crystals
Article
The Influence of Ni-Added Fe-Based Pre-Alloy on
Microstructure Evolution and Lifetime Extension of
Diamond Tools
Juan Pu 1, * , Yubo Sun 1 , Weimin Long 2 , Mingfang Wu 1 , Dashuang Liu 1 , Sujuan Zhong 2 and Songbai Xue 3






Citation: Pu, J.; Sun, Y.; Long, W.;
Wu, M.; Liu, D.; Zhong, S.; Xue, S.
The Influence of Ni-Added Fe-Based
Pre-Alloy on Microstructure
Evolution and Lifetime Extension of
Diamond Tools. Crystals 2021, 11,
1427. https://doi.org/10.3390/
cryst11111427
Academic Editor: Cyril Cayron
Received: 20 October 2021
Accepted: 17 November 2021
Published: 21 November 2021
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Copyright: © 2021 by the authors.
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This article is an open access article
distributed under the terms and
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Crystals 2021, 11, 1427. https://doi.org/10.3390/cryst11111427
1 School of Materials Science and Engineering, Jiangsu University of Science and Technology,
Zhenjiang 212003, China; suyub_513@163.com (Y.S.); wu_mingfang@163.com (M.W.);
dsliu@just.edu.cn (D.L.)
2 Zhengzhou Research Institute of Mechanical Engineering, Zhengzhou 450001, China;
brazelong@163.com (W.L.); sujuan_zh@163.com (S.Z.)
3 College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics,
Nanjing 210016, China; xuesb@nuaa.edu.cn
* Correspondence: pu_juan84@163.com; Tel.: +86-159-5281-5816
Abstract: Diamond tools were prepared by sintering Fe-Cu-Sn-Zn-Ni pre-alloyed powders and
diamonds. The effects of Ni contents in pre-alloyed powders on microstructure evolution of Fe-based
matrix, the properties of Fe-based matrix and the service life of diamond tools were investigated.
The results showed that adding 3~15 wt.% Ni into the Fe-Cu-Sn-Zn pre-alloyed powders refined the
microstructure of the Fe-based matrix and improved its density and hardness gradually. The addition
of Ni reduced the loss of low melting liquid phase at a low sintered temperature, thus resulting in
a decrease of the pores, an increase of the density and hardness of Fe-based matrix. When the Ni
content is less than 9 wt.%, the bending strength of Fe-based matrix and diamond tools, together with
the holding force of Fe-based matrix to diamonds increases sharply. They reached up to the optimal
value with the Ni content of 9 wt.%. At this sintering powder ratio, the sufficient Fe-Cu-Sn-Zn-Ni
liquid phase had a good wettability on the surface of diamonds, thus the optimal performance of
sintered matrix and diamond tools was obtained. The service life of diamond tools was prolonged
greatly owing to the excellent bonding capacity between matrix and diamonds. Once the Ni content
exceeded 9 wt.%, the corresponding value decreased gradually. The fracture morphologies of the
matrix changed from the brittle fracture into brittle-ductile fracture, then ductile fracture (with the Ni
content of 9 wt.%), brittle-ductile mixed fracture and brittle fracture.
Keywords: Fe-Cu-Sn-Zn-Ni pre-alloyed powders; diamond tools; density; bending strength;
holding ability
1. Introduction
Diamond tools are usually sintered by diamond particles and metal-based powders
through powder metallurgy technology such as hot pressing or cold pressing-sintering [1].
In order to maintain the sharpness of diamond tools and prolong their service life during
cutting or polishing, the holding force of the matrix to diamonds is very important. It is
generally known that Co-based matrix has a strong holding ability to diamonds, which
has excellent comprehensive properties, such as good red hardness, toughness and self-
sharpening. However, its price is high and its reserves are short, the application of Co-based
matrix is limited [2–4]. Therefore, researchers are committed to the development of Co free
or low Co metal matrix.
Fe is rich in resources and is low in price. It has many similar properties with Co.
Moreover, it has a good wettability on the surface of diamonds, which can produce a good
bonding force between Fe-based matrix and diamonds, finally, their interfacial bonding
https://www.mdpi.com/journal/crystals
Crystals 2021, 11, 1427 2 of 11

strength is improved [5,6]. Thus Fe has become a hot spot in the research of sintered matrix
materials in recent years [7,8].
In general, Fe is susceptible to eroding the diamond seriously at a high sintered
temperature (900~1100 ◦ C), thus the diamond is easy to be graphitized, which results in a
decrease in the strength and the service life of diamond tools. In this case, it is necessary
to decrease the sintered temperature of Fe-based metal matrix in order to improve its
comprehensive properties and expand its applications. Some research results [9–12] show
that using pre-alloyed powders to replace powders particles in a sintered matrix can
decrease the sintered temperature. Chen Zhengwei et al. [13] studied the application of Fe-
based pre-alloyed powders in diamond tools. He concluded that the properties of Fe-based
matrix material can reach the level of Co-based matrix material as long as the formulation
of Fe-based pre-alloyed powders was reasonable. In addition, some scholars insist on one
view that adding Cu, Sn and Zn into Fe powders can effectively decrease the sintered
temperature of Fe-based matrix and ensure its good comprehensive performance [14–17].
However, the melting point of Sn and Zn is low, so the loss of Fe-Cu-Sn-Zn liquid phase is
serious at a low sintered temperature, which weakens the binder action of Fe-Cu-Sn-Zn
liquid phase.
Ni has a high melting point and density, and it is a favorable strengthening and
toughening element for Fe-based powder metallurgical materials [18,19]. Therefore, in
this paper, different Ni contents are added into Fe-Cu-Zn-Sn powders, and then they are
prepared into pre-alloyed powders. These pre-alloyed powders and diamonds will be
sintered into diamond tools by powder metallurgy. The effects of different Ni contents in
pre-alloyed powders on the properties of Fe-based sintered matrix and diamond tools will
be discussed. The influence mechanism of Ni-containing pre-alloyed powders on the life
extension of diamond tools will be analyzed. These studies aim to enrich the theoretical
basis for the preparation of diamond tools.

2. Materials and Methods

2.1. Experimental Materials
The raw materials included iron powder, copper powder, tin powder, nickel powder,
zinc powder and self-made pre-alloyed powder. The particle size was 200 mesh. The pre-
alloyed powder was prepared by multistage tightly coupled atomization. The composition
ratio of pre-alloyed powder was listed in Table 1. The diamond with the brand of HTD2620
was chosen. Its size was 40 mesh. The concentration of diamond was 20% (based on 400%
concentration system). In order to study the effect of Ni content in the pre-alloyed powder
on the microstructure of Fe-based matrix and the performance of matrix and cutter head of
diamond tools, six kinds of composition design were formulated, which were marked as
T1, T2, T3, T4, T5 and T6, with Ni contents of 0%, 3%, 6%, 9%, 12% and 15%, respectively.

Table 1. The composition ratio of pre-alloyed powder.

Composition Ratio (wt.%)

Ni 0–15
Sn 2–10
Cu 15–25
Zn 10–15
Fe Balance

2.2. Experimental Process

The powders were weighted according to the composition design shown in Table 1.
The powders were mechanically mixed in a three-dimensional mixer for 30 min. In the
mixing process, about 2% paraffin or kerosene was added to prevent the segregation of
the powders and facilitate the press molding of the cutter head. Then, they were put into
the Graphite Mold to be sintered in the hot press sintering machine (SMVB60). During the
sintering process, the sintering parameters were the highest temperature of 800 ◦ C and the
 the powders and facilitate the press molding of the cutter head. Then, they were put into
the Graphite Mold to be sintered in the hot press sintering machine (SMVB60). During the
Crystals 2021, 11, 1427
sintering process, the sintering parameters were the highest temperature of 800 3°C of 11
and
the holding time of 60 s. After sintering, the size of samples was 40 mm × 8 mm × 3.2 mm.
The specific sintering process was shown in Figure 1.
holding time of 60 s. After sintering, the size of samples was 40 mm × 8 mm × 3.2 mm.
The specific sintering process was shown in Figure 1.

900
850 28
800 Temperature
Pressure
750 24
700
Temperature (℃)

Pressure(KN)
650 20
600
550 16
500
450 12

400
8
350
300
0 30 60 90 120 150 180
Time (s)

Figure 1. Sintering process of powders.

Figure 1. Sintering process of powders.
There are some details to pay attention to during the experiment. Cu and Ni in the
There areare
powders easily
some oxidized
details at room
to pay temperature.
attention to during Duethe
to the existence of
experiment. Cuoxides,
and Nion in
thethe
one hand, the graphitization of diamond will be intensified and the surface of the diamond
powders are easily oxidized at room temperature. Due to the existence of oxides, on the
will be strongly eroded, finally, the cutting performance of diamond will be reduced. On
one hand, the graphitization of diamond will be intensified and the surface of the dia-
the other hand, pores may be formed in the sintering process, which results in the reduction
mondofwill be strongly
the strength of theeroded, finally,
matrix and the
cutter cutting
head. performance
Therefore, of diamond
the powder will be re-
storage equipment
duced. On the other hand, pores may be formed in the sintering process, which
includes gas-making equipment and a reduction furnace. The reducing agent is hydrogen results in
the reduction of Moreover,
or coal gas. the strength of themold
graphite matrix and cutter
is selected as a head.
carrierTherefore, the powder
during powder sintering.storage
The
equipment includes
compressive gas-making
strength equipment
of graphite shall notand a reduction
be less than 40 MPa,furnace. The reducing
the porosity agent
of graphite
shall not be greater than 30%, and the density shall be above 1.6 g/cm 3.
is hydrogen or coal gas. Moreover, graphite mold is selected as a carrier during powder
sintering. The compressive strength of graphite shall not be less than 40 MPa, the porosity
2.3. Performance Testing and Microstructural Analysis
of graphite shall not be greater than 30%, and the density shall be above 1.6 g/cm3.
The immersion paraffin method was used to measure the sintering density of samples
according to the standards GB/T10451-2002 and GB 3850-83. The sample after being
2.3. Performance Testing and Microstructural Analysis◦
immersed in paraffin at the temperature of 170 C was weighed in the air and in the
The immersion
water, respectively.paraffin methoddensity
The sintering was


used to measure
of samples the sintering
was calculated by thedensity
formulationof sam-
of ρ = m ·
ples accordingairtowater ρ the standards
/ m p− air − mGB/T10451-2002
p−water , where m and
air GB 3850-83. The sample after being
is the weight of the samples in the air,
m p− airinisparaffin
immersed the weight of the
at the samples that
temperature are °C
of 170 immersed in paraffin
was weighed in air
in the air, m
theand inp−
the
water is
water,
the weight of the samples that are immersed in paraffin in the
respectively. The sintering density of samples was calculated by the formulation of = water and ρ water is the
∙density/( of the water. The theoretical density of samples was calculated according to the
− ), where is the weight of the samples in the air,
formula ρ0 = 100/( mρ 1 + mρ22 + mρ33 + · · · + mρnn ), where m1 , m2 · · · mn represents the mass
is the weight of the samples that are immersed in paraffin in the air,
1 is
percentage of each component in the sample and ρ1, ρ2 · · · ρn is the theoretical density of
the weight of the samples that are immersed in paraffin in the water
each component in the sample. The sample density was calculated by the formulation of and is the
densityη =ofρ/ρthe0 . water. The theoretical density of samples was calculated according to the
formula The=hardness 100/( of + sintered
+ matrixes
+ ⋯ ⋯ +was),measured
where perpendicular
, ⋯ ⋯ to therepresents
pressing di-the
rection by a Rockwell hardness tester (HRB).
mass percentage of each component in the sample and , ⋯ ⋯ The reported values are an average
is the theoreticalof five
den-
data points.
sity of each component in the sample. The sample density was calculated by the formula-
Three-point bending tests were carried out to measure the bending strength of the
= /matrix
tion ofsintered . and diamond tools on a universal testing machine (CMT5205) under the
 The hardness of sintered matrixes was measured perpendicular to the pressing di-
rection by a Rockwell hardness tester (HRB). The reported values are an average of five
data points.
Three-point bending tests were carried out to measure the bending strength of the
Crystals 2021, 11, 1427 sintered matrix and diamond tools on a universal testing machine (CMT5205) 4under of 11 the
loading speed of 1mm/min and span length of 30 mm. The bending test was repeated 5
times and the final result was taken as the average value.
The microstructure of the sintered matrix was observed by a ZEISS optical micro-
loading speed of 1mm/min and span length of 30 mm. The bending test was repeated
scope (OM,
5 times Oberkochen,
and Germany).
the final result was takenThe fracture
as the averagemorphologies
value. of the sintered matrix and
diamond Thetools were analyzed
microstructure by a JSM-6480
of the sintered matrix wasscanning
observedelectron microscope
by a ZEISS (SEM, JEOL,
optical microscope
Tokyo,
(OM,Japan). The chemical
Oberkochen, Germany).composition
The fractureof the fracture was
morphologies of tested by Energy
the sintered matrixDispersive
and
Spectrometer (EDS). The tissue of sintered matrix was analyzed by an XRD-6000 X-ray
diamond tools were analyzed by a JSM-6480 scanning electron microscope (SEM, JEOL,
Tokyo, Japan).instrument
diffractometer The chemical composition
(XRD, Shimadzu,of the fracture
Kyoto, was tested
Japan). X-ray bydiffraction
Energy Dispersive
(XRD) anal-
Spectrometer (EDS). The tissue of sintered matrix was analyzed by an
ysis was carried out with Cu-Kα radiation and scanning angles (2θ) between 10°and XRD-6000 X-ray 90°.
diffractometer instrument (XRD, Shimadzu, Kyoto, Japan). X-ray diffraction (XRD) analysis
was carried out with Cu-Kα radiation and scanning angles (2θ) between 10◦ and 90◦ .
3. Results and Discussion
3.1.3.Effect
Results and
of Ni Discussion
Content on the Microstructure
3.1. Effect of Ni Content on the Microstructure
Figure 2 shows the microstructure of sintered matrixes with different Ni contents.
When the Figure 2 shows the
pre-alloyed microstructure
powders contain of sintered
Ni-free, thematrixes
grain size withofdifferent
sinteredNi contents.
matrix is coars-
When the pre-alloyed powders contain Ni-free, the grain size of sintered matrix is coars-
ened, some light-colored copper-based bonding phase segregates at the grain boundary,
ened, some light-colored copper-based bonding phase segregates at the grain boundary,
some continuous “linear” pores and a few irregular pores appear, as shown in Figure 2a.
some continuous “linear” pores and a few irregular pores appear, as shown in Figure 2a.
Figure
Figure2b–f
2b–fshow
showthat
thatthe
the grains graduallybecome
grains gradually become fine
fine andand those
those light-colored
light-colored copper-
copper-
based
basedbonding
bonding phase
phasebegin
begintotodistribute
distributeuniformly
uniformly in in the
the sintered
sintered matrix, and those
matrix, and those con-
tinuous
continuous “linear” pores and irregular pores disappear gradually. It can be concluded that
“linear” pores and irregular pores disappear gradually. It can be concluded
thethat
addition of Ni of
the addition in Ni
pre-alloyed powders
in pre-alloyed plays
powders thethe
plays roleroleofofgrain
grainrefinement onthe
refinement on the sin-
sintered
tered matrix matrix and
and it canit reduce
can reduce
thethe number
number of of poresofofthe
pores thesintered
sintered samples.
samples. Moreover,
Moreover, the
the size
grain graingrows
size grows
finerfiner
withwith
the the increase
increase of of
thethe
NiNicontent.
content.

Figure 2. Microstructure
Figure of sintered
2. Microstructure matrixes
of sintered matrixeswith
withdifferent Ni content.
different Ni content.(a)
(a)Ni-free;
Ni-free;(b)(b) with
with 3. wt.%
3. wt.% Ni;with
Ni; (c) (c) with 6 wt.%
6 wt.% Ni; Ni;
(d) with 9 wt.%
(d) with Ni; (e)
9 wt.% Ni; with 12 12
(e) with wt.%
wt.%Ni; (f)(f)with
Ni; with15
15wt.%
wt.% Ni.
Ni.

Figure3 3shows
Figure shows thethe variation
variationofof
thethe
sintering density
sintering ρ, the theoretical
density density ρdensity
, the theoretical 0 and
the density η of sintered matrix under different Ni contents in pre-alloyed
and the density of sintered matrix under different Ni contents in pre-alloyed powders.powders. As
the addition of Ni in pre-alloyed powders is less, the theoretical density ρ0 of sintered
As the addition of Ni in pre-alloyed powders is less, the theoretical density of sintered
matrix changes little. The sintering density ρ as well as the density η increase gradually
matrix changes little. The sintering density as well as the density increase
and the porosity decreases with the increase of Ni content in the pre-alloyed powder. As
gradually
andSnthe
andporosity
Zn in the decreases withlow
powder have the melting
increasepoints,
of Ni they
content
can in theapre-alloyed
form liquid phasepowder.
at low As
Sn sintering
and Zn in temperature. Then these liquid phase fills the voids in the sintered matrix soat low
the powder have low melting points, they can form a liquid phase
that the density of the matrix is improved. However, the liquid phase with a low melting
point is easy to flow away at lower sintering temperatures, so the role of Cu, Zn and Sn
Crystals 2021, 11, x FOR PEER REVIEW 5 of 11
sintering temperature. Then these liquid phase fills the voids in the sintered matrix so tha
the density of the matrix is improved. However, the liquid phase with a low melting poin
is easy to flow away at lower sintering temperatures, so the role of Cu, Zn and Sn as bond
sintering temperature. Then these liquid phase fills the voids in the sintered matrix so that
Crystals 2021, 11, 1427
ing phase is weakened. Due to the high melting point of Ni, the addition of Ni5 reduces of 11
the
the density of the matrix is improved. However, the liquid phase with a low melting point
loss of low melting point liquid phase. Therefore, the sintering density as well as the
is easy to flow away at lower sintering temperatures, so the role of Cu, Zn and Sn as bond-
density increases with the increase of Ni contents.
ing phase is weakened. Due to the high melting point of Ni, the addition of Ni reduces the
loss of low phase
as bonding melting point liquid
is weakened. Duephase.
to the Therefore, the
high melting sintering
point density
of Ni, the additionasofwell
Ni as the
density
reduces theincreases
loss of lowwith the increase
melting of Ni
point liquid contents.
phase. Therefore, the sintering density ρ as
Sintering
well as the density density（ρ）
η increases with the increase of Ni contents.
8.4 99
Theoretical density（ρ0）
Density(η)
Sintering density（ρ）
8.28.4 Theoretical density（ρ0）
99
98
Density(η)
Density(g/cm3)

Density(%)
8.2 98
8.0 97
Density(g/cm3)

Density(%)
8.0 97
7.8 96

7.8 96
7.6 95

7.6 95
7.4 94
6 09 3 12 15
7.4 Ni (wt.%) 94
0 3 6 9 12 15
Ni (wt.%)
Figure 3. Density of the sintered matrix with different Ni contents.

3. Density
Figure 3.
Figure Densityofofthe sintered
the matrix
sintered withwith
matrix different Ni contents.
different Ni contents.
Figure 4 shows the XRD analysis results of the matrix phase with different Ni content
The matrixFigure 4 shows
phase the XRD analysis
is composed withresults
Cu3Sn, of Cu
the 5matrix phase
Zn8 and Fewith
as Ni different
is freeNiincontent.
the pre-alloy
The Figurephase
matrix 4 shows
is the XRD analysis
composed with Cu results
Sn, Cu of
Zn the matrix
and Fe as phase
Ni is with
free indifferent Ni content.
the pre-alloy
(see Figure 4a). When Ni is added into the 3 pre-alloy,
5 8 the new phase of Fe-Ni solid solution
The matrix4a).
(see Figure phase
When is Ni
composed withtheCu
is added into 3Sn, Cuthe
pre-alloy, 5Znnew
8 and Fe as
phase of Ni is free
Fe-Ni solidin the pre-alloy
solution
are (see
observed, as shown
Figure 4a). inisFigure 4b. With the addition of phase
Ni, Fe-Ni solid solution i
are observed, asWhen
shownNi added4b.
in Figure into
Withthe the
pre-alloy, the
addition ofnew
Ni, Fe-Ni of Fe-Ni
solid solid
solution issolution
formed
are in the
formed in the
observed, microstructure,
microstructure,
as shown in whichwhichrefines
Figure refines
4b. Withthethe matrix
matrix
the microstructure
microstructure
addition of Ni,and and
improves
Fe-Ni improves
solid solutionthe
the is
matrix density.
matrix density.
formed in the microstructure, which refines the matrix microstructure and improves the
matrix density.

Figure 4. XRD
4. XRD
Figure analysis
analysis resultsofofthe
results the matrix
matrix phase:
phase:(a)(a)
Ni-free; (b) with
Ni-free; 15 wt.%
(b) with Ni. Ni.
15 wt.%
Figure 4. XRD analysis results of the matrix phase: (a) Ni-free; (b) with 15 wt.% Ni.
3.2. Lifetime Extension of Ni-Added Fe-Based Pre-Alloy Brazing Coating in Diamond Tools
3.2. Lifetime Extension of Ni-Added Fe-Based Pre-Alloy Brazing Coating in Diamond Tools
3.2. Lifetime
3.2.1. Extension
Effect of Ni Content of Ni-Added
on HardnessFe-Based Pre-Alloy Brazing Coating in Diamond Tools
of Matrix
3.2.1. Effect of Ni Content onRockwell
Hardness of Matrix
3.2.1.Figure
Effect5of
shows that the
Ni Content hardness
on Hardness of sintered matrix with different Ni contents
of Matrix
inFigure 5 shows
powders. thatpowder
When the the Rockwell hardness
does not contain Ni, of
thesintered
hardnessmatrix withHRB.
is only 75.3 different
When Ni con
Figure 5 shows that the Rockwell hardness of sintered matrix with different Ni con-
tentstheinNi content isWhen
powders. increased
the from 0% todoes
powder 15%, not
the hardness
contain is increased
Ni, the from 75.3
hardness is HRB 75.3
only to HRB
tents in powders.
96.7 HRB. When
The results are the powder
explained as does not Firstly,
follows. containtheNi,sintered
the hardness is only 75.3
matrix consists of HRB.
WhenWhen thethe
Ni Nicontent is is
content increased
increasedfrom
from0% 0%toto15%,
15%,thethehardness
hardness is is increased from 75.3
increased from 75.3
Crystals 2021, 11, x FOR PEER REVIEW 6 of 11

HRB to 96.7 HRB. The results are explained as follows. Firstly, the sintered matrix consists
Crystals 2021, 11, 1427 6 of 11
of framework materials, pre-alloyed powders and diamonds. Diamonds are brazed in the
framework materials using the pre-alloyed powder as a bonding phase. The pre-alloyed
powder has higher hardness than the framework materials due to its preparation process.
framework
With the increasematerials, pre-alloyed
of Ni content, powders and
the proportion ofdiamonds.
pre-alloyedDiamonds
powderare brazed inso
increased, thethe
framework materials using the pre-alloyed powder as a bonding phase. The pre-alloyed
hardness of sintered matrix increased. Secondly, with the increase of Ni, the loss of liquid
powder has higher hardness than the framework materials due to its preparation process.
phaseWith
produced by low melting point material is reduced and more liquid phase fills the
the increase of Ni content, the proportion of pre-alloyed powder increased, so the
gaps among the
hardness of powders, thus increased.
sintered matrix the density and hardness
Secondly, with theincrease.
increase of Ni, the loss of liquid
phase produced by low melting point material is reduced and more liquid phase fills the
gaps among the powders, thus the density and hardness increase.

100

95
Hardness (HRB)

90

85

80

75

0 3 6 9 12 15
Ni (wt.%)
Figure 5. The hardness of the matrix of sintered samples with different Ni contents.
Figure3.2.2.
5. TheEffect
hardness
of Niof the matrix
Content of sintered
on Shearing samples
Strength with
and different
Bending Ni contents.
Strength of Matrix
Figure 6 shows the bending strength and shearing strength of sintered matrixes with
3.2.2. Effect of Ni Content on Shearing Strength and Bending Strength of Matrix
different Ni contents. The bending strength and shearing strength is 367 MPa and 573 MPa
Figure
without 6 shows thepowders.
Ni in the bendingWith strength and shearing
the increase strength
of Ni, the bendingof strength
sinteredandmatrixes
shearingwith
different Ni contents.
strength increases.The bending
When the Nistrength
contentand shearing
is from 3 to 9 strength
wt.%, theisbending
367 MPastrength
and 573and MPa
withoutshearing
Ni in strength increaseWith
the powders. rapidly.
the While the Ni
increase content
of Ni, the exceeds
bending9 wt.% and increased
strength and shearingto
15 wt.%, the bending strength and shearing strength decreases
strength increases. When the Ni content is from 3 to 9 wt.%, the bending strength and slightly. Some paper note
that the hardness, bending strength and shearing strength is closely relevant to the density
shearing strength increase rapidly. While the Ni content exceeds 9 wt.% and increased to
for powder metallurgy, meanwhile, these values increase with the increase of density [20].
15 wt.%, the bending strength and shearing strength decreases slightly. Some paper note
When the Ni content increases, the reduction of liquid phase loss leads to more liquid
that the hardness,
phase bending
filling the strength
gap between the and
powder,shearing
thus thestrength
hardness is closely
increaserelevant to the
and bending density
strength
for powder metallurgy, meanwhile, these values increase with the increase
together with shearing strength also increase. Moreover, Figure 2 shows the grain size of density [20].
Whenbecomes
the Ni content increases,
smaller with the reduction
the increase of liquid
of Ni content phase loss of
and compounds leads to phase
Cu3 Sn more andliquid
phaseCu filling
5 Zn 8 the
phasegap
are between
gradually the
fine powder,
and thus
dispersed. the
It can hardness
infer the increase
mechanical and bending
properties
increase,
strength togetherso the bending
with strength
shearing and shearing
strength strength
also increase. increase. However,
Moreover, the Ni content
Figure 2 shows the grain
size becomes smaller with the increase of Ni content and compounds of Culoss
exceeds 9 wt.%, the melting point of Fe-Cu-Sn-Ni-Zn is improved and the 3Sn of liquid
phase and
phase is decreased, thus the excessive Cu 3 Sn phase forms, and the
Cu5Zn8 phase are gradually fine and dispersed. It can infer the mechanical properties in- bending strength and
shearing strength of the sintered matrix decreases slightly.
crease, so the bending strength and shearing strength increase. However, the Ni content
exceeds 9 wt.%, the melting point of Fe-Cu-Sn-Ni-Zn is improved and the loss of liquid
phase is decreased, thus the excessive Cu3Sn phase forms, and the bending strength and
shearing strength of the sintered matrix decreases slightly.
 Crystals 2021, 11, x FOR PEER REVIEW 7 of 11

rystals 2021, 11, x FOR PEER REVIEW 7 of 11

Crystals 2021, 11, 1427 7 of 11

800
Bending strength
750 Shearing strength

Bending/shearing strength(MPa)
800
Bending strength
700
750 Shearing strength

Bending/shearing strength(MPa)
650
700
600
650
550
600
500
550
450
500
400
450
350
400
0 3 6 9 12 15
350 Ni(wt%)
0 3 6 9 12 15
Ni(wt%)
Figure 6. Bending strength and shearing strength of sintered matrix with different Ni contents.
Figure 6. Bending strength and shearing strength of sintered matrix with different Ni contents.
Figure 6.Figure
Bending 7 strength
shows the andSEM fracture
shearing morphology
strength of sinteredofmatrix
the sample after three-point
with different Ni contents.bending
Figure 7 shows the SEM fracture morphology of the sample after three-point bending
under different Ni contents. The Ni-free sample shows a brittle-ductile mixed fracture,
under different Ni contents. The Ni-free sample shows a brittle-ductile mixed fracture, and
Figure
and some 7 shows
dimples theexist
SEMatfracture morphology
the fracture, while theof the sampleinafter
particles three-point
the fracture
some dimples exist at the fracture, while the particles in the fracture are bigger and the
arebending
bigger and
under different
thenumber
number Ni
of contents.
pores is The
more. Ni-free
With sample
the Ni shows
content a brittle-ductile
increased up to 9 mixed
of pores is more. With the Ni content increased up to 9 wt.%, the fracture modefracture
wt.%, fracture,
the is
andmode
some isdimples
ductileductile exist
and
and there at
there
are morethe
are fracture,
at while
more dimples
dimples the particles
at the
the fracture offracture
samples.inofThe
the fracture
samples.
uneven Theareuneven
bigger
fracture and
fracture
surface
the surface
number of that
indicates pores
indicates is more.
that
these these
samples With
samples theexperience
Ni content
experience increased
large
large plastic plastic up to during
9 wt.%,the
deformation
deformation the
during fracture
the bend-
bending
modeingisprocess.
ductile and
process. However,there are
However, the Nithemore
content dimplesexceeds
exceeds
Ni content at the fracture
9 wt.%, 9 wt.%,ofthe
the fracturesamples.
shows The
mainly
fracture uneven
brittle
shows fracture
fracture.
mainly brittle
surfaceThere
fracture. are
indicatesobvious
There that cleavage
arethese
obvious stepsexperience
samples at the
cleavage fracture.
steps atlarge plastic deformation during the bend-
the fracture.
ing process. However, the Ni content exceeds 9 wt.%, the fracture shows mainly brittle
fracture. There are obvious cleavage steps at the fracture.

Figure 7. Fracture
Figure morphologies
7. Fracture morphologiesofofthe
the sintered matrixes
sintered matrixes with
with different
different Ni contents:
Ni contents: (a) Ni-free,
(a) Ni-free, (b) with(b) withNi,
3 wt.% 3 (c)
wt.%
withNi, (c)
with 66 wt.% Ni, (d) with 9 wt.% Ni, (e) with 12 wt.% Ni, (f) with 15 wt.%
wt.% Ni, (d) with 9 wt.% Ni, (e) with 12 wt.% Ni, (f) with 15 wt.% Ni. Ni.
Figure 7. Fracture morphologies of the sintered matrixes with different Ni contents: (a) Ni-free, (b) with 3 wt.% Ni, (c)
with 6 wt.% Ni, (d) with 9 wt.% Ni, (e) with 12 wt.% Ni, (f) with 15 wt.% Ni.
Crystals 2021, 11, x FOR PEER REVIEW 8 of 11

Crystals 2021, 11, 1427

3.2.3. Influence of Ni on Bending Strength of Cutter Head of Diamond Tools8 of 11
The cutter head is made by adding diamond into the mixture powder through the
process of mixing, pressing and sintering. Figure 8 shows the bending strength of dia
3.2.3. Influence of Ni on Bending Strength of Cutter Head of Diamond Tools
mond tools and the holding coefficient of the sintered matrix to diamond under differen
The
Ni contents cutter
in head is made powder.
pre-alloyed by addingThediamond
bendingintostrength
the mixture powderfirst,
increases through
thenthe
decreases
process of mixing, pressing and sintering. Figure 8 shows the bending strength of diamond
and reaches the maximum with the Ni content of 9 wt.%. Moreover, Ni has a significan
tools and the holding coefficient of the sintered matrix to diamond under different Ni
effect on the holding coefficient of sintered matrix to diamond. The holding coefficien
contents in pre-alloyed powder. The bending strength increases first, then decreases, and
represents the actingwith
reaches the maximum forcethe
of Ni
sintered
contentmatrix to diamond
of 9 wt.%. Moreover,forNithe
hasdiamond cutter
a significant head [18]
effect
The
on theholding
holding coefficient
coefficient ofissintered
consistent
matrixwith the bending
to diamond. strength
The holding of the represents
coefficient cutter head. The
value of holding coefficient is up to the maximum when the Ni
the acting force of sintered matrix to diamond for the diamond cutter head [18]. content is 9The
wt.%. This
indicates it has a good
holding coefficient holding
is consistent force
with the of sintered
bending matrix
strength to diamond
of the with
cutter head. Thethe Ni of
value content o
9holding
wt.%. coefficient is up to the maximum when the Ni content is 9 wt.%. This indicates it
has a good holding force of sintered matrix to diamond with the Ni content of 9 wt.%.

90
650

600
Bending strength (MPa)

Holding coefficient (%)

80
550

500
70
450

400 Bending strength

Holding coefficient 60
350

0 3 6 9 12 15
Ni (wt.%)
Figure
Figure 8.8.The
Theeffect
effectofof
NiNi content
content on the
on the bending
bending strength
strength of diamond
of diamond tools
tools and and holding
holding coefficien
coefficient
of thesintered
of the sinteredmatrix
matrixonon diamond.
diamond.

Figure
Figure9 shows
9 shows the the
bending fracture
bending morphologies
fracture of diamond
morphologies of tools
diamondundertools
pre-alloyed
under pre-al
powders with different Ni contents. It can be seen from Figure
loyed powders with different Ni contents. It can be seen from Figure 9a 9a that the fracture
that the of fracture
diamond tools contains continuous linear pores with Ni-free in the pre-alloyed powders,
of diamond tools contains continuous linear pores with Ni-free in the pre-alloyed pow
which corresponded to a low holding coefficient of the sintered matrix to the diamond and
ders,
a low which
bendingcorresponded to a low
strength of diamond holding
tools. Whencoefficient
the Ni content of the sintered matrix
of pre-alloyed powders to the dia
mond and
increases a low
from 3 tobending strength
9 wt.%, the number of of
diamond tools.
linear pores in When the Ni
the fracture of content
diamondoftools
pre-alloyed
powders
decreases, and the structure distribution of the matrix is uniform, thus improving thediamond
increases from 3 to 9 wt.%, the number of linear pores in the fracture of
tools
densitydecreases, and matrix,
of the sintered the structure distribution
enhancing the holding ofability
the matrix is uniform,
of the sintered matrixthus improving
to the
diamond
the andofincreasing
density the bending
the sintered strength of the
matrix, enhancing diamond
holdingtools (see Figure
ability of the 9b–d).
sinteredThematrix to
lifetime
the extension
diamond andof the diamond
increasing the tool reaches
bending the optimal
strength value with
of diamond toolsthe(see
Ni content of
Figure 9b–d). The
9 wt.%. When the Ni content exceeds 9 wt.%, there is some crack at the
lifetime extension of the diamond tool reaches the optimal value with the Ni content of fracture and the
corresponding service life of diamond tools is decreased (see Figure 9e,f).
9 wt.%. When the Ni content exceeds 9 wt.%, there is some crack at the fracture and the
corresponding service life of diamond tools is decreased (see Figure 9e,f).
 Crystals 2021, 11, 1427 9 of 11
Crystals 2021, 11, x FOR PEER REVIEW 9 of 11

FigureFigure
9. The9.bending fracture
The bending morphologies
fracture morphologiesof diamond
of diamondtools
toolsunder
underpre-alloyed
pre-alloyed powders with different
powders with differentNiNicontents:
contents: (a)
T1: Ni-free,
(a) T1: Ni-free, (b) T2: with 3 wt.% Ni, (c) T3: with 6 wt.% Ni, (d) T4: with 9 wt.% Ni, (e) T5: with 12 wt.% Ni, (f) T6:T6:
(b) T2: with 3 wt.% Ni, (c) T3: with 6 wt.% Ni, (d) T4: with 9 wt.% Ni, (e) T5: with 12 wt.% Ni, (f) with 15
with
wt.% 15
Ni.wt.% Ni.

The The
EDS EDS resultsofofthe
results theinterface
interfacebetween
between the matrix
matrixand andthe thediamond
diamondare listed
are in in
listed
Table 2. It can indicate that metallurgical reactions take place between
Table 2. It can indicate that metallurgical reactions take place between the matrix and the the matrix and
the diamond
diamond for allfor all samples
samples withwith different
different content
content of Ni.
of Ni. It isIt well
is well knownthat
known thatFe
Fehas
hasaa good
good wettability on the surface of the diamond. It diffuses to and reacts with diamonds to
wettability on the surface of the diamond. It diffuses to and reacts with diamonds to form
form carbides, which improve the holding ability of matrix to the diamond. When the Ni
carbides,
contentwhich improvepowders
in pre-alloyed the holdingis lessability
than 9 of matrix
wt.%, to the
Ni has good diamond.
solubilityWhen
with CutheandNi con-
tentFe,inunder
pre-alloyed
the action of solid solution strengthening and dispersion strengthening among Fe,
powders is less than 9 wt.%, Ni has good solubility with Cu and
under
them, the
theaction of solidofsolution
microstructure matrix can strengthening and dispersion
be refined, therefore the strengthstrengthening
and toughness of among
them,
matrixthe is
microstructure
improved. Thus, of the
matrix canlife
service beof refined,
diamond therefore the strength
tools is enhanced withand
the toughness
increase of
of Ni content. The holding ability of the matrix to the diamond
matrix is improved. Thus, the service life of diamond tools is enhanced with the increase reaches the optimum
value
of Ni with the
content. TheNiholding
contentability
of 9 wt.%. However,
of the matrix to when the Ni content
the diamond increases
reaches from 9 tovalue
the optimum
15 wt.%, the excessive Ni is added into the liquid phase
with the Ni content of 9 wt.%. However, when the Ni content increases from 9 to to improve the melting point
15 wt.%,
of Fe-Cu-Sn-Ni-Zn so that the Cu-Sn brittle phase is formed. Thus, the toughness of the
the excessive Ni is added into the liquid phase to improve the melting point of Fe-Cu-Sn-
matrix decreases, which leads to the decrease of the bending strength of diamond tools
Ni-Zn
and so the that
slightthe Cu-Sn brittle
deterioration of thephase
holding is ability
formed. Thus,
of the matrixthetotoughness
diamond, andof the matrix
finally the de-
creases, which leads to the decrease
service life of diamond tools is decreased. of the bending strength of diamond tools and the
slight deterioration of the holding ability of the matrix to diamond, and finally the service
lifeTable 2. EDS results
of diamond toolsofisthedecreased.
interface between the matrix and the diamond.

Chemical Elements/at.%
Table Ni Content
2. EDS (wt.%)
results of the interface
C between
Fe the matrix
Cu and the Sn
diamond. Ni Zn
0 98.07 1.12 0.50 0.12 - 0.16
Ni Content3 96.12 1.15 Chemical
0.63 Elements/at.%
2.03 0.07 0
(wt.%) 6 C 96.05 Fe 2.53 Cu 0.94 Sn0 0.29
Ni 0.18 Zn
9 80.69 13.72 3.46 0.99 0.45 0.69
0 12 98.07 98.59 1.12 1.27 0.500.09 0.12
0.01 0.01- 0.040.16
3 15 96.12 96.34 1.15 1.21 0.631.32 2.03
0.55 0.07
0.47 0.11 0
6 96.05 2.53 0.94 0 0.29 0.18
9 80.69 13.72 3.46 0.99 0.45 0.69
12 98.59 1.27 0.09 0.01 0.01 0.04
15 96.34 1.21 1.32 0.55 0.47 0.11

4. Conclusions
This present work studied the microstructure evolution of Ni-added Fe-based sin-
tered matrix and the lifetime extension of Ni-added diamond tools. The main conclusions
Crystals 2021, 11, 1427 10 of 11

4. Conclusions
This present work studied the microstructure evolution of Ni-added Fe-based sintered
matrix and the lifetime extension of Ni-added diamond tools. The main conclusions were
as follows:
• With the increase of Ni content in the pre-alloyed powders, the microstructure of the
matrix is refined and becomes more uniform; the hardness of the matrix increases.
• When the content of Ni increased from 0 to 15 wt.%, the bending strength and the
shearing strength both increased firstly, then reached the optimal value with the Ni
content of 9 wt.% and decreased finally. The fracture morphologies of the matrix
changed from brittle fracture into brittle-ductile fracture, then ductile fracture (with
the Ni content of 9 wt.%), brittle-ductile mixed fracture and brittle fracture.
• With the increase of Ni content in the pre-alloyed powders, the bending strength
of diamond tools and the holding coefficient of the sintered matrix to diamond in-
creased firstly, then reached up to the maximum with the Ni content of 9 wt.% and
decreased finally.
• The service life of diamond tools was greatly prolonged when adding the Ni content
of 9 wt.% into the pre-alloyed powder.

Author Contributions: Conceptualization: J.P., Y.S., W.L. and M.W.; methodology: D.L. and J.P.;
formal analysis: J.P. and S.Z.; resources: S.X.; data curation: S.X. and S.Z.; writing—original draft
preparation: J.P.; writing—review and editing: J.P. and W.L.; writing—manuscript finalization: J.P.,
W.L. and D.L.; supervision: S.X. and W.L.; project administration: W.L. and S.Z.; funding acquisition:
S.Z. and S.X. All authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by Jiangsu University (High-tech Ship) Cooperative Inno-
vation Centre and Institute of Marine Equipment, Jiangsu University of Science and Technology
(No. HZ2018008), and was supported by Jiangsu Province Undergraduate Innovation Project, and
supported by Jiangsu Key Laboratory Project of Green Ship Technology (No. 2019Z02).
Conflicts of Interest: The authors declare no conflict of interest. The funder had no role in the de-sign
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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