Author’s Accepted Manuscript

Microstructure, mechanical and tribological

properties of nickel-aluminium bronze alloys
developed via gas-atomization and spark plasma
sintering

Wenzheng Zhai, Wenlong Lu, Po Zhang, Mingzhuo

Zhou, Xiaojun Liu, Liping Zhou
www.elsevier.com/locate/msea

PII: S0921-5093(17)31203-0
DOI: http://dx.doi.org/10.1016/j.msea.2017.09.047
Reference: MSA35514
To appear in: Materials Science & Engineering A
Received date: 6 July 2017
Revised date: 9 September 2017
Accepted date: 11 September 2017
Cite this article as: Wenzheng Zhai, Wenlong Lu, Po Zhang, Mingzhuo Zhou,
Xiaojun Liu and Liping Zhou, Microstructure, mechanical and tribological
properties of nickel-aluminium bronze alloys developed via gas-atomization and
spark plasma sintering, Materials Science & Engineering A,
http://dx.doi.org/10.1016/j.msea.2017.09.047
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 Microstructure, mechanical and tribological properties of nickel-aluminium bronze

alloys developed via gas-atomization and spark plasma sintering

Wenzheng Zhai, Wenlong Lu1, Po Zhang, Mingzhuo Zhou, Xiaojun Liu, Liping Zhou

The State Key Laboratory of Digital Manufacturing Equipment and Technology, School of Mechanical Science and
Engineering, Huazhong University of Science and Technology (HUST), Wuhan 430074, PR China

Abstract: This work investigated the effect of sintering temperatures (600-750 °C) on mechanical and

tribological behaviors of nickel-aluminium bronze (NAB) alloys developed by gas atomization and spark

plasma sintering. Results indicated an increase of the volume fraction of B2-type NiAl precipitates with

increasing sintering temperature, leading to an improvement of the yield strength and the wear resistance.

Specifically, detailed microstructural analyses of sintered NAB alloys at 750 °C showed the presence of

ultrafine grains with an average size of 367 nm, nanoscale twins with a volume fraction of 11.7% and

dislocations with a density of 1.3 ± 0.1 × 1014 m-2. A much higher yield strength of 620 MPa was obtained in

NAB, if compared to that of conventional cast counterparts (280-440 MPa). Estimations of strengthening

mechanisms suggested the predominant mechanism of grain boundary strengthening (335MPa) for NAB

alloys with contributions from precipitate strengthening (54 MPa), dislocation strengthening (75 MPa), twin

boundary strengthening (89 MPa) and solid solution strengthening (50 MPa). Moreover, dislocations was

blocked at twin boundaries to form complex dislocation barriers and networks, further contributing to the high

strength. The high wear resistance of NAB could be ascribed to the reduction of the local stress around crack

tips due to the high elastic modulus mismatch (ENiAl/ECu), and to the crack extension toughening near the

interface of the matrix and the precipitate caused by the high plastic mismatch (σNiAl/σCu).

Keywords: Characterization; Copper alloys; Powder methods; Grains and interfaces

1
Corresponding author.
E-mail addresses: hustwenlong@mail.hust.edu.cn (W.L. Lu)

1
1. Introduction

Coherent twin boundaries (TBs) inside grain interiors show a strengthening effect similar to that of grain

boundaries (GBs), and ultrafine-grained copper containing a high density of nanoscale twins has the ultrahigh

strength [1-3]. Additionally, precipitation hardening is an attractive strengthening mechanism for malleable

materials, including most structural alloys of aluminium, magnesium, nickel, titanium, copper and stainless

steels [4-6]. Among these alloys, the nickel-aluminium bronze (NAB) has been extensively used in marine

engineering applications owing to its valuable mechanical and physical characteristics, as well as the

superior corrosion resistance [7, 8]. The fretting wear often occurs between contact surfaces, resulting in

severe galling failure and fretting fatigue of NAB. In the literature, many reports indicated that the

precipitation during aging could increase the strength, hardness and wear resistance of alloys without a

considerable decrease in the corrosion resistance [9-12]. However, previous studies also showed that the

precipitation strengthening of the NAB alloy by conventional aging might be limited due to the

non-uniformly distributed precipitates and coarse particles in the matrix [13, 14].

The cast NAB alloy presents complex microstructures which mainly consist of the Widmanstätten α

phase with coarse grains, intermetallic κ phases and the retained β phase [15]. The κ-phases containing κI-,

κII-, κIII- and κIV-phase are main precipitates in NAB which are distinguishable by the morphology, location

and distribution in the microstructure [13, 16, 17]. The coarse α grains in the cast NAB alloy significantly

decrease its tensile strength [18]. Also, these precipitates show strong effects on the corrosion, fatigue,

mechanical and tribological behaviors of NAB.

The corrosion resistance of the cast NAB alloy is reported to be initially confined to eutectoid α + κIII

structure with slight attack of the copper rich α-phase. This can be attributed to the presence of a greater

proportion of cathodic phase (κIII) in the eutectoid structure as compared to that in the α-grains and also to

2
the closely adjacent anodic and cathodic areas in the eutectoid structure [16]. The κIII-phase normally

appears in a lamellar or a globular (degraded lamellar) form and is described as the nickel-rich (NiAl) phase.

It often grows normal to the α/β boundary, as well as forms at the boundary of the κI-phase. Recently, the

effect of second phases on the fatigue crack growth behavior in the as-cast and annealed NAB has been

analyzed by Xu et al. [14]. The coarse dendritic κII particles in NAB were demonstrated to have an

accelerative effect on the fatigue crack propagation by cracking through α and κII interfaces. It is noteworthy

that the uniformly distributed κIV precipitates with fine grains improves the growth resistance of fatigue

crack in the NAB alloy without the expense of its corrosion resistance. The κIV-phase is a fine precipitate

within the α-phase and is considered to be iron-rich with the chemical compositions of 3Cu-11Al-7Ni-73Fe

(wt%) [15] or 8.12Al-Mn0.84-Fe42.70-Ni35.32-Cu13.01 (wt%) [19].

The mechanical and tribological behaviors of alloys depend on the amount, morphology and size of

precipitates [20, 21]. Although thermal treatments including dissolution and ageing usually control

characteristics of precipitates of casting parts, casting produces coarse segregated microstructures which

limit their broad applications. Powder metallurgy has demonstrated to be an effective way to reduce

segregations and promote a finer microstructure of alloys that can exhibit a good combination of mechanical

and tribological properties [22, 23]. Spark plasma sintering (SPS) is a consolidation technique combining a

uni-axial compaction with the current. With regard to alloy powders, densification can be achieved at

significantly lower temperatures and faster thermal cycles, thereby inhibiting grain growth and preserving a

fine microstructure. Meanwhile, gas-atomization with SPS offers many advantages including control of

contamination, grain refinement and avoidance of segregation [22]. Gas-atomization enables the large-scale

production of powders (2 kg/min) with a uniform microstructure due to rapid solidification [24, 25]. It has

been confirmed that precipitates presented in the gas-atomized powders and the fraction of precipitates could

remain rather constant after SPS process, which facilitated the enhancement of mechanical properties of

3
alloys [20]. The SPS technique has been applied recently to fabricate Cu alloys with finer grain sizes and

improved strength compared to cast Cu alloys [26-28].

While the SPS process has been proved to be one of the most promising and widely studied method to

consolidate Cu-based alloys keeping fine grain sizes, a very limited attention has been attracted to control

the precipitation of NAB alloys for enhancing their mechanical and tribological performance. To the best of

our knowledge, there has been no report on NAB alloys through the gas-atomization and SPS processes. In

order to gain a full knowledge of the mechanical and tribological behaviors of NAB alloys with

uniformly-distributed fine precipitates by SPS, a more precise relation among the sintering temperature, the

microstructure, as well as the mechanical and tribological properties is required.

Thus, the aim of the present work is to estimate quantitatively the impact of the SPS sintering

temperature on microstructures of the NAB alloy in terms of the grain size, the chemical composition, and

the size of precipitates. Additionally, the effect of precipitates and nanoscale twins on the mechanical and

tribological properties of NAB alloys is also systematically analyzed by taking into account the Orowan

strengthening mechanism and the Hall-Petch relationship. Mechanical and tribological properties of

SPS-sintered NAB alloys are compared with those of casting and heat-treated counterparts to highlight the

benefit of this powder metallurgy route.

2. Experimental details

2.1 Initial powders and SPS process

The gas-atomized NAB powders, supplied by Metal Products Trade Co. Ltd., were used as the initial

material for the SPS process. Scanning electron microscopy (SEM, JSM-7600F, Jeol Ltd., Tokyo, Japan)

image is shown that the raw powders mainly contain spherical particles having diameters between 5 and 25

μm (Fig. 1). Table 1 gives the chemical composition of the gas-atomized powders. Cylindrical specimens

with a diameter of 26 mm and a height of 7 mm were sintered from the gas-atomized NAB powders by an

4
SPS apparatus (LABOX-1575, SINTER LAND, Japan). From the analysis of Al-Fe [29] and Al-Ni [30]

binary phase diagrams for binary Fe-(20-25) at% Al and Ni-50 at% Al alloys, the Fe3Al (D03) and NiAl (B2)

domains can be obtained at the temperature above 400 ℃, while 650 ℃ is the temperature of the theoretical

ending of the Fe3Al phase. To track the potential phase transformation of the precipitate during the sintering

process, different final sintering temperatures varying from 600 to 750 ℃ were applied with a holding time

of 5 min and a pressure of 50 MPa in a graphite die. NAB-600, NAB-650, NAB-700 and NAB-750 denote

the samples sintered at 600, 650, 700 and 750 ℃.

Table 1. Chemical composition of the gas-atomized NAB powders

Weight percentage (wt%)

Cu Al Ni Fe Mn
Gas-atomized NAB powder 81.1 9.5 4.2 4 1.2

2.2. Microstructural analysis

The microstructures of SPS-consolidated bulk samples were investigated by a XRD-7000S X-ray

diffractometer with Cu Kα radiation, a JSM-7600F field emission scanning electron microscope (FE-SEM)

and a JEOL JEM 2100 transmission electron microscope (TEM) with Energy Dispersive X-Ray

Spectroscopy (EDX). To determine the evolution of the precipitation during the SPS process, the samples

were polished followed by etching with a solution of 5 g FeCl3 + 15 mL HCl + 80 mL H2O. The etched

specimens were examined and the volume fraction of the precipitation were analyzed using Image-Pro Plus

software. Morphologies of surfaces after wear tests were investigated by the combination of an OLYMPUS

DSX510 3D optical microscope (OM) and the FE-SEM. SEM imaging with the energy dispersive

spectroscopy (EDS) served for the investigation of wear mechanisms of sintered bulk materials, and

profilometry was conducted to provide a quantitative comparison of the wear volume to determine the wear

resistance of NAB alloys.

5
2.3. Mechanical characterization

Mechanical properties were assessed by rate-controlled: (i) compression tests on cylindrical specimens

with a diameter of 3.0 mm and a height of 4.5 mm; (ii) tensile tests on samples with a width of 2.0 mm, a

thickness of 1.8 mm and a gage length of 6.0 mm. All samples were sectioned by wire cutting from SPS

disks. The tests were conducted at a strain rate of 1.0 × 10-3 s-1 using a Shimadzu AG-100KN device. Five

specimens were tested for each sintering condition. The yield strength, the ultimate strength and the strain at

the ultimate strength were obtained based on stress-strain curves.

2.4. Tribological characterization

Friction and wear tests were carried out using a torsional fretting test system with a flat-on-flat

configuration under contact loads of 43-106 N and a frequency of 2 Hz for 20000 cycles. The diagram of the

configuration can be found in our previous study [31]. The angular displacement amplitude (θ) of tests was

1.5°. These experimental parameters were set based on the practical operating conditions [32]. The

counterpart was 42CrMo4 steel with a hardness of 25 HRC and a roughness of Ra = 0.2 μm. All tests were

conducted at least three times to make sure the repeatability of experimental results at same conditions, and

average results were reported.

3. Results

3.1. Microstructures of NAB alloys sintered by SPS

Fig. 2 shows the evolution of XRD patterns of NAB samples sintered at 600, 650, 700 and 750 °C,

which confirms that the main peak of all samples is indexed to the α phase (JCPDF no. 50-1295). Fe3Al

precipitates can be also observed in all samples, and the (220) peak related to the Fe3Al phase increases with

6
increasing the sintering temperature from 600 to 650 °C. Besides, the peak splitting presents on the right of

the Fe3Al peak (denoted by the dashed arrow) of the sample sintered at 700 °C (as shown in the inset of Fig.

2). In particular, complete bifurcation occurs for NAB-750 with the reduced Fe3Al content and the increased

NiAl content. As the sintering temperature increases, the (220) peak shifts to a higher angle and the NiAl

content increases, indicating a distortion of lattice parameters in the Fe3Al-NiAl system with an increased

mole fraction ratio of NiAl/Fe3Al. In the D03 structure, three types of ordered domain boundaries including

B2(I)-, B2(II)- and D03-types could be present at lower temperatures [33]; whereas, for the Fe3Al

composition, Ni substitute for the Fe position leads to the lattice distortion induced by different atomic radii

of Ni (rNi = 0.122 nm) [34] and Fe (rFe = 0.124 nm) [35], resulting in a shift of Fe3Al peak to a higher angle.

The partial substitution of Ni for Fe decreases the lattice parameter of Fe3Al, thus reducing the lattice misfit

strain energy for nucleation of nanoparticles. The critical energy for nucleation of NiAl nanoparticles is

reduced, which could promote to a transformation of precipitates from the Fe3Al phase to the NiAl phase.

Consequently, the peak of the Fe3Al phase in XRD patterns decreases with the raise of sintering temperature

(650-750 °C).

According to XRD information, the grain diameter d and microstrain ε of the NAB bulk materials can

be obtained from the true XRD peak broadening B of the samples based on the Williamson-Hall method as

[36]

𝐾𝜆
B cos 𝜃𝐵 = + s 𝜃𝐵 (1)
𝑑

where λ represents the wavelength of Cu Kα X-ray, K is ~0.9, and θB is the Bragg angle. Therefore, the

dislocation density ρ can be calculated from the grain diameter d and microstrain ε by [37]

2√3
𝜌= (2)
𝑑𝑏

√2
where b is the Burgers vector, and equals to a for face-centered cubic (fcc) metals (a is the lattice
2

parameter). Through Eqs. (1) and (2), the grain diameter and the dislocation density for sintered bulk

7
materials are ~281 nm and 1.3 ± 0.1 × 1014 m-2, respectively.

For each sintering temperature condition, the NAB bulk materials have a relative density close to 100%,

indicating the full densification of the alloy at the investigated temperature range. Fig. 3 gives SEM images

at two magnifications showing the microstructures for the bulk materials sintered at 600, 700 and 750 °C.

For each condition, the existence of Fe3Al and NiAl precipitates is observed both at the GBs and in grain

interiors. The amount the Fe3Al precipitate reduces with increasing sintering temperatures; in contrast, the

content of the B2-type NiAl precipitate increases. This confirms the increase of the NiAl peak observed by

XRD. From the SEM and XRD analyses, the total volume fraction of two precipitates is determined as 5%

for each bulk material.

Table 2. EDX composition analyses of the precipitates in the NAB alloy after the SPS process at 600 °C
Precipitate Al Mn Fe Ni Cu
1 13.9 1.1 40.7 7.3 37.0
2 16.5 1.9 47.1 10.7 23.8
3 13.0 1.6 39.6 10.8 34.9
4 10.2 2.5 38.6 9.2 39.5

Fig. 4 displays TEM characterizations of the sintered bulk sample at 750 °C. The average grain size of

367 nm is determined from Fig. 4a, which is larger than the grain diameter calculated by the XRD result.

This is because XRD measures coherent diffraction domains that include dislocation cells and subgrains [38,

39]. The selected-area electron diffraction (SAED) pattern (inset in Fig. 4a) illustrates that the ultrafine

grains have random crystallographic orientations. The precipitates also can be clearly observed either in

bright field (Fig. 4b) or dark field (Fig. 4c) images. The lamellar structure in Fig. 4c is confirmed to

correspond to the B2 phase, while the elliptical structure corresponds to the ordered Fe3Al phase, with their

diffraction patters given in the inset of Fig. 4c. The distribution of precipitates is quite uniform with an

average grain size of 47 nm (Fig. 4d). Since no needle-shape or disk-shape precipitates can be observed, the

8
precipitates are considered to have a spherical shape. Several larger precipitates appear in a lamellar

microstructure, which would be the NiAl phase. Fig. 4e gives an example of the EDX spectra of the

precipitates. Four spherical precipitates in the NAB specimen are examined, and composition results are

shown in Table 2. The composition of precipitates shows the Fe/Al atomic ratio of ~3, matching the XRD

results of Fe3Al phase. The high Cu concentrations arise from overlapping of the precipitate and the matrix.

TEM bright field images of NAB-750 also reveal twins in grains with the thickness of 45-67 nm, as

displayed in Fig. 5a. Besides, numerous twins are observed in the alloy (Fig. 5b). The occurrence of twins in

the NAB alloys would arise from the formation of precipitates with a local stress during the gas-atomization

process. Meanwhile, twins can be generated during the SPS process due to the compression condition. To

determine the mean value of the twin thickness, more than 60 twins are measured in order to guarantee a

good statistics. The distribution of the twin thickness based on the observation is summarized in Fig. 5c,

demonstrating that 83.4% of the twin thickness varies from 44 nm to 74 nm. The twin volume fraction (Fv)

can be obtained by the Fullman equation [40]:

Fv = 2e / (t + 2e) (3)

where e and t are the average twin thickness (Fig. 5c) and mean twin spacing (Fig. 5d), respectively. For the

mean twin spacing test, more than 30 areas are considered. However, the twins are not observed to be

present in all grains and their total volume fraction needs to be calculated by the consideration of the

concentration (26%) of grains distributed by twins. Therefore, the twin volume fraction is calculated to be

11.7%. This result of the twin volume fraction is consistence with the previous work of Cu-based alloys [38].

It has been proved that at the macro-scale, increasing the fraction of special boundaries could enhance the

bulk properties of structural and functional materials.

Fig. 6 displays further TEM observations of nanostructures around the twins, indicating that dislocations

are captured between TBs. The high magnification image displays the inhibition of dislocation movement at

9
the TB, as denoted by arrows in Fig. 6b. Previous studies also reported that TBs could act as dislocation

barriers and promot to a high fracture toughness and strengths due to the inhibition of the dislocation

movement [22, 41]. Some curved dislocations can be observed, suggesting that they could be introduced by

a dislocation multiplication mechanism. As discussed by Wen et al. [38] the pressure applied during the SPS

process would generate some dislocations. Meanwhile, a high density of precipitates in the sintered bulk

sample and a significant fraction of twins in the grain interiors further reduce the recovery rate.

3.2. Mechanical properties

Fig. 7a displays representative compressive stress-strain curves of sintered NAB alloys at 600 and

750 °C. The yield strengths of NAB-600 and NAB-750 are 540 ± 10 and 620 ± 10 MPa, respectively, and

the ultimate strengths are 1700 ± 30 and 1480 ± 30 MPa at strain of ~44%. Specifically, the values of the

compressive yield strength of NAB-600 and NAB-750 are close to those of the tensile yield strength (from

the tensile stress-strain curves given in Fig. 7b), which are 545 ± 10 and 630 ± 10 MPa, respectively. Table 3

gives the comparison of yield and ultimate strengths between NAB alloys in this work and in previously

reported works where the NAB alloys were fabricated by other methods [14, 42-45] such as casting,

annealing and normalizing. Our SPS-sintered bulk materials exhibit a high ultimate strength value for NAB

alloys, and show one of the highest reported yield strength values.

Table 3. Comparison of strengths of NAB-600 in this work and the previous reported NAB alloys.
Alloy Processing condition Yield strength (MPa) Ultimate strength (MPa) Ref.
NAB-750 Gas-atomization and SPS 620-630 1480 This work
NAB Casting 379 540 [42]
NAB - 295 800 [43]
NAB Casting 259 690 [14]
NAB Annealing 270 600 [14]
NAB Normalizing 432 760 [14]
NAB Casting 312 722 [45]
NAB Annealing 304 695 [45]
NAB Normalizing 439 791 [45]
NAB Quenching and aging 921 949 [45]

10
 NAB Quenching and aging 561 769 [45]
NAB Quenching and aging 521 758 [45]
NAB Casting 284 691 [44]
NAB Annealing 280 673 [44]

3.3. Tribological properties

Since friction and wear have traditionally been linked to mechanical properties and the composition,

tribological behaviors of NAB samples sintered at 600, 700 and 750 °C are compared in this subsection. Fig.

8a-c show evolutions of friction coefficients of NAB specimens as a function of fretting cycles tested at

contact loads of 43, 86 and 106 N. Friction coefficients evolve with the first 103 fretting cycles and finally

arrive at relatively stable values. It is essential to note that for any given contact load, no obvious difference

can be observed in the friction coefficients of NAB alloys, implying that the phase transformation of

precipitates from Fe3Al to Fe3Al + NiAl has a minimal effect on the friction behavior of bulk materials. As

the contact load increases, the friction coefficients of all samples slightly decrease. This can be explained by

the fact that the most of particles lost their cutting edges, accompanied by the particle damage during the

abrasive process [46, 47]. With different mechanical properties, the NAB alloys sintered at different

temperatures are expected to exhibit varying damage resistance. Many works have focused on investigating

the effect of mechanical properties on the abrasion resistance of materials and correlating their tribological

performances with their composition-related mechanical properties [48, 49]. Indeed, compared with NAB

alloys obtained at 650 and 700 °C, a relative higher damage resistance of the NAB alloy obtained at 750 °C

can be observed for all test conditions, as illustrated from the 3D morphologies of the wear tracks (Fig. 9).

Fig. 10a presents quantitative measurements of wear in NAB specimens. Values of the wear volume are

substantially higher for the NAB-600 compared to those of the NAB-750. This suggests that the precipitates

have a strong impact on the wear behavior of the NAB alloys, despite the minimal effect on the friction

performance. At 106 N, wear tracks of the NAB alloys sintered at 600 and 750 °C with different precipitates

are examined by SEM, as shown in Fig. 10b and c. In these images, the plastic deformation and abrasion
11
wear showing surface plowing by asperities, as well as cracked transfer layers can be seen, and some

patches of the compressed transfer layer remain on wear tracks (identified by white arrows). Specifically, the

crack propagation can be observed on the high-magnification image of the wear track of the NAB-600 (the

inset in Fig. 10b). Although such a crack could extend from its original length during the specimen

preparation, inter- or trans-granular cracks are not detected on the magnification image of the wear track of

the NAB-750 (the inset in Fig. 10c). Therefore, it can be assumed that NAB-750 with Fe3Al + NiAl

precipitates has a higher wear resistance than NAB alloys with a single Fe3Al-precipitate phase. This can be

further confirmed by the dissipated energy of NAB alloys during fretting, which can be defined as

Ed = μ‧ P‧ d (Joules) (4)

where μ is the average friction coefficient, P is the applied load and d is the total fretting distance. Fig. 10d

presents the wear volume as a function of the dissipated energy for NAB alloys. The wear volume and the

dissipated energy of all NAB specimens fit with linear relationships. The slope of NAB-600 is relatively

higher than that of NAB-600, indicating a higher wear rate of the NAB-600 (181397 μm3/J) compared with

those of the NAB-700 (157680 μm3/J) and the NAB-750 (150346 μm3/J).

4. Discussion

4.1. Influence of sintering temperatures on mechanical and tribological properties

Despite the application of different sintering temperatures during SPS processes, the final average grain

size of all bulk materials is maintained at ~ 400 nm (Fig. 3 and Fig. 4a) due to high cooling and fast

solidification rates. This work demonstrates that the gas-atomized and spark plasma sintered NAB alloys

with ultra-fine grains can exhibit extraordinary compressive ultimate strengths of 1480-1700 MPa at room

temperature with a plastic strain of > 40% (Fig. 7). NAB-750 shows the excellent yield strength of 620-630

MPa. Although these high ultimate strengths were obtained by the compression mode, the results would

12
boost more research interests and efforts into the methodology for the development of ultrahigh strength of

Cu-based alloys using gas-atomization and spark plasma sintering. This is inferred from results of the

comparison with strengths of many conventional high-strength NAB alloys, in which various heat treatment

methods were used (Table 3). The present bulk materials exhibit better strengths (yield strength of 540 MPa,

ultimate strength of 1480 MPa) even at the sintering temperature of 600 °C compared with the cast

counterparts.

Both the strength and the wear resistance of the sintered bulk materials increase with increasing the

sintering temperature. Besides the fine grain size of sintered alloys, microstructure characterizations indicate

that the volume fraction of the B2-type NiAl precipitate increases with the sintering temperature. With the

Fe3Al precipitate, the NiAl phase uniformly distributes in the NAB alloy to form intragranular and

intergranular precipitates. The increase in the strength and the wear resistance of SPS-consolidated NAB can

be attributed to the grain refinement and the fine dispersion of the precipitation in bulk materials, since

varying degrees of segregation are commonly observed in the cast alloys after heat treatment [50].

Compared with the Fe3Al precipitate, the NiAl phase with higher elastic modulus of 231 GPa and yield

strength of 400 MPa further promotes the wear resistance of NAB bulk materials. Consequently, NAB-750

exhibits the lowest wear rates at all wear test conditions.

Furthermore, a high dislocation density in the sintered bulk samples is observed. This could be caused

by the high density of precipitation existing in the grain interiors, which reduces the recovery rate.

Nanoscale twins are retained with average twin thickness of 50 nm, which all facilitate the high strength and

the wear resistance. Thus, based on microstructural observation as well as mechanical and tribological test

results, five contributions to the high strength and the excellent wear resistance of the sintered bulk samples

could be determined, which are GB strengthening, precipitate strengthening, dislocation strengthening, TB

strengthening and solid solution strengthening, as illustrated in Fig. 11.

13
4.2. Strengthening mechanisms for sintered bulk materials

The GB strengthening can be estimated through the Hall-Petch law [51]. A decrease of the grain size

could induce an increase of the total grain boundary length, hindering the motion of dislocations. For

precipitate strengthening, since the precipitates have an average particle size of 47 nm, the Orowan by-pass

mechanism is expected to be operative for the dislocation motion rather than the particle shearing

mechanism. In addition, the microstructural analysis shows a high dislocation density particularly at the TBs.

Therefore, the dislocation strengthening relation should be considered, which relates the critical stress for an

onset of slip to the square root of the dislocation density. Furthermore, coherent twins observed in ultrafine

grains contribute to the high strength similar to that of the GB via Hall-Petch type strengthening. Finally, the

solute atoms in the Cu solid solution contribute strengthening to the metal matrix through the generation of

an elastic strain caused by the atom misfit, and the mismatch of elastic moduli between solute and solvent

atoms.

4.2.1. GB strengthening

It is demonstrated that GB strengthening follows the Hall-Petch relationship, which relates the yield

stress enhancement to the grain size as [51]

1
Δσ𝐻𝑃 = σ0 + 𝐾𝐻𝑃 𝑑−2 (5)

where KHP is the Hall-Petch coefficient, σ0 constitutes the overall resistance of the crystal lattice to the

dislocation motion, and d is the average grain diameter (325 nm). KHP and σ0 are assumed to be 0.17

MPa‧ m1/2 and 36.2 MPa, respectively, for polycrystalline Cu with d > 2·10-7 m [52]. Therefore, the total

GB strengthening is 335 MPa.

14
4.2.2. Precipitate strengthening

The corresponding strengthening effect of precipitates by Orowan looping can be described by

̅
2𝑟
𝑀𝐺𝑏 ln 𝑏
Δσ𝑂𝑟 = (6)
2𝜋𝜆 √1−𝜈

𝑟̅ = √2/3𝑟 (7)

where M is the Taylor factor of the fcc polycrystalline matrix (3.06) [38], G and b are the shear modulus

(42.1 GPa) and the magnitude of the Burger vector (0.256 nm) [53] of the matrix, respectively. υ represents

the Poisson’s ratio (0.34) of the matrix [52]. r is the mean precipitate radius of 23.5 nm, and λ is the effective

inter-precipitate spacing which can be estimated by [51]

4𝑟(1−𝑓)
λ= (8)
3𝑓

where f is the volume fraction of precipitates (5%). Finally, the contribution from the precipitates

strengthening ΔσOr is 54 MPa.

4.2.3. Dislocation strengthening

The contribution from the dislocation strengthening Δσd, is [39]

1
Δσ𝑑 = 𝑀𝛼𝐺𝑏𝜌2 (9)

where α is a constant (taken as 0.2 for fcc metals), ρ is the dislocation density of 1.3 ± 0.1 × 1014 m-2. M, G

and b have the same significance as above. Hence, the calculated Δσd is 75 MPa.

4.2.4. TB strengthening

Coherent twins contribute to the strength via Hall-Petch type strengthening:

1
−
𝛥𝜎𝑇𝐵 = 𝑉𝑓 𝐾𝑇𝐵 𝜆 𝑇𝐵2 (10)

where KTB is a constant and can be approximated to the Hall-Petch constant of the corresponding material. Vf

is the total volume fraction of twins. λTB is the average TB thickness, which is 50 nm from the TEM

15
observation (Fig. 5c). Previous works by Wen et al. [38] demonstrated that the volume fraction of twins is

~10% in the SPS-consolidated Cu-based alloy, which is similar with the result in this work (11.7%). With

these parameters, the contribution of twins to strengthening is obtained to be 89 MPa.

4.2.5. Solid solution strengthening

This contribution solid solution strengthening (Δσss) also has a significant effect on the yield strength.

For conventional binary solid solutions, well-established models are valid for the related strengthening

mechanisms governed by elastic interactions between dislocations and the solute atom-induced stress

[54-56]. As NAB is the Cu-based alloy with a complex composition, Senkov et al. [57] proposed an equation

to estimate solid solution strengthening as

4 2
𝛥𝜎𝑠𝑠 = 𝐴𝐺 3 𝐶 3 (11)

where A is a dimensionless parameter of 0.1. G and C are the shear modulus and concentration of solute

atoms, respectively. ε is the lattice strain caused by solute atoms. In an AlCoCrCuFeNi system, Ganji et al.

[58] suggested that Al might cause more strain to the copper based lattice with a strain of 12%. For the

current composition (AlCuFeNiMn), it is approximated that the strain of 12% caused by Al atom could be

taken as the effective strain. Therefore, the concentration of Al solute atoms is 0.09 based on the analysis of

the fraction of Al in the matrix and precipitates. Hence, the strength increment of Δσss is 50 MPa.

With the above-mentioned calculation, the contribution proportions from ΔσHP, ΔσOr, Δσd, ΔσTB and Δσss,

are 54%, 8.7%, 12%, 14.4% and 8%. Meanwhile, a proportion from the slightly underestimated yield

strength (~3%) can be obtained, which may result from dislocation-twin interactions observed in Fig. 6. The

interactions between dislocation strengthening and TB strengthening mechanisms could create more

pronounced effects [43, 59, 60]. As noted, a fraction of dislocations is observed to present and concentrate at

TBs. Recent study demonstrates that the dislocation interaction with and accumulation at twin boundaries

significantly improve the strength of fcc metals and alloys [61] because dislocations are blocked by the TBs

16
due to the discontinuity in slip systems of two crystals. Thus, in order to slip from one grain to the twin,

cross slip or dislocation nucleation would occur at the TB. However, the sessile dislocations could serve as

barriers to the motion of other dislocations and prevent dislocation nucleation in the system. This is

consistent with TEM observations in which the NAB-750 sample contains a high-density of dislocations at

the TBs (Fig. 5). Molecular dynamics (MD) simulation works by Wu et al. [62] showed that the sessile and

glissile dislocations together with the TBs could form complex dislocation barriers and networks, as well as

point defects during the plastic deformation, contributing to the high strength.

4.3. Effect of precipitates on tribological behaviors

The XRD, SEM and TEM characterizations indicate that NAB alloys sintered at different temperatures

exhibit significant differences in the precipitation, which consequently has a strong effect on the tribological

properties of alloys as determined from the flat-on-flat fretting wear tests. NAB alloys sintered at 750 °C

consist of ultra-fine grains (the matrix) and a large number of Fe3Al + NiAl precipitates existing at the GBs

(Fig. 3e and f). Compared with NAB-750, the NAB alloys prepared at 600 °C contain the matrix and the

Fe3Al precipitate. Both NAB-600 and NAB-750 show friction coefficients between 0.4 and 0.5 at contact

loads of 43-106 N, which possibly benefit from the intrinsic friction behavior of the copper matrix [63-65].

However, obviously different wear behaviors of the two NAB alloys are evident from the fretting wear tests

and SEM observations, in which cracks can be identified on the wear tracks of NAB-600. This can be

concluded that the precipitation exhibits more significant effect on the wear performance than on the friction

behavior. It is rather intuitive that the relative higher wear rate of NAB-600 (181397 μm3/J) compared with

that of the NAB-750 (150346 μm3/J) is related to the crack initiation and propagation on the wear tracks of

NAB-600 during fretting (Fig. 10b and c). This difference of the wear resistance of NAB alloys sintered at

600 and 750 °C motivates the discussion of crack evolution mechanisms during wear in the following

17
sub-sections.

4.3.1. Elastic modulus mismatch between the matrix and precipitates

As mentioned previously, NAB alloys contain different precipitates with Fe3Al in NAB-600 and with

Fe3Al + NiAl in NAB-750. The elastic modulus for Fe3Al and NiAl is 141 GPa [66] and 231 GPa [67],

respectively; while the modulus of copper is 129.8 GPa [68]. We first explore the influence of the elastic

modulus mismatch, which may have a significant effect on crack-tip stress fields. Two cases that are the

moderate (𝐸𝐹𝑒3 𝐴𝑙 /ECu) and the high (ENiAl/ECu) plastic mismatches are addressed. During the wear process,

the high shear stress caused by asperities could locally exceed the yield stress of NAB alloys, leading to the

crack initiation on the surface. As fretting proceeds, the crack-tip stress field would be locally continuous

across a transformation boundary. Therefore, the stress continuity across interfaces can be maintained only

by the locally relieving strain [69] both in the matrix and precipitates. When the elastic modulus mismatch is

considered, Robertson et al. [69] observed strain reversals near the crack tip, effectively providing a strain

accommodation mechanism with the reduction of the local stress. MD simulations demonstrated that traction

distributions near the crack tips were noticeably lower for the high elastic mismatch case than for the

moderate one, whereas the total displacements were about the same; meanwhile, at a given displacement, the

high mismatch case caused a reduction in the stress [70].

It can be noted that the crack propagation observed in this work is also associated with the moderate

mismatch during the wear process. In addition, SEM observations indicate the complex nature of the

structural evolution including the severe plastic deformation in the NAB system during fretting. This result

strongly suggests that the elastic modulus mismatch could not be considered as the only cause of the crack

propagation at the surface during wear, since deformations of the matrix and precipitates will both occur.

Thus, the plastic mismatch between the matrix and precipitates is also discussed in the next sub-section.

18
4.3.2. Plastic mismatch between the matrix and precipitates

The yield strength of Fe3Al and NiAl are 330 MPa [71] and 400 MPa [14], respectively. Therefore,

compared with the yield strength of copper (250 MPa [14]), the moderate (𝜎𝐹𝑒3 𝐴𝑙 /σCu) and the high (σNiAl/σCu)

plastic mismatch cases will be considered. Since the volume fraction of precipitates is 5%, a microcrack

caused by the fretting wear tends to occur near the interface of the matrix and the precipitate, and the stress

intensity factor could decrease at a given applied load due to the build-up of plastic strains [72]. This

corresponds to an increase in effective toughness, which is strongly dependent on the distance of the crack

from the interface. Moreover, as the crack is very close to the interface, a decrease of crack-tip stresses

would occur with the crack extension at the high plastic mismatch. This was demonstrated by

Charalambides et al. [73]. For the case of the high plastic mismatch, the precipitate phase (NiAl) can be

considered as a more rigid material which would lead to a reduction of crack-tip stresses with the fewer

anti-shielding effect, resulting in higher failure loading. Therefore, more plastic deformations would occur

which increase the effective toughness in subsequent crack extension increments. The higher stress is then

required for the further crack propagation. Conversely, for the moderate plastic mismatch, a less rigid

precipitate (Fe3Al) could amplify crack-tip stresses, leading to a high anti-shielding effect and low failure

loads. It has been indicated that such high anti-shielding effect could cause the less plastic deformation, and

there would be less extension toughening [72]. The failure load in crack extension increments is then limited,

resulting in the reduction in structural reliability.

Consequently, it can be concluded that the higher plastic mismatch (σNiAl/σCu), which causes the crack

extension toughening near the interface of the matrix and the precipitate, may also have a strong effect on

the superior wear resistance of NAB-750.

19
5. Conclusions

Bulk nickel-aluminium bronze alloys with the excellent wear resistance and superior strengths were

developed via gas-atomization and SPS. Detailed comparative research was carried out to determine the

relationship between the sintering temperature and mechanical/tribological properties of samples.

Microstructural characterizations of NAB-750 showed that its high strength was attributed to the uniformly

distributed precipitates (Fe3Al and NiAl) both in ultrafine-grain interiors and at GBs, the high dislocation

density, the TBs inside grain interiors and the solid solution. The wear resistance could be related to the

elastic modulus mismatch and the plastic mismatch between the matrix and precipitates. The following

conclusions can be drawn:

 Fine intragranular and intergranular precipitates with a volume fraction of 5% are formed after the

sintering process. The NiAl content is increased by increasing the sintering condition to 750 °C, while

the Fe3Al content is decreased. Their total fraction and size remain rather constant for each sintering

temperature.

 At 750 °C, the sintered bulk materials show an average grain size of 367 nm with a high density of

twins (11.7 vol%), a dislocation density of 1.3 ± 0.1 × 1014 m-2 and an Al-solute concentration of 0.09.

Comprehensive analyses on strengthening mechanisms suggest that GB strengthening (335MPa) is the

predominant mechanism for the sintered bulk materials with contributions from precipitate

strengthening (54 MPa), dislocation strengthening (75 MPa), TB strengthening (89 MPa) and solid

solution strengthening (50 MPa). In addition, high-density dislocations are blocked at TBs to form

complex dislocation barriers and networks, further contributing to the high strength of NAB alloys.

 NAB alloys exhibit excellent wear properties, with an increase in wear resistance with increasing the

sintering temperature. The excellent wear resistance can be ascribed to the reduction of the local stress

around the crack tip due to the high elastic modulus mismatch (ENiAl/ECu), and the crack extension

20
 toughening near the interface of the matrix and the precipitate caused by the high plastic mismatch

(σNiAl/σCu).

Acknowledgments: The article was supported by the National Basic Research Program of China [grant

No. 2014CB046705]; the China Postdoctoral Science Foundation [Grant No. 2016M600586]; and the

National Natural Science Foundation of China (NSFC) [Grant No. 51421062].

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 Figure captions
Fig. 1. SEM image of raw powders, the inset shows the particle size between 5 and 25 μm.

Fig. 2. Evolution of XRD patterns of NAB samples sintered at 600, 650, 700 and 750 °C, the inset shows the
peak splitting of the Fe3Al peak at different sintering temperatures.

Fig. 3. SEM images at two magnifications showing the microstructures for the bulk materials sintered at (a
and b) 600, (c and d) 700 and (e and f) 750 °C

Fig. 4. TEM characterizations of the sintered bulk sample at 750 °C: (a) an average grain size of 367; (b and
c) both bright and dark field images indicate the presence of precipitates; (d) size distribution of precipitates;
(e) an example of the EDX spectra of the precipitates; the inset in the image a indicates the ultrafine grains
with random crystallographic orientations; the inset in b shows the SAED pattern of the matrix; the inset in c
gives the SAED patterns of the matrix, B2 phase NiAl and D03 phase Fe3Al in [1̅11]

Fig. 5. (a) TEM bright field image of NAB-750 reveals twins in grains; (b) numerous twins observed in the
NAB-750; (c) distribution of the twin thickness; (d) distribution of twin spacing.

Fig. 6. (a) TEM image showing dislocations between TBs; (b) a high magnification image displaying the
inhibition of dislocation movement at the TB.

Fig. 7. Representative (a) compressive and (b) tensile stress-strain curves of NAB-600 and NAB-750.

Fig. 8. Evolutions of friction coefficients of NAB-600, NAB-700 and NAB-750 as a function of fretting
cycles tested at contact loads of (a) 43, (b) 86 and (c) 106 N.

Fig. 9. 3D morphologies of the wear tracks of NAB-600, NAB-700 and NAB-750 after wear tests at 43, 86
and 106 N.

Fig. 10. (a) Wear volumes of NAB-600, NAB-700 and NAB-750 tested at 43, 86 and 106 N; (b and c) wear
tracks of NAB-600 and NAB-750 at 106 N; (d) the wear volume as a function of the dissipated energy for
NAB alloys.

Fig. 11. Strengthening mechanisms based on the microstructural observations including GB strengthening,
precipitate strengthening, dislocation strengthening, TB strengthening and solid solution strengthening.

29
Fig. 1. SEM iamge of raw powders, the inset shows the particle size between 5 and 25 μm.

30
Fig. 2. Evolution of XRD patterns of NAB samples sintered at 600, 650, 700 and 750 °C, the inset shows the
peak splitting of the Fe3Al peak at different sintering temperatures.

31
Fig. 3. SEM images at two magnifications showing the microstructures for the bulk materials sintered at (a
and b) 600, (c and d) 700 and (e and f) 750 °C

32
Fig. 4. TEM characterizations of the sintered bulk sample at 750 °C: (a) an average grain size of 367; (b and
c) both bright and dark field images indicate the presence of precipitates; (d) size distribution of precipitates;
(e) an example of the EDX spectra of the precipitates; the inset in the image a indicates the ultrafine grains
with random crystallographic orientations; the inset in b shows the SAED pattern of the matrix; the inset in c
gives the SAED patterns of the matrix, B2 phase NiAl and D03 phase Fe3Al in [1̅11]

33
Fig. 5. (a) TEM bright field image of NAB-750 reveals twins in grains; (b) numerous twins observed in the
NAB-750; (c) distribution of the twin thickness; (d) distribution of twin spacing.

34
Fig. 6. (a) TEM image showing dislocations between TBs; (b) a high magnification image displaying the
inhibition of dislocation movement at the TB.

35
Fig. 7. Representative (a) compressive and (b) tensile stress-strain curves of NAB-600 and NAB-750.

36
Fig. 8. Evolutions of friction coefficients of NAB-600, NAB-700 and NAB-750 as a function of fretting
cycles tested at contact loads of (a) 43, (b) 86 and (c) 106 N.

37
Fig. 9. 3D morphologies of the wear tracks of NAB-600, NAB-700 and NAB-750 after wear tests at 43, 86
and 106 N.

38
Fig. 10. (a) Wear volumes of NAB-600, NAB-700 and NAB-750 tested at 43, 86 and 106 N; (b and c) wear
tracks of NAB-600 and NAB-750 at 106 N; (d) the wear volume as a function of the dissipated energy for
NAB alloys.

39
Fig. 11. Strengthening mechanisms based on the microstructural observations including GB strengthening,
precipitate strengthening, dislocation strengthening, TB strengthening and solid solution strengthening.

40