Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

Learning to See: Making Sense of the Mathematics of Change in Middle School

In this article, we will describe the results of a study of 6th grade students learning about the mathematics of change. The students in this study worked with software environments for the computer and the graphing calculator that included a simulation of a moving elevator, linked to a graph of its velocity vs. time. We will describe how the students and their teacher negotiated the mathematical meanings of these representations, in interaction with the software and other representational tools available in the classroom. The class developed ways of selectively attending to specific features of stacks of centimeter cubes, hand-drawn graphs, and graphs (labeled velocity vs. time) on the computer screen. In addition, the class became adept at imagining the motions that corresponded to various velocity vs. time graphs. In this article, we describe this development as a process of learning to see mathematical representations of motion. The main question this article addresses is: How do students learn to see mathematical representations in ways that are consistent with the discipline of mathematics? This revised version was published online in July 2006 with corrections to the Cover Date.     

Monitoring photopolymerization reactions with optical pyrometry

This article describes the development of optical pyrometry (OP) as a new analytical technique for the continuous monitoring of the progress of both free‐radical and cationic photopolymerizations. The method is rapid, reproducible, and very easy to implement. A temperature profile of a photopolymerization can be obtained. Preliminary studies have shown that the temperatures of some polymerizing monomers can easily reach temperatures in excess of 250 °C. The effects of the mass and reactivity of the monomer, light intensity, structures, and concentrations of the photoinitiators and monomers as well as the presence or absence of oxygen on various free‐radical and cationic photopolymerizations were examined with this method. Coupling of real‐time infrared spectroscopy with OP provides a convenient method for simultaneously monitoring both the chemical conversion and the temperature of a photopolymerization. This combined technique affords new insights into the effects of temperature‐induced autoacceleration on the course of photopolymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 579–596, 2003     

Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

Cyclo[(6-amino-6-deoxy-d-galactonic acid)4]: a new class of carbopeptoid-cyclodextrin

The formation of the 28-membered ring cyclo[(6-amino-6-deoxy-d-galactonic acid)₄] by cyclisation of a protected open chain fully hydroxylated nylon 6 linear tetramer in modest yield provides the first example of a new class of carbopeptoid-cyclodextrin.     

An efficient synthesis of 5-aminoimidazol-2-ones via cyclization reactions of 2-aminoacetonitriles and isocyanates

The scope of a cyclization reaction between amino-acetonitriles and isocyanates was investigated. The study revealed that this reaction tolerates various functional groups leading to highly functionalized 5-amino-imidazole-2-ones, which are useful intermediates for purine synthesis.