Synthesis and Characterization of A Novel Macromolecular Hindered Phenol Antioxidant and Its Thermo-Oxidative Aging Resistance for Natural Rubber

A novel macromolecular hindered phenol antioxidant with high antioxidative efficiency, polyhydroxylated polybutadiene (PHPB)-bound 2, 2′-thiobis (4-methyl-6-tert-butylphenol) (PHPB-b-TPH), was prepared by binding 2, 2′-thiobis (4-methyl-6-tert-butylphenol) (TPH) onto PHPB with isophorone diisocyanate (IPDI), using dibutyltin dilaurate (DBTDL) as catalyst, via a two-step nucleophilic addition reaction. The PHPB was first synthesized from hydroxyl-terminated polybutadiene (HTPB) and 2-mercaptoethanol via a thiol-ene click reaction. The PHPB-b-TPH was characterized by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (¹H-NMR), gel permeation chromatography (GPC), and thermal gravimetric analysis (TGA). The thermo-oxidative aging resistance of natural rubber (NR) with PHPB-b-TPH was evaluated by an accelerated thermal aging test and the oxidation induction time (OIT). The results showed that the ?OH groups of PHPB first reacted with highly active secondary ?NCO groups of IPDI at 35°C to form the adduct PHPB-NCO, and the PHPB-b-TPH was successfully obtained by one of the phenolic ?OH in TPH reacting with the primary ?NCO groups of PHPB-NCO at 70°C. The PHPB-b-TPH had better thermal stability and thermo-oxidative aging resistance for NR than TPH.     

Fourier transform infrared spectroscopy to detect thermal degradation of vegetable and chrome-tanned leather

Abstract

The present experimental study determined the thermal degradation stages for vegetable and chrome-tanned leathers (goat and sheep) at 90, 100, and 130?°C by using Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis. Infrared spectra revealed that a temperature of 90?°C affected the adsorbed water band at 3400?cm^?1. Moreover, this temperature slightly reduced the vibrations of amide II and amid III (1340?cm^?1) confirming the preliminary decomposition of protein folds, but it is worth noting that the aliphatic side chains remained stable at this stage of aging. At 100?°C, there was a sharp rupturing in the phenolic-OH bond and side-by-side N–H vibrations decreased dramatically. The peak decomposition occurred at 130?°C, where the amide I and amide III intensities significantly increased, which can be considered indicative of protein unfolding. Those changes are substantiation of protein denaturation. Thermal analysis demonstrated that thermal aging significantly reduced the required temperature for the process of oxidation. The oxidation occurred at 217?°C in goat sample aged at 90?°C. Nevertheless, the reference sample suffered from oxidation at about 220?°C, while with increasing aging temperatures (at 100 and 130?°C), endothermic reactions were observed. Such reactions are usually associated with protein denaturation.     

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO₂ particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO₂) were obtained. The composites C(NR/nSiO₂) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO₂) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO₂ in NR were investigated. The results obtained were compared with the NR/SiO₂ composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent (Si69) in C(NR/nSiO₂), the vulcanizate had better mechanical properties, higher wet resistance, and lower rolling resistance than those without Si69. In the composites C(NR/nSiO₂) and their vulcanizates, the SiO₂ particles’ average grain diameter was 60 nm, and the good-dispersion of the in-situ generated SiO₂ in the rubber matrix were a significant contribution to the satisfactory properties of C(NR/nSiO₂) composites and their vulcanizates.     

Structural changes in Poly(lactic acid)–zeolite nanocomposites exposed to 60Co gamma rays

Poly(lactic acid) (PLA) nanocomposites containing 3%, 5% and 7% zeolite used in the present research study were prepared by solution casting. The PLA nanocomposites were structurally characterized by Scanning Electron Microscopy and Fourier-transform infrared spectroscopy. The effects of the gamma radiation at the absorbed doses of 10, 15 and 20?kGy on the structures and thermal properties of the nanocomposites were investigated in a tetrahydrofuran solvent. Thermodecomposition tests and analyses were carried within 30–500°C range at the rate of 10°C?min^?1 by thermogravimetric analysis (TG). The activation energies for thermal degradation of the nanocomposites were calculated from their TG data by Flynn–Wall–Ozawa method. The G values of the nanocomposites were calculated based on molecular weights which were measured by means of gel permeation chromatography before and after the gamma irradiation. The E_a and molecular weight results showed that addition of zeolite to the PLA affected the radiation resistance of the polymer.     

Electrochemical synthesis and characterization of a new conducting polymer: Polyrhodanine

An antimicrobial drug, rhodanine (Rh), was electrochemically polymerized on a Pt electrode using cyclic voltammetry (CV). The high quality and homogeneous polyrhodanine (pRh) films with a dark-purple color were obtained. The chemical structure characterization was investigated by Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy techniques. Further, thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques used to investigate thermal properties of the film. It is found that thermal stability of pRh films is relatively high. It is also observed that tetrahydrofurane (THF) and N-methyl-2-pyrrolidone (NMP) are good solvents for the polymer.     

反式二丁烯和氢气流量比对辉光放电聚合物热稳定性能的影响

用低压等离子体化学气相沉积法,以T2B和H2为工作气源,改变T2B与H2的流量比例制备了辉光放电聚合物(GDP)涂层。通过GDP碳氢涂层的傅里叶变换红外吸收光谱讨论了流量比例对其内部结构的影响,利用热重曲线表征了GDP碳氢涂层在50~600℃范围内的热失重情况,并且结合其结构讨论了流量比例变化对GDP碳氢涂层的热稳定性的影响,最后探讨了GDP碳氢涂层可能的热裂解过程。结果表明:随着T2B与H2流量比的增大,GDP碳氢涂层中C(sp2)-Hx/C(sp3)-Hx含量逐渐降低,-CH3含量增加,碳链逐渐变短而支链含量增加,其热稳定性逐渐变差。以T2B与H2流量比为0.04时,可以成功制备出ICF物理实验所需的靶丸烧蚀层。     

Synthesis and structural properties of polypyrrole/nano-Y2O3 conducting composite

In this work, polypyrrole/nano-Y₂O₃ conducting composite was synthesized by chemical oxidative polymerization. The composite was characterized using transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectra, UV-vis absorption spectra, X-ray photoelectron spectroscopy and electrical conductivity measurements. The results indicate that Y₂O₃ nanoparticles are almost enwrapped by polypyrrole. The addition of Y₂O₃ nanoparticles results in changes in the surface structure and conductivity of the composite. Thermogravimetric analysis shows that composite has better thermal stability than that of pure polypyrrole.     

Influence of Crosslink Density on Mechanical Properties of Natural Rubber Vulcanizates

Crosslink density is an important structural parameter for cured rubber. Natural rubber (NR) vulcanizates with different crosslink densities were obtained through using different sulfur and accelerator amounts and different accelerator types. The crosslink density was characterized by an ¹ H-NMR technique and its influence on mechanical properties, such as Shore A hardness, 300% modulus, tensile strength, and elongation at break, of NR vulcanizates was investigated. The results showed that both the sulfur amount and the accelerator type and amount had an influence on the crosslink density of the NR networks. The relationship between total crosslink density and mechanical properties was also studied. The results, by changing either the sulfur or the accelerator amount, showed that tensile strength of NR vulcanizates reached maximum value when the total crosslink density was around 13.5 × 10^?5 mol/cm³, equivalently the average molecular weight of the intercrosslink chains (Mc) was around 7000 g/mol. The maximum value of tensile strength came from the balance between contributions of crosslink joints and stretch-induced orientation and/or crystallization of intercrosslink chains. The study on influence of total crosslink density on Shore A hardness and 300% modulus of NR vulcanizates showed that they both increased linearly with the crosslink density, the slopes were 2.7 ～ 3.0 cm³/10^?5 mol and 0.27 ～ 0.31 MPa cm³/10^?5 mol for Shore A hardness and 300% modulus, respectively, whether the crosslink density was varied by sulfur or accelerator.     

Natural rubber blends with epoxidized natural rubber

Blends of NR with ENR have been prepared in full composition following the polymer blend technique. Basic properties (mastication behavior and thermal degradation of each rubber and Mooney viscosity, Flory-Huggins interaction parameters, and cure characteristics of the blends) of the uncured blends were determined, in addition to the reversion, cross-linking density, mechanical and dynamic mechanical properties, rebound, and solvent swell of the blend vulcanizates. It was found that the NR ENR blends are immiscible, showing two glass transition temperatures (T_g's) that showed outward migration in the blends. This was interpreted in terms of preferred migration of the curatives into the ENR phase. Retention of mechanical properties on aging, solvent resistance, and heat buildup were greater in NR-rich blends due probably to the higher cross-link density of the blends.     

Designing and Characterization of Poly(L-Lactide)/Poly(ϵ-Caprolactone) Multiblock Copolymers

A series of poly(L-lactide)/poly(?-caprolactone) (PLA/PCL) biodegradable multiblock copolymers was synthesized by a two-step process and characterized. Ring-opening polymerization was used to prepare a series of HO-PLA-PCL-PLA-OH copolymers initiated by hydroxyl-terminated PCL. Then the triblock copolymers and 1,6-hexamethylene diisocyanate (HDI) were reacted with different copolymer/HDI weight ratios. Consequently, a series of PLA/PCL multiblock copolymers with designed molecular chain structure was obtained. Gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and ¹H NMR were used to characterize these copolymers and the results showed that the designed PLA/PCL copolymers had been synthesized. Dynamic mechanical analysis (DMA) was applied to characterize their thermal properties. Stress–strain curves showed that a PLA/PCL copolymer with adjustable mechanical properties had been achieved.     

Surface-modified antibacterial TiO2/Ag nanoparticles: Preparation and properties

Studies were performed on surface modification of antibacterial TiO₂/Ag⁺ nanoparticles by grafting γ-aminopropyltriethoxysilane (APS). The interfacial structure of the modified particles was characterized by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The thickness of the surface layer was determined by using Auger electron spectroscopy (AES). The results show that APS is chemically bonded to the surface of antibacterial TiO₂/Ag⁺ nanoparticles. Furthermore, the modified particles were mixed in PVC to prepare composites whose antibacterial property was investigated. The results suggest that surface modification has no negative effect on antibacterial activity of TiO₂/Ag⁺ nanoparticles and PVC-TiO₂/Ag⁺ composites exhibits good antibacterial property.     

Synthesis and Characterization of Waterborne Epoxy–Acrylic Corrosion-Resistant Coatings

Waterborne acrylate (AC) and epoxy–acrylate (EAC), and the ether of melamine formaldehyde (EM) as cross-linker, were synthesized. The structures of AC and EAC were characterized by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopy. Their anticorrosive EM-cured AC and EAC coatings (referred to here as AC/EM and EAC/EM, respectively) were applied on mild steel strips and their properties were evaluated by physicomechanical and corrosion resistance tests, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The coating system EAC/EM exhibited superior performance in all aspects of physicomechanical performance, corrosion resistance, and thermal stability when compared with AC/EM.     

Comparison of the thermal stability of the α, β and γ phases in poly(vinylidene fluoride) based on in situ thermal Fourier transform infrared spectroscopy

The electroactive β phase of poly(vinylidene fluoride) (PVDF) is induced due to the aging time of PVDF solutions. The feasibility of the combination of the three crystalline polymorphs (α, β and γ) is demonstrated where their relative proportion within the PVDF film can be tailored by the simple monitoring of the preparation conditions. To identify all these phases, Fourier transform infrared (FT-IR) spectroscopy is carried out and it is spotlighted that the vibrational bands at 510 and 841 cm^?1 are not sufficient to state the formation of the β phase. The main aim of this work is devoted to develop a better understanding on the thermal stability of these several phases of PVDF, which has a longstanding ambiguity persisting in this area. It has been found that the in situ thermal FT-IR spectroscopy is one of the best alternatives to understand this important issue. It is ascertained that the β phase is the least thermally stable phase among α, β and γ phases, whereas the γ phase is the most thermally stable phase.     

The interface structure of nano-SiO2/PA66 composites and its influence on material's mechanical and thermal properties

The PA66-based nanocomposites containing surface-modified nano-SiO₂ were prepared by melt compounding. The interface structure formed in composite system was investigated by thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The influence of interface structure on material's mechanical and thermal properties was also studied. The results indicated that the PA66 chains were attached to the surface of modified-silica nanoparticles by chemical bonding and physical absorption mode, accompanying the formation of the composites network structure. With the addition of modified silica, the strength and stiffness of composites were all reinforced: the observed increase depended on the formation of the interface structure based on hydrogen bonding and covalent bonding. Furthermore, the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that the presence of modified silica could affect the crystallization behavior of the PA66 matrix and lead to glass transition temperature of composites a shift to higher temperature.     

Preparation of fluorocarbon thin film deposited by soft X-ray ablation and its electrical characteristics and thermal stability

Fluorocarbon films were deposited by soft X-ray ablation of polytetrafluoroethylene (PTFE) and characterized as low-dielectric-constant interlayer dielectrics. Very rapid deposition of such films at approximately 1500 nm/min could be achieved at room temperature. Fourier-transform infrared spectroscopy (FT-IR) measurement results suggest that the films deposited are primarily formed as one-dimensional chains of (-CF₂-)_n which are partially cross-linked. The cross-link density increases with increasing deposition temperature, which improves the thermal stability. However, the dielectric constant of the films increased abruptly above 300 °C. The dielectric constant and leakage current at 1.0 MV/cm of the film deposited at room temperature were approximately 2.1 and 2.0×10⁻⁹ A/cm², respectively.     

Synthesis of a New Nanosilica-Based Antioxidant and Its Influence on the Anti-Oxidation Performance of Natural Rubber

Nanosilica was modified with a silane coupling agent 3-Glycidoxypro- pyltrimethoxysilane (KH-560) and then reacted with p-aminodiphenylamine (RT) to obtain a new nanosilica-based antioxidant. Fourier transform infrared and thermogravimetric (TGA) analysis measurements confirmed the successful grafting of RT to the nanosilica surface. Scanning electron microscope analysis showed that the nanosilica-based antioxidant could be homogeneously dispersed in a natural rubber matrix. Differential scanning calorimetry and TGA were used to measure the thermal oxidative behavior of rubber vulcanizates with different types of fillers. It was found that the thermal oxidative stability of rubber vulcanizates with the nanosilica-based antioxidant was improved to a greater extent than that with other fillers examined.     

CexZr1-xO2固溶体储氧性能与结构的关系

采用加热回流技术制备了系列CexZr1-xO2(0.25≤x≤1)固溶体,通过N2物理吸附、XRD、Raman光谱、UV-Vis漫反射光谱表征了不同铈锆组成的铈锆复合氧化物结构对储氧性能的影响.结果表明,在铈锆组成比不同的样品之间,结构性质相差较大,随着载体中ZrO2 mol%的增加,载体结构从相对的有序经无序再回到相对的有序.Ce0.4Zr0.6O2样品具有最高的储氧性能,而Ce0.25Zr0.75O2样品具有较高的热稳定性.     

Syntheses and characterization of Sr(OH)2 and SrCO3 nanostructures by ultrasonic method

The Sr(OH)₂ and SrCO₃ nanostructures were synthesized by reaction of strontium(II) acetate and sodium hydroxide or tetramethylammonium hydroxide (TMAH) via ultrasonic method. Reaction conditions, such as the concentration of the Sr²⁺ ion, aging time, power of the ultrasonic device and alkali salts show important roles in the size, morphology and growth process of the final products. The pure crystalline SrCO₃ were obtained by heating of product at 400 °C. The Sr(OH)₂ and SrCO₃ nanostructures were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), thermal gravimetric (TG), differential thermal analyses (DTA) and the infrared spectroscopy (IR).     

Vulcanization and Thermal Properties of Silicone Rubber/Fluorine Rubber Blends

With the rapid development of automobile, aviation, aerospace, machinery and other fields, rubber products used in these fields required to meet higher requirements. Fluorine rubber (FKM) and silicone rubber (MVQ) have excellent performance in some areas. However, the FKM is poor in low-temperature resistance and processing performance, limiting its applicability. Although the MVQ has a wide range of temperature and excellent processing performance, but its mechanical properties and oil resistance are not good. In this work, the MVQ/FKM blends were prepared by two different mechanical blending methods. The effects of the mixing process, mass ratio, curing system and conditions of the blends were studied. The chemical compositions of the blends were analyzed by infrared spectroscopy (IR). The compatibility and the thermal properties of the blends were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. The results showed that the mechanical properties, compatibility and thermal stability of the blends were the best when they were prepared by kneading the FKM and MVQ individually in a two-rool mill roll, then mixing them together homegeneously with an MVQ/FKM mass ratio of 10/90, curing system of (4 phr, 1/9) dicumyl peroxide (DCP)/N, N-Dicinnamylidene-1, 6-hexanediamine (3^# Vulcanizer), first curing conditions at 170?°C under 10?MPa for 30?min and post curing conditions at 200?°C for 6?hours at 1 atmospheric pressure.     

Synthesis and properties of Sn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> nanoparticles obtained by a proteic sol–gel method

Iron-doped SnO₂ nanoparticles with chemical formula Sn_1?xFe_xO_2?y (x =?0.02, 0.05 and 0.10 at%) were successfully produced by a proteic sol–gel method. Thermogravimetric analysis and differential scanning calorimetry were performed to investigate the thermal behavior of the precursor powders as well as to select the appropriate calcination temperatures for oxide formation. X-ray absorption near-edge spectroscopy studies were carried out to determine the valence state of the transition metal used as dopant. Structural, morphological, and optical properties of the synthesized materials were studied by X-ray diffraction, Mössbauer spectroscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, and ultraviolet-visible spectroscopy. The results confirmed the formation of nanometric spherical particles of single-phased SnO₂ with rutile-type tetragonal structure. Iron doping was accomplished in the form of Fe³⁺ substituting for Sn⁴⁺ in the SnO₂ matrix, with the creation of oxygen vacancies to achieve charge balance. Band gaps of SnO₂ were found to be unaffected by the introduction of iron.