Multiple Transitions in Polyvinyl Alkyl Ethers at Low Temperatures

Abstract

A series of polyvinyl alkyl ethers, with the ether side chain ranging in length from methyl to n-decyl, has been studied from ～60°K to above the glass transition. A linear variable differential transformer was used to measure the linear expansion coefficient, α, complemented by mechanical loss measurements with a freely oscillating torsion pendulum and dielectric loss measurements. In addition to the glass transition, two low-temperature transitions have been observed in these systems. The first below T_g, T_gg(1), follows the same trend as the glass transition, i.e., as the side chain length increases the temperature at which the transition occurs decreases, until n-octyl, where side chain crystallization is manifested. The second transition below T_g, T_gg(2), occurs at ～100°K irrespective of side chain length. Because of their analagous dependence on side chain length, T_gg(1) is thought to be similar to the glass transition, i.e., due to main chain motion. Δα' at T_gg(2) is of greater magnitude than Δα' at T_gg(1) and is thought to be a result of reorientation of the side chain.     

Control of a coupled map lattice model for vortex shedding in the wake of a cylinder

The flow behind a vibrating flexible cable at low Reynolds numbers can exhibit complex wake structures such as lace-like patterns, vortex dislocations and frequency cells. These structures have been observed in experiments and numerical simulations, and are predicted by a previously developed low-order coupled map lattice (CML). The discrete (in time and space) CML models consist of a series of diffusively coupled circle map oscillators along the cable span. Motivated by a desire to modify the complex wake patterns behind flexible vibrating cables we have studied the addition of control terms into the highly efficient CML models and explored the resulting dynamics. Proportional, adaptive proportional and discontinuous non-linear (DNL) control methods were used to derive the control laws. The first method employed occasional proportional feedback. The adaptive method used spatio-temporal feedback control. The DNL method used a discontinuous feedback linearization procedure, and the controller was designed for the resulting linearized system using eigenvalue assignment. These techniques were applied to a modeled vortex dislocation structure in the wake of a vibrating cable in uniform freestream flow. Parallel shedding patterns were achieved for a range of forcing frequency-forcing amplitude combinations studied to validate the control theory. The adaptive proportional and DNL methods were found to be more effective than the proportional control method due to the incorporation of a spatially varying feedback gain across the cylinder span. The DNL method was found to be the most efficient controller of the low-order CML model. The required control level across the cable span was correlated to the 1/1 lock-on behavior of the temporal circle map.     

The development of information storage materials — How microscopy can help?

The response of giant magnetoresistance (GMR) devices depends critically on the film microstructure, with parameters such as layer thickness and interfacial abruptness being crucial. This paper presents results obtained using high resolution electron microscopy (HREM), chemical mapping and atom probe microanalysis. Local variations in the magnetic properties are induced by the microstructure and also when the films are patterned to form small elements. These lead to changes in the magnetization reversal mechanism. Some results of the studies of the magnetization reversal carried out using in situ in Lorentz transmission electron microscopy (LTEM) magnetizing experiments are also included.     

Use of measurement uncertainty analysis to assess accuracy of carbon mass balance closure for a cellulase production process

Closing carbon mass balances is a critical and necessary step for verifying the performance of any conversion process. We developed a methodology for calculating carbon mass balance closures for a cellulase production process and then applied measurement uncertainty analysis to calculate 95% confidence limits to assess the accuracy of the results. Cellulase production experiments were conducted in 7-L fermentors using Trichoderma reesei grown on pure cellulose (Solka-floc), glucose, or lactose. All input and output carbon-containing streams were measured and carbon dioxide in the exhaust gas was quantified using a mass spectrometer. On Solka-floc, carbon mass balances ranged from 90 to 100% closure for the first 48 h but increased to 101 to 135% closure from 72 h to the end of the cultivation at 168 h. Carbon mass balance closures for soluble sugar substrates ranged from 92 to 127% over the entire course of the cultivations. The 95% confidence intervals (CIs) for carbon mass balance closure were typically ±11 to 12 percentage points after 48 h of cultivation. Many of the carbon mass balance results did not bracket 100% closure within the 95% CIs. These results suggest that measurement problems with the experimental or analytical methods may exist. This work shows that uncertainty analysis can be a useful diagnostic tool for identifying measurement problems in complex biochemical systems.     

Analysis of biomass sugars using a novel HPLC method

The precise quantitative analysis of biomass sugars is a very important step in the conversion of biomass feedstocks to fuels and chemicals. However, the most accurate method of biomass sugar analysis is based on the gas chromatography analysis of derivatized sugars either as alditol acetates or trimethylsilanes. The derivatization method is time consuming but the alternative high-performance liquid chromatography (HPLC) method cannot resolve most sugars found in biomass hydrolysates. We have demonstrated for the first time that by careful manipulation of the HPLC mobile phase, biomass monomeric sugars (arabinose, xylose, fructose, glucose, mannose, and galactose) can be analyzed quantitatively and there is excellent baseline resolution of all the sugars. This method was demonstrated for standard sugars, pretreated corn stover liquid and solid fractions. Our method can also be used to analyze dimeric sugars (cellobiose and sucrose).     

Fermentation of Reactive-Membrane-Extracted and Ammonium-Hydroxide-Conditioned Dilute-Acid-Pretreated Corn Stover

Acid-pretreated biomass contains various compounds (acetic acid, etc.) that are inhibitory to fermentative microorganisms. Removing or deactivating these compounds using detoxification methods such as overliming or ammonium hydroxide conditioning (AHC) improves sugar-to-ethanol yields. In this study, we treated the liquor fraction of dilute-acid-pretreated corn stover using AHC and a new reactive membrane extraction technique, both separately and in combination, and then the sugars in the treated liquors were fermented to ethanol with the glucose–xylose-fermenting bacterium, Zymomonas mobilis 8b. We performed reactive extraction with mixtures of octanol/Alamine 336 or oleyl alcohol/Alamine 336. The best ethanol yields and rates were achieved for oleyl alcohol-extracted hydrolysates followed by AHC hydrolysates, while octanol-extracted hydrolysates were unfermentable because highly toxic octanol was found in the hydrolysate. Adding olive oil significantly improved yields for octanol-extracted hydrolysate. Additional work is underway to determine if this technology is a cost-effective alternative to traditional hydrolysate conditioning processes.     

High efficiency 165 W near-diffraction-limited Nd:YVO(4) slab oscillator pumped at 880 nm

We demonstrate a compact, efficient Nd:YVO(4) stable-unstable hybrid slab oscillator that was partially end pumped at 880 nm. A maximum output power of 165 W at 1064 nm was obtained with an optical-to-optical efficiency from absorbed pump power to laser output of up to 60% and a slope efficiency of up to 66%. The beam propagation factors M(2) were 1.7 in the stable direction and 1.4 in the unstable direction without sidelobes.     

Vendor test studies supporting the design of a biomass-to-ethanol pilot plant

Applied Biochemistry and Biotechnology - In support of the effort to develop the biomass-to-ethanol process, the National Renewable Energy Laboratory (NREL) is building a pilot plant based on the...     

Synthesis of pyrrolizidine and indolizidine ring systems via N-chloramine rearrangement

The silver ion induced rearrangement of bicyclic N-chloramines is reported. In addition to the expected reaction, oxidation of the rearrangement products was observed in two cases.