Chemical origins of permanent set in a peroxide cured filled silicone elastomer - tensile and H NMR analysis

The aging of a commercial filled siloxane polymeric composite in states of high stress and Co-60 γ-radiation exposure has been studied. DC-745 is a commercially available silicone elastomer consisting of dimethyl, methyl-phenyl, and vinyl-methyl siloxane monomers crosslinked with a peroxide vinyl specific curing agent. It is filled with ∼ 30 wt.% mixture of high and low surface area silicas. This filled material is shown to be subject to permanent set if exposed to radiation while under tensile stress. Tensile modulus measurements show that the material becomes marginally softer with combined radiation exposure and tensile strain as compared to material exposed to radiation without tensile strain. In addition, the segmental dynamics as measured by both uniaxial NMR relaxometry and Multiple Quantum NMR methods indicate that the material undergoes radiatively-induced crosslinking in the absence of tensile strain. In the presence of tensile strain, relaxometry and MQ NMR studies show a strain dependent change in the dynamic order parameter and in the number of polymer chains associated with the filler surface. Solvent swelling measurements indicated no dependence on network crosslink density on strain ratio. Variable tau CPMG echo experiments indicate that a fraction of the polymer chains diffuses through areas of strong magnetic field gradients both at the filler-polymer interface and adjacent to micro-voids within the network. The population of the polymer chains influenced by the field gradients was observed to be dependent on the cumulative dose and degree of tensile strain applied during exposure. The relative change in crosslink density from the NMR and solvent swelling data deviates from that predicted from the Tobolsky model, particularly at higher doses. The likely reasons for this deviation are changes in the filler-polymer interface, increasing deviation from Gaussian chain statistics, and/or the formation of increased numbers of elastically ineffective network chains.     

Characterization of radiation-induced aging in silica-reinforced polysiloxane composites

Changes in crosslink density and chemical structure of silica-reinforced silicone polymer composites due to aging in gamma radiation environments were examined in this study. Solvent swelling was utilized to determine the individual contributions of the matrix polymer and filler phase to the overall crosslink density of silica-reinforced silicone polymer composites. The results show how polymer–filler hydrogen bonding dominates the overall crosslink density of the material. Air-irradiated samples displayed decreased hydrogen bonding at the polymer–filler interface, while vacuum irradiation revealed the opposite effect. These results were supported by solid-state NMR experiments that correlated the motional dynamics of the polymer chains with crosslink density through T₂ relaxation time measurements. GC/MS analysis was used to identify degradation products formed as a result of irradiation and speculate upon likely degradation mechanisms.     

Influence of some crosslinking agents on thermal and mechanical properties of electron beam irradiated polylactide

The aim of this article was to determine and compare the influence of trimethylopropane trimethacylate (TMPTA) and trially isocyanurate (TAIC) crosslinking agents on thermal and mechanical properties of electron beam irradiated polylactide (PLA). The blends were made of PLA mixed with 3 wt% of TMPTA (PLA/TMPTA), and PLA mixed with 3 wt% of TAIC (PLA/TAIC). Injection moulded samples were irradiated with the use of high energy (10 MeV) electron beam at various radiation doses to crosslinking PLA macromolecules. Thermal and mechanical properties were investigated by means of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile strength, and impact strength measurements. The samples were also characterized by Fourier transform infrared spectroscopy (FTIR). It was found that under the influence of electron irradiation PLA/TMPTA samples underwent degradation while PLA/TAIC samples became crosslinked. Tensile and impact strengths of PLA/TMPTA samples decreased with increasing radiation dose while an enhancement of these properties for PLA/TAIC samples was observed.     

Thermal degradation in a trimodal poly(dimethylsiloxane) network studied by (1)H multiple quantum NMR

Thermal degradation of a filled, cross-linked siloxane material synthesized from poly(dimethylsiloxane) chains of three different average molecular weights and with two different cross-linking species has been studied by (1)H multiple quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting residual dipolar coupling () values of 200 and 600 Hz, corresponding to chains with high average molecular weight between cross-links and chains with low average molecular weight between cross-links or near the multifunctional cross-linking sites. Characterization of the values and changes in distributions present in the material were studied as a function of time at 250 degrees C and indicate significant time-dependent degradation. For the domains with low , a broadening in the distribution was observed with aging time. For the domain with high , increases in both the mean and the width in were observed with increasing aging time. Isothermal thermal gravimetric analysis reveals a 3% decrease in weight over 20 h of aging at 250 degrees C. Degraded samples also were analyzed by traditional solid-state (1)H NMR techniques, and off-gassing products were identified by solid-phase microextraction followed by gas chromatography-mass spectrometry. The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and postcuring cross-linking that both contribute to embrittlement.     

Core-shell type polymer microspheres prepared by domain fixing of block copolymer films

Well-defined poly[styrene(S)-b-isoprene(I)] diblock copolymers were prepared by sequential anionic addition. The crosslinking reactions of polyisoprene (PI) spherical domains of these block copolymers were carried out in a n-hexane solution of sulfur monochloride (S₂Cl₂). Electron micrograph of crosslinked products indicates the structure of core-shell type polymer microspheres. It is found from NMR and turbi+imetric measurements that the solubility of core-shell type polymer microspheres depends strongly on that of block chains comprising the shell portion. The particle size of these microspheres shows a narrow distribution.     

Photooxidation of polymers: Relating material properties to chemical changes

This paper is devoted to a comprehensive study of the photo-oxidation of polymeric materials with the goal of correlating modifications of the polymer properties at the molecular and macroscopic levels. Several techniques were used to characterise the modifications of the chemical properties and mechanical behaviour over time under UV light. The methodology was developed on materials used as organic coatings; initially, a well-characterised phenoxy resin (PKHJ^®) was chosen as a model and then the approach was applied to an acrylate-melamine thermoset currently used as a topcoat in the automotive industry. Analysis of degraded samples by IR spectroscopy allowed us to propose a photo-oxidation mechanism. This mechanism suggested that chain scission occurred under photo-oxidation. To entirely understand the degradation of the polymers, gel fraction, thermoporosimetry, DMA, AFM nanoindentation and micro-hardness determinations were performed. The results showed that crosslinking reactions occurred in competition with chain scission and explained for the first time why crosslinking reactions were quite prevalent. Based on the obtained results, quantitative correlations were made between the various criteria of degradation, thus relating the chemical structure changes to the mechanical property modifications.     

Radiation deterioration in mechanical properties and ion exchange capacity of Nafion N117 swelling in water

The base form Nafion N117 samples swelling in the oxygen-saturated distilled water were irradiated with γ-rays or with electron beams at various doses up to 1600 kGy at room temperature or at 343 K to obtain detailed information on the effect of oxygen on the radiation deterioration in the Nafion mechanical properties and in the ion exchange capacity. The contribution of the radical reactions where oxygen molecules did not participate was dominant for the radiation deterioration in the mechanical properties of the Nafion N117 membrane swelling in the oxygen-saturated distilled water at room temperature. The effect of oxygen molecules was not significant due to the little oxygen concentration in the distilled water even though oxygen was saturated in the water. The Nafion N117 membrane irradiated with γ-rays at 343 K became a weak and brittle material, since the rise of the temperature activated the reactions. Oxygen molecules, in contrast, have negligible part in the reactions at 343 K due to their lower solubility in the water. We observed the negligible effect of the radiation sources as well as of the dose rate below 10 kGy/h on the radiation deterioration in Nafion N117 mechanical properties at room temperature. The irradiation of the Nafion membrane with γ-rays or with electron beams is one of the acceleration tests of the Nafion degradation. We made clear that the dissolved fluorine measured using a fluoride ion meter is a hopeful index for the in situ judging of the Nafion mechanical deterioration. The ion exchange capacity of the membrane irradiated up to 1600 kGy was the 20% decrease of the initial capacity at room temperature. Nafion side chains terminating with –SO₃⁻ M⁺ groups were radiation-durable compared with the backbone.     

A thermodynamic study of the crosslinking of methyl silicone rubber

The crosslinking reaction in a two component methyl silicone rubber has been studied by thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The rubber was formed from two methyl silicone prepolymers; one containing reactive hydrogens every 50 to 100 groups and the other polymer containing pendant vinyl groups at the same frequency. In the presence of a platinum catalyst above 60°C crosslinking proceeds without a loss or gain in weight. The heat of reaction, energy of activation (calculated by two methods) crosslink density and elastic modulus (Young's) were studied as a function of prepolymer concentration, dilution and swelling. A preliminary value for the heat of reaction per mole of SiH and SiCHCH₂ has been calculated. From crosslink density measurements both by hexane swelling and TMA and DSC heats of reaction a qualitative picture has been obtained of the role of entangled chains in producing effective crosslinks.     

Crosslinking investigation of polybutadiene thermal degradation by carbon-13 nuclear magnetic resonance

Thermal degradation of polybutadiene (PBD) in anaerobic atmosphere at 250 °C had been studied by carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR) before complete crosslinking. In this investigation four types of low molecular weight PBD with different 1,2-vinyl isomer content had been chosen, then pure and mixed samples of PBD were heated in different time periods. ¹³C NMR spectra showed that two kinds of crosslinking mechanisms occur that both of them produce methyl groups. The first mechanism is a reaction between 1,2-vinyl isomers of two PBD chains, and the second one occurs between 1,2-vinyl isomer of one chain via methylene carbon of cis or trans isomer in another chain. Also ¹³C NMR results showed that the presence of 1,2-vinyl isomer in the PBD structure is necessary and without it none of the mentioned reactions will occur. Furthermore isomers sequence is another important parameter which affects crosslinking. Results show that cis or trans isomer which is not adjacent to 1,2-vinyl isomer does not take part in crosslinking reaction. Moreover such cis or trans isomer can take part in second mechanism of crosslinking that 1,2-vinyl isomer was attached from head to cis or trans isomer, thus in this arrangement of isomers second mechanism of crosslinking will become dominant rather than first mechanism of crosslinking.     

Studies on thermal degradation of 1-4 and 1-2 polybutadienes in inert atmosphere

The degradation of 1,2 and 1,4 polybutadienes by heating in inert atmosphere was characterized by FTIR, NMR and TGA/TCT/GC/MS for the volatile organic compounds. Two distinct mass change stages in the thermogravimetric analysis indicated different temperature ranges of degradation. Below 300 °C, the predominant reactions depend on the chemical structure of PBs. Thus, M1 and M2 formation by heating 1,4-PB at 260 °C allows us to prove crosslinking reaction. On the other hand, heating 1,2-PB at 260 °C leads to decahydronaphthalene and methyl formation by cycloaddition and rearrangement. At about 300 °C, only radical scission occurs for 1,2-PB whereas Diels Alder and proton transfer mechanisms are described for 1,4-PB. The products of reaction are respectively conjugated diene, cyclic and linear unsaturated compounds sometimes with methyl groups. Above 400 °C, the main process is aromatisation for both PBs.     

Effects of filler–polymer interactions on cold‐crystallization kinetics in crosslinked,silica‐filled polydimethylsiloxane/polydiphenylsiloxane copolymer melts

Crystallization in a series of variable crosslink density poly(dimethyl‐diphenyl)siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), nuclear magnetic resonance (NMR), and X‐ray diffraction (XRD). The silicone composite studied was composed of 94.6 mol % dimethoylsiloxane, 5.1 mol % diphenylsiloxane, and 0.3 mol % methyl‐vinyl siloxane (which formed crosslinking after peroxide cure). The polymer was filled with a mixture of 21.6 wt % fumed silica and 4.0 wt % precipitated silica previously treated with 6.8 wt % ethoxy‐end‐blocked siloxane processing aid. Molecular weight between crosslinks and filler–polymer interaction strength were modified by exposure to γ‐irradiation in either air or in vacuo. Isothermal DMA experiments illustrated that crystallization at ?85 °C occurred over a 1.8 hour period in silica‐filled systems and 2.2–2.6 hours in unfilled systems. The crystallization kinetics for irradiated samples were found to be dependent on crosslink density. Irradiation in vacuo resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface for samples irradiated in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1898–1906, 2006     

Properties of crosslinked polylactides (PLLA & PDLA) by radiation and its biodegradability

Crosslinked materials derived from poly(lactide) (PLA) have been produced by radiation modification in the presence of a suitable crosslinker (triallyl isocyanurate) (TAIC). The crosslinking structure introduced in PLA films has not only much improved the heat stability but also their mechanical properties. The properties of crosslinked samples are governed by crosslinking density and these improvement seemed to increase with radiation dose. This implied that the three dimensional networks have been introduced in material by radiation and the crosslinking density depended on the structure and length of PLA chains. Biodegradability of PLA was also determined by an enzymatic degradation test and burying in compost at 55 °C. Differing with PLLA, PDLA was insignificantly degraded by proteinase K. The degradation rate of PLA in compost was postponed with the introduction of crosslinks.     

Effect of electron radiation and triallyl isocyanurate on the average molecular weight and crosslinking of poly(ε‐caprolactone)

Investigation of the effect of electron radiation on the flow rate and average molecular weight of poly(ε‐caprolactone) (PCL) as well as on formation of the gel fraction of this polymer being irradiated in the presence of triallyl isocyanurate (TAIC) was the aim of the present paper. It was found that PCL macromolecules upon the electron radiation underwent both degradation and linking, because of which the polymer molecular weight increased. The processes associated with elongation of the polymer chains prevailed over the degradation ones. It was also found that PCL irradiated in the presence of TAIC underwent crosslinking resulting in formation of a significant amount of the gel fraction. The largest amount of this fraction was created upon the radiation with the dose of 60 kGy, which was confirmed by the results of determination of the swelling index. Changes in properties of PCL, occurring because of the electron radiation, are important for controlling viscosity of polymeric materials during processing of these materials. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of sensitizer length on radiation crosslinked shape–memory polymers

Shape–memory polymers (SMPs) are smart materials that can be designed to retain a metastable state and upon activation, recover a preprogrammed shape. In this study, poly(methyl acrylate) (PMA) is blended with poly(ethylene glycol) diacrylate (PEGDA) of various molecular weights in various concentrations and subsequently exposed to ionizing radiation. PEGDA sensitizes the radiation crosslinking of PMA, lowering the minimum absorbed dose for gelation and increasing the rubbery modulus, after crosslinking. Minimum dose for gelation, as determined by the Charlesby–Pinner equation, decreases from 25.57 kGy for unblended PMA to 2.06 kGy for PMA blended with 10.00 mole% PEGDA. Moreover, increase in the blend concentration of PEGDA increases the crosslinking density of the resulting networks. Sensitizer length, namely M_n of PEGDA, also affects crosslinking and final mechanical properties. Increase in the length of the PEGDA molecule at a constant molar ratio increases the efficacy of the molecule as a radiation sensitizer as determined by the increase in gel fraction and rubbery modulus across doses. However, at a constant weight ratio of PEGDA to PMA, shorter PEGDA chains sensitize more crosslinking because they have more reactive ends per weight fraction. Sensitized samples of PMA with PEGDA were tested for shape–memory properties and showed shape fixity of greater than 99%. Samples had a glass transition temperature near 28 °C and recovered between 97% and 99% of the induced strain when strained to 50%.     

Alkoxysilane Functional Acrylic Latexes: Influence of Copolymer Composition on Self-Curing Behavior and Film Properties

Reactive latexes based on acrylic polymers with trimethoxysilyl groups in the side chain were prepared by semi-continuous emulsion copolymerization. The properties of the latex film related to the polymer network structure and their evolution upon thermal curing were studied as a function of the content of the reactive comonomer, trimethoxysilylpropyl methacrylate (TSPMA), ranging between 8 and 25 wt-%. In particular, the sensitivity to both organic solvent (chloroform) and water and the thermomechanical properties were investigated by swelling experiments and dynamic-mechanical analysis (DMA). The results are interpreted in terms of a transition from uniform to microheterogeneous crosslinking regime, possibly as the result of formation of polyorganosilsesquioxane-like (POSS) crosslinking domains at higher TSPMA content.     

Dynamic mechanical analysis (DMA), 13c solid state nmr and micro-thermomechanical studies of historical parchment

DMA and solid state ¹³C NMR techniques were used to measure historical parchment samples within the framework of the project (MAP) Micro Analysis of Parchment (EC contract No. SMT4-96-2101) in collaboration with the School of Conservation in Copenhagen. DMA was used in both thermal scan and creep modes. Thermal scans provided information on the transitions associated with the collagen polymer. Microthermal analysis was also used to obtain information on the topography and thermal conductivity of sample areas of 100 μm. Localised heating enabled measurements of softening transitions in the sample. This behaviour is influenced by the chemical composition of parchment. 13C NMR provided information on the carbon atoms associated with the polypeptide chains of the collagen in parchment. The behaviour of samples immersed in water and measured in DMA creep mode was used to measure the shrinkage behaviour of the parchment samples. The different but complementary techniques provided a means for characterising the physicochemical state of parchment samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

Gamma radiation synthesis of comb-type graft hydrogels based on poly(acrylic acid) and 4-vinylpyridine

A pH-sensitive comb-type hydrogel was obtained by gamma radiation polymerization and crosslinking of acrylic acid (AAc) in solution. The pH-sensitive 4-vinylpyridine (4VP) was then grafted to the poly acrylic acid (PAAc) hydrogel using gamma radiation from a ⁶⁰Co source. The comb type graft polymers obtained (net-PAAc)-g-4VP has been studied through determination of graft yield and swelling behavior. The critical pH value was found to be 5.6. The apparent mechanical properties appear to be qualitatively better than hydrogels of PAAc upon swelling. The new comb-type system presents faster swelling response (30 h) than the polyacrylic acid hydrogel (50 h). The increase in dose rate from 7.3 to 11.3 kGy h⁻¹, increase the radiation grafting percentage of 4VP in the system. Comb-type polymers were also characterized by DSC, TGA and FTIR-ATR.     

Conformational Selection of Dimethylarginine Recognition by the Survival Motor Neuron Tudor Domain

Tudor domains bind to dimethylarginine (DMA) residues, which are post‐translational modifications that play a central role in gene regulation in eukaryotic cells. NMR spectroscopy and quantum calculations are combined to demonstrate that DMA recognition by Tudor domains involves conformational selection. The binding mechanism is confirmed by a mutation in the aromatic cage that perturbs the native recognition mode of the ligand. General mechanistic principles are delineated from the combined results, indicating that Tudor domains utilize cation–π interactions to achieve ligand recognition.     

Crosslinking study of polyethers containing pendent double bonds

This article studies the crosslinking reactions of some polyethers containing double bonds on the side chains. Thermal crosslinking takes place in all cases, but is overlapped by the degradation process. So, a catalyst has to be used to obtain the cured material and avoid degradation. The best initiator appears to be dicumyl peroxide and the maximum cross-linking degree is achieved only with 5% (w/w). Thermogravimetric analyses are used to test the quality of the cured materials. IR spectroscopy shows that crosslinking actually takes place by polymerizing pendent double bonds. Furthermore, activation energies for thermal and radical initiated crosslinking are determined by means of dynamic DSC studies. © 1995 John Wiley & Sons, Inc.     

Photolysis of thin films of cypermethrin using in situ FTIR monitoring: Products, rates and quantum yields

Cypermethrin is a synthetic pyrethroid insecticide commonly used both indoors and outdoors. Following its application, cypermethrin residues are exposed to atmospheric oxidants, such as ozone and OH radicals, as well as to solar radiation. The current work focuses on the photochemical degradation of cypermethrin under 254 nm, 310 nm, and solar radiation; including kinetic analysis, quantum yields, and identification of volatile and non-volatile products. The investigation was done using a combined FTIR set-up for parallel analysis of condensed and gas phases. Complementary GC–MS analysis was conducted on the pesticide’s residues. Quantum yields of 0.41 and 0.25 were obtained under 254 and 310 nm, respectively. These values are in agreement with outdoor studies and are higher than the known yields for aqueous solution. The values obtained under all tested conditions suggest that photodegradation of adsorbed cypermethrin is a major outdoor degradation pathway. Oxygen presence was found to increase degradation rate and quantum yield.The identified photoproducts include 3-phenoxybenzaldehyde, 3-phenoxybenzoic acid, acetonitrile (m-phenoxyphenyl), and cypermethrin isomers on the surface and formic acid, CO₂ and CO in the gas phase. The condensed phase products are more polar than the parent molecule, suggesting that they may be susceptible to a greater leaching rate in soils.