Study on tri-imidazole derivatives modified with triazine-trione structure as latent curing agents for epoxy resin

In this paper, four novel kinds of triazine-trione based tri-imidazole derivatives (IM-TT, 2MI-TT, 2EI-TT and EMI-TT) were synthesized through the addition reaction between triglycidyl isocyanurate (TGIC) and imidazole (IM), 2-methylimidazole (2MI), 2-ethylimidazole (2EI) and 2-ethyl-4-methylimidazole (EMI), respectively. The triazine-trione based tri-imidazole derivatives were blended with epoxy resin and the reactivity, thermal latency and thermal property were investigated. The results on curing behaviors indicated that the curing exothermic peaks of the blends with triazine-trione based tri-imidazole derivatives shifted to higher temperatures compared with those with commercial imidazoles. The curing exothermic peak temperatures (Tps) of the synthesized tri-imidazole derivatives were increased by 23–32 ℃ compared with the unmodified imidazoles. In addition, Rheological behavior results indicated that the EP blends with tri-imidazole derivatives also exhibited excellent storage stability which was as long as 38 days under room temperature. Last but not the least, the EP blends with triazine-trione based tri-imidazole derivatives also exhibited high glass transition temperatures due to introducing of triazine-trione structures with high crosslinking density. The glass transition temperatures (Tgs) of the prepared thermosets ranged from 128 to 152 ℃. The triazine-trione based tri-imidazole derivatives provide a way to prepare latency epoxy resin with high high glass transition temperature and long storage stability. Article Highlights Four novel kinds of triazine-trione based tri-imidazole derivatives were synthesized. The EP cured with the tri-imidazole derivatives displayed great thermostability. The EP cured with the tri-imidazole derivatives exhibited long storage stability.

Synthesis of Blend Polymer (PVA / PANI)/Copper (1) Oxide Nanocomposite: Thermal Analysis and UV-Vis Spectra Specifications

Copper (1) oxide nanoparticles together with matrix polymers of polyvinyl alcohol (PVA) and polyaniline (PANI) composite films were synthesized, as these materials are of importance in optoelectronic applications. ‎Nanoparticles of Cu2O were produced by chemical precipitation. Polymerization of aniline was carried out through polymerization in an acidic medium. Structural, thermal, and optical properties of PVA+PANI/Cu2O nanocomposite were inspected by x-ray diffraction (XRD), scanning electron microscopy (SEM), fourier-transform infrared (FTIR), differential scanning calorimeter (DSC) and ultraviolet-visible spectroscopy (UV-Vis spectroscopy). X-ray diffraction peaks at 29.53°, 36.34°, and 42.22° indicated the presence of cuprous oxide nanoparticles, having high dispersions and limited size distributions. The estimated average size of Cu2O nanoparticles was ~ 17.1525 nm. A characteristic peak at around 2θ = 18.5° was attributed to periodical parallel and perpendicular polymer chains, which denoted the formation of PANI. SEM results indicated the symmetrical dispersion of Cu2O nanoparticles inside the hybrid polymer of PVA and PANI matrix, being potentially useful for encapsulation and acting as a good capping agent. FTIR results established the formation of PANI and Cu2O with nanocrystalline nature. DSC results revealed the appearance of one single peak of Tg which decreased with Cu2O content of 4% wt, followed by an increase of that value by increasing Cu2O content up to 16%wt. Thermogram analysis of the PANI and PVA embedded with Cu2O form showed an exothermic peak at (240-292)℃ affiliated to the cross-linking reaction, while the Tm value of prepared nanocomposites is just about close to that of PVA polymer. The results indicated that there is an increase in thermal stability due to the presence of Cu2O NPS within the matrix of polymers. The distinguishing peaks at 330, 347, and 457 nm which refer to PANI are assigned to π−π* electron transitions among the benzenoid rings. The high absorption intensity of the peak at 470 nm for the blended PVA+PANI having 12% wt of Cu2O NPS is assigned due to the inter-band transitions for electrons of the core copper as well as copper oxide. This points out that the increasing quantity of Cu2O NPs leads to increases in the amounts of highly oxidized structures in PANI and decreases in the doping electrons and length of conjugation throughout the incorporation of Cu2O NPs into PANI matrix. Depending on the practical results, it can be said that these polymeric nanocomposites can be efficiently used in photovoltaic technology applications.

Preparation and Stabilization of High Molecular Weight Poly (acrylonitrile-co-2-methylenesuccinamic acid) for Carbon Fiber Precursor

Bifunctional comonomer 2-methylenesuccinamic acid (MLA) was designed and synthesized to prepare acrylonitrile copolymer P (AN-co-MLA) using mixed solvent polymerization as a carbon fiber precursor. The effect of monomer feed ratios on the structure and stabilization were characterized by elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), X-ray diffraction (XRD), proton nuclear magnetic (1H NMR), and differential scanning calorimetry (DSC) for the P (AN-co-MLA) copolymers. The results indicated that both the conversion and molecular weight of polymerization reduce gradually when the MLA content is increased in the feed and that bifunctional comonomer MLA possesses a larger reactivity ratio than acrylonitrile (AN). P (AN-co-MLA) shows improved stabilization compared to the PAN homopolymer and poly (acrylonitrile-acrylic acid-methacrylic acid) [P (AN-AA-MA)], showing features such as lower initiation temperature, smaller cyclic activation energy, wider exothermic peak, and a larger stabilization degree, which are due to the ionic cyclization reaction initiated by MLA, confirming that the as-prepared P (AN-co-MLA) is the potential precursor for high-performance carbon fiber.

Evaluation of the Thermal and Morphological Properties of γ-Irradiated Chitosan-Glycerol-Based Polymeric Films

Industry-sponsored research has intensified to find suitable substitutes for synthetic polymers. For this purpose, biopolymers are promising materials that are extracted from renewable resources. However, there are areas of concern (biopolymers are mostly brittle in the dry state) that require further research before they are used in advanced applications. To overcome this, plasticizers are often added to biopolymers to enhance their physicochemical properties. In this study, chitosan (CH)-glycerol (GL)-based polymeric films were prepared by a simple drop-casting technique, and the influence of a plasticizer (GL) on the properties of chitosan films was analyzed. Additionally, the as-prepared samples were irradiated with γ-rays (60Co γ rays with a dose of 102 kGy) to study the effect of γ-irradiation on the properties of polymeric composites. To achieve this, different samples were prepared by varying the amount of GL. FT-IR analysis revealed the interruption of hydrogen bonding in chitosan by the incorporation of GL. This led to the chain-spreading of CH, which ultimately increased the flexibility of the composite films (CH-GL). The DSC of the CH film showed two peaks: one endothermic peak below 100 °C (due to water vapor) and a second exothermic peak that appeared between 130 and 360 °C (degradation of the amino group). Plasticization of CH films with GL was confirmed by DSC, where the exothermic degradation was converted into an endothermic peak. Depending upon the amount of GL, γ-irradiation considerably affected the chemical structure of CH by breaking the carbohydrate and pyranose rings; this led to a decrease in the crystallinity of the composite films. The changes studied in the DSC and TGA analysis complemented each other. γ-irradiation also affected the morphology of the films, which changed from smooth and homogeneous to roasted structures, with random swelling on the surface of the films. This swelling reflected the degradation of the surfaces into thin layers. Considering the changes that occurred in the films post-γ-irradiation, it can be inferred that the irradiation dose of 102 kGy is sufficient to degrade as-prepared biopolymer composites.

Polymer for Internal Hydrophobization of Cement-Based Materials: Design, Synthesis, and Properties

A series of novel comb-like poly(butyl acrylate)-g-poly(dimethylaminoethyl methacrylate) (PBA-g-PDMAEMA) with different side chain lengths were designed and successfully synthesized by the “first main chain then side chain” method. Infrared Spectroscopy (IR), 1H Nuclear Magnetic Resonance (1H NMR), and gel permeation chromatography (GPC) were used for structural confirmation and molecular weight characterization. This polymer exhibited responsive behavior from hydrophilicity to hydrophobicity under the alkaline environment of cement-based materials, with the contact angle of 105.6°, a decreased evaporation rate, and a hydrophile–lipophile balance (HLB) value. A significant internal hydrophobic effect on cement mortar was shown in the water absorption rate, which decreased by 75.2%, and a dry shrinkage-reducing rate of more than 30%. Furthermore, this polymer can effectively slow the exothermic rate, reduce the heat release, and delay the exothermic peak of cement hydration. It was interesting that these properties showed a direct correlation with the side chain length of the comb polymer. The aims of this study are to provide a new avenue to synthesize polymers with the spontaneous hydrophilicity–hydrophobicity transition in the cement system, achieving excellent internal hydrophobicity of cement-based materials, and to offer a promising alternative to resist external erosion for improving the durability and service life of cement-based materials.

Non-isothermal crystallization of LiNaGe4O9 glass

The glass of lithium-sodium tetragermanate LiNaGe4O9 is crystallized on heating under the control of differential scanning calorimetry and thermal gravimetric analysis. The measurements were prepared in the temperature range 300-870 K and showed the relatively weak endothermic DSC anomaly and 40-50 K above the single exothermic peak. The endothermic anomaly observed at Tg testified to softening the glass structure whereas the exothermic peak at TC manifested crystallization of the amorphous phase. Studying of TGA demonstrated smooth nearly linear dependences without any visible anomalies. Varying the heating rate from 1.2 up to 40 K/min resulted in noticeable increase of the characteristic temperatures Tg and TC. Lower limit of the glass transition temperature Tg0 was estimated with the help of the existing model. The mechanism of the LiNaGe4O9 glass crystallization is discussed.

Evaluation and Characterization of Tamarind Gum Polysaccharide: The Biopolymer

Polymers from natural sources are widely used as excipients in the formulation of pharmaceutical dosage forms. The objective of this study was to extract and further characterize the tamarind gum polysaccharide (TGP) obtained from Tamarindus indica as an excipient for biomedical applications. Double distilled water was used as a solvent for the extraction of gum while Ethyl alcohol was used as an antisolvent for the precipitation. The results of the Hausner ratio, Carr’s index and angle of repose were found to be 0.94, 6.25, and 0.14, respectively, which revealed that the powder is free-flowing with good flowability. The gum was investigated for purity by carrying out chemical tests for different phytochemical constituents and only carbohydrates were found to be present. The swelling index was found to be 87 ± 1%, which shows that TGP has good water intake capacity. The pH of the 1% gum solution was found to be neutral, approximately 6.70 ± 0.01. The ash values such as total ash, sulphated ash, acid insoluble ash, and water-soluble ash were found to be 14.00 ± 1.00%, 13.00 ± 0.05%, 14.04 ± 0.57% and 7.29 ± 0.06%, respectively. The IR spectra confirmed the presence of alcohol, amines, ketones, anhydrides groups. The contact angle was <90°, indicating favorable wetting and good spreading of liquid over the surface The scanning electron micrograph (SEM) revealed that the particle is spherical in shape and irregular. DSC analysis shows a sharp exothermic peak at 350 °C that shows its crystalline nature. The results of the evaluated properties showed that TGP has acceptable properties and can be used as a excipient to formulate dosage forms for biomedical applications.

A Study on the Heat Effect and Kinetics During Magnesiothermic Reduction of Porous SiO2

Magnesiothermic reduction reaction (MRR) is an effective method to synthesis Si nanoparticles. In this paper, the heat effect and MRR kinetics were investigated by real-time temperature monitoring and analyzing the DSC curve of the MRR. It was found that the MRR onset temperature is about 465 °C, and the system temperature rose sharply at 535 °C. After the disappearance of the magnesium phase, the system temperature remained consistent with the set value. The exothermic peak lags and the spike decreases when adding NaCl into the system. The MRR was chemical reaction control, corresponding with the apparent activation energy was 193.456 kJ·mol-1 (without NaCl) and 191.434 kJ·mol-1 (with NaCl) in the temperature interval 465 °C −700 °C, respectively. NaCl affects the reaction mechanism by lowering the temperature of the system. Our work successfully prepared the spherical Si nanoparticles, which average grain size increased from 25 nm to 40 nm with the extended reaction duration. The conversion rate of porous SiO2 precursor was as high as 92%.

Laboratory Research and Evaluation on Design and Application Performance of High-Performance Cold-Mix Resin

To improve the safety of orthotropic steel bridge decks and the construction efficiency of bridge deck pavement by enhancing the performance of pavement materials, a new-generation, high-performance cold-mix resin was prepared by carrying out the combination of micro-characteristic analysis and performance test. Meanwhile, the pavement performance and fatigue performance of high-performance cold-mix resin mixtures and hot-mix epoxy saphalt mixtures as a control group were studied experimentally. The results show that different kinds of epoxy resins show bisphenol structure in essence. The curing exothermic peak temperature of the cold-mix resin increases with the heating rate. Both the specific heat capacity (△CP) of cold-mix resin and cold-mix resin asphalts exhibit a sudden change between −20 °C and 40 °C. In resin asphalt mixtures, cold-mix resin forms the network structure skeleton whereas the asphalt distributed in the form of tiny particles. The dosage of respective component has a significant effect on the tensile strength and elongation at break of cold-mix resin. Compared with hot-mix epoxy asphalt mixtures, cold-mix resin mixtures exhibit comparable water stability and high and low-temperature performance, as well as greater fatigue life.

Spray-Dried Quercetin-Lactose Powders for Oral Tablets with Improved Dissolution Rates and Modified Material Properties

This study is aimed at using spray drying method to codisperse it with the commonly used drug carrier lactose in different solvents and then pass it through a spray dryer to obtain different samples. The results showed that the dissolution rate and solubility of the samples obtained by dispersion in hot water and 25% ethanol were significantly higher. The water of crystallization peaks of the raw material disappeared at 105-125°C and 130-150°C (DSC). The excipient lactose had a small upward exothermic peak at 177°C and a significant heat absorption peak at 209°C before untreated (XRD). α-Lactose peaks were observed at 12.5°, 19.1°, 19.6°, and 19.9° at 2θ in both samples, and β-lactose peaks were found at 10.5° at 2θ in sample A, but not in sample B (FTIR). The complex sharp peaks of lactose at 1100 cm-1 and quercetin at 1700-1000 cm-1 became moderated (SEM). The sample obtained by spray drying has a slit-type mesoporous structure with an average pore size of about 9.3 nm.