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61.
We present a unified approach for linear and nonlinear sensitivity analysis for models of reaction kinetics that are stated in terms of systems of ordinary differential equations (ODEs). The approach is based on the reformulation of the ODE problem as a density transport problem described by a Fokker-Planck equation. The resulting multidimensional partial differential equation is herein solved by extending the TRAIL algorithm originally introduced by Horenko and Weiser in the context of molecular dynamics (J. Comp. Chem. 2003, 24, 1921) and discussed it in comparison with Monte Carlo techniques. The extended TRAIL approach is fully adaptive and easily allows to study the influence of nonlinear dynamical effects. We illustrate the scheme in application to an enzyme-substrate model problem for sensitivity analysis w.r.t. to initial concentrations and parameter values. 相似文献
62.
D. Duracher F. Sauzedde A. Elaissari A. Perrin C. Pichot 《Colloid and polymer science》1998,276(3):219-231
Cationic hydrophilic copolymer latexes were synthesized at 70 °C either by batch or two-step emulsifier-free emulsion poly-merization
of styrene (St), N-iso-propylacrylamide (NIPAM), and aminoethylmethacrylate hydro-chloride (AEM) using 2,2′-azobis (2-amidinopropane) dihydrochloride
as initiator. At first, batch polymerization kinetics were followed by gas chromatography (GC), revealing that NIPAM rapidly
homopolymerized, before the polymerization of styrene had started. Particle size analysis by quasi-elastic light scattering
(QELS) and transmission electron microscopy (TEM) showed that monodispersed particles were obtained with the formation of
a poly[NIPAM] rich shell. Adding a small amount of the cationic monomer caused a strong decrease of the particle size without
affecting the size monodispersity. When a shot process was used, a narrow particle size distribution was maintained, provided
that the monomer addition was performed at a relatively high conversion of the first batch step. The poly[NIPAM] rich shell
layer was larger with the shot process, but increasing the amino-containing monomer in the recipe resulted in a dramatic decrease
of the thickness. Combination of transmission, scanning and atomic force microscopy techniques showed that these hydrophilic
particles exhibited odd-shaped structures, the unevenness being dependent upon the performed process. Kinetic data and particle
morphology information were inferred for discussion of the polymerization mechanism of this system.
Received: 21 August 1997 Accepted: 22 October 1997 相似文献
63.
S. Shen E. D. Sudol M. S. El-Aasser 《Journal of polymer science. Part A, Polymer chemistry》1994,32(6):1087-1100
The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc. 相似文献
64.
We reported in this paper FTIR linear diehroic spectroscopy and anisotropic properties of the nanoparticulate α-Fe_2O_3-stearate alternating Langmuir-Blodgett films (Fe_2O_3-St LB films) a new inorganic-organic quantum superlattice system. A new method fitted to inorganic-organic alternating films is used to study the molecular orientation and discuss the order arrangement of the nanopartieles in the films. The the results show that a configuration of stearate ions bound to the surface of the nano-particles: COO~- group are spherically bound to the surface of the nanoparticles; the hydrocarbon chains are almost perpendicular (31°±5°) to the substrate (7 nm-Fe_2O_3-St LB films). The orientation of hydrocarbon chains and CH_2 scissors vibration show the existence of trans-zigzag planar structure for C—C broken bone of the hy7drocarbon chains, which is related to high-order structure of the alternate films. 相似文献
65.
P. Hazot J. P. Chapel C. Pichot A. Elaissari T. Delair 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1808-1817
Monodisperse, thermosensitive poly(N‐ethyl methacrylamide) microgel particles were prepared by the batch precipitation/emulsion polymerization of water‐soluble N‐ethyl methacrylamide and the hydrophobic crosslinker ethylene glycol dimethacrylate initiated by potassium persulfate. Particular attention was paid to the effect of the crosslinker agent on the polymerization process (kinetics, conversion, and water‐soluble oligomer content). Particles were characterized in terms of their size distribution and swelling capacity. A polymerization mechanism for the water‐soluble monomer and non‐water‐soluble crosslinker is proposed and discussed on the basis of a combination of both emulsion and precipitation polymerization processes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1808–1817, 2002 相似文献
66.
以金属硝酸盐为原料,分别采用高分子前驱体法、柠檬酸盐凝胶法制备了纳米级的Ce-Zr-Ba-O复合氧化物超细粒子,采用X-射线衍射(XRD)、透射电镜(TEM)、BET比表面测定、热重-差热(TG-DTA)技术对催化剂进行了表征,并考察了催化剂的CO氧化活性和热稳定性。实验结果表明,高分子前驱体法和柠檬酸盐凝胶法制备的催化剂粉体都达到了纳米级。两种方法中,高分子前驱体法所制得的催化剂的BET比表面达118.96m2·g-1,CO氧化反应活性较高,同时该方法制得的催化剂分散性好,无团聚,经1000℃高温焙烧后仍基本无烧结、无团聚现象,具有较高的热稳定性。 相似文献
67.
We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A2‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A2‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023). 相似文献
68.
69.
水煤浆添加剂与煤之间的相互作用规律研究 Ⅰ. 复合煤颗粒间的相互作用对水煤浆流变性的影响 总被引:10,自引:5,他引:10
使用12种不同分散剂对14种不同变质程度的煤进行了成浆性实验,分析了182个水煤浆(CWS)样品的流变性。结果表明,低变质程度和高灰煤浆多呈屈服假塑性,煤的性质起主导作用;变质程度高且灰分较低煤浆的流变性,主要依赖于分散剂的结构与性质;分子结构单元立体空间效应大,疏水基团与亲水基团呈立体间隔分布的分散剂,易形成屈服假塑性CWS;分子线度长,亲水基团与疏水基团呈线性间隔分布的分散剂,易形成胀塑性CWS。复合煤粒间的相互作用方式是决定CWS流变特性的关键。 相似文献
70.
乳状液法制备憎液溶胶Ⅰ.BaCO_3均匀粒子的制备 总被引:1,自引:0,他引:1
均匀胶体粒子的形成,除与反应条件(反应物浓度、陈化时间和温度、介质种类等)有关外,反应体系的环境也影响最终产物的形态,《至结晶结构.气溶胶法和微乳液法正是利用微环境中的‘水池效应”;分别制备出球形亚微米和纳米级的均匀粒子[‘-‘]、这些方法与水解法和相转化法等方法比较,反应物浓度要大几个数量级,而反应时间却短很多,因而受到研究人员的关注.乳状液也能提供亚微米、微米及以上级的微环境,因此,可以应用O/W乳状液乳液中的聚合反应制备亲液的分散体系.然而,极少有关利用w/O乳状液制备僧液溶胶的报导问;最近… 相似文献