CN103320758B - 硬质被膜、滑动部件、滑动部件的制造方法 - Google Patents
硬质被膜、滑动部件、滑动部件的制造方法 Download PDFInfo
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- CN103320758B CN103320758B CN201310053179.2A CN201310053179A CN103320758B CN 103320758 B CN103320758 B CN 103320758B CN 201310053179 A CN201310053179 A CN 201310053179A CN 103320758 B CN103320758 B CN 103320758B
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- hard film
- carbon
- boron
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Classifications
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- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B3/00—General-purpose turning-machines or devices, e.g. centre lathes with feed rod and lead screw; Sets of turning-machines
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本发明涉及硬质被膜、滑动部件、滑动部件的制造方法。提供一种硬质被膜,其长期保持硬质被膜的稳定的低摩擦特性。在含有硼和碳的硬质被膜(2)中,在表面分别具有多个凹部和凸部,所述凹部的碳浓度比所述凸部的碳浓度高,所述凸部的硼浓度比所述凹部的硼浓度高。另外,提供一种在基材(3)上设有含有硼和碳的硬质被膜的滑动部件的制造方法,所述硬质被膜采用非平衡磁控溅射法或高功率脉冲磁控溅射法的至少一种制作,使用含有硅、铬、钛、钨中的至少一种元素的靶、和碳化硼靶。
Description
技术领域
本发明涉及硬质被膜、滑动部件、滑动部件的制造方法。
背景技术
滑动部件的低摩擦化技术有助于内燃机的燃料费用降低及部件寿命的长期化等,因此,迄今为止已进行了积极研究。固体润滑被膜的开发、在表面形成所希望的凹凸形状的纹理技术的开发为其代表性的例子。具有在无润滑环境下固体润滑被膜显示优异的效果、另一方面,在以润滑油为媒介的环境下储存润滑油的结构的纹理技术起到有效的作用。
另外,作为综合这些技术的技术,对于润滑油的油膜厚度变化的滑动环境及油膜薄且不能忽视固体接触的润滑环境,研究了兼顾固体润滑被膜和纹理的技术,如专利文献1、2,开发了在被膜表面设置凹凸的技术。根据专利文献1,在表面上具有高台形状的被膜防止断油且在润滑油中显示低摩擦特性。根据专利文献2,具有平头凹凸形状的硬质被膜确保油的保持力且具有耐烧结性及耐磨性。
另一方面,作为固体润滑被膜的代表性材料有DLC(类金刚石碳),作为兼顾高硬度和自润滑特性的被膜而众所周知。DLC是也称为非晶质碳、a-C(无定形碳)、a-C:H(氢化无定形碳)、i-C(i碳)、硬质碳等的被膜材料,其成膜方法有溅射、电弧离子镀等PVD方式及等离子体CVD等,但是,在原材料利用了烃气体的情况下成为含有氢的碳膜。
DLC的微观结构作为碳原子彼此之间的键合包括sp2键和sp3键两者,是不具备明确的结晶结构(不具有晶粒边界)的非晶质结构体。DLC与TiN(氮化钛)、TiAlN(氮化钛铝)及CrN(氮化铬)等结晶性的硬质被膜相比较能够兼具高硬度和高韧性,另外,由于具有来自sp2键的自润滑性能,因此摩擦系数低。但是,DLC在300℃以上的温度范围发生膜硬度的降低及表面缺陷的形成等膜质恶化,若将其耐热温度与TiN的约500℃、TiAlN的约800℃等比较,则明显较低。在摩擦面由于摩擦热而成为局部的高温状态,因此,有时DLC由于滑动条件而显著地磨损。
以提高DLC的耐磨性为目的,开发了在DLC中添加了其它元素的被膜,专利文献3记述了在润滑油中使用的部件表面含有5~25原子%的氢和4~30原子%的硼的DLC。另一方面,以确保无润滑下的低摩擦特性为目的,在专利文献1中向润滑油中配合钼添加剂,在专利文献2中向润滑油中适量配合硫、磷、锌、钙、镁、钠、钡及铜。
另外,以提高耐热性为目的,还开发了向DLC中同时添加硼及氮的被膜。根据专利文献4,形成了作为含有硼及氮的非晶质碳的B-C-N层的转动装置改善了耐烧结性和耐磨性。根据专利文献5,以40原子%以上~小于99原子%的碳及1原子%以上~小于40原子%的氢且用硼和氮在10~80%范围置换了该碳的被膜覆盖滑动面的连接夹具显示优异的耐烧结性。
现有技术文献
专利文献
专利文献1:特开2002-235852号公报
专利文献2:特开平6-41721号公报
专利文献3:特开2011-26591号公报
专利文献4:特开2004-60668号公报
专利文献5:特开2005-282668号公报
发明内容
发明所要解决的课题
但是,上述的任一专利文献在耐久性方面都存在问题。
本发明以保持长期且稳定的低摩擦特性为目的。
用于解决课题的手段
为实现所述目的,本发明提供一种硬质被膜,其含有硼和碳,其特征在于,在表面分别具有多个凹部和凸部,所述凹部的碳浓度比所述凸部的碳浓度高,所述凸部的硼浓度比所述凹部的硼浓度高。
另外,提供一种滑动部件的制造方法,其为在基材上设有含有硼和碳的硬质被膜的滑动部件的制造方法,其特征在于,所述硬质被膜使用非平衡磁控溅射法或高功率脉冲磁控溅射法中的至少一种制作,使用含有硅、铬、钛、钨中至少一种元素的靶、和碳化硼靶。
发明效果
根据本发明,能够保持长期且稳定的低摩擦特性。
附图说明
图1是具有槽的硬质被膜表面的凹凸的立体图和表面的硼、碳及氮的组成分布图;
图2是硬质被膜的一个实施方式的剖面图和硬质被膜的厚度方向的组成分布图;
图3是通过AFM观察实施例1-3的表面凹凸而得到的图像、剖面凹凸分布和表面的示意图;
图4是实施例1-3的表面的凹凸部分的组成分布图;
图5是摩擦磨损试验装置的剖面示意图;
图6是表示使摩擦磨损试验的负荷升压时的实施例2-11及比较例2-2的摩擦系数的变化的图。
附图标记说明
1滑动部件
1′板状试样
1″盘状试样
2硬质被膜
3基材
4环状试样
5加热用加热器
6转矩测定用臂
7测力传感器
8浴槽
9浸渍液
10保温用油
11球状试样
20硬质保护层
21第一中间层
22第二中间层
23第三中间层
具体实施方式
(硬质被膜的构成)
作为与润滑油的成分没有关系、使润滑性能提高的方法,可考虑在硬质被膜的表面形成所希望的凹凸形状,但这时优选硬质被膜能够长期维持表面形状。作为现有例,在不添加其它元素而在耐热性低的DLC的表面形成纹理的情况下,虽在滑动初期显示优异的低摩擦特性,但在局部面压高的凸部摩擦热大,因此,随着滑动时间的经过磨损进展而平滑化,低摩擦特性不能持续。另外,作为其它的现有例,在成膜中于基材表面设置掩模体,在利用通过成膜后除去该掩模而在硬质被膜表面制作凹凸的方法的情况下,基材和被膜的界面、或表层和基底层的界面局部露出。在所露出的界面部不能耐受应力集中而成为界面剥离的起点,使被膜损伤。根据本发明,能够提供一种硬质被膜,其对于这样的多个被膜损耗具有优异的耐久性,同时,在表层具有适于润滑剂保持的凹凸形状。
图1表示硬质被膜表面的凹凸的立体图和表面的硼、碳及氮的组成分布图(元素分布)。硬质被膜2为至少含有硼和碳的非晶质被膜,在最表层具有多个槽。在将硬质被膜2于层合方向切断时的剖面中,在被膜表面形成多个凹部和凸部,槽成为凹部。该凹部的特征为碳浓度比凸部高。由此,能够将润滑剂保持于槽部,能够有助于润滑油中的低摩擦特性。另外,在凸部硼浓度比凹部高,因此,具有凸部耐热性更高的结构。因此,对于摩擦的耐久性在凸部更优异,难以发生因凸部的磨损而表面平滑化的现象。即,本发明在成为槽的凹部使碳浓度增高而容易保持润滑剂,由此,减小了摩擦系数,在与其它部件滑动的凸部使硼浓度增高而提高了耐热性,由此,提高了耐久性。因此,能够长期保持硬质被膜的凹凸形状,能够获得稳定的低摩擦特性。
本发明涉及的硬质被膜2还优选是除了含有硼及碳外,还含有氮的非晶质被膜。虽然氮显示容易与硼键合的倾向,与凸部相比在凹部显示低的浓度,但保持非晶质结构而不形成晶粒等。B-N键在保持高硬度特性的同时为热稳定的,有助于耐热性的提高,因此,优选以不超过硼浓度的1.1倍的浓度作为上限而含有氮。但是,在超过该范围而含有氮的情况下,氮形成多个C-N键,引起膜硬度的显著降低。
导入本发明涉及的硬质被膜2的最表层的多个槽优选长度方向为任意的且为各向同性的结构。在滑动面内润滑油容易朝向槽的长度方向流动,因此,在槽的长度方向平行且朝向一个方向的情况下,除了在该方向以外难以滑动,摩擦系数变大。即,滑动方向对摩擦特性产生影响。通过形成各向同性的结构,能够获得不依赖于滑动方向的低摩擦特性。
本发明涉及的硬质被膜2的膜硬度在ISO-14577记载的仪器压痕硬度试验中,在将压入的深度设为150nm以下的条件下,优选为20GPa以上。在低于该规定的范围时,由于滑动时的剪切力而容易发生剥离,因此不优选。
导入本发明涉及的硬质被膜2的最表层的槽在相对于长度方向垂直的宽度方向的大小为不超过100μm的范围,优选凹部和凸部的高低差为不超过0.5μm的范围。在宽度比该范围大的情况下,由于点接触及线接触,接触部的尺寸低于槽的宽度尺寸,难以获得充分的润滑效果。另外,在凹部和凸部的高低差比该范围大的情况下,因高低差的原因造成的抗剪阻力变大,摩擦系数变大。
图2表示硬质被膜的一个形态的剖面图和硬质被膜的厚度方向的元素分布。在此表示含有金属元素、硼、碳、氮的情况。本发明的硬质被膜2优选制成在硬质保护层20和基材3之间设有中间层21~23的多层结构。这时,在基材3的正上方形成金属的第一中间层21,在第一中间层21的正上方形成金属和金属碳硼化物为主成分的第二中间层22,在第二中间层22的正上方形成金属碳硼化物和非晶质碳为主成分的第三中间层23。中间层21~23的厚度方向的组成分布希望从与基材3的界面到与硬质保护层20的界面为连续地变化。换言之,各中间层与相邻的层越接近,越具有与该相邻的层相近的组成。通过形成这样的多层结构,能够缓和硬质被膜2的内部应力,并且,提高与基材3的附着性,能够抑止界面剥离,进一步提高耐久性。
用于本发明涉及的硬质被膜2的中间层21~23的金属优选硅(Si)、铬(Cr)、钛(Ti)及钨(W)的至少一种。这些元素在钢铁基材及Al合金基材上能够形成附着性良好的被膜。
有时本发明涉及的硬质被膜2中混入作为制造上不可避免的元素的氢、氧及氩。在该情况下,也优选控制为氢20原子%以下,氧12原子%以下,氩15原子%以下。在超过该规定的范围时,被膜脆化,容易引起滑动时的被膜损耗,因此不优选。
本发明涉及的硬质被膜优选形成在各种滑动部件的表面。作为配备于汽车用的内燃机内的滑动部件,可以列举:起阀器、顶杆、调整垫片、凸轮、凸轮轴、摇臂、活塞、活塞销、活塞环、定时齿轮、以及定时链条等。另外,作为配备于燃料供给泵及燃料喷射系统的滑动部件,可以列举:喷射器、柱塞、气缸、凸轮、叶片等。但是,本发明不限于这些,也可广泛地适用于其它的滑动部件。
(制造方法)
本发明涉及的硬质被膜优选以将碳化硼用于固体靶的PVD法制作,优选使用导入了等离子体的离子化率高的溅射技术即非平衡磁控管溅射技术及高功率脉冲溅射技术中的任一者或两者的被膜制造装置。在使用现有的溅射装置的情况下,对于等离子体具有的能量有限度,另外,由于等离子体主要在靶附近被激发,因此,难以在被成膜材料即基材附近保持高的激发状态。与之相对,非平衡磁控管溅射技术是能够控制等离子体分布且提高基材侧的等离子体密度的技术。另外,高能量脉冲溅射技术是能够提高在靶上的等离子体自身的能量的技术。在采用导入了这些技术的装置实施溅射的情况下,由难以离子化的碳及硼也能够获取更高次的激发状态而形成非平衡状态,能够形成具有固有的凹凸形状的被膜。另外,在等离子体控制中通常使用氩气。
在控制本发明涉及的硬质被膜的硼和碳的组成的情况下,准备碳化硼和石墨两种固体靶,优选通过调整各自的供给电力进行控制的方法。另外,在含有氮的情况下,优选在成膜中的真空炉内微量地封入并含有氮气或氨气的任一者或两者。
在制作本发明涉及的硬质被膜的情况下,以强化碳的还原反应并制作更高硬度的被膜为目的,也可以实施兼用氢气及烃气体的反应性溅射法,但是,硬质被膜内的氢优选限制为20原子%以下。在利用甲烷气体的情况下,甲烷气体的流入体积优选将“Ar:甲烷=90:10”设为上限,并限制为少量。通过溅射方式,在不含有氢而形成被膜的情况下,硬质被膜的硼浓度越高硬度越高,在硼浓度最高为“硼:碳=4:1”时获得最高硬度。另一方面,在含有的氢浓度为15原子%以下的范围制作被膜的情况下,硬质被膜的碳浓度越高硬度越高,硬质被膜的硬度取仅用石墨制作的现有的DLC和前述的“硼:碳=4:1”的被膜硬度间的值。
〔实施例〕
(实施例1)
利用能够实现高能量的等离子体的非平衡磁控管溅射(以下称为UBM溅射)及高功率脉冲溅射(以下称为HPPM溅射)的任一装置,考虑成为被膜的供给源的固体靶及气体,研究了能够获得固有的表面结构的条件。溅射的气体种类使用了氩气。
(实施例1-1)
在UBM溅射装置(神户制钢所制UBMSTM)中设置基材、铬靶、碳化硼靶。首先,一边使氩气流入一边向铬靶供给电力,在钢铁基材的表面形成第一中间层(厚度0.1μm),接着,向碳化硼靶追加供给电力形成第二中间层(厚度0.5μm)。在第二中间层的成膜中,调整靶电力和气体流量以使铬浓度逐渐减小,碳浓度和硼浓度逐渐增加。之后,将真空气压设为0.2Pa,将基材施加偏压设为150V,切断铬靶电力仅继续供给碳化硼靶电力,形成非晶质的BC被膜(厚度1.7μm)。被膜形成中的试样温度在等离子体的照射中特别地上升,但通常保持不超过200℃的状态。在被膜表面可看到固有的凹凸组织。进行被膜的组成分析时,确认了原子浓度比在凸部为“硼:碳=82:18”、在凹部为“硼:碳=69:31”,获得了所希望的结构。
(实施例1-2~1-4、比较例1-1~1-6)
使用与实施例1-1同样的方法,使固体靶及气氛气体的种类变化,在钢铁基材表面形成被膜。用于最表层的被膜形成的固体靶从碳化硼、石墨、硼及六方晶氮化硼中选择至少一种,Ar气氛中混合的气体任意地选择氮及甲烷。这时,调整靶供给电力及气体供给量使被膜中的碳的含量与硼及氮相比为相同程度,使将三种元素设为100时的碳的原子浓度为33~68原子%。但是,由于烃气体的过剩供给引起被膜的低硬度化,因此,对于甲烷气体的流入体积,将“Ar:甲烷=90:10”作为上限进行控制。另外,绝缘体即六方晶氮化硼的供给电源使用了高频电源。
具有固有的凹凸表面的被膜在使用碳化硼的实施例1-2~1-4中出现。另一方面,在使用硼及氮化硼制作的含有硼的比较例1-1~1-2、未使用含硼材料而使用石墨靶制作的比较例1-3~1-6中,固有的凹凸面未出现。
(实施例1-5~1-6、比较例1-7)
使用与实施例1-1同样的方法,使用碳化硼靶和石墨靶,改变试样温度形成被膜。实施例1-5中,通过不连续而是间歇地实施等离子体的照射,抑制了温度上升。另外,钢铁及Al合金由于高温处理而有时劣化,但任一材料均在将处理温度抑制为100℃以下时不发生劣化。实施例1-6及比较例1-7通过在被膜形成中使电热加热器工作而进行加热。其结果是,在将试样温度保持为560℃以下的环境下能够实现固有的凹凸面,但在接近580℃以上的气氛中形成被膜的比较例1-7中未出现所希望的凹凸面。可以认为在高温环境下,构成非晶质的原子的移动活泼,发生原子扩散使得浓度差消除,因此,未形成具有浓度差的凹凸。
(实施例1-7~1-8、比较例1-8~1-9)
使用与实施例1-1同样的方法,使用碳化硼靶和石墨靶,改变向基材施加的偏压形成被膜。其结果是,在施加偏压为30V~340V的条件下成膜时,在将固有温度保持在560℃以下的环境下时能够实现固有的凹凸面,但偏压为20V的比较例1-8及350V的比较例1-9中未出现所希望的凹凸面。
(实施例1-9)
在HPPM溅射装置(Hauzer社制Flexicoat(R)850)中设置基材、铬靶、碳化硼靶及石墨靶。首先,一边使氩气流入一边向铬靶供给电力,在钢铁基材的表面形成第一中间层(厚度0.2μm),之后,将真空气压设为0.2Pa,将基材施加偏压设为150V,切断铬靶电力仅对碳化硼靶继续供给电力,形成非晶质的BC被膜(厚度1.8μm)。被膜形成中的试样温度在等离子体的照射中尤其上升,但通常保持不超过350℃的状态。在被膜表面可看到固有的凹凸组织。进行被膜的组成分析时,确认了原子浓度比在凸部为“硼:碳=75:25”、在凹部为“硼:碳=54:46”,获得了所希望的结构。
(固有凹凸表面的分析)
准备碳化硼的固体靶,通过能够使高能量的等离子体产生的UBM溅射或HPPM溅射的任一方法,实施多个成膜试制,结果在特定的成膜条件时确认了能够实现下述所示的固有的被膜。制作的硬质被膜为在用透射型电子显微镜(TEM)的电子解说图形确认时表示晕圈图形的非晶质(无定形),在用X射线光电子能谱法(XPS)确认时至少含有硼和碳的被膜。在通过原子力显微镜(AFM)观察的被膜表面(图3),能够确认数十μm程度的组结构,在组的内部并列形成有多个宽度为数μm程度的槽。一个组内部的相邻的槽为在长度方向在一定程度上一致的结构,但是,在比较相邻的组时,槽的取向没有规则性,作为膜整体槽的长度方向的朝向是任意的。槽的高低差为数十nm,组边界的高低差也大体为相同的数十nm。在观察图像中能够确认组结构和导入组内的槽。在图像内的从起始点“S”到终点“E”之间的线分布中,在槽部分形成高低差。B1及B2为邻接的组的边界部位,但是,这里的高低差与槽部分的高低差没有大的不同。
在利用俄歇电子能谱法(AES)的分布分析研究了宽度数μm的纵槽部分的组成变化时,可知在凹部显示比凸部更高的碳浓度(图4)。在并用碳化硼和石墨两种固体靶制作使碳增多的被膜时,能够确认该纵槽的组织不限于富硼侧的组成,在富碳侧也能够形成。但是,对于仅用石墨制作的非晶质碳,未形成槽的结构,在以硼及氮化硼(h-BN)为原材料制作的B-C系非晶质被膜中也未形成纵槽的结构,暗示这是源自碳化硼的组织。另外,硬质被膜的表面凹凸形状的分析能够采用原子力显微镜(AFM)和激光显微镜实施,组成及微观结构的分析能够采用拉曼分光法、红外分光光度计(IR)、透射型电子显微镜(TEM)、电子能量损失能谱法(EELS)、X射线衍射法(XRD)、电子束衍射法(LEED/RHEED)、X射线光电子能谱法(XPS)及核磁共振法(NMR)等进行。
被膜的原子浓度采用XPS和AES分析,记述了硼、碳及氮3种元素的比率。氢采用XPS和AES不能检测,因此除外,但是,通过弹性反冲粒子检测法(ERDA)的组成分析,确认了在实施例的所有被膜中不超过20原子%。在超过该范围含有氢的情况下,被膜的硬度降低,因此不优选。另外,有混入作为制造上不可避免的元素的氧及氩的被膜,但能够将氧控制为12原子%以下,将氩控制为15原子%以下。在超过该范围含有的情况下,被膜的硬度降低,因此不优选。
(源自碳化硼的凹凸面形成机理)
以B4C为基本组成的碳化硼的结晶为菱面体晶,晶胞为包含12个硼原子的20面体和直链状的3个碳构成、且20面体用直链状CCC键合的B12≡C3的基本结构。但是,部分地直链状CCC的中央的碳置换为硼的结构稳定,为用(B11C)≡CBC≡(B11C)的结构式表示的分子性固体。作为一般的分子性固体,与分子内部的键合力相比分子间力小,因此,低熔点且低硬度的材料多。与之相对,碳化硼的分子间的键合力大,因此,为具有突出的高熔点和高硬度的材料。根据记载了热平衡状态的B-C系的相图,在9~19原子%碳的组成区域中成为碳化硼B4+σC的单相状态,在19原子%碳以上的区域中为B4C和石墨的两相状态。另一方面,在周期表内,由以IV族的碳为中心而相邻的硼、碳、氮及硅构成的固体的结晶化的临界冷却速度慢,为容易形成不具有结晶晶粒边界的均质的非晶质(非晶的)材料系。因此,在利用真空中的非平衡等离子体在抑制了反应速度的低温环境下制作材料时,能够期待热平衡状态大相径庭的微观结构。
形成源自碳化硼的固有被膜结构的机理尚未明确,但是,可考虑如下的假设。强调如下作用,通过形成非晶质结构,各原子键水平的规则性被损害,结果形成更大分子水平的宽松的集合体。将分子键合性的材料即碳化硼用于蒸镀源的结果是,以多个核为基点而分子结构相连接的方式形成集合体,由于被膜的应力和集合体的大小平衡,由此,形成观察到的组结构。可以认为在由分子性集合体构成的组内,硼原子容易进入20面体结构,碳原子容易进入直链状的CBC的部位,因此,由于分子结构的各向异性,碳以高浓度凝集的部位成为槽状。这种现象在其它的分子性固体中也有可能发现,但是,在将碳化硼与其它材料比较时,具有与分子内部的键合力相比分子间力更牢固的特征,可以说是更容易形成分子性集合体的材料。
表1
(实施例2)
利用UBM溅射装置,将碳化硼作为硼的供给源形成改变了组成的多个被膜,研究了与膜硬度的关系。膜硬度利用ISO-14577中记载的仪器压痕硬度试验(エリオニクス制ENT-110a),以使压入深度成为10~150nm范围的方式设定压入负荷进行测定。另外,实施润滑油中的摩擦磨损试验,研究了摩擦系数和被膜的损耗。
(实施例2-1~实施例2-23的制作)
采用与实施例1-1同样的方法,使固体靶及气氛气体的种类变化,在钢铁基材表面形成被膜。用于最表层的被膜形成的固体靶从碳化硼、石墨、硼及六方晶氮化硼中选择至少一种,在Ar气氛中混合的气体任意选择氮及甲烷。在形成表层时将真空气压设为0.2Pa,将基材施加偏压设为150V,将试样温度设为200℃,使用甲烷气体的试样将甲烷气体的流入体积控制为“Ar:甲烷=97:3”。
(比较例2-1~比较例2-4的制作)
采用与实施例1-1同样的方法,使固体靶及气氛气体的种类变化在钢铁基材表面形成被膜。比较例2-1使用石墨靶制作C被膜,比较例2-2使用石墨靶和甲烷气体制作CH被膜,比较例2-3使用硼靶和石墨靶制作BC被膜,比较例2-3使用六方晶硼靶和石墨靶制作BCN被膜。在表层形成时将真空气压设为0.2Pa,将基材施加偏压设为150V,将试样温度设为200℃,将比较例2-2的甲烷气体的流入体积控制为“Ar:甲烷=97:3”。
(摩擦磨损试验)
在边界润滑下,在摩擦磨损试验中使用了松原式摩擦磨损试验机(株式会社オリエンテック制、型式:EFM-III)(图5)。摩擦磨损试验装置由板状试样1′、环状试样4、加热用加热器5、转矩测定用臂6、测力传感器7、浴槽8、浸渍液9、及保温用油10构成。宽度3mm、长度20mm的板状试样是将SUS440B表示的钢铁材料用于基材,在成为滑动面的板状表面上形成各种被膜的试样。外半径5.5mm、内半径3.5mm的环状试样使用表面经气体氮化处理的钢铁材料(SKD10),成为滑动的相对材料。浸渍液使用聚α-烯烃,充满浴槽。摩擦磨损试验为将对于环状试样的负荷设为3.6kgJ(包括夹具类的自重2.6kgf)使试样接触,以滑动部外周的周向速度为1.0m/s的方式使板状试样旋转,以每分钟增加1kgf的方式使负荷从3.6kgJ增加到22.6kgf,进行加压,之后保持10小时(5.2×105周期)。另外,测定保温用油的试验温度,以试验温度成为80℃的方式用加热器进行调节实施试验。对于摩擦系数,比较了试验即将结束之前的保持10小时后的值。试验后观察板状试样的被膜,研究有无损耗。
在面接触的滑动试验中,润滑油的油膜厚度t在将润滑油的粘度设为η,将速度设为v,将表观接触面积设为a,将摩擦系数设为μ及将负荷设为P时,能够估算为:
数学式1
在油温为100℃时粘度η=1.60×10-3Pa·s,在油温为40℃时粘度η=5.11×10-3Pa·s,在式(1)中v=1.0m/s,a=1.22×10-5m2,将作为代表性的摩擦系数μ=0.15分别代入时,可知将油温设定为90℃时的油膜厚度t在5.9×10-10m<t<1.8×10-9m的范围。在实施例的被膜表面形成的纵槽的高低差为数十nm(~10-8m),比比较例的油膜厚度大,通过保持润滑油能够期待提高润滑性能。
图6比较了使负荷升压时的实施例2-11和比较例2-2的摩擦系数。比较例2-2的摩擦系数在刚滑动后显示为0.35,在将负荷升压到22.6kgJ后降低至0.14。但是,随着滑动时间的经过,在保持后10小时后增大到0.21。另一方面,实施例2-11的摩擦系数在初期显示为0.15,在比较低的摩擦下在将负荷设为22.6kgJ时显示相同程度的0.14,在保持10小时后也显示稳定的摩擦系数。比较例2-2的DLC使滑动面磨损并平滑化,由此在初期可低摩擦化,但由于磨损的进展基底露出,在10小时后摩擦系数变高。与之相对,实施例2-11的BCNH膜由于纹理的效果,从低加重侧到10小时保持后显示稳定的低摩擦特性,在试验后的被膜表面未确认到损耗。
可看出膜硬度在BC膜及BCN的情况下在硼浓度高的侧为高硬度,与之相对,在BCH膜及BCNH膜的情况下在碳浓度高的侧为高硬度。可认为在制作BCH膜及BCNH膜时混入炉内的甲烷气体与金刚石同样具有持有sp3电子轨道的碳原子,与从石墨供给的碳原子结合形成高硬度的晶格。
比较例2-1~2-4在保持10小时后显示高的摩擦系数,确认了被膜的磨损,与之相对,实施例2-1~2~23均显示了优异的低摩擦特性。但是,膜硬度为19GPa以下的实施例2-4、2-5、2-6、2-16、2-17在试验后能够看到局部的剥离。由此更优选被膜硬度为20GPa以上。
表2
Claims (12)
1.一种硬质被膜,其含有硼和碳,其特征在于,所述硬质被膜的表面是非晶质被膜,在所述非晶质被膜的表面分别具有多个凹部和凸部,所述凹部的碳浓度比所述凸部的碳浓度高,所述凸部的硼浓度比所述凹部的硼浓度高。
2.权利要求1所述的硬质被膜,其特征在于,在所述表面,所述凹部形成槽,多个所述槽并列。
3.权利要求2所述的硬质被膜,其特征在于,在所述表面形成多个组,在所述组内形成多个所述槽,在每个所述组中多个所述槽的取向不同。
4.权利要求2所述的硬质被膜,其特征在于,所述槽的宽度小于100μm,所述凹部和所述凸部的高低差小于0.5μm。
5.权利要求1所述的硬质被膜,其特征在于,还含有氢和氮中的至少1种,氢为20原子%以下,氮小于硼浓度的1.1倍。
6.权利要求1所述的硬质被膜,其特征在于,膜硬度为20GPa以上。
7.一种滑动部件,其特征在于,基材上设有权利要求1所述的硬质被膜。
8.权利要求7所述的滑动部件,其特征在于,所述硬质被膜在所述基材侧形成多个中间层,所述多个中间层从所述基材侧开始具备:含有金属的第一中间层、含有金属和金属碳硼化物的第二中间层、含有金属碳硼化物和非晶质碳的第三中间层。
9.权利要求7所述的滑动部件,其特征在于,所述硬质被膜在所述基材侧形成含有硅、铬、钛、钨中的至少1种元素的中间层,所述元素的浓度从所述基板侧朝向所述表面逐渐减小,硼、碳、氮中的至少1种元素的浓度从所述基板侧朝向所述表面逐渐增大。
10.权利要求7所述的滑动部件,其特征在于,所述基材为配备于内燃机内的起阀器、顶杆、可调整垫片、凸轮、凸轮轴、摇臂、活塞、活塞销、活塞环、定时齿轮、定时链条,配备于燃料供给系统内的喷射器、柱塞、气缸、凸轮及叶片中的任一种。
11.权利要求8所述的滑动部件,其特征在于,所述基材为配备于内燃机内的起阀器、顶杆、可调整垫片、凸轮、凸轮轴、摇臂、活塞、活塞销、活塞环、定时齿轮、定时链条,配备于燃料供给系统的喷射器、柱塞、气缸、凸轮及叶片中的任一种。
12.权利要求9所述的滑动部件,其特征在于,所述基材为配备于内燃机内的起阀器、顶杆、可调整垫片、凸轮、凸轮轴、摇臂、活塞、活塞销、活塞环、定时齿轮、定时链条,配备于燃料供给系统的喷射器、柱塞、气缸、凸轮及叶片中的任一种。
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2012
- 2012-03-23 JP JP2012066503A patent/JP5629716B2/ja not_active Expired - Fee Related
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2013
- 2013-02-12 US US13/765,254 patent/US9034461B2/en not_active Expired - Fee Related
- 2013-02-19 CN CN201310053179.2A patent/CN103320758B/zh not_active Expired - Fee Related
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JP2004060668A (ja) * | 2002-07-24 | 2004-02-26 | Nsk Ltd | 転動装置 |
JP2007099949A (ja) * | 2005-10-05 | 2007-04-19 | Toyota Motor Corp | 摺動構造及び摺動方法 |
CN101525734A (zh) * | 2009-03-31 | 2009-09-09 | 西安交通大学 | 一种制备硼碳氮硬质涂层的方法 |
Also Published As
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CN103320758A (zh) | 2013-09-25 |
JP2013194317A (ja) | 2013-09-30 |
US9034461B2 (en) | 2015-05-19 |
US20130251956A1 (en) | 2013-09-26 |
JP5629716B2 (ja) | 2014-11-26 |
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