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CHAPTER

18

What Is Meant by
Ferritic Nitrocarburizing?
FERRITIC NITROCARBURIZING accomplishes surface treatment of
a part in the ferrite region of the iron-carbon equilibrium diagram (Fig. 1).
As the process takes place in the ferrite region, both nitrogen and carbon
diffuse into the steel surface. The process is categorized as a thermochemical treatment and is carried out at temperatures between 525 and 650 C
(975 and 1200 F); the typical process temperature is approximately 565 C
(1050 F). The purpose of the process is to diffuse nitrogen and carbon
atoms into a solid solution of iron, thus entrapping the diffused atoms in the
interstitial lattice spaces in the steel structure (Ref 1).
As with the nitriding procedure, there are many methods and derivatives of ferritic nitrocarburizing. These are discussed in the chapters that
follow.

Process Benefits
Ferritic nitrocarburizing improves the surface characteristics of plain
carbon steels, low-alloy steels, cast irons, and sintered ferrous alloys. As
described in later sections of this chapter, resistance to wear, fatigue, and
corrosion are improved with the introduction of nitrogen and carbon.
Scuffing resistance means the resistance to wear on the metal surface. This is accomplished by changing the nature of the surface compound layer, which is also known as the white layer. The completed
compound layer will form with both epsilon () and gamma prime ( )
phases. The dominant -phase resists abrasive wear.
Fatigue properties of steel are greatly improved by altering the composition of the compound layer. This means that treated steel has greater
resistance to fatigue failure than an untreated steel (Ref 1).
Corrosion Resistance. After ferritic nitrocarburizing, steel parts can
withstand many hours in a salt spray environment, whereas an untreated
plain carbon steel will fail the corrosion test very rapidly.

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Fig. 1

The iron-carbon equilibrium diagram. The nitrocarburizing process is carried out in the ferrite region
(alpha iron) of the diagram.

Low Distortion. Another major advantage of the ferritic nitrocarburizing process is that the procedure is carried out at a low temperature that
prevents phase changes in the steel (from ferrite to austenite), thus reducing the risk of distortion. Distortion is the result of the release of induced
stresses, the thermal shock of quenching, and the risk of incomplete transformation to martensite. No phase change occurs during the ferritic nitrocarburizing treatment.

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Chapter 18: What Is Meant by Ferritic Nitrocarburizing?

Early History of Ferritic Nitrocarburizing

Ferritic nitrocarburizing has been a proven process for many years and
is now gaining much acceptance by engineers. This increased interest in
the process, the author believes, is due to engineers gaining a better understanding of materials selection and metallurgists gaining a greater understanding of process capabilities and restrictions. In addition, many furnace
manufacturers want to serve their clients by developing new and more
efficient process methods and equipment.
The early methods of ferritic nitrocarburizing were accomplished in
low-temperature (550 C, or 1020 F) salt baths working on the principle
of the decomposition of cyanide to cyanate (in the ferrite region). Imperial Chemical Industries in England pioneered the salt bath process,
which was called the Sulfinuz treatment (Ref 2). The salt also contained a sulfur compound in its chemistry. The process was based on the
formation of:

Nitrides: The nitrides were formed as a result of the nitrogen component contained in the cyanide salt. The nitrogen diffused into the steel
to form iron nitrides in low-alloy steels and stable nitrides in higher
alloyed steels.
Carbon: The carbon was supplied from the salt in limited quantities
and formed carbides, interspersed with the formed nitrides.
Sulfides: The sulfur addition to the salt formed sulfides in the case,
providing a self-lubricating property.

The action of the molten salt at the process temperature also caused
slight surface porosity on the treated steel. This allowed the surface pores
to become minute reservoirs, retaining lubricant on the immediate surface.
The net result was that the treated component resisted scuffing and
exhibited excellent resistance to frictional wear problems. The process
was a great success with high-speed spindles and high-speed cutting tools.
It did, however, require careful salt bath analysis on a daily basis (Ref 1).
Another challenge of the process was that the salt was not very water soluble. The treated component required extensive hot water cleaning after
treatment. Cleaning became a major issue.
Problems associated with salt bath processing led to experimentation
with gaseous methods of ferritic nitrocarburizing. Experiments were conducted in the late 1950s with gaseous methods by Cyril Dawes of Joseph
Lucas Ltd. in England. The company successfully applied for a patent on
the process in 1961 (Ref 3).
The gaseous procedure produced a porous layer very similar to the layer
produced with the Sulfinuz process (with the exception of forming surface
sulfides), which claimed to provide good antifrictional properties. The
process patent stated that the gaseous atmosphere consisted of ammonia,

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with a hydrocarbon gas and other small amounts of carbon-containing

gases (Ref 3).
An important study that contributed greatly to the scientific understanding of gas nitrocarburizing treatments and compound layer structure was
published by Prenosil in 1965 (Ref 4). As a result of the study, many companies developed variations of the original patented process and the procedure was accepted by engineers and metallurgists alike.
Advances in gaseous nitrocarburizing did not stop or hinder the process
technique of using salt baths for the ferritic nitrocarburizing process. If
anything, it spurred on the salt manufacturers to develop more environmentally friendly salts and cleaner procedures. Degussa of Germany
developed the salt bath process of Tufftride, a two-component process
that formed both nitrides and carbides in the immediate surface of the
steel (Ref 1). The process will produce only very shallow case depths,
approximately 0.05 mm (0.002 in.) deep, but with high surface hardness
values, good fatigue properties, and excellent corrosion resistance. The
process cycle times are relatively short (in the region of 1.5 h), followed
by a quench (Fig. 2).
Once again, the process relies on the decomposition of cyanide to
cyanate, which is accelerated by the introduction of a titanium aeration
tube. The aeration tube passes air through the molten salt from the bottom
of the salt pot. The system requires good operational maintenance in terms
of regular bath desludging, salt analysis, and periodic regeneration. This
requires raising the bath temperature to 575 C (1070 F) and holding for
approximately 2 h, followed by another desludging operation. The purpose is to precipitate out of the molten salt any free iron originating from
work support baskets and fastening wire used to wire the components in
place in the work basket (Fig. 3).

Fig. 2

Typical time-temperature process cycle for a ferritic nitrocarburizing

procedure using salt baths

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Chapter 18: What Is Meant by Ferritic Nitrocarburizing?

Fig. 3

Work-holding fixtures and wiring techniques used in liquid nitrocarburizing. (a) Typical holding basket for small parts, equipped with a
funnel for loading parts into the basket without splashing. Funnel, which is made
of sheet metal, also insures that parts are coated with salt before nesting together.
Basket may be made of carbon or alloy steel rod and steel wire mesh. Work must
be free from oil, or the parts will stick together. Parts must be dry. (b) Inconel basket of simple design. Upper loop of the handle is for lifting; lower loop accommodates a rod which supports the basket over the furnace. (c) Simple basket with
trays, intended for small parts. Trays provide a maximum of loading space without adversely affecting circulation. Entire fixture is made of Inconel. (d) Netted
fixture, of Inconel, for holding small parts with a head or shoulder. (e) Methods of
wiring small parts. Black annealed steel wire is used for parts weighing less than
10 lb; annealed stainless wire is used for heavier parts. (f) Hooks, made of nickel
alloy rod, for holding circular parts. (g) Method for holding large parts in which
tapped handling holes are available or can be provided. Nickel alloys are used
for such fixtures because of the need for high-temperature strength. Resistance to
oxidation is not a factor, as liquid carburizing salts are reducing. (h) Rack for
holding six small crankshafts; exploded view shows a crankshaft in position.
(i) Special rack for carburizing the outside diameters of bearing races. Holding
plates are made of mild steel; rods, of Inconel.

With the advent of pulsed plasma technology in the early 1980s for ion
nitriding, it did not take long to realize that another method of ferritic nitrocarburizing had been discovered. This procedure was soon commercialized. Advantages include faster process cycle times, less surface cleaning
and preparation, deeper case formation, and better control of surface metallurgy formation. Equipment is now being built that is capable of performing

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both pulsed plasma ion nitriding and ferritic nitrocarburizing in the same
process chamber and with the same pulsed power pack. The procedure
offers a more controllable, repeatable surface metallurgy.

Why Ferritic Nitrocarburize?

The physical benefits of ferritic nitrocarburizing have been listed. The
choice to nitrocarburize is an economic one, when compared to other
methods of achieving the same benefits. Figure 4 presents an approximate
cost comparison of various surface treatments (Ref 5). Besides the direct
cost of the equipment, the process selection procedure should consider the
total investment costs.
Cost of floor space involves direct purchase or rental of space.
Remember, floor space also includes storage area for fixtures and fittings
and workload preparation area.
Installation costs are sometimes overlooked. The cost of installation
means the cost of unloading equipment from the delivery vehicle and
positioning the equipment in place. Will riggers need to be hired? It also
means the cost of a new facility if one is built to accommodate the new
equipment, including all plumbing, electrical wiring, gas delivery systems, water delivery system, and effluent exhaust system.
Thermochemical:
Carburizing
Nitriding
Nitrocarburizing
Electrochemical:
Chromium
Cobalt + Cr3C2
Electroless:
Nickel
Plasma sprayed:
WC-Co
Al2O3
Combustion gun sprayed:
13% Cr wire
Ni-Cr-B and fuse
Ni-Cr-B + WC and fuse
Surface weld:
Iron-base
Cobalt-base
Vapor deposited:
CVD TiC
PVD TiN
Cost

Fig. 4

Approximate relative costs of various surface treatments. Source: Ref 5

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Chapter 18: What Is Meant by Ferritic Nitrocarburizing?

Cost of Insurance and Freight. What type of crating or container will

be used? After loading is complete, a visual inspection should be carried
out; if possible, digital photographs should be taken of the load in its position in the event of possible insurance claims when the contents are later
uncrated. Other related costs and concerns include:

Loading and delivery from the manufacture site to the point of departure
Type of shipping line (conference or nonconference)
Paperwork delays. If the equipment is shipped internationally, incomplete or improper paperwork can cause serious delays at either the port
of departure or the port of arrival. Such delays can be very costly.
Check on daily demurrage rates and duties payable.
Insurance. The equipment must leave the manufacturing facility fully
insured. Before installation, check the suitability of the intended site
with the insurance carrier. Does the room or building have the necessary fire protection? Would the existing fire protection system damage
the new equipment?
Road transport from the port of arrival. Road transportation permits
may be necessary if the vehicle load is considered a wide load.
Access. Be sure that before the equipment arrives, doors and wall
apertures are large enough to allow easy access of the equipment into
the facility. It can be embarrassing if the furnace will not fit through
the door. Preplanning models can sometimes be used to navigate large
equipment through plants.

Operating costs include materials, energy, disposal of spent chemicals,

labor (including training), rejected materials, and time. All these costs must
be evaluated on a per item or other basis before making a final decision.

Training
To ensure that the furnace goes together the first time (and hopefully
starts the first time), at least two primary discipline peoplethe operating
person and the maintenance personshould visit the manufacturing site
when the furnace is being assembled. They also should be present after the
hot trials to see how the furnace is dismantled. Photographically document the critical assembly areas using a camera or video recorder.
Project training can then be broken down into:

An understanding of both the process and its results: This means understanding the process principles, the method of nitrogen diffusion, and
the expected results in relation to the steel being treated.
An understanding of the equipment performance: This means understanding the operation, functions, and capabilities of the equipment, as
well as reactions of the process in relation to part geometry.

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While many more considerations may arise when preparing to ship a

furnace from one place to another, the previously mentioned ones will
serve to stimulate thinking between the team responsible for delivering
the equipment and the client. In order for a furnace project to be successful for both the purchaser and the seller, there must be clear lines of communication regarding each partys responsibilities. This must include
expectations of performance from both the furnace manufacturer and the
client.
REFERENCES
1. T. Bell, Ferritic Nitrocarburizing, Met. Eng. Q., May 1976, reprinted
in Source Book on Nitriding, P.M. Unterweiser and A.G. Gray, Ed.,
American Society for Metals, 1977, p 266278
2. The Cassel Manual of Heat-Treatment and Case Hardening, 7th ed.,
Imperial Chemical Industries Ltd., United Kingdom, 1964
3. Joseph Lucas Ltd., United Kingdom, British Patent 1,011,580
4. B. Prenosil, Structures of Layers Produced by Bath Nitriding and by
Nitriding in Ammonia Atmospheres with Hydrocarbon Additions,
Hrt.-Tech. Mitt., Vol 20 (No. 1), April 1965, p 4149 (BISI translation 4720)
5. J.R. Davis, Ed., Surface Engineering for Corrosion and Wear Resistance, ASM International, 2001, p 191

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