Preparation and chain extension of C100dicarboxylic acid

The selective degradation of polyethylene crystals with fuming nitric acid has been used to prepare a C₁₀₀ chain with terminal functional groups. After treating this product with concentrated sulphuric acid, it is shown by average molecular weight, titration and infra-red spectroscopy measurements that each molecule contains two carboxylic acid groups. This C₁₀₀ dicarboxylic acid is chain extended with several low molecular weight difunctional coupling agents. Block copolymers of this acid and poly(propylene glycol) have been prepared.     

Catalytic oxidative degradation of polyethylene crystals

Linear polyethylene crystals have been degraded with oxygen in the presence of a catalyst composed of cobaltous and bromide ions at temperatures between 60 and 130°. The number of carbonyl groups introduced into polyethylene increases as the oxidation temperature is raised. Infra-red spectroscopy and molecular weight evidence suggests that ketone groups are formed by a non-chain scission reaction, whereas aldehyde and carboxylic acid groups result from chain scission reactions. Molecular weight distributions of the degradation products show that reactions occur selectively in the amorphous regions at the crystal surfaces, when oxidations are performed below 110°. At higher temperatures, the chains are degraded randomly. The carbonyl groups introduced into polyethylene were oxidized to carboxylic acid groups with concentrated (～ 70 per cent) nitric acid. The results demonstrate that this two-stage process yields a polydisperse long-chain linear paraffin with carboxylic acid end-groups, when the catalytic oxidations are performed between 115 and 130°.     

Steady Sliding Frictional Contact Problems in Linear Elasticity

The existence and uniqueness of an equilibrium solution to frictional contact problems involving a class of moving rigid obstacles is studied. At low friction coefficient values, the steady sliding frictional contact problem is uniquely solvable, thanks to the Lions-Stampacchia theorem on variational inequalities associated with a nonsymmetric coercive bilinear form. It is proved that the coerciveness of the bilinear form can be lost at some positive critical value of the friction coefficient, depending only on the geometry and the elastic properties of the body. An example presented here, shows that infinitely many solutions can be obtained when the friction coefficient is larger than the critical value. This result is paving the road towards a theory of jamming in terms of bifurcation in variational inequality. The particular case where the elastic body is an isotropic half-space is studied. The corresponding value of the critical friction coefficient is proved to be infinite in this case. In the particular case of the frictionless situation, our analysis incidentally unifies the approaches developed by Lions-Stampacchia (variational inequalities) and Hertz (harmonic analysis on the half-space) to contact problems in linear elasticity.     

Dynamic control of volume phase transitions of poly(N‐isopropylacrylamide) based microgels in water using hydrazide‐aldehyde chemistry

We demonstrate that the volume phase transition temperature (VPTT) of copolymer microgel particles made from N‐isopropylacrylamide (NIPAm) and methacryloyl hydrazide (MH) can be tailored in a reversible manner upon the reaction of the hydrazide functional groups with aldehydes. The microgels were synthesized by precipitation polymerization in water. Due to the water‐soluble nature of the MH monomer, the VPTT at which the microgel particles contract shifts to higher values by increasing the incorporated amounts of methacryloyl hydrazide from 0 to 5.0 mol %. The VPTT of the copolymer microgel dispersions in water can be fine‐tuned upon addition of hydrophobic/hydrophilic aldehydes, which react with the hydrazide moiety to produce the hydrazone analogue. This hydrazone formation is reversible, which allows for flexible, dynamic control of the thermo‐responsive behavior of the microgels. The ability to “switch” the VPTT was demonstrated by exposing hydrophilic streptomycin sulfate salt incubated microgel particles to an excess of a hydrophobic aldehyde, that is benzaldehyde. The temperature at which these microgels contracted in size upon heating was markedly lowered in these aldehyde exchange experiments. Transformation into benzaldehyde hydrazone derivatives led to assembly of the microgel particles into small colloidal clusters at elevated temperatures. This control of supracolloidal cluster formation was also demonstrated with polystyrene particles which had a hydrazide functionalised microgel shell. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1745–1754     

A High-Resolution Analysis of the ν3 Absorption Band of Trifluoromethane

A high-resolution (up to 0.0018 cm⁻¹ unapodized) room temperature mid-infrared (650 to 750 cm⁻¹, 13.3 to 15.4 μm) absorption measurement of the ν₃ vibrational band of trifluoromethane (fluoroform, CHF₃, HFC-23) vapor was made with a Fourier transform spectrometer. A rovibrational analysis of over 1400 infrared transitions of the ν₃ band has yielded rotational constants, including sextic centrifugal distortion constants. The results are compared with two previous analyses of microwave and infrared spectra. The line positions of the lower J parts of the ν₃+ν₆−ν₆ and 2ν₃−ν₃ hot bands have been identified and constants obtained for the 2ν₃ state. The central Q branch and a few unblended transitions of the ν₃ band of ¹³CF₃H have been identified and the band origin has been determined. The relative intensities of the ν₃ band together with the 2ν₃−ν₃ hot band and ν₃ band of ¹³CF₃H have been calculated using the constants derived from this work.     

Multibody dynamics with unilateral constraints and friction

In the view of robotics or granular media mechanics, we ask for the statement of the dynamical evolution problem for multibody systems with contacts and friction. The “event driven” approach does not allow to state an evolution problem in a systematic way: it gives a peculiar status to the instants of impact and to the contact points although they are unknowns of the problem. This matter of fact has given rise to a new approach in the frictionless case [4, 6] we generalize to the case including friction. Following to the point of view of Lagrange on the equation of the dynamics, we emphasize the systematic use of virtual powers and duality. This bias suggests to put emphasis on generalized reaction forces in the statement of the evolution problem and not on local reaction forces of the real world. This point of view allows to escape from pathologies e.g. Painlevé paradox [5] and Kane Paradox [3]. The proposed evolution problem accounts for impacts and friction in case of multiple unilateral constraints. We prove the existence and uniqueness of the solution to the associated rate problem. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Atlas power-flow system-a status report

Atlas is a high-energy, pulsed-power facility under development to study materials properties and hydrodynamics under extreme conditions. Atlas will implode heavy liner loads (m ~ 45 gm) with a peak current of 27-32 MA delivered in 4 μs, and it is energized by 96, 240-kV Marx generators storing a total of 23 MJ. The power-flow system transports current from the Marx generators to the load. It includes a load protection switch to protect the load in case of a prefire; 24 oil-insulated, vertically oriented, radially converging, triplate transmission lines; a transition region that couples the transmission lines to the power-flow channel; and a radially converging, dielectric-insulated, horizontal and conical, power-flow channel. Proposed experiments, the design of the power-flow system, test results, and status are presented