Properties of sulfonated poly(butylene terephthalate)

The synthesis, morphology, and mechanical properties of sulfonated poly(butylene terephthalate) (PBT) and its unsulfonated analogs were studied. The morphology of these copolymers crystallized from the melt were examined by a combination of wide-angle x-ray scattering (WAXS), polarized light microscopy, and small-angle light scattering (SALS). Stress-strain measurements are correlated with the morphological results. Spherulitic morphology, with a maltese cross at 45°C with respect to the crossed polars, is formed at low sulfonate levels (≤ 5.0 mol %). At a higher ion content, the maltese cross rotates 45° to form a cross pattern. At still higher sulfonate contents, typically 13 mol %, the light scattering pattern disappears completely. Microscopic and WAXS examination of these functionalized PBT copolymers confirms that the crystallinity level decreases with increasing ion content and is eliminated completely at the higher sulfonation level. The spherulite radius, however, remains invariant until the highest functionalization level. On the contrary, the morphology and properties of the unsulfonated isophthalate copolymer analogs remain relatively constant over the entire composition range examined. In several compositions clearly inferior properties are noted compared with the ion-containing copolymers.     

Development of radiation-grafted FEP-g-polystyrene membranes: Some property–structure correlations

Property–structure correlation in proton exchange membranes, prepared by simultaneous radiation grafting of styrene into FEP films and their subsequent sulfonation, was evaluated. The distribution of ionic sites across the membrane matrix was determined by microprobe measurements. The properties of these membranes, such as ion exchange capacity, swelling and ionic resistivity as a function of the degree of grafting, were studied. The thermal stability of membranes was studied using thermogravimetric analysis and ion exchange capacity measurements. Membranes undergo considerable structural changes in terms of the increase in the ionic content, enhanced hydrophilicity and decrease in crystallinity with the increasing degree of grafting. A correlation between some physical properties and stuctural changes occurring during the membrane preparation was established.     

Biodegradable fibers of poly(3‐hydroxybutyrate) produced by high‐speed melt spinning and spin drawing

The effects of high‐speed melt spinning and spin drawing on the structure and resulting properties of bacterial generated poly(3‐hydroxybutyrate) (PHB) fibers were investigated. The fibers were characterized by their degree of crystallinity by differential scanning calorimetry (DSC) and wide‐angle X‐ray scattering (WAXS), their orientation by WAXS, and the textile physical properties. The WAXS studies revealed that the fibers spun at high speeds and high draw ratios possessed orthorhombic (α modification) and hexagonal (β modification) crystals, the latter as a result of stress‐induced crystallization. The fiber structures formed during these processes were fibril‐like as the atomic force microscopy images demonstrated. The maximum physical break stress, the modulus, and the elongation at break observed in the fibril‐like spin drawn fibers were about 330 MPa, 7.7 GPa, and 37%, respectively. The fibers obtained by a low draw ratio of 4.0 had spherulitic structures and poor textile physical properties. The PHB pellets were analyzed by their degradation during the processes of drying and spinning and by their thermal and rheological properties. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2841–2850, 2000     

INFLUENCE OF COMPOSITIONAL HETEROGENEITY ON MORPHOLOGY AND PROPERTIES OF SEGMENTED COPOLYMERS

Polyethylene terephthalate(PET)/polycaprolactone(PCL) segmented copolymers with different hard segment contents and a blend of two of them were studied by using DSC, WAXS, TEM and IR techniques and dynamic mechanical, stress-strain and isothermal crystallization measurements. Emphasis was laid on the studies of influence of compositional heterogeneity on the morphology and properties of these segmented copolymers. It was found that the solution cast specimens of the more heterogeneous sample exhibit better segregation of segments, high crystallinity and melting temperature. They have higher thermal stability of mechanical properties at small deformations. However, they are less stable against large deformations and may become softer than the more homogeneous ones.     

Radiation grafted poly(vinylidene fluoride)-graft-polystyrene sulfonic acid membranes for fuel cells: Structure-property relationships

<正>Structure-property relationships for poly(vinylidene fluoride)-graft-polystyrene sulfonic acid(PVDF-g-PSSA) fuel cell membranes prepared by a single step method involving radiation-induced grafting of sodium styrene sulfonate(SSS) onto electron beam(EB) irradiated poly(vinylidene fluoride)(PVDF) films were established.The physico-chemical properties of the membranes such as ion exchange capacity,water swelling and proton conductivity were correlated with the degree of grafting(G,%) and the structural changes taking place in the membrane matrix during the preparation procedure. The variation in the crystallinity and the thermal stability of membranes was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis(TGA),respectively.The membranes were found to undergo substantial structural changes in forms of ionic sites increase,hydrophilicity enhancement,hydrophobicity reduction and crystallinity decrease with the variation in G(%) and the preparation method.The structural and thermal properties of the obtained membranes were also compared with their counterparts prepared by a conventional two-steps method i.e.radiation induced grafting of styrene onto EB irradiated PVDF films followed by sulfonation.The PVDF-g-PSSA membranes obtained by a single-step method were found to have superior properties compared to those obtained by the conventional two-steps method.     

Flow-induced crystallization regimes and rheology of isotactic polypropylene

We investigated the effect of flow in combination with molecular architecture on crystallization for linear and branched polypropylenes by means of dynamical mechanical spectroscopy. Compared to the linear polymer, the branched one exhibits much slower relaxation after deformation, causing higher levels of molecular orientation and molecular stretch for the same flow conditions. Different regimes of flow-induced crystallization are observed as a function of an increased level of molecular orientation and stretch. These regime changes cause the structure development in the material to vary from 3-dimensional spherulitical growth to nearly 1-dimensional fiber-like growth. Intermediate behavior is observed when the flow is strong (for the linear polymer) or weak enough (for the branched polymer), or in time when the effect of flow is exhausting. It is important to note that dynamical mechanical measurements can be used to probe different aspects of the (flow induced) crystallization process, such as a relative level of crystallinity and timescales of the evolution, but do not give absolute values. A correlation is found with the level of crystallinity obtained from real-time WAXS measurements and the kinetics of linear viscoelastic properties, but this correlation is not unique and depends on the pre-shear conditions applied.     

Structure and properties of propylene-ethylene block copolymers and the corresponding blends

Structure and properties of presumed polypropylene(PP)-b-polyethylene(PE) block copolymers (PPPE) and the corresponding blends (PP/PE) have been investigated by wide-angle x-ray scattering (WAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), torsional pendulum apparatus, and other techniques measuring mechanical properties. Crystallinity, morphological structure, and mechanical properties of the block copolymers and blends vary with the PP and PE compositions. Compared with PP homopolymers and PP/PE blends, PP and PE segments in PP-PE block copolymers have a reduced crystallinity, especially PE segments. An additional peak at about ?40°C is observed in dynamic relaxation spectra; substantially different morphology is revealed; and mechanical properties are greatly improved for the sequentially copolymerized PP-PE block copolymers, indicating the existence of PP-PE block structure.     

不同磺化度下的磺化聚醚醚酮对全钒储能液流电池性质影响的研究

本文报道了采用浓硫酸作为磺化剂,成功合成了不同磺化度下的聚醚醚酮(PEEK)膜,并深入研究了磺化条件包括磺化时间和磺化剂的用量对所获薄膜性能的影响,获得了在不同磺化度（DS）下SPPEK膜的离子交换容,含水率,机械性能,质子电导率等参数,特别测定了在全钒液流电池工作条件下钒离子(Ⅳ)渗透率,首次为该类液流储能电池使用价廉质优的质子交换膜提供了基础实验数据。室温条件下的实验结果如下：1）磺化12小时后,膜的磺化度46%,含水量为28%,钒离子(Ⅳ)选择性最佳（钒离子渗透率为1.2×10-7 cm2/min-1,是Nafion117 (2.9×10-6 cm2/min-1)的1/24）,其质子电导率只有0.02 S/cm;2）磺化96小时其磺化度达79%的膜,质子电导率达0.16 S/cm,是Nafion117 (0.10S/cm) 的1.6倍, 但其机械性能最差;3）与Nafion117膜相比,磺化在36到48小时的SPPEK膜其机械力学性能好,薄膜的钒离子渗透率、离子交换容IEC、质子导电率和含水率高,且对钒离子的选择性佳,尤其价格仅为Nafion膜的1/13,是理想的Nafion膜的代替物,可望直接应用于全钒氧化还原液流（VRB）电池中。本文还讨论了磺化时间和不同磺化剂量对膜的性质的影响。     

Mechanical properties of amphiphilic urethane acrylate ionomer hydrogels having heterophasic gel structure

Amphiphilic urethane acryale hydrogels containing ionic groups (dimethylolpropionic acid) were prepared by varying the molecular weight of the soft segment (polyether type) and the type of diisocyanate, and their mechanical properties were examined. They showed heterophasic gel structure composed of ionic hard domains induced by aggregation of the ionic groups and polyether soft domains comprising the urethane acrylate network. This heterophasic structure could be confirmed by dynamic mechanical analysis (DMA) and by wide-angle X-ray scattering analysis (WAXS); the crystallinity detected by WAXS and the transition peak of the ionic hard domains detected by DMA strongly suggested that there were ionic aggregates. These ionic aggregates acted as reinforcing fillers in the network, which eventually enhanced the tensile strength of the hydrogels. Above all, the tensile properties of the hydrogels were of interest in that the trends of the stress-strain curves were consistent with the rubbery ones. It is believed that the higher purity of the polyether soft domains resulted from the heterophasic gel structure imparting further elastomeric properties on the network. Received: 31 July 1998 Accepted in revised form: 15 October 1998     

Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

Evaluation of new organosolv dissolving pulps. Part II: Structure and NMMO processability of the pulps

The supermolecular structure of dissolving pulps produced from hardwood by the organosolv processes Acetosolv, Formacell, and Milox was characterized by physical methods (TEM, WAXS, SAXS, NMR) and compared with conventional Sulfite and standard commercial dissolving pulps. The suitability of the pulps for the NMMO technology was tested by spinning fibres and blowing films, whose structural and mechanical properties have also been determined. With TEM it was shown that the TCF-bleached organosolv pulps have only the primary (Formacell), the primary and S1 (Milox), or mainly the S1 (Acetosolv) layers exposed to the surface, whereas Sulfite pulping exposes the S2 cell wall layer. Especially for Milox and Acetosolv Eucalyptus wood pulps, a reduced degree of crystallinity was found, both with WAXS and NMR. The SAXS results indicate a lower pore intersection length for the new pulps as compared to conventional pulps. Unbleached organosolv pulps show a lower crystallinity, very low pore intersection lengths, and an average crystallite shape different from their bleached counterparts. The dissolution behaviour in NMMO and the processability of the bleached organosolv pulps was satisfactory so far. Fibres and films could be produced with structural and mechanical properties comparable with conventional Sulfite and standard commercial dissolving pulp products. However, unbleached organosolv pulps did not meet the requirements of the NMMO process.     

Development of the morphology and crystalline state due to hybridization of reinforced toughened nylon containing a liquid‐crystalline polymer

A hybrid composite consisting of rubber‐toughened nylon‐6,6, short glass fibers, and a thermotropic liquid‐crystalline polymers (LCP) was investigated by the LCP content being varied. The thermal behavior, morphology, and crystallization behavior due to hybridization were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and wide‐angle X‐ray scattering (WAXS). DSC results indicated that the crystallinity of the glass‐fiber‐reinforced toughened nylon‐6,6 was reduced by LCP addition, particularly 5–10 wt % LCP. DMA data showed that the miscibility between the blended components was maximum at the 5 wt % LCP composition, and the miscibility decreased with increasing LCP content. SEM photomicrographs revealed information consistent with the thermal behavior on miscibility. It was also observed that the 10 wt % LCP composition showed predominantly an amorphous character with FTIR and WAXS. WAXS results indicated that LCP hybridization increased the interplanar spacing of the hydrogen‐bonded sheets of the nylon crystals rather than the spacing between the hydrogen‐bonded chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 549–559, 2003     

Kinetic study of the sulfonation of hydrogenated styrene butadiene block copolymer (HSBS): Microstructural and electrical characterizations

In this work homogeneous sulfonation kinetic and both, microstructural and electrical characterizations of hydrogenated styrene butadiene block copolymer (HSBS) were studied. The incorporation of sulfonic groups was checked by infrared spectroscopy (FTIR-ATR) and the sulfonation level was determined by both, elemental analysis (E.A.) and chemical titration. Thermal behavior was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), in order to determine thermal transitions and stability, respectively. Microstructure was studied, by means of dynamic mechanical analysis (DMA). Atomic force microscopy (AFM) was studied for several samples and evidenced a morphology change when the sulfonation level increases. Finally, electrical behavior was recorded by means of electrochemical impedance spectroscopy (EIS) and the four-probe technique (FPT). Results show that sulfonation of the benzene rings, in the styrene units, has effectively occurred and that the sulfonation level increases with reaction time. When incrementing the sulfonation level, a structural change in the copolymer was observed. Interconnected clusters allow proton conduction through the membrane. The ion conductivity obtained was about 10⁻² S/cm.     

Effect of stoichiometry and pH on the structure and properties of Chitosan/Chondroitin sulfate complexes

This work reports the formation of chitosan (CHT)/chondroitin sulfate (CS) polyelectrolyte complexes and evaluates the changes in their complexation-stoichiometries, crystallinity, and mechanical properties at different pHs used for both complex preparation and swelling. Through high-performance liquid chromatography, the changes in CHT/CS complex stoichiometry due to CS release from CHT/CS complexes, which occurred mainly during swelling at pH ??6, were determined. In addition, strong evidences of self-assembling on CHT/CS complex network as swelled at pH?12 buffer were observed by WAXS patterns. Such a new rearrangement of the network increases the CHT/CS complexes rigidity as well as their elastic moduli, E, as observed through compressive tests. The results found in this work provide new information to allow the tailoring of the biofunctionalities of the CHT/CS complex for the development of physiological pH-compatible materials.     

UV radiation induced graft copolymerization of allyl acetate onto poly(ethylene terephthalate) (PET) films for fuel cell membranes

Ultraviolet（UV）-induced graft copolymerization of allyl acetate（AA） monomer onto polyethylene terephthalate) （PET） films and the subsequent sulfonation on the monomer units in the grafting chain using chlorosulfonic acid（ClSO₃H） were carried out to prepare proton exchange membranes（PEMs） for fuel cells.A maximum grafting value of 12.8%was found for 35 vol%allyl acetate after 3 h radiation time.Optimum concentration of C1SO₃H was selected for the sulfonation reaction to be 0.05 mol/L based on the degree of sulfonation and the tensile strength studies of the membrane.The degree of sulfonation increased as the sulfonation reaction temperature and sulfonation time were increasing.The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as FTIR spectroscopy.The maximum ion exchange capacity（IEC） of 0.04125 mmol g^-1 was found at 12.1%degree of sulfonation and the maximum proton conductivity was found to be 0.035 S cm^-1 at 30℃and a relative humidity of 60%.The various physical and chemical properties of the PEMs such as water uptake,mechanical strength,thermal durability and oxidative stability were also studied.To investigate the suitability of the prepared membrane for fuel cell applications,its properties were compared with those of Nafion 117.     

Transreactions in poly trimethylene terephthalate/bisphenol-A polycarbonate (PC) blends analysed by pressure-volume-temperature measurements

The effect of annealing on the miscibility and thermal properties of poly trimethylene terephthalate (PTT)/bisphenol-A polycarbonate (PC) blends was examined using pressure-volume-temperature (PVT) measurements. The PTT/PC blends were thermally annealed at 260 °C for different times to induce various extents of transesterification reactions between the two polymers. The non-annealed blends are immiscible and exhibit the thermal properties of the blend components. Upon annealing, the original semi-crystalline morphology transforms to an increasingly amorphous nature. PVT and WAXS analysis confirmed that the PTT/PC blends completely lost their crystallinity when annealed at 260 °C for a period of 120 min or longer, indicating the formation of random co-polyesters due to chemical transreactions between the PTT and PC. The further increase in the specific volume with annealing time also indicates that after reaching a completely amorphous co-polymer the transesterification continuous until a fully random copolymer is formed.     

Proton mobility in hydrated sulfonated polystyrene: NMR and impedance studies

Different ionomers were obtained by sulfonation of a commercial polystyrene (PS), using acetyl sulfate as reagent. The sulfonation was assessed by FTIR and XPS spectroscopies and the thermal and mechanical properties were deduced from DMA measurements. The acid form of the ionomers was characterized by means of ¹H and ¹³C MAS-NMR spectroscopies. Polymer hydration under controlled humidity atmosphere was analyzed by gravimetric, NMR and complex impedance techniques. In the hydrated state, two stages associated with formation of hydronium (H₃O⁺) species and proton hopping between adsorbed water molecules were deduced from NMR data. Both processes are responsible for important changes detected in mechanical properties and conductivity of sulfonated polymers during hydration processes.     

Gamma Radiation-Induced Graft Copolymerization of Styrene Onto Polyethyleneterephthalate Films: Application in Fuel Cell Technology as a Proton Exchange Membrane

Polyethyleneterephthalate (PET) based proton exchange membrane for using in fuel cells was successfully prepared by gamma radiation-induced graft copolymerization of styrene monomer onto PET film and the consequent selective sulfonation of the grafting chain in the film state using chlorosulfonic acid (ClSO₃H). The effects of grafting conditions (e.g., monomer concentration, irradiation dose) on the degree of grafting and sulfonation condition (e.g., optimum concentration of ClSO₃H) on the degree of sulfonation were studied. The degree of grafting, the degree of sulfonation and the physico-chemical properties (such as, water uptake, mechanical strength, thermal durability, hydrolytic stability, oxidative stability) of the gamma radiation-induced grafted membrane were found to be better when compared to those of the UV-radiation grafted membrane. The membrane shows higher ion exchange capacity (0.9 mmol g^?1) and higher proton conductivity (0.075 S cm^?1), similar to those of Nafion membrane.     

Thermogravimetric and wide angle X-ray diffraction analysis of thermoplastic elastomers from nylon copolymer and EPDM rubber

Nylon copolymer (PA6, 66) and ethylene propylene diene (EPDM) blends with and without compatibilizer were prepared by melt mixing using Brabender Plasticorder. The thermal stability of nylon copolymer (PA6, 66)/ethylene propylene diene rubber (EPDM) blends was studied using thermogravimetric analysis (TGA). The morphology of the blends was investigated using scanning electron microscopy (SEM). In this work, the effects of blend ratio and compatibilisation on thermal stability and crystallinity were investigated. The incorporation of EPDM rubber was found to improve the thermal stability of nylon copolymer. The kinetic parameters of the degradation process were also studied. A good correlation was observed between the thermal properties and phase morphology of the blends. By applying Coats and Redfern method, the activation energies of various blends were derived from the Thermogravimetric curves. The compatibilization of the blends using EPM-g-MA has increased the degradation temperature and decreased the weight loss. EPM-g-MA is an effective compatibilizer as it increases the decomposition temperature and thermal stability of the blends. Crystallinity of various systems has been studied using wide angle X-ray scattering (WAXS). The addition of EPDM decreases the crystallinity of the blend systems.     

Supercritical Carbon Dioxide Isolation of Cellulose Nanofibre and Enhancement Properties in Biopolymer Composites

The physical properties, such as the fibre dimension and crystallinity, of cellulose nanofibre (CNF) are significant to its functional reinforcement ability in composites. This study used supercritical carbon dioxide as a fibre bundle defibrillation pretreatment for the isolation of CNF from bamboo, in order to enhance its physical properties. The isolated CNF was characterised through zeta potential, TEM, XRD, and FT-IR analysis. Commercial CNF was used as a reference to evaluate the effectiveness of the method. The physical, mechanical, thermal, and wettability properties of the bamboo and commercial CNF-reinforced PLA/chitin were also analysed. The TEM and FT-IR results showed the successful isolation of CNF from bamboo using this method, with good colloidal stability shown by the zeta potential results. The properties of the isolated bamboo CNF were similar to the commercial type. However, the fibre diameter distribution and the crystallinity index significantly differed between the bamboo and the commercial CNF. The bamboo CNF had a smaller fibre size and a higher crystallinity index than the commercial CNF. The results from the CNF-reinforced biocomposite showed that the physical, mechanical, thermal, and wettability properties were significantly different due to the variations in their fibre sizes and crystallinity indices. The properties of bamboo CNF biocomposites were significantly better than those of commercial CNF biocomposites. This indicates that the physical properties (fibre size and crystallinity) of an isolated CNF significantly affect its reinforcement ability in biocomposites. The physical properties of isolated CNFs are partly dependent on their source and production method, among other factors. These composites can be used for various industrial applications, including packaging.