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排序方式: 共有796条查询结果,搜索用时 15 毫秒
1.
Z. Ferhat-Hamida H. Phuong-Nguyen P. Bernazzani A. Haine G. Delmas 《Journal of Materials Science》2007,42(9):3138-3154
LLDPE samples synthesized with Ziegler–Natta (ZN) and Metallocene (MT) catalysts have been analyzed to investigate a potential
catalyst-dependent morphology and to find an explanation for the difficult processing of MT. Slow calorimetry at v = 0.02 K/min and IR at RT and in the melt are used. The differences between MT and ZN are assigned to their different composition,
MT not having the linear segments, which are present in ZN. Slow calorimetry is effectively a drawing process of the melt
with chain orientation followed by decay. The later event, characterized by an endotherm, ΔH
network, occurs at higher temperatures for MT, the presence of a regular distribution of methyl groups slowing down the process.
The rocking, gauche, bending and stretching regions of the IR spectra are analyzed. The nascent MT has more strained bands
in the rocking region. The wagging region reveals the more homogeneous environment of MT through the maximum absorbance at
1,368 cm−1. Decomposition of bands is made for the rocking and wagging regions. The orthorhombic crystallinity, αc (FTIR), measures the sum of long- and short-range orthorhombic order, the latter being obtained by αc (FTIR)-αc (X-rays). The values of αc (FTIR) for MT and ZN are very similar in conditions of equilibrium. The justifications for the molecular origin of ΔH
network are presented: (i) the slow relaxation of long chains strained and oriented in the melt measured by other techniques, (ii)
The correlation, for gels of a linear sample, made in different solvents, between the maximum drawability, λmax, and ΔH
network in a slow T-ramp. The range is 80–270 for λmax and 40–120 J/g for ΔH
network. (iii) The comparison of two traces of the same sample, between 140 °C and 270 °C, show that comparable events in the melt
appear in the integrated absorbance and in the slow calorimetry signal. Analysis on thin films of the little-studied CH2 stretching region reveals that their extinction coefficient, ε, and the shape of the bands are highly sensitive to the sample
history, ε diminishing by a large factor in slowly crystallized samples. Events in the slow T-ramp, followed by a fast crystallization, on the other hand, leads to materials with standard characteristics. Slow calorimetry
traces display more events (endothermic and exothermic) for MT than for ZN, a finding consistent with more flow irregularities
during processing. Equilibrium conditions and better processing could be reached for MT by extending time in the melt or using
higher temperatures. 相似文献
2.
Anastasiya Rybak Patrice A. Fokou Michael A. R. Meier 《European Journal of Lipid Science and Technology》2008,110(9):797-804
Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. In oleochemistry, this reaction is well known and has been applied for many decades. Examples include the functionalization of the double bonds of different oleochemicals or the (direct) polymerization of plant oils via metathesis. More recent developments, particularly the development of better and more robust catalysts, allow for highly efficient cross‐metathesis reactions opening new possibilities for the direct introduction of chemical functionalities. Within this contribution, the development of metathesis in oleochemistry will be discussed, covering self‐metathesis as well as more recent developments in the field of cross‐metathesis that lead to desired platform chemicals. 相似文献
3.
Gaussian Cramer-Rao bound for direction estimation of noncircular signals in unknown noise fields 总被引:1,自引:0,他引:1
This paper focuses on the stochastic Cramer-Rao bound (CRB) on direction of arrival (DOA) estimation accuracy for noncircular Gaussian sources in the general case of an arbitrary unknown Gaussian noise field parameterized by a vector of unknowns. Explicit closed-form expressions of the stochastic CRB for DOA parameters alone are obtained directly from the Slepian-Bangs formula for general noncircular complex Gaussian distributions. As a special case, the CRB under the nonuniform white noise assumption is derived. Our expressions can be viewed as extensions of the well-known results by Stoica and Nehorai, Ottersten et al., Weiss and Friedlander, Pesavento and Gershman, and Gershman et al. Some properties of these CRBs are proved and finally, these bounds are numerically compared with the conventional CRBs under the circular complex Gaussian distribution for different unknown noise field models. 相似文献
4.
Carole E. Baddour Cedric L. Briens Serge Bordere Didier Anglerot Patrice Gaillard 《Chemical Engineering and Processing: Process Intensification》2008,47(12):2195-2202
Since their observation in 1976 and 1991, carbon nanotubes (CNTs) have generated much interest due to their properties and potential applications. CNTs are tubular carbon molecules with remarkable mechanical, electrical, chemical and thermal properties, which make them useful in various applications. Industries producing CNTs via the fluidized bed chemical vapor deposition technique face challenges related to the size of CNT bundles. The two main challenges are agglomeration and agglomerate size distribution control. A solution to these challenges involves the use of jet mills to grind the CNT agglomerates. The goal of this study was to determine whether the nanotubes could be ground with air jets using a commercial jet mill and apply a two-parameter model to describe the grinding process. The present study has indicated that air-jet grinding of CNTs is feasible with a typical commercial jet mill. This paper presents the effect of operational parameters on the arithmetic mean diameter of the ground product. Sonic velocity through the grinding nozzles was required to obtain reasonable grinding rates and relatively narrow particle size distributions. This occurs at high air to solids feedrate ratios. Additionally, a simple attrition model can describe the grinding process in the spiral jet mill. 相似文献
5.
Catalytic chlorination of methane was studied over SO
4
2–
/ZrO2, Pt/SO
4
2–
/ZrO2, and Fe/Mn/SO
4
2–
/ZrO2 solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240°C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200°C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225°C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235°C in selectivities greater than 85%. No chloroform or carbon tetrachloride is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.Catalysis by solid superacids, 29. For part 28 see ref. [14]. 相似文献
6.
A necessary and sufficient condition is given for a connected bipartite graph to be the incidence graph of a contact family
of segments and points. We deduce that any four-connected three-colorable plane graph is the contact graph of a family of
segments and that any four-colored planar graph without an induced C4 using four colors is the intersection graph of a family of straight line segments. 相似文献
7.
A Pierres H Feracci V Delmas AM Benoliel JP Thiery P Bongrand 《Canadian Metallurgical Quarterly》1998,95(16):9256-9261
We describe a method allowing quantitative determination of the interaction range and association rate of individual surface-attached molecules. Spherical beads (1.4 micro(m) radius) were coated with recombinant outer domains of the newly described classical type II cadherin 11, a cell adhesion molecule. Beads were driven along cadherin-coated surfaces with a hydrodynamic force of approximately 1 pN, i.e., much less than the mechanical strength of many ligand-receptor bonds. Spheres displayed periods of slow motion interspersed with arrests of various duration. Particle position was monitored with 50 Hz frequency and 0.025 micro(m) accuracy. Nearly 1 million positions were recorded and processed. Comparison between experimental and computer-simulated trajectories suggested that velocity fluctuations might be related quantitatively to Brownian motion perpendicular to the surface. The expected amplitude of this motion was of order of 100 nm. Theoretical analysis of the relationship between sphere acceleration and velocity allowed simultaneous determination of the wall shear rate and van der Waals attraction between spheres and surface. The Hamaker constant was estimated at 2.9 x 10(-23) J. The frequency of bond formation was then determined as a function of sphere velocity. Experimental data were consistent with the view that the rate of association between a pair of adhesion molecules was approximately 1.2 x 10(-3) s-1 and the interaction range was approximately 10 nm. It is concluded that the presented methodology allows sensitive measurement of sphere-to-surface interactions (with approximately 10 fN sensitivity) as well as the effective range and rate of bond formation between individual adhesion molecules. 相似文献
8.
A new crystalline structure of poly 4-methylpentene-1 (P4MP1), modiification named modification V, is obtained from cyclopentane solutions and gels, for polymer volume fractions between 0.01 and 0.10. The effect of the thermal history imparted to the solution is analyzed. The relation between gelation, polymorphism and existence of helical conformations of P4MP1 in solution is discussed. Modification V is tentatively indexed on the basis of an hexagonal unit cell with dimensions a = 22.17 ± 0.14 Å and c = 6.69 ±0.02 Å. The crystal transforms into modification I at 130 ± 5°C, the heat of transition being + 15 ±2 J.g?1. 相似文献
9.
The Knoop hardnesses of five glasses decreased with increasing load in accordance with the classic indentation size effect (ISE). At moderate loads, cracking dramatically altered the indentation sizes and the ISE trends in three of the five glasses. Cracked indentations were as much as 10 μm longer than uncracked indentations made under identical conditions. Diagonal length readings must be corrected for optical resolution limitations if low power lenses are used. 相似文献
10.
Arezki Tagnit-Hamou Mladenka Saric-Coric Patrice Rivard 《Cement and Concrete Research》2005,35(1):99-107
This paper presents research results on the causes of a severe concrete deterioration, which occurred in many building foundations approximately 2 years after construction. Concrete samples were investigated with X-ray diffraction (XRD) analysis, a scanning electron microscope (SEM) and a petrographic examination performed with a stereomicroscope. It was found that the early cracking of concrete stemmed from the oxidation of the pyrrhotite found in the anorthosite aggregates used to produce the concrete. The oxidation process led to the precipitation of iron hydroxides having a higher volume than the original pyrrhotite does. The presence of micas (biotite) close to the pyrrhotite seemed to promote and accelerate the oxidation process. 相似文献