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Innovation and Discovery in Russian Science and Engineering

Stavros Syngellakis
Jerome J. Connor Editors
J.W. Newkirk · A.G. Illarionov
A.S. Zhilin Associate Editors

Advanced Methods
and Technologies in
Metallurgy in Russia
Innovation and Discovery in Russian Science
and Engineering

Series editors
Carlos Brebbia
Wessex Institute of Technology, Southampton, United Kingdom
Jerome Connor
Massachusetts Institute of Technology, Cambridge, Massachusetts, USA

More information about this series at http://www.springer.com/series/15790

Stavros Syngellakis • Jerome J. Connor
Editors

J.W. Newkirk • A.G. Illarionov • A.S. Zhilin

Associate Editors

Advanced Methods and

Technologies in Metallurgy
in Russia
Editors
Stavros Syngellakis Jerome J. Connor
Department of Materials and Structures Department of Civil and Environmental
Wessex Institute of Technology Engineering
Southampton, United Kingdom Massachusetts Institute of Technology
Cambridge, Massachusetts, USA
Associate Editors
J.W. Newkirk A.G. Illarionov
Materials Science and Engineering Institute of New Materials and Technologies
Department Ural Federal University
Missouri University of Science Yekaterinburg, Russia
and Technology
Rolla, MO, USA

A.S. Zhilin
Institute of New Materials
and Technologies
Ural Federal University
Yekaterinburg, Russia

ISSN 2520-8047 ISSN 2520-8055 (electronic)

Innovation and Discovery in Russian Science and Engineering
ISBN 978-3-319-66353-1 ISBN 978-3-319-66354-8 (eBook)
https://doi.org/10.1007/978-3-319-66354-8

Library of Congress Control Number: 2017959189

© Springer International Publishing AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
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from the relevant protective laws and regulations and therefore free for general use.
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Printed on acid-free paper

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Preface

The present book is devoted to the topical issues of industrial science with partic-
ular focus on advanced methods and technologies in metallurgy.
Rapidly developing industry demands fundamentally innovative materials
possessing enhanced mechanical, magnetic, and other specific properties.
Manufacturing a new product in metallurgy is inherently connected with a large
number of problems related to obtaining initial bars and their heat, mechanical, and
other types of treatment. Technological processes of production are determined by
the properties of the initial material.
A number of solutions to the problem of material characterization of compli-
cated alloys have been suggested. Constant improvements of the requirements for
materials result in the development of complex alloys with different elements. Such
industries as aviation force scientists to improve the characteristics of titanium and
invar alloys, high-strength steels, and nanocrystalline alloys. Alloying effects in
each element cannot be precisely predicted; therefore, it is essential to conduct
experiments analyzing the properties of new materials in order to introduce these
alloys into the technological process.
New approaches to heat and surface treatment of materials have been intro-
duced. In order to obtain the materials properties required, it is necessary to conduct
thorough research into the processes of phase transformations. The data about
quality and quantity composition of phases in materials guarantee their adequate
usage at various temperatures.
New data have been gathered in the field of ferrous metals metallurgy; more
specifically, the design calculation of ferroalloys based on raw materials has been
determined. Interest in the topic is mostly triggered by the problem of industrial
recycling. Solving the problem will allow improving the technological process
while minimizing electricity consumption, as well as reducing the toxic waste
disposal into the atmosphere.
Energy savings in pyrometallurgy enable proper control of blast furnace
smelting. The principles of selection of new technologies and risk assessment are

v
vi Preface

vitally important for the ironmaking process. Modeling thermophysical processes,

therefore, allow advancing the methods of production.
Finally, successful interaction between different fields of metallurgy eventually
results in better durability of the materials produced.
The editors would like to express their gratitude to all the authors for their
contribution and to the editorial board and other scientists who reviewed the papers
and thus ensured the quality of this book.
The book has been published with financial support of the key Centre of
Excellence “Industrial Mining Institute for Scientific Research and Applications,”
which is part of the program aimed at enhancing the competitiveness of Ural
Federal University, named after the first president of Russia, B.N. Yeltsin, from
2013 to 2020.
The editors also gratefully acknowledge the support of the vice-rector in science
of Ural Federal University, V.V. Kruzhaev, and director of the Institute of Materials
Science and Metallurgy of Ural Federal University, V.A. Maltsev.

Rolla, MO, USA J.W. Newkirk

Yekaterinburg, Russia A.G. Illarionov
Yekaterinburg, Russia A.S. Zhilin
Contents

Part I Material Characterization of Complicated Alloys

1 Effect of Microalloying on the Structure and Phase Composition
of Near-β-Titanium Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
S. Illarionova, A. Popov, and A. Illarionov
2 Microstructural Aspects of High-Strength Maraging Steel
Fracture Toughness Enhancement . . . . . . . . . . . . . . . . . . . . . . . . . 11
S. Gladkovskiy, V. Veselova, and E. Ishina
3 The Precipitation of Silicide Particles in Heat-Resistant
Titanium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Artemiy Popov, M.A. Zhilyakova, O. Elkina, and K.I. Lugovaya
4 Structure Formation and Thermal Expansion Analysis
of 0.6% Carbon-Containing Invar Alloy Crystallized
at Different Cooling Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
A. Zhilin, S. Grachev, M. Ryzhkov, N. Popov, and V. Tokarev
5 Effect of the Structural State of High-Nitrogen Cr-Mn-Mo
Steel on Mechanical and Magnetic Properties . . . . . . . . . . . . . . . . 35
V. Berezovskaya, Yu. Raskovalova, and M. Uimin
6 The Structural and Magnetic Properties of the Amorphous
and Nanocrystalline Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
V. Tsepelev, Yu. Starodubtsev, V. Konashkov, and V. Belozerov

Part II Heat and Surface Treatment

7 Gradient Complex Protective Coatings for Single-Crystal
Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
V.P. Kuznetsov, V.P. Lesnikov, N.A. Popov, I.P. Konakova,
and M.A. Popova

vii
viii Contents

8 Cooling Capacity of Jet Spraying Devices for Large Steel

Parts Heat Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
M. Maisuradze, Yu. Yudin, and M. Ryzhkov
9 Heat Treatment Technology Adjustment Using Experimental
and Simulation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
M. Ryzhkov, M. Maisuradze, and A. Kaletin
10 The Relationship of Pitting Potential to Chemical Composition
of Steels Alloyed with Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
E. Merkushkin, V. Berezovskaya, and M. Spiedel
11 The Formation of Eutectic Phases at the Crystallization
of High-Manganese Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
A. Berezovskiy and V. Berezovskaya

Part III Ferrous Metal Metallurgy

12 Complex Metallurgical Estimation of Manganese
Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
A.V. Zhdanov, V.I. Zhuchkov, V.Y. Dashevskiy, and L.I. Leontyev
13 Production of Manganese Ferroalloys from Russian
Manganese Ores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
V.Y. Dashevskiy, V.I. Zhuchkov, A.V. Zhdanov, and L.I. Leontyev
14 Waste Generation and Recycling in the Ferroalloy Industry . . . . . 113
A.V. Zhdanov, V.I. Zhuchkov, V.Y. Dashevskiy, and L.I. Leontyev
15 Influence of Impurities on Formation of Iron-Carbon Melt . . . . . . 121
A. Gudov, S. Burmasov, A. Murzin, and D. Poptsov
16 Advantages and Risks of Blast Furnace Operation
at Increased Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
S. Filatov, S. Zagaynov, L. Gileva, I. Kurunov, and V. Titov

Part IV Energy Savings in Pyrometallurgy

17 Mathematical Model and Software for the Control
of Commissioning Complex Energy-Intensive Units
in Metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
K. Shchipanov, N. Spirin, O. Onorin, V. Lavrov, and S. Kumar
18 Information Modeling System for Blast Furnace
Smelting Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
N. Spirin, L. Gileva, V. Lavrov, A. Istomin, and A. Sadri
19 Computer System for Production Control of a Blast Furnace . . . . . 161
V. Lavrov, N. Spirin, I. Gurin, L. Lazic, and V. Yarchuk
Contents ix

20 Improvement of the Energy Efficiency of Hot Blast Stove

Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
М. Aksyushin, М. Kalugin, G. Malikov, and Y. Yaroshenko
21 Carbon Dioxide Emissions on an Example of Metallurgical
Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
V. Lisienko, Ju. Chesnokov, A. Lapteva, and S. Kudelin
22 Principles of Selection of New Technology and Risk
Assessment: A Case Study for the Selection of Ironmaking
Process Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Y. Gordon, Y. Yaroshenko, and N. Spirin
23 Development of Techniques for the Characterization
of Thermophysical Properties of Iron Materials
with Internal Heat Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
B. Yur’ev, V. Goltsev, V. Yarchuk, and S. Kudelin

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

 Part I
Material Characterization
of Complicated Alloys
Chapter 1
Effect of Microalloying on the Structure
and Phase Composition of Near-β-Titanium
Alloy

S. Illarionova, A. Popov, and A. Illarionov

1 Introduction

Microalloying of near-β- and two-phase titanium alloys by an element such as

yttrium is used mainly to rule the grain structure [1–5]. It allows us to obtain a
number of important operational and functional characteristics, low elastic modulus
of biocompatible alloys [1, 3]; superplastic characteristics sustain [5]. The intro-
duction of yttrium into titanium alloys is most effective in the range of 0.05–0.1 wt.
% [1, 2, 5]. Adding of germanium provides the reduction of the martensitic starting
temperature in shape memory alloys, increasing of the β-solid solution stability for
β-α- and β-ω-transformations in biocompatible alloys of the system Ti-Nb-Ge, and
effect on the passing of deformation-induced martensitic transformation during
cold deformation in the biocompatible pseudo elastic β-titanium alloys [6–
8]. Until now, the influence of these additives on the decay of the metastable
β-phase in the heat was paid little attention, although Lütjering and Williams [9]
found that this process defines the property complex of the alloy in heat-treated
state (quench þ age). In the present work, a studied alloy was an alloy system close
to thermal-hardening alloy VТ35 [10]. The influence of a microalloying by yttrium
and germanium on formation of structure and phase content of the heat-treated
alloy type VT35 was studied.

S. Illarionova (*) • A. Popov • A. Illarionov

Institute of Materials Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia
e-mail: s.m.illarionova@urfu.ru; a.a.popov@urfu.ru

© Springer International Publishing AG 2018 3

S. Syngellakis, J.J. Connor (eds.), Advanced Methods and Technologies in Metallurgy
in Russia, Innovation and Discovery in Russian Science and Engineering,
https://doi.org/10.1007/978-3-319-66354-8_1
4 S. Illarionova et al.

2 Material and Research Methods

The studied materials were hot-rolled sheets after vacuum annealing at 700  C for
30 min of near-β-titanium alloy similar to VT35 of system Ti-Al-V-Cr-Sn-Zr,
(Aleq ¼ 4.3%, Moeq ¼ 16.8%) microalloyed with 0.1 wt.% yttrium (alloy 1) and
0.1 wt.% yttrium þ 0.1 wt.% germanium (alloy 2). Research of the structure was
carried out with optical and transmission electron microscopy (TEM) instruments
on the devices Neophot 2 and JEM-200C, respectively. The X-ray analysis was
realized on the diffractometer DRON-3 M in filter Cu Кα radiation. Thermal
analysis (DTA) was made on the DuPont thermoanalyzer with completed console
DSC-910. Microhardness was measured by means of the Neophot 2 device used
load 100 g.
The regular polyhedral β-grains with average sizes 90  5 (alloy 1) and
100  5 μm (alloy 2) were observed in the initial state structures (Fig. 1.1a). The
electron microscopic analysis showed the presence of dispersed second-phase
particles ranging in size from 50 to 100 nm (smaller particles were characteristic
of the alloy 2, larger for alloy 1) in the β-matrix for both alloys. The particles are
located predominantly near β-grain boundaries (Fig. 1.1b). The electron pattern
calculation for particle-rich regions allowed to identify particles as yttrium oxide
Y2O3 (Fig. 1.1c). There were diffuse bands associated with the matrix reflexes
β-solid solution on the electron patterns. The observed shape of the bands is
associated by Tyapkin [11] with the formation of preliminary precipitation α-
particles in the metastable β-phase. Developed dislocation structure with the for-
mation of planar dislocation clusters and “tangles” was fixed into β-grain bodies of
both alloys. This fact proved the incomplete removal of work hardening in the
sheets during vacuum annealing.
It was shown with X-ray analysis that a different micro-alloying of alloys 1 and
2 affects the initial β-solid solution state. β-solid solution lines was only fixed in the
alloy 1. While there were weak lines of orthorhombical α00 -phase in the alloy
2 additionally. Despite such difference of the phase composition the lattice
β-phase periods were close to 0.323 nm as alloy 1 as alloy 2. The microhardness
values of the alloys were nearby as well (2400–2450 MPa). The β-transus temper-
ature (Tβ) of alloy 2 (710  C) determined by DTA method was higher than that of
alloy 1 (Тβ ¼ 700  C). This fact and X-ray analysis suggested that germanium in the
alloy 2 works as α-stabilizer when it is in β-solid solution. It agrees with the data of
Liu et al. [12].
In common, yttrium microadding leads to formation of disperse particles of
Y2O3 oxide in the β-matrix, which mainly is situated in a grain boundary areas.
Additional germanium microadding slightly reduces the stability of β-phase and
increases Тβ due to of its α-stabilizing action. Germanium intermetallics or oxides
were not found.
Near-β-alloys can be effectively strengthened by quenching and subsequent
aging. The influence of the quenching temperature in the two cases βþα- and
β-quench on the structure and phase composition of alloys 1 and 2 was studied.
1 Effect of Microalloying on the Structure and Phase Composition of Near. . . 5

Fig. 1.1 The structures of alloys 1 (a)–(c) and 2 (d) in initial state: (а) optical microphotography
(OM), (b)–(d) TEM, (b) and (d) bright field, and (c) electron pattern from “b” axis zone [12–3]
Y2O3 [003]β

The first temperature of αþβ-region was 660  C, and the second one of β-region
was 730  C with endurance for 15 min and when water cooling.
Metastable β-solid solution was fixed by quenches in both alloys 1 and 2 from
660 С to 730 С. Apparently 15 min exposure at the (βþα)-temperature region
660 С does not provide the decomposition of initial metastable β-solid solution.
Illarionov et al. [13] saw the similar effect early in the alloy VТ35 during isother-
mal treatment. Therefore the β-phase lattice periods in the alloys after quenching
from both temperatures were equal to – 0.3228 nm (alloy 1) and 0.3235 nm (alloy
2). Higher β-lattice period of alloy 2 can be explained as follows. Firstly, Zwicker
[14] found that the lattice period β- and α-phases in titanium alloys strongly
influenced from the amount of impurities; in particular oxygen increases the lattice
period β-phase. Secondly electron microscopic researches of alloys 1 and
2 established that size and quantity of particles of Y2O3 in an alloy 1 were more
than in an alloy 2 (Fig. 1.2a, b). Thus we concluded an oxygen in the alloy
1 increasingly located into oxides, than in alloy 2. It resulted to eliminate the
6 S. Illarionova et al.

Fig. 1.2 Structure of the quenched alloys 1 (a), (c), (e), and (f) and 2 (b) and (d): (a)–(d) and (f)
TEM, dark field in reflex [602]Y2O3 (a); [420]Y2O3 (b), (c), and (d); (f) bright field; (e) OM

oxygen content of β-solid solution in the alloy 1 compared with the alloy 2. These
facts could be the reason of higher lattice period β-phase in alloy 2.
Strands on the electron diffraction, detected in an initial state, are present on
electron patterns in quenched from 730 С state of alloys 1 and 2 as well. Diffuse
strands after quenching form 660  C were not fixed. The structure of quenched
alloys from 660  C to 730  C had some difference. The quenching of alloys 1 and
2 from 730  C leads to forming of polygonal structure with small subgrains in the
1 Effect of Microalloying on the Structure and Phase Composition of Near. . . 7

β-grain body (Fig. 1.2c). The quench from 660  C gave the substructure with a high
density of dislocations (Fig. 1.2d). Thus, β-region is activated by the polygonization
process which leads to decrease dislocation density in structure compared to initial
state. At heating on 660  C low angles, a boundary doesn’t arise, and the high
density of dislocations in alloys remained as in initial state.
The perceptible movement of grain boundaries in quenched from 660  С alloys
wasn’t detected. There was another picture in the alloys quenched from 730  С.
Existing curved-convex boundaries in structure indicated their movement. How-
ever, the share of such boundaries was relatively small. The suppression of move-
ment was due to the presence of the yttrium oxide particles in the structure. The
electron microscope image of β-quenched alloy demonstrates breaking of borders
by an yttrium oxide particle (Fig. 1.2f). The particle fixed the boundary on its place.
It is confirmed also by other researchers [2, 4] who provided data that introduction
of yttrium additives to titanium alloys increases recrystallization temperature due to
Y2O3 oxide particle formation.
The calculation of the average β-grain sizes of the quenched alloys was
conducted by the secant method on optical images of the structure. It showed the
average β-grain size practically does not depend on the quenching temperature and
remains at the level of an initial state (for an alloy 1 it is 90 μm and for an alloy
2100 μm). In our opinion the phenomena are connected with the oxide particle
Y2O3 presence in the alloys which constrain the β-grain growth.
The microhardness of quenched alloys was close to the values in the initial state
2400–2450 MPa.
For definition of temperature intervals of aging of the studied alloys, the research
of the processes of decomposition of metastable β-solid solution obtained by
quenching from 730  C (β-region) were carried out with DuPont thermoanalyzer
(Fig. 1.3). The thermal analysis of the alloy 1 allows to reveal two exo- and one
endothermic effect on DSC curve (Fig. 1.3a). The first exothermic effect was fixed
in the range of temperatures 150–320  C and the second in the range of 450–600  C.
Between them a softly expressed endothermic effect was found. Unlike an alloy
1 three eхothermic effeсts were revealed on alloy 2 – curve in the temperature
intervals: 100–300 С (1st), 340–400  C (2nd), and 450–540 С (3rd). There were
two endothermic effects between eхothermic effeсts 1 and 2 and 2 and 3 (Fig. 1.3b).
It has been taken into account the data of Illarionov et al. [13], and calculation of
electron concentration of the alloys which is 4.21 el/at in the order of suggestion of
metastable β-phase transformations during heating. The first low-temperature exo-
thermic effect in the alloys was associated with the processes of preliminary
precipitation formation. It is unusual that ω-phase is the precipitation because the
electron concentration of the alloys is higher in a range of ω-phase presence in
titanium alloys (4.1–4.2 el/at (Zwicker [14])). Thus the preliminary precipitations
could be α-phase ones (Vα). Exothermic effects situated higher than 450  C of both
alloys were associated with the diffusion decay of β-solid solution with the equi-
librium α-phase formation. Exothermic effect in alloy 2 in the temperature range of
340–400  C is connected with the low-temperature α-phase (αlt) formation. This
phase that precipitated with the intermediate mechanism had some rhombic
8 S. Illarionova et al.

(a)
0.5 Dq, mW

0
0 100 200 300 400 500 600
-0.5

-1

-1.5

-2

(b)
0.5 Dq, mW

0
0 100 200 300 400 500 600
-0.5
T,°C
-1

-1.5

-2

Fig. 1.3 Heating thermograms of quenched alloys 1 (a) and 2 (b)

distortion. The first endothermic effects in both alloys were associated with pro-
cesses of dissolution of formed lower temperatures’ preliminary precipitations. The
comparative analysis of DSC curves showed a suppression of formation of inter-
mediate low-temperature αlt-phase in an alloy 1 unlike the alloy 2. This fact was
resulted by increasing stability β-solid solution in alloys 1 provided by decreasing
of oxygen content. Note volume part of Y2O3 particles was higher than in alloy 2.
According to the thermogram analysis, the formation of intermediate phases in
studied alloys is possible at below 450  C temperature aging. Their presence
according to data from Antipov et al. [10] negatively affects the mechanical
properties of the near-β-alloys, first of all on plasticity and toughness. Therefore,
we recommend carrying out the aging at 475–550  C to avoid the intermediate
phase formation.
1 Effect of Microalloying on the Structure and Phase Composition of Near. . . 9

3 Conclusions

1. Yttrium microalloying of near-β-alloys has been shown to result in precipitation

of disperse Y2O3 at grain boundaries. At the same time, additions of germanium
do not lead to formation of any chemical compounds.
2. The Y2O3 particles were found to prevent significant grain growth in single-
phase β-region in the alloys 1 and 2.
3. The decomposition of quenched β-phase during continuous heating up to 600  C
has a complex multistage nature. In the alloy 1, the process goes in the following
sequence – β!Vα!α – while in the alloy 2 the sequence is β!Vα!αlt!α. It is
explained by the behavior of oxygen content: lower oxygen concentration in a
β-phase of alloy 1 results in higher volume fraction of oxide particles in that
alloy.
4. The most favorable aging temperature was established to be in the range of
475–550  C to avoid the intermediate phase formation.
Acknowledgement The research was supported by the project № H976.42 FTP 47/14.

References

1. Hieda, J., Niinomi, M., Nakai, M., Cho, K., & Nagai, S. (2013). Effect of oxide particles
formed through addition of rare-earth metal on mechanical properties of biomedical β-type
titanium alloy. Materials Transactions, 54(8), 1361–1367.
2. Tomita, A., Ueda, M., & Ikeda, M. (2012). Effect of boron and yttrium slight addition on grain
refinement and mechanical properties of Ti-13Cr-1Fe-3Al alloys. In L. Zhou, H. Chang, Y. Lu,
& D. Xu (Eds.), Proceedings of the 12th world conference on titanium, (pp. 544–546). Beijing:
Science Press.
3. Song, X., Niinomi, M., Nakai, M., Tsutsumi, H., & Wang, L. (2012). Improvement in fatigue
strength while keeping low Young’s modulus of a β-type titanium alloy through yttrium oxide
dispersion. Materials Science and Engineering C, 32(3), 542–549.
4. Poorganji, B., Kazahari, A., Narushima, T., Ouchi, C., & Furuhara, T. (2010). Effect of yttrium
addition on grain growth of α, β and αþβ titanium alloys. Journal of Physics: Conference
Series, 240, Article number 012170.
5. Poorganji, B., Hotta, S., Murakami, T., Narushima, T., Iguchi, Y., & Ouchi, C. (2007). The
effect of small amounts of yttrium addition on static and under superplastic deformation grain
growth in newly developed αþβ type, Ti-4.5Al-6Nb-2Mo-2Fe alloy. Advanced Materials
Research, 15–17, 970–975.
6. Inamura, T., Fukui, Y., Hosoda, H., & Wakashima, K. (2005). Mechanical properties of Ti-Nb
biomedical shape memory alloys containing Ge or Ga. Materials Science and Engineering C,
25(3), 426–432.
7. Kim, W.-Y., & Kim, H.-S. (2008). Microstructure control and pseudoelasticity of Ti-Nb-Ge
alloy. Advanced Materials Research, 47–50(2), 1446–1449.
8. Kim, W.-Y., & Kim, H.-S. (2008). Effect of oxygen content on microstructure and mechanical
properties of Ti-Nb-Ge alloys for biomedical application. Advanced Materials Research,
47–50(2), 1450–1453.
9. Lütjering, G., & Williams, J. C. (2003). Titanium (pp. 310–315). Berlin: Springer.
10 S. Illarionova et al.

10. Antipov, A., Moiseev, V., & Moder, N. (1996). Age hardening of VT35 titanium alloy. Metal
Science and Heat Treatment, 38(11–12), 522–526.
11. Tyapkin, Y. D. (1977). Electronographia. Itogi nauki i techniki. Seriya: Metallovedenie i
termicheskaya obrabotka, 11, 152–214.
12. Liu, D., Yan, H., Yuan, X., Chung, Y., Du, Y., Xu, H., Liu, L., & Nash, P. (2011). Thermo-
dynamic modeling of the Ge-Ti system supported by key experiment. Thermochimica Acta,
521, 148–154.
13. Illarionov, A., Popov, A., & Pumpiansky, D. (2000). Study into decomposition of metastable
β-phase during isothermal treatment in the VT35 titanium-based alloy. In I. V. Gorynin & S. S.
Ushkov (Eds.), Proceedings of the 9th world conference on Titanium (pp. 223–230).
St. Petersburg: CRISM “Prometey”.
14. Zwicker, U. (1974). Titan und Titanlegierungen (pp. 143–199). Berlin: Springer.
Chapter 2
Microstructural Aspects of High-Strength
Maraging Steel Fracture Toughness
Enhancement

S. Gladkovskiy, V. Veselova, and E. Ishina

1 Introduction

Although maraging steels have found commercial application since the early 1960s
[1, 2], they still remain as high-strength prospective structural and aerospace
materials having high fracture resistance and ultimate strength exceeding
2000 MPa. Fracture toughness of maraging steels strongly depending on their
strength level varies in the range of K1c ¼ 30–160 MPam1/2. A vast data is
available on K1c values of the named steels for a period covering 30 years
[2, 3]. But many microstructural aspects of maraging steel fracture toughness
enhancement are not clear. So the purpose of the presented study is to evaluate
the contradictory role of microstructural evolution of maraging steels caused by
heat treatment and additional alloying in their brittle fracture resistance.

S. Gladkovskiy (*)
Institute of Materials Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia
Institute of Engineering Science of Urals Branch of RAS, Yekaterinburg, Russia
e-mail: gsv@imach.uran.ru
V. Veselova
Institute of Engineering Science of Urals Branch of RAS, Yekaterinburg, Russia
E. Ishina
Institute of Materials Science and Metallurgy, Ural Federal University, Yekaterinburg, Russia

© Springer International Publishing AG 2018 11

S. Syngellakis, J.J. Connor (eds.), Advanced Methods and Technologies in Metallurgy
in Russia, Innovation and Discovery in Russian Science and Engineering,
https://doi.org/10.1007/978-3-319-66354-8_2
12 S. Gladkovskiy et al.

2 Experimental

Experimental and industrial Fe-18Ni-9Co-4Mo-Ti, Fe-18Ni-2Mo-Ti, and Fe-11Cr-

10Ni-2Mo-Сu-Ti high-strength maraging steels of three basic types were studied:
01N18K9M5T, 01N18M4TYu, and 01Kh11N10M2DT. The content of basic
alloying elements varied in the following range: Mo ¼ 1.55–3.90;
Ti ¼ 0.33–1.47; Al ¼ 0.09–1.07; Cu ¼ 0.10–2.48 wt. %. The amount of carbon
does not exceed 0.03 wt. %. The researched experimental and industrial steels were
produced by vacuum induction melting and vacuum arc remelting. The sulfur and
phosphorus contents in the steels were between 0.005 and 0.011 wt. %. Hot-rolled
workpieces were subjected to single and double quenching in the temperature range
from 920 to 1200  C. All as-quenched steels had a martensitic structure. A special
thermal embrittlement heat treatment (1200 ! 950  C, 1 h) was used also in order
to form intergranular Ti(C, N) particles. High-temperature aging up to 600  C was
performed for producing reverted austenite phase in martensitic matrix. To obtain
retained austenite in maraging steels, a heat treatment regime including accelerated
heating of samples to the austenitic field (800–950  C) in molten salts was used.
Fracture surface analysis was performed by means of Tescan VEGA II XMU
scanning electron microscope and Wyko NT-1100 optical profilometer. DRON-3
diffractometer was used for X-ray diffraction examination of steel phase composi-
tion. Mechanical properties and fracture toughness were tested by the standard
methods (GOST-State Standard 1487-84, 9454-7884, and 25.506-85, respectively)
using universal testing machines EUS-20 and Instron8801 and instrumented impact
test machine “Tinius Olsen” IT542.

3 Results and Discussion

The role of intermetallic amount on strength and fracture resistance parameters was
evaluated for 13 compositions of Fe-11Cr-10Ni-2Mo-Ti maraging steels with
different contents of Ni3Ti and Fe2 (Ti, Mo) intermetallic forming elements such
as Mo, Ti, and Al. It is found that with growth of the total content of titan and
aluminum from 0.99 to 2.1 wt. %, yield stress increases from 1510 to 1790 MPa and
ultimate strength rises from 1570 to 1920 MPa (Fig. 2.1).
However, as presented in Fig. 2.1, it gives a sufficient decrease in fracture
toughness parameter K1c from the value 77 to 34 MPam1/2. So it may be
recommended to limit the total content the titan and aluminum (1.6 wt. %)
while alloying Fe-11Cr-10Ni-2Mo-Ti maraging steels.
In general, using pure raw materials and modern metallurgical technologies
provides very low content of impurities and nonmetallic inclusions in maraging
steels. However within one brand of Fe-18Ni-2Mo-Ti steel, the amount of nitrides,
oxides, and sulfides in various fusions can significantly vary (Table 2.1). It is shown
that the smallest K1c value corresponds to the composition of steel 2 with greatest
2 Microstructural Aspects of High-Strength Maraging Steel Fracture Toughness. . . 13

K1c, MPa • m1/2

90
9 7
80
70 4

60 5 3 8
10
2
50 11 1
12
6
40
30 y=-16,815x2 + 26,072x + 57,214 13

20
10
0
0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4
(Ti+A1),%

Fig. 2.1 Dependence of K1c values of Fe-11Cr-10Ni-2Mo-Ti steels on total content of (Ti þ Al)
wt. %

Table 2.1 Microstructural and mechanical parameters of Fe-18Ni-2Mo-Ti steel of different

composition
Microstructural and mechanical
parameters Composition 1 Composition 2 Composition 3
Total contamination by nonmetallic 0.29 0.36 0.35
inclusions, vol. %
Nitrides, vol. % 0.14 0.13 0.066
Oxides, silicates, vol. % 0.07 0.06 0.033
Sulfides, vol. % 0.086 0.166 0.25
Average particle size, μm 8–12 10–15 5
Distribution of particles Inhomogen. Highly inhomogen. More inhomogen.
(all particles)
σY, МPа 1920 1860 1880
К1с, МPаm1/2 65 58 71

total volume fraction of nonmetallic inclusions, average size, and extremely inho-
mogeneous character of distribution in matrix. The most negative role in maraging
steel fracture resistance is attributed to nitride particles which unlike round sulfides
have a square, triangular, or hexagonal form. Nitrides have poor deformation ability
and promote the creation of internal stress concentrators.
On the example of cobalt-free Fe-18Ni-2Mo-Ti steel, it is established that
increase of quenching temperature before aging from 920 to 1200  C, promoting
growth of austenitic grain, leads to decrease in characteristics of plasticity and
impact strength with a simultaneous abnormal growth of K1c values. This abnormal
effect first found in structural steels in [4] is associated with the different ratio of
pre-destruction zone size (zone of plastic deformation ahead of stress concentrator)
dzp  100 microns and the size of austenitic grain size (dg) after conventional
14 S. Gladkovskiy et al.

Fig. 2.2 Fracture surface of

Fe-18Ni-2Mo-Ti maraging
steel after thermal
embrittlement (heat
treatment 3) examined by
SEM

quenching (dg ¼ 25–40 microns) and quenching with overheating (dg ¼ 200–250
microns). Even greater decrease in plasticity and impact strength is resulted by
usage of thermal embrittlement heat treatment (transfer of a specimen from tem-
perature 1200 to 900  C for 1 h before cooling to room temperature which causes
the formation of brittle intergranular Ti (C, N) particles). The typical stonelike
specimens’ fracture surface after thermal embrittlement, examined by SEM and
optical profilometer, is shown in Figs. 2.2 and 2.3, respectively. It is necessary to
mention that the increased static fracture toughness remains high even in case of
thermal embrittlement. As resulted from comparative impact tests evaluating K1d
parameter dynamic fracture toughness, growth effect after overheating and thermal
embrittlement is not detected (Table 2.2). Repeated heating to 1200  C before water
quenching for the purpose of intergranular Ti(C,N) particle dissolution leads to
partial restoration of plastic properties and impact strength alongside with a notice-
able increase in K1c values (Table 2.2).
As one of the effective ways of maraging steel fracture resistance enhancement
introduction in their microstructure, a regulated share of retained and reverted
austenitic phase is considered [5]. Formation of 5% of retained austenite using
additional accelerated heating in austenite area allows us to increase strength
properties and K1c values at the same time (Table 2.3). The introduction of 14 %
reverted austenite phase in Fe-18Ni-4Mo-Ti steel microstructure gives a more
significant increase in fracture toughness. However, it leads to some decrease in
strength properties as compared with standard heat treatment processing. An
additional factor of high fracture toughness of γ-phase containing maraging steels
is connected with its partial transformation to martensitic α0 -phase in the plastic
zone ahead of crack by analogy with TRIP-steels [6].
2 Microstructural Aspects of High-Strength Maraging Steel Fracture Toughness. . . 15

Fig. 2.3 Fracture surface of

Fe-18Ni-2Mo-Ti maraging
steel after thermal
embrittlement (heat
treatment 3) examined by
optical profilometer

Table 2.2 The influence of heat treatment on mechanical properties and static and dynamic
fracture toughness of cobalt-free Fe-18Ni-2Mo-Ti maraging steel
KCU К1с/K1d
Heat treatment σY (МPа) σu (МPа) δ (%) Ψ (%) (MJ/m2) (МPаm1/2)
1 1730 1830 8 27 0.4 84/65
2 1740 1845 2 6 0.12 68/29
3 1870 1810 6 17 0.25 82/58
4 1880 1920 10 56 0.6 71/69
Heat treatment:
1. Quenching 920 þ 820  С þ aging 480  С, 3 h
2. Quenching 1200  С þ aging 48  С, 3 h
3. Heating up to 1200 ! 950  C, 1 h þ aging 480  С, 3 h
4. Heating up to 1200 ! 950  C, 1 h þ quenching 1200  С þ aging 48  С, 3 h

Table 2.3 The influence of retained and reverted austenite on yield stress, ultimate strength, and
fracture toughness of Fe-18Ni-9Co-4Mo-Ti maraging steel
γ-phasea σY σu К1с
No Heat treatment (%) (МPа) (МPа) (МPа.m1/2)
1 Quenching 920 þ 820  С þ aging 480  С, 0/0 1990 2080 72.5
3h
2 Quenching 920 þ 820  С þ heating to 5/2 2080 2114 84.0
820  С, 5 min. þ aging 480  С, 3 h
3 Quenching 920 þ 820  С þ aging 600  С, 14/4 1940 2020 94.0
3 h þ heating to 820  С, 5 min þ aging
480  С, 3 h
a
Austenite phase content in specimens’ body (numerator) and on specimens’ fracture surface
(denominator)

Analysis of experimental data showed that the ratio of various microstructural

factors of the fracture toughness varies significantly depending on the level of
resistance to brittle fracture. For example, at K1C values up to 50 MPam1/2, most
significant influence on maraging steel fracture toughness has intergranular pre-
cipitates and strengthening intermetallics (Fig. 2.4a). When K1c values are higher
16 S. Gladkovskiy et al.

a b
1
4 15% 20%
30%
45%
1 1
2 2
2 3 15% 3
25% 4 4

3 20%
30%

Fig. 2.4 Volume fraction of microstructural factors 1–4 attributing to maraging steel fracture
toughness enhancement at low (a) and high (b) level of maraging steel brittle fracture resistance:
1. impurities and nonmetallic inclusions; 2. grain size; 3. intergranular precipitates; 4, volume
fraction and morphology of intermetallics

than 70 MPam1/2, the dominating microstructural factors of fracture toughness

enhancement become the volume fraction and morphology of strengthening inter-
metallic phases (Fig. 2.4b).

4 Conclusions

It is pointed out that high level of maraging steel strength and fracture toughness
may be gained by eliminating nitrides and intergranular carbonitride particles,
adjusting the volume fraction and morphology of intermetallics, and providing
microstructure with metastable retained and reverted austenites. The accumulated
data could highlight the role of microstructural factors affected by alloying and heat
treatment in predicting fracture resistance of advanced high-strength maraging
steels.

Acknowledgments The authors are grateful to Mr. A. A. Kruglov, Mr. V. V. Yurovskihkh, and
Mrs. S. V. Kuteneva for useful discussion and experimental assistance.

References

1. Floreen, S., & Decker, R. F. (1962). Heat treatment of 18% Ni maraging steel. Transactions of
American Society for Metals, 55, 58–76.
2. Perkas, M. D., & Kardonskii, V. M. (1970). Vysokoprochnye martensitno-stareyushchie stali
(High-strength maraging steels) (р. 224). Moscow: Metallurgiya.
3. Georgiev, M. N., & Simonov Yu, N. (2013). Treschtinostoikost jelezouglerodistykh staley
(p. 419). Perm: National Research Polytechnic Institute.
2 Microstructural Aspects of High-Strength Maraging Steel Fracture Toughness. . . 17

4. Ritchie, R. O. (1978). What does the Charpy test really tell us (pp. 54–73). Metals Park: ASM.
5. Gladkovskii, S. V., Kaletina, Y. V., & Filippov, A. M. (1999). Role of metastable austenite in
the enhancement of structural strength of maraging steels. Physics of Metals and Metallogra-
phy, 87(3), 253–262.
6. Gerberich, W. W., Hemmings, P. L., Merz, M. D., & Zackay, V. F. (1968). Preliminary
toughness results on TRIP steels. Transactions of American Society for Metals, 61, 843–847.
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SYNTHETIC RESINS
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REPORT No. 131

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ERRATA
Since publication of the report on Synthetic Resins the
Commission’s attention has been called to certain necessary
corrections.
Page 37—2d line under heading “Production in the United
States”
Strike out “The Resinous Products and Chemical Co., Inc.,” and
insert “Rohm and Haas,”
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 UNITED STATES TARIFF COMMISSION

SYNTHETIC RESINS
AND THEIR RAW MATERIALS

A SURVEY OF THE TYPES AND USES OF SYNTHETIC

RESINS, THE ORGANIZATION OF THE INDUSTRY,
AND THE TRADE IN RESINS AND RAW
MATERIALS, WITH PARTICULAR
REFERENCE TO FACTORS
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UNDER THE GENERAL PROVISIONS OF SECTION 332, TITLE III,

PART II, TARIFF ACT OF 1930

REPORT No. 131

SECOND SERIES
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 TABLE OF CONTENTS
Page
Acknowledgment xi
1. Introduction 1
Scope and purpose 2
Fundamental definitions 2
Tariff history 3
Broadening use of synthetic resins 4
Relation of synthetic resins to their raw materials 5
Sources of information 7
2. Summary:
Growth of the industry 7
Raw materials 8
Resins 9
The industry abroad 10
International trade 10
3. Tar-acid resins 11
The three stages of a tar-acid resin 13
Classification of tar-acid resins 13
Processes of resin manufacture 14
Production in the United States 15
Imports into the United States 16
Exports from the United States 17
Tar-acid resins for molding:
Molding powders and pellets 18
The molding of tar-acid resins 19
Production of tar-acid molding resins 19
Cast phenolic resins:
Process of manufacture 20
Uses 20
 Patents and licensing 21
Production of cast phenolic resins 21
Imports and exports 21
Tar-acid resins for laminating 21
Uses of tar-acid resin laminated products 22
Production of tar-acid resins for laminating 23
Imports into the United States 24
Exports from the United States 24
Tar-acid resins for surface coatings:
Types of resin used and the resultant coatings 24
Production in the United States 25
Imports into and exports from the United States 25
Tar-acid resins in adhesives 25
Tar-acid resins for other uses 26
4. Alkyd resins:
Description and uses 26
Development and patents 27
Classification of alkyd resins:
Unmodified drying alkyd resins 28
Drying alkyd resins, modified with natural
materials 29
Drying alkyd resins, modified with other
synthetic resins 29
Drying alkyd resins, modified with other
synthetic resins and oil extended 29
Semidrying alkyd resins 29
Nondrying alkyd resins 30
Miscellaneous modified alkyd resins 30
Alkyd resins in water dispersion 30
Alkyd resins in molding compositions and
other uses 30
Pigments and solvents in alkyd resins 31
Production in the United States 31
Imports into and exports from the United States 32
 5. Urea resins:
Description and uses 32
Production in the United States 34
United States imports and exports 35
6. Acrylate resins:
Properties and uses 35
Production in the United States 37
Imports into and exports from the United States 38
7. Coumarone and indene resins:
Description and uses 38
Production in the United States 39
Imports into and exports from the United States 39
8. Petroleum resins:
Properties and uses 39
Production 41
Imports and exports 41
9. Polystyrene resins:
Properties and uses 41
Production in the United States 42
Imports into and exports from the United States 42
10. Vinyl resins 43
Description and uses:
Polyvinyl acetate resins 44
Copolymers of vinyl acetate and vinyl chloride 46
Polyvinyl chloride resins 47
Polyvinyl chloroacetate resins 47
Divinyl acetylene and synthetic rubber 47
Production in the United States 48
Imports into the United States 48
Exports from the United States 50
11. Other synthetic resins:
Adipic acid resins 50
Aniline resins 50
Citric acid resins 50
 Diphenyl resins 51
Furfural resins 51
Resins from sugar 51
Sulphonamide resins 51
12. The organization of the synthetic resin industry:
Horizontal relationships between resin producers 52
Vertical relationships between resin producers:
Tar-acid resins for molding 53
Tar-acid resins for laminating 54
Cast phenolic resins 54
Tar-acid resins for coatings 55
Tar-acid resins for miscellaneous uses 55
Alkyd resins made from phthalic anhydride 55
Alkyd resins made from maleic anhydride 55
Urea resins for molding 56
Urea resins for other uses 56
Coumarone and indene resins 56
Other resins 56
Relationship of the resin industry to other
industries:
The chemical industry 56
The surface-coating industry 57
The electric industry 57
The auto industry 57
13. The United States tariff and international trade in
synthetic resins 58
Rapid expansion in home markets 59
The effect of patents on international trade 59
The United States tariff on resins and resin
products:
Synthetic resins 60
Articles made of synthetic resin 61
14. Synthetic resin prices, properties, and uses:
Synthetic resins as substitutes 62
 Motives for substitution 63
Materials displaced by synthetic resins 63
Competition between synthetic resins 63
Resins classified by cost 64
The physical properties of a resin and its uses 65
15. Synthetic resins in other countries:
Germany:
Production 75
Tar-acid resins 75
Alkyd resins 76
Urea resins 76
Polystyrene and vinyl resins 76
Uses of synthetic resins 76
Organization 77
Foreign trade 77
Great Britain:
Production 78
Tar-acid resins 79
Urea resins 79
Acrylate resins 79
Aniline resin 79
Organization 79
Foreign trade 80
France:
Producers 80
Foreign trade 81
Czechoslovakia 82
Italy 82
Japan 83
Production 83
Canada 84
Union of Soviet Socialist Republics 85
Netherlands 85
Denmark 86
 Poland 86
16. Raw materials for alkyd resins 86
Naphthalene:
Recovery of naphthalene 87
Description and uses 87
United States production 88
Organization of the industry 89
Trend of production 89
World production 90
Germany 91
Great Britain 92
Belgium 93
Czechoslovakia 93
France 94
Poland 94
Netherlands 94
Canada 94
Union of Soviet Socialist Republics 94
Japan 94
United States imports:
Rates of duty 95
Import statistics 96
United States exports 98
Competitive conditions 98
Phthalic anhydride:
Description and uses 98
United States production 100
Production in other countries 101
United States foreign trade 101
Competitive conditions 101
Polybasic acids other than phthalic anhydride:
Maleic acid and anhydride 102
Malic acid and malomalic acid 102
Adipic acid 102
 Succinic acid and anhydride 102
Fumaric acid 102
Glycerin:
Description and uses 103
United States production 103
Production in other countries 104
International trade 104
United States imports 105
United States exports 107
Competitive conditions 108
17. Raw materials for tar-acid resins:
The tar acids 109
Phenol:
Description and uses 110
United States production 111
Grades produced for resins 112
Producers 112
World production 113
United States imports:
Rates of duty 114
Import statistics 114
United States exports 116
Competitive conditions 116
The cresols, xylenols, and cresylic acid:
Description and uses:
The cresols 117
Metacresol 118
Orthocresol 118
Paracresol 118
Metaparacresol 118
Cresol 118
The xylenols 118
Other high-boiling tar acids 119
Cresylic acid 119
 United States production:
The cresols 120
The xylenols 120
Other high-boiling tar acids 120
Cresylic acid 120
Foreign production 122
United States imports:
Rates of duty 124
Import statistics 125
United States exports 131
Competitive conditions 131
Synthetic tar acids other than phenol 132
Para tertiary amyl phenol 133
Para tertiary butyl phenol 133
Phenyl phenols 133
Resorcinol 133
Formaldehyde:
Description and uses 133
United States production 134
Production in other countries 134
United States imports and exports 134
Competitive conditions 135
Hexamethylenetetramine:
Description and uses 136
United States production 136
Production in other countries 136
United States imports and exports 136
Competitive conditions 137
Furfural 137
18. Raw materials for urea resins:
Urea 138
Thiourea 139
19. Raw materials for vinyl resins:
Description and uses 140
 United States production 140
United States imports 141
Competitive conditions 141
APPENDIXES
Appendix A. Statistical tables on foreign trade in raw material
for synthetic resins 144
Appendix B. Trade names for synthetic resins made in the
United States 153
Appendix C. Trade names for synthetic resins made in Great
Britain 155
Appendix D. Trade names for synthetic resins made in
Germany 156
Appendix E. List of United States manufacturers of raw
materials for synthetic resins 158
Appendix F. Glossary 160
TABLES
No.
1. Synthetic resins: United States production and sales,
1921-37 8
2. Tar-acid resins: United States production and sales, by
type of raw material, 1933-37 14
3. Tar-acid resins: United States production and sales,
1927-37 15
4. Synthetic resins of coal-tar origin: United States imports
for consumption, 1919-37 16
5. Synthetic resins of coal-tar origin: United States imports
for consumption, by principal sources, in specified
years 1929-37 17
6. Cast phenolic resins: United States production and
sales, 1934-37 21
7. Alkyd resins from phthalic and maleic anhydride: United
States production and sales, 1933-37 31
8. Urea resins: United States production and sales, 1933-
37 35