水介质中纳米金刚石表面改性研究

对纳米金刚石在水介质中的分散进行了探讨,利用机械力和化学力共同作用,对纳米金刚石表面进行改性,从而实现纳米金刚石在水介质中的分散和稳定,采用不同的机械化学处理工艺,可以使得体系在酸性和碱性介质条件下均保护良好的分散。对表面改性过程进行了机理分析。     

Effect of silica particles modified by in-situ and ex-situ methods on the reinforcement of silicone rubber

In-situ and ex-situ methods were applied to modify silica particles in order to investigate their effects on the reinforcement of silicone rubber. Surface area and pore analyzer, laser particle size analyzer, Fourier-transform infrared spectroscopy (FTIR), contact-angle instrument, and transmission electron microscope (TEM) were utilized to investigate the structure and properties of the modified silica particles. Dynamic mechanical thermal analyzer (DMTA) was employed to characterize the vulcanizing behavior and mechanical properties of the composites. Thermogravimetric analysis (TGA) was performed to test the thermal stability of the composites. FTIR and contact angle analysis indicated that silica particles were successfully modified by these two methods. The BET surface area and TEM results reflected that in-situ modification was more beneficial to preparing silica particles with irregular shape and higher BET surface area in comparison with ex-situ modification. The DMTA and TGA data revealed that compared with ex-situ modification, the in-situ modification produced positive influence on the reinforcement of silicone rubber.     

表面活性剂对相反转法制备金属颗粒的影响

采用相反转悬浮液体系中不同表面活性剂同步修饰的方法制备超细低熔点金属颗粒,研究阳离子和阴离子表面活性剂对金属颗粒的影响。通过沉降实验观察不同表面活性剂修饰的金属颗粒在水中的分散及稳定性,并采用激光粒度仪、扫描电镜对低熔点金属颗粒的粒径和形貌进行表征分析。结果表明:表面活性剂的种类对制备低熔点金属颗粒有重要的影响,其中阴离子表面活性剂的效果最好。对几种阴离子表面活性剂的研究表明:油酸钠的作用最明显,其浓度大小对低熔点金属颗粒的粒径、形貌和分散效果有显著的作用。采用质量分数为1%的油酸钠水溶液可制备出分散稳定、粒径分布窄和球状的超细低熔点金属颗粒,平均粒径为0.343μm。     

微纳米SiO2/PP复合材料增强增韧的实验研究

为了研究无机刚性颗粒对通用塑料聚丙烯 (PP) 的力学性能的影响, 采用熔融共混方法制备了经硅烷偶联剂A-151处理的SiO₂/PP 复合材料, 并通过其缺口冲击、 拉伸、 弯曲试验和冲击断面的形貌观察, 分析研究了微纳米SiO₂颗粒大小、 填充量、 表面改性以及不同颗粒大小SiO₂混合物对PP复合材料增韧、 增强效果的影响。实验结果表明: 纳米SiO₂的加入可以同时改善其韧性、 刚性和强度; 填充量相同, 颗粒越细, SiO₂/PP复合材料的力学性能越好。SiO₂经改性后填充到PP基体中, 明显改善了颗粒在基体中的分散性及基体与颗粒之间界面结合性能, 使复合材料的综合力学性能得到提高。不同颗粒大小的SiO₂混合后填充到PP基体中, 混合SiO₂的协同效应使复合材料拉伸、 弯曲性能进一步提高, 对PP基体具有更好的增强效果, 但其冲击性能下降。      

Preparation of TiO2 particles and surface silanization modification for electronic ink

In this study, a sol–gel method has been adopted to synthesize titanium dioxide (TiO₂) particles. In order to improve the surface properties of the TiO₂ particles, vinyl triethoxysilane (VTES) has been used for their modification by silanization. The particles have been characterized by FTIR, scanning electron microscope, transmission electron microscopy, and X-ray diffraction (XRD) techniques. The results confirmed that VTES had been successfully grafted onto the surface of the TiO₂ particles. The TiO₂ particle size was not changed by the silanization modification, remaining at 100–200 nm. XRD results have shown the crystalline phase of the TiO₂ particles to be of the anatase type, and this was also unaffected by the VTES modification. Dispersion properties and suspension stability characterization of TiO₂ particles showed that VTES-modified TiO₂ particles have better dispersion stability and suspension stability in the dispersant of tetrachloroethylene than that of unmodified TiO₂ particles.     

二甲基硅油对中铬黄颜料的表面改性

为了提高中铬黄颜料在漆料中的分散性,采用包覆改性法,以二甲基硅油为改性剂对中铬黄颜料进行表面改性,通过研究表面改性对颜料的吸油量、流动性、沉降时间、傅里叶红外光谱、扫描电镜图像的影响规律,对改性机理进行探讨。结果表明,使用二甲基硅油对中铬黄颜料进行表面改性可改善其在干燥状态下和有机聚合物基体中的分散性,随着改性剂用量的增大,中铬黄颜料的每百克吸油量由原来的30 g减小为16 g;经过二甲基硅油表面改性处理后,中铬黄粉体在煤油中的沉降时间由1 h延长到16 h左右;最佳工艺条件是二甲基硅油的质量为中铬黄质量的2.5%;二甲基硅油与中铬黄颗粒的表面吸附方式为物理涂覆;经过表面改性处理后,颗粒在干燥状态下的分散性明显提高。     

Manufacturing and physico-mechanical characterization of carbon nanohorns/polyacrylonitrile nanocomposites

The use of carbon nanohorns (SWCNHs) as a modifying filler in a polyacrylonitrile (PAN) matrix is studied with the goal of elaborating nanocomposites. The study deals with assessment of the dispersity of SWCNHs in a PAN polymer suspension. The SWCNHs were introduced into the PAN-based suspension using different methods, including mechanical stirring, ultrasonification and the combination of ultrasonification with addition of a surfactant. Agglomeration and dispersion processes of SWCNH in the polymer suspensions were studied using DLS technique and turbidimetry. The resulting properties of nanocomposite foils after solidification in water ambient were verified in various tests. The mechanical tensile properties (tensile strength, modulus and strain to fracture) of the nanocomposites before and after the dispersion process were compared. The nanocomposites obtained under optimally prepared suspension perform the highest strain to fracture in tensile test. Electrical resistivity and thermal conductivity of nanocomposites samples after appropriate dispersion of SWCNHs in the PAN suspension were also determined. The presence of SWCNH in the PAN suspension affects the structure of nanocomposites after solidification through changing structural ordering of the polymer. The study revealed that the polymeric suspensions prepared in optimum processing conditions contain the carbon aggregates the size of which correspond almost to the mean size of a dahlia flower-like structured particle, i.e., 50–250 nm and it was not possible to separate such particles into a single form of carbon nanohorn by the techniques used.     

A novel technology for powder dispersion and surface modification

A novel technology for powder dispersion and surface modification was studied by experiment in this paper. In the process, powders are dispersed by the nozzle and the atomized modifying agent is sprayed into the dispersed particles and coated on the surface at the same time. Silica, mica and talc powders were dispersed and modified by this technology, the performance of powder dispersion is evaluated by the scanning electron microscope (SEM), and the performance of surface modification is evaluated in advance by the viscosity of powder-paraffin suspension. In experiment, the modified silica was filled in the polypropylene (PP), the impact fractographs, notched impact and tensile properties of the PP composites were studied, the results indicate that the developed technology is effective for powders dispersion and surface modification.     

Facile synthesis of cationic polymer functionalized nanodiamond with high dispersity and antibacterial activity

In this work, a cationic polymer, N-alkylated poly (4-vinylpyridine) was applied for the surface functionalization of nanodiamond (ND). The facile route not only settled the problems of agglomeration and poor dispersion stability of ND but also rendered the nanomaterial antibacterial property. Chemical modification of the particles was confirmed by FT-IR spectroscopy and ¹HNMR, and the cationic polymer contents were determined by TGA studies. The particle diameters and dispersity of functionalized NDs were investigated by TEM and DLS measurements. It was found that extremely tight core aggregates (100–200 nm) were broken into tiny nanoparticles (20–30 nm) through functionalization with NPVP-propyl or NPVP-hexyl, which gave stable and homogeneous functionalized ND particles in colloidal solution. The antibacterial tests against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) showed that the cationic polymer-modified ND exerted certain antibacterial activity. The FE-SEM images indicated that NPVP-hexyl-ND particles were attached to the cell wall surface of E. coli, which subsequently led to the formation of nanoscale holes on cell membrane and eventually the serious destruction of cell wall. We suspected that the interaction of NPVP-hexyl-ND with bacteria may come from the electrostatic interactions, the intermolecular and surface forces between functionalized nanoparticles and cell membranes, which may damage the outer membranes of bacteria and result in cell death.     

在氯仿中合成纳米羟基灰石的研究

采用卵磷脂作为乳化剂,在氯仿-水所形成的乳液中制备纳米羟基磷灰石(HA)晶粒,并研究了卵磷脂对HA在氯仿中分散性的影响。FTIR及TEM分析结果表明,卵磷脂能吸附在HA晶粒表面,起着表面改性作用。通过分液除去水分后,HA仍能均匀地分散于氯仿中,没有产生团聚。因而,通过该法能制备出颗粒度在100nm左右、分散性好、能稳定存在的HA的氯仿悬浮液。在该悬浮液中加入聚甲基丙烯酸甲酯(PMMA)能形成HA/PMMA复合材料,并且HA晶粒在基体中分散均匀。因此,本文的制备方法对于制备具有良好两相分布形貌和具有高强力学性能的有机无机复合材料有着重要意义。     

Dispersion effect and auto-reconditioning performance of nanometer WS<Subscript>2</Subscript> particles in green lubricant

This paper reported on dispersion effect and dispersing techniques of nanometer WS₂ particles in the green lubricant concocted by us. And it also researched on auto-reconditioning performance of nanometer WS₂ particles to the abrasive surfaces of steel ball from four-ball tribology test and piston ring from engine lubrication test. The treated and untreated nanometer WS₂ particles were analysed by infrared spectrum. And the elementary component and interior elementary distribution of abrasive surface repaired by nanometer WS₂ particles were analysed by multifunction electron spectrometer. The results showed that the combinative method of ultrasonic dispersion, mechanical agitation and surface modification could improve the dispersion uniformity and stability of nanometer WS₂ particles in the green lubricant effectively. And the optimal ratio of the mass between surface modifier and nanometer WS₂ particles was 1: 2.5, the optimal treating time was 5 h. And IR analysis indicated that surface modifier could react with hydroxide radicals on surfaces of WS₂ particles and modify the surfaces, and the long lipophilic groups on surfaces of nanometer WS₂ particles could stretch in oil adequately and form steric hindrance layers between particles which prevented particles from conglomerating and depositing. In addition, tribological tests and surface analysis indicated that there were WS₂ adsorption film and reaction film on abrasive surfaces during the tribological tests, which could fill and level up the furrows on abrasive surfaces. As a result, the abrasive surfaces were repaired effectively by nanometer WS₂ particles.     

Surface modification to improve hydrophobicity of detonation nanodiamond

In this work, surface treatment of nanodiamonds (NDs) produced by a detonation technique has been conducted using oleic acid and dodecylamine in order to achieve a stable dispersion in oil. From Fourier transform infrared spectroscopy (FTIR) analyses, it was found that the NDs have various surface functional groups such as -NH2, -COOH, -OH, etc. By inducing covalent bonding between the carboxyl group of oleic acid and the amine group of the ND surface with high chemical reactivity, NDs were well-dispersed in oil for a lengthy period of time. High resolution transmission electron microscopy (HRTEM) images indicate that the surface treatment with oleic acid is highly effective in breaking down the aggregates of NDs into smaller sized particles. The dispersion stabilities of the oils containing as-received NDs and surface treated NDs were compared to each other using Turbiscan measurement.     

Influence of Ultrasonic on the Dispersibility of ZrB2 Particles

To obtain the better ZrB₂/Al(OH)₃-Y(OH)₃ core-shell composite particles, ZrB₂ particles must be adequately dispersed during the coating process. In this article, the dispersibility of ZrB₂ particles in the ZrB₂ suspension is investigated via the sedimentation method. Through test and analysis, the dispersibility is rapidly increased with prolonging the ultrasonic dispersion time before 10 minutes. After 30 minutes, the sedimentation grads using ultrasonic dispersion basically reach the sedimentation balance, but the grads using mechanical agitating dispersion does not basically change after 5 minutes. The ultrasonic dispersion is one of more effective ways between ultrasonic and mechanical agitating dispersion, the dispersion time for 10 minutes is chosen in the dispersibility of ZrB₂ particles via ultrasonic dispersion.     

亲水SiO2改性水性聚氨酯-聚丙烯酸酯的制备及性能

为了提高水性聚氨酯材料的耐热性、耐化学试剂性及力学性能,利用甲基丙烯酸甲酯(MMA)作为聚氨酯预聚合的连续相,同时采用羧酸型以及磺酸型亲水扩链剂,乳化时引入反应性的亲水性纳米二氧化硅(WSiO2),通过无有机溶剂法制备了稳定的耐温水性聚氨酯-聚丙烯酸酯(WPUA)乳液。利用透射电镜、红外光谱、X射线衍射和热重等手段研究了WPUA乳液及其膜的结构和性质。结果表明:随着样品中WSiO2含量的增加,WPUA乳液的平均粒径增大,WPUA膜的光泽度下降,硬度、附着力增加,WPUA薄膜的硬度和附着力增加,拉伸强度值先上升后下降,最佳WSiO2添加量为1%。适量的WSiO2可以改善WPUA材料的耐热行为。当热分解率为50%时,WSiO2改性后WPUA的分解温度比改性前提高了39℃。WSiO2改性使WPUA的力学和耐化学试剂性也得到了改善。     

Dispersion and stability of nanoparticles in electrophoretic displays

This work is focused on investigating the influence of morphologies and composition of polymer coating layers on the dispersion stability of the hybrid particles dispersed in non-aqueous solvent for use in electrophoretic displays. Black copper chromite/polymer core-shell nanoparticles are synthesized through radical grafting polymerization. A series of methylacrylate monomers containing a plurality of alkyl side chains with different length, methyl methacrylate (MMA), tert-butylmethacrylate (TBMA), 2-ethylhexyl methacrylate (EHMA) and lauryl methacrylate (LMA), are employed for polymer encapsulation. The morphologies and composition of Black 1G/polymer core-shell nanoparticles are characterized by a combination of TEM and FTIR measurements. The UV–vis transmittance results demonstrate that the longer or more branching the monomers used in polymer modification, the more stable the particle suspension. For homopolymer encapsulation, monomer with an alkyl chain containing more than about four carbon atoms will impart good dispersibility to particles. Moreover, incorporation of a second monomer into polymer backbone can adjust the dispersion stability of particle suspension. When 15 mol% of MMA or 5 mol% of TBMA is added into PLMA backbone, the particles will gain better dispersibility than particles coated with 100 mol% LMA. If EHMA acts as main monomer, addition of a second monomer will decrease the dispersibility instead. These findings may be a guideline to tune electrophoretic medium stability and improve life of EPDs. Within this study, A dual-particle electrophoretic dispersion of P (4-VP-co-LMA) anchored Black 1G particles and white TiO₂ was prepared to show black/white image under a bias voltage of 5 V.     

滑石粉粒径对PVC/滑石粉复合材料力学性能和热膨胀系数的影响

使用钛酸酯偶联剂对不同粒径的滑石粉改性,并通过熔融共混方法制备了PVC/滑石粉复合材料。通过力学性能测试、线性膨胀测试等方法研究了滑石粉粒径对复合物的形态结构、力学性能和线性膨胀系数的影响。实验结果表明,在实验范围内随着滑石粉含量的增加,400 mesh滑石粉会使复合体系拉伸强度降低较多,冲击强度基本不变;800 mesh及1250 mesh滑石粉则使复合体系拉伸强度降低明显减少,同时增加体系的冲击强度,1250 mesh滑石粉体系冲击强度在滑石粉含量为20份时有极大值。线性膨胀系数结果显示,滑石粉的引入能明显降低PVC体系的线性膨胀系数,滑石粉粒径尺寸为800 mesh和1250 mesh时降低幅度比400 mesh时明显。     

碳／蒙脱石复合材料和硅藻土粉体表面改性方法的研究

以自制的碳／蒙脱石复合材料、硅藻土为原料，用十六醇作为改性剂，研究超声分散和常规搅拌两种方法对碳／蒙脱石复合材料、硅藻土效果表面改性的影响，通过分光光度计、接触角测定仪和扫描电镜进行表征，结果表明，两种方法处理过的碳／蒙脱石复合材料、硅藻土粉体均较未处理前分散性好；超声分散方法有利于硅藻土的表面改性，而碳／蒙脱石复合材料用搅拌的方法效果更好。将不同改性方法制得的粉体材料及未改性粉体填充到天然橡胶中，其力学性能得到了提高。     

Effect of kneading process conditions on the particle fineness and the polydispersity in nanocomposites

This paper is part of a series of publications that cover the entire process chain to produce nanocomposites. The associated papers are published in the chronological sequence and broach the issues of: “production and dispersing of nanoparticles”, “characterisation of the liquid and reactive matrix” as well as “resulting composite properties by experimental and simulation methods”. Nevertheless, all resulting composite properties are strongly dependent on the method of particle incorporation and on the particle size distribution. Therefore, this study focuses on the optimisation of the dispersion referring to finest particles, smallest particle size distribution, shortest dispersing time and lowest specific energy. In order to prepare the matrix suspension, nano-fillers were dispersed conducting shear mixing techniques in a high performance laboratory kneader. As carrier fluid epoxy resin and a corresponding anhydride hardener system were chosen. Tests were performed using neat and surface modified alumina particles at different levels of particle concentrations. The particle size distribution was determined using dynamic light scattering directly after the dispersing process. Additionally each sample was characterised after 1, 3 and 7 days. Since similar examinations were performed for all formulations, a statement on the influence of re-agglomeration processes and the role of surface modification can be derived. By correlating the progress of the dispersing process to the mass fraction and the particle size distribution, the dispersion process can be evaluated regarding the dispersing time, specific energy and product quality. However, an optimum polydispersity can be found between 25 and 30 wt.%, even if the finest average particle size is reached at higher mass fractions around 45 wt.%. Silane modified alumina particles in epoxy resin constitute the most stable system against re-agglomeration, although the finest particles and the smallest specific energy are attained in non-modified systems. Moreover it can be concluded, that resulting properties of the cured composite are strongly related to the aspired optimisation, e.g. product fines, particle size distribution, required energy input and stability.     

Effect of hybridization of liquid rubber and nanosilica particles on the morphology, mechanical properties, and fracture toughness of epoxy composites

A liquid carboxyl-terminated butadiene–acrylonitrile copolymer (CTBN) and SiO₂ particles in nanosize were used to modify epoxy, and binary CTBN/epoxy composites and ternary CTBN/SiO₂/epoxy composites were prepared using piperidine as curing agent. The morphologies of the composites were observed by scanning electron microscope (SEM) and transmission electron microscope (TEM), and it is indicated that the size of CTBN particles increases with CTBN content in the binary composites, however, the CTBN particle size decreases with the content of nanosilica in the ternary composites. The effects of CTBN and nanosilica particles on the mechanical and fracture toughness of the composites were also investigated, it is shown that the tensile mechanical properties of the binary CTBN-modified epoxy composites can be further improved by addition of nanosilica particles, moreover, obvious improvement in fracture toughness of epoxy can be achieved by hybridization of liquid CTBN rubber and nanosilica particles. The morphologies of the fractured surface of the composites in compact tension tests were explored attentively by field emission SEM (FE-SEM), it is found that different zones (pre-crack, stable crack propagation, and fast crack zones) on the fractured surface can be obviously discriminated, and the toughening mechanism is mainly related to the stable crack propagation zone. The cavitation of the rubber particles and subsequent void growth by matrix shear deformation are the main toughening mechanisms in both binary and ternary composites.     

纳米CaCO3复合微粒增韧增强PC/ABS合金

经甲基丙烯酸甲酯和丙烯酸丁酯双单体聚合包覆的纳米碳酸钙形成了核壳结构增韧复合微粒。在双螺杆挤出机中采用二次挤出法制备出PC/ABS/纳米碳酸钙复合材料。研究纳米碳酸钙复合微粒对PC/ABS合金力学性能的影响表明:添加适量纳米CaCO3复合微粒,PC/ABS合金的缺口冲击强度和拉伸强度都得到提高。纳米CaCO3复合微粒具有无机纳米颗粒和弹性体双重协同增韧的作用,其表面的聚合物分子链与基体树脂起到嵌段增容作用。