CN118563258A - A high wear-resistant and corrosion-resistant Ni-based coating and preparation method thereof - Google Patents
A high wear-resistant and corrosion-resistant Ni-based coating and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 230000007797 corrosion Effects 0.000 title claims abstract description 32
- 238000005260 corrosion Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 238000007733 ion plating Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000013077 target material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001011 CMSX-4 Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 229910000601 superalloy Inorganic materials 0.000 claims 9
- 238000005299 abrasion Methods 0.000 claims 5
- 229910001005 Ni3Al Inorganic materials 0.000 claims 1
- 244000137852 Petrea volubilis Species 0.000 claims 1
- 230000001464 adherent effect Effects 0.000 claims 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 10
- 238000007731 hot pressing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- 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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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
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Abstract
本发明提供了一种高耐磨耐蚀Ni基涂层及其制备方法，属于材料表面技术领域，元素组成包括：以原子百分比计，49.5 at.%Al，0.05 at.%Hf，其余部分为Ni；其制备方法包括：靶材制备：根据Al、Hf和Ni的原子百分比含量，制备NiAlHf靶材；选取基材：选用高温合金基材，并对所述高温合金基材表面进行预处理；沉积NiAlHf涂层：将所述高温合金基材放入沉积炉中，采用电弧离子镀的方法，在所述高温合金基材的表面沉积所述NiAlHf涂层，将涂层经过真空热处理后，得到高耐磨耐蚀Ni基涂层。本发明通过对NiAl涂层掺杂0.05 at.%Hf，促进表面生成连续、致密、与涂层粘附性好的Al2O3层，以提供优异的抗高温氧化性能，提升了材料的硬度和耐磨性，赋予材料良好的高温力学性能，延长其使用寿命。
The present invention provides a highly wear-resistant and corrosion-resistant Ni-based coating and a preparation method thereof, belonging to the technical field of material surface, wherein the element composition includes: in terms of atomic percentage, 49.5 at.% Al, 0.05 at.% Hf, and the rest is Ni; the preparation method thereof includes: target material preparation: preparing NiAlHf target material according to the atomic percentage content of Al, Hf and Ni; selecting substrate: selecting a high-temperature alloy substrate, and pre-treating the surface of the high-temperature alloy substrate; depositing NiAlHf coating: placing the high-temperature alloy substrate in a deposition furnace, and using an arc ion plating method to deposit the NiAlHf coating on the surface of the high-temperature alloy substrate, and subjecting the coating to vacuum heat treatment to obtain a highly wear-resistant and corrosion-resistant Ni-based coating. The present invention promotes the generation of a continuous, dense Al 2 O 3 layer with good adhesion to the coating on the surface by doping the NiAl coating with 0.05 at.% Hf, so as to provide excellent high-temperature oxidation resistance, improve the hardness and wear resistance of the material, give the material good high-temperature mechanical properties, and extend its service life.
Description
技术领域Technical Field
本发明涉及材料表面技术领域，特别是涉及一种高耐磨耐蚀Ni基涂层及其制备方法。The invention relates to the technical field of material surface, in particular to a highly wear-resistant and corrosion-resistant Ni-based coating and a preparation method thereof.
背景技术Background Art
镍基高温合金由于其优异的高温力学性能，成为航空燃气涡轮叶片的首选材料。涡轮叶片在其工作时承受很大的交变载荷，与涡轮盘紧密配合的叶片榫齿极易发生微动磨损，诱发微动损伤，进而导致涡轮叶片失效，这已成为航空发动机故障高发的主要原因之一。用于高温服役环境中的部件，特别是位于燃气涡轮机工艺的部件，不仅需要抗氧化性以保持其相应的预期性能，还需要满足合金在长期使用中对抗摩擦、磨损等的实际要求。Nickel-based high-temperature alloys have become the preferred material for aviation gas turbine blades due to their excellent high-temperature mechanical properties. Turbine blades are subjected to large alternating loads during operation, and the blade tenons that fit closely with the turbine disk are prone to micro-motion wear, inducing micro-motion damage, which in turn leads to turbine blade failure, which has become one of the main reasons for the high incidence of aircraft engine failures. Components used in high-temperature service environments, especially those located in gas turbine processes, not only require oxidation resistance to maintain their corresponding expected performance, but also need to meet the actual requirements of the alloy to resist friction and wear during long-term use.
NiAl金属间化合物具有较高的比强度和比刚度、良好的导热性和导电性、优异的热稳定性和耐腐蚀性而被用作高温合金或涂层材料。将陶瓷颗粒加入NiAl金属间化合物基体中形成陶瓷颗粒增强增韧的NiAl金属间化合物复合材料，不仅可以强化NiAl金属间化合物，还能结合陶瓷材料的优秀性能，从而制备出具有优良的耐磨损性能、耐高温性能和耐氧化性能的NiAl金属间化合物/陶瓷基复合材料。目前制备NiAl金属间化合物/陶瓷基复合材料常用的工艺方法为机械合金化法，热压放热反应合成，热压烧结法和热压反应合成法等，其制备过程复杂，能源消耗大，对模具要求高，生产效率低，导致生产成本升高。NiAl intermetallic compounds have high specific strength and specific stiffness, good thermal conductivity and electrical conductivity, excellent thermal stability and corrosion resistance, and are used as high-temperature alloys or coating materials. Adding ceramic particles to the NiAl intermetallic compound matrix to form a NiAl intermetallic compound composite material reinforced and toughened with ceramic particles can not only strengthen the NiAl intermetallic compound, but also combine the excellent properties of ceramic materials to prepare NiAl intermetallic compound/ceramic matrix composite materials with excellent wear resistance, high temperature resistance and oxidation resistance. At present, the commonly used process methods for preparing NiAl intermetallic compound/ceramic matrix composite materials are mechanical alloying, hot pressing exothermic reaction synthesis, hot pressing sintering and hot pressing reaction synthesis, etc. The preparation process is complicated, the energy consumption is large, the mold requirements are high, the production efficiency is low, and the production cost is increased.
发明内容Summary of the invention
为了克服现有技术的不足，本发明的目的是提供一种高耐磨耐蚀Ni基涂层及其制备方法，通过对NiAl涂层掺杂0.05 at. % Hf，以促进表面生成连续、致密、与基体粘附性好的Al2O3层，提供优异的抗高温氧化性能，大幅度提升材料的硬度和耐磨性，赋予材料良好的高温力学性能，延长其使用寿命。In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a highly wear-resistant and corrosion-resistant Ni-based coating and a preparation method thereof, by doping the NiAl coating with 0.05 at. % Hf to promote the formation of a continuous, dense Al2O3 layer on the surface with good adhesion to the substrate, provide excellent resistance to high-temperature oxidation, greatly improve the hardness and wear resistance of the material, give the material good high-temperature mechanical properties, and extend its service life.
为实现上述目的，本发明提供了如下方案：To achieve the above object, the present invention provides the following solutions:
一种高耐磨耐蚀Ni基涂层，所述Ni基涂层的元素组成包括：按原子百分比计，49.5at. %的Al、0.05 at. %的Hf、其余部分为Ni；A highly wear-resistant and corrosion-resistant Ni-based coating, wherein the element composition of the Ni-based coating comprises: in atomic percentage, 49.5 at. % of Al, 0.05 at. % of Hf, and the remainder of Ni;
所述Ni基涂层的物相组成包括Al2O3、β-NiAl，γ′-Ni3Al，HfO2中的至少一种。The phase composition of the Ni-based coating includes at least one of Al 2 O 3 , β-NiAl, γ′-Ni 3 Al, and HfO 2 .
优选地，所述Ni基涂层的厚度范围为15~25 μm。Preferably, the thickness of the Ni-based coating is in the range of 15 to 25 μm.
本发明还提供了一种高耐磨耐蚀Ni基涂层的制备方法，包括以下步骤：The present invention also provides a method for preparing a highly wear-resistant and corrosion-resistant Ni-based coating, comprising the following steps:
S1、靶材制备：根据Al、Hf和Ni的原子百分比含量，制备NiAlHf靶材；S1. Target material preparation: preparing NiAlHf target material according to the atomic percentage content of Al, Hf and Ni;
S2、选取基材：选用高温合金基材，并对所述高温合金基材的表面进行预处理；S2. Selecting a substrate: selecting a high-temperature alloy substrate and pretreating the surface of the high-temperature alloy substrate;
S3、沉积NiAlHf涂层：将所述高温合金基材放入沉积炉中，并采用电弧离子镀的方法，在所述高温合金基材的表面沉积所述NiAlHf涂层，将所述NiAlHf涂层经过真空热处理后，得到高耐磨耐蚀Ni基涂层。S3. Depositing NiAlHf coating: placing the high-temperature alloy substrate into a deposition furnace, and using an arc ion plating method to deposit the NiAlHf coating on the surface of the high-temperature alloy substrate, and subjecting the NiAlHf coating to vacuum heat treatment to obtain a highly wear-resistant and corrosion-resistant Ni-based coating.
优选地，在步骤S2中，对所述高温合金基材的表面进行预处理过程为：首先对所述高温合金基材的表面采用砂纸进行打磨、抛光，随后依次采用丙酮、酒精对所述高温合金基材进行超声波清洗和烘干，以去除所述高温合金基材表面的氧化层、杂质和粘附物。Preferably, in step S2, the surface of the high-temperature alloy substrate is pretreated by first grinding and polishing the surface of the high-temperature alloy substrate with sandpaper, and then ultrasonically cleaning and drying the high-temperature alloy substrate with acetone and alcohol in sequence to remove the oxide layer, impurities and adhesions on the surface of the high-temperature alloy substrate.
优选地，在步骤S3，在将所述高温合金基材放入沉积炉中之前，还包括对所述沉积炉的内部进行高压离子清洗，所述高压离子清洗的条件为：炉内抽真空至5×10-3 Pa，炉内压强1.1 Pa，Ar气流量300 sccm，炉内负偏压500-900 V。Preferably, in step S3, before placing the high-temperature alloy substrate into the deposition furnace, the deposition furnace is further subjected to high-pressure ion cleaning. The conditions for the high-pressure ion cleaning are: the furnace is evacuated to 5×10 -3 Pa, the pressure in the furnace is 1.1 Pa, the Ar gas flow rate is 300 sccm, and the negative bias voltage in the furnace is 500-900 V.
优选地，在步骤S3中，采用电弧离子镀的方法条件包括：沉积炉内压强1.0 Pa，高温合金基材温度为300℃，电弧靶电流100 A，高温合金基材负偏压50 V，占空比70%。Preferably, in step S3, the conditions of the arc ion plating method include: a deposition furnace pressure of 1.0 Pa, a high-temperature alloy substrate temperature of 300° C., an arc target current of 100 A, a high-temperature alloy substrate negative bias of 50 V, and a duty cycle of 70%.
优选地，所述高温合金基材为CMSX-4镍基高温合金。Preferably, the high-temperature alloy substrate is CMSX-4 nickel-based high-temperature alloy.
优选地，还包括对沉积NiAlHf层后的所述高耐磨耐蚀Ni基涂层在950℃下进行6 h真空热处理。Preferably, the method further comprises subjecting the highly wear-resistant and corrosion-resistant Ni-based coating after the NiAlHf layer is deposited to a vacuum heat treatment at 950° C. for 6 h.
根据本发明提供的具体实施例，本发明公开了以下技术效果：According to the specific embodiments provided by the present invention, the present invention discloses the following technical effects:
（1）本发明在NiAl涂层的基础上掺杂0.05 at.% Hf，以增加氧化层与涂层间的粘附力，降低氧化层的生长速率，获得更具有保护性、寿命更长的Al2O3层。(1) The present invention doped 0.05 at.% Hf on the basis of NiAl coating to increase the adhesion between the oxide layer and the coating, reduce the growth rate of the oxide layer, and obtain an Al2O3 layer with better protection and longer life.
（2）本发明采用的NiAlHf涂层在高温下能够生成一层致密、连续的Al2O3层，Al2O3具有优异的耐磨、耐蚀、耐高温等性能，因此该涂层不仅能够提供良好的抗高温氧化性能，还能够增强其耐磨性能。且涂层表面通过氧化原位生成Al2O3层，既能避免传统外加法中硬质相与基体之间润湿性差、结合力弱等问题，又解决了硬质相在熔覆过程中易出现裂纹、气孔等缺陷的难题。(2) The NiAlHf coating used in the present invention can generate a dense and continuous Al 2 O 3 layer at high temperature. Al 2 O 3 has excellent wear resistance, corrosion resistance, high temperature resistance and other properties. Therefore, the coating can not only provide good high temperature oxidation resistance, but also enhance its wear resistance. In addition, the Al 2 O 3 layer is generated in situ by oxidation on the coating surface, which can avoid the problems of poor wettability and weak bonding between the hard phase and the substrate in the traditional external addition method, and solve the problem of defects such as cracks and pores in the hard phase during the cladding process.
（3）相较于机械合金化法、热压放热反应合成、热压烧结法和热压反应合成法等技术制备陶瓷颗粒增强增韧的NiAl金属间化合物复合材料，本发明采用电弧离子镀技术沉积速度快，离化率高，设备简单且成本低。(3) Compared with the preparation of ceramic particle reinforced and toughened NiAl intermetallic compound composite materials by mechanical alloying, hot pressing exothermic reaction synthesis, hot pressing sintering and hot pressing reaction synthesis, the arc ion plating technology used in the present invention has a fast deposition speed, a high ionization rate, simple equipment and low cost.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.
图1为本发明一种高耐磨耐蚀Ni基涂层的制备方法的流程图；FIG1 is a flow chart of a method for preparing a highly wear-resistant and corrosion-resistant Ni-based coating according to the present invention;
图2为本发明实施例一提供的高耐磨耐蚀Ni基涂层在20μm时的截面图；FIG2 is a cross-sectional view of a highly wear-resistant and corrosion-resistant Ni-based coating provided in Example 1 of the present invention at 20 μm;
图3为本发明实施例一提供的高耐磨耐蚀Ni基涂层的摩擦磨损曲线图。FIG3 is a friction and wear curve diagram of the highly wear-resistant and corrosion-resistant Ni-based coating provided in Example 1 of the present invention.
具体实施方式DETAILED DESCRIPTION
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
下面对本发明提供的高耐磨耐蚀Ni基涂层及其制备方法与应用进行说明。The highly wear-resistant and corrosion-resistant Ni-based coating provided by the present invention and its preparation method and application are described below.
NiAl金属间化合物由于其低密度(5.86 g/cm3)、高熔点(1638℃)、良好的导热性、高抗氧化性能等优点，在高温结构材料领域得到开发和应用。NiAl合金相图中较宽的成分比范围为改变其性能提供了很大的可能性，因此，许多研究开始探索采用合金化的方式来优化其室温塑性、硬度、耐蚀性等性能，力求扩大NiAl金属间化合物在社会生产和工程中的应用。在NiAl涂层中掺杂0.05 at. %Hf将会在氧化层和涂层界面处形成细小弥散的“氧化物栓”，以提高氧化层的附着力。Hf元素的添加，使涂层能够获得预想中的优良抗氧化性和抗腐蚀性，NiAl涂层的高硬度、低的表面粗糙度、较好的抗氧化性能以及与基体之间良好的粘附性能是涂层具有良好耐磨性能的主要原因。NiAl intermetallic compounds have been developed and applied in the field of high-temperature structural materials due to their low density (5.86 g/cm 3 ), high melting point (1638℃), good thermal conductivity, and high oxidation resistance. The wide composition ratio range in the NiAl alloy phase diagram provides great possibilities for changing its properties. Therefore, many studies have begun to explore the use of alloying to optimize its room temperature plasticity, hardness, corrosion resistance and other properties, and strive to expand the application of NiAl intermetallic compounds in social production and engineering. Doping 0.05 at. % Hf in NiAl coating will form fine and dispersed "oxide plugs" at the interface between the oxide layer and the coating to improve the adhesion of the oxide layer. The addition of Hf element enables the coating to obtain the expected excellent oxidation resistance and corrosion resistance. The high hardness, low surface roughness, good oxidation resistance and good adhesion between the NiAl coating and the substrate are the main reasons for the good wear resistance of the coating.
为使本发明的目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。In order to make the purpose, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.
实施例一Embodiment 1
如图1所示，本发明提供了一种高耐磨耐蚀Ni基涂层的制备方法，包括以下步骤：As shown in FIG1 , the present invention provides a method for preparing a highly wear-resistant and corrosion-resistant Ni-based coating, comprising the following steps:
S1、靶材制备：根据Al、Hf和Ni的原子百分比含量，制备NiAlHf靶材；S1. Target material preparation: preparing NiAlHf target material according to the atomic percentage content of Al, Hf and Ni;
S2、选取基材：选用高温合金基材，并对所述高温合金基材的表面进行预处理；S2. Selecting a substrate: selecting a high-temperature alloy substrate and pretreating the surface of the high-temperature alloy substrate;
S3、沉积NiAlHf层：将所述高温合金基材放入沉积炉中，并采用电弧离子镀的方法，在所述高温合金基材的表面沉积所述NiAlHf涂层，将所述NiAlHf涂层经过真空热处理后，得到高耐磨耐蚀Ni基涂层。S3, depositing a NiAlHf layer: placing the high-temperature alloy substrate into a deposition furnace, and using an arc ion plating method to deposit the NiAlHf coating on the surface of the high-temperature alloy substrate, and subjecting the NiAlHf coating to vacuum heat treatment to obtain a highly wear-resistant and corrosion-resistant Ni-based coating.
具体的，上述Al、Hf和Ni的原子百分比含量为：49.5 at. %Al，0.05 at.%Hf，其余部分为Ni。Specifically, the atomic percentage contents of the above-mentioned Al, Hf and Ni are: 49.5 at. % Al, 0.05 at. % Hf, and the rest is Ni.
其中，在步骤S2中，对高温合金基材的表面进行预处理过程为：首先对高温合金基材的表面采用砂纸进行打磨、抛光，随后依次采用丙酮、酒精对高温合金基材进行超声波清洗和烘干，以去除高温合金基材表面的氧化层、杂质和粘附物。Among them, in step S2, the surface of the high-temperature alloy substrate is pretreated as follows: first, the surface of the high-temperature alloy substrate is grinded and polished with sandpaper, and then the high-temperature alloy substrate is ultrasonically cleaned and dried with acetone and alcohol in sequence to remove the oxide layer, impurities and adhesions on the surface of the high-temperature alloy substrate.
具体的，在步骤S3，在将高温合金基材放入沉积炉中之前，还包括对沉积炉的内部进行高压离子清洗，高压离子清洗的条件为：炉内抽真空至5×10-3 Pa，炉内压强1.1 Pa，Ar气流量300 sccm，炉内负偏压650 V。Specifically, in step S3, before placing the high-temperature alloy substrate into the deposition furnace, the interior of the deposition furnace is also subjected to high-pressure ion cleaning. The conditions for high-pressure ion cleaning are: the furnace is evacuated to 5×10 -3 Pa, the pressure in the furnace is 1.1 Pa, the Ar gas flow rate is 300 sccm, and the negative bias voltage in the furnace is 650 V.
另外，采用电弧离子镀的方法条件包括：沉积炉内压强1.0 Pa，高温合金基材温度为300℃，电弧靶电流100 A，高温合金基材负偏压50 V，占空比70%。其中，上述高温合金基材优选为第二代镍基高温合金CMSX-4。相较于机械合金化法、热压放热反应合成法、热压烧结法和热压反应合成法等技术制备陶瓷颗粒增强增韧的NiAl金属间化合物复合材料，本实施例采用电弧离子镀方法，沉积速度快，离化率高，设备简单且成本低。此外在NiAlHf涂层表面高温氧化原位生成Al2O3层，既能避免传统外加法中硬质相与基体之间润湿性差、结合力弱等问题，又解决了硬质相在熔覆过程中易出现裂纹、气孔等缺陷的难题。由此，可参照图2，采用电弧离子镀的方法制备NiAlHf涂层，NiAlHf涂层与基体合金之间的结构致密，并未发现裂纹、孔隙等缺陷。另外，涂层的制备设备简单、工艺可控，制备的涂层与基体具有良好的界面结合力。In addition, the conditions of the arc ion plating method include: a deposition furnace pressure of 1.0 Pa, a high-temperature alloy substrate temperature of 300°C, an arc target current of 100 A, a high-temperature alloy substrate negative bias of 50 V, and a duty cycle of 70%. Among them, the above-mentioned high-temperature alloy substrate is preferably a second-generation nickel-based high-temperature alloy CMSX-4. Compared with the preparation of ceramic particle reinforced and toughened NiAl intermetallic compound composite materials by mechanical alloying, hot pressing exothermic reaction synthesis, hot pressing sintering and hot pressing reaction synthesis, this embodiment adopts an arc ion plating method, which has a fast deposition speed, high ionization rate, simple equipment and low cost. In addition, the Al 2 O 3 layer is generated in situ by high-temperature oxidation on the surface of the NiAlHf coating, which can avoid the problems of poor wettability and weak bonding between the hard phase and the substrate in the traditional addition method, and solve the problem that the hard phase is prone to cracks, pores and other defects during the cladding process. Therefore, referring to FIG. 2 , the NiAlHf coating is prepared by arc ion plating, and the structure between the NiAlHf coating and the base alloy is dense, and no defects such as cracks and pores are found. In addition, the coating preparation equipment is simple, the process is controllable, and the prepared coating has good interface bonding with the base.
更为具体的，在步骤S3，还包括对沉积NiAlHf层后的高耐磨耐蚀Ni基涂层在950℃下进行6 h真空热处理。More specifically, in step S3, the highly wear-resistant and corrosion-resistant Ni-based coating after the NiAlHf layer is deposited is further subjected to vacuum heat treatment at 950° C. for 6 h.
根据上述制备方法制备得到的高耐磨耐蚀Ni基涂层的物相组成包括Al2O3、β-NiAl，γ′-Ni3Al，HfO2中的至少一种，并测量其厚度约为20 μm。The phase composition of the highly wear-resistant and corrosion-resistant Ni-based coating prepared according to the above preparation method includes at least one of Al 2 O 3 , β-NiAl, γ′-Ni 3 Al, and HfO 2 , and its thickness is measured to be about 20 μm.
另外，参照图3，由Ni基涂层的摩擦磨损曲线图可知，由于Ni基涂层表面生成了致密连续的氧化铝层，从而制备得到的Ni基涂层的磨损率W为1.779×10-14 m3/(N·m)，以此证明了本实施例采用上述方法制备的Ni基涂层具有良好的耐蚀耐磨性能。In addition, referring to FIG3 , it can be seen from the friction and wear curve of the Ni-based coating that a dense and continuous aluminum oxide layer is formed on the surface of the Ni-based coating, and thus the wear rate W of the prepared Ni-based coating is 1.779×10 -14 m 3 /(N·m), which proves that the Ni-based coating prepared by the above method in this embodiment has good corrosion resistance and wear resistance.
因此，采用上述的一种高耐磨耐蚀Ni基涂层及其制备方法，通过对NiAl涂层掺杂0.05 at.%Hf，以促进表面生成连续、致密、与涂层粘附性好的Al2O3层，提供优异的抗高温氧化性能，大幅度提升材料的硬度和耐磨性，赋予材料良好的高温力学性能，延长其使用寿命。Therefore, the above-mentioned highly wear-resistant and corrosion-resistant Ni-based coating and its preparation method are adopted, and 0.05 at.% Hf is doped into the NiAl coating to promote the formation of a continuous, dense Al 2 O 3 layer on the surface with good adhesion to the coating, thereby providing excellent resistance to high-temperature oxidation, greatly improving the hardness and wear resistance of the material, giving the material good high-temperature mechanical properties, and extending its service life.
本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处。综上所述，本说明书内容不应理解为对本发明的限制。This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only used to help understand the method and core ideas of the present invention. At the same time, for those skilled in the art, according to the ideas of the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as limiting the present invention.
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