丙烯腈低聚物还原氧化铜制备氧化亚铜的研究

发布时间：2018-04-29 19:43

本文选题：丙烯腈低聚物 + 氧化亚铜　；参考：《深圳大学》2015年硕士论文

【摘要】：自20世纪70年代起,氧化亚铜作为海洋船舶防污涂料的辅助防污剂被广泛使用。但氧化亚铜与漆料的相容性差,影响深层粒子的有效释放,因此防污寿命仅为2-3年。如何对氧化亚铜进行表面改性,提高其防污性能,已成为当今的研究热点。目前工业上生产氧化亚铜多采用水热法、化学沉积法、电化学法、溶胶凝胶法、辐照还原法、化学气相沉积法和溶剂蒸发法等,这些方法工艺复杂,且成本高、产量低,还有待改进和发展。并且氧化亚铜在空气中易被氧化和发生团聚效应,增加了运输储藏和使用难度。基于以上方面的不足,本论文提出了一条创新的技术路线,即以价格低廉的氧化铜粉末为原料,以液态丙烯腈低聚物(LANO)作为还原剂,经过液相混合和球磨包覆,在惰性气氛下加热烧结制备得到介孔丙烯腈低聚物/氧化亚铜(ANO/Cu2O,简称为AC)纳米复合粒子。所制得的纳米Cu2O由于比表面积大,在实际使用中可减少单位面积使用量而不影响防污效果。外面包覆的ANO具有介孔结构,可以有效防止Cu2O被氧化和发生团聚效应,并且可以有效地控制Cu2O的释放,延长使用时间,降低使用成本。主要研究内容如下:(1)研究不同含量(包括AC10、AC20、AC30、AC40、AC50、AC60、AC70、AC80、AC90)的样品分别在250℃、300℃、350℃和400℃烧结温度下制得的物相和形貌变化规律,结果表明发现AC10-AC40低温烧结得到的产物都是ANO/(Cu/Cu2O);高温烧结产物是棒状结构的ANO/Cu;AC50、AC60和AC70低温烧结产物都是ANO/(Cu O/Cu2O);高温烧结产物是非棒状结构的ANO/Cu;AC80在300℃烧结得到较为纯净的ANO/Cu2O;AC90在350℃的烧结得到较为纯净的ANO/Cu2O,因此通过控制温度和配比可制备得到纯净的ANO/Cu2O;(2)改变溶剂体系制得不同烧结温度下不同含量的样品。利用XRD和TEM研究了水、乙醇和癸醇三种溶剂分别对AC40、AC80、AC90烧结产物的组成和对ANO表面介孔结构及形貌的影响。结果表明溶剂影响ANO的还原性。当Cu含量低于40%时,ANO在溶剂中的还原性顺序为水?乙醇?癸醇。当Cu含量高于40%时,ANO在溶剂中的还原性顺序为乙醇?水?癸醇。这可能是由于乙醇的极性介于水和癸醇之间,并且乙醇溶剂本身具有还原性,在高温下与ANO协同发挥还原作用,因此ANO在乙醇中的还原性最强;(3)根据XRD谱图分析比较了两个系列LANO(Z3和Z0.5)还原氧化铜的强弱。结果表明Z3系列还原性强于Z0.5,因此可降低制备温度。利用SEM谱图对比发现两个系列的的AC粒子分散性不同,其中Z0.5系列的AC粒子分散性较好;(4)选取合适的制备条件下的AC样品进行基础海港挂板实验,测试AC样品的防污性能。结果表明,本实验室合成的AC样品具有良好的防污性能,并且在相对较低含量下就可以表现出良好的防污效果,大大降低了防污成本,具有广阔的应用前景。
[Abstract]:Cuprous oxide has been widely used since 1970s as an auxiliary antifouling agent for marine marine antifouling coatings. But the compatibility of copper oxide with paint is poor, which affects the effective release of deep particles, so the antifouling life is only 2-3 years. How to modify the surface of cuprous oxide and raise its antifouling performance has become a hot spot of research. At present, most of the production of cuprous oxide in industry is hydrothermic, chemical deposition, electrochemistry, sol-gel, irradiation reduction, chemical vapor deposition and solvent evaporation. These methods are complex, high cost, low yield, and need to be improved and developed. And the effect of oxidation and agglomeration of cuprous oxide in air is increased. It is difficult to transport storage and use. Based on the inadequacy of the above aspects, an innovative technical route is proposed in this paper, that is, using low price copper oxide powder as raw material, liquid acrylonitrile oligomer (LANO) as reducing agent, liquid phase mixing and ball milling, and heating and sintering in inert atmosphere to prepare mesoporous acrylonitrile oligomerization. ANO/Cu2O (AC) nanocomposite particles. The prepared nano Cu2O, due to large specific surface area, can reduce the use of unit area without affecting the antifouling effect in actual use. The coated ANO has a mesoporous structure, which can effectively prevent the Cu2O from being oxidized and reunite, and can effectively control Cu2O. The main research contents are as follows: (1) study the changes of phase and morphology of different content (including AC10, AC20, AC30, AC40, AC50, AC60, AC70, AC80, AC90) at 250, 300, 350, and 400 C respectively. The results show that the products of AC10-AC40 low temperature sintering are found. It is ANO/ (Cu/Cu2O); high temperature sintering product is a ANO/Cu of rod like structure; AC50, AC60 and AC70 sintered products are ANO/ (Cu O/Cu2O); high temperature sintering products are non rod like ANO/Cu; AC80 is sintered at 300 degrees Celsius to get a more pure ANO/Cu2O; therefore, the sintering at 350 C is more pure, so the temperature and ratio can be controlled. The pure ANO/Cu2O was obtained. (2) the samples were prepared by changing the solvent system at different sintering temperatures. XRD and TEM were used to study the composition of the three solvents of water, ethanol and Decyl Alcohol on the composition of AC40, AC80, AC90 sintering products and the mesoporous structure and morphology of the ANO surface. The results show that the solvent affects the reducibility of ANO. When the Cu content is low At 40%, the order of ANO in the solvent is water, ethanol and Decyl Alcohol. When the content of Cu is higher than 40%, the reducing order of ANO in the solvent is ethanol water Decyl Alcohol. This may be because the polarity of the ethanol is between water and Decyl Alcohol, and the ethanol solvent itself is reductive, and the ANO is co - reduced with ANO at high temperature, so ANO is in B The reducibility of alcohol is the strongest; (3) analysis and comparison of two series of LANO (Z3 and Z0.5) reducing the strength of copper oxide according to the XRD spectrum. The results show that the reduction of Z3 series is stronger than Z0.5, so the preparation temperature can be reduced. The dispersion of AC particles in the two series is different with the SEM spectrum, and the Z0.5 series AC particle dispersion is better; (4) the selection of AC particles is better. The AC samples under the suitable preparation conditions are carried out on the basis of the seaport plate experiment to test the antifouling properties of the AC samples. The results show that the AC samples synthesized in this laboratory have good antifouling performance and can show good antifouling effect under relatively low content, greatly reducing the cost of antifouling, and has a broad application prospect.

【学位授予单位】：深圳大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ131.21

【参考文献】