Martensitic stainless steel

Martensitic stainless steel is a type of stainless steel alloy that has a martensite crystal structure. It can be hardened and tempered through aging and heat treatment.^[1]^[2]^[3]^[4] The other main types of stainless steel are austenitic, ferritic, duplex, and precipitation hardened.^[5]

History

In 1912, Harry Brearley of the Brown-Firth research laboratory in Sheffield, England, while seeking a corrosion-resistant alloy for gun barrels, discovered and subsequently industrialized a martensitic stainless steel alloy. The discovery was announced two years later in a January 1915 newspaper article in The New York Times.^[6] Brearly applied for a U.S. patent during 1915. This was later marketed under the "Staybrite" brand by Firth Vickers in England and was used for the new entrance canopy for the Savoy Hotel in 1929 in London.^[7]

The characteristic body-centered tetragonal martensite microstructure was first observed by German microscopist Adolf Martens around 1890. In 1912, Elwood Haynes applied for a U.S. patent on a martensitic stainless steel alloy. This patent was not granted until 1919.^[8]

Overview

Martensitic stainless steels can be high- or low-carbon steels built around the composition of iron, 12% up to 17% chromium, carbon from 0.10% (Type 410) up to 1.2% (Type 440C):^[9]

Up to about 0.4%C they are used mostly for their mechanical properties in applications such as pumps, valves, and shafts.
Above 0.4%C they are used mostly for their wear resistance, such as in cutlery surgical blades, plastic injection molds, and nozzles.

They may contain some Ni (Type 431) which allows a higher Cr and/or Mo content, thereby improving corrosion resistance and as the carbon content is also lower, the toughness is improved. Grade EN 1.4313 (CA6NM) with a low C, 13%Cr and 4%Ni offers good mechanical properties, good castability, and good weldability. It is used for nearly all the hydroelectric turbines in the world, including those of the huge "Three Gorges" dam in China.

Additions of B, Co, Nb, Ti improve the high temperature properties, particularly creep resistance. This is used for heat exchangers in steam turbines.

A specific grade is Type 630 (also called 17-4 PH) which is martensitic and hardens by precipitation at 475 °C (887 °F).

Chemical compositions

Chemical composition of a few common martensitic stainless steel grades from EN 10088-1 (2005) standard
Chemical composition (main alloying elements) in wt%
EN Steel designation	EN Number	AISI Number
Number			C	Cr	Mo	Others	Remarks
X12Cr13	1.4006	410	0.12	12.5	—	—	Base grade, used as stainless engineering steel
X20Cr13	1.4021	420	0.20	13.0	—	—	Base grade, used as stainless engineering steel
X50CrMoV15	1.4116	-	0.50	14.5	0.65	V: 0.15	Used chiefly for professional knives
X14CrMoS17	1.4104	430F	0.14	16.5	0.40	S: 0.25	Sulphur improves machinability
X39CrMo17-1	1.4122	-	0.40	16.5	1.10	—	Used chiefly for professional knives
X105CrMo17	1.4125	440C	1.10	17.0	0.60	—	Tool steel grade (440C), high wear resistance
X17CrNi16-2	1.4057	431	0.17	16.0	—	Ni: 2.00	Ni replaces some C for higher ductility & toughness
X4CrNiMo16-5-1	1.4418	-	≤ 0.06	16.0	1.10	Ni: 2.00	Highest corrosion resistance of martensitics
X5CrNiCuNb16-4	1.4542	630 (17-4PH)	≤ 0.07	16.0	-	Ni: 4.00 Cu: 4.00 Nb: 5xC to 0.45	Precipitation hardening grade High strength. Used in aerospace

There are many proprietary grades not listed in the standards, particularly for cutlery.

Mechanical Properties

They are hardenable by heat treatment (specifically by quenching and stress relieving, or by quenching and tempering (referred to as QT).^[10]^[11] The alloy composition, and the high cooling rate of quenching enable the formation of martensite. Untempered martensite is low in toughness and therefore brittle.Tempered martensite gives steel good hardness and high toughness as can be seen below; used largely for medical tools (scalpels, razors and internal clamps).^[12]

Mechanical properties of a few common martensitic stainless steel grades according to EN 10088-3 Standard
EN	Mininmum Yield stress	Tensile strength	Minimum Elongation, %	Heat treatment
1.4006	450 MPa (65 ksi)	650–850 MPa (94–123 ksi)	15	QT650
1.4021	600 MPa (87 ksi)	650–850 MPa (94–123 ksi)	12	QT800
1.4122	550 MPa (80 ksi)	750–950 MPa (109–138 ksi)	12	QT750
1.4057	700 MPa (100 ksi)	900–1,050 MPa (131–152 ksi)	12	QT900
1.4418	700 MPa (100 ksi)	840–1,100 MPa (122–160 ksi)	16	QT900
1.4542	790 MPa (115 ksi)	960–1,160 MPa (139–168 ksi)	12	P960

In the heat treatment column, QT refers to Quenched and Tempered, P refers to Precipitation hardened

Physical properties

Physical properties of a few common martensitic stainless steels from EN 10088-1 (2005) standard
EN Designation	EN	AISI	Young's Modulus at 20 °C (68 °F), Gpa	Mean coefficient of thermal expansion between 20 and 100 °C (68 and 212 °F) 10⁻⁶K⁻¹.	Thermal Conductivity at 20 °C *W m⁻¹K⁻¹**	Specific Thermal capacity at 20 °C *J Kg⁻¹ * K⁻¹**	Electrical resitivity 10⁻⁶Ω * m
X12Cr13	1.4006	410	215 GPa (31.2×10^⁶ psi)	10.5	30	460	0.60
X20Cr13	1.4021	420	215 GPa (31.2×10^⁶ psi)	10.5	30	460	0.65
X50CrMoV15	1.4116	420MoV	215 GPa (31.2×10^⁶ psi)	10.5	30	460	0.65
X39CrMo17-1	1.4122		215 GPa (31.2×10^⁶ psi)	10.4	15	430	0.80
X105CrMo17	1.4125	440C	215 GPa (31.2×10^⁶ psi)	10.4	15	430	0.80
X17CrNi16-2	1.4057	431	215 GPa (31.2×10^⁶ psi)	10.0	25	460	0.70
X3CrNiMo13-4	1.4313		200 GPa (29×10^⁶ psi)	10.5	25	430	0.60
X4CrNiMo16-5-1	1.4418		195 GPa (28.3×10^⁶ psi)	10.3	30	430	0.80
X5CrNiCuNb16-4	1.4542	630	200 GPa (29×10^⁶ psi)	10.9	30	500	0.71

Processing

When formability, softness, etc. are required in fabrication, steel having 0.12% maximum carbon is often used in soft condition. With increasing carbon, it is possible by hardening and tempering to obtain tensile strength in the range of 600 to 900 MPa (87 to 131 ksi), combined with reasonable toughness and ductility. In this condition, these steels find many useful general applications where mild corrosion resistance is required. Also, with the higher carbon range in the hardened and lightly tempered condition, tensile strength of about 1,600 MPa (230 ksi) may be developed with lowered ductility.

A common example of a Martensitic stainless steel is X46Cr13.

Martensitic stainless steel can be nondestructively tested using the magnetic particle inspection method, unlike austenitic stainless steel.

Applications

Martensitic stainless steels, depending upon their carbon content are often used for their corrosion resistance and high strength in pumps, valves, and boat shafts.^[4]

They are also used for their wear resistance in, cutlery, medical tools (scalpels, razors and internal clamps),^[12] ball bearings, razor blades, injection molds for polymers, and brake disks for bicycles and motorbikes.

References

^ "Premium Alloys 17-4 Stainless Steel". Retrieved 2019-11-26.
^ "Classifications of Stainless Steel". aws.org. American Welding Society. Retrieved 2019-04-02.
^ D. Peckner and I.M. Berstein (1977). Handbook of stainless steels. Mc Graw Hill. pp. Chapter 6. ISBN 978-0070491472.
^ ^a ^b "Martensitic Stainless Steels". International Stainless Steel Forum. 2018.
^ The International Nickel Company (1974). "Standard Wrought Austenitic Stainless Steels". Nickel Institute. Archived from the original on 2018-01-09. Retrieved 2018-01-09.
^ "A non-rusting steel". New York Times. 31 January 1915.
^ Sheffield Steel, ISBN 0-7509-2856-5.
^ Rodney Carlisle; Scientific American (2005-01-28). Scientific American Inventions and Discoveries: All the Milestones in Ingenuity – From the Discovery of Fire to the Invention of the Microwave Oven. John Wiley & Sons. p. 380. ISBN 978-0-471-66024-8.
^ http://metals.about.com/od/properties/a/Steel-Types-And-Properties.htm, http://www.totalmateria.com/page.aspx?ID=CheckArticle&site=kts&NM=199.
^ Dossett, Jon L; Totten, George E., eds. (2014). Heat treating of irons and steels. ASM International. pp. 382–396. ISBN 978-1-62708-168-9.
^ Budynas, Richard G. and Nisbett, J. Keith (2008). Shigley's Mechanical Engineering Design, Eight Edition. New York, NY: McGraw-Hill Higher Education. ISBN 978-0-07-312193-2.
^ ^a ^b Akhavan Tabatabae, Behnam; et al. (2009). "Influence of Retained Austenite on the Mechanical Properties of Low Carbon Martensitic Stainless Steel Castings". ISIJ International. 51 (3): 471–475. doi:10.2355/isijinternational.51.471.

[Premium_Alloys-1] "Premium Alloys 17-4 Stainless Steel". Retrieved 2019-11-26.

[aws-2] "Classifications of Stainless Steel". aws.org. American Welding Society. Retrieved 2019-04-02.

[3] D. Peckner and I.M. Berstein (1977). Handbook of stainless steels. Mc Graw Hill. pp. Chapter 6. ISBN 978-0070491472.

[:0-4] "Martensitic Stainless Steels". International Stainless Steel Forum. 2018.

[5] The International Nickel Company (1974). "Standard Wrought Austenitic Stainless Steels". Nickel Institute. Archived from the original on 2018-01-09. Retrieved 2018-01-09.

[NYT-6] "A non-rusting steel". New York Times. 31 January 1915.

[7] Sheffield Steel, ISBN 0-7509-2856-5.

[CarlisleAmerican2005-8] Rodney Carlisle; Scientific American (2005-01-28). Scientific American Inventions and Discoveries: All the Milestones in Ingenuity – From the Discovery of Fire to the Invention of the Microwave Oven. John Wiley & Sons. p. 380. ISBN 978-0-471-66024-8.

[9] ttp://metals.about.com/od/properties/a/Steel-Types-And-Properties.htm, http://www.totalmateria.com/page.aspx?ID=CheckArticle&site=kts&NM=199.

[10] Dossett, Jon L; Totten, George E., eds. (2014). Heat treating of irons and steels. ASM International. pp. 382–396. ISBN 978-1-62708-168-9.

[11] Budynas, Richard G. and Nisbett, J. Keith (2008). Shigley's Mechanical Engineering Design, Eight Edition. New York, NY: McGraw-Hill Higher Education. ISBN 978-0-07-312193-2.

[:1-12] Akhavan Tabatabae, Behnam; et al. (2009). "Influence of Retained Austenite on the Mechanical Properties of Low Carbon Martensitic Stainless Steel Castings". ISIJ International. 51 (3): 471–475. doi:10.2355/isijinternational.51.471.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]