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中华口腔医学研究杂志(电子版) ›› 2016, Vol. 10 ›› Issue (05) : 327 -332. doi: 10.3877/cma.j.issn.1674-1366.2016.05.005

所属专题： 文献；

基础研究

3D打印和铸造钴铬合金耐蚀性及力学稳定性比较
李小宇1, 郑美华1,†(), 王洁琪1, 杨桂成2, 何滔3, 李劲松1, 范松1   
  1. 1. 510120　广州，中山大学孙逸仙纪念医院口腔科
    2. 510275　广州，中山大学材料科学研究所，教育部重点实验室
    3. 510055　广州，中山大学光华口腔医学院·附属口腔医院，广东省口腔医学重点实验室
  • 收稿日期:2016-05-03 出版日期:2016-10-01
  • 通信作者: 郑美华

Comparison of the corrosion resistance and the mechanical stability after corrosion of 3D printing and cast cobalt-chromium alloy

Xiaoyu Li1, Meihua Zheng1,†(), Jieqi Wang1, Guicheng Yang2, Tao He3, Jingsong Li1, Song Fan1   

  1. 1. Department of Stomatology, Sun Yat-sen Memorial Hospital, Sun Yat-sen University, Guangzhou 510120, China
    2. Institution of Material Science Research, Sun Yat-sen University, Key Laboratory of Ministry of Education, Guangzhou 510275, China
    3. Guanghua School of Stomatology, Hospital of Stomatology, Sun Yat-sen University, Guangdong Provincial Key Laboratory of Stomatology, Guangzhou 510055, China
  • Received:2016-05-03 Published:2016-10-01
  • Corresponding author: Meihua Zheng
  • About author:
    Corresponding author: Zheng Meihua, Email:
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引用本文：

李小宇, 郑美华, 王洁琪, 杨桂成, 何滔, 李劲松, 范松. 3D打印和铸造钴铬合金耐蚀性及力学稳定性比较[J]. 中华口腔医学研究杂志(电子版), 2016, 10(05): 327-332.

Xiaoyu Li, Meihua Zheng, Jieqi Wang, Guicheng Yang, Tao He, Jingsong Li, Song Fan. Comparison of the corrosion resistance and the mechanical stability after corrosion of 3D printing and cast cobalt-chromium alloy[J]. Chinese Journal of Stomatological Research(Electronic Edition), 2016, 10(05): 327-332.

目的

研究3D打印和铸造钴铬合金的耐蚀性及腐蚀对其力学稳定性的影响。

方法

采用3D打印技术中选择性激光熔融技术（SLM）和传统铸造技术共制作钴铬合金试件72个，根据是否腐蚀采用随机数字法随机平均分为12组（每组6个），各组用于不同的测试及进入腐蚀。采用静态浸泡腐蚀法对试件进行腐蚀实验，激光扫描共聚焦显微镜（CLSM）检测试件表面粗糙度（Ra）及表面形貌，显微硬度计测量显微维氏硬度（VHN），万能测试机测试拉伸强度（TS）及弯曲强度（BS）。工艺和腐蚀对Ra、VHN、TS、BS等值的影响采用双因素析因方差分析进行分析（α= 0.05），Bonferroni法进行组间两两比较。

结果

工艺和腐蚀对Ra和BS无交互效应（FRa= 2.989，PRa= 0.099；FBS= 0.480，PBS= 0.496）。两因素对Co-Cr合金的Ra值的主效应均有统计学意义（F工艺=6.262，P工艺=0.021；F腐蚀= 6.581，P腐蚀= 0.018），3D组的Ra值[（0.084 ± 0.026）μm]低于铸造组[（0.111 ± 0.024）μm]，对照组的Ra值[（0.084 ± 0.025）μm]低于腐蚀组[（0.111 ± 0.025）μm]。两因素对Co-Cr合金的BS值的主效应均有统计学意义（F工艺= 6.753，P工艺= 0.013；F腐蚀= 7.384，P腐蚀= 0.017），3D组的BS值[（1651 ± 242）MPa]高于铸造组[（1371 ± 252）MPa]，对照组的BS值[（1645±183）MPa]高于腐蚀组[（1377±310）MPa]。两因素对VHN和TS有交互效应（FVHN=5.018，PVHN=0.037；FTS= 5.903，PTS= 0.025）。Bonferroni法组间两两比较结果显示，3D对照组VHN值和TS值[VHN3D=（469 ± 4）HV，TS3D=（1010 ± 46）MPa]与铸造对照组[VHN铸造=（418 ± 4）HV，TS铸造=（827 ± 25）MPa]比较，差异有统计学意义（PVHN<0.001，PTS<0.001）；3D腐蚀组VHN值及TS值[VHN3D=（418±3）HV，TS3D=（985 ± 30）MPa]与铸造腐蚀组[VHN铸造=（375 ± 5）HV，TS铸造=（728 ± 45）MPa]比较，差异有统计学意义（PVHN<0.001，PTS<0.001）；3D对照组VHN值与3D腐蚀组比较差异有统计学意义（P<0.001），3D对照组TS值与3D腐蚀组比较差异无统计学意义（P= 1.000）；铸造对照组VHN值及TS值与铸造腐蚀组差异有统计学意义（PVHN<0.001，PTS= 0.001）。

结论

3D打印钴铬合金较铸造钴铬合金耐蚀性更优；前者TS、BS的稳定性均大于后者，两者的VHN稳定性相当。

关键词: 3D打印, 选择性激光熔融, 钴铬合金, 耐蚀性, 力学稳定性
Objective

To compare the corrosion resistance and the mechanical stability after corrosion of 3D printing and cast cobalt-chromium (Co-Cr) alloy.

Methods

The Co-Cr alloys were fabricated by the selective laser melting (SLM) technique and casting technique with suitable parameters, seventy-two specimens were prepared and divided into 12 groups (n= 6) by random number method. Static immersion test was used to evaluate corrosion resistance and the effect of the corrosion on the mechanical stability of the alloys. Surface roughness (Ra) , vickers hardness (VHN) , tensile strength (TS) and bending strength (BS) of the samples were analyzed separately by confocal laser scanning microscope (CLSM) , vicker microhardness tester, universal testing machine. The results were analyzed by 2×2 factorial design analysis of variance (α= 0.05) , the pairwise comparison was performed with Bonferroni method.

Results

Manufacturing methods and corrosion had no interaction effects on Ra and BS (FRa= 2.989, PRa= 0.099; FBS= 0.480, PBS= 0.496) . The two factors′ main effects on Ra had significant differences (Fmethod= 6.262, Pmethod= 0.021; Fcorrosion= 6.581, Pcorrosion= 0.018) . The Ra of 3D group was lower than that of cast group [Ra3D= (0.084 ± 0.026) μm, Racast= (0.111 ± 0.024) μm]. The Ra of contrast group was lower than that of corrosion group[Racontrast= (0.084 ± 0.025) μm, Racorrosion= (0.111 ± 0.025) μm]. The two factors′ main effects on BS had significant differences (Fmethod= 6.753, Pmethod= 0.013; Fcorrosion= 7.384, Pcorrosion= 0.017) . The BS of 3D group was higher than that of cast group [BS3D= (1651 ± 242) MPa, BScast= (1371 ± 252) MPa]. The BS of contrast group was higher than that of corrosion group [BScontrast= (1645 ± 183) MPa, BScorrosion= (1377 ± 310) MPa]. Manufacturing methods and corrosion had interaction effects on VHN and TS (FVHN= 5.018, PVHN= 0.037; FTS= 5.903, PTS= 0.025) . The results of the pairwise comparison of Bonferroni method suggested significant differences on VHN and TS (PVHN<0.001, PTS<0.001) were found between the 3D contrast group [VHN3D= (469 ± 4) HV, TS3D= (1010 ± 46) MPa] and the cast contrast group [VHNcast= (418 ± 4) HV, TScast= (827 ± 25) MPa], significant differences on VHN and TS (PVHN<0.001, PTS<0.001) were observed between the 3D corrosion group [VHN3D= (418 ± 3) HV, TS3D= (985 ± 30) MPa] and the cast corrosion group [VHNcast= (375 ± 5) HV, TScast= (728 ± 45) MPa]. Significant differences on VHN (P<0.001) were found between the 3D contrast group and the 3D corrosion group. No significant differences on TS (P= 1.000) were found between the 3D contrast group and the 3D corrosion group. Significant differences on VHN and TS (PVHN<0.001, PTS<0.001) were observed between the cast contrast group and the cast corrosion group.

Conclusions

The 3D printing Co-Cr alloy has better corrosion resistance than that of the cast Co-Cr alloy. The 3D printing Co-Cr alloy has better stability of the TS and BS than that of the cast Co-Cr alloy. Both kinds of alloys have equal stability of VHN.

Key words: 3D printing, Selective laser melting, Cobalt-chromium alloy, Corrosion resistance, Mechanical stability
表1 3D打印和铸造钴铬合金试件表面粗糙度和力学性能测试时试件的生产标准及尺寸
测试指标 生产标准 尺寸(mm)
表面粗糙度及显微硬度 ISO6507?1?2005 φ6 × 2（圆柱体）
拉伸强度 ISO6892?1?2009 标距16、宽2、厚1（哑铃形）
弯曲强度 ISO7438?2005 20 × 1.5 × 1（长方体）
表2 3D打印和铸造钴铬合金试件表面粗糙度和力学性能测试的实验分组和样本量（个）
组别 表面粗糙度及显微硬度 拉伸强度 弯曲强度 总计
3D对照组 6 6 6 18
3D腐蚀组 6 6 6 18
铸造对照组 6 6 6 18
铸造腐蚀组 6 6 6 18
总计 24 24 24 72
表3 3D打印和铸造钴铬合金试件未腐蚀和经腐蚀后的表面粗糙度值和各项力学性能值（±s）
组别 试件数 （个） Ra （μm） VHN (HV) TS (MPa) BS (MPa)
3D对照组 6 0.079±0.029 469±4 1010±46 1749±208
3D腐蚀组 6 0.089±0.022 418±3 985±30 1553±275
铸造对照组 6 0.088±0.021 418±4 827±25 1541±158
铸造腐蚀组 6 0.133±0.027 375±5 728±45 1200±345
表4 工艺和腐蚀对钴铬合金试件耐蚀性和力学稳定性影响的2×2析因方差分析结果
生产工艺 Ra VHN TS BS
F值 P值 F值 P值 F值 P值 F值 P值
工艺 6.855 0.016 704.791 <0.001 204.187 <0.001 7.201 0.014
腐蚀 7.204 0.014 725.182 <0.001 16.082 0.001 6.586 0.018
工艺+腐蚀 2.989 0.099 5.018 0.037 5.903 0.025 0.480 0.496
表5 工艺和腐蚀对钴铬合金试件Ra和BS主效应的2×2析因方差分析结果
生产工艺 Ra BS
F值 P值 F值 P值
工艺 6.262 0.021 6.753 0.013
腐蚀 6.581 0.018 7.384 0.017
图1 激光扫描共聚焦显微镜测量3D打印和铸造钴铬合金试件表面粗糙度值所获得的三维微观形貌图
图2 激光扫描共聚焦显微镜测量3D打印和铸造钴铬合金试件表面粗糙度值所获得的表面形貌（× 200）
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