In-Out Surface Modification of Halloysite Nanotubes (HNTs) for Excellent Cure of Epoxy: Chemistry and Kinetics Modeling

In-out surface modification of halloysite nanotubes (HNTs) has been successfully performed by taking advantage of 8-hydroxyquinolines in the lumen of HNTs and precisely synthesized aniline oligomers (AO) of different lengths (tri- and pentamer) anchored on the external surface of the HNTs. Several analyses, including FTIR, H-NMR, TGA, UV-visible spectroscopy, and SEM, were used to establish the nature of the HNTs’ surface engineering. Nanoparticles were incorporated into epoxy resin at 0.1 wt.% loading for investigation of the contribution of surface chemistry to epoxy cure behavior and kinetics. Nonisothermal differential scanning calorimetry (DSC) data were fed into home-written MATLAB codes, and isoconversional approaches were used to determine the apparent activation energy (Eα) as a function of the extent of cure reaction (α). Compared to pristine HNTs, AO-HNTs facilitated the densification of an epoxy network. Pentamer AO-HNTs with longer arms promoted an Excellent cure; with an Eα value that was 14% lower in the presence of this additive than for neat epoxy, demonstrating an enhanced cross-linking. The model also predicted a triplet of cure (m, n, and ln A) for autocatalytic reaction order, non-catalytic reaction order, and pre-exponential factor, respectively, by the Arrhenius equation. The enhanced autocatalytic reaction in AO-HNTs/epoxy was reflected in a significant rise in the value of m, from 0.11 to 0.28. Kinetic models reliably predict the cure footprint suggested by DSC measurements.

Study on Properties of Heat-Resistant Hybrid Resin Containing Silicon and Composites

In recent years, one kind of novel hybrid polymer containing silicon has already been reported in the field of high-temperature resistance polymer. Gradually, it has been a research hotspot in the field of high-performance matrix resins because of excellent heat resistance and dielectric properties. The composite was prepared by M-aminophenylacetylene terminated polymethyldiphenylethynyl silane (MDPES-2) as a matrix and nonalkali glass cloth as reinforced material using a hot press process. The cure reaction of MDPES-2 was characterized. Meanwhile, heat resistance, mechanical properties, and dielectric properties of MDPES-2 composites were systematically studied in this paper. The results showed that flexural strength at room temperature is 321 MPa and flexural strength retention at 240°C was 98.3%. Flexural strength retention after thermal treatment at 500°C for 7 min was 84%. In addition, ε and dielectric dissipation factor ( tan δ ) were 3.9 and 2.0 × 10 − 3 (10 GHz).

Bulk-Surface Modification of Nanoparticles for Developing Highly-Crosslinked Polymer Nanocomposites

Surface modification of nanoparticles with functional molecules has become a routine method to compensate for diffusion-controlled crosslinking of thermoset polymer composites at late stages of crosslinking, while bulk modification has not carefully been discussed. In this work, a highly-crosslinked model polymer nanocomposite based on epoxy and surface-bulk functionalized magnetic nanoparticles (MNPs) was developed. MNPs were synthesized electrochemically, and then polyethylene glycol (PEG) surface-functionalized (PEG-MNPs) and PEG-functionalized cobalt-doped (Co-PEG-MNPs) particles were developed and used in nanocomposite preparation. Various analyses including field-emission scanning electron microscopy, Fourier-transform infrared spectrophotometry (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) were employed in characterization of surface and bulk of PEG-MNPs and Co-PEG-MNPs. Epoxy nanocomposites including the aforementioned MNPs were prepared and analyzed by nonisothermal differential scanning calorimetry (DSC) to study their curing potential in epoxy/amine system. Analyses based on Cure Index revealed that incorporation of 0.1 wt.% of Co-PEG-MNPs into epoxy led to Excellent cure at all heating rates, which uncovered the assistance of bulk modification of nanoparticles to the crosslinking of model epoxy nanocomposites. Isoconversional methods revealed higher activation energy for the completely crosslinked epoxy/Co-PEG-MNPs nanocomposite compared to the neat epoxy. The kinetic model based on isoconversional methods was verified by the experimental rate of cure reaction.

Mixed Carbon Nanomaterial/Epoxy Resin for Electrically Conductive Adhesives

The increasing complexity of printed circuit boards (PCBs) due to miniaturization, increased the density of electronic components, and demanding thermal management during the assembly triggered the research of innovative solder pastes and electrically conductive adhesives (ECAs). Current commercial ECAs are typically based on epoxy matrices with a high load (>60%) of silver particles, generally in the form of microflakes. The present work reports the production of ECAs based on epoxy/carbon nanomaterials using carbon nanotubes (single and multi-walled) and exfoliated graphite, as well as hybrid compositions, within a range of concentrations. The composites were tested for morphology (dispersion of the conductive nanomaterials), electrical and thermal conductivity, rheological characteristics and deposition on a test PCB. Finally, the ECA’s shelf life was assessed by mixing all the components and conductive nanomaterials, and evaluating the cure of the resin before and after freezing for a time range up to nine months. The ECAs produced could be stored at −18 °C without affecting the cure reaction.

Low Temperature Vulcanisation Technique for CR BIIR Blend for Encapsulation of Oceanic Sensors

Blend of chloroprene rubber (CR) and bromobutyl rubber (BIIR) is used for encapsulation of piezo sensors used in sea water. Conventional encapsulation method of these sensors involving high temperature vulcanisation (HTV) often leads to deterioration of piezo properties due to thermal degradation. This paper reports a low temperature vulcanisation (LTV) technique carried out at 90 °C for CR-BIIR blend using chlorinated polyethylene (CPE) as compatibiliser and LTV system consisting of modified di-o-tolyl guanidine and thiocarbanilide as accelerators and ZnO as curing agent. The conventionally used scavenger MgO was eliminated and only ZnO was used to boost the cure reaction. Properties specific to sonar sensors, namely, acoustic transparency, electrical resistivity, water absorption and physico‑mechanical properties were evaluated besides evaluation of morphology. The results are found to compare better than the conventional blend. Accelerated thermal ageing at 70 °C for 7 days yielded 97 % retention of tensile strength. The technique was implemented in a PZT hydrophone sensor and was successfully underwater tested.

Dynamic Cure Kinetics and Physical-Mechanical Properties of PEG/Nanosilica/Epoxy Composites

This study investigated the effect of polyethylene glycol (PEG) and nanosilica (NS) on the physical-mechanical properties and cure kinetics of diglycidyl ether of bisphenol-A-based epoxy (DGEBA-based EP) resin. For this purpose, tensile and viscometry tests, dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC) were carried out under dynamic conditions. The results showed that adding NS and PEG enhances the maximum cure temperature as well as the heat of cure reaction (ΔH) in EP-NS, while it decreases in EP-PEG and EP-PEG-NS. The cure kinetic parameters of EP-PEG-NS were calculated by Kissinger, Ozawa, and KSA methods and compared with each other. The Ea calculated from the Kissinger method (96.82 kJ/mol) was found to be lower than that of the Ozawa method (98.69 kJ/mol). Also, according to the KAS method, the apparent Ea was approximately constant within the 10-90% conversion range. Tensile strength and modulus increased by adding NS, while tensile strength diminished slightly by adding PEG to EP-NS. The glass transition temperature (Tg) was calculated using DMTA which was increased and decreased by the addition of NS and PEG, respectively. The results of the viscometry test showed that the viscosity increased with the presence of both PEG and NS and it prevented the deposition of solid particles.