metals

Article
Study of the Effect of Quenching and Tempering Modes
on the Strength Level of Alloyed Structural Steels Used to
Produce Fasteners
Alexander Zaitsev 1 , Anton Koldaev 1 , Alexey Stepanov 1 , Nataliya Arutyunyan 1,2, *, Alexey Stolyarov 3 ,
Mariya Zaytseva 3 and Dmitrii Konstantinov 4

1 Bardin Central Research Institute of Ferrous Metallurgy, 105005 Moscow, Russia

2 Faculty of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia
3 Magnitogorsk Hardware and Sizing Plant «MMK-METIZ», OJSC, 455019 Magnitogorsk, Russia
4 Department of Mechanical Engineering and Metallurgical Technologies, Nosov Magnitogorsk State Technical
University, 455000 Magnitogorsk, Russia
* Correspondence: [email protected]; Tel.: +7-495-939-1673

Abstract: The development of high-strength fasteners is required due to the modern trend of reducing
the weight of engineering structures. At present, structural bolts of property classes 8.8–10.9 are
widely used, and higher-strength bolts of property classes 12.9 and 14.9 are being developed. In
this paper, we analyzed the possibilities and conditions for manufacturing fasteners of different
strength categories from steels of seven grades, containing and not containing boron. The necessary
corresponding temperature ranges of processing are determined based on the study of hot-rolled
round steel. Tensile strength, yield strength, relative elongation, reduction in area, and Vickers
microhardness were measured. An analysis was made of the hardenability and the influence of the
holding time during tempering on the mechanical properties of the considered round steel. Using the
Citation: Zaitsev, A.; Koldaev, A.;
method of scanning electron microscopy, the effect of carbide precipitation during tempering on the
Stepanov, A.; Arutyunyan, N.;
mechanical properties of fasteners was established.
Stolyarov, A.; Zaytseva, M.;
Konstantinov, D. Study of the Effect
Keywords: high-strength fasteners; round bolts; property class 12.9; quenching; tempering;
of Quenching and Tempering Modes
austenitization; mechanical properties
on the Strength Level of Alloyed
Structural Steels Used to Produce
Fasteners. Metals 2022, 12, 1501.
https://doi.org/10.3390/met12091501
1. Introduction
Academic Editor: Giovanni Principi
Modern trends in reducing the weight of engineering structures to save both material
Received: 13 August 2022 and energy have led to the development of lighter and stronger materials, including in
Accepted: 8 September 2022 the automotive industry [1]. In turn, this require high-strength fasteners that can reduce
Published: 10 September 2022 the size of the fastening element. The traditional process of their manufacture is upsetting
Publisher’s Note: MDPI stays neutral
and/or cold forging of steel wire [2]. To obtain high indicators of the mechanical properties
with regard to jurisdictional claims in of finished products, they are subjected to final heat treatment, including austenitization,
published maps and institutional affil- quenching, and tempering [3]. In the last decade, structural bolts of property classes 8.8,
iations. 9.8, and 10.9 have been widely used [4]. At the same time, a number of studies have been
carried out to develop higher-strength bolts of classes 12.9 and 14.9 (tensile strength of at
least 1220–1400 MPa, with a yield strength coefficient of more than 0.9) [5–7]; however,
the available information for the selection of steel grades and their mass production is not
Copyright: © 2022 by the authors. enough.
Licensee MDPI, Basel, Switzerland. In global practice, in the production of high-strength bolts, medium-carbon and
This article is an open access article alloyed steels containing boron, manganese, and chromium are usually used, for example,
distributed under the terms and
10B21 [3], 20MnTiB [3], 32CrB4 [3,8], 33B2 [6], 34Cr4 [3,6], and 34CrNiMo6 [5]. These
conditions of the Creative Commons
alloying elements increase strength and hardenability. A feature of alloying with boron
Attribution (CC BY) license (https://
is a significant increase in hardenability at very low concentrations (thousandths of a
creativecommons.org/licenses/by/
percent) [9,10]. At the same time, the implementation of the positive effect of boron in
4.0/).

Metals 2022, 12, 1501. https://doi.org/10.3390/met12091501 https://www.mdpi.com/journal/metals

Metals 2022, 12, 1501 2 of 14

practice causes problems associated with the difficult-to-control behavior of this element in
steel, due to its high tendency to form boron oxide, nitride, and carboborides. In fact, only
that part of the boron present in the steel, which is in a solid solution, contributes to the
increase in hardenability, while the formation of a noticeable amount of boron oxide, nitride,
and carboborides leads to a decrease in hardenability [11]. This feature of boron-containing
steels leads to an instability of strengthening by quenching of the parts, and the production
of boron-containing steels is associated with certain difficulties. Among them, there are the
difficulties of a metallurgical nature: the need to obtain strictly normalized concentrations in
the process of steel smelting, maintaining the content of nitrogen, titanium, and aluminum
at a given level. In addition, there are still no scientifically based principles for choosing
a heat-treatment mode depending on the technological features of manufacturing and
the content of boron and carbon. In many cases, boron steels do not have sufficient
hardenability to make fasteners of a large size (diameter).
Therefore, not only boron-containing steels for the manufacture of high-strength
bolts are currently being developed, but also boron-free steels. The most studied steel
is 42CrMo [12–14]. Few works are devoted to steels with a lower carbon content, for
example, 35CrMo [15] and 34CrNiMo6 [5,16]. At the same time, the implementation of
hardening mechanisms in these steels is different and requires additional research. For
42CrMo, its higher carbon content promotes the formation of more carbide, and finer
grains are obtained after quenching [15]. However, by varying the tempering temperatures
after quenching, it becomes possible to change the amount of carbide precipitates, thereby
changing the contribution of precipitation strengthening and achieving different levels of
mechanical properties.
This work was aimed at studying the possibilities and conditions for manufacturing
fasteners of different strength categories from seven different steel grades, containing and
not containing boron.

2. Materials and Methods

Hot-rolled round steels of industrial production, with a diameter of 22, 21, and 19 mm
from steel of grades 42CrMo4, 32CrB4, and 40KhN2MA, respectively, as well as of labora-
tory production with a diameter of 20 mm from steel of grades 34CrNiMo6, 31CrMoB2,
32KhGMR, and 35KhNMFA, were studied. The chemical composition is presented in
Table 1. The 32KhGMR and 35KhNMFA steels are experimental, as their composition was
first developed in this work. All other steels are commonly used for the manufacture of
fasteners.

Table 1. Chemical composition of the studied steels (wt.%).

Steel C Si Mn S P Cr Ni Cu Mo Al Ti V B N Ca
32CrMo4 0.41 0.24 0.7 0.002 0.010 1.02 0.04 0.04 0.198 0.026 0.002 0.005 - 0.009 0.0017
32CrB4 0.32 0.21 0.65 0.003 0.010 0.91 0.03 0.04 0.002 0.024 0.040 0.005 0.0024 0.008 0.0026
40KhN2MA 0.39 0.25 0.53 0.002 0.008 0.67 1.27 0.03 0.17 0.025 0.002 0.003 - 0.008 0.0030
34CrNiMo6 0.38 0.21 0.66 0.005 0.005 1.53 1.3 0.02 0.29 0.02 - - - 0.007 -
31CrMoB2 0.29 0.30 0.94 0.005 0.005 0.53 0.18 0.02 0.15 0.02 0.04 - 0.006 0.007 -
32KhGMR 0.34 0.24 1.12 0.005 0.005 0.54 0.31 0.02 0.35 0.01 0.03 - 0.006 0.007 -
35KhNMFA 0.33 0.35 0.91 0.005 0.005 1.08 1.5 0.02 0.43 0.14 0.07 0.16 - 0.007 -

The austenitization temperature (Table 2) for each steel grade was determined using
proprietary software (Bardin TsNIIChermet, Moscow, Russia) based on data from the
steel atlas [17]. The temperature at which homogeneous austenite should form for the
case of metal heating at a rate of 1 ◦ C/s was taken as the austenitization temperature,
which approximately corresponds to the conditions for achieving a uniform temperature
distribution over the cross section of hardened fasteners in a furnace for 13–15 min. Since,
 2022, 12, x FOR PEER REVIEW 3 of 15

Metals 2022, 12, 1501 3 of 14

of metal heating at a rate of 1 °C/s was taken as the austenitization temperature, which
approximately corresponds to the conditions for achieving a uniform temperature distri-
bution over the cross section of hardened fasteners in a furnace for 13–15 min. Since, under
under
real conditions, real conditions,
the temperature the temperature
distribution distribution
in the furnace in from
may differ the furnace may differ from the
the theoretical
theoretical calculation, a positive temperature margin of 10–15 ◦ C was created.
calculation, a positive temperature margin of 10–15 °C was created.
Table 2. Austenitization temperature values for the studied steels.
Table 2. Austenitization temperature values for the studied steels.

Steel Steel
42CrMo4 42CrMo4 40KhN2MA
32CrB4 32CrB4 40KhN2MA
34CrNiMo6 34CrNiMo6
31CrMoB2 31CrMoB2
32KhGMR 32KhGMR
35KhNMFA 35KhNMFA
T845 ◦
ust, °C aust , C 860845 850860 850
850 850
860 860
850 850
850 850

To analyze theTohardenability, samples with samples

analyze the hardenability, a length of 150amm
with were
length ofheated
150 mm in awere
la- heated in a
boratory tubelaboratory
resistancetube
furnace SUOЛ-0.4.4/12
resistance (Tulaterm, Tula,
furnace SUOL-0.4.4/12 Russia) to
(Tulaterm, theRussia)
Tula, selectedto the selected
research temperature
research for 15 min, followed
temperature by holding
for 15 min, followedforby45holding
min, andforthen quenched
45 min, and thenintoquenched into
oil. Cylindersoil.
with a height
Cylinders of 5a height
with mm and of 5a mm
diameter
and a corresponding to rolled to
diameter corresponding products
rolled products were
were cut fromcutthefrom
obtained samplessamples
the obtained from thefrom
middle along the
the middle length,
along the and microsections
length, and microsections were
were made tomadestudytomicrohardness using a Struers Duramin-20 tester (Struers
study microhardness using a Struers Duramin-20 tester (Struers ApS,ApS,
Co- Copenhagen,
penhagen, Denmark).
Denmark). Vickers
Vickersmicrohardness
microhardnesswas wasmeasured
measuredininthree
threedifferent
differentareas
areas of
of the microsection,
microsection,according
accordingto tothe
thescheme
schemeshown
shownin inFigure
Figure1.1.

Figure 1. Conventional scheme of microhardness measurements on the cross section of a round bar
Figure 1. Conventional scheme of microhardness measurements on the cross section of a round
sample.
bar sample.
Samples of hot-rolled steels with a length of 65 mm were subjected to austenitization,
Samples of hot-rolled steels with a length of 65 mm were subjected to austenitization,
according to the selected mode, followed by oil quenching. After quenching, the samples
according to the selected mode, followed by oil quenching. After quenching, the samples
were tempered in a laboratory tube resistance furnace at temperatures of 450, 500, and 550
were tempered in a laboratory tube resistance furnace at temperatures of 450, 500, and
°C for 60 min. The tempering temperatures were chosen on the basis of the results [8],
550 ◦ C for 60 min. The tempering temperatures were chosen on the basis of the results [8],
which showed that when
which showed thethat
tempering temperature
when the temperingof 32CrB4 rolled
temperature products
of 32CrB4 decreases,
rolled products decreases,
especially below
especially below 450 ◦ C, the relative elongation sharply decreases. Inthe
450 °C, the relative elongation sharply decreases. In addition, for- the forma-
addition,
mation of thetion
microstructure of round of
of the microstructure rolled
roundproducts made of made
rolled products 40KhN2MA grade steel
of 40KhN2MA grade steel was
was studied after tempering at temperatures from 400 to 550
studied after tempering at temperatures from 400 to 550 C.°C. ◦
To substantiateTo the chosen duration
substantiate the chosenof tempering,
duration of the influence
tempering, theofinfluence
the holding time
of the holding time in
in the furnacethe
was studied, which was 30, 45, 60, 75, and 90 min. Samples with a diameter
furnace was studied, which was 30, 45, 60, 75, and 90 min. Samples with a diameter
of 5 mm and ofa length
5 mm of and25amm were
length of turned
25 mm from
were the obtained
turned samples
from the to determine
obtained samples to thedetermine the
mechanical properties.
mechanical The measurement
properties. was carried out
The measurement wasoncarried
an INSTRON-150LX tensile
out on an INSTRON-150LX tensile
testing machine (Illinois
testing Tool (Illinois
machine Works, Inc.,
Tool Norwood,
Works, Inc.,MA, USA). MA, USA).
Norwood,
The microstructure was studied using
The microstructure scanning
was studied electron
using microscopy
scanning electronon a JEOL JSM-
microscopy on a JEOL JSM-
6610LV microscope (JEOL Ltd, Tokyo, Japan).
6610LV microscope (JEOL Ltd., Tokyo, Japan).

3. Results and3.Discussion
Results and Discussion
3.1. Analysis of3.1.
theAnalysis of the of
Hardenability Hardenability of Rolled
Rolled Products underProducts
Study under Study
Table 3 shows the results of the study of the hardenability of rolled products of all
considered steels, based on the measurement of microhardness, according to the scheme
shown in Figure 1.
Metals 2022, 12, 1501 4 of 14

Table 3. Results of measurement of Vickers microhardness on samples of hot-rolled studied steel

after quenching.

Microhardness Value, HV
Deviation of HV in
Measurement Measurement Area
Steel Sample the Axial Zone from
Number
Surface Middle Axial Average the Average, %

1 660 659 644

42CrMo4 2 655 666 638 656.3 −1.9
3 664 672 649
1 547 560 556
32CrB4 2 546 546 542 549.9 −0.1
3 544 557 552
1 602 628 601
40KhN2MA 2 604 625 605 610.6 −0.9
3 599 621 610
1 627 629 635
34CrNiMo6 2 632 636 648 632.9 0.9
3 625 632 632
1 538 552 546
31CrMoB2 2 537 553 555 545.7 0.7
3 532 550 548
1 598 585 600
32KhGMR 2 604 591 598 598.1 0.6
3 606 594 607
1 604 596 604
35KhNMFA 2 597 606 603 601.7 0.8
3 598 595 612

From the data in Table 3, it can be seen that for all the studied samples of rolled
products, a uniform distribution of hardness is observed, namely there is no regular
decrease in hardness from the surface to the axial zone by more than 5% (relative). At
the same time, for samples of all considered steels, including those not containing boron
(40KhN2MA, 34CrNiMo6, 35KhNMFA), except for 42CrMo4 steel, the deviation is less
than 1%. This indicates a sufficiently high hardenability of the studied steels.

3.2. Regularities of Influence of Temperature and Duration of Tempering

To substantiate the optimal temperature and time parameters of tempering, the effect
of tempering temperature on the formation of the microstructure of round rolled prod-
ucts from 40KhN2MA grade steel, after quenching and tempering at temperatures from
400 to 550 ◦ C, was studied. Figure 2 shows the microstructure of 40KhN2MA steel after
austenitization at a temperature of 850 ◦ C for 45 min and subsequent oil quenching.
Figure 2 shows that after the austenitization, rolled products made of 40KhN2MA
grade steel have a uniform martensitic structure. Figure 3 shows a view of the microstruc-
ture of this steel at tempering temperatures of 400, 425, 450, 500, and 550 ◦ C for one hour.
Metals 2022, 12, x FOR PEER REVIEW 5 of 15

Metals 2022,
Metals 12, 12,
2022, 1501x FOR PEER REVIEW 5 of 515
of 14

(a) (b)
Figure 2. Microstructure of a round-rolled sample from 40KhN2MA grade steel after austenitization
at a temperature of 850 °C for 45 min and subsequent oil quenching: (a) magnification ×2000 and (b)
magnification
(a) ×5000. (b)
Figure 2. Microstructure
Figure 2 shows that of a round-rolled sample from 40KhN2MA grade steel after austenitization
Figure 2. Microstructure of aafter the austenitization,
round-rolled rolled products
sample from 40KhN2MA made
grade steel ofaustenitization
after 40KhN2MA
at a temperature of 850 °C for 45 min and subsequent oil quenching: (a) magnification ×2000 and (b)
grade steel
atmagnificationhave
a temperature a uniform
◦ martensitic structure. Figure 3 shows a view
of 850 C for 45 min and subsequent oil quenching: (a) magnification of the microstruc-
×2000 and
×5000.
ture of this steel at
(b) magnification ×5000. tempering temperatures of 400, 425, 450, 500, and 550 °C for one hour.
Figure 2 shows that after the austenitization, rolled products made of 40KhN2MA
grade steel have a uniform martensitic structure. Figure 3 shows a view of the microstruc-
ture of this steel at tempering temperatures of 400, 425, 450, 500, and 550 °C for one hour.

Metals 2022, 12, x FOR PEER REVIEW 6 of 15

(a) (b)

(a) (b)

(c) (d)
Figure 3. Cont.
Metals 2022, 12, 1501 6 of 14

(c) (d)

(e) (f)

Metals 2022, 12, x FOR PEER REVIEW 7 of 15

(g) (h)

(i) (j)
Figure 3. Microstructure of a round-rolled sample made of 40KhN2MA grade steel after quenching
Figure 3. Microstructure of a round-rolled sample made of 40KhN2MA grade steel after quenching
and tempering for 1 h at a temperature of: (a,b) 400 ◦°C; (c,d) 425 ◦°C; (e,f) 450 ◦°C; (g,h) 500 ◦°C; and
and tempering
(i,j) 550 for 1point
°C. Arrows h at atotemperature
carbides. of: (a,b) 400 C; (c,d) 425 C; (e,f) 450 C; (g,h) 500 C; and
(i,j) 550 ◦ C. Arrows point to carbides.
It can be seen from Figure 3 that at tempering temperatures of 400 and 425 °C, only
It can be seen from Figure 3 that at tempering temperatures of 400 and 425 ◦ C, only the
the initial stage of the formation of submicron carbide precipitates is observed directly
initial stage of the formation of submicron carbide precipitates is observed directly inside
inside the martensite. Starting from a temperature of 450 °C and higher, a sharp increase
in the intensity of the formation of carbide precipitates along the boundaries of martensite
blocks is seen, which compensates for the drop in strength due to the gradual decompo-
sition of martensite. This is certainly more preferable, since internal stresses in the metal
are significantly reduced, which can adversely affect the mechanical and other service
Metals 2022, 12, 1501 7 of 14

the martensite. Starting from a temperature of 450 ◦ C and higher, a sharp increase in the
intensity of the formation of carbide precipitates along the boundaries of martensite blocks
is seen, which compensates for the drop in strength due to the gradual decomposition of
martensite. This is certainly more preferable, since internal stresses in the metal are signifi-
cantly reduced, which can adversely affect the mechanical and other service properties of
high-strength fasteners. Thus, the data obtained explain the decrease in the plasticity of
round bars at tempering temperatures below 450 ◦ C [8].
In order to determine the optimal duration of tempering, its influence on the mechani-
cal properties of hot-rolled round bars made of 42CrMo4 steel was studied. The results of
the determination of mechanical properties are presented in Table 4 and Figure 4.

Table 4. Mechanical properties of samples of hot-rolled 42CrMo4 grade steel after quenching and
tempering at 500 ◦ C after various durations.

Tempering Mechanical Properties

Durations,
σ0.2 , MPa σB , MPa δ, % Ψ, % HV
min
30 1200 1300 12.0 54.0 413
45 1200 1290 12.0 50.0 407
60 1190 1280 12.5 54.5 403
Metals 2022, 12, x FOR PEER REVIEW 75 1180 1270 13.0 55.0 399 8 of 15
90 1170 1260 12.5 54.0 396

(a) (b)

(c) (d)

Figure 4. Cont.
Metals 2022, 12, 1501 8 of 14

(c) (d)

(e)
Figure 4. Dependences of mechanical properties of rolled products from 42CrMo4 grade steel on
Figure 4. Dependences of mechanical properties of rolled products from 42CrMo4 grade steel on
the duration of tempering at 500 °C: (a) tensile strength; (b) yield strength; (c) relative elongation;
the duration of tempering at 500 ◦ C: (a) tensile strength; (b) yield strength; (c) relative elongation;
(d) reduction in area; and (e) microhardness HV.
(d) reduction in area; and (e) microhardness HV.
From the data in Table 4 and Figure 4, it follows that in the entire investigated tem-
From the data in Table 4 and Figure 4, it follows that in the entire investigated temper-
pering time interval at a temperature of 500 °C, the required mechanical properties for
ing time interval at a temperature of 500 ◦ C, the required mechanical properties for property
class property class 12.9 However,
12.9 are achieved. are achieved. However,
it should it should
be noted that be
withnoted that withduration
a tempering a tempering
of du-
45 min, a decrease in the reduction in area value was detected. Since, when tempering tem-
ration of 45 min, a decrease in the reduction in area value was detected. Since, when
pering
for 60–90 foris60–90
min usedmin is used
at the at the
studied studied temperature,
temperature, the necessary
the necessary strength properties
strength properties are
are achieved, and the plasticity of the metal increases slightly, it is advisable to use the
achieved, and the plasticity of the metal increases slightly, it is advisable to use the duration
durationinofthis
of tempering tempering
range. in this range.

3.3. Investigation of the Possibility and Conditions for Manufacturing Fasteners of Various
Property Classes from the Studied Steels
The results of determining the mechanical properties of samples of hot-rolled round
bars from the studied steels after quenching and tempering at various temperatures are
presented in Table 5.
From Table 5, it follows that the property class 12.9 corresponds to rolled products
from steels 42CrMo4, 34CrNiMo6, and 32KhGMR, after tempering at temperatures of
450 and 500 ◦ C, and rolled products from steels 40KhN2MA, 31CrMoB2, and 32CrB4, after
tempering only at a temperature of 450 ◦ C. It should be noted that for 34CrNiMo6 steel in [5],
containing wt.% 0.035 C–0.649 Mn–0.129 Si–1.616 Cr–1.554 Ni–0.250 Mo–0.013P–0.008 S,
similar results were obtained after tempering for 60 min at 520 ◦ C. The tensile strength,
yield strength, and reduction in area were 1300 MPa, 1230 MPa, and 61%, respectively.
Rolled products from 35KhNMFA steel mainly meet the requirements for ultra-high-
strength property class 14.9, with an obvious possibility of obtaining fasteners of property
class 12.9 at a tempering temperature of 550 ◦ C and higher. The lowest strength properties
are found for steels 32CrB4 and 31CrMoB2. After tempering at temperatures of 500 ◦ C,
they correspond to property class 10.9.
In [6], KNDS4 steel of a similar composition was studied, with wt.% 0.39 C–0.45
Mn–0.05 Si–0.004 P–0.006 S–0.033 Al–1.07 Cr–1.09 Mo–0.042 Ti–0.085 V. After austenitization
at 925 ◦ C for 60 min and quenching and tempering at 550 ◦ C for 90 min, the tensile strength
and yield strength were obtained as higher than those of 35KhNMFA steel: 1504 MPa and
1267 MPa, respectively. At the same time, the ratio of yield strength to tensile strength
was only 0.84, while for 35KhNMFA steel, this value is 0.95. The authors attribute the
high tensile strength to the high austenitization temperature and the complete dissolution
of alloying elements during the austenitizing treatment, which increased the volume
fraction of carbides precipitated during tempering. Apparently, this was also facilitated
by a higher content of carbon and molybdenum. According to [18–20], the presence of
Metals 2022, 12, 1501 9 of 14

molybdenum in the steel composition facilitates the nucleation and inhibits the growth of
carbide precipitates, which increases the contribution of dispersion strengthening.

Table 5. Mechanical properties of hot-rolled round bars after quenching and tempering at various
temperatures.

Tempering Diameter, Mechanical Properties

Steel Temperature, mm σ0.2 , MPa σB , MPa δ, % Ψ, % HV
◦C
450 1320 1400 12.0 53 445
42CrMo4 500 22 1200 1280 14.0 55 404
550 1080 1180 15.0 58 376
450 1200 1270 14 62 390
32CrB4 500 21 1050 1110 17 63 342
550 880 960 19 66 297
450 1210 1300 14.0 54 407
40KhN2MA 500 19 1110 1210 15.5 62 379
550 980 1080 17.0 63 341
450 1330 1470 13.0 53 454
34CrNiMo6 500 20 1220 1330 14.5 57 417
550 1120 1230 16.0 60 382
450 1220 1270 14.0 62 392
31CrMoB2 500 20 1080 1130 15.5 63 353
550 930 1000 17.0 66 313
450 1300 1380 13.5 60 424
32KhGMR 500 20 1180 1250 15.0 60 390
550 1060 1140 16.5 60 359
450 1410 1490 12.0 55 457
35KhNMFA 500 20 1350 1420 14.0 55 443
550 1300 1360 15.5 56 430
ISO 898-1 requirements for property class 10.9 ≥940 ≥1040 ≥9.0 ≥48 320–380
ISO 898-1 requirements for property class 12.9 ≥1100 ≥1220 ≥8.0 ≥44 385–435

It is important to note that the relative elongation and reduction in area for rolled
products from all considered steels satisfies the requirements for property class 12.9 of
fasteners in the entire investigated tempering temperature range from 450 to 550 ◦ C.
Therefore, the tempering temperature range was refined to determine the interval, at which
the values of all mechanical properties are achieved, which meets the requirements for
property class 12.9 of fasteners for 42CrMo4, 34CrNiMo6, 32KhGMR, and 40KhN2MA steels.
For 32CrB4, 40KhN2MA, 31CrMoB2, and 32KhGMR rolled steels, tempering temperatures
were also analyzed to obtain property class 10.9.
Figure 5 shows the obtained values of tensile strength and microhardness depending
on tempering temperature. The horizontal lines represent the upper and lower limits of the
tensile strength and Vickers hardness values for fasteners of property classes 12.9 and 10.9.
The graphical analysis carried out by the method of linear interpolation made it possible to
determine the upper and lower limits of the tempering temperatures at which the required
mechanical properties are achieved (Table 6).
An analysis of the data in Table 6 shows that round bars made of 42CrMo4, 40KhN2MA,
34CrNiMo6, and 32KhGMR steels, meeting the requirements for property class 12.9, can
be obtained after tempering in a wide temperature range: about 60–70 ◦ C. For 31CrMoB2
rolled products, it is necessary to use an extremely narrow interval of tempering tempera-
tures. This, due to technological difficulties, can lead to an increase in the probability of
rejection by mechanical properties.
Rolled products made of 40KhN2MA and 32KhGMR steels can be used for the manu-
facturing fasteners of both property classes: 12.9 and 10.9. At the same time, compared with
40KhN2MA steel, 32KhGMR rolled products have a wider tempering temperature range to
obtain property class 10.9. In addition, it can be assumed that due to the need to use higher
 of carbides precipitated during tempering. Apparently, this was also facilitated by a
higher content of carbon and molybdenum. According to [18–20], the presence of molyb-
Metals 2022, 12, 1501 denum in the steel composition facilitates the nucleation and inhibits the growth of car-
10 of 14
bide precipitates, which increases the contribution of dispersion strengthening.
It is important to note that the relative elongation and reduction in area for rolled
products from all considered steels satisfies the requirements for property class 12.9 of
tempering temperatures and a lower carbon content, products made of 32KhGMR steel
fasteners in the entire investigated tempering temperature range from 450 to 550 °C.
will have higher service properties, including fatigue strength.
Therefore, the tempering temperature range was refined to determine the interval, at
which6.the
Table values
Upper andof all mechanical
lower properties
limits of tempering are achieved,
temperatures which
at which meets theproperties
mechanical requirements
corre-
for property
sponding class 12.9
to property of fasteners
classes for 42CrMo4,
10.9 and 12.9 34CrNiMo6,
are achieved, 32KhGMR,
as well as the arithmetic and
mean40KhN2MA
value of the
steels.temperature
found For 32CrB4, 40KhN2MA, 31CrMoB2, and 32KhGMR rolled steels, tempering tem-
range.
peratures were also analyzed to obtain property class 10.9.
Steel 42CrMo4 32CrB4
Figure 5 shows the 40KhN2MA
obtained values 34CrNiMo6 31CrMoB2
of tensile strength and microhardness 32KhGMR
depending
Property class 12.9 on tempering
10.9 12.9 temperature.
10.9 The
12.9horizontal
12.9lines represent
10.9 the12.9
upper and lower limits
10.9 12.9 of
Tmin, ◦ C 462 ± 5 the
467 ± 5tensile strength
450 ± 5 and
450 ± 5Vickers hardness
498 ± 5 values
476 ± 5 for fasteners
476 ± 5 of property
450 ± 5 classes
524 ± 5 450 ±and
12.9 5
10.9. The graphical analysis carried out by the method of linear interpolation made it pos-
Tmax, ◦ C 532 ± 5 523 ± 5 460 ± 5 485 ± 5 570 ± 5 546 ± 5 534 ± 5 465 ± 5 591 ± 5 509 ± 5
sible to determine the upper and lower limits of the tempering temperatures at which the
Tmean, ◦ C 497 495 455
required mechanical 468
properties534are achieved
511 (Table 6).505 458 558 480

(a) (b)

(c) (d)

(e) (f)

Figure 5. Cont.
Metals 2022, 12,
Metals 2022, 12, 1501
x FOR PEER REVIEW 11 of
11 of 14
15

(g) (h)

(i) (j)

(k) (l)

(m) (n)
Figure 5. Dependences of the tensile strength and HV hardness on the tempering temperature of
Figure 5. Dependences of the tensile strength and HV hardness on the tempering temperature of
rolled products made of steel of grades: (a,b) 42CrMo4; (c,d) 32CrB4; (e,f) 40KhN2MA; (g,h)
rolled products made of steel of grades: (a,b) 42CrMo4; (c,d) 32CrB4; (e,f) 40KhN2MA; (g,h) 34CrN-
34CrNiMo6; (i,j) 31CrMoB2; (k,l) 32KhGMR; and (m,n) 35KhNMFA. Orange horizontal lines corre-
iMo6;
spond(i,j) 31CrMoB2;
to the maximum (k,l)
and32KhGMR;
minimumand (m,n)
values of35KhNMFA. Orange
properties for horizontal
property linesgreen
class 12.9, correspond to
lines cor-
the maximum
respond and minimum
to property class 10.9.values of properties for property class 12.9, green lines correspond to
property class 10.9.
Metals 2022, 12, 1501 12 of 14

The results obtained indicate the possibility of manufacturing fasteners from 32CrB4
grade steel not only of property class 10.9, but also of lower property classes, including
8.8 and 9.8, by increasing the tempering temperature to 540–600 ◦ C. Despite the possibility
of achieving values of strength characteristics corresponding to property class 12.9, it is
clear that it is necessary to use an extremely narrow range of tempering temperatures
(Table 6). Therefore, it is advisable to use rolled steel of 32CrB4 grade for manufacturing
fasteners of property class 10.9, and, if necessary, 8.8 and 9.8.
Currently, the required properties for fasteners of property class 14.9 are not yet in-
cluded in ISO 898-1-2013 (σB ≥ 1400 MPa, σ0.2 ≥ 1260 MPa), so they are not shown in
Figure 5m,n. The graphical analysis carried out by the method of linear interpolation
showed that the achievement of the mechanical properties of 35KhNMFA rolled steel,
corresponding to the property class 14.9, is ensured at a tempering temperature below
520 ± 5 ◦ C. Thus, to obtain ultra-high-strength fasteners, the recommended tempering
temperature is 480–520 ◦ C. The obtained dependence of the decrease in strength charac-
teristics on the tempering temperature allows us to make an assumption that, in order to
obtain property class 12.9 from 35KhNMFA grade steel, it is possible to temper in a very
wide range, up to 700 ◦ C, which requires confirmation in further studies.
Thus, an analysis was made of the effect of tempering temperature on mechanical
properties that meet the requirements of various property classes according to ISO 898-1-
Metals 2022, 12, x FOR PEER REVIEW 13 of 15
2013, for steels of various chemical compositions. Figure 6 shows a summary diagram for
the studied steel grades.

Figure 6. Dependences of the tensile strength of rolled steels of various grades on the tempering
Figure 6. Dependences of the tensile strength of rolled steels of various grades on the tempering
temperature.
temperature.

From the data in Figure 6, it can be seen that for 35KhNMFA grade steel, the slope of
dependenceof
the dependence ofthe
theultimate
ultimatestrength
strengthononthe
the tempering
tempering temperature
temperature is much
is much lessless
than than
for
for steel
steel of allofother
all other grades.
grades. The difference
The difference between
between steel
steel of of grade
grade 35KhNMFA35KhNMFA and otherandgrades
other
grades
is is the presence
the presence of vanadium
of vanadium in its composition.
in its composition. An increase
An increase in tempering
in tempering temper-
temperature
ature to
leads leads
the to the formation
formation of dispersed
of dispersed precipitates
precipitates of vanadium
of vanadium carbonitride,
carbonitride, whichwhich
make
a significant
make contribution
a significant to thetodispersion
contribution strengthening
the dispersion strengtheningof steel. Therefore,
of steel. Therefore, thethe
loss of
loss
strength
of strength duedueto to
the tempering
the temperingofofmartensite
martensiteisislargely
largelycompensated
compensatedby bythethe formation
formation of
vanadium carbonitride
carbonitride precipitates.
precipitates. This testifies to the great promise of using the highest
strength categories of vanadium-containing
vanadium-containing steels steels for
for the
the manufacture
manufacture of of fasteners.
fasteners.

4. Conclusions
From the analysis of the data obtained, three main groups of steel grades can be dis-
tinguished.
− The first group of economically alloyed boron-containing steel grades (32CrB4 and
Metals 2022, 12, 1501 13 of 14

4. Conclusions
From the analysis of the data obtained, three main groups of steel grades can be
distinguished.
− The first group of economically alloyed boron-containing steel grades (32CrB4 and
31CrMoB2), in a wide range of tempering temperatures, makes it possible to man-
ufacture products of property classes 10.9 and 9.8, with the possibility of achieving
properties corresponding to class 12.9 in a narrow tempering temperature range.
− The second group of steels, alloyed with chromium and molybdenum (32KhGMR,
42CrMo4) and with chromium, nickel, and molybdenum (40KhN2MA, 34CrNiMo6),
makes it possible to consistently achieve mechanical properties corresponding to
property class 12.9. For 32KhGMR steel grade, with an economical alloying system,
it is possible to achieve high mechanical properties at a significantly lower carbon
concentration.
− The third group consists of steel alloyed with chromium, nickel, molybdenum, and
vanadium (35KhNMFA), the use of which makes it possible to manufacture ultra-high-
strength fasteners with a tensile strength of more than 1400 MPa.
The results of studying the effect of the tempering duration of 42CrMo4 rolled steel for
30, 45, 60, 75, and 90 min at a temperature of 500 ◦ C showed that the required mechanical
properties for property class 12.9 are achieved in the entire tempering duration interval
studied at a temperature of 500 ◦ C.
The results of studying the microstructure of round-rolled samples made of 40KhN2MA
grade steel after quenching and tempering at temperatures from 400 to 550 ◦ C showed that
it is advisable to restrict the lower limit of the tempering temperatures used at 450 ◦ C.

Author Contributions: Conceptualization, A.Z., A.S. (Alexey Stepanov) and A.K.; methodology, A.S.
(Alexey Stepanov); software, A.K.; formal analysis, N.A.; investigation, A.S. (Alexey Stepanov), A.K.,
A.S. (Alexey Stolyarov), M.Z. and D.K.; writing—original draft preparation, N.A.; writing—review
and editing, A.Z.; project administration, A.Z. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded under Contract No. MK 212117/15-FHO-21-2-4890/B, dated 1
December 2020, performed under an agreement between MMK-METIZ OJSC and the Ministry of
Industry and Trade of the Russian Federation No. 020-11-2020-1988, dated 26 December 2020. State
contract identifier No. 0000000002020PWF0002.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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