The kinetics and mechanism of cure of an amino-glycidyl epoxy resin by a co-anhydride as studied by FT-Raman spectroscopy

The thermal curing behavior of tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and a co-anhydride mixture consisting of maleic anhydride (MA) and hexahydrophthalic anhydride (HHPA) was studied from 55 to 100 °C by real-time FT-Raman spectroscopy. The quantitative changes in concentrations of anhydride, epoxy, and new-formed ester were measured and empirical reaction rate curves were constructed reflecting the kinetics of the curing process. After an induction period a simple kinetic scheme that is first order in both epoxy and anhydride monomer consumption described the reaction profile until the reaction was influenced by chemo-rheological changes due to vitrification transition.FT-Raman analysis revealed that curing propagation mainly occurs by polyesterification between epoxide and anhydride. Possible side reactions including the homopolymerization of MA are considered. The main side reaction is decarboxylation of MA that may produces some autocatalysis, but this is a minor contribution to the kinetics of cure. No conclusive evidence has been found for homopolymerization of MA or initiation of the curing reaction by the reaction product of TGDDM and MA, compared to the polyesterification.     

Positron annihilation spectroscopy of polyacrylonitrile-based carbon fibers embedded with multi-wall carbon nanotubes

Polyacrylonitrile (PAN)-based carbon fibers, embedded with multi-wall carbon nanotubes (MWCNT) in different concentrations, have been prepared by an electrospinning technique and investigated using scanning electron microscopy, Raman, and positron annihilation spectroscopy. An analysis of the positron lifetime and Doppler broadened spectral line shape has been made. Positron lifetime spectra for all the samples give best fit for three distinct lifetime components. Raman data has been used to estimate the sp² mole fraction in the fiber. It is found that the gradual changes incorporated in the fiber due to the addition of MWCNTs are reflected as well defined changes in the positron lifetime and the S parameter of the Doppler broadened spectral line. Annihilation parameters are discussed from the point of view of formation of distinct positron trapping sites in the form of vacancy type defects at the interfaces of MWCNTs and the PAN matrix, and their variations in concentration due to different amount of MWCNTs added.     

Surface composition of carbon fibers subjected to oxidation in nitric acid followed by oxygen plasma

Type II, PAN-based carbon fibers (unsized and commercially treated) have been exposed to nitric acid and oxygen plasma individually and also to combined nitric acid/oxygen plasma treatments and the surface compositions have been determined using angle-resolved X-ray photoelectron spectroscopy (ARXPS) and ion scattering spectroscopy (ISS). Most of the oxygen on the as-received carbon fibers resides within the outermost 10-15 Å of the surface. Fiber exposure to nitric acid at 115°C for 20-90 min enhances the oxygen surface concentration to a point of saturation and the oxygen depth distribution is increased and becomes more uniform within the maximum XPS sampling depth (~60-100 Å). In addition, the fiber surface area is believed to be increased. After treating fibers to various degrees in nitric acid, subsequent exposure to oxygen plasma yields an additional increase in the surface oxygen content, particularly in the outermost fiber layers (10-15 Å). Under the conditions of the investigation, the maximum amount of surface oxidation occurs after sequential fiber exposure to nitric acid at 25°C for 30 s and oxygen plasma. As the extent of initial nitric acid treatment is increased, the synergism with subsequent plasma oxidation decreases, and the oxygen concentration becomes more uniform within the outer layers of the oxidized fibers. Overall, the data are consistent with a proposed oxidation mechanism in which oxygen plasma acts to enhance the surface density of oxygen on roughened and pitted nitric acid-oxidized fiber surfaces. As the duration of nitric acid exposure is increased, it is hypothesized that subsequent exposure to oxygen plasma smoothes the fiber surfaces but the surface density of oxygen remains essentially constant.     

Comparison of different methods for lignin determination as a basis for calibration of near-infrared reflectance spectroscopy and implications of lignoproteins

Three commonly employed methods for lignin determination, i.e., the thioglycolic acid (TGA), the acetylbromide (AB), and the acid detergent fiber (ADF) method, were compared using leaves and xylem tissue from five species (Nicotiana tabacum, Populus x canescens, Fagus sylvatica. Quercus robur, and Picea abies). In each case, cell walls were isolated before lignin determination. Each of the three methods estimated a different lignin concentration in a given tissue, except for spruce wood. The lignin concentration determined with the AB method was strongly dependent on whether or not the cell walls were subjected to alkaline hydrolysis to remove covalently bound aromatic nonligneous components before lignin determination. Lignin concentrations determined in hydrolyzed cell walls of different tissues and species by the AB method showed a good correlation with those obtained by the TGA method and, thus, were convertible. In contrast, gravimetrically estimated ADF lignins did not or only moderately correlate with lignins measured with methods based on the UV absorbance of the solubilized lignin degradation products. Leaves of a given species generally contained higher ADF-lignin concentrations than the corresponding stem tissue. Both ADF and TGA lignin data of beech were used to calibrate near-infrared reflectance spectra (NIRS) for lignin prediction. Both NIRS calibration procedures gave good statistical fits with correlation coefficients close to 1, indicating that TGA and ADF lignin concentrations of beech can be estimated by NIRS with high accuracy. However, the two calibrations were based on different empirical terms, showing that TGA and ADF lignins did not share the same physical basis for calibration. C/N analysis revealed the presence of 3.1 and 1.4% nitrogen in ADF lignins of beech leaves and wood, respectively. The major fraction of this nitrogen was recovered in amino acids, which corresponded to 14% and 3% protein in ADF lignins of leaves and wood, respectively. These results show that ADF lignins contain significant concentrations of lignin-bound proteins, which renders this method unsuitable to determine genuine lignin.     

Influence of urea on the coloring ability of a low‐temperature coloring method of keratin fibers using polyethyleneimine

For the purpose of improving the coloring ability of keratin fibers at a lower temperature, we investigated the influence of urea on the coloring ability of a low‐temperature coloring method using polyethyleneimine (PEI) as a counter ion reagent (the human hair was previously treated with a PEI solution, and then was colored with acid dye). The coloring and color fastness to shampooing of the hair pretreated with a PEI solution containing urea clearly improved compared with those pretreated with a PEI solution not containing urea. Also, we prepared cross‐sectional samples of the treated hair and investigated the penetration of PEI and Orange II into human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into human hair pretreated with a PEI solution that contained urea clearly increased compared with those pretreated with a PEI solution that did not contain urea. From these experiments, we concluded that urea acts as a penetration accelerator for PEI; and PEI, which penetrates deeper into human hair by adding urea, exerts counter ionization on Orange II, thus increasing the penetration of Orange II into human hair and thereby improving the coloring ability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3827–3834, 2004     

Reduction of aging tendency in p‐aramide fibers using ultrasound

The impact of ultrasound pretreatment of p‐aramide fibers is investigated to reduce negative effects of fiber aging induced by artificial white light (Suntest), as well as by sunlight and weathering. The investigations indicate that such a pretreatment has a beneficial influence in reducing the aging tendency of the fibers. The ultrasound pretreatment reduces strength losses due to aging in a natural environment by up to 40%, and as much as 60% in artificial environment. A positive impact of the duration of ultrasound treatments is also established in assessing the resistance of p‐aramide fibers to aging. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2340–2345, 2000     

Structure of heat-treated Nylon 6 and 6.6 fibers. I. The shrinkage mechanism

Nylon 6 and 6.6 fibers were submitted to thermal annealing in a wide range of temperatures (below and above their glass transition temperatures) under inert atmosphere and slack condition, allowing free shrinkage. The structural changes due to the heat settings were analyzed by several techniques (differential scanning calorimetry analysis, wide- and small-angle X-ray scattering, and birefringence). The results revealed different recrystallization responses of the fibers to the applied thermal annealings and consequently different shrinkage mechanisms. In the recrystallization of the Nylon 6 fibers were involved a generation of nuclei crystallites in the interfibrillar regions, as well as growth and perfection of these new crystallites and preexisting ones. But, recrystallization of the Nylon 6.6 fiber was accompanied only by growth and perfection of the preexisting crystals. The existence of the nuclei crystallites at temperatures of heat treatments above 120°C was the major commanding factor for the Nylon 6 fiber to undergo less shrinkage than the Nylon 6.6 fiber. These very tiny crystallites worked as crosslinking points that would impose restrictions in the mobility of the chains segments, inhibiting subsequent disorientation of the amorphous regions and consequently intense shrinkage, thus resulting in recrystallization in a preferred direction of the fiber axis. The Nylon 6.6 fiber experienced an instantaneous shrinkage at the annealing temperature around 70°C. That was the temperature necessary to release its hydrogen bonds and the starting temperature for presenting its major structural changes, including global disorientation of the amorphous and crystalline regions. Thus, its recrystallization occurred with no preferred orientation. Also, it was suggested that the occurrence of so different shrinkage mechanisms reside in the different crystalline morphology that these fibers originally possessed before the heat treatments. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 441–452, 1998     

Diffuse reflectance Fourier transform infrared spectroscopy of oleic acid adsorption on silicic acid

Diffuse reflectance Fourier transform infrared spectroscopy was used to observe adsorption complexes of oleic acid and isopropanol (IPA) on silicic acid in hexane. The spectra provide definite evidence of the molecular nature of the surface interaction. In addition, the effect on oleic acid adsorption of modifying the solvent with IPA, which competes for adsorption sites and modifies the solvent polarity, was studied. Oleic acid adsorption was reduced in the presence of an equimolar IPA concentration in hexane, relative to that from hexane alone. This could be explained by a combination of competitive adsorption of IPA and IPA interacting with oleic acid in solution. IPA, in solution, and silica are probably competing for the lipid. This is additional evidence that suggests that lipid adsorption onto silicic acid is influenced by competitive adsorption. The adsorption of oleic acid and IPA, from a mixture of the two in hexane, was controlled by (i) the equilibrium between surface-bound species and molecules in solution and (ii) the polar interaction between oleic acid and IPA in solution. Thus, washing pre-bound oleic acid with hexane removed only a small amount of oleic acid, while washing with a solution of IPA in hexane removed most of the pre-bound oleic acid.     

聚天冬氨酸的生物降解性能及降解机理研究

应用摇床实验法对所合成的聚天冬氨酸(PASP)的生物降解性能进行了系统研究,分析讨论了PASP浓度、分子量以及合成原料与其生物降解性能的关系。对分子量为5 400左右的PASP来说,当接种物浓度为10 mg/L,其浓度低于50 mg/L时,第4 d降解率就达到100%;但对接种物浓度为1 001.30 mg/L的试液来说,分子量为9 700左右的PASP的生物降解性能最好,第4 d降解率可达到82.1%;以铵盐B为原料的PASP生物降解性能最佳,在第20 d,降解率就达到100%;同时,对实验试液的氨氮值进行了测定,降解后试液的氨氮值均达到直接排放的要求标准。利用红外光谱对PASP进行了结构表征,并进一步探讨了PASP的生物降解机理,认为PASP的生物降解是生物物理降解与生物化学降解协同作用的结果。     

Modification of polyester fibers by grafting with poly(acrylic acid)

The grafting of acrylic acid on PET using benzoyl peroxide has been investigated. The influence of the main parameters of grafting, the effect of additives on the degree of grafting, and the amount of homopolymer formed during the process have been determined. Futhermore, the values of apparent activation energy have been calculated. Also, the influence of the degree of grafting on the moisture sorption and swelling of modified fibers have been determined. By an additional treatment of the grafted fibers with antibiotics it is possible to provide the fibers with antibacterial properties. Liberation of antibiotics from fibers into solutions has been examined and mathematically described. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:967–977, 1997     

In vitro degradation of poly(L-lactic acid) fibers produced by melt spinning

In vitro degradation of poly(L -lactic acid) fibers was investigated for a period of 16 weeks in Ringer solution at 37°C. Two sets of fibers, with similar initial mechanical properties, molar mass, and crystallinity content, but markedly different in diameter (72 and 120 μm) were studied. Viscometric molar mass decreased during the immersion time at a faster rate for the thinner fibers compared to the thicker ones. As a consequence, the fiber mechanical properties changed; the elastic modulus was only slightly affected by the molar mass decrease whereas ultimate mechanical properties (stress and strain at break) showed a strong decrease. A quantitative correlation between tensile strength and viscometric-average molar mass was attempted. A possible explanation of the faster degradation rate of the thinner fibers was proposed on the basis of the higher surface/volume ratio and water uptake. Dynamic mechanical properties were also measured as a function of immersion time. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 213–223, 1997     

Diffuse-reflectance Fourier-transform infrared spectroscopy of vegetable oil triglyceride adsorption on silicic acid

The adsorption of triglyceride by silicic acid from hexane miscellas was observed with diffuse-reflectance Fouriertransform infrared spectroscopy. Triglyceride was adsorbed by hydrogen bonding to silanol groups through the ester carbonyl group. Addition of isopropanol (IPA) to the triglyceride-hexane solution prior to adsorption resulted in unchanged triglyceride adsorption on silicic acid despite IPA's ability to adsorb on silicic acid and hydrogen-bond with triglyceride. Washing the triglyceride, adsorbed on silicic acid, with hexane containing IPA resulted in partial desorption of the triglyceride and a small amount of IPA being adsorbed. Triglyceride desorption into fresh hexane-IPA is due to the establishment of a new equilibrium of lipid and IPA between hexane and silicic acid. The relative strengths of all the possible pairwise interactions among triglyceride, IPA and silicic acid are revealed by the relative amounts of adsorption under various conditions.     

Grafting of poly(acrylic acid) on polyamide yarn

Graft copolymerization of acrylic acid onto PA6 yarn was examined in this study. Prior to the grafting process, the fibers were activated with a benzene solution of benzoyl peroxide. Next, the fibers were put into a bath containing acrylic acid, a dispersing agent, and the activator of reaction. The effects of the main process parameters and auxiliary additives on the degree of grafting, quantity of the homopolymer formed during grafting, effectiveness of grafting, extent of conversion, and grafting ratio were determined. Using calculation factors such as the reaction efficiency, the extent of reaction, and the ratio of grafting, the conditions of grafting were found that made possible the reduction or elimination of the by‐product. Also determined were the influence of the degree of grafting on the moisture sorption and the swelling of modified fibers. In addition, the value of apparent activation energy was calculated (49.123 kJ/mol). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1914–1919, 2001     

Polymerization of maleic acid and itaconic acid studied by FT‐Raman spectroscopy

In this research, we used a new redox free radical initiation system consisting of potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂). In the presence of NaH₂PO₂, the thermal decomposition of K₂S₂O₈ is accelerated, and the temperature required for the formation of free radical is reduced. We polymerized maleic acid (MA) using the K₂S₂O₈/NaH₂PO₂ initiation system in an aqueous solution, and monitored the polymerization process with FT‐Raman spectroscopy. The Raman spectroscopy data indicate the formation of a saturated carboxylic acid with the disappearance of the characteristic bands of MA as the thermal decomposition of K₂S₂O₈ progresses, thus indicating the formation of poly(maleic acid) (PMA). We also found that itaconic acid (IA) polymerizes in the presence of the new initiation system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 223–228, 2001     

Diffuse reflectance fourier transform infrared spectroscopy of triacylglycerol and oleic acid adsorption on synthetic magnesium silicate

Diffuse reflectance fourier transform infrared (FTIR) was used to observe adsorption complexes of triacylglycerol and oleic acid on silica gel and synthetic magnesium silicate. The spectra provide evidence of the nature of the surface interaction. Triacylglycerol was shown to be physically adsorbed to both adsorbents. Oleic acid was physically adsorbed to the silica gel, but both physically and chemically adsorbed to the magnesium silicate. The FTIR spectrum of magnesium silicate that was used to treat a degraded frying oil was similar to that of oleic acid adsorbed on magnesium silicate.     

亚胺基二乙酸树脂对镨的吸附性能及其机理

研究了镨离子在亚胺基二乙酸树脂(D401)上的吸附行为,在pH5.73时吸附最佳。测得静态饱和吸附容量为162mg·g~(-1)(树脂);用0.1～3.0mol·L~(-1)_HCl可定量洗脱;表观速率常数k_(298)=2.96×10~(-5)s~(-1);表观活化能E_a=7.18kJ·mol~()-1;等温吸附服从Freundlich经验式;吸附热力学参数△H=10.4kJ·mol~(-1),△S=45.4J·mol~(-1)·K~(-1),△G=-3.10kJ·mol~()-1;树脂功能基与镨离子的配位摩尔比为3:1;用化学和红外光谱等方法探讨了吸附机理。     

First insights into the borohydride oxidation reaction mechanism on gold by electrochemical impedance spectroscopy

Direct borohydride fuel cells (DBFC) exhibit some potential regarding the powering of small portable electronic devices, thanks to their high energy density as well as the facile and safe storage of borohydride salts. However, DBFC are hindered because (i) the borohydride oxidation reaction (BOR) is complex, (ii) its mechanism imperfectly determined yet and (iii) no practical electrocatalyst exhibits both fast BOR kinetics and high faradaic efficiency. In this context, we characterized the BOR mechanism for polycrystalline bulk gold (a classical model BOR electrocatalyst) in the rotating disk electrode (RDE) setup. Modeling cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) data, we propose a simplified reaction pathway, the theoretical behavior of which agrees with the experimental findings. This pathway includes at least a first irreversible electrochemical step (E) for BH₄⁻ oxidation, which competes with the electrochemical adsorption reaction (EAR) of OH⁻ anions at high potentials.     

Studies on electrochemical hydrodebromination mechanism of 2,5-dibromobenzoic acid on Ag electrode by in situ FTIR spectroscopy

Cyclic voltammetry and in situ FTIR were employed to study the electrochemical hydrodebromination (EHB) mechanism of 2,5-dibromobenzoic acid (2,5-DBBA) in NaOH solution. Compared with titanium and graphite electrodes, silver electrode exhibited a high electrocatalytic activity for the hydrodebromination reaction of 2,5-DBBA. On the basis of in situ FTIR data, EHB reaction of 2,5-DBBA on Ag cathode might be represented as a sequence of electron additions and bromine expulsions. Firstly, from potential at approximately −1100 mV, 2,5-DBBA received an electron to form 2,5-DBBA radical anion, which lost a bromine ion in the 2-position to form 3-bromobenzoic acid (3-BBA) free radical. Then the free radical received a proton to give 3-BBA. Finally, 3-BBA further took off another bromine ion to produce benzoic acid free radical and the end product benzoic acid was obtained by receiving another electron and a proton with the potential shifting to more negative values.