Aleaciones Cobre-Niquel-Estaño

materials
Review
A Review of Cu–Ni–Sn Alloys: Processing, Microstructure,
Properties, and Developing Trends
Lang Guo, Pengcheng Zuo, Zequn Zhang, Qianwen Zhang, Mengya Zhao, Xinyu Hou, Junsheng Wu *
and Bowei Zhang *
Institute for Advanced Materials and Technology, University of Science and Techonlogy Beijing,
Beijing 100083, China
* Correspondence: wujs@ustb.edu.cn (J.W.); bwzhang@ustb.edu.cn (B.Z.)
Abstract: Cu–Ni–Sn alloys have been widely used in the aerospace industry, the electronics industry,
and other fields due to their excellent electrical and thermal conductivity, high strength, corrosion and
wear resistance, etc., which make Cu–15Ni–8Sn alloys the perfect alternative to Cu–Be alloys. This
paper begins with how Cu–Ni–Sn alloys are prepared. Then, the microstructural features, especially
the precipitation order of each phase, are described. In addition, the influence of alloying elements,
such as Si, Ti, and Nb, on its microstructure and properties is discussed. Finally, the effects of plastic
deformation and heat treatment on Cu–Ni–Sn alloys are discussed. This review is able to provide
insight into the development of novel Cu–Ni–Sn alloys with a high performance.
Keywords: Cu–Ni–Sn; alloy; processing; microstructure; property
1. Introduction
Copper and copper alloys are some of the most important materials in new-generation
information technology, new energy vehicles, rail transit equipment, aerospace and ocean
engineering, and other fields [1]. Among the copper alloys, the Cu–Be alloy used to play an
indispensable role in the economic industry and was called the “king of nonferrous elastic
Citation: Guo, L.; Zuo, P.; Zhang, Z.; materials” [2]. However, the production of Cu–Be alloys generates toxic dust, and their
Zhang, Q.; Zhao, M.; Hou, X.; Wu, J.; stress relaxation performance and conductive stability tend to dramatically deteriorate at
Zhang, B. A Review of Cu–Ni–Sn high temperatures. A costly and complex preparation technology is required to address
Alloys: Processing, Microstructure,
these issues, which limits their applications [3]. With the rapid movement of the electronics
Properties, and Developing Trends.
industry toward miniaturization, integration, and high reliability, it is of great significance
Materials 2023, 16, 444. https://
to prepare high-strength and elastic copper alloys that are safe, non-toxic, simple to prepare,
doi.org/10.3390/ma16010444
cost-effective, and provide a good service performance. A series of beryllium-free and
Academic Editor: Andrey Belyakov high-performance copper-based elastic alloys have been successfully developed, such as
Cu–Ti [4], Cu–Ni–Sn [5], Cu–Ni–Mn [6], Cu–Ni–Al [7], and Cu–Fe–P [8].
Received: 2 December 2022
Since their successful development by Bell Telephone Laboratories in the 1970s, Cu–
Revised: 25 December 2022
Ni–Sn alloys have received widespread attention [9]. The main Cu–Ni–Sn alloys are
Accepted: 27 December 2022
Published: 3 January 2023
Cu–9Ni–2Sn (UNS C72500), Cu–4Ni–4Sn (UNS C72600), Cu–9Ni–6Sn (UNS C72700), Cu–
10Ni–8Sn (UNS C72800), and Cu–15Ni–8Sn (UNS C72900). Among them, Cu–15Ni–8Sn
has the best wear resistance and the highest mechanical strength and hardness [10]. The
mechanical properties and wear resistance of Cu–Ni–Sn alloys are similar to those of Cu–Be
Copyright: © 2023 by the authors. alloys, while the thermomechanical workability and corrosion resistance of Cu–Ni–Sn
Licensee MDPI, Basel, Switzerland. alloys are better than those of Cu–Be alloys [11]. As an excellent spring material, Cu–15Ni–
This article is an open access article 8Sn alloys are used as friction materials for manufacturing high-performance aerospace
distributed under the terms and bearings, tooth wheel drill bits, and heavy-duty mobile industrial equipment, and have
conditions of the Creative Commons great prospects for application in bearing materials in, for example, the automotive, aircraft,
Attribution (CC BY) license (https:// drilling equipment, and machine tool industries [5]. Figure 1 shows a partial application of
creativecommons.org/licenses/by/ Cu-Ni-Sn alloy.
4.0/).
Materials 2023, 16, 444. https://doi.org/10.3390/ma16010444 https://www.mdpi.com/journal/materials

Materials 2021, 14, x FOR PEER REVIEW 2 of 20
bearings, tooth wheel drill bits, and heavy-duty mobile industrial equipment, and have
great prospects for application in bearing materials in, for example, the automotive, air-
Materials 2023, 16, 444 2 of 20
craft, drilling equipment, and machine tool industries [5]. Figure 1 shows a partial appli-
cation of Cu-Ni-Sn alloy.
Figure 1.
Figure 1. Application
Application of
of Cu–Ni–Sn
Cu–Ni–Sn alloys.
alloys.
After
After reviewing thethe existing
existingliterature
literatureon onCu–Ni–Sn
Cu–Ni–Snalloys,alloys,
in in this
this paper,
paper, wewefirstfirst
in-
introduce the development of Cu–Ni–Sn alloys in the past decade or so and
troduce the development of Cu–Ni–Sn alloys in the past decade or so and briefly describe briefly describe
the
the preparation
preparation process
process of
of the
the alloys,
alloys, including
including continuous
continuous casting,
casting, powder metallurgy,
powder metallurgy,
and
and the plasma spraying and rapid solidification methods. Specifically, we summarize the
the plasma spraying and rapid solidification methods. Specifically, we summarize the
application
applicationof ofaapromising
promisingrapid
rapidsolidification
solidificationmethod,
method, laser powder
laser powder bed fusion
bed (LPBF),
fusion (LPBF), in
the preparation
in the preparation of of
Cu–Ni–Sn
alloys.The
Thestrengthening
strengtheningmechanism
mechanismof ofthe
thehigh-strength
high-strength
copper
copper alloy,
alloy,Cu–15Ni–8Sn,
Cu–15Ni–8Sn,isisdiscussed
discussedinindetail, followed
detail, followed byby a discussion
a discussion of of
thethe
effects
effects of
adding different alloying elements on the structure of the alloy. Finally, we
of adding different alloying elements on the structure of the alloy. Finally, we illustrateillustrate the
influence of plastic
the influence deformation
of plastic and heat
deformation andtreatment on theon
heat treatment microstructure and properties
the microstructure and prop- of
erties of Cu–Ni–Sn alloys.
2. Microstructure of Cu–Ni–Sn Alloys
2. Microstructure of Cu–Ni–Sn Alloys
Cu–15Ni–8Sn is a typical precipitation hardening alloy. The strengthening mechanism
Cu–15Ni–8Sn is a typical precipitation hardening alloy. The strengthening mecha-
is the spinodal decomposition of the supersaturated solid solution. When Sn is added, at
nism is the spinodal decomposition of the supersaturated solid solution. When Sn is
least six different precipitation products can be formed in the aging process: the γ (DO3 )
added, at least six different precipitation products can be formed in the aging process: the
phase, which precipitates at the grain boundaries or in the grains, the ordered DO22 phase
γ (DO
((Cu 3) phase, which precipitates at the grain boundaries or in the grains, the ordered
x Ni1-x )3 Sn), the L12 phase, the spinodal-decomposition-induced amplitude modula-
DO 22 phase ((CuxNi1-x)3Sn), the L12 phase, the spinodal-decomposition-induced amplitude
tion structure, and the orthogonal β phase. Among them, the most studied phase is the
modulation(Cu
metastable structure, and the orthogonal β phase. Among them, the most studied phase
x Ni1-x )3 Sn phase with a DO22 lattice structure during spinodal decompo-
is the metastable
sition. (CuxNi1-x
Figure 2 presents )3Sn
the phasephase
ternary with adiagram
DO22 lattice structure during
of Cu–Ni–Sn. spinodal
Since the contentdecom-
of Ni
position. Figure 2 presents the ternary phase diagram of Cu–Ni–Sn.
is fixed at 15 wt%, the diagram can actually be regarded as a binary phase diagram. The Since the content of
Ni is fixed at 15 wt%, the diagram can actually be regarded as a binary
dotted line in the figure indicates that Sn is 8 wt%. At this composition, the alloy begins to phase diagram.
The dottedthe
precipitate lineα in the figure
phase indicates
(FCC) from that Snphase
the liquid is 8 wt%.
whenAt thethis composition,
temperature thebelow
drops alloy
beginsC.toAs
1150 ◦ precipitate the α phase
the temperature (FCC) further,
decreases from themore
liquidα phase
phase when the temperature
is formed. drops
Sn atoms precipi-
below
tate 1150 °C. Asinthe
continuously thetemperature decreases
form of a γ solid further,
solution in themore α phase
α phase, is formed.
leading Sn atoms
to precipitation
precipitate continuously
strengthening. The γ phase in the form
is an of a γ solid
important solution
factor in the
affecting theαproperties
phase, leading
of thetoalloy.
pre-
cipitation strengthening. The γ phase is an important factor affecting the
Different solution temperatures, times, and cooling rates directly influence the size, shape, properties of the
alloy. Different solution temperatures,
and distribution of the γ phase precipitates. times, and cooling rates directly influence the size,
shape, and distribution of the γ phase precipitates.
2021, 16,
Materials 2023, 14, 444
x FOR PEER REVIEW 33of
of 20
Figure 2. Cu–Ni–Sn ternary phase diagram (Ni fixed at 15 wt%) [12].

Figure
Figure 2. Cu–Ni–Sn ternary
2. Cu–Ni–Sn ternary phase
phase diagram
diagram (Ni
(Ni fixed
fixed at
at 15
15 wt%)
wt%) [12].
[12].
Zhao
Zhao et et al.
al. [12] established aa detailed
[12] established detailed TTT TTT diagram
diagram (see(see Figure
Figure 3)3) for
for thethe isothermal
isothermal
Zhao et al.of
decomposition [12] established a detailed(wt%)TTT diagram (see Figure 3) forofthe isothermal
decomposition of the alloy Cu–15Ni–8Sn (wt%) based on a large number of TEM charac-
the alloy Cu–15Ni–8Sn based on a large number TEM charac-
decomposition
teristic of the alloy Cu–15Ni–8Sn (wt%) based on a large number of TEM charac-
teristic and resistivity measurements.
and resistivity measurements. According
According to the diagram,
to the diagram, amplitude
amplitude modulation
modulation
teristic and resistivity
decomposition measurements. According to the diagram, fromamplitude modulation
decomposition does does not
not occur
occur above
above 500
500 °C◦ C and
and the
the precipitation
precipitation from the the matrix
matrix during
during
decomposition
tempering does not occur above 500 ◦°C and the precipitation from the matrix during
at a higher temperature (600 °C) is the discontinuous γ
tempering at a higher temperature (600 C) is the discontinuous γ (DO3 ) phase. With an (DO 3 ) phase. With an
tempering at a higher temperature (600 °C) is the discontinuous
extension of annealing time or a decrease in temperature, the ordered γ (DO
ordered DO 3) phase. With an
DO22 22 phase with a
extension
typical Al33of
Ti annealing timecrystalline
intermetallic or a decrease in temperature,
structure begins to the orderedat
precipitate DO 22 phase
500~350 with
°C, fol-a
◦ C, followed
Al Ti intermetallic crystalline structure begins to precipitate at 500~350
typical Althe
lowed 3Ti intermetallic crystalline structure begins to precipitate at 500~350 °C, fol-
by the byfurtherfurther precipitation
precipitation of the ordered
of the ordered L12 phase.
L12 phase. Finally,Finally,
when when the temperature
the temperature drops
lowed by the further precipitation of the ordered L12 along
phase.with
Finally,
the when the temperature
drops 300 ◦ C,300
below below °C, spinodal
spinodal decomposition
decomposition occurs occurs
along with simultaneous
the simultaneous appearanceappear-
of a
dropsofbelow
ance 300 °C, spinodal
a mixed-phase decomposition occurs along with the simultaneous appear-
mixed-phase structure structure of DO
of DO22 and L1222. and L12.
ance of a mixed-phase structure of DO22 and L12.
Figure 3.
Figure TTT diagram
3. TTT diagram of
of the
the alloy
alloy Cu–15Ni–8Sn
Cu–15Ni–8Sn [12]
[12]..
Figure 3. TTT diagram of the alloy Cu–15Ni–8Sn [12].
Figure 4 is a bright-field (BF) TEM image of a quenched sample of a Cu–15Ni–8Sn
Figure 4 is a bright-field (BF) TEM◦ image of a quenched sample of a Cu–15Ni–8Sn
alloy. After 4the asample is aged at 350 C for 60 min, a typicalsample
spinodal
of adecomposition
alloy.Figure
After theis sample
bright-field
is aged (BF) TEM°C
at 350 image
for 60ofmin,
a quenched
a typical spinodal Cu–15Ni–8Sn
decomposition
nanostructure
alloy. After theissample
formed.isTheaged Sn-rich
at 350region
°C foris60filled
min,with
a the skeleton
typical spinodalof decomposition
the amplitude
nanostructure is formed. The Sn-rich region is filled with the skeleton of the amplitude
modulation
nanostructurestructure, which
is formed. The is Sn-rich
interspersed
region with the surrounding
is filled Sn-poorofregion
with the skeleton to form a
the amplitude
modulation structure, which is interspersed with the surrounding Sn-poor region to form
braided nanostructure. The aging temperature determines the absence of discontinuous
amodulation structure, which
braided nanostructure. The is interspersed
aging temperaturewithdetermines
the surrounding Sn-poor
the absence region to form
of discontinuous
precipitation of γ. In [13], it
a braided nanostructure. is suggested that discontinuous precipitation
the absencewill occur after the
precipitation of γ. In [13],The
it isaging temperature
suggested determines
that discontinuous precipitationofwill
discontinuous
occur after
spinodal decomposition
precipitation in a
of γ. In [13], it isprolonged
suggested aging process,
thataging leading
discontinuous to a decrease
precipitation in yield
will occur stress.
after
the
In spinodal
addition, a decomposition
study carried in
out a
by prolonged
Luo [14] suggested process,
that leading
the to a decrease
discontinuous in yield
precipitation
the spinodal decomposition in a prolonged aging process, leading to a decrease in yield
Materials 2023, 16, 444 4 of 20
stress. In addition, a study carried out by Luo [14] suggested that the discontinuous pre-
of the γ (DO
cipitation ) phase
of3the can
γ (DO 3) also
phasebecan
achieved
also beby the decomposition
achieved of DO22 precipitated
by the decomposition after
of DO22 precip-
spinodal decomposition.
itated after spinodal decomposition.
Figure4.4.Bright-field
Figure Bright-field(BF)
(BF)TEM
TEMimage
imageof
ofaaquenched
quenchedCu–15Ni–8Sn
Cu–15Ni–8Snsample [12].
sample[12].
3. Preparation Process
3. Preparation Process
Continuous casting, powder metallurgy, plasma spraying, rapid solidification, and
Continuous casting, powder metallurgy, plasma spraying, rapid solidification, and
vacuum melting are some of the common methods of preparing Cu–Ni–Sn alloys.
vacuum melting are some of the common methods of preparing Cu–Ni–Sn alloys.
3.1. Continuous Casting
3.1. Continuous Casting
Continuous casting, an economical and efficient technology, is now widely used
Continuouscopper-based
to manufacture casting, an economical
materials. and For efficient technology,
copper alloys with aishigh nowSnwidely
content, used to
it is
manufacture copper-based materials. For copper alloys with a
common for the Sn to segregate during the continuous casting process and it is difficult tohigh Sn content, it is com-
mon for the
completely Sn to segregate
eliminate this Sn induring the continuous
the subsequent casting process
heat treatment, leadingand to theit is difficult to
degradation
completely eliminate this Sn in the subsequent heat treatment, leading
of the mechanical properties and corrosion resistance of the alloys. There are two types of to the degradation
of the mechanical
continuous casting:properties
horizontaland corrosion
casting resistance
and vertical of the alloys. There are two types of
casting.
continuous casting: horizontal casting and vertical casting.
In the case of horizontal casting, electromagnetic stirring technology is added and
In the metal
the molten case ofwith
horizontal casting, electromagnetic
current-carrying conductive properties stirring will
technology
form a largeis added and
electro-
the molten metal with current-carrying conductive properties
magnetic force with the action of an external electromagnetic field, which results in the will form a large electro-
magnetic
linear force with
or rotational the action
movement of of
theanmolten
external electromagnetic
metal. The essence of field, which results
electromagnetic in the
stirring
linear or rotational
technology is using movement
electromagneticof theforce
molten metal. The
to compel essencemetal
the molten of electromagnetic stirring
to move in a specific
technology
direction. Atistheusing
same electromagnetic force to compel
time, the temperature the molten metal
and concentration to move
fields of the moltenin a specific
metal
direction.
are At the same
made uniform time,the
to reduce thenucleation
temperature workand concentration
and fields radius
critical nucleation of the molten metal
and increase
are made uniform to reduce the nucleation work and critical
the number of equiaxed crystals during the solidification process, which can help achieve nucleation radius and in-
creaserefinement
grain the number and ofimprove
equiaxedthe crystals
quality during
of the the
castsolidification process, which
billet [15]. Horizontal casting can help
solves
achieve
the problem grainofrefinement and improveofthe
uneven solidification quality
liquid of the
metal cast billet
caused [15]. Horizontal
by gravity, refines thecasting
grain
solves
of billetthe problem
[16], of uneven
and improves the solidification
quality of continuousof liquidcasting
metal caused by gravity,the
billet. Moreover, refines
bridgesthe
grain
are of billet by
formatted [16],
theand improves growth
unbalanced the quality of continuous
of dendrites, which casting
preventsbillet.
theMoreover,
upper metal the
liquid
bridges fromareshrinking
formatteddownward, thus forming
by the unbalanced growtha central shrinkage.
of dendrites, However,
which prevents the the
dendritic
upper
growth conditions
metal liquid from can be improved
shrinking downward, effectively [17].
thus forming a central shrinkage. However, the
The advantage
dendritic of verticalcan
growth conditions casting is that it uses
be improved the additional
effectively [17]. factor of gravity and the
technology of hot topof
The advantage sovertical
that thecasting
copper is liquid
that can be injected
it uses uniformly
the additional at uniform
factor of gravity speed
and
and
the temperature,
technology ofso hotastop
to produce qualified
so that the copperbillets.
liquidHowever, at present,
can be injected electromagnetic
uniformly at uniform
stirring
speed and technology is mostly
temperature, applied
so as to tubequalified
to produce billets and the application
billets. However,of atslab, square,
present, and
electro-
round billet continuous casting is not mature [18]. Numerical simulation
magnetic stirring technology is mostly applied to tube billets and the application of slab, can also be used
to provide
square, and data support
round billetfor this technology
continuous castinginisthe notfuture.
mature [18]. Numerical simulation can
also be used to provide data support for this technology in the future.
Materials 2023, 16, 444 5 of 20
3.2. Powder Metallurgy

In powder metallurgy, metal powder or a mixture of metal powder and non-metallic
powder is used as the raw material to manufacture metal materials, composites, and
various products through forming and sintering. The basic process of preparing alloys by
the powder metallurgy method is as follows: First, some pre-alloyed powder is prepared
by atomization. Then, the alloy is prepared by conventional powder metallurgy processes,
such as pressing, forming, sintering. An alloy prepared by powder metallurgy is more
homogeneous, and the segregation of Sn in Cu–Ni–Sn alloys can partially be suppressed. To
prevent the addition of Ni from affecting the solid solubility of Sn in Cu, and to maximize
the solid solubility of Sn in Cu, there are generally two ways of obtaining raw material
powder: one is to add Cu powder or Ni powder into the partial pre-alloying powder
composed of the binary alloy powder tin bronze, and the other is to obtain Cu–Ni–Sn
ternary pre-alloying powder by rapid solidification atomization. In both methods, the
alloyed Sn is added to the raw material powder so that Sn segregation is restrained to
a certain extent. Therefore, even for alloys with a high Sn content, such as C72900 and
C72800, Cu–Ni–Sn alloys with uniform composition can be successfully prepared by this
method [19]. Then, the raw material powder above undergoes different forming and
sintering processes. For example, ternary pre-alloyed powders are capable of being directly
rolled into strips through a continuous production line. Conventional methods can also
be used for press and sinter forming. The operation involves mixing the lubricant into the
powders and pressing the mixture into shape under water pressure. Then, the intermediate
product is kept at a certain temperature for a period of time so the lubricant is fully
volatilized. Finally, sintering is carried out to produce the compact sample. In the sintering
process, the step-by-step sintering method can be used to prevent shape changes in the
pressed billet due to uniform heating. In the so-called step-by-step sintering method, the
blanks are kept in a low-temperature range for a specific time period and then heated up to
the high-temperature zone for sintering.
Experiments have proved that compared to normal isothermal sintering, when the
step-by-step sintering method is used, sintered samples with lower porosity, higher rela-
tive density, and more homogeneous composition can be obtained. Wu [20] prepared a
Cu/invar composite using powder metallurgy and investigated a series of preparation
parameters, such as optimal forming pressure and sintering temperature, achieving further
enhancements in electrical and thermal conductivity.
The advantages of preparing Cu–Ni–Sn alloys with the powder metallurgy method are
as follows [21]: (1) To a certain extent, the problem of Sn segregation in the preparation of
Cu–Ni–Sn alloys with a high Sn content using the traditional smelting method is overcome.
(2) The alloy composition can be controlled more precisely; a more homogeneous compo-
sition and finer grain size can be obtained for the subsequent age-hardening treatment.
However, at present, the process still has shortcomings due to the high production cost.
Furthermore, this method is only used to produce some products with simple shapes, such
as strips and wire rods.
3.3. Plasma Spraying

Plasma spraying strengthens the surface of the material to enhance its wear and
corrosion resistance. The method is also effective for preparing copper alloy coatings. A
semi-solid spray droplet is deposited on the formed substrate, casting a homogeneous
organization. Xiao [22] used thermal-spraying technology to prepare a Cu–15Ni–8Sn alloy
coating, and the optimal arc current was experimentally derived. The results of the studies
show that under the best arc current conditions, the number of the nonmelted or semi-
molten particles is reduced and the wear resistance of the coating is greatly improved
after aging. Low-segregation, fine-grain, high-density billets close to the final forming size
from liquid metal rapid solidification can be directly prepared by this method, which can
effectively inhibit the diffusion and aggregation of alloy elements and solve the problem
of Sn reverse segregation. However, the manufacturing cost is high, the size of the billet
Materials 2023, 16, 444 6 of 20
reverse segregation. However, the manufacturing cost is high, the size of the billet should
not be too large, and the microstructure of the bottom and middle positions of the alloy’s
deposited
should notbillet
be too varies
large,greatly.
and the microstructure of the bottom and middle positions of the
alloy’s deposited billet varies greatly.
3.4. Rapid Solidification Methods
3.4. Rapid Solidification Methods
Rapid solidification refers to a solidification process with a solidification rate much
fasterRapid solidification
than that refers to
of conventional a solidification
casting (generallyprocess with10a solidification
faster than mm/s). It is a rate much
non-equi-
librium solidification process that usually produces a metastable phase, resulting in a non-
faster than that of conventional casting (generally faster than 10 mm/s). It is a ma-
equilibrium
terial solidification
with excellent strength,process that usually
hardness, produces
and corrosion a metastable
resistance phase,
properties. resulting
Laser powder in
a material with excellent strength, hardness, and corrosion resistance
bed fusion (LPBF; Figure 5), which is one of the main technical approaches in the additive properties. Laser
powder bed fusion
manufacturing (LPBF;materials,
of metallic Figure 5), represents
which is one of thesolidification
a rapid main technical approaches
method. in the
In a protec-
additive manufacturing of metallic materials, represents a rapid
tive atmosphere, the metal powder is completely melted by a high-energy laser beam solidification method. In a
protective atmosphere, the metal powder is completely melted by a
along the laser path, followed by rapid solidification of the molten metal. By repeatinghigh-energy laser beam
along
this thethe
step, laser path,
layers arefollowed by rapid in
stacked, resulting solidification
a high-density,of the molten metal. By
high-performance metalrepeating
three-
this step, the layers are stacked, resulting in a high-density, high-performance
dimensional component. Compared with traditional processing methods, LPBF has many metal three-
dimensional component. Compared with traditional processing methods, LPBF has many
advantages [23]: during the LPBF forming process, the laser scanning rate and the solidi-
advantages [23]: during the LPBF forming process, the laser scanning rate and the solidifi-
fication cooling rate of the powder are fast, resulting in a fine and uniform grain structure
cation cooling rate of the powder are fast, resulting in a fine and uniform grain structure of
of the formed sample, and the segregation of elements can be effectively suppressed,
the formed sample, and the segregation of elements can be effectively suppressed, which
which improves the comprehensive performance of the formed components. LPBF tech-
improves the comprehensive performance of the formed components. LPBF technology
nology is a layer-by-layer stacking technique, making it possible to build prototypes with
is a layer-by-layer stacking technique, making it possible to build prototypes with com-
complex structures that are difficult to process by conventional methods. Compared with
plex structures that are difficult to process by conventional methods. Compared with the
the traditional preparation method, the process is relatively simple. The material utiliza-
traditional preparation method, the process is relatively simple. The material utilization
tion rate is high, and the unformed powder can be recycled. In Cu–Ni–Sn alloys of C72500
rate is high, and the unformed powder can be recycled. In Cu–Ni–Sn alloys of C72500 and
and C72900, macrosegregation is eliminated by rapid solidification but microsegregation
C72900, macrosegregation is eliminated by rapid solidification but microsegregation still
still exists in thin strips. Rapid solidification significantly reduces the degree and spacing
exists in thin strips. Rapid solidification significantly reduces the degree and spacing of
of segregation
segregation [24].
[24]. In addition,
In addition, duedue to the
to the fastfast solidification
solidification rate,rate, the grain
the grain cansignificantly
can be be signifi-
cantly refined, and it has been claimed that Cu–Ni–Sn alloys can
refined, and it has been claimed that Cu–Ni–Sn alloys can be prepared without segregation be prepared without
segregation through the design of preparation parameters [25]. Cu–15Ni–8Sn
through the design of preparation parameters [25]. Cu–15Ni–8Sn alloys prepared by LPBF alloys pre-
pared by LPBF
have good have good
strength strength and
and toughness, antoughness,
RM of 593.3 an MPa,
RM ofand 593.3
anMPa, and an elongation,
elongation, a, of 19.8%.
a, of 19.8%. The elastic modulus, E, of the LPBF alloy is
The elastic modulus, E, of the LPBF alloy is 144 GPa, which is 7% higher 144 GPa, which is 7%
thanhigher
that ofthan
the
that of the as-cast alloy. Complex-shaped parts can be manufactured
as-cast alloy. Complex-shaped parts can be manufactured by LPBF technology, which is by LPBF technology,
which
another is advantage
another advantage
[26]. [26].
Figure 5.
Figure LPBF principle
5. LPBF principle [27]
[27]..
Nevertheless, LPBF technology is still in the research stage due to its high cost, and
Nevertheless, LPBF technology is still in the research stage due to its high cost, and
has many problems: During the LPBF-forming process, large residual internal stress is
has many problems: During the LPBF-forming process, large residual internal stress is
generated in the formed components by the rapid cooling and solidification process of
metal materials, which can lead to cracks in the material. Depending on the construction
Materials 2023, 16, 444 7 of 20
direction and scanning strategy of LPBF technology, directional growth of grains can be
caused by the large temperature gradient and complex heat transfer caused by the laser,
and as a result of this, the microstructure and properties of the alloy tend to be anisotropic.
In addition, the quality of parts obtained by LPBF depends on the selection of process
parameters, such as laser power, scanning speed, scanning spacing, and layer thickness,
which are influenced by material properties, such as powder fluidity, particle size, shape,
and distribution, as well as the type and spot size of laser. Finally, inappropriate process
parameters can cause defects such as pellets, pores, cracks, and low density, significantly
reducing the comprehensive performance of LPBF parts.
3.5. Vacuum Melting Process

In vacuum melting, alloys are melted under the protection of vacuum or other gases
(hydrogen, argon, etc.) which can strictly control the composition of the alloy and ensure
that the material has a high degree of purity. During the melting process, the segregation
of Sn is not reduced by the vacuum melting process itself [28]. Therefore, various trace
alloying elements (such as Fe and Si) are added during the melting process, or the ingot is
homogenized after melting to reduce the segregation of Sn and improve the alloy properties.
Guo et al. prepared a Cu–15Ni–8Sn alloy by the vacuum melting method and investi-
gated the effect of adding Fe on the properties [29]. The results showed that the addition
of Fe to the Cu–15Ni–8Sn alloy could improve the alloy’s anti-aging resistance, hardness,
and tensile properties. Furthermore, when the Fe content was 0.1%, the maximum ultimate
tensile strength of the alloy was 123 MPa higher than that of the Fe-free alloy.
The advantages and disadvantages of the above preparation processes are summarized
and listed in Table 1.
Table 1. The advantages and disadvantages of various methods of preparing Cu–Ni–Sn alloys.
Preparation Process Advantages Disadvantages

Presence of elemental
Continuous casting Economical and efficient
segregation
Homogeneous composition High cost but only suitable for
Powder metallurgy
and fine grain size simple shapes
Finer grain, higher density, High cost and a wide variation in
Plasma spraying
and near-final formation different microstructures
Refined grain, suppressed
High cost, complex parameter
Rapid solidification segregation, high material
control, and large residual stresses
utilization, and simple process
Guaranteed high purity High equipment requirements and
Vacuum melting
of materials difficult to apply in industry
4. Effect of Alloying Elements on Tissue Properties

After heat treatment, the mechanical properties and corrosion resistance of Cu–15Ni–
8Sn alloys are greatly improved. In addition, a fourth element can be added to further
improve the alloy’s properties. Several common alloying elements are listed in this section,
and their effects on the microstructure and properties of the alloy are described. Intermetal-
lic compounds with Ni will be formed when elements such as Si, Ti, and Nb are added to
the alloy, which are diffusely distributed in the matrix, occupying the nucleation sites of
discontinuous precipitation, inhibiting the movement of grain boundaries, and refining
grains; thus, discontinuous precipitation is significantly inhibited. The precipitation of the
DP phase is inhibited when elements such as Fe and Co are added, which solidly dissolve
into the copper matrix as solute atoms and affect the organization and properties of the
alloy by influencing the aging precipitation behavior.
4.1. Si
The precipitation of phase γ0 in the matrix has been found to be delayed by the addition
of Si, thus retarding the hardening of the matrix [30]. Fine particles precipitated from the
tion of the DP phase is inhibited when elements such as Fe and Co are added, which sol-
idly dissolve into the copper matrix as solute atoms and affect the organization and prop-
erties of the alloy by influencing the aging precipitation behavior.
Materials 2023, 16, 444 4.1. Si 8 of 20

The precipitation of phase γ′ in the matrix has been found to be delayed by the addi-
tion of Si, thus retarding the hardening of the matrix [30]. Fine particles precipitated from
Nithe Si
Ni31Si12 phase were observed in the grain boundary and matrix of quenched samples
31 12 phase were observed in the grain boundary and matrix of quenched samples with
with a Si content
a Si content of more ofthan
more0.4%,thanand
0.4%,it isand it is considered
considered that these that these
fine fine particles
particles could
could occupy
occupy the nucleation position of crystal cells and inhibit the migration
the nucleation position of crystal cells and inhibit the migration of grain boundaries so of grain bounda-
asries
to so as to strengthen
strengthen the matrix theand
matrix
fineand fine Luo
grains. grains.
[31]Luo [31] prepared
prepared low-Sn Cu–Ni–Sn
low-Sn Cu–Ni–Sn alloys,
alloys,led
which which led to a reduced
to a reduced precipitation
precipitation strengthening strengthening
effect [32].effect [32]. Therefore,
Therefore, Si and Al
Si and Al elements
elements
were added were added
to the alloytoandthethe
alloy and showed
results the results
thatshowed that the
the strength strength
of the of thereach
alloy could alloy
could reach 861 MPa, comparable to that of Cu–15Ni–8Sn, and the
861 MPa, comparable to that of Cu–15Ni–8Sn, and the alloy had an elongation of up to 18%. alloy had an elongation
Asof up to 18%.
shown As shown
in Figure in average
6, the Figure 6,diameter
the average diameter recrystallized
of dynamic of dynamic recrystallized
grains of the grains
0 Si
of the 0 Si alloy is 46 ± 2.2 µm, and the average diameter of recrystallized
alloy is 46 ± 2.2 µm, and the average diameter of recrystallized grains of the 0.5 Si alloy grains of the 0.5
isSi34alloy
± 4.3 is 34
µm.± 4.3
Thisµm. Thistoisthe
is due dueformation
to the formation
of Ni3 Siof Ni3Si nanoparticles
nanoparticles by Si andbyNi,
Si and Ni,
which
which inhibits
inhibits grain recrystallization
grain recrystallization and thusand thus
refines refines
the grains.the grains. Moreover,
Moreover, due to the due to the
reduction
ofreduction of Sn, macroscopic
Sn, macroscopic segregation segregation
during theduring the alloy preparation
alloy preparation process isprocess
reduced is or
reduced
even
or even eliminated,
eliminated, resultingresulting
in a moreinhomogeneous
a more homogeneous microstructure.
microstructure.
(a) (b)
Figure6.6. Structure of the
Figure the extruded
extrudedCu–9Ni–2.5Sn–xSi
Cu–9Ni–2.5Sn–xSialloy
alloyasasshown
shown
byby
anan optical
optical microscope:
microscope: (a)
x =x0;= (b)
(a) x= x=
0; (b) [31]
0.50.5 .
[31].
4.2.
4.2.Ti
Ti
On
Onadding
addingTi,Ti,thethe
Ni3NiTi3phase is formed
Ti phase during
is formed solidification
during [33], and
solidification [33],the Ni3the
and Ti phase
Ni3Ti
does not dissolve in the subsequent solid solution treatment, leading to grain refinement
phase does not dissolve in the subsequent solid solution treatment, leading to grain re-
due to the inhibitory effect of the Ni3 Ti phase on grain boundary migration. Meanwhile,
finement due to the inhibitory effect of the Ni3Ti phase on grain boundary migration.
the nucleation sites of discontinuous precipitates are reduced on adding Ti, which inhibits
Meanwhile, the nucleation sites of discontinuous precipitates are reduced on adding Ti,
the discontinuous precipitates.
which inhibits the discontinuous precipitates.
Generally, more than one element is added to improve the properties of materials.
Generally, more than one element is added to improve the properties of materials.
Zhao [34] added Ti and Si to a Cu–15Ni–8Sn alloy, which led to the precipitation of the
Zhao [34] added Ti and Si to a Cu–15Ni–8Sn alloy, which led to the precipitation of the
Ni16 Si7 Ti6 intermetallic compound after hot extrusion and subsequent air cooling. Zhao
Ni16Si7Ti6 intermetallic compound after hot extrusion and subsequent air cooling. Zhao
found that (1) in the process of high-temperature hot extrusion, these kinds of micro- and
found that (1) in the process of high-temperature hot extrusion, these kinds of micro- and
nano-particles are evenly dispersed in the matrix and the nucleation of dynamic recrys-
nano-particles are evenly dispersed in the matrix and the nucleation of dynamic recrys-
tallization is effectively promoted by the micron particles due to the particle-stimulated
tallization is effectively promoted by the micron particles due to the particle-stimulated
nucleation (PSN) effect, and (2) during the subsequent air cooling process, the growth of
nucleation (PSN)
recrystallized effect,
grains and (2) during
is effectively the subsequent
inhibited air coolingthrough
by the nanoparticles process,pinning
the growth of
grain
recrystallized grains is effectively inhibited by the nanoparticles through
boundary migration, accelerating the transformation from small to large angular grain pinning grain
boundary migration,
boundaries [35]. Figure accelerating the image
7 is the TEM transformation
of Ni16 Si7from small toand
Ti6 particles largetheangular grain
dislocation
boundaries [35]. Figure 7 is the TEM image of Ni 16Si7Ti6 particles and the dislocation
boundary. Thus, the addition of elements leads to fine grain strengthening and grain
boundary strengthening. The tensile strength and elongation of the alloy can reach the
values of 909 MPa and 30%, respectively, with significantly improved tensile properties.
boundary. Thus, the addition of elements leads to fine grain strengthening and grain
Materials 2023, 16, 444
boundary. Thus, the addition of elements leads to fine grain strengthening and 9grain
of 20
Figure 7. TEM image of Ni16Si7Ti6 particles and the dislocation boundary [35].
Fe7.7.TEM
Figure
4.3.
Figure TEMimage
imageof
ofNi
Ni1616Si particles and the dislocation boundary [35]
Si77Ti6 particles [35]..
4.3. FeIn the late aging period, the properties of the alloy can significantly deteriorate due
4.3. Fe
to theIn rapid
the late nucleation
aging period, and the
growth of discontinuous
properties of the alloy can precipitates
significantlywith a γ (DO3)due
deteriorate structure.
to
The In the late
growth of aging period, theprecipitates
discontinuous properties of wastheinhibited
alloy can successfully
significantly deteriorate
by adding due
Fe [29].
the rapid nucleation and growth of discontinuous precipitates with a γ (DO3 ) structure.
to the rapid to
According nucleation andtheory growth[36],of discontinuous precipitates with a γbe(DO 3) structure.
The growth of Turnbull’s
discontinuous precipitates thewas
growth rate
inhibited of DP (G)
successfully can calculated
by adding Fe [29].by the
The growth
following to of
formuladiscontinuous
(Equation precipitates was inhibited successfully by adding Fe [29].
According Turnbull’s theory(1)):
[36], the growth rate of DP (G) can be calculated by the
According to Turnbull’s theory [36], the growth rate of DP (G) can be calculated by the
following formula (Equation (1)):
following formula (Equation (1)): G b
4δD , (1)
G= 2
, (1)
where δ is the cell boundary thickness and G S Db and , S are the solute diffusivity along (1) the
where δ is the cell boundary thickness and D and S are the
forward boundary and interlayer spacing, brespectively. In this study, δ is unknown and solute diffusivity along the
where δboundary
forward is the celland boundary thickness
interlayer spacing, and Db and S are
respectively. the solute
In this study, δdiffusivity
is unknown along
andthe is
is assumed
forward
to be constant.
boundary and interlayer spacing, respectively. In this study, δ is unknown and
assumed to be constant.
The rapid
is assumed to be diffusion
constant. of Fe atoms causes the preferential precipitation of Fe clusters in
The rapid diffusion of Fe atoms causes the preferential precipitation of Fe clusters
the discontinuous precipitates, which increases the interlayer spacing ofFeDP. Therefore,
in theThe rapid diffusion
discontinuous of Fe atoms
precipitates, whichcauses the preferential
increases the interlayer precipitation
spacing ofofDP. clusters
Therefore, in
after the addition
the discontinuous of Fe, the D b value decreases and the S value increases, which inhibits
after the addition ofprecipitates,
Fe, the Db valuewhichdecreases
increasesand thethe interlayer
S value spacing
increases, of which
DP. Therefore,
inhibits
the
after
the further
further growthof
the addition
growth ofofdiscontinuous
Fe,discontinuous
the Db value precipitates.
decreases
precipitates. As As
and theshown
shown S value inincreases,
in FigureFigure
8, the8, discontinuous
the discontinuous
which inhibits
precipitation
the further growth
precipitation ofofthethe γdiscontinuous
γofphasephase
waswas reduced
reduced significantly
precipitates.
significantly As by shownthe by in the
Figure
addition addition
of8,Fe. of Fe.
theThis This is be-
discontinuous
is because
cause
Fe Fe is enriched
precipitation
is mainly mainly
of the γenriched
inphase was
the core inofthethecore
reduced
DO22 ofordered
the DOphase,
significantly 22 ordered
by the phase,
addition
which which
of
increases Fe. increases
This
the is be- the
stability
stability
cause Fe of
is the
mainly DO
of the DO22 ordered phase, making it difficult to transform the DO22 ordered phaseordered
ordered
enriched
22 in phase,
the core making
of the it
DO difficult
22 ordered to transform
phase, which the DO
increases22 the
to
phase
stability
the γ (DO to of
3thetheγ (DO
) phase. 3) ordered
22 phase. Furthermore,
DOFurthermore, phase, making
the tensile the
it tensile
difficult
strength strength
of the tomaterial of the
transform material
canthe can reach
DOa22value
reach ordered of a
phase
value
1250 to 1250
of
MPa, the γMPa,
which (DO 3)which
is 123phase. Furthermore,
MPaishigher
123 MPa theoftensile
thanhigher
that than strength
that
the Fe-free theofFe-free
ofalloy. the material
alloy. can reach a
value of 1250 MPa, which is 123 MPa higher than that of the Fe-free alloy.
(a)
(a) (b)(b)
Figure 8. STEM image of a cold-rolled alloy Cu–15Ni–8Sn–xFe: (a) x = 0; (b) x = 0.5 [29].
Materials 2023, 16, 444 Figure 8. STEM image of a cold-rolled alloy Cu–15Ni–8Sn–xFe: (a) x = 0; (b) x = 0.5 [29]. 10 of 20
4.4. P
4.4. PThe addition of the trace element P (0.1 wt% and 0.2 wt%) can effectively inhibit the
nucleation and growth
The addition of DP,element
of the trace but thePeffect
(0.1 wt%on DP andis0.2
reversed
wt%) can when the content
effectively inhibitof the
the
nucleation and growth of DP, but the effect on DP is reversed when the content of theis
element P is greater than 0.3 wt% [37]. This is because the nucleation position of DP
occupiedP by
element the Ni10than
is greater SnP3 0.3
phasewt% located at theisgrain
[37]. This becauseboundary, which inhibits
the nucleation positionitsofnuclea-
DP is
tion. The grain can be refined by the addition of P. Although
occupied by the Ni10 SnP3 phase located at the grain boundary, which inhibits the content of its
thenucleation.
element P
is larger,
The grainthecangrain boundary
be refined areaaddition
by the fraction ofincreases and the
P. Although thegrain boundaries
content are the main
of the element P is
location
larger, theofgrain
DP nucleation.
boundary area Thus, DP nucleation
fraction increasescan andbe thepromoted by the increase
grain boundaries are the inmainthe
grain boundary
location area fraction.
of DP nucleation. In addition,
Thus, Ni10SnP
DP nucleation 3 will
can be precipitate
promoted by at the
thegrain boundary,
increase in the
absorbing
grain solutearea
boundary atoms in theInvicinity,
fraction. addition, andNias a result
10 SnP 3 willofprecipitate
this, the surrounding matrix so-
at the grain boundary,
lute is impoverished
absorbing solute atomsand unable
in the to precipitate
vicinity, and as a result ordered phases,
of this, which eventually
the surrounding matrix results
solute
isinimpoverished
the formationand of aunable
precipitation-free
to precipitatezone,orderedwhich is also
phases, a reason
which for theresults
eventually inhibition
in theof
the DP phase
formation of a by P. Figure 9 displays
precipitation-free zone,the TEMisbright-field
which also a reason image of the
for the Cu–15Ni–8Sn–xP
inhibition of the DP
alloy. by
phase TheP. interlayer spacingthe
Figure 9 displays of the
TEM DP phase is indicated
bright-field image of by thethe scale in the figure,
Cu–15Ni–8Sn–xP alloy.and
Theit
interlayer spacing
is found that of the DPspacing
the interlayer phase is of indicated
the DP phase by the scale inafter
increases the the
figure, and it
element found
P is added.
that the interlayer
As seen from Equationspacing of the
(1), the interlayer
DP phase increases after the element
spacing increases and the P DPis growth
added. As rateseen
de-
from Equation (1), the interlayer spacing increases and the DP growth rate decreases.
creases.
(a) (b)
Figure9.9.TEM
Figure TEMbright-field
bright-fieldimage
imageof
ofthe
thealloy
alloyCu–15Ni–8Sn–xP:
Cu–15Ni–8Sn–xP:(a)
(a)xx==0;0;(b)
(b)xx== 0.2
0.2 [37].
[37].
4.5. V
4.5. V
The grains can be refined by adding the element V to Cu–15Ni–8Sn. When the V
The grains can be refined by adding the element V to Cu–15Ni–8Sn. When the V
content is less than or equal to 0.4 wt%, grain refinement is mainly limited by growth.
content is less than or equal to 0.4 wt%, grain refinement is mainly limited by growth.
When the V content increases to 0.6 wt%, the grain refinement mechanism changes to
When the V content increases to 0.6 wt%, the grain refinement mechanism changes to
heterogeneous nucleation [38]. The production of DP can also be inhibited by the addition
heterogeneous nucleation [38]. The production of DP can also be inhibited by the addition
of V [39]. The original grain boundary (OGB) and layered structure can be clearly seen in
of V [39]. The original grain boundary (OGB) and layered structure can be clearly seen in
Figure 10. When no V is added, discontinuous precipitation occurs preferentially at the
Figure 10. When no V is added, discontinuous precipitation occurs preferentially at the
grain boundary and grows smoothly toward the matrix. The precipitated Ni3 V particles
grain
are boundary
located at the and
graingrows smoothly
boundary, toward
as shown the red
by the matrix. Theinprecipitated
arrows Ni3V particles
the figure. These particles
are located at the grain boundary, as shown by the red arrows in the figure.
occupy the nucleation position of discontinuous precipitation. In addition, the Ni3 V These particles
occupy the
particles nucleationatposition
precipitated the grainofboundary
discontinuous
haveprecipitation. In addition,
an obvious pinning effect the Ni3V
on the par-
grain
ticles precipitated at the grain boundary have an obvious pinning effect
boundary, increasing the activation energy of DP and making DP precipitation difficult. on the grain
boundary,
The additionincreasing
of V has athe activation
significant energy
effect of DP
on the and making
interlayer spacing DPofprecipitation difficult.
DP in the Cu–15Ni–
Thealloy,
8Sn addition
andoftheV interlayer
has a significant
spacingeffect on increases
of DP the interlayer
withspacing of DPininthe
the increase theVCu–15Ni–
content.
8Sn alloy, and the interlayer spacing of DP increases with the increase
When the V content is 0.4 wt%, the alloy’s resistance to softening can be improved in the V content.
with
When the Vheat
appropriate content is 0.4 wt%,
treatment and the
the alloy’s
tensile resistance to softening
strength can can be
reach a value ofimproved
990 MPa with[38].
appropriate
The OGB andheat treatment
layered and the
structure cantensile strength
be clearly seencan reach
in the a value
figure. of 990
When V MPa
is not[38]. The
added,
discontinuous precipitation occurs preferentially at the grain boundary and grows smoothly
toward the matrix.
OGB and layered structure can be clearly seen in the figure. When V is not added, discon-
OGB andprecipitation
tinuous layered structure can
occurs be clearly seen
preferentially in the
at the figure.
grain When and
boundary V is grows
not added, discon-
smoothly
Materials 2023, 16, 444 11 of to-
20
tinuous precipitation
ward the matrix. occurs preferentially at the grain boundary and grows smoothly to-
ward the matrix.
(a) (b) (c)

(a) (b) (c)
Figure 10. SEM image of discontinuous precipitation at grain boundary of Cu-15Ni-8Sn-xV alloy
Figure
(a) x = 10. SEM
SEM
0; (b) image
x = image
0.4; (c)ofof discontinuous
x =discontinuous
1.0 [38]. precipitationatatgrain
precipitation grainboundary
boundaryofof Cu-15Ni-8Sn-xV
Cu-15Ni-8Sn-xV alloy
alloy
(a) x = 0; (b) x == 0.4;
0.4; (c) 1.0[38]
(c) xx ==1.0 [38]..
4.6.Co
4.6. Co
4.6. Co
Co addition
Co addition can can inhibit
inhibit DP DP production,
production, but but thethe mechanism
mechanism isis different
different from
from those
those
above.Co On
addition
adding canCo,inhibit
the DP production,
dendritic structure but
of the alloy
the mechanism
becomes is shorter,
differentthe frombonythose
Sn-
above. On adding Co, the dendritic structure of the alloy becomes shorter, the bony Sn-rich
above.
rich On adding
region becomes Co,smaller,
the dendritic
the Sn structure
content inofthethematrix
alloy increases,
becomes shorter,and the the bonystruc-
as-cast Sn-
region becomes smaller, the Sn content in the matrix increases, and the as-cast structure
rich
ture region
the becomes smaller, the SnAtcontent in the matrix increases, and the
the as-cast struc-
of theofalloy alloy
is more is more
uniform. uniform. this point,
At this point, the
the alloy alloy is harder
is harder thanthanthe alloy alloy without
without the
ture
the of the alloy
addition of is more
Co. This uniform.
is because AtCo this point,
more the alloy
readily binds istoharder than The
vacancies. the alloy
lack without
of vacan-
addition of Co. This is because Co more readily binds to vacancies. The lack of vacancies of
the
ciesaddition
of Ni
Sn atoms
andof NiCo.atoms
This isinbecause Co more
Cu isbycaused by readily
the of binds to Co,
addition vacancies.
and theThe lack of vacan-
Sn and in Cu is caused the addition Co, andofthe segregation segregation
of Sn clusters of Sn
is
cies of
clustersSn isand Ni
suppressed atoms in
[40], Cu is caused
increasing by
the the addition
activation of
energy Co,
of and
the the
alloy segregation
and delaying of the
Sn
suppressed [40], increasing the activation energy of the alloy and delaying the formation of
clusters
formation is suppressed
of DP. [40], increasing theare
activation energy of the of alloy and delaying the
DP. In addition, CoInatoms
addition, Co atoms
are dissolved in thedissolved
core of the in the
L12corephase, the L12 enhances
which phase, which
the
formation
enhances
stability of
theDP.
ofthe L12Inphase
stabilityaddition,
of and Co atoms
the L12
thus phase
inhibits are
and dissolved
thethus in the
inhibits
conversion of core
the L1 of the L1of
conversion 2 phase,
L12 to which
DO3 at
2 to DO3 at the later stage
enhances
the later the
stage stability
of heat of the
treatment.L12 phase
The and
curve thus
of inhibits
microhardness
of heat treatment. The curve of microhardness (HV) of the Cu–15Ni–8Sn–xCo alloy with the conversion
(HV) of theof L1 2 to DO3 at
Cu–15Ni–8Sn–
the
xCo
an later
alloy
aging stage
withofan
temperature heat
agingtreatment.
of 773 The curve
temperature
K is shown ofin773ofKmicrohardness
Figure is 11.
shown
Adding (HV)
in Figure
the of the
11.
proper Cu–15Ni–8Sn–
Adding
amount theofproper
Co to
xCo alloy
amount
the alloy of with
canCo an aging
to the alloy
improve temperature
can improve
the hardness, of
delay 773
thethe K is
hardness, shown in Figure
delay the behavior,
aging hardening 11. Adding
aging hardening the
and improve proper
behavior,
the
amount of Co the
and improve
aging resistance to of
the alloy
aging
the can improve
resistance
alloy. of the the hardness, delay the aging hardening behavior,
alloy.
and improve the aging resistance of the alloy.
Figure11.
Figure 11.Aging
Aginghardening
hardeningcurves
curvesof
ofalloys
alloyswith
withdifferent
differentCo
Cocontents
contentstreated
treatedby
by773
773KKisothermal
isothermal
Figure
aging 11. Aging
[40]
aging[40]. . hardening curves of alloys with different Co contents treated by 773 K isothermal
aging [40].
4.7.
4.7.Nb
Nb
4.7. Nb
The
Thestrength
strengthandandtoughness
toughnessofof the alloy
the Cu–15Ni–8Sn
alloy Cu–15Ni–8Sn cancan
be improved by the
be improved addition
by the addi-
of Nb. In a study carried out by Ouyang et al. [25], some intergranular precipitates in
tion The strength
of Nb. and carried
In a study toughness outof
bythe alloy Cu–15Ni–8Sn
Ouyang et al. [25], somecan be improvedprecipitates
intergranular by the addi-
in
the Cu–15Ni–8Sn alloy rich in Ni, Sn, and Nb were observed through high-angle
tion of Nb. In a study carried out by Ouyang et al. [25], some intergranular precipitates in annular
dark-field imaging analysis. Ouyang et al. suggested that these precipitates contribute
to the alloy’s strength and toughness. Chen et al. [41] concluded that the increase in
strength and toughness of the Cu–15Ni–8Sn alloy is due to the formation of NbNi2 Sn
and NbNi3 phases, that the increase in strength is mainly due to grain boundary and
Materials 2023, 16, 444 12 of 20
precipitation strengthening, and that the increase in toughness is mainly due to grain
refinement. One of the studies carried out by Gao [42] found that the addition of Nb could
refine the grain, forming the NbNi3 compound and improving the strength and toughness
of Cu–9Ni–6Sn alloys.
Effect of alloy elements on microstructure and properties are summarized in Table 2.
Table 2. Effect of alloy elements on microstructure and properties.
Element Strengthening Phase Strengthening Mechanism Mechanical Properties

Strengthening of the grain boundary and inhibition of
Si Ni31 Si12 , Ni3 Si Tensile strength: 861 MPa
grain recrystallization
Strengthening of the grain boundary, inhibition of DP
Ti Ni3 Ti, Ni16 Si7 Ti6 Tensile strength: 909 MPa
phase precipitation, and strengthening of fine grains
Inhibition of DP phase precipitation and increase in
Fe – Tensile strength: 1282 MPa
the stability of the DO22 ordered phase
P Ni10 SnP3 Tensile strength: 1282 MPa Hardness: 400 HV
Refinement of grains and inhibition of DP
V Ni3 V Tensile strength: 990 MPa
phase precipitation
Inhibition of DP phase precipitation and enhancement
Co – Hardness: 412 HV
of L12 -phase stability
Strengthening of the grain boundary and
Nb NbNi2 Sn, NbNi3 Tensile strength: 590 MPa
strengthening of precipitation
5. Effect of Plastic Deformation and Heat Treatment on the Microstructure and

Properties of Cu–Ni–Sn Alloys
Cu–15Ni–8Sn alloys have good mechanical properties and corrosion resistance. These
alloys are often prepared by casting or other processes involving plastic deformation or heat
treatment which can bring out more excellent properties of the alloys. The most important
parameter of plastic deformation is the amount of deformation. If the deformation is too
low, it will not achieve the effect of strengthening, and if the deformation is too high, it will
lead to the precipitation of the DP phase, leading to a decline in the mechanical properties
and corrosion resistance. Therefore, the entire treatment process should be controlled
by controlling the deformation according to the alloy and with heat treatment. In the
process of heat treatment, tempering temperature and time are particularly important.
If the temperature or time is too low to achieve the effect of aging, the alloy will not be
strengthened. However, if the temperature is too high, it will lead to over-aging and the
mechanical properties of the alloy may be reduced.
5.1. Plastic Deformation

Deformation treatment is an important method of strengthening alloys. For Cu–Ni–Sn
alloys, the higher the Sn content, the higher the pre-cold processing level should be. In
addition, the momentum of continuous transformation is increased by cold working, which
is conducive to the subsequent transformation of the reinforced phase precipitation [43].
Deformation also affects the microstructure of the alloy. The deformation after homog-
enization influences the microstructural changes during aging. The dislocation created
during deformation and the spinodal structure interact, accelerating the process of phase
transformation of the aging alloys. The deformation before aging promotes the aging
microstructure changes and rapidly increases the size of forming phase [44].
One of the studies carried out by Guo [45] investigated the effect of deformation on
the microstructure and properties of the alloy during cold rolling. After pre-rolling, the
surface oxide scale is removed by heating the alloy to 850 ◦ C. Then, the alloy is rolled at
room temperature with different deformations, and finally tempered at 400 ◦ C. With the
increase in deformation, the tempering peak time is greatly reduced, reducing the cost and
significantly improving performance. Especially at 90% deformation, the yield strength of
the alloy can reach a value of 1256 MPa after aging, and the main strengthening mechanisms
are solution strengthening, dislocation strengthening, and precipitation strengthening.
the microstructure and properties of the alloy during cold rolling. After pre-rolling, the
surface oxide scale is removed by heating the alloy to 850 °C. Then, the alloy is rolled at
room temperature with different deformations, and finally tempered at 400 °C. With the
increase in deformation, the tempering peak time is greatly reduced, reducing the cost
Materials 2023, 16, 444 and significantly improving performance. Especially at 90% deformation, the yield 13 of 20
strength of the alloy can reach a value of 1256 MPa after aging, and the main strengthening
mechanisms are solution strengthening, dislocation strengthening, and precipitation
strengthening. Figure 12 shows the yield strength of the alloy with different rolling defor-
Figure 12 shows the yield strength of the alloy with different rolling deformations. It is
mations. It is worth noting that when the alloy deformation increases, DP is also more
worth noting that when the alloy deformation increases, DP is also more likely to precipitate,
likelyand
to precipitate, and the intracrystalline
the intracrystalline precipitation ofprecipitation of DPtoisthe
DP is transferred transferred to the grain
grain boundaries, which
boundaries,
may make the grain boundary more susceptible to corrosion. Hot extrusion is Hot
which may make the grain boundary more susceptible to corrosion. ex- of
a method
trusion
heatistreatment,
a method and of heat treatment, and
the temperature theextrusion
of hot temperature of hotlower
is slightly extrusion
than is
theslightly
quenching
lower than the quenching temperature. For this alloy, the hot extrusion
temperature. For this alloy, the hot extrusion temperature is about 830 C. In the process temperature
◦ is of
abouthot830 °C. In thedue
extrusion, process
to theofhigh
hot extrusion,
temperature duedynamic
to the high temperature
strain, aging (DSA) dynamic
occursstrain,
[46]. DSA
agingis(DSA) occurs [46]. DSA is the result of dynamic interactions
the result of dynamic interactions between mobile dislocations and diffusible between mobile dislo-
solutes.
cations
Forand diffusible
Cu–Ni–Sn solutes.
alloys, theFor Cu–Ni–Sn
element alloys,
Sn is the the element
diffusible soluteSninisDSA,
the diffusible
and DSAsolutecauses Sn
in DSA,
andand DSA
Ni to causes Sn
polarize. In and
hot Ni to polarize.
extrusion (whichIn hot extrusion
is the (which isphase
strengthening the strengthen-
L12 ), Ni3Sn is
ing phase L1 ), Ni3Sn is precipitated during the subsequent
precipitated during the subsequent aging. Due to the dislocation pinning
2 aging. Due to the dislocation
effect produced
pinning effect the
by DSA, produced
spinodal by decomposition
DSA, the spinodal decomposition
in subsequent aging in is
subsequent
inhibited, aging
but the is in-
time of
hibited,
agingbutisthe time of aging
considerably is considerably
reduced. reduced. It that
It is also noteworthy is also
hotnoteworthy
extrusion also thatpromotes
hot ex- DP
trusion also promotes
precipitation. DP precipitation.
Therefore, Therefore,
the strengthening theofstrengthening
effect hot extrusion effect of hot
on alloys extru-to be
remains
sion fully
on alloys remains to be fully investigated. In addition, it has been
investigated. In addition, it has been shown that the grain size exhibits heritability, shown that the
graini.e.,
size exhibits heritability, i.e., on the basis of the preparation
on the basis of the preparation of fine grains, the mechanical properties of of fine grains, the me-
alloy can
chanical properties
be further of the by
improved alloy
thecan be furtheroperation
subsequent improved ofby the subsequent
plastic deformation, operation
mainly of due to
plastic deformation,
additional mainly added
dislocations due to by additional
the graindislocations
refinement added
[47]. by the grain refinement
[47].
The variations in yield strength versus ◦ C [45].

Figure
Figure 12.variations
12. The in yield strength versus agingaging time after
time after agingaging treatment
treatment at 400at°C
400
[45] .
Good corrosion resistance is another property of Cu–15Ni–8Sn, and it is also of great

significance
Good corrosion to study the effect
resistance of heatproperty
is another treatment
of on this property.
Cu–15Ni–8Sn, andA itstudy carried
is also out by
of great
Zhang [48] investigated the effect of different thermomechanical treatments
significance to study the effect of heat treatment on this property. A study carried out byon the seawater
corrosion resistance of the alloy and found that cold rolling after hot rolling reduces the
Zhang [48] investigated the effect of different thermomechanical treatments on the sea-
precipitation of the discontinuous Sn- and Ni-rich phases and avoids the occurrence of
water corrosion resistance of the alloy and found that cold rolling after hot rolling reduces
local corrosion. This multi-stage thermomechanical treatment increases the amount of
the precipitation of the discontinuous Sn- and Ni-rich phases and avoids the occurrence
deformation in the material, resulting in more nano-sized ordered precipitates, which are
of local corrosion. This multi-stage thermomechanical treatment increases the amount of
more uniformly distributed in the subsequent aging process and provides better corrosion
resistance. A heat treatment process for the alloy involving cold rolling and hot rolling
was also carried out by Yang [49]. The difference between the studies by Yang [49] and
Zhang [48] is that Yang performed two-stage homogenization annealing prior to hot rolling
(800 ◦ C × 4 h + 830 ◦ C × 4 h) and the differences between peak aging and over-aging alloy
properties were investigated. The annual average corrosion rate after peak aging treatment
is 0.01529 mm/a, which is lower than that of over-aged samples. This is because over-aging
causes more DP phases to precipitate at the grain boundary, forming a micro-galvanic cell
with the matrix and accelerating the corrosion of the alloys.
ing (800 °C × 4 h + 830 °C × 4 h) and the differences between peak aging and over-aging
alloy properties were investigated. The annual average corrosion rate after peak aging
treatment is 0.01529 mm/a, which is lower than that of over-aged samples. This is because
over-aging causes more DP phases to precipitate at the grain boundary, forming a micro-
Materials 2023, 16, 444 galvanic cell with the matrix and accelerating the corrosion of the alloys. 14 of 20
5.2. Tempering
After an alloy has been prepared by processes such as casting and powder metal-
5.2. Tempering
lurgy, it isan
After often
alloysubjected
has beento quenching
prepared and tempering,
by processes such asduring
castingwhich the strengthening
and powder metallurgy,
phase is precipitated and the grains are refined. Generally,
it is often subjected to quenching and tempering, during which the strengthening the alloy is first heated
phase is to
850~830 °C in a vacuum, followed by 4 h of water quenching. The
precipitated and the grains are refined. Generally, the alloy is first heated to 850~830 C in choice of tempering
◦
atemperature
vacuum, followedis particularly
by 4 h of important. A study carried
water quenching. out by
The choice ofHu [50] explored
tempering the effects
temperature is
of tempering temperature and tempering time on the microstructure
particularly important. A study carried out by Hu [50] explored the effects of tempering and properties of the
alloy. After and
temperature the same tempering
tempering time,
time on the hardness ofand
the microstructure theproperties
alloy was of the highest
the at a tem-
alloy. After the
pering
same temperature
tempering time,of the350 °C, reaching
hardness 32 HRC
of the alloy waswith a strength
the highest of up to 900
at a tempering MPa. The
temperature
of 350 ◦ C, reaching
tempering time was32explored
HRC with at this temperature,
a strength of up toand900theMPa.hardness peaked attime
The tempering an aging
was
explored at this temperature, and the hardness peaked at an aging time of 1.5 h andto
time of 1.5 h and then decreased further with time. The increase in hardness is due the
then
decomposition of the solid solution into fine amplitude-modulated
decreased further with time. The increase in hardness is due to the decomposition of the zones, and the de-
crease
solid in hardness
solution into fineat amplitude-modulated
a later stage is due tozones,
the creation
and theofdecrease
the softinnew phase at
hardness γ a(DO
later3).
Figure
stage is 13
dueisto thetheSEM image
creation ofof the
the precipitated
soft new phasestrengthening
γ (DO3 ). Figure phase
13 isfrom γ grains.
the SEM imageThis of
wasprecipitated
the also confirmed in the study
strengthening by from
phase Congγ[51],
grains.who found
This was that
also the higher in
confirmed thethesolution
study
temperature,
by Cong [51], who the earlier
found thethatpeak of agethe
the higher strengthening. Cong alsothe
solution temperature, conducted
earlier theheat treat-
peak of
ment research on the Cu–15Ni–8Sn alloy and found that after
age strengthening. Cong also conducted heat treatment research on the Cu–15Ni–8Sn alloysolid solution and aging
treatment
and found (800 °C + 400
that after solid °Csolution
× 4 h), the
andtest alloy
aging can achieve
treatment (800 a◦ C + 400 ◦ Cof×354 HRC
hardness h), theand
testa
alloy
tensilecan achieveofa 1300
strength hardness
MPa.of 35 HRC and a tensile strength of 1300 MPa.
Figure13.
Figure 13.SEM
SEMimages
imagesof
ofthe
the precipitated
precipitatedstrengthening
strengtheningphase
phasefrom
fromγγgrains
grainsin
inthe
theaged
agedCu–Ni–Sn
Cu–Ni–Sn
[51].
alloy[51].
alloy
5.3. Heat Treatment Process of Cu–15Ni–8Sn Prepared by LPBF

LPBF is a new preparation process. As shown in Figure 14, the microstructure has
obvious
5.3. Heatdifferences from that
Treatment Process of ordinary casting,
of Cu–15Ni–8Sn Preparednamely
by LPBF that the microstructure is com-
posedLPBF
of fine
is equiaxed crystals and
a new preparation columnar
process. As crystals.
shown inThus, the14,
Figure heat
thetreatment processhas
microstructure is
different from that of an ordinary casting alloy. Moreover, the preparation of
obvious differences from that of ordinary casting, namely that the microstructure is com-Cu–15Ni–8Sn
alloys
posedbyof LPBF is still incrystals
fine equiaxed the research stage, and
and columnar there has
crystals. been
Thus, less
the research
heat intoprocess
treatment the heatis
treatment of the alloys. Due to the rapid cooling rate of the LPBF process and the low
precipitation of the alloy, a heat treatment process is required to strengthen the alloy. At
present, the heat treatment process is divided into solid solution aging and direct aging.
The DO22 and L12 ordered phases are further precipitated after aging. It is found that
after direct aging, the alloy has a higher yield strength, which is due to the retention of
the initial Sn-rich precipitation phase produced by the LPBF process when precipitation
strengthening dominates, while solid solution aging causes better plasticity, which is due
to the annealing twinning to inhibit the precipitation of DP during aging. The aging time
is generally 0.5 to 1 h, and it should not be too long. Otherwise, the layered DP begins
to nucleate and grow slowly, resulting in intergranular fracture [52]. If plasticity is not
considered, direct aging treatment is an economic and environmentally friendly method
for preparing high-strength LPBF-treated Cu–15Ni–8Sn alloys [53], which is potentially
initial Sn-rich precipitation phase produced by the LPBF process when precipitation
strengthening dominates, while solid solution aging causes better plasticity, which is due
to the annealing twinning to inhibit the precipitation of DP during aging. The aging time
is generally 0.5 to 1 h, and it should not be too long. Otherwise, the layered DP begins to
Materials 2023, 16, 444 nucleate and grow slowly, resulting in intergranular fracture [52]. If plasticity is15not con-
of 20
sidered, direct aging treatment is an economic and environmentally friendly method for
preparing high-strength LPBF-treated Cu–15Ni–8Sn alloys [53], which is potentially in-
structive for
instructive for improving
improving the mechanical properties
the mechanical propertiesofofother
other LPBF-treated
LPBF-treated precipitated
precipitated
phase-strengthened alloys.
phase-strengthened alloys.
As per
As per Wang
Wang [54],
[54], the
the LPBF
LPBF process
process shows
showspromise
promiseininthethemanufacture
manufactureofofeasily
easilyseg-
regated Cu–15Ni–8Sn
segregated Cu–15Ni–8Snalloys.
alloys.The
Thesolubility
solubilitylimit
limitof
ofthe
the solute
solute in
in the Cu–15Ni–8Snalloy
the Cu–15Ni–8Sn alloy is
issubstantially
substantiallyelevated.
elevated.InInaddition,
addition,numerous
numerousslender
slender cellular
cellular structures were observed
structures were observed in
the
in theLPBF-manufactured
LPBF-manufacturedalloy, alloy, and many
manydislocations
dislocationsandanddislocation
dislocation tangles
tangles appeared
appeared
around the precipitate dispersed between cellular structures. Thus, the LPBF-manufac-
around the precipitate dispersed between cellular structures. Thus, the LPBF-manufactured
tured Cu–15Ni–8Sn
Cu–15Ni–8Sn alloy exhibited
alloy exhibited a good combination
a good combination of strength
of strength and toughness.
and toughness.
Figure 14.Electron
Figure14. Electronbackscatter
backscatterdiffraction
diffractionimage of of
image LPBF [55].
LPBF [55].
6. Applications of Cu–Ni–Sn System Alloys
6. Applications of Cu–Ni–Sn System Alloys
As a new generation of elastic materials, Cu–Ni–Sn system alloys are widely used
in theAs a new generation
electronic of elastic
communication materials,
industry, Cu–Ni–Sn
aerospace, systemcircuits,
integrated alloys are
andwidely used in
the instru-
the electronic communication industry, aerospace, integrated circuits,
mentation industry. Where traditional copper-based elastic alloys have failed to meet and the instrumen-
tation
the industry.
various Where traditional
performance requirements, copper-based
Cu–Ni–Snelastic alloysalloys
meet have failed to
the higher meet the var-
performance
ious performance
requirements requirements,
for copper-based Cu–Ni–Sn
elastic materials:alloys
(1) meet
these the higher
alloys performance
are strong, and therequire-
size
ments
of for copper-based
the components can be elastic
reduced materials: (1) these
to save space; alloys
(2) in termsare
of strong,
the longand the size
working of the
hours
of the equipment, components made from these alloys have excellent
components can be reduced to save space; (2) in terms of the long working hours of the contact and reliable
stability;
equipment, andcomponents
(3) in different
madeworking environments,
from these alloys have the components
excellent have
contact andhigh temper-
reliable stabil-
ature resistance,
ity; and corrosion
(3) in different resistance,
working and other properties.
environments, Meanwhile,
the components due to
have high the low
temperature
production
resistance, cost, non-toxicity,
corrosion highand
resistance, thermal
otherstability,
properties.andMeanwhile,
high temperature
due tostrength,
the low these
produc-
alloys are considered as one of the substitutes for beryllium copper, with great
tion cost, non-toxicity, high thermal stability, and high temperature strength, these alloys potential in
the field of non-ferrous elastic alloys [56].
are considered as one of the substitutes for beryllium copper, with great potential in the
fieldInofthe 1970s, both
non-ferrous domestic
elastic alloysresearch
[56]. and research abroad was carried out on Cu–Ni–
Sn system alloys and a series of advances were made [43,57]. In the 1980s, a variety of
In the 1970s, both domestic research and research abroad was carried out on Cu–Ni–
Cu–Ni–Sn alloys were incorporated into production technology standards in the US, which
Sn system alloys and a series of advances were made [43,57]. In the 1980s, a variety of Cu–
greatly promoted the commercial application of the alloys. Domestic research on Cu–Ni–Sn
alloys also started earlier, and the gap between domestic research and that performed
internationally on alloy organization, mechanics, and electrical properties is not large.
There has been more research on the application of the alloys, which has promoted the
development of beryllium copper substitute materials.
Zhao [58] prepared a Cu–15Ni–8Sn alloy using the vacuum melting method. The
mechanical and physical properties of the resulting material are comparable to those of
beryllium copper, and the conductive contact reeds made by punching successfully passed
both electrical life and mechanical life tests and were introduced into industrial production
in bulk for use in the LXW5 series of microswitches. The following year, Zhao [59] prepared
a Cu–9Ni–6Sn alloy using the same method. The alloy was applied to conductive contact
reeds, and its performance also met the requirements. Moreover, an age-hardened high-
strength, high-elasticity, and corrosion-resistant deformed copper alloy was successfully
Materials 2023, 16, 444 16 of 20
prepared by Zhang [60] by multi-component alloying of copper–nickel–tin alloys, and it is

being used as a novel elastic alloy material. This Cu–Ni–Sn alloy is suitable for making
plates, strips, rods, wires, etc., for use in radio, instrumentation, electrical, and other
industries as electrically conductive pop-ups and contact reeds. This type of Cu–Ni–Sn
alloy is widely used and has obvious advantages: (1) The alloy has a high fatigue life. In
one study, it was used as a strip conductive spring and loaded into the actual instrument to
test the fatigue life. At the end of the experiment, the reed was not damaged nor fractured
and still continued to work. In addition, the spring fatigue life was several times higher
than the design requirements. (2) The alloy has a low stress relaxation rate. Compared with
beryllium copper reeds, the stress relaxation rate of both reeds is 3.5%, which meets design
requirements. (3) The alloy has a high wear life. In addition, the corrosion resistance of
this alloy was found to be slightly better than that of C72700 under the same experimental
conditions. Thus, the above results show that the new Cu–Ni–Sn alloy can partially replace
the original beryllium bronze and its precious metal composites.
Not only do Cu–Ni–Sn alloys have high elasticity and electrical conductivity, but they
also have high strength and wear and corrosion resistance. These alloys are a key basic
material for core components in the aerospace industry, heavy-duty equipment, petro-
chemicals, high-grade CNC machine tools, and robotics [61]. Compared to conventional
moderate-strength aluminum bronze, Cu–Ni–Sn is considered to be an improved bearing
alloy as it combines high strength and good tribological characteristics [62]. As a modern
bearing material, the Cu–Ni–Sn alloy has become the material of choice for bushings or
plain bearing components. In particular, Cu–15Ni–8Sn, commercially known as ToughMet
3, is an alternative or upgrade to conventional medium- to high-strength aluminum bronze
bearing alloys. Krus [63] carried out comparative evaluation tests of ToughMet 3 and
leaded tin bronze for bearing materials as well as gasket materials. In the wear experiments,
ToughMet 3 CX105 showed the lowest wear rate of 0.1 mg/h under normal lubrication
conditions, while C93200 showed the highest wear rate of 1.6 mg/h, with the surface of
the tin bronze alloy significantly darkened at the end of the experiment. Under limited
lubrication conditions, the bronze specimens showed severe distortion at the edges.
The mechanical properties of ToughMet 3 are significantly better than those of leaded
tin bronze, as shown in Table 3 [63].
Table 3. Properties of different alloys.
Materials Yield Strength (MPa) UTS (MPa) Elongation (%) Hardness (HB)
ToughMet 3
724 758 4 294
CX105
C93200 124 241 20 60
C93700 124 241 20 60
The high yield strength and oxidation resistance of ToughMet make it a candidate for
heavy equipment transmission and drive applications. Compared to leaded tin bronze
C93200 and C93700, ToughMet has similar frictional properties but is superior in resisting
surface deformation, rises in temperature, lubricant degradation, and oxide growth.
The Cu–Ni–Sn alloy can be used as a corrosion-resistant steel due to its excellent
corrosion resistance, and it greatly improves the corrosion resistance of hull steel in a
strongly acidic chloride environment. Cu is an effective element for improving the corrosion
resistance of steel. Its main mechanism is enrichment on the surface of steel in the form
of redeposited particles, which passivate the steel matrix, reduce the solubility of steel,
and inhibit the nucleation of pitting corrosion. The corrosion resistance of the steel will
be further enhanced by Sn. The main mechanism of action is the formation of a dense
protective film of corrosion products on the surface of the steel, which effectively prevents
any interaction between the substrate and the corrosive medium and inhibits the corrosion
of the steel in the medium [64].
Materials 2023, 16, 444 17 of 20
7. Summary
In this section, a preliminary summary of the Cu–Ni–Sn alloy is presented in terms of
preparation processes, strengthening mechanisms, etc. The conclusions are as follows:
(1) As a copper-based highly elastic conductive alloy, it can be used in precision instru-
mentation and the electrical industry to prepare various elastic components, such as
electronic connectors, springs, bearings, and bushings. In terms of preparation pro-
cesses, although element segregation is caused by continuous casting, a large amount
of segregation can be eliminated through continuous casting modifications, for ex-
ample, by the incorporation of electromagnetic stirring technology or by subsequent
heat treatment. At present, continuous casting is still an economical and effective
preparation process. In addition, powder metallurgy is a good preparation process
and can be applied in production. LPBF technology is still in the experimental stage
currently. However, whereas mechanistic studies are less transparent and difficult
to apply in practice due to excessive costs and the absence of systematic process
parameters, LPBF technology has shown its potential;
(2) The factors affecting the properties of Cu–15Ni–8Sn alloys are grain size, distribution,
and the size of the second phase, in addition to the main factor, i.e., the precipitation
of the DP phase. This is a brittle phase, and the mechanical properties and corrosion
resistance of the alloy will be negatively affected, especially at the grain boundary.
Grains can be refined, and the precipitation of the DP phase can be suppressed by
adding alloying elements such as V, Ti, and Co. Various elements have different
mechanisms of action, and some elements can also promote the precipitation of
the fine dispersed second phase, further enhancing the mechanical properties of
the alloy. However, there are obvious deficiencies in the research on microalloying
of B, Zr, Mn, and other elements, and there is a lack of systematic analysis and
detailed discussion, which is worthy of further discussion in follow-up research.
The purpose of heat treatment is to minimize the precipitation of the discontinuous
DP phase, but some heat treatment methods have the opposite effect. Therefore, to
improve the overall performance of the alloy, it is necessary to match the alloy with
its application environment;
(3) It can be seen from this review that Cu–Ni–Sn alloys have good mechanical properties,
with a tensile strength of up to 1300 MPa. Thus, they can be called ultra-high-strength
alloys. Therefore, these alloys have a wide range of applications, which will bring
more challenges for the alloys to overcome. For example, the requirements of coastal
areas or marine engineering regarding the corrosion resistance of alloys are strict and
the economic loss caused by corrosion is also large. However, there is little research on
the corrosion resistance of the alloys, especially those prepared by LPBF technology.
Therefore, a concerted effort is required to fill this gap in the studies of corrosion
resistance mechanisms of alloys.
Author Contributions: All authors conceived the research idea and the framework of this study. L.G.
prepared the final draft, P.Z. prepared the first part, Z.Z. prepared the second part, Q.Z. and M.Z.
prepared the third part, X.H. collected and sorted out papers related to the theme of the article, J.W.
analyzed the structure of the article, and B.Z. edited and modified the article. All authors have read
and agreed to the published version of the manuscript.
Funding: This work was supported by the National Natural Science Foundation of China (Grant
No. 51901018), Young Elite Scientists Sponsorship Program by China Association for Science and
Technology (YESS, 2019QNRC001), the Fundamental Research Funds for the Central Universities
(Grant No. FRF-AT-20-07, 06500119), the Natural Science Foundation of Beijing Municipality (Grant
No. 2212037), and the National Science and Technology Resources Investigation Program of China
(Grant No. 2019FY101400).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Materials 2023, 16, 444 18 of 20
Data Availability Statement: Not applicable.

Conflicts of Interest: The authors declare that there are no conflict of interest.
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materials

Keywords: Cu–Ni–Sn; alloy; processing; microstructure; property

Materials 2023, 16, 444. https://doi.org/10.3390/ma16010444 https://www.mdpi.com/journal/materials

Figure 2. Cu–Ni–Sn ternary phase diagram (Ni fixed at 15 wt%) [12].

3.2. Powder Metallurgy

3.3. Plasma Spraying

Materials 2023, 16, 444 6 of 20

3.5. Vacuum Melting Process

Preparation Process Advantages Disadvantages

4. Effect of Alloying Elements on Tissue Properties

Materials 2023, 16, 444 4.1. Si 8 of 20

(a) (b) (c)

Table 2. Effect of alloy elements on microstructure and properties.

Element Strengthening Phase Strengthening Mechanism Mechanical Properties

5. Effect of Plastic Deformation and Heat Treatment on the Microstructure and

5.1. Plastic Deformation

The variations in yield strength versus ◦ C [45].

Good corrosion resistance is another property of Cu–15Ni–8Sn, and it is also of great

5.3. Heat Treatment Process of Cu–15Ni–8Sn Prepared by LPBF

prepared by Zhang [60] by multi-component alloying of copper–nickel–tin alloys, and it is

Data Availability Statement: Not applicable.

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