Size distributions of coastal ocean suspended particulate inorganic matter: Amorphous silica and clay minerals and their dynamics
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Optimizing solution chemistry and the addition of titania and fumed silica powder reduces shrinkage. These materials would serve to increase thermal efficiency by providing thermal insulation to suppress lateral heat leaks. They would also serve to prolong operational lifetime by suppressing sublimation of certain constituents of thermoelectric materials (e.g., sublimation of Sb from CoSb3) at typical high operating temperatures. [The use of pure silica aerogels as cast-in-place thermal-insulation and sublimation-suppression materials was described in "Aerogels for Thermal Insulation of Thermoelectric Devices" (NPO-40630), NASA Tech Briefs, Vol. 30, No. 7 (July 2006), page 50.] A silica aerogel is synthesized in a solgel process that includes preparation of a silica sol, gelation of the sol, and drying of the gel in a solvent at a supercritical temperature and pressure. The utility of pure silica aerogel is diminished by a tendency to shrink (and, therefore, also to crack) during the gelation and supercritical-drying stages. Moreover, to increase suppression of sublimation, it is advantageous to make an aerogel having greater density, but shrinkage and cracking tend to increase with density. A composite material of the type under investigation consists mostly of titania oxide powder particles and a small addition of fumed silica powder, which are mixed into the sol along with other ingredients prior to the gelation stage of processing. The silica aerogel and fumed silica act as a binder, gluing the titania particles together. It is believed that the addition of fumed silica stiffens the aerogel network and reduces shrinkage during the supercritical-drying stage. Minimization of shrinkage enables establishment of intimate contact between thermoelectric legs and the composite material, thereby maximizing the effectiveness of the material for thermal insulation and suppression of sublimation. To some extent, the properties of the composite can be tailored via the proportions of titania and other ingredients. In particular (see figure), the addition of a suitably large proportion of titania (e.g., 0.6 g/cu cm) along with a 10-percent increase in the amount of tetraethylorthosilicate [TEOS (an ingredient of the sol)] to an aerogel component having a density 40 mg/cm3makes it possible to cast a high-average-density (>0.1 g/cm3) aerogel/particle composite having low shrinkage (2.3 percent).
Hygroscopic ceramic materials which are difficult to waterproof with a silane, substituted silane or silazane waterproofing agent, such as an alumina containing fibrous, flexible and porous, fibrous ceramic insulation used on a reentry space vehicle, are rendered easy to waterproof if the interior porous surface of the ceramic is first coated with a thin coating of silica. The silica coating is achieved by coating the interior surface of the ceramic with a silica precursor converting the precursor to silica either in-situ or by oxidative pyrolysis and then applying the waterproofing agent to the silica coated ceramic. The silica precursor comprises almost any suitable silicon containing material such as a silane, silicone, siloxane, silazane and the like applied by solution, vapor deposition and the like. If the waterproofing is removed by e.g., burning, the silica remains and the ceramic is easily rewaterproofed. An alumina containing TABI insulation which absorbs more that five times its weight of water, absorbs less than 10 wt. % water after being waterproofed according to the method of the invention.
An organic polybutadiene (PB) rubberbased aerogel insulation material was developed that will provide superior thermal insulation and inherent radiation protection, exhibiting the flexibility, resiliency, toughness, and durability typical of the parent polymer, yet with the low density and superior insulation properties associated with the aerogels. The rubbery behaviors of the PB rubber-based aerogels are able to overcome the weak and brittle nature of conventional inorganic and organic aerogel insulation materials. Additionally, with higher content of hydrogen in their structure, the PB rubber aerogels will also provide inherently better radiation protection than those of inorganic and carbon aerogels. Since PB rubber aerogels also exhibit good hydrophobicity due to their hydrocarbon molecular structure, they will provide better performance reliability and durability as well as simpler, more economic, and environmentally friendly production over the conventional silica or other inorganic-based aerogels, which require chemical treatment to make them hydrophobic. Inorganic aerogels such as silica aerogels demonstrate many unusual and useful properties. There are several strategies to overcoming the drawbacks associated with the weakness and brittleness of silica aerogels. Development of the flexible fiber-reinforced silica aerogel composite blanket has proven one promising approach, providing a conveniently fielded form factor that is relatively robust toward handling in industrial environments compared to silica aerogel monoliths. However, the flexible silica aerogel composites still have a brittle, dusty character that may be undesirable, or even intolerable, in certain applications. Although the cross-linked organic aerogels such as resorcinol-formaldehyde (RF), polyisocyanurate, and cellulose aerogels show very high impact strength, they are also very brittle with little elongation (i.e., less rubbery). Also, silica and carbon aerogels are less efficient radiation shielding materials due to their lower content of hydrogen element. The present invention relates to maleinized polybutadiene (or polybutadiene adducted with maleic anhydride)- based aerogel monoliths and composites, and the methods for preparation. Hereafter, they are collectively referred to as polybutadiene aerogels. Specifically, the polybutadiene aerogels of the present invention are prepared by mixing a maleinized polybutadiene resin, a hardener containing a maleic anhydride reactive group, and a catalyst in a suitable solvent, and maintaining the mixture in a quiescent state for a sufficient period of time to form a polymeric gel. After aging at elevated temperatures for a period of time to provide uniformly stronger wet gels, the micro porous maleinized polybutadiene- based aerogel is then obtained by removing interstitial solvent by supercritical drying. The mesoporous maleinized polybutadiene-based aerogels contain an open-pore structure, which provides inherently hydrophobic, flexible, nearly unbreakable, less dusty aerogels with excellent thermal and physical properties. The materials can be used as thermal and acoustic insulation, radiation shielding, and vibration-damping materials. The organic PB-based rubber aerogels are very flexible, no-dust, and hydrophobic organics that demonstrated the following ranges of typical properties: densities of 0.08 to 0.255 grams per cubic centimeters, shrinkage factor (raerogel/rtarget) = 1.2 to 2.84, and thermal conductivity values of 20.0 to 35.0 mW/m-K.
An analysis is presented of various ceramic design concepts intended to improve nozzle throat life and tunnel performance in the hypersonic Langley 8-Foot High-Temperature Structures Tunnel, which uses methane-air combustion products as the wind-tunnel test medium. Calculations of the axial pressure distribution and heating rates in the air-cooled nozzle throat are presented, and desirable characteristics of a ceramic material to be used in the nozzle throat are outlined, including high-temperature strength, thermal shock and erosion resistance, low conductivity and low thermal expansion. Ceramic nozzle throat design concepts are then examined, with attention given to monolithic and layered constructions of cast ceramics, reaction-bonded materials and a fiber-reinforced silica-silica ceramic. Results of a finite element analysis of the temperatures and stresses characteristic of the various concepts are then presented which indicate the monolithic silica-silica and the layered silica-silica/reaction bonded silicon nitride concepts to be the most promising of those investigated.
In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.
The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross section ratio, 4, however, the tetrasulfonate groups make the dye soluble in water which greatly facilitates its incorporation into the sol-gel matrix. The nonlinear transmission of CuPc4S in a pH 2 buffer solution and in a silica xerogel were compared. It is evident that the CuPc4S preserves its optical limiting behavior in the sol-gel matrix, indicating that the fundamental excited state absorption process is essentially the same for a molecule in solution or in the solid state. Although the spectroscopic details of energy level lifetimes are unknown, the significance is that passive optical limiting has been achieved in the solid state via incorporation of a dye into an inorganic host. The only compromise occurs at the extremely high energy regime where photobleaching is observed. This is a result of the limited mobility of the dye molecules in the solid silica host relative to a liquid host. The effects of photodegradation in the xerogel are additive, whereas the solution provides a supply of fresh molecules that are free to enter the active volume between pulses.
aerogel insulation material was developed that will provide superior thermal insulation and inherent radiation protection for government and commercial applications. The rubbery polyureabased aerogel exhibits little dustiness, good flexibility and toughness, and durability typical of the parent polyurea polymer, yet with the low density and superior insulation properties associated with aerogels. The thermal conductivity values of polyurea-based aerogels at lower temperature under vacuum pressures are very low and better than that of silica aerogels. Flexible, rubbery polyurea-based aerogels are able to overcome the weak and brittle nature of conventional inorganic and organic aerogels, including polyisocyanurate aerogels, which are generally prepared with the one similar component to polyurethane rubber aerogels. Additionally, with higher content of hydrogen in their structures, the polyurea rubber-based aerogels will also provide inherently better radiation protection than those of inorganic and carbon aerogels. The aerogel materials also demonstrate good hydrophobicity due to their hydrocarbon molecular structure. There are several strategies to overcoming the drawbacks associated with the weakness and brittleness of silica aerogels. Development of the flexible fiber-reinforced silica aerogel composite blanket has proven to be one promising approach, providing a conveniently fielded form factor that is relatively robust in industrial environments compared to silica aerogel monoliths. However, the flexible, silica aerogel composites still have a brittle, dusty character that may be undesirable, or even intolerable, in certain application environments. Although the cross - linked organic aerogels, such as resorcinol- formaldehyde (RF), polyisocyanurate, and cellulose aerogels, show very high impact strength, they are also very brittle with little elongation (i.e., less rubbery). Also, silica and carbon aerogels are less efficient radiation shielding materials due to their lower content of hydrogen element. The invention involves mixing at least one isocyanate resin in solvent along with a specific amount of at least one polyamine hardener. The hardener is selected from a group of polyoxyalkyleneamines, amine-based polyols, or a mixture thereof. Mixing is performed in the presence of a catalyst and reinforcing inorganic and/or organic materials, and the system is then subjected to gelation, aging, and supercritical drying. The aerogels will offer exceptional flexibility, excellent thermal and physical properties, and good hydrophobicity. The rubbery polyurea-based aerogels are very flexible with no dust and hydrophobic organics that demonstrated the following ranges of typical properties: densities of 0.08 to 0.293 g/cu cm, shrinkage factor (raerogel/rtarget) = 1.6 to 2.84, and thermal conductivity values of 15.2 to 20.3 mW/m K.
The JPL Aerogel Laboratory has made aerogels for NASA flight missions, e.g., Stardust, 2003 Mars Exploration Rovers and the 2011 Mars Science Laboratory, as well as NASA research projects for the past 14 years. During that time it has produced aerogels of a range of shapes, sizes, densities and compositions. Research is ongoing in the development of aerogels for future sample capture and return missions and for thermal insulation for both spacecraft and scientific instruments. For the past several years, the JPL Aerogel Laboratory has been developing, producing and testing a new composite material for use as the high temperature thermal insulation in the Advanced Sterling Radioisotope Generator (ASRG) being developed by Lockheed Martin and NASA. The composite is made up of a glass fiber felt, silica aerogel, Titania powder, and silica powder. The oxide powders are included to reduce irradiative heat transport at elevated temperatures. These materials have thermal conductivity values that are the same as the best commercially produced high temperature insulation materials, and yet are 40% lighter. By greatly reducing the amount of oxide powder in the composite, the density, and therefore for the value of the thermal conductivity, would be reduced. The JPL Aerogel Laboratory has experimented with using glass fiber felt, expanded glass fiber felt and loose fibers to add structural integrity to silica aerogels. However, this work has been directed toward high temperature applications. By conducting a brief investigation of the optimal combination of fiber reinforcement and aerogel density, a durable, extremely efficient thermal insulation material for ambient temperature applications would be produced. If a transparent thermal insulation is desired, then aerogel is an excellent candidate material. At typical ambient temperatures, silica aerogel prevents the transport of heat via convection and conduction due to its highly porous nature. To prevent irradiative thermal transport, silica aerogel can be used in conjunction with a transparent polymeric material that blocks infrared radiation. The transparency of silica aerogel is typically greater than 90% for visible wavelengths from 500 nm to 900 nm for a 5 mm long path length.
Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.
Composite flexible multilayer insulation systems (MLI), consisting of alternating layers of metal foil and scrim cloth or insulation quilted together using ceramic thread, were evaluated for thermal performance and compared with a silica fibrous (baseline) insulation system. The systems studied included: (1) alternating layers of aluminoborosilicate (ABS) scrim cloth and stainless steel foil, with silica, ABS, or alumina insulation; (2) alternating layers of scrim cloth and aluminum foil, with silica or ABS insulation; (3) alternating layers of alumininum foil and silica or ABS insulation; and (4) alternating layers of aluminum-coated polyimide placed on the bottom of the silica insulation. The MLIs containing aluminum were the most efficient, measuring as little as half the backface temperature increase of the baseline system.