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1.
Compared with linear polymers, more factors may affect the glass‐transition temperature (Tg) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. Tg's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of Tg to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. Tg's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. Tg values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. Tg values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of Tg versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that Tg increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004 相似文献
2.
Eric P. Bescher Atif Noori John D. Mackenzie 《Journal of Sol-Gel Science and Technology》2004,32(1-3):69-72
A fluorinated copolymer/metal oxide hybrid is fabricated by refluxing a high hydroxyl content fluorinated copolymer with tetraethoxysilane. The resulting organic-inorganic hybrids are transparent throughout the entire compositional range if processed with HCl as a catalyst. They exhibit a continuous variation in hardness, hydrophobicity, and abrasion resistance, intermediary between the properties of the pure polymer and that of a silica gel. The catalyst has a strong influence over the microstructure of the hybrid. 29Si MAS-NMR indicates the presence of highly condensed silica clusters within the structure of the hybrid. If a Nd(III) alkoxide is used instead of TEOS, a Nd 3+-doped fluoropolymer is obtained. These results indicate that when a fluorinated copolymer contains groups amenable to hydrolysis and condensation, cross-linking with a metal alkoxide is possible, leading to an interesting families of hybrids. 相似文献
3.
R. Eric Berson John S. Young Thomas R. Hanley 《Applied biochemistry and biotechnology》2006,130(1-3):612-620
Following detoxification of the liquid hydrolysate produced in a corn stover pretreatment process, inhibitor levels are seen
to increase with the re-addition of solids for the ensuing hydrolysis and fermentation processes. The solids that were separated
from the slurry before detoxification of the liquor contain approx 60% (w/w) moisture, and contamination occurs owing to the
diffusion of inhibitors from the moisture entrained in the porous structure of the corn stover solids into the bulk fluid.
This evidence suggests the need for additional separation and detoxification steps to purge residual inhibitors entrained
in the moisture in the solids. An overliming process to remove furans from the hydrolysate failed to reduce total organic
acids concentration, so acids were removed by treatment with an activated carbon powder. Smaller carbon doses proved more
efficient in removing organic acids in terms of grams of acid removed per gram of carbon powder. Sugar adsorption by the activated
carbon powder was minimal. 相似文献
4.
Numerical schemes for systems with multiple spatio-temporal scales are investigated. The multiscale schemes use asymptotic results for this type of systems which guarantee the existence of an effective dynamics for some suitably defined modes varying slowly on the largest scales. The multiscale schemes are analyzed in general, then illustrated on a specific example of a moderately large deterministic system displaying chaotic behavior due to Lorenz. Issues like consistency, accuracy, and efficiency are discussed in detail. The role of possible hidden slow variables as well as additional effects arising on the diffusive time-scale are also investigated. As a byproduct we obtain a rather complete characterization of the effective dynamics in Lorenz model. 相似文献
5.
Eric Flauraud Frdric Nataf Isabelle Faille Roland Masson 《Comptes Rendus Mecanique》2003,331(12):849-855
We present in this paper a domain decomposition method to treat faults in geological basin modeling. The particularity of this model is that the faults whose widths are very small in comparison with the basin size, are not characterized as subdomains any more but as interfaces between sedimentary blocks. The originality of this work lies in the formulation of this new fault model and in the definition and the computation of the interface conditions between the subdomains. To cite this article: E. Flauraud et al., C. R. Mecanique 331 (2003). 相似文献
6.
Exterior tomographic data are taken over lines outside a central region, and such data occur in the industrial nondestructive evaluation of large objects such as rockets. We explain, using microlocal analysis, which singularities are well reconstructed from exterior data, and we explain how this phenomenon is reflected in the singular value decomposition for the exterior transform [E.T. Quinto, Singular value decompositions and inversion methods for the exterior Radon transform and a spherical transform, J. Math. Anal. Appl. 95 (1983) 437–448]. We extend Lambda Tomography to exterior data and to limited angle exterior data. The algorithm is tested on industrial data from Perceptics, Inc. 相似文献
7.
We consider a single machine scheduling problem with two min-sum objective functions: the sum of completion times and the sum of weighted completion times. We propose a simple polynomial time (1+(1/γ),1+γ)-approximation algorithm, and show that for γ>1, there is no (x,y)-approximation with 1<x<1+(1/γ) and 1<y<1+(γ-1)/(2+γ). 相似文献
8.
Eric A. Pandiscio 《School science and mathematics》2002,102(5):216-221
This case study investigated how secondary preservice mathematics teachers perceive the need for and the benefits of formal proof when given geometric tasks in the context of dynamic geometry software. Results indicate that preservice teachers are concerned that after using dynamic software high school students will not see the need for proofs. The participants stated that multiple examples are not equivalent to a proof but, nonetheless, questioned the value of formal proof for high school students. Finally, preservice teachers found the greatest value of geometric software to be in helping students understand key relationships within a problem or theorem. Participants also tended to study a problem more deeply with the software than without it. 相似文献
9.
The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C3H7C(O)OONO2, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH3C(O)OONO2, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10?4 s?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10?4 s?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc. 相似文献
10.