Lignin-based carbon fibers: Oxidative thermostabilization of kraft lignin

The thermostabilization of lignin fibers used as precursors for carbon fibers was studied at temperatures up to 340 °C at various heating rates in the presence of air. The glass transition temperature (T_g) of the thermally treated lignin varied inversely with hydrogen content and was found to be independent of heating rate or oxidation temperature. A continuous heating transformation (CHT) diagram was constructed from kinetic data and used to predict the optimum heating rate for thermostabilization; a heating rate of 0.06 °C/min or lower was required in order to maintain T_g > T during thermostabilization. Elemental and mass analyses show that carbon and hydrogen content decrease during air oxidation at constant heating rates. The hydrogen loss is sigmoidal, which is consistent with autocatalytic processes. A net increase in oxygen occurs up to 200-250 °C; at higher temperatures, oxygen is lost. Spectroscopic analyses revealed the oxidation of susceptible groups within the lignin macromolecule to ketones, phenols and possibly carboxylic acids in the early stage of the reaction; the later stage involving the loss of CO₂ and water and the formation of anhydrides and possibly esters. Slower heating rates favored oxygen gain and, consequently, higher glass transition temperatures (T_g) as opposed to faster heating rates.     

Interdiffusion in a particle matrix system of two miscible polymers: An investigation by positron annihilation lifetime spectroscopy and differential scanning calorimetry

Positron annihilation lifetime spectroscopy (PALS) and differential scanning calorimetry (DSC) were used to study the interdiffusion in a particle matrix system consisting of (styrene‐maleic anhydride) copolymer containing 24% maleic anhydride (SMA) and poly(methyl methacrylate) (50:50). Starting from the phase separated state of the miscible components, the transition to the mixed state due to interdiffusion during annealing at 160 and 180 °C was investigated. The diffused mass fractions of both components were estimated by DSC; they increase linearly with the logarithm of the annealing time. Both components show the same behavior, suggesting an average interphase composition of 50:50. For subsequent annealing, the kinetic behavior differs from the earlier behavior, probably because of the different diffusion coefficients of the two components. Experimental evidence is presented that the ortho‐positronium (o‐Ps) intensity correlates to the interdiffusion process. The response is due to the diffusion of inhibitors for Ps formation from one phase into the other. A semiquantitative model is developed that allows the estimation of the interphase volume fraction from the relative change of the annihilation parameters. The PALS results are discussed in relation to those obtained by DSC. The results show that PALS is a useful tool to study mixing and demixing processes in polymer blends with a three‐dimensional morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 654–664, 2002; DOI 10.1002/app.10362     

Morphological changes in epoxy resin (DGEBA/TETA) exposed to low temperatures

Abstract

Epoxy resin (DGEBA/TETA) is commonly used as an adhesive material. When this material is subjected to low temperatures for an extended period of time, it undergoes changes in inter/intramolecular vibrations which has been probed in this research through a combination of terahertz spectroscopy, differential scanning calorimetry and infrared spectroscopy. Distinctive morphological changes of the virgin material are observed for the exposed material at cold temperature which can be attributed to incomplete reversibility of segmental as well as entire molecular chain mobility.     

Eutectic mixture of two bismaleimide monomers: thermal and mechanistic study in the molten state

Differential scanning calorimetry analysis of two bismaleimide monomers (N-N-diphenylmethane-4,4′-bismaleimide and m-phenylenebismaleimide) mixed in different proportions has enabled a phase diagram to be constructed. There is a relationship between the melting and solubility of each constituent of the binary system via the different liquid and solid phases. The concept of a eutectic mixture having special thermal properties has thus been demonstrated. The eutectic melting temperatures are very interesting because they are much lower than that of the compound with the lowest melting point, making easier the use of these monomers in the molten state. In addition, the reduction of the temperatures of crosslinking onset becomes maximal in these systems at the eutectic point, at which point there is a unique and perfectly homogeneous melting. In this unique liquid phase, the two monomers can combine to form the network after a copolymerization reaction. Once the network forms, m-phenylenebismaleimide radicals that are more highly stabilized by resonance are more reactive in the initial stages of the copolymerization reaction. © 1997 Elsevier Science Ltd.     

Detection of Adulteration in Iranian Olive Oils Using Instrumental (GC,NMR, DSC) Methods

This paper describes an investigation into the usefulness of some instrumental methods (GC, NMR, and DSC) in the detection of adulteration of olive oil with soybean, sunflower, and canola oils (that are relatively cheap oils mixed as adulterants with olive oil). These seed oils were compared with genuine and commercial olive oils, two of which appeared to have been adulterated. It was observed that from among physical and chemical indices, the iodine value and the refractive index in the two olive oil samples (named A and B) were significantly higher (P < 0.01) than in the reference (genuine) olive oil, both values being above standard limits established for olive oil. On the other hand, fatty acid (FA) profiles in these two samples exhibited higher amounts of linolenic and linoleic acids (5.34 and 39.92%, 6.38 and 54.42%, 0.79 and 12.88% for A, B and genuine olive oils respectively) but significantly lower amounts of oleic acid (30.07, 21.72 and 67.86%, respectively). The number and intensity of signals observed using ¹H NMR indicated that the peaks numbered 2 and 7 were useful in the determination of olive oil purity. Because of higher linolenic and linoleic acid contents in samples A and B, the intensity and integrated areas for these two signals were higher than those for other olive oil samples in which signal 2 was not observed and signal 7 had a very low intensity. Satisfactory results were achieved from quantitation of DSC parameters. The results show that due to increased unsaturated FAs in samples A and B and the consequent changes in triacylglycerol profiles, offset crystallization temperature and onset melting temperature in these two olive oils differed from those of the reference and clearly shifted to lower values. Crystallization and melting curves were similar to the corresponding curves observed for soybean and sunflower oils in terms of shape and number of peaks.     

The measurement of compositional heterogeneity in a propylene–ethylene block copolymer

¹³C nuclear magnetic resonance (n.m.r.) and Fourier transform infra-red (FTi.r.) spectroscopies, as well as wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (d.s.c.) and temperature rising elution fractionation (TREF), have been combined to measure the composional heterogeneity of a commercial propylene–ethylene block copolymer. It has been shown that the copolymer contains molecular species with a wide variation in composition, and the copolymer products range from amorphous ethylene–propylene rubbers (EPR) to crystallisable propylene–ethylene statistical copolymers, polyethylene and polypropylene homopolymers as well as blocks of various lengths. The so-called block copolymer was composed of about 15% amorphous EPR, 5% random copolymer, 28% block copolymers with long propylene and long ethylene sequences, and 52% homopolypropylene. The crystallisation and melting behaviour of these fractions have been investigated.     

A novel approach using differential scanning calorimetry to investigate the dissolved state in aqueous solutions of polymers used for papermaking

The size and conformations of dissolved polymer molecules of polyethylene glycol (PEG) in 5% aqueous solutions were examined through the use of differential scanning calorimetry (DSC). As long as the freezable bound water is considered to be the water enclosed by the entangled polymer chains in the solution, the appearance of the characteristics of a polymer begins to occur at a degree of polymerization (DP) between 11 and 21 and is largely completed at a DP of about 50. Assuming that the peak temperature of the DSC curve for the freezable bound water indicates the size of the entangled molecular coil, the lowering of the peak temperature with a decrease of molecular weight (MW) suggests a decrease in the size of the entangled molecular coil. The linear relationship between the peak temperature and the reciprocal of the number‐average MW suggests melting point depression as a plausible mechanism for the peak temperature lowering. Mixing of two polymers with different MWs—and thus, entangled molecular coils of different sizes—causes a kind of polymer–polymer interaction and the coil sizes change as follows. If the difference in the values of the two MWs is large, the sizes of the entangled molecular coil of each MW are brought closer to each other. The extent of approach is roughly proportional to the mixing ratio. If the difference in the values of the two MWs is not large, the original entangled molecular coils disappear and a single molecular coil of intermediate size appears instead. The size of the single intermediate molecular coil varies roughly according to the simple mixing law for the values of the two MWs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2798–2807, 2003     

Synthesis and Characterization of Urea Nitrate and Nitrourea

Urea nitrate (UN) has not found use as a legitimate explosive but is commonly used as an improvised explosive. The dehydration product of UN is nitrourea (NU). Visually both UN and NU are white solids that both melt around 160 °C. Other properties differ markedly as might be expected from an inorganic salt (UN) and an organic molecular compound (NU). An extensive physical characterization of NU and UN is reported. Two reported routes to the NU product are compared and a decomposition mechanism of UN proposed.     

Azo initiator selection to control the curing order in dimethacrylate/epoxy interpenetrating polymer networks

Differential Scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) spectroscopic studies have been undertaken of the cure of interpenetrating polymer networks (IPNs) formed with imidazole‐cured diglycidyl ether bisphenol‐A (DGEBA) and with either diethoxylated bisphenol‐A dimethacrylate (DEBPADM) or bisphenol‐A diglycidyl dimethacrylate (bisGMA), polymerized by a range of azo initiators (AIBN64, VAZ088, VR110 and AZO168). Due to the differing decomposition rates of the azo initiators, the neat dimethacrylate resin either cured faster than (with AIBN64 and VAZO88), or similar to (VR110), or slower than (AZO168), the neat epoxy resin. In the neat DGEBA/1‐methyl imidazole (1‐MeI), DEBPADM/AIBN64, DEBPADM/VAZO88 and DEBPADM/VR110 resins, close to full cure was achieved. For the neat, high‐temperature DEBPADM/AZO168 resin, full cure was not attained, possibly due to the compromise between using a high enough temperature for azo decomposition while avoiding depolymerization or decomposition of the methacrylate polymer. IPN cure studies showed that, by appropriate initiator selection, it was possible to interchange the order of cure of the components within the IPN so that either the dimethacrylate or epoxy cured first. In the isothermal cure of the 50:50 DEBPADM/AIBN64:DGEBA/1‐Mel IPN system, the cure rate of both species was less than in the parent resins, due to a dilution effect. For this system, the dimethacrylate cured first and to high conversion, due to plasticization by the unreacted epoxy, but the subsequent cure of the more slowly polymerizing epoxy component was restricted by the high crosslink density developed in the IPN. After post‐curing, however, high conversion of both reactive groups was observed and the fully cured IPN exhibited a single high‐temperature T_g, close to the T_g values of the parent resins. In the higher‐temperature, isothermal cure of the 50:50 DEBPADM/VR110:DGEBA/1‐Mel IPN system, the reactive groups cured at a similar rate and so the final conversions of both groups were restricted, while in the 50:50 DEBPADM/AZO168:DGEBA/1‐Mel system it was the epoxy which cured first. Both of these higher‐temperature azo‐initiated IPN systems exhibited single T_gs, indicating a single‐phase structure; however, the T_gs are significantly lower than expected, due to plasticization by residual methacrylate monomer and/or degradation products resulting from the high cure temperature. Copyright © 2004 Society of Chemical Industry     

Phase separation and thermal aging behavior of styrene‐butadiene rubber vulcanizates using liquid polymers as plasticizers studied by differential scanning calorimetry and dynamic mechanical spectroscopy

Styrene–butadiene rubber (SBR) vulcanizates were prepared using plasticizers including the four liquid types of styrene–butadiene copolymers (LPSB), polybutadiene (LPB), polyisoprene (LPI), and the hydrogenated polyisoprene (LHPI) as well as the conventional process oil, and their phase‐separated structures and mechanical properties were investigated by differential scanning calorimetry and dynamic mechanical spectroscopy. The phase separation was observed for the SBR vulcanizates when LPI and LHPI were used as the plasticizers, while the LPSB and LPB gave homogeneous structures because of the good miscibility with the SBR. The phase‐separated structure of the SBR vulcanizate prepared using LPI changed to the homogeneous during the thermal aging. We revealed the role of the liquid polymers as the plasticizers in maintaining the physical and mechanical properties of the SBR vulcanizates during the thermal aging process when the plasticizers were miscible to the SBR. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal dynamics of side-chain copolymethacrylates as studied by the dielectric spectroscopy and relaxation of second-harmonic generation

A series of copolymethacrylates with different contents of tolane-based mesogenic groups have been synthesized. The mesogenic group content was characterized with ¹H-n.m.r.. The phase behaviours were determined using a differential scanning calorimeter and optical polarizing microscopy. A smectic A phase was obtained when the mesogenic group content was increased up to 80 mol.%. Dielectric relaxation results indicated that the amplitude of the -relaxation was suppressed significantly due to the presence of the liquid crystalline phase. The reduction of the molecular motion is beneficial to the enhancement of the temporal stability of the effective second-harmonic coefficient for the polymer with a higher mesogenic group content. Moreover, the second harmonic coefficient is enhanced as the mesogenic group content increases. The self-alignment nature of the liquid crystal phase is favourable for alignment of the NLO-active mesogenic group under an applied electric field and preserving such alignment after removal of the electric field. The relationship between thermal dynamic behaviour and second-order nonlinear optical properties is also discussed.     

Enzymatic interesterification of lard and high-oleic sunflower oil with Candida antarctica lipase to produce plastic fats

Lard and high-oleic sunflower oil (Trisun® Extra) were interesterified at 55°C for 24 h with SP435 lipase from Candida antarctica to produce plastic fats. As the amount of trisun increased, percentage free fatty acid, unsaturated fatty acid/saturated fatty acid value, oxidizability, and the amount of 18:1 found at the sn-2 position of triglyceride products increased. Differential scanning calorimetry showed that the low-melting components in the product contained more 18:1 than the high-melting components. A 60:40 (w/w) ratio of lard to trisun had the widest plastic range (3–26°C). The scaled-up reaction to produce this blend resulted in a product that had 60.1% 18:1 at the sn-2 position compared to 44.9% for the physical blend. The solid fat content of the 60:40 interesterified mixture resembled soft-type margarine oil.     

Water structure in poly(2-hydroxyethyl methacrylate): Effect of molecular weight of poly(2-hydroxyethyl methacrylate) on its property related to water

Low molecular weight poly(2-hydroxyethyl methacrylate) (polyHEMA) with a number average molecular weight (Mn) <22,600, were prepared by atom transfer radical polymerization. The molecular weight and end groups of the polyHEMA were varied, and the water content equilibrium moisture sorption and water structure were analyzed using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Higher water content was observed for polyHEMA with Mn < 10,000. DSC revealed that the amounts of nonfreezing water are affected neither by the molecular weight nor by the end groups of the polyHEMA. On the other hand, the amount of freezing water was affected by both the molecular weight and end groups of polyHEMA, especially for polyHEMA with Mn < 20,000. The XRD-DSC measurements showed that water in polyHEMA form hexagonal ice and that the direction of crystal growth is dependent on the molecular weight. These findings indicate that the molecular weight of polyHEMA plays a significant role in the water structure in polyHEMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrochemical oxidation of cholesterol in acetonitrile leads to the formation of cholesta-4,6-dien-3-one

Cholesterol was shown to be oxidized at the glassy carbon electrode in an acetonitrile–2-propanol mixture and this oxidation reaction was applied to the determination of serum total cholesterol by high-performance liquid chromatography with electrochemical detection (K. Hojo, H. Hakamata, A. Ito, A. Kotani, C. Furukawa, Y.Y. Hosokawa, F. Kusu, J. Chromatogr. A 1166 (2007) 135–141). To gain insight into the detection mechanisms of cholesterol, an electrolytic product of cholesterol was collected and characterized by infrared spectroscopy, one- and two-dimensional nuclear magnetic resonance, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The three techniques, together with comparisons of literature spectral data, confirmed the formation of cholesta-4,6-dien-3-one. The conversion of cholesterol to cholesta-4,6-dien-3-one, a four-electron, four-proton electrochemical process, has been proposed as an electrochemical oxidation mechanism of cholesterol in acetonitrile.     

Crystallization and melting behaviour of photodegraded polypropylene - I. Chemi-crystallization

An investigation has been conducted into the effects of photodegradation on the crystallinity and melting behaviour of isotactic polypropylene (PP). PP samples having different structural characteristics were prepared and exposed to ultraviolet radiation (u.v.) in the laboratory for periods of up to 48 weeks. The changes in crystallinity during exposure were followed by X-ray diffraction and differential scanning calorimetry (d.s.c.), whereas the chemical degradation of the specimens sampled was evaluated by gel permeation chromatography (g.p.c.) and Fourier transform infrared spectroscopy (f.t.i.r.). An increase in fractional crystallinity during u.v. exposure was noted for all types of samples studied, and the gain in crystallinity was usually between 6% and 7% and was virtually independent of the initial structure of the polymer. Measurements conducted at different depths within the test bars indicated that the fractional crystallinity increased during u.v. exposure due to crystal growth using molecule segments released by the scission of molecules (probably taut molecules). This process, called chemi-crystallization, is restricted by the chemical defects introduced into the molecules by the photodegradation. Possible mechanisms for the chemi-crystallization process are discussed. The melting thermograms of most types of samples exhibited single peaks with melting range increasing with exposure time. The broadening of the melting thermograms occurred during the period between the commencement and the completion of the chemi-crystallization. Secondary crystallization proceeded much more slowly in the interior of the test bars because of the limited oxygen supply, but the final crystallinity was the same as the plateau value, which was attained more rapidly when the material in the interior was exposed by machining away the surface prior to u.v. exposure. © 1997 Elsevier Science Ltd.     

A method to crystallize substances that oil out

A new approach to crystallize oily substances is described. The tendency for liquid–liquid phase separation (LLPS) is reduced by decreasing the kinetics of self-association via the formation of an intermediate amorphous network. The path to initial crystal formation followed a sequence of first freeze-drying an emulsion of solute in the solvent system followed by suspending the dried solid in water to obtain a hydrated crystalline form. This new procedure was applied successfully to a pharmaceutical organic substance that was previously isolated only as a viscous oil. Once isolated, crystals of the drug were utilized as seeds to allow the successful transformation of an emulsion of the substance into a suspension of crystalline drug solid thus avoiding the freeze-drying step. The isolated crystalline solid retained its physical and chemical purity at room temperature for at least 3 months.     

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries

The solid electrolyte interphase (SEI) is a protecting layer formed on the negative electrode of Li-ion batteries as a result of electrolyte decomposition, mainly during the first cycle. Battery performance, irreversible charge “loss”, rate capability, cyclability, exfoliation of graphite and safety are highly dependent on the quality of the SEI. Therefore, understanding the actual nature and composition of SEI is of prime interest. If the chemistry of the SEI formation and the manner in which each component affects battery performance are understood, SEI could be tuned to improve battery performance. In this paper key points related to the nature, formation, and features of the SEI formed on carbon negative electrodes are discussed. SEI has been analyzed by various analytical techniques amongst which FTIR and XPS are most widely used. FTIR and XPS data of SEI and its components as published by many research groups are compiled in tables for getting a global picture of what is known about the SEI. This article shall serve as a handy reference as well as a starting point for research related to SEI.     

Novel developments in the multidimensional characterization of segmented copolymers

Controlled radical polymerization (CRP) provides the polymer chemist with the ability to produce tailor-made polymers with controlled molar masses, molar mass distributions, chemical compositions and macromolecular architectures. Segmented copolymers can be synthesized having polymer segments arranged in a linear fashion (linear block copolymers), however, polymer segments can also be attached to pre-synthesized macromolecules or to multifunctional core molecules to produce branched (graft) copolymers, polymer stars or dendrimers. Although there are many ways to control the chain growth and the architecture of the target macromolecules, side reactions cannot be completely avoided. Accordingly, even with CRP, obtained products exhibit chemical composition and topology distributions along with the molar mass distribution.     

Investigation of the chemical and morphological structure of thermally rearranged polymers

Reacting ortho-functional poly(hydroxyimide)s via a high-temperature (i.e., 350 °C–450 °C) solid-state reaction produces polymers with exceptional gas separation properties for separations such as CO₂/CH₄, CO₂/N₂, and H₂/CH₄. However, these reactions render these so-called thermally rearranged (TR) polymers insoluble in common solvents, which prevent the use of certain experimental characterization techniques such as solution-state nuclear magnetic resonance (NMR) from identifying their chemical structure. In this work, we seek to identify the chemical structure of TR polymers by synthesizing a partially soluble TR polymer from an ortho-functional poly(hydroxyamide). The chemical structure of this TR polymer was characterized using 1-D and 2-D NMR. By use of cross-polarization magic-angle spinning ¹³C NMR, the structure of the polyamide-based TR polymer was compared to that of a polyimide-based TR polymer with a nearly identical proposed structure. The NMR spectra suggest that oxazole functionality is formed for both of these TR polymers. Furthermore, gas permeation results are provided for the precursor polymers and their corresponding TR polymer. The differences in transport properties for these polymers result from differences in the isomeric nature of oxazole-aromatic linkages and morphological differences related to free volume and free volume distribution.     

Porous polymer particles—A comprehensive guide to synthesis, characterization, functionalization and applications

This review is written to fulfill the need of a comprehensive guide for the manufacture of porous polymer particles. The synthesis section discusses and for the first time compares microfluidics, membrane/microchannel, suspension, dispersion, precipitation, multistage polymerizations and a few other less known methods, microfluidics being in greater detail. The comparison includes on one hand simplicity, scaling-up possibilities and the ability to yield nonspherical particles for these methods and on the other hand size, size monodispersity, pore characteristics and chemical functionality of the obtained particles. This extensive comparison certainly makes this review also useful for the preparation of nonporous particles. In addition, functionalization/characterization techniques and applications of porous particles are also discussed, including some visionary recommendations. The review is expected not only to enable individual experts of each field to compare their methods with the other ones, but also to be a handbook for the newcomers to this field to guide them from the synthesis to the applications.