本文選題：丙烯腈低聚物 + 氧化亞銅��； 參考：《深圳大學(xué)》2015年碩士論文

【摘要】：自20世紀70年代起,氧化亞銅作為海洋船舶防污涂料的輔助防污劑被廣泛使用。但氧化亞銅與漆料的相容性差,影響深層粒子的有效釋放,因此防污壽命僅為2-3年。如何對氧化亞銅進行表面改性,提高其防污性能,已成為當(dāng)今的研究熱點。目前工業(yè)上生產(chǎn)氧化亞銅多采用水熱法、化學(xué)沉積法、電化學(xué)法、溶膠凝膠法、輻照還原法、化學(xué)氣相沉積法和溶劑蒸發(fā)法等,這些方法工藝復(fù)雜,且成本高、產(chǎn)量低,還有待改進和發(fā)展。并且氧化亞銅在空氣中易被氧化和發(fā)生團聚效應(yīng),增加了運輸儲藏和使用難度�；谝陨戏矫娴牟蛔�,本論文提出了一條創(chuàng)新的技術(shù)路線,即以價格低廉的氧化銅粉末為原料,以液態(tài)丙烯腈低聚物(LANO)作為還原劑,經(jīng)過液相混合和球磨包覆,在惰性氣氛下加熱燒結(jié)制備得到介孔丙烯腈低聚物/氧化亞銅(ANO/Cu2O,簡稱為AC)納米復(fù)合粒子。所制得的納米Cu2O由于比表面積大,在實際使用中可減少單位面積使用量而不影響防污效果。外面包覆的ANO具有介孔結(jié)構(gòu),可以有效防止Cu2O被氧化和發(fā)生團聚效應(yīng),并且可以有效地控制Cu2O的釋放,延長使用時間,降低使用成本。主要研究內(nèi)容如下:(1)研究不同含量(包括AC10、AC20、AC30、AC40、AC50、AC60、AC70、AC80、AC90)的樣品分別在250℃、300℃、350℃和400℃燒結(jié)溫度下制得的物相和形貌變化規(guī)律,結(jié)果表明發(fā)現(xiàn)AC10-AC40低溫?zé)Y(jié)得到的產(chǎn)物都是ANO/(Cu/Cu2O);高溫?zé)Y(jié)產(chǎn)物是棒狀結(jié)構(gòu)的ANO/Cu;AC50、AC60和AC70低溫?zé)Y(jié)產(chǎn)物都是ANO/(Cu O/Cu2O);高溫?zé)Y(jié)產(chǎn)物是非棒狀結(jié)構(gòu)的ANO/Cu;AC80在300℃燒結(jié)得到較為純凈的ANO/Cu2O;AC90在350℃的燒結(jié)得到較為純凈的ANO/Cu2O,因此通過控制溫度和配比可制備得到純凈的ANO/Cu2O;(2)改變?nèi)軇w系制得不同燒結(jié)溫度下不同含量的樣品。利用XRD和TEM研究了水、乙醇和癸醇三種溶劑分別對AC40、AC80、AC90燒結(jié)產(chǎn)物的組成和對ANO表面介孔結(jié)構(gòu)及形貌的影響。結(jié)果表明溶劑影響ANO的還原性。當(dāng)Cu含量低于40%時,ANO在溶劑中的還原性順序為水?乙醇?癸醇。當(dāng)Cu含量高于40%時,ANO在溶劑中的還原性順序為乙醇?水?癸醇。這可能是由于乙醇的極性介于水和癸醇之間,并且乙醇溶劑本身具有還原性,在高溫下與ANO協(xié)同發(fā)揮還原作用,因此ANO在乙醇中的還原性最強;(3)根據(jù)XRD譜圖分析比較了兩個系列LANO(Z3和Z0.5)還原氧化銅的強弱。結(jié)果表明Z3系列還原性強于Z0.5,因此可降低制備溫度。利用SEM譜圖對比發(fā)現(xiàn)兩個系列的的AC粒子分散性不同,其中Z0.5系列的AC粒子分散性較好;(4)選取合適的制備條件下的AC樣品進行基礎(chǔ)海港掛板實驗,測試AC樣品的防污性能。結(jié)果表明,本實驗室合成的AC樣品具有良好的防污性能,并且在相對較低含量下就可以表現(xiàn)出良好的防污效果,大大降低了防污成本,具有廣闊的應(yīng)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.

【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ131.21

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