Concurrent physical aging and degradation of crosslinked coating systems in accelerated weathering

Coating degradation is a combination of both chemical and physical processes; however, physical processes have not received much attention. Physical aging has a non-negligible effect on coatings’ mechanical properties and permeability etc. through the densification that continues as a polymer approaches its thermodynamic equilibrium below the glass transition temperature, T _g. Observations in recent work showed that physical aging affects coatings’ mechanical property response during accelerated weathering and is, itself, affected by the associated chemical degradation. Two crosslinked coating systems were studied in order to compare different chemical compositions, their T _g, and their thermal response in accelerated weathering. During thermal cycling, physical aging measured by enthalpy recovery exhibited different trends in the two coatings. A “rejuvenation” mechanism was observed in the coating with a T _g between the top and bottom limits of the exposure cycle; continued aging was observed for the coating with a high T _g. Stress relaxation tests detected aging and “memory” behavior over periods comparable with accelerated weathering cycles. Both thermal and mechanical responses changed in complicated and different ways as the coatings degraded. Different degrees of coating thickness reduction were observed in both isothermal relaxation and degradation. When various coatings are evaluated, simply judging their performance under the same weathering environment is not reliable since polymer relaxation behavior depends on the relationship between the exposure temperatures and the T _g of each polymer. This paper was awarded First Place in the 2007 Gordon Awards technical paper competition, held as part of the FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in Toronto, ON, Canada, on October 3–5, 2007.     

Interpenetrating polymer network from blocked isocyanates. I. Structure and properties of polyurethane-urea polyvinyl simultaneous interpenetrating networks

A series of polyurethane-urea/polyvinyl simultaneous interpenetrating polymer networks (SINs) were prepared starting from a mixture of isocyanate prepolymer blocked with N-(1-1′-dimethyl-3-cxobutyl) acrylamide oxime, chain extender, vinyl monomers, and catalysts. Their physical properties and morphology were investigated using differential scanning calorimetry, dynamic mechanical measurements, and small-angle X-ray scattering. The polyurethane-urea networks examined were two-phase in nature. The vinyl network was formed with diacetone acrylamide oxime, trimethylolpropane trimethacrylate, and N-vinyl-pyrrolidone. Calorimetric analyses revealed that the polyether soft segment phase separated within the SINs. At higher temperature, dynamic mechanical measurements demonstrated the presence of only one glass transition temperature (T_g) intermediate in temperature to the T_g of the vinyl network and the T_g of the urethane hard phase. This is indicative of chain entanglement (interpenetration) between the vinyl network and the polyurethane hard segments resulting in a two-phase morphology. Small-angle X-ray scattering analyses provided measurements of diffuse phase boundary thickness, phase mixing, and domain size distribution. Appreciable interfacial thickness was not observed and thus phase mixing occurred within the phases. Domain size distribution indicated that high network constraints hindered the development of domains and limited the phase segregation.     

Effect of post-cure on the glass transition temperature and mechanical properties of epoxy adhesives

The effects of post-curing and cure temperature on the glass transition temperature, T _g, and the mechanical properties of epoxy adhesives were studied. T _g was measured by a dynamic mechanical analysis apparatus developed in-house and the mechanical properties of the adhesives (yield strength, Young’s modulus and failure strain) were measured by a tensile machine. The relationships between T _g and mechanical performance under various post-cure conditions were investigated. The curing process was the same for all tests, consisting of an initial stage performed at different temperatures followed by cooling at room temperature. Three sets of specimens were considered, sharing the same initial cure process, but with a different post-curing procedure. In the first set, the specimens were only subjected to a curing process; in the second set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature below the T _g of the fully cured network, T _g∞; and in the third set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature above the T _g∞. When post-cured at a temperature above T _g∞, the mechanical and physical properties tend to have a constant value for any cure temperature.     

Characterization of polymer-coated optical fibers using a torsion pendulum

A freely oscillating torsion pendulum has been used to characterize the dynamic mechanical behavior of single polymer-coated optical fibers. The dynamical mechanical spectra of the polymer coatings exhibit a glass transition temperature (T_g), a cryogenic glassy-state relaxation (T_sec), and another cryogenic relaxation that is attributed to water present in the coating (TH₂O). The shear modulus (G′) of the coating was computed from the shear moduli of the composite specimen and the core, assuming that the coating and core deform through the same angle on oscillation. The glassy-state modulus was the same for both thin and thick coatings, although the intensity of the damping peaks, as measured by the logarithmic decrement, increased with coating thickness. Comparison of the dynamic mechanical behavior of a coated optical fiber and of a free film cast from the same reactive components shows that the polymer itself can absorb water at ambient conditions and display a mechanical relaxation at cryogenic temperatures. The T., H₂O and T_sec relaxations are coupled with respect to their intensities. Latent chemical reactivity was found in one coating above its maximum temperature of cure. In this, the temperature of cure determines the glass transition temperature.     

Effect of MoS2 content on friction and wear properties of Mo and S co-doped CrN coatings at 25–600 °C

With increasingly harsh working environments for mechanical systems and the rapid development of various high-tech industries, requirements for the stable operation of mechanical systems are increasing in a wide temperature range. Mo and S co-doped CrN coatings with different MoS₂ contents were prepared via unbalanced magnetron sputtering to provide better friction properties to the coatings at high temperatures. Scanning electron microscopy and nanoindentation were adopted to analyze the microstructure and mechanical performance. The mechanical performance of the coatings was enhanced by increasing the MoS₂ content, however, excessive MoS₂ reduced the mechanical properties of the coatings. Besides, the adhesion of the coatings first increased and then decreased rapidly with the increase of the MoS₂ content. In addition, the residual stress of the coating first decreased and then increased upon increasing the MoS₂ content. The high-temperature tribological behavior of the coatings was measured from room temperature (25 °C) to 600 °C. The CrN/MoS₂-0.6A coating was found to exhibit low friction and wear coefficient at room temperature and relatively good comprehensive properties at high temperature. This study provides a feasible design for engineering applications and lays the foundations for the preparation of coatings with superior high-temperature friction properties.     

Combined effect of relative humidity and temperature on dynamic viscoelastic properties and glass transition of poly(vinyl alcohol)

On the basis of the experimental studies on viscoelastic properties of poly vinyl alcohol (PVA) films at various relative humidity (RH) and temperature conditions by dynamic mechanical analysis (DMA), the influence of both temperature and RH on the glass transition are discussed and an improved property model is developed to relate the dynamic modulus to RH and temperature. The results indicate that (1) with increasing the RH, the storage modulus of PVA decrease remarkably, while both loss modulus and tanδ sharply increase to reach the peak and then markedly drops. The intensity of this variation is highly dependent upon temperature. (2) Moisture increase will cause the glass transition of PVA at isothermal condition and the transition point can be detected by glass transition relative humidity (RH_g) that obtained by isothermal RH scans. (3) Similar to the relationship between T_g and RH, the RH_g of PVA vary linearly with temperature. The state diagram of RH_g versus temperatures is nearly consistent with that of T_g versus RH. (4)The present equation based on model of Mahieux and Reifsnider (Mahieux and Reifsnider, Polymer 2001, 42, 3281) can predict well the dynamic modulus of PVA at various RHs and temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3161–3167, 2013     

Thermomechanical properties of blends of pectin and poly(vinyl alcohol)

Blends of citrus pectin and several types of poly(vinyl alcohol) were investigated to determine the effects of compositional variables and polymer type on film properties. Some films were also plasticized with glycerol. Films were cast from water onto Lexan™ plates, dried, and removed. Thermomechanical properties were obtained using a dynamic mechanical analyzer, and thermodynamic transitions were also obtained using a differential scanning calorimeter. Increasing the amount of poly(vinyl alcohol) in the blends reduced the storage and loss modulus of the films above the glass transition temperature (T_g). The T_g values observed decreased as the amount of PVOH in the blend increased. Addition of glycerol depressed the PVOH T_g and merged it into the T_g of the pectin/glycerol blend. Changes in the molecular weight and degree of ester hydrolysis of poly(vinyl alcohol) exerted a rather small effect on the blends. © 1996 John Wiley & Sons, Inc.

1 Reference to a brand or firm name does not constitute an endorsement by the U.S. Department of Agriculture over others of a similar nature.

     

Effects of molecular interactions on the viscoelastic and plastic behaviour of plasticized poly(vinyl chloride)

The mechanical behaviour of plasticized poly(vinyl chloride) in the glassy state was revisited in order to provide some understanding of the properties observed on the molecular scale. Nine samples were investigated, consisting either of pure poly(vinyl chloride) or of plasticized formulations including different amounts of di‐octyl phthalate or benzyl butyl phthalate in the range 5–20 wt%. Presence of the additives resulted in the depression of the glass transition temperature, T_g, and the main mechanical relaxation temperature, T_α, as determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. These expected results were related to the plasticizing character of the additives on the long‐range cooperative polymer motions. In addition, a marked reduction of the secondary mechanical relaxation β was observed for additive concentrations equal to or larger than 10 wt%. This antiplasticizing effect was interpreted as the hindrance of main‐chain local polymer motions, due to poly(vinyl chloride)–additive interactions. Occurrence of such interactions was confirmed by mid‐ and near‐infrared measurements. The plastic behaviour of the materials in the glassy state was also examined. Particular attention was paid to the strain‐softening amplitude (difference between yield stress and plastic flow stress), to the percentage of non‐elastic deformation and to the mechanical energy to yield. All these quantities are strongly affected by the chain‐mobility characteristics. Copyright © 2003 Society of Chemical Industry     

Novel aprotic polar polymers 3. Synthesis and properties of poly(phenyl vinyl sulfoxide)

Summary Poly(phenyl vinyl sulfoxide) 1 was prepared by anionic polymerization and its properties as a polymer homolog of dimethyl sulfoxide (DMSO) were examined. Polysulfoxide 1 was found to have good miscibility with poly(vinyl acetate) as well as poly(2-methyl-2-oxazoline) and poly(N-vinylpyrrolidone) by comparing glass transition temperature(s) (T_gs) of the mixture of these polymers with T_gs of the original polymers by differential scanning calorimetry. Received: 4 March 1998/Accepted: 23 March 1998     

Polymer coatings by electropolymerization of some vinyl monomers

Electroinitiated polymerization coatings are uniform, thin, tightly adherent, conformal, and economical to produce. This article describes use of a novel (for electropolymerization) persulfate initiator to rapidly polymerize a moderate T_g crosslinked acrylic coating. Polymer coatings derived from the monomers acrylamide, acrylonitrile, and N,N′-methylenebisacrylamide were synthesized on an aluminum cathode by persulfate electroinitiated polymerization at room temperature. The crosslinked polymer was brittle (T_g = 239°C) but thermally stable (degradation temperature = 310°C). The coatings were spongy and contained some small cracks when polymerized at low current density (0.1 mA/cm²). However, thicker coatings with fewer cracks were obtained at higher current densities. Persulfate was found to be an effective initiator for polymerization in this system, and the initiation mechanism was confirmed to be free radical. In general, it appears possible to produce thin, uniform coatings on aluminum by this route. © 1995 John Wiley & Sons, Inc.     

Analysis of the dielectric spectra of composite sealing coatings in a wide frequency range

Polymer coatings on the basis of the biphenol-Novolac potting epoxy compound with a 65% content of spherical particles of fused quartz as a filler were studied by the method of dielectric spectroscopy in a wide frequency range. Dielectric measurements were performed in frequency and temperature ranges of (10⁻² to 5 × 10⁹) Hz and 20 to 200°C, respectively, on film samples of composite coatings formed on different substrates. It was shown that the application of dielectric spectroscopy allows one to study the effect of the degree of the adhesion interaction with the substrate on the processes of structuring in the epoxy polymer matrix and to investigate the degradation processes in the coatings under the effect of high temperature and relative humidity. It was also shown that the values of the glass transition temperature (T _g ) of the composite determined by applying the method of low-frequency dielectric spectroscopy agree well with the T _g values obtained by applying the method of dynamic mechanical analysis (DMA).     

Processing-property relationships in compression molding of sheet molding compounds

An experimental investigation was conducted into establishing relationships between the processing variables and the mechanical properties of compression-molded parts of sheet molding compounds (SMC). Emphasis was placed on investigating the effects on the tensile properties, impact strength, and dynamic mechanical properties of composite specimens, of low-profile additives, and of treating glass fibers (for reinforcement) with sizing chemicals. The processing variables investigated were cure time, mold temperature, and mold pressure. It was found that: (1) An optimum cure time and mold temperature exist for achieving molded SMC composites of the greatest tensile and impact strengths; (2) Of the four different types of low-profile thermoplastic additives employed, the poly(vinyl acetate) modified with acrylic acid gives rise to molded SMC composites having the greatest tensile and impact strengths; (3) An optimum cure time and mold temperature exist for achieving the highest glass-transition (T_g) of the low-profile additive; (4) The values of cure time and mold temperature that have yielded the greatest tensile and impact strengths also yield molded specimens having the highest T_g of the low-profile additive.     

A study on the anticorrosion performance of the epoxy-polyamide nanocomposites containing ZnO nanoparticles

Epoxy nanocomposites were prepared using different loadings (2, 3.5, 5 and 6.5 wt%) of ZnO nanoparticles. Nanocomposites were applied on steel substrates. Samples were immersed in 3.5 wt% NaCl solution for 1344 h. Corrosion resistance of the coatings was studied by an electrochemical impedance spectroscopy (EIS). The effects of addition of nanoparticles on the mechanical properties of the epoxy coating were studied by a dynamic mechanical thermal analysis (DMTA). Curing behavior of the coatings containing nanoparticles was studied by a differential scanning calorimeter (DSC). Atomic force microscope (AFM) was utilized to investigate the surface topography and surface morphology of the coatings. Coating resistance against hydrolytic degradation was studied by FTIR (Fourier Transform Infrared).Results showed that addition of low loadings of nanoparticles can increase T_g of the composite. Decrease in T_g and cross-linking density of the coating were observed at high loadings of nanoparticles. It was found that nanoparticles can influence the curing behavior of the epoxy coating. Nanoparticles improved the corrosion resistance of the epoxy coating. Increase in coating resistance against hydrolytic degradation was obtained using nanoparticles.     

Pultruded fiber reinforced blocked polyurethane (PU) composites. II. Processing variables and dynamic mechanical properties

Unidirectional fiber reinforced blocked polyurethane (PU) composites have been prepared by the pultrusion process. The effects of processing variables on the mechanical properties and dynamic mechanical properties of fiber reinforced PU composites by pultrusion have been studied. The processing variables investigated included pulling rate (in-line speed), die temperature, postcure time and temperature, and filler type and content. The dynamic mechanical properties of the composites produced by the process were studied utilizing dynamic mechanical spectrometer. Results show that the composites possessed various optimum pulling rates at different die temperatures. From the DSC data analysis, swelling ratio, and mechanical properties, the optimum die temperature was determined. It was found that the mechanical properties increase with filler content for various types of filler. The increasing of mechanical properties depends on the optimum postcure temperature and time. However, the properties decreased for longer postcure times since the composite materials were degraded. The glass-transition temperature (T_g) increased slightly and the damping peak (tan δ) was broadened due to fiber reinforcement. The dynamic mechanical moduli (G′, G″) of pultruded PU composites are apparently higher than those of the matrices. The moduli (G′, G″) increase with increasing fiber and filler content, and the damping peak becomes broad. Effect of postcuring on the degree of crosslinking, T_g, and dynamic modulus will be discussed.     

Effect of methyl methacrylate content on coatings’ properties of palm oleic acid-based macromer

The macromer was synthesized using medium oil length oleic acid, phthalic anhydride, and glycerol. The synthesized macromer and methyl methacrylate (MMA) were copolymerized by free radical polymerization in toluene. The ratio between the macromer and MMA changed, and the effects on different properties of the copolymers, such as glass transition temperature (T _g) and film properties, were studied. The macromer and copolymer structures were characterized by FTIR and ¹H NMR spectroscopies. The coatings prepared with the highest ratio of MMA exhibited better overall physico-chemical properties. Alternatively, Tafel polarization curves showed that the corrosion rate value in NaCl solution decreases significantly when the MMA content is increased. Dynamic mechanical analysis results revealed that the increasing amounts of MMA lead to increasing T _g values of copolymers.     

Dynamic mechanical and thermal properties of fire-retardant high-impact polystyrene

The interaction of a series of fire-retardant additives with high-impact polystyrene (HIPS) has been inferred from their dynamic mechanical and thermal properties. High-melting additives phase separate and act as inert filler in both the rubber and polystyrene phases, while low-melting additives raise the T_g of the rubber phase and plasticize the polystyrene phase. Antimony oxide antiplasticizes the grafted rubber phase but acts as inert filler in the polystyrene phase. The impact strength of these fire-retardant HIPS's shows good correlation with the integrated loss tangent of the rubber T_g peak indicative of large energy dissipation in the rubbery region during impact causing the matrix to craze or flow. It is also suggested that additives which are compatible with, and localized in, the polystyrene phase help retain the impact strength of HIPS.     

Epoxy–lignin polyblends. III. Thermal properties and infrared analysis

Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and IR analysis were performed on a nonviscous epoxy polymer system (EP) with Kraft lignin (L) up to 20%. Mixtures of EP with similar amounts of silica (S) as in EP–L polyblends were used as a reference system for the analyses performed. EP–L polyblends cured at room temperature exhibit a single T_g, a fact characteristic for the monophasic systems. One-step tensile storage modulus vs. temperature curves, and related one-peak tensile loss modulus vs. temperature curves were found for all the EP–L polyblends. At about 30°C the tensile storage modulus of EP does not change in the presence of lignin in amounts up to 20% by weight. All these showed that L is miscible with EP and it does not affect the crosslinking at room temperature. IR spectra led to similar conclusions. The gradual decrease of the peak values of tan δ with the amount of L in polyblends is due to an increase in the tensile storage modulus and a decrease of the tensile loss modulus at temperatures close to T_g. This fact is explained by a stronger bond between EP and L, which could be formed at higher temperatures. The DSC and DMA data are in agreement with the mechanical properties of EP–L polyblends, which were reported previously.     

Mechanical properties of sol–gel prepared nanocomposite coatings in the presence of titania and alumina-derived nanoparticles

Hybrid nanocomposite coatings were prepared by sol–gel method using silica, titania and alumina nanoparticles derived from their alkoxides precursors; in the presence of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) on 1050 aluminium alloy substrate. The effect of type and ratio of nanoparticles on mechanical behaviour of the coatings were investigated by dynamic mechanical thermal analysis (DMA) and nanoindentation experiments. DMA results demonstrated that the values of the glass transition temperature (T_g) and the temperature at maximum tan (δ), (T_t) as well as the storage modulus of the hybrid samples depend mainly on the silane content and titania to alumina molar ratio of nanoparticles in the coating composition. In addition, nanoindentaion experiments were performed to study the mechanical properties such as hardness, elastic modulus and E/H ratio for the nanocomposite hybrid coatings. Nanoindentation results indicate that the homogenous reinforced structure was formed in the surface of nanocomposite coating with incorporation of titania and alumina-derived nanoparticles. The incorporation of TiO₂ in comparison with AlOOH nanoparticles in the GPTMS-based coatings showed an improving effect on E/H ratio.     

Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity

Poly(lactide) (PLA) is rapidly gaining interest as a biodegradable thermoplastic for general usage in degradable disposables. To improve mechanical properties, a PLA with low stereoregularity was blended with polyethylene glycol (PEG). Blends with up to 30 wt% PEG were miscible at ambient temperature. Blending with PEG significantly decreased the T_g, decreased the modulus and increased the fracture strain of PLA. However, the PLA/PEG 70/30 blend became increasingly rigid over time at ambient conditions. The mechanism of aging primarily under ambient conditions of temperature and humidity was studied. Changes in mechanical properties, thermal transitions and solid state morphology were examined over time. Aging was caused by slow crystallization of PEG. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the T_g. As T_g approached the aging temperature, reduced molecular diffusivity slowed the crystallization rate dramatically. Aging essentially ceased when T_g of the amorphous phase reached the aging temperature. The increase in matrix T_g and the reinforcing effect of the crystals produced a change in mechanical properties from elastomer-like to thermoplastic-like.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.