Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

The use of self‐assembling, pre‐polymer materials in 3D printing is rare, due to difficulties of facilitating printing with low molecular weight species and preserving their reactivity and/or functions on the macroscale. Akin to 3D printing of small molecules, examples of extrusion‐based printing of pre‐polymer thermosets are uncommon, arising from their limited rheological tuneability and slow reactions kinetics. The direct ink write (DIW) 3D printing of a two‐part resin, Epon 828 and Jeffamine D230, using a self‐assembly approach is reported. Through the addition of self‐assembling, ureidopyrimidinone‐modified Jeffamine D230 and nanoclay filler, suitable viscoelastic properties are obtained, enabling 3D printing of the epoxy–amine pre‐polymer resin. A significant increase in viscosity is observed, with an infinite shear rate viscosity of approximately two orders of magnitude higher than control resins, in addition to, an increase in yield strength and thixotropic behavior. Printing of simple geometries is demonstrated with parts showing excellent interlayer adhesion, unachievable using control resins.     

Synthesis of thermoset plastics by Lewis acid initiated copolymerization of fish oil ethyl esters and alkenes

The Lewis acid initiated cationic homopolymerization of Norway fish oil ethyl ester (NFO) or the corresponding conjugated fish oil (CFO) and their copolymerization with various alkene comonomers is investigated. Among the Lewis acids employed, boron trifluoride diethyl etherate (BFE, BF₃ · OEt₂) is found to be the most effective initiator for cationic polymerization of the NFO and CFO systems. The BFE‐initiated homopolymerization of NFO generally results in low molecular weight viscous oils, while that of CFO leads to a solid elastic gel with a gel time of more than 72 h at room temperature. Copolymerization of the NFO or CFO with some alkene comonomers significantly facilitates gelation. The gel times are largely dependent upon the stoichiometry, the type of fish oil, and the alkene comonomer. After postcuring at elevated temperatures, the cationic copolymerization affords polymers ranging from soft rubbery materials to rigid plastics. These NFO and CFO polymers are composed of highly crosslinked materials and a certain amount of free oils and are found to be fully cured thermosets. Generally, CFO polymers appear to be harder than the corresponding NFO polymers. However, the thermal properties of the bulk polymers are similar to each other, and their insoluble extracts exhibit much higher thermal stability than the bulk thermosets. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2001–2012, 2001     

The toughening effect and mechanism of styrene‐butadiene rubber nanoparticles for novolac resin

In this article, phenolic nanocomposites were prepared using styrene–butadiene rubber (SBR) nanoparticles with an average particle size of about 60 nm as the toughening agent. The mechanical and thermal properties of phenolic nanocomposites and the toughening mechanism were studied thoroughly. The results showed that when adding 2.5 wt % SBR nanoparticles, the notched impact strength of phenolic nanocomposites reached the maximum value and was increased by 52%, without sacrificing the flexural performance. Meanwhile, SBR nanoparticles had no significant effect on the thermal decomposition temperature of phenolic nanocomposites. The glass‐transition temperature (T_g) of phenolic nanocomposites shifted to a lower temperature accompanying with the increasing T_g of loaded SBR, which showed there was a certain compatibility between SBR nanoparticles and phenol‐formaldehyde resin (PF). Furthermore, the analysis of Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy indicated that there existed a weak chemical interaction between SBR nanoparticles and the PF matrix. The certain compatibility and weak chemical interaction promoted the formation of a transition layer and improved the interfacial bonding, which might be important reasons for the great enhancement of the toughness for phenolic nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41533.     

Synthesis and properties of cross‐linked polymers from epoxidized rubber seed oil and triethylenetetramine

A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the epoxidized oils with triethylenetetramine (in the absence of a catalyst) was carried out in a batch setup (1 : 1 molar ratio of epoxide to primary amine groups, 100°C, 100 rpm, 30 min) followed by casting of the mixture in a steel mold (180°C, 200 bar, 21 h) and this resulted in cross‐linked resins. The effect of relevant pressing conditions such as time, temperature, pressure, and molar ratio of the epoxide and primary amine groups was investigated and modeled using multivariable nonlinear regression. Good agreement between experimental data and model were obtained. The rubber seed oil‐derived polymer has a T_g of 11.1°C, a tensile strength of 1.72 MPa, and strain at break of 182%. These values are slightly higher than for commercial epoxidized soybean oil (T_g of 6.9°C, tensile strength of 1.11 MPa, and strain at break of 145.7%). However, the comparison highlights the potential for these novel resins to be used at industrial/commercial level. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42591.     

Mechanical and thermal properties of biphenyldiol formaldehyde resin/gallic acid epoxy composites enhanced by graphene oxide

In this study, the gallic acid‐based epoxy resin (GA‐ER) and alkali‐catalysed biphenyl‐4,4′‐diol formaldehyde resin (BPFR) are synthesized. Glass fibre‐reinforced GA‐ER/BPFR composites are prepared. Graphene oxide (GO) is used to improve the mechanical and thermal properties of GA‐ER/BPFR composites. Dynamic mechanical properties and thermal, mechanical, and electrical properties of the composites with different GO content are characterized. The results demonstrate that GO can enhance the mechanical and thermal properties of the composites. The glass transition temperature, T_g, of the BPFR/GA‐ER/GO composites is 20.7°C higher than the pure resin system, and the 5% weight loss temperature, T_d5, is enhanced approximately 56.6°C. When the BPFR: GA‐ER mass ratio is at 4 : 6 and GO content is 1.0–1.2 wt %, the tensile and impact strengths of composites are 60.97 MPa and 32.08 kJ/m² higher than the pure resin composites, respectively. BPFR/GA‐ER composites have better mechanical properties, and can replace common BPA epoxy resins in the fabrication of composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42637.     

Oil‐spill cleanup: The influence of acetylated curaua fibers on the oil‐removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil‐spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil‐absorbing capability of the composites. The obtained magnetic composites were studied by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil‐removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41732.     

Stress relaxation behavior of starch powder‐epoxy resin composites

The purpose of the present study is to investigate the quasi‐static and the viscoelastic behavior of epoxy resin reinforced with starch powder. An increase in the elastic modulus on the order of 42% was achieved; a behavior that was predicted by the modulus prediction model (MPM). Next, the composite was subjected to flexural relaxation experiments, in order to determine the relaxation modulus, at different filler‐weight fractions and flexural deflections imposed. The viscoelastic models of the standard linear solid, the power law model and the residual property model (RPM) were applied in order to simulate/predict the stress relaxation curves. Predicted values derived from the application of the above models were compared to each‐other as well as to respective experimental findings. From the above comparison it was proved the superiority of the RPM model in predicting both the linear and the nonlinear viscoelastic response of the materials investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41697.     

Silicone membranes to inhibit water uptake into thermoset polyurethane shape‐memory polymer conductive composites

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (T_g) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this study, a silicone membrane was used to inhibit water uptake into a thermoset SMP composite containing conductive filler. Thermoset polyurethane SMPs were loaded with either 5 wt % carbon black or 5 wt % carbon nanotubes, and subsequently coated with either an Al₂O₃‐ or silica‐filled silicone membrane. It was observed that the silicone membranes, particularly the silica‐filled membrane, reduced the rate of water absorption (37°C) and subsequent T_g depression versus uncoated composites. In turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41226.     

Cationic polymerization behavior of β‐methylglycidyl ether derivatives and physical properties of their cationically cured materials

β‐Methylglycidyl ethers have been applied to Electrical and Electronic adhesives. However, there is no report about the detailed polymerization behavior and physical properties of their cured products. Hence, we investigated cationic polymerization behavior of bisphenol A di(β‐methylglycidyl) ether (Me‐BADGE) and physical properties of the cured products containing Me‐BADGE. DSC analysis suggested that Me‐BADGE could be cured completely at lower temperature than bisphenol A diglycidyl ether (BADGE). Physical properties were analyzed by dynamic viscoelastic analysis. Glass transition temperature (T_g) of BADGE homopolymer was 194°C. In contrast, the copolymer of BADGE (50 wt %) with Me‐BADGE (50 wt %) showed T_g at 124°C. According to the data of E’ and tan δ, crosslink density of the cured products decreased with increasing the Me‐BADGE content. The analysis of cationic polymerization of monofunctional β‐methylglycidyl ether suggested that the cationic polymerization proceeded not only through oxonium cation but also through carbocation formed by ring‐opening reaction of oxonium cation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42377.