Self-Reinforced High-Density Polyethylene Prepared by Low Frequency Vibration-Assisted Injection Molding. II: Microstructure Investigation

Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) were employed to study the microstructure of self-reinforced high-density polyethylene (HDPE) prepared by conventional injection molding (CIM) and a low frequency vibration-assisted injection molding (VAIM). SEM micrographs following permanganic etching showed the self-reinforcement of HDPE is mainly due to the existence of shish-kebab morphology within the core region for VAIM-processed HDPE samples. Pronounced molecular alignment was identified by the WAXD data. An approximate 9% increase in the crystallinity was confirmed by DSC. Both preferred molecular orientation and increased crystallinity serve to yield stronger VAIM-processed injection moldings.     

Preparation and Surface Properties of Fluorinated Acrylates Copolymers

Copolymerization of acrylates and styrene (St) with perfluorooctylacyloxyethyl methacrylate (FA) monomer, prepared from the reaction of perfluorooctanoic acid and hydroxymethyl methacrylate, was carried out by solution polymerization. The fluorinated acrylate and St copolymers (PFA) were examined by GPC, FT-IR, and ¹H NMR. The surface tension of the PFA solution in N-methyl pyrrolidone was tested by the drop volume method. The results showed that the surface tension of the PFA solution decreased in exponential decay with increase of the PFA concentration, and the surface tension of the solution also decreased with increased addition of the FA monomer in the copolymer at the same concentration. Meanwhile, the adsorption of the PFA macromolecules in the air–solution interface increased and enrichment of the fluorinated segments on the solution surface occurred. The studies of the surface free energy, polarity, fluorine content, and morphology of the PFA films illustrated that the surface free energy and polarity of the PFA films were decreased with the augment of the FA monomer in the copolymers, and that the fluorine content and the surface roughness were increased. The surface free energy of the PFA film was as small as 16.6 mN·m^?1. The surface properties of the PFA copolymers obtained by one shot feed during polymerization were superior to those obtained by continuing feed procedure. More fluorine segregation occurred and induced the formation of a fluorine-enriched surface if the PFA copolymer was postheated. The posttreatment was thus beneficial to the improvement of the surface properties of the PFA film.     

Morphology and Pore Size Distribution of Biocompatible Interconnected Porous Poly(L-lactic acid) Foams with Nanofibrous Structure Prepared by Thermally Induced Liquid–Liquid Phase Separation

Biocompatible, highly interconnected microporous poly(L-lactic acid) (PLLA) foams with nanofibrous structure, containing pores with average diameter below 1 μm and fibers with diameters of 10² nm scale, were prepared through the thermally induced liquid–liquid phase separation (TIPS) method consisting of quenching of the PLLA solution, freeze extraction with ethanol, and vacuum drying. Diverse foam morphologies were obtained by systematically changing parameters involved in the TIPS process, such as polymer concentration, solvent composition, and quenching temperatures. The morphology of different foams was examined by scanning electron microscopy to characterize the pore size and the pore size distribution. The results showed that most porous foams had a nanofibrous structure with interconnected open pores. In the case of using tetrahydrofuran (THF) as solvent, the higher the PLLA concentration, the smaller the average pore diameter and the narrower the pore size distribution. In the case of using the mixed solvents of THF/DOX (1,4-dioxane) with higher than 6/4 volume ratio, there appeared a maximum value of average pore diameter and a widest pore size distribution at 0.09 g/mL PLLA concentration. The average pore diameter of the foams increased with increasing DOX content in the mixed solvent and ranged from 0.2 to 0.9 μm depending on the process parameters. When the DOX content reached 60% by volume, the morphology of the foams contained some large closed pores with diameter ranging from 1 to 10 μm. By decreasing the quenching temperature, the average pore diameter of foams decreased and the pore size distribution became narrower. All the pore size distribution fit F-distribution equations.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Study on the Molecular Mobility in the Polyamide/SrFeO Composites by In Situ Infrared Spectroscopy

Polyamide 6(PA6) and its composite with strontium ferrite (SrFeO) magnetic powders at different concentration levels (33%, 80%) are in situ investigated by temperature-dependent Fourier transform infrared spectroscopy (FT-IR). It is found that the intensity changes of the “free” (nonhydrogen bonded) N?H stretching vibration as a function of temperature can be used to determine the glass transition (T _g) and melting temperature (T _m); whereas the hydrogen-bonded N?H stretching vibration is only sensitive to T _m. Our results reveal that high SrFeO contents increase the T _g and T _m of PA6. These observations suggest that the molecular chains of PA6 are confined with increasing content of SrFeO.     

Preparation and Mechanical and Tribological Properties of High-Density Polyethylene/Hydroxyapatite Nanocomposites

High-density polyethylene (HDPE) nanocomposites reinforced with hydroxyapatite nanorods (nHA) were fabricated by means of extrusion and injection molding. The thermal, mechanical, and dry sliding wear properties of HDPE-based nanocomposites filled with nHA loadings up to 20 wt% were investigated. The results of mechanical property characterization showed that nHA additions improved the hardness, elastic modulus, and yield strength of HDPE at the expense of its tensile ductility and impact strength. Thermogravimetric analysis and heat deflection temperature measurements revealed that nHA fillers are very effective to enhance the thermal stability of HDPE. The wear behavior of HDPE/nHA nanocomposites was studied using a pin-on-disk tribometer. nHA fillers of a large aspect ratio improved the wear resistance of HDPE substantially because of their load-bearing effect and the formation of a continuous transfer film on the steel counterface.     

Hybrid Particle–Continuum Simulations of Polymer Brushes in Shear Flow

A hybrid particle–continuum method is used to study the shear flow confined between two opposing walls, one of which is coated with polymer chains. Molecular dynamics (MD) is used in the particle region near the brush and Navier–Stokes (NS) equations are applied in the remaining region where the continuum assumption holds. The information exchange from the continuum region to the particle region is implemented using the constrained particle dynamics. Both Couette shear flow and oscillatory flow are considered in the present work. The effect of the shear flow on the conformational characteristics of polymer brushes is analyzed. In the overlap region, the velocities obtained from MD simulations are smoothly connected with those from NS equations. Our investigations demonstrate that the hybrid particle–continuum model is valid in exploring the shear behavior of polymer brushes.     

Effect of β-Nucleating Agent on the Crystallization,Mechanical Properties,and Heat Resistance of Injection-Molded Isotactic Polypropylene

Injection-molded β-isotactic polypropylene (β-iPP) was prepared with a commercial β-nucleating agent (NT-A). The effect of NT-A on the crystallization, mechanical properties, and heat resistance of β-iPP was investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM), and mechanical and heat deflection tests. DSC and WAXD analysis showed that the content of β-crystals in the nucleated iPP was higher than that of pure iPP, and the content of β-crystals of the core was higher than that of the skin. PLM observations showed that injection-molded iPP had an obvious skin-core structure. NT-A induced abundant β-crystals and resulted in small spherulites which improved the Izod notched impact strength. When the content of NT-A was 0.075wt%, the Izod notched impact strength reached a maximum, 2.6 times more than that of pure iPP. The heat distortion temperature was also improved by NT-A.     

Half-Width Integral Method for Gas Concentration Measuring in Tunable Diode Laser Absorption Spectroscopy

ABSTRACT

We analyze the influence of random errors and absorption shape fitting errors on gas concentration measurement in tunable diode laser absorption spectroscopy. We then propose a new data processing method according to the characteristic of random errors and fitting absorption shape. This method only uses the integral value within the half width at half maximum of the fitting absorption shape to determine the gas concentration in actual measurements. Meanwhile, the O₂ transition at 13,150.197 cm^?1 is selected to measure the O₂ concentration using this method. Compared with the traditional method, the method established in this paper can accurately measure O₂ concentration.     

Interaction Between Neuroglobin and Caffeine by Multispectroscopic Methods

The interaction between neuroglobin (Ngb) and caffeine was studied by spectroscopy. UV-Vis spectra revealed that caffeine did not influence the native hexa-coordinated heme structure of neuroglobin. Fluorescence spectra indicated that caffeine could quench the intrinsic fluorescence of neuroglobin through static quenching mechanisms. The calculated thermodynamic parameters showed that the electrostatic force was the main intermolecular force in the reaction. Results also indicated that the microenvironmental changes of tryptophan and tyrosine residues within neuroglobin are inapparent. Furthermore, the circular dichroism (CD) spectra implied that caffeine could induce the formation of α-helix structure of neuroglobin.