JP2004100004A - Coated cemented carbide and production method therefor - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は切削工具、耐摩耗工具として用いられる耐摩耗性、耐欠損性に優れた被覆超硬合金に関する。
【０００２】
【従来の技術】
被覆超硬合金の用途として切削工具が挙げられるが、被覆超硬合金を用いた切削工具の従来技術として特開昭６２−９９４６７号公報がある。超硬合金基材表面部に１〜５０μｍの深さに亘って硬化表面層を形成した表面被覆超硬合金が特開昭５５−１０４４７５号公報に開示されている。
【０００３】
【発明が解決しようとする課題】
特開昭６２−９９４６７号公報には、超硬合金母材の表面に中温ＣＶＤ法によって厚さ０．５〜５．０μｍのＴｉＣＮおよび／またはＴｉＮを被覆させた被覆超硬合金が提案されているが、最下層であるＴｉＣＮおよび／またはＴｉＮと超硬合金母材との密着性が十分でなく、被膜が剥がれやすいという問題がある。特開昭５５−１０４４７５号公報には、被膜直下における超硬合金基材の表面部に１〜５０μｍの深さに亘って硬化表面層とした表面被覆超硬合金が提案されているが、硬化表面層が厚く切削工具として用いた場合、硬化表面層にクラックが生じやすいという問題がある。
【０００４】
本発明は、このような従来の技術が有していた問題を解決しようとするものである。すなわち被膜の最下層を窒化チタンおよび／または炭窒化チタンとし、被膜と超硬合金基材との間にＴｉとＷを含有した被膜密着相を形成させ、被膜と超硬合金基材とを強固に密着させた。密着性を向上させることにより、被膜が有する特性を十分に発揮させ、切削工具として用いた場合、耐摩耗性および／または耐欠損性に優れる被覆超硬合金とその製造方法の提供を目的とするものである。
【０００５】
【課題を解決するための手段】
本発明者らは、長年に亘って被覆超硬合金について研究に従事してきたが、窒化チタンおよび／または炭窒化チタンからなる最下層を含む被膜と超硬合金基材の間にＴｉとＷを含んだ炭化物、窒化物、炭窒化物の中から選ばれた少なくとも１種の金属化合物からなる被膜密着相を形成させると、被膜と超硬合金基材が強固に密着することを見出した。
【０００６】
被膜と超硬合金基材との間にＴｉとＷを含んだ炭化物、窒化物、炭窒化物の中から選ばれた少なくとも１種の金属化合物からなる被膜密着相を形成させる作用は次の通りである。Ｗを含有させた被膜密着相は超硬合金基材と共通した元素を有するため超硬合金基材との密着性が高い。また、被膜密着相にＴｉを含有させることにより最下層が窒化チタンおよび／または炭窒化チタンである被膜との密着性が高い。したがって被膜密着相が被膜と超硬合金基材の間に存在すると、被膜と超硬合金基材とを強固に密着させることができる。また、被膜密着相の機械的特性が、被膜最下層の機械的特性と超硬合金基材表面部の機械的特性との間にあると機械的特性に連続性が生じるため好ましい。
【０００７】
被膜密着相は、Ｔｉ、Ｗを含有する炭化物、窒化物、炭窒化物の中から選ばれた少なくとも１種の金属化合物で構成される。その中でもＴｉ、Ｗを含有する炭窒化物は、Ｔｉ、Ｗを含有する炭化物よりも靱性が高く、Ｔｉ、Ｗを含有する窒化物よりも硬さが高いので好ましい。また、被膜密着相の金属成分は、Ｔｉ、Ｗ以外に、Ａｌ，Ｓｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，およびＭｏからなる群から選ばれた少なくとも１種を含んでも良い。
【０００８】
具体的には、（Ｔｉ，Ｗ）Ｃ、（Ｔｉ，Ｗ，Ｎｂ）Ｃ、（Ｔｉ，Ｗ，Ｔａ）Ｃ、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ）Ｃ、（Ｔｉ，Ｗ，Ａｌ）Ｃ、（Ｔｉ，Ｗ，Ｓｉ）Ｃ、（Ｔｉ，Ｗ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ｎｂ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ｔａ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ａｌ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ｓｉ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ）Ｎ、（Ｔｉ，Ｗ，Ｎｂ）Ｎ、（Ｔｉ，Ｗ，Ｔａ）Ｎ、（Ｔｉ，Ｗ，Ｔａ，Ｎｂ）Ｎ、（Ｔｉ，Ｗ，Ａｌ）Ｎ、（Ｔｉ，Ｗ，Ｓｉ）Ｎなどが挙げられる。被膜密着相は結晶質であると好ましく、その中でも立方晶であると硬さが高いため、さらに好ましい。
【０００９】
被膜密着相の形態としては、被膜と超硬合金基材の間に平均厚さ０．００１〜０．４μｍの層状として存在するか、もしくは、平均厚さ０．００１〜０．４μｍの層状粒子が０．００１〜１０μｍ間隔で分散して存在している。被膜密着相が層状として存在する場合、平均厚さ０．００１μｍ未満であると超硬合金基材と被膜を密着させる効果が減少し、平均厚さ０．４μｍを超えると被覆超硬合金を切削工具として用いた場合に被膜密着相にクラックが生じやすく被膜の密着性が低下する。被膜密着相が層状である場合、平均厚さ０．０１〜０．１μｍの層状が好ましい。
【００１０】
被膜密着相が層状粒子として存在する場合、平均厚さ０．００１μｍ未満の層状粒子であると超硬合金基材と被膜を密着させる効果が減少し、平均厚さ０．４μｍを超える層状粒子であると被覆超硬合金を切削工具として用いた場合に被膜密着相にクラックが生じやすく被膜の密着性が低下する。被膜密着相が層状粒子であると連続的な層状に比べ被膜または超硬合金基材との接触面積が増加するとともに被膜密着相に生じるクラックが進展しにくいことから好ましい。層状粒子の間隔が０．００１μｍ未満では連続的な層状と変わらず、層状粒子の間隔が１０μｍを超えると被膜密着相の効果が少なく被膜の密着性が低下する。被膜密着相が層状粒子の場合、被膜と超硬合金基材の間に平均厚さ０．０１〜０．１μｍの被膜密着相の層状粒子が０．０１〜１μｍ間隔で分散していると、被膜密着相による密着性向上の効果が高く好ましい。
【００１１】
被膜密着相は、（Ｔｉａ，Ｗｂ）（Ｃｘ，Ｎｙ）ｚで表され、それぞれのモル比率が、０．６≦ａ≦０．９４、０．０６≦ｂ≦０．４、ａ＋ｂ＝１、０．１≦ｘ≦０．９、０．１≦ｙ≦０．９、ｘ＋ｙ＝１、ｚは金属元素Ｔｉ、Ｗ、の合計に対する非金属元素Ｃ，Ｎの合計のモル比率を示し、０．８≦ｚ≦１であると好ましい。０．６≦ａ≦０．９４としたのは、ａが０．６未満であるとＴｉ含有量が減少し被膜との密着性が減少する傾向が見られ、ａが０．９４を超えると相対的にＷ含有量が減少し超硬合金基材との密着性が減少する傾向が見られるためである。０．０６≦ｂ≦０．４としたのは、ｂが０．０６未満であると超硬合金基材との密着性が減少する傾向が見られ、ｂが０．４を超えるとＴｉ含有量が減少し被膜との密着性が減少する傾向が見られるためである。０．１≦ｘ≦０．９としたのは、ｘが０．１未満であると被膜密着相の硬さが低下する傾向が見られ、ｘが０．９を超えると被膜密着相の靱性が低下する傾向が見られるためである。０．１≦ｙ≦０．９としたのは、ｙが０．１未満であると被膜密着相の靱性が低下する傾向が見られ、ｙが０．９を超えると被膜密着相の硬さが低下する傾向が見られるためである。０．８≦ｚ≦１としたのは、ｚが０．８未満では被膜密着相の硬さが低下し、ｚが１．０を超える金属化合物は、被覆または熱処理によって得られにくいためである。
【００１２】
また、被膜密着相が（Ｔｉａ，Ｗｂ，Ｍｃ）（Ｃｘ，Ｎｙ）ｚで表され、ＭはＡｌ，Ｓｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，およびＭｏから選ばれた少なくとも１種の元素を示し、それぞれのモル比率が、０．６≦ａ≦０．９４、０．０６≦ｂ≦０．４、０＜ｃ≦０．１、ａ＋ｂ＋ｃ＝１、０．１≦ｘ≦０．９、０．１≦ｙ≦０．９、ｘ＋ｙ＝１、ｚは金属元素Ｔｉ、Ｗ、Ｍの合計に対する非金属元素Ｃ，Ｎの合計のモル比率を示し、０．８≦ｚ≦１であると好ましい。特に超硬合金基材または被膜にＡｌ，Ｓｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ，およびＭｏから選ばれた少なくとも１種の元素が含まれている場合、（Ｔｉａ，Ｗｂ，Ｍｃ）（Ｃｘ，Ｎｙ）ｚからなる被膜密着相による密着性向上の効果が高い。
【００１３】
モル比率の中でｃを０＜ｃ≦０．１としたのは、ｃが０．１を超えると、被膜密着相が立方晶以外の結晶型になることがあり硬さが低下する傾向が見られるためである。０．６≦ａ≦０．９４としたのは、ａが０．６未満であるとＴｉ含有量が減少し被膜との密着性が減少する傾向が見られ、ａが０．９４を超えると相対的にＷ含有量が減少し超硬合金基材との密着性が減少する傾向が見られるためである。０．０６≦ｂ≦０．４としたのは、ｂが０．０６未満であると超硬合金基材との密着性が減少する傾向が見られ、ｂが０．４を超えるとＴｉ含有量が減少し被膜との密着性が減少する傾向が見られるためである。０．１≦ｘ≦０．９としたのは、ｘが０．１未満であると被膜密着相の硬さが低下する傾向が見られ、ｘが０．９を超えると被膜密着相の靱性が低下する傾向が見られるためである。０．１≦ｙ≦０．９としたのは、ｙが０．１未満であると被膜密着相の靱性が低下する傾向が見られ、ｙが０．９を超えると被膜密着相の硬さが低下する傾向が見られるためである。０．８≦ｚ≦１としたのは、ｚが０．８未満では被膜密着相の硬さが低下し、ｚが１．０を超える金属化合物は、被覆または熱処理によって得られにくいためである。
【００１４】
超硬合金基材は、周期律表の４ａ，５ａ，６ａの炭化物、窒化物、炭窒化物の中の少なくとも１種からなる硬質相と鉄族金属を主成分とした結合相からなる超硬合金である。被覆超硬合金基材としてはＣｏを主成分とした結合相：３〜２０重量％とＷＣを主成分とした硬質相：８０〜９７重量％からなるＷＣ基超硬合金が好ましい。
【００１５】
超硬合金の結合相にはＣおよびＷが固溶しているが、、結合相中のＷの固溶量（以降、Ｗ固溶量と表す）が増加し、結合相中のＣの固溶量（以降、炭素量と表す）が減少すると、被膜密着相と超硬合金基材の密着性が向上する。結合相のＷ固溶量と結合相の格子定数は関係し、結合相の格子定数ｌａが３．５６０Å≦ｌａ≦３．５７５Åであると結合相中のＷ固溶量が高い。したがって、格子定数ｌａが３．５６０Å≦ｌａ≦３．５７５Åであると、超硬合金基材と被膜密着相とは高い密着性を示す。また、格子定数ｌａが、３．５６０Å≦ｌａ≦３．５７５Åを示す被覆超硬合金を熱処理すると被膜密着相の形成が容易になる。格子定数ｌａが３．５６０Å未満であると、Ｗ固溶量が減少し被膜密着相との密着性が低下する傾向が見られる。なお、実用的な超硬合金の組成領域で、格子定数ｌａが３．５７５Åを超えることはほとんどない。以上の理由から格子定数ｌａが３．５６０Å≦ｌａ≦３．５７５Åである超硬合金が被覆超硬合金基材として好ましい。なお、結合相中のＷ固溶量を測定するために飽和磁化率を測定する場合には、飽和磁化率６８％〜８０％を示す超硬合金基材が好ましい。飽和磁化率は
飽和磁化率＝（Ｍ／（（Ｃｏの重量％）×０．０１×１６１））×１００（％）
として表すことができ、ここで、Ｍはｅｍｕ／ｇにおける超硬合金基材の飽和磁化であり、Ｃｏの重量％は超硬合金中のＣｏの重量割合である。１６１はｅｍｕ／ｇにおける純Ｃｏの飽和磁化である。
【００１６】
被膜は、窒化チタンおよび／または炭窒化チタンからなる最下層を含んだ被膜である。窒化チタンおよび／または炭窒化チタンからなる最下層は、具体的にはＴｉＮ０．９、Ｔｉ（Ｃ０．１，Ｎ０．９）０．９を例示できる。被膜は窒化チタンおよび／または炭窒化チタンからなる最下層のみの単層膜、または、窒化チタンおよび／または炭窒化チタンからなる最下層を含む多層膜でもよい。最下層以外の上膜としては、周期律表の４ａ，５ａ，６ａ族元素、Ａｌ、Ｓｉの炭化物、窒化物、酸化物、ホウ化物、およびこれらの相互固溶体から選ばれた少なくとも１種の化合物からなる単層膜または多層膜であり、具体的な組成としては、ＴｉＣ０．９、ＴｉＮ０．９、Ｔｉ（Ｃ０．５，Ｎ０．５）０．９、Ａｌ２Ｏ３、（Ｔｉ０．５，Ａｌ０．５）Ｎ０．９などが挙げられる。被膜は、化学蒸着法または物理蒸着法によって超硬合金基材に被覆される。
【００１７】
被覆超硬合金の被膜と超硬合金基材の間に被膜密着相を形成させる方法としては、熱処理法と被膜法が挙げられる。被膜密着相の製造方法としては、被膜密着相が容易に得られることから熱処理法が好ましい。熱処理法は、通常の化学蒸着法または物理蒸着法によって窒化チタンおよび／または炭窒化チタンからなる最下層を超硬合金基材に被覆した後または上膜を被覆した後、還元雰囲気または真空雰囲気にして、最下層の被覆温度より２０〜４００℃高い温度で５〜４００分間保持する熱処理をおこなう。具体的な熱処理条件としては温度１１２０〜１２００℃、保持時間２０〜１２０分が好ましい。結合相の格子定数ｌａが３．５６０Å≦ｌａ≦３．５７５Åである超硬合金基材と窒化チタンおよび／または炭窒化チタンからなる最下層を被覆した被覆超硬合金を、最適な条件で熱処理すると被膜と超硬合金基材の間に被膜密着相が生成する。
【００１８】
熱処理工程は、被膜の被覆工程中または被覆終了後のいずれにおこなっても良く、被覆工程終了後に別の炉でおこなっても良い。また、超硬合金基材の表面に窒化チタンおよび／または炭窒化チタンからなる最下層を被覆した後、被覆温度が高い被膜を被覆すると被膜密着相が生成することがある。このときの生成原理は熱処理法と同じであり、生成した被膜密着相の作用は熱処理法と同一である。
【００１９】
熱処理法による被膜密着相として、被膜と超硬合金基材の結合相が接する界面に形成される層状粒子の被膜密着相を例示できる。被膜密着相形成には超硬合金基材の結合相が関与していると考えられる。図１に示すように熱処理法により生成した被膜密着相の層状粒子は、被膜側において平坦であるが、超硬合金基材側において層と粒子を組み合わせたような不規則な形状を示す。これは熱処理によって最下層と超硬合金基材の界面に最下層に含まれる元素Ｔｉ、Ｃ、Ｎと、結合相に含まれる元素Ｗ、Ｔｉ、Ｔａ、Ｎｂ、Ｃ、Ｎとが、被膜と超硬合金基材の結合相との界面で固相反応し、（Ｔｉ，Ｗ）Ｃ、（Ｔｉ，Ｗ）（Ｃ，Ｎ）、（Ｔｉ，Ｗ，Ｎｂ，Ｔａ）（Ｃ，Ｎ）などのＴｉとＷを含有した炭化物、窒化物、炭窒化物の少なくとも１種からなる金属化合物が形成するためと考えられる。
【００２０】
熱処理法により生成した被膜密着相の層状粒子は、超硬合金基材側において層と粒子を組み合わせたような不規則な形状を示すためアンカー効果が高く、例えば被膜法によって作製される界面に対して連続的な層状の被膜密着相に比較して被膜と超硬合金基材とを強固に密着させるため非常に好ましい。熱処理法においては、超硬合金基材の結合相Ｗ固溶量が高いほど被膜密着相を生成しやすいため、結合相の格子定数ｌａが３．５６０Å≦ｌａ≦３．５７５Åである超硬合金基材が好ましい。
【００２１】
被膜法は通常の化学蒸着法または物理蒸着法によって、ＴｉとＷを含んだ原料ガスまたはターゲットを用いて、ＴｉとＷを含んだ炭化物、窒化物、炭窒化物の中の少なくとも１種を被膜密着相として被覆する。
【００２２】
【実施試験１】
最終成分組成が８７．０％ＷＣ−２．０％ＴｉＣ−２．０％ＴａＣ−９．０％Ｃｏ（以上重量％）であり、結合相の格子定数は３．５７０ÅであるＪＩＳ規格ＣＮＭＧ１２０４０８形状の超硬合金基材を用意した。超硬合金基材の切刃には湿式ブラストホーニング処理をおこなった。超硬合金基材を外熱式化学蒸着装置内に置き、Ｈ２雰囲気にて所定温度まで昇温した。被覆温度９００℃，原料ガス２．５％ＴｉＣｌ４−４８．８％Ｈ２―４８．７％Ｎ２（以上モル％），圧力４０ＫＰａの条件でＴｉＮ膜を厚さ０．５μｍ被覆し、続いて被覆温度９００℃，原料ガス２．０％ＴｉＣｌ４−８７．０％Ｈ２−１．０％ＣＨ３ＣＮ−１０％Ｎ２（以上モル％），圧力６．７ＫＰａの条件でＴｉＣＮ柱状膜を厚さ６．０μｍ被覆した。引き続きＨ２雰囲気で炉内を所定温度に調整し、表１に示す条件で熱処理をおこなって、発明品１〜１０と比較品１、３〜９を作製した。比較品２は外熱式化学蒸着装置内での熱処理をおこなわず、真空焼結炉にて表１に示す条件で熱処理した。比較品１０は発明品１と同じ製造条件から熱処理を除いた製造方法で作製した。
【００２３】
【表１】
試料はダイヤモンドカッターで切断した後、試料の断面をダイヤモンドラップで鏡面研磨した。発明品１〜９および比較品３〜１０については試料断面をＴＥＭ観察用のサンプルに加工してＴＥＭ観察し被膜密着相の形態と大きさを測定し、ＴＥＭ付属のＥＤＳで被膜密着相の元素分析をおこない、被膜密着相の結晶型をＴＥＭ付属の電子回折を用いて測定し、これらの結果を表２に記載した。発明品１０および比較品１、２については鏡面研磨した断面をＦＥ−ＳＥＭにより観察し、被膜密着相の形態と大きさを測定し、ＦＥ−ＳＥＭ付属のＥＤＳで被膜密着相の元素分析をおこない、これらの結果を表２に記載した。さらに、発明品１０および比較品１、２の断面をＴＥＭ観察用のサンプルに加工した後、被膜密着相の結晶型をＴＥＭ付属の電子回折を用いて測定し、その結果を表２に記載した。
【００２５】
【表２】
発明品１〜１０および比較品１〜１０について被削材：ＳＵＳ３０４の丸棒、切削速度：Ｖ＝１００ｍ／ｍｉｎ、送り：ｆ＝０．２５ｍｍ／ｒｅｖ．、切り込み：ｄ＝５．０ｍｍ、切削時の雰囲気：乾式、切削時間２分間という条件でステンレス鋼の乾式連続切削試験をおこなった。試料の切刃の境界部摩耗量を測定し、その結果を表３に記載した。
【００２７】
【表３】
表３に示すように所定の厚さの被膜密着相が存在する発明品１〜１０は、被膜密着相が厚い比較品１、２および被膜密着相が観察されない比較品３〜１０に比較してステンレス鋼の乾式連続切削において優れた耐摩耗性を示す。
【００２９】
【実施試験２】
原料粉末として、市販の平均粒径２μｍのＷＣ粉末、（Ｔｉ，Ｗ）Ｃ粉末、（Ｔａ，Ｎｂ）Ｃ粉末、Ｔｉ（Ｃ，Ｎ）粉末、およびＣｏ粉末を用意し、これらの原料粉末を配合組成が（Ｔｉ，Ｗ）Ｃ：５重量％、（Ｔａ，Ｎｂ）Ｃ：４重量％、Ｔｉ（Ｃ，Ｎ）：０．５重量％、Ｃｏ：８重量％、ＷＣ：８２．５重量％、となるように配合し、さらに結合相炭素量の調整用として平均粒径０．２μｍの炭素粉末を所定量添加し、湿式ボールミルで２４時間混合し、乾燥した後、１１７．６ＭＰａの圧力でプレス成形し、この圧粉体を１３００Ｐａの真空中、１４８０℃の範囲で１時間保持し焼結して、最終組成が８５．０％ＷＣ−３．０％Ｔｉ（Ｃ，Ｎ）−２．０％ＴａＣ−２．０％ＮｂＣ−８．０％Ｃｏ（以上重量％）であり、焼結合金結合相の格子定数が異なるＪＩＳ規格ＣＮＭＧ１２０４０８形状の発明品１１〜１５と比較品１１〜１５の超硬合金基材を作製した。
【００３０】
作製した超硬合金基材の格子定数は表４に示す。作製した超硬合金基材には、表面から合金内部に向かって３０μｍの深さに亘り（Ｗ，Ｔｉ，Ｔａ，Ｎｂ）（Ｃ，Ｎ）組成の複合炭化物が消失した結合相富加層が存在する。結合相富加層はＷＣ粒子と結合相からなり結合相量が増加した組織を有する。発明１１〜１５と比較品１１〜１５における結合相富化層中心部の結合相量は１６重量％であった。超硬合金基材の切刃部分には湿式ブラストホーニング処理をおこなった。
【００３１】
超硬合金基材を外熱式化学蒸着装置内に置き、Ｈ２雰囲気にて所定温度まで昇温した。被覆温度９００℃，原料ガス２．５％ＴｉＣｌ４−４８．８％Ｈ２―４８．７％Ｎ２（以上モル％），圧力４０ＫＰａの条件で厚さ０．５μｍのＴｉＮ膜を被覆し、続いて被覆温度９００℃，原料ガス２．０％ＴｉＣｌ４−８７．０％Ｈ２−１．０％ＣＨ３ＣＮ−１０％Ｎ２（以上モル％），圧力６．７ＫＰａの条件で厚さ６．０μｍのＴｉＣＮ柱状膜を被覆した。引き続きＨ２雰囲気で炉内を１０００℃に調整し、被覆温度１０００℃，原料ガス２．５％ＴｉＣｌ４−４８．８％Ｈ２―４８．７％Ｎ２（以上モル％），圧力４０ＫＰａの条件で厚さ０．５μｍのＴｉＮ膜を被覆し、被覆温度１０００℃，原料ガス２．５％ＡｌＣｌ３−９３．０％Ｈ２―１．５％ＨＣｌ−３．０％ＣＯ２（以上モル％），圧力１３．３ＫＰａの条件で厚さ１．０μｍのＡｌ２Ｏ３膜を被覆し、被覆温度１０００℃，原料ガス２．５％ＴｉＣｌ４−４８．８％Ｈ２―４８．７％Ｎ２（以上モル％），圧力４０ＫＰａの条件で厚さ０．５μｍのＴｉＮ膜を被覆した。その後、引き続きＨ２雰囲気で炉内を１１００℃に調整し、Ｈ２雰囲気で炉内を１１００℃、４０分間熱処理をおこなって、発明品１１〜１５と比較品１１〜１５を作製した。
【００３２】
【表４】
各試料をダイヤモンドカッターで切断した後、試料断面をダイヤモンドラップで鏡面研磨した。また発明品１１〜１５および比較品１１〜１５については、試料断面をＴＥＭ観察用のサンプルに加工してＴＥＭ観察し被膜密着相の形態と大きさを測定し、ＴＥＭ付属のＥＤＳで被膜密着相の元素分析をおこなった。これらの結果は表５に記載した。
【００３４】
【表５】
次いで発明品１１〜１５および比較品１１〜１５を被削材：溝付きのＳ４５Ｃの丸棒、切削速度：Ｖ＝１６０ｍ／ｍｉｎ、送り：ｆ＝０．２５ｍｍ／ｒｅｖ．、切り込み：ｄ＝２．０ｍｍ、切削時の雰囲気：水溶性切削液使用という条件で鋼の湿式断続切削試験をおこなった。試料に欠損または逃げ面摩耗量ＶＢが０．３ｍｍを超える時間を工具寿命とした。試料の工具寿命を測定し、その結果を表６に記載した。
【００３６】
【表６】
表６に示されるように鋼の湿式断続切削試験において被膜密着相が存在する発明品１１〜１５は比較品１１〜１５にくらべ切削寿命を向上させることが明らかである。すなわち、発明品１１〜１５は比較品１１〜１５に比べて耐欠損性に優れる。
【００３８】
【実施試験３】
最終成分組成が９０．０％ＷＣ−１０．０％Ｃｏ（以上重量％）であり、結合相の格子定数は３．５７０ÅであるＪＩＳ規格ＣＮＭＧ１２０４０８形状のスローアウェイチップを用意した。アルカリ洗剤を使用し表面を洗浄した。スローアウェイチップは真空炉内に設置し真空排気をおこなった．真空炉内の圧力が１．３３×１０−２Ｐａ以下になったら設定温度５００℃まで加熱した．圧力が１．３３×１０−２Ｐａ以下に戻ったことを確認し、Ｔｉターゲット、アーク電圧３８Ｖ、アーク電流１２０Ａ、基材電圧−６００Ｖ、Ａｒガス流量５０ｃｃ／分、加熱温度５００℃、処理時間１５分間の条件でエッチングした。次いで表８、表９に示す条件で被膜密着相を形成した後、Ｔｉターゲット、アーク電圧３８Ｖ、アーク電流１５０Ａ、基材電圧−２００Ｖ、Ｎ２ガス流量２００ｃｃ／分、加熱温度５００℃、処理時間１５分間の条件でＴｉＮ被膜を０．５μｍ厚さ被覆し、ＴｉＡｌターゲット、アーク電圧３８Ｖ、アーク電流１５０Ａ、基材電圧−２００Ｖ、Ｎ２ガス流量２００ｃｃ／分、加熱温度５００℃、処理時間５０分間の条件でＴｉＡｌＮ被膜を２．５μｍ厚さ被覆し、発明品１６〜２５と比較品１６〜２４を作製した。比較品２５は被膜密着相の形成工程以外を除いた発明品２５と同じ製造方法により作製した。
【００３９】
【表７】
【表８】
作製した試料はダイヤモンドカッターで切断した後、試料断面を鏡面研磨した。発明品１６〜２５と比較品１６〜２４について試料断面をＴＥＭ観察用のサンプルに加工してＴＥＭ観察し被膜密着相の形態と大きさを測定し、ＴＥＭ付属のＥＤＳで元素分析をおこなった。これらの結果は表９に記載した。さらに被膜密着相の結晶型をＴＥＭ付属の電子回折を用いて測定し、その結果を表９に記載した。
【００４２】
【表９】
発明品１６〜２５および比較品１６〜２５について、被削材：４本溝付きＳＮＣＭ４３９（ＨＢ３１０）の丸棒、切削速度：Ｖ＝１８０ｍ／ｍｉｎ、送り：ｆ＝０．１ｍｍ／ｒｅｖ．、切り込み：ｄ＝３．０ｍｍ、切削時の雰囲気：乾式という条件で乾式断続切削試験をおこなった。試料に欠損または平均逃げ面摩耗量ＶＢが０．３ｍｍを超える時間を工具寿命とした。試料の工具寿命を測定し、その結果を表１０に記載した。
【００４４】
【表１０】
表１０に示すように被膜密着相を有する発明品１６〜２５は比較品１６〜２５に比較してステンレス鋼の乾式断続切削において優れた耐欠損性を示す。
【００４６】
【実施試験４】
原料粉末として、それぞれ市販の平均粒径２μｍのＷＣ粉末、Ｃｏ粉末、ＴａＣ粉末、ＮｂＣ粉末、およびＴｉＣ粉末を用意し、これらの原料粉末を最終成分組成が７１．１％ＷＣ−１０．５％Ｃｏ―１１．４％ＴａＣ―１．２％ＮｂＣ−５．８％ＴｉＣ（以上重量％）になるように配合し、結合相中の炭素量を調整するため平均粒径０．２μｍのＣ粉末を所定量混合し、溶媒を加えボールミル中で４８時間混合し、乾燥した後、プレス圧力１４７ＭＰａでＣＮＭＧ１２０４０８のスローアウェイチップ形状用の圧粉体を成形し、ついで真空中、温度：１４００℃に１時間保持して焼結し、焼結後上下面を研磨加工により所定形状に調整するとともに切刃に乾式ブラシホーニングを施すことによってスローアウェイチップ形状をもった超硬合金基体を製造した。こうして作製した超硬合金基材を基材記号Ａとする。基材Ａの結合相格子定数は３．５７０Åであった。ついで上記超硬合金基体を、窒素分圧ＰＮ２：２０ＫＰａ、一酸化炭素分圧ＰＣＯ：７ＫＰａを有する圧力：２７ＫＰａの減圧雰囲気中で温度１４００℃に２時間保持して再焼結することによって、前記超硬合金基材の表面部に、組成：３５．９％ＴｉＣ―２．０％ＴｉＮ―１７．７％ＴａＣ―１．９％ＮｂＣ―６．４％Ｃｏ―３６．１％ＷＣ（以上重量％）、厚さ：３０μｍ、およびビッカース硬さＨｖ：１６００を有する硬化表面層を形成した。なお、前記超硬合金基材の内部硬さはビッカース硬さＨｖ：１４５０であった。こうして作製した硬化表面層がある超硬合金基材を基材記号Ｂとする。基材Ｂの結合相格子定数は３．５７０Åであった。ついで超硬合金基材Ａ，Ｂを外熱式化学蒸着装置内に置き、Ｈ２雰囲気にて所定温度まで昇温した。被覆温度９００℃，原料ガス２．０％ＴｉＣｌ４−８７．０％Ｈ２−１．０％ＣＨ３ＣＮ−１０％Ｎ２（以上モル％），圧力７ＫＰａの条件で厚さ５．０μｍのＴｉＣＮ柱状膜を被覆した。基材Ｂは被覆後、炉外に取り出し比較品２６を得た。基材Ａは、被覆後引き続き、Ｈ２雰囲気で炉内を１１４０℃、６０分間熱処理をおこなって発明品２６を得た。
【００４７】
発明品２６はダイヤモンドカッターで切断した後、試料断面を鏡面研磨した。ＴＥＭ観察用のサンプルに加工し、ＴＥＭ観察によって被膜密着相の形態と大きさを測定した。被膜密着相の組成についてはＴＥＭ付属のＥＤＳで被膜密着相の元素分析をおこなった。発明品２６には被膜と超硬合金基材の間に（Ｔｉ０．７，Ｗ０．３）（Ｃ０．８，Ｎ０．２）１の組成である平均厚さ０．０５μｍの層状粒子を示す被膜密着相が０．５μｍ間隔で形成されていた。
【００４８】
得られた試料について、被削材：４本溝入りＳ４８Ｃ（硬さＨＢ：２５５）、切削速度：Ｖ＝１５０ｍ、送り：ｆ＝０．５ｍｍ／ｒｅｖ．、切り込み：ｄ＝２ｍｍ、切削時雰囲気：ｗｅｔという条件で鋼の湿式断続旋削試験をおこない、欠損に至るまでの時間を表１１に示した。
【００４９】
【表１１】
焼結時に生成する厚さ３０μｍの硬化表面層を有する比較品２６に比較して、被覆後の熱処理によって生成する平均厚さ０．０５μｍの被膜密着相の層状粒子を有する発明品２６は、鋼の湿式断続旋削試験において優れた耐欠損性を示す。
【００５１】
【発明の効果】
上述したように窒化チタンおよび／または炭窒化チタンからなる最下層を含む被膜と超硬合金基材との間に、Ｔｉ、Ｗを含有する炭化物、窒化物、炭窒化物から選ばれた少なくとも１種の金属化合物からなる被膜密着相を形成することによって、被膜と超硬合金基材との密着性が向上する。被膜の密着性向上によって、被膜が有する特性を十分発揮させることが可能になる。本発明の被覆超硬合金を切削工具として用いた場合、過酷な切削条件下においても優れた耐摩耗性および／または耐欠損性を示すとともに工具寿命の向上が可能になる。
【図面の簡単な説明】
【図１】図１は本発明の被覆超硬合金の被膜と基材との界面部を示すＦＥ−ＳＥＭ組成像である。図１は被膜と超硬合金基材の間に熱処理法により被膜密着相が生成していることを示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coated cemented carbide having excellent wear resistance and chipping resistance used as a cutting tool and a wear-resistant tool.
[0002]
[Prior art]
As a use of the coated cemented carbide, there is a cutting tool. As a conventional technique of the cutting tool using the coated cemented carbide, there is JP-A-62-99467. JP-A-55-104475 discloses a surface-coated cemented carbide in which a hardened surface layer is formed on the surface of a cemented carbide substrate over a depth of 1 to 50 μm.
[0003]
[Problems to be solved by the invention]
Japanese Patent Application Laid-Open No. 62-99467 proposes a coated cemented carbide in which the surface of a cemented carbide base material is coated with TiCN and / or TiN having a thickness of 0.5 to 5.0 μm by a medium temperature CVD method. However, there is a problem that the adhesion between the lowermost layer TiCN and / or TiN and the cemented carbide base material is not sufficient, and the coating is easily peeled off. Japanese Patent Application Laid-Open No. 55-104475 proposes a surface-coated cemented carbide in which a hardened surface layer is formed on a surface portion of a cemented carbide substrate immediately below a coating over a depth of 1 to 50 μm. When the surface layer is thick and used as a cutting tool, there is a problem that cracks easily occur in the hardened surface layer.
[0004]
The present invention is to solve such a problem of the related art. That is, the lowermost layer of the film is made of titanium nitride and / or titanium carbonitride, and a film adhesion phase containing Ti and W is formed between the film and the cemented carbide substrate, whereby the film and the cemented carbide substrate are firmly connected. In close contact. It is an object of the present invention to provide a coated cemented carbide having excellent wear resistance and / or fracture resistance when used as a cutting tool, and a method for producing the same, by sufficiently exhibiting the properties of the coating by improving the adhesion. Things.
[0005]
[Means for Solving the Problems]
The present inventors have been engaged in research on coated cemented carbides for many years. However, Ti and W are placed between the coating including the lowermost layer made of titanium nitride and / or titanium carbonitride and the cemented carbide substrate. It has been found that when a film adhesion phase made of at least one metal compound selected from the group consisting of carbides, nitrides and carbonitrides is formed, the film and the cemented carbide substrate are firmly adhered to each other.
[0006]
The effect of forming a coating adhesion phase composed of at least one metal compound selected from carbides, nitrides, and carbonitrides containing Ti and W between the coating and the cemented carbide substrate is as follows. It is. Since the coating adhesion phase containing W has an element common to the cemented carbide substrate, the adhesion to the cemented carbide substrate is high. In addition, by including Ti in the film adhesion phase, the adhesion to the film whose lowermost layer is titanium nitride and / or titanium carbonitride is high. Therefore, when the coating adhesion phase exists between the coating and the cemented carbide substrate, the coating and the cemented carbide substrate can be firmly adhered. Further, it is preferable that the mechanical properties of the coating adhesion phase be between the mechanical properties of the lowermost layer of the coating and the mechanical properties of the surface portion of the cemented carbide base material, since continuity occurs in the mechanical properties.
[0007]
The coating adhesion phase is composed of at least one metal compound selected from carbides, nitrides, and carbonitrides containing Ti and W. Among them, carbonitrides containing Ti and W are preferable because they have higher toughness than carbides containing Ti and W and have higher hardness than nitrides containing Ti and W. The metal component of the coating adhesion phase may include at least one selected from the group consisting of Al, Si, Zr, Hf, V, Nb, Ta, Cr, and Mo, in addition to Ti and W.
[0008]
Specifically, (Ti, W) C, (Ti, W, Nb) C, (Ti, W, Ta) C, (Ti, W, Ta, Nb) C, (Ti, W, Al) C, (Ti, W, Si) C, (Ti, W) (C, N), (Ti, W, Nb) (C, N), (Ti, W, Ta) (C, N), (Ti, W , Ta, Nb) (C, N), (Ti, W, Al) (C, N), (Ti, W, Si) (C, N), (Ti, W) N, (Ti, W, Nb) ) N, (Ti, W, Ta) N, (Ti, W, Ta, Nb) N, (Ti, W, Al) N, (Ti, W, Si) N. The film adhesion phase is preferably crystalline, and among them, a cubic crystal is more preferable because of high hardness.
[0009]
As a form of the coating adhesion phase, a layer having an average thickness of 0.001 to 0.4 μm exists between the coating and the cemented carbide substrate, or a layered particle having an average thickness of 0.001 to 0.4 μm. Are dispersed at intervals of 0.001 to 10 μm. When the coating adhesion phase exists as a layer, if the average thickness is less than 0.001 μm, the effect of adhering the coating to the cemented carbide substrate decreases, and if the average thickness exceeds 0.4 μm, the coated cemented carbide is cut. When used as a tool, cracks easily occur in the coating adhesion phase, and the adhesion of the coating decreases. When the coating adhesion phase is a layer, a layer having an average thickness of 0.01 to 0.1 μm is preferable.
[0010]
When the coating adhesion phase is present as layered particles, the effect of adhering the coating to the cemented carbide substrate and the coating is reduced when the layered particles have an average thickness of less than 0.001 μm, and the layered particles have an average thickness of more than 0.4 μm. If there is, when the coated cemented carbide is used as a cutting tool, cracks are easily generated in the coating adhesion phase, and the adhesion of the coating decreases. It is preferable that the coating adhesion phase is a layered particle because the contact area with the coating or the cemented carbide substrate increases as compared to a continuous layer, and cracks generated in the coating adhesion phase are less likely to develop. When the interval between the layered particles is less than 0.001 μm, the layer does not change to a continuous layered shape. When the interval between the layered particles exceeds 10 μm, the effect of the coating adhesion phase is small and the adhesion of the coating decreases. When the coating adhesion phase is a layered particle, when the layered particles of the coating adhesion phase having an average thickness of 0.01 to 0.1 μm are dispersed at an interval of 0.01 to 1 μm between the coating and the cemented carbide substrate, The effect of improving the adhesion by the coating adhesion phase is high and is preferable.
[0011]
The coating adhesion phase is (Ti a , W b ) (C x , N y ) z And each molar ratio is 0.6 ≦ a ≦ 0.94, 0.06 ≦ b ≦ 0.4, a + b = 1, 0.1 ≦ x ≦ 0.9, 0.1 ≦ y ≦ 0.9, x + y = 1, and z indicate the molar ratio of the sum of the nonmetallic elements C and N to the sum of the metal elements Ti and W, and is preferably 0.8 ≦ z ≦ 1. The reason for setting 0.6 ≦ a ≦ 0.94 is that if a is less than 0.6, the Ti content tends to decrease and the adhesion to the coating tends to decrease, and if a exceeds 0.94, This is because there is a tendency that the W content relatively decreases and the adhesion to the cemented carbide base material decreases. The reason for setting 0.06 ≦ b ≦ 0.4 is that if b is less than 0.06, the adhesion to the cemented carbide substrate tends to decrease, and if b exceeds 0.4, the Ti content This is because there is a tendency that the amount decreases and the adhesion to the coating film decreases. The reason for setting 0.1 ≦ x ≦ 0.9 is that when x is less than 0.1, the hardness of the coating adhesion phase tends to decrease, and when x exceeds 0.9, the toughness of the coating adhesion phase is observed. Is a tendency to decrease. The reason for setting 0.1 ≦ y ≦ 0.9 is that if y is less than 0.1, the toughness of the coating adhesion phase tends to decrease, and if y exceeds 0.9, the hardness of the coating adhesion phase is high. Is a tendency to decrease. The reason for setting 0.8 ≦ z ≦ 1 is that if z is less than 0.8, the hardness of the coating adhesion phase decreases, and a metal compound having z exceeding 1.0 is difficult to obtain by coating or heat treatment. .
[0012]
In addition, the coating adhesion phase is (Ti a , W b , M c ) (C x , N y ) z And M represents at least one element selected from Al, Si, Zr, Hf, V, Nb, Ta, Cr, and Mo, and the molar ratio of each is 0.6 ≦ a ≦ 0. 94, 0.06 ≦ b ≦ 0.4, 0 <c ≦ 0.1, a + b + c = 1, 0.1 ≦ x ≦ 0.9, 0.1 ≦ y ≦ 0.9, x + y = 1, z is It indicates the molar ratio of the sum of the nonmetallic elements C and N to the sum of the metal elements Ti, W and M, and is preferably 0.8 ≦ z ≦ 1. In particular, when the cemented carbide substrate or coating contains at least one element selected from Al, Si, Zr, Hf, V, Nb, Ta, Cr, and Mo, (Ti a , W b , M c ) (C x , N y ) z The effect of improving the adhesion by the coating adhesion phase of
[0013]
The reason why c is set to 0 <c ≦ 0.1 in the molar ratio is that if c exceeds 0.1, the coating adhesion phase may have a crystal form other than cubic and the hardness tends to decrease. To be seen. The reason for setting 0.6 ≦ a ≦ 0.94 is that if a is less than 0.6, the Ti content tends to decrease and the adhesion to the coating tends to decrease, and if a exceeds 0.94, This is because there is a tendency that the W content relatively decreases and the adhesion to the cemented carbide base material decreases. The reason for setting 0.06 ≦ b ≦ 0.4 is that if b is less than 0.06, the adhesion to the cemented carbide substrate tends to decrease, and if b exceeds 0.4, the Ti content This is because there is a tendency that the amount decreases and the adhesion to the coating film decreases. The reason for setting 0.1 ≦ x ≦ 0.9 is that when x is less than 0.1, the hardness of the coating adhesion phase tends to decrease, and when x exceeds 0.9, the toughness of the coating adhesion phase is observed. Is a tendency to decrease. The reason for setting 0.1 ≦ y ≦ 0.9 is that if y is less than 0.1, the toughness of the coating adhesion phase tends to decrease, and if y exceeds 0.9, the hardness of the coating adhesion phase is high. Is a tendency to decrease. The reason for setting 0.8 ≦ z ≦ 1 is that if z is less than 0.8, the hardness of the coating adhesion phase decreases, and a metal compound having z exceeding 1.0 is difficult to obtain by coating or heat treatment. .
[0014]
The cemented carbide substrate is a cemented carbide composed of a hard phase composed of at least one of carbides, nitrides and carbonitrides of 4a, 5a and 6a in the periodic table and a binder phase mainly composed of an iron group metal. Alloy. As the coated cemented carbide substrate, a WC-based cemented carbide composed of a binder phase containing Co as a main component: 3 to 20% by weight and a hard phase containing WC as a main component: 80 to 97% by weight is preferable.
[0015]
Although C and W are dissolved in the binder phase of the cemented carbide, the amount of solid solution of W in the binder phase (hereinafter referred to as the amount of solid solution of W) increases, and the solid solution of C in the binder phase increases. When the amount of dissolution (hereinafter referred to as the amount of carbon) decreases, the adhesion between the coating adhesion phase and the cemented carbide substrate improves. The amount of W solid solution in the binder phase and the lattice constant of the binder phase are related. When the lattice constant la of the binder phase is 3.560 {≦ la ≦ 3.575}, the amount of W solid solution in the binder phase is high. Therefore, when the lattice constant la is 3.560 ° ≦ la ≦ 3.575 °, the cemented carbide substrate and the coating adhesion phase exhibit high adhesion. Further, when a coated cemented carbide having a lattice constant la of 3.560 ° ≦ la ≦ 3.575 ° is heat-treated, formation of a coating adhesion phase is facilitated. When the lattice constant la is less than 3.560 °, there is a tendency that the amount of solid solution of W decreases and the adhesion to the coating adhesion phase tends to decrease. The lattice constant la rarely exceeds 3.575 ° in the composition region of a practical cemented carbide. For the above reasons, a cemented carbide having a lattice constant la of 3.560Å ≦ la ≦ 3.575Å is preferred as the coated cemented carbide substrate. When measuring the saturation magnetic susceptibility to measure the amount of W solid solution in the binder phase, a cemented carbide base material exhibiting a saturation magnetic susceptibility of 68% to 80% is preferable. The saturation susceptibility is
Saturation susceptibility = (M / ((% by weight of Co) × 0.01 × 161)) × 100 (%)
Where M is the saturation magnetization of the cemented carbide substrate in emu / g and the weight percent of Co is the weight fraction of Co in the cemented carbide. 161 is the saturation magnetization of pure Co at emu / g.
[0016]
The coating is a coating including a lowermost layer made of titanium nitride and / or titanium carbonitride. The lowermost layer made of titanium nitride and / or titanium carbonitride is specifically TiN 0.9 , Ti (C 0.1 , N 0.9 ) 0.9 Can be exemplified. The coating may be a single-layer film of only the lowermost layer made of titanium nitride and / or titanium carbonitride, or a multilayer film including the lowermost layer of titanium nitride and / or titanium carbonitride. As the upper film other than the lowermost layer, at least one compound selected from the group consisting of elements of groups 4a, 5a and 6a of the periodic table, carbides, nitrides, oxides and borides of Al and Si, and mutual solid solutions thereof A single-layer film or a multi-layer film made of 0.9 , TiN 0.9 , Ti (C 0.5 , N 0.5 ) 0.9 , Al 2 O 3 , (Ti 0.5 , Al 0.5 ) N 0.9 And the like. The coating is applied to the cemented carbide substrate by chemical vapor deposition or physical vapor deposition.
[0017]
As a method of forming a coating adhesion phase between the coating of the coated cemented carbide and the cemented carbide substrate, there are a heat treatment method and a coating method. As a method for producing the film adhesion phase, a heat treatment method is preferable because the film adhesion phase is easily obtained. The heat treatment is performed by coating the lowermost layer made of titanium nitride and / or titanium carbonitride on the cemented carbide base material or by coating the upper film by a usual chemical vapor deposition method or physical vapor deposition method, and then setting the atmosphere in a reducing atmosphere or a vacuum atmosphere. Then, heat treatment is performed at a temperature 20 to 400 ° C. higher than the lowermost layer coating temperature for 5 to 400 minutes. As specific heat treatment conditions, a temperature of 1120 to 1200 ° C. and a holding time of 20 to 120 minutes are preferable. Heat treatment of a cemented carbide substrate having a lattice constant la of the binder phase of 3.560 ° ≦ la ≦ 3.575 ° and a coated cemented carbide coated with a lowermost layer made of titanium nitride and / or titanium carbonitride under optimal conditions Then, a coating adhesion phase is generated between the coating and the cemented carbide substrate.
[0018]
The heat treatment step may be performed during or after the coating step of the coating, or may be performed in another furnace after the coating step. Further, if the surface of the cemented carbide substrate is coated with the lowermost layer made of titanium nitride and / or titanium carbonitride and then coated with a coating having a high coating temperature, a coating adhesion phase may be formed. The formation principle at this time is the same as that of the heat treatment method, and the action of the formed film adhesion phase is the same as that of the heat treatment method.
[0019]
An example of the coating adhesion phase by the heat treatment method is a coating adhesion phase of layered particles formed at the interface where the coating and the binder phase of the cemented carbide substrate are in contact. It is considered that the binder phase of the cemented carbide substrate is involved in the formation of the coating adhesion phase. As shown in FIG. 1, the layered particles of the coating adhesion phase formed by the heat treatment method are flat on the coating film side, but have an irregular shape such as a combination of layers and particles on the cemented carbide base material side. This is because the elements Ti, C, and N contained in the lowermost layer and the elements W, Ti, Ta, Nb, C, and N contained in the binder phase are formed at the interface between the lowermost layer and the cemented carbide substrate by the heat treatment. Solid phase reaction occurs at the interface with the binder phase of the cemented carbide substrate, and (Ti, W) C, (Ti, W) (C, N), (Ti, W, Nb, Ta) (C, N), etc. It is considered that a metal compound composed of at least one of carbide, nitride, and carbonitride containing Ti and W is formed.
[0020]
The layered particles of the coating adhesion phase generated by the heat treatment method have a high anchor effect because they show an irregular shape such as a combination of layers and particles on the cemented carbide base material side. It is very preferable because the film and the cemented carbide substrate are firmly adhered to each other as compared with a continuous layered film adhesion phase. In the heat treatment method, the higher the amount of the binder phase W dissolved in the cemented carbide base material, the easier the film adhesion phase is formed. Therefore, the cemented carbide having a lattice constant la of the binder phase of 3.560Å ≦ la ≦ 3.575Å. Substrates are preferred.
[0021]
The coating method is to coat at least one of carbides, nitrides, and carbonitrides containing Ti and W using a source gas or a target containing Ti and W by an ordinary chemical vapor deposition method or physical vapor deposition method. Coating as an adhesive phase.
[0022]
[Execution test 1]
The final component composition is 87.0% WC-2.0% TiC-2.0% TaC-9.0% Co (more than weight%), and the lattice constant of the binder phase is 3.570 °. Was prepared. The cutting edge of the cemented carbide substrate was subjected to wet blast honing. Place the cemented carbide substrate in the external thermal chemical vapor deposition 2 The temperature was raised to a predetermined temperature in an atmosphere. Coating temperature 900 ° C, raw material gas 2.5% TiCl 4 -48.8% H 2 -48.7% N 2 (At least mol%), a pressure of 40 KPa, and a TiN film of 0.5 μm in thickness, followed by a coating temperature of 900 ° C. and a source gas of 2.0% TiCl. 4 -87.0% H 2 -1.0% CH 3 CN-10% N 2 (At least mol%) and a pressure of 6.7 KPa, the column was coated with a TiCN columnar film having a thickness of 6.0 μm. Continue H 2 The inside of the furnace was adjusted to a predetermined temperature in an atmosphere, and heat treatment was performed under the conditions shown in Table 1 to produce Invention Products 1 to 10 and Comparative Products 1, 3 to 9. Comparative product 2 was heat-treated in a vacuum sintering furnace under the conditions shown in Table 1 without performing a heat treatment in an external heating type chemical vapor deposition apparatus. The comparative product 10 was manufactured by the same manufacturing method as the invention product 1 except that the heat treatment was omitted.
[0023]
[Table 1]
After the sample was cut with a diamond cutter, the cross section of the sample was mirror-polished with diamond wrap. For the inventive products 1 to 9 and the comparative products 3 to 10, the sample cross section was processed into a sample for TEM observation, and the TEM observation was performed to measure the form and size of the coating adhesion phase. Analysis was carried out, and the crystal form of the film adhesion phase was measured using electron diffraction attached to the TEM. The results are shown in Table 2. For the inventive product 10 and the comparative products 1 and 2, the mirror-polished cross sections were observed by FE-SEM, the form and size of the coating adhesion phase were measured, and the elemental analysis of the coating adhesion phase was performed using the EDS attached to the FE-SEM. The results are shown in Table 2. Furthermore, after processing the cross-sections of the inventive product 10 and the comparative products 1 and 2 into samples for TEM observation, the crystal form of the coating adhesion phase was measured using the electron diffraction attached to the TEM, and the results are shown in Table 2. .
[0025]
[Table 2]
Work material: round bar of SUS304, cutting speed: V = 100 m / min, feed: f = 0.25 mm / rev. A continuous cutting test of stainless steel was performed under the following conditions: cutting depth: d = 5.0 mm; cutting atmosphere: dry; cutting time: 2 minutes. The boundary wear of the cutting edge of the sample was measured, and the results are shown in Table 3.
[0027]
[Table 3]
As shown in Table 3, invention products 1 to 10 in which a film adhesion phase having a predetermined thickness is present are compared with comparative products 1 and 2 in which the film adhesion phase is thick and comparative products 3 to 10 in which no film adhesion phase is observed. It shows excellent wear resistance in dry continuous cutting of stainless steel.
[0029]
[Execution test 2]
Commercially available WC powder, (Ti, W) C powder, (Ta, Nb) C powder, Ti (C, N) powder, and Co powder having an average particle diameter of 2 μm are prepared as raw material powders. The composition is (Ti, W) C: 5% by weight, (Ta, Nb) C: 4% by weight, Ti (C, N): 0.5% by weight, Co: 8% by weight, WC: 82.5% by weight %, And a predetermined amount of carbon powder having an average particle diameter of 0.2 μm is added for adjusting the amount of carbon in the binder phase, mixed in a wet ball mill for 24 hours, dried, and then dried at a pressure of 117.6 MPa. This green compact is held in a vacuum of 1300 Pa in a range of 1480 ° C. for 1 hour and sintered to have a final composition of 85.0% WC-3.0% Ti (C, N) -2. 2.0% TaC-2.0% NbC-8.0% Co (or more by weight). Cemented carbide substrates of invention products 11 to 15 and comparison products 11 to 15 having JIS standard CNMG120408 shapes having different lattice constants were produced.
[0030]
Table 4 shows the lattice constants of the manufactured cemented carbide substrates. In the manufactured cemented carbide base material, there is a binder phase rich layer in which the complex carbide of (W, Ti, Ta, Nb) (C, N) composition has disappeared over a depth of 30 μm from the surface toward the inside of the alloy. I do. The binder phase rich layer has a structure composed of WC particles and a binder phase and having an increased binder phase amount. In the inventions 11 to 15 and the comparative products 11 to 15, the amount of the binder phase at the center of the binder phase-enriched layer was 16% by weight. The cutting edge portion of the cemented carbide substrate was subjected to wet blast honing.
[0031]
Place the cemented carbide substrate in the external thermal chemical vapor deposition 2 The temperature was raised to a predetermined temperature in an atmosphere. Coating temperature 900 ° C, raw material gas 2.5% TiCl 4 -48.8% H 2 -48.7% N 2 (At least mol%), a pressure of 40 KPa, a 0.5 μm-thick TiN film is coated, followed by a coating temperature of 900 ° C. and a source gas of 2.0% 4 -87.0% H 2 -1.0% CH 3 CN-10% N 2 (At least mol%) and a pressure of 6.7 KPa, a TiCN columnar film having a thickness of 6.0 μm was coated. Continue H 2 The furnace was adjusted to 1000 ° C in an atmosphere, the coating temperature was 1000 ° C, and the raw material gas was 2.5% TiCl. 4 -48.8% H 2 -48.7% N 2 (At least mol%), a pressure of 40 KPa, a TiN film having a thickness of 0.5 μm, a coating temperature of 1000 ° C., a raw material gas of 2.5% AlCl. 3 -93.0% H 2 -1.5% HCl-3.0% CO 2 (More than mol%), pressure of 13.3 KPa, thickness of 1.0 μm Al 2 O 3 Coating the film, coating temperature 1000 ° C, raw material gas 2.5% TiCl 4 -48.8% H 2 -48.7% N 2 (At least mol%) and a pressure of 40 KPa, a 0.5 μm thick TiN film was coated. After that, continue to H 2 The atmosphere inside the furnace was adjusted to 1100 ° C. 2 Heat treatment was performed in the furnace at 1100 ° C. for 40 minutes in an atmosphere to produce invention products 11 to 15 and comparative products 11 to 15.
[0032]
[Table 4]
After each sample was cut with a diamond cutter, the cross section of the sample was mirror-polished with diamond wrap. For the invention products 11 to 15 and the comparative products 11 to 15, the sample cross section was processed into a sample for TEM observation, and the TEM observation was performed to measure the form and size of the coating adhesion phase. Was subjected to elemental analysis. These results are shown in Table 5.
[0034]
[Table 5]
Then, the invention products 11 to 15 and the comparison products 11 to 15 were cut with a work material: a round bar of S45C having a groove, a cutting speed: V = 160 m / min, and a feed: f = 0.25 mm / rev. The steel was subjected to a wet intermittent cutting test under the following conditions: cutting depth: d = 2.0 mm; atmosphere during cutting: use of a water-soluble cutting fluid. The tool life was defined as the time during which the sample had a chipped or flank wear VB of more than 0.3 mm. The tool life of the sample was measured and the results are shown in Table 6.
[0036]
[Table 6]
As shown in Table 6, it is clear that the invention products 11 to 15 having the film adhesion phase in the wet intermittent cutting test of steel improve the cutting life as compared with the comparative products 11 to 15. That is, invention products 11 to 15 are more excellent in fracture resistance than comparison products 11 to 15.
[0038]
[Execution test 3]
A throw-away chip having a JIS standard CNMG120408 shape having a final component composition of 90.0% WC-10.0% Co (weight% or more) and a lattice constant of a binder phase of 3.570 ° was prepared. The surface was cleaned using an alkaline detergent. The throw-away tip was installed in a vacuum furnace and evacuated. The pressure inside the vacuum furnace is 1.33 × 10 -2 When it became Pa or less, it was heated to the set temperature of 500 ° C. The pressure is 1.33 × 10 -2 After confirming that the pressure returned to Pa or less, etching was performed under the conditions of a Ti target, an arc voltage of 38 V, an arc current of 120 A, a substrate voltage of −600 V, an Ar gas flow rate of 50 cc / min, a heating temperature of 500 ° C., and a processing time of 15 minutes. Next, after forming a coating adhesion phase under the conditions shown in Tables 8 and 9, a Ti target, an arc voltage of 38 V, an arc current of 150 A, a substrate voltage of -200 V, N 2 A TiN film was coated at a thickness of 0.5 μm under the conditions of a gas flow rate of 200 cc / min, a heating temperature of 500 ° C., and a processing time of 15 minutes, a TiAl target, an arc voltage of 38 V, an arc current of 150 A, a substrate voltage of −200 V, and N 2 Under conditions of a gas flow rate of 200 cc / min, a heating temperature of 500 ° C., and a processing time of 50 minutes, a TiAlN film was coated to a thickness of 2.5 μm to produce invention products 16 to 25 and comparative products 16 to 24. The comparative product 25 was produced by the same manufacturing method as that of the inventive product 25 except for the step of forming the coating adhesion phase.
[0039]
[Table 7]
[Table 8]
The prepared sample was cut with a diamond cutter, and the cross section of the sample was mirror-polished. The cross-sections of the inventive products 16 to 25 and the comparative products 16 to 24 were processed into TEM observation samples, the TEM observation was performed, the form and size of the coating adhesion phase were measured, and the element analysis was carried out with an EDS attached to the TEM. These results are shown in Table 9. Further, the crystal form of the film adhesion phase was measured using electron diffraction attached to the TEM, and the results are shown in Table 9.
[0042]
[Table 9]
Work material: round bar of SNCM439 (HB310) with four grooves, cutting speed: V = 180 m / min, feed: f = 0.1 mm / rev. , Depth of cut: d = 3.0 mm, atmosphere at the time of cutting: dry type, a dry intermittent cutting test was performed. The tool life was defined as the time during which the sample was defective or the average flank wear amount VB exceeded 0.3 mm. The tool life of the sample was measured, and the results are shown in Table 10.
[0044]
[Table 10]
As shown in Table 10, the invention products 16 to 25 having the coating adhesion phase show excellent fracture resistance in dry interrupted cutting of stainless steel as compared with the comparison products 16 to 25.
[0046]
[Test 4]
As raw material powders, commercially available WC powder, Co powder, TaC powder, NbC powder, and TiC powder each having an average particle diameter of 2 μm are prepared, and these raw material powders have a final component composition of 71.1% WC-10.5% Co-11.4% TaC-1.2% NbC-5.8% TiC (more than weight%), C powder having an average particle size of 0.2 μm to adjust the amount of carbon in the binder phase Is mixed in a ball mill for 48 hours after adding a solvent, and after drying, a green compact for a throw-away tip shape of CNMG120408 is formed at a pressing pressure of 147 MPa, and then, in a vacuum at a temperature of 1400 ° C. Carbide with a throw-away tip shape by sintering while holding for a while, adjusting the upper and lower surfaces to a predetermined shape by sintering and applying dry brush honing to the cutting blade after sintering A substrate was manufactured. The cemented carbide base material thus manufactured is referred to as base material symbol A. The binder phase lattice constant of Substrate A was 3.570 °. Then, the above-mentioned cemented carbide substrate was subjected to nitrogen partial pressure PN. 2 : 20 KPa, carbon monoxide partial pressure PCO: 7 KPa Pressure: 27 KPa in a reduced pressure atmosphere at a temperature of 1400 ° C. for 2 hours and re-sintering, the composition on the surface of the cemented carbide base material: 35.9% TiC-2.0% TiN-17.7% TaC-1.9% NbC-6.4% Co-36.1% WC (or more by weight), thickness: 30 μm, and Vickers hardness A cured surface layer having an Hv of 1600 was formed. The internal hardness of the cemented carbide substrate was Vickers hardness Hv: 1,450. The cemented carbide base material having the hardened surface layer thus produced is referred to as base material symbol B. Substrate B had a bound phase lattice constant of 3.570 °. Then, the cemented carbide substrates A and B are placed in an external heat type chemical vapor deposition apparatus, 2 The temperature was raised to a predetermined temperature in an atmosphere. 900 ° C coating temperature, 2.0% TiCl source gas 4 -87.0% H 2 -1.0% CH 3 CN-10% N 2 (At least mol%) and a pressure of 7 KPa, a TiCN columnar film having a thickness of 5.0 μm was coated. After coating, the base material B was taken out of the furnace to obtain a comparative product 26. Substrate A is continuously coated with H 2 A heat treatment was performed in the furnace at 1140 ° C. for 60 minutes in an atmosphere to obtain invention product 26.
[0047]
After cutting the inventive product 26 with a diamond cutter, the cross section of the sample was mirror-polished. The sample was processed into a sample for TEM observation, and the form and size of the coating adhesion phase were measured by TEM observation. With respect to the composition of the coating adhesion phase, an elemental analysis of the coating adhesion phase was performed using an EDS attached to the TEM. Inventive product 26 includes (Ti) between the coating and the cemented carbide substrate. 0.7 , W 0.3 ) (C 0.8 , N 0.2 ) 1 Was formed at intervals of 0.5 μm showing layered particles having an average thickness of 0.05 μm and having a composition of 0.5 μm.
[0048]
For the obtained sample, work material: S48C with four grooves (hardness H B : 255), cutting speed: V = 150 m, feed: f = 0.5 mm / rev. The steel was subjected to a wet intermittent turning test under the following conditions: cutting depth: d = 2 mm; cutting atmosphere: wet;
[0049]
[Table 11]
Compared to the comparative product 26 having a 30 μm thick hardened surface layer formed during sintering, the invention product 26 having the layered particles of the coating adhesion phase having an average thickness of 0.05 μm formed by heat treatment after coating is made of steel. It shows excellent fracture resistance in wet intermittent turning tests.
[0051]
【The invention's effect】
As described above, at least one selected from carbides, nitrides, and carbonitrides containing Ti and W is provided between the coating including the lowermost layer made of titanium nitride and / or titanium carbonitride and the cemented carbide substrate. The adhesion between the coating and the cemented carbide substrate is improved by forming the coating adhesion phase composed of the various metal compounds. By improving the adhesion of the coating, the properties of the coating can be fully exhibited. When the coated cemented carbide of the present invention is used as a cutting tool, excellent wear resistance and / or chipping resistance can be exhibited even under severe cutting conditions, and the tool life can be improved.
[Brief description of the drawings]
FIG. 1 is an FE-SEM composition image showing an interface between a coating of a coated cemented carbide according to the present invention and a substrate. FIG. 1 shows that a coating adhesion phase is formed between the coating and the cemented carbide substrate by a heat treatment method.
Claims (7)
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| JP2002265621A JP4330859B2 (en) | 2002-09-11 | 2002-09-11 | Coated cemented carbide and method for producing the same |
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| JP2002265621A JP4330859B2 (en) | 2002-09-11 | 2002-09-11 | Coated cemented carbide and method for producing the same |
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| JP2004100004A true JP2004100004A (en) | 2004-04-02 |
| JP4330859B2 JP4330859B2 (en) | 2009-09-16 |
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