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    THE re INA OF TRANSITION lt CARBIDES AND NITRIDES Edited by S. Ted Oyama eee ran Cee hard pee o) Sete eke es preemie epee cates retin ee eer CO ea un coo Cee ern sae’ i | The Chemistry of Transition Metal Carbides and Nitrides Edited by Sc. OYAMA Profesor naman 9 emi Eneing lcksburg. Visi, USA BLACKIE ACADEMIC & PROFESSIONAL Cp Ha, 24 Hoty Row, and SN, UK ai & ti Wow Cats Hn i ern aU, at Pa, Ame en Yor ‘awast, Ckpodek, Toke Eagan Aik) Pry We Ra Man, Ve, © mecurers Sa rien. pra nrc OK Cope Desa Sa Sieecn sere ont Sercthseceiss Son Coee Scearaanseee Ry eta tet aman Eocene DSGREEs etn ot a Lay ‘Sin ANSINISD Zvaeilnd (reac Pap ns nae net Ns Preface “This bok aos from 4 smpoium ied Transom Metal Caries sod ‘iti: Preparation, Propercs and Reactivity erganize ty Joe Sung tee, Mast Naga sod ml The spon was pat the 998 Congress of Pace Rin Chemist Sait, held in Hono, lai Setmecn December 17-2, 1985. The mesg wa the int jr ‘oncrenceo excel adres the thane of meal carbides and ite, Sd brought together many ofthe major rexarches the el. Over 50 Scientists and engineers reported thee atest fogs io ie sess of Phe bok dsl follow the topes covered in he coteene heory of bonding Structure al composition Catv properties Pye properticn ‘Now method of preparation Spectsaapy and mitoscopy The hook i unige in its coverge Ie peoviles a general iroducton to the properties and mature ofthe materia, but abo covers hee lest, psations in wide variety of ld. Ht shoo thas Be of intrest Boh perts and monespents in the lds of material scence, sollte homisy, phe, ceramics engineering, and stays The Bat chapter Bites an Overt: and many of the chapters provide summer of hanced topics Al catty were peer eviowed. The field a ranstion metal carbides and mids growing apy 2x ore uses fr tes sneresting matrins emerg, Interest ithe ub “vides bya recat workshop proceedings, 2 manngrph om theory. an Several reviews and eneslopedis ats, However, tote bas ben mo “comprehensive covere ofthe topic rine the 197s Te hoped ha this took wl fea milestone forthe feb documenting progres, a sersing 8 reference source for maty years to come, Tam very think to Mishel oust forthe nspiraton to produc this tome, nd 10 my wile Hieko, sod ern, Monika and L89, fr hit sopping preparation, sro. 1 Vandevelde ‘Vocus TC, Wallace, S| Wang MD. Wels 1, Wiesenberger Lxe APE, York Universit Lie de Brueles, Fut of Sciences Analyt Cem Department, ep 255, ‘Boulevard du Tromphe, 1030 Brus, Begum Akzo Nobel Cental Research Laboratry, Dobbs Ferry NY 1652-1401, USA {Los Alamos National Laboratory, POR 1683, MS {Gr55, Lin Alon NM BI545, USA Déparement Se Chimie, Université Laval, ‘Oubbes, Quebec G1K TPs, Canad Comporate Reseach Laboratories, Exxon Research and Engineering Compa. Annandsle ‘NFost01, USA Insite for Chemical Tecnology of Inorganic Mates, Vienna Unieraty of Teco. (Geuretdemarkt 61, A-1060 Viena, Ate Department of Chemkal Engiocering, Pusan National University of Teehaelogy, Pusan Center for Applied Energy Research University of Kentucky, 3572 Iron Works Pie, Lexington KY ssi, USA Iostiute of Sciemie and Indusal Research, (Osaka Universi, Osks 567, Japan Universite Louis Pasteur, Laboratoire de Chimie des Materia Catltigues, EHICS, I rue Base Pascal 700 Stshour, asce Contents 1 rodent he chemistry of ranson metal ‘arbidesand nitride Sir OYAMA ramen 1 Cooter PHYSICAL PROPERTIES anion mca carbides an tries a 2 Apptcaton of Industral ols ut, SANTHANAM 23 Geet msinetetos 24 Grae pin enon — 8 egennestrsssenee: 2 Review of aifesion and vaporization of Group 4 ‘snd transition metal ears Tie, WALLACE, Sead D.P. BUTT 3 Meg he prin earn cece, 35 Nese ne Amal danatacesatcnontce 5H Deaf cope apres 2 Bea ate pn 2 SORTA aponon ot (2b Alan atheaonatr net MCcteponpopie 44 Chea itson in ramon metl-arbon eltraniton nete-itropenysone W. LENGAUER, H. WIESENBERGER, M. JOGUET, DD. RAFAIA and P. ETTMAYER fa owes io mumoRy [5 The orgs ofthe sinartes between ate ransitin tmetals andar tranton metal mommies MGE. EBERHART a2dJ-M. MacLAREN 6 Fermisutacofhesagonal tungsten carbide YUISHIZAWA snd T. TANAKA. 35 athow"nan ene fcc 7 Orbital symmetry and supercondactviy i aries and brcarbdes Go). MILLER Aston [NEW MATERIALS Recent deelpmentin ternary itrideceistry H.-C, nur LOYE, J.D. HOUMES sod D.S. BEM (9 Tramiton metal iaeddoube nities SURIKKAWA, T. YAMAMOTO, K. O1TA, M. TAKAHASHI and F. KANAMARU S31" The momen SMa he (CaN f= <0.) alatanmeR noueon 32 Thegencmpomd aay oth erp Noe ela depot ma el er 10 Magnetic proper of rae earthiromcompoands ‘inaningcarbon ander nitrogen KU'MACHIDA sl G. ADACHT 1 Scena ih ieeeameem 1042 Pasmanisingandarboirng 1 Greaoptse ns td Ripe SvNTHESIS 11 ‘The synthesis of tani nde and tana carbone bys propagaingcombaton M.ESUAMLOO-GRAMI and Z.A., MUNIR vs 12 Combustion synthesis of tramston meta nitride VUHEAVACER and J. PUSZYNSKI >> eta rcrmateuee seaman 13. New route to molybdenum neds and oxynitride reparation and characterization fe phases RUMARCHAND, X. GOUIN, F. TESSIER Sot'¥, LAURENT 1 eiber oN gpecmedertine BBE Quimica 136 Omiaenmcasrrinethecatiephne 184 Henan penne sya edt pcs 14 Syntbesso thin sot Cr, Mo and W carbides and tres F. RENIERS, M. DETROYE, S. KACIM, P. KONS, Bi, MAOUIOUD, E. SILBERRERG, IM, SOUSGI cl BEGRANI, 1, VANDEVELDE snd yeas Soon 1S. Single-soure precarses for the chem vapor ‘eposton of aniam and vanadium carbide and nite [I'VALADE, R. CHOUKROUN, P. CASSOUX, F, TEYSSANDIER, L. POIRIER) M. DUCARROIR, [R. FEURER, P. BONNEFOND aad F. MAURY CATALYSIS 16 Carbide ranstion meatascaayts or xiation recto NiIv ILCHENKO snd YU.1. PYATNITSRY eens eeeeeuyuuuyeg 17 Surface molybdenum specs and ac sts on ‘ried ayn alana catalsts M. NAGAI, A. MIVATA, T- KUSAGAYA etwas 1 Caride-oide Interactions blk and supported ‘asen care catalysts for leah synthesis TO LECLERCQ, A. ALMAZOUARI, M. DUFOUR md G. LECLERCO us edd Santen 1 PucherTropsch synthesis and XRD characterization of Antroncaride catalsstspndheled laser page. RUL ORIEN, L. XU, XCX- BI, PLC. EKLUND snd BH. DAViS: 20 Study ofthe omerizaton of C, and Cy, atkanes over ‘molybdenum oxyearbidecatalss MJ. LEDOUX, C. PHAMCHUU, A.P.E YORK, EIA. BLEKKAN, P. DELPORTE’ snd P. DEL GALLO 2832 Shahn sin ape et sg He fan thmanyronen aetna 21. Characterization of oxyge-teatd carbides of ‘maybdenum and tnpren fora beane-ihy drogen reactions B'S: LEE, BJ. SONG, 5. I! and H.C. WOO 22 Synthesis and easy properties of angen carbide for tametation, reforming and hdrapenton Fr SHERIF sad W.VREUGDENHI 2234 sMopemeormngover W;CSIOALO, 2 eon [SPECTROSCOPY AND MICROSCOPY » ‘Chemisrpton CO and NO molybdenum carbide ls BWANG, M CASTONGUAY, P-Il. MDREEN, S. RAMANATHAN and $1. OYAMA BT Speman soweltonce (Cuarctertraton of the electeonie and eatayie properties of vanadium carbide: a comparative study of NCW mode surfaces and VC powder materia J.C. CHEN, B. FRONBERGER, M.D. WEISEL, ITE! BAUMGARTNER aod B.D. DE VRIES pie ee Surface shifts core level energie of traiton UI JOHANSSON ™ ‘Stay af the Auger meal pk of carbides and ‘nies by fcr analyss F. RENTERS SR} Ratranpnopcdts AES me ‘Tranahon mt ntride and carbide nanoparticles ROOCHOA, XX. Bly A.M. RAO and P.C. EKLUND aa Hi ren oseon crops ood Carbide formation daring actation of ion Fiser-Tropseh ena MD. SHROFF, D'S. KALAKKAD, MIS. HARRINGTON, N-B. JACKSON, K.E. COULTER, AvG. SAULT and A.K. DATYE segy s9ags eee Mwai Indexes 1 Introduction to the chemistry of transition metal ‘carbides and nitrides ST. OYAMA, Deparment of Chemical Engineering. Vigna Police tnsinae land Sate University, Blacksburg, Voge 9081-0211, USA Astras ‘pout Doig pase poets cathe Matte. prepara aa apt ‘Sep te he peste ao be debate irk nent acres ees ae Reiaeren cnn ieee pede eat ore me Smee, 1 ntodction ‘ransion metal carbides and nities conte a diverse clas of mite with many tcehaologcl applications. Because of thi peat Strength and darby, they have tadtonaly been sed at extreme ‘ondiiom of temperature and prewar: for example, n rocket mazes and {ill bt These hurdnca as ven them applation in cating tos al Shoe apie, and snow te, In ferous alloys they are the componente respon forthe tough of tech Hoever, thy ao ave etereing ‘pt elctonic, abd magni propertics and hye ben se for opal ‘tings elect contacts, onan baer,” and other sen * The ‘sanyapleatons re renewed inaction? and by Sanbanar(hapter 3) ‘Rect years have sean plethora of activi inthe field. A recent ‘ome! comptes the papesprescacd at workabop monograph ands fevien' summa he sate of theory inthe fell, and journal mae eviews emerging appikaions i eaahs6.* In adtion, @ number of ‘cncjeloedia atin cover the general properties ofthe marl 2m enews of TANSION METAL CARRIES AND NEON 1.2. Crstalineructre and compton ‘Cun und nitrogen form compounds with al transition meta except fr thelae coments ofthe second nd tied row. The ey suctures othe ‘bade and mide py considerable variation, Toward the let in the eviose abe the sractres end oe sinpl, very ote eseming tne ‘tine poe tannin metals themsches, However, toward he i in he Taher in compostons involving lecropastiv clement (eg. Groups for), the srortures adopted tend to he more complicated. These Wands Sere int sytematied in Hig’ aie” which states tat the suuctre formed depends onthe ais aor = yy whee ad fy ate he a ‘ofthe nonmetal and metal atoms, reapetely. When ris lo than 9, the tantion metals form the common sacar: faceted cae (Ge) exaponal ned packed (hp) oe simple hexagonal (ae. with the ‘Honmetal atoms placed inte age inert sts of octahedra or cabie Dromatic geomet When peter than 09 the metals arangerent ‘Suge to accommodate he lager nonmetal aos and to preserve ta Pat shows examples of compounds of Groupe 3-6, which ypc have simple eytl structures sp compositions. Im thes stuctures the lage sed spheres reprcsent mal atoms and te small ere spheres represent Cor N atoms The nonmetal atoms xp inter postons, ‘nor his reason the mater ae knw 2 leroy “Although Hagas rie provides a simple eeometric explanation forthe formation ofthe common structures the esta structures of eartdes and rides ar imate determined by hi itr proper. Te elect Of eleonie structure electd sn tematic tsa scr changes in ‘he metals and in the carbides and irides. In the ease of pure metal, ems to the lan the peri table apt the bodyeemtred cube (Gee) structure, but lements tm he centr prefer the hip statute td furthest tthe ih the oe rte. This progression neta sites fas been cxpitned hy the Engel Brower theory to depend onthe ‘umber of valence cleans per atm (e. When la = 1.5, the Bre Strcture formed: when f= 17-21 the hep sre adopted and sehen ela = 25", the fr stractae frets. The change om he open be sruure to the cosepacked structures in the ection of gst Briloin cells The 3p or op hybrid eectrons are believed 10. be esponsbl oloag-angeproperes such as stuctre beats the a the ‘otermont elerons and Winer. Tm contra, the pred lectons are Azeer sel cleron and ten tobe be ast to the nl Tretngly, the some cyl sociare progression occuring in mca fe observed in the Group 6 metal carbuic and nies of MX Stoichiometry (X= C.N} Although the parent metas ae Be, carbides fhermetale aangement hexagonal, ands mde cable (Tale ie m i “on hn Seen: 1.1. The sit in stature corelaes wth the numberof ven elses ‘a carbon and ntogen and sugges that these elements ineease the ncenaton of gp elerorsin the alloys. The Group #5 emmpounds aso follow these tends. However, because of thei MX solo. hey ‘ave a hph nonmetal content and high p leton density, and thi cases ‘he hexagonal strcture tobe bypassed ene and an fe arangement of ‘etal tome is onarves Pate 12 Geplye examples of Group 6-8 compounds, which show incresngly complex sritres compared to the Group 6 compound. ‘Thee ie also a nolsle change n wolchiomety. Whereas i The catly tsamstion metals the fomalas ME and MOX are prevalent, inthe et ‘Wanstion mets the stoichiometry shifts 0 MX and MX “The inca MUX ratio fn moving 0 the ph inte pride able seprctents rejection of Cand N by te etl and ees the docreasg| tity ofthe carbides and ides. The reduced say ea seen in ‘he meting points ofthe carbides and nities, whi re amestreo thee cohesive rent (Tigre 11) For the metas a maximum a meling point ‘Sobsered betwern Groups and, whl forthe aids the maxim 5 shied to Group 5 und forthe mids to Grogp 4, The masimam i the fmol fe amctted wih the filing of the Bonding and antibonding fontons of the metalic bund. (The secondary matimum observed dot {he occupation of a subband ) The Shit in the carbides and ities agin ortlate th the nmr of vale eletons in erbon a zope and Sugess a tater degree of banding in the compounds. The absence of| {Srbide an mide formation in the late element ofthe second a hid owas assed with he ig ofthe antibonding repion oF the hands ia {hove compounds For ead and aides containing moe than oe aston metal, 4 ‘more varied and complex Pte 1} shows examples wher the sendy mponent sx metal or man group clement Figure 12 shows examples ‘where one ofthe secondary components isan alka or alkane earth Matting Points of Elements and Compounds. = . mol aN gat ‘ en a ¥ con ot coy ‘ * A 5" | m Xe wot fo tHe Me " ne 2 a aS i MN Be bad eee Pot croup umber cee me clement Many of these comples compounds have ionic boning and! are Secondo or isso Tet very nich chessy i Ceibod by aut Toye eal (chapter 8) and Kikkava et a (chapter 9). "every Bealy tht fatare advance inthe ulation of carbides and rides wit ocr through the dcovery of nem phases wih unique Properties. Already, inctions of thn arc appearing. A recent sty Feport that 4 V-Mo onynitde catayst bar hphetatiy lathe ydraemtrogenation of inline andl eoncions than eps tr Mo nitide, or 2 commersial NrMo sulfide" Anew rtrd or ‘tpersonductingranstiontemperstre (Ty 23 K) forall intrmetc ‘ompound wast tyan ym pallasham bone carbide” Machida ‘Adachi (chapter 10) report on a seis of highperformance permanent ‘magnetic mates hase on carbons of StaFep, 1.3, Bonding and leone propestin ‘Recent work indicates that the Bonding in carbides an ides arises Som the nerastion of carbon or ntrogen 2 and portale with etal d nba Tn fat, the 2s oral end te load ot low ents, we the 2p ostitalsinteract withthe metal and a manflat propresiyy higher energies (pure 1.3). The fig show an augmented plane wane (AP and aeton for LN "whch pe for many cred <= tl ts ee 12 Cyt eee cols cde ds som) Cafe Sl Nase at Bash se cams coy? a's m 2-09 2g Fore 3 Eran sre fin cl ties nd i Ba aan pal ec ie (6 mit enewsry of rasan META eARBDES AND ATTUDES| Ever sine the observation that tungsten eatide has catalytic properis similar wo the of platinom, there ha been comiderale ttre! In Comparing the clecfonie sirius of cubis and mids to howe of ‘nota. In ths solume, Ebchart and MacLaren chapter 5) present sty ‘tihieinteresing topic. Analysis of de Has van Alpen oxiaons Bes information abut the Ferm surface an the nature of charge cami. An rampleof sch sty sven by Ihave Tana (taper 6) or tungsten carbie. The recent dcovery of superconduc x quneary toroearbides LnNi-B,C (Ln = thane), mentioned are, has me {ed eonsierable interest inthis type of material Miler (chapter amine the oni Iterations within howe extended sd. ‘One area of conroveny inthe bonding of carbides and nds is the decom ot election transer The previous scation showed that for Dropertis ike arusture snd composition the carbon and nrg atoms Eppear to ites the denaly of op electrons inthe compounas. This ‘pprt by studice of the chemical and atalti eatvy. = Hower, pyle measurements by Xray photcleom spectroscopy (XPS). and fearedge say asorpuon finestroiue (NEKAFS) messirements hy (Chen ea (hupet 20) show da ogative charge concentrated around “srbon and nitrogen. Ths fe conrborated by APWcalelatons* More ‘ork to res thi lope weeme waraned. Perhaps ne Way oto ths ‘Hlemma'i to recoge that thee i diferene betwee integrated harass round atoms and oxial populations Depending on what Dropery i Being examine, dierent sonlosons may be feared 1A Physica properties The carbides and nse are wel known fr thei hardness and sens and ths section wll brely compare number ofthese ropes wih those ofthe pure metals Conentation wil placed hereon theft 0 ompounds sae thes constitute compete eres, and Mo and W, since ‘here ze the most commonly sdied metas. Ax willbe shown, the pica and mechanical properss of cartes and nities resem those ‘of crams not those of metals Comparitons wile made with bavon arbi (ByC), lon cathide (SC), alumium ate (ANN), silcon ‘side (88) aluminium oxide (ALO), and diamond, as representative Table 12 comparss the meng pins of transition metal wth thos of the carbides and nitrides. Th trends thon acs were tea sessed in connection wi he electron properties the compounds. Here, note Smad ofthe levated emperateres ol he carbides and mies compared tothe pore meta Thoy are among the highs for an Pe of maa, ‘dare more akin to thon ofthe cerame materia. The ming pons eo Indicative ofthe hgh cohesive strength nthe materia <———— se ‘13 Vio ord) of hen a conn a ep s me yee wee = ERE ata ie” ards isa mea ofa material's resistance to loclred deformation {denting or scratching) Table 13 reports vals ofmcroarncs forthe rateras. Microhardness casted by a diamond indenter of quare> ‘bed (Vike) or hombi-ased (Knoop) geomety which fred ito Ihe surace of est pice using a elfrted mache with test Toad of T1000 ons) The diagonal ofthe micro-indematon are meswared by 4 mictoope. Accunte mesturements ae obtained even Wilh pobjerystalline mate ce oaly single pais are sampled. Table 1.3 Shows thst again n hadnes the cabs and nde resemble ceramic ‘marl eather han mas. Dmond the hardest malarial knoW8, 2h Stands alone among the feported compounds Table 1 reports value of the module of lasicy, or Young's roduls. Thi i another mechanical property which toprescas the flies ofthe material, ore esstanee fo ea sain More presely, ‘Young's modules the ress equird to prods sun sta by changing ‘ample length Table shows thatthe modus considerably Bighorn ‘he catides and mre than in the mt, with aes resembling tose ‘fhe ceramic mattis, Diamond, atin, special The summary provided here iatrate the mechani properties that haracerize the taniton metal carbides an mites. Tae mutts a6 hard stong, and Somewhat bite, and resomble cram sabsancs, These, popenca re felewed by” Santana (ehaper 2). who abo dese the comment sed eabs-binded comme. ‘Other mtr properties of portance in the hightemperature oe of caries and ities sre vaporization bebavon and soe tae ian ssasonvenon ° “o£ BO cae ‘Wallac and But (chipter 3) presenta extensive rvew of expoimental ‘erly in both azeas ax well as methods for modeling the incongruent ‘aporztion proces. Lengaer ef (Sapte 8), present iy data Tor Group 3 entides and ntdes and te Ince! phase diagram hee systems 1.5. Hectic and magnate propertie ‘The previous scton showed thatthe physi properties ofthe carbides and nines sired subway from tone the parent met nd ‘esembled thse of ceamie compounds The electro and magne Properties ofthe carbides and iis provide an neresing contest, eaise het here are ama wih the mets a “Matra can be cs x conductors, semicondotors or altors. ondetrs‘ypilly hve resign the Tangs 102-10 a on, Semcondacim approtinatclyW/-i0" 4 em, amd slatry. aboot W080 dem. Table 1 compres the cece resy of the ‘ements and compounds room temperature. Atop he aes and ‘rds have somewhat higher est tha do the pore met they i fave resin the exis of mea ondoos in compaion the ‘ramic mater ave ch higher vac, tnd ae tpl ust. “Te comp ih Hal cient o tect tov of the carbides and ite. The Hal cote se obtained Yy mesuring {he tramwere set potential in somes made to eat Cent int ‘mapnete fil. The oeficen vena mere othe cater concen 10 rieemesny oF masts MERE cas AND NBIES ‘le 1 al tists (0) oe the larger the cri concentration, the smaller the coeffi. The sign of the soctcnt ingles the sign of the charge carte, negative for "ectrons, postive for hols. Comparing the Hall coctiens ofthe metas {nd compounds shows no systematic nds in in o& Se. Howevet the Salus at ofthe sme order of magnitude. Ts somewhat sorpesing in ‘ew ofthe cincuon in section 2 hat sugested an crear np eetron {ematy in the compounds. The lack of tend maybe do tthe lied snd caltred ata svaabe forthe cartes and ita. Here, ain, {unter work with wel-charactenaed samples I ceded Magnetism is guintum mechanical phenomenon swat withthe ‘magne moments of ndviua elecrons in materials. teil en Be ‘Samagheti,puramaanei oF froma depending 0 the esos torenteraly pied mapnctic lds Diamagnetic materiale generate 4 “mal indaced magnetic moment ns direction opposite tho heaped ied, Paramagneic materiale produce magne momen inthe action ae 12s eneaste oF reason METAL exmmpes AN NED ofthe ld The magnet suscepuibity measures the dase of magetze- ‘on of 4 miter i an apped fed, snd i neative for damage . ‘materials and poutive for paramagnetic materi Tale 7 compares the 2a “gnc tsp’ ofthe elements and compan 3 rom tmp Sore, Thenon ran group mt and compound al show prumagntam ‘The later have sale? suse, but win. the same ower of smugntode a the parent metals ‘Wheres amagneue and paramagactc materials do not exhibit rmagntism inthe ascace of general fel, feromagetc materials possess permanent magnetic moment wits a kd The magnetic ‘moments fe de to uneaneoidelectron spins present an acanaequence of {he clecon suuctre. Typical mates that he fetsomagnee are Tare farh compounds and Fe, Co-and Ni Ferromagnetic ler are 2 Shuraceried by tha coercivity {F.), the magnte Fld nes 10 due the maghetiztion fo 20, and their Cune temperature (T,) the fenperstare a which random motion cause the magni ovat ‘Table 18 sammie these values fr number of materia “Tule 1, compaesthe heat capacity of elements and compound. Fora ea {oe eletom gus the eat capac proportional tthe density of aes at ‘he Fermi energy. Again iar ranges are found in the clement and ‘Sompound although the carbides and ities show systema bigher| Nalues. Athough the tanson meals and compounds are nt tee lection gases, the vals indicate that the carbides and mitrides have Iigher Sey of states at the For nergy. Th ences wih Oh Inger activity atl reactions. This section summarized leone properties ofthe pure metals andthe carbides and nitride. alesse the compound ad sir vals 1 the ‘meal Th enuon metal carded ides ae terlore ieresting ina) of et compat epee tes & i 14 nie ctesay oF Ranson MEFAL CARAS AND NDS ‘material that combine the propertiss ft completely silent ype of 1.6. Preparation Many methods have been develope fr the preparation of earides and ‘res, and ther wl be desea this section. General cere re Schwarshopf and Kifer" Iyra* Storms.” Toth” Benesovsky, Kiefer ‘nd Extmaer Sathanam,” and Stoll and Santhanam* Kowispoe tnd Prat provide a dtaled deserpn of the clement y-element Syne of Grids, covering the period prior v0 1971 "The various metus of preparation ae cad in three eatgoies spending onthe py form and composition ofthe produc. Those tatogoics ate no absolute, thee ate oreaps depend onthe pre fonations at which the preparations are cared ut. Seton 1.6.1 and ‘Taner doxerne methoe tht penerally wie high emporatre, sn therloe, produce ow sriace arcs materials. A numberof those methods fused inthe lage scale (up Con), commercial production of carbides ‘nd nitride. Seton 162 and Table IT desde methods that prod pdkrs, parties and sported form. These are generally moderate: Tomportare methods, tat produce high surface ace materiale Section 163 and Table 112 cover method for the preparation of fine and ‘tings Escaded ia thee summaies ae methade fr the sythe of rulicomponent materi and methods fr preparing pial matures of ‘omponents inthe form of cemented caries and composts. The ater sre doeribed by Santhanar (haps? 2). 161 Low surface area materia 16.11. The det reaction of mes and clement carbon and wiogen. Cabides ne prepared by contacting tlc power ands earbon Decne amorphere (Hy or vat), sometimes in the presence of cots hydrocarbons, at emgratves twee 150 and 20 K. Nes ‘Sreprepacdby racing the metals athpanous zogen. Thermedyaanic ‘aiclaton nda tha carb formation from the elements favorable ‘Stlomerempratres but high temperatures ure employed to overcome SSletsute difsion limitations Factor affecting the tection ne rowers ine and the sate of ivson ofthe mel 16412 The reacton of metal onde tn poder inthe presence of old faron. ‘Carbide te tained by closely ing metal oxide powers ‘wit carbon and Retin, again a wth be pare mot at omperatres i a t I tne z : is A f i oe Shirt = st (0 he pin ne cyte 16 te cuesey oF ANEIION METAL CARDS AND NTIS tetmcen 1500 and 230K, with or without the presence of hydacabon ‘The factions of ones with carbon are gain thermodynamic favored The diet traaformation a owes to sabi economia ‘vanageou ovr the use of mele sine the ced to separately reduce the oxide phase avoided. The reaction of metal oxides with carton Proceeds by iter reaction ofthe onde othe metal hd then sion {teatbon into the metal or by reduction of the oxide co suboide Toomed by formation of as oxyeartde The earbothermal mtndaton of oxides ix a common method of reparation of nds. T's generally applicable co ies of high thal EKulty ike TIN, VN’ and CIN. Tis msn drwback He dha it proces are pace LOLS Sepropagaing methods. Cates ad nitride have ako been Prepared by soi! combution symtbes, method winch probably des [Beck to Golechmide>™" The method, also cal el-popasting Mh temperature synthe, SHS, has been extensively sudied by 1 sup of Roclan slenta ed by Maphanor?o> Tiogal snd epctoeeesl ‘specs have Been feviewed by Gram\ and. Mune (chapter 1), Flavack and Puseyeki® (chapter 12) and others“ Tie teshnigoe taker avastge ofthe exceponally high thermniymanse abc of ‘ties and msde. AS the name imple, the preparation mln he ‘action of metal ad a second component, which ay be a reate gas, ‘na ellantaning mame, driven 8) the exthermsty of disolon of ‘iuogen or earn athe meta 16.14 The preparation of single erytals. ‘The need fo fundamental “tudes ofthe mech, let, and sara properties cabs sd brides have necessted the preparation of single ey” Carbide Single cysts te prepared by the Vernoul cchigu, the lating Yone {echnigot, and methods iolving prespiaton fom gud metas Nide Single etal are prepared by vapor tamport proses, 162 Ponders parle and wppored forme 162.1. The reactions of metals or metal compounds with ga phase reagents A dect metho of pepation of cafes the easton of ‘neal oF metal compound wih a cabon containing gat. The compound (antes cal hyde, oie, of hale and general sod. owing Sonia his hoon appied fo the symbenis of the mide of iron cbt and nekel* compounds th very Tow enthalpies of formation. ‘Azuin isothermal ondtons Were cmpoyed. Ammonia spefeted over ‘molelat itfogen to niide mca oF oxen becuse tmsponia Srngcrnteding agen 4 i & | Exec, me, toe rae Coe, C00. WE & 1 i i i (Dope of tal nde apr, oats g 1 - Tear pana mtd i Mancino, Tetsu, TST EET. ves co phe mts NN ra | i ian, 9 oesihice ta ts 18 mecutsasey oF MANSON METAL CAMDSS ND NIRIES 1422 Decompastion of meta halide wipers. Catbies ste prepared ftom volatile metal chlorides or onehlories by resting them, with ur hydrocarbons in the vit a» lesz heat source at 1 200 K (Van Askel proces). Because the elon starting mates can ibe obtained in preform the rection one of he mon convenient sd ‘este for producing all gross Of pare carbide The reaction Thexmosynumicly favorable The Ven Arkel proces tad variation te ted to make many metal ities lke BN, AIN, TN, ZX, HIN, GN, REN, FENN, FeQN and CN.” Altiough NH, em be wed ing fps. it tends to decompose at the Temperstues needed for ide Formation (1300-1900 Kad amature of Hy and Ns isofen wed 1.62.3 Decomposition of tl compounds. Various compounds spt from the cords dessin the previous section decompose opruce ‘abides and ities. For ekample, the reaction of molybenim #8 tungsten, carbons with hyogen can be wed to Make Mose 2nd WiC" “The reactions cam be card ov im the gat phase if the compounds are volte, or inthe sold ate, aterwise, Many rides can [e"aind fom the eeucion of oxynabdes {VO}, CrO.CL) oF mmoniun-oxo compeses(NH,VO,, NHREOQ "A saration of he method wis bse the eat our. Thi onequiibvium technic savlve fat gromth and rape etna ‘ites (100000 K =") i the reaction Zone, Ochow eta (chapter 27), [rovide a syns of the laser pyrolyss method and deste an FesC Proc sed Tor extabs 16.24 Tempernoe progronmed mehods. Temperature progtammes reaction (TPR) is « method of preparition conssing of treating «| precursor compound ina ete gar src we rang te empersre Ina uniform manner. "The precursor can bean oxide, slide, ai, oF ther compound, whe the reactive gus can bea sire of hydrocarbon (Ge methane) ad hydrogen for cuties or amon for made Buse ammonia decomposes at high emperatre (750 Kt skied to ow temperate synthe of compounds like theirs oT, V, Nb Mo and W The precursors wally nthe form of poder and Bld is packed bed in ow sector. By montonngchangs nthe ext gs phase ‘ompoution, the end ofthe reaction em be ssetined and The product juenched. Because the snes ivoves the areat aasformation of + ‘Sompound toacartie emir, ts posible typos the matali tte, Sich isthe most prone Yo sinter (owestTemmann tempera). tn Sat, the ise of the Temperature rowan lows an optimal talaace fetecen syns and sitenng ate and vests product with igh specie surface arest. The sue of TPR to prepare new compounds Iaslenum described by Marchand ea chap 13) etme eeno 8 1625 Uilisatn of hgh suroce oe suppor, The we of supports tsa er tag fhe eave conpmen’ au et Coal of foe arcx and pores dtriton,Highy depered cable ples may be prepeto by Seposting x pecesr on a igh surface wee Sep td tig Tw eeu ee ta, {orsupporng angen cab snr y Lele ea (ape 18), ‘The oe of acid tes on molbdcaum site on semi Is essed by Nau a. Chapter 17). 1.626. Rescton betmren metal oxide vapor and sold carbon. nan method of preparation of ultrhigh surface teu cates ove the Feaction of std carbon wth vaporized metal xi precunorte MoO, ‘oF WO>, The synthesis wes high specif ura aes acta carbo ‘the nal product appear 1 retain a memory of the porowsrcture ‘ofthe starting materi The carbon sts ike skeleton sound which he cubis are formed and citlycaly active spe with sutfoce areas between 100 nd dp mp are generated. Materia prepared by tis retod are eserbed by Ledoux ea. chapter 20), 14627 Liquid phase methods. The snes of MoxC and WiC via ‘emical redaction methods” scared ot by iting tetrahygrouran {G0 sispensons of the meta elorides, MOC. oC nd ‘Wr, 'a 263K wth lthium trthborohydrde LIBEAM, to generate ack cold powers (1-2 jum diameter) somiponed of sale 2 ied pats. These powders re subnegueny het ested st 2-779 "0 prace the heme phases, ‘Marcha eal (chapter 13) desert the preparation of «new Mo:N ‘hse bythe eaton of Moc in CulCaCl: molten bah contain Cay [black ponders recovered afer wish nan oc olin, [irogtvich nitdes are produced by the thermal decomposition of sides epared by pretation fom hgui ammonia. Exams ate CON fiom C(I)" and NN: fom NAN) The pracy ne not stalin, 163 Piso coatings 163.1 Plasma methods. Pasoas ate Sscharges in» lowe presare gas irnment (01-4102 Pa), that ane aed fo the dive pes ot foe powders, or for the deposition of coatings ho malor types a plier win stra procesig thermal ps equa, igvemperatre, or lama torch) eecttons an Eames ea somparabe tempore, whch sr pals hounds of depos, Sod | e138 Pe ome (2) Chk apr etn 1 & 5 (0) Poe adie ee ee Bes FER tx mac (6) cet eo i ermonueros| a reagents if se, are atomic in thi envronment, bat rap quenching cere outside the pana. In slow charge plownss (eoneguoam. low-temperature, oF plasmatton) eecons are found much higher fempertures than gates species, which are generally the sonnet temperature. Reactive speces ate generated by clcton inset, ind paripate in gurphuse reactors. This method is ued with gcous Fescanso forthe sara treatment of ois Pas procesng carried oti he are scl, industrial deposition ot protective coating om metal pce such cams, sprang, of fring Ser "The wor pies ae held catlode eecfods In glow ‘dbcharye chamber and may be independ ly heated Nailing genetaly ffes etter metas! contal ae lower temperatures cit be wed Gury seneraiy ress Beller case uilormiy for Sch ems 36 fears or other complex shapes, 1632 Chemical sapor deposition. Chic apr Seposton sin tito prepare thi fine and coving” and nrequcny apport parles!=" Theis are fomedby the chem econo es pe Fr rcactne geste NH, 5 puma” ele or Ines? ron ‘CVD costing ae appli i the ecto, tong cogeneration, and seosace ines Workpecen ae pneray laced i» gh nikal soy recom and ar sje os te temperate program reser oF amb reres sin ees ar (mote fresure CVD, ARCYD). Se the coin a thea chee Tacos bewecn high pny ganna 0, they ar genta eof {roy and inlons, CVD b gncrally eae ow a Tow pees tang nrane met spss ike Ras” The pn pine poses can ‘he te ote acta recur contig th coments Le" and 8) eect for compos ormaton, sin ths cs, he posse led ‘eu! oinic cemicd por seposton (MOCVD). These tel {Super ae sper to hides Deca ty low tesion a ve! tempers, avoiding probs itersee ome ison. and

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