Thermal and radio-oxidation of epoxy coatings

Degradation induced by thermal (50–110 °C) and radio-oxidation of low T_g epoxy-amine networks has been studied. It has been found that oxidation leads mainly to amide groups formation at the vicinity of tertiary amines whatever ageing conditions (thermal or radio-oxidation at 200 Gy h⁻¹). In addition, some species as acids, peracids or formates have been revealed indicating a chain scission process. Physical modifications as T_g decrease and soluble fraction increase due to chain scission process, have been correlated with chemical modifications.     

Reversible thickness control of polymer thin films containing photoreactive coumarin derivative units

The reversible control of the thickness of polymer thin films was investigated using (meth)acrylic polymers containing photoreactive coumarin derivative units in the side chain. Coumarin derivative units underwent dimerization and the reverse-dimerization by photoirradiation and were used as a reversible cross-linking point. The homopolymer of 7-methacryloyloxy-4-methylcoumarin (T_g = 194 °C) did not cause changes in film thickness after photoreactions. The homopolymer of 7-(2′-acryloyloxyethoxy)-4-methylcoumarin (AEMC) (T_g = 89 °C) decreased 19% of film thickness by photodimerization and 73% of the decreased thickness was recovered after the reverse-dimerization and the subsequent thermal annealing at 130 °C. The reverse-dimerization of the copolymer of AEMC and n-butyl acrylate (AEMC content = 19 mol%, T_g = 11 °C) resulted in 53% of recovery from the decreased film thickness without annealing. The mobility of polymer main-chain was revealed to be essential factor to change film thickness by photoreactions. Photodimerization of coumarin derivative units in low glass transition temperature (T_g) tended to proceed faster than in high T_g polymers and resulted in larger decrease in film thickness.     

Castor oil-based thermosets with varied crosslink densities prepared by ring-opening metathesis polymerization (ROMP)

Two castor oil-based monomers, (1) norbornenyl-functionalized castor oil (NCO), which has ∼0.8 norbornene rings per fatty acid chain and (2) norbornenyl-functionalized castor oil alcohol (NCA), which has ∼1.8 norbornene rings per fatty acid chain, have been prepared. Ring-opening metathesis polymerization (ROMP) of different ratios of NCO/NCA using the 2nd generation Grubbs catalyst results in rubbery to rigid biorenewable-based plastics with crosslink densities ranging from 318 to 6028 mol/m³. Increased crosslink densities result in shorter gelation times, better incorporation of the monomers into the polymer network, and much less soluble materials in the bulk materials. The increased crosslink densities obtained by adding NCA enhance the thermal properties, including the glass transition temperature (T_g) and room temperature storage modulus, which increase from −17.1 °C to 65.4 °C and from 2.4 MPa to 831.9 MPa, respectively. The TGA results, where T₁₀ increased from 285 °C to 385 °C, illustrate that improved thermal stabilities can be obtained for thermosets with higher crosslink densities. Young’s modulus (11-407 MPa), tensile strength (1.6-18 MPa) and toughness (0.14-1.6 MPa) are also improved dramatically with higher crosslink densities.     

Influence of DGEBA crosslinking on Li ion conduction in poly(ethyleneimine) gels

We characterize the DC conductivity (σ₀) of solution electrolytes prepared by adding LiCF₃SO₃ (LiTf) salt to a (50/50 w/w) solution of branched poly(ethyleneimine) (PEI) in N,N-dimethylformamide (DMF). The value of σ₀ increases with decreasing LiTf concentration over the range of compositions studied due to the formation of contact ion pairs at higher LiTf concentrations, with the highest value of σ₀ exceeding 10⁻³ S cm⁻¹ at 20 °C. Rubber-like gel electrolytes are prepared by epoxide-amine crosslinking of selected solutions by addition of diglycidyl ether of bisphenol A (DGEBA). Holding the [N]:[Li] mole ratio fixed, increasing the crosslink density dramatically decreases σ₀ at all temperatures studied. The decrease in σ₀ cannot be attributed to an increase in the glass transition temperature, as little variation in T_g is noted amongst the samples due to their high solvent content. Rather, we propose that the decrease in conductivity is due to loss of fast segmental motions associated with chain ends, which become tethered to the network upon crosslinking.     

Moisture absorption by cyanate ester modified epoxy resin matrices. Part I. Effect of spiking parameters

The moisture absorption of cyanate ester modified epoxy resin matrices has been studied under thermal spiking conditions. Enhanced moisture absorption has been observed at spike-temperatures above 120 °C. The results of the desorption studies on both control specimens and the spiked specimens showed that some of the water molecules remained entrained in the polymer. It is postulated that this water could be associated with that which is hydrogen bonded or from the hydrolysis of isolated residual cyanate ester groups because the concentration of entrained water remains constant at spike-temperatures below 180 °C. Above 180 °C a thermally activated process, leading to chain scission as indicated by a reduced recoverability of the glass transition temperature (T_g) on drying.On isothermal resorption, the moisture concentration was found to be similar to that achieved through thermal spiking, showing that the entrained water at the lower spike-temperatures can also be achieved under mild conditions. The T_g is reversibly recovered to within 5 °C, which indicates a degree of relaxation rather than degradation. The moisture diffusion coefficient estimated from the resorption curves is lower than those estimated from the absorption and desorption curves. The isothermal resorption diffusion coefficient also decreased with increasing spike temperature. It is proposed that thermal spiking induced a relaxation of the network but as the spike-temperature approaches the transition region of the wet polymer, further hydrolytically induced relaxation events become feasible.     

Influence of copolymerisation on fracture behaviour of aliphatic polyketones

High strain rate tensile impact properties of aliphatic polyketone terpolymers were investigated and related to the polymer chain structure. Aliphatic polyketones were used as a model system, by changing the termonomer content and type. Aliphatic polyketone is a perfectly alternating copolymer and the structure was changed with the addition of a few mol% of termonomer: propylene, hexylene and dodecene. Studied were the thermal properties with DSC and DMTA, tensile behaviour, notched tensile impact behaviour, notched Izod properties and the temperature development during deformation. The perfectly alternating copolymer had a melting point of 257 °C, a T_g at 15 °C, a high crystallinity (48%), a high yield stress (77 MPa) and yield strain (31%) but a relatively low fracture strain (85%) and an impact strength (notched Izod) of 13 kJ/m². Increasing the propylene content to 6%, lowered the melting temperature to 224 °C, without changing the T_g. The modulus and yield stress were lowered but the impact strength improved. Increasing the length of the termonomer while keeping the T_m at 224 °C lowered the T_g, the modulus, the yield stress but strongly improved the impact resistance. The longer termonomers, with a lower yield stress, reduced the necking behaviour. The temperature increase in front of the notch was about 85 °C. By adding termonomers to aliphatic ketones, the notched impact behaviour improved significantly at the cost of modulus and yield stress.     

Synthesis, preparation and properties of novel high-performance allyl-maleimide resins

Three novel allyl-maleimide monomers (i.e., A₂B, AB and AB₂) were designed, synthesized and thermally cured to yield a series of high-performance allyl-maleimide resins. All the monomers obtained are readily soluble in common organic solvents enabling an easy solution processing. The thermal properties of the three monomers were studied by the differential scanning calorimetry (DSC). A₂B and AB showed fairly low melting temperature (T_m < 90 °C) and wide processing window ranging from 90 °C to 260 °C. The thermal stability of the cured allyl-maleimide resins (i.e., PA₂B, PAB and PAB₂) was studied by the thermogravimetric analysis (TGA). Dynamic mechanical analysis (DMA) was used to investigate the dynamic mechanical properties of the composites based on the cured allyl-maleimide resins. PA₂B and PAB₂ showed good glass transition temperatures (T_g > 270 °C) and their corresponding composites showed high bending modulus (E′ > 1900 MPa). Allyl-compound-modified BMI resins based on AB monomer were prepared. Rheometer revealed that the processability of the prepolymer (BR-AB-pre) was improved by the addition of AB monomer. The cured BMI resins (BR and BR-AB) showed good thermal stability (T_d > 400 °C, both in nitrogen and in the air), high glass transition temperature (T_g > 320 °C), and good mechanical properties and low water uptake (<2.6%, 120 h).     

Synthesis of nitrile and benzoyl substituted poly(biphenylene oxide)s via nitro displacement reaction

A series of substituted poly(biphenylene oxide)s (PBPOs) was synthesized via nucleophilic nitro displacement reactions. High molecular weight PBPO's with nitrile groups were effectively synthesized from the polymerization of A-B type monomers with K₂CO₃ as a base in N-methyl-2-pyrrolidinone (NMP) at 140 °C. The polymers are completely amorphous, soluble in polar aprotic solvents, and formed flexible films on solution casting. Para-linked PBPO with nitrile groups showed excellent thermal properties such as high 5% weight loss temperature above 530 °C and T_g at 241 °C which is higher than those of commercially available PPO™ (T_g=210 °C). The pendent nitrile groups of PBPO were easily transformed to carboxylic acid groups by acidic hydrolysis.     

Synthesis and properties of novel sulfonated polyimides bearing sulfophenyl pendant groups for polymer electrolyte fuel cell application

A novel sulfonated diamine bearing sulfophenyl pendant groups of 2,2′-(4-sulfophenyl) benzidine (BSPhB) was synthesized. Sulfonated polyimides (SPIs) derived from 1,4,5,8-naphthalene tetracarboxylic dianhydride, BSPhB and other non-sulfonated diamines were successfully synthesized. The SPIs with ion exchange capacity (IEC) of 1.5-2.8 meq g⁻¹ showed high reduced viscosity of 3-10 dL g⁻¹ and high desulfonation temperature of 320 °C. The SPI membranes were tough and flexible, having high stress at break of more than 80 MPa and elongation of 80-100%. They showed highly anisotropic membrane swelling in water with larger swelling in thickness direction than in plane direction. They showed fairly high proton conductivity (σ). For example, the membrane with IEC of 1.77 meq g⁻¹ exhibited σ values of 120 and 260 mS cm⁻¹ at 60 and 120 °C, respectively, in water. They also showed fairly high water stability.     

Preparation, characterization and mechanical properties of epoxidized soybean oil/clay nanocomposites

New epoxidized soybean oil (ESO)/clay nanocomposites have been prepared with triethylenetetramine (TETA) as a curing agent. The dispersion of the clay layers is investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD and TEM data reveal the intercalated structure of ESO/clay nanocomposites has been developed. The thermogravimetric analysis exhibits that the ESO/clay nanocomposites are thermally stable at temperatures lower than 180 °C, with the maximum weight loss rate after 325 °C. The glass transition temperature, T_g, about 7.5 °C measured by differential scanning calorimetry (DSC) and T_g about 20 °C measured by dynamic mechanical study have been obtained. The difference in the T_g between DSC and dynamic measurements may be caused by different heating rate. The nanocomposites with 5-10 wt% clay content possess storage modulus ranging from 2.0×10⁶ to 2.70×10⁶ Pa at 30 °C. The Young's modulus (E) of these materials varies from 1.20 to 3.64 MPa with clay content ranging from 0 to 10 wt%. The ratio of epoxy (ESO) to hydrogen (amino group of TETA) greatly affects dynamic and tensile mechanical properties. At higher amount of TETA, the nanocomposites exhibit stronger tensile and dynamic properties.     

Lamella reorientation in thin films of a symmetric poly(l-lactic acid)-block-polystyrene upon crystallization at different temperatures

The thin films of a symmetric crystalline-coil diblock copolymer of poly(l-lactic acid) and polystyrene (PLLA-b-PS) formed lamellae parallel to the substrate surface in melt. When annealed at temperatures well above the glass transition temperature of PLLA block (T_g^PLLA), the PLLA chains started to crystallize, leading to reorientation of lamellae. Such reorientation behavior exhibited dependence on the correlation between the crystallization temperature (T_c), the glass transition temperature of PS (T_g^PS), the peak melting point of PLLA crystals (T_m^PLLA), and the end melting point of PLLA crystals (T_m,end^PLLA). When annealed at (T_c=) 80 °C (T_c < T_g^PS < T_ODT, order-disorder transition temperature), 123 °C (T_g^PS < T_c < T_m^PLLA < T_ODT), 165 °C (T_g^PS < T_m^PLLA < T_c < T_m,end^PLLA < T_ODT), the parallel lamellae became perpendicular to the substrate surface, exclusively starting at the edge of surface relief patterns. Meanwhile, the corresponding lamellar spacing was significantly enhanced. The PLLA crystallization between PS layers was hypothesized to account for the lamella reorientation during annealing. The crystallization, chain conformation, and possible chain folding mechanisms were discussed, based on detailed analysis of the lamellar structure before and after crystallization.     

Influence of oxidation on fatigue life of a carbon/silicon carbide composite in water vapor containing environments

The influence of oxidation on the fatigue life of two-dimensional carbon/silicon carbide composites in water vapor containing environments at 1300 °C was investigated. Tension–tension fatigue experiments were conducted at sinusoidal frequency of 3 Hz. Using a stress ratio (σ_min/σ_max) of 0.1, specimens were subjected to peak fatigue stresses of 90, 120 and 150 MPa. The mean residual strength of the specimens after survived 100,000 cycles with a peak stress of 90 MPa was 83.9% of that of the as-received composite. The mean fatigue lives of the specimens subjected to peak fatigue stresses of 120 and 150 MPa were 42,048 and 13,514 cycles, respectively. Oxidation was the dominant damage mechanism, which remarkably decreased the fatigue life. Oxidizing species diffusion within the composite defects was discussed. The higher the applied stresses, the larger the equivalent radius of the defect and the shorter the fatigue life.     

Thermo-sensitive sol-gel transition of poly(depsipeptide-co-lactide)-g-PEG copolymers in aqueous solution

A series of biodegradable graft copolymers composed of poly(ethylene glycol) side-chains and a poly(depsipeptide-co-dl-lactide) backbone (PDG-dl-LA-g-PEG) were prepared as a novel thermo-gelling system. An aqueous solution of PDG-dl-LA-g-PEG (20 wt%) with a certain PEG length and composition showed instantaneous temperature-sensitive gelation at 33 °C. The sol-gel transition temperature (T_gel) could be controlled from 33 to 51 °C by varying the PEG length and compositions without a decrease in mechanical strength of the hydrogels. The 20 wt% hydrogel was eroded gradually in PBS at 37 °C for 60 days. This research provides a molecular design approach to create biodegradable thermo-gelling polymers with controllable T_gel and mechanical toughness.     

Immobilization of polyvinylacetate macromolecules on hydroxyapatite nanoparticles

Concentration dependence of the storage modulus, E′, was investigated for polyvinylacetate (PVAc) filled with hydroxyapatite (HAP) nanoparticles. The filler volume fraction, v_f, varied from 0 to 0.05 and the E′ and loss tangent, tan δ, were measured below neat matrix T_g at −40 °C and above neat matrix T_g at +50 °C at 1 Hz. The T_g determined as the position of the maximum on the temperature dependence of tan δ increased by 14 °C compared to the neat PVAc (39 °C) by adding 5 vol.% of HAP. At −40 °C, the observed small increase of E′ with v_f was in agreement with the prediction based on the simple Kerner equation. At +50 °C, the increase of E′ with v_f observed was an order of magnitude greater than that predicted using the simple continuum mechanics model. An attempt was made to explain the observed deviation employing the hypothesis of immobilized entanglements.     

Recrystallization studies on isotropic cold-crystallized PET: Influence of heating rate

The nanostructural changes associated to the multiple melting behaviour of isotropic cold-crystallized poly(ethylene terephthalate) (PET) have been investigated by means of simultaneous wide- and small-angle X-ray scattering, using a synchrotron radiation source. Variations in the degree of crystallinity, coherent lateral crystal size and long period values, as a function of temperature, for two different heating rates are reported for cold-crystallized samples in the 100-190 °C range. The Interface Distribution Function analysis is also employed to provide the crystalline and amorphous layer thickness values at various temperatures of interest. Results suggest that samples crystallized at both low (T_a = 100-120 °C) and high (T_a = 160-190 °C) temperatures are subjected to a nearly continuous nanostructural reorganization process upon heating, starting immediately above T_g (≈80 °C) and giving rise to complete melting at ≈260 °C. For all the T_a investigated, a melting-recrystallization mechanism seems to take place once T_a is exceeded, concurrently to the low-temperature endotherm observed in the DSC scans. For low-T_a and slow heating rates (2 °C/min), a conspicuous recrystallization process is predominant within T_a + 30 °C ≤ T ≤ 200 °C. In contrast, for high-T_a, an increasingly strong melting process is observed. For both, high- and low-T_a, an extensive structural reorganization takes place above 200 °C, involving the appearance of new lamellar stacks simultaneously to the final melting process. The two mechanisms should contribute to the high-temperature endotherm in the DSC scan. Finally, the use of a high heating rate is found to hinder the material's overall recrystallization process during the heating run and suggests that the high-temperature endotherm is ascribed to the melting of lamellae generated or thickened during the heating run.     

Strain recovery of post-yield compressed semicrystalline poly(butylene terephthalate)

Cubic specimens of a semicrystalline poly(butylene terephthalate) (PBT) have been compressed up to post-yield deformation levels with a fast (3.0 × 10⁻² s⁻¹) and a slow (1.5 × 10⁻⁴ s⁻¹) strain rate at three different temperatures (25 °C, 45 °C, and 100 °C, i.e. below, close and above the glass transition temperature of the material, T_g, respectively). Differently from literature results reported for amorphous polymers, semicrystalline PBT shows that, after a post-yield deformation, recovery occurs also at temperatures higher than T_g, and that an irreversible deformation, ?_irr, is set in the material. The irreversible strain component has been evaluated as the residual deformation after a thermal treatment of 1 h at 180 °C.After unloading, isothermal strain recovery has been monitored for time periods of 1 h at various temperatures. From the obtained data, strain recovery master curves have been constructed by a time-temperature superposition scheme. The features of the recovery process for the various deformation conditions have been analysed. In particular, it appears that specimens deformed below T_g show a lower irreversible component, whereas, when deformed above T_g, they display a higher irreversible deformation and a slower recovery process. Moreover, the effect of deformation rate appears particularly marked for samples deformed above T_g.     

Lignin-based carbon fibers: Oxidative thermostabilization of kraft lignin

The thermostabilization of lignin fibers used as precursors for carbon fibers was studied at temperatures up to 340 °C at various heating rates in the presence of air. The glass transition temperature (T_g) of the thermally treated lignin varied inversely with hydrogen content and was found to be independent of heating rate or oxidation temperature. A continuous heating transformation (CHT) diagram was constructed from kinetic data and used to predict the optimum heating rate for thermostabilization; a heating rate of 0.06 °C/min or lower was required in order to maintain T_g > T during thermostabilization. Elemental and mass analyses show that carbon and hydrogen content decrease during air oxidation at constant heating rates. The hydrogen loss is sigmoidal, which is consistent with autocatalytic processes. A net increase in oxygen occurs up to 200-250 °C; at higher temperatures, oxygen is lost. Spectroscopic analyses revealed the oxidation of susceptible groups within the lignin macromolecule to ketones, phenols and possibly carboxylic acids in the early stage of the reaction; the later stage involving the loss of CO₂ and water and the formation of anhydrides and possibly esters. Slower heating rates favored oxygen gain and, consequently, higher glass transition temperatures (T_g) as opposed to faster heating rates.     

A model for initial-stage sintering thermodynamics of an alumina powder

A model was proposed to calculate several thermodynamic parameters for the initial-stage sintering of an alumina powder obtained after calcinations at 900 °C for 2 h of a precursor. The precursor was synthesized by an alumina sulphate-excess urea reaction in boiling aqueous solution. The cylindrical compacts of the powder with a diameter of 14 mm were prepared under 32 MPa by uniaxial pressing using oleic acid (12% by mass) as binder. The compacts were fired at various temperatures between 900 and 1400 °C for 2 h. The diameter (D) of the compacts before and after firing was measured by a micrometer. The D value after firing was taken as a sintering equilibrium parameter. An arbitrary sintering equilibrium constant (K_a) was calculated for each firing temperature by assuming K_a = (D_i − D) / (D − D_f), where D_i is the largest value before sintering and D_f is the smallest value after firing at 1400 °C. Also, an arbitrary change in Gibbs energy (ΔG _a°) was calculated for each temperature using the K_a value. The graphs of ln K_avs. 1 / T and ΔG _a° vs. T were plotted, and the real change in enthalpy (ΔH°) and the real change in entropy (ΔS°) were calculated from the slopes of the obtained straight lines, respectively. Inversely, real ΔG° and K values were calculated using the real ΔH° and ΔS° values in the ΔG° = − RT ln K = ΔH° − TΔS° relation. The best fitting ΔH° and ΔS° values satisfying this relation were found to be 157,301 J mol^− 1 and 107.6 J K^− 1 mol^− 1, respectively.     

Silicone-acrylic hybrid aqueous dispersions of core–shell particle structure and corresponding silicone-acrylic nanopowders designed for modification of powder coatings and plastics. Part I – Effect of silicone resin composition on properties of dispersions and corresponding nanopowders

Aqueous silicone-acrylic dispersions with core–shell particle structure can be obtained in the process of emulsion polymerization of acrylic or methacrylic monomers in previously synthesized silicone resin dispersions. If the glass transition temperature (T_g) of the shell is around +120 °C or higher, drying of such dispersions leads to “nanopowders” which can be applied as impact modifiers for powder coatings and plastics due to the presence of low T_g silicone resin contained in the hybrid nanoparticles. The aim of our study was to investigate the effect of silicone resin composition on the properties of dispersions and the corresponding nanopowders what, in turn, was expected to influence the properties of powder coatings modified with such nanopowders. Silicone resin dispersions (DSI) were synthesized by emulsion polymerization of three silicone monomers: octamethylcyclotetrasiloxane (D4), methyltrimethoxysilane (METMS) and methacryloyltrimethoxysilane (MATMS) in the presence of dodecylbenzenesulphonic acid playing the role of both surfactant and polymerization catalyst. Silicone-acrylic hybrid dispersions (DASI) having core–shell particle structure confirmed by TEM were further obtained by emulsion polymerization of methyl methacrylate in DSI, and eventually nanopowders (NP-DASI) were produced by spray-drying of DASI. A designed experiment was conducted where the different proportions of D4, METMS and MATMS were used in DSI synthesis and a range of properties of DSI, DASI and NP-DASI were tested. A significant effect of starting silicone monomers composition (reflected in silicone resin structure) on dispersion particle size was observed what could be explained by differences in their hydrophobicity. SEM investigations revealed that NP-DASI were produced in the form of 1–10 μm agglomerates of round-shaped nanoparticles of ca. 120 nm in size. Two clear glass transition temperatures (T_g) of NP-DASI were identified by DSC: one attributed to silicone part – around −120 °C – and the other attributed to poly(methyl methacrylate) (PMM) part – around +120 °C. T_g attributed to silicone part decreased with increased share of D4 and MATMS in the silicone monomers composition while T_g of PMM part showed a minimum for specific composition of silicone monomers.     

Microstructure and mechanical properties of silicon carbide processed by Spark Plasma Sintering (SPS)

The unique combination of SiC properties opens the ways for a wide range of SiC-based industrial applications. Dense silicon carbide bodies (3.18±0.01 g/cm³) were obtained by an SPS treatment at 2050 °C for 10 min using a heating rate of 400 °C/min, under an applied pressure of 69 MPa. The microstructure consists of fine, equiaxed grains with an average grain size of 1.29±0.65 μm. TEM analysis showed the presence of nano-size particles at the grain boundaries and at the triple-junctions, formed mainly from the impurities present in the starting silicon carbide powder. The HRTEM examination revealed high angle and clean grain boundaries. The measured static mechanical properties (H_V=32 GPa, E=440 GPa, σ_b=490 MPa and K_C 6.8 MPa m^0.5) and the Hugoniot Elastic Limit (HEL=18 GPa) are higher than those of hot-pressed silicon carbide samples.