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Hard Outer Coatings: Nitriding James Nix Material Engineering 3451 12/10/11

Table of Contents Abstract pg.3 Introduction. pg.4 Crystal Structure Aspects. pg.6 Nitriding Process pg.8 Properties Characterization.. pg.11 Summary pg.13 References. Pg.14

Abstract This research will help determine which nitriding techniques are most effective for different applications. Nitriding is a very popular treatment that results in a hard outer coating, improved corrosion resistance, and no negative deformations plus it is cheap when compared to other techniques. The history, process, and properties will discussed followed by a summary that will conclude the results of the research of the nitriding process. The high hardness found in the outer casing and corrosion resistance found after treatment has many applications that are useful in everyday applications.

Introduction Since its development in the early 1900s, nitriding has played an important role in industry when changing the mechanical properties of metals. Nitrided products can be found in a variety of products where hardness and corrosion resistance are necessary requirements of the material being used. Nitrided materials are very popular because the treatment process is fairly simple to perform. The main reasons behind nitriding include increased hardness at the surface, wear resistance, fatigue life, corrosion resistance and heat resistance. Before nitriding was developed carburizing was the primary heat treatment performed to increase hardness in steel. In this process steel would be heated to its critical temperature for an extended period of time, while heated charcoal would be applied to the steel followed by rapidly cooling the steel by quenching. The implanted carbon from the charcoal would leave a higher carbon content on the surface which would form a hard martensite structure on the outer surface. Although the required hardness can be achieved by carburization there is no added protection against corrosion at the end of the process and due to the high heat exposure deformation occurred. The first pioneer in nitriding was Adolf Machlet, an engineer for a petroleum company in New Jersey. The drilling tools used by the company often failed due to two reasons. First their lack of corrosion resistance and hardness hardness at high temperatures would cause premature failure in the equipment. Second the parts were exposed to high heat during the carburization causing distorted products that did not work as intended. After experimenting with different techniques he realized that nitrogen gas, once heated, would diffuse through steel and produce the desired results. Machlet

work was ahead of its time and was forgotten for years until Adolf Fry, from Germany picked up where Machet left off. Similar to Machlets technique, Fry used ammonia as the nitriding source but did not use hydrogen to control the process. This process is the same single-stage nitrization used today. More importantly, Fry discovered that steels with higher alloy contents produced a final product with a higher hardness. This discovery also brought about the creation and production of new specialized high alloy steels to be used in the process. In the United States Frys work was followed by McQuaid and Ketcham. After two years of research McQuaid and Ketcham significantly improved the process by maximizing the process at a lower temperature. Frys technique ranged from 480 to 980C while McQuaid and Ketchams technique only required temperatures from 540 to 650C. These lower temperatures also helped lower the cost of the process making it a more popular choice for the consumer when deciding between carburization and nitriding. They also discovered that the higher temperatures used by Fry had some negative effects on the steel such as lowered the hardness in the core of the steel. Another negative effect on the steel from these more extreme temperatures resulted in nitride networks at the corners of the products which are known to cause premature failure in the products. The two conducted 2 years worth of experiments isolating different variables and then testing the 5itride products, they made many important discoveries as far as nitriding is concerned and eventually concluded that nitriding is in most cases better than carburizing.

Crystal Structural Aspects The resulting crystal structure of the nitriding process is pretty unique when compared to other heat treating processes. The typical nitriding process occurs at temperatures ranging from 620 to 730C. The chart above shows that at this range of temperatures the molecular structure of the steel does not change during heat treatment to a face-centered cubic lattice typically found in austenite after carburization and instead it remains in the bodycentered cubic lattice. This eliminates any change in molecular size and most importantly any change of size in the final product. When the product has received proper prior initial treatment, such as annealing, beforehand there will be virtually no internal stresses at the end of nitriding.

The key to the nitriding process is controlling the temperature since the solubility of nitrogen in iron is temperature dependent, for example at 450C iron will accept 5.7 to 6.1% of the Nitrogen. After this the steel will begin to form the epsilon phase ( ) and gamma prime ( ), also known as the white layer which will be discussed later. The next variable to watch is the weight percent carbon; the higher the carbon content within the steel, the higher the epsilon level will be in the nitrided product. As the temperature increase up to 490C more gamma prime phase will be present. Once a temperature of 490C the solubility of the steel begins to drop off until it is basically nonexistent after about 650C. The important things to remember to control during nitriding include: y y y y Temperature of Furniture Time Gas Flow Weight Percent Carbon

Nitriding Process Nitriding is a surface hardening technique resulting from the diffusion of nitrogen into steel and the precipitation of nitrides after holding the metal at the required temperature. There are three different types of nitriding including gas, plasma, and a salt bath and each have some slightly different characteristics than the other methods. It is important to have already completed the hardening & tempering of the product to eliminate volumetric growth during the process.
 

There are a few initial steps required before the nitriding process to achive the best results. The first is to complete all prior heat treatments. Certain alloys require different heat treatments before they are susceptible to the nitriding process. The typical heat treatments that are preformed range from 620 to 730C. This initial heat treatment increases the core strength and helps the final product acquire the maximum hardness, if tempering is required in the

product it is performed next. After the initial heat treatment and tempering is finished the user can move onto surface preparation. Since nitriding is a white glove treatment, or a treatment in which all oils and grit must be removed from the exterior prior to completing the nitriding a special process, shown above, is followed to ensure cleanness. If decarburization is left on the surface is not removed before the nitriding process the case will spall and flake. The next step in the process is the actual nitriding process. As mentioned earlier there are three different types of nitriding available; gas, salt bath, and plasma. All the process follow the same basic procedure except they have different delivery methods for the nitride. First the products to be treated are loaded onto special racks. Next the racks with the products are lowered into sealable tanks to be treated. The next step is where the difference in the processes occurs. In the gas treatment heat is added to the tank until it reaches a temperature of 620 to 730C and then ammonia is added into the tank. The ammonia breaks down in the heat creating hydrogen gas and nitrogen gas. Once the nitrogen gas has broken away from the ammonia it is free to diffuse into the steel. In the salt bath the racks are lowered into molten salt molten salt. In the salt bath process cyanide is decomposed into cyanate releasing nitrogen from the salt to be diffused into the steel surface. The third method uses plasma to heat the steel surface and supply the nitrogen ions. The plasma technique does not require any chemical reactions to occur as in the other techniques because it is uses the ionization of single nitrogen atoms resulting in a much faster process. During the plasma nitriding the steel actually begins to glow a light pink color. When first developed in the early 1930s the process was to complex to produce repeatable results due to a lack in technology.

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During World War II research on plasma technology led to major advancements in plasma technology in general which helped the process become am accepted industrial technique by the early 1970s. As plasma technology has become more readily available the techniques popularity has increased.

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Properties Characterization The primary reason for performing the nitriding process on steel products is the case hardening obtained without the negative effects of carburization. The hardest results can be achieved with alloy steels containing .85 to 1.50% aluminum, when these steels are 11itride AIN particles are formed which strain the ferrite lattice. The strain on the ferrite lattice then creates strengthening dislocations in the steel which typically results in a very high surface hardness, about 67 HRC. The hardest part of the final product is in the white layer formed around the steel is approximately .0002 to .002 of an inch depending on the length of the cycle and what elements make up the steel. The white layer is very hard and brittle and is made up entirely of the gamma prime and epsilon phases. This layer can be undesirable in some applications because as hardness increases so does the brittleness. The white layer sometimes has a tendency to flake and spall during use so often the process is tailored to reduce this later as much as possible. The diffused layer is softer, about 40 HRC. This layer is important because it increases the yield strength of the product making it more impact resistant. When combining the two layers the final product exhibits high hardness and overall toughness.

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Another great benefit of nitriding is the corrosion resistance due to precipitation of CrN and the outer casing elements found in the white layer. One product that nitriding, particularly salt bath nitriding, is becoming increasingly popular in is treating barrels. In the past barrels have been chrome lined to help the barrel last longer although chroming the bore of the barrel is difficult and often results in poor accuracy due to uneven applications. WASP treatment, or weapons armament surface protection, is a nitriding process used by the military to surface harden the bore of the barrel to extend the number of cycles the barrel can withstand during its life. Since there is virtually no deformation there is no decrease in accuracy after treating. Corrosion resistance properties also decrease the friction between the bullet and the bore increasing the muzzle velocity and decreasing the wear on the barrel. The corrosion resistance also helps the bore resist carbon build-up from the burning gun powder, again increasing the muzzle velocity and also making wasp treated barrels easier to clean and maintain than barrels with other treatments. CMMG is the leader in using nitriding and has performed it on all their ar-15 platforms for the last 2 years and is beginning to apply it on more of their weapon systems as its popularity has increased.

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Summary In summary nitriding is a very useful final technique that can be used on products such as gears, crankshafts, diecast tools, and many other products requiring a high hardness and corrosion resistance. The softer inner core helps improve the fatigue life and improve its resistance to wear. Unlike carburization nitriding is performed at temperatures lower than levels where austenite is formed and the FCC lattice is formed. Since the 13itride steel remains in the BCC lattice there is essentially no growth or deformation afterwards. This helps retain the prescision of the product throughout the nitriding process. Compared to other hard outer coating processes available nitriding is much cheaper from $2/lb for a .005 case to $10/lb for .025 case except for carburizing, the cheapest technique available. The treatment can take can last from a very short time to up to 50 hrs. The variety of techniques also makes nitriding popular, especially the use of plasma, which heats the metal at even lower temperatures using heat from the plasma which also helps break apart the nitrogen gas and diffuse it through the steel.

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References y Askeland, Donald R., Pradeep P. Fulay, and Wendelin J. Wright. The Science And Engineering Of Materials. Thomson Engineering, 2012. y y
. "Wasp Tech Sheet." www.cmmginc.com. N.p., n.d. Web. 15 Dec 2011. Garzon, Carlos. "Microstructure and Chemical Characterization of Nitrided Steels." . 08/2002, n.d. Web. 15 Dec 2011.

"Heat Treatment Australia." Nitriding Processes. N.p., n.d. Web. 15 Dec 2011. <www.heat.com.au>.

"Practicial Nitriding." An Introduction to Nitriding. Web. 15