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These ~,aJers are extremely :lm:portant because their properties ~from a surf:a'e~'chemistry' :po:hl't of 'vieY(" can be' e11tin::~y di,fferent 'from the' annealed 'bunt metal or a.Uoy., Li,kem5!e" th,eir m,echan~caJjb e-havi or' is; ,019,'0 in,fl~llted by the amount and the' depth of de:~or.ml;tio:n of ftl,e surface :~ayers .. W'idl ceramlc materlals the oxide layer m,IY or :may not 'be 'present, For example, om alumin um oxide, 01~:~f'g,en an int~,gra~ part '0;£ the struet u.n~'5,0 is an oxide' surface layer' is, not expected. However ~ adsorbates may still 'be. present on the surface from tJtliC lenv:ir()nmlent:~ and these inc~ud,e' 'wallet"vapor' and hydr-ocmrbon:s ~ In addidon ~ 'w,i.tb carbon bodies (mecha.'ni,ca~ carbons that are Y~n{ frequently u:sed)~ adsorbates phl3t a very -arge role. lEVlf:ll though an ,()x.i.de may not be ,pt,eSe~lt,because the Q,xides of t,he carbon (ear'i..,(},iIi'!I' m" '0',', - n,n~~.~and 1",-8',' ,r', b :o!"fO 1 d.'1"0"' ..Ki.d~ 1. are vo.. ~ \ ,;lla'tn~, adso .. rbed ~:noc:ies, ~,r;,.,xy",en .. z IJ _ It"', and. \V,atet va,por as, wen as :hydroca.fbonJ~,) :pl,l,y a ve·fJy heavy role in rhe
1

1:11 ....

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!Mill, "'"',

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&,Il;00\,

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'1Ii

:1.-3)., Ole oxygen is present in. two 'form~': (1) combined whh the' ~:ro~1l the T ~Iil E:-- -'I 0 oxid-'" ;, -'I'd'-I -: '-:11' ' '.",' .' "'0'·' '" rorm nf ,;, non oxioe, ,Ill: ('2'J ' IIi presem on ~:I.., [sur·f··"ace, "'as ,an ,DL_80fua t,e' '4--' i~',a~f-' me : uY us.... _. or In comblnatlen with, ,e~ther carbon or sulfur" 'The iron sample examined hl figure ~..3 was c~ea-ned.w,i~.h solvent be:fQr1E!: was inserted in the vacuum ,I, it. L,."., ,iii.., " .-. '. ' '''d': --. ',', 'I ch am b'.' r. w I,del~was- ev,ac,uP,at_e' Ii,O a'1 pressure [ -0.-,f .~" 1- -I'-, ~ ,[.,. ,-, W~, u, Uti,to,.er medi, ,~,' •. e torr ith ': me mate bakeout ar 2~ l " C" Des;p1itc' these condi.dnns and the en vironmenr, the 5Ur-:face' 'contain s 'I number of cont ammant SI (fig~ 1... ).., Thus" ,IDlY examination 3 of an i:ron surtaee sueh a's;dll9!t, re,p,resented by the' data of figure 1,-,3:is niO~ 1:111. 'f-'- . . f;·· , -[b t' lI"a~~ler an ", "_ SUI"'.a,ce 'COtL~'_ sd Ilo.y 0:',-, and . ",,'L.. ",' . :f-- :' - - ver ",8,01, ,an. 1rol1. surace.'li.h IJon U'. 'xide __ __'.::: adsorbed films such as; those indicated in. fi81U1e' 1.- ll(lb)i. 'Low' enier,lJ' electron difft,action (L'BED) :is a surface ,anwyti;c~l tool used ~Q an alyze the structural ,arrang[mnent o:f atoms itl the outermost atom ic 13l.y~er '0 r ,50~id, surfaces, 'The' mechanism for ope~radnl 'with L;EEDI 'w.s described in detail in, ,c'h,a:pter 2. At this :point, however, it ~s suffleient to in ... dlca te th at LEE" can 'j;,Iil,d'I; ...ate the arran aem ent "0' f Q:l .. m- - ~ in the outerm ,,·"D·· ato atomic layer of a :s-o~:id surface ~I fa LEEDI pattem is ,0btained from the sur .. face shown i-Ill "d;gur,e 1. -3; the structural arrangements are as shown in the :ph.ot.om:icrogra;ph in. figure ~-4,. The iron surface before c~eani,nB showing sulfu f B."in,. monoxid 1 e···· nresent vn the surface as w~]. ~ 1"I""n-': xides is 0' ,!iU~ '-~' nd carbon _, r, 1I1_ ..... it""'r'!;riJ!Ii;;o~.n. ,.W.A""" _~ .... I, , ~:n·'i;('lo"ll'ta.d', ~ raetioned nattern to the_ ~.B·f~' ,.Iil !~~~ (fig,. ~4')1. The nattem contains a n~mber. of 'white spots" 'These, spots refleet the IcUffr,acdon from 'the surfaee an d. various sneei present on. n,h so,'I"d- ' sur r- ace, vanons speeies ne 1 > -':'_ 'Wh .... r' I .1.. ··-,_,~,[e,n. iron ,5,ttn::ace 1:5, very c_,ea'D"'---bila,t. is, ue a tee hthe ~ ,·IUqUf' SUCiI:l. as ,aI,S,on iron bo'mhardment :is 'Used to remove these surface contam ~na.ntsand onJy elean iron is left-s-a LE,BD' pattern such as t:ha~shown on. the right in. :figure :1:4 is obtained. The elean surface is represented by on],y- '[our 'wh:~Jt,e'dlffraction ,spot s in a reetaagular array. These rOULr difftact ~on spots are the ehaeaeteristie pattern for the' iron ('O~.]) cl,ea.n ICfYS~,al surface, AU the: add] ~ t i,anal diffraction :s,pot [5, on ! ,telt pattern in :figpre 1--4" p~jo:r- to IcleaniDI" he ate' due 'to II,he 'clon.tanliFlants, (inc]uding, oxygen" sulfur, and earboe) 0'11 ~he soUd surface .. Thus, from an elemental anrdysis[ of the solrud' surface (:f~g~ -3.) ] 1-,-4).", it beeoxnes 'readily aeQill d a stru .. ur. ,~'I- easternJll 0"-: ,'ie' th.'!lIlli' surface ('~f'l' _, hJilL, ,t"iIiiII,1IJ. ,,,",, . ~ _' "''!I.I .~. , .,. ~, F parent that 'w'ha~ mi,ght normal ~y'be considered a clean surface :is io ,realhy Qld~e hea;vUy contaminated, 'with surface n~ms;" Aclean surface such. as thai! _. indicated on t he 'rilh~ in fis:ure: I,-4 can only be: main t lined. ill a, geed vacuum,
-''-,''C' -'c' 1

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h ~O]U SURfACE' 18'tf'O Rf C ~EAIN.lIN1C. S UUUR ANI) iL,A~~,~!Jf.J

St~~FA!Ct

MO~OXi'lD\E I~IU.'S~ Nif

ON S·I!JIR\F AC~:

presen'& in,cludins; hydro,g'eJ]" Qxy,ge,fi~ carbon djjo,xid,e~, ,and, hydrogen s,lllf:~d,e ~ The data cl t,ab~"e l,~1.1 indi,ca;h'~;tllla.t in the absence of a'liY adsorbate, the friction coe:friC'ent varies with. orientation, 'friction being hl,g'hest 'On. the :[ 10l :surfaoe and, 'least on the [11. 'j surface ~ F'd,cdo,n, coe:f.flci,lents, for metals U O (:in geMr,1l ~bod:Ycentered euble, faee centered cubic ,Illd close packed hex ... 31(011) are usually lowest on the h.ig'tlJeit atomic den,sn'y'", ~ow surface en.er,IY planes in the meuJJl,. For 'the body -eentered ..cubic ,~Yltem this, generally' hi t,he ~ U ] 101 sU:F'ftwe~; the' face-ceatered-eabic Sy'5t ern, the :[. ,~ 1.] s;t~r'fa(',e; and for fo:r' J the ,cih)5,e-:ptl!c:k,ed~hcxago':nlaJ .sys;~emi' the :[()()olj surface. These surfaces are the high at.olm:~'den~ity low surface Irnergy phlittes in. their respectfve cry.sull sysnemS,t and th.~y ac,oordiI~ly emU=-, t the: lowest fri!c,U,on. characteristics, It is of' blteres.t to note in table 1 I I:that: even the presence of' a gas such ,U Ji,dro,g~!l" n[!ormally co!ul~de;red.~"obe a f1educing gas adsorbed :[,0' the su r faa;' of the tungsten, p,rc·d:uCleSa reduedon :i:othe fri~tlon. ooeffJJCient on each. of dt,e three t:ong;st,cn planes .. T11@' frietien ctlefficmnt IOn. the :[,100), surface is reduced ttl' neatly hi!df o:r wha;~ it w,a.~in the absence of Ul!eadsorbate. The' difference between the clean tungsten surface and the llydtu81en covered surlace is Iess for the (2l,O]:and, the' U :10]surfaces, but t sere is still a reduction
t

mil,e the infl uenee of orientation and 8jO$Or ate on. friction behavior. In b general, the' friction responds not only ro tbe: orientanon effects but, also ~tO the particular species that m,ay be present, on the solid surface, This ori,en.tCl"" ~ion.and adsorbaJt.e s;peci,fh::~lty are demonstrated 'by tbe data of '.a.ble ~..II~ Table ~-Il presents fficdan data. for' a. taFge-gf,ainoed tungstee sample con ~ tajrnilllg,~y,st,aUiiles10 f various orientations on the solid surface ~'Tbi8 was, one llf,l~e dls,k specimen. cant,lining various o.ri,eDUitiO(nS ~ Three gr,ain'!;, ar'e a I J.l0] surface, a [1,1.0]:,urf:a'oot, and ,8 ~I00 1 surface, with various chemisorbed ,ga.SI:S s

to

"OJ

:1-1.1:snows, ~h.a'nthe most effective adsorbed ,1;.ISlOOU;S species for reducing the friction ,ooeffi,cien.t for ,a.n three planes of'tuD;gsten. is o:xyg,ep. there are two trihollolica~ im'p~"ica.tilo'n,s0 f tbJ: data o'f figuf'e ,I... and table 8 'I~1~_ 'FI'~r~'"e'vitriI!il.Hlc·'I-y.,m-IO"l ifiilll ~ of on ,~ 'io'l',\"'i;lll" ~U met 'II sur.Il g-t,_ " face can, :mlr,k"edJ.y influence ;3, tribo'~olical property such as fric{ i,on
"'~"I!!I '_'

of frknon with adsorption of hydrog:en.,

Table

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'I'll

T AB.l.S, 1..11.,- iNf~L'UENCE IOf VA)]()US CHEMISOR'BEDI 'Q,A,SES ON' FiUCTION CO:EFFICIENT 'OF l'UN'Q-STEN ,IN VA'CU1JM [Rid~' ~mti!~" (~IOO)al'omii~ phl'O¢ of' tungs,ten; 'l:cad~ SO,8,: $41i'di'!l8,_'y~1~dlt~'~,
10,,,.001
'~/:sc(:j;

tem,~aU~ite~ 2C)," ,e:, pfe~5a~e:,,~trI0 'ton" ~],,,33 x U)·:e: 'Nlm:2:).]

II

'I Jlor ifl!. Un pl.an~

N'QI,tI;e ",2
i(l:z,

For

€,21~))pt.an,e "F,o,:r '(l'QiO) p1.a 1l€'

3~OOI

l~25
~'95

1. .'6(;

1.,,~'OI 1,.'15

1 ~,30
'il ~
A.fiIl .. ~

0°2 H,2S -

1~15
1..0 0
1

~,~:!,'iIi... 1t;!~~U

't:i'n-aetual ,---",--:-: -'---:-.-::-,'--, ,,- )~~u: ,-,-,--,0.'. ..1 I!I!.o~!Il.'i~~, mU;:;r05COpe ,ure b"j,,-,,'L.l-y ~~~,!O,iU. oompouDd lenses, for si:m,pHci.ty ~,h.e,are shown, :in. fig,lIre: 21'",:2; simple ~thin as
t--h,a
_,~,~IW

':-'Ib' .';~~,i;~IIa. ~,--,~ O~J~-~!!!,I,~""" ,~Fliu,

~'---::_ul' V Ot _,~I ar'' ,A,,"I

,__

i'!'ftiFTr'diofii-.' ... ",,"ViIi,,1

~~i!'I'~i!i!~,., _~iII.II~,;J __

.' ,, d 'II;;, 1 ,of"" :mtCFO$OOpe U~;8 :prO~_llC~,oi r- tne ~ ... ,~ ~~,era~, magmncenon the angular'

enl areed 'F~~'~ ~~~p,~ W~l',~:L 'ij,~ ~"', ,U,,.,u ,~~ ami:ned by the eenlar, U1Jt~ .overaU mlllllific~l'tion ,M :in. the co'm"poun.d
;S':i'n.,..~,the o-',kJ'r~t~'~JI'Si' "i"o-i ,I~ IiIlliII!,,",""" , , 'Ii<oU,_'!i..-'Iio;o 1,1I!''''''' 'Hffil~IIi:aly~,1!,11~I!!o,PJI!""'~_ .lP_ rms ,

g'nl
iI!L

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U,1iC!,,",'

,1II~1l

U.iI,"""'Q'IF

~'-¥~

"fi --'t"" ..'. up' 'T-b'1'iIi'~ ,u=a!l;,~Ol1i , Jl U\ru'., U 1Iila4'>; for manv ·~,radica.'~vstems-" the, stud'? of 'w,ear ood .adh~fL,,-, ofsurfaces em ,1'-, -- - - --- s~~- ----~- - - ,iI C5~on be 'V~fY' effecdv1ety carried 'O,'Ul~ within. the' r,a~s:e of :mqnifi,ea't:~on:s p:r1o'vid,ed by the otrdinary (),:ptica~ miemseepe. The' opfcaJ mieroseepe has a Umnadon in thatit docs not h,;3i,ve a great depth of focus; as, a conse.q uenee :many tribtllolh:~a~,surfaces {e""g wear ~ surfaces) and the 'topo,pa:phy of' wear cansot be ~o~~aUy' seen. A, further lim~ta~ion, of the ordmar:y -Qlpt leal, miereseope is the resohnlenllmlr, which is about :2-000 fUlgstro1m:s:; this means thaJt fe~am:ures oonulin,ed, in a surface Of' on a surfalOO th,at are: ;sJma]~,ler- than dlis dimension are net revealed by the or ..
if.A !LV 'IIi ~ - ---=,~ --= ---=-- , t, tl

u;A,g, ~ 'W,·'t'h, 01, '.,,- -~ ,-,' , 0,'. t,L,A o'L-j" ,1~~L.l.V \10 m,~nl - ~'I r:c T ~,'Ij"!I,,, '. ,I, u. Imm'l!oil'gLD:,g, ,,'-..U'V .,IIU'_ ~M ~ \01'" - 'AD'

Ma ()If th It oeular, The ,ord~na~ryoptical microscope is, an extrmD:et'y usefu'l '~ool i,n tTlbolasical studi,es,. It can promapdficatio'Q

'M '0'f" t~~eoojeenve ,art:, d_,',~ 'iL, bieeti

Flgure :2,~:1:no,w5tbat the ordinary microscope consists of' nothing more s 'tkM two. lenses: an. ocular (or' e-ye~pi,eoe) and an obj,ecU:Ye'O' The' sim,:p,l,es1t. form Q:f lin oip~dcall'ld,c,rosoope is p:roba,b~:~' toolmaker's microscooe ('fl'Q:~2""3')1,, lobe ," r-I

dlnary opd,cal mj,ao.soope",

,An ocu~~3!r land an. obj ective are mounted bl a, tube, The' : igbt source to'

[;1.'

l~~

'!J

e-

ooera _. ~ v~'¥~ .
II.

is n~th-:'l"n-mrm .!'t ~'ItiI', 'Il'Q:. ,0-, '~l"Q,'L,o,j as '1·"!J!IldlCll'll;~'Bd- bv 'Ii'bl rn .~;I[L' 'arrO'Wi in 'ngnre 2.-3~,The :I~b.t is 'incident, 0I1l a surfa.te ,jUist be'~eanl tile' eb' jietUve~ The '~ypi,cal toolmaker "8 m:i,c:ro~soope C3Lft, m,lani'fy a surface abol'Ut, - -"-.
':(-'Ift];iI1'-~,"-ii' , , . ~,~;rnl,?I('1~I'!i)~ I1,JLIl .... 1;1Iii!'.IJ UF'-~~'~llt'~
~ ,~~ ~

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In addidon, to using the o,pUca] microscope ~.O examine topogr,aphy of ,mUd surface a.-Inormal incidence to the surfaee, miereseope ~UIS been y,el'!{effeedve~y used, to, examin,e surfaces 'Uo:o by 't.uiin;, ,a, 'taper s:ecdon:i:ns u}cih'ni,qne to :magnif-,

'j 1 00times.
'., c.

in cross, seedJ..C! surface

the surface the !OprUca~,

- - d~j~1 CO,g1 p:i;;;::::.!Iitil

23

'face to bring out gr.a'in beundaries, which. are: gener:aUy bigh -en,ei£~!y sites, the. acid p,r,et~el<jeflt,iaUy reacts with. those :bigh-en!ergy' 's:iJ~,es., more r,ap~dly' OUUl it react s ytit h other re,g:ion:s o f the solid surface, such as, ~:he!Surface 0" the
Qi'liiIJI'l'H ~_!M, 111~,I!1

Dj,sIQ;cation8 are sur face defects which, exlst hI ,aU rea] solids ,; In tri bological systems it, i.s,treq uent ly desirable '(Oi kn(),. t he' amount of defer .. , marion that has taken place in a luUd surface ~'Etcb ,pluirng used in conjun,c-' UO'D wit h ,opUeal m:icrosoop:y "can, brill;S out thedislocation sites on a, sol id SUJ'fa.ce. and reflect it change in dis~ocation behavior i,n the solid;; Dis~oca,dons are 'nne def eets '~nthe solid and they are sites on. the surface of higher ,e:Il,ergysta~e,. Thus, they interact or 'react more rapid'~y with certain chemical agents than do the bulk grain. surfaces. As a result, pi.ts or cavitles are formed ion, the, solid surface at tb,e' dis,iocat'i,on sites:; exam.inlna;: a solid sur-

face carefu Uy with dislocation 'etch piUlng can give information ,about dis;~o;cat: act i.'v:i[ on the soUd surface. won y It is possible to ,e:ah1 some' j,tI1sisb.-tinto the not al concentration of d~:slocar dons i.n a, matler],al:f:rom the concestration of dlslo cat.ion s in a particular area of the saUdI surface" Disloc::alt,oiJ:l m,o'Yern,eot en the, 'sQlld surface can also be fOII~,()wed and, furthermore, tbe e,-tfecl.s of defo,-rmatjon, of tbe solid ean be seen by 'e;xa;mlni ng the disleeatlon structures ~ fjgure 2-10 ,sluJw,s a, s~nlle crysta't (00 1) 'sut'fllce,o,f li,thiom 'nuo,tide' ,ou "ihich ,8 :S8'pp:bir-e ban 'was, dropped, The point of contact between the sa,ppilire baU and the lidl lam
DUioride surface Is in the center of the photomicrograpa. The small squares thraugbout 'Ihe enti re p'not!l}micrO,BJ3'pb are dis;i,oCIJt lon etch pits breugln about, by' eu-:hing' t,he' lithium, :nuo:ride surface w~'lh,an etch pilt reagent, The

saUd surface odenUldo:ns ~ft ;8, ,re;lativel,,' C1ude ,fashion, on the surfaces, of solids ~:ParUculaJ'ly w:ith sing],,€: erystil:s!1! the va;r:~Olus orienut,dons, on the solid surface C1U1 be determined tO SOIUle extent by' sim:p1y oxiwzing 'U) ,a, iimit[oo desree the metal ,S;'U.1"_fao. e :in. ,In oxidiziili envk o~men~ ,and. th.en I~Aamini~I~: " ~- ~ --- .~- .. --~ -~~, .- ~!fl_ ~'eI~ ~. . - ~- ~- _. - _.- . .-- - - _. . .. - . , _. . - ~- ~ - - ~ , the' surface in the optical microscepe. 'On [a,:s;ing,'ie Cfyst,al metal surface, for f1t,(i;m~:·p·~,'Ii9i ~'lbl;till 1Lr:~,i)',"' atomic ". 'd['AflCl,j;J~'V p'·IJR..L"'~ !t' '('i e J1!!i;na j,1l..,n; ~nw surface JI~,. IUl~ ~I;~J_~ll;~J a~u ~ -_~II~ energy planes) oxidize at a m,uth slower rate than do the low ,atomic densi'ny, h:~ghsurface ,energy planes, This is, because' the' b:ig'hatomlc den;si'ty ~ low' 8Ul"face [en~rIY surfaces are more stable and mor.f resistant 1:0 :i.nter.acdonwith
I

for den W1h . - - . .. - - - de~ecf:io~n- is nresented ou ]:"n a a"IJt"!itmi;illi;iii'!iI.A,~:'!if I·h~.· '!o.:,jj:lA,It""Il'liO.'f., dislocanon ~ - ~ - - - - !'f:'i' ,It'" iv'- """QI!!ioIJI~1i it" l""-"JI,dJt~A ,~a. There are many' di,ff,erent. materials list.ed. therefn wh ich tall be used for etch .. tng various surfaces '~:nc~udinl,metals, non:m,et,als~, and semkonductors, i ". '~', .. ,··f· eenve iii", .. :111 ,;r;. ,'. T-~,~",",d~ 10,1'"\1 I' .h.I~ rmcroscepe '.' is M very: e ··fO: ~ '", ~OO,I ror e~n.nrung tb,ne [or"mar J 11· te' .,~. . .... , .. ,'.'
=.... In, _._IUI ltV [, ,
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. ,g~~

,j:~IA'

fashion" Those areas, wihich have low [alond.~ densities, and high surface .. ~ ,. 'L,'. It" ..AI '~" ,'~ energ~,es CD ntaul re Ianve y bdc:~ O](!iue~ an d thcseareas ecataini relatl,v[e~y :_' JOseareas oo'ntmnllig, u h:igh atomic density ~~,owsurface ener.gy'pla'nes, have a, 'N~r'ydlin. oxide .laJ,er'~ With. cont rol cd o:x,idalio,s. of rhe solid snrface and 'wiHl ~u.fonn;l!u.ons;u.ch . ~,_r a, . -,"'I· ~l"(-., 'v';d"'~'iIf!io'" '.' q ,IS 'the ·t' ava~,I,ai,ll}lesn 'itt', b . h~1 '. ki ,a.n,d H·., . ,r..,U c'.ascews ,1 '.. "O'J"AUIS . .r'e 'r', 8') on [o~ .iQd ....n~ "it ts possible to ,Ia'~n some in fo.rm,i,tion as to tbe' re]adv[e thickness [o,r rhe oxides in these 'various areas 'by a, color Icompa;l'iso-n~,:Pigurc' 2i1"13 is a, s:tlefeOiraplh'~c pnljection of' a, si:ns~,lecrysta~ surface :showbi,g some of the o.rien.tationSJ~ the hieh ~xiidJBlt· 'IV, 3 ulu..g,on~~, :""1·~-O··. i..~'~':"'"'h~,'~ftD indicates ~, '!;"or _ [~~; ,u.!!,"'~,,b~, .l!u,Lh QWU,.~ some of the ~_~ .... ., Ii. , ',,",,' areas 0".. 'r~ ,U,,;iISJ;" v '. ~_:t~~[n .d t hose of' m,'l:Jch lower oxidation;o The slereoyapbic ph')t ]in ftguf.'e 2~13 is for :8, copper gi:nB~c [c]",'sta~surface (ref ~ 9,)., Sinoe co'pper. 'is a face-centered -eubic .' ;1;,"'] ,~ l,iw, ~,S antu;~pa;".. mel!>[aJ. 'f ,'" '.' ""':"·'[:n"'ed~·lj'lh.·t· f:~I. unt1 elane •. (··t·,ch~I·~··' a.r~ '~,lh"",e 'h'~·,:mr';;'~':'II·:··C: !!.. , ill· ~u,e !., .I, p, an.es ..". ,~e ,," ,"," Iii' : . :Ii.!].I! ad) _111C de~nrdt:y", 5!ur:fl.-de lenergy planes) would, eont am the least amount of oxide ~o'W on th~b" solid surrace. Ineonrlrmatlea, these are reprclen£,ed in fi,gor,e 2,.,l3 IS, the Ic'~ear(~t,arUk,e) r-egions;" four areas ~nlr,rounding, the eentral portion of the' figure a'l the (00:1,') location The' regions 10:£ malimuiil oxidation ',,',ould occur' on. the '[O~ and {lIO]: iareas", These' are the cross.. atched areas in figure 1..l 3~ There Ire four such h areas located in and around tbe cent ral point (l,r tbe (001) surface,. LTh.ey an! ,~;tildicah~d s,irregular djlfullond -shaped regions Of pa!t,cheS'4' In ,addit,ioD", there a are somewhat trians.ublT reg,ions :neM the :periphery In four areas, The lOX,· ,"....:1"',. :', -. ,-"q- o,~ t,ue 1('"00"'.'-·1'1 )" •. " - ,fti: ~ ["." "1,..,, ,': ' i "), " '". ,mewiiaJl ,iy,a,tlon \',.'",!IJ> sur,l,a,ee:~~l1e cen.traa regiOI.!, 0 ·f: 't,:L 'f',. i '. '(a s .... . __ one JJ~gure_, ~O._,__ clover leaf pattern) w'tlu]d, be :~lruerm,edjjat,e between Ula'~,of the f ~ :111 sur .. faees, wh ich have the leas;t: amount o f ,oxidad.oJ1.~ and the {O,',~,]:s'lu"faces;, L, ., w hisen h .. me :mlXJmUm run,:O'lIInh, 0 'f' oxiaanon Q!I1, II"IE.. ~ sur ace, nave ~lo,. ' .. ,. . -, , .. ,., . ,·...iII·~,;· me ~. rfaee A.,mlil,d··· ,.~,.",,'~,~ ,,;, " " e' ,in all' can be used ..[.0 look, at, 'the. ,orJ.,eHtf:U,ion~ ','-,'-".'~x::d·.~I~t·'io,~ bv heatins " ." v . .. ,.. . ~ --- -~ _,~ on a ,po1:ycrysullU:ne ~.urf2ice [tD 'wen ~ The h,igh :at,omic density grains,~ t.bose grai:ns, w'h:i,ch tUlve :bilh [Slto'mic: de11si~:y'and low S1!Irfiarce'ene1,IYI' oxidize much "l iii' " .' ~ "t . _. lnore ,9,'('Pi".'Y t ,"an tl h~O~ gJRllFlS h ~ l' _~a,v,lnl[ _ow :aCjom~c d'ens~ ,'y an d':.[I, h'~h' 8ur,f-:'"ave ,~B" -~~. · '. " '. 'yo '&"Jf" energ, Th' u lI..w"Ji"", '~'ur' 'f:i'JIJ,t'!~, ,0' ,f;' il(h·· e' ir'ilif\J ,;:.""'" l"v¢' Iii' go' 11"'In,JiD,'~n"';;.,1 'W:'IIl:-iil'!!i'I O'!M'~d·'~'~.:!Id'- ' m" I~", .u,""''W',... It., ," It-o .... I~lQ!, u.... ,ioU ",~:Ii'lir~~ ,o!i1!!.~" ,w;.~ .. ," wleU -alPpear to be s:PQU,ed or p:H[cby as ,I; rJeSiul! «l;t t.be variadonJ, bl. ori,enta ... It,i,O'D ~he :soUd sur[aoe:; Ulle v,Ubltion and thickn e9s of dle olxide' 'On the 'in...I,~ '"',A ~I '. ~ ' T'h" teCmci:n:~,qi[~e ajr:i~ useu, :~,or exa'm~:n[D,g r UJti:Vbj,'Ua~ graIlls I'S i' 'h ,~~,eter"nIUltn:t,.,,J~11S ·c d , c 'k........1 ~ the amou:n:t Itlf t1elluring tha't has occur,red 00 a micUtl ~utface as a, mu:lt 10"
i

~,W ~~

,a1ji''V';J'oi''iiilit'iiom'~H'f,
~..I,l _!Il, V.'III,III, - ~llllllI:.lI'

MJ)

A[,",

"!al ~

..... onseouence ~v" .~·rw.-~I~

,.

~e¥11

~'t..IJ!Ii' 11"IJ~

~"

snrface
Jj;.

;;"ji.V'l··~~i!lJ',ji,~ v.a, g'JlL ....lk'-

';'D' A.' ·p··iIlIJlt"..!;ii.I~ ~ III., A-!ll'\r."IIJl,Il;j.1

,iIl,_

''C,

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'(""

I~

. ',"

,~~irni;~,;~

.,~,-~,~

~io';1I

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OJ

.'~I'

"Iii

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I'

1_ ',,'

'it

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.',.;-,',

.-

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...

~,"".' i,

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.'

' ' .'

',"1":

II'

:",

."

i,

",II;iL;1lI';j<

if'

t'~'1iil!!

,,;;1',.,'

;,"L..

,,;:IV

'!.]o

\]I'

on-

1:,;,"

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'.

l,W

broad based hills with an.g~esof ~n.c·nnati()ns, from the base line of' 'time' soUd surface of a'n~n,)lim.'el."; 1,S .•, The real surface' then can be. reeresented 'g' ,r'Y' 4 ,rl~ more corretd.:y' 'by' a. series of bumps on Ulif: surface as, opposed to adjiacent spikes.

nique' to measure tbe profile: of !o,~[dsurfaces, Far eD.m:ple~ the .Slty:~.us has a ,radius ,and dUB * for very sbar.,p'surfaces" :i.t is very difficult to :foLo,w'Ih,etrue surface :1)110,611£,., As a ,co,nsequenec. some :mQdifieatioos for the c~:i'lte:neeof
,f'.... -I -~ . !-

There are some inh.erent :limitadons, in using the' mechaniea] s ·,Ius teeh-

'-;,.-';h" me s~,y;1'- .ecln~qJJl'e m '.us.t, 1Ilo.;ii;, ,~--. - --'. -, PO,f,lii,--4I lll1 ,ILOJJII:Q'WU1,g ,r,.1io.- ,~, - -- - - - 'ilii'--b' y 0,-f'us t - ~ - "'--,--- .-.-. -. --. - '1lI'G meor --. -, .t~U ,~,-- .Il!~ 1il- -,~",-. ~,uC 1t,00polr~,p -,~IryoJ' f'.·.'o~h:Sltu'"faecs (,'C'onJtainin:-;-ver-;}' ,ir,[rtl-'ubu sur,face' sni,tcs or- ~aks):'"- An, - D -S-- -. -- -- . - .....---- - ---g, w --- -I ----- - -- - - .. - ,t"'- - -. - . ,!t"'--- - - . . - -example of :s,uc;h surface: Rlilht be a ,pindins wheel. or ,WI abr,uh.re 'paper ~ a, The pro:fUe:of' that. snrface l$ vIer,. irregular and would, be vter),' .tfilcult to, foUow 'with a ,oonv"liltionaJl ,1lf'io:fU.om.eter., Tec:hniq.ues, have been deveioped"

howe:ver ~ for ,chan:u:terlzinj suclh ab,aSlive surfaces using: a, pl,t)ifUe mea ... sur.lQg systJeDl coupled with a. oom:pu.ter,. In one 'such schem,e the tny:~-us 'o'5cUla'tel while the :s!u:rface: 'be[ow moves, i'o'crem,entaUy :10 that tile :sur'face is ii:!'ta"'u~,,ry-- ~ .. :J 'w'h---,~ ''''~Ie,~IIO,i:r ~ VD10U v _ __en~onll!~l1.~ _A ~~ U~""'" _ , :O-:jfil-t,ik, st}a'~'u-t!:~.!!g C!u--~a~ 'ii'A<~i_'"O.'n. it. ~ __ Jk_ "'"""',~~~d r __~ """ oo,n'tJoU~d'13,' I. digital ,oomputer,~,M:eatn~[fe.meRts. of slII:face' ,e:~.eva'Uon are nhe
~!L.. ·'~_i-~it,'illillf'f ....
-

U'~.

!C!~.~I'I'fI'~,,_,
-

U'I.[I,I

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j!i~,~

,!fliIIfii',~

luI"" -_.v

characterisdcs· .,e computed ~Emm.p~es of the

-I~i-',~I",-· D

'·'~!n:ut-. to 'j~,e" IW.U

"'_~I:m.-,!< Iil:_fI A"ij" II:' "'""U ~lYij~-iJ!

'~Oi"!o,:~' IA~n~lt'i!\!i'~, 1"'" ..... !I!'v~, ~ ~I

ro,',~tc!~~8:

'W'!!io--g!!;J'.I:IJ;J,c,

,~T!il~ 1!iU,,!IiI

uunn~ ,a:re

--p[1cse,1li[·-,A "'- ,i"::".".'Cu, ln, ,11:g'Ure ",,- .. u..

"-'Jr:.:

~1:t.s."····.~l-'~ ~tS ir-- ',IL11'Ure '" - 1U are, ,0,,-,, ji, ~U;. prOI,~' .liIl ~,."

:t,yP=t

0:£0 profUc' tbat

t,:'Jill:,e.: 'v'''!.Ii'~,o··.·.·liS sur:r.-IOi e if-' ..... ~,-I. _ _ _ ~,..,

,,_1J~:,--,,'_'['

caD,

'be

'U' lL~..:._~' f avorable ~v..__'ell !l"..n,1I'iIi f.! ~'O:-:'li~~4<iLi'''''''''' n"d1dlf 11It' _lU,_i~ con ._,~_~vllii~'~~~.' ,t)uan.tliu.lJti'v~ :inlor,ml.tio,f}, 'O.Elradio tracer speeles may' be 0btain,ed., The advantage of :anto'fadi.Il),lraph'y is that a 'piclHlre is ,obtained O''! the dbitrlbudo,n ,olf the radioactive species on the solid !surface; thus ~it, Is s, par .. tie u],ul:y usefu:~method for surface analysis"., ,A'Ill!~~of,adirO,Srap:hy is 'Y~Y' sim,pLe in, ,D rinci,pa1., Ho'wever t! as will. 'be discUlIOO~, ~~he' Ijoob:nO~,OI:Y' tends more to be :fJjJ1, art with ldgbly specialized em ll~sion,~ and dart, room :teclUldq,llles,~ Jn prlnO .,,~~ 1ii!!Afi'!i;]':n [n~ Ht ~,~,,;,:~,g, "It' '.,._.1 .·_._IIJPU"'~"I!··' e iI·'r'U\Q~, ~1J~1Ii 1!~'Y!gjJ11~~JI~,~"~'I~ ItlllJIi:f,C'o-"'rmI18' Ij"~n"
'._.,1jJ~,:_

1 _

:.·'f·!lf~·"·~'"

ci,p'al~ the: technique' is shown sche:m2dca~ly in riguIe ,2.."j R 'wbere a Fadi~oft.c,,,, It",y'~su:m,iP . il~ ~·.l,e' -~h'-: tlODr--;8~;"'i,"" _1~.1_"" ,_",IUrouCi~ht :~'nt·,-:"uimate e l-:ont-9n:t' with a P,--O--,e-'--,f"'U'-iliP, emulslon, ' _·_, ~J~"" 0 '~m' C_, __ __ , 1 ,~;::~ l __ OIUZID:g : Du -'F- __ ien _ ~_ _ '£'!f:"le _ ___ _~.L The' i~.'n-',radj-'~':Ion;s, in. l- he, sneci me_ :intef,~..,t,'wii~h bremide salls in the em:01-sio:o,~ ,bl, the presence of a de.veloping alent the aenvated sires catal,:y~e the loom,p,l,d[econversion 'Qf the s:Uver 'bromide cry8~.als to metallic silver. 'U' -- - - - d s ~I b --- ~d- [cry.sta ·s,are ·dlS;SO ,ve;_,ouIt o·f: I· h-.. ,emUL': ,on. 'il.. biB._' - ---- -,1-' T-' - - . , .. 'ne.XjlOlSe: rSIpj.'ver._,fo:nue L~ .,Ie' ..-----"Isi· - OIl' be develo,per '. The eOltire: teC!h'n~lqu.e' depen,ds '00, ,an ef'f:ici,e,nt. :in~~r,act,ioobet'w,een.
~1Ilii'~I c~ .~,-

._I!l;._.

-Iii..'I",_,

, __

.C-

l,

d"

--

'! :

t:h1eionization rad.lation and the ,pbot011 apbi4C' [cJDu18lon",

.....~,

"-QdISSi

:sdlilue

n.l

'IUr5Wn
t1/d:ut(JNdlolNl'hy.,

FitUN' ,2-"l8:, ~ SclJem.fl,rk "~f,Wtin,' l~h:i,ut

The type~,oj' radiatio[:n (a1pba:~ betat ,Iam.ma" etc .) lUll a" :pr[o~o'und ef:fect OIn, both the nature an,d ciar.Hy or 'the [autora,ai,op'8pl1" as, well as the, t,cchni-q.ue used 'to- obtain, the best exposure, There :i$, [gener,aUy,I co[m.ptomise between resohnlon and expo~uJre time. 'UnfOinu.nate]Yt the two Cr1iteria u'c mutnil.ny' 'exclusiv[e fO,f any giv,eo. radiajsotope since luge If,am lemulsions, are required to 'minJmlz'e exporulic times, whU'e '¥ef)" fine Inun em.ulsilllDS, are nl'oessary to obtain .'m",~_~_,. '1~lm~' _ ~VI '__"'JIU~~, Il V.;,~U~:- al11 8.'U- ,tt'\ii:'adi~Df-'-!i'li1fl'L', are~ ~ ~~1Iv made ~ from ~11J.i·l.I. _ 1~''!iI!'~m-' , r~iCl~'lu't';:ii"liIl" _~,.. __ __ ;au~ ~ ~~ -~ .v'Ci ~~~ __ ~ _ 1!.., "c '. ·'·,-t'lIng;, ,,(a.\U,DrwOilo"Ope!" ~:- ne ~'-,.-'-', 0 _ r~o:uo~opes, m S~,.,uy!ns ,;- Wl~ ...., ....d,:" ~,-.-- T' --, -",- '-, :I;, , ,.,,:II~' A-,,~,--~" - ~...:i..... neta eIn1.lt. use a" '~lar,i,eiy'of ,filet'wn, ,aDd. 'weu prob]ems, has beell conduc~ed by 'C1oilen, [(ref ..
,-:,,"1.' ,-'--~",;ii" '-'. ,~.: -,;., -I t

.2J.)~ Sh~H:eboth. friction and w,ear :bl}volve'tb,e rubbing of surfaces 'in, ,scUd... state conJtKt. it is D, p8:rUcularl.:y fenUe area fio'f'the use of r,ad1iol80tIOpes m itlUl[o'radiolr[apby'~ BurweU ,ud 'SltfaR;S, (n~~f.~, as 'wcd~ as 'Mercbant and 22)11' E-ru:st (I",ef'~ :23,)~:reoogmzed tbe 'URfulness, of t:bese techni,lques En fFict~on ad wear wort in. the very earl:y' 1950",8, and ef:fecti,ve"ly 'u.sedJtbe same :in studying:

s.urfaees~

'X.Rray Teehni.'qB,M[
,faee' tens;idve'~,s;iBt!ethey' penetrate the surface lay1eJs and move into the bw~k
In. general, X... techniques or met,h,ods, U~' nof. t;'boUlh.t r8,y
rOlF'

as be~Dgsur-

.- c,

specimen S in a, rough' ,J coUJJma1ed X,-ray 'beam R, so that II set of' t-----J p,', ]anes 1_ ,-, the n"li'Onpf B1aO'O' an-Ie fer dltfracdom;o The dirf:fac~ ~bld ,,',' nates - F~ ,!It ....iC), ---, --- -, tion image is recorded om a hi,I'h-:resolodon~ :fme,..rai'll,ed phOi:o,lf,apl'dc :plate !lei th i' '" ,'iL. '~dl ",;~ '" ',' " ,,'jit.,;I .... ' Iii,L" it, ,'-'~ '," " ,t,r ,iI;" ,II.I.:11,U,Cl_ ' 3'B: esose ,U Po SSl u.u;: La,tne speclm,m W~",L,'11Ii1~ 111ILewe:pdD,11tb'e,m__ ,b~u,O,IlIIl, '. ,'" - ~d-- - ---t 'b- -, - - - '"," R" • &1 eneam
",~l' 'O,
I
:::'

no ding;1 the
'J' , ' ,_: ,I

-,

source '0 f excit i:nl :radiatioll ava:Uab:~e ~Since 'the Un,e' width 0:( ,X~r.a'Yemission is propo,rUoioal to atom:ic' num bel ti' tOle ligbtes,t 'j!,nemt:lnt,s 'with 'w,~Il.de:fil,oo in . tease ,radiadom are 'the most dlf}s,iraJbl,e:sources and the most frequent~y u~d., ,A~U1QuDh""""",t"y' - a"nd - .roi'r''i'ofi(-m: eoeeer ainm W~;-~ used '~I~;~'f,IIRi-';!C'a~:II'U_ the t a·'1"0'&1',: In ," '-'~.'~ . 'C !;1!"'iltU Ui~..::!Il!j,ur!l!_ U"':!i' !J.U"" .r,e;,,,",'s ~.- m,o~1Il, I!COmmOR we today are al:um:i.num 0,' :magnes:i:um wb,h, ,K alpha, .lin.es at ~486,. 6 ,and ' 2S3 ~6 electron vohs", res,pectii;v\f!ly,~ A 'variety' o,f sampi,e' :soHd.surfaces Ic'an be 'e~amlned 'wi:lh XPS" One ,o:fthe r~qiUirernenlt.s, however, is that tbe slnn.,pl,e 'be in, a, ,cbamber :ma10ta'ined at a pressere of a.:ppro,x.im.Jely U)4J tor" or less, Dif:ferent,ial pum:piing tech~,';;n'lue'~~ 'h- 0-;WiBt.!'AI"'I I 10.""" '-U,.,.... . ·m·'Fll~'" 1l1~a~ li:lIn:ll"'d' l1C _ ~ A 'toe stu Av !t'ke ~iUJ! IO'u',_J.' , ~ur faces", I.D ad,dhi,olll* cryo!,enicaUy 'OOO'lIed] surfaces can be' used 'no condense
"",,!1!Ui Il10.''_
",fil;,r_.

'-.i!I!:"'1l_- ".4JJ:iI'

'I

' __

:~'''''~1

I~~IJ,

o!'"l~l"

[t,'d

Ii!ii'~ ~~iII'!I"'" I,,~.i, _. e.~~~'VI~

g.,.

t!,~

iU~Il,

i"iIiii'i

i!ll __ ~ l~

~ 1vo -au~1 matenars e

~l

tee h'", n:~n'Ueis that the material bel.np"examlned must not be a,dveJ"seJvaf:fec~ed or be' :s,ubject '~O deoompofsi'nion 'by the X,... beam impinging, ;o.n the solid. sur:ray face. If it: is,. the ,chemistry' can 'be ,chaos,ed 'by' t.he ana!:yt:'"cal ;too: it:se]f, .. :XPS is, a ver't1I-=-_nsl"t~:,¥ Ie.t"ii):tiilk'n~:nlll~' ~I!iij[U 1Ii1 'Yi~pv''''''mi'l,U ~moultn ts 0_ S~~~PI -:Ii :-::~:-:iilIil't;'il'i,-~~W,le _e 11\1 =, ~:;,u;__l~ _.I!!P ~,n"'b'Ii·.-"" C;",), ~ '5IL '~y:picaUy 0:( the order o:f 10'" g.f,am" fOT' 'me.asur,t:meDlt,s,~ Specu'a have been ob..amee ,'m. ,s~mp,IJl~S 'smau as, IIO·····~· tQ:~:..' "d- : - ,~, .. .'1.,· , as . .1I1,~ ,-- Iram~ B"'"'''''' '- .. . .' ..1 "~I _·t' '.--.' ",I . seeanse t'b'"ie ~Jec,u;.;u. eieetrons , d 0 :-'-'
1:'

lor

'. '" ,tXa'MIDaU.Qn, '·.J:ne 1;'"·" .. 0d'Wl't8lUOn

~

f" 'L.'~ ,. ~.... .. , 0'· 'l.IJllS particular

.,7-

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_-,J

r,;II

'~-'-I-I;"-

If'

1.

a,

.,"

,.

...

not, 'emera' from depdl;s, in,excess of about I 00 aRJ$~.'r!omB;,t :XPS is ,exllcme:ly wen suited 'to .s,tud, wlid surface film:s,~f. p\EU1jciU:~ady tri'i.lo,klgica] rUms~'When this pwticulu' t,edtnique is 'to be used for stud:riiq, solids [n 'the bruJ,k.,
'ttowever,. 'there: must be some assurance tha:.i, the bulk: is, representative of ,;t'L, . '.',' ,j!a'e T'"- ,m'" Id" 'lb···· ~k-' ,'," " der 'itilr- pro 6'"I,:·'In.g .' · 1.'-;, .. ,IIW" ]~ ~~\1i1 on, tne surr . C .'" ,,() ",w,g.' Y ,Ull,· c.gmpotil,l\~OID'!IJ IOn. - ep~,1IJ1i
w'L..i']lt ".rl' ,~,Bg'.· .. ' I" . -,';~·'·'-'·!·I ':',.."

(used. hl ,corduncdon wilUl XPS) Ican :pr'orvide Ico!Dsldlerab]e in.sig'hl into 'wh'etbe'f 'or not the surface :Ia}~ers com,pu'ab~e' in cormpoliJtioll to 'th,e bulk, ,are
'~~,liid'-' u~, surface
~~l
i' _~

chemi~trY' of' {h,e' n;~aJtJerial~ 11 beam sp1l!ltterin,8 ,(profilin,l) 1:10'

I~I....

,nular slit !,IO' ,a :s])he,rica] ,oonde_nsel an, elec croft, muldp]b~r'" and a oourn,!er ~ 'V,irj,ous; techniques are USiOO for reoordins; tn(t lo,ut,put'" me~.. dWb8 :mmicom ..
[j

are discussed in more detail ~, later ;in the '1I:' .... etion on i.fii"ii' ~,Il!~U _, Vol U~I. . I,_.:g, ~, u· u. beam tecbnlques (p., '17)'0 ~ '. '-"", J:;;_ .',.: "Il,t" ron -" .-,;.--",r,~gure L;...,,:]. 11, ft,I ,.'L,,-:::·_-. " '~"l·.. d'". senemane .-.laSF8m ·-··f··' :t·...,.1 X::_'-,UI,Y,-,'L;ii'-: 0, -.ne ~"_-' - p.!JJjO~OO_ecl .--. ,sP,OC.. trometer. The upper Pllnio:n of 'fil:!scltem.atic ~bowl rhe X,... ra'~'tube, which, pIDr,;rides 'the source for X..r;ays tba'~ strike dle :sa..rnple~;s;pe.cimm ~urfaoe~, 'the emitted pholoe'leetrons frOM, the swnp]e s;urfa,C<edlffl, 'pass, tbrouJh an an'~,qIV"_"it'!' ~UII,'~' ~g.J.~1.;J.! ._:_ ;I~' .
J.iIIl

or removal of
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peters,

CONlvemti,onra.1 ,1;")" recorders, [ind t,e,~et,ype~

An 'exa]nplc' of' '(hie informadon wbich can be generated 'with. the ,XPS sysnem~sshown by ,examining, the oxidation of' lead data pre Sel1t ed 'm, :[wgu-fe ." " ..41 bts 'm.·. .' , .... . - .. * ...'L"·· ~,~,~,~~·Th···· s,pec t" ora, are~O~I ~am~ -,.;II 'f'· .-' ft, ClJ.iea:n~e,V,iq)Of,iI!lC d 111 .......111,~11· aD:. 'f'or. lUllS , :-e ','. -' ',' ,~Df _, J)e~ j"Um - dl _
.10

fibn ill v.uitnlS :s!tq,es of o.xidladcrn (ref'," :(1)~,The I,pettra, reflect 'the ~D'nuen,ce ' of tbe' bin.ding ii:(Fliergy :shif' ,O'f the 4:f e~ectJo.:ns in ~ead as, an, oxide layer is fOlmlA4: on t(lI;-e',,~,-u..-,q·e,:~~·~·"['f(·iI.:IIl- !Iead ~;Q'ri?n'il~_ 'ThL e. seeetrur - i"i!'~;n..~~stte tbe ~u' , p .:!~.iliI,F,I~., '. . abscissa is for the 'ev;a,poral,tdj lead 'fUm,,. ~t.e the eleetren bmdi~ ettersy in N dectF,on, 'yo[ts :£O:f' the lewd peaks, parti,tululy the lead 4:f electrons ~,Aftc[' the s,1[rfl,e~:is e14:,pos~dto fdr' for about 4 ,seco,mds an oxide begins to f()llm,~N'otice hi ws UlJe ,A1at;tali',i' ;' \1 ,(.,Ie·, II I!lIild'_ !t--,...~A L,itj;.f. ~,I~ I' ,4 ~~" ~,a'k '~J;;"o····. a. .de;"!l<,,!",.i:ii';l:@e··: rm~', l"16J) j,IA I'~.I!-Ilg ~n ... . Il~. II~r e:V) ,at 136~ electron 'Volts~ W'it,h further a,posure to air ,.bOll't 8: :mi-n.'IJli~es~ S
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angstrcms ~or a, few microns for 'Y~ry b.iSh Vt)~Ulle,runstruments ~To ~tudY' the surfaces of so ids, there are fW'(ai :po:s~ibl,le approaches whieh lean 'be taken, In,
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bon reellea [m a,u be' made bv vacuum dep Qsi~'i a. ~00...to 1OOO~ll~Dar,o,m n,D' -tt-' ... J. _. '-'111 '_" _._.J'D' __ .
the ~nf:'!'''''''::;,i''iQ; than .•, "'iI3''P'~~U' nu 'lI!'.tiim'Q'u;;no ~It [i--v ;:-off'iI,ilin--;;;., .toill,iIf", ..... ~HD UiJII;:" lW}"-'~ ~I ~"E~: l~~ I :'~/"'l~~~ :aa.. [U';: s- V.I,· ~ ~1Ir.~JJIlJLIi~e, (,ecnnigut';, ,aD,d,'finaUy D1.i(Ulndng it, in the mlcroSioo,pe .. The ima,ge ,obtained
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'm,-"t:Ii,A,g,~fo,:, ~oA~~I.,lt"l'~~, r·· 'illifil!"I!:i,lt1t-;:~iIA . IQ,U.II!P.i·'1 .:....

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to dis'lOI:rti,ons, and ,Mb.facts that teroree. It. Fu rthermore ~ the p,'IIi"'-""I<~~:It.", -rr.'fl-- renlicanon y,~~ !LIlli. ..iIi V. ~[~ It'f!...a~,~VI..l. III" ]1 ~ ,m ,··.11..1 . he eiectron r\e!SQIIlUUQ:n. ttrUmlAt,eJ,Y- ,0 b" "tRLQlm)' e wu"h ,tl~e eleceron
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frequendy subject

from sac," a r~plica,does not rep,resen~.he surface to:PQ.lfap:hy because t

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mi mb~~ilo\Scope~~ .... is to- :p'1- - a slnt,!,~· Ie' -. iii omo t~le sur f''ace OJ!U1: '11.. ' .. b~ :mat,enrb - 'b. ,~., .. A ,seeonodl ,appro acn ate ~ terest and then to section il in dun, slices normal. '10 tha't surface ~The sa:don
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serio 'I:-~JI'" '("U·'~,iC' ,:d'-~w'T,'I!l , u...iiJ I' ~ iIlll 't- h.....

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"'.' ' '.'-'·d .' i the r ,"" .'.'-'.'., :r[U')'URi,t1,: ,f! ._'10.,," lor ooser 'V"!";'" _"a""IO.n on me U'll!~fOi8QOpei!' Iir'bg-'-I" 'li-u.~, -1':01;,"""'6, ~'-surraee lU pro, :f'-'~l-- TIIIo.", resoi'1- -,~',-J e. .' ne VU1S
-C"

be_ :ruu:1l ,ex,~I,oit~d'b1jrhis m.. _ _ _," ---l'" - _e ., t_ __ method " __ fne method ~The profile: method mas toe' ,aQdiUonw ,ad,va~ntqe of" relliev,iu-i, t:h,e sur fa-tie' to:pogr,apb,' in relatien tel the undedyins s{:r1!lcture 10:£ the ,; 'I, maler-law" An.other' ,approach wOluld, be to de,tundt a nOllco'nducting fUm OlD the: ~soUd. surface wbJ'ich one' desires to. exandne-tha:t lis del"lfisi~ a lz'y.er O'f some III . '.- .[',.'k - - 'I - - --. th- - ace and l.,~-, ~ -~, - - - r ... 1:.. -~,ii'1n, -- ~e ma enai I' use- ,8,,p0.ll.ymer en me- sur f""- -- '~IJ'_ t-'IJ,,,,,o,-ILe~Ll"o:pad~u'he 'S:~!l-J!p~:c'
. _ I ... l .• _' '_' _... .. _. . .. _

~H -~,,- ,n':t-'..... Tf'er 0.f' - t[l;.,A }~~Sf\.r "9ft''"' ean ,.1:l;~ ILIIm',,",!I-~J', WOQ,'--'w:h~,c~h lCommol:nly," referred to as the_ ero__1_ _ is, _ _ _ __ __ _ _ _ _ JO. _ Y' __
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L.-... ~ d. ancroscone .eaner seeuomna reencsuon ,.10,(bdfmUl'B'~ :mUSlne ,e:mnILIO'l'o'rl@··lD, 'r ~~, .~ ~~ ~ -~ ~.. ~~ ~ - ~ -- ,~. --~ ~-., ., 'II..
.~

from the (lilt-' Y 1 e-;,'id~ iafte_r .cullin;8 ,a th~n section---., clos~-.tO tblt! surfaee, .~,n()~tt K _ _ _ _ ___ .... __ ___ -. ------ . - - ver~ . -- -- - -_. The' ,Ioca~thlnn:ing, near the surface wo,uld enable an OblSeJV'eF to, sec: the rather' '~a.rlle areas of the snrfaee if the no'n,eo;rnductilllI1arelr' can 'be dissolved, by w,a,s'hin;s, it in a :suitable sol vent. 1'l1,\1'S~, in the u~an.smi'ssiion elea:r'o:n.
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order to ,effec1t:i:veht ,analyu surface :ta,y~r.s The :man;ner in which ,r-e,pJcaUQ'R cen be 1\t;chi,eved is, shown IchemadcaUy
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th,a~ cne d~sire5 fibn 0 f pla~dc material (r,et 32),., Arter the pi,uti,c: has set U:P'i ,~t,is stripped from 'the metal surface and backed 'with Scotch tape, 'The p~astic can then 'be

., -:"":iI:Jf, 1_ ~'_2~(':illI,',)'" ~~, mi ~ t surfa ee ,!Io:h'- e sn r,- I!iIi'if'!e' :f~-' a:... w~~"¥ to e.uminc' in the micreseepe. The snrfaee is, eoated 'with a
~

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coated by' depolsili,on

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of' a fUnl of ~u'bon; the fmaJ carbon f\epHca, is; ,a.v,~Ua'ble l(fi,I., 2-26(d») ,I,ftt,er removing ~.hepi~as;ticb~,.wuh:ins: whh. a, s:ui~able
The carbon l~,~ ~ _.rill)
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the transmission i, ,:~, -t '.. I,Bl'n !,(lime 'tUMI'"n' ' t mto - t ;'e 'sur 'f':'ace '5U;U-iJj[~,~ 'F.. '. - t'h- ' . - - -.et --- ·,-re'" 1 e:ecrron ml'CI'OrsCQ:p,e UJ nu.el1tl'~' a, U:D'htelr' d,e'l"losh of ,a, shadD'w,im~'iuetal ~s ann :ied. dur:ind" eva,~r,a, .. ""1- ',,lI" "~, -1"'!PI"" - - - ~,,11:<"''''' '~'o'n" .::-.,- --jl-- ...... '(n - b.I,Ifi;,U,,,,,~i!:.CU '~'n' f~ .,",,-..:;.-, ("d' ','.,. ~'n '!I...'l"~'Ii1!O!' '~'Ib- out- 'b· e~'t'ali" rlDilii'i 'llu''''l· o"'i;D' ~ 4,~,A,~ 1If--4i ~.. .. ~~'" iD" ' ' I16' -)1) "v. .... v', ., d _::,_ 00,_' ' .,",s 0:£ Smlrfa,iC'e' tOPGlra.:pbic;r:d, ,chU;f;acten:sdcs; ~
,r;'~ml ,!""!f.Irn. '[-,11,~j,iII, IU~ ,DY~'m'" ~'Hla)li ·)J~rD$'I'.~'V' ';:1i'jIi ,W,I,I· ,,~~~,~, . !l,.'cilIiit'iiJ ~~~ ~IJj~U. U:I_ ~,~~,~, ~~~
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Tbe' n!qu,iren,en.t of' eiJ~her ,section t.hinniul 01" l'\e;pUcadon ,is Ule ,A!c;hUle.s beei[ of [b,e tnlmmirn;ruon electflon micfoSlCope ~ It :req,'U'ires I, vwy well deveIJO:ped. a.bUhy tCl' pra(ti,ce' the' art of' ~ecdomln,g or thi:nni~l: :sa]B:p,l/eS :for "., II ~ '~'Ii" U',a1iilsm]ss~on e,-"ect:ron 'mlcr0800PY exam:~nauo:n" v..'", --11,ermme,~ hille' repllc'a,c Iu:n; ;' 'li.on,tech.ni~que reqJd~es it gr~at Ide,lf,ee of sldU :in pre:pafinl: the r'epUcatio:l o,f the ,so' id, ~U'rrace,., It, 'i;s, frequently 'v:e,I'Y dif:fiCtdt to d'";8SOlve: Ule :piasde fllm wi'lhoU'n lca"using disllitesrad.on, or ~he carbon ,rep.ic.a. :lkf,otre th,e pJ.ud'c di:ssoh~es,iit 'e~,pl,nds and, the: stl"oJns trau;J'mit,ted t'o, the, carbon repJlca, 'am be, , dest J1U(dv s WhUe' Q, ca.re:fuUy p.repafieQ ,r-e.plica, ,should ac(urat,ely' renect
III '.

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~ptjca] orienter w'hieh. bJ:mounted on a, u·~nrSla.tiof!la] S'Ut"e. Thil SUUl:e',ilmd "t,:;:..._"~,, '"am,ii'~ "'IiEI!t> ", t~' ,';~-..,II iU, aere _"Y tin",' 'll'i'P ·Ji~ onenrer are mH:f(UlI""ller COD,rOI~~, ,1I;~h'" b' WILO'w,mBvery pl'et1:se ", ,"t:';',,~,_ ~~_~" "'f- th ':1~:'" ~- on,- th "" ,__ un~_er ''''h-- ,--.,.--',~:--:, Il!ft:un~ -Th:'-Ie: ,arm In --:; ~' ',', ,,-,~~' '., :POSiLlllIUn!,O !L_C fJuet e 'd-',~,-'k:'"~-d'~'"_- I_C ,scannIng I,:SI!!~ wmcb ~ the st:oulus;~ ~ - -- - Is maunt,[ed conralns _ two. :n,,;x~_. . _ ,.~:,fber~U~.tl;, ~rider):' - .-~..~,_ .. _ _. __ _ bands 0 _ . ';'_I _m _ __ __ ~ ,_ _.J. _ m Clopper on whi~h ~u~ain sau,l~ are ,attacbed ~ n_f n.ormal IoaW 61: is Be.., QompUshed, by aUo,wing the :magnets :mouD(cd on the o,ptica1orienter riul, to puu ~b,e'arm do'Wn'W8Jd to' t.be'disk Iu.rface~ The strain 18'.oI,e output of the load-- sen:siinlD g --- ,0 - ':8 am,'"'fi'ned~ aDd dlsnll~d on, a, di,gitM munv~Umet.~- . - ~ ~~~ -·',I.uoe !. - -.t" I L -~ ~. ~ ,iIf",,~ 0 ~ - . eT -w'hieb." with suitable cali.brad,o.n,~:p'j',orv,ides ,I djrect readiq, o:f loa-d.~ Tbe fric:'·, 'lion ferce gauge is reid out on dther a :stdp chart recorder or an
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of' t~'Jf: :SU!:M~.!\,_, ~ ~ ,and the video srlDaI lSI fK'ord~ a~o:nl 'with audio Cf}'~lUIHi~nts v'woo t:fl'J.U~'to on, ~d A,n, d' Tt.· '11 ~ d p:rOVl e u;aUl ,reOOf\,JI1I,~- ne nlpe can 'b p,w8i,ye::,: [we~ ~n, 1110'.' monon ,OJ;: ee 'II d L,_. it.-..
'tI~ ••• ~~ •
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tlaDSJen,t m nature,
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'The~ entire ,ex~[ment~~~ ~_ v,h~'Wledan the 'te'l:e\vision monitor lis: .... _~ ~~~ .. _~ __ ~ . ¥w~..__. . .
"~,:M '~,~I!;,,.,.'\l

pictwes, can. readUy be made :from, the video tape, To provJJde for anai,y;sisof the wm' track, an 'l:tu::r,g)",.,wspcr,sive X..,ra:,)!' analy;sis s,ystem ]s mount,cd. on 'b'~ C''C''M'' Th:',' anwyz,c:r , h U At'lion.·. Ch.'iiUln!;l~ ,an.." :a fesO,~UuOn. o·'f'~ 17'0'"C(lICCliron 1,~- .... '11 A ,- , ~, .. ~ I-~.-~ It e 010: '.'.' . ,,' •. e ~ -..._ .' -, ,:' volts, The' capabl1~t" o:f e~,em,eniltal Imllppiq; ls also provided in the! ,s,ystem,.,
I ~.'

wii~h '~;'nn ale, lOu ~.o 4i'n ..... -:-,tU~,It'a.tI-l'~n-~QlPn '''''8' ,'f,i~" ' '~UI, Si.,"!;,O'y ,Ilg""'!l.d~, e !t"'(f!!iOi'I.:uon,;,

t ,Id. iillIId'd~:~t"n,'iP!li, ,.ID,,",,~OP!lr'!¥ "'ifiJ 01'·,,,,,,,,, fl 1M! I ,liuu:II t- ,", - .11~hi't, ,::' .. iii"!il..',"0' -,~' 1,
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Th.e use- -of' en[IrO'y,-d~s;~~sL;e ,X..:mv ana1,~sis in.- C-00J"UDcli,on- 'wlth, the SEM _~ -, . - ~-J --,J""~~ _- V . -4' - - -" ~'~. - - -~ - -penn:i.ts t'be' d'uect elemCl11~a1anaJysis, ic)':fthe wear and frlee,ian :sU'rfaQI,M \VIeU 81 all examinmUon ,o,f'W1eaI ~ ~'bris 'F:Of eu.mp~te,- the 'wlear dJ8bris ~,~'er\ated, from varlous speci'm,eft5Jtan be' idenlifi,ed ,se,pm"i t,e1y 'by' X~ra,y teeJllniques~
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'TJie 'SE:M: is, i,dean',' ~;uhed for ,studY,me; We1l11Uitfaca and ,.,ener,a,lsurfaces in t,-opogra,philcal tribelogieal studies 'because [0r it,s grea:t ~pith of' focus ~ Thus, ~ irrqula'f' nature of a 'worn SU.f'[w;'e can be seen :in detaU 'wi~'{h he' the
_., ~- d" 'b' s, .""." ~'it' '" ~-~ ~~ ~ ~- - - '1-" ,L-e::.I'S~!UJ -I ~'JE"M" .ur;nerm,()'re',~. ,wea.r ,- e'~,ns plie-senL on t-he S:Uf,lla.ce caD, 3_,SO b~ v~'-'iiil'Iii,11[~,~ S.. , ::.. F'-t'li... observed as w,eOas, itlJ. method of attachment ~,O ~~besoUd :8urface, ' RJ--d'il~;'-"<~I'I!'--~~, s.. ~ S~'M',i are '!;:bose ~'r··,b'···.n~OQi:"~~i'3I'l _~el! Y app~ elrl';1. m "~ ~ , __ _ '!l._ L 0 CllC~ s~tem-~S where_ a hard ~'''~ ___ _ _ _~ surface ~ssUding,on. a :Feltldve~,.softer' ml'E,erilal and a ;great degflee' of pht:sU, ~:for.madOfi oecurs to the so id surface, Furthermore, where wear
I.. ,_, li'!i1 U _

na

m!Cclull:d;~ms, 'inviQ~'V'ethe gmel,aiU.on, of surface cracks Of 'Iraa,uring o,-f the' surface ~the start of the cracks and their pr~p3,BadoD" as 'well as,their nature and~eu ~!.er ~,CQn '~:",,: reacr:I~~ ....... e~ :in '~'~,:-: ~ o , character, _~" If'~~~,_ @rq,:--,d _~UJi£ :S:BM" _ The depth of fi.eld,'wi~b the 'S-EMis appa't're,nt frOi'm, the, :;:,hotomlcrO:If:aph eresented ~n, ,~,Jio·_ ~ 2 ... 'TII1,..~: p. L'!Ii"iIiI!-,nml" ierosranh 'lilt!, for '~~n- ervstal v 'tii:"ur,~ 2f!" g-'~Je' of r..~ rw~"""Jj, ~::?'!I ' "JI" 'b, t, .'111111 " . , "'" " , d'~ ~~,t;:A,· "h"" h 'I.-. .. 'h ... 'f' ,.. "d·' 'iL."
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,crystal

breakilll

b,Y' fracture of the 'molybdenum, diSH fide crys~aJUt.e8 The ~ nuttlerla~, Sh.t)iW5 a larger' ~atttoe strufUlre., Th[eee are thin sih,ee~,s,0'£ tbe lamenOie'~the basa~ planes, of the n~,ol'Ybde'flum ms,uUlde: ,try;stalU.tes 'being, tbe

.,1--" '" OCCUFfUlll InOI,Y "~:uum,'I;SU!l,Jl,b.l/e; w, ,I.e, u;8S eeen rraeture IUJ 'it;, Examination ,g,f II breken edte gf a. 'Dl'oll"bdenum d"i-$,ul,fide the Sm~1J 'iTeV~a~8t In 'the upp~r :~eft,corner t ~:he smooth lines
~",'

,edge si,tes being

,~. IW', •

'YleTY'l~hin :sec:Uo-nsl 11e:neJated 'by the- fr.aCUlre of dIe, mol:~ibdellum disulfide c.rrs~alUte'.. The' ~indivjduallam,e~Ul1ear cf}~stanites 0 f ~ ~'h'~ ,m.'"",~,u'b,,',d· , [a.H'u,m.' :..,!I':~~il["~,d'liB!"pv;~,t~!11[m-nji!!; WoQW!liL, "" " ,,;r'Q!"~,I!iIIUIl"" L'..,.l'~d'" ,~_l'!iJm,n~,;Q;: "'IIp_R~M :~~ sh~;ts .-.:rvb ~ ~ yh'r" ~"t"""_'~_~ . '.i~'If,._ :m,uc't) H:k,e:~,hoseo'b~rved ,in mica,. ,~:f visualizes that the 'bonding: bet ween these ODie
dlO,8e'
Y~,;iI!
'!!o>Ui,
'!!;,r,L

lIi!'m' - - t L, in' 0 lit ~"~:"OO'd~, '_",y,'~ :5:1 if,-,~ ... 8 iift!C!';bla. :I'-~,U ..... ~!-1!~~',_,~Ji~~'~~" ;it'!i'rn'of!"J,nh-:,L_ ~ .. ~~!!!, -_'~ ~11.'L,a,' in1l.. fit- -1~C; ~~ ..

u-'f"a!~ -

m"; ,InC!' _'ir;.. ~ DUra

,'".. ,~:j a-n..:ll 'i't'!Uiw: "n: '. ~IL'U, ,!.; a .,

.rJ .P

iIl:,~:

fi,gur~: ,Z_,]O(a)are lCH~I,and become much more di,f:'fuse Md dirfie-ul~ to :i,[oen... d:f~,. :it'h ]ncreasi:~1 amounts of strai n '. The l~dln,'alshown in :6gur.e ,2,·,30{:aJ w and the series Ulereof :in r_.,wre 2 "lO(b) 'bec-ame' s;mo'Other' with hlsh,er de,grees o:f str.ailn, and a, loss in the actual CbaJUI,eUng lines, due: to. the increase In the .. '!II"..I e d-I ., ,..:Qi '1-' iL ~~,-' '11. ; JI i _'lSCUSS:e m more 'UJG!UIL I'll Otdlp'tcr de f,o:rm£\It,"!'on 0 f' h- e SOdu surrace. Thls IS-'d~ - ',..,L, "It;" n "1" 'WhtUl awresses, use ll' .s:petlj, ~,ca~:~y wear sur f. to races ~ One' o[f the inh[et,enl, diffirClddes in the S:~M is :~:h!aJ beam 00" elec~nlins the res1J~tsin, ,M accu:muladon of electrons [on the surface;, and ,this produces a surfaee charging t:r:rec~,~ihich results in de,gradad.an of the imal,e'" 'With v metals this, is n.o~a serious pro blem because nile eleetrons I.f\C dis'llp.,ed in the conductive solid ~WIth p-ol'ym,eric materials, ,,;bleh rue fre:que,nUy of interest in tr.i,bcdogy iand ceramic materlats it becomes a dl.ffit:u~.tas:k to obt tain geed surface micro,paDlhs or channel pattems wi,tboU'i reso:rtin,g '~O ·'11" i.. ~b .. Ii' -• some ,&UU:lltiarytee;h .ruqu,@,or metnoa,AI 0 f preparj:D,B tne specu~nm surrace prior
a C~,

,..j~1

'-~

I,

i,

1[.0

pairJIt the' specimeJil surface 'vdth to cond:ucdng' type of' rUm,,; tbi~ tends [,0 dissjpa'l[e, the surface char.8~ from tbe: electron beam ,IS it build's up.. There: are schemes, however ~that can be used, 'which in.vohfle wodif:ybl,g, dl,e SEM so that fnm~ th,at do clu.lrrge can, 'be studied, direcUy~

:ins-ening,.it in the' SEM ..,A fn:quenUy- :amd, [commonly used It,ech'oiq'UJc is to

'E-eci~-OD,Mlcro:pro:be
,Mother surface tool for s,uJ.dy,ing the charaetlerisUcs, of solld surfaces that uses the' e~ectro:n beam i~the electron mieroprobe. The basic :p'rin-c;lp'i,e' 'behind the technique of the electron microprobe is- reiadv'etv sbn'plle and ~tndghtfOlrwanf,. The electron beam strikes a" sample surface and produces X:-rays 'whose' w~~l.v'eleu8ths.and energies are characterlstic of the e'lements present in the saUd, surface hI the' reldion of the bnpiltging e~ectrOllbeam. The i:nt[tllsruiUes, of these X -rays are measured and [C,@lJ]1,be compared, W~iUl the inteasities 10((X ",rays,from a pure standard of tJ1e e~,em,eFlt nd the J"'lado'D,f in,.. a teRsiJties measured on t,b.t, sample to the in.t~n:si-t,'Y'measured O'D t.he ,s,peci:m"at can be' considered as ,I, measure 0 f the 1M11i,QU[)lt 10 f th.. el,em~nt:pre.sern, in the e s{tmp~e. In, other words, a caUbr.ati.orll standard can be' used and if com.. parisen m;ade' against an. unknown, The eerrelatlon, 'howev,err'~,Is :001, ~ntiEe'~y str;Idghi~,fofw,ard~There art sev.era.~faclors 'which tend to cOI:m,pUcate' the' inU!Fpll'etation ~ Mo',s.t i:m,portatu o;f these factors is the int1.uence of' oth.er elements. present :hl the :sa'mple which MIl absorb some .of t,lile X,... ray;s generated and prod.uce' fluorescent radiadon. ,ebfu'acterisdes 10r their [ow:ml elemental properties, 'y'e! another 'factor to be considered 'is the [ef:fect '0 f dep~h of penetration of the electron beam; I.bis is, a funcUoll of the atomic DUD1,'ber of the sa.r.up]e ~ 'I. 'f'1i'1<.,;jjny' if"a,!C\Q'~ however ,..-l .... ;\];,~'-t?U, q . ... 't'';;iI>;[J;t- '1°"-"8' ... hem ';:c-c"""~ 'triln;'il'llJl'U~~", l, ""-t .. [IUD· '0" ... 'n.f"'i;,'t ~R~f""~:; I. 'liwillu..:; au! n!eeded,; simp:~e,.qualli.taUv,e!!; a.nd semi -quanti tadve IllEdys~s: are ';suf'tlci,ent." While the electron mlcroprobe is, non, stri,cd.y ,S! SI:rface 1.'00:1 as is; the A,ug;e:r ana.lyze~'~ 'wbi,cll :wsdescribed tater, it does have a :ratba unique [ea.-lure'in, that -it can 8'Dal.yz-e various s;pots,~l'n tbe :so!Udsurface and, do a, point by poj:n~ analy:s\ls of' it 8urfa,ce,. This 'raciUt,a'~e~ study of such thing~ as wear tracks the
II Ii] &1I!l,g,
..

'I

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1 u i11111J.g. I ~ ~

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,~,11' i;I! I, ii).l ,WI'" JIl,il'V'

IIlJ.:Jl

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mueh to 'hetp 'id,en.Ufy the' source o-f elements on the solid surface and how hey 'iii. L~ are com m:.,.. ..-II wn,_~ various O~:,IIJ~!er temenr 8,., ~lneU! '. h e 'Whell elements com biine on the solid surface to' form, compounds, ~here is, L ~ '. h~ lb., takes ! " 'h 'II l p 'k-' rne ~ a cnaractettsttc ,energy .5,,; ~f_' I~~-~a~'!lr P'ltlC~ in tne ,e~emen~a~eax, T~' eiecin " iiI." d~'i ,~ tron energy :ma.y sr "'if' In one di ."~ '. 'Or :anonw~er A rrecnon oepenmng on the nature h ]'~-~ ,..:I ;'d~1 'iI!",1 f" ~ ., th (}f~'h Ic-ompCfll:n(JE, ,t/' tne rormecd~ n, conssc erame amount (}', Ins,:!:!, h'~1mto 1. "e' par.. d,cldaF type of com pound iJtua~i:s formed ~ and.~also, the \fIery formation of the compound 'i~$clfcan be ]learf!J!Sd f~~,otn 'e'xam,i.nat'loln of these shi,:f'ls in an ~1.. A~ Tilne 'Use: 0'1_' me c~,em,!c:tll ,$,,,1 1:9; t:s Vle'fY e f~f" r' ~ib III.. ,;. i 'h"f" " ~ tne ~~.u.g:er pectra. '-' s :' tecnve, ror exam:p,~e,in lit ud:yin,g the oxidat ion 0 r n1leta,'1surfaees because 'I he basic m,'et.a~:peak sbifts when oxidation takes place on ~he ioHd surface, One can, also di~ninguish between adso Ii:[ktt ~on and oxidau ~on" The shi fts, indicate whe~'he~]' 'L h f ld '. f' QF not the presence or t L oXYI}e:n, Ion t_;~e S urrace '. (I, resu I" 10':f oxtdauon or 0:_ ne 18, ,m: simple a.CltH}i])t i,on 'Cha.n,g iBm: a~'. have used ~hilS tecbniq ue to study Ule oxidadlon (1"f slUcon, (ref~ ,4,-)" IF"gure 2,,3,8 presents an Auger spectra ,~,'orthe element al sllicon peak before oxi dration and a,n,eJ" slHcon. oxide is formed on the !oUd surface. The two peaks are compared I.n :fim,uf1e!2,..,3:8 OD,e can see .~ the :~' "a diffe " u ,'1 ,I erenee .HI the i.11imi,lM,YllW "f~' th e pea, ian, _'1n.~""""."-'- 0":f': ,~,iL'_~" p~a:r.. ,-~ ~.A ,-,---ak -'~"'d·" ,J ~elre 1$ Ill" ~ 0 W.Q,e '- ~ne - -,~~"" anU.; size ~ 'iii.., ", f' 'h " ", f ill 'II.. iii 'h muen tI'M:)t,t nnportant -1-'~ mere '~:S ,8, s,~d:n,. tne pcsmon O'~.' tne :pea,~.,rn tne y,~, Ul lellement al silicon, dlrc peak occurs at ,a,ppr,oxiru,a;te~'y' 1620 eleet ron 'VO-~ts 'I 1 ' f' "'dl'" "d~1 'k hif Willen tne st1"~con surtaee 011-_,l,US ~ 'ill 'h ,$1. 'wean Q-}tl' e, t'11-e pea,l, !L,Lt s ,~,ntne 'il"' down ward. no' an electron ,ener-gy of approximately 1,6, electro n 'Vo~~" ~2 s These sill its occur w-it h the formation il)f :m,an.-ycompoends, 'but usi,ng the' Ichemilcal, $h~ft to ,ga:~n basic lnformat jon Is ,~om~wh,a~ ,lS,p~ci,nc hll nat ure so that ~'w'ith some parr:icu:l.iicr compounds" there is a teLaUv,e~y marked s'-hift alruJ nbc formerlon c)'f the compound can r-eadUy be disdn.gU1,sbed 'f-rom t he ,A:u,tg,ef' peak assoeiat ed wit h Ithe e~ej'nent.aJmaterial ~\Vidl others ~however 'i' ~ he shi ft m,ary 'be on~ Y' wna.r'ginal~ so it, m~y be' very di f'ficu.lt to give poslt wve i.denU :HcQ'"
i

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t'&50

1!:,LIEC"rte'N E:INE A~

PllW'e 24] :i~a blloc:'_' diagram of an..A'uscr cyl:in.drictd mirror anal:yz'eF'. In the ,c..~Undrtcal mirror ,Wlalyrer it pri'muy beam" jus~,as 11"1, the IconvenUon,w
.J

,J\;uscr'anmysis s:ystem is directed at the solid surface 'ro:m an electron gnn, AUa.]in>o the -!Cldoclron leneciilries are 'in the vo~ta.O)It~ranee of 10001h) 3000 'YQ~ts;, -e· ';, ~ '"_ "_'---_'_ . ~. -',ee elect -'-'-{ ,8, ,n..e ·tli...·· s,peClmeu- sur'f·c ,ac:e'i1 ",ln1c;a,e' ·d··· ,'as, a, ;',,,,'k_" ,'"--; ,fi"~··" ',-, '2-A-l ,·- ,ecli,.,rons'. '-'- .., ',' "d-'~'. " t" '_ -".; Th -,ue , .... "'-;' ---,.' itS ,10, lIU,re-..,·., · '" ,. ~.. etectrons 'Il~~ G'Oit.bIt A" '~I L, ~. h' ~ h ne nlcolm'~ng UDPJnIPI~g: A1C';', ,,''U,ge,r ew,ectF.ons W', IliC:" pass, bet'ween a;n loner and ,au outer ,cynnder' thro -"lit ,Ilt mdl apertufie to an elee.. ,
'ID '.. " .. '" ..
'.1 .J_ ' ••• ~ •. '~. ,"' , ••.• ~ . ~ ',. ~.~ ' •.

·t-· ---:""111.",.

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tron mu~tJpUer ~ The signal is, then :fred into a ,~lweep,B~n,er,atoiF' and from the swu:p Iten,efl;Jto:r thro ugb, an oseiUiOS:Qope 0.1" block-in ampli fier, The J\;u:!!et (fllta, can, then. be fcd, into an oscilloscope for direct rleadi:no. of U1C'Aug'er peaiks,on the o~cnloloope(.fas1tresponse), or 'tbey can 'be fed i:nto all, X~'Y' recorder for conv eDt:ional x-:y Jlllotdng as is done wifh th.e AJDg,er system,
"'n;o"'!ij.ad·d~t",iIi!~,.It'"
m"'- I &::1-- - --e ,_:'",~- r,. ~- !I! I,HUIl:;. i 34\
l

The ad,vlnh1;ge of the c,~:ind'deei~ irror Augcr an,aly;zel1" over t:he cenvenm lionaUy used s,:ys~lemis that 1'£ ,has is \fIery fas~,response tiime,~It lean deteet the presence of all elements, e'XCCipt, h:ydrO,gM and hel~Jjm'Fg:n iii solid surface in, less than '0",.1 second. and tan m:spla,y the AUI1ef' spectra on the OS,(;iUOiC~pe.. k .... _11 ,', ,,",1 • d;,,~ '" -Ib. 'IL_ ,. dis,-'' tn·'.wdll]:C'~, e.x.perlment an._' 'can looaun,uous~,:y momter tne cnan Se.5, m 1:' 'lb.. '.' 1: ~'I 'i '"d" L . .'. surraee cuem~!i:try w,~n~e'h ,ey ta -k:e pJJliC-e ... TIII-.,'; J)r,ovr~es tne- Itb~'111"" t ~ '~ I. ,IlLS, hllt:y' .'0' re lOW' adhesive' wear~, tur exampl,le~, 'whl,C'b iIn.VO,~,Vles, t ram, fer' o-f one' ma!teri:il 'to another sl1rfaee~when the two matedals io ,~oHd~state'eeetaet Ire' of' ai"feren,t e1~mental com:pos:itienl ~ It alse ,a[loiws the sEudy of the chemistrY of In'. f d,.,i"" lub '. Ai ., teracnon 01" ,aL'lu_lU,ve~, neants, an d aesor ......,., 'WIth' tne :m'c:hlll~ ,5;UfIE: ,~U~ bates '" .. 'L. J:Ia~ in
.

Thus, the researcher can cond.uct. a dvnamic exnerhnent

,~~~.~o>

s:ueh ,u a p,Jin-<JD

,1_

Ii... " f' ~ 1.. , . ~ OIntne s-Peclmen surrace so, zor exunp,~" a,wear trac 'I~, can ik... exammee. ..J tor .... oe ,. ,1.."' 'Ii.. ~ id 'h-' L its_. C'lemUi~.ru:. '1].Ien~Wit' h 'I h'e 11i,.;".-.,", 'U,~'n-··.....JI OUtS1 e. t;- 'e wear trae 'k- " tne neam ected _. ._. '_ _ -__ '__ ' J'.,." - - - _., ,L_:" 'I... '. . ,....~ ......oJ . 'CI:m;lUJJl!str" oJj' me Vlroln, Of' BOurn b d':e~ur,~,a.oe tall 'L.,... ini:u,Y.,Zw f'OF' com·'11~6, oe : c·'.' ~
,..II
.. ~I "'_ _. .". .' .
I J, '" _ _ I ~. • _. • . J __ .~. •, ~ ",. I ,_ • _.. • ,

£lae fricUoi1, contact zone, With. (I,e'flection plates. the beam esn be den.~cted

!/l'
.

'b-

,; t, 'iI" .10-. b' "004'." ¥\i h '~, f' 1!... :panson.. B 8.uC~JJanl,Yl,YIU~tf ., :reseaJlc.J)JJelS lie ,1_Ie to i(ten1:1~'Y me ro'~e 0:' lUI}'"
.. . I . ~ . ._ I •• ~. ~_.. •_ .. " I I. _ -. _.. •... I _.. _..:_ _ _ .. _ _ _. _

bing 01" the flrJ,ctiion process in ;s;urfiaoe' cb.ellllistry';; The ~llcor,po'ra;tion of the , 111'· d" 1- A' . I ~ k ~ .. (,)",11'0.····nea _ ~.' ~'uler iUi8llYle,r ~IJil a, p.ln~:n wS·' cl:Der.ooefll :~;S SliO'WD
_A~:

'it;;"

:scbemat:icaUy in fij,Ufe 242,~ In ligun: ,2",42 :8, wcuu:m ,s,ys~emeontains a ,pin...glll dis:t or a, ,rider""on disk friction appar.a:tus", The disk is; rotated :inside tbe 'yaC.UBl chamber':!1 and the :rider in oonta,.et w~th. the disk generates a,clrcu~ar track on. the dis:k surface", A'PP'Il(lxima.tei,J i:IO from w;here the f,lder' makes COI'lUllCn, 'wii~:, the disk surface rhe primary electroD, 'beam, 0 f 'Ute Aug,eJj' ua1yz~erts dill"ect,ed 10 the 'weo contact zone ('nhe wear track,),,, 'The surface ehem bul.Y' in th,e wear track then, IC'I_D 'be; ,oolltin'Uous,~y monitored, 'whUe the lubow,g 10'f sliding process: take;,s place, Disc:oD~jnuides Of w:ffeiieilCe8 :i3JiIJ surface cb,emist:ry along rhe length 0:( the' tfliCk, can 'be
i, Q

b, ,operadm,g the 8iystem at a Vier,. silo'\\" speed, WA,en ,a Kunin! sample poslti-one.r is: 1l1sedin coojiunet.ion 'MJtb the ,Auger ,analyze.r~ the surface can 'be- :mi;lifti:fi,edand 't:be' actual pc:dH'( or zone of the @mHninat.ion can be :i,dl£ndftled ~ 'This :~sa, vay useful t'0(chniq'le in ,studybq;: 'wear surfaces in
dm;eQ,edj
~,'b.~lit I~"!~H~,

~.'ble_ 1il:i~'t"".'i'ii1 I~=~l.' ~",'U-Q.I

-

'l1;!I~1ilI1I!" '",'~gljl

tra.ck~, tham, point,

ma.u~1!!
nAa

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be m.agnified~!1 ad an. exa:mblati,~):n o,f th,at "oint C~Ui be

-

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n-b.;u~led a'.'
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~l';n:t' p~ _ul\. ·iiH' 'it'lra-'.'iii ,!.{ilililil~t.. ~ l

71

• • ~II 'h he p~rlmary electron 'k ........ .grains are UlVOlt.VC·d' , SO' l,',lat tie: nri eeam can ·~_..I.i: ee oorect.~ at a
'11

-,_ second grid (le_ncr'aUy two gr:id-s,for better re sol,u don, in AU,B1er 'w,ork) he :repe'~s the sea- tered electron s but those that are f,' e :pri:m,lry' beam The all final grid is grounded in order ~.o shie~,d, the retardlng ,grids from the high voltage and the nuo:rescen~ screen [One '-ineo views 'L~iedif'fracuofi pat\ern on the fluoresoem screen, ~~hn);ug'b w,indow and ,I ,set of three grid'S" The ,I.
i,

d '. s,amp~e' IUr'[l'8Ce l~e,.,,1 c:rySUII,I' ~U\l, Ie'xamlne·',,:r Tb·' p'r:~miary'e IecttO,n 1l... "e veam IS S aerated "from an lenerlY' soerce such as ,3 heated fULm,enr 'wi.h. ,I, cathode, and the primar.y 'beam is directed in a, 'voltag,e range' of I) to 200' 'V,al'~tsat this I f .1, ~ L;' . dv ,-,n -h ., ]"d SOJL Icryst,a. sur f"ace : rom wdic~w, :11 IS: d]"·f-'f-'.r_-J::t[eH... O tne speennen ( ...., L te. crySl.a~) side of the 'OuoresJCen- screen " wi-deb is depicted schematicaUy in "gure. 2-46" Ulere' are lit set of ,grids (shlehi ,Iri.ds,~:s,uppr\e5sor Ir~d" and another shield ,grid) ..The first gr~d Is ..rounded and ,B~ves,a, fi.e~d free region
Ii ~ (..
. 'j

re1ati'ye~y s\maU Fe,gio, or 'within one' of the gr,ains, in the po],ycrysu\Ui:ne surA Il..., ..1 ~" ~...1[ .'......... ...1[.... f'lace'~ LE~-ED'lfi:'C"A' ugter an.~ ble' ot 'h:J!f ana.~,y J,caw IO(,"'~1 u.:eSC[1~1.IJl-!I)cr,eto f-' .-~:' c,t. ~L, I'o.re', must be operated in a vaeuum s:ysE[em. The. schema'U,c a'rr,angem,ent 0 f t e s.yst em, tar' LEED is presen ted ~ 'fw;gure n "i.~ T'h • j!!j,k ' ..:11 'L 2,4\).,.' n e 0 'L IJJSCfvef IS genera 111t..·' r oO,.~Jm.,g'hlrou~i a WID,uO'W at t h.e 'II.., k 0'r 'hie ![j;lC:, 'I:.,;

'I[) '1........ '

I

--

.-

r=

ld S ,gr~',I

of' th, 'cal 'bon contammam

.11
~ i

visu .~observer ion of the dif:fraction ,A t:ypica series [of LE\ED' paUerns from an i:ro:n «()J I J single cry,sud sur'face are presented :" 'fi,lure 2~,7 ~The' L,E'E·:Dpattern in [_be'upper' l,ef~,is for n the iron (01 ..) surface 'with normal carbon COH'E8m·'u8 ion present on, the .. soUd surface, The' four bright diff',act:ion S'PO~I in a rectangular arr'la.y are associated wi. n fhe :~r,o'nsingle eryst8J~, esh fr'ont the ir-oo 1(01 ,-,').1 orientation. , m Th .addit ional sm,a,~l pots arranged in a ring SI:r1!lCl' . re aboi t the four 'bdght, s ;'f"f- .racuon spots are: spots assc c .,al;;..i.a. ~ h t..r. e 1"1' I. ,ract •. f'rom car bo n con • ........1 Wlt'_,~, h ";;';'ff' :'~,Oi ~.o d:~. ~.' 'i.. 'm·...I 8Ulr:~·,ace.,'Th" '. careen it' L~. h lat,has '':'l~_UHL d :f'rom '1Y'e ·~·I"f -h UIJ,m.ln..a,Uo:n m tne SOJ.iY, o .: ~1,SI IS u 'b- Ilk or the iron ",0 the. soUd surface, 'This isbelieved ~[Obe a graphltic form
()D

hemse 1 t,.~ ves are

'h a f:" mes:: screen rme

i..' 'L.. uo ;, -~ wmen ...1 nor h iUllpet or ~m.,~\;le: " spot I, Ion the :nUofesoeO't screen.

the SQ,hd surface,

-. !I'

,"""",'

figure 2-46. - ,1.EElJ opt.la.

"].,5

spectroseo'I"Y lor soft ,X."",ray appear,mee pat~[en~,~al spetlr'OSlCo:P'Y (APSJ~ :~:n APS" the ;sample ~s bom balded. wit:h elecrrons 0 f' variab~,e en.ugY't and dle~ 'tolta~X",ra;y lemlssi.on lnt,en8ity itS measured as a function ,of 'the b'H:ident eleell '!\.., tron ene.flY ~eitements ,presre:nt on. ~,~UJe '~',.JI sur:r' SO.llu. lice' can b i,ue~.ti.il,~ eUil~,Y'.., ee .A ·.iF.:i: .... ,A "iI b' the 'e:ner,IY at whlch abru.pt cbanl'cs in int[cnsity o eeur " Th,e' ener,gy' va~:u\es
ecerespond

A<i'!iI~'bt(!;d line ~~~e"nltit'!''!thO' e seeetra :i"iI'b'Iio;t.l;';;nad- ,t'n'f 1[,-,. 'L. ·'_A,~ d' ntamum surtace~ C me ''L-'-"':,G. an: ' L ' ~'11 spectr,8, mJ:_' ., ,., r-h '" d .flI' b, ,. tne o,Xi,d.ze~_L",or nnes, hief1e'iS I, - ,_.d~. ...'!.."~ th 'pea.s assoaat:~wilt ,., h tne o:Xl~ho'n. process L ,. .... .d' 1", ~A,;;o;" " Ielear ancd_' wsunct ~~ht :10the -' I [md the redistrlburion of valence electrons, This is anailo,gou;s, t.o w'hat 'w,ts
~'_I~I

The sensi.tivi't:y of '~:nistec-hni,(iJjlUe'to ,che:mi,ca~,effects can be' Icl[ear~,y' seen from, the' dsta eresented 'in 'fi!~'I1l'e',;2,491 'for 'ii,,;;r':Dn'~ll~imbefore :!:ilI"nd aft~r' '(lddla.tic)o, (~ef .. .. - . p" _.. :-,,),.The solid li:ne represems the spectra ob-ud:ned. :tor the clean titanium
m

to

tbe coee Ie,Yle]j 'blii1db18 energies, for the atoms inv,oJvoo

'Ie"~ . ~
~iI!l"M&IIJllg ,I :~~!IiJ'" ~~ -~~ ~~,~ _. ~- - ~~-

~.

"

oo

··"-1\J\..... ,J' ~11

ul~;r-a-,lli~'1fIi,6 urfaee: ~Itl: _'_, .J.J~ s

~.

-il!.' ~III, . g"'~[jI

tib.,;F.l; l~~
I,

1Y.i1~_

...

_.

.'

'!If:;ilp,ll.

~-r::.~.·

I~

l~"1._

":_", il!,~"'~~

" '.' 'yl

i'~gJj 1

11II!i.. "-_

ill

observed_~ ~, ,A·'·'-··-·.E~'S-· ,jf>'b·~'i~..:!IIl in-, ,h".aIf"'~ v. _ ~~

I , ._ _

'W·

..

.'

~1L ~

;~!lill~~A

iil!_L'l'·f't:t:1 ~I[I., ~-i3-

wer·
..

'-iII' ~

observed u ._.~, ~.

a:f~er o:x~datl:'o["nl of a ~ _. . . ,~. ~

f

lUI

rnetaJ and se-micQ'pduet,of on. nonmetal S' rfaces, The chemical s:tdft 'wilth , ., '" - data ~n, lIlq:ure '" "2'0 tor .~ae OX1!wUon, 0"r '.i:.:i h ·'... . ,Aluget ,mul~Y,SiSwas[ seen 01 the d ~-,~o e 'SiUcom~The 41! in. :filure 24,9 represents Ule' CDllftle 0:" the ,actual. !cbmit~d
111, ... , "

sbi.ftlJ

1[ L..,,1

I[

tl
.

,
1;

i ~,
Ii' ".
I I r 1

I[
-

II .1

,.
,

,,' il "
[ ,

,J

,,
"

"

~.

"

•
450
,400

\'

410

480

,FiluN'

,.~ ,bejore .~d (JKidflti'81t1, •. RitdVrln&UfWd tJ,f NNIiG-e e~,~ 'r~~fm~/"" d(fl' 4E [;1.1,- t/ItruJ;,(JiJd (,Rtf;, ,J 1)~ -

2,'-49~,_'SUft

x~~" ,tdIu

~ot,em1lt:iall f~J'oll a;;

fHJ,rMti~

:6p~~

,.~~t't~m ddn piJlji£,,!MtdlltM' r,~ti~n[iu'm of

,prMflct!fS'

Chla:r-ge

nreutra ~ii'" za~ioo

s.ystell}

.....

',',"'""..-An,M}II,u;r ,,',"". sh l'lld

,detedioo _
~sy,st,e'l1~
~1IIIIIIIii!!III1IIiiiiiiiiiiii1iiii!!l!

Ion bellml

,countlngl
system, Prgu,re' ,2..J;J" .... .s:~hennrtic dMwin:1 ,of
op,alUtUij',
iolt ,X:QltM"~ lJBlM8CfJjJ,

IPu,lse

")(""

'_'_

_',lrlli"

y_:,1

R~'e-'~ "_00,,, -rder

' .•• -

J:

,It.:

'(:1S8~ ,experimtntlil'

:pa;raUel plm"e eJectr,o'sU"Uc 'en'ClIY aReJyz.u with a, 1::t i x ,~~} meter ('S,-udl) ..s

acceptance apenure ~splaeed 90 from, dIe' inl~;all'[beam to monitor the

0

tered ~Jle/t gas ions :~eavhig the sample surface Ions that pass, t:t~ro~ the' electrostatic analy,zer have u:nde,ygone ill simple binary' elastic oollis,ion wi~Il an. atom on the snrface and thefielry have had. t:heir en,er.gy' altered tu:,cor,(iing , 'h ~"~ "de " D' '. to tne etasnc scattertng enerlY OOiRSI~ra;t,tlon's",':etecuPg tihI,e: scattered ~O.D~ that. ha,y'e' passed thrOlllllll. the en,ergy anal:y~er' is done by am eJ,lccu'on ~:iI~ ,. h ·'.... 'h AI T'h '. f '-hi ..,Ji, fmu 1t~llll.ler WUu a, Spe¢iw'1 cat., oae, ",,-,e gam, ;actor 0;,r u 'IS Ute~ect,lorIS:or tne 'order of I 08:~ 'Tb'i.stype of detector is,'very stable; il caD 'wl'thltarn.d ,lir cyc~in,g with.ou.t any kind (~f l,gtl.dJation, Qr the unit,;; The entire ~YS~lemis housed :in d a vacuum ,c:ham ber w'hlch shotdd be capable of achievin:s pressures [l,r the
,,..J,II "
i

&CiU~'

'iii..,

i' ~ ...I ~ hll "d I.' -" purn,:ptng sy:Sltem 'tS 'u,e!Ur3_-!le 'to aVOI',!, snrrace Iconut.nnnants w hi' h Jl"C_-~ ma',yar~se from, other ty,pes ,of pump~ng $,ys.tenns The data 0btained from the ~
nJJl

order of lO~gi 1.0,,10 torr ~ or

A _, ..

IOn.

ICl!S: .~ !iJ!".
-

@.I

§f!',iDJ i'! 1,..OUiI'1riI

!\i!J~J;II~J

'~',Il'"

.... J' 'irii ~" "'iii " " I;} • V~

sa

n'

0"-

~'ni"i,~,;r;'~tu I~ ~~,I!~,~o,IJ.l~!I!, J' OIi1'

'8'

,_, '~'" ~, ,l~~l,

,IW-

,s;en,era_~F.yp lottied on an :X Y reeorder ~The p:~ot shows th.e presence o;f all of
-111

u-n' Ajtl"Oln-n',' atom

J ... '

1 IWI

Ipt.,

Vl

II~"

;.t'!I'

'mlllllli'iIl'lIil' l ,.at.:1!~1!

and , ..iL.;j,1l1' ,;~ ~ltI.'

~~.ililll!il! .I~

ion, Wne'Jl belium 'is the' barnbardin! .i.011 a,'] elements except bydrole:n and helium are anidy.zed ~In addition to the primary- ions fhat are scattered 'from Ute Siuf:faoc'I!S,puttcrins also ta,'keg. place as ,0, result of' the pirlmary beam
dis~;f'!j!Fi'"'iin. surface atomis
_ -_ U~ __.-.~ ,_.. _._~_~~ __It._ ,_,_~

the ions t~utJthave an Ito'wic mass grea'ier than, thalt of the bom baJd:ing: ,lIS

'ii-'LlOt·· !t.Jlg

achieve e:f~(l'I]e:'b omemum to leave the sur:.. m g..~

II .. _... .' ' __ .. -.~ I I· ..• I... "I J I ._" . I. , , I,·, '

I'

I 'S,~
~,
-

.~

;1

,~,O

(,~} GOld.

~O

Irmilo"'if

~.o

'I

1@

~o

;..

ii-

iii

d-

4(i1
ID/"-!i

~o
~

";

,.1-_:.

(IJ) Siltier"

t~~

.,

1- -"'Ir;t

'~

~'""=-"=~'~

1('('')

,PtlIiM-h;;m'..

~,o

20'

---

,iC;IOI

I~""'"

~al

1M

tOO

,_

~I~

i'in PIi:Um.iJ.R1.
'\. u-

nl

,~ili
•

".!_

.~

60
-

'__

IiJI

Im.le

--

FWfire ,2~j.,-',~~dmJ' r~~ ,maM' s;~r(J'$t;tf)py (SIMS,) ~iN ~per' ~' liOflff~; tNlrlQflf ,..10/4. (rt/~ $2],

ol~J~'

,o/' SiC

fln$i.H'

species, are t:hen admftted 10 the 'vaeu,um, ,system, 811d. allowed to nile eryosetUfa.U-y cooled 'pin,-ti:p sW'ra(·e·~
1

mounted in a. cryolenicaUy cooled hOllder :insi.de a 'vac;uum system"" At aoo1ut, ~n: ,""'~.f!,'l' meters f:J' -,;('Ilm.- ~ll..n'li< ~'d' i :~'f, Ithe ~·,L. ti'P' ta L-p1:.. oi?'i;.-C'!,I'Nibl1~lr'~~I!'liIi'.i!Ii'~ fi~~:~:t'~~'l!1J11;;lo iL.~, '1iI;o-.L1L ' nli'n _ ' JlJiIli".!!';;:!f"'" ,oIi"i;,n,+';<Jl'I _ v' ~!liU.. ,,""~:I', ~u:",!!!;o!'l;l window'~ or in earlier dmes,~:sim:ply_,a :phospbO(feSCeDj, screen, The systclu is ~yacua.ted, ktf ,I. vacuum, '",um,T"ri:nu' t,ecbn~n:ue~-and tbe ti,p"" T e-,--V,~.-l- -"caJ]]v _ _ __ -- __ -- I"'~ __ __ _ ,I'" -----t."L~~ I~_ ,, .. . . ISF;.' D,gCIlL _;; cooled 'to U'quid byd.r-og,en, OF lli,quid heUum, temperatures (fo:r' less io:pb:~s:U,cated, ork, ordInary li,qui.d nitro,gen is sufflcieRt)~ w Some IWSJOOiUS
,U,'
,'Il;0l'

It,

'"

it;

~;j,'",l .lijjl!

g,

,JI,I~,.l

.."

CQrnel,IOle

on,

A hi~tthveltaee is, th'eD a,p'"Ued_. to the ,p'~n r·~:, ._ ... a; -d. th\1 '.' . .. ___ ~__ _~ __ __ .. " . y,. . .... l ...~p:sU'rfaee~ .n_ ... I lenerates, _ .. heUum :i,OOJl., The' beU'Um~ whiCh its felting Ion 'till' pin,I's, radius ,sprfaee" oee.u.:pwessites; tn,,!: these in 'the m,eUt], ,itSielf~, 1:£,I, :high vo:~tage: is ,appBed and if

the h.e-1ium, toms that oD'fidmsed au fbc' so~i,d8,l!rfalCC are :i,onized", tle)" can a

then. be Pl·:,_,j!!e _ _ __ ~Oeendmeters_ from tb.e p- -- 'fi~ to the. n:h:o(J. 0:1"_ _. ,o~;:cted _ _ . __ ____ . _ _11 - Iw~ated - - -- - - - . ein -~F' . ., It . ~s,pih~ . ,pl,a!!f!or :fiber optic w1liJdow,. In the process, of mOIVin,g 1,0 ccn.t'im,eten,*, the: image' of th.le pill tiP is mllBoi:fied ,fr1l,m one '~O th-r-ee mUllon thnes, This ,bi,sh

degree of mqni,ftcat:ion ,olf' the :sD\lid surface ,aU'OrWS, one' to see' on, dIU;!: DboslJi_hor,-coated p~ate or. D,bet, optic windo,w tbe :lndj,vidUll ,atmn sit,eJ,oo the', .. land lu:rf fr~v"m...whi,~~ fh-. ,. ~ _!li_ -__ ,i~~,~, !Ia.:mli!l1- '~.~'~11~!~~ -~ nl' 'thoR!' hi~'hl _ '_ _ ,,~ ",,-,II!l _. 1e h~,rum ,vn~ € ow !Ij;.o,., v' _.~ __
tli..... ,~M!!Ia~
,~.I!

'm.llli,fica'tion.,. tach :~ndjjv,idtm~ atom :site on. the: solid snrface :U,:readil'y seen
~.Ill,
o I _,

,-~- - 'f UIF lum '.'- miiJ(1D1 f-- ~e ~ ~d'"- llS - - - -'. .' - d' up from ODie ~,Othree milUoR 'tunes is seen. ill. ngore 2,-58", IJ.,.. .... ~1--,divild!';u:...1 w'hjt~, -, eot b iIW . . _e s - ~,t"- in fiO'I'I?1~: 2-:5~',r~"-:~~~~~ ,~:n.~f:y;:~,'liI~a1 __ ,d.'HI a·'t,o··m ~ _ U~ );I;~ _ ~o'!!'y,e _ _.iD _~Fr""'i"'~""~"~ 1 UtI __u~ !lUI . site Ion the :soUd ;s,urfaee dIe iridium .. The' :riRSs seen are lISIOCiat,ed, 'wbh iL t ~d· c."! '" ~ ~ '" .Ji. the vaf,I,OUl atormc ptaBes, 1ft the SO~l'· _sur 1:'aee, ~:Inlce'tbe p1ft Up' ~ has ,RfaulU;S,~,
.' " • '" . J' "_ • '. ~.. _.". ..' .... ' .' • ." _ ",' l, _ ' • " ,

t"~-- "FI''M·' A ··..yp,[C, , lmage -IeeD, w,: ,en a t- - '" al i - --h - IllC', ,
I,' ~ ...

'" pin,

i'

. _..

0',11

'0,'
'.'

_!Ii;

iii

'"

there

~811 be n:ll the WelU ~_ _ Ui! _ ~..11-~~1 ~ur:(~l,~ generated by oom,pu.ter' lnalysis, u~mg'CFyst,aUo,gJ',a:phi,c eonslderadons. :P:01" example, in fig.-ure 2"".5,8" 'if the central plane is klul,w'n in the center of the phOrt~"mllcl0gr.apb:i' aU. 'the 3!dj!l.celu planes can be d,efined by ,compU'~er a--'ii!I'~\l~!'~ 8md.'- -- - --:~,-ed tb-D '" --~ -0 gC~--!!3~'ly 'U!I;W ,e!i.h Th-- . ~~,:_:any -n~~,.1'~IOl!I ,iUJi.' rcump.f:.<_ '~,O '~,.~ :~mM,I~ ~_:_-I~Ui.U,_;" .o'Litain-A ., _,,: tens from ~ll~·I_.I:.':~. '..,~ e r'.~·'~1 1i.. dii iI1ifP:tlt;,Qlil' i"1i!l!lj;('! IV;' IUr~t,,·.g~:III.U_~~~ 11,.IlI'~ ~:' ,~~---,'"1'dle!O;'.'1 ,-~1~1. U_Ll~ ~J'J~'~ , ~ been '.''~~"'~'IJ~~;';I~ln__ ~d.i l~O~~~,~-~~~1 nf .~I~. determ .. ~ d w~ iLo:--, -"_-,, ner ,aOi!h,SlS 0'-f' I~_; 'C-,rcil.1 sur race, :hUl(:': I, as j'h, .:al~,h ,own ,~-, g"(~ll!Jre'~..;J\O'!I' - --~"'~ - ~'h - ",",,11 - ,- &;- - - ' - -h I~, - to --sn ,- ,I.M.1 -,,.,, C'O uy compu e.r d"'l - ~ ..".AII can 'Ii;. rea~_Jlyascertamea, ee Another d;;stiuICt adval1tqe' in usi~S the 'AM by the tribo~,o,gi8~: fhal the is FIM is ,e-ssendaU:~f' t,ool 'wb.ich provides an, ,uperity ..free surface, The pi.ndp a '.' _. 10 ~ '"cO jJJJM, di 1~ -tree " '. I; ·' nat IS beJD:g examlne- d i i Ij,UFe' :~""...l'Q 1!.. a rae lU:S t-hat ] at,tua~y' f' a: f: aspertnes .. When kmllb~g first takes place at. the :rcdatlvely :tdgltily,oita,gcs, Un.~, ~,!h h
!Ii,.o:l.1I. 0.···· .

'image~,and the' varlous rings an the sond surtace :repJ,esentthose atomic p~anes
'Wbp,n
i,

are a nam ber of atomlc p:lanes exposed in, the' 'pJ-otcss,of Itncrl1tlq tbe
particular
"" _ . __

MA -11,1."

eartlcular orienta '•IvD .. ~'nI-:,,1 . _ ~~r n~",

il"'MiJ

~,o, :~'-j:~W-1Jiil! Ir'.nv

4O!i",_"..,

_"

tI+ -

i!ii~

,.dI~'IiJ~61+

M'rU,;i'l;i!'

i .....

H,t'

'h··

fQ.~

~!fI'

.:

'C"_

'vol't;llJe~oncentrates ·all the ,lSper.ities that an: p.n:'ml on 'the :s-oJiJd surtaee c ~ -'d ~au~..,..~ q'l· - deva ~ I-"";i - - 0,11 t·,'blo..... -'MIL_ lZtL ie ,~pora~,lon - ~ -_.OIse u;s,perlde5; k --i!!iiiU-'- e 0 f~-"iIi"L.- 'I:..'~-Ik .,.._-,-vec~ __ - ~ue.ullJU ~on'" s centrado:n ~)f.'efi,et,gy' ,at thOR :Iocmti,ofis ~ P:r.ior ['Cl0 braining ao, :imaae of '~he com,pl,et1e,s,urface'~little locaU~ed, b.right :5-pOrt ima.ps at'e obtained,; 'th'C'.se are cm~~tam'Uy le,hanglng 38 ev',apor.a:UcHl, tak~ place: untU, uIUma:tc~:y'; 'the as:perides are co:m,p]e~ely evaporated. f[l(lm, dlJe :BoUds:urface ,aDd on~Y'the' hn.... ~o:e of_ ~:hefr~dre _ srcrfa-e _ l:-, ,BlS--:~-fir": free .. ']'b:us" for ~,h-e t···ribolo·-:-·ist 'wilo IS ~ __ __= _ _ 11_~_ _ ~ r~ C J; ~ p:~ -y ___. __ __ _ __ -. __ __ _ __ _ __I "_ _ _ . _~ _ concerned, and i'D~erest;ed, :hl ~~h~ ,c-onUu:( 0'( M,perity",fliee' surfaoe-s w:ith :so,Uds~ be has sue'h 3" sur:ra£e in t.he' :neld. i,OR 'Up.
1i!'!I-'-'-e~
--!O; ~ - ;,.'"-

face layer. g,:in.ce' thb;, is done' in. a, vacuum ~y~U!nr.l, the atoms in, that outer .. mos~ hiyer evaporate f:ro:m the solid surface and travel in snr,ajsh:t. Un,es, roward the channel P,~~ltle,. 'particular atom IOf interest passes tbtoUSb ihe The hcdre ,in the channel p~a~,le-8~, through 'I be' hole in the mirror !and 'the lenses,~,and down the time' of fl$ght, mass speetrometer tube· where the' detector at t,he
le~d ._:-,J~,~_ d·' m easnres tbe m./:. '"'_.'ra'fI'l':yl:t a'P:lI.~'H n .lll'~, .E ing, some :in,for,madon about Oweatomic specles pn~~nt, on the soUd sur:facc., It. i~, then, a. conventional mass· spectrographic analysis, of !file atoms 'I!:min.s: a
iCRN!; ~~II,I(:":j·=-~"':__'.

S!!8

the pa"'IIi"~""-u- atom ~"f""l'nittn"iiQlIil~ '~,g,,.. ~,I,_

1~·J--·~',~~' :._!~I

~v.·I':1

_,_I_,I!Y-III~~~

(tih:ll'fli .. _, I~~ll

,I

r]

I~~W

.[~I

[Il.'_.~

~~iIIllll-]

The' com'billsdon of the atom probe w~~lh Ie F~:Mprovides the tr]boluli;st. d witb surface C'll.,m-I'cterizadcHl tools to idenf' fy 'the structural arrangement 0" atoms on the solid surface 01'8,wleU, as: the chem~s~r'Yf ChlS&ers, of',alom;s)1 or o even,o1'.lUe ,~,r'-":ur'le' ,Hi_" on the ,saUd surface. A. t'Ynic~'~ atom ~·--,be' 5~~tr-a fro-'-I- a atoms ., -.-_!Lit_ ,_ '_ ~ _. _"""~, . .J' p, '- ~- _.'-" ,~,ro._ -it""""""",._m. r.egi;om olf a solid surface ,of a. ,peiarntic steel is, presenf;cd in ilIon: 2,~61 '.'The mass spectrum :is for the cem,ienE~.te' phase of the pearU'irc steel (ref,. SS)'i The FIM was 'Used to locate the cementite phase 08 the' surf.te,;, that, 'pa:rticlllar phase 'w,a;s anal.'~ed with t~he assistance of the' atom pro 'bel' and the specsrusn .~If:' ~.~. '-~ .iii.':~1 " ......... th '..... rbon :~. _ U:'OI], .. - "'1'1l,." U ·~e~ ,n t. .-'. :~-. a ". ,-"f~ o I dlur~~, "I ...UIIJ RJ'I!I'~S .Ie ,~r.o.n ,an '0< ,.....' pea.f!;,S .-., 'IllU'- ~1.~ th e ,mu:ut",r ,peAI\;B, 0'. .' s:Uieon~,chromium;, and copper, 'which are :Ploblb~,y present 2S, im'puddes ~
.0
r., , ,'..-

"" nme.
.... ,(

[',"

0 fe.

'ii

'n',~g.1 mass specrrometer ancd'"' it scope. -h" .- . " .

1,'_." . -:-.:-; _":'."

I-"··.~·--i

- -·i,·

.. _.\_-

._'

['

1:"1 .",-

····Ir··

,"

q'II1.,-

:Neutrallrlild '1011 Impa~t :Radla!tiOul

then m,ea:s:uring the visJble. 'U tra vi:olet, and 'i,h fra.J100J ,['adiaUon tbat, produoed when, tb;e 'beaul olf iO',w'·~ne:rJjions or nW-t'ral 'panicles, Im.pacu~ on a soli,d sutfaee ~The s:o~~d, surface 'colJI,s;tituent,$ are determined by ,an iden.t~flclatio,n ana1ysi;sof the (jl:ptlcal lines tb.a't are produced in tbe 'oo,~]l~sion toass,~The P ions; and neutrals iuvnlv,ed, ,aturin, low' ,enerIY1. tbis conditio. makes rhe t,[elclniQue 've,ry sensitive to the surface reS:lon:s, -since the rangle into the solid is; Umiiu~d a't m,OSE a :rew :monolayer:s 'because of the energy' of the incident to projectiles:,. The tec'bwqu1e i.s,faldy nendestruetive: the damage to t]lit~, sample surtaee can be lev,eo further miElli,mized by 'usioglow 'bam 'bard:nten't en,ergi,es, as, well as :~OW'currens deo;sJlHes~Since' surface ,atoms ,al'e being removed con,.., ;jo':;'nu' b·fV ',~.Ii!l;i ineom ,i'in. beam of ;;...,.iIrl;l't'o ,""'"'"' n'eu, ~'T'6I,I,i.'1' .'Ii..., measurements '. function [of'bombarWn'e,nt time:) can be used to' provide depth plDlfUe IOIfor'" marion on. the solid, The mea,lS1Jremellit of .optic. , :r'adia.t:ion, :ind.uced 'ib:y the he-avy ,pardcl,le b:npac[ 0:0 the solid surface requires mOOOfi]leJ',let:ic beams of ions and neutrals :1.11 ',he Nln,le of ~ot,o, ,~o electron vcdts"" 000 An a:ppuat'Us used to stl1.d:y solid. ,s,urf.,ceti; with t'b:i:st,eebnique ~a neutral beam [and ion beam source' 0;( low ener,ly........"is, shown :sChematic-aU,. in 'f:lJ;urc
~:i, ... ...r'!I;1i'Ii:i~V .~ '"Ii ,ilL,A IVI~r;)W,~

tec;nrdq.ue' has :recmtly been dev1ehlped, tOI :st:udy t~h,e'oompolitioft ()f soUd s:u!rfaees biy em,:p'.o'ying, nr~urm and ilon impact of a solid surface and
Another

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", n._"._. r ~_ beam ~,~ a di,jlolf.;· adv,mtafJl':e ..,vet some of £h,e . I~u.t·,-,al ~ .'.___ ,Ul!iW __ _. l_n~: .. _. ..... _ . ,~_ 'v _ ~v _._ _ .__. _"""~ p,revi.ou~lydiscussed :s:ysl,e;rms, in. that 'it does 'Rot, p!£O'vi.de for.' 'the buildup of surface char,ges. on .n.on,tondud:m,g surface:s that ma "be e~miRed.~ The fir$,t step :!Il using this device' (sh.own Sch,enu,ticaU"ln fig,., 2-6.. is to ,Ienenne' a 2) source of iens Of neutrals as the bom ba:rding specJes'i' :EI,lectr'Oo bombard,"" ment ioai:zadon;, usually of' nlltro,jJ,en Ol'OI:iecutes, lor one of' the rare ,PSeB" is
1M i!, _;ii!J11,

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Iii. measurements
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~ia,;.o!iJli.'-i~' TL~r\Di' """ are b',~'I!l!!i;<oilUJL~' V,' fp'Wi'l: :It.'.'n~('t"ii,f·: measurem ents m ad-~, from III !I!,I~;;:!t "" U""" u, ""', !liiC!';""'....~l' u _ .... _. :perin1.e;n~ The' fttst -0 f these is tbe spectral ,analysis of the emined radiat ~on s, o btained by' SlC~MUll:ni the m.onochromam,or thJiough ~-hew,ave'iengt,h; range, ,t - - -" - -m'l-"- 1dl"U'V\ t,· c',cOO''-'' -.. . --. !ii' .~ll- .'- O~$IUY'-' '~" ..-.-- "yp!iCa~" ,""'uuu ~O ,1;).,< e,' angstroms. Th-' secane measurement :. :_,e. . - d- --- --, - -~IIlVOI~v-es in;; 'the hlltensity' of a, sme;ie j lne over a limited segment of the spectrum as a flnli~i,ii"ilon, f beam ~n, r 0-" or :1!lII,~, f"·l}n~"j;nln'of bomba rd ment time q'it' ,I,in~ o e a1d u~ ,liji'1li!':''''''''.;tJ. _ _~~ _v_ y IYv [ ener'IY using either a mcnochromaror or an, i,n~,er'reFence fiU}er~ A wide variety '0 f beam specles an d tlrl~t: materlals can be used to make
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spectral Une.sare proporti.{u}JJI,I to t he' all". Siohne concentrations of the ,s,pecific surface eon sdtucnt,s, wi,thln the nenetra. .. don de,pdll,of' the Incldent beam, of ions or' neutrals, M example of'th!!' t,y_Pf
_ ~'W

The '~il,tcn;si~:~esn the :individual i

of' radiation emiUed from excited states of' surface s,peciesin low energy i,on
_l ~

neutral :~m1r\l(;ton ~:he~o~iid.surface is, iUus,tra;i:ed in nu'uf,e ,2413 ,(n!~f 5:6;)~ The ~ JF' ~ s,:peetrai, Idbl,'~rilbudou of radiation produoed hl the im.:p&ilct of arion ions at 4JJ.I(Xj electron vo,:~~,s, coppeJ' and 'n];c:k,lel sur:faoes, is, shown, in 'f1r;u:re 2, ..:3,., Ion .6 'O·-'1i!'1i¥ these -~'I ' !'d- ----if,iLf-·· -d·' M',·_- oi"'i;·f' 11th· n-'e""'-C~.~.--;-ac,,·t' Ill!f"~~' h,!!i,~.1,~,,-~ ~,~e'!;,.,,"rg._ ,!l1i",~n:s 'h_~V'1I;Oi 1i.......ari '1,·:,_,eullj,. l'e:_ g'$ ,_ ,,'Ji1Ii~ v'· tt"',Fvmlll.'Ii;il'lL coming froim ~ow".ly,itll ,energy levels 0 f neu,tr,ad nickel and oopper ~llu.n,ered .
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face cODu\m.insru,s;,; the m,o~,ecuJar ','adiad,on, occurs at 4300 and 3900 anssaromsu ~ '''fii~, electron rr,i'Ell'i'!ii'i<'ti~'!,~n, '!'ti;··n·'~'~i~'D m ,~1.1;.,~ C .,HI'~ :it'1, fro !lbJLIl~ ••• m·i-'lt"',l,@;f!!,u-·I~'The ry-n-·i,,~·,.i'H' u.~ .. 0:' this radiation is 'beU,€:vcd to 'be due to the ,clOHisioJilia'l eclc:itaIUo:n of ads - "'l.", - d- .uy_-d" roeareon - c - - -. --,~ -- - 'p.-" - -. --" on" me - surrace to',r- 11-.. copper.'II:." " - -. 'k - comammams -... :_0_'~or've;_' resent - 1;.... - - - lit, ..- - III.Uel - -" - .' '('f th _e COpPel - :·:"1 - f'-,aoe _. ms e_ean ed-I W,~I_,._,_, th e-.argon Ion bea.--- lI:b-' oCOill_,a.m,m,IJLS, - -.. sur '.. ] -.... . ;'. .,~ - -- ~_ -- ·~'t-h __ -- - - '~-- .'~- --,mt, 1_,_ Ie - - .-~<". --- ~-- -- t _"'.' .'" " 1 can 'be 'oomJl~letely removed fr(J,m the ;SQ~]dsurface and the peaks occu:rrine,
!I.§.IJ~~!I~1l ~,~-"'!Ii.\ . U , , It..,g.Jjll!i>.Jllil,lu .~ M ,~Ij~IUI:'~ ," " u ~
J~!Ii,

off ~be surface In Ic;X)c;lt,ed states by the '~n,cidcnt :.011 beam ,. In a·Ad",t,,~.· t, 0 spec. r~~, '1nnes ~JJlom th e surraee'. ~,arBJ~:~, .' ' .£!'. 'ia,1 ,'.'nemon .. -., . - ct ,~~1," .. -,' L ,mi~L,en·.1'-n~lllu~~,y" ;, ke -rgHi.lU1Uf'!Ii" .. a~,ii!_o b b" ,-, ~ eh ..;, eenner Fl'1j' n'~jfii,,-, 1 ~w .A ~ ,; it', I ,"!I1'a~v_~dl W'C]IifI ill '~iIl:j:,:' aractensnc orr- SU:r-- _ v_~
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,Ra,dia'ti,IOID'E,nergy Sources
There are a number of surface tlnaiyd,cal tools that cmp~oy n!diaUon sources to analyze or energize the' solid sUIJ"faJCe 'for a:naJysi:s .. One such '~oo~ em,:ploys, Ole :M,loss'bauer' ,effect, or, as h. was ear'Uer known, gamma ra.y'
resona ..ljii'iII~~ '~,"'j3F!iIt'iiFAIi:'!'~li"\,'if!i<W. "lMJ.. '·M'·.; ss..'b·_Iil!i,u' ,~'1 ,hi!'''''''~ ii.r'~Iiif!' been l~lnl:t,@"iiI'iI;y!\@'il~ w~ '10' ~~,t'~iif"iI' Ii:'~UI~~""~: j ,~~I"", - ,_ il~~"l' '_ ~~~,~ 1~,'!i!"I!I,il~II,,!!',;;Ii,,, slaee Us' d is:ooftry in '[9 $1;,. btu lt has not been wide~y used ,bll surface i:n.aly:sis unti, recentl,:~1 {r.lt~f ,5:7)~ Most of the studies em,p~O'yin8 the ~ Mo'~I~&';l'b-.' <ijl'il~IIi"' effect h ave been 'Wl"'i"'h- ~il'il'II"L, sollds and 'i ~n'It~'!1 v,~:il'V -.r°C;,;ii;:rrt11l-l'u' sellr"", .~1Iii.P1Ir u~u",1\ ~
"'0M;.i!'~,1I __ ~Ii_'!;;!"'!;,i' ~,t;'-'Iio!I!i,,;o!!;.,1II V~'\,!V',It;",J' ~ IQ \i;Ii _ _.. . ~~l
1

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face effects w~re i,eneraLy di:stei.ar'ded ~The :pn~se of ,a,s:orfaoo:; hOlwevel"'~ noe __ dot-S affre-c~, ,M:,06s'bauer '~li1leasu:remeJ:lts,; this, e~ffect can~ th.erefo:re~ 1bt:' used ~o gain Bom,e 'in:forma.do,nJ on dle ,soUd ~urfac:e',"The Moo~ba,uer lllUJJ1)1:i,ca~ s.pec,a, t,ros-co:py ii~ relady~ly simple j,n. 'loper'aUon ,and in ,coneep.', ~ And t,he' :mel!Suremern S, of nu,c~ea.r erfec1.s-~-hat i,s,,~, d.etleeUon of recoUes;s gamma, t-he adso,:rptiil);:D-'"""="ls te~aU,vely easy,., Th.e basic Pf-~[ij.'c:iple invo:~ved bl Mosrsbaufr :m,euur:ements i"s sncfwn ,sch}emadca:1;, In figure 2-64,., The ~a;m,p~e' be ana -YlJed and tbe pm,m,l ['ay to ,SOU'foeare :m,o,v,ed r,el~t~,veto each. o~her ~ The ,absorp,t ion () f ,gamm,a, r,ays by'

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m:llili!fli~d' l,tilt ~-itatb,1IB '" "1;ti.'I:.., lI,e!il'r bO,rlnu..Il 1irn!C], ,,": "'Iii' :', I' ,''''''",'" "~ I~ , ," ~ 11 'j, ," do; .'" '~iI;it""""''_''''''' '" ,i,,", W1Ul en, unp:lng,emen" tc ,f' t"'k, : I,"" ~t" [Ir"-,' ' , "!Ilo t) diu, l~m'!Ii Jc, "b"""tullli.,s, .......... ~:fiII, ,- -.~ ~L.'~.,' i 'f '·n;- eeuon ~ ," ,'. '."'if'""'." ,-.~. I,· \ "':, ,aJ'l,g,les 0., ," '- '~"" ",." :TII:'"e ..11" ,. r" ,IKluenc"e:~ " ; ~nJ!"',pe:r'Cen~. tosses a.il. 8Ur.S£

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reasc.Ul the film is undetectable at normal incidenoe is that the lneom.iq;, and reOected Ugh-~wa yes Inreract to set 'up' a, stlllldill.l, w,ave widl ;I, node, zero

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el1ecbic field, at .trle~:n.1,:nectins, surfaee for internal reflection, :Exterl1a'",reflection has been ,m;gbly nesl~b:d ,u, a method of stud.ytns ,S.\I,(- .., faces, bu;t i,t is n.ow be-in,g, more w,i,d,e~ used" It bas, been used teo. det:ect tbe' .y .

presence: olf moft'ola:yer films adsorbed ,e"D surfaces. For ,I ,ei,ean :surrace" re'i1ecUon.measurments can also 'yi.eld in:forrwa'Ewo.n ,abou~ ,tbe Qhla.nge: in op ..,
lI'fi'A!~ [II;,,;-~.:;II

~ical ooosta:n-is of the material (te~wting from ,I change in atomic bondill8}1 as one' moves from the surface to the bu k, The reader 'is,referred to sur" _ 1;(", ·to·· .r;.J#_: ml~'i:'V n~lin.p1·~'_iI!'!i, "h"', ~, ~'~'I,I1.,i;tll,"""fn ',.....,,~A...'bn· iIU~, !t-~I"'''''''''' ,.., v,~~, !I. ~\!l'~" ~~ .. UiJI uu'" When nlh:~ :propwga.t,e;s to'ward the in~erf.aee, fllom a .. edi:um, w:bich. is jITi'A;'lj'Ie, ,d' "~:nIt.'!lI!i!I! ~It'iii ,ry,n,p ·W·'I,..:ji,r.:'--- ;:~ I~~~ 1..:Ii";ii!iiHl'C';i1!i, . t- 'L ii!-'i refl ~j~#'!i'l'll ';;~ ~au~ .. '~f\IIt, Iess U~iI'~~lt. I[L~ ~ ~~~~I,Bd:, _. Ii!1!ilf. r.~:n'~:, .. , llili'w.iU, it ~ .., " .~ :t:ikt· ,",n·· -It .',. ,t, "~ ", l~lo.ll~ IUuJS re.ueCdon 'ii..,a.'b" ~" .. , . ,-., lin. it:L, ,- same ·as,ex~er.naJ. r,e.f1" .,--;.,: 'f:' ~ "iaye,SmllCu II!.Ue' ." ,eC!UOn."rom -, .nor,.. rna] ill""i~..Iipn,""-A u:n,'fr:~1 ;"",11~,~;k.. t. ". :a-,~ a_eritie ...l. ,B1fio:l!n 1!";i1'Iiou,,"",Ji~,~V'W' (see ~1i . 2-'....~~:)":.... e ls ~~.r'!I''''",,",AI z t u,,", . ""ilL 5 !!!!loW'" t"~-m' ~ . ",fh~""m ~&'c;.I~ W' 1 llluu, .. 'O'"'"'VA'ffiA the :ii"i;r;t"t,...,...,1 ol!III'H"D'~a th ;,L:' t"·Ojo,~['~r--afl'-ai"!"t"'l"i"i;--:- ffl;·ir.j,d: the interface BM',~ ''!:II'' H ~,J.!·U\I~JJ(;lt ._lUE.I,-" ~ ·1., . .I"--iIJ liJ~' .~ ~)L __ ~, .. ~,~~~, ~n. ~,~J.' ~_:_~ ,.~~_~_, .. ~~ perfect mirror. There are Uilan, eemmon esamples of total in~elBaJreflee ~lo'l1!The hypotenuse of ,Q! prism 0:0 the side o:f a glass of 'WIMer' suddenly' ap~ : " --" '-. ,:,~, 1.-', .. !'f-' >", '_4' ·"~rt· ,1" ::":, --"'"':' ,t: " 1 pears ' '.su.veS'led'," ,l, Vleweu al~,reif.! "aul. I.nge.-s. .., ~"" '( fer. aps the ~n.os·com.mOD e"Xbn i .e p~e of to[a~ reflectlcn d11lit OCCUF_; in, nature is the :wdr,qe Ol,g,~:£..6'8)-.. mn. tbe' mirq~'1! a llyer of warm all"' adjaeent 'to a h,ot.road or ;1 sand surfaee is opI·-~- - ,.4- . -I,·' ," 'd'- ) th- ,.,'t..".- '.' ,~'" ,a,'"' d£A>_l)' ess aense \~ ,;,~, .'RS ;I, ~'ow r re' "1" ac !I. 1ve m ex I. Ian me eooier ai!' .e.. ",t bas .~ ~"" ..... I""'f: 'iIi,.'OI"~~ ~O'',,' a_u"'"," ~'f f(I'f 1" oriI'If-\i!f~ neles o·;if;" '~'." .... ~d"l~n';I"'I;..:i; it be oo···nA~]:·,It~i.t'li.'n'I,i.r it,.....t·,"'" I ""'4·flAli"ii~n..n ;,Ifl' 1fo'Iio_'i!>'""~" ~ilJ~Q!' m. ~,~l""~!IJ,.~,VU
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rUms present on file sohd su.r faces CLn n~adny' be' detecaed. An example 0 r Ul,is rus shown in the dat a of table 2,.. ~' · where a silieon si,ngJe crys;r:a~surfaee has been t.tt-ated, by various tech[il.IDque~~mechanical polis,hing, $puUered by argon ion. bom bar\(J,ment " Ic:,~e~ved~, cleaved and annealed ~ and chemically eolished, AU of these different surface treatments".1Iiresulted ln obtainlne d'·;jf'·;o""""M. 1;ii!U. 'IJI1!j,~ _ '~."'~l €etf1l1Jt. .8, amJd '~ values, as j,nd:ica.ted. in the table, As has alread.y been 'ex.pll;in.ed,~ the '~ad:a'U:on, in 4, is :au:ribut.ed to dlffeTIe;,nees in fil~,'m,~:hic·kne$s (:in, tills case, silicon oxide' whic,h bas "€o.ll'med.on the ,rdnglecrys(,aj, silicon surface
~..... _ ___ _ __ _ __ ~I!I

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after or' durins pre,patr-aUon) and U'lJe Vi variatlon in table 2-[ is anrlbuted '~,O .

',ada,t ions hi damag:es run th,le surfece laytr,

co:rres'l'uJnd,~n,.1to -the id.ea~ srrain ..free' surface, Computado:ns w~th. the eUiP50metrfc eq,lu,Uon reveal th ilt the surface la,y,e-ES! of the diamond ..potis'bed specimen have been. permanenUy' dens,i:fi,ed d1.ulng, mech anic ai, poU~hrnll;g"The optical parameters of' the densified :laJf'e'F' 11M a refractive index 'Of ].,530 and, a t.hfckr:lesS 0 f' '950 angstrom s, W'it,h the s;~ecirffiiiBnp' ,n..·ltt::'h: uilj1np' cerium oxide hcwever Ad '--'~~_:~D tr·La surface a:n,nQ;a~ to 1""'" _.~"_: -~~~~~~d [IL~ ' ._ .. .. ~,~I~ b'~''V __',~~~~ __ IIJ1: free .' ' U~~'~Iil! ,~, -0' ~, 'C~'!'lIin, be frem rhe ~l"'l~ t:"lfl- ~~~, ;'Iifi' !Ih,!I!J!~ .I.. ~~ '0:if' '~~~;~'l"~~~ ~IJ ~~Ul V 'iV s,p..ecimen;; The' hardo,css, ():(' V~jtreous slinc-a, and c-er,i,Ulln oxide are' 4.J) mohs illd 5~Omohs, r,es,pecdvely ~ T!his m a.y he why polishing' whh, eerinm ()J:iae Ai"llhc not inP'-:-m' nentlv d II of rreou !Ii:'~ll'.... y~~ ~-~r ,'. Uu,_ , ~~~ ~Ih' ~y, ,I lI~J v' ~-v ~1,Wl O~ in;s~.'eat1of 3,.,'79 52~'
0 y! 1Ii~~' ~~
1~!Iii!-~

,Ano~he~':in,'[eresdng example of' the' Information '~hanca.n 'be obtained ·w~(:h e~r--81----- -- :1;5preEen n 'eu Ul. t-ble 2 I~I T'-'-'b-1 - ~ liii '~I·'- ,tJ~v,a;FUlUi5 "& an·· ..'. - "d 'If I :: _l!p'~ometIiY ..- -- - - - -A' 112_'",,:. ~-!J!.. ,3JI,e ~~!.11 d~lts h ~ 1.._.. II "1" ., 'III ~ vames oeserve d- on, '(W'Osa~Dp~~s'0' f-"vitreous. S,t sea Wh'· h were, r,es;pect:~ve,~y _.' J ,jl(:. ptd~:shed 'with diamond paste and ted um oxide. The table :hl.dica.~esth,Hlt the' -'il '. ·-[1U' ·-11 d .' h d" .. v a]ue '0f· I¢ (In, t, ,Ie s.peClm,en mec',·h·' I', •.... anlC~l. Y PO',' ,S'.Ie· , Wlit". .•,lamon.' d' pas~le' 1$ ,
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The results of removal of the' deasified surface ~,ay,ers by ,et,c[td:ns the .. :.' ", -... '_: =;~',",1'::'''-'''1 ,'~"-"" ", -,_:' ": 'd "'YhrOOUS 8], U;S!.spectm -'1-' .' po wlS~ en , ,.·-.111",'·-,1"-','1"':'..1',' ,=~·tb, ",_samona p.aSd~ are ': also presen - ,t,ea:' In' ~re~,WI, ,U 'd"";" ," -: ~ab~,le' ~., From these data ilt em 'be seen t~hatboth yJ' and .4 increase :ra.pidly :2>;~ i: - ·d -d~O"'''iafi lUI(: vahies corsesponc d~ ~:O Une ideal~ease 'with. 'mo: erate etching .. :runS On comlnued etching, however thley' overshoct t be' ideal val ue, Wlth dbi;moad paste poll sl1iI1lI,~thls may be a r'es~.dt,0 f the surface roughness 00 '[he microievlCl w:-. iicib develops on a vitreo us; siUca. specimen ~
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ballyzers and electron eBeJ,gy ,a'D.&lyzers~· In addition to those shown

_-\T'tP.i ... __"_", '._" _

schematically in rmur,e 2-',12, 'tber-e Me iaR det,ta!OfS tOf' det'ootin,g ions Ilbuated. :from, so~fd, surfaces ........ exam'ple" mas's speotrOllD,etor'~ for D1llI'inD' tile last ~S veal's surface bal~'ical,too's a'nd 't~lm~nUeB, have been devtropln,g 'v,ery rapidi'Y .. In 'faclt~ :it ls ,pro'ball];Y 'safe to say 'that n,eady one , new device 'per 'month. is appearln,g, to assist th.e~ scientist intef1esl:oo :;:0. 'Clba-racterinOi! sOI:~id,:s:UJrfiaces~ Because of the proU:re:r,atioID of' surface lDa1Yi~i~a'l. teels, Daonyms. have deve~oped for descri,bin,. 'these pan:icu]ar devices,~,Far emm,:ple, iln this, ,chapter 'we referred to X,... ,pkotoel,ectro'D r,ay'
.. ~l __ " '. _,_", ~"_.. •. [I _ ," -. .1 __ ••.. ~t •••••••• ,

,-~, .. ',,--, -.~,--.' 'X""p~1 'III' .--, ,ener,gy 'e:IJj,ec",IOD-l u !r,ac. ,o.n as , _,'.' 'i 3;uu, ,s:o on"., . ' "', i!,p~~~f'os:oopys, ," ,~,,, ,~ow ,- -.- -. . :1iI , ..• ,--., ,- d"'f1f' ··u'"···· .. ' 'L'E'CD"'_AI a ~ The t-ecli!niq;ues ,deoSclri',b,oo' and t,he ~ools deta~~edin, this cba,pter are 'by no
means aU inclusive, metWiur!ist,~
....1i~
,i,

acronyms; in table ~2/!!!IIJref", 6:8) te ,slve: tb.e: readJe,r some' 'm,dicatio'ii of' 'nbc (
1

A number

of thcs.e devto~ art' disphl'yed by theiir

Mdle 'va.del.y 'Il,f tools available~ to die surface ph..,sicjlt~

ch~mjst;) or

10 table ,2...,1:1]he 'various 'techniques. ar-e ,e,lassi:fied in terms of the incidlell~ t pro'De (as S'ilOwm in, :f1l ~ 2..'12) wlu~re the incident pro be m,i',Y 'be phofion" eleetren, :ll,eJtltral :i'on" phonon" or an E/R field,. Then the the various 'techniques u£ C'I.iilfied ,(:-bl{i!' - 8CrObvm). under d""'~'ifSt'~ontecilninlres 'W1hether 'AJboton~ ,.1-' eleetron, neutral, io:n" phoulonj) .oilt E/H fie'ld~The ,pe!iUes,~:n.um'itler of deteefan devices use ,either p:h.olOtl, electron, ,OF' ion detection s,ystems., This list is, 'by no, ~means all in~lusfve; in, all pnl,babillty', 'while this, IClkapn,er:is beins: w'nt,,,,
___ '_ .. _". I._. '

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i,., i,

~1i~

in future yeiU',S"., 'T,'able~ 1V' l(re;Ct (9) is a, key' '[0 the ,acno.n'ynts; .'ppeariftl in table 2",11:1.." ,1..
IMit\-PtJ'lr '[S;"'~.o::!!:of ,~'1-.I;IJi more ~ ~a: ,'-I;il~'!'iiI'iI'" d~ -,m, IeVl'~:~~'. t,·, hcse . thajJ 8/-~r~~ 'to be: 'UlI!:~ most .U,IIlJi.~ U]~ . V,lII. Ji,~. .... .~~ --_1V~L _DA'!11 ,,AI A 'I (AE~cr ,appearance' :~Itentlfh 'ill f~y t'6u~y' re~;~u,ger e.:reC1tr'llID,pectroscopy ,' , _~)!~ a S -,
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,I III

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d.eplh pFofiUnl ~Hawl~~r:~ de;stfiljdiv1e treebniq.lIe8, can be subdivided im'~o the those b~cmoique-s; tba't liUlalyzt the ;sam.pJe·surface' as wei. as those that. detect
X,--ra'\t 'nihot,oelled:rI'lD v S~[:r'o, \S;;"iiO·'f\'U'XPS" ')-' l"g·'1Ii"i1 ,e"'a..·t_'I!'!~'nO' 1t:'~'IiO:D~n,p,. _~. ("IS'S)'P' .'_.,...... .' ¥~ (:.' VtI.1!~V- v .- '.. ,;04, - ,- ,- .. , . - .' .. '.," 'II 'spe""'Lr-oscOPJ '.. -, r~, '.' .' '1t'I!'i'- _' ... ''-'-,'.'' " I' ("A- PO:)' Ill:w ap,pear-anee po... "en.ua.1 ' T1hosetechiDiques tbat detect the s,pecia w,bic:'b ,UI ac~,uaUy rano,ved, trom ,~t.. . - 1;..:11· -r-;_ - b-~-" . - -,-, ',,- - 'Iioo.--- - - 'iii. -. JII ... -- - - '" ,. I A__ . - .. td . - :". --- ., . - -,,MI.e: ,SOuu Slur aee e s,puUer 'uOKluar[ulluenl m,c 'U~: IlCOn:uy ion mas·$ spec .. ·
.'-' , J' . '~'

tbe s:purC.teror ioo removed (surface' ,s.pee.i:Ct~ Am'ORg tho. tlCbm,qua that uta1yu the .sun:plle s-urf:acce are .Auger em'lss·io,. S,peet:ooSiOOp,' I(:A'BS), or
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f .'IL.. lL.!:t·, f' -... d-· d- - "li6d·i R !!3V,me0, tne ca:pIJI}.II'tliS an:d ,-" ,', ,brmttUl,ODS,OL t~~e,__ evtces I'~,etm~w,R ~18.ure ,2,-7:3, pr,esellt.ed :in table 2 ... In ,adtltion to a ,H.parad:oift Q,:f the derices ,IT,e' V,~ 'w'b·t:~h--'d'eAM!-"'--u.ii"iit·;1i~\Iii'tn '.L,C'~.C~'I!¥i.",'!I;ii!, ill' 0' m· these th '.11'6 nftll!'!itdi!li;l'l.'I"1I'II~.;''lI,i]i; ."'~ ~Il it _ tu~ ~"',iL u-~,Jl''''~I!I!J can see that. the [bldtat ions in the eleme-flUJ, 'can be del,lett-cd;, :PaJ",e;x_.'mpl,e, 'wltlh AE'S" all. the i~em:ents n.cept h.-ydro,.,eD and, belrium, can, 'be d.e1!ected on. a
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:C'"'~:rf:""..",,,:0b'''''m~'''-'i'I"''V' of, M": ~i r'l11'i!" . ~ 4' ~ ~~,~.~~ S~mioo1i)td~}lClOIliS,~H;aim'i!i:)r C. Oam!('ilIS,~ I~d 1I',~hn WffilJey &; SOj]\)t 1,i:BC,;,,~, 1900~,pp., ,82- ~M. ].." SLb1. C,Y L, E,.:: :il}mHl']lics of SolmdJ tubric~ion 1M Observed b;YO~ ~JCa,1 Mic[tQKOPY', ASLE 'Trr:Y$"I' vol, ,2: i. no .. ,2~ ru 'm:8... ~Ip'.lOO~117. ~ . .iIi ~: ,'!Ii"', 'IU 1[" J' " M' .' 'iI"l!.~""" H_~\r ~I ~ 'c,t'~ . .oJ; 'm·· , .. iIi'.iI . . II,ifi.il!:"'I' ",,'. ~,mJl~.I.q,i:,~~, 'iLo", ~~~~$ ~~~~e~Jc¢ ,l!,J1;JiI:)lf!;" '" oO:!!. ,~. ,r>O'UI~~~,!~!i,l""I' ,~,~gijm ~,~ ,if ,I :;:r~;lU'"
lLMj~· ~~j
~I!IIl _,

.w. 'Ilowcl}eu~ :F., ,P'.; and, Tijbo(r~ ,[),'~' 'The Friction ,and Ltibdcalioll of SO'J~id:s. an 1. 'Oxiord P Ci1al'\endlo-n P:I'\~S$ (Lo~d.ool'!. t 5tHl)..
.~tl!UI
~i:::I!II

Y-:L;I:I, all~

IlIII "

g~,

~,~.II~-I

oJIi;I!!;.!L

.'&11:1; ~

~lltilU

""!

~I

5'

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'~,j'.

;;:J.

~ M'"""i,~,B... H"""'d'!i,.~'k g..~~ __ ~~,~',

.':. [~~~JiJ! .:

w~

,',

. I!!

",1""1 Y-'~

.,!"

'!'. 'D ...."j;in:j!! .. "'.;:,~'" 'i!<in Ai t!i ;.;i,iit;<o!,.in ... ' '~,- .... -'0<; i ,,~ W".~ ~t!!~ ~!lig [~'Si~.~~ l~~~!

~rtt=~~,

'I,

SQcl~ty riar MeU'dsl~ ~918. Gilmialn,~ 1. 1.: :Effiec~ of Inl:per'~ec~:iiOFaS Q[I D~5.ml:u~,iJt!)n,. Tht S!Jrf~ Ohem~suy' of Miet.aJls and ~i,~~(W'd,lIDC~(J~" H. C. Gatos,., ~" ~ J'CIhfi WU~y &: ~n~,~, ,IJl~:." 1i~., .! 36·."1, :5Q., 1. ,AmeJwnck:M,~,S., i Th~' D~rt',ot ObShv,iDlliom, 'of Di81ocart:iY:D~+ At'ajj)emi~ P,r~J5'i 1I1c,.", :t 964,. 8,. KU~ewMdt. 0.,.; :and :Hopi~r:l;s\jB. E,,:: ,o.x idat:i10 11, of 'M¢1~~js, AUoY,$" S~O\l1d ed .." :l1hml~ and t-erw~l1h _d Co", (Pu~:~~~!;~s.)l'l:d~ (Lo~d-ofru)~ 1962" 9'"Ow~nblrn~y,. T, ~u;d. L!J!~J~·.5i~,! It. i 'Th~ [~flu.~~;OO of' Cry,~tal Ori~t~U;i()~,O\~ ~,b~'O~$d,a~ A" ]C" t,k~nof' :Mfta~s<, The Snrfacf' Ch~ml~,st:ry of' 'Fv1:eiJ,a&s;fWid Semlioondue~,lo(f,~tM., C~ 'GallO$" ed.,

~,r'lJ.l!n~, !lin,"!
!~~~,

iO.! "",yjj ,~,

~~l~~~'

N' .,.... i..;@..iII A ......""-, .... _: ~,~:~~,[~~9"g! ~lI!~!~r~~~~ 1

t (Ii..."

p,.

:W'OI.

r.ay]of~,U:ob50:1) Moo~ 3, Tally,sw-f

&l!iland,~
I'

Johtnl 'Y/Uey ,It ~nsjl

bLC,. l 900~ Pi'" 48]=:521."

1

]~~U~CdOtl

:Marl]~aL Ta'y'!o~'~Hob~~[t&lt lui,,!,

:UI(:e$IU,'tf'I'

'~1. W:iWliBIW son J '" B·, p",: T'@pGgm-a:phy 'i)f ,S~Ud, SU1Fra;e:~~~M Interd~isCjm)!.in.itlfy Appirna.dj~ 'to 'ffi>Ct~on ,and Wear!'., NASA SP- W '! 1'97,8~ pp. 8S;-,' 42,. :8,:~ '~1. S!nlh~G. N,.~:len, A. C ,.:j and, :MaUkjn, S,.: 'Qi\LMU~,at~VI@' 'Ctru~rad:er~mdO:I11, A'bra~iVle S~[",· (!!if faces UsUrn1Ig Sj,:New PI"O;fU~ MI~$urin8, :8yst¢m" W~!i 'Vol. ,4,1.~t~i" IP.p. ,~1:5)~·ll5,. ,~],. Y'o~ng~ R.. D.; F~e]d Em;i:s~io(f[!j lUtr,ami!cF0'mlll:ef., R~ S(':~+bl:iUUm,.,! \\'0\1, .31~ ne. ,3 MSlr" .
'114.'. J(eaes
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,iln:Sir~m"jI Vll'~,'h.,:J!!J!"

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A. M:,.: 'Th~ Pft.~:se MieD~.'f1emt'ml 0([ SHud~ Cl!pa~~tlne-es,.IRE Trsns., i ba;s~rllm,~ \I1ol. 1-i'~, ~.. 3,4,~ ~,. n J 9,58", '1'1" ,MS ..,2:5J. :. !ti\. ,Z'Lnn,~OUl.QI H. t ,and .Jac:ovem!, Pallll,.: ,Mal_~i\cf,iIU. 'Senmr. ~'" :S,t~,. In5tJrlJm~~''Vo~'' J6~ '[}O,. 1 l'u~y :196!l;,. :PP'. '9'11~g,~[t I,'. 'V~atm i' :t.L;: ChW"aCiIDefimtio~ o:f Sur:f~,. 1'l1j QI'fiaetmimt~ol~100f ~f,.iCrillsto :Re~dl: . .." 'Ctrlmi~,:and PO~lym~n~,J" ,J., I,ura ud. " WeliS:I,e(}[J ~yr,K~ U" 'Y,. 'lffi¥VSrty P ,'rcs:J",,' 1"'$ ~.5. 'fiIro!m~~~
I' fO c',

,~9'9'~p, to..94~

1,8. Rab~now.La~ E,,.:: ~d T:aJOOr 'I),:~ MelaUitc: TraRcSifitr IktWH'filJ :SID.idmns Mletal~:' ,Am, ~ Auno:rad.i:~wapm(i Study,. Proe .. kay" ~" (Lo~d,o.:n)~ ., ~ A~ ~'Ot ,118'1'00. U19:5't Sept.. 24~, 'W'95W :pp,. 4,:5;,5,-4·1,5", , _ . Ut Flii~hmd~:r" '0,,;; Kc:lin~d,r.'11J., 'W'~,;, Md, Mil'l~r'i'.J. M,,: No.clear ,a;l)}d ,iR.I.d.j,~h;~];n~~:r.y.:S«olld <,
~I

pp.,

SOl, ..j3i1"

'

2~1, ~ann.

N,,~ Jehn ~r'i~e,y'&; Son5". ]nc:.:I' 1.9tW,.

It. T ,,:;,:tmd

alrt,.,

_ __ " " H, .. M,:: R.a:diQ~sGtope 'Te-mllliq~" MeQr,aw',..,Hirui.'Boo:k 'Co, ~

1:1. '~heil~

I~c",~,:[900.. ,"".::.U'e' of itadi@lisl@tQpe:!ll:m MiCt~n~f;gi~

iR5ea:rd:\,. M~tS!ms

'~~"'!

vet ,2 n'O,. 10.:;

11

H~~I,,! p" 143,., ,22. :DW"~I:I~, J. T,,; and Stir,anl", C. :0.,: On i.he Em,p-ruri~a] Law ~r Adh;e~¥e' Wear,. J., A:PiPl. PhJ~I'.,~ y,ol, :2:3. ~\Q'" j ,',.Ja~" ~9,S2'i PPI" ,~8~,28", ,23. M,t1:t-C:bant!, M, E.; :Er.fi:Sl i' M.:: ,bd Kr.ab~het t E, .J .: I.tWIDacti'V,~' 'Owldns, TOO~:i, rOlf' Rl8l.p,idJ 'II ,. t: 'T .iIi, ~M' J~ 4 '~A !11il!Ioi!::'~ . T 00 'II-,16·h~ "II'" ,~'lIlis~lmg:., "r~fIIS., ,,.,.,,j ... 'Ie V>Q,u. "'II'Ii:~ IflEJIi." .. .no!~, iIJ~.;j.n,~ "p!, ,1i:'A,il\ C:~'A G" Ii',j~, Ji.t~~'Jdi'j;!.', ,2;4,. Siw~nk~, ,la.urrtri~ N" ~ ,ad Bra~,~ ,MalU!f~~ J.. Ra;pid NGndiestrucli'\l'~ Ev'aJ!~ l~ : to\liii; olf M~~~pi,c De~e~ts, iiili C;r,,'8t~JUii[i~ M:ateri~Ws,:' Tire 'Laiue TOPQ\Br,apllii-y ~.f I(Ms,! CdJ.l~~,. M,etaU .. Trans., vel, I,~ M.", 1,"iQ,i\' p,p., '2~34. 25. Wttil1:.er G,. A".: 'St:r~ttl!lJ',ail I~vesti8Qliol1l, ~:f Th~m. Fwbni5:.,,J., 'V ae, Sci. T~l:loL ,. ~o\l.i., DO. 4,
i" I' t

]6. &eJ,g~ Wlo.lf:ga.:~

Ube,r ,Ell!] :R.Oi!ltge.no£1la,Jd]~sche M,elhQde ~'Ur Un~er.,srUic'lfg un;g Vion C;;it ~ ierst.i@ru~81en ;0 :K:ris[aUell ,eAn X,-J{a, Method. POIr :Studly ,ot 'Larl.tlo: Dl~Mlrban'Cee:s. of Cnrstal~)I,:,at~r.wiis~e.~~ki@ft~n v,oJ" W W'311O pp,. 39l~,J96., ~II
i

n~n A~~ I"" ii!':ij'I' P,iWI " ~_, _ '

I'

A~'~,

l.j.

"C"'-H'-'A'-'P-T"E"R-' '3'
.•.• :. :'1 I' ~~' I I l, " .' I ,~-'."

Perfect State

-·0,.' l~ S
,,",

".

-·d' - -'
,'....

L~.','

S·-"", 'fi" aces In':,.,···.-B th un

.

-.

".

_'

<, '.'

..

."

-.

'.

.:•.. .

..

_','

....

.••

__ l '

rM

anions, find cado,ns '(ne,l:,ad,ve'~y cD,Rrl,ed 'ions, Wi'lh :po\S~dve\ly c'hars)ed :ions),
t his 'w,ou~.dbe ,!I,um_]n,um, 'o,xi,de!" a tf,ibo~ogjca1:m,l:teriai w'lIlich, has, inh~rendy high strength A third type' of bo-n.d~nl occurring in saUd, material :h& that has aweady ODe been digc:u~us.ed,;: b~ the metallic bond found in IIU metals, I,D, the metallic h bond de,ph;t,ed in :fi,lulle ,3~2J~c)"he m,eulUh;: iens are imm'eJ$ed! in a, sea of t electrons. 'The ~dect:r()(nl move 'freely 'bellow'em the cores of' ions aHo;w,iq for . -d ... n "~ " -, .- . - -'~'e - ,.''1 ' - - ... - .' .. '"e ,--' ~[le~.·_0\m in_:_ 'co_:~tnuut.mg'to many o 'f-- me ll1et;al,1'1ie matenats~- properties - ..Tb'"s f' 'd'-",II'_,of moveme~-It,In the_ sea ef eJieer-,ce'nB, 'im:na'ls, to :meuds_ ~bejjr ~. oood,_ the-nnal . . _ _ilL III . ..... 0 . ro _ . ,iF.'" _I' . .. . __ _ _ _.
'I

results ,~lii1 V"~'P~'; :stl r'~,nc' b"::n.di'n~-'forces ______ ~~y __ 0--1 0 __---.--1 - 0_

!I;;~g!

"1-- _Y'_ lie _O_l__ _ _ In 1,:inni':- :s,-,rdrs,~

A cl,i!lI~:si- mtant1i)~'-'::lf; _ _~ __ C ,~-e 0

SU~'b 3~, t, h- .c~: o ___ YIL _._~ .. ' V~i"

and electrical c,o-ndu,cdon, e,ilarac!terist:i,cs,,: 'With m,et,a~s;!~ there is~a wide range ID,f' strengths dll!!li calm. e 'round; the binding enu~ies may be :r,ebitively weak, b
qo('l.,po;9i;"""~'Q g~~Y~iIIU"-~Ui

¥ w'l"'~'h,", m· [' _' _

~l I I

f~

'be' r:elad.ve~y strong,

n u11ilJJten,.,

such-as

eta ls !III]k_e a ~ ~I~ J.

Iium those ~lem 'with metal s JUte osmium, and

i'II:"Ii,..-jlI~:II'IliTn an~rI.l~UJ,WJiIL~ _
J

d
'.".._'

~'L ~ t~llM

. II- _ .. _ =~ iif'I!i[' iEo'Mr:~' U,_~, IltWI""I.1 '1fj!:"fIl8\i1' Il~~-.-'.T-

,A four~b tY,pe 0:£ bondiog is that seen bl tryst aU il1.C' ,soUds, such as, the dia,·' mend fflg~ 3,"',~(:d»~It is referred to com:m,only ,as ,oO'vtiJ!ent banding,. In cova'h=n~, bonding;, neusral atoms appelt 'to be bound to~t,h,ei' by ,o,yefla~ 'ping thejr electron distribuUons ~ C~)'Val,ient bonding Is an e.nt~mely stronl bond as evideneed 'by' the Idgh rnciting, pt'llints and the hip hardness o-f material such ,a~ the dili'mond~ The ionic bond Oig;; ,3:-]I(:a)l)is, F,ep-resented by au ,arra',yof ions where 'we h,a,v,e alternatlng positive' and :olegadv'e cilars,ed. ions, makifUt; up' tbe c[:ystaUin.c, :so:~id In co'y:rdent bonding (fiS;,.,3;,.·3 (b»., IUt,e atoms are bonded in . a"n array to ~bnila'r atoms 'whereas in, :nu:.taUi,cbon,ding (flg,., 3,-,3(c» an a.:rr,ay of cations (positi"1/'el'),' chaJ'i,ed j,on:s,)'ls imm,leirsed in tb}esea of e1ectrons wh~:ch are free to mO've d.ltout ~ In addition to' the ionic, covalent, metanic" and, van dew W aal 's bondi-ng shown in figuf1e 3-2~,there ar~' other 'types, of bonding -h ~, · "",..,:I u)" 1.. ib ~ ,. - w _lng~ sn pamcu 1 'Mt,Wl I'· ~d, '. ~~ ar, .'-'i!.. !qUI'-, t :!aJ~~are expenencea t, 'hie i~:rLJo~ogl,SJ[ or ki lubricants. In organlc molecules. sueh as, Ulqtdd. lU,'brica,nts, there are' molecules widch have 'lu'-nPQ;~ar structures and there are others whi,'ch have potar structures. A, non:po~ar 'molecule is :shown, sc'ben1Jadca11.y' in nSu-re 3<J(dl, With a no:npo[ar motecule there is: no preferred char,le on, ~;he
i,
1

;1;,

molecule In the po'llar. molecule (fig,,. 3".,3{e»" however, a,dlpole moment develops in
co

the molecule such that one port in " of the molecule is push i,ve~ycharged wh:Wle another portion i,s,ll.1~I9JJtivel'y' charged .. This v,uiadon, in c!ha;rge' of the molec·u~e Ican be fu:ndamen-laUY v~ry i:m,:I'O':rumt where charge di:(ferenoes ,W8;O exist in the saUd ~urfla,ce~ For example, it a; solid surface is rich in elee .. trons, maklng U attract the po~lti ve end, 0-( a ,pt)~a[molecule ~~hat :pa.r~b:ul:ar end '~'f':the m ole.... "" .mav then 'b~iiI"i'dl o :; 11, """'YI t ~o~:;iIAi ..... ule ,'!Q;J I,U"..i1i ~ib lUi surface '.l!Ii'nd therebv deter'-"'i ,. 'm".... f' tne so l"'dl surtaee ... ·.nu&,~un'~erstancd-~ 'h e. TI:.., d nune to' a great lextent tne propernes or L_ hng the di.pole moment of moi,ecul1es, plrticularly 1ubricaHng molecnies, and the nature of charges on d1.C surface can ,live: lc:on~ldlerra]J~le ~n:dg'htinto the nature: of the bonding that OO~lU~ at the solid surface and the' t.ype to f pr.op'_ erties that Ire exhibited by' the su:r-iace layers IS a result of' that bondi:n,~, The dipole' aeti vit y of various moleeutes 'can. be ,o't)I;alned rrom ,oonvent:iio;n,al chemical texts (ref. I) ~A variation does eKjs~in. many molecular structures.
",,",1,111 _
!I;.;!'. ,~ _ ._

II!

. 'U'iIi II _

'''''

!W.Jj,IJ!Iw'

i'''~

""IY,

".""

~.mI,~ __

!Ii,,

i¥

,}.

_ ",.I!l,~,

Ol
'. o I ,[:

R,fNe ,3=:1", ~ ~at:~~ntelied..c-ubi" $trM;tu~.,

central atom ,. FlOE" the raice~entiflcd<:1ibic structure (:O:g., 3 -S(a.))I~,he atoms ·t on the :fOUI corners are bound to the central, atom in. addition to be~ng

bOll:nd to' ea.cb other ~ If W~ CU'~.through the cu be :~n:figure 3,..5,(:a) $0 as to p,ick up, the atoms thar make up the' (1.] m) surface referred to p:feviou,sly in. reference to fllll];re 3·~ (1 .e,""the h ~gh ,ato'~ld,cden~d~ plane 'where' we' ~lU,e.rlect the greatest number y of' a~om$).~we would ,get a, sHoe th:nJusll the ,crystal such as that shown hDl figure :1..5 (b)., In the fl l 1) p~ane:~ atoms are bonded to 'e-ach other in a U'H~;

td.angubu' array;, one:atom is,bonded by a nambet lOf nearest n.dghbors-esix

to be exact, The (] J I) orientatlon

sy8~e·m.~, are three priu,icip;le p,lanes whi~'h are ,of there'

31"'S,~C:)~,w'hl,ch indlcates a stacking sequ.ence of' the (1,11) planes, W,e have orien tation A, followed by orientations B and C~, am:d then orientation ,A repeats; ,A" B, C'~,A,~:B~,C, ,A" B ~C; and so on throughout the' crY-SIal lattiee, In borh thie' fl!ct-celuered, ..cubic s,Yitem and the 'body -eenrered-eubie
m.O'S!

the' orientadon

tbem:sc'i.v,es, in this p.arUrcu'~ar structural a:rr,an\g~m;en'[ o!f atoms, on le:1j',ery' fourth p,l~fie.,'fbtet' ,plane-oS ha 'it ·va~yir.i!g or:ien~,ad.on,B,Md the fourth t,epeat.s ~

is" ~,hen,tl diagon.al slioe 'nu~ou.g'h the crystalline a ;s.o~h:l,.Now' the (J Ll) planes, which, cut, ~:hmugh the cryst alline soli d repeat

,of the nrs~ 'plaflie~ This is

shown scb.em,a;d,caUy' in

fig'ure

and w'.hi~:h. are' the m,IOSl frequently referred to when d~:sClls:si'mJI, cryst:al~o,81a,ph,y(the cr)rstaJ~:il],enature of solids) ~These particular planes are the: (100,)" n~e I( 11O),~.a;n.dthe' ('1 ~ t) surfaces 'wh:~cb were already discussed in reference '~O figures ,3,~Sand ,3,...j~f w'e examine' th e cube surface, we see these I 'pardcular' 'p~all@g (fig,., ,3-6,)., '~'.iU:re ];-6(a) presents three (I()()) p~;ln,esl in. a. £oHd surface, The (U:XOplanes are, essenidaUy,; the' faces of the en hie; strueture shown hI :figure ,],-5I(a,)., 1:11. face-centered cuble umlt Icen ~:here wotdd the be nv,e~ atoms ill rhls 'pa.rd,cular plane for the ludt cell, whereas w,iUl the body -centered -cubic struet ure, there 'would 'be four in t his,plr· ieular plane. 'The' (110) surface iSJ depilc~td. in 'figure, ,3·-6(b)~There are six Qf these p~ane-s
that
'CU~

'frequelUit ineerest

throngh the

c~ysta~ at

various

orruentado:ns.,

L, • 'I [he atoms m t h sur r-:ace pllne' are b d d Ito, W,~I~"e re bondec " "' ....,...1;' 1 'dl b ~,'e en,ergy req!i.urlleu, no ~D ar ate two h" i'A atoms :If~ .~Jaoe,nt p anes), ~ ","DU, ae (1.1 I) p:~anes from each. other by' spH'tdn,l, or p'uUilll, aput the atomic bonds across the interface and. liberating two free, atoml"caUy clean surfaces, ,An exampte 0 f how the eoordh~u~,t:~,onnumber (number of nea liest neighbor,s, or atom has) ,can va;FY on the surface of a solid is given with 'the aid 0 r the' data 'in table J ... '. The coordination n umber for d],ffier~nl surfa.ce 1'.1 .A ~ ..... ~II A _,. .. " sites is Ulli,)1:~Ca!tw ,.' :M.J1, atom, '" t 11..,~e corner sne 'L., a, C.oOTd'" '. :OUM 'L 0',f in ~ nas 'JUI!t ion iller
'.

~ nowever ~ t..... ]'e~" cea, Now .. .....0'f" tat~k' in terms, ot oeen d' u d I:nS(eiKI ;log .'" eohesl Vie: energies we should. talk in. terms of surface energies ,(surt3Joeenergy' .' ~nvo:'I d 'h as t, vee
.I

'k

~J"

1/1'

1:5:,

tne
'I,..

'0l1tr.gy

• -'h t."i: W'lll', \V',IIUCih.

~·'~I ...

Co",

"'

s.

"'

'bondhl(~ of j" an edge site' bM a 'bo'udins' of '7, ,amdthe (l ~i) face has a CCMo,:r"" dination number ~)f onding '~O JUre' atoms o f 19~ On a (l 00). face the' coer ... b dinatlen number of' 'bonding, b;,,only' It

,I

Sg,:rf:aC!8 8itie: I,C''Oo rd.in:at:l"o'~

'l:ThYlJU 00 I."
"

Corher
Edge 1(1,1'1) face

5
]-

(lOtl" fae,€';

In chapter 2, :i~ was, :hJldi,cated duu :rea.11 sol,~d surfaces are not smooth to':pogr,a"phicaUy bllll~rattler contain su rfa.ce i:rre,g~darh,j.'es, 0:1' ,lSper.~d,es~hnls Jand vaUeys in, ~:hc~olid surface ~ These are im per fcc·tions in the' bu.] k soUd. s surtace on a maeroscate, :Even however, on. a microscate (a~ atomic ,Ind subatomic levels), variat ions, in sur face' properties and characterist ic:s do
j

,e'K~s~,.,

feren~ crys,t.aUogr,a:phic planes results ,i.ndlf:feren.ces, in the electronic nature of the solid surface, m f' we ,go ,00~tep below t- e pa,.ckhlg 'the 110ml and 'Io.ok . 'iii' ,",1..-], .. " _._. d· _ ,"' , .. "- -'J. ",',"- - , ,A,~-"iF'·~'''''' ti .... .. ..y or e eetron ~:s:~r] unon on ..-1..," .", .. f'-'·" o··f' tne 00. l"d' ,~~, a~ tne e eetron .~ nsa e e tne :s,ur, .ace . 1....~,'. 0'1" the various ,DJt(,micplanes d~p,ieted :hl :ugul,e 3-,~ it is t he electrons inv,olved. in a" ooHd surface tha:~contribure ~JO it s 'bind:bt,8, [,.0' other ,9,oUd:s; to adsorbed speeies ~and. to lubricants" Therefore, the electron distribution o'm, he solid t surface is 0 r gre'&t importance, If' we ~ook a~ rhe e~ectroRicarrangement of the' solid surfaces we find ~JUi't there' are vari ations :in the distribudon.s of electron densities on Ute solid sur ... rru;e" For example, :in the upper' ,schem,wdc of' fi.s:ur:e' ,3,~91,we' see' the dhltr:ibu ..

The variation

~:natomlc packing indi,cilled in figur,e 3,·' for t.he three di f~

0,'

,Ij

('liO) surface sbould have ,B, higher. surface ,energy than Ute (~OO,)surface, ,Ind we see this is true for- tungsten and ~antalnm, Since' the re:nergy reQuir,ed to separate t 'V'C) atomic planes of' t.he materlal '1... 'III h L 'I~dl(h ., vanes wrut.~.~ cryst.ajll.opal:tJ.c orienUU.l0n m ~ne SO.J.~ ',: _:at '~s~ it ta ktes II _~ tess
,. ri, ru " " • i

"SUFII,At"OV

..... iI,l"""'L,~\!,~

f........ ,~'e,!, :'I,u U,II:~ face-cent --: '''I!.,>'~,!liJh!," ,itlV~J~Aii'Tii' ~.V' I"",,_:I!!O~V\O' or lII'h examnle :1'50 --Ad' elea :VJ. ,iIO!II~",·~"",·n,~'e:r""",: ""I]jl'~~:~"" ~v separate (lil) surfaces, than lit doe-s'~O cleave or separate (,I,10) surfaces), one :mi,sht ,llntici:pat:e that hell ;1 cry:stalUne selld is fractured, the fracture process takes :p~,aee along the 'w,ealtest cr'ystaUos;raphic planes Jn the' so~id 10 us
'",,n..Q, iJ\;;'a, ;:)j'Q!I~'li!,.llU. ,t""", i'\i6, .,--.-' '~-f
i,

for- a Iaee-cemered-cebic crystiO[ ~ one 'might ,8lJ1tiei:~:uJ:le that the fr,aJ'!tuFe or' eleavage would occur for ,3, 'br~U soHd. (:s,udlali diamond or s,iUcon) along ~e the (~:n 1)1 planes, the h:ig'h atomic d)ens,ity', low surface energy' p'~anes~The ~OW' surface e ,ew-gy means that these ,plan}!:! requ,in~ the least amoun~ of en'c'f,@Yto 8eporrate one pl,aJ:l1"e"'rnll4Il Mo't ber' hi Ute :mattriat~ ~ In fact." U1i.s ls physmcaH,yobserved, The industrial cutting of d~,a,m,lorwds, jew,e~ry' and infor
dustrial cutdnl t..o1OI! relies very' hea,vily on ~~ fracmre -e
u ~.' -'0- "0---rd' - ':Ii
''f:il]!i'll!i;m-,I ,.~ .~, . ,"

:watlll.ra~ iamond along the cleavage plane, 'which. is the' (:11m,) surface in. ~'he d
'~'f'-OIj"i;B_;"o.g'n- ~UI ~'~ tered-eebic
~
,I,
~~~~~t ' ~~,

Or'

c eavage of the

'iI"'ill'm 'CC '='~l. ..',!IJ~ I~I.'~,~-.: -iI-

~t

jil'i'r-'~
~'f!

Clea,vlIge Planes
The p~arne8 along whi1ch ,clea,vl1tG,'e: occurs in 'various, materials are presented in table 3 -mv fo:r 'va.ria,us: stru,c~ure-s: diamond. (diamond" ~Ujjoon", and ger',.., m,anillnn]I~,"zinc ble[1ld metal old des ~ la:Y'ei ~a:t:' (:m;olybdenum disulfide', i.ce
t

TA:BLE. 3~IV, -,'fllMARY

Cl.EAVAGE ,AND SLlP PLANES FO'R VARIOUS, SULIDS,

StruCUIIDre

- ,;! Na,te:ri.a~,

urn
HIll
A._' ~ ~a~lill!mlirJj~,~, s.3,p~~~ir.,.e)'icr,?~.idil~.IIrn.llhil: ..1.0.' ')-:, t S:~02(q.u~ru::~ fused ~d~~)~ I' ,~!l~SOiU":(tItpy "0:1

,IkO~T~O,i

,P:fOftt!O'Un~,
.I!~I~\

,~~,

c",.,AI;,. ~-'I!J'Y!III'1;;!-~!!

V'i"i;

".:k'l! .... iI"',..1I ... 'iiC1,UI'!s.!'~ ,Iu..,."

-F,~ L"':C'f. :: . il:1_; '1(-' .. -I't 'fb:S ..M I·:-·~ ...-'_-.\ c ,1'-. :.110 ' 0-' ." ' AgiC"-'-1 ,;,", '
'ii..~ . .;~!~,,,,, 'Ih.~. n .L;,f;t' ;)J~~,\ '-NCo ,i£l r
. [ -",' '1'I', ' 1',-

C-!

HOO····1J l~' ,,'jJ

lP~ck,cd, (,11 .~'"P•.)

H~x.a;!on:ail,Clo~

,Z n,
''1j'" ,II:B,!
a, ~

rio.,iIII·

C-, ··it " -0lt' Z'·

r"-lI.!i:~1/;...-'.,

r"'dl

j;

'ft,,,,, ~i'

;fl' .....

~II~

t" ~"",r'~~_ ~'i' 'N". -a!. ~ U U Ii' .f\i;.1o T -'n° M- C',' dl M-"'0 W··:-,'.'
t

'

·C··:~· -r,~
Ul1}

'~

.•

..

••

'~'

(J. ~~

<

.... II
':.

il(:~ .
II

IJ
.

~,'. '

111 ,
,~fV\ 'U\iI'!U'

ifJ\'OO'" :.. 0.

T,'~~m~ra.tureJK.
ftgUf,t J'~/.t,=In.t,imic stmlfgt:h'
jram'
HertxiaJ!l ftflctg"l~' t:~~ ~"tt:~acuum~" (J.~f1ffl ,~~d~rgtJe~,,~:nd'...oJfderl' di£plfI:Cl't..re,0' '.... f1 tr~/l(J'm'Qd(ln IfJt 1"=,84'6,1(;,itll whitl;~ 8,~~ckm,'I ,SlOt ,lef:nMmRl.JJQss r:n'lo ,diMJ,dt;nd Jllte in I~ermm' ,mvd~~"ju'tBrj' ,;ri;l~m e'fecti~;r diM)lyje;rea ,at o:lll,~pmili~_reM: ('mf;, ,14), is

rif c-tySli1:tli'ne

,llIm'd amqrphCHB,/QI'ms

0/ Si01,

~t(J'

lflke'n

and ~ as a conseouence with an increase ,in temeerarore .. there 1: ,--e- ~~'~tl-~ls Y .• l.~ ~ , -_._, -.~" ",' " .. ,., _... ,,' f.-.... , , ,chan ee observed i:ij1, t_1~ _ i,~~,J~n,~.j',t'> treneeh ,n f ,., fused ,~'~'m,.n.'rT"!llh~u,! ~~~l',t~~'~ he s ~\ " !'."Il~ v' r ' ~I There ls ,a,tr-ans,f~):rma'nion 'in, the C-l"Js~anine' form o:f quanz, whic:h is, COlD '" m,om,~'y' err-ed to as the ,alpha. ..b eta tr,ans:formadon~, at about. 8,SOK., As [hat ref transformstion :is, approached, there Is a marked decrease bi the hltrinsic
f,)'
c """
..-J~I _ • _ _ _ ~,~

crystalline

structure

(:flS. 3",11 )1" These panes are' absent in. the fused sUica
~~I~_ ~~~__;.~~

~!Jl

r,~

'¥~III~I~,

'Y'~

~,~!

,I~~.

~JgJ

,I~

•.

ri;ll"I~'

~HiI

strength 0 f the' material w~th rhe increased mo bility of atoms associated with. the act ual cryst.al transforraatio n ~ AFb!f the quart z goes through the trensformarion there is a;gain. an increase in the' ~mtrl,nsic strength of the quartz in the beta farm, associated with Ule new cn/s"U:d street ure that is formed. The :bdleren~~weakness occurs only in, the trans formation re,iton,~ 'whef',e:the 'Cf:u31tlg}e: in struct nre :is t aliring plaee, Tbe structure change gives, rise to a very l~n'leamount of 1110l1Ui~y in ,.' atoms and 'perm'wtsa much greater hie'
h" '. - '. ;,', - 'l!.,

.. '~ 1 .' .II' d ,,",.4 .'.' '. · t '..' ease Q f is'he:arlng in rne so ] :Iu,all. a reaueu- '. on m u- s u - t unate :IDrmsic st reng~ ;;.' The' data of .6guT'e 3- I I were 0btained :in fa va.cuu.m environmene ~ wh,ieh ~I f' ~ ~ E' • L, ~I • m rasses an 1111 eresu.n:g point in tne st U'uY 0:: SOd'_;'d-. materia ],S, ,~O:r '~:rllpO~O:glca~, t appH,cations. The environment in which the marerial find~ '~tself is, extremely '~m,mOJ-c~,ant_ ince,_ it eaa b~va a mar ked influence ~it"iil ~iE-.,~ meehani beh ~1.v~i'f:ii-1(' ,II¥. . ~ ~~ s ~-~~II~ ~~~ 1l'i;.',""U I Wi... of saUd surfaces, FOf' eqmp~e ~the si ,]Icondio,dde:~, ,either in dlC fused, sll lea form or In the Quartz: :f;or,m,~is extr,eme'ly sens:i£,ive ~IOmoisture. The presence of adsorbed, 'wales on the surface of either g,-u~utz.Of' fused si nea can markedly alter its mechanical behavior; therefore, H rus extremely ~.m:po:r~,ant :inn~ea.surinl fundamenral properties to centro 1rhe environment, whether 1.1, be (lin ~dnoon dioxide or ot her materials, From a basic unders:ta.nd:in,g, -0 f the nature Q r bo:ocUng, in ,soUdsand properties. such as cohesive energies iBS, are presented in table ,3,-1 one, can ~ ~a~cu:~~tehe ,act ua~ st reng~hs, an d ma.n'y other m'ecban:ical p,r,o:~:u~:rUes scUd t of :m,at!eria'~s ased on atomic bondlng, that is ~the ,a,t,o'nl~C theory of :mat~da~8 b can be used. b) calculate the mechanics , behavior and properties of solids as was done :for theoretical cleavage and shear Sit rength s (:I ables ,].,:y- and .3'"VI),"
~I~ ,_
0;..

g._

,u,JIj,~

,_,'t.lf!!ooo ....

VI~

'Ii.Uo;..

~~III~IIII

r;;g,~ ,"'"'Ai[

,,"-C

_ !!iVI

:1,,$1,

r,_ ,__ ':_ '_' ,_c, -rJi.. ·I-. Before the mid-l'9S0"s one eoutd talk in (em'S ' t)'f vacancies _ and ~n~,ersUi~ 1:11 iah, so~id surfaces and dr a w schematic Idi,'iltuam~ such as those' ~n :ng:ures,,3... and. 3,- [3, to depict sehemat ~cany what the-se defects looked like" 12 iL!..iIIi1t_,_' no "O'na h~.d "!!ii""~--'iilill~l'\1 (1'e- -- one' _ 0:f-;- th - - - d'..,:i:- - ;;-'i:' and W v.E1_,_-' d-I--A'iiiiili" ., - - -- rIl,_:'es~:_e.wleCIL\~,.a ,._-I~: J'y - r,,,,~ tnIlUiu ,.,.,,;,,!iilIU . ~:~UQII,Wiseen ferences 1',-, .heir. existence f,rom, ,In ...;Ii! 1"- --.' ,experUll "en t_ , measu'1-'--'rements-.". '. 'W'" ILl ' , -;'., .. .- '___ Lot eu ":')":; . "--f'''' mrect ..... - ". _. '.', - ~ a _'..',",.,... n the advent of the Fl M:,t however i.t became posslble to see tt he-s€: efects on ,3 d eo- ..IIL' .. ""U rface -Th·-- p([",e.se~,1".e.'"of 'a~'" .- 5 In ~ot" d':, ,~" 'Ii" ,it' . - -' . n'e' ,' ~.' }Iidl . ~(lm_. a_ 1. .. U ~'~',""" ~ 't· ,~ ',": ,: 1,e, site {t!,- h as ~,~Jl1,g SI ..e \,~U!C" ;"
_ ,_.,_ ,_,~~,_ ._'_' '_' -',.,--: .... 'J " __ .'. '".' ,__ " I.,' ,[ ., __
_l '_",._: ],

---

I'i--

.:.

"--

~'II

.I

,,__ ',':

tnev ate lo.... I -!l·t ·..... TY\i'II'II~' in the ri.1IuWt!l .' _' surface ated the,. bulk ,0' ',.,W th material ~ l," Y-'~ 11" ~""'~:'i·d·· ~ ~, ~:W, . ... :F~,gure,3,-1.4 shows a fi.e~dion :m,~.crogr~phwith ,8 vlacancy ~na soli d surface, This p'ho~om:icfo,gFa,pn W2l$ taken b~,.Professor Muller and some of his col ... l (;' J11,e") . rne f in L,_e ide h ,'eagues, I~re,;".,l ~i.TI.., V',acan.cy Ul th iSOlid sur f' 1,· race ~'S, very eYl,, __ nt; '.. j,S the It ht:-,II..- s,pot , " . th .' ,llllJoulmu:Jogra,)),rn 'IlL.., 'W~ ' .. -'. -,t.,.. ' "'.,' , ,,' __~lC!l!!o, '.. In ,Ie .I!.. , i' i . !", I __ IlJefe' we see I,u'e row·s,"iW O.1j atom,s, '(il'h" e '.~, '1t'u!L,,"'~'.-' ~:,.:>t., ...). ." '",!I,~,~~epo,"~" If the ,',iII':'" - w-er )', ," sent ,. "~,,, , loeati 101il ·"-l~- of :t'-h'-e S,lIU'"'-":-" s Jj _ ,,,' e (110m e presen., Ul that ,oca. ,il all 0, Ii. - ;, '- aoe,
~ -·IJ. - -:-

"'. • • il 'k"' '" f~ '" h :~nt.'e~rs:u.tJawS suesntunona '"[ atoms or tne presence 0·, vacancies wnere ,i or .si:n,sl e!atom, is involved) ,are eommonlv referred to as pc)wntdefects, because
iII;.,
i

O}!

',RJIio;!W;"

_I~

,a,

--

!.;Ii

(i,,n,A~

,....

'IIii!'Ul!W;

. '!QI[

'M~ UJJ.l~,

_~~IIIIIJ.,

eI.... A'F ~ U\l

II

;iJj, tLb·,!,~

J. '_

·1jJ..II1ir, 'll _

il

,-

I-

I-C.

wOI!I~d cOIil:sistent ,0f nlWS o:f

while'

51,pOt.S, ~

Va can~:y,.......... \

·.-t .' - ,t-)'~ti·.A1 " ··:t--,··-- " .'. '-b-tii-I'-" tl .'."-I' .'-",. ·.U -. S':"S. _D,.lona: or, I" D_ers_-I __AI A'.. _o.ms ..

,In reference to fi gures ,3,-12and 3,- t3,~the presence 0 f impurity atoms ill the forms Qf s'Ub~thution,d and interst ~d.al,atoms was discussed, WheJ,e small co:nc~ntFadons' of 'im:p'LJU~by ma.y be' present in elemental :mel,al ~ rhat impud~ y 0:0 'the sur face can ~ake up ;a ,po\si~ rlep] a.cing, one' of the, surface ion ate ms of the metal ~ such an ,mtom 'would. be called a su,bs:ti't 1!1~:iclna~im:puri.ty : atom (:fig~, :3~ 1:5 (a»)~'The i,m,pur'it y can also fit into an huerr:n hial sit e, as ~rJ.""
.A'~:""~I'i' ".A ,:II I ,jf-iiau're " !yj!"",,gr,~,!I;lU iIi,1 ,~,~~ __ '!i;r "

n "J 'I ,J- lb' -)' T' h eo,.:.;~~ of 'I~'h--'~ ~ '- . n,i!iIj'lIPti eu,Iar I' Tiii'i,n~'~'f~~tvate--- whet': her ".iII.1! 1ioi"'LiII i ~[~ ' -i...... 'nI" '" in a substitutional or' ,1:11 jnterstitial posh ion" 'can,have' a, profound in tlUe'IlIC:e on t.he. nat ure of the solid surface and nbc lattice flC'gist.ry :imt:tutJm saUd SUI"'face ~ [f the atom I'S J:lehu:ively la,rge (i,arser' than the ho!H atoms which. sur,;:,' __

,.Ii•

'---, ,_,_'.... ~~~'Ii.<

.. '

Ij,_ '_"'"

~~~.

_ ~.I!i,;;<_~~_

,ill, _

U,I!Ii

!!i;;o~,

round '~t), causes a bulsing or st.rain in U

must aceo'mI modate U:" it undergees some 'dil'n,8e ~ Wltb. the interst ~tiJalatom, the degree 0", bondi'ng no t he hl~,erstiHa] atom (by the par-etU atoms j,n the

tm..e crys:tal lattiee, S\ince the' la'nice

dis; lee B ti on. "

$cr1ew

'\

s, 8, oys, an d"O[ h er S()'']"0' L., materials: hence, dlslocanons of 'the ~:hl:e type and the screw type are irnporf hn d ae ~1·,4 'l,- d-" 1" t ant. dome m a.y!ec', l L' at b eYlon.·:,t.h SO~l~ s nrtace nseu ~- ,W:!;oeat sons are 0·'f _ ~n,i aimal importance, In tt r ibolngi cal st ud:~e~,.~ however ~ d ~.doca~ can ions . .....-,'-:--. -- it, - --)\1' :".-. -, a ~,I, , ,} ..U iF' e,s but ...a·mts oeli.; ur f1lIOI~ Or.h." ,~,!Dl '.- '31'1-' QIE' .,~'NI'!DV surfa , ..... U - al (l'O' in the ~11Ii,~,'L,-r-]' ,m..... In...... th emselves, Organic nubdcating :Structures do have crysttd ~irn to I[ hem, and ~ty wit h th ~:I cryst al lin rul~y can be associated ihe presence: of dislocat iQn defect s . A .... -" .-. ,'~ ·,·F' -':~.'." ~"~, ..:; '--, II'I-,-A In ",l~ure "-,"" __ , ".'h" ,~n ex,am,p~e.ow InlS lS p.reS~rtIi~e'IU, ~" :r':" :" ,:.' '-3' "'0:1 'I whiH:,.' ,~s an ::·":0': -"''',.,' Of, ,lnary
"-:,,-,,-,-',-,',

'I",1"1 tnbo 'I ogu:::a:systems, ~"e concern IS lb l svst h . "

+.
.' , _.. : ",. 1.····' "'\-.~,-.~..

•. . wl[ '-fJn,meta
:-;--:'
1 .-",,'

•.

[','

.- ~-~

'_"','

,-_",

"

,"

····1

!['!

if,

'.

,;i:li~

IU,.~,

r;II/Ii",o .. : -

'.

..J! ... 1.

iI

W,llJI. ,-"

,!!;,o

.,

'I~,~

"I;'

','-'

F.~§;Ur:f

J ~2().

.P'h'f}.ilrlild~t:O:gropfl 101 ptJ,ojJi.~' ,cry.£tal

,(}i\il$

Qf which g're'w

sCFe'w dlsi(}.i[;{I'S,rlJl1'

(ref" 1'1),.

'! iLt,i'I;

lL

.,Ji."

I,
II

ii!!!',!",lt.i!'llll!" ~ IU"'II!!;:!I!I.

;U.

ST,.;!::
!

,m,
--

- - ~ --

densities are, however ~more difficult to remove ,am_d the tem"Jf~~" n~r:i!iI.tu'!I:"'~~ reauired u~ ~ som,I~'·n·~,~aJL '~d ~ il hieher ~,Jl.!J~ '_
Il,~' 0,_, __ ~~I .~
~-~.~._._,_~

fac~s,; The dislocation

{j

!I;.:.._,

,Oir,iit!;

~-vl ..

~.J.!;~-ill!tii

Plgu're 3... stage 2'1] shows that the" di:s:tocado-n.density is 'reduced in the ,23~, .200I'~' to '00 C region ~ In practlcal tri:bolo,~i,c'al ;sys"em 51 temperat ures M :~,igh as 200 ~ C ,a~:',e: '0 bserved in ]~brieated :s"st,etIIS, 'bu~ the h'is:h,er end of' :5Utg,e 2. {'sOO C) m:fOf OC'C:Ul~only in solid Iubricated. systems or in s,yst:euls ~ 'where there is", no ]ubricatlon 0 .e..~ where dle surfaces are ttU'lning dry), In
t,

,.'L.,.-_, .. ,

'iLl..l ,,11I.ose,·.·'t'Ui'l ~ous I' 'tL,.·'....:II,·',.l".· .. ,·'t:·,·· "_ ..,, _ -.. ..,!rllllo,n can- i!-.,·-_·~:lI' '.: -rl,:,-,,,··,"Al· ..e.r;a,uwy" 5l!, ...·_"t,··· .. ··..· . ~ we ulS aCR,d.onconeen ~ '- ,-,," .',ue r-euUctu CODJSh,
.c,

III!

t'hey are adjacenr [0 grain (or single 'crys~al) boundaries wtdch would teth "i' 'h aol 'I'" ~I'd separate '[ iem f rrom :1,.'d'" racent grains ~n ~te po Y-C:rysta.l me souc ;t:lc~!1 , Ag' "'a""- e '.'. ·' ,~.~,:. 1!J)",.iun. ~r.rue,j v",""" uf nl "-~, ~',,' "011,' y', ,gl~lI:.l G·'rq,·iin" ~n"I' -- da "I -c n('un'~'~'" ·'i -, nei:l.f "illy ,g",., 'fiir~,.... ~w, 1n'ib'.,ol ,u: ' ],'l!;rg,1I. :oJ,!WII r w, ~ ... :ea'., Although m:'bey are extremely importaru frequenm:t:y very H~r]e attenrion is id '\-., d' .~., ll' '.~' paid to them ano to t~,en' re'ch slwgn:h-]cance ., tne b h .. 10(' so 'l"d surraces. In iii.. benavior r L~ f A,typical grain boo n:dar)!'on a mo I.)dbden'Um. metal su rfaee is shown in figure .3r,2,1 There' are basica hree grains slli1c)wn in t he pho~om:icro',gr8,ph I~JI .r,-;:·O·IIIIti"e' '1' 2--:.7': W' ,:.if·!lL.1 ,"]; sr aln bound ,a,F J' "'Ii"o l",g ._ ~I~'b the ·t'h·' r senaratine ree iadividual ,1:;.Fi;;II.ln"" '. ~WQ ",.IIi·, J'''",', .h..W.~ g, ' ..•.... Ii I,th, '. . '-', The vler:y presence of the 'boundary indicates thaI the orlenrations of the adjace'n~ grains a~ the' surface are different, If this ·we.renot so, "0 gra;'in boun darv 'W' ~d'" n "AISA-lil'iIiIi' ~., .'e~'!i.iLm.t-'w.>" h the gr,oln ,~u.the UiiI"!Ijj"ij$i!:r- It''u,rll'O~w nn 1!':""'Iif'iI, lJUI" j _vLb·.e b t"":r .... cQ,r v-<:1!Ii - ole '.iIi" _'.1.1, ,',-.~.', l.U:' . It--........ of phot om h:ro-gr,ap:h~s II (:~l) sur face t he two adjacent grains J t he on e to' 1. 'I h~ right and t he one run tb e ower port ion '0 f the' photemicrogra ph -0 f II" ">" J>" . - ---"[" . ·t'·' ,- ~ '.~ -".' " 't' -, .Ia.: ide n e~ess] ,y, m " , have diffeer1en I 0 Flel1ll~:l,lons, .be l'cause . r I.h'ey h - d 1. ::, ern_It" ea US~ __- ,n. , orient atioas to, t he' upper gr'ain ~here W',()IU ld be no bo,unda.ry
i

'(Io.~~1

,,,.,~.'

;g

=.

ny' ~
,I!;~,"IIi..

!li.&11 III· ,

"l("ll'

til

l. .'!Ii.

'!;.!.

O'-';gj,'~Iii'!I'~

!;JIg

R'

''''Ifij

'-I'

.....

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:"

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Grai n boundaries can ,deve-~opwit h metals In the sol idiflcat ion pr-ocess.. They are nucleated by stresses, impurities, and. all sorts of things whi.c·htend
'~"""est 1['0 Y ~0 de
~"I"

he "gr;'Ii/ - b-' "'0"1"1 d!..~.; it.. _ n 1.'0" • om ere eraeh 'i fii'''ure , lIiIIi~n '~:.~!' aries ....n, 1!iJ', ~",,_,; 1.,/a _':'~ be seen "U e ~.J~:' iL.[o: ' " 'i.,::: '~,-!f4!. WOI,'., 3·-28, which is a. field ion mlcrograph of ,8 tungst.Clrnsurface sho,win:g,.a gr,ain boundary runni ng through the t ip The grain bou n a,ar), is, located j ust below
·_·1IiiIi";:!I! L",,'

ct '.1,,,,,,: P'~ 'U

~.fii... U If

0' f
•...•

unif .orm rt.;;.. " '('" --,~ 'h ".,'", ,,-·t· nmic urn ,"_-'"nomogeneous b enav tor o.f th'·e mater 'ru' 'I A·'" ar OITn ~a". :_ _JI]..
'::lIl!I" --c ,-,

.·.L

[I ~IL:.

1 .....

H,

"",:,j

II;'Ij Irn ~~,

I .•.:

f"II ,I,·I,

Pi!

IIII~ [!:;i - . _

,.

.liI' ~'!Ii ~~'JI'"" .• =. _' l

0·:' .rI' -·~tefi-~ c~ ".'1' .

.. t

l~i

"'!,.

~-

...

--~~ !liilllilili -

~d'-'~d--r"m' --tIl- ~'li ~ ..• c~·,n.... -._ n .....r«l' . -T1t(J;:.

I I-

_.

.'

.Pl,.,.... iI'

. ena', _~ _ . ... ='!!I!'

em· ,en'- -. .-, 'Y. 11- .13 -~-t5·""if'··' "·-·0 ... ... _
.1 ~ ~.

ton,a'' '
-.

,.

,1~1Il "
•~-

<!.....

a/"o:y. A' ~.~ ill D,.

-

._

than ordered, 'we'have what is commoml'~f'referred to as a ,diso'rder-ed, strue .. , mre (nl,~ -3:2(b»", The 'b'~ackeireles ef the' solute atoms are' in random l~h!5 ]'.. relative to the' pos:ido:ns, of the sol vent atoms; dley do n.o~,take up a regular r[egis.try rnnt _ crystal lattice. The :pbysic-al pr'operdes ~Ifthese two pa.r~'icula-r e materials are :m,lrk,edly djJrefe:n~,," For example, hardness in the' Ico'pper-g[o:id gY5lem, is di,ffe-fen~. 'OF the ordered copp-er ..gold ,aU.oY$, Cu,Au and. [Cn,!A.u
Ehlstic modulus as 'weUas other mechanical prope,ni,es are also i-nn,uenced b~!' o,rdering~ 1:11 bi:nm-y' ~y:s:tem$ the ordering exists over a particular tem llr·~.~r[a.rture n:UIQP'"U',W) sformat ~.oncain occur as it does for cru~naUoO'l"'a'I'lhic ,. ,. ,~l -~. .
J.~

.3 -l2{a) 'w,here U11e' ute atoms take' up regular posir ~ons in U~e'trySUtl lattice sol , relati ve £0 those po snlons of 'nile solvent atoms; an. ordered c~ys'nano.gr,a,p:tdc struct ure theretore resuIDt , TIle dark, [tirc~es repres'ent:ing, the solvent take up' s n:lular' peri,oait posirions throughou.t t.be crystal]: :~a't,tioe' i:n: relation ~O' the w '. ~) e: L ~ .rI ,. . so 1vent atoms il([,open Clim)~~le-s~" _ the ennre~ ,amq - sur ~ace 10'r tne ,S-Odu W,S : represented by that pau.m,clldar ordered struet u,r~~ Wbe'D. the atoms are distorted in a surface I,a.y[er and ~ake U'(J' POS"dODSr 'whic'b are random rather

-:iI!.. .. ~,-' ·r· - th diso AI:]·· "~ tnan- n :~sror It ,I,eI' tsor d erea a ,oys, or C' 'A"iU arruu.~ ,ur A U., ·u > . .AI C·"·~,
I ..

[~¥tp.

•.

,_..

,".'

_"

".'

_ .....

..

..

....

~.

strut'! ures wherein one transforms :from an ordered ~o a disordered state ~ M.os~ bina'f,- metallic s,ystems show u'ansfOf,m,aJiti()n from ordered to diso[idJe:red, at some s[:pecinc temperature as Indicated in figures ,3-32/(a], and fk) ,;--J"' Qm,p~n,ii" 0' !l!.JlJ!iII,~ tra·n· form . illv1;"I; ,'IiFA'm-..... ;,.f"I;' d~" ~d: '\v:... A·"" 0 -,-,---"",-:- U;'ii'i ... , . . . V. 0, or dered ,["on;; ~ .~~~Y',1i;_jfiI'r ......-i ..er~ .v state is, a [change in the' mechanical behavior of t.he' materials: [3JJ}lY m[ccbaruca] change, in tum, affects tr~'bo]ogi(~'a]behJav:ioF"i Such, things ,1lS 'f:ricdon and wear are ~:n-nue:r.u;~dy th,e order ldiso:rder reacHoD; experhnenb
JU,~ ,t.'1Ii., ~"
iI:!
~I.

;g,1t ,;billl

,1,1,

,~

I,,

,g.J,J

'!;t't"i;~..

[ol[j,

Jt!3n;

¥ ,IW

,t'!;I,11 ~L[~~!

data in the lit P"1t"!'JI'~"~'!:r"a:u..[~~~~~'~]';'"[h··a.d' have th th J!:-', Uu!\.?~ ,~IX'~io1'1t',· 11 To the tribol,o,lwst~ it ma'y' appear' that the mechanical properties are' cau;s,o; . t h 'I.. ~ al b h . ,. - f· h owever ~ a m1ilC'~,mOire b Ins ~:ecnanges m th tnoo 1-rOgl,c«a:··e_,.a,vior; In ,'.fu::t, ,.~ se it,. I :fun.dam,ental property ~the atomic arrengemem of tbe:' sol ute ,rela,dv,e' to the
. A. g ,iI.. . JIW~ ii. fliir.1 g~ U. ,~, 1IiP-;Q.IIJ_.pflJ!
.kIj~ ~ ~
~'!~I~'

~I+

lib

lI,~

~,~A~,

iIi,~

sol vent atoms b, responsible for the mechanical prope:rt'y' change, 'which in tum is, reflected hI tri'bological beil;;l'vior'., The diffen~"oe between an. ordered and. disordered crystaJ~ine state of :ma~,[tFbil the $(),iid surfaee can 'be seen bl the pho'(omi,lcrognlp'h in, .filuroe on ,3,~3l, This :ws a fi.eld ion mi,crogr8JJph for [a, pbJti_n1Jm~o:ba~t ano;y'~ The 'pl!a;t~:nnm""'oobfdt {P~'CO'~I noy 'which 'C(Jlnhdlls, ,SO atom:ic percent 'ph1.d:n um a and ,SO atomic percent, oo'bai~t.~ undergoes an order/disQrder transfcrmatlen.
I,
<}

~7]

l~

!;{l'

Ji.'!i

1[i'~,~C!

HiEAMN('i

,Z ::ii,

., ... ~

mOLING

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I

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::!b

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,4
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lE~PER!i\TilJRE O~ 'INDI~

gc
Iltmugh m:el't,rn;g; pgi~t

F;gUt-e
1 i!.lG=Jl

t ,~,('

j ~3J,'''''D,f/Jilsm~ '
~~

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'l'_.iil'lIo_ I

~I ,alYSeJ;j'

to'

,tlfiifl

,from

intJium' ~rJ~'

'rJ

iII'iii't:iOml- {"-r.' Ii II, O~''IJl

cooled ",if the' concensrarion of' that particular spectes exceeds me :801ubility
i _n
~'~L
IU UW "", ~

devoid of the IOXyg)e1], that is, present above the meldng pohl~ (fig,,. 3,..].5) .. Thus dissolved. eJI memtal species, present on a, metai sur facecs ,- b~"....--,' ex, .. ,,, -; -~',VII. :sso~_:e ele - -: tal :-.--.._,e 1ace lean __ eoom,e -," iil~I"O:11'lifU'ilili!!fj:'iilll"i'i:iI'tliOand y- ~~~v~,';'-'~~~~~ dissolve m'lIl'Ii ~'h'~.1- ~~'!'111~ '1 Y:L,~, W'·,~,L"Ii!It';~, ,:'Nl",jlliin ~J~., Il ,1' '-me obile ~ ,,., ~'U',IJ u~· _:,,~,~ l_:~'~~,...: ~~M ,~",. l~,~
,C" ,-', .. -_.-;, . ",-, , - .-:.. " :-,,.~ ...

temperatures to 2'OO~ C',. The process :~sreversible ,a.nd~,'if the :indium, Ws coo~ed,to :[,20~C',~ ,oxygen w'Ou~td t,ile a~a:in Se,B[1egmte on the saUd surface and rhus leave the '~n,dium, lU·-rB!C~ rich 'in ,oxy,gen and tbe bulk: of the 'indium, ~
l1'li; 'R '.Il!l!, ft'TI~~~ ,~tt~,~l,,~t

t he 'm"e~~ potnr, the (~xygen'cunO~nlf,a~ is; very ing i,on

~,OW' and

:re-rn,ains low at

,g.~~ : ' __

'W:

.',.

i!

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,-,~,,' segreg:a)~

.... -'f 1O'n. 0,.

tS;..··

~, '.. ,~sS:o ",O§",II 1l.il.lte.. """'. s,p-ec~es, itt... t IS d-'" '.' '1 v~ Il,JiIj,a",
ShUs'dOIll
';!i'-'-'

",--

tb In,w:~e

,-- 'I',i!;,en ,m,o, !I'-

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For example, iJ sugar is dissolved in water and the water' ls heaJt~,~ a b:igh.'er oonlcen~ ration IQ'f IUgfU can 'be dissol ved at elevated t.em,peraullus than at room, 'ternper am re, As, the, tern perat ure ls I~)wered" however, '~he :sugar C:Tjs.taJ~i.z;es ut of the so udoll €:if nuelel are a v',ailable:) because the sol ution o is essent ~;aUysupersat anij! 00 ~ In essence the indium 0 f flo,ure ],..15 'in, dlt~ 1:1 moben state is. supersaturated w~th loxYIf:n and ~'when cooling to the solid state, segregation takes p~ace'at the surface. The data, -of' 'figu:re 3~3S only indicate t.h,9Jt the' Qx,y.B,iell concentrates on the surface and that t hen': is, less on ~be surface :i:nthe mo~~en, :!U alt,e' than t here Is w;ben' the_. run- ~l'Ii,~ft'I; ~i''''in '_'Ilr':a 11;"0'· ];d. Th J!Jl' ]"iI1!, how mtu~~, ';;'il'!, present If -, ,,_,,__ !Im,~,' _ U, ill.. "_1~ : ~ .. -, , IS' an. extn::Ln.e,~y :sm,a.I~,ccneeetranon .0'·f": ,-',",1,'ute -. on-' ,--,'I!...- sur face0"if tr e- "" ,~ t --h' :!:iOI'-' mere ~', ...,-- _.,-,..-- . -,-1 ,- - '-:-] '--."-". _.. ,":- -"""."- so me - , 'ace it" ., '''L, I ~I vent us s~g.n,h,lC:lnce:n~,unponanee ,~n tnl.Wo_ogy may berel ,a,ttvewY m:~n~ma~,. a .A ., ~' re ., ill •• ~f'the" data, w:tdth are isotherms forcarbon segregation on an iron (100)'
1
l

'-T'-h':': '1$, an~!iQ,gOlllS - - """"~ " ". to ."IS _.0

on the solid surface.

me

iii'li... _.,

. '!if"

.-

,,--·11 ,-,AI' - ,-, .. -., .. I" .. - '. ,tnvo.~v~y, In supersaturatrng , a 'l~"~1 IqU1IU"
" -

·~,~,Ih~':Ij~

lJ,i~

~ ..

!i1!'t""ll'~'~ ~IIiJAlIll""!p.

"

(fII1(I;i!!idll'~';;~ii'io, ,~~~~"l!.l!I~JIIU~W,~

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Jl..-zl,

. III 1Iir.~~Ji"'._".'
1

,.

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.,

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'is,
Am~t!lfi't ,o:if '~.,
,~' jg,,;j',.
'=

,/~cergrr(1fr~iQr o~~~tr'(l.d()~ r

F~ 1't' (ll~(J~,

€d ~iJJ/~ri('Um_ fu'adiOlJ' q/ b~'k ~M~lj',',lia'ilon, iil'

data In :fig:O!'c! ), ..,3,8aglin serve to stress the i:m,p(l'rb.1D,lce ,of~m)a:Uconcentrations ,of'i'm,pu.rity atoms 0'.0 the behavior ofsolid surfaces .. 'Whil,e the rna] orjty of the, grain bOUJnda:rJ h,~,elf Is subsurface, the grawn bound,airY' do es termmate taU the sur face As a, conseqeence, tbe coaeentra ~ tions rene-(~ed i,n figure 3,,,,38,arc '(J':O the surface' in the region o f the grain boundary, This increased or enhanced concentration of the im'pnr~~yatom l:!ll the graln 'boundary re,l~danaffects the tdbo,'lOidcal beha vior .-; r example, o
,8, :m,o:rUJ;~a'Yef.,The
a,

of'

rubbin U.I
I

lyly

iOi It \e lllilil

he ~u'·'r
rlJ
f'

:,go("~
1 ~~~

t·

0.'"

'IJ'II ~1I1~ '. ~ ~ ~~~

~,dJl'iIH,~,~£"r,n'~!f': ~ 1It'1!,. ~,~l!ltr

gt~[., ~iI;P.~

~U

centrated ~nthe' gr,ain 'bcMlllnda!'lite~s tc become smeared out or rubbed a(r03,'S the entire sur face. Lrh~ySi~fV~ as! reservoirs for t'he :im:purity w:hicb ls present in '{hie bulk. This, can be desirable, ,8JS ~m. Ule case 0:[ '~leUur.huTI, M.d iron: teUuriu.m reduces the adhesion and, friction of iron. However ~ it, can be uruie:dr,a.ble,,, as; in •he case (If alumm um and iron:: aluminum increases b oth adb,esjlon ,and friction fer iron (see dw:scuss]o:n,g, in chs ~ oS and 6)", U':sinl ~'he,at,om probe in, con,jun(iUon with '(he' FIM (~descr'i"bedin. d,eud~in (;11,.2)" T'song was able to iden.t.1,:fy' the segraden to pain boundaries of , chromium in ~ ,4~, $ud "less steel ~ 'he established t halt not ord,:y do, 0 nonmetl,Ui,lc' impurities segregate ~Ol,~awn boundaries of metallic sy;s~,em:sbu~ that even metallic components ~scgn:lwt.leto grwn. bonndaries in metal '~O metal :s,y;sf,ems (fief~ :21)~ Some of ~:h,e a, obtained by N g: and Tseng art' da-~ presented. in table 3,-,V l, I

~,~'lr. face c:-~n-Ic-~'II'lllil'iDi' 't- 'L,,-.. materi 11~

': 1iiI'~1IW G ~~IY~. 1~ll~"~'

~I] ~~~,

eon ~
~I~ ,

WIO

(thesolid surface] and an atom associated with. the' adsorbate (the adsorbing specii,es)are separat ed, There ]lSI fform the merg~ldlagra'm; an optimum distance where -'~heeli.l,er,g:y a~soej,ated with bonding occurs, This ~-s inner the seet ~~'n,n.'f',,,], 'w~'~'h-,', I~ l';:''" ~ eenera fr'",,~ 1;\1 - W't1,'Ni ...,,. '~i~'t "0- Jni~,n.f :hl~'~r-section, s I i >0 -- ~,~, ~'h' iIIJJ'IU- J!,JU~, lY
i,

;;.'!!","""I~,:II'U',

,----

the' equ-iHbri.um bind~n8~ en~rgy ,3J_ssoclaterd with, the bonding 0" an adsorbed ',i,'IJ..", "'~"~d'- :sur'-'f~" , 'if"t ,", ia, i LUlc~~o,n1, 'L.._li'~, ,,'11.Ie' 'Ii",Sio'rlib,'· 'aud-:_ th' e' , ace., .it IS 'f~; ,- , ;', 0 ~Il,~ h -d' -,' -, .en1i, ' 'f' SpeclIC5. Wlbw ,a,SOd ~,',
-.' c-

'!;,;I'

I~,

,....

iII!iI,IIo""," ~"i;e.iJl'!W,

)I,~

,.,

!!!I!J,IJ"

_""!!j.",,

_"

--

"

aasor bate
,..,:I, .--:' :t.., .. '

. '. _',~,

from a very s,[:rcQiD,sly negative eUlergy val ue=-thar ]3~ a strong bindlng energy-'to repulsive lellelig~{. This repulsive en~rgy becomes slfongJy 'nnli::~t";'ug the 41:;~'!"lI!iIn;j'!lA L._"!ii'i,.nal!l1"i; t,\.a. ,~.!;.)I,i;;!i'"",~ ~d' lsorbent hi T,.... IC'U.. if~ A,U,C··..._~ ,I.,~ y...,11, ru'~!!!i' adsorbate an the dlstanee bet ween adsorbent and adsorbate atoms is Increased erway front
~ylQ!\~IIi.~,""~ 1l1;l:! ~
1[,__ ~

As; {be' adsorbate '~smoved closer to the solid surface" t hie e1l1ergy g'oes

$,p~Cle5".,

~- -

U~,;i!I~'Pi.!!;~IIk;....

'n

y"",,~!,,l I~

;r:~, ~.1Iili _,_. ir;J." ",1"111 ~'.

~U'I,.

'"'

~,

,I,~ ,'~,.

....

eq_uU:i rium binding energy force located ,9!! the intersecticn <0 f 10and ,_ 0)0, b W ,t '4,a.; b- iJ,d,_ "l':n··.;tf ':mT' ' deerea Old, . J. d,"~ ~t,~'R,c)e'is '~u.fnci,enth~ ~,u., ~ force gH.." u him , at ~I'U' when I _~<i.1'_~'" ,, __ J' large, drops to zero, The attract hfC f orce is essential ~y z'et().,.
Ibn ... • _ it",j!!iit1' UiII:'-'!!!..o u ...."'" ""',"i>I'Ii;,;o'" , ''ll
!Ii;t,

",-1,,1 i

j,'l!..;i3 _ "II.U"",

o;!I

.-:1_

:".J

:'by:sie .•• and: Chemifa] Adsa!,rpt~lon

energy' dbi,gram tn fig'tire 3,~4,l C:IU~,be used tO consider the binding of :phY$iicii,ny adsorbed species and chemil$iotbed species [0 solid sUr:fac)c$ of: ,aU.types ~This [basic energy diagram and the ,adsorpdoin process associated therewith Is a Iundameneal step In the dev,elo,pm,ent of surface :fiilms:Q f aH 'kind_s" In '(be formation o f surface compounds (Ie ..g,~ oxides due' ~ to oQxj,dl:Uo.n0, metal surfaces) t be :1' 'ecursor step is the in:hial adsorpt w,onto. 'The 'fundzlmen,tal
I

1[-, emend,

surface prior to the o,ddad-on :react:ioD., , n the

],-4)

ener'gy state wn ":lute

adsorptloa,

the equiUbri um po:sjj~ion of' en,trgy for binding: on the ~o,west

process

of :~~;hY8.:[.c:a:1

is

,al

fu:n'ctl,om,

10"

a balance

'bet ween a 'negative

tensitles aJL7r~s verv ~ ,i:' - ~ 'l!./

addition of'tOXYlen to the surface can on:ly' be present on the' surface ,M m.hv,sii"t3I:U .. ' adsorbed 1ii"11I':\l~'PiII1il ~ ,v. ';i'lI" l~l"f,'.U"""iJ~., ~fie', ~ - (tV",:l'~ g'~,,~ ;:l~'~l,:iIi:,~ I ,to -,-,,,- ~-~ Y ,~' ~:J "",,y, ........... ,au ~l·,j"!!i~~nlt ~u._.f~Io" "" ~u._e !!!;,O lorm , .. ;, ""d~ '.- - "'F h ' -" -1 -~~ ;',ace f '.~ k ~d _ ox!"d'e~ b"J oxic anon OJ, ' tl, e meUt, sur f'- - - 1:0- rorm n~,c.:'G._l 'OXI,': e B-- ut ,ch,emiso,rp~;ion Is le-ssellt:iaUy a, :m,on,ola:yeJ' process, and once th~ surfacc' becomes, covered with 2\ mcnlc.:iayer' of' oxy,gen ~ chemisorption C'CIJes as, a process, :Beli'!iil",aadd it ~'OC'i'I'~~ll"",,,""~\f7le, be~ taken 'I;,I'r' b.'\V th ....solid surface nnii!l!, in c ~y~ U IQA,,,,~o~ '.. ,1,_"IU;; : Ii:livIIL_ !!I,l'~~_" """,~",", of the other two m,ec:banisms must beg:in to. o-per,SJte" leit~her physical adsQr, ... Hon, 'O'f oxidatlon. ,AHveal metal surfaces contain at least chemisorbed gaseous s,p.eci,es"" and
"',~~~,I Ii"'Io'ii" V,II!II ,iI:~, H"MI~ ,t:h~ ~.lL
!

,~JIthree analvt ileal tools, iX,PS ~ A WS, 81~'Cd ,--, ,,' .l'-"''-'~~ Ii, ~'-~"" ,. -t --fli-, "S':' =1·""5'-)" A~"t~:' '-, ~,-- ~ ~- ,~,,], "ii!l::(l ~- , '-I-Ii" ,e- (t': ~ ., .ti!jWIiI·h ' "'" t:;, '. ri...,"'"', ~ "-", ,<,.,!"tl<~., ,', ",. ,a.pprox~ma"e$,)' 'JU dUl,Guu.nrs, . ::dB,• .,1~J' t, Ie: S,UfJJllce !:S, lveoo;muwg - --, ' th IL.," , A~ ~ h saturatea'.AI 'W1J:u o.X.yg'M"t M"d ,t".hi ie enermsorpuon process ceases, ",0.')" f'unner ,

'wren 'wiUl ~"

,IiU'\;O~_

11;,;;'_",""

it ~,!!;,,!!

"'_.

!UI',n,,I'~'

g't:' ,_IiI-J;J,

1Ii'~'~

,,!:llI

", ,- ,-;- '~I~~'U'-:-

in
• ..

soecles
i:lIi,~'~~
",

:::_,~~~.-\,' "I:ii,e- "i ,~ ", ,~, ::_ ~~ lan 04J!~,n-eonl~,W]unB,environment

'iiij~:,~ ,', ~ ,-

~-'~' ,.-,--, •

surface ~~,us ll~ oxvaen M,:','<,",>!c~' ,O~,~·~"he presence o.f:~' the oxvzen has isuallv v t s~i.II'~ J..'- _ _ resu ~t,[ed the oxidat ion; that is, the oxygen present on U'i.esolid surface has in. gone from ,81 ml~dy cbemisorbed oxygen to the formation of.' metal oxides, Wh:~1.e itt, is Ichem:i,c all Y' adsorbed: to the solid surface, tb.IC ;Qxyg,cn is vlery'
'-1 I IWg¥~ I~~ ~ .~ I~ D~111l
JIll

a. ed .' h~ ; "e s,peaJe~$, ,H:n,N:, ~," Wn.:I. t h~ OX'y,g)eD!,

-'1

~~

~'ii'\131 !UtI, ~

usuallvJ
. 1il! ~_IL_Ip,
I

P~'-;'Fl·ntl'!!~n'q.u,y,: f'No'!iioi"IV€llI',~rFiI, .- ~,dj,!II'~~r'o.~JJ.. " VAJ.- ,b.~\I..1.

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Thev m ~IV cornain other ,~:.;IJ~0'r'iLjiI;~, III~~r1 ' ll.ll,~ u~ y '-b t~ t, h~ pr,~n':lpa~~' '. ~ou:n,.. on ~ ,e so ~"d '. '. d, ~'-h ,'U ~ ie' s"pecu~! _1 _
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n its bond t'n 0 characteristics toe a..l metal surfaees. Ano~her' character of chemlsorptien 'wh~cb sets, :i~ aside from ehemieal reaction or ch,em~eaJ bondi:i:Wl,~ is that the: chemisor bed species can be' recovered in :i't 5,bd~:bll:idlendly withlOidt bilving, diuoci'M.i,o,:n or redee'tion of the part:~cular.' adsorbed spec.ies; ~akii1Q: p-~,Iaee~ ~ ~ ~ If a motecnle of ,a partic~u~,arspecies (S(lY' hydrogen sulfide~)adsorbs 1>0 the solid su -"fac,e,~ hydrogen sui fide would. adsorb as h,d:r-O~leJl sulfide' and, th.e the' su I, ur wonld bond to the surface 'with the hydrogen rem;al[idnS auached f to the sulfur.. In, faet ~ this J.oes not ilap'peo.; die hydrog1en di:ssociaJt.es from the: sulfur, If it does, nQt and the S,U],f"Uf bonds t,o the metal surface, dilm t.hreoired'caU:y' t he 'hydrogen sulfide: can 'be' removed. :E'ven 'tbClUIl1" i1. is ehemiserbed by the ~ldfur atom to the: iroflJ surface, :it. can 'be removed as hydrogen sulfide by a desorption process __,U'Ui![ is, by' salpp,ly.ing, $~J:rficienil surface enlers:y to the solid surface to' bt,eak, UlC :sulfur t,o iron bond., In true chemisorption this ~s effective~y and ,easily acoompUs:h,ed ,0 demonstrated 'by the data of fisur'e' ,3,·4:5 .. '~i,~ '--.' '3-,=ii ~ :-- ~~. ~.'./ ,-' ' th ., ¥..I' Ij'~' ,I:·,~ure '.' ""'"'t,.} presentsts t ,e .uea!t. OJJ ,.4, . . ;. . ,"','- .!tor su'l'r'" 'f' ,!rom:a p 11·· .,'" ~; ~J: m , u.esor.ptJQ:I1, ,t;'., - .' ~ ,ur ~ , " ~ , aunur __ i~ r~III'n·,l"'j.1;~'n ,"r 1·ill..1~ ~~ o ,!i.W:i~ surface eoveraee ,dI[!f':~,nmi'n.a 't'~l~a'~the SUI''''' ' [~~JJ, ~ _.. (-1100"1,)~' surface JL .._' '.' . 14J.~~' , ~~ i,~gl u _ _, . f~;O"e;(:".t"i;'U'.i!l;r:~I'ilII!A;d,: O<.;i!I!il'!, i'~"""'~' ~""''l'',~...~ ~""·n·JIi.. 'b,!q,mf·:' ,~f'",a,_m~,:o:"Ii,'H,0:ltiil'~r., ,An ~v:am~--'iBation ,of the dall ,~,::rf :rilure 3-45 bl(UCiiJtes, that th.e energy' :reQuired t.lO desorb a chiem:~sorbed ;sulfur' a'~,om fr-om a s,olid, ~urora.ce in.Cfle"ases as, the surface covera.~,e decreases (ref., 34Jt~T,luAS,~the bi,nd:ins, uf an, a.bsorbed ~peci,es 1o ,a, l',,~~' ::~'lf~,<I;C: ,IS a i.uD.CI~lOn. 0 ,311r.ace 00 ~tL q ::~~~·"W c~,eal1'-'~I~,,'I'I~,sur _Ice '~, ;', ,~'.'- .... :tr,~,~. 1'((' ~<"rf··-,-,~~'v'.-r,-,I'e~ -:J!' U~ _ '~i' It:iI·, ..:,,~ mer,l, ..~ ,me;~ ulOtdns The ,greliter the surface ,coY."~rq,ej,he 1ower. the: bi'Dd:~ng,~,er,IJ'~ "fbe en.ergy t '\.1iiJ'J!n·~e··W~'~'lill I~U:'1i"'~,;oJI.t"\~ ·"~r· iIiIlQ'e, T'~hd !,~~ ~'r'~'L,.e: ,~Ib···sl('t;,rbeds"eci-~ .M-. r'~,~:DS ~, 1~1~".-, ,oo~ '" r'h, 'G't, v, lUI. W ~ o,n the s;urf:ace the higher tbe ell,eT,gy req,u:ified to' ,[1em,o'v~ tbe r,emain,ing :ad... , - - ~-' - Th~-~-_'I~nergy ICM, 'L. IqUl'C~t- ,appireoll,~~e'~or e.xa~m,pje~,~. :1I.:~lure;'-' "j,~ ~ . ----:- " ·'b-'~ F" --" -,- -, ~-,~-II- In tf.":ii .... ~ ~~~ mrQ8'U';';. . e ve
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formed on copper is,the lower oxide CU20and the oxide formed Ion the silver ~;~ ......... tbe xide ,n,g,2\.hC'I Ii, -il, -'0 lIJ$ _u 'u~~' 1$ tii'1o. lo ,"-,cna: e 10f e --,,,,-,'I C,':_. 'lib, "', . the kt."i"1.. me ower "-·"d:'"'' copper, "'- u- eetng t e mgner - - ~'d-" • ' ith ",~.. -'h- ,- '[-- -;!- ~il" orme ~ A' '0 oX'~,; ; 'W~ suver u e 0]1, y oxme If' ~- 'dl ,JS: Il''-' , e tn 8'i~Ble crystal spheres were oxi dized ~n an oxyg,en en vi ronmen t . The results presented in table 3 ~_.vIII are -[J0I11 the classic 'work of' Gwa thOley' and 'Lawless (ref, 3,{O" In ~able :3~'V is a co~'Umn for pa:ran.e~planes 0. e. where III the p~,ane -0 f the oxide matches the plane 'Of t be m,letsJl. and 3. col ~mn 'for 'paraJle~axes, The p\anll~el planes cOilumn inel udes both :rnet 01 surface plane orientation and. oxjd,le' oritntad,(~n.. For exalnp~e'~fo:r' the (ll0) metal surface , plane, the same plane matches on the surface the (:1.10) oxide plane, Likewise, \vith the (~.ll) plane of the metal the surface oxide' also has a (:1, 1.) 1 • '. 'II' .JId'· ,. -to ~:,e mate h ed ara l~] Pi1anes or b~e OJ(l~e tn tne -'h ..JI r-'~ lde m Ilk, onenranon. .dl I.uluon :-il.e, " metal the ~,A.· s a :"f . the metal 3FliIi,J, o..-uU,II;,o' c§n , ~ J!,v be ,v-~r·gl-~;fIJ'!1 db ~,~ ---..J - ''Iil.~..;1~ '. ci!i;. also .... no"l, g,;I.'!IO;'W lndicat Q ~. ,;,--~ I~I!J.,O .r ,,," !Il.J:,\..,~,~,~,!l.~~ e ,iL,ih~g.· ed m
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19Mt.. , ~,. B(,)wt:,@u", ., M,.; 8ln4 Smwtih! D., A,,: Fl~licl ~'O!lllM~~rolS~lPiy, r"hlf"l.h-HoU.aifi'd Pu'bl:i,sti'i!Wl! C~If~· K
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M. 'y',.;. ~, am. ~ A COmIP3J.ra&i~e :S~,udy the iFratlll:re of V~ri.ousS~U~,SJ, of Modi fic3!t.il@nis USlI18. '~lle' ",~~l~~~ar.i 1'I~S!~" J. Mater,. Sct,~vol, S~ W9f3 p.. :11,S30 ' M:u:i~ef'I' Erwi~ ViI',,:; and. T~onlh Twen T ~:: Fi~lld 100 ~li!C~o:~cop~~i'. :1l::,'I!SIevjer P~,b~il~ Ce., ;1in,g
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rn AJn.d~rs"o;n~ N. (;,; and DawsO:I:b I. M:,,:: Th~ St'llldly (t)f Cr),:stiJl Onlrwt h Wi'lh 'I:~.eElie~tr,!l)rI, '1; Mkro.~o~" 1,1,~·~aj,'Ow~:h :Palu:rn~ ~~d I:h~' ~~ar.tion:ddpof G~o~:ih81;~jp ~i8hll:b) Sl~ R H MOilocillaf' Slrua.ll[~e' in :IilJ"ncnlatr~a<omu"be' and ~n S:1ea:r~!C:Add., PIf'Cl<C",,Ro:y., Soc. , '(Lnnd.~:n)~ ser. n33, 'vI01. 21.1J~ ~'9!S3 pp., ,2S,S'~'268., :11" Hla'5m~ :P.: ,PllYI1W MietaUu:rMY, Clmbt~ge Ur!IIi,l1C'!,sitY, R,SS. (Loni;!Jon), 1918. OIr~fjinaJUy P pUlblisned ~dl 'GermlJu by' Slpr:j~!eJ\I\~davg, lI!l:&ld~r [!he tide Ph,'S'U:an;eh~ M~taU~.ufidt
t 1

pan)" I(Atti'!iliu:,erd~m)~] '~,ntl.

Opdca~ a~d Et~~~,rQin Mi.cr.~cop~ i J., L. ~~i~b;:C~rnl, 'W,. M:. Mu~lh~r~. :pl~~u.rM ~1Pd, eds., Press, t 9'i'4 :P',. jJ 1.8,. 20. A:meU&jH!~k:i'l~:~l. ~!: al, eds.: :MlQ:dern 'D[:f.fr-aJct'i,01il ,im;rl ImaJldn:g Tech:mM!Q.1lWe~, in Mau~riia~~ ~ Seience, No:rth ... oU~~d, III:bruisil,i:f!!8 Compgy (Anl$t~dam,)I~ ,~i H P 9?O. 21" M~l..~an ~,D!iJiIiUlld.~ Ofai~1:10 un daries in M~ ai,s, O:l!;.$~;rdl 'Umra:v., ,(Cl;'\H'-ftdo:n) Press U~.ond0al, 1'91'1'. 22. iR,uQ, W. T.:; ~~'fd,.S'tm~;ck~e" W'.,: I:mpe.rf~~t.io~;~ llill:NeeJf~:Y P~f'f~I, Cf'J~H~I:$.V~i~~' & S@a,~" l N'e'~ 'y o.tt ~Ch~'nt~m, ~nd HaLl~,Lofil!diDn~ 1911,2.:P" JS;,l,. 10 23. W<est.b:r.ooJ'~ 1. ,H.•~ Surface' !E:f~ecis on the' M~c1fl!a'n~ca~, Pro,ert:ies 'i)f NO;rIlm.e1,als. S,'iuf3i;:es aDd J.me.;rf~ces, PbYiiical ;McW M~bafll1ca] :I?\ro~rti~s, it 1'+ Bl!!;rkre~ L, RE.~dt and 'V. N. W,eis~.,OO~"'i' S~,riliC:UK 'Uo:ivef:sity Pre~~! ]96S~,CD., ,3" pp. '95..~~UL . lA" G~~I'ilJ~~ M ra~d,,Ri'yifTe! j',. C.i: Poocffiphrtli,0i';l 8ln,d, R~~((tJ~tjo~, of l,m~~]",i1.ies, ~llt~~ S~ffaoe e] ,niUmUMI on' 'f [E",a'Yu.SIDng 'hILt: M ,eluln~ il:"1(!iienn:,. !t:'~~ It" ,AI" ",'~, ", &; (jl~' 'I; ~\., , :~', ': P:P~ ,~g ~!tI; ",Iji; 'I til"",. £JII o~ »un.ace i.M.o.l",."'0 I'V, 25. Orabke~ H, .J.; e~,;~J,,Eq!!iliUwbriu;~ S\llrf~~"e :S~~~!.Idon ,of ,[U'!.j·~iOll!J~ M'on'fifi~ULi AN).:f1E'I;,,1j; en lfiOi[l ifl00) F~~e~+:S.'t~.r:f.iace Sci, l' VIol. '\3, 1'971 ~ 'p]], :317'·:189", :26. MiCMahOtl!: C. J ,;,,~, and, :Mirtb~t ~ L, ,: So~uJl:e'Se,gre,laU(Ih!l iiFm, Iron~,:Ba:sed AI10iYS" J. V'ra~. J1:.~ Sci~T'~chnoL! vol. ~"S ~O,' ,i:~ Mar"..~,A,:pr 1.'9~~9,~, 4.s~. ,. pp.J 2'. N,i~ "Vee S,.; a!Rd 'T~mj;~ T" T.: ToF ,AU~M, ,P~,'O;beF.IM mnvlenipm:~~. f .surfa,c'C sej;i"t_tilO~l. o hf~. i'l wt~ AUoys. Surfa"~e~Sci. v~,]. iI" 1'9'7:8,PV. 41 '4a,8~ D :2:8, Ho:nO'r'O~!,iE, [),'; ~~d. Mt~n,~ D,:: :S\l!J:rf~.c~ jlqi~; E of S~Ud. );ld,al AUoy,$. :S~.rra~ :Pl~C'iI.Q.,ei1a, of :M~!als. :StC,J., M'O:I1~grttp:h nOI. 28" ;Sod"ety of 'Chf~anica[l :[!a1;id'UJ:!i t'ry
t ill

(lkmldl~Ii!); 1'914. i9;, Hiays:! ,C,'~:E'I~rupo]is~linB

of' Tbin ,Me1~~ !Fc~ls,.,Me1}tin08r,ap.:ml~ S,eci:m;en P:re,par~UO'lIJ~ '

e :,

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:29, 8lake1Jy,~ J;, M,,; ~r.id Sttcl~O\iilJJ C. ~ Equ:iI'Ibdum A.d:s.o~iPljonI.nd S~lf~gat~~n. S~:rf~« I' P.'hys~~s of :Mtni¢d~!;~,~, . M. 13~~ke:iy,~,oo'.~,V,~I~.,~,A£~d)~n~~clP[1r~~, 1.97'.5~,:p,,;, rn :239,. 11' I, :89.. ,1m. DalOlwoofll'i :$. '0 •.I' ed, ~Pro,gr,eM ~r:lS,u'f:face :$dcnc:e., v,o;~.. i, 'pan, i, :P1lu':gamo:n Press!, Ltd. (Ox:~ r:o!Td)" 1"7~. Ooodwh"h T. A. i and, M~k, P .; The :Irnlfiu~floeef Ch.emi:oo'r.])ti~~ (a:]1J the' E1e~tnca:l C'oncb:iC',tb!iily o:f Tilln :S~joon.d.'~cton, 'W'oJdecbowsk:i,t K,.. F.: The 'QoantU!m 'fhe@wy ,of ,A.stmrp~,~!I]'non Met.aJL S1Jr'~a.oe~,. '.Jl ~I 1"~~·'Ei.'i!!Ii..,i "T'·, 'f-,!.- ;o,o,'i,'ii'-'- - .. D;;;,t-- _'l'ilii..'~~~;i'~~~'!l1' .it. odl...... . _~ ules r~:Y,r.io'" ~nl""f""'''''''' ,.. ,~"" ,;}!!!. !Ii,g~'l'!!l"!l'lIIh,:I' e- •• ' ~,Il,~elli~,',.,,~,I~n~, ~""I:W"''''tl11 rn..1'~'~"~~~~' .;!"!'6'~'!.\Ilf-'b..,,'.:Ii ;_,!~~" ,~I!.-i!f! _,i!;5 .... r;::!~~',.~ vol, 6~ O[}. 20j 1'5f7S to pp,. 4S,-6l. 32. Aoo,e(r;sofl J", R,.': 'OI!~W~djaifP1liof'j R!ea<:l,'ons o:n M~t:arulit Fibi1llS", Vol:. I. Aud'emk Prtess ~ and
T

(Li)[lJd~fl)!I rn 1"'8 ~ p,. ji9"

'1Ii;.,~"",I ...... ,[\'1!!;,l![lJr";",,

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34", Fi~hf:r" 'fmu@iQ\U :E,.;,,and Kiel~m~n,- Sall1l1~'n, R,; The Adm~iPUon. of' S'U;]iUf on dH! Phld:num, (HJO) S1m~'!i:~. SUir~ Sci ,. vol .. 6'9"t ruM"1'jl vp. ru,~22., J~" BC~Uilldloft,~, ";; C H.,:; ~~!d 'Th~je:mte'j, hildal Oxidatio;rw 10[. Alumbrn~m oFiil~$ ~nT. [f',,;: vC5ti8:~ucd b, ,AE$II' V,""lfk. :func~;ioll.and 'Or8,v~metric; MeMUTcmmts" S~rface' Sci,,~ ,ttl ~ 'Yom.. ].'911. p,p~~9~"··1', ]6,. Owa!tInne:y,p At., T ..;, afiirlJ Law.]~s ~ K.. R ..: 'rnc~ In.n.oatc..c:' of CrYSlall Orientatio.n, 'O(i!lJ Oxidame '~iol1of M~I~ls., cTh,e SUff~c-e~ MJ~ti~tr~ ef M,~u~ls Se.mi'C(!t$i!ld:!Ilct~r~,!,H. C, 'Gatos~ ed., C ~d, J'offiin WiJey &: Son:5:~ Ine., :I ~oo,'p. '9S, 37. H'Qil~O"W'a,)1'~, H ..;; ,~ndH~d$M,!, ,J., :B,.~ Kffin~lic:s;~,f :the ·Re'a~i10n (at' O:'!ygelilJ te Ci.e8lfnJ N'1c~,el P,. SiDr~J~ CrY'il:aW Srawrf:ac.es. Paft! b Nid;;:t{~ (moo) S~!tf~a!ct',Surfa'Oe' :Sd.~ ~'OI~. ,i91'4,~Pi)" 4,~."

3,3. Conner to". R,.,;: C.om,biu,8!d!iUl A'1"I!.ail1ysis of :Me:u~dOxides, Using ESCA" ,AE;S" alnd S~,M:S.J. V:a.c" Sed. recb~.Ql. ~ 'iiiOl. l'~ no. 2'1 Mal'. ··Apr. 19'j8, P', 343,

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~ becomes ava.. i~,a!b~e' 'the surface dur~ng the rubbing process and an provides a co,:ntirtuous reservoir [0 r ,Iu'bricadng material ~ Th us, v'ery' f requem ~y in t he use of Stolid f1:l m 1ubrleants a" Fo,ugh rather than a, 'hlg'h.ly po~:ished,surface is used ~A ty,pk~a~, ... grit blasted alumln um surface that m:lgh'l. be emp[ioyed fOIT such burnish i.ng operat ions is shown I'n, filure 4...],.The , phOh)m:icti(~,s.raph in f:igure 4-3 reveals :readjly it he' hills 1fF.l:d valleys associated with gr~t..blasring ~,hesurface, The pockets in the surface are a function of the size Q f the gdt that ls being used to bombard the surface; the, ~ar'g"etthe gri[ 'I' ~ he larger the -vaUeys generated. :Be~,e:aththe' ph,Q~,o,:m'~CJiO,~Faph -ns.ure' 4,·.3 is the proftle trace of' the grir:iin blast ed surface shown ·in the ,phOh)m'icrograpb (fig'. ,4,·,3l.The surface is ex~:reme~yrough as Indic-ah~d by the surface :pro'file trace When this trace, Is compared w,ith the surface pf~),n,l,es 0 f :f1.g-ufles ~·1 ,~:nd 4·,,2 :it is app:arent w bat srW t-b lasting can do to roughen a solid surface, ..... 'P'I'[obab'l:y the smoothest. [s.u'ria,e,@that, the t:rfboiogbu. ·enoou.nter's, in pracIleal lubrieat loa ,syst.em,s ls the cleaved su:rf~tce, whi,c:h is the smoothest ato m '1'r.auIV '0~ AIIj'1~"CiU'\i h '0'- .'''''''''!I!e\~ ~ the cleaved surfa i,,," n'n~u' ~;'nmoreanic ~i!o": ·!l.lIi".t· " ,~U,i" . ,'-,
1herefore
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y'bdenum disul fid.e ~H)t'hat 'pole kets develop on the soUd surface to ,R[elas, reservoir, to retain and hold a solid. film lubricant; the solid lubricant,
t hie' mol

crystals and materials, such [as mica, that can be ,C'~ea,ved, a IOft.l; certain crystcd ~ol,lraphj'icplanes '. ,1\Ji~ hough it does n.o~no[:rmaUy exist in metals, some

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don" ,As a consequence, the surface :profile trace ~;s distorted hl the venleal dime don '. The amplitudes of the' iI're.l;ull:ride~ hl the vertical direcUo.:n are much. greater than 'those in, the hori z{utta~direetion ~,figufe 4-61(1b) is the ac'!Ii'M ~ ~

dca~ magnificado:n is ,i,f!n.er,aUy 'm,lu~h greater than the ,ho,:rimn,ud ma.gni,:fi,c'a,""

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technique are' efiminaeed. puter is, used in assisdq, to ~dend.fythe nature of dle actual solid surface, :Pigllfe 4.~6(b).,~,hen~, represents the true surfaee topo,a;ra.pby (ret ,2J~ The teehnlques used by WIUiam,son, are very' ,tftectJ;\!'t:.in. re~nlvinl the comp:le:xi,UeI of the surface pr'o,file and giving ,a, chareeterlstic picture 0.( the 'r,~,jIJjj11,~~'Il'~ I~~.face AI . ",',. fc ~h-' ~ so .Iou su r ace, U': n f':on UD3J"e. y . Om"_' ~ e ave:rqr:: ji"-(jl-.; ][ -:~'If sn u~I~e d!1IO'O _,Og.I$!~ r4bora10ty,~ :it, ls d'i.f'f'itu~t to incorporate the techniques em:ployed by 'iIi'" ",' " 1' "-, ,'! ror W,·\~·,··nll~'-; _.' lw .ruam~on,. H- -", ",', .. "-, ' tne surraee pron omerer is ,~ very use"f':U] toot f".· __owever!! iIi'II!..,·· ..:,-,' . "",,", -", ~' , ..~ '·I"AJl!IiHl~'l"fw~ir~iOi' d o"'!'E""'m' l""~-' ,iii,!;!, .:;I!v,hl;Jl. eiiiil,.,.,t;",?;.;:'i9~ ·T·"U,,~ d.o ,t;1f"9 :!!in' narlne 'I1'n:il~;.,;i _ La' 1to.;Q; ~'5iI!1JJlJi,A 'tn, ""'o:""m~ U!I!Fi!iIi~ ,1II"~,,..... o~ U ..... ~~""'U iLv ........ ,[.,. -',_, pare one surface with another and [,,0 s:~o w ~he di:ffe~@,Jl,ces 'that have taken :p'bleein the surface as a, result of, 'fo'f'eumpme ~'the process o'f wear. ~,nthe s]jdin,g~ ,raIUng,; or :ru,bbilll, process, the nature of the topo,'grap:hy of I, so-lid surface can change markedly frolln nlal~, 'prior t.o the ~m.wth?ttion relative moof doni between two sotld surfaces. """,~~ viIJ\Q, S;~,~· ......W ;'1'1 probably~ one of' the ,,'most_ eemmonlv -"-I,-,~~cl trib 0c··,'l,-'-,~:~,~~ ";1-:-*[.-' en,a:~,s ,. v' ,.,_, I~,_,_, v O~I co ,monll.,J" u:s~ ~,n.:: ,_ og~,ci!i.l!!o' a,!J, '·-;m", m In bearings, for example, a steel surface may be, in t~h.~' ground state, An ex'ammanon-. 1'(',"':' t~_ :. gn.)illj,n '. ", '1'0.ace '.wu. "\ ,T·.III: :" '. ",.~-: ": '.,.'" ,. or ine '". '-I I 'd: sur ;:· ',' .... , ~,' h tne ~,3i,lJysur. , a surraee .- . ;;>"'~II'i' "f";-" _"f,:, '-"',', ',' promometer,lnstrument, :revea.ls, a, trace such IS dUl t ~ho,wn,~m,fii;ure 4",'j(a,) Note t,ha;t the masnificaHon :in figuf1e 4-'7(31) is, '000 in the' vert ica] direetion and 2S in the berizontal di:recti.()n 'When ro Jinl or sliding, contact occurs between two solid surfaces over IftJ period of ~ime, tbe surfaces wear in, Ute adhesive mode and the ~opo.lra:pby'o f the surfaces ch,ange from t hiPJ charaeteristic of' the ,ground surface shown ~n figure 4 *'7 (a.}1o one simJl,a,Il"o that shown in, flgwe t t 4;0)] 7(ibJ~ (N'ote that the vertical :rn.a..gni:fica,Uon has changed front ,SOOt) to ,2S0~) In ngufi~ 4-l(b) the surface becomes 'blob ~y :irlreg,u~;ar"Wi~h a bac'k and forth, . .II.[I j;'I1'f!ll'ni:!C' if~'-'o'.m 'on,'e,sur,~,~oe ,tjJ ano~ner ~", 'li-b', ,a, 'llles~V'e'wear process ~ '~'iit1!..,~i,;",. ~"\F r,< ',-~ - ..-' -, Ul I,ue - d",'~',,.-.;" -", ,.' :-.' Sm,ce the vert i,ca,~ma,l:ni,:fiea.t.ion bas been. changed fro'm '(1M) '~Oo,:nJy 2S:O; an i.n,u~~rpreta'Uo:n o:F'figure 4 ... "(b) ~h,OW8 the surf8JC€ ,pr()fUe is, extremely '["HI)u,&h w:h;e~adbesive wear has taken pblce., In, centrast, when the surfaces are rubbed in. such ,g, manner M to produce ,(lb~as;hflewear o'r the surfaces 0:0 a
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-,n, '~ a,[!o~""""j'ilj ~:,-,,~, l~rrvr.;!1 ~~u'"'''~ itAd: , Wlu~, tll...,~, .lu!¥~,~,r.~ng ~""'!Ii!O' or """__ 1r- ,~~'!iOi ,',from the surface p,ro:Olo:meteBi' t oo~ and the comA i::I, ""!;;'5;,;;.t'!i~' :-, ' ~!I'
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of wear oecurring surface' or subsurface by d" 'he original surface level ~5 shown, The posit lve wear volume reflects ~ha t amoun 1: Q f materia I, t h,am, has been lost Irom the sur face as a, result of the adhesive p~u,clld 0 f m a 1: erial from ns the surface leaves pits~voids" cavities, (J1r alleys beneath the' original sur .. v , wace ~ ~I • ,i, ~eve:w ill" ad~d"· to L~,j l!h, '. tn n 1.0n. ' hi S, ;1 ~o\v'eve:1f~ m I,t ena~iii can kne t rans f"'erred 'from t ide
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oonta,cting surface back to the surface shown In figure 4=9" W'llen that O~'''' curs, material builds up above the 'otigJn,al sur face level because <0 f adhesive. transfer as 'in.di'cat-ed by the shaded areas above the original surface level

'isl t ransferred

('fig:" ~~'9) This is referred to. as. negative wear material ,; h Is rbe material rh at ~

face were sUding: on, a, steel, surf ace, 1h~' sh aded areas (w f the or:i!,runall surface of nl". ,41.-,9 ere I. steel surface) 'would re:nect transfer of 'CIQP:P~F ~,Olthe steel w su.rface. This W', , .'on "' re present neeatlve wear '·'0"" the "'*=,.0; ,'Ib~;~I~I"I1i' ~ ,,1 II."~ y I]d' , It.l! "" . _, wear 'I~~ . _ '.. v
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from, an opposite su r f alee. Til us.~ for example, ]f ,3 copper

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machinery, Also) a loposra.phy wh ie'h n~,ay be in it i,a'i~Y' resen I~,on th e so<~id p surface i:s changed very nl'pidly once soUd-sn a U~' cont act OCICU.rS bet ween 1:WO solids. A new' h)pogra,ph:y is generated that is continuously Chaol;rn:lllg w-~Ul, the sHdi ng", rollIng (H' rub b:irt:'l\[g process. Dependw:ng: 0:1], the w'e'ar' mechani s m, III b~rut w,aU::.v smooth surface may' become rougher :~,'ft he wear mechanism is one associated 'wit 11 adhesive wear ,~, r :8 ver)f' fOU:~J~, o surface m,a:y become
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the copper. , f copper' picked up steel from the steel su rface and left vo ~dS the surface w'ould reflect ,a 'c'a\i'~~y of steel below the original surface level, The data of figures 4= 1 to ,4,·,9 show th al init m,o.!. SiUJ race topographies can ii' varv in p'ract ~:""!!:II svsrem~~ ~n[!l.JIl '~ h ,oJl w., hese su rface t 0'-: oo ~w~, ph ;'I?"~ ch an b~ 'a~'~ ~P markedly jin the slidi ng,~rolli ng, lor ,Fu:bbi ng: process associated wit h practical
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p1rof'i]:c;' solid sur faces. These inel ude m,a;sswveadhesive transfer or welding of of 'surfaces when clean surfaces are in sliding eontact in an unlu briear ed suite" 'Under suc'b c()nd:!t,ion$,,;, adhesion :m,ay occur on two different scales-s-minute or massive ~ 'When adhesion occurs. {)':I:], a m wnut e sea Ie, the t rans fer 0 f material b~ a's, W,BS observed in the :StU' face prof ~e traces 0 f the earlier figures ~In, addition thereto ~in t he unlubricated S!( at ~ when the' loads are :suf:€:ic~end]{high and/or 'W he" ~ experimeats are cond ucted :i n a. he lid {I;~I'~1:I'n-~r1I,. environ m ,j:'i;o'it'ii'ilt "(MJ'hr~ ;:i;1it.\ifi' surface oxides ~ ~..,,~'n' re _f';ijiir'm'l 'm' assive adh.~ mot 'I!o-J ar,,-,~ ._.AU .. au esion that m,aI'yOC-CU:r ,altt he interrace between t wo solid surfaees can result in the pluckin,tt, our of lar.ge amoun~s 0 r materlal from one O;'f another 0 f the su.rfa.ce,s~ This phenomena is, 'very' f:'reguendy observed under severe operating conditions (vaeuum, inert, and reducing environments 'w'wth metals in ~Udlng:",:rro:~nng~r nibbi:ng: contact ill the absence of ~u.brrucatJonor o
§ ,..g~

in addi don to the normal wear processes whi.'c'h can bring abo ut changes in surface ~opolra,l:dl,Y, there are alb er meehani sms whi eh tend to alt er 1he

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when a lubrlcaticn system undergoes failure) The adhesion process ~s j,n.:i,t,ru:aued by ,eit her l,he' we,ad 11,1, a.w,at,' O'f :n~sidua] ~u.r.face ,o!jdes ~o that mer:al to mie~:aJ con~a,ct can o;ccu:r j,n the m,eta,~t,o rneta] s,y:s~em,o':r by' nile naptuF~ of t,he s:urfa,ce ();ddes due to. p':I,a~$~ic deforMaJ,tion .of :()() t'O ] em i1:l1,gstroms ~hick: depend:~n,g,on tlu~~co:n.dh Ion. i() r the ,21 u:m:~n.um,,, Thi,$, oxlde i.s V'lery h,arrd

s:urf:ace ,coin1: a:ins ,a, thin {ihn of

~:lrN~' acts :in so~id,..!.sUlte conuict under load,., For exarn:p~e an aJuminu,m :5,u.rf
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(£']1 Surja'Cil. ,stnD

rofff.pcment in sliQint dire"'~cm,

in
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(pan,i:c-ularly of a brittle mat em-ia,[) an. be very gJ~,ea~nd have a, marked ef .. c a · "feet on the topography' of a, solid surface, '~'- i"i -,'. t4' "iL. '''1'·' . .i r! ,-'" -- '-,1" --". ,~n ~,],I . 4_'"' a,re'."'W ' . ~h:" [o'm.~cr,og!'a,pnS fer a. s,~,~con·"\, .'"I)' :s~n.g,e~crysta, '-l UFe' it', ,,- t.,: ',0 . .. ,0 ." 1 or . It:'u' rfaee g:'ft,," ~:JI.~d;-'~'T'iiO 3j'...,. iron ",,' ele Ii:;; , al g ""ro"'~oC1 I'hat' :SO' II' UI er .::I':II.l, , l .. ;;'r\1'il'!"~' A, ;":Jii.... 'T' h g ,Ii ,W adhesion of the iron to the sili!conproduces strong. 'Dandjjlng ~U,the interface ..
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tact o:f the' ·~ron.·wi.th the sUic!on 'pnld1ilJces, SiUJ ffljc~ent force to p:roduce the fracture cracks observed, S'ince the. iron bonds, f'air~ystnlnl~Y to the slllcoa,
= -

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abrasive ,grit material wi~hsharp Icutting edges; these ,sharp edges rake out or remove '_c.t __.0 it: m8t"-, "a] :f'rom" :a,~',,'(:'1;-, w'0-, ...plCce 'Ib:- --,--"~:",e the ha ...;I ,C1ll,1l, Ulli ,_...1,.--., __cn _ -"--':' - :so,~cr __ rk-~,'""",--: ecause QJJ .. e - aru I 'iii,t,'", "',.' cu,~:e of the' ,abl\ISiv1e., 'Ev,e]],I, 8i~I;le pass of one o:f these ,lriil.s.~acn)Ss:the surface produces a marked ,chaQse: in, surface tOJ;uJ sr,ap:hy results, ,A number 0 f in'vcstiglJt"ors dU'iQ-ugh th,e '~tears 'h,aye· ,examiD,cd Uile'pla's.tic deformation ()f due'~ne'm!3!l,erial:s in the eontaer of' ndatj,'veiy b,ard materials again~t softer' ",",,~ ,1l.. ~.re!;-, ~~A,::_A T ki ", "apan marte-noos CO(AS t f'.• 8):a..i;IBJ· stuUtj,I;;U 'the' process ,81 we''1I-11 :as".sutme in J .. (:~e'fi' 9)., Courtell and his 'COn,tag.ue5. 'in France have done ,I VCJy detailed
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surfaces in contact has other dum at sph'erie:al.,shape,. For exa~m,:ple" in cutdng

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This deforma1i~):n:is ,eYCtn more severe w,here' l.he' harder surface ,of the twO'
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'Thus far only the two-body interaction problem relative '{IO Ute g,enerat:io,n .' th ~'"'··b··· '. ,". " . 'd' ' uere " . ":'iii" / ' . o 'f" \\, ,f:' lli.r,l {;I] 0lUC at sur fac s h ,as, ·b· ....., . _lSCllS~e,.! 'T"l\.., are,' 'ir-'W!V;" "eli ,Sld,a,'~ B;ces.. ,., een dl .,' J:lo'"e . • lved In, h ' ." iii'" u:ons, w'here at, h'· A ,50 J"g e',ement 'k ,~,ru, l~" 't becomes U1VQ, veu in 't_-I'egeneratron O'~' a tribelogical su ,I' face .,n"" -,~, ~''''·I''''1iI.. exam it'ii,i,ifi the_ form anon of ,_ we,"ar'debris In 'a 0-" ,l'!i.rJQ.J ~'!w!ll.~" .. l"',WIIi;.]~,iU . lIllu., _, .,
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, '. ", amca ·d'Ie ,Ice '." h·· .., . t.ue,W ear Ar;Ifo.,-'n s, ',fi'-In. s ,~t w·· ;,'",". ,..,..',.,' ,',' ,.., zone' . ' ·,·,·d: meetha ·,·,······,·1- " ·V:',····· were ,'Il.., , ,: I" ne u S "a1 10[,0 tne contact ,:",-i, between twov. surfaces 1'" solid __ te C' 0.'·,' nt a .... Wh.e·, hie debris does ,5' 0.', ~:~' can ·, ,m __ ~ ~~, ~ __ ~v ~ _CJ1'a~ u~~~ ._v~:~ ~!tJ: ~a abrade one. 0 f t hie' two' 8iu:r:Facts,in t he soli d-state eont 8:\:lt an d produce: ,a. mild
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wear effect over a pro~ong,ed. per,iod of' time", )J~however, the pardc:'~esize of Ifhe 'wear debris Is re~,~t lvely large or 'the part icle is harder than either o f the two ~ __ severe surface ·d· amae ....can occur 'TiIk!~t u - g..a~ can d··· g:m~,a,iOi u surfaces ln contact J~:~ Wa ' ,:-._ a t,•. '~'b· ~ or m nor surface ~'nlen; tat io 'DC or deferm ;g".]" '0-' soo ts I" ~:L ,~v~ ~ ~'r n n 1~1~'~ !i:'n~l:l".41 L.~.,~ r U''I¥.~.fu. face as, foil' example, 'where a 'ba.~land ,3 race of a. rolling element be,ar"in:g
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Pormation of tier-us .b'J' hard .partictes," I f the hard part kle 0 f db·'t or d bi:"- ~'". :'.'... , .~ 'b'et,. een. ""'h' b,' il·~1.8oJl-_ '.' ..',''.,.., ..;,,-'../,',' '("' ,'. 9j, part_c_e .... 'f' '_t,_CO_~ ' 'ic'~ 0 silicon _,e __, IS JS nap,pey 'W" ". " tie .. a - d r.ace conl,!act;C'.B"'!II earbi de) and t he ball rolls over the, part lele, i~ could gene r 8;1e a dimp~e Of
=
,W '-I ':'

dent 'ru'fI: the sohd surface, SU!~bsurface defects are' observed 'QU i~,efreq ueat 1,;1 .. . res Lib[ 0 Al ~'-.' n ~I bri ton .',' - . . A" n .- , ,- . ,- . f . dC,. . '~·W'· -as a ,--., ~(..r, ulin't I:'",- I~,tl,nc,alt.,.', s,ys~emi..;·:·· examp 1-.e 0,·i'S,UC.WIIl a,.. ent"," ~,S SnO, ,.n .. : 'in the pho~: mlcrograph in figure 4.. ~'. The circular area in t he center of the o 2 phoiomicrograph is 10 den~ produced :i:n the so~:id, urface as a result of the s
'I;..
'1

.,...11 presence 0 f a t rappea wear _

A'

. , r." .;;I .., an 'cl""11' ',e), co !II.... Vile an in 'ftc' uence na , - "-

effect on ~ubri cat won C.aJ.t1 be' seen in fie,tlf'e' 4;0.,21where the surface of figure ,4-21 is lubricated with an' oil fllm and an e'~astro'~hydr,,)d.yn,amic evice is d used to ~tudy the interface, ,1\ ~hirru lubricant 'film is, :pl,ac~d.On bo~h wHo' sur, g! ".'.

The :presence. of such su:rra.cle defects are reflected in. hI bricated systems, on ~I b'·· .. ·- . b'ienavier 1:0 ,3, CCJiliI,{,3'Ct zone. T:--'-· 1IJ,U meant : .ne
.1Il.., _.' ,~ -... . .

'I' ~~" --,"f' ",:!i, .' :,' 1.1.., .·!"I,.' · "-::' .al a eonseq uence,'. ~ne..d" em a,lIJ,so'appears 1110tie, ,(-,~Illrly sp·h'·enca '.' .'
')"r'C,.

.. 1 (rer. part ~,c,_,e: f

.,-C·.

11-1'\ .I;','.-T'hie _"

,iii,,',

· l ,. '"] "L ~ pan,H;':,e IS, f1U:r- ,y ,SP,df!TlCI"'I ~

,'p ..

"-I

.. L

fac es

.:Ii,.

T' he d - "',1:,1,"~!nt
"
,!!;,,_

,L.,
'!'r('

under the stee~lbaH., The inter'fac,e is vi.ewed, and P]U)~Olraphed th:ro'U,sl-i' 'the glas.s plhu~ LTh~ ,rings, :in ng'!JlTe 4=,22(,a) ,around ~h.e con (,act ,zone ar~ the ~
., "_"_ L

on 'a" .., <_,j . I, steel

.'.-.'-.-:-

iI;..'"'l:Il1I't IIlJd,w t "'i~iI=.'!·c· ,~~ "nW" 'h- \-

'HA,'e' "~ ,_nY, a g;i;!li,":S P,I.", te'~. L, ,~,. !~Ie.., ' '~' ' -'d' a,'-,A " - .'l'i!:i"r:;;·"",-~ ~a' -:o~'a~'-.:'l

,21'9

m t ne runure of the surface t opograpby. and the ccmposldon of ,I solid surface, For example some e~lli,pso'mletricstudies of Ilasses pclished wiidl cerium. ox~de under c·n or' wa~er reveal some strilkin_g,differe~lce,s ~n composition and densi ~:yof ~he surface ~ay·er.'s;; ome eni,:psiome~:ri:c: results o'budned f tom the S 'poUsh:b~,g f' glass surfaces wit h cerium oxide in oil Of' w,a.tet are presented in 0 table 4..-' (n:::f,. i,f))., ~n table ,4,..1, UlJcrle are four ,lblSSes 'w':nlch. hive' been polished ~rHh. cerium o:x~dteusinl: tit,her ail or w8'ier as a ~,ubri,can'f'. The wa'Ve~,eng~ 0 f the' :incidf'ntm]jghit source). is m. anlst.:n)ms:~ the angle 'between It the hlciden~ Ught beam and a fionna~,to Hue solid surf.,ce 'r; '1'$,S'9 ,and, the rar in of the reflected amplitude polarized par,all,el to the plan.e of 'incident ligh t. is given by ~ ~'The importaar tthhll, to recognize whh the data of table 4,m,[ is ~'hat when oU ts used as at lubricant. in ,ev'ery case, the surface laye~s ace densified. as shown. by' the decrease in. the val ue o'f w n·ow 'v'o~ On the other' hand" 'when 'waleI' is, used ,~~Sa '~'Ubficlnt~some of the cations in the' surface la.,ers~o:fthe' ,glass are leached out by the 'W,al'ef with a consequenr decrease in the refraenve ~,nde·~"., other words It his l~iu;hing out. ()f' the cations n,l'JJS du: .1m,
b_ Q' ,; l!

..... III;' A'· menuoned ..:1 earuer, 1.be environment s : e envi

can Pi,lay a 'yery strong

~I ~OW~· .

O"PO!dlt,IC:

effect of densifieation, ,Bifid 'w b,at one observes is Ute overall effect; iif still decreases, ho'wleifler ~

In addi t ~ to t he for€,~,oi:n,g."changes in the expertmenral parameters ean on alter the' densiflcation of the solid surfaces. For example, the load ~:ba~ ap:~s p~:iedwhile poU:~h~:n\~ surface 'with eerimn ox~de'influences the dens;ific8,;;; the tion of the' surface ~,a.ylers." The ,greateli the load, the greater the doo,si.fication; the ~()wer'~he ~oad ~ 'I he ~es,s, dens~ficanon of the t3oUd,surface of the four the

,g~,asses,nrJrucat:ed j

Thus, the nature of a tdbo~~),li,'c',d surface i,5, :in.. flneneed b~1' environment in which the surface is polished. the The in fi uence of environmem 0 .e., t he hi)bricant) 'when poU:sh:if),@; the four glasses was observed (ta'bh:'4 1) 10 make a d:irf;erence 'in. the densiflcarion of the sulid ~Iurface' ~,a,}lj~rs,. 'The, metU8~po:~i,s,:hlng material ru~.Slelfalso makes, a dlf ferenee, IF' the, material [,0 be, potis ned remai ns constant ,(!Imdt hie Iubrieant lre],0. table ., .. ". 1
g

a,

TABLlE 41..

GtASSfS

'POL~:S:HB'D' 'W WTHC~2;i!ll

~A~ :S46ru

,1,; IP"= s~r~'.l

~(I'

de~g 'deg
,SQdla Lim, e (13.:;
O(HjO
18o,'008~. ~c:~te: ((N),~ 2:4]-)
,ill V U'
'r.

,iI'oil' II "wllte:r'
d.'e~g;·
,3.._o~~ ,Q, A. .iII,S·:'O.·"

rn

',~ .0 ~1!le~I'JI'

s. ~O
4.95 I,

~ . ..".~

9'74.. 1

,50 res i.,t,ate (8,5,': 18) 70,~,,2,

A' 1-' --- il:-- ~ • "1-'·· t ,- '6'··2' '~Ii j!' ,ll!illrn.lIi.nJJlSl ~.'C;~"~ v- "::,JIl.
tj!,~

'c '..

:3: 21c

'-

3 1-3
i. ~

'"', iclI'l!O

'11 ,I!;!' J;.U

1"100

a . , , ,,_ .-,

Refe:irence 1-S",

ReO'lwllta11oD ~'Ordefjli:I.)1:Qn d RecDswlUZI,tion

'The' higher the' degree of strain en.,erIY,~ the lo\ver' the ~em:ptn~.t.Ufie' of
['ecrys.t~U~'z;ahon~ Consequently,
~ _'¥'_}'
- - Il ~ • -

betore rh.e surface m ""'l.,V otherwise '~J' \WIJ~ __ [ be f'eady for such recnfs.t~dliz'a'Uon The grai.ns in a, metal surface not only ~ undergo a high d~gj'~ 0 f serain in, a tribol(),gical surface, bu 1. she tribological surface maya: so' contain grtli:ns, 'whic::h are hi,ghi:yoriented as, a result of the ~~II'~d, 'r-'o-11'·'inu' U. r' r-'ur'b-':b:']'nO' p-~IjO-~aCl"" ~'n other ~!iHo_-'-':rd: !~L,,;iIIo srains tend !J. ~i'IfI,D' ~li~.I~~,t. 1~1Il alII!.- ~ ml beoome reoriented :I'n t hie surface so as to reflect the effects of the mechanical ])arame~!ersl.mposed on the surface. Tb~s Is d.(!lmonstr~ted with the aid of' figure 4..,30~1'which Ihow~ w'tuu can h.,Ill-ppen to' a s,urf3ice du.ring a ,~iIi';;dm,"i.1' '~1f'~';f'I,t iin'lf'1l ~tlW.y~ ", eerim ('ra;f" n,:), ~ ," ~l.IL!Il'._ la,~ ,~~, ;1'\.: ..F~gure 4-30(a) shows the no;rm,aJ. equiu ,gf.lruin:s (gr,aj,ns; :iil file normal confjgu:raUo-U! in the, annealed :!n,Slte); w,w.thou:~ pr~fetred oidenU,don ~)<:r d:irec~ ti,(~l1,aJ,i:ty to the indi vidual gl'lti.ns~ Wben sliding is, ~ nitiated across the sur .., f ace, however,. '{he orientat ion tends to become mere hi,!'-h~,ydfrectto~nd and progresses from (a) ~:hro'M\gb ()b )I~,(cl~ and. (d) deve'lopbiS a degree 10.1' directionality ~ ,At first ~the graJns; ~i-mpllychange their d:~reedofl,,M a result of' file' :b~lP,OSed direct ionsl movement (fig ~4-30(b))., 'W"ruh c(;uldnjllous :sUd~'nl~, a;nd the s.tr,illn associ,at.ed therewith, the' 'recrystaJb~at~on temperature .of rhe sur ... face can 'be reduced a:p'pr~cia:tJ1y., R~c'rysudUz;ad():n ca;m occur in. the surface ~
ill'if('i:r1ifs"~'!lII~'[~_~'!Jllt'i~n-i ,ifjt''f _IJ..~_ ~~~_V uW
"-". [!Iii-

the

~,AI~lt.4 ~~.~W.J.U ~~_

surface ~~~

b:~ghi:y strai:ned grains

rtJ "" " -"

~end
-

'~Q

promote

~,I:"i:HQ !liv.,IJ"~, I.J-.

~=

Ilhl

!\iT ri.1! _dl~

.~',

d!'~

~~,IIi·. _,lIllliJ.l~I~

I....

_._

.:

l~lIl~i

.;.J!

',- .~I¥"'~

~lIlUi

v.' W

I".

,'I

__ .~"

'!l'(

&lW

1~

1B.,~il,~..

1';"'ri; y

'lil

'@'

,I ".''tl

.B-¥

[II

'lllil(-'III'j. ,~~,~ L, \'

I~

I!!!

,~,

:and rIb. increases the n u:mber of ,graIns from ~ hose seen in :Hgure ,4,..,,30(1')'to the number seen in ngur,e 4-,,30(c)..'The n;rs~step in a fricUon experiment may 'be ,8. preferred olden'l.atio:n of the grains otherwise hacking 'that orlentation

235

'It.IJ~ I;....gl~

'wear resistance and maintain re'ia.-~i ely smooth surfaces in tribolosi'ca~ v systems" Materia.ls t:ha.-t exhibit this :pr()pert,y are the cast irons, 'F'Q<Jhunbelieved to be respo:nsJble for the good 'w'car characteristics associated Mih
_~

been
',' . '.. l
J

I"'

k-!Ii"II'O"WH ~nr ~2IL' '.. ~IUI~1~!tJ.I

r

sora 'f' tim • th at een ain :m' terlals have lnherentlv IIlIJIt~._
!ill.:
J _ ,"

III..

'

'"

! :.

~~

. ," _

JILI,L

,I

1'.. \' L~ 1

III .'

!.]II

g.'

" II~II!

L"-'dl&'"

;J"

11:(.' _'

DOO-' . ,,,4 ,~,

dreds, o,f years,~east irons have been used because tb,ey have inh-en:nUy B,ood ~ 'Il... "If )'" h 'w!ea:rresistance. Thie presence orf' car 'bon (" gra:pl,llle''_~orm:mtne cast ~ .. E : un non ~s cut irons. There are a number of cast irons, and they have va'r,y]~ng com'p----'o,-,sit,inli eonralnln 0' O'ra~'n'h' ,j,+"Q] '{n'P!' a- 'Ulnrnh' Aiirie carbon )-" So ie 'h' 'Y-Ie' better "'m-D D r: :1 u:u weill'-- --'-S:~~fa-- than -th- -- b t'bhave ~uer' W""-' ...... rec_m8~',_nce'~__a_-, o·~_,e-T,s,,].'.'Ul',,~ In. g,eneriU,~ t..,,11: cas~ ,1ron~,1w,!e 'k~,t,--~~J. ! ar
'"Hi:':' . -:_.>=I. ~VI'~~
'~ . A..l: .~
~I' -.

_tl~~,

~VJI

'

[I

'VIIIJ~'

,'U~~I

'1¥

>I!!

_~

.'

:Uf·· .-.'

_~i.

'1Ii.r._

·-it

".' -, -'- -, -.,-, -,..,,' .

'1tti :, ~,,,,,,, . 1fT V

---:-iIi-

,-. -

---

'n['.....,~Ft-~.iI:! ',iI:"" 'U,t" .... ,[Ii,.... '"' ,I1.-

than '~,~l·

!I.II,

iron-base ,1.1:,

'=!UIiI-~"'" ~lll~'Vi:!' ~. '~VJ!';.1Iij

h= ....h do not .... ontain gr"ap:bl'tA A'---:n': ''WA.u,liu.= ,l.l'u'_ ",",VJLI!!l.: ." '_' , -: ' ,:,,_,"L,~,',,·

'A''IIi'';!ilrH'ri;-

-,-",-, sur -'1"'''1,--: - '~-'V-- ~;- 'b'~!li,k' v";"'- _, ~,,~ce W-:5 I_QC - :_ 'tUi~ ~-c_ ehes :b1lt.he wear ~:nt:a(;~ lG.ne;; A carltfl!1~;examin8Jtion. of'th.,ese black, pa'-h~hes, 'wllb A'~S reveals 'them to be carbon. The ,gra.:pl1:it.'e from the east iron has Iio.... "" ubbed O'UI& ,.,rel'~ .,-- lave, .-. tormeo AI-, rfae b,1in'" aeeome- ru ;..·ea o It 0 I'll '''b--'e sur ,r·'·' " an.'d ,~,-, ' .... a ,pro,eCd_iii"",e" ,SUI' aee :f"'~' In es - - - - - th- - _:u_~~ straen - -- - th- - ~- ~ - -"-n I:_:.:.sence",',-. Ie: h- lk s,-mli;.,.;ure' o.f' '. ·"e 'cas-t.., u·on --,carnes; - ~-- 1, ill Lu~lt '.'--:s: - rd In .'. ~_~ uut-m ~:OJ,'_, lub"f~"cant' Th~' gr, a.--:h-it - be-e- --.-- ,smit::r-'OO' __Oef'._.JIL!t'n- - -_UL, __': =- 1_",_,~:- c'O'n' tact surface ·'n t'he' _;__,_CI, ,_ _:'_" _,_~_,,,, ,~-,e - - __,_, Ill_Ii _!_:--:omes -'---"--'a : --''V'- -- ' p zone and provides a, lu.b.ri,eating :rUm;,this minimizes the' i)(Uleslv'e WHr and transfers from one surface ttl another, An. example of' the cf.fecdvemess o,f tb;e smearing out of' the carbon across the' surface is indicated in the ' hl n 4 -se uy 'l k~ n,' -:.~(lnl J:ti ,Iotomb:::roSra.p, tn '~:Igure" 31:. 'L- ,ooLj.-ns; at, t'be aetuat ru 'b'b" C'OInl!8a ~ . b zone" both mside and outside, Outside me eentaer zone U1Qe' is yerJ tilde :graphiie'; it, ls seen OInl'y' as isolated. Uttle islands hl the matrix '"I:n the wear track ·(:tb~~, 'wAQ'..,@.rri;n'-!tQ,.,..'-!'J'nn-'.'p-'I"o··ftp{f")-·h·nwtVQ'I,",.~ . rhe I, AIiH"iI:iIi'ra""io'D" 'l'~ m nc:'1i.. een ._ ~.I ~IL, a .....'~ :,c I." r-I!Ir.I~:.. .. Iyl _. " _ '.a:· "_\~,~l hil:il:b"'e'Ji .. 'rkat, i~because lh~e_ , of ,~,--;olnh~!t- . :& __ ,IL,U ... ~_._JL __ s'mall is'I'A'odes . gr~ __ h',3,Ve' become _ rub-bed, Ji~ l_~ v_ _ _. __
'iI'\t:1IiS"~t)"--:'1
-j, "
I .. . . • _. .... ... ·1 \ -., .

ple of one such microstructure at the surface is presented in :Ogure 4"'16,., P'ilure 4..,36 is H, :p,huu)mic,rograp:h of a wear track all a gray cast ~:rO'Jilcom-,- r'1l..,C" 1'-' -,--xaml!lun.g -"f·c .'. ,r.i,;.o.:.Llon,_ wilLI ,], -- -r:-- --t", ,ea_ uon ~ E=--'-' -- ';-,,;' -, 00, ,th e ,Jl' n ,~-pe.LJ~~:en

f'

",~I

Ilf"~

~\,

It.

'_'

I~'

."U,

1~-~'IJ~Ii!IIH . :~,

.'"

239

'R---'
,

"e'l .erenees
1', ','c ' --,-

,-

-I

9 Tis.uldm!t:.; T.:: _d Si\kama,ohl ~1'.,:, f:riot.mn

1 ,

i8~,w~en

~o, :B.q1;m1ilOO$.~ :;,K'e~~l~ M.

SOl., L" Action.

Jap., Soc" ~b;

8,1-W]0. ~~.,Sau_lQ~QI~.. ~ ~ndJT~ukiro~, 1'.,~ ,Dd'ti)lmatiolnJ and 'F:ri~tffioolhhaviow of th;~ ]rgwf\loti~n ~Il, T Q~ast;;5c,rarlc:hl(rL~dO'n., 'Wleaf',~,\1\0:1"~'" 1978~ :PJ)'~ '9.'3--101. tl~, Ml,'OshJ.~ K,.: ,a:rIlB BtiC~kley~ H.,:: F:'rk:irno:m and W'C8.f ICbar,iW:buj!!Ut~, '0" 'h·oll."CbrD:r.uium, D" A[iij)"s, :in Contract wiori1, ThenlSleI,~~ iBI.ncl Si~i~ '~bitJe" NASA TP~1..38,1.I' 1'919 ~3~W'~~~'! L~ D'.~ hJ:f]~Ill~ o,t :Detl(fi~Dent I[Hl E}U) l~brlcatiioflj,. A&LE TritfllS!.. ""01.. :U 00,. ., :~II:i 9"8;~ PIP", 4J ~S:,2~ 14", Ytfmrt!liU!u .Jr.dlMrlres~ and '\Y'ettrtmM; JiU!l~_a, It.:: EL'e'mcID1Itary D.i51~d~!liIJ ~,),;, ,MacM~ 'lan ce, ~ 1w.4'" l 'S;", :Du:f~ooet K;,:_,.~,and 'Gla~r ~W,. A.:~ ' Rom!]! 'COf1U~ct:DefbUl]'uuiofaJ ,of MgO SiR\lle C'rYJitals.,
1 •

M,,.: ~d COtrrliC'l,~ It.~C:Om~'ru~~~1 D'e!l\fun~f:~mJtf!.1X:De C~iy,W'e l:Jit Cootac~. D"Ul1 f:r.ot[~CiLir Hel'ti1i'dsp:~ieriiq,'~e, w~ ~'Vol,.. ~:~'I Itti18", PiP"

EriWS,.BiIllJ~.~ VlOw.. 19~ no" ~21,',. 1M. ]"9j'6" alP. ,:54~.

'Hard :R.CIIlll@ljh, ,~d. S~ft

Smo01:b SUlrfa~,.

1i

i,

W~M~Vlot 3:7~ ~"(h 2J,~:12,p]J1,

l
-lli'iLifitlil ~ ~-",' ~J1jl!
.~ '. F.;']- ~I;'ngi""m-, n -11 ,"!ri' aE. " .& lIltllf .....'Y. ~,~~,rO;'i" ~~ '9iI~ nn. ",~'i!ll'~l,,o;ji';lil,
III

• '! ,;;t,
~l

'01P.

it[..... !t.,o;, iL,'... I! U.!!JU~A~

,!II-~

~~.

Ii.:"\o'ufl~ ,....f· Il~II.;., ~~.

'~ .....~ ;",~, '.~ ~'~ ,ry IL;""h'~-.I ,'1""0111:l' \

'G'.

:"-'!"·,_',Ir'~;f",'llI.tl ~,I[~ll!

~~d1!Li,_ ~~Ii i;!k-ui~ Ji~~-~ ~~~,.,

~i, .,.~~,¥

'l'~ g.~
I

of' :SlI:arDdm"dJs,~H;,lj', {AD",AO~~a,S}. 19',.o(ja~biJr ~ :t I:.~~rld, :SkQfb~ill:1J. V,.:' M'dal 'Su~'fft~ tl)"'er Stru~iliJ~ !Fo:rrnmj.o~, 'U~,d-et :S~ld[1i1 "'rid:i(!lliI!~ W'~ar ~ 'v-ot :s I. ~ 1918~,pp., 127~l16. 10" BlIl'I,C:j[ij<j' W," 'Ct: ItckriitalU~tiol'l. 'V'N.rorm~eil" ~tand U'nd Edl.ohiml., HMdbrucb, ,d:c-r MeutUII'1i<b'v,sik:,Rd,. III "f~.2, G,. ,M'~i.n~, ed~ Alademis~'8' 'V'~J"I!~~---~; lell~I"ft, ',,-,b-.. .. iJ! - .. ~!,!--_. ~:1!a, , .. -, m., it ,(Ui,p~eWg)~ j 941 ~ :1)., :3:S6·,. ;2.1.StiD'u,].t:is; 'L. :!E.:: 'Da11l18i,lm SUii'fatl~ :LllI,~: Mttam5,. 'Tht, SlIlffl.et' Chemiiluoy c,f' M'Rlls, ,udl
tiOrgall "i)llIreElU
t

l1.. Veam~ K.; ud So, S., .$.,:: 'C'hanK~,e:rin.t~o:n Real S'lIJ'raoes, b:)r EU~Plo.mtu,)',. :Sllfrao~' 3¢j.t oJ 'vl~l. 2:9~, 1~'l! ~,P., ,31'~J9S;~ :18" R:!LIDff~ . W .:: Studies of' De.forrmatooiil ,aDd SI:idwrJit 'ijj~ve'lr.'Tr,uts in :i'r~n" NBSIR, '1'~"2!,NlaA

~,_).I

._,l~,~

.-

!f.'"

-!

---

-~, - - -

-,

_.

- _..

iI'

,-

"

, --

--

I'

M'i~c'bcill~"M., R ..:: RCiri~ 'dJirtnt :M~bamcal Prtlpert'i~ of C8.'!;{St_ilS With E:m:~i1; iOIbl F"';aHt,iau\C~ ,.:t~a:vi'iLir ,i':JIi~dI i,b," l!IilJt'jiIi'.-, ..... Iifi;,f M".,..;-:i ..:II~IB~if"'~,ii;li[it~ii;t-':...e;., J. !l:i.uD" ..... 'I... ,t;ili·-.- , , _r:liIlIQ P'i'ilQ" --"0- - ---- - - - ~ .• -~~_!JI!""'''''' ...ih. . 'lOr. \!lot no, 4'1' O~L ~91i\~ j\2i'~,l43, :pp" :23. Cam~)b.e:m~, E"'i' ,ed,,: 'Hjp Tnn:piM'·a~Ul\~T~Ii1.'I'u,;do,gy., i., John W'il~ .& Soll$,! Inc,., l"6 ..
2,2,.

~:....' , d ':ru ~mt'OO:rL\U:'l1r$,!. H C':'0" - , ~-'. '," '-~t!()~".

"'""', W,'!!'

;1!11(~1Ii

r" •••:k.,.;,

W"~l ,iIili.,~ ll!.'ty

'

,Iji .... -

,~Il~~

1-'iIilC+~ ,l.7tN'I p..':;II'"",, .M

I~ ~~, . _

"I,!

---'¥

~=

YiII~~MIU,~Ml.,!Ii!!~

.Ii'!!"m

T·,-,*"",Jjj.,I-'-~'!"''"!I

·" .,41,tl:e i;iiJ~·le· ..u~,~

ch eleave literallvoJ theusends of_ in.. 0"la111c. 2nd. other types of crystals (ref" .2). The cleavage ex,:periimen~ is. ·im·portam because 'with c~ea,vage' t wo new surfaces arc .genenlited," In t he' process,~the en~rgy required ~'Q elea 'lie the crystal is,a refleetlon of the en.er,IY o{ cohesive bonding ..
't'b~\J' !I..... I11"'-" J'
'IiiIi~ .......!I Ulil:I<!;U.

a U.

hammer.. .uulum _

'~.I·-,A """., ~~ .. ~0" ·;'~e~ .riiHu . _. V

~L..

Surf.,ce: E -ergy. Effec'ts

experiments. Gilman expended considerable effort in study~bl;g, the c'le:a,vage n , ~.n ~1·1·"..2 su ~,. n en'il'i'Ol:I,~ n'n it' ,U~, U. th .... I~.'":~gl and ... ''--Y n'ft:lit ,"li'l Uriit"!i Iy r i:;I!vl~ ,y. ~: r ·f-.o. ces as wellas t" br~ (f~IIf'!ie:Ii'~~~ilion IV ·f: 1W~ ~AJi, i '_ Q~' '~'~"1W I preaches for 'c-;aJc:utali:n~ and determining the surface enC1.",ll-Y solids, Oth.'e;r of investigators have done Uk.ew.i:se.~ and many equations have been, p'l\cpared and. put rorth :10 predkt surface energies of solid surfaoes ~The GUm,an apPW'03(h. is is. :Felad,vet, simple one"
;~I~I~~ Ig,~ '_"~~J~I ~I~,~,i .. "\

The surface ,ener.I,'Y(ener,YY associated wi~:h the f'res:hly ,g,enerat.edsurface) i,s 'ext remely i:m'port,an( to audhefdorn~ and, t his can 'be arr iv,oo, at bY' cleavage
Q~ Jj,y'!I,lII.
'~I,J..lti;lll
J

:1' ....

'''ill

Oibn,on·ts si.mp,le equation fo:r ,c',aJcula.d:ng surface energy' i:s .

where

an
:E
Yo
":i!.i," ~

range or elastic distance '0 f the aur,ac~h~·e forces elastic mo d ulus equilibrium lattice' conSUUlj~, perpendicular to 'plane

sur face I~ :'~~

1j}!1. :_
[J

11i1Ii!ni.;M-~V !9.llI~Jl ,~.J~

The desirable fie ature .makin.s, the calculatlo

have argued that it is the close ..packed 'pla;nes, In. the sOI~id t h,at pre fer,tnt~aUy' cleave, but this does not ex:p~a.in the beba vior 01 f many Cf)1staJ UrtIle' olids wldl a zi:n.'c:~bltnd struct ure {e",.g ZnS or- blS) or a fluorite s .." structure (:e,..g. C;B),F 'Others have discussed the cleavage plane as behl~ the 2)" n~,ane' f ehem leal bonds il-'.... r, un it area__Th/_I.s ,I)- - ' ~ fi~ -, ar if" _. - wit,D the m hl im u m numbero _. ,_, . . . -' -~ ticular approaeh 'fans 'f rom the re~af ve~y v:t.ll,ue' meaning of chemical bond ~
SO-:I1U~'
t,
I. • • " .-

place ,a:~ong Icerud:n preferred planes En the ,c:ry;s~,aUln.e solid '. These are referred to as, the cleavage planes '" 'V,ar'~oustxplltlil,adon.s· have been given th Fough the years to ide~ndfy why rert,a:in I';~;~u~es eleave and other's do uot ~

of surface ,energy are readUy available. 'When one alt.e.m'pts to cleave at ·c<ry:stalUn.e ~oUd,. 'c:leafvag'e:g,en'fl'aUy takes
-1

>0

r this

equation. is that those parameters needled. for

"= - - -~

. -'--

-.

...,

• -' - '-

argument is ~.hat the anisotropic ,eh~s'~ constants determine the me cleavage pl~anieof a C: Ii yst alUnc: solid, And ~astly, and, probab:ly the ex:plan3'~'ion'wb'wch is most com,mo'n~ly su bseri bed ~O'~Ihe .p,l,an,'e minimum surface t of energy I,S the cleavage :p~,a:rnein rhe crystal line solid, Even wh'h this, 't1i ph~ulatio'n there are except ions ~ for example both iron and tungsten have the lowest surface energy on title ('J :1.0)p,~anes Y1et. these tw'o particular metals appLUU' to cleave along (~nO) planes ~However ~ other body ..centered -cubic metals ~ sueh as tanta um and V'~Radiwn,~ do elea ve along I( 1~'0) planes: tbalt is t.h~y· '~OU'O;Wan expected behavior ' '(t!iied on :t he explanatlon 0 f the lower surface ener gy' plane 'being the cletil'yage plane,
~I

s~j n another

'wi~h surface enl(!r.g,y· values for ~'he" dll ree metals ~ 'The ,coeffie.iient of adhe .. , sien is the ratio of 'the'force to separate 'the: solid. surfaces once brought i,i1J~IO solid-state contact to the load. 'with 'W'h~lchthe surfaces are i.niUaUy pressed
Platinum ~which has the h':ghest surface energy :illl. table $,.,ll. atso has the hi;Bhesi~ adhesion coefficruent.; zin.c'~vihicb has ~:heiowes~: urface energy also s 'has the lowest I,dhes~on coefficient. These data are consistent 'wit.h those one' mj,gb~: n~jc~ a pate 'ro,m 1he energetics of the solid surfaces ~nvol ved,
j jl

into oont.ac~.,

',~,
c:.
,I'

- ',," -,........,1'--1··I'; ]- 1-:' ~- r- i-I'

.........., ,
-

-'

............. -

I
,_ ~ :._ -

'1, '_ ._ L,

.'

,~.-~,..,~

E'i\i:l'~~'!"f"" I~

~=" _
l~.

'i''''''.·~EIi'.III,•. ;!I''''''t_;!"''.ti, J.',I:,m,.""j',."",,,,,,,.i"'ij'

~f~ffiUIH~·[1ii.II7~ ~~ U.~~~llHl~

,;"'''·.~t:~il'' ~v.~~;~~~ 'If......... P.,_ ~'Il J', !~~~l~

TABLE S,·II.,~ 8lJ1JitFjOiC"E, :NHIOIES AND E

SlELF-"AJ1JHESI'ON~'
J.",~.'g:'UnleM._
'N;jj' -,,",~_.,

'!J'R'

ooetiki,p.t
10f' PI;
I
I

adhefdoo
0'" 8
~'1 ~2
.

3,2100
',::__:)-_ 22100)
'

eu
'Zn
,R ',. '-., '.' .. ' '."

..

740

.Refel"'enC'E! 3~ 'b AU data ext:r~;nF~la;ted ,or in't,e~lated. .. ~~ mr'''!I.I'!' ltu:cept thfJ~lefO,f ,Al~ ,Mit 20*, u.d
[~\;,;, ~,~,~ r .

calculations Such mei.tsurem en~5, were made 'for ,g,o~d. and a :num ber of other I .' h ,~II ,~e~~leSiv,e 'inull ...:Ii~ ,. metals ., contact w~t.' tungsten, ano th ,,,.. ~ b" di energres 0'f' rnese tn vario us m,eta~ to m: 5, ungsten were calculated '(Jie:f ~ 4-).. The resu lu~, of these
i

'II!;.

m 1ro;og.'_,J<,,,4r,,,",m,e:ni!!.S
,;i!Ii';(;o'!l';'l~'~-''''--'C',-

of the' metal for various metals In adhesive contact 'witb rungsten, 'The' metal 'which exhibit.s: rhe st:ronge;s~ bindin.g force 'tto t.uAIS[,ell ~stungsten itSle']'f';, that is, the energy of ,co,hes~oFi(se~ -adheslon) '~sstronger than the energies of f di:ss,iln:Ua:r metals bonding to. the tungsten surface, That is, the first observa~a£: tJon ii1' ... L.,. '. _. .,....,!II , 'f'"rom ... ,doh,,; d ro ee mace ,e,B.III.i3;, 0 'f' f~i l~u]"\e,,.) 1U,~ Another observst Ion It,Qbe' made from figure ,5... ,is that ~he mem bets 0 f 6 the p-ia,dnurn :rn,letab~ famm~y (osmium i:ddiu:m, and ~I~,alt urn) show a in decreasing adhesive elle-rg,y to th,e: t,UU,I;st,e"l] as t,he cohesive energies 0 f the -[amUy members decrease. In other words, the ener'gy of cohesion in osmium j,s,greater Unan that ~JlI ir:iid~um" and t ha~ in iridium ls greater than, that :in plath1 um, If the cohesive 'bw nd:in,1 energies are compared with the ;adJh,ll.!ssve ell"er,gy va ues ploiued in figure 5;-6; at eorrelat ion 0 f cohesive binding energies o f the metals and the adhesive energies of the metals to t uagsten is seen. The bonding a~ the in~er face bet ween the metals and tungsten in each f" L 'L i..," ~I t case 0'f' ngure j~.. is stronger man tne b d'. '. tne ,ooueswve~y'w'ea;'er 0'f ~• eon ··~:ng 't., In ~be' ~wo mar erials ~ In '01 her words ~ in each cage run ft.gun~: ..6 ~the metal in 5 contact with It,ungs-ten Is",cohie5lii vle:ty weaker than It,u:D,lsten'. Censequemly, when tbe solid surfaces are' s.eparatoo after adhes;iv,e eontaet has, been. made, fracture occurs in the 00 -,~esjjv',e onds -bl ~he metal brought :illlto eontaet with b I - '. ~.' ~. b f me tungsten, F t-,at reason a corretanon exu;~s, Wlt· h tne mem"ers '0.:_ liflk --'Of' 'h p~athlu:m metals ramUy and their cohesive bi,nd.i~g, energies. ,Of all the met als brought into contact with ~ungsten runfigure 5;,~6,rp. SiO~d the bonds 'to. [he' tungsten 1]] the weakest fashion, DespU,~'this weak, bondins it was speculated t.hat a. ,8o~drungsten compound forms on the .saUd sur:fa;ce ... (ng, 5;.. Thus, despite lCom:pound rormadon, the bondiIl;g;, is sd,n 'not as . 5)., s,trOillg as i~is for the other metals (p:~atin:um~ iridlum, osmium, rheum urn J
:!',cIt, ilL', __ : 'C,.-'-. -'.' 'II t
i,
a,

in u~ c:s6:-6 ~ ,..4I' • leu,t;r_g:y .'is p"oU~, as '!t.-'.] ""..:Ii ~.' ~]1ngure S~", tne au. h~,eSlYe ~Uocalonesl per gr,mo atom
C'~',',

ned ,EU'~ ,prese-m.I!l-"" ' ,

,'C' ,::_; ',".,~,-.'",

,i,,'

'~'DU'I;",j!!j;

",I!;",

.)-"

'I;jj,'·

--,

1•

'200""-,'
.
1','-

.'

lIi,i!Ii"""~'m ,1!"L~~ro,;rllll ..

"!i],iI::~

~.J'.J.