CN105524495B - 涡轮叶片涂料成分及其方法 - Google Patents

涡轮叶片涂料成分及其方法 Download PDF

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CN105524495B
CN105524495B CN201510663509.9A CN201510663509A CN105524495B CN 105524495 B CN105524495 B CN 105524495B CN 201510663509 A CN201510663509 A CN 201510663509A CN 105524495 B CN105524495 B CN 105524495B
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particles
coating
hard particles
sacrificial
base substrate
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CN105524495A (zh
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K.阿南德
S.S.帕布拉
E.卡拉
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General Electric Co PLC
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General Electric Co
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12Blades
    • F01D5/28Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288Protective coatings for blades
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17Metallic particles coated with metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18Non-metallic particles coated with metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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    • C23COATING 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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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/324Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
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    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
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    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
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Abstract

本发明涉及涡轮叶片涂料成分及其方法。且具体而言,涉及用于强化的金属基质涂料的成分,和制备和涂布该成分的方法。该成分包括多个牺牲金属粘结剂粒子和多个坚硬粒子的给料粉末,该多个牺牲金属粘结剂粒子相对于基础衬底为阳极的。

Description

涡轮叶片涂料成分及其方法
技术领域
本发明涉及保护金属物体以用于减少由侵蚀和腐蚀导致的效率损耗的系统和方法。
背景技术
压缩机(诸如轴向压缩机、离心压缩机和旋转压缩机)经常面临由在压缩机系统中使用的涡轮叶片的腐蚀而造成的工作效率的降低的问题。涡轮由涡轮叶片的级形成,涡轮叶片包括转子和定子叶片。在叶片随着时间变化而被腐蚀或被污染时,效率趋向于下降。叶片趋向于聚集沉积物,诸如氧化铁微粒和来自压缩机涡轮的后级处的气体和流体的其他氧化物碎片。在操作期间由流体和气体导致的叶片表面的磨损,和/或与微粒沉积物的反应可为迅速的。这种表面损坏不可通过水洗而容易地移除,因为沉积物可能不是可水溶的。
在工业中公知的是,可通过使用多种涂布技术保护叶片表面来减少磨损。例如,已知通过叶片上的纯净涂料来保护叶片表面。US申请号No. 2007/0261965描述了提供具有耐高温性的涂布物体的成分和方法。涂布物体由一种或更多种金属或金属合金层在衬底上的电沉积和热处理涂布衬底,使得层和衬底部分地和/或完全地互相扩散而产生。
认为由于对涡轮叶片的潜在的腐蚀和侵蚀性的工作环境,坚硬、耐氧化的涂料的应用可为合乎需要的。此外,压缩机中的停机时间状态可导致腐蚀性环境中的可能的湿气冷凝,以进一步增强叶片表面的磨损。该问题的已知的解决方案包括在U.S专利申请公开号No. 2009/0297720和2011/0165433中的论述。
发明内容
认为为了相对于潜在的侵蚀和腐蚀环境保护金属物体,可产生合成物以耐受侵蚀和腐蚀的环境。该合成物可包括与基础金属表面相容的防护金属涂料,且该金属涂料可包括具有其他粒子(诸如坚硬粒子)的金属合金,以加强防护涂料且减少涂料的侵蚀,以延长保护。还认为,合乎需要的是,防护涂料为薄的,这可增大层的均匀性且减少过程和材料成本。
具体而言,本发明提供解决问题的途径,其可通过提供包括金属涂料的合成物来降低涡轮叶片磨损速率,该金属涂料具有强化的金属基质涂料成分,该成分在性质上是阳极的,包括在性质上是牺牲的金属基础合金,添加坚硬粒子,该坚硬粒子可作用为保护诸如涡轮叶片的基础金属。
本发明的合成物包括:基础衬底、和涂料,该涂料在基础衬底的表面上,包括多个坚硬粒子和多个牺牲金属粘结剂,该牺牲金属粘结剂粒子相对于基础衬底为阳极的。涂料具有相对于基础衬底的至少大约50 mV的电化学电势差。
制备本发明的给料粉末的方法包括:制备多个牺牲金属粘结剂粒子、制备多个坚硬粒子、在液体介质中将牺牲金属粘结剂粒子和坚硬粒子掺合在一起,以将牺牲金属粘结剂粒子和坚硬粒子结合在一起,以产生多个结合的粒子、将多个接合粒子从液体介质分离,以产生给料粉末、和干燥该给料粉末。
根据本发明的涂布基础衬底的方法包括:制备多包括多个牺牲金属粘结剂粒子和多个坚硬粒子的给料粉末、用该给料粉末对基础衬底进行喷雾,以在基础衬底的表面上形成涂料。该涂料具有相对于基础衬底的至少大约50 mV的电化学电势差。
技术方案1:一种合成物,其包括:
基础衬底501;和
涂料502,其在所述基础衬底501的表面上,包括多个坚硬粒子302、402和多个牺牲金属粘结剂粒子301、401,所述牺牲金属粘结剂粒子301、401相对于所述基础衬底501为阳极的;
其中,所述涂料502具有相对于所述基础衬底501的至少大约50 mV的电化学电势差。
技术方案2:根据技术方案1所述的合成物,其特征在于,所述多个牺牲金属粘结剂粒子301、401包括金属或金属合金。
技术方案3:根据技术方案1或2所述的合成物,其特征在于,所述多个牺牲金属粘结剂粒子301、401是从由以下构成的集合中选择的:铝、镁、锌、铝合金、镉、铍、和镍20%铝合金。
技术方案4:根据技术方案1到3中的任一项所述的合成物,其特征在于,所述多个坚硬粒子302、402是从由以下构成的集合中选择的:碳化钨、碳化钼、碳化钛、氮化钛、硼化钛、碳化铬、氧化铬、氮化铬、硼化铬、碳化硅、氧化硅、氮化硅、氮化硼、硼化镁、氮化镁、氧化镁、氮化铝、碳化铝、氧化铝、硼化铝、氧化锆、氧化钛、氧化铝钛、和它们的组合。
技术方案5:根据技术方案1到4中的任一项所述的合成物,其特征在于,所述牺牲金属粘结剂粒子301、401以在涂料的总重量的大约10 wt%到大约25 wt%之间的量存在。
技术方案6:根据技术方案1到5中的任一项所述的合成物,其特征在于,所述坚硬粒子302、402以在涂料的总重量的大约75 wt%到90 wt%之间的量存在。
技术方案7:根据技术方案1到6中的任一项所述的合成物,其特征在于,所述涂料502相对于所述基础衬底501具有在大约50 mV到大约1000 mV之间的电化学电势差。
技术方案8:根据技术方案1到7中的任一项所述的合成物,其特征在于,所述坚硬粒子302、402具有在大约5到大约10之间的莫氏硬度。
技术方案9:根据技术方案1到8中的任一项所述的合成物,其特征在于,所述坚硬粒子302、402具有范围在大约0.5微米到大约3微米之间的平均粒子尺寸。
技术方案10:根据技术方案1到9中的任一项所述的合成物,其特征在于,所述基础衬底501由不锈钢材料制造。
技术方案11:一种制备给料粉末200、300的方法,其包括:
制备多个牺牲金属粘结剂粒子301、401;
制备多个坚硬粒子302、402;
在液体介质中将所述牺牲金属粘结剂粒子301、401和所述坚硬粒子302、402掺合在一起,以将所述牺牲金属粘结剂粒子301、401和所述坚硬粒子302、402结合在一起,且产生多个结合的粒子;
将所述多个结合的粒子从所述液体介质分离,以产生给料粉末200、300,和
干燥所述给料粉末200、300。
技术方案12:根据技术方案11所述的制备给料粉末200、300的方法,其特征在于,所述牺牲金属粘结剂粒子301、401和坚硬粒子302、402通过机械合金化或通过粒子的聚结而结合。
技术方案13:根据技术方案11或12所述的制备给料粉末200、300的方法,其特征在于,通过喷雾干燥和烧结来干燥所述给料粉末200、300。
技术方案14:根据技术方案11到13中的任一项所述的制备给料粉末200、300的方法,其特征在于,所述给料粉末200、300包括球形的粒子。
技术方案15:根据技术方案11到14中的任一项所述的制备给料粉末200、300的方法,其特征在于,所述给料粉末200、300为可流动的。
技术方案16:根据技术方案11到15中的任一项所述的制备给料粉末200、300的方法,其特征在于,所述给料粉末200、300包括具有大约5到大约60微米的尺寸的粒子。
技术方案17:根据技术方案11到16中的任一项所述的制备给料粉末200、300的方法,其特征在于,所述液体介质为有机介质或无机介质。
技术方案18:一种涂布基础衬底501的方法,其包括:
制备给料粉末200、300,所述给料粉末200、300包括多个牺牲金属粘结剂粒子301、401和多个坚硬粒子302、402;和
用所述给料粉末200、300对基础衬底501进行喷雾,以在所述基础衬底501的表面上形成涂料502;
其中,所述涂料502具有相对于所述基础衬底501的至少大约50 mV的电化学电势差。
技术方案19:根据技术方案18所述的方法,其特征在于,喷雾的步骤使用从由以下构成的集合中选择的过程:冷喷雾涂布过程和热喷雾涂布过程。
技术方案20:根据技术方案18或19所述的方法,其特征在于,根据包括以下的步骤来制备所述给料粉末200、300:
制备多个牺牲金属粘结剂粒子301、401;
制备多个坚硬粒子302、402;
在液体介质中将所述牺牲金属粘结剂粒子301、401和所述坚硬粒子302、402掺合在一起,以将所述牺牲金属粘结剂粒子301、401和所述坚硬粒子302、402结合在一起,且产生多个结合的粒子;
将所述多个结合的粒子从所述液体介质分离,以产生给料粉末200、300,和
干燥所述给料粉末200、300。
附图说明
图1是图解基于相应的电化学电势的若干共通金属材料的,从更阳极的材料至更阴极的材料的图表;
图2示出仅包括铝粒子和坚硬粒子的示范给料粉末成分的透视图;
图3示出示范给料粉末成分的放大视图,示出以1.00 KX的放大率放大的粒子;
图4示出示范给料粉末成分的放大视图,示出以5.00 KX的放大率放大的粒子;
图5示出涂布物品的截面图,该涂布物品是使用示范给料粉末成分涂布的,该示范给料粉末成分仅包括铝粒子和坚硬粒子;
图6提供示范涂布物品的照片,该涂布物品是使用包括10 wt%铝和90 wt%坚硬粒子的实施例成分涂布的;
图7提供经历盐雾试验之后的图7的示范涂布物品的照片;
图8提供图7的示范样品涂布金属物品的放大照片,示出在经历盐雾试验之后的示范样品的表面细节;
图9提供示范涂布物品的照片,该涂布物品是使用包括20 wt%铝粒子和80 wt%坚硬粒子的实施例成分涂布的;且
图10提供经历盐雾试验之后的图9的示范涂布物品的照片。
部件列表
200 给料粉末
202 阳极穴
300 给料粉末
301 铝粒子
302 坚硬粒子
401 铝粒子
402 坚硬粒子
501 金属基础衬底
502 冷喷雾涂料
503 缺陷部位
504 界面
600 涂布物品
700 试验的涂布物品
900 涂布物品
1000 试验的涂布物品。
具体实施方式
本发明提供在诸如涡轮叶片的金属表面上的常规防护涂料的备选途径。本发明的实施例提供单层增强的金属基质涂料,该涂料可为耐侵蚀和耐腐蚀的。
认为为了提供用于经历侵蚀和腐蚀性环境的涡轮叶片的合适的防护涂料,有利的是用电负性的(即,阴极的)来涂布大体上电正性的(即,阳极的)金属基础衬底。常规涡轮防护涂料可包括两层涂料:基础防护涂料,和提供相对于侵蚀的保护的坚硬层。
本发明提供单层涂料,其包括相对于侵蚀和腐蚀二者保护基础衬底的两种特征。具体而言,本发明提供防护涂料层,其仅包括两种组分,牺牲金属粘结剂粒子和坚硬粒子。
如在本说明书和权利要求中使用的,如下定义用语。
“牺牲”定义为可比基础衬底更电负性的(即,阳极的)金属或金属合金的特征,使得阳极的金属或金属合金将首先被腐蚀环境中的腐蚀介质攻击。
“坚硬粒子”定义为化合物的多个粒子,其可耐受可在操作期间侵蚀涡轮叶片的材料的高速率冲击,且可具有大约5到大约10之间的莫氏硬度。
“金属基质”为遍及成分连续的化学基质。
“金属粘接剂”定义为金属或金属合金材料,其为可形成金属基质的单一材料。
“基础衬底”定义为可用于涡轮叶片的金属基础材料,诸如不锈钢403CB+基础材料等。
“阳极的”定义为具有比其比照的相应材料更电负性的电化学电势的材料的特征。
“阴极的”定义为具有比其比照的相应材料更电正性的电化学电势的材料的特征。
“给料”定义为在后续过程或设备中用作基础材料的材料。
“粉末”定义为由多个小尺寸粒子(诸如当摇动或歪斜时可自由地流动的非常细小的粒状粒子)组成的疏松物质。
在本发明中,金属或金属合金的牺牲特征定义为金属和金属合金的以下特征,其比基础衬底更电负性的(即,阳极的),使得阳极金属或金属合金将首先由腐蚀性环境中的腐蚀介质攻击。如所描述的,阳极金属或金属合金和具有相对于基础衬底的牺牲特征。
相对于基础衬底为牺牲性的任何阳极金属或金属合金可在本发明中用作牺牲的金属粘结剂粒子,包括诸如铝、镁、锌、铝合金、镉、铍、镍20%铝合金(nickel 20% aluminumalloy)等的金属和金属合金。
图1提供示出关于各材料的电化学电势而图解的不同材料的图表。铝、镁、锌、铍、铝合金和镉在该图表的顶部,图解为最电负性的(阳极的),且诸如石墨、金、铂、和钛的材料图解为最电正性的(即,阴极的)。
涂料层和基础衬底优选地具有在大约50 mV到大约1000 mV、50 mV到大约600 mV之间的电化学电势差,具体而言在大约50 mV到大约400 mV之间的差,且更具体而言在大约50 mV到大约300 mV之间的差。
在与本发明的参数联系地使用时,词语“大约”意指高于或低于指定参数10%的范围。
如果电化学电势差高于1000 mV,那么金属粘结剂粒子可能太容易腐蚀以至于不能作用为对基础衬底的防护介质。然而,如果差低于50 mV,那么该差可能太小,且金属粘结剂粒子可相对于基础材料不牺牲地起作用。
已发现存在于涂料成分中的坚硬离子基本上不影响涂料成分的电负性,且因此坚硬粒子的存在可不影响金属粘结剂粒子的牺牲特征。
根据本发明的涂料和成分的技术优点包括:
提供坚硬的不活泼涂料,其相对于基础材料为阳极的,具有对侵蚀性和腐蚀性材料的侵蚀和沉积的改善的耐性;
提供在停工期间的金属物体的改善的腐蚀保护;
具有更好地维持金属物体上的平坦表面光洁度的能力;
提供允许简单制造和应用的单层涂料;和
具有与用于涂料的简单应用的冷或热喷雾涂布过程机械地相容的能力和执行成分的烘烤涂布的能力。
根据本发明的涂料和成分的其他商业优点包括:
适中成本的涂布选项;和
更好地维持降低效率损耗的平坦表面光洁度的能力,这可相当于直到0.5%的效率损耗降低(例如,对于200 MW容量涡轮,损耗降低可为1 MW每小时,或$100收入增加每小时)。
提供上述优点的本发明的涂料包括使用牺牲金属基质坚硬粒子成分的涂料。该成分仅包括可形成金属基质的多个牺牲金属粘结剂粒子(诸如,阳极金属或金属合金粒子),和嵌入金属基质中的以强化和加强涂料的多个坚硬粒子。
如在本领域中已知的,金属粘结剂为单一材料,其可形成金属基质,强化粒子可嵌入该金属基质中。金属基质为金属粘结剂的化学基质,其遍及材料为连续的,且当前公开的成分可形成具有金属基质的涂料,该金属基质具有嵌入该基质中的强化材料。强化材料可具有连续的或不连续的基质结合。
根据本发明的成分的实施例包括两部分成分,它们包括:(1)使用阳极金属或金属合金的多个牺牲金属粘结剂粒子,和(2)多个坚硬粒子。
涂料的实施例可具有相对于基础衬底的多个阳极金属粘结剂粒子,诸如铝、镁、锌、铝合金、镉、铍、镍20%铝合金等。认为阳极金属粘结剂粒子可促进成分和涂料中的局部阳极单元(cell)的发展。金属粘结剂粒子的阳极特性相对于阴极基础金属衬底可为牺牲的,使得该金属粘结剂粒子可首先被腐蚀性环境腐蚀。
示范成分可具有在成分的总重量的大约0.5 wt%到大约30 wt%之间,具体而言大约5 wt%到大约20 wt%之间,更具体而言大约10 wt%到大约15 wt%之间的牺牲金属粘结剂粒子量。
根据本发明,用在成分中的坚硬粒子指可潜在地耐受可在操作期间侵蚀涡轮叶片的材料(诸如高速水滴、泥沙、沙等)的高速冲击的材料。坚硬粒子可具有在大约5到大约10之间的莫氏硬度,其中10为金刚石的硬度。具体而言,坚硬粒子可具有在大约6.5到大约9之间,具体而言在大约7.5到大约8.5之间的莫氏硬度。
在实施例中,用在成分中的坚硬粒子可为多个相同或不同的粒子,且该成分可具有在成分的总重量的大约70 wt%到99.5 wt%之间,具体而言大约75 wt%到90 wt%之间,更具体而言大约80 wt%到85 wt%之间的坚硬粒子的量。
坚硬粒子的示例包括碳化钨、碳化钼、碳化钛、氮化钛、硼化钛、碳化铬、氧化铬、碳化硅、氧化硅、氮化硅、氮化硼、硼化镁、氮化镁、氧化镁、氮化铝、碳化铝、氧化铝、硼化铝、氧化锆、氧化钛、氧化铝钛、和相对于用于压缩机中的涡轮叶片的常规基础金属材料可为阳极的任何过渡的金属碳化物、过渡的金属氧化物、和过渡的金属氮化物和它们的组合。
坚硬粒子可具有范围在大约0.5微米到大约3微米之间,具体而言大约1微米到大约2.3微米之间,更具体而言大约1.5到大约2微米之间的平均粒子尺寸。
在示范成分中,多个坚硬粒子包括碳化铬粒子,其具有在大约0.5到大约3微米之间的粒子尺寸。碳化铬具有碳化铬的大约50%的初生碳化物含量,使得碳化铬坚硬粒子可紧密地间隔,以确保粒子对涂料提供期望的硬度。
在实施例中,以给料粉末的形式提供成分,其包括牺牲金属粘结剂粒子和坚硬粒子。制备给料粉末的示范方法包括:
制备微粒形式的多个牺牲金属粘结剂粒子;
制备微粒形式的多个坚硬粒子;
在液体介质中将牺牲金属粘结剂粒子和坚硬粒子掺合在一起,以将牺牲金属粘结剂粒子和坚硬粒子结合在一起且产生多个结合的粒子;
将多个结合的粒子从液体介质分离以产生给料粉末;和
使粒子的块干燥。
在实施例中,液体介质可为无机介质,其促进牺牲金属粘结剂粒子和坚硬粒子的结合。在另一实施例中,液体介质可为有机介质,以当将潜在地易燃的金属粘结剂粒子和坚硬粒子掺合在一起时阻止燃烧。在优选成分中,铝粒子用作金属粘结剂,由多个坚硬粒子强化,且铝粒子和坚硬粒子在有机液体介质中掺合在一起。
粒子可通过机械合金化或通过粒子在混合器(诸如摇晃器-混合器)中的聚结而结合。在粒子之间可不存在化学结合。在结合之后,可使用喷雾干燥技术或通过将结合的粒子烧结至大约600℃来干燥结合的粒子。
在实施例中,所得的给料粉末可为可流动的球形粉末的形式,具有直径在大约5到60微米之间,具体而言直径在大约10到45微米之间,且更具体而言直径在大约15到25微米之间的粉末尺寸。
本发明的给料粉末可用作冷喷雾过程或热喷雾过程中的基础供应材料,以将强化的金属基质涂料应用到金属表面(诸如使用不锈钢403CB+材料的不锈钢涡轮叶片)上。强化的金属基质涂料被认为相对于待涂布的基础衬底是耐氧化和阳极的。
使用本发明的给料粉末来涂布基础衬底的方法包括:
制备包括多个牺牲金属粘结剂粒子和多个坚硬粒子的给料粉末;和
用该给料粉末来对基础衬底进行喷雾,以形成在该基础衬底的表面上的涂料。
常规403CB+钢基础材料例如可具有大约-400 mV的电化学电势。在实施例中,待应用到基础材料上的阳极涂料可具有包括铝基合金的成分,该铝基合金具有大约-1000 mV的电化学电势,且通过分散多个坚硬粒子(诸如碳化铬、碳化硅、氧化铬或氧化铝粒子)来加强。基础材料与强化金属基质涂料之间的电化学电势差优选地为在大约50 mV到1000 mV之间,更优选地在大约100 mV到600 mV之间,更优选地为在大约150 mV到300 mV之间。
强化的金属基质涂料可具有耐受至少大约900°F,具体而言至少大约1000°F,更具体而言至少大约1050°F的温度暴露的能力。
在实施例中,给料粉末可利用冷喷雾涂布过程应用至金属表面。
如在本领域中已知的,冷喷雾涂布过程使用典型地在10到50微米之间的给料粉末粒子,且粒子通过压缩气体而加速至非常高的速度,诸如在200到1500 m/s之间。粒子可在喷雾过程期间适度地加热至更高的温度。在与金属衬底冲击时,粒子经历极端和迅速的塑性变形,这使该粒子能够结合至暴露的金属表面。认为粒子尺寸、密度、温度和速度之间的良好平衡在实现期望的涂料方面是重要的。粒子保持固体状态且在涂布过程期间为相对冷的,使得粒子在涂布过程中不融化。
可利用在下面制备和试验的示例实施例来论证根据本发明的用在冷涂布过程中的强化的金属基质涂料成分的优点。
图2示出示范给料粉末200的电子成像,该粉末200仅包括牺牲金属粘结剂粒子(诸如铝粒子)和包括硅、铬、镍、钨粒子等的坚硬粒子。用于制备给料粉末的粒子可为球形的。给料粉末200已在摇晃器-混合器中混合大约4小时。在实施例给料粉末内,可存在多个阳极穴202。阳极穴202可由牺牲金属粘结剂粒子形成,包括铝粒子,具有嵌入牺牲金属粘结剂粒子内且环绕其的坚硬粒子。
图3提供1.00 KX放大率下的示范给料粉末300的放大视图。该图像示出遍布给料粉末300分散的更大尺寸的铝粒子301。铝粒子301可在混合过程期间被有角度地压平,且可具有一些坚硬粒子302,坚硬粒子302在混合期间物理地嵌入铝粒子301中。
图4提供5.00 KX放大率下的示范给料粉末的放大视图。可看见铝粒子401具有沟槽和穴,且球形的坚硬粒子402如果尺寸更小则可以以物理的方式容纳到铝粒子401中。
在实施例中,用于用在冷喷雾过程中的示范给料粉末可包括尺寸大于坚硬粒子的尺寸的金属和金属合金粒子。
对于冷喷雾过程,认为为了给料粉末粒子实现均匀的塑性变形,可期望粒子实现均匀的速度。然而,如在本领域中已知的,铝粒子例如可为比坚硬粒子更不致密。
为了适应密度的差异且实现粒子的均匀速度,可期望使用粒子尺寸能够比在相同成分中使用的坚硬粒子粒子尺寸的尺寸大的铝粒子。类似地,具有比坚硬粒子低的密度的其他金属或金属合金粒子也可用在成分中,且期望具有比坚硬粒子大的尺寸。
更不致密的金属或金属合金粒子(诸如铝粒子)的尺寸可为坚硬粒子尺寸的2、3、4或5倍。
图5提供金属基础衬底501上的冷喷雾涂料502的截面图,其使用包括铝粒子和坚硬粒子的示范成分。从图5可见,涂料502已通过涂料502和衬底501的界面504处的铝粒子和坚硬粒子的塑性变形而结合至基础衬底501。粒子的塑性变形可允许涂料良好地结合至基础衬底。
在界面504处,可看见坚硬粒子嵌入塑性变形的铝粒子中。甚至在涂料中的将腐蚀介质连接至基础材料的裂口的情况(即,形成缺陷部位503)中,在缺陷部位仍存在足够的铝粒子,以形成阳极岛且相对于腐蚀保护基础材料。
在包括10 wt%铝粒子和90 wt%坚硬粒子的示范实施例中,在涂布之前,聚集的坚硬粒子被测量为在没有铝粒子的情况下具有接近914 HV0.3的硬度。在涂布之后,整体涂料硬度(包括铝粒子)被测量为接近871 HV0.3。优选地,具有牺牲粒子和坚硬粒子的涂料具有>1000 HV的测得硬度。
如上所述,图6示出示范涂布物品600的照片,该涂布物品600使用10 wt%铝粒子和90 wt%坚硬粒子的给料粉末成分。可看见涂布物品700具有均匀地涂布的外表面。
随后使用盐雾试验模拟涡轮叶片可经历的潜在的腐蚀环境来试验涂布物品600。盐雾试验将样本暴露于湿润、含盐的气氛,且评定这种条件下的样本的腐蚀程度。涂布物品600在盐雾试验下经受143.47小时的暴露。图7示出盐雾试验之后的试验的涂布物品700的照片。可看见试验的涂布物品700具有白色粉末层。
图8进一步示出图7中示出的试验的涂布物品700的一部分的放大和详细的照片。可看见白色粉末层在试验的涂布物品700的表面上,且盐雾试验之后在试验的涂布物品700上没有看见锈。认为白色粉末为已从试验的涂布物品700析出的氢氧化铝。
认为在盐雾试验期间,牺牲金属粘结剂粒子(即,铝粒子)与湿润、含盐的气氛反应,以形成氢氧化铝。因为看见已形成氢氧化铝而没有形成锈,因此认为由于铝粒子的首先与环境反应的牺牲性质而相对于腐蚀的环境保护了基础金属衬底。通过盐雾试验,认为10%铝成分已证明了涂料的在具有如在上面联系本发明已描述的优点的情况下执行的能力。
已以如上所述的相同的方式制备和试验了包括20 wt%铝粒子和80 wt%坚硬粒子的另一示范实施例。
在涂布之前,聚集的坚硬粒子被测量为在没有铝粒子的情况下具有接近914 HV0.3的硬度。在涂布之后,整体涂料硬度(包括铝粒子)被测量为接近821 HV0.3,这比对10 wt%铝粒子涂料测量的硬度(测量为接近871 HV0.3)低。
图9是利用描述的实施例给料粉末成分的实施例涂布物品900的照片。可看见涂布物品900具有均匀地涂布的外表面。
也使用盐雾试验来试验涂布物品900。涂布物品900经历与以上关于图6描述的涂布物品600相同的盐雾试验。涂布物品900在盐雾试验下经受143.47小时的暴露。图15示出在盐雾试验之后的试验的涂布物品1000的照片。可看见试验的涂布物品1000在表面上具有白色粉末层。在试验的涂布物品1000上没有看见锈。
认为类似于试验的涂布物品700,白色粉末为已从涂布物品900析出的氢氧化铝。还认为在试验的涂布物品1000上形成白色粉末层的情况下缺乏锈的形成证明了防护涂料中的铝粒子可具有牺牲性质。
备选地,热喷雾涂布过程可用于在衬底金属上产生防护涂料。热喷雾涂布过程是在其中将熔化的(或加热的)材料喷雾到表面上的涂布过程。可通过使用本发明的给料粉末来采用的示范热喷雾涂布过程包括高速氧燃料喷雾(HVOF)、等离子喷雾、和爆炸喷雾。
在实施例中,给料粉末可用作使用HVOF过程的热喷雾给料。HVOF涂布过程可确保Al基合金的部分熔化,具有坚硬粒子的期望的部分分解,诸如在粘结剂中碳化铬分解成分离的铬和碳粒子,以形成所得金属基质中的富含铬的穴。坚硬粒子的密度可实现金属物体表面上的更好的钝化。在另一实施例中,其他热喷雾过程还可用于将坚硬阳极成分应用到金属物体上,包括等离子喷雾和温喷雾。
在牺牲金属粘结剂粒子(诸如铝粒子)与坚硬粒子(诸如碳化铬或氮化铬或硼化铬)掺合之后,可使用HVOF过程将粒子的掺合混合物喷雾到金属衬底表面上。由于高温,坚硬微粒可分解且释放铬粒子,从而将铬粒子嵌入铝基质中。当铝变得与其他粒子(诸如铬粒子)成合金时,基质与基础材料之间的电化学电势差可从>900 mV降低以变得小于600 mV、小于400 mV,且在大约400 mV到300 mV之间。尽管可保持涂料的阳极特性,但在操作期间驱动腐蚀速率的电动势差可降低,从而维持阳极性和耐腐蚀性的结合。
在另一实施例中,强化的金属基质涂料可通过使用粘合带而形成在金属表面上,该胶带包括铝合金和坚硬粒子的成分。将强化的金属基质涂料成分制备为粘合带的示范方法包括:
提供包括粘结剂聚合物的前体层。该前体层可包括作为烧结助剂的Sn粉末,以促进Al基合金和Sn扩散结合到基础金属物体上;
在前体层的顶部上沉积给料粉末层;
可使用包括以下的过程将制备的带应用至金属物体表面,诸如不锈钢涡轮叶片:。
将一层或更多层制备的带放置到金属物体表面上;和
燃烧该带,以烧掉存在于带中的聚合物,且促进Al和Sn扩散结合到金属物体表面上。
聚合物带(诸如具有粘合衬背的聚乙酸乙烯酯)可被喷洒有期望的合成物粉末,以及低温硬焊粉末,该合成物粉末包括坚硬粒子和阳极金属添加物(例如,牺牲金属粘结剂粒子)。带和粒子可经受适度的加压压延,以便粉末可机械地锚定至粘合衬背PVA带。所得的带可应用到水力涡轮中的翼型件表面上。
在成分应用至金属表面(诸如通过冷喷雾涂布过程、热喷雾涂布过程,或将示范粘合带应用至金属表面)之后,可使用拖曳式精加工技术(诸如经受包括逐渐更细的磨料的一系列研磨滚筒)来机械地精加工涂料。精加工的涂料可具有大约0到45微英寸,具体而言是大约5到30英寸,更具体而言是大约10到25微英寸的表面粗糙度。
虽然已经结合目前被认为最实用且优选的实施例描述了本发明,但应当理解的是,本发明不限于公开的实施例,而是相反地,意图覆盖包括在所附权利要求的精神和范围内的各种修改和等同布置。

Claims (16)

1.一种用于保护金属物体的合成物,其包括:
基础衬底(501);和
涂料(502),其在所述基础衬底(501)的表面上,包括多个坚硬粒子(302、402)和多个牺牲金属粘结剂粒子(301、401),所述牺牲金属粘结剂粒子(301、401)相对于所述基础衬底(501)为阳极的;
其中,所述涂料(502)具有相对于所述基础衬底(501)的至少大约50 mV的电化学电势差;
其中,所述牺牲金属粘结剂粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约0.5wt%的量存在,并且所述牺牲金属粘结剂粒子选自由铝和铝合金组成的集合;
其中,所述坚硬粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约99.5 wt%的量存在;以及
其中,所述涂料(502)相对于所述基础衬底(501)具有在50 mV到1000 mV之间的电化学电势差。
2.根据权利要求1所述的合成物,其特征在于,所述多个坚硬粒子(302、402)是从由以下构成的集合中选择的:碳化钨、碳化钼、碳化钛、氮化钛、硼化钛、碳化铬、氧化铬、氮化铬、硼化铬、碳化硅、氧化硅、氮化硅、氮化硼、硼化镁、氮化镁、氧化镁、氮化铝、碳化铝、氧化铝、硼化铝、氧化锆、氧化钛、氧化铝钛、和它们的组合。
3.根据权利要求1所述的合成物,其特征在于,所述涂料(502)相对于所述基础衬底(501)具有在50 mV到600 mV之间的电化学电势差。
4.根据权利要求1所述的合成物,其特征在于,所述坚硬粒子(302、402)具有在5到10之间的莫氏硬度。
5.根据权利要求1所述的合成物,其特征在于,所述坚硬粒子(302、402)具有范围在0.5微米到3微米之间的平均粒子尺寸。
6.根据权利要求1所述的合成物,其特征在于,所述基础衬底(501)由不锈钢材料制造。
7.一种制备给料粉末(200、300)的方法,其包括:
制备多个牺牲金属粘结剂粒子(301、401);
制备多个坚硬粒子(302、402);
在液体介质中将所述牺牲金属粘结剂粒子(301、401)和所述坚硬粒子(302、402)掺合在一起,以将所述牺牲金属粘结剂粒子(301、401)和所述坚硬粒子(302、402)结合在一起,且产生多个结合的粒子;
将所述多个结合的粒子从所述液体介质分离,以产生给料粉末(200、300),和
干燥所述给料粉末(200、300);
用所述给料粉末(200、300)对基础衬底(501)进行喷雾,以在所述基础衬底(501)的表面上形成涂料(502);
其中,所述牺牲金属粘结剂粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约0.5wt%的量存在,并且所述牺牲金属粘结剂粒子选自由铝和铝合金组成的集合;所述坚硬粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约99.5 wt%的量存在;以及其中,所述涂料(502)相对于所述基础衬底(501)具有在50 mV到1000 mV之间的电化学电势差。
8.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,所述牺牲金属粘结剂粒子(301、401)和坚硬粒子(302、402)通过机械合金化或通过粒子的聚结而结合。
9.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,通过喷雾干燥和烧结来干燥所述给料粉末(200、300)。
10.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,所述给料粉末(200、300)包括球形的粒子。
11.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,所述给料粉末(200、300)为可流动的。
12.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,所述给料粉末(200、300)包括具有5到60微米的尺寸的粒子。
13.根据权利要求7所述的制备给料粉末(200、300)的方法,其特征在于,所述液体介质为有机介质或无机介质。
14.一种涂布基础衬底(501)的方法,其包括:
制备给料粉末(200、300),所述给料粉末(200、300)包括多个牺牲金属粘结剂粒子(301、401)和多个坚硬粒子(302、402);和
用所述给料粉末(200、300)对基础衬底(501)进行喷雾,以在所述基础衬底(501)的表面上形成涂料(502);
其中,所述牺牲金属粘结剂粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约0.5wt%的量存在,并且所述牺牲金属粘结剂粒子选自由铝和铝合金组成的集合;所述坚硬粒子以在所述涂料中的所述坚硬粒子和所述牺牲金属粘结剂粒子的总重量的大约99.5 wt%的量存在;以及其中,所述涂料(502)具有相对于所述基础衬底(501)的至少50 mV到1000 mV之间的电化学电势差。
15.根据权利要求14所述的方法,其特征在于,喷雾的步骤使用从由以下构成的集合中选择的过程:冷喷雾涂布过程和热喷雾涂布过程。
16.根据权利要求14所述的方法,其特征在于,根据包括以下的步骤来制备所述给料粉末(200、300):
制备多个牺牲金属粘结剂粒子(301、401);
制备多个坚硬粒子(302、402);
在液体介质中将所述牺牲金属粘结剂粒子(301、401)和所述坚硬粒子(302、402)掺合在一起,以将所述牺牲金属粘结剂粒子(301、401)和所述坚硬粒子(302、402)结合在一起,且产生多个结合的粒子;
将所述多个结合的粒子从所述液体介质分离,以产生给料粉末(200、300),和
干燥所述给料粉末(200、300)。
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