CN102154640B - Method for enhancing bonding strength of aluminum coating - Google Patents

Method for enhancing bonding strength of aluminum coating Download PDF

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CN102154640B
CN102154640B CN 201110063715 CN201110063715A CN102154640B CN 102154640 B CN102154640 B CN 102154640B CN 201110063715 CN201110063715 CN 201110063715 CN 201110063715 A CN201110063715 A CN 201110063715A CN 102154640 B CN102154640 B CN 102154640B
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aluminum
powder
method
coating
strength
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CN 201110063715
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CN102154640A (en )
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卜恒勇
卢晨
李晓玲
陈彬
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上海交通大学
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Abstract

The invention provides a method for enhancing bonding strength of an aluminum coating, which belongs to the technical field of metal surface treatment; the method comprises the following steps of: aluminium powder and Mg17Al12 spherical powder are mechanically mixed, and the mixed powder is sprayed on the surface of a substrate. In the method, a cold-spraying method is used for depositing the mixed powder of intermetallic compound powder and aluminium powder, and does not worsen other mechanical performances and chemical performances of the aluminum layer while increasing the bonding strengthof the aluminium layer.

Description

铝涂层结合强度的提高方法 Aluminum coating method of improving the strength of the binding

技术领域 FIELD

[0001] 本发明涉及的是ー种金属表面处理技术领域的方法,具体是ー种铝涂层结合强度的提高方法。 [0001] The present invention relates to a metal surface ー art processing methods, in particular ー aluminate coating method for improving binding strength.

背景技术 Background technique

[0002] 铝及铝合金材料具有优异的机械性能和耐腐蚀性能,因此广泛地用于交通运输、航空航天、3°C和军事领域等。 [0002] Aluminum and aluminum alloy material having excellent mechanical properties and corrosion resistance, it is widely used in transportation, aerospace, 3 ° C and military fields. 除了作为结构材料外,铝及铝合金材料的ー个重要应用是作为涂层以保护基体材料,拓展基体材料的应用领域和提高基体材料的服役寿命。 In addition as a structural material, the ー important applications of aluminum and aluminum alloy as a coating to protect the substrate material, to expand the field of application of the matrix material and improve the service life of the base material. 目前,铝涂层的主要制备方法有热喷涂(等离子喷涂和火焰喷涂等)、激光熔覆、气相沉积和电镀等。 Currently, the main method of preparing an aluminum coating are, for cladding, vapor deposition, plating, and thermal spraying (plasma spraying and flame spraying, etc.) and the like. 然而,铝是化学性质比较活泼的金属之一,传统的沉积方法不可避免地使铝涂层在制备过程中发生晶粒长大,相变等缺陷;或者沉积速度太慢,沉积过程耗能过高和污染环境等。 However, aluminum is one of the chemical properties of active metal comparison, conventional deposition method inevitably occur aluminum coating grains grown in the manufacturing process, defects such as phase transition; or slow deposition rate, the deposition process is too energy-consuming high and environmental pollution. [0003] 冷喷涂是建立在合理利用空气动力学原理基础上的ー种新型涂层制备技术,它主要通过高压气体加速粉末粒子,粒子高速撞击基体并通过产生剧烈的塑性变形而在基体表面沉积为涂层,其中工作气体的预热温度一般小于600°C,压カ为1-3. 5MPa,喷涂粒子的典型尺寸为5-50 iim,粒子速度为300-1200m/s。 [0003] Cold spraying is based on the rational use ー new types of coating preparation technique on the principle base aerodynamics, it is mainly to accelerate the powder particles through a high-pressure gas, particle-speed impact matrix and by plastic deformation severe generated and deposited on the surface of the base body a coating, wherein the preheating temperature of the working gas is typically less than 600 ° C, pressure of grades 1-3. 5MPa, spray particle size is typically 5-50 iim, particle velocity of 300-1200m / s. 采用冷喷涂方法可以制备纯铝、铝合金、铝复合材料和铝纳米材料涂层。 Cold spray method may be prepared using pure aluminum, an aluminum alloy, aluminum and aluminum composite nano-material coating. 然而,纯铝涂层虽然具有较好的耐腐蚀性能,但其粘接強度,表面硬度都较低,限制了它的进一步应用;而在原材料铝粉中添加硬质相粒子,如氧化铝,碳化硅等陶瓷粒子虽然能够改善涂层硬度和粘接強度,但是其耐腐蚀性能随着涂层中陶瓷粒子含量的増加逐渐降低。 However, although the aluminum coating has good corrosion resistance, but its adhesive strength, surface hardness are low, limiting its further application; hard phase particles are added in the raw material aluminum powder, such as alumina, Although silicon carbide ceramic particles can improve the coating hardness and adhesion strength, but its corrosion resistance decreases with the enlargement of the ceramic particle content coating added. 同时,涂层中含量过高的陶瓷相粒子也会破坏涂层和基体界面,降低涂层和基体在界面处的结合強度。 Meanwhile, the ceramic coating with high levels of particles can also damage the coating and substrate interface, reducing the binding strength of the coating and the substrate at the interface.

[0004] 经过对现有技术的检索发现,中国专利文献号CN101058881A记载了ー种“金属间化合物涂层的制备方法”,该发明采用机械合金化方法制备原材料粉末,随后用冷喷涂的方法在基体上沉积Al/Ni和Al/Ti等涂层并在300-1200°C下热处理,涂层中的合金元素在高温下扩散,形成金属间化合物涂层。 [0004] After retrieval of the prior art found Chinese Patent Document No. CN101058881A discloses ー kind of "preparation of intermetallic compound coating", the invention is prepared using mechanical alloying raw material powder, followed by a cold spray method deposited on a substrate Al / Ni and Al / Ti and other coating and heat treated at 300-1200 ° C, the alloying elements in the coating at high temperature diffusion, formation of intermetallic compound coating. 值得注意的是该现有技术中需要使用高温热处理,虽然可以在一定程度上提高涂层的结合强度,但是高温扩散处理不可避免地会对基体金属产生热影响。 It is noted that this prior art requires the use of high temperature heat treatment, although the bonding strength can be improved to some extent, but the high temperature diffusion process will affect the base metal heat inevitably generated. 另外,铝镁中间化合物涂层也不能采用该技术制备,因为镁粉的性质极为活泼,不适合作为冷喷涂原材料。 Further, the intermediate compound of aluminum magnesium coating can not be employed in this preparation technique, because the very nature of the active magnesium powder, is not suitable as a cold spray material.

发明内容 SUMMARY

[0005] 本发明针对现有技术存在的上述不足,提供一种铝涂层结合強度的提高方法,使用冷喷涂方法沉积金属间化合物粉末和铝粉末的混合粉末,提高铝涂层结合強度的同吋,不会恶化铝涂层的其它机械性能和化学性能。 [0005] The present invention addresses the above shortcomings of the prior art, there is provided a method for improving bonding strength of the aluminum coating, cold spray method using the intermetallic compound powder and the mixed powder of the aluminum powder deposition, combined with an aluminum coating to improve the strength of inch, other mechanical and chemical properties of the aluminum coating does not deteriorate.

[0006] 本发明是通过以下技术方案实现的,本发明通过将铝粉和Mg17Al12球形粉末机械混合,并将混合后的粉体冷喷涂于基体表面。 [0006] The present invention is achieved by the following technical solutions, the present invention is by mechanical mixing and Mg17Al12 aluminum spherical powder, and the mixed cold spray powder to the substrate surface.

[0007] 所述的铝粉为质量分数大于99%且经过筛分取粒子直径小于45 ym的铝粉粒子; [0007] The aluminum powder is greater than 99% and the mass fraction of aluminum particles sieved through a particle diameter of less than 45 ym taken in;

[0008] 所述的Mg17Al12球形粉末的平均粒子直径为58 um。 [0008] The average particle diameter of powder of spherical Mg17Al12 58 um. [0009] 所述的机械混合的比例为原子比为25 : 75〜75 : 25。 [0009] The mechanical mixing ratio is an atomic ratio of 25: 75~75: 25.

[0010] 所述的基体表面经丙酮清洗并干燥。 [0010] The substrate surface cleaning with acetone and dried.

[0011] 所述的基体为T6态的A16061铝合金或铸态的AZ91D镁合金。 [0011] A16061 said substrate is an aluminum alloy or a magnesium alloy AZ91D cast T6 temper.

[0012] 所述的冷喷涂是指:采用氦气作为工作气体和粒子载气,工作气体在喷枪入口处的压カ和温度分别为0. 98MPa和300°C,载气的压カ为I. 04MPa,温度为室温;送粉速率控制在15g/min左右,喷枪的出口到基体表面的距离为10-15mm且基体相对于喷枪的移动速度为I_3mm/so [0012] The cold spray means: the use of helium as the working gas and the particles in a carrier gas, the working gas pressure and temperature of the lance ka is 0. 98MPa respectively at the inlet and 300 ° C, carrier gas pressure is I ka . 04MPa, temperature was room temperature; feed rate controlled at 15g / min, from the lance outlet to the substrate surface is 10-15mm and the base relative to the spray gun moving speed of I_3mm / so

[0013] 本发明涉及上述方法得到的涂层,单道次沉积其厚度可达2369 ± 46 ym,孔隙率低于0. 2%, Mg17Al12在涂层中的含量为4.6 + 2. 8%,涂层硬度为56. 8±4. 2 (HvlOOg),涂层的粘接强度为27. 9 + 3. 6MPa (根据EN15340标准)。 [0013] The present invention relates to the coating obtained by the method described above, a single pass is deposited up to a thickness of 2369 ± 46 ym, a porosity of less than 0.2%, the content of Mg17Al12 in the coating was 4.6 + 2.8%, coating hardness was 56. 8 ± 4. 2 (HvlOOg), the adhesive strength of the coating was 27. 9 + 3. 6MPa (according to EN15340 standard). [0014] 同现有エ艺相比较,本发明的优点为: [0014] Compared with the prior arts Ester, advantages of the present invention are:

[0015] (I)金属间化合物的主要成分为铝和镁,镁是铝合金中的ー种重要的合金元素;同时该化合物的熔点低于660°C,因此该金属间化合物作为ー种硬质相粒子加入到原材料铝粉末中,不会影响铝的易回收性能。 [0015] (I) a main component an intermetallic compound of aluminum and magnesium, magnesium is an important alloying element in aluminum alloys ー; while the melting point of the compound is less than 660 ° C, and therefore the intermetallic compound as a hard seed ーhard phase particles are added to the raw material powder in the aluminum, the aluminum will not affect the performance of the easy recovery.

[0016] (2)该金属间化合物为球形,硬度较高,不易变形,在沉积过程中大部分球形粒子从涂层表面反弾,因此它在铝涂层中的含量很低,不会影响涂层与基体在界面处的结合。 [0016] (2) the intermetallic compound is spherical, high hardness, easily deformed, most of the deposition process in the spherical particles from the coating surface anti Tan, so that the aluminum content in the coating is low, does not affect coating and substrate binding at the interface. 该方法提高铝涂层结合強度的同时,对铝涂层的化学性能,尤其是耐腐蚀性能几乎没有影响。 The method improves the bonding strength while the aluminum coating, an aluminum coating on the chemical properties, especially the corrosion resistance is almost no effect.

[0017] (3)得到的铝涂层更加致密,由于硬质相粒子的夯实作用,铝粒子之间几乎没有孔隙,得到的涂层不仅致密度高,而且铝粒子的沉积效率也有所改善,单道次得到的涂层厚度也有所提闻。 [0017] (3) more dense aluminum coating obtained, since the effect of tamping the hard phase particles, almost no voids between the aluminum particles, the resultant coating is not only high density, and deposition efficiency is also improved aluminum particles, single-pass coating thickness obtained also referred smell.

[0018] (4)若金属间化合物粉末在原料粉末中的含量高于ー特定值,基体表面在喷涂前便不需要经过喷砂处理。 [0018] (4) If the content of the compound powder in the raw material powder intermetallic ー above a certain value, the surface of the substrate prior to coating eliminates the need to sandblasted.

[0019] (5)喷涂前金属间化合物粉末和铝粉末只需简单机械混合,不需要在保护气体下进行球磨等特殊处理,简化了操作エ序,节约了制备涂层的成本。 [0019] (5) prior to metal spraying compound between the powder and the aluminum powder simply mechanical mixing, ball milling does not require special treatment under protective gas, to simplify the operation sequence Ester, prepared coating cost savings.

附图说明 BRIEF DESCRIPTION

[0020] 图I原材料粉末粒子形貌; [0020] Figure I the raw material powder particle morphology;

[0021] 其中:(a)为招粒子粉末形貌图,(b) Mg17Al12粒子粉末形貌图。 [0021] wherein: (a) as the particles move powder topography, (b) Mg17Al12 particle powder topography.

[0022] 图2冷喷涂50% Al+50% Mg17Al12混合粉末涂层截面形貌图。 [0022] FIG. 2 Cold Spray 50% Al + 50% Mg17Al12 mixed powder coating cross-sectional topography.

[0023] 图3冷喷涂25% Al+75% Mg17Al12混合粉末涂层截面形貌图。 [0023] FIG Cold Spray 3 25% Al + 75% Mg17Al12 mixed powder coating cross-sectional topography.

具体实施方式 detailed description

[0024] 下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。 [0024] Hereinafter, embodiments of the present invention will be described in detail, the present embodiments In order aspect of the present invention is a premise is given and the specific operation detailed embodiments, but the scope of the present invention is not limited to the Example embodiments described below.

[0025] 实施例I [0025] Example I

[0026] 选择的铝粉末为高纯铝粉末,纯度(质量分数)大于99%,不规则外形,经过筛分取粒子直径小于45 ym的粒子;选择的铝镁金属间化合物粉末为Mg17Al12球形粉末,平均粒子直径为58 um。 [0026] The selected high purity aluminum powder is an aluminum powder, purity (mass fraction) is greater than 99%, an irregular shape, sieving particle diameter of less than 45 ym taken particles; metal selected among aluminum-magnesium compound powder is a spherical powder Mg17Al12 the average particle size of 58 um. 两种粉末的原始形貌如图I所示。 To the original topography of the two powders as shown I FIG. 采用的基体为T6态A16061铝合金。 The substrate used was an aluminum alloy A16061 T6 temper. 将高纯铝粉末和Mg17Al12球形粉末按照原子比为75 : 25混合后,然后机械混合10-30分钟,得到混合粉末。 The high-purity aluminum powder and the spherical powder according Mg17Al12 atomic ratio of 75: 25 After mixing, mechanical mixing and 10-30 minutes to obtain a mixed powder. 将铝基体表面用丙酮清洗,并干燥,之后采用上述混合粉末进行冷喷涂。 The aluminum surface cleaned with acetone, and dried, then the mixed powder using cold spraying. 冷喷涂中工作气体和粒子载气均为氦气,工作气体在喷枪入口处的压力和温度分别为0. 98MPa和300°C,载气的压カ为1.04MPa,温度为室温。 And the working gas in the cold spray particles are helium carrier gas, the working gas pressure and temperature at the inlet of the lance and 0. 98MPa respectively 300 ° C, carrier gas pressure ka is 1.04MPa, at room temperature. 送粉速率控制在15g/min左右,喷枪出口到基体表面的距离为15mm,基体相对于喷枪的移动速度为3mm/s,单道次沉积。 Feed rate controlled at 15g / min, gun distance from the outlet to the substrate surface is 15mm, the moving speed of the substrate relative to the spray gun is 3mm / s, single pass deposition. 得到的涂层厚度为612±37 iim,孔隙率低于0.3%,Mg17Al12在涂层中的含量为3. 2±1. I %,涂层硬度为53. 4±3. 6 (HvlOOg),涂层的粘接强度为18. I ±2. 7MPa (根据EN15340 标准)。 Coating thickness obtained was 612 ± 37 iim, a porosity of less than 0.3%, content in the coating was Mg17Al12 3. 2 ± 1. I%, the coating hardness was 53. 4 ± 3. 6 (HvlOOg), the adhesive strength of the coating was 18. I ± 2. 7MPa (according to EN15340 standard).

[0027] 实施例2 [0027] Example 2

[0028] 选择和实施例I相同的铝粉末,铝镁金属间化合物粉末和基体。 [0028] The same as Example I chosen and aluminum powder, aluminum magnesium between the substrate and the metal compound powder. 将高纯铝粉末和Mg17Al12球形粉末按照原子比为50 : 50混合后,然后机械混合10-30分钟,得到混合粉末。 The high-purity aluminum powder and the spherical powder according Mg17Al12 atomic ratio of 50: 50 After mixing, mechanical mixing and 10-30 minutes to obtain a mixed powder. 将铝基体表面用丙酮清洗并干燥。 The aluminum surface cleaned and dried with acetone. 之后采用上述混合粉末进行冷喷涂。 After the mixed powder using the cold spray. 冷喷涂中工作气体和粒子载气均为氦气,工作气体在喷枪入口处的压力和温度分别为0. 98MPa和300°C,载气的压カ为I. 04MPa,温度为室温。 And the working gas in the cold spray particles are helium carrier gas, the lance inlet of the working gas pressure and temperature are 0. 98MPa and 300 ° C, carrier gas pressure for the ka I. 04MPa, temperature is room temperature. 送粉速率控制在15g/min左右,喷枪出口到基体表面的距离为10mm,基体相对于喷枪的移动速度为lmm/s,单道次沉积。 Feed rate controlled at 15g / min, gun distance from the outlet to the substrate surface is 10mm, the moving speed of the substrate relative to the spray gun is lmm / s, single pass deposition. 得到的涂层如图2所示,其厚度为2369±46ii m,孔隙率低于0. 2%, Mg17Al12在涂层中的含量为4. 6±2. 8%,涂层硬度为56. 8 ±4. 2 (HvlOOg),涂层的粘接强度为27. 9 ±3. 6MPa。 The resulting coating shown in FIG. 2, having a thickness of 2369 ± 46ii m, a porosity of less than 0.2%, content in the coating was Mg17Al12 4. 6 ± 2. 8%, hardness of the coating 56. 8 ± 4. 2 (HvlOOg), the adhesive strength of the coating was 27. 9 ± 3. 6MPa.

[0029] 实施例3 [0029] Example 3

[0030] 选择和实施例I相同的铝粉末和铝镁金属间化合物粉末。 [0030] The choice between Example I and the same aluminum powder and aluminum magnesium metal compound powder. 采用的基体为铸态的AZ91D镁合金。 The base used is a cast magnesium alloy AZ91D. 将高纯铝粉末和Mg17Al12球形粉末按照原子比为25 : 75混合后,然后机械混合10-30分钟,得到混合粉末。 The high-purity aluminum powder and the spherical powder according Mg17Al12 atomic ratio of 25: 75 After mixing, mechanical mixing and 10-30 minutes to obtain a mixed powder. 将镁基体表面用丙酮清洗并干燥。 The magnesium substrate surface washed with acetone and dried. 之后采用上述混合粉末进行冷喷涂。 After the mixed powder using the cold spray. 冷喷涂中工作气体和粒子载气均为氦气,工作气体的压カ和温度为0. 98MPa和300°C,载气的压カ为1.04MPa,温度为室温。 And the working gas in the cold spray particles are helium carrier gas, the working gas pressure ka and 0. 98MPa and a temperature of 300 ° C, carrier gas pressure ka is 1.04MPa, at room temperature. 送粉速率为15g/min左右,喷枪出口到基体表面的距离为10mm,基体相对于喷枪的移动速度为2mm/s,双道次沉积。 Feed rate of about 15g / min, an outlet from the lance to the surface of the substrate is 10mm, the moving speed of the substrate relative to the spray gun was 2mm / s, double-pass deposition. 得到的涂层如图3所示。 The resulting coating as shown in FIG. 其厚度为1873±42 um,孔隙率低于0. 35%,Mg17Al12在涂层中的含量为7. 8±2. 3%,涂层硬度为58. 8 ±2. 9,涂层的粘接强度为19. 7±1. 6MPa。 A thickness of 1873 ± 42 um, a porosity of less than 0.35%, the content in the coating was Mg17Al12 7. 8 ± 2. 3%, the coating hardness was 58. 8 ± 2. 9, anchor coat layer bonding strength was 19. 7 ± 1. 6MPa.

[0031] 冷喷涂纯铝涂层的硬度为46. 2±1. 9,粘接强度为8. 7±0. 5MPa。 [0031] Hardness was cold sprayed aluminum coating 46. 2 ± 1. 9, the adhesive strength was 8. 7 ± 0. 5MPa. 可以发现Mg17Al12粒子在涂层中的含量虽然很低,但是仍然改善了涂层的硬度,同时大幅提高了涂层的粘接強度。 Can be found in the content of particles in the coating Mg17Al12, although low, but still improving the hardness of the coating, and greatly increases the adhesion strength of the coating. 应当指出,如果要进一步提高涂层的硬度,可以在冷喷涂过程中,采用更高的工作气体压カ和温度,或者使用不规则形貌的Mg17Al12粒子代替球形形貌的Mg17Al12粒子,用来提高硬质相粒子在涂层中的含量。 It is noted that, if to further enhance hardness of the coating, cold spray process may be, the use of higher grades of working gas pressure and temperature, or particles of irregular topography using Mg17Al12 Mg17Al12 spherical particles instead of topography, to improve content of the hard phase particles in the coating. 然而当硬质相粒子的含量超过ー特定的临界值后,涂层和基体在界面处的结合強度可能会下降。 However, when the content of the hard phase particles exceeds a certain threshold ー, and the bonding strength at the interface of the substrate may be decreased.

Claims (5)

  1. 1. 一种铝涂层结合强度的提高方法,其特征在于,通过将铝粉和球形金属间化合物Mg17Al12粉末机械混合,并将混合后的粉末在特定的工艺条件下,冷喷涂于基体表面,所述的特定的工艺条件为:采用氦气作为工作气体和粒子载气,工作气体在喷枪入口处的压力和温度分别为0. 98MPa和300°C,载气的压力为I. 04MPa,温度为室温,送粉速率为15g/min,喷枪的出口到基体表面的距离为10-15mm且基体相对于喷枪的移动速度为l-3mm/s。 CLAIMS 1. A method of improving the strength of the aluminum coating of the binding, characterized by mechanically mixing the compound Mg17Al12 between aluminum and spherical metal powder, and the mixed powder under specific conditions, cold spray to the substrate surface, the specific conditions were: use of helium as the working gas and the particles in a carrier gas, the working gas pressure and temperature at the inlet of the lance and 0. 98MPa respectively 300 ° C, carrier gas pressure I. 04MPa, temperature at room temperature, feed rate of 15g / min, from the lance outlet to the substrate surface is 10-15mm and the moving speed of the substrate relative to the lance l-3mm / s.
  2. 2.根据权利要求I所述的铝涂层结合强度的提高方法,其特征是,所述的铝粉为高纯铝,质量分数大于99%且经过筛分取粒子直径小于45 ym的铝粒子。 Aluminum coating according to claim I of the method of improving the strength of binding, wherein said aluminum powder is a high purity aluminum, mass fraction greater than 99% and sieved particle diameter of less than 45 ym taken aluminum particles .
  3. 3.根据权利要求I所述的铝涂层结合强度的提高方法,其特征是,所述的Mg17Al12球形粉末的平均粒子直径为58 um。 Aluminum coating according to claim I of the method of improving the binding strength, characterized in that the average particle diameter of spherical powder Mg17Al12 58 um.
  4. 4.根据权利要求I所述的铝涂层结合强度的提高方法,其特征是,所述的基体表面经丙酮清洗并干燥。 Aluminum coating according to claim I of the method of improving the strength of binding, wherein said substrate surface washed with acetone and dried.
  5. 5.根据权利要求I或4所述的铝涂层结合强度的提高方法,其特征是,所述的基体为T6态的A16061铝合金或铸态的AZ91D镁合金。 I according to claim 4 or aluminum coating method of improving the binding strength, characterized in that said matrix is ​​an aluminum alloy in the T6 temper or A16061 AZ91D magnesium alloy is cast.
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CN105525286A (en) * 2016-01-06 2016-04-27 中国石油大学(华东) Cold spraying aluminum-based self-lubrication abrasion-resistant coating and preparation method thereof
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CN105525287B (en) * 2016-01-06 2018-06-12 中国石油大学(华东) Three cold sprayed aluminum coating and self-lubricating wearable preparation

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