Interpenetrating polymer networks based on thermoplastic polyurethanes (TPUS) and cis-1,4-polyisoprene

Semi-interpenetrating polymer networks based on two elastomers, cis-1,4-polyisoprene (PI) and thermoplastic polyurethane elastomers (TPUs) were prepared in varying compositions. The PI component was cross-linked using peroxide initiators. Modulus and mechanical properties were investigated as a function of composition and temperature. Slight synergisms were observed in mechanical properties, particularly for compositions containing 10% PI by weight. Little or no molecular mixing is shown by differential scanning calorimetry (DSC) for these two-phase materials. © 1994 John Wiley & Sons, Inc.     

Nanoindentation of shape memory polymer networks

This work examines the small-scale deformation and thermally induced recovery behavior of shape memory polymer networks as a function of crosslinking structure. Copolymer shape memory materials based on diethylene glycol dimethacrylate and polyethylene glycol dimethacrylate with a molecular weight of 550 crosslinkers and a tert-butyl acrylate linear chain monomer were synthesized with varying weight percentages of crosslinker from 0 to 100%. Dynamic mechanical analysis is used to acquire the bulk thermomechanical properties of the polymers, including the glass transition temperature and the elastic modulus over a wide temperature range. Instrumented nanoindentation is used to examine ambient temperature deformation of the polymer networks below their glass transition temperature. The glassy modulus of the networks measured using nanoindentation is relatively constant as a function of crosslinking density, and consistent with values extracted from monotonic tensile tests. The ambient temperature hardness of the networks increases with increasing crosslinking density, while the dissipated energy during indentation decreases with increasing crosslinking density. The changes in hardness correlated with the changes in glass transition but not changes in the rubbery modulus, both of which can scale with a change in crosslink density. Temperature induced shape recovery of the indentations is studied using atomic force microscopy. For impressions placed at ambient temperature, the indent shape recovery profile shifts to higher temperatures as crosslink density and glass transition temperature increase.     

Morphology and mechanical properties of blends of polycarbonate and segmented copolyetherester

The solid state features and the mechanical properties of melt mixed polycarbonate (PC)/segmented copolyetherester (CPEE) blends were investigated over the full composition range. The partially crystallized blends were composed of two amorphous phases but with only small composition differences in most blend compositions. The specific interactions, and the free volume decreases observed, gave rise to a decrease in the γ relaxation strength. The dependence on composition of both the decreases in the γ relaxation strength and in the free volume, as well as that of the modulus of elasticity and yield stress, were very similar to those of miscible blends. The nature of the amorphous phases of the blends at room temperature, changed from glassy to partially rubbery as the CPEE content was increased. As a consequence, to discuss the plots of the properties against composition at room temperature, the properties of the rubbery materials in the glassy state had to be determined. The synergistic modulus and yield stress behaviors appeared to be mainly determined by the γ relaxation strength and specific volume decrease, and that of ductility additionally by the T_g change.     

Effect of sub-micron silica fillers on the mechanical performances of epoxy-based composites

Solid state thermo-mechanical properties, as well as low and large strain mechanical behaviour, of epoxy composites filled with sub-micron pyrogenic silica are discussed in this paper. The reinforcement mechanisms involved are investigated. Two distinct series of pyrogenic silica were used: hydrophilic silica with various specific surface areas and silica grafted with various organo-modifications. Furthermore, two series of networks, having either a high or low crosslink density, and resulting thus either in glassy or rubbery materials at room temperature, were considered. Dynamic mechanical analysis, uniaxial tensile tests and fracture mechanic tests were performed.All our results showed that pyrogenic silica leads to an improvement of network mechanical properties both in the glassy and rubbery states. The simultaneous increase of stiffness and toughness was observed, demonstrating the great potential of pyrogenic silica for the reinforcement of thermosetting systems. This exceptional behaviour has been interpreted in terms of the interactions and morphology developed.     

Synergistic blends of natural polymers,pectin and sodium alginate

A wide range of Pectin and Sodium Alginate blends have been investigated by casting films from aqueous solution. Blends showed synergy both in mechanical properties and water vapor permeation rate. Previously observed synergism in gels at low pH is also maintained in cast films of blends having up to 40% Pectin. Films were made water‐insoluble by post‐treatment with CaCl₂, which develops physical crosslinks among the molecules of both polymers. After CaCl₂ treatment, mechanical properties are drastically changed due to development of physically crosslinked tie points in the molecular network structure. The modulus and tensile strength of the resulting network structure are dependent on the nature of the polymers. Even in water insoluble films, synergism in mechanical and water barrier properties is retained in films having up to 20% Pectin content. Structural reorganization before and after CaCl₂ treatment was investigated by X‐ray and dynamic mechanical analysis. The synergism observed in mechanical properties of the films before and after CaCl₂ treatment is attributed to reduction in molecular mobility and change in molecular network structure. Structural reorganization in CaCl₂‐treated films, and thereby film properties, is dependent on the compositions of the blends; blended films show sharp glassy‐rubbery transition in the storage modulus—temperature plot, which is not the case in untreated films. Film flexibility increases with increasing Pectin content in the blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamic Mechanical Properties of Block Copolymer Blends–A Study of the Effects of Terminal Chains in Elastomeric Materials

Abstract

Three different polystyrene-1,4 polybutadiene (SB) diblock copolymers were blended with a single polybutadiene continuous SBS triblock to form rubbery networks with controlled amounts of terminal chains of known molecular weight. The mechanical properties of these materials were studied in dynamic uniaxial compression from 0.1 to 1000 Hz at various temperatures between –87 and 85°C. At high reduced frequencies in the glassy and polybutadiene transition regions the terminal chains have no perceptible effect on the components of the complex compliance. At intermediate reduced frequencies a temperature dependent entanglement coupling phenomenon appears if the terminal chains are sufficiently long. At low reduced frequencies the terminal chains contribute to entanglement slippage processes which result in an increase in both the storage and loss compliance.     

The effect of chemistry on the polymerization, thermo-mechanical properties and degradation rate of poly(β-amino ester) networks

Poly(β-amino ester) networks are gaining attention as a scaffold material for tissue engineering applications where it is important to have tailorable degradation rate and elastic modulus. The objective of this work is to characterize and understand the relationships between chemical structure, polymerization, thermo-mechanical properties, and degradation in poly(β-amino esters) networks. The networks were synthesized from a primary amine with systematically varied molar ratios and chemical structures of diacrylates. Fundamental trends were established between the chemical structure, conversion during polymerization, macromer molecular weight, rubbery modulus, and degradation rate. The thermo-mechanical properties were dependent upon both polymerization steps. The rubbery modulus was tailorable over a range of several MPa by changing molar ratio and diacrylate molecular weight. The degradation rate ranged from hours to months depending upon the composition. Select chemical structures showed degradation rate independent of modulus. This work provides a basis for designing poly(β-amino esters) networks with specific thermo-mechanical properties and degradation rates for biomedical scaffolds.     

Heterogeneous polymer–polymer composites. II. Preparation and properties of model systems

A two-stage emulsion polymerization procedure has been developed and used to prepare relatively uniform populations of heterogeneous acrylic latex particles (HLP). One class of particles (HLP1) can be described as composite materials comprising a glassy continuous phase and a rubbery discrete phase. Another class (HLP2) can be described (at high rubber content) as composite materials comprising a rubbery continuous phase and a glassy discrete phase. The phase structure of the HLP1 is sufficiently stable to allow fabrication of composites having a uniform spatial distribution of inclusions by direct compression molding. Although the observed particle structure of the HLP2 does not depend markedly on crosslinking, the phase structure and mechanical properties of compression moldings do. Crosslinking of the glassy stage appears to stabilize HLP2 phase structure during molding, while crosslinking of the rubbery stage favors phase inversion. The observed HLP2 particle structures and the morphology of molded HLP1 specimens are consistent with a shell-core model. It is found that the modulus and thermal expansion coefficient of many of these materials can be adequately described in terms of a simple theoretical model for the elastic and thermoelastic properties of particulate composites, provided that an interaction parameter interpreted as a maximum packing fraction is introduced.     

Effect of orientation of two-dimensional filler on dynamic mechanical properties of cured epoxy resin

Dynamic mechanical properties of cured epoxy resin filled with mica flake, as two-dimensional filler, were investigated over the temperature range from room temperature to 200°C. Two series of composite specimens were examined. One is series RM, containing ill-oriented mica flakes, and another is RMB, containing mica flakes oriented in the direction parallel to the specimen surface. Both tensile and shear moduli for RMB series were determined by dynamic mechanical experiments. The tensile modulus for RMB series was always higher than that for RM series over the whole temperature range. The shear modulus for RMB series was low, compared with that of the tensile modulus in the rubbery state. The behavior of the modulus reinforcement, observed both in the glassy and rubbery states, was compared with recently proposed theories of Wu and Padawer and Beecher. In the glassy state, the tensile modulus of RM series follows Wu's theory, while that of the RMB series agrees with Padawer and Beecher's theory. In the rubbery state, the tensile modulus of each series cannot be well explained by either theory. It was proposed that the tensile stress applied to the specimen was converted to shear stress in a thin resinous layer sandwiched by two mica flakes. The modulus behavior of the RMB series can be fully explained by this model.     

Polyurethanes having shape memory effects

Segmented polyurethanes (PUs) were prepared from polycaprolactone diols (PCLs), 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol, and tested for shape memory effects. Effects of soft segment molecular weight (M_n = 2000, 4000 and 8000), soft segment content (50–90%), and maximum strain (_m = 100, 200, and 600%) on the cyclic tensile properties as well as the dynamic mechanical, and mechanical properties below (25°C) and above (65°C) the shape recovery temperatures were studied. With increasing soft segment contents: i) glassy state modulus increased and rubbery state modulus decreased; ii) hardness increased at room temperature, and decreased at 65°C; iii) recovery strain decreased with PCL 2000, and increased with PCL 8000 based PUs. On the other hand, the increase in soft segment length resulted in: i) increased rubbery state modulus as well as glass state modulus; ii) increased hardness at room and high temperatures; iii) increased recovery strain at high soft segment content. Tensile yielding became clear with increasing soft segment length and content. Strain upon cooling and unloading (_u) and residual strain (_p) increased, and recovery strain (_r) decreased with cycling. Among these, residual strain was most sensitive to the cycling. Most of the cycling effects were confined during the first one or two cycles. These results were interpreted in terms of soft segment-hard segment phase separation and soft segment crystallization.     

Shape-memory behavior of poly (methyl methacrylate-co –N-vinyl-2-pyrrolidone) / poly (ethylene glycol) semi-interpenetrating polymer networks based on hydrogen bonding

Based on hydrogen bonding interactions, Poly(methyl methacrylate-co-N-vinyl-2-pynolidone) (P(MMA-co-VP)) networks and linear poly(ethylene glycol) (PEG) can form semi-interpenetrating polymer networks (semi-IPNs), i.e. P(MMA-co-VP)/PEG semi-IPNs, which has shape memory behaviour; its maximum storage modulus ratio can be more than 400, and its shape recovery ratio could reach 99%. The morphology, thermal behaviors and dynamic mechanical properties of P(MMA-co-VP)/PEG semi-IPNs were studied by FTIR, TEM, DSC and DMA. When PEG with higher molecular weight was introduced into P(MMA-co-VP) networks, they possess higher glassy state modulus and higher recovering rate. In such a system, the maximum molecular weight of PEG required for the semi-IPN formation reaches 1000.     

Mechanical behavior of gradient polymers

Gradient polymers are multicomponent networks which contain a spatial gradient in the concentration of the components in the blend. In this study, the properties of a system of gradient polymers consisting of a rubbery addition to a glassy matrix [poly(methyl methacrylate)] and a glassy addition to a rubbery matrix [poly(2-chloroethyl acrylate)] were investigated. Dynamic mechanical spectroscopy was used to characterize the compatibility of the polymers. The PMMA matrix gradients were found to be incompatible, while the PCIEA matrix gradients and the interpenetrating network exhibited compatibility. The tensile properties and the fracture strength of the polymers were measured and interpreted in terms of the composition and the deformation mechanism of the materials.     

Preparation and characterization study on maleic acid cross-linked poly(vinyl alcohol)/chitin/nanocellulose composites

In the quest on improving composite formulations for environmental sustainability, maleic acid (MA) cross-linked poly(vinyl alcohol) (PVA)-α-chitin composites reinforced by oil palm empty fruit bunch fibers (OPEFB)-derived nanocellulose crystals (NCC) had been successfully prepared. Based on the Fourier transform infrared (FTIR) spectroscopic analysis, it was proven that molecular interactions of the cross-linker to the polymeric networks was through conjugated ester linkage. Differential scanning calorimetry (DSC) showed that the influence of MA was minimal toward crystallization in the PVA/chitin/NCC composite. Maximum tensile strength, elongation at break and Young's modulus of the respective PVA/chitin/NCC composites were achieved at different content of MA, dependent on the PVA/chitin mass ratio. Among all compositions, a maximum Young's modulus was achieved at 30 wt% MA loading in PVA/chitin-30/NCC, amounting to 2,413.81 ± 167.36 MPa. Moreover, the mechanical properties and selected physicochemical properties (swelling, gel content, and contact angle) of the PVA/chitin/NCC composites could be tailored by varying the chitin content (10–30 wt%) and MA content (10–50 wt% based on total mass of composite). In brief, this chemically cross-linked PVA-based biocomposites formulated with sustainable resources exhibited tunable physicochemical and mechanical properties.     

A dynamic mechanical thermal analysis on allylester polymers and composites filled with alumina

A dynamic mechanical thermal analysis (DMTA) was performed on allylester polymers and composites filled with alumina. We determined the glass transition temperatures and the values of the storage moduli in both the glassy and rubbery states in each system and compared the mechanical-thermal behavior of pristine allylester polymers with that of composites filled with alumina. To supplement the result of DMTA, we also carried out viscometry, gel permeation chromatography, and differential scanning calorimetry. The molecular structures had an influence on the viscosity, the glass transition temperature, and the storage modulus. Allylester composite filled with 20 phr alumina showed peculiar mechanical—thermal behavior. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of rubbery highly fluorinated siloxane–imide segmented copolymers

The synthesis and characterization of a series of poly(siloxane–imide) block (or segmented) copolymers obtained by copolymerization of amine‐terminated polydimethylsiloxane with fluorinated aromatic compounds containing anhydride and amine functionality are reported. New fluorinated block copolymers have been synthesized to obtain organophilic polyimides potentially interesting for molecular membrane separations. The new aspects of this work relative to the literature are (1) a comparison of solution and solid‐state approaches in the imidization step to generate the target poly(siloxane–imide) copolymers and (2) exploration of new compositions involving fluorinated aromatic polymers derived from added diamine compounds. It is shown that the copolymer properties can be tailored from glassy to rubbery materials by varying the amount and the type of oligosiloxane used; the transition between glassy and rubbery properties is characterized at a siloxane content of 60 wt%. As a main result, it is shown that the solid‐state approach for inducing the cyclo‐imidization step is the more efficient one for synthesizing polymers with good mechanical properties, when the amount of siloxane block is increased in the copolymer series. Physical and chemical methods (thermogravimetric analysis, Fourier transform infrared spectroscopy, viscosity measurements) were used to characterize the copolymer properties obtained according to the two different synthesis routes. The obtained siloxane–imide copolymers are well soluble in a large variety of moderately polar solvents and exhibit very good thermal stability up to 400 °C. Hence the prepared copolyimides would seem to be promising candidates as organophilic membranes as well as gas permeation membranes. © 2012 Society of Chemical Industry     

Rheological characterization of styrene acrylonitrile copolymers

The relationship between copolymer composition, molecular weight distribution, and rheological properties of random styrene acrylonitrile copolymers synthesized by radical polymerization in bulk was investigated. From differential scanning calorimetry analysis, glass transition temperature was obtained and increases with the acrylonitrile content. The knowledge of the glass transition is a key factor to compare the different copolymers in an iso‐free volume condition for melt rheology. Owing to time temperature superposition, a large frequencies window ranging from the terminal zone until the glassy plateau can be obtained. Thus, the mechanical spectroscopy was used to estimate the rubbery plateau modulus and the Newtonian viscosity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1316–1321, 2000     

Influence of solvent size on the mechanical properties and rheology of polydimethylsiloxane-based polymeric gels

Soft polymeric gels have utility in a broad range of medical, industrial, and military applications, which has led to an extensive research investment over the past several decades. While most gel research exploits a cross-linked polymer network swollen with small molecule solvents, this article systematically investigates the impact of the solvent molecular weight on the resulting gel mechanical properties. The model polymer gel was composed of a chemically cross-linked polydimethylsiloxane (PDMS) network loaded with a non-reactive PDMS solvent. In addition to investigating the impact of solvent loading, the solvent molecular weight was varied from 423,000 g/mol to 1250 g/mol, broadly spanning the molecular weight of entanglement for PDMS (MW_ENT ∼29,000 g/mol). The gels exhibited a strong frequency dependent mechanical response when the solvent molecular weight >MW_ENT. In addition, scaling factors of shear storage modulus versus solvent loading displayed a distinct decrease from the theoretical value for networks formed in a theta solvent of 2.3 with increasing measurement frequency and solvent molecular weight. The frequency dependent shear storage modulus could be shifted by the ratio of solvent molecular weights to the 3.4 power to form a master curve at a particular solvent loading indicating that mobility of entangled solvent plays a critical role for the mechanical response. In addition, the incorporation of entangled solvent can increase the toughness of the PDMS gels.     

The effects of temperature and molecular weight on the mechanical response and strength of elastomers

Summary Constitutive equations are derived for the mechanical behavior of rubbery polymers at finite strains. The model is based on the concept of rigid-rod networks, where breakage of chains is treated as bond scission. Adjustable parameters in the stress-strain relations are found by fitting observations in tensile tests for ethylene-octene copolymers. It is revealed that the constitutive equations correctly describe stress-strain curves up to the break points. Young's modulus and the critical strength per bond monotonically decrease with temperature and increase with molecular weight. Received: 17 January 2001/Accepted: 27 February 2001     

Reinforcing effect of organoclay in rubbery and glassy epoxy resins,part 1: Dispersion and properties

The reinforcing effect of organoclay in two epoxy matrices, one rubbery and one glassy, was studied. The rubbery and glassy epoxy matrices were chosen to have a very similar chemistry to minimize its impact on the comparison of properties. The epoxy resin was EPON? 828, and the two hardeners were amine‐terminated polyoxypropylene diols, having different average molecular weights (MW) of 2000 and 230 g/mol, namely Jeffamine® D‐2000 and Jeffamine® D‐230, respectively. The nanocomposites were prepared with the organoclay Cloisite® 30B from Southern Clay Products. The quality of dispersion and intercalation/exfoliation was analyzed by means of X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEGSEM), and transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to study the curing reactivity and the thermal stability of the epoxy resin systems, respectively. Tensile properties and hardness of epoxy resin and epoxy nanocomposites were measured according to ASTM standards D638‐02 and D2240‐00, respectively. Fracture surfaces were also analyzed by FEGSEM. These two epoxy systems as well as their nanocomposites display totally different physical and mechanical behavior. It is found that the quality of clay dispersion and intercalation/exfoliation, and the mechanical behavior of the glassy and rubbery epoxy nanocomposites are distinct. The results also indicate that the presence of the clay does not significantly affect the T_g of either the rubbery or the glassy epoxy; however, the fracture surface and mechanical properties were found to be influenced by the presence of nanoclay. Finally, several different reinforcing mechanisms are proposed and discussed for the rubbery and glassy epoxy nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Dynamic mechanical behaviour of polyamide 11/Barium titanate ferroelectric composites

Dynamic mechanical analysis and tensile test have been used to characterize the mechanical behaviour of hybrid composites. Barium titanate (BaTiO₃) is the submicron filler and polyamide 11 (PA 11) the matrix. The influence of volume fraction and particles size (ranging from 100 nm to 700 nm) of the inorganic phase on the composites mechanical properties have been checked. BaTiO₃ dispersion in the matrix increases the tensile modulus of the composites and an evolution from ductile to fragile is observed for volume fractions above 12 vol%. The volume fraction dependence of the glassy shear modulus is well described by the Hashin and Shtrikman model indicative of an interaction lack between the organic and inorganic phases. The decrease of the glassy shear modulus with the filler size has been associated with the existence of softer organic/inorganic interfaces, in agreement with the previous hypothesis. The non linear variation of the rubbery modulus versus particles content is well described by the rubber elasticity model applied to a hydrogen bond network.