离子束改性AZ31镁合金耐磨抗蚀复合性能研究
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摘要
本文采用MEVVA 80-10型金属蒸发真空弧离子注入装置和TEMP-6型强流脉冲离子束(HIPIB)装置,分别开展了Al离子常温和高温注入、强流脉冲离子束辐照AZ31镁合金实验研究,揭示了离子束改性的表面成分、结构和性能变化规律,获得了具有耐磨抗蚀复合性能的改性表面,阐明了Al离子常温和高温注入、HIPIB辐照AZ31镁合金耐磨抗蚀复合改性机理。
注入剂量分别为2×10~(16),6×10~(16)和1×10~(17)/cm~2的Al离子常温和300℃高温注入AZ31镁合金,1×10~(17)/cm~2注入剂量下,常温和300℃高温注入Al离子的峰值浓度分别为10 at.%和8 at.%,注入深度为840和1200 nm。原始试样主要由α-Mg相组成,同时还含有少量的金属间化合物β-Mg_(17)Al_(12)相和MgO相。常温1×10~(17)/cm~2注入剂量下,表面β相含量增加,300℃高温2×10~(16)/cm~2注入剂量下,即有新的β相析出。
Al离子常温和300℃高温注入AZ31镁合金,在载荷为5 N和20 N,滑动速度为2mm/s的往复式干滑动磨损条件下,以及在pH=12的0.01-0.08 mol/l NaCl溶液中,获得了具有耐磨抗蚀复合性能的改性表面。载荷为5 N,磨损10 min,注入剂量为2×10~(16)/cm~2的常温注入试样,磨损量降低约20%。载荷为20 N,磨损20 min,注入剂量为2×10~(16)/cm~2的常温注入试样磨损量降低约30-40%,注入剂量为6×10~(16)/cm~2的300℃高温注入试样磨损量降低约15-20%。载荷为5 N条件下,原始镁合金呈现以显微切削为主的磨粒磨损机理,Al离子注入没有改变镁合金的磨损机理,但塑性变形程度和磨粒磨损倾向明显减小。载荷为20 N条件下,发生了从原始试样金属磨粒磨损到离子注入试样氧化磨损机理的转变。在pH=12的0.01 mol/l NaCl溶液中,Al离子注入试样阳极极化性能较原始试样明显改善,注入剂量为6×10~(16)/cm~2的Al离子300℃高温注入试样,具有优异的抗蚀性能,腐蚀电位和孔蚀击穿电位较原始试样分别提高约400和800 mV,维钝电流密度比原始试样降低了约一个数量级。在pH=12的0.08 mol/l NaCl溶液中,注入剂量为1×10~(17)/cm~2的Al离子常温和300℃高温注入试样,腐蚀电位较原始试样分别提高约180和280 mV,孔蚀击穿电位分别提高约150和220 mV。Al离子常温及300℃高温注入AZ31镁合金耐磨抗蚀复合性能的改善,主要归因于镁合金表面富集Al的固溶增强作用,以及β-Mg_(17)Al_(12)的第二相弥散增强作用。
束流密度为100-300A/cm~2,辐照次数为1-10,HIPIB辐照AZ31镁合金表面形成了以局部烧蚀坑和熔融扰动为主要特征的烧蚀形貌。随着束流密度和辐照次数增加,熔化层和热影响区的显微组织较原始试样明显细化。由于HIPIB重复的快速熔化和凝固,镁合金表面化学成分趋于均匀化,显微结构细化,第二相β-Mg_(17)Al_(12)分布均匀。
利用HIPIB辐照AZ31镁合金,在载荷为0.1-0.5 N,滑动速度为0.08 m/s,磨损时间为5 min的球盘式干滑动磨损条件下,以及在pH=12的0.01-0.5 mol/l NaCl溶液中,获得了具有耐磨抗蚀复合性能的改性表面。载荷为0.1 N条件下,300 A/cm~2,10次辐照试样具有最优的耐磨减摩性能,摩擦系数由原始试样的0.378减小到0.338,磨损量较原始试样降低约75%。载荷为0.2和0.5 N条件下,300 A/cm~2,10次辐照试样的摩擦系数分别由原始试样的0.364和0.361减小到0.334和0.313,磨损量较原始试样分别降低约40%和15%。HIPIB辐照镁合金试样仍然以磨粒磨损为主,但被辐照试样的磨粒磨损倾向较原始试样大大降低,主要表现为塑性变形程度的减轻和磨痕表面犁沟的变细变浅,同时磨痕局部呈现氧化磨损特征。在pH=12的0.01 mol/l NaCl溶液中,HIPIB辐照试样的阳极极化性能较原始试样明显改善,100 A/cm~2,5次辐照试样具有优异的抗蚀性能,腐蚀电位和孔蚀击穿电位较原始试样分别提高约560和630 mV。原始试样形成的大块腐蚀产物及在腐蚀过程中发生的开裂现象,在被辐照试样表面得到明显减轻,可观察到面积较大的未遭受腐蚀破坏的表面钝化特征。随着Cl~-浓度增大,原始试样和被辐照试样的抗蚀性能均降低,但被辐照试样的抗蚀性能仍然优于原始试样。被辐照表面化学成分的均匀化和显微组织的细化是HIPIB辐照AZ31镁合金耐磨抗蚀复合性能改善的主要原因。
Al ion implantation and HIPIB irradiation into AZ31 magnesium alloy are carried out in a MEVVA 80-10 ion implantation system and in TEMP-6 type HIPIB apparatus,respectively. The changes in composition,structure and properties of ion beams modified AZ31 magnesium alloy are revealed and the combined improvement in wear and corrosion resistance of AZ31 magnesium alloy is achieved.The modification mechanism in the wear and corrosion resistance of Al ion implanted and H1PIB irradiated AZ31 magnesium alloy are also illustrated in terms of the changes in composition,structure and properties of modified surface.
The Al ion implantation into AZ31 magnesium alloys is carried out at an implantation dose of 2×10~(16),6×10~(16) and 1×10~(17) ions/cm~2 at room temperature and at 300℃.The concentration depth profiles of implanted Al in AZ31 magnesium alloys with an implantation dose of 1×10~(17) ions/cm~2 at room temperature and at 300℃C were a Gaussian-type distribution in the depth up to about 840 and 1200 nm with the maximum Al concentration up to about 10 and 8 at.%respectively,measured by using Rutherford backscattering spectrometry(RBS). The microstructure,which is mainly composed ofα-Mg phase,and small amount of intermetallicβ-Mg_(17)Al_(12) and MgO phase is also observed on the original and implanted samples by X-ray diffraction(XRD).The new diffraction peak ofβphase is observed on the Al ion implanted AZ31 magnesium alloys with the higher implantation dose of 1×10~(17) ions/cm~2 at room temperature,whereas the new diffraction peak ofβphase is observed on the Al ion implanted AZ31 magnesium alloys with the lower implantation dose of 2×10~(16) ions/cm~2 at 300℃.
The combined improvement in wear and corrosion resistance is achieved for the Al ion implanted AZ31 magnesium alloys at room temperature and at 300℃using a reciprocating tribometer in a ball-on-flat configuration where the applied load is 5 and 20 N at a sliding speed of 2 mm/s and potentiodynamic polarization technology in the 0.01 mol/1 NaCl solution with a pH value of 12,respectively.For the Al ion implanted sample with a dose of 2×10~(16) ions/cm~2 at room temperature,the wear volume is reduced by 20%respectively,compared with that of the original sample under a load of 5 N for a sliding time of 10 min,and the wear volume is reduced by 30-40%under a load of 20 N for a sliding time of 20 min.For the Al ion implanted sample with a dose of 6×10~(16) ions/cm~2 at a temperature of 300℃,the wear volume is reduced by 1.5-20%under a load of 20 N for a sliding time of 20 min.Under a load of 5 N,the original sample exhibited a typical abrasive wear mechanism,characterized by microcutting and plastic deformation,and Al ion implantation did not change the wear mechanism of magnesium alloy.Under a load of 20 N for a sliding time of 20 min,the transitions in wear mechanism from severe metallic wear to oxidational wear for the Al ion implanted samples at room temperature and at 300℃were observed.The potentiodynamic polarization curves show that the corrosion resistance of Al ion implanted samples with an. implantation dose of 2×10~(16),6×10~(16) and 1×10~(17) ions/cm~2 at room temperature and at 300℃are superior to that of the original one in the 0.01 mol/l NaCl solution with a pH value of 12. The sample with an implantation dose of 6×10~(16) ions/cm~2 has the superior corrosion resistance,and the corrosion potential and pitting corrosion breakdown potential are 400 and 800 mV higher than those of the original sample,respectively.For the sample implanted with an implantation dose of 1×10~(17) ions/cm~2 at room temperature and at 300℃,corrosion potential is higher 180 and 280 mV,and the pitting corrosion breakdown potential is higher 150 and 220 mV than those of the original sample,in the 0.08 mol/l NaCl solution with a pH value of 12.It is believed that the combined improvement in wear and corrosion resistance for Al ion implanted samples at room temperature and at 300℃is attributed to the solid solution enhancing effects and the second phaseβenhancing effects induced by Al enrichment.
HIPIB irradiation into AZ31 magnesium alloy at ion current densities of 100-300 A/cm~2 with shot number of 1-10 led to a typical surface morphology with crater formation and waviness features in local region due to a selective ablation and disturbance of the molten surface.Compared with the original sample,the microstructure of remelted layer and heat-affected layer are significantly refined with increasing the ion current density and the shot number.HIPIB irradiation results in the significant chemical homogeneity, microstructural refinement and the homogenous redistribution of the second phase ofβon the irradiated surface due to the repetitive rapid melting and resolidification of surface irradiated by HIPIB.
The combined improvement in wear and corrosion resistance is achieved for HIPIB irradiated AZ31 magnesium alloys using a tribometer in a ball-on-disk configuration where the applied load is 0.1-0.5 N at a sliding speed of 0.08 m/s and potentiodynamic polarization technology in the 0.01-0.5 mol/1 NaC1 solution with a pH value of 12,respectively.The irradiated sample at 300 A/cm~2 with 10 shots exhibited the superior wear resistance,the friction coefficient decreased from 0.378 for original sample to 0.338,and the wear volume is reduced about 75%compared with the original one.The friction coefficient for the original and irradiated samples at 300 A/cm~2 with 10 shots decreases from 0.364 and 0.334 at a load of 0.2 N to 0.361 and 0.313 at a load of 0.5 N,and the wear volume is reduced about 40%and 15%compared with the original one,respectively.The wear mechanism for HIPIB irradiated samples is still typical of abrasive wear,however,the degree of abrasive wear is significantly reduced,and the improved wear resistance is characterized by reduced localized plastic deformation and shallower grooves,and the oxidational wear is observed on the local region of wear track.The apparent improvement in corrosion resistance is achieved for all the irradiated samples in 0.01 mol/l NaCl solution with a pH value of 12.The corrosion potential and pitting corrosion breakdown potential for the samples irradiated at 100 A/cm~2 with 5 shots are 560 and 630 mV higher than those of the original sample,respectively.Typical corroded surface morphologies for the original and irradiated samples revealed that the original sample suffered from a severe pitting corrosion attack,leading to the formation of voluminous corrosion products that crack severely during corrosion process.In contrast to the original sample,less pitting corrosion attack is observed for the irradiated samples,indicating the enhanced protective properties of surface formed on the irradiated samples due to remelted effect induced by HIPIB irradiation.Corrosion resistance for both the original and irradiated samples decreased with increasing the Cl~-concentration in NaCI solution,however,improved corrosion resistance of irradiated sample is still obtained in NaCl solution containing higher Cl~- concentration.The chemical homogeneity and microstructural refinement of the irradiated surface induced by HIPIB irradiation are the main reasons for the combined improvement in wear and corrosion resistance of AZ31 magnesium alloys.
注入剂量分别为2×10~(16),6×10~(16)和1×10~(17)/cm~2的Al离子常温和300℃高温注入AZ31镁合金,1×10~(17)/cm~2注入剂量下,常温和300℃高温注入Al离子的峰值浓度分别为10 at.%和8 at.%,注入深度为840和1200 nm。原始试样主要由α-Mg相组成,同时还含有少量的金属间化合物β-Mg_(17)Al_(12)相和MgO相。常温1×10~(17)/cm~2注入剂量下,表面β相含量增加,300℃高温2×10~(16)/cm~2注入剂量下,即有新的β相析出。
Al离子常温和300℃高温注入AZ31镁合金,在载荷为5 N和20 N,滑动速度为2mm/s的往复式干滑动磨损条件下,以及在pH=12的0.01-0.08 mol/l NaCl溶液中,获得了具有耐磨抗蚀复合性能的改性表面。载荷为5 N,磨损10 min,注入剂量为2×10~(16)/cm~2的常温注入试样,磨损量降低约20%。载荷为20 N,磨损20 min,注入剂量为2×10~(16)/cm~2的常温注入试样磨损量降低约30-40%,注入剂量为6×10~(16)/cm~2的300℃高温注入试样磨损量降低约15-20%。载荷为5 N条件下,原始镁合金呈现以显微切削为主的磨粒磨损机理,Al离子注入没有改变镁合金的磨损机理,但塑性变形程度和磨粒磨损倾向明显减小。载荷为20 N条件下,发生了从原始试样金属磨粒磨损到离子注入试样氧化磨损机理的转变。在pH=12的0.01 mol/l NaCl溶液中,Al离子注入试样阳极极化性能较原始试样明显改善,注入剂量为6×10~(16)/cm~2的Al离子300℃高温注入试样,具有优异的抗蚀性能,腐蚀电位和孔蚀击穿电位较原始试样分别提高约400和800 mV,维钝电流密度比原始试样降低了约一个数量级。在pH=12的0.08 mol/l NaCl溶液中,注入剂量为1×10~(17)/cm~2的Al离子常温和300℃高温注入试样,腐蚀电位较原始试样分别提高约180和280 mV,孔蚀击穿电位分别提高约150和220 mV。Al离子常温及300℃高温注入AZ31镁合金耐磨抗蚀复合性能的改善,主要归因于镁合金表面富集Al的固溶增强作用,以及β-Mg_(17)Al_(12)的第二相弥散增强作用。
束流密度为100-300A/cm~2,辐照次数为1-10,HIPIB辐照AZ31镁合金表面形成了以局部烧蚀坑和熔融扰动为主要特征的烧蚀形貌。随着束流密度和辐照次数增加,熔化层和热影响区的显微组织较原始试样明显细化。由于HIPIB重复的快速熔化和凝固,镁合金表面化学成分趋于均匀化,显微结构细化,第二相β-Mg_(17)Al_(12)分布均匀。
利用HIPIB辐照AZ31镁合金,在载荷为0.1-0.5 N,滑动速度为0.08 m/s,磨损时间为5 min的球盘式干滑动磨损条件下,以及在pH=12的0.01-0.5 mol/l NaCl溶液中,获得了具有耐磨抗蚀复合性能的改性表面。载荷为0.1 N条件下,300 A/cm~2,10次辐照试样具有最优的耐磨减摩性能,摩擦系数由原始试样的0.378减小到0.338,磨损量较原始试样降低约75%。载荷为0.2和0.5 N条件下,300 A/cm~2,10次辐照试样的摩擦系数分别由原始试样的0.364和0.361减小到0.334和0.313,磨损量较原始试样分别降低约40%和15%。HIPIB辐照镁合金试样仍然以磨粒磨损为主,但被辐照试样的磨粒磨损倾向较原始试样大大降低,主要表现为塑性变形程度的减轻和磨痕表面犁沟的变细变浅,同时磨痕局部呈现氧化磨损特征。在pH=12的0.01 mol/l NaCl溶液中,HIPIB辐照试样的阳极极化性能较原始试样明显改善,100 A/cm~2,5次辐照试样具有优异的抗蚀性能,腐蚀电位和孔蚀击穿电位较原始试样分别提高约560和630 mV。原始试样形成的大块腐蚀产物及在腐蚀过程中发生的开裂现象,在被辐照试样表面得到明显减轻,可观察到面积较大的未遭受腐蚀破坏的表面钝化特征。随着Cl~-浓度增大,原始试样和被辐照试样的抗蚀性能均降低,但被辐照试样的抗蚀性能仍然优于原始试样。被辐照表面化学成分的均匀化和显微组织的细化是HIPIB辐照AZ31镁合金耐磨抗蚀复合性能改善的主要原因。
Al ion implantation and HIPIB irradiation into AZ31 magnesium alloy are carried out in a MEVVA 80-10 ion implantation system and in TEMP-6 type HIPIB apparatus,respectively. The changes in composition,structure and properties of ion beams modified AZ31 magnesium alloy are revealed and the combined improvement in wear and corrosion resistance of AZ31 magnesium alloy is achieved.The modification mechanism in the wear and corrosion resistance of Al ion implanted and H1PIB irradiated AZ31 magnesium alloy are also illustrated in terms of the changes in composition,structure and properties of modified surface.
The Al ion implantation into AZ31 magnesium alloys is carried out at an implantation dose of 2×10~(16),6×10~(16) and 1×10~(17) ions/cm~2 at room temperature and at 300℃.The concentration depth profiles of implanted Al in AZ31 magnesium alloys with an implantation dose of 1×10~(17) ions/cm~2 at room temperature and at 300℃C were a Gaussian-type distribution in the depth up to about 840 and 1200 nm with the maximum Al concentration up to about 10 and 8 at.%respectively,measured by using Rutherford backscattering spectrometry(RBS). The microstructure,which is mainly composed ofα-Mg phase,and small amount of intermetallicβ-Mg_(17)Al_(12) and MgO phase is also observed on the original and implanted samples by X-ray diffraction(XRD).The new diffraction peak ofβphase is observed on the Al ion implanted AZ31 magnesium alloys with the higher implantation dose of 1×10~(17) ions/cm~2 at room temperature,whereas the new diffraction peak ofβphase is observed on the Al ion implanted AZ31 magnesium alloys with the lower implantation dose of 2×10~(16) ions/cm~2 at 300℃.
The combined improvement in wear and corrosion resistance is achieved for the Al ion implanted AZ31 magnesium alloys at room temperature and at 300℃using a reciprocating tribometer in a ball-on-flat configuration where the applied load is 5 and 20 N at a sliding speed of 2 mm/s and potentiodynamic polarization technology in the 0.01 mol/1 NaCl solution with a pH value of 12,respectively.For the Al ion implanted sample with a dose of 2×10~(16) ions/cm~2 at room temperature,the wear volume is reduced by 20%respectively,compared with that of the original sample under a load of 5 N for a sliding time of 10 min,and the wear volume is reduced by 30-40%under a load of 20 N for a sliding time of 20 min.For the Al ion implanted sample with a dose of 6×10~(16) ions/cm~2 at a temperature of 300℃,the wear volume is reduced by 1.5-20%under a load of 20 N for a sliding time of 20 min.Under a load of 5 N,the original sample exhibited a typical abrasive wear mechanism,characterized by microcutting and plastic deformation,and Al ion implantation did not change the wear mechanism of magnesium alloy.Under a load of 20 N for a sliding time of 20 min,the transitions in wear mechanism from severe metallic wear to oxidational wear for the Al ion implanted samples at room temperature and at 300℃were observed.The potentiodynamic polarization curves show that the corrosion resistance of Al ion implanted samples with an. implantation dose of 2×10~(16),6×10~(16) and 1×10~(17) ions/cm~2 at room temperature and at 300℃are superior to that of the original one in the 0.01 mol/l NaCl solution with a pH value of 12. The sample with an implantation dose of 6×10~(16) ions/cm~2 has the superior corrosion resistance,and the corrosion potential and pitting corrosion breakdown potential are 400 and 800 mV higher than those of the original sample,respectively.For the sample implanted with an implantation dose of 1×10~(17) ions/cm~2 at room temperature and at 300℃,corrosion potential is higher 180 and 280 mV,and the pitting corrosion breakdown potential is higher 150 and 220 mV than those of the original sample,in the 0.08 mol/l NaCl solution with a pH value of 12.It is believed that the combined improvement in wear and corrosion resistance for Al ion implanted samples at room temperature and at 300℃is attributed to the solid solution enhancing effects and the second phaseβenhancing effects induced by Al enrichment.
HIPIB irradiation into AZ31 magnesium alloy at ion current densities of 100-300 A/cm~2 with shot number of 1-10 led to a typical surface morphology with crater formation and waviness features in local region due to a selective ablation and disturbance of the molten surface.Compared with the original sample,the microstructure of remelted layer and heat-affected layer are significantly refined with increasing the ion current density and the shot number.HIPIB irradiation results in the significant chemical homogeneity, microstructural refinement and the homogenous redistribution of the second phase ofβon the irradiated surface due to the repetitive rapid melting and resolidification of surface irradiated by HIPIB.
The combined improvement in wear and corrosion resistance is achieved for HIPIB irradiated AZ31 magnesium alloys using a tribometer in a ball-on-disk configuration where the applied load is 0.1-0.5 N at a sliding speed of 0.08 m/s and potentiodynamic polarization technology in the 0.01-0.5 mol/1 NaC1 solution with a pH value of 12,respectively.The irradiated sample at 300 A/cm~2 with 10 shots exhibited the superior wear resistance,the friction coefficient decreased from 0.378 for original sample to 0.338,and the wear volume is reduced about 75%compared with the original one.The friction coefficient for the original and irradiated samples at 300 A/cm~2 with 10 shots decreases from 0.364 and 0.334 at a load of 0.2 N to 0.361 and 0.313 at a load of 0.5 N,and the wear volume is reduced about 40%and 15%compared with the original one,respectively.The wear mechanism for HIPIB irradiated samples is still typical of abrasive wear,however,the degree of abrasive wear is significantly reduced,and the improved wear resistance is characterized by reduced localized plastic deformation and shallower grooves,and the oxidational wear is observed on the local region of wear track.The apparent improvement in corrosion resistance is achieved for all the irradiated samples in 0.01 mol/l NaCl solution with a pH value of 12.The corrosion potential and pitting corrosion breakdown potential for the samples irradiated at 100 A/cm~2 with 5 shots are 560 and 630 mV higher than those of the original sample,respectively.Typical corroded surface morphologies for the original and irradiated samples revealed that the original sample suffered from a severe pitting corrosion attack,leading to the formation of voluminous corrosion products that crack severely during corrosion process.In contrast to the original sample,less pitting corrosion attack is observed for the irradiated samples,indicating the enhanced protective properties of surface formed on the irradiated samples due to remelted effect induced by HIPIB irradiation.Corrosion resistance for both the original and irradiated samples decreased with increasing the Cl~-concentration in NaCI solution,however,improved corrosion resistance of irradiated sample is still obtained in NaCl solution containing higher Cl~- concentration.The chemical homogeneity and microstructural refinement of the irradiated surface induced by HIPIB irradiation are the main reasons for the combined improvement in wear and corrosion resistance of AZ31 magnesium alloys.
引文
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