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CN101977874A - 用于生成包含碳化物纳米粒子的弥散硬化物的方法和设备 - Google Patents

用于生成包含碳化物纳米粒子的弥散硬化物的方法和设备 Download PDF

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CN101977874A
CN101977874A CN2009801086505A CN200980108650A CN101977874A CN 101977874 A CN101977874 A CN 101977874A CN 2009801086505 A CN2009801086505 A CN 2009801086505A CN 200980108650 A CN200980108650 A CN 200980108650A CN 101977874 A CN101977874 A CN 101977874A
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马库斯·肯尼迪
迈克尔·津内博尔德
马克-曼努埃尔·马特
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Abstract

本发明涉及一种生成包含碳纳米粒子的弥散硬化物的方法，所述方法包括通过热喷涂方法生成该弥散硬化物。根据本发明，至少一种前体在燃烧室的下游处通过载气的方式提供给气流，所述前体在气流中发生反应从而生成碳化物，或者，通过受到热负荷的外部纳米粒子生成器提供碳纳米粒子。这样便得到一种弥散硬化物，例如，内燃机的组件如活塞环。该方法通过热喷涂设备来执行，该设备在燃烧室的下游除了有用于供应热喷涂粉末的至少一个管线之外，还包括通过载气的方式供应前体的至少一个管线。

Description

用于生成包含碳化物纳米粒子的弥散硬化物的方法和设备
技术领域
本发明涉及一种用于生成包含碳化物纳米粒子的弥散硬化物的方法和设备。此外，本发明涉及采用根据本发明的方法所生成的弥散硬化物，例如，内燃机的组件，尤其是活塞环。
背景技术
对于活塞环来说，例如带有往复运动活塞的内燃机的活塞环，必须保证较高的抗磨损性，否则，也就是在较低的抗磨损性的情况下，覆盖涂层会变得较薄。因此，活塞环的壁厚减小，密封效果变差，漏气和耗油增加，引擎的性能变差。由于活塞环受到磨损，气缸壁与活塞之间的间隙持续增大，使得燃烧气体更容易通过活塞环、逸出(即所谓的漏气)，从而降低了引擎的效率。此外，由于间隙增大，没有被去除的剩余油膜将会变得更厚，因此每单位时间将会损失更多的油，因此增加了油耗。
如今，在活塞环的热喷涂领域，优选通过等离子喷涂法、使用钼基材料。但是，高负荷引擎中的活塞环的磨损率非常高。
高速氧燃料热喷涂技术(HVOF)使得以下情况成为可能：以较低的热影响和较高的动能在基底上沉积粒子，可生成高黏附性的致密层。此外，为了确保在较高负荷下改进抗磨损性能，近来开始使用金属碳化物粒子，例如WC或者Cr3C2，它们不能通过等离子喷涂法进行喷涂，因为它们在高达20000℃的等离子温度下会发生分解，或者形成非常易碎的状态，例如，W2C。所述金属碳化物粒子确实提供了更高的抗磨损性能，但是由于它们的物体特性(例如较低的热膨胀系数和较低的导热性)和机械特性(例如，较低的延展性)与基底不同，它们也具有缺点，即具有较高的脆性和较低的断裂韧度。在引擎工作过程中，尤其是在混合摩擦和无效润滑的情况下，这些缺点会带来影响。在这些状态下，在摩擦过程中另外引入的热能会导致出现松弛过程，其中由于完全不同的热膨胀系数，活塞环层不能跟上基底的膨胀，从而生成裂缝网。这种结果最终导致在重复的负荷后发生断裂。此外，金属碳化物经常被引入到金属基(例如NiCr合金)中，其中润湿只发生在合金表面，而不会获得冶金学上的互锁。因此，金属碳化物(例如WC或者Cr3C2)的黏附性可以提供和硬材料区域一样的高耐磨性，但是这种黏附性是有限的。
为了增加材料的强度，除其它以外，还可执行弥散硬化。这种情况下出现的粒子形成障碍，阻止机械负荷过程中材料内的错位运动。在负荷过程中产生和出现的这种错位不能穿过粒子，事实上，它们不得不在粒子之间膨胀。这又形成必须被绕过的错位环。当绕过时，比穿过需要更高的能量输入。错位前进过程中的屈服应力随着粒子距离的减小和粒子尺寸的减小而增加。因此，材料强度也增加了。
通过引入纳米粒子形式的碳化物，可实现弥散硬化。此处的术语“纳米粒子”指的是尺寸为1-200nm的粒子。之前仅通过成团纳米粒子的方式来执行纳米晶热喷涂涂层的生产。这种纳米粒子团的直径可达到0.1-100μm。只有粒子尺寸大于1-2μm时，正常压力状态下的粒子传送才是可能的。由于以下事实：对于气流中的定向传输，纳米粒子必须通过与气体分子的碰撞吸收最小量的能量，且被吸收的最大能量随着粒子尺寸的减小而减小，因此，纳米粒子仅在达到一个最小尺寸时，才能以定向方式传送。这只有通过更小的处理压力或者通过为粒子充电才可能实现。特别是，在粒子尺寸小于800nm的情况下，粒子的特性类似于气体分子。因此如果可得到成团的纳米晶粉末，才可以生成纳米晶HVOF层。因此，必须仍然在粉末内执行粒子强化。这导致生成的涂层包含有微粒和纳米粒子团，但是没有精细分散的离散纳米粒子。在例如DE 102007 018 859 A1、DE 100 57 953 A1、US 5,939,146A、US 6,723,387B1和US2004/0131865A1中描述了包含纳米粒子团的涂层。
发明内容
因此，本发明的目的是提供一种生成弥散硬化物(特别是包含碳化物纳米粒子的活塞环)的方法。
根据本发明，该目的通过以下方法解决，该方法包括通过热喷涂方法生产物体，其中燃烧室的下游处，通过载气(carrier gas)的方式，向气流提供至少一种碳化物纳米粒子前体，该纳米例子前体在气流中发生反应，生成碳化物。因此，根据本发明，通过来自气相的纳米粒子，可以实现弥散加固，其中纳米粒子在气相中产生，并接下来与喷涂粉末中的微晶粒子凝结，接着，以常规的参数确保进一步传送纳米粒子团。载气优选地包括化学惰性气体。化学惰性气体包括例如稀有气体或者氮气，优选采用氮气。
碳化物纳米粒子前体优选地采用过渡金属卤化物。特别优选地是较便宜的过渡金属卤化物，例如WCl6。并且，可使用例如Si、V、W或者钛之类的元素，它们在外部反应器中蒸发，并且在包括C的气氛中发生反应，形成各种碳化物。
热喷涂设备或者受到热负荷的外部纳米粒子生成器(例如，管式炉)内的热能被用于使前体材料或基本材料系统地分解，从而获得期望的材料作为气相中的纳米粒子。作为热喷涂方法，优选高速氧燃料热喷涂技术(HVOF)。使用外部纳米粒子生成器可生成纳米粒子增强的涂层系统，从而生成纳米粒子增强的组件，例如活塞环。
同样，碳化物纳米粒子前体可与其他气体发生化学反应。这包括燃烧气体或添加到载气中的气体。合适的气体碳源是气态碳氢化合物，例如甲烷。作为还原剂，例如，可以添加氢。示范性的反应如化学式1所示。
WCl6+CH4+H2→WC+6HCl                    (1)
但是，也可能通过两个碳电极之间的电弧在外部反应器中蒸发金属，例如，钨、钛或者钒，从而生成WC。
本发明还涉及一种弥散硬化物，其包含碳化物纳米粒子，且根据本发明的方法生成。所述弥散硬化物优选地包括内燃机的组件，尤其优选活塞环。
最后，本发明涉及用于执行根据本发明的方法的设备。所述设备涉及热喷涂设备，其在燃烧室的下游除了有用于供应热喷涂粉末的至少一个管线之外，还包括通过载气的方式供应碳化物纳米粒子前体或者由外部反应器生成的纳米粒子的至少一个管线。通过载气的方式供应碳化物纳米粒子前体的管线优选地由石墨制成，石墨可以耐受热喷涂的高温。所述设备特别优选地涉及用于高速氧燃料热喷涂(HVOF)的设备。
附图说明
图1是通过热喷涂和外部纳米粒子生成器生成纳米粒子加强层的示意图。
具体实施方式
图1是通过热喷涂和外部纳米粒子生成器生成纳米粒子加强层的示意图。纳米粒子加强层系统的生成可通过高速氧燃料热喷涂(HVOF)来实现，例如，通过在外部反应器1中提供纳米粒子，在该外部反应器1中，材料以受控的方式被蒸发(参见图1)。以这种方式生成的纳米粒子在第二炉2中在用于特定设置粒子形状的气流中被烧结，并在气流被馈送到喷枪4之前不久，与气流中的微粒凝结成团。通过载气传送纳米粒子的管线可以与传送微粒的管线以简单的方式连接，例如，通过T形连接器连接。附图标号3表示粉末运输器。所获得的基底用附图标号5表示。

Claims (17)

1.一种用于生成包含纳米粒子的弥散硬化物特别是活塞环的方法，包括通过热喷涂方法生成所述弥散硬化物，其特征在于，在燃烧室的下游处，通过载气的方式，向气流提供至少一种碳化物纳米粒子前体或者外部生成的纳米粒子，该纳米例子前体或者纳米粒子在气流中发生反应生成碳化物，或者是以碳化物的形式提供的。
2.根据权利要求1所述的方法，其特征在于，所述碳化物纳米粒子前体包括过渡金属卤化物。
3.根据权利要求2所述的方法，其特征在于，所述碳化物纳米粒子前体包括过渡金属氯化物。
4.根据权利要求3所述的方法，其特征在于，所述碳化物纳米粒子前体包括WCl6。
5.根据前述权利要求任一项所述的方法，其特征在于，从外部热操作的反应器中生成的所述碳纳米粒子被送入喷涂室。
6.根据前述权利要求任一项所述的方法，其特征在于，从外部热操作的反应器中生成的所述碳纳米粒子包括SiC、TiC、WC或者VC。
7.根据前述权利要求任一项所述的方法，其特征在于，所述热喷涂方法包括高速氧燃料热喷涂。
8.根据前述权利要求任一项所述的方法，其特征在于，所述载气包括碳氢化合物。
9.根据权利要求8所述的方法，其特征在于，所述碳氢化合物包括甲烷。
10.根据前述权利要求任一项所述的方法，其特征在于，所述载气包括氢气。
11.一种根据前述权利要求任一项所述的方法生成的包含碳化物纳米粒子的弥散硬化物。
12.根据权利要求11所述的弥散硬化物，其特征在于，所述弥散硬化物包括内燃机的组件。
13.根据权利要求11所述的弥散硬化物，其特征在于，所述弥散硬化物包括活塞环。
14.一种用于执行根据权利要求1至11任一项所述方法的设备，其特征在于，所述设备包括热喷涂设备，所述热喷涂设备在燃烧室的下游除了有用于供应热喷涂粉末的至少一个管线之外，还包括通过载气的方式供应碳化物纳米粒子前体的至少一个管线。
15.根据权利要求14所述的设备，其特征在于，所述通过载气的方式供应碳化物纳米粒子前体的至少一个管线由石墨制成。
16.根据权利要求15所述的设备，其特征在于，所述至少一个管线用于通过载气的方式提供外部生成的碳化物纳米粒子。
17.根据权利要求14至16任一项所述的设备，其特征在于，所述设备包括用于高速氧燃料热喷涂的设备。
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