'US 2006004 «i» United States STAI c2) Patent Application Publication co) Pub. No.: US 2006/0042417 AL Gash et al. (1) PREPARATION OF POROUS PYROPHORIC IRON USING SOL-GEL METHODS Inventors: Alexander E. Gash, Brentwood, CA, (US); Joo H. JR., Paterson, CA (US); Randall L. Simpson, Livermore, CA (US) Correspondence Address: John P. Wooldeidge ‘ATTORNEY 2 PL i, HI 96753 (US) (73) Assignee: ‘The Regents of the University of CA (21) Appl. Nos 11/N65;734 (2) Filed Jun. 24, 2008 He Q) porous Fe,O; gel (43) Pub. Date: Mar. 2, 2006 Related U.S. Application Data (60) Provisional application No, 60/583,155, filed on Jun 24, 2008, Publication Classi 1) Inc. €2B 5112200601) 2) US. 7si4ts on ABSTRACT [New sol-gel methods ean be employed to generate high seface area porous iron (II oxide-based sols, Chemical reduction of such porous sols at low temperatures allows the preparation of high sueface area pocous iron with litle simerng, withthe only byproguct being water. The material isreadily pyeophorie and has utility in new decoy fare, The ‘material, prepared by this synthetic route, eliminates the use ff hot caustic leaching solutions. It does aot require the incorporation of say hazardous materials or processes that fate not already used in cuerent production methods, T = 360-600 C +H,0 porous Fe metalPatent Application Publication Mar. 2,2006 Sheet 1 of 8 US 2006/0042417 AL Figure 1Patent Application Publication Mar. 2,2006 Sheet 2 of 8 US 2006/0042417 AL +H porous FeO, gel porous Fe metal Figure 3Patent Application Publication Mar.2,2006 Sheet 3 of 8 US 2006/0042417 AL 1100 800 100.0 700 100% Hy 600 Kose 50 scom 500 80.00 3 g 40 3 700 mo 8 60.00 50.00 NL} 100 40.00 ° 0 2 4 6 8 w 4 16 time (hr) Figure 4Patent Application Publication Mar. 2,2006 Sheet 4 of 8 US 2006/0042417 AL Transmittance 3600 3200 2800 2400 2000 1600 1200 800 400 wavenumbers (cm ~*) Figure 5Patent Application Publication Mar. 2,2006 Sheet 5 of 8 300 250 200 500 400 aa 200 100 157-9 - reduction product Fettto] 35 4045808 2 theta 151-13 reduction product 60 US 2006/0042417 AL FIG. BA FIG.6BPatent Application Publication Mar. 2,2006 Sheet 6 of 8 2006/0042417 ALPatent Application Publication Mar. 2, 2006 Sheet 7 of 8 US 2006/0042417 AL FIG. SCPatent Application Publication Mar. 2,2006 Sheet 8 of 8 US 2006/0042417 ALUS 2006/0042417 AI PREPARATION OF POROUS PYROPHORIC IRON USING SOL-GEL METHODS [0001] This application claims priority lo U.S. Provisional Patent Application Ser No. 60/583,155, fled Jun. 24, 200, led:~ Preparation of Porous Pyrophoric Iron Using Sol-Gel fethods,” incorporated herein by reference. [0002] The United States Government has sighs ia this fvention pursuant to Contract No, W-7405-ENG4S between the United States Department of Energy and the University of California Tor the operation of Lawrence Livermore National Laboratory. BACKGROUND OF THE INVENTION [0003] 1, Field of the Invention [0004] The present invention relates to sol-gel chemistry, and more specifically, it relates to sol-gel methods for producing porous pyrophoric iron. [0005] 2. Description of Related Art [0006] Pyrotechnics can be grouped into six families; ‘decoy flares, illuminating flaws, colored flares, smokes, Jgntersstartes and miscellaneous pyrotechnic items Decoy flares include infrared (IR) and solid pytophoric flares. Aire pyrophoric decoy flares are solid pyrotechnic devices ejected asa precautionary measure or in response (0 ‘missile warning system. The most significant requement ‘ofthe device is that it develops a high-intensity, character- ‘stc signature, rapidly. In order to meet ths requirement, the ‘encrgy radiated by the fare is typically. provided by a PYrolechnie reaction, Pyrotechnic compositions bave been shown to provide high enetgy densities and reasonable Storage life at moderate cost, The most common composi tion of a conventional pyrotechnic Mare consists of pyro photic iton, This composiion provides the high energy density required for the decoy. and also produces. solid ‘combustion products for good radiation ellcieney. The nel feaction is shown below: 2Pe(s)+¥s0,-+Fe,0, (3)sheat [0007] Decoy materials of this composition undergo the shove reaction to reach temperatures of $20" C. in less tha ‘one second and shave 750°C. for twelve seconds afer thie ‘exposure lo air The thermal response ean be increased oF ‘decreased with the addition of metals that undergo very ‘exothermic reactions when heated in air eg, B,Al, Ze. Ti) ‘or inert metal oxides (¢2,, SIO, I,O3), respectively, [0008] The current pyrophoric decoy fare is composed of pyrophoric iron coated onto ste! foil The pyrophore oo ‘couling i prepared by mixing Fe and Al powders in a slurry ‘contzining 1 suitable solvent and binder. A very thin steel foil is then coated with the sluery by ether dip coating or spraying. The resulting material is then rapidly heated to 500. to drive off the solvent and binder to yield a coating ‘of the metallic powders. The coated substrate is then heated ‘o relatively high temperatures (~800-1000" C.) in bob Hs and Ar atmospheres to from an iron/aluminum alloy. The resulting alloy can be leached with « hot (~100-200° F) ‘caste aqueous solution of 10-20% sodium hydroxide (by ‘mass) 10 leach the aluminum fom the alloy and render the Femaining iron porous and highly pyrophori. Some patent processes claim that use of stanite (dissolved as Sal, of 3) in the aqueous leaching salutin increases the activity (e., makes the iron more pyrophorie) and te lifetime ofthe Mar. 2, 2006 setive decoy, There are several variations of the described ‘manvfacturing technique that allow the preparation of the pyrophori iron as a powder of a coating on a metal fo Pyrophore foils are particulaely atractve for heir ability to be dispersed from the aireraltin 4 cloudl-like pattern, The hgh surface area to mass ratio of the foils equires that they ‘luter after being ejected from the arerat and take on the appearance of 2 moving hot cloud when several decoys are fected in rapid succession. This signal is attractive to the -sceking missile. Current pyrophoric decoy composition and performance can be modified through manipulation of the manufacturing process, Wa small amount ofa substance in intimate the pyrophorc iron that undergoes an exoter= ‘mic reaction whea bested can increase the pyophoric action of the decoy flare material. Metals, such as boron or ti nium, can be added to the pyrophorie foils to achieve this esiréd result. Alternatively, the pyrophoric iron can be coated with aqueous solutions of commercially available alumina o silica sol that coat the porous base metal. The ince oxide coating blocks O. from geting fo the io 100 rapidly and hence slows down the buen rate and makes the Dyrophorie response of the material less intense. ‘The pyro- hore ion generated by the above processes can be sored Jn solvents such as acetone, ethanol, and methanol, under certain conditions, with lite loss in their pyrophorie per- formance. Although this process is well documented) and provides functional and effective pyrotechnic flares it ean And should be improved. The current process relies heavily ‘upon the use of hot caustic leaching solutions to prepare the high surface area porous pyrophorie Fe metal. These solu- ‘dons are corosive and represent both a safety and environ- ‘mental hazard [0010] Magnus reported that pyrophoric irom could be ‘generated from reduction of iron compounds in a stream af I, at relatively low temperatures (360-420° C.) as early as ince then many researchers have repeated this result using the iron (IM) oxides asthe ion-conlaining reagent [0011] Sot-gel chemisey uilizes the hydeolysis andl cor ‘Sensation of molecular chemical precursors, in solution, to produce nanometer-sized primary particles, called “sols” Through further condensation the “Sols” are linked (fo 4 three-dimensional solid network, refered 10 a8 a “gel”, ‘ith the solvent liquid preseat in its pores. Evaporation of the liquid phase results in a dense porous solid referred 0 as 4 "xerogel”. Superertcal extraction of the pore liguid liminates the surface tension of the retreating liquid phase and results in solids called, “aerogels”. Sol-gel materials are distinctive in that they typically posses high surface areas, high porosities and seal primary particle size, The proper. ties unique lo sol-gel materials lead to their enhanced reactivity. Therefore, sol-gel chemical routes are very attrae- tive because they olfer low temperature routes to synthesize homogeneous materials with variable compositions, mx phologies, and densities. A schematie representation of the Solel process and materials is shown in FIG. 1 [0012] Scientists atthe Naval Research Laboratory have ‘prepared and charseterized thermally emitting aeroges. Ton ‘metal was deposited into the framework of silica, resorinol- formaldehyde, and carbon aerogel materials using a metal ‘organic chemical vapor deposition (MOCVD) system. One serogel, the iron doped-catbon material, was Seong therUS 2006/0042417 AI ‘mal emitter and burned st 600-700? C. The results shown i this study are encouraging that sol-gel techniques ean be used to prepae thermal emitters, However, the iron precut- sor used in the MOCVD process, iron pentacarbonyl, is highly pyrophoric and toxic [0013] Production of pyrophoric iron ina simple and safe ‘manner would be advantageous from a safety ahd environ- ‘mental point of view, SUMMARY OF THE INVENTION [0014] Is an object of the present invention to provide “sol-gel” chemical techniques that ean be used in environ- mentally acceptable solvents to prepare high surface area porous iron (ID) oxides. [0015] I is another object of the invention to provide a “sol-gel” methodology for producing nanostructured ener _gctic materials while minimizing or eliminating the health and environmental hazards associated with their current fabrication [0016] These and other objects will be apparent to those skilled in the art based oa this diselosure [0017] The present inveation provides combined sol-gel and elevated temperature processing metiods for producing Porous nanostructured pyrophorie metals. One’ or mote hydrated-netal ion inorganic alls and one or more sovents are combined in a soltion. The pl of the solution is Adjusted with & proton scavenger induce gel formation, ‘This ests in the formation of « nanostructured metal ‘xide-hased ge, which is then died by ane of two methods ‘To produce xeoge, the gel is ered by atmospheric evapo: ration To produce a nanostructured melal-oide-based ator tok the gel is died by super crcl savent extraction. The ‘ried nabosiuctied metal-oxide-based matral (eroge of ‘rogel is thes treated thermally, under adyaamie vacuum, {oremove aby impurities or surface bound chemical species, ‘A redaction sep includes heating the thermally Wealed material in the presence of chemical redetant (6, hydrogen gas I, carbon monoxide (CO)) dled wil a inert eactiet 388 10 an elevated temperature [0018] Highly porous sol-gel derived iron (II) oxide ‘materials ein be ruduced to sub-micron-sized metallic ion by heating the materials to intermediate temperatures in & hydrogen atmosphere. Through a lange number of experi- ments, complete reduction of the sol-gel based materials was realized with a variety of hydrogen-based atmospheres (25- 100% Hy in Ar, Ns, COs, oF CO) at intermediate temper tures (350° C. to 700" C. Sol-gelderived metallic iron powders that were produced were ignitable by thermal ‘methods. The present inveation teaches techniques for pro- ‘ducing sol-gel-derived metallic iron powders that are pyto~ phoric. For comparison several types of commercial micron Sized iton oxides (Fe:0,, and NANOCAT™) were also feduced under identical conditions, AIL eesulting materials ‘were characterized by thermal gravimetric analysis (TGA), ‘lifferental thermal analysis (DTA), powder X-ray diffrac tion (PXRD), as well as seanning and transmission electron imieroscopies (SEM and TEM). In addition, the reduction of the iron oxide materials was monitored by TGA. In general the sol-gel materials were more rapidly reduced to metalic jon and the resulting iron powders had smaller particle sizes and were more easily oxidized than the metallic powders Mar. 2, 2006 derived from the mieroo sized materials. Impurities in the smaller fine metalic powders ean prevent pyrophoricity if = passivation layer is on te iron BRIEF DI RIPTION OF THE DRAWINGS [0019] The accompanying drawings, which are incorpo- ‘ated into and form part of this dislesu, ilusteate embed ‘meals of the invention and together with the description, serve o explain the principles of the invention, [0020] FIG. 1 illustrates sol-gel process and mat [0021] | FIG. 2ilusicates pseudomorphic transition of ion fxd aerogel material [0022] FIG. 3 shows » SEM image of icon (Ill) oxide aerogel starting material [0023] FIG. 4 shows « TGA trce following reduction of fron (Il) oxide aerogel with H, [0028] FIG. § shows the FTIR spectra of “ss-made” and heat-treated iron oxide acrogel [0025] FIG. 6 shows PXRD patterns of products from reduction of iron oxide serogels. [0026] FIG. 7 shows a TEM image of metallic Fe from ‘eduction of sol-gel materials. [0027] FIGS. 8A-C show SEM images of metallic Fe powder from reduction of sol-gel [0028] FIG, 9 shows « TEM image of hest-teated too (ID oxide serogel DETAILED DESCRIPTION OF THE, INVENTION [0029] The invention demonstrates that “sol-gel” chemical techniques canbe used in water-, oF another environmentally acceplable solvent, based processing to prepare high surface tea porous iron (Il) oxides. These materials can then be reduced using molecular hydrogen, at elevated tempera- tures, to produce high surface area porous pyrophorie oa ‘metal, This material will be used to provide a decoy with ‘comparable performance characteristics to that curently ‘used withour the environmental nd health concerns of using hot caustic leaching solutions that are needed in the con- ventional production process of pyraphoric decoys, Alte natively, "solege” techniques can also be used to immobilize the pyrophoric iron generated by reduetion of the sol-gel erived iron (Il) oxides, or [rom some alternative source, in an inert mati, which can be cas o pacts witha Variely of Shapes and sizes. This second approach allows the resulling pyrophorie pycotechnie to be easily and desieably released, aswell to control the composition ff the matsix and tailor the material to provide 4 specitic ‘pat response. The sol-gel approach enables high control ‘ver chemical compositions and reaction rates of energetic ‘materials and tht the process is sale. [0030] A “sol-gel” methodology is used for producing ‘nanostructured energetic materials (i.e pyrotechnics) whi ‘minimizing or eliminating the health and enviroomental hazards associated with their curent fabrication, This sol- gel approach for preparing pyrotechnic formulations Javolves a fundamental chinge in the conventional man- facturing and fabrication processes of energetic materialsUS 2006/0042417 AI One particular application of this methodology can be used to climinate the use of caustic leching solutions associated with pyrophorie decoy flare manufacture, while maintaining ‘or improving performance of the final products. Low tem= perature reduction of high surface area porous sol-gel- derived iron (HII) oxide with molecular hydrogen results in the formation of porous pyrophorc ion meta, suitable for use in pymphorie decoy flares. Processing and preparation ‘with environmentally acceptable media under neutal con= ditions replaces the process curreally used in pysaphoric flare manufacturing. [0031] Preparation of FeO, gels from Fe(II) salts. Ferrie hitale onahydrate, Fe(NO.),9H,0, ferrle chloride herabydrate, FeCl, 6H,O, and FeCl, salts were obtained from Aldrich Chemical Co. and used as received. The symthesis of FeO, nanosinictured gels was performed i the following solvents, ll of which were eagenl grade or better: ‘ethanol (00 proof; Aaper), L-propanol (J. T- Baker), bu ‘anol (J.T. Baker), acetonitrile (EM Science), water (is- tilled), ethyl acetate (Mallinckrodt), 2-ethoxy ethanol (Chemical Samples Co.), NJN-dimethylformamide (Fluks), and the methanol, tetrahydrofuran (THF), acetone, ethylene elycol, propylene glycol, formamide, 1,4dioxane, benzyl alcohol, nitrobenzene, fexanes, and dimethyl sulfoxide (DMSO) were all from Aldtich Chemical Co. Some ofthese solvents, in particular elhanol and water, are highly desirable for this process as they are environmentally benign com pared to solvents currently utilized such as acetone and henzene. ‘The propylene oxide was also obtained. from Aldrich Chemical Co, All syntheses were performed under Aambiont conditions [0032] In typical experiment, 0.65 g of Pe(NO,), 91.0 (16 mmol) was dissolved ia 35 mL.of 200 proof ethanol to give a clear red-orange solution that remained unchanged Upon storage, under room conditions, for several mont. I instead, a LO g portion of propylene oxide (17 mmol; propylene oxide/Fe=11) was added tothe solution there was rapid (<1 min.) color change as the solution became an Jntense dark red-brown eofor. With time, the solution rans- formed into a rigid red-brown gel. Gel formation ustally ‘occurred within several minutes. Unless otherwise stated, all, ‘synthesis experiments used 3.5 ml_of solvent, [Fe(IID]-0.35, M, and an epoxide/Fe ratio of 11 [0033] As an example of one embodiment of the preseat vention, the processing of Fe.0, nanostructured gels is deserbed. Acrogel samples were processed in a Polaron™ ‘supereitieal point deer. The solvent liquid in the wet gel pores was exchanged for CO.(0) for 3-4 days, after which the temperature of the vessel was ramped up to ~A5" C, ‘while maintaining a pressure of ~100 bars. The vessel was then depressurized al arate of about 7 baes per hour. For acrogel processing we prefered to use polyetylene vals to hold the gels during the extraction process. This was done because much less monolith eracking was observed than ‘when Fe,0, gels were processed in glass vials, [0034] Xerogel samples were processed by drying ia a fume hood! at room temperature for 14-30 days. Under these ‘conditions high vapor pressure solvents, like ethanol, were ‘evaporated and the wet gels were converted to xerogels. [0035] A 1 gram postion of dried ion oxide aerogel was, heat treated under 2 vacttim atmosphere at 150° C. Mea ‘surements were preformed on an oa oxide nanostructured Mar. 2, 2006 le was heated to 375° C, while having Atmosphere consisting of 50% argon and 50% hyd lowing through the reactor, The oxide can be reduced in pure Hy or mistures of ArH, and For the same heating rates, te rate of reduetion was found to vary with the concentration of H. nthe gas miture, thus the reduction ‘does not appear to be diffusion limited, Te sample had a ‘weightloss of 48% at temperatures above 350° C. According to calculations, based on the elemental analysis of the ‘nanostructured ion (II) oxide, this weight loss corresponds to complete conversion of the metal oxide material to too seta, This sto be expected ifthe iron (Ill) oxide species js converted quantitatively to Fe metal [0036] The powder X-Ray dillaction pattems were ‘obtained using a Siemens DIFFS00 diffractometer. The sol-gel nanostructured materials are amorphous to X-rays. For the sample that showed a 486 % loss, the X-ray {ifration pattern show the material to consist of metalic iron. That i 0 Say that the starting porous ion (Il) oxide ‘vas chemically transformed to iron metal. The surlace area of this material was 27 mig, This value indicates tht the ‘material is sill porous and has 2 high surface area, charac- teristics tha lend themselves 1 the pyrophoric nature ofthe ‘material I also suggests thatthe nanoporous nature of the etal oxide is maintained upon reduction [0037] Sol-gel techniques can be used to produce sub- Strate for immobilization ofthe pyrophorie material in the Tare and allow suitable dispersion when deployed. The extremely versatile nature of sol-gel chemistry allows forthe reformulation of materials that i not possible or practical ‘with conventional systems, to allow decoy Hares with spe- cial features to be readily and safely prepared. This inven- tion advances the use of nanotechnology in defease appl cations, Preliminary work bas demonstrated that this approach enables high control over chemical compositions, particle size and distribution, and reaction rates and thatthe process is se. Although sol-gel technology has the por {ial to impact a number of defense and energy nocd, the focus will be on pyraphoric pyrotechnic needs in decoys, The disclosed process provides a pyrophorie decoy whose processing andl composition is aeceplable by OSHA, EPA, {he Clean Air Act, Clean Water Act, snd Resource Recovery ‘Act standards, [0038] One aspect ofthe invention includes the reduction of solyelderived high surface area porous iron (Il) oxide fserogels and xerogels (© pyrophoric iron using molecular hydrogen at elevated temperatures. Since first reported in 1825, many researchers have found that reduction of pow= dered ferric oxide ‘with hydrogen gas. at temperatures between 360-600" C. yields pyrophoric ia, Reduction at temperatures higher than 650" C. resulted in non-pyrophiic iron. The general bypotbesis used to rationalize these obser- vation i hat the temperature of reduction is low enough so a8 0 reduce the itoa species to metallic ison with miniaal Sintering of the final product At the lower temperatures the ‘movement of atoms 10 orient them in a dense and more ‘compact crystalline state isso slow that it does not occur to fn appreciable extent. The esult isthe production of a very Beri porous Fs) power tt tts ape cama with aie [0039] The iron (III) oxides procuced using the present nethod have surface areas and porosities. significantlyUS 2006/0042417 AI higher than those ceported previously. The dey porous itr Ul) oxides can be prepared using benign and environmen: tally acooptable solvents like water and ethanol, Fe (Il) inorganic sali (chloride and nial), and propylene oxide. ‘This material ean be reduced to porous iron metal using hydrogen at temperatures between 360-600° C. Typical sol-gel particle and pore morphology is shown in FIG. 2 [0040] In FIG. 1 the porous irom (ll) oxide is reduced to Fe(S) while retaining a significant amount of the porous skeletal framework of the precursor oxide material. This is, feasible, provided thatthe redvtion temperature is kept Tow ‘enough to prevent sintering. Certainly there will be some Sintering of the porous slid; however, iis highly likely tat material like that shown on the right side of FIG. 2 would be pyrophoric as it woul have many ofthe characterises (Ca, small particle size, high surface area) of finely divided ‘eon tat is pyrophorie, FIG. 3 shows iron (Il) oxide sol-gel ‘materials with 1 microstructure similar o that described and shown in FIG. 2 [0041] In the present invention synthesis, the pyrophorie fron is produced using water or elhanol, Fe (ID) sali, propylene oxide, and hydrogen. This method is not without hazards. The flammable nature of hydrogen requires that necessary safety steps be taken. However, hydrogen is both used asa reagent and generated as a byproduct of the caustic Jeach process in the current manufacturing method. [0042] The catalyzed hydrolysis and condensation of tia alkoxides in aleaholie media followed by rapid high-tem- perature supercritical extuction yields products that com bust on exposure to aie: Preliminary investigations have indicated thatthe high temperature extraction step results ia the reduction of some of the oxide to high surface area porous pysophorie tin metal. Prous pyrophorie metals ea therefore be prepared uilizing aspects ofthe sol-gel method. “The pytophorie tin oxide could be eoated onto a variety of lfferent substrates fora myriad of energetic need related to ‘decoy flares, The application of sol-gel methods to decoy ‘couniemessure devices extends beyond the preparation of pyrophorie icon. [0043] Solel methodology can be wllized to provide a ‘effective medium for he dispersion of the pyrophoce iron in ‘decoy fares. Small particle sized native metals can be Incorporated into a sol-gel metal oxide network composite ‘decoy miterials ean involve the generation of the pyrophorie Jon in the gel matrix in situ. This has been performed previously on Fe,O,-doped SiO, and AO, gels. Reduction ff the dried mixed Fe,O,-doped! metal oxide matrix with molecular hydrogen at elevated temperatures gives nano- Particles of Fe(s) inthe oxide matrix. The particles generally have very small diameters (2-20 nm), high surface areas, and ate pyrophorie. The spatial isolation of FeO, particles from ‘one another precludes them from diflusing together and Sintering to larger particles, Numerous metal oxidevioa (I) ‘oxide gels have been readily prepared using the epoxide Audition method from solutions of mixed AI (ID oF $i (IV) tnd Fe(lll) moleculae precursors with high levels of iron, The matrix oxide will act as a burn rate modifier in these types of materials as well asa subsiate for processing into decoy parts, [0044] The rheological properties ofthe sl allow gels of {to be cast and processed into a varity of complex and precise sizes and shapes. Iis certain thatthe eompesite sols Mar. 2, 2006 could be east and processed to wive parts (e.g thin diss or wafers) that have a large surface area to mass ratio. Pats ‘with tis property respood to ejection from a moving ateraft by Mlutering in the air as do the conventional pyrophorie decoy foils, In addition, the lange surface area to volume ratio ofthese composites ensures rapid diffusion of ie into the part and complete ignition of the pyrophoric icon. The praduction of thin aerogel or xerogel SiO. discs containing yrophoric ron isan appropriate way fo achieve a desirable ispetsion of the decoy material once deployed. The pore size ofthe matrix material is dependent upon its processing conditions and can be readily varied with some degree of precision. This might allow the preparation of decoy fares ‘with varied burn ates. For example, for faster bum ates one ‘would employ processing conditions that yielded larger pores and conversely smaller pore sizes may result in slower buro times. [0045] Iron (Il) oxide aerogel and xeroge! materials used Jn this study were made from tbe salts FeCl, GH,0 and Fe(NO.},9H,0 using sol-gel techniques described else- ‘where, Asa conto, samples of Fe,0, (Aldrich) and NANO- CAT™ (a commercial source of 3 nm particle size amor- phous iron (IT) oxide) were aso reduced. etic analyzer (TGA) was se up to forthe reduction of ion (Il) oxide aerogels. TGA measurements were performed using a Cahn ‘model 141 TGA balance, Measurements were preformed oa ‘so iron oxide nanocomposites. The oxides eam be reduced in pure H, of mistures of ACH, and Nu/H,, For the same hetting ries, the rate of reduction was found to vary with the concentration of H. nthe gas mixture, thus the reduction does nat appear to be diffusion limited, ‘The samples ‘decrease to about 52-0 foe maximum temperatures above 350° C. This weight loss corresponds lo 3 moles of exygen {o 1 mole of iron in the starting composite, assuming only the presence of iron and oxygen, The reduced material splays a small amouat of weight gain on cooling, probably {due to the surface re-osidation from reaction with water in the pases. Background measurements confiem that this increase is not de to buoyancy changes in the sytem, [0047] The powder X-Ray diffraction patterns were ‘obiained using a Siemens DIFFSU0 diffractometer. The ion oxide aerogel materials are amorphous, For samples reduced to 52-0, the patterns show the presenee of metallic iron. For samples not fully reduced, the patterns show the pees: tence of Fe,0,. Fourier transform-infrared (FTIR) spectra ‘were collected on pressed pellets containing KBr (IR-grade) nd a small amount of solid sample. The spectra were collected with Polaris™ FTIR spectrometer. [0048] Surface area and pore volume and size analyses ‘were performed by BET (Brunauer-Emmet-Tellet) methods using an ASAP 2000 Surface Area Analyzer (Micromeriics Insttument Corporation). Samples of approximately 0.1-0.2 Were heated to 200" C. under vaca (107° Tort) For at Teast 24 hours to remove all adsorbed species. Nitrogen adsorption data was taken at five relative pressures fr (005 to 0.20 at 77K, to calculate the surface area by BET theory [0049] Scanning electron microscopy (SEM) was carried ‘out using a Hitachi S-4500 cold eld emission SEM, Typical fccelerating voltages used for aerogel samples ranged from 1846 KV and depended on sample conductivity: No sampleUS 2006/0042417 AI preparation (ce. coating with conductive layer of Au) was Performed on the samples. The SEM micrograph showed the products ofthe TGA reduction to consist of lange (-100 tioton) porous chunks. These pices Were Found 0 consist fof chistes of smaller particles of about 200 nm. The transmission electon microscopy (TEM) was performed on 4 Philips CMBOOPEG operating at 300 kev using z¢oloss ‘coergy filtering with a Gatan energy Imaging Filler (GIF) 40 femove inelastic scattering. The images weve taken undee TBE (bright fick) conditions and slightly defocwsed to inewease const. The images were also recorded on & 2KQK CCD camera attached lathe GIF [0030] Consiseration of the composition and phase ofthe Initia iron (I) oxide material is extremely important. The presence of trace impurities can affect the propertics of Iaterals dramatically. To complicate the situation, there are thirteen known phases of iron oxides, each having distinct properties and chemical characteristics, A solget derived {ron (ll) oxide material made by the peesent method was ‘determined to consist mainly ofthe compound Fersinydrit,, FesHO,.4H,0 (Formula. Weight=480. gimol). This is highly hycrated poorly erystalline iron (ID) oxide phase that was determined by XRD. Elemental analyses on the sol-gel derived materials indicated significant levels of carbon (2-6 ‘wt %) and hydrogen (1-3 wt %) and chloride (1-54; note chloride only” present inthe samples made ” fom FeC, 61,0). [OSI] The central hypothesis of this work was to dem= ‘onsale thit sol-gel iron (II) oxide materials would be reduced by molecular hydrogen to metallic ion while maine taining the small particle size and porosity that are charac- teristics ofthe reactant sol-gel material. To demonstrate this 4 umber syntbetie experiments were performed, The objec tive being to optimize the syathetic and processing condi ns that would result in Fe production, while atthe same time minimizing the concentration of hydrogen needed as ‘well as keeping the reduction temperature low. This ojo live serves two purposes: 1) safely and 2) materials perfor [00s2] By using the minimum amount of H; (mixed with an inert gas like Ar or hazards associated withthe vse of pure hydrogen would be diminished, The use of the lowest possible reduction fem= perature would minimize all of the processes involved in Sintering (surface, vapor, and volume diffusion). This leads to the production of elemental Fe that retains the high ‘surface area porous structure ofthe reactant iron (HII oxide sol-gel material. Such a material would be pyrophoric [0083] As can be scen in Table 1 numerous synthetic ‘experiments Were run lo determine optimal condition for the reduction of ion (ID) oxide aerogel to porous Fe metal Parameters that were varied ined the composition of the reduction gas, the beating rate, and temperature [0084] For the sake of brevity, and in veordanee with our ‘objective, the synthesis results willbe summarized, Samples ‘of iron (it) oxide aerogel can be redueed to metallic Fe in the following reducing atmospheres at given temperature ranges: 25-100% Hz in Ar of Ny al temperatures between S350" C. and 700" C. 75% H./25% CO, at 70" C, and 754% 25% CO at 650°C. Table | also contains the final weight perevot as wel a the weight percent at maximum tempera- ture during the reduction process. These values were moni tored by TGA and will be discussed shorty [0085] From the entses in Table 1 it is apparent that hydrogen levels below ~20% are ao sulicient to bring about Mar. 2, 2006 ‘complete seduction of the sol-gel iro (II) oxide material [Even at temperatures up to G0" C. the reaction docs nol go {o completion at lower hydrogen concentration levels (2.5% TH). That temperature is signlicanly higher than those reported in patents from several decades ago, Certainly lower reduction temperatures Would be more desirable (en, 200-400" C:) [0086] 11 appears that there is a temperature threshold for ‘complete reduction, For example at 300" C. and LOOP 1; the reduction is incomplete. However, at 350° C. the rea tion goes to completion. From the ents in Table 1 itis not lear that heating rate allets the reaction to a discernable degre. ‘TABLE 1 fans ll ne age ch ‘Temp _Amowphee Wee me T (Cina) dic mene i 2, at SR Rei comple fas S$ ReO4 Rede Somplte eo HN, Td Feo ede - comple 80) 282HN) 780 S Fes Rede Fes0@ donot Somplte so 2H, A Fe ewe ase, sees Soe in: S02 IN: SORRY SSD -S890 Se {© into tx ming or ge when BedUS 2006/0042417 AI 10057] Thermogsavimetie analysis (TGA) proved to be a very valuable technique for monitoring the progress of the reductoa reaction, This tecnigue permits monitoring ofthe ‘extent of reaction with ime and thus, determines when the reaction is completed. When iron oxide is reduoed t0 meta Tie iron and water (sce FIG. 1), at elevated temperatures, there is a net Toss inthe solid mass of the sysiem. By monitoring the mass of the sample under reducing condic tions, the onset and end of the chemical reactions thal produce the transformation can be determined. Once the mass loss levels off, one ean reasonably conclude thatthe reaction has gone © completion under these conditions. In Audition, by examining any weight gain ofthe sample a i ‘cools the fidelity ofthe experimental sytem o atmospheric impurities (¢,, 0s oF water) can be evalated If the system § prising there should be no weight change. If thete is a source of contamination (eg, leak) the sample will ‘oxidize, ad likely passivate, and as such a weight gai would be observed. [0088] FIG. 4 shows atypical TGA tac for he eduction ‘of an ion (Ii) oxide aerogel in a 100% hydrogen aimo- sphere at 700° C. From this TGA trace ican he sen that the mass loss levels out after about four ours under these ‘conditions. Therefore it ean be inferred thatthe reduetion i ‘complete at tis time, Inspection of the region ofthe weight loss gain curve in the cooling region (from 10-16 hours) indicates a weight guin of 15%, tis dificult (0 assign any significant meaning to this weight gain, asi is very sight [0059] It was observed that the sol-gel derived oo (IN) ‘ide materia had mass loses of between H-18% weight percent upon completion ofthe reduction, Again completion ‘was infered from a lack of weight gin after prolonged reaction time. If one considers the iron (Il) oxide aerogel materi o be Fetihydit, the reduction ofthis iron oxide phase to metalic iron would result in 2 42% mass loss FecHO,4H1,0 (EWon480 wil) -05 Fe (EW.n55.9 gino [0060] As previously stated, elemental analyses indicate a background level of organie contaminant (C and H) of 49 ‘wt 6, Talking this into account, as well as the reduction ‘mass loss aod the dehydration, the expected weight loss of the irom (ID) aerogel should be range from 46 to 51 weight pereent. It i therefore reasonable to infer that the mass losses seem in these experiments and tabulated in Tube 1 are ‘consistent with the reduction and dehydration of Ferrihy= rite, The presence of water and hydrocarbon based impu- es inthe base iron (ID) oxide serogel material was also ‘confirmed using Fourier-Transform infrared (FT-IR) spec ttoscopy. [0061] FIG. 5 isan overay of the FTIR ypectra of the iron {UD oxide aerogel and its Vacuum dried (200° C:) product ‘The spectrum of the “asis” aerogel (Trace A in FIG. 8) ‘contzins several prominent absorptions, The inlense and broad absoeption in the 320-3600 em” region likely cot responds to v(O—H) stretching vibrations of adsorbed water (Sample was synthesized, stored, and FTIR spectrum was, taken under room conditions) and OH motes present in the solid. In audition, the absogption st ~1630 emis ikely ‘due to the bending mode of water (1,0). The presence of (O—H groups in the IR of iron(II) oxides synthesized by solution methods is very common. [0062] The absorptions present at 2800-3000 cm" are due fo MCI) vibrations, These, as well 8 the absorptions Mar. 2, 2006 present from 1400-800 em“ are probably due to ethanol (solvent used), residual propylene oxide, ose products of the ring opening of the propylene oxide. The propylene oxide is used in the symtbesis of the aerogel materials as @ gelstion agen. The absorptions between 700 em” and 500 fem are those from the FeO linkages that make up the framework ofthe aerogel. Al of the phases of iron oxides and oxyhydroxides have characteristic IR vibrations in this region. The assignment of the spectrum shown in Trace B of FIG. $ to one particular phase of iron oxide is at strug forward. Notwithstanding, with the FTIR evidence shown here we tentatively conclude thatthe non-heat-treated aero- gel material is probably an iron oxyhydronide phase. [0063] The spectrum shown in Trace B of FIG. $ is that ofthe aerogel material that has been beated to 200°C. under dynamic vacuum. This heat ireatment results in a mass loss ‘of -30% of the malerial. There are three notable differences between this spectrum and that of the iron (II) oxide acrogel. Fist, the absorption in the 3200-3600 em” region ff the spectzum is much less intense in the heat-treated sample. This is possibly due to the removal of a large percentage of the O—H moictics present in the original aerogel through condensation of wo neighboring OH ‘groups to give a single oxygen bridge. Second, there is no {race ofthe absorptions assigned to C—H bonds present in the heat-treated sample. These organic constituents have also been removed ia the heating process. And finally, the {wo intense absorptions at 510 al 615 em” in the origin acrogel have shifted and split into three peaks at 565, 585, and 630 cnr respectively. The location of the IR bands present in the heat-treated sample match very well to those reported for maghemite, the y-phase of Fe,O,, It is worth- ‘while to note that maghemite is magnetic ancl that the heat-treated material in Trace B of FIG. § i also magnetic. [0068] The primary analytical tools used to evaluate the relative success of exch experiment to reduce the aerogel taterials to metallic iron were TGA and powder X-ray iraction. By monitoring the mass loss or gain under reciucing or oxidizing conditions and knowing the compo- sition of the stating material one could determine if the reaction went t completion. This has already been dis- cessed, Analyzing the reaction products by PXRD and ‘comparing the results to known standardsallosed adalitional contention [0065] _ Representative XRD patterns for eaction products fre shown in FIG. 6. The lop XRD patter indicates prominent lines for the compound Fe,0,, magnetite, & ‘well-kaawn magnetic form of iron oxide ia whiet The ion stom in the lattice have either 8 42 or 43 oxidation This compound is often observed as an intermediate in the reduction of iron (ID) oxides to elemental iron and is representative of incomplete reduetion. The bottom XRD pattem in FIG. 6 has diffraction peaks from metallic ion And isa fine example of wha is observed when reduction is ‘complete. [0066] _ Using TGAA-monitored reduction several iron oxide based powders were examined. Powders from commer sources, different phases of iron oxides, a8 well as sol-gel Serived aerogels and xerogels were evaluated. According t0 the resulis a solgel based composition, iron (Il) oxide scrogel (made with Fe(NO,)9H,O precursor) reduced t0 petallic iron the most rapidly under constant conditionsUS 2006/0042417 AI (50% 150 Ae @ 450°C), This is possibly elated othe ‘extremely high surface area of the aerogel mates [0067] Simultaneous differential thermal analysis (combi hation of TGA and DTA) was shown to be an effective method to monitor the oxidation of native iron powders produced via this approach. t appears that iron produced from the reduction of aerogel ima (Il) oxide material oxi- izes al~340° C. This temperature isat east 75°C. less thao is seen forthe exidation of iron particles made from com- mercial Fes0, (Aldrich) (Fyjaia415° C.), This is poten- tially is very interesting rest Tt is known that ultrafine rained Al powders prepared by vapor phase condensation ‘oxidize al_much lower temperatures than micron sized powders. The UFG gained AL has shown exceptional ‘enhancement in energy release rales in mixtures wilh oxi= dizers and is curently being examined for a myriad of applications in energetic compositions. [0068] To more fully characterize the final Fe metalic powders both scanning and transmission electron ‘microscopies (SEM and TEM) were utilized. These methods will allow good characterization of the particle size, mor- phology, and disirbution of the metallic Fe products from Feduetion of sol-gel iron (Ill) oxide materials. FIG. 7 ‘contains a TEM image of the Fe metal powder produet from the reduction of an iron (Il) oxide acrogel material. This ‘TEM image is atypical image obtained from this analysis and provides a fine representation of the overall sample analyzed. The sample appears (© consist of nominally spherical particles with a diameter or approximately 200- 500 nm, These diameters are submieson but ate signiticanty rger than the primary particle size ofthe aerogel staring ‘material (~5-20 nm), This indicates that significant sintering hs taken place upon transformation, The particles are so thick that suitable surface imaging with the TEM is dificult. For « good look at the surface of these types of materials, SEM was utilized, [0069] SEM has proven to be a more useful method of surface characterization of these materials, FIGS. 8A-C show several SEM images of Fe metallic materials, From these images one can get an estimation of the nature of the surfaces. [0070] 1 appears that the reduced metallic eon powder is ‘made up of submicron-sized particles, From FIG. SB it ‘seems thatthe metalic iron has felained some ofthe porosity ofits precursor materia [0071] The objective of this work was to produce pyro= photic Fe for decoy flares in a safe and non-toxic mannet using sol-gel methods and materials, ‘Therefore, the phe- rnomenological behavior of the metallic powders on expo- sure (0 the almosphere is of ertical importance. Alter reduction in the TGA, samples were cooled and kept in an inert environment (AF or N,)- Once cool, the sample was Femoved from the TGA apparatus and rapidly exposed to oom atmosphere [0072] The fine metallic powders, produced via the sdeserbed synthesis and processing conditions, could be burned with the application ofa thermal source (Hlame, and soldering iron were used). Once ignited, the powders burned, ‘smoothly with a blue fame and left behind a red residue, a telltale sign of hematite FeO, Initially there was some ‘concern that the sample size of the powders may not be Mar. 2, 2006 sulicient to facilitate self-heating to combustion. That isthe surface area to volume ratio ofa small amount (100-200) mg) of metallic powder may be high enovgh that localized heating didnot occur to an appreciable extent; any heat generated by oxidation of the submieron Fe particles was rapidly dissipated tothe surtoundings. To ty and mitigate this potential scale effet, larger samples of sol-gel iron (I) oxide aeogel were reduced in tube furnace (up 1 2500) mg sta time). [0073] As aset of control experiments, the same TOA and tube furnace set up were used to reduee some commer svoes of iron oxide, Hematite (Fe,0,-30 microns) ftom Aldrich, and NANOCAT® (a commercial source of 3 nm Giametr iron oxide panicles from MACH [ Iae., King of Prussia, Pa.) were reduced under the same conditions asthe ‘noo oxide arogel material, These experiments were eee- tive in reducing the oxide to the base Fe metal [0074] The reduetion of iron oxide ores to iron, being & ‘major step ia the commercial production of se, is the subject of an extemely lage number of pateats. Many of these patents refer to processing conditions that leave the final Fe metal in a variety of forms (consolidated brick, powders, pellets). These conditions are particularly impor. {ant to determine asthey dictate the final form ofthe product metal. However, ioour knowledge tere are ao reports the conditions needed to effet the reduction of sol-gel-derived lton oxides to metallic ion. Sol-gl materials ae unique in that they typically posses high surface areas, high porosities and small primary particle size. The properties Unigue to sol-gel materials lead to their enhanced reactivity. In our «timation, the iron powder products from the reduction of sole ion oxides may be highly reactive and will be very ‘sel in applications involving energetic materials, [0075] One important result ofthis sty was the ident Fication of optimum redvetion conditions fr the production of sub-micron Fe powders from sol-gel derived-iron (I) ‘oxide precursors. Previous publications indicate that finely Gived iron powders can Be pyrophoric. Taking the ch acterization dane here into aecount, there is tle doubt tat the particle sizes ofthe powders made by this approach are 438, or more finely divided than pyrophorie powders. The Stsing materials in those reposts Were micron-szed iron oxides, It is very likely that significant agglomeration and consolidation occurred upon reduction. While in our case, the reactant oxide particles are much smaller and more highly porows. [0076] Iron metal eadiy reats with oxygen or water to passivate ils surface and generate heat. Wi high surface tea powders, the heat generated canbe significant enough {o ignite the entire iron particle. These are the processes that Jead tothe pyrophorie nature of finely divided iron, However with a suitable oxide coating the iron particles ean be very stable. The oxidation ean come from the ineraetion of the sewly formed Fe surface with water or O. impurities in the reduction gases of withthe water produced asa byproduct Of the reduction. Additionally the sol-gel material is the compound Ferrihydite (FesHOy4H,0), which contains bighly levels of wate init [0077] Percival and co-workers report ina patent issved in 1959 on the importance of low water content inthe system used to reduce finely divided Fe,0, to pytophore iron [0078] The eduction of porous igh surface area iron (1M) Oxide sol-gel materials gives submieron metallic iron pow:US 2006/0042417 AI ‘ders, The prexluction of iron powders via this approach is benclicial from a safety and environmental standpoint as i ‘eliminates the need foe caustic leaching solutions used inthe ‘cureal prediction of pyrophorie decoy flares. [0079] The present inventors recommend that sol-gel ‘rived starting materials be heated to and held atclevated temperatuees for some time before staring reduction. Tem- peratures used will be high enough to drive off organic impurities as well as any bound or unbound water without ‘causing the sintering ofthe porous iroa (Il) oxide network. Heat teatment to temperatures below 300° C. lead 0 ‘contaminant removal and phase changes in the ion (Ill) ‘oxide sol-gel material without a significant reduction in frease in primary particle size (See FIG. 9). [0080] Ir will be useful 10 use two separate redution steps That is initial reduction followed by cooling and then a second reduction step, This type of methodology is used ‘current prlution of pyrophotic fils and serves to reduce any last small amounts of surface oxide on the metalic powders [0081] All sol-gel materials used should be derived from ‘chloride-ree precursors. This isto minimize the chance for residual chloride ions in the solid forming iron chloride ‘species that are believed to inhibit the pyrophorie nature of the solid. In the future, residual chloride in the stating material may be used to tune the degree of pyrophoricity; however, for this initial work it should be avoided. [0082] Impurities play a role in the behavior of these ‘materials and therefore all attempts to make this material ‘mst emphasize rigorous elemental analyses on all eactanis and prosiucts [0083] To increase the pyrophoricity of these materials, Jncomporate small amounts of more reactive metas ato the final product powders as an igniter using sol-gel techniques. ‘Two specific materials, tungsten and or tin oxide, are of particular interest, Both tungsten and tin oxide precursors ‘Can be incorporated inta the iron oxide sol and gelation will, ‘reate a mixed oxide. Upon reduction, after drying, the tin fo tungsten oxide particles will he reduced to their native metal along withthe ir powder. When exposed to ai the reactive tungsten of tin metal will ignite which will help ite the less reactive Fe powders, This approach does not ike the process any less acceptable from an environmental aun safety standpoint, I bas been already boea demonstrated that pyrophore tin oxide materials ean be made with sol-gel techniques [0084] The foregoing description of he invention hasbeen presented for purposes of ilustation and description and is ot intended tobe exhaustive oto limit the invention to the precise frm disclosed. Many mexiications and variations ae possible in light of the above teaching. The embodiments «disclosed were meant only 10 explain the principles of the invention and its practical application to thereby enable ‘others skilled inthe art fo best se the invention in various ‘embovliments and with various modifications suited to the particular use contemplated. The scope ofthe inveation isto bre defined by the following claims. We claim: 1. A method for producing porous nanosirctused pyro- phorie metal, comprising: Mar. 2, 2006 ooming a solution containing a least one bydrated-metal fom inorganic salt and at least one solvent; adjusting the pH of said solution with a proton seaveager to induce gel formation of said solution to form 3 nansructured metal-oxide-based gel: ying said nanostructured metsl-oxie-based gel o form ‘nanostructured melalxide-based porous material; thermally treating said nanostructured metal-oxide-based ‘porous material to produce a thermally treated! nano~ ‘Serutured metal-oxide-based porous material; and heating said thermally treated nanostructured metal-ox- ide-based porous material in the presence of «chemical reductant cuted with an inert eaeier gas to produce 8 porous nanosinictured pyrophoric metal 2.’The method of claim 1, wherein said sanostructured metaboxide-based porous material is selected from the {group consisting of a xerogel and an aerogel 3.'The method of claim 1, wherein the step of drying ‘comprises drying said nanosinictured metal-oxide-based gel by atmospheric evaporation, wherein said nanostructured mietal-oxide-based porous. material comprises. nanostru tured metal-onide-based xerogel ‘4. The method of claim 1, whersin the step of drying ‘comprises drying said nanosinictured metal-oxide-based gel by supercritical solvent extraction, wherein said nanostric- tured metal-oxide-based porous materi comprises nano- structured melal-oxide-based acrogel. 8. The method of claim 1, wherein the sep of thermally ‘weating said oanestructured metal-oxide-basedl porous mate- fial includes removing at least one impurity from said nanostructured) metal-oxide-based porous material 6. The method of claim 1, whesein the step of thermally treating said nanostructured metal-oxide-based porous mate- rial includes removing at east one surface bound chemical species from said nanostructured metal-oxide-based porous material 7. The method of claim 1, whesein the step of thermally treating sed nanostructured metal-oxide-based! porous mat ial is carried out while said nanostnictured metal-oxide- based porous material is under a dynamic vacuum. '8. The method of claim 1, wherein said chemical reduc- tant is selected from a group consisting of hydrogen gas (H,) and earbon monoxide (CO) 9. The method of claim 1, wherein said porous nanostr tured pyrophorie metal comprises porous nanostructured pyrophorie iron 10, The method of claim 9, wherein sad at Teast one Dhydrated-metal ion inorganic salt comprises Fe (I) salt. 11. The method of claim 10, wherein said Fe (II) salt is selected from the group consisting of Ferric nieate nonaly Grate, Fe(NO,),9H,0, fei chloride hexabydrat FeCl, 6H,0, andl FeCl, 12, The method of claim 9, wherein sad at least one solveat i selected fram the group consisting of ethanol (200 ‘r00!},L-propanol, -butanol, acetonitrile, water (distilled), ethyl acetate, 2ethoxy elhapol, N.N-dimetbylformamide, ‘methanol, tettabydroturan (THF), acetone, ethylene glycol, propylene glycol, formamide, 1,4-lioxane, benzyl aleobal, Ditebenzene, hexanes, and dimethyl sulfoxide (DMSO), 13. The method of claim 9, wherein suid at least one solvent is selected from the geoup consisting of ethanol and waterUS 2006/0042417 AI 14, The method of claim 13, wherein suid of ethanel is about 200 proof and stid water is distilled, 15. The method of claim 9, wherein sid nanostructured melal-oxide-based gel comprises Fe.0, gel. 16. The method of claim 9, wherein the step of forming «solution is eared out under ambient conditions. 17. The method of elsim 10, wherein ssid solution com- prises about 0.65 g of Fe(NO,), 91,0 (1.6 mmol) dissolved in 3.25 ml. of 200 proof ethanol. 18. The metliod of claim 17, wherein the step of adjusting the pH comprises providing an epoxide/Fe ratio of about 1 19. Porous nanesiuctured pycophorie metal produced by 1 method comprising {forming a solution containing a least one hydated-metal joo inorganic salt and at Teast one solvent; adjusting the pH of std solution with proton scavenger fo induce gel formation of said solution to form a nanostructured metaloxide-based gel; drying said nanostructured metal-oxide-based gel wo form ‘nanostructured metal-oxide-based poraus material; thermally treating said nanostructured metal-oxide-based ‘porous material to produce a thermally treated nano- ructused metal-oxide-based porous material; and beting said thermally treated nanostructured meta-ox- ide-hased porous material inthe presence of a chemical reduetant diluted with an inert curser gas to produce & porous nanostructured pyrophoric metal. 20, The porous nanostructured pyrophorie metal of clam 19, wherein said nanostructured metaloxide-based porous material is selected from the group consisting of a Xerogel and an. serogel Mar. 2, 2006 21. The porous nanostructured pyrophorie metal of ela 19, wherein said porous nanostructured pyrophorie metal comprises porous nanosicucured pyrophoric iron 22. The porous nanostructured pyrophorie metal of elaim 21, wherein std at least one hydated-metal ion inorganic salt comprises Fe (IID) sal. 23. The porous nanostructured pyrophorie metal of claim 22, wherein sad) Fe (IID) salt is selected from the group consisting of Ferrie nitrate nonahydrate, Fe(NO,), 9h ferric chloride hexahydate, PeCl,6H,0, and FeCl, 24, The porous nanostructured pytophorie metal of claim 21, wherein said at least one solvent is selected from the r0up consisting of ethanol (200 proo!), I-propanol, t-hu- ‘anol, acetonitrile, water (distilled), ethyl acetate, ethoxy ethanol, N,N-dimethylformamide, methanol, tetrahydrofu- ‘an (THE), acetone, ethylene glycol, propylene glycol, for ‘amie, Iy4-dioxane, benzyl aleohol, nitrobenzene, bex- anes, and dimethyl sulloxide (DMSO) 25. The porous nanostructured pyrophorie metal of claim 21, wherein said at least one solvent is selected from the up consisting of ethanol and water, 26. The porous nanostructured pyrophorie metal of claim 21, wherein sad nanostructured metal-oxide-based gel com- prises Fe,0, gel 27. The porous nanostructured pyrophorie metal of claim 22, wherein ssid solution comprises about 065 g of Fe(NO.),9H,O (1.6 mmol) dissolved in 3.25 mL. of 200 proof ethanol