Metallurgy
Metallurgy
Metallurgy
The best way to understand the metallurgy of carbon steel is to study the Iron Carbon
Diagram. The diagram shown below is based on the transformation that occurs as a result of
slow heating. Slow cooling will reduce the transformation temperatures; for example: the A1
point would be reduced from 723C to 690 C. However the fast heating and cooling rates
encountered in welding will have a significant influence on these temperatures, making the
accurate prediction of weld metallurgy using this diagram difficult.
Austenite This phase is only possible in carbon steel at high temperature. It has a
Face Centre Cubic (F.C.C) atomic structure which can contain up to 2% carbon in
solution.
Ferrite This phase has a Body Centre Cubic structure (B.C.C) which can hold very
little carbon; typically 0.0001% at room temperature. It can exist as either: alpha or
delta ferrite.
Carbon A very small interstitial atom that tends to fit into clusters of iron atoms. It
strengthens steel and gives it the ability to harden by heat treatment. It also causes
major problems for welding , particularly if it exceeds 0.25% as it creates a hard
microstructure that is susceptible to hydrogen cracking. Carbon forms compounds
with other elements called carbides. Iron Carbide, Chrome Carbide etc.
Cooling of a steel below 0.8% carbon When a steel solidifies it forms austenite.
When the temperature falls below the A3 point, grains of ferrite start to form. As
more grains of ferrite start to form the remaining austenite becomes richer in carbon.
At about 723C the remaining austenite, which now contains 0.8% carbon, changes to
pearlite. The resulting structure is a mixture consisting of white grains of ferrite
mixed with darker grains of pearlite. Heating is basically the same thing in reverse.
Martensite If steel is cooled rapidly from austenite, the F.C.C structure rapidly
changes to B.C.C leaving insufficient time for the carbon to form pearlite. This
results in a distorted structure that has the appearance of fine needles. There is no
partial transformation associated with martensite, it either forms or it doesnt.
However, only the parts of a section that cool fast enough will form martensite; in a
thick section it will only form to a certain depth, and if the shape is complex it may
only form in small pockets. The hardness of martensite is solely dependant on carbon
content, it is normally very high, unless the carbon content is exceptionally low.
internal stresses. This reduces hardness and increases toughness, but it also tends to
reduce tensile strength. The degree of tempering is dependant on temperature and
time; temperature having the greatest influence.
Annealing This term is often used to define a heat treatment process that produces
some softening of the structure. True annealing involves heating the steel to austenite
and holding for some time to create a stable structure. The steel is then cooled very
slowly to room temperature. This produces a very soft structure, but also creates very
large grains, which are seldom desirable because of poor toughness.
Normalising Returns the structure back to normal. The steel is heated until it just
starts to form austenite; it is then cooled in air. This moderately rapid transformation
creates relatively fine grains with uniform pearlite.
Welding If the temperature profile for a typical weld is plotted against the carbon
equilibrium diagram, a wide variety of transformation and heat treatments will be
observed.
Note, the carbon equilibrium diagram shown above is only for illustration, in reality it will
be heavily distorted because of the rapid heating and cooling rates involved in the welding
process.
Residual Stress
Alloying Elements
Manganese
Increases strength and hardness; forms a carbide; increases hardenability; lowers the transformation
temperature range. When in sufficient quantity produces an austenitic steel; always present in a steel to
some extent because it is used as a deoxidiser
Silicon
Strengthens ferrite and raises the transformation temperature temperatures; has a strong graphitising
tendency. Always present to some extent, because it is used with manganese as a deoxidiser
Chromium
Increases strength and hardness; forms hard and stable carbides. It raises the transformation
temperature significantly when its content exceeds 12%. Increases hardenability; amounts in excess of
12%, render steel stainless. Good creep strength at high temperature.
Nickel
Strengthens steel; lowers its transformation temperature range; increases hardenability, and improves
resistance to fatigue. Strong graphite forming tendency; stabilizes austenite when in sufficient quantity.
Creates fine grains and gives good toughness.
Nickel And Chromium
Used together for austenitic stainless steels; each element counteracts disadvantages of the other.
Tungsten
Forms hard and stable carbides; raises the transformation temperature range, and tempering
temperatures. Hardened tungsten steels resist tempering up to 6000C
Molybdenum
Strong carbide forming element, and also improves high temperature creep resistance; reduces temperbrittleness in Ni-Cr steels. Improves corrosion resistance and temper brittleness.
Vanadium
Strong carbide forming element; has a scavenging action and produces clean, inclusion free steels. Can
cause re-heat cracking when added to chrome molly steels.
Titanium
Strong carbide forming element. Not used on its own, but added as a carbide stabiliser to some
austenitic stainless steels.
Phosphorus
Increases strength and hardnability, reduces ductility and toughness. Increases machineability and
corrosion resistance
Sulphur
Reduces toughness and strength and also weldabilty.
Sulphur inclusions, which are normally present, are taken into solution near the fusion temperature of
the weld. On cooling sulphides and remaining sulphur precipitate out and tend to segregate to the grain
boundaries as liquid films, thus weakening them considerably. Such steel is referred to as burned.
Manganese breaks up these films into globules of maganese sulphide; maganese to sulphur ratio >
20:1, higher carbon and/or high heat input during welding > 30:1, to reduce extent of burning.
heated for prolonged periods. Small quantities of either titanium (321) or niobium (347)
added to stabilise the material will inhibit the formation of chrome carbides.
To resist oxidation and creep high carbon grades such as 304H or 316H are often used.
Their improved creep resistance relates to the presence of carbides and the slightly
coarser grain size associated with higher annealing temperatures. Because the higher
carbon content inevitably leads to sensitisation, there may be a risk of corrosion during
plant shut downs, for this reason stabilised grades may be preferred such as 347H.
The solidification strength of austenitic stainless steel can be seriously impaired by small
additions of impurities such as sulphur and phosphorous, this coupled with the materials
high coefficient of expansion can cause serious solidification cracking problems. Most
304 type alloys are designed to solidify initially as delta ferrite, which has a high
solubility for sulphur, transforming to austenite upon further cooling. This creates an
austenitic material containing tiny patches of residual delta ferrite, therefore not a true
austenitic in the strict sense of the word. Filler metal often contains further additions of
delta ferrite to ensure crack free welds.
The delta ferrite can transform to a very brittle phase called sigma, if heated above 550C
for very prolonged periods (Could take several thousand hours, depending on chrome
level. A duplex stainless steel can form sigma phase after only a few minutes at this
temperature)
The very high coefficient of expansion associated with this material means that welding
distortion can be quite savage. I have seen thick ring flanges on pressure vessel twist
after welding to such an extent that a fluid seal is impossible. Thermal stress is another
major problem associated with stainless steel; premature failure can occur on pressure
plant heated by a jacket or coils attached to a cold veesel. This material has poor thermal
conductivity, therefore lower welding current is required (typically 25% less than carbon
steel) and narrower joint preparations can be tolerated. All common welding processes
can be used successfully, however high deposition rates associated with SAW could cause
solidification cracking and possibly sensitisation, unless adequate precautions are taken.
To ensure good corrosion resistance of the weld root it must be protected from the
atmosphere by an inert gas shield during welding and subsequent cooling. The gas shield
should be contained around the root of the weld by a suitable dam, which must permit a
continuous gas flow through the area. Welding should not commence until sufficient
time has elapsed to allow the volume of purging gas flowing through the dam to equal at
least the 6 times the volume contained in the dam (EN1011 Part 3 Recommends 10).
Once purging is complete the purge flow rate should be reduced so that it only exerts a
small positive pressure, sufficient to exclude air. If good corrosion resistance of the root
is required the oxygen level in the dam should not exceed 0.1%(1000 ppm); for extreme
corrosion resistance this should be reduced to 0.015% (150 ppm). Backing gasses are
typically argon or helium; Nitrogen Is often used as an economic alternative where
corrosion resistance is not critical, Nitrogrn + 10% Helium is better. A wide variety of
proprietary pastes and backing materials are available than can be use to protect the root
instead of a gas shield. In some applications where corrosion and oxide coking of the
weld root is not important, such as large stainless steel ducting, no gas backing is used.
A pdf guide to weld purging
Huntingdon Fusion Techniques Limited
Carbon content:
304 L grade Low Carbon, typically 0.03% Max
304 grade Medium Carbon, typically 0.08% Max
304H grade High Carbon, typically Up to 0.1%
The higher the carbon content the greater the yield strength. (Hence the stength
advantage in using stabilised grades)
Typical Alloy Content
304
316
316 Ti
320
321
347
308
309
(18-20Cr, 8-12Ni)
(16-18Cr, 10-14Ni + 2-3Mo)
(316 with Titanium Added)
(Same as 316Ti)
(17-19Cr, 9-12Ni + Titanium)
(17-19Cr, 9-13Ni + Niobium)
(19-22Cr, 9-11Ni)
(22-24Cr, 12-15Ni)
304 + Molybdenum
304 + Moly + Titanium
304 + Titanium
304 + Niobium
304 + Extra 2%Cr
304 + Extra 4%Cr + 4% Ni
All the above stainless steel grades are basic variations of a 304. All are readily weldable
and all have matching consumables, except for a 304 which is welded with a 308 or 316,
321 is welded with a 347 (Titanium is not easily transferred across the arc) and a 316Ti is
normally welded with a 318.
Molybdenum has the same effect on the microstructure as chrome, except that it gives
better resistance to pitting corrosion. Therefore a 316 needs less chrome than a 304.
310
904L
The Nickel and other elements that form Austenite, are plotted against Chrome and other
elements that form ferrite, using the following formula:Nickel Equivalent = %Ni + 30%C + 0.5%Mn
Chrome Equivalent = %Cr + Mo + 1.5%Si + 0.5%Nb
Example, a typical 304L = 18.2%Cr, 10.1%Ni, 1.2%Mn, 0.4%Si, 0.02%C
Ni Equiv = 10.1 + 30 x 0.02 + 0.5 x 1.2 = 11.3
Cr Equiv = 18.2 + 0 + 1.5 x 0.4 + 0 = 18.8
A typical 309L welding consumable Ni Equiv = 14.35, Cr Equiv = 24.9
The main disadvantage with this diagram is that it does not represent Nitrogen, which is a
very strong Austenite former.
Ferrite Number
The ferrite number uses magnetic attraction as a means of measuring the proportion of
delta ferrite present. The ferrite number is plotted on a modified Shaeffler diagram, the
Delong Diagram. The Chrome and Nickel equivalent is the same as that used for
the Shaeffler diagram, except that the Nickel equivalent includes the addition of 30 times
the Nitrogen content.
Examples
The Shaeffler diagram above illustrates a carbon steel C.S , welded with 304L filler.
Point A represents the anticipated composition of the weld metal, if it consists of a
mixture of filler metal and 25% parent metal. This diluted weld, according to the
diagram, will contain martensite. This problem can be overcome if a higher alloyed filler
is used, such as a 309L, which has a higher nickel and chrome equivalent that will tend to
pull point A into the austenite region.
If the welds molten pool spans two different metals the process becomes more
complicated. First plot both parent metals on the shaeffler diagram and connect them
with a line. If both parent metals are diluted by the same amount, plot a false point B on
the diagram midway between them. (Point B represents the microstructure of the weld if
no filler metal was applied.)
Next, plot the consumable on the diagram, which for this example is a 309L. Draw a line
from this point to false point B and mark a point A along its length equivalent to the total
weld dilution. This point will give the approximate microstructure of the weld metal. The
diagram below illustrates 25% total weld dilution at point A, which predicts a good
microstructure of Austenite with a little ferrite.
Evaluating Dilution
The above picture is of a new pressure vessel that failed during its hydraulic test. The
vessel had been stress relieved, but some parts of it did not reach the required temperature
and consequently did not experience adequate tempering. This coupled with a small
hydrogen crack, was sufficient to cause catastrophic failure under test conditions. It is
therefore important when considering PWHT or its avoidance, to ensure that all possible
failure modes and their consequences are carefully considered before any action is taken.
The post weld heat treatment of welded steel fabrications is normally carried out to reduce
the risk of brittle fracture by:
Reducing residual Stresses. These stresses are created when a weld cools and its
contraction is restricted by the bulk of the material surrounding it. Weld distortion
occurs when these stresses exceed the yield point. Finite element modelling of
residual stresses is now possible, so that the complete welding sequence of a joint
or repair can be modelled to predict and minimise these stresses.
The risk of brittle fracture can be assessed by fracture mechanics. Assuming worst-case
scenarios for all the relevant variables. It is then possible to predict if PWHT is required to
make the fabrication safe. However, the analysis requires accurate measurement of HAZ
toughness, which is not easy because of the HAZs small size and varying properties.
Some approximation is possible from impact tests, providing the notch is taken from the
Super Duplex: Stronger and more corrosion resistant than standard duplex.
S32760(Zeron 100) 25Cr 7.5Ni 3.5Mo 0.23N PREn = 40
Duplex solidifies initially as ferrite, then transforms on further cooling to a matrix of ferrite
and austenite. In modern raw material the balance should be 50/50 for optimum corrosion
resistance, particularly resistance to stress corrosion cracking. However the materials
strength is not significantly effected by the ferrite / austenite phase balance.
The main problem with Duplex is that it very easily forms brittle intermetalic phases, such
as Sigma, Chi and Alpha Prime. These phases can form rapidly, typically 100 seconds at
900C. However shorter exposure has been known to cause a drop in toughness, this has
been attribute to the formation of sigma on a microscopic scale.
Prolonged heating in the range 350 to 550C can cause 475C temper embrittlement.
For this reason the maximum recommended service temperature for duplex is about 280C.
Sigma (55Fe 45Cr) can be a major problem when welding thin walled small bore pipe
made of super duplex, although it can occur in thicker sections. It tends to be found in the
bulk of the material rather than at the surface, therefore it probably has more effect on
toughness than corrosion resistance. Sigma can also occur in thick sections, such as
castings that have not been properly solution annealed (Not cooled fast enough).
However most standards accept that deleterious phases, such as sigma, chi and laves, may
be tolerated if the strength and corrosion resistance are satisfactory.
Nitrogen is a strong austenite former and largely responsible for the balance between
ferrite and austenite phases and the materials superior corrosion resistance. Nitrogen cant
be added to filler metal, as it does not transfer across the arc. It can also be lost from
molten parent metal during welding. Its loss can lead to high ferrite and reduced corrosion
resistance. Nitrogen can be added to the shielding gas and backing gas, Up to about 10%;
however this makes welding difficult as it can cause porosity and contamination of the
Tungsten electrode unless the correct welding technique is used. Too much Nitrogen will
form a layer of Austenite on the weld surface. In my experience most duplex and super
duplex are TIG welded using pure argon.
Backing / purge gas should contain less than 25ppm Oxygen for optimum corrosion
resistance.
Fast cooling from molten will promote the formation of ferrite, slow cooling will promote
austenite. During welding fast cooling is most likely, therefore welding consumables
usually contain up to 2 - 4% extra Nickel to promote austenite formation in the weld.
Duplex should never be welded without filler metal, as this will promote excessive ferrite,
unless the welded component is solution annealed. Acceptable phase balance is usually 30
70% Ferrite
Duplex welding consumables are suitable for joining duplex to austenitic stainless steel or
carbon steel; they can also be used for corrosion resistant overlays. Nickel based welding
consumables can be used but the weld strength will not be as good as the parent metal,
particularly on super duplex.
Good impact test results are a good indication that the material has been successfully
welded. The parent metal usually exceeds 200J. The ductile to brittle transition
temperature is about 50C. The transition is not as steep as that of carbon steel and
depends on the welding process used. Flux protected processes, such as MMA; tend to
have a steeper transition curve and lower toughness. Multi run welds tend to promote
austenite and thus exhibit higher toughness
Tight controls and the use of arc monitors are recommended during welding and automatic
or mechanised welding is preferred. Repair welding can seriously affect corrosion
resistance and toughness; therefore any repairs should follow specially developed
procedures. See BS4515 Part 2 for details.
Production control test plates are recommended for all critical poduction welds.
Welding procedures should be supplemented by additional tests, depending on the
application and the requirements of any application code:
A ferrite count using a Ferro scope is probably the most popular. For best accuracy
the ferrite count should be performed manually and include a check for deleterious
phases.
Good impact test results are also a good indication of a successful welding
procedure and are mandatory in BS4515 Part 2.
A corrosion test, such as the G48 test, is highly recommended. The test may not
model the exact service corrosion environment, but gives a good qualative
assessment of the welds general corrosion resistance; this gives a good indication
that the welding method is satisfactory. G48 test temperature for standard duplex is
typically 22C, for super duplex 35C
Position 6G
Temperature at the end of welding < 250C
Recommended Testing
1. Ferric Chloride Pitting Test To ASTM G48 : Method A
2. Chemical analysis of root
3. Ferrite count