铜材料的激光表面强化研究
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摘要
铜及铜合金因其优异的导电导热性能而广泛应用于电子、电力、冶金、航空航天等工业领域。但是铜的强度较低,不能完全满足工业应用,尤其是一些极端条件下使用的零部件,如电磁炮导轨、高铁机车电力线等。强度的提高一直是铜合金研究的主要方向,传统方法制备的铜合金在强度显著提高的同时,却是以牺牲其导电性能为代价的,且导电性随着合金化程度的提高而降低；而表面改性技术则可以实现增强表面强度且保持铜合金整体的高导电性,激光技术在众多表面改性技术中因其独特的优势而具有较强的竞争力,已广泛应用于工业制造领域中。但目前利用激光技术对铜合金进行表面强化的研究较少,主要受铜的光反射率高、导热快等特性影响。因此,如何寻找或改进工艺,有效地提高铜材料表面强度是目前激光强化铜合金技术研究的重点。
本论文研究目的是利用激光技术对纯铜进行表面强化,使其兼具表面高耐磨性和整体高导电性。基于此,通过对激光表面强化的工艺设计,选择相对激光熔覆而言对导电性影响更小的激光合金化工艺,并使用预置粉末法来提高基体的光吸收；根据合金化材料的选择原则使用润湿性较好的Ni基合金粉末作为强化材料。通过大量前期实验进行工艺优化,获得了最佳参数,不同样品尺寸对应的工艺参数略有不同,重点研究了扫描速度对合金强化层的组织和性能的影响。在此基础上,使用Ni基合金对纯铜进行表面强化,然后利用激光原位合成技术分别将两种陶瓷颗粒(TaC和NbC)加入Ni基合金强化层以提高其耐磨性,分析了不同合金强化层的组织特征和形成机理,研究了样品的显微硬度、耐磨性能和导电性能的变化。主要结论如下：
1.通过预涂粉末方法提高纯铜对CO2激光的吸收,有效完成铜基材的激光表面强化,工艺参数：基材尺寸50mm×30mm×5mm,激光功率2.2kW,扫描速度4mm/s,离焦量50mm,预涂层厚度0.9mm,搭接率40%。而在基材尺寸为50mm×25mm×5mm,只需激光功率改为2kW即可。
2.扫描速度是本论文工艺中的关键参数,随扫描速度在一定范围内的增加,晶粒细化,硬度提高,合金化程度高,稀释率大,因此可以制备出表面高耐磨的高导电铜基材料。
3.强化层均无裂纹,组织细小、致密,均匀弥散分布在基体中,具有典型的快速凝固特征。(Cu, Ni, Fe)固溶体的形成表明Ni基合金与铜材料有很好的浸润性,为冶金结合。
4.Ni合金强化层的平均硬度高达HV0.1650,是纯铜基材的7倍；耐磨性提高了4倍,主要是颗粒强化、固溶强化和细晶强化共同作用的结果。而两种陶瓷颗粒强化层的硬度和耐磨性均有显著提高,其中TaC颗粒强化层效果更好,平均硬度是Ni基合金强化层的1.56倍；磨损失重仅为Ni基合金强化层的2/5。这主要归因于原位生成的细小的高硬度的陶瓷颗粒及其弥散分布。
5.激光表面强化技术并未使铜基材的导电性能明显降低,而导电性能的下降程度取决于合金化程度(稀释率)的影响,稀释率大,则导电率高,合适的稀释率可以保持导电率在90%IACS以上。因此,优化工艺参数控制合适的稀释率是制备出表面高耐磨高导电铜基复合材料的关键。
6.铜材料的导电性能主要受Ni基合金的影响,而受陶瓷颗粒的加入影响很小。不同的陶瓷颗粒对导电性能的影响有所差别,就本文两种陶瓷颗粒比较而言,NbC颗粒的加入影响略小。适量加入陶瓷颗粒可以大幅提高铜材料的表面性能而对导电性能仅有微小的影响,为制备陶瓷颗粒增强表面改性铜基复合材料提供了实验基础。
7.相对于其他表面技术,激光表面强化使合金层与基材形成了牢固的冶金结合,而且极大地提高了表面性能,甚至赋予表面特殊性能,扩大了铜合金的应用范围,具有很好的经济效益和应用前景。
Copper and its alloys with excellent electrical and thermal conductivity are widely applied to electronics, electricity, metallurgy, aerospace industrial fields, etc. However, the low strength of copper are unable to meet all the requirements of the applications in industry, especially the parts used in extreme conditions, such as the conducting rails of electromagnetic railgun, contact wires for high speed electric railway, etc. The enhancement of strength is always primary investigation in copper alloys. Copper alloys prepared by traditional methods have the strength enhanced at the expense of its conductive properties, which lowers with increasing the strength of alloys. Surface modification technique (SMT) attracts wide attentions due to enhanced surface strength and remaining high conductive properties of the integral copper alloy. In all SMTs, laser technique possesses stronger competition and is widely used in the industrial manufacturing field. Whereas, so far, the investigation of employing laser technique to enhance the strength of copper alloys is relatively less because of high reflection and rapid thermal conductivity of copper. Consequently, finding or improving technology to enhance effectively surface strength of copper is the emphases of laser surface modification on copper.
The intention of the dissertation is to strengthen the surface of copper employing laser surface modification to confer the surface with high wear resistance and high electrical conductivity. For this purpose, the technology for laser surface modification of copper is designed. Laser surface alloying is selected because it has less influence on electrical conductivity of copper than laser cladding. The light absorption of copper is increased with pre-placed powders. Ni-based alloy powders with better wettability are used as strengthening material depending on selecting principle of alloying materials. The optimal parameters have been obtained through a large amount of prior experiments, which have small difference for different sizes of samples. The effects of scanning speed on microstructure and properties are investigated especially. Based on these works, firstly, the surface of copper is strengthened by employing Ni-based alloy, and then two ceramic particles (TaC and NbC) are added into Ni-based alloy layer by in-situ laser synthesis, respectively. The microstructure and formation mechanism of three modified layers are discussed. The micro-hardness, wear resistance and electrical conductivity are investigated also. The primary conclusions are as follows:
1. The absorption to CO2laser of copper is improved through pre-placed powders. Therefore, laser surface modification of copper is accomplished with low laser power. The optimal parameters are as follows:copper substrate sizes,50mm x30mm x5mm; laser power,2.2kW; scanning speed,4mm/s; defocusing amount,50mm; depth of pre-placed powders,0.9mm; overlapping ratio,40%. For copper substrate with sizes of50mm x25mm x5mm, laser power of2kW is enough.
2. Scanning speed is key parameter of laser surface modification in the dissertation. With increasing the scanning speed within a certain scope, grain refinement, increased hardness, high alloying degree and high dilution rate are obtained. Consequently, Cu-based materials are prepared with high surface wear resistance and high integral electrical conductivity.
3. All of three modified layers are free from cracks with the characteristic of rapid solidification, which have homogeneous fine microstructures dispersed uniformly in the matrix. The presence of (Cu, Ni, Fe) solid solution exhibits good wettability between Ni-based alloy and copper, and the formation of metallurgical bonding between the modified layer and the substrate.
4. The average hardness of Ni-based alloy modified layer is enhanced to HV0.1650, which is7times of that of copper substrate. The wear resistance is improved by4times. It is attributed to particulate reinforcement, solid solution strengthening and grain refinement. The hardness and wear resistance of two ceramic particles reinforced Ni-based alloy modified layer are improved remarkably. TaC reinforcements has better effects on hardness and wear resistance of the modified layer, which has average hardness of1.56times and wear mass loss of2/5of Ni-based alloy modified layer. This result is attributed to the presence and the uniform distribution of in-situ synthesized ceramic particles.
5. The electrical conductivity of copper substrate is slightly affected by laser surface modification. The level of decrease of electrical conductivity depends on alloying degree (dilution rate). High dilution rate leads to high electrical conductivity. The electrical conductivity can remain above90%IACS with suitable dilution rate. Therefore, optimizing parameters to control suitable dilution rate is critical to prepare Cu-based composite material with high surface wear resistance and high integral electrical conductivity.
6. The electrical conductivity is affected primarily by Ni-based alloy. Adding ceramic particles have little influence on it. The influence of different ceramic particles on electrical conductivity is not same. For the two ceramic particles in this dissertation, the addition of NbC particles has less effect. Suitable doping of ceramic particles can improve greatly the surface property and has little effect on the electrical conductivity, which provides primary experimental foundation to prepare particulate reinforced surface modified Cu-based composite materials.
7. Comparing to other surface techniques, laser surface modification leads to metallurgical bonding between the modified layer and the substrate, and can enhance the characteristics of the metal surface, especially gives the surface special characteristics. It breaks the using limits of copper alloys, which possesses better economic benefits and promising applications.
本论文研究目的是利用激光技术对纯铜进行表面强化,使其兼具表面高耐磨性和整体高导电性。基于此,通过对激光表面强化的工艺设计,选择相对激光熔覆而言对导电性影响更小的激光合金化工艺,并使用预置粉末法来提高基体的光吸收；根据合金化材料的选择原则使用润湿性较好的Ni基合金粉末作为强化材料。通过大量前期实验进行工艺优化,获得了最佳参数,不同样品尺寸对应的工艺参数略有不同,重点研究了扫描速度对合金强化层的组织和性能的影响。在此基础上,使用Ni基合金对纯铜进行表面强化,然后利用激光原位合成技术分别将两种陶瓷颗粒(TaC和NbC)加入Ni基合金强化层以提高其耐磨性,分析了不同合金强化层的组织特征和形成机理,研究了样品的显微硬度、耐磨性能和导电性能的变化。主要结论如下：
1.通过预涂粉末方法提高纯铜对CO2激光的吸收,有效完成铜基材的激光表面强化,工艺参数：基材尺寸50mm×30mm×5mm,激光功率2.2kW,扫描速度4mm/s,离焦量50mm,预涂层厚度0.9mm,搭接率40%。而在基材尺寸为50mm×25mm×5mm,只需激光功率改为2kW即可。
2.扫描速度是本论文工艺中的关键参数,随扫描速度在一定范围内的增加,晶粒细化,硬度提高,合金化程度高,稀释率大,因此可以制备出表面高耐磨的高导电铜基材料。
3.强化层均无裂纹,组织细小、致密,均匀弥散分布在基体中,具有典型的快速凝固特征。(Cu, Ni, Fe)固溶体的形成表明Ni基合金与铜材料有很好的浸润性,为冶金结合。
4.Ni合金强化层的平均硬度高达HV0.1650,是纯铜基材的7倍；耐磨性提高了4倍,主要是颗粒强化、固溶强化和细晶强化共同作用的结果。而两种陶瓷颗粒强化层的硬度和耐磨性均有显著提高,其中TaC颗粒强化层效果更好,平均硬度是Ni基合金强化层的1.56倍；磨损失重仅为Ni基合金强化层的2/5。这主要归因于原位生成的细小的高硬度的陶瓷颗粒及其弥散分布。
5.激光表面强化技术并未使铜基材的导电性能明显降低,而导电性能的下降程度取决于合金化程度(稀释率)的影响,稀释率大,则导电率高,合适的稀释率可以保持导电率在90%IACS以上。因此,优化工艺参数控制合适的稀释率是制备出表面高耐磨高导电铜基复合材料的关键。
6.铜材料的导电性能主要受Ni基合金的影响,而受陶瓷颗粒的加入影响很小。不同的陶瓷颗粒对导电性能的影响有所差别,就本文两种陶瓷颗粒比较而言,NbC颗粒的加入影响略小。适量加入陶瓷颗粒可以大幅提高铜材料的表面性能而对导电性能仅有微小的影响,为制备陶瓷颗粒增强表面改性铜基复合材料提供了实验基础。
7.相对于其他表面技术,激光表面强化使合金层与基材形成了牢固的冶金结合,而且极大地提高了表面性能,甚至赋予表面特殊性能,扩大了铜合金的应用范围,具有很好的经济效益和应用前景。
Copper and its alloys with excellent electrical and thermal conductivity are widely applied to electronics, electricity, metallurgy, aerospace industrial fields, etc. However, the low strength of copper are unable to meet all the requirements of the applications in industry, especially the parts used in extreme conditions, such as the conducting rails of electromagnetic railgun, contact wires for high speed electric railway, etc. The enhancement of strength is always primary investigation in copper alloys. Copper alloys prepared by traditional methods have the strength enhanced at the expense of its conductive properties, which lowers with increasing the strength of alloys. Surface modification technique (SMT) attracts wide attentions due to enhanced surface strength and remaining high conductive properties of the integral copper alloy. In all SMTs, laser technique possesses stronger competition and is widely used in the industrial manufacturing field. Whereas, so far, the investigation of employing laser technique to enhance the strength of copper alloys is relatively less because of high reflection and rapid thermal conductivity of copper. Consequently, finding or improving technology to enhance effectively surface strength of copper is the emphases of laser surface modification on copper.
The intention of the dissertation is to strengthen the surface of copper employing laser surface modification to confer the surface with high wear resistance and high electrical conductivity. For this purpose, the technology for laser surface modification of copper is designed. Laser surface alloying is selected because it has less influence on electrical conductivity of copper than laser cladding. The light absorption of copper is increased with pre-placed powders. Ni-based alloy powders with better wettability are used as strengthening material depending on selecting principle of alloying materials. The optimal parameters have been obtained through a large amount of prior experiments, which have small difference for different sizes of samples. The effects of scanning speed on microstructure and properties are investigated especially. Based on these works, firstly, the surface of copper is strengthened by employing Ni-based alloy, and then two ceramic particles (TaC and NbC) are added into Ni-based alloy layer by in-situ laser synthesis, respectively. The microstructure and formation mechanism of three modified layers are discussed. The micro-hardness, wear resistance and electrical conductivity are investigated also. The primary conclusions are as follows:
1. The absorption to CO2laser of copper is improved through pre-placed powders. Therefore, laser surface modification of copper is accomplished with low laser power. The optimal parameters are as follows:copper substrate sizes,50mm x30mm x5mm; laser power,2.2kW; scanning speed,4mm/s; defocusing amount,50mm; depth of pre-placed powders,0.9mm; overlapping ratio,40%. For copper substrate with sizes of50mm x25mm x5mm, laser power of2kW is enough.
2. Scanning speed is key parameter of laser surface modification in the dissertation. With increasing the scanning speed within a certain scope, grain refinement, increased hardness, high alloying degree and high dilution rate are obtained. Consequently, Cu-based materials are prepared with high surface wear resistance and high integral electrical conductivity.
3. All of three modified layers are free from cracks with the characteristic of rapid solidification, which have homogeneous fine microstructures dispersed uniformly in the matrix. The presence of (Cu, Ni, Fe) solid solution exhibits good wettability between Ni-based alloy and copper, and the formation of metallurgical bonding between the modified layer and the substrate.
4. The average hardness of Ni-based alloy modified layer is enhanced to HV0.1650, which is7times of that of copper substrate. The wear resistance is improved by4times. It is attributed to particulate reinforcement, solid solution strengthening and grain refinement. The hardness and wear resistance of two ceramic particles reinforced Ni-based alloy modified layer are improved remarkably. TaC reinforcements has better effects on hardness and wear resistance of the modified layer, which has average hardness of1.56times and wear mass loss of2/5of Ni-based alloy modified layer. This result is attributed to the presence and the uniform distribution of in-situ synthesized ceramic particles.
5. The electrical conductivity of copper substrate is slightly affected by laser surface modification. The level of decrease of electrical conductivity depends on alloying degree (dilution rate). High dilution rate leads to high electrical conductivity. The electrical conductivity can remain above90%IACS with suitable dilution rate. Therefore, optimizing parameters to control suitable dilution rate is critical to prepare Cu-based composite material with high surface wear resistance and high integral electrical conductivity.
6. The electrical conductivity is affected primarily by Ni-based alloy. Adding ceramic particles have little influence on it. The influence of different ceramic particles on electrical conductivity is not same. For the two ceramic particles in this dissertation, the addition of NbC particles has less effect. Suitable doping of ceramic particles can improve greatly the surface property and has little effect on the electrical conductivity, which provides primary experimental foundation to prepare particulate reinforced surface modified Cu-based composite materials.
7. Comparing to other surface techniques, laser surface modification leads to metallurgical bonding between the modified layer and the substrate, and can enhance the characteristics of the metal surface, especially gives the surface special characteristics. It breaks the using limits of copper alloys, which possesses better economic benefits and promising applications.
引文
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