Thermal Properties of Polyacrylates at Metal Interfaces

Summary  The thermal properties of polyacrylates films sandwiched with metal were studied by differential scanning calorimetry. There were two glass transition relaxations, and the relaxation at the lower temperature, which was almost the same as the glass transition temperature of a bulk sample, diminished with thinning the polymer film. The glass transition relaxations at the higher temperature can be explained by the segmental motion of polymer chains interacting with metal surfaces at the interface. The results for the dielectric measurements for the sandwiched films also showed the similar relaxation modes.     

Influence of the Salt Concentration on the Properties of Salt‐Free Polyelectrolyte Complex Membranes

Polyelectrolyte complexes (PECs) prepared by solution mixing of cationic poly(diallyldimethylammonium chloride) and anionic poly(sodium 4‐styrene sulfonate) with various NaCl content are processed into films. Salt‐free (SF‐PEC) membranes are produced by rinsing the PEC in water overnight. The main finding of this paper is that SF‐PEC films have different properties depending on the NaCl concentration used during the processing step. Dynamic mechanical analysis measurement confirms that hydrated SF‐PEC film processed from higher salt content has a higher modulus than when processed without salt and the glass transition temperature appears to shift to higher values. Processing the PECs films in the presence of salt also has an interesting effect on their shape memory characteristics. SF‐PEC films prepared with high‐salt concentration are shown to maintain a programmed temporary shape better than materials prepared with low salt, while recovery is possible within a short period of time when immersed in hot water.     

Effects of film thickness on moisture sorption, glass transition temperature and morphology of poly(chloro-p-xylylene) film

Moisture sorption, glass transition temperature (T_g) and morphology of ultra thin poly(chloro-p-xylylene) (parylene-C) are greatly influenced by geometrical confinement effects. For film <50 nm, the equilibrium moisture saturation is a decreasing function of film thickness. However, the T_g of film <50 nm is about 10 °C higher than thicker films. The above phenomena are attributed to the effect of geometrical confinement on the thermal properties and the morphology of parylene-C film. Surface confinement results in an increased in T_g, but a decreased in crystallinity for films <50 nm. In this study, we show that the increase in moisture sorption for parylene-C films <50 nm is dominated by the crystallinity variation.     

Investigation of structural and mechanical properties of copper-chloride-doped nylon-6 films. II. Elastic and viscoelastic studies

The article reports the effect of variation in the concentration of copper chloride on the elastic and viscoelastic properties of nylon-6 films. The elastic modulus for the film is determined using sonic velocity measurement technique. The glass transition temperatures are determined from dynamic mechanical studies with the Rheovibron. It is observed that the glass transition temperature of the doped films increases with increase in the dopant concentration. It is also observed that at low concentrations of doping (up to 1.25%) the salt acts as a plasticizer, whereas for higher concentration of doping (up to 12.5%) it acts as an antiplasticizer.     

Aluminum‐enhanced alkali diffusion from float glass to PVD‐sputtered silica thin films

Interdiffusion processes between aluminum enriched PVD‐sputtered silica thin films and industrial float soda‐lime silicate glass substrates are quantitatively studied using SIMS analysis. Heat treatments are performed at temperatures close or above the glass transition temperature of the float glass. Aluminum doping of the film is shown to strongly increase the migration of alkali from the glass substrate to the silica thin film. In particular the final alkali content in the film exhibits a linear scaling with the aluminum concentration. An interdiffusion process is evidenced between bulk alkali ions and protons originating from a significant water content in the as‐deposited silica film. Experimental measurements of sodium concentration are shown to be consistent with a simple thermodynamic model based on the equilibration of the activity of sodium between the film and the glass substrate.     

Characterization of Optical Thin Films by Spectroscopic Ellipsometry

Spectroscopic ellipsometry was used to rapidly and nonde- structively characterize ion-plated SiO₂ and Ta₂O₅ films on glass substrates as a function of temperature. The analysis provided the density (as a function of depth) and optical properties of the films. The SiO₂ film had a higher refractive index than is typical for thermally grown SiO₂. This was attributed to compaction of the film during the deposition process. Similarly, the ion-plated Ta₂O₅ film had the high refractive index characteristic of a high-density film. The films were not affected strongly by temperature during heating >100°C.     

Reactive diluents and properties of ultraviolet-cured polycarbonate urethane acrylates

Polymer films obtained from photocurable formulations were investigated by tensile methods and dynamic mechanical analysis. The polymer formulations contained photoinitiator, urethane diacrylate oligomer, and acrylic reactive diluent. It was found that diluent concentration may strongly affect the glass transition temperature and elastic modulus of the cured coating. When the diluent homopolymer glass transition temperature is larger than that of oligomer homopolymer, the glass transition temperature and elastic modulus of the coating film increase with the increase of the diluent concentration. When the diluent homopolymer has lower glass transition temperature than the homopolymer of the oligomer, the increase in diluent concentration leads to a decrease in glass transition temperature and elastic modulus of the UV-cured coating film. The effect of the testing temperature on tensile storage modulus of the films containing different concentrations of reactive diluents was studied as well. The data indicated that a variety of coatings with wide ranging but predictable properties can be formulated from previously examined starting materials but used at different concentrations. © 1995 John Wiley & Sons, Inc.     

Metallization of UV‐cured acrylate resins by reduction of polymer‐incorporated cobalt ion

The surface of UV‐cured films of poly(ethylene glycol) diacrylate (PEGAc)/tetrahydrofurfuryl acrylate (THFAc) (weight ratio 100/0, 90/10, and 80/20) was metallized by the reduction of polymer‐incorporated cobalt chloride with aqueous sodium borohydride at 20°C. The electron probe microanalysis (EPMA) and X‐ray photoelectron spectroscopy measurement revealed that the cobalt ion, which was homogeneously distributed in the inner part of the film before reduction, migrated to both sides of the film, and then reduced to pure metal by the reduction treatment. The surface resistance of the UV‐cured PEGAc/THFAc film increased with increasing THFAc content. Especially, the trend was prominent at the glass side of the metallized films. The glass transition temperature of the cured resin measured by dynamic viscoelastic analysis slightly rose with an increase of THFAc content. The EPMA map of cobalt and carbon in the depth direction of the metallized film showed that the cobalt layer, generated at the glass side of the film with a higher THFAc content, contains more polymer component, in agreement with the order of surface resistance. The X‐ray diffraction analysis of the reduced films revealed that the degree of crystallinity of the generated cobalt was low. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1627–1632, 2006     

Water‐soluble urethane acrylate ionomers: Effect of molecular structure on ultraviolet coating properties

Water‐soluble urethane acrylate ionomers containing dimethylolpropionic acid (DMPA) were synthesized, changing the molecular components, and their ultraviolet (UV) coating properties were studied. It was found that the UV coating properties of the urethane acrylate ionomer films were very dependent on the molecular weight of the soft segment, the type of the diisocyanate, and the amount of neutralization. In general observations, the cured films displayed much improved mechanical properties, compared with conventional urethane acrylate film not containing ionic groups. The main reason for the improved film properties seemed to be attributed to the presence of ionic groups in the network. In dynamic mechanical analysis, two distinct glass transition temperatures, corresponding to the ionic hard domains and soft domains, were detected at high content of ionic groups. This suggested that the urethane acrylate network be composed of two phases. Consequently, the ionic hard domains formed by the phase separation from crosslinked network could act as a reinforcing filler, which possibly explains the improved film properties of the urethane acrylate ionomer films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1853–1860, 2000     

Solution casting,characterization, and performance evaluation of perfluorosulfonic sodium type membranes for chlor‐alkali application

This investigation describes solution casting, characterization and performance evaluation of perfluorosulfonic sodium (PFSS) type membranes prepared by three different methods from Nafion solution and Nafion‐117 for Chlor‐Alkali (CA) application. A Chlor‐Alkali experimental set‐up was designed and constructed for performance evaluation of the recast membranes. The chemical structure of solution cast films was studied and confirmed by FTIR (Fourier Transform infrared spectroscopy) and ATR (Attenuated total reflection) techniques. The physical properties of solution cast films including mechanical strength, thermal behavior, water sorption, ion‐exchange capacity (IEC), morphology, and crystallinity were also evaluated. All the recast polymeric films behave like elastomers with low modulus but high elongation at break. Differential scanning calorimetric (DSC) thermograms of solution cast films showed two endothermic peaks at 180°C and 250°C attributed to matrix glass transition (T_gm) and ionic cluster glass transition (T_gc) of the Nafion polymer, respectively. The water uptake of polymeric films was reasonable in comparison with Nafion‐117. Solution casting has no significant effect on ion exchange capacity of the recast films. The scanning electron microscope (SEM) micrograph showed that the morphology of recast films is reasonably similar with Nafion‐117. However, the as‐cast films have some micro pores, which are produced during solution casting. The crystallinity of annealed film, because of the heat treatment was slightly high due to local ordering. According to the experimental results, which obtained from performance evaluation in CA cell, the properties of recycled films are similar to commercial membranes such as Nafion‐117 and can be used in CA process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rosin derivatives: novel film forming materials for controlled drug delivery

Two new rosin derivatives (RD-1 and RD-2) were synthesized in the laboratory and evaluated for physicochemical properties, molecular weight (M_w), polydispersity (M_w/M_n) and glass transition temperature (T_g). Plasticizer free films of the derivatives were produced by casting/solvent evaporation method. The surface morphology (SEM), water vapour transmission and mechanical properties (tensile strength, percent elongation and modulus of elasticity) of the films were investigated. The derivatives were further evaluated for pharmaceutical film coating by characterizing the release of a model drug (diclofenac sodium) from non-pariel seeds (pellets) coated with the derivatives. Pellet film coating could be achieved without agglomeration of the pellets within a reasonable operation time. Drug release from the coated pellets was sustained up to 10 h with the two rosin derivatives. These findings suggest the possible application of rosin derivatives (RD-1 and RD-2) for film coating.     

Synthesis and characterization of waterborne polyurethane emulsions based on poly(butylene itaconate) ester

Waterborne polyurethane (WPU) prepolymer was synthesised by the reaction of poly(butylene itaconate) ester (PBI, Mn = 1109 g/mol), 1,6-hexanediol, dimethylol propionic acid (DMPA), 2,4-toluene diisocynate (TDI), hydroxyethyl acrylate (HEA), and absolute ethanol as blocking agent, triethylamine as neutralizer. Cross-linked WPU was synthesized by trimethylolpropane (TMP) as crosslinker. The influences of PBI, DMPA, and TMP content on WPU emulsions and films were investigated. The structure of WPU was determined by Fourier transform infrared (FTIR) spectra, thermal properties and glass transition temperature of WPU films were determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively, and morphology of the emulsion particles was observed by transmission electron microscopy (TEM). Through TGA, the heat resistance of the cross-linked WPU film was better than WPU film. By DSC analysis, glass transition temperature of cross-linked WPU film (21 °C) was higher than WPU film (10 °C).     

Water absorbance and thermal properties of sulfated wheat gluten films

Wheat gluten films of various thicknesses formed at 30–70°C were treated with cold sulfuric acid to produce sulfated gluten films. Chemical, thermal, thermal stability, and water uptake properties were characterized for neat and sulfated films. The sulfated gluten films were able to absorb up to 30 times their weight in deionized water. However, this value dropped to 3.5 when the film was soaked in a 0.9% (w/w) NaCl solution. The films were also soaked 4 times in deionized water, and each soaking resulted in a reduced water uptake capacity. The temperature of film formation had no effect on the final water uptake properties. Also, thinner films had higher concentrations of sulfate groups than thicker films; this resulted in higher water uptake values. In addition, sulfated gluten films had comparable glass‐transition temperatures but lower thermal stabilities than the neat gluten films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Packing effect on latex film formation: a photon transmission study

A photon transmission method has been used to study interdiffusion processes during film formation from hard latex particles. Films with different latex content were prepared separately by annealing poly(methyl methacrylate) (PMMA) particles above the glass transition temperature. The transmitted photon intensity from these films increases as the annealing temperature is increased. Monte Carlo simulations are performed for photon transmission through a rectangular lattice. The increase in the transmitted photon intensity (I_tr) is attributed to the latex content (film thickness) for the annealed film samples. It is observed that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. A negative absorbance coefficient has been measured above the 180 °C annealing temperature. Packing coefficients are obtained for films having various latex contents. © 2000 Society of Chemical Industry     

The detachment behavior of polycarbonate on thin films above the glass transition temperature

When producing mono‐axially stretched films made of amorphous polycarbonate, a self‐reinforcement is generated due to the stretching process. This leads to an increase of the strength and stiffness. The mono‐axial stretching process is conducted at temperatures above the glass transition temperature, whereas better mechanical properties are obtained at higher stretching temperatures. However, the film tends to adhere to the rolls, especially at temperatures from 10°C above the glass transition temperature. The rolls of the mono‐axial stretching unit are made of an induction hardened and polished quenched and tempered steel 1.7225 – 42CrMo4. This work reports on the investigation of the detachment behavior of polycarbonate on different coatings as a function of the temperature and contact time. The main intention is to find a suitable coating on which the polycarbonate film adheres only slightly at temperatures clearly exceeding the glass transition temperature. POLYM. ENG. SCI., 56:786–797, 2016. © 2016 Society of Plastics Engineers     

Quartz crystal resonator study of glass transitions in polyvinylbutyral (PVB) films

Glass transitions in polyvinylbutyral (PVB) films deposited on a gold substrate have been studied using a quartz crystal resonator technique by measuring the resonant frequency shift and resonant peak broadening of the quartz crystal coated with a PVB film. Using the measured frequency shift and peak broadening of the resonance of the quartz crystal due to changes in the coated PVB film, the storage moduli of the film were derived. The results show rapid drops in the storage moduli of the PVB films at temperature closer to that of glass transition of bulk PVB. The transitions at different frequencies were assessed by simultaneously measuring the resonance of the quartz crystal at multiple harmonics. No significant change in the glass transition temperature at multiple harmonics was observed. The results of the storage moduli for PVB films of different thickness show that glass transition temperatures in the films decrease with the film thickness; the decrease become more noticeable as the film thickness is less than 500 nm where the characteristic of changing of storage moduli become distinctly different from that in thicker film and in bulk materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45433.     

热塑性聚酰亚胺微电子薄膜的制备

以微电子业所急需的聚酰亚胺薄膜为背景,采用一种热塑性聚酰亚胺树脂(TPI),实验测定了聚合物溶液特性、干燥工艺及热拉伸性能。在化学环化过程中聚合物溶液粘度随时间逐步增大;15 h后粘度和重均相对分子质量及分布趋于稳定。薄膜溶剂含量在干燥初期急剧下降,干燥速率随干燥温度升高而增大。TPI树脂表现出良好的热塑拉伸性能,当温度高于其玻璃化温度时,最大拉伸比随升温速率降低而增大,而随拉伸载荷增加呈现出先增后降。TPI薄膜经拉伸处理后其力学性能得到明显提高,综合性能与日本钟渊TP E薄膜相当。     

Effect of ultrasonication and other processing conditions on the morphology,thermomechanical, and piezoelectric properties of poly(vinylidene difluoride‐trifluoroethylene) copolymer films

This study is carried out on the effect of processing conditions including preparation methods, ultrasonication, film thickness, and thermal annealing on the thermal, mechanical, and piezoelectric properties of copolymer of poly(vinylidene difluoride‐trifluoroethylene) (P(VDF‐TrFE)). Free‐standing films and films on substrates are prepared by solvent casting and spin‐coating, respectively. The results obtained by differential scanning calorimetry show that the Curie transition of the copolymer films was influenced by the preparation methods, with very little difference in the melting transition. The difference was attributed to a less uniform distribution of TrFE comonomer units within the crystalline and amorphous regions of the spin‐coating films. However, no effect of the preparation methods on the piezoelectric properties of the films was observed. It is also found that the short ultrasonication, film thickness higher than critical value of crystallization of P(VDF‐TrFE) (about 100 nm), and drying before annealing did not have a significant effect on the properties of the films. Surprisingly, the ultrasonication had a clear impact on the relaxations at high temperature of the polymer chains. In addition, this study indicates that a short annealing by 10 min at 140°C was enough to obtain well‐crystallized films, which is interesting from the industrial point of view. POLYM. ENG. SCI., 54:1280–1288, 2014. © 2013 Society of Plastics Engineers     

Effects of solid substrate on structure and properties of casting waterborne polyurethane/carboxymethylchitin films

We prepared two series of semiinterpenetrating polymer network (semi-IPN) films from cross-linked waterborne polyurethane (WPU) and carboxymethylchitin (CMCH) in the aqueous solution on the glass and Teflon as the hydrophilic and hydrophobic substrates, respectively, by casting method. The chemical compositions, structure and morphologies of the films were examined by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM). The miscibility, thermal stability and mechanical properties of the films were investigated by density measurement, dynamic mechanical analysis (DMA), ultraviolet (UV) spectroscopy, thermogravimetric analysis (TGA), tensile testing and solvent swelling testing. The results revealed that the semi-IPN films exhibited good miscibility when CMCH content was lower than 35 and 65 wt% for the films prepared on the glass and Teflon, respectively, resulting in higher light transmittance, thermal stability and tensile strength than the WPU film. Interestingly, the films prepared with the Teflon as the substrate possessed better miscibility and higher storage modulus, thermal stability, tensile strength and solvent-resistance than that with the glass as the substrate over the entire composition range studied here. This difference can be attributed that a strong intermolecular interaction occurred between WPU and CMCH to form a dense architecture, owing to that two kinds of macromolecules all were repulsed from the Teflon surface and forced to concentrate into inner surface. It has been confirmed that the hydrophility and hydrophobility of the solid substrate significantly influenced the structures and properties of the casting films, and using Teflon solid substrate can more effectively improve the miscibility and properties of the semi-IPN materials with hydrophilic character than glass one. We proposed a model describing the formation of WPU/CMCH semi-IPN films cast on the hydrophilic and hydrophobic substrates to illustrate the different structures of two types of films.     

Heterogeneous method of chitosan film preparation: Effect of multifunctional acid on film properties

The heterogeneous crosslinking method was applied to chitosan films with citric acid to observe and understand the effect of a multifunctional acid at a low concentration on film properties. Neat and neutralized chitosan films and films containing 15% (w/w) citric acid (denoted as CA films) were characterized by mechanical, water vapor permeability (WVP), and thermogravimetric analysis tests. The CA films displayed a higher tensile strength by 10%, lower WVP by 30%, and higher thermal stability, compared to neutralized films. The crystalline structure converted back from tendon to Type II after the addition of citric acid, as determined by X-ray diffraction. Neat films displayed a lower water contact angle (72°) compared to neutralized and CA films (78°–79°). The heterogeneous method was also applied to incorporate a plasticizer into a neutralized film to potentially observe the glass transition using dynamic mechanical analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48648.