Structure and Properties of Self-reinforced Material Made from Ultra-high Molecular Weight Polyethylene-montmorillonite Nanocomposite

High-strength and high-modulus ultra-high molecular weight polyethylene (UHMWPE), named self-re-inforced material, was obtained by the elongation of UHMWPE-montmorillonite nanocomposite at melting temperature. According to the scanning electron microscope (SEM) analysis, a great deal of fibrillar texture formed in the direction of elongation, and the tensile fractured surface was similar to that of highly oriented fiber. The transmission electron microscope (TEM) and selective area electron diffraction (SAED) analyses reveal that the reinforced phase of the self-reinforced material is an extended chain crystal and its size is about 50--200 nm wide and several microns long, and the montmorillonite layers are broken up to pieces in the size from 100 to 10 nm. The broken layers which have a huge surface area interacting strongly with macro-molecules reduces the entanglement density of UHMWPE and induces the chain orientation in flow field. It is supposed that the astriction of montmorillonite layers to polyethylene chains is not only end-tethered but also side-tethered. The differential scan calorimetry(DSC) analysis shows that there are two endothermal peaks for the self-reinforced material, of which the peak at a higher temperature(136.4℃) is ascribed to the melt-ing of the reinforced phase.     

STUDIES ON THE NATURE OF THE MACROMOLECULAR CONDENSED STATE OF "NASCENT" ULTRA HIGH MOLAR MASS POLYETHYLENE*

 Ultra high molar mass polyethylene (UITPE) powder as polymerized in a slurry process has been studied, in its nascent state, after recrystallization on rapid cooling from the melt and after hot compression molding to a film, by DSC,effect ofannealing the recrystallized specimen at 120～I30℃, morphology by polarizing optical microscopy and small angle X-ray scattering. Based on the experimental results obtained the macromolecular condensed state of the nascent UHPE powder is a rare case of a multi-chain condensed state of non-interpenetrating chains, involving interlaced extended chain crystalline layers and relaxed parallel chain amorphous layers. On melting, a nematic rubbery state of nanometer size domain resulted. The nematic-isotropic transition temperature was judged from literature data to be at least 220℃, possibly higher than 300℃, the exact temperature is however not sure because of chain degradation at such high temperatures. The recrystallization process from the melt is a crystallization from a nematic rubbery state. The drop of remelting peak temperature by 10 K of the specimen recrystallized from its melt as compared to the nascent state has its origin in the decrease both of the crystalline chain stem length and of the degree of crystallinity. The remelting peak temperature could be returned close to that of the nascent state by annealing at 120～130℃.     

Surface Modification of Montmorillonites by Chlorosilanes

Montmorillonite was modified by chlorosilane derivatives (trimethylchlorosilane and tert-butyldimethylchlorosilane)based on the reaction between OH group and chlorosilane,Fourier-transformed infrared spectra(FTIR)confirmed that chlorosilanes did react with the OH groups of montmorillonite.The effect of reaction time and dispersing agents on the intercalation was studied by wide angle X-ray diffraction(WAXD) method.Further experiments proved that there is no reactive OH group on the surface of layers in the interlayer galleries of montmorillonite.The cation exchange capacity(CEC) of montmorillonites was measured.showing that after modification by chlorosilane derivatives,CEC values drastically decreased.The dispersibility measurements of montmorillonites were conducted.which showed that the dispersibility of modified montmorillonites both in H2O and toluene wer improved due to the decrease of attractions of particles and layers.     

Preparation of Monodispersed Copper Nanoparticles by an Environmentally Friendly Chemical Reduction

In this paper, highly dispersive nanosized copper particles with a mean particle size of less than 6 nm are prepared by an environmentally friendly chemical reduction method. Non-toxic L-ascorbic acid acts as both reducing agent and antioxidant in ethylene glycol in the absence of any other capping agent. Transmission electron microscopy （TEM） is used to characterize the size and morphology of Cu nanoparticles. The results of UV-Vis spectroscopy （UV-Vis）, energy dispersive spectroscopy （EDS） and high resolution TEM （HRTEM） illustrate that the resultant product is pure Cu nanocrystals. The size of Cu nanoparticles is remarkably impacted by the order of reagent addition, and the investigation reveals the reaction procedure of Cu^2＋ ions and L-ascorbic acid.     

Encapsulation of ultrafine Pd nanoparticles within the shallow layers of UiO-67 for highly efficient hydrogenation reactions

Metal-organic frameworks(MOFs)have been used to encapsulate active metal nanoparticles(MNPs)to fabricate MNPs@MOFs composites with high catalytic efficiencies.However,the diffusion of reactants and the accessibility of MNPs located in the center of MOFs may be hindered due to the inherent microporous structures of MOFs,which would affect the catalytic activities of MNPs.Herein,we report a solvent assisted ligand exchange-hydrogen reduction(SALE-HR)strategy to selectively encapsulate ultrafine MNPs(Pd or Pt)within the shallow layers of a MOF,i.e.,UiO-67.The particle sizes of the encapsulated MNPs and the thickness of the MNPs-embedded layers can be adjusted easily by controlling the SALE conditions(e.g.time and temperature).Crucially,the LE-Pd@UiO-80-0.5 composite with the thinnest Pd-embedded layers displays remarkable catalytic efficiency with a high turnover frequency(TOF)value of 600 h^-1towards hydrogenation of nitrobenzene under 1 atm H_2at room temperature.The results indicate that the catalytic efficiency and the utilization of MNPs can be enhanced by compactly encapsulating MNPs within the shallow layers of MOFs as close to their outer surfaces as possible,owing to the short masstransfer distance and enhanced accessibility of overall MNPs.     

Effect of nano-fillers on conductivity of polyethylene/low melting point metal alloy composites

A novel method for preparing conductive polyethylene(PE) composites has been developed. In the method, the powder of low melting point metal alloy(LMPA) is filled into the PE matrix by using twin screw extruder at a temperature below the melting point of the LMPA, and followed by a die drawing process at a temperature around the melting point of the metal alloy. It has been found that die drawing process, repeating the die drawing process and adding nano-fillers, such as montmorillonite(MMT) and multi-wall carbon nanotubes(MWCNTs), all help reduce the metal particle size in the PE matrix, thus improve the conductivity of the composite. The conductivity improvement is attributed to an increased number of the smaller metal particles. Therefore, conductive composites of polymer/metal alloy/nano-filler with high conductivity are possible to be prepared by using the new method.     

三维有序大孔SiO2中的纳米银

A multi-step process was used for preparation of three-dimensionally ordered macroporous (3DOM) SiO2, in which fully accessible Ag nanoparticles are incorporated. The method involves the processes of assembly of polystyrene colloidal crystal, preparation of 3DOM SiO2, and incorporation of Ag nanoparticles within 3DOM SiO2 through in situ Tollens‘ reaction. XRD, SEM and EDXS determination show that the Ag particles deposited on the macroporous walls in nano dimension. The results indicate that lower concentration of silver ammoniate and for-maldehyde in the solution is favorable for forming a very narrow size distribution and uniform shape of nanoparticles. However, the higher the concentration of the solution and the more the loading times, the larger the possibility to form un-uniform particles. Ag nanoparticles can be sintered into larger and spheral particles by calcination at 600℃, but can resist sintering owing to their high dispersivity when loading amount is small. The study provided a simple approach to tailor Ag/3DOM SiO2 composite materials with desired morphology and size of Ag particles within the macropores.     

PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE(SPI)/MONTMORILLONITE(MMT) BIONANOCOMPOSITES

 The bionanocomposites of soy protein isolate (SPI)/montmorillonite (MMT) have been prepared successfully via simple melt mixing, in which MMT was used as nanofiller and glycerol was used as plasticizer. Their structures and properties were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermogravimetric analysis and tensile testing. XRD、TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by simple melt processing. The exfoliated MMT layers were randomly dispersed in the protein matrix as MMT content was low (less than 5 wt%), an incomplete exfoliation was evident from SEM results, and some primary particles were observed as the MMT content was high (from 5 wt% to 9 wt%). A significant improvement of the mechanical strength and thermal stability of SPI/MMT nanocomposites has been achieved. Our work suggests that simple melt processing is an efficient way to prepare SPI/MMT nanocomposites with exfoliated structure.     

Catalytic Combustion of Methane over Ti-Pillared Clay Supported Copper Catalysts

A natural montmorillonite, produced from Laiyang of Shandong Province, was pillared by Tipolycations to form Ti-pillared clay (Ti-PILC), and characterized by BET surface area, infrared spectra and thermal analysis. The characterization results show that Ti-PILC has a larger surface area and more hydroxyl groups than that of the natural clay, thus was used as the catalytic carriers to prepare supported Cu catalysts (Cu/TiopILC). The 20%Cu/Ti-PILC with 10mmol/g of Ti/clay shows a high catalytic performance of methane combustion in the temperature range of 400-500℃.     

用于甲烷水蒸气重整的镍基催化剂的失活和再生

The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),transmission electron microscopy(TEM),and carbon & sulfur analyzer. The Ni particle size was estimated from XRD patterns and TEM graphs. The agglomeration of nickel particle and the poison by sulfur components were recognized as the main reasons in deactivation of Arak and Razi catalysts,respectively. The activity of the used catalysts before and after regeneration was measured on methane steam reforming at a CH4:H2O ratio of 1:3 at 850 oC. The regeneration processes for Arak and Razi samples were performed with CO2 as an oxidative atmosphere and steam as a regenerating agent,respectively. The results show that,(1) no residual sulfur components were on the regenerated Razi catalyst surface without changing the structure of the catalyst and the regenerated catalyst has gained 80% of its catalytic activity,and that(2) the nickel particle size of regenerated Arak specimen decreased remarkably as measured by Debye-Scherrer equation from XRD patterns. TEM images were in agreement with the XRD results and indicated a decrease in nickel particle size of regenerated catalyst. Additionally,in both regenerated catalysts all the coke on the surface of the support was eliminated after regeneration.