JP2013076124A - Method for manufacturing coated article with excellent corrosion resistance, and coated article - Google Patents
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Abstract
Description
本発明は、例えばプラスチックやゴムの成形に用いられる金型、工具、および射出成形用部品といった、耐食性が求められる被覆物品の製造方法および被覆物品に関する。 The present invention relates to a method for producing a coated article and a coated article that require corrosion resistance, such as a mold, a tool, and an injection molding part used for molding plastics and rubber, for example.
従来、プラスチック（樹脂）やゴムの成形においては、その被成形材によってもたらされる腐食環境から、成形に使用される金型や工具等の物品には優れた耐食性が求められている。例えば射出成形の場合、そのプラスチック等の被成形材には耐熱性や強度を向上させるための各種の添加剤が加えられる。そして、射出成形中には、その加熱または発熱によってプラスチックが分解する一方で、上記の添加剤からも腐食性ガスが発生するので、射出成形用部品（例えば、スクリューヘッドや、シールリング、など）は激しい腐食環境に曝され、孔食やガス焼付き等の要因となる。 Conventionally, in the molding of plastics (resins) and rubbers, excellent corrosion resistance is required for articles such as molds and tools used for molding because of the corrosive environment caused by the molding material. For example, in the case of injection molding, various additives for improving heat resistance and strength are added to a material to be molded such as plastic. During injection molding, the plastic is decomposed by heating or heat generation, and corrosive gas is also generated from the above additives. Therefore, injection molding parts (for example, screw heads, seal rings, etc.) Is exposed to a severe corrosive environment, causing pitting corrosion and gas seizure.
そこで、腐食環境下で使用される各種物品の耐食性を向上する手法としては、該部品への表面処理が一般的に用いられている。例えば、厚膜のハードクロムメッキを被覆することで耐食性を改善する手法がある。また、物理蒸着法（以下、ＰＶＤと略す）や化学蒸着法によって被覆されるＴｉＮ、ＣｒＮ、ＴｉＣＮ等の硬質皮膜は、その優れた耐食性に加えて、高硬度による耐摩耗性も備えていることから、有効な手法である。 Therefore, as a technique for improving the corrosion resistance of various articles used in a corrosive environment, surface treatment on the component is generally used. For example, there is a technique for improving the corrosion resistance by coating a thick hard chrome plating. In addition, hard coatings such as TiN, CrN, TiCN, etc. coated by physical vapor deposition (hereinafter abbreviated as PVD) or chemical vapor deposition have high wear resistance in addition to their excellent corrosion resistance. Therefore, it is an effective method.
例えば、射出成形用部品の表面を窒化処理した後、アークイオンプレーティング法によるＣｒＮやＴｉＮ皮膜を被覆することで、耐摩耗性や皮膜密着性を改善する手法がある（特許文献１）。また、同じくＣｒＮやＴｉＮ皮膜を被覆する手法においては、基材との密着性および耐食性に優れたＣｒＮ皮膜を先に被覆した上に、高硬度のＴｉＮ皮膜を複層被覆することで、耐食性を付与する手法がある（特許文献２）。 For example, there is a technique for improving wear resistance and film adhesion by nitriding the surface of an injection molding part and then coating a CrN or TiN film by an arc ion plating method (Patent Document 1). Similarly, in the method of coating a CrN or TiN film, the CrN film having excellent adhesion and corrosion resistance to the base material is coated first, and then a high-hardness TiN film is coated in multiple layers, thereby improving the corrosion resistance. There is a method of giving (Patent Document 2).
また、上記の皮膜成分の改良による一方では、その構造を改良することで、皮膜特性を向上させる手法がある。例えば切削工具の分野では、その工具表面に硬質皮膜を被覆する際、被覆途中に中間イオンエッチング（ボンバード処理）を行なうことで亀裂破壊の要因となるドロップレットを除去し、ボイドやポアの発生しない平滑な皮膜を得る手法がある（特許文献３）。そして、上記のドロップレットを除去する手法には、サンドブラストによる機械的処理を適用する手法もある（特許文献４）。 On the other hand, there is a technique for improving the film properties by improving the structure on the other hand by improving the film components. For example, in the field of cutting tools, when coating a hard film on the tool surface, intermediate ion etching (bombarding) is performed in the middle of the coating to remove droplets that cause crack fracture, and no voids or pores are generated. There is a technique for obtaining a smooth film (Patent Document 3). As a method for removing the above-described droplets, there is a method in which mechanical processing by sandblasting is applied (Patent Document 4).
硬質皮膜の被覆手段にＰＶＤを採用することは、基材に掛かる熱的負荷が小さいことから有効である。しかしながら、ＰＶＤで被覆した皮膜中には上記のドロップレットやパーティクル等が少なからず存在する。これらに起因したボイドやポア、ピンホール状の隙間欠陥が、特に基材にまで貫通すると、その部位では腐食が激しく進行し、早期の孔食やガス焼付きの要因となる。そのため、特許文献１の硬質皮膜は、それが耐食性に優れたＣｒＮであっても、皮膜中に上記の欠陥が存在することで本来の耐食性が得られないという課題がある。また、特許文献２の硬質皮膜は、そのＣｒＮ皮膜上にＴｉＮ皮膜を被覆したとしても、ＣｒＮ皮膜中に一旦形成された欠陥はそのまま覆い隠すことが難しい。 Adopting PVD as the coating means for the hard coating is effective because the thermal load applied to the substrate is small. However, the droplets and particles described above are not a little present in the film coated with PVD. When voids, pores, or pinhole-like gap defects due to these penetrate into the base material in particular, the corrosion progresses violently at the site, which causes early pitting corrosion and gas seizure. Therefore, even if it is CrN which was excellent in corrosion resistance, the hard film of patent document 1 has the subject that original corrosion resistance cannot be obtained because the said defect exists in a film. Moreover, even if the hard film of patent document 2 coat | covers the TiN film | membrane on the CrN film | membrane, it is difficult to cover the defect once formed in the CrN film | membrane as it is.
そこで、特許文献１や２の硬質皮膜に対しては、その表面に特許文献３のイオンエッチングを導入することが考えられる。しかし、イオンエッチングによっても、耐食性の向上に効果を発揮する程のドロップレット等の除去することは必ずしも容易ではない。そして、特許文献４のサンドブラストを適用すれば、これは皮膜表面に粒子を吹付けるという、専ら研削作用によった粗加工方法であることから、耐食性の向上にとって好ましい平滑な表面が得られ難い。 Therefore, it is conceivable to introduce ion etching of Patent Document 3 on the surface of the hard film of Patent Documents 1 and 2. However, even with ion etching, it is not always easy to remove droplets and the like that are effective in improving corrosion resistance. And if the sandblasting of patent document 4 is applied, since this is a rough processing method exclusively by the grinding action of spraying particles on the surface of the film, it is difficult to obtain a smooth surface preferable for improving corrosion resistance.
本発明の目的は上記の課題に鑑み、硬質皮膜の耐食性を向上した被覆物品の製造方法および被覆物品を提供することである。 In view of the above problems, an object of the present invention is to provide a method for producing a coated article and a coated article having improved corrosion resistance of a hard film.
本発明者は、皮膜の中間に平滑な界面を形成してドロップレット等の不純物の影響を遮断することが、耐食性の向上に重要であることを知見し、ドロップレット等の除去後の皮膜表面には耐食性の向上に好ましい形態があることも突きとめた。そして、皮膜への負荷が大きい使用環境下でも十分な耐食性を保つためには、基材と皮膜の密着性がより重要となり、被覆前の基材表面を窒化処理することが有効であることを見出し、本発明に到達した。 The present inventor has found that it is important to improve the corrosion resistance by forming a smooth interface in the middle of the film to block the influence of impurities such as droplets, and the surface of the film after removing the droplets and the like It has also been found that there is a preferred form for improving corrosion resistance. And in order to maintain sufficient corrosion resistance even in a use environment where the load on the film is large, the adhesion between the substrate and the film becomes more important, and it is effective to nitride the substrate surface before coating. The headline, the present invention has been reached.
すなわち本発明は、物品の基材表面にＰＶＤによって硬質皮膜を被覆した被覆物品の製造方法であって、前記硬質皮膜は、前記基材表面に被覆された第１の硬質皮膜と、その直上に被覆された第２の硬質皮膜の少なくとも２層以上からなり、前記基材表面は窒化処理されており、前記第２の硬質皮膜を被覆する前に、前記第１の硬質皮膜の表面を算術平均粗さＲａは０．０５μｍ以下、かつ最大高さＲｚは１．００μｍ以下となるように研磨することを特徴とする耐食性に優れた被覆物品の製造方法である。 That is, the present invention is a method for manufacturing a coated article in which a base film surface of an article is coated with a hard film by PVD, and the hard film includes a first hard film coated on the surface of the base material, It consists of at least two layers of the coated second hard film, the surface of the base material is nitrided, and before coating the second hard film, the surface of the first hard film is arithmetically averaged It is a method for producing a coated article excellent in corrosion resistance, characterized by polishing so that the roughness Ra is 0.05 μm or less and the maximum height Rz is 1.00 μm or less.
第１および／または第２の硬質皮膜は、クロム系窒化物であることが好ましい。そして更には、これらの硬質皮膜は、Ｍｏ、Ｎｂ、Ｗ、Ｓｉ、Ｂから選択される１種または２種以上の元素を含むクロム系窒化物であることが好ましい。 The first and / or second hard coating is preferably a chromium nitride. Furthermore, these hard coatings are preferably chromium nitrides containing one or more elements selected from Mo, Nb, W, Si, and B.
第１および／または第２の硬質皮膜は、成分組成が（Ｃｒ１−ａＸａ）Ｎで示されるクロム系窒化物であって（但し、下付き数字はＣｒと元素Ｘの原子比を表す）、ＸはＳｉ、Ｂから選択される１種または２種の元素であり、ａは０．０１〜０．１０であることが好ましい。 The first and / or second hard coating is a chromium-based nitride having a component composition of (Cr 1−a X a ) N (provided that the subscript number represents the atomic ratio of Cr to element X) ), X is one or two elements selected from Si and B, and a is preferably from 0.01 to 0.10.
また、物理蒸着法はアークイオンプレーティング法であることが望ましく、これらによる被覆物品は、射出成形用部品または金型であることが好ましい。 The physical vapor deposition method is preferably an arc ion plating method, and the coated article formed by these is preferably an injection molding part or a mold.
また、本発明の被覆物品は、上述した本発明の製造方法で得られるものであり、物品の基材表面に物理蒸着法によって硬質皮膜を被覆した被覆物品であって、前記基材表面は窒化層を有し、前記硬質皮膜は、前記窒化処理された基材表面に被覆された後に研磨された第１の硬質皮膜と、前記第１の硬質皮膜の直上に被覆された第２の硬質皮膜の少なくとも２層以上からなり、かつ前記第１の硬質皮膜と前記第２の硬質皮膜の界面をまたぐ長径１μｍ以上のドロップレットが断面組織観察における界面長さ５０μｍあたり２個未満（０を含む）である耐食性に優れた被覆物品である。 The coated article of the present invention is obtained by the above-described production method of the present invention, and is a coated article in which a hard film is coated on the surface of the substrate of the article by physical vapor deposition, and the surface of the substrate is nitrided A first hard film that is polished after being coated on the surface of the substrate that has been nitrided, and a second hard film that is coated directly on the first hard film. Less than 2 droplets (including 0) per 50 μm of interface length in cross-sectional structure observation, having at least two layers of and having a major axis of 1 μm or more straddling the interface between the first hard film and the second hard film It is a coated article having excellent corrosion resistance.
第１および／または第２の硬質皮膜は、クロム系窒化物であることが好ましい。そして更には、これらの硬質皮膜は、Ｍｏ、Ｎｂ、Ｗ、Ｓｉ、Ｂから選択される１種または２種以上の元素を含むクロム系窒化物であることが好ましい。また、第１および／または第２の硬質皮膜は、成分組成が（Ｃｒ１−ａＸａ）Ｎで示されるクロム系窒化物であって（但し、下付き数字はＣｒと元素Ｘの原子比を表す）、ＸはＳｉ、Ｂから選択される１種または２種の元素であり、ａは０．０１〜０．１０であることが好ましい。
また、第２の硬質皮膜の表面が研磨されていることが好ましい。また、物理蒸着法はアークイオンプレーティング法であることが望ましく、本発明の被覆物品は、射出成形用部品または金型であることが好ましい。
The first and / or second hard coating is preferably a chromium nitride. Furthermore, these hard coatings are preferably chromium nitrides containing one or more elements selected from Mo, Nb, W, Si, and B. The first and / or second hard coating is a chromium-based nitride whose component composition is (Cr 1−a X a ) N (provided that the subscript number is the atomic ratio of Cr to element X) X represents one or two elements selected from Si and B, and a is preferably 0.01 to 0.10.
The surface of the second hard film is preferably polished. The physical vapor deposition method is preferably an arc ion plating method, and the coated article of the present invention is preferably an injection molding part or a mold.
本発明の製造方法によれば、その硬質皮膜を被覆途中の第１の硬質皮膜の表面を最適に研磨することで、第２皮膜を被覆後には基材に向けて貫通する欠陥が非常に少なく調整できた被覆物品となる。また、皮膜の密着性も優れるため、負荷が大きな使用環境下でも優れた耐食性を発揮させることができる。よって本発明は、腐食環境に曝される射出成形用部品、工具、金型の製造に有用である。 According to the manufacturing method of the present invention, the surface of the first hard film that is being coated with the hard film is optimally polished so that there are very few defects penetrating toward the substrate after the second film is coated. The coated article can be adjusted. Moreover, since the adhesion of the film is also excellent, excellent corrosion resistance can be exhibited even under a use environment where the load is large. Therefore, the present invention is useful for manufacturing injection molding parts, tools, and molds that are exposed to corrosive environments.
本発明者は、皮膜の腐食を抑制する手法を鋭意研究する中で、第１硬質皮膜上のドロップレットやパーティクル等を起点にする凹凸から、局所的な腐食が引き起こされること突き止めた。そして、硬質皮膜を第１の硬質皮膜と第２の硬質皮膜に別けて複層被覆することに加えて、その、第１の硬質皮膜を被覆した後にそのまま続けて第２の硬質皮膜を被覆するのではなく、まず、第１の硬質皮膜を研磨して平滑化し、その上に第２の硬質皮膜を被覆することで皮膜全体の耐食性を大幅に改善出来ることを見出し、更には耐食性に優れる皮膜構造をも見出した。そして、被覆前には基材表面を窒化処理することで、皮膜への負荷が大きな使用環境下でも皮膜の密着強度が十分に保たれ、優れた耐食性を持続的に発揮できることを見出した。以下、その詳細を説明する。 The present inventor has intensively studied a method for suppressing the corrosion of the film, and has found out that local corrosion is caused by irregularities starting from droplets or particles on the first hard film. Then, in addition to the hard coating being divided into the first hard coating and the second hard coating, the second hard coating is continuously applied after the first hard coating is coated. Instead, the first hard film is polished and smoothed, and then the second hard film is coated thereon to find that the corrosion resistance of the entire film can be greatly improved. Furthermore, the film has excellent corrosion resistance. I also found the structure. And it discovered that the adhesion strength of a film | membrane was fully maintained even in the use environment where the load to a film | membrane is large by nitriding the base-material surface before coating | covering, and the outstanding corrosion resistance can be exhibited continuously. Details will be described below.
本発明の製造方法において、第１の硬質皮膜上を研磨するのは、ドロップレットやパーティクル等を除去して、平滑な表面状態にするためである。これによって、第２の硬質皮膜の被覆時には、第１の硬質皮膜表面の微細な凹凸を埋めるように被覆され、皮膜全体の耐食性を大幅に改善できる。
本発明の製造方法で被覆される第１の硬質皮膜の表面は、具体的にはＪＩＳ−Ｂ−０６０２−２００１に定められる表面粗さにおける算術平均粗さＲａは０．０５μｍ以下とし、かつ最大高さＲｚは１．００μｍ以下に研磨することで耐食性を向上させる。より好ましくは、Ｒｚは０．５μｍ以下に研磨する。
In the production method of the present invention, the reason why the first hard film is polished is to remove droplets, particles, and the like to obtain a smooth surface state. Thus, when the second hard film is coated, the first hard film surface is coated so as to fill fine irregularities, and the corrosion resistance of the entire film can be greatly improved.
Specifically, the surface of the first hard film to be coated by the production method of the present invention has an arithmetic average roughness Ra of 0.05 μm or less at the surface roughness specified in JIS-B-0602-2001, and a maximum. The corrosion resistance is improved by polishing the height Rz to 1.00 μm or less. More preferably, Rz is polished to 0.5 μm or less.
第１の硬質皮膜の表面をこの好ましい表面粗さにするには、イオンエッチングやサンドブラスト（ショットブラスト）等の研削作用によるものでは、皮膜表面の平滑化が不十分であり、皮膜の耐食性に劣る場合がある。そこで、ドロップレットやパーティクル等を確実に除去し、且つ、平滑な表面状態にするためには、次のような研磨方法を採用することが好ましい。
（１）機械部品の仕上げを行う場合に部品表面が正しい均一面を持つように精密に仕上げていく研磨手段であって、例えば定盤を使用して、その硬質皮膜との間にラップ剤を挟み、硬質皮膜を摺動させて研磨する方法
（２）ダイヤモンドペースト等の研磨剤を保持した研磨布で硬質皮膜の表面を磨く方法
（３）ダイヤモンド粒子と湿度を持った研磨剤を用い、基材に被覆された皮膜に高速に滑走させて、発生する摩擦力によって磨く、いわゆるエアロラップ（エアロラップは株式会社ヤマシタワークス殿の登録商標である）等による研磨方法
（４）エアーを使用せずに弾性と粘着性を持った研磨剤を噴射することで磨く、いわゆるスマップ（ＳＭＡＰ）（合資会社亀井鉄工所製の鏡面ショットマシンである）等による研磨方法
更に、これらの処理後には３μｍ以下のダイヤモンドペースト磨きをすることで、より好ましい平滑化が実現できる。
また、耐食性を向上させるために、第２の硬質皮膜の表面上も同様の研磨方法で平滑化し、Ｒａは０．０５μｍ以下とし、かつ最大高さＲｚは１．００μｍ以下にすることが好ましい。
In order to make the surface of the first hard coating have this preferable surface roughness, the surface of the coating is not sufficiently smoothed by the grinding action such as ion etching or sand blasting (shot blasting), and the corrosion resistance of the coating is poor. There is a case. Therefore, in order to reliably remove droplets and particles and to obtain a smooth surface state, it is preferable to employ the following polishing method.
(1) A polishing means that precisely finishes the surface of the part to have a correct uniform surface when finishing machine parts. For example, using a surface plate, a lapping agent is placed between the hard film and the hard film. (2) A method of polishing the surface of a hard film with a polishing cloth holding a polishing agent such as diamond paste. (3) A polishing agent having diamond particles and humidity is used. Polishing method by so-called aero wrap (Aero wrap is a registered trademark of Yamashita Towers Co., Ltd.) etc. that slides at high speed on the film covered with the material and polishes by the generated frictional force (4) Without using air Polishing method by spraying an abrasive with elasticity and adhesion to the surface, so-called SMAP (mirror surface shot machine manufactured by Kamei Iron Works) etc. More smoothing can be realized by polishing diamond paste of 3 μm or less after the treatment.
In order to improve the corrosion resistance, it is preferable that the surface of the second hard film is smoothed by the same polishing method, Ra is 0.05 μm or less, and the maximum height Rz is 1.00 μm or less.
硬質皮膜の被覆前には基材表面を窒化処理することで、基材と硬質皮膜の密着性が高まるため皮膜剥離が発生せず、負荷が大きな使用環境下でも、耐食性が極めて優れたものとなる。
窒化処理は、窒化層の深さが２００μｍ以下になるように、処理時間と温度を制御することが好ましい。これよりも窒化層が厚くなると、基材自体の耐食性が著しく低下するので、好ましくない。より好ましくは１５０μｍ以下である。
By nitriding the substrate surface before coating the hard coating, the adhesion between the substrate and the hard coating is increased, so that the coating does not peel off, and the corrosion resistance is extremely excellent even under heavy load environments. Become.
In the nitriding treatment, it is preferable to control the treatment time and temperature so that the depth of the nitrided layer is 200 μm or less. If the nitride layer is thicker than this, the corrosion resistance of the substrate itself is remarkably lowered, which is not preferable. More preferably, it is 150 μm or less.
本発明の硬質皮膜の総膜厚は、１μｍ〜１０μｍとすることが好ましい。これよりも、薄くなると耐食性が十分でない場合がある。これよりも厚くなると、皮膜剥離が発生し易く、耐食性が低下し易い。より好ましくは２μｍ以上および／または８μｍ以下である。また、第１硬質皮膜と第２硬質皮膜は同程度であることが好ましい。 The total film thickness of the hard coating of the present invention is preferably 1 μm to 10 μm. If it is thinner than this, the corrosion resistance may not be sufficient. If it is thicker than this, film peeling tends to occur and corrosion resistance tends to decrease. More preferably, it is 2 μm or more and / or 8 μm or less. Moreover, it is preferable that a 1st hard film and a 2nd hard film are comparable.
上記製造方法により、物品の基材表面にＰＶＤによって硬質皮膜を被覆した被覆物品であって、基材表面は窒化層を有し、前記硬質皮膜は、前記窒化層を有した基材表面に被覆された第１の硬質皮膜と、研磨された前記第１の硬質皮膜の直上に被覆された第２の硬質皮膜の少なくとも２層以上からなり、
かつ前記第１の硬質皮膜と前記第２の硬質皮膜の界面をまたぐ長径１μｍ以上のドロップレットが断面組織観察における界面長さ５０μｍあたり１個以下（０を含む）である耐食性に優れた本発明の被覆物品を得ることができる。
粗大なドロップレットが存在すると、その上面に堆積する皮膜との間に空隙等の内部欠陥が形成される。この欠陥を通して腐食が進行する。従い硬質皮膜の形成工程の中間で研磨処理を行い平滑化することは、硬質皮膜の深さ方向の内部欠陥の連通を遮断するのに有効である。
本発明では、平滑化された界面を第１の硬質皮膜と第２の硬質皮膜の界面をまたぐ長径１μｍ以上のドロップレットが断面組織観察における界面長さ５０μｍあたりの平均個数が１個以下（０を含む）として規定した。これは長径１μｍ未満のドロップレットおよび長径１μｍ以上であっても５０μｍあたり２個未満の存在は耐食性に大きな影響はないためである。
By the said manufacturing method, it is the coated article which coat | covered the hard film with PVD on the base-material surface of an article | item, Comprising: The base-material surface has a nitride layer, and the said hard film coat | covers the base-material surface which has the said nitride layer A first hard film formed and at least two layers of a second hard film coated directly on the polished first hard film,
In addition, the present invention is excellent in corrosion resistance in which the number of droplets having a major diameter of 1 μm or more straddling the interface between the first hard coating and the second hard coating is 1 or less (including 0) per 50 μm of interface length in cross-sectional structure observation. Coated articles can be obtained.
When coarse droplets are present, internal defects such as voids are formed between the film deposited on the upper surface thereof. Corrosion proceeds through this defect. Accordingly, polishing and smoothing in the middle of the process of forming the hard film is effective for blocking communication of internal defects in the depth direction of the hard film.
In the present invention, the average number of droplets having a major axis of 1 μm or more straddling the smoothed interface across the interface between the first hard coating and the second hard coating is 1 or less per 50 μm interface length in cross-sectional structure observation (0 Included). This is because even if the droplet has a major axis of less than 1 μm and the major axis is 1 μm or more, the presence of less than two per 50 μm does not significantly affect the corrosion resistance.
第１および／または第２の硬質皮膜の表面粗さを平滑に調整するには、その被覆前の基材の表面粗さを、表面粗さは平均粗さＲａ０．５０μｍ以下、Ｒｚは１．００μｍ以下に研磨しておくことが好ましい。 In order to smoothly adjust the surface roughness of the first and / or second hard coating, the surface roughness of the base material before coating is the average roughness Ra of 0.50 μm or less, the Rz is 1. It is preferable to polish to 00 μm or less.
本発明の製造方法で被覆される、第１および／または第２硬質皮膜は、皮膜自体が耐食性に優れるクロム系窒化物であることが好ましい。なお、本発明においてクロム系窒化物とは、耐食性の優れるクロム量が、その金属（半金属を含む）部分において５０原子％以上あるものをいう。より好ましくは７０原子％以上である。
また、該第１および／または第２の硬質皮膜は、Ｍｏ、Ｎｂ、Ｗ、Ｓｉ、Ｂから選択される１種または２種以上の元素を含むクロム系窒化物であることが好ましい。Ｍｏ、Ｎｂ、Ｗが皮膜中へ添加されることで、硬度が向上し耐摩耗性が向上する。そして、Ｓｉ、Ｂが皮膜中に添加されることで、皮膜が微細になり高硬度になる。好ましい皮膜硬度は２０ＧＰａ以上である。そして皮膜が微細化されることで、より耐食性が向上する。
硬質皮膜に高い硬度をも付与することで、耐摩耗性の向上に加えては、摩耗腐食も抑制できるので、例えば被成形材にガラス繊維等の強化物質が添加された場合であっても、摩耗に起因する被覆物品の腐食防止に著しい効果を発揮する。
これらの効果を発揮しクロム系窒化物自体の靭性と密着性を低下させないためには、成分組成が（Ｃｒ１−ａＸａ）Ｎで示されるクロム系窒化物であって（但し、下付き数字はＣｒと元素Ｘの原子比を表す）、ＸはＳｉ、Ｂから選択される１種または２種の元素であり、ａは０．０１〜０．１０であることが好ましい。
The first and / or second hard coating that is coated by the production method of the present invention is preferably a chromium-based nitride that is excellent in corrosion resistance. In the present invention, the chromium-based nitride means that the amount of chromium having excellent corrosion resistance is 50 atomic% or more in the metal (including metalloid) portion. More preferably, it is 70 atomic% or more.
The first and / or second hard coating is preferably a chromium nitride containing one or more elements selected from Mo, Nb, W, Si, and B. By adding Mo, Nb, and W into the film, the hardness is improved and the wear resistance is improved. And Si and B are added in a film | membrane, a film | membrane becomes fine and it becomes high hardness. A preferable film hardness is 20 GPa or more. And corrosion resistance improves more because a membrane | film | coat is refined | miniaturized.
By imparting high hardness to the hard film, in addition to improving wear resistance, it is possible to suppress wear corrosion, so even when a reinforcing material such as glass fiber is added to the molding material, It has a remarkable effect in preventing corrosion of coated articles due to wear.
In order to exert these effects and not to lower the toughness and adhesion of the chromium nitride itself, the component composition is a chromium nitride represented by (Cr 1−a X a ) N (however, subscript The number represents the atomic ratio of Cr and element X), X is one or two elements selected from Si and B, and a is preferably 0.01 to 0.10.
本発明の製造方法で用いる被覆手段は、その被覆する硬質皮膜が皮膜密着性の高い物理蒸着法であることが必要である。例えばスパッタリング法やアークイオンプレーティング法があるが、その中でも特に皮膜密着性が高いアークイオンプレーティング法が好ましい。 The coating means used in the production method of the present invention requires that the hard film to be coated is a physical vapor deposition method with high film adhesion. For example, there are a sputtering method and an arc ion plating method. Among them, the arc ion plating method having particularly high film adhesion is preferable.
耐食性の優れる本発明の被覆物品は、プラスチックやゴムの成形に用いられる射出成型用部品や金型への適用が特に有効である。 The coated article of the present invention having excellent corrosion resistance is particularly effective when applied to injection molding parts and molds used for molding plastics and rubber.
硬質皮膜の被覆手段には、アークイオンプレーティング装置を用いた。成膜チャンバー中には、各種のターゲット（カソード）を装着する複数のアーク放電式蒸発源と、基材を搭載するための基材ホルダーを有する。基材ホルダーの下には回転機構があり、基材は基材ホルダーを介して、自転かつ公転する。そして、基材が各種のターゲットに対峙したときに、該ターゲットによる皮膜が被覆される。なお、本実施例で使用したターゲットは、粉末冶金法で作製した金属ターゲットである。 An arc ion plating apparatus was used as the means for coating the hard film. The film forming chamber has a plurality of arc discharge evaporation sources on which various targets (cathodes) are mounted, and a substrate holder for mounting the substrate. There is a rotation mechanism under the substrate holder, and the substrate rotates and revolves through the substrate holder. And when a base material opposes various targets, the membrane | film | coat by this target is coat | covered. Note that the target used in this example is a metal target produced by a powder metallurgy method.
蒸発源には、硬質皮膜の金属成分を構成するターゲットと、金属イオンエッチング用のターゲットを適宜装着した。基材には５７〜６０ＨＲＣに調質したＪＩＳ−ＳＫＤ１１相当鋼材を用いた。試料Ｎｏ．１〜８、１１の基材は、窒素雰囲気で処理時間と温度を変えて窒化処理をした。
基材に第１皮膜被覆する前の表面粗さは平均粗さＲａ０．０１μｍ、Ｒｚは０．０７μｍに研磨した。これを脱脂洗浄して、基材ホルダーに固定した。そして、チャンバーに設置された加熱用ヒーターにより、基材を５００℃付近に加熱し、５０分間保持した。次に、Ａｒガスを導入し、基材には−６００Ｖのバイアス電圧を印加して、３０分間のプラズマクリーニング処理（Ａｒイオンエッチング）を行った。続いて、基材には−８００Ｖのバイアス電圧を印加して、約２０分間のＴｉ金属イオンエッチングを行った。
A target constituting the metal component of the hard film and a target for metal ion etching were appropriately attached to the evaporation source. A JIS-SKD11 equivalent steel material tempered to 57-60 HRC was used as the base material. Sample No. The base materials 1 to 8 and 11 were subjected to nitriding treatment by changing the treatment time and temperature in a nitrogen atmosphere.
The surface roughness before coating the first film on the substrate was polished to an average roughness Ra of 0.01 μm and Rz of 0.07 μm. This was degreased and washed and fixed to a substrate holder. And the base material was heated to about 500 degreeC with the heater for heating installed in the chamber, and was hold | maintained for 50 minutes. Next, Ar gas was introduced, a bias voltage of −600 V was applied to the substrate, and a plasma cleaning process (Ar ion etching) was performed for 30 minutes. Subsequently, a bias voltage of −800 V was applied to the substrate, and Ti metal ion etching was performed for about 20 minutes.
各試料、基材に−１５０Ｖのバイアス電圧を印加して、基材温度５００℃、反応ガス圧力３．０Ｐａの条件で、硬質皮膜を成膜した。
本発明例である試料Ｎｏ．１〜８は、第１の硬質皮膜としてＣｒＮを約３μｍ被覆後には、基材をチャンバーから取り出して、その途中表面を研磨する手段として、株式会社ヤマシタワークス製エアロラップ装置(ＡＥＲＯ ＬＡＰ ＹＴ‐３００)使用）を使用して表面処理を行った。その後、１μｍのダイヤモンドペーストにてポリッシング研磨し、更に続いては、合資会社亀井鉄工所製鏡面ショットマシンＳＭＡＰ-II型を使用して表面処理を行った。そして、脱脂洗浄を行った後には、再びチャンバー内に戻して、ＡｒイオンエッチングおよびＴｉ金属イオンエッチングを行い、第２の硬質皮膜を被覆した。
試料Ｎｏ．１〜４は、第２の硬質皮膜として、（９２％Ｃｒ３％Ｓｉ５％Ｂ）Ｎを約３μｍ被覆した（数値は原子比）。
試料Ｎｏ．５〜８は、第２の硬質皮膜として、ＣｒＮを約３μｍ被覆した。
試料Ｎｏ．９は、ＣｒＮを約３μｍ被覆後、研磨せずにそのままＴｉＮを約３μｍ被覆した。
試料Ｎｏ．１０〜１３は、研磨せずに、単層の皮膜を約６μｍ被覆した。
そして、各試料の最表面をダイヤモンドペーストで磨いた。
A hard film was formed under the conditions of a substrate temperature of 500 ° C. and a reaction gas pressure of 3.0 Pa by applying a bias voltage of −150 V to each sample and substrate.
Sample No. which is an example of the present invention. Nos. 1 to 8 are coated with about 3 μm of CrN as the first hard film, and after removing the base material from the chamber and polishing the surface on the way, an aero lapping device (AERO LAP YT-300 manufactured by Yamashita Towers Co., Ltd.) is used. ) Use) to perform the surface treatment. Thereafter, polishing was polished with a 1 μm diamond paste, and further, surface treatment was performed using a mirror surface shot machine SMAP-II manufactured by Kamei Iron Works. And after performing degreasing washing | cleaning, it returned in the chamber again, Ar ion etching and Ti metal ion etching were performed, and the 2nd hard film was coat | covered.
Sample No. 1-4 covered about 3 μm of (92% Cr3% Si5% B) N as the second hard film (the numerical value is an atomic ratio).
Sample No. Nos. 5 to 8 were coated with about 3 μm of CrN as the second hard film.
Sample No. No. 9 was coated with about 3 μm of TiN without being polished after being coated with about 3 μm of CrN.
Sample No. Nos. 10 to 13 were coated with a monolayer film of about 6 μm without polishing.
Then, the outermost surface of each sample was polished with diamond paste.
そして、これらの試料について、その第１および第２の硬質皮膜の表面粗さ測定、硬度測定、スクラッチ試験、耐食性の評価を行った。各評価試験方法を以下に示す。 And about these samples, the surface roughness measurement of the 1st and 2nd hard film, hardness measurement, a scratch test, and corrosion resistance evaluation were performed. Each evaluation test method is shown below.
（表面粗さ測定）
ＪＩＳ−Ｂ−０６０２−２００１に従って、粗さ曲線より算術平均粗さＲａと最大高さＲｚを測定した。測定条件は、評価長さ：４．０ｍｍ、測定速度：０．３ｍｍ／ｓ、カットオフ値：０．８ｍｍとした。
(Surface roughness measurement)
According to JIS-B-0602-2001, the arithmetic average roughness Ra and the maximum height Rz were measured from the roughness curve. The measurement conditions were as follows: evaluation length: 4.0 mm, measurement speed: 0.3 mm / s, cut-off value: 0.8 mm.
（耐食性評価試験）
実際の射出成形中に発生するハロゲンガス、硫化ガスなどの腐食ガスを模擬して、試料を１０％硫酸水溶液中に１０時間浸漬する試験を実施した。前記水溶液の温度は５０℃とし、ＪＩＳ−Ｇ−０５９１−２００７に従って、試験片の被覆された面以外はマスキングした。そして、浸漬後には、その腐食による減量を記録するとともに、表面に現れる孔食（ピット）の観察を行った。試験面に対する腐食の面積率は、顕微鏡写真（倍率：８倍）にて評価した。
孔食数の評価は、その顕微鏡写真に現れる孔食(ピット)のうち、０．８ｍｍ以上のものをＡクラス、０．２〜０．８ｍｍ未満のものをＢクラスとして、それぞれのサイズの孔食数を測定した。顕微鏡写真から腐食面の面積率を求めた。孔食評価結果を表１に示す。
(Corrosion resistance evaluation test)
A test was conducted in which a sample was immersed in a 10% sulfuric acid aqueous solution for 10 hours while simulating a corrosive gas such as a halogen gas and a sulfide gas generated during actual injection molding. The temperature of the aqueous solution was 50 ° C., and the surfaces other than the coated surface of the test piece were masked according to JIS-G-0591-2007. After immersion, the weight loss due to the corrosion was recorded, and pitting corrosion (pits) appearing on the surface was observed. The area ratio of corrosion on the test surface was evaluated by a micrograph (magnification: 8 times).
The number of pitting corrosion is evaluated as follows. Of the pitting corrosion (pits) appearing in the micrograph, those with a size of 0.8 mm or more are class A and those with a size of 0.2 to less than 0.8 mm are class B. The number of meals was measured. The area ratio of the corroded surface was determined from the micrograph. The pitting corrosion evaluation results are shown in Table 1.
（硬度測定）
エリオニクス製のナノインデンテーション装置を用い、硬質皮膜の硬度を測定した。皮膜の硬度を測定するために、試験片を５度傾けて鏡面研磨した。基材の影響を除去するために皮膜の研磨面内で最大押し込み深さが各層厚の略１／１０以下となる領域を選定した。このとき１／５程度でも基材の影響がないことを確認した。
押込み荷重４９ｍＮ、最大荷重保持時間１秒、荷重負荷後の除去速度０．４９ｍＮ／秒の測定条件で１０点測定し、最大と最小の値を除いた８点の平均値から求めた。
本測定方法における皮膜硬度は、圧子の微細形状、測定時の温度、湿度、試料の表面状態に左右され易く、得られる数値は必ずしもビッカース硬さと一致しない。そのため、標準試料である溶融石英を測定した。そのときの溶融石英の皮膜硬さは１１ＧＰａであり、本測定結果をもとに相対比較することができる。測定結果を表１に示す。
(Hardness measurement)
The hardness of the hard coating was measured using an Elionix nanoindentation device. In order to measure the hardness of the film, the test piece was tilted 5 degrees and mirror-polished. In order to remove the influence of the base material, a region where the maximum indentation depth is approximately 1/10 or less of the thickness of each layer in the polished surface of the film was selected. At this time, it was confirmed that there was no influence of the substrate even at about 1/5.
Ten points were measured under the measurement conditions of an indentation load of 49 mN, a maximum load holding time of 1 second, and a removal rate after loading of 0.49 mN / second, and the average value of 8 points excluding the maximum and minimum values was obtained.
The film hardness in this measurement method is easily influenced by the fine shape of the indenter, the temperature, humidity at the time of measurement, and the surface condition of the sample, and the obtained numerical values do not necessarily match the Vickers hardness. Therefore, the fused quartz which is a standard sample was measured. The film hardness of the fused quartz at that time is 11 GPa, and a relative comparison can be made based on this measurement result. The measurement results are shown in Table 1.
（スクラッチ試験）
皮膜の密着性を評価するために、ＣＳＭ社製スクラッチ試験機（ＲＥＶＥＴＥＳＴ）を用いて剥離荷重を測定した。
測定条件は、測定荷重：４０〜２００Ｎ、荷重スピード：９９．２５Ｎ／ｍｉｎ、スクラッチスピード：１０ｍｍ／ｍｉｎ、スクラッチ距離：１６ｍｍ、ＡＥ感度：５、圧子：ロックウェル、ダイヤモンド、先端半径：２００μｍ、ハードウェア設定：Ｆｎコンタクト０．９Ｎ、Ｆｎスピード：５Ｎ／ｓ、Ｆｎ除去スピード ：１０Ｎ／ｓ、アプローチスピード：２％／ｓとした。
皮膜の剥離荷重は、最表層の初期チッピング発生荷重をＡ荷重とし、スクラッチ痕底部の膜が基材から全て剥がれた時（スクラッチ痕底部の基材が完全に露出した時）の荷重をＢ荷重とした。測定結果を表１に示す。
(Scratch test)
In order to evaluate the adhesion of the film, the peel load was measured using a scratch tester (REVETEST) manufactured by CSM.
Measurement conditions are: measurement load: 40 to 200 N, load speed: 99.25 N / min, scratch speed: 10 mm / min, scratch distance: 16 mm, AE sensitivity: 5, indenter: Rockwell, diamond, tip radius: 200 μm, hard Wear setting: Fn contact 0.9 N, Fn speed: 5 N / s, Fn removal speed: 10 N / s, approach speed: 2% / s.
For the peeling load of the film, the initial chipping load of the outermost layer is A load, and the load when the film at the bottom of the scratch mark is peeled off from the base material (when the base material at the bottom of the scratch mark is completely exposed) is B load. It was. The measurement results are shown in Table 1.
耐食性評価試験後の皮膜表面については、図１〜３に示す（図中において、球状に確認される薄色部が孔食である）。 About the film | membrane surface after a corrosion-resistance evaluation test, it shows in FIGS. 1-3 (in the figure, the light-colored part confirmed spherically is pitting corrosion).
表１より、本発明の製造方法を満たした硬質皮膜は、密着性および耐食性に優れていることが分かる。途中で平滑研磨していない従来例は本発明例と比べて耐食性が低下した。本発明例の耐食性評価試験後の皮膜表面は、図１、２の通り、孔食が確認されなかった。 From Table 1, it can be seen that the hard coating satisfying the production method of the present invention is excellent in adhesion and corrosion resistance. Corrosion resistance of the conventional example that was not smooth-polished during the process was lower than that of the inventive example. As shown in FIGS. 1 and 2, pitting corrosion was not confirmed on the surface of the film after the corrosion resistance evaluation test of the inventive example.
本発明例の試料について、耐食性向上の要因を探るため複数視野の断面観察を行った。
また、本発明例のすべての試料では、１μｍ以上のドロップレットは界面長さ５０μｍあたり１個以下であった。また、本発明例では界面に存在するドロップレット自体が、除去されるか、研磨されて界面をまたぐことのない平滑面を構成していることが確認された。
本発明例では、このような粗大なドロップレットの影響を研磨処理により排除できており、これにより耐食性が向上していることがわかる。
With respect to the sample of the present invention example, cross-sectional observation of a plurality of visual fields was performed in order to find a factor for improving the corrosion resistance.
Moreover, in all the samples of the present invention example, the number of droplets of 1 μm or more was 1 or less per 50 μm of interface length. Further, it was confirmed that the droplets present at the interface in the present invention example were removed or polished to constitute a smooth surface that did not cross the interface.
In the example of the present invention, it can be seen that the influence of such coarse droplets can be eliminated by the polishing treatment, thereby improving the corrosion resistance.
本発明は、プラスチックやゴムを成形する金型や工具、射出成形用部品の他には、例えば皮膜成分等を調整して、被成形材との離型性をも付与することで、ＭＩＭ（メタルインジェクションモールディング）用金型や、そして各種の機械部品にも適用し得る。
In the present invention, in addition to molds and tools for molding plastics and rubber, and injection molding parts, for example, a film component is adjusted to provide release properties from a molding material. It can be applied to metal injection molding dies and various machine parts.
Claims (14)
前記基材表面は窒化処理されており、前記第２の硬質皮膜を被覆する前に、前記第１の硬質皮膜の表面を算術平均粗さＲａは０．０５μｍ以下、かつ最大高さＲｚは１．００μｍ以下となるように研磨することを特徴とする耐食性に優れた被覆物品の製造方法。 A method for producing a coated article in which a base film surface of an article is coated with a hard film by a physical vapor deposition method, wherein the hard film is coated with a first hard film coated on the surface of the base material and directly thereon. Consisting of at least two layers of the second hard coating,
The surface of the base material is nitrided, and before coating the second hard film, the surface of the first hard film has an arithmetic average roughness Ra of 0.05 μm or less and a maximum height Rz of 1. A method for producing a coated article excellent in corrosion resistance, characterized by polishing to 0.000 μm or less.
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| WO2016027832A1 (en) * | 2014-08-20 | 2016-02-25 | 日立金属株式会社 | Method for manufacturing coated mold for die casting |
| JP2018168397A (en) * | 2017-03-29 | 2018-11-01 | アイシン精機株式会社 | Method of manufacturing amorphous carbon coating, amorphous carbon coating, and cutting tool |
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| JP2000178720A (en) * | 1998-12-14 | 2000-06-27 | Sumitomo Metal Mining Co Ltd | Material with solid lubrication film |
| JP2001011603A (en) * | 1999-07-02 | 2001-01-16 | Sumitomo Metal Mining Co Ltd | Member with laminated film and laminated film |
| JP2008080353A (en) * | 2006-09-27 | 2008-04-10 | Hitachi Metals Ltd | Member for casting |
| JP2010058135A (en) * | 2008-09-02 | 2010-03-18 | Hitachi Metals Ltd | Die casting coated die and method of manufacturing the same |
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| JP2000178720A (en) * | 1998-12-14 | 2000-06-27 | Sumitomo Metal Mining Co Ltd | Material with solid lubrication film |
| JP2001011603A (en) * | 1999-07-02 | 2001-01-16 | Sumitomo Metal Mining Co Ltd | Member with laminated film and laminated film |
| JP2008080353A (en) * | 2006-09-27 | 2008-04-10 | Hitachi Metals Ltd | Member for casting |
| JP2010058135A (en) * | 2008-09-02 | 2010-03-18 | Hitachi Metals Ltd | Die casting coated die and method of manufacturing the same |
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| WO2016027832A1 (en) * | 2014-08-20 | 2016-02-25 | 日立金属株式会社 | Method for manufacturing coated mold for die casting |
| JPWO2016027832A1 (en) * | 2014-08-20 | 2017-04-27 | 日立金属株式会社 | Manufacturing method of die casting coating mold |
| KR101862526B1 (en) | 2014-08-20 | 2018-05-29 | 히타치 긴조쿠 가부시키가이샤 | Method for manufacturing coated mold for die casting |
| JP2018168397A (en) * | 2017-03-29 | 2018-11-01 | アイシン精機株式会社 | Method of manufacturing amorphous carbon coating, amorphous carbon coating, and cutting tool |
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