PAST PRESENT AND FUTURE OF STAINLESS STEEL

Erdal YAVUZ-Huseyin ZENGIN-Mustafa SEYREK

UNIVERSITY OF SHEFFIELD MARCH-2013

1. INTRODUCTION Stainless steel is the common name for various types of steels which contain 10.5% or more chromium by weight. The addition of chromium makes steel stainless. It has therefore been widely used in many different industries because of its unique features such as resistance to corrosion, fire and heat, as well as hygiene and strength. (BP, 2013) Scientists discovered stainless steel in the the 19th century, but there has been a much dispute regarding who actually discovered this alloy. It is generally accepted that Harry Brearley discovered stainless steel in 1913 in Sheffield England while he was working on a project to prolong the life of rifle barrels from erosion during use (The New York Times, 1915). During this project, Brearley made a certain number of alloys which contained different rate of carbon from 6% to 15%. Through his experimentation, Brearley produced a steel with 12.8 chromium and 0.24% carbon on the 13th August 1913 (BSSA, 2013).

At this time, he needed to etch his samples with nitric acid in order to examine them under a microscope. Based on nitric acid, Harry Brearley found that these steels extremely resisted chemical attacks. He then exposed his specimen to vinegar, lemon juice and other food acids but he found same results. Afterwards, he recognized how these steels could contribute to cutlery industry. He subsequently manufactured knives and initially decided to call his invention Rustless Steel but it was Ernest Stuart, the manager of Mosleys cutlery, who first used term Stainless Steel after some experiment with vinegar (VW, 2013). Accordingly, martensitic chromium stainless steel was, to an extent, accidently discovered by Harry Brearley while he was seeking corroding-resistant alloy for gun barrels (BSSA, 2013).

Between 1912 and 1914 employees of the Krupp Iron Works in Germany developed austenitic stainless steel by using 15-40% chromium, <20% nickel and <1% carbon. Ferritic stainless steel has been firstly worked by Becket and Dantsizen in America between 1911 and 1914 which contains 14-16% chromium and 0.07-0.15% carbon (BSSA, 2013). Moreover during the 1930s duplex stainless steel was produced in Sweden in order to use in sulphite paper industry (Alvarez, 2007).

2. AN OVERVIEW OF DEVELOPMENTS IN STAINLESS STEELS INTERMS OF TYPES, MARKETING AND PRODUCTION

2.1.Types and Marketing After stainless steel was discovered and commercialized, the awareness of its superior and unique properties created an appealing research area and a growing demand for an immense number of applications. Several types of stainless steels have been developed based on their microstructure so far. Those types of steels are used numerous applications: hand tools, reinforcing bars, roofing, claddings, automobile parts (exhaust, engine, fasteners etc.), marine constructions, catering equipment, kitchen appliances, water pipes, pressure vessels, chemical and surgical equipment and transportation (cars, trucks, trains etc.), to name but a few. The number of stainless steels applications and the usage rate of stainless steels have always increased due to the development of new types of stainless steels that offer lower product costs and better or comparable corrosion resistance and mechanical properties. The line graph below Fig.1 presents the growth rate of crude stainless steel production in the world for the last around 50 years. As it can be seen, the annual growth showed a gradual increase until the mid-1970s and then rose steeply until 2011 except the slight falls because of the crises. Undoubtedly, that rate will continue to go up in the future due to the developments in more advantageous new types of stainless steel alloys in terms of cost and material properties.

Figure1. Annual growth rate of world stainless crude steel production (1950 2011) 2

International Stainless Steel Forum As it is stated before, stainless steels attain their stainlessness by chromium addition at least 10.5 wt%. This composition of chromium forms a self-repairing chromium oxide on steel surface that protects steel from corrosion. The addition of some other particular alloying elements can enhance the properties of stainless steels. The major alloying elements apart from chromium are nickel, molybdenum, nitrogen and manganese. Nickel is added in high compositions, over 8%, primarily to increase the corrosion resistance, toughness and strength of stainless steels and to form heat-resisting steels with stabilizing austenite phase. Molybdenum enhances the pitting and crevice corrosion resistance of stainless steels. Despite these good properties, nickel and molybdenum are expensive elements. Because of that, in recent years, developers have been more focused on reducing the composition of these elements with trying to obtain the same or comparable properties as high nickel and molybdenum added stainless steels. For instance, nitrogen and manganese are austenite stabilizers like nickel and they provide good corrosion resistance, strength and toughness as well so that their presence can be an alternative to nickel.

Stainless steel can have mainly three different microstructures and the types of stainless steel are based on these microstructural properties. These are ferritic, austenitic and martensitic. They are achieved by changing the chemical compositions of elements in stainless steels. Apart from the main microstructure, stainless steels are divided into several classes that are ferritic stainless steels, austenitic stainless steels, martensitic stainless steels, duplex stainless steels and precipitation hardening stainless steels. Austenitic stainless steel is the most common type of stainless steels and is used for various applications. It has a FCC crystal structure and has its austenitic structure is because of the high concentration of nickel in it. Austenitic stainless steels are non-magnetic, weldable and excellent corrosion resistant materials and have good mechanical properties. Ferritic stainless steels are iron-chromium alloys and have BCC crystal structure. Although these stainless steels are ductile and formable, their high-temperature strengths are not as good as austenitic steels. Alloying with carbon and nitrogen can increase corrosion resistance to chloride. Ferritic stainless steels can be utilized in some kitchen appliances and are the most affordable stainless steels. Martensitic stainless steels have a composition balance of carbon and nickel versus chromium and molybdenum. The carbon content of these stainless steels influences the formability and weldability properties. Duplex stainless steels have almost the same amounts of ferrite and austenite structure. These types of steels include around 21-25 % chromium and 5% nickel 3

with a small amount of nitrogen and molybdenum. In recent years, duplex stainless steels have become very popular and preferable type of stainless steels due to their competitive properties. These steels may have greater strength and corrosion resistance and lower cost than any other types of stainless steels. Besides, leaner duplex steels can offer much less cost and comparable properties due to the low compositions of expensive alloying elements such as nickel and molybdenum. Precipitation hardening stainless steel contain chromium and nickel but have different alloying elements that can form precipitates to increase the strength. The alloying elements can be aluminum, copper or titanium.

Figure 2. Stainless Steels Family Chart

2.2.Production of Stainless Steels With particular restrictions in some types, stainless steels could be fabricated and shaped in traditional ways. The manufacturing processes are casting, wrought form production and powder metallurgy (P/M). A wrought stainless steel product can form as wire, strip, plate, sheet, pipe, bar, tubing and semi-finished products such as blooms, slabs, and billets. Most of the stainless steel products are plate, sheet and strip (cold-rolled flat products). Figure 3 4

demonstrates the most common mill processes for producing numerous wrought products of stainless steel. The production process of stainless steels consists of two main steps (ASM, 2000).

Figure 3. Manufacturing process of stainless steels

First stage is the ferroalloys and scrap melting process in electric arc furnace (EAF) and the second stage is the refinement process by argon oxygen decarburization (AOD) illustrated in Figure 4. AOD adjusts the carbon composition and removes impurities. It is the most economical method for stainless steel production with minimizing the loss of precious elements (ASM, 2000).

Figure 4. Argon Oxygen Decarburization (AOD) Process

The main advantage of the combination of EAF and AOD is the size. EAF can supply 45000 pounds of powder, which is a much larger amount of powder than that of induction furnace (1000-4000 pounds). Therefore, some properties such as flow, density, sintered and green properties are kept constant by production in one batch with such that large capacity. Another advantage of the EAF/AOD process is decarburization. The oxidation of carbon in AOD is more preferential than that of chromium. Hence, the wider range of materials can be used such as green scrap and high carbon ferro-chromium. Decarburization is obtained in liquid steel by the oxidation of carbon so that carbon monoxide is released from the melt (Ian, 2002).

Alternatively, for melting process; electron beam melting, vacuum induction melting, electroslag remelting and vacuum arc remelting can be used. However, electric arc furnace (EAF) and argon oxygen decarburization (AOD) are the most commonly employed melting and refining processes for stainless steel production. For the mill forms of sheet, plate, bar and strip, the final stage consist of annealing, hot reduction, cold rolling and cleaning whereas there are further processes for the forms such as tube and wire to give the stainless steel product required size (Ian, 2002).

3. Applications of Stainless Steel 3.1. Stainless Steel in Buildings and Civil Engineering Stainless steels have not been considered as indispensable structural materials for all civil engineering applications. There have always been some imperative needs in where the stainless steels have been used such as bridges, roofs, dams, parking garages, tunnels, sea walls, claddings and so on. The major requirements that make stainless steels more desirable for those applications than other conventional structural steels are primarily high corrosion and staining resistance, low maintenance, longevity and aesthetic purposes. Furthermore, stainless steels could meet all expectations as structural materials in terms of mechanical properties. However, the use of stainless steel in structural applications has remained low because of its high cost. Today, developments in new types of stainless steel are providing with an opening for the future of stainless steel with bringing down the cost of stainless steels in civil engineering applications. Stainless steel refers to a broad range of types and alloys. For civil engineering applications, there are two main alloys: the austenitic and duplex stainless steels. Both these types contain 6

iron, chromium, nickel and molybdenum. As it is well known, the corrosion resistance of stainless steels is highly dependent on the composition of chromium and it can be increased by nitrogen and molybdenum. Nickel ensures the fine microstructure and good mechanical properties of the steel (Lo&Shek&Lai, 2009).

In civil engineering applications, selecting an appropriate grade of stainless steel is based highly on the factors that are related to corrosion risk of environment and properties of stainless steel. These factors may include exposure to chloride, micro and macro environmental effects, surface roughness and ability of corrosion resistance at joints (fabrications effect) (Gedge, 2008).

Austenitic stainless steels have always been the most prevalent type of stainless steels in civil engineering applications by engineers. High composition of nickel in austenitic stainless steels stabilizes austenitic structure, enhances ductility and workability. Moreover, hot-rolled austenitic steels have excellent toughness and weldability. However, the mill cost of stainless steels is highly dependent on nickel (rare element) content because the influence of the prices of nickel is the most important factor on keeping out stainless steel with high nickel and molybdenum compositions from all civil engineering applications. As it can be seen from table 1 and table 2, austenitic stainless steels have larger compositions of nickel than that in duplex stainless steels. Therefore, it can be deduced that austenitic stainless steels are the most affected by the nickel price which has experienced a significant fluctuation because of stock market factors (Gedge, 2008).

Table 1. Composition of three alloys of austenitic stainless steel.

For many civil engineering applications, duplex stainless steels have become an appealing alternative to austenitic stainless steels in recent years on account of their excellent strength

and low expense for raw materials or alloying elements. Both the significance of conservation of the rare elements (primarily nickel and molybdenum) and the need for reducing the cost of final product bring about new developments effectively in duplex stainless steels with low nickel and molybdenum content. These types are called lean duplex stainless steels. The compositions of two types of lean duplex steels (1.4162 and 1.432) are shown in Table 2. As it can be seen from the table, lean duplex steels have much less nickel and molybdenum composition than established duplex and austenitic steels. Lean duplex stainless steels can also be as high strength as traditional duplex steels and as high corrosion resistance as established austenitic stainless steels with affording low cost. Therefore, it can be predicted that these steels will be chosen over other types of stainless steels for construction purposes (Baddoo&Burgan, 2001; Gedge, 2008; Lo&Shek&Lai, 2009).

Table 2: Composition of four alloys of duplex stainless steel.

A corrosion resistance comparison between duplex and austenitic steels is shown below in Figure 1. 1.4462 type steels are the most suitable for all circumstances but not as economical as 1.4301 and LDX2101. Unless there is an extreme corrosive environment, LDX2101, which is a type of lean duplex stainless steel, would be the best choice considering its low cost.

Figure 5. Comparison of corrosion resistance of duplex and austenitic stainless steels It is likely that the tendency to increasing usage of duplex and lean duplex stainless steels as structural materials will carry on in the future with regard to low material cost, high strength and comparable corrosion resistance. The awareness of the advantages of duplex stainless steels has encouraged researchers to develop competitive alloys of stainless steel for civil engineering applications. Taking into account of production cost of steel making and variable prices of alloying elements designated by The Alloy Adjustment Factor (AAF), lean duplex stainless steels step forward as structural materials due to low compositions of expensive alloying elements combining with comparable mechanical properties and corrosion resistance and these are projected to be widely used in civil engineering applications. In addition to the improvements in lowering fabrication cost of stainless steels, avoiding from the potential expensive and disrupting maintenance and the need for sustainable structures are significant for civil engineering applications. As long as leaner stainless steels meet these requirements, they can be expected to be the most preferred structural materials in all civil engineering applications in the near future.

3.2 Stainless Steel in Food and Beverage Industry The invention of stainless steel at the beginning of the 20th century was very important milestone for the food and beverage industries. Stainless steel has been chosen in the food industry because it is resistant to corrosion, inert and it surfaces can be easily cleaned. It can also be produced with several techniques, relatively easy to recycle and can exhibit an eye catching appearance (Newson, 2003). Stainless steels have, therefore, been substantially used in kitchen equipment for the preparation, storage, and food displays (SSAS, 2000). As the material can be easily cleaned it has played important role in improving kitchen equipment hygiene. Stainless steels cleanability is similar to that of glass and porcelains, but superior to plastics (Mohan, 2012). Moreover, stainless steel in contact with food or beverage, than this situation may affect colour and taste. The property of stainless steels surface finish can not only provide cleanability and corrosion resistance, but also preserve food colour or smell (SSAS, 2000).

Table 3. Typical Applications of Stainless Steels used in Food Preparation. (SSAS, 2000)

Most foodstuff and drinking water contact material in stainless steels are widely produced from austenitic stainless steel because of its perfect corrosion resistance, fabrication feature and great deal of mechanical properties. Martensitic stainless steel is vastly used for cutlery and grinding equipment. Besides, high-quality knives are manufactured by martensitic stainless steel which contain high carbon, vanadium and molybdenum (T. Newson, 2003). Furthermore, ferritic and duplex stainless steels have also used in food and beverage industry. Table 1 illustrate the applications of stainless steel which is used in food industry. Currently, approximately 38% of all stainless steel have been manufactured for food and beverage industry and also it has begun to use in new area such as sugar industry. Sugar is highly corrosive on various kinds of metals. Ferritic stainless steel, however, can be used to 10

use in sugar industry machinery in order to enhance performance. Nevertheless, even though CS444 stainless steel is not normally used in drinks industry, it is used du its suitability for this application. Moreover, ferritic stainless steel has thus replaced 304 austenitic stainless steel for industrial kitchen hob applications (ASSDA, 2006). The consumption of duplex stainless steel has substantially increased as a result of greater food and beverage applications. It is also a suitable steel for storage tank application because of its high strength and cost reduction. Moreover, its corrosion resistance is better than austenitic stainless steel: this property therefore makes it attractive to manufacturers (OUTOKUMPU, 2010).

3.3.

Stainless Steel in Medical Devices

Stainless steels are used for medical purposes approximately for 90 years. It means that medical devices are one of the main application fields of stainless steels. As looked at historical background, chronology could be shown briefly as follow;

In 1926, E. W. Groves used screws which are made of 18-8 Cr-Ni austenitic stainless steel for fixing of femoral neck fractures. In 1936, Intermedullary nail produced stainless steel was used for comminuted ulna fracture by Rush. In 1947, American College of Surgeons decided that 19Cr-9Ni and 18Cr-8Ni Stainless steel alloys were suitable for implantation. In 1958, The use of stainless steel for hip components, Charnley practised with the total hip replacement In 1960s, To correct spinal curvature, Rods known Harrrington rods were developed. In 2000s, Nickel Free stainless steels are being researched (Heubner&Wedohl,2009).

Today, A wide range of medical applications where they come into contact with human tissue and skin are made from stainless steels. This situation could be explained that stainless steels are expected to perform without any negative effetcs on health system

(Santonen&Stockman&Zitting, 2010).

Within Medical devices, Implants are more concerned materials so they are generaly made of austenitic type of stainless steel. The essential reasons are that austenitic stainless steels

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have excellent ductility, toughness, formability, ductility and also they are non-magnetic (Bombac&Brojan&Krkovic, 2007).

Figure 6. A Picture of Knee and Hip Implant

However, typical austenitic stainless steels contain 8-10 % Ni. So the presence of high quantity of nickel , these materials have toxic and allergic effects on human body. The Ni ions could cause cutaneous iflammations which has negative reactions such as eczema, reddening, and itching for the itching. Therefore Nickel is the critical element in austenitic stainless steels which can impart FCC crystal lattice due to Nickel content. It means Nickel is the most effective austenite stabilizer element. Moreover, Nickel has price speculation in Metal World beacuse of high cost and low availability (Bombac&Brojan&Krkovic, 2007).

As taken account of all these issues, If Nickel-Free stainless steel is being expected to be common, it means that we need another austenite stabiliser alloying element. Recent researches focus on Nitrogen which would be used austenite austenite forming element . In addition, Researches showed that nitrogen makes austenitic stainless steel stronger and more wear and fatigue resistant. Moreover Nitrogen can be found everywhere easily. (i.e. no more speculations on cost). Therefore It is expected that nitrogen containig austenitic stainless steels ( known 200 series stainless steel ) would be more considerably used in the future

(Bombac&Brojan&Krkovic, 2007).

As mentioned earlier, Austenitic stainless steels are non-magnetic materials. Implants are checked out regularly and this could only be possible using MRI method. Because widespread use of magnetic resonans imaging , Implants must not be affected by strong magnetic field (Bombac&Brojan&Krkovic, 2007). 12

Now another important application field which concerns Medical is Surgical devices. Easy cleaning and sterilisation of these instruments are so important. These are known as Nonimplant medical devices. Generally , Martensitic and austenitic stainless steels are used for making these tools such as clips, scissors, forceps but mostly martensitic stainless steels to keep sharp tools and harder than austenitic stainless steel. However, Martensitic stainless steels could be corrode and stain more likely than others because of higher carbon content and It is known that blood is a highly corrosive and surgical instruments are generally subjected to blood (Bombac&Brojan&Krkovic, 2007).

Figure 7. Some Surgical Instruments

4. CONCLUSION Stainless steels are known Iron-Chromium-Nickel alloys and alloying elements are added to enhance their microstructure and make main requirements possible. Stainless steels have unique values that make hem useful for materials engineer and designers. Generally, stainless steels provide good corrosion resistance and a wide range of mechanical and physical properties for intended applications. They have played inestimable role to the well being of humankind. However , Their duty are set to carry on to the future by providing current and future needs.

If we look at the production rate of world crude stainless steels annualy at Fig 1 , we would see that the amount of demanding stainless steel would not decrease in the future. Conversely, stainless steels are getting popular in the world. 13

Among stainless steel types austenitic stainless steels cover a great majority of stainless steel market with. However, Duplex stainless steels are being search to replace other grades with some effective properties, even though they cover just 1 percent of total stainless steel market.

Today , Recyclability is the key for environmental issues.Corrosion resistance of stainless steels provide 100 per cent recyclability. This has positive effects on recovery on scraps. These scraps can be charged into directly melting furnace. So All these make stainless steels sustainable materials.

Material selection and design criteria cause new seekings and New grades stainless steel series could appear largely. These are mainly results of economical and environmental issues and also meeting needs of desirable applications. For example, Arcelor Mittal has designed a new grade, K44X, stainless steel to meet demanding higher temperature resistance in automotive industry because of smaller engines being used.

All new developments are to meet higher corrosion resistance, mechanical strength, fatigue and wear resistance. However, Nickel Free stainless steels are being researched due to the fact that Nickel prices are getting higher because of low availability and also nickel has negative effetcs on human body and tissue. It seems nitrogen would take place of nickel in foreseeable future.

Finally, Stainless steels establish a quite wide market presence from domestic to medical, and also from food and drink to transportation because of their good properties.

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References: ASM, 2000, Introduction to Stainless Steel, Available: http://www.asminternational.org/content/ASM/StoreFiles/06940G_Chapter_1.pdf (Accessed: 2013, March 5)

ASSDA, 2006, September, Industrial Meat Processing Machinery, Available: http://www.worldstainless.org/Files/issf/non-imagefiles/PDF/FoodandBeverageIndustry_2009.pdf (Accessed: 2013, March 12)

Baddoo, N., Burgan, B., 2001, Structural design of stainless steel, SCI P291, SCI 2001. Bombac,D., Brojan,M., Krkovic,M., 2007, Characterization of titanium and stainless steel medical implant surfaces, Materials and Geoemvironment, 54(2), p.151-164

BSSA, 2001, March 12, SSAS Information Sheet No.3.21, Available: http://www.bssa.org.uk/cms/File/SSAS3.21Stainless%20Steels%20for%20Food%20Processing%20Industries.pdf(Accessed:2013, March 5)

BSSA, 2007, The Discovery of Stainless Steel, Available: http://www.bssa.org.uk/about_stainless_steel.php?id=31 (Accessed: 2013, March 7)

BP, 2013, All About Stainless Steel, Available: http://www.berkeleypoint.com/learning/stainless.html (Accessed: 2013, March 11)

Heubner, U.,Werdohl, D., 2009, Stainless Steel-When Health Comes First, Environment and Human Health Series 2, P.1-40

Gedge, G., 2008, Structural uses of stainless steel buildings and civil engineering, Journal of Constructional Steel Research, 64 (3), p1194-1198. 15

Lo,K.H., Shek,C.H., Lai,J.K.L., 2009, Recent developments in stainless steels, Materials Science and Engineering, 65 (3), p39-104

Ian, A.W., 2002, Stainless Steel Powders Manufacturing Techniques and Applications, Stainless Steel Powders, pp.90-115

Iris Alvarez(2007, October 2) Duplex Stainless Steel: Brief History and Some Recent Alloys Recent Patents on Mechanical Engineering,1,p. 51-57

OUTOKUMPU, 2010, November, Stainless steel for the food and drink industry, Available: http://www.outokumpu.com/SiteCollectionDocuments/Stainless_for_food_and-drinkBrochure.pdf (Accessed: 2013, March 12)

Santonen,T., Stockmann,H., Zitting,A., 2010, Review on Toxicity of Stainless Steel, Finnish Institute of Occupational Health, p.1-87

Tony Newson, 2003, Stainless Steel for Hygienic Applications, BSSA Conference: 2

V.Mohan , 2012, Hygienic importance of stainless steel in developing countries, International Stainless Steel Forum: 1

V.W., 2013, A Brief History of Stainless Steels, Available: http://www.valveworld.net/basicfacts/ShowPage.aspx?pageID=462 (Accessed: 2013, March 11)

The New York Times, 1915, January 31, History of Stainless Steel Alloys, Available: http://www.aerodynealloys.com/products/stainless/history.php (Accessed: 2013, March 9)

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