JP2003096577A - Surface hardening material and method of manufacturing the same - Google Patents
Surface hardening material and method of manufacturing the sameInfo
- Publication number
- JP2003096577A JP2003096577A JP2001288391A JP2001288391A JP2003096577A JP 2003096577 A JP2003096577 A JP 2003096577A JP 2001288391 A JP2001288391 A JP 2001288391A JP 2001288391 A JP2001288391 A JP 2001288391A JP 2003096577 A JP2003096577 A JP 2003096577A
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- JP
- Japan
- Prior art keywords
- thin film
- carbon
- corrosion resistance
- substrate
- hardening material
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、基板表面にＦｅ、
Ｃｒ、Ｎｉを主成分とする合金の硬質薄膜を有する材料
とその製造方法に関するものである。TECHNICAL FIELD The present invention relates to Fe on the surface of a substrate,
The present invention relates to a material having a hard thin film of an alloy containing Cr and Ni as main components and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】腕時計、ネックレス、ピアスなどの装飾
用外装部品は主にステンレス鋼が主流となっており、そ
の高耐食性、良好な加工性、また白色の色合いにより、
低価格品から高価格品にいたるまで広く用いられてい
る。また他の素材としてはチタンおよびチタン合金、ア
ルミニウムおよびアルミニウム合金、黄銅などの金属材
料からなっているが、これらはいずれも軟質材料である
ことや、低耐食性のために様々な表面処理が行われてい
る。2. Description of the Related Art Stainless steel is mainly used for decorative exterior parts such as wristwatches, necklaces and piercings. Due to its high corrosion resistance, good workability and white tint,
Widely used from low-priced products to high-priced products. Other materials include metal materials such as titanium and titanium alloys, aluminum and aluminum alloys, brass, etc., all of which are soft materials and are subjected to various surface treatments for low corrosion resistance. ing.
【０００３】チタンまたはチタン合金では、窒化処理、
ガラスコーティング等の表面硬化処理を施しているが、
チタンそのものの色の特性上、ステンレス鋼より暗い色
合いとなっている。そこで、白色の色合いを出すために
ＰｔまたはＰｄなどの貴金属の薄膜をコーティングして
いるが、これらの薄膜硬度は小さく、耐傷性に劣る欠点
を持っている。With titanium or titanium alloys, nitriding treatment,
It has been given a surface hardening treatment such as glass coating,
Due to the color characteristics of titanium itself, it is a darker shade than stainless steel. Therefore, a thin film of a noble metal such as Pt or Pd is coated in order to obtain a white tint, but the thin film hardness of these is small, and it has a defect of poor scratch resistance.
【０００４】また、アルミニウムおよびアルミニウム合
金、および黄銅は、耐食性を保つために各種コーティン
グ法により薄膜が形成される。薄膜を形成する方法に
は、陽極酸化、湿式メッキ、乾式メッキの手法がある。
陽極酸化はアルミニウムおよびアルミニウム合金におい
てなされ、表面の硬度は上昇するが耐食性は向上しな
い。また、黄銅に対してはニッケルメッキ、ニッケルリ
ンメッキなど各種湿式金属メッキがなされ、耐食性には
効果があり、ある程度の硬質化も可能であるが、ステン
レス鋼とは異なった色合いとなり、また、アレルギー性
材料であることから、人の肌に触れる時計外装部品には
適用ができない。また、乾式メッキにはイオンプレーテ
ィング、スパッタリング、ＣＶＤなどの手法による窒化
チタン膜、炭化チタン膜などがあり硬質薄膜として使用
されているが、ステンレス鋼のような白色の色合いを有
する硬質薄膜はできなかった。In addition, aluminum, aluminum alloys, and brass are formed into thin films by various coating methods in order to maintain corrosion resistance. Methods for forming a thin film include anodic oxidation, wet plating, and dry plating.
Anodization is performed on aluminum and aluminum alloys, the surface hardness increases but the corrosion resistance does not improve. In addition, brass is plated with various wet metals such as nickel plating and nickel phosphorous plating, which has an effect on corrosion resistance and can be hardened to some extent, but it has a different color from stainless steel, and it has allergies. Since it is a conductive material, it cannot be applied to watch exterior parts that come into contact with human skin. Further, dry plating includes titanium nitride film, titanium carbide film, etc. by a method such as ion plating, sputtering, and CVD and is used as a hard thin film, but a hard thin film with a white tint such as stainless steel can be formed. There wasn't.
【０００５】[0005]
【発明が解決しようとする課題】以上説明したように、
本発明の目的は、ステンレス鋼のような白色の色合いを
有する高耐食性である硬質合金薄膜を有する材料、およ
びその製造方法を提供することである。As described above,
An object of the present invention is to provide a material having a hard-corrosion hard alloy thin film having a white tint such as stainless steel, and a method for manufacturing the same.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、Ｆｅ、Ｃｒ、Ｎｉを主成分とするステンレス鋼合金
薄膜の種々の改質法を検討した結果、上記薄膜に炭素を
固溶させることにより、ステンレス鋼の色合いを保ち、
さらに耐食性を損なうことなく硬質化することを見出し
た。すなわち、Ｆｅ、Ｃｒ、Ｎｉを主成分とするステン
レス鋼合金薄膜に炭素が固溶することにより炭素が結晶
格子間に入り、その結果生じる高い歪みエネルギーのた
めに強度が上昇し硬化するものである。一般に大気中で
の３００℃以上の高温熱処理では、平衡論的に炭素はク
ロムと反応し炭化クロムを生じ、結果的にステンレス合
金中でクロムが枯渇して耐食性が劣化する。本発明で
は、このような炭化クロムが生成しない条件をつくり出
すことに成功したものである。In order to solve the above problems, as a result of studying various reforming methods of a stainless steel alloy thin film containing Fe, Cr and Ni as main components, carbon is dissolved in the above thin film. By keeping the color of stainless steel,
Further, they have found that they harden without impairing the corrosion resistance. That is, when carbon is dissolved as a solid solution in a stainless steel alloy thin film containing Fe, Cr, and Ni as main components, carbon enters between crystal lattices, and the resulting high strain energy increases the strength and causes hardening. . Generally, in a high temperature heat treatment at 300 ° C. or higher in the atmosphere, carbon reacts with chromium in a balanced manner to form chromium carbide, and as a result, chromium is depleted in the stainless alloy and corrosion resistance deteriorates. The present invention has succeeded in creating such a condition that chromium carbide is not generated.
【０００７】すなわち、本発明の表面硬化材料は、基板
表面にＦｅ、Ｃｒ、Ｎｉを主成分とする合金の薄膜を有
する材料であって、その薄膜中に炭素が固溶したことを
特徴とする。That is, the surface-hardened material of the present invention is a material having a thin film of an alloy containing Fe, Cr, and Ni as the main components on the surface of the substrate, and carbon is solid-dissolved in the thin film. .
【０００８】さらにその薄膜中の炭素の固溶量は、０．
１〜２．０ｗｔ％であることが好ましい。Further, the solid solution amount of carbon in the thin film is 0.
It is preferably 1 to 2.0 wt%.
【０００９】また、本発明の表面硬化材料の製造方法
は、上記表面硬化材料を得るために、基板にＦｅ、Ｃ
ｒ、Ｎｉ基からなる合金の薄膜を析出させる第１の工程
と、炭素を固溶させる第２の工程の連続した工程を有す
ることを特徴とする。Further, in the method for producing a surface-hardened material according to the present invention, in order to obtain the above-mentioned surface-hardened material, Fe and C are applied to the substrate.
The method is characterized by having a continuous step of a first step of depositing a thin film of an alloy composed of r and Ni bases, and a second step of solid solution of carbon.
【００１０】さらに説明すれば、第１の工程では、金
属、ガラス、セラミック等の基板上に蒸着、スパッタリ
ング、ＣＶＤ等の方法によりＦｅ、Ｃｒ、Ｎｉ基からな
るいわゆるステンレス鋼の組成からなる合金の薄膜を所
定の膜厚で析出させる。この場合の膜厚は任意の厚さで
よい。第２の工程では、第１の工程後装置内雰囲気を大
気に戻すことなく、直ちに、基板加熱温度が３００〜５
００℃、真空度が０．１〜１０Ｐａ、ＣＯのガスの場合
は濃度が１０００〜３０００ｐｐｍ、ＣＯ 2のガスの場
合は濃度が２０００〜４０００ｐｐｍの条件下で所定時
間処理することを特徴とするものであり、炭素が合金薄
膜中に拡散し、０．１〜２．０ｗｔ％の炭素を固溶した
表面硬化材料を製造することが可能となった。この第１
の工程と第２の工程は連続した工程からなることを特徴
とする。More specifically, in the first step, an alloy having a composition of so-called stainless steel composed of Fe, Cr, and Ni bases is formed on a substrate of metal, glass, ceramic or the like by a method such as vapor deposition, sputtering or CVD. A thin film is deposited with a predetermined film thickness. In this case, the film thickness may be any thickness. In the second step, immediately after the first step, the substrate heating temperature is 300 to 5 without returning the atmosphere in the apparatus to the atmosphere.
Characterized by treating at a temperature of 00 ° C., a vacuum degree of 0.1 to 10 Pa, a CO gas concentration of 1000 to 3000 ppm, and a CO 2 gas concentration of 2000 to 4000 ppm for a predetermined time. That is, the carbon diffused into the alloy thin film, and it became possible to manufacture a surface-hardened material in which 0.1 to 2.0 wt% of carbon was solid-dissolved. This first
And the second step are characterized by comprising consecutive steps.
【００１１】したがって本発明により、上述の表面硬化
材料を有することを特徴とする時計部品等の装飾部品の
提供が可能となった。Therefore, according to the present invention, it is possible to provide a decorative part such as a watch part which is characterized by having the above-mentioned surface-hardened material.
【００１２】（作用）大気中での平衡論では、炭素は合
金薄膜表面の酸化クロムからなる不動態膜の存在により
炭素表面から内部に拡散できないが、本発明では第１の
工程と第２の工程が連続して行われ、しかも第１の工程
後合金膜が大気に触れることがないために不動態膜が生
成されず、しかも減圧下での合金薄膜とＣＯまたはＣＯ
2の炭素との反応であることから炭素の拡散が容易に進
むものである。また、ＣＯ、ＣＯ 2の還元作用により表
面の酸化は抑えられ、また比較的低温度での反応である
ことから炭化クロムの析出なしに炭素が固溶するもので
ある。(Action) In equilibrium theory in the atmosphere, carbon cannot diffuse inward from the carbon surface due to the presence of the passivation film made of chromium oxide on the surface of the alloy thin film, but in the present invention, the first step and the second step The steps are continuously performed, and since the alloy film does not come into contact with the atmosphere after the first step, a passivation film is not formed, and the alloy thin film and CO or CO under reduced pressure are not formed.
Since it is a reaction with carbon of 2 , the diffusion of carbon easily proceeds. Further, the oxidation of the surface is suppressed by the reducing action of CO and CO 2 , and since the reaction is performed at a relatively low temperature, carbon is solid-dissolved without precipitation of chromium carbide.
【００１３】ここで、基板加熱温度が３００℃未満では
十分な硬度が得られず、５００℃を越えると耐食性が劣
化する可能性がある。より好ましくは３５０〜４５０℃
が安定した条件である。ＣＯの濃度が１０００ｐｐｍ未
満では硬度上昇がなく、３０００ｐｐｍを越えると硬度
は上昇するが耐食性が劣化する可能性がある。また、Ｃ
Ｏ 2の濃度が２０００ｐｐｍ未満では硬度上昇がなく、
４０００ｐｐｍを越えると硬度は上昇するが耐食性が劣
化する可能性がある。また好ましくは１〜５００Ｐａの
減圧下で処理するのが好ましい。なお、ＣＯの方がＣＯ
2よりも比較的低濃度で炭素の拡散が進行するのは、Ｃ
ＯがＣＯ 2よりも活性なためである。If the substrate heating temperature is lower than 300 ° C., sufficient hardness cannot be obtained, and if it exceeds 500 ° C., corrosion resistance may deteriorate. More preferably 350-450 ° C
Is a stable condition. If the CO concentration is less than 1000 ppm, the hardness does not increase, and if it exceeds 3000 ppm, the hardness increases but the corrosion resistance may deteriorate. Also, C
When the concentration of O 2 is less than 2000 ppm, there is no increase in hardness,
If it exceeds 4000 ppm, the hardness increases but the corrosion resistance may deteriorate. Further, it is preferable to perform the treatment under a reduced pressure of 1 to 500 Pa. In addition, CO is CO
Carbon diffusion progresses at a relatively lower concentration than 2
This is because O is more active than CO 2 .
【００１４】また、炭素の固溶量が、０．１ｗｔ％〜
２．０ｗｔ％の範囲にあることが好ましい。炭素の固溶
量が２．０ｗｔ％を越えると耐食性が劣化する可能性が
ある。これは炭化クロムの生成によるものである。炭素
の固溶量が、０．１ｗｔ％未満であると、硬度上昇が見
られない可能性がある。これは、十分に炭素の固溶が進
行しないためである。すなわち、炭素濃度が０．１ｗｔ
％未満では硬度が５００Ｈｖ以下となる可能性がある。Further, the solid solution amount of carbon is 0.1 wt% to
It is preferably in the range of 2.0 wt%. If the solid solution amount of carbon exceeds 2.0 wt%, the corrosion resistance may deteriorate. This is due to the formation of chromium carbide. If the solid solution amount of carbon is less than 0.1 wt%, the hardness may not increase. This is because solid solution of carbon does not proceed sufficiently. That is, the carbon concentration is 0.1 wt.
If it is less than%, the hardness may be 500 Hv or less.
【００１５】本発明により、ステンレス鋼の色合いで高
耐食性の表面硬化材料が得られ、さらにこの表面硬化材
料を有した腕時計ケース、腕時計バンド、ネックレス、
ピアス等の装飾外装外装部品を得ることが可能となっ
た。また、基体が黄銅、アルミニウム等の比較的低価格
の外装であっても、ステンレス鋼の色合いを持つ高級感
を具備した、しかも耐傷性があって美しさを持続できる
装飾用外装製品が得られるようになった。According to the present invention, a surface-hardened material having a color tone of stainless steel and high corrosion resistance can be obtained, and further, a wristwatch case, a wristwatch band, a necklace, and the like, which have the surface-hardened material.
It became possible to obtain decorative exterior parts such as piercings. Further, even if the base is a relatively low-cost exterior such as brass or aluminum, it is possible to obtain a decorative exterior product having a high-grade feeling with a tint of stainless steel, and having scratch resistance and maintaining beauty. It became so.
【００１６】[0016]
【発明の実施の形態】以下、本発明を実施するための最
良の形態における表面硬化材料とその製造方法および、
この表面硬化材料を有する装飾用外装部品とその製造方
法について説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a surface-hardened material in the best mode for carrying out the present invention, a method for producing the same, and
A decorative exterior part having the surface-hardened material and a method for manufacturing the same will be described.
【００１７】まず、本発明における高耐食性の表面硬化
材料の定義について説明する。まず、高耐食性とは、Ｃ
ＡＳＳ試験（ＪＩＳ）で腐食が発生しないことが合格の
基準である。次に、ステンレス鋼の色合いの定義に関し
ては、その基準として、ＣＩＥ表色系の色差（Ｌ＊ａ＊
ｂ＊）が２．５以下を基準とした。さらに、被膜の硬度
は、時計外装として耐傷性が合格となるビッカース硬度
５００（Ｈｖ）以上を合格の基準とした。なおビッカー
ス硬度測定条件として、荷重は５ｇｆとした。First, the definition of the surface-hardened material having high corrosion resistance in the present invention will be described. First, high corrosion resistance means C
The criterion for passing is that corrosion does not occur in the ASS test (JIS). Next, regarding the definition of the tint of stainless steel, as a reference, the color difference (L * a *) of the CIE color system is used.
b *) was 2.5 or less as a standard. Furthermore, the hardness of the coating was determined to be Vickers hardness of 500 (Hv) or more, which is acceptable for the scratch resistance of the timepiece exterior, as a criterion of acceptance. The load was 5 gf as the Vickers hardness measurement condition.
【００１８】本発明において、基板としては金属、ガラ
ス、セラミック等、材料は５００℃までの処理温度に耐
えられるものであれば任意でよい。In the present invention, the substrate may be made of any material such as metal, glass and ceramics, as long as it can withstand a processing temperature of up to 500.degree.
【００１９】また、第１の工程で得られる合金薄膜はＦ
ｅ、Ｃｒ、Ｎｉを主成分とするステンレス鋼合金の組成
を有する合金薄膜であり、ＪＩＳで定められたフェライ
ト系、オーステナイト系、マルテンサイト系等任意に選
択できる。好ましくは、耐食性の高いオーステナイト系
ステンレス鋼の合金組成が選ばれる。さらに成膜方法
も、蒸着、イオンプレーティング、スパッタリング、Ｃ
ＶＤ等任意でよいが、合金成分をある程度制御するため
には、スパッタリングが好ましい。The alloy thin film obtained in the first step is F
It is an alloy thin film having a composition of a stainless steel alloy containing e, Cr, and Ni as main components, and can be arbitrarily selected from ferrite type, austenite type, martensite type, etc. defined by JIS. Preferably, an alloy composition of austenitic stainless steel having high corrosion resistance is selected. Further, the film forming method is vapor deposition, ion plating, sputtering, C
VD or the like may be used, but sputtering is preferred in order to control the alloy components to some extent.
【００２０】また、第２の工程では、第１の工程後一旦
１０ - 4Ｐａまで排気後、ランプヒータにて基板を２０
０〜４００℃に加熱し、所定の温度に到達したら、Ａｒ
またはＨｅ、Ｎ2等の不活性ガス中に１０００〜３００
０ｐｐｍ含有するＣＯガスを導入し、真空度が１〜５０
０Ｐａになるように排気側で制御し、所定時間処理す
る。なお、ＣＯ 2ガスの場合は、濃度は２０００〜４０
００ｐｐｍとする。ここで処理時間は任意でよいが、３
〜５時間が実用的な表面硬化材料が得られる条件となる[0020] In the second step, once 10 after the first step - after evacuated to 4 Pa, the substrate at the lamp heater 20
After heating to 0-400 ℃ and reaching the specified temperature, Ar
Or 1000 to 300 in an inert gas such as He or N 2.
CO gas containing 0 ppm was introduced, and the degree of vacuum was 1 to 50.
The exhaust side controls so that the pressure becomes 0 Pa, and the process is performed for a predetermined time. In the case of CO 2 gas, the concentration is 2000-40
It is set to 00 ppm. Here, the processing time may be arbitrary, but 3
~ 5 hours is a condition for obtaining a practical surface-hardening material
【００２１】（実施例１）基板は、１０ｍｍ×１５ｍｍ
×０．３ｍｍの黄銅の板状テストピースの片面を鏡面研
磨したのち、有機洗浄を施した。第１の工程ではこの基
板を真空装置内に配置し、真空装置内を１×１０ - 4Ｐ
ａまで排気した後Ａｒガスを導入し、圧力０．５Ｐａに
保った雰囲気で、７０％Ｆｅ−２０％Ｃｒ−１０％Ｎｉ
（ｗｔ％）合金ターゲットを使用し、ＤＣマグネトロン
スパッタリング法により膜厚が約３μｍのＦｅ，Ｃｒ，
Ｎｉからなる合金薄膜を得た。ここで、得られた合金薄
膜の組成はＥＰＭＡで定量分析を行ったところ、７３．
７％Ｆｅ−１８．５％Ｃｒ−７．８％Ｎｉ（ｗｔ％）で
あった。Example 1 A substrate is 10 mm × 15 mm
One side of a 0.3 mm brass plate-shaped test piece was mirror-polished and then subjected to organic cleaning. In the first step, this substrate is placed in a vacuum device and the inside of the vacuum device is 1 × 10 −4 P
After exhausting to a, Ar gas was introduced, and 70% Fe-20% Cr-10% Ni was introduced in an atmosphere kept at a pressure of 0.5 Pa.
(Wt%) alloy target is used, and DC, magnetron sputtering method is used to form Fe, Cr with a film thickness of about 3 μm,
An alloy thin film made of Ni was obtained. The composition of the obtained alloy thin film was quantitatively analyzed by EPMA.
It was 7% Fe-18.5% Cr-7.8% Ni (wt%).
【００２２】第２の工程では、第１の工程後直ちに真空
度を５×１０ - 4Ｐａまで排気し、ランプヒータによ
り基板を２００〜６００℃に加熱した。その後、Ａｒに
７００〜３５００ｐｐｍ含有したＣＯガスを導入し圧力
が５０Ｐａになるように排気側で制御し５時間保持し炭
素の拡散を行った。その後、基板温度が１００℃以下に
なるように冷却し基板を取り出し、ＥＰＭＡによるＣの
定量分析、ビッカース硬度、耐食性試験としてＣＡＳＳ
試験（４８時間）を行った。これらの結果を表１に示
す。これより、本発明による条件のもと（太線内）で
は、硬度が５００Ｈｖ以上で耐食性良好な被膜が得ら
れ、色彩色差計での測定では、いずれも色差（Ｌ＊ａ＊
ｂ＊）は２．５以下でありステンレスの色調を有するも
のであった。また、第１の工程後取り出し、第２の工程
を通さない比較例としての試料は、硬度２３０Ｈｖで、
耐食性は良好（○）であった。なお、基板加熱温度が３
００℃未満では硬度が上がらず、５００℃を越えると耐
食性が不良となった。また、ＣＯの濃度が１０００ｐｐ
ｍ未満では硬度が５００Ｈｖに到達しなく、３０００ｐ
ｐｍを越えると耐食性が不良となった。これは、炭素の
固溶量と対応し、炭素の固溶量が０．１ｗｔ％未満では
硬度が５００Ｈｖ以下であり、２．０ｗｔ％を越えると
耐食性が不良となった。[0022] In a second step, immediately vacuum after the first step 5 × 10 - was evacuated to 4 Pa, the substrate was heated to 200 to 600 ° C. by a lamp heater. After that, CO gas containing 700 to 3500 ppm in Ar was introduced, the pressure was controlled to 50 Pa on the exhaust side, and the gas was held for 5 hours to diffuse carbon. After that, the substrate is cooled so that the substrate temperature is 100 ° C. or lower, the substrate is taken out, and the quantitative analysis of C by EPMA, Vickers hardness, and CASS as a corrosion resistance test are performed.
A test (48 hours) was conducted. The results are shown in Table 1. From this, under the conditions according to the present invention (inside the thick line), a coating having a hardness of 500 Hv or more and good corrosion resistance can be obtained, and any color difference (L * a *) was measured by a colorimeter.
b *) was 2.5 or less and had a color tone of stainless steel. Further, a sample as a comparative example which is taken out after the first step and not passed through the second step has a hardness of 230 Hv,
The corrosion resistance was good (○). The substrate heating temperature is 3
If it is less than 00 ° C, the hardness does not increase, and if it exceeds 500 ° C, the corrosion resistance becomes poor. The CO concentration is 1000 pp
If it is less than m, the hardness does not reach 500 Hv and 3000 p
If it exceeds pm, the corrosion resistance becomes poor. This corresponds to the solid solution amount of carbon, and when the solid solution amount of carbon is less than 0.1 wt%, the hardness is 500 Hv or less, and when it exceeds 2.0 wt%, the corrosion resistance becomes poor.
【００２３】ここで、黄銅のテストピースの代わりに、
時計外装用ケース、バンド、またピアス、ネックレス等
への応用も同様に行うことが可能で、表面硬化材料を有
する装飾用外装部品品の提供ができるようになった。な
お部品材質としては、黄銅、チタン、チタン合金、アル
ミニウム、アルミニウム合金等金属材料はもちろん、セ
ラミック、ガラスなどに適用可能である。Here, instead of the brass test piece,
The invention can be applied to the case for external case of watch, band, piercing, necklace, etc. in the same manner, and it has become possible to provide the decorative exterior part product having the surface hardened material. In addition, as the material of the parts, not only metal materials such as brass, titanium, titanium alloy, aluminum and aluminum alloy but also ceramic, glass and the like can be applied.
【００２４】[0024]
【表１】 [Table 1]
【００２５】（実施例２）ＣＯ 2の濃度以外は実施例１
と同等の方法で行った。基板は、１０ｍｍ×１５ｍｍ×
０．３ｍｍの黄銅の板状テストピースの片面を鏡面研磨
したのち、有機洗浄を施した。第１の工程ではこの基板
を真空装置内に配置し、真空装置内を１×１０ - 4Ｐ
ａまで排気した後Ａｒガスを導入し、圧力０．５Ｐａに
保った雰囲気で、７０％Ｆｅ−２０％Ｃｒ−１０％Ｎｉ
（ｗｔ％）合金ターゲットを使用し、ＤＣマグネトロン
スパッタリング法により膜厚が約３μｍのＦｅ，Ｃｒ，
Ｎｉからなる合金薄膜を得た。ここで、得られた合金薄
膜の組成はＥＰＭＡで定量分析を行ったところ、７３．
７％Ｆｅ−１８．５％Ｃｒ−７．８％Ｎｉ（ｗｔ％）で
あった。(Example 2) Example 1 except the concentration of CO 2
The same method was used. Substrate is 10mm x 15mm x
One surface of a 0.3 mm brass plate-shaped test piece was mirror-polished and then subjected to organic cleaning. In the first step, this substrate is placed in a vacuum device and the inside of the vacuum device is 1 × 10 −4 P
After exhausting to a, Ar gas was introduced, and 70% Fe-20% Cr-10% Ni was introduced in an atmosphere kept at a pressure of 0.5 Pa.
(Wt%) alloy target is used, and DC, magnetron sputtering method is used to form Fe, Cr with a film thickness of about 3 μm,
An alloy thin film made of Ni was obtained. The composition of the obtained alloy thin film was quantitatively analyzed by EPMA.
It was 7% Fe-18.5% Cr-7.8% Ni (wt%).
【００２６】第２の工程では、第１の工程後直ちに真空
度を５×１０ - 4Ｐａまで排気し、ランプヒータによ
り基板を２００〜６００℃に加熱した。その後、Ａｒに
１０００〜５０００ｐｐｍ含有したＣＯ 2ガスを導入し
圧力が５０Ｐａになるように排気側で制御し５時間保持
し炭素の拡散を行った。その後、基板温度が１００℃以
下に冷却し基板を取り出し、ＥＰＭＡによるＣの定量分
析、ビッカース硬度、耐食性試験としてＣＡＳＳ試験
（４８時間）を行った。これらの結果を表２に示す。こ
れより、本発明による条件のもと（太線内）では、硬度
が５００Ｈｖ以上で耐食性良好な被膜が得られ、色彩色
差計での測定では、いずれも色差（Ｌ＊ａ＊ｂ＊）は
２．５以下でありステンレスの色調を有するものであっ
た。また、第１の工程後取り出し、第２の工程を通さな
い比較例としての試料は、硬度２３０Ｈｖで、耐食性は
良好（○）であった。なお、基板温度が３００℃未満で
は硬度が上がらず、５００℃を越えると耐食性が不良と
なった。また、ＣＯ 2の濃度が１０００ｐｐｍ未満では
硬度が５００Ｈｖに到達しなく、３０００ｐｐｍを越え
ると耐食性が不良となった。これは、炭素の固溶量、す
なわち炭素の濃度と対応し、炭素濃度が０．１ｗｔ％未
満では硬度が５００Ｈｖ以下であり、２．０ｗｔ％を越
えると耐食性が不良となった。[0026] In a second step, immediately vacuum after the first step 5 × 10 - was evacuated to 4 Pa, the substrate was heated to 200 to 600 ° C. by a lamp heater. After that, CO 2 gas containing 1000 to 5000 ppm of Ar was introduced, the pressure was controlled to 50 Pa on the exhaust side, and the pressure was maintained for 5 hours to diffuse carbon. Then, the substrate temperature was cooled to 100 ° C. or lower, the substrate was taken out, and a CASS test (48 hours) was performed as a quantitative analysis of C by EPMA, Vickers hardness, and corrosion resistance test. The results are shown in Table 2. From this, under the conditions according to the present invention (inside the thick line), a coating having a hardness of 500 Hv or more and good corrosion resistance was obtained, and the color difference (L * a * b *) was 2 in any measurement with a colorimeter. It was less than 0.5 and had a color tone of stainless steel. A sample as a comparative example that was taken out after the first step and not passed through the second step had a hardness of 230 Hv and good corrosion resistance (◯). When the substrate temperature was lower than 300 ° C, the hardness did not increase, and when it exceeded 500 ° C, the corrosion resistance was poor. Further, when the concentration of CO 2 is less than 1000 ppm, the hardness does not reach 500 Hv, and when it exceeds 3000 ppm, the corrosion resistance becomes poor. This corresponds to the solid solution amount of carbon, that is, the carbon concentration. When the carbon concentration is less than 0.1 wt%, the hardness is 500 Hv or less, and when it exceeds 2.0 wt%, the corrosion resistance becomes poor.
【００２７】ここで、黄銅のテストピースの代わりに、
時計外装用ケース、バンド、またピアス、ネックレス等
への応用も同様に行うことが可能で、表面硬化材料を有
する装飾用外装部品の提供ができるようになった。なお
基板、すなわち部品材質としては、黄銅、チタン、チタ
ン合金、アルミニウム、アルミニウム合金等金属材料は
もちろん、セラミック、ガラスなどに適用可能である。Here, instead of the brass test piece,
The invention can be applied to cases for watch exteriors, bands, piercings, necklaces, and the like as well, and it has become possible to provide decorative exterior parts having a surface-hardened material. It should be noted that the substrate, that is, the material of the component, can be applied not only to metal materials such as brass, titanium, titanium alloy, aluminum and aluminum alloy but also to ceramic, glass and the like.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】以上述べたように、本発明により、Ｆ
ｅ、Ｃｒ、Ｎｉを主成分とする高耐食、高硬度のステン
レス鋼組成の薄膜を有する表面硬化材料が得られ、装飾
性の高い外装部品の提供が可能となった。また、基板が
黄銅、アルミニウム等金属部材またはガラス、セラミッ
クに至るまで比較的低価格の外装であっても、ステンレ
ス鋼の色合いを持つ高級感を具備した、しかも耐傷性が
あって美しさを持続できる装飾用外装製品が得られるよ
うになった。As described above, according to the present invention, F
A surface-hardened material having a thin film of stainless steel composition having high corrosion resistance and high hardness, which contains e, Cr, and Ni as the main components, can be obtained, and it is possible to provide an exterior part with high decorativeness. In addition, even if the substrate is a relatively low-cost exterior such as brass, aluminum, or other metal members, glass, or ceramics, it has a high-grade feeling with the color tone of stainless steel, and is scratch-resistant to maintain its beauty. A decorative exterior product that can be obtained is now available.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K028 AA01 AB01 AC08 CA01 CB06 CC01 CD01 CE02 4K029 AA02 AA24 BA07 BA09 BA12 BA21 BA34 BC01 CA05 DC04 EA00 4K044 AA01 AA12 AA13 AB06 BA06 BA18 BB03 BC09 CA12 CA13 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4K028 AA01 AB01 AC08 CA01 CB06 CC01 CD01 CE02 4K029 AA02 AA24 BA07 BA09 BA12 BA21 BA34 BC01 CA05 DC04 EA00 4K044 AA01 AA12 AA13 AB06 BA06 BA18 BB03 BC09 CA12 CA13
Claims (8)
する合金の薄膜を有し、該薄膜中に炭素が固溶している
表面硬化材料。1. A surface-hardened material having a thin film of an alloy containing Fe, Cr, and Ni as a main component on the surface, and carbon being a solid solution in the thin film.
２．０ｗｔ％の範囲にあることを特徴とする請求項１に
記載の表面硬化材料。2. The solid solution amount of carbon is 0.1 wt% to
The surface-hardened material according to claim 1, which is in a range of 2.0 wt%.
分とする合金の薄膜を析出させる第１の工程と、前記薄
膜中に炭素を固溶させる第２の工程とを有する表面硬化
材料の製造方法。3. A surface hardening material comprising a first step of depositing a thin film of an alloy containing Fe, Cr and Ni as a main component on the surface of a substrate, and a second step of forming a solid solution of carbon in the thin film. Production method.
０℃〜５００℃の範囲にあることを特徴とする請求項３
に記載の表面硬化材料の製造方法。4. The substrate heating temperature in the second step is 30.
It is in the range of 0 ° C to 500 ° C.
The method for producing a surface-hardened material according to.
スを使用することを特徴とする請求項３または請求項４
に記載の表面硬化材料の製造方法。5. The CO gas is used as the atmospheric gas in the second step, according to claim 3 or 4.
The method for producing a surface-hardened material according to.
３０００ｐｐｍの範囲にあることを特徴とする請求項５
に記載の表面硬化材料の製造方法。6. The concentration of the CO gas is 1000 ppm to
6. It is in the range of 3000 ppm.
The method for producing a surface-hardened material according to.
ガスを使用することを特徴とする請求項３または請求項
４に記載の表面硬化材料の製造方法。7. The atmosphere gas used in the second step is CO 2
Gas is used, The manufacturing method of the surface hardening material of Claim 3 or Claim 4 characterized by the above-mentioned.
００ｐｐｍの範囲にあることを特徴とする請求項７に記
載の表面硬化材料の製造方法。8. The concentration of the CO 2 gas is 2000 to 40.
It is in the range of 00 ppm, The manufacturing method of the surface hardening material of Claim 7 characterized by the above-mentioned.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019530863A (en) * | 2016-09-16 | 2019-10-24 | イーストマン ケミカル カンパニー | Biosensor electrodes manufactured by physical vapor deposition |
| US11624723B2 (en) | 2016-09-16 | 2023-04-11 | Eastman Chemical Company | Biosensor electrodes prepared by physical vapor deposition |
| US11835481B2 (en) | 2016-06-15 | 2023-12-05 | Eastman Chemical Company | Physical vapor deposited biosensor components |
| US11881549B2 (en) | 2017-06-22 | 2024-01-23 | Eastman Chemical Company | Physical vapor deposited electrode for electrochemical sensors |
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|---|---|---|---|---|
| JPH07278783A (en) * | 1994-04-11 | 1995-10-24 | Nippon Steel Corp | Surface hardening method |
| JPH0971854A (en) * | 1995-06-27 | 1997-03-18 | Daido Hoxan Inc | Carbohardened watch member or ornament and production thereof |
| JP2001073110A (en) * | 1999-09-07 | 2001-03-21 | Citizen Watch Co Ltd | Outer ornament parts for watch, and their manufacture |
-
2001
- 2001-09-21 JP JP2001288391A patent/JP4777558B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278783A (en) * | 1994-04-11 | 1995-10-24 | Nippon Steel Corp | Surface hardening method |
| JPH0971854A (en) * | 1995-06-27 | 1997-03-18 | Daido Hoxan Inc | Carbohardened watch member or ornament and production thereof |
| JP2001073110A (en) * | 1999-09-07 | 2001-03-21 | Citizen Watch Co Ltd | Outer ornament parts for watch, and their manufacture |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11835481B2 (en) | 2016-06-15 | 2023-12-05 | Eastman Chemical Company | Physical vapor deposited biosensor components |
| JP2019530863A (en) * | 2016-09-16 | 2019-10-24 | イーストマン ケミカル カンパニー | Biosensor electrodes manufactured by physical vapor deposition |
| JP7111698B2 (en) | 2016-09-16 | 2022-08-02 | イーストマン ケミカル カンパニー | Biosensor electrodes fabricated by physical vapor deposition |
| US11624723B2 (en) | 2016-09-16 | 2023-04-11 | Eastman Chemical Company | Biosensor electrodes prepared by physical vapor deposition |
| US11630075B2 (en) | 2016-09-16 | 2023-04-18 | Eastman Chemical Company | Biosensor electrodes prepared by physical vapor deposition |
| US11881549B2 (en) | 2017-06-22 | 2024-01-23 | Eastman Chemical Company | Physical vapor deposited electrode for electrochemical sensors |
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