The migration of styrene butadiene latex during the drying of coating suspensions: when and how does migration of colloidal particles occur?

Surface elemental compositions of model latex clay coatings on an impervious substrate consolidated under various conditions were measured using the XPS technique, in order to clarify when and how colloidal latex particles migrate to the surface during drying. Under similar drying conditions, surface carbon content decreased with the addition of a water-soluble polymer to the coating colors, while remaining virtually unchanged for coatings of different coat weights made with a given color, indicating that surface carbon content variation is mainly caused by migration of latex rather than of water-soluble polymer. The results also showed that for coatings made with a given suspension, surface carbon content decreased with increasing delay time between coating and heating. For coatings frozen during consolidation and dried by sublimation, surface carbon content increased with increasing drying time before freezing. These results suggest that for the model coatings studied, latex migration mainly occurs after coating application before capillary formation during the initial drying stage when coatings are in the liquid phase, contradicting both the conventional capillary transport and boundary wall migration mechanisms. An alternative mechanism which attributes latex migration to surface trapping effect and to higher Brownian mobility of the smaller latex particles compared with pigment appears to provide a systematically consistent explanation to those phenomena. The new particle migration mechanism implies that segregation of colloidal particles is a ubiquitous phenomenon that would occur not only during the drying of paper coatings but also during consolidation of colloidal films containing particles of different sizes. This is of great importance in the control of surface compositions of nanocomposite coatings.     

Deposition and characterization of TiAlSiN coatings prepared by hybrid PVD coating system

TiAlSiN coatings with different Si contents were deposited on silicon and high‐temperature alloy by using a hybrid physical vapor deposition coating system, where the cathodic arc ion plating was combined with a twin target mid‐frequency magnetron sputtering. The chemical composition, microstructure, cross‐sectional structure and morphology were carried out by X‐ray photoelectron spectroscope (XPS), X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscope (TEM), respectively. NanoTest 600 nanomechanical system and ball‐on‐disc friction tester were used to investigate the mechanical and friction properties of TiAlSiN coatings. The worn surface of the TiAlSiN coatings and counterballs were investigated by means of surface profilometer and optical microscope. The wear rates were also measured by surface profilometer. The results showed that the Si addition did not change the coatings growth orientation, and the coating transfered into amorphous phase when the Si content reached about 13.9 at.%. The tribological properties and the hardness were improved by solid solution of Si atoms and grain boundary strengthening of SiN_x amorphous phase with moderate Si content addition. In addition, the SiNx amorphous phase improved oxidation resistance of TiAlN coating, but with a high Si content (more than 8.3 at.% in this work) the agglomeration of SiN_x amorphous phase would reduce the mechanical properties and oxidation resistance of the coating. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of hydrophobicity on the stability of sol–gel silica coatings in vacuum and their laser damage threshold

Silica antireflective coatings modified by hexamethyldisilazane (HMDS) were deposited on clean substrates (silicon wafer or K9 glass blanks) by sol–gel processing. The effects of HMDS on the contamination resistant capability and laser-induced damage threshold (LIDT) of coatings were investigated. Transmission electron microscopy revealed that a stable sol with uniformly distributed silica particles with an average particle size of about 15 nm was acquired by adding appropriate amount of HMDS into the standard SiO₂ sol. With the modified sol the resultant coatings were hydrophobic and the contact angle for water increased with increasing amount of HMDS in the reaction mixture. Such increase in hydrophobicity was not the result of surface roughness. The antireflective properties were retained after HMDS-treatment and the maximum transmission values were above 99 %. The introduction of HMDS into silica sols had also increased the LIDT of coatings from 24.3 to 37.0 J cm^?2 when the molar ratio of HMDS to tetraethoxysilane was 0.05:1. The increase in LIDT was attributed to the decrease of nodular defect and uniform microstructures of coatings as an effect of the HMDS modification. After some of the hydroxyl groups on the surface of the SiO₂ particle were replaced by methyl groups, from which the SiO₂ particle gained a water-repellent surface, the stability of coatings in vacuum was increased. The maximum transmission values of modified coatings decreased by only 0.25 % after storage under vacuum for 168 h. In contrast, the standard sol–gel silica coatings decreased about 2 % under similar conditions. The LIDT of modified coatings remained as high as 30.8 J cm^?2, more than that of standard coatings stored for the same duration in air.     

Preparation and Performance of HGM/PPENK-based High Temperature-resistant Thermal Insulating Coatings

Novel high temperature-resistant coatings with high mechanical strength and thermal-insulating performance were prepared with poly(ether nitrile ketone)(PPENK) resin as matrix and hollow glass microspheres(HGMs) as thermal-insulating filler. The corresponding mechanical and thermal-insulating study indicated that the mechanical properties of the coatings decreased with the increase of HGM content,and were improved after surface modification of HGM by KH570 resulting in enhancement of interaction between HGM and PPENK resin. The thermal conductivity of HGM/PPENK thermal-insulating coating decreased with the increase of HGM content and coating thickness, along with the decrease of the true density. It also showed slight increase trend due to HGMs surface modification. The HGM/PPENK coating filled with modified HGMs showed better thermal resistance than that of unmodified HGM/PPENK coating. The thermal decomposition temperature at 5%weight loss of the coating containing modified HGMs was 10 °C lower than that of pure PPENK, and 40 °C higher than that of neat HGM/PPENK coating. The coating exhibited commendable appearance after 400 °C for 30 min. The merits of HGM/PPENK-based thermal coatings obviously demonstrated promising prospect in thermal protection fields.     

钌镧氧化物涂层在NaCl 溶液中的电化学阻抗谱(EIS)研究

测量了钌镧氧化物涂层的电化学阻抗谱(EIS), 结合循环伏安(CV)及扫描电子显微镜形貌分析, 研究了钌镧氧化物涂层阳极在3.5% NaCl 溶液中电化学表面结构及电化学行为. 在非析氯反应区间, 该涂层EIS 数据的最佳拟合等效电路是R_s(R_ctQ_dl), 在析氯反应区间, 其等效电路为R_s(R_fQ_f)(R_ctWQ_dl). 高频段阻抗行为对应涂层的物理阻抗, 低频段对应涂层与溶液界面的电化学反应阻抗. 实验结果表明, 随着La 浓度增加, 氧化膜及双电层的伪电容增大, 且在La 含量30mol%时达到最大值, 与CV实验结果一致, 证明了加入La 能提高RuO₂涂层的电催化活性. 但在析氯反应区间, 涂层氧化膜的导电性在含La 大于30 mol%之后迅速下降, 在低频段产生Warburg 阻抗, 与其表面钝化和特性吸附现象有关,这是导致含La 70 mol%时电催化活性急剧下降的原因.     

铝镧共掺杂的氧化锌红外隐身涂料在帐篷织物上的应用

以水性聚氨酯为粘合剂,掺杂Al和La的ZnO为填料,配以其它助剂制成了红外隐身涂料,应用在帐篷织物表面,探究涂层厚度以及填料含量对红外发射率的影响,并研究了导热系数和红外隐身性能之间的关系。 研究发现,涂层厚度和填料含量对涂层织物的红外发射率有着显著的影响。 当填料质量分数为70%时,得到的帐篷涂层织物的红外发射率可降至0.622,调节填料含量和涂层厚度,可以的得到红外发射率在0.622~0.932之间的帐篷涂层织物。 此外,发现导热系数对红外隐身性能也有一定的影响,红外隐身性能随着导热系数的增加而提高。 通过调节填料含量和涂层厚度制作不同红外发射率的涂层帐篷织物,放在不同背景下拍摄红外热成像图,发现涂层在不同的环境中均具有良好的伪装能力。     

Influence of pyrogenic particles on the micromechanical behavior of thin sol-gel layers

Coatings based on sol-gel technology with different types of nanoparticles embedded into the sol-gel matrix were fabricated, and the resulting properties were investigated. Pyrogenic silica nanoparticles were added to the sol before coating. The silica particles varied in primary particle size and agglomerate size, and in their surface modification. The particles were wetted in ethanol and dispersed to certain finenesses. The difference in agglomerate size was partly caused by varying particle types, but also by the dispersing processes that were applied to the particles. The resulting coatings were examined by visual appearance and SEM microscopy. Furthermore, their micromechanical properties were determined by nanoindentation. The results show an important influence from the added nanoparticles and their properties on the visual appearance as well as the micromechanical behavior of the sol-gel coatings. It is shown that, in fact, the particle size distribution can have a major impact on the coating properties as well as the surface modification.     

The optimal structure-conductivity relation in epoxy-phthalocyanine nanocomposites

Phthalcon-11 (aquocyanophthalocyaninatocobalt (III)) forms semiconducting nanocrystals that can be dispersed in epoxy coatings to obtain a semiconducting material with a low percolation threshold. We investigated the structure-conductivity relation in this composite and the deviation from its optimal realization by combining two techniques. The real parts of the electrical conductivity of a Phthalcon-11/epoxy coating and of Phthalcon-11 powder were measured by dielectric spectroscopy as a function of frequency and temperature. Conducting atomic force microscopy (C-AFM) was applied to quantify the conductivity through the coating locally along the surface. This combination gives an excellent tool to visualize the particle network. We found that a large fraction of the crystals is organized in conducting channels of fractal building blocks. In this picture, a low percolation threshold automatically leads to a conductivity that is much lower than that of the filler. Since the structure-conductivity relation for the found network is almost optimal, a drastic increase in the conductivity of the coating cannot be achieved by changing the particle network, but only by using a filler with a higher conductivity level.     

TiO2表面包覆SiO2和Al2O3的机理和结构分析

在二氧化钛的表面上包覆一层保护膜,使二氧化钛的表面和周围介质之间产生屏障,从而降低二氧化钛的光化学活性,有利于提高二氧化钛的分散性、耐光性、耐候性和抗粉化性.     

Effects of trace water on charging of silica particles dispersed in a nonpolar medium

This paper presents an investigation of the effects of trace water on the charging of silica (SiO(2)) particles dispersed in a nonpolar medium. There are a growing number of applications that seek to use electrostatic effects in apolar media to control particle movement and aggregation stability in such systems. One factor that is often overlooked in the preparation of nonpolar colloidal dispersions is the amount of water that is introduced to the system by hygroscopic particles and surfactants. The amount and location of this water can have significant effects on the electrical properties of these systems. For nonpolar surfactant solutions it has been shown that water can affect the conductivity, and it has been speculated that this is due to swelling of the polar cores of inverse micelles, increasing the fraction of them that are charged. Some studies have suggested that particle surface charging may also be sensitive to water content, but a clear mechanism for the process has not been fully developed. The situation with particles is further complicated by the fact that it is often unclear whether the water resides on the particle surfaces or in the polar cores of inverse micelles. The current work explores not only the effect of water content on reverse micelle and particle charging but seeks to differentiate between water bound to the particles and water located in the micelles. This is accomplished by measuring the solution conductivity and the electrophoretic mobility of silicon dioxide particles dispersed in solutions of Isopar-L and OLOA 11000. The water content is determined for both the dispersion and the supernatant after centrifuging the particles out. It is found that at equilibrium the majority of the water in the system adsorbs to the surface of the hygroscopic silica particles. In addition, the effect of water on particle electrophoretic mobility is found to be dependent on surfactant concentration. At small OLOA concentrations, additional water results in an increase in particle mobility due to increased particle charging. However, at large OLOA concentrations, additional water leads to a decrease in particle mobility, presumably as a result of increased electrostatic screening or neutralization. Thus, particle charging and electrophoretic mobility in an apolar surfactant solution are found to be highly sensitive to both the total water content in the system and to its concentration relative to the amount of surfactant present.     

液相沉积法制备TiO2颗粒表面包覆SiO2纳米膜

研究了用液相沉积法在TiO2颗粒表面包覆SiO2纳米膜的过程.通过透射电镜(TEM)和酸溶实验分析,证实本实验在TiO2颗粒表面包覆了一层连续、致密的SiO2纳米膜.ζ-电位分析表明,颗粒表面只需少量包覆就可以显著改变颗粒表面的电动力学行为.采用 X射线荧光光谱分析仪（XRF）测定SiO2包覆量随包覆过程的变化.通过X射线光电子能谱（XPS）分析,获得Ti 2p、Si 2p及 O 1s电子结合能及其相对强度随包覆过程的变化规律,揭示硅酸分子在TiO2颗粒表面的包覆过程.分析表明,初期形成的活性硅酸分子与TiO2颗粒表面的羟基反应形成Ti－O－Si键,后期形成的硅酸分子与已键合在表面的硅酸发生缩合反应,形成连续致密的硅膜,膜层在陈化过程中继续缓慢生长.     

锂离子电池用多孔硅/石墨/碳复合负极材料的研究

在两步高能球磨和酸蚀条件下制得了多孔硅/石墨复合材料，并对其进行碳包覆制成多孔硅/石墨/碳复合材料。通过TEM，SEM等测试手段研究了多孔硅材料的结构。作为锂离子电池负极材料，电化学测试结果表明多孔硅/石墨/碳复合材料相比纳米硅/石墨/碳复合材料有更好的循环稳定性。同时，改变复合体配比、热解碳前驱物、粘结剂种类和用量也会对材料的电化学性能产生较大的影响。其中使用质量分数为10％的LA132粘结剂的电极200次循环以后充电容量保持在649.9 mAh·g^-1，几乎没有衰减。良好的电化学性能主要归因于主活性体-多孔硅颗粒中的纳米孔隙很好地抑制了嵌锂过程中自身的体积膨胀，而且亚微米石墨颗粒和碳的复合也减轻了电极材料的体积效应并改善了其导电性。     

硅纳米粒子聚苯胺包覆改性及其嵌/脱锂电化学性能

利用直流电弧等离子体蒸发法合成硅纳米粒子(SiNPs),粒径为20~30 nm。采用对氨基苯甲酸(ABA)处理SiNPs,并在ABA-SiNPs表面进行苯胺(ANi)原位化学氧化聚合,形成核/壳型聚苯胺包覆硅纳米复合粒子(PANi-SiNPs)。FTIR、DSC、XRD、TEM等分析结果表明,ABA与SiNPs之间形成了化学键,粒子表面引入了ANi基团,复合粒子中PANi质量含量约为62%。电化学性能测试表明,PANi包覆层的存在大幅度提高了SiNPs的循环稳定性能,在100 mA·g~(-1)的电流密度下循环100次后,电池容量保持率为92.5%,远高于未改性的SiNPs的性能。聚苯胺包覆改性SiNPs,改善其导电性能的同时,可以极大地缓冲充/放电过程中的体积变化,提高电极的循环稳定性能。     

Preparation of photocurable silica–titania hybrid coatings by an anhydrous sol–gel process

Photocurable silica-titania hybrid coatings were prepared through an anhydrous sol–gel process. Moreover, test samples were prepared by the addition of definite ratios of fluoro acrylate oligomers into the formulations to manage the optical properties of transmitted light. Formulations were applied to corona-treated polycarbonate substrates. Upon adding the inorganic component to the coating material, thermal, mechanical, and other properties, such as hardness, gloss, contact angle, and flame resistance were improved. The photocured hybrid films showed an increase in the refractive index with increasing the titanium tetraisopropoxide content. As expected, a decrease was observed in the refractive index of the coatings with the incorporation of fluoro acrylate resin. The surface morphology of the hybrid films was characterized by ESEM analysis. In addition the chemical composition of the surface of the coatings was identified by ESEM–EDS technique. ESEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

硅纳米粒子聚苯胺包覆改性及其嵌/脱锂电化学性能

利用直流电弧等离子体蒸发法合成硅纳米粒子（Si NPs）,粒径为20~30 nm。采用对氨基苯甲酸（ABA）处理Si NPs,并在ABA-Si NPs表面进行苯胺（ANi）原位化学氧化聚合,形成核/壳型聚苯胺包覆硅纳米复合粒子（PANi-Si NPs）。FTIR、DSC、XRD、TEM等分析结果表明,ABA与Si NPs之间形成了化学键,粒子表面引入了ANi基团,复合粒子中PANi质量含量约为62%。电化学性能测试表明,PANi包覆层的存在大幅度提高了Si NPs的循环稳定性能,在100 mA·g^-1的电流密度下循环100次后,电池容量保持率为92.5%,远高于未改性的Si NPs的性能。聚苯胺包覆改性Si NPs,改善其导电性能的同时,可以极大地缓冲充/放电过程中的体积变化,提高电极的循环稳定性能。     

Scanning thermal microscopy techniques for polymeric thin films using temperature contrast mode to measure thermal diffusivity and a novel approach in conductivity contrast mode to the mapping of thermally conductive particles

Advances in production are leading to increasing use of polymeric thin films in applications such as automotive bearings. Two approaches have been developed to study the thermophysical properties of these thin films: The first technique based on Flash theory uses a scanning thermal microscopy (SThM) tip in temperature contrast mode to measure thermal diffusivity over a nano-scale area. The SThM tip is in contact with the upper surface of the film to detect a heat pulse delivered by a microelectromechanical heater platform from the lower surface. The second technique is a conductivity contrast mode SThM based approach for measuring the size and distribution of thermally conducting particles in thin film polymeric coatings. Topographical and thermal conductivity data are combined to produce a “correlation analysis value” 3D particle map of the coating. Good practice and a case study are highlighted.     

Temperature-responsive formation of colloidal nanoparticles from poly(N-isopropylacrylamide) grafted with single-stranded DNA

The thermal properties and temperature-responsive nanoparticle formation of poly(N-isopropylacrylamide) grafted with single-stranded DNA (PNIPAAm-g-DNA) were investigated. Copolymerization between nonamer single-stranded DNA with a vinyl group at its 5' terminus (DNA macromonomer) and NIPAAm was carried out so that the DNA macromonomer unit content should be less than 1 mol %. The turbidimetry and differential scanning calorimetry of the copolymer showed that the transition temperature increased and the enthalpy change of the phase transition decreased with increasing DNA macromonomer content in the copolymers, indicating that the DNA macromonomer behaves as a hydrophilic part in the copolymer and that the hydrophilicity is greater than that of sodium styrenesulfonate. Above the phase transition temperature, the copolymers formed colloidal nanoparticles with a dehydrated PNIPAAm core surrounded by DNA. When the formation of particles was conducted at higher temperatures, the dehydration of the copolymers proceeded such that the hydrodynamic radius (Rh) of the particles decreased. From the results of light scattering measurements, we calculated the surface area of particles occupied by one DNA (S(DNA)). The S(DNA) value decreased with increasing formation temperature, indicating that the DNA density on the particle surface increases with increasing formation temperature. The increase in the DNA density was also confirmed from the zeta-potential measurement of the particle. When MgCl2 was added to the copolymer solutions, the anionic charge of DNA was neutralized by Mg2+ so that Rh and the molecular weight of the particles increased with the increasing MgCl2 concentration. The turbidimetric detection of a target DNA was successfully demonstrated by utilizing the stability decrease of the colloidal particle upon hybridization on the particle surface.     

SiCp/ Al复合材料与化学镀镍层结合机理研究

根据结构化学理论，用SEM, EDAX和XPS等测试手段研究了镀层和碳化硅颗粒增强铝基复合材料(SiC_p/ Al)的表面、断面形貌及界面的结合状态，分析了镀层和基体之间的结合机理。结果表明，Ni镀层与复合材料界面有良好的结合，在复合材料表面的SiC-Al界面，初期沉积物Ni按Al的晶格外延生长出现微晶层，然后吸附原子扩散迁移、碰撞结合并与界面上的SiC晶格匹配生长，在镍层中诱发了拉伸应力。镍晶格和基体粒子之间产生了键合作用，形成的键显示出共价键和离子键的混合性质。     

含氟高分子/SiO_2杂化疏水材料的制备及涂层表面性质

采用自由基溶液聚合与溶胶-凝胶法相结合的方法制备了含氟高分子/SiO2杂化疏水材料.通过甲基丙烯酸十二氟庚酯(FA)与乙烯基三乙氧基硅烷(VTES)共聚合成了含氟硅共聚物(PFAS),进一步通过原硅酸乙酯(TEOS)与PFAS共聚物溶液共水解缩聚制备了具有含氟侧基的碳碳主链高分子和硅氧网络的含氟高分子/SiO2杂化疏水材料.研究结果表明,SiO2组分含量提高可以显著增加杂化材料薄膜的涂敷厚度,改善其耐久性能,而对杂化材料疏水性能的影响不大.     

Synthesis, characterization and flame retardant of UV-curable hybrid coatings containing SiO2–P2O5–B2O3 via sol–gel method

A ternary sol containing silicon, phosphorus and boron modified by ??-methacryloxypropyltrimethoxysilane was synthesized by sol?Cgel method. The ternary sol was incorporated into the organic matrix and UV-curable organic/inorganic hybrid coating materials were obtained. Hardness, transmittance, haze, cross-cut adhesion and abrasion resistance results showed that the mechanical properties of the hybrid coatings improved effectively with no comprising on optical properties by increasing sol content. Scanning electron microscopy and Energy Dispersive X-ray spectrometer studies indicated that inorganic particles were homogenously dispersed in the organic matrix. The flame retardancy of the UV-curable coatings was investigated by thermogravimetric analysis and microscale combustion calorimeter. The results showed that the incorporation of sol into the organic network led to an improvement in the thermal stability and flame retardancy of the hybrid coating materials. It is a desirable achievement to improve simultaneously both flame retardancy and mechanical properties of the coatings.