CN118076766A - 用于钢或铁基合金发动机活塞的氧化保护层 - Google Patents
用于钢或铁基合金发动机活塞的氧化保护层 Download PDFInfo
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000962 organic group Chemical group 0.000 claims description 2
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- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/125—Process of deposition of the inorganic material
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- C23C18/127—Preformed particles
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
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Abstract
本发明涉及一种用于减少内燃机活塞高温氧化的涂层。这种涂层是通过含有钛酸酯或锆酸酯的组合物获得的，其中至少有一种金属颜料被引入该涂层中。
Description
技术领域
本发明涉及一种用于钢或其他铁基合金发动机活塞的涂层，其可以减少或防止活塞的氧化和可能的腐蚀。
背景技术
由于导热性较低，钢活塞在发动机中的温度要比铝活塞高得多。因此，钢表面会引发各种反应。例如，在活塞冠的燃烧凹槽边缘会形成氧化层，氧化层会剥落并导致该处的材料层厚度减少。在最坏的情况下，活塞会因此开裂，导致材料失效。
迄今为止，只能通过昂贵或因其他原因而不利的措施来消除这种氧化的后果。一种方法是增大活塞的尺寸，这样活塞就会变得更重。不过，特别是对于LVD活塞，即用于轿车或轻型商用车柴油发动机的活塞，活塞重量轻更有优势。
另一种减少氧化的方法是使用铬和镍含量较高的特殊合金。不过，这种合金价格昂贵，而且表面处理(如锰磷化处理)更加困难。电镀保护层或陶瓷喷涂层的应用也很复杂，而且成本高昂。
因此，需要一种用于钢或其他铁基合金制成的活塞的涂层，这种涂层不仅能提供良好的氧化保护，必要时还能起到防腐蚀的作用。
US 8,6288,827描述了一种用于金属零件的涂层，其目的是在室温下保护表面免受大气腐蚀。该涂层是通过涂布含有钛酸酯或锆酸酯的组合物并固化而获得的。为使涂层具有光泽，可在组合物中加入少量锌、铝或锌铝合金。这种涂层用于内燃机活塞或其他暴露在高达550℃高温下的部件中的用途尚未公开。
令人惊奇的是，现在已经证明可以通过在活塞上涂布一层由钛酸酯或锆酸酯组成并含有至少一种金属颜料的组合物来解决上述问题。尤其令人惊奇的是，如果在通过钛酸酯或锆酸酯获得的涂层中加入金属颜料，则层的内聚力会得到改善。这样，就得到了一种适用于内燃机活塞的涂层。
附图说明
图1显示了发动机运行测试后有涂层和无涂层活塞的显微照片。
具体实施方式
因此，本发明涉及一种活塞，特别是内燃机活塞，由钢或其他铁基合金制成，其中，在活塞的至少一个部分上涂布一层，该层可从含有钛酸酯或锆酸酯的组合物中获得并含有至少一种金属颜料。此外，本发明还涉及一种生产该层的方法及其用于防止活塞高温氧化或热气氧化的用途。
在本发明中，优选的是，从含有钛酸酯的组合物中获得涂层。
在生产本发明的涂层时，组合物中所含的钛酸酯或锆酸酯被用作前体。通过部分或完全裂解(解离)有机残留物，形成基于Ti-O或Zr-O单元的层。
这种解离过程可以在使用适当的组合物后，通过暴露于湿气(包括大气中的湿气)或使用能量(例如通过辐照或加热)来启动。这种解离过程会导致涂层固化。
优选的是，在完全固化状态下，从含有钛酸酯或锆酸酯的组合物中得到的层含有20-40wt％的氧化钛或20-40wt％的氧化锆，以整个层为基准。术语“完全固化状态”是指使用喷枪喷涂，然后在烘箱中以大约250℃的温度加热30分钟后得到的层。
由于有机残留物的部分或完全解离，钛酸酯或锆酸酯分子会“收缩”，因此产生的层会出现裂缝和气孔。这就导致层的内聚力出现问题。
现在研究表明，如果在涂层中加入至少一种金属颜料，内聚力就会显著提高。这样，涂层就能更好地保护活塞免受氧化，从而解决了本发明的根本问题。
根据本发明，以下通式(I)的化合物可用作钛酸酯或锆酸酯：
其中R1、R2、R3和R4各自独立地代表H或有机基；优选H、苯基或C1-C6烷基；尤其优选苯基或C1-C4烷基。R1,R2,R3和R4可以有取代基，但优选是未取代基。M代表Ti或Zr，优选Ti。n代表自然数，优选1至4。
在本发明的一个特别有利的实施方案中，使用的钛酸酯选自钛酸四甲酯、钛酸四异丙酯、钛酸四丁酯和钛酸四苯酯组成的组。锆酸酯优选选自锆酸四甲酯、锆酸四异丙酯、锆酸四丁酯和锆酸四苯酯组成的组。
在本发明中，钛酸酯和锆酸酯也可以螯合物的形式使用。
通过含钛酸酯或锆酸酯组合物获得的涂层至少含有一种金属颜料。
锌基、镁基或铝基合金尤其适合用作金属颜料。优选的是铝镁合金和锌镁合金。
在本发明中，金属颜料例如以粉末形式使用，最好是颗粒直径小于或等于50μm的粉末。
优选的是，根据本发明的层的厚度在5-100μm之间，更优选的是，在10-50μm之间，特别是在10-30μm之间。
本发明的涂层也可以是多层系统的一部分。换句话说，除了本发明的层之外，还可以在活塞上使用其他层，以便以不同的方式影响活塞的特性。这些层可以应用在本发明层的下面或上面。
本发明的层适用于内燃机活塞中常用的所有钢和铁基合金。
带有本发明所述层的活塞可通过以下步骤生产：
a)将包含至少一种通式(I)的钛酸酯或锆酸酯的组合物涂抹在活塞上；
b)将至少一种金属颜料涂抹在活塞上；
c)部分或完全解离钛酸酯或锆酸酯；以及
d)固化组合物。
在本发明的方法中，步骤a)和b)可以独立进行，也可以一起进行。优选的是，将含钛酸酯或锆酸酯的组合物和金属颜料一起涂布。尤其优选的是，在将金属颜料涂布到活塞上之前，先将其加入到含钛或锆的组合物中。为此，金属颜料可以例如以粉末或糊状等形式使用。
然后按照所述方法解离钛酸酯或锆酸酯，并固化该层。
通过使用本发明的层，可以减少活塞的高温氧化或热气腐蚀。
本发明的效果
将含有钛酸酯和锌镁合金颜料的组合物喷涂到42CrMo4制成的活塞上。随后，将组合物放入烘箱中，在大约250℃的温度下加热30分钟，使其固化。
涂有涂层的活塞和未涂涂层的活塞接受了516小时的发动机运行测试，其中发动机在满负荷和怠速状态下交替运行30分钟和2分钟。
图1显示了测试完成后两个活塞的显微照片。从图1中可以看出，没有涂层的活塞上形成了厚度约为43μm的氧化层。与此相反，本发明的含钛酸酯涂层防止了高温氧化(热气腐蚀)。
Claims (10)
1.活塞，特别是用于内燃机的活塞，所述活塞的至少部分上具有一层，
其中该层可通过包含至少一种通式(I)的钛酸酯或锆酸酯的组合物获得；以及
该层包含至少一种金属颜料，
其中R1、R2、R3和R4各自独立地代表H或有机基；优选H、苯基或C1-C6烷基；尤其优选苯基或C1-C4烷基；M代表Ti或Zr；n代表整数。
2.根据权利要求1所述的活塞，其中所述组合物包括钛酸酯，优选是钛酸四甲酯、钛酸四异丙酯、钛酸四丁酯和/或钛酸四苯酯。
3.根据权利要求1或2所述的活塞，其中所述至少一种金属颜料为基于锌、镁或铝的合金，优选为基于铝镁合金或锌镁合金。
4.根据权利要求1至3中任一项所述的活塞，其中该层可通过涂布该组合物、部分或完全解离通式(I)的钛酸酯以及固化该组合物来获得。
5.一种内燃机，包括根据权利要求1至4中任一项所述的活塞。
6.一种制造活塞的方法，包括以下步骤：
a)将包含至少一种通式(I)的钛酸酯或锆酸酯的组合物涂布在活塞上；
b)将至少一种金属颜料涂布在所述活塞上；
c)部分或完全解离所述钛酸酯或锆酸酯；以及
d)固化所述组合物。
7.根据权利要求6所述的方法，其中通式(I)的所述钛酸酯的解离是通过暴露于湿气、加热或辐照启动的。
8.根据权利要求6或7所述的方法，其中所述钛酸酯和所述金属颜料通过相同的组合物涂布。
9.根据权利要求6至8中任一项所述的方法，其中在步骤b)中，将至少一种基于锌、镁或铝合金的金属颜料，优选是基于铝镁合金或锌镁合金的金属颜料涂布在所述活塞上。
10.一种根据权利要求1至4中任一项所述的防止内燃机活塞高温氧化的层的用途。
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| DE102021210995.0A DE102021210995A1 (de) | 2021-09-30 | 2021-09-30 | Oxidationsschutz-Schicht für Motorkolben aus Stahl oder einer eisenbasierten Legierung |
| DE102021210995.0 | 2021-09-30 | ||
| PCT/EP2022/076178 WO2023052215A1 (de) | 2021-09-30 | 2022-09-21 | Oxidationsschutz-schicht für motorkolben aus stahl oder einer eisenbasierten legierung |
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| FR2866029B1 (fr) | 2004-02-11 | 2006-05-26 | Dacral | Composition de revetement anti-corrosion en dispersion aqueuse comprenant un titanate et/ou un zirconate organique |
| DE102005006671A1 (de) * | 2005-02-15 | 2006-08-17 | Ks Kolbenschmidt Gmbh | Schutzschicht gegen Heißgaskorrision im Verbrennungsraum einer Brennkraftmaschine |
| US20090098289A1 (en) * | 2007-10-12 | 2009-04-16 | Deininger Mark A | Pig and Method for Applying Prophylactic Surface Treatments |
| JP6339118B2 (ja) * | 2015-04-08 | 2018-06-06 | アイシン精機株式会社 | 車両用機械部品およびピストン |
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| DE102021210995A1 (de) | 2023-03-30 |
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