Synthesis of Polyurethane/Poly(urea-formaldehyde) Double-shelled Microcapsules for Self-healing Anticorrosion Coatings

One-component, catalyst-free self-healing coatings with double-shelled polymer microcapsules have drawn considerable attention due to wide applications. In this work, the synthesis parameters of double-shelled polymer microcapsules and the mechanism of the self-healing process were systematically investigated. Apart from the chemical structure of the microcapsule shell, the shell thickness, the microcapsule size,and the core fraction could affect the self-healing anticorrosion properties. The synthesis parameters were further optimized in terms of the agitation rate, p H, weight ratio of core to shell, and temperature. Under these conditions, the microcapsule shell consisting of a rough surface formed by poly(urea-formaldehyde) and a smooth inner wall by polyurethane was prepared. The size of the microcapsules and core fraction were calculated to be approximately 30 μm and 75%, respectively. The self-healing anticorrosion coating incorporating as-synthesized microcapsules exhibited corrosion resistance in artificially scratched areas, which was further characterized by electrochemical impedance spectroscopy.     

Microencapsulation of dodecyl acetate by complex coacervation of whey protein with acacia gum and its release behavior

Complex coacervation of whey protein(WP) with acacia gum(AG) was carried out in water with the presence of dodecyl acetate (DA),a component of insect sex pheromones,in order to obtain microcapsules with DA as the core material and WP-AG coacervate as the wall materials.Through variations in wall/core ratios,concentrations of the wall materials in capsule preparations,DA encapsulation was optimized,which showed a high DA encapsulation was achieved when coacervation was conducted at pH 3.5 with wall/core mass ratio at 3 combined with concentration of wall materials at 1.0 wt%.Morphology and the structure of DA loaded microcapsules were examined by scanning electron microscope,which showed the microcapsules were of core/shell structure with DA encapsulated in the inner of the microcapsules.DA release was examined and the behavior of the release was discussed.     

SYNTHESES AND STRUCTURES OF POLYPHENYLSILSESQUIOXANES

Phenyltrichlorosilane was hydrolyzed both ifi. toluene and in ether from which two kinds of prepolymers were obtained with different structures, molecular weights, and molecular weight distributions. Polymers were prepared from the prepolymers in various polymerization conditions. The ladderlike, branched, and crosslinked structures formed under different polymerization conditions were characterized by means of FTIR, ~1H and ~(29)Si-NMR, and elemental analysis. Azeotropic distillation of solvents and H_2O formed during polymerization was found useful in removing H_2O from the system and high molecular weight products with perfect ladderlike structure were obtained.     

The effect of silica morphology on properties of PVA/silica nano-composites

Two kinds of poly(vinyl alcohol)(PVA)-silica composites were prepared with different methods. One composite was prepared by directly mixing PVA with 80 nm silica nano-particles which were made from tetraethoxysilane(TEOS). The another was obtained by the mixing PVA and hydrolyzed TEOS in the presence of acid-catalyst. The properties of the two PVA/silica hybrids were characterized by means of scanning electron microscopy(SEM), UV-Visible spectroscopy,solubility tests, limiting oxygen index(LOI) test, tensile test and dynamical mechanical analysis(DMA), respectively. The results indicate that PVA-TEOS composites(PT for short) display more transparency than PVA-silica nano-particles hybrids(PS for short). At the same time, The PT composites presented more excellent performance than PS in water resistance, fire resistance and mechanical properties. Moreover, the Tg of PT increased with increasing TEOS content, while that of PS decreased.     

Synthesis of vegetable oil based polyol with cottonseed oil and sorbitol derived from natural source

In order to prepare the polyol with all bio-based components as raw materials,cottonseed oil was first epoxidized by peroxyformic acid generated in situ from hydrogen peroxide and formic acid,and the cottonseed oil based polyols with variable hydroxyl value were then prepared by the ring-opening of epoxidized cottonseed oil with sorbitol,which is a multi-functional hydroxyl compound derived from a natural source.The chemical structure of the products was characterized with FTIR analysis, and the residual...     

Preparation and Characterization of Microcapsules for Self-healing Materials

The urea-formaldehyde(UF) capsules filled with a healing agent, a mixture of epoxy resins(epoxy 711 and E-51) as core material, were produced by means of one step in-situ polymerization. The characteristics of these microcapsules were studied via scanning electron microscopy(SEM), particle size analysis, FTIR and DSC/TGA. The results show that the dispersed and integrated microcapsules of 5 μm in shell thickness were synthesized successfully. The capsules were produced with diameters ranging from 10 to 250 μm via controlling agitation rate. Young’s modulus of the capsule was a little lower than those of the epoxy resins, but the microcapsules having such a shell thickness were robust enough to survive handling during manufacturing self-healing composites. When damage occurred in the epoxy matrix, the crack could rupture the microcapsule to make the repairing agent release.     

Hierarchical crystalline structures induced by temperature profile in HDPE bars during melt penetration process

The hierarchical crystalline morphologies and orientation structures across the thickness direction in high-density polyethylene(HDPE) molded bars were investigated via a novel melt-penetrating processing method named multi-melt multi-injection molding(M3IM). The samples with various mold temperatures(20, 40 and 60 °C) were prepared, and the effects of the external temperature profile on the evolution of crystalline microstructures were studied. With scanning electron microscopy(SEM), the transition of crystalline morphology from ring-banded structure to oriented lamellae was observed with decreasing mold temperature, and the oriented lamellae were formed at the sub-skin layer of the samples at the lowest mold temperature, which was further testified by differential scanning calorimetry(DSC). With the decline of mold temperature, the degree of orientation, obtained from two-dimensional small angle X-ray scattering(2D-SAXS), was increased and long periods rose a little. Thus, decreasing mold temperature was beneficial to the formation of orientation structures because the relaxation of chains was weakened.     

Performance enhancement of bimetallic Co-Ru/CNTs nano catalysts using microemulsion technique

Bimetallic cobalt-ruthenium nano catalysts supported on carbon nanotubes(CNTs)are prepared using microemultion technique with water-to-surfactant ratios of 0.5—1.5.The nano catalysts were extensively characterized by different methods and their activity and selectivity in Fischer-Tropsch synthesis(FTS)have been assessed in a fixed-bed microreactor.The physicochemical properties and performance of the nanocatalysts were compared with the catalyst prepared by impregnation method.Very narrow particle size distribution has been produced by the microemulsion technique at relatively high loadings of active metals(15 wt%Co and 1 wt%Ru).According to TEM images,small Co particles(2—7 nm)were mostly confined inside the CNTs.Comparing with the catalyst prepared by impregnation,the use of microemulsion technique with water to surfactant ratio of 0.5 decreased the average cobalt oxide particle size to 4.8 nm,the dispersion was almost doubled and the reduction increased by 28%.Activity and selectivity were found to be dependent on the catalyst preparation method and water-to-surfactant ratio(as well as cobalt particle sizes).CO conversion increased from 59.1%to 75.1%and the FTS rate increased from 0.291 to0.372 gHC/(gcath).C5+liquid hydrocarbons selectivity decreased from 92.4%to 87.6%.     

Facile fabrication of drug-loaded PEGDA microcapsules for drug evaluation using droplet-based microchip

Droplet-based microfluidic technology can be utilized as a microreactor to prepare novel functional monodisperse microcapsules. In this study, a droplet-based microfluidic chip with surface modification,which allowed the one-step preparation of double emulsion microcapsules. An O/W/O double emulsion using polyethylene(glycol) diacrylate(PEGDA) solution as the intermediate water phase was prepared by regulating the hydrophilicity and hydrophobicity of the chip surface, with PEGDA microcapsules pr...     

Electrochemical Determination of Alkaline Phosphatase in Human Serum by Differential Pulse Voltammetry

Differential pulse voltammetry(DPV) was applied to the determination of alkaline phosphatase(ALP) activity in human serum with phenyl phosphate as the substrate. Phenyl phosphate can enzymatically be hydrolyzed to produce phenol which is quantified by DPV at 660 mV(vs. Ag/AgCl) in the concentration rangeof 2.0--100 μmol/L. The standard curve for ALP is linear over the range from 0.06 to 1000U/L with a relative standard deviation of 3.0%. The conditions for the enzymatic reaction and voltammetric detection were optimized and the kinetic constants were also examined. The human serum samples were tested by this method and the results were in good agreement with those obtained by the routine p-nitrophenyl phosphate spectrophotometric method.     

电泳显示微胶囊的制备和性能

以有机颜料联苯胺黄为显色粒子, 四氯乙烯和甲苯混合溶液为分散介质, 油溶性蓝N为吸光染料, 用超分散剂CH-2C分散颜料粒子, 脲醛树脂为壁材, 通过一步原位聚合法制备了电泳显示微胶囊. 通过显微镜检查微胶囊的表面形貌及粒径, 并对微胶囊内颜料粒子的电场响应特性和显示性能进行考察. 结果表明, 所得微胶囊表面光滑, 囊壁透明, 囊内颜料粒子对电场变化能够快速可逆地响应, 并具有双稳显示特性.     

脲甲醛缩聚物制备电子墨水微胶囊研究

在原位聚合法制备脲甲醛树脂微胶囊的过程中 ,使用水溶性低分子量脲甲醛缩聚物代替传统的脲甲醛预聚体 (一羟甲基脲、二羟甲基脲 )作为反应单体 ,由于脲甲醛缩聚物比后者更容易吸附在分散相液滴表面 ,解决了用原位聚合法制备脲甲醛微胶囊所常有的结块、粘连、表面粗糙、产率低的问题 .研究了低分子量脲甲醛缩聚物水溶液的粘度特征和表面活性及其与胶囊包封率的关系 .使用这种方法制备出了电子墨水微胶囊     

XPS evidence for structure-performance relationship in selective hydrogenation of crotonaldehyde to crotyl alcohol on platinum systems supported on natural phosphates

The design of the oppositely charged ink particles based on titanium dioxide and carbon black for the monochrome electrophoretic display (EPD) was reported. The white ink particles with acidic surface and black ink particles with basic surface were synthesized and sterically stabilized by long alkyl chains, which were charged oppositely by mixing with basic surfactant (OLOA 1200) and acidic surfactant (Span 80), respectively. The electrophoretic mobility and the Zeta potential were −3.87 × 10⁻¹⁰ m² V⁻¹ s⁻¹ and −25.1 mV for the white ink particles, 3.79 × 10⁻¹⁰ m² V⁻¹ s⁻¹ and 24.6 mV for the black ink particles. In addition, the block copolymer, poly(lauryl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (PLMA-b-PDMAEMA) synthesized by atom transfer radical polymerization (ATRP), was first incorporated in the modification of the pigments for the fine encapsulation. Then, a stable dual-particle electronic ink with contrast ratio of 120:1 was prepared and encapsulated with the gelatin (GE)/sodium carboxymethylcellulose (NaCMC)/sodium dodecyl sulfate (SDS) microcapsules by complex coacervation method. Finally, the matrix character display prototype driven at a low voltage exhibited excellent performance, the contrast ratio of which was 8:1 at 9 V DC.     

Electrophoretic mobility of the polymer-like micelles of tetradecyldimethylamine oxide hemihydrochloride

Effects of the surfactant concentration C_d and the NaCl concentration C_s on the electrophoretic mobilities U of the well-characterized polymer-like micelles have been investigated by the electrophoretic light scattering, using tetradecyldimethylamine oxide hemihydrochloride (C14DMAO·1/2HCl). At the high ionic strength of 0.1 mol kg⁻¹ NaCl, the electrophoretic mobilities were independent of C_d (5 mM < C_d < 100 mM), despite the concentration-dependent micelle growth of the polymer-like micelles. This suggests that the electrophoretic mobility of the polymer-like micelle at high ionic strengths is independent of the contour length (i.e., the molecular weight), as found on linear polyelectrolytes. Somewhat surprisingly, the entanglements of the polymer-like micelles gave small effect on the electrophoretic mobilities in the examined range of the surfactant concentration above an overlap concentration. The mobilities of the polymer-like micelle decreased with √C_s in a single exponential manner in the range of C_s from 0.02 to 0.3 mol kg⁻¹. It is suggested that the cylinder model can be applied to the electrophoretic mobilities of the polymer-like micelles at high ionic strengths (i.e. a free-draining behavior), since the persistence length of the polymer-like micelle (20 nm) is much larger than the Debye length at high ionic strength.     

基于电泳沉积法碳纤维表面改性的研究进展及应用

近些年来,碳纤维(CF)由于具有优异的力学性能,被用作复合材料的增强体。但CF表面缺少极性基团,呈现化学惰性,使CF与树脂(EP)之间的界面粘结性能较差。为了改善该问题,需要对CF表面进行改性。氧化石墨烯(GO)和碳纳米管(CNT)具有大的比表面积,且表面含有大量的极性基团,将二者引入CF表面,可以有效改善CF与EP之间的界面问题。利用电泳沉积技术成功地制备了GO和CNT/EP复合材料,并显示出各种优异的界面性能。本文对国内外通过电泳沉积方法在CF表面沉积CNT和GO的改性以及电泳沉积GO和CNT的应用现状进行了综述和分析,并在此基础上,对电泳沉积碳纳米材料改性CF的研究趋势及前景进行展望。     

Electrophoretic behaviour of calcium oxalate monohydrate in liquid mixtures

An experimental investigation on electrophoresis of calcium oxalate monohydrate in several liquid mixtures (methanol-, ethanol-, 2-propanol-, and methanol-acetonewater) is described.The electrophoretic transport is considered from the view-point of the Thermodynamics of Irreversible Processes. Linear relations have always been found between the mass flux and the applied electric field. The -potential of the interface C.O.M./liquid mixture has been estimated by using the classial theory of electrophoretic mobility of colloidal particles. The influence of the composition of the mixture on the electrophoretic coefficient has been discussed on the basis of the variation of -potential, viscosity and dielectric constant with the molar fraction of alcohol for binary mixtures and acetone for ternary mixtures. The concentration dependence of the electrophoretic coefficient is found to be linear only in the latter case.     

Electrophoretic deposition of bacterial cells

The possibility to use alternating current electrophoretic deposition (AC-EPD) to deposit living cells in the form of Staphylococcus aureus and Escherichia coli on stainless steel was assessed. The experimental results revealed that these bacteria can be successfully deposited on metallic surfaces from demineralized water and sucrose based solutions using asymmetric unbalanced electric fields. Cell viability of the deposited bacteria was influenced by the strain and deposition medium.     

Electrophoretic deposition of calcium phosphates from non-aqueous media

Electrophoretic deposition of ultrafine calcium phosphates from non-aqueous suspensions onto metallic substrates was attempted in order to obtain coatings with varying porosities. Aging effects were studied by measuring changes in the electrophoretic deposition behavior of the calcium phosphate particles in the non-aqueous suspensions. It was observed that the surfaces of the calcium phosphates develop significant electrostatic charge during aging in order to enable the formation of a dense and uniform deposit. The addition of surface charge conditioners such as HCl was found to have a similar effect. Dispersion conditions were varied to obtain coatings of the desired green densities, which were sintered to different microporosities.     

High compact melamine-formaldehyde microPCMs containing n-octadecane fabricated by a two-step coacervation method

Microcapsules containing n-octadecane were successfully fabricated by an in-situ polymerization process with melamine-formaldehyde (MF) prepolymer and a hydrolyzed copolymer of styrene and maleic anhydride (SMA) as shell materials. To achieve a long service time of microcapsules containing phase change materials (microPCMs), the compactness of shells was improved by adding the MF prepolymer twice. The mechanism of this method was a two-step coacervation (TSC) under the help of hydrolyzed SMA compared to a one-step coacervation (OSC). To understand the influence of both coacervations, properties of shells were investigated in terms of morphologies, density, thickness, and stability by means of scanning electron microscopy (SEM), transmission electron microscopy, and thermal gravimetric analysis (TGA). The data of shells thickness were achieved from the cross-section SEM images. It shows that the average thickness of shells from two kinds of process are 0.1 μm. The density and stability in water of shells fabricated by TSC are both higher than that of shells by OSC. TGA curves show the expected microPCMs of TSC losing weight from 200 to 400 °C. The release curves, relationship between time and logarithmic residual weight of core, show there are two decrease-linear steps after curve regression. It can be concluded from all these results that the TSC method may be a promising method leading to a compact shell structure for various application.     

Electrophoretic rotation of doublets composed of two spheres almost in contact

Colloidal doublets formed from spheres with different zeta potentials rotate as dipoles into alignment with an applied electric field. The rate of rotation is proportional to the difference in the electrophoretic mobilities of the isolated spheres times a dimensionless rotation coefficient (N). The coefficient N, which describes the interaction effects between the particles, has been previously calculated numerically under the assumptions of infinitesimal double layers and uniform zeta potentials on each sphere. These numerical values have been used to interpret experiments which probe the tangential forces between two particles almost in contact. But since these assumptions might not hold for the small gaps in actual experiments, it is important to know how N is affected when the double layers of two spheres overlap or when the charge is nonuniformly distributed on the sphere surfaces (especially in the gap region). Using an extension of the Lorentz reciprocal theorem for Stokes flow, we have developed a semi-analytical solution for N which is valid in the asymptotic limit of small (but finite) gaps of fluid between the spheres. For infinitesimal double layers and uniform zeta potentials, this result shows that N is weakly singular in the gap between the spheres. Our method also enables us to examine the effects of overlapping double layers and nonuniform zeta potentials in the gap region, and an important result of this paper is that even when these effects are considered, the result for infinitesimal double layers and uniform zeta potentials remains a very good approximation.