Investigation on the structure-property relationships for films obtained from UV curable coatings

A number of poly(ethyleneglycol)- and poly(propyleneglycol)- , ω-diacrylates, with different MW in the range 200–2000, were subjected to UV curing as thin films and the properties of the obtained crosslinked polymers were investigated. The total double bond conversion was determined by Fourier transform infrared spectroscopy (FTIR). Direct scanning calorimetry (DSC), thermal mechanical analysis (TMA) and dynamic-mechanical thermal analysis (DMTA) were used to evaluate the thermal and dynamic-mechanical behaviour of the networks obtained. The double bond conversion was found to be always complete, with the exception of the lowest MW oligomers. T_g values were found to decrease with increasing the MW of the oligomers used for both series. The equilibrium swelling in water was found to increase with increasing MW that is with decreasing the crosslinking density of the network. Mixtures of different oligomers with a typical epoxyacrylate resin were also examined. A sharp increase of the total double bond conversion in the presence of the oligomers was observed. The T_g values of the obtained films were found to decrease with increasing oligomer MW in agreement with the data obtained by using the pure acrylate oligomers. The results obtained are discussed in terms of the crosslinking density of the networks formed in the curing process.     

Preparation and properties of disyndiotactic poly(alkyl crotonate)s

Ethyl, n-propyl, iso-propyl and n-butyl crotonates were polymerized by group transfer polymerization (GTP) using ketene trialkylsilyl acetals as initiators in the presence of mercury (II) iodide as catalyst and iodotriethylsilane as co-catalyst. Predominantly disyndiotactic polymers with number-average molecular weights ranging from 56,000 to 90,000 were obtained almost quantitatively. Thermal and mechanical properties of poly(alkyl crotonate)s, such as glass transition temperature (T_g), refractive index, transmissivity, Izod impact strength, Young's modulus, hardness, tensile strength, tensile elongation at break, gas permeability coefficient and density were measured. All the polycrotonates have 65–90 °C higher T_g than the corresponding polymethacrylates.     

Preparation and properties of novel poly(urethane-imide)s

A series of poly(urethane-imide)s were prepared by a novel approach. Polyurethane (PU) prepolymer was prepared by the reaction of polyester polyol and 2,4-tolylenediisocyanate (2,4-TDI), and then end-capped with phenol. The PU prepolymer was blended with poly(amide acid) or oligo(amide acid) prepared from 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and oxydianiline (ODA) at room temperature in various weight ratios. The blend films obtained by casting and then drying were not transparent, suggesting that phase separation occurred between the polyimide (PI) and PU components. The films became transparent, however, after thermal treatment at 100°C and then 200°C for 1 h each, irrespective of the ratio of the two components. The poly(urethane-imide) films showed good solvent-resistance. Dynamic mechanical analysis of the films showed that glass transition temperatures (T_g) shifted depending on the ratio of PI and PU components. This shift of T_g, along with the transparency of the films, suggests that the PU and PI components employed here are miscible to some extent and that domains of each phase by microphase separation are small. Tensile measurement of the blend films from poly(amide acid) showed that the films are plastic or elastic, depending on the ratio of the components. Thermal stability of the PU was found to increase by the incorporation of polyimide component.     

Imide-aryl ether benzoxazole random copolymers

Novel imide-aryl ether benzoxazole copolymers were prepared and their morphology and mechanical properties investigated. A key feature of these copolymers is the incorporation of a benzoxazole moiety by the use of 2,2′-bis[4-(3-aminophenoxy)phenyl]-6,6′-bibenzoxazole or 2,2′-bis[4-(4-aminophenoxy)-phenyl]-6,6′-bibenzoxazole as co-diamines in polyimide syntheses. The preparation of these diamines involved the nucleophilic aromatic substitution of 2,2′-bis(4-fluorophenyl)-6,6′-bibenzoxazole with either 3- or 4-aminophenol in the presence of K₂CO₃. The diamines were co-reacted with various compositions of pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) to synthesize the desired poly(amic acids). Films were cast and cured (350°C) to effect the imide formation, affording films with elongations between 40 and 110% and moduli in the 2000–2750 MPa range. The copolymers exhibited good dimensional (T_g in excess of 300°C) and thermal stability. Wide-angle X-ray diffraction measurements on the copolymers showed that the ordered morphology characteristic of PMDA/ODA polyimide was retained. Improvements in the auto-adhesion were observed, particularly in those copolymers which displayed a T_g.     

Effect of water on relaxations in the glassy and liquid states of poly(propylene oxide) of molecular weight 4000

The complex relative permittivity of poly(propylene oxide) (PPO) of molecular weight 4000 containing 1.23 wt% water has been measured in the temperature range 77 to 325 K and frequency range 12 Hz to 500 kHz, and the results are compared with the corresponding study of pure PPO-4000. On the addition of water, all the three processes, namely the β-process (at T < T_g) and the - and ′-processes (at T > T_g), are shifted to higher temperatures. The strength of the β-process remained unchanged but that of the and ′-processes increased. The halfwidths of the three processes remained unchanged on dilution with water. The decrease in the relaxation rate of the β-process is suggested to be due to hydrogen bonding of the ---CH(CH₃)---O---CH₂--- group with water molecules. Water antiplasticizes PPO-4000 and this is interpreted as due to the increased chain length when the chain ends become linked via hydrogen bonds. The static permittivity is increased by 30% on addition of 1.23 wt% water.     

The glass temperature of polymer blends

The entropy theory of glasses is used to derive the glass temperature, T_g, of a binary polymer blend in terms of the glass temperatures of the two substituents. The formula is T_g = B₁T_g1 + B₂T_g2, where B_i is the fraction of flexible bonds of substituent i. A bond is flexible if rotation about it changes the shape of the molecule. Bonds in side groups as well as in the backbone are to be counted. This formula assumes that the free volume, taken here to be the volume fraction of empty lattice sites, is the same for each of the three materials. It has no parameters. The above equation expressed in weight fractions, W_i, is (T_g − T_g1)W₁(γ₁/ω₁) + (T_g − T_g2)W₂(γ₂/ω₂) = 0, where ω_i is the weight of a monomer unit and gg_i is the number of flexible bonds per monomer unit. A more general treatment is given. One variation of the more general treatment which expresses the properties of the blend in purely additive terms gives T_g = B₁T_g1 + B₂T_g2 + KB₁B₂(T_g1 − T_g2)(V₀₁ − V₀₂), where V_0i are the free volume fractions of the homopolymers at their glass temperatures and K is a constant. The added term is usually small. The most general form of the equation requires the energy of interaction between the two unlike molecules, which can be estimated by volume measurements on the blend.     

Cooperative relaxations in amorphous polymers studied by thermally stimulated current depolarization

Thermally stimulated current depolarization (t.s.c.) was used to study the relaxations in amorphous polymers including poly (ethyl methacrylate) (PEMA), poly (methyl methacrylate) (PMMA), polystyrene (PS), polycarbonate (PC) and polyarylate (PAR) over temperature ranges covering the β and (glass transition) regions. A.c. dielectric was used to obtain activation energies (E_a) for PS and PC to verify the accuracy of those values determined by the t.s.c. thermal sampling method. At temperatures below the glass transition (T_g) the values of E_a were found to agree with those predicted using an activated states equation with a zero activation entropy. This is evidence of the localized, non-cooperative nature of the low temperature secondary β relaxations which are found to be characterized by a continuous variation of activation energies as a function of temperature. The measured values of E_a depart from the zero activation entropy curve and exhibit a prominent maximum at T_g. This behaviour is known to be due to an enhanced degree of cooperativity of segmental relaxations near T_g. The results indicate that the main advantage of the thermal sampling method is the high sensitivity and high temperature resolution for cooperative relaxations. For the polymers studied here, only PEMA and PMMA show a substantial population of cooperative relaxations more than 60°C below T_g. This is tentatively explained in terms of structural heterogeneity due to variable tacticity in the methacrylates. Compensation of the t.s.c. relaxation spectra plotted in Arrhenius or Eyring plots was found for all polymers to differing degrees. Some discussion of compensation is made in terms of independently measured values of the coefficient of thermal expansion.     

Structure/property studies of MF-cured powder coatings

Thermoset powder coating films have been prepared from commercial hydroxy-functional polyester resins (PE) by crosslinking with toluene sulfonamide-modified melamine formaldehyde crosslinkers (TS-MF). Solvent resistance, hardness and impact resistance determinations have been made on films cured over a wide range of temperatures and with numerous variations in composition and characteristics of PE and TS-MF components. Cure behavior, as revealed by these ‘property profiles’, is discussed in terms of component structures and curing reactions. Selected films from property-profile studies have been characterized by dynamic mechanical analysis (DMA). Properties are compared for solvent-applied and powder-applied films prepared from the same compositions. Unexpected and potentially important new findings are reported on catalysis and pigment reinforcement. Crosslink densities from DMA and theory are compared.     

Effects of freeze-drying on the glass temperature of cyclic polystyrenes

The calorimetric glass temperature was measured for three cyclic polystyrenes with apparent molecular weights ranging from 4.0×10³ to 195.5×10³ g/mol for both bulk material and for samples freeze-dried from dilute solution. Freeze-drying from dilute solution was found to reduce the glass temperature by 7–14 K depending on the sample. These T_g depressions are 5–12 K greater than those found previously for freeze-dried linear polystyrene. Annealing at 403.2 and 443.2 K (130 and 170 °C) resulted in recovery of the T_g back to the bulk value with the time scales depending on both temperature and the magnitude of the T_g reduction; the low apparent activation energy dependence of the recovery of T_g precludes its being due to viscous flow.     

Inversion to obtain aerosol size distributions from measurements with a differential mobility analyzer

To measure size distributions of submicrometer aerosols with an electrical differential mobility analyzer (DMA) requires an inversion procedure. The Knutson (1976) and the Hoppel (1978) inversion procedures were numerically investigated for the case of log-normal aerosol size distributions. It was found that the Hoppel procedure converges to the same result as that given by the Knutson procedure. The computational range for geometric mean diameter ( _g) was 0.025-0.25 μm, and for geometric standard deviation (σ_g) was 1.1–2.4. The inversion error was found to be greater than 10% in certain “forbidden zones” of _g and σ_g values. For the case of an ideal DMA having no lower mobility limit, only one forbidden zone exists, this consisting of small σ_g values. The boundary of this forbidden zone intercepts the computational range boundaries at σ_g = 1.25, and σ_g = 1.62, . These results also apply to an actual DMA when the size distribution of particles larger than the DMA singly charged mobility limit is available a priori. If such information is not available, the concentration of these larger particles is assumed to be zero in performing the inversion. This assumption adds a second forbidden zone, consisting of large σ_g values and having the intercepts σ_g = 2.44, and σ_g = 1.50, . The first forbidden zone remains nearly the same.     

Relations between structure and properties in bisphenol A polyester carbonates

A range of hydroxy-terminated polybisphenol A terephthalate and isophthalate blocks have been prepared with molecular weights 800–5000, which were then coupled with phosgene to give alternating polyester copolycarbonates. These materials have been characterized by their physical, thermal and mechanical properties. The thermal properties have been investigated using differential scanning calorimetry and the glass transition temperatures, specific heats and Δcps′ (at the T_g) values obtained. A relationship appears to exist between Δcp and the reciprocal molecular weight of the polyester blocks, and the molar ratio of ‘ester’ to carbonate of the copolycarbonates. A maximum in the glass transition temperature has also been observed in the copolycarbonates, corresponding to a certain ‘ester’: CO₃ ratio. Tensile mechanical analyses have been performed on cast or moulded films of the copolycarbonates. The terephthalates can give films which extend uniformly but the isophthalates always neck.     

Small angle neutron scattering studies of composite latex film structure

The mechanical properties and structure of composite films made of high T_g polystyrene (PS) nodules dispersed in a low T_g polybutylacrylate (PBuA) matrix were studied by means of dynamic mechanical spectrometry and small angle neutron scattering. For films cast from mixtures of PS and PBuA latexes, film mechanical reinforcement was obtained above a percolation threshold of about 30% PS volume fraction. A segregation of PS particles into dense clusters in the PBuA continuous matrix, reminiscent of a phase separation, was observed. For films cast from core-shell particles, this segregation phenomenon may be prevented, depending on the coverage of the PS core by the PBuA shell. An efficient core encapsulation in the core-shell morphology leads to poor contact between PS cores, and the elastic moduli are then close to that of the PBuA matrix. Upon annealing the films above the T_g of PS, extensive coalescence of PS particles occurred when large contacts were already present in the dry film at room temperature, and a percolating network of coalesced PS domains provides large elastic moduli at temperatures between the T_g of PBuA and PS. The coalescence was prevented when PS particles were taken apart by the PBuA shell.     

Ultraviolet light absorber mobility in crosslinked coatings: Experiments and modeling

The diffusion of an ultraviolet absorber (UVA) across a concentration step change in an acrylic melamine clearcoat was measured via micro-ultraviolet spectroscopy. Concentration profiles were obtained after diffusion times of 4–200 h at steady temperatures of 70, 80, and 90 °C. The glass transition temperature of the coating was measured via dynamic mechanical analysis for each time–temperature pair, and T_g was observed to increase with thermal aging, with a faster rate of increase at higher aging temperatures. The change in T_g was modeled using a first-order dependence on the deviation from a long-time T_g asymptote. The diffusion coefficient was then represented by a free volume expression, and the combination provided an accurate model of the measured concentration profiles. The time-dependent increases in glass transition temperature helped to explain why UVA diffusion does not alleviate concentration gradients created by photooxidation under natural weathering conditions.     

Intermacromolecular complexes by in situ polymerization

Hydrogen-bonded complexes of poly(acrylic acid) and poly(ethyl oxazoline) (PEOx) were prepared by photopolymerization of acrylic acid in which PEOx was dissolved. The glass transition temperatures (T_g) of the complexes are not only higher than those of the blends but also higher than the T_g value of either component polymer. The complexes dissolve in strong proton-accepting solvents like dimethyl formamide or dimethyl sulphoxide (DMSO), are swollen to various degrees in water and methanol, but are resistant to swelling by dioxane. When the density of hydrogen bond donor groups in the chain is reduced by 50% with the use of a copolymer of acrylic acid and methyl methacrylate, intermolecular association still takes place, although the affinity of complexation is reduced to some extent. When interpenetrating networks (semi-IPNs) are prepared by this method, about half of the PEOx can be extracted by DMSO after 4 days. The incomplete removal is probably a result of topographical constraints against diffusion.     

Film formation from cationic electropaint systems containing resins with different glass transition temperature

Some phenomena in the deposition process of electropainting have not been well elucidated till now. In this paper, to investigate an influence of glass transition temperature (T_g) on film formation, the deposited film was observed with an atomic force microscope and the electrochemistry was investigated, using two kinds of cationic acrylate resin with different T_g (methyl methacrylate system (MMAs): T_g=70°C, and methyl acrylate system (MAs): T_g=5°C). Electrodeposition was performed under constant voltage or current condition.

At constant voltage, the deposition behavior in the two resin systems differed extremely. The MMAs, the resin with high T_g, produced a high resistance film. The MAs, the resin with low T_g, was deposited forming a film at a voltage lower than 20 V. At constant current, the film formation did not result in a rise in voltage. It behaved like a conductive film. When the resin with high T_g was used, particulate deposits were observed by AFM even in the induction period. The resin with low T_g formed flat deposits. These results suggest that paint deposition is initiated once electrolysis of water starts. In addition, there are two types of film formation on the cationic electropainting: high resistance film formation for the resin with high T_g, and ion-permeable film formation for the resin with low T_g. In both cases, film growth occurs at the film/bulk solution interface.     

Towards anti-corrosion coatings from surfactant-free latexes based on maleic anhydride containing polymers

We report on the film formation of surfactant-free, artificial latexes based on copolymers containing maleic anhydride. Different metallic substrates, such as aluminum, steel and magnesium alloys, were coated with three different latexes. A commercial polyester based coating was used as a comparative sample. Two of the latexes were based on polymer with a high T_g (resp. 100 and 130 °C), and one on a polymer with a T_g of −70 °C. The wetting of the substrates could be optimized by etching the metal substrate, acidic or alkaline, leading to homogenous film formation and improved adhesion. For aluminum substrates an alkaline pretreatment improved the adhesion with the polymer films, whereas for magnesium the acidic pretreatment improved the adhesion. Furthermore, acid pretreatment increased the corrosion resistance of the coated magnesium substrate, when compared to an alkaline pretreatment. The films formed from latex displayed comparable or better anti-corrosive properties when compared to the commercial polyester.     

Diffusion controlled kinetics of crosslinking

Reactions of polymer formation and crosslinking become diffusion controlled when, during the reaction, the increasing glass transition temperature T_g comes close to the reaction temperature, the reaction still goes on below T_g but the reaction rate decreases steeply. A theory is presented relating the apparent rate constant to the difference between the reaction temperature and T_g based on the free volume or the Adam-Gibbs theory of glass transition. The theory is correlated with experiments on curing of diglycidyl ether of bisphenol A with 1,3-propanediamine. The implications for formation of protective films chemically crosslinked are discussed. The presence of a solvent and its evaporation affects the reaction rate through a change in concentrations of reactants as well as in T_g.     

Blends of amorphous and crystalline polylactides with poly(methyl methacrylate) and poly(methyl acrylate): a miscibility study

Blends of amorphous and crystalline polylactides (PDLA and PLLA) with poly(methyl methacrylate) (PMMA) and poly(methyl acrylate) (PMA) have been prepared. Thermal behaviour and miscibility of these blends along the entire composition interval were studied by differential scanning calorimetry (d.s.c.). The results were compared with those obtained by dynamic mechanical analysis (DMTA). Only one T_g was found in PDLA/PMA and PDLA/PMMA blends, indicating a high degree of miscibility in both systems. Nevertheless, the PDLA/PMMA blend presented enlargements of the T_g width at high PMMA contents. In this case, additional evidence of complete miscibility was obtained by studying the evolution of the enthalpic recovery peaks which appear after different thermal annealing treatments. When the polylactide used was semicrystalline (PLLA), once the thermal history of the blends had been destroyed, crystallization of PLLA was disturbed in both blends PLLA/PMMA and PLLA/PMA, but in a rather different fashion: in the first case crystallization was almost prevented while in the second one it was favoured. This behaviour was explained in terms of the effect of the higher stiffness as indicated by the value of T_g for PMMA compared to that for PMA.     

Tetrafunctional acrylates based on β-hydroxy alkyl amides as crosslinkers for UV curable coatings

Ultraviolet (UV) curable coating formulations were prepared from novel crosslinking acrylates synthesized from β-hydroxy alkyl amides. Variations were done with respect to the nature of the monomer backbone by introducing aliphatic, aromatic and cycloaliphatic structures in between the amide groups. The synthesized multifunctional alcohols and acrylates were subjected to IR and NMR analysis for structure confirmation. The acrylates were dissolved in chloroform and the UV–vis spectrum was recorded to substantiate the presence of carbonyl group conjugated to the vinyl group. The new acrylates were added to basic formulation and exposed to UV radiation to get transparent films. The dynamic mechanical properties of the films cast from the formulations were assessed and studies on the effect of the synthesized crosslinking acrylate content and their nature on the viscoelastic properties of the films were carried out. Improvements in glass transition temperature (T_g) were observed with increasing percentage of crosslinker. Acrylates based on aromatic acid amides showed higher T_g than aliphatic acid amides. The storage modulus (E′) increased up to 10% and further increases in the crosslinker percentage led to a decrease in the modulus. The rubbery modulus depended on percentage of crosslinker and not on crosslinker structure.     

Energy storage during inelastic deformation of glassy polymers

In this paper, aspects of the microstructural state of glassy polymers that evolve during physical ageing and inelastic deformation were studied. Differential scanning calorimetric (d.s.c.) measurements were performed on specimens of three glassy polymers: polystyrene (PS), polycarbonate (PC) and poly(methyl methacrylate) (PMMA). Materials were subjected to both a quenched and a well annealed heat treatment and subsequently deformed in compression to various levels of strain. Stress-strain curves and companion d.s.c. scans were compared.

The well known enthalpy overshoot at T_g was observed for the annealed samples, showing that ageing is accompanied by enthalpy relaxation. The annealed material was also found to require a higher stress to yield, and the additional work required to strain-soften the annealed polymer to the flow stress level of its quenched companion was found to correlate well with the area of the enthalpy overshoot of the annealed specimen.

Inelastic deformation was found to increase the specific enthalpy of both annealed and quenched specimens. In the annealed material, the enthalpy overshoot at T_g was found to decrease with inelastic strain and was completely erased by about −20% strain. Simultaneously, a pre-T_g exotherm was observed to develop with inelastic strain over a wide range of temperature. The pre-T_g exotherm was found to evolve until essentially reaching a steady-state profile at approximately −25% strain. This evolution coincided with the strain-softening phenomenon observed in the corresponding stress-strain results. A pre-T_g exotherm was also found to evolve with straining of the quenched material. Furthermore, the steady-state exotherms of the quenched and annealed materials were found to be nearly identical, as were their corresponding flow stress values after strain softening.

Finally, a second, post-T_g exotherm was found to develop with further straining beyond strains of −25%. This exotherm was found to increase with inelastic strain and coincided with the occurrence of strain hardening (due to chain orientation) in the materials.

The presence of two distinct and separately evolving exotherms in the inelastically deformed polymers indicates the existence of two separate deformation resistances in glassy polymers, one related to the initial yield and strain-softening behaviour, and the other to the orientation-induced strain hardening of the material. The observation that the pre-T_g exotherm is spread over a wide temperature range reflects the distributed nature of the structural state and may be quantified using a distribution in activation energy for the local rearrangements. The results therefore provide valuable information about the processes that must be accounted for in the development of accurate constitutive models of mechanical behaviour.