DECARBURIZATION DURING
HEAT TREATMENT
HADI KHARESTANI
APR 2022
PREFACE:
When metallic parts are heated above 5608C (10408F) (this is the temperature at which the creation of wustite or FeO
begins), after creation of the first part of the layer in the starting phase, the reaction follows by diffusion of Fe 2þ ions from
the steel toward the outside and the diffusion of oxygen ions at the scale–metal interface toward the inside. As time passes,
the linear law of oxidation valid for the starting phase changes to a parabolic law.
The growth of the oxide layer (scale) depends very much on the chemical composition of the steel. Different alloying
elements, having different diffusion abilities, have different influences on the oxidation process and the build-up of scale.
The chemical composition of the original material on the surface is subject to changes.
According to their affinity for oxygen, the alloying elements in steel can be
divided into three groups with respect to their influence on the scaling
process :
Group I: contains those elements whose oxygen affinity is less than the
affinity of the richest oxide compound wustite (FeO), e.g., Ni and Co. After
saturation of the basic metal with oxygen, the outer oxidation of iron begins
with the creation of wustite. The alloying elements become richer at the
scale–metal interface.
Group II: contains those elements whose oxygen affinity is greater than that
of iron (Cr, Si, V, Al). After saturation of the basic metal with oxygen, inner
oxidation begins. Because of the creation of internal oxides of alloying
elements, a diffusion barrier builds up against the diffusion of metal and
oxygen ions, hampering the development of scale.
Figure 2:Influence of Cr on the oxidization of
a steel at temperatures of 600, 700, and
Group III: contains those elements whose oxygen affinity is similar to that 800°C.
of wustite (Mo, W). No inner oxidation takes place. The alloying elements
become richer in the basic metal at the scale–metal interface.
FURNACE ATMOSPHERES PROVIDE PROTECTION AND CONTROLLED MATERIAL MODIFICATION
Gases are often introduced to furnaces during heat treatments to provide a protective environment, controlled oxidation, or to
act as a carrier for substances intended to modify the material or surface.
One of the most common atmospheres used during heat treatments are endothermic gas compositions, which are typically
used as a ‘neutral’ hardening gas, or a carrier for gas carburizing or carbonitriding.
Endothermic gas mixtures are typically produced by endogas generators, which heat natural gas and air in the presence of a
catalyst to produce endothermic gas. The reaction consumes heat- hence the term ‘endothermic gas.
DECARBURIZATION:
Under conditions that cause the oxidation of iron, the oxidation of carbon is also to be expected. Decarburization of a metal is
based on the oxidation at the surface of carbon that is dissolved in the metal lattice.
It should be noted that, depending on the carbon potential of the surrounding atmosphere, decarburization can take place
independently of scaling.
However, in heat treatment processes iron and carbon usually oxidize simultaneously. During the oxidation of carbon, gaseous
products (CO and CO2) develop. In the case of a scale layer, substantial decarburization is possible only when the gaseous
products can escape, i.e., when the equilibrium pressures of the carbon oxides are high enough to break the scale layer or when
the scale is porous.
The carbon consumed on the surface has to be replaced by diffusion from the inside. Hence the process of decarburization
consists of three steps:
1. Oxygen transport within the gas to the metal surface
2. 2. Carbon exchange at the gas–metal interface
3. 3. Diffusion of carbon within the meta
Generally the diffusion of carbon within the metal is the most important factor in controlling the rate of decarburization, which
after a short starting period follows a parabolic time law. When a mild steel is heated below 9108C (16708F), a surface layer of
ferrite is formed that acts as a barrier to carbon transport owing to the very low solubility of carbon in ferrite. Above 9108C
(1670°F) the steel remains austenitic throughout, and decarburization becomes severe. The model used to represent
decarburization in the fully austenitic condition is shown in Figure3. The steel surface is continually oxidized to form a scale,
while the carbon is oxidized to form the gases CO and CO2. The scale is assumed to be permeable to these gases, which escape
to the atmosphere.
FIGURE 3: Model for decarburization in fully austenitic condition.
To calculate the depth of decarburization, the distribution of carbon in the metal is calculated by solving Fick’s second law for the
relevant boundary condition:
indicates that initially the carbon concentration was uniform throughout the specimen; Equation 6.26 indicates that the carbon
concentration at the metal–scale interface is constant (in equilibrium with the scale). It is assumed that decarburization does not
extend to the center of the specimen and that the diffusion coefficient of carbon in austenite is independent of composition;
enhanced diffusion down grain boundaries is neglected. Under these conditions the solution at a constant temperature (for which
the diffusion coefficient is valid) reads:
where C0 is the original carbon content of the metal, Cs is the carbon concentration at the metal–scale interface, D is the
carbon diffusion coefficient, t is time, erfc=1- erf (here erf is the error function), and kc is the corrosion constant of the metal
(kc = 𝑥 2 /2t). Equation 6.27 provides the carbon content within the metal for x > X as a function of time and position.
The value of kc for the relevant steel in the relevant atmosphere is expressed as
CONTROLLING ATMOSPHERE AND AIR FLOW IN INDUSTRIAL FURNACES:
Heat-treatment processes like carbonitriding, annealing and sintering are used to create crucial components for the aerospace,
petrochemical and automotive industries, so the industrial furnaces used to perform these tasks must be able to produce
precise and repeatable results. This is done by carefully monitoring and controlling furnace atmospheres, temperatures and air
flow. This article will explain the importance of each of these factors.
INDUSTRIAL FURNACE ATMOSPHERE CONTROL:
The atmosphere in industrial furnaces can either encourage or prevent chemical reactions. When the industrial
furnace atmosphere acts as a carrier, it reacts with the surface of the metal being treated to create an
environment that supports the processes like hardening.
When the atmosphere plays a protective role, it prevents the material being treated from reacting with harmful
elements. If the atmosphere is not closely monitored and controlled, unwanted chemical reactions could leave the
parts produced unsuitable for their intended purpose.
Furnace atmospheres are made up of either hydrogen, inert gases like argon, nitrogen or helium or endothermic
gas mixtures.
IMPORTANCE OF INERT ATMOSPHERE GASES:
Inert atmospheres are protective, and they are used in industrial furnaces when chemical reactions like
decarburization or oxidation must be avoided. Inert atmospheres allow furnace environments to be controlled
with great precision during processes like sintering and hot isostatic pressing, which leads to extremely clean
and consistent parts. Nitrogen, helium and argon are the gases most commonly used to create an inert
industrial furnace atmosphere.
Heat-treating furnaces can be gas heated with two methods: direct or indirect fired. Direct firing consists of
burners placed in the refractory walls pointing just above and/or just below the parts being heated. Burners are
never positioned to fire directly at parts since the temperature of the flame is near 2,000°F (1,093°C). Special
flat-flame burners are the exception where the burner flame is designed to spread along the refractory wall, not
straight out as a jet. Direct firing produces CO2, H2O, and nitrogen as mentioned above. Small amounts in the
ppm range of oxides of nitrogen (NOx) are also produced. Since both CO2, and H2O contain oxygen, they will,
depending on temperature, be oxidizing to iron and steel. Where oxidation cannot be tolerated, indirect firing is
the option.
Indirect fired furnaces attach burners to radiant tubes made from heat-resisting nickel, chromium, and iron alloys.
This method is used where a special atmosphere is used to protect parts with nitrogen or carburize with
endothermic gas. Endo gas consists of 20 percent CO, 40 percent hydrogen, and 40 percent nitrogen with trace
amounts for CO2, H20, and methane (CH4). We all know hydrogen, like natural gas, can be explosive if not
handled properly. Heat-treating furnaces are designed to handle those gases appropriately. Take, for example,
the batch furnace represented in my March/April Hot Seat column shown in Figure 1. In general, most people
outside the heat-treating industry, and many even within the arena, believe that explosive gases and heat are not
a good combination.
Whenever I encounter a furnace with a combustible atmosphere, I want it to be above 1,400°F (760°C). Why?
1,400°F is the auto ignition temperature above which natural gas and hydrogen will burn with air if they’re within
the combustible limit. The situation you want to avoid is combustible gases mixed with air below the ignition
temperature; this is how explosions occur with premix combustible gases. For fuels such as natural gas and
hydrogen to burn, the ratios of air-to-fuel must fall between the lower explosive limit (LEL) and the upper
explosive limit (UEL). Anywhere outside of those limits, combustion can’t occur. For natural gas, the LEL is 5
percent — meaning if the gas concentration in air is less than 5 percent, it’s too lean to burn or explode. If the
gas concentration is high, allowing only 15 percent of air, it’s too rich to burn or explode. So, for an explosion to
occur the mix must be between 5 to 15 percent air. Hydrogen’s LEL and UEL are 4 percent and 75 percent
respectively. The other combustible gas in endo is CO. Its LEL is 12.5 percent and UEL is 74 percent. The limits
can be explained further in Figure 2.
HOW TO MEASURE FURNACE ATMOSPHERE:
The composition of the atmospheres in industrial furnaces changes constantly when metals are heat treated, which
means sophisticated measurement and control devices are needed to keep things consistent and maintain the
quality of the finished product. These devices were once monitored and adjusted by furnace operators, but they are
now more likely to be linked to a sophisticated electronic control panel like Abbott Furnace’s S.M.A.R.T. System.
ENDOTHERMIC ATMOSPHERE CLASSIFICATIONS:
Protective endothermic industrial furnace atmospheres are usually made up of a mixture containing nitrogen,
hydrogen, carbon monoxide, carbon dioxide and traces of water. They are used when a reducing atmosphere is
needed for processes like sintering and bright hardening.
The American Gas Association has developed the following three endothermic atmosphere classifications.
•Class 200: This is the most basic atmosphere classification and is made by removing carbon dioxide and water
vapor from a nitrogen base.
•Class 300: This endothermic atmosphere is created by adding a mixture of fuel and air to a heated chamber
containing a catalyst.
•Class 600: This atmosphere is based on ammonia.
CONTROLLED AIR FLOW IN FURNACES:
The internal temperatures of industrial furnaces must be kept as uniform as possible to maintain part quality.
Recirculating the air inside a furnace more frequently is one of the techniques used to achieve this goal. When
extremely tight uniformity tolerances are required, furnaces may be fitted with higher capacity motors and larger
fans. This can increase the cost of a furnace substantially, so it is prudent to determine the allowable temperature
variances for the processes that will be performed before investing in equipment.
CONTROLLED VS. UNCONTROLLED AIRFLOW:
Air flow may be uncontrolled in less sophisticated heating equipment like batch ovens that can produce acceptable
results, even when temperatures fluctuate by plus or minus 10 degrees Fahrenheit. But control systems are
required when temperature tolerances are tighter. When determining whether air flow should be controlled or
uncontrolled, engineers consider the materials that will be heat treated and the processes they will be subjected to.
AIR PRESSURE AND MOVEMENT:
When determining the optimal industrial furnace air flow, engineers consider both the way the air will circulate inside
the heating chamber and the amount of air pressure needed to achieve the desired results. To run these
calculations, engineers need to know the kind of heat-treating process the furnace will be used for, how quickly the
furnace will be heated up, and how long the desired temperature will be maintained.
ENDOTHERMIC PROCESS AND HEAT TREATMENT FURNACES – CO AND CO₂ CONTROL
CONSIDERATIONS:
Endothermic process and heat treatments are essential for ensuring high-quality metal and alloy products.
Endothermic gas (CO/H₂/N₂) is often used as a ‘neutral’ protective gas or carrier gas during heat treatment process. Monitoring
and controlling the furnace gas composition is essential to ensure metallic products retain their desired properties. This article
outlines why CO and CO₂ levels must be precisely controlled, and the best way to measure CO and CO₂ concentrations in
endothermic heat treatment furnaces.
Heat treatments are commonly used to alter the physical or chemical properties of materials such as metals and alloys,
including steel. Heat treatments result in changes in material microstructures that provide increased hardness, temperature
resistance, ductility, and strength.
Although the name ‘heat treatment’ suggests a simple procedure, process parameters including time, temperature, and
atmosphere during heat treatments must be carefully controlled to obtain the desired material characteristics and ensure high-
quality products.
SELECTION OF ATMOSPHERE:
The surrounding in the thermal enclosure (furnace) is termed atmosphere. The atmosphere consists of gases and is usually
air. However, in some heat treatment, thermo‐mechanical processing, sintering etc special type of atmosphere is required to
• Prevent oxide formation, if the heating material is prone to oxidation.
• Decarburize steel.
• Control the surface chemistry of steel which means the elements must not be oxidized or reduced during heating.
• Produce “blueing” effect in steel. The blueing effect imparts a wear‐resistant and oxidation‐ resistant surface finish.
• Reduce oxides formed on the surface.
• Make the surface hard by allowing carburizing or nitriding.
TOOLS FOR MEASURING AND SAMPLING:
Industrial furnace atmosphere control functions are carried out by a series of probes and sensors.
These components measure and control gas ratios and oxygen, water vapor and carbon dioxide levels during the
entire furnace cycle.
The devices most commonly used for controlling an industrial furnace atmosphere include:
•Oxygen probes
•Oxygen analyzers
•Combustion analyzers
•Dew-point analyzers
•Non-dispersive infrared analyzers
ENDOTHERMIC PROCESS OF GAS COMPOSITION MUST BE CAREFULLY CONTROLLED TO ENSURE
PRODUCT QUALITY:
The main objective of a protective furnace atmosphere is to prevent undesired decarburization, hydrogen embrittlement,
oxidation, surface bluing, and soot formation.
For the desired metal treatment to be successful, the gas composition must be carefully monitored and strictly controlled.
Measuring the concentrations of CO, CO₂, H₂, H₂O, N₂ and CH₄ in the generated endothermic gas atmosphere can help ensure
that both the endogas generator and the furnace are operating correctly and prevent any undesired reactions. The presence of O₂
or excess CO₂ in endothermic gas can result in oxidation reactions, such as iron oxidation.
Fe + CO2 ⇌ FeO + CO
Iron oxide can form a visible layer on the surface, known as scale. To maintain the brightness of steel, oxidation of
iron should be limited, be eliminating oxygen from the furnace and limiting the presence of CO₂.4,7
The properties of steels strongly depend on their carbon content, so it is important to prevent undesired
decarburization during heat treatment. Decarburization causes carbon to diffuse towards the surface of the steel,
reducing overall strength and fatigue resistance.
Fe3C + CO2 ⇌ 3Fe + 2CO
Oxidizing gases like O₂ and CO₂ induce decarburization, while maintaining the presence of reducing gases such
as an excess of CO and H₂ can help prevent undesired decarburization by pushing the equilibrium in the direction
of the carburized product.
Measuring the Endothermic Process of Gas Composition in Furnaces:
Endothermic furnaces are commonly monitored using dew point analyzers or oxygen sensors. However, this
method of monitoring a furnace assumes that the endothermic gas mixture has a consistent composition, which
may not always be the case.
Ideally, furnaces should be equipped with a combination of measurement solutions, including dew point analyzers
O₂ probes, and CO/CO₂ analyzers, enabling all the important parameters to be monitored and controlled.
The latest endothermic generators measure the furnace gas composition and automate the delivery of methane
and air to the endogas generator to provide consistent endothermic gas delivery to the furnace.
Using CO and CO₂ analyzers to monitor the furnace atmosphere provides precise information about the
endothermic gas composition delivered to the furnace. infrared sensors offer the ideal solution for measuring CO
and CO₂ in endothermic furnaces, as they are simple to use, provide rapid measurements, and easy to interpret
results. What’s more, infrared sensors can be easily incorporated into systems intended to alter endothermic gas
production and delivery automatically.
It seems ironic that the one constant in atmosphere heat treating is that the composition of the furnace atmosphere
is always changing. As such, we must use measurement and control devices to ensure the proper atmosphere
composition necessary to achieve the desired metallurgical quality and mechanical/physical properties throughout
the workload. Let’s learn more.
The trend today is to use multiple measurement tools to obtain the most accurate snapshot of the atmosphere in
real time. In addition, the industry is rapidly moving toward automated control systems.
Manual or Automatic Control?
In one form or another, atmosphere control has been around for decades, and the control method may be
categorized as either manual or automatic. There are benefits and limitations to both(table1):
In a manual control scheme, success depends on the vigilance of the people operating the equipment, relying on
their experience coupled with either trial and error or historical records/information. A typical example of this type
of control would be as follows.
A furnace operator sets up a load, charges it into the furnace and manually adjusts temperature and atmosphere
parameters. As process values approach set point, the operator begins periodically checking the atmosphere with
sensor devices (e.g., dew-point instruments) and logging values on a heat-treat form of some design.
If process deviation occurs, the operator intervenes and attempts to make adjustments “on the fly” based on
experience. At the end of the process, the heat treated checks the load to confirm it does not need to be reworked
or scrapped. Essentially, operators learn what works and what does not on a case-by-case basis over time, adding
to their knowledge base. For key parameters or data records, a form, a recorder or a printer would provide a paper
copy to be filed.
Automated control differs from manual control mainly in that sensors, computers and specially designed software
are used during the heat-treatment process to monitor, control and record data about the furnace atmosphere.
Load-entry software can even be used to control the timing of a charge and electronically record all load
parameters set up by the operator. Output is set and changed by a process controller, such as a loop controller,
designed specifically for heat-treatment processes or a PLC.
If the controller detects a process deviation or a condition likely to result in one, it can make adjustments and/or
generate a process alarm if operator intervention is needed. Information is delivered through mobile devices to
operators, supervisors or even maintenance based on an escalation and profile of the alarm and recipient. Data
logging is electronic. Logged data points can be accessed at any point in the future.
Measurement Devices and Sensors:
Monitoring and/or controlling the heat-treatment process is accomplished by use of sensors and measurement
devices. The most common of these are:
•Oxygen (carbon) probes
•Non-dispersive infrared analyzers (NDIR) – single- or multiple-gas
•Dew-point analyzers
•Oxygen analyzers
•Combustion analyzers
Whether neutral or case hardening, annealing or normalizing, a number of variables determine how well a furnace
does its job. Throughout the entire cycle it is critical to the process that we control the percentage of carbon
dioxide, oxygen and water vapor as well as the ratio of enriching gas (or air) to carrier gas.
For example, surface carbon can be controlled within ±0.05% C during carburizing by measuring one or more of
the gases mentioned above and adjusting the addition gases (hydrocarbon and/or air) accordingly.
Oxygen (Carbon) Probes:
The oxygen (aka carbon) probe (Fig. 1) is an in-situ device that looks similar to a thermocouple for measuring
temperature and typically sits inside the furnace, inside the generator (typically above the catalyst bed or in a
separate heated “well” into which the furnace atmosphere is pumped). In whatever location, the oxygen probe
measures minute changes in oxygen concentration of the furnace atmosphere.
A difference in partial pressure of oxygen in the furnace atmosphere and the partial pressure of oxygen in the
room air induces a voltage across the electrodes in the probe. At any given temperature, there is a known
relationship between the probe millivolt output and the oxygen potential of the atmosphere. The oxygen
potential can be directly related to the carbon potential. Hence, monitoring the furnace temperature and the
probe output can control the carbon potential of the furnace atmosphere.
The oxygen probe uses a conductive ceramic sensor, most often manufactured from zirconium oxide (Zr2O3).
Operating range of the probe is normally 650-980˚C (1200-1800˚F). Oxygen probes can be used for a variety of
atmosphere compositions, but they need to be calibrated for the specific one in use. They are fast-response
devices and subject to contamination by carbon, zinc and certain stop-off paint vapors. When used in
carbonitriding applications, the presence of ammonia will shorten the life of the probe.
An oxygen probe in a carburizing atmosphere must incorporate periodic air burnouts (Table 2). The carburizing
process in use will determine the burnout frequency.
Measuring an Endothermic Atmosphere in a Furnace:
Carbon (oxygen) probes, shim stock or carbon analyzers and dew point are typically used to measure the carbon
potential of the endothermic atmosphere in a heat-treatment furnace. An infrared analyzer can also be used. The
CO2 value – similar to water vapor and oxygen – varies based on furnace temperature and carbon potential but will
typically lie between 0.25 and 0.50%. Multiplying the CO2 value by 100 can roughly approximate the dew point (in
˚F). Charts and tables can also be used and are available from most manufacturers.
If a radiant tube is leaky in a gas-fired furnace, the leak (oxygen and moisture) will dilute the atmosphere carbon
potential in the heat chamber when the furnace goes to high fire. As a result, the carbon controller will compensate
by calling for more enriching gas to increase the carbon potential coincidental with high fire. A “saw-tooth” trend
appears on the recorder. Setting the control to low fire will eliminate the saw tooth if the tube is cracked and leaking.
Oxygen probes and infrared analyzers are often used in conjunction when monitoring and controlling a nitrogen-
methanol atmosphere. Using NDIR, values between 14-28% CO have been reported (target 20%). CO2 values
typically range from 0.10-0.80%, and free methane can be as high as 8% depending on the carbon setpoint. All
testing should occur without hydrocarbon (e.g., natural or propane) gas additions. For nitrogen/methanol systems,
the CO percentage is largely determined by furnace temperature and the relative flows of nitrogen and methanol.
Combination furnace oxygen probe and infrared control
Measuring an Endothermic Atmosphere in a Generator:
Another popular trend, especially in the control of endothermic gas generators, is to use an oxygen probe in
combination with a dew-point analyzer.
Using an oxygen sensor to measure and control the dew point in an endothermic generator is done either in-situ, in
a thermal well or by use of an oxygen probe with an integral thermal well/sheath arrangement. The millivolt signal
can be converted to a dew-point value or, in some of the more advanced dew-point control systems, by calculation.
This calculation uses the millivolts generated by the probe, the hydrogen factor of the controlling instrument and the
temperature of the oxygen sensor. The temperature is required for the calculation, but the dew point of the gas is not
temperature-dependent.
Oxygen sensors are often run at 1040˚C (1900˚F), although they will provide the same reading when operating at
815˚C (1500˚F). The generator gas exiting the retort is sent through a heat exchanger to freeze the composition. As
long as the sensor is accurately measuring the millivolts of the gas, the temperature of the sensor can be as low as
593˚C (1100˚F).
Changes in sensor location have occurred over the years. Initially, a sensor would be mounted on the top of a retort
in an air-cooled, fabricated fixture to measure the oxygen. Then a ceramic reheat well mounted through the sidewall
of the generator was used. Now a modified sheath with an integral reheat well makes the installation much easier.
The sheath and the integral well are aluminized prior to assembly so that the nickel in the sheath material does not
react with the endothermic gas. This is especially important between 705˚C and 480˚C (1300˚F and 900˚F) where,
over time, the endothermic reaction will reverse if nickel is present.
Lambda-style probes like those used in an automobile engine are also used in generator applications. While less
expensive, they often lack the long-term stability of the zirconia technology and must be re-oxidized to avoid drift.
