Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

Epoxy based coatings on glass: strengthening mechanisms

Glass may be strengthened by epoxy coatings although the strengthening mechanisms remain unclear. Possible strengthening mechanisms are reviewed and are used to analyse strength data for both a solvent based and a water based coating system. The coatings either fill (solvent based coatings), or partially fill (water based coatings) surface cracks and it is shown that closure stresses arising from the thermal expansion mismatch of the coating within these cracks can account for the observed degrees of strengthening. It is also demonstrated that other suggested mechanisms such as flaw healing cannot fully account for the observed degree of strengthening.     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Crack path instabilities in DCDC experiments in the low speed regime

We studied the low speed fracture regime (10⁻⁴-10⁻⁹ m s⁻¹) in different glassy materials (soda-lime glass, glass ceramics) with variable but controlled length scale of heterogeneity. The chosen mechanical system enabled us to work in pure mode I (tensile) and at a fixed load on double cleavage drilled compression specimen. The internal residual stresses of studied samples were carefully relaxed by appropriate thermal treatment. By means of optical and atomic force microscopy techniques fracture surfaces have been examined. We have shown for the first time that the crack front line underwent an out-of-plane oscillating behavior as a result of a reproducible sequence of instabilities. The wavelength of such a phenomenon is in the micrometer range and its amplitude in the nanometer range. These features were observed for different glassy materials providing that a typical length scale characterizing internal heterogeneities was lower than a threshold limit estimated to few nanometers. This effect is the first clear experimental evidence of crack path instabilities in the low speed regime in a uniaxial loading experiment. This phenomenon has been interpreted by referring to the stability criterion for a straight crack propagation as presented by Adda-Bedia et al. [Phys. Rev. Lett. 76 (1996) 1497].     

A study of the atmospheric lead pollution in Seville, Spain. Influence of meteorology and traffic, and relationship with other traffic-generated pollutants

A study of the atmospheric pollution by suspended particulate lead in the city of Seville, Spain, was carried out during the period between March 1983 and February 1984. The results obtained from seven sampling stations allowed us to study the site to site variations; there are two locations with average annual concentrations higher than 2 micrograms X m-3. In one station, the meteorological and traffic effects and relationship with other traffic-related pollutants, were investigated. The regression analyses performed on the average monthly data have shown an inverse correlation with wind speed and temperature and a direct correlation with carbon monoxide and smoke concentrations, but no significant correlation was found with the lead deposition levels.     

Homogeneous renewal equation

Let F be a non-arithmetic distribution on the line , and W be the class of bounded functions w without discontinuity of the second kind such that

.In this paper, we show that the solution of the homogeneous renewal equation w = w F in the class W is a constant-function.     

Kinetics of Hydrogen Peroxide Decomposition in Guaiacol Solution, Catalyzed by Hexacyanoferrate(II)

The kinetics of hydrogen peroxide decomposition in a guaiacol solution, catalyzed by potassium hexacyanoferrate(II), were studied. The reaction mainly follows the pathway of guaiacol hydroxylation. The reaction order is 1 with respect to H₂O₂, 0.5 with respect to hexacyanoferrate, and from 0.4 to 0 with respect to guaiacol (the latter parameter decreases with increasing guaiacol concentration). The apparent activation energy is 105 kJ mol^{- 1}. A kinetic scheme of the process was proposed. An expression consistent with the experiment was obtained for the rate of hydrogen peroxide decomposition in the presence of guaiacol, catalyzed by hexacyanoferrate(II).