MAT373 Thermal and Thermochemical Surface Treatments
MAT373 Thermal and Thermochemical Surface Treatments
MAT373 Thermal and Thermochemical Surface Treatments
Dr Adrian Leyland
[email protected]
1) INTRODUCTION
There are many other forms which carbon can take up in steels when they
are cooied, depending on variables such as the carbon content and the
COOLING RATE. One important form is known as MARTENSITE. This
appears to have a fine needle-like structure and is VERY HARD. It can be
formed when steel is RAPIDLY QUENCHED from high temperature.
Thermal & Thermochemical Treatments
The resulting phase(s) on cooling are
characterised by TIME TEMPERATURE
TRANSFORMATION (TTT) diagrams. Curve
(1) enters the transformation region at a, thus
MARTENSITE is formed between a and b. This
is the SLOWEST CURVE for martensite only to
be formed, since it just misses point n.
It therefore represents a CRITICAL COOLING
RATE. Curves (2), (3) & (4) show successively
slower cooling - and phases other than
MARTENSITE can form. NOTE that the final
phase obtained depends on the first exit point
of the transformation region. For curve (3), the
first exit point is at c; thus FINE PEARLITE is
obtained, even though the curve subsequently
re-enters the BAINITE and MARTENSITE
regions. Bainite is comparable in composition
to pearlite but is extremely fine structured,
Flame hardening: Acetylene, propane or natural gas flame is moved slowly over the
surface, followed by a quenching spray (which may be part of the burner assembly).
Similar to induction methods but operation is more costly and less easily controlled.
However, capital cost is lower and odd shapes can be more easily treated.
Laser and electron beam transformation hardening: Rapid surface heating by laser
(usually CO2) in air – or electron beam in vacuum. Highly localised heating, hence
bulk material provides a self-quenching effect. Case depths up to 1 mm can be
obtained. Generally used for components which might distort from induction
hardening, such as cutting blades, shaft splines, etc. (ie. thin components).
Thermal & Thermochemical Treatments
Thermochemical treatments
Like thermal treatments, THERMOCHEMICAL TREATMENTS
rely on modifying the existing surface of a material, rather than
adding a coating.
Carburising Methods:
Carbonitriding
This is a VARIATION OF THE CARBURISING PROCESS, where up to
0.5% NITROGEN (as well as carbon) is applied to the steel surface.
This IMPROVES HARDEN ABILITY and reduces FERRITE-AUSTENITE
TRANSFORMATION temperature.
Gives RELATIVELY SHALLOW CASE (< 0.75 mm) – hence carbonitrided
components may not be suitable for high load applications.
Otherwise, property improvements are similar to carburising – and the
LOWER PROCESSING TEMPERATURES (~ 750–850ºC) can reduce
potential distortion problems.
Methods employed are similar to those of carburising (components still
need to be quenched!).
Thermal & Thermochemical Treatments
Nitriding
This typically involves the DIFFUSION OF NITROGEN INTO A STEEL SURFACE
at 490-530ºC. Below 490ºC, nitrogen diffusion becomes too slow and above
530ºC, coarsening of the substrate microstructure (eg. through dissolution of grain-
boundary carbide precipitates) may reduce core strength – and negate surface
hardness improvements. A superficial "WHITE" LAYER forms during processing –
which comprises a mixture of Fe-N compounds. Nitrogen diffuses from this layer
into the underlying steel to form finely dispersed needles of alloy nitrides and, by
reaction with carbon in the steel, carbonitrides. The white layer is only about 20 µm
thick but is brittle. To prevent spalling in service, it is usually removed by grinding
or by chemical treatment.
QUENCHING IS NOT REQUIRED – since there is no phase transformation on
cooling. Case depth is typically 0.2-0.7 mm; hardness is 900-1100 HV – which is
temper-resistant to about 500ºC.
The RELATIVELY LOW PROCESSING TEMPERATURE gives less distortion than
carburising or carbonitriding and it can produce excellent fatigue performance and
abrasion resistance.
STEELS MUST CONTAIN NITRIDE FORMING ELEMENTS to obtain a sufficient
hardening effect: Al and Ti have a pronounced effect – even at low concentrations;
Cr is also used. Hot working tool steels such as AISI H13 (5% Cr) are often nitrided.
Thermal & Thermochemical Treatments
Nitriding Methods:
(i) Gas nitriding:
Dry ammonia is circulated through gas-tight retorts containing the
components. The ammonia dissociates on heating, resulting in
nitrogen diffusion into the steel surface:
2NH3 ▬► 2N (into steel) + 3H2
Processing @ 515ºC for ~ 45 hrs gives a case depth of ~ 0.5 mm.
Nitrocarburising
This is usually performed at about 570ºC and involves diffusion of nitrogen
with a small proportion of carbon. Similar to nitriding, QUENCHING IS NOT
REQUIRED. Methods involve the use of ammonia gas with a carburising
agent, or a molten (fused) salt bath containing sodium cyanide or sodium
cyanate (although non-cyanide based alternatives are now widely available).
A 2 hour treatment time gives a 20 µm thick carbonitride phase which has
good resistance to adhesive wear. A thicker layer of alloy nitrides may also
be formed – but only the carbonitride layer is usually exploited, hence
PLAIN CARBON STEELS (in addition to alloy nitriding steels) can be
effectively processed.
A small amount of surface porosity occurs, which is useful for oil retention
under marginally lubricated conditions.
Thermal & Thermochemical Treatments
COMPARISON OF
THERMOCHEMICAL TREATMENT PROPERTIES (I)
SLIDING WEAR RESISTANCE
Carburising can form a surface hardness of up to 850 HV, depending upon the steel
composition. In high load abrasion it is important that the core is strong enough to
adequately support the hardened case.
Carbonitriding provides a case of similar hardnes to carburising, but usually on plain
carbon steels with a relatively weak core – so not suitable for high load applications.
Nitriding provides layers with hardness up to 1100 HV on high strength cores.
Nitrocarburised layers have hardness of 600 HV, giving resistance to mild abrasion.
SUMMARY OF APPLICATIONS:
CARBURISING: where thick cases required on heavily loaded components; distortion
is a problem.
NITRIDING: used where distortion is otherwise a problem & design stresses are high.
CARBONITRIDING: where parts are small (requiring only a shallow case) and design
stresses are low; generally used to improve performance of plain carbon steels in thin
sections. (stampings & pressings, fabricated sections, gearshaft splines, etc.)
NITROCARBURISING: where adhesive wear is a problem; eg. running-in of components.
Thermal & Thermochemical Treatments
Chromising
This involves the diffusion of Cr into high carbon steel by heating at 950-1300ºC
in Cr-rich media. The treated surface provides oxidation and wear resistance.
In pack chromising, the component is embedded in a mixture of source metal
(fine powders of ferro-chromium), an activator (ammonium halides) and inert fillers
(alumina or silica) and heated for 12-15 hours in an inert or reducing atmosphere.
In liquid chromising, the component is heated at 900-1000ºC in a molten bath of
CrCl2 or ferrochromium and BaCl or MgCl2 (which act as an activator to enhance
reaction and improve diffusion).
Gas chromising is achieved by heating the steel component in the presence of
vapours of CrCl2 and CrC3 and a reducing gas (H2) at 950-1050ºC.
In high carbon steels the chromised layer consists of complex chromium carbides
such as (Fe,Cr)7C3. A continuous layer forms, due to outward diffusion of carbon
from the core – and Cr inwards. Typical hardnesses are 1200-1300 HV.
Applications include turbine bins and steel components to resist nitric acid attack.
Thermal & Thermochemical Treatments
Aluminising (‘Calorising’)
In this process Al is diffused into low- and medium-carbon steel surfaces to impart
resistance to corrosion and oxidation at high temperatures. In pack aluminising, the
component is heated with fine powders of ferro-aluminium, ammonium chloride
(activator) and inert fillers at 750–1000ºC for 3-6 hours. This is followed by
annealing at 800–980ºC for 12-48 hours which reduces the brittleness of the layer,
and causes further diffusion of the Al (to depths of 0.6-1.0 mm) in low carbon steel.
Liquid aluminising consists of immersing the component in a both of molten Al (with
6-8% Fe added) at 750–800ºC. The Fe is added to prevent the Al from dissolving
excessively the steel substrate; an initial treatment of 1-1.5 hours’ duration produces
a case of 0.2-0.35 mm depth.
The aluminised layer is a solid solution of Al and Fe, giving excellent resistance to
heat and corrosion by sulphurous gases. The usual content of ~25% Al is enough to
ensure adequate resistance to heat and corrosion. Typical applications are turbine
blades, burner pipes, flue stacks and high temperature fasteners.
Sometimes platinum is also introduced (called PLATINUM ALUMINISING) to further
improve high temperature corrosion properties (often used for jet engine applications).
Thermal & Thermochemical Treatments
Siliconising
Silicon is diffused into the surface of steels (or ductile iron) to provide high resistance
to wear, to oxide scaling at high temperatures and to hot corrosion (eg. molten salt,
or sulphide / chloride attack).
Pack siliconising (infrequently used) heats the component in a powder of ferro-silicon
(50-95% Si) activated with ammonium chloride at 1100-1200ºC for 2 to 24 hours.
Typical case depths of 0.2-0.8 mm.
Gas siliconising uses retort furnaces in which the substrate is heated at 950-1050ºC
for 2 to 5 hours in the presence of solid silicon carbide powder and SiCl4 vapour.
Typical case depths of 0.5-1.25 mm.
The case is a solid solution of Si in a-Fe (~14% Si), exhibits high brittleness and
moderate hardness (200-300 HV) and high porosity. There is also significant thermal
distortion. Siliconised steel components are however very effective at reducing wear
under poorly lubricated conditions, and exhibit good corrosion & oxidation resistance.
Typical applications include rollers in bottle washing machines, slurry pump shafts
and associated pipework.
Thermal & Thermochemical Treatments
Sherardising
Zn is diffused into an iron or steel surface by heating the component in fine
zinc powder (95% Zn) at 350-450ºC. Temperature uniformity is important
for consistent alloying all over the surface. Powder size is also important,
with finer powder producing a smoother, less porous surface.
The mechanical properties of the steel are not usually affected. Ideally
suited for treating high tensile steels which are susceptible to hydrogen
embrittlement (ie. not suitable for electroplated Zn), providing sacrificial
corrosion protection in aqueous, humid environments.
Typical applications include domestic electrical appliances (e.g. washing
machines, fridges, microwaves), outdoor telecommunications devices,
automotive components, scaffolding clips and fasteners used in the
construction industry.
Thermal & Thermochemical Treatments
Thermochemical treatment of non-ferrous metals
Copper Alloys
In the ‘DELSUN’ process, a layer of tin is electroplated onto brass, bronze or
aluminium bronze, followed by a diffusion treatment at 400-450ºC to produce a thin
(≈15 µm) scuff resistant layer above a thicker hardened layer. Layer hardness is
usually 450-600 HV; typical applications in include valves, gears, pistons and
reduction gear wheels / synchroniser rings for HGV gearboxes.
Aluminium Alloys
The ‘ZINAL’ process improves the frictional characteristics of aluminium alloys.
An indium alloy containing zinc and copper is electroplated, then a low temperature
diffusion treatment is carried out (120-150ºC). The case consists of two parts, an
In-rich outer layer 15-20 µm thick and an inner Cu-rich zone 3-7 µm thick.
These layers remain sufficiently ductile to deform without cracking and improve
scuffing / fretting resistance – even under poor lubrication. There is no significant
effect on the corrosion resistance. Typical applications include diesel and petrol
engine pistons, connecting rods, water pump bearings and helicopter rotor parts.
Thermal & Thermochemical Treatments
Titanium Alloys (I)
NITRIDING
Usually gas (and more recently plasma) nitriding used to produce a 1-2 µm thick
TiN compound layer and a thicker (25–250 µm) diffusion zone beneath. Typical
treatment temperatures are 650–1050ºC. The (very poor) friction and wear
characteristics of Ti-alloys are markedly improved – and the corrosion resistance
is further enhanced – but fatigue strength can be reduced significantly at higher
treatment temperatures. Typical applications include racing car components (eg.
cam followers, wheel hubs and bolts), lightweight gear applications in aircraft.
CARBURISING
Not widely used for titanium, but gas carburising is relatively common – and a
pack-type system has also been developed. Tends to give good wear resistance
but treatment temperatures need to be high (850ºC+) so distortion on cooling is
a major problem.
OXIDATION
Usually performed in a fused salt bath (although gaseous and plasma processes
are being developed) at 650-800°C for 2-4 hours; the bath contains mixtures of
lithium and potassium carbonates. Wear resistance is significantly improved but
(again) fatigue life can be reduced.
Thermal & Thermochemical Treatments
Titanium Alloys (II)
OTHER SALT BATH TREATMENTS
Cyanide salt baths can be used to produce a diffusion layers which are rich in C, N
and / or O. Oxygen content in particular must be closely controlled to avoid excessive
Ti loss and brittleness. Treatment at 800ºC for 2 hours followed by water quenching
produces a friable outer layer of TiO2 and C (which appears black). This ‘compound
layer’ can be removed by glass bead blasting without impairing the wear properties.
No loss in fatigue resistance is reported, as a result.
BORIDING
Not commercially available, but can be performed in BCI3 / H2 gas mixtures or using
high purity amorphous B in a vacuum environment. Several hours’ treatment at
1000ºC is required to produce a 50 µm thick layer of hardness 2500 HV.
The layer is usually duplex in nature containing both TiB and TiB2.
CHROMO-SILICIDING
Components are packed into a mixture containing 50% Cr / 50% Si in a vacuum
furnace at 850ºC for 8 hours. A tough composite layer of TiCr2 (containing hard
intermetallic compounds such as Ti3Si5, TiSi2 and TiSi) is produced. A surface
hardness of 1000 HV is obtained and wear resistance is significantly improved.