Molecular weight dependence of diblock copolymer segregation at a polymer/polymer interface

Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess z_i^* 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 (z_i^*/R_g), where R_g 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.     

Domain size equilibration in sphere‐forming block copolymers

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     

An unusual 1,2-N→C acyl migration in urea derivatives of α-aminoorganolithiums

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.     

Constants of Motion for Several One-Dimensional Systems and Problems Associated with Getting Their Hamiltonians

The constants of motion of the following systems are deduced: a relativistic particle with linear dissipation; a no-relativistic particle with a time explicitly depending force; a no-relativistic particle with a constant force and time depending mass; and a relativistic particle under a conservative force with position depending mass. The Hamiltonian for these systems, which is determined by getting the velocity as a function of position and generalized linear momentum, can be found explicitly at first approximation for the first system. The Hamiltonians for the other systems are kept implicitly in their expressions for their constants of motion.     

Assessment of the Formant Frequencies in Normal and Laryngectomized Individuals Using Linear Predictive Coding

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.     

Composition of the Canadian Total Force: Issues and Findings for the Air Components

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.     

Annealing effects on the magnetization of Co–Ni–B amorphous nanoparticles

Chemically prepared (Co_xNi_1−x)_1−yB_y (x=0.5, 0.75, 1; y≈0.4) amorphous fine particles were characterized by X-ray diffraction, DTA and TGA, and in situ magnetic measurement as a function of annealing temperature in an inert atmosphere. Magnetic measurement performed in as-prepared and 150°C annealed samples shows an increase of the saturation magnetization and magnetic moment after thermal treatment. Room temperature magnetization increases by factors of 3.5, 1.8, and 1.5, for x=0.5, 0.75, and 1, respectively. These measurements may indicate a local re-ordering of the amorphous phase at temperatures much lower than the full crystallization temperature.     

Entropy and ergodic probability for differentiable dynamical systems and their bundle extensions

We answer a problem of Liao [S.T. Liao, Standard systems of differential equations and obstruction sets—from linearity to perturbations, in: System Researches, Proceedings Dedicated to the 85th Anniversary of Qian Xue-Sen, Zhejiang Education Press, Hangzhou, China, 1996, pp. 279-290 (in Chinese)]: A C¹ vector field or a C¹ diffeomorphism on an n-dimensional manifold has equal entropy with that of its bundle extensions. We also prove that each ergodic probability with simple Lyapunov spectrum has at most n²n! covering probabilities on each bundle extension.