SPECTROSCOPIC CHARACTERIZATION OF SOLVENT SOLUBLE FRACTIONS OF PETROLEUM VACUUM RESIDUES

ABSTRACT

NMR and FTIR spectroscopic techniques were used to investigate the effect of different solvent extraction schemes on the composition and chemical nature of species of vacuum residues of two Indian crude oils (namely Jodhpur and Heera) extractable into polar (ethyl acetate) and non-polar (n-pentane and n-heptane) solvents. The obtained soluble fractions were found to consist of mainly simple aliphatic and naphthenic ring structures, while insoluble fractions consisted primarily aromatic compounds. The results were used to draw inferences on the relative utility of different extraction schemes to upgrade vacuum residues as feedstocks for secondary conversion processes in petroleum industry.     

Online monitoring of the thermal degradation of POM during melt extrusion

Because of its high stiffness, chemical resistance, and low viscosity, Poly (oxymethylene) (POM) is of high relevance for technical applications. The thermal degradation of POM during processing affects its final properties and decreases the long‐term stability. The degradation is indicated by the emission of formaldehyde (FA) gas. The aim of this study is to monitor the thermal degradation of POM online, during the melt extrusion in a co‐rotating twin screw extruder (TSE). The effect of the processing conditions on the thermal stabilisation of the POM is observed by FA emission and online viscosity measurements. The effect of processing conditions on the compounding of POM with two different FA scavengers is also studied. Fourier transform infrared (FTIR) spectroscopy is used for the online measurement of FA gas and acetyl acetone colour measurement for the offline characterisation. The online viscosity is measured by passing the melt through a slit die at constant volume flow rate. An enhanced thermal degradation is found with decreasing throughput and increasing screw speed. A good correlation between the online viscosity and offline FA measurement is observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In situ FTIR study of the decomposition of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ionic liquid during cathodic polarization of lithium and graphite electrodes

In this work we analyzed the cathodic reactions of an important ionic liquid (IL) based electrolyte solution, namely lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)/N-methyl-N-methylpyrrolidinium (BMP) TFSI. In situ FTIR spectroscopy was used for the analysis of gaseous products of the electrochemical decomposition of this IL solution during cathodic polarization of lithium metal and graphite electrodes. The main volatile product of the reductive decomposition of the anion in these BMPTFSI solutions is trifluoromethane. BMP cations decompose to mixtures of tertiary amines and hydrocarbons. The composition of the products is influenced by the nature of the anode material. Graphite possesses a catalytic activity in the electroreduction process of BMP cations which occurs along with their intercalation into the graphite structure. The liquid phase after cathodic polarization of graphite electrodes was analyzed by multinuclear NMR spectroscopy coupled with FTIR spectroscopy. ¹⁵N NMR and FTIR spectra revealed an increase in the Li cations content in the electrolyte solution, as a result of BMP cations decomposition during repeated cycling of graphite electrodes.     

Effect of chlorine dioxide gas on physical,thermal, mechanical,and barrier properties of polymeric packaging materials

The effects of gaseous chlorine dioxide (ClO₂) on properties and performance of 10 selected polymeric packaging materials, including polyethylene (PE), biaxially oriented poly(propylene), polystyrene, poly(vinyl chloride), poly(ethylene terephthalate) (PET), poly(lactic acid), nylon, and a multilayer structure of ethylene vinyl acetate (EVA)/ethylene vinyl alcohol (EVOH), were evaluated. Physical, mechanical, barrier, and color properties as well as infrared (IR) spectra were assessed before and after polymer samples were exposed to 3600 ppmV ClO₂ gas at 23°C for 24, 168, and 336 h. The IR spectra of the ClO₂‐treated samples revealed many changes in their chemical characteristics, such as the formation of polar groups in the polyolefin, changes in functional groups, main chain scission degradation, and possible chlorination of several materials. The ClO₂‐treated PE samples showed a decrease in tensile properties compared with the untreated (control) films. Decreases in moisture, oxygen, and/or carbon dioxide barrier properties were observed in the treated PE, PET, and multilayer EVA/EVOH/EVA samples. A significant increase (P < 0.05) in the barrier to O₂ was observed in the ClO₂‐treated nylon, possibly the result of molecular reordering, which was found through an increase in the crystallinity of the material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,crystal growth,thermal studies and scaled quantum chemical studies of structural and vibrational spectra of the highly efficient organic NLO crystal: 1-(4-Aminophenyl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one

A new chalcone derivative, 1-(4-aminophenyl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one (DMAC) was synthesized and single crystals were grown by slow evaporation technique. The FT-Raman and FT-IR spectra of the sample were recorded in the region 3700–100 cm⁻¹ and 4000–400 cm⁻¹, respectively. The spectra were interpreted with the aid of normal coordinate analysis following structure optimizations and force field calculations based on density functional theory (DFT) at the B3LYP/6-311+G(d,p) level of theory. Normal coordinate calculations were performed using the DFT force field, corrected by a recommended set of scaling factors, yielding fairly good agreement between the observed and calculated wavenumbers. DMAC is thermally stable up to 220.0 °C and optically transparent in the visible region. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). The SHG efficiency of DMAC is observed to be 10 times that of standard urea crystal of identical particle size.     

Spectroscopic studies and evaluation of thermorheological properties of softwood and hardwood lignin

Fourier transform infrared spectroscopy ( FTIR) was used to determine characteristic absorption peaks of softwood kraft lignin and soda hardwood lignin. Remarkable spectral differences were noticed between the different lignins due to their various chemical structures. Proton nuclear magnetic resonance spectrometry (¹H NMR) was employed to analyze the structure of lignin. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry ( MALDI‐TOF) provided important data regarding the molecular weight distribution of lignin. Thermal stability of softwood lignin was found to be remarkably higher than that of hardwood lignin. Softening temperature and glass transition temperature of lignin were measured by differential scanning calorimetry (DSC) which was useful in selecting an optimal temperature profile during extrusion process. Rheological studies provided valuable information about the viscosity of lignins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Epoxy curing reaction studied by using two‐dimensional correlation infrared and near‐infrared spectroscopy

The isothermal curing process of bisphenol A epoxy resin with polyamine reagent (1,6‐diaminohexane) was monitored in situ by using temperature‐controlled Fourier‐transform infrared (FTIR) and Fourier‐transform near infrared (FTNIR) spectroscopy to elucidate the relative changes in functional groups during the curing reaction. It was shown that generalized two‐dimensional correlation spectroscopy can provide new information about the mechanisms and kinetics of the curing process, and the band assignments for complex NIR spectrum associated with this system. The sequential order of relative changes in functional groups during the curing process was examined by generalized 2D correlation spectroscopy and NIR‐IR hetero‐correlation spectroscopy, and the details of the complex epoxy curing reaction involving both primary and secondary amino group were revealed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Accelerated weathering of pectin/poly(vinyl alcohol) blends studied by spectroscopic methods

The blends of pectin (PEC) and poly(vinyl alcohol) (PVA) at different components ratios were prepared by mixing in water. Thin polymeric films of PEC/PVA blends and pure polymers were obtained by casting method. All samples were then artificially aged using Suntest apparatus (Atlas) up to 780 h. The changes in chemical structure during sample ageing have been monitored by infrared and ultraviolet‐visible absorption spectroscopies. The first stage of weathering (up to ～ 300 h) was very slow and alteration of chemical structure was negligible in all samples. Prolonged ageing (>300 h) caused more significant degradation processes. FTIR spectra exhibited the highest changes in hydroxyl and carbonyl band ranges indicating the efficient photooxidation of macromolecules. The mechanisms of the observed processes have been discussed. It was found that PVA undergoes faster photoxidative degradation than pectin aged at the same conditions. The PEC/PVA blends exhibited the improved resistance to weathering comparing with both polymers aged individually. Mutual stabilization effect can be explained by intermolecular interactions between PEC and PVA confirmed by spectroscopic methods. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

煤矿用高水无机膨胀充填材料泌水分析表征

通过化学方法检测分析了榆阳煤矿高水无机充填材料的泌水组分，分析确定硫酸根离子的浓度为1344mg／L；红外分析发现，溶液中含有机物量少，且都是对人体无害的水泥添加剂组分；原子吸收光谱检测钙、镁离子、硅酸根浓度，其中硅酸根和钙离子超出了仪器的检测范围，即〉1000mg／L，Mg2＋含量为362mg／L。综合检测分析发现，充填泌水主要为高水充填材料中的石膏、水泥、粉煤灰、水泥外加剂等可溶成分。