Solute diffusion through degradable semicrystalline polyethylene glycol/poly(l-lactide) copolymers

Summary The diffusion of C.I. direct orange 34(MW=299) and benzoic acid(MW=122) through degraded semicrystalline polyethylene glycol(PEG)/poly(L-lactide)(PLLA) block copolymers with various PEG contents and PEG segment lengths at 37°C was studied by UV-visible spectroscopy, differential scanning calorimetry(DSC), wide angle X-ray diffractometer (WAXS) and scanning electron microscopy(SEM). The influences of the PEG contents, PEG segment lengths and hydrolytic degradation of PEG/PLLA copolymers on the solute diffusion coefficient and mode for transport were investigated. It is concluded that the diffusion rate increases with the increase of PEG contents and PEG segment lengths in PEG/PLLA copolymers. This is understandable that the increase of PEG content and PEG segment length both make the degree of crystallinity decrease. The steady state of mass flux could not be reached at the diffusion times up to 1000 h, because the copolymers underwent hydrolysis reaction during this period. Furthermore, it is understood that the characteristic time of diffusion as defined by the square of film thickness at an instant of time over the diffusion coefficient of solute through polymer decreases with the increasing diffusion time.     

Thermally reversible cross-linked polyamides and thermo-responsive gels by means of Diels-Alder reaction

Cross-linked polyamides and polyamide gels were prepared from maleimide-containing polyamides and a tri-functional furan compound and showed thermal reversibility in cross-linking behavior and in gel formation through Diels-Alder (DA) and retro-DA reactions. The rate constant k of the DA cross-linking reaction were 1.25-4.83×10⁻⁵ dm³ mol⁻¹ s⁻¹ in the temperature range of 20-60 °C with an activation energy of 32.1 kJ mol⁻¹. The cross-linking densities, thermal properties, and thermal reversibility of the polyamides/furan polymers were adjustable with the contents of maleimide groups in polyamides.     

Cure monitoring via different techniques: Isothermal cure of an epoxy-novolac molding compound

The isothermal cure of an epoxy-novolac molding compound was studied by means of Fourier-transform infrared spectroscopy (FTIR) and dielectrometry (DE). Results obtained were compared with previous differential scanning calorimetric (DSC) observations. The behavior of epoxide conversion (_FTIR) measured via FTIR was found similar to (but not exactly coinciding with) the extent of cure (_DSC) determined previously by means of DSC. As for the DE analysis, directly measurable properties such as permittivity () and loss factor () varied in a complicated manner during the course of cure, showing strong dependence on both temperature and frequency. Other dielectric parameters (such as ionic conductivity, relaxed permittivity, and characteristic relaxation time) previously suggested in the literature as suitable for cure monitoring purposes were found difficult to determine within the limited frequency range (10⁰ to 10⁴ Hz) here. With some arbitrariness, the relative drop in log (at 100 Hz) was taken as an index (_DE) for the extent of cure. It was observed that _DE behaves in a manner similar to _FTIR and _DSC Comments on the application of these three techniques in the characterization of thermosetting systems were given.     

Synthesis and kinetic studies of UV‐curable urethane‐acrylates

The UV‐curable urethane‐acrylates based on 2‐hydroxyethyl methacrylate (HEMA)‐terminated polyurethane (PU) for lithographic and coating applications are investigated in this study. Series of PU prepolymers were made from 4,4‐diphenyl methane diisocyanate (MDI), poly(propylene oxide) glycol (PPG 400), poly(butylene adipate)glycol (PBA 500), or poly(tetramethylene oxide) glycol (PTMO 1000) and are terminated with HEMA. The 2,2‐azobisisobutyronitrile (AIBN) was used as a UV‐initiator under air atmosphere. The curing kinetics of HEMA‐terminated PU film were studied. The curing analysis, using FTIR and reaction kinetics, indicate the reaction rate equation correlates well with the film thickness [T], initiator concentration [I], unreacted double bond concentration [C?C], and exposed energy [E] of the reaction system. The kinetic rate equation for the UV‐curable reaction can be written as © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3162–3166, 2004     

Morphology and characterization of conductive films based on polyaniline‐coated polystyrene latexes

The polyaniline (PANI)‐coated polystyrene (PS) latexes were synthesized, and the electrically conductive films were prepared thereafter. The weight ratio of PANI was 5%. Thermal analysis of the latices was performed using DSC and TGA. In this study, the electrically conductive films were prepared above the PS glass transition temperature (T_g). During the film formation, the effects of the annealing temperature and atmosphere (air or N₂) on the film resistance were investigated. In addition, the film morphology was observed utilizing scanning electron microscopy. The film resistance decreased in the initial heating stage due to the increasing temperature and the compaction of film. Then the film resistance increased with further annealing due to the aging of PANI. Typically, the film resistance was about 6000 Ω/sq, and the conductivity was 0.3 S/cm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5406–5413, 2006     

Surface modification and physical properties of various UHMWPE‐fiber‐reinforced modified epoxy composites

Two surface modification methods—plasma surface treatment and chemical agent treatment—were used to investigate their effects on the surface properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers. In the analyses, performed using electron spectroscopy for chemical analysis, changes in weight, and scanning electron microscope observations, demonstrated that the two fiber‐surface‐modified composites formed between UHMWPE fiber and epoxy matrix exhibited improved interfacial adhesion and slight improvements in tensile strengths, but notable decreases in elongation, relative to those properties of the composites reinforced with the untreated UHMWPE fibers. In addition, three kinds of epoxy resins—neat DGEBA, polyurethane‐crosslinked DGEBA, and BHHBP‐DGEBA—were used as resin matrices to examine the tensile and elongation properties of their UHMWPE fiber‐reinforced composites. From stress/strain measurements and scanning electron microscope observations, the resin matrix improved the tensile strength apparently, but did not affect the elongation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 655–665, 2007     

Influence of dietary long-chain PUFA on premature baboon lung FA and dipalmitoyl PC composition

One of the major survival challenges of premature birth is production of lung surfactant. The lipid component of surfactant, dipalmitoyl PC (DPPC), increases in concentration in the period before normal term birth via a net shift in FA composition away from unsaturates. We investigated the influence of dietary DHA and arachidonic acid (AA) on lung FA composition and DPPC concentration in term and preterm baboons. Pregnant animals/neonates were randomized to one of four groups: breast-fed (B), term formula-fed (T⁻), preterm formulafed (P⁻), and preterm fed formula supplemented with DHA-AA (P⁺). Breast milk contained 0.68%wt DHA and the P⁺ group formula contained 0.61%wt DHA. In the preterm groups (P⁻ and P⁺), pregnant females received a course of antenatal corticosteroids. At the adjusted age of 4 wk, neonate lung tissue was harvested, and FA composition and DPPC were analyzed. Palmitate was ∼28%wt of lung total FA and no significant differences were found among the four treatment groups. In contrast, DPPC in the B group lung tissue was significantly greater than DPPC in the unsupplemented groups, but not compared with the P⁺ group. The B and P⁺ groups were not significantly different in DHA and AA, but were different compared with the unsupplemented (T, P⁻) groups. These results indicate that LCP supplementation increases lung DHA and AA, without compromising overall lung 16∶0 or DPPC. The shift in FA composition toward greater unsaturation in the groups consuming LCP supported improved surfactant lipid concentration in preterm neonate lungs.     

Improvements in seismic event locations in a deep western U.S. coal mine using tomographic velocity models and an evolutionary search algorithm

Methods of improving seismic event locations were investigated as part of a research study aimed at reducing ground control safety hazards. Seismic event waveforms collected with a 23-station three-dimensional sensor array during longwall coal mining provide the data set used in the analyses. A spatially variable seismic velocity model is constructed using seismic event sources in a passive tomographic method. The resulting three-dimensional velocity model is used to relocate seismic event positions. An evolutionary optimization algorithm is implemented and used in both the velocity model development and in seeking improved event location solutions. Results obtained using the different velocity models are compared. The combination of the tomographic velocity model development and evolutionary search algorithm provides improvement to the event locations.     

Formation and Properties of Chalcogenide Glasses in the GeSe2–As2Se3–CdSe System

The glass-forming region in a GeSe₂–As₂Se₃–CdSe system and the dependence of properties on glass compositions as a formula of 70GeSe₂–(30− x )As₂Se₃– x CdSe ( x =0–25) were investigated. Measurements included density, micro-hardness, differential scanning calorimetry (DSC), X-ray diffraction, and IR transmission spectra. A large glass-forming region was shown while addition of Cd increases the crystallization trend of the system. Besides, the Cd content accommodated by the system to form glass is found to be lower in the As₂Se₃-rich region than in the GeSe₂-rich region. With the introduction of CdSe, density, micro-hardness, and T _g of glasses increase whereas an exothermal peak in the DSC curve appears and thermal stability (Δ T ) decreases. The activation energy of crystallization and the Avrami exponent were also obtained using the modified Ozawa equation.     

Kinetics and mechanism of ?-caprolactone and l,l-lactide polymerization coinitiated with zinc octoate or aluminum acetylacetonate: The next proofs for the general alkoxide mechanism and synthetic applications

Following our previous papers on mechanism of cyclic esters' polymerization coinitiated by tin(II) octoate [tin(II) bis-(2-ethylhexanoate), (Sn(Oct)₂)] in the presence of either the low molar mass coinitiator (an alcohol, hydroxy acid, or H₂O) or a macromolecule fitted with a hydroxy end group (ROH), the present work deals with ?-caprolactone (CL) and l,l-lactide (LA) polymerizations coinitiated with zinc octoate (Zn(Oct)₂) or aluminum acetylacetonate (Al(Acac)₃). A series of kinetic measurements revealed that similarly as in the Sn(Oct)₂ coinitiated process, these polymerizations proceed by simple monomer insertion into the …Mt-OR bond, reversibly formed in the reaction -Mt-L + ROH ? …-Mt-OR + LH (where Mt = Sn, Zn or Al; L = Oct or Acac), taking place throughout the whole polymerization process. MtL_n itself does not play an active role in the polymerization. Applicability of the commercially available Zn(Oct)₂ or Al(Acac)₃ for the aliphatic polyester (10³ ≤ M_n ≤ 4 × 10⁵) synthesis is also discussed.