基于3D打印的导电复合材料基板制备及在铜电解精炼中的应用

发布时间：2018-06-16 03:29

本文选题：碳纳米管 + ABS　；参考：《桂林理工大学》2017年硕士论文

【摘要】：电解精炼铜是实现铜纯化的有效手段。在电解精炼铜设备中阴极基板多为工业纯钛,其价格昂贵,而且在电解过程中会不断损耗,同时剥离过程也需要专用的设备。本论文探索将工程塑ABS(料丙烯腈-丁二烯-苯乙烯塑料)与多壁碳纳米管(MWNTs)经双螺杆共混制备导电3D打印材料,借助3D打印技术便捷制备实验室铜电解槽及基板,采用纳米导电复合材料基板代替纯钛,研究了MWNTs/ABS导电基板铜的电沉积过程及电解铜形貌。围绕导电3D打印耗材的制备,本论文先后制备了MWNTs/ABS颗粒复合材料、MWNTs/掺混型ABS复合材料以及SBS(苯乙烯系热塑性弹性体)增韧掺混型MWNTs/ABS复合材料,对材料进行了力学性能测试、动态力学性能测试、拉曼光谱测试、断口SEM测试、热稳定性测试、熔体流速测试,得到以下结论:1、ABS颗粒制备导电复合材料时,随着MWNTs含量增加复合材料的导电性、拉伸强度、硬度、储能模量、损失模量、玻璃转化温度不断提高,复合材料的热稳定性未受到明显影响,但是韧性以及熔体流速下降;复合材料的导电性随双螺杆共混次数增加而提高。2、掺混型ABS的拉伸强度、弯曲强度随着ABS高胶粉含量增加而减小,冲击强度不断提高,当ABS高胶粉∶SAN树脂为25∶75时制备的掺混型ABS性能最接近通用级别ABS。掺混型MWNTs/ABS复合材料的导电性、拉伸强度、硬度、储能模量、损失模量、玻璃转化温度随着MWNTs含量的增加不断提高,但是冲击强度以及熔体流速变小,复合材料变脆,而且当添加量超过5%之后复合材料的热稳定性下降。3、SBS添加到复合材料中后,复合材料的韧性以及热稳定性得到了一定程度的提高,但导电性、拉伸强度、弯曲强度储能模量、损失模量随着添加量的增加而降低,MWNTs在ABS中的分散性变差。4、在优化条件下,制备出符合FDM型3D打印使用要求的导电功能(直径1.75 mm)打印耗材,并且直接打印制备出实验室铜电解槽及导电复合材料基板。5、在硫酸体系电解液中进行导电复合材料基板电解精炼铜实验,结果发现导电复合材料基板导电性能良好,XRD分析表明沉积物成分为立方晶系铜单质,其结构致密且便于剥离。循环伏安分析表明,Cu2+在导电复合材料表面晶粒形核以及晶粒长大过程与纯钛基板相近。SEM分析发现,如果在电解液中添加微量的明胶和硫脲,铜在导电复合材料基板表面的沉积更加平整。
[Abstract]:Electrolytic refining of copper is an effective means of copper purification. In the electrolytic copper refining equipment, the cathode substrate is mostly industrial pure titanium, which is expensive, and will be continuously worn out in the electrolysis process. At the same time, special equipment is also needed in the stripping process. In this paper, the conductive 3D printing materials were prepared by blending engineering plastic ABS (acrylonitrile-butadiene-styrene plastics) with multi-walled carbon nanotubes (MWNTs) by twin-screw, and the copper electrolysis cells and substrates were prepared conveniently by 3D printing technology. The electrodeposition process and electrolysis copper morphology of MWNTs / ABS conductive substrates were studied by using nano-conductive composite substrates instead of pure titanium. According to the fabrication of conductive 3D printing consumables, MWNTs / ABS composites and SBS toughened MWNTs / ABS composites were prepared successively. The mechanical properties of MWNTs / ABS composites were tested. Dynamic mechanical properties, Raman spectroscopy, fracture SEM, thermal stability test, melt flow rate test, obtained the following conclusion: when the content of MWNTs increases, the electrical conductivity and tensile strength of the composites are increased with the increase of MWNTs content. The hardness, storage modulus, loss modulus, glass transition temperature and the thermal stability of the composites were not significantly affected, but the toughness and melt flow rate decreased. The electrical conductivity of the composite increases with the increase of the number of twin-screw blending. The tensile strength and bending strength of the blended ABS decrease with the increase of the content of ABS high rubber powder, and the impact strength increases continuously. When ABS high rubber powder / San resin is 25:75, the properties of blended ABS are the closest to that of general grade ABS. The electrical conductivity, tensile strength, hardness, storage modulus, loss modulus and glass conversion temperature of MWNTs / ABS composites increase with the increase of MWNTs content, but the impact strength and melt flow rate decrease, and the composites become brittle. Moreover, the thermal stability of the composites decreased after adding more than 5% SBS. The toughness and thermal stability of the composites were improved to some extent, but the electrical conductivity, tensile strength, flexural strength and storage modulus of energy storage were improved to some extent. The loss modulus decreases the dispersion of MWNTs in ABS with the increase of adding amount. Under the optimized conditions, the conductive function (diameter 1.75 mm) which meets the requirements of FDM 3D printing is prepared. The lab copper electrolysis cell and the conductive composite substrate. 5 were prepared by direct printing. The copper refining experiment was carried out in the electrolyte of the sulfuric acid system by conducting the electrolysis of the conductive composite material substrate. The results showed that the conductive properties of conductive composites were good. XRD analysis showed that the sediment composition was cubic system copper simple material, its structure was compact and easy to peel off. The cyclic voltammetry analysis shows that the nucleation and grain growth process of Cu2 on the surface of conductive composite is similar to that of pure titanium substrate. SEM analysis shows that if microamounts of gelatin and thiourea are added to the electrolyte, The deposition of copper on the substrate of conductive composite is more smooth.
【学位授予单位】：桂林理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TF811;TB332

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