Changes in the structural parameters and molecular dynamics of polyhydroxybutyrate-chitosan mixed compositions under external influences

Differential scanning calorimetry (DSC), EPR probe analysis, large-angle X-ray diffraction (XRD), and UV spectroscopy are used to study the molecular dynamics and structure of hydroxybutyrate (PHB) copolymer, chitosan, and mixed compositions thereof upon thermal treatment in an aquatic medium. It is shown that, in mixed compositions, starting from 30% PHB, the correlation time increases by an order of magnitude, indicative of a sharp slowdown of the molecular mobility of the probe, and, concurrently, the degree of crystallinity decreases abruptly, as evidenced by DSC and XRD analyses. The diffusion coefficient of rifampicin in mixed compositions also decreases with increasing PHB content. A short-term (1 h) thermal treatment (at 70°C) in water results in an increase in the molecular mobility of the probe in the system. Crystallinity changes in complex ways.     

Effect of Benzoic Acid on the Crystallization Behavior of Poly(3-Hydroxybutyrate)

The effect of benzoic acid (BA) on the crystallization behavior of poly(3-hydroxybut yrate; PHB) was studied. A differential scanning calorimeter was used to monitor the crystallization kinetics and thermal behavior. During the crystallization process from the melt, the presence of BA led to a decrease of the crystallization temperature of PHB compared with that for pure PHB. From the depression of the melting and glass transition temperatures of PHB, it can be concluded that BA is miscible, and has a strong plasticization effect on PHB. Isothermal crystallization at 80°C results showed that the addition of BA caused a decrease in the overall crystallization rate of PHB. Polarized optical micrographs of PHB/BA showed that the nucleation density of PHB spherulites decreased with increasing weight percentage of BA.     

Transmission Electron Microscopic Investigation of the Morphology of High-Speed Spun Poly(Ethylene Terephthalate) Fibers

Permanganic etching was performed on high-speed spun (HSS) and regular fibers of poly(ethylene terephthalate) (PET), and their surface morphologies were investigated via the two-stage carbon replica method using a transmission electron microscope (TEM). The HSS PET fibers, with disordered amorphous regions, showed peculiar surface morphology; many small warts corresponding to the pits of etched disordered amorphous regions were observed. Such unevenness, however, was hardly observed on the surface of the permanganic-etched regular PET fibers, with well-oriented amorphous regions, or on the surface of alkali-etched HSS PET fibers. The permanganic etchant removed the disordered amorphous regions more preferentially compared with the alkali etchant.     

Structural,thermal, and electrical studies of sodium iodide (NaI)-doped hydroxypropyl methylcellulose (HPMC) polymer electrolyte films

Solid polymer electrolyte films based on hydroxypropyl methylcellulose (HPMC) complexed with sodium iodide (NaI) were prepared using solution cast method. The dissolution of the salt into the polymer host and the structural properties of pure and complexed HPMC polymer electrolyte films were confirmed by X-ray diffraction (XRD) studies. XRD results revealed that the amorphous domains of HPMC polymer matrix were increased with increase in NaI salt concentration. The degree of crystallinity was found to be high in pure HPMC samples. The thermal properties were studied using differential scanning calorimetry (DSC). DSC results revealed that the presence of NaI in the polymer matrix increases the melting temperature; however, it is observed that fusion heat is high for pure HPMC films. The variation of film morphology was examined by scanning electron microscopy. Fourier transform infrared spectral studies revealed vibrational changes that occurred due to the effect of dopant salt in the polymer. Direct current conductivity was measured in the temperature range of 313–383 K. The magnitude of electrical conductivity was found to increase with the increase in salt and temperature concentration. The data on the activation energy regions (regions I and II) indicated the dominance of ion-type charge transport in these polymer electrolyte films. The composition HPMC:NaI (5:4) is found to exhibit the least crystallinity and the highest conductivity.     

Investigation of the mobility in poly(vinylidene fluoride) ferroelectric films with different structures

The molecular mobility in two isotropic poly(vinylidene fluoride) samples crystallized in the α phase from the melt with different crystallinities and lattice perfections has been investigated by broadband dielectric spectroscopy. It has been revealed that the local-mobility parameters are insensitive to structural features. The average relaxation times of micro-Brownian motion in the disordered phase are found to be identical in the samples under consideration, which can be associated with the localization of the mobility in the interphase layer at the crystal-amorphous phase interface. The motion in the crystal (α _c transition) has been described using the soliton mechanism of relaxation. It has been found that, as should be expected, the average relaxation time increases with an increase in the longitudinal crystal size; however, in this case, a strict quantitative correlation is absent. According to the small-angle X-ray scattering data, this is caused by different microstructures of interlamellar amorphous regions. It has been demonstrated that the samples with a higher degree of crystallinity are characterized by a larger difference in the electron densities of the crystalline and amorphous phases and a larger size of the amorphous layer. It has been assumed that an increase in the concentration of chemical defects in the interlamellar layers with a simultaneous increase in their length is responsible for the increased probability of attenuation of the solitary wave (conformational defect) in its passage between neighboring lamellar crystals.     

Annealing Effect on Chain Segment Motion and Charge Trapping and Detrapping in Nylon 1010

The chain segment motion and charge trapping and detrapping in nylon 1010 films were investigated by means of thermally stimulated depolarization current (TSDC). There were three current peaks (named α, ρ1, and ρ2 peaks, respectively) in the experimental TSDC spectra above room temperature. The α peak is attributed to a background dipole relaxation by the motion of chain segments and space charge contribution, the ρ1 peak is originated from a space charge trapped in the bulk amorphous regions and the interphase between crystalline and amorphous regions, the ρ2 peak is originated from space charge trapped in crystalline regions. By analyzing the characteristic parameters of these peaks, it was found that with in increase of the degree of crystallinity the activation energy of the a peak increased from 1.12 to 1.22 eV and the trap depth of the ρ2 peak increased from 2.70 to 2.82 eV, while the trap depth of the ρ1 peak decreased from 1.50 to 1.29 eV. Annealing induced a decrease of the chain segment mobility and promoted the creation of traps in nylon 1010. Annealing also decreased the stability of the trapped charges in the bulk amorphous and the interphase regions and increased the stability of the trapped charges in the crystalline regions.     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学

本文在150~370 K温度范围内,采用固体核磁共振（NMR）测定了半晶聚-3-羟基丁酸酯（PHB）,以及3-羟基戊酸酯单体质量分数分别为5%（PHBV5）和12%（PHBV12）的聚羟基丁酸戊酸酯共聚物在实验室坐标系和旋转坐标系条件下质子的自旋-晶格弛豫时间T₁和T_1ρ.通过弛豫时间随温度变化的理论拟合,分别获得上述半晶聚合物晶区和结晶区的分子动力学参数（包括E_a和τ₀）.这些结果从分子水平上阐述了PHB结构修饰和增强的原因.     

The study of gamma irradiation effects on poly (glycolic acid)

We have investigated the effects of gamma irradiation on chemical structure, thermal and morphological properties of biodegradable semi-crystalline poly (glycolic acid) (PGA). PGA samples were subjected to irradiation treatment using a ⁶⁰Co gamma source with a delivered dose of 30, 60 and 90?kGy, respectively. Gamma irradiation induces cleavage of PGA main chains forming ～O?H₂ and ?H₂COO～ radicals in both amorphous and crystalline regions. The free radicals formed in the amorphous region abstract atmospheric oxygen and convert them to peroxy radicals. The peroxy radical causes chain scission at the crystal interface through hydrogen abstraction from methylene groups forming the ～?HCOO～ (I) radical. Consequently, the observed electron spin resonance (ESR) doublet of irradiated PGA is assigned to (I). The disappearance of the ESR signal above 190°C indicates that free radicals are formed in the amorphous region and decay below the melting temperature of PGA. Fourier transform infrared and optical absorption studies confirm that the groups are not influenced by gamma irradiation. Differential scanning calorimetry (DSC) studies showed that the melting temperature of PGA decreased from 212°C to 202°C upon irradiation. Degree of crystallinity increased initially and then decreased with an increase in radiation as per DSC and X-ray diffraction studies. Irradiation produced changes in the physical properties of PGA as well as affecting the morphology of the material.     

Preparation of High-Quality Polyacrylonitrile Precursors for Carbon Fibers Through a High Drawing Ratio in the Coagulation Bath During a Dry-Jet Wet Spinning Process

Excellent poly(acrylonitrile-co-itaconic acid) (99/1) (PAI) nascent fibers, which have an important role in preparing high-quality precursors for carbon fibers, were prepared by a dry-jet wet spinning process. Their structures were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and an ultrasound solvent etching method, as well their properties being determined by a strength and extension meter and a fineness meter, both designed specifically for fibers. When a high drawing ratio, over 300%, was applied to the fibers in the dry-jet wet spinning coagulation bath, the molecular chains were easy to orient and regularly arrange, resulting in the relative crystallinity, crystal size and amorphous orientation degree of the nascent fibers being improved. The fibrils with large diameter were formed, increasing the bulk density with the overall porosity and pore numbers decreasing. Therefore, the nascent fibers had smaller diameters, higher strength, higher rupture elongation and smaller coefficients of variation. The optimum high performance PAI precursor fibers, with 0.59dtex in titer, 7.51cN/dtex in tensile strength, 7.9% in rupture elongation and the final carbon fiber with 5.54GPa in tensile strength, were obtained through a post-spinning treatment in which they were subjected to a high coagulation bath draw ratio and carbonization.     

Characterization of structural modifications in poly-tetra-fluoroethylene induced by electron beam irradiation

The effects of electron beam irradiation doses on the poly-tetra-fluoroethylene (PTFE) have been studied. Several techniques, such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical properties and Fourier transform infrared spectroscopy (FTIR) were applied to characterize the PTFE samples and to study the radiation effects on the crystal structure of the polymer.The irradiation dose up to 150 kGy showed an increase in the crystallinity degree of PTFE, which has been observed and confirmed during the DSC and XRD measurements. The increase in crystallinity was attributed to the scissions of the chain in the amorphous region. Moreover, the number-average molecular weights were estimated from the heat of crystallization measured by DSC technique. The results indicated that the molecular weights were decreased by increasing the heat of crystallization due to irradiation with doses up to 150 kGy. Radiation resistance of the irradiated and non-irradiated PTFE was investigated during its mechanical properties at room temperature. The dose at half value of the elongation at break is about 3.10 kGy while the dose at half value of the tensile strength is about 1.70 kGy.     

Miscibility and Hydrogen Bonding Interactions in Blends of Poly(hydroxyether ketone) and Poly(4-vinyl pyridine)

The influence of silica nanoparticles on the tensile properties of poly(ethylene terephthalate)(PET) fibers was investigated. The results showed that mechanical properties of PET fibers were improved through nano‐silica incorporation. Two maxima of the modulus‐strain curves of PET/silica nanocomposites (PETS) fibers are always higher than those of pure PET (PET0) fibers. The results of microstructure investigations suggested that the amorphous orientation factor of PETS fibers is higher than that of PET0 fibers. It is suggested that the increase of amorphous orientation factor contributed to the improvement of tensile properties of PET fibers. Considering the difference in modulus‐strain curves of PET0 and PETS fibers, it is believed that the addition of nanoparticles not only improved the amorphous orientation factor but also changed the load units of PET fibers when strained, which also resulted in the improvement of tensile properties.     

Piezoelectric properties of electron-irradiated poly (vinylidene fluoride)

Some of the piezoelectric constants of PVDF are strictly stress dependent. This behaviour is assumed to originate in a contribution of the interphase region between crystalline and amorphous phases to the piezoelectric effect in this material. This assumption is supported by the changes in piezoelectricity after irradiation with fast electrons. Such treatment causes crosslinking predominantly in the amorphous regions and, consequently, significant changes in the mobility of molecular electric moments. The piezoelectric constants become smaller upon irradiation, this being caused by a reduced permanent polarization, by increased mechanical stiffness, and by the reduced reorientability of the molecular electric moments in the interphase. One of the nonlinear piezoelectric coefficients changes its sign at a certain irradiation dose.     

Fabrication of Polypropylene (PP)/Poly Trimethylene Terephthalate (PTT)/Nanoclay Nanocomposite Fibers with Tailored Properties

Abstract

The main aim of this study was to deal with one of the major drawbacks of polypropylene (PP) fibers, i.e., low resiliency and low dyeability, by incorporating polytrimethylene terephthalate (PTT) fibrils, as a dispersed material, and organoclay, as a nano-filler, into the PP polymer matrix. The presence of 10?wt% of PTT and 0.5–1?wt% organoclay in the PP nanocomposite fibers led to an approximately 18.5% and 45.5% increase in the resilience behavior and dye uptake, respectively, compared to pure PP fibers, without using highly toxic carriers. The lowest mean diameter of the nano-fibrils was 75?nm for the hot drawn nanocomposite fiber samples as measured by scanning electron microscopy (SEM). The results of DSC indicated that the presence of both PTT and organoclay significantly influenced the crystallinity of the PP which also confirmed their nucleating effects in the nanocomposite fiber.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

几种高分子材料的域结构、分子动力学和相互作用的固体NMR研究

聚3-羟基丁酸酯(PHB)是微生物细胞在其生长的特定时期在胞内合成的具有相应生物功能的聚羟基烷酸酯类物质, 是一种具有潜在的广泛应用前景的生物可降解的高分子材料. 由于天然的PHB其较高的结晶度和较窄的温度处理范围,它在应用过程中受到较大的局限性. 人们将结构相似的单体3-羟基戊酸(HV)与3-羟基丁酸(HB)共聚形成共聚物(PHBV)以后, 显著改善了PHB的物理机械性能,譬如:冲击强度和韧性有所增加，而硬度脆性有一定程度的下降. 人们虽然在这些降解高分子材料的开发、制备和物理机械性能以及这些材料的应用等方面有很多研究，但是有关分子水平的问题并未得到系统的探索. 因此，针对这些分子基础问题(结构域特征和分子动力学等)做了一些初步的研究.  全氟磺酸树脂(Nafion)是杜邦公司生产的一种燃料电池电极薄膜材料，其较低的使用温度(<100℃)严重地限制了它的应用范围. 人们发现，当把层状硅酸盐(蒙脱土)和Nafion合成为有机无机纳米复合材料之后，在一定程度上提高了它的使用温度. 虽然这种复合材料很容易合成出来并且已经运用到了实际工业应用之中，但是这种热稳定性提高的原因却不甚清楚. 通过固体NMR等分析方法从微观相互作用方面来认识这种宏观性能改善的原因.  使用固体¹³C CP MAS、¹³C SPE MAS NMR以及XRD方法测定了PHB和两种PHBV的结晶度(X_c)，发现随着HV的引入它们的X_c 逐渐减小. 研究同时发现在测量X_c 的这几种方法中¹³C SPE MAS NMR误差较小. 实验中我们利用质子弛豫诱导谱编辑(PRISE)、质子自旋扩散(Spin-diffusion)等固体NMR技术研究了PHB以及不同含量HV的PHBV的结构域特征和相应结构域的运动性. 实验结果表明随着HV含量的增加，它们的非晶相结构域尺寸增大，晶相结构域尺寸减小，可以看出HV的引入导致PHB的结构域特征的变化是其宏观性能改善的原因.  进一步通过低分辨固体NMR测量了PHB和PHBV的变温质子弛豫时间(T₁, T_1ρ, T₂), 然后通过理论拟合获得了它们不同运动状态的分子运动相关频率(τ_c)和分子活化能(E_a)等动力学信息，研究发现随着HV含量的增加，分子运动加快，活化能减小，在分子水平上认识了HV的引入使得PHB宏观性能改善的微观原因.  通过溶胶凝胶法合成了燃料电池电极薄膜(Nafion)和层状硅酸盐(蒙脱土)纳米复合材料来提高Nafion的使用温度，FT-IR和²⁹Si MAS NMR实验结果表明在杂化材料中虽然质子化的十二烷基胺修饰的蒙脱土(MMT)的引入没有导致MMT的骨架结构发生明显变化，而且Nafion也没有插入到MMT的层间，但是TGA分析表明杂化材料中的Nafion的热稳定性比纯的Nafion高. 通过一系列固体NMR技术包括¹⁹F MAS、¹H-¹³C CP MAS NMR和¹H-¹³C HETCOR 2D NMR实验初步证实了这种材料的热稳定性的提高可能是由于MMT表面吸附的NH⁺₃与Nafion侧链上的SO^-₃之间存在较强的静电相互作用，初步可以认为这种相互作用是导致电极材料性能改善的原因.     

Surface Modification of Ultrahigh-molecular-weight Polyethylene Fibers with Coupling Agent during Extraction Process

Ultrahigh molecular weight polyethylene (UHMWPE) fibers were treated with a coupling agent following the extraction of gel fibers, resulting in modified fibers after subsequent ultra-drawing. The structure and morphology of the modified UHMWPE fibers were characterized and their surface wetting, interfacial adhesion, and mechanical properties were investigated. It was found that the coupling agent was absorbed into the UHMWPE fiber and trapped on the fiber surface. Compared with unmodified UHMWPE fibers, the modified fibers had smaller contact angle, higher crystallinity, and smaller crystal size. The interfacial adhesion and mechanical properties of UHMWPE fibers were significantly improved with increasing coupling agent concentration and gradually reached a plateau value. After treatment with 1.5 wt% solution of a silane coupling agent (γ -aminopropyl triethoxysilane, SCA-KH-550), the interfacial shear strength of the UHMWPE-fiber/epoxy composites was increased by 108% and the tensile strength and modulus of modified UHMWPE fibers were increased by 11% and 37% respectively.     

Effect of Polarization Temperature on the Chain Segment Motion and Space Charge Detrapping in Polyamide 610 Film Electrets

The effect of polarization temperature on the chain segment motion and charge trapping and detrapping in polyamide 610 films has been investigated by means of thermally stimulated depolarization current (TSDC) and wide-angle X-ray diffraction (WAXD). A small part of the amorphous phase of quenched polyamide 610 changes into the crystalline state with increasing polarization temperature. There are three current peaks (named α, ρ₁, and ρ₂ peak, respectively) in the TSDC spectra. The α peak corresponds to the glass transition, the ρ ₁ peak is attributed to space charge trapped in the amorphous phase, and interphase between crystalline and amorphous phases, and the ρ ₂ peak originates from space charge trapped in the crystalline phase. By analyzing the characteristic parameters of these peaks, it was found that the increase of polarization temperature induced a decrease of the chain segment mobility and promoted the creation of structural traps in polyamide 610. The decrease of the chain segment mobility in the amorphous phase made the intensity of the α peak weak and the activation energy increased. The higher the polarization temperature, the higher the degree of crystallinity and the more charge carriers trapped in the crystalline phase. So, the increase of polarization temperature made the intensity of the ρ ₂ peak strong and increased the stability of trapped charge in the crystalline phase. The increase of polarization temperature also made the intensity of the ρ ₁ peak strong and decreased the stability of trapped charge in the amorphous phase and interphase.     

Electrospinning of biodegradable poly-3-hydroxybutyrate. Effect of the characteristics of the polymer solution

The effect of viscosity and electric conductivity of the polymer solution of poly-3-hydrobutyrate (PHB) on the formation of ultrafine fibers was studied. It was found that these parameters largely determine the geometrical parameters and morphology of the ultrafine fibers of PHB obtained by electrostatic forming. The increase in the viscosity of solutions at increased concentration and/or molecular mass of the polymer leads to an increase in the thickness uniformity of fibers and affects the diameter and diameter distribution width of the ultrathin fibers. Modification of the solutions with an ionogen electrolyte and hydrolytic agent (formic acid) decreases the initial molecular mass of the polymer and leads to increased viscosity of the system. The obtained fibers have found use in biomedicine, in particular, in the design of the elements of the locomotor system.     

Crystalline and relaxation properties of ethylene copolymer films inserted between two steel sheets

The relaxation and crystalline properties of ethylene vinyl acetate (EVA) co-polymers inserted in steel/polymer/steel assemblies were studied. To investigate the properties of the interfacial region, polymers of different thickness inserted in the assemblies were analyzed. The studied EVA copolymers are semicrystalline polymers. The relaxation properties of the amorphous phase were investigated by dynamic mechanical measurements performed on the steel/polymer/steel assemblies, and the crystalline properties were studied by differential scanning calorimetry (DSC). The results indicate that, for low polymer thicknesses, the mobility of the amorphous phase is significantly reduced. Significant changes in the crystalline organization also were observed when the polymer thickness decreased, with the presence of more numerous disorganized crystals for thin EVA layers. These crystals can act as physical ties that reduce the mobility of the neighboring amorphous chains. These results indicate the formation of an interphase layer of reduced mobility.