Effect of ionic content,solid content,degree of neutralization,and chain extension on aqueous polyurethane dispersions prepared by prepolymer method

There are many variables in the preparation of aqueous polyurethane (PU) dispersions. Carboxylic acid content, solid content, degree of pre/postneutralization of the carboxylic acids, and chain extension all impact dispersion particle size, viscosity, pH, molecular weights, and glass transition temperature. This study evaluated the impact of these variables on a given PU dispersion formulation prepared from isophorone diisocyanate, an aliphatic polyester polyol, dimethylol propionic acid, and hexamethylene diamine with triethyl amine as the neutralizing base and N‐methyl pyrrolidone as the cosolvent. Changes in carboxylic acid content, degree of preneutralization, and chain extension were found to have the expected impacts on dispersions properties. Increased ionic content in the dispersion step led to lower particle size and higher viscosity, increased chain extension with its concurrent increase in molecular improved subsequent film properties. Surprising results were obtained by varying the amount of postneutralization and from increased solids content at the time of dispersion. Unexpectedly, both of these variations led to much higher dispersion viscosities and particle size in solution. To have these changes take place, it is theorized that there is a major change in solution morphology caused by these modifications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2514–2520, 2005     

Dynamic vulcanisation of EPDM/PE-based thermoplastic vulcanisates studied along the extruder axis

Simple blending and dynamic vulcanisation of EPDM/PE blends using the resol/SnCl₂ system was studied in an extruder using a series of sampling devices. The melting of the PE pellets occurs just in front of and in the first kneading zone. Upon complete melting of the PE phase, the EPDM/PE blends reach very quickly their final morphology. Crosslinking of the EPDM phase to high levels occurs already when the PE phase is not yet fully molten. The higher the EPDM content, the higher the viscous dissipation, the higher the melt temperature and, consequently, the higher the crosslinking rate. For the EPDM/PE (50/50; w/w) TPV a transition from continuous via co-continuous to fully dispersed EPDM is observed, which is driven by crosslinking. Although the degree of crosslinking of the EPDM rubber is very high, this does not prevent phase inversion of the blend. The EPDM/PE interface is rather blurred, because PE crystalline lamellae are growing into the EPDM domains, probably because of the high compatibility between PE and EPDM (60 wt% of ethene). This study shows that dynamic vulcanisation in extruders proceeds quite differently from that in batch kneaders, where melting, mixing and crosslinking are separated in time. In extruders mass and heat transport, melting of the thermoplastic, morphology development (including dispersion and phase inversion), distribution and dissolution of (crosslinking) chemicals and crosslinking of the rubber do not occur as independent phenomena, but mutually and/or continuously interact.     

Fast determination of critical eluent composition for polymers by gradient chromatography

Gradient chromatography was applied in order to calculate the composition at elution for different methacrylates on normal phase columns. In addition the composition at elution was determined for polyethyleneoxide on a reverse phase column. It is shown that high molar mass polymers elute for a given homopolymer irrespective of their molar mass at the same eluent composition, which varies only slightly with gradient slope. In general the composition at elution in gradient chromatography is expected to be slightly lower than the true critical composition. For high molar mass polymers we found this composition to be close to the critical composition determined by isocratic experiments. The difference between the composition at elution and the true critical composition for a variety of polymethacrylates and for polyethyleneglycol was found to be only between 0.2 and 5%. Thus, after estimating the composition at elution, only a small number of additional isocratic experiments is needed to find the exact critical composition.     

A Monte Carlo simulation study of the mechanical and conformational properties of networks of helical polymers. I. General concepts

We study the mechanical and conformational properties of networks of helical polymers with a combination of Monte Carlo simulations based on the Wang-Landau algorithm and the three-chain model. We find that the stress-strain behavior of these networks has novel features not observed in typical networks made of synthetic polymers. In particular, we find that as these networks are stretched they first strengthen, then soften and finally strengthen again. This non-monotonic behavior of the stress correlates with the one of the helical content and is rationalized by the elongation-induced formation and melting of the helical structure of the polymer. We complement these results with a study of other conformational properties of the polymer strands that clarify the molecular mechanisms behind the mechanical behavior of these networks. Finally, we present a qualitative comparison of some of our results with the theoretical ones recently reported by Kutter and Terentjev.     

High Pressure Conductivity and Photoconductivity of Polyveratrole

Summary Electropolymerization of o-(CH₃O)₂C₆H₄ (Veratrole) in dry acetonitrile/tetrabutylammonium tetrafluoroborate at platinum electrode, yields a green polymeric conducting solid. As the pressure is increased, the material becomes more conductive, but sharp changes towards lower conductivity occur at 4.2 and 6.2 metric tons pressure, probably due to phase transitions. The photoconductivity shows an exponential increase as temperature is increased, but it shows reversible changes at 200 K, 225 K and 250 K during slow warming, also attributable to phase transitions. Photoconductivity of Polyveratrole increases with the radiation frequency, being higher under blue light than under red of infrared radiation and there is a linear increase of photoconductivity with radiation density. Conductivity transients show that the conductivity increases exponentially with time to the saturation point within few minutes, and it also decreases exponentially when the light is turned off and the circuit is open. This behaviour can be explained by formation and encounter of electron and hole as current carriers. A preliminary study indicates a piezoelectric effect for the material. absorption spectroscopy allowed the measurements of the material band gap.     

The effect of plastic deformation on Al2CuLi (T 1) precipitation

The enhancement ofT ₁ precipitation in Al-Li-Cu alloys by plastic deformation prior to aging (that is, cold work) and the subsequent increase in alloy strength is investigated. The increased understanding of the role of matrix dislocations in the nucleation and growth ofT ₁ plates, discussed in the previous paper,^[1] permits a detailed study of the phenomenon. In this paper, the effect of different levels of plastic strain on theT ₁ particle distributions as a function of aging time at 190 °C is quantified, and the subsequent influence on tensile properties is thereby described. The effect of plastic deformation is shown to decrease theT ₁ plate length and thickness, increase the number density by almost two orders of magnitude, increase the yield strength by 100 MPa, while simultaneously reaching peak strength in 20 pct of the time required without plastic deformation. Formerly Graduate Student, Department of Materials Science, University of Virginia,     

Construction and performance of a multiparameter focal plane detector for use on a QMG/2 magnetic spectrometer

The design, construction and performance of a modular, two pressure focal plane detector, 550 mm long, 1000 mm deep and with an active height of 60 mm are described. The detector has been operated with ions ranging from 50 MeV ¹H to 200 MeV ³⁶S. Typical results achieved are 0.5 mm and 0.3° for the spatial and angular resolutions, and 0.7% and 3% for the total energy and energy loss measurements. A height signal is also provided.