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1.
The surface free energy of non-F and F-containing ladder polyepoxysilsesquioxanes was calculated by two- and three-liquid methods based on contact angle measurements. These ladder polyepoxysilsesquioxanes exhibited lower surface free energy (<17 mJ/m2) because of their main chain packing on the surface of the films where the side chain alignment was promoted by their ladder structure. And the surface free energy of the polyepoxysilsesquioxanes could be reduced further by the incorporation of perfluoroalkyl group into the side chains (∼13 mJ/m2). The X-ray diffraction results revealed that the F-containing side chain lead to the ladder main chain much more flattening on the surface of the films, explaining the contributions of side and main chain arrangements to the surface free energy.  相似文献   

2.
Thermo-oxidative effects on the surface energy of polypropylene were measured by inverse gas chromatography as a function of exposure time and temperature. Unaltered polypropylene had a surface energy of 33 mJ/m2. Oxidized polypropylene, after exposure to air at temperatures of 100 °C and 110 °C, had a range of maximum surface energies from 38 to 41 mJ/m2. Comparisons between FTIR carbonyl peak growth and the surface energy showed that both methods detect oxidation, though the increase in surface energy is detected before the carbonyl peak growth is noticeable. The work of adhesion predicted by the surface free energies obtained in this work between a coated calcium carbonate and polypropylene changes by 10% due to the oxidation of the polymer at 110 °C.  相似文献   

3.
Fluoroacrylate copolymer miniemulsion was prepared by miniemulsion polymerization under microwave irradiation. The composition of the copolymer was determined by FTIR, DSC, 1H NMR and 19F NMR. The morphology, size, and size distribution of the latex particles as well as changes in the size during polymerization were characterized by TEM and photon correlation spectroscopy (PCS). The effects of kinetic parameters on the polymerization were evaluated. The particle size of latex underwent almost no change during microwave irradiation polymerization. The diameters of latex particles prepared by microwave irradiation were smaller and more monodispersed than those prepared by conventional heating and the latex had good centrifugal stability. Polymerization under microwave irradiation had a higher reaction rate and higher conversion than traditional heating. By using 10 wt% fluoromonomer, the surface energy of the latex film could be reduced from 27.24 mJ/m2 (latex film of fluorine-free) to 17.59 mJ/m2 and the decomposition temperature increased by 25 °C.  相似文献   

4.
The nylon 6/MgAl layered double hydroxide (MgAl-LDH) nanocomposites have been prepared by melt intercalation of nylon 6 into the part organic dodecyl sulfate (DS) anion-modified MgAl(H-DS) interlayers. The structures and properties of MgAl(H-DS) and corresponding nanocomposites were characterized by ion chromotography, X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and cone calorimeter test (CCT). The nanoscale dispersion of MgAl(H-DS) layers in the nylon 6 matrix has been verified by the disappearance of d001 XRD diffraction peak of MgAl(H-DS) and the observation of TEM image. DSC tests evince that these exfoliated MgAl(H-DS) layers play the role of nucleating agents with strong heterogeneous nucleation effect on the crystallization of nylon 6 and increase its crystallization temperature over 12 °C with only 5 wt% MgAl(H-DS). TGA tests show that the effect of alkaline catalysis degradation from LDH on nylon 6 decreases the thermal stability of nylon 6/MgAl-LDH nanocomposites. The data from the cone calorimeter tests show that the HRR and MLR values of the sample with 5 wt% MgAl(H-DS) decrease considerably to 664 kW/m2 and 0.161 g/m2 s from 1064 kW/m2 and 0.252 g/m2 s of pure nylon 6, respectively. This kind of exfoliated nanocomposite is promising for the application of flame-retardant polymeric materials.  相似文献   

5.
The long-term stability of Pd–23%Ag/stainless steel composite membranes has been examined in H2/N2 mixtures as a function of both temperature and feed pressure. During continuous operation, the membrane shows a good stability at 400 °C while the N2 leakage increases very slowly at a temperature of 450 °C (Pfeed = 10 bar). After 100 days of operation (Pfeed = 5–20 bar, T = 350–450 °C), the N2 permeance equals 7.0 × 10−9 mol m−2 s−1 Pa−1, which indicates that the H2/N2 permselectivity still lies around 500, based on a H2 permeance equal to 3.0 × 10−6 mol m−2 s−1 Pa−1. Despite the generation of small pinholes, a membrane life-time of several (2–3) years (T ≤ 425 °C) is estimated for the experimental conditions employed based on long-term stability tests over 100 days. Post-process characterisation shows a considerable grain growth and micro-strain relaxation in the Pd–23%Ag membrane after the prolonged permeation experiment. Changes in surface area are relatively small. In addition, segregation of Ag to the membrane surfaces is observed. The formation of pinholes is identified as the main source for the increased N2 leakage during testing at higher temperature.  相似文献   

6.
A poly(amidoamine) (PAMAM) dendrimer composite membrane with an excellent CO2/N2 separation factor was developed in-situ. The In-situ Modification (IM) method was used to modify the surface of commercial porous membranes, such as ultrafiltration membranes, to produce a gas selective layer by controlling the interface precipitation of the membrane materials in the state of a received membrane module. Using the IM method, a chitosan layer was prepared on the inner surface of a commercially available ultrafiltration membrane as a gutter layer, in order to affix PAMAM dendrimer molecules on the porous substrate. After chitosan treatment, the PAMAM dendrimer was impregnated into the gutter layer to form a PAMAM/chitosan hybrid layer. The CO2 separation performance of the resulting composite membrane was tested at a pressure difference of 100 kPa and a temperature of 40 °C, using a mixed CO2 (5 vol%)/N2 (95 vol%) feed gas. The PAMAM dendrimer composite membrane, with a gutter layer prepared from ethylene glycol diglycidyl ether and a 0.5 wt% chitosan solution of two different molecular weight chitosans, revealed an excellent CO2/N2 separation factor and a CO2 permeance of 400 and 1.6 × 10−7 m3 (STP) m−2 s−1 kPa−1, respectively. SEM observations revealed a defect-free chitosan layer (thickness 200 nm) positioned directly beneath the top surface of the UF membrane substrate. After PAMAM dendrimer treatment, the hybrid chitosan/PAMAM dendrimer layer was observed with a thickness of 300 nm. XPS analysis indicated that the hybrid layer contained about 20–40% PAMAM dendrimer.  相似文献   

7.
Poly(amidoamine) (PAMAM) dendrimers showed high CO2 separation properties and were successfully immobilized in a poly(ethylene glycol) (PEG) network upon photopolymerization of PEG dimethacrylate. The PAMAM dendrimer incorporation ratio was readily controlled, and a stable self-standing membrane containing up to 75 wt.% PAMAM dendrimer was obtained. The CO2 separation properties over smaller H2 were investigated by changing the PAMAM dendrimer content or generation and CO2 partial pressure (ΔPCO2ΔPCO2) under atmospheric conditions. Especially, a polymeric membrane containing 50 wt.% PAMAM dendrimer (0th generation) exhibited an excellent CO2/H2 selectivity of 500 with CO2 permeability of 2.74 × 10−14 m3(STP)m/(m2 s Pa) or 3.65 × 103 barrer (1 barrer = 7.5 × 10−18 m3(STP)m/(m2 s Pa)) when a mixture gas (CO2/H2: 5/95 by vol.) was fed at 25 °C and 100 kPa with 80% relative humidity. This polymeric materials are promising for a novel CO2 separation membrane.  相似文献   

8.
An all-solid-state polymeric membrane Pb2+ ion-selective electrode (Pb2+-ISE) based on bimodal pore C60 (BP-C60) as solid contact has been developed. A BP-C60 film can be readily formed on the surface of a glassy carbon electrode by electrochemical deposition. Cyclic voltammetry and electrochemical impedance spectroscopy have been employed to characterize the BP-C60 film. The large double layer capacitance and fast charge-transfer capability make BP-C60 favorable to be used as solid contact for developing all-solid-state ISEs. The all-solid-state BP-C60-based Pb2+-ISE shows a Nernstian response in the range from 1.0 × 10−9 to 1.0 × 10−3 M with a detection limit of 5.0 × 10−10 M. The membrane electrode not only displays an excellent potential stability with the absence of a water layer between the ion-selective membrane and the underlying BP-C60 solid contact, but also is insensitive to interferences from O2, CO2 and light. The proposed solid-contact Pb2+-ISE has been applied to determine Pb2+ in real water samples and the results agree well with those obtained by anodic stripping voltammetry.  相似文献   

9.
Niobium germanosilicate glasses are potential candidates for the fabrication of transparent glass ceramics with interesting non-linear optical properties. A series of glasses in the (Ge,Si)O2-Nb2O5-K2O system were prepared by melting and casting and their characteristic temperatures were determined by differential thermal analysis. Progressive replacement of GeO2 by SiO2 improved the thermal stability of the glasses. Depending on the composition and the crystallization heat-treatment, different nanocrystalline phases—KNbSi2O7, K3Nb3Si2O13 and K3.8Nb5Ge3O20.4 could be obtained. The identification and characterization of these phases were performed by X-ray diffraction and Raman spectroscopy.The 40 GeO2-10 SiO2-25 Nb2O5-25 K2O (mol%) composition presented the higher ability for volume crystallization and its nucleation temperature was determined by the Marotta's method. An activation energy for crystal growth of ∼529 kJ/mol and a nucleation rate of 9.7×1018 m−3 s−1 was obtained, for this composition. Transparent glass ceramics with a crystalline volume fraction of ∼57% were obtained after a 2 h heat-treatment at the nucleation temperature, with crystallite sizes of ∼20 nm as determined by transmission electron microscopy.  相似文献   

10.
A simple and sensitive method for the determination of nanomolar levels of hydrogen peroxide (H2O2) in seawater has been developed and validated. This method is based on the reduction of H2O2 by ferrous iron in acid solution to yield hydroxyl radical (OH) which reacts with benzene to produce phenol. Phenol is separated from the reaction mixture by reversed phase high performance liquid chromatography and its fluorescence intensity signals were measured at excitation and emission of 270 and 298 nm, respectively. Under optimum conditions, the calibration curve exhibited linearity in the range of (0-50) × 103 nmol L−1 H2O2. The relative standard deviations for five replicate measurements of 500 and 50 nmol L−1 H2O2 are 1.9 and 2.4%, respectively. The detection limit for H2O2, defined as three times the standard deviation of the lowest standard solution (5 nmol L−1 H2O2) in seawater is 4 nmol L−1. Interference of nitrite ion (NO2) on the fluorescence intensity of phenol was also investigated. The result indicated that the addition of 10 μmol L−1 NO2 to seawater samples showed no significant interference, although, the addition of 50 μmol L−1 NO2 to the seawater samples decreases the fluorescence intensity signals of phenol by almost 40%. Intercomparison of this method with well-accepted (p-hydroxyphenyl) acetic acid (POHPAA)-FIA method shows excellent agreement. The proposed method has been applied on-board analysis of H2O2 in Seto Inland seawater samples.  相似文献   

11.
Simon FX  Penru Y  Guastalli AR  Llorens J  Baig S 《Talanta》2011,85(1):527-532
Biochemical oxygen demand (BOD) is a useful parameter for assessing the biodegradability of dissolved organic matter in water. At the same time, this parameter is used to evaluate the efficiency with which certain processes remove biodegradable natural organic matter (NOM). However, the values of BOD in seawater are very low (around 2 mg O2 L−1) and the methods used for its analysis are poorly developed. The increasing attention given to seawater desalination in the Mediterranean environment, and related phenomena such as reverse osmosis membrane biofouling, have stimulated interest in seawater BOD close to the Spanish coast. In this study the BOD analysis protocol was refined by introduction of a new step in which a critical quantity of autochthonous microorganisms, measured as adenosine triphosphate, is added. For the samples analyzed, this improvement allowed us to obtain reliable and replicable BOD measurements, standardized with solutions of glucose-glutamic acid and acetate. After 7 days of analysis duration, more than 80% of ultimate BOD is achieved, which in the case of easily biodegradable compounds represents nearly a 60% of the theoretical oxygen demand. BOD7 obtained from the Mediterranean Sea found to be 2.0 ± 0.3 mg O2 L−1 but this value decreased with seawater storage time due to the rapid consumption of labile compounds. No significant differences were found between two samples points located on the Spanish coast, since their organic matter content was similar. Finally, the determination of seawater BOD without the use of inoculum may lead to an underestimation of BOD.  相似文献   

12.
We have optimized the analytical parameters of a homemade instrument for the simultaneous measurement of the chlorofluorocarbons CCl2F2 (CFC-12), CCl3F (CFC-11) and C2Cl3F3 (CFC-113) in seawater. Seawater samples are flame sealed into 60 ml glass ampoules avoiding any contact with the atmosphere and stored in cold, dark condition until analysis. In the laboratory, after cracking the ampoule in an enclosed chamber filled with ultra-pure nitrogen, the seawater sample is transferred to a stripping chamber, where ultra-pure nitrogen is used to purge the dissolved CFCs from the seawater. The extracted gases are then cryogenically trapped, subsequently the trap is isolated and heated and the CFCs are transferred by a carrier gas stream into a precolumn and then are separated on a gaschromatographic packed column. To separate adequately CFC-12 from N2O, during the early part of the chromatographic run, the gas stream passes through a molecular sieve, which is then isolated and backflushed. The CFCs are detected on an electron capture detector (63Ni ECD). After a careful choice of the experimental conditions, the performances of the system were evaluated. The detection limits for seawater samples are: 0.0081 pmol kg−1 for CFC-12, 0.0073 pmol kg−1 for CFC-11 and 0.0043 pmol kg−1 for CFC-113. The reproducibility of replicate samples lies within 5% for the three CFCs. The system has been successfully employed for CFC measurements in seawater samples collected in the Ross Sea (Antarctica) in the framework of the Italian Antarctic research project.  相似文献   

13.
The redox water splitting is one of the most promising routes for sustainable hydrogen production. Towards this goal, serious technological obstacles are set: (i) by the non-isothermal operation of the redox process, that causes serious reactor construction problems, and (ii) by the need for efficient high temperature oxygen/hydrogen separation technology which is a very challenging development. In this paper, perovskite materials having the formula La0.3Sr0.7FeO3 were synthesized and subsequently tested for their high temperature oxidation/reduction behavior. The redox activity of the materials in relation to the water splitting reaction has been also investigated. Dense, disc shaped membranes of the materials were synthesized and placed in a membrane reactor. Experiments at 1133 K revealed the possibility of performing the reduction and oxidation steps simultaneously and isothermally on each side of the membrane reactor. A steady-state situation was thereby achieved where hydrogen was continuously produced on one side while the material was simultaneously regenerated on the other side. The created oxygen vacancy gradient formed the driving force for a continuous flux of vacancies from the membrane reduction surface to the membrane oxidation surface. The hydrogen production rate under the particular experimental conditions estimated to be ∼47.5 cm3 H2 (STP) m−2 min−1. It could be increased by a factor of approximately 3, up to ∼145 cm3 H2 (STP) m−2 min−1, if the membrane reduction was enhanced with a reductant such as carbon monoxide. This approach resulted in an efficient execution of the water gas shift reaction towards high purity hydrogen production.  相似文献   

14.
An autonomous multi-parameter flow-through CO2 system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO2), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO2 optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO2 is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO2. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO2, and DIC during the CLIVAR/CO2 A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO2, and 2.4 μmol kg−1 for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO2, and 2.2 ± 6.0 μmol kg−1 for DIC. This system integrates spectrophotometric measurements of multiple CO2 parameters into a single package suitable for observations of both seawater and freshwater.  相似文献   

15.
Isothermal crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)   总被引:1,自引:0,他引:1  
Isothermal crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was investigated by means of differential scanning calorimetry and polarized optical microscopy (POM). The Avrami analysis can be used successfully to describe the isothermal crystallization kinetics of PHBV, which indicates that the Avrami exponent n=3 is good for all the temperatures investigated. The spherulitic growth rate, G, was determined by POM. The result shows that the G has a maximum value at about 353 K. Using the equilibrium melting temperature (448 K) determined by the Flory equation for melting point depression together with U∗=1500 cal mol−1, T=30 K and Tg=278 K, the nucleation parameter Kg was determined, which was found to be 3.14 ± 0.07 × 105 (K2), lower than that for pure PHB. The surface-free energy σ=2.55×10−2 J m−2 and σe=2.70±0.06×10−2 J m−2 were estimated and the work of chain-folding (q=12.5±0.2 kJ mol−1) was derived from σe, and found to be lower than that for PHB. This implies that the chains of PHBV are more flexible than that of PHB.  相似文献   

16.
Currently, H2 production techniques for application to proton exchange membrane fuel cells (PEMFC) are intensively investigated, aiming to realize a clean hydrogen society. Due to the limitation by the thermodynamics of methane steam reforming (MSR), multi-reactions and multi-steps should be performed before the generated H2-rich gas could be delivered to PEMFC, which inevitably increases the cost of H2. However, using a thermodynamic shifting membrane reformer, H2 could be produced compactly from MSR, provided that the catalyst showed high performance for MSR reaction and membrane efficiently removed H2 from the reaction zone. We presented here a Pd-based membrane reformer for MSR reaction. In contrast with previous reports, nickel-based catalyst pre-reduced at high temperature was applied in this work, as well as high performance Pd-based membrane. The performances of the membrane reformer in terms of H2 production capacity were also widely investigated. It was found that combination of an active catalyst for MSR and a H2 ultra-permeable Pd membrane obtained high flux of H2 across the membrane and recovery rate of H2 in the membrane reformer. For instance, 98.8% methane conversion, over 97.0% selectivity to CO2 and over 95.0% recovery rate of H2 were obtained under mild working conditions. Simultaneously, the hydrogen flux across the membrane reached 18.6 m3/(m2 h), and Pd-based pure H2 production capacity significantly increased and reached around 387.5 m3/(kgPd h) in membrane reformer. Further work on stability investigation may develop an efficient on-site route of H2 production process for application to on-site power generation using PEMFC.  相似文献   

17.
Novel nanofiltration (NF) membrane was developed from hydroxyl-ended hyperbranched polyester (HPE) and trimesoyl chloride (TMC) by in situ interfacial polymerization process using ultrafiltration polysulfone membrane as porous support. Fourier transform infrared spectroscopy (FTIR-ATR), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and water contact angle (CA) measurements were employed to characterize the resulting membranes. The results indicated that the crosslinked hyperbranched polyester produced a uniform, ultra-thin active layer atop polysulfone (PSf) membrane support. FTIR-ATR spectra indicated that TMC reacted sufficiently with HPE. Water permeability and salts rejection of the prepared NF membrane were measured under low trans-membrane pressures. The resulting NF membranes exhibited significantly enhanced water permeability while maintaining high rejection of salts. The salts rejection increase was accompanied with the flux decrease when TMC dosage was increased. The flux and rejection of NF 1 for Na2SO4 (1 g/L) reached to 79.1 l/m2 h and 85.4% under 0.3 MPa. The results encourage further exploration of NF membrane preparation using hyperbranched polymers (HBPs) as the selective ultra-thin layer.  相似文献   

18.
Proton-conducting membranes based on phosphotungstic acid (PWA) and 3-glycidoxypropyl-trimethoxysilane (GPTMS) was investigated as the electrolyte for low temperature H2/O2 fuel cell. Parameters determining the conductivity and elastic modulus of the membranes were characterized by thermogravimetry/differential thermal analysis and infrared spectroscopic measurements. The composite containing 5% of PWA exhibited an elastic modulus below 100 MPa at room temperature and a high proton conductivity of 1.0 × 10−2 S/cm at 80 °C and 100% RH. Low elastic modulus of the membrane was found to be useful for both the reduction of the membrane thickness and the better contact with the electrodes. The performance of the membrane electrode assemblies (MEA) was systematically studied as an effect of preparation conditions. A maximum power density of 45 mW/cm2 and the current density of 175 mA/cm2 at 0.2 V were achieved at 90 °C and 100% RH for the membrane of 5PWA·95GPTMS composition and 0.2 mm thickness.  相似文献   

19.
This paper investigates the microfiltration of skim milk in order to separate caseins micelles from two whey proteins, α-lactalbumin (α-La) and β-lactoglobulin (β-Lg), using a modified dynamic filtration pilot (MSD) consisting in 6 ceramic 9-cm diameter membrane disks of 0.2 μm pores, rotating around a shaft inside cylindrical housing. A comparison was made with another dynamic filtration module consisting in a disk rotating near a fixed PVDF 15.5 cm diameter membrane with 0.15 μm pores. Maximum permeate fluxes were 120 L h−1 m−2 with the MSD module at 1930 rpm and at 40 °C, and 210 L h−1 m−2 at 2500 rpm and 45 °C, with the rotating disk module. Casein rejection was around 99% at high speed for both membranes. α-La transmission decreased with increasing transmembrane pressure (TMP) from 75% to 60% for ceramic membranes and from 25% to 10% for the PVDF one. β-Lg transmissions were lower, ranging from 23% to 15% for ceramic membranes and from 20% to 5% for the PVDF one. In a concentration test with the PVDF membrane at 2000 rpm, the flux decayed from 200 L h−1 m−2 at initial concentration to 80 L h−1 m−2 at VRR = 3.2 and 22.1% of the initial α-La mass was recovered in the permeate, against 8.1% for β-Lg. Permeate fluxes in the mass transfer limited regime (Jlim) of the MSD and rotating disk module operated at various speeds were well correlated by the equation Jlim = 17.13 Vav where Vav denoted the disk azimuthal velocity averaged over the membrane area. Measurements of Jlim, taken from Ref. [G. Samuelsson, P. Dejlmek, G. Tragardh, M. Paulsson, Minimizing whey protein retention in crossflow microfiltration of skim milk. Int. Dairy J. 7 (1997) 237–242] during MF of skim milk using tubular ceramic membranes at velocities from 1.5 to 8 m s−1 with permeate co-current recirculation were found to obey the same correlation.  相似文献   

20.
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