TC4表面激光熔覆硬质涂层的制备与分析

doi:10.12141/j.issn.1000-565X.220605

摘要/Abstract

摘要：

为解决TC4钛合金硬度低、耐磨性差等缺点，利用激光熔覆技术，采用4 kW大功率Laser4000半导体激光器，在TC4表面制备了以HfC、TaC和ZrC等比例三元陶瓷相（比例分别为0%、5%、10%、15%）为增强相的钛基硬质涂层。熔覆结束后对熔覆件进行切割、打磨、抛光和腐蚀制备金相试样，利用电子显微镜（EM）、扫描电镜（SEM）、EDS能谱仪、X射线衍射仪（XRD）等试验手段对不同材料组分的熔覆涂层进行了宏观形貌、微观组织和性能的对比分析；利用TH120A里氏硬度计测熔覆层的宏观硬度值，利用Qness型号维氏显微硬度计分析熔覆试样截面微观硬度变化规律。研究结果表明：三元陶瓷相的添加，使熔覆层与基材形成了良好的冶金结合，并且基材与熔覆层有着明显的平滑的分界线；熔覆层主要由α+β针状马氏体基体及析出的棒状和块状α相组成，其中添加质量分数为15%的三元陶瓷增强相的涂层熔覆层由块状晶组成，且晶粒最为粗大，添加质量分数为5%和10%的三元陶瓷增强相的涂层，棒状和块状的α相尺寸明显变小，晶粒明显被细化，组织更加均匀致密；熔覆层柱状和块状α相的主要成分为Ti以及微量的Al、Zr、Hf和V元素，涂层的针状马氏体中含有较高的Al、Zr、Ta和V元素，在晶间的黑色β相中含有微量的Zr和Ta元素。测试发现，Hf、Ta元素通常存在于不同的物相中；激光熔覆后的试件的硬度都有所提高，当三元陶瓷添加量的质量分数为10%时，熔覆层晶粒最为细小，分布均匀，硬度最高，达到715 HV，是TC4基材的2.31倍。

关键词: TC4钛合金, 激光熔覆, 金属陶瓷涂层, 显微硬度

Abstract:

In order to solve the shortcomings of low hardness and poor wear resistance of TC4 titanium alloy, this study prepared titanium-based hard coatings reinforced by HfC, TaC and ZrC ternary ceramic phases (0%, 5%, 10%, 15%, respectively ) on TC4 surface by 4 kW high-power Laser4000 semiconductor laser with laser cladding technology. After the cladding, the cladding parts were cut, polished and corroded to prepare metallographic samples. The macroscopic morphology, microstructure and properties of the cladding coatings with different material components were compared and analyzed by EM electron microscope, SEM scanning electron microscope, EDS energy spectrometer and XRD diffractometer. The macro hardness value of the cladding layer was measured by TH120 A Leeb hardness tester, and the micro hardness change rule of the cladding sample section was analyzed by Qness type Vickers microhardness tester. The results show that the addition of ternary ceramic phase makes the cladding layer and the substrate form a good metallurgical bonding, and the substrate and the cladding layer have a clear smooth boundary. The cladding layer is mainly composed of α+β acicular martensite matrix and precipitated rod-like and block-like α phases. The cladding layer of the ternary ceramic reinforcement phase with a mass fraction of 15% is composed of block-like crystals, and the grains are the most coarse. For the coating of the ternary ceramic reinforcement phase with a mass fraction of 5% and 10%, the size of the rod-like and block-like α phases is significantly reduced, the grains are obviously refined, and the structure is more uniform and dense. The main components of the columnar and massive α phases in the cladding layer are Ti and trace Al, Zr, Hf and V elements. The acicular martensite of the coating contains high Al, Zr, Ta and V elements, and the black β phase between the crystals contains trace Zr and Ta elements. It is found that Hf and Ta elements usually exist in different phases. The hardness of the specimens is improved after laser cladding. When the mass fraction of the ternary ceramic addition is 10%, the grain of the cladding layer is the smallest, the distribution is uniform, and the hardness is the highest, reaching 715 HV, which is 2.31 times that of TC4 substrate.

Key words: TC4 titanium alloy, laser cladding, metal ceramic coating, microhardness

中图分类号:

TG174

郑立娟, 胡紫涛, 刘绍峰, 等. TC4表面激光熔覆硬质涂层的制备与分析[J]. 华南理工大学学报(自然科学版), 2023, 51(6): 146-152.

ZHENG Lijuan, HU Zitao, LIU Shaofeng, et al. Preparation and Analysis of Laser Cladding Hard Coating on TC4 Surface[J]. Journal of South China University of Technology(Natural Science Edition), 2023, 51(6): 146-152.

图/表 11

图1

表1

图2

图3

图4

图5

图6

图7

表2

图8

图9

参考文献 22

1	赵永庆，葛鹏，辛社伟．近五年钛合金材料研发进展［J］．中国材料进展，2020，39（Z1）：527-534，557-558.
	ZHAO Yongqing， GE Peng， XIN Shewei ．Progresses of R＆D on Ti-alloy materials in recent 5 years ［J］．Materials China，2020，39（Z1）：527-534，557-558.
2	覃鑫，祁文军，左小刚．TC4钛合金表面激光熔覆 NiCrCoAlY-Cr₃C₂复合涂层的摩擦和高温抗氧化性能［J］．材料工程，2021，49（12）：107-114.
	QIN Xin， QI Wenjun， ZUO Xiaogang ．Friction and high temperature oxidation resistance of laser cladding NiCrCoAlY-Cr₃C₂ composite coating on TC4 titanium alloy ［J］．Journal of Materials Engineering，2021，49（12）：107-114.
3	LIU Y， LIANG C P， LIU W S ．Dilution of Al and V through laser powder deposition enables a continuously compositionally Ti/Ti6Al4V graded structure ［J］．Journal of Alloys and Compounds，2018，763：376-383.
4	孟祥军，沈颖，张少瑜，等．Ti6Al4V合金激光熔覆Co-Ti₃SiC₂复合涂层的组织和摩擦学性能［J］．金属热处理，2021，46（12）：199-203.
	MENG Xangjun， SHEN Ying， ZHANG Shaoyu，et al ．Microstructure and tribological properties of laser clad Co-Ti₃SiC₂ composite coating on Ti6Al4V alloy ［J］．Heat Treatment of Metals，2021，46（12）：199- 203.
5	柯金，刘秀波，庄宿国，等．Ti6Al4V合金激光熔覆NiMoSi复合涂层的高温抗氧化性能［J］．中国表面工程，2018，31（6）：109-117.
	KE Jin， LIU Xiubo， ZHUANG Suguo，et al ．High temperature oxidation resistance of NiMoSi composite coatings on Ti6AI4V alloy by laser cladding ［J］．China Surface Engineering，2018，31（6）：109-117.
6	王涛，刘佳奇，秦令超．激光功率对CoNiCrAlY熔覆涂层显微组织及硬度的影响［J］．热加工工艺，2018，47（24）：142-145，151.
	WANG Tao，LIU Jiaqi，QIN Lingchao，Effects of laser power on microstructure and hardness of CoNiCrAlY cladding coatings ［J］．Hot Working Technology，2018，47（24）：142-145，151.
7	林英华，雷永平，符寒光，等．激光原位制备硼化钛与镍钛合金增强钛基复合涂层［J］．金属学报，2014，50（12）：1513-1519.
	LIN Yinghua， LEI Yongping， FU Hanguang，et al ．Laser in-situ synthessized titanium diboride and nitinol reinforce titanium matrix composite coatings ［J］．Acta Metallurgica Sinica，2014，50（12）：1513-1519.
8	ZHANG Q， ZHANG P L， LI M H，et al ．Microstructure wear resistanceand oxidation behavior of Ni-Ti-Si coatings fabricated on Ti6Al4V by laser cladding ［J］．Materials，2017，10（11）：1248-1250．
9	FENG Y Q， FENG K， TAO C W，et al ．Microstructure and properties of in-situ synthesized （Ti₃Al+TiB）/Ti composites by laser cladding ［J］．Materials & Design，2018，157：258-272.
10	林基辉，温亚辉，范文博，等．钛合金表面激光改性技术研究进展［J］．金属热处理，2022，47（3）：215-221.
	LIN Jihui， WEN Yahui， FAN Wenbo，et al ．Research progress of laser modification technology for titanium alloy surface ［J］．Heat Treatment of Metals，2022，47（3）：215-221.
11	LI J N， CHEN C Z， ZONG L ．Microstructure characteristics of Ti₃Al/TiC ceramic layer deposited by laser cladding［J］．International Journal of Refractory Metals and Hard Materials，2011，29（1）：49-53.
12	LI J， CHEN C， SQUARTINI T，et al ．A study on wear resistance and microcrack of the Ti₃Al/TiAl+TiC ceramic layer deposited by laser cladding on Ti-6Al-4V Alloy ［J］．Applied Surface Science，2010，257（5）：1550-1555.
13	GAO Q S， YAN H， QIN Y， al et，Laser cladding Ti-Ni/TiN/TiW+TiS/WS self-lubricating wear resistant composite coating on Ti-6Al-4V alloy ［J］．Optics & Laser Technology，2019，113：182-191.
14	SONG R， LI J， SHAO J Z，et al ．Microstructural evolution and wear behaviors of laser cladding Ti₂Ni/α（Ti） dual-phase coating reinforced by TiB and TiC ［J］．Applied Surface Science，2015，355：298-309.
15	孙帅，李崇桂，李帅，等．WC含量对激光熔覆Al₂O₃/TiO₂涂层组织与性能的影响［J］．金属热处理，2018，43（12）：78-82.
	SUN Shuai， LI Chonggui， LI Shuai，et al ．Effect of WC content on microstructure and properties of laser cladding Al₂O₃/TiO₂ coating ［J］．Heat Treatment of Metals，2018，43（12）：78-82.
16	唐友亮，蔡维平，张锦．激光熔覆TiC-WC增强NiCrMn合金涂层组织与性能［J］．热加工工艺，2017，46（16）：152-157.
	TANG Youling， CAI Weiping， ZHANG Jin ．Microstructure and property of laser cladding NiCrMn alloy coating reinforced by TiC-WC ［J］．Hot Working Technology．2017，46（16）：152-157.
17	ZHOU S， LEI J， DAI X，et al ．A comparative study of the tructure and wear resistance of NiCrBSi/50 wt% WC composite coatings by laser cladding and laser induction hybrid cladding ［J］．International Journal of Refractory Metals and Hard Materials，2016，60：17-27.
18	LUO X， LI J， LI G J ．Effect of NiCrBSi content on microstructural evolution，cracking susceptibility and wear behaviors of laser cladding WC/Ni-NiCrBSi composite coatings ［J］．Journal of Alloys and Compounds，2015，626：102-111.
19	张海云，张金，朱磊，等．WC含量对激光熔覆TC4涂层组织及性能的影响［J］．热加工工艺，2022，51（8）：83-87，93.
	ZHANG Haiyun， ZHANG Jin， ZHU Lei，et al ．Effects of WC content on microstructure and properties of TC4 composite prepared by laser cladding ［J］．Hot Working Technology，2022，51（8）：83-87，93.
20	李蕊，王浩．Ti811和TC4钛合金基材属性对激光熔覆自润滑耐磨复合涂层组织与性能的影响［J］．复合材料学报，2022，39（12）：5984-5995.
	LI Rui， WANG Hao. Effect of Ti811 and TC4 Titanium alloy substrate on microstructures and properties of laser cladding self-lubricating composite coatings ［J］．Acta Materiae Compositae Sinica，2022，39（12）：5984-5995.
21	刘丹，陈志勇，陈科培，等．TC4钛合金表面激光熔覆复合涂层的组织和耐磨性［J］．金属热处理，2015，40（3）：58-62.
	LIU Dan， CHEN Zhiyong， CHEN Kepei，et al ．Microstructure and wear resistance of laser clad composite coating on TC4 titanium alloy surface ［J］．Heat Treatment of Metals，2015，40（3）：58-62.
22	孙荣禄，杨贤金．激光熔覆TiC陶瓷涂层的组织和摩擦磨损性能研究［J］．光学技术，2006，32（2）：287-289.
	SUN Ronglu， YANG Xianjin ．Microstructure and friction wear properties of TiC laser clad layer ［J］．Optical Technique，2006，32（2）：287-289.

粉末编号	ZrC	TaC	HfC	TC4
T0	0.00	0.00	0.00	100
T1	1.67	1.67	1.67	95
T2	3.33	3.33	3.33	90
T3	5.00	5.00	5.00	85

元素	图7（a）点1	图7（a）点2	图7（a）区域1	图7（b）点1	图7（b）点2	图7（b）点3	图7（b）点4
Ti	95.45	94.77	95.41	93.54	92.53	83.78	94.50
Al	4.55	5.23	4.59	0.58	1.07	7.51	2.99
Zr	0.00	0.00	0.00	1.83	1.91	3.19	0.98
Hf	0.00	0.00	0.00	4.05	4.49	0.00	0.00
Ta	0.00	0.00	0.00	0.00	0.00	5.52	1.53

[1]	付宇明, 马顺芯, 刘绍峰, 等. TC4表面激光熔覆硬质复合涂层组织与性能研究[J]. 华南理工大学学报(自然科学版), 2024, 52(3): 10-17.
[2]	康澜, 邬彬, 陈志邦. 激光熔覆技术修复局部腐蚀钢板后修复件的力学性能[J]. 华南理工大学学报(自然科学版), 2022, 50(5): 137-146.
[3]	曹发祥, 孔金星, 杜东兴. Nd: YAG 晶体表面性能等离子体改性研究[J]. 华南理工大学学报（自然科学版）, 2021, 49(3): 55-61.
[4]	吕非田宗军梁绘昕谢德巧沈理达肖猛. AlSi10Mg铝合金激光熔化沉积显微组织及力学性能[J]. 华南理工大学学报（自然科学版）, 2018, 46(10): 117-125.
[5]	孔金星邓飞赵威何宁. 冷却润滑方式对纯铁车削表面完整性的影响[J]. 华南理工大学学报（自然科学版）, 2015, 43(6): 89-95.