Materials II.

Content
1. The phase rule
2. Binary alloys with non-mixable elements.
3. Binary alloys with a continuous series of mixing crystals
4. Binary alloys with partly mixable solid phases. Complicated diagrams.
5. Cast structure of metals.
. !echanical properties and heat treatment of alloys.
". The annealing of unalloyed steel.
#. $ardening of steel
%. Carbonating and nitrating.
&'. Cast iron.
&&. (luminium and (luminium alloys.
&2. !agnesium- and magnesium alloys.
&3. Copper and Copper alloys.
)roblems
1. The phase rule
( metallic element combined with one or more other elements forms an alloy if the result
macroscopically consist of one metal sort. *xamples are steel+ cast iron+ bron,e+ messing+
solder+ aluminium-+ magnesium-+ titanium- lead-+ tin alloys+ etc.
(n alloy that consists of 2 atom sorts is called binary+ of 3 atom sorts tertiary+ of 4 atom
sorts -uaternary+ etc. The most important element is called the base metal+ the other
elements are called alloy elements.
Admixtures and irregularities.
.n metals there are irregularities which are not accounted for as alloys. Copper produced
electrolytically that is used for electric conductions contains a little oxygen. Because
oxygen hardly influences the conduction it is considered a undangerous admixture. .n
many cases a desoxydation substance is added+ which added in abundance+ increases the
admixtures.
/arious alloys carry names which are used for centuries. 0teel is an alloy of iron and
carbon+ bron,e of copper and tin+ messing of copper and ,inc and so is tombac. ( patent
for a new in1ented substance expires+ but the name can be protected permanently+ so that
each factory used to use its own name for an alloy. .n the nomenclature the base metal
comes behind and the alloy element before. 0o aluminium-copper is copper alloyed with
copper.
(n mixture of crystals can be distinguished microscopically+ but not macroscopically.
The crystals themsel1es in an alloy don2t need to be either of the base metal or the pure
alloy elements. They can be mixing-crystals themsel1es. The alloy elements can form
chemical connections with the base metal or mutually. .f the connections purely concerns
metals we spea3 of intermetallic connections. .n mixing-crystals the atoms of the alloy
element can replace those of the base metal4 they are placed 5substitutional6+ or can be
absorbed by those of the base metal4 they are 5interstitial6 placed.
.n substitiutional crystals often there is ordering. 7e consider a mixed-crystal consisting
of e-ual numbers of ( and B atoms. .n the unordered state they are placed arbitrary o1er
the a1ailable lattice positions. .f there is ordering the (-atoms will try to surround
themsel1es with as many as possible B-atoms and 1ice 1ersa. 0ee figure below
8ig. 9rdering in a body centered cubic lattice with 5': ( and 5': B
This case also appears in Cu-;n alloys with around 5': ;n <2-messing=. .n general the
ordering will decrease at higher at increasing temperature+ to abruptly stop at the so-
called critical temperature. .n this example this is at about 4' C> abo1e that we ha1e
an unordered mixing-crystal <2-messing=. 8or ordering the ratio need not be 5'-5' it can
also be "5-25. (lloys can be produced by melting or sintering.
Definition of Phase
( system of substances can be thought of mechanical separated in parts which in
themsel1es ha1e a homogenous composition and structure. The homogenous parts with
the same composition are called a phase. ( system with more than & phase is called
heterogeneous. There is only & gas phase. The bordering plane between gas and li-uid or
between gas and solid state can be thought of as a physical border-plane. There can be
more than & li-uid phase. ( system consisting of water+ oil and -uic3 sil1er consists of 3
li-uid phases. .t is thin3able to separate the 3 parts mechanically. The number of solid
phases can be 1ery large. *ach sort of crystals forms an apart phase because this can be
separated mechanically. ( mixing-crystal is & solid phase because it can only be separated
chemically.
( pure chemical substance will usually appear in 3 phase+ corresponding to the 3
aggregation states. ( 4
th
phase occurs when the material has more than & modification in
the solid state. <*.g. copper has 3+ but iron has 4 phases+ because abo1e %&' it has a
different crystal lattice than below it=.
( component is a substance needed to form a phase. 7ith metals these are simply the
atom sorts which appear in the crystals. .n many other cases a certain solid atom
combination <molecules+ connections= can be considered the components. The number of
components of a system is the smallest number of comprising parts with which that
system <and so each phase= can be built. 7ith metals this is usually the number of atom
sorts which appears in the common crystals.
Equilibrium state.
The e-uilibrium is the state in which the number and composition of the phases stay the
same in the long run. The number of phases has no influence on the composition+ so that
in e-uilibrium state+ namely the number and composition of the phases is not influenced.
( system stri1es to e-uilibrium. .f it really reaches e-uilibrium depends on the transition
1elocity+ which is determined by factors li3e mo1ability of atoms+ the gap of energy
difference which must be bridged etc. *-uilibrium will be reached more -uic3ly if the
temperature is higher+ because then the mo1ability and transition 1elocity increase.
Equilibrium conditions.
.n a 1essel which contains water and water 1apour in e-uilibrium the macroscopic state is
constant in time. Both phases ha1e mutual interactions with each other. 9pposite
tendencies towards minimal energy and maximal disorder are caught in the
thermodynamic potential+ which only depends on the state of the substance <for a simple
substance4 pressure and temperature=.
.n the considered 1essel there is e-uilibrium if the thermodynamic potential per molecule
<or mole= in the 1apour is e-ual to the thermodynamic potential in the li-uid4
?1ap @ ?li-.
Both -uantities are dependent on temperature and pressure. .f we consider the system at a
certain temperature+ then only the pressure-dependency remains. 8or more components in
& phase then also the concentration in that phase is a -uantity on which the chemical
potential depends.
Phaserule
7e consider 2 independent e-uations with 3 un3nowns x+ y and x. This system normally
is undetermined. (t one of the 1ariables <,= a 1alue is assigned+ and the system is
determined and gi1es 1alues for , and y. The system has one degree of freedom <8=. 7e
apply this to a thermodynamic system of c components and p phases .n each phase there
are c components. Their concentrations are the un3nowns. .f in a phase the concentration
of <c-&= components is gi1en+ then that of component c is also determined. .n each phase
we thus ha1e <c-&= un3nowns> this for the whole system gi1es p<c-&= un3nowns. 8urther
there are 2 1ariables+ the temperature <T= and the pressure <p=. .n total there are p<c-&= A
2 1ariables.
8or each component there must hold that in the e-uilibrium state its thermodynamic
potential in each phase must be the same> so for the first component we ha1e4
?&
&
@?&
2
@?&
3
@?&
p

The symbol ?n
m
represents the thermodynamic potential <per mole= of the n-th component
in the m-th phase. The mentioned e-uilibrium condition is e-ual to <p-&= independent
e-uations+ we can write it as follows4
0uch a set of e-uations can be written for each component.+ so that in total there are c<p-
&= e-uations. The number of degrees of freedom thus becomes4
8 @ p <c-&= A 2 - c<p-&= @ 2 A c -p
with which we can write4
p A 8 @ c A 2
This is called the phaserule. .t is deri1ed for the general case that in each phase there
appears each component. .f & component is missing then the number of relations is
lessened with & one the phase-rule still applies.
!"stems #ith 1 component $unar" s"stems%.
.n this system there are only 2 1ariables+ namely the temperature and the pressure.
(ccording to the phase-rule 4 8 @ 3 - p. 8rom this there follows that there are maximal 3
phases in e-uilibrium with each other+ because 8 cannot become negati1e. Because there
is at least & phase+ we obtain the following possibilities4
p @ & B 8 @ 2
p @ 2 B 8 @ &
p @ 3 B 8 @ '
.f there is & phase there are 2 degrees of freedom. .f there are 2 phase there is & degree of
freedom. 9ne of the 1ariables+ e.g. T can be chosen freely+ but then the other <)= is
fixed. . .n the simplest case in which there are possibilities 0<olidus=+ C<i-uidus= and
D<as=+ there will in general be 3 two-phase-lines+ namely for e-uilibriums 0-C+ 0-D+ C-D.
.f there are 3 phases then the number of degrees of freedom is ,ero. The system is
soluble. .n the )-T diagram the e-uilibrium is gi1en by & point. .n the abo1e example this
point is gi1en by the triple-point+ which gi1es the position of the only possible three-
phase-e-uilibrium 0-C-D. 7e gi1e the )-T diagrams of water
8ig. 0tate diagram of waterand of copper
8ig. 0tate diagram of copper.
The cross-point of the 3 two-phase-lines is the triple-point. <for water A'.''"E C and
'.'' atmosphere=. 8or most substances the triple-point is far beneath & atmosphere.
Carbon acid has a triple-point pressure larger than & atmosphere < a atm=. (s a
conse-uence li-uid carbon acid under atmospheric pressure canFt coexist with solid or
gas- carbon acid.
The slope of a 2-phase-line+ which gi1es the e-uilibrium between phases & and 2+ is gi1en
by the law of Clapeyron4
$ere &-2 is the transition heat from phase & to phase 2 and /2-/& is the 1olume change at
transition from state & to state 2+ both -uantities related to the same -uantity of matter.
Because in the system of GwaterG besides a positi1e meting heat there is a negati1e
1olume difference + the slope is negati1e and the triple-point lies abo1e 'EC.
7e consider H-iron <identical to I-iron= with a cubic centred structure and J-iron with a
cubic plane centred lattice. The )-T diagram for this case is gi1en in the figure below 4
8ig. 0tate-diagram of iron.
There are more triple-points now <the triple-point pressure are below & atm=. .f iron is
heated at & atm+ at %&'EC there will be a transition of H to J and at &4''EC from J to I+
while the I-iron at &53%EC will melt. There is supposed e-uilibrium . .K practice the
e-uilibrium donFt settle -uic3.
Cooling and #arming cur&es of copper and iron.
The phase-transitions of a simple substance are always paired with the emission or
absorption of an amount of heat <transition heat=. (t the transition 0-C this is the melting
heat+ at the transition 0--D this is the sublimation heat and at the transition C-D this is
called the e1aporation heat. .f the solid state 3nows more modifications then transition of
the one to the other is called a transformation.
.f heat is added to or extracted from a simple substance in a regular manner+ the
temperature course will be monotonous increasing L decreasing+ except for when the
phase-transition or transformation is passed> the then needed freed heat causes a strong
irregularity in the temperature-time-cur1e. .n the ideal case <approximated by cooling the
metal 1ery slowly= the temperature at the melting point will be some time constant <line
a=.
8ig. Cooling cur1es of copper
a. normal b. Mnder-cooled
.n practice there is an under-cooling. The solidification only begins if the temperature has
decreased far below the melting point. 0ometimes the under-cooling is so large that the
melting point is not reached <line b=.
(ccording to the following figure iron has 3 modifications in the solid state.
8ig. $eating- and cooling cur1e of iron
(t ""'EC <curie-point= there occur there appear <cooling=L disappear <heating=
ferromagnetic properties with a heat-effect. The transformation at %&'EC at heating is
found at higher 1alues. The transformation cause a temporary halt or arrest <8r4 (rret= in
the cooling- or warming cur1es. They are denoted with ( <at 8e=.
The transformation are paired with 1olume-changes. (t the HBJ transition the 1olume
decreases + because the J-structure is the densest sphere pac3ing and the H-structure not.
The 1olume change cause length change which are determined with a so-called
dilatometer.
8ig. Nilatometer cur1e of the HBJ transition.
'. (inar" allo"s #ith nonmixable elements.
A statediagram at binar" s"stems.
( binary alloy consists of 2 components. Onown examples are lead-tin <soft-solder=+
copper-tin <messing= and copper-tin <bron,e= etc.
The phase-rule in this case is4 8 @ 4-p.There is at least & phase+ so the number of degrees
of freedom at most is 3. This means that all states can be gi1en in a spatial diagram+
whereby along the axes the pressure+ the temperature and the composition of the alloy is
set. The composition can be gi1en in weight percentages+ but more it is more important
to use the atom percentages. *xample 8e3C contains 25: C+ which is ." weight
percentage C. <8e @5+ C@&2=. The abo1e diagram in practice is hard to use+ howe1er
most processes occur at & atm so that we can use this cross section of the state diagram.
$ere the temperature is put 1ertically and the concentration is put hori,ontally.
8ig. )rinciple of the binary state diagram
The concentrations of both components ( and B together are &'':. )oint ) consists of x
: B <or &'' P x: (= at a temperature of T) QC.
.n a system with more than & phase+ from the e-uilibrium condition it follows that the
phases ha1e e-ual temperature and lie on a hori,ontal line in the diagram. .f in the system
there are 2 phases C and N then by mixing these in all ratios+ of the both phases all gross
compositions are obtained that lie between C and N+ but no other. *ach intermediate
gross composition can be split into the compositions C and N. The composition )2
between C and N+ can be obtained by mixing of <)2CLCN=.&'': of the composition N
with <)2NLCN=.&'': of composition C. This is the le1er rule. This applies to a linear
concentration scale+ thus for weight percentages if the concentration scale is linear in
weight percentages and for atomic percentages if the atomic-percentages-scale is linear.
The 1ertical axes of the binary state diagram are formed by the temperature axes of the
pure components.
7e consider a binary system. The pressure is fixed at & atm+ so that already ha1e one of
the degrees of freedom. The remaining numbers are 82@ 3 P p. 7e then obtain the
following possibilities4
a. p @ &+ so 82@2
The 1ariables then are 4 the temperature T and the concentration of ( <that of B already
lies fixed=4 C(. The number of degrees of freedom allows an arbitrary choice of T and
C( > a one-phase area in the binary system is gi1en by a surface.
b. p @2+ so 82@&
There are now 3 1ariables4 the temperature T+ the concentration of ( in the first phase
C(
&
+ and the concentration of ( in the second phase C(
2
.
9ne of these 1ariables can be chosen freely+ the other lie fixed. .f we choose e.g. a certain
temperature then there follow the concentrations C(
&
and C(
2
of both phases in
e-uilibrium. .n the diagram the chosen temperature is gi1en by two corresponding points
lying at the same height
8ig. The two-phase e-uilibrium.
(t each temperature we chose we find a pair of points in the diagram. The pair of points
forms 2 lines. The cross-points of the line pair with a hori,ontal line gi1e the phase in
e-uilibrium at that temperature belonging to the hori,ontal line.
c. p @3+ so 82@'
There are now 4 1ariables+ namely the temperature and the concentrations of ( in the 3
phases4 C(
&
+ C(
2
and C(
3
.
The number of degrees of freedom is ,ero+ the system gi1es the solution. This means that
a 3-phase-system is only found at certain temperatures determined by the system+ and that
the composition of the participating phases lie fixed.
The 3-phase-e-uilibrium thus is gi1en by a hori,ontal line+ on which 3 points gi1e the
composition of the 3 phases.
8ig. The three-phase e-uilibrium.
(s an example we consider the binary system gold-nic3el which lies beneath %''QC.
8ig. )art of the binary system (u-Ki <Kic3el content in atomic percentages=.
$ere there is the 2-phase area (OB+ whereby (O and BO represent the mentioned line
pair. <in this case the lines meet each other+ but this is not always the cases=. 8rom the
diagram we read4 (t "5' QC about 4' atomic percent Ki can sol1e in (u+ and about &'
atomic percent (u in Ki. .f we ma3e an alloy with 2' atomic percent Ki then at "5'QC
this consist of & 3ind of mix-crystals.
(n alloy of ' atomic percentage Ki at "5' QC cannot be homogeneous+ because there
can2t sol1e so much Ki in (u. The alloy at room temperature will consist of a mixture of
2 3inds of mix-crystals ) and R+ with 4' and %' atomic percentage Ki respecti1ely. The
relati1e amounts of both can be read from the diagram with the le1er rule4 the distances
)S and RS relate as 243+ so the amounts will relate as 342+ in other words ' atomic
percentage of the alloy consists of mix-crystals of composition ) and 4' atomic
percentage of the alloy consists of mix-crystals of composition R. .n general alloys
represented by (OB+ in e-uilibrium state will consist of 2 phases> this are of the diagram
is called the demixing-area. 8rom the diagram there follows that the mentioned alloy
with 2' atomic percentage Ki at cooling from "5'QC on+ at 5%'QC will demix <if the
demixing is slow enough for the new e-uilibrium to settle=. (T temperatures abo1e that of
O <but not too far abo1e it+ else melting= we see that solid (u and solid Ki are mixable in
all ratio2s.
Categorising binar" s"stems.
0ystems with one li-uid phase when solidifying+ can gi1e in the one extreme a mixture of
crystals <full demixability= and in the other extreme form a mixing crystal <full
mixability=. The first case seldom occurs> the second more often> the most usual is part-
mixability.
The state ) diagram in the solid state at nonmixabilit".
.n the area abo1e the melting points there can exist only li-uid+ there is only & phase
there. ( li-uid in which there is much ( and little B is considered a sol1ent ( with sol1ed
matter B. .f there is more matter sol1ed the solidification point is lowered. /an2t $off
ga1e4
$ere x is the number of !oles sol1ed matter per !ole sol1ent+ S is the gas constant per
!ole+ T is the solidification point in O and - is the melting heat of the sol1ent per !ole.
The formula only holds for ideal+ thinned solutions.
*xample4 we calculate the free,ing point lowering of the sol1ent sil1er.
T @ %& C <melting point of (g= @&234 O.
- @ 24.% calLg @ 2%' calL!ole <atomic weight (g @ &'#=.
0o TT @ &&3' x O.
(t thinned solution x can be e-uated with the atomic fraction+ the free,ing point lowering
per atomic percentage sol1ed matter becomes &&.3 O. This holds for any substance+
pro1ided it is soluble in li-uid (g and insoluble in solid (g.
This formula ma3es possible to draw a line in the state diagram from the melting point 0'
which gi1es the e-uilibrium between li-uid and solid state. This is called the li-uid-line
of substance B in (> it tra1els downwards and in the beginning if the solution is thinned
is straight.
8ig. 0olidification lowering of a dissol1ed substance.
( li-uid with composition )' at cooling at )& will gi1e solid matter ( <0&=+ the
solidification- or free,ing point has bee reached. The li-uid becomes richer in B+ so that
this is cooled. )& is not the solidifying point but a solidifying traUectory. .f the
temperature has lowered to )2+ and the e-uilibrium between li-uid and solid state
continues to exist+ then the solid goes through point 02 and the li-uid through C2+. .n
ground of the le1er rule the relation between both phase is gi1en by4
solid (
and
li-uid C2.
( mixture of ( and B+ with composition and temperature such that the state goes through
a point in the angle 020'C2+ must exist of 2 phases in e-uilibrium4 the solid ( and a li-uid.
(t a certain temperature there belongs a certain composition of the li-uid and 1ice 1ersa.
The mentioned area is a 2-phase area.
The line pair that determines this area+ consists of the 1ertical 0'02 and the obli-ue line
0'C2. Through e-uality of ( and B at the B-side of the diagram the same deduction can be
made. The cross point * of both soluble lines gi1es the e-uilibrium of the li-uid with
both solid states 0( and 0B.
8ig. Binary state diagram of non-mixable phases.
(t cooling both solid states will crystalli,e simultaneously at constant temperature.
Beneath this temperature the li-uid has disappeared and there are only the solid phases 0(
and 0B. The hori,ontal line <CN= through point * thus is a 3-phase line. .t represents the
e-uilibrium between the solids 0( and 0B and the li-uid C*. (t cooling of the li-uid C* the
following three-phase reaction occurs4 C*B 0( A 0B.
The eutecticum.
(ll li-uids with a higher concentration of ( than * will first gi1e 0( at cooling and all
with a higher concentration of B than * will first gi1e 0B at cooling. .n both cases the
li-uid reaches the composition C*. This at temperature T* solidifies wholly. (n alloy
which exactly has the composition *+ solidifies fully+ has a solidifying point. The point *
is called the eutectic <@ good melting= point> we spea3 of eutectic temperature and
composition. ( solid ally with this composition is called an eutecticum. The eutecticum is
a mixture of pure ( and B crystals.
Cooling cur&es.
7ith help of the state diagram it is possible to predict the cooling cur1e of an arbitrary
alloy. 7e suppose that per unit of time the same heat is extracted and that the solidifying
heat and specific heat are constant. + then the solidifying cur1es can be constructed.
8ig. Cooling cur1es of alloys with an eutecticum.
$ereby use is made of the property that ratio of the phases can be read from the diagram.
The alloy )2 at T& is solidified for half while at T2 for V. 0uch a series of cooling cur1es
can be deduced from the state-diagram.
*onsoluble components and bondings in solid state.
( bonding will be represented by the general formula (xBy. The indices are integers. This
bonding / consists of WxL<xAy=X &'' atomic percentage ( and WxL<xAy=X &'' atomic
percentage B. The weight percentages are to calculated from the atomic weights.
.f neither the components nor the bonding from mixing crystals then the state diagram
can be deduced from by first placing the state diagram of ( and (xBy beside that of B and
(xBy. 8igure <a= below.
8ig. Binary alloy with bonding without mixing crystals.
Because in the li-uid area there is no phase separation there doesn2t exist a full mixability
there and in this area the common axis expires. The temperature axis is rounded because
the bonding in the li-uid will more or less dissociate in atoms which lower the theoretical
melting point. 8igure <b= abo1e.
( special case occurs if the bonding has already fallen apart before the melting point is
reached. $ereby 2 phases will originate which in the diagram lie at the side of the
bonding+ e.g. a li-uid and one of the components. The bonding and the 2 new phases
together determine a 3-phase-line on which the reaction is gi1en by4
0/ Y C A 0B.
This is called an incongruent melting bonding. .n such a state diagram the li-uid line 8C*
will ha1e a 3in3 at the point C.
8ig. Binary alloy with dissecting bonding.
This 3in3 must lie such+ that the extended of both parts of the li-uid lines comes in a
heterogeneous area. This is based on the theorem that the stable phase has the smallest
solubility. 9n the dashed line D$O the solubility of B in the li-uid is gi1en by D and the
solubility of the bonding will be $. The li-uid $ will howe1er gi1e B because it is
o1ersaturated with it and thus can2t be stable. The thermodynamic potential of the li-uid
$ is greater than that of li-uid D plus the detached -uantity B.
Examples of binar" allo"s #ith nonmixable solid phases.
The system bismuth-cadmium is an example of a binary alloy with unmixable solid
phases <8ig. below.=
8ig. 0tate-diagram bismuth-cadmium.
(n alloy with 2': Cd+ melted and afterwards solidified + has a structure as gi1en in fig.a.
below> the eutectic alloy with 4': Cd that of fig.b. and with "': Cd that of fig. c.
8ig. 0tructure of bismuth-cadmium alloys.
The eutectic structure gi1es as intimate mixture of both phases. 7ith help of the micro-
photographs it is possible to construct the course of the solidification.
The system sil1er-lead is 3nown because a method for concentrating small amounts of
sil1er in lead is based on this diagram.
8ig. 0tate-diagram of sil1er-lead.
The lead is first melted and afterwards cooled to abo1e the eutectic temperature. Kow
only pure lead can crystalli,e out. .f at this temperature the remaining melt is fully cast
away+ this theoretically contains all the sil1er. This process is called patinsonating.
.n the case of a strong asymmetric eutecticum li3e that o (g-)b it often occurs that + if the
large component present in the eutecticum is also the primary detached phase+ that the
eutecticum cannot be recognised as such. The mentioned primary crystals continue to
grow during the solidification of the eutecticum and thereby enclose the crystals of the
other component. The last lie as round spheres or continuous layer along the crystal
borders of the first. 0uch a structure is called degenerated eutecticum.
.ntermetallic bondings which are completely unmixable with the components seldom
occur. The system (u-)b is an example that also shows the rarity of 2 incongruent
melting bondings.
8ig. 0tate diagram gold-lead.
Bondings of metals with metalloids on the other hand are usually unmixable and often
occur. 0uch bondings mostly are impurities or admixtures which occur in a technical pure
metal+ li3e sulphides+ phosphides+ oxides+ nitrides+ carbides+ etc. .n these cases the part of
the state diagram between the bonding and the metalloid is not important+ so that the part
between metal and bonding is sufficient.
(n example is the system Cu-Cu29<figure below=+ whereby the eutecticum lies at &'3 C
and 3.5 : Cu29 <or '.3%: oxygen=.
8ig. 0tate diagram copper-copper oxidule.
(t small -uantities of Cu29 there forms a degenerated eutecticum.<figure below=
8ig. Negenerated eutecticum at copper-copperoxidule.
(t larger percentages of Cu29 this percentage can be estimated by metric estimate of the
amount eutecticum in the micro-picture.
+. (inar" allo"s #ith a continuous series of mixing cr"stals
!tate diagram at complete mixabilit"
There exist some systems in which the components form mix crystals in all ratio2s+ so that
there is only solid state+ at least in the e-uilibrium state. ( necessary condition for
complete mixability is that both components ha1e the same crystal lattice and the
parameters don2t differ too much mutual.
The state diagram at high temperature shows one homogeneous li-uid area and at low
temperature one area of the homogeneous solid state. .n both cases the number of degrees
of freedom is two because the temperature and the concentration can be changed
simultaneously without a change of phases occurring. These both areas are separated by a
2-phases area.
.f an alloy in half melted state is in e-uilibrium the composition of the li-uid and the
solid state will not be the same. .n the e-uilibrium li-uid-solid the li-uid will be richer in
the low melting component and the solid state richer in the high melting one. Because
this holds for all concentrations in such a system between the melting points of the
components there lie 2 lines.
8ig. 0tate diagram at complete mixability and complete diffusion
The upper line is called the li-uidus-line the lower one is called the solidus line. ( point
between these lines represents a 2-phase state. $ereby the both coexisting phases lie on
the crossing points of the hori,ontal line through this point.
Cooling cur&es.
( melted alloy with a certain composition ) at cooling after reaching the li-uidus line <*=
will separate off a solid state of which the composition lies on the same height on the
solidus line <8=. ( further solidification is only possible at a lower temperature because
the phase separated off ma3es the li-uid richer with the lower melting component. The
solidification has ended the moment the solid state has completely reached the
composition ). This only holds while the system is continuously in e-uilibrium.
(t an arbitrary point in the heterogeneous area the relation between li-uid and solid state
can be deduced from the relation between the hori,ontal distances of this point to the
solidus- and li-uidus line. 7ith help of this rule the cooling cur1es for all alloys can be
drawn <8igure below=.
8ig. Cooling cur1es at complete mixability.
Diffusion in the solid state.
The in the beginning originated crystals at further solidification will grow with a layer+
which is richer in the layer melting component than the nucleus. To maintain the
e-uilibrium the atoms of this component in the crystal will diffuse inwards and the that of
the other outwards. ( diffusion in the solid state is much slower than in a li-uid+ where
the unordered motion promotes a continuous mixing of the atom sorts.
.f atoms B diffuse in the metal (+ they must be sol1ed in (4 either substitutional or
interstitial.
.n a substitional mixing crystal diffusion is possible because there are empty spaces+
1acancies+ in the lattice. They are a direct conse-uence of the heat motion of the atoms> at
high temperatures there are more 1acancies in thermal e-uilibrium than at lower ones.
.n an intersitional mixing crystal the sol1ed atoms can Uump from the one to the other
lattice-position+ because there are wide 5canals6 which connects these positions.
Cr"stal segregation.
To approximate the practice case+ we assume that in the solid state there is no diffusion
possible. The solidification then is according to the figure below.
8ig. 0tate diagram at complete mixability and without diffusion.
The li-uid ) at begin of solidifying will gi1e a solid state 8 which forms the nucleus of
the crystals. The nucleus during solidification will not change in composition so that it
stays on the 1ertical line 87. The li-uid becomes (-poorer and must be cooled for further
solidification. The segregated solid state + which has the composition gi1en by the solidus
line+ forms the outer layer of the crystals. The a1erage composition of the crystals thereby
comes one a line between the 1ertical 87 and the solidus line. .n . this is the ratio .O4
.!.
.f the point $ is reached <temperature where the solidification will end at complete
e-uilibrium=+ there remains a -uantity KD of li-uid. The solidification traUectory is
prolonged. (t further solidification the outer layer of the crystals will become more richer
in B. The last bit of li-uid will consist of pure B and this will become the last rest of
solid. (t that moment the a1erage composition of the solid will be 9 and that of the
original li-uid will be ). The solidification traUectory thus stretches from the solidification
beginning to the melting line of B. The phenomenon is called crystal segregation.
8ig+ 0tate diagram at complete mixability and incomplete diffusion.
The crystal segregation of a dendrite can be seen sharply.
8ig. Nendrites with crystal segregation <messing=.
,omogenous glo#ing.
$omogenous glowing undoes the crystal segregation+ whereby the temperature is chosen
high to 3eep the time short. <beneath the melting point of B=. .n a metal that had crystal
segregation after homogeneous glowing this will be seen+ but less sharply. This can be
seen e1en after rolling and recrystalli,ing.
8ig. $omogeneous glowed <annealed= dendrites.
De&iating forms of the state diagram.
The two-phase area that lies between the one-phase areas does not need the ha1e the
pre1ious shown fish-from. Two-phase areas with maximum and minimum also appear.
8ig. Two-phase-diagram of mixing crystals with a maximum <a. )b-Ti= and a minimum
<b. Cs-Sb+ O-Sb+ O-Cs+ Ti-/+ Cu-Be=.
.n the maximum or minimum the solidus- and the li-uidus-line ha1e a common
hori,ontal tangent line. (lloys which ha1e the composition of the maximum or minimum
possess a solidification point and no crystal segregation.
Examples of binar" mixing cr"stals.
The most 3nown is the state diagram of copper and nic3el.
8ig. 0tate diagram of copper and nic3el.
(n example of a two-phase area with a minimum can be found in the upper part of the
state-diagram titanium-1anadium.
8ig. The state diagram titanium-1anadium.
-. (inar" allo"s #ith partl" mixable solid phases. Complicated
diagrams.
state diagram #ith a eutecticum of mixing cr"stals.
Binary systems in which both components are soluble in each other+ can gi1e an
eutecticum+ whereby the two phases are not the components+ but the mixing crystals+
represented by the points C and N below.
8ig. 0tate diagrams with an eutecticum of mixing crystals. <sil1er-copper=.
Between such a point and the melting point of the corresponding component there wal3s
a solidus line+ which encloses a heterogeneous area <together with li-uidus line+ the
eutectic point and that same melting point=+ that corresponds with a part of the loop of the
system with complete mixability.
.n the solid state beneath the eutectic temperature+ lies the two-phase area of both sorts of
mixing crystals. The boundaries of this area gi1e the mutual solubility4 at the (-side the
solubility of B in solid ( and at the B-side the solubility of ( in solid B.
To find the solubility-line alloys with different compositions are heated so long that
e-uilibrium has settled. (fterwards it can be suddenly cooled and in1estigated
microscopically. The results are gi1en below.
8ig. Netermination of the position of the solubility line
Z one-phase alloy [ two-phase alloy
(nother method is to measure the physical properties all samples glowed at &
temperature. These obser1ations are other glow temperatures to find more points of the
solubility line.
7e consider the alloy a of the following figure+ where part of a binary system is drawn.
.n an ideal e-uilibrium case the solidification will be complete at R+ an after cooling a &-
phase alloy will be found under the microscope.
8ig. Crystal segregation.
.f there is no or little diffusion then the a1erage composition of the solid state will go e.g.
along the line 9S. .n this case the solidification e1en at the eutectic temperature isn2t
complete+ but there will remain a -uantity li-uid of the eutectic composition+ which
relates to the amount of solid matter as S04 0*.
!tate diagram #ith a peritecticum
(t diagrams with an eutecticum the solidus- and li-uidus- line of both components lower
when adding the other. .t is also possible that the one pair lowers and the other one rises.
.f this is the case a diagram with a peritecticum originates.
8ig. 0tate diagram with a peritectum <platina-sil1er=
This diagram must ha1e this form because the li-uidus line of both heterogeneous li-uid-
solid-areas cross each other in & point. (t this point the li-uid is simultaneously in
e-uilibrium with both solid phases. .t is 3-phase-line which lies such that the composition
of the li-uid phase comes at one of the ends. (t cooling the following three-phase-
reaction occurs4
C A 0( B 0B
(n alloy lying between C and N at solidification will gi1e mixing crystals of ( till the
temperature of the three-phase-line is reached.
Allo"s #ith a demixing area in the solid state.
( special case occurs if in the area of the homogeneous solid phase there is demixing.
8ig. Nemixing area in the solid state without bonding <platina-gold=.
.n this case the mutual solubility of both components+ which ha1e the same crystal
structure+ increases -uic3ly+ so that the heterogeneous area disappears before melting
begins.
.t is also possible that of a bonding which at low temperature is stable+ the solubility in
the components increases such that at high temperature it is completely sol1ed. <fig.a
below=. 8urther this bonding can form mixing crystals <0/= with the components <fig b
below=. The line which the composition of a real bonding gi1es then is broadened to an
area.
8ig. Nemixing area in the solid state. The bonding forms no mixing crystals <a= and <b=
mixing crystals.
Components and bondings of a transition point.
( component with a transition point will+ at complete demixability of both modifications+
with the other component in the state diagram gi1e a hori,ontal line+ which separates the
phase-areas. This line is independent of the character of the second phase. <figures
below=.
8ig. 0tate diagrams with a transition point+ without mixing crystals.
.f the 2
nd
phase is a li-uid the li-uidus line at this temperature will ha1e a 3in3. .f one or
both modifications form mixing crystals with the other component then the transition
point will change by addition of this last. <8igure below=
8ig. 0tate diagram with transition point with mixing crystals.
a. with open -area <8e-Ki= b. with closed -area <8e-Cr=
.n fig.a. the component ( <iron= has two transition points of which the one is increased
and the other one is decreased by addition of B. .n this scheme the middle modification
of ( must ha1e the same lattice as B because these mutually gi1e a series mixing crystals.
(nother case is gi1en in fig.b+ whereby the outer modifications of ( ha1e the same lattice
as the element B.
!tate diagrams #ith a demixing area in the liquid phase.
.f metals in the li-uid state are not or little mixable+ then there are 2 li-uid phases. (t
solidification there originate 2 solid phases abo1e each other which don2t form an alloy. .t
is 3nown that lead gi1es 2 li-uid phases with different metals li3e copper+ ,inc+ iron and
aluminium. (t high temperature the solubility often increases and the demixing area can
disappear. ( 3nown example is the system ,inc-lead. <8igure below=.
8ig. 0tate diagram ,inc-lead
.n this diagram there appear 2 three-phase-lines. .n the lower part we recognise the
normal eutecticum+ in the upper part we spea3 of a monotecticum <only & phase melts
there=.
.f the 2
nd
component is a metalloid then it often occurs that there originate 2 non-mixable
layers.
.eading complicated binar" state
diagrams
(T each temperature and each concentration it can be gi1en from which phases the
system in the e-uilibrium state consists.
(T a 3-phase-line there originate 3 two-phase areas+ which describe the e-uilibrium of
the 3 pair-wise combinations of the 3 phases. .f+ from these 3 two-phase areas there lie 2
abo1e the 3-phase-line+ then the 3-phase-e-uilibrium is eutectic in type> the opposite case
is the peritectic type.
8ig. Three-phase-e-uilibria <with + and are solid phases and C is the li-uid phase=.
Ternar" state diagrams
The 3 components ma3e that the number of degrees of freedom is maximal 4. (t a certain
pressure in the &-phase area there are 3 left+ namely temperature and 2 concentrations.
8or this a spatial diagram is needed. <( prismatic spatial figure with e-ual-sided as base
plane. =.
8ig. Base of a ternary state diagram. ( point ) within this triangle consists of a : (+ b:
B and c: C+ whereby a is found by aline parallel to BC <opposite to (= etc. .t is clear that
aAbAc @&'':.
8ig. Ternary 0tate diagram
8ig. )roUection of a ternary diagram.
/. Cast structure of metals.
0ormation of nuclei and solidification in a simple metal.
.n the solid state the atoms are ordered in a lattice+ where the 1ibrate around their
e-uilibrium state. (s a conse-uence of this heat motion+ at high temperatures a number of
these lattice positions will be unoccupied. These 1acancies ma3e that neighbouring atoms
can Uump to another unoccupied place. .n the neighbourhood of the melting point each
atom ma3es around &'

Uumps per second. (t melting the regular structure is not lost.

*ach atom will ha1e other neighbours. .n solid metal with close pac3ed structure each
atom is surrounded by &2 nearest neighbours. .n the li-uid state this continuously changes
but seldom smaller than &2. The li-uid state has another structure than the close pac3ed
structure and thus has a lower specific weight. (ll close pac3ed metals at melting ha1e a
1olume increase> this is in most cases 4-5:. Cubic body centered metals at melting ha1e
a 1olume increase of 2-3:. 0ome metals at melting ha1e a 1olume decrease+ bismuth+
germanium+ and gallium. .n the )-T diagram the melt line will incline to the left.
The continuous change in the mutual position of the atoms ma3es that the specific heat
fluctuates+ whereby it can reach a maximum. This is the first step in the solidification
process4 the formation of a crystal nucleus. The chance that a density fluctuation causes at
the melting point causes a nucleus is small. Therefore The li-uid can be cooled far below
the melting point before solidification begins. This phenomenon is called undercooling.
This is the lowering of the temperature of a li-uid beyond the free,ing temperature and
still maintaining a li-uid form. Kormal free,ing occurs when the atoms of the container
walls impose an ordering on the li-uid atoms causing them to arrange themsel1es into a
crystalline structure and begin to grow. 7ithout the container+ the onset of free,ing
<called nucleation= has a good chance of not happening. But+ at some lower temperature
nucleation will occur and 1ery rapid free,ing ta3es place <called recalescence=.
The nucleation is often influenced by presence of small solid particles+ e.g. oxide
particles+ in the melt. The nuclei form there upon. These will grow into crystals.
Cast structure at a simple metal.
The grow 1elocity of a crystal nucleus is not e-ual in all crystallographic directions. They
dominate in certain directions. Thereby there originate branches+ o that a dendritic crystal
originates. (t a fast cooling e.g. in a metal form+ there originate in the outer layer a large
number of arbitrary oriented crystals. 0ome of these are oriented such that the direction
for the -uic3est growth coincides with that of the largest temperature that is perpendicular
to the wall. These crystals will grow fastest and from a ,one of stem crystals. .f the
sample cast is thic3 enough the temperature gradient which originates at -uic3 cooling+
will be undone by the freed solidification heat+ through which the remaining li-uid is
heated to till the solidification point. The inner part cools without a fa1ourite direction.
.n the sample 2 ,ones can be distinguished4 the ,one of the fine+ arbitrary oriented
crystals+ the ,one of the trans-crystalli,ation with directed dendritic stem crystals and the
nucleus with the arbitrary oriented slower solidified crystals. <8ig.below=
8ig. 0tructure of -uic3ly cooled copper <3 ,ones=.
(t slow cooling+ li3e that of casting in a dried+ <or warmed= sand form+ at reaching the
solidification temperature the form wall of the molten metal will be warmed to about the
temperature of the melt itself. The solidified metal by missing of a temperature gradient
has no transcrystalli,ation ,one and shows a more uniform pattern+ be it that the si,e of
the crystals is much larger at -uic3 cooling. <8ig. below=
8ig. 0tructure of slowly cooled copper
!olidification and cast structure of allo"s.
.n melted alloys the formed nuclei in general has a different composition than that of the
li-uid.
The cast structure at alloys which form mixing crystals at large is the same as those in
simple metals.
The difference is that there is a solidification traUectory instead of a solidification point.
(s a conse-uence the dendritic s3eleton propagates through the whole li-uid and that the
li-uid between the braches only solidifies later.
(n alloy with the eutectic composition will solidify differently than a simple metal
because both 3inds of crystals influence each other solidification.
.t often occurs that there originate a structure in which both phases appear as alternating
layers <fig. a below=. These then ha1e grown 1ane-li3e <fig. b below=. 0uch a combination
separated off in space often gi1es & crystal4 we spea3 of eutectic crystals.
0ometmes in an eutecticum there is a clear dendritic structure. <fig. c below=. 8iannly a
phas e can be separated off sphere-li3e+ so that the other phase comes as a closed
networ3 around the first. <fig. d=
8ig. *xamples of eutectica
a. lamellar+ b. 1ane-li3e + c. dendritic+ d. globular.
.f the li-uid alloy has a structure different from that of the eutecticum +one of the phases
will begin to solidify and the eutecticum will fill the space which remains after
solidification of a primary formed crystals. $ere also the primary solidification 1an be
dendritic or globular. The difference with the pre1ious is the last case the intermediate
spaces are filled with eutecticum. .f the amount of primary solidified phase is large and
there remains little eutecticum then at solidification of this the primary phase will settle
on the present crystals and the remaining space will be exclusi1ely filled with the second
phase. $ere there originate small holes between the branches of the dendrites or a thin
networ3 around the spheroid crystals. The last case is called degenerated eutecticum.
The shrin1 hole
( metal expands a few percentages ate melting. (t solidification the 1olume will become
smaller. (t casting the difference in 1olume causes shrin3 holes. .n a cast bloc3 the shrin3
hole lies in the middle of the cross section an penetrates deep into the metal. .f the after-
flow at casting by -uic3 solidification of transition between cast sample and riser is not
possible+ there will originate a shrin3 hole in the cast sample.
8ig. 0hrin3 holes in risers <out-gates= and cast funnels <gates=.
The slag inclusions.
Ci-uid metals usually are refined <and protected from outside atmosphere= by the slag
floating on the metal. (t casting there mostly comes slag with the li-uid metal in the
form. Because the metal is saturated by particles of the slag+ at solidification there also
originate a slag-li3e phase. (n example is he off-separation of copper oxydule at
solidification of copper. 0lag particles carried off ser1e as a nucleation center and are
found in the crystal. .f the slag particles are li-uid they ha1e the form of spheres.
By addition of manganese to steel the low melting networ3 of iron sulfide is replaced by
a higher melting manganese sulfide present as spheres+ this will influence the formation
of slag inclusions.
2as inclusions
.n the li-uid different gasses are sol1ed of which oxygen. Kitrogen and hydrogen are the
most important. The solubility of these gasses in solid state is 1ery small+ so that they
freed at solidification. By the low specific weight the gasses rise and ma3e the metal
bubble.
(t a certain cast method of steel by the freeing of C9-gas the 1olume of the solidified
metal is much greater that the shrin3 hole can disappear. (t rolling and forging the flaws
or gas bells in the solidified metal are welded off.
2ra&itation segregation.
.t is possible that a solidifying metal has a specific weight that differs from that of melt
from which it originates. (s a conse-uence these crystals will float or sin3. This
phenomenon is called gra1itation segregation. The most 3nown example is an alloy of
%': 0n and &': 0b. The primary 0b0n crystals separated off gather in the upper part
where hardness is much higher than in the lower part. <fig a below=.
8ig. 0tructure of metal with 0b0n-bloc3 and Cu0n5-needles.
To pre1ent this we choose an alloy of #':0n+&':0b and &':Cu. Kow there first
crystalli,e a networ3 of Cu0n5 which pre1ents the following 0b0n-crystals to rise. <fig
b abo1e and fig below.
3. Mechanical properties and heat treatment of allo"s.
The mechanical beha&iour of mixing cr"stals.
The atoms of an alloy element will + if they are placed interstitial+ deform the lattice of
the base metal+ because they push the surrounding atoms apart. 0ubstitional placed alloy
atoms will also cause a deformation because they are larger or smaller than the atoms of
the base metal and so will not fit into the base lattice. The originated tension fields in the
mixing crystals will hinder the shift processes along the slide planes+ though which e.g. in
one-crystals of mixing crystal forming alloys the critical tensile force will be higher than
in the pure metal. This tensile strength will also be higher if the concentration of the
alloying metals will be chosen higher. The higher critical tensile strength can be expected
at about 5': atomic percents+ because at a further increasing content the alloying
component will become the base metal and the concentration of he new alloy element
thus decreases. <fig. below=
8ig. Critical tensions at a continuous series of mixing crystals.
.n the case of polycrystalline alloys+ consisting of mixing crystals+ the course of rupture
limit+ pull strength and hardness with concentration is as described abo1e.
The mechanical beha&iour of a mixture of cr"stals.
Contrary to a mixing crystal at a mixture of crystals the properties as strength+ hardness
and toughness lie in between those of the composing crystals.
The geometric distribution of the both crystal sorts in the metal has a large influence on
the mechanical properties. .f the structure consists of a networ3 of brittle crystal sort
which encloses the tough one then the metal will be brittle compared with a metal with
the same amount brittle imbedded in the matrix of the other crystal sort. .f the base metal
solidifies in dendrite form then a brittle bonding forms between the branches of will not
as large a influence as at a spheroid solidification of the base metal whereby the bonding
forms a closed networ3. (fter casting and solidification the impurities often such a
networ3.
.ntermetallic bondings often will be brittle > their complicated crystal structure does not
allow plastic deformation. (lso the ordering phenomena gi1es a lowering of the
toughness.
The glo#ing of cast pieces.
.f the casting occurs slowly then the e-uilibrium will ha1e settled and a glow treatment
will ha1e little influence. !ostly the cooling will be so -uic3 that the e-uilibrium has not
<or hardly= settled. .n a cast piece tensions will originate due to shrin3ing during cooling.
(nother cause of tensions is the gi1ing of a form during solidification. 8or a cast piece
that must be prepared precisely then repair glowing is needed.
The soft glo#ing.
.f a multiple-phased metal contains & phase in the form of lamellas + needles or a networ3
then at heating there can occur a structure change+ whereby this phase goes into the
sphere form. The tendency to transition of the lamellar into globular form comes from the
difference in the surface-energy. This is smallest in the at the globe form because here the
surface is the smallest relati1e to the content. This energy per unit of surface decreases
with increasing radius of cur1ature+ in other words at increasing si,e of grains. The most
stable form thus is a single spheroid crystal. (t longtime glowing the lamellas slowly go
into spheres <globes=+ which become larger at continued glowing. <fig. below=
8ig. 0oft-glowing a. iron-cementite b. copper-copper sulfide.
To reach this it is needed that the atoms from which the lamellas consist+ are soluble in
the base metal and that they can diffuse in it.
Because spheres hinder the sliding less than lamellas a metal with a globular structure
will be more easy deformable than with a lamellar. This heat treatment therefore is called
soft glowing.

.epair glo#ing and the glo#ing out of allo"s.
The difference between the glowing of alloys and simple metals is not large. .n both
cases the internal tensions must be lessened. This can also be obtained by repair glowing
and recrystalli,ing in alloys.
(n example of the repair glowing is the application of this heat treatment on cold
deformed messing. !essing is susceptible to corrosion+ whereby the effect penetrates
deep into the metal along the grain boundaries. The internal tensions let the corroded
messing burst along the crystal boundaries <fig. below=.
8ig. !essing pipe immersed in -uic3sil1er nitrate solution. a. without repair glowing b.
after repair glowing.
The inter-crystalline corrosion which at messing is called the 5season sic3ness5 + does not
occur if the metal is glowed> thereby it is sufficient to warm the messing during half a
hour at 2"5-3''C. This heat treatment has little influence on the hardness+ toughness+
and strength.
The precipitation hardening.

This hardening method is also called 1apour or mist hardening and does not occur in pure
metals+ but only in alloys. 7e consider a simple binary system (-B <fig.a below=. The
heat treatment is gi1en in the fig. b below. The alloy has a composition b+ such that by a
glow treatment at a temperature T

<solubility glowing= there originate homogeneous -

mixing crystals> this state is called atomic dispersion.
8ig. a.. binary system with solubility line tra1eling bac3
b. heat treatment
.f after solubility glowing cooling is done 1ery slowly to room temperature+ then
according to the e-uilibrium diagram a mixture of two crystals and is obtained. .f
precipitation hardening is done then this demixing is suppressed by -uenching <-uic3
cooling or chilling= of Tp to room temperature <TR=. The homogeneous state then is
fro,en. The thus obtaine material + because it consists of mixing crystals+ is harder than
the pure base metal (+ because in general it is so soft and though that it can be deformed
plastically. The so obtained state isn2t stable thermodynamically 4 it is a unsaturated
solution of B in + which in general has the tendency to separate off -crystals. <8ig.
below=
8ig. a. unsaturated mixing crystal. b. coherent intermediate state c. precipitation of .
0tarting from the unsaturated &-phased state a> after some time there occur the first
submicroscopic separations <precipitations=+ often in the form of fine needles or discs+
with a crystal structure which in many cases don2t exactly loo3 that of + but fits well in
the -lattice. The name 4ones is gi1en to them. They don2t exactly fit into the -lattice >
because the direct atomic coherence is maintained <fig. b=+ in the crystal there originate
strong tension fields. These hinder the sliding processes needed for plastic deformation. .f
the glowing time is too long or the glowing temperature too high+ from the s3etched
intermediate state+ there can originate -separation <- precipitation fig. b=. The
surrounding crystal lattice is+ because the coherence is lost+ undisturbed by this. (s a
conse-uence the elongation limit and hardness ha1e become lower. 7e say that the state
of critical dispersion is passed.
Example of precipitation hardening.

8ig. precipitation hardening of duraluminium4
a. (fter-annealing temperature 2'C.
b. (fter-annealing temperature &5'C.
5. The annealing of unallo"ed steel.
Iron forms.
martensite
FFF!artensiteFFF+ named after the Derman metallurgist (dolf !artens+ is a class of hard minerals occurring as lathe- or plate-shaped
crystals. 7hen 1iewed in cross-section+ the crystals appear acicular <needle-shaped=+ which is how they are sometimes incorrectly
described. The crystals are a face-centred tetragonal <8CT= form of iron and carbon+ and result from the rapid cooling of austenite
during -uenching. .n the &#%'s+ !artens studied samples of different steels under a microscope+ and found that the hardest steels had a
regular crystalline structure. $e was the first to explain the cause of the widely differing mechanical properties of steels
!artensite is a body-centered cubic form of iron in which some carbon is dissol1ed.
!artensite forms during -uenching+ when face centered cubic austenite changes to the
body centered cubic structure without the precipitation of cementite. .nstead+ the carbon
is retained in the iron crystal structure+ which is stretched slightly so that it is no longer
cubic. !artensite is more or less ferrite supersaturated with carbon. Compare the grain
si,e with tempered martensite.
8ig. 0tructure martensite
Tempered Martensite
7hen martensite is tempered+ it partially
decomposes into ferrite and cementite.
Tempered martensite is not as hard as Uust-
-uenched martensite+ but it is much tougher.
Kote also that it is much finer-grained than
Uust--uenched martensite.
Austenite
(ustenite is a face centered cubic form of
iron in which some carbon is dissol1ed.
(ustenite forms abo1e the critical
temperature.
8ig. (ustenite
Cementite
Cementite is .ron Carbide+ with the formula
8e
3
C.
0errite
8errite is a body-centered cubic form of iron
in which some carbon is dissol1ed.
6nallo"ed steel
0teel is an iron alloy which is forgeable. 0ome steel sorts ha1e more than &.5:
carbon+ so it hard to gi1e an exact definition. The best definition would be 4 an + in
solidified or sintered state+ forgeable iron alloy in which there is no free carbon.
Besides iron and carbon there are 1arious other impurities in the steel.
The differences in cast steel and rolled steel lie in the different production techni-ues.
(T solidification of steel there originate a relati1ely large dendrite structure. The last
solidifying matter between the dendrites due to segregation is less pure. .n these there
can also originate gas P or shrin3 holes. (t rolling the steel the structure becomes
finer by recrystalli,ation> the pores are pressed closed> the segregation areas are
stretched into large paths.
Ironcarbon diagram
This holds for alloys of iron and carbon+ other elements don2t occur. .t was drawn
after research of Bramley+ Cord+ !ehl and 7e1er. The e-uilibrium state and the 3-
phase reactions can be deduced from the diagram. The li-uid-area <C= is bordered by
the lines (-B+ where there is e-uilibrium with -iron+ the line B-C with -8e or
austenite + and C-N with cementite. There are three three-phase lines4
-iron A C austenite <&4%2 C=
C austenite A cementite <&&3' C=
austenite ferrite A cementite
The eutectoide here is called pearlite
8ig. .ron-carbon diagram.
structure of glo#ed steel.
Kormal glowing consists of heating the <unalloyed+ rolled= steel in the austenite area+
followed by a poor -uic3 cooling. The last is cooling in calm air. Mnder these
circumstances the austenite of eutectic composition <'.# :C= beneath "23C will go
into a lamellar structure of ferrite and cementite. This structure is called pearlite after
the pearl-li3e gloss of this polished steel. Both structure parts ferrite and cementite
can be accessed microscopically. (s a etch agent a 2: solution of nitric acid in
alcohol is used P the pearlite becomes dar3er and the ferrite lighter.
8ig. Camellar pearlite.
(t steel with a low carbon content at cooling in the autenite area there first will form
ferrite and afterwards at reaching '.# : C in the austenite + transition in pearlite will
occur. (t ':C all is light and at '.# :C all is dar3. <8ig. below=
8ig.
8rom the boundary of the pearlite it can be seen that the ferrite crystals are formed
globularly. (t a low C content this leads to triangular pearlite 5islands6.
(t steel with a higher carbon content larger than '.#: <abo1e-eutectic=+ which is
cooled+ first there will be separation from the austenite area of cemenetite+ whereby
the carbon content decreases to '.#:> afterwards the remaining austenite will be
transformed into pearlite. 0o &.5: C only gi1es &': cementite and %': pearlite.
8ig. 0tructure of normal glowed abo1e-eutectic steel.
*ormal glo#ing $annealing%
This is defined as heating of steel in the austenite area followed by cooling in calm air
or4 cooling such that the pearlite is obtained in lamellar state.
8ig. 0chematic representation in time of normal glowing.
&-2 states at steel fabrication
2 deli1ery state
3- normal glowing
The structure before and after normal glowing is seen in the figure below.
Before normal glowing
(fter normal glowing
7. ,ardening of steel
The simplest method of hardening consists of heating the steel till the austenite area+
till abo1e "23C+ followed by -uenching in water. By the high cooling 1elocity the
carbon diffusion is suppressed so far that there can not form pearlite or troostite.
Nuring -uenching the austenite will transform into ferrite+ and such that the carbon
atoms cannot escape in time and in unsaturated state stay behind in the ferrite. The so
formed structure is called martensite. <fig. below=

8ig. !artensite.
.n hardened unalloyed steel of pearlitic composition + the martensite forms flat+ dis3-
formed crystals+ which under a microscope loo3 li3e needles. These martensite dis3s
grow 1ery fast> their formation time is less than &'
-"
sec> in such short times the
diffusion processes hardly play a role. The transition form austensite to martensite is
considered a um3lapp process> of which the principle is s3etched below.
8ig. ( future martensite-cell in austensite.
$ere two cells of the cubic body plane austensite is s3etched. The bold lines indicate
that the structure can be described as a tetragonal body centered with an axis ratio4 cLa
@ 2
&L2
.
(t the transformation of the austenite lattice in the -lattice the displacements of
neighbouring atom relati1e to each other is small. Because of this the -lattice can
um3lapp and this process can propagate with large 1elocity through the -lattice.
There exist an orientation relation between the austenite and the formed martensite
crystals. (t the transformation the tetragonal cell goes into a cube.
(t hardening there is a 1olume increase of &.3 :. The martensite dis3s are pressed
out of the austenite. By this there originate tensile stresses in the austenite+ which
hinder a further growth of the martensite dis3s and new dis3s. (s a conse-uence in
hardened steel there is an amount of non-transformed austenite+ which is called rest-
austenite.
8ig. Sestaustenite.
The T.T.T diagram.
7e1er and *ngel around &%3' did experiments about austenite transformation and the
hardening of steel. These were put in a diagram as a function of temperature + the
T.T.T diagram <transformation-time-temperature diagram= or the ..T. diagram
<isothermal transformation diagram=. The simplest T.T.T. diagram is that of unalloyed
pearlitic steel <'.#: C=.
0uppose we want to study the isothermal transformation at 3"'C. (fter austenitating
the sample is -uenched to 3"' C+ <e.g. in a lead bath=+ after which the course of the
transformation at that temperature is studied.
8ig. Course of an isothermal transformation.
.t appears that the transformation begins after a waiting period <incubation time= of
about &' sec. (fter this the transformation 1elocity increases to decrease again. .n our
example the transformation is complete after about 25' sec. By repeating this test at
different temperatures and putting the begin- and end-times in a temperature-time-
graph we find 2 cur1ed lines which gi1e the beginning and end of the isothermal
transformations. <Because begin- and end-point are difficult to obser1e we often ta3e
the moment at which 5: and %5: of the austenite are transformed=.
(t -uench temperatures <temperature of the coolant= beneath 2''C + the state is
different. Then there directly originates martensite+ and much more so if the -uench
temperature is lower. <0ee fig. below=
8ig. The amount martensite as a function of the -uench temperature.
.n the course of time the martensite content don2t increase isothermally+ and in a
temperature-time-graph the martensite content is represented by hori,ontal lines.
8ig. The T.T.T diagram of unalloyed pearlitic steel. <schematic=.
.sothermal transformation at high temperature always gi1es pearlite+ at lower
temperature we obtain a fine pearlite-li3e structure+ called troostite+ and a e1en lower
temperature a different structure called bainite. (T 4''C there originates high bainite
and at 35'C low bainite.
8ig. Bainite. a. $igh bainite b. Cow bainite. !agnification 25''x.
The structures originated are
a. )earlite. 8irst there originates a 8e3C-nucleus> for this carbon is needed. This is
extracted from the near surroundings+ which therefore unm3lapps to a ferrite
lamella > in this there only sol1es little carbon.
b. Bainite. $ereby the -lattice um3lapps to ferrite after the incubation time has
passed. .n this carbon can diffuse much -uic3er than in austenite+ through which
in the um3lapped areas direct separation of 8e3C originates+ which is finer is the
transformation temperature is higher.
c. martensite. $ere the -lattice goes into the -lattice+ thereby catching the carbon
which can2t escape.
.
,ardenings methods
8rom the TTT diagrams the hardening methods used in practice can be described.
8ig. Cooling diagrams in the TTT diagram.
The beha1iour of steel can be described by CCT <continuous cooling transformation=-
diagrams.
.n the TTT diagrams cooling lines are drawn <e.g. line & abo1e=. (nd we suppose that
the transformation begins at the time on whereby the cooling line cuts the begin
transformation line and ends whereby the cooling line cuts the end transformation
line.
The ordinary hardening in the fig is represented by line 2. The large cooling 1elocity
is obtained by -uenching in water. By the large temperature gradient there are internal
tension which cause rupture or crac3. There is less tendency to crac3 by trapped
hardening or martempering + cur1e 4. $ereby there is not -uenched in water+ but e.g.
in a salt bath of the desired temperature <her 2'C=. (fter -uenching the sample is
held at this temperature+ so that the heat tensions disappear.
The sample can be 3ept in the salt bath till the isothermal transformation is
completed> the end product is high bainite+ less hard but tougher than martensite
<cur1e 3=> we spea3 of isothermal refinement <or austempering=. (t a lower salt bath
temperature <cur1e 3a= the end product is low bainite.
The critical cooling speed.
The smallest cooling speed+ needed to obtain the martensite is called the critical
cooling speed. .f this speed is not reached then at about 5''C+ in the area of the
5nose6of the TTT diagram+ pearlite in fine form will originate. This grow sphere-li3e+
e1en if the temperature has lowered. This process howe1er will come to a standstill at
lowering of the temperature. This structure + troostite+ can be affected by the ordinary
etchants . The spheres which occur if part of the austenite is transformed into troostite
is seen in fig below.
8ig. 0phere-shaped troostite.
(n insufficient cooled steel+ shows + due to impairment after annealing or tempering+
coloured places <interference-colours= + which are 3nown are troostite stains.
0tarting from '.#:+ the carbon content is lowered+ the austenite transformation begins
more -uic3er+ so that we ha1e to -uench more -uic3er to a1oid the 5nose6 of the
transformation cur1e4 in other words the critical cooling 1elocity increases if the
carbon content is chosen lower. <8ig. below=
8ig. The relation between the critical cooling 1elocity and the carbon content at
unalloyed steel.
The hardening depth.
.f a steel sample is -uenched the outer ,one cools much -uic3er than the inward
directed parts. The thic3ness of the 5shell6 in which there is complete hardening is
called hardening depth. To measure this the steel must be grinded+ prepared and
etched. Because the troostite can be affected the border can me seen and measured.
( well-3nown method is the method of \ominy+ whereby a cylinder heated at
hardening temperature+ is -uenched by a water stream. (lso 2 thic3 dis3s with smooth
surfaces can be pressed against each other and -uenched commonly. .n both cases
the course of the hardness is measured perpendicularly to the hardened surface. This
course+ measured at hardened steel with '.#:C is gi1en below.
8ig. Course of the hardness perpendicular to the surface of hardened pearlitic steel.
The corresponding structure image is gi1en below.
8ig. 0tructure of hardened pearlitic steel from the border to the 3ernel.
.t will be clear that a sample can only be hardened thoroughly if the maximal
thic3ness is not bigger than ca. 2 x the hardening depth. 9f the unalloyed steel sorts
the eutectic ones ha1e the largest hardening depth> this is ca 3-&'mm + so samples
from unalloyed cannot be hardened thoroughly if they are thic3er than -2' mm.
7e consider the beha1iour of unalloyed undereutectic steel. This steel after hardening
is less hard than eutectic steel+ because martensite with a lower carbon content has
less internal tension and thus is less hard. <fig below=.
8ig. The hardness of hardened unalloyed steel as a function of the carbon content
<-uenched with water=.
(T '.3 : C the brinell-hardness after hardening is higher than 4'' 3gLmm
2
. This is
about the highest 1alue whereby steel can be processed with hardened steel tools.
This is called the hardenability limit.
Austenitic circumstances.
(t hardening of pearlitic and under-pearlitic steel before -uenching this must ne
brought in the austenitic state. The temperature at which this happens is called the
austenitic temperature. This is done by a glow treatment in the austenite area. The
purpose is the solubility of the obtained carbon atoms in the austenite. (t a
temperature too high or too large glow time there will a strong growth of austenite
crystals+ which ate hardening gi1es rise to rough+ brittle martesite+ so that the chance
to hardening crac3s increases. Mnder these circumstances the martensite
transformation will be less complete so that there remains restaustenite.
.t appears that for pearlitic and under-pearlitic steel a hardening temperature of 5'-
"':C abo1e (3 in most cases gi1es the best results+ see figure below.
8ig. the hardening temperature in dependency of the carbon content.
The austenitation of abo1e-pearlitic steel doesn2t occur in the austenitic area+ but 5'-
"'C abo1e (&. (fter glowing at this temperature this temperature the steel consists of
<much= austenite and <little= cementite. The cementite is 1ery hard and remains
unchanged after hardening> after hardening the structure consists of 2 phases + namely
cementite and martensite. (ustenitating in the austenitic area + thus at a temperature
abo1e (cm> doesn2t ma3e sense> the end product cannot become harder.
The diffusion 1elocity of the carbon atoms is 1ery large due to the interstitial
positioning. The heating in the austenitic area for small samples doesn2t ha1e the
occur more than &'-&5 minutes. (t larges samples the center warms less -uic3 than
the borders so that austenitation remains there.
Tempering and refinement.
0teel hardened by -uenching is too brittle for use+ and after some time can crac3.
Therefore another treatment is needed4 annealing or tempering. The higher the
tempering temperature the softer the and also tougher the end product.
T9 remo1e the largest brittleness without hardness loss it is sufficient to heat the steel
at &#' C during ] to & hour. $ereby there originates fine hexagonal iron carbide <-
carbide=. (s a conse-uence the carbon content of martensite decreases+ which
therefore looses its tetragonality and transforms in cubic martensite.
(t a tempering temperature of 2''-3'' C the restaunite transform to bainite.
(t a tempering temperature of 3''-4'' C there originate normal <orthorhombic=
cementite.
(t higher tempering temperature these separations become somewhat rougher+ e1en if
the tempering temperature lies close beneath (&.
(T high tempering temperature the martensite disappear wholly+ and there remains
cementite grains embedded into ferrite.
The structure which originates at tempering at 4''-5'' C + consisting of the fading
martensite and the cementite spheres is called sorbite. By tempering the hardness and
the strength ha1e decreased+ but the rupture strength and the notch bar 1alue.
8ig. 0orbite structure.
The heat treatment 5hardening followed by high tempering6 is called refinement. <not
to be mista3en by the pre1ious isothermal refinement=.
!oft glo#ing in ' stages
The soft steel is first austenitated in such a way+ that all cementite is sol1ed in
austenite. 8or abo1e-pearlitic steel this means4 glowing abo1e (& but beneath (cm>
for pearlitic or under-pearlitic steel this must be glowed during short time abo1e (&.
whereby the steel is transformed isothermally. The remaining cementite particles in
the austenite function as nuclei+ from which the transformation begins. There
originates a soft glow structure of globular cementite. .f the austenitic temperature is
so high that all cementite in the austenite is sol1ed then the bac3-transformation is
much slower+ while the resulting structure if finer and partly lamellar + so that the
hardness is higher.
This soft glowing gi1es the globular structure much faster than other methods. (
disad1antage is that the temperature area + in which the globular transformation must
occur <(& to (& P3'C= + is 1ery small + so that glowing with factory o1ens is hard to
reali,e. Therefore in factory glowing the isothermal bac3-transformation is replaced
by a bac3-transformation during a 1ery slow cooling <ca &' C per hour= from the
austenitic temperature to circa 5' C.
The full heat treatment is gi1en in the figure below.
8ig. $ardening of abo1e-pearlitic steel.
,eat treatment of allo"ed steel.
8or alloyed steel sorts we use TTT diagrams. Beneath an example of K-Cr-!o-steel
is gi1en.
8ig. TTT diagram of a wea3ly alloyed Ki-Cr-!o-steel <schematic=
8. Carbonating and nitrating.
The carbonating consists of absorption of carbon in the surface of a steel obUect
followed by a diffusion of this element in the steel. The result is a shell with a higher
carbon content than the nucleus.
The purpose of carbonating is to obtain a hard+ wear-resistant surface layer combined
with a soft tough nucleus. This is obtained by hardening of the carbonated obUect. The
ad1antage of carbonated steel is the smaller thic3ness of the hardened steel and the
larger toughness of the nucleus.
Carbonating resources
T9 obtain an uniform carbonation a li-uid or gas resource is used. 0olid carbon in an
inert surrounding will only gi1e local carbonation+ after the contact is bro3en.
( li-uid carbonation substance consists of a bath of molten salt mixture+ mostly
chlorides of natrium <sodium= and 3alium <potassium=+ at which cyanides are added to
neutrali,e the decoaling oxygen in the bath.
( gas carbonating substance is light gas. Because of the little rendement it is mixed
with carbon rich gasses li3e propane and butane.
(nother method is the gasification of a certain amount of oil+ to use the gas product
as carbonation substances.
The carbonation process.
The original present oxygen from the air is transformed at the surface in a mixture of
C9 and C92 in the ratio which corresponds with the e-uilibrium
C92 + C 2C9
.f this gas comes in e-uilibrium comes in contact with carbon not in e-uilibrium with
carbon+ the reaction
2C9 C92 + C
will occur.
The theoretical end state is reached if there is e-uilibrium between oxygen+ gas and
metal. To increase the carbon content in the austenitic area the steel must be heated.
The carbonation occurs at temperatures in the neighbourhood of %'' C. The steel
surface thereby obtains a carbon content of '. &.2 :+ depending on the
temperature and the C9content of the carbonating gas. .f the carbon concentration at
the surface is much higher than in the nucleus+ the carbon atoms will diffuse inwards.
8ig. )enetration cur1es at carbonating + schematically. a. after t hours. b after 4 t
hours.
.f the air consists of #': of nitrogen+ and this gas is inert relati1e to the carbonation
reaction+ the process is accelerated by remo1ing nitrogen. This is done by addition of
barium carbonate+ that during carbonation slowly dissects according to
BaC93 Ba9 + C92
The occurring C92 dri1es away the air and participates and the carbonation process.
8ig. 0tructure of the carbonated shell.
,ardening of carbonated steel.
.t seems attracti1e to harden the carbonated samples directly and sa1e the cost heat
costs at hardening.
(n obUection against this method is + that the structure of the austenite during
carbonating+ which is short+ becomes rough. (t unalloyed steel this method is
applicable in the simplest cases. To use this method in more general cases+ light
alloyed steel sorts must be used+ li3e chromiummolybdenumsteel. (t such a steel at
normal carbonation e1en after hours gi1es no grain growth+ so direct hardening has no
obUections. (n ad1antage of such a steel is that complete hardening is reached by
-uenching in oil+ whereby the danger of crac3ing is much less than -uenching in
water. The whole heat treatment is gi1en in the scheme below.
8ig. Carbonating and direct hardening of an alloyed carbonating steel+ schematic
(nother ad1antage of the use of unalloyed steel is that at -uenching there are also
structure impro1ements in the nucleus+ so that this becomes tougher and stronger than
in the case of unalloyed steel. (t the direct hardening there is -uenched at the
carbonation temperature (%''%5'C=. this is much higher than the hardening
temperature which due to the carbon content at the border (0.8:) would be ideal
(around ""0 C). The process then is as s3etched below.
8ig. Carbonating and nondirect hardening.
Nue to grain growth there will be used a light alloyed carbonating steel. The first
cooling a must be done at such a 1elocity that there originates a fine troostite
structure+ if possible also in the nucleus. (T the following austenitating at the border
there originates 1ery fine grained cementite in the austenitic ground mass. The
-uenching b is done in oil.
0uch a treatment can also be done with unalloyed steel. The nucleus will then ha1e a
1ery rough structure. This can be fixed by adding an extra growth phase =normal
flowing of the nucleus2 after carbonating.
*itrating.
(T gas nitrating the steel to be hardened at about 5''55'C is glowed fro a long time
in an ammoniac stream. Mnder these circumstances the ammoniac at the steel surface
will dissect according to
2K$3 2K + 3$2+
whereby the iron wor3s a catalyst. The nitrogen in atomic form+ which hereby
originates+ can sol1e interstitial in the steel =at 5''C some promilles and diffuses
inwards.
8or gas nitration special steel sorts are used. ( nitration steel usually contains '.3
'.4: C+ about &: (l and about &: Cr+ and further a few promille of !o. The
mentioned alloy elements ha1e a large affinity to Kitrogen+ but the inward diffusing
Katoms will bond with the (l+ Cr+ and !o atoms to nitrides. This 1ery fine
dispersion of nitrides increases the hardness (well abo1e hardened steel= to more than
&''' 3g-mm
2
according to /ic3ers method. The difference with carbonating is that
here the hardening occurs during the diffusion process and need not be obtained by
-uenching.
The diffusion is slow and is slower is the carbon content is higher. .n practice a
nitration depth of some mm is obtained after hours of nitrating. Thus it is expensi1e.
Temperature rise doesn2t speed the process because abo1e 5#'C there forms austenite
which at cooling transforms into soft braunite+ a eutectoid of ferrite and 8e4K
corresponding with pearlite. Kitrating is applied to impro1e wear resistance and
fatigue properties.
19. Cast iron.
The bonding 8e3C or cementite doesn2t appear to be stable. The dissection 1elocity is
so small that is appeared the cemenitite was apparently stable. 7e spea3 of metastable
bonding.
The dissection relation 8e3C B 38e A C is ending and cannot be written as a
e-uilibrium reaction. 8or reaching a reasonable dissection 1elocity a high temperature
is needed.
There are certain elements which accelerate the reaction4 silicium+ nic3el. 9ther
elements ha1e an opposite effect4 manganese and chromium.
!etastability of cementite implies that also the iron-carbon diagram is metastable.
The solubilit" of cementite and graphite.
.ron+ at a suitable chosen temperature brought into contact with cementite + will
absorb this bonding till there is saturation. The same is the case with iron in contact
with graphite. The solubility of cementite+ expressed in percents of carbon+ will be
different than that of graphite. ( stable substance will ha1e less inclination to go into
solution than a metastable substance. The solubility of graphite at a certain
temperature will be less that that of cementite. This holds for the solubility in
austenite as that in ferrite.
The stable ironcarbon diagram.
8rom the abo1e their follows that the 3 solubility lines N2C2+ *202 and )2R2 for
graphite are to the left of the corresponding solubility lines for cementite. The
cementite line expires+ so that the 3 mentioned solubility lines form the border of 2-
phase areas in which graphite occurs besides li-uid+ austenite and ferrite. The
diagrams extends to &'':C.
The 3-phase line austenite-li-uid-graphite becomes higher than that of the 3-phase-
line ferrite-austenite-cementite. The upper line is followed. The li-uid solidifies as a
mixture of austenite and graphite.
IronIron Carbide Phase Diagram
8ig
8igure shows the e-uilibrium diagram for combinations of carbon in a solid solution of
iron. The diagram shows iron and carbons combined to form 8e-8e3C at the .":C end
of the diagram. The left side of the diagram is pure iron combined with carbon+ resulting
in steel alloys. Three significant regions can be made relati1e to the steel portion of the
diagram. They are the eutectoid *+ the h"poeutectoid (+ and the h"pereutectoid B. The
right side of the pure iron line is carbon in combination with 1arious forms of iron called
alpha iron <ferrite=+ gamma iron <austenite=+ and delta iron. The blac3 dots mar3
clic3able sections of the diagram.
(llotropic changes ta3e place when there is a change in crystal lattice structure. 8rom
2#'2E-2552E8 the delta iron has a bod"centered cubic lattice structure. (t 2552E8+ the
lattice changes from a body-centered cubic to a facecentered cubic lattice type. (t
&4''E8+ the cur1e shows a plateau but this does not signify an allotropic change. .t is
called the Curie temperature+ where the metal changes its magnetic properties.
Two 1ery important phase changes ta3e place at '.#3:C and at 4.3: C. (t '.#3:C+ the
transformation is eutectoid+ called pearlite.
gamma <austenite= --^ alpha A 8e3C <cementite=
(t 4.3: C and 2'E8+ the transformation is eutectic+ called ledeburite.
C<li-uid= --^ gamma <austenite= A 8e3C <cementite=
Examples of IronIron Carbide Phase Transformations on the TTT Diagram
8igure . 8e-8e3C T-T-T Niagram+
The time-temperature transformation cur1es correspond to the start and finish of
transformations which extend into the range of temperatures where austenite transforms
to pearlite. (bo1e 55' C+ austenite transforms completely to pearlite. Below 55' C+ both
pearlite and bainite are formed and below 45' C+ only bainite is formed. The hori,ontal
line C-N that runs between the two cur1es mar3s the beginning and end of isothermal
transformations. The dashed line that runs parallel to the solid line cur1es represents the
time to transform half the austenite to pearlite. Below we ha1e listed some simple
examples as an exercise at other temperatures that result in different phase
transformations and hence different microstructures.
Example
8ig . Time-Temperature )aths on .sothermal Transformation Niagram
a. <Sed= The specimen is cooled rapidly to 433 O and left for 2' minutes. The cooling
rate is too rapid for pearlite to form at higher temperatures> therefore+ the steel remains in
the austenitic phase until the !s temperature is passed+ where martensite begins to form.
0ince 433 O is the temperature at which half of the austenite transforms to martensite+ the
direct quench con1erts 5': of the structure to martensite. $olding at 433 O forms only a
small -uantity of additional martensite+ so the structure can be assumed to be half
martensite and half retained austenite.
b. <Dreen= The specimen is held at 523 O for &'' seconds+ which is not long
enough to form bainite. Therefore+ the second -uench from 523 O to room
temperature de1elops a martensitic structure.
c. <Blue= (n isothermal hold at 5"3 O for 5'' seconds produces a half-bainite and
half-austenite structure. Cooling -uic3ly would result in a final structure of
martensite and bainite.
d. <9range= (ustenite con1erts completely to fine pearlite after eight seconds at
#"3 O. This phase is stable and will not be changed on holding for &''+'''
seconds at #"3 O. The final structure+ when cooled+ is fine pearlite.
Cast irons typically contain 2-4 wt: of carbon with a high silicon concentrations and a
greater concentration of impurities than steels. The carbon equivalent <C*= of a cast iron
helps to distinguish the grey irons which cool into a microstructure containing graphite
and and the white irons where the carbon is present mainly as cementite. The carbon
e-ui1alent is defined as4
( high cooling rate and a low carbon e-ui1alent fa1ours the formation of white cast iron
whereas a low cooling rate or a high carbon e-ui1alent promotes grey cast iron.
Nuring solidification+ the maUor proportion of the carbon precipitates in the form of
graphite or cementite. 7hen solidification is Uust complete+ the precipitated phase is
embedded in a matrix of austenite which has an e-uilibrium carbon concentration of
about 2 wt:. 9n further cooling+ the carbon concentration of the austenite decreases as
more cementite or graphite precipitates from solid solution. 8or con1entional cast irons+
the austenite then decomposes into pearlite at the eutectoid temperature. $owe1er+ in grey
cast irons+ if the cooling rate through the eutectoid temperature is sufficiently slow+ then a
completely ferritic matrix is obtained with the excess carbon being deposited on the
already existing graphite.
7hite cast irons are hard and brittle> they cannot easily be machined.
The iron-carbon phase diagram showing the eutectic and eutectoid reactions.
Drey cast irons are softer with a microstructure of graphite in transformed-austenite and
cementite matrix. The graphite fla3es+ which are rosettes in three dimensions+ ha1e a low
density and hence compensate for the free,ing contraction+ thus gi1ing good castings free
from porosity.
The fla3es of graphite ha1e good damping characteristics and good machinability
<because the graphite acts as a chip-brea3er and lubricates the cutting tools. .n
applications in1ol1ing wear+ the graphite is beneficial because it helps retain lubricants.
$owe1er+ the fla3es of graphite also are stress concentrators+ leading to poor toughness.
The recommended applied tensile stress is therefore only a -uarter of its actual ultimate
tensile strength.
0ulphur in cast irons is 3nown to fa1our the formation of graphite fla3es. The graphite
can be induced to precipitate in a spheroidal shape by remo1ing the sulphur from the melt
using a small -uantity of calcium carbide. This is followed by a minute addition of
magnesium or cerium+ which poisons the preferred growth directions and hence leads to
isotropic growth resulting in spheroids of graphite. The calcuim treatment is necessary
before the addition of magnesium since the latter also has an affinity for both sulphur and
oxygen+ whereas its spheroidising ability depends on its presence in solution in the li-uid
iron. The magnesium is fre-uently added as an alloy with iron and silicon <8e-0i-!g=
rather than as pure magnesium.
$owe1er+ magnesium tends to encourage the precipitation of cementite+ so silicon is also
added <in the form of ferro-silicon= to ensure the precipitation of carbon as graphite. The
ferro-silicon is 3nown as an inoculant.
0pheroidal graphite cast iron has excellent toughness and is used widely+ for example in
cran3shafts.
The latest brea3through in cast irons is where the matrix of spheroidal graphite cast iron
is not pearlite+ but bainite. This results in a maUor impro1ement in toughness and strength.
The bainite is obtained by isothermal transformation of the austenite at temperatures
below that at which pearlite forms.
:hite cast iron.
Because cast iron besides iron and carbon also contains 0i+ !n and ) + it can ne1er be
considered a binary 8e-C diagram. The course of the solidification cannot be deduced
from the iron-carbon diagram.
7hite cast iron melts wholly according to the metastable diagram. The carbon content
lies abo1e 2:. There originates ledeburite. Between 2 and 4.3: carbon there first
originates austenite+ at more than 4.3: carbon first cementite. Msually the carbon
content lies at about 3:. The cast iron will between the beginning solidification point
and the ledeburite point separate off austenite <if we use the binary diagram=. (t the
three-phase-line the structure consists of W<4.3 -3=L<4.3 -2=X &'' @5": austenite with
2:C and 43: li-uid with 4.3:C. The last phase solidifies into ledeburite in which
W<."-4.3=L<."-2=X&'' @5&: austenite and 4%: cementite is present.
Nirectly after solidification the structure will consist of dendrites of austenite with
between it ledeburite.
(t further cooling the carbon content of the austenite will become smaller by
formation of cementite+ the composition changes from * at &&3'QC to 0 at "23QC.
(rri1ed at "23QC the structure consists of W<."-3XL<."-'.#== &'' @3: austenite
with '.#: C and 3": cementite.
(fter passing the lowest 3-phase line the asuetnite goes into pearlite. .f we neglect the
formation of tertiar cementite after this point there are no changes.
2re" ferritic cast iron.
(t solidification of ferritic cast iron the stable diagram is completely followed <till
cooling=. 8or this is needed that the cementite dissection is promoted by suitable
admixtures <e.g. Ki=. <Noes nt apply for binary 8e-C alloys=. 0olidification according
to the stable diagram means that ferritic cast iron cosists exclusi1ely of ferrite and
graphite. ( cast iron with 3: carbon+ which solidifies according to the stable
diagram+ will consist of W<&''-3=L&''X&'' @%": ferrite and 3: graphite. This cast
iron will be 1ery soft by absence of cementite.
2ra" pearlitic cast iron.
The pearlitic cast iron consist of pearlite and graphite. (t solidification first the stable
diagram is followed and the eutecticum C2 originates. The presence of pearlite
indicates that later when cooled the austenite will dissect according to the metastable
3-phase line. 0omewhere between &&35Q and "23Q there is a transition from the stable
to the metastable system. (ssuming we may describe the structure using the iron-
carbon diagram+ we can calculate the composition of grey pearlitic cast iron with 3:
C will be W<&''-3=L<&''-'.#=X&'' @%".#: pearlite and 2.2: graphite.
Drey cast iron+ 8e-3.2C-2.50i wt:+ containing graphite fla3es in a matrix which is
pearlitic. The spec3led white regions represent a phosphide eutectic. *tchant4 Kital 2:
Drey cast iron+ 8e-3.2C-2.50i wt:+ containing graphite fla3es in a matrix which is
pearlitic. The lamellar structure of the pearlite can be resol1ed+ appearing to consist of
alternating layers of cementite and ferrite. The spec3led white regions represent a
phosphide eutectic. *tchant4 Kital 2:

.n decreasing order of carbon content we ha1e white+ grey pearlitic and grey ferritic cast
iron. There is no sharp transition between these sorts.
!hrin1ing and gro#th of cast iron.
(n alloy in general is more castable is the melting point is lower an the 1olume change
during solidification and further cooling is smaller. Drey cast iron satisfies these
conditions. ( cast temperature of &2''-&35'QC is easily obtained.
Because dissection of cementite into iron and graphite is paired with a 1olume increase+
cast iron at solidification will shrin3 less than cast iron and the less if it is more ferritic. (
ferritic cast iron with much carbon will expand e1en at solidification. The cooling after
solidification is paired with graphite separation+ so the shrin3 is relati1ely small. <this
doesn2t occur at white cast iron=.
Dray cast iron containing cementite at use log use at high temperature will ha1e a slow
1olume increase by dissecting of the cementite. This growth is halted if the cementite has
disappeared wholly. 9ften the growth continues because the graphite disappears by
oxidation and ma3es place for iron oxide.
The carbon factor
The eutectic alloy in general is better castable than a non-eutectic of the same sort
because4 there is no solidification traUectory+ the solidification point is low and the alloy
stays thin and li-uid till full solidification. The carbon factor is the ratio between the
percentage present carbon and that of the corresponding eutecticum. (t a eutectic cast
iron the carbon factor is one+ at a under-eutectic iron it is smaller and at abo1e-eutectic
larger. .n the iron-carbon diagram the eutectic carbon content is 4.3:. Because
manganese and sulphur are to be neglected we following formula is used for the eutectic
carbon content 4
4.3 P <:0i A :)=L3
The graphite separation.
The amount of graphite formed during cooling or solidification depends on the cooling
1elocity and the composition. Cow cooling 1elocity <and this long time stay at high
temperature= will encourage graphite separation and dissection of cementite. The cooling
1elocity is small when iron a piece with thic3 walls is cast in a dry+ pre-heated sand form+
at high cast temperature. Mnder these circumstances the form material has a bad heat
conduction power and the melt has a large heat-content.
The most important accelerators of graphite separation are the carbon and the silicium.
!anganese has a delaying effect. 7eichelt used round rods of 3'+ 2' + &'+ and 3 mm for
different iron sorts. 0ee the !aurer-7echelt diagram below.
8ig. 7eichelt diagram for thic3ness of 3' and mm.
The form of graphite.
(s can be seen in the following figures the graphite has the form of lamellas+ because the
structure of the graphite is hexagonal. The si,e of the graphite lamellas relates to their
number4 the more there are+ the finer they are.
8ig. Drey ferritic cast iron. 0tructure composites4 graphite+ ferrite+ and steadite <ternary
8e3C-8e2) - - eutecticum=.
8ig. 9rdinary cast iron.
8ig. Drey pearlitic cast iron.
!pheroidal 2raphite Cast Iron
The chemical composition of the cast iron is similar to that of the grey cast iron but with
'.'5 wt: of magnesium. (ll samples are etched using 2: nital.
0pheroidal graphite cast iron+ 8e-3.2C-2.50i-'.'5!g wt:+ containing graphite nodules in
a matrix which is pearlitic. 9ne of the nodules is surrounded by ferrite+ simply because
the region around the nodule is decarburised as carbon deposits on to the graphite.
*tchant4 Kital 2:
0pheroidal graphite cast iron usually has a pearlitic matrix. $owe1er+ annealing causes
the carbon in the pearlite to precipitate on to the existing graphite or to form further small
graphite particles+ lea1ing behind a ferritic matrix. This gi1es the iron e1en greater
ductility. (ll samples are etched using 2: nital.
Graphite nodules in a ferritic matrix.
Draphite nodules in a ferritic matrix. 0ome carbon deposited during tempering is also
1isible. *tchant4 Kital 2:
(lac1heart Cast Iron
Blac3heart cast iron is produced by heating white cast iron at %''-%5'
o
C for many days
before cooling slowly. This results in a microstructure containing irregular though
e-uiaxed nodules of graphite in a ferritic matrix. The term Gblac3heartG comes from the
fact that the fracture surface has a grey or blac3 appearance due to the presence of
graphite at the surface. The purpose of the heat treatment is to increase the ductility of the
cast iron. $owe1er+ this process is now outdated since spheroidal graphite can be
produced directly on casting by inoculating with magnesium or cerium. (ll samples are
etched using 2: nital.
Blac3heart cast iron. Blac3heart cast iron. *tchant4 Kital 2:

Mechanical properties
7hite cast iron is due to its content of cementite 1ery hard and brittle and can only be
processed by grinding. .t is used for its hardness in e.g. bullets.
Drey cast iron contains graphite in the forms of lamellas which causes a change in
mechanical properties compared with cast steel. The round mass which consists of
pearlite and <or= ferrite + has a pull strength of &'' to "' 3gLmm
2
. This high 1alues
originate because the alloying elements li3e silicon and manganese strengthen the ferrite.
The graphite+ which ta3es 5 to &5 1olume percentages has a higher 1alue than expected4
at pulling the lamellas will stand open+ because of the little resistance which graphite has.
7hen the load increase more lamellas will stand open+ so that $oo3e2s law doesn2t apply
here. The elasticity modulus will become smaller if the load inter1al becomes larger. The
tensions in the groundmass of the cast iron are larger than calculated from load and rod
cross section because4 a. the cross section consists of 5 a &5 : of graphite which ta3es no
tensions+ so that the rest is loaded higher. b. the tensile stress along the borders of the
graphite lamellas will be larger tan in between the lamellas because of tension
concentrations. 0ee fig. below
8ig. *xplanation of the mechanical properties of grey cast iron.
.f the tension at the border of a graphite lamella surpasses the pull strength then the
lamella crac3s open. Because of this the tension in the remaining ground mass increases
further and the crac3 expands o1er the whole surface. (T the pull test a low pull strength
and low stretch is found.
(t the pressure test the lamellas are pressed closed and gi1e resistance. The thumb rule
that the hardness is trice the pull strength doesn2t hold for cast iron. (nother conse-uence
is that the elasticity modulus at pressure is larger than at pull+ so that the bending strength
is larger than the pull strength. The nodular cast iron is stronger+ tougher and stiffer than
the corresponding lamellar because the spheroid graphite influences the structure much
less and causes tension concentration than the lamellar. 0ee fig.
8ig. Kodular ferritic cast iron.
Internal tensions in cast pieces.
.n a cast piece there are internal tensions. The character of these tensions is determined
by the way of casting+ solidifying and cooling and by the form
(t a cylindrical rod the solidification will start at the outside. The inner will shrin3 and at
cooling shrin3 e1en further than the shell because the temperature is higher. (s a
conse-uence in the nucleus there will originate pull- and in the shell pressure tensions. .f
the cylinder is closed off at the outer side it will become shorter.
8ig. ( cast piece for pro1ing internal tensions. The side-rods solidify first+ the middle
piece later> the first will ha1e pressure the last load. This is shown by increase of the
distance between the mar3s.
2lo#ing of cast iron
The heat treatment of cast iron is mostly restricted to tension free glowing at about
5''QC. .f also the processability must be impro1ed there is glowed at a higher
temperature. .n both cases there is chance at growing which deteriorates the mechanical
properties.
The processability becomes larger if there is more grain+ and by disappearance of
cementite. Tension free glowing of white cast iron doesn2t ma3e sense because there the
ledeburite net doesn2t change much. Because the internal tensions mostly appear in the
shell + the glowing occurs after the preprocessing.
$ardening and tempering of cast iron is applied little. 0amples of white cast iron will
crac3 at hardening by 1olume increase. Drey pearlite cast iron is hardened in oil to a1oid
crac3s. The present alloy elements silicon+ manganese+ phosphor+ etc+ delay the critical
cooling 1elocity by obtaining hardening in oil by -uenching. The tempering temperature
depends on the desired properties.
0orging and rolling of cast iron.
Drey cast iron in the austenite area is forgeable because there all cementite is ta3en in the
austenite> white cast iron difficult. The forgeability is not as good as that of steel because
the cast lamellas gi1e rise to crac3s and because the silicon ma3es the austenite stiffer and
less tough. (t enduring forging the graphite lamellas are stretched in the direction of the
forging or rolling. .n this stadium the originated crac3s can be welded closed.
Kodular cast iron is better forgeable than ordinary.
0orgeable cast iron.
Cac3 of toughness is a disad1antage for cast pieces. This can be undone by ma3ing cast
iron that contains no graphite lamellas. This is the case at nodular cast iron. There are 2
methods of heat treatment to obtain the desired result.
The oldest process is researched by Seamur in &"&-&"25+ consist of heating of white
cast iron in a wea3 oxidi,ing surrounding. The carbon is oxidi,ed+ but not the iron
C92 A C 2C9 This C9 gas can reduce iron ore according to4
C9 A 38e293 C92 A 28e394
By diffusion there originates a carbon stream from the middle to the surface. .f the
process is long then the result is wholly ferritic iron without carbon. This method is called
glow freshening> it is only applicable on cast pieces with small wall thic3ness.
The other process+ the tempering4 white cat iron is heated in a neutral surroundings under
such circumstances that the cementite is dissected. The carbon that hereby originates+
forms no lamellas but nests of sphere-li3e separations of temper carbon.
Tempering
The white cast iron to be tempered will ha1e to contain more silicon than the sort
destined for anneal freshening. This content must be low enough to pre1ent separation of
graphite during solidification. To obtain this the process must be split into 2 parts. The
first part occurs at high temperature <%'' to %5'=. 7hite cast iron at this temperature
consists of austenite and cementite + whereby the austenite is saturated with carbon in
e-uilibrium with cementite. .8 there form nuclei of temper carbon then the state changes+
because these particles will be surrounded by austenite saturated with carbon in
e-uilibrium with graphite. The solubilibty of graphite is smaller than that of cementite so
that at the border layer between the cementite particles and the austenite the cementite
dissol1es. The carbon diffuses from this layer to that of austenite and temper carbon
forms here. .f the process has ended the structure consists of austenite and temper carbon.
.n the austenite there is ca &.5: carbon and to remo1e this the temperature is gradually
lowered+ so that the solubility decreases till reaching the 3-phase-e-uilibrium 4 austenite
ferrite A temper carbon. (t this moment the carbon content has lowered to about
'.#:C. .f the temperature is lowered e1en further then the austenite will dissect. .f the
cooling 1elocity is slow then ferrite will originate. .f the process is not slwo enough to
end the process then pearlite will originate.
8ig. 0tructure of completely tempered cast iron.

:ear.esistant ,ighChromium Cast
Iron
This cast iron is used in circumstances where a 1ery high wear resistance is desirable. 8or
example+ during the 1iolent crushing of roc3s and minerals. .t contains a combination of
1ery strong carbide-forming alloying elements. .ts chemical composition is+ therefore+
8e-2.C-&"Cr-2!o-2Ki wt:.
The white phase is a chromium-rich
carbide 3nown as !"C3. The matrix
consists of dendrites of austenite+ some
of which may ha1e transformed into
martensite. There may also be
relati1ely small -uantities of other
alloy carbides.
The white phase is a chromium-rich
carbide 3nown as !"C3. The matrix
consists of dendrites of austenite+ some
of which may ha1e transformed into
martensite. There may also be
relati1ely small -uantities of other
alloy carbides.

Austempered Ductile Cast Iron
The chemical composition of the cast iron is 8e-3.52C-2.5&0i-'.4%!n-'.&5!o-'.3&Cu
wt:. (ll samples are etched using 2: nital. Colour micrographs are produced by first
etching with 2: nital+ followed by open air heat treatment of the metallographic sample
at 2"'
o
C for 3 h. This oxidises the sample and produces interference colours which are
phase dependent.
Nuctile iron as-cast. Kodules of graphite+ pearlite <dar3 islands= and ferrite <light
bac3ground=. *tchant4 Kital 2:
Nuctile iron as-cast. Kodules of graphite+ pearlite <dar3 islands= and ferrite <light
bac3ground=. *tchant4 Kital 2:

(ustenitised %5'_C+ austempered 35'_C for 4 min.
Austenitised at 950C, austempered at 350C for 64 min.

11. Aluminium and Aluminium allo"s.
The base rough material is bauxite which in general consists of 5'-': (l293+ &'-2':
8e393+ 2-5: 0i92+ &-3: Ti92+ some other impurities and $29. By a series of chemical
treatments from this pure (l293 is won+ which contains some hundredths of percents 0i92
and 8e293. 8rom the (l293 there can be won (l with electrolysis. The (l293 then is sol1ed
in molten 3ryolite <(l8e3.3Ka8=. The electrolysis occurs at a temperature of &'''C. The
aluminium collects at the negati1e pole of the + at the bottom of the electrolysis 1essel
and is tapped from time to time. The oxygen oxidi,es the positi1e pole+ which consists of
graphite+ to C92+ and by the current flow there is de1eloped so much heat that the bath
temperature is maintained without adding energy. The so obtained aluminium is pure and
only contains some promilles impurities mainly 8e and 0i.
The aluminium production re-uires much energy. 8or & ton of aluminium 4-5 tons of
bauxite is re-uired. T9 ma3e 2 tons of pure (l293+ there is re-uired 25.&'

3cal heat+ to
be obtained from e.g. # tons of brown coal. To ma3e & ton (l from this (l293 by
electrolysis+ there is re-uired &5''' 37h of electrical energy> abo1e that ] ton of anode
graphite is used.
8or some applications+ li3e reflectors+ electrolytic capacitors etc+ the obtained aluminium
isn2t pure enough. By a second electrolysis+ which re-uires about 2'''' 37h per ton the
purity can be increased to %%.%#:. This product is sometimes called 5raffinal6.
Properties of unallo"ed aluminium.
)roperty 8e Cu (l !g
0pecific weight <gLcm
2
= ".% #.% 2." &."
0pecific electrical resistance <+ 2'C= %.# &." 2." 4.5
$eat conduction <cal.cm.sec C+ 2'C= '.2 '.% '.5 '.4
Cinear expansion coefficient <C
-&
.&'

+ 2'C= &2 &" 24 2

!elting point <C= &54' &'#' ' 5'
*lasticity modulus <3gLmm
2
+ 2'C= 2'''' &2''' "''' 4'''
The specific weight of aluminium is about &L3 of that of steel. Compared to steel the
electric resistance is large+ and the expansion coefficient is high.
Allo"s of the t"pe Al!i
The binary system aluminium-silicium is shown in fig. below.
8ig. The binary state diagram (l-0i.
The alloy with about &3: 0i+ is called silumin+ is the classical aluminium-cast alloy. The
shrin3 is about half of that of pure aluminium.
(t slow cooling there originates rough+ plate-formed crystals+ which ma3e the alloy
brittle. The eutecticum degenerates so that the 0-crystals become extra large. This can be
tac3led by casting of '.&: Ka to the melt in the form of some Ka slat <refinement=. By
this there originates grain refinement. By adding the sodium the eutectic temperature
decreases from 5"" to 54C+ while the eutectic concentration shifts from &2 to &4: 0i.
(n alloy with &3: 0i by refining becomes under-eutectic and has aluminium dendrites
under a microscope+ embedded in a ground mass of 1ery fine grained eutecticum.
( modern cast alloy of the type (l-0i is (l0i " !g '.3 <aluminium with ": 0i and '.3:
!g=. 0ilicium and magnesium can form an intermetallic bonding !g20i.
Allo"s of the t"pe AlCu.
.n this group there are both cast- and 3neading alloys. The binary system is gi1en below.
8ig. Ceft part of the binary state diagram (l-Cu.
( well-3nown alloy of this type is (lCu 4.5 + with a elongation limit of &' 3gLmm
2
. This
has a good processability.
(n alloy which at high temperatures has good properties + originates by addition of 8e <or
Ki= and !g to (l-Cu-alloys. (K example is (l Cu &' 8e & !g 3+ a piston alloy.
Allo"s of the t"pe AlMg.
The binary system is gi1en below.
8ig. The aluminium rich part of the binary state diagram (l-!g.
Technical (l-!g alloys which contain till &': !g.;e+ ha1e a good resistance against
corrosion by the atmosphere+ by sea water and by wea3 al3aline li-uids.
7ith increasing !g-content the strength increases+ the expansion coefficient also+ but the
castability and the fatigue stress decrease. (t solidification of (l-!g there occur strong
segregation phenomena+ due to the strong < AC= loop. (s a conse-uence in cast alloys
with more than 5: !g in general there is an amount of the eutectoid present> in (l !g 5
little+ in (l !g % much.
Allo"s of the t"pe Al;n.
)ure (l-;n alloys+ pre1iously used much+ are nowadays seldom used because of poor
mechanical and corrosion properties.
The alloy (l;n&' P &2Cu4- 2 has good cast properties and reasonable strength+ used fro
motor bloc3s.
( 3nown alloy for sand casting is (l;n 5.5 !g '. Cr '.5 Ti '.2. (fter casting and
cooling there occurs precipitaion hardening at room temperature> the full strength is
obtained after 3 wee3s. The hardening time can be shortened by after annealing at higher
temperatures <e.g. &' hours at &#'=.
1'. Magnesium and magnesium allo"s.
)ure magnesium has a specific weight of &."4. .t is much lighter than (l+ that has a
specific weight of &."4. The price of !agnesium and its alloys are higher than that of (l.
The production of !agnesium is done mainly by the following processes4
a. by electrolysis of magnesium chloride <!gCl2=. The !gCl2 can be won from e.g.
dolomite <CaC93.!C93=+ from carnelllite <!gCl2.OCl.$29= from seawater <!g-
content '.&5:= or by chlorating of !g9. (t the electrolysis the .!gCl2 is
dissol1ed in a suitable mixture of al3ali- or al3ali-chlorides. The energy use is
about 2'''' 37h per ton magnesium. The purity of the !g is about %%.#:. The
main impurities are 8e+ (l+ 0i and Cl. 8urther refinement is possible by
sublimation.
b. By reduction of !g9+ usually with 0ilicon. The !g9 can for example be
obtained by calcinating of magnesite <!gC93=. .t is more fa1oritable to start from
the double oxide Ca9.!g9 <to obtained by calcinating of dolomite=. By heating
this together with 0i in retorts + !g is obtained+ which escapes as 1apor4
2!g9.Ca9 A0i <Ca9=2.0i92 A 2!g
Properties of unallo"ed magnesium.
The elasticity modulus is much lower than that of aluminium. !agnesium is 1ery
ignoble <base=. The corrosion tendency can be reduced strongly by a1oiding specific
impurities li3e 8e+ Ki and Cu. By the chromate treatment <pic3ling in a watery
solution of &'-&5: nitric acid and -&': bichromate= there originates a protecting
layer.
The crystal structure of !g is the hexagonal close sphere pac3ing. (t room
temperature the base plane is the only slide plane> in this plane there are 3 slide
directions possible+ the number of slide system thus is 3. This is too less for plastic
deformation in polycrystalline !g.
(T temperature abo1e 22'C other planes also occur as slide planes+ to ma3e large
plastic deformatios possible. (t temperatures of 3''-4'' it is possible to extrude+
forge and roll the metal.
The allo" MgAl.
)art of the binary system !g-(l is gi1en in the figure below. The simplest cast alloys
of thus type contain till &': ( and a few promilles !n.
8ig. Ceft part of the state diagram !g-(l.
(s a conse-uence of the large width of the <AC=-loop and of the low diffusion
1elocity at solidification of such alloys there occur segregation-phenomena+ e1en at
slow cooling. (lloys cast in sand already at an (l content of 3: there will be
eutecticum> this is degenerated> there are isolated -areas in the -ground metal. By
the deformation of the -phase the (l-content of the -matrix will be smaller than
corresponds with the nominal composition.
.f the (l-content increase this effect becomes stronger. Because the strength of the
!g-(l-alloys is mainly determined by that of the -mixing crystal+ the !g-(l alloys
cast in sand will ha1e increasing strength with the nominal (l-percentage. This will
ha1e a maximum at around : to decrease afterwards.
8ig. )ull strength B and rupture stress <= of !g-(l-alloys cast in sand.
The hard -phase causes a decrease of the brea3ing strength at high (l percentages.
By homogenous annealing followed by -uenching+ the homogeneous phase at room
temperature can be obtained + with an impro1ement of the properties.
1+. Copper and Copper allo"s.
Copper is mainly won from sulphidic minerals+ e.g. copper stone <Cu8e02=. Because
copper ores usually are poor <less than &: copper=+ they are bro3en+ grinded and
flotated and are processed to concentrations of a few tens of percents. By <oxidi,ing=
roosting the sulfur is remo1ed from the concentrate. The conce4ntrate is then melted
in a furnace under wea3 oxidi,ing circumstances. $ere part of the sulfur again
disappears while the run stones are ta3en by the slag. !atte is obtained of which the
composition is mainly determined by the used ores. .t contains Cu+ 0 and 8e in the
ratio 24&4& and 5: impurities. The matte is oxidi,ed + the iron is transformed into
8e9+ which is ta3en into the acid slag. .n a later stadium there forms copper oxidule
<Cu29=+ which together with the present Cu20 forms copper according to4
2Cu29 A Cu20 Cu A 092
whereby 092 escapes. .n this way raw copper is produced which contains %#-%%:
Cu.
This raw copper is refined in an o1en. (ll elements more ignoble <base= than copper
are oxidi,ed till their e-uilibrium concentration with the oxygen concentration in the
bath. The last at the end of the oxidation period is '.-'.#:> the oxygen is present in
the form of Cu29. (fter refinery the melt is again deoxidi,ed by poling> tree trun3s of
green wood are put into the melt. The reducing gasses ta3e away the oxygen in the
bath. This process ends if the oxygen content in the melt has decreased to about
'.'5:.
The largest part of the obtained refined copper is cast directly into anode plates and
subUected to electrolytic refinement in a watery bath of sulfur acid and copper sulfate.
The anodes dissol1e at electrolysis+ the impurities deposit as a mud and remain in the
solution. The thus obtained cathode plates contain %%.%: or more copper.
Properties of unallo"ed copper.
Copper has a good conduction power for electricity and heat. The copper used for
electricity must ha1e high purity+ because impurities lower the conduction power.
<0ee figure below=
8ig. Change of electrical conduction of copper by different elements.
8rom the figure it shows that especially phosphor is damaging.
The crystal structure of copper is plane centered cubic <fcc= Copper and copper alloys
can be deformed plastically. .n recrystallised copper there are many twins. Copper
has a good corrosion resistance.
Messing $Cu<;n%
The binary system Cu-;n is gi1en below.
8ig. Binary state diagram Cu-;n.
The -phase has + li3e copper+ the cubic face centered structure. The -phase has the
cubic body centered structure. $ereby the -phase is unordered. .n the 2-phase there
is ordering> the 2-alloys can be considered intermetallic bondings Cu;n.
-mixing crystals ha1e a cubic structure with 52 atoms per unit cell. They ha1e the
character of an intermetallic bonding with formula Cu5;n#. The remaining structures
<++= for the messing sorts are not important.
(t production+ the 1apor pressure of ,inc is 1ery high <coo3ing point %''C=+ so that
at melting part of the ,inc will e1aporate.
!essing with 3%: ;n at room temperature consists of homogeneous -crystals> it is
called -messing. .t is deformable at room temperatures+ especially if the ;n-content
is about 3':. The warm deformability of -messing between 3''-#''C is poor+ but
comes higher at higher temperatures. 7arm rolling is doen at relati1ely high
temperature.
!essing sorts with a ;n-content between 4 and 5': at high temperature consist of
homogeneous -crystals> these are well warm deformable. Below 45'C there is
ordering and the alloys consist of 2-crystals. These are hard and brittle + so that such
alloys aren2t usable technically.
( ;n-content between 3% and 4: gi1es <A=-messing. (t room temperature it
consists of and crystals. The -phase gi1es toughness. (t high temperature such a
messing sort consists wholly of -crystals.> this causes a good warm deformability.
(fter etching in <A=-messing the - and - crystals can be obser1ed. .f the ;n-
content is close to 3%: then the 2-crytals are embedded in the ground mass of >
the alloy is relati1ely tough. (t percentages close to 4: the crystal are surrounded
completely by the 2. The brea3ing stress is small.
8ig. )ull strength of 3nead messing in different states as a function of the ;n-content.
(ron4e.<Cu A0n=
The binary system CuA0n is gi1en below.
8ig. The binary state diagram Cu-0n for 0n-contents `4':.
The - phase has the fcc or cubic plane centered structure.> the -phase is bcc li3e the
-phase. The -phase loo3s li3e the -phase in messing4 it has the structure Cu3&0n#
and is hard and brittle. The transition 1elocities below 5''C are so small that the
theoretical -solubility line is ne1er followed. .n practice the -solubility below 5''
is temeparture independent. Because the reaction A at 33'C is slow+ a bron,e
sort at 4''C containing the -phase in general at room temperature will also consists
aprtly of the .
The <CA=-loop is 1ery wide. (t the used cooling 1elocities there will be segregation
phenomena. (T bron,e sorts with less than &5:0n+ the -phase can be remo1d by
homogenous annealing in the -area.
8ig. Brinell hardness <3gLmm
2
=+ pull strength <3gLmm
2
= and brea3 stress <:= of binary
Cu-0n-alloys in the cast state.
Aluminium copper.
The binary Cu-(C alloys ha1e a good strength and reasonable heat strength. They
ha1e a good resistance against oxidation at high temperatures in air+ a good corrosion
resistance against not too strong acids. The structure of the -phase is fcc+ the-phase
is bcc and the 2-phase is a complicated intermetallic bonding.
8ig. Binary state diagram Cu-(l for (l-contents ` 2':.
(er"llium copper.
This is one of the most 3nown precipitation-hardening alloys. They ha1e high
strength and good conduction of electricity and heat. )art of the state diagram is gi1en
below.
8ig. )art of state diagram Cu-Be.
The most used composition is CuBe&.%Co '.2+ whereby cobalt is added to lesse the
chance to discontinuous precipitation during after-annealing. The temperature for
solubility annealing lies at about #''C+ while the temperature for after annealing
usually lies between 3&' and 35' C. The mechanical properties can be impro1ed by
applying cold deformation <rolling= between solubility and after annealing.
0tate B <OgLmm
2
= '.& <OgLmm
2
= <:=
(fter solubility glowing 5' 22 5'
(fter solubility annealing and after annealing &22 &'" 5
(fter sol. ann.+ hard rolling and after annealing &45 &3' 2
Cast + after solubility P and after annealing &&' #' 2
Coppernic1el )allo"s
The binary system is simple.
8ig. The binary state diagram Cu-Ki.
Copper and nic3el form in the solid state a continuous series of fcc mixing crystals.
The strength of copper-nic3el alloys rises with the Ki content> at about ': Ki the
maximal 1alue is obtained at a still good toughness> the brea3ing stress there is more
than 4':. !uch used Cu-Ki alloys are4
Cupronic3el+ Cu with &'-3'a Ki and about &:8e. The presence of 8e impro1es the
corrosion resistance against sea water.
Constantan + CuKi45. 9f all Cu-Ki alloys it has the largest electrical resistance.
!onel4 CuKi#8e3!n&+ with a little 0i and C. .t is used fro its good corrosion
against seawater.
!older
!ostly consist of a tin-lead-alloy. .n the figure below the binary state diagram of tin-
lead is gi1en.
8ig. Binary system )b-0n.
Problems
IronIron Carbide Phase Diagram Example
8ig &4 8e-8e3C )hase Niagram
8igure & shows the e-uilibrium diagram for combinations of carbon in a solid solution of
iron. The diagram shows iron and carbons combined to form 8e-8e3C at the .":C end
of the diagram. The left side of the diagram is pure iron combined with carbon+ resulting
in steel alloys. Three significant regions can be made relati1e to the steel portion of the
diagram. They are the eutectoid *+ the h"poeutectoid (+ and the h"pereutectoid B. The
right side of the pure iron line is carbon in combination with 1arious forms of iron called
alpha iron <ferrite=+ gamma iron <austenite=+ and delta iron.
(llotropic changes ta3e place when there is a change in crystal lattice structure. 8rom
2#'2E-2552E8 the delta iron has a bod"centered cubic lattice structure. (t 2552E8+ the
lattice changes from a body-centered cubic to a facecentered cubic lattice type. (t
&4''E8+ the cur1e shows a plateau but this does not signify an allotropic change. .t is
called the Curie temperature+ where the metal changes its magnetic properties.
Two 1ery important phase changes ta3e place at '.#3:C and at 4.3: C. (t '.#3:C+ the
transformation is eutectoid+ called pearlite.
gamma <austenite= --^ alpha A 8e3C <cementite=
(t 4.3: C and 2'E8+ the transformation is eutectic+ called ledeburite.
C<li-uid= --^ gamma <austenite= A 8e3C <cementite=
Equilibrium Calculations
&. Di1en the 8e-8e3C phase diagram+ 8ig. &+ calculate the phases present at the eutectoid
composition line at4
a. T @ 3'''E8
b. T @ 22''E8
c. T @ &333E8
d. T @ 4&'E8
2. Calculate the phases in the cast-iron portion of the diagram at the eutectic
composition of 4.3: C in combination with %5.": ferrite at4
a. T @ 3'''E8
b. T @ &"'E8
c. T @ &333E8
3. ( eutectoid steel <about '.#:C= is heated to #''EC <&4"2E8= and cooled slowly
through the eutectoid temperature. Calculate the number of grams of carbide that
form per &''g of steel.
4. Netermine the amount of pearlite in a %%.5: 8e-'.5:C alloy that is cooled
slowly from #"'EC gi1en a basis of &''g of alloy.
!olutions
&. a. T @ 3'''E8. 0ince the composition * is eutectoid+ the carbon content is
'.#3:.
b. T @ 22''E8. (t this temperature+ austenite exists as a single-phase solid.
c. T @ &333E8. Two phases exist+ ferrite and austenite. The percentages are
determined by the le1er rule4 X b <XAY= @ <Cy-C= b <Cy-Cx=.
proeutectoid ferrite @ <'.#3 - '.&#= L <'.#3 - '.'25= x &'' @ #'.":
austenite @ <'.&# - '.'25= L <'.#3 - '.'25= x &'' @ &%.3:
d. T @ 4&'E8. ( small amount of cementite will precipitate following the solubility
line from '.'25: C at &333E8 to '.''#: C at room temperature. The o1erall
percentages of ferrite and cementite are4
ferrite @ <." - '.&#= L <." - '.'&= x &'' @ %".4
cementite @ <'.&# - '.'&= L <." - '.'&= x &'' @ 2.:
2. a. T @ 3'''E8. (t this temperature+ the eutectic is all li-uid.
b. T @ &"'E8. 0ince there is a change of the solubility line+ there will be a change
in the austenite composition+ that will transform to the eutectoid at &333E8. The
o1erall austenite and cementite composition will be4
austenite @ <." - 4.3= L <." - &.2= x &'' @ 43.3:
cementite @ <4.3 - &.2= L <." - &.2= x &'' @ 5.":
c. T @ &333E8. (t this temperature the austenite has a eutectoid composition and
will transform into pearlite. The compositions of proeutectoid cementite and
austenite are4
eutectoid austenite @ <." - 4.3= L <." - '.#3= x &'' @ 4'.:
proeutectoid cementite @ <4.3 - '.#3= L <." - '.#3= x &'' @ 5%.4:
The austenite has a eutectoid composition that is4
eutectoid ferrite @ <." - '.#3= L <." - '.'25= x &'' @ ##:
eutectoid cementite @ <'.#3 - '.'25= L <." - '.'25= x &'' @ &2:
3. .nterpolate between alpha <'.'2:C= and 8e3C <.":= at &333E8
Carbide @ <'.# - '.'2= L <." - '.'2= x &'' @ &2g
4. 0ince pearlite originates from austenite of eutectoid composition+ determine the
amount of gamma Uust prior to the eutectoid reaction.
8rom #"'EC - "#'EC 4 &''g austenite with '.5: C
8rom "#'EC - "2"EC 4 ferrite separates from austenite and the carbon content of
the austenite increases to about '.#: C
(t "2"EC <A= 4 proeutectoid ferrite4 composition of ferrite @ '.'2: C+ amount of
carbon @ 3#g
Damma that transforms to pearlite4 compostion of austenite @ '.#: C. (mount of
austenite @ 2g.
(t "2"EC <-=4 (mount of pearlite @ 2g
Example
8ig 2. Time-Temperature
)aths on .sothermal Transformation Niagram
&. Di1en 8ig. 2+ describe what transformations happen in4
a. )ath & <Sed line=
b. )ath 2 <Dreen line=
c. )ath 3 <Blue line=
d. )ath 4 <9range line=
!olution
a. <Sed= The specimen is cooled rapidly to 433 O and left for 2' minutes. The
cooling rate is too rapid for pearlite to form at higher temperatures> therefore+ the
steel remains in the austenitic phase until the !s temperature is passed+ where
martensite begins to form. 0ince 433 O is the temperature at which half of the
austenite transforms to martensite+ the direct quench con1erts 5': of the
structure to martensite. $olding at 433 O forms only a small -uantity of additional
martensite+ so the structure can be assumed to be half martensite and half retained
austenite.
b. <Dreen= The specimen is held at 523 O for &'' seconds+ which is not long
enough to form bainite. Therefore+ the second -uench from 523 O to room
temperature de1elops a martensitic structure.
c. <Blue= (n isothermal hold at 5"3 O for 5'' seconds produces a half-bainite and
half-austenite structure. Cooling -uic3ly would result in a final structure of
martensite and bainite.
d. <9range= (ustenite con1erts completely to fine pearlite after eight seconds at
#"3 O. This phase is stable and will not be changed on holding for &''+'''
seconds at #"3 O. The final structure+ when cooled+ is fine pearlite.