Steels the Basics Revisited

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

600 400 200 0 0

Fe

(L

id

ph it

e)

6
2: 1

wt% Carbon

Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts

Eutectoid (0.8wt%C) Carbon Steels

1200 1100

T (C)
1000 900 800

Austenite Fe FCC + Fe3C + 50 500 m

Ferrite Fe 700 BCC

600 500

+ Fe3C wt% Carbon

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
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Plain Carbon Steels

1200 1100

T (C)
1000 900 800

Austenite Fe FCC

+ Fe3C 50 500 m

Ferrite Fe 700 BCC

600 500

+ Fe3C wt% Carbon

400 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2

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Plain Carbon Steels

0%C 0.15%C

0.45%C

0.65%C

0.8%C

10m Typical microstructures and properties of normalised (slow cooled) carbon steels.

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T (C) 800

Quenched steels - Martensite

Slow cooling:

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.
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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

M90 4: Decomposition of the into and pearlite is complete.

100

1000

10000

T (C) 800

Quenched steels - Martensite

Rapid cooling (quenching):

700 + 600 500 400

2 1

++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.

300 200 100 0 0.1

Ms

M50

M90

10 time (s)

100

1000

Time Temperature Transformation diagram for 2340 steel: 0.37% C, 0.7% Mn, 3.4% Ni.
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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.

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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
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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

0.2 0.4 0.6 Carbon, wt%

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

fract (%), Impact energy (J)

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

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Alloying elements in Steels

Element Mn Al Si Cr Ni Mo Co W Ti V Nb Stabilises Hardenability +++ + + ++++ + ++ + + + + + C N, C N, C N, C + + (in ) ++ C C N +++ + +++ Carbides / Nitrides? Solid soln Strength? +++ + Grain refine? Other
Deoxidiser, Desulphuriser Deoxidiser, esp. for low C steels Deoxidiser, esp. for high C steels >10% for corrosion resistance >20% in maraging steels Promotes bainite Mostly used in maraging steels >12% in high speed tool steels

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Engineering Nickel-Chromium Steels

Nickel alone grain refines, but tends to promote graphitisation of carbides. Chromium alone forms stable carbides, but tends to promote grain growth. Ni stabilises FCC phase, Cr stabilises BCC phase. Both elements are good solid solution hardeners, provide corrosion resistance (esp Cr) retard the + Fe3C transformation A balanced mixture (2-3x as much Ni as Cr) gives steels which can be easily quenched to give martensite, tempered to give a good trade-off between strength and ductility can be case-hardened (carbon diffused in to give ~0.9% C in surface) to give extra wear resistance. High alloy content (>4% Ni, 1.5% Cr) can give airhardening steels. Typical compositions and applications: 0.3% C, 0.6% Mn, 3.0% Ni, 0.8% Cr, [0.65%Mo]
(Mo to avoid temper brittleness in larger section components)

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.

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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.

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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

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High Strength Low Alloy (HSLA) Steels

HSLA steels are microalloyed: Typically 0.1 0.25% C, 1.0 1.7% Mn,
140

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

microalloy content (%)

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High Strength Low Alloy (HSLA) Steels

As well as strengthening via grain refinement, microalloyed steels are often heat-treated to give a fine dispersion of hard precipitates. On cooling from FCC -Fe to BCC -Fe, solubility of C decreases markedlly. Some C is precipitated as very fine (and very hard) particles of NbC, VC, etc. at the interface as the grows stepwise into the . Typical properties: Y: UTS: F: 450 650 MPa
(depends on C, N content)

0.1 m

Check data 0.3 m

550 700 MPa 10 20%

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.
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Fe: 0.75%V, 0.15%C; after 5 mins at 750C

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High Speed Tool Steels

Typical composition: Fe: 18% W, 4% Cr, 1% V, 0.75%C

(+ maybe 6-10% Co)

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.

Austenite Fe FCC + complex carbides +

1000

800

600

+ complex carbides wt% Carbon

400 0 0.2 0.4 0.6

2 0.8

Fe: 18% W, 4% Cr, 1% V.

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High Speed Tool Steels

Microstructure is globules of complex carbide in matrix of tempered martensite with fine distribution of W, V and Cr carbides. local heating precipitates more W, V and Cr carbides secondary hardening

1000

18-4-1, 12%Co

Hardness (kg mm-2)

800

18-4-1

50 m

600

Applications: 18-4-1: Tool-tips, hot punches, saw blades

400

100

200

300

400

500

600

700

800

Tempering temperature, C
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+6-12% Co: severe duties as above, high-speed drills, milling cutters.

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T (C) 800

Bainitic high strength Steels

Slow cooling:

700 + 600 500 400 300 200 100

1min 1hr 1day

+C

Pearlite Nose

++C 1% Ms M50 M90

50% 99% Bainite Nose +C

0 1 10 100 time (s) 1000 104 105

Fe: 0.42%C, 0.78% Mn, 1.79% Ni, 0.8% Cr 0.33% Mo

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Bainitic high strength Steels

What is Bainite ? As in diffusionless formation of Martensite, units cells of FCC Fe transform by minor atomic re-arrangements to BCC -Fe - but carbon has to come out of solution for this to happen. As in diffusional formation of Ferrite /Pearlite, excess carbon comes out of solution to form carbides - but carbides formed are finely-divided and closely-spaced within or on the bainite laths.

3m

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Bainitic steels: Applications

Typical Bainitic steel: A533B Fe: 0.24%C, 1.4%Mn, 0.5%Mo, 0.5%Ni. Y: UTS: F: KIc: 400 450 MPa 700 800 MPa 12 20% >100 MPa on upper shelf ~40 MPa on lower shelf

Beware brittle-ductile transition! Uses: pressure vessels (e.g. Nuclear reactor containment).

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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

T (C) 800 600 400 200 90% 10% 10% 90%

Add 2-3% Mo and 1% Ti

Add ~8% Co

0 0 10 % Ni Martensitic transformations in Fe - Ni 20 30

Other possible additions:

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Maraging Steels
200

160

KIc (MPam1/2)

120

Ma rag ing

Tem per ed

Ste

els

80

Ma rten site

Ste els

40

100nm Fe7Mo6 and Ni3Ti precipiates in a peakaged maraging steel.

0 1250

1500

1750

2000

2250

UTS (MPa)

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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.

Strength maintained to typically 500C

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Maraging Steels - Applications

Aerospace
Rocket motor cases Jet engine and helicopter drive shafts Landing gear Hinges for swing-wings Shock absorbers on Lunar Rover! Drive shafts connecting rods Engine valves Extrusion rams Machine tool gears Al and Zn casting dies Index plates Rolls Splined shafts etc.

Automotive

Tooling

BM006 - Maraging steel face Maraging steel face offers a super hard striking surface.

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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

Family of Cr Mo steels for use in 300 600C range:

0.15% C, 1.2% Cr, 0.5% Mo 0.15% C, 2.5% Cr, 1% Mo 0.15% C, 9% Cr, 1% Mo

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

Upper temperature limit steels Inconels ~ 40% Ni, Cr, Co.

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Engineering C High Perfomance Alloys: HT 2000 S.G. Roberts

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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% `

Temperature (C) 0.2 m

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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:

Mo, W: solid soln strengthening of Ni

Hf: Y: Re:

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Typical Ni-based Superalloys

Nimonic 115: Ni, 14.5% Cr, 13.3% Co, 3.8% Ti, 5.0% Al, 3.3% Mo, 0.15% C, 0.05% Zr, 0.016% B - an early wrought alloy MAR M200: Ni, 9% Cr, 10% Co, 1.5% Ti, 5.5% Al, 0.15% C, 0.05% Zr, 0.015% B, 10% W, 2.5% Ta, 1.5% Hf - standard cast alloy SRR99: Ni, 8.5% Cr, 5% Co, 2.2% Ti, 5.5% Al, 9.5% W, 2.8% Ta. - Rolls Royce single crystal alloy CMSX-4: Ni, 6.5% Cr, 9% Co, 1% Ti, 5.6% Al, 0.6% Mo, 6% W, 6.5% Ta, 3% Re, 0.1% Hf - advanced single crystal alloy CMSX-4 turbine blade

30 Creep Strain (%)

Directionally Solidified

20

MAR M200 982C 206 MPa

Conventionally Cast Single Crystal

10

Yield strength, UTS, fracture strain, etc, rather less important than creep behaviour and fatigue behaviour.
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0 0 20 40
2: 30

60

80

100

120

Time (h)