Nitriding Nitriding process, first developed in the early 1900s, continues to play an important role in many industrial applications.

It is a heat treating process that diffuses nascent nitrogen into the surface of a metal to create a case hardened surface at higher temperatures (510C590C). The secret of the nitriding process is that it does not require a phase change from ferrite to austenite, nor does it require a further change from austenite to martensite. In other words, the steel remains in the ferrite phase (or cementite, depending on alloy composition) during the complete procedure. Though wrapped in a bit of alchemical mystery, it remains the simplest of the case hardening techniques. It is predominantly used on steel, but also titanium, aluminium and molybdenum. Typical applications include Camshafts, Bushes, Rocker Shafts, Tappets, Shafts, Oil/Fuel & Water Feed Pumps, Gears, Spindles, Bearings, Cylinder Liners, Sprockets, Guides, Cages, Valves, Rocker Arms, Slides, Crankshafts, Valve Guides, Shafts, Flanges, Pins, Tools, Dies, Sheet Metal Parts, Machine Parts, Stainless Steel Components, Cast Iron Items, Transmission Parts etc., A number of operating process parameters must be adhered to and controlled in order to successfully carry out the nitriding process. Most of these parameters can be controlled with relatively simple instrumentation and methods. Examples of process parameters for nitriding include: Furnace temperature Process control Time Air or Gas flow Process chamber maintenance

All these factors help to reduce distortion during the process, with the exception of induced residual stresses. Another benefit of nitriding is that it acts as a stabilizing process by providing an additional temper to the processed steel.

Types of Nitriding The processes are named after the medium used to donate. The three main methods used are: gas nitriding, salt bath nitriding, and plasma nitriding. Gas nitriding In gas nitriding the donor is a nitrogen rich gas, usually ammonia (NH3), also known as ammonia nitriding. When ammonia comes into contact with the heated work piece it disassociates into nitrogen and hydrogen. The nitrogen then diffuses onto the surface of the material creating a nitride layer.

Salt bath nitriding

In salt bath nitriding the nitrogen donating medium is a nitrogen-containing salt such as cyanide salt. The temperature used is typical of 550590 C. Plasma nitriding Plasma nitriding is also known as ion nitriding, plasma ion nitriding. In this technique intense electric fields are used to generate ionized molecules of the gas (plasma) around the surface to be nitrided. The gas used for plasma nitriding is usually pure nitrogen. Advantages and Disadvantages of various Nitriding process: Process Advantages Disadvantages Controlling parameter: Ammonia dissociation rate inadequate for control of layer properties In many cases process produces a brittle white layer which requires removal Stainless steels require special activation techniques

Gas nitriding Low temperature in comparison with carburizing Simple control techniques

Process Salt bath nitriding

Advantages Ease of obtaining good nitrided layers on low carbon and low alloy steels in repeatable production

Disadvantages Processes limited to those steels, which can be heated to higher temperatures, without losing core hardness. Requires thorough washing to remove salt residues which may cause corrosion Health hazard and waste disposal problems

Rapid heating and processing No in-process control

Plasma nitriding

Simple mechanical masking Problems with temperature of surfaces to be free of nitriding Ease of surface activation through cathodic sputtering Low temperature processes possible Short saturation cycles measurement and uniformity Ease of overheating if not closely monitored Results sensitive to part geometry and arrangement in furnace retort Requires highly skilled and experienced operator

Liquid Nitriding or salt bath nitriding: Liquid nitriding or nitriding in a molten salt bath uses the principle of the decomposition of cyanide to cyanate and the liberation of nitrogen within the salt for diffusion into the steel surface at the temperature range of 510 to 580C and thereby forming a iron nitride layer (Hard and Wear resistant layer). The case hardening medium is a molten, nitrogen-bearing, fused-salt bath containing either cyanides or cyanates.

Liquid nitriding is a sub-critical casehardening process and hence processing of finished parts is possible because dimensional stability can be maintained. Also, liquid nitriding adds more nitrogen and less carbon to ferrous materials than that obtained through higher-temperature diffusion treatments. The liquid nitriding process has several proprietary modifications and is applied to a wide variety of carbon, low-alloy steels, tool steels, stainless steels, and cast irons. One such proprietary modification is the Sursulf Process.

Sursulf Equipment: The Sursulf equipment consists of 1) Stainless steel pot for holding of salts used for nitriding purpose. 2) Electrically heated furnace to heat the Sursulf bath. 3) Aerator or purging ring for agitating the bath to increase the chemical activity. 4) Desludging baskets for cleaning the nitrided components.

Typical nitrided furnace with jig and aerator arrangement

Sursulf Process: The Sursulf bath consists of mixture containing cyanates and carbonates salts of Lithium, Sodium and Potassium with small amounts of Potassium sulphide. Cyanates salts are the source for nitrogen and Potassium sulphide is the source for sulphur. Cyanates decompose the nitrogen and carbon monoxide and nitrogen diffuses into the metal by chemical reaction.

4CNO- CO32- + CO + 2N+2CN2CNO- + O2 CO32- + CO + 2N Carbonates formed are again converted into cyanates itself with the addition of regenerator salts (amines group) and partly by reduction reaction with potassium sulphide and partly by atmospheric oxidation. 2CN- + O2 2CNOSO32- + 3CN- 3CNO- + S2-

In general the following are the steps involved in Sursulf process. 1) Degreasing Prior to Sursulf process the components which are to be nitrided are thoroughly degreased with per chloro ethylene or alkaline solution to remove any dirt, oil or grease in order to get uniform case hardened layer. 2) Preheating- Preheating to 400C for 30 minutes is generally used in order to eliminate distortion of the components 3) Sursulf treatment The temperature of the bath is raised to 565 5C and the process is activated using air flow at desired levels. The components are soaked for prolonged periods, normally 4-8 hours depending upon the material composition and required case depth. 4) Cooling- Can be done by any one of the medium like cold water, hot water, oil, air etc., 5) Washing- Generally washing is done in agitated hot water (about 80C).

Effect of various process parameters on Sursulf process 1) Steel Composition.

Although the properties of alloy steels are improved by the compound and diffusion layers, relatively greater improvement is achieved with plain carbon steels of low and medium carbon content.

2)

Operating Procedures

Initial preparation and heating of the salt bath, aging of the molten salts (when required), and analysis and maintenance of salt bath composition are to be looked out. Virtually all steels must be quenched and tempered for core properties before being nitrided or stress relieved for distortion control. So, prior heat treatment may be considered an essential part of the operating procedure.

3)

Prior Heat Treatment.

Alloy steels usually are given a prior heat treatment similar to that preferred for gas nitriding. Maintenance of dimensional and geometric stability during liquid nitriding is enhanced by hardening of parts prior to nitride treatment. Tempering temperatures should be no lower than the nitriding temperature and preferably slightly above. Depending on steel composition, the effect of core hardness is similar to that encountered in gas nitriding.

4)

Starting the Bath.

The commercial salt mixture is melted at 540 to 595C. During the melting period, a cover should be placed over the retort to guard against spattering or explosion of the salt, unless the equipment is completely hooded and vented.

5)

Externally Heated Salt Baths.

Salt baths may be heated externally or internally. For externally heated salt baths, start up power should be limited to 37% of total capacity until signs of melting are apparent on all sides of the salt bath. For internally heated salt baths, natural gas flame torches having a moderate flame are effective in melting a pool of molten salt for a conductive path between electrodes.

Liquid Nitriding Applications Crankshafts, Camshafts, Tappets, Shafts, Gears, Spindles, Rocker Arms, Shafts,

Flanges, Pins, Tools, Dies etc., and for components requiring improved wear resistance, anti galling properties and increased fatigue resistance.

Typical Sursulf nitrided components

Definition of the Problem

Low hardness and non uniform case depth were observed in Sursulf nitrided pinion for gear reducer components in which the bath is loaded more than 80% of the maximum capacity of the furnace. Hence a root cause analysis was made in order to identify the reason for non conformance observed.

Investigation:
1. Material aspect & analysis: The pinion for gear reducer is made of SA 193 B7 chromium molybdenum ferritic low alloy steel. The following are the chemical and hardness requirements. Chemical Requirements for SA 193 B7 material Element Carbon Manganese Phosphorus, max Sulfur, max Silicon Chromium Molybdenum Iron Percent 0.370.49 0.651.10 0.035 0.040 0.150.35 0.751.20 0.150.25 Base

Hardness Requirement: 35 HRc Maximum

The chemistry of the failed component was analysed using Vacuum emission spectrometer and the values are given below. Element Carbon Manganese Phosphorus Sulphur Silicon Chromium Molybdenum Iron Percent 0.41 0.89 <0.010 0.015 0.29 0.98 0.21 Base

The core hardness of the failed component was tested using Rockwell hardness tester and the hardness values are found to be 32, 30, 30 HRc. The above observation rules out the possibility of material problem for non conformance of pinions case hardened by Sursulf process.

2.

Process aspect: Chemistry of salt bath: Log sheets of the corresponding failed lots were checked and found that chemistry of the bath is maintained as per norms. Procedure: Review of log sheets revealed that the bath was operated as per norms and no deviation from standard procedure was observed during the process. Loading of the bath: The bath was loaded around 0.43 tons in the corresponding failed lot as against the highest loaded capacity of 0.4 tons. The capacity of the furnace being 0.5 tons. A general nomenclature is that the furnace should loaded around 80% of the maximum capacity. Air flow rate (litres/hour): The standard air flow rate for agitating the bath for 0.4 tons is 250 ltr/hr and for 0.5 tons is 300 ltr/ hr. Upon examining the log sheet it was found that for loading of 0.43 tons an air flow rate of 300 ltr/hr was used. Hence deviation from standard procedure is observed w.r.t loading of the bath and the correspondence air flow rate for the failed lot.