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51.
Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess zi* of diblock copolymers of poly (d8-styrene-b-2-vinylpyridine) (dPS-PVP) at the interface between the homopolymers PS and PVP as a function of ?∞, the volume fraction of diblock copolymer remaining in the host homopolymer. All the samples were analyzed after annealing at temperatures and times sufficient to achieve equilibrium segregation. The effect of the degree of polymerization of both the diblock copolymers and the host homopolymers on the segregation isotherm is investigated. When the degree of polymerization of the homopolymer is much larger than that of the diblock copolymer, the normalized interfacial excess (zi*/Rg), where Rg is the radius of gyration of an isolated block copolymer chain, is a universal function of that portion of the block copolymer chemical potential due to chain stretching. The existence of such a universal function is predicted by theory and its form is in good agreement with self-consistent mean field calculations. Using these results, one can predict important aspects of the block copolymer segregation (e.g., the saturation interfacial excess) without recourse to the time-consuming numerical calculations. © 1994 John Wiley & Sons, Inc. 相似文献
52.
The kinetics of domain size equilibration were studied for asymmetric poly(ethylene‐alt‐propylene)‐b‐poly(dimethyl siloxane) (EPDMS) and polyisoprene‐b‐poly(dimethyl siloxane) (IDMS) block copolymers in the body‐centered cubic ordered phase. Small‐angle X‐ray scattering measurements of the principal peak position (q*) were made as a function of time after temperature jumps within the ordered state. The equilibration times were remarkably long, especially on cooling and for temperatures below 100 °C. For example, after a quench to 40 °C, q* for EPDMS had not fully equilibrated even after several weeks of annealing; IDMS required several days to equilibrate at the same temperature. In contrast, a lamella‐forming EPDMS sample was able to adjust q* within the timescale of the measurements (i.e., minutes) with both heating and cooling over the same temperature range. Measurements of tracer diffusion indicated that chain mobility was not the rate‐limiting step, although differences in mobility did account for the differences between EPDMS and IDMS. Rather, the limiting step was the required reduction in the number density of spheres on cooling; the disappearance of spheres, either by evaporation or by fusion, provided a large kinetic barrier. Lamellae, however, could adjust domain dimensions simply by local displacements of individual chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 715–724, 2003 相似文献
53.
E.M. Rabinovich D.W. Johnson Jr. A. Mishkevich E.A. Chandross J. Thomson Jr. 《Journal of Sol-Gel Science and Technology》2003,28(1):19-29
Particulate sol-gel technology uses larger particles than that of alkoxide-derived gels and provides larger pore sizes in the gelled object. This allows relatively rapid drying and fabrication of large rods or tubular shapes. However, the formation of more complex or flat shapes, which require extensive surface contact with a mold, is more difficult. The shrinkage during drying, with the significantly greater stress of surface friction due to adhesion, frequently leads to cracking.We have demonstrated a solution to this problem by floating the gel on the surface of a dense liquid. Dry silica panels up to 28 × 40 × 0.7 cm3 were prepared in this way. The use of patterning molds allowed the fabrication of more sophisticated shapes. These bodies were sintered to transparent vitreous silica articles of near net dimensions. 相似文献
54.
Kevin W Kells 《Tetrahedron》2004,60(10):2247-2257
Transmetalation of urea derivatives of α-aminoorganostannanes with alkyllithiums provides α-aminoorganolithiums which undergo rapid N to C acyl migration to afford α-aminocarboxamides. The stereochemical course of the transmetalation/migration process depends on the substituents on the urea and varies from complete retention of configuration to complete racemization. 相似文献
55.
J. Odeurs R. Coussement C. L'abbé G. Neyens G.R. Hoy E.E. Alp W. Sturhahn T. Toellner C. Johnson 《Hyperfine Interactions》1998,113(1-4):455-463
A new time integrated method for the study of resonant nuclear scattering of synchrotron radiation in the forward direction
or in Bragg directions is introduced. This method gives in principle similar information as the well known time differential
method. A brief comparison of both methods is presented. The idea is to excite coherently the nuclei incorporated in two absorbers,
one moving with respect to the other. The fields radiated by the nuclei from both absorbers interfere and each time the nuclear
energy in one absorber matches, by Doppler modulation, the nuclear energy of the other, an extremum in the time integrated
intensity is observed. The results of the first experiments at the Advanced Photon Source at the Argonne National Laboratory
will be presented.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
56.
We prove the following. Let G be an undirected graph. Every partially specified symmetric matrix, the graph of whose specified entries is G and each of whose fully specified submatrices is completely positive (equal to BBT for some entrywise nonnegative matrix B), may be completed to a completely positive matrix if and only if G is a block-clique graph (a chordal graph in which distinct maximal cliques overlap in at most one vertex). The same result holds for matrices that are doubly nonnegative (entrywise nonnegative and positive semidefinite). 相似文献
57.
Rehan A. Kazi Vyas M.N. Prasad Jeeve Kanagalingam Christopher M. Nutting Peter Clarke Peter Rhys-Evans Kevin J. Harrington 《Journal of voice》2007,21(6):661-668
The objective of this study was to assess the difference in voice quality as defined by acoustical analysis using sustained vowel in laryngectomized patients in comparison with normal volunteers. This was designed as a retrospective single center cohort study. An adult tertiary referral unit formed the setting of this study. Fifty patients (40 males) who underwent total laryngectomy and 31 normal volunteers (18 male) participated. Group comparisons with the first three formant frequencies (F1, F2, and F3) using linear predictive coding (LPC) (Laryngograph Ltd, London, UK) was performed. The existence of any significant difference of F1, F2, and F3 between the two groups using the sustained vowel /i/ and the effects of other factors namely, tumor stage (T), chemoradiotherapy, pharyngectomy, cricothyroid myotomy, closure of pharyngoesophageal segment, and postoperative complication were analyzed. Formant frequencies F1, F2, and F3 were significantly different in male laryngectomees compared to controls: F1 (P<0.001, Mann-Whitney U test), F2 (P<0.001, Student's t test), and F3 (P=0.008, Student's t test). There was no significant difference between females in both groups for all three formant frequencies. Chemoradiotherapy and postoperative complications (pharyngocutaneous fistula) caused a significantly lower formant F1 in men, but showed little effect in F2 and F3. Laryngectomized males produced significantly higher formant frequencies, F1, F2, and F3, compared to normal volunteers, and this is consistent with literature. Chemoradiotherapy and postoperative complications significantly influenced the formant scores in the laryngectomee population. This study shows that robust and reliable data could be obtained using electroglottography and LPC in normal volunteers and laryngectomees using a sustained vowel. 相似文献
58.
In 1987 the Canadian Department of National Defence enunciated the Total Force concept. The Total Force is comprised of Regular and Reserve components. The intention is to make maximum use of the Reserve to reduce defence expenditures and at the same time to ensure that military capability remains adequate to support national policy objectives. This paper discusses some of the governing parameters that affect the modelling of the composition of the Total Force and analyses the mix of regular and reserve forces. The interplay between the key factors and their marginal costs will be stressed. The models are employed to study two units in the Canadian Forces, a maintenance support unit and a tactical unit with high operational activity cost. The lessons drawn from these studies are highlighted. 相似文献
59.
60.
D. A. Johnson A. G. Maddock M. Taylor 《Journal of Radioanalytical and Nuclear Chemistry》1987,119(1):43-50
When anhydrous EuCl3, GdCl3, DyCl3 or Eu2O3 are irradiated with fast neutrons and then dissolved in dilute hydrochloric acid, small amounts of reducing species, believed to be divalent lanthanide cations, are revealed. The amount produced increases with the thermodynamic stability of the Ln2+ species /Eu>Dy>Gd>/. 相似文献