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Bullet points: Materials science of steels

Part 1: Low alloy steels:
General:

Properties of steel: E=210 GPa; density = 7.9 g/cm³; yield stress = 200-4000 MPa; critical crack length
= 100-0.1 mm; fourth most abundant element in the earth's crust; increasing cooling rate:
ferrite+perlite, bainite, martensite

World production = 1.7 billion t/year; flat steel in industrialized countries, steel beams in developing
countries; in Austria: VOEST, Marienhütte and Breitenfeld

Classification: Mostly classified by application (structural steel/tool steel). Also by chemistry

(alloyed/unalloyed), grade (basic steel/quality steel/stainless steel),.....

According to EN10020:2000: unalloyed steels (quality steels/special steels), stainless steels (at least
10.5% Cr), other alloyed steels (quality steels/special steels if criteria for unalloyed steels are not
met)

Marking: By application (if no heat treatment provided, letter, e.g.: S235J2GR), by chemistry (if heat
treatment provided, or certain chemistry provided, 4 subgroups).

• Unalloyed steels with <1% Mn (C+100*C-content+additional symbol, e.g.: C35E)

• Unalloyed steels with >1% Mn and each less than 5% other elements (100*C-
content+alloying elements+contents with factors+additional symbol, e.g.: 22CrNiMo 7-3)
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• Alloyed steels with at least one element >5% (X+100*C- content+alloying elements+contents
without factors+additional symbol, e.g.: X10CrNiMo 17-20- 2-N5)
• HSS (HS+content tungsten+content molybdenum+content vanadium+content cobalt+
additional symbol, e.g.: HS2-9-1-8+N)

Further marking according to material number (ÖNORM EN 10027-2) or UNS (unified numbering
system), or SAE (Society of Automotive Engineers, USA)

General structural steels

No heat treatment. Good weldability (≤ 0.2% C, ≤ 1.5% Mn). Marking: S+yield strength+ additional
mark (e.g.: S235JR). Unkilled/killed (Si)/full-killed (Si+Al) steel. Main alloying elements are carbon and
manganese. "Rule of eight" for carbon content. Carbon equivalent for weldability. Grain growth zone
around weld most critical, as embrittlement here.

Reinforcing steels

For reinforced concrete, accept tensile loads. Good cold formability. Good weldability (≤ 0.2% C).
Mainly used yield strengths > 500MPa (strain hardening and Mxx by Mn).

Free cutting steels

Machinability in the foreground (short chips). Addition of sulfur (0.3%) forms primary MnS, does not
precipitate on KG. MnS is deformable and initiates crack (progression). Carbon content and heat
treatment determine machinability. Too little C: ferrite, too tough, long chips. Too much C: pearlite,
too hard, short chips. Soft annealed microstructure is ideal.

Weather resistant structural steels

For high SO2 concentrations near sea or industry. Use without painting or galvanization. Cu and Cr
form barrier layer (phosphates and sulfates) between base material and rust. This is constantly
renewed (δ-FeOOH). However, rust never remains (allow for thickness allowance). Welding only with
appropriately alloyed filler materials.

Case hardening steels

Carbon, nitrogen, boron and metals are diffused into the surface layer. Steels with
≤0.25% C are not hardenable. Surface hardening produces residual compressive stresses - better
alternating strength (60-62 HRC). Mostly used for gears. Carbon on surface should not exceed 0.6%,
otherwise residual austenite remains. Alloying elements (substitutional) increase through
hardenability, C content increases maximum edge hardness. Working steps: Carburizing - Hardening -
Tempering. Carburizing takes place in the austenite region (high C solubility). Mostly gaseous
carburizing agent (CO, CO4) is used. Local carburizing by covering with Cu or ceramic paste.
Hardening either as direct hardening, single hardening, after isothermal transformation or double
hardening. Target: tough core and hard, wear-resistant surface.
Chromium: increases through-hardenability and forms carbides (good for wear resistance).
Manganese: increases through-hardenability and increases core strength (Mxx).
Nickel: greatly increases through-hardenability and lowers DBTT. Attention: austenite stabilizer.
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Nitriding steels

Nitriding produces a high-strength, wear-resistant surface layer through nitrides. Nitrocarburizing

introduces additional carbon (slightly lower hardness). Higher surface hardness than case-hardened
steels and improved corrosion properties. No deformation due to martensite formation. Layer
consists of a compound layer (high N content, very outside N2 - pore fringe) and a diffusion layer
(decreasing N content). Nitride formers are Al, Ti, Cr, V, Mo, Mn and Ni. Nitriding depth where
hardness is 50HV above core hardness. Nitriding agents are liquid (cyanide, toxic), gaseous(ammonia)
or plasma (nitrogen).

Alloy concept: heat-treatable steels with nitride formers.

Spring steels

Exhibit high, elastic ductility (energy storage/absorption) and high fatigue strength. Alloying similar to
quenched and tempered steels (0.4-0.7%C). High hardness due to work hardening and/or tempering.
High purity and surface finish important for fatigue strength. Silicon increases ferrite strength and
thus Rp /Rm . Used for spiral and leaf springs.

Cold heading steels

Well suited for cold forming (upsetting and extrusion). Low work hardening required. Low yield
strength required, therefore low C-content (ferritic-pearlitic microstructure, ideally soft annealed).
High purity to prevent crack initiation by NMEs. Generally three classes: unalloyed steels with low C-
content without heat treatment, non- and low-alloyed steels with subsequent heat treatment, and
high-alloyed steels with ferritic or austenitic microstructure.

Fine-grained structural steels

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Strength and toughness due to fine grain consolidation ) is increased (limit approx. 45µm). Fully
(Δσ~ calmed
√𝐷𝐷
steels (Al and Si in the casting process) for very high purity. AlN precipitates in the austenite region
(950°C) and serves as nucleus during transformation. Good weldability as less C is required due to
fine grain hardening. Further improvement by lowering S content and affecting sulfide form. Also
microalloying elements (Ti, Nb and V) which suppress grain growth in the austenite region. Rolling in
the austenite region (thermomechanical rolling) followed by normalizing leads to very fine
microstructures. In some cases, they are subsequently quenched and tempered.

Thermomechanically rolled steels

For higher strength steels with high toughness and good weldability (0.1-0.2 %C). Temperature and
degree of forming are time controlled during hot forming. Generally normalized and
thermomechanically rolled. Toughness is improved by less S and higher purity. The coarse austenite
is rolled (rough-rolled), causing it to recrystallize finely. It is then finish-rolled at lower temperatures
to produce a rolled structure (no recrystallization, microalloying elements, TM (ferrite+pearlite) and
TMAC (ferrite+bainite/martensite)) or finish-rolled at even higher temperatures to produce a normal
structure (recrystallization, N). Cooling is done by quench (water, TMAC) or air (TM, N).

Cold rolled steels

Thin sheet 0.5<s<3 mm (automotive). Pickling (descaling) is required before cold rolling, for good
surface quality. The skin pass is used to stop the flow figures. The
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mechanical properties are adjusted by the heat treatment (bell furnace (slow) or continuous strip
furnace (fast)). The r-value is the ratio of the logarithmic width decrease and the logarithmic
thickness decrease (r>1, flows from width/ r>1, flows from thickness). Mean anisotropy rm and plane
anisotropy Δr. The strain hardening exponent n indicates how uniform the deformation distribution
is. It is approximately as large as the true uniform strain φg . Ideal: rm =1, Δr=0, n high. Best deep
drawability for very low C content (<0.01%) and IF- steels (interstitial free, C bound by Ti and N). Also
dual-phase steels, TRIP-TWIP-and PH steels, and bake-hardening steels used.

BH steels: (bake hardening). during paint baking (170°C), the C Cottrell clouds around the dislocations
and pins them or forms fine ε-carbides.

Dual-phase steels: Martensite islands in ferritic matrix lead to high n-values and good formability due
to dislocation concentration at the interface.

TRIP steels: (transformation induced plasticity). Ferrite+bainite+austenite. The metastable austenite

transforms into martensite during deformation and thus displaces the stress peaks, hence high n-
value. The austenite is stabilized by intercritical annealing in the α-γ region followed by quenching.

TWIP steels: (twinning induced plasticity). The formation of mechanical twins under load dissipates a
lot of energy and increases the n-value. Produced by high Mn content.

PH steels: (press hardening). The austenitized steel is quenched in a press by the metal-to-metal
contact and transforms into martensite. Indirect: first forming, then hardening. Direct: forming and
hardening at the same time.

Research currently on 3rd generation AHSS (Medium-Mn, TBF, Q&P). TBF and Q&P have a
martensitic/bainitic matrix with retained austenite.

Active corrosion protection: Zinc serves as a sacrificial anode and forms zinc oxide when the coating
is damaged. Applied in the hot-dip galvanizing tank, where the layer thickness is adjusted via
stripping nozzles. Through a furnace can still be diffused in, which is then called "galvannealed". Can
also be applied electrolytically.

Passive corrosion protection: Only protection as long as the coating is not damaged. Otherwise
pitting corrosion will occur.

Quenched and tempered steels

Quenching and tempering = hardening + tempering. High toughness, good machinability and good
(through)hardenability. Heat treatment mainly influences toughness (Ak , notched bar impact work).
C contents between 0.2-0.6%. The surface hardness depends on the C content, the hardening depth
on the alloying elements. CrMo steels in particular can be through-hardened well at low quenching
rates (low distortion). VWater>VÖl >VLuft . Through hardenability can be determined with Jominy test.
Tempering temperature is a compromise between strength (Rp0,2 ) and toughness (A,Z). Temperature
(always subcritical) has a stronger influence than holding time. Tempering resistance can be
significantly improved by V,M,Cr,Mo and Co and a secondary hardness maximum is formed by
secondary carbides at about 550°C.

Boron: Enrichment to the austenite CG. Delays the diffusion-controlled transformations. N must be
bound by Ti, otherwise embrittlement of the KG. Boron thus leads to higher yield strengths and
better toughness.
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Application for highly stressed parts. For dynamically stressed parts, special purity and low S and P
content is required. Machining is performed in the soft annealed condition with subsequent
quenching and tempering. Only grades with low C-content are weldable, higher alloyed grades
embrittle strongly in the area of coarse grain formation.

Alternative to quenched and tempered steels: Precipitation hardened (VC) ferritic-pearlitic steels.
Simpler heat treatment (only controlled cooling from forming heat). Fine-grained due to Ti addition.

Cold toughened steels

High impact energy at low temperatures with sufficient strength and good weldability required.
Achieved by very fine microstructure (microalloying elements Ti, Nb, Al). Mn and Ni stabilize γ and
thus lower TÜ . Low C and Si contents further increase toughness, as does quenching and tempering.
High purity (low S and P). Partial Ni content so high (>9%) that austenite becomes stable.

Rail steels

Fine pearlitic rail head (0.5-0.8% C) with increasing lamella spacing towards the rail foot. Achieved by
immersion of the head in the quenchant. Wear resistance due to small lamella spacing. Bainitic steels
currently under research. Welded via thermite reaction: Fe2 O3 +Al -> Fe + Al2 O3 + heat.

Creep resistant steels

For high temperature applications (T>500°C, const.). High creep rupture strength Rmt/T . Low
coefficient of thermal expansion and high thermal conductivity required, as well as good oxidation
resistance. Creep starts from T ≥ 0.4*Tm [K] and is the time and temperature dependent strain.
Progression in 3 ranges: 1st strain hardening > softening, 2nd strain hardening = softening, 3rd strain
hardening < softening. Control via replicate techniques. Short term experiments are extrapolated,
error prone when changing creep mechanism. Alloy concept: CrMoV steels. In general, coarse-
grained microstructures are more suitable because grain boundary and surface diffusion are
activated before bulk diffusion.

Heat resistant steels

Main load by oxidation, mechanical load only secondary. The oxide layer is reinforced by stable Cr,Si
and aluminum oxides and can thus be used up to approx. 1150°C. On the metal surface they form
spinel (FeCr2 O4 , FeAl2 O4 ) or fayalite (Fe2 SiO4 ) and thus hinder oxygen transport. Ferritic and
austenitic steels are used.

Part 2: Stainless steels:

General:

Stainless steels designated "S", approx. 3% of total steel production (~50 million t/year). General
requirements: Corrosion resistance, adequate mechanical properties (dynamic and static),
formability, weldability and price.

Corrosion: Fe + H2 O + ½ O2 -> FeO(OH)...rust. The water (acid, etc.) is the electrolyte. Local differences
(chemistry, microstructure) create potential difference and thus corrosion current. Chromium lowers the
corrosion current and thus the removal rate (from approx. 12% "corrosion resistant"). Intergranular corrosion
occurs when the KG are depleted of Cr (welding, etc.). Due to lower C content, or bonding of the C with Ti
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and Nb, formation of Cr carbides can be suppressed. Pitting and crevice corrosion due to insufficient oxygen
supply to form passive layers. PREN = pitting resistance equivalent incl. N (high = good). Combination of
mechanical and chemical stress: stress corrosion cracking. No fatigue strength is achieved in corrosive media.

The Fe-Fe3C diagram changes strongly in high-alloy steels. Chromium(equivalent) stabilizes the ferrite.
Nickel(equivalent) stabilizes the austenite. Influence of alloying elements according to Schäffler diagram. Nickel
can preserve residual austenite for hardening in spite of chromium: CrNi steels.

Production: After the arc furnace (melting) either into the AOD (Argon Oxygen Decarburization) or into the
VOD (Vacuum Oxygen Decarburization) converter. There, C content is reduced and alloying elements are
added. Subsequently, in ladle metallurgy, fine-tuning of the alloy, final deoxidation and modification of the
NMEs. For particularly high purity, remelting is performed in ESR (Electric Slag Remelting), PESR (Pressure
Electric Slag Remelting) or VAR (Vacuum Arc Remelting). Subsequently, forming (high forces due to Mxx), heat
treatment and finishing.

(Super)Ferritic stainless steels

Located in the ferrite range of the Schäffler diagram (high Cr, low Ni). Subdivision into three classes
according to Cr content (10.5-13/16-18/>20). The TÜ is above room temperature.
"Superferritic" if very low C and N contents and additional ferrite stabilization (application in highly
corrosive media, e.g. seawater).

(Super)Martensitic stainless steels

Up to C-content of 0.6% heat treatable only, above that hardenable. Exhibit high tempering
resistance (up to 500°C). Only low toughness under room temperature. Problem of Cr carbide
precipitation during tempering (lower corrosion protection). Achievable hardness after quenching
depends on C content (50-60 HRC). Increased nitrogen content produces fine carbonitrides,
increasing corrosion protection (fewer Cr carbides). Soft-martensitic steels (also super-martensitic
steels) are based on increased Ni content (disequilibrium transformation of Ni instead of C) and very
high tempering temperatures, resulting in reformed austenite (TÜ ~ -100°C).

(Super)Austenitic stainless steels

Very high elongation at fracture (up to 50%) and very low TÜ . Strength increase mainly via solid
solution strengthening with N (simultaneously increases PREN as Cr carbides are inhibited). Md30
temperature = temperature at which 50% of the volume at 30% cold working in martensite
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convert. "Super austenitic" grades are at very high Ni and Cr contents (top right of Schäffler diagram).
Austenitic steels are used for medical implants because they encapsulate (Ni often substituted by Mn
because many people are allergic to Ni).

Duplex steels

Optimum usually at 50% austenite and 50% ferrite. Rp0,2 and Rm higher than single phases, A and Ak
compromise. "Super duplex" has increased PREN. Very sensitive to embrittlement when
microstructure is set (avoid formation of σ-phase).

Part 3: Tool steels:

General:

Special steels for machining and processing materials. Therefore, high hardness, wear resistance (and
possibly toughness). Used in extrusion, sawing, industrial knives, punching, stamping, etc. Machining
limit at approx. 450HV, otherwise the tool becomes too hot.

Ni increases the through hardenability, Mo and V form the primary and secondary carbides. Primary
carbides from the melt (eutectoid carbides, MC, M2 C, M6 C,.., V forms the hardest carbides). The
orientation of the primary carbides is crucial for crack propagation (propagation along the carbide-
matrix interface).

Wear (abrasive, adhesive, tribo-chemical and rolling contact) can be reduced by fine, homogeneously
distributed carbides. Thermal conductivity (hot cracking, etc.) decreases with increasing alloy
content, as well as hardness and strength.

Heat treatment: first austenitizing (stepwise against thermal stresses), then quenching. Then 2-3
times tempering for secondary hardness carbides and transformation of retained austenite to
martensite. Higher austenitizing temperatures result in more retained austenite due to dissolution of
more C and also more secondary hardness carbides (higher secondary hardness).

Cold work steels: Primary carbides, high initial hardness, below 200°C

Hot work steels: Secondary hardness, above 200°C, below 600°C

HSS (high speed steels): primary carbides and secondary hardness, up to 600°C

As an alternative to tool steels, coatings and hard metals are also used. The main advantage of steels
over carbides is toughness.

Cold work tool steels

The main requirement is the stability of cutting edges and edges in general. Therefore, the hardness,
strength (compressive strength) and toughness are important. Application in punching, cutting,
stamping, cold rolling and deep drawing. The primary carbides should be fine, uniform and evenly
distributed (better alternating strength).

Classification according to C-content in 3 classes (hypoeutectoid (tough), hypereutectoid (hard) and

hypoeutectoid (carbide-rich)). Hypoeutectoid steels are tough because they do not reach full
martensite hardness (retained austenite, no carbides). Hypereutectoid steels achieve full martensite
hardness and form secondary hardness carbides during hot working. Hypoeutectoid (ledburitic)
steels contain primary carbides. The primary carbides are present in rows after rolling (exception:
cross rolling).
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For very high carbide volumes, powder metallurgy must be used. It also allows the carbides to be
finely and evenly distributed.

HSS

Mainly used for cutting tools (milling cutters, drills, etc.) and punching tools. The alloy is based on Cr,
Mo, W and V. Specification e.g. HS 6-5-2 (6% W, 5%Mo, 2% V, most widely used HSS). Generally,
primary carbides and eutectic carbides in a secondary hard matrix are used. MC carbides are ideal
because they are the hardest and they use the alloying elements most efficiently. Stress relief
annealing is performed prior to austenitizing. The secondary hardness maximum is between 500-
600°C. Powder metallurgical production leads to longer tool life.

New development with cobalt matrix in which intermetallic phases rather than carbides are
responsible for the hardness.

The surface of the tools is often further reinforced with coatings (PVD, CVD or nitriding).

Hot work tool steels

Are intended for chipless hot forming (temperatures constantly above 200°C). They must be
particularly temper-resistant (through Cr, W, Mo and V).

Wear resistance at high temperatures is given by Mxx and intermetallic phases. Toughness is
achieved by a homogeneous, fine microstructure without primary carbides. For higher tempering
resistance, tempering is slightly above the secondary hardness maximum. The ideal hardness range is
44-52 HRC, as this is where the susceptibility to hot cracking is lowest.

Plastic mold steels

Used for molding (extrusion, blow molding, injection molding) of plastics. Partly very complex tools,
where only the active parts are made of tool steel. Fillers (glass fibers, carbon, etc.) have a strong
wearing effect. Plastics, their degradation products and coolants can have a corrosive effect. Good
heat dissipation (good thermal conductivity) is necessary for fast processes (short cycle times).