Thermal conductivity of poly(vinyl chloride)/polycaprolactone blends

Thermal diffusivity, heat capacity, and density of polyvinyl chloride/polycaprolactone (PVC/PCL) blends were measured by the laser flash method, DSC, and pycnometry, respectively. The thermal conductivity of the PVC/PCL blends was determined from the results. The miscibility of the blend and crystallinity of PCL were determined by DSC. The effect of blend structure on thermal conductivity is discussed. The phase compositions of the PVC/PCL blends are of three types depending on PCL content: i.e., up to 33%, from 33 to 70%, and above 70% PCL by weight. Thermal conductivity, thermal diffusivity, and heat capacity of the PVC/PCL blends are strongly affected by the phase composition of the blend, which changes in a complicated way with PCL content. © 1994 John Wiley & Sons, Inc.     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

A note on an SOR-like method for augmented systems

Golub et al. (2001, BIT, 41, 71–85) gave a generalizedsuccessive over-relaxation method for the augmented systems.In this paper, the connection between the SOR-like method andthe preconditioned conjugate gradient (PCG) method for the augmentedsystems is investigated. It is shown that the PCG method isat least as accurate (fast) as the SOR-like method. Numericalexamples demonstrate that the PCG method is much faster thanthe SOR-like method.     

Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Novel ethero atoms containing polyesters based on 2,6‐naphthalendicarboxylic acid: A comparative study with poly(butylene naphthalate)

Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the T_g value, a decrement of T_m, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

Motion Control by ZV Shaper Synthesis Extended for Fractional Systems and Its Application to CRONE Control

Shaping command input or preshaping is used for reducing system oscillation in motion control. Desired systems inputs are altered so that the system finishes the requested move without residual oscillation. This technique, developed by N.C. Singer and W.P. Seering, is used for example in the aerospace field, in particular in flexible structure control. This paper presents the study of ZV shaper for explicit fractional derivative systems (generalized derivative systems). A robustness study of ZV shaper is then presented and applied to improve second generation CRONE control response time. Results from simulation and from a DC motor bench are also given.     

Preparation,thermal properties,and flame retardance of epoxy–silica hybrid resins

A novel epoxy system was developed through the in situ curing of bisphenol A type epoxy and 4,4′‐diaminodiphenylmethane with the sol–gel reaction of a phosphorus‐containing trimethoxysilane (DOPO–GPTMS), which was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) with 3‐glycidoxypropyltrimethoxysilane (GPTMS). The preparation of DOPO–GPTMS was confirmed with Fourier transform infrared, ¹H and ³¹P NMR, and elemental analysis. The resulting organic–inorganic hybrid epoxy resins exhibited a high glass‐transition temperature (167 °C), good thermal stability over 320 °C, and a high limited oxygen index of 28.5. The synergism of phosphorus and silicon on flame retardance was observed. Moreover, the kinetics of the thermal oxidative degradation of the hybrid epoxy resins were studied. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2354–2367, 2003     

Integrable Deformations of Tops Related to the Algebra so(p,q)

We propose an integrable deformation of the known model of two interacting tops on the algebra so(p,q). We consider particular cases including the generalized Lagrange and Kovalevskaya tops. We construct the Lax matrices and the corresponding classical R-matrices.     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003