CN103339283B - 硬质层叠被膜 - Google Patents
硬质层叠被膜 Download PDFInfo
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Abstract
对于本实施例的硬质层叠被膜20,通过将由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22和由TiB2构成的第2被膜24在母材12、62、84的表面上交替地层叠而构成硬质层叠被膜20,构成第1被膜22的(TiaCrbBc)合金的原子比a、b、c存在a=1-b-c这样的相互关系,原子比b为0<b≤0.4的范围内的值,原子比c为0<c≤0.3的范围内的值,第1被膜22的膜厚为0.1μm以上5.0μm以下,第2被膜24的膜厚为0.1μm以上5.0μm以下,硬质层叠被膜20的总膜厚为0.2μm以上10.0μm以下,因此能获得在耐磨损性、耐热性、耐熔敷性和密合性(附着强度)上都能满足的特性。
Description
技术领域
本发明涉及将组成彼此不同的2种被膜在母材的表面上交替地层叠的硬质层叠被膜,特别涉及该硬质层叠被膜的特性的改进。
背景技术
作为在高速度工具钢、超硬合金等的工具母材的表面设置的耐磨损性的硬质被膜,提出了将组成彼此不同的第1被膜和第2被膜这2种交替地层叠的各种的硬质层叠被膜。专利文献1、2中记载的硬质层叠被膜是其一例,将由元素周期表的IVa族、Va族、VIa族的金属元素、或Al等的氮化物、碳化物等构成的2种被膜按规定的层叠厚度周期反复层叠。即,采用第1被膜和第2被膜的薄膜化、多层化、金属元素的合金化等各种手段,实现了被膜硬度、耐磨损性的提高。
现有技术文献
专利文献
专利文献1:特开平7-205361号公报
专利文献2:特开2005-256081号公报
发明内容
发明要解决的课题
但是,使用由这样的硬质层叠被膜被覆的切削工具,特别地,对インコネル(镍基超硬合金的商标)、钛合金等耐热合金、包含它们的复合材料进行切削加工的情况下,在耐熔敷性、耐磨损性上尚未获得具有能够充分满足的性能的切削工具,存在由于磨损大,无法获得长寿命的缺点。
本发明以以上的实际情况为背景而完成,其目的在于提供即使对インコネル、钛合金等耐热合金、包含它们的复合材料进行切削加工的情况下也能充分地获得耐熔敷性、耐磨损性的硬质层叠被膜。
用于解决课题的手段
本发明人以上述的实际情况为背景,反复进行了各种研究,结果发现:如果使Ti系的硬质层叠被膜中含有硼元素B,则使高温硬度和耐熔敷性改善,但无法充分地获得耐磨损性、附着强度,另一方面,如果在使构成Ti系的硬质层叠被膜的第1被膜和第2被膜的一者含有包含硼元素B的TiCr合金的氮化物、碳化物、碳氮化物的同时,使另一者含有硼元素B,交替地层叠,则在耐磨损性和密合性(附着强度)上适宜地改善。本发明基于这样的见识而完成。
即,第1发明,其特征在于,(a)是将组成彼此不同的第1被膜和第2被膜这2种在母材的表面上交替地多个层叠的硬质层叠被膜,(b)上述第1被膜是(TiaCrbBc)的氮化物、碳化物或碳氮化物,(c)上述第2被膜是TiB2,(d)上述第1被膜中的原子比a、b、c为a=1-b-c的相互关系,为0<b≤0.4、0<c≤0.3,(e)上述第1被膜的膜厚为0.1μm以上5.0μm以下,(f)上述第2被膜的膜厚为0.1μm以上5.0μm以下,(g)上述硬质层叠被膜的总膜厚为0.2μm以上10.0μm以下,(h)上述硬质层叠被膜的层叠数为2层以上100层以下。
发明的效果
根据第1发明的硬质层叠被膜,通过将作为(TiaCrbBc)的氮化物、碳化物或碳氮化物的第1被膜与作为TiB2的第2被膜在母材的表面上交替地层叠,从而构成硬质层叠被膜,其第1被膜中的(TiaCrbBc)的原子比a、b、c存在a=1-b-c这样的相互关系,为0<b≤0.4、0<c≤0.3,上述第1被膜的膜厚为0.1μm以上5.0μm以下,上述第2被膜的膜厚为0.1μm以上5.0μm以下,上述硬质层叠被膜的总膜厚为0.2μm以上10.0μm以下,构成该硬质层叠被膜的第1被膜和第2被膜的层叠数为2层以上100层以下,因此在耐磨损性和耐熔敷性上,都能获得满足需要的特性。
其中,优选地,上述硬质层叠被膜,除了适用于立铣刀、丝锥、钻头等旋转切削工具的至少刃部以外,也可适宜地应用于在刨刀等非旋转式的切削工具、或滚轧工具等各种加工工具的表面设置的硬质层 叠被膜,也可适用于半导体装置等的表面保护膜等在加工工具以外的部件的表面设置的硬质层叠被膜。作为工具母材等设置硬质层叠被膜的母材的材质,适合使用超硬合金、高速度工具钢,也可为其他的金属材料。
此外,优选地,作为形成上述硬质层叠被膜的PVD法(物理蒸镀法),优选使用电弧离子镀法、溅射法。第1被膜和第2被膜的膜厚能够通过对于靶的投入电力量、转台的旋转速度等适当地设定。
此外,优选地,上述第1被膜中的(TiaCrbBc)的原子比a、b、c具有a=1-b-c这样的关系,原子比b可为比0大且0.4以下的值,原子比c可为比0大且0.3以下的值,能够根据金属元素的种类、要求特性等适当地设定。如果原子比b和c成为0,或者大于0.4和0.3,难以获得耐磨损性。此外,第1被膜可为(TiaCrbBc)的氮化物、碳化物、碳氮化物的任何物质。
此外,优选地,上述第1被膜和第2被膜中的组成中,除了(TiaCrbBc)的氮化物、碳化物、碳氮化物和TiB2以外,可含有不可避免的杂质元素、不对性质产生影响的其他的元素。
此外,优选地,上述第1被膜的膜厚为0.1μm以上5.0μm以下,第2被膜的膜厚为0.1μm以上5.0μm以下,硬质层叠被膜的总膜厚为0.2μm以上10.0μm以下。第1被膜或第2被膜的膜厚低于0.1μm,或者硬质层叠被膜的总膜厚低于0.2μm的情形下,至少在耐磨损性上无法获得能满足的特性。第1被膜或第2被膜的膜厚超过0.5μm的情形和硬质层叠被膜的总膜厚超过10.0μm的情形下,制造成本升高。
此外,优选地,第1被膜和第2被膜的合计的层叠数可为2层以上100层以下的范围。如果层叠数低于2,第1被膜或第2被膜不存在,对于耐磨损性,无法获得能满足的特性。此外,层叠数越超过100,制造成本越升高。
第1被膜和第2被膜可以以任一者在先在构件(工具母材等)的表面上形成,希望根据被膜的组成在先设置例如密合性优异的一方,也能够无特别限定地形成。此外,可使第1被膜和第2被膜成对地层叠,也能够使合计的层数为奇数,在先形成了第1被膜的情况下,最上层也可以为第1被膜,在先形成了第2被膜的情况下,最上层也可为第2被膜。再有,在本发明的硬质层叠被膜与构件表面之间,根据需要也能够存在其他的硬质被膜,也能够在最上层设置另外的被膜。
附图说明
图1为表示应用了本发明的硬质层叠被膜的立铣刀的图,是从与轴心的直角方向看到的正面图。
图2为表示图1的立铣刀的图,是将在其刃部的表面部分层叠的硬质层叠被膜的构成放大说明的截面图。
图3为对采用PVD法能够适宜地形成图1的硬质层叠被膜的电弧离子镀装置的一例进行说明的概略构成图。
图4为说明图3的电弧离子镀装置中的转台和靶的位置关系的平面图。
图5为应用了本发明的硬质层叠被膜的球头立铣刀从与其轴心的直角方向看到的正面图。
图6为图5的球头立铣刀的刃部从轴心方向看到的侧面图。
图7为应用了本发明的硬质层叠被膜的丝锥从与其轴心的直角方向看到的正面图。
图8为表示图7的丝锥的刃部的斜视图。
图9为在图7的丝锥的刃部形成本发明的硬质层叠被膜,将其硬质层叠被膜的组成比、膜厚、层叠数、耐磨损性的评价结果与在大致 的数值范围之外的试验品和由1种被膜构成的硬质成层被膜被覆的现有品的组成比、膜厚、层叠数、耐磨损性评价结果对比而表示的图。
具体实施方式
以下参照附图对本发明的实施例详细说明。
实施例1
图1是对作为本发明的硬质层叠被膜被覆工具的一例的立铣刀10进行说明的图,是从与轴心C的直角方向看到的正面图。该立铣刀10在由超硬合金构成的工具母材12一体地设置有刀柄和刃部14。在刃部14设置有螺线状的外周刃16和直线状的底刃18作为切削刃,通过围绕轴心C被旋转驱动,利用其等的外周刃16和底刃18进行切削加工,同时在其刃部14的表面涂覆有硬质层叠被膜20。图1的斜线部表示硬质层叠被膜20。
图2是将在刃部14的表面部分涂覆的硬质层叠被膜20的构成放大表示的截面图。立铣刀10为旋转切削工具,工具母材12相当于将硬质层叠被膜20设置在表面的基材。
由图2可以看到,硬质层叠被膜20是将彼此不同的组成的第1被膜22和第2被膜24在工具母材12的表面上交替地多个层叠而成的。第1被膜22由(TiaCrbBc)合金的氮化物、碳化物、碳氮化物或碳氧氮化物构成。其(TiaCrbBc)合金的原子比a、b、c存在a=1-b-c的相互关系,原子比b为0<b≤0.4的范围内的值,即大于0且0.4以下的范围内的值,原子比c为0<c≤0.3的范围内的值,即大于0且0.3以下的范围内的值。此外,第1被膜22以其膜厚成为0.1μm以上5.0μm以下的方式形成。第2被膜24由TiB2合金构成。该第2被膜24以其膜厚成为0.1μm以上5.0μm以下的方式形成。而且,通过这些第1被膜22和第2被膜24的层叠构成的硬质层叠被膜20由2层以上100层以下的层叠数构成,以其膜厚成为0.2μm以上10.0μm以下的方式形成。
图3为对形成上述硬质层叠被膜20时适合使用的电弧离子镀装置30的概略的构成进行说明的图。图4为相当于图3的A-A截面的图, 为平面图。该电弧离子镀装置30具有:大致水平的第1转台32;将该第1转台32围绕大致垂直的一中心线O旋转驱动的旋转驱动装置33;在第1转台32的外周部配置多个(图4中为4个),而且保持多个工件即形成了被覆硬质层叠被膜20前的切削刃16、18等的工具母材12的第2转台34;对工具母材12施加负的偏压的偏置电源36;作为将工具母材12等收纳于内部的处理容器的腔室38;向腔室38内供给规定的反应气体的反应气体供给装置40;将腔室38内的气体用真空泵等排出并减压的排气装置42;第1电弧电源44;第2电弧电源46等。该电弧离子镀装置30相当于被膜形成装置。应予说明,图4中,将安装于第2转台34的工具母材12省略了。
将上述第2转台34与第1转台32平行地配设,围绕与该第1转台32的一中心线O平行的自身的中心线(第2中心线)旋转的同时,将多个工具母材12以其轴心与第2中心线平行、刃部14向上的垂直的姿势保持。因此,将多个工具母材12围绕第2转台34的中心线(第2中心线)旋转驱动的同时,通过第1转台32,围绕一中心线O旋转驱动。在第1转台32的周围,围绕一中心线O,将第1靶48和第2靶52以180°间隔交替地位置固定地配设,通过第1转台32的连续旋转,工具母材12与第2转台34一起,交替地周期性地通过其等的第1靶48和第2靶52前。本实施例中,第1靶48和第2靶52各自围绕一中心线O,以180°间隔平均配设2个。再有,多个第2转台34以例如被独自的旋转驱动装置独立地旋转驱动的方式构成,也能够通过齿轮机构等与第1转台32的旋转连动,被机械地旋转驱动。
上述反应气体供给装置40具有氮气(N2)、烃气体(CH4、C2H2等)、氧气(O2)等的槽,根据第1被膜22、第2被膜24的组成,例如氧化物的情形下只供给氧气,氮化物的情形下只供给氮气,碳化物的情形下只供给烃气体,碳氮化物的情形下供给氮气和烃气体,碳氧氮化物的情形下供给氧气、氮气和烃气体。形成硼化物、氧氮化物、硼氮化物等其他化合物的情形下,也可同样地供给规定的反应气体。
在与上述一中心线O对向的位置配设的第1靶48由作为上述第1 被膜22的构成物质的(TiaCrbBc)合金构成,另一方面,在同样地与一中心线O对向的位置配设的第2靶52由作为上述第2被膜24的构成物质的TiB2合金构成。而且,上述第1电弧电源44,将上述第1靶48作为阴极,在与阳极50之间通入规定的电弧电流,使其电弧放电,从而从第1靶48使(TiaCrbBc)合金蒸发,蒸发的(TiaCrbBc)合金成为正(+)的金属离子,附着于施加着负(-)的偏压的工具母材12。此时,与供给的规定的反应气体反应,形成由上述(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22。此外,第2电弧电源46,将上述第2靶52作为阴极,在与阳极54之间通入规定的电弧电流,使其电弧放电,从而从第2靶52使TiB2合金蒸发,蒸发的TiB2合金成为正(+)的金属离子,附着于施加着负(-)的偏压的工具母材12。
使用这样的电弧离子镀装置30在工具母材12的刃部14的表面形成硬质层叠被膜20时,预先用排气装置42排气,同时从反应气体供给装置40供给规定的反应气体以使腔室38内保持在规定的压力(例如1.33Pa~3.99Pa左右),同时通过偏置电源36向工具母材12施加规定的偏压(例如-50V~-150V左右)。此外,将第2转台34围绕中心线旋转驱动,同时使第1转台32围绕一中心线O沿一方向以一定速度连续旋转,从而使工具母材12与第2转台34一起围绕第2中心线旋转,同时交替地周期性地通过第1靶48和第2靶52前。
由此,工具母材12通过第1靶48前时,使由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22附着于工具母材12的表面,通过第2靶52前时,使由TiB2构成的第2被膜24附着于工具母材12的表面。由此,在工具母材12的表面将第1被膜22和第2被膜24交替地连续地层叠,形成硬质层叠被膜20。本实施例中,由于在第1转台32的周围配设第1靶48和第2靶52,因此通过第1转台32旋转,将第1被膜22和第2被膜24层叠。各电弧电源44、46的电弧电流的电流值根据第1被膜22、第2被膜24的膜厚确定。这样的硬质层叠被膜20的形成能够通过包括计算机的控制装置自 动地进行。
再有,由于第1被膜22由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成,第2被膜24由TiB2构成,因此必须分别形成第1被膜22和第2被膜24,进行从反应气体供给装置40供给的反应气体的切换,使第1电弧电源44和第2电弧电源46选择性地ON、OFF,将第1靶48和第2靶52切换。
实施例2
图5和图6表示对于前述的硬质层叠被膜20经过与实施例1的立铣刀10同样的硬质被膜形成工序而在刃部64的表面形成的球头立铣刀60,从与其轴心C正交的方向看到的正面图和从轴心C的方向观察刃部64的侧面图。该球头立铣刀60是在由超硬合金构成的工具母材62将刀柄和刃部64一体地设置。在刃部64,作为切削刃,设置有螺线状的外周刃66和2片半圆状的球形刃(底刃)68,通过围绕轴心旋转驱动,利用其等的外周刃66和球形刃68进行切削加工,同时在其刃部64的表面涂布有图2中所示的硬质层叠被膜20。图5和图6的斜线部表示该硬质层叠被膜20。
实施例3
图7和图8表示对于前述的硬质层叠被膜20经过与立铣刀10同样的硬质被膜形成工序而在刃部76的表面形成的丝锥70,从与其轴心C正交的方向看到的正面图和从轴心C方向观察其刃部76的截面图。该丝锥70是例如具有用超硬合金制的轴状的工具母材84一体地构成的3个螺旋槽80的螺旋槽丝锥,在轴心方向依次具有用于被把持于主轴的刀柄72、首部74和刃部76。刃部76通过将外螺纹78用螺旋槽80分断,从而沿其螺旋槽80设置有切削刃82。此外,刃部76具有完全的螺纹牙相连的完全牙部76a和螺纹牙越成为轴端越以锥状变小的切削部76b。在该刃部76的表面涂布有图2中所示的硬质层叠被膜20。图7的斜线部表示该硬质层叠被膜20。
接下来,作成使在上述丝锥70的刃部76的表面被覆的硬质层叠被膜的组成、膜厚、层叠数如图9中所示改变的多种的试验丝锥,基 于在以下的螺纹切削试验条件下切削时的加工孔数进行评价,将结果示于图9的表中。图9中,A层对应于第1被膜22,B层对应于第2被膜24。此外,A层的组成中末尾的“N”表示氮化物,“C”表示碳化物,“CN”表示碳氮化物,“CON”表示碳氧氮化物。此外,图9中,所谓加工孔数,是加工直至第1完全牙的顶面的宽度由于磨损而达到0.3mm的孔数,所谓合格,是评价耐磨损性,以其加工孔数超过了140为基准判断。
<切削试验条件>
丝锥:带有硬质层叠被覆的超硬合金制丝锥(M4×0.7)
被削材料:インコネル718(镍基超硬合金的商标)
使用机械:立型マシニングセンタ
切削速度:3m/分钟
螺纹长度:9.5mm(通孔)
下孔径:φ3.3mm
切削油:非水溶性
在上述的螺纹切削试验中,形成了由第1被膜22和第2被膜24的交替层叠构成的硬质层叠被膜20的试验丝锥对于熔敷性、耐热性、密合性,均能够满足,但对于耐磨损性,如图9的判定结果所示,看到了差异。如图9中所示,对于形成了由第1被膜22和第2被膜24的交替层叠构成的硬质层叠被膜20的试验丝锥中的合格评价的试验丝锥,标以本发明品1乃至46的名称,对于不合格评价的试验丝锥,标以试验品1乃至10的名称,对于形成了由1种被膜的层叠构成的硬质层叠被膜的试验丝锥,标以现有品1乃至8的名称。
作为合格评价的试验丝锥的本发明品1乃至46,在其刃部被覆的硬质层叠被膜20由第1被膜22(A层)和第2被膜24(B层)的交替层叠构成,第1被膜22由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成。其(TiaCrbBc)合金的原子比a、b、c存在a=1-b-c这样的相互关系,原子比b为0<b≤0.4的范围内的值,原子比c为0<c≤0.3的范围内的值。此外,第1被膜22以其膜厚成为0.1μm以 上5.0μm以下的方式形成。第2被膜24由TiB2构成。该第2被膜24以其膜厚成为0.1μm以上5.0μm以下的方式形成。而且,由这些第1被膜22和第2被膜24的层叠构成的硬质层叠被膜20由2层以上100层以下的层叠数构成,以其膜厚成为0.2μm以上10.0μm以下的方式形成。如这些本发明品1乃至46的评价结果中所示,对于第1被膜22(A层)和第2被膜24(B层)中的哪一个为最下层或最上层,都没有关系。
而作为不合格评价的试验丝锥的试验品1乃至10,在其刃部被覆的硬质层叠被膜20由第1被膜22和第2被膜24的交替层叠构成,第1被膜22由(TiaCrbBc)或(Ti1-aBa)的氮化物构成,第2被膜24由TiB2构成,原子、原子比a、膜厚、层数的任一个在上述本发明品的范围之外。此外,作为形成了由1种被膜的层叠构成的硬质层叠被膜的试验丝锥的现有品1乃至8,不仅耐磨损性大幅地低,而且虽然图9中没有示出,但存在耐熔敷性、耐热性、密合性的任一者欠缺的方面。
如上所述,对于本实施例的硬质层叠被膜20,由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22和由TiB2合金构成的第2被膜24在母材12、62、84的表面上交替地层叠而构成硬质层叠被膜20,因此能够获得在耐磨损性、耐热性、耐熔敷性和密合性(附着强度)上都能满足的特性。
此外,根据本实施例的硬质层叠被膜20,在由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22中,其(TiaCrbBc)合金的原子比a、b、c存在a=1-b-c这样的相互关系,原子比b为0<b≤0.4的范围内的值,原子比c为0<c≤0.3的范围内的值,第1被膜22的膜厚为0.1μm以上5.0μm以下,第2被膜24的膜厚为0.1μm以上5.0μm以下,硬质层叠被覆20的总膜厚为0.2μm以上10.0μm以下,因此能够获得在耐磨损性、耐热性、耐熔敷性和密合性(附着强度)上都能满足的特性。
此外,根据本实施例的硬质层叠被膜20,构成其的第1被膜22和第2被膜24的层叠数为2层以上100层以下,因此能够获得在耐磨 损性、耐热性、耐熔敷性和密合性(附着强度)上都能满足的特性。
以上基于附图对本发明的实施例详细地进行了说明,但其等只是一实施方式,本发明基于本领域技术人员的知识能够以加以各种变形、改进的方式实施。
产业上的利用可能性
本发明的硬质层叠被膜通过将由(TiaCrbBc)的氮化物、碳化物、碳氮化物或碳氧氮化物构成的第1被膜22和由TiB2构成的第2被膜24在母材12、62、84的表面上交替地层叠而构成硬质层叠被膜20,因此能够获得在耐磨损性、耐热性、耐熔敷性和密合性(附着强度)上都能满足的特性,特别是耐磨损性进一步提高,因此适合用作旋转切削工具等的硬质被膜。
附图标记的说明
10:立铣刀(带有硬质层叠被膜的切削工具)
12、62、84:工具母材
20:硬质层叠被膜
22:第1被膜
24:第2被膜
60:球头立铣刀(带有硬质层叠被膜的切削工具)
70:丝锥(带有硬质层叠被膜的切削工具)
Claims (1)
1.硬质层叠被膜,是将组成彼此不同的第1被膜(22)和第2被膜(24)这2种在母材(12、62、84)的表面交替地多个层叠的硬质层叠被膜(20),其特征在于,上述第1被膜为(TiaCrbBc)的氮化物、碳化物或碳氮化物,上述第2被膜为TiB2,上述第1被膜中的原子比a、b、c为a=1-b-c,为0<b≤0.4、0<c≤0.3,上述第1被膜的膜厚为0.1μm以上5.0μm以下,上述第2被膜的膜厚为0.1μm以上5.0μm以下,上述硬质层叠被膜的总膜厚为0.2μm以上10.0μm以下,上述硬质层叠被膜的层叠数为2层以上100层以下。
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JP (1) | JP5651712B2 (zh) |
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CN (1) | CN103339283B (zh) |
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JP6577037B2 (ja) * | 2015-09-04 | 2019-09-18 | オーエスジー株式会社 | 硬質被膜および硬質被膜被覆部材 |
KR102395885B1 (ko) * | 2020-01-30 | 2022-05-09 | 한국야금 주식회사 | 절삭공구용 경질피막 |
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CN1846990A (zh) * | 2005-04-13 | 2006-10-18 | 日立金属株式会社 | 具有优异粘合力和滑动性能的多层被覆层及其制备方法 |
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JPH10204618A (ja) * | 1997-01-13 | 1998-08-04 | Nachi Fujikoshi Corp | 立方晶窒化ほう素被覆複合材料及びその製造方法 |
SE522722C2 (sv) * | 2001-03-28 | 2004-03-02 | Seco Tools Ab | Skärverktyg belagt med titandiborid |
JP4408231B2 (ja) | 2004-03-11 | 2010-02-03 | 株式会社神戸製鋼所 | 硬質積層皮膜および硬質積層皮膜の形成方法 |
JP4950499B2 (ja) * | 2006-02-03 | 2012-06-13 | 株式会社神戸製鋼所 | 硬質皮膜およびその成膜方法 |
JP2008105106A (ja) * | 2006-10-23 | 2008-05-08 | Mitsubishi Materials Corp | 高速切削加工で硬質被覆層がすぐれた耐摩耗性を発揮する表面被覆切削工具 |
ES2431168T3 (es) * | 2007-12-06 | 2013-11-25 | Ceratizit Austria Gmbh | Herramienta recubierta |
CN101214744A (zh) * | 2007-12-28 | 2008-07-09 | 天津师范大学 | 射频磁控溅射法制备超硬TiB2/TiAlN纳米多层膜 |
JP5027760B2 (ja) * | 2008-08-20 | 2012-09-19 | 株式会社神戸製鋼所 | 硬質皮膜形成部材 |
JP5424103B2 (ja) | 2008-09-24 | 2014-02-26 | 日立金属株式会社 | 塑性加工用被覆金型 |
EP2598329A1 (en) * | 2010-07-26 | 2013-06-05 | National Institute Of Aerospace Associates | High kinetic energy penetrator shielding materials fabricated with boron nitride nanotubes |
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CN103339283A (zh) | 2013-10-02 |
US20130309470A1 (en) | 2013-11-21 |
KR101544660B1 (ko) | 2015-08-17 |
JPWO2012105002A1 (ja) | 2014-07-03 |
KR20130118976A (ko) | 2013-10-30 |
DE112011104820T5 (de) | 2013-10-31 |
JP5651712B2 (ja) | 2015-01-14 |
DE112011104820B4 (de) | 2016-10-27 |
WO2012105002A1 (ja) | 2012-08-09 |
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