Morphology and preferred orientation of Y2O3 film prepared by high-speed laser CVD

Yttria (Y₂O₃) films were prepared at high deposition rates of up to 83 nm/s (300 μm/h) by laser chemical vapor deposition (LCVD) using an Y(dpm)₃ precursor. The effects of deposition conditions, mainly total gas pressure and laser power, on morphology, deposition rate and preferred orientation were studied. Plasma was produced around the substrate over a critical laser power resulting in significant increases in deposition temperature and deposition rate. The high deposition rate (300 μm/h) by LCVD was about 100 to 1000 times as high as those by conventional CVD. The morphology of Y₂O₃ films changed from faceted and columnar structures with high (400) orientation to a columnar structure with high (440) orientation, and finally to a cone-like structure with moderate (440) orientation with increasing total gas pressure (P_tot).     

Evaluation of oxidative stability of canola oils by headspace analysis

Lipid oxidation is a major factor affecting flavor quality and shelf life of vegetable oils. Oxidative stability is therefore an important criterion by which oils are judged for usefulness in various food applications. In this study a method based on headspace analysis was developed to evaluate relative oxidative stability of canola oils. The method does not require the use of chemicals, involves minimal sample preparation, and can be performed on a relatively small sample size in comparison with traditional wet chemical methods. Canola oils freshly extracted in the laboratory from different seed samples were subjected to accelerated oxidation and analyzed for PV by standard methods and headspace volatiles by solid phase microextraction/GC-MS. Forward stepwise regression analysis of the data revealed a relationship between PV and headspace concentration of the volatile lipid oxidation products hexanal and trans,trans-2,4-heptadienal. The PV calculated using this formula correlated (R ²=0.73) with those measured by conventional methods. Presented in part at the 96th Annual Meeting of the AOCS, 1–4 May 2005, Salt Lake City, UT.     

Determination of the vapor pressures of select polychlorinated dibenzo-p-dioxins and dibenzofurans at 75-275 °C

Vapor pressures were determined for several polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at 75-275 °C, extending the available literature data to more relevant temperature regions and providing the first experimental data for 2,3,7-trichlorodibenzo-p-dioxin (2,3,7-TriCD). A modification of the effusion technique, based upon controlling the diffusion of the target compound and subsequent high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS) analysis, was proven comparable to other accepted methods for determining the vapor pressures of semi-volatile organic compounds (SVOCs). Vapor pressures for octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) were in excellent agreement with those reported in literature. The application of the current method for the vapor pressure determinations of eight polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) in the extended temperature range (up to 275 °C) is reported. The extension of the vapor pressures to such temperatures, unprecedented for the PCDDs/Fs, is important for vapor-particle partitioning modeling in regions relevant to PCDD/F formation and control. Estimates for the melting temperatures and enthalpies of sublimation and vaporization are also reported, the latter for which no experimentally determined values have been found in the literature. The use of the method to deliver reproducible, trace concentrations (ppt-ppb) of targets was applied to the calibration of the jet-REMPI/TOFMS as an online detector for low chlorinated PCDDs/Fs.     

Crystallization behavior of oxyethylene/oxybutylene diblock and triblock copolymers

The crystallization behavior of poly(oxyethylene)-b-poly(oxybutylene) block copolymers with different compositions, morphologies and architectures (E_mB_n diblock copolymers and E_mB_nE_m, B_nE_mB_n triblock copolymers) were investigated and the effect of volume fraction and architecture on the crystallization temperature (T_c) in non-isothermal crystallization was determined. It is found that the E_mB_n diblock copolymers having long E blocks exhibit similar crystallization temperatures, irrespective of volume fraction and morphology, but for the block copolymers with shorter E blocks the crystallization temperature increases with both the volume fraction, φ_E, and the length, m, of the E block. Some block copolymers with extremely low T_c, which fall into the temperature range normally associated with homogenous nucleation, were chosen for time-resolved small-angle X-ray scattering (SAXS) and isothermal crystallization kinetics experiments. The results show that breakout crystallization occurs in all these block copolymers. Therefore, unlike E_mB_n/B_h blends, there is no obvious relationship between T_c and crystallization behavior in neat block copolymers and homogeneous nucleation does not definitely lead to confined crystallization. The values of χ_c/χ_ODT for all the block copolymers with hex and bcc morphology were also calculated. It is found that all the block copolymers have χ_c/χ_ODT<3, in agreement with the previously reported critical value and consistent with their breakout crystallization behavior.     

Dietary stearic acid and risk of cardiovascular disease: Intake,sources, digestion,and absorption

Individual FA have diverse biological effects, some of which affect the risk of cardiovascular disease (CVD). In the context of food-based dietary guidance designed to reduce CVD risk, fat and FA recommendations focus on reducing saturated FA (SFA) and trans FA (TFA), and ensuring an adequate intake of unsaturated FA. Because stearic acid shares many physical properties with the other long-chain SFA but has different physiological effects, it is being evaluated as a substitute for TFA in food manufacturing. For stearic acid to become the primary replacement for TFA, it is essential that its physical properties and biological effects be well understood.     

A Fully Continuous Supercritical Fluid Extraction System for Contaminated Soil

A fully continuous lab scale supercritical fluid extraction system has been designed, built and tested. The system continuously pumps carbon dioxide under supercritical conditions and soil slurry into a counter‐current contacting column. Delhi Loamy Sand, spiked with approximately 10 mg/g of naphthalene, was used as the testing soil. The soil slurry ranged from 0.0028 g dry soil per g slurry to 0.072 g/g. The operating temperature was 43°C and the operating pressure was 7.7 MPa. Near steady state, fully continuous flow was achieved with runs lasting as long as 2 h. All carbon dioxide samples contained measurable quantities of naphthalene and the measured mass transfer coefficients were as high as 4.6×10^?4 s^?1.     

Implications of variable fluid resistance caused by start-up flow in microfluidic networks

Electrical circuit analogies are often used to design microfluidic systems because they simplify device design, providing simple relationships between fluid flow rate, driving forces, and channel dimensions. However, such approximations often significantly overestimate flow rates in situations where start-up energy losses from establishing kinetic head are similar in magnitude to the energy required to overcome viscous shear stresses, as is often the case within complex microfluidic networks. These reduced flows can be more accurately predicted within an electrical analogy framework that accounts for the nonlinear flow resistance generated on the transient regime of start-up flow. In this work, standard flow resistance expressions are modified to account for such effects, and the onset of nonlinear resistance is predicted by a dimensionless parameter, $\xi = Re\frac{D}{L},$ which is dependent on the Reynolds number and the channel length. As a demonstration, variable fluid resistance is shown to dramatically affect the flow performance of common microfluidic units such as T-junctions and serpentine channels, and the change in performance is accurately predicted. Experimental and theoretical analysis of T-junctions further shows that variable flow resistance causes the ratio of flows through the junction to converge toward unity with respect to an increasing total flow rate. In addition, serpentine channels are shown to exaggerate these start-up effects, owing to compounded energetic demand associated with changing a flow’s direction. As a result, serpentine channels cause the ratio of flow rates exiting a T-junction to diverge from unity with respect to an increasing flow rate.     

An engineering study of the film embossing process

A mathematical model of the dynamics and heat transfer of the film embossing process has been developed. The thermal analysis around the preheat roll is determined from an unsteady, two-dimensional heat conduction equation along with appropriate boundary conditions by neglecting the curvature of the preheat roll and choosing a Lagrangian reference frame. The heat transfer occurring between the preheat roll and the embossing rolls is based on a one-dimensional analysis, including both convective and radiative effects. The deformation occurring in the nip region is analyzed for two different situations. For the case where the surface features are small in comparison with the film thickness, a modified one-dimennsional calendering analysis is given, accounting for the irregular geometry of the embossing roll surface. For the case where the polymer does not make complete contact with the surface of the engraved channel, the local deformation is determined by means of a simple one-dimensional cavity filling model. The required pressure distribution is determined by means of a simple one-dimensional cavity filling model, The required pressure distribution is determined by means of a conventional calendering analysis. The analysis for the case of a Newtonian and power-law model is presented in detail. The model yields qualitatively correct results and is computationally simple.     

Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers

The effect of molecular architecture on the evolution of viscoelastic properties during crystallization was investigated using ethylene-hexene copolymers manufactured via metallocene (M-LLDPE) and Ziegler-Natta (ZN-LLDPE) processes. Differences in branching distribution were shown to have a drastic effect on the viscoelastic properties near the gel point. It is shown that the branching distribution rather than branch content is the determining parameter for the evolution of the rheological properties during isothermal and non-isothermal crystallization, and for the width of the solidification interval. We developed a partial melting technique for the preparation of stable critical gels of LLDPE whose viscoelastic properties correspond to the intermediate state between melt and solid. Local molecular conformation and crystallinity in these gels were characterized by Raman spectroscopy, which shows that the transition from melt-like to solid-like rheological behavior (physical gelation) in LLDPE occurs at a very low overall crystallinity of less than 5%.     

A model for studying LCAT reaction: In vitro cholesterol esterification in pig ovarian follicular fluid

Phosphatidylcholine acyltransferase (lecithin:cholesterol acyltransferase or LCAT; EC 2.3.1.43) activity was found to be present in pig ovarian follicular fluid (POFF), in addition to pig serum (PS). The cholesterol esterification rate in both POFF and PS is linear with incubation time up to 2 hr. The mean absolute rate of POFF-cholesterol esterification was 8.1±0.4 nmoles per ml per hr approximately one-fourth of that in PS. However, the fractional rate (percent of labeled cholesterol esterified per hr) of POFF-cholesterol esterification was similar to that observed in PS. There was little variation of absolute rate of cholesterol esterification in the fluid obtained from different sizes of follicles. Fatty acid or triacylglycerol did not participate in the reaction of cholesterol esterification in POFF. No appreciable change in enzymatic activity was found from storing POFF at 4 C for periods of time up to 24 hr or at −70 C up to 2 months, but activity was lost thereafter. On the other hand, PS showed a much longer period of stability (5 days at 4 C and 9 months at −70 C). A discrepancy between the fatty acid composition of cholesteryl esters formed by the LCAT reaction and the fatty acid composition at the C-2 position of phosphatidylcholine led us to propose a two-step mechanism for the LCAT reaction. It is concluded that the LCAT of POFF, as well as that of plasma, is specific for individual fatty acids rather than for the fatty acid composition of phosphatidylcholine. The fatty acid concentration of lysophosphatidylcholine decreased during prolonged incubation times (6 to 21 hr) suggesting that the increased lysophosphatidylcholine formed as a product of the LCAT reaction may be reused as substrate for the LCAT reaction or for hydrolysis by lysophosphatidylcholine hydrolase. Presented at the AOCS Meeting, New York, May 1977.