The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Associative properties of perfluorooctyl end‐functionalized polystyrene–poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3‐tetrahydro‐perfluoroundecanoyl end‐functionalized polystyrene–poly(ethylene oxide) block (PS‐block‐PEO‐R_F) copolymers and their matching PS‐block‐PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and ¹⁹F NMR studies show that the PS‐block‐PEO copolymers, in contrast to their matching PS‐block‐PEO‐R_F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end‐functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS—and R_F—mediated micellization. Copyright © 2004 Society of Chemical Industry     

Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

Effect of exponentially graded base doping on the performance ofGaAs/AlGaAs heterojunction bipolar transistors

The authors have fabricated n-p-n GaAs/AlGaAs heterojunction bipolar transistors (HBTs) with base doping graded exponentially from 5×10¹⁹ cm^-3 at the emitter edge to 5×10¹⁸ cm^-3 at the collector edge. The built-in field due to the exponentially graded doping profile significantly reduces base transit time, despite bandgap narrowing associated with high base doping. Compared to devices with the same base thickness and uniform base doping of 1×10¹⁹ cm^-3 , the cutoff frequency is increased from 22 to 31 GHz and maximum frequency of oscillation is increased from 40 to 58 GHz. Exponentially graded base doping also results ill consistently higher common-emitter current gain than uniform base doping, even though the Gummel number is twice as high and the base resistance is reduced by 40%     

Effect of precyclic loading on stress-corrosion-cracking initiation in an X-65 pipeline steel exposed to near-neutral pH soil environment

A study was carried out to understand the effect of precyclic loading on stress-corrosion-crack initiation in an X-65 pipeline steel exposed to a near-neutral-pH soil environment. The test specimens were precyclically loaded before corrosion exposure to represent a service history of up to about 20 years, depending on the severity of pressure fluctuation. Microcracks had initiated on the polished surface of the X-65 pipeline steel after long-time exposure at open-circuit potential (OCP) in a near-neutral-pH synthetic soil solution. These microcracks were mostly initiated from pits at metallurgical discontinuities such as grain boundaries, pearlitic colonies, and banded phases in the steel. Strong preferential dissolution was observed along planes of the banded structures in the steel. The selective corrosion attack at these metallurgical discontinuities is attributed to the galvanic nature of those areas to their neighbors. Cyclic loading prior to corrosion exposure had significant effects on microcrack initiation and propagation during subsequent corrosion exposure. Cyclic loading prior to corrosion exposure either reduced or increased the probability of crack initiation and the rate of crack propagation, depending upon the magnitude of the stress cycles. The largest reduction was seen at a peak cyclic stress of about 0.8 of the yield strength. This cyclic-loading-dependent cracking behavior might be related to the alteration of the substructures and the residual stress in the steel as a result of precyclic loading.