JP2004068068A - Composite material, method of manufacturing the same - Google Patents
Composite material, method of manufacturing the same Download PDFInfo
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Abstract
【課題】摺動性や耐久性に優れた銅系合金材を提供することである。特に、銅系合金材表面にＰＴＦＥや二硫化モリブデンなどの固体潤滑剤が強固に密着固定され、無給油環境下や腐食性環境下においても良好な摺動性や耐焼付性を有する銅系合金材（複合材）を提供することである。
【解決手段】例えば、過酸化物、ペルオキソ化合物、クロム酸および過マンガン酸の群の中から選ばれる一種または二種以上の化合物、更にはりん酸、硫酸、硝酸、塩酸、フッ化水素酸、ジルコンフッ酸、チタンフッ酸、チタン酸、モリブデン酸、タングステン酸、バナジン酸、ニオブ酸、及び有機キレート剤の群の中から選ばれる一種または二種以上の化合物を含む選択的化学エッチング液で銅系合金材を処理することにより、銅系合金材における銅系合金に含まれる易腐食性成分とか酸化物が選択的に除去されて該銅系合金材表面に形成された凹凸部と、
前記凹凸部が形成された銅系合金材の表面に設けられた皮膜とを具備する複合材。An object of the present invention is to provide a copper alloy material excellent in slidability and durability. In particular, a solid lubricant such as PTFE or molybdenum disulfide is firmly adhered to the surface of the copper-based alloy material and has good sliding properties and anti-seizure properties even in an oil-free environment or a corrosive environment. Material (composite material).
For example, one or more compounds selected from the group consisting of peroxides, peroxo compounds, chromic acid and permanganic acid, and phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, Copper-based alloy with a selective chemical etching solution containing one or more compounds selected from the group of zircon hydrofluoric acid, titanium hydrofluoric acid, titanic acid, molybdic acid, tungstic acid, vanadic acid, niobic acid, and organic chelating agent By treating the material, the corrosive components or oxides contained in the copper-based alloy in the copper-based alloy material are selectively removed, and uneven portions formed on the surface of the copper-based alloy material,
And a coating provided on a surface of the copper-based alloy material on which the uneven portions are formed.
Description
【０００１】
【発明の属する技術分野】
本発明は、自動車や船舶等の輸送機械、その他の一般産業機械、家電製品、ＯＡ機器、或いは建築材料や印刷等に使用される銅系合金の複合材に関する。特に、摺動性や耐食性に優れた銅系合金の複合材に関する。
【０００２】
【発明が解決しようとする課題】
銅系合金は、熱・電気伝導性が良く、又、耐食性・加工性も良好な為、建築・印刷・電機・自動車などの各種産業分野において利用されている。特に、耐食性・摺動性が良好な為、各種ギヤ、ガイドレール、自動車部品、家電部品、ポンプ、モータ、ＯＡ機器などの摺動部品に幅広く使用されている。
【０００３】
ところで、潤滑油が使用できない環境や、長期の耐久性が要求される場合には、摺動面に表面処理を施すことが行われている。
【０００４】
例えば、高耐候性や汚れ付着防止、撥水性、潤滑性に優れたフッ素樹脂系の塗膜や、耐熱性、耐磨耗性、親水性、光触媒性、遠赤外線反射機能を持つ機能性セラミック膜を設けることが提案されている。
【０００５】
しかしながら、これらの膜は、一般的に、基材である銅系合金との密着性が良くなく、耐久性に乏しい。
【０００６】
例えば、特開平５−１５７１１５号公報には、焼結銅合金中にポリアミド、ポリイミドなどの樹脂を含浸させる方法が開示されている。しかしながら、この種の樹脂は、焼結銅合金の気孔中への含浸が可能なことから、密着性が良いものの、摺動性の面ではポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素系樹脂に比較して劣っている。この為、十分な摺動性能が得られ無い。そして、ポリアミド、ポリイミドなどの樹脂に代えて潤滑性が良いフッ素系樹脂を用いた場合には、含浸し難く、密着性が良くない。すなわち、ＰＴＦＥや二硫化モリブデン等の固体潤滑剤は、耐熱性、摺動性に優れているものの、含浸や塗布が困難であり、基材である銅合金材との密着性に劣っている。
【０００７】
そこで、密着性を改善する為、銅系合金材を砂やセラミック粒子でブラストすることが考えられた。
【０００８】
しかしながら、この技術は、密着性は改善するものの、軟質な銅系合金材にブラスト粒子が刺さる為、この刺さったブラスト粒子によって相手材が摩耗し、又、基材が変形したり、更には耐焼付性や耐久性が低下すると言った新たな問題が起きる。
【０００９】
従って、本発明が解決しようとする課題は上記欠点を解決することである。
【００１０】
すなわち、摺動性や耐久性に優れた銅系合金材を提供することである。特に、銅系合金表面にＰＴＦＥや二硫化モリブデンなどの低接着性の固体潤滑剤が強固に密着固定され、無給油環境下や腐食性環境下においても良好な摺動性や耐焼付性が得られた銅系合金材（複合材）を提供することである。
【００１１】
【課題を解決するための手段】
上記の課題を解決する為の研究を鋭意押し進めて行った結果、厳しい腐食環境下では銅系合金中の亜鉛などの腐食し易い成分（易腐食性成分）が腐食して酸化生成物を作り、これによって焼き付きが速まることが判って来た。又、これを防止する為、ＰＴＦＥや二硫化モリブデンなどの固体潤滑剤を表面に塗布しても、基材である銅系合金材との密着性が悪く、十分な効果が得られないことも判って来た。
【００１２】
そこで、更なる検討を鋭意押し進めて行くうちに、過酸化物、ペルオキソ化合物、クロム酸および過マンガン酸の群の中から選ばれる一種または二種以上の化合物を含む溶液を用いて易腐食性成分や酸化生成物を選択的に除去し、この除去によって表面に凹凸を形成した場合、表面に設けられたＰＴＦＥや二硫化モリブデンなどの固体潤滑剤による皮膜が前記凹凸に喰い込み、密着性が向上し、しかも腐食性成分が少なくなることから、耐久性（耐食性）も向上していることが判って来た。
【００１３】
上記知見を基にして本発明が達成されたものである。
【００１４】
すなわち、上記の課題は、銅系合金材と、
前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が除去されて該銅系合金材表面に形成された凹凸部と、
前記凹凸部が形成された銅系合金材の上に設けられた皮膜
とを具備することを特徴とする複合材によって解決される。
【００１５】
特に、摺動性および耐食性に優れた複合材であって、
銅系合金材と、
前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が選択的に除去されて該銅系合金材表面に形成された凹凸部と、
前記凹凸部が形成された銅系合金材の上に設けられた皮膜
とを具備することを特徴とする複合材によって解決される。
【００１６】
更には、上記凹凸部が形成された銅系合金材の上で、かつ、皮膜の下に、金属リン酸塩および／または金属酸化物の層を具備する複合材によって解決される。
【００１７】
又、選択的化学エッチング液で銅系合金材を処理するＡ工程と、
前記Ａ工程の後、表面に皮膜を設けるＣ工程
とを具備することを特徴とする複合材製造方法によって解決される。
【００１８】
特に、選択的化学エッチング液で銅系合金材を処理するＡ工程と、
前記Ａ工程の後、表面に金属リン酸塩および／または金属酸化物の層を設けるＢ工程と、
前記Ｂ工程の後、表面に皮膜を設けるＣ工程
とを具備することを特徴とする複合材製造方法によって解決される。
【００１９】
本発明における銅系合金材表面の凹凸部は、選択的化学エッチング液で銅系合金材を処理することで形成される。処理液の温度や処理時間は特に限定されないが、例えば室温〜５０℃の温度で、１〜１０分程度の時間である。これによって、凹凸深さが０．０５〜１０μｍ程度、好ましくは０．５〜７μｍのものが得られる。
【００２０】
この選択的化学エッチング液としては、好ましくは過酸化物、ペルオキソ化合物、クロム酸および過マンガン酸の群の中から選ばれる一種または二種以上の化合物を含む溶液である。特に、過酸化物やペルオキソ化合物を含む水溶液である。ペルオキソ化合物としては、例えばペルオキソ硫酸、ペルオキソりん酸、ペルオキソバナジン酸、ペルオキソニオブ酸、ペルオキソタンタル酸、ペルオキソほう酸、ペルオキソチタン酸、ペルオキソタングステン酸、ペルオキソモリブデン酸、ペルオキソクロム酸などやこれらの可溶性塩が好ましい。特に、ペルオキソ硫酸やその塩である。中でも、ペルオキソ二硫酸のアンモニウム塩、ナトリウム塩、カリウム塩は特に好ましい。好ましい過酸化物は過酸化水素である。これらの水溶液における過酸化物やペルオキソ化合物等の好ましい濃度は１〜３０質量％、特に３〜２０質量％である。これは、濃度が低すぎると、易腐食性成分や酸化物の選択除去効果が小さく、逆に、濃度が高すぎると、結晶が析出し、液が不安定となるからである。
【００２１】
選択的化学エッチング液には、過酸化物あるいはペルオキソ化合物と共に、りん酸、硫酸、硝酸、塩酸、フッ化水素酸、ジルコンフッ酸、チタンフッ酸、チタン酸、モリブデン酸、タングステン酸、バナジン酸、ニオブ酸、及び有機キレート剤（銅に対してキレート効果を持つものが好ましく、例えば酒石酸、クエン酸、ＥＤＴＡ、有機ホスホン酸、フィチン酸など）の群の中から選ばれる一種または二種以上の化合物も含まれているのが好ましい。
【００２２】
好ましい組み合わせの選択的化学エッチング液としては、例えばリン酸−ペルオキソ硫酸、ペルオキソりん酸−硫酸、りん酸−過酸化水素、酒石酸−過酸化水素、りん酸−硝酸−過酸化水素、硫酸−過酸化水素などの水溶液である。
【００２３】
選択的化学エッチング液のｐＨは、特に好ましくは１〜５である。このｐＨ調整は、アンモニア水、炭酸アンモニウム、水酸化ナトリウム、炭酸ナトリウム、水酸化カリウムなどのアルカリを適宜用いることで行える。
【００２４】
本発明において、特に過酸化物やペルオキソ化合物を用いるのは、ブラスト処理による機械的な表面粗化方法や、通常の酸とかアルカリによる化学エッチングでは、易腐食性成分や酸化物の選択除去が出来ず、過酸化物やペルオキソ化合物等を用いることによって、易腐食性成分や酸化物の選択除去が効果的に出来、この選択除去された表面上に設けられた皮膜に対するアンカー効果が非常に高かったからである。
【００２５】
上記選択的化学エッチング処理の後、亜鉛、カルシウム、マグネシウム、マンガン、ニッケル、コバルト、モリブデン、タングステン、銅、錫、チタン、ジルコニウム、バナジウム、インジウム、及びクロムの群の中から選ばれる一種または二種以上の金属の化合物を含む溶液で銅系合金材を処理することが好ましい。例えば、上記金属の硫酸塩、酢酸塩、塩化物、リン酸塩、炭酸塩、若しくは水酸化物と言った金属イオン水溶液の形態、若しくは酸化物のコロイドゾルと言った形態のもので銅系合金材を処理する。これにより、選択的化学エッチングを受けて凹凸が形成されている銅系合金材の表面に、金属リン酸塩および／または金属酸化物の層が設けられる。好ましい厚さは０．１〜２μｍ、特に０．２〜１μｍである。そして、この層によって、耐食性が向上し、かつ、上層の皮膜の密着性が向上する。
【００２６】
上記処理（選択的化学エッチング処理あるいは金属リン酸塩および／または金属酸化物層形成処理）が終わった後、速やかに水洗し、銅系合金材に残存する酸を除去することは好ましい。例えば、銅系合金材に酸が残存すると、耐食性低下の原因となる。特に、超音波洗浄すると、銅系合金材表面に残存しているスマット等も除去され、より密着性に優れた表面が得られる。
【００２７】
上記水洗処理の後、アルカノールアミン等の有機アルカリ化合物を含む水溶液で処理することが好ましい。これによって、前工程における合金中に残存した酸が中和され、耐食性が向上する。かつ、この上に形成される皮膜の密着性が向上する。有機アルカリ化合物としては、分子構造中に少なくとも一つのアミノ基を有する低分子化合物が好ましい。例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンの外、モルホリンやこれらの誘導体、各種アミノ基を有するアルコキシシランが挙げられる。これらの化合物は、表面の固体潤滑性皮膜の密着性や塗料の濡れ性を高め、実用上さらに優れた効果を与える。
【００２８】
上記のようにして処理された銅系合金材の表面に皮膜、特に固体潤滑剤系皮膜が設けられる。
【００２９】
この皮膜としては、固体潤滑剤を含む塗膜がある。固体潤滑剤としては、例えばポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロパーフルオロアルキルビニルエーテル共重合体（ＴＰＡ）、グラファイト、二硫化モリブデン、二硫化タングステン、窒化ホウ素、フッ化タングステン、窒化チタン等が挙げられる。塗膜のバインダ成分としては、例えばポリエステル、ポリオレフィン、ポリウレタン、ポリアクリル、ポリアミドやポリイミド、エポキシ、更にはシリケート等の熱可塑性樹脂を適宜用いることが出来る。これらの塗料としては、例えば日本パーカライジング（株）製のＦＬ−Ｊ４６６８や川邑研究所（株）製のＥＢ３，ＬＨＦ４Ｂ等を用いることが出来る。そして、これら各種の成分を含む塗料をスプレー法、ディップ法やロールコータ法などにより塗布し、焼き付けることによって塗膜が得られる。又、粉体法や電着法を用いることも出来る。塗膜の厚みは、例えば２〜２０μｍ、特に１〜１０μｍが好ましい。
【００３０】
本発明が対象とする銅系合金材は銅合金からなるものであれば良い。好ましくは、銅含有量が２０〜９５質量％、特に５０〜９０質量％の銅合金である。その他の成分としては、腐食し易いＺｎ、若しくはＳｎ，Ｎｉ等の金属元素が含まれる。例えば、ＪＩＳ Ｃ２６００，Ｃ２６８０，Ｃ２８０１等の黄銅、Ｃ３５６０，Ｃ３７１０等の快削黄銅、Ｃ４２５０等のＳｎ含有黄銅、その他にもＣ６１４０等の青銅、Ｃ７０６０等の白銅、ＹＢｓＣ１等の黄銅鋳物、ＨＢｓＣ１，ＨＢｓＣ３等の高力黄銅鋳物、ＢＣ１，ＢＣ２，ＢＣ６等の青銅鋳物、ＰＢＣ２等のりん青銅鋳物などがある。
【００３１】
尚、選択的化学エッチング処理に先だって、脱脂洗浄などによって予め銅系合金材表面の付着油分を除去しておくことは好ましい。
【００３２】
そして、上記のようにして得られた複合材は、耐久性や耐焼付性（摺動性）が大幅に向している。
【００３３】
【発明の実施の形態】
本発明になる複合材は、銅系合金材と、前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が除去されて該銅系合金材表面に形成された凹凸部と、前記凹凸部が形成された銅系合金材の上に設けられた皮膜とを具備する。特に、摺動性および耐食性に優れた複合材であって、銅系合金材と、前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が選択的に除去されて該銅系合金材表面に形成された凹凸部と、前記凹凸部が形成された銅系合金材の上に設けられた皮膜とを具備する。更には、凹凸部が形成された銅系合金材の上で、かつ、皮膜の下に、金属リン酸塩および／または金属酸化物の層を具備する。
【００３４】
本発明になる複合材製造方法は、選択的化学エッチング液で銅系合金材を処理するＡ工程と、前記Ａ工程の後、表面に皮膜を設けるＣ工程とを具備する。特に、選択的化学エッチング液で銅系合金材を処理するＡ工程と、前記Ａ工程の後、表面に金属リン酸塩および／または金属酸化物の層を設けるＢ工程と、前記Ｂ工程の後、表面に皮膜を設けるＣ工程とを具備する。
【００３５】
本発明における銅系合金材表面の凹凸部は、選択的化学エッチング液で銅系合金材を処理（例えば、浸漬やスプレー或いはフローコート等の手法により、選択的化学エッチング液に銅系合金材を接触させる。）することで形成される。処理条件は、例えば室温〜５０℃の温度で、１〜１０分程度の時間である。これによって、凹凸深さが０．０５〜１０μｍ程度、特に０．５〜７μｍのものが得られる。
【００３６】
選択的化学エッチング液としては、好ましくは過酸化物、ペルオキソ化合物、クロム酸および過マンガン酸の群の中から選ばれる一種または二種以上の化合物を含む溶液である。特に、過酸化物やペルオキソ化合物を含む水溶液である。ペルオキソ化合物としては、例えばペルオキソ硫酸、ペルオキソりん酸、ペルオキソバナジン酸、ペルオキソニオブ酸、ペルオキソタンタル酸、ペルオキソほう酸、ペルオキソチタン酸、ペルオキソタングステン酸、ペルオキソモリブデン酸、ペルオキソクロム酸などやこれらの可溶性塩が好ましい。特に、ペルオキソ硫酸やその塩である。中でも、ペルオキソ二硫酸のアンモニウム塩、ナトリウム塩、カリウム塩は特に好ましい。好ましい過酸化物は過酸化水素である。これらの水溶液における過酸化物やペルオキソ化合物等の好ましい濃度は１〜３０質量％、特に３〜２０質量％である。選択的化学エッチング液は、好ましくは、過酸化物あるいはペルオキソ化合物と共に、りん酸、硫酸、硝酸、塩酸、フッ化水素酸、ジルコンフッ酸、チタンフッ酸、チタン酸、モリブデン酸、タングステン酸、バナジン酸、ニオブ酸、及び有機キレート剤（有機キレート剤としては特に限定されないが、銅に対してキレート効果を持つものが好ましく、例えば酒石酸、クエン酸、ＥＤＴＡ、有機ホスホン酸、フィチン酸など）の群の中から選ばれる一種または二種以上の化合物も含む。特に好ましい組み合わせの選択的化学エッチング液は、例えばリン酸−ペルオキソ硫酸、ペルオキソりん酸−硫酸、りん酸−過酸化水素、酒石酸−過酸化水素、りん酸−硝酸−過酸化水素、硫酸−過酸化水素などの水溶液である。選択的化学エッチング液のｐＨは、特に、１〜５である。このｐＨ調整は、アンモニア水、炭酸アンモニウム、水酸化ナトリウム、炭酸ナトリウム、水酸化カリウムなどのアルカリを用いて行える。尚、選択的化学エッチング液に、りん酸、硫酸、硝酸、塩酸、フッ化水素酸、ジルコンフッ酸、チタンフッ酸、チタン酸、モリブデン酸、タングステン酸、バナジン酸、ニオブ酸、及び有機キレート剤が含まれていなかった場合、工程数の増加にはなるが、選択的化学エッチング処理の後、前記の液で後処理する。
【００３７】
選択的化学エッチング処理の後、好ましくは、亜鉛、カルシウム、マグネシウム、マンガン、ニッケル、コバルト、モリブデン、タングステン、銅、錫、チタン、ジルコニウム、バナジウム、インジウム、及びクロムの群の中から選ばれる一種または二種以上の金属の化合物を含む溶液で銅系合金材を処理する。例えば、上記金属の硫酸塩、酢酸塩、塩化物、リン酸塩、炭酸塩、若しくは水酸化物と言った金属イオン（例えば、０．０２〜２質量％程度）水溶液の形態、若しくは酸化物のコロイドゾルと言った形態のもので銅系合金材を処理する。これにより、選択的化学エッチングを受けて凹凸が形成されている銅系合金材の表面に、厚さが０．１〜２μｍ、特に０．２〜１μｍの金属リン酸塩および／または金属酸化物の層が設けられる。
【００３８】
上記処理（選択的化学エッチング処理あるいは金属リン酸塩および／または金属酸化物層形成処理）が終わった後、好ましくは、速やかに水洗、特に超音波洗浄し、銅系合金材に残存する酸を除去する。
【００３９】
上記水洗処理の後、好ましくは、アルカノールアミン等の有機アルカリ化合物を含む水溶液で処理する。有機アルカリ化合物としては、分子構造中に少なくとも一つのアミノ基を有する低分子化合物が挙げられる。例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンの外、モルホリンやこれらの誘導体、各種アミノ基を有するアルコキシシランが挙げられる。
【００４０】
上記のようにして処理された銅系合金材の表面に皮膜、特に固体潤滑剤系皮膜が設けられる。この皮膜としては、固体潤滑剤を含む塗膜がある。固体潤滑剤としては、例えばＰＴＦＥ，ＴＰＡ，グラファイト、二硫化モリブデン、二硫化タングステン、窒化ホウ素、フッ化タングステン、窒化チタン等が挙げられる。塗膜のバインダ成分としては、例えばポリエステル、ポリオレフィン、ポリウレタン、ポリアクリル、ポリアミドやポリイミド、エポキシ、更にはシリケート等の熱可塑性樹脂を適宜用いることが出来る。これらの塗料としては、例えば日本パーカライジング社のＦＬ−Ｊ４６６８や川邑研究所（株）製のＥＢ３，ＬＨＦ４Ｂ等を用いることが出来る。そして、これら各種の成分を含む塗料をスプレー法、ディップ法やロールコータ法、或いは粉体法や電着法などにより塗布し、焼き付けることによって、例えば２〜２０μｍ、特に１〜１０μｍの厚さの塗膜が得られる。
【００４１】
皮膜として、めっき膜も考えられる。例えば、Ｓｎめっき、鉛めっき、Ｃｕ／Ｓｎめっき、固体潤滑剤分散ニッケルめっきなどの固体潤滑剤を含むめっきを、電気めっき、無電解めっき、又は置換めっき等の手法で、例えば２〜２０μｍ、特に１〜１０μｍの厚さ形成できる。その他にも、りん酸塩などの無機化合物皮膜も考えられる。尚、表面の皮膜は一層に限られない。例えば、めっき膜の上に固体潤滑剤塗膜を形成してものでも良い。
【００４２】
又、皮膜は潤滑性のものだけでなく、例えば着色顔料（例えば、クロム系顔料、ニッケル系顔料、亜鉛系顔料、鉄系顔料、チタン系顔料などの無機系顔料）および／または防錆顔料（例えば、クロム酸バリウム、クロム酸亜鉛、酸化亜鉛）を含む膜であっても良い。勿論、これら着色顔料および／または防錆顔料が固体潤滑剤と共に含まれたものでも良い。
【００４３】
本発明が対象とする銅系合金材は銅合金からなるものであれば良い。好ましくは、銅含有量が２０〜９５質量％、特に５０〜９０質量％の銅合金である。その他の成分としては、腐食し易いＺｎ、若しくはＳｎ，Ｎｉ等の金属元素が含まれる。例えば、ＪＩＳ Ｃ２６００，Ｃ２６８０，Ｃ２８０１等の黄銅、Ｃ３５６０，Ｃ３７１０等の快削黄銅、Ｃ４２５０等のＳｎ含有黄銅、その他にもＣ６１４０等の青銅、Ｃ７０６０等の白銅、ＹＢｓＣ１等の黄銅鋳物、ＨＢｓＣ１，ＨＢｓＣ３等の高力黄銅鋳物、ＢＣ１，ＢＣ２，ＢＣ６等の青銅鋳物、ＰＢＣ２等のりん青銅鋳物などがある。
【００４４】
以下、具体的な実施例を比較例と共に挙げて説明する。
【実施例】
尚、実施例１，４，７，９及び比較例１の銅系合金材は黄銅系合金：Ｃ２６００（Ｃｕ：７０％，Ｚｎ：３０％）であり、実施例２，３，５，６，８及び比較例２の銅系合金材は青銅鋳物合金ＢＣ−６（Ｃｕ：８５％，Ｚｎ：５％，Ｓｎ：５％，Ｐｂ：５％）である。そして、これらの銅系合金材を切断し、機械加工して試験片を作製し、この試験片をアルカリ脱脂剤（ＦＣ−３１５：日本パーカライジング（株）製）を使用して濃度２０ｇ／ｌ，６０℃で２分間脱脂、水洗した。そして、実施例では下記に示す選択的化学エッチング処理を行った。尚、用いた試薬は和光純薬（株）製の試薬１級品であり、希釈に用いた水は脱イオン水である。
【００４５】
［実施例１］
上記の銅系合金材を、ペルオキソ二硫酸アンモニウム（濃度１０質量％）水溶液に２７℃で１８０秒間浸漬し、そして流水で洗浄した。
【００４６】
この後、日本パーカライジング（株）製のＦＬ−Ｊ４６６８（主成分はＰＴＦＥ）を乾燥厚が３μｍとなるようにスプレーガンで塗布し、２００℃で焼き付けた。
【００４７】
［実施例２］
上記の銅系合金材を、過酸化水素（濃度０．５質量％）と硫酸（濃度５質量％）とを含む水溶液に２７℃で６０秒間浸漬し、そして流水で洗浄した。
【００４８】
この後、川邑研究所（株）製ＬＨＦ４Ｂ（主成分はＰＴＦＥ）を乾燥膜厚が４μｍとなるようスプレーガンで塗布し、２００℃で焼き付けた。
【００４９】
［実施例３］
上記の銅系合金材を、ペルオキソリン酸ナトリウム（濃度５質量％）とリン酸（１０質量％）とを含む水溶液に２７℃で１２０秒間浸漬し、そして流水で洗浄した。
【００５０】
この後、川邑研究所（株）製ＬＨＦ４Ｂ（主成分はＰＴＦＥ）を乾燥膜厚が４μｍとなるようスプレーガンで塗布し、２００℃で焼き付けた。
【００５１】
［実施例４］
上記の銅系合金材を、過酸化水素（濃度２質量％）とリン酸（濃度８質量％）とを含む水溶液に２７℃で３００秒間浸漬し、そして流水で洗浄した。
【００５２】
次いで、リン酸（５質量％）と硫酸ニッケル（２質量％）とを含む水溶液に４５℃で６０秒間浸漬し、そして超音波（２５ＫＨｚ×３０秒）水洗した。
【００５３】
この後、日本パーカライジング（株）製のＦＬ−Ｊ４６６８（主成分はＰＴＦＥ）を乾燥厚が３μｍとなるようにスプレーガンで塗布し、２００℃で焼き付けた。
【００５４】
［実施例５］
上記の銅系合金材を、過酸化水素（濃度０．８質量％）とジルコンフッ酸（濃度２質量％）とを含む水溶液に２７℃で２４０秒間浸漬し、そして流水で洗浄した。
【００５５】
次いで、りん酸（濃度１０質量％）と硝酸亜鉛（濃度２質量％）と硝酸カルシウム（濃度１質量％）とを含む水溶液に４５℃で６０秒間浸漬し、そして水洗した。
【００５６】
この後、川邑研究所（株）製ＬＨＦ４Ｂ（主成分はＰＴＦＥ）を乾燥膜厚が４μｍとなるようスプレーガンで塗布し、２００℃で焼き付けた。
【００５７】
［実施例６］
上記の銅系合金材を、バナジン酸（濃度５質量％）と過酸化水素（濃度２質量％）とを含む水溶液に２７℃で１８０秒間浸漬し、そして流水で洗浄した。
【００５８】
次いで、モノエタノールアミン（濃度０．５質量％）水溶液中に１５秒間浸漬し、引き上げてから１２０℃で１０秒間乾燥した。
【００５９】
この後、川邑研究所（株）製ＥＢ−３（主成分は二硫化モリブデン）を乾燥膜厚が３μｍとなるよう塗布した。
【００６０】
［実施例７］
上記の銅系合金材を、フッ化水素酸（濃度５質量％）と過酸化水素（濃度１質量％）とを含む水溶液に２７℃で３００秒間浸漬し、そして流水で洗浄した。
【００６１】
次いで、クロム酸（濃度３質量％）と硝酸（濃度０．５質量％）とを含む水溶液に４５℃で６０秒間浸漬し、そして水洗した。
【００６２】
次いで、トリエタノールアミン（濃度０．５質量％）水溶液中に１５秒間浸漬し、引き上げてから１２０℃で１０秒間乾燥した。
【００６３】
この後、日本パーカライジング（株）製のＦＬ−Ｊ４６６８（主成分はＰＴＦＥ）を乾燥厚が３μｍとなるようにスプレーガンで塗布し、２００℃で焼き付けた。
【００６４】
［実施例８］
上記の銅系合金材を、ペルオキソ二硫酸カリウム（濃度５質量％）と酒石酸（濃度５質量％）とを含む水溶液に２７℃で１８０秒間浸漬し、そして流水で洗浄した。
【００６５】
次いで、リン酸（濃度５質量％）と水酸化マグネシウム（濃度２質量％）とを含む水溶液に４５℃で６０秒間浸漬し、そして超音波（２５ＫＨｚ×３０秒）水洗した。
【００６６】
次いで、γ−アミノプロピルトリメトキシシラン（濃度１質量％）水溶液中に１５秒間浸漬し、引き上げてから１２０℃で１０秒間乾燥した。
【００６７】
この後、日本パーカライジング（株）製のＦＬ−Ｊ４６６８（主成分はＰＴＦＥ）を乾燥厚が３μｍとなるようにスプレーガンで塗布し、２００℃で焼き付けた。
【００６８】
［実施例９］
上記の銅系合金材を、過マンガン酸（濃度５質量％）とリン酸（濃度３質量％）とを含む水溶液に２７℃で２４０秒間浸漬し、そして流水で洗浄した。
【００６９】
次いで、ジルコンフッ酸（濃度２質量％）と硝酸ジルコニウム（濃度２質量％）とを含む水溶液に４５℃で６０秒間浸漬し、そして超音波（２５ＫＨｚ×３０秒）水洗した。
【００７０】
次いで、モノエタノールアミン（濃度０．５質量％）とジエタノールアミン（濃度０．５質量％）とを含む水溶液中に１５秒間浸漬し、引き上げてから１２０℃で１０秒間乾燥した。
【００７１】
この後、川邑研究所（株）製ＥＢ−３（主成分は二硫化モリブデン）を乾燥膜厚が３μｍとなるよう塗布した。
【００７２】
［比較例１］
上記の銅系合金材に何らの処理も施さないで、日本パーカライジング（株）製のＦＬ−Ｊ４６６８（主成分はＰＴＦＥ）を乾燥厚が３μｍとなるようにスプレーガンで塗布し、２００℃で焼き付けた。
【００７３】
［比較例２］
上記の銅系合金材を、硫酸（濃度１５質量％）水溶液に２７℃で２４０秒間浸漬し、そして流水で洗浄した。
【００７４】
この後、川邑研究所（株）製ＥＢ−３（主成分は二硫化モリブデン）を乾燥膜厚が３μｍとなるよう塗布した。
【００７５】
［特性］
上記各例で得たものについて、潤滑膜の密着性、耐食性、摺動性を調べたので、その結果を表−１に示す。又、エッチング処理後における銅系合金材表面における凹凸性の有無（多孔質性の有無および選択的エッチングの有無）を調べたので、これについても併せて表−１に示す。
【００７６】
密着性：カッターナイフを使用し、１ｍｍ各の碁盤目を１００個カットしてセロハン粘着テープを貼り付け、引き剥がして全く剥離しなかったものを◎、３個以内のものを○、４〜２０個剥離したものを△、２０個を超えて剥離したものを×で表示した。
【００７８】
耐食性：ＪＩＳ−Ｋ５４００塩水噴霧試験法に準じて耐食性試験を行い、４８０時間錆の発生が認められなかったものを合格（○）とし、錆の発生が認められたものを不合格（△）とした。
【００７９】
摺動性：ＳＲＶ摩擦磨耗試験機を使用し、焼き付きが発生するまでの荷重（Ｎ）が５０００Ｎ以上のものを◎、４０００〜５０００Ｎのものを○、２０００〜４０００Ｎのものを△、２０００Ｎ未満のものを×で表示した。荷重は５０Ｎ／ｍｉｎの速度でステップアップし、振動数が５０Ｈｚ、振幅が２ｍｍ、相手剤として１０ｍｍφのＳＵＪ−２製鋼球を使用した。尚、潤滑剤は使用しなかった。
【００８０】
銅系合金材表面の特性：化学エッチング後の表面における多孔質性の有無は、日本電子（株）製の走査型電子顕微鏡を用いて凹凸性を調べた。又、化学エッチング後の表面を（株）島津製作所製のＸＰＳ（Ｘ線光電子分光分析装置）を用いて表面分析し、選択的エッチングが行われているか否かを調べた。
【００８１】
これによれば、本発明になる複合材は、選択的化学エッチング液による処理によって、銅系合金材における銅系合金に含まれる易腐食性成分や酸化物が除去され、銅系合金材表面に多孔質性の凹凸が形成されており、このような特徴の凹凸が形成されている為、その上に設けられた皮膜の密着性に優れており、かつ、耐食性や摺動性にも優れていることが判る。
【００８２】
尚、比較例２からも判る通り、単なるエッチングでは選択的化学エッチングが行われず、即ち多孔質性の凹凸が形成されておらず、このような表面特性を持つ基材の上に実施例と同様な皮膜が設けられても、皮膜の密着性は悪く、しかも耐食性・摺動性も劣っている。
【００８３】
【発明の効果】
ＰＴＦＥや二硫化モリブデンなどの固体潤滑剤の膜を強固に密着固定でき、無給油環境下や腐食性環境下においても良好な摺動性や耐焼付性の銅系合金材が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a copper-based alloy composite material used for transportation machines such as automobiles and ships, other general industrial machines, home appliances, OA equipment, building materials, printing, and the like. In particular, it relates to a composite material of a copper-based alloy having excellent slidability and corrosion resistance.
[0002]
[Problems to be solved by the invention]
Copper-based alloys are used in various industrial fields such as construction, printing, electric machines, and automobiles because of their good thermal and electrical conductivity and good corrosion resistance and workability. In particular, because of its excellent corrosion resistance and slidability, it is widely used for sliding parts such as various gears, guide rails, automobile parts, home electric parts, pumps, motors, and OA equipment.
[0003]
By the way, in an environment where lubricating oil cannot be used or when long-term durability is required, a surface treatment is performed on a sliding surface.
[0004]
For example, a fluororesin-based coating film with excellent weather resistance, dirt adhesion prevention, water repellency, and lubricity, and a functional ceramic film with heat resistance, abrasion resistance, hydrophilicity, photocatalytic properties, and far-infrared reflection function It has been proposed to provide
[0005]
However, these films generally have poor adhesion to a copper-based alloy as a base material and have poor durability.
[0006]
For example, JP-A-5-157115 discloses a method of impregnating a sintered copper alloy with a resin such as polyamide or polyimide. However, this type of resin has good adhesiveness because it can impregnate pores of a sintered copper alloy, but has a slidability in comparison with a fluororesin such as polytetrafluoroethylene (PTFE). And inferior. For this reason, sufficient sliding performance cannot be obtained. When a fluorine-based resin having good lubricity is used instead of a resin such as polyamide or polyimide, the resin is hardly impregnated and has poor adhesion. That is, solid lubricants such as PTFE and molybdenum disulfide are excellent in heat resistance and slidability, but are difficult to impregnate and apply, and have poor adhesion to a copper alloy material as a base material.
[0007]
Therefore, in order to improve the adhesion, it has been considered to blast the copper-based alloy material with sand or ceramic particles.
[0008]
However, although this technique improves the adhesiveness, the blast particles pierce the soft copper-based alloy material, so that the blasted particles wear the mating material, deform the base material, and further resist the blast particles. A new problem arises, such as reduced seizure and durability.
[0009]
Therefore, the problem to be solved by the present invention is to solve the above drawbacks.
[0010]
That is, an object of the present invention is to provide a copper-based alloy material having excellent slidability and durability. In particular, a low-adhesion solid lubricant such as PTFE or molybdenum disulfide is firmly adhered and fixed to the surface of the copper-based alloy, and good sliding and seizure resistance can be obtained even in an oil-free environment or a corrosive environment. It is an object of the present invention to provide a copper-based alloy material (composite material).
[0011]
[Means for Solving the Problems]
As a result of intensive research into solving the above problems, in a severely corrosive environment, easily corrosive components such as zinc in copper-based alloys (corrosive components) corrode to form oxidation products, It has been found that this speeds up burning. In order to prevent this, even if a solid lubricant such as PTFE or molybdenum disulfide is applied to the surface, the adhesion to the copper-based alloy material as the base material is poor, and a sufficient effect may not be obtained. I understand.
[0012]
Therefore, as we proceeded with further investigation, we found that a solution containing one or more compounds selected from the group consisting of peroxides, peroxo compounds, chromic acid, and permanganic acid, And oxidized products are selectively removed, and the unevenness is formed on the surface by this removal. The solid lubricant such as PTFE or molybdenum disulfide provided on the surface bites into the unevenness to improve the adhesion. In addition, it has been found that the durability (corrosion resistance) is also improved because the corrosive components are reduced.
[0013]
The present invention has been achieved based on the above findings.
[0014]
That is, the above-mentioned problems are caused by a copper alloy material,
Irregularities formed on the surface of the copper-based alloy material by removing easily corrosive components and / or oxides contained in the copper-based alloy in the copper-based alloy material;
Coating provided on the copper-based alloy material on which the irregularities are formed
And a composite material characterized by comprising:
[0015]
In particular, a composite material having excellent slidability and corrosion resistance,
Copper-based alloy material,
Irregularities formed on the surface of the copper-based alloy material by removing easily corrosive components and / or oxides contained in the copper-based alloy in the copper-based alloy material;
Coating provided on the copper-based alloy material on which the irregularities are formed
And a composite material characterized by comprising:
[0016]
Further, the problem is solved by a composite material having a metal phosphate and / or metal oxide layer on the copper-based alloy material on which the irregularities are formed and below the film.
[0017]
A step of treating the copper-based alloy material with a selective chemical etching solution;
After the step A, a step C for providing a film on the surface
And a method for manufacturing a composite material, comprising:
[0018]
In particular, an A step of treating the copper-based alloy material with a selective chemical etching solution;
After the step A, a step B of providing a metal phosphate and / or metal oxide layer on the surface;
After the step B, a step C for providing a film on the surface
And a method for manufacturing a composite material, comprising:
[0019]
The uneven portion on the surface of the copper-based alloy material in the present invention is formed by treating the copper-based alloy material with a selective chemical etching solution. The temperature of the processing solution and the processing time are not particularly limited, but are, for example, a temperature of room temperature to 50 ° C. and a time of about 1 to 10 minutes. As a result, an unevenness having a depth of about 0.05 to 10 μm, preferably 0.5 to 7 μm is obtained.
[0020]
The selective chemical etching solution is preferably a solution containing one or more compounds selected from the group consisting of peroxides, peroxo compounds, chromic acid and permanganic acid. Particularly, it is an aqueous solution containing a peroxide or a peroxo compound. As the peroxo compound, for example, peroxosulfuric acid, peroxophosphoric acid, peroxovanadic acid, peroxoniobic acid, peroxotantalic acid, peroxoboric acid, peroxotitanic acid, peroxotungstic acid, peroxomolybdic acid, peroxochromic acid and the like and soluble salts thereof. preferable. In particular, peroxosulfuric acid and its salts. Among them, ammonium salts, sodium salts, and potassium salts of peroxodisulfuric acid are particularly preferable. The preferred peroxide is hydrogen peroxide. The preferred concentration of a peroxide, a peroxo compound or the like in these aqueous solutions is 1 to 30% by mass, particularly 3 to 20% by mass. This is because if the concentration is too low, the effect of selectively removing easily corrosive components and oxides is small, while if the concentration is too high, crystals precipitate and the liquid becomes unstable.
[0021]
Selective chemical etchants include peroxide, peroxo compounds, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, zircon hydrofluoric acid, titanium hydrofluoric acid, titanic acid, molybdic acid, tungstic acid, vanadic acid, niobic acid And one or more compounds selected from the group of organic chelating agents (preferably those having a chelating effect on copper, such as tartaric acid, citric acid, EDTA, organic phosphonic acid, and phytic acid). It is preferred that
[0022]
Preferred combinations of selective chemical etchants include, for example, phosphoric acid-peroxosulfuric acid, peroxophosphoric acid-sulfuric acid, phosphoric acid-hydrogen peroxide, tartaric acid-hydrogen peroxide, phosphoric acid-nitric acid-hydrogen peroxide, sulfuric acid-peroxide. An aqueous solution of hydrogen or the like.
[0023]
The pH of the selective chemical etchant is particularly preferably between 1 and 5. The pH can be adjusted by appropriately using an alkali such as aqueous ammonia, ammonium carbonate, sodium hydroxide, sodium carbonate, potassium hydroxide, or the like.
[0024]
In the present invention, the use of a peroxide or a peroxo compound is particularly effective in a mechanical surface roughening method by blast treatment or a chemical etching with a usual acid or alkali, whereby selective removal of easily corrosive components and oxides is possible. In addition, by using peroxides and peroxo compounds, etc., the selective removal of easily corrosive components and oxides was effectively performed, and the anchor effect on the film provided on the selectively removed surface was extremely high. It is.
[0025]
After the selective chemical etching treatment, one or two selected from the group of zinc, calcium, magnesium, manganese, nickel, cobalt, molybdenum, tungsten, copper, tin, titanium, zirconium, vanadium, indium, and chromium It is preferable to treat the copper-based alloy material with a solution containing a compound of the above metals. For example, in the form of a metal ion aqueous solution such as a sulfate, acetate, chloride, phosphate, carbonate, or hydroxide of the above metal, or in the form of a colloid sol of an oxide, a copper-based alloy material Process. As a result, a metal phosphate and / or metal oxide layer is provided on the surface of the copper-based alloy material having the irregularities formed by the selective chemical etching. The preferred thickness is between 0.1 and 2 μm, especially between 0.2 and 1 μm. And, by this layer, the corrosion resistance is improved, and the adhesion of the upper layer film is improved.
[0026]
After the above-mentioned treatment (selective chemical etching treatment or metal phosphate and / or metal oxide layer formation treatment) is completed, it is preferable to immediately wash with water to remove the acid remaining in the copper-based alloy material. For example, when an acid remains in a copper-based alloy material, it causes a reduction in corrosion resistance. In particular, when ultrasonic cleaning is performed, smut and the like remaining on the surface of the copper-based alloy material are also removed, and a surface having more excellent adhesion can be obtained.
[0027]
After the above-mentioned water washing treatment, it is preferable to carry out treatment with an aqueous solution containing an organic alkali compound such as alkanolamine. Thereby, the acid remaining in the alloy in the previous step is neutralized, and the corrosion resistance is improved. In addition, the adhesion of the film formed thereon is improved. As the organic alkali compound, a low molecular weight compound having at least one amino group in the molecular structure is preferable. For example, in addition to monoethanolamine, diethanolamine, and triethanolamine, morpholine, a derivative thereof, and alkoxysilane having various amino groups can be given. These compounds enhance the adhesion of the solid lubricating film on the surface and the wettability of the paint, and provide a more excellent effect in practical use.
[0028]
A film, particularly a solid lubricant-based film, is provided on the surface of the copper-based alloy material treated as described above.
[0029]
The coating includes a coating containing a solid lubricant. Examples of the solid lubricant include polytetrafluoroethylene (PTFE), tetrafluoroperfluoroalkyl vinyl ether copolymer (TPA), graphite, molybdenum disulfide, tungsten disulfide, boron nitride, tungsten fluoride, titanium nitride, and the like. Can be As a binder component of the coating film, for example, a thermoplastic resin such as polyester, polyolefin, polyurethane, polyacryl, polyamide, polyimide, epoxy, and silicate can be used as appropriate. As these paints, for example, FL-J4668 manufactured by Nippon Parkerizing Co., Ltd., EB3, LHF4B manufactured by Kawamura Institute, Ltd., and the like can be used. Then, a paint containing these various components is applied by a spray method, a dip method, a roll coater method, or the like, and baked to obtain a coating film. Also, a powder method or an electrodeposition method can be used. The thickness of the coating film is, for example, preferably 2 to 20 μm, particularly preferably 1 to 10 μm.
[0030]
The copper-based alloy material targeted by the present invention may be made of a copper alloy. Preferably, it is a copper alloy having a copper content of 20 to 95% by mass, particularly 50 to 90% by mass. Other components include metal elements such as Zn or Sn, Ni which are easily corroded. For example, brass such as JIS C2600, C2680 and C2801, free-cutting brass such as C3560 and C3710, Sn-containing brass such as C4250, etc., bronze such as C6140, white copper such as C7060, brass casting such as YBsC1 and HBsC1 and HBsC3 And the like, bronze castings such as BC1, BC2 and BC6, and phosphor bronze castings such as PBC2.
[0031]
Prior to the selective chemical etching treatment, it is preferable to remove oil adhering to the surface of the copper-based alloy material in advance by degreasing and the like.
[0032]
And, the composite material obtained as described above is greatly improved in durability and seizure resistance (slidability).
[0033]
BEST MODE FOR CARRYING OUT THE INVENTION
The composite material according to the present invention includes a copper-based alloy material and irregularities formed on a surface of the copper-based alloy material by removing easily corrosive components and / or oxides contained in the copper-based alloy in the copper-based alloy material. And a coating provided on the copper-based alloy material on which the irregularities are formed. In particular, a composite material having excellent slidability and corrosion resistance, wherein a copper-based alloy material and a readily corrosive component and / or oxide contained in a copper-based alloy in the copper-based alloy material are selectively removed. An uneven portion formed on the surface of the copper-based alloy material, and a film provided on the copper-based alloy material on which the uneven portion is formed. Further, a metal phosphate and / or metal oxide layer is provided on the copper-based alloy material on which the uneven portions are formed and below the film.
[0034]
The method for producing a composite material according to the present invention includes a step A for treating a copper-based alloy material with a selective chemical etching solution, and a step C for providing a film on the surface after the step A. In particular, Step A of treating the copper-based alloy material with a selective chemical etching solution, Step B of providing a metal phosphate and / or metal oxide layer on the surface after Step A, and Step B after the step B. And C step of providing a film on the surface.
[0035]
The irregularities on the surface of the copper-based alloy material according to the present invention are obtained by treating the copper-based alloy material with a selective chemical etching solution (for example, by applying a copper-based alloy material to the selective chemical etching solution by a technique such as immersion, spraying or flow coating). Contact). The processing conditions are, for example, a temperature of room temperature to 50 ° C. for a time of about 1 to 10 minutes. As a result, an unevenness with a depth of about 0.05 to 10 μm, particularly 0.5 to 7 μm is obtained.
[0036]
The selective chemical etching solution is preferably a solution containing one or more compounds selected from the group consisting of peroxides, peroxo compounds, chromic acid and permanganic acid. Particularly, it is an aqueous solution containing a peroxide or a peroxo compound. As the peroxo compound, for example, peroxosulfuric acid, peroxophosphoric acid, peroxovanadic acid, peroxoniobic acid, peroxotantalic acid, peroxoboric acid, peroxotitanic acid, peroxotungstic acid, peroxomolybdic acid, peroxochromic acid and the like and soluble salts thereof. preferable. In particular, peroxosulfuric acid and its salts. Among them, ammonium salts, sodium salts, and potassium salts of peroxodisulfuric acid are particularly preferable. The preferred peroxide is hydrogen peroxide. The preferred concentration of a peroxide, a peroxo compound or the like in these aqueous solutions is 1 to 30% by mass, particularly 3 to 20% by mass. The selective chemical etching solution is preferably phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, zircon hydrofluoric acid, titanium hydrofluoric acid, titanic acid, molybdic acid, tungstic acid, vanadic acid, together with a peroxide or a peroxo compound. Niobic acid and organic chelating agents (organic chelating agents are not particularly limited, but those having a chelating effect on copper are preferable, such as tartaric acid, citric acid, EDTA, organic phosphonic acid, and phytic acid). And one or more compounds selected from the group consisting of: Particularly preferred combinations of selective chemical etchants include, for example, phosphoric acid-peroxosulfuric acid, peroxophosphoric acid-sulfuric acid, phosphoric acid-hydrogen peroxide, tartaric acid-hydrogen peroxide, phosphoric acid-nitric acid-hydrogen peroxide, sulfuric acid-peroxide. An aqueous solution of hydrogen or the like. The pH of the selective chemical etchant is in particular between 1 and 5. This pH adjustment can be performed using an alkali such as aqueous ammonia, ammonium carbonate, sodium hydroxide, sodium carbonate, potassium hydroxide and the like. The selective chemical etching solution contains phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, zircon hydrofluoric acid, titanium hydrofluoric acid, titanic acid, molybdic acid, tungstic acid, vanadic acid, niobic acid, and an organic chelating agent. If not, the number of steps increases, but after the selective chemical etching treatment, post-treatment with the above-mentioned liquid is performed.
[0037]
After the selective chemical etching treatment, preferably one selected from the group of zinc, calcium, magnesium, manganese, nickel, cobalt, molybdenum, tungsten, copper, tin, titanium, zirconium, vanadium, indium, and chromium. A copper-based alloy material is treated with a solution containing a compound of two or more metals. For example, in the form of an aqueous solution of a metal ion (for example, about 0.02 to 2% by mass) such as a sulfate, acetate, chloride, phosphate, carbonate, or hydroxide of the above metal, or A copper-based alloy material is treated with a colloid sol. Thereby, the metal phosphate and / or metal oxide having a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm is formed on the surface of the copper-based alloy material having the irregularities formed by the selective chemical etching. Are provided.
[0038]
After the above-mentioned treatment (selective chemical etching treatment or metal phosphate and / or metal oxide layer formation treatment) is completed, preferably, the substrate is immediately washed with water, particularly ultrasonically, to remove the acid remaining in the copper-based alloy material. Remove.
[0039]
After the water washing treatment, treatment is preferably performed with an aqueous solution containing an organic alkali compound such as alkanolamine. Examples of the organic alkali compound include a low molecular weight compound having at least one amino group in a molecular structure. For example, in addition to monoethanolamine, diethanolamine, and triethanolamine, morpholine, a derivative thereof, and alkoxysilane having various amino groups can be given.
[0040]
A film, particularly a solid lubricant-based film, is provided on the surface of the copper-based alloy material treated as described above. The coating includes a coating containing a solid lubricant. Examples of the solid lubricant include PTFE, TPA, graphite, molybdenum disulfide, tungsten disulfide, boron nitride, tungsten fluoride, titanium nitride and the like. As the binder component of the coating film, for example, a thermoplastic resin such as polyester, polyolefin, polyurethane, polyacryl, polyamide, polyimide, epoxy, and silicate can be used as appropriate. As these paints, for example, FL-J4668 manufactured by Nippon Parkerizing Co., Ltd., and EB3, LHF4B manufactured by Kawamura Laboratory Co., Ltd. can be used. Then, a paint containing these various components is applied by a spray method, a dip method, a roll coater method, a powder method, an electrodeposition method, or the like, and baked, for example, to a thickness of 2 to 20 μm, particularly 1 to 10 μm. A coating is obtained.
[0041]
A plating film is also conceivable as the film. For example, plating including a solid lubricant such as Sn plating, lead plating, Cu / Sn plating, and solid lubricant dispersed nickel plating is performed by a method such as electroplating, electroless plating, or displacement plating, for example, to 2 to 20 μm, particularly A thickness of 1 to 10 μm can be formed. In addition, inorganic compound films such as phosphates are also conceivable. The surface film is not limited to a single layer. For example, a solid lubricant film may be formed on the plating film.
[0042]
Further, the film is not limited to a lubricating one, and may be, for example, a color pigment (for example, an inorganic pigment such as a chromium pigment, a nickel pigment, a zinc pigment, an iron pigment, a titanium pigment, etc.) and / or an antirust pigment ( For example, a film containing barium chromate, zinc chromate, and zinc oxide) may be used. Of course, these color pigments and / or rust preventive pigments may be contained together with the solid lubricant.
[0043]
The copper-based alloy material targeted by the present invention may be made of a copper alloy. Preferably, it is a copper alloy having a copper content of 20 to 95% by mass, particularly 50 to 90% by mass. Other components include metal elements such as Zn or Sn and Ni which are easily corroded. For example, brass such as JIS C2600, C2680 and C2801, free-cutting brass such as C3560 and C3710, Sn-containing brass such as C4250, etc., bronze such as C6140, white copper such as C7060, brass casting such as YBsC1 and HBsC1 and HBsC3 And the like, bronze castings such as BC1, BC2, and BC6, and phosphor bronze castings such as PBC2.
[0044]
Hereinafter, specific examples will be described together with comparative examples.
【Example】
The copper alloys of Examples 1, 4, 7, 9 and Comparative Example 1 were brass alloys: C2600 (Cu: 70%, Zn: 30%). 8 and Comparative Example 2 are bronze casting alloys BC-6 (Cu: 85%, Zn: 5%, Sn: 5%, Pb: 5%). Then, these copper-based alloy materials are cut and machined to prepare test specimens, and the test specimens are concentrated at a concentration of 20 g / l using an alkaline degreaser (FC-315: manufactured by Nippon Parkerizing Co., Ltd.). It was degreased at 60 ° C. for 2 minutes and washed with water. Then, in the example, the following selective chemical etching treatment was performed. The reagent used was a first-class reagent manufactured by Wako Pure Chemical Industries, Ltd., and the water used for dilution was deionized water.
[0045]
[Example 1]
The copper alloy material was immersed in an aqueous solution of ammonium peroxodisulfate (concentration: 10% by mass) at 27 ° C. for 180 seconds, and washed with running water.
[0046]
Thereafter, FL-J4668 (main component: PTFE) manufactured by Nippon Parkerizing Co., Ltd. was applied by a spray gun to a dry thickness of 3 μm and baked at 200 ° C.
[0047]
[Example 2]
The copper-based alloy material was immersed in an aqueous solution containing hydrogen peroxide (concentration: 0.5% by mass) and sulfuric acid (concentration: 5% by mass) at 27 ° C. for 60 seconds, and washed with running water.
[0048]
Thereafter, LHF4B (main component: PTFE) manufactured by Kawamura Laboratory Co., Ltd. was applied by a spray gun so as to have a dry film thickness of 4 μm, and baked at 200 ° C.
[0049]
[Example 3]
The copper-based alloy material was immersed in an aqueous solution containing sodium peroxophosphate (concentration: 5% by mass) and phosphoric acid (10% by mass) at 27 ° C. for 120 seconds, and washed with running water.
[0050]
Thereafter, LHF4B (main component: PTFE) manufactured by Kawamura Laboratory Co., Ltd. was applied by a spray gun so as to have a dry film thickness of 4 μm, and baked at 200 ° C.
[0051]
[Example 4]
The copper alloy material was immersed in an aqueous solution containing hydrogen peroxide (concentration: 2% by mass) and phosphoric acid (concentration: 8% by mass) at 27 ° C. for 300 seconds, and washed with running water.
[0052]
Next, it was immersed in an aqueous solution containing phosphoric acid (5% by mass) and nickel sulfate (2% by mass) at 45 ° C. for 60 seconds, and washed with ultrasonic waves (25 KHz × 30 seconds).
[0053]
Thereafter, FL-J4668 (main component: PTFE) manufactured by Nippon Parkerizing Co., Ltd. was applied by a spray gun to a dry thickness of 3 μm and baked at 200 ° C.
[0054]
[Example 5]
The copper-based alloy material was immersed in an aqueous solution containing hydrogen peroxide (concentration 0.8% by mass) and zircon hydrofluoric acid (concentration 2% by mass) at 27 ° C. for 240 seconds, and washed with running water.
[0055]
Next, it was immersed in an aqueous solution containing phosphoric acid (concentration: 10% by mass), zinc nitrate (concentration: 2% by mass) and calcium nitrate (concentration: 1% by mass) at 45 ° C. for 60 seconds, and washed with water.
[0056]
Thereafter, LHF4B (main component: PTFE) manufactured by Kawamura Laboratory Co., Ltd. was applied by a spray gun so as to have a dry film thickness of 4 μm, and baked at 200 ° C.
[0057]
[Example 6]
The copper alloy material was immersed in an aqueous solution containing vanadic acid (concentration: 5% by mass) and hydrogen peroxide (concentration: 2% by mass) at 27 ° C. for 180 seconds, and washed with running water.
[0058]
Next, it was immersed in an aqueous solution of monoethanolamine (concentration: 0.5% by mass) for 15 seconds, pulled up, and dried at 120 ° C. for 10 seconds.
[0059]
Thereafter, EB-3 (main component is molybdenum disulfide) manufactured by Kawamura Laboratory Co., Ltd. was applied so that the dry film thickness became 3 μm.
[0060]
[Example 7]
The copper-based alloy material was immersed in an aqueous solution containing hydrofluoric acid (concentration: 5% by mass) and hydrogen peroxide (concentration: 1% by mass) at 27 ° C. for 300 seconds, and washed with running water.
[0061]
Next, it was immersed in an aqueous solution containing chromic acid (concentration: 3% by mass) and nitric acid (concentration: 0.5% by mass) at 45 ° C. for 60 seconds, and washed with water.
[0062]
Next, it was immersed in an aqueous solution of triethanolamine (concentration: 0.5% by mass) for 15 seconds, pulled up, and dried at 120 ° C. for 10 seconds.
[0063]
Thereafter, FL-J4668 (main component: PTFE) manufactured by Nippon Parkerizing Co., Ltd. was applied by a spray gun to a dry thickness of 3 μm and baked at 200 ° C.
[0064]
Example 8
The copper-based alloy material was immersed in an aqueous solution containing potassium peroxodisulfate (concentration: 5% by mass) and tartaric acid (concentration: 5% by mass) at 27 ° C. for 180 seconds, and washed with running water.
[0065]
Next, it was immersed in an aqueous solution containing phosphoric acid (concentration of 5% by mass) and magnesium hydroxide (concentration of 2% by mass) at 45 ° C. for 60 seconds, and washed with ultrasonic waves (25 KHz × 30 seconds).
[0066]
Next, it was immersed in an aqueous solution of γ-aminopropyltrimethoxysilane (concentration: 1% by mass) for 15 seconds, pulled up, and dried at 120 ° C. for 10 seconds.
[0067]
Thereafter, FL-J4668 (main component: PTFE) manufactured by Nippon Parkerizing Co., Ltd. was applied by a spray gun to a dry thickness of 3 μm and baked at 200 ° C.
[0068]
[Example 9]
The copper alloy material was immersed in an aqueous solution containing permanganic acid (concentration: 5% by mass) and phosphoric acid (concentration: 3% by mass) at 27 ° C. for 240 seconds, and washed with running water.
[0069]
Next, it was immersed in an aqueous solution containing zircon hydrofluoric acid (concentration 2% by mass) and zirconium nitrate (concentration 2% by mass) at 45 ° C. for 60 seconds, and washed with ultrasonic waves (25 KHz × 30 seconds).
[0070]
Next, it was immersed in an aqueous solution containing monoethanolamine (concentration: 0.5% by mass) and diethanolamine (concentration: 0.5% by mass) for 15 seconds, pulled up, and then dried at 120 ° C. for 10 seconds.
[0071]
Thereafter, EB-3 (main component is molybdenum disulfide) manufactured by Kawamura Laboratory Co., Ltd. was applied so that the dry film thickness became 3 μm.
[0072]
[Comparative Example 1]
The above-mentioned copper alloy material is not subjected to any treatment, and FL-J4668 (main component is PTFE) manufactured by Nippon Parkerizing Co., Ltd. is applied with a spray gun to a dry thickness of 3 μm and baked at 200 ° C. Was.
[0073]
[Comparative Example 2]
The copper-based alloy material was immersed in an aqueous solution of sulfuric acid (concentration: 15% by mass) at 27 ° C. for 240 seconds, and washed with running water.
[0074]
Thereafter, EB-3 (main component is molybdenum disulfide) manufactured by Kawamura Laboratory Co., Ltd. was applied so that the dry film thickness became 3 μm.
[0075]
[Characteristic]
The adhesion, corrosion resistance, and slidability of the lubricating film obtained from each of the above examples were examined. The results are shown in Table 1. In addition, the presence / absence of unevenness (the presence / absence of porosity and the presence / absence of selective etching) on the surface of the copper-based alloy material after the etching treatment was examined, and this is also shown in Table 1.
[0076]
Adhesion: Using a cutter knife, cut 100 squares of 1 mm each and apply cellophane adhesive tape. Peel off and not peel off at all. Those peeled off are indicated by Δ, and those peeled off by more than 20 are indicated by x.
[0078]
Corrosion resistance: Corrosion resistance test was conducted in accordance with JIS-K5400 salt water spray test method. Those which did not show rust for 480 hours were regarded as pass (○), and those which showed rust were failed (不). did.
[0079]
Sliding property: Using an SRV friction and wear tester, when the load (N) until seizure occurs is 5000N or more: ◎, 4000 to 5000N: ○, 2000 to 4000N: Δ, less than 2000N Those were indicated by x. The load was stepped up at a speed of 50 N / min, and a SUJ-2 steel ball having a frequency of 50 Hz, an amplitude of 2 mm, and a mating agent of 10 mmφ was used. No lubricant was used.
[0080]
Properties of copper-based alloy material surface: The presence or absence of porosity on the surface after chemical etching was checked for irregularities using a scanning electron microscope manufactured by JEOL Ltd. Further, the surface after the chemical etching was subjected to surface analysis using XPS (X-ray photoelectron spectroscopy) manufactured by Shimadzu Corporation to check whether or not selective etching was performed.
[0081]
According to this, the composite material according to the present invention, by the treatment with a selective chemical etching solution, the easily corrosive components and oxides contained in the copper-based alloy in the copper-based alloy material are removed, and the surface of the copper-based alloy material is removed. Since the porous irregularities are formed and the irregularities with such characteristics are formed, the film provided thereon has excellent adhesion, and also has excellent corrosion resistance and slidability. It turns out that there is.
[0082]
In addition, as can be seen from Comparative Example 2, selective etching is not performed by simple etching, that is, no porous unevenness is formed, and the same as in Example on a substrate having such surface characteristics. Even if a good coating is provided, the adhesion of the coating is poor, and the corrosion resistance and slidability are also poor.
[0083]
【The invention's effect】
A film of a solid lubricant such as PTFE or molybdenum disulfide can be firmly adhered and fixed, and a copper-based alloy material having good slidability and anti-seizure properties can be obtained even in an oilless environment or a corrosive environment.
Claims (15)
前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が除去されて該銅系合金材表面に形成された凹凸部と、
前記凹凸部が形成された銅系合金材の上に設けられた皮膜
とを具備することを特徴とする複合材。Copper-based alloy material,
Irregularities formed on the surface of the copper-based alloy material by removing easily corrosive components and / or oxides contained in the copper-based alloy in the copper-based alloy material;
And a coating provided on the copper-based alloy material on which the irregularities are formed.
銅系合金材と、
前記銅系合金材における銅系合金に含まれる易腐食性成分および／または酸化物が選択的に除去されて該銅系合金材表面に形成された凹凸部と、
前記凹凸部が形成された銅系合金材の上に設けられた皮膜
とを具備することを特徴とする複合材。A composite material having excellent slidability and corrosion resistance,
Copper-based alloy material,
Irregularities formed on the surface of the copper-based alloy material by removing easily corrosive components and / or oxides contained in the copper-based alloy in the copper-based alloy material;
And a coating provided on the copper-based alloy material on which the irregularities are formed.
前記Ａ工程の後、表面に皮膜を設けるＣ工程
とを具備することを特徴とする複合材製造方法。An A step of treating the copper-based alloy material with a selective chemical etching solution;
A method for producing a composite material, comprising a step C of providing a film on the surface after the step A.
前記Ａ工程の後、表面に金属リン酸塩および／または金属酸化物の層を設けるＢ工程と、
前記Ｂ工程の後、表面に皮膜を設けるＣ工程
とを具備することを特徴とする複合材製造方法。An A step of treating the copper-based alloy material with a selective chemical etching solution;
After the step A, a step B of providing a metal phosphate and / or metal oxide layer on the surface;
A method for manufacturing a composite material, comprising: a step C of providing a film on the surface after the step B.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006137497A1 (en) * | 2005-06-24 | 2006-12-28 | Mitsubishi Gas Chemical Company, Inc. | Etching composition for metal material and method for manufacturing semiconductor device by using same |
| JP2007119803A (en) * | 2005-10-25 | 2007-05-17 | Sumitomo Light Metal Ind Ltd | Cleaning method for inner surface of copper tube or copper alloy tube |
| JP2008008434A (en) * | 2006-06-30 | 2008-01-17 | Jtekt Corp | Rolling bearing |
| CN100376721C (en) * | 2005-09-21 | 2008-03-26 | 中国海洋大学 | Chemical Etching Solutions for Molybdenum |
| JP2009174050A (en) * | 2007-12-27 | 2009-08-06 | Kansai Paint Co Ltd | Metal surface treatment composition and surface-treated metal material having a metal surface treatment layer obtained from the metal surface treatment composition |
| JP2009174051A (en) * | 2007-12-27 | 2009-08-06 | Kansai Paint Co Ltd | Composition for metal surface treatment, and surface treated metallic material having metal surface treatment film obtained from the composition for metal surface treatment |
| CN105256315A (en) * | 2015-09-16 | 2016-01-20 | 昆山全亚冠环保科技有限公司 | Metallographic corrosive agent and method for nickel-vanadium alloy |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| CN110453231A (en) * | 2018-05-07 | 2019-11-15 | 南京晶质新型复合材料科技有限公司 | A kind of nanometer of copper alloy composite material surface treatment method |
| WO2020217519A1 (en) * | 2019-04-26 | 2020-10-29 | 朝日化学工業株式会社 | Smut removal composition |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
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| US8658053B2 (en) | 2005-06-24 | 2014-02-25 | Mitsubishi Gas Chemical Company, Inc. | Etching composition for metal material and method for manufacturing semiconductor device by using same |
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| CN100376721C (en) * | 2005-09-21 | 2008-03-26 | 中国海洋大学 | Chemical Etching Solutions for Molybdenum |
| JP2007119803A (en) * | 2005-10-25 | 2007-05-17 | Sumitomo Light Metal Ind Ltd | Cleaning method for inner surface of copper tube or copper alloy tube |
| JP2008008434A (en) * | 2006-06-30 | 2008-01-17 | Jtekt Corp | Rolling bearing |
| JP2009174050A (en) * | 2007-12-27 | 2009-08-06 | Kansai Paint Co Ltd | Metal surface treatment composition and surface-treated metal material having a metal surface treatment layer obtained from the metal surface treatment composition |
| JP2009174051A (en) * | 2007-12-27 | 2009-08-06 | Kansai Paint Co Ltd | Composition for metal surface treatment, and surface treated metallic material having metal surface treatment film obtained from the composition for metal surface treatment |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| CN105256315A (en) * | 2015-09-16 | 2016-01-20 | 昆山全亚冠环保科技有限公司 | Metallographic corrosive agent and method for nickel-vanadium alloy |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
| CN110453231A (en) * | 2018-05-07 | 2019-11-15 | 南京晶质新型复合材料科技有限公司 | A kind of nanometer of copper alloy composite material surface treatment method |
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