Synthesis and characterization of a novel biodegradable, thermoplastic polyurethane elastomer

A series of biodegradable, thermoplastic polyurethane elastomers poly (epsilon-caprolactone-co-lactide)polyurethane [PCLA-PU] were synthesized from a random copolymer Of L-lactide (LA) and epsilon-caprolactone (CL), hexamethylene diisocyanate, and 1,4-butanediol. The effects of the LA/CL monomer ratio and hard-segment content on the thermal and mechanical properties of PCLA-PUs were investigated. Gel permeation chromatography, IR, C-13 NMR, and X-ray diffraction were used to confirm the formation and structure of PCLA-PUs. Through differential scanning calorimetry, tensile testing, and tensile-recovery testing, their thermal and mechanical properties were characterized. Their glass-transition temperatures were below -8 degrees C, and their soft domains became amorphous as the LA content increased. They displayed excellent mechanical properties, such as a tensile strength as high as 38 MPa, a tensile modulus as low as 10 MPa, and an elongation at break of 1300%. Therefore, they could find applications in biomedical fields, such as soft-tissue engineering and artificial skin.

Poly(L-lactide)/starch blends compatibilized with poly(L-lactide)-g-starch copolymer

The poly(L-lactide) (PLLA)/starch blends were prepared by the PLLA grafting starch (PLLA-g-St) copolymers as a compatibilizer, and their thermal, mechanical and morphological characterizations were performed to show the better performance of these blends compared to the virgin PLLA/starch blend without the compatibilizer, including PLLA crystallinity, interfacial adhesion between the PLLA matrix and starch dispersive phases, mechanical test, medium resistance, and contact angle. The 50/50 composite of PLLA/starch compatibilized by 10% PLLA-g-St gave a tensile strength of 24.7 MPa and an elongation at break of 8.7%, respectively, vs. 11.3 MPa and 1.5%, respectively, for the simple 50/50 blend of PLLA/starch.

Stress transfer and damage evolution simulations of fiber-reinforced polymer-matrix composites

The stress transfer from broken fibers to unbroken fibers in fiber-reinforced thermosetting polymer-matrix composites and thermoplastic polymer-matrix composites was studied using a detailed finite element model. In order to check the validity of this approach, an epoxy-matrix monolayer composite was used as thermosetting polymer-matrix composite and a polypropylene (PP)-matrix monolayer composite was used as thermoplastic polymer-matrix composite, respectively. It is found that the stress concentrations near the broken fiber element cause damage to the neighboring epoxy matrix prior to the breakage of other fibers, whereas in the case of PP-matrix composites the fibers nearest to the broken fiber break prior to the PP matrix damage, because the PP matrix around the broken fiber element yields. In order to simulate composite damage evolution, a Monte Carlo technique based on a finite element method has been developed in the paper. The finite element code coupled with statistical model of fiber strength specifically written for this problem was used to determine the stress redistribution. Five hundred samples of numerical simulation were carried out to obtain statistical deformation and failure process of composites with fixed fiber volume fraction.

Preparation and properties of ternary polyimide/SiO2/polydiphenyisiloxane composite films

A series of novel ternary polyimide/SiO2/polydiphenylsiloxane (PI/SiO2/PDPhS) composite films were prepared through co-hydrolysis and condensation between tetramethoxysilane, diphenyldimethoxysilane (DDS) and aminopropyltriethoxysilane-terminated polyamic acid, using an in situ sol-gel method. The composite films exhibited good optical transparency up to 30 wt% of total content of DDS and SiO2. SEM analysis showed that the PDPhS and SiO2 were well dispersed in the PI matrix without macroscopic separation of the composite films. TGA analysis indicated that the introduction of SiO2 could improve the thermal stability of the composite films. Dynamic mechanical thermal analysis showed that the composite films with low DDS content (5 wt%) had a higher glass transition temperature (T-g) than pure PI matrix. When the content of DDS was above 10 wt%, the T-g of the composite decreased slightly due to the plasticizing effect of flexible PDPhS linkages on the rigid PI chains. The composite films with high SiO2 content exhibited higher values of storage modulus. Tensile measurements also showed that the modulus and tensile strength of the composite films increased with increasing SiO2 content, and the composite films still retained a high elongation at break due the introduction of DDS.

Microstructure and properties of new polyimide/polysiloxane composite films

A series of novel polyimide/polydiphenylsiloxane) (PI/PDDS) composite films with different contents of DDS were prepared using sol-gel method. The noncrosslinked PI-DDS and crosslinked PIS-DDS were synthesized through cohydrolysis and condensation between DDS and polyamic acid (PAA) or aminopropyltriethoxysilane(APTES)-terminated polyamic acid (PAAS). All the composite films have high thermal stability near pure PI. Field emission scanning electron microscopy (FE-SEM) study shows that the polysiloxane from hydrolyzed DDS well dispersed in polyimide matrix, without macroscopic separation for the composite films with low content of DDS, while large domain of polysiloxane was formed in films with high DDS content. The microstructure of composite films is in accordance with the transparency of corresponding films. X-ray study shows the PDDS is amorphous in PI matrix. The introduction of DDS into PI can improve the elongation at break and at the same time, the composite films still remained with higher modulus and tensile strength. The density and water absorption of the composite films decreased with the increasing DDS content. The composite films with DDS content below 10 wt % exhibit good solvent resistance.

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3-butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T-g) and the melting temperature (T-m) of PLA. Moreover, crystallinity of PLA increased with increasing the con-tent of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break.

Syntheses and properties of polyimides derived from diamines containing 2,5-disubstituted pyridine group

A Series of novel homo- and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5-bis (4-aminophenyl) pyridine and 2-(4aminophenyl)-5-aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60-9.64 dL/g (c = 0.5 g/dL in DMAC, 30 degrees C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548-598 degrees C in air. The glass transition temperatures of the PMDA-based samples are in the range of 395-438 degrees C, while the BPDA-based polyimides show two glass transition temperatures (T(g)1 and T(g)2), ranging from 268 to 353 degrees C and from 395 to 418 degrees C, respectively. The flexible films possess tensile modulus in the range of 3.42-6.39 GPa, strength in the range of 112-363 MPa and an elongation at break in the range of 1.2-69%. The strong reflection peaks in the wide-angle X-ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity.

Syntheses and properties of novel polyimides derived from 2-(4-aminophenyl)-5-aminopyrimidine

2-(4-Aminophenyl)-5-aminopyrimidine (4) is synthesized via a condensation reaction of vinamidium salts and amidine chloride salts, followed by hydrazine palladium catalyzed reduction. A series of novel homo- and copolyimides containing pyrimidine unit are prepared from the diamine and 1,4-phenylenediamine (PDA) with pyromellitic dianhydride (PMDA) or 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidization method. The poly(amic acid) precursors had inherent viscosities of 0.97-4.38 dL/g (c = 0.5 g/dL, in DMAc, 30 degrees C) and all of them could be cast and thermally converted into flexible and tough polyimide films. All of the polyimides showed excellent thermal stability and mechanical properties. The glass transition temperatures of the resulting polyimides are in the range of 307-434 degrees C and the 10% weight loss temperature is in the range of 556-609 degrees C under air. The polyimide films possess strength at break in the range of 185-271 MPa, elongations at break in the range of 6.8-51%, and tensile modulus in the range of 3.5-6.46 GPa. The polymer films are insoluble in common organic solvents, exhibiting high chemical resistance.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

Improvement of mechanical property of polyimide blends with Co-60-irradiation

Radiation effects on polyimide blends' were studied at different irradiation temperatures and with different irradiation doses. The irradiation polyimides were the blends of linear polyimide (HQDPA/ODA) and 4-phenylethynyl phthalic anhydride end-capped oligomer polyimide. The tensile strength and the elongation at break of irradiated films were determined as the function of irradiation temperature and dose. Under proper conditions crosslinking reaction occurred when the polyimide blends were irradiated at high temperature. The mechanical properties of irradiated polyimide blends were found to be different from the linear polyimide.

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.

Cardo polyarylethersulfones and polyaryletherketones bearing alkyl substituents on the phenylene unit

A series of cardo polyaryletherketones and polyaryletersulfones containing alkyl substituents of a different kind, number and volume were synthesized from bis(4-nitrophenyl)ketone or bis(4-fluorophenyl)sulfone with various alkyl substituted phenolphthaleins by polycondensation using K2CO3 as catalyst. Their chemical and aggregation structures were confirmed by FT-IR, H-1-NMR and WAXD. The resulting polymers were soluble in a variety of common polar solvents and, transparent, colorless, and tough films could be easily cast from 1,1,2-trichluoroethane solution. Their tensile strength, elongation at break and tensile modulis were in the range of 70.5 similar to 97.1MPa, 4.49%similar to7.81%, and 1.69 similar to2.27GPa, respectively. The prepared polymers had reasonably high glass transition temperatures at 207 to 269 degreesC, and showed fairly good thermal stability with 5% thermal decomposition loss above 410 degreesC.

Toughening PA1010 with a functionalized saturated polyolefin elastomer

Polyamide (PA)1010 is blended with a saturated polyolefin elastomer, ethylene-cu-olefin copolymer (EOCP). To improve the compatibility of PA1010 with EOCP, different grafting rates of EOCP with maleic anhydride (MA) are used. The reaction between PA1010 and EOCP-g-MA during extrusion is verified through an extraction test. Mechanical properties, such as notched Izod impact strength, elongation at break, etc., are examined as a function of grafting rate and weight fraction of elastomer. It was found that in the scale of grafting rate (0.13-0.92 wt %), 0.51 wt % is an extreme point for several mechanical properties. Elastomer domains of PA1010/ EOCP-g-MA blends show a finer and more uniform dispersion in the matrix than that of PA1010/EOCP blends. For the same grafting rate, the average sizes of elastomer particles are almost independent on the contents of elastomer, but for different grafting rates, the particle sizes are decreased with increasing grafting rate. The copolymer formed during extrusion strengthens the interfacial adhesion and acts as an emulsifier to prevent the aggregation of elastomer in the process of blending. (C) 2000 John Wiley & Sons, Inc.

Study of elastic modulus and yield strength of polymer thin films using atomic force microscopy

Nanometer-scale elastic moduli and yield strengths of polycarbonate (PC) and polystyrene (PS) thin films were measured with atomic force microscopy (AFM) indentation measurements. By analysis of the AFM indentation force curves with the method by Oliver and Pharr, Young's moduli of PC and PS thin films could be obtained as 2.2 +/- 0.1 and 2.6 +/- 0.1 GPa, respectively, which agree well with the literature values. By fitting Johnson's conical spherical cavity model to the measured plastic zone sizes, we obtained yield strengths of 141.2 MPa for PC thin films and 178.7 MPa for PS thin films, which are similar to2 times the values expected from the literature. We propose that it is due to the AFM indentation being asymmetric, which was not accounted for in Johnson's model. A correction factor, epsilon, of similar to0.72 was introduced to rescale the plastic zone size, whereupon good agreement between theory and experiment was achieved.

Radiation effects on the immiscible polymer blend of nylon1010 and high-impact strength polystyrene (II): mechanical properties and morphology

The paper studies the morphology and mechanical properties of immiscible binary blends of the nylon 1010 and HIPS through the radiation crosslinking method. In this blend, the HIPS particles were the dispersed phases in the nylon 1010 matrix. With increasing of dose, the elastic modulus increased, However, the tensile strength. elongation at bleak and the energy of fracture increased to a maximum at a dose of 0.34 MGy, then reduced with the increasing of dose. SEM photographs show that the hole sizes are not changed obviously at low dose and at high dose, remnants that cannot be dissolved in formic acid and THF can be observed in the holes and on the surface. TEM photographs showed that radiation destroys the rubber phases in the polymer blend. (C) 2001 Elsevier Science Ltd. All rights reserved.