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1.
The morphology of selenium has been studied in light of present concepts of crystallinity in crystalline organic polymers. Spherulitic crystallization and resultant morphology were examined as a function of temperature by transmission and replication electron microscopy, electron diffraction, and optical microscopy. Evidence is given for polymer chain folding during crystallization of trigonal selenium. Theoretical thermodynamic calculations presented yield several thermodynamic values including an equilibrium melting point of 219.2°C, a fold surface energy of 337 ergs/cm2 and a lateral surface energy of 9.8 ergs/cm2.  相似文献   

2.
The investigation of the interfacial toughness of polymer layered laminar composites with two different approaches produced results differing by up to an order of magnitude and following opposite trends with respect to the strain rates. The flexural modulus and neutral axis of a constrained epoxy‐adhesive layer bound to a painted metal substrate varied with the thickness of the adhesive layer. The adhesion energy depended on the rate at which the force was transmitted to the adhesion bonds—not just on the strength of the adhesion bonds—and on the concomitant strain hardening at high strain rates. As the strain rate and thickness of the polymer layer increased, the transition from a cohesive mode to an adhesive–cohesive (polymer–polymer interface) mode of debonding led to the observed high adhesion energy. The high adhesion energy and increased strain hardening were attributed to the formation of organic–inorganic composites and nanocomposites within the polymer matrix, which evolved as a result of the interactions between the metal oxide pigments and fillers with the polymer matrix during curing. Scission of the polymer chains at the interface was proposed to be the predominant fracture mechanism; it was based on the high relaxation time (~1017 s) and the high activation energy (~175 kJ mol?1). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3822–3835, 2004  相似文献   

3.
The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm?1), which is more than an order of magnitude greater than that of the MWCNT‐SO3H (527 µS cm?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (kapp≈19.73×10?3 cm s?1)>MWCNT‐SO3H (kapp≈11.63×10?3 cm s?1)>nanoCoTCPc (kapp≈1.09×10?3 cm s?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10?4 F cm?2)>nanoCoTCPc (2.57×10?4 F cm?2)>MWCNT‐SO3H (2.28×10?4 F cm?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.  相似文献   

4.
Gas permeation properties of poly(lactic acid)   总被引:2,自引:0,他引:2  
The need for the development of polymeric materials based on renewable resources has led to the development of poly(lactic acid) (PLA) which is being produced from a feedstock of corn rather than petroleum. The present study examines the permeation of nitrogen, oxygen, carbon dioxide, and methane in amorphous films of PLA cast from solution. The properties of PLA are compared to other commodity plastics and it is shown that PLA permeation closely resembles that of polystyrene. At 30°C, N2 permeation in PLA is 1.3 (10−10 cm3 (STP) cm/cm2 s cmHg) and the activation energy is 11.2 kJ/mol. For oxygen the corresponding values are 3.3 (10−10 cm3(STP) cm/cm2 s cm Hg) and 11.1 kJ/mol. The values for carbon dioxide permeation are 1.2 (10−10 cm3 (STP) cm/cm2 s cmHg) and 6.1 kJ/mol. For methane values of 1.0 (10−10 cm3 (STP) cm/cm2 s cmHg) and an activation energy of 13.0 kJ/mol are found. Studies with pure gases show that polymer chain branching and small changes in l:d stereochemical content have no effect on permeation properties. Crystallinity is found to dominate permeation properties in a biaxially oriented film. The separation factor for a CO2/CH4 mixed gas system is measured between 0 and 50°C and does not deviate significantly from the calculated ideal separation factor; at 0°C the separation factor is 16, a value that suggests continued studies of PLA as a separation medium are warranted.  相似文献   

5.
The sputtering of bismuth (Bi/Si) thin films deposited onto silicon substrates and irradiated by swift Cuq+ heavy ions (q = +4 to +7) was investigated by varying both the ion energy over the 10 to 26‐MeV range and the ion fluence ϕ from 5.1 × 1013 cm−2 to 3.4 × 1015 cm−2. The sputtering yields were determined experimentally via the Rutherford backscattering spectrometry technique using a 2‐MeV He+ ion beam. The measured sputtering yields versus Cu7+ ion fluence for a fixed incident energy of 26 MeV exhibit a significant depression at very low ϕ‐values flowed by a steady‐state regime above ~1.6 × 1014 cm−2, similarly to those previously pointed out for Bi thin films irradiated by MeV heavy ions. By fixing the incident ion fluence to a mean value of ~2.6 × 1015 cm−2 in the upper part of the yield saturation regime, the measured sputtering yield data versus ion energy were found to increase with increasing the electronic stopping power in the Bi target material. Their comparison to theoretical predicted models is discussed. A good agreement is observed between the measured sputtering yields and the predicted ones when considering the contribution of 2 competitive processes of nuclear and electronic energy losses via, respectively, the SRIM simulation code and the inelastic thermal spike model using refined parameters of the ion slowing down with reduced thermophysical proprieties of the Bi thin films.  相似文献   

6.
Abstract— Protection by acridine orange against ultraviolet light effects in resting cells of E. coli B/r/1, try- was studied with special reference to a possible oxygen effect. Dose-response relationships were described by the function S= 1–(1 - e-kD)n where S is the surviving fraction and D is the u.v. dose in ergs/mm2. For cells suspended in 5 × 10--6M acridine orange (AO) in air, the radiation sensitivity k was reduced from 0.010 (ergs/mm2))-1 in the absence of the dye to 0.0053 (ergs/mm2)-1 in the presence of the dye. Under anoxia at this AO concentration, k was further reduced to 0.0015 (ergs/mm2)-1. The oxygen effect ratio, kO2/kN2, was 3.5 at this concentration of AO. Greater protection was observed in cells suspended in 2 × 10--5M AO, the oxygen effect ratio was unchanged. No oxygen effect was detected in the u.v. response in the absence of the dye. The value of n was reduced from about 12 with no dye to about 5 at dye concentrations of 5 × 10--6M AO or more when oxygen was present. Under anoxia, in the presence of AO, n was further reduced to about 1.3. Atebrin, an efficient u.v. protective agent but an inefficient photodynamic agent, had no oxygen effect for protection against u.v. inactivation. Acridine orange protected against u.v.-induced reversion to tryptophan indepence in E. coli WP2 to about the same extent as it did for inactivation. A similar oxygen effect was observed for both inactivation and mutagenesis.  相似文献   

7.
《中国化学快报》2022,33(11):4761-4765
Typically, rational interfacial engineering can effectively modify the adsorption energy of active hydrogen molecules to improve water splitting efficiency. NiFe layered double hydroxide (NiFe LDH) composite, an efficient oxygen evolution reaction (OER) catalyst, suffers from slow hydrogen evolution reaction (HER) kinetics, restricting its application for overall water splitting. Herein, we construct the hierarchical MoS2/NiFe LDH nanosheets with a heterogeneous interface used for HER and OER. Benefiting the hierarchical heterogeneous interface optimized hydrogen Gibbs free energy, tens of exposed active sites, rapid mass- and charge-transfer processes, the MoS2/NiFe LDH displays a highly efficient synergistic electrocatalytic effect. The MoS2/NiFe LDH electrode in 1 mol/L KOH exhibits excellent HER activity, only 98 mV overpotential at 10 mA/cm2. Significantly, when it assembled as anode and cathode for overall water splitting, only 1.61 V cell voltage was required to achieve 10 mA/cm2 with excellent durability (50 h).  相似文献   

8.
The bottleneck of alkaline hydrogen evolution reaction lies in the kinetically sluggish brought from multistep reaction processes involving water adsorption and dissociation, as well as hydrogen adsorption. In this work, we successfully synthesized o-CoSe2/c-CoSe2 heterostructures anchored on MoSe2 nanosheets to powerfully promote reaction processes. As an electrocatalyst, it exhibits a low overpotential of 112 mV at 10 mA/cm2 and a Tafel slope of 96.9 mV/dec for an alkaline hydrogen evolution reaction. Moreover, the as-prepared catalyst can behave as both cathode and anode for overall water splitting, which only requires 1.61 V cell voltage at 10 mA/cm2. Significantly, the cell voltage can be further reduced to 1.53 V at 10 mA/cm2 for water electrolysis under the simulated solar irradiation owing to such a semiconductor-based heterostructure that facilitates the separation of photogenerated charges. Here, the improving overall performance of this ternary electrocatalyst is attributed to the multifunctionality and synergistic interaction of different components in this heterogeneous material. The work provides a novel strategy to design active catalysts simultaneously using electric energy and solar energy for effective water splitting.  相似文献   

9.
The failure of an adhesive layer in a 180° peel test is analyzed by the modeling of the peel as an elastica. The adhesive is assumed to fail by a process of cavitation and fibrillation. The resistance of the fibrillated material to deformation gives rise to a rate‐dependent peel force F. Governing equations, which take into account the large deformation of the fibrillated materials, are derived. Numerical solutions are obtained for the special case of a linear, viscous adhesive. Assuming a critical strain failure criterion for the fibrils, we show that the peel rate is inversely proportional to the square root of the adhesive thickness and directly proportional to F3/4. The connection between the peel test and the tack test is also discussed. The maximum traction on the peel arm is found to be directly proportional to the peel force and inversely proportional to the adhesive thickness. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2277–2291, 2002  相似文献   

10.
Constructing a solid electrolyte interface (SEI) is a highly effective approach to overcome the poor reversibility of lithium (Li) metal anodes. Herein, an adhesive and self-healable supramolecular copolymer, comprising of pendant poly(ethylene oxide) (PEO) segments and ureido-pyrimidinone (UPy) quadruple-hydrogen-bonding moieties, is developed as a protection layer of Li anode by a simple drop-coating. The protection performance of in-situ-formed LiPEO–UPy SEI layer is significantly enhanced owing to the strong binding and improved stability arising from a spontaneous reaction between UPy groups and Li metal. An ultrathin (approximately 70 nm) LiPEO–UPy layer can contribute to stable and dendrite-free cycling at a high areal capacity of 10 mAh cm−2 at 5 mA cm−2 for 1000 h. This coating together with the promising electrochemical performance offers a new strategy for the development of dendrite-free metal anodes.  相似文献   

11.
Photodynamic therapy (PDT), carried out at low fluence rates, may enhance tumor response as well as affect treatment selectivity. We have studied the effects of fluence rate on the response of the murine radiation-induced fibrosarcoma (RIF) to PDT using Photofrin® (5 mg/kg). Tumor response was tested over a large range of fluence rates (10-200 mW/cm2) and fluences (25-378 J/ cm2). Low fluence rates were more efficient; -60 J/cm2 at 10 mW/cm2 was needed to achieve the same tumor growth delay as -100 J/cm2 at 150 mW/cm2 and -150 J/cm2 at 200 mW/cm2. Despite this increased efficiency, lower fluence rates still required longer treatment times for equivalent anti-tumor effects: 95 min for 57 J/cm2 at 10 mW/cm2versus 11 min for 100 J/cm2 at 150 mW/cm2. Effects of fluence rate on the PDT toxicity to normal tissue were examined through the response of the murine (C311) foot to Photofrin® PDT. Treatment with conditions that produced equivalent tumor responses, i.e. 57 J/cm2 at 10 mW/cm2 and 100 J/cm2 at 150 mW/cm2, resulted in a more severe foot response at the higher fluence rate (median peak response: 0.9 at 10 mW/cm2, 1.5 at 150 mW/cm2) with more time required for tissue to return to normal (8 days at 10 mW/cm2, at least 30 days at 150 mW/cm2). However, when feet were treated with an equal fluence of 100 J/cm2 at various fluence rates, longer healing times accompanied the lower fluence rate treatments. Overall, this paper demonstrates that lower PDT fluence rates are associated with increased efficiency of tumor response. If this increased efficiency is accounted for by lowering treatment fluence, lower fluence rates also may result in a more favorable normal tissue response to treatment.  相似文献   

12.
N-Acetyl-proline-methylamide (APMA) was synthesized by the mixed anhydride method and investigated by IR. spectroscopy and chemical relaxation measurements. The temperature-induced variation of the IR. absorption bands of the internally hydrogen bonded (b) and of the extended, unbonded (e) species at 3330 and 3450 cm?1 respectively, were used to evaluate the molar absorptivities, a(b) = 280 and a(e) = 50 l/mol · cm, the equilibrium constant K = 0.70, and the molar enthalpy of reaction ΔH = ? 2280 ± 60 cal/mol. The entropy was estimated to be in the range ? 8 to ? 9 e.u. The reaction rates of this conformational transition were measured by the chemical dipole field effect. The relaxation time of the rate process is τ = 2.7 · 10?9s, the rate constant for the formation of the hydrogen bond k(b) is 2.2 · 108 s?1, and that for the unfolding accompanied by the breakage of the amide hydrogen bond k(e) is 1.5 · 108s?1.  相似文献   

13.
A systematic study is presented in order to reveal the occurrence of wall slip of pre-prepared elastomeric samples characterized with the use of rotational rheometry. To exclude effects that could be attributed to additional functional fillers, both an unfilled (primarily used) and lightly silica reinforced (complementary system) silicone rubber are evaluated. Cylindrical samples are prepared by casting using a standardized methodology and examined by means of a stress-controlled parallel-plate rotational rheometer. As a control test, samples are also cured within the rheometer (in situ), thereby fixing them to the measuring plates and firmly establishing their response in “no-slip” conditions. The experiments suggest that wall slip, postulated to be caused by an adhesive failure at the sample-plate interface, may occur if the deformation is sufficiently large and no cohesive failure is present. It is detected by an increase in the loss modulus that is related to the adhesive failure associated with local dynamic friction, resulting in increased dissipated energy. Direct (via raw waveform data and normalized Lissajous figures) and indirect (via fast-Fourier-transformation) analysis of the overall system response for a single steady state deformation cycle provided further insights into the mechanism of wall slip.  相似文献   

14.
Calcium phosphate (CaP) coatings are used to improve the biological performance of an implant. A technique that is often used to measure the composition of this material is XPS. When extremely thin coatings are measured, for example to study the interface between CaP and a substrate, the quantification of the XPS results is complicated by the varying attenuation lengths (ALs) of the photoelectrons at different energies. To correct for this, AL data are needed. In this work we measured these ALs by comparing XPS yields with the coating coverage (as measured by Rutherford backscattering spectrometry). We were able to determine the AL for several calcium and phosphorus peaks. Determination of the oxygen ALs was not possible owing to diffusion of oxygen into the polymeric substrates. For the peaks that are most often used for quantification of XPS yields (the Ca 2p and the P 2p peak), we found ALs of 21.8 × 1015 atoms cm?2 and 26.8 × 1015 atoms cm?2, respectively. Concentration profiles near the interface, growth mode and interfacial roughness appeared to have no measurable effect on the measured ALs. For the ALs, an energy dependence with an exponent of 0.55 was found. The measured ALs are best predicted by the empirical CS1 equation of Cumpson and Seah. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

15.
The effect of polypyrrole (PPy) on the polyvinyl alcohol (PVA)-potassium iodide (KI)-iodine (I2) polymer electrolytes has been investigated and optimized to use in a dye-sensitized solar cell (DSSC). The different weight ratios of PVA: PPy (93: 2, 91: 4, 89: 6, 87: 8, and 85: 10 wt%) polymer electrolytes (PE) were prepared by solution casting. Structural, complex formation and surface roughness of the prepared electrolytes was confirmed by X-ray diffraction, FTIR, and atomic force microscopy (AFM) respectively. Conductivity plots of all polymer films showed increasing trend with temperature and concentration of PPy. The activation energy of the optimized system found to be 0.871 kJ mol?1. UV-visible spectrum was adopted to characterize the absorption spectra of the material revealed that increase in the absorbance with increasing PPy content and shifting the absorbance maximum towards lower energy. The indirect band gap decreased from 3.78 to 2.14 eV and direct band gap decreased from 3.88 to 2.71 eV. The EIS analyses revealed the lower charge transfer resistance of 3.029 Ω cm2 at the interface between CE and PE. The excellent performance was observed in the fabricated DSSCs using PVA (85%)/PPy (10%)/KI (5%)/I2 polymer electrolyte with a short-circuit current density of 11.071 mA cm?2, open-circuit voltage of 0.644 V, fill factor of 0.575, and photovoltaic conversion efficiency of 4.09% under the light intensity of 100 mW cm?2. Hence, the PPy content in polymer electrolyte influences the remarkable performance of low-cost DSSC.  相似文献   

16.
To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10?4 cm2/s, 2.6 × 10?4 cm2/s, 3.0 × 10?4 cm2/s, 3.2 × 10?4 cm2/s, and 3.3 × 10?4 cm2/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.  相似文献   

17.
Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation-induced water flow inside nanochannels. The device can yield direct current with a short-circuit current density of over 55 μA cm−2, which is three orders larger than a previously reported analogous device (approximately 40 nA cm−2). Moreover, it exhibits a constant output power density of over 6 μW cm−2 and an open-circuit voltage of up to 400 mV. Our finding may pave a way for developing energy-harvesting devices from ubiquitous evaporation-driven internal water flow in nature with semiconductor material of silicon.  相似文献   

18.
This study aimed to improve the performance of the activated carbon-based cathode by increasing the Li content and to analyze the effect of the combination of carbon and oxidizing agent. The crystal structure and chemical structure phase of Li-high surface area activated carbon material (Li-HSAC) was analyzed by X-ray diffraction (XRD) and Raman spectroscopy, the surface state and quantitative element by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) and the surface properties with pore-size distribution by Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH) and t-plot methods. The specific surface area of the Li-YP80F is 1063.2 m2/g, micropore volume value is 0.511 cm3/g and mesopore volume is 0.143 cm3/g, and these all values are higher than other LiOH-treated carbon. The surface functional group was analyzed by a Boehm titration, and the higher number of acidic groups compared to the target facilitated the improved electrolyte permeability, reduced the interface resistance and increased the electrochemical properties of the cathode. The oxidizing agent of LiOH treated high surface area of activated carbon was used for the cathode material for EDLC (electric double layer capacitor) to determine its electrochemical properties and the as-prepared electrode retained excellent performance after 10 cycles and 100 cycles. The anodic and cathodic peak current value and peak segregation of Li-YP80F were better than those of the other two samples, due to the micropore-size and physical properties of the sample. The oxidation peak current value appeared at 0.0055 mA/cm2 current density and the reduction peak value at –0.0014 mA/cm2, when the Li-YP80F sample used to the Cu-foil surface. The redox peaks appeared at 0.0025 mA/cm2 and –0.0009 mA/cm2, in the case of using a Nickel foil, after 10 cycling test. The electrochemical stability of cathode materials was tested by 100 recycling tests. After 100 recycling tests, peak current drop decreased the peak profile became stable. The LiOH-treated high surface area of activated carbon had synergistically upgraded electrochemical activity and superior cycling stability that were demonstrated in EDLC.  相似文献   

19.
Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation‐induced water flow inside nanochannels. The device can yield direct current with a short‐circuit current density of over 55 μA cm?2, which is three orders larger than a previously reported analogous device (approximately 40 nA cm?2). Moreover, it exhibits a constant output power density of over 6 μW cm?2 and an open‐circuit voltage of up to 400 mV. Our finding may pave a way for developing energy‐harvesting devices from ubiquitous evaporation‐driven internal water flow in nature with semiconductor material of silicon.  相似文献   

20.
Constructing a solid electrolyte interface (SEI) is a highly effective approach to overcome the poor reversibility of lithium (Li) metal anodes. Herein, an adhesive and self‐healable supramolecular copolymer, comprising of pendant poly(ethylene oxide) (PEO) segments and ureido‐pyrimidinone (UPy) quadruple‐hydrogen‐bonding moieties, is developed as a protection layer of Li anode by a simple drop‐coating. The protection performance of in‐situ‐formed LiPEO–UPy SEI layer is significantly enhanced owing to the strong binding and improved stability arising from a spontaneous reaction between UPy groups and Li metal. An ultrathin (approximately 70 nm) LiPEO–UPy layer can contribute to stable and dendrite‐free cycling at a high areal capacity of 10 mAh cm?2 at 5 mA cm?2 for 1000 h. This coating together with the promising electrochemical performance offers a new strategy for the development of dendrite‐free metal anodes.  相似文献   

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