A novel approach to interpenetrating networks of epoxy resin and polydimethylsiloxane

A novel methodology for preparing interpenetrating polymer networks (IPNs) between an epoxy resin, diglycidylether of bisphenol A (DGEBA) and polydimethylsiloxane (PDMS) was proposed. The vinyl‐terminated PDMS (vinyl‐PDMS) was partially crosslinked with hydrogen‐containing PDMS (H‐PDMS) and was mixed with DGEBA, modified silica (m‐silica), and a methyl tetrahydrophtalic anhydride (MTHPA) curing agent. Subsequently, the curing reactions of the DGEBA/m‐silica and PDMS were allowed to occur separately and simultaneously leading to an IPN. The m‐silica played a double‐fold role: Cocuring with DGEBA and H‐bonding with the oxygen atoms on the PDMS segments, and thus acted as a compatibilizer between DGEBA and PDMS and promoted the generation of the IPN structure. The resulted partially miscible structure was characterized through the dispersion of silica particles and the glass transition behavior of the samples. The mechanical properties of the IPNs were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of nanocellulose reinforced full‐interpenetrating polymer network based on poly(vinyl alcohol) and polyacrylamide (both crosslinked) composite films

An interpenetrating polymer network (IPN) is a novel blend of two polymers at least one of which is synthesized or crosslinked in the immediate presence of the other so that there is the least possibility of any gross phase separation. Full‐IPNs, prepared from poly(vinyl alcohol) and polyacrylamide, have shown superior performances over the conventional individual polymers. The ranges of applications have grown rapidly for such class of materials. Cellulose nanoparticles extracted from sugarcane bagasse in‐house are used to reinforce this PVA/PAAm (80:20) full‐IPN in different proportions during the synthesis of IPN. The characteristics of this new series of IPN composite materials have been evaluated by Fourier transform infrared spectroscopic analysis, mechanical, thermal (thermogravimetric analysis and differential scanning calorimetry), and scanning electron microscopy techniques. A loading of 5 wt% of nanocellulose lead to the highest tensile strength amongst the different IPN composite films. Although the non‐reinforced full‐IPN and the various reinforced composites with nanocelluloses are almost identical in their thermal stability, they prove to be much superior compared to the neat polymers. POLYM. COMPOS., 38:1720–1731, 2017. © 2015 Society of Plastics Engineers     

Preparation and properties of poly(methylmethacrylate)-silica hybrid materials incorporating reactive silica nanoparticles

In this study, poly(methylmethacrylate) (PMMA)-based hybrid materials were prepared from reactive silica nanoparticles. These nanoparticles were obtained by the reaction of 2-(methacryloyloxy)ethyl isocyanate with colloidal silica dispersed in ethyl acetate, and they were copolymerized in various ratios with methyl methacrylate. Dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and visible spectrometry were performed to evaluate the physical properties of the resulting hybrid materials. The PMMA-silica hybrid copolymers maintained high transparency, and their storage elastic modulus and surface hardness increased with increasing silica content. Moreover, in comparison with PMMA, the hybrid copolymers had greater heat resistance and lower volume contraction.     

Preparation and characterization of epoxidate poly(1,2‐butadiene)–toughened diglycidyl ether bisphenol‐A epoxy composites

By the oxidation of liquid poly(1,2‐butadiene) (LPB) with H₂O₂/HCOOH, epoxidate poly(1,2‐butadiene) (ELPB) was obtained as a toughening agent to prepare diglycidyl ether bisphenol‐A (DGEBA) epoxy composites by using V115 polyamide(PA) as a cross‐linking agent. DGEBA, ELPB, and the composites were effectively cured by PA at 100°C for 2 h followed by postcuring at 170°C for 1 h. Thermal gravimetric analysis results in air and nitrogen atmosphere showed that the thermal stability of composites could be improved by the addition of ELPB. Compared with DGEBA/PA, the composites exhibited a decrease in strength at yield but an increase in strain at break with the increase in ELPB amount. The composite with 10% ELPB exhibited both thermal stability and tenacity superior to those of DGEBA/PA and composites with 5 and 20% ELPB, respectively. The improvements in thermal and mechanical properties of composites depended on the formation of Inter Penetrating Networks (IPN) among DGEBA/PA/ELPB and their distributions in the matrix. At an appropriate ELPB amount, the IPN, mostly made of DGEBA/PA/ELPB, may be distributed more evenly in the matrix; less ELPB resulted in the formation of IPN mainly made of DGEBA/PA; excessive addition of ELPB resulted in the local aggregation of ELPB/PA and phase separations. The toughening mechanism was changed from chemically forming IPN made of DGEBA/PA/ELPB to physically reinforcing DGEBA/PA by ELPB/PA with the increase in ELPB addition. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Damping analysis of polyurethane/polyacrylate interpenetrating polymer network composites filled with graphite particles

The graphite‐filled polyurethane/poly(methyl methacrylate‐butyl methacrylate) (PU/P(MMA‐BMA)) semi‐interpenetrating polymer networks (IPNs) were synthesized by sequential method. The influences of graphite particle content and size on the 60/40 PU/P(MMA‐BMA) IPNs were studied. The damping properties of IPN composites were evaluated by dynamic mechanical thermal analysis (DMA) and cantilever beam resonance methods. The mechanical performances were investigated using tensile and hardness devices. DMA results revealed that the incorporation of graphite particles improved damping properties of IPNs significantly. The 5% graphite‐filled IPN composite exhibited the widest temperature range and the highest loss factor (tan δ) when the test frequency was 1 Hz. As to the damping properties covering a wide frequency range from 1 to 3,000 Hz, the addition of graphite particles broadened the damping frequency range (Δf, where tan δ is above 0.3) and increased the tan δ value of IPNs. Among them, the composite with 7.5% graphite showed the best damping capacity. And the hardness and the tensile strength of IPN composites were also improved significantly. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

The stability of poly(ether urethane)/polydimethylsiloxane interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) are a special type of polymer blend consisting of two polymer networks synthesized and/or cross-linked independently within each other. One potential approach for the preparation of composite materials from polymers having desirable physical characteristics obtained by modifying their surfaces with physiologically acceptable polymers involves IPN technology. An IPN based on a poly(ether urethane) and polydimethylsiloxane has been synthesized and charaterized using optical microscopy, dynamic mechanical analysis, and scanning electron microscopy. The stability of poly(ether urethane)/polydimethylsiloxane composites were studied in hydroxyl radical aqueous solutions over 30 weeks. The data suggest that these composites have good potential for biomedical applications. © 1995 John Wiley & Sons, Inc.     

Chemorheology on simultaneous IPN formation of epoxy resin and unsaturated polyester

Study of the simultaneous interpenetrating polymer network (IPN) between diglycidyl ether of bisphenol-A (DGEBA) and unsaturated polyester (UP) was carried out at ambient temperature. Fourier transform infrared (FTIR) spectroscopy was employed to investigate the intermolecular H-bonding and functional group changes. Viscosity changes due to H-bonding and crosslinking were examined with a Brookfield viscometer. Gelation time was measured by a Techne gelation timer. Complexation between Co(II) (the promoter for UP cure) and diamine (the curing agent for DGEBA) was detected with UV-visible spectrometer. Experimental evidence revealed that intermolecular interactions were observed in systems such as DGEBA/UP, DGEBA/diamine, Co(II)/diamine, DGEBA/uncured UP, and UP/uncured DGEBA. All such interactions had measurable effects on the curing behaviors for both networks, as were indicated by the viscosity changes and gelation time. The IPNs thus obtained were further characterized with rheometric dynamic spectroscopy (RDS) and differential scanning calorimetry (DSC). Partial compatibility between UP and DGEBA networks was evidenced from a main damping peak with a shoulder near glass transition temperature (T_g) for lower UP content; while at higher UP content, only a main damping peak near T_g was observed. DSC revealed a broad glass transition for all IPNs. The resultant IPN materials were all transparent. © 1992 John Wiley & Sons, Inc.     

Effect of the structure of silane‐coupling agent on dynamic mechanical properties of dental resin‐nanocomposites

This work was aimed at the study by dynamic mechanical analysis (DMA) of dental composites consisted of a Bis‐GMA/TEGDMA (50/50 wt/wt) matrix and silica nanoparticles (Aerosil OX50) as filler, silanized with various silanes. The silanes used were 3‐[(1,3(2)‐dimethacryloyloxypropyl)‐2 (3)‐oxycarbonylamido] propyltriethoxy‐silane (UDMS), 3‐methacryloxypropyl‐trimethoxysilane (MPS), octyltrimethoxysilane (OTMS), blends of UDMS/OTMS (50/50 wt/wt), or MPS/OTMS (50/50 wt/wt). The total amount of silane was kept constant at 10% by weight fraction relative to the filler weight. The silanized nanoparticles were mixed with the dimethacrylate matrix (60% filler by weight fraction). The composites were light cured and tested by DMA for the determination of storage modulus (E′), loss modulus (E″), tangent delta (tan δ), and glass transition temperature (T_g). Measurements were performed in samples immediately after curing and samples stored in water at 37°C for 1, 7, 30, or 120 days. OTMS‐composite in which OTMS does not form covalent bond with the dimethacrylate matrix showed lower elastic modulus both in dry and wet conditions. The ability of bifunctional UDMS for crosslinking was found not to increase the elastic behavior of the composite, as it was expected, compared with that of MPS‐composite, because of the high amount of the silane used. After immersion in water the elastic modulus of OTMS‐composite remained constant, while that of the other composites increased after 1 day and then remained constant up to 120 days. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tensile creep behaviour of polymethylpentene–silica nanocomposites

For the first time, poly(4‐methyl‐1‐pentene) (PMP) nanocomposites were prepared by melt compounding 2 vol% of fumed silica nanoparticles, in order to study the role of the nanofiller surface area and functionalization on the tensile mechanical response of the material, with particular focus on its creep behaviour. The high optical transparency of the polymer matrix was substantially preserved in the nanocomposites, while the mechanical properties (in particular the creep stability) were improved. Dynamic mechanical thermal analysis showed an improvement of the storage modulus, more evident above the glass transition temperature of the polymer matrix. Uniaxial tensile tests evidenced that the elastic modulus of the material was positively affected by the presence of silica nanoparticles, even if a slight reduction of the strain at break was detected. The reduction of the tensile creep compliance was proportional to the surface area of the nanofiller, being more evident at high stresses and elevated temperatures. Findley's law furnished a satisfactory fitting of the creep behaviour of the composites, even at high temperatures. It clearly emerges that the incorporation of fumed silica nanoparticles in PMP can be an effective way to overcome the problem of the poor creep stability of polyolefins, especially at high temperatures and high stresses. Moreover the possibility of retaining the original transparency of the material is fundamental for the production of completely transparent PMP components. Copyright © 2010 Society of Chemical Industry     

Preparation and physical properties of transparent organic–inorganic nanohybrid materials based on urethane dimethacrylate

The aim of this study was to prepare transparent organic–inorganic nanohybrid materials with improved physical properties in comparison with the matrix polymer. Polymerizable silica nanoparticles were synthesized via the reaction of silanol groups on the surface of silica nanoparticles (particle diameter ≈ 12 nm) with isocyanate groups of 2‐(methacryloyloxy)ethyl isocyanate (MOI) in ethyl acetate. In addition, the matrix monomer, urethane dimethacrylate, was prepared by the reaction of an MOI isocyanate group with the hydroxyl group of 2‐hydroxyethyl methacrylate, and novel organic–inorganic nanohybrid materials were obtained at various silica contents with bulk polymerization. The surface treatment of the silica nanoparticles and preparation of the matrix monomer were carried out in a one‐pot reaction. The prepared hybrid materials retained high transparency, and the elastic modulus and surface hardness improved with increasing silica content. Moreover, the strength of the material containing 20 wt % silica was up to 30 MPa higher than that of the matrix polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and thermo‐mechanical properties of heat‐resistant epoxy/silica hybrid materials

Diglycidyl ether of bisphenol‐A (DGEBA) based epoxy/silica hybrid materials filled with various amounts of 3‐glycidoxypropyltrimethoxysilane (GPTMS) and silica nanoparticles were prepared, using 4,4′‐diaminodiphenyl sulfone (DDS) as curing agent. The obtained hybrid materials were analyzed by means of Fourier‐transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated that the introduction of GPTMS and silica nanoparticles had synergistic effect. The addition of GPTMS not only ameliorated the compatibility between silica and the epoxy matrix but also increased the crosslinking density of the epoxy system; meanwhile the nano‐silica further reinforced the inorganic network of the hybrid system. Consequently, the hybrid materials showed much improved heat‐resistant properties. The storage modulus of the hybrid systems showed no obvious decrement in the glass transition region and kept at a high value even in the temperature region up to 300°C. The integral thermal stability of the resulting hybrid materials was also improved compared with the corresponding pure epoxy resin. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Effect of fumed silica nanoparticles on glass fiber filled thermotropic liquid crystalline polymer composites

Glass fiber filled thermotropic liquid crystalline polymer (gLCP)/silica composites were prepared by melt compounding. The total torque of the gLCP/silica composites decreased and the melt flow index increased with increasing silica content, which indicates that the fumed silica nanoparticles act as good processing aids and enhance the processing behavior of gLCP/silica composites. The rheological properties of the gLCP/silica composites were significantly dependent on the silica content. The complex viscosity and storage modulus (G′) of the gLCP/silica composites decreased with increasing silica content. This was attributed to the ability of the silica nanoparticles to break the glass fiber–glass fiber interactions in the gLCPs. The storage modulus and loss modulus (G″) of the gLCP/silica composites increased with increasing frequency, and the increment was more significant at low frequency. Incorporation of a small quantity of silica nanoparticles improved the thermal stability and mechanical properties of gLCP/silica composites. However, at high silica nanoparticle content the mechanical properties of gLCP/silica composites decreased because of the aggregation of silica nanoparticles. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis,characterization, and properties of interpenetrating polymer networks containing functionalized latex particles

Three-component interpenetrating polymer networks (IPNs) comprising polyurethane (PUR), poly(n-butyl methacrylate) (PBMA), and polystyrene (PS) latex particles were prepared in a modified one-shot synthesis. The hydroxy-functionlized and unmodified polystyrene latex particles were synthesized via a seeded emulsion polymerization. The incorporation of hydroxyethyl methacrylate into the latex particles was confirmed via diffuse reflectance infrared analysis and modulated-temperature differential scanning calorimetry. The IPNs were characterized by dynamic mechanical thermal analysis, tensile testing, hardness measurements, and transmission electron microscopy. The three-component materials exhibited higher values for the Young's modulus and the Shore A hardness and for the dynamic storage modulus in the higher temperature range from 80 to 140°C than did the PUR/PBMA IPN alone. The latex particles with the hydroxyl functionality exhibited a better miscibility with the microheterogeneous PUR/PBMA IPN than did unfunctionalized PS latex particles, and, therefore, resulted in materials with better damping properties in the temperature range between 80 and 140°C. Transmission electron micrographs confirmed the imporved miscibility of the functionalized latex particles. The latex particles were not, however, dispersed on an individual level but formed agglomerates of between 2 and 20 μm. © 1996 John Wiley & Sons, Inc.     

The effect of the interface structure of different surface‐modified nano‐SiO2 on the mechanical properties of nylon 66 composites

The nylon 66‐based nanocomposites containing two different surface‐modified and unmodified SiO₂ nanoparticles were prepared by melt compounding. The interface structure formed in different composite system and their influences on material mechanical properties were investigated. The results indicated that the interfacial interactions differed between composite systems. The strong interfacial adhesion helped to increase tensile strength and elastic modulus of composites; whereas, the presence of modification layer in silica surface could enhance the toughness of composites, but the improvement of final material toughness was also correlated with the density of the adhered nylon 66 chains around silica nanoparticles. In addition, the results also indicated that the addition of surface‐modified silica nanoparticles has a distinct influence on the nonisothermal crystallization behavior of the nylon 66 matrix when compared with the unmodified silica nanoparticle. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Curing behaviour of compatible interpenetrating polymer networks based on epoxy and methacrylated epoxy

Compatible interpenetrating polymer networks (IPNs) based on diglycidyl ether of bisphenol A (DGEBA) and methacrylated diglycidyl ether of bisphenol A (MADGEBA) in weight ratios of 100/0, 75/25, 50/50, 25/75 and 0/100 were blended and cured simultaneously by using dicumyl peroxide (DICUP) and hexahydrophthalic anhydride (HHPA) as curing agents. Fourier transform infrared spectroscopy (FTIR) was employed to investigate the intermolecular interactions and functional group changes. Viscosity increases during crosslinking were examined with a Brookfield viscometer. Curing exothermic peaks were studied with differential scanning calorimetry (DSC). The gel fractions of various IPN compositions were measured with a Soxhlet extractor. Samples thus prepared were checked for their compatibility by measuring glass transitions with DSC and damping peaks with rheometric dynamic spectroscopy (RDS). Experimental results revealed that good compatibility between components induced a network interlock, which subsequently resulted in incomplete cure of the IPN materials. ©1997 SCI     

Preparation and properties of polyurethane‐modified epoxy cured in different simulated gravity environments

Great attention has been paid to the composites with interpenetrating polymer networks (IPNs) because of their special performance. However, the influence of sedimentation and convection from different gravity environments on the formation of IPNs and the properties of IPNs blends has received little attention. To understand their influence, environments with different gravity accelerations of 0g, 1g, and 2g were simulated with a superconducting magnet, and tests, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), coefficient of thermal expansion (CTE), scanning electron microscopy, and three‐point bending, of the IPNs blends cured in different gravity environments were conducted and analyzed. Fourier transform infrared spectroscopy, DSC, and DMA proved the formation of IPNs during the reaction between the polyurethane prepolymer (PUP) and epoxy resin (E51). The curves of DSC also certified the differences in the curing degree between the different parts along the direction of gravity of a sample. With the increase of mass fraction of PUP, the change trends of the storage modulus presented a linear decrease when samples cured in microgravity environment, but presented a parabolic trend when samples were cured in terrestrial environment. The damping properties of samples cured in simulated microgravity environments are better than those cured in terrestrial environment. With the increase in the simulated acceleration of gravity, the diameter of dispersed phase in a sea‐island structure increased, but their number decreased and the bending stress and CTE of the IPN blends all decreased. These results show the formation of IPNs was affected by different gravity values, and the thermal and mechanical properties of the IPN composites were influenced by the changed IPN components. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42063.     

Synthesis and Properties of Interpenetrating Polymer Networks Composed of Epoxy Resins and Polysulphones with Cross-linkable Pendant Vinylbenzyl Groups

Polysulphones with cross-linkable pendant vinylbenzyl groups (PSF-VB) were prepared via chloromethylation of commercial polysulphones. The curing reactivity of PSF-VB was investigated by differential scanning calori-metry. Interpenetrating polymer networks (IPNs) were prepared based on bisphenol A diglycidyl ether (DGEBA) and PSF-VB, where DGEBA was cured by 4,4′-diaminodiphenyl sulphone and VB groups of PSF-VB were radically polymerized using dicumyl peroxide (DCP). Polysulphones having pendant benzyl groups (PSF-Bz) were also prepared and used as non-reactive modifiers. The fracture toughness (K_IC) for the resulting epoxy/PSF-VB IPN increased by 65% with no loss of mechanical properties on 10wt% addition of PSF-VB (7·9mol% VB unit, MW 74000). Non-reactive PSF-Bz was less effective than PSF-VB. Although the PSF-Bz modified resin had a particulate structure, the morphologies of the PSF-VB/epoxy IPNs were not clear from scanning electron micrographs. Furthermore, the epoxy/PSF-VB IPNs had higher solvent resistance than the epoxy/PSF-Bz blends. Morphological behaviour, modification results and high solvent resistance of the cured epoxy/PSF-VB resins indicate that cross-linked PSF-VB and the epoxy network entangled fully in the presence of DCP. © of SCI.     

Characterization of Short Glass Fiber–Reinforced Castor Oil–Based Polyurethane Polystyrene Interpenetrating Networks

ABSTRACT

Chopped strand glass fiber–reinforced particle-filled castor oil–based polyurethane polystyrene composites with varying weight fractions of glass fibers were investigated for morphology, tensile strength, and absorption of various chemicals. The short glass fiber fraction was varied from 1% to 16% (by wt.) of the total composite system. The tensile strength of these composites was much higher than that of unfilled IPNs for the same concentration of polystyrene. The tensile strength of the IPN composites increases with the increase in fiber content up to a fiber percentage of 9%. After that, there is a sharp decline in tensile modulus as well as elongation at break. The chemical absorption showed an increase with increasing glass fiber content.     

Biomimetic strain hardening in interpenetrating polymer network hydrogels

In this paper, we present the systematic development of mechanically enhanced interpenetrating polymer network (IPN) hydrogels with Young's moduli rivaling those of natural load-bearing tissues. The IPNs were formed by synthesis of a crosslinked poly(acrylic acid) (PAA) network within an end-linked poly(ethylene glycol) (PEG) macromonomer network. The strain-hardening behavior of these PEG/PAA IPNs was studied through uniaxial tensile testing and swelling measurements. The interaction between the independently crosslinked networks within the IPN was varied by (1) changing the molecular weight of the PEG macromonomer, (2) controlling the degree of PAA ionization by changing pH, and (3) increasing the polymer content in the PAA network. Young's moduli and the maximum stress-at-break of the swollen hydrogels were normalized on the basis of their polymer content. Strain hardening in the IPNs exhibited a strong dependence on the molecular weight of the first network macromonomer, the pH of the swelling buffer, as well as the polymer content of the second network. The results indicate that the mechanical enhancement of these IPNs is mediated by the strain-induced intensity of physical entanglements between the two networks. The strain can be applied either by mechanical deformation or by changing the pH to modulate the swelling of the PAA network. At pHs below the pK_a of PAA (4.7), entanglements between PEG and PAA are reinforced by interpolymer hydrogen bonds, yielding IPNs with high fracture strength. At pHs above 4.7, a “pre-stressed” IPN with dramatically enhanced modulus is formed due to ionization-induced swelling of the PAA network within a static PEG network. The modulus enhancement ranged from two-fold to over 10-fold depending on the synthesis conditions used. Variation of the network parameters and swelling conditions enabled “tuning” of the hydrogels' physical properties, yielding materials with water content between 58% and 90% water, tensile strength between 2.0 MPa and 12.0 MPa, and initial Young's modulus between 1.0 MPa and 19.0 MPa. Under physiologic pH and salt concentration, these materials attain “biomimetic” values for initial Young's modulus in addition to high tensile strength and water content. As such, they are promising new candidates for artificial replacement of natural tissues such as the cornea, cartilage, and other load-bearing structures.     

Synthesis and characterization of interpenetrating networks from polycarbonate and cellulose acetate butyrate

Polycarbonates (PC) are currently used for organic optical glass; nevertheless they show a poor impact resistance which may be increased by combination with cellulose acetate butyrate (CAB) into a PC/CAB interpenetrating polymer network (IPN), without altering the material transparency as we show here. A series of rigid IPNs based on an aliphatic polycarbonate and CAB was prepared through in situ polymerization techniques. The kinetics of the formation of two networks in the IPNs were studied by FTIR spectroscopy. Effects of the CAB cross-linking and weight proportions of the two components in the IPNs were investigated by dynamic mechanical thermal analysis.