Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Impact behavior of sawdust/recycled–PP composites

The instrumented Izod and Charpy tests were performed on the sawdust–polypropylene (PP) composites to study the nature of impact resistance in the thermoplastic wood composites. The notched Izod strength was found to increase with filler content in composites containing the Maleic–anhydride–grafted PP (MAPP) additive. The Izod strength even exceeds that of the neat matrix resin at higher filler contents, indicating a methodology for applying the recycled PP and also for reinforcing the thermoplastics with wood powders. While the static tensile results show evidences for the reinforcing role of the wood filler, a fracture mechanics characterization through the Charpy impact tests effects of MAPP under the impact loading rates. The choice of MAPP as the additive was discussed accordingly for application of the sort of materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1420–1428, 2001     

Synthesis and characterization of functionalized MWCNTs/PMMA composites: device fabrication for RH sensing

ABSTRACT

Functionalization of multiwalled carbon nanotubes (MWCNTs) with amine group using 4,4′-diaminodiphenyl sulfone (DDS) is achieved after carboxylation of pure MWCNTs (p-MWCNTs). p-MWCNTs, a-MWCNTs (acid functional MWCNTs) and f-MWCNTs (amine functional MWCNTs) were used to fabricate their nanocomposite with PMMA. A comparative study of the humidity characteristics of p-MWCNTs/PMMA, a-MWCNTs/PMMA and f-MWCNTs/PMMA-based capacitive humidity sensors was carried. f-MWCNTs/PMMA-based capacitive humidity sensor shows low hysteresis loss (5%), good response recovery behavior and highest sensitivity (S ~ 9736%) among all the studied composites. The maximum capacitance drift under different relative humidity was 1%RH.     

Thermal and thermomechanical behavior of amino functionalized and metal decorated MWCNTs/PMMA nanocomposite films

The homogeneous nanocomposites (NC) films of amino modified and metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) were synthesized through in‐situ free radical polymerization. Silver metal nanohybrids (Ag/MWCNTs) were prepared by two strategies, that is, reduction of metal salt in presence of sodium dodecyl sulfate and in‐situ growth from AgNO₃ aqueous solution. The amino functionalization by ball milling enhanced the dispersion of MWCNT in monomer and produced a new class of radiation resistant NC. These synthesized films were characterized by FTIR, TGA, TEM, EDX, TC, DMA, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. Microscopic studies reflect the homogeneous mixing of amino functionalized and metal decorated MWCNTs in polymer matrix contributing in the enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of NC even at 0.25 wt% addition of modified nanofiller. The thermal stability of NC film at 0.25 wt% loading was increased around ≂50°C and the raise of thermo‐mechanical properties was observed up to 85% at 100°C in the presence of adsorbed surfactant. Thermal and thermomechanical behavior of pre and post UV/O₃ irradiated NC films has been compared with neat polymer. The results revealed that amino modified nanofiller embedded network in polymer matrix can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 35:1807–1817, 2014. © 2013 Society of Plastics Engineers     

Friction spot welding of PMMA with PMMA/silica and PMMA/silica-g-PMMA nanocomposites functionalized via ATRP

In the present study, the feasibility of Friction Spot Welding (FSpW) of a commercial-grade poly(methyl methacrylate) (PMMA) (PMMA GS) and PMMA 6N/functionalized silica (SiO₂) nanocomposites was investigated. The silica nanoparticles were functionalized via atom transfer radical polymerization (ATRP) with PMMA chains to achieve a uniform dispersion in the polymer matrix. The successful functionalization of silica nanoparticles with PMMA chains via ATRP was evaluated by ATR-FT-IR and TGA measurements. Rheological investigations of the silica nanocomposites showed a plateau of the storage modulus G′ at low frequencies (0.01–0.03 rad/s) as a result of elastic particle–particle interactions. Overlap friction spot welds consisting of PMMA GS and a 2 wt% SiO₂-g-PMMA nanocomposite were successfully prepared and compared to spot joints of PMMA GS welded with PMMA 6N and PMMA 6N/silica nanocomposite with 2 wt% unfunctionalized silica nanoparticles. Raman mappings of selected areas of cross-sectional plastographic specimens revealed an increased mixing behavior between the two polymer plates in the case of PMMA GS/2 wt% SiO₂-g-PMMA joints. Although the joints welded with PMMA 6N/silica nanocomposites showed a reduction of 22% in lap shear strength and 21% displacement at peak load compared with the neat PMMA spot welds, they can compete with other state-of-the-art PMMA welding techniques such as thermal bonding and ultrasonic welding, which indicates the potential of friction spot welding as an alternative fabrication technology for joining future nanocomposite engineering parts.     

Terminally functionalized polyethylenes as compatibilizers for wood–polyethylene composites

Isocyanate‐terminated polyethylenes (PE), PE‐MDI and PE‐PMDI, were synthesized by reacting polyethylene monoalcohol (PEA) with 4,4′‐methylenediphenyl diisocyanate (MDI) and polymeric methylene diphenyl diisocyanate (PMDI), respectively. Effects of PEA, PE–MDI, and PE–PMDI on the mechanical properties and water resistance of wood–PE composites were investigated. All three compatibilizers increased the strength of the wood–PE composites. Composites containing PE–MDI or PE–PMDI exhibited a higher modulus of rupture (MOR) than those with PEA. The addition of PE–MDI and PE–PMDI decreased the water uptake rate of the composites while PEA increased this rate. The superior compatibilization effects of PE–MDI and PE–PMDI were attributed to the formation of covalent bonding between isocyanate and wood. This covalent bonding was demonstrated by the FTIR spectra of the wood residues after a p‐xylene extraction. Scanning electron microscope (SEM) images revealed that isocyanate‐terminated PE samples improved the interfacial adhesion between wood and PE. POLYM. ENG. SCI., 46:108–113, 2006. © 2005 Society of Plastics Engineers     

High performance polyurethane composites with isocyanate‐functionalized carbon nanotubes: Improvements in tear strength and scratch hardness

A microwave‐assisted functionalization of carbon nanotubes (CNTs) with isocyanate groups allowed a reduction of functionalization time from 24 h to 30 min with no change in the degree of functionalization or in the nanotube characteristics. Polymer nanocomposites with enhanced mechanical properties were obtained because of the tailored interface by the covalent linkage between the surface‐modified multiwalled‐carbon nanotubes (MWCNTs) and an elastomeric polyurethane (PUE) matrix. The mechanical data revealed that the composite containing 0.25 wt % of MWCNT‐NCO showed an increase of 31% in tear strength and 28% in static toughness. A good adhesion between the matrix and individually dispersed nanotubes was observed in the scanning electron microscopy and transmission electron microscopy images. Nanoindentation and nanoscratch experiments were conducted to investigate the properties on the sub‐surface. An increase by a factor of 3 in the scratch hardness was observed for the composite with 0.50 wt % of MWCNT‐NCO with respect to the neat PUE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44394.     

Dual-curing behavior and scratch characteristics of hydroxyl functionalized urethane methacrylate oligomer for automotive clearcoats

UV–thermal dual-curable, hydroxyl- and methacrylate-functionalized urethane oligomers with different contents of unsaturated double bonds and hydroxyl groups have been synthesized and incorporated into automotive clearcoats to investigate their curing and scratch behaviors. Dynamic mechanical analyses (DMA) and FT-IR analyses were performed to observe the variation of the crosslinking networks that resulted from the chemical reactions by UV and thermal dual-curing operations with varying curing conditions, such as UV dose, thermal curing time, thermal curing temperature, and curing sequence. The scratch behaviors of dual-cured automotive clearcoats were analyzed via nano-scratch tests, accompanied with scratch images simultaneously visualized using scanning electron microscopy (SEM). The mechanical and chemical properties, such as impact resistance, pencil hardness, acid-etch resistance, and stone-chip resistance, of dual-curable clearcoats were also compared with those of UV mono-cure and 1 K thermal-cure clearcoats. The results clearly showed that the dual-curing process induced a considerably higher degree of crosslinking for the cured clearcoats prepared from the dual-curable oligomers, melamine crosslinkers, and photoinitiators. Their mechanical properties including scratch resistance were also noticeably improved via the UV–thermal curing sequence, which led to an increased conversion rate of double bonds compared with clearcoats produced using the thermal–UV curing sequence. The best conditions for high crosslinking density as well as high hardness and modulus were 2400 mJ/cm² at 150 °C for 10 min in the UV–thermal curing process. This result was corroborated from the reaction kinetics and surface images of the scratched clearcoats captured by SEM.     

Crystallization and melt behavior of magnesium hydroxide/polypropylene composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/polypropylene (PP) composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased crystallization temperatures of PP attributed to the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization because of the decreased regularity of the PP chain. For the Mg(OH)₂/PP composites, addition of Mg(OH)₂ increased the crystallization temperatures of PP attributed to a heterogeneous nucleation effect of Mg(OH)₂. Addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect of Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, but crystallization temperatures of PP were not influenced by the AA content, a phenomenon explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, the crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by the addition of FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3899–3908, 2004     

Internal friction behavior of carbon–carbon composites

The fundamental internal friction behavior of carbon–carbon composites is studied. Two internal friction mechanisms are proposed according to the special internal friction characteristics in carbon–carbon composites. A thermoelastic mechanism, which is independent of amplitude, mainly leads to the internal friction increase with increasing frequency. The other is a static hysteresis mechanism that internal friction depends on the amplitude but is independent of frequency. Moreover, it is very interesting that some abnormal internal friction phenomena can be observed. The variation characteristics of internal friction and dynamic modulus versus temperature in carbon–carbon composites are quite different from other materials. This special behavior may be a result of interfacial CTE effects, as well as the coordination effects of the individual response of the fibers, matrix and interface of carbon–carbon composites. Finally, the validity of internal friction analysis methods for densification process monitoring and non-destructive inspection of carbon–carbon composites is discussed for the first time. The results indicate that internal friction testing methods have great potential for monitoring process and inspecting components of carbon–carbon composites non-destructively.     

Blends of polyolefin/PMMA for improved scratch resistance,adhesion and compatibility

Functionalized poly(propylene-co-ethylene) (PPE) made via reactive extrusion dramatically improved the performance of their blends with poly(methyl methacrylate) (PMMA). Adhesion, compatibility, modulus, hardness and scratch resistance were all increased for blends with functional PPEs compared to non-modified PPE, greatly expanding the applications of polyolefins. Three types of functional PPEs including maleic anhydride grafted PPE (PPE-MA), hydroxyl group grafted PPE (PPE-OH) and secondary amine group grafted PPE (PPE-NHR) were melt blended with PMMA at different compositions and with PMMA of different molecular weights. Compatibility of each functional PPE with PMMA was compared by investigating the binary blends using mechanical (nano-indentation, nano-scratch and tensile tests), morphological (scanning electron microscopy with image analysis, particle size analysis) and adhesion tests. Compatibility of functional PPEs with PMMA is confirmed consistently from various tests and ranked in a decreasing order as follows: PPE-NHR > PPE-OH > PPE-MA > PPE. We also drastically improved the compatibility and adhesion between PPE and PMMA by blending a small amount of PMMA grafted PPE copolymer.     

Dynamic mechanical behavior of LCP fiber/glass fiber–reinforced LLDPE composites

Liquid crystalline polymer (LCP) fibers and glass fibers have been used to rein force linear low density polyethylene (LLDPE) by using an elastic melt extruder and the compression molding technique. The impact behavior of hybrid composites of different composition is compared and is explained on the basis of the volume frac tion of the fibers. Addition of glass fibers decreases the Izod impact strength LLDPE. The impact strength of the composites increases when glass fibers are placed by LCP fibers. Dynamic mechanical α and β relaxations are studied and effect of variation of fiber composition on these relaxations is reported in the tem perature range from −50 to 150°C at 1 Hz frequency, a relaxation shifts toward higher temperatures with addition of fibers in LLDPE. Addition of fibers increases the storage modulus of LLDPE.     

Flammability behavior of fiber–fiber hybrid fabrics and composites

The effect of heat flux levels on burning behavior and heat transmission properties of hybrid fabrics and composites has been investigated using cone calorimeter and heat transmission techniques. The hybrid fabric structures woven out of E‐glass (warp) and polyether ether ketone (PEEK) (weft) and E‐glass (warp) and polyester (weft) have been studied at high heat flux levels keeping in view the flame retardant requirements of structural composites. The performance of the glass–PEEK fabric even at high heat flux levels of 75 kW/m² was comparable with the performance of glass–polyester fabric evaluated at 50 kW/m². The results further demonstrate that glass–PEEK hybrid fabrics exhibit low peak heat release rate, low heat release rate, low heat of combustion, suggesting an excellent combination of materials and fall under the low‐risk category and are comparable with the performance of carbon fiber‐epoxy‐based systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Expansion of core–shell PS/PMMA particles

Structured micrometric polystyrene/poly(methyl methacrylate) particles were obtained by suspension polymerization and their expansion behavior was investigated using n‐pentane as blowing agent. The expanded particles presented two distinct microstructures with an outer region (PMMA‐rich shell) composed by cells of about 10 µm while the center of the particle (PS‐rich core) had much larger cells (50–100 μm). The core–shell particles did not expand at 100°C meaning that the PMMA shell hindered the expansion of the particles. Maximum expansion was dependent on the PMMA concentration and also on the heating temperature and the increase in the PMMA molar mass led to a delay in the onset of the process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4521–4527, 2013     

Mechanical behavior at nanoscale of chitosan‐coated PE surface

Chitosan coating of polyethylene (PE) was proposed as a new procedure to improve its biocompatibility and surface properties. The functionalization of the PE film surface by covalent bonding of chitosan coating and its effect on the surface mechanical properties, as surface elasticity, stiffness, and adhesion (that are important in different biological processes) were investigated by nano‐indentation, scratch, and atomic force microscopy. It has been established that chitosan grafting onto corona functionalized PE surface using various coupling agents significantly improves the surface hardness and elastic modulus although they decrease in depth of the layer. Compared to the neat PE substrate, the chitosan coated samples show significant improved friction properties and tear resistance. The surface roughness features correlate with the micro‐mechanical parameters. Therefore, the covalent immobilization of the chitosan onto PE leads to a stable coating with better mechanical performance being recommended as a promising material for medical applications and food packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42344.     

Indentation Fracture Mechanics for Toughness Assessment of PMMA/SiO2 Nanocomposites

Summary: Based on the results from agglomerate‐free PMMA nanocomposites with 10 and 20 wt.‐% spherical SiO₂ nanoparticles, it has been shown that indentation fracture mechanics is a straightforward, powerful, cost‐effective and time‐effective tool for analyzing the fracture resistance of novel polymer materials, such as brittle nanostructured polymer‐ceramic hybrids. In contrast to pure PMMA, the R‐curve effect, i.e., the enhancement in crack resistance as a function of crack size, was not observed in the nanocomposites investigated. Fracture toughness was found to depend on the SiO₂ nanoparticle content, and the maximum value was observed at 10 wt.‐%. A significant reduction in fracture toughness occurred at 20 wt.‐% SiO₂ nanoparticles, which is associated with a percolation of the bound layers (interfacial layers) around the SiO₂ particles. From DSC data, the thickness of the interfacial polymer layer was estimated to be about 9 nm.

Hardness, elastic modulus and fracture toughness of PMMA/SiO₂ composites as a function of nanoparticle fraction.     

Stress–strain behavior of SAN/glass bead composites above the glass transition temperature

Relaxation and stress–strain behavior of SAN–glass bead composites are studied above the glass transition temperature. The strain imposed on the polymeric matrix of the composite is defined as ?_p = ?_c/(1 ? ?^?). Stress relaxation data for the filled polymer which is independent of strain can be calculated by multiplying the relaxation modulus (at a certain strain) by (1 + ?_p). Stress–strain curves at constant strain rate and for different concentrations of the filler can be shifted to form a master curve independent of filler content if the tensile stress is plotted versus ?^p. The relaxation modulus increases with increasing the filler concentration and can be predicted by a modified Kerner equation at 110°C.     

PMMA composites of single‐walled carbon nanotubes‐graft‐PMMA

To facilitate the dispersion of single‐walled carbon nanotubes (SWCNT) into poly(methyl methacrylate) (PMMA), SWCNT were functionalized with a RAFT chain transfer agent, and PMMA was grafted from the SWCNT by reversible addition–fragmentation transfer (RAFT) polymerization to give SWCNT‐g‐PMMA containing 6 wt % PMMA. SWCNT‐g‐PMMA in the form of small bundles was dispersed into PMMA matrices. The SWCNT‐g‐PMMA filler increased the glass transition temperature (T_g) of the composite when the matrix molecular weight M_n was less than the graft molecular weight, but not when the matrix M_n was equal to or greater than the graft M_n. The threshold of electrical conductivity of the composites as a function of weight percent SWCNT increased from 0.2% when matrix M_n was less than graft M_n to about 1% when matrix M_n was greater than graft M_n. Dynamic mechanical analyses of the composites having graft M_n less than or equal to matrix M_n showed broader rubbery plateaus with increased SWCNT content but no significant differences between samples with different grafted PMMAs. The results indicate that lower M_n matrix wets the SWCNT‐g‐PMMA whereas higher M_n matrix does not wet the SWCNT‐g‐PMMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39884.