The effect of catalysts on the thermal decomposition of sodium superoxide

Simultaneous differential thermal, thermogravimetric and differential thermogravimetric analysis have been made on samples of sodium superoxide and sodium superoxide containing l% (w/w) copper(I) oxide. Decomposition of the superoxide involving oxygen production (weight loss) does not occur at a meaningful rate until temperatures approach 250°. The effects of 12 metallic oxide catalysts and one metalloorganic catalyst on the decomposition of sodium superoxide have been studied by differentialthermal analysis. Six metallic oxides had no effect while 3 oxides, (palladium oxide, titanium oxide and cadmium oxide) caused small but distinct changes in the DTA plots. A polymeric phthalocyanine, and the oxides of vanadium(III), vanadium(V) and manganese (IV) apparently reacted with the superoxide above 250°. Pretreatment of the superoxide by brief exposure to 100% humidity resulted in the formation of peroxyhydrates of sodium peroxide which upon dissociation produced water vapor in turn causing the release of oxygen from the superoxide and peroxide at lower temperatures than those experienced with untreated superoxide samples.     

Physical characterization of poly(ω‐pentadecalactone) synthesized by lipase‐catalyzed ring‐opening polymerization

The Candida antarctica lipase B (Novozyme‐435)‐catalyzed ring‐opening polymerization of ω‐pentadecalactone in toluene was performed. Poly(ω‐pentadecalactone) [poly(PDL)] was obtained in a 93% isolated yield in 4 h with a number‐average molecular weight of 64.5 × 10³ g/mol and a polydispersity index of 2.0. The solid‐state properties of poly(PDL) were investigated by thermogravimetric analysis (TGA) coupled with mass spectrometry, differential scanning calorimetry (DSC), stress–strain measurements, wide‐angle X‐ray diffraction, and dynamic mechanical and dielectric spectroscopies. Poly(PDL) is a crystalline polymer that melts around 100 °C. The polyester shows good thermal stability, with a main TGA weight loss centered at 425 °C. Because of the high degree of poly(PDL) crystallinity, the glass transition (?27 °C) is revealed by relaxation techniques such as dynamic mechanical and dielectric spectroscopies, rather than by DSC. In addition to the glass transition, the viscoelastic spectrum of poly(PDL) also shows two low‐temperature secondary relaxations centered at ?130 (γ) and ?90 °C (β). They are attributed to local motions of the long methylene sequence (γ) and complex units involving water associated with the ester groups (β). The mechanical properties of poly(PDL) are typical of a hard, tough material, with an elastic modulus and yield parameters comparable to those of low‐density polyethylene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1721–1729, 2001     

Thermal degradation of nadic methyl anhydride-crosslinked novolac epoxy resin

The physicochemical high-temperature reactions of a nadic methyl anhydride-cross-linked novolac epoxy resin were investigated by means of differential thermal analysis, thermogravimetric analysis, and by other analytical procedures. The thermogravimetric study revealed that decomposition involving weight loss occurred in two stages. Chemical analysis showed that the major gaseous products formed during weight loss were 2-methylcyclopentadiene, carbon dioxide, and carbon monoxide. The formation of a fine mist of solid particles was observed during the second stage of degradation. Changing various experimental parameters affected the degradation processes. The kinetics of degradation were also investigated. The method of Freeman and Carroll was used to find that a zero-order rate law was followed at the beginning of both first and second stages of reaction. The activation energy associated with the major portion of the first stage of weight loss was 15 kcal/mole. There was good agreement between the observed reaction rates and the reaction rates calculated from a theoretical model which depended on desorption as the rate-controlling step. The activation energy for the beginning of the second stage of weight loss was 24 kcal/mole. By using DTA, the heat of exothermal reaction during this latter phase of decomposition was evaluated as 65 cal/g.     

Protein adsorption capability of zinc ferrite nanoparticles formed by a low-temperature solution-based process

We report successful synthesis of zinc ferrite nanoparticles (ZFs) by a facile low-temperature (90 °C) solution-based process from ferric nitrate nonahydrate and zinc nitrate hexahydrate precursors in presence of hydrazine hydrate. X-ray diffraction analysis and transmission electron microscopy confirmed the presence of ZFs, which were further characterized by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric measurements for identification of characteristic chemical bond vibrations and thermal weight loss behavior, respectively. Measurements of magnetic properties at room temperature revealed that the sample showed quite high saturation magnetization (22.0 emu/g at ~19,200 G), implying the presence of less impurities/surface defects in the ZFs. The material also showed zero coercivity as a soft-magnetic material. The protein adsorption performance of the ZFs was checked using bovine serum albumin (BSA) as model protein. Excellent protein adsorption capacity of 210 mg/g (close to the value of 218.81 mg/g calculated using the Langmuir model) for BSA concentration of 0.3 mg/mL was obtained at optimized solution pH of 5. This simple process could be adopted for synthesis of different magnetic nanomaterials for use in biomedical applications.     

Polyamides incorporating phosphine oxide groups. II. Aromatic polymers containing sulfone functionality

Four novel polyamides have been prepared in high yields by the polycondensation reactions of bis(3-carboxyphenyl)- and bis(4-carboxyphenyl)phenylphosphine oxide with 3,3′- and 4,4′-diaminodiphenylsulfone. The thermal properties of these materials were studied using differential scanning calorimetry and thermogravimetric analysis. It was found that the presence of both phosphine oxide and sulfonyl groups within the polymer backbone brought about remarkable modifications in the thermal behavior. Glass transition temperatures 40–50°C lower than those of conventional polyamides i.e., in the range 170–200°C, were recorded. However, we observed greater thermooxidative stability (5% weight loss at >410°C) and high char yield upon prolonged heating at 800°C (20–34%). Also, good solubility in polar aprotic solvents was observed for all polyamides together with some solubility in aqueous solvent mixtures, e.g. tetrahydrofuran/water (95:5). © 1997 John Wiley & Sons, Inc.     

Real‐time electro‐diffusion method to discriminate carbon nanomaterials

We report both the experimental and theoretical insights of differential electro‐diffusion behavior of carbon nanomaterials (e.g. single wall, multiwall carbon nanotubes, and graphene). We thus discriminate one from the other in a soft gel system. The differential mobility of such material depends on their intrinsic properties, both extend and rate of migration bearing the discriminatory signature. The mobility analysis is made by a real time monitoring of the respective bands.     

Thermal behaviour of transition metal complexes of dithiocarbazic esters

The thermal behaviour of the square-planar dithiocarbazate derivative complexes Pt[NRNC(S)SR']₂ (R=n-hexyl, R′ = methyl or benzyl) has been investigated. Simultaneous TG and DTA measurements provided evidence of the presence of an exothermic process, which proceeds without weight loss. This is attributed to the occurrence of a disproportionation reaction: The products, which were isolated and characterized, form a 1:1eutectic mixture.     

Thermogravimetric investigation of the pyrolysis of pitch materials. A compensation effect and variation in kinetic parameters with heating rate

Thermogravimetric measurements of weight loss accompanying the pyrolysis of four pitches have been made over a range of linear heating rates. For three of the samples, the data at each heating rate could be described by an integral and a differential method of analysis, assuming a simple order function for f(α), with the result that the apparent activation energy increased with heating rate. The data for all four samples could also be satisfactorily described by the Ozawa or Friedman multiple heating rate methods, and these resulted in apparent activation energies (E_a) which increased with the value of β at which they were determined. It is suggested that this tendency for the apparent activation energy to increase, as the temperature is raised, is due to a change in the relative importance of the different reactions which lead to weight loss in this system. The apparent kinetic parameters all fall on a common compensation plot which is used to explain the relative magnitude of E_a values from Ozawa and Doyle methods of analysis. The higher values of E_a from Friedman than from Ozawa analyses are also explained.     

Base Hydrolysis of Poly(Ethylene Terephthalate) in Methanolic and Aqueous Solutions

Abstract

Hydrolysis of poly(ethylene terephthalate) fibers (intrinsic viscosity: 0.819 dL/g) using methanolic sodium methoxide was compared to that using aqueous sodium hydroxide. Weight and tenacity loss occurred more rapidly with methanolic NaOCH₃. After the methanolic NaOCH₃ treatment, the surface appeared far rougher, much of which was due to low molecular weight material present on the fibers. Intrinsic viscosity measurements indicated virtually no difference between the two treatments in the small amount of chain cleavage obtained at a given weight loss. Fiber density increased after the reaction with methanolic NaOCH₃, probably due to the presence of the methyl ester end groups formed during the ester interchange reaction, while fiber density was essentially unaffected by treatment in aqueous NaOH. Density decreased after the methanolic NaOCH₃-treated fiber was hydrolyzed with aqueous NaOH. Thermal analysis revealed a small increase in the melting temperature after methanolic NaOCH₃ treatment. The shoulder present in the melting region of this sample was markedly affected by chloroform extraction of low molecular weight products resulting from the reaction. While hydrolysis using methanolic NaOCH₃ was more severe than that using aqueous NaOH, both reactions appeared to be confined to the fiber surface.     

Polyurethane/polystyrene one-shot interpenetrating polymer networks with good damping ability: Transition broadening through crosslinking,internetwork grafting and compatibilization

Good damping materials should exhibit a high loss factor value over a broad temperature range. Polyurethane and polystyrene are highly immiscible polymers with glass transition regions far apart. The interpenetrating polymer network topology can restrict phase separation and result in materials with a broad transition region. Simultaneous polyurethane/polystyrene interpenetrating polymer networks were synthesized by the one-shot route. Different methods of improving the miscibility of the two polymers were investigated. These included the vanation of the crosslink level in both polymer networks, the controlled introduction of internetwork grafting and the incorporation of compatibilizers into the polystyrene network. Dynamic mechanical thermal analysis indicated that the latter two were successful in achieving a compatibilization of the polymer components. With some materials, a high, broad transition region exhibiting a loss factor > 0.3 over more than 135°C was obtained. The morphology observed via transmission electron microscopy ranged from macrophase separated materials in the lightly crosslinked IPNs to a fine, microheterogeneous morphology in the grafted ones. Modulated differential scanning calorimetry measurements confirmed the trend of the glass transition locations observed with dynamic mechanical thermal analysis.     

Electrochemically addressed cross-links in polyelectrolyte multilayers: cyclic duravoltammetry

In situ nanoindentation was performed on a multilayer of poly(acrylic acid) and a high molecular weight, pendant chain polyviologen under controlled electrochemical potential. The modulus of the thin film of polyelectrolyte complex was reversibly modulated, by about an order of magnitude, upon changing the state of charge within the material using the electrochemically active and addressable viologen repeat units. The applied potential, under aqueous conditions, is believed to control the extent of cross-link formation. Simultaneous quartz crystal microbalance measurements revealed the flux of ions into or out of the multilayer during redox cycling. Apparent film modulus also depends on the identity of the last layer.     

Mapping the location of grafted PNIPAAM in mesoporous SBA-15 silica using gas adsorption analysis

The thermoresponsive polymer poly-N-isopropylacrylamide (PNIPAAM) was grafted in mesoporous SBA-15 silica. The grafting process consists of three steps: (i) increasing the amount of surface silanol groups of SBA-15 by hydroxylation, (ii) attachment of an anchor (1-(trichlorosilyl)-2-(m/p-(chloromethylphenyl)ethane) and finally (iii) the polymerization of the monomers (NIPAAM) onto the anchor. After each step, the materials were characterized regarding the porosity, using inert gas (argon, nitrogen) physisorption measurements. Also, the structure was investigated by small-angle X-ray diffraction analysis and thermogravimetric analysis was used for determination of the amount of grafted material. A total of 17% by weight of organic material was introduced in the porous host and the structure was preserved during the grafting process. Physisorption measurements revealed that the anchor is mainly located in the intrawall pores present in SBA-15. Consequently, the polymer is preferentially located in the intrawall pores or in the vicinity thereof. The final mesopore volume is 0.47 cm(3) g(-1) as compared to 0.96 cm(3) g(-1) for the pure SBA-15. The surprisingly large loss of mesopore volume and an almost constant mesopore diameter is consistent with a partial sealing of the mesopore volume in the composite materials. The potential thermocontrol combined with the large mesoporosity and the possible "storage space" provided by the sealed mesopore volume leads to a material with possibilities for various applications.     

Effect of photooxidation of polystyrene on its dielectric properties. II. Use of dielectric loss measurements to study photooxidation

Dielectric loss measurements have been applied to study the short-wave (λ = 254 nm) and long-wave (λ > 300 nm) photooxidation of polystyrene which had been prepared using both free radical and anionic initiator. The high-frequency loss peak, attributable to carbonyl products of oxidation is a sensitive monitor of the rate of oxidation, the sensitivity being greater than that of manometric measurements. The data are specific to carbonyl compounds and the technique is particularly suitable for studying the surfaces, on which most of the above photooxidation occurs with polystyrene. Effects of radiation intensity and oxygen pressure were also studied. The measurements have permitted a more detailed study of the long-wave photooxidation process than has previously been undertaken, and the results emphasize differential reactivities of radically and anionically prepared polymers. Results are interpreted in terms of initiation by both impurities and charge-transfer complexes.     

Enzymatic degradation of 3D scaffolds of starch-poly-(?-caprolactone) prepared by supercritical fluid technology

Starch-based polymers have been proposed for different tissue engineering applications due to their inherent properties. In this work, a polymeric blend of starch-poly-(?-caprolactone) (SPCL) was processed using supercritical fluid technology, namely, by supercritical assisted phase inversion. As SPCL is a biodegradable polymer, the matrices produced are susceptible of undergoing enzymatic degradation upon implantation in the human body. In vitro assessment of the enzymatic degradation of SPCL was carried out in different buffer solutions containing α-amylase and/or lipase. The effect of the presence of these enzymes was studied by monitoring different parameters in order to characterise both bulk and the surface of the scaffolds. As regards to bulk analysis, weight loss of the samples incubated for 1, 3, 7, 14 and 21 days was determined, further differential scanning calorimetry was carried out. The morphology of the scaffolds after these periods was analysed by micro-computed tomography (μ-CT) and surface chemistry was characterised by infra-red spectroscopy and contact angle measurements. Results suggest that SPLC scaffolds undergo bulk degradation, which is typically characterised by hydrolysis of chemical bonds in the polymer chain at the centre of the matrix, resulting in a highly porous material.     

Iodoacetamide-alkylated methionine can mimic neutral loss of phosphoric acid from phosphopeptides as exemplified by nano-electrospray ionization quadrupole time-of-flight parent ion scanning

Formation of S-carbamidomethylmethionine (camMet) occurs as a side reaction during cysteine alkylation with iodoacetamide (IAA). In collision-induced dissociation, peptides with camMet show an abundant neutral loss of 2-(methylthio)acetamide (C3H7NOS = 105.025 Da) at moderate collision offset values which are similar to those optimal for loss of phosphoric acid (H3PO4 = 97.977 Da). Neutral loss analysis is used for spotting of phosphopeptides which contain phosphoserine (pSer) or phosphothreonine (pThr) residues. In the case where precursor ions cannot be accurately assigned in the survey spectrum (e.g. due to low ion abundance or signal overlap), the mass accuracy of a neutral loss tandem mass spectrometry (MS/MS) analysis depends on the precursor ion isolation window. For the charge states 2+, 3+ or 4+, a typical 3.5 Da precursor isolation window results in neutral loss windows of 7, 10.5 or 14 Da, respectively. Consequently, neutral loss of 105 Da from alkylated methionine residues can mimic the phosphoserine/phosphothreonine-specific neutral loss of 98 Da. In the evaluation of quadrupole time-of-flight (QTOF) parent ion scan data for neutral loss of H3PO4, this interference was frequently observed. It is illustrated in this study using the analysis of ovalbumin phosphorylation as an example. The +80 Da molecular weight shift connected with phosphorylation at serine or threonine may also be mimicked by carbamidomethylation of methionine through a combination with sodium adduction (+57 Da +22 Da = +79 Da). For highly sensitive neutral loss analysis of serine and threonine phosphorylation, careful data inspection is recommended if reduction and alkylation by IAA is employed.     

A study of electron scattering from benzene: excitation of the 1B1u, 3E2g, and 1E1u electronic states

We report results from measurements for differential and integral cross sections of the unresolved (1)B(1u) and (3)E(2g) electronic states and the (1)E(1u) electronic state in benzene. The energy range of this work was 10-200 eV, while the angular range of the differential cross sections was ～3°-130°. To the best of our knowledge there are no other corresponding theoretical or experimental data against which we can compare the present results. A generalized oscillator strength analysis was applied to our 100 and 200 eV differential cross section data, for both the (1)B(1u) and (1)E(1u) states, with optical oscillator strengths being derived in each case. The respective optical oscillator strengths were found to be consistent with many, but not all, of the earlier theoretical and experimental determinations. Finally, we present theoretical integral cross sections for both the (1)B(1u) and (1)E(1u) electronic states, as calculated within the BEf-scaling formalism, and compare them against relevant results from our measurements. From that comparison, an integral cross section for the optically forbidden (3)E(2g) state is also derived.     

Thermal degradation and isothermal crystalline behavior of poly（trimethylene terephthalate）

Poly(trimethylene terephthalate)(PTT) is an excellent fiber material.Its thermal degradation and isothermal crystalline behaviors were in this study investigated using thermogravimetric analysis(TGA),thermogravimetric analysis-Fourier transform infrared spectroscopy(TGA-FTIR) analysis,differential scanning calorimetry(DSC) and X-ray diffraction(XRD).The thermal degradation mechanism of PTT follows Mclafferty rearrangement principle.The PTTwithintrinsicviscosity(Ⅳ) of 0.74 dL/g has a maximum crystallinity...     

Poly(enamine-ketones) from hydrogen-terminated aromatic dipropynones and aromatic diamines

Poly(enamine-ketones) were prepared by the nucleophilic (Michael-type) addition of various aromatic diamines to 1,1′-(1,3- or 1,4-phenylene)bis(2-propyn-1-one)(1,3 or 1,4-PPO) in m-cresol at 5–23°C. The low molecular weight polymers (inherent viscosity of 0.25 dL/g) exhibited limited solubility in organic solvents. Glass transition temperatures were generally undetectable by differential scanning calorimetry while polymer decomposition temperatures (10% weight loss), as measured by thermogravimetric analysis, were observed from 355 to 419°C. Polymers prepared from 1,4-PPO were semi-crystalline as shown by wide-angle X-ray diffraction. The poly(enamine-ketone) structure was confirmed by matching infrared spectral characteristics of the polymers with those of well-characterized model enamine ketones.     

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical–chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material.     

New certified reference material for general use in the determination of trace elements in the environment: Single cell protein

The way of certification of trace element contents in a sample of single cell protein (SCP) is presented together with the results of the homogeneity and stability studies, carried out on this sample (BCR 274). The elements As, Cd, Co, Cu, Mn, Pb, Se and Zn are certified using different spectrometric, electrochemical or activation techniques after a thorough sample treatment. The material is not only useful in SCP-analysis, but can also be applied for analytical background measurements and control or for the analysis of similar materials (e.g. sea food).