抗氧化超细铜粉和铜导体浆料的制备及性能研究

发布时间：2018-05-13 07:51

本文选题：超细铜粉 + 铜盐　；参考：《昆明理工大学》2017年硕士论文

【摘要】：超细铜粉由于具有小尺寸效应、表面界面效应、量子尺度效应和量子隧道效应等基本特征,因此在力学、电学、化学等领域有许多优势。本论文采用液相两步还原法来制备超细铜粉,首先采用葡萄糖预还原制得氧化亚铜,然后选用其它还原剂进行二次还原制得超细铜粉。实验设计两条技术路线:一条是选用不同铜盐(乙酸铜、氯化铜、硫酸铜和硝酸铜)制得C1、C2、C3和C4超细铜粉;另一条是选用不同二次还原剂(水合肼、次亚磷酸钠、抗坏血酸和硼氢化钠)制备出C5、C6、C7和C8超细铜粉,然后对超细铜粉元素种类、微观形貌、粒径分布、松装密度以及导电性进行表征,从中选择较佳铜盐和二次还原剂。研究结果表明:当铜盐选用硫酸铜时制得C3铜粉为类球形,粒径分布相对均匀,松装密度最大可达1.65 g/cm3,电阻最小为0.037Ω;当选择水合肼为二次还原剂时,制得C5铜粉为球形,粒径分布均匀,平均粒径为1.89μm,松装密度最大可达1.78 g/cm3,电阻最小为6.71mΩ,这为制备抗氧化超细铜粉提供了科学依据。以铜粉、玻璃粉和有机载体为原料可制备铜导体浆料,经过研磨、丝网印刷、流平、烘干、烧结等工艺,可在陶瓷基片上制得铜膜,广泛应用于现代化技术领域。玻璃粉作为铜导体浆料中不可或缺的一部分,在铜浆烧结时与铜颗粒形成网络状结构组织,调节铜浆热膨胀系数,并满足电极和基板粘结强度要求,因此玻璃粉组成及其含量对铜膜微观形貌、导电性、附着力、抗氧化性和抗老化性能有重要影响。实验设计两条技术路线:一条是选择四种不同组成玻璃粉(SiO2-B2O3-CaO、SiO2-B2O3-Sb2O3、SiO2-B2O3-ZnO、SiO2-B2O3-TiO2),此时铜浆中玻璃粉含量为1.6wt%,制得G1、G2、G3和G4铜膜:另一条是控制铜浆中玻璃粉含量(1.6wt%、3.2wt%、4.8wt%)制得G3、G5和G6铜膜,然后对铜膜元素种类、微观形貌、导电性、附着力和氧化增重等性能进行表征,从中选择最佳玻璃粉组成及其含量。研究结果表明:当玻璃粉组成为SiO2-B2O3-2nO时,制得铜膜G3表面平整,孔洞较少,导电性较好,附着力较大;当玻璃粉含量为4.8wt%时,制得铜膜G6较致密,方阻为9.5mΩ/□,附着力为24N/mm2。为验证G6铜膜使用可靠性,对其进行抗氧化性和抗老化性能测试,发现G6铜膜室温氧化28天后增重率为3.5%,电阻变化率为0.79%;经20℃～160℃高温老化后其电阻变化率为12.63%,氧化增重率为4.63%,具有良好抗氧化性和抗老化性能。
[Abstract]:The ultrafine copper powder has many advantages, such as small size effect, surface interface effect, quantum scale effect and quantum tunneling effect. Therefore, it has many advantages in the fields of mechanics, electricity, chemistry and so on. In this paper, the superfine copper powder was prepared by two step reduction method in liquid phase. First, the copper oxide was prepared by glucose prereduction, and then other reduction was selected. The ultrafine copper powder was prepared by two times reduction. Two technical routes were designed: one was made of copper salts (copper acetate, copper chloride, copper sulfate and copper nitrate) made of C1, C2, C3 and C4 ultrafine copper powder; the other was the preparation of C5, C6, C7 and C8 ultrafine copper with two different reductants (hydrazine, sodium hypophosphite, ascorbic acid and sodium borohydride). Powder, then characterizing the types, micromorphology, particle size distribution, bulk density and conductivity of superfine copper powder, select better copper salt and two reducing agent. The results show that when copper salt is made of copper sulfate, the C3 copper powder is spherical, the particle size distribution is relatively uniform, the bulk density is up to 1.65 g/cm3, and the minimum resistance is 0.03. 7 Omega, when hydrazine hydrate is selected as the two reducing agent, the C5 copper powder is spherical, the particle size distribution is uniform, the average particle size is 1.89 mu m, the bulk density is up to 1.78 g/cm3 and the resistance minimum is 6.71m Omega. This provides a scientific basis for the preparation of antioxidant superfine copper powder. Copper powder, glass powder and organic carrier can be used as raw materials to prepare copper conductor slurry. Grinding, screen printing, leveling, drying, sintering and so on, can be made of copper film on ceramic substrate and widely used in modern technology. As an integral part of the copper conductor paste, glass powder forms a network structure with copper particles during the sintering of copper slurry, regulates the thermal expansion coefficient of copper pulp and satisfies the bonding strength between the electrode and the substrate. The composition and content of glass powder have important influence on the microstructure, conductivity, adhesion, oxidation resistance and aging resistance of the copper film. Two technical routes are designed: one is to choose four different kinds of glass powder (SiO2-B2O3-CaO, SiO2-B2O3-Sb2O3, SiO2-B2O3-ZnO, SiO2-B2O3-TiO2), and the content of glass powder in the copper slurry is 1. .6wt%, G1, G2, G3 and G4 copper films are prepared. The other is to control the glass powder content in the copper slurry (1.6wt%, 3.2wt%, 4.8wt%) to produce G3, G5 and G6 copper films. Then the properties of copper film elements, micromorphology, electrical conductivity, adhesion and oxidation weight gain are characterized, and the optimum composition and content of glass powder are selected. The results show that the composition of glass powder is made up of glass powder. When SiO2-B2O3-2nO, the copper film G3 surface is smooth, the hole is less, the conductivity is better, and the adhesion is great. When the glass powder content is 4.8wt%, the copper film G6 is more compact, the square resistance is 9.5m OMEGA / *, the adhesion is 24N/mm2. to verify the reliability of the G6 copper film, and the oxidation resistance and the aging resistance of the copper film are tested. It is found that the G6 copper film is oxidized at room temperature 28. The weight gain rate is 3.5% and the resistance change rate is 0.79%. The resistance change rate is 12.63% and the oxidation weight gain rate is 4.63% after high temperature aging at 20 ~ 160 C. It has good oxidation resistance and aging resistance.

【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TG146.11;TM241

【参考文献】