metals

Article
Numerical Simulation of Low-Pressure Carburizing and Gas
Quenching for Pyrowear 53 Steel
Bartosz Iżowski 1,2,∗ , Artur Wojtyczka 1,2 and Maciej Motyka 2,3

1 Research and Development Center, Pratt & Whitney Rzeszów S.A., 35-078 Rzeszów, Poland
2 Faculty of Mechanical Engineering and Aeronautics, Rzeszow University of Technology,
12 Powstańców Warszawy Ave., 35-959 Rzeszów, Poland
3 Research and Development Laboratory for Aerospace Materials, Rzeszow University of Technology,
4 Żwirki i Wigury Str., 35-959 Rzeszów, Poland
* Correspondence: [email protected]

Abstract: The hardness and phase composition are, among other things, the critical material prop-
erties considered in the quality control of aerospace gears made from Pyrowear 53 steel after high-
pressure gas quenching. The low availability of data on and applications of such demandingstructures
justify investigating the choice of the material and the need to improve its manufacturability. In this
study, computational finite-element analyses of low-pressure carburizing followed by oil and gas
quenching of Pyrowear 53 steel were undertaken, the objective of which was to examine the influence
of the process parameters on the materials’ final phase composition and hardness. The material input
was prepared using JMatPro. The properties computed by the CALPHAD method were calibrated
by the values obtained from physical experiments. The heat transfer coefficient was regarded as
an objective variable to be optimized. A 3D model of the Standard Navy C-ring specimen was
utilized to predict the phase composition after the high-pressure gas quenching of the steel and the
hardness at the final stage. These two parameters are considered good indicators of the actual process
parameters and are used in the industry. The results of the simulation, e.g., optimized heat transfer
coefficients, cooling curves, and hardness and phase composition, are presented and compared with
experimental values. The accuracy of the simulation was validated, and a good correlation of the data
Citation: Iżowski, B.; Wojtyczka, A.; was found, which demonstrates the quality of the input data and setup of the numerical procedure.
Motyka, M. Numerical Simulation of A computational approach to heat treatment processes’ design could contribute to accelerating new
Low-Pressure Carburizing and Gas procedures’ implementation and lowering the development costs.
Quenching for Pyrowear 53 Steel.
Metals 2023, 13, 371. https://doi.org/ Keywords: steel; modeling; simulation; Pyrowear 53; inverse heat transfer; DEFORM3D; low
10.3390/met13020371 pressure carburizing; high-pressure gas quenching; simufact; phase transformations; latent heat;
Academic Editors: Jelena Srnec Koistinen–Marburger
Novak, Francesco De Bona and
Francesco Mocera

Received: 31 December 2022

1. Introduction
Revised: 6 February 2023
Accepted: 6 February 2023 Quenching is a critical heat treatment operation in the manufacturing process, which
Published: 12 February 2023 determines the enhancement of the fatigue durability and wear resistance of carburized
steel components, such as power-transmitting gears. Aerospace gearbox development
requires the application of modern materials with more resistance to tempering at elevated
temperatures. In the 1970s, the Pyrowear 53 low-alloy steel was developed when a new
Copyright: © 2023 by the authors. material for power transmission was needed due to the limitations of the commonly used
Licensee MDPI, Basel, Switzerland. 9310 steel and its tendency to score and scuff under high-temperature conditions. This steel
This article is an open access article was designed to operate mainly in power transmission components such as gears due
distributed under the terms and to its surface durability and fatigue resistance, enhanced by the compressive residual
conditions of the Creative Commons stress generated during carburizing and related to the delayed formation of martensite
Attribution (CC BY) license (https://
near the surface. Gears made of Pyrowear 53 are able to maintain their properties even
creativecommons.org/licenses/by/
when no lubrication is present due to the material’s wear resistance. The outstanding
4.0/).

Metals 2023, 13, 371. https://doi.org/10.3390/met13020371 https://www.mdpi.com/journal/metals

Metals 2023, 13, 371 2 of 17

properties of Pyrowear 53 are achieved thanks to, among other things, the high content
of silicon, providing resistance to softening during tempering, nickel, responsible for
added toughness and fabricability, molybdenum, to ensure hot hardness, and vanadium,
providing secondary hardening, whichalso increases the material’s susceptibility to grain
refinement [1]. In contrast to typical steel grades for carburizing, Pyrowear 53 contains
molybdenum and copper. The addition of these two elements distinguishes it among
the variety of steel grades. Molybdenum is responsible for increasing the heat and wear
abrasion resistance, and copper improves the lubrication properties and shock load [2].
The carburization process of Pyrowear 53 is recommended at temperatures between 870
and 927 ◦ C, while hardening from 904 to 921 ◦ C. To obtain the maximum hardness and
dimensional stability, subzero treatment is recommended at −73 ◦ C. Double-tempering is
recommended for applications requiring elevated dimensional stability [3,4]. For parts with
tight dimensional tolerances, such as power transmission components, distortions, being
an effect of heat treating, have a substantial economic impact on the following machining
processes, increasing the overall production costs by 20–40% to eliminate dimensional
deviations [5].
The analysis of the metallurgical effects during quenching is of great importance.
Due to the complexity of the interrelation between the phenomena and their transient
characteristics, it is challenging to capture the sequence and magnitude of these effects
experimentally. Numerical simulations of heat treatment processes have been developed
and used in the industry to analyze transient processes such as quenching thanks to con-
stantly growing computational capabilities and commercial software availability. There are
multiple systems based on the finite-element method, specifically dedicated to heat treat-
ment processes’ design and optimization; among them, DANTE [6], DEFORM2D/3D [7,8],
and Simufact [9] are either fully dedicated or provide specific modules to solve the thermo-
mechano-metallurgical problems often coupled with diffusion models for carburization or
nitriding analyses. For the computational approach to be efficient, this requires detailed
input data, which, in the case of steels’ heat treatment analysis, may be difficult to find in the
literature or to determine experimentally, as the key to numerical simulation is predicting
that the final property of the material is an effect of the stress evolution caused by the
phase transformation, as well as the difference between the properties of the coexisting
phases. Therefore, the precise definition of the input data for specific phases present in the
system is crucial. To define the temperature-dependent thermophysical and mechanical
properties of each phase or the TTT/CCT diagrams, software such as JMatPro [10–12] or
Thermo-Calc [13] based on the CALPHAD method can be used.
Witness specimens are commonly used to eliminate the need to cut up production
parts, leading to increased costs for development efforts. Standard Navy C-ring-type
specimens are known to reflect the dimensional change of the actual components under
investigation. Its asymmetric geometry prevents uniform cooling and delays the begin-
ning of phase transformation in thicker sections, causing distortion. The relatively simple
geometry of the specimens makes it easy to use as, usually, three characteristics are mea-
sured: the outer diameter, inner diameter, and gap. Numerous research works utilizing the
computational approach and using the C-ring-type specimens as the baseline have been
conducted to predict the distortions that are an effect of the heat treatment, confirming the
accuracy of simulations’ capabilities and the geometry of the specimen [5,14–16].
This paper describes the simulation procedure to predict the influence of the carbon
content and quenching process parameters on the phase composition and hardness dis-
tribution after heat treatment. Because of the relatively new process of high-pressure gas
quenching of Pyrowear 53 for applications in demanding structures, such as aerospace
gears, and the limited amount of literature references related to its properties, the objective
of this work was to research them. To achieve this, numerical simulations were used to
predict the material’s behavior under specific process conditions. Quenching by high-
pressure gas quenching (HPGQ) and OH70 quenching oil was employed to validate the
computational results.
Metals 2023, 13, 371 3 of 17

2. Materials, Methods, and Modeling

2.1. Test Specimen
Twelve Navy C-ring-type specimens, as presented in Figure 1, were analyzed in this
study. The choice of the specimen geometry was dictated by the fact that it is widely known
and accepted in the heat treatment industry as having numerous advantages, among which
the most important is the ability to analyze rapid temperature changes during quenching
and their effects on various cross-sections of the treated parts [17–19]. The Navy C-ring is a
short cylinder with an eccentric hole open at one extreme. Each cross-section has a different
size and, therefore, cooling rate, which leads to variations in the metallurgical effects and,
finally, the properties of the material being analyzed. Due to the transient size change,
the C-ring specimen is a good indicator of actual parts’ behavior during heat treatment.
Six specimens were carburized, while another six were left without carburization. All
specimens underwent cryogenic treatment and tempering. Quenching was performed in
OH70 quenching oil. Low-pressure carburizing (LPC) and high-pressure gas quenching
(HPGQ) were performed in an ALD MonoTherm HK.446.VC.10.gr vacuum furnace. The
details of the heat treatment procedure for all samples are presented in Table 1.

Figure 1. The geometry of the C-ring specimen used in the research. Dimensions are in mm.

Table 1. Test plan description for all specimens.

Specimen No. LPC HPGQ Oil Q.

1 + +
2 + +
3 + +
4 + +
5 + +
6 + +
7 +
8 +
9 +
10 +
11 +
12 +

Specimen Nos. 1 to 6 were processed by LPC at 921 ◦ C, which consisted of 16 boost–

diffusion cycles. The carbon carrier boosts’ total time was 17 min, while the entire process
time was approximately 9.5 h. After the LPC was finished, specimens were cooled down
slowly to room temperature. The load, containing three carburized specimens, Nos. 1,
2, and 3, and three that were kept uncarburized, Nos. 7, 8, and 9, was then heated up to
913 ◦ C and held at this temperature for a sufficient period of time to ensure obtaining a ho-
mogeneous temperature and, therefore, the austenitic microstructure in the whole volume,
then quenched. A standard industrial procedure for parts requiring dimensional stability
cryogenic treatment at −75 ◦ C was performed to finish the martensitic transformation.
Metals 2023, 13, 371 4 of 17

Tempering was performed at 230 ◦ C for 4 h. As two different techniques of quenching

were employed in this research, a variety of heat-transfer-related parameters had to be
incorporated into the simulation. A protective copper cladding was employed for speci-
mens hardened in oil to prevent surface oxidation and decarburization. The copper coating
and stripping were performed electrochemically. Oil quenching was performed in the
RIVA automatic quenching system, which includes a rotary furnace RDLS with a heating
power of 10 kW, a quenching bath OQ-1000 equipped with a 1.1 kW agitation pump, and
vertical collectors to ensure vertical stirring of the OH70 oil. The oil temperature was 45 ◦ C.
The heat transfer coefficient of the oil is shown in Figure 2. The heat transfer in the gas
quenching was considered convective and almost constant [20], which is not realistic and
constitutes the need for optimization to find realistic values. For the sake of this research,
the value of the heat transfer coefficient (HTC) to the environment during gas quenching
was optimized utilizing parabola optimization methods. The cooling curves captured
during an experiment were the objectives. As shown in Figure 3, three heat transfer zones
were defined, and specific upper and lower bounds and initial guesses were initialized for
each. The HTCHPGQ optimization results were further used in the simulations.

3500
HTC OH70
3000

2500
HTC (W/m2 °C)

2000

1500

1000

500

0
0 200 400 600 800
Temperature (°C)

Figure 2. Heat transfer Heat transfer coefficients of OH70 oil’s dependence on temperature (adapted
with permission from Ref. [21], Copyright 2019, Stal, Metale & Nowe Technologie).

Figure 3. Heat transfer zones’ definition.

Hardness was measured using the NEXUS 4303 tester and Vickers method under a
500 g load in the transverse and longitudinal cross-sections of the specimens, as shown in
Figure 4, performed according to aerospace standards to confirm the effective case depth.
Metals 2023, 13, 371 5 of 17

(a) (b)

Figure 4. Hardness check locations in C-ring cross-sections: transverse (a) and longitudinal (b).

Carbon concentration measurement using glow discharge optical emission spec-

troscopy (GD-OES) was performed to provide validation data to correlate the simulation
results with the empirical ones.

2.2. The Material

The material analyzed in this study was the Pyrowear 53 low-alloy steel. The steel’s
chemical composition (wt.%) was measured using a Thermo ARL 3460 optical emission
spectrometer. Table 2 presents the main alloying elements’ content.

Table 2. Chemical composition of Pyrowear 53 steel.

Item C Si Ni Cu Mn Cr Mo V S P Al
Result 0.138 0.945 1.873 1.776 0.319 1.060 3.320 0.092 0.005 0.007 0.002
SD * 0.004 0.008 0.011 0.011 0.001 0.041 0.019 - - - -
* Standard deviation.

In order to obtain an accurate description of the materials’ properties for each phase
present in the material during the whole thermal cycle, which may be further used, the JMat-
Pro simulation was utilized. The CAPLHAD results were then validated and adjusted
by the experimental results. The main adjustments of the inputs made by the authors
consisted of defining the carbon concentration’s influence on the martensite properties,
such as hardness, as shown in Figure 5.

800

700
Hardness [HV0 5]

600

500

400

300
0 0.2 0.4 0.6 0.8 1 1.2
Carbon concentration [wt %]

Figure 5. Dependency of the martensite hardness on carbon concentration for Pyrowear 53 steel.

The model of carbon diffusivity Equation (1) described in [22] and supplemented
with an alloy correction factor Equation (2) [23] that incorporates the influence of alloying
elements on the diffusivity of carbon was used in this research. Thermal data such as
Version February 6, 2023 submitted to Metals 6 of 2
Metals 2023, 13, 371 6 of 17

heat capacity also required adjustments; therefore, experimental data were used [24]. A 146
thermal conductivity
simulation that utilizedand heat capacity
diffusion alsoasrequired
coefficient adjustments;
a function therefore, experimental
of carbon concentration, tempera- 147

ture and alloying elements concentration was performed. The results are presented in thisof
data were used [24]. A simulation that utilized the diffusion coefficient as a function 148
carbon concentration, temperature, and alloying elements’ concentration was performed.
paper. 149
The results are presented in this paper.  
 −(37000 − 6600%C ) 
D = 0.47 · exp(−1.6%C ) · exp −(37, 000 − 6600%C ) · q (1)
D = 0.47 · exp(−1.6%C ) · exp R·T ·q (1)
R·T
where R and T are Boltzmann constant and the carburizing temperature, respectively. 150
where R(2)
The equation and T are the
describes Boltzmann
the constant
alloy correction and the carburizing temperature, respec-
factor. 151
tively. Equation (2) describes the alloy correction factor.

q = 1 + [%Si ] · (0.15 + 0.033[%Si ]) − [%Mn] · 0.0365+

q = 1 + [%Si ] · (0.15 + 0.033[%Si ]) − [%Mn] · 0.0365+
− [%Cr ] · (0.13 − 0.0055 · [%Cr ]) + [%Ni ] · (0.03 − 0.03365 · [%Ni ])+
− [%Cr ] · (0.13 − 0.0055 · [%Cr ]) + [%Ni ] · (0.03 − 0.03365 · [%Ni ])+ (2)
− [%Mo ] · (0.025 − 0.01[%Mo ]) − [%Al ] · (0.03 − 0.02[%Al ])+ (2)
− [%Mo ] · (0.025 − 0.01[%Mo ]) − [%Al ] · (0.03 − 0.02[%Al ])+
− [%Cu] · (0.016 + 0.0014[%Cu]) − [%V ] · (0.22 − 0.01[%V ])
− [%Cu] · (0.016 + 0.0014[%Cu]) − [%V ] · (0.22 − 0.01[%V ])
2.2.1. Heat treatment 152

Heat Treatment
The Continuous Cooling Transformation (CCT) diagram shown in Figure 6 was de- 153

The experimentally
termined continuous cooling transformation
[24]. According to(CCT) diagram shown
it, martensitic in Figure 6starts
transformation was determined
at 438 °C. 154

experimentally [24]. According to it, martensitic transformation starts at 438 ◦ C. Other data may
Other data may be found in the literature where values of 437°C[25], 510°C[4], or 460°C[26] 155

be mentioned.
are found in the Because
literatureofwhere
the untypical 437 ◦ C [25],
values of chemical 510 ◦ C [4], or
composition of 460
◦ C [26] are mentioned.
the Pyrowear 53, which 156

Because
may exceedof the untypical
JMatPro chemical
limits, it wascomposition
found thatofcompared
Pyrowear 53, which mayresults,
to empirical exceed data
the JMatPro
lacks 157

limits, it was
precision. found that,
Therefore compared
attempts to thetaken
have been empirical results,
to adjust andthe data lack
validate precision. model
a numerical Therefore,
of 158

attempts
the material.were made to adjust and validate a numerical model of the material. 159

1000
Ac3=918 ◦ C

800 Ac1 = 774 ◦ C

Ferrite + Carbides
Temperature (°C)

600

Ms = 438°C Bainite
400
Martensite

200

CR 100 20 10 5 1 0.1 0.01

[◦ C/s]
EXP P1 cooling curve
0

100 101 102 103 104 105

Time [s]

Figure6.6.CCT
Figure CCTdiagram
diagramfor
forPyrowear
Pyrowear5353.

Theadjustment
The adjustmentofof the
the martensite
martensite start temperature
temperature(M (Mss))consisted
consistedofofaamodification
modificationof 160

ofthe model
the modelpresented
presentedin [27] by the
in [27] wasauthor.
made byThethe
results
author. of the modification
Results were compared
of modification were 161

to the experimental
confronted resultsresults
by experimental and showed
and showa good
a good fit,fit,asasillustrated
illustratedinin Figure
Figure 7. ItItmust
must 162

be noted that the carbides present in Pyrowear 53 have a remarkable influence

be noted that carbides present in Pyrowear 53 have a remarkable influence on the material’s on the 163

material’showever,
hardness; hardness;
inhowever, in this simulation,
this simulation, martensite ismartensite
the only phase is theformed
only phase
fromformed from
austenite’s 164

austenite’s decomposition; its hardness depends on the carbon content. Both the carbon
Metals 2023, 13, 371 7 of 17

concentration and hardness shown in Figure 5 are empirical data, and their origin, whether
from structural martensite or carbides, are negligible from the numerical point of view in
this case.

500
Original model
Martensite start temperature [◦ C] Modified model
400 Exp. MS of core
Exp. MS of case
300

200

100

0
0 0.2 0.4 0.6 0.8 1 1.2
Carbon concentration [wt %]

Figure 7. Comparison of martensite start temperature models. Original vs. modified by the author.

2.3. Modeling and Simulation

The simulation presented in this paper was based on the finite-element method. Two
computational systems, DEFORM3D and Simufact Forming, were used in this study.
An analysis of the thermo-mechano-metallurgical problem coupled with the carbon diffu-
sion phenomenon is presented, and due to the model’s symmetry, a quarter of the specimen
was used, as shown in Figure 8. The models were meshed using 895,845 tetrahedral
elements. Surface refinement was implemented to ensure results’ accuracy close to the
computational domain boundary. Boundary conditions, both thermal and diffusional, were
assigned to the outer surface of the model. The elasto-plastic model of the material was
used in the simulation. Hardness computations were based on a mixture of the volume
fractions of specific phases.

(a) (b)

Figure 8. Computational domain (a) and FE model with control points P1 and P2 and symmetry
planes (b).

2.3.1. Inverse Heat Transfer Analysis

Heat transfer capabilities of gaseous coolants depend on factors such as gas type, pres-
sure, flow rates, turbulent behavior, or the complexity of parts being treated. The present
research deals with two different quenching procedures. The first is well-researched and
uses liquid quenchant OH70 quenching oil in this case, while the second is high-pressure
gas quenching (HPGQ)—a technique in which convection is the primary mode of heat
Metals 2023, 13, 371 8 of 17

transfer during quenching. Because no precise data are available, the heat transfer co-
efficients for the high-pressure gas quenching were optimized, using the DEFORM3D
Inverse Heat Transfer module, to obtain a realistic input for the quenching simulation. The
cooling curves captured from the experiment were used as the optimization objectives,
Broyden–Fletcher–Goldfarb–Shannon as the optimization algorithm, and B-spline as the
interpolation method [8].

2.3.2. Thermal Field and Latent Heat

The thermal field is described by Fourier’s heat conduction equation for transient
heat transfer. Considering the fact that the phase transformation taking place during rapid
cooling of overcooled austenite, i.e., martensite creation, is exothermic, the latent heat of
the phase transformation alters the thermal field, and therefore, Fourier’s equation can be
written as
∂T
ρC p = ∇(∇(λT )) + L (3)
∂t
where ρ, C p , and λ are the density, specific heat, and thermal conductivity, respectively [28].
L is the latent heat of transformation considered as an additional heat source that influences
the thermal field during quenching.

ζ n +1 − ζ n ∆ζ
L = ∆E = ∆E · (4)
t n +1 − t n ∆t

where ∆E is the enthalpy of austenite transformation to a child phase (see Figure 9) and
ζ n+1 and ζ n are the volume fractions of the specific phase that transformed at tn and tn+1
simulation time steps, respectively [29]. The initial condition at time step t = 0 is defined
as
T |t=0 = T0 ( x, y, z) (5)
and the boundary condition for temperature field calculation during quenching can be
expressed as
∂T  
−λ = hc ( Ts − Te ) + R · e Ts4 − Te4 (6)
∂n
where Te and Ts are the temperatures of the environment and the steel surface. Because the
product of the Boltzmann constant R and the emissivity e is considered as the radiation
heat transfer coefficient,
R · e = hr (7)
Equation (6) can be written as

∂T  
−λ = hc ( Ts − Te ) + hr Ts4 − Te4 = h( Ts − Te ) (8)
∂n
where hc and hr are the convection and radiation coefficients, respectively, and where h
is the total heat transfer coefficient [30,31], which combines the effect of convective and
radiative heat transfer, as both of these phenomena take place simultaneously with a varied
intensity along the quenching time. The determination of the total heat transfer coefficient
was the main goal of the inverse heat transfer analysis.
Metals 2023, 13, 371 9 of 17

700
%C=0.13
600 %C=0.98
500

Enthalpy (J/g)
400

300

200

100

0
−100
0 200 400 600 800 1000
Temperature (°C)

Figure 9. Enthalpies of Pyrowear 53 calculated in JMatPro [24].

2.3.3. Carbon Diffusion Modeling

A low-pressure carburizing process was used to create the gradient profile of the
carbon concentration. The Neumann-type boundary conditions were used to calculate the
carbon content on the surface [2]. The necessary data were the diffusion coefficient, carbon
content at the surface in the equilibrium condition, and the mass transfer coefficient.

∂C
= ∇( D (∇C )) (9)
∂t
where D is the diffusion coefficient, t is time, and C is the carbon concentration at a
specific position. This type of equation requires initial and boundary conditions’ definition.
The initial condition for t = 0 is given as

C ( x, y, z) = C0 (10)

where C0 is the initial carbon content in the steel before carburizing. In this work, carbides’
precipitation was neglected, and the assumption of no soot formation on the steel surface
was made; therefore, the equation for the Neumann-type boundary condition expressing
the mass balance at the surface may be simplified [32,33] as

− D (∇C ) = β(Ce − Cs ) (11)

where Ce is the carbon concentration in equilibrium with the atmosphere and Cs is the
carbon content in the gas–solid interface that reacts with the hot surface of the steel [33].
The surface carbon concentration Ce is required to calculate the mass transfer coefficient
β. The value of this coefficient was determined from the experiment, where the carbon
saturation was constant in time and equal to 60 min. Then, for processes realized at a
constant temperature, T = 921 ◦ C in this research, the value of the mass transfer coefficient
β can be calculated from Equation (12).
 
∆m
A
β= (12)
t(Ce − CS )

where ∆m is the mass of carbon that the specimen could absorb with no soot formation on
the surface and A is the specimen’s surface that underwent carburizing. For cyclic processes
such as low-pressure carburizing, the determinative parameters are the number of cycles
and the total time of the saturation kinetic model given as a function of temperature and
Metals 2023, 13, 371 10 of 17

time factors may be used [33–35]. The approach described above allows determining
the carbon concentration in equilibrium with the atmosphere Ce and the mass transfer
coefficient β as 1.47 (wt.%) and 9.87 × 10−3 ( mm
s ), respectively.

2.3.4. Phase Transformation Kinetics

Depending on the cooling rate, phase transformations may be classified as diffusion-
controlled and diffusionless. For transformation during which diffusion is the governing
phenomenon, the Johnson–Mehl–Avrami–Kolmogorov (JMAK) model is widely accepted
to describe the kinetics of isothermal phase transformation through the nucleation and
growth of the new phase. Cooling the austenite leads to phase transformation into ferrite
(F), pearlite (P), or bainite (B), and the volume fraction of the newly transformed phase can
be predicted according to the JMAK model [36,37].
n
ζ ( F,P,B) = 1 − e−b·t (13)

where ζ ( F,P,B) stands for the volume fraction of ferrite, pearlite, and bainite, respectively,
and b and n are material kinetic parameters defined as:

ln(1−ζ )
ln ln(1−ζ 1 )
n=  2 (14)
ln tt12

ln(1 − ζ 1 )
b=− (15)
t1n
The isothermal times of a certain temperature, t1 and t2 , and the corresponding
volume phase fractions ζ 1 and ζ 2 are defined by means of TTT diagram analysis [29].
Volume fractions of 1% and 99% of the specific phase are usually used as the beginning and
the end of certain phase transformations.
The martensitic transformation is a diffusionless transformation that occurs upon
quick quenching of the austenite phase, and it is characterized by the martensite start
and martensite finish temperatures. As the martensitic transformation is athermal, that
is not being controlled by the thermal history of the material, the volume fraction of the
transformed phase is calculated based on an equation incorporating the degree of under-
cooling of the material. For transformation’s kinetics description, a Koistinen–Marburger
model [38] was used.  
ζ M = ζ A 1 − e−K M ( MS −T (t)) (16)

where
MS − M f
KM = (17)
ln 0.1
While both the martensite start and martensite finish temperatures depend on the
alloying elements’ concentration, the K M parameter is considered [39] as

∑ Si · xi = 0.14x Mn + 0.21xSi + 0.11xCr + 0.08x Ni + 0.05x Mo . (18)

i

where T (t) is the temperature at a specific time step and ζ M and ζ A represent the volume
phase fractions of martensite and austenite, respectively.

2.3.5. Hardness Prediction

Several technological parameters are considered when the heat treatment process is
designed. Hardness is the most-important among them because it is a good indicator of
the overall strengthening of the material while being simple to measure simultaneously.
Metals 2023, 13, 371 11 of 17

The overall hardness of the material is calculated based on the rule of phases mixture,
which defines the total material’s hardness as a weighted sum of the volume fraction of

HV = ζ M HVM + ζ B HVB + ζ P HVP + ζ F HVF (19)

where ζ i is the volume fraction of the i-th phase and HVi is its hardness for i = M, B, P, F,
representing martensite, bainite, pearlite, and ferrite, respectively.
Multiple models are available in the literature describing models for hardness calcu-
lations, among which the Maynier model Equation (20) is considered reliable, although
limited to carbon concentration up to 0.5%wt [40]. An additional Equation (21) for marten-
site hardness containing over 0.5% of carbon was proposed by Leslie [41]:
• For %C < 0.5,

HV =ζ M · (949%C + 156.73 + 21 · log( T85time[s]))+

+ζ B · (185%C + 29.14 + (53 · %C + 36.39) · log( T85time[s]))+ (20)
+(ζ A + ζ F + ζ P ) · (223 · %C + 84.368 + 16.47 · log( T85time[s]))

• For %C > 0.5,

HV =ζ M · (1667%C − 926%C2 + 150)+

+ζ B · (185%C + 29.14 + (53 · %C + 36.39) · log( T85time[s]))+ (21)
+(ζ A + ζ F + ζ P ) · (223 · %C + 84.368 + 16.47 · log( T85time[s]))

Both cases were used for the computations of the carburized case in steel, as the appro-
priate carbon concentration point has a trespassed point of 0.5% of carbon concentration.

3. Results and Discussion

3.1. Heat Transfer Coefficient Optimization
The inverse thermal analysis and optimization result were that heat removal from
the top, side, and bottom surfaces proceeds at different rates. Such behavior is related
to the transient characteristic of cooling and the turbulent flow of the gas, which heats
up at different rates during the cooling of the sample, changing its ability to accumulate
energy. As a result, different heat transfer coefficient values are locally active on the
surface. The DEFORM3D Inverse Heat Transfer module was utilized for this part of the
simulation due to its capability to determine heat transfer coefficients based on an objective
function, which in the case of quenching are the cooling curves at specific points and an
environmental temperature drop as a boundary condition [42]. Optimization revealed that
the heat transfer coefficient values vary depending on the temperature and the specimen’s
location. The highest values were found for the outer diameter surface (Zone 1) reaching its
maximum, i.e., 1.2 mkW ◦
2 ·◦ C for a temperature of approximately 800 C. Intermediate values

of around 1.1 mkW2 ·◦ C were determined for the specimen’s flat faces (Zone 3). In contrast,

the lowest heat transfer of a maximum of 0.87 mkW 2 ·◦ C was found for the inner diameter
(Zone 2).
The results showed the heat transfer coefficients as a function of temperature at the
computational boundary, so influenced by the thermal field only with no accounting of
time. The dashed lines in Figure 10 represent the results of the simulation, which did
not take the latent heat of martensitic transformation into account; therefore, a dimple
in the curves, reaching the minimum at 0.5 mkW 2 ·◦ C , is visible. This is a numerical artifact
caused by the apparent heat capacity of the material. Further analyses of the heat transfer
allowed us to optimize the apparent heat capacity and compute the value of the latent heat
of the martensitic transformation by integrating the function described by the heat capacity
peak’s data points. Integration with the trapezoid method and 100 steps were utilized,
and eventually, the latent heat of 244 gJ was determined and used in further simulations.
Metals 2023, 13, 371 12 of 17

Figure 11 shows the optimization results for the heat capacity and the cooling, where the
determined value of martensitic transformation latent heat was used.

1.2

Optimized HTC (kW/m2 °C) 1

0.8

0.6

0.4
Zone 1
0.2 Zone 2
Zone 3
0
0 200 400 600 800 1000
Temperature (°C)

Figure 10. Optimized values of the heat transfer coefficients for specific zones.

40 1000
Baseline EXP P1
Peak SIM P1
800
Heat capacity ( mmN2 ·K )

30
Temperature (°C)

600
20
400

10
200

0 0
0 200 400 600 800 1000 0 50 100 150 200
Temperature (°C) Time (s)

(a) (b)
Figure 11. The latent heat of martensitic transformation’s optimization results. Optimized apparent
heat capacity (a) and simulated cooling curve with optimized latent heat (b).

A more detailed analysis, which may include a time factor on the change of the
quenching gas temperature and, therefore, impacting the heat transfer between the gas and
the specimen’s surface, would require a CFD approach and computations of the transient
thermal field in the whole volume of the vacuum chamber, which was not the goal of the
current research.

3.2. Low-Pressure Carburizing

Carbon diffusion was simulated and compared with the GD-OES experimental results.
Figure 12 compares the carbon profiles. Sixteen cycles of carbon boosts followed by a
period of diffusion were modeled. The slight discrepancy of the carbon concentration
curves in Figure 12b is an effect of modeling the diffusion coefficient in the steel and may
be improved in further efforts.
The results of the carbon concentration simulation did not vary between the oil
and high-pressure gas quenching processes. Diffusion coefficient model Equation (1)
supplemented with the q factor implementing the chemical composition’s influence on
material’s diffusivity Equation (2) and mass transfer coefficient Equation (12) allowed
computing the diffusion of carbon with a good fit to the experimental values for Pyrowear
53 steel.
Metals 2023, 13, 371 13 of 17

1.2
GD-OES

Carbon concentration (% wt.)

1 Simulated (LPC)

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Depth (mm)

(a) (b)

Figure 12. Simulated carbon concentration. Visualization of the carburized case (a) and comparison
of the experimental and predicted concentration profiles (b) .

3.3. Cooling Behavior

Cooling was analyzed at two control points of the specimen marked in Figure 8. Point
P1 was located in the middle of the thickest cross-section and was the indicator of the core
material behavior. At the same time, the position of point P2 was aimed at carburized
case analysis and, therefore, was located in the thinnest zone 0.05 mm circumferentially
under the surface. Quenching started at time point t = 0. As presented in Figure 13a, in
the first 10 s, the temperature did not drop, which is related to the location of the control
point P1 in the center of the thickest cross-section, 7.95 mm from the surface. Because of the
material’s heat conductivity, a temperature dropin the experimental curve may be observed.
Martensitic transformation starts at approximately 421 ◦ C, and because it is exothermic,
the latent heat released during transformation contracts the quenching extraction, causing
a plateau in the cooling curve. The amount of latent heat for Pyrowear 53 was calculated
as presented in Section 3.1, and it was found to be equal to 244 gJ . Figure 13b presents
a simulated cooling curve for control point P2 located 0.05 mm from the surface. Here,
the temperature decreases much faster with no initial period of constant temperature.
Because of the carbon concentration in the surface layer is equal to approximately 1.1% wt.
and the martensitic transformation starts slightly above 100 ◦ C (see Figure 7), the plateau
in the cooling curve may not be observed.

1000 1000
EXP P1 HPGQ SIM P2 HPGQ
SIM P1 HPGQ
800 800
Temperature (°C)

Temperature (°C)

600 600

400 400

200 200

0 0
0 50 100 150 200 250 0 25 50 75 100 125 150
Time (s) Time (s)
(a) (b)

Figure 13. Cooling curves for the core material at P1 (a) and the carburized case at P2 (b).
Metals 2023, 13, 371 14 of 17

The computed cooling rates presented similarity to those obtained from the experiment.
The choice of a cooling rate of 11 ◦ C/s was found for a temperature T = 715 ◦ C, which
corresponds to a time point of t = 26 s of the quenching process. The decrease of the
cooling rate value corresponding to a temperature of 422 ◦ C was related to the temperature
dropduring the exothermic martensitic transformation, as may be observed in Figure 14.

12 12
EXP P1 EXP P1
SIM P1 10 SIM P1
10

Cooling rate (°C/s)

Cooling rate (°C/s)

8 8

6 6

4 4

2 2

0 0
0 50 100 150 200 250 300 350 400 1000 800 600 400 200 0
Time (s) Temperature (°C)

(a) (b)

Figure 14. Cooling rates as a function of the process time (a) and the temperature (b).

3.4. Phase Composition and Hardness

All specimens were tested against hardness. Both longitudinal and transverse cross-
sections, as shown in Figure 4, were measured and showed similar results. The carburized
material presented a similar carbon concentration profile, which did not depend on the
quenching technique. The average hardness at a distance of 0.1 mm from the surface for
carburized specimens was 760 HV. According to the AGMA standards, the effective case
depth (ECD) is the distance from the surface of the specimen where the hardness is 50 HRC,
corresponding to approximately 513 HV. For the analyzed process parameters, an effective
case depth of 1.1 mm can be obtained for Pyrowear 53. Figure 15 compares the hardness
distribution curves obtained from the simulation with the experimental curves, being the
arithmetic average of all carburized specimens. The presented hardness profiles showed
that the differences were barely noticeable, which means the carbon concentration profile
was not affected by the quenching method. Figure 16 presents the transformation and final
distribution of the phases after the quenching. Only two phases were present in Pyrowear
53 after heat treatment by the analyzed process. Although the cooling curve measured
at P1 shown in the CCT diagram in Figure 6 crosses the point of the beginning of bainite
transformation, the bainite was not observed, probably because of its content in the range
of a few percent. Based on that, it was found that no products of austenite decomposition
other than martensite formed with the cooling rates as analyzed, which is in agreement
with other research [26].
Metals 2023, 13, 371 15 of 17

900
Exp LPC+HPGQ
800 Exp LPC+Oil
SIM LPC+HPGQ

Hardness (HV0.5)
700 SIM LPC+Oil

600

500

400
ECD
300
0 0.4 0.8 1.2 1.6 2
Depth (mm)

Figure 15. Results of hardness profile simulation comparison with the experimentally measured after
the HPGQ and oil quenching processes.

A Vol. Frac = 0.073

0.75
Volume fraction [−]

Austenite
0.5
Martensite

0.25

M Vol.Frac = 0.927
0
0 75 150 225 300 375 450 525 600 675
Time [s]

Figure 16. Computed phase volume fraction changes during quenching for a control point P1.

4. Conclusions
This paper presented the results of heat-treated specimens made from Pyrowear
53 low-alloy steel. The simulation of the quenching of previously carburized and non-
carburized specimens was analyzed. The analysis of the C-ring, which went through LPC,
followed by different quenching techniques, also concluded that high-pressure gas quench-
ing provides results comparable to standard oil quenching. The numerical simulation of
the heat treatment processes could accelerate new procedures’ implementation and lower
development costs. The simulation of the heat-treatment process using Simufact Forming
supplied with the input of JMatPro material’s properties, although requiring validations
and some adjustments, provided a good correlation with the experimental measurements
for all analyzed variables. A computational approach as presented in this paper’s procedure
for phase composition and hardness analysis may be successfully applied to the analy-
sis of production parts made from different alloys to optimize the process by providing
metallurgical analysis with a limited testing campaign.

Author Contributions: Conceptualization, B.I. and M.M.; methodology, B.I. and A.W.; software, B.I.;
validation, B.I. and M.M.; formal analysis, M.M.; investigation, B.I. and A.W.; resources, B.I. and
Metals 2023, 13, 371 16 of 17

A.W.; data curation, B.I.; writing—original draft preparation, B.I.; writing—review and editing, B.I.;
visualization, B.I.; supervision, M.M.; project administration, B.I.; funding acquisition, M.M. All
authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Not applicable.
Acknowledgments: For calculations and simulations in this work, some of the results gathered within
the framework of the development project in the TECHMATSTRATEG2/406725/1/NCBR/2020
program of the National Centre for Research and Development were used. In particular, the CCT
diagram (Figure 6) was prepared by W. Zalecki from the Łukasiewicz Research Network - Upper
Silesian Institute of Technology. The authors would also like to express their gratitude to FIN Sp. z o.o.
for the preparation of the C-ring specimens that were used in the experiments described in this article.
Conflicts of Interest: The authors declare no conflict of interest.

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