中国腐蚀与防护学报, 2026, 46(1): 25-36 DOI: 10.11902/1005.4537.2025.106

增材制造与腐蚀专题

激光熔覆液压支架立柱防腐耐磨涂层研究进展

胡红钰1, 王跃飞1, 严海心1, 史建军2, 吴多利,1

1.扬州大学机械工程学院 江苏省表面强化与功能化制造重点实验室(扬州大学) 扬州 225127

2.南京工程学院工业中心 南京 211167

Research Progress on Laser Cladding Anti-corrosion and Wear-resistant Coatings for Hydraulic Support Column

HU Hongyu1, WANG Yuefei1, YAN Haixin1, SHI Jianjun2, WU Duoli,1

1.Jiangsu Key Laboratory of Surface Strengthening and Functional Manufacturing College of Mechanical Engineering, Yangzhou University, Yangzhou 225127, China

2.Industrial Center, Nanjing Institute of Technology, Nanjing 211167, China

通讯作者: 吴多利,E-mail:dlwu@yzu.edu.cn,研究方向为高温腐蚀与防护涂层

收稿日期: 2025-04-01   修回日期: 2025-04-30  

基金资助: 国家自然科学基金.  52101100
国家自然科学基金.  52471097
扬州市校合作项目.  YZ2023208
扬州大学青蓝工程项目

Corresponding authors: WU Duoli, E-mail:dlwu@yzu.edu.cn

Received: 2025-04-01   Revised: 2025-04-30  

Fund supported: National Natural Science Foundation of China.  52101100
National Natural Science Foundation of China.  52471097
Yangzhou City-Yangzhou University Cooperation Foundation.  YZ2023208
Qing Lan Project of Yangzhou University

作者简介 About authors

吴多利,扬州大学机械工程学院副教授,硕士生导师,博士毕业于丹麦科技大学。入选中国科协科技智库青年人才计划、江苏省高层次创新创业引进人才、江苏省“科技副总”、扬州市“绿扬金凤”人才计划、扬州大学“青蓝工程”中青年学术带头人和扬州大学“青蓝工程”优秀青年骨干教师。主要研究领域为新能源发电先进高温腐蚀防护涂层、激光熔覆防腐耐磨涂层关键技术和金属材料的腐蚀与防护等。主持国家自然科学基金面上项目、国家自然科学基金青年基金、江苏省自然科学基金、江苏省高校面上项目等10余项科研项目。在CorrosionScience、Surface&CoatingsTechnology等国内外期刊发表论文40余篇,获授权发明专利8件。兼任中国腐蚀与防护学会高温专业委员会委员、中国机械工程学会表面工程分会特邀专家、中国光协激光应用分会青年委员、CorrosionCommunications、《表面技术》、《中国腐蚀与防护学报》和《材料开发与应用》等期刊青年编委。

摘要

作为煤矿井下综采作业的核心支护装备,液压支架立柱油缸长期处于高湿、高腐蚀性、高机械载荷的复杂井下工况。这些环境因素促使点蚀、电化学腐蚀的发生,进而导致其表面腐蚀与磨损失效问题,严重威胁矿井的安全生产。本文聚焦激光熔覆表面改性技术,系统总结了热喷涂、电镀、化学镀等传统防护涂层的制备机理及其在耐蚀耐磨性能、界面结合强度、工艺适用性等方面的技术局限性。针对立柱油缸内外表面差异化服役条件,重点探讨了铁基、镍基合金及金属陶瓷复合材料的成分设计与性能适配原则,揭示了熔覆层微观组织与耐蚀耐磨性能的构效关系。最后基于工程应用需求,从涂层材料体系优化和复合制备技术创新两个维度,提出了液压支架关键部件表面功能涂层的发展方向。

关键词: 激光熔覆 ; 液压支架 ; 耐腐蚀性 ; 耐磨性 ; 研究现状

Abstract

Hydraulic support is one of the important coal mining machinery equipment for underground coal mining, whilst, the reliability of the hydraulic support has a direct impact on the safety of underground coal mining operations. Which is long-term exposed to complex underground service conditions featuring high humidity, high corrosive media containing chloride ions, hydrogen sulfide, sulfur oxide and various adhesive dusts, as well as high mechanical load. Hence, the surface of hydraulic support column cylinder will be suffered from corrosion wear. Therefore, to improve the reliability of the hydraulic support and extend its service life is the key to ensure safe mining operations. The preparation of high-performance coatings on the surface of hydraulic support columns is an important technical means to solve the problem of corrosion and wear and improve safety and reliability. Coating preparation technology in industrial applications has a variety of forms, which can be directly in the active stent surface preparation of anti-corrosion wear-resistant coatings, enhance the hydraulic stent column cylinder surface performance, to extend the service life, can also be used as a means of remanufacturing, such as to repair damaged cylinders, reduce mining costs, to ensure the sustainable development of resources. This paper first summarizes the common protective coating preparation methods, describes several preparation methods of hydraulic support column protective coatings, including electroplating, thermal spraying, laser cladding, arc melting copper, etc., and discusses the preparation methods, in terms of their advantages and disadvantages. Secondly, the materials with excellent comprehensive performance used in the laser cladding technology are further reviewed, and different coating materials are analyzed from aspects of different processing conditions and different needs of the inner and outer surfaces of the bracket cylinder, including Fe-based self-fusing powder, Ni-based self-fusing powder, Cu-based powder and composite powder. Finally, from the two aspects of coating preparation technology and material system, the anticorrosion and wear-resistant coating of laser cladding hydraulic support column is expected.

Keywords: laser cladding ; hydraulic support ; corrosion resistance ; wear resistance ; research status

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本文引用格式

胡红钰, 王跃飞, 严海心, 史建军, 吴多利. 激光熔覆液压支架立柱防腐耐磨涂层研究进展. 中国腐蚀与防护学报[J], 2026, 46(1): 25-36 DOI:10.11902/1005.4537.2025.106

HU Hongyu, WANG Yuefei, YAN Haixin, SHI Jianjun, WU Duoli. Research Progress on Laser Cladding Anti-corrosion and Wear-resistant Coatings for Hydraulic Support Column. Journal of Chinese Society for Corrosion and Protection[J], 2026, 46(1): 25-36 DOI:10.11902/1005.4537.2025.106

我国作为煤炭大国,能源资源呈现“富煤、缺油、少气、缺铀”的特点,因此煤炭成为我国最主要的基础能源[1]。井下采煤法是目前主要采矿方法之一[2],井下采矿的前提是矿洞的可靠支撑。为此,液压支架成为矿用机械重要组成部分。与露天煤矿开采作业环境相比,井下作业的环境更为恶劣。矿洞内湿度较高,存在较浓的Cl-、H2S、SO42-等腐蚀介质[3,4],同时矿井内部粉尘较多,并伴有掉落的细小坚硬碎石,使得所服役液压支架暴露表面极易被腐蚀、磨损。液压支架主要承重部分为其立柱中的液压油缸,当液压油缸工作内外表面产生缺陷后,其表面粗糙度的改变将使得承重能力也发生改变,进而影响液压支架的整体寿命[5],严重时将直接导致矿井安全事故。目前,我国液压支架的使用数量不断增加,因此对已故障设备或关键零件的再制造,以及对即将投入使用设备的升级显得尤为重要[6~8]

在材料表面保护方面,主要包括:物理化学功能化、表面涂层技术、机械结构功能化[9]。涂层技术是一种表面改性的方法,可以将高性能材料复合到普通材料表面,从而赋予材料和零部件特定的性能,提升其使用价值。涂层技术主要包括电镀[10]、热喷涂[11]、激光熔覆[12,13]以及各种堆焊技术[14]等。现役的液压支架由于井下的腐蚀环境,表面容易产生腐蚀和磨损等缺陷,因此可以采用涂层技术制备防护涂层,以延长其使用寿命[15]。对于已失效或局部损坏的液压支架,涂层技术也可以作为再制造和修复的手段,确保资源的可持续发展[16]

本文将从液压支架腐蚀与耐腐蚀机理,涂层的制备方式及基本材料体系3个方面对液压支架立柱油缸防腐耐磨涂层的国内外最新研究成果进行综述。总结电镀、热喷涂、激光熔覆、电弧熔铜等不同涂层制备方式及其特点,讨论激光熔覆技术所采用的基本材料体系,最后围绕技术和材料体系两方面,对激光熔覆在液压支架立柱油缸的防腐耐磨涂层研究领域下一阶段发展方向进行展望。

1 液压支架腐蚀及耐腐蚀机理

1.1 腐蚀环境影响

在液压支架的服役过程中,井下环境及其所使用的润滑油中均存在多种腐蚀介质,如Cl-、S2-、SO42-等。这些腐蚀介质的分布因位置而异,呈现出不均匀性。这种不均匀的分布导致液压支架主要发生局部腐蚀,而非均匀腐蚀现象。其中点蚀是液压支架常见的失效形式之一[17]。点蚀通常与所接触到的特定阴离子有关,如Cl-。金属表面通常会形成一层保护膜(氧化层、钝化膜等),当Cl-向保护膜迁移并达到一定浓度时,会与金属反应形成氯化物,由于金属氯化物摩尔体积较大,会直接导致保护膜的破裂。保护膜破裂后金属暴露在腐蚀性环境中点蚀会逐渐形成并长大[18]。S及硫化物对材料的耐腐蚀性也具有显著的不利影响。尽管这些物质并不直接引发材料表面缺陷,但S与金属反应会影响材料表面的保护膜的形成、保护膜的厚度,降低材料的整体耐腐蚀性能,从而影响其长期使用的可靠性[19~21]。Wang等[22]研究表明,在H2S环境下,材料表面的氧化膜呈3层结构,最外层为氢氧化物,中间层及内层为硫化物和氧化物,H2S的存在会抑制保护性的氧化物生成,降低耐腐蚀性。

1.2 电化学腐蚀影响

液压支架电化学腐蚀主要发生在特定位置,如裂纹、气孔缺陷处。王志华[4]研究了镀铁镀铬双层复合镀层的电化学腐蚀反应。在液压支架工作时,其表面会形成水膜,腐蚀性气体会溶解在水膜之中,而水膜会随着缺陷渗入基体内部发生电化学腐蚀。镀层表面极易出现裂纹和针孔。当含有腐蚀离子的水膜由裂纹从镀铬层渗入到镀铁层时,Fe在缺陷内部作为阳极失去电子,如 式(1)所示。在缺陷内部,Fe2+不断增多,电场强度提高,S2-、Cl-迁移至缺陷内部并与Fe2+发生反应。Fe2+与腐蚀介质S2-、Cl-、SO42-反应并产生沉淀以及腐蚀盐(式(2~ 4))。之后FeCl2与FeSO4继续发生 式(5)和(6)反应生成新的沉淀及腐蚀酸。由于缺陷内部的水膜不流通,生成的HCl、H2SO4会提高水膜的酸度,加速电化学反应。所生成的沉淀在坑洞内不断堆积,增加膨胀力,最终使涂层出现鼓泡缺陷。

FeFe2++2e-
Fe2++S2-FeS
Fe2++Cl-FeCl2
Fe2++SO42-FeSO4
FeCl2+2H2OFe(OH)2+2HCl
FeSO4+2H2OFe(OH)2+H2SO4

1.3 材料耐腐蚀机理

尽管当前液压支架采用了多种耐腐蚀措施,其耐腐蚀机理可概括为以下几种主要形式:首先,对于所有耐腐蚀材料而言,钝化膜的生成是涂层耐腐蚀的重要机制。在腐蚀环境中,材料中的钝化元素(如Cr、Al等)能够形成保护性钝化膜,从而有效隔绝基体金属与腐蚀介质的接触。其次,针对各种材料的强化工艺或保护涂层,通过不同优化加工工艺和掺入稀土元素等手段,可以改善涂层的微观组织,细化晶粒结构并实现组织均匀性。这种优化不仅减少了涂层中的缺陷,还减少了腐蚀的起始点。最后,硬质相的引入也是提升涂层耐腐蚀性能的有效途径。通过向熔覆材料中添加硬质相,或在涂层熔池中反应生成如尖晶石等,可以显著提高涂层的硬度和耐腐蚀性。这些机制共同作用,增强了涂层在恶劣环境下的耐久性。

2 常见液压支架立柱油缸涂层制备方式

液压支架立柱在长期服役后油缸内外表面均会产生失效。防腐蚀耐磨涂层的制备是目前普遍的液压油缸修复和防护手段。针对液压油缸活塞杆外表面及活塞缸内表面,采取电镀、热喷涂、激光熔覆、电弧熔铜等方式制备涂层(表1),限制或延缓基体材料的磨损及腐蚀,提高液压支架整体使用寿命。内外表面涂层制备时加工条件不同,所采取的加工方式也不同。图1a为液压支架外表面腐蚀状况,对于外表面的修复,其散热条件良好,加工空间大,电镀、热喷涂、激光熔覆均可实现(图1b)。图2a为液压支架内表面腐蚀状况,与外壁服役条件相同,内壁也同样会产生不同程度的腐蚀缺陷,由于内表面加工空间受限,且散热条件较差,目前主要采用激光熔覆和电弧熔铜实现涂层制备(图2b)。

表1   液压支架涂层制备常用工艺优缺点

Table 1  Advantages and disadvantages of common preparation processes of coatings for the repair of hydraulic support columns

ProcessingAdvantageDisadvantage
Electroplating① Low process costs① Prone to defects
② High hardness② Generating hazardous substances during the process
Thermal spray① Wide choice of coating materials① The coating and the substrate are mainly mechanically bonded, and the bonding strength is weak
② Good overall performance② Cracks may occur when unmelted powder hits the substrate at high speeds
Laser cladding① Metallurgical bonding of the coating to the substrate① The coating is susceptible to cracking due to thermal stress
② Good density
Arc melting copper① Metallurgical bonding of the coating to the substrate① High equipment costs
② Good electrical conductivity, thermal conductivity, self-lubricating properties② Single copper coating performance is weak, need to add other alloying elements

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图1

图1   液压支架立柱外表面腐蚀及涂层修复状况[3]

Fig.1   Corrosion (a) and coating repair (b) of external surfaces of hydraulic support columns[3]


图2

图2   液压支架立柱内表面腐蚀及涂层修复[23]

Fig.2   Corrosion (a) and coating repair (b) of inner surfaces of hydraulic support columns[23]


2.1 电镀

电镀是在金属离子溶液中,不溶性合金(铅、铂等)作为阳极、待镀金属作为阴极,施加电流后从正极处的阳极溶解的金属沉积在另一极处的阴极上,从而形成涂层[24,25]。电镀镀层连续性与均匀性较好,且对试件形状无限制[26]。液压油缸的防腐耐磨涂层通常采用硬铬涂层,Cr的加入提高了表面的硬度和耐腐蚀性。Abdullah等[27]在416不锈钢上制备不同厚度硬铬涂层,并测试其力学性能。416不锈钢的杨氏模量为(179 ± 4) MPa,所制备的涂层杨氏模量提高到(290 ± 67) MPa,同时涂层的平均硬度为基体的4.5倍,且硬度与涂层厚度无关。纪正君等[28]对27SiMn材料的液压支架立柱电镀硬铬涂层进行168 h的Cu加速盐雾腐蚀试验,其耐腐蚀性能可达到9级标准,能满足井下生产需求。电镀在工艺成本上有一定的优势,同时电镀涂层硬度较高,耐腐蚀性能也能满足基本使用需求。但铬涂层存在固有的裂纹和气孔(如图3),很大程度上影响电镀涂层的耐腐蚀性能。此外,电镀液中的Cr6+对环境和人体均有不良影响[29]

图3

图3   镀铬前后416不锈钢基底的表面显微照片[27]

Fig.3   Micrographs of of 416 stainless steel before (a) and after (b) chromiumplating[27]


2.2 热喷涂

热喷涂是将金属或非金属颗粒加热融化或呈现熔融状态,加速撞击到母材表面,形成涂层[30]。根据热源不同,热喷涂技术可分为火焰喷涂、电弧喷涂、爆炸喷涂、等离子喷涂等[31]。液压油缸涂层的制备常用超音速火焰喷涂,并选用碳化钨、镍基合金、不锈钢等材料,使得涂层提高硬度并具有一定的防腐性能。Wu等[8]使用超音速火焰喷涂(HVOF)在液压支架立柱表面制备Ni60、WC10Co4Cr、316L 3种涂层,涂层厚度在420~450 μm。在加载载荷100 g加载时间15 s的条件下,WC10Co4Cr涂层显微硬度最高,可达(1163.6 ± 12.4)HV300。在盐雾腐蚀试验中,WC10Co4Cr涂层在120 h后出现锈蚀,Ni60合金、316L不锈钢涂层耐腐蚀性更好,在720 h后出现锈蚀。张景河等[32]通过超音速火焰喷涂在27SiMn材料的液压支架立柱表面制备WC-Cr3C2-M涂层,涂层显微组织致密,不存在贯穿性裂纹,WC的加入使得涂层硬具有更高的硬度,达到951.4HV0.3,远高于27SiMn。经过Cu加速盐雾腐蚀试验,H2S,SO2腐蚀试验,涂层均表现出良好的耐腐蚀性。热喷涂涂层表现出较好的耐腐蚀性能主要归因于涂层致密的组织,以及部分元素(Cr、Al等)氧化后形成保护性氧化膜,二者共同作用延缓腐蚀介质向内部扩散。尽管热喷涂涂层一定程度上能提升油缸材料的耐磨性和耐腐蚀性,但其制备过程仍存在一定短板。未完全熔融粉末在高速撞击到基体时易形成裂纹,同时涂层与基材的结合形式主要是机械结合,涂层易脱落。王勇等[33]在液压支架用27SiMn钢上通过超音速火焰喷涂制备WC-10Co-4Cr涂层,并分析涂层组织及沉积机理。观察到在涂层与基体结合处有WC颗粒嵌入基体中,产生明显裂纹,但并未留下轨迹痕迹,其中必定产生了冶金结合(如图4)。通过从基体到涂层中的扫描能谱可以看到,基体中的Fe有向涂层内部扩散的趋势,而W也有向基体扩散的现象,因此涂层与基体的结合形式为机械结合并伴随少量冶金结合和元素扩散。

图4

图4   利用超音速火焰喷涂在液压支架用27SiMn钢上制备的WC-10Co-4Cr涂层与基体的界面结合形貌[33]

Fig.4   Enlarged images of the interface between HVOF deposited WC-10Co-4Cr coating and 27SiMn steel substrate: (a) metallurgical bonded area and crack, (b) crack[33]


2.3 激光熔覆

激光熔覆是一种材料沉积技术,利用激光束融化粉末材料,在另一种材料上形成冶金结合和完全致密的熔覆层[34]。激光熔覆因为其冶金结合的性质,有较好的结合强度,更多元素的加入也使得涂层有较好的耐磨、耐腐蚀性能。Bai等[35]通过激光熔覆在27SiMn液压支架上制备了铁基合金涂层,熔覆层尺寸相对均匀,车削后观察到熔覆层无裂纹、气泡或大颗粒凹坑。经过硬度测试,熔覆层中部和上部硬度均大于基体硬度,其中上部硬度为500.1HV0.3达到最大值,基材摩擦系数为0.59,熔覆层最低摩擦系数降低至0.36。陈刚等[36]在27SiMn液压缸立柱表面熔覆不同厚度的316L不锈钢涂层,不同厚度的涂层硬度、耐腐蚀性相对基体均有提高,此外,随着涂层厚度的增加,自腐蚀电位、极化电阻率增高,腐蚀电流密度降低,涂层更易于钝化,耐腐蚀性能更好。虽然激光熔覆加热及冷却过程中所产生的热应力可能导致萌生裂纹[37,38],但通过优化加工工艺,选择合适的工艺参数、基体预热或采用重熔工艺等方式仍能获得高质量的涂层[39,40]

2.4 电弧熔铜

电弧熔铜是电弧熔丝增材制造在液压液压支架涂层中的一项具体应用,技术通过电子控制焊接电流和电压,结合铜合金焊材的特点,完成熔滴短路过渡,在基材表面形成铜层熔覆[41]。电弧熔铜呈冶金结合,结合力强。Cu本身具有较好的导热性导电性以及自润滑性,但硬度和耐腐蚀性不佳,通过在熔覆材料中加入合金材料,能有效改善熔覆材料的耐腐蚀性、耐磨性[42]。陶小松等[43]以27SiMn为基材,在其内壁熔铜涂层。熔铜层微观组织主要是α相铜基固溶体、γ相Fe、AlFe3等,硬度仅为200HV0.5。经过电化学腐蚀,涂层中的Cu和Al、Fe电位不同,形成腐蚀微电池,使得铜涂层耐腐蚀性能略差。焦阳等[44]在27SiMn液压油缸内表面通过电弧熔铜制备了加入不同合金的铜涂层,表征其微观组织,并通过浸泡腐蚀、电化学腐蚀、摩擦磨损实验研究其服役行为。涂层主要由α-Cu相以及K相组成,且K相以球形和枝晶形态为主。通过浸泡腐蚀和电化学腐蚀,合金元素(Ni、Si、Zn等)的加入使得涂层具有更好的耐腐蚀性和耐磨性。虽然电弧熔铜的工艺有研究已经取得一定进展,在一些煤矿机械企业中使用,但该工艺复杂,工艺成本高,耐磨性能仍需优化。

表2总结了部分液压支架防护涂层的案例及其性能测试指标。综合表1中所归纳的各种工艺特点及表2的性能指标。需要指出的是,电镀和热喷涂由于其工艺特性,往往会产生固有缺陷。此外,激光熔覆技术在受到热应力影响时可能会出现裂纹,但通过优化工艺参数和工艺路线,可以有效改善这一问题。电弧熔铜设备的成本较高,且单一铜涂层的性能有限,Cu与其他合金材料的结合仍需进一步深入研究。综上所述,激光熔覆加工工艺具有良好的可控性和稳定的涂层质量,是当前综合性能较为优异的涂层制备技术。

表2   液压支架防护涂层的应用案例

Table 2  Application examples of protective coatings for hydraulic supports

SubstrateCoating materialThickness / μmHardnessCorrosion test methodCorrosion test results
Electroplating416 stainless steelHard chrome[27]11-194 (Depends on plating time)900HV
27SiMnCu-Cr[28]30-45800HVCopper accelerated acetic acid salt spray (CASS)Meeting production needs
Thermal45 steelWC10Co4Cr[8]420-450(1163.6 ± 12.4)HV300CASSRusting after 120 h
spraying
27SiMnWC-Cr3C2-M[32]300-350951.4HV0.3CASSNo visible corrosion
spots after 312 h
Hydrogen sulfideNo visible corrosion
corrosion testspots after 240 h
Sulfur dioxideNo visible corrosion
corrosion testspots after 312 h
27SiMnWC[33]1200HV[27]
Laser cladding27SiMnFe-based alloy500.1HV0.3
powder[35]
27SiMn316L[36]1000400HV0.23.5%NaCl electrochemicalEcorr = 0.053 V
corrosionRp = 22.881 Ω·cm²
Icorr = 1.018 A/cm²
Arc melting27SiMnAluminum200HV0.53.5%NaCl electrochemicalEcorr = -0.53 V
copperbronze[43]corrosionDense holes in the
surface of the coating
CASSCorrosion material
after 100 h
27SiMnAluminum540HV0.53.5%NaCl electrochemicalEcorr = -0.85 V
bronze[44]corrosion
Aluminum bronze +550HV0.5Ecorr = -0.8 V
Ni、Mn[44]
Aluminum bronze +550HV0.5Ecorr = -0.6 V
Si[44]

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3 液压支架立柱涂层材料体系

液压油缸常见材料为27SiMn、30CrMo、30Cr-MnSi,目前国内外学者主要围绕27SiMn液压油缸材料表面修复展开研究。对于较为理想的激光熔覆涂层制备技术,其涂层制备材料体系如图5所示,主要有自熔性合金粉末、铜基粉末以及复合粉末,其中自熔性合金粉末分为铁基自熔性粉末,镍基自熔性粉末。对于液压油缸不同位置的使用需求及加工条件,选择不同加工材料,油缸活塞杆外表面一般采用自熔性粉末或复合粉末,而内表面则采用铜基粉末或复合粉末。

图5

图5   激光熔覆涂层材料体系

Fig.5   Laser cladding material systems


3.1 自熔性粉末

自熔性合金粉末指在合金粉末中加入具有强烈脱氧和自熔作用的元素,如Si、B元素等。Si和B等元素具有造渣功能,在激光熔覆过程中,其与涂层材料以及基体表面的氧化物可熔融生成低熔点的硼硅酸盐等覆盖在熔池表面,防止液态金属过度氧化,从而改善熔体对金属的润湿能力,减少熔融层中的夹杂和含氧量,提高熔覆层的工艺性能[45]。目前所采用的自熔性合金粉末根据其主要成分的不同可划分为镍基自熔性粉末、铁基自熔性粉末、钴基自熔性粉末3大类,这几类自熔性合金粉末对碳钢、不锈钢、合金钢、铸钢等多种基材均有较好的适应性。其中,钴基粉自熔性粉末主要用于高温场合,且成本较高,因此其在液压油缸中研究较少。

3.1.1 铁基自熔性粉末

铁基自熔性粉末涂层硬度高、耐磨性能好,涂层中的Cr易于氧化生成保护性氧化膜,使其有一定的耐腐蚀性,可用于局部易磨损的零件,因此其常见于液压油缸立柱的修复中。菅含含[46]在27SiMn上通过激光熔覆JG-3铁基粉末制备涂层,通过改变工艺参数获得不同的组织结构分析其拉伸性能和耐磨性能。结果表明,在选择合适的激光工艺参数的条件下,抗拉强度能达到820.03 MPa,最高显微硬度达到601.4HV。对比基体与涂层的金相组织,合金粉末中的C、Cr、B形成金属碳化物,有效提高了涂层的强度与硬度,进而提高耐磨性。Ouyang等[47]通过激光熔覆在27SiMn上制备铁基涂层,在涂层顶部形成了较细的树枝晶结构(如图6a)。涂层主要由α-Fe固溶体和金属间化合物M7C3、M2B、Cr3Si组成。涂层中的Ni、Mo相对Fe有更高的还原电位,尽管Cr平衡电位低于Fe,但其易钝化提高了涂层腐蚀电位,最终涂层材料耐腐蚀性提升。在盐雾实验中,Cr所形成的钝化膜,涂层中的碳化物、硼化物,Ce3Si共同作用下,可以有效阻止O2及Cl-穿过涂层向基体渗透。

图6

图6   铁基涂层[47],镍基涂层[52],铜基涂层[56]和Ni25/CeO2复合涂层[60]微观形貌

Fig.6   Microscopic morphologies of several coatings: (a) Fe-based coating[47]; (b) Ni-based coating[52]; (c) Cu-based coating[56];(d) Ni25/CeO2 composite coating[60]


3.1.2 镍基自熔性粉末

镍基自熔性粉末具有良好的力学性能和耐蚀性,以及一定的耐热腐蚀性,适用于局部要求耐磨、耐腐蚀的场合[48,49]。de Sousa等[50]开展了镍基涂层的耐磨性的研究,在低碳钢基体上熔覆Ni-Cr-B-Si涂层。通过对微观组织的分析,不同熔覆参数的涂层中均有不同含量,不同大小的树枝状CrC晶粒(图7),在后续的硬度及摩擦测试中,CrC的含量与尺寸对涂层的显微硬度和耐磨性有积极的影响。CrC硬度较高,受到磨料的影响较小,其在涂层基质中可以有效减少涂层在摩擦时的损失。Naghiyan等[51]在Inconel738基板上熔覆Inconel625涂层,并涂覆腐蚀盐置于通过管式炉中进行热腐蚀试验。经过高温腐蚀,涂层顶部与内部均产生腐蚀,顶部直接与腐蚀盐接触,而涂层内部则由腐蚀离子及氧的扩散导致。高温下,涂层中的Ni、Cr形成NiO,Cr2O3及尖晶石NiCr2O4相,这些相作为保护性氧化层,有效阻止氧扩散到涂层中,降低腐蚀速率。Ding等[52]使用超高速激光熔覆在液压支架材料27SiMn钢表面熔覆Inconel625粉末。高冷却速率使得晶粒进一步细化(图6b),高速熔覆过程中的动态再结晶怎强涂层的耐磨性,涂层表面平均显微硬度为324.4HV0.5,摩擦系数在0.5~0.8间波动。经过三电极电化学腐蚀,涂层有较好的耐腐蚀性。尽管超高速激光熔覆涂层性能得到改善,但在离心作用和冷却速度过快的条件下,易导致涂层元素分布不均匀,要避免元素偏析的问题,需要进行高速激光重熔处理[53]

图7

图7   Ni-Cr-B-Si涂层中心区域微观结构[50]

Fig.7   Microstructures of the central regions of Ni-Cr-B-Si coatings[50]


3.2 铜基粉末

在电弧熔丝增材制造技术应用后,不少学者及机构探索通过激光熔覆在内壁制备铜熔覆层。铜导热性优良有较好的自润滑性[54],但其对激光的吸收率较低,纯铜对激光的高反射使得其在成形过程中极易损坏激光器[55],并且纯铜硬度较低。因此以Cu为基体粉末,加入一定量其他元素粉末(Mo、Si、Zn等)提高熔覆材料对激光的吸收率成为一种有效解决方案。Zhang等[56]将Cu与Mo、Si混合,在AISI 4140钢表面制备Cu-Mo-Si涂层。涂层具有致密的微观结构(如图6c),涂层相主要由Mo-Si金属硅酸盐和Cu固溶体组成。此时Mo-Si金属硅酸盐成为影响涂层硬度的主要因素,其中Mo5Si3相显著提高了涂层的硬度和耐磨性。许金宝[57]在液压支架油缸母材27SiMn上通过激光熔覆制备铜基优化粉末涂层。以传统的CuAl系列青铜焊丝为基础,优化Fe、Al质量分数比例,并加入Zn、Ni等元素。涂层自润滑性好,成形后易加工。此外,Zn、Ni的加入有效提高耐磨和耐腐蚀性能。

3.3 复合粉末

复合粉末通过在自熔性粉末中加入硬质相粉末、陶瓷粉末或稀土元素,粉末中杂质可以作为反应稀释剂,控制反应动力学及反应产物,有效改善涂层性能。镍基粉末有较好的耐腐蚀性,但其抗磨损性能有限,在其中加入硬质相粉末或陶瓷粉末能有效增强涂层耐磨性能[58]。李刚等[59]通过激光熔覆在27SiMn钢表面制备Ni35掺杂高碳铬铁粉复合涂层。未掺杂高碳铬铁粉,熔覆层显微组织呈短棒状有方向性树枝晶组织,而掺入高碳铬铁粉后开始有细小板条状组织析出,并随着掺杂量在提高而增多,在掺杂量不断提高至75%后,显微组织开始变得粗大且尖端出现交叉。由于掺杂后Cr的增加,复合涂层的硬度也相应增加,且掺杂量过高并不会影响硬度提升,但硬度分布均匀性会受到影响。经过电化学腐蚀,复合涂层的耐腐蚀性能随掺杂量增加先提高后降低。Ye等[60]在镍基粉末中掺杂CeO2陶瓷粉末,通过激光熔覆在钛合金表面制备复合涂层。Ce原子有很强的化学活性,在液态金属中容易填充合金相的表面缺陷,使两相界面上的表面张力较低,增加有效成核数量,在Ce偏析在晶界时,也可以阻碍晶粒的生长,减小晶界,最终细化显微组织(图6d)。此外,稀土氧化物溶于固溶体中,起固溶强化剂的作用,在激光熔覆后获得稀土元素的过饱和固溶体,进而提高涂层的硬度、耐腐蚀性。铁基粉末虽然成本较低,在工业领域有着广泛的应用,但其综合性能仍有较大的提升空间。王强等[61]通过在铁基粉末中添加稀土氧化物颗粒改善材料的力学性能。其通过激光熔覆在27SiMn上制备La2O3/JG-8复合粉末涂层,稀土元素的加入使得形核率增加、晶粒细化、组织均匀。随着La2O3含量的改变,涂层表面硬度先增大后减小,最高可达27SiMn基体硬度的3.1倍,相对于未添加稀土提升了19.4%。

4 发展趋势

4.1 液压支架立柱涂层激光熔覆技术发展趋势

4.1.1 激光熔覆技术革新

液压支架的涂层制备技术很大程度上受到所加工零件尺寸影响,对于直径较大的零件,采用传统的激光熔覆方法能够有效地实现预期的涂层效果。然而,对于直径较小的零件,由于其散热速度较慢和热堆积现象的严重性,受热应力的影响更加显著,从而导致涂层缺陷的产生。因此,中小尺寸液压支架的表面涂层制备仍然是一个亟待解决的技术难题。超高速激光熔覆技术作为新兴的表面涂层技术,熔覆速度比传统激光熔覆快100~250倍,这一技术通过缩短激光能量作用于基体的时间,显著降低了基体所受的热影响,从而提高了生产效率。此外超高速激光熔覆技术改变粉末熔化位置,降低稀释率,提高结合强度[62,63]。目前超快激光熔覆技术在部分煤矿机械中已经投入使用[64]。该技术有很大潜力解决中小型液压支架因热堆积而难以加工的难题,同时也是未来液压支架涂层制备的技术发展方向之一。

4.1.2 熔覆层缺陷控制

激光熔覆层的质量尚不稳定,主要由于熔池冷却过程中产生的裂纹和气孔等缺陷。尽管通过优化工艺参数,改善涂层材料元素配比等方面可以进行调控,但在实际生产过程中,企业往往难以针对特定工件灵活调整工艺。因此,通常采用提高搭接率和增加熔覆层厚度的方式,在熔覆完成后通过车削去除部分缺陷表面,以确保生产效率。因此在涂层制备阶段降低缺陷率是未来的一大发展趋势,针对由热应力引起的裂纹缺陷,可以通过降低温度梯度来改善。在熔覆设备中增设感应加热模块及温度监测模块。通过温度监测关注熔池温度动态变化,当温度梯度过大时通过感应加热模块加热,降低冷却速率、减小热应力从而抑制裂纹的产生。此外,由于冷却过快所导致熔池中气体未排出导致的气孔问题可通过超声波、电磁场等辅助能场改善。在冷却过程中由辅助能场产生震动或电磁力作用在熔池,达到搅拌效果,加速气体排出进而减少或避免气孔缺陷。

4.1.3 熔覆层后处理技术

液压支架在井下作业环境中,碎石的产生会对支架表面造成磨粒磨损,这种磨损区域更容易发生腐蚀。此外,液压支架的长期工作会产生疲劳损坏。因此,在将来的涂层制备可以增加后处理技术,如激光冲击强化工艺或车削-滚压复合工艺。激光冲击强化工艺具有显著的优势:一方面,它能够有效细化晶粒,增加表面硬度,并植入残余应力,从而提高疲劳强度,满足涂层性能的需求;另一方面,激光熔覆与激光冲击强化的能量来源相似,这使得在设备搭建方面具有可行性。对于车削-滚压复合工艺,车削可以去除熔覆层表面明显缺陷层,再通过滚压成形,在涂层表面形成更高的残余应力,细化表层晶粒,提高组织致密性。同时车削-滚压复合工艺在实际应用时,滚压工具置于车刀后方,一次进给即可同时完成车削与滚压,效率高、不存在二次装夹所导致的误差。

4.2 液压支架立柱涂层材料发展趋势

目前,液压支架立柱油缸外表面熔覆材料已初步形成系统化的体系。大多数企业采用常规的铁基材料,并基于FeCrBSi粉末,根据设备条件及加工过程中涂层缺陷的情况,适当调整各元素的配比,以实现理想的涂层性能。这一方法旨在优化涂层的结构和性能,从而提高液压支架的耐磨性和使用寿命。然而,油缸内表面材料体系研究较为薄弱,为了达到良好配合效果,采用具有良好自润滑作用的铜基材料,尽管性能满足预期需求,但铜成本较高并不利于工业的可持续发展。未来内壁熔覆材料的发展要从铜基向铁基转型,主要围绕FeCrBSi系列粉末展开研究,在其中加入Cu、Zn、Sn等元素,增加涂层的自润滑作用。通过优化工艺,对涂层进行重熔或固溶强化热处理[65,66],改善涂层微观组织,从而有效弥补传统铁基涂层的耐腐蚀性和耐磨性的不足。最终目标是建立专用材料体系,以满足液压支架立柱油缸内壁使用需求。

5 结语

本文针对液压支架立柱防腐蚀耐磨涂层制备的问题,综述了液压支架的腐蚀机理、几种不同涂层制备方法及涂层材料体系。研究结果表明,采用激光熔覆技术制备铁基涂层及铁基为基础复合涂层,在液压支架立柱防腐耐磨涂层的应用中展现出良好的应用前景。

在液压支架立柱油缸防腐耐磨涂层的研究中,未来主要集中在以下四个方面:

(1) 超高速激光加工技术引入。采用超高速激光熔覆技术通过改变粉末熔化位置将显著改善传统激光熔覆工艺中存在的效率低、热影响区大的问题。

(2) 辅助能场引入。通过增设超声波和电磁场,借助能场产生的震动或电磁力,改善熔池内部组织,细化晶粒,减少缺陷的产生。

(3) 后处理技术引入。引入激光冲击强化技术或及车削-滚压复合工艺,有效细化晶粒,提高表面硬度,并植入残余应力增加疲劳强度,提高支架使用寿命。

(4) 专用材料体系构建。基于现有的铁基材料体系的耐磨耐腐蚀性研究,加入Cu、Zn等元素以提高涂层的自润滑性,构建出液压支架内壁涂层的专用材料体系。

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In this study, laser cladding technology was used to prepare Fe-based alloy coating on a 27SiMn hydraulic support, and a turning treatment was used to obtain samples of the upper and middle regions of the cladding layer. The influence of microstructure, phase composition, hardness, and wear resistance in different areas of the cladding layer was studied through scanning electron microscopy (SEM), X-ray diffractometry (XRD), friction and wear tests, and microhardness. The results show that the bcc phase content in the upper region of the cladding layer is less than that in the middle region of the cladding layer, and the upper region of the cladding layer contains more metal compounds. The hardness of the middle region of the cladding layer is higher than that of the upper region of the cladding layer. At the same time, the main wear mechanism of the upper region of the cladding layer is adhesive wear and abrasive wear. The wear mechanism of the middle region of the cladding layer is mainly abrasive wear, with better wear resistance than the upper region of the cladding layer.

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Development of high speed and high performance of mechanical equipments requires higher strength and better wear resistance of wear-resistant copper alloys. Although performance of traditional aluminum bronze series, manganese brass series and lead brass series alloys has been improved, their application scope is limited by various factors, such as material characteristics, processing technology and environmental protection, respectively. The application status and research progress of five typical wear-resistant copper alloys with high application values including Cu-Ni-Sn series, Cu-Al<sub>2</sub>O<sub>3</sub> series, Cu-Nb series, Cu-C series (including copper/graphite, copper/graphene and copper/carbon nanotubes) and complex brass are described from preparation process, properties and application field. The problems in their development and application are analyzed, and their development prospect is also discussed.

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机械设备高速度化及高性能化的发展要求耐磨铜合金具备更高的强度和更优异的耐磨性能。传统的铝青铜系、锰黄铜系和铅黄铜系等合金的性能虽已有所提升,但因受材料自身特性、加工工艺、环境保护等因素制约,其应用范围受限。从制备工艺、性能、应用领域等方面介绍了具备较高开发价值的Cu-Ni-Sn系、Cu-Al<sub>2</sub>O<sub>3</sub>系、Cu-Nb系、Cu-C系(包括铜/石墨、铜/石墨烯和铜/碳纳米管)和复杂黄铜等5种典型耐磨铜合金的应用现状和研究进展,对其开发应用中所存在的问题进行了分析,并对其发展前景进行了展望。

Tao X S, Zhang H Y, Gong C, et al.

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DOI      URL     [本文引用: 3]

In this paper, the corrosion performance of a laser cladding Fe-based alloy coating on the surface of 27SiMn steel was studied. The Fe-based alloy coating was prepared on a 27SiMn steel surface by high-speed laser cladding. The microstructure, morphological characteristics, element content, and phase composition of the cladding layer were analyzed by an optical microscope (OM), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), and X-ray diffractometer (XRD), respectively. The corrosion resistance of the 27SiMn substrate and Fe-based coating in different corrosive environments was tested through an electrochemical experimental station, a salt spray corrosion test box, and an immersion experiment. The Fe-based alloy cladding layer is mainly composed of a-Fe, M7C3, M2B, and Cr3Si. The cladding layer structure forms planar, cellular, dendrite, and equiaxed dendrite during rapid solidification. The corrosion potential of the cladding layer is higher than that of the substrate, and the arc radius of the cladding layer is larger than that of the substrate. After salt spray corrosion, a large number of red and black corrosion products appeared on the surface of the substrate; the surface of the cladding layer sample was still smooth, and the morphology was almost unchanged. The weight loss results of the cladding layer and 27SiMn matrix after 120 h of immersion are 0.0688 and 0.0993 g·cm−2, respectively. The weight loss of the cladding layer is 30.7% less than that of the matrix. Conclusion: Laser cladding an Fe-based alloy coating on the surface of 27SiMn has better corrosion resistance than the substrate, which improves the corrosion resistance of hydraulic supports.

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DOI      [本文引用: 1]

本文研究了(Ni, Pt)Al涂层氧化不同时间后涂层退除及再涂覆,尤其不同服役时间氧化后涂层及下方基体合金组织结构的演变。采用电镀Pt层和化学气相渗铝的方法在镍基单晶高温合金上制备了(Ni, Pt)Al涂层,然后对涂层试样在1100 ℃中分别氧化300、1000和3000 h。表明不同时间氧化后涂层表面生成的氧化产物都为Al<sub>2</sub>O<sub>3</sub>;随着氧化时间的增长,涂层退化严重且涂层下方析出的TCP相增多。在HCl和C<sub>6</sub>H<sub>8</sub>O<sub>7</sub>·H<sub>2</sub>O的混合溶液中成功退除不同时间氧化后的(Ni, Pt)Al涂层,涂层的退除主要是沿晶界溶解,并随着Al含量的减少,溶解速率下降,而重新沉积的(Ni, Pt)Al涂层微观组织结构差异不大,长时间氧化后的试样单晶基体侧粗大TCP相析出增多。

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DOI      URL     [本文引用: 3]

In this study, ultra-high-speed laser cladding (UHSLC) and traditional low-speed laser cladding (LSLC) were employed to prepare high-quality Inconel625 coatings on 27SiMn substrates. UHSLC has cladding speeds of 30 m/min, which are 15 times faster than those of LSLC, and it produces a much greater cladding efficiency, which is 13.9 times greater than LSLC. The microstructure of the Inconel625 coatings was investigated in detail utilizing field emission scanning electron microscopy (FESEM) and electron probe microanalyzer (EPMA). According to the FESEM results, UHSLC Inconel625 coatings have more refined crystals than LSLC Inconel625 coatings. Nevertheless, the EPMA results indicate that the UHSLC Inconel625 coatings exhibit much more severe elemental segregation. Moreover, the hardness, wear and corrosion resistance of Inconel625 coatings are significantly enhanced by increasing the laser cladding speed. Furthermore, the reasons for the differences in microstructure and properties of Inconel625 coatings prepared by UHSLC and LSLC were clarified by finite element simulation. UHSLC technique is, therefore, more suitable for preparing Inconel625 coatings on 27SiMn steel surfaces than LSLC.

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DOI      [本文引用: 1]

首先总结了涂层材料元素组成对耐腐蚀性能的影响;其次,从钝化膜、显微组织、位错、低角度晶界、热腐蚀动力学等几个方面总结了其与耐腐蚀性的联系;第三,综述了EHLA与场外辅助技术结合对所制备涂层耐腐蚀性的影响;最后,总结和展望了超高速激光熔覆所制备涂层耐腐蚀性能的强化方法。

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