24

ENGINEERING METAI,LURGY

"Minerals Yearbook," U.S. Department of Interior, Bureau of Mines, Washington " (publihed annually). Newton, J.: "An Introduction to Metallurgy," John Wiley & Sons, Inc., New York,

t9.

Schuhrna,nn,

R.:'"Metallurgical Engineering,'l Addison-Wesley Publishing Company,

Ca,mbridge, Mass., 1953.

Stoughton, B.: "The Metallurgy of Iron and Steel," McGraw-Hill Book Company, Inc., New York, 1934. Yan Arsdale, G. D.: "Hydrometallurgy of Base Metals," McGraw-Hill Book Company, fnc,, New York, 1953.

iP

CHAPTER 2

ATOMS AND CRYSTALS

ATOMIC STRUCTURE

Free Atoms. Atoms are the smallest particles of matter which have l,lrc properties characteristic of the elements. Atoms are composed of llrrrrc parts: protons, neu,trons, and electrons. Protons and neutrons
r'{)rrl)ose the nucleus rvhich is positively charged, and the negatively llrrr,r'gcd electrons rotate around it and spin around their axes. The rrrol,i<n of the electrons around the nucleus cannot be known with cerlrr,irrl,.y since it is impossible to measure iL (Hei,se'nberg uncertaintg princi|lr'), ltr{, it is possible to calculate probabilities of electrons being in r'r'r'l,rr,in positions and the internal energy corresponding to the most proba-

lrlo rositions. Thus any representation of the atom does not show the nll,rnl rlistrrrrution of electrons within it, but rather the mostprobableone. lr)krcl,r<ns more around the nucleus in orbits such that the energy of the h,cl,r'rns is constant within the orbit. IrIo more than two electrons can lil, irr rr,rry one orbit, and in order to fit together, they must spin in opposite rlilorr(,iorrs (l'auli erclusion principle). Each orbit differs from the others lrv orro or rnore energy quanta, the energy level increasing with the orbit's rlixl,rlrrcc l'rom the nucleus. The orbits are grouped in shells, and within llrr' lrclls l;here are subdivisiorrs called energy leuels. The maximum frtrlrol ol'clcctrons that can fit in each shell is 2N2, in which N is the uh,ll rurnlror'. 'Ihus the first shell contains up to two electrons, the .'r,rrrrl rr, rnrr,xirnum of eight, the third eighteen, etc. 'l'lrr' r.hrcl,r'ons tcnd to move to the lower-energy-level orbits. Usually llr!l r,or'r'c$p<rr<l to the levels in the inner shells, and the inner shells are fllh,rl l,r'l'rr'c clcctrons take positions in the next shell. 'Ihis is not always Itrrr', rr rrrrr,rr.y clcmonts the upper energy levels of an inner shell may be ltllr,t' I,lurrr l,lrc lowur cncrgy levels of the next, shell. In those elements, nirrr,l,t'orrt l,rr,krr rosit,ions in thc outer shell before filling the inner one. l,'illr'rl lrrlls rlrc sl;tltlc; rulfilletl ones are unstable and they tend to lmlrnrr, lillcrl. 'l'his ci,rr l,ir,l<c plilcc cithcr by the formation of chemical trrilrllrltllr ln ot' lrv l,lrc I'olnlrt,t,i<lrr ol' rn<lcr:ttlcs. Aluttt lhn<ling. 'l'lrc rrrrrcsrrnl,lr,{,iorr of t,lle lll,oln irl rvhirrh thc clcctrons lltrrtttlr.v llrrt lorvosl, rossilrlc ()nclg.y lovcls is l,rrtc orrly I'or'r,rr (,otn irt the
'h

freo ;ae, Whorr atrmn rpprouoh ouor, o*Ll,l]nn lntnrotlot lrctwecr them takos placo antl tho intornnl onorgy of hn utomx i affootttl by two forces: a force of attraction betweon tha atons which tontlr to bring thom closer together, and a repulsion arising whtn tho outer shclls stort to ovorlap. The first force tends to lower the internal onergy of tho atom, while the second raises it. The two forces balance each other when the atoms are at a certain distance, where the internal energy of the atoms reaches a minimum (FiS. 2-1). Since equilibrium corresponds to a minimum of internal energy, the atoms tend to assume positions at a fixed distance

Total internal energy

lnter:nal energy ncrease caused by repulsion

Distance between atoms

lnternal energy decrease caused by attraction

R=atomlc radius

Er:
Frc.lZ-|. Energy
as a

bonding energy

function of distance between atoms.

from each other. These distances, which are characteristic for eavh element, are considered the atomic diameters. The atomic diamoter is
usually determined by measuring the distance of closest approach of two
atoms in the solid state.

The atomic diameter is controlled by several factors, the two most important being the number of occupied shells and the strength of the attraction forces. When only few shells are occupied the diameter is small; it, increases as the number of occupied shells increases. Table 3 shows the electronic configuration and the atomic diameter of the elements of the first two groups of the periodic tablq. The strength of the attraction forces increases as the number of bonding electrons (valence electrons) inereases, and correspondingly the atomic diameter decreases. Thus the atomic diameter decreases as the

It, i l,o lur rol,orl l,hal, matry elements, especially the higher valence ouor, rkl not; ulwu,ys display their full valence in the metallic state and
'ltlll,,: iJ. A'uurc l)reuu'r'nn ,tu .Er,ucrnoN CoNnrcun,TroN oF rgn Er,urunxrs oF THE Frnsr ,c.tr Sncoo Gnoups
Number of electrons lenrent Atomic
ntrmber

v4lrlnor! irrcronnox, wil,lrirr lx)ri(xl. As tt,tt ttxntrtrlu, l;lto t,ttltritl rlitlttll,rrrl wil,lritr t,lro l'rttt'1,1 lxlri(xl u,r'o sllowtt in'I'uble 4.

^'rrM ()n,oh

ANl,

llltYl

Allt

a,

Atomic diameter,
A

Li
Na
11

3.04 3.72
4.62 4.54 5.32

K
Rb
Cs

19

8
18
18

37
rb

Be

Mg
Ca Sr

4 L2

3.t2
2 8
18 18

3.20
3.93 4.31

Ba

20 38 56

4.35
THE

T,u 4. Atourc Drunr:nns ev Vlr,ncs oF

Er,unts or

rHE

Gnoup oF THE Fountu Pnno

Atomic diameter, A

Element

K
Ca
Sc

,
3 4

4.62 3.93

3.20
2. 93

Ti
V Cr Mn
Fe
Co

2.63

Ni

5.8 5.8 5.8 5.8 5.8

2.45-2.7L 2.24-2.96
2.48

2.5r
2.49

iometimes may display valences which are fra,ctiona,l, zero, or even nega-

,ive. For
iero and

example, nickel

ther combinations

it will show valences ranging all the way

to -0.7
(electron absorber).

in its crystal will show a valence of 5.8; in

down to

in some

cases even down

28

ENGINEDRING ME'I'AITIJU RGY

CRYSTAL STRUCTURE

rial. The atoms are not statically located; rather, they are in dynamic equilibrium, and they continuously oscillate about fixed sites which are the centers of all the positions which the atoms can assume. These centers constitute the lattice points of the crystal. Many different types of crystals are formed and the reasons for this variety are little known. There is evidence that the number of valence electrons is one of the controlling factors. When this number is lorv, the elements tend to form face-eentered cubic crystals; somervhat higher numbers of electrons favor hexagonal, close-packed lattices; still higher values favor body-centered cubic crystals.l There are many exceptions to this rule. Some of them can be explained by the fact that several of the elements in the metallic state do not always display their full valences, as mentioned previously. Other exceptions, as for example the body-centered cubic lattices of sodium, potassium, etc., indicate that the number of valence electrons is not the only factor controlling crystal structure. There are some types of crystals rvhich can be considered molecules. In these, each atom shares the valence electrons with its close neighbors, resulting in the formation of closed shells. The "diamond-type" crystal (Fig. 2-2), formed by such tetravalent elements as carbon, silicon, germanium, and tin, allorvs such a sharing; some penta- and hexavalent eloments also have crystals in which the atoms are arranged in such a \4'a) as to have three or trvo close neighbors, respectively. All the known types of crystals can be classified in seven systems: (1) cubic, or isometric; (2) hexagonal; (3) tetragonal; (4) orthorhombic; (5) rhombohedral; (6) triclinic; and (7) monoclinic. Figure 2-2 shows some of the typical crystals of each system. Most of the important metals crystallize either in the cubic or hexagonal system, and only three types of crystals are commonly encounterc<l in the metals: the face-centered cubic, the body-centered cubi<r, arrrl thc hexagonal close-packed. Other types of crystals,"althotrgh sornet,imcs encountered in less important metals and in compotrnds, arc ol'irrtrrcsl, only to the specialist; no detailed krrorvlerlge of hern is rrrrrtirrrrl lot'rr basic understanding of metallrrrgical phorr<lm<lnrr,. The number of toms whiclr rronsl,il,rrl,c:r, r,t'.yst,ll is vrrr.y lrr,r'gc rr,rrrl cvcrr t,lrc srnrlltsl, r,rystllls:Ir(] (,ourlx)scrl ol'lrillirrrs ol l,l'illiors rl'lr,l,os. 'l'1r,,
rl,'o lr rlistusirr ol llrllc r.ll,slrrl lr'x.s, srr'r,211,

Crystal Types. The tendency of atoms to assume fixed positions with respect to each other gives rise to the crystalline structure of solids. The crystalline form is characterized by the fact that the atoms are distributed in a regular pattern at distances which are the same throughout the mate-

AI'OMS AND

CRYSTALS

29

ouping of atoms whose repetition will produce the crystal is called the cell. The number of atoms in the unit cell is very small since it does rot constitute a crystal in itself but is only the building block of the rystal. For this reason atoms at the corner of the cells belong to several clls at the same time and are counted only as fractions. For example, rr the cubic lattice each atom at the corner may belong to eight different clls, so that only one-eighth of each atom can be counted in one cell. In lris way the face-centered cubic unit cell has
t,n,,t

8 atoms at the corners X ),(

:1

?iffiiin

the faces

x )l

I'lrr: body-centered cubic has

8 atoms at the corners X 1 atom at the center

)( :1

:1

Total
rr l,he hexagonal lattices the tr)n, rrs shown in rrrrrl <rlose-packed

unit cell contains only one-third of the hexaFig. 2-2b by the heavy lines. Accordirrgly, the hexagunit cell has
8 atoms at the corners X I atom inside the cell

Total llnit,
<rclls

ft :1 :1 ,

can be defined by giving their types and parameters. The

,rrlric <rcll, in which the faces are all of the same dimensions, requires only rrrr, rrrrilmcter o; the hexagonal cell requires two parameters, one which x llrrr rvirlt;h of the hexagons o, the other the height of the side faces c. {rrrcl,ilncs, instcatl of this last parameter, the axial ratio c,/o is given. 'l'lrrr rlirnursiorrs of the parameters are usually expressed in angstrom rrril.H (l A : l0 " cm). Iinit cells of elements range from 2 to 6 A; comroutrrls wlliclr lut,v<r morc complex lattices may range up to 30 or 35 A. ,ll tllt'r ittlt',r's lrrr rrsctl l,o designate a certain set of planes through a ,r',,rrlll. ( )lrc trolrrcr ol' t,lrrr clystal is assumed as the origin of space coordiurlu rr,rrrl r,rr.y scl, ol' rltrrrrs t,hrrlrgh the crystal is identified by the recipro,nlrr ,rl'il,s slur,llcsl, irr{,crsc<:t,iorrs wit,h thos< coordinates, the unit of the ,rrnt'rlirrrr,{r's lrt'irrg I,lrc lrr,l,t,irrc xlrlr,m<ll,cr <lf thc crystal. For example, in r lrrlril llysl,rrl (1,'ig. :J-ll) l,lrc rll,rrc (ll)ltll inl,ct'scr:ts thc axis at a disrur'.

ol l

rnil,

lr.l

licc

rrrrr,rrrcl,rrr ;r,, lxrirrg r:rr':r,llcl l,o thc

1t7

and z axes,

30

ENGINEERING

METALI,URGY

r_-o*-:+l

r--o---1

Face - centered

l*-'--l

Simple Hexagonal

Hexagonal close

packed (HcP)

'

(b)

/':tazt

Hexagonal

Lattices

systems' Frc. 2-2' Some typical crystals of the seven

ATOMS AND CR,YSTAIJS

_Face. centered Tetragonat ( Fct)

Body. centered

Tetragonal (Bct)

(c)

TAagonat.lattices

o*/3+W
Rhombohedral Simple

Monocllnlc

Simpte
(el

d,*/3*W
rrdilc'simpre

Fa. &2 (Continuad)

ENGINEERING. METALI,RGY

'7i
\
It

r --:rlrt
(a

ll t!

Di ,

Fo, 2-8,

?llnu

through the oryrtdr,

ATOI\IS AND

cftY$'raLs

33

rl,()rsccts them at

infinite distance.
I

Its Miller indexes are for the xis

t rr l,lrc y axis

I
co

l,lr<t

z axis

I
oo

'lrrs {,lre plane CDI'E has Miller indexes (100). All the other planes rrlrrllcl to plane CDFE have the same indexes. The plane HDFG has r,llxcs (010), the plane BCDII (001). In the cubic crystal these three ,lrr ol' rlanes are all equivalent and generally.ane referred to as the {100} llrrr,s. In this case braces re used instead of parentheses to enckse the urrlrcrs, to indicate reference to a family of like planes. The diagonal lnn IIGEC intersects at distances 1, l, "o and is desigru,ted by (110). 'l1' rlrrrc HCF ll.as indexes (111). The plane ABDC shown in Fig. 2-3b rlrr'ocl,s the r axis at a distance 2, the y axis at a distance 1, and the a iirr nl, rr, distance .o. Its indexes arc (rl, 1,0) or, in whole numbers, l:lol. 'l'he plane EFHG is also a {120} plane, since it intersects at 1, ',, ,, lrnd has indexes (210). Irr rr lrcxagonal crystal the most common method is t,o use four axes \lrllr,r'-llrr,vais system) as shown in Fig. 2-3c. Then the plate ABCDEIT r', nr(l('\('s (0001),the plane EfGH (10T0), the plane ACLN (1120), where r l,rr,r's rr,bove the o and at and z indexes denote intersections in the 'prrl,ivrr rlirections of the axes. Three indexs o1, o2, and c are sufficient r rlr,rrigrlrt,r: elny planes in the hexagonal crystal because the index on the , rrir is rclted to the indexes on the or a,nd oz &xes by the equation ( 'f n,2). Thus the (0001) plane becomes (00.1) or (001), the , llll{)) lrccorncs (10.0) or (100), and so on. Itrrrrll,iorrs irr thc clystal are designated by indexes enclosed in brackets. r llrl rulrir, rrr.ystal a given direction is perpendicular to the plane with |r: rinnr('irrrkrxrrs; lot'example, in a cubic crystal the [110] direction is ,rlx'!rli(:ul:rr' (;o l,lro (l l0) plane, but in a tetragonal or hexagonal crystal r', rrrp,lr, lxrl,wrxrrr I I l0l and (l l0) is a function of the cfa rato. 'l'lrr, rrrrrl rcrnrsurl;rr{;ion of urystals as shown in Fig. 2-2isvery useful , ,'lr, t\\' r.\,ru rno{,r'.y clrrrrrcrr 1,s, lrlanes irr the crystal, etc., but it is misleading rur, rl t'or\/c.ys l,lrc irnrrcssiorr that crystals are formed of atoms with lrl+' r.rrpl,v sl):r,corJ rvit,lrirr t,lrcrn. A lrtbttr representation is given in lp, '.1 l. I rrry Arrrrl.ysis of Crystals. ()cr:rrsionlr,llv cr.ystitls tre found which ,:rr! lrlrrlrl utrrlct lorrrliliotrs xrt'tttil,ling l,lrc [rrll tlcvclopmcnl, of l,he

34

ENGINEERING METALLURGY

faces. Typicalarequartz andsnowcrystals with clearly visible hexagonal structures and sodium chloride crystals, formed from solutions, with cubic structure. In most cases, however, and especially in metals, perfectly formed crystals cannot be obtained and other methods are needed

I'e . 2-4. Tht three rnost common lattices in metals: body-centered cubic (left), facecentered cubic (center), and hexagonal close-packed (right). Each sphere represents an atom.

XIAYt:1rgaY" CB:BD

AB-d

CB+BD*2d sin O Fre. 2-5. Bragg's law of reflection from crystal planes.

to study the crystal structure. The crystal structure can be strrdied h.y X-ray diffraction. In Fig. 2-5 is shown a series of planes in a crystal with a Bp&oing 1. When a radiation with a waye length }, strikcs thc pltnes nt rin &ngl() //, refleetions result,. If the lefluctions lnl irr phn,sc nl, lllnc N (lhol,ogrn,rlrir. film) a reinforcing r'()rJulls; il'tlrc.y l,r'o ()ltt, of llrrlnc rn,rl,inl or cornrkrlr, lrt,trctrlitrg r()Hull,s. lrr llrc firnl, r'rr,o l,lro filrr iH rlrlrkortcrl, ilr l,ho 1'1ron{l

A.IONTS

ANI} IIIS'I.,ri'Li

lt

Film for back reflection pattern

Film for transmission

pattern

-t 02

.l
oTe

'0le
i':

,,'

ll.s.,,:

# toa
(lt

r':

r,: 't, l:rrr, r:rllr.rrr (rr) 'l'lr' rtllllr. (/,) I,,rcli rcflcr:lior lr,l,lr:r'rr ol :l Il,cr'rl,,l rlrr'r't\rll ortlrrlr',1 lillr ll,'110(l) rlrrrr'llr'r'lrl'li('ltllu lo illc lx.run. 'l'lrr. rrrrrrrlrlll rrlrourr ',lr' llr rrr l lr,,l,rL, rtr,lr,rrlrr', ol rr llrrrlol,l r\rrrrr.lrl ' tlrr. rr,1,.,,,.r, rl llr. l,,1,,rr

36

ENGINEERING METAI,I,URGY

case little or no darkening results. To be in phase the two reflections must move along a path which diffeus by one or more whole wavelengths. Thus reinforcing can be obtained if the following equation is satisfied:

n\ :

2d, sin 0

in which : integer number tr : wavelength d : spacing between reflecting planes

a

angle of incidence of the radiation

This is Bragg's law and is the equation on which X-ray analysis of crystals

is based. Assuming d to be unknown, the equation can be resolved if either )t or g is known and fixed.
oo
pole

010 pole

Fre. 2-7. The poles of crystal faces.

A fixed d and variable \ give a Laue pattern. These conditions can bc obtained experimentally by using a fixed single crystal of known orientation (d constant) and "white radiation," that is, a radiation with a widr: range of wavelengths. Figure 2-6 shows the setup and the type of paltern obtained. To analyze a Laue pattern the crystal is imagined to lxr at the center of a sphere, as shown in Fig. 2-7. The perpendicular 1,o r,nv given plane of the crystal which passes through the centor of thc sJrlrclo intersects the sphere at a point which is the polc of that planc. 'l'ho srol,s in the patterns correspond to the poles of tho <lifl'crcnt plurrcs irr l,lrc crystal. By measuring oII l;hc propor s<rlll<l l,hc rlist,rr,rrcc lrcl;wccrr l,lrc
poles, the angles lrctrvcett l,hrr <lifTrrrrrrrl, lltrtrcs ol'l,ltrr clvsl,rr,l rrrltt lrc rlc{,ct' mined alrrl thus somo kn<lrvlrxlgc ol'l,lrrr rrr'.ynl,rrl sl,rrrrrlrrlc is ol rl,lrirrcrl.

ATOMS AND CNYSTAI,S

6l

X-ray beam
(

A-const)

pattern. (o) The setup. (b) Pattern of a facerrrysttl witl the (100) face perpendicular to the beam. Notice absence tflooliorrc for tho (100), (110), etc., planes.
lhrt,nt,irrg sirrglc crystal
crrbic

38

ENGINEERING METAI,I,URGY
d

variable. A fixed tr is obtained by using "characteristic radiation,"

that is, a radiation with a wavelength that is characteristic of the target material of the X-ray tube. A variable d can be obtained in two ways: by using a single crystal and rotating or oscillating it around one of its principal axes, or by using polycrystalline material with crystals having random orientations. The setup for rotating a single crystal and the pattern obtained are shown in Fig. 2-8. Each spot in the pattern corresponds to a different plane in the crystal as shown in the figure. The distance betrveen spots, measured in the proper scale, is a measure of the distance betrveen the planes, from which the unit lattice dimensions can be calculated. In addition, in most crystals some planes do not give reflections because the atoms in them are placed in such a, way that the effect of one atom cancels that of the othe-c one. These extinctions are very important sint:e they give clues as to the type of crystal. For example, in a face-centered cubic crystal the reflections from the {100} and { 110} planes are missing, in a body-centered crystal the {100} and {111} reflecrtions are missing. In the powder pattern the material to be examined is generally eithet a porvder of less than 200 mesh or a very fine-grained material. Thus the large number of crystals and the random orientation ensure t'he variable , especially if the specimen is rotated in the beam. Characteristic radiation (constant ),) is used. Figure 2-9 shows the most common setup and the type of patterns obtained. Each curved line in the pattern corresponds to a different plane in the crystal and the radius of each line is a measure of the spacing between planes. X-ray diffraction patterns can be used to determine the type of crystal (cubic, hexagonal, monoclinic, etc.), the type of lattice (face-centered, body-centered, etc.), and the lattice size. The extinctions and intensities of the reflections can be measured and used to determine the position of the atoms in the lattice. This is especially useful with crystals composed of different kinds of atoms. In addition, X-ray diffraction can be used to determine lattice distortion, orientation relationship between differenl, crystals, amount of imperfections in a crystal, et,c. Diffraction of electron beams can also be used for the same purposcs, but because of the low penetrating power of electrons, only the surflcc layers can be examined. Anisotropy. The distribution and spacing of atoms in a crystal vlt'it,s from one direction to another. In each crystal therc are dirt:<rt,iolls irr which the atoms are closer together than in other <lirections. Sirrcc lrrosl of the properties of I cryst,:il rrc rclilted to t,hc tlisl,:r,rrrro lrcl,lvccrr t,lrc rr,l,orrrs, the propcrl,ics vu,r'.y rvit,lr tlirrrc(,iorr. 'l'lris vrr,r'ir,t,iotr is crr,llrrrl rt,tt,i.solrtryt All rrr.ysl,:r,ls trrr rrnisol,rorir', lrrt(, l,lrrr rlrrgt'rrrr vlrt'ics rvil,lr l,lrc l,.ylc ol'rrryl,rr,l
.

Two different types of patterns can be obtained when tr is fixed and

ATOMS AND

CRYSTALS

39

rnd to a certain extent u'ith the property considered. In the more symnetrical crystals-(face-centered cubic or body-centered cubic)-differ)nces are seldom very pronounced; in less symmetrical crystals they may re appreciable. For example, the coeffi.cient of thermal expansion in rubic metals varies only slightly with direction; in hexagonal or less lymmetrical crystals the difference may be of the order of ,l: I or greater. When a crystalline aggregate forms, unless special conditions exist, the lrystals are generally randomly oriented. In such a case averaging of the lroperties results and the material behaves as an isotropic solid. If the
Film

X-ray beam
(

l.=const)
(

Specimen,

rotatng powder)

ilr

200

220 3il222 400 33t

(b)

420 422

313/5il

lltl,

2-l). Powder patterns. (a) The setup. () Porvder pattern of a face-centered rrrystal. Notice absence of reflections for the (100), (110), etc., planes and the llfitr'r'c of intensity between the different lines.
rlllrlo

llxrr of crvstals in an aggregate is small, it may be possible that there 116 nol, srtfficient orientations to give a complete averaging of properties; n tltir crse thc aggregate is only partially isotropic. The same happens ll atr rlggrcgrtc of a large number of crystals in which the formation of ll/l,rr,ln lrtr lrc<ln lfTectcd in such a way that the majority of them are florrt,rxl in l;hc samc dilcction. This effect, which can be produced by lpeolrr,l clyst,rllizrr,l;ion or llv rleformation, is called preferred orientation. Cryttal Transformations. 'l'hc simple lrttices have basie similarities. I lttttrrl,ot'ol'lrlr,rrl srlrrrrrrs rilcrl orrc lrr top of the other, as closely packed ll trnnilrlc, rt'rxlttcrr ci l,lrrrr l,lrc lrcxrl,gorlll or thc faco-centered cubic as lhown in l"igH.2-10r trrrrl l. 'l'ltrr srlrrrrcs rrrcl<url :ls shown in Fig.2-10b

40

ENGINEERING METAI,I,URGY

give the hexagonal lattice, with a basal plane containing seven atomsone at the center and six at the edges of the hexagon-a second plane with three atoms in a triangle, and a top plane with seven atoms again. ff, instead, the spheres are packed as in Fig. 2-70a, four planes result: one basal plane with the seven atoms in the hexagon, a second plane with three atoms in a triangle, a third plane with three atoms in a triangle but rvith its base where the preceding triangle had its apex, and a fourth plarre

Hcp

()
Fcc

(a)
Fc. 2-10. Sirnilarity between face-centered cubic and hexagonal close-packed
latti<r<rs.

lvith seven atoms in a hexagon. This structure is the face-centered cubi<t lattice, which is drawn using the diagonal from one corner to the opposil;c one &s the main axis, rather than the axis parallel to a cube edge, ts shown in Fig. 2-10c. If the atoms in positions 1, 2, and 3 movc itt sttr,lt a way that they occupy the positions marked by crosses, thc fa<rtl-<:ctttered cubic structure is transformed to the hexagonal. 'I'htls t sllll,ll movement of the atoms produces a structural t:hange. That the similarity betweerr the body- r,lr<l frr:c-<:crrl,cr<xl crrlric s(,r'trt:tures is evcn moro <:l<lsc is sh<lwrr irr l,'ig.2-ll, llont lvlriclr il, cr,n lrc iqrxrn thrt the ftr(:c-<r<lnt,crctl r:tlric sl,rt:t,tttrr r:rr,n lrc lrlso cortnirkrrctl r[H tt, l,rxl.1,.

ATOMS AND CRYSTALS

4t

inverse transformation. These and similar transformations actually take place in a large number of metals and alloys. When no change in composition is involved, crystal changes are called allotrop'ic transformations. The best known metal rvhich undergoes allotropic transformations is iron, which at room temperature is bodycentered cubic but which at 910"C (1670'F) changes to face-centered cubic and then reverses to the bodycentered cubic lattice at 1400'C (2552"F). Other important metals which undergo allotropic transfortnations are cobalt and nickel, which -l change from face-centered cubic to ---i. t\ Iulxagonal close-packed; tin, which @t I trhanges from a diamond cubic lattice i lo a tetragonal one; and titanium l alul zirconium, which change from hoxagonal close-packed to body-cenI I

centered tetragonal. Thus to transform a face-centered cubic structure to a body-centered cubic only a slight movement of atoms is necessary, by which the dimensions o and c become equal. Figure 2-11b shows the

I
I

tnt'cd cubic.

()hanges

accompanied by appreciable tthtnges in crystal properties, and The shaded atoms are those tltose changes are exploited commercommon to the two unit lattices t,inlly, as will be seen later. (c) Imperfections in Crystals. Up to Frc. 2-10. (C onnueil.) t,ltin point crystals have been disottxstxl as having perfect arrangements of atoms. This is the idealized naxo; real crystals contain a large number and variety of imperfections. M rxt metallic products are not composed of a single crystal but are pol.yrrrystalline. The different crystals have different orientations;thereflnr whurc two crystals meet a mismatching of atomic planes is present (UiH, !- l2). This mismatching gives rise to an array of irregularly placed El,or wlrich <ronstitutes the crystal boundary (grain boundary). Misnrrr,l,r'lrirrg is not limited to the crystal boundary alone but can also occur wll,lrirr l,1ro crysl,al, giving rise to subboundaris and a mosaic structure. tl'lttl lttr lrtr(,rltrl trrvstrll ctln be considered to be made up of many blocksErrl rorlrlisirrg t,horrsnrlrls to rnillions of atoms-with sufficient disregistry lrol,rvoorr l,ltcrl l,o rnnkc llcrn scpalate units but not sufficient to perntll, l,lrr, l'orrrrr,l,iorr ol' (,rrro glrr,irr horrnrlrlri<ls lxltw<lon them.

ally

in crystal form

are usu-

+2

IINGINEI'RING ME'TALI,UITGY

(a)

() Frc. 2-11. Relation of face-centered cubic to body-centered tetragonal and bodycentered cubic to face-centered tetragonal.

ltu. 2-12.

,grlrrr,'l'lrr, r''0xlilllfl'rl Ilolilri

Schrrtttrtl,ic trrtrcscttl,tt,liott Nol,ir:o l,lrrr,l, rlr l,lro grtt,irr I'rttttrlltr! i

oi rr
tt r tt

gt'rr.itr
I

lrornrllrtJ' lrr,lwrr,lt l,rvo ct'llttlH.

otti'ltlr Ilrrr llr,iI,ir.rr lrlcl,g l,1 11 llrttt tllr' I lrorr, tv lrillr ,'r,nl i I r r I r l.lr I rlrnrr ltr'.y lrrtt I lt'itl

ATOMS AND

CRYSTALS

43

Even the purest metal contains foreign atoms in its lattice. These atoms, with different diameters, act as another source of imperfections, since the lattice around them becomes distorted. Dislocations (Fig. 2-13) refer to all those imperfections of a lattice that result from a mismatching of atomic planes within a crystal. Although dislocations are generally too small to be detected directly, the evidence for their existence is continuously irrcreasing, since they explain many

The mechanism of crystallizalion

from vapors, plastic deformation, and the actual strength of metals can be oxplained by the existence of dislocations; grain boundaries and subboundaries can be considered arrays rf dislocations. In addition to dislocations and the dirtortion of the lattice produced by foreign atoms, another type of defeet

phenomena in metals which otherwise could not be easily understood.

oxists

in

crystals, namely, uacant

Although it would seem that vacant rltes would tend to fiIl, calculations (b) lntlicate that vacant sites are stable Frc. 2-13. Dislocations. (o) Edge disEtrd that equilibrium corresponds to location. () Screw dislocation. oorbain number of vacancies in the httico, this number increasing with increasing temperature. All these imperfections result in zones in which the lattice is distorted. Imporfections are present in all crystals, but the number of imper{ections lnd the resulting distortion can be appreciably increased. The most lnrportant means of producing distortion are alloying, cold working, and ha-lroatment, which will be discussed farther on. Distortion decidedly lfioot,s cr.ystal properties, and-regardless of the method by which lattice ltrlrl,iorr is pr<xluced---the effects are the sarne and depend mainly on the dcruu nnrl <listrilnrtion of the distortion.
CRYSTAL COMPOSITION

titas. As the name implies, vacant ltos are places in the lattice where oRo or more atoms are missing.

(!ryt,rr,lx vrt'y rtltlottt conl,n,irr n,l;rrns of <lrtly rrto r:lcmc'nt. Even in blglr-rrrril, 1r,tnls sonr l'orrrigrr rr,i,orrs trro rrcxorrl,, whiolr guncrully

4+
become

DNGINEERING MEIAI,I,URGY

ATOMS AND CRYSTALS

\l:

part of the crystal' Commonly' many different nttd some as alloying additions' present in any .ryrtui, Jo-e as imp.urities .fhe intermi*ing o atoms of different elements in the same crystal and the

elements are

gi;;;;';two

asic

intermediate Phase. two elements'-although Solid Solution. In a solid solution containing of atoms of each element composition is fixed' ihe percentage tft" """rug" cen is clifferent and corresponds to a random distribution' in each unit, element per cent If the number of unit cells containing a certain "l "?:l a probability curve, -t"*fti' h ;ifu;r;; a function of rhe per ceni of the element, of the cells have As can be seen' most as shown in Fig. Z f+,

lyp", "f

combinations, the solid solution

between those of metals, the most common being carbon, oxygen, nitrogen, and hydrogen. When the atoms of the trvo elements are of approximately the same size, the atoms of one element can substitute for the atoms of the other in the lattice (substi,tutional solid solution, Fig. 2-15b). The maximum concentration of solute depends mainly on the relative size of solvent and solute atoms. If the difference in size is less than 15 per cent, wide miscibility can be expected (Hume-Rothery ru,le). With larger size differences only limited solubility is possible; the miscibility decreases with increasing size difference to the point where eventually not only is the miscibility in the solid state negligible, but even misci-

bility in the liquid state is limited. For example, copper and nickel,
rvith a size difference of less than 3 per cent, can intermix completely. On the other hand, copper and sodium, with a difference of 45 per <rent, have solid solubilities of the <rder of 0.001 per cent in each other rirrd are also almost completely imrniscible in the liquid state. Size is not the only factor conl,rolling solubility; relative valence is l,rrother factor. Of two metals with rlill'crent valence, more of the higherrrrrt,ll valence dissolves in the lower vnklnce one than vice versa. The l,yrc of crystal also affects solulrili{,.y; if two metals have different clvsl,ill structure, complete miscilrilil,.y is impossible, even if the size rlil'lcrrlrcc bet'rveen atoms is very r,lrur,ll. Other factors may also affect
rrolrtlrility.

ro,u.n,u,om

ro,ur"^ro^,

a (,

o
(

o
o o
J z

Fro. 2-1,1. solid solution.

.I.he

bctrveen lattices in a -%B stalistical distribution of the two typcs of atoms

of the alloy' but there compositions Yery close to the average composition the ranges alt th" way from one pre -metal t'o are cells rvhose instead "o*po.itio" r"hetr the alloy, other one. trr" ,u*" ,urrdor,r i.tribution e*ists

()

four' or more' This of containing only two elements, contains three'

randomdistributionisthemostimportantcharacteristicofsolid
solutions.

Frc. 2-15. Types of solid solutions. (o) An interstitial solid solution in which the solute atoms are much smaller than the solvent atoms. (b)
A substitutional solid solution in which both atoms are similr in size.

Foreignatomsinthelatticeassumesubstitutionalorinterstitialposiatoms of the two tions, depending mainly on the relative size of the
comPonentsea<lh sphcrc reprt> A crystal can be represented by assembled spheres' a,re l.ft, whi.lt, ev.rl se.ting an atom. ,tseiween the atoms small spaces [f tlrtl ,trlrns ol .tltr i. a close-packecl lattice, are nevet' .omplebttlv fillotl. ol'lttrl':t'i'otns ilr l;lltr r'.t'lu srnr'll rvitJl rrtsp<"'t' t't t'lrtr of tho olcmerlts g.(i), Llr.v il, irr {,1r. srlrlrll "r,r .r,.ys(;ul (*lt;io .f <lilr,r.*i.r.s ..t, lrr,lrr t,lrlr' lr,rrrl :t ittlt'rsl ilittl *ilitl' i't,.r.si,it,r,s lr.t,rv..rr I,lrrr lrrr.g.r'rrl,rns (lriH 2 l5r), ctlt'ttglr t'o lil' sttlttlittt is I't,rlttl'rl. tl,'lv " 1'11: '11'r'll(rr llltt't'ltlolt:t ';tttltll
f

structure of a solid solution is basically that of the solvent variations in the lattice parameter. If the solute atom irr lrr,r'grrr l,lrn,rr l,hr,t of the solvent, an expansion results;if smaller, a conl,r'rrr'1iorr. 'l'lrcorctically the parameter of the solution is linearly proporlionrrl 1,o l,lro lrrn<rult of solute (Iregard's law); in reality, deviations in ,,rl lrct' rlit'r.r't ioll or,r,uI'. lnlcrmcdia.te Phases. Comlrinations of metals other than solid solulrr11 nl'(! lurorvrr rr,s irrl,clrnrxlitt,rr phllsos or intermetllic compounds. A Ilt'p,,. r'rrlir,l,v ol l,vrr,s r,risl, t':rtrgittg t'olll,ittttottsl\' I'r'om eombinations
ln,t;{,i<re

'l'lrc

rnll,rrl, rvil;h

smr,ll

46

ENGINEER,ING METALLURGY

which obey the chemical valence rule and have properties typical of chemical compounds to combinations whose structure and properties are very similar to those of solid solutions. The most irnportant factors controlling the formation of compounds are relative valence, size factor,
and electron-atom ratio. Valence compounds, in which the relative valence is the controlling factor, have compositions corresponding to chemical compounds. Generally they have a narrow range of composition, very high melting points, high hardness, and low electrical conductivity and plasticity. Typical valence compounds are MgzSi, CaAl2, AlSb, and CuzSe. Interstitial compounds are formed when size is the controlling factor; the smaller atoms fit in the interstices of the lattice, sometimes expanded

to accommodate the interstitial atoms. Interstitial compounds are formed by those elements which also form interstitial solid solutions. Nitrides, borides, carbides, and hydrides are generally interstitial compounds. They have high hardness, very high melting points, and narrow ranges of composition. The Laues phases include a group of compounds in which the electronatom,ratio and atomic size are the controlling factors. Laves phases are formed with electron-atom ratios from 1.33 to 2.2 and with a size difference of approximately 20 per cent. Typical Laves phases are MgCu2, MgNi2, MgZn2, PbAu2, TiFe2, etc. Laves phases have narrow ranges of composition, relativelv high electrical conductivity, and low plasticity. The el,ectrot compound.s constitute one of the most important groups. They are formed at fixed electron-atom ratios between metals of different valence, u'ith size difference not exceeding 15 per cent. Best known is the group called "B brass" with an electron-atom ratio 3:2 and cubic lattice. To this group belong CuBe, CtZn, Cu3Al, CuuSn, CusSi, FeAl, NiAl, and CoAl, in which iron, nickel, and cobalt have zero valence. Other electron compounds are formed at ratios 2I:13, 7 :4, etc. Many electron compounds have properties similar to those of solid solutions; these include wide range of composition, high ductility, Iorv hardness, and sometimes random distribution of atoms. Horvever, randomness is not characteristic, and those compounds rvhich may shor'v randomness at some temperature tend to assume an ordered arrangemont, of atoms at lower temperatures. "Ihe nicltel arsenide type of compound is the link between the eltx:trorr compounds and the chemical valence compounds. Compoun<ls of l;lris type form at, the electron-atom ratio of approximately 5 :2 rrl l,1'c colllri.. nations of metals such as nickel, cobalt, gold, and coppor, c(,c., wit,lr lriglr valence elements such as arscrric, selenium, tcllulirrrn, urrt,irrrorr.y, rr,rrtl t,irr. They have hoxagonal lat,t,i<rc, vrlry high llurrlncs rr,rrrl lrlil,t,krrrcsi-t, rr,url rrrlat,ivcly high cklcl;ri<:rl <lorr<lttct,ivit,v.

ATOMS AND CRYSTALS

17

DIFFUSION

r,r'ound fixed positions

rrystal. This

As mentioned previously, atoms in a lattice oscillate continuously in the iattice. Occasionally they move from one lrce to another, and thus any particular atom can move through the

movement is called difusi,on. I)iffusion is one of the most important phenomena in alloys, since most lrrnsformations in the solid state require it. In spite rf this irnportarrce r,rrrl in spite of much research work, no complete agreement has bectr cru:hed as to its mechanism. Manv theories have been proposed, among vlri<rh three have emerged as the most probable: the vacant-sitcs theory, lrc interchange theory, and the inter-qtitial theory. According to the vacant-sites theory, an atom moves into the vacant il,c, Ieaving behind another va,caucy, and so on; thus diffusion takes rlrrr:o by the shifting of vacant sites. The interchange theory, on the ,l,lrr',r' hand, a,ssumes that atoms rre comprossible and that at a given nrl,rrrrt it is possible for two adjacent atoms to have all their electronic l'lrit,s flattened in a plane in such a l'ay that the' 1,r move past each l,lrrrr'. The ilrterstitial theory a,ssllmes that an atom may move into an rlcrst,ice in the lattice nd from there on through the lattice. Energy orr.{irlcratiorrs favor thc vcant-sites theory. llrrgrlldless of the mcr:hanism, diffusion is a movement tou,rd equilrlirrrn. llhe ernergy for the movement is supplied by the atoms themr,lvcs, ts they try to move from l rroncquilibrium (high energy) position ,, rrrrcruilibriurn position (loiv energy). The amcunt of energy available, rr,l Ilrcrcfore the rate of diffusion, depends on the difference of energy r,l \vrrrrn 1,he trvo states. If the nonequilibrium condition has an errelgy ,rll rnrr<:h higher than the equilibrium crondition, the driving force for ilr\'r'ilr(!n1, is la,rge and the movement toward equilibrium is fast. If vert ll[' rlif l'clrrrr,e of energy exists between the nonequilibrium and the rtrililrrirrrlr condition, the driving force is small and the reaction is slou,. \lrl,lr.r'l'lrcl,or rvhicrh loverrrs the rate of diffusion is the resistance tcr rr' til.\'r'nrcr)1, of the ltoms. If the mobilitv of the toms is high, rapid lll tltriott r,rrrr lrc olttailrr:d even 1vith a small flrjying force;if the mobility I I lr. rr I onrs is lou', il lilrgc driving force is necessary to produce diffusion

rrtr rrrrtrrcirrllrl lu,l,c. l'1r,, r'rrl.r' rr,1 rvlriclr rIil]'rrsion takes place c,rr be expressed by

,,:,i,: I)A ()
t
tr

ltt,'lt ./ is l lrc

t'rt

lt' ol lrurss llorl (rrrrrnirt:r

Irlr'), /,'llr.rlr.i virrg

o[' llt orns ]riovi ng in onc unit of l'or.r:tr (rliffirlrrrrr:c ol't',lrcr.g.y lrcl,rvcor l,hu norr<t<uilib_

ttllr rrrrrl r,rrrilil,r'irrr r.olrrliliolrs), /i I,lrc r.r.sisl,rr,rrr:c I,o ntovctncr1, of tll<l

48

ENGINEERING MaTAI,I,URGY

atoms, D the difiusion coefficient or diffusivity, A the cross-seetional area, and L the distance of atomic movement. Depending on the relative values of I' and R, three cases can be distinguished. If E is very large as compared to F, little or no diffusion

takes place. This is the case of many transformations when the temperature is so low that the mobility of atoms is practically zero. If the values of F and .E are of the same order of magnitude, a finite rate of diffusion is obtained. This is the case in most reactions in the solid state,

such as diffusion of one element into another, recrystallizatiorr, age hardening, etc. If the value of I' is very large compared to E, then the rate of reaction is enormously rapid. This may be the case for diffusion in the liquid state. When the driving force is a concentration gradient, the general equation can be written as
dm,

dt

_DA*

d,r

Fick's law

in yhich

dm dt

rate of mass flow

D: A:

diffusivity
area

d,c

dr

concentration gradient
increases

The diffusivity is mainly a function of temperature; it

exponentially with increasing temperature and can be expressed by the formula

D:
inwhich

g-arar

C: : Q: R: ?:

a constant
base of the natural logarithms

aclivalion energy
gas constant

absolute temperature.

The activation energy is a measure of the resistance to atomic movcment and can be considered as the barrier that the atoms must surmourtt, before they can move to equilibrium positions. If two dissimilar metals are brought in intimate contact, diffusion ol' each metal into the other takes place provided that the resistan<xr 1,o atomic movement is not too high. The driving force for this dilTrrsiorr is the difference of energy between the two mctals rnd tho ulloy l,hrll, forms. Since this differcnce of enorgy is rrol, tho .1lrn<l f'or tJro two tnul;tlr, the ratc of dilTusion il not l,lro slmo. If<lr oxnrnllo, il r:orxrr tlrrl zittc urc mado to tlifl'uso irl,o rr<rh ol,hor', tho higlurr ncl,ivil,y ol' l,lro zinr: ('r,uH(!H rnor('

ATOMS AND ainc to diffuse

CRYSI'ALS

49

'lhe copper side of the couple

becomes porous.

into the copper than copper into the zinc (Kirltendall effect). srvells, and the zinc side either shrinks or

Diffusion is one of the reasons for the high friction between unlubricated metals;it also helps to explain the hardening of dental fillings. It is commercially exploited in pressure welding (Chap. 11) and powder metallurgy (Chap. 12). Diffusion is also necessary for recrystallization (Ohap. 7) and for most phase transformations in the solid state (Chap. 9).
PROBLEMS

1. The energy levels within a shell of electrons are customarily designated by the Il,lcrss, p,d,arldf. Thenurnberof electronsthatcanexistineachlevelisgivenby l,lrrr relation 2(2n - 1), where : l forthe slevel, r:2for the plevel, etc. The rrlr,cfron structue of the sodium atom (atomic number 11 and valenoe I) may thus be
written

(ls)' (2s)2(2p)6 KLM

f

(ils)r

Wlul, re the electron structrrrcs of the free atoms of the elenrents of the periodi<r table

lorn lithium to argon?

2. What ae thc tomic dimeters of coppcr arrd iron, as calculated {om the
r,krxcst clistance of approach of the atoms in the crystals? Copper is face-centered r,ttlric with : 3.6080 A; iron is body-centered cubic with : 2.8606 A.

8. Calculate the density of copper from the data of crystal structure, lattice rnl,rlnt, atomic weight of 63.57, and Avogadro's number, 6.0228 X 1023. 4. What is the interplanar distance d of the { 110 } planes in a iron ? 0. t.lsing the formula d : a/l/nz + ttz + lz determine the interplanar distance rrl l,lrrr lilill ) planes in copper. 0, ( )r,loulate the change irr density of iron (atomic vv'eight 55.85) rvhen it undergoes I ltl rr llol,'opic modilication at 910"C. Parameter of o iron body-centercd cubic (b.c.c.) nl 2()"(j is 2.85 A and the coefficient of expansion between these temperatures is l X l0 'l pt-'r deglec centigrade. Parameter of 7.iron face-centered cubic (f.c.c.) at
lllf l"( I i :|.(i5 A.

7. Wlrnl, :inglc is required for first-order rcflection of coblt Ko radiation ll - l.7lJ1) A) frorn the {110} planes of iron? t, ( jorrsirlrrr t,ht: fitting of small atoms of diameter lr into the spaoes bctween tt,ltrlivr,l), lnrgtrr a,toms of diameter d2 arrangcd in a face-centered cubic lattice. ff'grrlrlirrg l,lrc:l{,orns as sphercs, calculate the largest ratio of dtto tl,z that will permit Itrllr'slil,irr,l fil,l,irrg of thc small atoms into the lattice of the larger atoms without
rlhlu liol ol' l,lro sl,nr<ltrrrc. 0. l)r,lcrrtitttr Llrtr l:ltti<rc pllrametcr of a 75 per cent nickel-copper alloy from the llBtlltr'lr,rH lirr corxrr:rrrrl rrick<ll tf ll.(i08 A nd 3.517 A, respectively. tfl, ( llrrHilv I,lrc lirllolving cornporrntls according to electron-atom ratio: AgCd, l'tt.Ztto, ,\rtZlr, Nrrl'lrn, Arr Mg, ArrrSn, Il<rZrr7, \tt5Zn21. f l, '\r'r'rrtrlitrg lo Slrrttk.' ('l'ntns. ,1 I 14 Al It, r'ol. 185, 1t.752, 1949), the value of D

lrrt llr.rlrllrriorr ol crr,rl)orr ir.v irrn is 7.2 X l0-? s<1 (fnl per sec at 700'C nd lUl . lll i rr r'rrr rr,rsr,r:rl,7lil"(). l)cl,rrnrrirc l,lrcv:rlrrcof l,hcllctiva,tioncnergvin
,,,,llt
rr.rr rr.r' g,r'rrrrr rrIorrr.

I
L

50

ENGINEEBING METALI,URGY REFERENCES

"ASM Atom Movements," American Society for Metals, Cleveland, 1951. Barrett, C. S.: "Streture.of Metals," Mc.Graw-Hill Book Company, fne., New York,
1952.

Cottrell, A. H.: "Theoretical Structural Metallurgy," Edward Arnold & Co., London,
1961.

Guy, A. G.: "Elements of Phyoical Metallurgy," Addison-Wesley Publishing Com-

Hune-Rothery, W.: ttAtomic Theory for

Suderrte of Metallurgy," The Insitute of Metals, Lndon, 1952. , and Raynor, d. V., "Th" Structure of Mehis and Alloys," The fnstitute of Metals, London, 1954. Raynor, G. V.: "An Introduction to the Electron Theory of Metalsr" The Insiute of

pany, Cambridge, Mass., 1951.

Metals, London, 1949.

CHAPTER 3

EqUILIBRIUM DIAGRAMS

Any substanee which has a homogeneous structure bounded by definite ulfaces is a phase. Thus a liquid or a gas in a container constitutes a llrnsc. In the solid state a crystal with a definite lattice structure is also r rhase. Another crystal of the same structure. is still the same phase,

rrrl a crystal with a different structure is a different phase. When a

irlrrid solidifies, a phase change takes place, since a new phase is formed rutl of the liquid phase; the same is true when a metal undergoes an transformation, since a change of crystal type takes place.

'lloh'opic 'l'ho properties of a material are related to the n&ture, number, and lixl,r'ibution of the phases which compose it. A knorvledge of the strucurrr of an alloy greatly assists in the prediction of its properties. Equillrrirrm diagrams, also known as phase or constitution diagrams, show in ;rrr,rhi<r form the constitution of alloys as a function of temperature under

rrtililrlium conditions. 'l'lrrr simplest type of diagram is that of a pure substance, which is r,rrrrscnl;ed by a vertical line. Melting and boiling temperatures ancl llol,roric transformations are shown as points on this line. Generally Irrr itrl'ornration that can be plotted on this type of diagram can be easily trlrttlrrlcrl, and diagrams of single substances are plotted only when the ll'r'r'1, ol'srlrro other variable (e.g., pressure) is to be shorvn. llirr.grrrrns r'c usecl rvhen tu'o or more substances make up the materiai. f1,rlrrrlirrg on (,he rrrrmber ol elements present, binary, ternary, or quaternt', rlirr,glnnts cn be plotted.
BINARY DIAGRAMS

lflrrttlng. ll' l,wo rnctals, ,'l and B,

an'e

plotted as two points on

nllnll,rrl lirrrr, t,lrc scgnr<rnt, bet,ween them represents all the possible llrrvn lotrl,rr.inirrg (,lrc {,wo metals. Any point in this segment represents rlllitrilr, rrll,\', rrrtl il,s rlist,nr:c lrorn either end represents the pelcentage f rttrr,lr rrrr'1rl in llrc rr,llov.

lrrrrlll llr.rronr irnrort,rr,rrt, rncl,rr,l (llilsu rnctal) is plott,cd at the left

tlt,rrrrl Ilrr llsr irnror'1,rrrrl, (rr,llo.yirrg olonrorrt,) lr,l, {,lur lig}r1, sidc; }xrl, lrhis is Itlt'tt gr,trr,r'rl crnvr,rr(iorr, rr.rrrl rrorlillt'rrrrrrr, r'csttll,s irr ltvcrsing I,lrrr orrlct'
t