Basic Metallurgy

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BASIC METALLURGY

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1. THE STRUCTURE OF METALS

The simplest structure in which ions may combine is SIMPLE CUBIC. where each ion is surrounded by six oppositely charged ions at equal distance. This is the structure of common salt. a mixture of sodium ions (Na+) and chloride ions (en. as sodium chloride (NaCI). The ions are held together weakly by electrostatic attraction. There are a number of ionic structures. many of complicated geometry.

Metals are also built up of recognisable structures of atoms (not ions); however. with few exceptions, there are only three main metallic structures.

1.

Body centred cubic {B.C.C.} - atoms occur at each corner of a cube with 1 atom in the cube centre.

e.q. a - Fe (ferrite), Cr. Mo, Na, W. The B.C.C. structure is built up of connected cubes.

2.

Face centred cubic (F.e.C.) - atoms occur at each corner of a cube with 1 atom in the centre of each face.

e.g. y - Fe (austenite), Ni, AI, Cu, Au.

3.

Close packed hexagonal (C.P.H.) - atoms are built up in a hexagonal array.

e.g. Mg. Cd, Zn, Co.

The three main atomic structures have high symmetry and. in general, give metals their ductility and malleability. Other metals have arrangements of lower symmetry and are somewhat brittle, e.g. Bi and Sb (simple rhombohedral). Mn (complex cubic). Unlike ionic structures, electrons in a metal are shared by several atoms and are thus free to move, giving metals their characteristic high electrical conductivity. There are no bonds between atom and atom in a metal and. in fact, the positively charged cores repel each other. The atomic structure is made coherent by the common negative electron cloud within it, which causes the atoms to pack closely together.

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OF THE ATOM CENTRES AA£ SHOWN 'OR THESE STRUCTURES.

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IRON(-') CHROMfUM (el)

-The three principal types of structure "in which metallic elements crystallise.

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lattIce Parameters

The simplest form from which the atomic structure is built up is called the unit cell. The lattice parameter is then the length of the edge of the cube .

a y <5

. 287 nM .365 nM ,293 nM

In CPH structures. the tattice parameter is specified by the height/side ratio of the hexagonal unit cell.

Atoms are not static but vibrate about a mean point; increasing the temperature increases the vibration and hence increases the lattice parameter. Thus metals expand with increasing temperatures. The differences in lattice parameter and atomic structure account for changes in co-efficient of expansion

e.g. y - Fe expands more than a - Fe.

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Atomic structure and mechanical properties

Deformation in metals occurs largely by a process of slip. where atomic planes slide over each other. Slip occurs on the most densely packed planes.

FCC has 4 close packed planes (octahedral places) and 3 possible slip directions giving 12 slip systems.

BCC is less closely packed than FCC; however, it has 6 close packed planes (on cube diagonals) and 2 directions, and therefore 12 systems. Slip. however, is more difficult than for FCC.

CPH has 1 close packed plane and 3 directions giving 3 slip systems. Because of the limited slip systems CPH metals tend to be more brittle.

MORE DUCTILE

MORE BRITTLE

F.C.C.

B.C.C.

C.P.H.

chromium iron (steel) molybdenum· tungsten

aluminium copper gold

lead

nickel silver

stainless steel (austenitic)

cadmium cobalt magnesium zinc zirconium

Because of these structure differences, austenitic stainless steels are tough down to very low temperatures but steel becomes embritlled as temperatures are decreased.

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Effects of alloying on atomic structure

The addition of alloying elements to a metal results in the formation of solid solutions or compounds. If the added atoms are similar in size to the parent metal atoms then they can occupy their position as SUBSTITUTIONAL solid solutions, e.g. Zn in Cu, Cu in Ni. If the added atoms are small enough to fit into the spaces or interstices between the original atoms, they form INTERSTITIAL solid solutions, e.g. C and N in iron.

Solid solutions are random mixing of atoms. Some mixtures can also form definite compounds, arrangements of atoms in a particular ratio e.g. N~Bi, FeaC are particularly important in the properties of steels.

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Copper - Nickel Phase Diagram

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Solid Solutions

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Sometimes metals which are soluble in the Hquld state remain in solution after crystallization has taken place and are termed Solid Solutions. For this to happen the elements need to have roughly the same properties and atoms which are approximately the same size On most cases). During solidification, if the atoms of one metal replace the atoms of the other within the lattice structure, then a ·substitutional solid solution- will result

Substitutional Solid Solution

Atoms of one metal are replaced by atoms of the other e.g. Chromium and Iron.

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Interstitial Solid Solution

Smaller ato:ns are able to fit into the spaces between the larger atoms e.g. Carbon/Iron.

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If the atoms of one metal are much smaller than the other, the smaller atoms are able to fit in the voids between the larger atoms. In this case an "Interstitial Solid Solution" results.

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Some metals when alloyed will form a complex chemical structure which bears no resemblance to the parent metals.

IntermetaJlic compounds usually occur when the metals are different in their physical and chemical properties and usually When one is strongly electro positive and the other is weakly electro positive.

Compounds on their own are of no use whatsoever as they are hard and brittle. However. when combined with solid solutions. they give the resulting alloy the property of hardness, which with the solid solution, makes the metal extremely tough.

DendrHlc Growth

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6 1. Nuclei form, sometimes known as seed crystals .

2. Dendrites being to form in the direction of cooling.

3. Secondary arms form on the Dendrites.

4. Arms grow until they tough the next Dendrite When the arms begin to thicken.

5. Crystallization is complete and only the grain boundaries are visible.

6. The impurities collect at the grain boundaries.

When the temperature of motten metal falls to its freezing point, single units of the crystaf lattice begin to form. From these single cells. the dendrites form in the direction of cooling and interlock until the grain structure is complete.

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2. THE INFLUENCE OF ALLOYING ELEMENTS

The importance of C as an alloying element in steel is discussed below. This section looks at the effect of other elements on the property of steels. Alloying elements may have the following effects:

1.

go into solid solution, which causes a mismatch in atomic size, and hence local distortion, and enhances strength.

2.

formation of carbides In high C steel, increasing wear resistance, e.g. V, W. Mo, Cr.

3.

. increase In creep strength and resistance to oxidation. Creep strength improves from a dispersion of fine carbides, e.g. Cr, Mo. V; resistance to oxidation results from stable oxide formation, e.g. Cr. Si.

4.

increase in resistance to hydrogen attack. e.g. Cr, Mo (stabilise Fe3CJ·

5.

increase in corrosion resistance. e.g. Cr. Ni.

Classification of. alloying elements is difficult because of the wide range of effects. Groupings.howElver. may ~e made in terms or.

(a) the effect on carbide stability

(b) the effect 'on austenite stability

(a)

Elements which tend to form carbides:

Cr, w n Nb, V, Mo, Mn

"Sif

Elements which tend to graphitise (break down) carbides:

SI, Co, Al, Ni.

{b}

Elements which stabilise austenite:

Ni, Mn, Co, Cu - all FCC elements and thus more soluble in FCC austenite than BCC ferrite.

Elements which stabilise ferrite:

Cr, Mo, W. V, Si - all BCe elements.

Basic Metallurgy

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The characteristics of the important alloying elements in steel are summarised below:

Sulphur

present as a residual element from manufacture. Forms low melting point FeS (1193°C) and makes steels "hot short" and brittle at high temperatures; therefore limited to 0.05% in most steels.

Manganese combats effect of S by preferential formation of MnS; forms solid solutions with a-iron and increases strength and hardenability; C-Mn steels have approximately 1.3 - 1.6%Mn.

Nickel behaves similarly to Mn in increasing strength and hardenability improves toughness, e.g. O.3%C 3.5%Ni steels as crankshafts, axles etc.

ChromIum dissolves in Q-iron and forms carbides; improves strength, hardenability, wear resistance, corrosion and oxidation resistance, e.g. flIes 1.0%C 1.S%Cr •

Molybdenum Mo carbides are very stable and give improved high temperature ,$trength and creep reslstance, e.g. C-O.5%Mo in lloiler service.

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Tungsten

stable, hard carbides for Wear and abraslon resistance. e.g. 1.0%C 2.0%W O.5%Cr for drills and blades.

Silicon

improves oxidation resistance, e.g. automotive valves 8%Cr 3.5%Si .

Basic Metallurgy

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METALLURGICAL DEFINITIONS OF ALLOTROPIC PHASE CHANGES IN STEELS

Ferrite a

An interstitial solid solution of carbon in body centred cubic iron (also known as aJpha iron), the atomic spacing being .2B7nM. the phase occurs below the upper critical temperature, l.e. below 91 oDe - 723°C depending on e content. the maximum solubility of carbon being .025% carbon at 723DC.

Delta Ferrite .5

Similar to alpha ferrite, the atomic spacing between the lattice being .293nM, the phase occurs in the peritectic region.

Austenite y

An interstitial solid solution of carbon in face-centred cubic iron (also known as gamma Iron), the atomic spacing being .365nM. the phase occurring above the upper critical temperature, l.e, 910 - 723DC depending on carbon content. Maximum solubility 2.06% carbon at 114rC.

Cementite

An intermetallic compound of carbon and iron. (FesC also known as iron

carbide) .

~~~rut~·". . . .... ... ..... - ..•. ,;

,. A"?mihateqstructure of ferrite and cementite (c~n.also be-defined-asa

mechanical miXture of a solid solution and an intermetalJic compound).

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Martensite

A super-saturated interstitial solid solution of carbon in body centred tetragonal iron (caused by rapid cooling from austenite and entrapment of carbon in solution).

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3. PHASE DIAGRAMS

The various structures or phases present during mixing of metals may be represented by phase diagrams where alloy composition is plotted versus temperature. The simplest phase system is where both metals completely mix in the solid and liquid states. e.g. Cu-Ni. Note that pure metals melt at one definite temperature but alloys melt (and solidify) over a range of temperatures.

In the second type, total mixing occurs in the liquid with no mixing in the solid. e.g. Pb-Sb. More commonly some mixing does occur in the solid as in the AgCu systems. Such phase diagrams are known as EUTECTIC systems, meaning with low melting point.

The iron-carbon diagram

An outlined Fe-C diagram is presented overleaf. Details of the phases can be added from the following Information:

Pure iron exists in 3 forms and melts at 15399C. BCC alpha iron (a-ferrite} < 910°C

FCC gamma iron (y-austenite) >910 - <14000e BCe delta iron (6-ferrite) > 1400°C

. Garbqndissolvesin ihterstitialsplidsolutjon . to,6.925% ·hla7Fe~t~~~~G....· .. t6'1.i~·· . . jn.y~~e ·at ft'4:7°C

to 0.10%;n o;_Fe at 1492~C

Fe and C form a compound (Fe3 C, cementite). The equivalent weight % is 93.3%Fe 6.7%C.

A eutectic exists between austenite and cementite at 4.3%C.

A eutectold (similar to a eutectic but in the solid phase) exists between a-ferrite and cementite at 0.83%C. Known as PEARLITE it has a lamellar structure with

alternating bands of ferrite and iron carbide. .

Under equilibrium conditions alloys below 0.83%C consist of mixtures of ferrite and pearlite, whilst alloys above 0.83%C consist of mixtures of cementite and pearlite ..

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Most alloys of interest in welded systems are in the range of approximately 0.10-0.25% although steels of higher C levels can be welded. In this range the room temperature structure of the steel consists of ferrite and pearlite. The higher the carbon content then the higher is the strength and hardness of the steel.

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Iron-carbon phase diagram

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4.

THE EFFECTS OF COOLING RATE ON STRUCTURE

Temperature - time - transformation (TTT) dIagrams

Very slow cooling of carbon steels gives a soft structure of equilibrium phases of ferrite and pearlite, whilst rapid cooling will produce martensite, a hard and

brittle phase, which causes a reduction in toughness and ductility of the steel. Intermediate cooling rates may produce different levels of hardening and structure variations. The effect of different cooling rates on a steel's final structure can be shown in a TIT diagram.

Annealing of steel involves heating to approximately 925°C and slow cooling in a furnace. This produces a relatively large grain size. coarse pearlite and a soft structure. Normalising Involves air cooling, from around 925°C which results in both a finer grain size and pearlite spacing and strengthens and hardens the steel. Even faster cooling, such as oil or water quenching, gives increased

levels of strength and hardness and may produce a non equilibrium phase change to martensite instead of the usual ferrite and pearlite phases.

The phase changes that occur depend particularly upon material composition and cooling rate. Low carbon steels. for example, are almost impossible to harden by quenching. Whilst increasing carbon levels, which favour a larger proportion of pearlite in the structure. lead to increased hardenability. Other elements too, such as manganese. chromium and molybdenum cause an increased hardenabllity. as seen in carbon-manganese and low alloy steels.

The properties of a steel, then. will depend critically on its composition and its heat treatment (or cooling rate). It is evident therefore. that during welding. which involves rapid cooling from high temperatures, significant changes can occur in the structure of the weldment which may have important implications on the properties of the Joint.

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TENSILE STRENGTH Kg/mm~

% PEARLITE

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100

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% CARBON Effect of carbon on mechanical properties and microstructure of iron

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500

300

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Typical T - T - T diagram

Basic Merullurgy

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Heat affected zone formation

During welding. a region of the parent material adjacent to the solidifying weld metal is heating to high temperature and changes in structure occur, producing a heat affected zone (HAZ). The properties of the HAZ depend critically on material composition and cooling rate.

Taking a O.15%C steel and referring to the iron - carbon diagram, the HAZ structure varies as shown overleaf.

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Note that the changes that occur in the HAZ on cooling of a weld are saUd state changes and therefore require time to take place. If austenite is cooled very rapidly, diffusion of carbon is not possible and a distorted structure of MARTENSITE is formed. Martensite is a BODY CENTRED TETRAGONAL {BCn structure, supersaturated with respect to carbon. The high lattice strains induced give martensite its characteristic high hardness and this is influenced by carbon content:

%C

0.1 0.3

0.5 0.7 0.9

VPN

390 640

810 920 920

By comparison, a-ferrite is 90 VPN and pearlite 200 - 450 VPN depending on the fineness of the structure.

Busic Metallurgy

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TRANSITION

UNAFFECTED

Phases Formed

Ferrite and pearlite Ferrite and austenite

Austenite

Liquid metal

HAZ formation during welding of steel

Basic \,1dallllrgy

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\ STRUCTURE OF THE WELDED JOINT

Fusion welding involves a very intense heat source which melts the base material and any consumable which is used, forming a weld pool between items being jOined. This weld pool solidifies and cools, uniting the base materials. The way in which this takes place has a profound effect upon the properties of the joint, the three most-Important characteristics of the welding process being the intensity of the heat source, the rate of heat input and the efficiency of the method used to protect the weld from the atmosphere.

The welded joint consists of three distinct areas - the weld metal, the heat affected zones and the unaffected parent materiaJ.

HEAT INPUT

Most welding processes - MMA. MIG, TIG, SAW, produce a weld poor which is roughly semicircular in cross section, the size of the pool increasing or decreasing as the heat input is increased or decreased. Deeply penetrating heat sources such as the electron beam or laser, however, give a deep, finger-like weld poor. The heat input rate is govemed by current, voltage and

travel speed: yolts x amps: and is one of the most Important variables

travel speed

since it controls heating and cooling rates and weld pool size. In generaf terms, the higher the heat input rate the lower the cooling rate and the larger Is the weld pool - this is very important In the weldIng of carbon and ferritlc aJloy steels, since slow cooling rates decrease the chances of hydrogen induced cracking.

On the other hand, slow cooling rates increase the grain size in both the HAZ's and the weld metal due to grain growth - the longer the time spent above the grain coarsening temperature, the courser the structure in HAZ and weld metal will be - electro-slag welding for example has a very long welding thermal cycle and produces very coarse large grained I-lAZ's and weld metal.

Basic ivklallurgy

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THE HEAT AFFECTED ZONE (HAZ)

The HAZ may be divided into two regions - the high temperature regions in which major microstructural changes such as grain growth occur, and the low temperature region in which secondary effects such as precipitation or tempering may take place. The peak temperature which will be reached will be at the fusion boundary which will be at the melting temperature of the weld metal.

In metaJs which have been cold worked, grain growth may be preceded by recrystallization which wiJI result In a softening and loss of tensile strength. Alloys hardened by precipitation will usually be softened by fusion welding.

The time at high temperatures can be reduced by the use of a process WhIch proauces a aeap narrow weld pool and/or by a reduction In neat input. Electron beam and laser welding have these characteristics and therefore minimize th9 metaJlurgical effects in and width of the HAl. The effects of the various thermal treatments experienced by a welded. jOint in a Single pass fusion weld In carbon steel are illustrated below.

This diagram is for a single pass weld - in a multi-pass weld the same effects are produced except that additionally weld passes are "heat treated- by passes laid on top of them, producing a highly complex range of different structures.

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8asic Metallurgy

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METALLURGY OF WELDING

CARBON AND LOW ALLOY STEELS

5.

In the following sections the major problems associated with the welding of carbon and low alloy steels are discussed in terms of the main failure mechanisms. with particular attention given to problems of weldment cracking.

Cold Cracking

Cold cracking or hydrogen cracking is probably the most important metallurgical defect which occurs in carbon-manganese and low alloy steel welds. This is reflected In the wide terminology used to describe this defect type, which is also often referred to as heat affected zone (HAZ) cracking or underbead cracking, to describe its usual area of occurrence.

As its name Implies, this cracking phenomenon occurs at low temperatures. usually below about 300°C. It requires a susceptible weldment microstructure, associated with a hardened region, and the presence of hydrogen. The occurrence of significant stress levels In the neighbourhood of the weldment is also likely to increase the tendency for cracking to occur.

Hydrogen plays an important role in cold cracking because of its reduced solubility In· steel at lower temperatures. During solidification and coofing, hydrogen is rejected from solution and, in a hardened microstructure, promotes cracking. Because of this, welding with low hydrogen processes may be required. For manual metal arc (MMA) welding, basic electrodes which produce low weldment hydrogen contents are available. Gas shielded welding (tungsten inert gas, TIG or metal Inert gas, MIG) are also low hydrogen processes. Note that appropriate drying of welding consumabJes is also necessary to minimise hydrogen uptake and this applies equally to coated MMA electrodes and to flux used in the submerged arc welding (SAW) process.

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As noted earlier, low carbon steels are not readily harden able; they are thus not normally considered susceptible to cold cracking. The presence of manganese, however, in carbon-manganese steels, increases harden ability. This is reflected in the carbon equivalent (CE) formula which is a measure of the hardenability of the steel:

CE =

%C +

% Mn 6

For low alloy steels, where other alloying elements increase the harden ability a more extensive formula is applied :

CE = %C + % Mn + (%Cr + %Mo + %!? + (%Ni + %Cu)

6 5 15

Based on the CE of a particular steel. appropriate precautions may be taken to minimise the risk of cold cracking.

The hardness of a particular joint is related not only to the steel composition, and its effect on microstructure, but also on the COOling rate. Thus the joint design and material thickness may also affect the susceptibility to cold cracking. The control of COOling rate, in fact, is an important method for minimising cold cracking, since sloWing the cooling rate aJlowsa longer time at higher temperature which permits hydrogen to diffuse away from the joint before cracking can take place.

-.

The cooling rate may be affected by increasing the heat input to a joint or slowing the welding speed. The most common method applied, however, is preheating of the joint which not only allows hydrogen removal at temperatures above the critical cracking temperature but also gives some reduction in HAl hardness .

Basic Metallurgy

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The amount of preheat applied depends on material composition and hence carbon equivalent (CE). In general. with a CE of up to 0.45 preheat is optional. From 0.45 - 0.55 a preheat of 150 - 200°C may be applied, whilst from 0.55 - 0.60 preheats of 200 - 300°C may be necessary to prevent cracking. For extremely hardenable steels (CE above 0.6) the use of austenitic stainless steel consumables may be considered. Because of the high solubility of hydrogen in austenite there is less risk of hydrogen diffusing to the hardened HAZ.

Note that for thick materials In particular, preheat is also often applied at CE levels below 0.45. Where multipass welding is applied. it is important that the weld joint be maintained at the preheat temperature between runs 0.8. interpass temperature control Is also important). For hardenable low alloy steels. post weld heat treatment (PWHn is usually necessary to improve mechanical properties of the weldment. even where the risks of hydrogen cracking have been overcome.

British Standard BS 5135: 1984 ·Process of arc welding of carbon and carbon manganese steels" gives a precise recommendations on welding procedure to avoid hydrogen induced cold cracking .

Attention is given to carbon equivalent values; hydrogen levels. material thickness. arc energies and required preheat levels.

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APPLICATION OF PRE HEAT

lS

0
0

0
,
- r-··
0

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125 1/75:150
100 / / Minimum
0 /'~// preheahng- -
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14

Diffu.iblt hydrogen content Scar.
mLJ100 II of deposited m~11
Over Up to .nd includiflll
15 - A
10 15 B
5 10 C
- 5 D
Sci' .. (see 21.2.31
A B C 0
To btl used (e) 0.39 0.41 0.43 0.48
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not 8xcaeding 12

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Figure 4 (continued)

20

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Arc E'nergy kJlmm

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EXAMPLE ONE:

CALCUlATE THE PRE-HEAT FOR THE FOLLOWING

Material Thickness

75mm

Material Type

Joint Type

Single Vee Butt

Heat input level 2.0Kj/mm.

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Hot Cracking (Solidification Cracking)

Hot cracking occurs at high temperatures above the solidus temperature. Prerequisites for cracking are that the material should have a low ductility and high contraction stresses should be present.

On cooling of a liquid metal, solidification begins at one temperature (the liquidus) and is complete at a somewhat lower temperature (the solidus). Between the two, the alloy forms a coherent incompletely solidified mass, and acquires mechanical strength. It Is, however, brittle and has no ductility until cooled to lower temperatures. Alloys solidifying over a wide temperature range have a equivalent wide brittle range and are particularly prone to hot cracking (e.g. certain aluminium and magnesium alloys).

Brittleness in the solidus region is caused by intergranular or interdendritic liquid films: under the influence of contraction stresses hot c'racking may result. In steel, the main element contributing to cracking Is sulphur (S) which promotes the formation of low melting polnt iron sulphide (FeS). Other elements are phosphorus (P) and boron (8). The sulphur in steer can be rendered harmless by additions of manganese (Mn) which promotes the formation of manganese sulphide inclusions. As the carbon content of the steel increases, so the level of Mn to Inhibit cracking must also be increased.

Weld cracking may also result from inadequate ~feeding". This effect is named from foundry casting terminology used to describe the filling or feeding of shrinkage gaps by liquid metal during casting. FusiOn welds are normally selffeeding; however •. if the penetration is too deep relative to the weld width, shrinkage or solidification cracks may occur.

The risk of hot cracking in carbon steel weldments can be minimised by:

(i) maintaining a low C in the weld deposit;

(ii) keeping S and P levels as low as possible

(iii) keeping Mn sufficiently high to allow for dilution from the parent (and hence ingress of S)

(iv) minimising restraint and dilution

Although less common as a cause of cracking, attention to inadequate weld geometry may also be required.

General guidance on the avoidance of solidification cracking is given in BS . 5135: 1984.

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900

NO PREHEAT

700

......... a

TACK IllELD

sao

300

-

--.. 270 HV
--.
-
-
310 HV
..
.. .. .- • ,. .. 01 •
. '" ., . 420 HV
10 20 30 40 50 100

Time (sec) after 870·C

Effect of preheat on cooling rate and hardness

Ii
•
50
.\
40
NO
!>In/S
30 CRACKING
RATIO
I 20
CRACKING
10 0.10 0.12 0.14 0.16

% C

Effect of Mn/S ratlo and C content on susceptibility of C steel to hot cracking

n<lSIC Metallurgy

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Lamellar Tearing

Lamellar tearing is a cracking phenomenon which may occur in thick plate subjected to high transverse welding stresses. The problem is related to elongated non-metallic inclusions (sulphides and silicates) lying parallel to the plate surface and producing poor ductility in the through thickness (short transverse) direction. It is not necessary for the inclusions to be present in large sheets (e.g. as laminations) but often as a large number of small areas in' slightly different planes. These may produce stepped cracks originating in the parent material close to the HAZ and progressing through thickness.

Where lamellar tearing may be a particularly serious problem (e.g. in offshore platform construction) steels of low sulphur level may be required {e.g. <o.007%}. In addition minimum levels of ductility in the transverse direction

may be specified. This requires a STRA test, to determine the Short Transverse Reduction in Area. Generally a minimum value of 20% may be specified.

Where possible. design should avoid heavy contraction stresses in the through thickness direction (i.e. heavy fillets and cruciform joints). Since lamellar tearing can also be adversely affected by hydrogen, appropriate precautions to minimise hydrogen levels should be taken (see cold cracking).

General guidance on the avoidance of lamellar tearing is given in as 5135: 1984.

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Reheat Cracking

Reheat or stress relaxatlon (or stress relief) cracking can occur in the HAZ of thick wall low alloy steel weldments subjected to high temperature stress relief or service (e.g. boiler plant).

The phenomenon is the result of both high temperature (600DC) embrittlement of the HAZ and the presence of residual welding stresses. Weldments over approxImately 50mm in thickness are most susceptible to failure •

. ;,

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During service or stress relief, precipitation of carbides occurs, strengthening the grains within the HAZ. Stress relaxation thus occurs at the weaker grain boundaries leading to intergranular cracking of the HAZ. Mo-V and Mo-8 steels are especially susceptible to this type of failure, although other elements such as Cr, Cu, Nb and Ti can also promote embrittlement.

Susceptibility to reheat cracking is determined by hot tensife testing (600DC) of a specimen subjected to a simulated weld thermal cycle. If tensile strength is beJow that of the parent material and reduction of area is below 20% then susceptibility to reheat cracking is indicated.

Coarse grained HAZs are more susceptible than fine grained to cracking; hence low heat input welding is likely to be beneficial. Other aspects to be considered include restriction of V Jevels (to 0.1 %). design to avoid high restraint, the dressing of Weld toes to remove areas of potential stress concentration, and the application of intermediate stress relief to partially completed welds.

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Stress Corrosion Cracking

Stress corrosion cracking (SeC) is a failure mechanism that requires the joint action of corrosion and a tensile stress. Although not limited to weld regions, this type of cracking is very often associated with weldments, where the resIdual welding stresses produce conditions suitable for cracking.

sec occurs in most alloy systems in specific corrosive environments. Where corrosion is the dominant factor, cracking is usually intergranular and where stress is the more important. transgranular cracking is mostly seen. There are, however, several exceptions to this general rule.

Carbon steels are susceptible to sec in hot caustic and hot nitrate solutions, at temperatures above approximately 70llC and sOlle respectively. In anhydrous ammonia, cracking can occur at ambient temperature. AU of these environments produce intergranular cracking. Cracking in ammonia is particularly serious in regard to ammonia storage tanks.

Transgranular cracking in high strength steels occurs in sulphide environments, where corrosion produces iron sulphide and hydrogen. Cracking results from ingress of hydrogen into the stressed region and, in this respect, is similar to cold cracking in steels. In practice sulphide sec is controlled by limiting the hardness of the steel weldment to 22HRC (Rockwell e scale hardness) which is equivalent to 246 Vickers hardness, Note that cracking is not exclusively transgtanular in nature and that some intergranular cracking may be seen in this environment.

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WELDABILITY OF LOW CARBON, MICROALLOYED STEELS.

BACKGROUND

Microalloyed steels are C-Mn steels with small additions of alloying elements which are carbide, nitride or carbonitride formers e.g. Nb, Ti, V, Al, Ta and Zr. Microalloying elements usually have a combined level of 0.15% maximum. (In America these steels are known as HSLA steels, for High Strength Low Alloy). The steels have good strength and toughness and normally a ferritic and pearlitic structure, produced by normalising or controlled rolling. In the latter case finishing temperatures of 800 - 850°C are below the usual hot rolling temperatures and result in increased strength levels.

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Microalloyed steets were developed as improved alloys over conventional C-Mn steels, where limits on strength were set by problems of reduced weld ability and toughness at higher C and Mn levels. The addition of microalloying elements such as Nb and V increases strength through preCipitation hardening and grain refining whilst allowing lower C levels. Typical C levels of less than 0.12% are seen for normalised grades while even lower levels are available in controlled rolled steels. The low C levels mean low carbon equivalent (CE}values and good weldability. Other aJloying elements such as Mn, Ni, Cu, Cr and Mo improve strength levels by solid solUtion hardening of the ferrite, whilst NI.and

Mn decrease the austenite transfonnation temperature giving a finer structure of . improved toughness. SmaJladditions of elements such as Ni, Cu, Cr and Mo . are made, for example. to increase the strength of thicker sections of

microalloyed steels.

USES OF MICROALLOYED STEELS

Microalloyed steels are used as weldable constructional steels e.g. for offshore platform structures (such as as 4360 Grade 500, weldable structuraJ steels), and high pressure pipelines (such as APr Sl, Grade X6S, line pipe).

WELDABIUTY

Although usuaUy less serious for microalloyed steels. problems associated with welding are essentially the same as experienced for conventional C-Mn steels.

---~-. _ ... _ .. _-------------------------

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T M C P STEELS

Developments in steel making practice have led to high strength steels produced with progressively lower levels of carbon. These steels are ThermomechanicaJly Controlled Process or TMep steels with high toughness and I because of their reduced CE values, good weldability.

TMCP steels are produced by a combination of controlled rolling and on line accelerated cooling. Three stages are involved :

roughing rolling

finished rolling

accelerated cooling.

Roughing rolling - relatively high temperature where deformation of the austenite gives rapid recrystalllsation ar.d finer austenite grains.

Finished rolling - lower temperature rolling below region of rapid recrystalJisation; deformation bands act as subsequent sites for austenite transformation.

The main aim of both of these stages ;s to decrease the grain size and increase both strength and toughness.

AcCelerated cooling - typically· 5-150C/sec from BOO~500DC followed by air COOling below 500°C: additional strengthening results

from refinement of the ferrite grain and enhanced precipitation hardening in the case of microaJJoyed steels.

A typical TMCP steel used in 32mm constructional plate for Arctic service is:

0.07%C 0.3%Si 1.S%Mn <0.002%S <0.025%P <O.2%Cu O.35%Ni

(IfW CE = 0.36)

Such steels have high resistance to HAZ hydrogen cracking during welding.

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H.S.L.A. STEELS

Low carbon micro alloyed hot rolled steels are high strength structural steels with less than O. t2%C. These steels are micro alloyed by Nb, Ti or V and cover the yield strength range from 290-700 N/mm2• For pearlite reduced steels a pearlite content of about 25% is not exceeded. For pearlite free steels, the pearlite content is under 5%. Low carbon microalloyed hot rolled steels are used for pipes, for automotive components, offshore structures and pressure vessels. To achieve higher impact shelf energies in rolled products, the steel must have lower sulphur contents or sulphide shape control must be used. For sour gas service the steel must be very clean and the formation of low temperature transformation products must be minimised.

Weldability

~ Compared with other structural steels, low carbon microalloyed hot rolled steels have improved weldability. This means that they are less sensitive to any type of cracking in the HAZ and weld metal.

Achievement of an adequate fracture toughness in the HAZ and weld metal may be ona of the principal weldability problems. Very low carbon content. high purity 'and optimised microstructure make this type of steel less sensitive to transformation embrittlement and ageing. High weld input energies (over approximately 30kJJmm) may cause an increase of HAZ sottsnmq,

Welding consumables and welding procedure

For welding low carbon microalloyed steels, all arc welding processes are used. Resistance welding, as well as other non-arc processes, such as friction

welding and electron beam welding, can also be used. For each application, the welding consumables must be selected to provide the weld with required properties, soundness and corrosion resistance. Low hydrogen consumables are normally used for welding higher strength steels."

Post-weld heat treatment

.... Post-weld heat treatment of welded joints in law carbon microaUoyed hat rolled steels is generally performed when the thickness is more than 4O-50mm or when there is a need to ensure adequate resistance to sulphide stress corrosion. The temperature range for heat treatment is usually between 575

.. and 625°C.

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PRODUCTION

High strength low alloy steels are primarily hot rolled into usual wrought product forms and are commonly supplied in the as-hot rolled condition. However, the production of bot rolled HSLA products may also involve special hot mill processing that further improves the mechanical properties of some product forms. These include:

1.

Controlled rolling of precipitation strengthened steels to obtain fine austenite grains and/or highly deformed austenite grains (pancaked), which during cooling transforms into fine ferrite grains that greatly enhance toughness while improving yield strength.

2.

Accelerated cooling of, preferably controlled rolled HSLA steels to produce fine ferrite grains during the transformation of austenite. These cooling rates cannot be rapid enough to form acicular ferrite, nor can they be slow enough so that high cooling temperatures result and thereby causing the overageing of precipitates.

.. , )

3. The quenching or accelerated air or water cooling of low carbon steels (less than 0.08% C) that possess adequate hardenability to transform into acicular ferrite. This micro-structure offers excellent weldability and high toughness. although controlled rolling is sometimes necessary.

4. The nonnaIising of vanadium containing HSLA steels to refine grain size.

5. The inter-critical annealing of HSLA steels (and also carbon manganese steels with low carbon content) to obtain a dual-phase micro-structure of martensite islands in a ferrite matrix.

The usefulness and cost-effectiveness of the above methods are dependent on both alloy content and product form.

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Interstitia' Solid Solution

Smaller atoms are able to fit into the spaces between the larger atoms e.g. Carbon/Iron.

,

If the atoms of one metal are much smaller than the other. the smaller atoms are able to fit in the voids between the larger atoms. In this case an "Interstitial Solid Solution" results.

Metals which form substitutional solid solutions in any proportions are:-

Copper Chromium Silver

- Nickel

-Iron

- Gold.

And partially:-

Copper Coper Copper

- nn

- Zinc

- Aluminium

A problem which can exist with solid solution is that during solidification the atoms of the two metals may not be evenly distributed throughout the two metals and may not be evenly distributed throughout the grain boundaries. This problem is known as "corinq", where the centre of the grain will consist mainly of atoms of the metal with the higher melting point. Whereas the outer fringes of the crystal will consist mainly of atoms from the metal with the lower melting point.

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ATTAINMENT OF TOUGHNESS IN WELDMENTS

INTRODUCTION

The recognition of factors controlling toughness of weldments is especially important since brittle fracture can initiate from several defects which may be present in weld joints, either within the HAZ or weld metal e.g. hydrogen cracking, solidification cracking or lack of fusion defects. The risk of fracture will be determined by the properties of the microstructure which loCally surrounds the defect tip. Because of the weld thermal cycle a wide range of microstructures can be seen between welds depending on welding conditions and material composition. Moreover within any given weldment microstructural variation is associated with significant differences in local toughness. The problem of toughness in weldments will be examined by conSidering the HAZ and weld metal regions separately.

HAZ TOUGHNESS IN FERRITIC STEEL WELDMENTS.

In ferritic steets variations in HAZ structures may be considered in terms of three temperature ranges:

the fully transformed HAZ heated to temperatures above Ac; (above approx. 900°C).

the intercriticaJ HAl heated to temperatures between Ac, and AS {approx. 700 - 900°C}.

the subcritical HAl heated to temperatures below Ac, (below approx. 700°C).

In addition the fully transformed HAZ may be descrtbec in terms of two temperature ranges:

the coarse grained transformed HAZ heated to temperatures above approx. 1200°C.

the grain refined transformed HAZ heated to temperatures in the range of approx. 900 - 120QoC.

The microstructures of the four HAZ regions vary significantly; however, precise separation of the HAZ into these areas may not be easy since they merge into one another. The exception perhaps is the subcritical HAZ which visibly is no different from the original parent material (although metallurgical changes may have occurred).

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Generally, maximum HAZ embrittJement is observed in the coarse grained transformed HAZ adjacent to the weld fusion boundary. This is particularly of significance since it is this region which may often contain weldment defects.

The highest HAl toughness is usually found in the grain refined transformed HAl. This is also of significance since, in multipass welds, the coarse grained HAZ may be refined by successive weld passes and hence its toughness improved. The worst tough ness therefore may often be associated with single pass coarse grained (unrefined) HAZ areas.

Note that in un reheated grain coarsened HAZs the toughness may be lower or higher than the toughness of the parent metal. Generally the HAZ is less tough than the parent for fine grained C-Mn and fow alloy steels. For C or C-Mn steels which are not grain refined, the HAZ toughness usually matches or is higher than the parent.

In toughness testing of ferritic steel HAZs failure generally occurs by brittle (cleavage) fracture or ductile (micro void coalesence or mvc) fracture. Occasionally intergranular fracture may also be experienced In low alloy steel HAl's due to brittle grain boundary precipitates.

Cleavage resistance of transformed HAZs.

At higher temperaturesductile fracture occurs at all heat inputs. As temperature decreases the resistance of cleavage decreases. This is shown by tests for toughness, e.g, the Charpy impact test, where the energy absorbed to break a specimen red uces as temperature is lowered.

At low heat inputs the prior austenite grain size is mall (e.g. 70llm). However, the faster cooling gives relatively high levels of martensite in the structure and a hardness of350 HV. The presence of martensite leads to poor roughness, By comparison at higher heat inputs the slow cooling produces no martensite and a hardness 0[200 HV. However a coarse grain size develops (approx. 300Jlffi) and toughness is again reduced.

At intermediate heat inputs the toughness is optimised by a combination of grain size and microstructural properties.

Cleavage resistance of intercriticaJ and subcriticaJ HAZs.

These HAZ regions are tougher than the grain coarsened areas adjacent to the fusio~ boundary. They may be embrittled relative to the parent, however. by low heat Inputs (martensite formation) and by strain ageing embrittlement due to nitrogen.

G~nera"y adequate HAZ toughness is seen in fine grained C-Mn, C-Mnrnicroalloyed and low alloy steels which are aluminium treated and supplied in the normalised or quenched and tempered conditian.

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MVC resistance of HAZs

The resistance to ductile mvc failure in all steel grades is a function of the cleanliness with respect to non metallic inclusions. Reduction of inclusions and inclusion shape control both benefit toughness levels.

Improving HAZ toughness

Subcritical PWHT of C-Mn steels at 600°C is beneficial to HAZ toughness at low arc energies because of the tempering of martensite.

If high arc energies are desired, control should be exercised over travel speed. Higher travel speeds give a reduction in grain size and an increase in toughness since travel speed has a large effect on thermal cycle retention time above Ac). for a given heat input.

WELD METAL TOUGHNESS IN FERRITIC STEEL WELDMENTS

Compared with HAZ toughness, a complicating factor in weld metals is that the deposit composition and hence microstrcture can vary through thickness due to dilution effects (e.g. 70% at root to 5% at surface).

i . j

Improving resistance to cleavage fracture •

.• ,1

~ ,

Major microstructural constituents of ferritic weld metals placed in order of decreasing transformation temperature (increasing toughness) are:

; -.1

proeutectoid ferrite nucleated at austenite grain boundaries

.ferrite-carbide aggregates

ferrite platelets in bainitic structure

acicular ferrite (narrow interlocking ferrite plates)

The weld metal may also show some retained austenite and martensite.

The relative amounts of the above microstructures control the resistance ot weld metal cleavage.

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CHROMIUM-MOLYBDENUM STEELS

DESCRIPTION

Alloy steels of this family contain 0.5 to 9% chromium and 0.5 or 1 %

molybdenum. The carbon content is normally less than 0.20% for good weldability, but the alloys have high hardenabiUty. The chromium provides improved oxidation and corrosion resistance and the molybdenum increases strength at elevated temperatures. They are normally supplied in the annealed or normaJized-and-tempered condition.

Chromium-molybdenum (Cr-Mo) steels are widely used in the petroleum industry and in steam power generating for elevated temperature applications.

<, )

COMPosmON AND PROPERTIES

Some alloys may contain small additions of niobium, titanium, or vanadium, or

increased amounts of carbon or silicon for specific applications. Some castings or forging alloys may contain up to 0.35% carbon.

Chromium-molybdenum steels are air hardenable. and undergo the high- and low-temperature metaliurgicaJ transfonnations common to low alloy steels. 111e mechanical properties depend upon the condition of heat treatment. TIle tensile property requirements for these steels vary with the product form and the type of heat treatment Because of the wide range of properties of some product forms. the user must be. aware of the actual specification to which the product was produced.

HEAT TREATMENT

The types of heat treatment normaJly applied to Cr-Mo steels are the same as those applied to other hardenable steels, namely: annealing, narmaJizing-andtempering, ·quenching-and-tempering treatments are used to obtain desired grain size or required mechanical properties for the application ..

Heat treatment of these steels is used to advantage when fabricating large heavy-waned pressure vessels. Such vessels are usually constructed from 2V .. Cr-1 Mo steel that has been normalized or quenched and tempered. These treatments result in a microstructure of bainite or low-carbon martensite which has good ductility. Regardless of the heat treatment given to the steel, proper control of the tempering treatment is required. The tempering temperature and time at temperature are both important.

WELDING METALLURGY

The welding metallurgy of the chromium-molybdenum steels is similar to that of the other hardenable, low aHoy steels discussed previously. These steels wiJl harden when quenched from the austenitizing temperature, and are sensitive to hydrogen-induced cracking.

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The Cr-Mo steels, as with other low alloy steeJs, are subject to creep (temper) embrittlement during long time service at temperatures in the 380° to 593"C range. The degree of ambottJement of the steet is influenced by chemical composition as wef! as heat treatment. There is evidence that non-equilibrium segregation of residual elements in prior austenite grain boundaries is a contributing factor to creep embrittlement of Cr-Mo steel weld metal.

JOINT CES1GN

Joint designs used for welding carbon steel by a specific process are suitable for welding the Cr-Mo steels. The joint geometry should minimize any notch conditions that might contribute to stress concentration. Sharp comers and rapid changes in section size are to be avoided. Butt joints are preferred; fiUet welds should only be used under conditions of' Jow stress. Fit-up for singlewelded joints should assure complete joint penetration without excessive meltthru.

PREHEAT

Preheat ;s required in most cases to prevent hardening and cracking . Recommended minimum preheat and interpass temperatures for various thicknesses of Cr-Mo steels generally increase with the aIloy content and the section thickness.

Lower-preheat temperatures may be used if the welding heat input is relatively high or the available hydrogen is very low, 'as with gas tungsten arc welding. The preheat temperature should be increased if cracking is encountered. particularly if hydrogen is suspected as the cause. The temperature of the completed weld should be raised and held at temperature for a sufficient time to allow excessive hydrogen to diffuse to the surface and escape. The preheat temperature should be increased when the carbon content of the steel exceeds 0.15%.

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Creep resistance is a common attribute of steels and it is relatively easy by a combination of composition, mechanical working and heat treatment to enhance this property. However, there is a tendency for such routes to improved creep resistance to confer other less desirable properties, i.e. high strength, reheat cracking, hydrogen cracking etc.

In materiaJ selection during the design stage, assessments must be made of all the requirements and a compromise made between them and the cost/availability of any actual aJloy.

(

In practice the dominant factors become the service temperature and. environment compared to the aegree of creep which is acceptable.

There are a number of important factors which are necessary in a metal when used at elevated temperatures.

1. Resistance to oxidation and scaling

2. Retention of strength at the working temperature

3. Microstructural stability with regard to carbide precipitation, spheroidisation, sigma phase formulation and temper embrittlement,

Note that other properties may also be required.

A wide range of steel compositions may be used but characteristically we find that Cr and Mo are used as alloying additions according to the service requirements.

For many years the principal high temperature applications were steam power, oil refineries and chemical plants with temperatures up to about 600°C. But with the advent of gas-turbines the requirements are in a working temperature of 900°C and currently materials have to be developed to operate at 1200°C.

The characteristic of high strength requirement is that it must be considered with respect to a time scale.

At elevated temperatures the strength becomes dependent on both strain rate and time. A metal at high temperatures may in fact behave like a viscoelasic material. The metal creeps and undergoes a time-dependent increase in length.

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TERTIARY CREEP

SECONDARY CREEP

FRACTURE

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STEADy STATE CREEP

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de is the creep rate dt

TIME t

As can be seen after an initial rapid elongation the strain rate decreases and reaches a steady state, finally the creep rate increases rapidly until fracture occurs. It is the onset of the last phase which is in practice of particular interest. This type of behaviour is exhibited under constant load due to the increased stress but not usually under constant stress unless significant metallurgical changes occur.

The initial and steady state creep are the sum of

a) sudden strain

b) transient creep

c) viscous creep

The steady state creep represents a baJance between the competing processes of strain hardening and recovery.

The third stage mainly occurs in constant load condition when high stresses are experienced at high temperatures. This tertiary creep is not due solely to the necking of the material but is also the result of structural changes within the material, i.e. void formation and extensive (micro) crack formation.

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WELDING PROCESSES

The Cr-Mo steels are read fly joined by arc welding and brazing processes commonly used tor carbon steel. They can also be joined by electroslag, electron beam, laser beam, friction. and resistance welding. Brazing procedures are similar to those given for other steels, but the thermal effects of the brazing cycle on the properties of Cr-Mo steel must be considered.

ARC WELDING CONSUMABLES

The filler metal should have the same nominaJ composition as the base metal, except for carbon content Normally. the carbon content is lower than that of the base metal. Suggested welding consumables (rods, electrodes. fluxes. and shielding gases) fer arc welding the Cr-Mo stee's to themselves are given below.

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Suggested. welding consumables for joining chromium-molybdenum steels

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Sreel SMAWo
112Cr·I I2Mo E80XX·Bl
ICHt2Mo. ESOXX-B2
1-II4Cr-l!2Mu or B2l
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E.502-XX
SCr-IMo E502·XX crrAW.~
GMAW· FCAW' S.4.W·
ER80X·82l E8ITI·BI F8XX-EXXX-F4
ER80X·B2 E8XTX~B2 F8XX·EXXX·Bl
or B2l or 82X or B2H
ER90X~B3 S9XTX.,83 F9XX·EXXX"BJ
or an, ~r BJX or.B4
ER90X~B3 E9XTXS·83
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ER502 ES02T·1 or 2 f9XX-EXXX·B6
or B6H
ER502 ES02T-1 or 2
ER50S ESOST·lor2
ERSOS E50ST-1 or 2 i· .. --... 7Cr-1/2Mo E7Cr-XX
I '~
9Cr-IMo £SOS·XX a. Sbielded melal arc welding electrodes from AWS Specification A5.4-78 or A5.5·81.

b. Welding rod or eJecrrode from AWS Specification AS.9-77 or A5.28-79. Argon or argolJ plus f 10 5 percent oxygen is used for shielding with CiMAW.

c. Aux cored eJeclrodes from AWS SpeCification A5.22·80 or AS.19-80 uliing CO~ or argon - 2 percent oxygen shielding.

d. EJectrode-lJUI combination 10 produce the desired weld metal composition and strength from AWS Specification AS.2J-80.

Basic Mcuillurgy

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Recommended stress-relief temperature ranges for chromiummolybdenum steels

Steel

Temperature range, cC

1I2Cr-1/2Mo

620-700

1Cr-1/2Mo 1-1/4Cr-1/2Mo

620-730

2-1/4Cr-1 Mo 3Cr-1Mo

670-745

SCr-1/2Mo 7Cr-112Mo 9Cr-1 Mo

670-760

,-, ..

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The stress-relief temperature should not exceed the tempering temperature of normalized and tempered or quenched and tempered steel. Also, the temperature should be in the low end of the recommended range for high creep strength, and in the high end of the range for good resistance to corrosion or hydrogen embrittlement. Welded joints to be used in acid or caustic service should always be heat treated.

It may be necessary to anneal or normalize and temper a weldmant that is fabricated witt:J a high heat-input welding process. such as electroslag welding. One of these heat treatments is required to refine the grain size in the weld metal and heat-affected zone and thus improve toughness.

Whether the welded joint must be held at the preheat temperature until it is heat-treated depends upon the compositions of the base metal and weld metaJ, the welding procedures, the degree of restraint. and the steps taken to avoid the formation of martensite prior to cooling. Welds in Cr-Mo steels containing 1.25% Cr or less can be safely cooled to ambient temperature prior to heat treatment, provided the carbon content is in the normal range.

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WELDABIUTY OF CRYOGENIC STEELS

Cryogenic steels are alloys used at low temperatures particularly in the transportation and storage of liquified gases. Depending on service temperature and fracture safety criteria they range from fine grain AI-killed steels to 9% Ni steels, with Ni alloyed steels being used below approximately - 50°C.

Typical materials used for low temperature (cryogenic) service.

Gas Uquefaction

temperature,OC

Recommended material

Ammonia -33.4

Propane -42.1

Fine grained, AI killed steel

_.i

Propylene -47.7

Carbon disulphide -50.2

2.25% NI steel

Carbon dioxide Ethane

-78.5

-88.4

3.5% Ni steel

Ethylene Methane Oxygen

-103.8

-163.0

-182.9

5-9% Ni steel

Nitrogen

-195.8

Austenitic stainless steel.

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WELDING PROCEDURES AND WELDABIUTY

1. Fine grained AI killed steels.

Welding precautions include preheat and the use of Jow hydrogen conditions to void HAl cracking. Ni containing consumables are often applied (e.g. 2% Ni alloy MMA or TIG consumables) to ensure good weld toughness.

2. Steels with low NI content (1-3.5%).

Ni steels solidify initially as austenite rather than ferrite and since austenite has a low solubility for impurities CP,S,C} there is some risk of liquation cracking due to low melting point NilS. The use of low heat Input or pulsed welding techniques are beneficial.

Cold cracking can occur in the HAl or weld metal of 2.0 - 3.5% Nf steels because of their high hardenability. Control of hydrogen levels and preheat in the range 150 - 250°C are applied. Post weld heat treatment (PWHn at

580 - 630°C may also be used.

All welding processes can be employed. MMA electrodes are-either matching composition or more usually high Ni electrodes of the Inconel type.

3. 5-6% HI steel.

The properties of this grade of steel which match 9% Ni steels at -196°C are achieved by complex double normalising and quenching treatments. Welding causes a change in properties in the HAZ with some reduction in toughness. The HAZ toughness can be improved by PwrtT at 650°C followed by rapid cooling.

4. 9% NI steels.

After full heat treatment the parent material structure consists of tempered martensite with apprOXimately 5% retained austenite. In the high temperature HAZ the level of austenite decreases in a narrow band adjacent to the fusion boundary and hardening occurs (e.g. from 250 HV to 350HV). However little or no decrease in toughness is observed.

Under normaJ low hydrogen welding conditions 9% Ni steel is not susceptible to HAZ cracking and no preheat is required. This is due to the presence of austenite in the structure which acts as a sink for any hydrogen present.

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Steels for Low Temperature Service

As the temperature of service is reduced the level of alloying is increased to yield the properties required. The main concern is toughness at the design temperature and the development of toughness at low temperatures is achieved by alloying steel with nickel.

Service to -400 C

Service to these temperatures can be achieved with C-Mn steel provided they are clean and fine grained. Most commonly aluminium is added to give the desired microstructure. These so-called 'aluminium killed steels' have good toughness as measured by, for example the Charpy impact test, to -50 or -600 C. Structures for service in the North Sea require toughness at these temperatures, not because they will ever be exposed to such levels, but because it has been determined that if Charpy impact shows full ductility at -500 C there is no risk that a larger structure will suffer brittle fracture at -100 C.

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These tough C-Mn steels are usually welded by MMA, SAW or FCA Wand consumables have been developed which, with controlled heat input, can give matching toughness to the parent plate. These consumables usually contain 1 to 2% of nickel although both FCA Wand SAW consumables based on C-Mn with addition of very small amounts ofTi and B have been developed. This combination appears to work well at the higher heat inputs a f these processes but has proved di fficu It to control in MMA. TIG welding may be used although it is most often used for root

runs in pipe followed by FCA W or MMA fill and cap. For some specific applications hot wire automated TIO has been employed, Fillers containing 2.5% Ni are used for this process.

The IlW formula for the calculation of Carbon Equivalent may be used with these steels to determine the need for preheat. For thick material preheat up to 1500 C may be used ifheat input is relatively low. Heat input is controlled to below 4 kl/rnm for most applications to avoid deterioration of toughness in the HAZ.

Nickel Steels with 1 to 2.5% Ni

Al-killed C-Mn steels have a sharp transition in toughness as the temperature drops. They rapidly change from showing fully ductile behaviour to brittleness. By adding nickel to the steel this transition is smoothed somewhat. Nickel containing steels can therefore be used to lower temperatures than the C-Mn and find use for LPG containers and tanks.

Depending on thickness preheat up to 2500 C may be used. Welding consumables are usually chosen to slightly overmatch the nickel content of the base p late as the thermornechanical treatment of the plate used by the steelmaker to achieve optimum properties is unavailable to the welder, However modem 2.5% Ni consumables can be used for most applications, provided heat input is controlled to relatively low levels.

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3.5% Nickel Steels

With this level of nickel toughness to _100° C may be achieved. This allows the use of 3.5% Ni steel for liquid ethene storage (boiling point -102° C). Whilst matching fillers are available they tend to be hot crack sensitive and the more usual choice is Ni-Cr-Fe of the Inconel type.

5 to 9% Nickel Steels

European steel makers produced straight forward 5% Ni steel to give more assurance of properties at liquid ethene temperatures, but as the skill in producing 3.5% Ni steel increased this became an expensive alternative finding little use these days. The Japanese found however that at 5.5% Ni, with very particular heat treatment thew could rival the performance of9% Ni and reach operating temperatures of -164° C; the boiling point ofIiquid methane (natural gas).

9% Ni steels, produce by carefully controlled quenching and tempering or a double normalising and tempering treatment, give good toughness at -196° C; the temperature of liquid nitrogen. They can therefore be used in vessels and tanks for the storage and transport of LNG (-164° C),liquid oxygen

(-183° C) and liquid nitrogen (-196° C). Ofthese the most important is LNG. Tanks are built at strategic points in countries using natural gas to 'peak shave'. This is required as demand is not constant and pipelines from the source, e.g. The North Sea, may not be able to cope with a rapid increase. Storage tanks are therefore used to supply the short term excessive demand. The gas is stored as liquid in large vertical cylindrical tanks made from 9° Ni steel.

The fractionation of air to produce oxygen, nitrogen and argon is another application for 9% Ni steel. The principle employed is the distillation of liquefied air and the largest fractionating columns are now made from 9% Ni steel.

9% Ni steels are tough to very low temperatures because nickel produces a ductile rnartensitic microstructure and helps to stabilise small amounts of austenite which remain as 'retained austenite' even to the sub zero temperatures. So even though the structure is martensite it is very tough and it will not transform to any form so the material does not suffer a 'transition temperature' in Charpy testing.

Although experiments have been tried with matching or 12% Ni fillers, these have not proved to be commercially successful. They require careful control of oxygen to stand any chance of giving good toughness in the as-deposited condition so can only be used in TIG welding with perfect shielding. The most common type of filler for these steels are Ni-Cr-Mo (alloy 625) types. They may be welded by 1v[MA, MIG. TlG or SA W. They do not suffer from hydrogen cracking sensitivity and do not require preheating. The heat input needs to be controlled to fairly low levels to avoid the development of large grains in the HAZ which can lead 10 a loss of toughness,

Stress relieving is not normally required but if excessive stress builds up in the lower strength weld metal it is sometimes advisable to reduce this with a stress relief treatment. This requires careful control to avoid taking the parent plate into the tempering range and changing its properties.

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WElDABILITY OF STAINLESS STEELS

Stainless steels are iron alloys containing a minimum of 12% chromium, which improves both corrosion and oxidation resistance (Fig.1). Discovered by Brearley in England in 1913 these steels became the forerunners of the three major categories of stainless materials, the austenitic grades based on ironchromium-nickel (Fe-Cr-Ni) alloys and the martensitic and ferritic grades, both developed from Fe-Cr alloys. In the 19405 high strength, precipitation hardened stainless steels with alloying additions such as aluminium (AI), copper (Cu) or titanium (Ti), were also developed. More recently the duplex ferritic-austenitic grades of stainless steel and the high molybdenum (Mo) austenitic stainless steels have been introduced, especially for oilfield and petrochemical plant.

The large variety of stainless steels offers a wide range of properties, including toughness at very low temperatures, high temperature strength and oxidation resistance and freedom from corrosion in many environments. These properties may be met in wrought or cast materials and considerable quantities of stainless steel are used in these forms, such as heat exchanger tubing or pump bodies. With welded constructions, however, the weld metal has essentially a chill cast structure differing significantly from that of the parent. In addition the temperature changes during welding produce a heat affected zone (HAZ) in the parent material, and the as-welded region may contain significant residual stresses. These factors influence the weldability of all stainless steels to a greater or lesser degree, depending on the material grade, and may have important consequences on service performance.

1.

METALLURGY OF STAINLESS STEELS

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19

The properties of stainless steels depend significantly not only on chemical composition but also on phase structure and it is important to understand how these factors may influence behaviour, The phase structure may be austenitiC, ferritic or martensitic and in addition a mixed structure, territic - austenitic (or duplex) may exist. The mechanical properties. corrosion resistance and weldability associated with these structure types vary considerably.

The most common grades of stainless steels are those with austenitic atomic structure, the so called face centred cubic (or f.c.c) structure; for example the type 300 series of alloys such as 304 (18 Cr 8 Ni grade). Materials of f.c.c. structure are generally ductile and have good toughness at low temperatures. These include AI, Cu, Ni and gold (Au).

in addition there are important non-metallic alloying elements in stainless steels which promote the formation of an austenitic structure. Of particular importance are carbon (C) and nitrogen (N) which significantly influence material properties and weldability.

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12

stainless steels

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% chromIum

Alloy

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Oxidation of steeJ and

Jron-chromJum alloys at 1000·C

Maximum service temperature in air, °C

565 595 620 650 705 705 870

1090 1150

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Carbon steel

1.0Cr O.SMo steel 2.2SCr 1.0Mo steel 5Cr O.SMo steel 9Cr 1.0Mo steel

12Cr stainless steel (e.g. 410)

18Cr 8Ni stainless steel (e.g. 304) 25Cr 12Ni stainless steel (e.g. 309) 25Cr 20Ni stainless steel (e.g. 310)

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Ferritic stainless steels are generally Fe-Cr alloys and have a territic atomic structure, which is a body centred cubic (or b.c.c.) structure. A characteristic of the b.c.c. structure is that a ductile - brittle transition is exhibited at lower temperatures. Ferritic stainless steels are therefore very much less tough than austenitic stainless steels.

A further important property difference is that in the more open (Jess closely packed) b.c.c. structure, diffusion rates are higher, which results in rapid grain growth during heating; this has important implications on weldablllty.

Whilst carbon and nitrogen may be beneficial in austenitic stainless steels, they may be detrimental to ferritic grades. The higher corrosion resistant ferritic alloys therefore (e.g. 26% Cr) have controlled, very low levels of C and N producing the so caned ELI steels (Extra Low Interstitial). Particular care to avoid contamination is required during welding.

In addition to the territic stainless steels, material with a b.c.c. structure include iron (carbon steel). Cr, molybdenum (Mo).

Duplex stainless steels are alloys containing two distinct phases, the b.c.c. ferritlc and the t.c.c. austenitic, usually in approximately similar proportions. The properties of the alloys are therefore a balance between the properties of the discreet phases, which significantly influences weldability. One important property difference is that the ferritic phase is magnetic and the austenitic phase non-magnetic, which is used to assess the phase balance in these materials.

The third important phase structure in stainless steels is the martensitic structure. This is particularly common in rapidly cooled low alloy steels (e.g. 21.4 Cr/1 Mo) as well as in some C-Mn steels. The structure is a distorted form of b.c.c., called body centred tetragonal (or b.c.t.) r and is super saturated with carbon. This gives the martensitic structure its characteristic high strength and hardness, and leads to problems of weldability.

Because of the importance of Cr and C on the properties of the various stainless steels, it is convenient to compare the range of the different grades in terms of carbon and chromium contents (Fig.2).

1.1

Phase Diagrams

Phase diagrams or constitution diagrams describe the composition - temperature relationships in alloy systems and may be used to show the phases which exist under equilibrium conditions, that is under conditions of slow cooling or heating.

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c- CONTENT Jwt_o,.

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During welding. non equilibrium conditions exist (i.e. rapid heating and cooling); nonetheless, phase diagrams may still be helpful in understanding the changes that may occur during welding processes.

The Fe-Ni binary phase diagram is shown in Fig.3. Note that pure Fe exists in three phases, which with increasing temperature are:

alpha iron (a - Fe) or a-ferrite gamma iron (y - Fe) or austenite delta iron (6 - Fe) or 0 - ferrite .

a - ferrite and c5 - ferrite are both b.c.c. and essentially identical phases; austenite is f.c.c.

Unlike Fe. pure Ni exists only in the single f.c.c. or austenitic structure. The FeNi alloy system. therefore, exists totally in an austenitic structure only at higher temperatures.

The Fe-Cr 'binary phase diagram is shown in Fig.4. Unlike Ni. Cr has a b.c.c. structure, which Fe also exhibits at both higher (c5-ferrite) and lower temperatures (a-ferrite). For this reason the Fe-Cr alloy system exists totally in a territic structure at higher or lower temperatures and the austenitic region is restricted.

The Fe-Cr diagram also shows another important phase which is present in stainless steels, the sigma phase (0). Sigma is an intermetallic phase of approximate composition 55% Fe 45% Cr. It is very hard and brittle and may affect not only the mechanical properties but also the corrosion resistance of stainless steels.

Because sigma forms at elevated temperatures it may develop during welding or high temperature service and may adversely affect weldment properties.

Whilst binary phase diagrams are used to represent only two elements, in practice alloy systems often contain additional major elements. In stainless steels, therefore, the equilibrium phases are represented in the threedimensional ternary Fe-Cr-Ni diagram. For convenience this may be represented in two dimensions in terms of concentration profiles at a fixed value of one element. Fig.5 shows such a diagram for a range of stainless steel alloys containing 70% Fe with varying Ni and Cr contents.

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