A more direct approach to polyenes by the direct polymerization of acetylenes has been achieved. We were able to show that polymerization of acetylene itself can be controlled with a well- characterized alkylidene catalyst, but only if a base such as quinuclidine is present in order to slow down the rate of propagation relative to initiation. (Quinuclidine may also stabilize vinylalkylidene intermediates formed in the reaction). Unfortunately, living polyenes'' were no more stable than isolated polyenes, and so this approach had its limitations. Direct polymerization of acetylene by Mo(CH-t-Bu)(NAr)(O-t-Bu){sub 2} was more successful, but inherent polyene instability was still a problem. The most important result of the past grant period is the finding that dipropargyl derivatives (HC=CCH{sub 2}XCH{sub 2}C=CH; X = CH{sub 2}, C(CO{sub 2}R){sub 2}, SiR{sub 2}, etc.), which have been reported to be cyclopolymerized by various classical catalysts by as yet unknown mechanisms, are polymerized by Mo(CH-t-Bu)(NAr)(OCMe(CF{sub 3}){sub 2}){sub 2} in dimethoxyethane. We speculate that intramolecular formation of a five-membered ring in the product of {alpha} addition is fast enough to yield another terminal alkylidene on the time scale of the polymerization reaction, while a six-membered ring is formed in a reaction involving a more reaction terminal alkylidene. …

In an effort to encourage the maximum cost-effective level of energy efficiency in new building design, energy-efficiency standards have become more location-specific and performance-based. As a result, standards often provide more than one path for ensuring and demonstrating that a design complies, but at the cost of increased complexity. In addition, the burden of remedying a noncompliant design rests on the designers' knowledge and experience, with only general guidance provided by the standards. As part of efforts in the US Department of Energy's (DOE's) Advanced Energy Design and Operation Technologies (AEDOT) project, a team at DOE's Pacific Northwest Laboratory is developing a computer program known as the Energy Standards Intelligent Design Tool (ES-IDT). The ES-IDT is one component of a prototype computer-based building design environment. It performs automatic compliance checking for parts of ASHRAE/IES Standard 90.1-1989 and provides designers assistance in bringing noncomplying designs into compliance. This paper describes the ES-IDT, the functions it provides, and how it is integrated into the design process via the AEDOT prototype building design environment. 9 refs.

Economic analysis of this fossil resin project mainly focused on the flotation plant which is intended to be designed with data obtained from the current proof-of-concept flotation test program. It is believed that the analysis of this step is fairly accurate. The other two economic aspects of fossil in resin recovery/utilization are refining and marketing. Cost data used for refining were from an estimated base and are believed to have a large variance. Marketing data used were obtained from two independent marketing studies which were made available on confidentiality basis. Nevertheless, the data used are believed to be fairly accurate with respect to the market potential.

The Refrigerant Database consolidates and facilitates access to information to assist industry in developing equipment using alternative refrigerants. The underlying purpose is to accelerate phase out of chemical compounds of environmental concern. The database provides bibliographic citations and abstracts for publications that may be useful in research and design of air- conditioning and refrigeration equipment. The complete documents are not included, though some may be added at a later date. The database identifies sources of specific information on R-32, R-123, R-124, R- 125, R-134a, R-141b, R142b, R-143a, R-152a, R-290 (propane), R-717 (ammonia), ethers, and others as well as azeotropic and zeotropic blends of these fluids. It addresses polyalkylene glycol (PAG), ester, and other lubricants. It also references documents addressing compatibility of refrigerants and lubricants with metals, plastics, elastomers, motor insulation, and other materials used in refrigerant circuits.

The experimental high energy physics program is directed toward the execution of experiments that probe the basic constituents of matter and the forces between them. These experiments are carried out at national and international accelerator facilities. At the current time, we are primarily concentrating on the following projects: Direct photon production in hadronic reactions (Fermilab E706); Production of hybrid mesons in the nuclear Coulomb field; The D-Zero experiment at the Tevatron collider; Deep inelastic neutrino- and electron-nucleon scattering at FNAL and SLAC; Nonlinear QED at critical field strengths at SLAC; The Experiments at KEK (AMY, 17keV neutrino); The CDF experiment at the Tevatron collider; and SSC-related detector R D on scintillating tile- and diamond-based calorimetry and microstrip tracking detectors.

The overall goal of this project is to find biological methods to remove carboxylic functionalities from low-rank coals under ambient conditions and to assess the properties of these modified coals towards coal liquefaction. The main objectives of this quarter were: (1) continuation of microbial consortia development, (2) evaluation of the isolated organisms for decarboxylation, (3) selection of best performing culture (known cultures vs. new isolates), and (4) coal decarboxylation using activated carbon as blanks. The project began on September 12, 1990.

The overall objective of the research carried out under this program is to determine the principles of collisional energy transfer and use them in predictive models and theories. In order to accomplish this goal, energy transfer properties must be determined and then analyzed to discern the underlying principles involved. In this laboratory, the experimental determination of energy transfer parameters is based on techniques that use physical properties to monitor the amount of energy in excited molecules. These techniques differ from chemical methods, based on unimolecular reaction studies, which are susceptible to interferences from complex chemical mechanisms and other complications. The physical methods have their own weaknesses and limitations, however, and much of our effort has been directed toward gaining a better understanding of these deficiencies. Two physical techniques have been proved to be particularly useful: time-resolved infrared fluorescence and time-dependent thermal lensing. As described later, we will shortly begin work using resonance enhanced multiphoton ionization techniques to investigate energy transfer in bulbs and half collisions'' in free jets. We also have been completing some calculational efforts to model formation of polycyclic aromatic hydrocarbons in stellar atmospheres.

This project involves the design, synthesis and photophysical study of complex molecular systems engineered to achieve long lived charge separated states by a biomimetic, photoinitiated multistep electron transfer process. The use of these artificial systems to investigate different electron and energy transfer strategies will allow the evolution of more efficient molecular devices for the gathering of light energy and its transformation into chemical potential energy. The three major aspects of the work emphasized in the initial proposal are: design and synthesis of molecular devices incorporating new quinone moieties, synthesis and spectroscopic studies of molecular tetrads and pentads featuring modified porphyrin-diquinone linkages, and new photochemical and photophysical investigations of tetrads and pentads, including the development of methods for harvesting the energy stored in long-lived charge separated states.

The overall objective of this program is to integrate EER's expertise in boiler reburning performance evaluation into a package of analytical computer tools. Specific objectives of the program are to develop a computational capability with the following features: (1) can be used to predict the impact of gas reburning application on thermal conditions in the boiler radiant furnace, and on overall boiler performance; (2) can estimate gas reburning NO{sub x} reduction effectiveness based on specific reburning configurations and furnace/boiler configurations; (3) can be used as an analytical tool to evaluate the impact of boiler process parameters (e.g., fuel switching and changes in boiler operating conditions) on boiler thermal performance; (4) is adaptable to most boiler designs (tangential and wall fire boilers) and a variety of fuels (solid, liquid, gaseous and slurried fuels); (5) is sufficiently user friendly to be exercisable by engineers with a reasonable knowledge of boilers, and with reasonable computer skills. Here, user friendly'' means that the user will be guided by computer codes during the course of setting up individual input files for the boiler performance model.

This report will focus on means of pyrite removal from coal using surface-based coal cleaning technologies. The major subjects being addressed in this study are the natural and modulated surface properties of coal and pyrite and how they may best be utilized to facilitate their separation using advanced surface-based coal cleaning technology. Emphasis is based on modified flotation and oil agglomerative processes and the basic principles involved. The four areas being addressed are: (1) Collectorless flotation of pyrite; (2) Modulation of pyrite and coal hydrophobicity; (3) Emulsion processes and principles; (4) Evaluation of coal hydrophobicity.

Mathematical solutions to the problem consisting of a partially-full waste tank subjected to seismic loading, embedded in soil, is classically difficult in that one has to address: soil-structure interaction, fluid-structure interaction, non-linear behavior of material, dynamic effects. Separating the problem and applying numerous assumptions will yield approximate solutions. This paper explores methods for generating these solutions accurately.

Liquid high-level nuclear waste at the Savannah River Site (SRS) will be immobilized by vitrification in borosilicate glass. The glass will be produced and poured into stainless steel canisters in the Defense Waste Processing Facility (DWPF). Other waste form producers, such as West Valley Nuclear Services (WVNS) and the Hanford Waste Vitrification Project (HWVP), will also immobilize high-level radioactive waste in borosilicate glass. The canistered waste will be stored temporarily at each facility for eventual permanent disposal in a geologic repository. The Department of Energy has defined a set of requirements for the canistered waste forms, the Waste Acceptance Preliminary Specifications (WAPS). The current Waste Acceptance Preliminary Specification (WAPS) 1.3, the product consistency specification, requires the waste form producers to demonstrate control of the consistency of the final waste form using a crushed glass durability test, the Product Consistency Test (PCT). In order to be acceptable, a waste glass must be more durable during PCT analysis than the waste glass identified in the DWPF Envirorunental Assessment (EA). In order to supply all the waste form producers with the same standard benchmark glass, 1000 pounds of the EA glass was fabricated. The chemical analyses and characterization of the benchmark EA glass …

Project Objectives are to develop hydrogen-permselective ceramic membranes for water-gas shift membrane-reactor suitable for hydrogen production from coal gas and evaluate the technical and economic potential of the membrane-reactor. During the reporting period exploratory experiments begun on a membrane preparation technique aimed at providing higher membrane permeance. The new preparation technique involves two stages. The first stage is the formation of a layer of silica gel by a two-phase interfacial reaction within the pores of the substrate. The gel is then dried and calcined yielding a microporous (pore diameter below 10 [Angstrom]) silica layer within the pores of the substrate tube. The second stage involves one-sided chemical vapor deposition using the SiCl[sub 4]-H[sub 2]O reaction to close up the micropores of the gel layer and produce the final hydrogen permselective membrane. Chemical reactions involved are described.

If late washing of precipitate is available, it is possible to modify the normal washing phase of the ITP process so that tank corrosion is prevented by inhibiting with sodium hydroxide rather than sodium nitrite. Hydroxide inhibition has numerous advantages to a hydroxide/nitrite flowsheet.1 However, the rate of hydroxide depletion due to radiolysis and C0[sub 2] absorption were uncertainties. Based on recent experiments and calculations: hydroxide consumption by radiolysis will be 0.01 molar per month during Tank 49 storage, hydroxide depletion due to C0[sub 2] absorption will vary from 0.0006 to 0.025 molar per month for waste volumes between 50,000 and 1 million gallons and air flowrates between 100 and 200 cfm. A nominal rate of 0.006 molar/month (or less) is expected in Tank 49 after the first two ITP cycles have been completed. A material balance for the ITP process based on hydroxide inhibition has been calculated and the potential savings have been estimated.

The effort is divided into the following: high pressure transitions (Fe, RbCl), XAFS studies of perovskites under pressure (ReO[sub 3], high-[Tc] superconductors), studies of XANES of alkali halides, and Moessbauer studies (iron silicate spinel).

This report documents studies on the effects of gas sorption on coal, with the intent of eventually evaluating how sorption and strain affect permeability. These studies were, carried out at the University of Alabama during the period from 1989 through 1992. Two major experimental methods were developed and used. In the strain experiments, electronic strain gauges were attached to polished blocks of coal in order to measure linear and volumetric swelling due to gas sorption. The effects of bedding plane orientation, of gas type, and of coal type were investigated. In the gravimetric experiment the weight of small samples of coal was measured during exposure to high pressure gases. Sample measurements were corrected for buoyancy effects and for sample swelling, and the results were plotted in the form of Langmuir isotherms. Experiments were conducted to determine the effect of grain size, coal type, moisture, and of sorbant gas. The advantage of this method is that it can be applied to very small samples, and it enabled comparison liptinite versus vitrinite concentrates, and kerogen rich versus kerogen depleted oil shales. Also included is a detailed discussion of the makeup of coal and its effect on gas sorption behavior.

Several processing options for dissolving plutonium oxide (PuO[sub 2]) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO[sub 2] typically generated by burning plutonium metal and PuO[sub 2] produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO[sub 2] in canyon dissolvers. The options involve solid solution formation of PuO[sub 2] With uranium oxide (UO[sub 2]) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO[sub 2] with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO[sub 2] materials may warrant further study.

This report describes a laboratory-scale study, in which electrokinetic migration technology was used to remove chromium and uranium, as well as other ions, from soil taken from a bore hole adjacent to the 904-A trench at the Savannah River Technology Center. Imposition of an electric current on humid (not saturated) soil successfully caused cations to migrate through the pore water of the soil to the cathode, where they were captured in an ISOLOCKTm polymer matrix and in a cation exchange resin incorporated in the polymer. Chemicals circulated through the anode/polymer and cathode/polymer were able to control pH excursions in the electrokinetic-cells by reacting with the H[sup +] and OH[sup [minus]] generated at the anode and cathode, respectively. The study indicates that ions adsorbed on the surface of the soil as well as those in the pores of soil particles can be caused to migrate through the soil to an appropriate electrode. After 10 days of operation at 20--25 V and 2 mA, approximately 65% of the chromium was removed from two 3.5 kg soil samples. A 57% removal of uranium was achieved. The study shows that electrokinetic migration, using the ISOLOCK[trademark] polymer will be effective as an in situ treatment …

Scanning electron microscope (SEM) images of polished surfaces, electron probe microanalysis, and X-ray powder diffractometry indicated the presence of a continuous Zr[sub 2]Fe phase with secondary phases of ZrFe[sub 2], Zr[sub 5]FeSn, [alpha]-Zr, and Zr[sub 6]Fe[sub 3]O. A statistically-designed experiment to determine the effects of temperature, time, and vacuum quality On activation of St 198 revealed that when activated at low temperature (350[degrees]C) deuterium absorption rate was slower when the vacuum quality was pwr (2.5 Pa vs. 3[times]10[sup [minus]4] Pa). However, at higher activation temperature (500[degrees]C), deuterium absorption rate was fast and was independent of vacuum quality. Deuterium pressure-composition-temperature (P-C-T) data are reported for St 198 in the temperature range 200--500[degrees]C. The P-C-T data over the full range of deuterium loading and at temperatures of 350[degrees]C and below is described by: K[sub 0e]-([Delta]H[sub [alpha]]/RT)=PD[sub 2]q[sup 2]/(q*[minus]q)[sup 2] where [Delta]H[alpha] and K[sub 0] have values of 101.8 kJ[center dot]mole[sup [minus]1] and 3.24[times]10[sup [minus]8]Pa[sup [minus]1], and q* is 15.998 kPa[center dot]L[sup [minus]1][center dot]g[sup [minus]1]. At higher temperatures, one or more secondary reactions in the solid phase occur that slowly consume D[sub 2] from the gas phase. XRD suggests these reactions to be: 2 Zr[sub 2]FeD[sub x] [yields] x ZrD[sub 2] + x/3 …

This research project designed to investigate how atmospheric remote sensing technology can best be applied to the characterization of the cloudy atmosphere. Our research program addresses basic atmospheric remote sensing questions, but at the same time is clearly directed toward providing information crucial to the ARM (Atmospheric Remote Sensing) program and for application to the Clouds and Radiation Testbed (CART). The instrumentation that is being brought into play includes a variety of art-of-the-art sensors. Available at NOAA WPL are polarization Doppler K{sub a}-band (0.86 mm) and X-band (3.2 cm) radars, a C0{sub 2}(10.6 {mu}m) Doppler lidar with sequential ' polarization measurement capabilities, a three-channel (20.6, 31.65 and 90 GHz) microwave radiometer, and variety of visible and infrared radiometers. Instrumentation at the University of Utah Facility for Atmospheric Remote Sensing (FARS) includes a polarization ruby (0.643 {mu}m) lidar, a narrow-beam (0.14{degree}) mid-infrared (9.5--11.5 {mu}m) radiometer coaligned with the lidar, several other radiometers in the visible and infrared spectral regions, and an advanced two-color (1.06 and 0.532 {mu}m), four-channel Polarization Diversity Lidar (PDL) and all-sky video imaging system that have only recently been developed under the ARM IDP.

The Integrated DWPF Melter System (IDMS) for the vitrification of high-level radioactive wastes is designed and constructed to be a 1/9th scale prototype of the full scale Defense Waste Processing Facility (DWPF) melter. The IDMS facility is the first engineering scale melter system capable of processing mercury, and flowsheet levels of halides and noble metals. In order to determine the effects of mercury on the feed preparation process, the off-gas chemistry, glass melting behavior, and glass durability, a three-run mercury (Hg) campaign was conducted. The glasses produced during the Hg campaign were composed of Batch 1 sludge, simulated precipitate hydrolysis aqueous product (PHA) from the Precipitate Hydrolysis Experimental Facility (PHEF), and Frit 202. The glasses were produced using the DWPF process/product models for glass durability, viscosity, and liquidus. The durability model indicated that the glasses would all be more durable than the glass qualified in the DWPF Environmental Assessment (EA). The glass quality was verified by performing the Product Consistency Test (PCT) which was designed for glass durability testing in the DWPF.

In this project it was proposed that the selectivity of the HDN reaction can be affected by an alteration of the catalyst acidity since it is possible that an acidic Hofmann-like deamination C--N--C bonds. Such a possibility was verified in this work by studying the denitrogenation of piperidine over acidic catalysts, and it was demonstrated that Bronsted acid sites are active for the denitrogenation of N-heterocycles, whereas Lewis sites are not. To better understand the role of acidic sites in the presence of hydrogenation and hydrogenolysis sites, molybdena was supposed on a series of acidic aluminas, and the resulting new acidity and molybdic phases were characterized. The oxidized catalysts supported on silica-aluninas showed increases from 3 to 150% of weak, medium and strong acid sites, which were produced by the molybdena phases. The new acidity was both of Lewis and Bronsted type, the predominance of one over the other depending upon support composition, as well as on loading and state of oxidation of Mo. High-alumina supports and low Mo loading favor dispersed Mo species, in particular bidentate and monodentate di-oxo Mo species. The latter is responsible for the new Bronsted acidity. Coordinative unsaturation of polymolybdates is responsible for the new …

A phase II study has been initiated to investigate surfactant-assisted coal liquefaction, with the objective of quantifying the enhancement in liquid yields and product quality. This publication covers the first quarter of work. The major accomplishments were: (1) the refurbishment of the high-pressure, high-temperature reactor autoclave, (2) the completion of four coal liquefaction runs with Pittsburgh [number sign]8 coal, two each with and without sodium lignosulfonate surfactant, and (3) the development of an analysis scheme for the product liquid filtrate and filter cake. Initial results at low reactor temperatures show that the addition of the surfactant produces an improvement in conversion yields and an increase in lighter boiling point fractions for the filtrate.

The objectives of this task were to describe and evaluate selected existing sources of information on occupational safety and health with emphasis on hazard and exposure assessment, abatement, training, reporting, and control identifying for exposure and outcome in preparation for developing DOE performance benchmarks. Existing resources and methodologies were assessed for their potential use as practical performance benchmarks. Strengths and limitations of current data resources were identified. Guidelines were outlined for developing new or improved performance factors, which then could become the basis for selecting performance benchmarks. Data bases for non-DOE comparison populations were identified so that DOE performance could be assessed relative to non-DOE occupational and industrial groups. Systems approaches were described which can be used to link hazards and exposure, event occurrence, and adverse outcome factors, as needed to generate valid, reliable, and predictive performance benchmarks. Data bases were identified which contain information relevant to one or more performance assessment categories . A list of 72 potential performance benchmarks was prepared to illustrate the kinds of information that can be produced through a benchmark development program. Current information resources which may be used to develop potential performance benchmarks are limited. There is need to develop an occupational safety …