CN108350316A - 防止内燃机的活塞氧化的保护层 - Google Patents

防止内燃机的活塞氧化的保护层 Download PDF

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CN108350316A
CN108350316A CN201680064944.2A CN201680064944A CN108350316A CN 108350316 A CN108350316 A CN 108350316A CN 201680064944 A CN201680064944 A CN 201680064944A CN 108350316 A CN108350316 A CN 108350316A
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piston
coating
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M·丹恩菲尔德特
M·布鲁姆
T·富尔曼
D·莱特兹曼
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Federal Mogul Nuernberg GmbH
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F02F3/12—Pistons  having surface coverings on piston heads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B23/00—Other engines characterised by special shape or construction of combustion chambers to improve operation
    • F02B23/02—Other engines characterised by special shape or construction of combustion chambers to improve operation with compression ignition
    • F02B23/06—Other engines characterised by special shape or construction of combustion chambers to improve operation with compression ignition the combustion space being arranged in working piston
    • F02B23/0696—W-piston bowl, i.e. the combustion space having a central projection pointing towards the cylinder head and the surrounding wall being inclined towards the cylinder wall
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00—Other material characteristics; Treatment of material
    • F05C2253/12—Coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Paints Or Removers (AREA)

Abstract

公开了一种用于减少或防止内燃机中的活塞的热气氧化的涂层。所述涂层包含聚硅氮烷系聚合物。

Description

防止内燃机的活塞氧化的保护层
技术领域
本发明涉及聚硅氮烷系层在减少或防止内燃机中的活塞氧化中的应用，以及具有该涂层的活塞。
背景技术
钢活塞由于其较低的导热性而在发动机中比铝活塞更热得多。其结果是在钢表面触发不同的反应。因此，例如在活塞冠中的燃烧室边缘上形成氧化物层，该氧化物层可以脱离并由此导致该位点处材料层厚度的减小。在最坏的情况下，活塞因此变得破裂，这导致材料失效。
到目前为止，这种氧化的结果出于其他原因只能通过昂贵或不利的措施来应对。一种可能性是活塞的加强尺寸，这使其更重。然而，低活塞重量有利于LVD活塞，即轿车或轻型商用车辆中柴油发动机的活塞。
减少氧化的另一种可能性是使用具有高铬和镍含量的特殊合金。然后，这样的合金是昂贵的。此外，高铬含量会干扰锰磷酸化过程中的层形成，而且还增加了维持浴所涉及的工作。在钢活塞上施加保护性电镀涂层也会导致高成本。
到目前为止，在活塞上使用聚硅氮烷或聚硅氧烷系涂层以便降低热导率或避免油-碳结块(参见例如WO 2012/024415、US 2007/011382和WO 2006/087113)。
通常，这样的涂层仅施加在活塞冠的空腔中，即所谓的冷却通道中。这可以防止油-碳堵塞冷却通道，从而使活塞冷却得更差。在运行过程中由此产生的较高的活塞温度继而会导致活塞的机械故障。
WO 2006/087113中使用的聚硅氧烷层通过溶胶-凝胶工艺制造。然而，该工艺导致多孔层，因此这些层是透气的并且不适于避免氧化。
与油-碳结块不同，氧化会导致问题，特别是在燃烧室边缘区域的问题，因为此位点出现最高的部件温度和大机械负荷。
由于迄今为止防止活塞的热气腐蚀的可能性不足，因此需要一种可以容易且经济地施加并有效防止热气氧化的涂层。
该目的根据本发明通过聚硅氮烷系涂层的应用和施加该涂层的特定方法来解决。
具体实施方式
本发明涉及包含聚硅氮烷系聚合物的涂层在减少或防止内燃机中的活塞氧化中的应用。
在本发明的范围内，特别是受到氧化损伤最大的燃烧室边缘和相邻表面可以以有利的方式得到保护。因此，根据本发明，优选燃烧室的边缘，特别是整个外活塞冠区域被涂覆。在一个特别优选的实施方式中，包括燃烧室的整个活塞冠被涂覆。
根据本发明，使用包含聚硅氮烷系聚合物的涂层(下面也称作聚硅氮烷系涂层)。可使用无机和有机聚硅氮烷作为基体。根据本发明使用的无机聚硅氮烷形成Si和N原子的非晶形网络，其具有式-(H2Si-NH)n-的组分，也被称作全氢聚硅氮烷。在有机聚硅氮烷中，所述网络通过有机基团改性，产生式-(R1R2Si-NH)-的组分。显然，还可以使用含有无机和有机聚硅氮烷单元的聚合物。
聚硅氮烷系涂层通常用于电子部件。可为此商购的产品可以在本发明的范围内使用。
可使用全氢聚硅氮烷在溶剂中的溶液来形成无机聚硅氮烷。例如，可使用20％全氢聚硅氮烷的二丁醚溶液(例如，得自AZ Electronic Materials公司)。
有机聚硅氮烷可具有不同的取代基R1和R2，例如，可使用用乙烯基改性的聚硅氮烷。它们可溶于不同的溶剂，例如乙酸丁酯。这些溶液能够可选地含有其它有机掺混剂。合适的有机聚硅氮烷的实例是HTT 1800(Merck KGaA)和HTA 1500(KiON DefenseTechnologies)。
涂层的厚度优选为0.2μm至400μm，并且高的层厚度通常仅能借助于有机聚硅氮烷产生。
特别是当使用无机聚硅氮烷时，涂层的厚度优选为0.2μm至10μm，特别优选0.5μm至2μm。
聚硅氮烷与湿气、水或醇的反应形成聚硅氧烷层，该层在无机聚硅氮烷的情况下为非晶石英玻璃层。
借助于本发明，特别能够有效地防止CrMo合金钢的活塞氧化。这被证明对于42CrMo4活塞是特别有利的。这种合金通常只能用于低到中等负荷，因为其在高负荷下通过热气腐蚀而令人无法接受地迅速氧化。
此外，本发明涉及减少或防止内燃机中的活塞氧化的方法。该方法包括对活塞的区域施加上述聚硅氧烷系涂层。聚硅氮烷对活塞的施加可例如以本领域技术人员知晓的方式通过漆涂、浇注和喷涂来进行。
以这种方式施加的组合物优选被加热至15℃至255℃的温度以便于交联。
聚硅氮烷系涂层在接下来的几天内在湿气、水或醇的影响下至少部分转化为聚硅氧烷系涂层。本发明的方法以特别合适的方式进行，使得聚硅氮烷网络完全转化为聚硅氧烷网络。
与现有技术中已知的通过溶胶-凝胶工艺生产的层相反，以这种方式生产的聚硅氧烷层不是多孔的并因此是气密的，从而防止了活塞的氧化。
在另一个实施方式中，本发明涉及一种活塞，其中燃烧室的至少边缘、更优选整个外活塞冠区域，特别是包括燃烧室的整个活塞冠设置有上述聚硅氮烷系涂层。

Claims (10)

1.一种包含聚硅氮烷系聚合物的涂层在减少或防止内燃机中的活塞氧化中的应用。
2.如权利要求1所述的应用，其中活塞冠的区域被涂覆。
3.如权利要求1或2所述的应用，其中燃烧室的至少边缘、优选整个燃烧室被涂覆。
4.如权利要求1至3中任一项所述的应用，其中使用无机或有机聚硅氮烷、优选无机聚硅氮烷作为聚合物的基体。
5.如权利要求1至4中任一项所述的应用，其中所述涂层的厚度为0.2μm至400μm，优选为0.2μm至10μm，特别为0.5μm至2μm。
6.如权利要求1至5中任一项所述的应用，其中它是钢活塞，优选CrMo合金钢活塞，特别是42CrMo4活塞。
7.一种减少或防止内燃机中的活塞氧化的方法，所述方法包括将权利要求1至6中任一项限定的涂层施加至所述活塞的区域。
8.如权利要求1至7中任一项所述的方法，其中所述聚硅氮烷在15℃至255℃的温度下交联。
9.如权利要求7或8所述的方法，其中所述涂层随后至少部分转变成聚硅氧烷系涂层。
10.一种活塞，特别是内燃机的活塞，其包括权利要求1至6中任一项所述的涂层，其中燃烧室的至少边缘设置有所述涂层。
CN201680064944.2A 2015-11-09 2016-11-08 防止内燃机的活塞氧化的保护层 Pending CN108350316A (zh)

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DE102015221960.7A DE102015221960A1 (de) 2015-11-09 2015-11-09 Schutzschicht gegen die Oxidation des Kolbens eines Verbrennungsmotors
DE102015221960.7 2015-11-09
PCT/EP2016/076947 WO2017080986A1 (de) 2015-11-09 2016-11-08 Schutzschicht gegen die oxidation des kolbens eines verbrennungsmotors

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EP (1) EP3374458B1 (zh)
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DE (1) DE102015221960A1 (zh)
WO (1) WO2017080986A1 (zh)

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JP2019502867A (ja) 2019-01-31
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Application publication date: 20180731