The Effect of Crystallization on the Solid State Polycondensation of Poly(L‐lactic Acid)

Melt solid polycondensation is an approach to increase the molecular weight of poly (L‐lactic acid) (PLLA). For this report, the effect of crystallization time of PLLA prepolymer on the molecular weight of the biomaterial was studied. In this process, PLLA prepolymer with a molecular weight of 18,000 was first prepared by the ordinary melt‐polycondensation process. The prepolymer was crystallized at 105°C for various times, and then heated at 135°C for 15–50 h for further solid state polycondensation (SSP). The differential scanning calorimetry (DSC) and viscosity measurements were used to characterize the crystalline properties and molecular weight of the resulting PLLA polymers, respectively. The results showed that the molecular weight of PLLA reached a maximum value under the condition of a crystallization time of 30 min and SSP of 35 h.     

用1H-NMR法分析线性聚氨酯预聚体

利用¹H-NMR法测定聚氧化丙烯醚-纯2,4二异氰酸甲苯酯体系的聚氨酯预聚体中的NCO与OH的克分子比以及体系中所使用的聚氧化丙烯醚的数均分子量,最后可计算出预聚体的分子量。     

Numerical Simulation of Phase Separation Kinetic of Polymer Solutions Using the Spectral Discrete Cosine Transform Method

A spectral discrete cosine transform (DCT) method was used to solve numerically the spatio-temporal nonlinear Cahn-Hilliard equation for a temperature-induced phase separation process of a polymer solution. The properties of a high molecular weight polystyrene solution were used in the model to reflect the behavior of a real world polymer system. Based on the value of the initial concentration, three different final morphologies of the phase separated system, granular, interconnected, and microcellular, were identified. It was shown that the initial concentration is the main factor to determine the high rate of the phase separation when the phase separation time is the primary desired parameter. The degree of phase separation, as a quantitative measure of the phase separation process, indicates the rate and amount of separated polymer material for practical applications. The model is capable of providing quantitative information of morphology evolution during phase separation processes for microstructure control purposes. The structure factor profile was extracted as a theoretical output that enables comparison with scattering experiments observations as the finger-print of phase separation morphological evolution. It is shown that the DCT method is a very suitable and feasible method for solution of the nonlinear partial differential equation of phase separation kinetics.     

Optimization of ultrasonic-assisted ultrafiltration process for removing bacterial endotoxin from diammonium glycyrrhizinate using response surface methodology

Ultrasonic-assisted ultrafiltration (UAU) removing bacterial endotoxin from diammonium glycyrrhizinate, was firstly applied to surfactant separation. Separation efficiency was related with four variables, including ultrafiltration molecular weight cut off (MWCO), ultrasonic power, concentration and pH. The SCQ-9200E ultrasonic system was provided for the study with adjustable ultrasonic power 80 W to 800 W, and the ultrasonic frequency was 40 KHz. On the basis of response surface methodology (RSM), the optimal separation conditions were determined to be the ultrafiltration MWCO as 10 kDa, the ultrasonic power as 570 W, diammonium glycyrrhizinate concentration as 150.00 μg/mL and the pH as 4.70. The experimental rejection of bacterial endotoxin was 94.08%, meanwhile the transmittance of diammonium glycyrrhizinate was 93.65%. Based on the ultrasonic power, solution volume, and ultrasonic container size, the experiments with UAU at different power intensities showed that ultrasonic at a power intensity of 57 W/L and the power density of 0.32 W/cm² could solve the separation contradiction between diammonium glycyrrhizinate and bacterial endotoxin. This study indicated that UAU could be an innovation in ultrasonic separation fields, and had a vast range of prospects for making use in pharmaceutical preparation area.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.     

Mechanochemical degradation kinetics of high-density polyethylene melt and its mechanism in the presence of ultrasonic irradiation

In this paper, the effect of ultrasonic intensity on the degradation of high-density polyethylene (HDPE) melt, degradation mechanism, ultrasonic degradation kinetics of HDPE melt as well as the development of molecular weight distribution of HDPE melt during ultrasonic degradation were studied. In the initial stage, the ultrasonic degradation of HDPE melt shows a random scission process, and the molecular weight distribution broadens. After that, the ultrasonic degradation of HDPE melt shows a nonrandom scission process, and the molecular weight distribution of HDPE melt narrows with ultrasonic irradiation time. The average molecular weight of HDPE decreases with the increase of ultrasonic intensity and increases and trends forward that of undegraded HDPE with the increase of distance from ultrasonic probe tip, indicating that attenuation of ultrasonic intensity in HDPE melt is very quick. Ultrasonic degradation kinetics of HDPE melt obeys the equation: Mt=M(infinity) + Ae(-kt). The theoretic calculation by this equation accords well with the experimental results. The plausible ultrasonic degradation mechanism of polymer melt based on molecular relaxation was also proposed in this paper.     

Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.     

Effect of Polydispersity on the Phase Behavior of Polystyrene (PS)/Poly (Vinyl Methyl Ether) (PVME)

The thermodynamics and kinetics of phase separation in partially miscible blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS) with the same weight average molecular weight but different polydispersity were studied. The miscibility of PS/PVME with the monodisperse PS was better than that of PS/PVME with the polydisperse PS. Different morphology was observed for the two kinds of PS/PVME (10/90) blends during the nonisothermal phase separation process. The blend with monodisperse PS presented a co-continuous structure while the blend with polydisperse PS presented a viscoelastic phase separated network structure at a quench depth of 29°C. With increase of the heating rate, the increase of cloud point of PS/PVME (30/70) with polydisperse PS was smaller than that of PS/PVME (30/70) with monodisperse PS. During the isothermal phase separation of the critical composition (20/80) of PS/PVME with a quench depth of 30°C, it was found that the phase morphology of the two kinds of blends was nearly the same at the early stage of phase separation. However, as the dispersed phase, an approximately spherical droplet structure was observed in the blend with monodisperse PS at the late stage of phase separation, which did not appear in the blend with polydisperse PS.     

Processing of ultra-high molecular weight polyethylene/graphite composites by ultrasonic injection moulding: Taguchi optimization

Ultrasonic injection moulding was confirmed as an efficient processing technique for manufacturing ultra-high molecular weight polyethylene (UHMWPE)/graphite composites. Graphite contents of 1 wt%, 5 wt%, and 7 wt% were mechanically pre-mixed with UHMWPE powder, and each mixture was pressed at 135 °C. A precise quantity of the pre-composites mixtures cut into irregularly shaped small pieces were subjected to ultrasonic injection moulding to fabricate small tensile specimens. The Taguchi method was applied to achieve the optimal level of ultrasonic moulding parameters and to maximize the tensile strength of the composites; the results showed that mould temperature was the most significant parameter, followed by the graphite content and the plunger profile. The observed improvement in tensile strength in the specimen with 1 wt% graphite was of 8.8% and all composites showed an increase in the tensile modulus. Even though the presence of graphite produced a decrease in the crystallinity of all the samples, their thermal stability was considerably higher than that of pure UHMWPE. X-ray diffraction and scanning electron microscopy confirmed the exfoliation and dispersion of the graphite as a function of the ultrasonic processing. Fourier transform infrared spectra showed that the addition of graphite did not influence the molecular structure of the polymer matrix. Further, the ultrasonic energy led oxidative degradation and chain scission in the polymer.     

The influence of frequency on the mechanical and radical effects for the ultrasonic degradation of dextranes

The ratio of mechanical and radical effects for the ultrasonic degradation of dextranes in aqueous solutions was studied in dependence of frequency and molecular weight of the dextranes. For low ultrasound frequency (35 kHz) a stronger increase of the polymer degradation with increasing molecular weight was found as expected on the basis of the radicals present. This is due to the mechanical effects of ultrasound. Applying higher frequencies (>500 kHz) only radical reactions are responsible for the degradation. Below a molecular weight limit of 40000 the mechanical effects vanish.     

Formation of a grating of submicron nematic layers by photopolymerization of nematic-containing mixtures

A submicron, spatially periodic, structure consisting of a sequence of oriented layers of a nematic liquid crystal (NLC), separated by isotropic polymeric walls, was obtained experimentally. This was accomplished by polymerization induced by the interference pattern of UV laser radiation in a NLC-containing prepolymer mixture. It was established that such a structure occurs when phase separation and nematic ordering are prevented during the polymerization process. These structures are the diffraction elements, whose efficiency is much greater than that of a standard grating of polymer-dispersed liquid crystals [1–4] which is obtained in the same initial mixture. Specifically, a diffraction efficiency of 60–70% was obtained for structures with the period Δ = 0.2 μm, even in mixtures where a grating with Δ < 6 μm cannot be obtained at all by the standard technique.     

Sensitivity enhancement in membrane separation flow injection analysis by ultrasound

The effect of ultrasound on gas-diffusion and pervaporation flow injection separation was investigated. Ammonia and three aliphatic amines (propylamine, tri-ethylamine and di-n-butylamine) with different volatility and surface activity were used as model analytes. Under the experimental conditions used, sonication did not enhance gas-diffusion separation efficiency and resulted in up to 62% improvement in pervaporation mass transfer. Based on these findings and taking into account the surface activity of the analytes studied which decreased with their molecular mass it was postulated that ultrasound-induced surface rippling was primarily responsible for the enhanced evaporation in the donor chamber of the pervaporation cell. The results reported in this paper suggest that ultrasonic pervaporation separation could extend the applicability of this on-line flow injection separation technique to the direct determination of higher molecular mass volatile and semi-volatile analytes in 'dirty' samples.     

Ultrasonic effects on the degradation kinetics,preliminary characterization and antioxidant activities of polysaccharides from Phellinus linteus mycelia

In this study, a high-molecular-weight polysaccharide PL-N isolated from the alkaline extract of Phellinus linteus mycelia was degraded by ultrasound. Results showed that ultrasound treatment at different ultrasonic intensities decreased the intrinsic viscosity and molecular weight of PL-N, as well as narrowed the molecular weight distribution. A larger reduction in intrinsic viscosity and molecular weight was caused by a higher ultrasonic intensity. The degradation kinetics model was fitted to (1/M_t − 1/M₀) = k·t, and the reaction rate constant (k) increased with increasing ultrasonic intensity. Ultrasound degradation did not change the primary structure of PL-N, and scanning electron microscopy analysis indicated that the morphology of the original PL-N was different from that of degraded PL-N fractions. Antioxidant activity assays in vitro indicated that the degraded PL-N fraction with low molecular weight had stronger hydroxyl radical scavenging capacity and higher TEAC and FRAP values.     

Effects of ultrasonic vibration on the micro-molding processing of polylactide

A new ultrasonic micro-molding system was used to process polylactide (PLA) and fabricate reduced dimension specimens. Plasticization and molding of PLA were achieved by applying ultrasonic waves after feeding the polymer into a plasticizing chamber. Chemical and physical characteristics of processed PLA varied depending on the processing window (i.e. changes in ultrasonic wave amplitude between 14.2 and 48.1 μm and molding pressure between 0.5 in 6 bars). In terms of chemical effects, the application of ultrasound can lead to lower molecular weights (e.g. decreases of more than 45% in the weight average molecular weight), revealing partial degradation of the material. Also, the processed materials exhibited slightly higher thermal degradability than pure PLA because ultrasonic vibrations break molecular linkages and worsen the polymer structure. Finally, the processing conditions for the preparation of PLA specimens could be optimized without causing degradation and preserving structural characteristics and mechanical properties. Specifically, the use of an amplitude of 48.1 μm and a pressure of 3 bars gave samples with the same molecular weight as the raw material (i.e. 117,500 g/mol as opposed to 117,300 g/mol for M_w).     

The compatibility and transesterification for blends of polyethylene terephthalate)/poly(bisphenol-A carbonate)

A study has been made of the influence of transesterification on the miscibility in binary blends of poly(ethylene terephthalate) and poly(bisphenol-A carbonate). The blends were melt mixed in the range 260–300°C and studied by differential scanning calorimetry, dynamic mechanic analysis, and by Fourier transform infrared spectrometry. It was found that copolymer produced by a transesterification reaction can enhance the miscibility of this system. The new compositions were uniquely identified by FTIR. Gel permeation chromatography showed that molecular weight decreases were not the origin of miscibility. The ester exchange reaction itself was found to be initiated by the residual catalyst in the commercial polymers selected for study. This has been shown by the absence of reaction after polymer purification by solution and reprecipitation prior to melt mixing.     

基于变分模态分解与多尺度排列熵的生物组织变性识别

根据高强度聚焦超声(HIFU)治疗中超声散射回波信号的特点,本文利用变分模态分解(VMD)与多尺度排列熵(MPE)对生物组织变性识别进行了研究.首先对生物组织中的超声散射回波信号进行变分模态分解,根据各阶模态的功率谱信息熵值分离出噪声分量和有用分量;对分离出的有用信号进行重构并提取其多尺度排列熵;然后通过Gustafson-Kessel (GK)模糊聚类确定聚类中心,采用欧氏贴近度与择近原则对生物组织进行变性识别.将所提方法应用于HIFU治疗中超声散射回波信号实验数据,用遗传算法对多尺度排列熵的参数优化后,对293例未变性组织和变性组织的超声散射回波信号数据进行了多尺度排列熵分析,发现变性组织的超声散射回波信号的多尺度排列熵值要高于未变性组织;多尺度排列熵可以较好地识别生物组织是否变性.相对于EMD-MPE-GK模糊聚类以及VMD-小波熵(WE)-GK模糊聚类变性识别方法,本文所提方法中变性与未变性组织特征交叠区域数据点更少,聚类效果和分类性能更好;本实验环境下生物组织变性识别结果表明,该方法的识别率更高,高达93.81%.     

Ultrasonic-microwave-assisted extraction for enhancing antioxidant activity of Dictyophora indusiata polysaccharides: The difference mechanisms between single and combined assisted extraction

The purpose of this study is to investigate the effects of different extraction methods (hot water-assisted extraction (HWE), microwave-assisted extraction (MAE), ultrasonic-assisted extraction (UAE), and ultrasonic-microwave- assisted extraction (UAME)) on the yield, chemical structures and antioxidant activity of Dictyophora indusiata polysaccharides (DPs). The research results showed that UMAE treatment had greater degree of damage to the cell wall of DPs and better comprehensive antioxidant capacity. Different extraction methods had no obvious effect on the types of glycosidic bonds and sugar rings, similar chemical composition and monosaccharide composition, with different absolute molecular weight (Mw) and molecular conformation. In particular, DPs for UMAE method had the highest polysaccharides yield, which was related to the conformational stretching and degradation avoidance of DPs in the higher molecular weight components under the simultaneous action of microwave and ultrasonic. These findings suggest that the UMAE technology has good potential for modification and application of DPs in the functional food industry.     

Particle separation in microfluidics using different modal ultrasonic standing waves

Microfluidic technology has great advantages in the precise manipulation of micro and nano particles, and the separation of micro and nano particles based on ultrasonic standing waves has attracted much attention for its high efficiency and simplicity of structure. This paper proposes a device that uses three modes of ultrasonic standing waves to continuously separate particles with positive acoustic contrast factor in microfluidics. Three modes of acoustic standing waves are used simultaneously in different parts of the microchannel. According to the different acoustic radiation force received by the particles, the particles are finally separated to the pressure node lines on both sides and the center of the microchannel. In this separation method, initial hydrodynamic focusing and satisfying various equilibrium constraints during the separation process are the key. Through numerical simulation, the resonance frequency of the interdigital transducer, the distribution of sound pressure in the liquid, and the relationship between the interdigital electrode voltage and the output sound pressure are obtained. Finally, the entire separation process in the microchannel was simulated, and the separation of the two particles was successfully achieved. This work has laid a certain theoretical foundation for the rapid diagnosis of diseases in practical applications.     

Ultrasonic degradation of poly(vinyl alcohol) in aqueous solution

Solution of poly(vinyl alcohol) in water with different concentrations (by weight 1%, 1.5%, 2%) and different volumes (50, 75 and 100 ml) were subjected to ultrasonic degradation. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The degradation rate constant was correlated with the power input due to ultrasonic irradiation and reaction volume. It was found that rate constant decreases as the reaction volume and concentration increases. The proportionality index of the relation between rate constant, power input and reaction volume was found to be nearly equal for all concentrations studied. The proportionality constant was found to be approximately equal for 1% and 1.5% solution and for 2% solution it was approximately half the value for that of 1% and 1.5% solutions. The decrease in rate constant and proportionality constant is attributed to the fact that at higher concentration and at higher volume, the intensity of cavitation phenomenon is depressed and therefore the extent of polymer chain breaking decreases. The difference in the values of limiting viscosities (constant solution viscosity which does not decrease by further ultrasonic irradiation) for 50, 75 and 100 ml solutions for each of 1% and 1.5% concentration was negligible. But 2% solution at 100 ml volume showed slightly higher value of limiting viscosity than that for 50 and 75 ml.     

聚氨酯改性TDE-85/MeTHPA环氧树脂的力学性能研究

 采用自制的聚氨酯预聚体(PUP)制备聚氨酯(PU)改性TDE-85/ MeTHPA环氧树脂体系,探讨了聚醚二元醇(PPG)分子量的大小、PUP加入量等因素对PU改性TDE-85/ MeTHPA环氧树脂体系力学性能的影响。研究结果表明,PU改性TDE-85/ MeTHPA环氧树脂的拉伸强度和冲击强度随着合成的PUP加入量的增加先呈上升趋势,达到最大值后又开始下降。采用的PPG分子量不同,得到的改性材料的力学性能相差悬殊。当PPG分子量为1 000,PUP质量分数为15%时,改性材料的拉伸强度达到69.39 MPa,冲击强度达到23.56 kJ/m²,力学综合性能显著提高。