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1.
Several semicrystalline polymers show a recrystallization after melting during a heating scan. We have studied the mechanisms of such recrystallization processes for two different polymers, namely syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS). This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multi-stage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we have observed such a mechanism which resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though, when crystallization sets in an entangled polymer melt, it follows the multi-stage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism. Received 23 July 2001 and Received in final form 4 October 2001  相似文献   

2.
In this paper we determine the features of the thermophysical processes involved in the interaction of laser radiation with metals that have cryogenic temperature. To do so, we use a one-dimensional model that involves heating a semi-infinite solid by a point thermal source with a constant flux density. Temperature fields, heating and cooling rates in the laser-irradiated zone for iron and titanium at the ambient temperatures of 77 (liquid nitrogen), 293 and 573 K were calculated. The intensity of the laser irradiation enabled the melting temperatures of 1933 K and 1812 K on the Ti and Fe surface, respectively, to be reached. The duration of the laser pulse was 4.5 ms. We show that a drop in ambient temperature from 573 to 77 K leads to a rise in cooling rate from 3.25 × 103 and 6.4 × 106 K/s to 4.25 × 103 and 1.3 × 107 K/s in the Ti and Fe targets, respectively. Agreement was good between the calculated depths of melting and phase transformation isotherms and the experimental depths of the interfaces of melting and heat-affected zones.  相似文献   

3.
Molecular dynamics simulations are employed here to study the melting and superheating behaviors of bulk Palladium at high heating rates. Quantum Sutton-Chen many body potential is used for these simulations. Being heated, the superheating and melting behavior is found to be strongly affected by the heating rate, and heating rate induced randomization during non-equilibrium heating processes is found to be the main driving force for phase transformation, and it eliminates the energy barrier for nucleation. Not only Pd crystals but also Pd crystals with defects are studied. And the upper limit of heating rate induced superheating is determined to be around 2100?K.  相似文献   

4.
We present results on the ultrafast dynamics of mass-selected neutral Ag4 clusters using NeNePo (negative ion - neutral - positive ion) femtosecond pump-probe spectroscopy. One-color pump-probe spectra of the Ag4 -/Ag4/Ag4 + system measured at 385 nm and an internal cluster temperature of 20 K display a complex beat structure over more than 60 ps. The oscillatory structure is attributed to vibrational wave packet dynamics in an excited “dark" state of neutral Ag4. A dominant 740 fs wave packet period as well as wave packet dephasing and rephasing are observed in the spectra. Fourier analysis of the spectra yields a group of frequencies centered around 45 cm-1 and an anharmonicity χ eχ eχ e of 2.65 cm-1 for the active vibrational mode. Received 30 November 2000  相似文献   

5.
Resonant Auger spectra of O2 clusters excited at the O1s edge are reported. After excitation to the repulsive 1s-1* state, the resulting resonant Auger spectrum displays features that remain constant in kinetic energy as the photon energy is detuned. The shift between known atomic fragment features and these features is consistent with that observed for atoms and clusters in singly charged states in direct photoemission. These findings are strong evidence for the existence of molecular ultrafast dissociation processes within the clusters or on their surface.  相似文献   

6.
The superheating of condensed noble gases (argon, krypton, xenon) was investigated by the techniques of continuous heating of liquid specimen in a glass capillary. Experiments covered the pressure range 1–35 bar at the nucleation rates ≈105 cm-3 s-1. The superheating data obtained here were compared with the results of calculations based on the Volmer-Becker-Döring-Zeldovich-Frenkel homogeneous nucleation theory. A good agreement between theory and experiment as well as the thermodynamic similarity of the studied substances with respect to the fluctuation nucleation was found.  相似文献   

7.
By differential Scanning Calorimetry (DSC), at low heating rate and using a technique of fractionation, we have measured the equilibrium DSC signal (heat flow) J q 0 of two families of porous glass saturated with water. The shape of the DSC peak obtained by these techniques is dependent on the sizes distribution of the pores. For porous glass with large pore size distribution, obtained by sol-gel technology, we show that in the domain of ice melting, the heat flow Jq is related to the melting temperature depression of the solvent, ΔT m , by the scaling law: J q 0∼ΔT m - (1 + D). We suggest that the exponent D is of the order of the fractal dimension of the backbone of the pore network and we discuss the influence of the variation of the melting enthalpy with the temperature on the value of this exponent. Similar D values were obtained from small angle neutron scattering and electronic energy transfer measurements on similar porous glass. The proposed scaling law is explained if one assumes that the pore size distribution is self similar. In porous glass obtained from mesomorphic copolymers, the pore size distribution is very sharp and therefore this law is not observed. One concludes that DSC, at low heating rate ( q? 2°C/min) is the most rapid and less expensive method for determining the pore distribution and the fractal exponent of a porous material. Received 23 July 1999 and Received in final form 16 February 2001  相似文献   

8.
The morphology of polyethylene single crystals prepared isothermally in solution was found to be independent of molecular weight. The enthalpy of fusion, lamellar fold period, and optical appearance were invariant for samples grown from fractions ranging from 20,000 to 2,000,000 in molecular weight. The mass fraction of lamellae which thicken during heating decreased linearly with increasing log molecular weight. The melting temperature of the crystals was also nearly independent of molecular weight.

The superheating of polyethylene crystals was observed to be a function of molecular weight and morphology. At a comparatively high molecular weight the heating rate of the calorimeter exceeded the crystal melting rate, which shifted the observed melting temperature to an anomalously high value. The incorporation of defects within the crystals by irradiation-induced cross-links or chain entanglements increased the melting rate of the high molecular weight samples and thereby minimized the effects of superheating.

The apparent heat of fusion of melt crystallized polyethylene decreased linearly with increasing log molecular weight. In contrast to this behavior the crystallinity of single crystals from dilute solution was independent of molecular weight.

In previous papers we have shown that reorganization of polymer single crystals is suppressed by cross-linking [1—3]. With the appropriate selection of heating rate and irradiation dose, the melting temperatures of solution grown crystals of various morphologies were determined in the absence of lamellar thickening. The observed melting temperatures of polyethylene single crystals with different X-ray fold periods were found to fit the following expression:

Tm = Tm0[1—2σe/Hf?] with an equilibrium melting temperature (Tm0) of 145.8 ± 1.0°C and a surface free energy (σe) of 89 ± 5 ergs cm?2 for a polyethylene crystal of infinite dimensions. In addition, at a constant heating rate it was observed that the fraction of crystals which thickened prior to melting decreased with increasing fold period.

Since cross-linking polyethylene increases the molecular weight of the material, it is instructive to investigate the reorganization characteristics of single crystals prepared from polyethylene fractions. Single crystals were prepared in xylene from molecular weight fractions of polyethylene and the effect of molecular weight upon the structure and thermal properties of the crystals was determined.  相似文献   

9.
We present 69,71Ga-NMR experiments on microcrystalline samples of the recently discovered supramolecular compound Ga 84 [ N ( SiMe 3 ) 2 ] 20 Li 6 Br 2 ( thf ) 20 . 2 toluene, which is composed of ligand-coordinated Ga84 metal clusters, packed together in a fully ordered crystalline matrix. The compound is highly conducting and even shows superconductivity below T c ~ 7.2 K. Our preliminary results between 10-300 K show a metallic-like behavior: the nuclear spin-lattice relaxation rate T 1 -1 follows the Korringa law 69 ( T 1 T ) -1 = 0.36 s -1 K -1 , but with a relaxation rate approximately three times smaller than in bulk -Ga metal. No quantum-size effects are observed, the Korringa law being followed down to 10 K, whereas the quantum-gaps for individual clusters should amount to ~ 10 3 K. These results therefore suggest a transport process based on intermolecular charge transfer, similar as in alkali-doped fullerenes and silicon-clathrates.  相似文献   

10.
The ablation process of thin copper films on fused silica by picosecond laser pulses is investigated. The ablation area is characterized using optical and scanning electron microscopy. The single-shot ablation threshold fluence for 40 ps laser pulses at 1053 nm has been determinated toF thres = 172 mJ/cm2. The ablation rate per pulse is measured as a function of intensity in the range of 5 × 109 to 2 × 1011 W/cm2 and changes from 80 to 250 nm with increasing intensity. The experimental ablation rate per pulse is compared to heat-flow calculations based on the two-temperature model for ultrafast laser heating. Possible applications of picosecond laser radiation for microstructuring of different materials are discussed.  相似文献   

11.
An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO2 lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10-7 W cm-1/z. The 9R(30) transition of the CO2 laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com  相似文献   

12.
Rapid initiation of reactions in Al/Ni multilayers with nanoscale layering   总被引:3,自引:0,他引:3  
Research into nanoenergetic materials is enabling new capabilities for controlling exothermic reaction rates and energy output, as well as new methods for integrating these materials with conventional electronics fabrication techniques. Many reactions produce primarily heat, and in some cases it is desirable to increase the rate of heat release beyond what is typically observed. Here we investigate the Al-Ni intermetallic reaction, which normally propagates across films or foils at rates lower than 10 m/s. However, models and experiments indicate that local heating rates can be very high (107 K/s), and uniform heating of such a multilayer film can lead to a rapid, thermally explosive type of reaction. With the hopes of using a device to transduce electrical energy to kinetic energy of a flyer plate in the timescale of 100's of nanoseconds, we have incorporated a Ni/Al nanolayer film that locally heats upon application of a large electrical current. We observed flyer plate velocities in the 2-6 km/s range, corresponding to 4-36 kJ/g in terms of specific kinetic energy. Several samples containing Ni/Al films with different bilayer thicknesses were tested, and many produced additional kinetic energy in the 1.1-2.3 kJ/g range, as would be expected from the Ni-Al intermetallic reaction. These results provide evidence that nanoscale Ni/Al layers reacted in the timescale necessary to contribute to device output.  相似文献   

13.
We report synthesis, structure/micro-structure, resistivity under magnetic field [ρ(T)H], Raman spectra, thermoelectric power S(T), thermal conductivity κ(T), and magnetization of ambient pressure argon annealed polycrystalline bulk samples of MgB2, processed under identical conditions. The compound crystallizes in hexagonal structure with space group P6/mmm. Transmission electron microscopy (TEM) reveals electron micrographs showing various types of defect features along with the presence of 3–4 nm thick amorphous layers forming the grain boundaries of otherwise crystalline MgB2. Raman spectra of the compound at room temperature exhibited characteristic phonon peak at 600 cm-1. Superconductivity is observed at 37.2 K by magnetic susceptibility χ(T), resistivity ρ(T), thermoelectric power S(T), and thermal conductivity κ(T) measurements. The power law fitting of ρ(T) give rise to Debye temperature (ΘD) at 1400 K which is found consistent with the theoretical fitting of S(T), exhibiting Θ D of 1410 K and carrier density of 3.81 × 1028/m3. Thermal conductivity κ(T) shows a jump at 38 K, i.e., at Tc, which was missing in some earlier reports. Critical current density (Jc) of up to 105 A/cm2 in 1–2 T (Tesla) fields at temperatures (T) of up to 10 K is seen from magnetization measurements. The irreversibility field, defined as the field related to merging of M(H) loops is found to be 78, 68 and 42 kOe at 4, 10 and 20 K respectively. The superconducting performance parameters viz. irreversibility field (Hirr) and critical current density Jc(H) of the studied MgB2 are improved profoundly with addition of nano-SiC and nano-diamond. The physical property parameters measured for polycrystalline MgB2 are compared with earlier reports and a consolidated insight of various physical properties is presented.  相似文献   

14.
The residence-time of the flue gas in a furnace is an important parameter for a complete and clean combustion. A new method to determine the residence-time has been developed and is presented for the first time. It is based on the injection of alkali compounds as a tracer. Alkali atoms that are produced by thermal decomposition of the tracer are detected in the hot flue gas after passage of the combustion facility. This is done without any gas sampling using direct tunable diode laser based absorption spectroscopy. Different diode laser (DL) types (Fabry–Pérot DLs, external-cavity DLs, and vertical-cavity surface-emitting lasers) were analyzed and used to develop several spectrometers for the in situ detection of lithium (671 nm), potassium (770 nm), and rubidium (780 nm). Various spectrometers were built for single- or multi-species detection using a single laser, for time-multiplexed multi-species detection using two lasers, and for multi-path detection at two different locations along the flue-gas duct. To evaluate the system performance the potassium atom background caused by the fuel was continuously monitored in the post-combustion chamber (PCC) for several weeks. A typical concentration range of 1 ng to 1 μg at STP (800 ppq to 800 ppt; ppq=10-15) was observed. By averaging 100 individual absorption scans the response time was 2.7 s. The minimum detectable absorption was about 10-4 optical density, corresponding to a detection limit of 4×1011 K atoms/m3 at 1200 K instead of ‘°K’. (K(D2) absorption line; 1.9-m absorption path). This is equivalent to a detection limit of 0.1 ng/m3 at STP or 80 ppq. The fastest response time (0.16 s) was achieved by evaluating single absorption scans. Two combustion facilities at the Forschungszentrum Karlsruhe (a batch combustor and a 3-MW special waste incinerator with a rotary kiln followed by a PCC) were investigated. Alkali chlorides were added to the combustion chamber in different forms, of which short spray pulses of an aqueous salt solution was the method of choice for the residence-time measurement. Flow-time distributions were measured and the mean residence-time was calculated for various operation conditions. A simultaneous flow-time measurement at two different locations (8.4 m/17.0 m from the tracer discharge location) was realized with a binary K/Rb tracer and a multi-species spectrometer. Mean residence-times of (±) 151s and (±) 261s were observed and met the expected values. Received: 29 April 2002 / Revised version: 21 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +49-6221/5450-50, E-mail: volker.ebert@pci.uni-heidelberg.de This paper is dedicated to Prof. Dr. Gottfried Huttner on the occasion of his 65th birthday.  相似文献   

15.
Characteristics of the Stark broadened and overlapping 447.1 nm He I spectral line and its forbidden 447.0 nm components have been measured at electron densities between 4.4×1022 m-3 and 8.2×1022 m-3 and electron temperatures between 18 000 K and 33 000 K in plasmas created in five various discharge conditions using the low pressure pulsed arc as an optically thin plasma source operated in helium-nitrogen-oxygen gas mixture. Good agreement was found among our measured line characteristics and their existing calculated values, based on the quasistatic approximation. Possible influence of the singly ionized oxygen impurity atoms (O II) on the intensity values of the dip between allowed and forbidden components was found that can explain the disagreement among some existing experimental and calculated line characteristics data, at higher electron temperatures and densities. On the basis of the observed asymmetry of the 447.1 nm spectral line profile we have obtained the ion contribution parameter at 1022 m-3 electron density and 8 000 K electron temperature. Received 20 February 2001 and Received in final form 25 April 2001  相似文献   

16.
The mechanical and electrical properties in lanthanum modified lead zirconate-titanate ceramics of 5/50/50 and 10/50/50 were studied by mechanical loss Q - 1, Young's modulus E, electric permittivity ε and tangent of dielectric loss of angle tgδ measurements. The internal friction Q - 1 and Young modulus E measured from 290 K to 600 K shows that Curie temperature TC is located at 574 K and 435 K (1st cycle of heating) respectively for ceramic samples 5/50/50 and 10/50/50. The movement of TC in second cycle of heating to lower temperature (561 K for 5/50/50 and 420 K for 10/50/50) has been observed. Together with Q - 1 and E measurements, temperature dependences of ε=f(T) and tgδ=f(T) were determinated in temperature range from 300 K to 730 K. The values of TC obtained during ε and tgδ measurements were respectively: 560 K for 5/50/50 and 419 K for 10/50/50. These temperatures are almost as high as the temperatures obtained by internal friction Q - 1 measurements in second cycle of heating. In ceramic sample 10/50/50 the additional maximum on internal friction Q - 1 curve at the temperature 316 K was observed.  相似文献   

17.
The trap levels in nominally undoped Ga3InSe4 crystals were investigated in the temperature range of 10-300 K using the thermally stimulated currents technique. The study of trap levels was accomplished by the measurements of current flowing along the c-axis of the crystal. During the experiments we utilized a constant heating rate of 0.8 K/s. Experimental evidence is found for one hole trapping center in the crystal with activation energy of 62 meV. The analysis of the experimental TSC curve gave reasonable results under the model that assumes slow retrapping. The capture cross-section of the trap was determined as 1.0×10−25 cm2 with concentration of 1.4×1017 cm−3.  相似文献   

18.
Commercially purchased CR-39 and PET polymers were irradiated by 100 MeV O7+ ions of varying fluences, ranging from 1×1011 to 1×1013 ions/cm2. The effects of swift heavy ions (SHI) on the structural, optical and chemical properties of CR-39 and PET polymers were studied using X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The XRD patterns of CR-39 show that the intensity of the peak decreases with increasing ion fluence, which indicates that the semicrystalline structure of polymer changes to amorphous with increasing fluences. The XRD patterns of PET show a slight increase in the intensity of the peaks, indicating an increase in the crystallinity. The UV-visible spectra show the shift in the absorbance edge towards the higher wavelength, indicating the change in band gap. Band gap in PET and CR-39 found to be decrease from 3.87 to 2.91 and 5.3-3.5 eV, respectively. The cluster size also shows a variation in the carbon atoms per cluster that varies from 42 to 96 in CR-39 and from 78 to 139 in PET. The FTIR spectra show an overall reduction in intensity of the typical bands, indicating the degradation of polymers after irradiation.  相似文献   

19.
Effects of a new plasticizer, polysorbate 80, on the structural and electrochemical properties of PEO–NH4PF6 polymer electrolyte system have been investigated. X-ray diffraction studies show significant increase in amorphicity of the solid polymer electrolyte on introduction of the plasticizer, which is also supported by lesser-dense spherulites observed in the SEM micrographs. The room temperature ionic conductivity of the electrolyte shows an increase of about two orders of magnitude (σmax~10?5 S/cm) on plasticization. The frequency dependence of the conductivity has been found to obey the Jonscher’s power law and slower backward ion hopping on plasticization. The polymer electrolyte shows protonic conduction as confirmed using cyclic voltammetry study. The studies show that polysorbate 80 is a promising plasticizer for semicrystalline polymer electrolytes.  相似文献   

20.
A high-temperature, high-pressure flat-flame burner reactor was developed to prepare char at different pressures. This system achieves particle heating rates of 105 K/s, which better mimics industrial conditions than conventional drop tube or radiative flow reactors. Previous data at atmospheric pressure demonstrated a significant decrease in particle swelling during devolatilization as heating rates increased from 104 K/s (the typical drop tube heating rate) to 105 K/s. Pyrolysis experiments were performed at pressures from 1 to 15 atm at 1300 °C for two bituminous coals and a lignite. Average swelling was determined from a combination of the mass release and the average density. The results indicate significantly lower swelling ratios at elevated pressures than reported in the literature. Scanning electron micrographs show that the bubbles in the bituminous coal particles popped before significant swelling at these elevated heating rates. Lignite particles exhibited shrinkage rather than swelling, but still showed a small effect of pressure. TGA oxidation reactivities were determined for the Pitt #8 and Knife River lignite char samples at their respective char preparation pressures. The oxidation reactivities of both the bituminous and lignite chars decreased with increasing pressure.  相似文献   

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