共查询到20条相似文献,搜索用时 31 毫秒
1.
J. Castillo Montes D. CadouxJ. Creus S. TouzainE. Gaudichet-Maurin O. Correc 《Polymer Degradation and Stability》2012,97(2):149-157
In France, hot water quality control inside buildings is occasionally assured by disinfection treatments using sodium hypochlorite (between 0.5 and 1 ppm residual free chlorine). This disinfectant is a strong oxidizer and it could interact with metallic and polymer pipes used in hot water systems. To assess the long-term performance of these pipes, it is then necessary to study the impact of these treatments on the material behaviour, in particular for polymeric materials, even at relatively low disinfectant concentrations as used in potable water treatments. The objective of this work was to study the influence of sodium hypochlorite concentration on PERT/Al/PERT (PolyEthylene Raised Temperature) pipe degradation. Pipe samples were filled with chlorinated water solutions (concentrations ranging between 0 and 100 ppm) and maintained in static conditions during 270 days at 70 °C. The antioxidant depletion profile through a PERT wall was monitored using the oxidation induction time (OIT) method, which is a conventional technique of Differential Scanning Calorimetry. Chemical changes on the aged polymer were checked by Infrared Spectrometry. OIT change showed that the PERT stabilizing system was rapidly chemically consumed by the action of chlorinated water at 25 and 100 ppm concentrations. However, PERT degradation was strictly confined to the immediate inner wall. Only a 0.3 mm thick layer (inner part of the pipe) showed significant antioxidant depletion. An increase of the OH and C-O-C infrared bands was also observed on inner part of any samples during ageing which characterize the oxidation of the PERT on the inner wall. 相似文献
2.
M. Ekelund 《Polymer Degradation and Stability》2008,93(9):1704-1710
Cable samples with plasticized poly(vinyl chloride) insulations were aged in air at temperatures between 80 and 155 °C. The concentrations of the plasticizer (di-(2-ethylhexyl) phthalate, DEHP) in the insulations of the aged cables were determined by extraction of samples in tetrahydrofuran followed by analysis of the extract by liquid chromatography. The plasticizer concentration data for different ageing times were analysed by numerical methods, fitting Fick's second law with a concentration-dependent diffusivity. The analysis showed that the transport of the plasticizer to the surrounding air phase was controlled by diffusion at 120 and 155 °C with an activation energy of 89 kJ mol−1. The evaporation of the plasticizer from the outer boundary was rate controlling at lower temperatures (≤100 °C). The rate of evaporation was initially constant and independent of the plasticizer concentration at both 80 and 100 °C. The activation energy for the initial DEHP loss rate from PVC at these temperatures was the same as that obtained for evaporation of pure DEHP on a glass plate at 60-100 °C measured by thermogravimetry, 98 ± 2 kJ mol−1. Furthermore, the evaporation rate of pure DEHP on a glass plate was also of the same order of magnitude as the rate of plasticizer loss from the cable insulation. Extrapolation of the plasticizer loss rate data (from the cable at 80 °C and from pure liquid DEHP at temperatures between 60 and 100 °C) to 25 °C predicted a maximum loss of plasticizer of 1% over 25 years. This is in accordance with earlier presented data and with the data presented in this report. 相似文献
3.
A green BaZr0.1Ce0.7Y0.2O3−δ (BZCY) electrolyte layer was deposited on porous anode substrate (BZCY:NiO = 35:65, in weight ratio) by a suspension spray. In this process, the suspension was prepared by directly ball-milling the mixed BaCO3, CeO2, ZrO2 and Y2O3 powders in ethanol for 24 h. Then the bi-layers were co-sintered at 1400 °C for 5 h in air to obtain dense and uniform electrolyte membrane in the thickness of 10 μm. With Nd0.7Sr0.3MnO3−δ cathode, a fuel cell was assembled. It was tested from 600 °C to 700 °C using humid hydrogen as fuel and air as oxidant. The cell at 700 °C exhibited 1.02 V for open circuit voltage (OCV), 450 mW/cm2 for peak output and 0.18 Ω cm2 for electrode polarizations under open circuit conditions, respectively. The results indicate that it is feasible to fabricate thin electrolyte membrane for solid oxide fuel cells (SOFCs) by this simple, cost-effective and efficient technique. 相似文献
4.
Jing-Xiao Liu Yoshihiko Ando Fei Shi Kenji Adachi Akikazu Tanaka 《Journal of solid state chemistry》2010,183(10):2456-2460
Cesium tungsten oxides (CsxWO3) were synthesized by solvothermal reactions using ethanol and 57.1 vol% ethanol aqueous solution at 200 °C for 12 h, and the effects of post annealing in ammonia atmosphere on the microstructure and electrical-optical properties were investigated. Agglomerated particles consisting of disk-like nanoparticles and nanorods of CsxWO3 were formed in the pure ethanol and ethanol aqueous solutions, respectively. The samples retained the original morphology and crystallinity after annealing in ammonia atmosphere up to 500 °C, while a small amount of nitrogen ion were incorporated in the lattice. The as-prepared CsxWO3 sample showed excellent near infrared (NIR) light shielding ability as well as high transparency in the visible light region. The electrical resistivity of the pressed pellets of the powders prepared in pure ethanol and 57.1 vol% ethanol aqueous solution greatly decreased after ammonia annealing at 500 °C, i.e., from 734 to 31.5 and 231 to 3.58 Ω cm, respectively. 相似文献
5.
M.O. Boussoum 《Polymer Degradation and Stability》2006,91(3):579-584
Commercial sunflower oil was epoxidised and used as organic co-stabiliser for rigid and plasticised poly(vinyl chloride) (PVC) containing Zn and Ca stearates as primary stabilisers and stearic acid as lubricant. For applications in the packaging of foodstuffs, migration testing must be performed. The detection and the quantification of contaminants migrating from the polymer into the food simulants are essential for the safety assessment of food contact plastic packaging materials. For that purpose, two food simulants were used: olive oil and 15% (v/v) aqueous ethanol. These represent fatty and moist food and beverages, respectively. The test conditions were 12 days at 40 °C. Circular samples of rigid PVC and PVC plasticised with dioctyl phthalate were immersed in a known volume of food simulant. A circular sample and 10 ml of food simulant were taken off every day to be analysed. Each sample was wiped and weighed. The rate of variation of the mass was determined as a function of time. The evolution of the peroxide index of olive oil with time was analysed. The specific migrations of the present additives were investigated by using two analytical methods (atomic absorption spectrometry and Fourier transform infrared spectroscopy). The influence of various parameters such as the nature of food simulant, the presence or the absence of the plasticiser, the agitation and time of contact was considered. 相似文献
6.
Long-term performance of poly(vinyl chloride) cables. Part 1: Mechanical and electrical performances
Cables insulated with plasticized poly(vinyl chloride) were aged in air at temperatures between 80 °C and 180 °C and their conditions were assessed by indenter modulus measurements, tensile testing, infrared (IR) spectroscopy and differential scanning calorimetry (DSC). Electrical testing of oven-aged cable samples was performed in order to relate the electrical functionality during a high-energy line break (HELB) to the mechanical properties and to establish a lifetime criterion. The mechanical data taken at room temperature after ageing could be superimposed with regard to ageing time and temperature. The ageing-temperature shift factor showed an Arrhenius temperature dependence. The jacketing material showed an immediate increase in stiffness (indenter modulus and Young's modulus) and a decrease in the strain at break on ageing; these changes were dominated by loss of plasticizer by migration which was confirmed by IR spectroscopy and DSC. The core insulation showed smaller changes in these mechanical parameters; the loss of plasticizer by migration was greatly retarded by the closed environment, according to data obtained by IR spectroscopy and DSC, and the changes in the mechanical parameters were due to chemical degradation (dehydrochlorination). A comparison of data obtained from this study and data from other studies indicates that extrapolation of data for the jacketing insulation can be performed according to the Arrhenius equation even down to service temperatures (20-50 °C). The low-temperature deterioration of the jacketing is, according to this scheme, dominated by loss of plasticizer by migration. 相似文献
7.
This paper presents a fully automated method for determining ten primary amines in wastewater at ng/L levels. The method is based on simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to ion trap tandem mass spectrometry (GC–IT-MS–MS). The influence of main factors on the efficiency of derivatization and of HS-SPME is described in detail and optimized by a central composite design. For all species, the highest enrichment factors were achieved using a 85 μm polyacrylate (PA) fiber exposed in the headspace of stirred water samples (750 rpm) at pH 12, containing 360 g/L of NaCl, at 40 °C for 15 min. Under optimized conditions, the proposed method achieved detection limits ranging from 10 to 100 ng/L (except for cyclohexylamine). The optimized method was then used to determine the presence of primary amines in various types of wastewater samples, such as influent and effluent wastewater from municipal and industrial wastewater treatment plants (WWTPs) and a potable water treatment plant. Although the analysis of these samples revealed the presence of up to 1500 μg/L of certain primary amines in influent industrial wastewater, the concentration of these compounds in the effluent and in municipal and potable water was substantially lower, at low μg/L levels. The new derivatization–HS-SPME–GC–IT-MS–MS method is suitable for the fast, reliable and inexpensive determination of primary amines in wastewater in an automated procedure. 相似文献
8.
Manfred A. Bohn 《Thermochimica Acta》2003,401(1):27-41
New types of rocket propellant batches have been formulated with the objective of achieving higher burning rates. The main ingredients are (1) the energetic plasticizers glycidyl azide polymer-α,ω-diazide (GAP)-A (short chain GAP with azide end groups), trimethylolethane trinitrate (TMETN) and 1,2,4-butanetriol trinitrate (BTTN), (2) the energetic substances ammonium perchlorate (AP) and ε-CL20 (ε-HNIW, hexanitrohexazaisowurtzitane, crystallised in ε-phase). The binder is GAP (glycidyl azide polymer, diol component) cured with the polyisocyanate Desmodur™ N100. From the point of view of stability and ageing, the interesting fact is that the formulations contain none of the typical stabilisers for the nitric acid ester components TMETN and BTTN, although their contents range up to 21 mass%. One reason for doing so is to increase the content of the high energy ingredients. Seven formulations were examined in more detail. To assess basic stability the autoignition temperature test, Dutch mass loss test and vacuum stability test were used. To investigate ageing, two measurement quantities are applied: heat generation rate (heat flow) as function of time at 70, 80 and 89 °C and mass loss as function of time at the temperatures of 70, 80 and 90 °C. The evaluation of the measurements was done with reaction kinetic models. One batch (#189) containing BTTN shows significantly lower activation energy and pre-exponential factor. From mass loss one gets as activation energy for #189 of 101 kJ mol−1 in comparison to the range of 126-135 kJ mol−1 for the six other batches. But, based on the ageing caused by chemical decomposition reactions, all seven batches showed a good ageing behaviour. A use time period of up to 20 years of use seems realistic. 相似文献
9.
An anion substitution route was utilized for lowering the dielectric loss in CaCu3Ti4O12 (CCTO) by partial replacement of oxygen by fluorine. This substitution reduced the dielectric loss, and retained a high dielectric constant that was essentially temperature independent from 25 to 200 °C. In particular, CaCu3Ti4O11.7F0.3 exhibited a giant dielectric constant over 6000 and low dielectric loss below 0.075 at 100 kHz within a temperature range of 25-200 °C. Fluorine analysis confirmed the presence of fluorine in all samples measured. 相似文献
10.
Spruce sulphite cellulose (number average degree of polymerization 620) dissolved in an aqueous solution of 8% (w/w) LiOH*H2O and 12% (w/w) urea was methylated with dimethyl sulphate (DMS). By varying the reaction temperature between 22 and 50 °C, the molar ratio between 9 and 15 mol DMS per mol anhydroglucose unit, and the reaction time from 4 to 24 h, methyl cellulose (MC) with degree of substitution (DS) values in the range of 1.07 and 1.59 was prepared. The chemical structure of MC was analysed by FTIR and 1H NMR spectroscopy. The turbidity (given in nephelometric turbidity units, NTU) of the aqueous solution of MC reached an optimum of 10 NTU for a product obtained with 12 mol DMS/mol AGU at 50 °C. GPC measurements revealed polymer degradation to a certain extent. The intrinsic viscosity and the Huggins constant k of the MC samples increased with increasing DS value. The MC samples possess k values higher than 0.8, indicating association of the polymer chain. The zero-shear viscosity decreased with increase of both temperature and the amount of methylation agent due to the depolymerization. During the heating/cooling cycle (20-90 °C) of the aqueous solutions of MC, it was observed that samples synthesized at 22 °C with DS values lower than 1.3 did not undergo phase separation in aqueous solution. Phase separation hysteresis with a precipitation temperature up to 80 °C was obtained for aqueous solutions of MC with DS values between 1.07 and 1.66 synthesized at higher temperatures. The functionalization pattern determined by GLC of the corresponding partially methylated glucitol acetates is close to randomness and comparable with those of commercial MC samples. 相似文献
11.
A method for the determination of Ag, Cd, Cu, Pb and Tl in fuel alcohol by isotope dilution electrothermal vaporization inductively coupled plasma mass spectrometry (ID ETV-ICP-MS) is proposed. The analytes were separated in two groups: Ag and Cu were determined without modifier and Cd, Pb and Tl with the use of Pd as chemical modifier. The employed ETV operational conditions were pyrolysis temperature of 800 °C for Cd, Pb and Tl and of 900 °C for Ag and Cu and vaporization temperature of 2400 °C for both groups. Seven common, one with additive and one anhydrous fuel ethanol samples were analyzed. The spiked and reference isotopes were, respectively, 109Ag and 107Ag, 112Cd and 111Cd, 63Cu and 65Cu, 206Pb and 208Pb and 203Tl and 205Tl. The added amounts of the enriched isotope material were the same for all samples: 4.6 ng of 109Ag, 5 ng of 112Cd, 21.1 ng of 63Cu, 9 ng of 206Pb and 0.21 ng of 203Tl. The blank was bi-distilled ethanol, acidified with 0.3% (v/v) nitric acid, as the samples. The limits of detection (LODs) were calculated as three times the standard deviation of the concentrations in the blank (n = 10) and were, in μg L−1, for Ag: 0.02, for Cd: 0.08, for Cu: 0.1, for Pb: 0.05 and for Tl: 0.001. The obtained concentrations in the samples were in agreement with those obtained by external calibration (EC), according to the paired t-test. The isotope dilution (ID) showed to be a robust, fast and simple calibration technique for the analysis of fuel ethanol. 相似文献
12.
A poly-ε-caprolactam (PA6) taken as a reference and its nanocomposite (PNC) containing 1.6 wt.% of montmorillonite were examined. The specimens as discs were prepared by compression moulding at 235 °C and 70 MPa. Using the novel version of TMA, in the PA6 and PNC specimens, within the temperature range from −100 to 250 °C, a semi-crystalline structure with anisotropy of distribution of the more ordered (crystalline?) portion was found in the surface layer up to 0.5 mm thick. The amorphous regions have differed in a state of order (different transition temperatures) and related compactness. The free volume fraction in amorphous regions determined in machine direction (normal to the surface) is increased when in transverse direction is reduced; simultaneously molecular weights of polymer chains between junctions were increased by incorporation of the nanofiller. 相似文献
13.
This paper presents an alternative analytical method employing energy dispersive X-ray fluorescence (EDXRF) to determine copper, iron, nickel and zinc ions in ethanol fuel samples after a pre-concentration procedure. Our pre-concentration strategy utilizes analyte retention on cation exchange chromatography paper, a convenient substrate for direct EDXRF measurements. The repeatability, expressed in terms of RSD of standard solutions containing 0.25 μg mL−1 of Cu, Fe, Ni and Zn, and calculated from fifteen consecutive measurements, was 2.5, 2.8, 3.0, and 2.7%, respectively. The limits of detection (LOD), defined as the analyte concentration that gives a response equivalent to three times the standard deviation of the blank (n = 10), were found to be 13, 15, 15 and 12 μg L−1 for Cu, Fe, Ni and Zn, respectively. The proposed method was applied to Cu, Fe, Ni and Zn determination in hydrated ethanol fuel samples collected from different gas stations. 相似文献
14.
The volatile composition from four types of multifloral Portuguese (produced in Madeira Island) honeys was investigated by a suitable analytical procedure based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography-quadrupole mass spectrometry detection (GC-qMS). The performance of five commercially available SPME fibres: 100 μm polydimethylsiloxane, PDMS; 85 μm polyacrylate, PA; 50/30 μm divinylbenzene/carboxen on polydimethylsiloxane, DVB/CAR/PDMS (StableFlex); 75 μm carboxen/polydimethylsiloxane, CAR/PDMS, and 65 μm carbowax/divinylbenzene, CW/DVB; were evaluated and compared. The highest amounts of extract, in terms of the maximum signal obtained for the total volatile composition, were obtained with a DVB/CAR/PDMS coating fibre at 60 °C during an extraction time of 40 min with a constant stirring at 750 rpm, after saturating the sample with NaCl (30%). Using this methodology more than one hundred volatile compounds, belonging to different biosynthetic pathways were identified, including monoterpenols, C13-norisoprenoids, sesquiterpenes, higher alcohols, ethyl esters and fatty acids. The main components of the HS-SPME samples of honey were in average ethanol, hotrienol, benzeneacetaldehyde, furfural, trans-linalool oxide and 1,3-dihydroxy-2-propanone. 相似文献
15.
The effects of temperature on the stability of a soil humic acid were studied in the present work. Solid samples of Gohy-573 humic acid (HA) and dissolved ones in aqueous solution (pH 6.0, 0.1 mol L−1 NaClO4) were investigated in order to understand the impact of temperature on the chemical properties of the material. The methods applied to solid samples in the present investigation were thermogravimetric analysis (TGA), temperature-programmed desorption coupled with mass spectrometry (TPD-MS), and in situ diffuse reflectance infrared Fourier transformed spectroscopy (in situ DRIFTS). Humic acid samples were studied in the 25-800 °C range, with focus on thermal/chemical processes up to 250 °C. The reversibility of the changes observed was investigated by cyclic changes to specified temperature ranges (40-110 °C). All measurements were conducted under inert-gas atmosphere in order to avoid samples combustion at increased temperatures. Aqueous solutions were analyzed by UV-vis absorption spectroscopy after storage at temperatures up to 95 °C, and storage times up to 1 week. For temperatures below 100 °C experiments on solid and aqueous samples have shown results which were consistent to each other. The amount of water desorbed is temperature dependent and up to 70 °C this process was totally reversible. Above 70 °C an irreversible loss of water was also observed, which according to UV-vis spectroscopy corresponds to water produced by condensation leading to more condensed polyaromatic structures. The water released up to 110 °C was about 7 wt% of the total mass of the dried humic acid, where less than 50% corresponded to reversibly adsorbed water. At higher temperatures (>110 °C), gradual decomposition resulting in the formation of carbon dioxide (110-240 °C), and carbon monoxide (140-240 °C) takes place. Hence, thermal treatment of Gohy-573 humic acid above 70 °C results in irreversible structural changes, that could affect chemical properties (e.g., complex formation) of the material. 相似文献
16.
M. Lundbäck 《Polymer Degradation and Stability》2006,91(7):1571-1580
Plaques of linear polyethylene (LPE) and branched polyethylene (BPE) were exposed to oxygen-free media (nitrogen or water) at 75, 90 and 95 °C. The polymers were stabilized with one of the following three bifunctional phenolic antioxidants: Santonox R, Irganox 1081 or Lowinox 22M46. The initial concentration of antioxidant in the plaques was ∼0.09 wt.%. After ageing, the oxidation induction time profiles obtained by differential scanning calorimetry often became very flat, which indicated that migration was controlled by the boundary loss process. The unexpected higher migration rate from LPE than from BPE was due to the dominance of the boundary loss process. It is proposed that the low boundary loss rate in BPE was due to the presence of a thin liquid-like (oligomeric) surface layer which developed during ageing of this polymer. A qualitative relationship was found between the boundary loss rate to water and the polarity of the antioxidant. The antioxidant diffusivities in LPE and BPE were approximately equal, a finding which, in view of the morphological analysis estimating the geometrical impedance factor, indicated that the constraining effect of the crystals on the non-crystalline fraction was not sensed by the antioxidant molecules. It is suggested that the large molecular size and the low segmental flexibility of the antioxidant molecules inhibited their ability to penetrate the interfacial component. 相似文献
17.
Jaroslav Kratochvíl Adriana Šturcová Antonín Sikora Ji?í Dybal 《European Polymer Journal》2009,45(6):1851-1040
Critical overview of literature data on the glass transition temperature Tg of poly(4-vinylphenol) PVPh revealed a large scatter of values ranging between 53 and 194 °C, which can only partially be attributed to molecular-mass effect. The reason could be seen in residual moisture and/or solvent in samples subjected to insufficient or even no drying. Based on selected two thirds of literature data, a regression equation is proposed for the dependence of Tg on 1/Mn. Two samples of commercial PVPh (Mn 11,500; Mw 22,100) and (Mn 19,700; Mw 40,900) were studied by DSC, ATR-FTIR, and SEC methods. A procedure of preparing well defined samples is proposed: PVPh vacuum-dried at 140 °C for 24 h is dissolved in tetrahydrofuran and precipitated in hexane. The precipitate is vacuum-dried at 40 °C for 24 h, weighed into a pierced DSC pan. After final vacuum drying at 140 °C for 24 h, the sample is analyzed. The PVPh samples treated in this way showed Tg of 175.0 °C and 179.6 °C, respectively. 相似文献
18.
The ageing of filled and cross-linked ethylene propylene diene elastomer (EPDM) has been studied under accelerated UV irradiation (λ ≥ 290 nm) at 60 °C, thermal ageing at 100 °C and in nitric acid vapours for different time intervals. Hardness measurements were performed. DSC-thermoporosimetry was used to estimate the mesh size distribution and cross-linking densities for each ageing. The development of functional groups was monitored by ATR spectroscopy. An increase in oxidation with exposure time after the different types of ageing was observed. The thermal stability of EPDM was assessed by TGA and evolved volatile gases were identified using FTIR spectroscopy. 相似文献
19.
Anita Quye David Littlejohn Richard A. Pethrick Robert A. Stewart 《Polymer Degradation and Stability》2011,96(10):1934-1939
Cellulose nitrate is susceptible to hydrolysis as well as loss of plasticiser when left in a humid atmosphere. A comparison of the ageing behaviour of cellulose nitrate samples prepared from cotton linters was used to simulate the artefacts studied in a previous study. Certain artefacts were also subjected to accelerated ageing at 12%, 55% and 75% relative humidity at 70 °C. The rate of degradation was observed to vary with the RH, indicating the connection between the absorption of moisture and the hydrolysis process. The effect of varying the sulphate level on the rate of hydrolysis was studied using concentrations similar to those detected in artefacts. The study was carried out using <0.1 mg g−1, 2 mg g−1 and 5 mg g−1 of sulphate and distinct differences were observed which is consistent with the conclusions drawn for a study of a number of artefacts. The observed rates of degradation are consistent with previous studies on cellulose nitrate. The degradation was studied using a combination of infrared spectroscopy, ion chromatography and gel permeation chromatography. The analysis was complemented by a study of the weight changes which occur during ageing. 相似文献
20.
Ivana Šeděnková Miroslava Trchová Jaroslav Stejskal 《Polymer Degradation and Stability》2008,93(2):428-435
Polyaniline films were produced in situ at room temperature from aniline hydrochloride oxidized with ammonium peroxydisulfate on glass surfaces immersed in an aqueous reaction mixture. A notable change in the character of the time dependence of resistivity at fixed temperature was observed when the temperature of ageing exceeded 85 °C. The ageing was much faster above this limit. This observation is reflected in the FTIR spectroscopic measurements on the aged protonated, as well as deprotonated, samples. The FTIR spectral variation may be explained by a conformational transition of the polymer chain at about 85 °C. The fact that a similar transition has been found with deprotonated samples indicates that this feature is an inherent property of polyaniline, and is not caused by the acid component of the PANI salt. 相似文献