CN107699889A - 陶瓷微球热障涂层 - Google Patents

陶瓷微球热障涂层 Download PDF

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CN107699889A
CN107699889A CN201710665259.1A CN201710665259A CN107699889A CN 107699889 A CN107699889 A CN 107699889A CN 201710665259 A CN201710665259 A CN 201710665259A CN 107699889 A CN107699889 A CN 107699889A
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insulating barrier
sealant
thermal barrier
barrier coating
microballoon
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R·P·达雷特
P·M·纳吉特
P·P·安德勒斯凯维奇四世
G·P·希尔
T·A·舍德勒
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GM Global Technology Operations LLC
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GM Global Technology Operations LLC
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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Abstract

用于部件的热障涂层包括施加至基底的表面的绝缘层。绝缘层包含多个陶瓷微球。密封层与绝缘层接合。密封层是不渗透的，使得密封层密封绝缘层。将热障涂层施加至部件的基底的表面的方法包括提供多个陶瓷微球并将多个陶瓷微球施加至基底的表面。对部件表面上的多个陶瓷微球施加至少一种热处理，以在基底的表面上形成绝缘层。

Description

陶瓷微球热障涂层
技术领域
本公开涉及一种用于内燃机的热障涂层。
背景技术
一些车辆包括用于推进的发动机组件。发动机组件可以包括内燃机和燃料喷射系统。内燃机包括一个或多个汽缸。每个汽缸限定燃烧室。在运行中，内燃机在燃烧室中燃烧空气/燃料混合物，以便移动设置在汽缸中的活塞。
可以基于发动机组件的配置和各种部件的功能来限制发动机组件中的维持温度环境。不均匀的温度分布会影响部件的效率。在内燃机中，涂层使热燃烧气体与冷的水冷式发动机缸体隔离，以避免由燃烧气体向冷却水输送热量而导致的能量损失。此外，在进气循环期间，涂层应迅速冷却，以免在点火之前加热燃料空气混合物。
发明内容
热障涂层包含施加至基底的表面的绝缘层。绝缘层包含多个陶瓷微球。密封层与绝缘层接合。密封层是不渗透的，使得密封层密封绝缘层。
热障涂层的绝缘层可以具有至少约75％的孔隙率和约50微米至约1毫米的厚度。绝缘层还可以包含配置成与多个微球接合的基质材料。
基质材料还包含与球体一起熔合的三氧化硼、氧化铝、硅酸铝、二氧化硅或硅酸盐玻璃或其混合物，由选自在绝缘层的热处理过程中氧化成金属氧化物的金属、金属合金和金属硝酸盐(诸如铝、铝合金或硝酸铝)的群组组成的颗粒，或与由选自硅氧烷、硅烷、碳硅烷、硅氮烷和硼硅烷的群组组成的陶瓷前体聚合物，陶瓷前体聚合物在绝缘层热处理时转化为陶瓷。
密封层可以包含选自由氧化铝，硅酸铝，氧化硅，硅酸盐玻璃或其混合物，包括镍、钴、铁、铬、难熔金属和相应的合金的高温金属和金属合金组成的群组的一种或多种元素。或者，密封层可以由包含选自硅氧烷、硅烷、碳硅烷、硅氮烷和硼硅烷组成的群组的一种或多种元素的陶瓷前体聚合物形成，其中在绝缘层热处理时，陶瓷前体聚合物转化为陶瓷。
多个陶瓷微球还包含约0wt％至约100wt％的氧化硅和约0wt％至约100wt％的氧化铝。或者，多个陶瓷微球还包含约50wt％至约70wt％的氧化硅和约30wt％至约50wt％的氧化铝。密封层的厚度为约1微米至约20微米。
在本公开的另一实施例中，一种将热障涂层施加至部件的基底的表面的方法包括提供多个陶瓷微球。可以对多个陶瓷微球进行分拣以选择使用的陶瓷微球。可以将基质的颗粒添加到所选择的微球中。颗粒可以包括各种混合物，并且可以以微球的约5wt％至约50wt％的重量分数加入。对部件表面上的多个陶瓷微球和基质施加至少一种热处理。在一个实施例中，提供多个陶瓷微球的步骤还包含分拣和选择直径约10微米至约50微米的陶瓷微球。从以下结合附图对用于实施本公开的最佳模式的详细描述中，本公开的上述特征和优点以及其他特征和优点是显而易见的。
附图说明
图1是车辆的示意性示意图，示出了具有设置在多个部件上的热障涂层的单汽缸内燃机的侧视图；
图2是设置在部件上的热障涂层的示意性横截面侧视图；
图3A-3B是施加至部件的基底的热障涂层的接合微球的示意性横截面侧视图；以及
图4A-4B是具有设置在部件上的密封层的热障涂层的示意性横截面侧视图，示出了施加至基底的热障涂层。
具体实施方式
现在将详细参考在附图中示出的本公开的几个实施例。只要有可能，在附图和说明书中使用相同或相似的附图标记来表示相同或相似的零件或步骤。附图是简化的形式，而不是精确的尺度。为了方便和清楚的目的，可以使用关于附图的方向性用词，例如顶部、底部、左面、右面、上面，在……上面，在……之上，在……下面，在……之下，后面和前面。这些和类似的方向性用词不应被解释为以任何方式限制本公开的范围。
参考附图，其中在几个附图中相同的附图标记对应于相同或相似的部件，根据本公开的示例性实施例的具有推进系统12的车辆10的一部分在图1中示意性地示出。推进系统12可以是内燃机、燃料电池、马达等中的任何一种。推进系统12可以是车辆10的一部分，车辆10可以包括机动车辆，诸如但不限于标准乘用车、运动型多功能车、轻型卡车、重型车辆、小型货车、公共汽车、运输车辆、自行车、机器人、农具、运动相关设备或任何其他运输装置。为了清楚的目的，下面将推进系统12称为内燃机或发动机12。
车辆10的发动机12可以包括一个或多个部件14。部件14具有施加至其上的本文公开的类型的热障涂层(TBC)16。在本公开的一个实施例中，TBC 16可以包括复合或多层结构或配置。虽然图1的车辆10和发动机12是适用于本文公开的TBC 16的典型示例应用，但是本设计不限于车辆和/或发动机应用。
任何其中其部件暴露于热量的固定或移动的机器或产品可能受益于使用本设计。为了说明的一致性，下面将车辆10和发动机12作为示例系统进行描述，而并不限制在这样的实施例中使用TBC 16。
图1示出了限定单汽缸18的发动机12。然而，本领域技术人员将认识到，本公开也可以应用于具有多个汽缸26的发动机12的部件14。每个汽缸18限定燃烧室22。发动机12配置成为车辆10的推进提供能量。发动机12可以包括但不限于柴油发动机或汽油发动机。发动机12还包括各自与燃烧室22流体连通的进气组件28和排气歧管30。发动机12包括往复运动的活塞20，活塞20在汽缸18内可滑动地移动。
燃烧室22配置成燃烧空气/燃料混合物以为车辆10的推进提供能量。空气可以通过进气组件28进入发动机12的燃烧室22，在此处，从进气歧管进入燃料室22的气流由至少一个进气阀24控制。燃料被喷射到燃烧室22中以与空气混合，或通过提供空气/燃料混合物的进气阀32引入。空气/燃料混合物在燃烧室22内点燃。空气/燃料混合物的燃烧产生废气，废气排出燃烧室22并被吸入排气歧管30。更具体地，排出燃烧室22的气流(排气流)由至少一个排气阀26控制。
参考图1和图2，TBC 16可以设置在发动机12的一个或多个部件14的面或表面上，包括但不限于活塞20、进气阀24、排气阀26、排气歧管30的内壁等。在本公开的一个实施例中，TBC 16可以施加至发动机12的高温部分或部件，并接合到部件14，以形成绝缘体，该绝缘体配置成在发动机12运行期间降低传热损失，增加效率并增加废气温度。
TBC 16配置成提供低热导率和低热容量以增加发动机效率。因此，低热导率降低了传热损失，并且低热容量意味着在温度波动和加热进入汽缸的冷空气期间TBC 16的表面随气体温度的变化最小化。在本公开的一个非限制性实施例中，TBC 16的厚度可以为约200微米(μm)，将TBC 16施加至表现出约0.09W/mK的计算热导率和240kJ/m3K的热容量的部件14的表面42，以最小化热量损失并增加发动机效率。应当理解，TBC 16可以施加至除了在发动机12内的部件。更具体地，TBC 16可以施加至航天器、火箭、注射模具等的部件。
现在参考图2，每个部件14包括具有至少一个外部或呈现表面42的基底40。TBC 16可以包括施加和/或接合到基底40的表面42的至少一个层44。TBC 16的至少一个层44可以包括多层，诸如第一或绝缘层46以及第二或密封层48。
绝缘层46可以包括多个微球50，微球50被烧结在一起以产生具有极高孔隙率和大部分闭孔结构的层。优选地，绝缘层46的孔隙率可以为至少约75％，更具体地，孔隙率为约75％至约95％。绝缘层46的高孔隙率提供了要包含在其中的相应体积的空气和/或气体，因此提供了低有效热导率和低有效热容量所需的绝缘性能。
设想绝缘层46中的孔隙率的体积分数越高，则热导率和容量越低。孔隙率水平需要与机械要求平衡，诸如承受发动机12中的高压水平所需的抗压强度。绝缘层的厚度T1可以在约50微米(μm)和约1000μm或1毫米(mm)之间。密封层48的厚度T2可以在约1μm和约20μm之间。绝缘层46配置成承受至少1000摄氏度(℃)的表面温度。
微球50可以由聚合物、金属、玻璃和/或陶瓷材料的组合构成。在一个非限制性实施例中，为了耐久性和耐高温下的氧化和腐蚀，微球50使用诸如玻璃气泡之类的陶瓷或诸如之类的空心微珠等形成。微球50可以具有在约10μm和约100μm之间的直径D1和约为微球50直径的约2％至约5％的壳厚度。
在本公开的一个实施例中，陶瓷微球50可以包含约0wt％至约100wt％的氧化硅(SiO2)和约0wt％至约100wt％的氧化铝(Al2O3)。或者，多个陶瓷微球可以包含约50wt％至约70wt％的氧化硅和约30wt％至约50wt％的氧化铝以实现更高的熔点。
或者，如果材料具有足够的高温能力和大于8ppm/C的热膨胀系数(CTE)，则氧化铝或其他氧化物或陶瓷可用于形成微球50。非限制性示例性材料可以包括氧化钇稳定的氧化锆、稀土锆酸盐烧绿石和稀土钛酸盐烧绿石，其中稀土选自由钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)和镥(Lu)组成的群组。
微球50可以通过一种或多种物理因素(诸如通过尺寸或密度)进行分拣，以达到目标尺寸分布。在一个非限制性实施例中，微球50的平均直径将为TBC 16厚度的约四分之一，但是应当理解，对于较薄的TBC 16，微球50的直径将较小。例如，微球50可以被分拣和选择，其直径为约10微米至约50微米。
参考图3A和3B，在本公开的一个实施例中，微球50可以与通常由标记56表示的基质形成合金的颗粒54组合。图3A示出了在加热之前的一部分TBC 16，其中颗粒54定位在相邻微球50之间的空腔中。颗粒54在基质56中与微球50结合，以增加绝缘层46的结构耐久性和鲁棒性。
颗粒54可以是在比微球50更低的温度下熔化或烧结的组合物，以将相邻的微球50熔合在一起，并与基底40的表面42与基质56熔合而不会使微球50变形或损坏。如果颗粒54的熔点低于约1000摄氏度(℃)(即标准推进系统运行温度)，则可使颗粒54与微球50或其他材料成为合金以形成熔点大于1000摄氏度(℃)的基质56。
颗粒54可以包含陶瓷或玻璃，诸如三氧化硼、氧化铝、硅酸铝、二氧化硅、硅酸盐玻璃或其混合物，这些物质具有比中空球更低的熔点并促进烧结和接合。或者，颗粒54可以包含在低于1000摄氏度(℃)的温度下熔化的金属，诸如铝或铝合金，以熔合微球50并通过氧化转化成氧化铝。或者，颗粒54可以包含金属硝酸盐或金属醇盐前体，诸如硝酸铝或异丙醇钛或四乙氧基硅烷，所述金属硝酸盐或金属醇盐前体可被热解为氧化物，例如氧化铝或氧化钛或氧化硅。在该实施例中，微球50与金属硝酸盐或醇盐前体或纯前体的溶液混合。
在另一替代实施例中，颗粒54可以包含陶瓷前体聚合物，例如硅氧烷、硅烷、碳硅烷、硅氮烷、硼硅烷和被热解成氧化物的类似分子。可以设想，可以限定用于基质56的颗粒54的尺寸分布。在一个实施例中，可以从基质中排除小于涂层厚度的约十分之一或大于涂层厚度的约三分之一的任何颗粒54，以通过避免微球50之间的大间隙来确保基质的结构耐久性和鲁棒性。
返回参考图2，更详细地描述了将第一或绝缘层46施加至基底40的表面42。将微球50置于浆料中。浆料可以包括作为比微球50的尺寸更细的粉末、经由化学反应、扩散或合金化促进烧结的添加剂，并且可以通过加入适量的溶剂、粘合剂、润滑剂、凝结剂和/或抗絮凝剂调节流变性以最小化和/或去除残留在其中的碳质或其他污染物，这些碳质或其他污染物可影响烧结过程或最终涂料组合物。
浆料可以由溶剂(诸如水)、水溶性粘合剂(例如羟丙基纤维素、聚乙烯醇、聚乙烯吡咯烷酮或纤维素聚合物衍生物)和三氧化硼作为烧结助剂形成。或者，粘合剂可以包括有机聚合物，诸如聚乙烯醇、聚乙烯吡咯烷酮或纤维素聚合物衍生物，这些物质在约0.1wt％至约8wt％浓度中使用，所述有机聚合物在随后的热处理期间大部分被除去。还可以将有机溶剂(诸如异丙醇或丙酮)加入水中或完全代替溶剂，在这种情况下粘合剂必须适当地溶于混合物中(诸如聚乙烯醇缩丁醛树脂)。
可以使用其他浆料添加剂，例如聚乙二醇和甘油，用于流变性调节，诸如抗絮凝、润滑和消泡，以最大化浆料施用时的包装效率。优选地，通过加入刚好足够的溶剂液化浆料用于施加，以平稳地流过基底40的表面42，例如针对10克(g)干燥微球50为约10毫升(ml)，并且最小量的粘合剂也加入以减少燃料烧尽后的残留碳。
涂层中基质56的体积分数为约5％至约20％，由此较低的体积分数可导致较高的总涂层孔隙率。基质56还可以密封TBC 16以免碳质燃烧残余物的进入，从而增加TBC 16中的开放孔隙率，从而增加热导率和容量。在涂层表面的高体积分数的基质56产生抑制燃烧气体和残余物进入的致密层，涂层中基质56的体积分数为约3％至约20％。或者，可以形成较低体积分数的基质56，以通过最初限制基质部分形成涂层，然后将薄层的额外的基质材料施加至涂层的顶部来降低热导率和容量，其中约10μm至约100μm的该致密基质中的基质56的体积分数为约20％至约40％。
可以通过将微球50的浆料施加至部件14的基底40的表面42来形成第一或绝缘层46。浆料可以经由加压喷枪作为喷涂涂层施加至基底40的表面42，加压喷枪被调节以将均匀的浆料涂层分散到表面42上。或者，浆料中的微球50可以在基底40的表面42上用刀片涂覆或刮涂，从而在约850摄氏度(℃)烧结约2小时。
如上所述，氧化物或金属颗粒54可以与微球50和溶剂和添加剂混合以形成浆料。将浆料的涂层施加至基底40的表面42，进行干燥和热处理以形成TBC 16。基底40的表面42上的浆料可以分两个阶段进行热处理。第一阶段可以是低温干燥工艺以足够缓慢地除去多余的溶剂以避免形成破裂。优选的温度范围为约20摄氏度(℃)至约250摄氏度(℃)。第二阶段可以是熔化或烧结步骤，以将微球50彼此和基底40的表面42熔合，以在约700摄氏度(℃)至约900摄氏度(℃)的温度范围内改善结构完整性。
在另一实施例中，将所得浆料的涂层施加至基底40的表面42，进行干燥和热处理以将前体热解成氧化物。在另一实施例中，可将陶瓷前体单体与溶剂混合以产生可与微球50混合的液体。然后可将该浆料作为涂层施加至基底40的表面42。在使溶剂蒸发之后，然后通过紫外线曝光或热退火来固化单体/微球涂层。固化使单体交联并形成刚性聚合物基质。然后将该聚合物基质在空气或惰性气氛中热解成陶瓷，例如在氩气中为1000摄氏度(℃)，精确的热解条件取决于陶瓷前体聚合物。
现在参考图4A和4B，密封层48设置在绝缘层46上面，使得绝缘层46设置在密封层48和部件14的基底40的表面42之间。密封层48可以是位于包含如图4A所示的微球的绝缘层的顶部上的通常不渗透、致密的薄膜，或者其可以是含有如图4B所示的微球的通常不渗透的层。更具体地，密封层48包含配置成承受大约1100摄氏度(℃)的温度的材料。密封层48可以配置成约1μm至约20μm的厚度。密封层优选由包括氧化铝、硅酸铝、氧化硅、硅酸盐玻璃或其混合物的材料形成。或者，密封层可以由高温金属或金属合金(诸如镍、钴、铁、铬、难熔金属及其合金)形成。或者，密封层可以由选自硅氧烷、硅烷、碳硅烷、硅氮烷和硼硅烷组成的群组组成的陶瓷前体聚合物形成，陶瓷前体聚合物在绝缘层热处理时转化为陶瓷。
密封层48可能对燃烧气体是不渗透的，使得在密封层48和绝缘层46之间提供密封。这种密封防止来自燃烧气体的碎屑(诸如未燃烧的碳氢化合物、烟灰、部分地反应的燃料、液体燃料等)进入由微球50限定的多孔结构。如果允许这种碎屑进入绝缘层46的多孔结构，则设置在多孔结构中的空气将最终被碎屑取代，并且绝缘层46的绝缘性能将被降低或消除。
密封层48可以配置成呈现光滑的外表面58。具有光滑的密封层48对于防止当空气流过密封层48的外表面58时产生湍流气流非常重要。此外，具有光滑表面的密封层48将防止增加的传热系数。在一个非限制性示例中，密封层48可以经由电镀施加至绝缘层46。在另一个非限制性示例中，密封层48可以在烧结绝缘层46的同时施加至绝缘层。
密封层48配置成具有足够的弹性，以便在暴露于碎屑期间抵抗压裂或破裂。此外，密封层48配置成具有足够的弹性，以便承受下面的绝缘层46的任何膨胀和/或收缩。此外，绝缘和密封层46、48各自配置成具有相容的热膨胀特性系数以承受热疲劳。
在本公开的一个实施例中，TBC 16可以包括形成为陶瓷微球50的微球，其组成具有约50wt％至约60wt％的氧化硅、约34wt％至约42wt％的氧化铝和小于2％的氧化铁(Fe2O3)。将微球50与氧化铝和三氧化硼(B2O3)颗粒56以微球50的质量的约0wt％至约50wt％、优选约10wt％至约20wt％的比例混合作为基质形成材料，以提供液相并充分降低微球50涂层的熔化温度，以使得能够在部件14的基底40的不锈钢表面42上形成TBC 16。
用微球50、氧化铝和三氧化硼颗粒56以及约1wt％至约2wt％的作为粘合剂加入的羟丙基纤维素形成浆料。向混合物中加入水以达到低粘度。将该浆料用喷枪喷涂到基底40的表面42上，在烘箱中在约125摄氏度(℃)下干燥，随后在约725摄氏度(℃)下在空气中烧结2小时。
更详细地描述了将热障涂层(TBC)16施加至部件14的基底40的表面42的方法。该方法包括提供多个陶瓷微球。可以对多个陶瓷微球进行分拣，使得直径为约10微米至约100微米，优选约10微米至约50微米的陶瓷微球被选择使用。
可以将基质56的颗粒54加入所选择的微球50。颗粒54可以包括多种混合物，并且可以按微球50的约5wt％至约50wt％的重量分数添加。在一个实施例中，基质56混合物可包括氧化硼和约0wt％至约50wt％的氧化铝。在另一实施例中，基质56混合物可以包括硼硅酸盐玻璃。在另一实施例中，基质56混合物可以包括铝金属或铝合金，铝金属或铝合金经熔化以将微球50熔合在一起并随后氧化成氧化物基质56。
在另一实施例中，基质56混合物可以包括二氧化硅前体，二氧化硅前体包括四乙氧基硅烷，将微球50熔合在一起并随后热解成氧化物基质。在另一实施例中，基质56混合物可以包括包含硅氧烷、硅烷、碳硅烷、硅氮烷、硼硅烷合类似的分子及其混合物的陶瓷前体，陶瓷前体随后通过热或UV固化交联，然后在惰性气氛中热解至陶瓷基质56。
用如上所述的多个陶瓷微球50、基质56以及溶剂和粘合剂中的至少一种制备浆料。使用由喷涂、浸涂和刮涂组成的群组中的工艺将浆料施加至部件14的基底40的表面42。对浆料和部件14的表面42施加至少一种热处理。至少一种热处理可以包括在烘箱中在约125摄氏度(℃)下干燥浆料和部件14的表面42，随后在空气中在约725摄氏度(℃)下将浆料和部件14烧结2小时。不渗透的密封层48可以接合到浆料，使得不渗透的密封层48密封浆料。
详细描述和附图或图是对本公开的支持和描述，但是本公开的范围仅由权利要求来限定。虽然已经详细描述了用于实施所要求公开的一些最佳模式和其他实施例，但是存在用于实践所附权利要求中限定的公开内容的各种可选设计和实施例。此外，附图中所示的实施例或本说明书中提到的各种实施例的特征不一定被理解为彼此独立的实施例。相反，可以将实施例的一个示例中描述的每个特征与来自其他实施例的一个或多个其他期望特征组合，从而产生未以文字或参照附图描述的其他实施例。因此，这样的其他实施例落在所附权利要求的范围的框架内。

Claims (10)

1.一种热障涂层，其包含：
绝缘层，其施加至厚度在约50微米和约1毫米之间的基底的表面，其中所述绝缘层包含多个陶瓷微球，并且孔隙率为至少75％；以及
与所述绝缘层接合的密封层，其中所述密封层是不渗透的，使得所述密封层密封所述绝缘层。
2.根据权利要求1所述的热障涂层，其中，所述绝缘层还包含配置成与所述多个微球接合的基质材料。
3.根据权利要求2所述的热障涂层，其中，所述基质材料还包含三氧化硼、氧化铝、硅酸铝、二氧化硅或硅酸盐玻璃或其混合物。
4.根据权利要求2所述的热障涂层，其中，所述基质材料还包含选自由硅氧烷、硅烷、碳硅烷、硅氮烷和硼硅烷的群组组成的陶瓷前体聚合物。
5.根据权利要求1所述的热障涂层，其中，所述多个陶瓷微球还包含约0wt％至约100wt％的氧化硅和约0wt％至约100wt％的氧化铝。
6.根据权利要求1所述的热障涂层，其中，所述多个陶瓷微球还包含约50wt％至约70wt％的氧化硅和约30wt％至约50wt％的氧化铝。
7.根据权利要求1所述的热障涂层，其中，所述密封层可以包含选自由氧化铝、硅酸铝、氧化硅、硅酸盐玻璃或其混合物，包括镍、钴、铁、铬、难熔金属以及相应的合金的高温金属和金属合金组成的所述群组的一种或多种元素。
8.根据权利要求1所述的热障涂层，其中，所述密封层可以由包含选自由以下各项组成的所述群组的一种或多种元素的陶瓷前体聚合物形成：硅氧烷、硅烷、碳硅烷、硅氮烷和硼硅烷，其中所述陶瓷前体聚合物在所述绝缘层热处理时转化为陶瓷。
9.一种将热障涂层施加至部件的表面的方法，其包含：
提供多个陶瓷微球；
从所述多个陶瓷微球中选择直径在约10微米至约50微米之间的陶瓷微球；
将所述多个陶瓷微球施加至所述基底的所述表面；并且
对所述多个陶瓷微球施加至少一种热处理以在所述基底的所述表面上形成绝缘层。
10.根据权利要求9所述的方法，还包含：
提供配置成与所述多个微球接合的基质材料；并且
组合所述基质材料和所述多个微球以施加至所述基底的所述表面。
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