present invention. It came to do.
すなわち、本発明による硬質皮膜被覆部材は、ＮとＣとＢとＳｉからなる硬質皮膜が基材上に形成され、硬質皮膜のビッカース硬さＨＶが８００以上であり且つ縦弾性係数が１００ＧＰａ以下であることを特徴とする。この硬質皮膜被覆部材において、硬質皮膜のビッカース硬さＨＶが１０００以上であるのが好ましく、硬質皮膜の縦弾性係数が９５ＧＰａ以下であるのが好ましい。また、硬質皮膜のスクラッチ強度が４０Ｎ以上であるのが好ましい。 That is, in the hard coating member according to the present invention, a hard coating composed of N, C, B, and Si is formed on a substrate, the Vickers hardness HV of the hard coating is 800 or more, and the longitudinal elastic modulus is 100 GPa or less. It is characterized by being. In this hard film-coated member, the hard film preferably has a Vickers hardness HV of 1000 or more, and the hard film preferably has a longitudinal elastic modulus of 95 GPa or less. Moreover, it is preferable that the scratch strength of a hard film is 40 N or more.
また、本発明による硬質皮膜被覆部材の製造方法は、プラズマＣＶＤ法により６００℃以下の温度でＮとＣとＢとＳｉからなる硬質皮膜を基材上に形成することを特徴とする。この硬質皮膜被覆部材の製造方法において、原料ガスとして、Ｎ源ガスとＣ源ガスとＢ源ガスとＳｉ源ガスを使用し、ガス圧力を３００〜１００００Ｐａとするのが好ましい。この場合、Ｎ源ガスがＮ２ガスおよびＮＨ３ガスの少なくとも一方であり、Ｃ源ガスがＣＨ４、Ｃ２Ｈ２、Ｃ３Ｈ８、モノメチルシラン（ＭＭＳ）およびトリメチルボロン（ＴＭＢ）からなる群から選ばれる少なくとも１種のガスであり、Ｂ源ガスがトリメチルボロン（ＴＭＢ）、三フッ化ホウ素（ＢＦ３）、ジボランおよびホウ酸からなる群から選ばれる少なくとも１種のガスであり、Ｓｉ源ガスがモノメチルシラン（ＭＭＳ）、シラン、ジシランおよびトリメチルシランからなる群から選ばれる少なくとも１種のガスであるのが好ましい。また、原料ガスとしてＨ２ガスを使用してもよい。また、上記の硬質皮膜被覆部材の製造方法において、原料ガスとして、Ｈ２とＮ２とモノメチルシランとトリメチルボロンを含むガスを使用するのが好ましく、原料ガスがＣＨ４を含んでもよい。また、プラズマＣＶＤ法が、パルス放電プラズマＣＶＤ法であるのが好ましい。 The method for producing a hard film-coated member according to the present invention is characterized in that a hard film composed of N, C, B, and Si is formed on a substrate at a temperature of 600 ° C. or less by a plasma CVD method. In this method for producing a hard coating member, it is preferable to use N source gas, C source gas, B source gas, and Si source gas as the source gas, and to set the gas pressure to 300 to 10,000 Pa. In this case, the N source gas is at least one of N 2 gas and NH 3 gas, and the C source gas is composed of CH 4 , C 2 H 2 , C 3 H 8 , monomethylsilane (MMS), and trimethylboron (TMB). At least one gas selected from the group, and the B source gas is at least one gas selected from the group consisting of trimethylboron (TMB), boron trifluoride (BF 3 ), diborane and boric acid, and Si The source gas is preferably at least one gas selected from the group consisting of monomethylsilane (MMS), silane, disilane, and trimethylsilane. It may also be used H 2 gas as a material gas. In the above-described method for fabricating the hard coating covering member, as a source gas, it is preferable to use a gas containing H 2 and N 2 and monomethyl silane and trimethyl boron source gas may include CH 4. The plasma CVD method is preferably a pulse discharge plasma CVD method.
本発明によれば、ヤング率（縦弾性係数）が低く、熱衝撃性に優れた硬質皮膜で基材が被覆された硬質皮膜被覆部材を製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, the hard film coating | coated member with which the base material was coat | covered with the hard film with a low Young's modulus (longitudinal elastic modulus) and excellent thermal shock property can be manufactured.
本発明による硬質皮膜被覆部材の製造方法の実施の形態では、プラズマＣＶＤ法により６００℃以下の温度でＮとＣとＢとＳｉからなる硬質皮膜を基材上に形成して硬質皮膜被覆部材を製造する。 In the embodiment of the method for producing a hard film covering member according to the present invention, a hard film made of N, C, B and Si is formed on a substrate at a temperature of 600 ° C. or less by a plasma CVD method. To manufacture.
基材として、熱間ダイス鋼（例えばＳＫＤ６１）、冷間ダイス鋼（例えばＳＫＤ１１）、高速度工具鋼（例えばＳＫＨ５１）などを使用することができる。 As the base material, hot die steel (for example, SKD61), cold die steel (for example, SKD11), high speed tool steel (for example, SKH51), or the like can be used.
プラズマＣＶＤ法としては、減圧下（または大気圧下）で反応性ガスのプラズマ放電分解によって薄膜を形成することができる方法であればよいが、パルス放電プラズマＣＶＤ法であるのが好ましい。この場合、原料ガスとしてＮ源、Ｃ源、Ｂ源およびＳｉ源となるガスをパルス放電プラズマＣＶＤ装置に供給して、６００℃以下の温度でＮとＣとＢとＳｉからなる硬質皮膜を基材上に形成することができる。Ｎ源としては、Ｎ２やＮＨ３などを使用することができる。Ｓｉ源としては、モノメチルシラン（ＭＭＳ）、シラン、ジシラン、トリメチルシランなどを使用することができる。Ｂ源としては、トリメチルボロン（ＴＭＢ）、三フッ化ホウ素（ＢＦ３）、ジボラン、ホウ酸などを使用することができる。Ｃ源としては、ＣＨ４、Ｃ２Ｈ２、Ｃ３Ｈ８、ＭＭＳ、ＴＭＢなどを使用することができる。また、原料ガスにＨ２ガスを添加してもよい。 The plasma CVD method may be any method that can form a thin film by plasma discharge decomposition of a reactive gas under reduced pressure (or atmospheric pressure), but is preferably a pulse discharge plasma CVD method. In this case, N source, C source, B source, and Si source gas are supplied to the pulse discharge plasma CVD apparatus as source gases, and a hard film composed of N, C, B, and Si is formed at a temperature of 600 ° C. or lower. It can be formed on a material. As the N source, N 2 , NH 3 or the like can be used. As the Si source, monomethylsilane (MMS), silane, disilane, trimethylsilane, or the like can be used. As the B source, trimethylboron (TMB), boron trifluoride (BF 3 ), diborane, boric acid, or the like can be used. As the C source, CH 4 , C 2 H 2 , C 3 H 8 , MMS, TMB, and the like can be used. It may also be added H 2 gas as a source gas.
パルス放電プラズマＣＶＤ法によって硬質皮膜を形成する場合、例えば、パルス放電プラズマＣＶＤ装置の真空チャンバ内に基材をセットし、真空チャンバ内を１０Ｐａ以下まで排気した後、Ｎ源ガスを流量１〜１０００ｃｃｍ（ｃｃ／分）、好ましくは８０〜４００ｃｃｍ、Ｓｉ源ガスを流量０．０５〜１００ｃｃｍ、好ましくは０．１〜５ｃｃｍ、Ｂ源ガスを流量０．１〜１００ｃｃｍ、好ましくは１〜１０ｃｃｍ、Ｃ源ガスを流量０．０５〜２００ｃｃｍ、好ましくは０．１〜１００ｃｃｍで供給し、ガス圧力Ｐｇを３００〜１００００Ｐａ、好ましくは５００〜２０００Ｐａ、基材温度Ｔｓを２００〜６００℃、好ましくは３８０〜５００℃、処理時間ＤＴを１０〜１２０分間、好ましくは２０〜８０分間、パルス周波数ｆを０．１〜１０ｋＨｚ、好ましくは０．５〜５ｋＨｚ、パルスデューティ比ＤＲを２〜３０％、好ましくは３〜２５％として、パルス放電プラズマＣＶＤ法により基材上に硬質皮膜を形成して硬質皮膜被覆部材を得ることができる。なお、Ｃ源ガスとしてＣＨ４ガスを使用する場合には、流量１００ｃｃｍ以下、好ましくは２０ｃｃｍ以下で供給し、Ｃ２Ｈ２ガスやＣ３Ｈ８ガスなどを使用する場合には、流量２００ｃｃｍ以下、好ましくは１０〜１００ｃｃｍで供給する。また、原料ガスにＨ２ガスを添加する場合には、流量１〜１０００ｃｃｍで供給するのが好ましい。
When forming a hard film by the pulse discharge plasma CVD method, for example, after setting the substrate in the vacuum chamber of the pulse discharge plasma CVD apparatus and exhausting the vacuum chamber to 10 Pa or less, the N source gas is supplied at a flow rate of 1 to 1000 ccm. (Cc / min), preferably 80-400 ccm, Si source gas flow rate 0.05-100 ccm, preferably 0.1-5 ccm, B source gas flow rate 0.1-100 ccm, preferably 1-10 ccm, C source The gas is supplied at a flow rate of 0.05 to 200 ccm, preferably 0.1 to 100 ccm, the gas pressure Pg is 300 to 10000 Pa, preferably 500 to 2000 Pa, and the substrate temperature Ts is 200 to 600 ° C., preferably 380 to 500 ° C. The treatment time DT is 10 to 120 minutes, preferably 20 to 80 minutes, and the pulse frequency f is 0.1. A hard coating member is obtained by forming a hard coating on a substrate by pulse discharge plasma CVD method at 10 kHz, preferably 0.5 to 5 kHz, and a pulse duty ratio DR of 2 to 30%, preferably 3 to 25%. be able to. When CH 4 gas is used as the C source gas, it is supplied at a flow rate of 100 ccm or less, preferably 20 ccm or less, and when C 2 H 2 gas or C 3 H 8 gas is used, the flow rate is 200 ccm or less. , Preferably 10 to 100 ccm. Further, in the case of adding H 2 gas to the source gas is preferably supplied at a
このようにして得られた硬質皮膜被覆部材では、ＮとＣとＢとＳｉからなる硬質皮膜が基材上に形成され、硬質皮膜のビッカース硬さＨＶが８００以上、好ましくは１０００以上と高く、ヤング率（縦弾性係数）が１００ＧＰａ以下、好ましくは９５ＧＰａ以下と低く、スクラッチ強度が好ましくは４０Ｎ以上である。このように低ヤング率（低縦弾性係数）であることから、耐熱衝撃性に優れた硬質皮膜を基材上に形成することができる。 In the thus obtained hard coating member, a hard coating composed of N, C, B and Si is formed on the substrate, and the Vickers hardness HV of the hard coating is 800 or higher, preferably 1000 or higher, The Young's modulus (longitudinal elastic modulus) is as low as 100 GPa or less, preferably 95 GPa or less, and the scratch strength is preferably 40 N or more. Thus, since it has a low Young's modulus (low longitudinal elastic modulus), a hard coating excellent in thermal shock resistance can be formed on the substrate.
なお、本発明による硬質皮膜被覆部材の硬質皮膜上にさらにＢＮやＤＬＣ（ダイヤモンドライクカーボン）などの高硬度の皮膜を形成してもよい。このように、本発明による硬質皮膜被覆部材の硬質皮膜をＢＮやＤＬＣの下地膜として用いると、高硬度の皮膜と低い硬度の基材との間に生じる応力を緩和することができる。 Note that a hard film such as BN or DLC (diamond-like carbon) may be further formed on the hard film of the hard film-coated member according to the present invention. As described above, when the hard film of the hard film-coated member according to the present invention is used as a base film of BN or DLC, the stress generated between the high-hardness film and the low-hardness base material can be relaxed.
以下、本発明による硬質皮膜被覆部材およびその製造方法の実施例について詳細に説明する。 Examples of the hard film-coated member and the manufacturing method thereof according to the present invention will be described in detail below.
［実施例１］
基材としてＳＫＤ６１を用意し、パルス放電プラズマＣＶＤ装置の真空チャンバ内に基材をセットし、容積０．１７ｍ３の真空チャンバ内を１０Ｐａ以下まで排気した後、Ｎ２ガスを流量１００ｃｃｍ、Ｈ２で希釈した１０％のＣＨ４ガスを流量１０ｃｃｍ、Ｈ２で希釈した５％のモノメチルシラン（ＭＭＳ）を流量１０ｃｃｍ、Ｈ２で希釈した１０％のトリメチルボロン（ＴＭＢ）を流量２５ｃｃｍで供給し、ガス圧力Ｐｇを７５０Ｐａ、基材温度Ｔｓを４００℃、処理時間ＤＴを３０分間、パルス周波数ｆを１ｋＨｚ、パルスデューティ比ＤＲを２０％、ピーク電流Ａｐを１Ａ、ピーク電圧Ｖｐを４．５ｋＶ、電極間距離を１５０ｍｍとして、パルス放電プラズマＣＶＤ法により基材上に硬質皮膜を形成して硬質皮膜被覆部材を得た。
[Example 1]
SKD61 is prepared as a base material, the base material is set in a vacuum chamber of a pulse discharge plasma CVD apparatus, the inside of a vacuum chamber having a volume of 0.17 m 3 is evacuated to 10 Pa or less, N 2 gas is supplied at a flow rate of 100 ccm, and H 2. in supplying 10% of CH 4 gas diluted flow 10 ccm, 5% of the monomethyl silane diluted with H 2 (MMS) flow rate 10 ccm, 10% of trimethyl boron diluted with H 2 (TMB) at a flow rate 25Ccm, Gas pressure Pg is 750 Pa, substrate temperature Ts is 400 ° C., processing time DT is 30 minutes, pulse frequency f is 1 kHz, pulse duty ratio DR is 20%, peak current Ap is 1 A, peak voltage Vp is 4.5 kV, electrode A hard film coating member was obtained by forming a hard film on a substrate by a pulse discharge plasma CVD method with an interval of 150 mm.
このようにして得られた硬質皮膜被覆部材について、断面を走査電子顕微鏡（ＳＥＭ）で観察したところ、厚さ１〜２μｍ程度の薄皮状の皮膜が形成され、微細欠陥が少ないことが確認された。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、マーカス型高周波グロー放電発光表面分析装置（ＧＤ−ＯＥＳ）により、ＮとＣとＢとＳｉからなる皮膜であることが確認された。 The hard film-coated member thus obtained was observed with a scanning electron microscope (SEM), and it was confirmed that a thin film having a thickness of about 1 to 2 μm was formed and there were few fine defects. . In addition, the hard film formed on the base material of the hard film coating member is confirmed to be a film composed of N, C, B, and Si by a Marcus type high-frequency glow discharge luminescence surface analyzer (GD-OES). It was done.
また、得られた硬質皮膜被覆部材のビッカース硬さ、ヤング率およびスクラッチ強度を求めた。 Further, the Vickers hardness, Young's modulus, and scratch strength of the obtained hard film-coated member were determined.
ビッカース硬さおよびヤング率は、フィッシャー硬度計（超微小硬さ試験機）（株式会社フィッシャー・インストルメント製のＦＩＳＣＨＥＲＳＣＯＰＥＨ１００Ｃｘｙ−ｐ）を使用して、バーコビッチ圧子により測定荷重１０ｍＮ／１０ｓを加えて室温で測定した塑性変形硬さに基づいて算出した。その結果、塑性変形硬さは１４．７ＧＰａ（最大値１５．８ＧＰａ、最小値９．４ＧＰａ）、ビッカース硬さＨＶは１０８５であり、ヤング率（縦弾性係数）は７９ＧＰａと低かった。 The Vickers hardness and Young's modulus were measured using a Fischer hardness tester (ultra-micro hardness tester) (FISCHERSCOPEH100C xy-p manufactured by Fischer Instrument Co., Ltd.), with a measurement load of 10 mN / 10 s applied by a Berkovich indenter. Calculation was based on the plastic deformation hardness measured at room temperature. As a result, the plastic deformation hardness was 14.7 GPa (maximum value 15.8 GPa, minimum value 9.4 GPa), the Vickers hardness HV was 1085, and the Young's modulus (longitudinal elastic modulus) was as low as 79 GPa.
スクラッチ強度として、スクラッチ試験機（ＣＳＭ社製のＲＥＶＥＴＥＳＴ、ＡＥセンサー付スクラッチ試験機）を使用し、最小荷重０．９Ｎ、最大荷重１５０Ｎ、荷重速度９０．０６Ｎ／分、スクラッチ速度６．０４ｍｍ／分、スクラッチ距離１０ｍｍとして、０．２ｍｍＲのダイヤモンド圧子（型式Ｒｏｃｋｗｅｌｌ、シリアルＮｏ．Ｎ２−３１２２）によってスクラッチ試験を行い、スクラッチの周辺の皮膜が破壊されたときの荷重（臨界荷重Ｌｃ）を測定した。その結果、図１に示すように、スクラッチ強度（スクラッチ摩擦力が大きく変化する荷重（臨界荷重Ｌｃ））は約４０Ｎであった。 As a scratch strength, a scratch tester (REVEST made by CSM, scratch tester with AE sensor) is used, minimum load 0.9N, maximum load 150N, load speed 90.06N / min, scratch speed 6.04mm / min A scratch test was conducted with a diamond indenter (model Rockwell, serial No. N2-3122) of 0.2 mmR at a scratch distance of 10 mm, and a load (critical load Lc) when the film around the scratch was broken was measured. As a result, as shown in FIG. 1, the scratch strength (the load at which the scratch friction force greatly changes (critical load Lc)) was about 40 N.
［実施例２］
１０％のＣＨ４ガスを供給せず、ガス圧力Ｐｇを１０００Ｐａとし、基材温度Ｔｓを４６０℃とした以外は、実施例１と同様の方法により、基材上に硬質皮膜を形成して硬質皮膜被覆部材を得た。
[Example 2]
A hard film is formed on the substrate in the same manner as in Example 1 except that 10% CH 4 gas is not supplied, the gas pressure Pg is 1000 Pa, and the substrate temperature Ts is 460 ° C. A film-coated member was obtained.
このようにして得られた硬質皮膜被覆部材について、断面を走査電子顕微鏡（ＳＥＭ）で観察したところ、厚さ１〜２μｍ程度の硬質皮膜が形成され、微細欠陥が多いことが確認された。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、ＧＤ−ＯＥＳにより、ＮとＣとＢとＳｉからなる皮膜であることが確認された。 When the cross section of the hard film-coated member thus obtained was observed with a scanning electron microscope (SEM), it was confirmed that a hard film with a thickness of about 1 to 2 μm was formed and there were many fine defects. Moreover, it was confirmed by GD-OES that the hard film formed on the base material of this hard film coating member is a film made of N, C, B, and Si.
また、得られた硬質皮膜被覆部材のビッカース硬さ、ヤング率およびスクラッチ強度を実施例１と同様の方法により求めたところ、塑性変形硬さは１１．１ＧＰａ（１２点の平均値）、ビッカース硬さＨＶは８３２であり、ヤング率（縦弾性係数）は９０ＧＰａと低く、図２に示すように、スクラッチ強度は約７０Ｎであった。 Further, when the Vickers hardness, Young's modulus, and scratch strength of the obtained hard film-coated member were determined in the same manner as in Example 1, the plastic deformation hardness was 11.1 GPa (average of 12 points), and Vickers hardness The thickness HV was 832, the Young's modulus (longitudinal elastic modulus) was as low as 90 GPa, and the scratch strength was about 70 N as shown in FIG.
［実施例３］
基材としてＳＫＤ６１を用意し、パルス放電プラズマＣＶＤ装置の真空チャンバ内に基材をセットし、容積０．１７ｍ３の真空チャンバ内を１０Ｐａ以下まで排気した後、Ｈ２ガス流量を４００ｃｃｍ、Ｎ２ガスを流量３６０ｃｃｍ、Ｈ２で希釈した５％のモノメチルシラン（ＭＭＳ）を流量５ｃｃｍ、Ｈ２で希釈した１０％のトリメチルボロン（ＴＭＢ）を流量２５ｃｃｍで供給し、ガス圧力Ｐｇを１４００Ｐａ、基材温度Ｔｓを４３０℃、処理時間ＤＴを５０分間、パルス周波数ｆを３ｋＨｚ、パルスデューティ比ＤＲを５％、ピーク電流Ａｐを１Ａ、ピーク電圧Ｖｐを４．５ｋＶ、電極間距離を１５０ｍｍとして、パルス放電プラズマＣＶＤ法により基材上に硬質皮膜を形成して硬質皮膜被覆部材を得た。
[Example 3]
SKD61 is prepared as a base material, the base material is set in a vacuum chamber of a pulse discharge plasma CVD apparatus, the inside of a vacuum chamber having a volume of 0.17 m 3 is evacuated to 10 Pa or less, an H 2 gas flow rate is set to 400 ccm, N 2 gas flow 360ccm, 5% of monomethyl silane diluted with H 2 (MMS) flow rate 5 ccm, 10% of trimethyl boron diluted with H 2 and (TMB) was fed at a flow rate 25ccm, 1400Pa gas pressure Pg, the substrate Pulse discharge at a temperature Ts of 430 ° C., a processing time DT of 50 minutes, a pulse frequency f of 3 kHz, a pulse duty ratio DR of 5%, a peak current Ap of 1 A, a peak voltage Vp of 4.5 kV, and a distance between electrodes of 150 mm A hard film was formed on the substrate by plasma CVD to obtain a hard film coated member.
このようにして得られた硬質皮膜被覆部材について、断面を走査電子顕微鏡（ＳＥＭ）で観察したところ、厚さ１〜２μｍ程度の皮膜が形成され、微細欠陥がないことが確認された。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、ＧＤ−ＯＥＳにより、ＮとＣとＢとＳｉからなる皮膜であることが確認された。 When the cross section of the hard film-coated member thus obtained was observed with a scanning electron microscope (SEM), a film having a thickness of about 1 to 2 μm was formed, and it was confirmed that there were no fine defects. Moreover, it was confirmed by GD-OES that the hard film formed on the base material of this hard film coating member is a film made of N, C, B, and Si.
また、得られた硬質皮膜被覆部材のビッカース硬さ、ヤング率およびスクラッチ強度を実施例１と同様の方法により求めたところ、塑性変形硬さは１６．９ＧＰａ（１２点の平均値）、ビッカース硬さＨＶは１２２０であり、ヤング率（縦弾性係数）は９２ＧＰａと低く、図３に示すように、スクラッチ強度は約７５Ｎであった。 Further, when the Vickers hardness, Young's modulus and scratch strength of the obtained hard film-coated member were determined by the same method as in Example 1, the plastic deformation hardness was 16.9 GPa (average value of 12 points), and Vickers hardness The thickness HV was 1220, the Young's modulus (longitudinal elastic modulus) was as low as 92 GPa, and the scratch strength was about 75 N as shown in FIG.
［比較例１］
Ｈ２で希釈した５％のモノメチルシラン（ＭＭＳ）と、Ｈ２で希釈した１０％のトリメチルボロン（ＴＭＢ）を供給せず、処理時間ＤＴを１２０分間とした以外は、実施例１と同様の方法により、基材上に硬質皮膜を形成して硬質皮膜被覆部材を得た。
[Comparative Example 1]
5% of monomethyl silane diluted with H 2 (MMS), without supplying the diluted 10% trimethyl boron (TMB) in H 2, except that the treatment time DT was set to 120 minutes, in the same manner as in Example 1 By the method, a hard film was formed on the substrate to obtain a hard film-coated member.
このようにして得られた硬質皮膜被覆部材について、断面を走査電子顕微鏡（ＳＥＭ）で観察したところ、皮膜の形成が明確には確認されなかった。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、ＧＤ−ＯＥＳにより、ＮとＣからなる皮膜であることが確認された。 When the cross section of the hard film-coated member thus obtained was observed with a scanning electron microscope (SEM), the formation of the film was not clearly confirmed. Moreover, it was confirmed that the hard film | membrane formed on the base material of this hard film | membrane coating | coated member is a film | membrane which consists of N and C by GD-OES.
また、得られた硬質皮膜被覆部材のビッカース硬さ、ヤング率およびスクラッチ強度を実施例１と同様の方法により求めたところ、塑性変形硬さは１１．６ＧＰａ（１２点の平均値）、ビッカース硬さＨＶは８７７であり、ヤング率（縦弾性係数）は２０９ＧＰａ、スクラッチ強度は約７０Ｎであった。 Further, when the Vickers hardness, Young's modulus, and scratch strength of the obtained hard film-coated member were determined in the same manner as in Example 1, the plastic deformation hardness was 11.6 GPa (an average value of 12 points), and Vickers hardness The HV was 877, the Young's modulus (longitudinal elastic modulus) was 209 GPa, and the scratch strength was about 70N.
［比較例２］
基材としてＳＫＤ６１を用意し、パルス放電プラズマＣＶＤ装置の真空チャンバ内に基材をセットし、真空チャンバ内を１０Ｐａ以下まで排気した後、水素ガスを流量１５０ｃｃｍで供給し、ガス圧力Ｐｇを５０００Ｐａ、基材温度Ｔｓを３９０℃、処理時間Ｔｄを２０分間、パルス周波数ｆを３ｋＨｚ、パルスデューティ比ＤＲを５％、ピーク電流Ａｐを０．９Ａ、ピーク電圧Ｖｐを１．５Ｖ、電極間距離を３０ｍｍとして、水素プラズマ処理を行った。
[Comparative Example 2]
SKD61 is prepared as a base material, the base material is set in a vacuum chamber of a pulse discharge plasma CVD apparatus, the inside of the vacuum chamber is exhausted to 10 Pa or less, hydrogen gas is supplied at a flow rate of 150 ccm, a gas pressure Pg is 5000 Pa, The substrate temperature Ts is 390 ° C., the processing time Td is 20 minutes, the pulse frequency f is 3 kHz, the pulse duty ratio DR is 5%, the peak current Ap is 0.9 A, the peak voltage Vp is 1.5 V, and the distance between the electrodes is 30 mm. As a result, hydrogen plasma treatment was performed.
このようにして基材の水素プラズマ処理を行った後、真空チャンバ内を１０Ｐａ以下まで排気し、その後、水素ガスを流量４０ｃｃｍ、Ｎ２ガスを流量１６０ｃｃｍで供給し、ガス圧力Ｐｇを５０００Ｐａ、基材温度Ｔｓを４９０℃、処理時間Ｔｄを９０分間、パルス周波数ｆを３ｋＨｚ、パルスデューティ比ＤＲを５％、ピーク電流Ａｐを１．１Ａ、ピーク電圧Ｖｐを５．２Ｖとして、プラズマ窒化処理を行った。 After performing the hydrogen plasma treatment of the base material in this way, the inside of the vacuum chamber is evacuated to 10 Pa or less, and then hydrogen gas is supplied at a flow rate of 40 ccm, N 2 gas is supplied at a flow rate of 160 ccm, and the gas pressure Pg is 5000 Pa. Plasma nitriding is performed at a material temperature Ts of 490 ° C., a processing time Td of 90 minutes, a pulse frequency f of 3 kHz, a pulse duty ratio DR of 5%, a peak current Ap of 1.1 A, and a peak voltage Vp of 5.2 V. It was.
このようにして基材のプラズマ窒化処理を行った後、真空チャンバ内を１０Ｐａ以下まで排気し、その後、水素ガスを流量４００ｃｃｍ、Ｎ２ガスを流量３６０ｃｃｍ、Ｈ２で希釈した１０％のトリメチルボロン（ＴＭＢ）を流量２５ｃｃｍで供給し、ガス圧力Ｐｇを３０００Ｐａ、基材温度Ｔｓを４６０℃、処理時間Ｔｄを２０分間、パルス周波数ｆを３ｋＨｚ、パルスデューティ比ＤＲを５％、ピーク電流Ａｐを０．９Ａ、ピーク電圧Ｖｐを４．８Ｖとして、パルス放電プラズマＣＶＤ法により基材上にＢＮ膜を形成して硬質皮膜被覆部材を得た。 After performing the plasma nitriding treatment of the base material in this manner, the inside of the vacuum chamber is exhausted to 10 Pa or less, and then 10% trimethylboron diluted with hydrogen gas at a flow rate of 400 ccm, N 2 gas at a flow rate of 360 ccm, and H 2. (TMB) is supplied at a flow rate of 25 ccm, the gas pressure Pg is 3000 Pa, the substrate temperature Ts is 460 ° C., the processing time Td is 20 minutes, the pulse frequency f is 3 kHz, the pulse duty ratio DR is 5%, and the peak current Ap is 0. The hard film-coated member was obtained by forming a BN film on the base material by a pulse discharge plasma CVD method with a peak voltage Vp of 4.9 V and a peak voltage Vp of 4.8 V.
このようにして得られた硬質皮膜被覆部材について、断面を走査電子顕微鏡で観察したところ、厚さ１〜２μｍ程度の硬質皮膜が形成され、微細欠陥がないことが確認された。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、ＧＤ−ＯＥＳにより、ＮとＣとＢからなる皮膜であることが確認された。 When the cross section of the hard film-coated member thus obtained was observed with a scanning electron microscope, it was confirmed that a hard film having a thickness of about 1 to 2 μm was formed and there were no fine defects. Moreover, it was confirmed that the hard film | membrane formed on the base material of this hard film | membrane covering member is a film | membrane which consists of N, C, and B by GD-OES.
また、得られた硬質皮膜被覆部材のビッカース硬さおよびヤング率を実施例１と同様の方法により求めたところ、塑性変形硬さは３．１５ＧＰａ（１０点の平均値）、ビッカース硬さＨＶは約２２０、ヤング率（縦弾性係数）は３５８ＧＰａであった。 Further, when the Vickers hardness and Young's modulus of the obtained hard film-coated member were obtained by the same method as in Example 1, the plastic deformation hardness was 3.15 GPa (10-point average value), and the Vickers hardness HV was The Young's modulus (longitudinal elastic modulus) was about 358 GPa.
[実施例４]
基材としてＳＫＤ６１を用意し、パルスプラズマＣＶＤ装置の真空チャンバ内に基材をセットし、容積０．１７ｍ３の真空チャンバ内を１０Ｐａ以下まで排気した後、Ｈ２ガスを流量４００ｃｃｍ、Ｎ２ガスを流量３６０ｃｃｍ、Ｈ２で希釈した５％のモノメチルシラン（ＭＭＳ）を流量５ｃｃｍ、Ｈ２で希釈した１０％のトリメチルボロン（ＴＭＢ）を２５ｃｃｍで供給し、ガス圧力Ｐｇを１５００Ｐａ、基材温度Ｔｓを４００℃、処理時間ＤＴを６０分間、パルス周波数ｆを１ｋＨｚ、パルスデューティ比ＤＲを５％、ピーク電流Ａｐを１Ａ、ピーク電圧Ｖｐを０．７５ｋＶ、電極間距離を３０ｍｍとして、パルス放電プラズマＣＶＤ法により基材上に硬質皮膜を形成して硬質皮膜被覆部材を得た。
[Example 4]
SKD61 is prepared as a base material, the base material is set in a vacuum chamber of a pulse plasma CVD apparatus, the inside of a vacuum chamber having a volume of 0.17 m 3 is evacuated to 10 Pa or less, H 2 gas is supplied at a flow rate of 400 ccm, and N 2 gas. the flow 360Ccm, supplying 5% of monomethyl silane diluted with H 2 (MMS) flow rate 5 ccm, 10% of the trimethyl boron diluted with H 2 and (TMB) in 25ccm, 1500Pa gas pressure Pg, the substrate temperature Ts Pulse discharge plasma CVD with 400 ° C., processing time DT 60 minutes,
このようにして得られた硬質皮膜被覆部材について、断面をＳＥＭで観察したところ、厚さ３．５μｍ程度の被膜が形成され、微細欠陥がないことが確認された。また、この硬質皮膜被覆部材の基材上に形成された硬質皮膜は、ＧＤ−ＯＥＳにより、ＮとＣとＢとＳｉからなる皮膜であることが確認された。 When the cross section of the hard film-coated member thus obtained was observed with an SEM, it was confirmed that a film having a thickness of about 3.5 μm was formed and there were no fine defects. Moreover, it was confirmed by GD-OES that the hard film formed on the base material of this hard film coating member is a film made of N, C, B, and Si.
また、得られた硬質皮膜被覆部材のビッカース硬さおよびヤング率を実施例１と同様の方法により求めたところ、ビッカース硬さＨＶは１０６７であり、ヤング率は７９．８ＧＰａと低かった。 Further, when the Vickers hardness and Young's modulus of the obtained hard film-coated member were determined by the same method as in Example 1, the Vickers hardness HV was 1067 and the Young's modulus was as low as 79.8 GPa.
本発明による硬質皮膜被覆部材は、自動車などの摺動部品や機械部材、金型の表面の部材などの様々な部材として利用することができる。 The hard coating member according to the present invention can be used as various members such as sliding parts such as automobiles, mechanical members, and members on the surface of a mold.
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| JP2536492B2 (en) * | 1986-09-04 | 1996-09-18 | 日新電機株式会社 | Tool material |
| JPH0672303B2 (en) * | 1987-05-29 | 1994-09-14 | 日本電気株式会社 | Hard amorphous carbon film |
| JP2001277250A (en) * | 2000-03-29 | 2001-10-09 | Bridgestone Corp | Thin film for molding mold, and mold |
| JP2001277251A (en) * | 2000-03-29 | 2001-10-09 | Bridgestone Corp | Thin film for molding mold, and mold |
| JP2005282668A (en) * | 2004-03-29 | 2005-10-13 | Rikogaku Shinkokai | Fastening tool member with fastening sliding face covered with hard coating, fastener mounted therewith and fastening tool member manufacturing method |
| JP4380622B2 (en) * | 2005-11-04 | 2009-12-09 | 日立ツール株式会社 | Multilayer coating member and method for producing the same |
| EP2443267B1 (en) * | 2009-06-18 | 2020-01-08 | Oerlikon Surface Solutions AG, Pfäffikon | Protective coating, a coated member having a protective coating as well as method for producing a protective coating |
| JP5656010B2 (en) * | 2009-12-04 | 2015-01-21 | ノベラス・システムズ・インコーポレーテッドＮｏｖｅｌｌｕｓ Ｓｙｓｔｅｍｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | Method for forming hard mask film and apparatus for forming hard mask film |
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