Photo-polymerisation of composite resins measured by micro-Raman spectroscopy

The micro-Raman spectroscopy was used for measuring the photo-polymerisation of composite resins. The elevated spatial resolution of the technique revealed surface non-homogeneities via the intensity variations of a strong band at 1400 cm⁻¹ and the presence of weak bands around the CC and CO stretching frequencies. Values of the degree of monomer conversion (DC) were determined for samples of Z100 commercial composite irradiated with different wavelength laser beams. Two methods were used for obtaining DC values. The first one exploits band decompositions in the spectral region of interest around 1608 and 1637 cm⁻¹. The non-uniqueness of the decomposition introduces relevant uncertainties, which are amplified by unwanted weak bands. An alternative method, avoiding any fit procedure and exploiting the band shape conservation under irradiation, was found producing more reliable results. The 632 nm line of the He-Ne laser was used as an exciting source. The measurements of the DC versus time are reported for three different wavelengths of the irradiation light. Preliminary studies of the CO stretching bands are also reported. Their intensities decrease under irradiation and there are indications of a behaviour similar to that of the CC aliphatic band.     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

A kinetic modelling study of ethane cracking for optimal ethylene yield

Current generation steam cracking plants are considered to be mature. As a consequence it is becoming more and more important to know whether the underlying mechanistic cracking process offers still scope for further improvements. The fundamental kinetic limits to cracking yields have recently been researched in detail for different feed stocks with a new synthesis reactor model, d-RMix, incorporating a large scale mechanistic reaction scheme, SPYRO^® [M.W.M. van Goethem, S. Barendregt, J. Grievink, J.A. Moulijn, P.T.J. Verheijen “Model-based, thermo-physical optimisation for high olefin yield in steam cracking reactors”, Chemical Research and Engineering Developments 88 (2010) 1305–1319]. Mathematical optimization revealed for ethane cracking a maximum ethylene yield of about 67 wt%. with a linear-concave optimal temperature profile along the reaction coordinate with a maximum temperature between 1200 and 1300 K. Further mechanistic analysis of these results showed that the linear-concave shape not only suppresses the successive dehydrogenation and condensation reactions of ethylene, but mainly reduces the role of the ethane initiation reaction to form two methyl radicals.     

On the Performance of the Fluctuation Test for Structural Change

Abstract

We discuss the performance of “closed-end” fluctuation tests, used to detect changes in the structural stability of a model, in the case where the time horizon is large and the observations do not possess high enough moments. It is demonstrated via a simulation study that, in the latter case, the choice of the boundary function should take into account the number of moments existing; otherwise the actual size of the test may exceed the nominal level. We suggest an alternative “open-end” fluctuation procedure and study its asymptotic behavior. It turns out that if an improper boundary function is chosen, then the null hypothesis may be rejected even if it is true. This means that an appropriate choice of the boundary function requires some prior information about the tail heaviness of the observations. This is different from the cumulative sum-based monitoring schemes suggested by Chu et al. (1996 Chu , C. S. J. , Stinchcombe , M. and White , H. ( 1996 ). Monitoring Structural Change , Econometrica 64 : 1045 – 1065 .[Crossref], [Web of Science ®] , [Google Scholar]) and further studied by Horváth et al. (2004 Horváth , L. , Hu?ková , M. , Kokoszka , P. , and Steinebach , J. ( 2004 ). Monitoring Changes in Linear Models , Journal of Statistical Planning and Inference 126 : 225 – 251 .[Crossref], [Web of Science ®] , [Google Scholar]).     

Vanadium-Zeolite Interactions in Fluidized Cracking Catalysts

Metal levels on equilibrium fluidized cracking catalysts (FCC) have been increasing through the years (Fig. 1), indicating that the study of the physicochemical properties of metal resistant FCC has remained an important topic to refiners [1]. After the crude oil price collapse of 1986, Ni levels on equilibrium FCC have remained fairly constant whereas V levels have somewhat decreased owing to the greater availability (and lower cost) of high-quality crudes; Fig. 2. At the metals levels shown in Fig. 1, Ni and V catalyze the undesirable cracking of hydrocarbons in the gasoline boiling range, thus increasing coke and hydrogen yields. Vanadium-induced activity losses can be easily circumvented with the proper catalyst management and increased makeup rates. However, should refiners in the future undertake the cracking of residual oils or crack certain readily available crudes from Venezuela and Mexico, metals (especially V) will probably increase well above the levels shown in Fig. 1 and novel FCC will have to be found to negate the severe effects of V on cracking activity.     

3‐Chlorooxindoles: Versatile Starting Materials for Asymmetric Organocatalytic Synthesis of Spirooxindoles

3‐Chlorooxoindoles have emerged as versatile precursors in the synthesis of spirocyclopropyl oxindoles. High enantio‐ and diastereoselectivity was attained under conditions of both iminium/enamine and H‐bonding catalysis.     

Oxygen Vacancy Relaxation and Domain Wall Hysteresis Motion in Cobalt-Doped Barium Titanate Ceramics

Mechanical and dielectric loss measurements were carried out in the BaTiO₃ ceramics doped with Co at frequencies between 0.01 Hz and 1 MHz as a function of temperature from −150° to 150°C. The relaxation peak observed in the ferroelectric phase with an activation energy of 0.27 eV is assumed to be related to the motion of oxygen vacancies. This peak could be because of the reorientation of an electrical dipole made of oxygen vacancies and Co³⁺ ions in the lattice. Furthermore, another loss peak located just below the Curie temperature T _c could be interpreted as hysteretic motion of the domain walls in a regime where the domain wall density is changing.     

Targeting optimum resource allocation using reverse problem formulations and property clustering techniques

Decoupling the constitutive equations from the balance and constraint equations allows for reformulating a conventional forward problem into two reverse problems. The first reverse problem is the reverse of a simulation problem, where the process model is solved in terms of the constitutive (synthesis/design) variables instead of the process variables, thus providing the synthesis/design targets. The second reverse problem (reverse property prediction) solves the constitutive equations to identify unit operations, operating conditions and/or products by matching the synthesis/design targets. Visualization of the problem is achieved by employing recently developed property clustering techniques, which allows a high-dimensional problem to be visualized in two or three dimensions. The clusters by definition satisfy intra-stream and inter-stream conservation through linear “mixing” rules, which allows for the development of consistent additive rules along with their ternary representation.