Surface Hardening en
Surface Hardening en
Surface Hardening en
Euro Inox
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ISBN 978-2-87997-387-6
SWISS INOX
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Contents
Surface Hardening of Stainless Steels
First Edition 2013
(Materials and Applications Series, Volume 20)
Euro Inox 2013
Publisher
Euro Inox
Diamant Building, Bd. A. Reyers 80
1030 Brussels, Belgium
Phone: +32 2 706 82 67
Fax: +32 2 706 82 69
E-mail: info@euro-inox.org
Internet: www.euro-inox.org
1 Introduction
2 Principle
3
Thermochemical diffusion methods
3.1 Carburising
3.2 Gas nitriding
3.3 Plasma (ion) nitriding and liquid nitriding
3.4 Nitrocarburising
3.5 Boriding or boronising
4
Applied energy methods
4.1 Induction hardening
5 Costs
6 Summary
7 References
2
3
5
6
7
10
11
13
14
14
15
16
17
Author
Alenka Kosma, Brussels (B)
Cover photos
Expanite, Hillerd (DK) (left)
Heat & Surface Treatment, Eindhoven (NL) (bottom right)
iStockphoto (top right)
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disclaim any liability or responsibility for loss, damage or injury, resulting from the use of the information
contained in this publication.
1
1 Introduction
Scratch resistance of
the surface is often
requested for highvisibility applications.
2 Principle
Surface hardening includes a wide variety of
techniques. Most often it is used to improve
the wear resistance of parts without affecting the softer, tough interior necessary to
resist impact occurring during operation.
Wear involves the physical removal of
material from a solid object. It can be
divided into three categories: abrasive,
adhesive and fatigue wear.
Abrasive wear is when two surfaces rub
together and the harder surface grinds
away the softer. It can be characterized
by a rough appearance. Often, work
hardening of the surface can occur.
Adhesive wear, like abrasive wear, is
caused by loaded surfaces rubbing together. With adhesive wear, high localized temperatures are created by friction
at the tips of opposing asperities on rubbing surfaces. These tips can deform and
weld together, due to localized temperatures. They usually break and fall
away as debris.
Fatigue wear occurs whenever a surface
is subjected to repeated high-stress
load. Wear rates are less affected by temperature than is corrosion [6].
Carburising
Nitriding
Nitrocarburising
Thermal spraying
Carbonitriding
Weld hardfacing
Boriding or boronising
Ion implantation
Flame hardening
Induction hardening
Laser-beam hardening
Electron-beam hardening
Physical vapour deposition is discussed in the Euro Inox publication Colouring Stainless Steel, Materials and Applications
Series, Volume 16, http://www.euro-inox.org/pdf/map/ColouringStainlessSteel_EN.pdf
Table 2. Typical characteristics of thermochemical diffusion treatments for stainless steels [7, 8]
Process
Name of case
Process
temperature
C
Typical case
depth
m
Case
hardness
HV
Process characteristics
Nitriding/Carburising/Nitrocarburising
Gas
420600
10200
7501600
Ion
380600
10200
7501600
7001000
1050
1500 to over
2800
Other
Boriding or
boronising
3.1 Carburising
Grain boundary
M23C6
25
20
15
10
Boundary of passivity
since they form nitrides that are stable at nitriding temperatures. Because of their chromium content, all stainless steels can be
nitrided to some degree [9]. However, the
high chromium content of some stainless
steels makes them more difficult to nitride.
This is because chromium forms a passive
layer on the stainless steel surface, which
has to be removed before nitriding. Once
the passive film is broken down (by dry honing, wet blasting, pickling, chemical reduction in a reducing atmosphere, submersion
in molten salts or one of several proprietary
processes), nitriding is effective. The positive side of this is usually a high surfacehardness value. Other alloying elements,
such as nickel, copper and manganese,
have little if any effect on nitriding characteristics [7]. Nitridable stainless steels are:
Martensitic stainless steels. The hardenable martensitic stainless steels are
capable of providing high core strength
to support the nitrided case. Hardening,
followed by tempering at a temperature
at least 15 C higher than the nitriding
temperature, should precede the nitriding operation.
Austenitic stainless steels. Austenitic
stainless steels are the most difficult to
nitride. Nevertheless most can be successfully nitrided [9]. If nitrided, parts
must be in the annealed condition, to
prevent flaking or blistering of the nitrided case. Stabilised or low-carbon grades
are recommended for nitriding, for the
More information on specific heat treatment conditions of different stainless steels can be found in the Euro Inox publication Stainless Steels: Tables of Fabrication Parameters, Materials and Applications Series, Volume 17,
http://www.euro-inox.org/pdf/map/Tables_Fabrication_Parameters_EN.pdf
0
1600
0
1600
(302)
800
400
1600
1600
1.4016 (430)
5 suppliers
1.4749 (446)
1200
Hardness, HK
5 suppliers
800
5 heats
800
400
400
0
0
1.4541 (321)
800
400
1200
1200
5 suppliers
Hardness, HK
Hardness, HK
1200
Hardness, HK
50
100
150
200
250
0
0
50
100
150
200
250
Figure 1. Hardness related to case depth for four stainless steels that were annealed prior to nitriding. The annealing temperature was 1065 C for steel grades 302 and 1.4541 (321), 980 C for steel grade 1.4016 (430) and 900 C
for steel grade 1.4749 (446). Hardness is measured in Knoop values [9].
Table 3. Surface hardness ranges and case depth for some corrosion-resistant and acid-resistant steels [7]
Steel designation
Hardness
HV
Nitride hardness
depth
mm
EN Number
EN Name
Approximate
AISI/ASTM
1.4028
X30Cr13
420
9501200
0.2 max.
1.4104
X14CrMoS17
9501200
0.2 max.
1.4112
X90CrMoV18
440 B
9501200
0.2 max.
1.4117
X38CrMoV15
9501200
0.2 max.
1.4301
X5CrNi18-10
304
9501600
0.2 max.
1.4305
X10CrNiS18-9
303
9501600
0.2 max.
1.4401
X5CrNiMo17-12-2
316
9501600
0.2 max.
1.4535
X90CrCoMoV17
9501600
0.2 max.
300
200
100
Stainless steel
2035% dissociation
Depth of case, m
0
0
10
20
30
40
50
Duration of nitriding, h
Figure 2. Comparison of the nitriding characteristics of austenitic (300 series) and martensitic (400 series) stainless steels, single-stage nitride at 525 C and 550 C [9]
10
Plasma (or ion) nitriding is a method of surface hardening that uses glow-discharge
technology to introduce elemental nitrogen to the surface of a metal part, for subsequent diffusion into the material. In a
vacuum, high-voltage electrical energy is
used to form plasma, through which nitrogen ions are accelerated to impinge on the
workpiece. This ion bombardment heats
the workpiece, cleans the surface and provides active nitrogen. It actually avoids the
need to remove the passive layer, as this is
removed by sputtering prior to the nitriding
phase. Ion nitriding provides better control of case chemistry and uniformity and
has other advantages, such as lower part
distortion than conventional gas nitriding.
For most ferrous alloys, the diffusion zone
formed by nitriding cannot be seen in a metallographic image, because the coherent
precipitates are generally not large enough
to resolve. In stainless steels, however, the
chromium level is high enough for extensive nitride formation, which can be seen
3.4 Nitrocarburising
Some gas-based and plasma-based processes dissolve carbon and/or nitrogen atoms in the surface region of the material.
Dissolution of carbon and nitrogen atoms is
possible due to their smaller size compared
to the alloy metal atoms. The surface hardening results not in a coating but in a surface zone with a high concentration of carbon and/or nitrogen [1, 2, 3]. Large amounts
of atomic nitrogen and/or carbon dissolve
in stainless steel at temperatures below
approximately 450550 C, expanding the
original microstructure. The maximum lattice
expansion can reach nearly 40 % (by
volume) for nitrogen. The thickness of the
zone is approximately 2040 m. Expanded
austenite surfaces are four to eight times
harder than those of the base material.
Along with the increase in hardness and
wear resistance, corrosion resistance is fully
maintained [15, 16].
11
Nitrocarburising can
also be successfully
applied in small bores
and even in very small
cavities. Photos: Bodycote Hardiff, Apeldoorn
(NL) left and Expanite,
Hillerd (DK) right
12
phase and tends to decompose upon prolonged thermal exposure [16]. Nitrocarburising should not be confused with carbonitriding, which is a higher temperature process
used for low-carbon steels.
EN Name
Approximate
AISI/ASTM
Applications
302
1.4401
X5CrNiMo17-12-2
316
1.4006
X12Cr13
410
1.4031
X39Cr13
420
Valve components, plunger rods, fittings, guides, parts for chemical plants
13
Table 5. Induction-hardenable stainless steels and their approximate induction austenitising temperatures
Steel designation
14
Carbon,
in mass
%
Austenitising
temperature
C
EN Number
EN Name
Approximate
AISI/ASTM
1.4005
X12CrS13
416
< 0.15
1065
1.4021
1.4028
1.4031
1.4034
X20Cr13
X30Cr13
X39Cr13
X46Cr13
420
> 0.15
1065
1.4125
X105CrMo17
440C
0.951.20
1065
5 Costs
Cost must be weighed against the performance required from the surface-treatment
system. A low-cost surface treatment that
fails to perform its function is a wasted expense. Unfortunately, it is nearly impossible
to give absolute comparative costs for different surface-engineering options. Probably the most important factor concerning
the cost of producing a wear-resistant surface on a part is part quantity. Treating many
parts usually allows economies in treatment and finishing. Another consideration
when assessing surface-treatment costs is
part size. There are critical sizes for each
surface-treatment process above which the
cost of obtaining the treatment may be high.
Other factors to be considered are:
15
6 Summary
There are several processes by which the
surface of stainless steels can be successfully hardened. These processes not only
improve the hardness of the surface but also
increase the materials scratch and wear
resistance. Such surfaces are also used in
applications where galling is an issue or
cutting edges are required (for example, in
medical equipment). All processes showed
in this publication are based on altering the
original surface without an additional layer
being applied, which might peel or wear off.
16
7 References
[1] Expanite Surface Hardening of Stainless Steel, available from http://www.expanite.com/
[2] Specialty Stainless Steel Processes (S3P) Benefits available from http://www.bodycote.com/services/heat-treatment/specialty-stainless-steel-processes.aspx
[3] Stainihard NC Surface Hardening of Stainless Steel, Heat &Surface Treatment B.V.,
available from http://www.stainihard.nl/
[4] Formosa, D., Hunger R., Spiteri, A., Dong, H., Sinagra, E., & Buhagiar, J. (2012) Corrosion behaviour of carbon S-phase created on Ni-free biomedical stainless steel, Surf.
Coat. Technol., 206, 34793487
[5] Hunger H.-J., Wear Protection by Boronizing, available from http://www.bortec.de/
images/bortec/wear_protection_e.pdf
[6] Handbook of Hard Coatings, Deposition Technologies, Properties and Applications,
edited by R.F. Bunshah, Noyes Publications, 2001
[7] Surface Hardening of Steels, Understanding the Basics, edited by J.R. Davis, ASM International 2002
[8] Christiansen, T.L., Somers, M.A.J., Characterisation of Low Temperature Surface Hardened Stainless Steel, Struers Journal of Materialography 9/2006
[9] ASM Specialty Handbook, Stainless Steels, edited by J.R. Davis, ASM International, 1994
[10] Kumar, T., Jambulingam, P., Gopal, M., Rajadurai, A. Surface Hardening of AISI 304,
316, 304L and 316L SS Using Cyanide Free Salt Bath Nitriding Process, ISRS, 2004
[11] Kolsterising, Bodycote, available from http://internet.bodycote.org/kolsterising/
brochures/147-302_body_kolst_rd_gb_finr.pdf
[12] Faccoli, M., Cornacchia, G., Roberti, R., Bordiga, V., Effect of Kolsterising Treatment on
Surface Properties of a Duplex Stainless Steel, 7th European Stainless Steel Conference
Science and Market, 2011
[13] Van Der Jagt, R. H., Kolsterising surface hardening of austenitic and duplex stainless
steels without loss of corrosion resistance. Heat Treatment of Metals (2000), Issue 27,
pp. 62 - 65
[14] Heat Treaters Guide, Practices and Procedures for Irons and Steels, edited by H.
Chandler, ASM International, 1995
[15] Hummelshj, T.S., Christiansen, T.L., Somers, M.A.J., Towards Commercialisation of Fast
Gaseous Nitrocarburising of Stainless Steel, available from http://www.expanite.com/
papers/DMS2010_Towards.pdf
[16] Christiansen, T.L., Hummelshj, T.S., Somers, M.A.J, Low Temperature Thermochemical
Treatment of Stainless Steel; Bridging from Science to Technology, 7th European Stainless Steel Conference Science and Market, 2011
[17 Hunger, H. J.; Trute, G.; Lbig, G., Rathjen, D.: Plasmaaktiviertes Gasborieren mit
Bortrifluorid. HTM 52 (1997) 1, pp. 39-45
[18] Induction Hardening, Bodycote, available from http://www.bodycote.com/services/
heat-treatment/harden-and-temper/induction-hardening.aspx
17
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