Thermal and mechanical properties of nanocomposites based on a PLLA‐b‐PEO‐b‐PLLA triblock copolymer and nanohydroxyapatite

Composites which combine biocompatible polymers and hydroxyapatite are unique materials with regards to their mechanical properties and bioactivity in the development of temporary bone‐fixation devices. Nanocomposites based on a biocompatible and amphiphilic triblock copolymer of poly(l‐ lactide) (PLLA) and poly(ethylene oxide) (PEO) —PLLA‐b‐PEO‐b‐PLLA— and neat (nHAp) or PEO‐modified (nHAp@PEO) hydroxyapatite nanoparticles were prepared by dispersion in benzene solutions, followed by freeze‐drying and injection moulding processes. The morphology of the copolymers of a PEO block dispersed throughout a PLLA matrix was not changed with addition of the nanofillers. The nHAp particles were spherical and, after modification, the nHAp@PEO nanoparticles were partially agglomerated. In the nanocomposites, these particles characteristics remained unchanged, and the nHAp particles and nHAp@PEO agglomerates were uniformly dispersed through the copolymer matrix. These particles acted as nucleating agents, with nHAp@PEO being more efficient. The incorporation of nHAp increased both the reduced elastic modulus (～22%) and the indentation hardness (～15%) in comparison to the copolymer matrix, as determined by nanoindentation tests, while nHAp@PEO addition resulted in lower increments of these mechanical parameters. The incorporation of untreated nHAp was, therefore, more beneficial with regards to the mechanical properties, since the amphiphilic PLLA‐b‐PEO‐b‐PLLA matrix was already efficient for nHAp nanoparticles dispersion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44187.     

Influence of PS‐b‐PEO diblock copolymers on the compatibility of syndiotactic polystyrene modified epoxy blends

Homogeneous solutions of syndiotactic polystyrene (sPS) in diglycidylether of bisphenol A (DGEBA), containing 2.5, 5 and 7.5 wt % of thermoplastic with or without 0.5 and 1 wt % of poly(styrene‐b‐ethylene oxide) (PS‐b‐PEO) block copolymer, were polymerized using a stoichiometric amount of an aromatic amine hardener, 4,4′‐methylene bis (3‐chloro‐2,6‐diethylaniline) (MCDEA). The dynamic‐mechanical properties and morphological changes of sPS‐(DGEBA/MCDEA) compatibilized with different amount of PS‐b‐PEO have been investigated in this paper. The addition of the block copolymer produced significant changes in the morphologies generated. The size of the dispersed spherical sPS spherulites does not change significantly, but less spherulites of sPS appeared upon network formation in the systems with compatibilizer, what means that addition of compatibilizer in this system delayed crystallization of sPS in sPS‐(DGEBA/MCDEA) systems and change phase separation mechanism from crystallization‐induced phase separation (CIPS) and reaction‐induced phase separation (RIPS) almost only to RIPS. Moreover, PS‐b‐PEO with higher molecular weight of PS block seems to be a more effective compatibilizer than one with lower molecular weight of PS block. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 479–488, 2006     

Preparation,morphology, and properties of silane‐modified MWCNT/epoxy composites

Both epoxy resin and acid‐modified multiwall carbon nanotube (MWCNT) were treated with 3‐isocyanatopropyltriethoxysilane (IPTES). Scanning electron microscopy (SEM) and transmission electronic microscope (TEM) images of the MWCNT/epoxy composites have been investigated. Tensile strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 41% comparing to the neat epoxy. Young's modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 52%. Flexural strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 145% comparing to neat epoxy. Flexural modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 31%. Surface and volume electrical resistance of MWCNT/epoxy composites were decreased with IPTES‐MWCNT content by 2 orders and 6 orders of magnitude, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies of the properties of a thermosetting epoxy modified with block copolymers

Poly[(n‐butyl acrylate)‐block‐poly(methyl methacrylate)‐co‐(glycidyl methacrylate)] (BMG) diblock copolymers incorporating an epoxy‐reactive functionality in one block have been synthesized and used as modifiers for the model epoxy resin E‐51 cured with 4,4′‐diaminodiphenyl methane (DDM). The properties and morphologies of the modified epoxy thermosets were investigated by dynamic mechanical analysis (DMA), impact testing and scanning electron microscopy (SEM). The results reveal that addition of the block copolymers leaves the glass transition temperatures of the blends relatively unchanged, with small decreases in the storage moduli at room temperature. The toughening effect is dependent on the chemical structures of the block copolymers and an increase in the impact strength by a factor of two was obtained by the addition of ‘relatively symmetrical’ block copolymers. Moreover, the impact test results are consistent with the morphologies of the fracture surfaces as evidenced by SEM. Copyright © 2005 Society of Chemical Industry     

Polyether and polyester polyol based glycidyl-terminated polyurethane modified epoxy resins: Mechanical properties and morphology

A glycidyl-terminated polyurethane prepolymer was synthesized and used to enhance the properties of epoxy resins. Some properties of glycidyl-terminated PU/epoxy with polyether based (PPG) and polyester based (PBA) glycidyl-terminated PU were investigated in this research. The polyether based glycidyl-terminated PU(PPG) modified epoxy resin proved to be superior to conventional epoxy resins in improved impact strength and fracture energy, but not tensile strength, tensile modulus, flexural strength and flexural modulus. On the other hand, the polyester based glycidyl-terminated PU(PBA) modified epoxy resin had increased mechanical properties while showing slight variation of impact strength and fracture energy. Different mechanisms for this behaviour are advanced in this paper.     

Effect of molecular weight and content of PDMS on morphology and properties of silicone‐modified epoxy resin

To achieve a stable blend of a bisphenol A type epoxy resin and poly(dimethylsiloxane) (PDMS), reaction between hydroxyl (OH) groups of the epoxy and silanol groups of hydroxyl‐terminated(HT) PDMS has been investigated. The chemical structures of the HTPDMS‐modified epoxies were characterized by Fourier transform infrared (FTIR) and ¹H‐ and ¹³C‐NMR spectroscopy. To allow further understanding of the influence of viscosity and content of HTPDMS on the blend morphology, four different viscosities of HTPDMS were used in three content levels. The morphologies of modified epoxy resins were observed with optical microscopy. The modified epoxies were cured with a cycloaliphatic polyamine. The morphologies of modified epoxies were investigated by using scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) technique. The cured films showed droplet in matrix morphology with different mean droplets size which was influenced by the viscosity and the content of the incorporated HTPDMS. To illustrate the effect of the morphologies of the cured samples on mechanical properties, tensile strength tests were performed. The introduction of HTPDMS into the epoxy altered the tensile behavior according to its viscosity and content. Surface properties of the cured films were evaluated by sessile drop method. The results clearly indicate that the hydrophilic surface of the epoxy turns to a hydrophobic one due to the modification with HTPDMS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Physico‐mechanical properties of nano‐polystyrene‐decorated graphene oxide–epoxy composites

Nano‐polystyrene (nPS)‐decorated graphene oxide (GO) hybrid nanostructures were successfully synthesized using stepwise microemulsion polymerization, and characterized using Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), field‐emission scanning electron microscopy and transmission electron microscopy. XRD and FTIR spectra revealed the existence of a strong interaction between nPS and GO, which implied that the polymer chains were successfully grafted onto the surface of the GO. The nPS‐decorated GO hybrid nanostructures were compounded with epoxy using a hand lay‐up technique, and the effect of the nPS‐decorated GO on the mechanical, thermal and surface morphological properties of the epoxy matrix was investigated using a universal tensile machine, Izod impact tester, thermogravimetric analysis and contact angle measurements with a goniometer. It was observed that in the epoxy matrix, GO improved the compatibility. © 2017 Society of Chemical Industry     

Control of morphologies and mechanical properties of thermoplastic‐modified epoxy matrices by addition of a second thermoplastic

Ternary mixtures based on stoichiometric mixtures of the diglycidyl ether of bisphenol‐A (DGEBA) and 4,4′‐diaminodiphenyl sulfone (DDS) and two miscible thermoplastics, poly(methyl methacrylate) (PMMA) and the poly(hydroxy ether of bisphenol‐A) (phenoxy), were investigated by optical microscopy (OM), atomic force microscopy (AFM) and dynamic mechanical analysis (DMA). Mechanical testing was used to study the ultimate behavior. All the modified epoxy mixtures were heterogeneous. DMA has been shown to be an excellent technique for detecting the morphologies generated after curing when the loss modulus is used for analysis. Morphology varied with the thermoplastic content on the mixtures. The addition of a second thermoplastic in small amounts changed the morphological features from particulated to co‐continuous and from that to phase‐inverted morphologies. A significant increase in fracture toughness was observed above all for the mixtures with some level of co‐continuity within the epoxy‐rich matrix. Phase inversion led to poor strength and also fracture toughness. Copyright © 2003 Society of Chemical Industry     

Influence of reactant concentration on formation of AgCl particles in PEO–PPO–PEO microemulsion and morphology and performance of AgCl–PMMA membranes

AgCl/poly(methyl methacrylate) (PMMA) organic–inorganic hybrid membrane has been synthesized by reverse microemulsion polymerization using triblock copolymer polyoxyethylene–polyoxypropylene–polyoxyethylene as surfactant and MMA as oil phase. The results by ultraviolet–visible spectrum, transmission electron microscopy, and scanning electron microscopy showed that small AgCl nanoparticles distributed well in the F127 microemulsions and hybrid membranes at low reactant concentration. AgCl nanoparticles in the microemulsion became smaller with increasing reactant concentration. However, AgCl nanoparticles aggregated obviously in hybrid membranes, when reactant concentration was more than 0.15 mol L^?1. The performance of different hybrid membranes for separation of the benzene and cyclohexane was measured. The results indicated that the separation performance of membrane was promoted obviously due to presence of more well‐dispersed AgCl particles in hybrid membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Toughening of epoxy resins modified with polyetherester block copolymers: the influence of modifier molecular architecture on mechanical properties

Thermoplastic elastomers based on polyetheresters with polyoxytetramethylene soft segments and poly(hexamethyleneterephthalate) hard segments were used to toughen anhydride‐cured epoxy resins. The ratio between hard and soft segments and the crystallinity of the hard segments prepared by incorporating poly(hexamethyleneisophthalate) in the block copolymer were varied in order to examine the effect of the modifier's molecular architecture on morphology and mechanical properties of the resin, such as toughness, strength, and stiffness. The experimental data show that segmented polyetheresters are suitable toughening agents for epoxies. The compatibility between resin and toughener and also the mechanical properties of the modified resin depend on the ratio between the hard and soft segments. Epoxy resins blended with 10 wt % of the polyetherester exhibit an increase in toughness by 50–150%, while strength and modulus decrease by 20% or less. An optimal phase adhesion at levels between 70 and 85 wt % of soft segments in the modifier results in a maximum of toughness enhancement (by about 150%) of the resin accompanied with only a slight drop in strength and stiffness (by about 15%). The glass transition temperature is only slightly affected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 623–634, 2000     

Bulk properties of epoxy resin modified by epoxy–aminosilane copolymers

A linear epoxy–aminopropyltriethoxysilane addition polymer was used as a new epoxy modifier. In this paper, the thermal and mechanical properties have been determined by differential scanning calorimetry (DSC) and mechanical testing. The experimental results show that this copolymer modifier can effectively improve the toughness of resins without sacrificing their thermal resistance, stiffness and strength. As a comparison, the properties of epoxy resin blended with aminopropyltriethoxysilane (γ-APS) have been carried out simultaneously. © 1999 Society of Chemical Industry     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Thermoreversible gelation of a polystyrene–poly(ethylene/butylene)–polystyrene triblock copolymer in n‐octane/4‐methyl‐2‐pentanone solutions

The thermoreversible gelation of a triblock copolymer polystyrene‐block‐poly(ethylene/butylene)‐block‐polystyrene in n‐octane and two solvent mixtures of n‐octane and 4‐methyl‐2‐pentanone with a high n‐octane content has been studied. n‐Octane and 4‐methyl‐2‐pentanone are selective solvents for the middle poly(ethylene/butylene) block and the end polystyrene blocks, respectively. The influence of the solvent composition on the sol–gel transition and the mechanical properties of the gels was studied. The gel formation temperature increased with the copolymer concentration and the n‐octane content in the solvent system. The mechanical properties of the different gels were studied through oscillatory shear measurements. The concentration dependence of the elastic storage modulus showed an exponent close to that expected for gels in good solvents (2.25) that possess a structure similar to those of chemical networks. © 2002 Society of Chemical Industry     

Mechanical properties and morphology of epoxidized soyabean‐oil‐modified epoxy resin

Epoxidized soyabean oil (ESO) has been used to toughen epoxy resin cured with an ambient temperature hardener. The ESO was prepolymerized before blending with epoxy resin to obtain modified networks having various concentrations of ESO. The modified networks were also made by blending the ESO with epoxy resin by a one‐stage process. All the modified networks were characterized for their thermal, flexural and impact properties, and compared to the parent epoxy network. The optimum properties were obtained at 20 parts per hundred grams of resin (phr) of ESO. The impact behaviour is explained in terms of morphology observed by scanning electron microscopy. © 2001 Society of Chemical Industry     

Preparation and evaluation of nano‐epoxy composite resins containing electrospun glass nanofibers

In this study, electrospun glass (structurally amorphous SiO₂) nanofibers (EGNFs) with diameters of ～ 400 nm were incorporated into epoxy resin for reinforcement and/or toughening purposes; the effects of silanization treatment (including different functional groups in silane molecules) and mass fraction of EGNFs on strength, stiffness, and toughness of the resulting nano‐epoxy composite resins were investigated. The experimental results revealed that EGNFs substantially outperformed conventional glass fibers (CGFs, with diameters of ～ 10 μm) in both tension and impact tests, and led to the same trend of improvements in strength, stiffness, and toughness at small mass fractions of 0.5 and 1%. The tensile strength, Young's modulus, work of fracture, and impact strength of the nano‐epoxy composite resins with EGNFs were improved by up to 40, 201, 67, and 363%, respectively. In general, the silanized EGNFs with epoxy end groups (G‐EGNFs) showed a higher degree of toughening effect, while the silanized EGNFs with amine end groups (A‐EGNFs) showed a higher degree of reinforcement effect. The study suggested that electrospun glass nanofibers could be used as reinforcement and/or toughening agent for making innovative nano‐epoxy composite resins, which would be further used for the development of high‐performance polymer composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical properties of conducting H‐type polysiloxane–polypyrrole graft copolymers and polytetrahydrofuran–polypyrrole block copolymers

The mechanical properties of block copolymers of polypyrrole and pyrrolyl‐ended azobis‐polytetrahydrofuran (TPPy) and graft copolymers of pyrrolyl‐ended H‐type polydimethylsiloxane (SPPy) were investigated and compared with those of polypyrrole (PPy). Conducting films were prepared electrochemically at a constant potential and doped with p‐toluene sulfonate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1663–1666, 2002     

Benzoxazine–epoxy copolymers: effect of molecular weight and crosslinking on thermal and viscoelastic properties

Bisphenol‐A‐based benzoxazine was copolymerized with epoxy and chain‐extended epoxies in order to study the effect of molecular weight on cured resin properties. Cure behaviour of the copolymers was studied using differential scanning calorimetry, which indicated a single exothermic curing peak at 248 °C. Dynamic mechanical thermal analysis was used to study the viscoelastic properties of the cured resins. A decrease in tan δ peak position and an increase in storage modulus and tan δ peak height were observed due to chain extension. Higher char yield was observed for the copolymer chain extended with tetrabromobisphenol‐A. Copyright © 2005 Society of Chemical Industry     

A comparative study on the preparation and characterization of aromatic and aliphatic bismaleimides‐modified polyurethane–epoxy interpenetrating polymer network matrices

Interpenetrating polymer networks of bismaleimide‐modified polyurethane–epoxy systems were prepared using the aliphatic and aromatic bismaleimides‐ and polyurethane‐modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the polyurethane‐crosslinked epoxy (PU–EP). The matrices developed were characterized by mechanical, thermal, electrical, and morphological studies. The results obtained from the mechanical studies indicate that the incorporation of polyurethane and bismaleimides into epoxy increased the tensile strength, flexural strength, and impact strength, according to their nature and percentage concentration. The results obtained from the thermal and electrical studies indicate that the incorporation of polyurethane into epoxy decreased the thermal properties (glass transition temperature, heat distortion temperature (HDT), thermal stability) and electrical properties (dielectric strength, volume and surface resistivity, and arc resistance). The incorporation of aromatic bismaleimide into the polyurethane‐modified epoxy system increased the glass transition temperature, thermal stability, and electrical properties. Decreased values of glass transition and HDT were obtained in the case of aliphatic bismaleimide‐modified polyurethane–epoxy system. Surface morphology of modified epoxy systems was studied using scanning electron microscopy, and it was found that the polyurethane‐modified epoxy systems exhibited heterogeneous morphology and bismaleimides‐modified epoxy systems showed a homogeneous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3592–3602, 2006     

Synthesis,characterization and surface properties of poly(lactic acid)–perfluoropolyether block copolymers

Laboratory‐scale synthesis and morphological and surface energy characterization of triblock A–B–A copolymers based on poly(lactic acid) (PLA; A segment) containing various block lengths of perfluoropolyether (PFPE; B segment) at 5 wt% PFPE content are reported. Incorporation of PFPE segments in PLA lowers significantly both the polar and dispersive components of total surface energy. Total surface energy is lowered from ca 35 to ca 17 mN m^?1 on copolymerization of PLA with 5 wt% PFPE. Thermal analysis data reveal that lower molecular weight PFPE segments lower significantly the glass transition, crystallization and melting temperatures of the PLA matrix. Although block length variation of the PFPE segment does not affect surface energies of copolymer films, smaller PFPE segments increase significantly the low‐temperature modulus as observed from dynamic mechanical analysis. Copyright © 2010 Society of Chemical Industry