CN110699664B - 磨损防护层组件和具有磨损防护层的构件 - Google Patents
磨损防护层组件和具有磨损防护层的构件 Download PDFInfo
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Abstract
本发明涉及一种磨损防护层组件(10)，具有衬底(11)、构造在衬底上的附着剂层(12)和至少一个向外终止的防护层(15)，将所述磨损防护层组件设置为以硅作为掺杂剂掺杂含氢非晶碳层(15)的衬底侧区域(15’)，并且外侧区域(15”)保持未掺杂。在所述附着剂层(12)和含氢非晶碳层(15)之间构造两个过渡层(13、14)，能够以硅作为掺杂剂连贯地掺杂所述过渡层。所述过渡层(13、14)与非晶碳层(15)的衬底侧区域(15’)相比分别能够具有更低的硅掺杂。
Description
技术领域
本发明涉及一种磨损防护层组件，其具有衬底、构造在衬底上的附着剂层和至少一个向外终止的防护层，所述防护层构造为含氢非晶碳层。本发明还涉及一种具有磨损防护层组件的构件以及一种用于制造所述磨损防护层组件的方法。
背景技术
暴露在高温和高压下的构件配套地设有磨损防护层，在高压喷射系统(共轨喷射器)的组件中尤其是这种情况。使用含氢非晶碳层作为磨损防护层，借助等离子支持的沉积方法将该含氢非晶碳层涂覆到构件上并且具有针对直至约350℃的耐热性。
在薄碳层的生成和特征方面的基础研究结果(参见[1]S.S.Camargo,Jr,A.L.BaiaNeto,R.A.Santos,F.L.Freire,Jr,R.Carius,F.Finger，，Improved high-temperaturestability of Si incorporated a-C:H films“,Diamond and Related Materials 7，1998年，第1155-1162页；[2]A.L.Baia Neto,R.A.Santos,F.L.Freire,Jr,S.S.Camargo,Jr,R.Carius,F.Finger,W.Beyer，，Relation between mechanical and structuralproperties of silicon-incorporated hard a-C:H films“,Thin Solid Films 293，1997年，第206-211页)表明，尽管薄非晶碳层的硅掺杂提高了针对更高温度的耐热性，然而由此显着降低了这种碳层的耐磨性。
发明内容
根据本发明的磨损防护层组件具有衬底、构造在衬底上的附着剂层和至少一个向外终止的防护层，所述防护层构造为含氢非晶碳层，其中，含氢非晶碳层的衬底侧区域掺杂有作为掺杂剂的硅，并且外侧区域保持未掺杂。
根据本发明的磨损防护层组件具有以下优点：该磨损防护层组件在高耐磨性实际不减弱的情况下针对直至约500℃具有扩展的耐热性。为此设置为，以硅作为掺杂剂掺杂含氢非晶碳层的衬底侧区域，并且外侧的区域保持未掺杂。通过对非晶碳层的衬底侧区域的选择性硅掺杂能够将嵌入在那里的硅与氧气键合成为二氧化硅化合物，该氧气扩散经过网状结构中的在温度提高时扩大的空腔，由此在那里构造对于氧气的扩散障碍，该扩散障碍防止由铬组成的下面的附着剂层的氧化与由此导致的附着剂层和非晶碳层之间的裂纹形成和后者的至少部分的脱落；其方式是，非晶碳层的上部区域保持未掺杂、即没有作为掺杂剂的硅，在该衬底侧区域中构造具有特定微观结构并因此具有其表征硬度或耐磨性的“纯”碳氢化合物网络。
通过优选实施方式提及的措施说明本发明的另外有利的扩展方案和构型。
本发明的能够实现在耐磨性方面的恒定高质量的优选扩展方案在于，含氢非晶碳层的衬底层侧区域具有硅掺杂分布，该掺杂分布设置为，相比于含氢非晶碳层的网状成分，该硅掺杂分布位于1至20％原子百分比的浓度值域中。在此，硅掺杂分布从碳层的边界面开始包括硅浓度增大的上升分布区段、具有近似恒定走势的硅掺杂剂最大浓度的平台区域和具有降低到零水平的硅浓度的下降分布区段。达到零水平限定衬底侧区域的结束并且同时限定非晶碳层的外侧区域的开始。
系列测试已示出，适宜的是，非晶碳层的以硅掺杂的衬底侧区域的厚度为碳层的层厚度的大约20％至80％、优选大约50％。
通过根据本发明的一构型能够实现在约500℃的情况下具有层硬度为大约35Gpa的非晶碳层的磨损防护层组件的特别高的耐磨性，该构型设置至少一个过渡层，该过渡层构造在附着剂层和含氢非晶碳层之间，其中，所述至少一个过渡层能够以硅作为掺杂剂连续地掺杂。在此，所述至少一个过渡层与非晶碳层的衬底侧区域相比具有更低的硅掺杂，以便产生通向非晶碳层的衬底侧区域的“流畅”走势的掺杂过渡。
本发明的对此替代的实施方式能够在于，两个彼此相继的过渡层构造在附着剂层和非晶碳层之间，其中，与非晶碳层邻接的过渡层具有与位于下面的并且邻接到附着剂层上的过渡层相比至少同样大或者稍大的硅掺杂浓度。由此，在该实施方式中产生对于从外部扩散的氧气在层厚度方面更宽的扩散障碍。
具有这种磨损防护层组件的构件适用于在高温和高压的情况下使用并且因此适合作为高压喷射系统的组件、尤其作为喷射器。
根据本发明提出用于制造磨损防护层组件的方法，其中，在衬底上构造有附着剂层，然后直接地或间接地产生至少一个含氢非晶碳层作为防护层，在所述方法中设置，在产生所述至少一个含氢非晶碳层时以硅作为掺杂剂掺杂非晶碳层的衬底侧区域并且非晶碳层的外侧区域不掺杂地构造。在此，构造具有硅掺杂分布的衬底侧区域，该硅掺杂分布选择为，使得相比于产生非晶碳层时所使用的工艺气体，该掺杂分布在平台中位于1％原子百分比至20％原子百分比的浓度值域中，由此能够实现可复制的高制造质量。对于掺杂分布，从碳层的边界面开始在衬底侧的区域中构造硅浓度增长的上升分布区段、具有近似恒定走势的硅最大浓度的平台区域和具有几乎降低到零水平的硅浓度的下降分布区段。借助离子诱导沉积(PEVCD：“等离子体化学气相沉积”)实施非晶碳层的制造，其中，在一个或多个薄层上通过生长构造非晶碳层，所述薄层可以是由金属、例如铬组成的附着剂层或者是施加在附着剂层上的一个或多个过渡层。
附图说明
在下面的说明书和附图中进一步阐明本发明的实施例。后者在示意图中示出：
图1A根据本发明的磨损防护层组件的截面图，该磨损防护层组件包括衬底、附着剂层、两个过渡层和向外终止的功能层，其中，构造为非晶碳层的功能层具有以硅掺杂的衬底侧区域和未掺杂的表面侧区域。
图1B表明用于功能层的衬底侧区域的典型硅掺杂分布的图示，其中，沿着横坐标表示功能层的层厚度并且沿着纵坐标表示作为功能层厚度的函数的硅掺杂分布。
图2A根据第二实施方式的本发明的磨损防护层组件的截面图，包括衬底、附着剂层和构造为非晶碳层的功能层，其中，功能层具有以硅掺杂的衬底侧区域和未掺杂的表面侧区域，以及
图2B表明根据图2A的第二实施方式用于层组件的功能层的衬底侧区域的硅掺杂分布，其中，沿着横坐标表示功能层的衬底侧区域的层厚度并且沿着纵坐标表示硅掺杂分布的浓度。
具体实施方式
图1A示出根据本发明的磨损防护层组件10的强烈简化的横截面视图，该磨损防护层组件相继由衬底11、施加在衬底11上的附着剂层12、第一过渡层13、第二过渡层14和最后的防护或功能层15构成。在此，将一般由钢组成的构件用作为衬底11，该构件设置为用于涂覆，以便改善该构件的耐磨性和耐热性。施加在衬底11上的附着剂层12由结晶铬组成，而施加在该附着剂层上的两个过渡层13、14构造为碳化铬-化合物结构并且相对彼此主要在铬/碳比方面不同，以便产生对随后施加在所述过渡层上的功能层15的微观适配。向外终止的功能层15构造为含氢非晶碳层(a-C:H层)并且借助等离子支持的沉积方法在第二过渡层14上施加根据应用情况约为0.1微米至几微米的层厚度。
为了提高含氢非晶防护层15的耐热性，以硅掺杂该防护层的衬底侧区域15’，即与位于该其下方的第二过渡层14邻接的区域。在此，这种掺杂区域15’的厚度大约为防护层15的总厚度的20％至80％。为了同时保证防护层15的耐磨性，将其余的外部区域15"、即朝着功能层15的外侧或表面15”’指向的表面侧区域或者说背离第二过渡层14的区域保持不掺杂。
布置在附着剂层12和功能层15之间的两个过渡层13、14用于建立从衬底11的晶体结构到功能层15的非晶网状结构的逐步过渡；在此，实施例中的两个过渡层13、14可以掺杂硅并且第二过渡层14具有比第一过渡层13稍高的硅掺杂浓度，以便减小从边界面到边界面的内应力。两个过渡层13、14分别具有比非晶碳层的衬底侧区域15’明显更低的硅掺杂浓度。
图1B在强烈简化的图示中说明硅掺杂分布与非晶碳层15的层厚度z函数相关的定性走势。在此，横坐标表示防护层15的层厚度z，而纵坐标表示硅掺杂度N(Si)。以梯形形状构造的掺杂分布20具有上升沿21，该上升沿在衬底侧区域15’朝向第二过渡层14的边界面16中开始，其中，工艺气体中的硅混入量或者说硅含量升高，使得达到掺杂分布20的平台区域22，在该平台区域中，硅混入量维持在相对恒定的最大水平Nmax，接着最后出现掺杂分布20的下降沿23，硅混入量随着该下降沿从恒定的最大水平Nmax减小到零水平、即0％原子百分比；在下降沿23中达到零水平一方面限定衬底侧的区域15’的结束并且另一方面限定防护层15的外部未掺杂区域15"的开始。因此，硅掺杂分布在碳层15的衬底侧区域15’上变化。另外，如此选择非晶碳层15的衬底侧区域15’中的硅掺杂分布，使得该掺杂分布位于以下浓度值区域中，相比于用于沉积碳层而导入的含碳氢化合物的工艺气体、例如乙炔(C2H2)、甲烷或其他碳氢化合物，该浓度值区域从1％原子百分比延伸至20％原子百分比，其中，为了硅掺杂在沉积过程期间供应或混入含硅的工艺气体、例如硅烷。在平台区域22中的硅浓度的恒定最大水平Nmax在实施例中大约为20％原子百分比。在热处理之后得出，碳层15的层厚度和层硬度直到T≈450℃分别显示大约恒定的走势并且在450℃≤T≤500℃的情况下层厚度和层硬度才分别减少了约30％。
图2A示出了根据第二实施方式的磨损防护层组件100，该第二实施方式与图1中所示出的实施方式的区别在于：缺少中间的过渡层，使得磨损防护层组件100相继由衬底110、铬附着剂层120和作为功能层的含氢非晶碳层150构成。在此，与第一实施方式一致地，碳层150具有两个彼此相邻的区域150’和150”，以硅作为掺杂剂掺杂这两个区域中的与朝向附着剂层120的边界面160直接邻接的衬底侧区域150’，而面向外侧150”’的外侧区域150”保持不掺杂。
图2B在强烈简化的图示中示出根据图2A的第二实施方式的硅掺杂分布200与层组件100的非晶碳层150的层厚度或层生成z函数相关的定性走势。硅掺杂分布200在衬底侧区域150’上变化并且包括三个分布区段，即首先是上升沿210，然后是平台220，最后是下降沿230，区域150’的三个区间z1、z2、z3分配给所述三个分布区段；在此，区域150’划分成第一区间z1、中间的第二区间z2和第三区间z3，该第一区间构成朝向边界面160的边缘区间，该第三区间构成朝向外侧区域150”的边缘区间。上升沿210沿着z轴延伸经过区域150’的第一区间z1，其值域为非晶碳层150的层厚度的10％≤z1≤25％，平台区域220延伸经过区域150’的第二区间z2，其值域为碳层150的层厚度的5％≤z2≤40％，并且下降沿230沿z轴延伸经过区域150’的第三区间z3，其值域为非晶碳层150的层厚度的1％≤z3≤20％。相对平的上升沿210导致晶体边界面160和非晶区域150’的邻接边缘之间的内应力仅会在低水平出现，而相对陡峭走向的下降沿230出现在第三区间和与该第三区间邻接的同样非晶的区域150”之间，并因此几乎不引起结构相关的内应力。出现与图1B的实施方式相同的性能。
在方法技术方面为了制造磨损防护层组件设置以下步骤：首先在衬底上或衬底表面上通过借助阴极溅射(“喷涂”)的沉积构造铬附着剂层；然后在可选步骤中在铬附着剂层上通过沉积构造两个过渡层，其中，借助CVD(“化学气相沉积”)沉积乙炔并且为了过渡层的硅掺杂供应含硅的气体；最终在最后的方法步骤中产生非晶含氢碳层15、150，其方式是，以硅作为掺杂剂掺杂非晶碳层15、150的衬底侧区域15’、150’并且非晶碳层15、150的外侧区域15”、150”不掺杂地构造，其中，构造具有硅掺杂分布20、200的衬底侧区域15’、150’，该硅掺杂分布这样选择，使得相比于在产生非晶碳层15、150时所使用的工艺气体、即例如乙炔或甲烷，该硅掺杂分布位于1％原子百分比至20％原子百分比的浓度值域中。对于掺杂分布，从碳层的边界面开始在衬底侧的区域中构造硅浓度增大的上升分布区段、具有近似恒定走势的硅最大浓度的平台区域和具有大致降低到零水平的下降分布区段。借助等离子支持的沉积(PEVCD：等离子体化学气相沉积)产生非晶碳层。
Claims (7)
1.磨损防护层组件，该磨损防护层组件具有衬底、构造在所述衬底上的附着剂层和至少一个向外终止的防护层，该防护层构造为含氢非晶碳层，其特征在于，所述含氢非晶碳层（15；150）的衬底侧区域（15’；150’）掺杂有作为掺杂剂的硅，并且外侧区域（15’’；150’’）保持未掺杂，其中，所述含氢非晶碳层（15、150）的所述衬底侧区域（15’；150’）具有硅掺杂分布（20；200），所述硅掺杂分布（20；200）从所述含氢非晶碳层（15；150）的边界面（16；160）开始包括硅浓度增大的上升分布区段（21；210）、具有恒定走势的硅掺杂剂最大浓度的平台区域（22；220）和具有降低到零水平的硅浓度的下降分布区段（23；230），其中，所述硅掺杂分布（20；200）设置为，使得相比于所述含氢非晶碳层（15；150）的网状成分，所述掺杂分布位于1%原子百分比至20%原子百分比的浓度值域中，其中，所述含氢非晶碳层（15；150）的以硅掺杂的所述衬底侧区域（15’；150’）的厚度为所述含氢非晶碳层（15；150）的层厚度的20%至80%。
2.根据权利要求1所述的磨损防护层组件，其特征在于，设置至少一个过渡层（13、14），所述过渡层构造在附着剂层（12）和所述含氢非晶碳层（15；150）之间，其中，所述至少一个过渡层（13、14）以硅作为掺杂剂连续地掺杂。
3.根据权利要求2所述的磨损防护层组件，其特征在于，所述至少一个过渡层（13、14）与所述含氢非晶碳层（15；150）的所述衬底侧区域（15’；150’）相比具有更低的硅掺杂。
4.根据权利要求2所述的磨损防护层组件，其特征在于，两个彼此相继的过渡层（13、14）构造在所述附着剂层（12）和所述含氢非晶碳层（15；150）之间，其中，邻接到所述含氢非晶碳层（15；150）上的所述过渡层（14）与位于下面并且邻接到所述附着剂层（12）上的所述过渡层（13）相比具有至少同样大的硅掺杂浓度。
5.根据权利要求1至4中任一项所述的磨损防护层组件，其特征在于，所述含氢非晶碳层（15；150）作为功能层直接衔接到所述附着剂层（120）上，其中，所述功能层具有以硅掺杂的衬底侧区域（15’；150’）和未掺杂的表面侧区域（150’’）。
6.一种构件，该构件具有根据权利要求1至5中任一项的磨损防护层组件。
7. 用于制造根据权利要求1至5中任一项所述的磨损防护层组件的方法，其中，在衬底上构造附着剂层，然后直接地或间接地产生至少一个含氢非晶碳层作为防护层，其特征在于，在产生所述至少一个含氢非晶碳层（15；150）时以硅作为掺杂剂对所述含氢非晶碳层（15；150）的衬底侧区域（15’；150’）进行掺杂，而所述含氢非晶碳层（15；150）的外侧区域（15"；150"）不掺杂地构造，其中，所述含氢非晶碳层（15、150）的所述衬底侧区域（15’；150’）具有硅掺杂分布（20；200），所述硅掺杂分布（20；200）从所述含氢非晶碳层（15；150）的边界面（16；160）开始包括硅浓度增大的上升分布区段（21；210）、具有恒定走势的硅掺杂剂最大浓度的平台区域（22；220）和具有降低到零水平的硅浓度的下降分布区段（23；230）,所述衬底侧区域（15’；150’）构造具有硅掺杂分布（20；200），所述掺杂分布选择为，相比于在产生所述含氢非晶碳层（15；150）时所使用的工艺气体，所述硅掺杂分布位于1%原子百分比至20%原子百分比的浓度值域中。
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| CN105734527A (zh) * | 2016-03-08 | 2016-07-06 | 仪征亚新科双环活塞环有限公司 | 一种用于活塞环表面的类金刚石镀层、活塞环及制备工艺 |
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