摘要
随着对原子级制造工艺越来越多的认识,纳米技术成为21世纪各个领域都十分关心的重点技术,碳纳米管(CNTs)以其优异的性能倍受科学界的关注,被认为具有广泛的应用前景。碳纳米管作为一种新型的材料,显示出了现有传统纤维无法比拟的优异特性,有望成为先进复合材料的理想增强体。尤其是在聚合物基和无机非金属基复合材料方面,含CNTs复合材料的研究已取得了不少研究成果,在改善基体性能方面取得了明显效果。
为了对CNTs与聚合物、金属粉末的复合行为及体系性能进行更深入的研究,本论文对CNTs进行表面改性,并将其与环氧树脂和金属银进行复合,以改进环氧树脂材料的力学性能、电学性能；将CNTs与微／纳米铁粉复合,并对体系的流变特性进行系统评价,以研究其对金属粉末注射成型的影响,以解决注射成型工艺中存在的一些关键问题。
主要研究结果如下：
1.采用超声波分散及真空浇铸成型法制备的碳纳米管/环氧树脂复合材料能明显提高环氧树脂的力学性能和电性能。碳纳米管的添加量在1.7wt%以下时能有效提高复合材料的力学性能。当碳纳米管的添加量为0.75wt%时,复合材料的综合力学性能最佳,其拉伸强度、拉伸模量、断裂伸长率较环氧树脂基体分别提高了18.2%,16.1%和85.5%。进一步分析表明：断裂时能量主要分三部分吸收,分别是碳纳米管的拔出功,碳纳米管的断裂功以及碳纳米管与基体的脱粘功。其中碳纳米管拔出时吸收能量最多,为5kJ/m2,断裂功为1.1kJ/m2,碳纳米管与基体的脱粘功为0.15kJ/m2。显微结构分析表明：随着碳纳米管的加入,复合材料的断面形貌从光滑变得粗糙,裂纹扩展受阻,表明碳纳米管对复合材料的增强效果显著。碳纳米管/环氧树脂复合材料的电阻大幅度下降,体系的导电性增强,体系的两个渗流阈值分别出现在碳纳米管含量约为0.3wt%时和1.1wt%时。
2.添加改善碳纳米管分散性的添加剂十二烷基苯磺酸钠(SDB)有助于提高碳纳米管的分散性,从而进一步提高复合材料的力学性能。加入2.25wt%的SDB时,复合材料的拉伸强度、拉伸模量、断裂伸长率分别提高21.4%、26.0%、40.7%。体系的两个渗流阈值出现在SDB的含量为0.4wt%和2.25wt%时。显微结构分析表明添加剂处理后的碳纳米管在复合材料中的分散程度增加,裂纹更加不平,断面出现类似韧窝状特征,因此,复合材料的强度更高。
3.分别用机械球磨法和化学镀的方法制备了两种银／碳纳米复合管。当球磨法制备的复合管加入量为25wt%时,复合材料的拉伸强度、拉伸模量、断裂伸长率分别比未加银粉时增加19.6%、16.6%、15.3%；复合材料的两个渗流阈值分别出现在复合管含量为15wt%和31wt%处。化学镀法制备的复合管加入量为20wt%时,复合材料的拉伸强度、拉伸模量、断裂伸长率分别比未加碳纳米管时增加34.1%、33.3%、19.3%；该复合材料的两个渗流阈值分别出现在复合管含量为11wt%和25wt%时。相对于机械球磨法制备的复合管和纯碳纳米管增强相,用化学镀法制备的银／碳纳米复合管能更大幅度提高环氧树脂的力学和电性能的作用。
4.用机械合金化方法制备了微米铁粉／碳纳米管复合粉体,将传统粘结剂体系进行优化后,将该复合粉体与优化后的经典粘接剂混合,制备了微米铁粉注射成型喂料。研究发现,微米铁粉／碳纳米管复合粉体可以改善铁粉在粘结剂中的分散效果,0.2wt%的碳纳米管与微米铁粉复合后制备的喂料装载量可达54vo1%,粘流活化能E=16.5kJ/mol,应变敏感因子n=0.39。红外光谱研究表明,碳纳米管加入可以诱导C=O双键的打开,强化铁粉与粘结剂连接,这种结构有助于铁粉颗粒在粘结剂中的分散,避免铁粉的团聚。
5.用超声分散结合机械合金化的方法制得了纳米铁粉／碳纳米复合粉末。将纳米铁粉与碳纳米管以20：1的比例制备的复合粉末加入传统的微米级粉末注射成型喂料中,装载量可提高至58vo1%,改进后的喂料粘流活化能以及应变敏感性因子最小,分别是14.79kJ/mol和0.2,对温度以及剪切速率变化敏感,微观结构分散均匀,缺陷较少。研究表明复合粉末可以在苯环其它C原子位置上取代功能团,从而与其他粘结剂分子形成比较紧密的键合作用,有助于提高喂料生坯稳定性,减少产品的变形。另外,复合粉末的加入使得铁粉与粘结剂的连接加强,这种结构有助于防止注射成形过程中由于剪切速率过高而导致铁粉与粘结剂产生分离,从而减少铁粉的团聚以及由此引发的各种缺陷。
6.首次制备了全纳米铁粉喂料,研究发现,随温度升高或者剪切速率增大,全纳米喂料的粘度均降低。但由于高比表面积的关系,相同温度或剪切速率下,其粘度比微米粉末制备的喂料粘度高。显微结构分析表明0.2wt%的碳纳米管可以在纳米铁粉之间维持一定的分散距离以防止团聚,增加粉末之间的流动性,降低应变敏感因子。当装载量为35vo1%时,粘流活化能及应变敏感因子分别是15.87kJ/mol和0.2,微观结构均匀,缺陷较少。对纳米铁粉喂料颗粒间的相互作用能的计算结果表明,对于球形Fe粉,随着颗粒尺寸的减少,吸引势能和排斥势能逐渐靠近。当颗粒直径为40nm,装载量在33vo1%左右时,体系的能量处于平衡状态,系统可以处于热力学的稳定状态,理论与实验结果比较一致。
7.对含有碳纳米管的全纳米喂料作了热分析评价,结果表明：纳米铁粉喂料的脱脂分为两个步骤,第一步骤为PW热解,热重损失约为16wt%,第二步骤为EVA热解,脱脂量为6wt%,热解相互衔接且阶段明显,可以满足MIM脱脂工艺的分步脱脂的要求。
Nano technology is one of the most important technologies in the21century. Carbon nanotube(CNTs) has been paid much attention for its excellent properties and abroad application potential. As a new one-dimension material, CNTs exposed more excellent properties than traditional materials, which have the potential to be the ideal reinforce filler of advanced composite. Great research of CNTs reinforced polymer matrix or inorganic matrix composite has been done in recent years, which acquired a lot of achievements.
To make a focused research on the preparation and its properties of CNTs compound with polymers or metals, the main work of this paper include the surface modification of CNTs and its compound with resin and silver in order to improve the mechanical and electronical properties of epoxide resin. The effect of CNTs and its compound with micro/nano iron powder on metal injection molding is researched. The rheological properties are evaluated to resolve some of the traditional problems in MIM industry.
The main results can be summarized as follows:
1. Prepared by ultrasonic and vacuum casting, CNTs can enhance the mechanical and electronical properties of epoxide resin with the content no more than1.7wt%. When CNTs content is0.75wt%, the tensile-strength, tensile-modules and the fracture extensibility of the composite increase18.2%,16.1%and85.5%respectively. The broken energy is absorbed by three parts, one is pulling Cnts out, the other is broken Cnts and the last one is debonding of Cnts and matrix. The values of the three parts are5kJ/m,1.1kJ/m2and0.18kJ/m2, respectively. Micro structure observation shows that with the adding of CNTs, the fracture surface of composite become more and more coarse, and the crack can not expand through the sample very easy. For these reason, the composite gains enhanced mechanical properties. The electron resistance drop down and two seepage threshold values appear when the content of CNTs is0.3wt%and1.1wt%.
2. Additives of SDB is used to improve the separation of CNTs. Adding2.25wt%SDB can help to increase the tensile-strength, tensile-modules and the fracture extensibility of the composite by21.4%,26.0%and40.7%respectively. The two seepage threshold values appear when the additives content is0.4wt%and2.25wt%. Microstructure shows that after treated by additives, the CNTs disperse much better, the cracks expand even harder, and a dimple-like fracture shape appears.
3. Two kinds of Ag/C compound nanotube are prepared by ball milling and chemical plating. When the milling-tube is25wt%, the tensile-strength, tensile-modules and the fracture extensibility of the composite increase19.6%,16.6%and15.3%. The seepage threshold values appear when the content is15wt%and31wt%. When the plating-tube is20wt%, the tensile-strength, tensile-modules and the fracture extensibility of the composite increase34.1%,33.3%and19.3%. The seepage threshold values appear when the content is llwt%and25wt%. Compared with milling Ag/C nanotube and pure CNTs, plating Ag/C nanotube can increase the mechanical and electronical properties to a greater extent for the reason that the plating nanotube can achieve a more uniform silver coat around CNTs, which will double the reinforce effect of the fillers.
4. Micro iron/CNT compound powder is prepared by mechanical alloying and the traditional binder system was optimized. Proper content of the compound powder was added into optimized binders to prepare micro iron MIM feedstock. Study shows that the compound powders can increase the iron separation in the binders and improve powder loading to54vol%, of which the viscos activation energy E and strain sensitive factor n are16.5kJ/mol and0.39respectively. IR analyze shows CNTs can open the C=O bond, improve the connection of powders with binders.
5. Nano iron compound CNTs is prepared by ultrasonic dispersing and mechanical alloying. Adding this compound powders with the ratio of nano iron and CNTs of20:1into traditional micro iron MIM feedstock can help to increase the powder loading to58vol%with the best rheological properties, when the viscos activation energy E and strain sensitive factor n are14.79kJ/mol and0.2and the micro structure has the lest defect. The compound powder can add some functional group on the benzene molecular, which can combine with other binders to improve the strength of the green product. Besides, it can strength connection effect of particles and binders, which to prevent the separation of particles and binders in MIM procedure.
6. The toal nano iron powder MIM feedstock with CNTs is prepared and the related properties have been studied for the first time, which shows a pseudo-plastic behavior similar as micro iron feedstock. But, nano iron feedstock has a higher viscosity than that of micro iron feedstock in the same temperature or shear rate for its high surface area. When powder loading is35vol%, the viscos activation energy E and strain sensitive factor n are15.87kJ/mol and0.2. Calculation shows that feedstock system can reach the energy balance when the particle diameter is40nm and the powder loading is around33vol%, which is according to the experimental results.
7. Thermal analyze of the total nano iron MIM feedstock with CNTs shows that the degrease stage has two steps, one is the PW decomposition with the weight lose of16wt%, the other is EVA decomposition with weigh lose of6%. This grease pattern can be applied into the real MIM operation.
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