Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Thermo-oxidative stability of poly(methyl methacrylate)/poly(methyl methacrylate)-grafted SiO2 nanocomposites

Thermo-oxidative stability of PMMA-grafted SiO₂ and PMMA/PMMA-grafted SiO₂ nanocomposites was investigated by conventional non-isothermal gravimetric technique. It was interesting to find that PMMA-grafted SiO₂ nanoparticles exhibited higher thermo-oxidative stability than that of PMMA. The apparent activation energy of PMMA-grafted SiO₂ nanoparticles increased with the grafting ratio of PMMA from SiO₂, which was estimated by Kissinger method. This indicates that the strong interactions existing between the grafted chains are responsible for the enhanced thermo-oxidative stability of PMMA-grafted SiO₂ nanoparticles. However, the grafting ratio of PMMA from SiO₂ in nanoparticles has only limited effect on the thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites due to a much lower content of grafted PMMA in the nanoparticles relative to PMMA. The increased thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites is possibly resulted from the increased SiO₂ content in the nanocomposites, in which the grafting ratio of PMMA in PMMA-grafted SiO₂ nanoparticles is kept almost as a constant. The glass transition temperature (T _g) of PMMA/PMMA-grafted SiO₂ nanocomposites is about 25 °C and is higher than that of PMMA. The grafting ratio of PMMA from SiO₂ in the nanoparticles has no qualitative effects on the T _g of the nanocomposites.     

Toughened poly(methyl methacrylate) nanocomposites by incorporating polyhedral oligomeric silsesquioxanes

We have investigated the toughenability of poly(methyl methacrylate) (PMMA) using polyhedral oligomeric silsesquioxane (POSS) nanocages at loadings between 0 and 15 wt%. Three distinct POSS species were used: a crystallizable type that did not disperse on a molecular scale within the PMMA matrix (cyclohexyl-POSS), and two types of POSS that formed homogeneous mixtures over the loadings we have investigated (methacryl-POSS and trisilanol-phenyl-POSS). Each of the three types of POSS was able to toughen PMMA in slow-speed tension tests at loadings ≤5 wt%; however, the reproducibility was poor due to the high flaw sensitivity of these binary blends. Ternary blends containing both cyclohexyl-POSS and methacryl-POSS showed the greatest increase in tensile toughness and also excellent reproducibility of toughening. A blend containing 2.5 wt% of both cyclohexyl-POSS and methacryl-POSS maintained the same modulus as the unfilled PMMA while increasing the toughness by a factor of 4. Electron micrographs showed extensive particle-matrix debonding of the PMMA from the cyclohexyl-POSS crystallites and some evidence of plastic deformation on the fracture surface. In high rate (1000 s⁻¹) split-Hopkinson pressure bar (SHPB) tests, binary blends of POSS and PMMA were able to improve the impact toughness of PMMA; however, once again the combined addition of both cyclohexyl-POSS and methacryl-POSS led to the greatest reproducibility of toughening. Comparison with previous results suggests that in order to toughen PMMA with rigid fillers, weakly-adhering particles with sizes on the order of 100 nm are required.     

The effect of molecular weight on the lamellar structure, thermal and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerates)

A poly(hydroxybutyrate-co-hydroxyvalerate) with 9% hydroxyvalerate content has been thermally degraded to give a set of materials of different molecular weights. The effect of molecular weight on the lamellar structure, thermal and mechanical properties was investigated. The long period, lamellar and amorphous thickness all increase as molecular weight increases; their values vary linearly with 1/(molecular weight). Observed melting temperatures increase with molecular weight, following the same functional form, while melting enthalpy and non-isothermal crystallization temperature decrease. Young's modulus varies by 13% with molecular weight; changes in crystallinity cannot explain this effect in detail. Ultimate tensile strength increases rapidly with molecular weight and then levels off at 28.5 MPa above 10⁵ g/mol. This can also be seen as a linear variation with 1/(molecular weight). The strain at the point of ultimate tensile strength also increases rapidly up to 10⁵ g/mol but then continues to increase at a slower rate.     

Viscoelastic properties of blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) having various acrylonitrile contents

Dynamic viscoelastic properties of blends of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with various AN contents were measured to evaluate the influence of SAN composition, consequently χ parameter, upon the melt rheology. PMMA/SAN blends were miscible and exhibited a terminal flow region characterized by Newtonian flow, when the acrylonitrile (AN) content of SAN ranges from 10 to 27 wt %. Whereas, PMMA/SAN blends were immiscible and exhibited a long time relaxation, when the AN content in SAN is less than several wt % or greater than 30 wt %. Correspondingly, melt rheology of the blends was characterized by the plots of storage modulus G′ against loss modulus G″. Log G′ versus log G″ plots exhibited a straight line of slope 2 for the miscible blends, but did not show a straight line for the immiscible blends because of their long time relaxation mechanism. The plateau modulus, determined as the storage modulus G′ in the plateau zone at the frequency where tan δ is at maximum, varied linearly with the AN content of SAN irrespective of blend miscibility. This result indicates that the additivity rule holds well for the entanglement molecular weights in miscible PMMA/SAN blends. However, the entanglement molecular weights in immiscible blends should have “apparent” values, because the above method to determine the plateau modulus is not applicable for the immiscible blends. Effect of χ parameter on the plateau modulus of the miscible blends could not be found. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Toughening of dimethacrylate resins by addition of ultra high molecular weight polyethylene (UHMWPE) particles

The effects of the addition of UHMWPE particles, of nominal 〈80 μm〉 size, on the fracture toughness, flexural modulus and strength of composites made with dimethacrylate resins (60/40 wt/wt BisGMA-TEGMA) were investigated as a function of volume fraction of UHMWPE (0-60 vol%) and particle surface treatment. Interfacial shear strengths (τ) were measured via microbond shear strength tests using Spectra900™ (UHMWPE) fibers and BisGMA-TEGMA beads. τ increased by a factor of 4 compared with untreated UHMWPE, and surface treated particles improved the mechanical properties of the composite. Fracture toughness (K_IC) and flexural modulus (E) increased with increased volume fraction of UHMWPE, with maximum K_IC/E increases (at 60 vol%) of 238%/25% compared with the neat resin. SEM images showed debonding as well as yielding and fibrillation of the UHMWPE particles, suggesting that these were significant toughening mechanisms.     

Modification of bisphenol-A based bismaleimide resin (BPA-BMI) with an allyl-terminated hyperbranched polyimide (AT-PAEKI)

As a continuation of previous work involving synthesis of an allyl-functionalized hyperbranched polyimide, AT-PAEKI, we have studied the use of this reactive polymer as a modifier of bisphenol-A based bismaleimide resin (BPA-BMI). This was pursued in anticipation of improvements in processability as well as physical properties including glass transition temperature, elastic modulus, and fracture toughness. Apparent miscibility, indicated by optical clarity with a single T_g, was observed for compositions containing up to 16 wt% AT-PAEKI. Additionally, we observed complete suppression of monomer crystallization and a slight increase in the overall cure exotherm. By rheological characterization, blends containing 4 wt% AT-PAEKI were found to feature a dramatic (65-fold) reduction in the viscosity minimum during heating. Dynamic mechanical analysis (DMA) showed that the addition of 2, 4, 8 wt%. AT-PAEKI increases the cured modulus by approximately 10% from a base value of 3.4 GPa, while adding 16 wt% AT-PAEKI decreases the modulus slightly to 3.3 GPa. DMA also revealed that the cured glass transition temperature increases monotonically with the addition of AT-PAEKI. Fracture toughness was gauged using the single edge notched beam methodology to yield the critical stress intensity factor, K_IC. Our results showed a modest toughening effect (from 0.48 to 0.55 MPa m^1/2) upon the addition of AT-PAEKI. We conclude that AT-PAEKI may serve as an effective reactive processing aid with slight improvements in T_g, modulus, and fracture toughness.     

In situ polymerization approach to multiwalled carbon nanotubes-reinforced nylon 1010 composites: Mechanical properties and crystallization behavior

A series of polyamide 1010 (PA1010 or nylon 1010) and multiwalled carbon nanotubes (MWNTs) composites were prepared by in situ polymerization of carboxylic acid-functionalized MWNTs (MWNT-COOH) and nylon monomer salts. Mechanical tensile tests and dynamic mechanical analysis (DMA) show that the Young modulus increases as the content of the nanotubes increases. Compared with pure PA1010, the Young's modulus and the storage modulus of MWNTs/PA1010 in situ composites are significantly improved by ca. 87.3% and 197% (at 0 °C), respectively, when the content of MWNTs is 30.0 wt%. The elongation at break of MWNTs/PA1010 composites decreases with increasing proportion of MWNTs. For the composites containing 1.0 wt% MWNTs, the Young modulus increases by ca. 27.4%, while the elongation at break only decreases by ca. 5.4% as compared with pure PA1010 prepared under the same experimental conditions. Compared with mechanical blending of MWNTs with pure PA1010, the in situ-prepared composites exhibit a much higher Young's modulus, indicating that the in situ polycondensation method improves mechanical strength of nanocomposites. Scanning electron microscopy (SEM) imaging showed that MWNTs on the fractured surfaces of the composites are uniformly dispersed and exhibit strong interfacial adhesion with the polymer matrix. Moreover, unique crystallization and melting behaviors for MWNTs/PA1010 in situ composites are observed using a combination of differential scanning calorimetry (DSC) and X-ray diffraction methods. It was shown that only the α-form crystals are observed in our MWNTs/PA1010 in situ composites. This result is quite different from PA1010/montmorillonite and PA6-clay composites, where both of α- and γ-form crystals were found.     

Preparation of the Pt nanoparticles decorated poly(N-acetylaniline)/MWNTs nanocomposite and its electrocatalytic oxidation toward formaldehyde

In this work, a novel 3D nanocomposite is presented, which is consisted of poly(N-acetylaniline) (PAANI)/multi-walled carbon nanotubes (MWNTs) nanorods (in which the inner layer was comprised of MWNTs and the outer layer was PAANI, forming a core-shell structure) and the decorated Pt nanoparticles. Electrochemical techniques (such as electrochemical impedance spectroscopy (EIS)), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) are used to characterize the nanocomposite. The resulting Pt/PAANI/MWNTs nanocomposite can be served as a higher efficient catalyst for the electrochemical oxidation of formaldehyde at 0.41 V with the catalytic current of 0.73 mA, which was accompanied with about 45 mV potential negative shifts and two-fold increase in peak current comparison to the Pt/PAANI. These results reveal that the Pt/PAANI/MWNTs nanocomposite film is quite promising in the fuel cell applications.     

Effects of compatibilizer on the morphological,mechanical, and rheological properties of poly(methyl methacrylate)/poly(N‐methyl methacrylimide) blends

The effects of compatibilizer on the morphological, thermal, mechanical, and rheological properties of poly(methyl methacrylate) (PMMA)/poly(N‐methyl methacrylimide) (PMMI) (70/30) blends were investigated. The compatibilizer used in this study was styrene–acrylonitrile–glycidyl methacrylate (SAN‐GMA) copolymer. Morphological characterization of the PMMA/PMMI (70/30) blend with SAN‐GMA showed a decrease in PMMI droplet size with an increase in SAN‐GMA. The glass‐transition temperature of the PMMA‐rich phase became higher when SAN‐GMA was added up to 5 parts per hundred resin by weight (phr). The flexural and tensile strengths of the PMMA/PMMI (70/30) blend increased with the addition of SAN‐GMA up to 5 phr. The complex viscosity of the PMMA/PMMI (70/30) blends increased when SAN‐GMA was added up to 5 phr, which implies an increase in compatibility between the PMMA and PMMI components. From the weighted relaxation spectrum, which was obtained from the storage modulus and loss modulus, the interfacial tension of the PMMA/PMMI (70/30) blend was calculated using the Palierne emulsion model and the Choi‐Schowalter model. The results of the morphological, thermal, mechanical, and rheological studies and the values of the interfacial tension of the PMMA/PMMI (70/30) blends suggest that the optimum compatibilizer concentration of SAN‐GMA is 5 phr. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43856.     

Enhancement of interfacial adhesion and dynamic mechanical properties of poly(methyl methacrylate)/multiwalled carbon nanotube composites with amine-terminated poly(ethylene oxide)

We have studied the dynamic mechanical behavior of poly(methyl methacrylate) (PMMA)/acidified multiwalled carbon nanotube (MWNT) composites compatibilized with amine-terminated poly(ethylene oxide) (PEO-NH₂). PEO-NH₂ is ionically associated with acidified MWNTs via ionic interaction as shown by XPS and FTIR. The miscibility between PEO and PMMA improves the interfacial adhesion between polymer matrix and MWNTs, leading to an increase in the storage modulus values of the composites. The effects of PEO-NH₂ on storage modulus and glass transition temperature are discussed.     

Investigation on the early and late stage phase-separation dynamics of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) blends through rheological and scattering functions

The phase-separation behavior of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) (PMMA/α-MSAN) blends with two different compositions was studied by time-resolved small angle light scattering (SALS) in the spinodal decomposition (SD) regime from 160 to 210 °C. The rheological function (WLF-like equation) was introduced into the processing of light scattering data. It was found that the WLF-like equation was applicable to describe the temperature dependence of apparent diffusion coefficient D_app and the relaxation time τ of normalized scattering intensity (I(t)−I(0))/(I_m−I(0)) at the early stage of SD, as well as the relaxation time τ of maximum scattering intensity I_m and characteristic scattering vector q_m with I_m at the late stage of SD for PMMA/α-MSAN blends with two different compositions. This is in consistence with the phase-separation behavior of PMMA/SAN reported in our previous paper.     

Miscibility of copolycarbonate blends with poly(styrene-co-acrylonitrile) copolymer and their interaction energies

The phase behavior of dimethyl polycarbonate-tetramethyl polycarbonate (DMPC-TMPC) blends with poly(styrene-co-acrylonitrile) copolymers (SAN) and the interaction energies of binary pairs involved in blend has been explored. DMPC-TMPC copolycarbonates containing 60 wt% TMPC or more were formed miscible blends with SAN containing limited amounts of AN. The miscibility of copolycarbonate with SAN decreases as the DMPC content increases. The miscible blends showed the LCST-type phase behavior or did not phase separate until thermal degradation. The binary interaction energies involved in the miscible blends were calculated from the phase boundaries using the lattice-fluid theory combined with binary interaction model. The phenyl ring substitution with methyl groups did not lead to interactions that are favorable for miscibility with polyacrylonitrile (PAN). The interaction energies of the polycarbonates blends with SAN copolymers as a function of AN content were obtained. It was revealed that the incline of the number of methyl groups on the phenyl rings of bisphenol-A unit acts favorably for the miscibility with SAN copolymer when SAN contains less than about 30 wt% AN and shifts the most favorable interaction to the low AN content.     

Rheological behavior of blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-stat-styrene)-graft-polybutadiene (ABS)

The rheological behavior of blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-stat-styrene)-graft-polybutadiene (ABS) was investigated using a cone-and-plate rheometer. The rheological properties measured were shear stress (σ₁₂), viscosity (η), and first normal stress difference (N₁) as functions of shear rate (\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$ \end{document}) in steady shearing flow, and storage modulus (G′) and loss modulus (G″) as functions of frequency (ω) in oscillatory shearing flow. It has been found that the rheological behavior of blends of ABS and PMMA was very similar to that of blends of poly(styrene-stat-acrylonitrile) (SAN) and PMMA, in that N₁ in logarithmic plots of N₁ versus σ₁₂, and G′ in logarithmic plots of G′ versus G″, vary regularly with blend composition. This has led us to conclude that the rubber particles that are grafted on an SAN resinous matrix in ABS resin plays only a minor role in influencing the compatibility of ABS/PMMA blends, and that the SAN chains attached to the surface of rubber particles, and the SAN matrix phase, play a major role in compatibilizing ABS resin with PMMA.     

Swelling and mechanical behavior of poly(N-isopropylacrylamide)/Na-montmorillonite layered silicates composite gels

Clay-polymer hydrogel composites have been synthesized based on poly(N-isopropylacrylamide) (PNIPAM) gels containing 0.25-4 wt% of the expandable smectic clay Na-montmorillonite layered silicates (Na-MLS). The morphology of the composite gels has been studied using a polarized optical microscope. The size of Na-MLS aggregates increases with Na-MLS concentration. The swelling ratio of the Na-MLS/PNIPAM composite in water is increased at the low Na-MLS concentration but decreases as the concentration increases. Correspondingly, the shear modulus of the gel is found to exhibit a distinct minimum against clay concentration. For Na-MLS concentrations ranging from 2.0 to 3.2 wt%, the composite gels have larger swelling ratio and stronger mechanical strength than those for a pure PNIPAM. The presence of Na-MLS does not affect the value of the lower critical solution temperature (LCST) of the PNIPAM. However, the gel volume change at the LCST is first increased and then decreased upon the increase of the Na-MLS. No pH induced phase transition is observed for the Na-MLS/PNIPAM composites. The experimental results can be explained by considering that Na-MLS is physically entrapped inside rather than chemically bonded into the gel.     

Preparation of a microporous polymer electrolyte based on poly(vinyl chloride)/poly(acrylonitrile-butyl acrylate) blend for Li-ion batteries

Poly(acrylonitrile-co-butyl acrylate) (P(AN-co-BuA))/poly(vinyl chloride) (PVC) blend-based gel polymer electrolyte (BGPE) was prepared for lithium-ion batteries. The P(AN-co-BuA)/PVC BGPE consists of an electrolyte-rich phase, which is mainly composed of P(AN-co-BuA) and liquid electrolyte, acting as a conducting channel and a PVC-rich phase that provides mechanical strength. The dual phase was just simply developed by the difference of miscibility properties in solvent, PC, between P(AN-co-BuA) and PVC. The mechanical strength of this new blend electrolyte was found to be much higher, with a fracture stress as high as 29 MPa in dry membrane and 21 MPa in gel state, than that of a previously reported P(AN-co-BuA)-based gel polymer electrolyte. The blended gel polymer electrolyte showed ionic conductivity of higher than 1.5 × 10⁻³ S cm⁻¹ and electrochemical stability up to at least 4.8 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for lithium-ion batteries.     

Comparison of morphologies and mechanical properties of crosslinked epoxies modified by polystyrene and poly(methyl methacrylate)) or by the corresponding block copolymer polystyrene-b-poly(methyl methacrylate)

Polystyrene (PS, M_n=28,400, PI=1.07), poly(methyl methacrylate) (PMMA, M_n=88,600, PI=1.03), and PS (50,000)-b-PMMA (54,000) (PI=1.04), were used as modifiers of an epoxy formulation based on diglycidyl ether of bisphenol A (DGEBA) and m-xylylene diamine (MXDA). Both PS and PMMA were initially miscible in the stoichiometric mixture of DGEBA and MXDA at 80 °C, but were phase separated in the course of polymerization. Solutions containing 5 wt% of each one of both linear polymers exhibited a double phase separation. A PS-rich phase was segregated at a conversion close to 0.02 and a PMMA rich phase was phase separated at a conversion close to 0.2. Final morphologies, observed by scanning electron microscopy (SEM), consisted on a separate dispersion of PS and PMMA domains. A completely different morphology was observed when employing 10 wt% of PS-b-PMMA as modifier. PS blocks with M_n=50,000 were not soluble in the initial formulation. However, they were dispersed as micelles stabilized by the miscible PMMA blocks, leading to a transparent solution up to the conversion where PMMA blocks began to phase separate. A coalescence of the micellar structure into a continuous thermoplastic phase percolating the epoxy matrix was observed. The elastic modulus and yield stress of the cured blend modified by both PS and PMMA were 2.64 GPa and 97.2 MPa, respectively. For the blend modified by an equivalent amount of block copolymer these values were reduced to 2.14 GPa and 90.0 MPa. Therefore, using a block copolymer instead of the mixture of individual homopolymers and selecting an appropriate epoxy-amine formulation to provoke phase separation of the miscible block well before gelation, enables to transform a micellar structure into a bicontinuous thermoplastic/thermoset structure that exhibits the desired decrease in yield stress necessary for toughening purposes.     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Thermodynamic, morphological, mechanical and fracture properties of poly(methyl methacrylate)(PMMA) modified divinylester(DVE)/styrene(St) thermosets

Modified St/DVE cured materials were formulated with a commercial DVE_C (M_n=1015 g/mol) and a synthesized (583 g/mol) DVE_L resins and styrene, adding a high molecular weight PMMA as modifier. A thermodynamic analysis of the initial miscibility for the St-PMMA and DVE-PMMA quasibinary systems was realized using the experimental cloud-point curves (CPC), in order to determine the binary interaction parameters. Calculated CPC for the quasiternary St/DVE/PMMA at 25 °C showed that St/DVE_L/PMMA is miscible in the whole concentration range, while the St/DVE_C/PMMA becomes partially miscible almost at the start of curing reaction (very low conversions). This miscibility behavior originates quite different morphologies in the systems cured at room temperature. Final materials with DVE_L showed typical nodular microphase morphologies generated by polymerization induced phase separation (PIPS) mechanism. Materials with DVE_C showed typical macrophase morphologies characterized by droplets-like domains, with secondary phase separation inside the droplets and in the mother phase. These morphological structures were directly related to the thermal and mechanical properties of the final systems. The low molecular weight resin generates a thermoset of higher glass transition temperature, bending modulus, and compression yield stress, but lower fracture resistance than the high molecular weight commercial resin. The addition of a thermoplastic modifier allowed to improve the fracture resistance without the unwanted reduction in modulus, which is inevitable when using elastomeric additives. The reason for the existence of an optimum modifier concentration is also discussed.     

Effect of chemical structure and crosslinking density on the thermo-mechanical properties and toughness of (meth)acrylate shape memory polymer networks

The objective of this work is to characterize and understand structure-mechanical property relationships in (meth)acrylate networks. The networks are synthesized from mono-functional (meth)acrylates with systematically varying sidegroup structure and multi-functional crosslinkers with varying mole fraction and functionality. Fundamental trends are established between the network chemical structure, crosslink density, glass transition temperature, rubbery modulus, failure strain, and toughness. The glass transition temperature of the networks ranged from −29 to 112 °C, and the rubbery modulus (E_r) ranged from 2.8 to 129.5 MPa. At low crosslink density (E_r < 10 MPa) network chemistry has a profound effect on network toughness. At high crosslink densities (E_r > 10 MPa), network chemistry has little influence on material toughness. The characteristic ratio of the mono-functional (meth)acrylates' components is unable to predict trends in network toughness as a function of chemical structure, as has been demonstrated in thermoplastics. The cohesive energy density is a better tool for relative prediction of network mechanical properties. Due to superior mechanical properties, networks with phenyl sidegroups are further investigated to understand the effect of phenyl sidegroup structure on toughness.