Life Origination Hydrate Hypothesis (LOH-Hypothesis)

PubMed Central

Ostrovskii, Victor; Kadyshevich, Elena

2012-01-01

The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis), according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides), DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor. PMID:25382120

Process Model of A Fusion Fuel Recovery System for a Direct Drive IFE Power Reactor

NASA Astrophysics Data System (ADS)

Natta, Saswathi; Aristova, Maria; Gentile, Charles

2008-11-01

A task has been initiated to develop a detailed representative model for the fuel recovery system (FRS) in the prospective direct drive inertial fusion energy (IFE) reactor. As part of the conceptual design phase of the project, a chemical process model is developed in order to observe the interaction of system components. This process model is developed using FEMLAB Multiphysics software with the corresponding chemical engineering module (CEM). Initially, the reactants, system structure, and processes are defined using known chemical species of the target chamber exhaust. Each step within the Fuel recovery system is modeled compartmentally and then merged to form the closed loop fuel recovery system. The output, which includes physical properties and chemical content of the products, is analyzed after each step of the system to determine the most efficient and productive system parameters. This will serve to attenuate possible bottlenecks in the system. This modeling evaluation is instrumental in optimizing and closing the fusion fuel cycle in a direct drive IFE power reactor. The results of the modeling are presented in this paper.

Chemical Applications for Enhanced World Security

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leibman, Christopher Patrick

The purpose of this project is to reduce complexity of chemical analysis by combining chemical and physical processing steps into on package; develop instrumentation that cost less and is easy to use in a field laboratory by non-experts; and develop this "chemical application" so uranium enrichment can be measured onsite, eliminating the need for radioactive sample transport.

Design and operation of a continuous integrated monoclonal antibody production process.

PubMed

Steinebach, Fabian; Ulmer, Nicole; Wolf, Moritz; Decker, Lara; Schneider, Veronika; Wälchli, Ruben; Karst, Daniel; Souquet, Jonathan; Morbidelli, Massimo

2017-09-01

The realization of an end-to-end integrated continuous lab-scale process for monoclonal antibody manufacturing is described. For this, a continuous cultivation with filter-based cell-retention, a continuous two column capture process, a virus inactivation step, a semi-continuous polishing step (twin-column MCSGP), and a batch-wise flow-through polishing step were integrated and operated together. In each unit, the implementation of internal recycle loops allows to improve the performance: (a) in the bioreactor, to simultaneously increase the cell density and volumetric productivity, (b) in the capture process, to achieve improved capacity utilization at high productivity and yield, and (c) in the MCSGP process, to overcome the purity-yield trade-off of classical batch-wise bind-elute polishing steps. Furthermore, the design principles, which allow the direct connection of these steps, some at steady state and some at cyclic steady state, as well as straight-through processing, are discussed. The setup was operated for the continuous production of a commercial monoclonal antibody, resulting in stable operation and uniform product quality over the 17 cycles of the end-to-end integration. The steady-state operation was fully characterized by analyzing at the outlet of each unit at steady state the product titer as well as the process (HCP, DNA, leached Protein A) and product (aggregates, fragments) related impurities. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1303-1313, 2017. © 2017 American Institute of Chemical Engineers.

Xylitol: a review on bioproduction, application, health benefits, and related safety issues.

PubMed

Ur-Rehman, Salim; Mushtaq, Zarina; Zahoor, Tahir; Jamil, Amir; Murtaza, Mian Anjum

2015-01-01

Xylitol is a pentahydroxy sugar-alcohol which exists in a very low quantity in fruits and vegetables (plums, strawberries, cauliflower, and pumpkin). On commercial scale, xylitol can be produced by chemical and biotechnological processes. Chemical production is costly and extensive in purification steps. However, biotechnological method utilizes agricultural and forestry wastes which offer the possibilities of economic production of xylitol by reducing required energy. The precursor xylose is produced from agricultural biomass by chemical and enzymatic hydrolysis and can be converted to xylitol primarily by yeast strain. Hydrolysis under acidic condition is the more commonly used practice influenced by various process parameters. Various fermentation process inhibitors are produced during chemical hydrolysis that reduce xylitol production, a detoxification step is, therefore, necessary. Biotechnological xylitol production is an integral process of microbial species belonging to Candida genus which is influenced by various process parameters such as pH, temperature, time, nitrogen source, and yeast extract level. Xylitol has application and potential for food and pharmaceutical industries. It is a functional sweetener as it has prebiotic effects which can reduce blood glucose, triglyceride, and cholesterol level. This review describes recent research developments related to bioproduction of xylitol from agricultural wastes, application, health, and safety issues.

Further Investigation Into the Use of Laser Surface Preparation of Ti-6Al-4V Alloy for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Crow, Allison; Zetterberg, Anna; Hopkins, John; Wohl, Christopher J.; Connell, John W.; Belcher, Tony; Blohowiak, Kay Y.

2014-01-01

Adhesive bonding offers many advantages over mechanical fastening, but requires robust materials and processing methodologies before it can be incorporated in primary structures for aerospace applications. Surface preparation is widely recognized as one of the key steps to producing robust and predictable bonds. This report documents an ongoing investigation of a surface preparation technique based on Nd:YAG laser ablation as a replacement for the chemical etch and/or abrasive processes currently applied to Ti-6Al-4V alloys. Laser ablation imparts both topographical and chemical changes to a surface that can lead to increased bond durability. A laser based process provides an alternative to chemical-immersion, manual abrasion, and grit blast process steps which are expensive, hazardous, environmentally unfriendly, and less precise. In addition, laser ablation is amenable to process automation, which can improve reproducibility to meet quality standards for surface preparation. An update on work involving adhesive property testing, surface characterization, surface stability, and the effect of laser surface treatment on fatigue behavior is presented. Based on the tests conducted, laser surface treatment is a viable replacement for the immersion chemical surface treatment processes. Testing also showed that the fatigue behavior of the Ti-6Al-4V alloy is comparable for surfaces treated with either laser ablation or chemical surface treatment.

Surface Modified Particles By Multi-Step Michael-Type Addition And Process For The Preparation Thereof

DOEpatents

Cook, Ronald Lee; Elliott, Brian John; Luebben, Silvia DeVito; Myers, Andrew William; Smith, Bryan Matthew

2005-05-03

A new class of surface modified particles and a multi-step Michael-type addition surface modification process for the preparation of the same is provided. The multi-step Michael-type addition surface modification process involves two or more reactions to compatibilize particles with various host systems and/or to provide the particles with particular chemical reactivities. The initial step comprises the attachment of a small organic compound to the surface of the inorganic particle. The subsequent steps attach additional compounds to the previously attached organic compounds through reactive organic linking groups. Specifically, these reactive groups are activated carbon—carbon pi bonds and carbon and non-carbon nucleophiles that react via Michael or Michael-type additions.

Chemical vapor deposition of mullite coatings

DOEpatents

Sarin, Vinod; Mulpuri, Rao

1998-01-01

This invention is directed to the creation of crystalline mullite coatings having uniform microstructure by chemical vapor deposition (CVD). The process comprises the steps of establishing a flow of reactants which will yield mullite in a CVD reactor, and depositing a crystalline coating from the reactant flow. The process will yield crystalline coatings which are dense and of uniform thickness.

Sampling procedure for lake or stream surface water chemistry

Treesearch

Robert Musselman

2012-01-01

Surface waters collected in the field for chemical analyses are easily contaminated. This research note presents a step-by-step detailed description of how to avoid sample contamination when field collecting, processing, and transporting surface water samples for laboratory analysis.

Thermochemical water decomposition processes

NASA Technical Reports Server (NTRS)

Chao, R. E.

1974-01-01

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Evolution of Taste Compounds of Dezhou-Braised Chicken During Cooking Evaluated by Chemical Analysis and an Electronic Tongue System.

PubMed

Liu, Dengyong; Li, Shengjie; Wang, Nan; Deng, Yajun; Sha, Lei; Gai, Shengmei; Liu, Huan; Xu, Xinglian

2017-05-01

This paper aimed to study the time course changes in taste compounds of Dezhou-braised chicken during the entire cooking process mainly consisting of deep-frying, high-temperature boiling, and low-temperature braising steps. For this purpose, meat samples at different processing stages were analyzed for 5'-nucleotides and free amino acids, and were also subjected to electronic tongue measurements. Results showed that IMP, Glu, Lys, and sodium chloride were the main compounds contributing to the taste attributes of the final product. IMP and Glu increased in the boiling step and remained unchanged in the following braising steps. Meanwhile, decrease in Lys content and increase in sodium chloride content were observed over time in both boiling and braising steps. Intensities for bitterness, saltiness, and Aftertaste-B obtained from the electronic tongue analysis were correlated with the concentrations of these above chemical compounds. Therefore, the electronic tongue system could be applied to evaluate the taste development of Dezhou-braised chicken during processing. © 2017 Institute of Food Technologists®.

Metal-assisted etch combined with regularizing etch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yim, Joanne; Miller, Jeff; Jura, Michael

In an aspect of the disclosure, a process for forming nanostructuring on a silicon-containing substrate is provided. The process comprises (a) performing metal-assisted chemical etching on the substrate, (b) performing a clean, including partial or total removal of the metal used to assist the chemical etch, and (c) performing an isotropic or substantially isotropic chemical etch subsequently to the metal-assisted chemical etch of step (a). In an alternative aspect of the disclosure, the process comprises (a) performing metal-assisted chemical etching on the substrate, (b) cleaning the substrate, including removal of some or all of the assisting metal, and (c) performingmore » a chemical etch which results in regularized openings in the silicon substrate.« less

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

NASA Astrophysics Data System (ADS)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

Formation of silicon nanowire packed films from metallurgical-grade silicon powder using a two-step metal-assisted chemical etching method.

PubMed

Ouertani, Rachid; Hamdi, Abderrahmen; Amri, Chohdi; Khalifa, Marouan; Ezzaouia, Hatem

2014-01-01

In this work, we use a two-step metal-assisted chemical etching method to produce films of silicon nanowires shaped in micrograins from metallurgical-grade polycrystalline silicon powder. The first step is an electroless plating process where the powder was dipped for few minutes in an aqueous solution of silver nitrite and hydrofluoric acid to permit Ag plating of the Si micrograins. During the second step, corresponding to silicon dissolution, we add a small quantity of hydrogen peroxide to the plating solution and we leave the samples to be etched for three various duration (30, 60, and 90 min). We try elucidating the mechanisms leading to the formation of silver clusters and silicon nanowires obtained at the end of the silver plating step and the silver-assisted silicon dissolution step, respectively. Scanning electron microscopy (SEM) micrographs revealed that the processed Si micrograins were covered with densely packed films of self-organized silicon nanowires. Some of these nanowires stand vertically, and some others tilt to the silicon micrograin facets. The thickness of the nanowire films increases from 0.2 to 10 μm with increasing etching time. Based on SEM characterizations, laser scattering estimations, X-ray diffraction (XRD) patterns, and Raman spectroscopy, we present a correlative study dealing with the effect of the silver-assisted etching process on the morphological and structural properties of the processed silicon nanowire films.

Formation of silicon nanowire packed films from metallurgical-grade silicon powder using a two-step metal-assisted chemical etching method

PubMed Central

2014-01-01

In this work, we use a two-step metal-assisted chemical etching method to produce films of silicon nanowires shaped in micrograins from metallurgical-grade polycrystalline silicon powder. The first step is an electroless plating process where the powder was dipped for few minutes in an aqueous solution of silver nitrite and hydrofluoric acid to permit Ag plating of the Si micrograins. During the second step, corresponding to silicon dissolution, we add a small quantity of hydrogen peroxide to the plating solution and we leave the samples to be etched for three various duration (30, 60, and 90 min). We try elucidating the mechanisms leading to the formation of silver clusters and silicon nanowires obtained at the end of the silver plating step and the silver-assisted silicon dissolution step, respectively. Scanning electron microscopy (SEM) micrographs revealed that the processed Si micrograins were covered with densely packed films of self-organized silicon nanowires. Some of these nanowires stand vertically, and some others tilt to the silicon micrograin facets. The thickness of the nanowire films increases from 0.2 to 10 μm with increasing etching time. Based on SEM characterizations, laser scattering estimations, X-ray diffraction (XRD) patterns, and Raman spectroscopy, we present a correlative study dealing with the effect of the silver-assisted etching process on the morphological and structural properties of the processed silicon nanowire films. PMID:25349554

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

1987-12-29

A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

Development of a 3-step straight-through purification strategy combining membrane adsorbers and resins.

PubMed

Hughson, Michael D; Cruz, Thayana A; Carvalho, Rimenys J; Castilho, Leda R

2017-07-01

The pressures to efficiently produce complex biopharmaceuticals at reduced costs are driving the development of novel techniques, such as in downstream processing with straight-through processing (STP). This method involves directly and sequentially purifying a particular target with minimal holding steps. This work developed and compared six different 3-step STP strategies, combining membrane adsorbers, monoliths, and resins, to purify a large, complex, and labile glycoprotein from Chinese hamster ovary cell culture supernatant. The best performing pathway was cation exchange chromatography to hydrophobic interaction chromatography to affinity chromatography with an overall product recovery of up to 88% across the process and significant clearance of DNA and protein impurities. This work establishes a platform and considerations for the development of STP of biopharmaceutical products and highlights its suitability for integration with single-use technologies and continuous production methods. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:931-940, 2017. © 2017 American Institute of Chemical Engineers.

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

2004-01-01

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HCl vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow-chemical ionization mass spectrometry and optical ellipsometry, among others.

Algae to Bio-Crude in Less Than 60 Minutes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, Doug

Engineers have created a chemical process that produces useful crude oil just minutes after engineers pour in harvested algae -- a verdant green paste with the consistency of pea soup. The PNNL team combined several chemical steps into one continuous process that starts with an algae slurry that contains as much as 80 to 90 percent water. Most current processes require the algae to be dried -- an expensive process that takes a lot of energy. The research has been licensed by Genifuel Corp.

Algae to Bio-Crude in Less Than 60 Minutes

ScienceCinema

Elliott, Doug

2018-01-16

Engineers have created a chemical process that produces useful crude oil just minutes after engineers pour in harvested algae -- a verdant green paste with the consistency of pea soup. The PNNL team combined several chemical steps into one continuous process that starts with an algae slurry that contains as much as 80 to 90 percent water. Most current processes require the algae to be dried -- an expensive process that takes a lot of energy. The research has been licensed by Genifuel Corp.

Chemistry of rubber processing and disposal.

PubMed Central

Bebb, R L

1976-01-01

The major chemical changes during the processing of rubber occur with the breakdown in mastication and during vulcanization of the molded tire. There is little chemical change during the compounding, calendering, extrusion, and molding steps. Reclaiming is the process of converting scrap rubber into an unsaturated, processible product that can be vulcanized with sulfur. Pyrolysis of scrap rubber yields a complex mixture of liquids, gas, and residue in varying ratios dependent on the nature of the scrap and the conditions of pyrolysis. PMID:799964

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bakel, Allen J.; Conner, Cliff; Quigley, Kevin

One of the missions of the Reduced Enrichment for Research and Test Reactors (RERTR) program (and now the National Nuclear Security Administrations Material Management and Minimization program) is to facilitate the use of low enriched uranium (LEU) targets for 99Mo production. The conversion from highly enriched uranium (HEU) to LEU targets will require five to six times more uranium to produce an equivalent amount of 99Mo. The work discussed here addresses the technical challenges encountered in the treatment of uranyl nitrate hexahydrate (UNH)/nitric acid solutions remaining after the dissolution of LEU targets. Specifically, the focus of this work is themore » calcination of the uranium waste from 99Mo production using LEU foil targets and the Modified Cintichem Process. Work with our calciner system showed that high furnace temperature, a large vent tube, and a mechanical shield are beneficial for calciner operation. One- and two-step direct calcination processes were evaluated. The high-temperature one-step process led to contamination of the calciner system. The two-step direct calcination process operated stably and resulted in a relatively large amount of material in the calciner cup. Chemically assisted calcination using peroxide was rejected for further work due to the difficulty in handling the products. Chemically assisted calcination using formic acid was rejected due to unstable operation. Chemically assisted calcination using oxalic acid was recommended, although a better understanding of its chemistry is needed. Overall, this work showed that the two-step direct calcination and the in-cup oxalic acid processes are the best approaches for the treatment of the UNH/nitric acid waste solutions remaining from dissolution of LEU targets for 99Mo production.« less

Vitamin B1-catalyzed acetoin formation from acetaldehyde: a key step for upgrading bioethanol to bulk C₄ chemicals.

PubMed

Lu, Ting; Li, Xiukai; Gu, Liuqun; Zhang, Yugen

2014-09-01

The production of bulk chemicals and fuels from renewable biobased feedstocks is of significant importance for the sustainability of human society. The production of ethanol from biomass has dramatically increased and bioethanol also holds considerable potential as a versatile building block for the chemical industry. Herein, we report a highly selective process for the conversion of ethanol to C4 bulk chemicals, such as 2,3-butanediol and butene, via a vitamin B1 (thiamine)-derived N-heterocyclic carbene (NHC)-catalyzed acetoin condensation as the key step to assemble two C2 acetaldehydes into a C4 product. The environmentally benign and cheap natural catalyst vitamin B1 demonstrates high selectivity (99%), high efficiency (97% yield), and high tolerance toward ethanol and water impurities in the acetoin reaction. The results enable a novel and efficient process for ethanol upgrading. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of High Quality Chemical XOR Gates with Noise Reduction.

PubMed

Wood, Mackenna L; Domanskyi, Sergii; Privman, Vladimir

2017-07-05

We describe a chemical XOR gate design that realizes gate-response function with filtering properties. Such gate-response function is flat (has small gradients) at and in the vicinity of all the four binary-input logic points, resulting in analog noise suppression. The gate functioning involves cross-reaction of the inputs represented by pairs of chemicals to produce a practically zero output when both are present and nearly equal. This cross-reaction processing step is also designed to result in filtering at low output intensities by canceling out the inputs if one of the latter has low intensity compared with the other. The remaining inputs, which were not reacted away, are processed to produce the output XOR signal by chemical steps that result in filtering at large output signal intensities. We analyze the tradeoff resulting from filtering, which involves loss of signal intensity. We also discuss practical aspects of realizations of such XOR gates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion welding. [heat treatment of nickel alloys following single step vacuum welding process

NASA Technical Reports Server (NTRS)

Holko, K. H. (Inventor)

1974-01-01

Dispersion-strengthened nickel alloys are sanded on one side and chemically polished. This is followed by a single-step welding process wherein the polished surfaces are forced into intimate contact at 1,400 F for one hour in a vacuum. Diffusion, recrystallization, and grain growth across the original weld interface are obtained during postheating at 2,150 F for two hours in hydrogen.

Superhydrophobic aluminum alloy surfaces by a novel one-step process.

PubMed

Saleema, N; Sarkar, D K; Paynter, R W; Chen, X-G

2010-09-01

A simple one-step process has been developed to render aluminum alloy surfaces superhydrophobic by immersing the aluminum alloy substrates in a solution containing NaOH and fluoroalkyl-silane (FAS-17) molecules. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle measurements have been performed to characterize the morphological features, chemical composition and superhydrophobicity of the surfaces. The resulting surfaces provided a water contact angle as high as ∼162° and a contact angle hysteresis as low as ∼4°. The study indicates that it is possible to fabricate superhydrophobic aluminum surfaces easily and effectively without involving the traditional two-step processes.

Automation of route identification and optimisation based on data-mining and chemical intuition.

PubMed

Lapkin, A A; Heer, P K; Jacob, P-M; Hutchby, M; Cunningham, W; Bull, S D; Davidson, M G

2017-09-21

Data-mining of Reaxys and network analysis of the combined literature and in-house reactions set were used to generate multiple possible reaction routes to convert a bio-waste feedstock, limonene, into a pharmaceutical API, paracetamol. The network analysis of data provides a rich knowledge-base for generation of the initial reaction screening and development programme. Based on the literature and the in-house data, an overall flowsheet for the conversion of limonene to paracetamol was proposed. Each individual reaction-separation step in the sequence was simulated as a combination of the continuous flow and batch steps. The linear model generation methodology allowed us to identify the reaction steps requiring further chemical optimisation. The generated model can be used for global optimisation and generation of environmental and other performance indicators, such as cost indicators. However, the identified further challenge is to automate model generation to evolve optimal multi-step chemical routes and optimal process configurations.

Integrated aerobic biological-chemical treatment of winery wastewater diluted with urban wastewater. LED-based photocatalysis in the presence of monoperoxysulfate.

PubMed

Solís, Rafael R; Rivas, Francisco Javier; Ferreira, Leonor C; Pirra, Antonio; Peres, José A

2018-01-28

The oxidation of Winery Wastewater (WW) by conventional aerobic biological treatment usually leads to inefficient results due to the presence of organic substances, which are recalcitrant or toxic in conventional procedures. This study explores the combination of biological and chemical processes in order to complete the oxidation of biodegradable and non-biodegradable compounds in two sequential steps. Thus, a biological oxidation of a diluted WW is carried out by using the activated sludge process. Activated sludge was gradually acclimated to the Diluted Winery Wastewater (DWW). Some aspects concerning the biological process were evaluated (kinetics of the oxidation and sedimentation of the sludge produced). The biological treatment of the DWW led to a 40-50% of Chemical Oxygen Demand (COD) removal in 8 h, being necessary the application of an additional process. Different chemical processes combining UVA-LEDs radiation, monoperoxysulfate (MPS) and photocatalysts were applied in order to complete the COD depletion and efficient removal of polyphenols content, poorly oxidized in the previous biological step. From the options tested, the combination of UVA, MPS and a novel LaCoO 3 -TiO 2 composite, with double route of MPS decomposition through heterogeneous catalysis and photocatalysis, led to the best results (95% of polyphenol degradation, and additional 60% of COD removal). Initial MPS concentration and pH effect in this process were assessed.

B827 Chemical Synthhesis Project - Industrial Control System Integration - Statement of Work & Specification with Attachments 1-14

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wade, F. E.

The Chemical Synthesis Pilot Process at the Lawrence Livermore National Laboratory (LLNL) Site 300 827 Complex will be used to synthesize small quantities of material to support research and development. The project will modernize and increase current capabilities for chemical synthesis at LLNL. The primary objective of this project is the conversion of a non-automated hands-on process to a remoteoperation process, while providing enhanced batch process step control, stored recipe-specific parameter sets, process variable visibility, monitoring, alarm and warning handling, and comprehensive batch record data logging. This Statement of Work and Specification provides the industrial-grade process control requirements for themore » chemical synthesis batching control system, hereafter referred to as the “Control System” to be delivered by the System Integrator.« less

Kinetics in the real world: linking molecules, processes, and systems.

PubMed

Kohse-Höinghaus, Katharina; Troe, Jürgen; Grabow, Jens-Uwe; Olzmann, Matthias; Friedrichs, Gernot; Hungenberg, Klaus-Dieter

2018-04-25

Unravelling elementary steps, reaction pathways, and kinetic mechanisms is key to understanding the behaviour of many real-world chemical systems that span from the troposphere or even interstellar media to engines and process reactors. Recent work in chemical kinetics provides detailed information on the reactive changes occurring in chemical systems, often on the atomic or molecular scale. The optimisation of practical processes, for instance in combustion, catalysis, battery technology, polymerisation, and nanoparticle production, can profit from a sound knowledge of the underlying fundamental chemical kinetics. Reaction mechanisms can combine information gained from theory and experiments to enable the predictive simulation and optimisation of the crucial process variables and influences on the system's behaviour that may be exploited for both monitoring and control. Chemical kinetics, as one of the pillars of Physical Chemistry, thus contributes importantly to understanding and describing natural environments and technical processes and is becoming increasingly relevant for interactions in and with the real world.

Environmental Benign Process for Production of Molybdenum Metal from Sulphide Based Minerals

NASA Astrophysics Data System (ADS)

Rajput, Priyanka; Janakiram, Vangada; Jayasankar, Kalidoss; Angadi, Shivakumar; Bhoi, Bhagyadhar; Mukherjee, Partha Sarathi

2017-10-01

Molybdenum is a strategic and high temperature refractory metal which is not found in nature in free state, it is predominantly found in earth's crust in the form of MoO3/MoS2. The main disadvantage of the industrial treatment of Mo concentrate is that the process contains many stages and requires very high temperature. Almost in every step many gaseous, liquid, solid chemical substances are formed which require further treatment. To overcome the above drawback, a new alternative one step novel process is developed for the treatment of sulphide and trioxide molybdenum concentrates. This paper presents the results of the investigations on molybdenite dissociation (MoS2) using microwave assisted plasma unit as well as transferred arc thermal plasma torch. It is a single step process for the preparation of pure molybdenum metal from MoS2 by hydrogen reduction in thermal plasma. Process variable such as H2 gas, Ar gas, input current, voltage and time have been examined to prepare molybdenum metal. Molybdenum recovery of the order of 95% was achieved. The XRD results confirm the phases of molybdenum metal and the chemical analysis of the end product indicate the formation of metallic molybdenum (Mo 98%).

Reflow process stabilization by chemical characteristics and process conditions

NASA Astrophysics Data System (ADS)

Kim, Myoung-Soo; Park, Jeong-Hyun; Kim, Hak-Joon; Kim, Il-Hyung; Jeon, Jae-Ha; Gil, Myung-Goon; Kim, Bong-Ho

2002-07-01

With the shrunken device rule below 130nm, the patterning of smaller contact hole with enough process margin is required for mass production. Therefore, shrinking technology using thermal reflow process has been applied for smaller contact hole formation. In this paper, we have investigated the effects of chemical characteristics such as molecular weight, blocking ratio of resin, cross-linker amount and solvent type with its composition to reflow process of resist and found the optimized chemical composition for reflow process applicable condition. And several process conditions like resist coating thickness and multi-step thermal reflow method have been also evaluated to stabilize the pattern profile and improve CD uniformity after reflow process. From the experiment results, it was confirmed that the effect of crosslinker in resist to reflow properties such as reflow temperature and reflow rate were very critical and it controlled the pattern profile during reflow processing. And also, it showed stable CD uniformity and improved resist properties for top loss, film shrinkage and etch selectivity. The application of lower coating thickness of resist induced symmetric pattern profile even at edge with wider process margin. The introduction of two-step baking method for reflow process showed uniform CD value, also. It is believed that the application of resist containing crosslinker and optimized process conditions for smaller contact hole patterning is necessary for the mass production with a design rule below 130nm.

Effects of a modular two-step ozone-water and annealing process on silicon carbide graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webb, Matthew J., E-mail: matthew.webb@cantab.net; Lundstedt, Anna; Grennberg, Helena

By combining ozone and water, the effect of exposing epitaxial graphene on silicon carbide to an aggressive wet-chemical process has been evaluated after high temperature annealing in ultra high vacuum. The decomposition of ozone in water produces a number of oxidizing species, however, despite long exposure times to the aqueous-ozone environment, no graphene oxide was observed after the two-step process. The systems were comprehensively characterized before and after processing using Raman spectroscopy, core level photoemission spectroscopy, and angle resolved photoemission spectroscopy together with low energy electron diffraction, low energy electron microscopy, and atomic force microscopy. In spite of the chemicalmore » potential of the aqueous-ozone reaction environment, the graphene domains were largely unaffected raising the prospect of employing such simple chemical and annealing protocols to clean or prepare epitaxial graphene surfaces.« less

Biological conversion of pyrolytic products to ethanol and lipids

NASA Astrophysics Data System (ADS)

Lian, Jieni

Pyrolysis is a promising technology that can convert up to 75 % of lignocellulosic biomass into crude bio-oil. However, due to the complex chemical compositions of bio-oil, its further refining into fuels and high value chemicals faces great challenges. This dissertation research proposed new technologies for biological conversion of pyrolytic products derived from cellulose and hemicellulose, such as anhydrosugars and carbolic acids to fuels and chemicals. First, the pyrolytic anhydrosugars (chiefly levoglucosan (LG)) were hydrolysed into glucose followed by neutralization, detoxification and fermentation to produce ethanol by ethanogenetic yeast and lipids by oleaginous yeasts. Second, a novel process for the conversion of C1-C4 pyrolytic products to lipid with oleaginous yeasts was investigated. Third, oleaginous yeasts that can directly convert LG to lipids were studied and a recombined yeast with LG kinase was constructed for the direct convertion of LG into lipids. This allowed a reduction of existing process for LG fermentation from four steps into two steps and eliminated the need for acids and bases as well as the disposal of chemicals. The development of genetic modified organisms with LG kinase opens a promising avenue for the direct LG fermentation to produce a wide range of fuels and chemicals. The simplification of LG utilization process would enhance the economic viability of this technology.

Modified Unzipping Technique to Prepare Graphene Nano-Sheets

NASA Astrophysics Data System (ADS)

Al-Tamimi, B. H.; Farid, S. B. H.; Chyad, F. A.

2018-05-01

Graphene nano-sheets have been prepared via unzipping approach of multiwall carbon nanotubes (MWCNTs). The method includes two chemical-steps, in which a multi-parameter oxidation step is performed to achieve unzipping the carbon nanotubes. Then, a reduction step is carried out to achieve the final graphene nano-sheets. In the oxidation step, the oxidant material was minimized and balanced with longer curing time. This modification is made in order to reduce the oxygen-functional groups at the ends of graphene basal planes, which reduce its electrical conductivity. In addition, a similar adjustment is achieved in the reduction step, i.e. the consumed chemicals is reduced which make the overall process more economic and eco-friendly. The prepared nano-sheets were characterized by atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. The average thickness of the prepared graphene was about 5.23 nm.

Process for the conversion of and aqueous biomass hydrolyzate into fuels or chemicals by the selective removal of fermentation inhibitors

DOEpatents

Hames, Bonnie R.; Sluiter, Amie D.; Hayward, Tammy K.; Nagle, Nicholas J.

2004-05-18

A process of making a fuel or chemical from a biomass hydrolyzate is provided which comprises the steps of providing a biomass hydrolyzate, adjusting the pH of the hydrolyzate, contacting a metal oxide having an affinity for guaiacyl or syringyl functional groups, or both and the hydrolyzate for a time sufficient to form an adsorption complex; removing the complex wherein a sugar fraction is provided, and converting the sugar fraction to fuels or chemicals using a microorganism.

Biocatalytic conversion of methane to methanol as a key step for development of methane-based biorefineries.

PubMed

Hwang, In Yeub; Lee, Seung Hwan; Choi, Yoo Seong; Park, Si Jae; Na, Jeong Geol; Chang, In Seop; Kim, Choongik; Kim, Hyun Cheol; Kim, Yong Hwan; Lee, Jin Won; Lee, Eun Yeol

2014-12-28

Methane is considered as a next-generation carbon feedstock owing to the vast reserves of natural and shale gas. Methane can be converted to methanol by various methods, which in turn can be used as a starting chemical for the production of value-added chemicals using existing chemical conversion processes. Methane monooxygenase is the key enzyme that catalyzes the addition of oxygen to methane. Methanotrophic bacteria can transform methane to methanol by inhibiting methanol dehydrogenase. In this paper, we review the recent progress made on the biocatalytic conversion of methane to methanol as a key step for methane-based refinery systems and discuss future prospects for this technology.

Kinetic and Mechanism Study of Vanadium Acid Leaching from Black Shale Using Microwave Heating Method

NASA Astrophysics Data System (ADS)

Wang, Jing-peng; Zhang, Yi-min; Huang, Jing; Liu, Tao

2018-04-01

The leaching kinetics of the vanadium leaching process were investigated by the comparison of microwave heating and conventional heating methods. Microwave heating with CaF2 had a synergistic effect and improved the vanadium leaching efficiency. In contrast to conventional heating leaching, microwave heating accelerated the vanadium leaching rate by approximately 1-3% and by approximately 15% when CaF2 was also used. The kinetics analysis showed that the calculated activation energy decreased in the microwave heating method in the presence and absence of CaF2. The control procedure of leaching also changed from a chemical reaction control step to a mixed chemical diffusion control step upon the addition of CaF2. Microwave heating was shown to be suitable for leaching systems with diffusion or mixed chemical diffusion control steps when the target mineral does not have a microwave absorbing ability.

Kinetic and Mechanism Study of Vanadium Acid Leaching from Black Shale Using Microwave Heating Method

NASA Astrophysics Data System (ADS)

Wang, Jing-peng; Zhang, Yi-min; Huang, Jing; Liu, Tao

2018-06-01

The leaching kinetics of the vanadium leaching process were investigated by the comparison of microwave heating and conventional heating methods. Microwave heating with CaF2 had a synergistic effect and improved the vanadium leaching efficiency. In contrast to conventional heating leaching, microwave heating accelerated the vanadium leaching rate by approximately 1-3% and by approximately 15% when CaF2 was also used. The kinetics analysis showed that the calculated activation energy decreased in the microwave heating method in the presence and absence of CaF2. The control procedure of leaching also changed from a chemical reaction control step to a mixed chemical diffusion control step upon the addition of CaF2. Microwave heating was shown to be suitable for leaching systems with diffusion or mixed chemical diffusion control steps when the target mineral does not have a microwave absorbing ability.

A Miniature Wastewater Cleaning Plant to Demonstrate Primary Treatment in the Classroom

ERIC Educational Resources Information Center

Ne´el, Bastien; Cardoso, Catia; Perret, Didier; Bakker, Eric

2015-01-01

A small-scale wastewater cleaning plant is described that includes the key physical pretreatment steps followed by the chemical treatment of mud by flocculation. Water, clay particles, and riverside deposits mimicked odorless wastewater. After a demonstration of the optimization step, the flocculation process was carried out with iron(III)…

LC-MS/MS and UPLC-UV evaluation of anthocyanins and anthocyanidins during rabbiteye blueberry juice processing

USDA-ARS?s Scientific Manuscript database

Blueberry juice processing includes multiple steps and each affect the chemical composition of the berries, including thermal degradation of anthocyanins. Not from concentrate juice was made by heating and enzyme processing blueberries before pressing followed by ultrafiltration and pasteurization. ...

40 CFR 161.162 - Description of production process.

Code of Federal Regulations, 2010 CFR

2010-07-01

... applicant must submit information on the production (reaction) processes used to produce the active... continuous (a single reaction process from starting materials to active ingredient), but is accomplished in...) A flow chart of the chemical equations of each intended reaction occurring at each step of the...

40 CFR 161.162 - Description of production process.

Code of Federal Regulations, 2011 CFR

2011-07-01

... applicant must submit information on the production (reaction) processes used to produce the active... continuous (a single reaction process from starting materials to active ingredient), but is accomplished in...) A flow chart of the chemical equations of each intended reaction occurring at each step of the...

Terraforming - Making an earth of Mars

NASA Astrophysics Data System (ADS)

McKay, C. P.

1987-12-01

The possibility of creating a habitable environment on Mars via terraforming is discussed. The first step is to determine the amount, distribution, and chemical state of water, carbon dioxide, and nitrogen. The process of warming Mars and altering its atmosphere naturally divides into two steps: in the first step, the planet would be heated by a warm thick carbon dioxide atmosphere, while the second step would be to convert the atmospheric carbon dioxide and soil nitrates to the desired oxygen and nitrogen mixture. It is concluded that life will play a major role in any terraforming of Mars, and that terraforming will be a gradual evolutionary process duplicating the early evolution of life on earth.

Optimum processing of mammographic film.

PubMed

Sprawls, P; Kitts, E L

1996-03-01

Underprocessing of mammographic film can result in reduced contrast and visibility of breast structures and an unnecessary increase in radiation dose to the patient. Underprocessing can be caused by physical factors (low developer temperature, inadequate development time, insufficient developer agitation) or chemical factors (developer not optimized for film type; overdiluted, underreplenished, contaminated, or frequently changed developer). Conventional quality control programs are designed to produce consistent processing but do not address the issue of optimum processing. Optimum processing is defined as the level of processing that produces the film performance characteristics (contrast and sensitivity) specified by the film manufacturer. Optimum processing of mammographic film can be achieved by following a two-step protocol. The first step is to set up the processing conditions according to recommendations from the film and developer chemistry manufacturers. The second step is to verify the processing results by comparing them with sensitometric data provided by the film manufacturer.

Pollution prevention in the pulp and paper industry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jenkins, P.G.

1995-09-01

Probably no other industry has made as much progress as the kraft pulp and paper industry in reclaiming waste products. About half of the wood used in making pulp is cellulose; the reclamation of the other ingredients in the wood constitutes a continuing evolution of pollution prevention and economic success. The by-products of chemical pulping include turpentine used in the paint industry, lignosulfonates used as surfactants and dispersants, ``tall oil`` used in chemical manufacturing, yeast, vanillin, acetic acid, activated carbon, and alcohol. Sulfamic turpentine recovered in the kraft process is used to manufacture pine oil, dimethyl sulfoxide (DMSO), and othermore » useful chemical products. In addition, the noncellulose portion of the wood is used to provide energy for the pulping process through the combustion of concentrated black liquor. Over 75% of the pulp produced in the US is manufactured using the kraft process. Because of the predominance of the kraft process, the remainder of this section will address pollution prevention methods for kraft pulp and paper mills. Some of these techniques may be applicable or adaptable to other pulping processes, especially sulfite mills. The major steps in the kraft process are described, followed by a discussion of major wastestreams, and proven pollution prevention methods for each of these steps.« less

Validating Signs and Symptoms From An Actual Mass Casualty Incident to Characterize An Irritant Gas Syndrome Agent (IGSA) Exposure: A First Step in The Development of a Novel IGSA Triage Algorithm.

PubMed

Culley, Joan M; Richter, Jane; Donevant, Sara; Tavakoli, Abbas; Craig, Jean; DiNardi, Salvatore

2017-07-01

• Chemical exposures daily pose a significant threat to life. Rapid assessment by first responders/emergency nurses is required to reduce death and disability. Currently, no informatics tools for Irritant Gas Syndrome Agents (IGSA) exposures exist to process victims efficiently, continuously monitor for latent signs/symptoms, or make triage recommendations. • This study uses actual patient data from a chemical incident to characterize and validate signs/symptoms of an IGSA Syndrome. Validating signs/symptoms is the first step in developing new emergency department informatics tools with the potential to revolutionize the process by which emergency nurses manage triage victims of chemical incidents. Chemical exposures can pose a significant threat to life. Rapid assessment by first responders/emergency nurses is required to reduce death and disability. Currently, no informatics tools for irritant gas syndrome agents (IGSA) exposures exist to process victims efficiently, continuously monitor for latent signs/symptoms, or make triage recommendations. This study describes the first step in developing ED informatics tools for chemical incidents: validation of signs/symptoms that characterize an IGSA syndrome. Data abstracted from 146 patients treated for chlorine exposure in one emergency department during a 2005 train derailment and 152 patients not exposed to chlorine (a comparison group) were mapped to 93 possible signs/symptoms within 2 tools (WISER and CHEMM-IST) designed to assist emergency responders/emergency nurses with managing hazardous material exposures. Inferential statistics (χ 2 /Fisher's exact test) and diagnostics tests were used to examine mapped signs/symptoms of persons who were and were not exposed to chlorine. Three clusters of signs/symptoms are statistically associated with an IGSA syndrome (P < .01): respiratory (shortness of breath, wheezing, coughing, and choking); chest discomfort (tightness, pain, and burning), and eye, nose and/or throat (pain, irritation, and burning). The syndrome requires the presence of signs/symptoms from at least 2 of these clusters. The latency period must also be considered for exposed/potentially exposed persons. This study uses actual patient data from a chemical incident to characterize and validate signs/symptoms of an IGSA syndrome. Validating signs/symptoms is the first step in developing new ED informatics tools with the potential to revolutionize the process by which emergency nurses manage triage victims of chemical incidents. Copyright © 2017 Emergency Nurses Association. Published by Elsevier Inc. All rights reserved.

New Laboratory Course for Senior-Level Chemical Engineering Students

ERIC Educational Resources Information Center

Aronson, Mark T.; Deitcher, Robert W.; Xi, Yuanzhou; Davis, Robert J.

2009-01-01

A new laboratory course has been developed at the University of Virginia for senior- level chemical engineering students. The new course is based on three 4-week long experiments in bioprocess engineering, energy conversion and catalysis, and polymer synthesis and characterization. The emphasis is on the integration of process steps and the…

Rapid Production of a Porous Cellulose Acetate Membrane for Water Filtration Using Readily Available Chemicals

ERIC Educational Resources Information Center

Kaiser, Adrian; Stark, Wendelin J.; Grass, Robert N.

2017-01-01

A chemistry laboratory experiment using everyday items and readily available chemicals is described to introduce advanced high school students and undergraduate college students to porous polymer membranes. In a three-step manufacturing process, a membrane is produced at room temperature. The filtration principle of the membrane is then…

Preparation, characterization and dissolution of passive oxide film on the 400 series stainless steel surfaces

NASA Astrophysics Data System (ADS)

Sathyaseelan, V. S.; Rufus, A. L.; Chandramohan, P.; Subramanian, H.; Velmurugan, S.

2015-12-01

Full system decontamination of Primary Heat Transport (PHT) system of Pressurised Heavy Water Reactors (PHWRs) resulted in low decontamination factors (DF) on stainless steel (SS) surfaces. Hence, studies were carried out with 403 SS and 410 SS that are the material of construction of "End-Fitting body" and "End-Fitting Liner tubes". Three formulations were evaluated for the dissolution of passive films formed over these alloys viz., i) Two-step process consisting of oxidation and reduction reactions, ii) Dilute Chemical Decontamination (DCD) and iii) High Temperature Process. The two-step and high temperature processes could dissolve the oxide completely while the DCD process could remove only 60%. Various techniques like XRD, Raman spectroscopy and SEM-EDX were used for assessing the dissolution process. The two-step process is time consuming, laborious while the high temperature process is less time consuming and is recommended for SS decontamination.

Physico-Chemical Conversion of Lignocellulose: Inhibitor Effects and Detoxification Strategies: A Mini Review.

PubMed

Kim, Daehwan

2018-02-01

A pretreatment of lignocellulosic biomass to produce biofuels, polymers, and other chemicals plays a vital role in the biochemical conversion process toward disrupting the closely associated structures of the cellulose-hemicellulose-lignin molecules. Various pretreatment steps alter the chemical/physical structure of lignocellulosic materials by solubilizing hemicellulose and/or lignin, decreasing the particle sizes of substrate and the crystalline portions of cellulose, and increasing the surface area of biomass. These modifications enhance the hydrolysis of cellulose by increasing accessibilities of acids or enzymes onto the surface of cellulose. However, lignocellulose-derived byproducts, which can inhibit and/or deactivate enzyme and microbial biocatalysts, are formed, including furan derivatives, lignin-derived phenolics, and carboxylic acids. These generation of compounds during pretreatment with inhibitory effects can lead to negative effects on subsequent steps in sugar flat-form processes. A number of physico-chemical pretreatment methods such as steam explosion, ammonia fiber explosion (AFEX), and liquid hot water (LHW) have been suggested and developed for minimizing formation of inhibitory compounds and alleviating their effects on ethanol production processes. This work reviews the physico-chemical pretreatment methods used for various biomass sources, formation of lignocellulose-derived inhibitors, and their contributions to enzymatic hydrolysis and microbial activities. Furthermore, we provide an overview of the current strategies to alleviate inhibitory compounds present in the hydrolysates or slurries.

Oxidation-driven surface dynamics on NiAl(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Hailang; Chen, Xidong; Li, Liang

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

Oxidation-driven surface dynamics on NiAl(100)

DOE PAGES

Qin, Hailang; Chen, Xidong; Li, Liang; ...

2014-12-29

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

The Hazard Analysis and Critical Control Points (HACCP) generic model for the production of Thai fermented pork sausage (Nham).

PubMed

Paukatong, K V; Kunawasen, S

2001-01-01

Nham is a traditional Thai fermented pork sausage. The major ingredients of Nham are ground pork meat and shredded pork rind. Nham has been reported to be contaminated with Salmonella spp., Staphylococcus aureus, and Listeria monocytogenes. Therefore, it is a potential cause of foodborne diseases for consumers. A Hazard Analysis and Critical Control Points (HACCP) generic model has been developed for the Nham process. Nham processing plants were observed and a generic flow diagram of Nham processes was constructed. Hazard analysis was then conducted. Other than microbial hazards, the pathogens previously found in Nham, sodium nitrite and metal were identified as chemical and physical hazards in this product, respectively. Four steps in the Nham process have been identified as critical control points. These steps are the weighing of the nitrite compound, stuffing, fermentation, and labeling. The chemical hazard of nitrite must be controlled during the weighing step. The critical limit of nitrite levels in the Nham mixture has been set at 100-200 ppm. This level is high enough to control Clostridium botulinum but does not cause chemical hazards to the consumer. The physical hazard from metal clips could be prevented by visual inspection of every Nham product during stuffing. The microbiological hazard in Nham could be reduced in the fermentation process. The critical limit of the pH of Nham was set at lower than 4.6. Since this product is not cooked during processing, finally, educating the consumer, by providing information on the label such as "safe if cooked before consumption", could be an alternative way to prevent the microbiological hazards of this product.

Strategies for Stabilizing Nitrogenous Compounds in ECLSS Wastewater: Top-Down System Design and Unit Operation Selection with Focus on Bio-Regenerative Processes for Short and Long Term Scenarios

NASA Technical Reports Server (NTRS)

Lunn, Griffin M.

2011-01-01

Water recycling and eventual nutrient recovery is crucial for surviving in or past low earth orbit. New approaches and syste.m architecture considerations need to be addressed to meet current and future system requirements. This paper proposes a flexible system architecture that breaks down pretreatment , steps into discrete areas where multiple unit operations can be considered. An overview focusing on the urea and ammonia conversion steps allows an analysis on each process's strengths and weaknesses and synergy with upstream and downstream processing. Process technologies to be covered include chemical pretreatment, biological urea hydrolysis, chemical urea hydrolysis, combined nitrification-denitrification, nitrate nitrification, anammox denitrification, and regenerative ammonia absorption through struvite formation. Biological processes are considered mainly for their ability to both maximize water recovery and to produce nutrients for future plant systems. Unit operations can be considered for traditional equivalent system mass requirements in the near term or what they can provide downstream in the form of usable chemicals or nutrients for the long term closed-loop ecological control and life support system. Optimally this would allow a system to meet the former but to support the latter without major modification.

A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal-Organic Framework Materials HKUST-1 and Cu-MOF-2.

PubMed

Kim, Hong Ki; Yun, Won Seok; Kim, Min-Bum; Kim, Jeung Yoon; Bae, Youn-Sang; Lee, JaeDong; Jeong, Nak Cheon

2015-08-12

Open coordination sites (OCSs) in metal-organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative "chemical route" for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu(2+) center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films.

Electrochemical Probing through a Redox Capacitor To Acquire Chemical Information on Biothiols

PubMed Central

2016-01-01

The acquisition of chemical information is a critical need for medical diagnostics, food/environmental monitoring, and national security. Here, we report an electrochemical information processing approach that integrates (i) complex electrical inputs/outputs, (ii) mediators to transduce the electrical I/O into redox signals that can actively probe the chemical environment, and (iii) a redox capacitor that manipulates signals for information extraction. We demonstrate the capabilities of this chemical information processing strategy using biothiols because of the emerging importance of these molecules in medicine and because their distinct chemical properties allow evaluation of hypothesis-driven information probing. We show that input sequences can be tailored to probe for chemical information both qualitatively (step inputs probe for thiol-specific signatures) and quantitatively. Specifically, we observed picomolar limits of detection and linear responses to concentrations over 5 orders of magnitude (1 pM–0.1 μM). This approach allows the capabilities of signal processing to be extended for rapid, robust, and on-site analysis of chemical information. PMID:27385047

Electrochemical Probing through a Redox Capacitor To Acquire Chemical Information on Biothiols.

PubMed

Liu, Zhengchun; Liu, Yi; Kim, Eunkyoung; Bentley, William E; Payne, Gregory F

2016-07-19

The acquisition of chemical information is a critical need for medical diagnostics, food/environmental monitoring, and national security. Here, we report an electrochemical information processing approach that integrates (i) complex electrical inputs/outputs, (ii) mediators to transduce the electrical I/O into redox signals that can actively probe the chemical environment, and (iii) a redox capacitor that manipulates signals for information extraction. We demonstrate the capabilities of this chemical information processing strategy using biothiols because of the emerging importance of these molecules in medicine and because their distinct chemical properties allow evaluation of hypothesis-driven information probing. We show that input sequences can be tailored to probe for chemical information both qualitatively (step inputs probe for thiol-specific signatures) and quantitatively. Specifically, we observed picomolar limits of detection and linear responses to concentrations over 5 orders of magnitude (1 pM-0.1 μM). This approach allows the capabilities of signal processing to be extended for rapid, robust, and on-site analysis of chemical information.

40 CFR 161.162 - Description of production process.

Code of Federal Regulations, 2012 CFR

2012-07-01

... PROGRAMS DATA REQUIREMENTS FOR REGISTRATION OF ANTIMICROBIAL PESTICIDES Product Chemistry Data Requirements...) A flow chart of the chemical equations of each intended reaction occurring at each step of the...

Processes to remove acid forming gases from exhaust gases

DOEpatents

Chang, S.G.

1994-09-20

The present invention relates to a process for reducing the concentration of NO in a gas, which process comprises: (A) contacting a gas sample containing NO with a gaseous oxidizing agent to oxidize the NO to NO[sub 2]; (B) contacting the gas sample of step (A) comprising NO[sub 2] with an aqueous reagent of bisulfite/sulfite and a compound selected from urea, sulfamic acid, hydrazinium ion, hydrazoic acid, nitroaniline, sulfanilamide, sulfanilic acid, mercaptopropanoic acid, mercaptosuccinic acid, cysteine or combinations thereof at between about 0 and 100 C at a pH of between about 1 and 7 for between about 0.01 and 60 sec; and (C) optionally contacting the reaction product of step (A) with conventional chemical reagents to reduce the concentrations of the organic products of the reaction in step (B) to environmentally acceptable levels. Urea or sulfamic acid are preferred, especially sulfamic acid, and step (C) is not necessary or performed. 16 figs.

Studies of carbon incorporation on the diamond [100] surface during chemical vapor deposition using density functional theory.

PubMed

Cheesman, Andrew; Harvey, Jeremy N; Ashfold, Michael N R

2008-11-13

Accurate potential energy surface calculations are presented for many of the key steps involved in diamond chemical vapor deposition on the [100] surface (in its 2 x 1 reconstructed and hydrogenated form). The growing diamond surface was described by using a large (approximately 1500 atoms) cluster model, with the key atoms involved in chemical steps being described by using a quantum mechanical (QM, density functional theory, DFT) method and the bulk of the atoms being described by molecular mechanics (MM). The resulting hybrid QM/MM calculations are more systematic and/or at a higher level of theory than previous work on this growth process. The dominant process for carbon addition, in the form of methyl radicals, is predicted to be addition to a surface radical site, opening of the adjacent C-C dimer bond, insertion, and ultimate ring closure. Other steps such as insertion across the trough between rows of dimer bonds or addition to a neighboring dimer leading to formation of a reconstruction on the next layer may also contribute. Etching of carbon can also occur; the most likely mechanism involves loss of a two-carbon moiety in the form of ethene. The present higher-level calculations confirm that migration of inserted carbon along both dimer rows and chains should be relatively facile, with barriers of approximately 150 kJ mol (-1) when starting from suitable diradical species, and that this step should play an important role in establishing growth of smooth surfaces.

Removal of sulphates acidity and iron from acid mine drainage in a bench scale biochemical treatment system.

PubMed

Prasad, D; Henry, J G

2009-02-01

The focus of this study was to develop a simple biochemical system to treat acid mine drainage for its safe disposal. Recovery and reuse of the metals removed were not considered. A three-step process for the treatment of acid mine drainage (AMD), proposed earlier, separates sulphate reducing activity from metal precipitation units and from a pH control system. Following our earlier work on the first step (biological reactor), this paper examines the second step (i.e. chemical reactor). The objectives of this study were: (1) to determine the increase in pH and the reduction of iron in the chemical reactor for different proportions of simulated AMD, and (2) to assess the capability of the chemical reactor. A series of experiments was conducted to study the effects of addition of alkaline sulphidogenic liquor (ASL) derived from a batch sulphidogenic biological reactor (operating with activated sludge and a COD/SO4 ratio of 1.6) on the simulated AMD characteristics. At 60-minute contact time, addition of 30% ASL (pH of 7.60-7.76) to the chemical reactor with 70% AMD (pH of 1.65-2.02), increased the pH of the AMD to 6.57 and alkalinity from 0 to 485 mg l(-1) as CaCO3, respectively and precipitated about 97% of the iron present in the simulated AMD. Others have demonstrated that metals in mine drainage can be precipitated by bacterial sulphate reduction. In this study, iron, a common and major component of mine drainage was used as a surrogate for metals in general. The results indicate the feasibility of treating AMD by an engineered sulphidogenic anaerobic reactor followed by a chemical reactor and that our three-step biochemical process has important advantages over other conventional AMD treatment systems.

Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods.

PubMed

Suleimanov, Yury V; Green, William H

2015-09-08

We present a simple protocol which allows fully automated discovery of elementary chemical reaction steps using in cooperation double- and single-ended transition-state optimization algorithms--the freezing string and Berny optimization methods, respectively. To demonstrate the utility of the proposed approach, the reactivity of several single-molecule systems of combustion and atmospheric chemistry importance is investigated. The proposed algorithm allowed us to detect without any human intervention not only "known" reaction pathways, manually detected in the previous studies, but also new, previously "unknown", reaction pathways which involve significant atom rearrangements. We believe that applying such a systematic approach to elementary reaction path finding will greatly accelerate the discovery of new chemistry and will lead to more accurate computer simulations of various chemical processes.

Nanorods on surface of GaN-based thin-film LEDs deposited by post-annealing after photo-assisted chemical etching

NASA Astrophysics Data System (ADS)

Chen, Lung-Chien; Lin, Wun-Wei; Liu, Te-Yu

2017-01-01

This study investigates the optoelectronic characteristics of gallium nitride (GaN)-based thin-film light-emitting diodes (TF-LEDs) that are formed by a two-step transfer process that involves wet etching and post-annealing. In the two-step transfer process, GaN LEDs were stripped from sapphire substrates by the laser lift-off (LLO) method using a KrF laser and then transferred onto ceramic substrates. Ga-K nanorods were formed on the surface of the GaN-based TF-LEDs following photo-assisted chemical etching and photo-enhanced post-annealing at 100 °C for 1 min. As a result, the light output power of GaN-based TF-LEDs with wet etching and post-annealing was over 72% more than that of LEDs that did not undergo these treatments.

PILOT PLANT STUDY OF CONVERSION OF COAL TO LOW SULFUR FUEL

EPA Science Inventory

The report gives results of a program to develop, on bench and pilot scales, operating conditions for the key step in the IGT process to desulfurize coal by thermal and chemical treatment. This process, to date, uses the 'sulfur-getter' concept. (A sulfur-getter is a material tha...

Isothermal DNA origami folding: avoiding denaturing conditions for one-pot, hybrid-component annealing

NASA Astrophysics Data System (ADS)

Kopielski, Andreas; Schneider, Anne; Csáki, Andrea; Fritzsche, Wolfgang

2015-01-01

The DNA origami technique offers great potential for nanotechnology. Using biomolecular self-assembly, defined 2D and 3D nanoscale DNA structures can be realized. DNA origami allows the positioning of proteins, fluorophores or nanoparticles with an accuracy of a few nanometers and enables thereby novel nanoscale devices. Origami assembly usually includes a thermal denaturation step at 90 °C. Additional components used for nanoscale assembly (such as proteins) are often thermosensitive, and possibly damaged by such harsh conditions. They have therefore to be attached in an extra second step to avoid defects. To enable a streamlined one-step nanoscale synthesis - a so called one-pot folding - an adaptation of the folding procedures is required. Here we present a thermal optimization of this process for a 2D DNA rectangle-shaped origami resulting in an isothermal assembly protocol below 60 °C without thermal denaturation. Moreover, a room temperature protocol is presented using the chemical additive betaine, which is biocompatible in contrast to chemical denaturing approaches reported previously.The DNA origami technique offers great potential for nanotechnology. Using biomolecular self-assembly, defined 2D and 3D nanoscale DNA structures can be realized. DNA origami allows the positioning of proteins, fluorophores or nanoparticles with an accuracy of a few nanometers and enables thereby novel nanoscale devices. Origami assembly usually includes a thermal denaturation step at 90 °C. Additional components used for nanoscale assembly (such as proteins) are often thermosensitive, and possibly damaged by such harsh conditions. They have therefore to be attached in an extra second step to avoid defects. To enable a streamlined one-step nanoscale synthesis - a so called one-pot folding - an adaptation of the folding procedures is required. Here we present a thermal optimization of this process for a 2D DNA rectangle-shaped origami resulting in an isothermal assembly protocol below 60 °C without thermal denaturation. Moreover, a room temperature protocol is presented using the chemical additive betaine, which is biocompatible in contrast to chemical denaturing approaches reported previously. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04176c

Colorimetric detection of uranium in water

DOEpatents

DeVol, Timothy A [Clemson, SC; Hixon, Amy E [Piedmont, SC; DiPrete, David P [Evans, GA

2012-03-13

Disclosed are methods, materials and systems that can be used to determine qualitatively or quantitatively the level of uranium contamination in water samples. Beneficially, disclosed systems are relatively simple and cost-effective. For example, disclosed systems can be utilized by consumers having little or no training in chemical analysis techniques. Methods generally include a concentration step and a complexation step. Uranium concentration can be carried out according to an extraction chromatographic process and complexation can chemically bind uranium with a detectable substance such that the formed substance is visually detectable. Methods can detect uranium contamination down to levels even below the MCL as established by the EPA.

Evolution of Volatile Compounds during the Distillation of Cognac Spirit.

PubMed

Awad, Pierre; Athès, Violaine; Decloux, Martine Esteban; Ferrari, Gérald; Snakkers, Guillaume; Raguenaud, Patrick; Giampaoli, Pierre

2017-09-06

Cognac wine spirit has a complex composition in volatile compounds which contributes to its organoleptic profile. This work focused on the batch distillation process and, in particular, on volatile compounds specifically produced by chemical reactions during the distillation of Cognac wine spirit, traditionally conducted in two steps with charentais pot stills. The aim of this study was to characterize these volatile compounds formed during distillation. Sampling has been performed on the distillates and inside the boiler during a typical Cognac distillation. The analysis of these samples allowed us to perform a mass balance and to point out several types of volatile compounds whose quantities strongly increased during the distillation process. These compounds were distinguished by their chemical family. It has been found that the first distillation step was decisive for the formation of volatile compounds. Moreover, 2 esters, 3 aldehydes, 12 norisoprenoids, and 3 terpenes were shown to be generated during the process. These results suggest that some volatile compounds found in Cognac spirit are formed during distillation due to chemical reactions induced by high temperature. These findings give important indications to professional distillers in order to enhance the product's quality.

Biomass in the manufacture of industrial products—the use of proteins and amino acids

PubMed Central

Peter, Francisc; Sanders, Johan

2007-01-01

The depletion in fossil feedstocks, increasing oil prices, and the ecological problems associated with CO2 emissions are forcing the development of alternative resources for energy, transport fuels, and chemicals: the replacement of fossil resources with CO2 neutral biomass. Allied with this, the conversion of crude oil products utilizes primary products (ethylene, etc.) and their conversion to either materials or (functional) chemicals with the aid of co-reagents such as ammonia and various process steps to introduce functionalities such as -NH2 into the simple structures of the primary products. Conversely, many products found in biomass often contain functionalities. Therefore, it is attractive to exploit this to bypass the use, and preparation of, co-reagents as well as eliminating various process steps by utilizing suitable biomass-based precursors for the production of chemicals. It is the aim of this mini-review to describe the scope of the possibilities to generate current functionalized chemical materials using amino acids from biomass instead of fossil resources, thereby taking advantage of the biomass structure in a more efficient way than solely utilizing biomass for the production of fuels or electricity. PMID:17387469

STEP wastewater treatment: a solar thermal electrochemical process for pollutant oxidation.

PubMed

Wang, Baohui; Wu, Hongjun; Zhang, Guoxue; Licht, Stuart

2012-10-01

A solar thermal electrochemical production (STEP) pathway was established to utilize solar energy to drive useful chemical processes. In this paper, we use experimental chemistry for efficient STEP wastewater treatment, and suggest a theory based on the decreasing stability of organic pollutants (hydrocarbon oxidation potentials) with increasing temperature. Exemplified by the solar thermal electrochemical oxidation of phenol, the fundamental model and experimental system components of this process outline a general method for the oxidation of environmentally stable organic pollutants into carbon dioxide, which is easily removed. Using thermodynamic calculations we show a sharply decreasing phenol oxidation potential with increasing temperature. The experimental results demonstrate that this increased temperature can be supplied by solar thermal heating. In combination this drives electrochemical phenol removal with enhanced oxidation efficiency through (i) a thermodynamically driven decrease in the energy needed to fuel the process and (ii) improved kinetics to sustain high rates of phenol oxidation at low electrochemical overpotential. The STEP wastewater treatment process is synergistic in that it is performed with higher efficiency than either electrochemical or photovoltaic conversion process acting alone. STEP is a green, efficient, safe, and sustainable process for organic wastewater treatment driven solely by solar energy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of microbial community shifts in two parallel multi-step drinking water treatment processes.

PubMed

Xu, Jiajiong; Tang, Wei; Ma, Jun; Wang, Hong

2017-07-01

Drinking water treatment processes remove undesirable chemicals and microorganisms from source water, which is vital to public health protection. The purpose of this study was to investigate the effects of treatment processes and configuration on the microbiome by comparing microbial community shifts in two series of different treatment processes operated in parallel within a full-scale drinking water treatment plant (DWTP) in Southeast China. Illumina sequencing of 16S rRNA genes of water samples demonstrated little effect of coagulation/sedimentation and pre-oxidation steps on bacterial communities, in contrast to dramatic and concurrent microbial community shifts during ozonation, granular activated carbon treatment, sand filtration, and disinfection for both series. A large number of unique operational taxonomic units (OTUs) at these four treatment steps further illustrated their strong shaping power towards the drinking water microbial communities. Interestingly, multidimensional scaling analysis revealed tight clustering of biofilm samples collected from different treatment steps, with Nitrospira, the nitrite-oxidizing bacteria, noted at higher relative abundances in biofilm compared to water samples. Overall, this study provides a snapshot of step-to-step microbial evolvement in multi-step drinking water treatment systems, and the results provide insight to control and manipulation of the drinking water microbiome via optimization of DWTP design and operation.

Shape-dependent guidance of active Janus particles by chemically patterned surfaces

NASA Astrophysics Data System (ADS)

Uspal, W. E.; Popescu, M. N.; Tasinkevych, M.; Dietrich, S.

2018-01-01

Self-phoretic chemically active Janus particles move by inducing—via non-equilibrium chemical reactions occurring on their surfaces—changes in the chemical composition of the solution in which they are immersed. This process leads to gradients in chemical composition along the surface of the particle, as well as along any nearby boundaries, including solid walls. Chemical gradients along a wall can give rise to chemi-osmosis, i.e., the gradients drive surface flows which, in turn, drive flow in the volume of the solution. This bulk flow couples back to the particle, and thus contributes to its self-motility. Since chemi-osmosis strongly depends on the molecular interactions between the diffusing molecular species and the wall, the response flow induced and experienced by a particle encodes information about any chemical patterning of the wall. Here, we extend previous studies on self-phoresis of a sphere near a chemically patterned wall to the case of particles with rod-like, elongated shape. We focus our analysis on the new phenomenology potentially emerging from the coupling—which is inoperative for a spherical shape—of the elongated particle to the strain rate tensor of the chemi-osmotic flow. Via detailed numerical calculations, we show that the dynamics of a rod-like particle exhibits a novel ‘edge-following’ steady state: the particle translates along the edge of a chemical step at a steady distance from the step and with a steady orientation. Moreover, within a certain range of system parameters, the edge-following state co-exists with a ‘docking’ state (the particle stops at the step, oriented perpendicular to the step edge), i.e., a bistable dynamics occurs. These findings are rationalized as a consequence of the competition between the fluid vorticity and the rate of strain by using analytical theory based on the point-particle approximation which captures quasi-quantitatively the dynamics of the system.

Guiding gate-etch process development using 3D surface reaction modeling for 7nm and beyond

NASA Astrophysics Data System (ADS)

Dunn, Derren; Sporre, John R.; Deshpande, Vaibhav; Oulmane, Mohamed; Gull, Ronald; Ventzek, Peter; Ranjan, Alok

2017-03-01

Increasingly, advanced process nodes such as 7nm (N7) are fundamentally 3D and require stringent control of critical dimensions over high aspect ratio features. Process integration in these nodes requires a deep understanding of complex physical mechanisms to control critical dimensions from lithography through final etch. Polysilicon gate etch processes are critical steps in several device architectures for advanced nodes that rely on self-aligned patterning approaches to gate definition. These processes are required to meet several key metrics: (a) vertical etch profiles over high aspect ratios; (b) clean gate sidewalls free of etch process residue; (c) minimal erosion of liner oxide films protecting key architectural elements such as fins; and (e) residue free corners at gate interfaces with critical device elements. In this study, we explore how hybrid modeling approaches can be used to model a multi-step finFET polysilicon gate etch process. Initial parts of the patterning process through hardmask assembly are modeled using process emulation. Important aspects of gate definition are then modeled using a particle Monte Carlo (PMC) feature scale model that incorporates surface chemical reactions.1 When necessary, species and energy flux inputs to the PMC model are derived from simulations of the etch chamber. The modeled polysilicon gate etch process consists of several steps including a hard mask breakthrough step (BT), main feature etch steps (ME), and over-etch steps (OE) that control gate profiles at the gate fin interface. An additional constraint on this etch flow is that fin spacer oxides are left intact after final profile tuning steps. A natural optimization required from these processes is to maximize vertical gate profiles while minimizing erosion of fin spacer films.2

Synthesis of Ultrathin Si Nanosheets from Natural Clays for Lithium-Ion Battery Anodes.

PubMed

Ryu, Jaegeon; Hong, Dongki; Choi, Sinho; Park, Soojin

2016-02-23

Two-dimensional Si nanosheets have been studied as a promising candidate for lithium-ion battery anode materials. However, Si nanosheets reported so far showed poor cycling performances and required further improvements. In this work, we utilize inexpensive natural clays for preparing high quality Si nanosheets via a one-step simultaneous molten salt-induced exfoliation and chemical reduction process. This approach produces high purity mesoporous Si nanosheets in high yield. As a control experiment, two-step process (pre-exfoliated silicate sheets and subsequent chemical reduction) cannot sustain their original two-dimensional structure. In contrast, one-step method results in a production of 5 nm-thick highly porous Si nanosheets. Carbon-coated Si nanosheet anodes exhibit a high reversible capacity of 865 mAh g(-1) at 1.0 A g(-1) with an outstanding capacity retention of 92.3% after 500 cycles. It also delivers high rate capability, corresponding to a capacity of 60% at 20 A g(-1) compared to that of 2.0 A g(-1). Furthermore, the Si nanosheet electrodes show volume expansion of only 42% after 200 cycles.

Toward intensifying design of experiments in upstream bioprocess development: An industrial Escherichia coli feasibility study.

PubMed

von Stosch, Moritz; Hamelink, Jan-Martijn; Oliveira, Rui

2016-09-01

In this study, step variations in temperature, pH, and carbon substrate feeding rate were performed within five high cell density Escherichia coli fermentations to assess whether intraexperiment step changes, can principally be used to exploit the process operation space in a design of experiment manner. A dynamic process modeling approach was adopted to determine parameter interactions. A bioreactor model was integrated with an artificial neural network that describes biomass and product formation rates as function of varied fed-batch fermentation conditions for heterologous protein production. A model reliability measure was introduced to assess in which process region the model can be expected to predict process states accurately. It was found that the model could accurately predict process states of multiple fermentations performed at fixed conditions within the determined validity domain. The results suggest that intraexperimental variations of process conditions could be used to reduce the number of experiments by a factor, which in limit would be equivalent to the number of intraexperimental variations per experiment. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1343-1352, 2016. © 2016 American Institute of Chemical Engineers.

Physical and mathematical modeling of antimicrobial photodynamic therapy

NASA Astrophysics Data System (ADS)

Bürgermeister, Lisa; López, Fernando Romero; Schulz, Wolfgang

2014-07-01

Antimicrobial photodynamic therapy (aPDT) is a promising method to treat local bacterial infections. The therapy is painless and does not cause bacterial resistances. However, there are gaps in understanding the dynamics of the processes, especially in periodontal treatment. This work describes the advances in fundamental physical and mathematical modeling of aPDT used for interpretation of experimental evidence. The result is a two-dimensional model of aPDT in a dental pocket phantom model. In this model, the propagation of laser light and the kinetics of the chemical reactions are described as coupled processes. The laser light induces the chemical processes depending on its intensity. As a consequence of the chemical processes, the local optical properties and distribution of laser light change as well as the reaction rates. The mathematical description of these coupled processes will help to develop treatment protocols and is the first step toward an inline feedback system for aPDT users.

Biointervention makes leather processing greener: an integrated cleansing and tanning system.

PubMed

Thanikaivelan, Palanisamy; Rao, Jonnalagadda Raghava; Nair, Balachandran Unni; Ramasami, Thirumalachari

2003-06-01

The do-undo methods adopted in conventional leather processing generate huge amounts of pollutants. In other words, conventional methods employed in leather processing subject the skin/hide to wide variations in pH. Pretanning and tanning processes alone contribute more than 90% of the total pollution from leather processing. Included in this is a great deal of solid wastes such as lime and chrome sludge. In the approach described here, the hair and flesh removal as well as fiber opening have been achieved using biocatalysts at pH 8.0 for cow hides. This was followed by a pickle-free chrome tanning, which does not require a basification step. Hence, this tanning technique involves primarily three steps, namely, dehairing, fiber opening, and tanning. It has been found that the extent of hair removal, opening up of fiber bundles, and penetration and distribution of chromium are comparable to that produced by traditional methods. This has been substantiated through scanning electron microscopic, stratigraphic chrome distribution analysis, and softness measurements. Performance of the leathers is shown to be on par with conventionally processed leathers through physical and hand evaluation. Importantly, softness of the leathers is numerically proven to be comparable with that of control. The process also demonstrates reduction in chemical oxygen demand load by 80%, total solids load by 85%, and chromium load by 80% as compared to the conventional process, thereby leading toward zero discharge. The input-output audit shows that the biocatalytic three-step tanning process employs a very low amount of chemicals, thereby reducing the discharge by 90% as compared to the conventional multistep processing. Furthermore, it is also demonstrated that the process is technoeconomically viable.

Pectin gelation with chlorhexidine: Physico-chemical studies in dilute solutions.

PubMed

Lascol, Manon; Bourgeois, Sandrine; Guillière, Florence; Hangouët, Marie; Raffin, Guy; Marote, Pedro; Lantéri, Pierre; Bordes, Claire

2016-10-05

Low methoxyl pectin is known to gel with divalent cations (e.g. Ca(2+), Zn(2+)). In this study, a new way of pectin gelation in the presence of an active pharmaceutical ingredient, chlorhexidine (CX), was highlighted. Thus chlorhexidine interactions with pectin were investigated and compared with the well-known pectin/Ca(2+) binding model. Gelation mechanisms were studied by several physico-chemical methods such as zeta potential, viscosity, size measurements and binding isotherm was determined by Proton Nuclear Magnetic Resonance Spectroscopy ((1)H NMR). The binding process exhibited similar first two steps for both divalent ions: a stoichiometric monocomplexation of the polymer followed by a dimerization step. However, stronger interactions were observed between pectin and chlorhexidine. Moreover, the dimerization step occurred under stoichiometric conditions with chlorhexidine whereas non-stoichiometric conditions were involved with calcium ions. In the case of chlorhexidine, an additional intermolecular binding occurred in a third step. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method for conversion of carbohydrate polymers to value-added chemical products

DOEpatents

Zhang, Zongchao C [Norwood, NJ; Brown, Heather M [Kennewick, WA; Su, Yu [Richland, WA

2012-02-07

Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120.degree. C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.

The Procter and Gamble Decaffeination Project: A Multimedia Instruction Module.

ERIC Educational Resources Information Center

Squires, R. G.; And Others

1996-01-01

Purdue University (Indiana) is developing a series of computer modules of state-of-the-art chemical engineering processes to serve as the basis for computer-simulated experiments. One, sponsored by Procter and Gamble, models the extraction step in the decaffeination process and allows students to determine the optimal extraction conditions for…

ECUT: Energy Conversion and utilization Technologies program biocatalysis research activity. Generation of chemical intermediates by catalytic oxidative decarboxylation of dilute organic acids

NASA Technical Reports Server (NTRS)

Distefano, S.; Gupta, A.; Ingham, J. D.

1983-01-01

A rhodium-based catalyst was prepared and preliminary experiments were completed where the catalyst appeared to decarboxylate dilute acids at concentrations of 1 to 10 vol%. Electron spin resonance spectroscoy was used to characterize the catalyst as a first step leading toward modeling and optimization of rhodium catalysts. Also, a hybrid chemical/biological process for the production of hydrocarbons has been assessed. These types of catalysts could greatly increase energy efficiency of this process.

Nanorods on surface of GaN-based thin-film LEDs deposited by post-annealing after photo-assisted chemical etching.

PubMed

Chen, Lung-Chien; Lin, Wun-Wei; Liu, Te-Yu

2017-12-01

This study investigates the optoelectronic characteristics of gallium nitride (GaN)-based thin-film light-emitting diodes (TF-LEDs) that are formed by a two-step transfer process that involves wet etching and post-annealing. In the two-step transfer process, GaN LEDs were stripped from sapphire substrates by the laser lift-off (LLO) method using a KrF laser and then transferred onto ceramic substrates. Ga-K nanorods were formed on the surface of the GaN-based TF-LEDs following photo-assisted chemical etching and photo-enhanced post-annealing at 100 °C for 1 min. As a result, the light output power of GaN-based TF-LEDs with wet etching and post-annealing was over 72% more than that of LEDs that did not undergo these treatments.

Argon–germane in situ plasma clean for reduced temperature Ge on Si epitaxy by high density plasma chemical vapor deposition

DOE PAGES

Douglas, Erica A.; Sheng, Josephine J.; Verley, Jason C.; ...

2015-06-04

We found that the demand for integration of near infrared optoelectronic functionality with silicon complementary metal oxide semiconductor (CMOS) technology has for many years motivated the investigation of low temperature germanium on silicon deposition processes. Our work describes the development of a high density plasma chemical vapor deposition process that uses a low temperature (<460 °C) in situ germane/argon plasma surface preparation step for epitaxial growth of germanium on silicon. It is shown that the germane/argon plasma treatment sufficiently removes SiO x and carbon at the surface to enable germanium epitaxy. Finally, the use of this surface preparation step demonstratesmore » an alternative way to produce germanium epitaxy at reduced temperatures, a key enabler for increased flexibility of integration with CMOS back-end-of-line fabrication.« less

Regeneration of glass nanofluidic chips through a multiple-step sequential thermochemical decomposition process at high temperatures.

PubMed

Xu, Yan; Wu, Qian; Shimatani, Yuji; Yamaguchi, Koji

2015-10-07

Due to the lack of regeneration methods, the reusability of nanofluidic chips is a significant technical challenge impeding the efficient and economic promotion of both fundamental research and practical applications on nanofluidics. Herein, a simple method for the total regeneration of glass nanofluidic chips was described. The method consists of sequential thermal treatment with six well-designed steps, which correspond to four sequential thermal and thermochemical decomposition processes, namely, dehydration, high-temperature redox chemical reaction, high-temperature gasification, and cooling. The method enabled the total regeneration of typical 'dead' glass nanofluidic chips by eliminating physically clogged nanoparticles in the nanochannels, removing chemically reacted organic matter on the glass surface and regenerating permanent functional surfaces of dissimilar materials localized in the nanochannels. The method provides a technical solution to significantly improve the reusability of glass nanofluidic chips and will be useful for the promotion and acceleration of research and applications on nanofluidics.

Method for verification of constituents of a process stream just as they go through an inlet of a reaction vessel

DOEpatents

Baylor, Lewis C.; Buchanan, Bruce R.; O'Rourke, Patrick E.

1995-01-01

A method for validating a process stream for the presence or absence of a substance of interest such as a chemical warfare agent; that is, for verifying that a chemical warfare agent is present in an input line for feeding the agent into a reaction vessel for destruction, or, in a facility for producing commercial chemical products, that a constituent of the chemical warfare agent has not been substituted for the proper chemical compound. The method includes the steps of transmitting light through a sensor positioned in the feed line just before the chemical constituent in the input line enters the reaction vessel, measuring an optical spectrum of the chemical constituent from the light beam transmitted through it, and comparing the measured spectrum to a reference spectrum of the chemical agent and preferably also reference spectra of surrogates. A signal is given if the chemical agent is not entering a reaction vessel for destruction, or if a constituent of a chemical agent is added to a feed line in substitution of the proper chemical compound.

Method for verification of constituents of a process stream

DOEpatents

Baylor, L.C.; Buchanan, B.R.; O`Rourke, P.E.

1993-01-01

This invention is comprised of a method for validating a process stream for the presence or absence of a substance of interest such as a chemical warfare agent; that is, for verifying that a chemical warfare agent is present in an input line for feeding the agent into a reaction vessel for destruction, or, in a facility for producing commercial chemical products, that a constituent of the chemical warfare agent has not been substituted for the proper chemical compound. The method includes the steps of transmitting light through a sensor positioned in the feed line just before the chemical constituent in the input line enters the reaction vessel, measuring an optical spectrum of the chemical constituent from the light beam transmitted through it, and comparing the measured spectrum to a reference spectrum of the chemical agent and preferable also reference spectra of surrogates. A signal is given if the chemical agent is not entering a reaction vessel for destruction, or if a constituent of a chemical agent is added to a feed line in substitution of the proper chemical compound.

Harmonised framework for ecological risk assessment of sediments from ports and estuarine zones of North and South Atlantic.

PubMed

Choueri, R B; Cesar, A; Abessa, D M S; Torres, R J; Riba, I; Pereira, C D S; Nascimento, M R L; Morais, R D; Mozeto, A A; DelValls, T A

2010-04-01

This paper presents a harmonised framework of sediment quality assessment and dredging material characterisation for estuaries and port zones of North and South Atlantic. This framework, based on the weight-of-evidence approach, provides a structure and a process for conducting sediment/dredging material assessment that leads to a decision. The main structure consists of "step 1" (examination of available data); "step 2" (chemical characterisation and toxicity assessment); "decision 1" (any chemical level higher than reference values? are sediments toxic?); "step 3" (assessment of benthic community structure); "step 4" (integration of the results); "decision 2" (are sediments toxic or benthic community impaired?); "step 5" (construction of the decision matrix) and "decision 3" (is there environmental risk?). The sequence of assessments may be interrupted when the information obtained is judged to be sufficient for a correct characterisation of the risk posed by the sediments/dredging material. This framework brought novel features compared to other sediment/dredging material risk assessment frameworks: data integration through multivariate analysis allows the identification of which samples are toxic and/or related to impaired benthic communities; it also discriminates the chemicals responsible for negative biological effects; and the framework dispenses the use of a reference area. We demonstrated the successful application of this framework in different port and estuarine zones of the North (Gulf of Cádiz) and South Atlantic (Santos and Paranaguá Estuarine Systems).

Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

PubMed

Laborda, Eduardo; Gómez-Gil, José María; Molina, Angela

2017-06-28

A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

Physico-chemical, colorimetric, rheological parameters and chemometric discrimination of the origin of Mugil cephalus' roes during the manufacturing process of Bottarga.

PubMed

Caredda, Marco; Addis, Margherita; Pes, Massimo; Fois, Nicola; Sanna, Gabriele; Piredda, Giovanni; Sanna, Gavino

2018-06-01

The aim of this work was to measure the physico-chemical and the colorimetric parameters of ovaries from Mugil cephalus caught in the Tortolì lagoon (South-East coast of Sardinia) along the steps of the manufacturing process of Bottarga, together with the rheological parameters of the final product. A lowering of all CIELab coordinates (lightness, redness and yellowness) was observed during the manufacture process. All CIELab parameters were used to build a Linear Discriminant Analysis (LDA) predictive model able to determine in real time if the roes had been subdued to a freezing process, with a success in prediction of 100%. This model could be used to identify the origin of the roes, since only the imported ones are frozen. The major changes of all the studied parameters (p < 0.05) were noted in the drying step rather than in the salting step. After processing, Bottarga was characterized by a pH value of 5.46 (CV = 2.8) and a moisture content of 25% (CV = 8), whereas the typical per cent amounts of proteins, fat and NaCl, calculated as a percentage on the dried weight, were 56 (CV = 2), 34 (CV = 3) and 3.6 (CV = 17), respectively. The physical chemical changes of the roes during the manufacturing process were consistent for moisture, which decreased by 28%, whereas the protein and the fat contents on the dried weight got respectively lower of 3% and 2%. NaCl content increased by 3.1%. Principal Component Analyses (PCA) were also performed on all data to establish trends and relationships among all parameters. Hardness and consistency of Bottarga were negatively correlated with the moisture content (r = -0.87 and r = -0.88, respectively), while its adhesiveness was negatively correlated with the fat content (r = -0.68). Copyright © 2018. Published by Elsevier Ltd.

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

2003-01-01

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HC1 vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow- chemical ionization mass spectrometry and optical ellipsometry, among others. The next section summarizes our research activities during the first year of the project, and the section that follows consists of the statement of work for the second year.

An approach in building a chemical compound search engine in oracle database.

PubMed

Wang, H; Volarath, P; Harrison, R

2005-01-01

A searching or identifying of chemical compounds is an important process in drug design and in chemistry research. An efficient search engine involves a close coupling of the search algorithm and database implementation. The database must process chemical structures, which demands the approaches to represent, store, and retrieve structures in a database system. In this paper, a general database framework for working as a chemical compound search engine in Oracle database is described. The framework is devoted to eliminate data type constrains for potential search algorithms, which is a crucial step toward building a domain specific query language on top of SQL. A search engine implementation based on the database framework is also demonstrated. The convenience of the implementation emphasizes the efficiency and simplicity of the framework.

Processes to remove acid forming gases from exhaust gases

DOEpatents

Chang, Shih-Ger

1994-01-01

The present invention relates to a process for reducing the concentration of NO in a gas, which process comprises: (A) contacting a gas sample containing NO with a gaseous oxidizing agent to oxidize the NO to NO.sub.2 ; (B) contacting the gas sample of step (A) comprising NO.sub.2 with an aqueous reagent of bisulfite/sulfite and a compound selected from urea, sulfamic acid, hydrazinium ion, hydrazoic acid, nitroaniline, sulfanilamide, sulfanilic acid, mercaptopropanoic acid, mercaptosuccinic acid, cysteine or combinations thereof at between about 0.degree. and 100.degree. C. at a pH of between about 1 and 7 for between about 0.01 and 60 sec; and (C) optionally contacting the reaction product of step (A) with conventional chemical reagents to reduce the concentrations of the organic products of the reaction in step (B) to environ-mentally acceptable levels. Urea or sulfamic acid are preferred, especially sulfamic acid, and step (C) is not necessary or performed.

Industrial production of L-ascorbic Acid (vitamin C) and D-isoascorbic acid.

PubMed

Pappenberger, Günter; Hohmann, Hans-Peter

2014-01-01

L-ascorbic acid (vitamin C) was first isolated in 1928 and subsequently identified as the long-sought antiscorbutic factor. Industrially produced L-ascorbic acid is widely used in the feed, food, and pharmaceutical sector as nutritional supplement and preservative, making use of its antioxidative properties. Until recently, the Reichstein-Grüssner process, designed in 1933, was the main industrial route. Here, D-sorbitol is converted to L-ascorbic acid via 2-keto-L-gulonic acid (2KGA) as key intermediate, using a bio-oxidation with Gluconobacter oxydans and several chemical steps. Today, industrial production processes use additional bio-oxidation steps with Ketogulonicigenium vulgare as biocatalyst to convert D-sorbitol to the intermediate 2KGA without chemical steps. The enzymes involved are characterized by a broad substrate range, but remarkable regiospecificity. This puzzling specificity pattern can be understood from the preferences of these enyzmes for certain of the many isomeric structures which the carbohydrate substrates adopt in aqueous solution. Recently, novel enzymes were identified that generate L-ascorbic acid directly via oxidation of L-sorbosone, an intermediate of the bio-oxidation of D-sorbitol to 2KGA. This opens the possibility for a direct route from D-sorbitol to L-ascorbic acid, obviating the need for chemical rearrangement of 2KGA. Similar concepts for industrial processes apply for the production of D-isoascorbic acid, the C5 epimer of L-ascorbic acid. D-isoascorbic acid has the same conformation at C5 as D-glucose and can be derived more directly than L-ascorbic acid from this common carbohydrate feed stock.

Effects of preparation steps on the physical parameters and electromechanical properties of IPMC actuators

NASA Astrophysics Data System (ADS)

Wang, Yanjie; Zhu, Zicai; Chen, Hualing; Luo, Bin; Chang, Longfei; Wang, Yongquan; Li, Dichen

2014-12-01

The electromechanical properties of ionic polymer-metal composites (IPMC) are affected by many factors, including resistivity of surface electrodes, bending stiffness and dielectric modulus, etc, which are closely related to physical and chemical preparation steps. This paper focuses on the effects of preparation steps on these physical parameters and electromechanical properties of IPMC actuators. The mechanisms of electrode formation in the preparation steps are also clarified and investigated. To obtain samples with different features, one or more of the crucial process steps, including pretreatment, impregnation-reduction and chemical plating, were selected to fabricate IPMC. The experimental observations revealed that the physical parameters of IPMC strongly depend on their electrode morphologies caused by different steps, which were reasonable from the standpoint of physics. IPMC with the characteristics of low surface resistance and low bending stiffness, and a large area of interface electrode exhibits a perfect performance. The improvements were considered to be attributed to the double-layer electrostatic effect, induced by the broad dispersion of penetrated electrode nanoparticles. An electrical component, consisting of an equivalent circuit of a parallel combination of the serial circuit of the resistance and the electric double-layer capacitance, is introduced to qualitatively explain the deformation behaviors of IPMC. This research helps to improve the preparation steps and promote the understanding of IPMC.

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

PubMed Central

Den, Walter; Sharma, Virender K.; Lee, Mengshan; Nadadur, Govind; Varma, Rajender S.

2018-01-01

Anthropogenic climate change, principally induced by the large volume of carbon dioxide emission from the global economy driven by fossil fuels, has been observed and scientifically proven as a major threat to civilization. Meanwhile, fossil fuel depletion has been identified as a future challenge. Lignocellulosic biomass in the form of organic residues appears to be the most promising option as renewable feedstock for the generation of energy and platform chemicals. As of today, relatively little bioenergy comes from lignocellulosic biomass as compared to feedstock such as starch and sugarcane, primarily due to high cost of production involving pretreatment steps required to fragment biomass components via disruption of the natural recalcitrant structure of these rigid polymers; low efficiency of enzymatic hydrolysis of refractory feedstock presents a major challenge. The valorization of lignin and cellulose into energy products or chemical products is contingent on the effectiveness of selective depolymerization of the pretreatment regime which typically involve harsh pyrolytic and solvothermal processes assisted by corrosive acids or alkaline reagents. These unselective methods decompose lignin into many products that may not be energetically or chemically valuable, or even biologically inhibitory. Exploring milder, selective and greener processes, therefore, has become a critical subject of study for the valorization of these materials in the last decade. Efficient alternative activation processes such as microwave- and ultrasound irradiation are being explored as replacements for pyrolysis and hydrothermolysis, while milder options such as advanced oxidative and catalytic processes should be considered as choices to harsher acid and alkaline processes. Herein, we critically abridge the research on chemical oxidative techniques for the pretreatment of lignocellulosics with the explicit aim to rationalize the objectives of the biomass pretreatment step and the problems associated with the conventional processes. The mechanisms of reaction pathways, selectivity and efficiency of end-products obtained using greener processes such as ozonolysis, photocatalysis, oxidative catalysis, electrochemical oxidation, and Fenton or Fenton-like reactions, as applied to depolymerization of lignocellulosic biomass are summarized with deliberation on future prospects of biorefineries with greener pretreatment processes in the context of the life cycle assessment. PMID:29755972

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals.

PubMed

Den, Walter; Sharma, Virender K; Lee, Mengshan; Nadadur, Govind; Varma, Rajender S

2018-01-01

Anthropogenic climate change, principally induced by the large volume of carbon dioxide emission from the global economy driven by fossil fuels, has been observed and scientifically proven as a major threat to civilization. Meanwhile, fossil fuel depletion has been identified as a future challenge. Lignocellulosic biomass in the form of organic residues appears to be the most promising option as renewable feedstock for the generation of energy and platform chemicals. As of today, relatively little bioenergy comes from lignocellulosic biomass as compared to feedstock such as starch and sugarcane, primarily due to high cost of production involving pretreatment steps required to fragment biomass components via disruption of the natural recalcitrant structure of these rigid polymers; low efficiency of enzymatic hydrolysis of refractory feedstock presents a major challenge. The valorization of lignin and cellulose into energy products or chemical products is contingent on the effectiveness of selective depolymerization of the pretreatment regime which typically involve harsh pyrolytic and solvothermal processes assisted by corrosive acids or alkaline reagents. These unselective methods decompose lignin into many products that may not be energetically or chemically valuable, or even biologically inhibitory. Exploring milder, selective and greener processes, therefore, has become a critical subject of study for the valorization of these materials in the last decade. Efficient alternative activation processes such as microwave- and ultrasound irradiation are being explored as replacements for pyrolysis and hydrothermolysis, while milder options such as advanced oxidative and catalytic processes should be considered as choices to harsher acid and alkaline processes. Herein, we critically abridge the research on chemical oxidative techniques for the pretreatment of lignocellulosics with the explicit aim to rationalize the objectives of the biomass pretreatment step and the problems associated with the conventional processes. The mechanisms of reaction pathways, selectivity and efficiency of end-products obtained using greener processes such as ozonolysis, photocatalysis, oxidative catalysis, electrochemical oxidation, and Fenton or Fenton-like reactions, as applied to depolymerization of lignocellulosic biomass are summarized with deliberation on future prospects of biorefineries with greener pretreatment processes in the context of the life cycle assessment.

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

NASA Astrophysics Data System (ADS)

Den, Walter; Sharma, Virender K.; Lee, Mengshan; Nadadur, Govind; Varma, Rajender S.

2018-04-01

Anthropogenic climate change, principally induced by the large volume of carbon dioxide emission from the global economy driven by fossil fuels, has been observed and scientifically proven as a major threat to civilization. Meanwhile, fossil fuel depletion has been identified as a future challenge. Lignocellulosic biomass in the form of organic residues appears to be the most promising option as renewable feedstock for the generation of energy and platform chemicals. As of today, relatively little bioenergy comes from lignocellulosic biomass as compared to feedstock such as starch and sugarcane, primarily due to high cost of production involving pretreatment steps required to fragment biomass components via disruption of the natural recalcitrant structure of these rigid polymers; low efficiency of enzymatic hydrolysis of refractory feedstock presents a major challenge. The valorization of lignin and cellulose into energy products or chemical products is contingent on the effectiveness of selective depolymerization of the pretreatment regime which typically involve harsh pyrolytic and solvothermal processes assisted by corrosive acids or alkaline reagents. These unselective methods decompose lignin into many products that may not be energetically or chemically valuable, or even biologically inhibitory. Exploring milder, selective and greener processes, therefore, has become a critical subject of study for the valorization of these materials in the last decade. Efficient alternative activation processes such as microwave- and ultrasound irradiation are being explored as replacements for pyrolysis and hydrothermolysis, while milder options such as advanced oxidative and catalytic processes should be considered as choices to harsher acid and alkaline processes. Herein, we critically abridge the research on chemical oxidative techniques for the pretreatment of lignocellulosics with the explicit aim to rationalize the objectives of the biomass pretreatment step and the problems associated with the conventional processes. The mechanisms of reaction pathways, selectivity and efficiency of end-products obtained using greener processes such as ozonolysis, photocatalysis, oxidative catalysis, electrochemical oxidation, and Fenton or Fenton-like reactions, as applied to depolymerization of lignocellulosic biomass are summarized with deliberation on future prospects of biorefineries with greener pretreatment processes in the context of the life cycle assessment.

Estimation of environment-related properties of chemicals for design of sustainable processes: development of group-contribution+ (GC+) property models and uncertainty analysis.

PubMed

Hukkerikar, Amol Shivajirao; Kalakul, Sawitree; Sarup, Bent; Young, Douglas M; Sin, Gürkan; Gani, Rafiqul

2012-11-26

The aim of this work is to develop group-contribution(+) (GC(+)) method (combined group-contribution (GC) method and atom connectivity index (CI) method) based property models to provide reliable estimations of environment-related properties of organic chemicals together with uncertainties of estimated property values. For this purpose, a systematic methodology for property modeling and uncertainty analysis is used. The methodology includes a parameter estimation step to determine parameters of property models and an uncertainty analysis step to establish statistical information about the quality of parameter estimation, such as the parameter covariance, the standard errors in predicted properties, and the confidence intervals. For parameter estimation, large data sets of experimentally measured property values of a wide range of chemicals (hydrocarbons, oxygenated chemicals, nitrogenated chemicals, poly functional chemicals, etc.) taken from the database of the US Environmental Protection Agency (EPA) and from the database of USEtox is used. For property modeling and uncertainty analysis, the Marrero and Gani GC method and atom connectivity index method have been considered. In total, 22 environment-related properties, which include the fathead minnow 96-h LC(50), Daphnia magna 48-h LC(50), oral rat LD(50), aqueous solubility, bioconcentration factor, permissible exposure limit (OSHA-TWA), photochemical oxidation potential, global warming potential, ozone depletion potential, acidification potential, emission to urban air (carcinogenic and noncarcinogenic), emission to continental rural air (carcinogenic and noncarcinogenic), emission to continental fresh water (carcinogenic and noncarcinogenic), emission to continental seawater (carcinogenic and noncarcinogenic), emission to continental natural soil (carcinogenic and noncarcinogenic), and emission to continental agricultural soil (carcinogenic and noncarcinogenic) have been modeled and analyzed. The application of the developed property models for the estimation of environment-related properties and uncertainties of the estimated property values is highlighted through an illustrative example. The developed property models provide reliable estimates of environment-related properties needed to perform process synthesis, design, and analysis of sustainable chemical processes and allow one to evaluate the effect of uncertainties of estimated property values on the calculated performance of processes giving useful insights into quality and reliability of the design of sustainable processes.

Pre-eruptive magmatic processes re-timed using a non-isothermal approach to magma chamber dynamics.

PubMed

Petrone, Chiara Maria; Bugatti, Giuseppe; Braschi, Eleonora; Tommasini, Simone

2016-10-05

Constraining the timescales of pre-eruptive magmatic processes in active volcanic systems is paramount to understand magma chamber dynamics and the triggers for volcanic eruptions. Temporal information of magmatic processes is locked within the chemical zoning profiles of crystals but can be accessed by means of elemental diffusion chronometry. Mineral compositional zoning testifies to the occurrence of substantial temperature differences within magma chambers, which often bias the estimated timescales in the case of multi-stage zoned minerals. Here we propose a new Non-Isothermal Diffusion Incremental Step model to take into account the non-isothermal nature of pre-eruptive processes, deconstructing the main core-rim diffusion profiles of multi-zoned crystals into different isothermal steps. The Non-Isothermal Diffusion Incremental Step model represents a significant improvement in the reconstruction of crystal lifetime histories. Unravelling stepwise timescales at contrasting temperatures provides a novel approach to constraining pre-eruptive magmatic processes and greatly increases our understanding of magma chamber dynamics.

Pre-eruptive magmatic processes re-timed using a non-isothermal approach to magma chamber dynamics

PubMed Central

Petrone, Chiara Maria; Bugatti, Giuseppe; Braschi, Eleonora; Tommasini, Simone

2016-01-01

Constraining the timescales of pre-eruptive magmatic processes in active volcanic systems is paramount to understand magma chamber dynamics and the triggers for volcanic eruptions. Temporal information of magmatic processes is locked within the chemical zoning profiles of crystals but can be accessed by means of elemental diffusion chronometry. Mineral compositional zoning testifies to the occurrence of substantial temperature differences within magma chambers, which often bias the estimated timescales in the case of multi-stage zoned minerals. Here we propose a new Non-Isothermal Diffusion Incremental Step model to take into account the non-isothermal nature of pre-eruptive processes, deconstructing the main core-rim diffusion profiles of multi-zoned crystals into different isothermal steps. The Non-Isothermal Diffusion Incremental Step model represents a significant improvement in the reconstruction of crystal lifetime histories. Unravelling stepwise timescales at contrasting temperatures provides a novel approach to constraining pre-eruptive magmatic processes and greatly increases our understanding of magma chamber dynamics. PMID:27703141

Investigation into the structural, morphological, mechanical and thermal behaviour of bacterial cellulose after a two-step purification process.

PubMed

Gea, Saharman; Reynolds, Christopher T; Roohpour, Nima; Wirjosentono, Basuki; Soykeabkaew, Nattakan; Bilotti, Emiliano; Peijs, Ton

2011-10-01

Bacterial cellulose (BC) is a natural hydrogel, which is produced by Acetobacter xylinum (recently renamed Gluconacetobacter xylinum) in culture and constitutes of a three-dimensional network of ribbon-shaped bundles of cellulose microfibrils. Here, a two-step purification process is presented that significantly improves the structural, mechanical, thermal and morphological behaviour of BC sheet processed from these hydrogels produced in static culture. Alkalisation of BC using a single-step treatment of 2.5 wt.% NaOH solution produced a twofold increase in Young's modulus of processed BC sheet over untreated BC sheet. Further enhancements are achieved after a second treatment with 2.5 wt.% NaOCl (bleaching). These treatments were carefully designed in order to prevent any polymorphic crystal transformation from cellulose I to cellulose II, which can be detrimental for the mechanical properties. Scanning electron microscopy and thermogravimetric analysis reveals that with increasing chemical treatment, morphological and thermal stability of the processed films are also improved. Copyright © 2011 Elsevier Ltd. All rights reserved.

Chemical interaction matrix between reagents in a Purex based process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brahman, R.K.; Hennessy, W.P.; Paviet-Hartmann, P.

2008-07-01

The United States Department of Energy (DOE) is the responsible entity for the disposal of the United States excess weapons grade plutonium. DOE selected a PUREX-based process to convert plutonium to low-enriched mixed oxide fuel for use in commercial nuclear power plants. To initiate this process in the United States, a Mixed Oxide (MOX) Fuel Fabrication Facility (MFFF) is under construction and will be operated by Shaw AREVA MOX Services at the Savannah River Site. This facility will be licensed and regulated by the U.S. Nuclear Regulatory Commission (NRC). A PUREX process, similar to the one used at La Hague,more » France, will purify plutonium feedstock through solvent extraction. MFFF employs two major process operations to manufacture MOX fuel assemblies: (1) the Aqueous Polishing (AP) process to remove gallium and other impurities from plutonium feedstock and (2) the MOX fuel fabrication process (MP), which processes the oxides into pellets and manufactures the MOX fuel assemblies. The AP process consists of three major steps, dissolution, purification, and conversion, and is the center of the primary chemical processing. A study of process hazards controls has been initiated that will provide knowledge and protection against the chemical risks associated from mixing of reagents over the life time of the process. This paper presents a comprehensive chemical interaction matrix evaluation for the reagents used in the PUREX-based process. Chemical interaction matrix supplements the process conditions by providing a checklist of any potential inadvertent chemical reactions that may take place. It also identifies the chemical compatibility/incompatibility of the reagents if mixed by failure of operations or equipment within the process itself or mixed inadvertently by a technician in the laboratories. (aut0010ho.« less

A Guide for Developing Standard Operating Job Procedures for the Sludge Conditioning & Dewatering Process Wastewater Treatment Facility. SOJP No. 11.

ERIC Educational Resources Information Center

Schwing, Carl M.

This guide describes standard operating job procedures for the sludge conditioning and dewatering process of wastewater treatment facilities. In this process, sludge is treated with chemicals to make the sludge coagulate and give up its water more easily. The treated sludge is then dewatered using a vacuum filter. The guide gives step-by-step…

Fabrication and characterization of CNT-based smart tips for synchrotron assisted STM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Hui; Cummings, Marvin; Camino, Fernando

Determination of chemical composition along with imaging at the atomic level provides critical information towards fundamental understanding of the surface of materials and, hence, yields the capability to design new materials by tailoring their ultimate functionalities. Synchrotron X-ray assisted scanning tunneling microscopy (SX-STM) is a promising new technique to achieve real space chemically specific atomic mapping. Chemical sensitivity of SX-STM relies on excitation of core electrons by incident X-rays when their energy is tuned to an absorption edge of a particular element. However, along with core-level electrons, photoelectrons are also excited, which yield additional current and interfere with the tunnelingmore » current. To reduce the background photoelectron current and to improve ultimate resolution of SX-STM, we have developed and fabricated multiwalled carbon nanotubes (MWCNT) based “smart tips” using plasma enhanced chemical vapor deposition and focused ion beam milling. As a result, the newly developed CNT-based smart tips, characterized step by step by scanning electron microscopy (SEM) during the fabrication process, demonstrate good performance and provide opportunity for realizing atomic chemical mapping.« less

Fabrication and characterization of CNT-based smart tips for synchrotron assisted STM

DOE PAGES

Yan, Hui; Cummings, Marvin; Camino, Fernando; ...

2015-08-05

Determination of chemical composition along with imaging at the atomic level provides critical information towards fundamental understanding of the surface of materials and, hence, yields the capability to design new materials by tailoring their ultimate functionalities. Synchrotron X-ray assisted scanning tunneling microscopy (SX-STM) is a promising new technique to achieve real space chemically specific atomic mapping. Chemical sensitivity of SX-STM relies on excitation of core electrons by incident X-rays when their energy is tuned to an absorption edge of a particular element. However, along with core-level electrons, photoelectrons are also excited, which yield additional current and interfere with the tunnelingmore » current. To reduce the background photoelectron current and to improve ultimate resolution of SX-STM, we have developed and fabricated multiwalled carbon nanotubes (MWCNT) based “smart tips” using plasma enhanced chemical vapor deposition and focused ion beam milling. As a result, the newly developed CNT-based smart tips, characterized step by step by scanning electron microscopy (SEM) during the fabrication process, demonstrate good performance and provide opportunity for realizing atomic chemical mapping.« less

Solving the chemical master equation using sliding windows

PubMed Central

2010-01-01

Background The chemical master equation (CME) is a system of ordinary differential equations that describes the evolution of a network of chemical reactions as a stochastic process. Its solution yields the probability density vector of the system at each point in time. Solving the CME numerically is in many cases computationally expensive or even infeasible as the number of reachable states can be very large or infinite. We introduce the sliding window method, which computes an approximate solution of the CME by performing a sequence of local analysis steps. In each step, only a manageable subset of states is considered, representing a "window" into the state space. In subsequent steps, the window follows the direction in which the probability mass moves, until the time period of interest has elapsed. We construct the window based on a deterministic approximation of the future behavior of the system by estimating upper and lower bounds on the populations of the chemical species. Results In order to show the effectiveness of our approach, we apply it to several examples previously described in the literature. The experimental results show that the proposed method speeds up the analysis considerably, compared to a global analysis, while still providing high accuracy. Conclusions The sliding window method is a novel approach to address the performance problems of numerical algorithms for the solution of the chemical master equation. The method efficiently approximates the probability distributions at the time points of interest for a variety of chemically reacting systems, including systems for which no upper bound on the population sizes of the chemical species is known a priori. PMID:20377904

Chemical kinetic simulation of kerosene combustion in an individual flame tube.

PubMed

Zeng, Wen; Liang, Shuang; Li, Hai-Xia; Ma, Hong-An

2014-05-01

The use of detailed chemical reaction mechanisms of kerosene is still very limited in analyzing the combustion process in the combustion chamber of the aircraft engine. In this work, a new reduced chemical kinetic mechanism for fuel n-decane, which selected as a surrogate fuel for kerosene, containing 210 elemental reactions (including 92 reversible reactions and 26 irreversible reactions) and 50 species was developed, and the ignition and combustion characteristics of this fuel in both shock tube and flat-flame burner were kinetic simulated using this reduced reaction mechanism. Moreover, the computed results were validated by experimental data. The calculated values of ignition delay times at pressures of 12, 50 bar and equivalence ratio is 1.0, 2.0, respectively, and the main reactants and main products mole fractions using this reduced reaction mechanism agree well with experimental data. The combustion processes in the individual flame tube of a heavy duty gas turbine combustor were simulated by coupling this reduced reaction mechanism of surrogate fuel n-decane and one step reaction mechanism of surrogate fuel C12H23 into the computational fluid dynamics software. It was found that this reduced reaction mechanism is shown clear advantages in simulating the ignition and combustion processes in the individual flame tube over the one step reaction mechanism.

Chemical kinetic simulation of kerosene combustion in an individual flame tube

PubMed Central

Zeng, Wen; Liang, Shuang; Li, Hai-xia; Ma, Hong-an

2013-01-01

The use of detailed chemical reaction mechanisms of kerosene is still very limited in analyzing the combustion process in the combustion chamber of the aircraft engine. In this work, a new reduced chemical kinetic mechanism for fuel n-decane, which selected as a surrogate fuel for kerosene, containing 210 elemental reactions (including 92 reversible reactions and 26 irreversible reactions) and 50 species was developed, and the ignition and combustion characteristics of this fuel in both shock tube and flat-flame burner were kinetic simulated using this reduced reaction mechanism. Moreover, the computed results were validated by experimental data. The calculated values of ignition delay times at pressures of 12, 50 bar and equivalence ratio is 1.0, 2.0, respectively, and the main reactants and main products mole fractions using this reduced reaction mechanism agree well with experimental data. The combustion processes in the individual flame tube of a heavy duty gas turbine combustor were simulated by coupling this reduced reaction mechanism of surrogate fuel n-decane and one step reaction mechanism of surrogate fuel C12H23 into the computational fluid dynamics software. It was found that this reduced reaction mechanism is shown clear advantages in simulating the ignition and combustion processes in the individual flame tube over the one step reaction mechanism. PMID:25685503

Catalytic amino acid production from biomass-derived intermediates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Weiping; Wang, Yunzhu; Zhang, Sui

Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived a-hydroxyl acids into a-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supportedmore » on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH 3 on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components.« less

Catalytic amino acid production from biomass-derived intermediates

PubMed Central

Deng, Weiping; Zhang, Sui; Gupta, Krishna M.; Hülsey, Max J.; Asakura, Hiroyuki; Liu, Lingmei; Han, Yu; Karp, Eric M.; Jiang, Jianwen; Tanaka, Tsunehiro; Wang, Ye

2018-01-01

Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived α-hydroxyl acids into α-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supported on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH3 on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components. PMID:29712826

Catalytic amino acid production from biomass-derived intermediates

DOE PAGES

Deng, Weiping; Wang, Yunzhu; Zhang, Sui; ...

2018-04-30

Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived a-hydroxyl acids into a-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supportedmore » on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH 3 on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components.« less

Techno-economic analysis of biocatalytic processes for production of alkene expoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borole, Abhijeet P

2007-01-01

A techno-economic analysis of two different bioprocesses was conducted, one for the conversion of propylene to propylene oxide (PO) and other for conversion of styrene to styrene expoxide (SO). The first process was a lipase-mediated chemo-enzymatic reaction, whereas the second one was a one-step enzymatic process using chloroperoxidase. The PO produced through the chemo-enzymatic process is a racemic product, whereas the latter process (based on chloroperoxidase) produces an enantio-pure product. The former process thus falls under the category of high-volume commodity chemical (PO); whereas the latter is a low-volume, high-value product (SO).A simulation of the process was conducted using themore » bioprocess engineering software SuperPro Designer v6.0 (Intelligen, Inc., Scotch Plains, NJ) to determine the economic feasibility of the process. The purpose of the exercise was to compare biocatalytic processes with existing chemical processes for production of alkene expoxides. The results show that further improvements are needed in improving biocatalyst stability to make these bioprocesses competitive with chemical processes.« less

Mechanism of amino acid interaction with silicon nitride surface during chemical mechanical planarization

NASA Astrophysics Data System (ADS)

America, William George

Chemical-Mechanical Planarization (CMP) has become an essential technology for making modern semiconductor devices. This technique was originally applied to overcome the depth of focus limitations of lithography tools during pattern development of metal and dielectric films. As features of the semiconductor device became smaller the lithographic process shifted to shorter exposure wavelengths and the useable depth of focus became smaller. The topography differences on the wafer's surface from all of the previous processing steps became greater than the exposure tools could properly project. CMP helped solve this problem by bringing the features of the wafer surface to the same plane. As semiconductor fabrication technology progressed further, CMP was applied to other areas of the process, including shallow trench isolation and metal line Damascene processing. In its simplest application, CMP polishes on features projecting upward and higher than the average surface. These projections experience more work and are polished faster. Given sufficient time the surface becomes essentially flat, on a micro-scale, and the lithographic projection tools has the same plane onto which to focus. Thus, the pattern is properly and uniformly exposed and subsequent reactive ion etching (RIE) steps are executed. This technique was initially applied to later steps in the wafer processing scheme to render a new flat surface at each metal layer. Building on this success, CMP has been applied to a broad range of steps in the wafer processing particularly where surface topography warrants and when RIE of dielectric or metallic films is not practical. CMP has seen its greatest application in semiconductor logic and memory devices and most recently, a Damascene processing for copper lines and shallow trench isolation. This pattern dependent CMP issue is explored in this thesis as it pertains primarily to shallow trench isolation CMP coupled with a highly selective slurry chemistry.

[The workplace injury trends in the petrochemical industry: from data analysis to risk management].

PubMed

Campo, Giuseppe; Martini, Benedetta

2013-01-01

The most recent INAIL data show that, in 2009-2011, the accident frequency rate and the severity rate of workplace injuries in the chemical industry are lower than for the total non-agricultural workforce. The chemical industry, primarily because of the complex and hazardous work processes, requires an appropriate system for assessing and monitoring specific risks.The implementation of Responsible Care, a risk management system specific for the chemical industry, in 1984, has represented a historical step in the process of critical awareness of risk management by the chemical companies. Responsible Care is a risk management system specifically designed on the risk profiles of this type of enterprise, which integrates safety, health and environment. A risk management system, suitable for the needs of a chemical company, should extend its coverage area, beyond the responsible management of products throughout the entire production cycle, to the issues of corporate responsibility.

Mechanical Adaptivity as a Process: Implications to New Materials and Material System Design

DTIC Science & Technology

2012-08-01

Deliver. Rev. 2004 Microactuators and valves Uses: • Drug delivery • Microfluidic actuators, valves , and pumps • Chemical and biological Sensors... paper where they did a study with f the stoichiometric parameter involved in the reduction step, and they looked at 2 X* - both far away from the...through strain? How do varying material properties affect behavior? Smith, Vaia et al. submitted 2012 23 Fibrous Paper Next Step: Heterogeneous

Isolated human/animal stratum corneum as a partial model for 15 steps in percutaneous absorption: emphasizing decontamination, Part I.

PubMed

Hui, Xiaoying; Lamel, Sonia; Qiao, Peter; Maibach, Howard I

2013-03-01

Since the advent of World War II, governments and laboratories have made a concerted effort to improve prophylactic and therapeutic interventions counteracting cutaneously directed chemical warfare agents (CWA), and by inference, common industrial and consumer dermatotoxicants. In vitro percutaneous penetration assays, first utilized by Tregear in the 1940s and presently in various modifications, have been fundamental to this effort. Percutaneous penetration, often considered a simple one-step diffusion process, consists of at least 15 steps. The first part of this review covers the initial steps related to absorption and excretion kinetics, vehicle characteristics, and tissue disposition. Importantly, the partitioning behavior and stratum corneum (SC) diffusion by a wide physicochemical array of compounds shows that many compounds have similar diffusion coefficients determining their percutaneous absorption in vivo. After accounting for anatomical SC variation, the penetration flux value of a substance depends mainly on its SC/vehicle partition coefficient. Additionally, the SC acts as a 'reservoir' for topically applied molecules and application of tape stripping has been found to quantify the chemical remaining in the SC which can predict total molecular penetration in vivo. Decontamination is of particular concern and even expediting standard washing procedures after dermal chemical exposure often fails to remove chemicals. This overview summarizes knowledge of percutaneous penetration extending insights into the complexities of penetration, decontamination and potential newer assays that may be of practical importance. Copyright © 2012 John Wiley & Sons, Ltd.

Melt Conditioning of Light Metals by Application of High Shear for Improved Microstructure and Defect Control

NASA Astrophysics Data System (ADS)

Patel, Jayesh B.; Yang, Xinliang; Mendis, Chamini L.; Fan, Zhongyun

2017-04-01

Casting is the first step toward the production of majority of metal products whether the final processing step is casting or other thermomechanical processes such as extrusion or forging. The high shear melt conditioning provides an easily adopted pathway to producing castings with a more uniform fine-grained microstructure along with a more uniform distribution of the chemical composition leading to fewer defects as a result of reduced shrinkage porosities and the presence of large oxide films through the microstructure. The effectiveness of high shear melt conditioning in improving the microstructure of processes used in industry illustrates the versatility of the high shear melt conditioning technology. The application of high shear process to direct chill and twin roll casting process is demonstrated with examples from magnesium melts.

Nonequilibrium thermodynamics and a fluctuation theorem for individual reaction steps in a chemical reaction network

NASA Astrophysics Data System (ADS)

Pal, Krishnendu; Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2015-09-01

We have introduced an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the propensities of the individual elementary reactions and the corresponding reverse reactions. The method is a microscopic formulation of the dissipation function in terms of the relative entropy or Kullback-Leibler distance which is based on the analogy of phase space trajectory with the path of elementary reactions in a network of chemical process. We have introduced here a fluctuation theorem valid for each opposite pair of elementary reactions which is useful in determining the contribution of each sub-reaction on the nonequilibrium thermodynamics of overall reaction. The methodology is applied to an oligomeric enzyme kinetics at a chemiostatic condition that leads the reaction to a nonequilibrium steady state for which we have estimated how each step of the reaction is energy driven or entropy driven to contribute to the overall reaction.

Investigations for Thermal and Electrical Conductivity of ABS-Graphene Blended Prototypes

PubMed Central

Singh, Rupinder; Sandhu, Gurleen S.; Penna, Rosa; Farina, Ilenia

2017-01-01

The thermoplastic materials such as acrylonitrile-butadiene-styrene (ABS) and Nylon have large applications in three-dimensional printing of functional/non-functional prototypes. Usually these polymer-based prototypes are lacking in thermal and electrical conductivity. Graphene (Gr) has attracted impressive enthusiasm in the recent past due to its natural mechanical, thermal, and electrical properties. This paper presents the step by step procedure (as a case study) for development of an in-house ABS-Gr blended composite feedstock filament for fused deposition modelling (FDM) applications. The feedstock filament has been prepared by two different methods (mechanical and chemical mixing). For mechanical mixing, a twin screw extrusion (TSE) process has been used, and for chemical mixing, the composite of Gr in an ABS matrix has been set by chemical dissolution, followed by mechanical blending through TSE. Finally, the electrical and thermal conductivity of functional prototypes prepared from composite feedstock filaments have been optimized. PMID:28773244

Process concept of retorting of Julia Creek oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sitnai, O.

1984-06-01

A process is proposed for the above ground retorting of the Julia Creek oil shale in Queensland. The oil shale characteristics, process description, chemical reactions of the oil shale components, and the effects of variable and operating conditions on process performance are discussed. The process contains a fluidized bed combustor which performs both as a combustor of the spent shales and as a heat carrier generator for the pyrolysis step. 12 references, 5 figures, 5 tables.

Economic-Oriented Stochastic Optimization in Advanced Process Control of Chemical Processes

PubMed Central

Dobos, László; Király, András; Abonyi, János

2012-01-01

Finding the optimal operating region of chemical processes is an inevitable step toward improving economic performance. Usually the optimal operating region is situated close to process constraints related to product quality or process safety requirements. Higher profit can be realized only by assuring a relatively low frequency of violation of these constraints. A multilevel stochastic optimization framework is proposed to determine the optimal setpoint values of control loops with respect to predetermined risk levels, uncertainties, and costs of violation of process constraints. The proposed framework is realized as direct search-type optimization of Monte-Carlo simulation of the controlled process. The concept is illustrated throughout by a well-known benchmark problem related to the control of a linear dynamical system and the model predictive control of a more complex nonlinear polymerization process. PMID:23213298

Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

DOE PAGES

Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; ...

2016-08-16

Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyreneblock-poly(methyl methacrylate). Faster assembly kinetics aremore » observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. Lastly, the rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.« less

Novel Cyclosilazane-Type Silicon Precursor and Two-Step Plasma for Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride.

PubMed

Park, Jae-Min; Jang, Se Jin; Lee, Sang-Ick; Lee, Won-Jun

2018-03-14

We designed cyclosilazane-type silicon precursors and proposed a three-step plasma-enhanced atomic layer deposition (PEALD) process to prepare silicon nitride films with high quality and excellent step coverage. The cyclosilazane-type precursor, 1,3-di-isopropylamino-2,4-dimethylcyclosilazane (CSN-2), has a closed ring structure for good thermal stability and high reactivity. CSN-2 showed thermal stability up to 450 °C and a sufficient vapor pressure of 4 Torr at 60 °C. The energy for the chemisorption of CSN-2 on the undercoordinated silicon nitride surface as calculated by density functional theory method was -7.38 eV. The PEALD process window was between 200 and 500 °C, with a growth rate of 0.43 Å/cycle. The best film quality was obtained at 500 °C, with hydrogen impurity of ∼7 atom %, oxygen impurity less than 2 atom %, low wet etching rate, and excellent step coverage of ∼95%. At 300 °C and lower temperatures, the wet etching rate was high especially at the lower sidewall of the trench pattern. We introduced the three-step PEALD process to improve the film quality and the step coverage on the lower sidewall. The sequence of the three-step PEALD process consists of the CSN-2 feeding step, the NH 3 /N 2 plasma step, and the N 2 plasma step. The H radicals in NH 3 /N 2 plasma efficiently remove the ligands from the precursor, and the N 2 plasma after the NH 3 plasma removes the surface hydrogen atoms to activate the adsorption of the precursor. The films deposited at 300 °C using the novel precursor and the three-step PEALD process showed a significantly improved step coverage of ∼95% and an excellent wet etching resistance at the lower sidewall, which is only twice as high as that of the blanket film prepared by low-pressure chemical vapor deposition.

Microscale technology and biocatalytic processes: opportunities and challenges for synthesis.

PubMed

Wohlgemuth, Roland; Plazl, Igor; Žnidaršič-Plazl, Polona; Gernaey, Krist V; Woodley, John M

2015-05-01

Despite the expanding presence of microscale technology in chemical synthesis and energy production as well as in biomedical devices and analytical and diagnostic tools, its potential in biocatalytic processes for pharmaceutical and fine chemicals, as well as related industries, has not yet been fully exploited. The aim of this review is to shed light on the strategic advantages of this promising technology for the development and realization of biocatalytic processes and subsequent product recovery steps, demonstrated with examples from the literature. Constraints, opportunities, and the future outlook for the implementation of these key green engineering methods and the role of supporting tools such as mathematical models to establish sustainable production processes are discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Design-for-manufacture of gradient-index optical systems using time-varying boundary condition diffusion

NASA Astrophysics Data System (ADS)

Harkrider, Curtis Jason

2000-08-01

The incorporation of gradient-index (GRIN) material into optical systems offers novel and practical solutions to lens design problems. However, widespread use of gradient-index optics has been limited by poor correlation between gradient-index designs and the refractive index profiles produced by ion exchange between glass and molten salt. Previously, a design-for- manufacture model was introduced that connected the design and fabrication processes through use of diffusion modeling linked with lens design software. This project extends the design-for-manufacture model into a time- varying boundary condition (TVBC) diffusion model. TVBC incorporates the time-dependent phenomenon of melt poisoning and introduces a new index profile control method, multiple-step diffusion. The ions displaced from the glass during the ion exchange fabrication process can reduce the total change in refractive index (Δn). Chemical equilibrium is used to model this melt poisoning process. Equilibrium experiments are performed in a titania silicate glass and chemically analyzed. The equilibrium model is fit to ion concentration data that is used to calculate ion exchange boundary conditions. The boundary conditions are changed purposely to control the refractive index profile in multiple-step TVBC diffusion. The glass sample is alternated between ion exchange with a molten salt bath and annealing. The time of each diffusion step can be used to exert control on the index profile. The TVBC computer model is experimentally verified and incorporated into the design- for-manufacture subroutine that runs in lens design software. The TVBC design-for-manufacture model is useful for fabrication-based tolerance analysis of gradient-index lenses and for the design of manufactureable GRIN lenses. Several optical elements are designed and fabricated using multiple-step diffusion, verifying the accuracy of the model. The strength of multiple-step diffusion process lies in its versatility. An axicon, imaging lens, and curved radial lens, all with different index profile requirements, are designed out of a single glass composition.

Fast wettability transition from hydrophilic to superhydrophobic laser-textured stainless steel surfaces under low-temperature annealing

NASA Astrophysics Data System (ADS)

Ngo, Chi-Vinh; Chun, Doo-Man

2017-07-01

Recently, the fabrication of superhydrophobic metallic surfaces by means of pulsed laser texturing has been developed. After laser texturing, samples are typically chemically coated or aged in ambient air for a relatively long time of several weeks to achieve superhydrophobicity. To accelerate the wettability transition from hydrophilicity to superhydrophobicity without the use of additional chemical treatment, a simple annealing post process has been developed. In the present work, grid patterns were first fabricated on stainless steel by a nanosecond pulsed laser, then an additional low-temperature annealing post process at 100 °C was applied. The effect of 100-500 μm step size of the textured grid upon the wettability transition time was also investigated. The proposed post process reduced the transition time from a couple of months to within several hours. All samples showed superhydrophobicity with contact angles greater than 160° and sliding angles smaller than 10° except samples with 500 μm step size, and could be applied in several potential applications such as self-cleaning and control of water adhesion.

Chemical Vapor Deposition Of Silicon Carbide

NASA Technical Reports Server (NTRS)

Powell, J. Anthony; Larkin, David J.; Matus, Lawrence G.; Petit, Jeremy B.

1993-01-01

Large single-crystal SiC boules from which wafers of large area cut now being produced commerically. Availability of wafers opens door for development of SiC semiconductor devices. Recently developed chemical vapor deposition (CVD) process produces thin single-crystal SiC films on SiC wafers. Essential step in sequence of steps used to fabricate semiconductor devices. Further development required for specific devices. Some potential high-temperature applications include sensors and control electronics for advanced turbine engines and automobile engines, power electronics for electromechanical actuators for advanced aircraft and for space power systems, and equipment used in drilling of deep wells. High-frequency applications include communication systems, high-speed computers, and microwave power transistors. High-radiation applications include sensors and controls for nuclear reactors.

The Use of Lean Six Sigma Methodology in Increasing Capacity of a Chemical Production Facility at DSM.

PubMed

Meeuwse, Marco

2018-03-30

Lean Six Sigma is an improvement method, combining Lean, which focuses on removing 'waste' from a process, with Six Sigma, which is a data-driven approach, making use of statistical tools. Traditionally it is used to improve the quality of products (reducing defects), or processes (reducing variability). However, it can also be used as a tool to increase the productivity or capacity of a production plant. The Lean Six Sigma methodology is therefore an important pillar of continuous improvement within DSM. In the example shown here a multistep batch process is improved, by analyzing the duration of the relevant process steps, and optimizing the procedures. Process steps were performed in parallel instead of sequential, and some steps were made shorter. The variability was reduced, giving the opportunity to make a tighter planning, and thereby reducing waiting times. Without any investment in new equipment or technical modifications, the productivity of the plant was improved by more than 20%; only by changing procedures and the programming of the process control system.

Non-equilibrium calculations of atmospheric processes initiated by electron impact.

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.

2007-05-01

Electron impact in the atmosphere produces ionisation, dissociation, electronic excitation and vibrational excitation of atoms and molecules. The products can then take part in chemical reactions, recombination with electrons, or radiative or collisional deactivation. While most such processes are fast, some longer--lived species do not reach equilibrium. The electron source (photoelectrons or auroral electrons) also varies over time and longer-lived species can move substantially in altitude by molecular, ambipolar or eddy diffusion. Hence non-equilibrium calculations are required in some circumstances. Such time-step calculations need to have sufficiently short steps so that the fastest processes are still calculated correctly, but this can lead to computation times that are too large. Hence techniques to allow for longer time steps by incorporating equilibrium calculations are described. Examples are given for results of atmospheric non-equilibrium calculations, including the populations of the vibrational levels of ground state N2, the electron density and its dependence on vibrationally excited N2, predictions of nitric oxide density, and detailed processes during short duration auroral events.

Sub-500 fs electronically nonadiabatic chemical dynamics of energetic molecules from the S1 excited state: Ab initio multiple spawning study

NASA Astrophysics Data System (ADS)

Ghosh, Jayanta; Gajapathy, Harshad; Konar, Arindam; Narasimhaiah, Gowrav M.; Bhattacharya, Atanu

2017-11-01

Energetic materials store a large amount of chemical energy. Different ignition processes, including laser ignition and shock or compression wave, initiate the energy release process by first promoting energetic molecules to the electronically excited states. This is why a full understanding of initial steps of the chemical dynamics of energetic molecules from the excited electronic states is highly desirable. In general, conical intersection (CI), which is the crossing point of multidimensional electronic potential energy surfaces, is well established as a controlling factor in the initial steps of chemical dynamics of energetic molecules following their electronic excitations. In this article, we have presented different aspects of the ultrafast unimolecular relaxation dynamics of energetic molecules through CIs. For this task, we have employed ab initio multiple spawning (AIMS) simulation using the complete active space self-consistent field (CASSCF) electronic wavefunction and frozen Gaussian-based nuclear wavefunction. The AIMS simulation results collectively reveal that the ultrafast relaxation step of the best energetic molecules (which are known to exhibit very good detonation properties) is completed in less than 500 fs. Many, however, exhibit sub-50 fs dynamics. For example, nitro-containing molecules (including C-NO2, N-NO2, and O-NO2 active moieties) relax back to the ground state in approximately 40 fs through similar (S1/S0)CI conical intersections. The N3-based energetic molecule undergoes the N2 elimination process in 40 fs through the (S1/S0)CI conical intersection. Nitramine-Fe complexes exhibit sub-50 fs Fe-O and N-O bond dissociation through the respective (S1/S0)CI conical intersection. On the other hand, tetrazine-N-oxides, which are known to exhibit better detonation properties than tetrazines, undergo internal conversion in a 400-fs time scale, while the relaxation time of tetrazine is very long (about 100 ns). Many other characteristics of sub-500 fs nonadiabatic decay of energetic molecules are discussed. In the end, many unresolved issues associated with the ultrafast nonadiabatic chemical dynamics of energetic molecules are presented.

Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

PubMed

Ambler, Brett R; Altman, Ryan A

2013-11-01

The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

Designing Systems for Environmental Sustainability

EPA Science Inventory

Dr. Smith will describe his U.S. EPA research which involves elements of design, from systems as diverse as biofuel supply chains to recycling systems and chemical processes. Design uses models that rate performance as part of a synthesis approach, where steps of analysis and sy...

Endpoints for Neural Connectivity Including Neurite Outgrowth, Synapse Formation, and Function

EPA Science Inventory

A strategy for alternative methods for developmental neurotoxicity testing (DNT) focuses on assessment of chemical effects on conserved neurodevelopmental processes. The development of the brain is an integrated series of steps from the commitment of embryonic cells to become neu...

Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst.

PubMed

Zhang, Bo; Zhong, Zhaoping; Xie, Qinglong; Liu, Shiyu; Ruan, Roger

2016-07-01

A novel technology of two-step fast microwave-assisted pyrolysis (fMAP) of corn stover for bio-oil production was investigated in the presence of microwave absorbent (SiC) and HZSM-5 catalyst. Effects of fMAP temperature and catalyst-to-biomass ratio on bio-oil yield and chemical components were examined. The results showed that this technology, employing microwave, microwave absorbent and HZSM-5 catalyst, was effective and promising for biomass fast pyrolysis. The fMAP temperature of 500°C was considered the optimum condition for maximum yield and best quality of bio-oil. Besides, the bio-oil yield decreased linearly and the chemical components in bio-oil were improved sequentially with the increase of catalyst-to-biomass ratio from 1:100 to 1:20. The elemental compositions of bio-char were also determined. Additionally, compared to one-step fMAP process, two-step fMAP could promote the bio-oil quality with a smaller catalyst-to-biomass ratio. Copyright © 2016. Published by Elsevier B.V.

Overview of several applications of chemical downstream etching (CDE) for IC manufacturing: advantages and drawbacks versus WET processes

NASA Astrophysics Data System (ADS)

de Buttet, Côme; Prevost, Emilie; Campo, Alain; Garnier, Philippe; Zoll, Stephane; Vallier, Laurent; Cunge, Gilles; Maury, Patrick; Massin, Thomas; Chhun, Sonarith

2017-03-01

Today the IC manufacturing faces lots of problematics linked to the continuous down scaling of printed structures. Some of those issues are related to wet processing, which are often used in the IC manufacturing flow for wafer cleaning, material etching and surface preparation. In the current work we summarize the limitations for the next nodes of wet processing such as metallic contaminations, wafer charging, corrosion and pattern collapse. As a replacement, we promoted the isotropic chemical dry etching (CDE) which is supposed to fix all the above drawbacks. Etching steps of SI3N4 layers were evaluated in order to prove the interest of such technique.

Solvent exchange in a metal–organic framework single crystal monitored by dynamic in situ X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cox, Jordan M.; Walton, Ian M.; Bateman, Gage

2017-07-25

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy) 0.5(H 2O)]·2H 2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

Characterization of stainless steel surface processed using electrolytic oxidation and titanium complex ion solution

NASA Astrophysics Data System (ADS)

Kang, Yubin; Choi, Jaeyoung; Park, Jinju; Kim, Woo-Byoung; Lee, Kun-Jae

2017-09-01

This study attempts to improve the physical and chemical adhesion between metals and ceramics by using electrolytic oxidation and a titanium organic/inorganic complex ion solution on the SS-304 plate. Surface analysis confirmed the existence of the Tisbnd Osbnd Mx bonds formed by the bonding between the metal ions and the Ti oxide at the surface of the pre-processed SS plate, and improved chemical adhesion during ceramic coating was expected by confirming the presence of the carboxylic group. The adhesion was evaluated by using the ceramic coating solution in order to assess the improved adhesion of the SS plate under conditions. The results showed that both the adhesion and durability were largely improved in the sample processed with all the pre-processing steps, thus confirming that the physical and chemical adhesion between metals and ceramics can be improved by enhancing the physical roughness via electrolytic oxidation and pre-processing using a Ti complex ion solution.

Latest development in the synthesis of ursodeoxycholic acid (UDCA): a critical review

PubMed Central

Tonin, Fabio

2018-01-01

Ursodeoxycholic acid (UDCA) is a pharmaceutical ingredient widely used in clinics. As bile acid it solubilizes cholesterol gallstones and improves the liver function in case of cholestatic diseases. UDCA can be obtained from cholic acid (CA), which is the most abundant and least expensive bile acid available. The now available chemical routes for the obtainment of UDCA yield about 30% of final product. For these syntheses several protection and deprotection steps requiring toxic and dangerous reagents have to be performed, leading to the production of a series of waste products. In many cases the cholic acid itself first needs to be prepared from its taurinated and glycilated derivatives in the bile, thus adding to the complexity and multitude of steps involved of the synthetic process. For these reasons, several studies have been performed towards the development of microbial transformations or chemoenzymatic procedures for the synthesis of UDCA starting from CA or chenodeoxycholic acid (CDCA). This promising approach led several research groups to focus their attention on the development of biotransformations with non-pathogenic, easy-to-manage microorganisms, and their enzymes. In particular, the enzymatic reactions involved are selective hydrolysis, epimerization of the hydroxy functions (by oxidation and subsequent reduction) and the specific hydroxylation and dehydroxylation of suitable positions in the steroid rings. In this minireview, we critically analyze the state of the art of the production of UDCA by several chemical, chemoenzymatic and enzymatic routes reported, highlighting the bottlenecks of each production step. Particular attention is placed on the precursors availability as well as the substrate loading in the process. Potential new routes and recent developments are discussed, in particular on the employment of flow-reactors. The latter technology allows to develop processes with shorter reaction times and lower costs for the chemical and enzymatic reactions involved. PMID:29520309

Processing of LEU targets for {sup 99}Mo production--testing and modification of the Cintichem process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, D.; Landsberger, S.; Buchholz, B.

1995-09-01

Recent experimental results on testing and modification of the Cintichem process to allow substitution of low enriched uranium (LEU) for high enriched uranium (HEU) targets are presented in this report. The main focus is on {sup 99}Mo recovery and purification by its precipitation with {alpha}-benzoin oxime. Parameters that were studied include concentrations of nitric and sulfuric acids, partial neutralization of the acids, molybdenum and uranium concentrations, and the ratio of {alpha}-benzoin oxime to molybdenum. Decontamination factors for uranium, neptunium, and various fission products were measured. Experiments with tracer levels of irradiated LEU were conducted for testing the {sup 99}Mo recoverymore » and purification during each step of the Cintichem process. Improving the process with additional processing steps was also attempted. The results indicate that the conversion of molybdenum chemical processing from HEU to LEU targets is possible.« less

Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Gokcen, Tahir; Meyyappan, M.

2002-01-01

A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

Kinetics of Alkaline Decomposition and Cyaniding of Argentian Rubidium Jarosite in NaOH Medium

NASA Astrophysics Data System (ADS)

Rodríguez, Eleazar Salinas; Sáenz, Eduardo Cerecedo; Ramírez, Marius; Cardona, Francisco Patiño; Labra, Miguel Pérez

2012-10-01

The alkaline decomposition of Argentian rubidium jarosite in NaOH media is characterized by an induction period and a progressive conversion period in which the sulfate and rubidium ions pass to the solution, leaving an amorphous iron hydroxide residue. The process is chemically controlled and the order of reaction with respect to hydroxide concentration in the range of 1.75 and 20.4 mol OH- m-3 is 0.94, while activation energy in the range of temperatures of 298 K to 328 K (25 °C to 55 °C) is 91.3 kJ mol-1. Cyaniding of Argentian rubidium jarosite in NaOH media presents a reaction order of 0 with respect to NaCN concentration (in the range of 5 to 41 mol m-3) and an order of reaction of 0.62 with respect to hydroxide concentration, in the range of 1.1 and 30 mol [OH-] m-3. In this case, the cyaniding process can be described, as in other jarosites, as the following two-step process: (1) a step (slow) of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation. The activation energy during cyaniding in the range of temperatures of 298 K to 333 K (25 °C to 60 °C) is 43.5 kJ mol-1, which is characteristic of a process controlled by chemical reaction. These results are quite similar to that observed for several synthetic jarosites and that precipitated in a zinc hydrometallurgical plant (Industrial Minera México, San Luis Potosi).

Study on characteristics of printed circuit board liberation and its crushed products.

PubMed

Quan, Cui; Li, Aimin; Gao, Ningbo

2012-11-01

Recycling printed circuit board waste (PCBW) waste is a hot issue of environmental protection and resource recycling. Mechanical and thermo-chemical methods are two traditional recycling processes for PCBW. In the present research, a two-step crushing process combined with a coarse-crushing step and a fine-pulverizing step was adopted, and then the crushed products were classified into seven different fractions with a standard sieve. The liberation situation and particle shape in different size fractions were observed. Properties of different size fractions, such as heating value, thermogravimetric, proximate, ultimate and chemical analysis were determined. The Rosin-Rammler model was applied to analyze the particle size distribution of crushed material. The results indicated that complete liberation of metals from the PCBW was achieved at a size less than 0.59 mm, but the nonmetal particle in the smaller-than-0.15 mm fraction is liable to aggregate. Copper was the most prominent metal in PCBW and mainly enriched in the 0.42-0.25 mm particle size. The Rosin-Rammler equation adequately fit particle size distribution data of crushed PCBW with a correlation coefficient of 0.9810. The results of heating value and proximate analysis revealed that the PCBW had a low heating value and high ash content. The combustion and pyrolysis process of PCBW was different and there was an obvious oxidation peak of Cu in combustion runs.

Development and validation of an affinity chromatography step using a peptide ligand for cGMP production of factor VIII.

PubMed

Kelley, Brian D; Tannatt, Molly; Magnusson, Robert; Hagelberg, Sigrid; Booth, James

2004-08-05

An affinity chromatography step was developed for purification of recombinant B-Domain Deleted Factor VIII (BDDrFVIII) using a peptide ligand selected from a phage display library. The peptide library had variegated residues, contained both within a disulfide bond-constrained ring and flanking the ring. The peptide ligand binds to BDDrFVIII with a dissociation constant of approximately 1 microM both in free solution and when immobilized on a chromatographic resin. The peptide is chemically synthesized and the affinity resin is produced by coupling the peptide to an agarose matrix preactivated with N-hydroxysuccinimide. Coupling conditions were optimized to give consistent and complete ligand incorporation and validated with a robustness study that tested various combinations of processing limits. The peptide affinity chromatographic operation employs conditions very similar to an immunoaffinity chromatography step currently in use for BDDrFVIII manufacture. The process step provides excellent recovery of BDDrFVIII from a complex feed stream and reduces host cell protein and DNA by 3-4 logs. Process validation studies established resin reuse over 26 cycles without changes in product recovery or purity. A robustness study using a factorial design was performed and showed that the step was insensitive to small changes in process conditions that represent normal variation in commercial manufacturing. A scaled-down model of the process step was qualified and used for virus removal studies. A validation package addressing the safety of the leached peptide included leaching rate measurements under process conditions, testing of peptide levels in product pools, demonstration of robust removal downstream by spiking studies, end product testing, and toxicological profiling of the ligand. The peptide ligand affinity step was scaled up for cGMP production of BDDrFVIII for clinical trials.

Automated workflows for modelling chemical fate, kinetics and toxicity.

PubMed

Sala Benito, J V; Paini, Alicia; Richarz, Andrea-Nicole; Meinl, Thorsten; Berthold, Michael R; Cronin, Mark T D; Worth, Andrew P

2017-12-01

Automation is universal in today's society, from operating equipment such as machinery, in factory processes, to self-parking automobile systems. While these examples show the efficiency and effectiveness of automated mechanical processes, automated procedures that support the chemical risk assessment process are still in their infancy. Future human safety assessments will rely increasingly on the use of automated models, such as physiologically based kinetic (PBK) and dynamic models and the virtual cell based assay (VCBA). These biologically-based models will be coupled with chemistry-based prediction models that also automate the generation of key input parameters such as physicochemical properties. The development of automated software tools is an important step in harmonising and expediting the chemical safety assessment process. In this study, we illustrate how the KNIME Analytics Platform can be used to provide a user-friendly graphical interface for these biokinetic models, such as PBK models and VCBA, which simulates the fate of chemicals in vivo within the body and in vitro test systems respectively. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

A Novel Surface Treatment for Titanium Alloys

NASA Technical Reports Server (NTRS)

Lowther, S. E.; Park, C.; SaintClair, T. L.

2004-01-01

High-speed commercial aircraft require a surface treatment for titanium (Ti) alloy that is both environmentally safe and durable under the conditions of supersonic flight. A number of pretreatment procedures for Ti alloy requiring multi-stages have been developed to produce a stable surface. Among the stages are, degreasing, mechanical abrasion, chemical etching, and electrochemical anodizing. These treatments exhibit significant variations in their long-term stability, and the benefits of each step in these processes still remain unclear. In addition, chromium compounds are often used in many chemical treatments and these materials are detrimental to the environment. Recently, a chromium-free surface treatment for Ti alloy has been reported, though not designed for high temperature applications. In the present study, a simple surface treatment process developed at NASA/LaRC is reported, offering a high performance surface for a variety of applications. This novel surface treatment for Ti alloy is conventionally achieved by forming oxides on the surface with a two-step chemical process without mechanical abrasion. This acid-followed-by-base treatment was designed to be cost effective and relatively safe to use in a commercial application. In addition, it is chromium-free, and has been successfully used with a sol-gel coating to afford a strong adhesive bond after exposure to hot-wet environments. Phenylethynyl containing adhesives were used to evaluate this surface treatment with sol-gel solutions made of novel imide silanes developed at NASA/LaRC. Oxide layers developed by this process were controlled by immersion time and temperature and solution concentration. The morphology and chemical composition of the oxide layers were investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Bond strengths made with this new treatment were evaluated using single lap shear tests.

Comparison of different advanced oxidation process to reduce toxicity and mineralisation of tannery wastewater.

PubMed

Schrank, S G; José, H J; Moreira, R F P M; Schröder, H Fr

2004-01-01

Many organic compounds contained in wastewater are resistant to conventional chemical and/or biological treatment. Because of this reason different degradation techniques are studied as an alternative to biological and classical physico-chemical processes. Advanced Oxidation Processes (AOPs) probably have developed to become the best options in the near future. AOP while making use of different reaction systems, are all characterised by the same chemical feature: production of OH radicals (*OH). The versatility of AOPs is also enhanced by the fact that they offer different possibilities for OH radical production, thus allowing them to conform to specific treatment requirements. The main problem with AOPs is their high cost. The application of solar technologies to these processes could help to diminish that problem by reducing the energy consumption required for generating UV radiation. In this work, different AOPs (O3, TiO2/UV, Fenton and H2O2/UV) were examined to treat tannery wastewater or as a pre-treatment step for improving the biodegradation of tannery wastewater, at different pH and dosage of the chemicals. Under certain circumstances retardation in biodegradation and/or an increase in toxicity may be observed within these treatment steps. Two different bioassays (Daphnia magna and Vibrio fischeri) have been used for testing the progress of toxicity during the treatment. In parallel other objectives were to analyse and identify organic compounds present in the untreated wastewater and arising degradation products in AOP treated wastewater samples. For this purpose substance specific techniques, e.g., gas chromatography-mass spectrometry (GC-MS) in positive electron impact (El(+)) mode and atmospheric pressure ionisation (API) in combination with flow injection analysis (FIA) or liquid chromatography-mass and tandem mass spectrometry (LC-MS or LC-MS-MS) were performed.

Direct Growth of Graphene Film on Germanium Substrate

PubMed Central

Wang, Gang; Zhang, Miao; Zhu, Yun; Ding, Guqiao; Jiang, Da; Guo, Qinglei; Liu, Su; Xie, Xiaoming; Chu, Paul K.; Di, Zengfeng; Wang, Xi

2013-01-01

Graphene has been predicted to play a role in post-silicon electronics due to the extraordinary carrier mobility. Chemical vapor deposition of graphene on transition metals has been considered as a major step towards commercial realization of graphene. However, fabrication based on transition metals involves an inevitable transfer step which can be as complicated as the deposition of graphene itself. By ambient-pressure chemical vapor deposition, we demonstrate large-scale and uniform depositon of high-quality graphene directly on a Ge substrate which is wafer scale and has been considered to replace conventional Si for the next generation of high-performance metal-oxide-semiconductor field-effect transistors (MOSFETs). The immiscible Ge-C system under equilibrium conditions dictates graphene depositon on Ge via a self-limiting and surface-mediated process rather than a precipitation process as observed from other metals with high carbon solubility. Our technique is compatible with modern microelectronics technology thus allowing integration with high-volume production of complementary metal-oxide-semiconductors (CMOS). PMID:23955352

Improving the Desulfurization Degree of High-Grade Nickel Matte via a Two-Step Oxidation Roasting Process

NASA Astrophysics Data System (ADS)

Xi, Zhao; Wang, Zhixing; Li, Xinhai; Guo, Huajun; Yan, Guochun; Wang, Jiexi

2018-05-01

Generally, sulfur elimination from nickel matte was incomplete in the one-step oxidation roasting process. In this work, X-ray diffraction, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and chemical analysis of the roasted products were carried out to explain this phenomenon. The results indicated that the melting of heazlewoodite was the main limiting factor. Thereafter, the oxidation mechanism of high-grade nickel matte from room temperature to 1000 °C was studied. It was found that the transformation from heazlewoodite (Ni3S2) to nickel sulfide (NiS) took place from 400 °C to 520 °C. Considering that the melting temperature of NiS was much higher than that of Ni3S2, a low-temperature roasting step was suggested to suppress the melting of heazlewoodite. Under the optimum conditions (520 °C for 120 minutes followed by 800 °C for 80 minutes), the degree of desulfurization reached 99.52 pct. These results indicated that the two-step oxidation roasting method could be a promising process for producing low-sulfur calcine from high-grade nickel matte.

Chemical and biological processes for multi-metal extraction from waste printed circuit boards of computers and mobile phones.

PubMed

Shah, Monal B; Tipre, Devayani R; Dave, Shailesh R

2014-11-01

E-waste printed circuit boards (PCB) of computers, mobile-phones, televisions, LX (LongXiang) PCB in LED lights and bulbs, and tube-lights were crushed to ≥250 µm particle size and 16 different metals were analysed. A comparative study has been carried out to evaluate the extraction of Cu-Zn-Ni from computer printed circuit boards (c-PCB) and mobile-phone printed circuit boards (m-PCB) by chemical and biological methods. Chemical process showed the extraction of Cu-Zn-Ni by ferric sulphate was best among the studied chemical lixiviants. Bioleaching experiments were carried out with the iron oxidising consortium, which showed that when E-waste and inoculum were added simultaneously in the medium (one-step process); 60.33% and 87.50% Cu, 75.67% and 85.67% Zn and 71.09% and 81.87% Ni were extracted from 10 g L(-1) of c-PCB and m-PCB, respectively, within 10-15 days of reaction time. Whereas, E-waste added after the complete oxidation of Fe(2+) to Fe(3+) iron containing medium (two-step process) showed 85.26% and 99.99% Cu, 96.75% and 99.49% Zn and 93.23% and 84.21% Ni extraction from c-PCB and m-PCB, respectively, only in 6-8 days. Influence of varying biogenerated Fe(3+) and c-PCB concentrations showed that 16.5 g L(-1) of Fe(3+) iron was optimum up to 100 g L(-1) of c-PCB. Changes in pH, acid consumed and redox potential during the process were also studied. The present study shows the ability of an eco-friendly process for the recovery of multi-metals from E-waste even at 100 g L(-1) printed circuit boards concentration. © The Author(s) 2014.

Characterization of landfill leachates by molecular size distribution, biodegradability, and inert chemical oxygen demand.

PubMed

Amaral, Míriam C S; Ferreira, Cynthia F A; Lange, Liséte Celina; Aquino, Sérgio F

2009-05-01

This work presents results from a detailed characterization of landfill leachates of different ages from a landfill in a major Brazilian city. This characterization consists of determining the molecular size distribution and the inert chemical oxygen demand (COD) and the biodegradability of both aerobic and anaerobic processes. Results show that leachate with a high COD concentration leachate has low biodegradability. A significant fraction of the COD is not characterized as protein, carbohydrate, or lipids, which reinforces the hypothesis that the remaining fraction was present in all leachate fractions (less than 1 kDa; between 1 and 10 kDa; between 10 and 100 kDa; and greater than 100 kDa) and is refractory. These results suggest that leachates with such characteristics require treatment systems that use physical-chemical processes as a pre- or post-treatment step to biological processes.

Catalytic amino acid production from biomass-derived intermediates.

PubMed

Deng, Weiping; Wang, Yunzhu; Zhang, Sui; Gupta, Krishna M; Hülsey, Max J; Asakura, Hiroyuki; Liu, Lingmei; Han, Yu; Karp, Eric M; Beckham, Gregg T; Dyson, Paul J; Jiang, Jianwen; Tanaka, Tsunehiro; Wang, Ye; Yan, Ning

2018-05-15

Amino acids are the building blocks for protein biosynthesis and find use in myriad industrial applications including in food for humans, in animal feed, and as precursors for bio-based plastics, among others. However, the development of efficient chemical methods to convert abundant and renewable feedstocks into amino acids has been largely unsuccessful to date. To that end, here we report a heterogeneous catalyst that directly transforms lignocellulosic biomass-derived α-hydroxyl acids into α-amino acids, including alanine, leucine, valine, aspartic acid, and phenylalanine in high yields. The reaction follows a dehydrogenation-reductive amination pathway, with dehydrogenation as the rate-determining step. Ruthenium nanoparticles supported on carbon nanotubes (Ru/CNT) exhibit exceptional efficiency compared with catalysts based on other metals, due to the unique, reversible enhancement effect of NH 3 on Ru in dehydrogenation. Based on the catalytic system, a two-step chemical process was designed to convert glucose into alanine in 43% yield, comparable with the well-established microbial cultivation process, and therefore, the present strategy enables a route for the production of amino acids from renewable feedstocks. Moreover, a conceptual process design employing membrane distillation to facilitate product purification is proposed and validated. Overall, this study offers a rapid and potentially more efficient chemical method to produce amino acids from woody biomass components. Copyright © 2018 the Author(s). Published by PNAS.

Chemomics-based marker compounds mining and mimetic processing for exploring chemical mechanisms in traditional processing of herbal medicines, a continuous study on Rehmanniae Radix.

PubMed

Zhou, Li; Xu, Jin-Di; Zhou, Shan-Shan; Shen, Hong; Mao, Qian; Kong, Ming; Zou, Ye-Ting; Xu, Ya-Yun; Xu, Jun; Li, Song-Lin

2017-12-29

Exploring processing chemistry, in particular the chemical transformation mechanisms involved, is a key step to elucidate the scientific basis in traditional processing of herbal medicines. Previously, taking Rehmanniae Radix (RR) as a case study, the holistic chemome (secondary metabolome and glycome) difference between raw and processed RR was revealed by integrating hyphenated chromatographic techniques-based targeted glycomics and untargeted metabolomics. Nevertheless, the complex chemical transformation mechanisms underpinning the holistic chemome variation in RR processing remain to be extensively clarified. As a continuous study, here a novel strategy by combining chemomics-based marker compounds mining and mimetic processing is proposed for further exploring the chemical mechanisms involved in herbal processing. First, the differential marker compounds between raw and processed herbs were rapidly discovered by untargeted chemomics-based mining approach through multivariate statistical analysis of the chemome data obtained by integrated metabolomics and glycomics analysis. Second, the marker compounds were mimetically processed under the simulated physicochemical conditions as in the herb processing, and the final reaction products were chemically characterized by targeted chemomics-based mining approach. Third, the main chemical transformation mechanisms involved were clarified by linking up the original marker compounds and their mimetic processing products. Using this strategy, a set of differential marker compounds including saccharides, glycosides and furfurals in raw and processed RR was rapidly found, and the major chemical mechanisms involved in RR processing were elucidated as stepwise transformations of saccharides (polysaccharides, oligosaccharides and monosaccharides) and glycosides (iridoid glycosides and phenethylalcohol glycosides) into furfurals (glycosylated/non-glycosylated hydroxymethylfurfurals) by deglycosylation and/or dehydration. The research deliverables indicated that the proposed strategy could advance the understanding of RR processing chemistry, and therefore may be considered a promising approach for delving into the scientific basis in traditional processing of herbal medicines. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of the chemical pathway of gaseous nitrogen dioxide formation during flue gas desulfurization with dry sodium bicarbonate injection

NASA Astrophysics Data System (ADS)

Stein, Antoinette Weil

The chemical reaction pathway for the viable flue gas desulfurization process, dry sodium bicarbonate injection, was investigated to mitigate undesirable plume discoloration. Based on a foundation of past findings, a simplified three-step reaction pathway was hypothesized for the formation of the plume-discoloring constituent, NO2. As the first step, it was hypothesized that sodium sulfite formed by sodium bicarbonate reaction with flue gas SO 2. As the second step, it was hypothesized that sodium nitrate formed by sodium sulfite reaction with flue gas NO. And as the third step, it was hypothesized that NO2 and sodium sulfate formed by sodium nitrate reaction with SO2. The second and third hypothesized steps were experimentally investigated using an isothermal fixed bed reactor. As reported in the past, technical grade sodium sulfite was found to be un-reactive with NO and O2. Freshly prepared sodium sulfite, maintained unexposed to moist air, was shown to react with NO and O2 resulting in a mixture of sodium nitrite and sodium nitrate together with a significant temperature rise. This reaction was found to proceed only when oxygen was present in the flue gas. As reported in the past, technical grade sodium nitrate was shown to be un-reactive with SO2. But freshly formed sodium nitrate kept unexposed to humidity was found to be reactive with SO2 and O 2 resulting in the formation of NO2 and sodium sulfate polymorphic Form I. The NO2 formation by this reaction was shown to be temperature dependent with maximum formation at 175°C. Plume mitigation methods were studied based on the validated three-step reaction pathway. Mitigation of NO2 was exhibited by limiting oxygen concentration in the flue gas to a level below 5%. It was also shown that significant NO2 mitigation was achieved by operating below 110°C or above 250°C. An innovative NO2 mitigation method was patented as a result of the findings of this study. The patented process incorporated a process step of sodium sulfite injection to remove flue gas NO prior to sodium bicarbonate injection.

Preparation and Optical Properties of CuS Nanofilms by a Facile Two-Step Process

NASA Astrophysics Data System (ADS)

Cui, Zhankui; Zhou, Junqiang; Ge, Suxiang; Zhao, Hongxiao

CuS nanofilms were prepared by a facile two-step process including chemical bath deposition of Cu nanofilms first and the subsequent thermal sulfuration step. The composition and structure of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and Raman spectroscopy. The optical properties of CuS nanofilms were determined by Ultraviolet-visible (UV-Vis) technique. The results show that the nanofilms composed by Cu spherical nanoparticles were completely transformed to the nanofilms composed by CuS nanosheets when the sulfuration temperature was 350∘C. The light absorption edges of CuS nanofilms exhibit red shift when sulfuration occurred at lower temperature. A plausible growth mechanism related with gas phase reaction for formation of CuS nanofilms was also proposed.

Quantifying chemical reactions by using mixing analysis.

PubMed

Jurado, Anna; Vázquez-Suñé, Enric; Carrera, Jesús; Tubau, Isabel; Pujades, Estanislao

2015-01-01

This work is motivated by a sound understanding of the chemical processes that affect the organic pollutants in an urban aquifer. We propose an approach to quantify such processes using mixing calculations. The methodology consists of the following steps: (1) identification of the recharge sources (end-members) and selection of the species (conservative and non-conservative) to be used, (2) identification of the chemical processes and (3) evaluation of mixing ratios including the chemical processes. This methodology has been applied in the Besòs River Delta (NE Barcelona, Spain), where the River Besòs is the main aquifer recharge source. A total number of 51 groundwater samples were collected from July 2007 to May 2010 during four field campaigns. Three river end-members were necessary to explain the temporal variability of the River Besòs: one river end-member is from the wet periods (W1) and two are from dry periods (D1 and D2). This methodology has proved to be useful not only to compute the mixing ratios but also to quantify processes such as calcite and magnesite dissolution, aerobic respiration and denitrification undergone at each observation point. Copyright © 2014 Elsevier B.V. All rights reserved.

Approaches to eliminating chlorofluorocarbon use in manufacturing.

PubMed Central

Boyhan, W S

1992-01-01

Until quite recently, chlorofluorocarbons (CFCs) had been considered the safest and most benign of industrial chemicals. Their physical and chemical properties made them an integral part of manufacturing processes for electronics products. The recognition that CFCs destroy the stratospheric ozone layer, with consequent enormous consequences to all forms of life on earth, has led to international agreements which will end virtually all possibly before. This impending phaseout of CFCs has caused electronics manufacturers to examine alternative chemicals and processing methods. This manuscript documents the steps AT&T has taken to reach its goal of 100% phaseout of CFCs by years-end 1994. These actions include top-down management support with combined bottom-up thrusts, an internal information gathering and dissemination center, internal technology transfer, and external corporate activism. Images PMID:11607258

X-ray coherent diffraction imaging of cellulose fibrils in situ.

PubMed

Lal, Jyotsana; Harder, Ross; Makowski, Lee

2011-01-01

Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize.

Investigating Students' Similarity Judgments in Organic Chemistry

ERIC Educational Resources Information Center

Graulich, N.; Bhattacharyya, G.

2017-01-01

Organic chemistry is possibly the most visual science of all chemistry disciplines. The process of scientific inquiry in organic chemistry relies on external representations, such as Lewis structures, mechanisms, and electron arrows. Information about chemical properties or driving forces of mechanistic steps is not available through direct…

Production of polyol oils from soybean oil through bioprocess

USDA-ARS?s Scientific Manuscript database

Soy-polyol oils (oxygenated acylglycerols) are important starting materials for the manufacture of polymers such as polyurethane. Currently, they are produced by a two-step chemical process involving epoxidation and then the subsequent opening of the oxirane ring. The objective of this study is to d...

Microwave-assisted maleation of tung oil for bio-based products

USDA-ARS?s Scientific Manuscript database

In this work, a simple, “green” and convenient chemical modification of tung oil for maleinized tung oil (TOMA) was developed via microwave-assisted one-step maleation. This modifying process did not involve any solvent, catalyst, or initiator, but demonstrated the most efficiency of functionalizing...

Multi-step process for concentrating magnetic particles in waste sludges

DOEpatents

Watson, John L.

1990-01-01

This invention involves a multi-step, multi-force process for dewatering sludges which have high concentrations of magnetic particles, such as waste sludges generated during steelmaking. This series of processing steps involves (1) mixing a chemical flocculating agent with the sludge; (2) allowing the particles to aggregate under non-turbulent conditions; (3) subjecting the mixture to a magnetic field which will pull the magnetic aggregates in a selected direction, causing them to form a compacted sludge; (4) preferably, decanting the clarified liquid from the compacted sludge; and (5) using filtration to convert the compacted sludge into a cake having a very high solids content. Steps 2 and 3 should be performed simultaneously. This reduces the treatment time and increases the extent of flocculation and the effectiveness of the process. As partially formed aggregates with active flocculating groups are pulled through the mixture by the magnetic field, they will contact other particles and form larger aggregates. This process can increase the solids concentration of steelmaking sludges in an efficient and economic manner, thereby accomplishing either of two goals: (a) it can convert hazardous wastes into economic resources for recycling as furnace feed material, or (b) it can dramatically reduce the volume of waste material which must be disposed.

Multi-step process for concentrating magnetic particles in waste sludges

DOEpatents

Watson, J.L.

1990-07-10

This invention involves a multi-step, multi-force process for dewatering sludges which have high concentrations of magnetic particles, such as waste sludges generated during steelmaking. This series of processing steps involves (1) mixing a chemical flocculating agent with the sludge; (2) allowing the particles to aggregate under non-turbulent conditions; (3) subjecting the mixture to a magnetic field which will pull the magnetic aggregates in a selected direction, causing them to form a compacted sludge; (4) preferably, decanting the clarified liquid from the compacted sludge; and (5) using filtration to convert the compacted sludge into a cake having a very high solids content. Steps 2 and 3 should be performed simultaneously. This reduces the treatment time and increases the extent of flocculation and the effectiveness of the process. As partially formed aggregates with active flocculating groups are pulled through the mixture by the magnetic field, they will contact other particles and form larger aggregates. This process can increase the solids concentration of steelmaking sludges in an efficient and economic manner, thereby accomplishing either of two goals: (a) it can convert hazardous wastes into economic resources for recycling as furnace feed material, or (b) it can dramatically reduce the volume of waste material which must be disposed. 7 figs.

Controlling the Local Electronic Properties of Si(553)-Au through Hydrogen Doping

NASA Astrophysics Data System (ADS)

Hogan, C.; Speiser, E.; Chandola, S.; Suchkova, S.; Aulbach, J.; Schäfer, J.; Meyer, S.; Claessen, R.; Esser, N.

2018-04-01

We propose a quantitative and reversible method for tuning the charge localization of Au-stabilized stepped Si surfaces by site-specific hydrogenation. This is demonstrated for Si(553)-Au as a model system by combining density functional theory simulations and reflectance anisotropy spectroscopy experiments. We find that controlled H passivation is a two-step process: step-edge adsorption drives excess charge into the conducting metal chain "reservoir" and renders it insulating, while surplus H recovers metallic behavior. Our approach illustrates a route towards microscopic manipulation of the local surface charge distribution and establishes a reversible switch of site-specific chemical reactivity and magnetic properties on vicinal surfaces.

Highly efficient chemical process to convert mucic acid into adipic acid and DFT studies of the mechanism of the rhenium-catalyzed deoxydehydration.

PubMed

Li, Xiukai; Wu, Di; Lu, Ting; Yi, Guangshun; Su, Haibin; Zhang, Yugen

2014-04-14

The production of bulk chemicals and fuels from renewable bio-based feedstocks is of significant importance for the sustainability of human society. Adipic acid, as one of the most-demanded drop-in chemicals from a bioresource, is used primarily for the large-volume production of nylon-6,6 polyamide. It is highly desirable to develop sustainable and environmentally friendly processes for the production of adipic acid from renewable feedstocks. However, currently there is no suitable bio-adipic acid synthesis process. Demonstrated herein is the highly efficient synthetic protocol for the conversion of mucic acid into adipic acid through the oxorhenium-complex-catalyzed deoxydehydration (DODH) reaction and subsequent Pt/C-catalyzed transfer hydrogenation. Quantitative yields (99 %) were achieved for the conversion of mucic acid into muconic acid and adipic acid either in separate sequences or in a one-step process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Occupational exposure in the fluorescent lamp recycling sector in France

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimmermann, François, E-mail: francois.zimmermann@inrs.fr; Lecler, Marie-Thérèse; Clerc, Frédéric

Highlights: • Chemical risks were assessed in the five fluorescent lamp recycling facilities. • The main hazardous agents are mercury vapors and dust containing lead and yttrium. • Exposure and pollutant levels were correlated with steps and processes. • All the stages and processes are concerned by worrying levels of pollutants. • We suggest recommendations to reduce chemical risk. - Abstract: The fluorescent lamp recycling sector is growing considerably in Europe due to increasingly strict regulations aimed at inciting the consumption of low energy light bulbs and their end-of-life management. Chemical risks were assessed in fluorescent lamp recycling facilities bymore » field measurement surveys in France, highlighting that occupational exposure and pollutant levels in the working environment were correlated with the main recycling steps and processes. The mean levels of worker exposure are 4.4 mg/m{sup 3}, 15.4 μg/m{sup 3}, 14.0 μg/m{sup 3}, 247.6 μg/m{sup 3}, respectively, for total inhalable dust, mercury, lead and yttrium. The mean levels of airborne pollutants are 3.1 mg/m{sup 3}, 9.0 μg/m{sup 3}, 9.0 μg/m{sup 3}, 219.2 μg/m{sup 3}, respectively, for total inhalable dust, mercury, lead and yttrium. The ranges are very wide. Surface samples from employees’ skin and granulometric analysis were also carried out. The overview shows that all the stages and processes involved in lamp recycling are concerned by the risk of hazardous substances penetrating into the bodies of employees, although exposure of the latter varies depending on the processes and tasks they perform. The conclusion of this study strongly recommends the development of a new generation of processes in parallel with more information sharing and regulatory measures.« less

Mapping the Limitations of Breakthrough Analysis in Fixed-Bed Adsorption

NASA Technical Reports Server (NTRS)

Knox, James Clinton

2017-01-01

The separation of gases through adsorption plays an important role in the chemical processing industry, where the separation step is often the costliest part of a chemical process and thus worthy of careful study and optimization. This work developed a number of new, archival aspects on the computer simulations used for the refinement and design of these gas adsorption processes: 1. Presented a new approach to fit the undetermined heat and mass transfer coefficients in the axially dispersed plug flow equation and associated balance equations 2. Examined and described the conditions where non-physical simulation results can arise 3. Presented an approach to determine the limits of the axial dispersion and LDF mass transfer terms above which non-physical simulation results occur.

Nano-Electrochemistry and Nano-Electrografting with an Original Combined AFM-SECM

PubMed Central

Ghorbal, Achraf; Grisotto, Federico; Charlier, Julienne; Palacin, Serge; Goyer, Cédric; Demaille, Christophe; Ben Brahim, Ammar

2013-01-01

This study demonstrates the advantages of the combination between atomic force microscopy and scanning electrochemical microscopy. The combined technique can perform nano-electrochemical measurements onto agarose surface and nano-electrografting of non-conducting polymers onto conducting surfaces. This work was achieved by manufacturing an original Atomic Force Microscopy-Scanning ElectroChemical Microscopy (AFM-SECM) electrode. The capabilities of the AFM-SECM-electrode were tested with the nano-electrografting of vinylic monomers initiated by aryl diazonium salts. Nano-electrochemical and technical processes were thoroughly described, so as to allow experiments reproducing. A plausible explanation of chemical and electrochemical mechanisms, leading to the nano-grafting process, was reported. This combined technique represents the first step towards improved nano-processes for the nano-electrografting. PMID:28348337

Sequential lignin depolymerization by combination of biocatalytic and formic acid/formate treatment steps.

PubMed

Gasser, Christoph A; Čvančarová, Monika; Ammann, Erik M; Schäffer, Andreas; Shahgaldian, Patrick; Corvini, Philippe F-X

2017-03-01

Lignin, a complex three-dimensional amorphous polymer, is considered to be a potential natural renewable resource for the production of low-molecular-weight aromatic compounds. In the present study, a novel sequential lignin treatment method consisting of a biocatalytic oxidation step followed by a formic acid-induced lignin depolymerization step was developed and optimized using response surface methodology. The biocatalytic step employed a laccase mediator system using the redox mediator 1-hydroxybenzotriazole. Laccases were immobilized on superparamagnetic nanoparticles using a sorption-assisted surface conjugation method allowing easy separation and reuse of the biocatalysts after treatment. Under optimized conditions, as much as 45 wt% of lignin could be solubilized either in aqueous solution after the first treatment or in ethyl acetate after the second (chemical) treatment. The solubilized products were found to be mainly low-molecular-weight aromatic monomers and oligomers. The process might be used for the production of low-molecular-weight soluble aromatic products that can be purified and/or upgraded applying further downstream processes.

Breathe easy with proper respiratory protection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bidwell, J.

1996-05-01

Evaluating the need for respiratory protection in chemical process industries (CPI) plants and selecting the appropriate respirator involves several steps. The Occupational Safety and Health Administration (OSHA) general industry standard for respiratory protection (29 CFR 1910.134(b)) requires the employer to establish a program to help reduce exposures to occupational contaminants. When feasible, employers must eliminate contaminants by using engineering controls (such as general and local ventilation, enclosure or isolation, or substitution of a less-hazardous process or material). Establishing a respiratory protection program consists of four steps: (1) Identify respiratory hazards and concentrations; (2) Understand the contaminants` effects on workers` health;more » (3) Select appropriate respiratory protection; and (4) Train in proper respirator use and maintenance. Consult applicable state and OSHA requirements to ensure that your program satisfies these steps. Industrial respirator manufacturers can assist with on-site training and fit testing. The paper discusses these four steps, program guidelines, determination of the hazard, and styles of respirators.« less

Lipid extraction methods from microalgal biomass harvested by two different paths: screening studies toward biodiesel production.

PubMed

Ríos, Sergio D; Castañeda, Joandiet; Torras, Carles; Farriol, Xavier; Salvadó, Joan

2013-04-01

Microalgae can grow rapidly and capture CO2 from the atmosphere to convert it into complex organic molecules such as lipids (biodiesel feedstock). High scale economically feasible microalgae based oil depends on optimizing the entire process production. This process can be divided in three very different but directly related steps (production, concentration, lipid extraction and transesterification). The aim of this study is to identify the best method of lipid extraction to undergo the potentiality of some microalgal biomass obtained from two different harvesting paths. The first path used all physicals concentration steps, and the second path was a combination of chemical and physical concentration steps. Three microalgae species were tested: Phaeodactylum tricornutum, Nannochloropsis gaditana, and Chaetoceros calcitrans One step lipid extraction-transesterification reached the same fatty acid methyl ester yield as the Bligh and Dyer and soxhlet extraction with n-hexane methods with the corresponding time, cost and solvent saving. Copyright © 2013 Elsevier Ltd. All rights reserved.

Challenges in Liquid-Phase Exfoliation, Processing, and Assembly of Pristine Graphene.

PubMed

Parviz, Dorsa; Irin, Fahmida; Shah, Smit A; Das, Sriya; Sweeney, Charles B; Green, Micah J

2016-10-01

Recent developments in the exfoliation, dispersion, and processing of pristine graphene (i.e., non-oxidized graphene) are described. General metrics are outlined that can be used to assess the quality and processability of various "graphene" products, as well as metrics that determine the potential for industrial scale-up. The pristine graphene production process is categorized from a chemical engineering point of view with three key steps: i) pretreatment, ii) exfoliation, and iii) separation. How pristine graphene colloidal stability is distinct from the exfoliation step and is dependent upon graphene interactions with solvents and dispersants are extensively reviewed. Finally, the challenges and opportunities of using pristine graphene as nanofillers in polymer composites, as well as as building blocks for macrostructure assemblies are summarized in the context of large-scale production. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of activated carbon from white lotus via single step chemical activation

NASA Astrophysics Data System (ADS)

Andas, Jeyashelly; Midon, Muhammad Dzulfiqar

2017-08-01

Highly porous activated carbon was successfully fabricated from the stalk of Nymphaea odorata via single step chemical activation. ZnCl2 was used as the chemical activating agent in the activation process. The raw material was preliminary characterized using Fourier Transform Infrared (FTIR), ultimate analysis (CHNS/O Analyzer) and Scanning Electron Microscope (SEM). The percentage yield, iodine number (IN) and the textural properties of the activated carbon were optimized under the influence of several synthesizing parameters such as impregnation ratio, activation temperature and activation time using ZnCl2. High IN (750.11 mg/g - 967.16 mg/g) was obtained from Sodium thiosulphate volumetric method and represents the porosity of the synthesized materials. Reduction in several functional groups was observed in the FTIR spectrum of the synthesized activated carbon. SEM analysis of the activated carbon verified the formation of highly porous surface compared to the raw Nymphaea odorata. This study provides a facile synthesis of activated carbon from waste natural resources at benign condition.

Porous polycarbene-bearing membrane actuator for ultrasensitive weak-acid detection and real-time chemical reaction monitoring.

PubMed

Sun, Jian-Ke; Zhang, Weiyi; Guterman, Ryan; Lin, Hui-Juan; Yuan, Jiayin

2018-04-30

Soft actuators with integration of ultrasensitivity and capability of simultaneous interaction with multiple stimuli through an entire event ask for a high level of structure complexity, adaptability, and/or multi-responsiveness, which is a great challenge. Here, we develop a porous polycarbene-bearing membrane actuator built up from ionic complexation between a poly(ionic liquid) and trimesic acid (TA). The actuator features two concurrent structure gradients, i.e., an electrostatic complexation (EC) degree and a density distribution of a carbene-NH 3 adduct (CNA) along the membrane cross-section. The membrane actuator performs the highest sensitivity among the state-of-the-art soft proton actuators toward acetic acid at 10 -6  mol L -1 (M) level in aqueous media. Through competing actuation of the two gradients, it is capable of monitoring an entire process of proton-involved chemical reactions that comprise multiple stimuli and operational steps. The present achievement constitutes a significant step toward real-life application of soft actuators in chemical sensing and reaction technology.

Continuous bind-and-elute protein A capture chromatography: Optimization under process scale column constraints and comparison to batch operation.

PubMed

Kaltenbrunner, Oliver; Diaz, Luis; Hu, Xiaochun; Shearer, Michael

2016-07-08

Recently, continuous downstream processing has become a topic of discussion and analysis at conferences while no industrial applications of continuous downstream processing for biopharmaceutical manufacturing have been reported. There is significant potential to increase the productivity of a Protein A capture step by converting the operation to simulated moving bed (SMB) mode. In this mode, shorter columns are operated at higher process flow and corresponding short residence times. The ability to significantly shorten the product residence time during loading without appreciable capacity loss can dramatically increase productivity of the capture step and consequently reduce the amount of Protein A resin required in the process. Previous studies have not considered the physical limitations of how short columns can be packed and the flow rate limitations due to pressure drop of stacked columns. In this study, we are evaluating the process behavior of a continuous Protein A capture column cycling operation under the known pressure drop constraints of a compressible media. The results are compared to the same resin operated under traditional batch operating conditions. We analyze the optimum system design point for a range of feed concentrations, bed heights, and load residence times and determine achievable productivity for any feed concentration and any column bed height. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:938-948, 2016. © 2016 American Institute of Chemical Engineers.

Virus elimination during the purification of monoclonal antibodies by column chromatography and additional steps.

PubMed

Roberts, Peter L

2014-01-01

The theoretical potential for virus transmission by monoclonal antibody based therapeutic products has led to the inclusion of appropriate virus reduction steps. In this study, virus elimination by the chromatographic steps used during the purification process for two (IgG-1 & -3) monoclonal antibodies (MAbs) have been investigated. Both the Protein G (>7log) and ion-exchange (5 log) chromatography steps were very effective for eliminating both enveloped and non-enveloped viruses over the life-time of the chromatographic gel. However, the contribution made by the final gel filtration step was more limited, i.e., 3 log. Because these chromatographic columns were recycled between uses, the effectiveness of the column sanitization procedures (guanidinium chloride for protein G or NaOH for ion-exchange) were tested. By evaluating standard column runs immediately after each virus spiked run, it was possible to directly confirm that there was no cross contamination with virus between column runs (guanidinium chloride or NaOH). To further ensure the virus safety of the product, two specific virus elimination steps have also been included in the process. A solvent/detergent step based on 1% triton X-100 rapidly inactivating a range of enveloped viruses by >6 log inactivation within 1 min of a 60 min treatment time. Virus removal by virus filtration step was also confirmed to be effective for those viruses of about 50 nm or greater. In conclusion, the combination of these multiple steps ensures a high margin of virus safety for this purification process. © 2014 American Institute of Chemical Engineers.

Simulation and flavor compound analysis of dealcoholized beer via one-step vacuum distillation.

PubMed

Andrés-Iglesias, Cristina; García-Serna, Juan; Montero, Olimpio; Blanco, Carlos A

2015-10-01

The coupled operation of vacuum distillation process to produce alcohol free beer at laboratory scale and Aspen HYSYS simulation software was studied to define the chemical changes during the dealcoholization process in the aroma profiles of 2 different lager beers. At the lab-scale process, 2 different parameters were chosen to dealcoholize beer samples, 102mbar at 50°C and 200mbar at 67°C. Samples taken at different steps of the process were analyzed by HS-SPME-GC-MS focusing on the concentration of 7 flavor compounds, 5 alcohols and 2 esters. For simulation process, the EoS parameters of the Wilson-2 property package were adjusted to the experimental data and one more pressure was tested (60mbar). Simulation methods represent a viable alternative to predict results of the volatile compound composition of a final dealcoholized beer. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biohydrogen and methane production via a two-step process using an acid pretreated native microalgae consortium.

PubMed

Carrillo-Reyes, Julian; Buitrón, Germán

2016-12-01

A native microalgae consortium treated under thermal-acidic hydrolysis was used to produce hydrogen and methane in a two-step sequential process. Different acid concentrations were tested, generating hydrogen and methane yields of up to 45mLH 2 gVS -1 and 432mLCH 4 gVS -1 , respectively. The hydrogen production step solubilized the particulate COD (chemical oxygen demand) up to 30%, creating considerable amounts of volatile fatty acids (up to 10gCODL -1 ). It was observed that lower acid concentration presented higher hydrogen and methane production potential. The results revealed that thermal acid hydrolysis of a native microalgae consortium is a simple but effective strategy for producing hydrogen and methane in the sequential process. In addition to COD removal (50-70%), this method resulted in an energy recovery of up to 15.9kJ per g of volatile solids of microalgae biomass, one of the highest reported. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transfection in perfused microfluidic cell culture devices: A case study.

PubMed

Raimes, William; Rubi, Mathieu; Super, Alexandre; Marques, Marco P C; Veraitch, Farlan; Szita, Nicolas

2017-08-01

Automated microfluidic devices are a promising route towards a point-of-care autologous cell therapy. The initial steps of induced pluripotent stem cell (iPSC) derivation involve transfection and long term cell culture. Integration of these steps would help reduce the cost and footprint of micro-scale devices with applications in cell reprogramming or gene correction. Current examples of transfection integration focus on maximising efficiency rather than viable long-term culture. Here we look for whole process compatibility by integrating automated transfection with a perfused microfluidic device designed for homogeneous culture conditions. The injection process was characterised using fluorescein to establish a LabVIEW-based routine for user-defined automation. Proof-of-concept is demonstrated by chemically transfecting a GFP plasmid into mouse embryonic stem cells (mESCs). Cells transfected in the device showed an improvement in efficiency (34%, n = 3) compared with standard protocols (17.2%, n = 3). This represents a first step towards microfluidic processing systems for cell reprogramming or gene therapy.

Process for purification of silicon

NASA Technical Reports Server (NTRS)

Rath, H. J.; Sirtl, E.; Pfeiffer, W.

1981-01-01

The purification of metallurgically pure silicon having a silicon content of more than 95% by weight is accomplished by leaching with an acidic solution which substantially does not attack silicon. A mechanical treatment leading to continuous particle size reduction of the granulated silicon to be purified is combined with the chemical purification step.

Microwave-assisted maleation of tung oil for bio-based products with versatile applications

USDA-ARS?s Scientific Manuscript database

In this work, a simple, “green” and convenient chemical modification of tung oil for maleinized tung oil (TOMA) was developed via microwave-assisted one-step maleation. This modifying process did not involve any solvent, catalyst, or initiator, but demonstrated the most efficiency of functionalizing...

A CHEMICAL METHOD OF TREATING FISSIONABLE MATERIAL

DOEpatents

Olson, C.M.

1959-09-01

One step of a process for separating plutonium from uranium and fission products is presented. A nitric acid solution containing these constituents is treated with formic acid to reduce simultaneously the plutonium to a valence state of not greater than +4 and destroy and eliminate the excess nitric acid.

Effect of laser fluence and ambient gas pressure on surface morphology and chemical composition of hydroxyapatite thin films deposited using pulsed laser deposition

NASA Astrophysics Data System (ADS)

Nishikawa, Hiroaki; Hasegawa, Tsukasa; Miyake, Akiko; Tashiro, Yuichiro; Komasa, Satoshi; Hashimoto, Yoshiya

2018-01-01

The dependence of the surface morphology and chemical composition of hydroxyapatite (HA) thin films on the laser fluence and ambient gas pressure during their formation by pulsed laser deposition was studied as the first step to investigate the effect of physical and chemical interactions between the ablated chemical species and ambient gas molecules on HA film formation. It was found that a higher fluence could decrease the number of large protrusions on the surface of HA thin films. However, too high a fluence caused a phosphorus deficiency from the stoichiometric value, particularly in the case of lower ambient gas pressure. It was also found that for lower fluences, the atomic species among the ablated chemical species were easily scattered by collision processes with ambient gas molecules. This was caused by the lower velocity of the ablated chemical species and higher ambient gas pressure, which induced a shorter mean free path. In addition, these collision processes played an important role in the adsorption, migration, and re-evaporation of the ablated chemical species on the substrate via chemical reactions.

One-Step Method to Prepare PLLA Porous Microspheres in a High-Voltage Electrostatic Anti-Solvent Process

PubMed Central

Wang, Ying; Zhu, Li-Hui; Chen, Ai-Zheng; Xu, Qiao; Hong, Yu-Juan; Wang, Shi-Bin

2016-01-01

A one-step method using a high-voltage electrostatic anti-solvent process was employed to fabricate poly-l-lactide (PLLA) porous microspheres (PMs). To address the simplification and control of the preparation process, a 24 full factorial experiment was performed to optimize the operating process and analyze the effect of the factors on the morphology and aerodynamic properties of the PLLA PMs, and various characterization tests were also performed. The resulting PLLA PMs exhibited an even and porous morphology with a density less than 0.4 g/cm3, a geometric mean diameter (Dg) of 10–30 μm, an aerodynamic diameter (Da) of 1–5 μm, a fine particle fraction (FPF) of 56.3%, and a porosity of 76.2%, meeting the requirements for pulmonary drug delivery. The physicochemical characterizations reveal that no significant chemical change occurred in the PLLA during the process. An investigation of its in vitro cytotoxicity and pulmonary toxicity shows no obvious toxic response, indicating good biosafety. This study indicates that the one-step method using a high-voltage electrostatic anti-solvent process has great potential in developing an inhalable drug carrier for pulmonary drug delivery. PMID:28773489

Activated carbon fibers and engineered forms from renewable resources

DOEpatents

Baker, Frederick S

2013-02-19

A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

Activated carbon fibers and engineered forms from renewable resources

DOEpatents

Baker, Frederick S.

2010-06-01

A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

Chemical footprint: a methodological framework for bridging life cycle assessment and planetary boundaries for chemical pollution.

PubMed

Sala, Serenella; Goralczyk, Malgorzata

2013-10-01

The development and use of footprint methodologies for environmental assessment are increasingly important for both the scientific and political communities. Starting from the ecological footprint, developed at the beginning of the 1990s, several other footprints were defined, e.g., carbon and water footprint. These footprints-even though based on a different meaning of "footprint"-integrate life cycle thinking, and focus on some challenging environmental impacts including resource consumption, CO2 emission leading to climate change, and water consumption. However, they usually neglect relevant sources of impacts, as those related to the production and use of chemicals. This article presents and discusses the need and relevance of developing a methodology for assessing the chemical footprint, coupling a life cycle-based approach with methodologies developed in other contexts, such as ERA and sustainability science. Furthermore, different concepts underpin existing footprint and this could be the case also of chemical footprint. At least 2 different approaches and steps to chemical footprint could be envisaged, applicable at the micro- as well as at the meso- and macroscale. The first step (step 1) is related to the account of chemicals use and emissions along the life cycle of a product, sector, or entire economy, to assess potential impacts on ecosystems and human health. The second step (step 2) aims at assessing to which extent actual emission of chemicals harm the ecosystems above their capability to recover (carrying capacity of the system). The latter step might contribute to the wide discussion on planetary boundaries for chemical pollution: the thresholds that should not be surpassed to guarantee a sustainable use of chemicals from an environmental safety perspective. The definition of what the planetary boundaries for chemical pollution are and how the boundaries should be identified is an on-going scientific challenge for ecotoxicology and ecology. In this article, we present a case study at the macroscale for the European Union, in which the chemical footprint according to step 1 is calculated for the year 2005. A proposal for extending this approach toward step 2 is presented and discussed, complemented by a discussion on the challenges and the use of appropriate methodologies for assessing chemical footprints to stimulate further research and discussion on the topic. © 2013 SETAC.

Alkaline-sulfite pretreatment and use of surfactants during enzymatic hydrolysis to enhance ethanol production from sugarcane bagasse.

PubMed

Mesquita, Jéssica Faria; Ferraz, André; Aguiar, André

2016-03-01

Sugarcane bagasse is a by-product from the sugar and ethanol industry which contains approximately 70 % of its dry mass composed by polysaccharides. To convert these polysaccharides into fuel ethanol it is necessary a pretreatment step to increase the enzymatic digestibility of the recalcitrant raw material. In this work, sugarcane bagasse was pretreated by an alkaline-sulfite chemithermomechanical process for increasing its enzymatic digestibility. Na2SO3 and NaOH ratios were fixed at 2:1, and three increasing chemical loads, varying from 4 to 8 % m/m Na2SO3, were used to prepare the pretreated materials. The increase in the alkaline-sulfite load decreased the lignin content in the pretreated material up to 35.5 % at the highest chemical load. The pretreated samples presented enhanced glucose yields during enzymatic hydrolysis as a function of the pretreatment severity. The maximum glucose yield (64 %) was observed for the samples pretreated with the highest chemical load. The use of 2.5 g l(-1) Tween 20 in the hydrolysis step further increased the glucose yield to 75 %. Semi-simultaneous hydrolysis and fermentation of the pretreated materials indicated that the ethanol yield was also enhanced as a function of the pretreatment severity. The maximum ethanol yield was 56 ± 2 % for the sample pretreated with the highest chemical load. For the sample pretreated with the lowest chemical load (2 % m/m NaOH and 4 % m/m Na2SO3), adding Tween 20 during the hydrolysis process increased the ethanol yield from 25 ± 3 to 39.5 ± 1 %.

The lignol approach to biorefining of woody biomass to produce ethanol and chemicals.

PubMed

Arato, Claudio; Pye, E Kendall; Gjennestad, Gordon

2005-01-01

Processes that produce only ethanol from lignocellulosics display poor economics. This is generally overcome by constructing large facilities having satisfactory economies of scale, thus making financing onerous and hindering the development of suitable technologies. Lignol Innovations has developed a biorefining technology that employs an ethanol-based organosolv step to separate lignin, hemicellulose components, and extractives from the cellulosic fraction of woody biomass. The resultant cellulosic fraction is highly susceptible to enzymatic hydrolysis, generating very high yields of glucose (>90% in 12-24 h) with typical enzyme loadings of 10-20 FPU (filter paper units)/g. This glucose is readily converted to ethanol, or possibly other sugar platform chemicals, either by sequential or simultaneous saccharification and fermentation. The liquor from the organosolv step is processed by well-established unit operations to recover lignin, furfural, xylose, acetic acid, and a lipophylic extractives fraction. The process ethanol is recovered and recycled back to the process. The resulting recycled process water is of a very high quality, low BOD5, and suitable for overall system process closure. Significant benefits can be attained in greenhouse gas (GHG) emission reductions, as per the Kyoto Protocol. Revenues from the multiple products, particularly the lignin, ethanol and xylose fractions, ensure excellent economics for the process even in plants as small as 100 mtpd (metric tonnes per day) dry woody biomass input a scale suitable for processing wood residues produced by a single large sawmill.

Solubilization of phosphorus from phosphate rocks with Acidithiobacillus thiooxidans following a growing-then-recovery process.

PubMed

Calle-Castañeda, Susana M; Márquez-Godoy, Marco A; Hernández-Ortiz, Juan P

2017-12-29

Phosphorus is an essential nutrient for the synthesis of biomolecules and is particularly important in agriculture, as soils must be constantly supplemented with its inorganic form to ensure high yields and productivity. In this paper, we propose a process to solubilize phosphorus from phosphate rocks, where Acidithiobacillus thiooxidans cultures are pre-cultivated to foster the acidic conditions for bioleaching-two-step "growing-then-recovery"-. Our method solubilizes 100% of phosphorus, whereas the traditional process without pre-cultivation-single-step "growing-and-recovery"-results in a maximum of 56% solubilization. As a proof of principle, we demonstrate that even at low concentrations of the phosphate rock, 1% w/v, the bacterial culture is unviable and biological activity is not observed during the single-step process. On the other hand, in our method, the bacteria are grown without the rock, ensuring high acid production. Once pH levels are below 0.7, the mineral is added to the culture, resulting in high yields of biological solubilization. According to the Fourier Transform Infrared Spectroscopy spectrums, gypsum is the dominant phosphate phase after both the single- and two-step methods. However, calcite and fluorapatite, dominant in the un-treated rock, are still present after the single-step, highlighting the differences between the chemical and the biological methods. Our process opens new avenues for biotechnologies to recover phosphorus in tropical soils and in low-grade phosphate rock reservoirs.

Sludge Washing and Demonstration of the DWPF Nitric/Formic Flowsheet in the SRNL Shielded Cells for Sludge Batch 9 Qualification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pareizs, J.; Newell, D.; Martino, C.

Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) to qualify the next batch of sludge – Sludge Batch 9 (SB9). Current practice is to prepare sludge batches in Tank 51 by transferring sludge to Tank 51 from other tanks. The sludge is washed and transferred to Tank 40, the current Defense Waste Process Facility (DWPF) feed tank. Prior to sludge transfer from Tank 51 to Tank 40, the Tank 51 sludge must be qualified. SRNL qualifies the sludge in multiple steps. First, a Tank 51 sample is received, then characterized, washed, and again characterized. SRNL thenmore » demonstrates the DWPF Chemical Process Cell (CPC) flowsheet with the sludge. The final step of qualification involves chemical durability measurements of glass fabricated in the DWPF CPC demonstrations. In past sludge batches, SRNL had completed the DWPF demonstration with Tank 51 sludge. For SB9, SRNL has been requested to process a blend of Tank 51 and Tank 40 at a targeted ratio of 44% Tank 51 and 56% Tank 40 on an insoluble solids basis.« less

Toward a conceptual approach for assessing risks from chemical mixtures and other stressors to coastal ecosystem services.

PubMed

Syberg, Kristian; Backhaus, Thomas; Banta, Gary; Bruce, Peter; Gustavsson, Mikael; Munns, Wayne R; Rämö, Robert; Selck, Henriette; Gunnarsson, Jonas S

2017-03-01

Growth of human populations and increased human activity, particularly in coastal areas, increase pressure on coastal ecosystems and the ecosystem services (ES) they provide. As a means toward being able to assess the impact of multiple stressors on ES, in the present study we propose an 8-step conceptual approach for assessing effects of chemical mixtures and other stressors on ES in coastal areas: step A, identify the relevant problems and policy aims; step B, identify temporal and spatial boundaries; step C, identify relevant ES; step D, identify relevant stressors (e.g., chemicals); step E, translate impacts into ES units; step F, assess cumulative risk in ES units; step G, rank stressors based on their contribution to adverse effects on ES; and step H, implement regulation and management as appropriate and necessary. Two illustrative case studies (Swedish coastal waters and a coastal lagoon in Costa Rica) are provided; one focuses on chemicals that affect human food supply and the other addresses pesticide runoff and trade-offs among ES. The 2 cases are used to highlight challenges of such risk assessments, including use of standardized versus ES-relevant test species, data completeness, and trade-offs among ES. Lessons learned from the 2 case studies are discussed in relation to environmental risk assessment and management of chemical mixtures. Integr Environ Assess Manag 2017;13:376-386. © 2016 SETAC. © 2016 SETAC.

Advantages offered by high average power picosecond lasers

NASA Astrophysics Data System (ADS)

Moorhouse, C.

2011-03-01

As electronic devices shrink in size to reduce material costs, device size and weight, thinner material thicknesses are also utilized. Feature sizes are also decreasing, which is pushing manufacturers towards single step laser direct write process as an attractive alternative to conventional, multiple step photolithography processes by eliminating process steps and the cost of chemicals. The fragile nature of these thin materials makes them difficult to machine either mechanically or with conventional nanosecond pulsewidth, Diode Pumped Solids State (DPSS) lasers. Picosecond laser pulses can cut materials with reduced damage regions and selectively remove thin films due to the reduced thermal effects of the shorter pulsewidth. Also, the high repetition rate allows high speed processing for industrial applications. Selective removal of thin films for OLED patterning, silicon solar cells and flat panel displays is discussed, as well as laser cutting of transparent materials with low melting point such as Polyethylene Terephthalate (PET). For many of these thin film applications, where low pulse energy and high repetition rate are required, throughput can be increased by the use of a novel technique to using multiple beams from a single laser source is outlined.

Rapid low-temperature epitaxial growth using a hot-element assisted chemical vapor deposition process

DOEpatents

Iwancizko, Eugene; Jones, Kim M.; Crandall, Richard S.; Nelson, Brent P.; Mahan, Archie Harvin

2001-01-01

The invention provides a process for depositing an epitaxial layer on a crystalline substrate, comprising the steps of providing a chamber having an element capable of heating, introducing the substrate into the chamber, heating the element at a temperature sufficient to decompose a source gas, passing the source gas in contact with the element; and forming an epitaxial layer on the substrate.

Advanced Ceramic Technology for Space Applications at NASA MSFC

NASA Technical Reports Server (NTRS)

Alim, Mohammad A.

2003-01-01

The ceramic processing technology using conventional methods is applied to the making of the state-of-the-art ceramics known as smart ceramics or intelligent ceramics or electroceramics. The sol-gel and wet chemical processing routes are excluded in this investigation considering economic aspect and proportionate benefit of the resulting product. The use of ceramic ingredients in making coatings or devices employing vacuum coating unit is also excluded in this investigation. Based on the present information it is anticipated that the conventional processing methods provide identical performing ceramics when compared to that processed by the chemical routes. This is possible when sintering temperature, heating and cooling ramps, peak temperature (sintering temperature), soak-time (hold-time), etc. are considered as variable parameters. In addition, optional calcination step prior to the sintering operation remains as a vital variable parameter. These variable parameters constitute a sintering profile to obtain a sintered product. Also it is possible to obtain identical products for more than one sintering profile attributing to the calcination step in conjunction with the variables of the sintering profile. Overall, the state-of-the-art ceramic technology is evaluated for potential thermal and electrical insulation coatings, microelectronics and integrated circuits, discrete and integrated devices, etc. applications in the space program.

Theoretical NMR correlations based Structure Discussion.

PubMed

Junker, Jochen

2011-07-28

The constitutional assignment of natural products by NMR spectroscopy is usually based on 2D NMR experiments like COSY, HSQC, and HMBC. The actual difficulty of the structure elucidation problem depends more on the type of the investigated molecule than on its size. The moment HMBC data is involved in the process or a large number of heteroatoms is present, a possibility of multiple solutions fitting the same data set exists. A structure elucidation software can be used to find such alternative constitutional assignments and help in the discussion in order to find the correct solution. But this is rarely done. This article describes the use of theoretical NMR correlation data in the structure elucidation process with WEBCOCON, not for the initial constitutional assignments, but to define how well a suggested molecule could have been described by NMR correlation data. The results of this analysis can be used to decide on further steps needed to assure the correctness of the structural assignment. As first step the analysis of the deviation of carbon chemical shifts is performed, comparing chemical shifts predicted for each possible solution with the experimental data. The application of this technique to three well known compounds is shown. Using NMR correlation data alone for the description of the constitutions is not always enough, even when including 13C chemical shift prediction.

Engineered soy oils for new value added applications

NASA Astrophysics Data System (ADS)

Tran, Phuong T.

Soybean oil is an abundant annually renewable resource. It is composed of triglycerides with long chain saturated and unsaturated fatty acids. The presence of unsaturated fatty acids allows for chemical modification to introduce new functionalities to soybean oil. A portfolio of chemically modified soy oil with suitable functional groups has been designed and engineered to serve as the starting material in applications such as polyamides, polyesters, polyurethanes, composites, and lubricants. Anhydride, hydroxyl, and silicone functionalities were introduced to soy oil. Anhydride functionality was introduced using a single-step free radical initiated process, and the chemically modified soy oils were evaluated for potential applications as a composite and lubricant. Hydroxyl functionalities were introduced in a single-step catalytic ozonolysis process recently developed in our labs, which proceeds rapidly and efficiently at room temperature without solvent. The transformed soy oil was used to successfully prepare bio-lubricants with good thermal/oxidative stability and bio-plastics such as polyamides, polyesters, and polyurethanes. A new class of organic-inorganic hybrid materials was prepared by curing vinyltrimethoxysilane functionalized soy oil. This hybrid material could have potential as biobased sealant through a moisture initiated room temperature cure. These new classes of soy-based materials are competitive both in cost and performance to petroleum based materials, but offer the advantage of being biobased.

Influence of coating steps of perovskite on low-temperature amorphous compact TiO x upon the morphology, crystallinity, and photovoltaic property correlation in planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Shahiduzzaman, Md.; Furumoto, Yoshikazu; Yamamoto, Kohei; Yonezawa, Kyosuke; Azuma, Yosuke; Kitamura, Michinori; Matsuzaki, Hiroyuki; Karakawa, Makoto; Kuwabara, Takayuki; Takahashi, Kohshin; Taima, Tetsuya

2018-03-01

The fabrication of high-efficiency solution-processable perovskite solar cells has been achieved using mesostructured films and compact titanium dioxide (TiO2) layers in a process that involves high temperatures and cost. Here, we present an efficient approach for fabricating chemical-bath-deposited, low-temperature, and low-cost amorphous compact TiO x -based planar heterojunction perovskite solar cells by one-step and two-step coatings of the perovskite layer. We also investigate the effect of the number of perovskite coating steps on the compact TiO x layer. The grazing incidence wide-angle X-ray scattering technique is used to clarify the relationship between morphology, crystallinity, and photovoltaic properties of the resulting devices. Analysis of the films revealed that one-step spin-coating of perovskite exhibited an enhancement of film quality and crystallization that correlates to photovoltaic performance 1.5 times higher than that of a two-step-coated device. Our findings show that the resulting morphology, crystallinity, and device performances are strongly dependent on the number of coating steps of the perovskite thin layer on the compact TiO x layer. This result is useful knowledge for the low-cost production of planar perovskite solar cells.

Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar

DOE PAGES

Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J.; ...

2016-02-09

Background: Strategies to improve copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment of hybrid poplar were investigated. These improvements included a combination of increasing hydrolysis yields, while simultaneously decreasing process inputs through (i) more efficient utilization of H 2O 2 and (ii) the addition of an alkaline extraction step prior to the metal-catalyzed AHP pretreatment. We hypothesized that utilizing this improved process could substantially lower the chemical inputs needed during pretreatment. Results: Hybrid poplar was pretreated utilizing a modified process in which an alkaline extraction step was incorporated prior to the Cu-AHP treatment step and H 2O 2 was added batch-wise overmore » the course of 10 h. Our results revealed that the alkaline pre-extraction step improved both lignin and xylan solubilization, which ultimately led to improved glucose (86 %) and xylose (95 %) yields following enzymatic hydrolysis. An increase in the lignin solubilization was also observed with fed-batch H 2O 2 addition relative to batch-only addition, which again resulted in increased glucose and xylose yields (77 and 93 % versus 63 and 74 %, respectively). Importantly, combining these strategies led to significantly improved sugar yields (96 % glucose and 94 % xylose) following enzymatic hydrolysis. In addition, we found that we could substantially lower the chemical inputs (enzyme, H 2O 2, and catalyst), while still maintaining high product yields utilizing the improved Cu-AHP process. This pretreatment also provided a relatively pure lignin stream consisting of ≥90 % Klason lignin and only 3 % xylan and 2 % ash following precipitation. Two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR and size-exclusion chromatography demonstrated that the solubilized lignin was high molecular weight (Mw ≈ 22,000 Da) and only slightly oxidized relative to lignin from untreated poplar. In conclusion: This study demonstrated that the fed-batch, two-stage Cu-AHP pretreatment process was effective in pretreating hybrid poplar for its conversion into fermentable sugars. Results showed sugar yields near the theoretical maximum were achieved from enzymatically hydrolyzed hybrid poplar by incorporating an alkaline extraction step prior to pretreatment and by efficiently utilizing H 2O 2 during the Cu-AHP process. Significantly, this study reports high sugar yields from woody biomass treated with an AHP pretreatment under mild reaction conditions.« less

Integration of Nine Steps into One Membrane Reactor To Produce Synthesis Gases for Ammonia and Liquid Fuel.

PubMed

Li, Wenping; Zhu, Xuefeng; Chen, Shuguang; Yang, Weishen

2016-07-18

The synthesis of ammonia and liquid fuel are two important chemical processes in which most of the energy is consumed in the production of H2 /N2 and H2 /CO synthesis gases from natural gas (methane). Here, we report a membrane reactor with a mixed ionic-electronic conducting membrane, in which the nine steps for the production of the two types of synthesis gases are shortened to one step by using water, air, and methane as feeds. In the membrane reactor, there is no direct CO2 emission and no CO or H2 S present in the ammonia synthesis gas. The energy consumption for the production of the two synthesis gases can be reduced by 63 % by using this membrane reactor. This promising membrane reactor process has been successfully demonstrated by experiment. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile fabrication of superhydrophobic surfaces from austenitic stainless steel (AISI 304) by chemical etching

NASA Astrophysics Data System (ADS)

Kim, Jae-Hun; Mirzaei, Ali; Kim, Hyoun Woo; Kim, Sang Sub

2018-05-01

Stainless steels are among the most common engineering materials and are used extensively in humid areas. Therefore, it is important that these materials must be robust to humidity and corrosion. This paper reports the fabrication of superhydrophobic surfaces from austenitic stainless steel (type AISI 304) using a facile two-step chemical etching method. In the first step, the stainless steel plates were etched in a HF solution, followed by a fluorination process, where they showed a water contact angle (WCA) of 166° and a sliding angle of 5° under the optimal conditions. To further enhance the superhydrophobicity, in the second step, they were dipped in a 0.1 wt.% NaCl solution at 100 °C, where the WCA was increased to 168° and the sliding angle was decreased to ∼2°. The long-term durability of the fabricated superhydrophobic samples for 1 month storage in air and water was investigated. The potential applicability of the fabricated samples was demonstrated by the excellent superhydrophobicity after 1 month. In addition, the self-cleaning properties of the fabricated superhydrophobic surface were also demonstrated. This paper outlines a facile, low-cost and scalable chemical etching method that can be adopted easily for large-scale purposes.

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-02-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

Optimization of a Sample Processing Protocol for Recovery of ...

EPA Pesticide Factsheets

Journal Article Following a release of Bacillus anthracis spores into the environment, there is a potential for lasting environmental contamination in soils. There is a need for detection protocols for B. anthracis in environmental matrices. However, identification of B. anthracis within a soil is a difficult task. Processing soil samples helps to remove debris, chemical components, and biological impurities that can interfere with microbiological detection. This study aimed to optimize a previously used indirect processing protocol, which included a series of washing and centrifugation steps.

Methanol from CO2 by organo-cocatalysis: CO2 capture and hydrogenation in one process step.

PubMed

Reller, Christian; Pöge, Matthias; Lißner, Andreas; Mertens, Florian O R L

2014-12-16

Carbon dioxide chemically bound to alcohol-amines was hydrogenated to methanol under retrieval of these industrially used CO2 capturing reagents. The energetics of the process can be seen as a partial cancellation of the exothermic heat of reaction of the hydrogenation with the endothermic one of the CO2 release from the capturing reagent. The process provides a means to significantly improve the energy efficiency of CO2 to methanol conversions.

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

NASA Technical Reports Server (NTRS)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Enantioselective Total Synthesis of (−)-Minovincine in Nine Chemical Steps: An Approach to Ketone Activation in Cascade Catalysis

PubMed Central

Laforteza, Brian N.; Pickworth, Mark

2014-01-01

More cycling–fewer steps The first enantioselective total synthesis of (−)-minovincine has been accomplished in nine chemical steps and 13% overall yield. A novel, one-step Diels–Alder/β-elimination/conjugate addition organocascade sequence allowed rapid access to the central tetracyclic core in an asymmetric manner. PMID:24000234

Direct writing of gold nanostructures with an electron beam: On the way to pure nanostructures by combining optimized deposition with oxygen-plasma treatment

PubMed Central

Belić, Domagoj; Shawrav, Mostafa M; Bertagnolli, Emmerich

2017-01-01

This work presents a highly effective approach for the chemical purification of directly written 2D and 3D gold nanostructures suitable for plasmonics, biomolecule immobilisation, and nanoelectronics. Gold nano- and microstructures can be fabricated by one-step direct-write lithography process using focused electron beam induced deposition (FEBID). Typically, as-deposited gold nanostructures suffer from a low Au content and unacceptably high carbon contamination. We show that the undesirable carbon contamination can be diminished using a two-step process – a combination of optimized deposition followed by appropriate postdeposition cleaning. Starting from the common metal-organic precursor Me2-Au-tfac, it is demonstrated that the Au content in pristine FEBID nanostructures can be increased from 30 atom % to as much as 72 atom %, depending on the sustained electron beam dose. As a second step, oxygen-plasma treatment is established to further enhance the Au content in the structures, while preserving their morphology to a high degree. This two-step process represents a simple, feasible and high-throughput method for direct writing of purer gold nanostructures that can enable their future use for demanding applications. PMID:29259868

IRIS Toxicological Review of Tetrahydrofuran (THF) ...

EPA Pesticide Factsheets

EPA is releasing the draft report, Toxicological Review of Tetrahydrofuran, that was distributed to Federal agencies and White House Offices for comment during the Science Discussion step of the IRIS Assessment Development Process. Comments received from other Federal agencies and White House Offices are provided below with external peer review panel comments. EPA is undertaking an Integrated Risk Information System (IRIS) health assessment for tetrahydrofuran. IRIS is an EPA database containing Agency scientific positions on potential adverse human health effects that may result from chronic (or lifetime) exposure to chemicals in the environment. IRIS contains chemical-specific summaries of qualitative and quantitative health information in support of two steps of the risk assessment paradigm, i.e., hazard identification and dose-response evaluation. IRIS assessments are used in combination with specific situational exposure assessment information to evaluate potential public health risk associated with environmental contaminants.

Recycle technology for recovering resources and products from waste printed circuit boards.

PubMed

Li, Jia; Lu, Hongzhou; Guo, Jie; Xu, Zhenming; Zhou, Yaohe

2007-03-15

The printed circuit board (PCB) contains nearly 28% metals that are abundant non-ferrous metals such as Cu, Al, Sn, etc. The purity of precious metals in PCBs is more than 10 times higher than that of rich-content minerals. Therefore, recycling of PCBs is an important subject not only from the treatment of waste but also from the recovery of valuable materials. Chemical and mechanical methods are two traditional recycling processes for waste PCBs. However, the prospect of chemical methods will be limited since the emission of toxic liquid or gas brings secondary pollution to the environment during the process. Mechanical processes, such as shape separation, jigging, density-based separation, and electrostatic separation have been widely utilized in the recycling industry. But, recycling of waste PCBs is only beginning. In this study, a total of 400 kg of waste PCBs was processed by a recycle technology without negative impact to the environment. The technology contained mechanical two-step crushing, corona electrostatic separating, and recovery. The results indicated that (i) two-step crushing was an effect process to strip metals from base plates completely; (ii) the size of particles between 0.6 and 1.2 mm was suitable for corona electrostatic separating during industrial application; and (iii) the nonmetal of waste PCBs attained 80% weight of a kind of nonmetallic plate that expanded the applying prospect of waste nonmetallic materials.

Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline–oxidative pretreatment of hybrid poplar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhalla, Aditya; Fasahati, Peyman; Particka, Chrislyn A.

2018-05-17

When applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H2O2) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significant loss inmore » sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified.« less

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films.

PubMed

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-09-29

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite crystalline phases and good ionic conductivity were developed during the second annealing step. These films showed properties comparable to those of thermally annealed films. This process is much faster than conventional annealing processes (e.g. halogen furnaces); a few seconds compared to tens of hours, respectively. The significance of this work includes the treatment of solid-state electrolyte oxides for SOFCs and the demonstration of the feasibility of other oxide components for solid-state energy devices.

Data Needs and Modeling of the Upper Atmosphere

NASA Astrophysics Data System (ADS)

Brunger, M. J.; Campbell, L.

2007-04-01

We present results from our enhanced statistical equilibrium and time-step codes for atmospheric modeling. In particular we use these results to illustrate the role of electron-driven processes in atmospheric phenomena and the sensitivity of the model results to data inputs such as integral cross sections, dissociative recombination rates and chemical reaction rates.

Construction and curation of a large ecotoxicological dataset for the EcoTTC

EPA Science Inventory

The Ecological Threshold for Toxicological Concern, or ecoTTC, has been proposed as a natural next step to the well-known human safety TTC concept. The ecoTTC is particularly suited for use as an early screening tool in the risk assessment process, in situations where chemical h...

Physical pretreatment – woody biomass size reduction – for forest biorefinery

Treesearch

J.Y. Zhu

2011-01-01

Physical pretreatment of woody biomass or wood size reduction is a prerequisite step for further chemical or biochemical processing in forest biorefinery. However, wood size reduction is very energy intensive which differentiates woody biomass from herbaceous biomass for biorefinery. This chapter discusses several critical issues related to wood size reduction: (1)...

COMMON ISSUES IN HUMAN AND ECOSYSTEM EXPOSURE ASSESSMENT: THE SIGNIFICANCE OF PARTITIONING, KINETICS, AND UPTAKE AT BIOLOGICAL EXCHANGE SURFACES

EPA Science Inventory

Exogenous chemicals enter organisms through critical surfaces in the lung, gills, gut, and skin. Transfer across these boundaries is the first step in characterizing the ratio of tissue dose to external exposure. Surface processes and fugacity are important elements of both human...

Substrate-Related Factors Affecting Enzymatic Saccharification of Lignocelluloses: Our Recent Understanding

Treesearch

Shao-Yuan Leu; J.Y. Zhu

2013-01-01

Enzymatic saccharification of cellulose is a key step in conversion of plant biomass to advanced biofuel and chemicals. Many substrate-related factors affect saccharification. Rather than examining the role of each individual factor on overall saccharification efficiency, this study examined how each factor affects the three basic processes of a heterogeneous...

Effect of chemical compounds on electronic tongue response to citrus juices

USDA-ARS?s Scientific Manuscript database

The electronic tongue system mimics the process of taste detection by human taste buds and recognition by the brain, hence helping in prediction of taste. With this unique capability, the electronic tongue has been used for taste detection of a wide range of food products. As a preliminary step in p...

Sweet sorghum biorefinery for production of fuel ethanol and value-added co-products

USDA-ARS?s Scientific Manuscript database

An integrated process has been developed for a sweet-sorghum biorefinery in which all carbohydrate components of the feedstock were used for production of fuel ethanol and industrial chemicals. In the first step, the juice was extracted from the stalks. The resulted straw (bagasse) then was pretreat...

Treatment of olive mill wastewater by chemical processes: effect of acid cracking pretreatment.

PubMed

Hande Gursoy-Haksevenler, B; Arslan-Alaton, Idil

2014-01-01

The effect of acid cracking (pH 2.0; T 70 °C) and filtration as a pretreatment step on the chemical treatability of olive mill wastewater (chemical oxygen demand (COD) 150,000 m/L; total organic carbon (TOC) 36,000 mg/L; oil-grease 8,200 mg/L; total phenols 3,800 mg/L) was investigated. FeCl3 coagulation, Ca(OH)2 precipitation, electrocoagulation using stainless steel electrodes and the Fenton's reagent were applied as chemical treatment methods. Removal performances were examined in terms of COD, TOC, oil-grease, total phenols, colour, suspended solids and acute toxicity with the photobacterium Vibrio fischeri. Significant oil-grease (95%) and suspended solids (96%) accompanied with 58% COD, 43% TOC, 39% total phenols and 80% colour removals were obtained by acid cracking-filtration pretreatment. Among the investigated chemical treatment processes, electrocoagulation and the Fenton's reagent were found more effective after pretreatment, especially in terms of total phenols removal. Total phenols removal increased from 39 to 72% when pretreatment was applied, while no significant additional (≈10-15%) COD and TOC removals were obtained when acid cracking was coupled with chemical treatment. The acute toxicity of the original olive mill wastewater sample increased considerably after pretreatment from 75 to 89% (measured for the 10-fold diluted wastewater sample). An operating cost analysis was also performed for the selected chemical treatment processes.

Fully solar-driven thermo- and electrochemistry for advanced oxidation processes (STEP-AOPs) of 2-nitrophenol wastewater.

PubMed

Nie, Chunhong; Shao, Nan; Wang, Baohui; Yuan, Dandan; Sui, Xin; Wu, Hongjun

2016-07-01

The STEP (Solar Thermal Electrochemical Process) for Advanced Oxidation Processes (AOPs, combined to STEP-AOPs), fully driven by solar energy without the input of any other forms of energy and chemicals, is introduced and demonstrated from the theory to experiments. Exemplified by the persistent organic pollutant 2-nitrophenol in water, the fundamental model and practical system are exhibited for the STEP-AOPs to efficiently transform 2-nitrophenol into carbon dioxide, water, and the other substances. The results show that the STEP-AOPs system performs more effectively than classical AOPs in terms of the thermodynamics and kinetics of pollutant oxidation. Due to the combination of solar thermochemical reactions with electrochemistry, the STEP-AOPs system allows the requisite electrolysis voltage of 2-nitrophenol to be experimentally decreased from 1.00 V to 0.84 V, and the response current increases from 18 mA to 40 mA. STEP-AOPs also greatly improve the kinetics of the oxidation at 30 °C and 80 °C. As a result, the removal rate of 2-nitrophenol after 1 h increased from 19.50% at 30 °C to 32.70% at 80 °C at constant 1.90 V. Mechanistic analysis reveals that the oxidation pathway is favorably changed because of thermal effects. The tracking of the reaction displayed that benzenediol and hydroquinone are initial products, with maleic acid and formic acid as sequential carboxylic acid products, and carbon dioxide as the final product. The theory and experiments on STEP-AOPs system exemplified by the oxidation of 2-nitrophenol provide a broad basis for extension of the STEP and AOPs for rapid and efficient treatment of organic wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fabrication of lightweight Si/SiC LIDAR mirrors

NASA Technical Reports Server (NTRS)

Goela, Jitendra S.; Taylor, Raymond L.

1991-01-01

A new, chemical vapor deposition (CVD) process was developed for fabricating lightweight, polycrystalline silicon/silicon-carbide (Si/SiC) mirrors. The process involves three CVD steps: (1) to produce the mirror faceplate; (2) to form the lightweight backstructure, which is deposited integral to the faceplate; and (3) to deposit a layer of optical-grade material, e.g., Si, onto the front surface of the faceplate. The mirror figure and finish are fabricated into the faceplate.

TSCA Work Plan: 2012 Scoring of Potential Candidate Chemicals Entering Step 2

EPA Pesticide Factsheets

In 2012, EPA scored these chemicals based on hazard, exposure and persistence/bioaccumulation criteria as part of Step 2 in the Work Plan methodology in order to identify candidate chemicals for near-term review and assessment under TSCA.

Multiscale Interfacial Strategy to Engineer Mixed Metal-Oxide Anodes toward Enhanced Cycling Efficiency.

PubMed

Ma, Yue; Tai, Cheuk-Wai; Li, Shaowen; Edström, Kristina; Wei, Bingqing

2018-06-13

Interconnected macro/mesoporous structures of mixed metal oxide (MMO) are developed on nickel foam as freestanding anodes for Li-ion batteries. The sustainable production is realized via a wet chemical etching process with bio-friendly chemicals. By means of divalent iron doping during an in situ recrystallization process, the as-developed MMO anodes exhibit enhanced levels of cycling efficiency. Furthermore, this atomic-scale modification coherently synergizes with the encapsulation layer across a micrometer scale. During this step, we develop a quasi-gel-state tri-copolymer, i.e., F127-resorcinol-melamine, as the N-doped carbon source to regulate the interfacial chemistry of the MMO electrodes. Electrochemical tests of the modified Fe x Ni 1- x O@NC-NiF anode in both half-cell and full-cell configurations unravel the favorable suppression of the irreversible capacity loss and satisfactory cyclability at the high rates. This study highlights a proof-of-concept modification strategy across multiple scales to govern the interfacial chemical process of the electrodes toward better reversibility.

Hazardous Chemicals on the Job: A Workers Guide to Reducing Exposure.

ERIC Educational Resources Information Center

Conrad, Fran; Kayman, Lindsey

This guide is intended to assist workers in reducing their exposure to hazardous chemicals on the job. It describes a systematic preventive approach to hazardous chemicals that is based on the following steps: determining which chemicals are in use at a particular worksite (techniques for asking the company and steps to take if the company is…

Coordinated Chemical and Isotopic Imaging of Bells (CM2) Meteorite Matrix

NASA Technical Reports Server (NTRS)

Clemett, S. J.; Messenger, S.; Naklamura-Messenger, K.; Thomas-Keprta, K. L.

2014-01-01

Meteoritic organic matter is a complex conglomeration of species formed in distinct environments and processes in circumstellar space, the interstellar medium, the Solar Nebula and asteroids. Consequently meteorites constitute a unique record of primordial organic chemical evolution. While bulk chemical analysis has provided a detailed description of the range and diversity of organic species present in carbonaceous chondrites, there is little information as to how these species are spatially distributed and their relationship to the host mineral matrix. The distribution of organic phases is nevertheless critical to understanding parent body processes. The CM and CI chondrites all display evidence of low temperature (< 350K) aqueous alteration that may have led to aqueous geochromatographic separation of organics and synthesis of new organics coupled to aqueous mineral alteration. Here we present the results of the first coordinated in situ isotopic and chemical mapping study of the Bells meteorite using a newly developed two-step laser mass spectrometer (mu-L(sup 2)MS) capable of measuring a broad range of organic compounds.

Rapid, chemical-free breaking of microfluidic emulsions with a hand-held antistatic gun

PubMed Central

Shahi, Payam; Abate, Adam R.

2017-01-01

Droplet microfluidics can form and process millions of picoliter droplets with speed and ease, allowing the execution of huge numbers of biological reactions for high-throughput studies. However, at the conclusion of most experiments, the emulsions must be broken to recover and analyze their contents. This is usually achieved with demulsifiers, like perfluorooctanol and chloroform, which can interfere with downstream reactions and harm cells. Here, we describe a simple approach to rapidly and efficiently break microfluidic emulsions, which requires no chemicals. Our method allows one-pot multi-step reactions, making it useful for large scale automated processing of reactions requiring demulsification. Using a hand-held antistatic gun, we pulse emulsions with the electric field, coalescing ∼100 μl of droplets in ∼10 s. We show that while emulsions broken with chemical demulsifiers exhibit potent PCR inhibition, the antistatic-broken emulsions amplify efficiently. The ability to break emulsions quickly without chemicals should make our approach valuable for most demulsification needs in microfluidics. PMID:28794817

Integrating Thermodynamic Models in Geodynamic Simulations: The Example of the Community Software ASPECT

NASA Astrophysics Data System (ADS)

Dannberg, J.; Heister, T.; Grove, R. R.; Gassmoeller, R.; Spiegelman, M. W.; Bangerth, W.

2017-12-01

Earth's surface shows many features whose genesis can only be understood through the interplay of geodynamic and thermodynamic models. This is particularly important in the context of melt generation and transport: Mantle convection determines the distribution of temperature and chemical composition, the melting process itself is then controlled by the thermodynamic relations and in turn influences the properties and the transport of melt. Here, we present our extension of the community geodynamics code ASPECT, which solves the equations of coupled magma/mantle dynamics, and allows to integrate different parametrizations of reactions and phase transitions: They may alternatively be implemented as simple analytical expressions, look-up tables, or computed by a thermodynamics software. As ASPECT uses a variety of numerical methods and solvers, this also gives us the opportunity to compare different approaches of modelling the melting process. In particular, we will elaborate on the spatial and temporal resolution that is required to accurately model phase transitions, and show the potential of adaptive mesh refinement when applied to melt generation and transport. We will assess the advantages and disadvantages of iterating between fluid dynamics and chemical reactions derived from thermodynamic models within each time step, or decoupling them, allowing for different time step sizes. Beyond that, we will expand on the functionality required for an interface between computational thermodynamics and fluid dynamics models from the geodynamics side. Finally, using a simple example of melting of a two-phase, two-component system, we compare different time-stepping and solver schemes in terms of accuracy and efficiency, in dependence of the time scales of fluid flow and chemical reactions relative to each other. Our software provides a framework to integrate thermodynamic models in high resolution, 3d simulations of coupled magma/mantle dynamics, and can be used as a tool to study links between physical processes and geochemical signals in the Earth.

Tequila production.

PubMed

Cedeño, M

1995-01-01

Tequila is obtained from the distillation of fermented juice of agave plant, Agave tequilana, to which up to 49% (w/v) of an adjunct sugar, mainly from cane or corn, could be added. Agave plants require from 8 to 12 years to mature and during all this time cleaning, pest control, and slacken of land are required to produce an initial raw material with the appropriate chemical composition for tequila production. Production process comprises four steps: cooking to hydrolyze inulin into fructose, milling to extract the sugars, fermentation with a strain of Saccharomyces cerevisiae to convert the sugars into ethanol and organoleptic compounds, and, finally, a two-step distillation process. Maturation, if needed, is carried out in white oak barrels to obtain rested or aged tequila in 2 or 12 months, respectively.

75 FR 14628 - Notice of Commission Decision

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-26

... complete, third recited step of claim 1, i.e., ``depositing a tungsten layer by chemical vapor deposition, said tungsten layer covering said glue layer on said dielectric and said exposed material.'' The... to the third step only includes the step of ``depositing a tungsten layer by chemical vapor...

Diffraction Techniques in Structural Biology

PubMed Central

Egli, Martin

2010-01-01

A detailed understanding of chemical and biological function and the mechanisms underlying the activities ultimately requires atomic-resolution structural data. Diffraction-based techniques such as single-crystal X-ray crystallography, electron microscopy and neutron diffraction are well established and have paved the road to the stunning successes of modern-day structural biology. The major advances achieved in the last 20 years in all aspects of structural research, including sample preparation, crystallization, the construction of synchrotron and spallation sources, phasing approaches and high-speed computing and visualization, now provide specialists and non-specialists alike with a steady flow of molecular images of unprecedented detail. The present chapter combines a general overview of diffraction methods with a step-by-step description of the process of a single-crystal X-ray structure determination experiment, from chemical synthesis or expression to phasing and refinement, analysis and quality control. For novices it may serve as a stepping-stone to more in-depth treatises of the individual topics. Readers relying on structural information for interpreting functional data may find it a useful consumer guide. PMID:20517991

Facile one-step construction of covalently networked, self-healable, and transparent superhydrophobic composite films

NASA Astrophysics Data System (ADS)

Lee, Yujin; You, Eun-Ah; Ha, Young-Geun

2018-07-01

Despite the considerable demand for bioinspired superhydrophobic surfaces with highly transparent, self-cleaning, and self-healable properties, a facile and scalable fabrication method for multifunctional superhydrophobic films with strong chemical networks has rarely been established. Here, we report a rationally designed facile one-step construction of covalently networked, transparent, self-cleaning, and self-healable superhydrophobic films via a one-step preparation and single-reaction process of multi-components. As coating materials for achieving the one-step fabrication of multifunctional superhydrophobic films, we included two different sizes of Al2O3 nanoparticles for hierarchical micro/nano dual-scale structures and transparent films, fluoroalkylsilane for both low surface energy and covalent binding functions, and aluminum nitrate for aluminum oxide networked films. On the basis of stability tests for the robust film composition, the optimized, covalently linked superhydrophobic composite films with a high water contact angle (>160°) and low sliding angle (<1°) showed excellent thermal stability (up to 400 °C), transparency (≈80%), self-healing, self-cleaning, and waterproof abilities. Therefore, the rationally designed, covalently networked superhydrophobic composite films, fabricated via a one-step solution-based process, can be further utilized for various optical and optoelectronic applications.

Neuronal differentiation of human mesenchymal stem cells in response to the domain size of graphene substrates.

PubMed

Lee, Yoo-Jung; Seo, Tae Hoon; Lee, Seula; Jang, Wonhee; Kim, Myung Jong; Sung, Jung-Suk

2018-01-01

Graphene is a noncytotoxic monolayer platform with unique physical, chemical, and biological properties. It has been demonstrated that graphene substrate may provide a promising biocompatible scaffold for stem cell therapy. Because chemical vapor deposited graphene has a two dimensional polycrystalline structure, it is important to control the individual domain size to obtain desirable properties for nano-material. However, the biological effects mediated by differences in domain size of graphene have not yet been reported. On the basis of the control of graphene domain achieved by one-step growth (1step-G, small domain) and two-step growth (2step-G, large domain) process, we found that the neuronal differentiation of bone marrow-derived human mesenchymal stem cells (hMSCs) highly depended on the graphene domain size. The defects at the domain boundaries in 1step-G graphene was higher (×8.5) and had a relatively low (13% lower) contact angle of water droplet than 2step-G graphene, leading to enhanced cell-substrate adhesion and upregulated neuronal differentiation of hMSCs. We confirmed that the strong interactions between cells and defects at the domain boundaries in 1step-G graphene can be obtained due to their relatively high surface energy, which is stronger than interactions between cells and graphene surfaces. Our results may provide valuable information on the development of graphene-based scaffold by understanding which properties of graphene domain influence cell adhesion efficacy and stem cell differentiation. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 43-51, 2018. © 2017 Wiley Periodicals, Inc.

Non-aqueous homogenous biocatalytic conversion of polysaccharides in ionic liquids using chemically modified glucosidase.

PubMed

Brogan, Alex P S; Bui-Le, Liem; Hallett, Jason P

2018-06-25

The increasing requirement to produce platform chemicals and fuels from renewable sources means advances in biocatalysis are rapidly becoming a necessity. Biomass is widely used in nature as a source of energy and as chemical building blocks. However, recalcitrance towards traditional chemical processes and solvents provides a significant barrier to widespread utility. Here, by optimizing enzyme solubility in ionic liquids, we have discovered solvent-induced substrate promiscuity of glucosidase, demonstrating an unprecedented example of homogeneous enzyme bioprocessing of cellulose. Specifically, chemical modification of glucosidase for solubilization in ionic liquids can increase thermal stability to up to 137 °C, allowing for enzymatic activity 30 times greater than is possible in aqueous media. These results establish that through a synergistic combination of chemical biology (enzyme modification) and reaction engineering (solvent choice), the biocatalytic capability of enzymes can be intensified: a key step towards the full-scale deployment of industrial biocatalysis.

Coupled thermal/chemical/mechanical modeling of energetic materials in ALE3D

NASA Technical Reports Server (NTRS)

Nichols, A. L.; Couch, R.; Maltby, J. D.; McCallen, R. C.; Otero, I.

1996-01-01

We must improve our ability to model the response of energetic materials to thermal stimuli and the processes involved in the energetic response. We have developed and used a time step option to efficiently and accurately compute the hours that the energetic material can take to react. Since on these longer film scales, materials can be expected to have significant motion, it is even more important to provide high-order advection for all components, including the chemical species. We show an example cook-off problem to illustrate these capabilities.

Influence of ageing on self-etch adhesives: one-step vs. two-step systems.

PubMed

Marchesi, Giulio; Frassetto, Andrea; Visintini, Erika; Diolosà, Marina; Turco, Gianluca; Salgarello, Stefano; Di Lenarda, Roberto; Cadenaro, Milena; Breschi, Lorenzo

2013-02-01

The aim of this study was to evaluate microtensile bond strength (μTBS) to dentine, interfacial nanoleakage expression, and stability after ageing, of two-step vs. one-step self-etch adhesives. Human molars were cut to expose middle/deep dentine, assigned to groups (n = 15), and treated with the following bonding systems: (i) Optibond XTR (a two-step self-etch adhesive; Kerr), (ii) Clearfil SE Bond (a two-step self-etch adhesive; Kuraray), (iii) Adper Easy Bond (a one-step self-etch adhesive; 3M ESPE), and (iv) Bond Force (a one-step self-etch adhesive; Tokuyama). Specimens were processed for μTBS testing after 24 h, 6 months, or 1 yr of storage in artificial saliva at 37°C. Nanoleakage expression was examined in similarly processed additional specimens. At baseline the μTBS results ranked in the following order: Adper Easy Bond = Optibond XTR ≥Clearfil SE = Bond Force, and interfacial nanoleakage analysis showed Clearfil SE Bond = Adper Easy Bond = Optibond XTR> Bond Force. After 1 yr of storage, Optibond XTR, Clearfil SE Bond, and Adper Easy Bond showed higher μTBS and lower interfacial nanoleakage expression compared with Bond Force. In conclusion, immediate bond strength, nanoleakage expression, and stability over time were not related to the number of steps of the bonding systems, but to their chemical formulations. © 2012 Eur J Oral Sci.

Cooking with Active Oxygen and Solid Alkali: A Promising Alternative Approach for Lignocellulosic Biorefineries.

PubMed

Jiang, Yetao; Zeng, Xianhai; Luque, Rafael; Tang, Xing; Sun, Yong; Lei, Tingzhou; Liu, Shijie; Lin, Lu

2017-10-23

Lignocellulosic biomass, a matrix of biopolymers including cellulose, hemicellulose, and lignin, has gathered increasing attention in recent years for the production of chemicals, fuels, and materials through biorefinery processes owing to its renewability and availability. The fractionation of lignocellulose is considered to be the fundamental step to establish an economical and sustainable lignocellulosic biorefinery. In this Minireview, we summarize a newly developed oxygen delignification for lignocellulose fractionation called cooking with active oxygen and solid alkali (CAOSA), which can fractionate lignocellulose into its constituents and maintain its processable form. In the CAOSA approach, environmentally friendly chemicals are applied instead of undesirable chemicals such as strong alkalis and sulfides. Notably, the alkali recovery for this process promises to be relatively simple and does not require causticizing or sintering. These features make the CAOSA process an alternative for both lignocellulose fractionation and biomass pretreatment. The advantages and challenges of CAOSA are also discussed to provide a comprehensive perspective with respect to existing strategies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ampoule Failure System

NASA Technical Reports Server (NTRS)

Watring, Dale A. (Inventor); Johnson, Martin L. (Inventor)

1996-01-01

An ampoule failure system for use in material processing furnaces comprising a containment cartridge and an ampoule failure sensor. The containment cartridge contains an ampoule of toxic material therein and is positioned within a furnace for processing. An ampoule failure probe is positioned in the containment cartridge adjacent the ampoule for detecting a potential harmful release of toxic material therefrom during processing. The failure probe is spaced a predetermined distance from the ampoule and is chemically chosen so as to undergo a timely chemical reaction with the toxic material upon the harmful release thereof. The ampoule failure system further comprises a data acquisition system which is positioned externally of the furnace and is electrically connected to the ampoule failure probe so as to form a communicating electrical circuit. The data acquisition system includes an automatic shutdown device for shutting down the furnace upon the harmful release of toxic material. It also includes a resistance measuring device for measuring the resistance of the failure probe during processing. The chemical reaction causes a step increase in resistance of the failure probe whereupon the automatic shutdown device will responsively shut down the furnace.

Effect of Phosphoric Acid Concentration on the Characteristics of Sugarcane Bagasse Activated Carbon

NASA Astrophysics Data System (ADS)

Adib, M. R. M.; Suraya, W. M. S. W.; Rafidah, H.; Amirza, A. R. M.; Attahirah, M. H. M. N.; Hani, M. S. N. Q.; Adnan, M. S.

2016-07-01

Impregnation method is one of the crucial steps involved in producing activated carbon using chemical activation process. Chemicals employed in this step is effective at decomposing the structure of material and forming micropores that helps in adsorption of contaminants. This paper explains thorough procedures that have been involved in producing sugarcane bagasse activated carbon (SBAC) by using 5%, 10%, 20%, 30% phosphoric acid (H3PO4) during the impregnation step. Concentration of H3PO4 used in the process of producing SBAC was optimized through several tests including bulk density, ash content, iodine adsorption and pore size diameter and the charactesristic of optimum SBAC produced has been compared with commercial activated carbon (CAC). Batch study has been carried out by using the SBAC produced from optimum condition to investigate the performance of SBAC in removal of turbidity and chemical oxygen demand (COD) from textile wastewater. From characteristic study, SBAC with 30% H3PO4 has shown the optimum value of bulk density, ash content, iodine adsorption and pore size diameter of 0.3023 g cm-3, 4.35%, 974.96 mg/g and 0.21-0.41 µm, respectively. These values are comparable to the characteristics of CAC. Experimental result from the batch study has been concluded that the SBAC has a promising potential in removing turbidity and COD of 75.5% and 66.3%, respectively which was a slightly lower than CAC which were able to remove 82.8% of turbidity and 70% of COD. As a conclusion, the SBAC is comparable with CAC in terms of their characteristics and the capability of removing contaminants from textile wastewater. Therefore, it has a commercial value to be used as an alternative of low-cost material in producing CAC.

LBNL: Secure Buildings

Science.gov Websites

Blue steps Blue steps Indoor Environment Department Advice for Safeguarding Buildings Against Chemical building operators. It contains our current advice for dealing with a biological or chemical release in a protecting buildings and occupants from chemical or biological attack. Click on the title bar, above, for

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Foam and gel methods for the decontamination of metallic surfaces

DOEpatents

Nunez, Luis; Kaminski, Michael Donald

2007-01-23

Decontamination of nuclear facilities is necessary to reduce the radiation field during normal operations and decommissioning of complex equipment. In this invention, we discuss gel and foam based diphosphonic acid (HEDPA) chemical solutions that are unique in that these solutions can be applied at room temperature; provide protection to the base metal for continued applications of the equipment; and reduce the final waste form production to one step. The HEDPA gels and foams are formulated with benign chemicals, including various solvents, such as ionic liquids and reducing and complexing agents such as hydroxamic acids, and formaldehyde sulfoxylate. Gel and foam based HEDPA processes allow for decontamination of difficult to reach surfaces that are unmanageable with traditional aqueous process methods. Also, the gel and foam components are optimized to maximize the dissolution rate and assist in the chemical transformation of the gel and foam to a stable waste form.

Comprehensive Chemical Fingerprinting of High-Quality Cocoa at Early Stages of Processing: Effectiveness of Combined Untargeted and Targeted Approaches for Classification and Discrimination.

PubMed

Magagna, Federico; Guglielmetti, Alessandro; Liberto, Erica; Reichenbach, Stephen E; Allegrucci, Elena; Gobino, Guido; Bicchi, Carlo; Cordero, Chiara

2017-08-02

This study investigates chemical information of volatile fractions of high-quality cocoa (Theobroma cacao L. Malvaceae) from different origins (Mexico, Ecuador, Venezuela, Columbia, Java, Trinidad, and Sao Tomè) produced for fine chocolate. This study explores the evolution of the entire pattern of volatiles in relation to cocoa processing (raw, roasted, steamed, and ground beans). Advanced chemical fingerprinting (e.g., combined untargeted and targeted fingerprinting) with comprehensive two-dimensional gas chromatography coupled with mass spectrometry allows advanced pattern recognition for classification, discrimination, and sensory-quality characterization. The entire data set is analyzed for 595 reliable two-dimensional peak regions, including 130 known analytes and 13 potent odorants. Multivariate analysis with unsupervised exploration (principal component analysis) and simple supervised discrimination methods (Fisher ratios and linear regression trees) reveal informative patterns of similarities and differences and identify characteristic compounds related to sample origin and manufacturing step.

Flow chemistry vs. flow analysis.

PubMed

Trojanowicz, Marek

2016-01-01

The flow mode of conducting chemical syntheses facilitates chemical processes through the use of on-line analytical monitoring of occurring reactions, the application of solid-supported reagents to minimize downstream processing and computerized control systems to perform multi-step sequences. They are exactly the same attributes as those of flow analysis, which has solid place in modern analytical chemistry in several last decades. The following review paper, based on 131 references to original papers as well as pre-selected reviews, presents basic aspects, selected instrumental achievements and developmental directions of a rapidly growing field of continuous flow chemical synthesis. Interestingly, many of them might be potentially employed in the development of new methods in flow analysis too. In this paper, examples of application of flow analytical measurements for on-line monitoring of flow syntheses have been indicated and perspectives for a wider application of real-time analytical measurements have been discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Environmental sampling and analysis in support of NTI-3

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGuire, R.R.; Harrar, J.E.; Haas, J.S.

1991-04-06

The third National Trail Inspection took place at the Monsanto Chemical Plant in Luling, Louisiana. In order to test the effectiveness of environmental sampling (soil, water and air) in determining the nature of the chemical process in a given production plant and to examine the distance from a process building that samples can effectively be taken, we needed to select some materials that constituted components of process streams. Three materials were selected: 1. isopropyl amine for air monitoring, 2. 4-nitrophenol, one of the precursors in the acetaminophen process, and 3. an intermediate in the production of glyphosate for ROUNDUP thatmore » is known simply as glyphosate intermediated. LLNL did not participate in the air sampling nor the analysis for isopropyl amine. This paper discussed the steps in this experiment including sample collection, sample workshop, sample analysis the results and discussion and the conclusion. 3 figs., 6 tabs.« less

High Fidelity Tape Transfer Printing Based On Chemically Induced Adhesive Strength Modulation

NASA Astrophysics Data System (ADS)

Sim, Kyoseung; Chen, Song; Li, Yuhang; Kammoun, Mejdi; Peng, Yun; Xu, Minwei; Gao, Yang; Song, Jizhou; Zhang, Yingchun; Ardebili, Haleh; Yu, Cunjiang

2015-11-01

Transfer printing, a two-step process (i.e. picking up and printing) for heterogeneous integration, has been widely exploited for the fabrication of functional electronics system. To ensure a reliable process, strong adhesion for picking up and weak or no adhesion for printing are required. However, it is challenging to meet the requirements of switchable stamp adhesion. Here we introduce a simple, high fidelity process, namely tape transfer printing(TTP), enabled by chemically induced dramatic modulation in tape adhesive strength. We describe the working mechanism of the adhesion modulation that governs this process and demonstrate the method by high fidelity tape transfer printing several types of materials and devices, including Si pellets arrays, photodetector arrays, and electromyography (EMG) sensors, from their preparation substrates to various alien substrates. High fidelity tape transfer printing of components onto curvilinear surfaces is also illustrated.

Purification process for vertically aligned carbon nanofibers

NASA Technical Reports Server (NTRS)

Nguyen, Cattien V.; Delziet, Lance; Matthews, Kristopher; Chen, Bin; Meyyappan, M.

2003-01-01

Individual, free-standing, vertically aligned multiwall carbon nanotubes or nanofibers are ideal for sensor and electrode applications. Our plasma-enhanced chemical vapor deposition techniques for producing free-standing and vertically aligned carbon nanofibers use catalyst particles at the tip of the fiber. Here we present a simple purification process for the removal of iron catalyst particles at the tip of vertically aligned carbon nanofibers derived by plasma-enhanced chemical vapor deposition. The first step involves thermal oxidation in air, at temperatures of 200-400 degrees C, resulting in the physical swelling of the iron particles from the formation of iron oxide. Subsequently, the complete removal of the iron oxide particles is achieved with diluted acid (12% HCl). The purification process appears to be very efficient at removing all of the iron catalyst particles. Electron microscopy images and Raman spectroscopy data indicate that the purification process does not damage the graphitic structure of the nanotubes.

An integrated process for the extraction of fuel and chemicals from marine macroalgal biomass

NASA Astrophysics Data System (ADS)

Trivedi, Nitin; Baghel, Ravi S.; Bothwell, John; Gupta, Vishal; Reddy, C. R. K.; Lali, Arvind M.; Jha, Bhavanath

2016-07-01

We describe an integrated process that can be applied to biomass of the green seaweed, Ulva fasciata, to allow the sequential recovery of four economically important fractions; mineral rich liquid extract (MRLE), lipid, ulvan, and cellulose. The main benefits of our process are: a) its simplicity and b) the consistent yields obtained from the residual biomass after each successive extraction step. For example, dry Ulva biomass yields ~26% of its starting mass as MRLE, ~3% as lipid, ~25% as ulvan, and ~11% as cellulose, with the enzymatic hydrolysis and fermentation of the final cellulose fraction under optimized conditions producing ethanol at a competitive 0.45 g/g reducing sugar. These yields are comparable to those obtained by direct processing of the individual components from primary biomass. We propose that this integration of ethanol production and chemical feedstock recovery from macroalgal biomass could substantially enhance the sustainability of marine biomass use.

Process for the combined removal of SO.sub.2 and NO.sub.x from flue gas

DOEpatents

Chang, Shih-Ger; Liu, David K.; Griffiths, Elizabeth A.; Littlejohn, David

1988-01-01

The present invention in one aspect relates to a process for the simultaneous removal of NO.sub.x and SO.sub.2 from a fluid stream comprising mixtures thereof and in another aspect relates to the separation, use and/or regeneration of various chemicals contaminated or spent in the process and which includes the steps of: (A) contacting the fluid stream at a temperature of between about 105.degree. and 180.degree. C. with a liquid aqueous slurry or solution comprising an effective amount of an iron chelate of an amino acid moiety having at least one --SH group; (B) separating the fluid stream from the particulates formed in step (A) comprising the chelate of the amino acid moiety and fly ash; (C) washing and separating the particulates of step (B) with an aqueous solution having a pH value of between about 5 to 8; (D) subsequently washing and separating the particulates of step (C) with a strongly acidic aqueous solution having a pH value of between about 1 to 3; (E) washing and separating the particulates of step (D) with an basic aqueous solution having a pH value of between about 9 to 12; (F) optionally adding additional amino acid moiety, iron (II) and alkali to the aqueous liquid from step (D) to produce an aqueous solution or slurry similar to that in step (A) having a pH value of between about 4 to 12; and (G) recycling the aqueous slurry of step (F) to the contacting zone of step (A). Steps (D) and (E) can be carried out in the reverse sequence, however the preferred order is (D) and then (E). In another preferred embodiment the present invention provides a process for the removal of NO.sub.x, SO.sub.2 and particulates from a fluid stream which includes the steps of (A) injecting into a reaction zone an aqueous solution itself comprising (i) an amino acid moiety selected from those described above; (ii) iron (II) ion; and (iii) an alkali, wherein the aqueous solution has a pH of between about 4 and 11; followed by solids separation and washing as is described in steps (B), (C), (D) and (E) above. The overall process is useful to reduce acid rain components from combustion gas sources.

Generalized binomial τ-leap method for biochemical kinetics incorporating both delay and intrinsic noise

NASA Astrophysics Data System (ADS)

Leier, André; Marquez-Lago, Tatiana T.; Burrage, Kevin

2008-05-01

The delay stochastic simulation algorithm (DSSA) by Barrio et al. [Plos Comput. Biol. 2, 117(E) (2006)] was developed to simulate delayed processes in cell biology in the presence of intrinsic noise, that is, when there are small-to-moderate numbers of certain key molecules present in a chemical reaction system. These delayed processes can faithfully represent complex interactions and mechanisms that imply a number of spatiotemporal processes often not explicitly modeled such as transcription and translation, basic in the modeling of cell signaling pathways. However, for systems with widely varying reaction rate constants or large numbers of molecules, the simulation time steps of both the stochastic simulation algorithm (SSA) and the DSSA can become very small causing considerable computational overheads. In order to overcome the limit of small step sizes, various τ-leap strategies have been suggested for improving computational performance of the SSA. In this paper, we present a binomial τ-DSSA method that extends the τ-leap idea to the delay setting and avoids drawing insufficient numbers of reactions, a common shortcoming of existing binomial τ-leap methods that becomes evident when dealing with complex chemical interactions. The resulting inaccuracies are most evident in the delayed case, even when considering reaction products as potential reactants within the same time step in which they are produced. Moreover, we extend the framework to account for multicellular systems with different degrees of intercellular communication. We apply these ideas to two important genetic regulatory models, namely, the hes1 gene, implicated as a molecular clock, and a Her1/Her 7 model for coupled oscillating cells.

One-step microwave plasma enhanced chemical vapor deposition (MW-PECVD) for transparent superhydrophobic surface

NASA Astrophysics Data System (ADS)

Thongrom, Sukrit; Tirawanichakul, Yutthana; Munsit, Nantakan; Deangngam, Chalongrat

2018-02-01

We demonstrate a rapid and environmental friendly fabrication technique to produce optically clear superhydrophobic surfaces using poly (dimethylsiloxane) (PDMS) as a sole coating material. The inert PDMS chain is transformed into a 3-D irregular solid network through microwave plasma enhanced chemical vapor deposition (MW-PECVD) process. Thanks to high electron density in the microwave-activated plasma, coating can be done in just a single step with rapid deposition rate, typically much shorter than 10 s. Deposited layers show excellent superhydrophobic properties with water contact angles of ∼170° and roll-off angles as small as ∼3°. The plasma-deposited films can be ultrathin with thicknesses under 400 nm, greatly diminishing the optical loss. Moreover, with appropriate coating conditions, the coating layer can even enhance the transmission over the entire visible spectrum due to a partial anti-reflection effect.

Exploding Nitromethane in Silico, in Real Time.

PubMed

Fileti, Eudes Eterno; Chaban, Vitaly V; Prezhdo, Oleg V

2014-10-02

Nitromethane (NM) is widely applied in chemical technology as a solvent for extraction, cleaning, and chemical synthesis. NM was considered safe for a long time, until a railroad tanker car exploded in 1958. We investigate the detonation kinetics and explosion reaction mechanisms in a variety of systems consisting of NM, molecular oxygen, and water vapor. Reactive molecular dynamics allows us to simulate reactions in time-domain, as they occur in real life. High polarity of the NM molecule is shown to play a key role, driving the first exothermic step of the reaction. Rapid temperature and pressure growth stimulate the subsequent reaction steps. Oxygen is important for faster oxidation, whereas its optimal concentration is in agreement with the proposed reaction mechanism. Addition of water (50 mol %) inhibits detonation; however, water does not prevent detonation entirely. The reported results provide important insights for improving applications of NM and preserving the safety of industrial processes.

Low Temperature Metal Free Growth of Graphene on Insulating Substrates by Plasma Assisted Chemical Vapor Deposition

PubMed Central

Muñoz, R.; Munuera, C.; Martínez, J. I.; Azpeitia, J.; Gómez-Aleixandre, C.; García-Hernández, M.

2016-01-01

Direct growth of graphene films on dielectric substrates (quartz and silica) is reported, by means of remote electron cyclotron resonance plasma assisted chemical vapor deposition r-(ECR-CVD) at low temperature (650°C). Using a two step deposition process- nucleation and growth- by changing the partial pressure of the gas precursors at constant temperature, mostly monolayer continuous films, with grain sizes up to 500 nm are grown, exhibiting transmittance larger than 92% and sheet resistance as low as 900 Ω·sq-1. The grain size and nucleation density of the resulting graphene sheets can be controlled varying the deposition time and pressure. In additon, first-principles DFT-based calculations have been carried out in order to rationalize the oxygen reduction in the quartz surface experimentally observed. This method is easily scalable and avoids damaging and expensive transfer steps of graphene films, improving compatibility with current fabrication technologies. PMID:28070341

Biodiesel from dewatered wastewater sludge: a two-step process for a more advantageous production.

PubMed

Pastore, Carlo; Lopez, Antonio; Lotito, Vincenzo; Mascolo, Giuseppe

2013-07-01

Alternative approaches for obtaining biodiesel from municipal sludge have been successfully investigated. In order to avoid the expensive conventional preliminary step of sludge drying, dewatered sludge (TSS: 15wt%) was used as starting material. The best performance in terms of yield of fatty acid methyl esters (18wt%) with the lowest energy demand (17MJkgFAME(-1)) was obtained by a new two-step approach based on hexane extraction carried out directly on dewatered acidified (H2SO4) sludge followed by methanolysis of extracted lipids. It was found that sulphuric acid plays a key role in the whole process not only for the transesterification of glycerides but also for the production of new free fatty acids from soaps and their esterification with methanol. In addition to biodiesel production, the investigated process allows valorization of primary sludge as it turns it into a valuable source of chemicals, namely sterols (2.5wt%), aliphatic alcohols (0.8wt%) and waxes (2.3wt%). Copyright © 2013 Elsevier Ltd. All rights reserved.

Operator Approach to the Master Equation for the One-Step Process

NASA Astrophysics Data System (ADS)

Hnatič, M.; Eferina, E. G.; Korolkova, A. V.; Kulyabov, D. S.; Sevastyanov, L. A.

2016-02-01

Background. Presentation of the probability as an intrinsic property of the nature leads researchers to switch from deterministic to stochastic description of the phenomena. The kinetics of the interaction has recently attracted attention because it often occurs in the physical, chemical, technical, biological, environmental, economic, and sociological systems. However, there are no general methods for the direct study of this equation. The expansion of the equation in a formal Taylor series (the so called Kramers-Moyal's expansion) is used in the procedure of stochastization of one-step processes. Purpose. However, this does not eliminate the need for the study of the master equation. Method. It is proposed to use quantum field perturbation theory for the statistical systems (the so-called Doi method). Results: This work is a methodological material that describes the principles of master equation solution based on quantum field perturbation theory methods. The characteristic property of the work is that it is intelligible for non-specialists in quantum field theory. Conclusions: We show the full equivalence of the operator and combinatorial methods of obtaining and study of the one-step process master equation.

Waste to chemicals for a circular economy.

PubMed

Iaquaniello, Gaetano; Centi, Gabriele; Annarita Salladini, Annarita; Palo, Emma; Perathoner, Siglinda

2018-06-25

The implementation of a circular economy is a fundamental step to create a greater and more sustainable future for a better use of resources and energy. Wastes and in particular municipal solid waste represent an untapped source of carbon (and hydrogen) to produce a large range of chemicals from methane to alcohols (as methanol or ethanol) or urea. The waste to chemical (WtC) process and related economics are assessed in this concept article to show the validity of such solution both from an economic point of view and from an environmental perspective considering the sensible reduction in greenhouse gas emissions with respect to conventional production from fossil fuels. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the surface morphology of aluminium doped zinc oxide thin films by arrayed nanorods through chemical growth process

NASA Astrophysics Data System (ADS)

Devasia, Sebin; Anila, E. I.

2018-04-01

Here we report the growth and characterization of chemically grown aluminium doped zinc oxide nanorods on seed layers. The seed layers were prepared by chemical spray pyrolysis which acted as the growth centers. The growth duration of nanorods were varied from 3h to 12h in steps of 3h. Further, investigations on their structural, morphological, electrical and optical properties. The SEM images confirmed the hexagonal shaped nanorod arrays grown on the seed layers. Later, the x-ray diffraction measurements revealed the pure zinc oxide phase of the samples. Photoluminescence and photoconductivity studies were carried out to analyze the potential of its optoelectronic properties.

Physics-based signal processing algorithms for micromachined cantilever arrays

DOEpatents

Candy, James V; Clague, David S; Lee, Christopher L; Rudd, Robert E; Burnham, Alan K; Tringe, Joseph W

2013-11-19

A method of using physics-based signal processing algorithms for micromachined cantilever arrays. The methods utilize deflection of a micromachined cantilever that represents the chemical, biological, or physical element being detected. One embodiment of the method comprises the steps of modeling the deflection of the micromachined cantilever producing a deflection model, sensing the deflection of the micromachined cantilever and producing a signal representing the deflection, and comparing the signal representing the deflection with the deflection model.

Removal of Aromatic Pollutant Surrogate from Water by Recyclable Magnetite-Activated Carbon Nanocomposite: An Experiment for General Chemistry

ERIC Educational Resources Information Center

Furlan, Ping Y.; Melcer, Michael E.

2014-01-01

A general chemistry laboratory experiment using readily available chemicals is described to introduce college students to an exciting class of nanocomposite materials. In a one-step room temperature synthetic process, magnetite nanoparticles are embedded onto activated carbon matrix. The resultant nanocomposite has been shown to combine the…

Reduced Order Models for Reactions of Energetic Materials

NASA Astrophysics Data System (ADS)

Kober, Edward

The formulation of reduced order models for the reaction chemistry of energetic materials under high pressures is needed for the development of mesoscale models in the areas of initiation, deflagration and detonation. Phenomenologically, 4-8 step models have been formulated from the analysis of cook-off data by analyzing the temperature rise of heated samples. Reactive molecular dynamics simulations have been used to simulate many of these processes, but reducing the results of those simulations to simple models has not been achieved. Typically, these efforts have focused on identifying molecular species and detailing specific chemical reactions. An alternative approach is presented here that is based on identifying the coordination geometries of each atom in the simulation and tracking classes of reactions by correlated changes in these geometries. Here, every atom and type of reaction is documented for every time step; no information is lost from unsuccessful molecular identification. Principal Component Analysis methods can then be used to map out the effective chemical reaction steps. For HMX and TATB decompositions simulated with ReaxFF, 90% of the data can be explained by 4-6 steps, generating models similar to those from the cook-off analysis. By performing these simulations at a variety of temperatures and pressures, both the activation and reaction energies and volumes can then be extracted.

Impact of different post-harvest processing methods on the chemical compositions of peony root.

PubMed

Zhu, Shu; Shirakawa, Aimi; Shi, Yanhong; Yu, Xiaoli; Tamura, Takayuki; Shibahara, Naotoshi; Yoshimatsu, Kayo; Komatsu, Katsuko

2018-06-01

The impact of key processing steps such as boiling, peeling, drying and storing on chemical compositions and morphologic features of the produced peony root was investigated in detail by applying 15 processing methods to fresh roots of Paeonia lactiflora and then monitoring contents of eight main components, as well as internal root color. The results showed that low temperature (4 °C) storage of fresh roots for approximately 1 month after harvest resulted in slightly increased and stable content of paeoniflorin, which might be due to suppression of enzymatic degradation. This storage also prevented roots from discoloring, facilitating production of favorable bright color roots. Boiling process triggered decomposition of polygalloylglucoses, thereby leading to a significant increase in contents of pentagalloylglucose and gallic acid. Peeling process resulted in a decrease of albiflorin and catechin contents. As a result, an optimized and practicable processing method ensuring high contents of the main active components in the produced root was developed.

Environmental and risk screening for prioritizing pollution prevention opportunities in the U.S. printed wiring board manufacturing industry.

PubMed

Lam, Carl W; Lim, Seong-Rin; Schoenung, Julie M

2011-05-15

Modern manufacturing of printed wiring boards (PWBs) involves extensive use of various hazardous chemicals in different manufacturing steps such as board preparation, circuit design transfer, etching and plating processes. Two complementary environmental screening methods developed by the U.S. EPA, namely: (i) the Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts (TRACI) and (ii) Risk-Screening Environmental Indicators (RSEI), are used to quantify geographic and chemical environmental impacts in the U.S. PWB manufacturing industry based on Toxics Release Inventory (TRI) data. Although the release weight percentages of industrial chemicals such as methanol, glycol ethers and dimethylformamide comprise the larger fraction of reported air and water emissions, results indicate that lead, copper and their compounds' releases correspond to the highest environmental impact from toxicity potentials and risk-screening scores. Combining these results with further knowledge of PWB manufacturing, select alternative chemical processes and materials for pollution prevention are discussed. Examples of effective pollution prevention options in the PWB industry include spent etchant recovery technologies, and process and material substitutions. In addition, geographic assessment of environmental burden highlights states where promotion of pollution prevention strategies and emissions regulations can have the greatest effect to curb the PWB industry's toxic release impacts. Copyright © 2011 Elsevier B.V. All rights reserved.

A 3D numerical study of LO2/GH2 supercritical combustion in the ONERA-Mascotte Test-rig configuration

NASA Astrophysics Data System (ADS)

Benmansour, Abdelkrim; Liazid, Abdelkrim; Logerais, Pierre-Olivier; Durastanti, Jean-Félix

2016-02-01

Cryogenic propellants LOx/H2 are used at very high pressure in rocket engine combustion. The description of the combustion process in such application is very complex due essentially to the supercritical regime. Ideal gas law becomes invalid. In order to try to capture the average characteristics of this combustion process, numerical computations are performed using a model based on a one-phase multi-component approach. Such work requires fluid properties and a correct definition of the mixture behavior generally described by cubic equations of state with appropriated thermodynamic relations validated against the NIST data. In this study we consider an alternative way to get the effect of real gas by testing the volume-weighted-mixing-law with association of the component transport properties using directly the NIST library data fitting including the supercritical regime range. The numerical simulations are carried out using 3D RANS approach associated with two tested turbulence models, the standard k-Epsilon model and the realizable k-Epsilon one. The combustion model is also associated with two chemical reaction mechanisms. The first one is a one-step generic chemical reaction and the second one is a two-step chemical reaction. The obtained results like temperature profiles, recirculation zones, visible flame lengths and distributions of OH species are discussed.

Surface Modification of Ti-35Nb-10Ta-1.5Fe by the Double Acid-Etching Process

PubMed Central

Amigó, Angélica

2018-01-01

Surface topography and composition influence the osteoblastic proliferation and osseointegration rates, which favor the biomechanical stability of bone anchoring and implants. In recent years, beta titanium alloys have been developed, and are composed of biocompatible elements, have low elastic modulus, high corrosion resistance, and mechanical properties to improve the long performance behavior of biomaterials. In the present research, the influence of the acid-etching process was studied in Ti6Al4V ELI and Ti35Nb10Ta1.5Fe. Samples were etched in a two-step acid treatment. Surface roughness parameters were quantified under a confocal microscope, topography was studied by scanning electron microscopy, and surface composition was analyzed with energy dispersive X-ray spectroscopy. The results revealed that the two-step acid treatment changes the topography of the β alloy, increases the surface area, and changes the chemical composition of the surface. Two differentiated regions were identified in the Ti35Nb10Ta1.5Fe alloy after the acid-etching process: The α + β region with higher values of mean roughness due to the lower chemical resistance of this region; and the β region with lower values of roughness parameters. PMID:29587427

ExcelAutomat: a tool for systematic processing of files as applied to quantum chemical calculations

NASA Astrophysics Data System (ADS)

Laloo, Jalal Z. A.; Laloo, Nassirah; Rhyman, Lydia; Ramasami, Ponnadurai

2017-07-01

The processing of the input and output files of quantum chemical calculations often necessitates a spreadsheet as a key component of the workflow. Spreadsheet packages with a built-in programming language editor can automate the steps involved and thus provide a direct link between processing files and the spreadsheet. This helps to reduce user-interventions as well as the need to switch between different programs to carry out each step. The ExcelAutomat tool is the implementation of this method in Microsoft Excel (MS Excel) using the default Visual Basic for Application (VBA) programming language. The code in ExcelAutomat was adapted to work with the platform-independent open-source LibreOffice Calc, which also supports VBA. ExcelAutomat provides an interface through the spreadsheet to automate repetitive tasks such as merging input files, splitting, parsing and compiling data from output files, and generation of unique filenames. Selected extracted parameters can be retrieved as variables which can be included in custom codes for a tailored approach. ExcelAutomat works with Gaussian files and is adapted for use with other computational packages including the non-commercial GAMESS. ExcelAutomat is available as a downloadable MS Excel workbook or as a LibreOffice workbook.

Framework for the quality assurance of 'omics technologies considering GLP requirements.

PubMed

Kauffmann, Hans-Martin; Kamp, Hennicke; Fuchs, Regine; Chorley, Brian N; Deferme, Lize; Ebbels, Timothy; Hackermüller, Jörg; Perdichizzi, Stefania; Poole, Alan; Sauer, Ursula G; Tollefsen, Knut E; Tralau, Tewes; Yauk, Carole; van Ravenzwaay, Ben

2017-12-01

'Omics technologies are gaining importance to support regulatory toxicity studies. Prerequisites for performing 'omics studies considering GLP principles were discussed at the European Centre for Ecotoxicology and Toxicology of Chemicals (ECETOC) Workshop Applying 'omics technologies in Chemical Risk Assessment. A GLP environment comprises a standard operating procedure system, proper pre-planning and documentation, and inspections of independent quality assurance staff. To prevent uncontrolled data changes, the raw data obtained in the respective 'omics data recording systems have to be specifically defined. Further requirements include transparent and reproducible data processing steps, and safe data storage and archiving procedures. The software for data recording and processing should be validated, and data changes should be traceable or disabled. GLP-compliant quality assurance of 'omics technologies appears feasible for many GLP requirements. However, challenges include (i) defining, storing, and archiving the raw data; (ii) transparent descriptions of data processing steps; (iii) software validation; and (iv) ensuring complete reproducibility of final results with respect to raw data. Nevertheless, 'omics studies can be supported by quality measures (e.g., GLP principles) to ensure quality control, reproducibility and traceability of experiments. This enables regulators to use 'omics data in a fit-for-purpose context, which enhances their applicability for risk assessment. Copyright © 2017 Elsevier Inc. All rights reserved.

ExcelAutomat: a tool for systematic processing of files as applied to quantum chemical calculations.

PubMed

Laloo, Jalal Z A; Laloo, Nassirah; Rhyman, Lydia; Ramasami, Ponnadurai

2017-07-01

The processing of the input and output files of quantum chemical calculations often necessitates a spreadsheet as a key component of the workflow. Spreadsheet packages with a built-in programming language editor can automate the steps involved and thus provide a direct link between processing files and the spreadsheet. This helps to reduce user-interventions as well as the need to switch between different programs to carry out each step. The ExcelAutomat tool is the implementation of this method in Microsoft Excel (MS Excel) using the default Visual Basic for Application (VBA) programming language. The code in ExcelAutomat was adapted to work with the platform-independent open-source LibreOffice Calc, which also supports VBA. ExcelAutomat provides an interface through the spreadsheet to automate repetitive tasks such as merging input files, splitting, parsing and compiling data from output files, and generation of unique filenames. Selected extracted parameters can be retrieved as variables which can be included in custom codes for a tailored approach. ExcelAutomat works with Gaussian files and is adapted for use with other computational packages including the non-commercial GAMESS. ExcelAutomat is available as a downloadable MS Excel workbook or as a LibreOffice workbook.

Biosynthesis of cis,cis-muconic acid and its aromatic precursors, catechol and protocatechuic acid, from renewable feedstocks by Saccharomyces cerevisiae.

PubMed

Weber, Christian; Brückner, Christine; Weinreb, Sheila; Lehr, Claudia; Essl, Christine; Boles, Eckhard

2012-12-01

Adipic acid is a high-value compound used primarily as a precursor for the synthesis of nylon, coatings, and plastics. Today it is produced mainly in chemical processes from petrochemicals like benzene. Because of the strong environmental impact of the production processes and the dependence on fossil resources, biotechnological production processes would provide an interesting alternative. Here we describe the first engineered Saccharomyces cerevisiae strain expressing a heterologous biosynthetic pathway converting the intermediate 3-dehydroshikimate of the aromatic amino acid biosynthesis pathway via protocatechuic acid and catechol into cis,cis-muconic acid, which can be chemically dehydrogenated to adipic acid. The pathway consists of three heterologous microbial enzymes, 3-dehydroshikimate dehydratase, protocatechuic acid decarboxylase composed of three different subunits, and catechol 1,2-dioxygenase. For each heterologous reaction step, we analyzed several potential candidates for their expression and activity in yeast to compose a functional cis,cis-muconic acid synthesis pathway. Carbon flow into the heterologous pathway was optimized by increasing the flux through selected steps of the common aromatic amino acid biosynthesis pathway and by blocking the conversion of 3-dehydroshikimate into shikimate. The recombinant yeast cells finally produced about 1.56 mg/liter cis,cis-muconic acid.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osmanlioglu, Ahmet Erdal

Pre-treatment of radioactive waste is the first step in waste management program that occurs after waste generation from various applications in Turkey. Pre-treatment and characterization practices are carried out in Radioactive Waste Management Unit (RWMU) at Cekmece Nuclear Research and Training Center (CNRTC) in Istanbul. This facility has been assigned to take all low-level radioactive wastes generated by nuclear applications in Turkey. The wastes are generated from research and nuclear applications mainly in medicine, biology, agriculture, quality control in metal processing and construction industries. These wastes are classified as low- level radioactive wastes. Pre-treatment practices cover several steps. In thismore » paper, main steps of pre-treatment and characterization are presented. Basically these are; collection, segregation, chemical adjustment, size reduction and decontamination operations. (author)« less

Membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

PubMed

Rivero, M J; Parsons, S A; Jeffrey, P; Pidou, M; Jefferson, B

2006-01-01

Urban water recycling is now becoming an important issue where water resources are becoming scarce. This paper looks at reusing grey water; the preference is treatment processes based on biological systems to remove the dissolved organic content. Here, an alternative process, photocatalysis is discussed as it is an attractive technology that could be well-suited for treating the recalcitrant organic compounds found in grey water. The photocatalytic process oxidises organic reactants at a catalyst surface in the presence of ultraviolet light. Given enough exposure time, organic compounds will be oxidized into CO2 and water. The best contact is achieved in a slurry reactor but a second step to separate and recover the catalyst is need. This paper discusses a new membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

Beyond Solar Fuels: Renewable Energy-Driven Chemistry.

PubMed

Lanzafame, Paola; Abate, Salvatare; Ampelli, Claudio; Genovese, Chiara; Passalacqua, Rosalba; Centi, Gabriele; Perathoner, Siglinda

2017-11-23

The future feasibility of decarbonized industrial chemical production based on the substitution of fossil feedstocks (FFs) with renewable energy (RE) sources is discussed. Indeed, the use of FFs as an energy source has the greatest impact on the greenhouse gas emissions of chemical production. This future scenario is indicated as "solar-driven" or "RE-driven" chemistry. Its possible implementation requires to go beyond the concept of solar fuels, in particular to address two key aspects: i) the use of RE-driven processes for the production of base raw materials, such as olefins, methanol, and ammonia, and ii) the development of novel RE-driven routes that simultaneously realize process and energy intensification, particularly in the direction of a significant reduction of the number of the process steps. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silicon Chemical Vapor Deposition Process Using a Half-Inch Silicon Wafer for Minimal Manufacturing System

NASA Astrophysics Data System (ADS)

Li, Ning; Habuka, Hitoshi; Ikeda, Shin-ichi; Hara, Shiro

A chemical vapor deposition reactor for producing thin silicon films was designed and developed for achieving a new electronic device production system, the Minimal Manufacturing, using a half-inch wafer. This system requires a rapid process by a small footprint reactor. This was designed and verified by employing the technical issues, such as (i) vertical gas flow, (ii) thermal operation using a highly concentrated infrared flux, and (iii) reactor cleaning by chlorine trifluoride gas. The combination of (i) and (ii) could achieve a low heating power and a fast cooling designed by the heat balance of the small wafer placed at a position outside of the reflector. The cleaning process could be rapid by (iii). The heating step could be skipped because chlorine trifluoride gas was reactive at any temperature higher than room temperature.

Self-assembly of Nano-rods in Photosensitive Phase Separation

NASA Astrophysics Data System (ADS)

Liu, Ya; Kuksenok, Olga; Maresov, Egor; Balazs, Anna

2012-02-01

Computer simulations reveal how photo-induced chemical reactions in polymeric mixtures can be exploited to create long-range order in materials whose features range from the sub-micron to the nanoscale. The process is initiated by shining a spatially uniform light on a photosensitive AB binary blend, which thereby undergoes both a reversible chemical reaction and phase separation. When a well-collimated, higher intensity light is rastered over the sample, the system forms defect-free, spatially periodic structures. We now build on this approach by introducing nanorods that have a preferential affinity for one the phases in a binary mixture. By rastering over the sample with the higher intensity light, we can create ordered arrays of rods within periodically ordered materials in essentially one processing step.

Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Tai, Lixuan; Zhu, Daming; Liu, Xing; Yang, Tieying; Wang, Lei; Wang, Rui; Jiang, Sheng; Chen, Zhenhua; Xu, Zhongmin; Li, Xiaolong

2018-06-01

The metal-free synthesis of graphene on single-crystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed, single-crystal silicon substrate using metal-free, ambient-pressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates. [Figure not available: see fulltext.

Steps Towards Industrialization of Cu–III–VI2Thin‐Film Solar Cells:Linking Materials/Device Designs to Process Design For Non‐stoichiometric Photovoltaic Materials

PubMed Central

Chang, Hsueh‐Hsin; Sharma, Poonam; Letha, Arya Jagadhamma; Shao, Lexi; Zhang, Yafei; Tseng, Bae‐Heng

2016-01-01

The concept of in‐line sputtering and selenization become industrial standard for Cu–III–VI2 solar cell fabrication, but still it's very difficult to control and predict the optical and electrical parameters, which are closely related to the chemical composition distribution of the thin film. The present review article addresses onto the material design, device design and process design using parameters closely related to the chemical compositions. Its variation leads to change in the Poisson equation, current equation, and continuity equation governing the device design. To make the device design much realistic and meaningful, we need to build a model that relates the opto‐electrical properties to the chemical composition. The material parameters as well as device structural parameters are loaded into the process simulation to give a complete set of process control parameters. The neutral defect concentrations of non‐stoichiometric CuMSe2 (M = In and Ga) have been calculated under the specific atomic chemical potential conditions using this methodology. The optical and electrical properties have also been investigated for the development of a full‐function analytical solar cell simulator. The future prospects regarding the development of copper–indium–gallium–selenide thin film solar cells have also been discussed. PMID:27840790

Steps Towards Industrialization of Cu-III-VI2Thin-Film Solar Cells:Linking Materials/Device Designs to Process Design For Non-stoichiometric Photovoltaic Materials.

PubMed

Hwang, Huey-Liang; Chang, Hsueh-Hsin; Sharma, Poonam; Letha, Arya Jagadhamma; Shao, Lexi; Zhang, Yafei; Tseng, Bae-Heng

2016-10-01

The concept of in-line sputtering and selenization become industrial standard for Cu-III-VI 2 solar cell fabrication, but still it's very difficult to control and predict the optical and electrical parameters, which are closely related to the chemical composition distribution of the thin film. The present review article addresses onto the material design, device design and process design using parameters closely related to the chemical compositions. Its variation leads to change in the Poisson equation, current equation, and continuity equation governing the device design. To make the device design much realistic and meaningful, we need to build a model that relates the opto-electrical properties to the chemical composition. The material parameters as well as device structural parameters are loaded into the process simulation to give a complete set of process control parameters. The neutral defect concentrations of non-stoichiometric CuMSe 2 (M = In and Ga) have been calculated under the specific atomic chemical potential conditions using this methodology. The optical and electrical properties have also been investigated for the development of a full-function analytical solar cell simulator. The future prospects regarding the development of copper-indium-gallium-selenide thin film solar cells have also been discussed.

Demand driven salt clean-up in a molten salt fast reactor - Defining a priority list.

PubMed

Merk, B; Litskevich, D; Gregg, R; Mount, A R

2018-01-01

The PUREX technology based on aqueous processes is currently the leading reprocessing technology in nuclear energy systems. It seems to be the most developed and established process for light water reactor fuel and the use of solid fuel. However, demand driven development of the nuclear system opens the way to liquid fuelled reactors, and disruptive technology development through the application of an integrated fuel cycle with a direct link to reactor operation. The possibilities of this new concept for innovative reprocessing technology development are analysed, the boundary conditions are discussed, and the economic as well as the neutron physical optimization parameters of the process are elucidated. Reactor physical knowledge of the influence of different elements on the neutron economy of the reactor is required. Using an innovative study approach, an element priority list for the salt clean-up is developed, which indicates that separation of Neodymium and Caesium is desirable, as they contribute almost 50% to the loss of criticality. Separating Zirconium and Samarium in addition from the fuel salt would remove nearly 80% of the loss of criticality due to fission products. The theoretical study is followed by a qualitative discussion of the different, demand driven optimization strategies which could satisfy the conflicting interests of sustainable reactor operation, efficient chemical processing for the salt clean-up, and the related economic as well as chemical engineering consequences. A new, innovative approach of balancing the throughput through salt processing based on a low number of separation process steps is developed. Next steps for the development of an economically viable salt clean-up process are identified.

Theoretical study of gas hydrate decomposition kinetics--model development.

PubMed

Windmeier, Christoph; Oellrich, Lothar R

2013-10-10

In order to provide an estimate of the order of magnitude of intrinsic gas hydrate dissolution and dissociation kinetics, the "Consecutive Desorption and Melting Model" (CDM) is developed by applying only theoretical considerations. The process of gas hydrate decomposition is assumed to comprise two consecutive and repetitive quasi chemical reaction steps. These are desorption of the guest molecule followed by local solid body melting. The individual kinetic steps are modeled according to the "Statistical Rate Theory of Interfacial Transport" and the Wilson-Frenkel approach. All missing required model parameters are directly linked to geometric considerations and a thermodynamic gas hydrate equilibrium model.

An integrated one-step system to extract, analyze and annotate all relevant information from image-based cell screening of chemical libraries.

PubMed

Rabal, Obdulia; Link, Wolfgang; Serelde, Beatriz G; Bischoff, James R; Oyarzabal, Julen

2010-04-01

Here we report the development and validation of a complete solution to manage and analyze the data produced by image-based phenotypic screening campaigns of small-molecule libraries. In one step initial crude images are analyzed for multiple cytological features, statistical analysis is performed and molecules that produce the desired phenotypic profile are identified. A naïve Bayes classifier, integrating chemical and phenotypic spaces, is built and utilized during the process to assess those images initially classified as "fuzzy"-an automated iterative feedback tuning. Simultaneously, all this information is directly annotated in a relational database containing the chemical data. This novel fully automated method was validated by conducting a re-analysis of results from a high-content screening campaign involving 33 992 molecules used to identify inhibitors of the PI3K/Akt signaling pathway. Ninety-two percent of confirmed hits identified by the conventional multistep analysis method were identified using this integrated one-step system as well as 40 new hits, 14.9% of the total, originally false negatives. Ninety-six percent of true negatives were properly recognized too. A web-based access to the database, with customizable data retrieval and visualization tools, facilitates the posterior analysis of annotated cytological features which allows identification of additional phenotypic profiles; thus, further analysis of original crude images is not required.

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Xia; Department of Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL 35487; Park, Jihoon

2015-02-15

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particlesmore » are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.« less

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozian, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The essentially nonoscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozin, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The Essentially NonOscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Enhancing the functional properties of thermophilic enzymes by chemical modification and immobilization.

PubMed

Cowan, Don A; Fernandez-Lafuente, Roberto

2011-09-10

The immobilization of proteins (mostly typically enzymes) onto solid supports is mature technology and has been used successfully to enhance biocatalytic processes in a wide range of industrial applications. However, continued developments in immobilization technology have led to more sophisticated and specialized applications of the process. A combination of targeted chemistries, for both the support and the protein, sometimes in combination with additional chemical and/or genetic engineering, has led to the development of methods for the modification of protein functional properties, for enhancing protein stability and for the recovery of specific proteins from complex mixtures. In particular, the development of effective methods for immobilizing large multi-subunit proteins with multiple covalent linkages (multi-point immobilization) has been effective in stabilizing proteins where subunit dissociation is the initial step in enzyme inactivation. In some instances, multiple benefits are achievable in a single process. Here we comprehensively review the literature pertaining to immobilization and chemical modification of different enzyme classes from thermophiles, with emphasis on the chemistries involved and their implications for modification of the enzyme functional properties. We also highlight the potential for synergies in the combined use of immobilization and other chemical modifications. Copyright © 2011 Elsevier Inc. All rights reserved.

Isolated human and animal stratum corneum as a partial model for the 15 steps of percutaneous absorption: emphasizing decontamination, part II.

PubMed

Hui, Xiaoying; Lamel, Sonia; Qiao, Peter; Maibach, Howard I

2013-03-01

Cutaneously directed chemical warfare agents can elicit significant morbidity and mortality. The optimization of prophylactic and therapeutic interventions counteracting these agents is crucial, and the development of decontamination protocols and methodology of post dermal exposure risk assessments would be additionally applicable to common industrial and consumer dermatotoxicants. Percutaneous (PC) penetration is often considered a simple one-step diffusion process but presently consists of at least 15 steps. The systemic exposure to an agent depends on multiple factors and the second part of this review covers absorption and excretion kinetics, wash and rub effects, skin substantivity and transfer, among others. Importantly, the partitioning behavior and diffusion through the stratum corneum (SC) of a wide physicochemical array of compounds shows that many compounds have approximately the same diffusion coefficient which determines their percutaneous absorption in vivo. After accounting for anatomical variation of the SC, the penetration flux value of a substance depends mainly on its SC/vehicle partition coefficient. Additionally, the SC acts as a 'reservoir' for topically applied molecules, and tape stripping methodology can quantify the remaining chemical in the SC which can predict the total molecular penetration in vivo. The determination of ideal decontamination protocols is of utmost importance to reduce morbidity and mortality. However, even expeditious standard washing procedures post dermal chemical exposure often fails to remove chemicals. The second part of this overview continues to review percutaneous penetration extending insights into the complexities of penetration, decontamination and potential newer assays that may be of practical importance. Copyright © 2012 John Wiley & Sons, Ltd.

Energy balance for uranium recovery from seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneider, E.; Lindner, H.

The energy return on investment (EROI) of an energy resource is the ratio of the energy it ultimately produces to the energy used to recover it. EROI is a key viability measure for a new recovery technology, particularly in its early stages of development when financial cost assessment would be premature or highly uncertain. This paper estimates the EROI of uranium recovery from seawater via a braid adsorbent technology. In this paper, the energy cost of obtaining uranium from seawater is assessed by breaking the production chain into three processes: adsorbent production, adsorbent deployment and mooring, and uranium elution andmore » purification. Both direct and embodied energy inputs are considered. Direct energy is the energy used by the processes themselves, while embodied energy is used to fabricate their material, equipment or chemical inputs. If the uranium is used in a once-through fuel cycle, the braid adsorbent technology EROI ranges from 12 to 27, depending on still-uncertain performance and system design parameters. It is highly sensitive to the adsorbent capacity in grams of U captured per kg of adsorbent as well as to potential economies in chemical use. This compares to an EROI of ca. 300 for contemporary terrestrial mining. It is important to note that these figures only consider the mineral extraction step in the fuel cycle. At a reference performance level of 2.76 g U recovered per kg adsorbent immersed, the largest energy consumers are the chemicals used in adsorbent production (63%), anchor chain mooring system fabrication and operations (17%), and unit processes in the adsorbent production step (12%). (authors)« less

Confined-plume chemical deposition: rapid synthesis of crystalline coatings of known hard or superhard materials on inorganic or organic supports by resonant IR decomposition of molecular precursors.

PubMed

Ivanov, Borislav L; Wellons, Matthew S; Lukehart, Charles M

2009-08-26

A one-step process for preparing microcrystalline coatings of known superhard, very hard, or ultraincompressible ceramic compositions on either inorganic or organic supports is reported. Midinfrared pulsed-laser irradiation of preceramic chemical precursors layered between IR-transmissive hard/soft supports under temporal and spatial confinement at a laser wavelength resonant with a precursor vibrational band gives one-step deposition of crystalline ceramic coatings without incurring noticeable collateral thermal damage to the support material. Reaction plume formation at the precursor/laser beam interface initiates confined-plume, chemical deposition (CPCD) of crystalline ceramic product. Continuous ceramic coatings are produced by rastering the laser beam over a sample specimen. CPCD processing of the Re-B single-source precursor, (B(3)H(8))Re(CO)(4), the dual-source mixtures, Ru(3)(CO)(12)/B(10)H(14) or W(CO)(6)/B(10)H(14), and the boron/carbon single-source precursor, o-B(10)C(2)H(12), confined between Si wafer or NaCl plates gives microcrystalline deposits of ReB(2), RuB(2), WB(4), or B(4)C, respectively. CPCD processing of Kevlar fabric wetted by (B(3)H(8))Re(CO)(4) produces an oriented, microcrystalline coating of ReB(2) on the Kevlar fabric without incurring noticeable thermal damage of the polymer support. Similarly, microcrystalline coatings of ReB(2) can be formed on IR-transmissive IR2, Teflon, or Ultralene polymer films.

Dissolvable fluidic time delays for programming multi-step assays in instrument-free paper diagnostics.

PubMed

Lutz, Barry; Liang, Tinny; Fu, Elain; Ramachandran, Sujatha; Kauffman, Peter; Yager, Paul

2013-07-21

Lateral flow tests (LFTs) are an ingenious format for rapid and easy-to-use diagnostics, but they are fundamentally limited to assay chemistries that can be reduced to a single chemical step. In contrast, most laboratory diagnostic assays rely on multiple timed steps carried out by a human or a machine. Here, we use dissolvable sugar applied to paper to create programmable flow delays and present a paper network topology that uses these time delays to program automated multi-step fluidic protocols. Solutions of sucrose at different concentrations (10-70% of saturation) were added to paper strips and dried to create fluidic time delays spanning minutes to nearly an hour. A simple folding card format employing sugar delays was shown to automate a four-step fluidic process initiated by a single user activation step (folding the card); this device was used to perform a signal-amplified sandwich immunoassay for a diagnostic biomarker for malaria. The cards are capable of automating multi-step assay protocols normally used in laboratories, but in a rapid, low-cost, and easy-to-use format.

Dissolvable fluidic time delays for programming multi-step assays in instrument-free paper diagnostics

PubMed Central

Lutz, Barry; Liang, Tinny; Fu, Elain; Ramachandran, Sujatha; Kauffman, Peter; Yager, Paul

2013-01-01

Lateral flow tests (LFTs) are an ingenious format for rapid and easy-to-use diagnostics, but they are fundamentally limited to assay chemistries that can be reduced to a single chemical step. In contrast, most laboratory diagnostic assays rely on multiple timed steps carried out by a human or a machine. Here, we use dissolvable sugar applied to paper to create programmable flow delays and present a paper network topology that uses these time delays to program automated multi-step fluidic protocols. Solutions of sucrose at different concentrations (10-70% of saturation) were added to paper strips and dried to create fluidic time delays spanning minutes to nearly an hour. A simple folding card format employing sugar delays was shown to automate a four-step fluidic process initiated by a single user activation step (folding the card); this device was used to perform a signal-amplified sandwich immunoassay for a diagnostic biomarker for malaria. The cards are capable of automating multi-step assay protocols normally used in laboratories, but in a rapid, low-cost, and easy-to-use format. PMID:23685876

Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.

PubMed

Gao, Erping; Wang, Wenzhong

2013-11-21

Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2˙(-) anions as the major oxidation species instead of ˙OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25.

Enriching the biological space of natural products and charting drug metabolites, through real time biotransformation monitoring: The NMR tube bioreactor.

PubMed

Chatzikonstantinou, Alexandra V; Chatziathanasiadou, Maria V; Ravera, Enrico; Fragai, Marco; Parigi, Giacomo; Gerothanassis, Ioannis P; Luchinat, Claudio; Stamatis, Haralambos; Tzakos, Andreas G

2018-01-01

Natural products offer a wide range of biological activities, but they are not easily integrated in the drug discovery pipeline, because of their inherent scaffold intricacy and the associated complexity in their synthetic chemistry. Enzymes may be used to perform regioselective and stereoselective incorporation of functional groups in the natural product core, avoiding harsh reaction conditions, several protection/deprotection and purification steps. Herein, we developed a three step protocol carried out inside an NMR-tube. 1st-step: STD-NMR was used to predict the: i) capacity of natural products as enzyme substrates and ii) possible regioselectivity of the biotransformations. 2nd-step: The real-time formation of multiple-biotransformation products in the NMR-tube bioreactor was monitored in-situ. 3rd-step: STD-NMR was applied in the mixture of the biotransformed products to screen ligands for protein targets. Herein, we developed a simple and time-effective process, the "NMR-tube bioreactor", that is able to: (i) predict which component of a mixture of natural products can be enzymatically transformed, (ii) monitor in situ the transformation efficacy and regioselectivity in crude extracts and multiple substrate biotransformations without fractionation and (iii) simultaneously screen for interactions of the biotransformation products with pharmaceutical protein targets. We have developed a green, time-, and cost-effective process that provide a simple route from natural products to lead compounds for drug discovery. This process can speed up the most crucial steps in the early drug discovery process, and reduce the chemical manipulations usually involved in the pipeline, improving the environmental compatibility. Copyright © 2017 Elsevier B.V. All rights reserved.

The automated array assembly task of the low-cost silicon solar array project, phase 2

NASA Technical Reports Server (NTRS)

Coleman, M. G.; Pryor, R. A.; Sparks, T. G.; Legge, R.; Saltzman, D. L.

1980-01-01

Several specific processing steps as part of a total process sequence for manufacturing silicon solar cells were studied. Ion implantation was identified as the preferred process step for impurity doping. Unanalyzed beam ion implantation was shown to have major cost advantages over analyzed beam implantation. Further, high quality cells were fabricated using a high current unanalyzed beam. Mechanically masked plasma patterning of silicon nitride was shown to be capable of forming fine lines on silicon surfaces with spacings between mask and substrate as great as 250 micrometers. Extensive work was performed on advances in plated metallization. The need for the thick electroless palladium layer was eliminated. Further, copper was successfully utilized as a conductor layer utilizing nickel as a barrier to copper diffusion into the silicon. Plasma etching of silicon for texturing and saw damage removal was shown technically feasible but not cost effective compared to wet chemical etching techniques.

Emergence of Coding and its Specificity as a Physico-Informatic Problem

NASA Astrophysics Data System (ADS)

Wills, Peter R.; Nieselt, Kay; McCaskill, John S.

2015-06-01

We explore the origin-of-life consequences of the view that biological systems are demarcated from inanimate matter by their possession of referential information, which is processed computationally to control choices of specific physico-chemical events. Cells are cybernetic: they use genetic information in processes of communication and control, subjecting physical events to a system of integrated governance. The genetic code is the most obvious example of how cells use information computationally, but the historical origin of the usefulness of molecular information is not well understood. Genetic coding made information useful because it imposed a modular metric on the evolutionary search and thereby offered a general solution to the problem of finding catalysts of any specificity. We use the term "quasispecies symmetry breaking" to describe the iterated process of self-organisation whereby the alphabets of distinguishable codons and amino acids increased, step by step.

Fiber pushout test: A three-dimensional finite element computational simulation

NASA Technical Reports Server (NTRS)

Mital, Subodh K.; Chamis, Christos C.

1990-01-01

A fiber pushthrough process was computationally simulated using three-dimensional finite element method. The interface material is replaced by an anisotropic material with greatly reduced shear modulus in order to simulate the fiber pushthrough process using a linear analysis. Such a procedure is easily implemented and is computationally very effective. It can be used to predict fiber pushthrough load for a composite system at any temperature. The average interface shear strength obtained from pushthrough load can easily be separated into its two components: one that comes from frictional stresses and the other that comes from chemical adhesion between fiber and the matrix and mechanical interlocking that develops due to shrinkage of the composite because of phase change during the processing. Step-by-step procedures are described to perform the computational simulation, to establish bounds on interfacial bond strength and to interpret interfacial bond quality.

From minerals to hillslopes: Towards an integrated framework for interpreting chemical and physical erosion

NASA Astrophysics Data System (ADS)

Hahm, W.; Riebe, C. S.; Ferrier, K.; Kirchner, J. W.

2011-12-01

Traditional frameworks for conceptualizing hillslope denudation distinguish between the movement of mass in solution (chemical erosion) and mass moved via mechanical processes (physical erosion). At the hillslope scale, physical and chemical erosion rates can be quantified by combining measurements of regolith chemistry with cosmogenic nuclide concentrations in bedrock and sediment, while basin-scale rates are often inferred from riverine solute and sediment loads. These techniques integrate the effects of numerous weathering and erosion mechanisms and do not provide prima facie information about the precise nature and scale of those mechanisms. For insight into erosional process, physical erosion has been considered in terms of two limiting regimes. When physical erosion outpaces weathering front advance, regolith is mobilized downslope as soon as it is sufficiently loosened by weathering, and physical erosion rates are limited by rates of mobile regolith production. This is commonly termed weathering-limited erosion. Conversely, when weathering front advance outpaces erosion, the mobile regolith layer grows thicker over time, and physical erosion rates are limited by the efficiency of downslope transport processes. This is termed transport-limited erosion. This terminology brings the description of hillslope evolution closer to the realm of essential realism, to the extent that measurable quantities from the field can be cast in a process-based framework. An analogous process-limitation framework describes chemical erosion. In supply-limited chemical erosion, chemical weathering depletes regolith of its reactive phases during residence on a hillslope, and chemical erosion rates are limited by the supply of fresh minerals to the weathering zone. Alternatively, hillslopes may exhibit kinetic-limited chemical erosion, where physical erosion transports regolith downslope before weatherable phases are completely removed by chemical erosion. We show how supply- and kinetic-limited chemical erosion can be distinguished from one another using data from a global compilation of physical and chemical erosion rates. As a step towards understanding these rates at the level of essential realism, we explore how the hillslope-scale regimes of supply- and kinetic-limited chemical erosion relate to existing conceptual frameworks that interpret weathering rates in terms of transport- and kinetic-limitation at the mineral scale.

Chemical and process mineralogical characterizations of spent lithium-ion batteries: an approach by multi-analytical techniques.

PubMed

Zhang, Tao; He, Yaqun; Wang, Fangfang; Ge, Linhan; Zhu, Xiangnan; Li, Hong

2014-06-01

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (-2+0.25 mm) and Co and graphite-enriched fraction (-0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from -0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Wafer-scale Thermodynamically Stable GaN Nanorods via Two-Step Self-Limiting Epitaxy for Optoelectronic Applications

NASA Astrophysics Data System (ADS)

Kum, Hyun; Seong, Han-Kyu; Lim, Wantae; Chun, Daemyung; Kim, Young-Il; Park, Youngsoo; Yoo, Geonwook

2017-01-01

We present a method of epitaxially growing thermodynamically stable gallium nitride (GaN) nanorods via metal-organic chemical vapor deposition (MOCVD) by invoking a two-step self-limited growth (TSSLG) mechanism. This allows for growth of nanorods with excellent geometrical uniformity with no visible extended defects over a 100 mm sapphire (Al2O3) wafer. An ex-situ study of the growth morphology as a function of growth time for the two self-limiting steps elucidate the growth dynamics, which show that formation of an Ehrlich-Schwoebel barrier and preferential growth in the c-plane direction governs the growth process. This process allows monolithic formation of dimensionally uniform nanowires on templates with varying filling matrix patterns for a variety of novel electronic and optoelectronic applications. A color tunable phosphor-free white light LED with a coaxial architecture is fabricated as a demonstration of the applicability of these nanorods grown by TSSLG.

From mess to mass: a methodology for calculating storm event pollutant loads with their uncertainties, from continuous raw data time series.

PubMed

Métadier, M; Bertrand-Krajewski, J-L

2011-01-01

With the increasing implementation of continuous monitoring of both discharge and water quality in sewer systems, large data bases are now available. In order to manage large amounts of data and calculate various variables and indicators of interest it is necessary to apply automated methods for data processing. This paper deals with the processing of short time step turbidity time series to estimate TSS (Total Suspended Solids) and COD (Chemical Oxygen Demand) event loads in sewer systems during storm events and their associated uncertainties. The following steps are described: (i) sensor calibration, (ii) estimation of data uncertainties, (iii) correction of raw data, (iv) data pre-validation tests, (v) final validation, and (vi) calculation of TSS and COD event loads and estimation of their uncertainties. These steps have been implemented in an integrated software tool. Examples of results are given for a set of 33 storm events monitored in a stormwater separate sewer system.

Laser-induced Self-organizing Microstructures on Steel for Joining with Polymers

NASA Astrophysics Data System (ADS)

van der Straeten, Kira; Burkhardt, Irmela; Olowinsky, Alexander; Gillner, Arnold

The combination of different materials such as thermoplastic composites and metals is an important way to improve lightweight construction. As direct connections between these materials fail due to their physical and chemical properties, other joining techniques are required. A new joining approach besides fastening and adhesive joining is a laser-based two-step process. Within the first step the metal surface is modified by laser-microstructuring. In order to enlarge the boundary surface and create undercuts, random self-organizing microstructures are generated on stainless steel substrates. In a second process step both joining partners, metal and composite, are clamped together, the steel surface is heated up with laser radiation and through heat conduction the thermoplastic matrix is melted and flows into the structures. After cooling-down a firm joint between both materials is created. The presented work shows the influence of different laser parameters on the generation of the microstructures. The joint strength is investigated through tensile shear strength tests.

Health risk assessment and the practice of industrial hygiene.

PubMed

Paustenbach, D J

1990-07-01

It has been claimed that there may be as many as 2000 airborne chemicals to which persons could be exposed in the workplace and in the community. Of these, occupational exposure limits have been set for approximately 700 chemicals, and only about 30 chemicals have limits for the ambient air. It is likely that some type of health risk assessment methodology will be used to establish limits for the remainder. Although these methods have been used for over 10 yr to set environmental limits, each step of the process (hazard identification, dose-response assessment, exposure assessment, and risk characterization) contains a number of traps into which scientists and risk managers can fall. For example, regulatory approaches to the hazard identification step have allowed little discrimination between the various animal carcinogens, even though these chemicals can vary greatly in their potency and mechanisms of action. In general, epidemiology data have been given little weight compared to the results of rodent bioassays. The dose-response extrapolation process, as generally practiced, often does not present the range of equally plausible values. Procedures which acknowledge and quantitatively account for some or all of the different classes of chemical carcinogens have not been widely adopted. For example, physiologically based pharmacokinetic (PB-PK) and biologically based models need to become a part of future risk assessments. The exposure evaluation portion of risk assessments can now be significantly more valid because of better dispersion models, validated exposure parameters, and the use of computers to account for complex environmental factors. Using these procedures, industrial hygienists are now able to quantitatively estimate the risks caused not only by the inhalation of chemicals but also those caused by dermal contact and incidental ingestion. The appropriate use of risk assessment methods should allow scientists and risk managers to set scientifically valid environmental and occupational standards for air contaminants.

Solving satisfiability problems using a novel microarray-based DNA computer.

PubMed

Lin, Che-Hsin; Cheng, Hsiao-Ping; Yang, Chang-Biau; Yang, Chia-Ning

2007-01-01

An algorithm based on a modified sticker model accompanied with an advanced MEMS-based microarray technology is demonstrated to solve SAT problem, which has long served as a benchmark in DNA computing. Unlike conventional DNA computing algorithms needing an initial data pool to cover correct and incorrect answers and further executing a series of separation procedures to destroy the unwanted ones, we built solutions in parts to satisfy one clause in one step, and eventually solve the entire Boolean formula through steps. No time-consuming sample preparation procedures and delicate sample applying equipment were required for the computing process. Moreover, experimental results show the bound DNA sequences can sustain the chemical solutions during computing processes such that the proposed method shall be useful in dealing with large-scale problems.

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik

2014-09-28

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partiallymore » hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.« less

DNA Bipedal Motor Achieves a Large Number of Steps Due to Operation Using Microfluidics-Based Interface.

PubMed

Tomov, Toma E; Tsukanov, Roman; Glick, Yair; Berger, Yaron; Liber, Miran; Avrahami, Dorit; Gerber, Doron; Nir, Eyal

2017-04-25

Realization of bioinspired molecular machines that can perform many and diverse operations in response to external chemical commands is a major goal in nanotechnology, but current molecular machines respond to only a few sequential commands. Lack of effective methods for introduction and removal of command compounds and low efficiencies of the reactions involved are major reasons for the limited performance. We introduce here a user interface based on a microfluidics device and single-molecule fluorescence spectroscopy that allows efficient introduction and removal of chemical commands and enables detailed study of the reaction mechanisms involved in the operation of synthetic molecular machines. The microfluidics provided 64 consecutive DNA strand commands to a DNA-based motor system immobilized inside the microfluidics, driving a bipedal walker to perform 32 steps on a DNA origami track. The microfluidics enabled removal of redundant strands, resulting in a 6-fold increase in processivity relative to an identical motor operated without strand removal and significantly more operations than previously reported for user-controlled DNA nanomachines. In the motor operated without strand removal, redundant strands interfere with motor operation and reduce its performance. The microfluidics also enabled computer control of motor direction and speed. Furthermore, analysis of the reaction kinetics and motor performance in the absence of redundant strands, made possible by the microfluidics, enabled accurate modeling of the walker processivity. This enabled identification of dynamic boundaries and provided an explanation, based on the "trap state" mechanism, for why the motor did not perform an even larger number of steps. This understanding is very important for the development of future motors with significantly improved performance. Our universal interface enables two-way communication between user and molecular machine and, relying on concepts similar to that of solid-phase synthesis, removes limitations on the number of external stimuli. This interface, therefore, is an important step toward realization of reliable, processive, reproducible, and useful externally controlled DNA nanomachines.

Independently recruited oxidases from the glucose-methanol-choline oxidoreductase family enabled chemical defences in leaf beetle larvae (subtribe Chrysomelina) to evolve

PubMed Central

Rahfeld, Peter; Kirsch, Roy; Kugel, Susann; Wielsch, Natalie; Stock, Magdalena; Groth, Marco; Boland, Wilhelm; Burse, Antje

2014-01-01

Larvae of the leaf beetle subtribe Chrysomelina sensu stricto repel their enemies by displaying glandular secretions that contain defensive compounds. These repellents can be produced either de novo (iridoids) or by using plant-derived precursors (e.g. salicylaldehyde). The autonomous production of iridoids, as in Phaedon cochleariae, is the ancestral chrysomeline chemical defence and predates the evolution of salicylaldehyde-based defence. Both biosynthesis strategies include an oxidative step of an alcohol intermediate. In salicylaldehyde-producing species, this step is catalysed by salicyl alcohol oxidases (SAOs) of the glucose-methanol-choline (GMC) oxidoreductase superfamily, but the enzyme oxidizing the iridoid precursor is unknown. Here, we show by in vitro as well as in vivo experiments that P. cochleariae also uses an oxidase from the GMC superfamily for defensive purposes. However, our phylogenetic analysis of chrysomeline GMC oxidoreductases revealed that the oxidase of the iridoid pathway originated from a GMC clade different from that of the SAOs. Thus, the evolution of a host-independent chemical defence followed by a shift to a host-dependent chemical defence in chrysomeline beetles coincided with the utilization of genes from different GMC subfamilies. These findings illustrate the importance of the GMC multi-gene family for adaptive processes in plant–insect interactions. PMID:24943369

Tailoring gas sensor arrays via the design of short peptides sequences as binding elements.

PubMed

Mascini, Marcello; Pizzoni, Daniel; Perez, German; Chiarappa, Emilio; Di Natale, Corrado; Pittia, Paola; Compagnone, Dario

2017-07-15

A semi-combinatorial virtual approach was used to prepare peptide-based gas sensors with binding properties towards five different chemical classes (alcohols, aldehydes, esters, hydrocarbons and ketones). Molecular docking simulations were conducted for a complete tripeptide library (8000 elements) versus 58 volatile compounds belonging to those five chemical classes. By maximizing the differences between chemical classes, a subset of 120 tripeptides was extracted and used as scaffolds for generating a combinatorial library of 7912 tetrapeptides. This library was processed in an analogous way to the former. Five tetrapeptides (IHRI, KSDS, LGFD, TGKF and WHVS) were chosen depending on their virtual affinity and cross-reactivity for the experimental step. The five peptides were covalently bound to gold nanoparticles by adding a terminal cysteine to each tetrapeptide and deposited onto 20MHz quartz crystal microbalances to construct the gas sensors. The behavior of peptides after this chemical modification was simulated at the pH range used in the immobilization step. ΔF signals analyzed by principal component analysis matched the virtually screened data. The array was able to clearly discriminate the 13 volatile compounds tested based on their hydrophobicity and hydrophilicity molecules as well as the molecular weight. Copyright © 2016 Elsevier B.V. All rights reserved.

Extract from Fructus cannabis activating calcineurin improved learning and memory in mice with chemical drug-induced dysmnesia.

PubMed

Luo, Jing; Yin, Jiang-Hua; Wu, He-Zhen; Wei, Qun

2003-11-01

To investigate the effects of extract from Fructus cannabis (EFC) that can activate calcineurin on learning and memory impairment induced by chemical drugs in mice. Bovine brain calcineurin and calmodulin were isolated from frozen tissues. The activity of calcineurin was assayed using p-nitrophenyl phosphate (PNPP) as the substrate. Step-down type passive avoidance test and water maze were used together to determine the effects of EFC on learning and memory dysfunction. EFC activated calcineurin activity at a concentration range of 0.01-100 g/L. The maximal value of EFC on calcineurin activity (35 %+/-5 %) appeared at a concentration of 10 g/L. The chemical drugs such as scopolamine, sodium nitrite, and 45 % ethanol, and sodium pentobarbital induced learning and memory dysfunction. EFC administration (0.2, 0.4, and 0.8 g/kg, igx7 d) prolonged the latency and decreased the number of errors in the step-down test. EFC, given for 7 d, enhanced the spatial resolution of amnesic mice in water maze test. EFC overcome amnesia of three stages of memory process at the dose of 0.2 g/kg. EFC with an activation role of calcineurin can improve the impaired learning and memory induced by chemical drugs in mice.

A two-in-one process for reliable graphene transistors processed with photo-lithography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahlberg, P.; Hinnemo, M.; Song, M.

2015-11-16

Research on graphene field-effect transistors (GFETs) has mainly relied on devices fabricated using electron-beam lithography for pattern generation, a method that has known problems with polymer contaminants. GFETs fabricated via photo-lithography suffer even worse from other chemical contaminations, which may lead to strong unintentional doping of the graphene. In this letter, we report on a scalable fabrication process for reliable GFETs based on ordinary photo-lithography by eliminating the aforementioned issues. The key to making this GFET processing compatible with silicon technology lies in a two-in-one process where a gate dielectric is deposited by means of atomic layer deposition. During thismore » deposition step, contaminants, likely unintentionally introduced during the graphene transfer and patterning, are effectively removed. The resulting GFETs exhibit current-voltage characteristics representative to that of intrinsic non-doped graphene. Fundamental aspects pertaining to the surface engineering employed in this work are investigated in the light of chemical analysis in combination with electrical characterization.« less

Fluidized-Bed Cleaning of Silicon Particles

NASA Technical Reports Server (NTRS)

Rohatgi, Naresh K.; Hsu, George C.

1987-01-01

Fluidized-bed chemical cleaning process developed to remove metallic impurities from small silicon particles. Particles (250 micrometer in size) utilized as seed material in silane pyrolysis process for production of 1-mm-size silicon. Product silicon (1 mm in size) used as raw material for fabrication of solar cells and other semiconductor devices. Principal cleaning step is wash in mixture of hydrochloric and nitric acids, leaching out metals and carrying them away as soluble chlorides. Particles fluidized by cleaning solution to assure good mixing and uniform wetting.

Pre-Finishing of SiC for Optical Applications

NASA Technical Reports Server (NTRS)

Rozzi, Jay; Clavier, Odile; Gagne, John

2011-01-01

13 Manufacturing & Prototyping A method is based on two unique processing steps that are both based on deterministic machining processes using a single-point diamond turning (SPDT) machine. In the first step, a high-MRR (material removal rate) process is used to machine the part within several microns of the final geometry. In the second step, a low-MRR process is used to machine the part to near optical quality using a novel ductile regime machining (DRM) process. DRM is a deterministic machining process associated with conditions under high hydrostatic pressures and very small depths of cut. Under such conditions, using high negative-rake angle cutting tools, the high-pressure region near the tool corresponds to a plastic zone, where even a brittle material will behave in a ductile manner. In the high-MRR processing step, the objective is to remove material with a sufficiently high rate such that the process is economical, without inducing large-scale subsurface damage. A laser-assisted machining approach was evaluated whereby a CO2 laser was focused in advance of the cutting tool. While CVD (chemical vapor deposition) SiC was successfully machined with this approach, the cutting forces were substantially higher than cuts at room temperature under the same machining conditions. During the experiments, the expansion of the part and the tool due to the heating was carefully accounted for. The higher cutting forces are most likely due to a small reduction in the shear strength of the material compared with a larger increase in friction forces due to the thermal softening effect. The key advantage is that the hybrid machine approach has the potential to achieve optical quality without the need for a separate optical finishing step. Also, this method is scalable, so one can easily progress from machining 50-mm-diameter samples to the 250-mm-diameter mirror that NASA desires.

Gallium arsenide processing for gate array logic

NASA Technical Reports Server (NTRS)

Cole, Eric D.

1989-01-01

The development of a reliable and reproducible GaAs process was initiated for applications in gate array logic. Gallium Arsenide is an extremely important material for high speed electronic applications in both digital and analog circuits since its electron mobility is 3 to 5 times that of silicon, this allows for faster switching times for devices fabricated with it. Unfortunately GaAs is an extremely difficult material to process with respect to silicon and since it includes the arsenic component GaAs can be quite dangerous (toxic) especially during some heating steps. The first stage of the research was directed at developing a simple process to produce GaAs MESFETs. The MESFET (MEtal Semiconductor Field Effect Transistor) is the most useful, practical and simple active device which can be fabricated in GaAs. It utilizes an ohmic source and drain contact separated by a Schottky gate. The gate width is typically a few microns. Several process steps were required to produce a good working device including ion implantation, photolithography, thermal annealing, and metal deposition. A process was designed to reduce the total number of steps to a minimum so as to reduce possible errors. The first run produced no good devices. The problem occurred during an aluminum etch step while defining the gate contacts. It was found that the chemical etchant attacked the GaAs causing trenching and subsequent severing of the active gate region from the rest of the device. Thus all devices appeared as open circuits. This problem is being corrected and since it was the last step in the process correction should be successful. The second planned stage involves the circuit assembly of the discrete MESFETs into logic gates for test and analysis. Finally the third stage is to incorporate the designed process with the tested circuit in a layout that would produce the gate array as a GaAs integrated circuit.

Pressure modulates the self-cleavage step of the hairpin ribozyme

NASA Astrophysics Data System (ADS)

Schuabb, Caroline; Kumar, Narendra; Pataraia, Salome; Marx, Dominik; Winter, Roland

2017-03-01

The ability of certain RNAs, denoted as ribozymes, to not only store genetic information but also catalyse chemical reactions gave support to the RNA world hypothesis as a putative step in the development of early life on Earth. This, however, might have evolved under extreme environmental conditions, including the deep sea with pressures in the kbar regime. Here we study pressure-induced effects on the self-cleavage of hairpin ribozyme by following structural changes in real-time. Our results suggest that compression of the ribozyme leads to an accelerated transesterification reaction, being the self-cleavage step, although the overall process is retarded in the high-pressure regime. The results reveal that favourable interactions between the reaction site and neighbouring nucleobases are strengthened under pressure, resulting therefore in an accelerated self-cleavage step upon compression. These results suggest that properly engineered ribozymes may also act as piezophilic biocatalysts in addition to their hitherto known properties.

Interaction of tetraethoxysilane with OH-terminated SiO2 (0 0 1) surface: A first principles study

NASA Astrophysics Data System (ADS)

Deng, Xiaodi; Song, Yixu; Li, Jinchun; Pu, Yikang

2014-06-01

First principles calculates have been performed to investigate the surface reaction mechanism of tetraethoxysilane (TEOS) with fully hydroxylated SiO2(0 0 1) substrate. In semiconductor industry, this is the key step to understand and control the SiO2 film growth in chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes. During the calculation, we proposed a model which breaks the surface dissociative chemisorption into two steps and we calculated the activation barriers and thermochemical energies for each step. Our calculation result for step one shows that the first half reaction is thermodynamically favorable. For the second half reaction, we systematically studied the two potential reaction pathways. The comparing result indicates that the pathway which is more energetically favorable will lead to formation of crystalline SiO2 films while the other will lead to formation of disordered SiO2 films.

Step-by-step seeding procedure for preparing HKUST-1 membrane on porous α-alumina support.

PubMed

Nan, Jiangpu; Dong, Xueliang; Wang, Wenjin; Jin, Wanqin; Xu, Nanping

2011-04-19

Metal-organic framework (MOF) membranes have attracted considerable attention because of their striking advantages in small-molecule separation. The preparation of an integrated MOF membrane is still a major challenge. Depositing a uniform seed layer on a support for secondary growth is a main route to obtaining an integrated MOF membrane. A novel seeding method to prepare HKUST-1 (known as Cu(3)(btc)(2)) membranes on porous α-alumina supports is reported. The in situ production of the seed layer was realized in step-by-step fashion via the coordination of H(3)btc and Cu(2+) on an α-alumina support. The formation process of the seed layer was observed by ultraviolet-visible absorption spectroscopy and atomic force microscopy. An integrated HKUST-1 membrane could be synthesized by the secondary hydrothermal growth on the seeded support. The gas permeation performance of the membrane was evaluated. © 2011 American Chemical Society

Single-step affinity purification of enzyme biotherapeutics: a platform methodology for accelerated process development.

PubMed

Brower, Kevin P; Ryakala, Venkat K; Bird, Ryan; Godawat, Rahul; Riske, Frank J; Konstantinov, Konstantin; Warikoo, Veena; Gamble, Jean

2014-01-01

Downstream sample purification for quality attribute analysis is a significant bottleneck in process development for non-antibody biologics. Multi-step chromatography process train purifications are typically required prior to many critical analytical tests. This prerequisite leads to limited throughput, long lead times to obtain purified product, and significant resource requirements. In this work, immunoaffinity purification technology has been leveraged to achieve single-step affinity purification of two different enzyme biotherapeutics (Fabrazyme® [agalsidase beta] and Enzyme 2) with polyclonal and monoclonal antibodies, respectively, as ligands. Target molecules were rapidly isolated from cell culture harvest in sufficient purity to enable analysis of critical quality attributes (CQAs). Most importantly, this is the first study that demonstrates the application of predictive analytics techniques to predict critical quality attributes of a commercial biologic. The data obtained using the affinity columns were used to generate appropriate models to predict quality attributes that would be obtained after traditional multi-step purification trains. These models empower process development decision-making with drug substance-equivalent product quality information without generation of actual drug substance. Optimization was performed to ensure maximum target recovery and minimal target protein degradation. The methodologies developed for Fabrazyme were successfully reapplied for Enzyme 2, indicating platform opportunities. The impact of the technology is significant, including reductions in time and personnel requirements, rapid product purification, and substantially increased throughput. Applications are discussed, including upstream and downstream process development support to achieve the principles of Quality by Design (QbD) as well as integration with bioprocesses as a process analytical technology (PAT). © 2014 American Institute of Chemical Engineers.

Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

DOEpatents

Lowden, Richard A.

1994-01-01

A process for chemical vapor deposition of crystalline silicon nitride which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide.

Food processing strategies to enhance phenolic compounds bioaccessibility and bioavailability in plant-based foods.

PubMed

Ribas-Agustí, Albert; Martín-Belloso, Olga; Soliva-Fortuny, Robert; Elez-Martínez, Pedro

2017-06-13

Phenolic compounds are important constituents of plant-based foods, as their presence is related to protective effects on health. To exert their biological activity, phenolic compounds must be released from the matrix during digestion in an absorbable form (bioaccessible) and finally absorbed and transferred to the bloodstream (bioavailable). Chemical structure and matrix interactions are some food-related factors that hamper phenolic compounds bioaccessibility and bioavailability, and that can be counteracted by food processing. It has been shown that food processing can induce chemical or physical modifications in food that enhance phenolic compounds bioaccessibility and bioavailability. These changes include: (i) chemical modifications into more bioaccessible and bioavailable forms; (ii) cleavage of covalent or hydrogen bonds or hydrophobic forces that attach phenolic compounds to matrix macromolecules; (iii) damaging microstructural barriers such as cell walls that impede the release from the matrix; and (iv) create microstructures that protect phenolic compounds until they are absorbed. Indeed, food processing can produce degradation of phenolic compounds, however, it is possible to counteract it by modulating the operating conditions in favor of increased bioaccessibility and bioavailability. This review compiles the current knowledge on the effects of processing on phenolic compounds bioaccessibility or bioavailability, while suggesting new guidelines in the search of optimal processing conditions as a step forward towards the design of healthier foods.

Compound immobilization and drug-affinity chromatography.

PubMed

Rix, Uwe; Gridling, Manuela; Superti-Furga, Giulio

2012-01-01

Bioactive small molecules act through modulating a yet unpredictable number of targets. It is therefore of critical importance to define the cellular target proteins of a compound as an entry point to understanding its mechanism of action. Often, this can be achieved in a direct fashion by chemical proteomics. As with any affinity chromatography, immobilization of the bait to a solid support is one of the earliest and most crucial steps in the process. Interfering with structural features that are important for identification of a target protein will be detrimental to binding affinity. Also, many molecules are sensitive to heat or to certain chemicals, such as acid or base, and might be destroyed during the process of immobilization, which therefore needs to be not only efficient, but also mild. The subsequent affinity chromatography step needs to preserve molecular and conformational integrity of both bait compound and proteins in order to result in the desired specific enrichment while ensuring a high level of compatibility with downstream analysis by mass spectrometry. Thus, the right choice of detergent, buffer, and protease inhibitors is also essential. This chapter describes a widely applicable procedure for the immobilization of small molecule drugs and for drug-affinity chromatography with subsequent protein identification by mass spectrometry.

Sequence-dependent base pair stepping dynamics in XPD helicase unwinding

PubMed Central

Qi, Zhi; Pugh, Robert A; Spies, Maria; Chemla, Yann R

2013-01-01

Helicases couple the chemical energy of ATP hydrolysis to directional translocation along nucleic acids and transient duplex separation. Understanding helicase mechanism requires that the basic physicochemical process of base pair separation be understood. This necessitates monitoring helicase activity directly, at high spatio-temporal resolution. Using optical tweezers with single base pair (bp) resolution, we analyzed DNA unwinding by XPD helicase, a Superfamily 2 (SF2) DNA helicase involved in DNA repair and transcription initiation. We show that monomeric XPD unwinds duplex DNA in 1-bp steps, yet exhibits frequent backsteps and undergoes conformational transitions manifested in 5-bp backward and forward steps. Quantifying the sequence dependence of XPD stepping dynamics with near base pair resolution, we provide the strongest and most direct evidence thus far that forward, single-base pair stepping of a helicase utilizes the spontaneous opening of the duplex. The proposed unwinding mechanism may be a universal feature of DNA helicases that move along DNA phosphodiester backbones. DOI: http://dx.doi.org/10.7554/eLife.00334.001 PMID:23741615

One-step synthesis of bioactive glass by spray pyrolysis

NASA Astrophysics Data System (ADS)

Shih, Shao-Ju; Chou, Yu-Jen; Chien, I.-Chen

2012-12-01

Bioactive glasses (BGs) have recently received more attention from biologists and engineers because of their potential applications in bone implants. The sol-gel process is one of the most popular methods for fabricating BGs, and has been used to produce BGs for years. However, the sol-gel process has the disadvantages of discontinuous processing and a long processing time. This study presented a one-step spray pyrolysis (SP) synthesis method to overcome these disadvantages. This SP method has synthesized spherical bioactive glass (SBG) and mesoporous bioactive glass (MBG) particles using Si-, Ca- and P-based precursors. This study used transmission electron microscopy, selected area electron diffraction and X-ray dispersive spectroscopy to characterize the microstructure, crystallographic structure, and chemical composition for the BG particles. In addition, in vitro bioactive tests showed the formation of hydroxyl apatite layers on SBG and MBG particles after immersion in simulated body fluid for 5 h. Experimental results show the SP formation mechanisms of SBG and MBG particles.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Alternating SiCl4/O2 passivation steps with SF6 etch steps for silicon deep etching

NASA Astrophysics Data System (ADS)

Duluard, C. Y.; Ranson, P.; Pichon, L. E.; Pereira, J.; Oubensaid, E. H.; Lefaucheux, P.; Puech, M.; Dussart, R.

2011-06-01

Deep etching of silicon has been investigated in an inductively coupled plasma etch reactor using short SiCl4/O2 plasma steps to passivate the sidewalls of the etched structures. A study was first carried out to define the appropriate parameters to create, at a substrate temperature of -20 °C, a passivation layer by SiCl4/O2 plasma that resists lateral chemical etching in SF6 plasma. The most efficient passivation layer was obtained for a SiCl4/O2 gas flow ratio of 2:1, a pressure of 1 Pa and a source power of 1000 W. Ex situ analyses on a film deposited with these parameters show that it is very rich in oxygen. Silicon etching processes that alternate SF6 plasma etch steps with SiCl4/O2 plasma passivation steps were then developed. Preliminary tests in pulsed-mode conditions have enabled etch rates greater than 2 µm min-1 with selectivities higher than 220. These results show that it is possible to develop a silicon deep etching process at substrate temperatures around -20 °C that uses low SiCl4 and O2 gas flows instead of conventional fluorocarbon gases for sidewall protection.

Photoresist removal using gaseous sulfur trioxide cleaning technology

NASA Astrophysics Data System (ADS)

Del Puppo, Helene; Bocian, Paul B.; Waleh, Ahmad

1999-06-01

A novel cleaning method for removing photoresists and organic polymers from semiconductor wafers is described. This non-plasma method uses anhydrous sulfur trioxide gas in a two-step process, during which, the substrate is first exposed to SO3 vapor at relatively low temperatures and then is rinsed with de-ionized water. The process is radically different from conventional plasma-ashing methods in that the photoresist is not etched or removed during the exposure to SO3. Rather, the removal of the modified photoresist takes place during the subsequent DI-water rinse step. The SO3 process completely removes photoresist and polymer residues in many post-etch applications. Additional advantages of the process are absence of halogen gases and elimination of the need for other solvents and wet chemicals. The process also enjoys a very low cost of ownership and has minimal environmental impact. The SEM and SIMS surface analysis results are presented to show the effectiveness of gaseous SO3 process after polysilicon, metal an oxide etch applications. The effects of both chlorine- and fluorine-based plasma chemistries on resist removal are described.

Designing monitoring programs for chemicals of emerging concern in potable reuse--what to include and what not to include?

PubMed

Drewes, J E; Anderson, P; Denslow, N; Olivieri, A; Schlenk, D; Snyder, S A; Maruya, K A

2013-01-01

This study discussed a proposed process to prioritize chemicals for reclaimed water monitoring programs, selection of analytical methods required for their quantification, toxicological relevance of chemicals of emerging concern regarding human health, and related issues. Given that thousands of chemicals are potentially present in reclaimed water and that information about those chemicals is rapidly evolving, a transparent, science-based framework was developed to guide prioritization of which compounds of emerging concern (CECs) should be included in reclaimed water monitoring programs. The recommended framework includes four steps: (1) compile environmental concentrations (e.g., measured environmental concentration or MEC) of CECs in the source water for reuse projects; (2) develop a monitoring trigger level (MTL) for each of these compounds (or groups thereof) based on toxicological relevance; (3) compare the environmental concentration (e.g., MEC) to the MTL; CECs with a MEC/MTL ratio greater than 1 should be prioritized for monitoring, compounds with a ratio less than '1' should only be considered if they represent viable treatment process performance indicators; and (4) screen the priority list to ensure that a commercially available robust analytical method is available for that compound.

New approach for producing chemical templates over large area by Molecular Transfer Printing

NASA Astrophysics Data System (ADS)

Inoue, Takejiro; Janes, Dustin; Ren, Jiaxing; Willson, Grant; Ellison, Christopher; Nealey, Paul

2014-03-01

Fabrication of well-defined chemically patterned surfaces is crucially important to the development of next generation microprocessors, hard disk memory devices, photonic/plasmonic devices, separation membranes, and biological microarrays. One promising patterning method in these fields is Molecular Transfer Printing (MTP), which replicates chemical patterns with feature dimensions of the order of 10nm utilizing a master template defined by the microphase separated domains of a block copolymer thin film. The total transfer printing area achievable by MTP has so far been limited by the contact area between two rigid substrates. Therefore, strategies to make conformal contact between substrates could be practically useful because a single lithographically-defined starting pattern could be used to fabricate many replicates by a low-cost process. Here we show a new approach that utilizes a chemically deposited SiN layer and a liquid conformal layer to enable transfer printing of chemical patterns upon thermal annealing over large, continuous areas. We anticipate that our process could be integrated into Step and Flash Imprint Lithography (SFIL) tools to achieve conformal layer thicknesses thin and uniform enough to permit pattern transfer through a dry-etch protocol.

Physico-Chemical Alternatives in Lignocellulosic Materials in Relation to the Kind of Component for Fermenting Purposes

PubMed Central

Coz, Alberto; Llano, Tamara; Cifrián, Eva; Viguri, Javier; Maican, Edmond; Sixta, Herbert

2016-01-01

The complete bioconversion of the carbohydrate fraction is of great importance for a lignocellulosic-based biorefinery. However, due to the structure of the lignocellulosic materials, and depending basically on the main parameters within the pretreatment steps, numerous byproducts are generated and they act as inhibitors in the fermentation operations. In this sense, the impact of inhibitory compounds derived from lignocellulosic materials is one of the major challenges for a sustainable biomass-to-biofuel and -bioproduct industry. In order to minimise the negative effects of these compounds, numerous methodologies have been tested including physical, chemical, and biological processes. The main physical and chemical treatments have been studied in this work in relation to the lignocellulosic material and the inhibitor in order to point out the best mechanisms for fermenting purposes. In addition, special attention has been made in the case of lignocellulosic hydrolysates obtained by chemical processes with SO2, due to the complex matrix of these materials and the increase in these methodologies in future biorefinery markets. Recommendations of different detoxification methods have been given. PMID:28773700

Electrogenerated chemiluminescence. 59. Rhenium complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richter, M.M.; Debad, J.D.; Bard, A.J.

Re(L)(CO){sub 3}Cl complexes (where L is 1,10-phenanthroline, 2,2`-bipyridine, or a phenanthroline or bipyridine derivative containing methyl groups) are photoluminescent in fluid solution at room temperature. In acetonitrile solutions, these complexes display one chemically reversible one-electron reduction process and one chemically irreversible oxidation process. {lambda}{sub max} for the luminescence is dependent on the nature of L, and a linear relationship between {lambda}{sub max} and the difference in electrode potentials for oxidation and reduction is evident. Electrogenerated chemiluminescence (ECL) was observed in acetonitrile solutions of these complexes (Bu{sub 4}NPF{sub 6} as electrolyte) by stepping the potential of a Pt disk working electrodemore » between potentials sufficient to form the radical anionic and cationic species. The relative amount of light produced during the anodic and cathodic pulses was dependent on the potential limits and pulse duration. ECL was also generated in the presence of coreactants, i.e., with tri-n-propylamine upon stepping the potential sufficiently positive to form the deprotonated tri-n-propylamine radical and the cationic rhenium(II) species Re{sup II}(L)(CO){sub 3}Cl{sup +}. When S{sub 2}O{sub 8}{sup 2-} was present in solution, ECL was also observed for all of the complexes upon stepping to potentials sufficient to form (Re{sup I}(L)(CO){sub 3}Cl){sup -} and the strong oxidant SO{sub 4}{sup .-}. 44 refs., 8 figs.« less

Electrical property of macroscopic graphene composite fibers prepared by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Sun, Haibin; Fu, Can; Gao, Yanli; Guo, Pengfei; Wang, Chunlei; Yang, Wenchao; Wang, Qishang; Zhang, Chongwu; Wang, Junya; Xu, Junqi

2018-07-01

Graphene fibers are promising candidates in portable and wearable electronics due to their tiny volume, flexibility and wearability. Here, we successfully synthesized macroscopic graphene composite fibers via a two-step process, i.e. first electrospinning and then chemical vapor deposition (CVD). Briefly, the well-dispersed PAN nanofibers were sprayed onto the copper surface in an electrified thin liquid jet by electrospinning. Subsequently, CVD growth process induced the formation of graphene films using a PAN-solid source of carbon and a copper catalyst. Finally, crumpled and macroscopic graphene composite fibers were obtained from carbon nanofiber/graphene composite webs by self-assembly process in the deionized water. Temperature-dependent conduct behavior reveals that electron transport of the graphene composite fibers belongs to hopping mechanism and the typical electrical conductivity reaches 4.59 × 103 S m‑1. These results demonstrated that the graphene composite fibers are promising for the next-generation flexible and wearable electronics.

Toxicological benchmarks for potential contaminants of concern for effects on soil and litter invertebrates and heterotrophic process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Will, M.E.; Suter, G.W. II

1995-09-01

An important step in ecological risk assessments is screening the chemicals occur-ring on a site for contaminants of potential concern. Screening may be accomplished by comparing reported ambient concentrations to a set of toxicological benchmarks. Multiple endpoints for assessing risks posed by soil-borne contaminants to organisms directly impacted by them have been established. This report presents benchmarks for soil invertebrates and microbial processes and addresses only chemicals found at United States Department of Energy (DOE) sites. No benchmarks for pesticides are presented. After discussing methods, this report presents the results of the literature review and benchmark derivation for toxicity tomore » earthworms (Sect. 3), heterotrophic microbes and their processes (Sect. 4), and other invertebrates (Sect. 5). The final sections compare the benchmarks to other criteria and background and draw conclusions concerning the utility of the benchmarks.« less

Fine structuration of low-temperature co-fired ceramic (LTCC) microreactors.

PubMed

Jiang, Bo; Haber, Julien; Renken, Albert; Muralt, Paul; Kiwi-Minsker, Lioubov; Maeder, Thomas

2015-01-21

The development of microreactors that operate under harsh conditions is always of great interest for many applications. Here we present a microfabrication process based on low-temperature co-fired ceramic (LTCC) technology for producing microreactors which are able to perform chemical processes at elevated temperature (>400 °C) and against concentrated harsh chemicals such as sodium hydroxide, sulfuric acid and hydrochloric acid. Various micro-scale cavities and/or fluidic channels were successfully fabricated in these microreactors using a set of combined and optimized LTCC manufacturing processes. Among them, it has been found that laser micromachining and multi-step low-pressure lamination are particularly critical to the fabrication and quality of these microreactors. Demonstration of LTCC microreactors with various embedded fluidic structures is illustrated with a number of examples, including micro-mixers for studies of exothermic reactions, multiple-injection microreactors for ionone production, and high-temperature microreactors for portable hydrogen generation.

Winery wastewater treatment by a combined process: long term aerated storage and Fenton's reagent.

PubMed

Lucas, Marco S; Mouta, Maria; Pirra, António; Peres, José A

2009-01-01

The degradation of the organic pollutants present in winery wastewater was carried out by the combination of two successive steps: an aerobic biological process followed by a chemical oxidation process using Fenton's reagent. The main goal of this study was to evaluate the temporal characteristics of solids and chemical oxygen demand (COD) present in winery wastewater in a long term aerated storage bioreactor. The performance of different air dosage daily supplied to the biologic reactor, in laboratory and pilot scale, were examined. The long term hydraulic retention time, 11 weeks, contributed remarkably to the reduction of COD (about 90%) and the combination with the Fenton's reagent led to a high overall COD reduction that reached 99.5% when the mass ratio (R = H(2)O(2)/COD) used was equal to 2.5, maintaining constant the molar ratio H(2)O(2)/Fe(2+)=15.

Adsorption of phenolic compound by aged-refuse.

PubMed

Xiaoli, Chai; Youcai, Zhao

2006-09-01

The adsorption of phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol by aged-refuse has been studied. Adsorption isotherms have been determined for phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol and the data fits well to the Freundlich equation. The chlorinated phenols are absorbed more strongly than the phenol and the adsorption capacity has an oblivious relationship with the numbers and the position of chlorine subsistent. The experiment data suggests that both the partition function and the chemical adsorption involve in the adsorption process. Pseudo-first-order and pseudo-second-order model were applied to investigate the kinetics of the adsorption and the results show that it fit the pseudo-second-order model. More than one step involves in the adsorption process and the overall rate of the adsorption process appears to be controlled by the chemical reaction. The thermodynamic analysis indicates that the adsorption is spontaneous and endothermic.

A parallel algorithm for step- and chain-growth polymerization in molecular dynamics.

PubMed

de Buyl, Pierre; Nies, Erik

2015-04-07

Classical Molecular Dynamics (MD) simulations provide insight into the properties of many soft-matter systems. In some situations, it is interesting to model the creation of chemical bonds, a process that is not part of the MD framework. In this context, we propose a parallel algorithm for step- and chain-growth polymerization that is based on a generic reaction scheme, works at a given intrinsic rate and produces continuous trajectories. We present an implementation in the ESPResSo++ simulation software and compare it with the corresponding feature in LAMMPS. For chain growth, our results are compared to the existing simulation literature. For step growth, a rate equation is proposed for the evolution of the crosslinker population that compares well to the simulations for low crosslinker functionality or for short times.

A parallel algorithm for step- and chain-growth polymerization in molecular dynamics

NASA Astrophysics Data System (ADS)

de Buyl, Pierre; Nies, Erik

2015-04-01

Classical Molecular Dynamics (MD) simulations provide insight into the properties of many soft-matter systems. In some situations, it is interesting to model the creation of chemical bonds, a process that is not part of the MD framework. In this context, we propose a parallel algorithm for step- and chain-growth polymerization that is based on a generic reaction scheme, works at a given intrinsic rate and produces continuous trajectories. We present an implementation in the ESPResSo++ simulation software and compare it with the corresponding feature in LAMMPS. For chain growth, our results are compared to the existing simulation literature. For step growth, a rate equation is proposed for the evolution of the crosslinker population that compares well to the simulations for low crosslinker functionality or for short times.

Removal of fouling species from brackish water reverse osmosis reject stream.

PubMed

Ayoub, G M; Korban, L; Al-Hindi, M; Zayyat, R

2018-03-01

Brine disposal from reverse osmosis (RO) systems remains a major challenge for the desalination industry especially in inland areas where discharge options are very limited. Solutions will entail the introduction of economic treatment processes that will alleviate the brine's negative impact on the environment and reduce its discharge volume. Such processes could act as an intermediary treatment process for the recycling of the brine through an additional RO stage which, for brackish water (BW) desalination, could lead to saving valuable water while reducing the amount of brine discharge. In this context, the study at hand attempts to evaluate the effectiveness of a one-step chemical process for the treatment of BWRO brine. This study seeks to determine optimal operating conditions relative to type, ratio, and dosage of alkalizing chemicals, pH and temperature, for substantially reducing the concentrations of scaling parameters such as calcium, magnesium, silica, and strontium. The results indicate that precipitation softening at pH = 11.5 using combined chemical dosages of NaOH and Na 2 CO 3 in a ratio of 2:1 leads to substantial removal of calcium and magnesium (>95%) and moderately high removal of strontium and silica (>71%).

Simplified Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two time step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting rates of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx are obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Magnetically Enhanced Solid-Liquid Separation

NASA Astrophysics Data System (ADS)

Rey, C. M.; Keller, K.; Fuchs, B.

2005-07-01

DuPont is developing an entirely new method of solid-liquid filtration involving the use of magnetic fields and magnetic field gradients. The new hybrid process, entitled Magnetically Enhanced Solid-Liquid Separation (MESLS), is designed to improve the de-watering kinetics and reduce the residual moisture content of solid particulates mechanically separated from liquid slurries. Gravitation, pressure, temperature, centrifugation, and fluid dynamics have dictated traditional solid-liquid separation for the past 50 years. The introduction of an external field (i.e. the magnetic field) offers the promise to manipulate particle behavior in an entirely new manner, which leads to increased process efficiency. Traditional solid-liquid separation typically consists of two primary steps. The first is a mechanical step in which the solid particulate is separated from the liquid using e.g. gas pressure through a filter membrane, centrifugation, etc. The second step is a thermal drying process, which is required due to imperfect mechanical separation. The thermal drying process is over 100-200 times less energy efficient than the mechanical step. Since enormous volumes of materials are processed each year, more efficient mechanical solid-liquid separations can be leveraged into dramatic reductions in overall energy consumption by reducing downstream drying requirements have a tremendous impact on energy consumption. Using DuPont's MESLS process, initial test results showed four very important effects of the magnetic field on the solid-liquid filtration process: 1) reduction of the time to reach gas breakthrough, 2) less loss of solid into the filtrate, 3) reduction of the (solids) residual moisture content, and 4) acceleration of the de-watering kinetics. These test results and their potential impact on future commercial solid-liquid filtration is discussed. New applications can be found in mining, chemical and bioprocesses.

Laser Ablation Surface Preparation of Ti-6A1-4V for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Watson, Kent A.; Morales, Guillermo; Williams, Thomas; Hicks, Robert; Wohl, Christopher J.; Hopkins, John W.; Connell, John W.

2012-01-01

Adhesive bonding offers many advantages over mechanical fastening, but requires certification before it can be incorporated in primary structures for commercial aviation without disbond-arrestment features or redundant load paths. Surface preparation is widely recognized as the key step to producing robust and predictable bonds. Laser ablation imparts both topographical and chemical changes to a surface which can lead to increased bond durability. A laser based process provides an alternative to chemical-dip, manual abrasion and grit blast treatments which are expensive, hazardous, polluting, and less precise. This report documents preliminary testing of a surface preparation technique using laser ablation as a replacement for the chemical etch and abrasive processes currently applied to Ti-6Al-4V alloy adherends. Failure mode, surface roughness, and chemical makeup were analyzed using fluorescence enhanced visualization, microscopy, and X-ray photoelectron spectroscopy, respectively. Single lap shear tests were conducted on bonded and aged specimens to observe bond strength retention and failure mode. Some promising results showed increasing strength and durability of lap shear specimens as laser ablation coverage area and beam intensity increased. Chemical analyses showed trends for surface chemical species which correlated with improved bond strength and durability. Combined, these results suggest that laser ablation is a viable process for inclusion with or/and replacement of one or more currently used titanium surface treatments. On-going work will focus on additional mechanical tests to further demonstrate improved bond durability.

Examination of Wildland Fire Spread at Small Scales Using Direct Numerical Simulations and High-Speed Laser Diagnostics

NASA Astrophysics Data System (ADS)

Wimer, N. T.; Mackoweicki, A. S.; Poludnenko, A. Y.; Hoffman, C.; Daily, J. W.; Rieker, G. B.; Hamlington, P.

2017-12-01

Results are presented from a joint computational and experimental research effort focused on understanding and characterizing wildland fire spread at small scales (roughly 1m-1mm) using direct numerical simulations (DNS) with chemical kinetics mechanisms that have been calibrated using data from high-speed laser diagnostics. The simulations are intended to directly resolve, with high physical accuracy, all small-scale fluid dynamic and chemical processes relevant to wildland fire spread. The high fidelity of the simulations is enabled by the calibration and validation of DNS sub-models using data from high-speed laser diagnostics. These diagnostics have the capability to measure temperature and chemical species concentrations, and are used here to characterize evaporation and pyrolysis processes in wildland fuels subjected to an external radiation source. The chemical kinetics code CHEMKIN-PRO is used to study and reduce complex reaction mechanisms for water removal, pyrolysis, and gas phase combustion during solid biomass burning. Simulations are then presented for a gaseous pool fire coupled with the resulting multi-step chemical reaction mechanisms, and the results are connected to the fundamental structure and spread of wildland fires. It is anticipated that the combined computational and experimental approach of this research effort will provide unprecedented access to information about chemical species, temperature, and turbulence during the entire pyrolysis, evaporation, ignition, and combustion process, thereby permitting more complete understanding of the physics that must be represented by coarse-scale numerical models of wildland fire spread.

A spectral radius scaling semi-implicit iterative time stepping method for reactive flow simulations with detailed chemistry

NASA Astrophysics Data System (ADS)

Xie, Qing; Xiao, Zhixiang; Ren, Zhuyin

2018-09-01

A spectral radius scaling semi-implicit time stepping scheme has been developed for simulating unsteady compressible reactive flows with detailed chemistry, in which the spectral radius in the LUSGS scheme has been augmented to account for viscous/diffusive and reactive terms and a scalar matrix is proposed to approximate the chemical Jacobian using the minimum species destruction timescale. The performance of the semi-implicit scheme, together with a third-order explicit Runge-Kutta scheme and a Strang splitting scheme, have been investigated in auto-ignition and laminar premixed and nonpremixed flames of three representative fuels, e.g., hydrogen, methane, and n-heptane. Results show that the minimum species destruction time scale can well represent the smallest chemical time scale in reactive flows and the proposed scheme can significantly increase the allowable time steps in simulations. The scheme is stable when the time step is as large as 10 μs, which is about three to five orders of magnitude larger than the smallest time scales in various tests considered. For the test flames considered, the semi-implicit scheme achieves second order of accuracy in time. Moreover, the errors in quantities of interest are smaller than those from the Strang splitting scheme indicating the accuracy gain when the reaction and transport terms are solved coupled. Results also show that the relative efficiency of different schemes depends on fuel mechanisms and test flames. When the minimum time scale in reactive flows is governed by transport processes instead of chemical reactions, the proposed semi-implicit scheme is more efficient than the splitting scheme. Otherwise, the relative efficiency depends on the cost in sub-iterations for convergence within each time step and in the integration for chemistry substep. Then, the capability of the compressible reacting flow solver and the proposed semi-implicit scheme is demonstrated for capturing the hydrogen detonation waves. Finally, the performance of the proposed method is demonstrated in a two-dimensional hydrogen/air diffusion flame.

Step-by-Step Simulation of Radiation Chemistry Using Green Functions for Diffusion-Influenced Reactions

NASA Technical Reports Server (NTRS)

Plante, Ianik; Cucinotta, Francis A.

2011-01-01

Radiolytic species are formed approximately 1 ps after the passage of ionizing radiation through matter. After their formation, they diffuse and chemically react with other radiolytic species and neighboring biological molecules, leading to various oxidative damage. Therefore, the simulation of radiation chemistry is of considerable importance to understand how radiolytic species damage biological molecules [1]. The step-by-step simulation of chemical reactions is difficult, because the radiolytic species are distributed non-homogeneously in the medium. Consequently, computational approaches based on Green functions for diffusion-influenced reactions should be used [2]. Recently, Green functions for more complex type of reactions have been published [3-4]. We have developed exact random variate generators of these Green functions [5], which will allow us to use them in radiation chemistry codes. Moreover, simulating chemistry using the Green functions is which is computationally very demanding, because the probabilities of reactions between each pair of particles should be evaluated at each timestep [2]. This kind of problem is well adapted for General Purpose Graphic Processing Units (GPGPU), which can handle a large number of similar calculations simultaneously. These new developments will allow us to include more complex reactions in chemistry codes, and to improve the calculation time. This code should be of importance to link radiation track structure simulations and DNA damage models.

Demand driven salt clean-up in a molten salt fast reactor – Defining a priority list

PubMed Central

Litskevich, D.; Gregg, R.; Mount, A. R.

2018-01-01

The PUREX technology based on aqueous processes is currently the leading reprocessing technology in nuclear energy systems. It seems to be the most developed and established process for light water reactor fuel and the use of solid fuel. However, demand driven development of the nuclear system opens the way to liquid fuelled reactors, and disruptive technology development through the application of an integrated fuel cycle with a direct link to reactor operation. The possibilities of this new concept for innovative reprocessing technology development are analysed, the boundary conditions are discussed, and the economic as well as the neutron physical optimization parameters of the process are elucidated. Reactor physical knowledge of the influence of different elements on the neutron economy of the reactor is required. Using an innovative study approach, an element priority list for the salt clean-up is developed, which indicates that separation of Neodymium and Caesium is desirable, as they contribute almost 50% to the loss of criticality. Separating Zirconium and Samarium in addition from the fuel salt would remove nearly 80% of the loss of criticality due to fission products. The theoretical study is followed by a qualitative discussion of the different, demand driven optimization strategies which could satisfy the conflicting interests of sustainable reactor operation, efficient chemical processing for the salt clean-up, and the related economic as well as chemical engineering consequences. A new, innovative approach of balancing the throughput through salt processing based on a low number of separation process steps is developed. Next steps for the development of an economically viable salt clean-up process are identified. PMID:29494604

Implementation of the fugitive emissions system program: The OxyChem experience

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshmukh, A.

An overview is provided for the Fugitive Emissions System (FES) that has been implemented at Occidental Chemical in conjunction with the computer-based maintenance system called PassPort{reg_sign} developed by Indus Corporation. The goal of PassPort{reg_sign} FES program has been to interface with facilities data, equipment information, work standards and work orders. Along the way, several implementation hurdles had to be overcome before a monitoring and regulatory system could be standardized for the appropriate maintenance, process and environmental groups. This presentation includes step-by-step account of several case studies that developed during the implementation of the FES system.

Advances in primary recovery: centrifugation and membrane technology.

PubMed

Roush, David J; Lu, Yuefeng

2008-01-01

Significant and continual improvements in upstream processing for biologics have resulted in challenges for downstream processing, both primary recovery and purification. Given the high cell densities achievable in both microbial and mammalian cell culture processes, primary recovery can be a significant bottleneck in both clinical and commercial manufacturing. The combination of increased product titer and low viability leads to significant relative increases in the levels of process impurities such as lipids, intracellular proteins and nucleic acid versus the product. In addition, cell culture media components such as soy and yeast hydrolysates have been widely applied to achieve the cell culture densities needed for higher titers. Many of the process impurities can be negatively charged at harvest pH and can form colloids during the cell culture and harvest processes. The wide size distribution of these particles and the potential for additional particles to be generated by shear forces within a centrifuge may result in insufficient clarification to prevent fouling of subsequent filters. The other residual process impurities can lead to precipitation and increased turbidity during processing and even interference with the performance of the capturing chromatographic step. Primary recovery also poses significant challenges owing to the necessity to execute in an expedient manner to minimize both product degradation and bioburden concerns. Both microfiltration and centrifugation coupled with depth filtration have been employed successfully as primary recovery processing steps. Advances in the design and application of membrane technology for microfiltration and dead-end filtration have contributed to significant improvements in process performance and integration, in some cases allowing for a combination of multiple unit operations in a given step. Although these advances have increased productivity and reliability, the net result is that optimization of primary recovery processes has become substantially more complicated. Ironically, the application of classical chemical engineering approaches to overcome issues in primary recovery and purification (e.g., turbidity and trace impurity removal) are just recently gaining attention. Some of these techniques (e.g., membrane cascades, pretreatment, precipitation, and the use of affinity tags) are now seen almost as disruptive technologies. This paper will review the current and potential future state of research on primary recovery, including relevant papers presented at the 234th American Chemical Society (ACS) National Meeting in Boston.

Understanding current steam sterilization recommendations and guidelines.

PubMed

Spry, Cynthia

2008-10-01

Processing surgical instruments in preparation for surgery is a complex multistep practice. It is impractical to culture each and every item to determine sterility; therefore, the best assurance of a sterile product is careful execution of every step in the process coupled with an ongoing quality control program. Perioperative staff nurses and managers responsible for instrument processing, whether for a single instrument or multiple sets, must be knowledgeable with regard to cleaning; packaging; cycle selection; and the use of physical, chemical, and biological monitors. Nurses also should be able to resolve issues related to loaner sets, flash sterilization, and extended cycles.

Prilezhaev dihydroxylation of olefins in a continuous flow process.

PubMed

van den Broek, Bas A M W; Becker, René; Kössl, Florian; Delville, Mariëlle M E; Nieuwland, Pieter J; Koch, Kaspar; Rutjes, Floris P J T

2012-02-13

Epoxidation of both terminal and non-terminal olefins with peroxy acids is a well-established and powerful tool in a wide variety of chemical processes. In an additional step, the epoxide can be readily converted into the corresponding trans-diol. Batch-wise scale-up, however, is often troublesome because of the thermal instability and explosive character of the peroxy acids involved. This article describes the design and semi-automated optimization of a continuous flow process and subsequent scale-up to preparative production volumes in an intrinsically safe manner. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Friction stir weld tools having fine grain structure

DOEpatents

Grant, Glenn J.; Frye, John G.; Kim, Jin Yong; Lavender, Curt A.; Weil, Kenneth Scott

2016-03-15

Tools for friction stir welding can be made with fewer process steps, lower cost techniques, and/or lower cost ingredients than other state-of-the-art processes by utilizing improved compositions and processes of fabrication. Furthermore, the tools resulting from the improved compositions and processes of fabrication can exhibit better distribution and homogeneity of chemical constituents, greater strength, and/or increased durability. In one example, a friction stir weld tool includes tungsten and rhenium and is characterized by carbide and oxide dispersoids, by carbide particulates, and by grains that comprise a solid solution of the tungsten and rhenium. The grains do not exceed 10 micrometers in diameter.

Block and Graft Copolymers of Polyhydroxyalkanoates

NASA Astrophysics Data System (ADS)

Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

2004-03-01

Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

Isolation and Purification of Biotechnological Products

NASA Astrophysics Data System (ADS)

Hubbuch, Jürgen; Kula, Maria-Regina

2007-05-01

The production of modern pharma proteins is one of the most rapid growing fields in biotechnology. The overall development and production is a complex task ranging from strain development and cultivation to the purification and formulation of the drug. Downstream processing, however, still accounts for the major part of production costs. This is mainly due to the high demands on purity and thus safety of the final product and results in processes with a sequence of typically more than 10 unit operations. Consequently, even if each process step would operate at near optimal yield, a very significant amount of product would be lost. The majority of unit operations applied in downstream processing have a long history in the field of chemical and process engineering; nevertheless, mathematical descriptions of the respective processes and the economical large-scale production of modern pharmaceutical products are hampered by the complexity of the biological feedstock, especially the high molecular weight and limited stability of proteins. In order to develop new operational steps as well as a successful overall process, it is thus a necessary prerequisite to develop a deeper understanding of the thermodynamics and physics behind the applied processes as well as the implications for the product.

Applying chemical engineering concepts to non-thermal plasma reactors

NASA Astrophysics Data System (ADS)

Pedro AFFONSO, NOBREGA; Alain, GAUNAND; Vandad, ROHANI; François, CAUNEAU; Laurent, FULCHERI

2018-06-01

Process scale-up remains a considerable challenge for environmental applications of non-thermal plasmas. Undersanding the impact of reactor hydrodynamics in the performance of the process is a key step to overcome this challenge. In this work, we apply chemical engineering concepts to analyse the impact that different non-thermal plasma reactor configurations and regimes, such as laminar or plug flow, may have on the reactor performance. We do this in the particular context of the removal of pollutants by non-thermal plasmas, for which a simplified model is available. We generalise this model to different reactor configurations and, under certain hypotheses, we show that a reactor in the laminar regime may have a behaviour significantly different from one in the plug flow regime, often assumed in the non-thermal plasma literature. On the other hand, we show that a packed-bed reactor behaves very similarly to one in the plug flow regime. Beyond those results, the reader will find in this work a quick introduction to chemical reaction engineering concepts.

Using Equation-Free Computation to Accelerate Network-Free Stochastic Simulation of Chemical Kinetics.

PubMed

Lin, Yen Ting; Chylek, Lily A; Lemons, Nathan W; Hlavacek, William S

2018-06-21

The chemical kinetics of many complex systems can be concisely represented by reaction rules, which can be used to generate reaction events via a kinetic Monte Carlo method that has been termed network-free simulation. Here, we demonstrate accelerated network-free simulation through a novel approach to equation-free computation. In this process, variables are introduced that approximately capture system state. Derivatives of these variables are estimated using short bursts of exact stochastic simulation and finite differencing. The variables are then projected forward in time via a numerical integration scheme, after which a new exact stochastic simulation is initialized and the whole process repeats. The projection step increases efficiency by bypassing the firing of numerous individual reaction events. As we show, the projected variables may be defined as populations of building blocks of chemical species. The maximal number of connected molecules included in these building blocks determines the degree of approximation. Equation-free acceleration of network-free simulation is found to be both accurate and efficient.

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

NASA Astrophysics Data System (ADS)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

Simulating the control of molecular reactions via modulated light fields: from gas phase to solution

NASA Astrophysics Data System (ADS)

Thallmair, Sebastian; Keefer, Daniel; Rott, Florian; de Vivie-Riedle, Regina

2017-04-01

Over the past few years quantum control has proven to be very successful in steering molecular processes. By combining theory with experiment, even highly complex control aims were realized in the gas phase. In this topical review, we illustrate the past achievements on several examples in the molecular context. The next step for the quantum control of chemical processes is to translate the fruitful interplay between theory and experiment to the condensed phase and thus to the regime where chemical synthesis can be supported. On the theory side, increased efforts to include solvent effects in quantum control simulations were made recently. We discuss two major concepts, namely an implicit description of the environment via the density matrix algorithm and an explicit inclusion of solvent molecules. By application to chemical reactions, both concepts conclude that despite environmental perturbations leading to more complex control tasks, efficient quantum control in the condensed phase is still feasible.

Self-cleaning poly(dimethylsiloxane) film with functional micro/nano hierarchical structures.

PubMed

Zhang, Xiao-Sheng; Zhu, Fu-Yun; Han, Meng-Di; Sun, Xu-Ming; Peng, Xu-Hua; Zhang, Hai-Xia

2013-08-27

This paper reports a novel single-step wafer-level fabrication of superhydrophobic micro/nano dual-scale (MNDS) poly(dimethylsiloxane) (PDMS) films. The MNDS PDMS films were replicated directly from an ultralow-surface-energy silicon substrate at high temperature without any surfactant coating, achieving high precision. An improved deep reactive ion etching (DRIE) process with enhanced passivation steps was proposed to easily realize the ultralow-surface-energy MNDS silicon substrate and also utilized as a post-treatment process to strengthen the hydrophobicity of the MNDS PDMS film. The chemical modification of this enhanced passivation step to the surface energy has been studied by density functional theory, which is also the first investigation of C4F8 plasma treatment at molecular level by using first-principle calculations. From the results of a systematic study on the effect of key process parameters (i.e., baking temperature and time) on PDMS replication, insight into the interaction of hierarchical multiscale structures of polymeric materials during the micro/nano integrated fabrication process is experimentally obtained for the first time. Finite element simulation has been employed to illustrate this new phenomenon. Additionally, hierarchical PDMS pyramid arrays and V-shaped grooves have been developed and are intended for applications as functional structures for a light-absorption coating layer and directional transport of liquid droplets, respectively. This stable, self-cleaning PDMS film with functional micro/nano hierarchical structures, which is fabricated through a wafer-level single-step fabrication process using a reusable silicon mold, shows attractive potential for future applications in micro/nanodevices, especially in micro/nanofluidics.

Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

PubMed

Djikaev, Yuri S; Ruckenstein, Eli

2018-05-03

We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

Investigating the feasibility of scale up and automation of human induced pluripotent stem cells cultured in aggregates in feeder free conditions☆

PubMed Central

Soares, Filipa A.C.; Chandra, Amit; Thomas, Robert J.; Pedersen, Roger A.; Vallier, Ludovic; Williams, David J.

2014-01-01

The transfer of a laboratory process into a manufacturing facility is one of the most critical steps required for the large scale production of cell-based therapy products. This study describes the first published protocol for scalable automated expansion of human induced pluripotent stem cell lines growing in aggregates in feeder-free and chemically defined medium. Cells were successfully transferred between different sites representative of research and manufacturing settings; and passaged manually and using the CompacT SelecT automation platform. Modified protocols were developed for the automated system and the management of cells aggregates (clumps) was identified as the critical step. Cellular morphology, pluripotency gene expression and differentiation into the three germ layers have been used compare the outcomes of manual and automated processes. PMID:24440272

Pulse plating of Pt on n-GaAs ( 1 0 0 ) wafer surfaces: Synchrotron induced photoelectron spectroscopy and XPS of wet fabrication processes

NASA Astrophysics Data System (ADS)

Ensling, D.; Hunger, R.; Kraft, D.; Mayer, Th.; Jaegermann, W.; Rodriguez-Girones, M.; Ichizli, V.; Hartnagel, H. L.

2003-01-01

Preparation steps of Pt/n-GaAs Schottky contacts as applied in the fabrication process of varactor diode arrays for THz applications are analysed by photoelectron spectroscopy. Pulsed cathodic deposition of Pt onto GaAs (1 0 0) wafer surfaces from acidic solution has been studied by core level photoelectron spectroscopy using different excitation energies. A laboratory AlKα source as well as synchrotron radiation of hν=130 and 645 eV at BESSY was used. Chemical analyses and semiquantitative estimates of layer thickness are given for the natural oxide of an untreated wafer surface, a surface conditioning NH 3 etching step, and stepwise pulse plating of Pt. The structural arrangement of the detected species and interface potentials are considered.

Oxygen plasma etching of graphene: A first-principles dynamical inspection of the reaction mechanisms and related activation barriers

NASA Astrophysics Data System (ADS)

Koizumi, Kenichi; Boero, Mauro; Shigeta, Yasuteru; Oshiyama, Atsushi; Dept. of Applied Physics Team; Institute of Physics and Chemistry of Strasbourg (IPCMS) Collaboration; Department Of Materials Engineering Science Collaboration

2013-03-01

Oxygen plasma etching is a crucial step in the fabrication of electronic circuits and has recently received a renovated interest in view of the realization of carbon-based nanodevices. In an attempt at unraveling the atomic-scale details and to provide guidelines for the control of the etching processes mechanisms, we inspected the possible reaction pathways via reactive first principles simulations. These processes involve breaking and formation of several chemical bonds and are characterized by different free-energy barriers. Free-energy sampling techniques (metadynamics and blue moon), used to enhance the standard Car-Parrinello molecular dynamics, provide us a detailed microscopic picture of the etching of graphene surfaces and a comprehensive scenario of the activation barriers involved in the various steps. MEXT, Japan - contract N. 22104005

A citrus waste-based biorefinery as a source of renewable energy: technical advances and analysis of engineering challenges.

PubMed

Rivas-Cantu, Raul C; Jones, Kim D; Mills, Patrick L

2013-04-01

An assessment of recent technical advances on pretreatment processes and its effects on enzymatic hydrolysis as the main steps of a proposed citrus processing waste (CPW) biorefinery is presented. Engineering challenges and relevant gaps in scientific and technical information for reliable design, modeling and scale up of a CPW biorefinery are also discussed. Some integrated physico-chemical pretreatments are proposed for testing for CPW, including high speed knife-grinding and simultaneous caustic addition. These new proposed processes and the effect of parameters such as particle size, surface area and morphology, pore volume and chemical composition of the diverse fractions resulting from pretreatment and enzymatic hydrolysis need to be evaluated and compared for pretreated and untreated samples of grapefruit processing waste. This assessment suggests the potential for filling the data gaps, and preliminary results demonstrate that the reduction of particle size and the increased surface area for the CPW will result in higher reaction rates and monosaccharide yields for the pretreated waste material.

Production of Chitin from Penaeus vannamei By-Products to Pilot Plant Scale Using a Combination of Enzymatic and Chemical Processes and Subsequent Optimization of the Chemical Production of Chitosan by Response Surface Methodology.

PubMed

Vázquez, José A; Ramos, Patrícia; Mirón, Jesús; Valcarcel, Jesus; Sotelo, Carmen G; Pérez-Martín, Ricardo I

2017-06-16

The waste generated from shrimp processing contains valuable materials such as protein, carotenoids, and chitin. The present study describes a process at pilot plant scale to recover chitin from the cephalothorax of Penaeus vannamei using mild conditions. The application of a sequential enzymatic-acid-alkaline treatment yields 30% chitin of comparable purity to commercial sources. Effluents from the process are rich in protein and astaxanthin, and represent inputs for further by-product recovery. As a last step, chitin is deacetylated to produce chitosan; the optimal conditions are established by applying a response surface methodology (RSM). Under these conditions, deacetylation reaches 92% as determined by Proton Nuclear Magnetic Resonance (¹H-NMR), and the molecular weight (Mw) of chitosan is estimated at 82 KDa by gel permeation chromatography (GPC). Chitin and chitosan microstructures are characterized by Scanning Electron Microscopy (SEM).

Field programmable chemistry: integrated chemical and electronic processing of informational molecules towards electronic chemical cells.

PubMed

Wagler, Patrick F; Tangen, Uwe; Maeke, Thomas; McCaskill, John S

2012-07-01

The topic addressed is that of combining self-constructing chemical systems with electronic computation to form unconventional embedded computation systems performing complex nano-scale chemical tasks autonomously. The hybrid route to complex programmable chemistry, and ultimately to artificial cells based on novel chemistry, requires a solution of the two-way massively parallel coupling problem between digital electronics and chemical systems. We present a chemical microprocessor technology and show how it can provide a generic programmable platform for complex molecular processing tasks in Field Programmable Chemistry, including steps towards the grand challenge of constructing the first electronic chemical cells. Field programmable chemistry employs a massively parallel field of electrodes, under the control of latched voltages, which are used to modulate chemical activity. We implement such a field programmable chemistry which links to chemistry in rather generic, two-phase microfluidic channel networks that are separated into weakly coupled domains. Electric fields, produced by the high-density array of electrodes embedded in the channel floors, are used to control the transport of chemicals across the hydrodynamic barriers separating domains. In the absence of electric fields, separate microfluidic domains are essentially independent with only slow diffusional interchange of chemicals. Electronic chemical cells, based on chemical microprocessors, exploit a spatially resolved sandwich structure in which the electronic and chemical systems are locally coupled through homogeneous fine-grained actuation and sensor networks and play symmetric and complementary roles. We describe how these systems are fabricated, experimentally test their basic functionality, simulate their potential (e.g. for feed forward digital electrophoretic (FFDE) separation) and outline the application to building electronic chemical cells. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minitti, Michael

2015-06-22

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

DOEpatents

Lowden, R.A.

1994-04-05

A process for chemical vapor deposition of crystalline silicon nitride is described which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide. 5 figures.

Comparative Metabolism of Hydrazine and Naphthalene.

DTIC Science & Technology

1980-09-01

compounds and chemicals like those in cigarette smoke. Another question of considerable importance to the Air Force is whether animal species currently...the pulmonary cytochrome P-450 monooxygenases differ between species or that enzymes responsible for the detoxification of the "toxic" metabolite(s...metabolic steps in the activation and detoxification of a compound like naphthalene are undertaken in animal lung tissue so that such processes can be

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

ScienceCinema

Minitti, Michael

2018-02-14

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

Fiber-Coupled Acousto-Optical-Filter Spectrometer

NASA Technical Reports Server (NTRS)

Levin, Kenneth H.; Li, Frank Yanan

1993-01-01

Fiber-coupled acousto-optical-filter spectrometer steps rapidly through commanded sequence of wavelengths. Sample cell located remotely from monochromator and associated electronic circuitry, connected to them with optical fibers. Optical-fiber coupling makes possible to monitor samples in remote, hazardous, or confined locations. Advantages include compactness, speed, and no moving parts. Potential applications include control of chemical processes, medical diagnoses, spectral imaging, and sampling of atmospheres.

A process for the preparation of cysteine from cystine

DOEpatents

Chang, Shih-Ger; Liu, David K.; Griffiths, Elizabeth A.; Littlejohn, David

1989-01-01

The present invention in one aspect relates to a process for the simultaneous removal of NO.sub.x and SO.sub.2 from a fluid stream comprising mixtures thereof and in another aspect relates to the separation, use and/or regeneration of various chemicals contaminated or spent in the process and which includes the steps of: (A) contacting the fluid stream at a temperature of between about 105.degree. and 180.degree. C. with a liquid aqueous slurry or solution comprising an effective amount of an iron chelate of an amino acid moiety having at least one --SH group; (B) separating the fluid stream from the particulates formed in step (A) comprising the chelate of the amino acid moiety and fly ash; (C) washing and separating the particulates of step (B) with an aqeous solution having a pH value of between about 5 to 8; (D) subsequently washing and separating the particulates of step (C) with a strongly acidic aqueous solution having a pH value of between about 1 to 3; (E) washing and separating the particulates of step (D) with an basic aqueous solution having a pH value of between about 9 to 12; (F) optionally adding additional amino acid moiety, iron (II) and alkali to the aqueous liquid from step (D) to produce an aqueous solution or slurry similar to that in step (A) having a pH value of between about 4 to 12; and (G) recycling the aqueous slurry of step (F) to the contacting zone of step (A). Steps (D) and (E) can be carried out in the reverse sequence, however the preferred order is (D) and then (E). In a preferred embodiment the present invention provides an improved process for the preparation (regeneration) of cysteine from cystine, which includes reacting an aqueous solution of cystine at a pH of between about 9 to 13 with a reducing agent selected from hydrogen sulfide or alkali metal sulfides, sulfur dioxide, an alkali metal sulfite or mixtures thereof for a time and at a temperature effective to cleave and reduce the cystine to cysteine with subsequent recovery of the cysteine. In another preferred embodiment the present invention provides a process for the removal of NO.sub.x, SO.sub.2 and particulates from a fluid stream which includes the steps of (A) injecting into a reaction zone an aqueous solution itself comprising (i) an amino acid moiety selected from those described above; (ii) iron (II) ion; and (iii) an alkali, wherein the aqueous solution has a pH of between about 4 and 11; followed by solids separation and washing as is described in steps (B), (C), (D) and (E) above. The overall process is useful to reduce acid rain components from combustion gas sources.

A workflow for improving estimates of microplastic contamination in marine waters: A case study from North-Western Australia.

PubMed

Kroon, Frederieke; Motti, Cherie; Talbot, Sam; Sobral, Paula; Puotinen, Marji

2018-07-01

Plastic pollution is ubiquitous throughout the marine environment, with microplastic (i.e. <5 mm) contamination a global issue of emerging concern. The lack of universally accepted methods for quantifying microplastic contamination, including consistent application of microscopy, photography, an spectroscopy and photography, may result in unrealistic contamination estimates. Here, we present and apply an analysis workflow tailored to quantifying microplastic contamination in marine waters, incorporating stereomicroscopic visual sorting, microscopic photography and attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. The workflow outlines step-by-step processing and associated decision making, thereby reducing bias in plastic identification and improving confidence in contamination estimates. Specific processing steps include (i) the use of a commercial algorithm-based comparison of particle spectra against an extensive commercially curated spectral library, followed by spectral interpretation to establish the chemical composition, (ii) a comparison against a customised contaminant spectral library to eliminate procedural contaminants, and (iii) final assignment of particles as either natural- or anthropogenic-derived materials, based on chemical type, a compare analysis of each particle against other particle spectra, and physical characteristics of particles. Applying this workflow to 54 tow samples collected in marine waters of North-Western Australia visually identified 248 potential anthropogenic particles. Subsequent ATR-FTIR spectroscopy, chemical assignment and visual re-inspection of photographs established 144 (58%) particles to be of anthropogenic origin. Of the original 248 particles, 97 (39%) were ultimately confirmed to be plastics, with 85 of these (34%) classified as microplastics, demonstrating that over 60% of particles may be misidentified as plastics if visual identification is not complemented by spectroscopy. Combined, this tailored analysis workflow outlines a consistent and sequential process to quantify contamination by microplastics and other anthropogenic microparticles in marine waters. Importantly, its application will contribute to more realistic estimates of microplastic contamination in marine waters, informing both ecological risk assessments and experimental concentrations in effect studies. Copyright © 2018 Australian Institute of Marine Science. Published by Elsevier Ltd.. All rights reserved.

Mature landfill leachate treatment by coagulation/flocculation combined with Fenton and solar photo-Fenton processes.

PubMed

Amor, Carlos; De Torres-Socías, Estefanía; Peres, José A; Maldonado, Manuel I; Oller, Isabel; Malato, Sixto; Lucas, Marco S

2015-04-09

This work reports the treatment of a mature landfill leachate through the application of chemical-based treatment processes in order to achieve the discharge legal limits into natural water courses. Firstly, the effect of coagulation/flocculation with different chemicals was studied, evaluating the role of different initial pH and chemicals concentration. Afterwards, the efficiency of two different advanced oxidation processes for leachate remediation was assessed. Fenton and solar photo-Fenton processes were applied alone and in combination with a coagulation/flocculation pre-treatment. This physicochemical conditioning step, with 2 g L(-1) of FeCl3 · 6H2O at pH 5, allowed removing 63% of COD, 80% of turbidity and 74% of total polyphenols. Combining the coagulation/flocculation pre-treatment with Fenton reagent, it was possible to reach 89% of COD removal in 96 h. Moreover, coagulation/flocculation combined with solar photo-Fenton revealed higher DOC (75%) reductions than single solar photo-Fenton (54%). In the combined treatment (coagulation/flocculation and solar photo-Fenton), it was reached a DOC reduction of 50% after the chemical oxidation, with 110 kJ L(-1) of accumulated UV energy and a H2O2 consumption of 116 mM. Toxicity and biodegradability assays were performed to evaluate possible variations along the oxidation processes. After the combined treatment, the leachate under study presented non-toxicity but biodegradability increased. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical and morphological characterization of sugarcane bagasse submitted to a delignification process for enhanced enzymatic digestibility

PubMed Central

2011-01-01

Background In recent years, biorefining of lignocellulosic biomass to produce multi-products such as ethanol and other biomaterials has become a dynamic research area. Pretreatment technologies that fractionate sugarcane bagasse are essential for the successful use of this feedstock in ethanol production. In this paper, we investigate modifications in the morphology and chemical composition of sugarcane bagasse submitted to a two-step treatment, using diluted acid followed by a delignification process with increasing sodium hydroxide concentrations. Detailed chemical and morphological characterization of the samples after each pretreatment condition, studied by high performance liquid chromatography, solid-state nuclear magnetic resonance, diffuse reflectance Fourier transformed infrared spectroscopy and scanning electron microscopy, is reported, together with sample crystallinity and enzymatic digestibility. Results Chemical composition analysis performed on samples obtained after different pretreatment conditions showed that up to 96% and 85% of hemicellulose and lignin fractions, respectively, were removed by this two-step method when sodium hydroxide concentrations of 1% (m/v) or higher were used. The efficient lignin removal resulted in an enhanced hydrolysis yield reaching values around 100%. Considering the cellulose loss due to the pretreatment (maximum of 30%, depending on the process), the total cellulose conversion increases significantly from 22.0% (value for the untreated bagasse) to 72.4%. The delignification process, with consequent increase in the cellulose to lignin ratio, is also clearly observed by nuclear magnetic resonance and diffuse reflectance Fourier transformed infrared spectroscopy experiments. We also demonstrated that the morphological changes contributing to this remarkable improvement occur as a consequence of lignin removal from the sample. Bagasse unstructuring is favored by the loss of cohesion between neighboring cell walls, as well as by changes in the inner cell wall structure, such as damaging, hole formation and loss of mechanical resistance, facilitating liquid and enzyme access to crystalline cellulose. Conclusions The results presented herewith show the efficiency of the proposed method for improving the enzymatic digestibility of sugarcane bagasse and provide understanding of the pretreatment action mechanism. Combining the different techniques applied in this work warranted thorough information about the undergoing morphological and chemical changes and was an efficient approach to understand the morphological effects resulting from sample delignification and its influence on the enhanced hydrolysis results. PMID:22122978

Apatite grown in niobium by two-step plasma electrolytic oxidation.

PubMed

Pereira, Bruno Leandro; Lepienski, Carlos Maurício; Mazzaro, Irineu; Kuromoto, Neide Kazue

2017-08-01

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1μL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb 2 O 5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition. Copyright © 2016 Elsevier B.V. All rights reserved.

Recovery of permittivity and depth from near-field data as a step toward infrared nanotomography.

PubMed

Govyadinov, Alexander A; Mastel, Stefan; Golmar, Federico; Chuvilin, Andrey; Carney, P Scott; Hillenbrand, Rainer

2014-07-22

The increasing complexity of composite materials structured on the nanometer scale requires highly sensitive analytical tools for nanoscale chemical identification, ideally in three dimensions. While infrared near-field microscopy provides high chemical sensitivity and nanoscopic spatial resolution in two dimensions, the quantitative extraction of material properties of three-dimensionally structured samples has not been achieved yet. Here we introduce a method to perform rapid recovery of the thickness and permittivity of simple 3D structures (such as thin films and nanostructures) from near-field measurements, and provide its first experimental demonstration. This is accomplished via a novel nonlinear invertible model of the imaging process, taking advantage of the near-field data recorded at multiple harmonics of the oscillation frequency of the near-field probe. Our work enables quantitative nanoscale-resolved optical studies of thin films, coatings, and functionalization layers, as well as the structural analysis of multiphase materials, among others. It represents a major step toward the further goal of near-field nanotomography.

Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Dong; Liu, Dan; Harris, Joshua B.

The mechanism of the sulfur cathode in Li-S batteries has been proposed. It was revealed by the real-time quantitative determination of polysulfide species and elemental sulfur by means of the high performance liquid chromatography in the course of the discharge and recharge of a Li-S battery. A three-step reduction mechanism including two chemical equilibrium reactions was proposed for the sulfur cathode discharge. The typical two-plateau discharge curve for sulfur cathode can be explained. A two-step oxidation mechanism for the Li 2S and Li 2S 2 with a single chemical equilibrium among soluble polysulfide ions was proposed. In conclusion, the chemicalmore » equilibrium among S 5 2-, S 6 2-, S 7 2- and S 8 2- throughout the entire oxidation process resulted for the single flat recharge curve in Li-S batteries.« less

Plasmonic hot carrier dynamics in solid-state and chemical systems for energy conversion

DOE PAGES

Narang, Prineha; Sundararaman, Ravishankar; Atwater, Harry A.

2016-06-11

Surface plasmons provide a pathway to efficiently absorb and confine light in metallic nanostructures, thereby bridging photonics to the nano scale. The decay of surface plasmons generates energetic ‘hot’ carriers, which can drive chemical reactions or be injected into semiconductors for nano-scale photochemical or photovoltaic energy conversion. Novel plasmonic hot carrier devices and architectures continue to be demonstrated, but the complexity of the underlying processes make a complete microscopic understanding of all the mechanisms and design considerations for such devices extremely challenging.Here,we review the theoretical and computational efforts to understand and model plasmonic hot carrier devices.We split the problem intomore » three steps: hot carrier generation, transport and collection, and review theoretical approaches with the appropriate level of detail for each step along with their predictions. As a result, we identify the key advances necessary to complete the microscopic mechanistic picture and facilitate the design of the next generation of devices and materials for plasmonic energy conversion.« less

Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge

DOE PAGES

Zheng, Dong; Liu, Dan; Harris, Joshua B.; ...

2016-09-09

The mechanism of the sulfur cathode in Li-S batteries has been proposed. It was revealed by the real-time quantitative determination of polysulfide species and elemental sulfur by means of the high performance liquid chromatography in the course of the discharge and recharge of a Li-S battery. A three-step reduction mechanism including two chemical equilibrium reactions was proposed for the sulfur cathode discharge. The typical two-plateau discharge curve for sulfur cathode can be explained. A two-step oxidation mechanism for the Li 2S and Li 2S 2 with a single chemical equilibrium among soluble polysulfide ions was proposed. In conclusion, the chemicalmore » equilibrium among S 5 2-, S 6 2-, S 7 2- and S 8 2- throughout the entire oxidation process resulted for the single flat recharge curve in Li-S batteries.« less

2'-O-methylation in mRNA disrupts tRNA decoding during translation elongation.

PubMed

Choi, Junhong; Indrisiunaite, Gabriele; DeMirci, Hasan; Ieong, Ka-Weng; Wang, Jinfan; Petrov, Alexey; Prabhakar, Arjun; Rechavi, Gideon; Dominissini, Dan; He, Chuan; Ehrenberg, Måns; Puglisi, Joseph D

2018-03-01

Chemical modifications of mRNA may regulate many aspects of mRNA processing and protein synthesis. Recently, 2'-O-methylation of nucleotides was identified as a frequent modification in translated regions of human mRNA, showing enrichment in codons for certain amino acids. Here, using single-molecule, bulk kinetics and structural methods, we show that 2'-O-methylation within coding regions of mRNA disrupts key steps in codon reading during cognate tRNA selection. Our results suggest that 2'-O-methylation sterically perturbs interactions of ribosomal-monitoring bases (G530, A1492 and A1493) with cognate codon-anticodon helices, thereby inhibiting downstream GTP hydrolysis by elongation factor Tu (EF-Tu) and A-site tRNA accommodation, leading to excessive rejection of cognate aminoacylated tRNAs in initial selection and proofreading. Our current and prior findings highlight how chemical modifications of mRNA tune the dynamics of protein synthesis at different steps of translation elongation.

Toxicant-induced loss of tolerance--an emerging theory of disease?

PubMed Central

Miller, C S

1997-01-01

This paper attempts to clarify the nature of chemical sensitivity by proposing a theory of disease that unites the disparate clinical observations associated with the condition. Sensitivity to chemicals appears to be the consequence of a two-step process: loss of tolerance in susceptible persons following exposure to various toxicants, and subsequent triggering of symptoms by extremely small quantities of previously tolerated chemicals, drugs, foods, and food and drug combinations including caffeine and alcohol. Although chemical sensitivity may be the consequence of this process, a term that may more clearly describe the observed process is toxicant-induced loss of tolerance. Features of this yet-to-be-proven mechanism or theory of disease that affect the design of human exposure studies include the stimulatory and withdrawallike nature (resembling addiction) of symptoms reported by patients and masking. Masking, which may blunt or eliminate responses to chemical challenges, appears to have several components: apposition, which is the overlapping of the effects of closely timed exposures, acclimatization or habituation, and addiction. A number of human challenge studies in this area have concluded that there is no physiological basis for chemical sensitivity. However, these studies have failed to address the role of masking. To ensure reliable and reproducible responses to challenges, future studies in which subjects are evaluated in an environmental medical unit, a hospital-based facility in which background chemical exposures are reduced to the lowest levels practicable, may be necessary. A set of postulates is offered to determine whether there is a causal relationship between low-level chemical exposures and symptoms using an environmental medical unit. Images Figure 2. Figure 8. PMID:9167978

Densitometric evaluation of three intra-oral radiographic films.

PubMed

Seeliger, J E; Prinsloo, J J

1989-05-01

The radiographic, or diagnostic, quality of the processed radiograph depends upon a number of factors, one of the most important being the characteristics of the film. The purpose of this study was to determine which of three intra-oral radiographic films, obtainable in this country, would give the best results in terms of density range, speed, contrast and base plus fog values. Agfa Dentus, Flow X-Ray and Kodak (all speed group D films) were exposed, using a calibrated G.E. 1000 x-ray generator at 65 kVp, 10 mA and 50 impulses (1 second) exposure time. The target-film-distance was 40 cm, the total filtration 2.0 mm Aluminium and the half-value layer 2.7 mm Aluminium equivalent. An aluminium step-wedge with 8 steps, in steps of 1.5 mm, and a natural premolar tooth, with a carious lesion, embedded in acrylic, were used as phantoms. An 8 mm-thick layer of base-plate wax and a 3 mm-thick lead plate were used to simulate tissue-scatter and prevent back-scatter, respectively. To determine the base plug fog value, an unexposed film from the same batch was processed simultaneously with each of the three films evaluated. All processing was done in a Dürr AC 245 L processor with automatic replenishment and a 6-minute cycle. The processing chemicals, viz., Kolchem High Stability X-ray developer and fixer, were mixed and used in strict accordance with the manufacturer's recommendations. The radiographic densities of each step of the step-wedge, and of carious and normal dentine of the phantom tooth, were determined by means of an RMI Digital Densitometer.(ABSTRACT TRUNCATED AT 250 WORDS)

Converting Panax ginseng DNA and chemical fingerprints into two-dimensional barcode.

PubMed

Cai, Yong; Li, Peng; Li, Xi-Wen; Zhao, Jing; Chen, Hai; Yang, Qing; Hu, Hao

2017-07-01

In this study, we investigated how to convert the Panax ginseng DNA sequence code and chemical fingerprints into a two-dimensional code. In order to improve the compression efficiency, GATC2Bytes and digital merger compression algorithms are proposed. HPLC chemical fingerprint data of 10 groups of P. ginseng from Northeast China and the internal transcribed spacer 2 (ITS2) sequence code as the DNA sequence code were ready for conversion. In order to convert such data into a two-dimensional code, the following six steps were performed: First, the chemical fingerprint characteristic data sets were obtained through the inflection filtering algorithm. Second, precompression processing of such data sets is undertaken. Third, precompression processing was undertaken with the P. ginseng DNA (ITS2) sequence codes. Fourth, the precompressed chemical fingerprint data and the DNA (ITS2) sequence code were combined in accordance with the set data format. Such combined data can be compressed by Zlib, an open source data compression algorithm. Finally, the compressed data generated a two-dimensional code called a quick response code (QR code). Through the abovementioned converting process, it can be found that the number of bytes needed for storing P. ginseng chemical fingerprints and its DNA (ITS2) sequence code can be greatly reduced. After GTCA2Bytes algorithm processing, the ITS2 compression rate reaches 75% and the chemical fingerprint compression rate exceeds 99.65% via filtration and digital merger compression algorithm processing. Therefore, the overall compression ratio even exceeds 99.36%. The capacity of the formed QR code is around 0.5k, which can easily and successfully be read and identified by any smartphone. P. ginseng chemical fingerprints and its DNA (ITS2) sequence code can form a QR code after data processing, and therefore the QR code can be a perfect carrier of the authenticity and quality of P. ginseng information. This study provides a theoretical basis for the development of a quality traceability system of traditional Chinese medicine based on a two-dimensional code.

Double-Vacuum-Bag Process for Making Resin-Matrix Composites

NASA Technical Reports Server (NTRS)

Bradford, Larry J.

2007-01-01

A double-vacuum-bag process has been devised as a superior alternative to a single-vacuum-bag process used heretofore in making laminated fiber-reinforced resin-matrix composite-material structural components. This process is applicable to broad classes of high-performance matrix resins including polyimides and phenolics that emit volatile compounds (solvents and volatile by-products of resin-curing chemical reactions) during processing. The superiority of the double-vacuum-bag process lies in enhanced management of the volatile compounds. Proper management of volatiles is necessary for making composite-material components of high quality: if not removed and otherwise properly managed, volatiles can accumulate in interior pockets as resins cure, thereby forming undesired voids in the finished products. The curing cycle for manufacturing a composite laminate containing a reactive resin matrix usually consists of a two-step ramp-and-hold temperature profile and an associated single-step pressure profile as shown in Figure 1. The lower-temperature ramp-and-hold step is known in the art as the B stage. During the B stage, prepregs are heated and volatiles are generated. Because pressure is not applied at this stage, volatiles are free to escape. Pressure is applied during the higher-temperature ramp-and-hold step to consolidate the laminate and impart desired physical properties to the resin matrix. The residual volatile content and fluidity of the resin at the beginning of application of consolidation pressure are determined by the temperature and time parameters of the B stage. Once the consolidation pressure is applied, residual volatiles are locked in. In order to produce a void-free, high-quality laminate, it is necessary to design the curing cycle to obtain the required residual fluidity and the required temperature at the time of application of the consolidation pressure.

Assessment of an improved bone washing protocol for deceased donor human bone.

PubMed

Eagle, M J; Man, J; Rooney, P; Hogg, P; Kearney, J N

2015-03-01

NHSBT Tissue Services issues bone to surgeons in the UK in two formats, fresh-frozen unprocessed bone from living donors and processed bone from deceased donors. Processed bone may be frozen or freeze dried and all processed bone is currently subjected to a washing protocol to remove blood and bone marrow. In this study we have improved the current bone washing protocol for cancellous bone and assessed the success of the protocol by measuring the removal of the bone marrow components: soluble protein, DNA and haemoglobin at each step in the process, and residual components in the bone at the end of the process. The bone washing protocol is a combination of sonication, warm water washes, centrifugation and chemical (ethanol and hydrogen peroxide) treatments. We report that the bone washing protocol is capable of removing up to 99.85 % soluble protein, 99.95 % DNA and 100 % of haemoglobin from bone. The new bone washing protocol does not render any bone cytotoxic as shown by contact cytotoxicity assays. No microbiological cell growth was detected in any of the wash steps. This process is now in use for processed cancellous bone issued by NHSBT.

Novel Chemical Process for Producing Chrome Coated Metal

PubMed Central

Pelar, Christopher; Greenaway, Karima; Zea, Hugo; Wu, Chun-Hsien

2018-01-01

This work demonstrates that a version of the Reduction Expansion Synthesis (RES) process, Cr-RES, can create a micron scale Cr coating on an iron wire. The process involves three steps. I. A paste consisting of a physical mix of urea, chrome nitrate or chrome oxide, and water is prepared. II. An iron wire is coated by dipping. III. The coated, and dried, wire is heated to ~800 °C for 10 min in a tube furnace under a slow flow of nitrogen gas. The processed wires were then polished and characterized, primarily with scanning electron microscopy (SEM). SEM indicates the chrome layer is uneven, but only on the scale of a fraction of a micron. The evidence of porosity is ambiguous. Elemental mapping using SEM electron microprobe that confirmed the process led to the formation of a chrome metal layer, with no evidence of alloy formation. Additionally, it was found that thickness of the final Cr layer correlated with the thickness of the precursor layer that was applied prior to the heating step. Potentially, this technique could replace electrolytic processing, a process that generates carcinogenic hexavalent chrome, but further study and development is needed. PMID:29303977

Novel Chemical Process for Producing Chrome Coated Metal.

PubMed

Pelar, Christopher; Greenaway, Karima; Zea, Hugo; Wu, Chun-Hsien; Luhrs, Claudia C; Phillips, Jonathan

2018-01-05

This work demonstrates that a version of the Reduction Expansion Synthesis (RES) process, Cr-RES, can create a micron scale Cr coating on an iron wire. The process involves three steps. I. A paste consisting of a physical mix of urea, chrome nitrate or chrome oxide, and water is prepared. II. An iron wire is coated by dipping. III. The coated, and dried, wire is heated to ~800 °C for 10 min in a tube furnace under a slow flow of nitrogen gas. The processed wires were then polished and characterized, primarily with scanning electron microscopy (SEM). SEM indicates the chrome layer is uneven, but only on the scale of a fraction of a micron. The evidence of porosity is ambiguous. Elemental mapping using SEM electron microprobe that confirmed the process led to the formation of a chrome metal layer, with no evidence of alloy formation. Additionally, it was found that thickness of the final Cr layer correlated with the thickness of the precursor layer that was applied prior to the heating step. Potentially, this technique could replace electrolytic processing, a process that generates carcinogenic hexavalent chrome, but further study and development is needed.

Internal and external atomic steps in graphite exhibit dramatically different physical and chemical properties.

PubMed

Lee, Hyunsoo; Lee, Han-Bo-Ram; Kwon, Sangku; Salmeron, Miquel; Park, Jeong Young

2015-04-28

We report on the physical and chemical properties of atomic steps on the surface of highly oriented pyrolytic graphite (HOPG) investigated using atomic force microscopy. Two types of step edges are identified: internal (formed during crystal growth) and external (formed by mechanical cleavage of bulk HOPG). The external steps exhibit higher friction than the internal steps due to the broken bonds of the exposed edge C atoms, while carbon atoms in the internal steps are not exposed. The reactivity of the atomic steps is manifested in a variety of ways, including the preferential attachment of Pt nanoparticles deposited on HOPG when using atomic layer deposition and KOH clusters formed during drop casting from aqueous solutions. These phenomena imply that only external atomic steps can be used for selective electrodeposition for nanoscale electronic devices.

Effects-based chemical category approach for prioritization of low affinity estrogenic chemicals.

PubMed

Hornung, M W; Tapper, M A; Denny, J S; Kolanczyk, R C; Sheedy, B R; Hartig, P C; Aladjov, H; Henry, T R; Schmieder, P K

2014-01-01

Regulatory agencies are charged with addressing the endocrine disrupting potential of large numbers of chemicals for which there is often little or no data on which to make decisions. Prioritizing the chemicals of greatest concern for further screening for potential hazard to humans and wildlife is an initial step in the process. This paper presents the collection of in vitro data using assays optimized to detect low affinity estrogen receptor (ER) binding chemicals and the use of that data to build effects-based chemical categories following QSAR approaches and principles pioneered by Gilman Veith and colleagues for application to environmental regulatory challenges. Effects-based chemical categories were built using these QSAR principles focused on the types of chemicals in the specific regulatory domain of concern, i.e. non-steroidal industrial chemicals, and based upon a mechanistic hypothesis of how these non-steroidal chemicals of seemingly dissimilar structure to 17ß-estradiol (E2) could interact with the ER via two distinct binding types. Chemicals were also tested to solubility thereby minimizing false negatives and providing confidence in determination of chemicals as inactive. The high-quality data collected in this manner were used to build an ER expert system for chemical prioritization described in a companion article in this journal.

Single-step enantioselective amino acid flux analysis by capillary electrophoresis using on-line sample preconcentration with chemical derivatization.

PubMed

Ptolemy, Adam S; Tran, Lara; Britz-McKibbin, Philip

2006-07-15

Capillary electrophoresis (CE) represents a versatile platform for integrating sample pretreatment with chemical analysis because of its ability to tune analyte electromigration and band dispersion properties in discontinuous electrolyte systems. In this article, a single-step method that combines on-line sample preconcentration with in-capillary chemical derivatization is developed for rapid, sensitive, and enantioselective analysis of micromolar levels of amino acids that lack intrinsic chromophores by CE with UV detection. Time-resolved electrophoretic studies revealed two distinct stages of amino acid band narrowing within the original long sample injection plug occurring both prior to and after in-capillary labeling via zone passing by ortho-phthalaldehyde/N-acetyl l-cysteine (OPA/NAC). This technique enabled direct analysis of d-amino acids in a 95% enantiomeric excess mixture with sub-micromolar detection limits and minimal sample handling, where the capillary functions as a preconcentrator, microreactor, and chiral selector. On-line sample preconcentration with chemical derivatization CE (SPCD-CE) was applied to study the enantioselective amino acid flux in Escherichia coli bacteria cultures, which demonstrated a unique l-Ala efflux into the extracellular medium. New strategies for high-throughput analyses of low-abundance metabolites are important for understanding fundamental physiological processes in bacteria required for screening the efficacy of new classes of antibiotics as well as altered metabolism in genetically modified mutant strains.

Alternatives Assessment Frameworks: Research Needs for the Informed Substitution of Hazardous Chemicals

PubMed Central

Jacobs, Molly M.; Malloy, Timothy F.; Tickner, Joel A.; Edwards, Sally

2015-01-01

Background Given increasing pressures for hazardous chemical replacement, there is growing interest in alternatives assessment to avoid substituting a toxic chemical with another of equal or greater concern. Alternatives assessment is a process for identifying, comparing, and selecting safer alternatives to chemicals of concern (including those used in materials, processes, or technologies) on the basis of their hazards, performance, and economic viability. Objectives The purposes of this substantive review of alternatives assessment frameworks are to identify consistencies and differences in methods and to outline needs for research and collaboration to advance science policy practice. Methods This review compares methods used in six core components of these frameworks: hazard assessment, exposure characterization, life-cycle impacts, technical feasibility evaluation, economic feasibility assessment, and decision making. Alternatives assessment frameworks published from 1990 to 2014 were included. Results Twenty frameworks were reviewed. The frameworks were consistent in terms of general process steps, but some differences were identified in the end points addressed. Methodological gaps were identified in the exposure characterization, life-cycle assessment, and decision–analysis components. Methods for addressing data gaps remain an issue. Discussion Greater consistency in methods and evaluation metrics is needed but with sufficient flexibility to allow the process to be adapted to different decision contexts. Conclusion Although alternatives assessment is becoming an important science policy field, there is a need for increased cross-disciplinary collaboration to refine methodologies in support of the informed substitution and design of safer chemicals, materials, and products. Case studies can provide concrete lessons to improve alternatives assessment. Citation Jacobs MM, Malloy TF, Tickner JA, Edwards S. 2016. Alternatives assessment frameworks: research needs for the informed substitution of hazardous chemicals. Environ Health Perspect 124:265–280; http://dx.doi.org/10.1289/ehp.1409581 PMID:26339778

Design of two-column batch-to-batch recirculation to enhance performance in ion-exchange chromatography.

PubMed

Persson, Oliver; Andersson, Niklas; Nilsson, Bernt

2018-01-05

Preparative liquid chromatography is a separation technique widely used in the manufacturing of fine chemicals and pharmaceuticals. A major drawback of traditional single-column batch chromatography step is the trade-off between product purity and process performance. Recirculation of impure product can be utilized to make the trade-off more favorable. The aim of the present study was to investigate the usage of a two-column batch-to-batch recirculation process step to increase the performance compared to single-column batch chromatography at a high purity requirement. The separation of a ternary protein mixture on ion-exchange chromatography columns was used to evaluate the proposed process. The investigation used modelling and simulation of the process step, experimental validation and optimization of the simulated process. In the presented case the yield increases from 45.4% to 93.6% and the productivity increases 3.4 times compared to the performance of a batch run for a nominal case. A rapid concentration build-up product can be seen during the first cycles, before the process reaches a cyclic steady-state with reoccurring concentration profiles. The optimization of the simulation model predicts that the recirculated salt can be used as a flying start of the elution, which would enhance the process performance. The proposed process is more complex than a batch process, but may improve the separation performance, especially while operating at cyclic steady-state. The recirculation of impure fractions reduces the product losses and ensures separation of product to a high degree of purity. Copyright © 2017 Elsevier B.V. All rights reserved.

Growth of multiwalled-carbon nanotubes using vertically aligned carbon nanofibers as templates/scaffolds and improved field-emission properties

NASA Astrophysics Data System (ADS)

Cui, H.; Yang, X.; Baylor, L. R.; Lowndes, D. H.

2005-01-01

Multiwalled-carbon nanotubes (MWCNTs) are grown on top of vertically aligned carbon nanofibers (VACNFs) via microwave plasma-enhanced chemical vapor deposition (MPECVD). The VACNFs are first grown in a direct-current plasma-enhanced chemical vapor deposition reactor using nickel catalyst. A layer of carbon-silicon materials is then deposited on the VACNFs and the nickel catalyst particle is broken down into smaller nanoparticles during an intermediate reactive-ion-plasma deposition step. These nickel nanoparticles nucleate and grow MWCNTs in the following MPECVD process. Movable-probe measurements show that the MWCNTs have greatly improved field-emission properties relative to the VACNFs.

Quantitative analysis of the thermal requirements for stepwise physical dormancy-break in seeds of the winter annual Geranium carolinianum (Geraniaceae)

PubMed Central

Gama-Arachchige, N. S.; Baskin, J. M.; Geneve, R. L.; Baskin, C. C.

2013-01-01

Background and Aims Physical dormancy (PY)-break in some annual plant species is a two-step process controlled by two different temperature and/or moisture regimes. The thermal time model has been used to quantify PY-break in several species of Fabaceae, but not to describe stepwise PY-break. The primary aims of this study were to quantify the thermal requirement for sensitivity induction by developing a thermal time model and to propose a mechanism for stepwise PY-breaking in the winter annual Geranium carolinianum. Methods Seeds of G. carolinianum were stored under dry conditions at different constant and alternating temperatures to induce sensitivity (step I). Sensitivity induction was analysed based on the thermal time approach using the Gompertz function. The effect of temperature on step II was studied by incubating sensitive seeds at low temperatures. Scanning electron microscopy, penetrometer techniques, and different humidity levels and temperatures were used to explain the mechanism of stepwise PY-break. Key Results The base temperature (Tb) for sensitivity induction was 17·2 °C and constant for all seed fractions of the population. Thermal time for sensitivity induction during step I in the PY-breaking process agreed with the three-parameter Gompertz model. Step II (PY-break) did not agree with the thermal time concept. Q10 values for the rate of sensitivity induction and PY-break were between 2·0 and 3·5 and between 0·02 and 0·1, respectively. The force required to separate the water gap palisade layer from the sub-palisade layer was significantly reduced after sensitivity induction. Conclusions Step I and step II in PY-breaking of G. carolinianum are controlled by chemical and physical processes, respectively. This study indicates the feasibility of applying the developed thermal time model to predict or manipulate sensitivity induction in seeds with two-step PY-breaking processes. The model is the first and most detailed one yet developed for sensitivity induction in PY-break. PMID:23456728

Manipulation of surface morphology of flower-like Ag/ZnO nanorods to enhance photocatalytic performance

NASA Astrophysics Data System (ADS)

U-thaipan, Kasira; Tedsree, Karaked

2018-06-01

The surface morphology of flower-like Ag/ZnO nanorod can be manipulated by adopting different synthetic routes and also loading different levels of Ag in order to alter their surface structures to achieve the maximum photocatalytic efficiency. In a single-step preparation method Ag/ZnO was prepared by heating directly a mixture of Zn2+ and Ag+ precursors in an aqueous NaOH-ethylene glycol solution, while in the two-step preparation method an intermediate of flower-shaped ZnO nanorod was obtained by a hydrothermal process before depositing Ag particles on the ZnO surfaces by chemical reduction. The structure, morphology and optical properties of the synthesized samples were characterized using TEM, SEM, XRD, DRS and PL techniques. The sample prepared by single-step method are characterized with agglomeration of Ag atoms as clusters on the surface of ZnO, whereas in the sample prepared by two-step method Ag atoms are found uniformly dispersed and deposited as discrete Ag nanoparticles on the surface of ZnO. A significant enhancement in the adsorption of visible light was evident for Ag/ZnO samples prepared by two-step method especially with low Ag content (0.5 mol%). The flower-like Ag/ZnO nanorod prepared with 0.5 mol% Ag by two-step process was found to be the most efficient photocatalyst for the degradation of phenol, which can decompose 90% of phenol within 120 min.

Two-Step Oxidation of Refractory Gold Concentrates with Different Microbial Communities.

PubMed

Wang, Guo-Hua; Xie, Jian-Ping; Li, Shou-Peng; Guo, Yu-Jie; Pan, Ying; Wu, Haiyan; Liu, Xin-Xing

2016-11-28

Bio-oxidation is an effective technology for treatment of refractory gold concentrates. However, the unsatisfactory oxidation rate and long residence time, which cause a lower cyanide leaching rate and gold recovery, are key factors that restrict the application of traditional bio-oxidation technology. In this study, the oxidation rate of refractory gold concentrates and the adaption of microorganisms were analyzed to evaluate a newly developed two-step pretreatment process, which includes a high temperature chemical oxidation step and a subsequent bio-oxidation step. The oxidation rate and recovery rate of gold were improved significantly after the two-step process. The results showed that the highest oxidation rate of sulfide sulfur could reach to 99.01 % with an extreme thermophile microbial community when the pulp density was 5%. Accordingly, the recovery rate of gold was elevated to 92.51%. Meanwhile, the results revealed that moderate thermophiles performed better than acidophilic mesophiles and extreme thermophiles, whose oxidation rates declined drastically when the pulp density was increased to 10% and 15%. The oxidation rates of sulfide sulfur with moderate thermophiles were 93.94% and 65.73% when the pulp density was increased to 10% and 15%, respectively. All these results indicated that the two-step pretreatment increased the oxidation rate of refractory gold concentrates and is a potential technology to pretreat the refractory sample. Meanwhile, owing to the sensitivity of the microbial community under different pulp density levels, the optimization of microbial community in bio-oxidation is necessary in industry.

Optimization of an incubation step to maximize sulforaphane content in pre-processed broccoli.

PubMed

Mahn, Andrea; Pérez, Carmen

2016-11-01

Sulforaphane is a powerful anticancer compound, found naturally in food, which comes from the hydrolysis of glucoraphanin, the main glucosinolate of broccoli. The aim of this work was to maximize sulforaphane content in broccoli by designing an incubation step after subjecting broccoli pieces to an optimized blanching step. Incubation was optimized through a Box-Behnken design using ascorbic acid concentration, incubation temperature and incubation time as factors. The optimal incubation conditions were 38 °C for 3 h and 0.22 mg ascorbic acid per g fresh broccoli. The maximum sulforaphane concentration predicted by the model was 8.0 µmol g -1 , which was confirmed experimentally yielding a value of 8.1 ± 0.3 µmol g -1 . This represents a 585% increase with respect to fresh broccoli and a 119% increase in relation to blanched broccoli, equivalent to a conversion of 94% of glucoraphanin. The process proposed here allows maximizing sulforaphane content, thus avoiding artificial chemical synthesis. The compound could probably be isolated from broccoli, and may find application as nutraceutical or functional ingredient.

Demonstration of ultra-low NA rare-earth doped step index fiber for applications in high power fiber lasers.

PubMed

Jain, Deepak; Jung, Yongmin; Barua, Pranabesh; Alam, Shaiful; Sahu, Jayanta K

2015-03-23

In this paper, we report the mode area scaling of a rare-earth doped step index fiber by using low numerical aperture. Numerical simulations show the possibility of achieving an effective area of ~700 um² (including bend induced effective area reduction) at a bend diameter of 32 cm from a 35 μm core fiber with a numerical aperture of 0.038. An effective single mode operation is ensured following the criterion of the fundamental mode loss to be lower than 0.1 dB/m while ensuring the higher order modes loss to be higher than 10 dB/m at a wavelength of 1060 nm. Our optimized modified chemical vapor deposition process in conjunction with solution doping process allows fabrication of an Yb-doped step index fiber having an ultra-low numerical aperture of ~0.038. Experimental results confirm a Gaussian output beam from a 35 μm core fiber validating our simulation results. Fiber shows an excellent laser efficiency of ~81%and aM² less than 1.1.

Modeling Growth of Nanostructures in Plasmas

NASA Technical Reports Server (NTRS)

Hwang, Helen H.; Bose, Deepak; Govindan, T. R.; Meyyappan, M.

2004-01-01

As semiconductor circuits shrink to CDs below 0.1 nm, it is becoming increasingly critical to replace and/or enhance existing technology with nanoscale structures, such as nanowires for interconnects. Nanowires grown in plasmas are strongly dependent on processing conditions, such as gas composition and substrate temperature. Growth occurs at specific sites, or step-edges, with the bulk growth rate of the nanowires determined from the equation of motion of the nucleating crystalline steps. Traditional front-tracking algorithms, such as string-based or level set methods, suffer either from numerical complications in higher spatial dimensions, or from difficulties in incorporating surface-intense physical and chemical phenomena. Phase field models have the robustness of the level set method, combined with the ability to implement surface-specific chemistry that is required to model crystal growth, although they do not necessarily directly solve for the advancing front location. We have adopted a phase field approach and will present results of the adatom density and step-growth location in time as a function of processing conditions, such as temperature and plasma gas composition.

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2004-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Rapid prototyping of microstructures in polydimethylsiloxane (PDMS) by direct UV-lithography.

PubMed

Scharnweber, Tim; Truckenmüller, Roman; Schneider, Andrea M; Welle, Alexander; Reinhardt, Martina; Giselbrecht, Stefan

2011-04-07

Microstructuring of polydimethylsiloxane (PDMS) is a key step for many lab-on-a-chip (LOC) applications. In general, the structure is generated by casting the liquid prepolymer against a master. The production of the master in turn calls for special equipment and know how. Furthermore, a given master only allows the reproduction of the defined structure. We report on a simple, cheap and practical method to produce microstructures in already cured PDMS by direct UV-lithography followed by chemical development. Due to the available options during the lithographic process like multiple exposures, the method offers a high design flexibility granting easy access to complex and stepped structures. Furthermore, no master is needed and the use of pre-cured PDMS allows processing at ambient (light) conditions. Features down to approximately 5 µm and a depth of 10 µm can be realised. As a proof of principle, we demonstrate the feasibility of the process by applying the structures to various established soft lithography techniques.

Controlled electrochemical doping of graphene-based 3D nanoarchitecture electrodes for supercapacitors and capacitive deionisation.

PubMed

Abdelkader, A M; Fray, D J

2017-10-05

Chemically-doped graphenes are promising electrode materials for energy storage and electrosorption applications. Here, an affordable electrochemical green process is introduced to dope graphene with nitrogen. The process is based on reversing the polarity of two identical graphene oxide (GO) electrodes in molten KCl-LiCl-Li 3 N. During the cathodic step, the oxygen functional groups on the GO surface are removed through direct electro-deoxidation reactions or a reaction with the deposited lithium. In the anodic step, nitrogen is adsorbed onto the surface of graphene and subsequently reacts to form nitrogen-doped graphene. The doping process is controllable, and graphene with up to 7.4 at% nitrogen can be produced. The electrochemically treated electrodes show a specific capacitance of 320 F g -1 in an aqueous KOH electrolyte and maintain 96% of this value after 10 000 cycles. The electrodes also display excellent electrosorption performance in capacitive deionisation devices with the salt removal efficiency reaching up to 18.6 mg g -1 .

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

A combined electrocoagulation-sorption process applied to mixed industrial wastewater.

PubMed

Linares-Hernández, Ivonne; Barrera-Díaz, Carlos; Roa-Morales, Gabriela; Bilyeu, Bryan; Ureña-Núñez, Fernando

2007-06-01

The removal of organic pollutants from a highly complex industrial wastewater by a aluminium electrocoagulation process coupled with biosorption was evaluated. Under optimal conditions of pH 8 and 45.45 Am(-2) current density, the electrochemical method yields a very effective reduction of all organic pollutants, this reduction was enhanced when the biosorption treatment was applied as a polishing step. Treatment reduced chemical oxygen demand (COD) by 84%, biochemical oxygen demand (BOD(5)) by 78%, color by 97%, turbidity by 98% and fecal coliforms by 99%. The chemical species formed in aqueous solution were determined. The initial and final pollutant levels in the wastewater were monitored using UV-vis spectrometry and cyclic voltammetry. Finally, the morphology and elemental composition of the biosorbent was characterized with scanning electron microscopy (SEM) and energy dispersion spectra (EDS).

Centrifugal step emulsification applied for absolute quantification of nucleic acids by digital droplet RPA.

PubMed

Schuler, Friedrich; Schwemmer, Frank; Trotter, Martin; Wadle, Simon; Zengerle, Roland; von Stetten, Felix; Paust, Nils

2015-07-07

Aqueous microdroplets provide miniaturized reaction compartments for numerous chemical, biochemical or pharmaceutical applications. We introduce centrifugal step emulsification for the fast and easy production of monodisperse droplets. Homogenous droplets with pre-selectable diameters in a range from 120 μm to 170 μm were generated with coefficients of variation of 2-4% and zero run-in time or dead volume. The droplet diameter depends on the nozzle geometry (depth, width, and step size) and interfacial tensions only. Droplet size is demonstrated to be independent of the dispersed phase flow rate between 0.01 and 1 μl s(-1), proving the robustness of the centrifugal approach. Centrifugal step emulsification can easily be combined with existing centrifugal microfluidic unit operations, is compatible to scalable manufacturing technologies such as thermoforming or injection moulding and enables fast emulsification (>500 droplets per second and nozzle) with minimal handling effort (2-3 pipetting steps). The centrifugal microfluidic droplet generation was used to perform the first digital droplet recombinase polymerase amplification (ddRPA). It was used for absolute quantification of Listeria monocytogenes DNA concentration standards with a total analysis time below 30 min. Compared to digital droplet polymerase chain reaction (ddPCR), with processing times of about 2 hours, the overall processing time of digital analysis was reduced by more than a factor of 4.

Supervised extensions of chemography approaches: case studies of chemical liabilities assessment

PubMed Central

2014-01-01

Chemical liabilities, such as adverse effects and toxicity, play a significant role in modern drug discovery process. In silico assessment of chemical liabilities is an important step aimed to reduce costs and animal testing by complementing or replacing in vitro and in vivo experiments. Herein, we propose an approach combining several classification and chemography methods to be able to predict chemical liabilities and to interpret obtained results in the context of impact of structural changes of compounds on their pharmacological profile. To our knowledge for the first time, the supervised extension of Generative Topographic Mapping is proposed as an effective new chemography method. New approach for mapping new data using supervised Isomap without re-building models from the scratch has been proposed. Two approaches for estimation of model’s applicability domain are used in our study to our knowledge for the first time in chemoinformatics. The structural alerts responsible for the negative characteristics of pharmacological profile of chemical compounds has been found as a result of model interpretation. PMID:24868246

Batch bioethanol production via the biological and chemical saccharification of some Egyptian marine macroalgae.

PubMed

Soliman, Ramadan M; Younis, Sherif A; El-Gendy, Nour Sh; Mostafa, Soha S M; El-Temtamy, Seham A; Hashim, Ahmed I

2018-04-19

Marine seaweeds (macroalgae) cause eutrophication problem and affects the touristic activities. The success of the production of the third generation bioethanol from marine macroalgae depends mainly on the development of an ecofriendly and eco-feasible pretreatment (i.e. hydrolysis) technique, a highly effective saccharification step and finally an efficient bioethanol fermentation step. Therefore, this study aimed to investigate the potentiality of different marine macroalgal strains, collected from Egyptian coasts, for bioethanol production via different saccharification processes. Different marine macroalgal strains; red Jania rubens, green Ulva lactuca. and brown Sargassum latifolium, have been collected from Egyptian Mediterranean and Red Sea shores. Different hydrolysis processes were evaluated to maximize the extraction of fermentable sugars; thermo-chemical hydrolysis with diluted acids (HCl and H 2 SO 4 ) and base (NaOH), hydrothermal hydrolysis followed by saccharification with different fungal strains and finally, thermo-chemical hydrolysis with diluted HCl, followed by fungal saccharification. The hydrothermal hydrolysis of Sargassum latifolium followed by biological saccharification using Trichoderma asperellum RM1 produced maximum total sugars of 510 mg g -1 macroalgal biomass. The integration of the hydrothermal and fungal hydrolyses of the macroalgal biomass with a separate batch fermentation of the produced sugars using two Saccharomyces cerevisiae strains, produced approximately 0.29 g bioethanol g -1 total reducing sugars. A simulated regression modeling for the batch bioethanol fermentation was also performed. This study, supported the possibility of using seaweeds as a renewable source of bioethanol, throughout a suggested integration of macroalgal biomass hydrothermal- and fungal- hydrolysis with a separate batch bioethanol fermentation process of the produced sugars. The usage of marine macroalgae (i.e. seaweeds) as feedstock for bioethanol; an alternative and/or complimentary to petro-fuel, would act as triple fact solution; bioremediation process for ecosystem, renewable energy source and economy savings. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

New Materials and Methods for Hierarchically Structured Tissue Scaffolds

DTIC Science & Technology

2005-01-01

to the fabrication of hierarchically structured scaffolds. In order to achieve this goal, photopolymerizable materials must be developed that are... photopolymerizable materials that can also be selectively chemically modified during the SL part building process. This paper provides an update on our work...which uses a laser to "write" patterns into a vat containing a photopolymerizable resin. The first step in performing SL is generating a computer

Sample preservation, transport and processing strategies for honeybee RNA extraction: Influence on RNA yield, quality, target quantification and data normalization.

PubMed

Forsgren, Eva; Locke, Barbara; Semberg, Emilia; Laugen, Ane T; Miranda, Joachim R de

2017-08-01

Viral infections in managed honey bees are numerous, and most of them are caused by viruses with an RNA genome. Since RNA degrades rapidly, appropriate sample management and RNA extraction methods are imperative to get high quality RNA for downstream assays. This study evaluated the effect of various sampling-transport scenarios (combinations of temperature, RNA stabilizers, and duration) of transport on six RNA quality parameters; yield, purity, integrity, cDNA synthesis efficiency, target detection and quantification. The use of water and extraction buffer were also compared for a primary bee tissue homogenate prior to RNA extraction. The strategy least affected by time was preservation of samples at -80°C. All other regimens turned out to be poor alternatives unless the samples were frozen or processed within 24h. Chemical stabilizers have the greatest impact on RNA quality and adding an extra homogenization step (a QIAshredder™ homogenizer) to the extraction protocol significantly improves the RNA yield and chemical purity. This study confirms that RIN values (RNA Integrity Number), should be used cautiously with bee RNA. Using water for the primary homogenate has no negative effect on RNA quality as long as this step is no longer than 15min. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluorescent silica nanoparticles with chemically reactive surface: Controlling spatial distribution in one-step synthesis.

PubMed

Vera, María L; Cánneva, Antonela; Huck-Iriart, Cristián; Requejo, Felix G; Gonzalez, Mónica C; Dell'Arciprete, María L; Calvo, Alejandra

2017-06-15

The encapsulation of fluorescent dyes inside silica nanoparticles is advantageous to improve their quality as probes. Inside the particle, the fluorophore is protected from the external conditions and its main emission parameters remains unchanged even in the presence of quenchers. On the other hand, the amine-functionalized nanoparticle surface enables a wide range of applications, as amino groups could be easily linked with different biomolecules for targeting purposes. This kind of nanoparticle is regularly synthesized by methods that employ templates, additional nanoparticle formation or multiple pathway process. However, a one-step synthesis will be an efficient approach in this sort of bifunctional hybrid nanoparticles. A co-condensation sol-gel synthesis of hybrid fluorescent silica nanoparticle where developed. The chemical and morphological characterization of the particles where investigated by DRIFTS, XPS, SEM and SAXS. The nanoparticle fluorescent properties were also assessed by excitation-emission matrices and time resolved experiments. We have developed a one-pot synthesis method that enables the simultaneous incorporation of functionalities, the fluorescent molecule and the amino group, by controlling co-condensation process. An exhaustive characterization allows the definition of the spatial distribution of the fluorescent probe, fluorescein isothiocyanate, inside the particle and reactive amino groups on the surface of the nanoparticle with diameter about 100nm. Copyright © 2017 Elsevier Inc. All rights reserved.

Utilization of agricultural wastes for production of ethanol. Progress report, October 1979-May 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, B.

1980-05-01

The project proposes to develop methods to utilize agricultural wastes, especially cottonseed hulls and peanut shells to produce ethanol. Initial steps will involve development of methods to break down cellulose to a usable form of substrates for chemical or biological digestion. The process of ethanol production will consist of (a) preparatory step to separate fibrous (cellulose) and non-fibrous (non-cellulosic compounds). The non-cellulosic residues which may include grains, fats or other substrates for alcoholic fermentation. The fibrous residues will be first pre-treated to digest cellulose with acid, alkali, and sulfur dioxide gas or other solvents. (b) The altered cellulose will bemore » digested by suitable micro-organisms and cellulose enzymes before alcoholic fermentation. The digester and fermentative unit will be specially designed to develop a prototype for pilot plant for a continuous process. The first phase of the project will be devoted toward screening of a suitable method for cellulose modification, separation of fibrous and non-fibrous residues, the micro-organism and enzyme preparations. Work is in progress on: the effects of various microorganisms on the degree of saccharification; the effects of higher concentrations of acids, alkali, and EDTA on efficiency of microbial degradation; and the effects of chemicals on enzymatic digestion.« less

Woody biomass: Niche position as a source of sustainable renewable chemicals and energy and kinetics of hot-water extraction/hydrolysis.

PubMed

Liu, Shijie

2010-01-01

The conversion of biomass to chemicals and energy is imperative to sustaining our way of life as known to us today. Fossil chemical and energy sources are traditionally regarded as wastes from a distant past. Petroleum, natural gas, and coal are not being regenerated in a sustainable manner. However, biomass sources such as algae, grasses, bushes and forests are continuously being replenished. Woody biomass represents the most abundant and available biomass source. Woody biomass is a reliably sustainable source of chemicals and energy that could be replenished at a rate consistent with our needs. The biorefinery is a concept describing the collection of processes used to convert biomass to chemicals and energy. Woody biomass presents more challenges than cereal grains for conversion to platform chemicals due to its stereochemical structures. Woody biomass can be thought of as comprised of at least four components: extractives, hemicellulose, lignin and cellulose. Each of these four components has a different degree of resistance to chemical, thermal and biological degradation. The biorefinery concept proposed at ESF (State University of New York - College of Environmental Science and Forestry) aims at incremental sequential deconstruction, fractionation/conversion of woody biomass to achieve efficient separation of major components. The emphasis of this work is on the kinetics of hot-water extraction, filling the gap in the fundamental understanding, linking engineering developments, and completing the first step in the biorefinery processes. This first step removes extractives and hemicellulose fractions from woody biomass. While extractives and hemicellulose are largely removed in the extraction liquor, cellulose and lignin largely remain in the residual woody structure. Xylo-oligomers and acetic acid in the extract are the major components having the greatest potential value for development. Extraction/hydrolysis involves at least 16 general reactions that could be divided into four categories: adsorption of proton onto woody biomass, hydrolysis reactions on the woody biomass surface, dissolution of soluble substances into the extraction liquor, and hydrolysis and dehydration decomposition in the extraction liquor. The extraction/hydrolysis rates are significantly simplified when the reactivity of all the intermonomer bonds are regarded as identical within each macromolecule, and the overall reactivity are identical for all the extractable macromolecules on the surface. A pseudo-first order extraction rate expression has been derived based on concentrations in monomer units. The reaction rate constant is however lower at the beginning of the extraction than that towards the end of the extraction. Furthermore, the H-factor and/or severity factor can be applied to lump the effects of temperature and residence time on the extraction process, at least for short times. This provides a means to control and optimize the performance of the extraction process effectively. Copyright 2010 Elsevier Inc. All rights reserved.

Quantification of triglyceride content in oleaginous materials using thermo-gravimetry

DOE PAGES

Maddi, Balakrishna; Vadlamani, Agasteswar; Viamajala, Sridhar; ...

2017-10-16

Laboratory analytical methods for quantification of triglyceride content in oleaginous biomass samples, especially microalgae, require toxic chemicals and/or organic solvents and involve multiple steps. We describe a simple triglyceride quantification method that uses thermo-gravimetry. This method is based on the observation that triglycerides undergo near-complete volatilization/degradation over a narrow temperature interval with a derivative weight loss peak at 420 °C when heated in an inert atmosphere. Degradation of the other constituents of oleaginous biomass (protein and carbohydrates) is largely complete after prolonged exposure of samples at 320 °C. Based on these observations, the triglyceride content of oleaginous biomass was estimatedmore » by using the following two-step process. In Step 1, samples were heated to 320 °C and kept isothermal at this temperature for 15 min. In Step 2, samples were heated from 320 °C to 420 °C and then kept isothermal at 420 °C for 15 min. The results show that mass loss in step 2 correlated well with triglyceride content estimates obtained from conventional techniques for diverse microalgae and oilseed samples.« less

Quantification of triglyceride content in oleaginous materials using thermo-gravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maddi, Balakrishna; Vadlamani, Agasteswar; Viamajala, Sridhar

Laboratory analytical methods for quantification of triglyceride content in oleaginous biomass samples, especially microalgae, require toxic chemicals and/or organic solvents and involve multiple steps. We describe a simple triglyceride quantification method that uses thermo-gravimetry. This method is based on the observation that triglycerides undergo near-complete volatilization/degradation over a narrow temperature interval with a derivative weight loss peak at 420 °C when heated in an inert atmosphere. Degradation of the other constituents of oleaginous biomass (protein and carbohydrates) is largely complete after prolonged exposure of samples at 320 °C. Based on these observations, the triglyceride content of oleaginous biomass was estimatedmore » by using the following two-step process. In Step 1, samples were heated to 320 °C and kept isothermal at this temperature for 15 min. In Step 2, samples were heated from 320 °C to 420 °C and then kept isothermal at 420 °C for 15 min. The results show that mass loss in step 2 correlated well with triglyceride content estimates obtained from conventional techniques for diverse microalgae and oilseed samples.« less

Biomass-to-electricity: analysis and optimization of the complete pathway steam explosion--enzymatic hydrolysis--anaerobic digestion with ICE vs SOFC as biogas users.

PubMed

Santarelli, M; Barra, S; Sagnelli, F; Zitella, P

2012-11-01

The paper deals with the energy analysis and optimization of a complete biomass-to-electricity energy pathway, starting from raw biomass towards the production of renewable electricity. The first step (biomass-to-biogas) is based on a real pilot plant located in Environment Park S.p.A. (Torino, Italy) with three main steps ((1) impregnation; (2) steam explosion; (3) enzymatic hydrolysis), completed by a two-step anaerobic fermentation. In the second step (biogas-to-electricity), the paper considers two technologies: internal combustion engines and a stack of solid oxide fuel cells. First, the complete pathway has been modeled and validated through experimental data. After, the model has been used for an analysis and optimization of the complete thermo-chemical and biological process, with the objective function of maximization of the energy balance at minimum consumption. The comparison between ICE and SOFC shows the better performance of the integrated plants based on SOFC. Copyright © 2012 Elsevier Ltd. All rights reserved.

Study on Potential Changes in Geological and Disposal Environment Caused by 'Natural Phenomena' on a HLW Disposal System

NASA Astrophysics Data System (ADS)

Kawamura, M.; Umeda, K.; Ohi, T.; Ishimaru, T.; Niizato, T.; Yasue, K.; Makino, H.

2007-12-01

We have developed a formal evaluation method to assess the potential impact of natural phenomena (earthquakes and faulting; volcanism; uplift, subsidence, denudation and sedimentation; climatic and sea-level changes) on a High Level Radioactive Waste (HLW) Disposal System. In 2000, we had developed perturbation scenarios in a generic and conservative sense and illustrated the potential impact on a HLW disposal system. As results of the development of perturbation scenarios, two points were highlighted for consideration in subsequent work: improvement of the scenarios from the viewpoints of reality, transparency, traceability and consistency and avoiding extreme conservatism. Subsequently, we have thus developed a new procedure for describing such perturbation scenarios based on further studies of the characteristics of these natural perturbation phenomena in Japan. The approach to describing the perturbation scenario is effectively developed in five steps: Step 1: Description of potential process of phenomena and their impacts on the geological environment. Step 2: Characterization of potential changes of geological environment in terms of T-H-M-C (Thermal - Hydrological - Mechanical - Chemical) processes. The focus is on specific T-H-M-C parameters that influence geological barrier performance, utilizing the input from Step 1. Step 3: Classification of potential influences, based on similarity of T-H-M-C perturbations. This leads to development of perturbation scenarios to serve as a basis for consequence analysis. Step 4: Establishing models and parameters for performance assessment. Step 5: Calculation and assessment. This study focuses on identifying key T-H-M-C process associated with perturbations at Step 2. This framework has two advantages. First one is assuring maintenance of traceability during the scenario construction processes, facilitating the production and structuring of suitable records. The second is providing effective elicitation and organization of information from a wide range of investigations of earth sciences within a performance assessment context. In this framework, scenario development work proceeds in a stepwise manner, to ensure clear identification of the impact of processes associated with these phenomena on a HLW disposal system. Output is organized to create credible scenarios with required transparency, consistency, traceability and adequate conservatism. In this presentation, the potential impact of natural phenomena in the viewpoint of performance assessment for HLW disposal will be discussed and modeled using the approach.

Safety in the Chemical Laboratory: Flood Control.

ERIC Educational Resources Information Center

Pollard, Bruce D.

1983-01-01

Describes events leading to a flood in the Wehr Chemistry Laboratory at Marquette University, discussing steps taken to minimize damage upon discovery. Analyzes the problem of flooding in the chemical laboratory and outlines seven steps of flood control: prevention; minimization; early detection; stopping the flood; evaluation; clean-up; and…

Anaerobic digestion of microalgal biomass: Challenges, opportunities and research needs.

PubMed

Gonzalez-Fernandez, Cristina; Sialve, Bruno; Molinuevo-Salces, Beatriz

2015-12-01

Integration of anaerobic digestion (AD) with microalgae processes has become a key topic to support economic and environmental development of this resource. Compared with other substrates, microalgae can be produced close to the plant without the need for arable lands and be fully integrated within a biorefinery. As a limiting step, anaerobic hydrolysis appears to be one of the most challenging steps to reach a positive economic balance and to completely exploit the potential of microalgae for biogas and fertilizers production. This review covers recent investigations dealing with microalgae AD and highlights research opportunities and needs to support the development of this resource. Novel approaches to increase hydrolysis rate, the importance of the reactor design and the noteworthiness of the microbial anaerobic community are addressed. Finally, the integration of AD with microalgae processes and the potential of the carboxylate platform for chemicals and biofuels production are reviewed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Single-Step Reagentless Laser Scribing Fabrication of Electrochemical Paper-Based Analytical Devices.

PubMed

de Araujo, William R; Frasson, Carolina M R; Ameku, Wilson A; Silva, José R; Angnes, Lúcio; Paixão, Thiago R L C

2017-11-20

A single-step laser scribing process is used to pattern nanostructured electrodes on paper-based devices. The facile and low-cost technique eliminates the need for chemical reagents or controlled conditions. This process involves the use of a CO 2 laser to pyrolyze the surface of the paperboard, producing a conductive porous non-graphitizing carbon material composed of graphene sheets and composites with aluminosilicate nanoparticles. The new electrode material was extensively characterized, and it exhibits high conductivity and an enhanced active/geometric area ratio; it is thus well-suited for electrochemical purposes. As a proof-of-concept, the devices were successfully employed for different analytical applications in the clinical, pharmaceutical, food, and forensic fields. The scalable and green fabrication method associated with the features of the new material is highly promising for the development of portable electrochemical devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pretreatment of Cellulose By Electron Beam Irradiation Method

NASA Astrophysics Data System (ADS)

Jusri, N. A. A.; Azizan, A.; Ibrahim, N.; Salleh, R. Mohd; Rahman, M. F. Abd

2018-05-01

Pretreatment process of lignocellulosic biomass (LCB) to produce biofuel has been conducted by using various methods including physical, chemical, physicochemical as well as biological. The conversion of bioethanol process typically involves several steps which consist of pretreatment, hydrolysis, fermentation and separation. In this project, microcrystalline cellulose (MCC) was used in replacement of LCB since cellulose has the highest content of LCB for the purpose of investigating the effectiveness of new pretreatment method using radiation technology. Irradiation with different doses (100 kGy to 1000 kGy) was conducted by using electron beam accelerator equipment at Agensi Nuklear Malaysia. Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction (XRD) analyses were studied to further understand the effect of the suggested pretreatment step to the content of MCC. Through this method namely IRR-LCB, an ideal and optimal condition for pretreatment prior to the production of biofuel by using LCB may be introduced.

Biochemical Conversion Processes of Lignocellulosic Biomass to Fuels and Chemicals - A Review.

PubMed

Brethauer, Simone; Studer, Michael H

2015-01-01

Lignocellulosic biomass - such as wood, agricultural residues or dedicated energy crops - is a promising renewable feedstock for production of fuels and chemicals that is available at large scale at low cost without direct competition for food usage. Its biochemical conversion in a sugar platform biorefinery includes three main unit operations that are illustrated in this review: the physico-chemical pretreatment of the biomass, the enzymatic hydrolysis of the carbohydrates to a fermentable sugar stream by cellulases and finally the fermentation of the sugars by suitable microorganisms to the target molecules. Special emphasis in this review is put on the technology, commercial status and future prospects of the production of second-generation fuel ethanol, as this process has received most research and development efforts so far. Despite significant advances, high enzyme costs are still a hurdle for large scale competitive lignocellulosic ethanol production. This could be overcome by a strategy termed 'consolidated bioprocessing' (CBP), where enzyme production, enzymatic hydrolysis and fermentation is integrated in one step - either by utilizing one genetically engineered superior microorganism or by creating an artificial co-culture. Insight is provided on both CBP strategies for the production of ethanol as well as of advanced fuels and commodity chemicals.

Method of drying passivated micromachines by dewetting from a liquid-based process

DOEpatents

Houston, Michael R.; Howe, Roger T.; Maboudian, Roya; Srinivasan, Uthara

2000-01-01

A method of fabricating a micromachine includes the step of constructing a low surface energy film on the micromachine. The micromachine is then rinsed with a rinse liquid that has a high surface energy, relative to the low surface energy film, to produce a contact angle of greater than 90.degree. between the low surface energy film and the rinse liquid. This relatively large contact angle causes any rinse liquid on the micromachine to be displaced from the micromachine when the micromachine is removed from the rinse liquid. In other words, the micromachine is dried by dewetting from a liquid-based process. Thus, a separate evaporative drying step is not required, as the micromachine is removed from the liquid-based process in a dry state. The relatively large contact angle also operates to prevent attractive capillary forces between micromachine components, thereby preventing contact and adhesion between adjacent microstructure surfaces. The low surface energy film may be constructed with a fluorinated self-assembled monolayer film. The processing of the invention avoids the use of environmentally harmful, health-hazardous chemicals.

Electroless silver plating of the surface of organic semiconductors.

PubMed

Campione, Marcello; Parravicini, Matteo; Moret, Massimo; Papagni, Antonio; Schröter, Bernd; Fritz, Torsten

2011-10-04

The integration of nanoscale processes and devices demands fabrication routes involving rapid, cost-effective steps, preferably carried out under ambient conditions. The realization of the metal/organic semiconductor interface is one of the most demanding steps of device fabrication, since it requires mechanical and/or thermal treatments which increment costs and are often harmful in respect to the active layer. Here, we provide a microscopic analysis of a room temperature, electroless process aimed at the deposition of a nanostructured metallic silver layer with controlled coverage atop the surface of single crystals and thin films of organic semiconductors. This process relies on the reaction of aqueous AgF solutions with the nonwettable crystalline surface of donor-type organic semiconductors. It is observed that the formation of a uniform layer of silver nanoparticles can be accomplished within 20 min contact time. The electrical characterization of two-terminal devices performed before and after the aforementioned treatment shows that the metal deposition process is associated with a redox reaction causing the p-doping of the semiconductor. © 2011 American Chemical Society

A History of the Chemical Innovations in Silver-Halide Materials for Color PhotographyIII. Dye Tranfer Process — Instant Color Photography

NASA Astrophysics Data System (ADS)

Oishi, Yasushi

A historical review of the technological developments of instant color photographic process, is presented with emphasis on the innovation processes at the following main turning points: 1) the creation of instant photography by E. H. Land in 1948 (one step processing by transfer of image-forming materials), 2) the advent of instant color photography based on dye developer, by Polaroid Corp., in 1963 (departing from dye-forming development, forming a direct positive preformed-dye image with a negative emulsion, but constraining the sensitive-material designs), 3) the introduction of a color instant product containing redox dye releaser with improved auto-positive emulsion, by Eastman Kodak Co., in 1976 (producing much improved color image quality, freed from the design constraints), and 4) the realization of absolute one-step photography by the integral film- unit system, by Polaroid in 1972. And the patent litigation (1976-86) raised by Polaroid against Kodak allegedly infringing on the integral film-unit patents caused the vast impacts on the industry.

Surfactant-aided recovery/in situ bioremediation for oil-contaminated sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ducreaux, J.; Baviere, M.; Seabra, P.

1995-12-31

Bioremediation has been the most commonly used method way for in situ cleaning of soils contaminated with low-volatility petroleum products such as diesel oil. However, whatever the process (bioventing, bioleaching, etc.), it is a time-consuming technique that may be efficiency limited by both accessibility and too high concentrations of contaminants. A currently developed process aims at quickly recovering part of the residual oil in the vadose and capillary zones by surfactant flushing, then activating in situ biodegradation of the remaining oil in the presence of the same or other surfactants. The process has been tested in laboratory columns and inmore » an experimental pool, located at the Institut Franco-Allemand de Recherche sur l`Environnement (IFARE) in Strasbourg, France. Laboratory column studies were carried out to fit physico-chemical and hydraulic parameters of the process to the field conditions. The possibility of recovering more than 80% of the oil in the flushing step was shown. For the biodegradation step, forced aeration as a mode of oxygen supply, coupled with nutrient injection aided by surfactants, was tested.« less

The function of advanced treatment process in a drinking water treatment plant with organic matter-polluted source water.

PubMed

Lin, Huirong; Zhang, Shuting; Zhang, Shenghua; Lin, Wenfang; Yu, Xin

2017-04-01

To understand the relationship between chemical and microbial treatment at each treatment step, as well as the relationship between microbial community structure in biofilms in biofilters and their ecological functions, a drinking water plant with severe organic matter-polluted source water was investigated. The bacterial community dynamics of two drinking water supply systems (traditional and advanced treatment processes) in this plant were studied from the source to the product water. Analysis by 454 pyrosequencing was conducted to characterize the bacterial diversity in each step of the treatment processes. The bacterial communities in these two treatment processes were highly diverse. Proteobacteria, which mainly consisted of beta-proteobacteria, was the dominant phylum. The two treatment processes used in the plant could effectively remove organic pollutants and microbial polution, especially the advanced treatment process. Significant differences in the detection of the major groups were observed in the product water samples in the treatment processes. The treatment processes, particularly the biological pretreatment and O 3 -biological activated carbon in the advanced treatment process, highly influenced the microbial community composition and the water quality. Some opportunistic pathogens were found in the water. Nitrogen-relative microorganisms found in the biofilm of filters may perform an important function on the microbial community composition and water quality improvement.

TRAX-CHEM: A pre-chemical and chemical stage extension of the particle track structure code TRAX in water targets

NASA Astrophysics Data System (ADS)

Boscolo, D.; Krämer, M.; Durante, M.; Fuss, M. C.; Scifoni, E.

2018-04-01

The production, diffusion, and interaction of particle beam induced water-derived radicals is studied with the a pre-chemical and chemical module of the Monte Carlo particle track structure code TRAX, based on a step by step approach. After a description of the model implemented, the chemical evolution of the most important products of water radiolysis is studied for electron, proton, helium, and carbon ion radiation at different energies. The validity of the model is verified by comparing the calculated time and LET dependent yield with experimental data from literature and other simulation approaches.

Method for cold stable biojet fuel

DOEpatents

Seames, Wayne S.; Aulich, Ted

2015-12-08

Plant or animal oils are processed to produce a fuel that operates at very cold temperatures and is suitable as an aviation turbine fuel, a diesel fuel, a fuel blendstock, or any fuel having a low cloud point, pour point or freeze point. The process is based on the cracking of plant or animal oils or their associated esters, known as biodiesel, to generate lighter chemical compounds that have substantially lower cloud, pour, and/or freeze points than the original oil or biodiesel. Cracked oil is processed using separation steps together with analysis to collect fractions with desired low temperature properties by removing undesirable compounds that do not possess the desired temperature properties.

Integrated conversion of food waste diluted with sewage into volatile fatty acids through fermentation and electricity through a fuel cell.

PubMed

Pant, Deepak; Arslan, Doga; Van Bogaert, Gilbert; Gallego, Yolanda Alvarez; De Wever, Heleen; Diels, Ludo; Vanbroekhoven, Karolien

2013-01-01

In this study, domestic wastewater was given a second life as dilution medium for concentrated organic waste streams, in particular artificial food waste. A two-step continuous process with first volatile fatty acid (VFA)/hydrogen production and second electricity production in microbial fuel cells (MFCs) was employed. For primary treatment, bioreactors were optimized to produce hydrogen and VFAs. Hydrolysis of the solids and formation of fermentation products and hydrogen was monitored. In the second step, MFCs were operated batch-wise using the effluent rich in VFAs specifically acetic acid from the continuous reactor of the first step. The combined system was able to reduce the chemical oxygen demand load by 90%. The concentration of VFAs was also monitored regularly in the MFCs and showed a decreasing trend over time. Further, the anode potential changed from -500 to OmV vs. Ag/AgCl when the VFAs (especially acetate) were depleted in the system. On feeding the system again with the effluent, the anode potential recovered back to -500 mV vs. Ag/AgCl. Thus, the overall aim of converting chemical energy into electrical energy was achieved with a columbic efficiency of 46% generating 65.33 mA/m2 at a specific cell potential of 148 mV.

Effect of Two-Step Metal Organic Chemical Vapor Deposition Growth on Quality, Diameter and Density of InAs Nanowires on Si (111) Substrate

NASA Astrophysics Data System (ADS)

Yu, Hung Wei; Anandan, Deepak; Hsu, Ching Yi; Hung, Yu Chih; Su, Chun Jung; Wu, Chien Ting; Kakkerla, Ramesh Kumar; Ha, Minh Thien Huu; Huynh, Sa Hoang; Tu, Yung Yi; Chang, Edward Yi

2018-02-01

High-density (˜ 80/um2) vertical InAs nanowires (NWs) with small diameters (˜ 28 nm) were grown on bare Si (111) substrates by means of two-step metal organic chemical vapor deposition. There are two critical factors in the growth process: (1) a critical nucleation temperature for a specific In molar fraction (approximately 1.69 × 10-5 atm) is the key factor to reduce the size of the nuclei and hence the diameter of the InAs NWs, and (2) a critical V/III ratio during the 2nd step growth will greatly increase the density of the InAs NWs (from 45 μm-2 to 80 μm-2) and at the same time keep the diameter small. The high-resolution transmission electron microscopy and selected area diffraction patterns of InAs NWs grown on Si exhibit a Wurtzite structure and no stacking faults. The observed longitudinal optic peaks in the Raman spectra were explained in terms of the small surface charge region width due to the small NW diameter and the increase of the free electron concentration, which was consistent with the TCAD program simulation of small diameter (< 40 nm) InAs NWs.

Advances in polycrystalline thin-film photovoltaics for space applications

NASA Technical Reports Server (NTRS)

Lanning, Bruce R.; Armstrong, Joseph H.; Misra, Mohan S.

1994-01-01

Polycrystalline, thin-film photovoltaics represent one of the few (if not the only) renewable power sources which has the potential to satisfy the demanding technical requirements for future space applications. The demand in space is for deployable, flexible arrays with high power-to-weight ratios and long-term stability (15-20 years). In addition, there is also the demand that these arrays be produced by scalable, low-cost, high yield, processes. An approach to significantly reduce costs and increase reliability is to interconnect individual cells series via monolithic integration. Both CIS and CdTe semiconductor films are optimum absorber materials for thin-film n-p heterojunction solar cells, having band gaps between 0.9-1.5 ev and demonstrated small area efficiencies, with cadmium sulfide window layers, above 16.5 percent. Both CIS and CdTe polycrystalline thin-film cells have been produced on a laboratory scale by a variety of physical and chemical deposition methods, including evaporation, sputtering, and electrodeposition. Translating laboratory processes which yield these high efficiency, small area cells into the design of a manufacturing process capable of producing 1-sq ft modules, however, requires a quantitative understanding of each individual step in the process and its (each step) effect on overall module performance. With a proper quantification and understanding of material transport and reactivity for each individual step, manufacturing process can be designed that is not 'reactor-specific' and can be controlled intelligently with the design parameters of the process. The objective of this paper is to present an overview of the current efforts at MMC to develop large-scale manufacturing processes for both CIS and CdTe thin-film polycrystalline modules. CIS cells/modules are fabricated in a 'substrate configuration' by physical vapor deposition techniques and CdTe cells/modules are fabricated in a 'superstrate configuration' by wet chemical methods. Both laser and mechanical scribing operations are used to monolithically integrate (series interconnect) the individual cells into modules. Results will be presented at the cell and module development levels with a brief description of the test methods used to qualify these devices for space applications. The approach and development efforts are directed towards large-scale manufacturability of established thin-film, polycrystalline processing methods for large area modules with less emphasis on maximizing small area efficiencies.

Quantifying variability in removal efficiencies of chemicals in activated sludge wastewater treatment plants - a meta-analytical approach.

PubMed

Douziech, Mélanie; Conesa, Irene Rosique; Benítez-López, Ana; Franco, Antonio; Huijbregts, Mark; van Zelm, Rosalie

2018-01-24

Large variations in removal efficiencies (REs) of chemicals have been reported for monitoring studies of activated sludge wastewater treatment plants (WWTPs). In this work, we conducted a meta-analysis on REs (1539 data points) for a set of 209 chemicals consisting of fragrances, surfactants, and pharmaceuticals in order to assess the drivers of the variability relating to inherent properties of the chemicals and operational parameters of activated sludge WWTPs. For a reduced dataset (n = 542), we developed a mixed-effect model (meta-regression) to explore the observed variability in REs for the chemicals using three chemical specific factors and four WWTP-related parameters. The overall removal efficiency of the set of chemicals was 82.1% (95% CI 75.2-87.1%, N = 1539). Our model accounted for 17% of the total variability in REs, while the process-based model SimpleTreat did not perform better than the average of the measured REs. We identified that, after accounting for other factors potentially influencing RE, readily biodegradable compounds were better removed than non-readily biodegradable ones. Further, we showed that REs increased with increasing sludge retention times (SRTs), especially for non-readily biodegradable compounds. Finally, our model highlighted a decrease in RE with increasing K OC . The counterintuitive relationship to K OC stresses the need for a better understanding of electrochemical interactions influencing the RE of ionisable chemicals. In addition, we highlighted the need to improve the modelling of chemicals that undergo deconjugation when predicting RE. Our meta-analysis represents a first step in better explaining the observed variability in measured REs of chemicals. It can be of particular help to prioritize the improvements required in existing process-based models to predict removal efficiencies of chemicals in WWTPs.

Process for the enhanced capture of heavy metal emissions

DOEpatents

Biswas, Pratim; Wu, Chang-Yu

2001-01-01

This invention is directed to a process for forming a sorbent-metal complex. The process includes oxidizing a sorbent precursor and contacting the sorbent precursor with a metallic species. The process further includes chemically reacting the sorbent precursor and the metallic species, thereby forming a sorbent-metal complex. In one particular aspect of the invention, at least a portion of the sorbent precursor is transformed into sorbent particles during the oxidation step. These sorbent particles then are contacted with the metallic species and chemically reacted with the metallic species, thereby forming a sorbent-metal complex. Another aspect of the invention is directed to a process for forming a sorbent metal complex in a combustion system. The process includes introducing a sorbent precursor into a combustion system and subjecting the sorbent precursor to an elevated temperature sufficient to oxidize the sorbent precursor and transform the sorbent precursor into sorbent particles. The process further includes contacting the sorbent particles with a metallic species and exposing the sorbent particles and the metallic species to a complex-forming temperature whereby the metallic species reacts with the sorbent particles thereby forming a sorbent-metal complex under UV irradiation.

A nonchromatographic process for purification of secretory immunoglobulins from caprine whey.

PubMed

Matlschweiger, Alexander; Himmler, Gottfried; Linhart, Clemens; Harasek, Michael; Hahn, Rainer

2017-05-01

Secretory immunoglobulins are an important antibody class being primarily responsible for immunoprotection of mucosal surfaces. A simple, non-chromatographic purification process for secretory immunoglobulins from caprine whey was developed. In the first process step whey was concentrated 30-40-fold on a 500 kDa membrane, thereby increasing the purity from 3% to 15%. The second step consisted of a fractionated PEG precipitation, in which high molecular weight impurities were removed first and in the second stage the secretory immunoglobulins were precipitated, leaving a majority of the low molecular weight proteins in solution. The re-dissolved secretory immunoglobulin fraction had a purity of 43% which could then be increased to 72% by diafiltration at a volume exchange factor of 10. Further increase of purity was only possible at the expense of very high buffer consumption. If diafiltration was performed directly after ultrafiltration, followed by precipitation, the yield was higher but purity was only 54%. Overall, filtration performance was characterized by high concentration polarization, therefore process conditions were set to low trans-membrane pressure and moderate protein concentration. As such purity and to a lesser extent throughput were the major objectives rather than yield, since whey, as a by-product of the dairy industry, is a cheap raw material of almost unlimited supply. Ultra-/diafiltration performance was described well by correlations using dimensionless numbers. Compared with a theoretical model (Graetz/Leveque solution) the flux was slightly overestimated. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:642-653, 2017. © 2017 American Institute of Chemical Engineers.

High density and taper-free boron doped Si{sub 1−x}Ge{sub x} nanowire via two-step growth process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Periwal, Priyanka; Salem, Bassem; Bassani, Franck

2014-07-01

The authors study Au catalyzed chemical vapor growth of Si{sub 1−x}Ge{sub x} alloyed nanowires in the presence of diborane, serving as a dopant precursor. Our experiments reveal that introduction of diborane has a significant effect on doping and morphology. Boron exposure poisons the Au catalyst surface, suppresses catalyst activity, and causes significantly tapered wires, as a result of conformal growth. The authors develop here a two-step method to obtain high density and taper-free boron doped Si{sub 1−x}Ge{sub x} alloy nanowires. The two-step process consists of: (1) growth of a small undoped Si{sub 1−x}Ge{sub x} section and (2) introduction of diboranemore » to form a boron doped Si{sub 1−x}Ge{sub x} section. The catalyst preparation step remarkably influences wire yield, quality and morphology. The authors show that dopant-ratio influences wire resistivity and morphology. Resistivity for high boron doped Si{sub 1−x}Ge{sub x} nanowire is 6 mΩ-cm. Four probe measurements show that it is possible to dope Si{sub 1−x}Ge{sub x} alloy nanowires with diborane.« less

Chemical reactions at aqueous interfaces

NASA Astrophysics Data System (ADS)

Vecitis, Chad David

2009-12-01

Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1) Adsorption of dilute PFOS(aq) and PFOA(aq) to acoustically cavitating bubble interfaces was greater than equilibrium expectations due to high-velocity bubble radial oscillations; 2) Relative ozone oxidation kinetics of aqueous iodide, sulfite, and thiosulfate were at variance with previously reported bulk aqueous kinetics; 3) Organics that directly chelated with the anode surface were oxidized by direct electron transfer, resulting in immediate carbon dioxide production but slower overall oxidation kinetics. Chemical reactions at aqueous interfaces can be the rate-limiting step of a reaction network and often display novel mechanisms and kinetics as compared to homogeneous chemistry.

Highly efficient conversion of plant oil to bio-aviation fuel and valuable chemicals by combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating.

PubMed

Wang, Meng; Chen, Mojin; Fang, Yunming; Tan, Tianwei

2018-01-01

The production of fuels and chemicals from renewable resources is increasingly important due to the environmental concern and depletion of fossil fuel. Despite the fast technical development in the production of aviation fuels, there are still several shortcomings such as a high cost of raw materials, a low yield of aviation fuels, and poor process techno-economic consideration. In recent years, olefin metathesis has become a powerful and versatile tool for generating new carbon-carbon bonds. The cross-metathesis reaction, one kind of metathesis reaction, has a high potential to efficiently convert plant oil into valuable chemicals, such as α-olefin and bio-aviation fuel by combining with a hydrotreatment process. In this research, an efficient, four-step conversion of plant oil into bio-aviation fuel and valuable chemicals was developed by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating. Firstly, plant oil including oil with poor properties was esterified to fatty acid methyl esters by an enzyme-catalyzed process. Secondly, the fatty acid methyl esters were partially hydrotreated catalytically to transform poly-unsaturated fatty acid such as linoleic acid into oleic acid. The olefin cross-metathesis then transformed the oleic acid methyl ester (OAME) into 1-decene and 1-decenoic acid methyl ester (DAME). The catalysts used in this process were prepared/selected in function of the catalytic reaction and the reaction conditions were optimized. The carbon efficiency analysis of the new process illustrated that it was more economically feasible than the traditional hydrotreatment process. A highly efficient conversion process of plant oil into bio-aviation fuel and valuable chemicals by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreatment with prepared and selected catalysts was designed. The reaction conditions were optimized. Plant oil was transformed into bio-aviation fuel and a high value α-olefin product with high carbon utilization.

A novel biochemical route for fuels and chemicals production from cellulosic biomass.

PubMed

Fan, Zhiliang; Wu, Weihua; Hildebrand, Amanda; Kasuga, Takao; Zhang, Ruifu; Xiong, Xiaochao

2012-01-01

The conventional biochemical platform featuring enzymatic hydrolysis involves five key steps: pretreatment, cellulase production, enzymatic hydrolysis, fermentation, and product recovery. Sugars are produced as reactive intermediates for subsequent fermentation to fuels and chemicals. Herein, an alternative biochemical route is proposed. Pretreatment, enzymatic hydrolysis and cellulase production is consolidated into one single step, referred to as consolidated aerobic processing, and sugar aldonates are produced as the reactive intermediates for biofuels production by fermentation. In this study, we demonstrate the viability of consolidation of the enzymatic hydrolysis and cellulase production steps in the new route using Neurospora crassa as the model microorganism and the conversion of cellulose to ethanol as the model system. We intended to prove the two hypotheses: 1) cellulose can be directed to produce cellobionate by reducing β-glucosidase production and by enhancing cellobiose dehydrogenase production; and 2) both of the two hydrolysis products of cellobionate--glucose and gluconate--can be used as carbon sources for ethanol and other chemical production. Our results showed that knocking out multiple copies of β-glucosidase genes led to cellobionate production from cellulose, without jeopardizing the cellulose hydrolysis rate. Simulating cellobiose dehydrogenase over-expression by addition of exogenous cellobiose dehydrogenase led to more cellobionate production. Both of the two hydrolysis products of cellobionate: glucose and gluconate can be used by Escherichia coli KO 11 for efficient ethanol production. They were utilized simultaneously in glucose and gluconate co-fermentation. Gluconate was used even faster than glucose. The results support the viability of the two hypotheses that lay the foundation for the proposed new route.

A Novel Biochemical Route for Fuels and Chemicals Production from Cellulosic Biomass

PubMed Central

Fan, Zhiliang; Wu, Weihua; Hildebrand, Amanda; Kasuga, Takao; Zhang, Ruifu; Xiong, Xiaochao

2012-01-01

The conventional biochemical platform featuring enzymatic hydrolysis involves five key steps: pretreatment, cellulase production, enzymatic hydrolysis, fermentation, and product recovery. Sugars are produced as reactive intermediates for subsequent fermentation to fuels and chemicals. Herein, an alternative biochemical route is proposed. Pretreatment, enzymatic hydrolysis and cellulase production is consolidated into one single step, referred to as consolidated aerobic processing, and sugar aldonates are produced as the reactive intermediates for biofuels production by fermentation. In this study, we demonstrate the viability of consolidation of the enzymatic hydrolysis and cellulase production steps in the new route using Neurospora crassa as the model microorganism and the conversion of cellulose to ethanol as the model system. We intended to prove the two hypotheses: 1) cellulose can be directed to produce cellobionate by reducing β-glucosidase production and by enhancing cellobiose dehydrogenase production; and 2) both of the two hydrolysis products of cellobionate—glucose and gluconate—can be used as carbon sources for ethanol and other chemical production. Our results showed that knocking out multiple copies of β-glucosidase genes led to cellobionate production from cellulose, without jeopardizing the cellulose hydrolysis rate. Simulating cellobiose dehydrogenase over-expression by addition of exogenous cellobiose dehydrogenase led to more cellobionate production. Both of the two hydrolysis products of cellobionate: glucose and gluconate can be used by Escherichia coli KO 11 for efficient ethanol production. They were utilized simultaneously in glucose and gluconate co-fermentation. Gluconate was used even faster than glucose. The results support the viability of the two hypotheses that lay the foundation for the proposed new route. PMID:22384058

[Interview study on autonomous chemical management system and the contribution of occupational health specialists in companies].

PubMed

Mori, Koji; Takebayashi, Toru

2004-09-01

Under the circumstance that autonomous risk management for chemicals is required in Japan, it is necessary to define fundamental steps for developing chemical management system that are applicable in various types of companies and to understand the effective contribution of chemical or occupational health specialists to the system. For the purposes, we conducted interviews with companies which have an advanced chemical management system in Japan. As the result, each company had a certain policy about detailedness level of collected hazard and exposure information, and also had an efficient risk management system to ensure workers' health in depending on the business type and situations. Moreover, it was commonly observed that the specialists played major roles in developing tools for risk assessment and control, and then business lines led execution of the risk management with their supports. Based on the interviews, we showed a hypothesis of basic steps in introducing autonomous chemical risk management system at the workplaces. It is necessary to verify the hypothesis and to develop a simple system that is applicable to middle or small size companies as the next step.

Noncatalytic transformation of the crude lipid of ChlorellaI vulgaris into fatty acid methyl ester (FAME) with charcoal via a thermo-chemical process.

PubMed

Kwon, Eilhann E; Jeon, Young Jae; Yi, Haakrho

2013-02-01

The noncatalytic transformation of the crude lipid of Chlorella vulgaris (C. vulgaris) into fatty acid methyl ester (FAME) via a thermo-chemical process was mainly investigated in this work. The crude lipid of C. vulgaris was recovered by means of solvent extraction from C. vulgaris cultivated in a raceway pond. The conventional catalyzed transesterification of crude lipid of C. vulgaris is notably inhibited by the impurities contained in the crude lipid of C. vulgaris. These impurities are inevitably derived from the solvent extraction process for C. vulgaris. However, this work presents the noncatalytic transesterification of microalgal lipid into FAME, which could be an alternative option. For example, the noncatalytic transformation of microalgal lipid into FAME provides evidence that the esterification of free fatty acids (FFAs) and the transesterification of triglycerides can be combined into a single step less susceptible to the impurities and with a high conversion efficiency (∼97%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Electrical property of macroscopic graphene composite fibers prepared by chemical vapor deposition.

PubMed

Sun, Haibin; Fu, Can; Gao, Yanli; Guo, Pengfei; Wang, Chunlei; Yang, Wenchao; Wang, Qishang; Zhang, Chongwu; Wang, Junya; Xu, Junqi

2018-07-27

Graphene fibers are promising candidates in portable and wearable electronics due to their tiny volume, flexibility and wearability. Here, we successfully synthesized macroscopic graphene composite fibers via a two-step process, i.e. first electrospinning and then chemical vapor deposition (CVD). Briefly, the well-dispersed PAN nanofibers were sprayed onto the copper surface in an electrified thin liquid jet by electrospinning. Subsequently, CVD growth process induced the formation of graphene films using a PAN-solid source of carbon and a copper catalyst. Finally, crumpled and macroscopic graphene composite fibers were obtained from carbon nanofiber/graphene composite webs by self-assembly process in the deionized water. Temperature-dependent conduct behavior reveals that electron transport of the graphene composite fibers belongs to hopping mechanism and the typical electrical conductivity reaches 4.59 × 10 3 S m -1 . These results demonstrated that the graphene composite fibers are promising for the next-generation flexible and wearable electronics.

Ceramization of low and intermediate level radioactive wastes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fiquet, O.; Berson, X.

1993-12-31

A ceramic conditioning is studied for a large variety of low and intermediate level wastes. These wastes arise from several waste streams coming from all process steps of the fuel cycle. The physical properties of ceramics can advantageously be used for radioactive waste immobilization. Their chemical durability can offer a barrier against external aggression. More over, some minerals have possible host sites in their crystal structure for heavy elements which can confer the best immobilization mechanism. The general route for development studies is described giving compositions and process choices. Investigations have been conducted on clay materials and on the processmore » parameters which condition the final product properties. Two practical examples are described concerning chemical precipitation sludge resulting from liquid waste treatment and chamot used as a fluidized bed in a graphite incinerator. Important process parameters are put in evidence and the possibility of a pilot plant development is briefly mentioned. Results of investigations are promising to define a new route of conditioning.« less

Hybridizing energy conversion and storage in a mechanical-to-electrochemical process for self-charging power cell.

PubMed

Xue, Xinyu; Wang, Sihong; Guo, Wenxi; Zhang, Yan; Wang, Zhong Lin

2012-09-12

Energy generation and energy storage are two distinct processes that are usually accomplished using two separated units designed on the basis of different physical principles, such as piezoelectric nanogenerator and Li-ion battery; the former converts mechanical energy into electricity, and the latter stores electric energy as chemical energy. Here, we introduce a fundamental mechanism that directly hybridizes the two processes into one, in which the mechanical energy is directly converted and simultaneously stored as chemical energy without going through the intermediate step of first converting into electricity. By replacing the polyethylene (PE) separator as for conventional Li battery with a piezoelectric poly(vinylidene fluoride) (PVDF) film, the piezoelectric potential from the PVDF film as created by mechanical straining acts as a charge pump to drive Li ions to migrate from the cathode to the anode accompanying charging reactions at electrodes. This new approach can be applied to fabricating a self-charging power cell (SCPC) for sustainable driving micro/nanosystems and personal electronics.

Effect of Chemical and Physical Properties on the In Vitro Degradation of 3D Printed High Resolution Poly(propylene fumarate) Scaffolds.

PubMed

Walker, Jason M; Bodamer, Emily; Krebs, Olivia; Luo, Yuanyuan; Kleinfehn, Alex; Becker, Matthew L; Dean, David

2017-04-10

Two distinct molecular masses of poly(propylene fumarate) (PPF) are combined with an additive manufacturing process to fabricate highly complex scaffolds possessing controlled chemical properties and porous architecture. Scaffolds were manufactured with two polymer molecular masses and two architecture styles. Degradation was assessed in an accelerated in vitro environment. The purpose of the degradation study is not to model or mimic in vivo degradation, but to efficiently compare the effect of modulating scaffold properties. This is the first study addressing degradation of chain-growth synthesized PPF, a process that allows for considerably more control over molecular mass distribution. It demonstrates that, with greater process control, not only is scaffold fabrication reproducible, but the mechanical properties and degradation kinetics can be tailored by altering the physical properties of the scaffold. This is a clear step forward in using PPF to address unmet medical needs while meeting regulatory demands and ultimately obtaining clinical relevancy.

Experimental study of defoaming by air-borne power ultrasonic technology

NASA Astrophysics Data System (ADS)

Rodríguez, Germán; Riera, Enrique; Gallego-Juárez, Juan A.; Acosta, Víctor M.; Pinto, Alberto; Martínez, Ignacio; Blanco, Alfonso

2010-01-01

Foam is a dispersion of gas in a liquid in which the distances between the gas bubbles are very small. Foams are frequently generated in the manufacture of many products as result from the aeration and agitation of liquids, from the vaporization of the liquid and also from biological or chemical reactions. Foams are generally an unwanted product in industrial processes because they cause difficulties in process control and in equipment operation. The most efficient conventional method for defoaming is the use of chemical agents but they contaminate the product. High-intensity ultrasonic waves offer a clean procedure to break foam bubbles. The potential use of ultrasound for foam breaking that was known since many years has been recently reinforced by the application of a new type of ultrasonic defoamer based on the stepped-plate high-power transducers to generate air-borne ultrasound. This defoamer has been successfully applied in several industrial problems such as the control of excess foam produced during the filling operation of bottles and cans on high-speed canning lines and in fermenting vessels and other reactors of great dimensions. The treatment of such industrial problems requires the proper characterization and quantification of the main parameters involved in the mechanisms of the defoaming effect. This paper deals with an experimental study about the separate influence of such parameters with the aim of improving the application of the stepped-plate power ultrasonic generators for the production of the defoaming action on industrial processes

A simplified bioprocess for human alpha-fetoprotein production from inclusion bodies.

PubMed

Leong, Susanna S J; Middelberg, Anton P J

2007-05-01

A simple and effective Escherichia coli (E. coli) bioprocess is demonstrated for the preparation of recombinant human alpha-fetoprotein (rhAFP), a pharmaceutically promising protein that has important immunomodulatory functions. The new rhAFP process employs only unit operations that are easy to scale and validate, and reduces the complexity embedded in existing inclusion body processing methods. A key requirement in the establishment of this process was the attainment of high purity rhAFP prior to protein refolding because (i) rhAFP binds easily to hydrophobic contaminants once refolded, and (ii) rhAFP aggregates during renaturation, in a contaminant- dependent way. In this work, direct protein extraction from cell suspension was coupled with a DNA precipitation-centrifugation step prior to purification using two simple chromatographic steps. Refolding was conducted using a single-step, redox-optimized dilution refolding protocol, with refolding success determined by reversed phase HPLC analysis, ELISA, and circular dichroism spectroscopy. Quantitation of DNA and protein contaminant loads after each unit operation showed that contaminant levels were reduced to levels comparable to traditional flowsheets. Protein microchemical modification due to carbamylation in this urea-based process was identified and minimized, yielding a final refolded and purified product that was significantly purified from carbamylated variants. Importantly, this work conclusively demonstrates, for the first time, that a chemical extraction process can substitute the more complex traditional inclusion body processing flowsheet, without compromising product purity and yield. This highly intensified and simplified process is expected to be of general utility for the preparation of other therapeutic candidates expressed as inclusion bodies. (c) 2006 Wiley Periodicals, Inc.

Detoxification of olive mill wastewater by electrocoagulation and sedimentation processes.

PubMed

Khoufi, Sonia; Feki, Firas; Sayadi, Sami

2007-04-02

Olive mill wastewater (OMW) is characterised by its high suspended solids content (SS), high turbidity (NTU), chemical oxygen demand (COD) concentration up to 100 gl(-1) and toxic phenolic compounds concentration up to 10 gl(-1). This study examined the effect of a physico-electrochemical method to detoxify olive mill wastewater prior an anaerobic biotreatment process. The proposed pre-treatment process consisted in a preliminary electrocoagulation step in which most phenolic compounds were polymerised, followed by a sedimentation step. The BOD(5)/COD ratio of the electrocoagulated OMW increased from 0.33, initial value, to 0.58. Furthermore, the sedimentation step yielded the removal of 76.2%, 75% and 71% of phenolic compounds, turbidity and suspended solid, respectively, after 3 days of plain settling. The combination of electrocoagulation and sedimentation allowed a COD reduction and decoloration of about 43% and 90%, respectively. This pre-treatment decreases the inhibition of Vibrio fisheri luminescence by 66.4%. Continuous anaerobic biomethanization experiments conducted in parallel with raw OMW and electrocoagulated OMW before and after sedimentation at a loading rate of 6g COD l(-1)day(-1), proved that the final pre-treated OMW was bioconverted into methane at high yield while raw OMW was very toxic to anaerobic microorganisms.

Sequential electrokinetic treatment and oxalic acid extraction for the removal of Cu, Cr and As from wood.

PubMed

Isosaari, Pirjo; Marjavaara, Pieti; Lehmus, Eila

2010-10-15

Removal of Cu, Cr and As from utility poles treated with chromated copper arsenate (CCA) was investigated using different one- to three-step combinations of oxalic acid extraction and electrokinetic treatment. The experiments were carried out at room temperature, using 0.8% oxalic acid and 30 V (200 V/m) of direct current (DC) or alternating current in combination (DC/AC). Six-hour extraction removed only 15%, 11% and 28% and 7-day electrokinetic treatment 57%, 0% and 17% of Cu, Cr and As from wood chips, respectively. The best combination for all the metals was a three-step process consisting of pre-extraction, electrokinetics and post-extraction steps, yielding removals of 67% for Cu, 64% for Cr and 81% for As. Oxalic acid extraction prior to electrokinetic treatment was deleterious to further removal of Cu, but it was necessary for Cr and As removal. Chemical equilibrium modelling was used to explain the differences in the behaviour of Cu, Cr and As. Due to the dissimilar nature of these metals, it appeared that even more process sequences and/or stricter control of the process conditions would be needed to obtain the >99% removals required for safe recycling of the purified wood material. 2010 Elsevier B.V. All rights reserved.

Optimization of Electrical Methods for Sub -surface Monitoring of Biological Contamination: From Micro-scale to Macroscopic one through Sub-micrometric Topographic and Electrochemical Studies of Oxydation/Reduction Processes Provoked by Bacteria

NASA Astrophysics Data System (ADS)

Dhahri, S.; Marliere, C.

2012-12-01

The presence of biological matter (bacteria) in deep geological sites for storage of, for instance, radioactive elements or groundwater in aquifers was clearly proved. That biomass triggers physical and chemical processes which greatly modify the durability and the sustainability of the storage sites. These processes, mainly from oxidative/reductive reactions, are poorly understood. This is mainly due to the fact that former studies were done at the macroscopic level far away from the micrometric scale where relevant processes induced by bacteria take place. Investigations at microscopic level are needed. Thus, we developed an experimental set -up based on the combined use of optical microscopy (epifluorescence and transmission), atomic force microscopy (AFM) and scanning electro -chemical microscopy (SECM) in order to get simultaneous information on topographic and electro -chemical processes at different length scales. The first highly sensitive step was to use AFM and optical microscopy with biological samples in liquid environment: We will present a new, non -perturbative method for imaging bacteria in their natural liquid environment using AFM. No immobilization protocol, neither chemical nor mechanical, is needed, contrary to what has been regarded till now as essential. Furthermore we were able to follow the natural gliding movements of bacteria, directly proving their living state during the AFM investigation: we thus directly prove the low impact of these breakthrough AFM observations on the native behavior of the bacteria. The second delicate step was to combine AFM and optical measurements with electrical ones. We mounted a new experimental set-up coupling real -time (i) monitoring of optical properties as the optical density (OD) evolution related to bulk bacterial growth in liquid or as the counting of number of bacteria adhering on the surface of the sample as well and (ii) electrical and electrochemical measurements. We thus will present results on the observed crossed correlations between physical, chemical and biological processes induced by the studied bacteria and the resulting variations of electrical signals as measured at different length scales. We indeed used variable sizes for the electrodes - from 10cm -square (colonies of around 10000 bacteria) to 0.1-1microns -square (the scale of an individual cell) thanks to newly manufactured AFM -SECM probes (using Focused Ion Beam - FIB method). These experiments were done with several bacterial strains, various medias (inoculated by bacteria versus non -inoculated). Furthermore, these results will shortly be applied to the optimized monitoring of the in -situ activity of bacteria consuming oil pollutants, following this way, in real -time, the bioremediation of an oil -contaminated soil (ANR ECOTECH_BIOPHY program).

Chemicals from coal - The Eastman experience. [Anhydride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larkins, T.H.

1986-03-01

Tennessee Eastman Company is a major producer of chemicals, fibers and plastics. It is located in Kingsport, Tennessee, headquarters for the Eastman Chemicals Division of Eastman Kodak Company. Eastman Companies employ a total of 12,250 people in Kingsport. Other domestic Eastman Chemicals Division plants are located in Texas, South Carolina, Arkansas and New York. The authors began to witness a flow of products from one of the most highly technical and sophisticated chemical processes in operation in the world. The Eastman ''Chemicals-from-Coal'' facility is not a sunfuel plant. To be sure, we are producing syngas from coal, but the syngasmore » is used to produce acetic anhydride. Acetic anhydride is very important to Eastman. This chemical intermediate eventually finds its way into such diverse products as aspirin, cigarette filters, tool handles, and photographic film. It also is used to make other chemical intermediates such as cellulose esters, anhydrides, triacetin, and acetate ester solvents, all of which have a variety of end uses. The chemicals-from-coal project had its inception in the late 1960's when Eastman stepped up its program of energy conservation and began a search for lower cost chemical feedstocks. Our concern started before the national concern caused by a ten-fold increase in petroleum prices during the past decade.« less

Discovery of optimal zeolites for challenging separations and chemical conversions through predictive materials modeling

NASA Astrophysics Data System (ADS)

Siepmann, J. Ilja; Bai, Peng; Tsapatsis, Michael; Knight, Chris; Deem, Michael W.

2015-03-01

Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure and the type or location of active sites. To date, 213 framework types have been synthesized and >330000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol beyond the ethanol/water azeotropic concentration in a single separation step from fermentation broths and the hydroisomerization of alkanes with 18-30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modeling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds. Financial support from the Department of Energy Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG02-12ER16362 is gratefully acknowledged.

Mid-infrared (MIR) photonics: MIR passive and active fiberoptics chemical and biomedical, sensing and imaging

NASA Astrophysics Data System (ADS)

Seddon, Angela B.

2016-10-01

The case for new, portable, real-time mid-infrared (MIR) molecular sensing and imaging is discussed. We set a record in demonstrating extreme broad-band supercontinuum (SC) generated light 1.4-13.3 μm in a specially engineered, step-index MIR optical fiber of high numerical aperture. This was the first experimental demonstration truly to reveal the potential of MIR fibers to emit across the MIR molecular "fingerprint spectral region" and a key first step towards bright, portable, broadband MIR sources for chemical and biomedical, molecular sensing and imaging in real-time. Potential applications are in the healthcare, security, energy, environmental monitoring, chemical-processing, manufacturing and the agriculture sectors. MIR narrow-line fiber lasers are now required to pump the fiber MIR-SC for a compact all-fiber solution. Rare-earth-ion (RE-) doped MIR fiber lasers are not yet demonstrated >=4 μm wavelength. We have fabricated small-core RE-fiber with photoluminescence across 3.5-6 μm, and long excited-state lifetimes. MIR-RE-fiber lasers are also applicable as discrete MIR fiber sensors in their own right, for applications including: ship-to-ship free-space communications, aircraft counter-measures, coherent MIR imaging, MIR-optical coherent tomography, laser-cutting/ patterning of soft materials and new wavelengths for fiber laser medical surgery.

Characterization of sildenafil citrate tablets of different sources by near infrared chemical imaging and chemometric tools.

PubMed

Sabin, Guilherme P; Lozano, Valeria A; Rocha, Werickson F C; Romão, Wanderson; Ortiz, Rafael S; Poppi, Ronei J

2013-11-01

The chemical imaging technique by near infrared spectroscopy was applied for characterization of formulations in tablets of sildenafil citrate of six different sources. Five formulations were provided by Brazilian Federal Police and correspond to several trademarks of prohibited marketing and one was an authentic sample of Viagra. In a first step of the study, multivariate curve resolution was properly chosen for the estimation of the distribution map of concentration of the active ingredient in tablets of different sources, where the chemical composition of all excipients constituents was not truly known. In such cases, it is very difficult to establish an appropriate calibration technique, so that only the information of sildenafil is considered independently of the excipients. This determination was possible only by reaching the second-order advantage, where the analyte quantification can be performed in the presence of unknown interferences. In a second step, the normalized histograms of images from active ingredient were grouped according to their similarities by hierarchical cluster analysis. Finally it was possible to recognize the patterns of distribution maps of concentration of sildenafil citrate, distinguishing the true formulation of Viagra. This concept can be used to improve the knowledge of industrial products and processes, as well as, for characterization of counterfeit drugs. Copyright © 2013. Published by Elsevier B.V.

Chemistry Cook-Off

ERIC Educational Resources Information Center

McCormick, Cynthia

2012-01-01

For this activity, high school chemistry students compete in a cooking contest. They must determine the chemical and physical changes that occur in the food they prepare, present their recipe as a step-by-step procedure similar to a lab procedure, identify chemicals in the food, and present all measurements in both metric and English units. The…

Laser surface structuring of AZ31 Mg alloy for controlled wettability.

PubMed

Gökhan Demir, Ali; Furlan, Valentina; Lecis, Nora; Previtali, Barbara

2014-06-01

Structured surfaces exhibit functional properties that can enhance the performance of a bioimplant in terms of biocompatibility, adhesion, or corrosion behavior. In order to tailor the surface property, chemical and physical methods can be used in a sequence of many steps. On the other hand, laser surface processing can provide a single step solution to achieve the designated surface function with the use of simpler equipment and high repeatability. This work provides the details on the surface structuring of AZ31, a biocompatible and biodegradable Mg alloy, by a single-step laser surface structuring based on remelting. The surfaces are characterized in terms of topography, chemistry, and physical integrity, as well as the effective change in the surface wetting behavior is demonstrated. The results imply a great potential in local or complete surface structuring of medical implants for functionalization by the flexible positioning of the laser beam.

A chemical-biological similarity-based grouping of complex substances as a prototype approach for evaluating chemical alternatives.

PubMed

Grimm, Fabian A; Iwata, Yasuhiro; Sirenko, Oksana; Chappell, Grace A; Wright, Fred A; Reif, David M; Braisted, John; Gerhold, David L; Yeakley, Joanne M; Shepard, Peter; Seligmann, Bruce; Roy, Tim; Boogaard, Peter J; Ketelslegers, Hans B; Rohde, Arlean M; Rusyn, Ivan

2016-08-21

Comparative assessment of potential human health impacts is a critical step in evaluating both chemical alternatives and existing products on the market. Most alternatives assessments are conducted on a chemical-by-chemical basis and it is seldom acknowledged that humans are exposed to complex products, not individual substances. Indeed, substances of U nknown or V ariable composition, C omplex reaction products, and B iological materials (UVCBs) are ubiquitous in commerce yet they present a major challenge for registration and health assessments. Here, we present a comprehensive experimental and computational approach to categorize UVCBs according to global similarities in their bioactivity using a suite of in vitro models. We used petroleum substances, an important group of UVCBs which are grouped for regulatory approval and read-across primarily on physico-chemical properties and the manufacturing process, and only partially based on toxicity data, as a case study. We exposed induced pluripotent stem cell-derived cardiomyocytes and hepatocytes to DMSO-soluble extracts of 21 petroleum substances from five product groups. Concentration-response data from high-content imaging in cardiomyocytes and hepatocytes, as well as targeted high-throughput transcriptomic analysis of the hepatocytes, revealed distinct groups of petroleum substances. Data integration showed that bioactivity profiling affords clustering of petroleum substances in a manner similar to the manufacturing process-based categories. Moreover, we observed a high degree of correlation between bioactivity profiles and physico-chemical properties, as well as improved groupings when chemical and biological data were combined. Altogether, we demonstrate how novel in vitro screening approaches can be effectively utilized in combination with physico-chemical characteristics to group complex substances and enable read-across. This approach allows for rapid and scientifically-informed evaluation of health impacts of both existing substances and their chemical alternatives.

CheNER: a tool for the identification of chemical entities and their classes in biomedical literature.

PubMed

Usié, Anabel; Cruz, Joaquim; Comas, Jorge; Solsona, Francesc; Alves, Rui

2015-01-01

Small chemical molecules regulate biological processes at the molecular level. Those molecules are often involved in causing or treating pathological states. Automatically identifying such molecules in biomedical text is difficult due to both, the diverse morphology of chemical names and the alternative types of nomenclature that are simultaneously used to describe them. To address these issues, the last BioCreAtIvE challenge proposed a CHEMDNER task, which is a Named Entity Recognition (NER) challenge that aims at labelling different types of chemical names in biomedical text. To address this challenge we tested various approaches to recognizing chemical entities in biomedical documents. These approaches range from linear Conditional Random Fields (CRFs) to a combination of CRFs with regular expression and dictionary matching, followed by a post-processing step to tag those chemical names in a corpus of Medline abstracts. We named our best performing systems CheNER. We evaluate the performance of the various approaches using the F-score statistics. Higher F-scores indicate better performance. The highest F-score we obtain in identifying unique chemical entities is 72.88%. The highest F-score we obtain in identifying all chemical entities is 73.07%. We also evaluate the F-Score of combining our system with ChemSpot, and find an increase from 72.88% to 73.83%. CheNER presents a valid alternative for automated annotation of chemical entities in biomedical documents. In addition, CheNER may be used to derive new features to train newer methods for tagging chemical entities. CheNER can be downloaded from http://metres.udl.cat and included in text annotation pipelines.

Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

NASA Astrophysics Data System (ADS)

Aleksandrova, E. O.; Novichkov, R. V.; Olenin, A. Yu.; Zuev, B. K.

2017-03-01

Silica nanoparticles are obtained according to the Stober-Fink-Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50-200 nm) form during primary chemical process; the average size of the particles can be increased to 400-500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

Metal ferrite spinel energy storage devices and methods for making and using same

DOEpatents

Weimer, Alan W [Niwot, CO; Perkins, Christopher [Boulder, CO; Scheffe, Jonathan [Westminster, CO; George, Steven M [Boulder, CO; Lichty, Paul [Westminster, CO

2012-05-29

1-100 nm metal ferrite spinel coatings are provided on substrates, preferably by using an atomic layer deposition process. The coatings are able to store energy such as solar energy, and to release that stored energy, via a redox reaction. The coating is first thermally or chemically reduced. The reduced coating is then oxidized in a second step to release energy and/or hydrogen, carbon monoxide or other reduced species.

Metal ferrite spinel energy storage devices and methods for making and using same

DOEpatents

Weimer, Alan W.; Perkins, Christopher; Scheffe, Jonathan; George, Steven M.; Lichty, Paul

2013-03-19

1-100 nm metal ferrite spinel coatings are provided on substrates, preferably by using an atomic layer deposition process. The coatings are able to store energy such as solar energy, and to release that stored energy, via a redox reaction. The coating is first thermally or chemically reduced. The reduced coating is then oxidized in a second step to release energy and/or hydrogen, carbon monoxide or other reduced species.

Hydrocarbon Synthesis from Carbon Dioxide and Hydrogen: A Two-Step Process

DTIC Science & Technology

2013-08-14

Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef4011115 • Publication Date (Web): 14 Aug 2013 Downloaded from http://pubs.acs.org on August 19...2013 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication . They are posted online prior to technical...editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community

Atomically Traceable Nanostructure Fabrication

PubMed Central

Ballard, Josh B.; Dick, Don D.; McDonnell, Stephen J.; Bischof, Maia; Fu, Joseph; Owen, James H. G.; Owen, William R.; Alexander, Justin D.; Jaeger, David L.; Namboodiri, Pradeep; Fuchs, Ehud; Chabal, Yves J.; Wallace, Robert M.; Reidy, Richard; Silver, Richard M.; Randall, John N.; Von Ehr, James

2015-01-01

Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure. PMID:26274555

Atomically Traceable Nanostructure Fabrication.

PubMed

Ballard, Josh B; Dick, Don D; McDonnell, Stephen J; Bischof, Maia; Fu, Joseph; Owen, James H G; Owen, William R; Alexander, Justin D; Jaeger, David L; Namboodiri, Pradeep; Fuchs, Ehud; Chabal, Yves J; Wallace, Robert M; Reidy, Richard; Silver, Richard M; Randall, John N; Von Ehr, James

2015-07-17

Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure.

More Genetic Engineering With Cloned Hemoglobin Genes

NASA Technical Reports Server (NTRS)

Bailey, James E.

1992-01-01

Cells modified to enhance growth and production of proteins. Method for enhancing both growth of micro-organisms in vitro and production of various proteins or metalbolites in these micro-organisms provides for incorporation of selected chromosomal or extrachormosomal deoxyribonucleic acid (DNA) sequences into micro-organisms from other cells or from artificial sources. Incorporated DNA includes parts encoding desired product(s) or characteristic(s) of cells and parts that control expression of productor characteristic-encoding parts in response to variations in environment. Extended method enables increased research into growth of organisms in oxygen-poor environments. Industrial applications found in enhancement of processing steps requiring oxygen in fermentation, enzymatic degradation, treatment of wastes containing toxic chemicals, brewing, and some oxidative chemical reactions.

Role of excited N2 in the production of nitric oxide

NASA Astrophysics Data System (ADS)

Campbell, L.; Cartwright, D. C.; Brunger, M. J.

2007-08-01

Excited N2 plays a role in a number of atmospheric processes, including auroral and dayglow emissions, chemical reactions, recombination of free electrons, and the production of nitric oxide. Electron impact excitation of N2 is followed by radiative decay through a series of excited states, contributing to auroral and dayglow emissions. These processes are intertwined with various chemical reactions and collisional quenching involving the excited and ground state vibrational levels. Statistical equilibrium and time step atmospheric models are used to predict N2 excited state densities and emissions (as a test against previous models and measurements) and to investigate the role of excited nitrogen in the production of nitric oxide. These calculations predict that inclusion of the reaction N2[A3Σu +] + O, to generate NO, produces an increase by a factor of up to three in the calculated NO density at some altitudes.

Influence of fluid dynamic conditions on enzymatic hydrolysis of lignocellulosic biomass: Effect of mass transfer rate.

PubMed

Wojtusik, Mateusz; Zurita, Mauricio; Villar, Juan C; Ladero, Miguel; Garcia-Ochoa, Felix

2016-09-01

The effect of fluid dynamic conditions on enzymatic hydrolysis of acid pretreated corn stover (PCS) has been assessed. Runs were performed in stirred tanks at several stirrer speed values, under typical conditions of temperature (50°C), pH (4.8) and solid charge (20% w/w). A complex mixture of cellulases, xylanases and mannanases was employed for PCS saccharification. At low stirring speeds (<150rpm), estimated mass transfer coefficients and rates, when compared to chemical hydrolysis rates, lead to results that clearly show low mass transfer rates, being this phenomenon the controlling step of the overall process rate. However, for stirrer speed from 300rpm upwards, the overall process rate is controlled by hydrolysis reactions. The ratio between mass transfer and overall chemical reaction rates changes with time depending on the conditions of each run. Copyright © 2016 Elsevier Ltd. All rights reserved.

Direct synthesis of graphene on silicon oxide by low temperature plasma enhanced chemical vapor deposition.

PubMed

Muñoz, Roberto; Martínez, Lidia; López-Elvira, Elena; Munuera, Carmen; Huttel, Yves; García-Hernández, Mar

2018-06-27

Direct graphene growth on silicon with a native oxide using plasma enhanced chemical vapour deposition at low temperatures [550 °C-650 °C] is demonstrated for the first time. It is shown that the fine-tuning of a two-step synthesis with gas mixtures C2H2/H2 yields monolayer and few layer graphene films with a controllable domain size from 50 nm to more than 300 nm and the sheet resistance ranging from 8 kΩ sq-1 to less than 1.8 kΩ sq-1. Differences are understood in terms of the interaction of the plasma species - chiefly atomic H - with the deposited graphene and the native oxide layer. The proposed low temperature direct synthesis on an insulating substrate does not require any transfer processes and improves the compatibility with the current industrial processes.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing he evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-06-23

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-11-24

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

Conceptual design report for the project to install leak detection in FAST-FT-534/548/549

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galloway, K.J.

1992-07-01

This report provides conceptual designs and design recommendations for installing secondary containment and leak detection systems for three sumps at the Fluorinel and Storage Facility (FAST), CPP-666. The FAST facility is located at the Idaho Chemical Processing Plant (ICPP) at the Idaho National Engineering Laboratory (INEL). The three sumps receive various materials from the FAST water treatment process. This project involves sump upgrades to meet appropriate environmental requirements. The steps include: providing sump modifications or designs for the installation of leak chases and/or leakage accumulation, coating the sump concrete with a chemical resistant sealant (except for sump VES-FT-534 which ismore » already lined with stainless steel) to act as secondary containment, lining the sumps with a primary containment system, and providing a means to detect and remove primary containment leakage that may occur.« less

A review on the fermentation of foods and the residues of pesticides-biotransformation of pesticides and effects on fermentation and food quality.

PubMed

Regueiro, Jorge; López-Fernández, Olalla; Rial-Otero, Raquel; Cancho-Grande, Beatriz; Simal-Gándara, Jesús

2015-01-01

Residues of pesticides in food are influenced by processing such as fermentation. Reviewing the extensive literature showed that in most cases, this step leads to large reductions in original residue levels in the fermented food, with the formation of new pesticide by-products. The behavior of residues in fermentation can be rationalized in terms of the physical-chemical properties of the pesticide and the nature of the process. In addition, the presence of pesticides decrease the growth rate of fermentative microbiota (yeasts and bacterias), which provokes stuck and sluggish fermentations. These changes have in consequence repercussions on several aspects of food sensory quality (physical-chemical properties, polyphenolic content, and aromatic profile) of fermented food. The main aim of this review is to deal with all these topics to propose challenging needs in science-based quality management of pesticides residues in food.

A review on applications of nanotechnology in the enhanced oil recovery part A: effects of nanoparticles on interfacial tension

NASA Astrophysics Data System (ADS)

Cheraghian, Goshtasp; Hendraningrat, Luky

2016-01-01

Chemical enhanced oil recovery is another strong growing technology with the potential of a step change innovation, which will help to secure future oil supply by turning resources into reserves. While Substantial amount of crude oil remains in the reservoir after primary and secondary production, conventional production methods give access to on average only one-third of original oil in place, the use of surfactants and polymers allows for recovery of up to another third of this oil. Chemical flooding is of increasing interest and importance due to high oil prices and the need to increase oil production. Research in nanotechnology in the petroleum industry is advancing rapidly and an enormous progress in the application of nanotechnology in this area is to be expected. Nanotechnology has the potential to profoundly change enhanced oil recovery and to improve mechanism of recovery. This paper, therefore, focuses on the reviews of the application of nano technology in chemical flooding process in oil recovery and reviews the application nano in the polymer and surfactant flooding on the interfacial tension process.

Monitoring and Evaluation of Alcoholic Fermentation Processes Using a Chemocapacitor Sensor Array

PubMed Central

Oikonomou, Petros; Raptis, Ioannis; Sanopoulou, Merope

2014-01-01

The alcoholic fermentation of Savatiano must variety was initiated under laboratory conditions and monitored daily with a gas sensor array without any pre-treatment steps. The sensor array consisted of eight interdigitated chemocapacitors (IDCs) coated with specific polymers. Two batches of fermented must were tested and also subjected daily to standard chemical analysis. The chemical composition of the two fermenting musts differed from day one of laboratory monitoring (due to different storage conditions of the musts) and due to a deliberate increase of the acetic acid content of one of the musts, during the course of the process, in an effort to spoil the fermenting medium. Sensor array responses to the headspace of the fermenting medium were compared with those obtained either for pure or contaminated samples with controlled concentrations of standard ethanol solutions of impurities. Results of data processing with Principal Component Analysis (PCA), demonstrate that this sensing system could discriminate between a normal and a potential spoiled grape must fermentation process, so this gas sensing system could be potentially applied during wine production as an auxiliary qualitative control instrument. PMID:25184490

Guidelines for performing systematic reviews in the development of toxicity factors.

PubMed

Schaefer, Heather R; Myers, Jessica L

2017-12-01

The Texas Commission on Environmental Quality (TCEQ) developed guidance on conducting systematic reviews during the development of chemical-specific toxicity factors. Using elements from publicly available frameworks, the TCEQ systematic review process was developed in order to supplement the existing TCEQ Guidelines for developing toxicity factors (TCEQ Regulatory Guidance 442). The TCEQ systematic review process includes six steps: 1) Problem Formulation; 2) Systematic Literature Review and Study Selection; 3) Data Extraction; 4) Study Quality and Risk of Bias Assessment; 5) Evidence Integration and Endpoint Determination; and 6) Confidence Rating. This document provides guidance on conducting a systematic literature review and integrating evidence from different data streams when developing chemical-specific reference values (ReVs) and unit risk factors (URFs). However, this process can also be modified or expanded to address other questions that would benefit from systematic review practices. The systematic review and evidence integration framework can improve regulatory decision-making processes, increase transparency, minimize bias, improve consistency between different risk assessments, and further improve confidence in toxicity factor development. Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.

Scalable high-mobility MoS2 thin films fabricated by an atmospheric pressure chemical vapor deposition process at ambient temperature

NASA Astrophysics Data System (ADS)

Huang, Chung-Che; Al-Saab, Feras; Wang, Yudong; Ou, Jun-Yu; Walker, John C.; Wang, Shuncai; Gholipour, Behrad; Simpson, Robert E.; Hewak, Daniel W.

2014-10-01

Nano-scale MoS2 thin films are successfully deposited on a variety of substrates by atmospheric pressure chemical vapor deposition (APCVD) at ambient temperature, followed by a two-step annealing process. These annealed MoS2 thin films are characterized with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), micro-Raman, X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-VIS-NIR spectrometry, photoluminescence (PL) and Hall Effect measurement. Key optical and electronic properties of APCVD grown MoS2 thin films are determined. This APCVD process is scalable and can be easily incorporated with conventional lithography as the deposition is taking place at room temperature. We also find that the substrate material plays a significant role in the crystalline structure formation during the annealing process and single crystalline MoS2 thin films can be achieved by using both c-plane ZnO and c-plane sapphire substrates. These APCVD grown nano-scale MoS2 thin films show great promise for nanoelectronic and optoelectronic applications.

Low-Cost alpha Alane for Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fabian, Tibor; Petrie, Mark; Crouch-Baker, Steven

This project was directed towards the further development of the Savannah River National Laboratory (SRNL) lab-scale electrochemical synthesis of the hydrogen storage material alpha-alane and Ardica Technologies-SRI International (SRI) chemical downstream processes that are necessary to meet DoE cost metrics and transition alpha-alane synthesis to an industrial scale. Ardica has demonstrated the use of alpha-alane in a fuel-cell system for the U.S. Army WFC20 20W soldier power system that has successfully passed initial field trials with individual soldiers. While alpha-alane has been clearly identified as a desirable hydrogen storage material, cost-effective means for its production and regeneration on a scalemore » of use applicable to the industry have yet to be established. We focused on three, principal development areas: 1. The construction of a comprehensive engineering techno-economic model to establish the production costs of alpha-alane by both electrochemical and chemical routes at scale. 2. The identification of critical, cost-saving design elements of the electrochemical cell and the quantification of the product yields of the primary electrochemical process. A moving particle-bed reactor design was constructed and operated. 3. The experimental quantification of the product yields of candidate downstream chemical processes necessary to produce alpha-alane to complete the most cost-effective overall manufacturing process. Our techno-economic model shows that under key assumptions most 2015 and 2020 DOE hydrogen storage system cost targets for low and medium power can be achieved using the electrochemical alane synthesis process. To meet the most aggressive 2020 storage system cost target, $1/g, our model indicates that 420 metric tons per year (MT/y) production of alpha-alane is required. Laboratory-scale experimental work demonstrated that the yields of two of the three critical component steps within the overall “electrochemical process” were sufficiently high to meet this production target. In the case of the yield of the third step, the crystallization of alpha-alane from the primary alane-related product of the electrochemical reaction, further development is required.« less

First Principles Simulations of Hydrocarbon Conversion Processes in Functionalized Zeolitic Materials

NASA Astrophysics Data System (ADS)

Mazar, Mark Nickolaus

With increasing demand for chemicals and fuels, and finite traditional crude oil resources, there is a growing need to invent, establish, or optimize chemical processes that convert gasifiable carbon-based feedstocks (e.g., coal, natural gas, oil sands, or biomass) into the needed final products. Catalysis is central to almost every industrial chemical process, including alkane metathesis (AM) and the methanol-to-hydrocarbons (MTH) process, which represent final steps in a sequence of hydrocarbon conversion reactions. An in depth understanding of AM and MTH is essential to the selective production of the desired end products. In this dissertation, ab initio density functional theory simulations provide unique mechanistic and thermodynamic insight of specific elementary steps involved in AM and MTH as performed on zeolite supports. Zeolites have been employed throughout the petroleum industry because of their ability to perform acid-catalyzed reactions (e.g., cracking or MTH). The crystalline structure of zeolites imparts regular microporous networks and, in turn, the selective passage of molecules based on shape and functionality. Many different elements can be grafted onto or substituted into zeolites, resulting in a broad range of catalytic behavior. However, due to the variety of competing and secondary reactions that occur at experimental conditions, it is often difficult to extract quantitative information regarding individual elementary steps. ab initio calculations can be particularly useful for this purpose. Alkane metathesis (i.e., the molecular redistribution or chain length averaging of alkanes) is typically performed by transition metal hydrides on amorphous alumina or silica supports. In Chapter 3, the feasibility of AM in zeolites is assessed by using a grafted Ta-hydride complex to explore the full catalytic cycle in the self-metathesis of ethane. The decomposition of a Ta-metallacyclobutane reaction intermediate that forms during olefin metathesis is responsible for the largest activation energy of the catalytic cycle. This assessment is similar to the findings of alkane metathesis studies on alumina/silica supports and indicates that the entire AM cycle can be performed in zeolites by isolated single-atom transition metal hydrides. Performed over acid form zeolites, MTH is used in the conversion of methanol into a broad range of hydrocarbons, including alkenes, alkanes, and aromatics. For reasons that are not yet rigorously quantified, product selectivities vary dramatically based on the choice of catalyst and reaction conditions. The methylation of species containing double bonds (i.e., co-catalysts) is central to the overall process. Distinct structure-function relationships were found with respect to the elementary steps in the methylation and beta-scission of olefins. In Chapter 4, the role of zeolite topology in the step-wise methylation of ethene by surface methoxides is investigated. Elementary steps are studied across multiple frameworks (i.e., BEA, CHA, FER, MFI, and MOR) constituting a wide variety of confinement environments. The reaction of surface methoxides with ethene is found to require a transition state containing a primary carbocation. The barrier height is found to decrease nearly monotonically with respect to the degree of dispersion interactions stabilizing the primary carbocationic species in the transition state. In addition, quantification of the ``local'' dispersion energy indicates that confinement effects can not be simply correlated to pore size. The beta-scission of olefins plays an important role in the product selectivities of many important chemical processes, including MTH. In Chapter 5, beta-scission modes involving C6 and C8 isomers are investigated at a single, isolated Bronsted acid site within H-ZSM-5. We find that the relative enthalpic barriers of beta-scission elementary steps can be rationalized by the substitution order of the two different carbocationic carbon atoms that are present in the reactant (C+) and transition states (betaC). In fact, the increase in charge required by the betaC atom to go from the physi/chemi-sorbed reactant state to the beta-scission transition state (+0.23e-0.33e) is found to correlate almost linearly with the intrinsic activation energy (89-233 kJ mol-1). The charge of the betaC atom depends, to a large extent, on the substitution order of both the C+ and betaC atoms and, therefore, each beta-scission mode is a sub-category onto itself. Isomerization reactions, which are fast with respect to beta-scission, enable reactant hydrocarbons to explore and find low barrier beta-scission pathways. Selectivities predicted on the basis of the relative barrier heights of beta-scission modes accessible to C6 and C8 species indicate general agreement with experimental observations.

Recent Advances and Challenges towards Sustainable Polyhydroxyalkanoate (PHA) Production.

PubMed

Kourmentza, Constantina; Plácido, Jersson; Venetsaneas, Nikolaos; Burniol-Figols, Anna; Varrone, Cristiano; Gavala, Hariklia N; Reis, Maria A M

2017-06-11

Sustainable biofuels, biomaterials, and fine chemicals production is a critical matter that research teams around the globe are focusing on nowadays. Polyhydroxyalkanoates represent one of the biomaterials of the future due to their physicochemical properties, biodegradability, and biocompatibility. Designing efficient and economic bioprocesses, combined with the respective social and environmental benefits, has brought together scientists from different backgrounds highlighting the multidisciplinary character of such a venture. In the current review, challenges and opportunities regarding polyhydroxyalkanoate production are presented and discussed, covering key steps of their overall production process by applying pure and mixed culture biotechnology, from raw bioprocess development to downstream processing.

An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization.

PubMed

Folgueiras-Amador, Ana A; Philipps, Kai; Guilbaud, Sébastien; Poelakker, Jarno; Wirth, Thomas

2017-11-27

Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Continuous-flow synthesis of functionalized phenols by aerobic oxidation of Grignard reagents.

PubMed

He, Zhi; Jamison, Timothy F

2014-03-24

Phenols are important compounds in chemical industry. An economical and green approach to phenol preparation by the direct oxidation of aryl Grignard reagents using compressed air in continuous gas-liquid segmented flow systems is described. The process tolerates a broad range of functional groups, including oxidation-sensitive functionalities such as alkenes, amines, and thioethers. By integrating a benzyne-mediated in-line generation of arylmagnesium intermediates with the aerobic oxidation, a facile three-step, one-flow process, capable of preparing 2-functionalized phenols in a modular fashion, is established. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of an aggressive medium on discontinuous deformation of aluminum-magnesium alloy AlMg6

NASA Astrophysics Data System (ADS)

Shibkov, A. A.; Denisov, A. A.; Zolotov, A. E.; Kochegarov, S. S.

2017-01-01

It is experimentally shown that the molecular (chemical) process of surface etching of deformed aluminum-magnesium alloy AlMg6 causes the development of a macroscopic plastic strain step with an amplitude of a few percent. Using numerical simulation of the polycrystalline solid etching process, it is shown that the corrosion front morphology varies during etching from Euclid (flat) to fractal (rough). The results obtained show the key role of the surface state on the development of macroscopic mechanical instability of a material exhibiting the Portevin-Le Chatelier effect.

Low-temperature ({<=}200 Degree-Sign C) plasma enhanced atomic layer deposition of dense titanium nitride thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samal, Nigamananda; Du Hui; Luberoff, Russell

Titanium nitride (TiN) has been widely used in the semiconductor industry for its diffusion barrier and seed layer properties. However, it has seen limited adoption in other industries in which low temperature (<200 Degree-Sign C) deposition is a requirement. Examples of applications which require low temperature deposition are seed layers for magnetic materials in the data storage (DS) industry and seed and diffusion barrier layers for through-silicon-vias (TSV) in the MEMS industry. This paper describes a low temperature TiN process with appropriate electrical, chemical, and structural properties based on plasma enhanced atomic layer deposition method that is suitable for themore » DS and MEMS industries. It uses tetrakis-(dimethylamino)-titanium as an organometallic precursor and hydrogen (H{sub 2}) as co-reactant. This process was developed in a Veeco NEXUS Trade-Mark-Sign chemical vapor deposition tool. The tool uses a substrate rf-biased configuration with a grounded gas shower head. In this paper, the complimentary and self-limiting character of this process is demonstrated. The effects of key processing parameters including temperature, pulse time, and plasma power are investigated in terms of growth rate, stress, crystal morphology, chemical, electrical, and optical properties. Stoichiometric thin films with growth rates of 0.4-0.5 A/cycle were achieved. Low electrical resistivity (<300 {mu}{Omega} cm), high mass density (>4 g/cm{sup 3}), low stress (<250 MPa), and >85% step coverage for aspect ratio of 10:1 were realized. Wet chemical etch data show robust chemical stability of the film. The properties of the film have been optimized to satisfy industrial viability as a Ruthenium (Ru) preseed liner in potential data storage and TSV applications.« less