Ultrasound monitoring of the cure kinetics of an epoxy resin: Identification,frequency and temperature dependence

In this paper the monitoring of ultrasonic parameters of a thermosetting resin during an isothermal curing process is described. The ultrasonic properties are studied within the context of the monitoring of composite plate production by resin transfer molding (RTM). These ultrasonic characteristics can be related directly to cure kinetic models. An ultrasonic method, based on the measurement of the elastic constant and associated mechanical loss has been developed to identify the variations of the phase transformation. To study the reaction kinetics, the time dependence of the elastic coefficient is modeled using a Weibull distribution. The approximate time derivative form of this Weibull model makes it possible to find the relationship between ultrasonic parameters and the chemical Kamal model. The ultrasonic monitoring of a cooling process was also performed to study the temperature sensitivity after curing. Thanks to experimental measurements of the ultrasonic velocity and attenuation, the power law coefficient variations and their temperature sensitivity can be examined. The resulting viscoelastic Cole-Cole parameters were estimated and a frequency-temperature (f, T) model was proposed.     

Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Photopatternable thin films from silyl hydride containing silicone resins and photobase generators

The photopatternability of various silyl hydride containing organosilicone resins containing the photobase generators N‐methylnifedipine or O‐(2‐nitrobenzyl)‐N‐octyl carbamate have been examined, with the goal of identifying potential photopatternable compositions with high thermal stability after cure. Two different categories of silicone resins have been prepared from combinations of diphenylsiloxane and methyl and hydrogen silsesquioxane units and a combination of phenyl and hydrogen silsesquioxane monomer units. The photobase generators were incorporated into these resins at concentrations up to 10 weight percent. UV‐irradiation of micrometer thick silicone resin‐photobase films through a photomask, under an air atmosphere, yielded micrometer scale features after development. Photopatternable compositions have been identified with photosensitivities of less than 50 mJ/cm2. The photopatterning process is believed to proceed by base‐catalyzed reaction of resin‐based silanol groups with neighboring silyl hydride groups to yield thermally stable siloxane crosslinks. Copyright © 1999 John Wiley & Sons, Ltd.     

New polymers of carbonic acid. XXV. Photoreactive cholesteric polycarbonates derived from 2,5‐bis(4′‐hydroxybenzylidene)cyclopentanone and isosorbide

Several binary copolycarbonates were prepared by polycondensation of 2,5‐bis(4‐hydroxybenzylidene)cyclopentanone, BHBC, with methylhydroquinone, MHQ, hydroquinone 4‐hydroxybenzoate, HQHB, or isosorbide. Furthermore, five ternary copolycarbonates were prepared based on the aforementioned monomers. All polycondensations were conducted in pyridine with trichloromethyl chloroformate as condensing agent. All polycarbonates were characterized by elemental analyses, viscosity and DSC measurements, IR and ¹H‐ and ¹³C‐NMR spectroscopy, optical microscopy, and the WAXS powder pattern. All isosorbides containing binary and ternary copolycarbonates were found to form a cholesteric melt, but only three of them were capable to form a stable Grandjean texture upon shearing. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1125–1133, 1999     

Chemistry of novolac resins. X. Polymerization studies of HMTA and strategically synthesized model compounds

The reactions between hexamethylenetetramine (HMTA) and compounds which model novolac resins have been studied by ¹³C‐ and ¹⁵N‐NMR techniques. The dimer and tetramer compounds vary in molecular size and structure and react with HMTA to yield benzylamines and benzoxazine as the major initial‐formed intermediates and convert to methylene linked compounds at increased temperatures. The reaction of the compounds with only ortho reactive sites paralleled the 2,4‐xylenol–HMTA case reported by us previously; however, increasing molecular weight favored the formation of benzylamines and not benzoxazines. Those compounds with only para reactive sites paralleled the 2,6‐xylenol–HMTA case. The reactivity of the systems containing both ortho and para reactive sites depends on the ratio of ortho/para sites and various aspects such as the chemical structure and molecular weight of the compound, the HMTA level, and the melting point and pH of the system. These results parallel those obtained from novolac/HMTA systems. The xylenol/HMTA reactions formed similar products but showed quite different relative reaction rates by varying the HMTA ratio and structures of the materials. The importance of careful selection of model systems is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1347–1355, 1999     

Monomers,polymers, copolymers,resins, and coated silicas containing benzylamine residues planned as artificial substrates of benzylamine oxidase

The new monomers 3-(3-methacryloxypropoxy)benzylamine and 4-(3-methacryloxypropoxy)benzylamine in the form of hydrochlorides have been synthesized and radically copolymerized under various conditions with comonomers of different hydrophilicity, including N-acryloylmorpholine, N-acryloylpyrrolidine, N,N-dimethylacrylamide, and N-vinylbenzoylmorpholine, to obtain linear soluble, granular crosslinked, and silica-based macromolecular systems designed for investigating the action mechanism of benzylamine oxidase. Some characteristics of the prepared materials, including scanning electron microscopy photographs, are reported. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3109–3118, 1999     

Analytical characterization of diterpenoid resins present in pictorial varnishes using pyrolysis-gas chromatography-mass spectrometry with on line trimethylsilylation

A procedure based on the technique of the pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been applied, in this work, in order to determine the composition of diterpenoid resin employed in art works. The method is based on the on line derivatization of these resins using hexamethyldisilazane (HMDS). Results obtained were compared with those previously reported in literature from Venice turpentine, Strasbourg turpentine, colophony, sandarac and Manila copal using this same method and with those others from in situ thermally assisted hydrolysis and methylation with tetramethylammonium hydroxide (TMAH). Canada balsam, copper resinate and Copaiba balsam have been also analyzed extending the scope of this method in the field of the analysis of artwork materials. Several non-reported trimethylsilylated derivatives of compounds present in the diterpenoid resins have been identified. An improvement in sensitivity has been obtained by using HMDS as derivatizing reagent, together with a better resolution of the most representative peaks. Additionally, this method reduces the number of pyrolytic fragmentation, recombination, dehydration and isomerization products formed during the pyrolysis process and, in consequence, more simplified chromatograms are obtained. Finally, the reported procedure has been successfully used for characterizing two diterpenoid resin-based varnishes present in the canvas painting "The Betrothal of the Virgin" (Anonymous, 17th century) which is included in the pictorial collection of Saint Joseph Church in Taormina (Italy) and the Magdalena Tryptich (Master of Alzira, 16th century, Valencia, Spain).     

Changes in poly-vinylidene fluoride produced by electron irradiation

A study was made of the effects of electron irradiation of poly-vinylidene fluoride, using the DSC, FTIR, and X-ray techniques, as well as determining the percent cross-linking. Changes in crystallinity and melting point of the sample as a function of dose were found, the latter due to competition between cross-linking and crystallinity. The cross-linking was observed to increase with radiation dose. Chemical changes observed include the formation of carbonyl groups and double bonding, associated with the loss of HF.     

Isothermal curing of an epoxy resin by alternating differential scanning calorimetry

The quasi-isothermal curing of a diepoxide resin with a triamine of polyoxypropylene was studied by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The complex heat capacity measurements allows to analyse the vitrification process at curing temperatures (T_c) below the maximum glass transition of the fully cured epoxy (T_g∞=85.8°C). Initially, the modulus of the complex heat capacity, |C^*_p|, increases until a maximum (conversion between 0.42 and 0.56) and then decreases. This step is followed by an abrupt decay of |C^*_p|, due to the vitrification of the system, which allows the determination of the vitrification time. This value agrees well with that determined by the partial curing method. The phase angle and out-of-phase heat capacity show an asymmetric wide peak during the vitrification process. The change in |C^*_p| at vitrification decreases with the increase of T_c becoming zero at temperature T_g∞. This epoxy-triamine system shows a delay of the vitrification process respect to other model epoxy systems probably due to the presence of polyoxypropylene chains in the network.

The decay of |C^*_p| during vitrification may be normalised between unity and zero by defining a mobility factor. This mobility factor has been used to simulate the reaction rate during the stage where the reaction is controlled by diffusion. The observed reaction rate is simulated by the product of the kinetic reaction rate, determined by the autocatalytic model, and the mobility factor.     

UV assisted photo reactive polyether-polyesteramide resin for future applications in 3D printing

Among additive manufacturing, photocuring 3D printing technologies are very relevant because of its high printing speed and high precision. However, the limited performance of photosensitive thermoset polymers is the bottleneck for the application of photocuring 3D printing in some fields, particularly in the biomedical sector. Thus, the development of biodegradable and biocompatible materials is highly desirable and of utmost importance. In this work, a biodegradable and non-cytotoxic thermoset polymer for photocuring 3D printing is reported. It consists of an unsaturated polyesteramide bearing phenylalanine, 2-butene-1,4-diol and fumarate building blocks, which is photocured under UV irradiation using a low molecular weight poly(ethylene glycol) diacrylate as crosslinker. The main characteristics of the new thermoset are: (1) very high volumetric and mechanical integrity stabilities, comparable to that of photocured epoxides; (2) very high degradation temperature; (3) very low water absorption capacity; (4) relatively fast enzymatic degradation, reaching 16.5% after 3 months; and (5) non-cytotoxic response in presence of epithelial cells, even when soluble molecular fragments coming from biodegradation are considered. These properties favor the future utilization of the new polyether-polyesteramide resin in the manufacturing of more sustainable products via 3D printing methods, such as stereolithography, that uses UV sources.