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5 10 at% Carbon 15 Liquid Fe BCC 20 25 Most steels are based on the metastable phase diagram Fe Fe3C. The region of most interest is around the eutectoid reaction + Fe3C. Cementite Fe3C
1800
+G ra
Austenite Fe FCC Fe + Cementite Fe + Cementite
1600
Fe
iqu
1400 1200
+ Liq uid
T (C) 1000
800
Ferrite Fe BCC
(L
id
ph it
e)
6
2: 1
wt% Carbon
T (C)
1000 900 800
400 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2
Pearlite
1-10m
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts 2: 2
T (C)
1000 900 800
Austenite Fe FCC
+ Fe3C 50 500 m
400 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2
2: 3
0.45%C
0.65%C
0.8%C
10m Typical microstructures and properties of normalised (slow cooled) carbon steels.
2: 4
T (C) 800
700 + 600 500 400 1% 300 200 100 0 0.1 1 10 time (s) Time Temperature Transformation diagram for 2340 steel: 0.37% C, 0.7% Mn, 3.4% Ni.
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts 2: 5
1 2 3
1: nucleates at grain boundaries and grows into grains. 2: Cementite starts to form: and C grow together into grains as pearlite. 3: 50% of the has been transformed
++C 50%
+C
4
99%
Ms
M50
100
1000
10000
T (C) 800
++C 1%
3
1: is supercooled past the diffusioncotrolled transformation nose . Too fast for to nucleate. +C 50% 99% 2: now well below normal transformation T, but diffusion is very slow; carbon is stuck in supersaturated solution. 3: At Ms temperature, free energy change big enough to force rapid diffusionless transformation to near- structure but with trapped carbon atoms martensite 10000 4: martensite transformation is complete.
Ms
M50
M90
10 time (s)
100
1000
Time Temperature Transformation diagram for 2340 steel: 0.37% C, 0.7% Mn, 3.4% Ni.
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts 2: 6
Formation of Martensite
The face-centred cubic structure can distort to give a body centred structure. Each BCC unit cell is directly related to the parent fcc unit cells.
2: 7
Formation of Martensite
The interstitial holes which house dissolved carbon and nitrogen are much smaller in the BCC structure than in the FCC structure. More C or N can dissolve in FCC than BCC. Quenched-in supersaturated C or N distorts the martensites unit cells along three possible directions. Large locked-in stresses result. a
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts
c (>a)
2: 8
Structure of Martensite
1000 Hardness (VPN = kgmm-2) 800 1.5 600 400 200 0 0 Air-cooled (pearlitic) 1.0 0.5 0 0.8 Yield stress (GPa) As-quenched martensite 2.0
50m
Iron-Carbon martensites: many interfaces interiors of laths heavily twinned or dislocated high and strongly varying local stresses around each locked-in C between laths between colonies of different orientation All these give very high resistance to dislocation motion.
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts
The high local stresses can easily feed energy required to extend cracks. As-quenched martensites are very hard but very brittle.
2: 9
Tempering Martensite
1200 80
UTS
Y, UTS (MPa)
Impact energy
1000 Y 800
60
Low temperatures (<~350C): carbon precipitates as -carbide (~Fe2C5) internal stresses disappear Moderate temperatures (~350C - ~500C) -carbide precipitates transform to cementite High temperatures (>~500C) cementite precipitates coarsen (larger and more widely spaced) Spheroidised
40
600
fract
20
400 100
200
300
400
500
600
0 700
Tempering trades off strength for toughness. Compromise selected depends on application. Typical tempering range for engineering steels is 250 - 450C. Lower T (and higher C) for blades, etc; Higher T (and lower C) for shafts, gears, etc.
Tempering temperature (C) Effects of tempering on a 0.5% C, 0.7% Mn steel, quenched into water from 830C
2: 10
2: 11
Quench into oil from ~830C, temper 550-650C. Y 600-800 MPa, UTS 800-1000 MPa F 16-20%, Impact ~50 J Highly stressed general engineering parts: shafts, conrods, rockers etc. 0.12% C, 0.45% Mn, 3.3% Ni, 1% Cr Carburise at ~850C, quench into oil from ~770C, temper 150C. Y 850 MPa, UTS 900 MPa F 13%, Impact ~40 J Case hardening variant high core strength, hard wearing surface.
2: 12
Stainless Steels
Based on Fe Cr Ni system, possibly with added Austenitic Stainless Steels C. Typical composition: 18% Cr, 8% Ni, <0.1% C. Type 304. 18/8 Ni stabilises FCC phase (strongly) Cr stabilises BCC phase (less strongly) > 12% Cr provides thin tenacious oxide film. Basic types: austenitic: 17-25% Cr, 8-20% Ni ferritic: 12-30% Cr, low C martensitic: 12-17% Cr, 0.1-1.0% C duplex: 25-30% Cr, 2-7% Ni, + Ti. Mo precipitation hardened: ferritic or martensitic with added Cu, Ti, Nb, Mo. stabilising Ni wins over - stabilising Cr. Ni also helps protect against corrosion in Cl- -containing acids and solutions. C content must be kept low, or small amounts or Ti, Nb, Mo added to tie C up as carbides if not, Cr carbides will form at grain boundaries, (esp. during welding) locally depleting Cr content and leading to enhanced corrosive attack at grain boundaries. Type 316 is 18%Cr, 12%Ni, 2.5% Mo. Highly formable, ductile to low temperatures. Can only strengthen (not much) by work-hardening. Y ~550 MPa, F ~40%. Uses: Chemical industries for vats, pipes, etc. General structural parts. Decorative work.
North Sea oil rig: living quarters clad in type 316 stainless steel.
2: 13
Stainless Steels
Ferritic + martensitic stainless steels Typical Ferritic:
1800
liquid
1600
13%Cr, 0.45% Mn, <0.05% C. Type 403 Poor mans stainless Stainless iron Y ~ 350 MPa, UTS ~ 500 MPa, F ~ 30% Domestic ware: spoons, forks, sinks, etc.
Temperature (C)
1400
1200
0% C
0.1% C
Typical Martensitic: 13%Cr, 0.5% Mn, 0.3% C. Type 420. Quench from ~1000C, temper at ~150 400C Y ~ 1000-1200 MPa. UTS ~ 1400-1700 MPa Sharp edged tools, springs.
1000
800
600 0 5 10 15 20 25
% Cr
2: 14
with very small additions of V, Ti, Nb. Use carefully controlled hot-rolling in the phase to achieve a fine grain size. In hot rolling, there is competition between: - work hardening: reduces grain size; - diffusion controlled grain growth. Nb(C,N) has very low solubility in -Fe, comes out of solution as as fine grain boundary precipitates as rolling temperature drops; these pin movement of grain boundaries. Result: small -Fe grains during rolling. Grain size of resultant -Fe is even finer. ferrite grain size (m2)
120 100 80 60 40
Ti
Nb
20 0 0 0.02 0.04 0.06 0.08 0.1 0.12
2: 15
0.1 m
Strength level about 2x that of normal mild steel, tough, formable and weldable. Also not much more expensive than the equivalent mild steel. Applications: Automotive sheet (body panels), strip, plate. Off-shore platforms, ships.
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts
T (C)
1400
1200
Substutional alloying elements modify Fe-C phase diagram 1: Soak just below eutectic line, forming g and dissolving as much carbon as possible (some W, V carbides remain) 2: Quench into oil bath 3: Temper to 500-600C.
1000
800
600
2 0.8
2: 17
1000
18-4-1, 12%Co
800
18-4-1
50 m
600
400
100
200
300
400
500
600
700
800
Tempering temperature, C
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts
T (C) 800
+C
Pearlite Nose
2: 19
3m
2: 20
Beware brittle-ductile transition! Uses: pressure vessels (e.g. Nuclear reactor containment).
2: 21
Maraging Steels
Do not contain carbon (0.03% max) Hardening is via intermetallic precipitates Design philosophy Start with Fe 18-20% Ni
will give 100% martensite on air cooling not very hard (y ~ 700MPa) and not brittle as no C. ageing at 475-525C (several hours) gives Ni3Ti, Fe7Mo6 Ti also ties up any residual carbon depress MS, MF temperatures. depresses solubility of Mo in Fe; hence more precipitates elevates MS, MF temperatures. V, Nb, W, Cu more precipitates Cr corrosion resistance
Add ~8% Co
0 0 10 % Ni Martensitic transformations in Fe - Ni 20 30
2: 22
Maraging Steels
200
160
KIc (MPam1/2)
120
Ma rag ing
Tem per ed
Ste
els
80
Ma rten site
Ste els
40
0 1250
1500
1750
2000
2250
UTS (MPa)
2: 23
Maraging Steels
Good points Dont need to quench no quench cracking problems On the other hand VERY expensive (20 000 / tonne, 1988) Uses Co a strategic metal with limited sources of supply and volatile pricing Co free grades have been developed.
Workable and machinable in the martensitic condition Can hot and cold work Good weldability Can nitrocarburize during maraging Very good combination of strength and toughness typical y = 2000 MPa typical KIc = 100 MPam1/2
Fatigue strength and wear resistance not as good as might be expected for their y and KIc.
2: 24
Automotive
Tooling
BM006 - Maraging steel face Maraging steel face offers a super hard striking surface.
2: 25
Creep-resistant Steels
1000hr Rupture Stress (MPa) Conventional plain C steels begin to lose strength rapidly above ~ 300C
Not much use above ~ 400C 1600 1200 800 400 0 200 Martensitic / Ferritic Low-C steels 400 600 Austenitic Inconels 800 1000 Precipitation hardening steels
Used in quenched and heavily tempered state. (may have up to 0.75% V) For the most highly stressed components (turbine blades), use:
martensitic stainless (12%Cr) austenitic stainless (better creep resistance) precipitation hardened stainless: eg. FV520B, Fe: 0.05% C, 5.5% Ni, 14% Cr, 1.6% Mo, 1.5% Cu, 0.3% Nb.
Temperature (C) Commonly used in power-generating turbines, etc. Large, highly-stressed components, requiring long life (20+ years) Steam temperatures now >500C
2: 26
2: 27
Nickel-based Superalloys
Nimonics Key component of the microstructure is precipitates of (Ni, Fe)3Al: `. A modern superalloy might be 60 - 85% ` - nickel is effectively a glue holding the ` together. The yield stress of `increases with increasing temperature (up to about 700C). Yield stress (MPa)
600 20% ` 500 40% 400 300 200 100 0 0 200 400 600 800 1000 1200 60% 80% 100% `
2: 28
Nickel-based Superalloys
Microstructure must be stable: Any finely divided precipitate distribution will tend to coarsen driving force is lowering of interfacial energy. ` is nearly exactly lattice-matched to the Ni matrix. Interfacial energy is nearly zero. Co: Alloy Additions: Ti: Cr: goes into ` - Ni3(Al, Ti) solid soln strengthening of ` goes into Ni matrix, solid soln strengthening, corrosion resistance goes into both Ni and ` oxidation and corrosion resistance lowers solubility of Al in Ni, so enhances ` formation, improves g` high T stability combines with Cr, gives precipitates in Ni solid soln strengthening of ` improves grain boundary and carbide / matrix adhesion, so suppresses cavity formation in creep <0.5%, improves high T ductility (scavenges impurities?) improves oxidation resistance the latest magic dust: 3% extends operating temperature considerably. (why?)
2: 29
C: Ni Ni Al Ta: B:
Hf: Y: Re:
Directionally Solidified
20
10
Yield strength, UTS, fracture strain, etc, rather less important than creep behaviour and fatigue behaviour.
Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts
0 0 20 40
2: 30
60
80
100
120
Time (h)