The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si,as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.     

Investigation of the “Surface” and “Interphase” Composition of Adhesion Promoter/Thermoplastic Olefin Systems: The Effect of Adhesion Promoter Bake Temperature

The interfacial chemistry of model systems consisting of two adhesion promoting primers and a single Thermoplastic Olefin (TPO) substrate was examined. Two commercial adhesion promoter (AP) materials were applied to a commercially-available TPO material and either flash dried at room temperature or baked at 100°C. The surface composition of the AP films and TPO substrate, and the interfacial compositions of the AP/TPO systems were characterized using x-ray photoelectron spectroscopy (XPS). The AP films studied were based upon a chlorinated polyolefin (CPO). For one adhesion promoter film (AP-1), no chlorine was present at the surface suggesting a nonhomogeneous system. For the second adhesion promoter film (AP-2), the surface composition was about 15% CPO and 85% AP matrix. No changes in AP surface composition were evident for the different bake conditions for either AP. Interfacial compositions of the room temperature flashed materials were found to be very similar for both AP/TPO systems, with CPO being present for each and at similar concentrations. Interfacial compositions for the baked materials were also similar for the two systems, although the level of CPO at the interface increased for both the AP-1 and AP-2 relative to the unbaked materials. The relative increases observed were 46% and 41% for the AP-1 and AP-2 systems, respectively. The increase in the relative concentration of CPO at the interface with bake temperature suggests that there is a stronger interaction between the AP and TPO. The implication of these data is that a baked AP should result in a more robust paint system with respect to AP/TPO adhesion.     

Characterization of hydrogels prepared by the γ irradiation of aqueous solutions of acrylamide and N‐vinyl‐2‐pyrrolidone comonomers

Copolymer hydrogels were prepared through the γ irradiation of aqueous solutions composed of different ratios of acrylamide (AAm) and vinyl pyrrolidone (VP) monomers. The chemical structure, thermal stability, and structural morphology of the hydrogels were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy, respectively. The IR spectroscopy analysis showed the formation of copolymerization and the presence of hydrogen bonding. The TGA study showed that the AAm/VP‐based hydrogels possessed higher thermal stability than polyacrylamide (PAAm). However, the thermal stability of the AAm/VP hydrogels increased with an increasing ratio of the VP component. The study of the swelling kinetics in water showed that all the hydrogels reached the equilibrium state after 24 h. However, the AAm/VP‐based hydrogels showed swelling in water that was lower than that of the hydrogel based on pure AAm. Meanwhile, the degree of swelling of the AAm/VP‐based hydrogels decreased with an increasing ratio of VP in the feeding solutions. The results showed that the PAAm and AAm/VP‐based hydrogels prepared at 50 kGy were affected by a change in the temperature around 25°C, whereas the hydrogels prepared at 25 kGy did not show this characteristic. However, the hydrogels prepared at different doses displayed reversible pH character. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Kinetic study by FTIR,TMA, and DSC of the curing of a mixture of DGEBA resin and γ‐butyrolactone catalyzed by ytterbium triflate

A mixture of diglycidylether of bisphenol A (DGEBA) and γ‐butyrolactone (γ‐BL) was cured in the presence of ytterbium triflate as a catalyst. The kinetics of the various elemental processes that occur in the curing process were studied by means of isothermal curing in the FTIR spectrometer. The kinetics of the contraction during the curing was also evaluated by TMA. In both cases, the kinetics was analyzed by means of isoconversional procedure and the kinetic model was determined with the so‐called compensation effect (isokinetic relationship). The isothermal kinetic analysis was compared with that obtained by dynamic curing in DSC. We found that all the reactive processes and the contraction follow a surface‐controlled reaction type of kinetic mechanism, R₃. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 381–393, 2004     

The influence of the draw ratio of melt-spun polyethylene fibres on γ-irradiation induced effects as observed by ESR

The influence of draw ratio on free radical behaviour in melt-spun polyethylene fibres has been examined using ESR spectroscopy. The stability of free radicals produced by γ-irradiation is greatest some where between draw ratio 1 and 10. The general trend of radical stability has been found to correlate with the trend of gel content with draw ratio. The possible link between the extent of crosslinking and the production of stable radicals has been discussed in terms of morphological aspects.     

Synthesis and characterization of copolymeric aliphatic–aromatic esters derived from terephthalic acid, 1,4‐butanediol,and ε‐caprolactone by physical,thermal, and mechanical properties and NMR measurements

In this study, a series of aliphatic–aromatic poly(butylene terephthalate‐co‐ε‐caprolactone) (PBTCL) copolyesters were synthesized from various monomeric compositions of terephthalic acid (TPA), 1,4‐butanediol (BDO), and ε‐caprolactone (CL) in the presence of tetrabutyl titanate (Ti(Obu)₄) and stannous octoate (Sn(Oct)₂) as catalysts through a combination of polycondensation and ring opening polymerization. A significant increase in the melting temperature (T_m) of copolyesters was observed by increasing the TPA/(CL+TPA) molar ratio, starting from the low end (T_m 66.2°C) of pure poly‐ε‐caprolactone PCL upward. We found that PBTCL‐50, which has a TPA/(CL+TPA) 50% molar ratio and polycondensation at 260°C for 1.5 h, resulted in a proper T_m of 139.2°C that facilitates thermal extrusion from biomass or other biodegradable polymers of similar T_m. The number–average molecular weight (M_n) of 7.4 × 10⁴ for PBTCL‐50 was determined from the intrinsic viscosity [η] by using the Berkowitz model of M_n = 1.66 × 10⁵[η]^0.9. Good mechanical properties of PBTCL‐50 have been shown by tensile stretching experiment that indicates tensile strength, elongation, and Young's modulus are 11.9 MPa, 132%, and 257 MPa, respectively. Polymers with aforementioned properties are suitable for manufacturing biodegradable plastic films for downstream agricultural applications or merely for trash bag. This article reveals that the PBTCL‐50 contains all five monomers with different molar ratios and characteristical linkages between each other. The novel structure was furthermore analyzed by ¹H‐ and ¹³C‐NMR spectroscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013