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1.
A novel thermosetting resin based on cyano functionalized benzoxazine (BZCN) has been synthesized from 2,6-bis(4-diaminobenzoxy)benzonitrile phenol and formaldehyde by solution reaction. The structure of the monomer is supported by FTIR, 1H NMR and 13C NMR spectra, which have exhibited that the reactive benzoxazine rings and cyano group exist in the molecular structure of BZCN. The curing reactions of BZCN are monitored by the disappearance of the nitrile peak and the tri-substituted benzene ring that is attached with oxazine ring peak at 2231 and 930 cm−1, respectively. The complete cured materials could achieve char yields up to 70% at 800 °C in nitrogen atmosphere, above 64% at 600 °C in air (20% oxygen) environments and the glass transition temperature up to 250 °C. The thermally activated curing polymerization reaction of BZCN follows multiple polymerization mechanisms via the ring-opening polymerization of oxazine rings and the triazine ring-formation of cyano groups, which contribute to the stability of the polymer.  相似文献   

2.
Medium-chain-length poly(3-hydoxyalkanoates) (mcl-PHA), comprising six to fourteen carbon-chain-length monomers, are natural thermoplastic polyesters synthesized by fluorescent pseudomonades. In this study, mcl-PHA was produced by Pseudomonas putida from oleic acid in aerobic shake flask fermentation. Thermal degradation of mcl-PHA was performed at temperatures in the range of 160-180 °C. Thermodynamic parameters of mcl-PHA thermal degradation were determined where degradation activation energy, Ed and pre-exponential factor, A equal to 85.3 kJ mol−1 and 6.07 × 105 s−1, respectively; and exhibited a negative activation entropy (?S) of −139.4 J K−1 mol−1. Titration was carried out to determine the carboxylic terminal concentration and used to correlate number-average molecular weight (Mn) of the polymers. Thermally-degraded PHA contained higher amount of carboxylic terminals and lower Mn compared to the initial PHA and these results coincide with the decreased Mn in GPC analysis. Thermal properties of initial and degraded mcl-PHA were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal decomposition mechanism was investigated following the analyses of the degradation products using 400-MHz 1H NMR, FTIR spectroscopy and GC analysis. The overall decomposition reaction is the hydrolysis of ester linkages to produce hydroxyl and carboxylic terminals. A small proportion of unsaturated side chain fragments would undergo oxidative cleavage at CC linkages, producing minor amount of low-molecular weight esters and acids. At higher temperatures, the hydroxyl terminal can undergo dehydration to form an alkenyl terminal.  相似文献   

3.
Polyaniline base has been exposed to various temperatures between 100 °C and 1000 °C for 2 h in air. The mass loss has increased with increasing temperature. FTIR and Raman spectroscopies show the gradual destruction of the PANI structure, the possible formation of intermediate oxime and nitrile groups, and the final conversion to graphitic material. The elemental analysis confirmed the dehydrogenation while the content of nitrogen was nearly constant even after treatment at 800 °C. The conductivity of PANI base, 10−8 S cm−1, increased to ∼10−4 S cm−1 after treatment at 1000 °C; most of the products, however, were non-conducting. Another series of experiments involved the polyaniline base heated at 500 °C for 1-8 h. The studies were performed in connection with the potential flame-retardant application of polyaniline.  相似文献   

4.
The thermal stability of starch cross-linked with tetraethylene glycol diacrylate was studied under nitrogen atmosphere by thermogravimetry (TG) and infrared spectroscopy (FTIR). The cross-linking reaction was confirmed by the increase in intensity of the absorption band at ca. 3330 cm−1 indicating the reinforcement of hydrogen bonds and the appearance of a new band at 1726 cm−1 associated with the carbonyl group of the cross-linking agent. After cross-linking the solubility of starch in water decreased to the range 9%-16%. The thermogravimetric curves of pure and cross-linked starches showed an initial stage of degradation (up to ca. 150 °C) associated with the loss of water. The main stage of degradation occurred in the range 250-400 °C corresponding to ca. 60%-70% mass loss. The activation energy (E) for the degradation process increased from 145 kJ mol−1 (pure starch) to 195 kJ mol−1 and 198 kJ mol−1 for starch treated for 60 min by UV (30 °C) and at 90 °C, suggesting high stability after cross-linking. A higher value (240 kJ mol−1) was obtained for starch treated by UV for 120 min. The main volatile products determined by FTIR which correspond to hydrocarbons and carbonyl groups are apparently associated with the scission of weak bonds in the chain (probably branched groups) and the scission of stronger bonds (glycosidic linkages), respectively.  相似文献   

5.
A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 °C during the collection stage and is heated up to 675 °C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min− 1 Ar with 75 ml min− 1 H2 during the collection step and 112.5 ml min− 1 Ar with 450 ml min− 1 H2 in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% (n = 11) for 0.10 µg l− 1 Se using peak height measurements.  相似文献   

6.
Ethanol organosolv lignin extracted from Miscanthus × giganteus (using the following conditions: T = 190 °C, t = 60 min, sulfuric acid = 1.2% w/w, EtOH/H2O = 0.65) and milled wood lignin from Miscanthus × giganteus were subjected to a comprehensive structural characterization by 13C, 31P NMR, FTIR, UV spectroscopies and size exclusion chromatography. The results showed that Miscanthus lignin is an H/G/S type (4%, 52%, 44% respectively) with ∼0.41 β-O-4 linkage per aromatic ring and contains coumarylate linkages (0.1/Ar). It was shown that during organosolv treatment, cleavage of β-O-4 linkages and of ester bond (acetyl and coumaryl residues) was the major mechanisms of lignin breakdown but the process did not significantly change the core of the lignin structure.  相似文献   

7.
Nanocrystalline single-phase samples of Zn1−xNixFe2O4 ferrites (0<x<1) have been obtained via a soft-chemistry method based on citrate-ethylene glycol precursors, at a relatively low temperature (650 °C). The influence of the nickel and zinc contents as well as that of heat treatments were investigated by means of X-ray powder diffraction, Brunauer-Emmett-Teller (BET) surface area, scanning electron microscopy (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy. Higher Ni content increases the surface areas, the largest one (∼20 m2/g) being obtained for NiFe2O4 annealed at 650 °C for 15 h. For all compositions, the surface area decreases for prolonged annealing at 650 °C and for higher annealing temperatures. Those results were correlated to the particle size evolution; the smallest particles (∼50 nm) observed in the NiFe2O4 sample (650 °C, 15 h) steadily increase as Ni ions were replaced by Zn, reaching ∼100 nm in the ZnFe2O4 sample (650 °C, 15 h). For all the Zn1−xNixFe2O4 samples and, whatever the heat treatments was, the FTIR spectra show two fundamental absorption bands in the range 650-400 cm−1, characteristics of metal vibrations, without any superstructure stating for cation ordering. The highest ν1-tetrahedral stretching, observed at ∼615 cm−1 in NiFe2O4, shifts towards lower values with increasing Zn, whereas the ν2-octahedral vibration, observed at 408 cm−1 in NiFe2O4, moves towards higher wavenumbers, reaching 453 cm−1 in ZnFe2O4.  相似文献   

8.
Borsdorf H  Mayer T 《Talanta》2011,83(3):815-822
Ion mobility spectrometry (IMS) with handheld and transportable devices permits the sensitive detection of chlorinated compounds which are important in environmental monitoring. The ion mobility spectra in negative measuring modus mostly show one product ion peak [(H2O)nCl] due to dissociative electron attachments. In this paper, we investigated relevant chlorinated compounds (R-Cl) where R represents allyl-, benzyl-, phenyl-, alkyl- and vinyl-groups. These groups cause differences in the R-Cl bond strength and differences in the cleavage of chlorine can therefore be expected. All chlorinated substances investigated provide the same product ion peak at 2.75 cm2 Vs−1 independent on the different C-Cl bond strength. However, distinct influences of structural features on the peak intensities of the (H2O)nCl product ion peak were established. Generally, increasing sensitivities were obtained in the order chlorobenzenes < vinyl- < allyl- < alkyl compounds < benzylchlorides. Sensitivities and limits of detection (LODs) of aromatic compounds depend on the nature and position of second substituent. Electron-withdrawing substituents (chlorine, fluorine, nitrile) enhance sensitivity while electron-repelling substituents decrease it. A dependence of sensitivity on the chain length or ring size can be observed for alkyl compounds. Additional influences of intramolecular interactions on the sensitivity were found for di-halogenated compounds. Therefore, the quantification of negative product ion peaks of chlorinated compounds requires a consideration of structural features of analytes.  相似文献   

9.
A straight forward room-temperature synthesis of V(III) containing complex fluoride K3VF6, using KF and vanadium(III) acetylacetonate is reported. The pale green colored powder was characterized by chemical analysis, powder X-ray diffraction; diffuse reflectance spectroscopy, infrared spectroscopy, Raman spectroscopy, differential scanning calorimetry, scanning electron microscopy, photoluminescence spectroscopy, magnetic susceptibility measurements and photoluminescence spectroscopy. The powder X-ray diffraction pattern was fitted in P21/n space group (monoclinic) with a = 12.106 (1) Å, b = 17.685 (0) Å, c = 11.802 (0) Å, β = 92.23° (1). Differential scanning calorimetry showed phase transitions, occurring at 158 °C and 190 °C. In the FT-IR spectrum, characteristic band for the VF63− group was observed at 508 cm−1. The bands observed in the 335-361 cm−1 region and at 504 cm−1 in the room temperature Raman spectrum of K3VF6 corresponded to the F2g and A1g modes, respectively. The ratio of the frequencies (F2g/A1g) observed in the diffuse reflectance spectrum was fitted on the Tanabe-Sugano diagram to determine the Racah parameter B value of 712 cm−1. Magnetic ordering was not observed down to the lowest measured temperature of 5 K.  相似文献   

10.
Considering the rapidity and lesser sample amount required, the Fourier Transform Infrared Spectra (FTIR) was often used to quantitatively determine the rubber content of Russian dandelion, guayule, etc. This is because their chemical structure are cis-1,4-polyisoprene (CPI) which has a unique and isolate skeleton stretching vibration peak at 835 cm−1 band, and is convenient for determining the rubber content. However, this method is not suitable for Eucommia Ulmoides (EU) gum which will crystallize easily at room temperature due to the regular chemical structure of trans-1,4-polyisoprene (TPI), that will restrict the skeleton stretching vibration of TPI greatly. As a result, its FTIR spectrum only shows a very small peak at 845 cm−1 band hiding among a number of crystalline peaks around nearby, thus it cannot be used to determine the rubber content of Eucommia ulmoides oliv (E. ulmoids) directly. Actually, these crystalline peaks could be eliminated easily by elevating the temperature over 60 °C, and a unique and isolate skeleton stretching vibration characteristic band at 845 cm−1 was left alone in the TPI's FTIR spectrum which can be used expediently to determine the content of EU gum. At the present paper, the Variable Temperature Fourier Transform Infrared Spectroscopy (VTFTIR) was used to determine the rubber content of E. ulmoides. The results indicate that the rubber content of E. ulmoides samples (1–40, 5–35, 22–11) provided by Northwest Agriculture and Forestry University (NAFU) are 4.66%, 4.04%, 4.32% respectively, and the errors of average value were less than 5% compared with Soxhlet Extraction.  相似文献   

11.
The synthesis of indolo[3,2-b]carbazole-based mono- and dihydrazones with reactive vinylbenzyl or vinyloxyethyl functional groups at the nitrogen atom of hydrazine moiety is reported. The thermal, optical, photophysical, electrochemical and photoelectrical properties of the synthesized compounds are described. They exhibit moderate thermal stability with 5% weight loss temperatures ranging from 273 to 343 °C. Self-polymerization of the monomers with vinylbenzyl functional groups starts at around 180 °C. The values of ionization potentials of the compounds measured by cyclic voltammetry are in the range of 4.94–5.00 eV and those estimated by electron photoemission in air range from 4.99 to 5.21 eV. Electron affinities range from −2.28 to −2.23 eV. The molecular structure of these hydrazones allows stable amorphous films to be prepared and the hole drift mobilities of the films exceed 10−3 cm2/V s at high electric fields.  相似文献   

12.
The structural evolution and thermal behavior of polyacrylonitrile (PAN) homopolymer and copolymer [P(AN-IA)] containing about 1.5 mol% itaconic acid (IA) during stabilization in air were studied by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetry (TG). A new parameter Es=A1595cm−1/A2243cm−1 was defined to evaluate the extent of stabilization. The kinetic parameters, viz. activation energy (Ea) and pre-exponential factor (A) of the stabilization reactions were calculated by Kissinger method and Ozawa method. FTIR analysis indicated that the cyclization of nitrile groups was initiated at a lower temperature by the IA comonomer and the stabilization proceeded at a more moderate pace in P(AN-IA) than in PAN, while an IA additive was found to be decomposed and failed to initiate the cyclization at a lower temperature. The improvement effect of IA comonomer on the stabilization reactions was further confirmed by the dynamic thermal analysis and kinetic study.  相似文献   

13.
Teflon AF 2400 (Du Pont) is an amorphous, glassy perfluorinated copolymer containing 87 mol% 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole and 13 mol% tetrafluoroethylene. The polymer has an extremely high fractional free volume of 0.327. Permeability coefficients for helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, propane, and chlorodifluoromethane (Freon 22) were determined at temperatures from 25 to 60°C and pressures from 20 to 120 psig. Permeation properties were also determined at a feed pressure of 200 psig at 25°C with a 2 mol% n-butane/98 mol% methane mixture. Permeabilities of permanent gases in Teflon AF 2400 are among the highest of all known polymers; the oxygen permeability coefficient at 25°C is 1600 × 10−10 cm3 (STP) cm/cm2 s cmHg and the nitrogen permeability coefficient is 780 × 10−10 cm3 (STP) cm/cm2 s cmHg. The permeabilities of organic vapors increase up to 20-fold as the vapor activity increases from 0.1 to unity, indicating that Teflon AF 2400 is easily plasticized. Although Teflon AF 2400 is an ultrahigh-free-volume polymer like poly(1-trimethylsilyl-1-propyne) [PTMSP], their gas permeation properties differ significantly. Teflon AF 2400 shows gas transport behavior similar to that of conventional, low-free-volume glassy polymers. PTMSP, on the other hand, acts more like a nanoporous carbon than a conventional glassy polymer.  相似文献   

14.
Polycarbonate (Makrofol-N) and polystyrene thin films were irradiated with protons (3 MeV) under vacuum at room temperature with the fluence ranging from 1×1014 to 1×1015 protons cm−2. The change in optical properties, degradation of the functional groups and crystallinity of the proton-irradiated polymers were investigated with UV–vis, Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) techniques, respectively. The UV–vis analysis revealed that the optical band gap of irradiated Makrofol-N is reduced by 30% as compared to 27.5% in polystyrene at highest fluence of 1×1015 protons cm−2, owing to higher electronic energy loss of protons in Makrofol-N. The calculations of the number of carbon atoms per conjugation length, N and number of carbon atoms per clusters, M embedded in the network of polymers further revealed that Makrofol-N is more modified as compared to polystyrene on proton irradiation. FTIR results reveal the reduction in absorption intensity of the main characteristic bands of both the polymers after irradiation. The proton-irradiated Makrofol-N shows a strong decrease of almost all of its characteristic absorption bands at about 1×1014 protons cm−2. Beyond a critical dose an increase of almost all its characteristic bands are noticed, however, no such effect had been observed in polystyrene at this particular fluence. Appearance of new –OH groups was observed at the higher fluences in the FTIR spectra of both proton-irradiated polymers. XRD measurements show the decrease of the main peak intensity and the crystallite size, confirming the increase of amorphization in polymers under irradiation.  相似文献   

15.
For polymer electrolyte membrane fuel membrane cell (PEMFC) applications, the effect of electron-withdrawing groups on the properties of sulfonated poly(arylene ether) (SPE) ionomer membranes was investigated. A series of poly(arylene ether)s containing fluorenyl groups and electron-withdrawing groups (sulfone, nitrile, or fluorine) was synthesized, which were sulfonated with chlorosulfonic acid using a flow reactor to obtain the title ionomers. The ionomers had high molecular weight (M> 77 kDa, Mw > 238 kDa) and gave tough, ductile membranes by solution casting. The ion exchange capacity (IEC) of the membranes ranged from 1.6 to 3.5 mequiv/g as determined by titration. The electron-withdrawing groups did not appear to affect the thermal properties (decomposition temperature higher than 200 °C). The presence of nitrile groups, especially at positions meta to the ether linkages, improved the oxidative stability of the SPE membranes, while it led to a deterioration of the hydrolytic stability. The perfluorinated biphenylene groups were effective in providing high mechanical strength with reasonable dimensional change, probably due to a somewhat decreased water absorbability. The SPE membrane containing sulfone groups showed the highest proton conductivity (10−3-10−1 S/cm) at 20-93% RH (relative humidity) and 80 °C. The nitrile-containing SPE membrane showed smaller apparent activation energies for oxygen and hydrogen permeability and is thus considered to be a possible candidate for applications in PEMFCs.  相似文献   

16.
Coumarin-functionalized poly(ethylene glycol) (PEG) monols and diols were isothermally crystallized at temperatures between 20 and 35 °C before and after exposure to approximately 110 J cm−2 of ultra-violet A (λ > 300 nm, UVA) irradiation. Irradiation dimerized the coumarin groups and chain-extended the coumarin-functionalized PEG oligomers. The higher molecular weights reduced the crystal growth rate by as much as 50% compared to the non-irradiated coumarin-functionalized PEG oligomers under ambient crystallization conditions. Hoffman’s kinetic nucleation theory was utilized to evaluate the types of nucleation that occurred for the coumarin-functionalized PEG diols (COU-PEG-COU). Crystallization regimes II and III were observed for the coumarin-modified PEG oligomers before and after exposure to UVA light.  相似文献   

17.
Miscanthus x giganteus was treated with formic acid/acetic acid/water (30/50/20 v/v) for 3 h at 107 °C and 80 °C, and soaking in aqueous ammonia (25% w/w) for 6 h at 60 °C. The effects of these fractionation processes on chemical structure, physico-chemical properties and antioxidant activity of extracted lignins were investigated. Lignins were characterized by their purity, carbohydrate composition, thermal stability, molecular weight and by Fourier transform infrared (FTIR), 1H and quantitative 13C nuclear magnetic resonance (NMR), adiabatic broadband {13C-1H} 2D heteronuclear (multiplicity edited) single quantum coherence (g-HSQCAD). The radical scavenging activity towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) was also investigated. Formic/acetic acid pretreatment performed in milder conditions (80 °C for 3 h) gave a delignification percentage of 44.7% and soaking in aqueous ammonia 36.3%.Formic/acetic acid pretreatment performed in harsh conditions (107 °C for 3 h) was more effective for extensive delignification (86.5%) and delivered the most pure lignin (80%). The three lignin fractions contained carbohydrate in different extent: 3% for the lignin obtained after the formic/acetic acid pretreatment performed at 107 °C (FAL-107), 5.8% for the formic/acetic acid performed at 80 °C (FAL-80) and 13.7% for the ammonia lignin (AL). The acid pretreatment in harsh conditions (FAL-107) resulted in cleavage of β-O-4′ bonds and aromatic C-C. Repolymerisation was thought to originate from formation of new aromatic C-O linkages. Under milder conditions (FAL-80) less β-O-4′ linkages were broken and repolymerisation took place to a lesser extent. Ammonia lignin was not degraded to a significant extent and resulted in the highest weight average 3140 g mol−1. Despite the fact of FAL-107 repolymerisation, significant phenolic hydroxyls remained free, explaining the greater antioxidant activity.  相似文献   

18.
Gold was determined by electrothermal atomic absorption spectrometry after electrochemical preconcentration on the graphite ridge probe used as a working electrode and sample support. The probe surface was electrochemically modified with Pd, Re and the mixture of both. The electrolysis of gold was performed under galvanostatic control at 0.5 mA. Maximum pyrolysis temperature for the probe surface modified with Pd was 1200 °C, with Re 1300 °C. The relative standard deviation for the determination of 2 μg l− 1 Au was not higher than 5.6% (n = 8) for 2 min electrodeposition. The sensitivity of gold determination was reproducible for 300 electrodeposition and atomization cycles. When the probe surface was modified with a mixture of Pd and Re the detection limit was 31 ng l− 1 for 2 min electrodeposition, 3.7 ng l− 1 for 30 min, 1.5 ng l− 1 for 1 h and 0.4 ng l− 1 for 4 h electrodeposition, respectively. The procedure was applied to the determination of gold in river water samples. The relative standard deviation for the determination of 2.5 ng l− 1 Au at 4 h electrodeposition time at 0.5 mA was 7.5%.  相似文献   

19.
The design, fabrication and microwave properties of distributed coplanar waveguide (CPW) phase shifters using etched Ba0.6Sr0.4TiO3 (BST) thin films on Ф 3″ LaAlO3 (100) substrates were investigated. The BST thin films employed in the circuits are deposited by RF magnetron sputtering, and then annealed at 800 °C for 30 min in air. BST thin films parallel-plate capacitors were fabricated by photolithography and etching process. At 10 kHz and 600 kV/cm electric field, the dielectric tunability, remanent polarization (2Pr) and the coercive electric field (2EC) of BST film were 28.7%, 2.265 μC/cm2 and 38.8 kV/cm, respectively. The loss tangent was 0.005 at zero electric field. The CPW phase-shifter designed was subsequently fabricated by optimum BST thin films and thickened top electrodes. At 21.3 GHz and 35 V, 360° phase shift was achieved, the insertion loss was −8.5 dB, the ?gure-of-merit (FOM) was 42.4°/dB, and the return loss was −12.1 dB.  相似文献   

20.
A series of novel fluorinated heat-resistant poly(amide imide)s (PAIS) based on non-coplanar diimide-diacid monomer (DIDA) were synthesized and characterized. The poly(amide imide)s were obtained in high yields and possessed inherent viscosities in the range of 0.47-0.91 dL g−1. All of the polymers were amorphous in nature, showed outstanding solubility and could be readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinoned, dimethyl sulfoxide, N,N-dimethylformamide, pyridine and tetrahydrofuran. Glass transition temperatures were in the range of 221-263 °C, as determined by differential scanning calorimetry. Degradation temperatures for 10% weight loss occurred all above 520 °C and char yields was more than 50% at 700 °C in nitrogen atmosphere. Moreover, these PAIs possessed low refractive indexes (n = 1.58-1.59), birefringence (Δn = 0.008-0.013), and dielectric constants (? ≈ 2.5) due to the trifluoromethyl pendent groups and ortho-catenated aromatic rings that interrupt chain packing and increase free volume.  相似文献   

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