Mechanical and tribological properties of epoxy modified by liquid carboxyl terminated poly(butadiene-co-acrylonitrile) rubber

Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin was modified using liquid carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) rubber. The liquid CTBN contents used ranged from 2.5 to 20 parts per hundred parts of resin (phr). Mechanical properties of the modified resins were evaluated and the microstructures of the fracture surfaces were examined using SEM technique. The changes in storage modulus and the glass transition temperature were also evaluated using dynamic mechanical analysis (DMA). The tribological tests were performed using a ball-on-disc tribometer. The worn surfaces and the ball counter-mates after tribological tests were investigated using optical microscope technique. The results revealed the influence of liquid CTBN content on mechanical and tribological properties, and also microstructure of the modified epoxy resins. Impact resistance increased whereas the storage modulus and the hardness decreased when the CTBN rubber was introduced to the epoxy network. The coefficient of friction of the CTBN-modified epoxy was lower than that of the neat epoxy. The CTBN content of lower than 10 phr was recommended for improving the wear resistance of epoxy resin. Changes in tribological properties of the CTBN-modified epoxy correspond well to those in mechanical changes, especially the toughness properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Graft copolymers with poly(ethylene oxide) segments

Graft copolymers containing poly(ethylene oxide) as side chains attached to the backbone have attracted significant interest because of their unique properties. They have expanded a class of materials important for science and biomedicine. This review article describes a variety of synthetic procedures, i.e. directly by the macromonomer method or by the ‘grafting from’ technique as well as indirect routes via a polymeric precursor. The uses of these graft copolymers in numerous applications are presented to show their versatile nature and their potential. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of anionic graft copolymers containing poly(ethylene oxide) grafts

Graft copolymers containing poly(ethylene oxide) side chain attached to maleic anhydride‐alt‐vinyl methyl ether (MA‐VME) copolymer were prepared by coupling MA‐VME and poly(ethylene glycol) monomethyl ether (MPEG) by esterification in DMF at 90°C. MPEG and dodecyl alcohol (DA) were grafted onto MA‐VME copolymer in o‐xylene at 140°C in the presence of p‐toluene sulfonic acid as catalyst. The molecular weights of MPEG were found to influence the rate of the grafting reaction and the final degree of conversion. The graft copolymers were characterized by IR, GPC, and ¹H‐NMR. DSC was used to examine thermal properties of the graft copolymers. The analysis indicates that grafts have phase‐separated morphology with the backbone and the MPEG grafts forming separate phases. The properties in aqueous solutions of these grafts were studied with respect to aggregation behavior and viscometric properties. In aqueous solution, the polymers exhibited polyelectrolyte behavior (i.e., a dramatic increase of the viscosity upon neutralization). Graft copolymers with DA have lower viscosities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1138–1148, 2002     

Mechanical properties of epoxy resins reinforced with synthetic boehmite (AlOOH) nanosheets

In this article, sheet boehmite (AlOOH), which was synthesized via a facile and environmental friendly method, was used as reinforcing agent to toughen Bisphenol A epoxy resin. The result of X–ray Diffraction (XRD) and IR spectrum indicated that the as–synthesized product was pure crystalline and high purity AlOOH. The effects of sheet AlOOH on the mechanical properties of AlOOH/epoxy nanocomposites were investigated. The results indicated that the introduction of AlOOH significantly improved the mechanical properties of epoxy resin. Compared with neat epoxy resin, the tensile strength and the fracture toughness (K_IC) of the AlOOH/epoxy nanocomposites filled with 4 wt % AlOOH increased by 24.2% and 28.7%, respectively, while the flexural strength increased from 40.92 to 50.00 MPa. From Scanning Electron Microscope (SEM), a phase‐separated morphology and plenty of cervices and river branches were observed in the fractured surfaces of composites. With the increase of sheet AlOOH content, river‐shaped cracks became more and more intensive. Overall, the addition of sheet AlOOH is shown as a promising method for mechanical properties enhancement of epoxy matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41409.     

A new SiC precursor with high ceramic yield: Synthesis and characterization of CHxMeSiH2-containing poly(methylsilane-carbosilane)

A new poly(methylsilane-carbosilane) (PMSCS) for silicon carbide precursor was prepared using Wurtz-type copolymerization of methyldichlorosilane (MeHSiCl₂), chloromethyldichloromethylsilane (ClCH₂MeSiCl₂), and (dichloromethyl)methylsilane (Cl₂CHMeSiH₂), with (chloromethyl)methylsilane (ClCH₂MeSiH₂) or trimethylchlorosilane (Me₃SiCl) as terminated reagent. The ceramic yield of PMSCS was markedly increased by introduction of Cl₂CHMeSiH₂ comonomer and capped with ClCH₂MeSiH₂. The H₂MeSiCH₂-capped PMSCS with CHMeSiH₂ structure unit in main chain produced SiC ceramic with 1.21 of C/Si atomic ratio in a ceramic yield of 78 wt % upon pyrolyzed at 1000 °C. The excellent pyrolytic properties, combining with its economical preparation, good storage stability in air, and favorable processabilty, make the CH_xMeSiH₂-containing PMSCS a new cost-effective SiC ceramic precursor. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47618.     

Biodegradable block copolymers with poly(ethylene oxide) and poly(glycolic acid‐valine) blocks

Biodegradable ABA triblock copolymers with poly(ethylene oxide) and poly(glycolic acid‐valine) blocks were synthesized via ring‐opening polymerization of cyclo(glycolic acid‐valine) using Ca‐alcoholates of hydroxytelechelic PEO as the initiator. The L‐valine residue racemized during copolymerization of cyclo(glycolic acid‐valine). The crystallization of the block copolymers decreases with decreasing PEO content in the triblock copolymers and with increasing length of the poly(glycolic acid‐valine) block. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2916–2919, 2002     

Six‐arm star‐shaped polymer with cyclophosphazene core and poly(ε‐caprolactone) arms as modifier of epoxy thermosets

A six‐arm star‐shaped poly(ε‐caprolactone) (s‐PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy‐teminated cyclophosphazene derivative and subsequent initiation of the ring‐opening polymerization of ε‐caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star‐shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy‐anhydride formulation by the addition of s‐PCL. The s‐PCL‐modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s‐PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star‐shaped modifier had little harmful effect on the thermal stability of the material. Thus s‐PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44384.     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystalline structure and mechanical properties of poly(ethylene terephthalate) filament embedded with nanosize clay particles

The properties of poly(ethylene terephthalate) (PET) filaments embedded with nanosize clay powder were evaluated. The moisture management function and thermal properties of the textile were found to be improved; however, the strength of the filament was lowered with a little increase in elongation. In situ analysis of the crystalline structure with small‐angle X‐ray scattering and wide‐angle X‐ray diffraction during the tensile testing showed an unstable change in intensities during the elongation. This phenomenon is related to the earlier rearrangement and breaks down the microstructure in local regions with an increase in strain. This is expected to be due to the low adhesion strength between the matrix and the embedded nanosize clay particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46321.     

Reaction‐induced phase separation and resulting thermomechanical and surface properties of epoxy resin/poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) blends cured with 4,4′‐diaminodiphenylsulfone

We investigated the phase separation, cure kinetics and thermomechanical properties of diglycidyl ether of bisphenol‐A/4,4′‐diaminodiphenylsulfone/poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer (TBCP) blends. Fourier transform infrared spectroscopy, differential scanning calorimetry, and atomic force microscopy revealed that the blends exhibited heterogeneous phase morphology in which the TBCP formed dispersed domains in epoxy matrix, due to reaction induced phase separation. A fraction of phase‐separated PEO phase underwent partial crystallization whereas another fraction formed interphases between the dispersed domains and epoxy matrix. Moreover, the dispersed PEO chains improved the compatibility and interfacial adhesion between the matrix and domains and, consequently, significantly improved the mechanical properties of epoxy resin. Furthermore, the thermal degradation studies and contact angle measurements disclosed that the dispersed domains were well protected by the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44406.     

Mechanical properties of poly(ethylene terephthalate) nanofiber three‐dimensional structure prepared by CO2 laser supersonic drawing

CO₂‐laser supersonic drawing method can produce bulky fluffy poly(ethylene terephthalate) (PET) nanofibers (NFs) by only irradiating CO₂‐laser to as‐spun PET fibers in the supersonic air jet. Cylindrical PET NF three‐dimensional structure (NF‐3DS) was fabricated by compression‐molding the obtained fluffy PET NFs using the cylindrical metal mold. NF‐3DS mold was completely disordered 3DS without a laminated structure because NFs were disorderly packed in the metal mold. The porosity of NF‐3DS can be changed by varying the filling weight of NF into the metal mold, and the highest porosity was 95.4%. The shape recovery ratio after 50% uniaxial compression in the height of NF‐3DS increases as the porosity increases, and NF‐3DS with a porosity of 95.4% had a shape recovery ratio of 98.1%. NF‐3DS with a desired shape will be produced if the metal mold can be prepared. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45763.     

Physico-mechanical properties of poly (vinyl alcohol), poly (vinyl alcohol)/boric acid,and poly (vinyl alcohol) nanocomposites incorporated with amino-functionalized and pristine halloysite nanotubes films

Eco-friendly poly(vinyl alcohol) (PVA), PVA/boric acid, PVA/halloysite nanotubes (HNTs), and PVA/amino-functionalized HNTs (APTES-HNTs) films were fabricated by a solution casting technique. The samples were characterized by fourier transform infrared, X-ray diffraction, differential scanning calorimetry, scanning electron microscope, and energy-dispersive spectroscopy. The characterization results proved the chemical and physical interactions between the PVA and different additives. The viscoelastic behavior of the films was evaluated by DMA and creep analysis. The storage modulus, loss factor, and both α_α and β_β transitions affected by APTES-HNTs as a potential filler to form effective cross-links. APTES-HNTs existence enhanced creep-recovery beyond expectations. Tensile and impact strength were measured to understand samples' mechanical stability. PVA/APTES-HNTs and PVA/boric acid showed more yield behavior after the elastic limit. Furthermore, the subsequent rupture and impact strength were increased significantly compared with neat PVA and PVA/HNTs. The viscoelastic and mechanical behaviors were linked to each other by the area under Tanδ curve and the work of rupture and impact strength, which their linear correlation coefficient is statistically significant at 95% confidence limits. It seems that the presence of APTES-HNTs provides new cross-links, which altered (improved) the physico-mechanical properties of PVA, offering a bionanocomposite suitable for further applications. From the literature, possible explanations are provided for these observations.     

Synthesis and characterization of poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate) triblock copolymers

Novel, monodispersed, and well‐defined ABA triblock copolymers [poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate)] were synthesized by oxyanionic polymerization with potassium tert‐butanoxide as the initiator. Gel permeation chromatography and ¹H‐NMR analysis showed that the obtained products were the desired copolymers with molecular weights close to calculated values. Because the poly(dimethylamino ethyl methacrylate) block was pH‐ and temperature‐sensitive, the aqueous solution behavior of the polymers was investigated with ¹H‐NMR and dynamic light scattering techniques at different pH values and at different temperatures. The micelle morphology was determined with transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Increase in the length of poly(ethylene oxide) blocks in amphiphilic copolymers facilitates their cellular uptake

Amphiphilic nonionic block copolymers induce different biological effects on living cells. In particular, the hydrophobic members of the Pluronics family suppress drug efflux systems in multidrug‐resistant cells, whereas hydrophilic Pluronics support cell viability. However, the relationship between the copolymer structure and its binding to cells is still unclear. Using a tritium‐labeling approach, we analyzed interactions of nine Pluronics and three diblock copolymers with human and murine cells in vitro and revealed that the binding efficiency of the copolymers increased in line with the length of their poly(ethylene oxide) (PEO) blocks. In contrast, partitioning of the same polymers into artificial lipid bilayers determined by Isothermal Titration Calorimetry (ITC) decreased with increasing length of the PEO block. The opposite influence of hydrophilic blocks on the copolymer affinity to living cells and artificial lipid bilayers implied the binding of long PEO blocks to the hydrophilic moieties of cellular membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45492.     

Preparation and characterization of magnetic nanofibers with iron oxide nanoparticles and poly(ethylene terephthalate)

Iron oxide nanoparticle/Poly(ethylene terephthalate) (PET) nanowebs were obtained by electrospinning. To achieve superparamagnetic properties, iron oxide nanoparticles with diameters below 25 nm were used. Diameter distribution of iron oxide nanoparticles was measured by a particle size analyzer. Iron oxide nanoparticles were added into 16 wt % PET solution in the ratio of 5, 10, and 15 wt % to PET. The morphology of iron oxide nanoparticle/PET nanowebs was observed using field emission-scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The nanofiber diameter increased as increasing iron oxide nanoparticle concentration. The superparamagnetic behavior of iron oxide nanoparticle/PET nanofiber was confirmed using superconducting quantum interference device (SQUID). The degree of crystallinity of iron oxide nanoparticle/PET nanowebs was calculated from a differential scanning calorimeter (DSC) results. The change of flexural rigidity and tensile properties of electrospun iron oxide nanoparticle/PET nanowebs with the external magnetic field were examined ISO 9073-7 testing method, universal testing machine and an appropriate magnet. Also, the elastic modulus of iron oxide nanoparticle/PET nanofiber was measured using nanoindentation. With applying magnetic field, the improvement in mechanical properties of field-responsive magnetic nanofibers and nanowebs was confirmed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of octadecane/polyurea nanocapsule‐embedded poly(ethylene oxide) nanofibers

This article describes the preparation and characterization of latent heat storage poly(ethylene oxide) nanofibers (LHS‐PEO nanofibers) with octadecane/polyurea (PCM/PU) nanocapsules. PCM/PU nanocapsules were prepared by interfacial polycondensation from toluene 2,4‐diisocyanate and ethylene diamine in a resin‐fortified emulsion system. LHS‐PEO nanofibers were prepared using an electrospinning procedure with varying PCM/PU nanocapsules content, i.e., from 0 to 8 wt %. The PCM/PU nanocapsules were polydisperse with an average diameter of 200 nm. The melting and freezing temperatures were determined as 23.7 and 28.2°C, respectively, and the corresponding latent heats were determined as 123.4 and 124.1 kJ kg^?1, respectively. The encapsulation efficiency of the PCM/PU nanocapsules was 78.1%. The latent heat capacity of the LHS‐PEO nanofibers increased as the PCM/PU nanocapsules content increased. Defects, such as holes and disconnection of the nanofibers, were observed, particularly inside the LHS‐PEO nanofibers. For packaging applications, mats were fabricated from the nanocapsules‐embedded nanofibers with varying nanocapsule content and the mats’ surface temperatures were monitored with a thermal imaging camera. The results proved the feasibility of using the LHS‐PEO nanofibers for thermal energy storage and functional packaging materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42539.     

Modification of epoxy–anhydride thermosets with a hyperbranched poly(ester amide). II. Thermal,dynamic mechanical,and dielectric properties and thermal reworkability

An epoxy–anhydride formulation used for the coating electrical devices was modified with a commercially available hyperbranched poly(ester amide), Hybrane S2200, to improve the thermal degradability of the resulting thermoset and, thus, facilitate the recovery of substrate materials after the service life of the component. The thermomechanical, mechanical, and dielectric properties and thermal degradability were studied and interpreted in terms of the composition and network structure of the cured thermosets. Although the crosslinking density was significantly reduced with the incorporation of S2200, the glass transition temperature of the fully cured material (T_g∞) of the modified thermoset was hardly affected because of the enhancement of H‐bonding interactions in the presence of S2200. Despite the different network structures, the combined dielectric and dynamic mechanical analysis revealed that the relaxation dynamics of both networks were very similar. In terms of application, improvements in the dielectric and mechanical properties were observed. The incorporation of S2200 accelerated the thermal decomposition of the material and, thus, facilitated the recovery of the valuable parts from the substrate at the end of the service life of the apparatus. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Toughening of poly(lactic acid) with the renewable bioplastic poly(trimethylene malonate)

The aim of this work was to enhance poly(lactic acid)'s (PLA) flexibility and ductility by blending it with another bioplastic. Poly(trimethylene malonate) (PTM), developed as part of this study, was synthesized from 1,3‐propane diol and malonic acid via melt polycondensation. Blend films of PLA and PTM were prepared by solvent casting from chloroform. Differential scanning calorimetry and thermogravimetric analysis were used to show shifted phase transitions and a single glass‐transition temperature, indicating miscibility of PTM in the blend films. Morphology and mechanical characterizations of the PLA/PTM blend films were performed by atomic force microscopy using a quantitative nanomechanical property mapping mode, tensile testing, and scanning electron microscopy. Miscible blends exhibited Young's modulus and elongation at break values that can significantly extend the usefulness of PLA in commercial applications. The blending of PTM with PLA resulted in films with a 27‐fold increase in toughness compared with neat PLA film. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40888.     

Micellization of pH‐sensitive poly(butadiene)‐block‐poly(2 vinylpyridine)‐block‐poly(ethylene oxide) triblock copolymers: Complex formation with anionic surfactants

The micellization of three tailor‐made triblock copolymers, such as PB₁₀₀–P2VP₁₀₀–PEO₁₀₄, PB₁₈₅–P2VP₁₀₈–PEO₁₅₄, and PB₃₇–P2VP₁₁₅–PEO₂₄₁, having similar total molecular weights and constant poly(2‐vinylpyridine) (P2VP) sequence lengths, was investigated as a function of pH and sodium dodecyl sulfate (SDS) concentration. At pH 7 the formation of intermicellar aggregates was observed, especially for copolymers of low poly(ethylene oxide) (PEO) content. A pH decrease from 7 to 3 leads to a particle size increase due to the electrostatic repulsion of the protonated P2VP chains. The influence of the PEO sequence length was also observed for zeta potential values. At pH 3, in the absence of SDS, core–shell–corona micelles are formed whereas in the presence of small amount of SDS (degree of neutralization DN = 0%–50%), a complex is formed between SDS and the protonated P2VP which leads to the shrinkage of the shell and thus to a decrease of the micellar sizes. For higher DN values, the micellar sizes increase due to the formation of large agglomerates and a transition occurs from a monomodal to a bimodal size distribution. Furthermore, it turned out that secondary aggregation, such as intermicellar aggregation, can completely be avoided if the degree of polymerization (DPn) of the water‐soluble block is significantly higher than the DPn of the water‐insoluble sequence. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45313.