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Stewart, Frederick F

Publications and source records attributed to Stewart, Frederick F.

Project Final Report - Advanced Oxygen Separation from Air Using a Novel Mixed Matrix Membrane

This report describes a summary of the findings of the project. The technical work was divided into three activities: 1) technoeconomic analysis; 2) membrane component development (support layer, selective layer development, and gutter layer formulation); and 3) hollow fiber formation. The technoeconomic analysis includes operating, capital, and materials costs of an oxygen enrichment system with 1-3 stages. The analysis concluded that the desired gas quality (90-95% O2) cannot be reached with a single stage. The triple stage system yielded the best overall product quality at lower membrane performance levels but with the highest cost. For the membrane development activities, functionalized nanodiamonds have been shown to slightly improve membrane formation behaviors and gas permeability performance. For example, support layers based on polysulfone-nanodiamond composites have been formed that increase the material’s O2 permeability by over a factor of 150, however, at the cost of selectivity that suggests a change in transport mechanism. Furthermore, nanodiamonds have been found to improve membrane durability. Improvements in selective and gutter layers also have been accomplished. An additional accomplishment is the demonstration of phase inversion of polysulfone-nanodiamond composites that ensures that hollow fiber formation can be performed. Finally, the interfaces between support, gutter, and selective layers were briefly examined and the resulting membrane material consisting of all three layers gave good performance in an O2 separation from N2. The three-layer prototype membrane gave permeability of 29.2-32.2 Barrers, which equates to permeance of approximately 290-320 GPU, which is lower than the TEA informed goal of 500 GPU. O2/N2 selectivity ranged from 5.2-6.2, which is consistent with the less costly two-stage implementation of the technology. In summary, new materials have been developed for O2 concentration from air and are well-suited to a hollow fiber format.

20 FOSSIL-FUELED POWER PLANTS↗

Analysis of Various Polysulfone-nanodiamond Mixed-Matrix Membranes

Historically, coal combustion systems have contributed to the extensive network of energy production across the world. Oxycombustion has been shown to be more energy efficient and can facilitate carbon capture from fossil energy utilization. The challenge for small modular deployment of coal combustion or gasification systems is that current O2 enrichment technologies do not scale downward cost-effectively. Fortunately, membrane processes have been developed to offer a more viable polymer-based technology for this application. The central focus is to deliver a high-performance polymer membrane capable of enriching O2 to 90-95% in oxycombustion systems for small modular coal-based power or gasification plants. To accomplish this, various properties of polysulfone-nanodiamond mixed-matrix membrane are examined to determine the appropriate conditions for applicable use. The polymers are infused with nanoparticles to increase the mechanical functionality of the structure which in turn alters the permeability and selectivity of the membrane. Furthermore, the thermal history can also impact the functionality and characteristics of these polymer systems. This study primarily discusses the structure and function of these assorted membranes in terms of permeability and thermomechanical characteristics.

01 COAL, LIGNITE, AND PEAT↗

Thermomechanical Analysis of Polysulfone-Nanodiamond Mixed Matrix Membranes

Idaho National Laboratory is developing a polymer membrane designed to concentrate oxygen from air to assist in cleaner coal combustion and other gasification processes. These membranes were formed by adding nanodiamond particles to enhance their transport properties. This study focuses on the thermomechanical analysis (TMA) of these membranes to probe the behavior between the nanodiamond particles and the polymer.

20 FOSSIL-FUELED POWER PLANTS↗

Thermal Analysis of Mixed Matrix Membranes Involved in Gas Separation

Idaho National Laboratory is developing a mixed matrix membrane that can separate oxygen from air. The enriched oxygen stream is intended to be used in gasification systems and coal combustion. This study evaluated the thermal properties of polymer membranes that were cast from different solvents and contained various concentrations of nanodiamonds, where the polymer-nanodiamond composites acted as the selective layer. Measuring these properties helped to understand the membrane formation process to yield membranes that give reproducible performance. Thermomechanical Analysis determined that nanodiamonds cause a physical effect on the membrane when exposed to heating. Thermogravimetric Analysis and Differential Scanning Calorimetry determined residual solvent in the membrane after formation. Residual solvent tended to decrease the performance of membranes. From this work, we developed a method of forming solvent-free polysulfone membrane composites containing nanodiamond particles that gave reproducible permeability and selectivity data.

25 ENERGY STORAGE↗

Electrodes including a polyphosphazene cyclomatrix, methods of forming the electrodes, and related electrochemical cells

An electrode comprising a polyphosphazene cyclomatrix and particles within pores of the polyphosphazene cyclomatrix. The polyphosphazene cyclomatrix comprises a plurality of phosphazene compounds and a plurality of cross-linkages. Each phosphazene compound of the plurality of phosphazene compounds comprises a plurality of phosphorus-nitrogen units, and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. Each phosphorus-nitrogen unit is bonded to an adjacent phosphorus-nitrogen unit. Each cross-linkage of the plurality of cross-linkages bonds at least one pendant group of one phosphazene compound of the plurality of phosphazene compounds with the at least one pendant group of another phosphazene compound of the plurality of phosphazene compounds. A method of forming a negative electrode and an electrochemical cell are also described.

25 ENERGY STORAGE↗

Taggants, method for forming a taggant, and a method for detecting an object

A taggant comprising at least one perfluorocarbon compound surrounded by a polyphosphazene compound. The polyphosphazene compound has the chemical structure: ##STR00001## wherein G.sub.1 and G.sub.2 are pendant groups having different polarities, m is an integer greater than or equal to 100, and each of A and B is independently selected from hydrogen, an alkyl, an alkene, an alkoxide, a polyether, a polythioether, a siloxane, and --X(CH.sub.2).sub.nY.sup.1(CH.sub.2)p.sub.1Y.sup.2(CH.sub.2)p.sub.2 . . . Y.sup.i(CH.sub.2)p.sub.iCH.sub.3, where n ranges from 1 to 6, X and Y are independently selected from oxygen, sulfur, selenium, tellurium, and polonium, and p.sub.1 through p.sub.i range from 1 to 6. Cyclic polyphosphazene compounds lacking the A and B groups are also disclosed, as are methods of forming the taggant and of detecting an object.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Alkyl Substitution on the Physical Properties and Gas Transport Behavior in Selected Poly(R-phenoxyphosphazenes)

A systematic preparation of alkyl substituted phenoxy-phosphazene polymers was performed. In this study, phosphazenes substituted with 4-methylphenol, 4-ethylphenol, and 4-isopropylphenol are reported. An additional polymer substituted with 4-tert-butylphenoxy-1-ethanol also was synthesized in this work. Data derived for these materials, including chemical, thermal and gas transport characterization, were compared to previous reports discussing poly[bis-phenoxyphosphazene] and its analog with tert-butyl substitution: poly[bis-(4-tert-butylphenoxy)phosphazene]. The tert-butyl moiety influences orderly chain packing, presumably through steric hindrance that can influence aromatic p-stacking. For the new poly[(alkylphenoxy)phosphazenes], semi-crystallinity is maintained and the added steric bulk serves to decrease the Tg and increase both permeability and selectivity for the gas pairs: O2/N2 and CO2/CH4. Removal of the tert-butyl moiety from the immediate vicinity of the backbone through a flexible spacer serves to depress the Tg as compared to poly[bis-(4-tert-butylphenoxy)phosphazene], but provides no performance enhancement for gas transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Separation of Dimethyl Ether from Syn-Gas Components by Poly(dimethylsiloxane) and Poly(4-methyl-1-pentene) Membranes

Permeability and selectivity in gas transport through poly(4-methyl-1-pentene) (TPX) and poly(dimethylsiloxane) (PDMS) using variable temperature mixed gas experiments is reported. Selected gases include H2, CO, CH4, CO2, and dimethyl ether (DME). The DME data is the first to be reported through these membranes. In this paper, the chosen polymers reflect both rubbery and crystalline materials. Rubbery polymers tend to be weakly size sieving, which, in this work, has resulted in larger permeabilities, lower separation factors, and lower activation energies of permeation (Ep). Conversely, the crystalline TPX membranes showed much greater sensitivity to penetrant size; although the gas condensability also played a role in transport.

36 MATERIALS SCIENCE↗

Phosphazenes (2010)

A review of the literature published in 2009 shows an increase in the number of publications addressing phosphazene chemistry over 2008, which suggests a continued strong interest in these intriguing materials. Prominently is the emphasis in the bioactive and biocompatible nature of these materials; although many other applications also exist. Phosphazenes are formed from a phosphorus and nitrogen backbone with pendant group attachments at phosphorus. Typically, they are drawn with alternating single and double bonds between the alternating phosphorus and nitrogen atoms. However, unlike the familiar poly(acetylenes) or poly(thiophenes), the phosphazene backbone is not electrically conductive as there are orbital nodes at phosphorus. Thus, electron delocalization occurs between phosphorus atoms, but not through them. The result of this bonding is a highly flexible backbone that can be controlled through adoit pendant group attachment revealing numerous materials and structures. In this review, novel aspects of the chemistry, structure, and applications of phosphazenes will be discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗