‘US008317978B1 «2 United States Patent (10) Patent No.: US 8,317,978 BI Manning et al (45) Date of Patent: Nov. 27, 2012 (64) NITRIDING OF CARBON NANOTUBES 2on90087899 AIS 42009 Dace ak 24999 Jonoonscas Als sb3o09 La “oan : « Suioonoisee AIS 12200 Tours sass (716) tovenors: Thelma G. Manning, Montville, piano ite seeneh ene gene (US); Zafar Iqbal, Morristown, NJ (US) 20100152326 AL* 62010 Kurz 523/339, Soroowsiss AIS 2010 Lineal ie (*) Notie: Subjectio any disclaimer thetenm ofthis. 210027199 AL* 112010 Tanww eal uot fonao74 ALS L2010. Kian sal isos patent is extended or adjusted under 35 iq 30178 AL* 122010 Suhetal 3inai0 USC. 154(b) by 0 days. 1010304215 AI* 122010 Sub etal. 4291209 AIS 122010 Siem et a si8 (21) Appl. Nos 139080867 008676 A+ Yoon aa ‘eran eitorsatas Ale hid soe ius AIS 32011 Lever (2) Filed: Ape. 6,2011 10240480 AL* 102011 Farrow ecal Doitnowso1 Ale 102011 Helmet Related U.S. Application Data 20110281034 AL* 1/2011 Leeet al (@) Provisional pplication No. 61/321.584, lon Ape INMPRIOT AL* 112011 Mia eal ee 156124 A1* 6/2012 Goyal et al. 420447.3 DIOS ALS 92012 hanes Saat G1) mech ee : mean aa omens FOREIGN PATENT DOCUMENTS Dur 912 (2006.01) Wo woroone? 42> 9206 328 900 (2006.01) Eo Vos aes BOSD S/12 (2006.01) 7 pgp ate ce Dai tis (2006.01) OTHER PUBLICATIONS in 2700 (2o06.01) ee eg (52) US.CV sn 16182; 162/100; 160103; 1621106; here “atbon nate ee for ube lal ses” “eG; 264/101; 264/109, 42714432; 4271446, Done Convl 1D yp sh VoN coopera spe) sas aavaur i977. 979740, 977781, aarp 2A, Now ee a Sop O77752 9778 9TT892; OTTRGD ered carbon naottbs? 2008 Nanotecheoloey 15 pp 1-6 (68) Field of Classification Search 162/100, st catfon nanotubes” 2008, Nanctchclow | 162/103, 106,182; 427/122, 443.2. 446, Wanget al, "rocesng and propery invesigstion of single-vallad 421/532-535, 569-570, 902, 906, 25/500, Crbon niatbe (GNI). ackypper pony oun a 250/802; 428/447.1 447.3; 208331-432, ‘Sanocmporten” 2004, Compote pat A ecpp- 23SeL232 2080-81, 382; 210660, 665: 269101, ft 264/109; 977/734-735, 742, 749, 750, 752, ‘ened by examiner STIS 84, #47, 890-892, 895 428367, primary Ecaminer— ose A Fotina . : 74) Attorney, Agent, or Firm — Henry S.Golafine ‘See application file for complete search history. ¢ ‘ge mid (56) References Cited on ee A method of fabricating snon-britle carbon nanopspe om U.S. PATENT DOCUMENTS Single wall, multvall and combination hero, from erboa 6479030 BI 112002 Finich 42344471 nanotubes, using a vacinm deposition, high temperate earn BI? Nea a “O9SI8 annealing, and polystyrene polymer rinse process Which N29 22 112008 Mb ta 210660 anopaper can be niided by either a plasmaven Saztey ART ES ah fal ZRH mannan cane nied by eer» plasmirenaneed Tiseial bes Tao tena Sigg chemical vapor deposition (PECVD) proces, or an by an Fast BES aslo Levee 2Gt%o1__ electochemical method, to obtain a useful eemiclly fne- Fei Bes 62011 tan cal G2zesi — tonalized substrate, «substrate containing metstable Ny oosidnasige Ai? 2003 Plutetewtll""""a34298 Ny. and longer chain polymeric nitogen closers. Sich 200810007528 1/2004 Bakajin eta 210680 pjtrided carbon nanopaper can be used to enhance the ballistic doovorsaras Als Talnd Were aunt : poovoussraa Aly 72004 Weber 23111 performance of gin ponent, while reducing gun bare Joosooorses AIS 32008 Toursta “ihiaint — Nearand ension hecor Soovomicd AI* 102007 Hmph da 4337 | doovoione Al "73008 Ziaagecd nana 9 Claims, 2 Drawing SheetsUS 8,317,978 BL Sheet 1 of 2 Nov. 27, 2012 U.S, Patent Kf] omen zanesst s9M0d 4H afnep unsaid seoay sayawouuay) EE Te ie t SMOS aqni Tueny aqn, AeA 5 juafonin aoewn atdnooouayt 4 zuenp BAIA yay mold T OldU.S. Patent Nov. 27,2012 Sheet 2 of 2 US 8,317,978 B1 Fig 2. ‘SCE (RE) ‘Pt Wire (CE) Immersed UV source (WE) Nanotube sheetUS 8,317,978 BI 1 ITRIDING OF CARBON NANOTUBES (CROSS REFERENCE TO RELATED APPLICATION ‘This application claims the benefit of U.S. Provisional Pateat Application 61/321,584 filed Apr. 7, 2010 the entire file wrapper contents of Which provisional application are incomporated herein, as if'set forth in its complete length PEDERAL INTEREST STATEMENT “The inventions described herein may be manufactured, used and Tieensed by the United States Govemmment for United States Government purposes without payment ofany royalties thereon or therefore, FIELD OF THE INVENTION ‘This invention relates generally to a method of signifi= ‘cantly increasing certain propellants burn rates, by adding thereto a aanopsper formed of carbon nanotubes, which nanotubes have been chemically functionalized by adding 10 the inner and outer sidewalls thereof polymeric nitrogen, BACKGROUND OF THE INVENTION State ofthe art propellant formulations and plastic bonded ‘explosive compositions, at their most basie level, are com= posed of an oxidizer ana fuel. The composition reaction tundengsne by these to materials provides the energy neces sary {0 propel the rocket, missle, shell, or bullet. Since the ‘oxidizer fuel combination must sustain the stresses of han= ‘ling, aging, storage, and use—under an extreme range of ‘conditions itistypically compounded ina formula consisting ‘ofa binder, plasticizer, and various solid ingredients. Ideally, all ofthe components in the formulation acta ether oxi ‘ers or fuels, conteibuting (0 the energy necessary for ma ‘mim proplsion performance; although in practice, certain nocestary ingredients such as stabilizers and burn rate cata- Iystsimodifers, have litle or no energy to impart tothe reac- The performance of the propellant is directly proportional to the enthalpy’ release ofthe oxidize anu fuel ingredients as they undergo combustion, and inversely proportional to the molecular weight ofthe gases produced in the combustion reaction. In practice, some tradeoffs are necessary to gin the best performance from available ingredients and formula tions. Aluminum, for instance, is a fuel whose combustion products ate relatively high in molecular weight, and re in most eases, not gasesat al, but solids. However the enthalpy release by the combustion of aluminum iso great in propor 1210 anything else, which would ouberwise be available as fol ingredient that the metal is commonly used asa fuel in high-performance tatial and stategie rocket motor appli ‘ations. Another material commonly utilized, despite some ‘drawbacks, is the oxidizer ammonium perchlorate. This ‘material has high negative enthalpy of formation, limiting its enengy release upon combustion, and, in addition, it pro- “duces hydrogen chloride upon combustion, a relatively high- ‘molecular-weight toxie gas, However, ammonium perchlor- is inexpensive, easy to formllate, bas very trctable ballistics and favorable bu characteristics, and 80, despite its limitations its the state-of the-art oxidizer for most soli propellant rocket motor formulations “The ation of nanosized particles as an energetic ingro= ent in propellant formulations, because of their small size 0 o 2 ‘and high surface area-to-volume rato enables the propellant ‘oachjevehigher burning rates and impetus. Theoretically. an advantage of using aluminum particles in nano-dimensions is tat they have a short ignition delay and combustion tine If the particles burn close to the propellant surface, the heat feedback rate into the propellant surlace can be increased, ‘causing an inerease in the overall burn rate. However, the dition of nano-sized aluminum particles to fast bumning HE (high-energy) propellants, e.g. RDX or CL-20 based prupel- Janis, di not modify the burn rates expected. An article by Manning, etal, fects of Nano-sized Fnengetic Ingredients in High Performance Solid Gun Propellant, available at the Defease Technical Information Cente, Et, Belvoir, Va. of line att “wwwalicamilleg U2sedoe-GetTRDoe pdRGAD- ADAASI943 May, 2008", sclses thatthe addition of nano-sized aluminum particles ‘oan HE formulation slighty deereased the propellant burn rateat pressures below 41-4 MPa, while exhibiting almost no effect n the buen rate above this pressure ‘The Manning article further sated thatthe addition of ‘nano-sized boron to HE propellant formulations produced the same lack of effect as did the addition of nano-sied alu ‘num panicles. Whereas prior (0 the experimentation, one ‘would have logically thought that nano-sized boron particles ‘would enhance the burn rate of any HE propellant consid- ring that boron has the highest Volumetric heat of oxidation ‘ofall common fuels, 137.45 kllem*, a high gravimetric heat of oxidation, $8.74'kligm, and a density of 234 gmiem, ‘which is much lower than aluminum and should have increased the mass buming rate ofthe propels Kuhl etal, Detonation of Metastable Clusters, 39 ICL Conference on Energetic Materials, Je 2008, reported that polymere nitrogen can accumulate 4 ev/stom in its NS face- ceatened-cube gauche (FCC) structure, releasing energy by cluster fission: N8—»4N2, Kul tndied the oeus of states in thermodynamic tate space forthe detonation of sucha me stable polymere nitrogen. In particular the equilibrium isen- ‘cope, starting atthe Chapman-Jouguet state, and expanding down to 1 atmosphere was calculated wit the Choetah code Large detonation pressures (3 Mba, temperatures (12 klo- K) and velocities (20 kis) area consequence of the large beat of detonation (6.6 kilo-callg) for sch a trogen luster ‘based polymer. Kuhl concluded that if such metastable nitro- gen cluster-hased polymer could be syathesized, it woud fff the potential or large increases in the energy density of vaterils Therefore thereis anced in heat fora nitrided aano-sized particle that can be ade to propellants to enhance the bura ‘ates thereof, particularly such a particle incorporating asyn- thesized metastable nitrogen cluster based polymer that Will ‘add very signifieant energy upon detonation thereof. SUMMARY OF THE INVENTION ‘To fulfil the above detiled need, there is provided by the present invention # method for synthesizing and chemically unctionalizing metastable N,, N, and longer chain poly- meric nitrogen ehisters, eg. Noy, on carbon nanotubes; incliding, oa the inner and outer sidewalls of carbon single ‘wall nanotubes ("SWNT"), on the various wall surfaces of ‘multivall carbon nanotubes (°MWNT"), and preferably on ‘mixtures thereof which nanotubes are first formed into sheets of non-britle nanopaper, to provide a usable substrate for the nitriding process. Such nitrided carbon nanotubes have been shown to exhibit an endothermic onset at 300 degrees Centigrade, similar to that experimentally sbown by Wang et al, Nanoscale Energetics with Carbon Nanotubes,US 8,317,978 BI 3 Mat. Res. Soe. Symp. Proc, 800, 351 (2004), with respect © nitrided carbon nanotubes, The coatinwed reaction of nato- tubes nitrides by the synthesis othe present invention, led 0 arapid exothermic onset at 350 degrees Centigrade, similarto ‘what is typically seen in an energetic material like eyelotet- ramethylene-teimmsitramine (also known as HIMX) Further, similar results were also obtained using Raman specteoscopy, SEM, laserablation mass spectrometry, DSC and FTIR-ATR. Use of such ntrided carbon nanotubes should improve the ballistic performance of gun propellants by making it easier to achieve the desirable burn rate differential of 3:1 between the fast and slow propellants in fast core configurations. Fur- ther, the polymeric nitrogen in the propellant formulation, should increase gun propellant performance by lowering the COICO, ratio of the combustion gases, and further stil, should reduce gun barrel wear and erosion by increasing the [NICO ratio ofthese same combustion gases. ‘Te present inventive process for nitriding carbon nanopa per comprises first forming a handlable, iv. relatively non- britle and flexible, earbon nunopaper from commercially available, ic, bulk, earbon nanotube particles —irectnitid- ing of svch individoal earhon nanotubes being inpractcal swith today’s technology—the resulting nanopaper being nitrdable by eithera plasma enhanced chemical vapor depo- sition method (PECVD), orby an clecttochemical deposition method under ultraviolet itadiaton. ‘The anopaper is Jormed by fist preparing a uniform dispersion of earbon nanotube particles, in deionized (DD water containing astall ‘quantity of a surfactant, which mixture is subjected to an Ultasonic hora sonieator to obtain a uniform dispersion, ie. suspension, ofthe carkon nanotube particles, which suspen- son i vacuum filtered through a micron sized membrane tut a bed of fom about 0.5 to about I mam in thickness is ‘obtained; then sand under Nowing ammonia oe nitrowea preferably ammonia, at about $00 to about 1000 degrees C. Tor about | hour: and then rinsed witha Ito $ weight solution ‘ofpalystyrne polymer nan organic solvent, suchas toluene. “The rinsed sheets ware then died under ambient conditions until filly dry—about 6 to 8 hours-—and pocled off the ilta- tion membrane—providing a handlable free-standing sheet ‘of anapaper consisting entirely of earbon nanotube bundles, the nanopaper sheet being from about 0:3 to about 1 mm in thickness According to the present invention, the nanopaper can be nitrded using a plasta-eahanced chemical vapor deposition (PECVD) method, wherein a length of carbon nanopaper substrate is placed in a temperature controlled, gas flow through farce, heated from sbout 150 to about 200 degrees Cand a radiofrequency (ef) energy source, about S00 about 7H watts of power, excites anittogen-hydrogen sas stream, oF nitrgen-argon gas stream; which stream is passed over the rhanopaper substrate ata rate of about 25 to about 50 standard ‘cubic centimeters per minute ata pressure af about Iw about 1.4 Tor, fora period of about I hour. Preferably: the nitrogen- hydrogen oF nitrogen-argon mixture is about 25% to about 50% nitrogen to about 75% to about 50% hydrogen oF ‘angon-—most preferably, the nitrgen-hydrogen mixture is used, and the ratio i about 50% nitrogen to 50% hydrogen. The nitrogen gas provides the chemically functionalized metastable N., Ny and longer chain polymeric nitrogen clus- ‘ees that will then deposit on, ie. nitride, the earbon nanopa- per substrate, ‘Altematively, according f0 the present invention, the ear- bon nanotube nanopaper substrate canbe nitride in anelec- trolyte cell, wherein the earbon nanotube nanopsper is sus- pended within the electrolyte cell asthe working electrode, the cell containing an about Ito about 2 molar, preferably 0 o 4 about IM, aqueous (preferably DI water) solution of sou ‘azide (NaN), to providean eloetolyte at pF equal to about Also, suspended inthe cell are a platinum fail counter elee- ‘wode, anda saturated calomel electrode, asa reference elee- tmnde, A computer controlled standant cyelic vollammetic potentiostatgalvanostat ean be used to monitor the oxida tion-redhiction reaction in the cell and will indicate the end- point of then flew — which shouldbe within from about 30 ites to about 1 our The nature of the subject vention will be more clearly understood by reference to the following detailed description and the appended eli. BRIEE DESCRIPTION OF THE DRAWINGS. Punter features and advantages of the present invention ‘may be understood from the drawings in whieh: TFIG. 1 isa schematic of the plasma-enhanced chemicel vapor deposition process used in the present invention +0 ‘obtain nitride earhom nanopaper FIG. 2 isa schematic of a 3-electrode electrochemical cell deposition process used in the present invention to obtain niteided carbon nanopaper. DETAILED DESCRIPTION ‘Te present invention provides a method for nitriding ear- ‘bon nanotubes by synthesizing and chemically funetionaliz~ ‘ng metastable Ny, Np. an longer chain nitrogen polymeric clusters on SWNT, MWNT, and combinations thereof on ‘non-britle nanopaper formed ofthe earhon nanotubes. The method requires high quality, impurity free, earhon nanotube particles, which particles are initially formed into nanotube sheets, refered to as Buckypaper, or nanopaper, which car bon nanotube nanopaper sheets provilea substrate which ean more effectively manipulated during the required niteiding processes, and subsequently ean be easily converted back 10 particle size and added to propellant formulations ‘Pursuant to the present invention, the nasopapers formed by frst preparing a uniform dispersion of SWNT, MWNT, andar combination thereof, n deionized (DI) water, which ‘isporsion process is added a small quantity i. about 1% by weight, ofa surfactant, for example, a nonionic surfactant sch as Teiton X100" avaiable from Sigma-Aldrich, St. Louis, Mo, of an anionic surfactant such as sodium dodecy] sulfate will also funetion wel, in fact, most common non- ionic, anionic, or eationie surfactants will function equally well to redice the surface tension of the water, thereby allowing the nanocarbon particles tobe wetted, and thereby allowing the particles to go into dispersion or suspension ‘more easly. To provide the required unifonn dispersion, i, suspension, ater adding the carbon nanotubes, and small {quantity of surfactant, to dhe DI water the mixture was sub- jected for from about 15 to about 60 minskes, preferably for rom about 15 to about 30 minutes, to an itrasonie hora sonicator (Fisher Scientific Sonicator 3000), at 300 W, t0 achieve the desired dispersion The now uniform suspension, ‘was vacuum filtered, at about 0.2 atm pressure, through & jeron sized membrane, preferably, throgh a Fluoropors™™ ‘Mitex™ membrane, hydrophobie PTFE membrane bonded {01 high density polyethylene support fer, avilable from Millipore, Billerica, Mass, which has a 10 um pore size and i 25 mm in diameter—though, generally, about 0.5 to about TO micron pore sized Teflon coated membranes should work equally well, The vacuum fering process is continued until {hed of layer of nanoearbon particles of from about 0.5 to about I mm is deposited on the membraneUS 8,317,978 BI 5 The vacuum filtered carbon nanopaper sheets, were thes amealed under owing ammonia or nitrogen, preferably ‘ammoaia, a about 800 to about 1000 degrees C, for about 1 hour-to burn off any residual surfactant, or other contami- rans (such as small amounts of metal catalyst found 0 be present in the carbon SWNT provided by Cheap Tubes Ine). Prior experiments of annealing the filtered nanopaper sheets with ammonia mixed with argon at $00 degrees C. for 30 rites were not successful-the resulting nanopaper was ‘much too bitl. Regardless, tis believed, thatthe annealing js erucial to removal of any surface impurities on the earbon rnanopaper, to improve the bonding of the nitrogen thereto, in the subsequent nitration steps and avoid the potential foran ‘explosion de to an impurity. Th subject annealing process, ‘with the specified environment (i. ammonia oF nitrogen osphere)and elevated temperature conditions ean be done using atmospheric pressure chemical vapor deposition (APCYD) equipment such asisavailable commercially rem CVD Equipment Corporation, Ronkonkoma, N.Y. ‘To provide the necessary structural functionality the annealed carbon nanopaper ofthe present inventive process, was enforced by simply insing the annealed material with to 5 weight percent solution of polystyrene polymer in 8 solvent, preferably an organic solvent, and most preferably toluene. The rinsed sheets were then dried under ambient > ‘conditions until flly dry-—about 6 hours—and peeledoff the filtration membrane — providing a frve-standing sheet of nanopaper consisting entirely of carbon nanotube Bundles. ‘Thisrinse resulted in carbon nanopaper sheets that displayed significant improvements in Young's modulus and tensile ‘trength—such thatthe resulting carhon nanopaper was func- ‘ional forthe subsequent required processing ‘SWNT particles are most preferred in the present invention ‘dueto the fer length ofeach tube and the resulting exibility ‘of the nanopaper produced. Particular, high quality, impurity Jee, carbon SWNT particles useful inthe present invention ‘canbe obtained from Southwest Nanotechnoogies Ine, Nor- man, Okla, or from Cheap Tubes Ine, Brattleboro, Vt, the ‘importance of having impurity fre carbon nanotubes i to avoid the potential of an impurity causing an unforeseen, reaction and detonation during the inventive niteiing pro- ‘ess, The Southwest Nanotechnologies Ine. estbon SWNTS. haveanouter diameter of 112m andan average fiber length ‘of about 1.02 jum, Whereas, the Cheap Tubes Ine. carbon. rhanolubes havean outer diameter of lo 2am andlan average fiber length of 5 to 30 ym significantly longer than the ‘earhon nanoruhes from Southwest Nanotechnologies —how= ‘ever this dference did notaffect the quality ofthenanopaper produced by the subject inventive method. The MWNT particles are shorter than SWNT particles and the resulting nanopaper is not as flexible as tbat produced from SWNT particles and is more brite. However, MWNT particles are less expensive ad ithas been found tha using @ ‘combination of MWNT and SWNT panicles produces an ‘acceptable, non-belte, Nexible nanopsper that is less expen sive than the pure SWNT nanopaper. Preferably, the ratio of MINT to SWNT should be about a 3:1 wut ratio. A source ‘of acceptable, pure MWNT useful inthe present invention is, from Nana Inc, Waltham, Mass, The presen inventive method provides two sterntive pro ‘cesses loenitriding ofthe carbon nanopaper, formes pursuant to the present inventive method, as detailed above. The fst niteing method, as istrated in FIG. 1, tilizs a plasma- ‘enhanced chemical vapor deposition (PECVD) method, wherein carbon nanopaper substrate (the “substrate” shown Jn FIG. 1) is placed ina temperature controlled tube furnace heated to from about 150 te about 200 degrees, and a radio o 6 Frequency (ef) energy source, about 50 0 about 70 watts of power, excites a nitrogen hydrogen gs stream (not shown in FIG. 1), or nitrogen-argon gas stream (shown in FIG. 1) which is passed over the nanopapersubstrateat arate of about 25 to about $0 standard cubie centimeters per minute, at @ pressure of shout Ito about 1.4 Tor. fora period of about 1 hour. Preferably, the nitrogen-hydrogen or nitrogen-angon ixtureis about 25% to about 50% nitrogen and to about 75% to about 50% hydrogen or argon—mos preferably, the nitto- sen-hydrogen mixture is used, and the ratio is about $0% nitrogen t0 50% hycrogen, The nitrogen gas provides the chemically Functionalized metastable N,, Ny and longer chit, €_8. Nap, polymeric nitrogen clusters that will then deposit on, ie. nitride, the carbon nanopaper subir PECVD oquipment ase in forthe subject process is svi able commertally, suck as from the First Nano Division of the CVD Equipment Corporation, Ronkonkoma, N.Y. “The second method of depositing ofthe desired nitrogen sroupsonto the carbon nanotube nanopaper substrate accor ng tothe present invention, involves first preparing the ca- ‘bon nanotube nanopaper, as detailed above, which nanopaper| is used as the working electrode (WE) a an electrochemical nitriding process, as illustrated in FIG. 2. The nanopaper clecimndes suspended in an elecirolytic cell, contsining a 110 2 molar, preferably 1 M, aqueous (preferably Dl wate) sol tion of sodium azide (NaN), to provide an elevgolytesolw- tion a pH equal to about 4” Also, suspended inthe cell area platinum fol, or platinum wire counter electrode (CE), and a Saturated ealomel electrode, as a reference electrode (RE). Computer controlled eyeic voltammetry data ws collected ‘using a computer controled potentiosta-galvanostat such as available from Flehema, Potsdam, N.Y, during the eleeto- funetionalization of the nanopaper working electrode with nitrogen, that occurs as per equation (I), immediately below. INF TANS 2e ANN PONE © ‘The potentiostat-galvanosta will indicate the slowing of te ion How and therefore the end-point inthe eletrochem cal rection which shouldbe within a period of from about 30 minutes to about 1 hou. ‘Within the subject reaction, N,° and N° radicals will form via oxidation of N,7 fons and reduetion will erate radials tnd further reduction will convert the radicals back to Ny” anions I active sites are present on the nitrogen-doped care ‘on nanopaper and excess radicals are present inthe sluton 'Nq radicals wll convet to Nq chisters, and Na radicals will form Nand clusters, which cluster will be encapsulated fon the carbon nanopaper sidewalls by covalent bonding ‘benwcen the carbon onthe naopaper sidewalls wth the cus ‘ernitrogen atoms. Oxidation reactions would then predom tate and in-situ ultaviolet radiation applied will yenerate uditonal Ny radicals to inerease the production of Ny hi temper the proces detailed above and in Equation 1 “The invention claimed is: 1A process for forming and nitriding carbon nanopaper ‘comprising (@) adding carbo nanotube particles in an aqueous solu tion of 1 weight pereent surfactants (subjecting the aqueous solution to an ultrasonic Dorn Sonicator antl a uniform dispersion ofthe carbon nano tubo partiles is obiained within the aqueons solution; (c) vactum filtering the aqueous solution thnowgh a micron sized membrane to obiain a coating of deposited carbon hanotube patiles from about 0.5 to about mim onthe ‘membraneUS 8,317,978 BI 1 (@) annealing the carbon nanotube coated membrane under owingammoaia,atabout 800 0 about L000 degeeesC., for about 1 hour, (rising the annealed carbon nanotube costed membrane ‘wih I wo 5 weight solution of polystyrene polymer in an organic solvent () dying the rinsed annealed carbon nanotube coated ‘membrane under ambient conditions until fully dried (g) peeling off the itration membrane asa carbon nano paper (h) placing the carbon nanopaper in a temperature con- ‘rolled, gas flow through Furnace, heated 19 about 150%0 about 200 degrees C. (@) subjecting a nittogen-hylogen gas mixture to an about 50 to about 70 watts of radiofrequency energy 10 gen cme an excited nitrogen-hydgen gas 6) passing the excited gas over the heated carbon nanopa per, located in the gas ow through furnace, a arate of About 25 to about 50 standaat cubic centimeters per ‘mine, ata pressure of about 1 to about 1 Torr, for 8 period of about 1 hour, (s) removing from the gas flow through fumace a chemi cally functionalized nitriding carbon nanopaper. 2. The process for forming and nitriding carbon nanopapce ‘of claim 1, wherein the annealing of the carbon nanotube ‘costed membrane is under lowing nitrogen gas. 3. The process for forming and niding carbon nanopaper ‘ofelaim 1, wherein the gas passing overthe carbon nanopaper isa nitrogen argon gas plasma 4. The process for forming and nitriding carbon nanopaper ‘ofclaim I, wherein the carbon nanotube paticles ae selected fom a group consisting of single wall carbon nantes, ‘nutival carbon nanotubes, and a combination thereof 5. The process for forming and nitriding earboa nanopaper ‘of claim 4, wherein the carbon nanotube particles are 23:1 ‘WUE mitio of muliwall fo single wall carbon nanotube par- files 6. A process for forming and nitriding earbon nanopaper ‘comprising: (@) adding carbon nanotube particles in an aqueous solu tion of 1 weight pereet surfactant; 8 (subjecting the aqueous solution to an ultrasonic born ‘onicator antl a uniform dispersion ofthe carbon nano tube particles is obsained within the aqueous solution: (c) vactum filtering the aqueous solution thnowgh a micron sized membrane to obtain 2 coating of deposited carbon nanotube particles from about 0.5 to about mm on the membrane (@)anacalng the carbon nanotube costed membrane under Flowing ammonia, atabout 8 oabout 1000degrees, for about 1 hour: (rinsing theanneated carbon nanotube coated membrane will a 1 10 5 weight solution of polystyrene polymer ia ‘an organic solvent (D drying the rinsed annealed carbon nsnotube coated membrane under ambient conditions until fully dried (@) peeling off the filtration membrane asa carbon nano Peper: (suspending the carbon naaopaper within an clectrolytic ‘ell asthe working electrode; the cell containing an fbout 1 © about 2 molar aqueous solution of sodium azide to provide an electrolyte at pH equal to about 4: ) suspending in the electrolytic cell are a platinum fei ‘counter electrode, anda saturated calomel electrode, as a reference electrode; (using computer controled standard eyeic vollammet- ‘rie potentosta-galvanostat to monitor the oxidation- reduction reaction inthe cell indicate the end-point of the fon ow: whereupon, the carbon nanopaper will Be fully nitride. 7. The process for forming and nitriding carbon nanopaper of claim 6, wherein there isan immersed UV source withia the electrolytic eel '8. The process for forming and nitriding carbon nanopaper ‘ofelaim: 6, wherein the carbon nanotube particles are selected tom a group consisting of single wall carbon nanotubes, :multivall carbon nanotubes, and a combination thereof, '9. The process for forming and nitriding earbon nanopaper of eaim &, wherein the cazbon nanotube particles ae 2 3:1 ‘wUwt ratio of multiwal o single wall carbon nanotube par tiles.