“蒸发成核法”研究KDP晶核大小及形状

提出一种有望用于研究临界或近临界晶核大小及形状的新方法,借助于原子力显微镜(AFM),对磷酸二氢钾(KDP)晶核的大小以及形状进行了研究。结果表明,应用"蒸发成核法"可得到纳米尺寸的晶核,随溶液浓度的增大,晶核直径从25.8nm增大至59.1nm。其中最小尺寸的晶核,与低过饱和度下的理论预测值较接近。一般情况下,晶核呈球缺型,与经典理论假设形状相符。但蒸发温度低时,晶核可呈矩形(柱状),与KDP晶体的宏观形状更为接近。在蒸发速度较快时,晶核难以形成,只会出现溶质的堆积体。     

Effect of crystallization on morphology-conductivity relationship in polypyrrole/poly(?-caprolactone) blends

Electrically conducting blends, based on polypyrrole (PPy) as the conductive polymer and poly(?-caprolactone) (PCL) as an insulating polymeric matrix, were prepared by polymerizing pyrrole (Py) in its vapor state inside the PCL matrix. The roles of specific interactions between blend components as well as the crystallization of PCL matrix in the resulting morphology have been analyzed by Fourier-transform infrared spectroscopy (FTIR), thermo-optical analysis (TOA) and atomic force microscopy (AFM). The results indicate that PPy is located within both the intra and interspherulitic regions of the PCL matrix achieving a well-developed connected network. Compared with amorphous matrices, considerable conductivity (around 1 S/cm) was raised with the crystalline PCL matrix with only a relatively low level of the conductive polymer (∼5%) in the blend.     

Preparation of photo curable highly hydrophobic coatings using a modified castor oil derivative as a sol-gel component

Modification and use of natural products have gained a lot of interest in recent years due to their environmental friendliness and their availability from different sources. In this study castor oil based photo curable highly hydrophobic coatings were prepared and characterized. Castor oil (CO) was first modified with 3-isocyanato propyl triethoxy silane and then it was hydrolyzed prior to the coating preparation. The resulting precursor was mixed with norbornyl acrylate, hexane diol diacrylate and hydrophobic coatings were prepared with the aid of fluorinated and nonfluorinated alkoxy silane coupling agents. The addition of fluorine showed a significant impact on the properties of the coatings. As the fluorine content was increased in the formulations, flame retardancy and the contact angle values of the coatings increased. The highest amount of fluorine containing coating showed a contact angle of 119°. Then with the addition of nonfluorinated alkoxysilane compounds, a contact angle of 130° was reached. Also the effect of post-cure temperature on contact angle values was investigated.     

Studies on the interactions between bovine β-lactoglobulin and chitosan at the solid-liquid interface

Chitosan ultrathin films have been formed on polycrystalline Au substrates using the LbL technique with the purpose of studying its interaction with bovine β-lactoglobulin (β-LG) at the solid-liquid interface. The immobilization of chitosan was followed by Quartz Crystal Microbalance with energy dissipation (QCM-D), Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The behavior of the chitosan films in the presence of β-LG solutions with different bulk concentrations ([β-LG]), ionic strength (I), and pH has been investigated using the same techniques plus Atomic Force Microscopy (AFM). The results showed that for pHs lower than protein's pI, weak intermolecular forces (H bonding, Van der Waals, hydrophobic, etc.) are established between β-LG and chitosan (especially close to the pI) leading to low coverage nonspecific adsorption. On the contrary when pH > pI, strong ionic bonding through attractive electrostatic interactions lead to high coverage adsorbed phases composed of large β-LG aggregates. The adsorption process was shown to consist of a relatively fast step (in which these interactions are predominant) which is followed, once the β-LG monolayer is exceeded, by the slow formation of thicker and increasingly viscoelastic films through β-LG self-aggregation. QCM-D and AFM experiments unveiled the role of [β-LG] and I on the formation of these aggregates. The adsorption isotherm built from impedance data in the medium-low [β-LG] range (0.001-0.3 mg mL⁻¹), showed good fitting to the Langmuir model confirming that the formation of one β-LG monolayer is achieved in this concentration range.     

A morphological view of the sodium 4,4′‐distyrylbiphenyl sulfonate fluorescent brightness distribution on regenerated cellulose fibers

Evidence of the sorption of the whitening agent sodium 4,4′‐distyrylbiphenyl sulfonate in the presence of the anionic surfactant sodium dodecylsulfate or the cationic surfactant dodecyl trimethyl ammonium chloride on regenerated cellulose fibers is given by several microscopy techniques. Scanning electron microscopy provided images of the cylindrical fibers with dimensions of 3.5 cm (length) and 13.3 μm (thickness), with empty cores of 1 μm diameter and a smooth surface. Atomic force microscopy showed a fiber surface with disoriented nanometric domains using both tapping‐mode height and phase image modes. Atomic force microscopy also showed that the whitening agent and surfactant molecules were sorbed onto the fiber surface, in agreement with the adsolubilization sorption model. Transmission electron microscopy showed fibers with nanometric parallel cylinders, surrounded by holes where the fluorescent whitening molecules accumulated. On the basis of these techniques, we conclude that the sorption process occurs preferentially on the fiber surface in contact with the water solution, and under saturated conditions, the whitening agent penetrates into the pores and are simultaneously sorbed on the pore walls bulk, forming molecular aggregates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel process for isolating fibrils from cellulose fibers by high‐intensity ultrasonication. II. Fibril characterization

High‐intensity ultrasonication with a batch process was used to isolate fibrils from several cellulose sources, and a mixture of microscale and nanoscale fibrils was obtained. The geometrical characteristics of the fibrils were investigated with polarized light microscopy, scanning electron microscopy, and atomic force microscopy. The results show that small fibrils with diameters ranging from about 30 nm to several micrometers were peeled from the fibers. Some fibrils were isolated from the fibers, whereas some were still on the fiber surfaces. The lengths of untreated and treated cellulose fibers were investigated by a fiber size analyzer. The crystallinities of some cellulose fibers were evaluated by wide‐angle X‐ray diffraction and Fourier transform infrared spectroscopy. The high‐intensity ultrasonication technique is an environmentally benign method and a simplified process that conducts fiber isolation and chemical modification simultaneously and helps significantly reduce the production cost of cellulose nanofibers and their composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Applications of wittig reactions in dibenzo 18‐crown‐6‐ether substituted phenylenevinylene oligomer—synthesis,photo luminescent,and dielectric properties

Novel phenylenevinylene oligomer substituted dibenzo 18‐crown‐6 ether ring (DB‐OPV) was synthesized using dibenzo 18‐crown‐6 with terephthaldicarboxaldehyde via Wittig reaction. Formation of the oligomer was confirmed by spectral (FT‐IR, ¹H and¹³C‐NMR), gel‐permeation chromatography and elemental analysis. The morphology of the oligomer film of one‐dimensional and three‐dimensional architectures was observed using atomic force microscopy. The oligomer showed excellent photoluminescence with bluish green emission maxima at shorter wavelengths of 505 nm. Stability of the oligomer was analyzed using UV spectroscopy with varying time and temperature. The dielectric properties such as dielectric constant and loss factor for the oligomer have also been studied with respect to change of frequency (50 Hz–5 MHz) and temperature (30–60°C). The value of dielectric constant decreased with increasing frequency, which indicates that the major contribution to the polarization comes from orientation polarization. The value of dielectric constant increased with increasing temperature which is due to greater freedom of movement of the dipole molecular chains within the oligomer at high temperature © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hybrid polymer networks of unsaturated polyester–urethane as composite matrices for jute reinforcement

Reactions of unsaturated polyester resin and 4,4′ diphenyl methane diisocyanate were carried out at different NCO/OH ratios in presence of catalysts to form the hybrid polymer networks. Chain extender (1,4 butanediol) added in the hybrid network (NCO/OH ratio: 0.76) was optimized at a level of ～ 3 wt % only of the polyester resin. The curing of these networks was studied by a rigid body pendulum type (RPT) method in terms of reduced damping ratio and increased frequency. Lack of multiple glass transition temperatures, sharp Tan delta peak, and particulate composite type morphology clearly demonstrated the formation of phase mixed domains in the hybrid networks. The storage modulus and loss modulus master curves obtained by dynamic mechanical analysis indicate that hybrid polymer networks retained higher modulus at lower and intermediate frequencies over the polyester resin showing their superior time‐dependent response. Efficacy of these hybrid network resins was examined as matrices in the jute composites and compared with those of polyester resin and unsaturated polyester–polyurethane interpenetrating network matrices. It is found that the hybrid polymer network matrix composites exhibited superior physicomechanical properties under both dry and boiling water age test. Fractographic evidences such as fiber–matrix adhesion, hackle markings, and fiber breakage also supported their superior behavior over other composite matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

大气状态下AFM阳极氧化加工Si的研究

Si纳米氧化线是构筑基于Si的纳米器件的基础。通过AFM针尖诱导阳极氧化加工的n型Si(100)的实验得到凸出的n型Si(100)氧化物高度和偏置电压成线性关系,与针尖扫描速度成负对数关系,并在前人的基础上深化了AFM针尖诱导氧化加工的机理和理论模型,得到了合适的加工条件为偏压8 V和扫描速度1μm/s。     

Preparation of poly (isophthalamide-graft-methacrylamide) and its utilization in the modification of cellulose acetate ultrafiltration membranes

Methacrylamide was grafted on to poly (isophthalamide) (PIPA-g-MAA) to improve its solubility and hydrophilicity. Then, PIPA-g-MAA incorporated high performance cellulose acetate ultrafiltration (CA) membranes were prepared by phase inversion technique and physical properties of the membranes were studied by various analytical methods. The efficiency of these membranes in the removal of arsenic from aqueous stream was studied and an effort has been taken to correlate the separation efficiency with morphology. Overall results suggest that membrane hydrophilicity, structure and performance were improved significantly by the addition of PIPA-g-MAA. Thus PIPA-g-MAA can be considered as an effective modification agent for CA membranes.