Thermal stabilities of end groups in hydroxyalkyl terminated polydimethylsiloxane oligomers

Summary Thermal stabilities of α,ω-hydroxypropyl, α,ω-hydroxybutyl, α,ω-2-hydroxypentyl and α,ω-hydroxyhexyl terminated polydimethylsiloxane (PDMS) oligomers were studied. Hydroxypropyl and hydroxybutyl terminated polydimethylsiloxane oligomers showed degradation upon heating, through the loss of functional end groups as determined by FT-IR spectroscopy and gel permeation chromatography. α,ω-Hydroxyhexyl and α,ω-2-hydroxypentyl terminated polydimethylsiloxane oligomers were stable under similar conditions. Instability of the end groups is due to the back biting of the terminal silicon in the PDMS by the primary hydroxyl oxygen, leading to the formation of 5 and 6 membered, stable, heterocylic compounds. Loss of end groups also resulted in a dramatic increase in the molecular weights of the oligomers produced, as determined by gel permeation chromatography. Received: 19 January 1998/Revised version: 27 February 1998/Accepted: 5 March 1998     

Steady‐state analysis of a novel ZVT interleaved boost converter

In this paper, a novel soft‐switched interleaved boost converter composed of two‐cell boost conversion units and an auxiliary circuit is proposed and investigated. The proposed auxiliary circuit is implemented using only one auxiliary switch and a minimum number of passive components without an effective increase in the cost and the complexity of the converter. The main advantage of this auxiliary circuit is that it not only provides zero‐voltage‐transition (ZVT) for the main switches but also provides soft switching for the auxiliary switch and diodes. Though all semiconductor devices operate under soft switching, they do not have any additional voltage and current stresses. The proposed converter operates successfully in soft‐switching operation mode for a wide range of input voltage level and the load. In addition, it has advantages such as fewer structure complications, lower cost and ease of control. Since the two‐cell interleaved boost units are identical, operational analysis and design for the converter module become quite simple. In this study, the detailed steady‐state theoretical analysis of the proposed converter is presented, which is verified exactly by simulation and experiments carried out on a prototype of a 120 W and 50 kHz/cell interleaved boost converter. The practical results confirm the results obtained from theoretical analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Novel supercritical fluid techniques for polymer fractionation and purification

Summary , -carboxypropyl terminated polydimethylsiloxane oligomers (PSX) having molecular weights (Mn) of 2000 and 6400 g/mole respectively were fractionated by using supercritical carbon dioxide. Parent materials and the fractions were characterized by FT-IR spectroscopy, end group titrations and GPC. Polydispersity of each fraction was determined from the analysis of GPC curves. A calibration curve was also plotted by using Mn values from titration and peak elution volumes from GPC. Even without process optimization we were able to obtain fractions having (Mw/Mn) values between 1.1 and 1.3 compared to the parent materials (PSX-2000 and PSX-6400) which showed polydispersities of 1.6 and 2.1 respectively. The ability to prepare such narrow fractions should be of considerable interest both for academic studies as well as for polymeric biomaterials.     

Evaluating Missile Fuels

This paper presents simple and relatively efficient methods to estimate some physical and chemical properties of polycyclic alkanes. These properties are melting point, normal boiling point, standard enthalpy of vaporization at 298 K, standard enthalpy of formation at 298 K, standard enthalpy of combustion at 298 K, density (specific gravity) and flash point. These methods are validated, despite the scarcity of experimental data, with several tens of polycyclic alkanes. Then the methods are used to estimate properties of some polycyclic alkanes, which are currently in use as missile fuels: JP‐10, RJ‐4 and RJ‐5. Estimates and experimental data are found in good agreement for these fuels. This methodology is then used to evaluate missile fuel candidates to be used pure or as additive to JP‐10 or to blends such as RJ‐6. Several compounds are probably of interest for this task and their advantages and drawbacks are discussed.     

Fumed silica filled poly(dimethylsiloxane-urea) segmented copolymers: Preparation and properties

Novel fumed silica filled thermoplastic poly(dimethylsiloxane-urea) (TPSU) segmented copolymers were synthesized and characterized. TPSU copolymers were prepared from a cycloaliphatic diisocyanate, aminopropyl terminated PDMS oligomers with number average molecular weights of 3,200, 10,800 and 31,500 g/mol and 2-methyl-1,5-diaminopentane chain extender. Two different types of fumed silica HDK H2000 (hydrophobic) and HDK N20 (hydrophilic) were utilized and incorporated into silicone-urea copolymers in amounts of 1-60% by weight. Influence of the silica type (hydrophilic versus hydrophobic), amount of silica loading and the PDMS soft segment molecular weight on the morphology, tensile properties and modulus-temperature behavior of the nanocomposites were determined. Major observations of this study were: (i) under the blending conditions used, incorporation of silica does not seem to interfere significantly with the hydrogen bonding between urea groups, (ii) incorporation of silica does not affect the glass transition temperature of PDMS, (iii) incorporation of silica influences the tensile and thermomechanical properties of silicone-urea segmented copolymers significantly, (iv) average molecular weight of the PDMS soft segment in the silicone-urea copolymer plays a critical role on the improvement of the tensile properties of the fumed silica/TPSU composites.     

Rheology and extrusion of medical‐grade thermoplastic polyurethane

The selection of operating conditions and geometry for the processing of thermoplastic polyurethane, TPU, is a complicated task. This complication arises from the relatively high melting temperature of the crystalline hard blocks and the oxidative and thermal degradation and crosslinking that occur at temperatures that are relatively close to the melting temperature of the TPU. This article documents the rheology, extrusion, and structure development of a medical‐grade TPU. The medical application requires that the additives commonly utilized in the development of polymeric resins, i.e., stabilizers, antioxidants, and lubricant, should be minimized; the TPU of this study contains no additives. At temperatures 10–20°C lower than the melting temperature of the TPU, the morphology of the hard blocks continues to evolve to generate a reversible increase in elasticity and shear viscosity of the TPU with increasing time. At temperatures greater than the melting temperature, the TPU undergoes degradation and crosslinking reactions, which give rise to a permanent increase in the elasticity and the shear viscosity of the TPU. The ramifications of the degradation and crosslinking at temperatures greater than 200°C and morphology modification upon the continuing evolution of the hard blocks at temperatures less than 200°C on the rheology and processing were investigated.     

Understanding the influence of hydrogen bonding and diisocyanate symmetry on the morphology and properties of segmented polyurethanes and polyureas: Computational and experimental study

Quantum mechanical calculations (QMC) and dissipative particle dynamics (DPD) simulations were utilized to understand the nature of the short and long-range hydrogen bonding and its influence on the microphase morphology in segmented polyurethanes and segmented polyureas prepared without chain extenders through the stoichiometric reactions of hydroxy or amine terminated poly(tetramethylene oxide) (PTMO-1000) with 1,4-phenylene diisocyanate (PPDI) and 1,3-phenylene diisocyanate (MPDI). The possibility of long-range connectivity due to a network of well-ordered hydrogen bonds between symmetrical PPDI and kinked MPDI based model urethane and urea compounds were also investigated. Special emphasis was given on the understanding of the influence of diisocyanate symmetry and nature of the hydrogen bonding between hard segments on the morphology development. QMC results obtained clearly indicated the possibility of long-range ordering of hydrogen bonds between PPDI based urethane and urea groups, while MPDI based systems did not display such a behavior. DPD results strongly supported the QMC studies and clearly demonstrated the possibility of long-range connectivity of hydrogen bonds between urethane and urea groups in PPDI based segmented copolymers, leading to the formation of microphase separated morphologies in these systems, which was not observed in the kinked MPDI based segmented urethane and urea copolymers. Computational results obtained strongly supported the experimental observations reported on the morphology and thermal and mechanical properties of these segmented polyurethanes and polyureas based on PPDI and MPDI.     

Measurements and model calculations of activation cross sections for 232Th(n,2n)231Th reaction between 13.57 and 14.83 MeV neutrons

In this study, activation cross sections were measured for the reaction of ²³²Th(n,2n)²³¹Th (T_1/2 = 25.5 h) by using neutron activation technique at six different neutron energies from 13.57 and 14.83 MeV. Neutrons were produced via the ³H(²H,n)⁴He reaction using SAMES T-400 neutron generator. Irradiated and activated high purity Thorium foils were measured by a high-resolution γ-ray spectrometer with a high-purity Germanium (HpGe) detector. In cross section measurements, the corrections were made for the effects of γ-ray self-absorption in the foils, dead-time, coincidence summing, fluctuation of neutron flux, low energy neutrons. For this reaction, statistical model calculation, which the pre-equilibrium emission effects were taken into consideration, were also performed between 13.57 and 14.83 MeV energy range. The cross sections were compared with previous works in literature, with model calculation results, and with evaluation data bases (ENDF/B-VII, ENDF/B-VI, JEFF-3.1, JENDL-4.0, JENDL-3.3, and ROSFOND-2010).