钛合金表面激光熔覆TiCrAlSi系多主元合金涂层的研究
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摘要
钛合金具有密度低、比强度高、疲劳蠕变性能好、耐蚀性能优异等特点,在航空、航天、船舶、兵器等领域得到较广泛的应用。但是在高温和剧烈摩擦的情况下,钛合金的应用受限于较差的摩擦性能、抗氧化性能和有燃烧的危险(即“钛火”)。表面改性技术在解决这些问题的同时,能够保留块体材料的机械性能,因而受到了广泛的关注。其中,激光表面技术具有极高的加热冷却速率,能精确改进表面性能。多主元合金是一种新的合金设计理念,它包含接近等原子比的多种主要合金元素,而传统合金一般只有一个主要元素。通过选择适当的合金元素,这类合金能得到所需的性能,例如高硬度、良好的热稳定性、优异的耐磨、抗氧化和耐腐蚀性能。因此,多主元合金被看作具有吸引力的表面涂层材料。
本研究的目的是开发能同时提高钛合金耐磨性、抗高温氧化性和阻燃性的多主元合金涂层。采用激光熔覆的方法,在钛合金基体上制得了TiCrAlSi-V和TiCrAlSi-Ni两种多主元合金涂层,研究了激光熔覆工艺参数、微观组织、耐热性、摩擦磨损性能、抗高温氧化性和阻燃性等方面的内容。并用CALPHAD(相图计算)技术分析了涂层的相形成规律和阻燃性能。完成的主要工作和结论如下：
(1)采用优化的激光熔覆工艺在Ti-6A1-4V钛合金基体上激光熔覆制得裂纹和孔洞很少的TiCrAlSi-V和TiCrAlSi-Ni两种多主元合金涂层。
(2)XRD、SEM和EDS分析表明,激光熔覆TiCrAlSi-V多主元合金涂层由(Ti,V)5Si3和BCC相组成；800℃真空退火24小时后,析出了新相Al8(V,Cr)5。激光熔覆TiCrAlSi-Ni多主元合金涂层由(Ti,Cr)5Si3和NiAl相组成；800℃真空退火24小时后,相组成没有发现明显的变化。结果表明,不是所有的多主元合金都会如许多学者所强调的那样,生成简单固溶体。
(3)建立了用于TiCrAlSi-V和TiCrAlSi-Ni多主元合金的热力学数据库。基于这个数据库,采用CALPHAD方法计算出了涂层材料随温度变化平衡相组成的演化规律,并用实验进行了验证。对TiCrAlSi-V合金,实验与计算结果一致；而对TiCrAlSi-Ni合金,实验与计算结果略有出入。
(4)真空退火后,TiCrAlSi-V多主元合金涂层的硬度略有上升,这是由于退火过程中析出了金属间化合物Al8(V,Cr)5。而TiCrAlSi-Ni涂层在热处理前后,硬度没有明显变化。两种涂层的硬度都远大于Ti-6Al-4V钛合金基体。
(5)干滑动磨损实验表明,Ti-6Al-4V钛合金激光熔覆多主元合金涂层后,耐磨性明显提高。在不同的频率下,涂层的比磨损率都远小于钛合金基体,尤其是TiCrAlSi-Ni涂层,比磨损率减小了两个数量级。TiCrAlSi-V涂层的摩擦系数明显小于Ti-6A1-4V钛合金基体。在本研究所采用的实验条件下,钛合金基体的磨损机制为粘着磨损和严重的磨粒磨损,而两种涂层均为轻微磨损,其磨耗过程为氧化、粘着和粘着材料(包括氧化物)的开裂与剥落。
(6)氧化实验表明,两种涂层都能有效提高钛合金在800℃的抗氧化性。TiCrAlSi-V涂层表面形成的氧化层由SiO2、Cr2O3、TiO2、Al2O3和少量的V2O5构成,TiCrAlSi-Ni涂层表面的氧化层由Cr2O3、TiO2、Al2O3和少量的SiO2与NiO构成。两种氧化层都连续致密,没有裂纹和孔洞。
(7)通过计算绝热燃烧温度研究了阻燃性。TiCrAlSi-V和TiCrAlSi-Ni多主元合金的绝热燃烧温度都比Ti-6A1-4V钛合金低,因此两种涂层在理论上都有较好的阻燃性。用激光烧蚀法初步评价了涂层及钛合金基体的阻燃性,实验结果和理论分析一致。
Titanium alloys play an important role in the field of aerospace, aviation, ships and weapons etc. because of their characteristics of low density, high specific strength, good fatigue and creep resistance, and excellent corrosion resistance. Nevertheless, their applications at high service temperature and in wear-intensive situations, have been limited by the poor tribological properties, insufficient oxidation resistance and risk of combustion. Surface modification is an attractive method to solve the aforementioned problems, while combining with the required bulk mechanical properties. Laser surface technology, characterized by an extremely high heating/cooling rate, allows the precise adaptation of surface properties. Multi-principal element alloy, containing several main elements at near equiatomic concentrations, instead of a single major element for the traditional alloy, is a new concept in alloy design. By appropriate selection of the alloying elements, these alloys can have their properties tailored to the desired performance, such as high hardness, good thermal stability, excellent wear, oxidation and corrosion resistance. Due to these properties, multi-principal element alloys are also considered attractive coating materials for enhancing surface behaviour.
The purpose of the present study is to develop multi-principal element alloy coatings that improve simultaneously the oxidation resistance, tribological properties and burn-resistance of titanium alloys. The TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys are deposited by laser cladding on Ti-6Al-4V substrate. The processing parameters, microstructure, thermal stability, tribological properties, oxidation behavior and burn-resistance are investigated. The CALPHAD method is employed to assist the analysis of phase constitution and burn-resistance. The major work completed and the results obtained are as follows:
(1) TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings with few cracks and pores are obtained on Ti-6A1-4V substrates by using the optimized processing parameters.
(2) SEM, XRD and EDS analysis show that, the as-clad TiCrAlSi-V coating is composed of (Ti,V)5Si3and a BCC solid solution. After annealing at800℃for24hours under vacuum, a new phase Al8(V,Cr)5precipites. The as-clad TiCrAlSi-Ni coating is composed of (Ti,Cr)5Si3and NiAl. After annealing at800℃for24hours under vacuum, there is no apparent change in phase composition. The results demonstrate that not all multi-principal element alloys form simple FCC or BCC solid solution phases, which are emphasized by many researchers.
(3) A thermodynamic database for TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys is established. Based on the database, the temperature-dependent equilibrium phase diagram for the coating materials are calculated by using the CALPHAD method. And the results are validated by experiment. The experimental phase composition for TiCrAlSi-V alloy agrees well with the thermodynamic calculations, while there is a small inconsistency for TiCrAlSi-Ni alloy.
(4) After vacuum annealing, there is a small increase of hardness for the laser clad TiCrAlSi-V coating, which is due to the formation of Al8(V,Cr)5. There is no apparent difference of hardness for the TiCrAlSi-Ni coating before and after the heat treatment. Both coatings are much harder than the Ti-6A1-4V substrates.
(5) The dry sliding wear tests showed the wear resistance of Ti-6Al-4V is significantly improved after laser clad TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings. At different frequencies, the specific wear rates of the coatings are much lower than that of the substrates. Especially for the TiCrAlSi-Ni coatings, they reduce the specific wear rates by two orders of magnitude. The friction coefficients of the TiCrAlSi-V coatings are much lower than that of the Ti-6A1-4V substrates. The Ti-6Al-4V substrates suffer adhesive wear and severe abrasive wear. The worn surface morphologies of the TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings indicate that, the test occurred in the mild wear regime, the main material loss mechanism includes oxidation, slight adhesive material transfer and fragmentation and spalling of the adhered material, as well as oxides.
(6) The oxidation tests of Ti-6A1-4V alloys and the multi-principal element alloy coatings show that the laser clad TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings can effectively improve the oxidation resistance of Ti-6A1-4V alloys at800℃in air. The oxide scale formed on TiCrAlSi-V consists of SiO2, Cr2O3, TiO2, Al2O3and a small amount of V2O5, while the oxide scale on TiCrAlSi-Ni consists of Cr2O3, Al2O3, a small amount of NiO and SiO2. Both scales are continuous and dense, without any cracks and pores.
(7) The burn resistance is investigated by calculating adiabatic temperature. The adiabatic temperatures of the TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys are lower than Ti-6Al-4V alloy, indicating good burn resistance of the coatings. A primitive experimental evaluation on the burn resistance is conducted by laser ablation. The result agrees with the theoretical analysis.
本研究的目的是开发能同时提高钛合金耐磨性、抗高温氧化性和阻燃性的多主元合金涂层。采用激光熔覆的方法,在钛合金基体上制得了TiCrAlSi-V和TiCrAlSi-Ni两种多主元合金涂层,研究了激光熔覆工艺参数、微观组织、耐热性、摩擦磨损性能、抗高温氧化性和阻燃性等方面的内容。并用CALPHAD(相图计算)技术分析了涂层的相形成规律和阻燃性能。完成的主要工作和结论如下：
(1)采用优化的激光熔覆工艺在Ti-6A1-4V钛合金基体上激光熔覆制得裂纹和孔洞很少的TiCrAlSi-V和TiCrAlSi-Ni两种多主元合金涂层。
(2)XRD、SEM和EDS分析表明,激光熔覆TiCrAlSi-V多主元合金涂层由(Ti,V)5Si3和BCC相组成；800℃真空退火24小时后,析出了新相Al8(V,Cr)5。激光熔覆TiCrAlSi-Ni多主元合金涂层由(Ti,Cr)5Si3和NiAl相组成；800℃真空退火24小时后,相组成没有发现明显的变化。结果表明,不是所有的多主元合金都会如许多学者所强调的那样,生成简单固溶体。
(3)建立了用于TiCrAlSi-V和TiCrAlSi-Ni多主元合金的热力学数据库。基于这个数据库,采用CALPHAD方法计算出了涂层材料随温度变化平衡相组成的演化规律,并用实验进行了验证。对TiCrAlSi-V合金,实验与计算结果一致；而对TiCrAlSi-Ni合金,实验与计算结果略有出入。
(4)真空退火后,TiCrAlSi-V多主元合金涂层的硬度略有上升,这是由于退火过程中析出了金属间化合物Al8(V,Cr)5。而TiCrAlSi-Ni涂层在热处理前后,硬度没有明显变化。两种涂层的硬度都远大于Ti-6Al-4V钛合金基体。
(5)干滑动磨损实验表明,Ti-6Al-4V钛合金激光熔覆多主元合金涂层后,耐磨性明显提高。在不同的频率下,涂层的比磨损率都远小于钛合金基体,尤其是TiCrAlSi-Ni涂层,比磨损率减小了两个数量级。TiCrAlSi-V涂层的摩擦系数明显小于Ti-6A1-4V钛合金基体。在本研究所采用的实验条件下,钛合金基体的磨损机制为粘着磨损和严重的磨粒磨损,而两种涂层均为轻微磨损,其磨耗过程为氧化、粘着和粘着材料(包括氧化物)的开裂与剥落。
(6)氧化实验表明,两种涂层都能有效提高钛合金在800℃的抗氧化性。TiCrAlSi-V涂层表面形成的氧化层由SiO2、Cr2O3、TiO2、Al2O3和少量的V2O5构成,TiCrAlSi-Ni涂层表面的氧化层由Cr2O3、TiO2、Al2O3和少量的SiO2与NiO构成。两种氧化层都连续致密,没有裂纹和孔洞。
(7)通过计算绝热燃烧温度研究了阻燃性。TiCrAlSi-V和TiCrAlSi-Ni多主元合金的绝热燃烧温度都比Ti-6A1-4V钛合金低,因此两种涂层在理论上都有较好的阻燃性。用激光烧蚀法初步评价了涂层及钛合金基体的阻燃性,实验结果和理论分析一致。
Titanium alloys play an important role in the field of aerospace, aviation, ships and weapons etc. because of their characteristics of low density, high specific strength, good fatigue and creep resistance, and excellent corrosion resistance. Nevertheless, their applications at high service temperature and in wear-intensive situations, have been limited by the poor tribological properties, insufficient oxidation resistance and risk of combustion. Surface modification is an attractive method to solve the aforementioned problems, while combining with the required bulk mechanical properties. Laser surface technology, characterized by an extremely high heating/cooling rate, allows the precise adaptation of surface properties. Multi-principal element alloy, containing several main elements at near equiatomic concentrations, instead of a single major element for the traditional alloy, is a new concept in alloy design. By appropriate selection of the alloying elements, these alloys can have their properties tailored to the desired performance, such as high hardness, good thermal stability, excellent wear, oxidation and corrosion resistance. Due to these properties, multi-principal element alloys are also considered attractive coating materials for enhancing surface behaviour.
The purpose of the present study is to develop multi-principal element alloy coatings that improve simultaneously the oxidation resistance, tribological properties and burn-resistance of titanium alloys. The TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys are deposited by laser cladding on Ti-6Al-4V substrate. The processing parameters, microstructure, thermal stability, tribological properties, oxidation behavior and burn-resistance are investigated. The CALPHAD method is employed to assist the analysis of phase constitution and burn-resistance. The major work completed and the results obtained are as follows:
(1) TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings with few cracks and pores are obtained on Ti-6A1-4V substrates by using the optimized processing parameters.
(2) SEM, XRD and EDS analysis show that, the as-clad TiCrAlSi-V coating is composed of (Ti,V)5Si3and a BCC solid solution. After annealing at800℃for24hours under vacuum, a new phase Al8(V,Cr)5precipites. The as-clad TiCrAlSi-Ni coating is composed of (Ti,Cr)5Si3and NiAl. After annealing at800℃for24hours under vacuum, there is no apparent change in phase composition. The results demonstrate that not all multi-principal element alloys form simple FCC or BCC solid solution phases, which are emphasized by many researchers.
(3) A thermodynamic database for TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys is established. Based on the database, the temperature-dependent equilibrium phase diagram for the coating materials are calculated by using the CALPHAD method. And the results are validated by experiment. The experimental phase composition for TiCrAlSi-V alloy agrees well with the thermodynamic calculations, while there is a small inconsistency for TiCrAlSi-Ni alloy.
(4) After vacuum annealing, there is a small increase of hardness for the laser clad TiCrAlSi-V coating, which is due to the formation of Al8(V,Cr)5. There is no apparent difference of hardness for the TiCrAlSi-Ni coating before and after the heat treatment. Both coatings are much harder than the Ti-6A1-4V substrates.
(5) The dry sliding wear tests showed the wear resistance of Ti-6Al-4V is significantly improved after laser clad TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings. At different frequencies, the specific wear rates of the coatings are much lower than that of the substrates. Especially for the TiCrAlSi-Ni coatings, they reduce the specific wear rates by two orders of magnitude. The friction coefficients of the TiCrAlSi-V coatings are much lower than that of the Ti-6A1-4V substrates. The Ti-6Al-4V substrates suffer adhesive wear and severe abrasive wear. The worn surface morphologies of the TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings indicate that, the test occurred in the mild wear regime, the main material loss mechanism includes oxidation, slight adhesive material transfer and fragmentation and spalling of the adhered material, as well as oxides.
(6) The oxidation tests of Ti-6A1-4V alloys and the multi-principal element alloy coatings show that the laser clad TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloy coatings can effectively improve the oxidation resistance of Ti-6A1-4V alloys at800℃in air. The oxide scale formed on TiCrAlSi-V consists of SiO2, Cr2O3, TiO2, Al2O3and a small amount of V2O5, while the oxide scale on TiCrAlSi-Ni consists of Cr2O3, Al2O3, a small amount of NiO and SiO2. Both scales are continuous and dense, without any cracks and pores.
(7) The burn resistance is investigated by calculating adiabatic temperature. The adiabatic temperatures of the TiCrAlSi-V and TiCrAlSi-Ni multi-principal element alloys are lower than Ti-6Al-4V alloy, indicating good burn resistance of the coatings. A primitive experimental evaluation on the burn resistance is conducted by laser ablation. The result agrees with the theoretical analysis.
引文
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