Kinetic Monte-Carlo simulation of network formation

Summary the simulation described in Part I was applied to random step polyaddition of a trifunctional monomer and the results were compared with exact solution for an infinite system. The gel point conversions, the weight-average degree of polymerization before (P _w) and beyond (P _w,sol) the gel point, the sol fraction and the cycle rank were used for comparison. The best way for detection of the gel point conversion is the extrapolation of the gel fraction, w _g, to w _g=0. The largest fluctuations are exhibited by P _w and P _w,sol. To get results closer to the exact ones, one can repeat several experiments with smaller number of units or increase the number of units, the former way being somewhat more economical. Typical orders of magnitude used were 10⁷ monomeric units.     

Colour constancy of vat prints on cotton fabrics

Colour constancy of prints with vat dyes on cotton fabrics was investigated by computing the CMCCON02 colour inconstancy index with the key element CAT02 for chromatic adaptation transform. The results show that the highest changes in colour appearance can be expected when the average daylight is replaced with fluorescent light. If D65 daylight is replaced with some other type of daylight, such as D50 or D55, only minor colour deviations occur which do not substantially change the colour appearance of the prints. The analysis of the influence of the lightness and chromaticity of prints shows that the chromaticity of the samples significantly affects their colour constancy. The change of appearance of the prints with lower chroma because of changed illumination conditions is less probable. The influence of a dye blend composition was also investigated. On average, multi‐coloured dye blends have proved to be more colour constant.     

Multiscale approach to the morphology,structure, and segmental dynamics of complex degradable aliphatic polyurethanes

A multiscale approach spanning from the segmental (subnanometer) up to micrometer level was applied for detailed study of the self‐assembly of aliphatic block polyurethane (PU) elastomers. To understand the principles of the self‐organization of hard and soft segments in the complex multi‐component systems, several two‐component model PU samples, that is, the products of 1,6‐diisocyanatohexane (HDI) with three diols differing in the length and constitution were also prepared, characterized, and investigated: (i) polycarbonate‐based macrodiol (MD), (ii) biodegradable oligomeric diol (DL‐L; product of butane‐1,4‐diol and D,L‐lactide), and (iii) butane‐1,4‐diol (BD). The study (particularly ¹³C‐¹H PILGRIM NMR spectra) reveals complex internal organization and interesting (application appealing) behavior of multi‐component PUs. Hard segments (HDI+BD products) feature self‐assembled and significantly folded chain conformations with interdomain spacing 15–22 nm (small‐angle X‐ray scattering analysis). The small domains are hierarchically assembled in various structural formations of µm size (spherulites) depending on PU composition, as detected by transmission electron microscopy and atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41590.     

Nanolayer CrAlN/TiSiN coating designed for tribological applications

With the goal to produce a hard and tough coating intended for tribological applications, CrAlN/TiSiN nanolayer coating was prepared by alternative deposition of CrAlN and TiSiN layers. In the first part of the article, a detailed study of phase composition, microstructure, and layer structure of CrAlN/TiSiN coating is presented. In the second part, its mechanical properties, fracture and tribological behavior are compared to the nanocomposite TiSiN coating. An industrial magnetron sputtering unit was used for coating deposition. X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used for compositional and microstructural analysis. Mechanical properties and fracture behavior were studied by instrumented indentation and focused ion beam techniques. Tribological properties were evaluated by ball-on-disk test in a linear reciprocal mode. A complex layer structure was found in the nanolayer coating. The TiSiN layers were epitaxially stabilized inside the coating which led to formation of dislocations at interfaces, to introduction of disturbances in the coating growth, and as a result, to development of fine-grained columnar microstructure. Indentation load required for the onset of fracture was twice lower for the nanolayer CrAlN/TiSiN, compared to the nanocomposite TiSiN coating. This agrees very well with their mechanical properties, with H³/E² being twice higher for the TiSiN coating. However, the nanolayer coating experienced less severe damage, which had a strong impact on tribological behavior. A magnitude of order lower wear rate and four times lower steady state friction coefficient were found for the nanolayer coating.     

POLYCYCLIC AROMATIC HYDROCARBONS IN PRODUCTS OF A BEET SUGAR FACTORY IN VOJVODINA: LEVELS AND INTAKES

The levels of 16 EPA polycyclic aromatic hydrocarbons (PAHs) were investigated in samples of sugar beets and their products representative for a beet sugar factory located in the central part of Vojvodina, the main agricultural region in Serbia. The sum of the detected PAHs ranged from 51 pg g ^?1 ww for molasses to 391 pg g ^?1 ww for dried sugar beet pulp. The concentration of benzo(a)pyrene (BaP) for all sample types was about or less than 100 pg g ^?1 ww, which is far less than the existing Serbian and EU tolerances set for some foodstuffs. The Serbian intake of BaP via total sugar consumption that ranged from 70–85 g per capita day ^?1 , was assessed to be from 0.029 to 0.035 ng kg ^?1 b.w. day ^?1 . Furthermore, the toxic equivalency factor (TEF) approach was used to estimate the carcinogenicity of PAH mixture found in analyzed samples.     

Thermal behavior of mullite between 4 K and 1320 K

The evolution of metric parameters of 2:1 and 3:2 mullites have been measured between 4 K and 1320 K using neutron and X‐ray powder diffraction. Negative thermal expansion was observed at low temperature for the a‐cell parameter and consequently for the cell‐volume, which is more pronounced for 2:1 mullite than those for 3:2 mullite. Each parameter is simulated using Grüneisen first‐order approximation for the zero pressure equation of state at 0 K, where the vibrational energy was calculated using microscopic approach. While the b‐ and c‐cell parameters require only one Debye term, a second Debye spectrum with negative Grüneisen parameter was required to fit the a‐cell parameter as well as the cell volume. At 4 K, 300 K and 1320 K the model, respectively, calculates the volume thermal expansion coefficients of 0.09x10^?6 K^?1, 9x10^?6 K^?1, and 17.3x10^?6 K^?1 for 2:1 mullite, and 0.09x10^?6 K^?1, 8.7x10^?6 K^?1, and 17.3x10^?6 K^?1 for 3:2 mullite. Temperature‐dependent Raman spectra and phonon density of states hint for the possible microscopic sources of the cell contraction at low temperature. A simple polynomial approach is presented to calculate the elastic stiffness coefficients of the 3:2 mullite, which are not available from experiments.     

Corrosion of NiTi Wires with Cracked Oxide Layer

Corrosion behavior of superelastic NiTi shape memory alloy wires with cracked TiO₂ surface oxide layers was investigated by electrochemical corrosion tests (Electrochemical Impedance Spectroscopy, Open Circuit Potential, and Potentiodynamic Polarization) on wires bent into U-shapes of various bending radii. Cracks within the oxide on the surface of the bent wires were observed by FIB–SEM and TEM methods. The density and width of the surface oxide cracks dramatically increase with decreasing bending radius. The results of electrochemical experiments consistently show that corrosion properties of NiTi wires with cracked oxide layers (static load keeps the cracks opened) are inferior compared to the corrosion properties of the straight NiTi wires covered by virgin uncracked oxides. Out of the three methods employed, the Electrochemical Impedance Spectroscopy seems to be the most appropriate test for the electrochemical characterization of the cracked oxide layers, since the impedance curves (Nyquist plot) of differently bent NiTi wires can be associated with increasing state of the surface cracking and since the NiTi wires are exposed to similar conditions as the surfaces of NiTi implants in human body. On the other hand, the potentiodynamic polarization test accelerates the corrosion processes and provides clear evidence that the corrosion resistance of bent superelastic NiTi wires degrades with oxide cracking.