Metals: Strengthening Mechanisms in Nickel-Copper Alloys: A Review

metals
Review
Strengthening Mechanisms in Nickel-Copper Alloys:
A Review
Olexandra Marenych and Andrii Kostryzhev *
School of Mechanical, Materials, Mechatronic and Biomedical Engineering, University of Wollongong,
Wollongong, NSW 2500, Australia; om753@uowmail.edu.au
* Correspondence: andrii@uow.edu.au; Tel.: +61-02-4221-3034

Received: 2 September 2020; Accepted: 30 September 2020; Published: 12 October 2020
Abstract: Nickel-Copper (Ni-Cu) alloys exhibit simultaneously high strength and toughness, excellent
corrosion resistance, and may show good wear resistance. Therefore, they are widely used in the
chemical, oil, and marine industries for manufacturing of various components of equipment, such as:
drill collars, pumps, valves, impellers, fixtures, pipes, and, particularly, propeller shafts of marine
vessels. Processing technology includes bar forging, plate and tube rolling, wire drawing followed
by heat treatment (for certain alloy compositions). Growing demand for properties improvement
at a reduced cost initiate developments of new alloy chemistries and processing technologies,
which require a revision of the microstructure-properties relationship. This work is dedicate to
analysis of publicly available data for the microstructure, mechanical properties and strengthening
mechanisms in Ni-Cu alloys. The effects of composition (Ti, Al, Mn, Cr, Mo, Co contents) and heat
treatment on grain refinement, solid solution, precipitation strengthening, and work hardening
are discussed.
Keywords: Ni-Cu alloys; microstructure characterisation; mechanical properties; strengthening

mechanisms
1. Introduction
The Ni-Cu system forms the basis for the Monel alloy family (Table 1). Monel was discovered
by Robert Crooks Stanley who was employed by the International Nickel Company (INCO) in 1901.
The new alloy was named in honour of the company president, Ambrose Monell. The name is now a
trademark of Special Metals Corporation [1].
Table 1. Chemical compositions of Monel alloys (wt.%).
Monel Alloys Ni Cu C Mn Fe Co S Si Al Ti
Max - 34.0 0.3 2.0 2.5 - 0.024 0.5 - -
Monel 400
Min 63.0 28.0 - - - - - - - -
Max 45.0 Balance 0.1 2.25 0.75 0.25 0.015 0.25 - -
Monel 401
Min 40.0 - - - - - - - - -
Max 57.0 Balance 0.15 0.1 0.5 - 0.024 0.1 0.05 -
Monel 404
Min 52.0 - - - - - - - - -
Max - 34.0 0.3 2.0 2.5 - 0.060 0.5 - -
Monel R405
Min 63.0 28.0 - - - - 0.025 - - -
Max - 33.0 0.18 1.5 2.0 0.25 0.006 0.5 3.15 0.85
Monel K500
Min 63.0 27.0 - - - - - - 2.3 0.35
Ni and Cu exhibit very similar atomic characteristics. They both have face centred cubic (fcc) crystal
structure type, less than three percent difference in atomic radii, and exhibit similar electronegativity
Metals 2020, 10, 1358; doi:10.3390/met10101358 www.mdpi.com/journal/metals

Metals 2020, 10, 1358 2 of 18
and valence state. The Ni-Cu system has complete solid solubility, which allows production of single
phase alloys over the entire composition range [2]. Although the Ni-Cu system exhibits complete solid
solubility [3], the large differences in melting points between Ni (1455 ◦ C) and Cu (1085 ◦ C) can result in
Cu segregation. Following equilibrium solidification at slow cooling rates, dendrites become enriched
in Ni and interdendritic regions get enriched in Cu [4–6]. However, with an increase in cooling rate
during solidification the compositional gradient decreases and the microstructure morphology changes
from dendritic to cellular [7]. Higher undercoolings during solidification also lead to finer and more
equiaxed grain sizes after annealing [8].
Monel alloys can be easily fabricated by hot and cold metal forming processes and
machining. Recrystallisation studies determined the optimum hot deformation temperatures to be
950–1150 ◦ C [9,10], which are quite similar to other Ni-base alloys and steels. However, heat treatment
schedule requires rigorous development: usually a two-step age-hardening heat treatment in the
temperature range of 650–480 ◦ C is used for Ni-Cu alloys [11,12]. The higher temperature stage helps
to quickly nucleate precipitates of alloying elements, and the lower temperature stage provides a
superior distribution of higher number density of smaller-sized particles. Ni-Cu alloys are usually quite
weldable to each other and to other Ni alloys and stainless steels [13,14]. Lower heat inputs produce
finer grain microstructures with random texture and higher strength and ductility [15]. Monel alloys are
expensive, with their cost reaching up to 3 times that of Ni and 7 times that of Cu [16–18]. Hence their
use is limited to those applications where they cannot be replaced with a cheaper alternative.
Major additions of copper (28–40 wt.%) improve corrosion resistance of Ni in many agents,
in particular nonoxidizing acids, nonaerated sulphuric and hydrofluoric acids [19–21]. This determines
areas of application of Ni-Cu alloys. They are widely used for manufacturing various components of
equipment in chemical, oil and marine industries (such as drill collars, pumps, valves, fixtures, piping,
fasteners, screws, propeller shafts, steam generators, turbines [22–27]), for protective coating [28,29],
for manufacturing electrical and electronic equipment (resistors, bimetal contacts, capsules for
transistors and ceramic-to-metal sealing [30,31]), and in fuel cells [32,33].
2. Role of Alloying Elements

Ni can dissolve high concentrations of alloying elements compared to other metals [34]. Alloying
elements increase mechanical strength via solid solution [35–40] or precipitation strengthening [41–45].
However, the solid solution strengthening effect of Cu is much lower compared to other elements [19,46].
For example, in recently developed nanocrystalline Ni-Cu alloys both strength and ductility increased
with Cu content by only 40% for Cu concentrations increasing by 5 times (from 6 to 32 wt.%) [47].
This was associated with grain refinement and solid solution strengthening. Work hardening also
increased with Cu content, as the stacking fault energy decreased, leading to increased dislocation
densities and twinning. Due to the substantial increase in strength-to-weight ratio, achieved by
precipitation hardening, the weight of turbine engines was significantly reduced, which enhanced
development of the aerospace industry [22]. Although Ti and Al provide some solid solution
strengthening effect, they typically improve strength by precipitation of γ0 -Ni3 (Ti,Al) particles during
heat treatment [19,48]. Aluminium (2.3–3.15%) provides excellent corrosion resistance resulting from
the formation of a protective Al2 O3 surface oxide layer. Titanium (0.35–0.85%) forms TiC carbides [49].
Together Al and Ti are often used in minor amounts to increase corrosion resistance via deoxidation [20].
They both combine with oxygen to form oxides, thus controlling porosity in welds [2]. Carbon
(<0.25 wt.%) is required for carbide formation, which not only increase strength at room temperature
but also creep resistance [50]. Manganese (<1.5%) improves corrosion resistance and weldability,
promotes formation of M23 C6 type carbides [3,51]. Iron (<2.0%) provides solid solution strengthening
at reduced costs, but may be detrimental for corrosion resistance [20]. Fe also increases the solubility of
C in Ni; this improves resistance to high-temperature carburizing environments [19]. Cobalt (<0.25%)
increases high-temperature strength via solid solution strengthening, and resistance to carburization
and sulphidation [20]. Additions of Co also raise solvus temperature of γ0 phase [19]. Sulphur
Metals 2020, 10, 1358 3 of 18
Metals 2020, 10, x FOR PEER REVIEW 3 of 19
raise solvus
(<0.006%) temperature
enhances of γ′ phase
machinability [52].[19]. Sulphur
Silicon (<0.006%)
(<0.5%) enhances
is typically machinability
present [52].
only in minor Silicon
amounts
(<0.5%)
as is typically
a residual elementpresent only in minor
from deoxidation or amounts as a residual
as an intentional element
addition from deoxidation
to promote or as an
high-temperature
intentional
oxidation addition[19].
resistance to promote high-temperature oxidation resistance [19].
3.
3. Microstructure
Microstructure
Ni-Cu
Ni-Cu alloys
alloys have
have fcc
fcc matrix
matrix (γ)
(γ) with
with aa lattice
lattice parameter
parameter ofof 0.3534
0.3534 nm nm [53].
[53]. Due
Due toto full
full mutual
mutual
solubility
solubility of
of Ni
Ni and
and Cu,
Cu, the
the second
second phase
phase does
does not
not form
form (Figure
(Figure 1),
1), although
although particles
particles ofof various
various
chemistries
chemistries can precipitate.
precipitate.Therefore,
Therefore,in in
thisthis alloy
alloy strengthening
strengthening occursoccurs via mechanisms:
via four four mechanisms: grain
grain refinement,
refinement, solid solution,
solid solution, precipitation
precipitation and dislocation
and dislocation strengthening
strengthening (work (work hardening).
hardening). Grain
Grain refinement
refinement is achieved
is achieved as a as a result
result of recrystallization
of recrystallization during
during hothotdeformation
deformationin the 870–1150 ◦°C
in the C
temperature range [54]. A required level of precipitation strengthening is usually obtained
temperature range [54]. A required level of precipitation strengthening is usually obtained after age after age
hardening
hardening heat
heat treatment.
treatment. Dislocation
Dislocation strengthening
strengthening follows
followscold
coldrolling
rollingor ordrawing
drawing[55–57].
[55–57].
Figure 1.
Figure 1. Typical
Typicalmicrostructure
microstructureofofMonel
MonelK500
K500rod
rodinin
(a)(a)
hothot rolled
rolled and
and (b)(b) annealed
annealed at 1100
at 1100 C for
◦ C for 15
15 min
min conditions
conditions (the(the authors’
authors’ unpublished
unpublished data).
data).
After
Afterananappropriate
appropriate heatheat
treatment, the following
treatment, intermetallic
the following particlesparticles
intermetallic can precipitate: Ni3 (AlX),
can precipitate:
Ni Ti, and NiFe (AlFe) [49,58]. Ni
Ni33(AlX), Ni3Ti,3and NiFe3(AlFe) [49,58]. 3 (Al,X) particles, where X can be Cu, Mn, Ti, or Si, are
Ni3(Al,X) particles, where X can be Cu, Mn, Ti, or Si, are known as
gamma
known as prime
gamma precipitates (γ’). Gamma
prime precipitates (γ’).prime
Gamma (γ’)prime
particles(γ’)have an ordered
particles have anfcc crystal fcc
ordered structure
crystal
(Figure
structure2a)(Figure
with close crystallographic
2a) with matchingmatching
close crystallographic to the Ni to fccthe
matrix
Ni fcc(<1% mismatch)
matrix [59]. The[59].
(<1% mismatch) Al
atoms
The Aloccupy the cube
atoms occupy thecorners while the
cube corners whileNithe
ones
Nireside on theonface
ones reside thecentres. In Ni-Cr-Fe
face centres. alloys
In Ni-Cr-Fe Co
alloys
and Fe can
Co and substitute
Fe can substituteNi Ni
[60], while
[60], Cu,Cu,
while Mn, Mn,and
andSi Si
tend
tendtotosubstitute
substituteAl.Al.Gamma
Gammaprime primeparticles
particles
homogeneously
homogeneously nucleate
nucleate through
through thethe volume,
volume, and and maintain
maintain spherical
spherical shape
shape and
and coherency
coherency withwith the
the
Ni
Ni matrix
matrix even
even after
after many
many hours
hours ofof aging
aging (Figure
(Figure 3).
3). The
The precipitates
precipitates do do not
not show
show anyany tendency
tendency forfor
alignment
alignmentor ornucleation
nucleationat atdislocations.
dislocations. Close
Close crystallographic
crystallographicmatching
matchingbetween
betweenthe theγγmatrix
matrixandandγγ′0
precipitates
precipitatesleads
leadsto to
a very low surface
a very energyenergy
low surface that, consequently, results inresults
that, consequently, very lowin particle
very low coarsening
particle
rates and increased
coarsening rates andnumber density
increased of fine density
number particlesof[61]. The
fine coarsening
particles [61].process is controlled
The coarsening by bulk
process is
diffusion
controlled of by
thebulk
γ’-forming elements.
diffusion of the The activation
γ’-forming energy ofThe
elements. theactivation
coarseningenergy
processofis the
closecoarsening
to that of
diffusion
process isofclose
Al intoNi.
thatThe
of average
diffusionγ’ofparticle
Al in Ni.radius
The remains
average proportional to theremains
γ’ particle radius cube root of ageing
proportional
time. ◦ C [49].
to theThe
cubevolume
root offraction of precipitates
ageing time. The volume canfraction
reach 6–7% after agingcan
of precipitates at 700
reach 6–7% after aging at 700
The Ni-Al and Ni-Ti phase diagrams (Figure 4) can help to analyse precipitation in Ni-base
°C [49].
alloys [62]. Most Ni-base alloys contain below 10 wt.% of (Al + Ti). However, even minor additions
of Al or Ti result in precipitation of Ni3 Al or Ni3 Ti particles. The γ’ solvus temperature is ranging
between 700 and 750 ◦ C for the solution treated and quenched alloys [49]. Therefore, the solution
annealing temperature is usually above 950 ◦ C. The solubility temperature of γ’ particles in Monel
is relatively lower compared with those in high temperature precipitation strengthened Ni-base
superalloys. This is associated with much lower Al and Ti contents in Monel K500 compared to
Al, Ti, Nb, and Ta concentrations in other Ni-base alloys [63]. Decomposition of the supersaturated
austenite may not occur during quenching, meaning that even very fine nano-scale particles do
not precipitate [49]. This is contrarily to other Ni-Al and Ni-Ti alloys, where γ’ forms readily on
Metals 2020, 10, 1358 4 of 18
quenching [64,65]. The substitution of some neighbouring elements in the periodic table (Cr, Fe,
and Co) for Ni in alloy composition is known to decrease γ’ solubility and increase the γ’-particle
volume fraction even for the same Al + Ti contents [66]. Precipitation of γ’ in Monel K500 at 750 ◦ C,
while the solubility of Al in Ni at this temperature is quite high and is reaching 5 wt.% in binary
Ni-A1 system, suggests that Cu also decreases the solubility of γ’ [67]. The γ0 precipitation provides
significant strengthening effect with temperatures increasing up to ~800 ◦ C [68]. This is believed to
occur due to ordering in the particle lattice and the relatively low mobility of super lattice dislocations
that
Metalsoccurs with
2020, 10, increasing
x FOR temperature.
PEER REVIEW 4 of 19
Figure 2. (a) Ordered face centred cubic (fcc) crystal structure of a γ′-Ni03(Ti,Al) particle and (b) TiC
Figure
Figure 2. (a)Ordered
2. (a) Orderedface
facecentred
centredcubic
cubic(fcc)
(fcc) crystal
crystal structure
structure of of a γ -Ni
a γ′-Ni 3 (Ti,Al)
3(Ti,Al) particle
particle and and (b)
(b) TiC
particle.
TiC particle.
particle.
Figure
Figure 3. TEM
TEM dark field images
images illustrating
illustratingthe
thehomogeneous
homogeneousdistribution
distributionandandthethe spherical
spherical shape
shape of
Figure 3. TEM dark field images illustrating the homogeneous distribution and the spherical shape
of γ0 γ′
thethe precipitates
precipitates retained
retained even
even after
after prolonged
prolonged aging
aging at◦700
at 700 °C(a)
C for for64(a)
h, 64
(b)h, (b)h,128
128 andh,(c)and (c)h1000
1000 [49].
of the10,
Metalsh2020,
γ′ precipitates retained even after prolonged aging at 700 °C for (a) 64 h, (b) 128 h, and (c) 10005 of 19
[49]. x FOR PEER REVIEW
h [49].
of Al or Ti result in precipitation of Ni3Al or Ni3Ti particles. The γ’ solvus temperature is ranging
of Al or Ti result in precipitation of Ni3Al or Ni3Ti particles. The γ’ solvus temperature is ranging
between 700 and 750 °C for the solution treated and quenched alloys [49]. Therefore, the solution
between 700 and 750 °C for the solution treated and quenched alloys [49]. Therefore, the solution
annealing temperature is usually above 950 °C. The solubility temperature of γ’ particles in Monel is
annealing temperature is usually above 950 °C. The solubility temperature of γ’ particles in Monel is
relatively lower compared with those in high temperature precipitation strengthened Ni-base
relatively lower compared with those in high temperature precipitation strengthened Ni-base
superalloys. This is associated with much lower Al and Ti contents in Monel K500 compared to Al,
superalloys. This is associated with much lower Al and Ti contents in Monel K500 compared to Al,
Ti, Nb, and Ta concentrations in other Ni-base alloys [63]. Decomposition of the supersaturated
Ti, Nb, and Ta concentrations in other Ni-base alloys [63]. Decomposition of the supersaturated
austenite may not occur during quenching, meaning that even very fine nano-scale particles do not
austenite may not occur during quenching, meaning that even very fine nano-scale particles do not
precipitate [49]. This is contrarily to other Ni-Al and Ni-Ti alloys, where γ’ forms readily on
precipitate [49]. This is contrarily to other Ni-Al and Ni-Ti alloys, where γ’ forms readily on
quenching [64,65]. The substitution of some neighbouring elements in the periodic table (Cr, Fe, and
quenching [64,65]. The substitution of some neighbouring elements in the periodic table (Cr, Fe, and
Co) for Ni in alloy composition is known to decrease γ’ solubility and increase the γ’-particle volume
Co) for Ni in alloy composition is known to decrease γ’ solubility and increase the γ’-particle volume
fraction even for the same Al +4.Ti
Figure
contents
Binary
[66].and
(a) Ni-Al
Ni-Al
Precipitation
(b) Ni-Ti
of γ’diagrams
Ni-Ti phase
in Monel[62].K500 at 750 °C, while the
fraction even for the same Al 4.
Figure + Ti contents
Binary (a) [66].and
Precipitation
(b) of γ’diagrams
phase in Monel K500 at 750 °C, while the
[62].
solubility of Al in Ni at this temperature is quite high and is reaching 5 wt.% in binary Ni-A1 system,
solubility of Al in Ni at this temperature is quite high and is reaching 5 wt.% in binary Ni-A1 system,
suggests that
The Ni TiCu
33Ti also designated
phase, decreases the as etasolubility of γ’stoichiometric
(η), exhibits [67]. The γ′ precipitation
composition provides
of 75 at.%significant
Ni-25 at.%
The Ni
suggests that phase,
Cu alsodesignated
decreases as theeta (η), exhibits
solubility of γ’stoichiometric composition of
[67]. The γ′ precipitation 75 at.% Ni-25
provides at.%
significant
strengthening
Ti and a stableeffect with temperatures
hexagonal closed packed increasing up to ~800
crystal structure. °C [68]. This
Although is believed
the η-Ni to occur
33Ti particles may
Ti particles due to
have
Ti and a stable hexagonal closed packed crystal structure. Although the η-Ni
strengthening effect with temperatures increasing up to ~800 °C [68]. This is believed to occur due to may have
ordering
ordered in the particle
metastable fcc lattice and
structure at the
lowerrelatively low mobility
temperatures. Ti of super
additions lattice formation
promote dislocations of that
the occurs
η-Ni Ti
ordered
orderingmetastable fcc lattice
in the particle structure
andat thelower temperatures.
relatively low mobility
0
Ti additions promote
of super lattice formationthat
dislocations the3η-
of occurs
with
phase,increasing
while Al temperature.
additions promote formation of the γof -Ni 3 Alγ′-Ni
phase. The hexagonal η-Ni3 Ti usually
Ni 3Tiincreasing
with phase, while Al additions
temperature. promote formation the 3Al phase. The hexagonal η-Ni3Ti
usually appears as coarse disk-shaped particles of low number density that does not provide
reasonable strengthening. Thus, fine γ′-Ni3Al particles of high number density are preferred [68].
Appreciable C levels, 0.18 wt.% in Monel K500, result in precipitation of carbides. Carbides
composition, size, and number density depend on the alloy composition and processing history, and
may vary in service [2]. The Ti-rich MC carbide is the main carbide phase in Monel K500, (Figure 2b).
Metals 2020, 10, 1358 5 of 18
appears as coarse disk-shaped particles of low number density that does not provide reasonable
strengthening. Thus, fine γ0 -Ni3 Al particles of high number density are preferred [68].
Appreciable C levels, 0.18 wt.% in Monel K500, result in precipitation of carbides. Carbides
composition, size, and number density depend on the alloy composition and processing history,
and may vary in service [2]. The Ti-rich MC carbide is the main carbide phase in Monel K500,
(Figure 2b). Coarse TiC particles randomly precipitate within the grains or along the grain boundaries
(Figure 5) [69]. They possess the fcc crystal structure and usually form at the end of solidification by the
eutectic-type reaction [70]. The morphology and distribution of TiC do not change with heat treatment
below 980 ◦ C. However, these particles may slightly grow during heat treatment [69]. TiC do not easily
dissolve during re-heating for metal forming operations and, thus, may appear as stringers along the
rolling direction. The MC carbides can often be replaced by M23 C6 carbides during thermomechanical
processing or high temperature service [48]. Due to absence of Cr, the M23 C6 carbides in Monel K500 are
generally Mn rich and precipitate in the temperature range of 760–980 ◦ C. These carbides preferentially
form on grain boundaries and, thus, can improve creep resistance via restricting grain boundary
migration (Figure 5c). Presence of carbides retards recrystallization, refines grain size, and improves
the high temperature strength and ductility. However, the carbides type and morphology should be
carefully controlled to avoid fracture initiation at the particle-matrix interface during a component
manufacturing or in service [71]. The MCN carbonitrides are similar to MC carbides in morphology
and crystallography, except that substantial levels of C are substituted by N. The eutectic-type reactions
leading to formation of carbides and carbonitrides are facilitated by the strong tendency of C, N,
and Ti to segregate to the liquid during solidification. As a result, carbonitrides may precipitate in the
interdendritic regions and grain boundaries [71,72]. Recent studies of boron addition to Monel 400
showed a possibility to increase hardness by 4 times (from 200 HV to 800 HV) and wear resistance by
60% following precipitation of Ni borides [73,74].
Figure
Figure 5. precipitation: (a)
5. Particle precipitation: (a) TiC
TiC within
within the
the grains,
grains, (b)
(b) TiC at the grain boundaries, and (c)
M
M23 C66-type
23C -typecarbides
carbides
at at
thethe grain
grain boundaries
boundaries [69].[69].
AA moderate
moderate density
density of
of dislocations
dislocations havehave been
been observed
observed in in Monel
Monel K500K500 thin
thin (0.2
(0.2 mm)
mm) sheets
sheets that
that
were solution annealed, aged, and water quenched [49]. It was proposed that
were solution annealed, aged, and water quenched [49]. It was proposed that the dislocations were the dislocations were
formed
formed following
following micro-deformations
micro-deformations under under the
the quenching
quenching stresses.
stresses. These
These dislocations
dislocations of of moderate
moderate
density
density did not exhibit any distribution pattern in the form of planar arrays or pairing. This suggests
did not exhibit any distribution pattern in the form of planar arrays or pairing. This suggests
aa quite
quite high
high level
level of
of stacking
stacking fault
fault energy
energy of of the
the alloy
alloy and
and absence
absence of of short-range
short-range ordering
ordering inin the
the
solution-annealed and quenched material. The arrangement of dislocations
solution-annealed and quenched material. The arrangement of dislocations in the solution-treated in the solution-treated
and
and deformed
deformed (3% (3% strain)
strain) specimens
specimens was was found
found to to be
be nonplanar
nonplanar in in several
several regions
regions ofof the
the grains
grains
(Figure 6a) [49]. Although the stacking fault energy of Ni alloys is high [75], alloying
(Figure 6a) [49]. Although the stacking fault energy of Ni alloys is high [75], alloying may decrease may decrease this
value, as has
this value, as been observed,
has been for example,
observed, in many
for example, in manyNi-Cr-base
Ni-Cr-base alloys [76].[76].
alloys However,
However, CuCuadditions to
additions
Ni do not reduce the stacking fault energy of the alloy [77,78]. The concentrations
to Ni do not reduce the stacking fault energy of the alloy [77,78]. The concentrations of other alloying of other alloying
elements
elements ininMonel
MonelK500K500are
aretoo
toolow
lowto to
substantially
substantially reduce
reducethethestacking faultfault
stacking energy of the
energy ofmatrix [49].
the matrix
Therefore, deformation
[49]. Therefore, twins are
deformation usually
twins are not observed.
usually However,However,
not observed. annealing annealing
twins do formtwins(Figure 6b).
do form
Annealing twins in Monel K500 are prevalent in solution annealed, water quenched,
(Figure 6b). Annealing twins in Monel K500 are prevalent in solution annealed, water quenched, air- air-cooled, or aged
material
cooled, or[49,72]. The solution
aged material annealed
[49,72]. alloy annealed
The solution was found to contain
alloy was found a moderate
to contain density of annealing
a moderate density
twins, which usually appeared as parallel bands bounded by coherent (111)
of annealing twins, which usually appeared as parallel bands bounded by coherent (111) planes. planes.
to Ni do not reduce the stacking fault energy of the alloy [77,78]. The concentrations of other alloying
elements in Monel K500 are too low to substantially reduce the stacking fault energy of the matrix
[49]. Therefore, deformation twins are usually not observed. However, annealing twins do form
(Figure 6b). Annealing twins in Monel K500 are prevalent in solution annealed, water quenched, air-
cooled,
Metals or10,
2020, aged
1358material [49,72]. The solution annealed alloy was found to contain a moderate density
6 of 18
of annealing twins, which usually appeared as parallel bands bounded by coherent (111) planes.
Figure 6.
Figure 6. (a) Non-planar dislocation arrangement in a slightly deformed (3% strain) sample [49] and
(b) annealing
(b) annealing twins
twins in
in the
the fully
fully annealed
annealed Monel
Monel K500
K500 [69].
[69].
4. Strengthening Mechanisms
4. Strengthening Mechanisms
As Monel K500
As Monel K500isisa asingle
single phase
phase alloy,
alloy, fourfour strengthening
strengthening mechanisms
mechanisms operate
operate in it:
in it: grain
grain refinement,
refinement, solid solution,
solid solution, precipitation,
precipitation, and dislocation
and dislocation strengthening
strengthening (work hardening).
(work hardening). Depending
Depending on the microalloying element content (in particular, Ti, Al, Co, Fe) and
on the microalloying element content (in particular, Ti, Al, Co, Fe) and processing schedule processing
(age
schedule (age hardening heat treatment), either the solid solution strengthening or precipitation
hardening heat treatment), either the solid solution strengthening or precipitation strengthening
strengthening
dominates. dominates.
4.1. Grain Refinement

4.1. Grain Refinement
Figure
Figure 7a7a shows
shows anan example
example ofof grain
grain size
size strengthening
strengthening in in Monel
Monel 400. With an
400. With an increase
increase in
in grain
grain
size
size from
from 9.5
9.5x to
to 202
202 µm the
the stress-strain
µ mREVIEWstress-strain curve
curve moves
moves downwards
downwards along along the
the stress
stress axis
axis and
and the
the7yield
yield
Metals 2020, 10, FOR PEER of 19
stress
stress value
value decreases
decreases from
from about
about 290
290 to
to 130
130 MPa. However, this
MPa. However, this variation
variation in in grain
grain size
size did not affect
did not affect
the
the work-hardening
parallel. Independence
work-hardening behaviour,
of work i.e.,
behaviour, thethe
hardening
i.e., stress-strain curves
rate on grain
stress-strain wasforobserved
curves allfor
theall
grain sizes
grainare
in other
the fcc essentially
metals,
sizes parallel.
are especially
essentially
at low initial dislocation densities, when a possible dislocation accumulation at grain boundariesatdoes
Independence of work hardening rate on grain was observed in other fcc metals, especially low
initial dislocation densities, when a possible dislocation accumulation at grain boundaries
not restrict the dislocation motion in the grain interior [79]. With strain rate increasing from the quasi- does not
restrict
static tothe dislocation
dynamic, motion in thecurves
the stress-strain grain interior
move up [79]. With
along strain
the stress rate increasing
axis (Figure from
7b); athe quasi-static
similar trend
to dynamic, the stress-strain curves move up along the stress axis (Figure
was observed in other fcc materials [80]. However, the effect of strain rate on the stress-strain 7b); a similar trend was
curve
observed in other fcc materials [80]. However, the effect of strain rate on the
dependence on grain size is weak: the work hardening rate at a high strain rates remains invariant of stress-strain curve
dependence
grain size [81].on grain size is weak: the work hardening rate at a high strain rates remains invariant of
grain size [81].
Figure 7. The stress-strain curves of Monel 400 for various grain sizes at (a) low and (b) high strain
rates [81].
Figure 7. The stress-strain curves of Monel 400 for various grain sizes at (a) low and (b) high strain
rates [81].
4.2. Solid Solution Strengthening

The solid solution strengthening effect is known to increase with the atomic size difference
between the primary element and a solute. Addition of the substitutional alloying elements results
in expansion of the fcc lattice leading to strengthening [46,82]. Table 2 summarizes approximate
atomic diameter variations between Ni and some other elements and solubility data for these
Metals 2020, 10, 1358 7 of 18
4.2. Solid Solution Strengthening

The solid solution strengthening effect is known to increase with the atomic size difference between
the primary element and a solute. Addition of the substitutional alloying elements results in expansion
of the fcc lattice leading to strengthening [46,82]. Table 2 summarizes approximate atomic diameter
variations between Ni and some other elements and solubility data for these elements in Ni at 1000 ◦ C.
As can be seen, Ta, W, Mo, Ti, V, Cr, and Mn provide the best combination of atomic radii mismatch
and appreciable solubility needed for solid solution strengthening. Therefore, Mo, Ti, Cr, and Mn are
frequently used in many single phase Ni-base alloys for solid solution strengthening. Fe, Co and Cu also
can be used for solid solution strengthening due to their high solubility in Ni [83]. The solid solution
strengthening from additions of these elements will be effective only if the element concentrations
do not exceed their solubility limits in Ni-based austenite, otherwise particle precipitation will take
place. Although Ti, Al, and Nb can be effective solid solution strengtheners, they typically improve
strength via precipitation of γ0 -Ni3 (Ti,Al) or Ni3 Nb intermetallic particles, or carbides [2]. In addition
to the atomic size misfit, electron configuration [84], diffusion coefficients [39], and γ-γ0 lattice misfit
(dependent on element partitioning between γ-matrix and γ0 -particles) [85] were shown to influence
the solid solution strengthening at high temperatures. Thus, slow diffusing elements Re, Os, Ir, Tc, Ru,
and W provide the best high temperature strength and creep resistance.
Table 2. Approximate atomic size variations and solubility limits of some elements in Ni.
Approximate Atomic Size Approximate Solubility in Ni at

Element
Difference Compared to Ni, % 1000 ◦ C, wt.% [34]
Ta −51 14
W −44 38
Mo −41 34
Ti −27 10
V −22 20
Cr −17 40
Mn −12 20
Nb −49 6
Al 31 7
Si 38 8
C 82 0.2
Fe −9 100
Co −3 100
Cu 4 100
4.3. Precipitation Strengthening

In Monel K500 significant hardening is associated with the precipitation of gamma prime (γ’)
particles. The γ’ precipitates have an ordered fcc crystal structure; therefore, the dislocation interaction
mechanisms with the ordered precipitates dictate the level of strengthening. Initially, the particles
nucleate and grow at a relatively short distance from each other. In this case of small interparticle
spacing the particle shearing mechanism prevails. With coarsening, as the interparticle spacing
increases, dislocation looping between the particles starts dominating. When precipitate shearing
occurs, the strengthening of an alloy can arise from the (a) lattice mismatch between particles and
the matrix, (b) order hardening, and (c) modulus mismatch. In Monel K500, the order hardening
prevails over other shearing mechanisms. The lattice mismatch contribution to the total precipitation
strengthening effect is small, because the coherency strain value is extremely small (less than 0.003) [69].
The precipitation strengthening mechanism may change with aging, due to the precipitate size variation
with aging. In the under-aged and peak-aged condition, precipitation strengthening is governed
predominantly by the particle shearing. This is associated with a lower shear stress required for particle
shearing compared to the Orowan stress arising during looping of dislocations around precipitates [86].
Metals 2020, 10, 1358 8 of 18
In the overaged condition, two processes may operate simultaneously or one after another: (i) shearing
in slightly overaged conditions and (ii) looping in significantly overaged conditions. When a dislocation
pair approaches a particle surrounded by a loop, the first dislocation is blocked by this dislocation loop.
The second dislocation approaching the first increases the shear stress between the first dislocation and
the loop. Consequently, the particle shearing (accompanied by the loop annihilation) occurs even when
the looping mechanism dominates. Thus, planar slip may be observed in an alloy containing slightly
overaged γ’ particles. The reduction in stress due to the coarsening of precipitates is compensated by
the transition of dislocation pairs to single dislocations, and thus, there is a net increase in strength in
the initial stages of overaging. Order hardening originates from the interaction of dislocations with
ordered precipitates (Figure 8). The cutting of an ordered precipitate by the first dislocation shifts one
half of a particle crystal plane by one interatomic distance against the other half plane (Figure 8b).
This results in creation of an antiphase boundary (APB) across the slip plane that represents an atomic
layer of incorrect order. After the second dislocation passing through the same particle, the second
shift of a crystal half plane occurs (Figure 8c,d). This restores the atomic order. Thus, dislocations
travelling in pairs (often referred to as superlattice dislocations) maintain the ordered structure after
precipitate
Metals shearing.
2020, 10, x FOR PEER REVIEW 9 of 19
Figure 8. Schematic illustration of dislocations interacting with an ordered Ni3 Al precipitate [83]: (a)
Figure 8. Schematic illustration of dislocations interacting with an ordered Ni3Al precipitate [83]: (a)
the original condition prior to particle cutting, (b) the first dislocation penetrated a particle, (c) the
second dislocation penetrated a particle, and (d) shifting of one half of the particle against the other
half by two interatomic distances restored the atomic order .
Figure 9 shows examples of such paired superlattice dislocations and particle cutting in a Ni-base
alloy.Figure 9 shows examples
This deformation involvesofcross-slip
such paired superlattice
of segments dislocations
of the and
superlattice particle cutting
dislocations in a{111}
from the Ni-
base alloy.toThis
slip plane deformation
{001} involves
cross-slip plane. Thesecross-slip of segments
cross-slipped segmentsof the superlattice
cannot dislocations
move without formingfrom the
an APB
{111} slip plane to {001} cross-slip plane. These cross-slipped segments cannot move
and thus resist deformation. Strengthening from cross-slip becomes more important with increasingwithout forming
an APB and because
temperature thus resist
thedeformation. Strengthening
cross-slip is thermally from cross-slip becomes more important with
activated.
increasing temperature because the cross-slip is thermally activated.
The initial cutting of an ordered particle by a single dislocation requires a stress increase. This stress
increase provides energy for formation of the antiphase boundary. With increasing the antiphase
boundary energy larger forces are required to cut the precipitates. Thus, the yield stress increases.
The antiphase boundary energy provides a significant contribution to strengthening and was observed
varying with alloy composition and particle chemistry. In particular, Ti, Co, Mo, and Fe were reported
to effectively increase the antiphase boundary energy [87].
Finer particles (<20 nm) may be too small to hold two dislocations (Figure 10a), this is called
a weak pair coupling. With larger particles, the second dislocation may start interacting with the
particle before the first dislocation moves away (Figure 10b), this is called a strong pair coupling.
In both cases, the strengthening contribution is due to the creation of an APB within the precipitate.
The dislocation–particle interaction mechanism changes from shearing to looping with a particle size
increase. Figure 10c qualitatively illustrates a dependence of precipitation strengthening on particle
Figure 9. TEM images showing (a) paired super lattice dislocations and (b) γ′ precipitate being cut by
the moving dislocations in a Ni superalloy [83].
The initial cutting of an ordered particle by a single dislocation requires a stress increase. This
stress increase provides energy for formation of the antiphase boundary. With increasing the
Metals 2020, 10, 1358 9 of 18
Figure 8. Schematic illustration of dislocations interacting with an ordered Ni3Al precipitate [83]: (a)
size: this dependence shows a maximum. As the particle size varies with ageing, the precipitation
strengthening contribution depends on the aging temperature and time [68]. At first, precipitation of
the γ’ from the supersaturated Ni matrix leads to an increase in strength with increasing temperature
and time. However, with further increase in temperature/time, an over-aging may lead to the particle
Figure 9 shows examples of such paired superlattice dislocations and particle cutting in a Ni-
coarsening and a decrease in particle volume fraction (Figure 10d). A decrease in particle volume
base alloy. This deformation involves cross-slip of segments of the superlattice dislocations from the
fraction should be avoided as it results in a decrease in potential number of dislocation–particle
{111} slip plane to {001} cross-slip plane. These cross-slipped segments cannot move without forming
interaction sites and strengthening capacity. Therefore, a careful design of heat treatment schedule is
an APB and thus resist deformation. Strengthening from cross-slip becomes more important with
required to simultaneously maximise the particle size and particle volume fraction.
increasing temperature because the cross-slip is thermally activated.
coarsening and a decrease in particle volume fraction (Figure 10d). A decrease in particle volume
fraction should be avoided as it results in a decrease in potential number of dislocation–particle
interaction
Figure sites
Figure 9.
9. TEM
TEMand strengthening
images
images showing
showing (a)(a)capacity.
paired Therefore,
paired super
super lattice a careful design
lattice dislocations
dislocations (b)of
and (b)
and γ0 heat
γ′ treatment
precipitate
precipitate beingschedule
being cut
cut by
by is
required
the to simultaneously
the moving
moving dislocations inmaximise
dislocations in aa Ni the particle
Ni superalloy
superalloy [83]. size and particle volume fraction.
[83].
The initial cutting of an ordered particle by a single dislocation requires a stress increase. This
stress increase provides energy for formation of the antiphase boundary. With increasing the
antiphase boundary energy larger forces are required to cut the precipitates. Thus, the yield stress
increases. The antiphase boundary energy provides a significant contribution to strengthening and
was observed varying with alloy composition and particle chemistry. In particular, Ti, Co, Mo, and
Fe were reported to effectively increase the antiphase boundary energy [87].
Finer particles (<20 nm) may be too small to hold two dislocations (Figure 10a), this is called a
weak pair coupling. With larger particles, the second dislocation may start interacting with the
particle before the first dislocation moves away (Figure 10b), this is called a strong pair coupling. In
both cases, the strengthening contribution is due to the creation of an APB within the precipitate. The
dislocation–particle interaction mechanism changes from shearing to looping with a particle size
increase. Figure 10c qualitatively illustrates a dependence of precipitation strengthening on particle
size: this dependence shows a maximum. As the particle size varies with ageing, the precipitation
strengthening contribution depends on the aging temperature and time [68]. At first, precipitation of
the γ’Figure
from 10.
theSchematic
10. supersaturated
Schematic Ni matrix
illustration
illustration ofof
(a)(a) leads
weak
weak to an increase
dislocation
dislocation in strength
coupling,
coupling, with
(b) strong
(b) strong increasing
dislocation
dislocation temperature
coupling,
coupling, and
and time. However,
andstrengthening
(c) with
strengthening further
effect increase
variation with inparticle
temperature/time, an over-aging may on lead 0
γtosize
theand
particle
(c) effect variation with particle sizesize [46];
[46]; (d)(d) effect
effect ofofaging
agingtime
time on the γ′
the size and
volume fraction ◦ C, 2–650 ◦ C, 3–700 ◦ C [88].
volume fraction in
in Monel
Monel K500
K500 for
for various
various aging
aging temperatures:
temperatures: 1–600
1–600 °C, 2–650 °C, 3–700 °C [88].
Precipitate morphology 0 lattice mismatch (Figure 11) [89]. The precipitate

Precipitate morphology may may change
change with
with aa γ/γ
γ/γ′ lattice mismatch (Figure 11) [89]. The precipitate
shape varies
shape varies toto minimise
minimise strain
strain inin the
the vicinity
vicinity of
of particles
particles and
and the
the particle
particle surface
surface energy.
energy. AtAt low
low
levels of lattice mismatch, the strain is low and the spherical shape is favourable for
levels of lattice mismatch, the strain is low and the spherical shape is favourable for the decrease of the decrease of
surface energy.
surface energy. At At higher
higher levels
levels of
of lattice
lattice mismatch,
mismatch, the the strain
strain increases
increases and and becomes
becomes orientation
orientation
dependent. The orientation relationship between the γ-matrix and γ 0 -particle promotes a cuboidal
dependent. The orientation relationship between the γ-matrix and γ′-particle promotes a cuboidal
shape. These
shape. γ0 -particles typically
These γ′-particles typically align
align along
along the <100>directions
the <100> directionsof of the
the matrix
matrix which
which have
have the
the
lowest elastic
lowest elasticstiffness.
stiffness.The
Theprecipitate
precipitatemorphology
morphology alsoalso
varies withwith
varies coarsening. Thus,Thus,
coarsening. on initial
on stages
initial
of nucleation and growth the particles are spherical, and then gradually
stages of nucleation and growth the particles are spherical, and then gradually change to change to cubes, arrays of
cubes,
cubes, of
arrays and dendritic
cubes, shape as shape
and dendritic coarsening proceeds.proceeds.
as coarsening The lattice
Themismatch betweenbetween
lattice mismatch particlesparticles
and the
matrix contributes to strengthening of an alloy.
and the matrix contributes to strengthening of an alloy.
shape. These γ′-particles typically align along the <100> directions of the matrix which have the
lowest elastic stiffness. The precipitate morphology also varies with coarsening. Thus, on initial
stages of nucleation and growth the particles are spherical, and then gradually change to cubes,
arrays of cubes, and dendritic shape as coarsening proceeds. The lattice mismatch between particles
Metals 2020, 10, 1358 10 of 18
and the matrix contributes to strengthening of an alloy.
Figure 11. Optical

Figure 11.images
Optical images of γ0 particles
of γ′ particles ininaaNi-Al-Mo alloy
Ni-Al-Mo alloy at different
at different lattice mismatches
lattice mismatches overlaid in overlaid
Metals the
2020,top
10,right
x FORcorner [89].
PEER REVIEW 11 of 19
in the top right corner [89].
Theγ′
The γ0precipitates
precipitatescan
canbe behardened
hardenedby bysolid
solidsolution
solutionstrengthening
strengthening(Figure
(Figure12).
12).Mo,Mo,Si,
Si,and
andTiTi
were shown to be the most effective elements for this. Although Cu and Co exhibit
were shown to be the most effective elements for this. Although Cu and Co exhibit substantial substantial solubility
in the particles,
solubility in the they do not
particles, increase
they do notthe strength
increase γ0 . The lattice
theofstrength parameter
of γ′. The of both theof
lattice parameter γ matrix and
both the γ
γ 0 precipitates depends on type and concentrations of alloying elements. Various elements partition
matrix and γ′ precipitates depends on type and concentrations of alloying elements. Various elements
differently
partition to the matrix
differently and
to the particles
matrix and and change
particles andtheir lattice
change parameters.
their Therefore,Therefore,
lattice parameters. the degreetheof
0
γ/γ lattice mismatch depends on the relative partitioning of alloyingofelements
degree of γ/γ′ lattice mismatch depends on the relative partitioning alloyingand lattice parameters
elements and lattice
variations with alloying (Figure 13).
parameters variations with alloying (Figure 13).
Figure12.
Figure (a)Solubility
12.(a) Solubilityof
ofvarious
variouselements
elementsin γ0particles
inγ′ particlesatat1150 ◦ C in Ni-Al-X alloy system, (b) effect
1150°C in Ni-Al-X alloy system, (b) effect
0 ◦
of various elements on the hardness of γ particles at 25 C [90].
of various elements on the hardness of γ′ particles at 25 °C [90].
MetalsFigure 12.
2020, 10, (a) Solubility of various elements in γ′ particles at 1150 °C in Ni-Al-X alloy system, (b) effect
1358 11 of 18
of various elements on the hardness of γ′ particles at 25 °C [90].
Figure 13. Effect of Ti/Al ratio γ/γ′0 mismatch for Ni-20Cr-Al-Ti and Ni-20Cr-5Mo-Al-Ti alloys
ratio on the γ/γ
with a constant (Al +
constant (Al + Ti) content of 3.5 wt.% [34].
4.4. Dislocation Strengthening

4.4. Dislocation Strengthening (Work
(Work Hardening)
Hardening)
Ni-Cu
Ni-Cu alloys
alloys exhibit
exhibit rapid
rapid work
work hardening,
hardening, characteristic for all
characteristic for all Ni-base alloys due
Ni-base alloys due to
to their
their fcc
fcc
crystal structure [91]. This allows to increase the room temperature hardness and
crystal structure [91]. This allows to increase the room temperature hardness and strength applyingstrength applying
large
large strains
strains ofof cold
cold deformation. However, to
deformation. However, to illuminate
illuminate fracture
fracture development,
development, (i) (i) the
the number
number of of
deformation passes in a processing technology should be controlled, (ii) strain per
deformation passes in a processing technology should be controlled, (ii) strain per pass must pass must be reducedbe
with eachwith
reduced deformation stage, andstage,
each deformation (iii) intermediate annealing should
and (iii) intermediate annealingbe applied
should to
berestore
applied ductility for
to restore
further processing [57].
ductility for further processing [57].
The
The rate
rate of
of work
work hardening
hardening inin the
the presence
presence of of precipitates
precipitates was
was found
found toto be
be higher
higher than
than in
in aa
precipitate-free
precipitate-free (solution-treated)
(solution-treated) matrix
matrix and
and increased
increased with
with increasing
increasing precipitate
precipitate size
size [92].
[92]. In
In alloys
alloys
where the particles were small and shearing mechanism operated, the increase
where the particles were small and shearing mechanism operated, the increase in work hardening in work hardening
rate
rate was
was minor.
minor. TheThe passage
passage ofof dislocations
dislocations through
through particles
particles reduced
reduced their
their diameters,
diameters, making
making the the
passage of the following dislocations easier. A relative reduction in diameter for a small particle
would be larger than that for a large particle. With growing particle size the work hardening rate
increased, even when particle shearing occurred. Looping increases the work hardening rate. This can
be explained by a gradual reduction in the interparticle spacing with the formation of dislocation loops
around precipitates, making passage of the successive dislocations difficult [93].
With an increase in cold deformation the strength of Monel K500 increases and ductility decreases
(Figure 14a). The optimum deformation strain for Monel K500 was found to be about 20% [88]:
at this strain an increment to the yield stress is quite substantial (about 300 MPa) and the remaining
ductility is still significant (about 30% of elongation to failure). Cold deformation has been shown
to affect the strength variation during aging (Figure 14b). With an increase in aging temperature up
to 600 ◦ C, the strength increased for 0 and 10% cold worked samples. However, the samples cold
worked to 20% and 25% showed strength peaks in the range of 560–600 ◦ C followed by the strength
decrease. Obviously with an increase in cold deformation the strain induced precipitation occurs faster;
this leads to faster particle growth accompanied by a decrease in particle number density and strength
decrease. Irrespective of the aging temperature the strength showed a minimum for 10% of prior cold
worked material (Figure 14c). This could be explained if small amounts of deformation facilitated the
dislocation breaking from their pinning points, increasing the dislocation mobility and decreasing the
yield stress.
Since work hardening is related to solute element concentrations and presence of precipitates,
the work hardening rate generally increases with complexity of alloy composition. Similarly,
the age-hardenable alloys have higher work hardening rates than their solid solution equivalents [94].
In the annealed condition, Monel K500 can be cold-worked using traditional processing technology.
It has excellent ductility, although deformation forces may be high. Work hardening of Monel K500
remaining ductility is still significant (about 30% of elongation to failure). Cold deformation has been
shown to affect the strength variation during aging (Figure 14b). With an increase in aging
temperature up to 600 °C, the strength increased for 0 and 10% cold worked samples. However, the
samples cold worked to 20% and 25% showed strength peaks in the range of 560–600 °C followed by
the strength decrease. Obviously with an increase in cold deformation the strain induced
Metals 2020, 10, 1358 12 of 18
precipitation occurs faster; this leads to faster particle growth accompanied by a decrease in particle
number density and strength decrease. Irrespective of the aging temperature the strength showed a
minimum
with for 10% of prior
cold deformation cold worked
is shown in Figurematerial (Figure 14c).
15 in comparison This
with could
other be explained
materials: Monelif K500,
small
amounts of deformation
precipitation hardenable facilitated the dislocation
with Ni3 (Ti,Al) breaking from
and TiC, approaches their pinning
Inconel points, increasing
600, precipitation hardenablethe
dislocation mobility
with Cr-rich carbides. and decreasing the yield stress.
a b c
Figure 14. (a) Mechanical properties variation with cold deformation, (b) effect of age hardening
Figure 14. (a) Mechanical properties variation with cold deformation, (b) effect of age hardening
temperatures on properties for various strains of prior cold deformation: 1–0, 2–0.10, 3–0.20, and 4–0.25,
temperatures on properties for various strains of prior cold deformation: 1–0, 2–0.10, 3–0.20, and 4–
and (c) effect of prior cold deformation on the yield stress after aging at various temperatures, all for
0.25, and (c) effect of prior cold deformation on the yield stress after aging at various temperatures,
MetalsMonel K500
2020, 10, [88].
x FOR PEER REVIEW 13 of 19
all for Monel K500 [88].
Since work hardening is related to solute element concentrations and presence of precipitates,
the work hardening rate generally increases with complexity of alloy composition. Similarly, the age-
hardenable alloys have higher work hardening rates than their solid solution equivalents [94]. In the
annealed condition, Monel K500 can be cold-worked using traditional processing technology. It has
excellent ductility, although deformation forces may be high. Work hardening of Monel K500 with
cold deformation is shown in Figure 15 in comparison with other materials: Monel K500,
precipitation hardenable with Ni3(Ti,Al) and TiC, approaches Inconel 600, precipitation hardenable
with Cr-rich carbides.
Figure
Figure 15.15.Comparison
Comparisonofofwork
work hardening
hardening capacity
capacity of
ofMonel
MonelK500
K500toto
other Ni-base
other alloys
Ni-base [53].[53]
alloys
(reproduced with a permission from the Special Metals Corporation).
5. Mechanical Properties
5. Mechanical Properties
Room temperature tensile properties of Monel 400 and K500 are shown in Table 3 [20]. In hot-
rolled and temperature
Room tensile properties
annealed conditions Monel of Monel
K500 400 and
shows K500 areMPa
a 100–200 shown in Table
higher 3 [20].
yield stressIn hot-rolled
(YS) and
and annealed
ultimate conditions
tensile strength Monel K500Monel
(UTS) than shows 400,
a 100–200
due toMPa
solidhigher yield
solution andstress (YS) and ultimate
precipitation tensile
strengthening.
strength
In both alloys YS and UTS are slightly higher for cold formed products, due to work hardening.YS
(UTS) than Monel 400, due to solid solution and precipitation strengthening. In both alloys In
and
hot UTS are slightly
finished Monel higher
K500, for cold formed
annealing mayproducts,
lead to due to work
strength hardening.
decrease In hot30%,
by about finished Monel
following
K500, annealing
dissolution may lead to
of precipitates andstrength decrease
dislocation by about 30%,
annihilation. following
In contrast, dissolution of
age-hardening mayprecipitates and
result in 1.3–
dislocation annihilation. In contrast, age-hardening may result in 1.3–2.5 times increase
2.5 times increase in strength due to precipitation. For the cold formed products, annealing decreases in strength due
to precipitation. For the cold formed products, annealing decreases strength by about
strength by about 40–50%; although, age-hardening may increase strength by up to 1.3 times. As seen, 40–50%; although,
age-hardening
the age-hardening mayheat
increase strength
treatment by up
is more to 1.3 times.
effective As seen,strength
in increasing the age-hardening heat treatment
of the hot finished products, is
more effective in increasing
compared to the cold finished. strength of the hot finished products, compared to the cold finished.
High and low temperature tensile properties of Monel K500 are shown in Figure 16. For hot rolled
product, with an increase in temperature
Table 3. Mechanicaltheproperties
YS and UTS do not
of Monel vary
400 K500 [20]. until 650 ◦ C (1200 ◦ F)
andsignificantly
◦ ◦
and 150 C (300 F), respectively. Age-hardening increases YS and UTS by about 1.5 and 2 times,
Yield Strength, Tensile Elongation,
respectively. However,
Processing the YS stability at high temperature decreases, YS starts going down
Condition HBat a lower
MPa Strength, MPa %
temperature of 430 ◦ C (800 ◦ F) compared to the non-aged material. In contrast, the stability of UTS
Monel 400
Hot-Finished 280–690 550–760 30–60 140–240
Hot-Finished,
170–340 520–620 35–60 110–150
Annealed
Cold-Drawn 380–690 580–830 22–40 160–225
Monel K500
Metals 2020, 10, 1358 13 of 18
increases, UTS starts decreasing at a higher temperature of 300 ◦ C (550 ◦ F) compared to the non-aged
material. The decrease in YS stability after ageing can be associated with destruction of the dislocation
sub-structure during ageing, and the increase in UTS stability follows particle precipitation. Annealing
prior age-hardening does not provide any strength gain compared to the hot-rolled and age-hardened
product, however the stability of elongation increase. This is a consequence of significantly reduced
dislocation density after annealing and increased distance of dislocations free pass. With a decrease in
temperature, the tensile strength and yield stress both increase while ductility and toughness remain
virtually the same (Figure 16d). No ductile-to-brittle transition occurs even at temperatures as low as
that of
Metals liquid
2020, 10, x hydrogen. Thus, this alloy is suitable for many cryogenic applications.
FOR PEER REVIEW 14 of 19
(1200 °F) and 150 °C (300 °F),3.respectively.

Table Age-hardening
Mechanical properties of Monelincreases YS and
400 and K500 [20].UTS by about 1.5 and 2
times, respectively. However, the YS stability at high temperature decreases, YS starts going down at
Processing Condition Yield Strength, MPa Tensile Strength, MPa Elongation, % HB
a lower temperature of 430 °C (800 °F) compared to the non-aged material. In contrast, the stability
Monel 400
of UTS increases, UTS starts decreasing
Hot-Finished at a higher temperature
280–690 of 300 °C (550 °F)
550–760 compared140–240
30–60 to the
non-aged material.
Hot-Finished, The decrease in YS170–340
Annealed stability after ageing can be associated with35–60
520–620 destruction of the
110–150
dislocationCold-Drawn
sub-structure during ageing, 380–690 and the increase 580–830
in UTS stability22–40follows 160–225
particle
Monel K500
precipitation. Annealing prior age-hardening
Hot-Finished 280–760 does not provide any strength gain45–20
620–1070 compared140–315
to the
hot-rolled and age-hardened
Hot-Finished, Aged product, however the stability
690–1034 of elongation increase.
965–1310 30–20 This is a
265–346
Hot-Finished,
consequence Annealed
of significantly reduced280–414
dislocation density after 621–760 45–25
annealing and increased 140–185of
distance
Hot-Finished, Annealed and Aged 586–830 896–1140 35–20 250–315
dislocations freeAs-Drawn
Cold-Drawn, pass. With a decrease in temperature, the690–965
483–860 tensile strength and35–13yield stress both
175–260
increaseCold-Drawn,
while ductility
Aged and toughness remain virtually the 931–1280
655–1100 same (Figure 16d). No ductile-to-brittle
30–15 255–370
Cold-Drawn,
transition occurs Annealed
even at temperatures 280–414
as low as that of liquid 621–760
hydrogen. Thus, this 50–25 140–185
alloy is suitable
Cold-Drawn, Annealed and Aged 586–830 896–1310 30–20 250–315
for many cryogenic applications.
a b c d
Figure 16. High temperature tensile properties of Monel K500: (a) hot-rolled, (b) hot-rolled and
Figure 16. High temperature tensile properties of Monel K500: (a) hot-rolled, (b) hot-rolled and age-
age-hardened, and (c) annealed and age-hardened; (d) low temperature tensile properties of Monel
hardened, and (c) annealed and age-hardened; (d) low temperature tensile properties of Monel K500
K500 [53] (reproduced with a permission from the Special Metals Corporation).
[53].
In view of excellent corrosion resistance coupled with high strength and toughness at cryogenic
In view of excellent corrosion resistance coupled with high strength and toughness at cryogenic
temperatures [95,96] Monel alloys are good candidates for structural components of machinery and
temperatures [95,96] Monel alloys are good candidates for structural components of machinery and
storage of liquefied gases in aerospace and chemical industry. High temperature application of Monel
storage of liquefied gases in aerospace and chemical industry. High temperature application of Monel
is limited by low melting temperature of Cu. However, the precipitation strengthening capacity in the
is limited by low melting temperature of Cu. However, the precipitation strengthening capacity in
Ni-Cu alloy system can be improved with appropriate alloying element additions and heat treatment.
the Ni-Cu alloy system can be improved with appropriate alloying element additions and heat
Ni-Cu alloys are easily weldable [97] and were successfully used as an input material in powder
treatment. Ni-Cu alloys are easily weldable [97] and were successfully used as an input material in
based [98] and wire arc additive manufacturing [99]. Development of these modern technologies
powder based [98] and wire arc additive manufacturing [99]. Development of these modern
allows to apply the Ni-Cu alloys as a surface cladding material for protection of less corrosion resistant
technologies allows to apply the Ni-Cu alloys as a surface cladding material for protection of less
core or in components with mechanical properties gradient.
corrosion resistant core or in components with mechanical properties gradient.
6. Conclusions
Due to Ni and Cu exhibiting complete solid solubility, their alloys are single phase. Thus, in Ni-
Cu alloy four strengthening mechanisms operate: grain refinement, solid solution, precipitation, and
dislocation strengthening (work hardening). Composition of an alloy determines whether the solid
solution or precipitation strengthening dominates. Mo, Ti, Cr, and Mn are the most frequently used
Metals 2020, 10, 1358 14 of 18
6. Conclusions
Due to Ni and Cu exhibiting complete solid solubility, their alloys are single phase. Thus,
in Ni-Cu alloy four strengthening mechanisms operate: grain refinement, solid solution, precipitation,
and dislocation strengthening (work hardening). Composition of an alloy determines whether the
solid solution or precipitation strengthening dominates. Mo, Ti, Cr, and Mn are the most frequently
used solid solution strengthening elements, due to their significant difference in atomic sizes from
Ni. Such elements as Fe, Co, and Cu are the second order solid solution strengtheners, due to their
high solubility in Ni. Al and Ti are the most effective precipitation strengthening elements in Ni-Cu
alloys, as they tend to form NiAlTi-rich intermetallic particles. Sometimes Mn-rich M23 C6 or Ti-rich
MC carbides can also precipitate. The dislocation strengthening capacity of Ni-Cu alloys is substantial,
which is determined by their fcc crystal structure. However, cold deformation above 20% would
decrease ductility below the practically reasonable limits of 30% elongation. In presence of particle
forming elements in alloy composition, age hardening heat treatment is frequently used as the final
strengthening operation.
Author Contributions: O.M. carried out the literature analysis and paper writing; A.K. contributed to the
discussion of results. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: Olexandra Marenych is thankful for a scholarship sponsored by the Defence Materials
Technology Centre at the University of Wollongong (Australia), which was established under the initiative of the
Australian Government’s Defence Future Capability Technology Centre.
Conflicts of Interest: The authors declare no conflict of interest.
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© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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Keywords: Ni-Cu alloys; microstructure characterisation; mechanical properties; strengthening

Table 1. Chemical compositions of Monel alloys (wt.%).

Metals 2020, 10, 1358; doi:10.3390/met10101358 www.mdpi.com/journal/metals

2. Role of Alloying Elements

4.1. Grain Refinement

4.2. Solid Solution Strengthening

4.2. Solid Solution Strengthening

Approximate Atomic Size Approximate Solubility in Ni at

4.3. Precipitation Strengthening

Metals 2020, 10, x FOR PEER REVIEW 10 of 19

Precipitate morphology 0 lattice mismatch (Figure 11) [89]. The precipitate

Figure 11. Optical

4.4. Dislocation Strengthening

(1200 °F) and 150 °C (300 °F),3.respectively.

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