Microstructure and properties of carbon fiber sized with pickering emulsion based on graphene oxide sheets and its composite with epoxy resin

The Graphene oxide (GO) sheets were used for preparing the epoxy resin Pickering emulsion. The particle size and the zeta potential of the Pickering emulsion were measured to evaluate its stability. The stable emulsion could be served as the film former of sizing agent for carbon fiber (CF). The effect of the Pickering emulsion stabilized by GO sheets on the properties of CF and the interfacial adhesion property of CF reinforced composite were investigated. Scanning electron microscopy (SEM) images showed that there existed a layer of sizing agent film with GO sheets evenly on the CF surface. Abrasion resistance and stiffness values of CF were tested and the results indicated that the sized CF conformed to the requirement of CF handleability. The interlaminar shear strength (ILSS) test indicated that the interfacial adhesion of the composite could be greatly improved. The fracture surfaces of CF composites were examined by SEM after ILSS tests. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42285.     

层层自主装法制备GO杂化多壁微胶囊及其稳定性的影响探究

氧化石墨烯(GO)纳米粒子片层结构可用作Pickering乳液分散剂,芯材离子液体的稳定分散是制备微胶囊的关键,以GO作为Pickering乳液分散剂,并设计以GO为单一壁材制备了自润滑微胶囊,考虑到GO具有优异的耐摩擦性能和良好的热稳定性,再通过层层自主装法,使得壁层之间可以通过静电吸附和氢键作用连接,从而合成多层GO壁自润滑微胶囊。重点研究pH值、油水比、GO的质量浓度对GO的Pickering乳液的影响及GO杂化多壁微胶囊制备的最佳稳定条件。实验证明在pH值为2,油水质量比为5%,GO质量浓度为0.1 mg/L的实验条件下制备的微胶囊最佳。     

Au nanoparticle/graphene oxide hybrids as stabilizers for Pickering emulsions and Au nanoparticle/graphene oxide@polystyrene microspheres

Gold nanoparticle/graphene oxide hybrids (AuNP/GO) were easily fabricated by a redox reaction between GO and chloroauric acid without using any additional reductant and then used to stabilize Pickering emulsions. Factors affecting the properties of the emulsions were studied, including the HAuCl₄/GO mass ratio used to prepare the AuNP/GO, the oil/water ratio, the AuNP/GO concentration, the pH value, and the type and concentration of electrolytes. The emulsions were more stable when stabilized by AuNP/GO made from HAuCl₄/GO mass ratios of 0.375–0.5. High pH values and AuNP/GO concentrations that were too high or too low were unfavorable to the stability of the Pickering emulsions. Adding electrolytes to the systems improved the stability of the Pickering emulsions owing to the reduction of repulsive interactions between AuNP/GO sheets. The AuNP/GO stabilized Pickering emulsions were used to prepare AuNP/GO supported polystyrene (PS) microspheres (AuNP/GO@PS) by polymerizing the Pickering emulsion. The catalytic performance of AuNP/GO@PS for the reduction of 4-nitrophenol was then studied.     

The construction of pseudo-Janus silica/surfactant assembly and their application to stabilize Pickering emulsions and enhance oil recovery

Nanoparticles with high surface energy and chemical activity have drawn substantial attention in petroleum industry. Recently, Janus nanoparticles exhibited tremendous potential in enhanced oil recovery (EOR) due to their asymmetric structures and properties. In this study, a series of amphiphilic pseudo-Janus@OTAB (PJ@C18) nanoparticles with different concentrations of stearyltrimethylammoium bromide (OTAB) were successfully fabricated. The structures and properties of PJ@C18 were characterized by Fourier transform infrared spectroscopy and ζ-potential measurements. Based on the emulsification experimental results, the interaction models and the self-assembly behavior between hydrophilic nanoparticles (SiO₂@NH₂) and OTAB molecules at the oil/water interface were proposed, which was further confirmed via the measurements of the contact angle and dynamic interfacial tension. Interestingly, it was found that the change of pH value from 7.5 to 4.0 caused the type reversal of the PJ@C18-1000 stabilized Pickering emulsions. Furthermore, the PJ@C18-1000 stabilized Pickering emulsion system with excellent salt and temperature tolerances (10000 mg∙L^–1, 90 °C) significantly improved the oil recovery in the single-tube (more than 17%) and double-tube (more than 25%) sand pack model flooding tests. The findings of this study could help to better understand the construction mechanism of pseudo-Janus silica/surfactant assembly and the potential application of PJ@C18-1000 stabilized Pickering emulsions for EOR.     

两亲Janus纳米片的制备及胶体与界面性质研究进展

该文首先综述了两亲Janus纳米片制备方法的研究进展，包括界面保护法、乳液界面自组装溶胶-凝胶法、模板辅助溶胶-凝胶法以及嵌段共聚物自组装法。接着，系统介绍了两亲Janus纳米片在水溶液中的胶体特性及其在油水体系中的界面特性。最后，简要介绍了两亲Janus纳米片的应用领域，并对未来两亲Janus纳米片制备方法和胶体与界面特性的研究方向进行了展望。     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

改性蜡质玉米淀粉稳定Pickering乳液的制备及应用

采用辛烯基琥珀酸酐(OSA)对蜡质玉米淀粉(WS)疏水改性制得辛烯基琥珀酸酐改性蜡质玉米淀粉(OSA-WS),以不同取代度OSA-WS制备了稳定的Pickering乳液。测定了OSA-WS取代度(DS)、反应效率(RE)及三相接触角,对其进行了FT-IR、XRD和SEM表征。结果表明,OSA通过与淀粉表面羟基反应对其进行改性并未改变淀粉颗粒结构;随着取代度的增大,淀粉颗粒乳化性增加,制得Pickering乳液稳定性增强;以OSA-WS为乳化剂制得包埋辅酶Q10的Pickering乳液,通过透皮运输实验可知,与辅酶Q10的油溶液相比,包埋辅酶Q10的Pickering乳液更有利于辅酶Q10的透皮运输。     

乳化环氧改性的丙烯酸系乳液室温固化体系

将乙二醇二缩水甘油醚分散在水中制成环氧化合物乳液,并以其为交联剂,用以对丙烯酸系单体/胺基单体乳液共聚物的改性,制成了双组分室温固化乳液涂料。研究了乳化剂种类和胺基单体用量对聚合稳定性的影响,结果表明,若采用p 壬基酚聚氧化乙烯醚硫酸钠为乳化剂,且胺基单体用量低于单体总量2 5%时,可以制得稳定的带胺基的共聚物乳液。将丙烯酸系共聚物乳液和环氧乳液复合并在室温下干燥成膜,通过对聚合物膜的DSC和力学性能测试均表明,双组分体系在成膜过程中发生了交朕反应,而未加环氧化合物的单组分聚合物乳液成膜时则不发生交联。     

Janus polymeric cages

Janus polymeric cages are fabricated by Pickering emulsion interfacial polymerization. The modified silica particles are used to stabilize the emulsions. Oil-soluble monomers and water-soluble monomers copolymerized in between the voids among the silica particles at the interface, forming amphiphilic Janus polymer shell in which the silica particles are embedded. After removal of the silica particles and the oil core, the corresponding Janus polymeric cages are achieved with uniform and regularly arrayed holes across the shell. The Janus cages are permeable to both organic molecules and particles.     

Janus三角纳米片和"三明治"三角纳米片消光特性的数值研究

基于离散偶极近似法(DDA)计算了不同组分的Janus三角纳米片和“三明治”三角纳米片的消光特性,两种纳米片在紫外-可见光波段均出现了明显的吸收峰。当纳米片较小时,消光特性主要以吸收为主,当纳米片逐渐增大,散射作用开始明显。当纳米片增大时,吸收峰向长波方向移动并且峰会变宽。二氧化硅与银的组合能在较宽的波段内激发表面等离激元效应,因此波峰比金银组合纳米片的波峰宽,但是吸收峰值较后者低。增加纳米片的层数,或者添加纳米片的组分,可以在一定范围内对纳米片的消光特性进行调节,从而提高太阳能光热转换效率。     

Forward osmosis water desalination: Fabrication of graphene oxide-polyamide/polysulfone thin-film nanocomposite membrane with high water flux and low reverse salt diffusion

This paper investigates the synthesis of graphene oxide (GO)-incorporated polyamide thin-film nanocomposite (TFN) membranes on polysulfone substrate for forward osmosis applications. The GO nanosheets were embedded into polyamide layer using different concentrations (0.05?0.2 wt%). The results represented the alteration of polyamide surface by GO nanosheets and enhancing the surface hydrophilicity by increasing the GO loading. The results showed that the water flux for 0.1 wt% GO embedded nanocomposite (TFN) membrane was 34.7 L/m² h, representing 90% improvement compared to the thin-film composite, while the salt reverse diffusion was reduced up to 39%.     

A green approach for the reduction of graphene oxide nanosheets using non-aromatic amino acids

A simple and green chemistry approach for the preparation of reduced graphene oxide nanosheets through the reduction of graphene oxide (GO) using non-aromatic and thiol-free amino acids as the reductant was successfully demonstrated. l-Aspartic acid and valine amino acids were used as models to prove that the reduction method is generic to other amino acids. The significance of the proposed method is that it eliminates the use of toxic and harmful chemicals to humans and the environment, which makes it compatible for the large-scale production of graphene. Reduced GO nanosheets showed good stability in aqueous dispersions due to the strong electrostatic repulsion on the graphene surface. Structural studies confirmed the deoxygenation of GO from the loss of hydroxyl, carbonyl and epoxy groups, and preparation of graphene sheets between 20 and 70 nm suitable for broad biomedical applications.     

基于纤维素纳米晶稳定的亚微米Pickering乳液制备

与传统表面活性剂稳定的乳液相比,固体纳米颗粒稳定的Pickering乳液具有较强的界面稳定性、多功能性、低毒性等优势,在生物医药领域具有较大的应用潜力。而相较于尺寸较大的微米级Pickering乳液,亚微米Pickering乳液具有更大的比表面积、更有效的递送效率,有望进一步拓展Pickering乳液在生物医药领域的应用。但由于Pickering乳液的制备影响因素众多,且相互制约,刚性的固体颗粒难以在较小的有限油水界面排布,增加了亚微米Pickering乳液的制备难度。本工作以制备稳定的亚微米Pickering乳液为研究目标,采用具有良好生物相容性的天然多糖–纤维素纳米晶(CNCs)为颗粒乳化剂,角鲨烯作为油相,考察了颗粒浓度、油水比例、水相成分、超声时间及频率对Pickering乳液粒径分布及稳定性的影响,最终得到了具有良好的储存稳定性和抗离心稳定性的粒径为638.7?8.40 nm的亚微米Pickering乳液(CNCs-PE)。通过激光共聚焦显微镜证实了CNCs吸附在油水界面,形成了Pickering乳液结构。利用CCK-8法评价了CNCs和CNCs-PE的细胞毒性,结果表明,两者都具有良好的细胞安全性。此外,将其用于吸附模型抗原OVA,吸附率达到约80%,且肌肉注射部位的切片结果也表明其注射安全性良好。此结果为亚微米Pickering乳液进一步研究提供了参考,并有望拓展CNCs稳定的亚微米Pickering乳液在生物医药领域的应用。     

乳液法制备聚乙烯醇-石墨烯气凝胶及其对纯有机物的吸附

采用氧化石墨烯(GO)稳定的Pickering乳液为软模板，制备聚乙烯醇-石墨烯气凝胶。探究GO浓度、均质转速、油水比、乙二胺(EDA)和聚乙烯醇(PVA)用量等因素对乳液稳定性、粒径分布及气凝胶成型的影响，发现改变乳液配比可控制乳液粒径的大小，进而对气凝胶的密度和孔隙率进行调控。通过SEM、FT-IR、Raman、XRD对最优制备条件下制得的聚乙烯醇-石墨烯气凝胶(PGA)进行表征，可知GO经水热反应后被还原组装形成三维网络气凝胶结构(PGA)且其孔道直径与乳液粒径基本一致。对PGA进行挤压实验发现其具有轴、径双向挤压回弹性，且重复挤压200次以上PGA仍然具良好的弹性。PGA对纯有机物的吸附量最高可达280 g·g^?1，且每克PGA吸附的有机物的体积为恒定值。     

智能响应型Pickering乳液的制备及在物质分离中的应用进展

Pickering乳液是指由微纳米固体粒子代替传统表面活性剂作为乳化剂而稳定的乳液,具有较强的稳定性和超高油/水界面,能够为多相界面反应和物质传输提供高效稳定的场所。Pickering乳液的乳滴结构和性质与固体颗粒的尺寸形貌及表面性质密不可分,通过调控固体颗粒本身或表面的性质可以赋予Pickering乳液特定的响应性功能,拓宽其应用领域。本文对近年来不同响应型（磁性、CO₂、pH、光、温度等响应型）的Pickering乳液的主要研究成果进行了综述,重点介绍了Pickering乳液的稳定性原理、响应型Pickering乳液的制备方法和结构调控策略,以及近年来Pickering乳液在物质分离提取中的应用研究进展,最后对智能响应型Pickering乳液应用研究的发展趋势进行了展望。     

非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性,将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右,分散均匀;Fc⁺A成功修饰到纳米颗粒表面,且随Fc⁺A浓度的增加,改性颗粒的接触角明显增大;Fc⁺A浓度为12.5 mmol/L,乳化剂浓度为0.3%(质量),油水比为4∶6,搅拌速率为10000 r/min,得到的Pickering乳液具有良好的稳定性。而且,所得乳液具双重响应性,通过氧化还原和磁场可实现对乳液稳定性的可逆调控。     

Fabrication of covalently-bonded polystyrene/SiO<Subscript>2</Subscript> composites by Pickering emulsion polymerization

Pickering emulsion polymerization has attracted considerable attention in material fabrication due to its unique surfactant-free character and versatile association of oil, water and particles for a large set of materials. In this study, SiO₂ modified with Methacryloxypropyltrimethoxysilane (MPTMS) was employed to prepare Pickering emulsion, and subsequently covalently-bonded polystyrene/SiO₂(PS/SiO₂) composites were synthesized by Oil-in-water Pickering emulsion polymerization. Optical micrograph, contact angle, thermogravimetric analysis (TGA), Fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM) and dynamic laser scattering (DLS) were employed to characterize the modified SiO₂, Pickering emulsion and prepared composites. It was found that prepared composites possess ragged surface morphology and SiO₂ concentration has an important effect on the morphology of as-prepared composites. In addition, covalent bond between PS core and SiO₂ shell was evidenced by FT-IR.     

基于多巴胺亲水改性下Janus膜的制备及其油水乳液分离

目前用于处理含油废水的特殊润湿材料通常分为去油型和去水型,其仅局限分离单一乳液。本文基于多巴胺改性的聚偏氟乙烯(PVDF)膜,通过交替浸渍工艺和无纺布剥离,制备了具有不对称润湿性的Janus膜。通过调整交替次数以及剥离无纺布,可分别获得超亲水/水下超疏油的表面以及超疏水/超亲油的底面,水/水下油接触角(CA)差异高达150°。基于Janus膜的非对称润湿性,仅通过切换跨膜方向,对表面活性剂稳定的水包油(O/W)和油包水(W/O)乳液渗透通量高达367L/(m²·h)和1729L/(m²·h),其中水包油渗透液化学需氧量(COD)符合石油化工排放标准,油包水渗透液中水含量小于80mg/L,实现了对O/W和W/O乳液的高效分离。此外,Janus膜在牛血清蛋白(BSA)溶液分离过程中表现出理想的防污性能和可重复使用性。     

软模板法石墨烯气凝胶的可控制备及其吸油性能

以环己烷为油相,氧化石墨烯（GO）为稳定剂,采用Pickering乳液法制备石墨烯气凝胶,利用电子显微镜对Pickering乳液进行表征,利用扫描电镜（SEM）、傅里叶红外光谱（FTIR）、拉曼光谱（Raman）、X射线衍射（XRD）对制得的石墨烯气凝胶进行表征。对比Pickering乳液的液滴大小与气凝胶的孔径大小可知,通过软模板法实现了对气凝胶的孔径控制,通过控制均质机的转速来调控气凝胶的孔径大小,当均质机转速分别为10000r/min、12000r/min和15000r/min时,所得石墨烯气凝胶的孔径分别为45μm、35μm和30μm左右,通过调节油水比实现了气凝胶的密度与孔隙率的控制,油水比越大,所得气凝胶的密度越小,孔隙率越大,通过延长还原时间可增强石墨烯气凝胶的机械性能。将所得气凝胶用于油品的吸附,可快速吸附水上浮油及水底重油,而且几乎不吸附水;对同一油品而言,气凝胶的吸附能力与其制备时的油水比呈正相关,采用挤压的方式实现石墨烯气凝胶的循环利用,经过10次循环再生后气凝胶的吸附能力仅有15%的损失。     

In Situ Synthesis of Ultrahigh Molecular Weight Polyethylene/Graphene Oxide Nanocomposite Using the Immobilized Single-site Catalyst

We address the immobilization of single-site catalyst on the graphite oxide (GO) surface using methylaluminoxane. Ethylene polymerization was performed using the immobilized catalyst and the nanocomposite of ultrahigh molecular weight polyethylene (UHMWPE)/GO with less entanglement density was obtained. It was observed that the drawability, mechanical and thermal properties of the produced polymer significantly are affected by the anchoring of polymer chains to the GO nanosheets. The orientation and location of crystalline lamellae and nanosheets were verified by microscopic techniques. Besides, X-ray analysis demonstrated the dispersion of GO within the UHMWPE phase and crystallinity of UHMWPE/GO nanocomposites enhanced during drawing process.