materials

Article
Reactivity and Penetration Performance Ni-Al and
Cu-Ni-Al Mixtures as Shaped Charge Liner Materials
Miao Sun 1 , Chao Li 2 , Xuguang Zhang 3 , Xiaomin Hu 1 , Xiaoyan Hu 1 and Yingbin Liu 1, *
1 School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China;
[email protected] (M.S.); [email protected] (X.H.); [email protected] (X.H.)
2 Beijing Special Vehicle Institute, Beijing 100000, China; [email protected]
3 School of Mechanical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China;
[email protected]
* Correspondence: [email protected]; Tel.: +86-155-3687-0915




Received: 18 October 2018; Accepted: 7 November 2018; Published: 13 November 2018


Abstract: Energetic structural materials (ESMs) have many potential military applications due to
their unique functions. In this work, the reactivity and penetration performance of ESMs have been
examined as a shaped charge liner material. The penetration experiments of nickel-aluminum (Ni-Al)
and copper-nickel-aluminum (Cu-Ni-Al)-shaped charge liners (SCLs) have been designed and fired
into 45# steel. The targets were recovered and analyzed by optical microscopy, electron microscopy,
energy dispersive spectroscopy, and Vickers microhardness measurements. The head and tail of the
crater walls penetrated by two reactive jets demonstrated unique microstructures. The jet rapidly
decayed with the penetration process, but the “white” zone (a mixture of martensite and austenite)
was more prominent in the tail, and the microhardness of the tail was much higher than that of the
head. The results showed the continued exotherm of Ni-Al reactive jet when it was fired into the
target. The addition of Cu reduced the exotherm of Ni-Al, Cu could not only increase the average
crater size, but also raise the average penetration depth by 42%. These results offer valuable insight
for utilizing ESM as shaped charge liner materials.

Keywords: shaped charge liner; Ni-Al; energetic structural materials; penetration performance;
microstructure analysis

1. Introduction
Energetic structural materials (ESMs) or reactive metal materials (RMMs) possess desired
mechanical properties and shock release energy. An ESM can be an ideal platform for the combined
ballistic delivery of chemical and kinetic energies [1], and thus it can be utilized as reactive fragments
and reactive liners for producing large and effective perforations in broad military applications.
To achieve good properties of an ESM, the following three perspectives should be taken into account:
(1) an ESM is sufficiently insensitive to the explosion environment during the acceleration of the
explosion; (2) it has a sufficient penetration capability; and (3) it can combine kinetic energy with
chemical reaction energy to increase its damage capacity [2,3]. Reactive metal materials have better
density and sound velocity than fluorine-based reactive materials; thus, RMMs demonstrate better
characteristics as shaped charge liner materials.
Nickel-aluminum (Ni-Al) powders are reactive metals that have been widely studied in recent
years. A systematic review of the shock-induced chemical reaction (SICR) in Ni-Al powders can be
found in the study from Thadhani [4]. Zhang [5] investigated the effect of sintering temperature on
mechanical properties and energy density of Ni-Al materials. The results revealed that a certain amount
of energy was transferred during the sintering procedure to enhance limited mechanical properties

Materials 2018, 11, 2267; doi:10.3390/ma11112267 www.mdpi.com/journal/materials

Materials 2018, 11, 2267 2 of 11

of Ni-Al materials. Subsequently, other metals were added to Ni-Al, and their SICR characteristics
have shown an increase or decrease. Homan [6] studied the effects of the addition of three metals,
namely magnesium (Mg), molybdenum (Mo), and copper (Cu), on the initiation and combustion
properties of Ni-Al.
Materials 2018, 11, The
x FORresults showed that the addition of Cu significantly increased the2initial
PEER REVIEW of 12 SICR
temperature and the reaction time. Xiong [7] analyzed the effects of Cu/PTFE on SICR behaviors
properties of Ni-Al
and energy-releasing materials. Subsequently,
characteristics other metals The
of Ni-Al composites. were experimental
added to Ni-Al,and andtheoretical
their SICR results
characteristics have shown an increase or decrease. Homan [6] studied the effects of the addition of
suggested that Cu could increase the critical shock pressure for the initiation of SICR and decreased
three metals, namely magnesium (Mg), molybdenum (Mo), and copper (Cu), on the initiation and
the reaction efficiency
combustion underofthe
properties same
Ni-Al. Theimpact conditions.
results showed that the addition of Cu significantly increased
Thethepenetration performance
initial SICR temperature and theof reaction
reactive-shaped
time. Xiong charge
[7] analyzedliners (RSCL)
the effects has been
of Cu/PTFE on widely
investigated. Laszlo [8]
SICR behaviors andstudied RSCL fabricated
energy-releasing by Zr
characteristics of 57 Nb5composites.
Ni-Al Cu15.4 Ni12.6The Al10experimental
. The results andshowed
theoretical
RSCL could form results
particle suggested
streamsthatandCu thecould increase the
penetration depthcritical shock
of Zr pressure for the initiation of
57 Nb5 Cu15.4 Ni12.6 Al10 was shallower
SICR and decreased the reaction efficiency under the same impact conditions.
than that of the copper liner for the same structure (no chemical reaction), but it had better lateral
The penetration performance of reactive-shaped charge liners (RSCL) has been widely
damage. On the other hand, Ni-Al as a shaped charge liner material was analyzed in the stages of
investigated. Laszlo [8] studied RSCL fabricated by Zr57Nb5Cu15.4Ni12.6Al10. The results showed
energy RSCL
release.
couldAformtriaxial loading
particle streamssystem
and thewas designed
penetration depth byofPhilip
Zr57Nb5[9] toNidetermine
Cu15.4 shock reaction
12.6Al10 was shallower

thresholds of Ni-Al reactive powders. The simple press tool could fragment Ni-Al
than that of the copper liner for the same structure (no chemical reaction), but it had better lateral RSCL, and the jet
damage. On the other hand, Ni-Al as a shaped charge liner material
was recovered from the sand target. It also showed that Ni-Al RSCL reacted during the formationwas analyzed in the stages of
energy release. A triaxial loading system was designed by Philip [9] to
process of liner. However, it is challenging to determine whether the reaction would continue in thedetermine shock reaction
thresholds of Ni-Al reactive powders. The simple press tool could fragment Ni-Al RSCL, and the jet
sand target due to the reaction exotherm.
was recovered from the sand target. It also showed that Ni-Al RSCL reacted during the formation
Here we investigate whether Ni-Al reactive jets react in the steel target and how the penetration
process of liner. However, it is challenging to determine whether the reaction would continue in the
performance changes
sand target due to after passivation
the reaction exotherm. by addition of Cu. Two kinds of RSCLs made of Ni-Al
and Cu-Ni-Al Herewere studied for
we investigate penetrating
whether 45# steel
Ni-Al reactive jetstargets.
react in After the target
the steel penetration
and how experiments,
the
penetration
the penetration performance
depths changes
and crater after
sizes ofpassivation
the RSCLsbywereaddition of Cu. Two
compared. Tokinds of RSCLsthe
investigate made of
reactivity of
Ni-Al and Cu-Ni-Al were studied for penetrating 45# steel targets.
Ni-Al and the influence of Cu on SICR of Ni-Al when they penetrated the target as jets, we examined After the penetration
experiments, the penetration depths and crater sizes of the RSCLs were compared. To investigate
the microstructure of the crater walls. By comparing the microstructural differences between the
the reactivity of Ni-Al and the influence of Cu on SICR of Ni-Al when they penetrated the target as
head andjets,tail
we ofexamined
the crater the walls, it couldofbethe
microstructure inferred whether
crater walls. By the jet released
comparing energy during the
the microstructural
penetration
differences between the head and tail of the crater walls, it could be inferred whether the of
progress. These investigations could provide a reference for the applications jet ESM in
shaped released
charge liners.
energy during the penetration progress. These investigations could provide a reference for
the applications of ESM in shaped charge liners.
2. Materials and Methods
2. Materials and Methods
The powders used to prepare the reactive liners were obtained by mechanical mixtures of Ni, Al,
The powders used to prepare the reactive liners were obtained by mechanical mixtures of Ni,
and Cu Al,
of different morphologies and sizes, as illustrated in Figure 1. The powders’ characteristics are
and Cu of different morphologies and sizes, as illustrated in Figure 1. The powders’
listed incharacteristics
Table 1. are listed in Table 1.

Figure
Figure 1. The
1. The powders used
powders used to
toprepare
preparethethe
reactive liners.
reactive (a) Ni;(a)
liners. (b)Ni;
Al; (b)
and Al;
(c) Cu.
and (c) Cu.
Table1.
Table 1. The
Thecharacteristics
characteristicsof powder mixtures.
of powder mixtures.
Material Shape Size (μm) Purity (Pct)
Material Shape Size (µm) Purity (Pct)
Nickel Powder thorny rounded 2–6 99.9
Nickel Powder
Aluminum Powder thornyrounded
rounded 2–6
6–15 99.9
Aluminum
CopperPowder
Powder rounded
rounded 6–15
20–50 99.9
Copper Powder rounded 20–50 99.9
Materials 2018, 11, 2267 3 of 11

It is essential to produce RSCL without initiating any reactions to maximize the potential energy
of RSCL. Powder metallurgy was implemented without sintering to produce all the RSCL. Table 2
shows the properties of two kinds of RSCL. Archimedes drainage method was used to measure the
actual material density (AMD) of RSCL. The cross-sections of two kinds of RSCL were characterized
by Mira3Materials
LMH2018,
scanning electron microscope (SEM, Tescan, Brno, Czech Republic).
11, x FOR PEER REVIEW 3 of 12

It isTable 2. The
essential to properties of twowithout
produce RSCL kinds of reactive-shaped
initiating chargetoliners
any reactions (RSCLs).
maximize the potential
energy of RSCL. Powder metallurgy was implemented without sintering to produce all the RSCL.
Table 2 shows Type
the properties of two kinds AMD Height Thickness Porosity
Number wt (%) Mass of
(g)RSCL. Archimedes
3)
drainage method was used to
measure the actual material density (AMD) of RSCL. (g/cm (mm) of two
The cross-sections (mm) (%) were
kinds of RSCL
characterized
A-1 by Mira3 LMH66:34
Ni-Al scanning electron
27.5 microscope
4.73 (SEM, Tescan,
47 Brno, Czech Republic).
1.78 6.2
A-2 Ni-Al 66:34 27.9 4.76 47 1.78 5.5
A-3 Table 2. The properties
Ni-Al 66:34 of two kinds
27.4of reactive-shaped
4.75 charge
47 liners (RSCLs).
1.78 5.7
B-1 Cu-Ni-Al 30:35:35 27.3 4.78 47
Height 1.72
Thickness 3.3
Porosity
Number Type wt (%) Mass (g) AMD (g/cm3)
B-2 Cu-Ni-Al 30:35:35 27.7 4.75 47
(mm) 1.78
(mm) 3.9
(%)
B-3A-1 Ni-Al
Cu-Ni-Al 66:34
30:35:35 27.5
27.5 4.73
4.77 4747 1.78
1.75 6.2
3.5
A-2 Ni-Al 66:34 27.9 4.76 47 1.78 5.5
A-3 Ni-Al 66:34 27.4 4.75 47 1.78 5.7
B-1 Cu-Ni-Al 30:35:35 27.3 4.78 47 1.72 3.3
All linersB-2used Cu-Ni-Al
in these experiments
30:35:35
had
27.7
a conical
4.75
geometry.47
The tolerance
1.78
dimensions
3.9
of the
thickness (t) on
B-3 the Cu-Ni-Al
surface of the liners were less than 0.1 mm. Figure 2 shows RSCLs and
30:35:35 27.5 4.77 47 1.75 3.5 the
schematic of a shaped charge device; 45# steel was used as the shaped charge casing. The shaped
All liners used in these experiments had a conical geometry. The tolerance dimensions of the
charge was loaded with 8701, a hexogen-based (RDX) explosive. Charge diameter (CD) and the
thickness (t) on the surface of the liners were less than 0.1 mm. Figure 2 shows RSCLs and the
liner diameter
schematic (LD)
of a were
shaped both 44 device;
charge mm. The RSCLs
45# steel was were
used assubjected
the shapedtocharge
explosive loading
casing. The shapedunder the
same conditions,
charge was loaded with 8701, a hexogen-based (RDX) explosive. Charge diameter (CD) and the used
including stand-off distances, and 45# steel target columns as targets were
in the penetration
liner diameter experiments.
(LD) were both The
44 schematic
mm. The RSCLs of the penetration
were subjected toexperiment is shown
explosive loading underinthe
Figure 3.
same conditions, including stand-off distances, and 45# steel target columns as targets
The target columns were retrieved and cut along the centerline of the crater by electrical discharge were used in
the penetration experiments. The schematic of the penetration experiment is shown in Figure 3. The
machining. Two kinds of RSCLs were compared regarding their penetration performance. Some parts
target columns were retrieved and cut along the centerline of the crater by electrical discharge
of the cross-section from the head and tail of the crater walls were cut from the targets, polished,
machining. Two kinds of RSCLs were compared regarding their penetration performance. Some
and etched
partsbyof the solution composed
the cross-section of 100
from the head mL
and tailethanol and 4walls
of the crater mL were
hydrogen nitrates
cut from to prepare
the targets,
samplespolished,
for microstructural
and etched by the solution composed of 100 mL ethanol and 4 mL hydrogen nitrates tooptical
analysis. These samples were investigated by Axio Lab A1
prepare samples
microscope (OM, CarlZeiss, for microstructural
Jena, Germany), analysis. These X-MaxN
and SEM. samples were investigated
Energy Dispersiveby Spectroscopy
Axio Lab A1 (EDS,
optical microscope (OM, CarlZeiss, Jena, Germany), and
Oxford-instruments, High Wycombe, UK) was applied along with SEM to determine SEM. X-MaxN Energy Dispersive
the elements
Spectroscopy (EDS, Oxford-instruments, High Wycombe, UK) was applied along with SEM to
of the residual jet zone. To investigate the properties of different zones in penetration crater walls,
determine the elements of the residual jet zone. To investigate the properties of different zones in
we performed Vickers
penetration cratermicrohardness measurements
walls, we performed (JMHVS-1000AT)
Vickers microhardness using(JMHVS-1000AT)
measurements a standard diamond
indenterusing
at a 0.98 N load for 15 s.
a standard diamond indenter at a 0.98 N load for 15 s.

(a) (b)
Figure
Figure 2. (a)2. Reactive-shaped
(a) Reactive-shapedcharge
charge liners
linersand
and(b)(b)
thethe
schematic of a shaped
schematic charge device.
of a shaped charge device.
Materials 2018, 11, 2267 4 of 11
Materials 2018, 11, x FOR PEER REVIEW 4 of 12

Materials 2018, 11, x FOR PEER REVIEW 4 of 12

FigureFigure 3. The
3. The schematic of
schematic ofthe penetration
the experiments.
penetration experiments.

3. Results 3. Results
Figure 3. The schematic of the penetration experiments.
The SEM images of the fabricated Ni-Al and Cu-Ni-Al RSCLs are shown in Figure 4, and the
The SEM images
3.EDS points of
Results
the offabricated
results A–E are shownNi-Al and Cu-Ni-Al
in Figure 5. It indicatesRSCLs areE shown
that A and in Figure
are Al powders, B and4,Cand the EDS
points resultsare
of Ni
A–Epowders, and D is
are shown inCu powder.
Figure 5. Nickel particlesthat
It indicates tightly
A surrounded
and E are Al Alparticles
powders, in Ni-Al
B and C are Ni
RSCL,Theand
SEM Alimages of the
particles hadfabricated Ni-Al and Figure
slight deformation. Cu-Ni-Al
4b RSCLs
shows are
the shown in Figureof4,Cu-Ni-Al
microstructure and the
powders, andEDS D points
is Curesults
powder.of A–ENickel particles
are shown tightly
in embedded
Figure surrounded
5. Itwithin
indicates AlE are
particles in Ni-Al RSCL, and Al
RSCLs, where larger Cu particles were the that A and
matrix of Ni and Al
Al powders,
particles. B and C
particles hadare
slight deformation.
Ni powders, and D isFigure 4b shows
Cu powder. the microstructure
Nickel particles of Cu-Ni-Al
tightly surrounded Al particlesRSCLs,
in Ni-Al where larger
Cu particles RSCL,
were and Al particles had slight deformation. Figure 4b shows the microstructure of Cu-Ni-Al
embedded within the matrix of Ni and Al particles.
RSCLs, where larger Cu particles were embedded within the matrix of Ni and Al particles.

Figure 4. The SEM images of (a) Ni-Al RSCL and (b) Cu-Ni-Al RSCL.

Figure 4. The SEM images of (a) Ni-Al RSCL and (b) Cu-Ni-Al RSCL.
Figure
Materials 2018, 4. The
11, x FOR SEM images
PEER REVIEW of (a) Ni-Al RSCL and (b) Cu-Ni-Al RSCL. 5 of 12

Figure5.5.The
Figure The point
pointEDS results
EDS of A-E.of A-E.
results
Figure 6 shows the macroscopic targets penetrated by Ni-Al and Cu-Ni-Al reactive jets. The
Figure 6surface
shows the macroscopic targets penetrated by Ni-Al and Cu-Ni-Al reactive jets.
of the walls of crater were rough, and the crater sizes were relatively large. The entire
The surface of the walls
penetration ofwere
walls crater were
clean, rough,that
suggesting andno the
slug crater sizes
remained after were relatively
penetration. large. The entire
The average
penetration penetration
walls were depth of Cu-Ni-Al
clean, jet was increased
suggesting that noby 42% compared
slug to the average
remained penetration depthThe average
after penetration.
of Ni-Al jet. The data of penetration performance is shown in Table 3.
penetration depth of Cu-Ni-Al jet was increased by 42% compared to the average penetration depth of
Ni-Al jet. The data of penetration performance is shown in Table 3.
 Figure 5. The point EDS results of A-E.

Figure 6 shows the macroscopic targets penetrated by Ni-Al and Cu-Ni-Al reactive jets. The
surface of the walls of crater were rough, and the crater sizes were relatively large. The entire
penetration walls were clean, suggesting that no slug remained after penetration. The average
Materials 2018, 11, 2267
penetration depth of Cu-Ni-Al jet was increased by 42% compared to the average penetration depth 5 of 11
of Ni-Al jet. The data of penetration performance is shown in Table 3.

Figure
Figure 6. The 6. The macroscopic
macroscopic featuresof
features ofthe
the targets
targetspenetrated by (a) Cu-Ni-Al
penetrated and (b) Ni-Al
by (a) Cu-Ni-Al andjet. (b) Ni-Al jet.

Table 3. The penetration depth and entrance aperture data of RSCLs.

Table 3. The penetration depth and entrance aperture data of RSCLs.
Average
Penetration Crater Size Average Crater Size
NumberPenetration Average Penetration
Penetration Crater Size Average Crater
Number Depth (mm) (mm × mm) (mm × mm)
Depth (mm) Depth (mm)
Depth (mm) (mm × mm) Size (mm × mm)
A-1 A-1 75 75 2020× ×
20 20
A-2 A-2 78 78 76 76 2121× ×
20 20 21 ×2120× 20
A-3 A-3 76 76 2121× ×
20 20
B-1 105 23 × 25
B-1 105 23 × 25
B-2 112 108 21 × 22 22 × 23
B-2 112 108 21 × 22 22 × 23
B-3 109 23 × 22
B-3 109 23 × 22

Figures 7 and 8 show OM images of the head and tail of the walls penetrated by Ni-Al and
Cu-Ni-Al reactive jet. The microstructural characteristics indicate that the crater walls can be divided
into four zones: the residual jet zone, “white” zone, deformation zone, and matrix. Table 4 lists the
thickness parameters of the affected zones in crater walls. Residual jet zone and “white” zone in the
head of the walls were thinner than that in the tail of the walls. No obvious deformation zone was
observed in the tail of the walls penetrated by Ni-Al reactive jet. However, the deformation zone was
observed in the tail of the walls penetrated by Cu-Ni-Al reactive jet.
Higher impact pressures tend to indicate higher temperature rises, and the head of the crater
walls is subject to higher impact pressures from the jet, but it is worth noting that the “white” zone
in the tail, encountering small impact pressure is much wider than that in the head. The severely
deformed “white” zone and ferrite are visible from the head of the target, so the “white” zone of the
head is mainly caused by jet impact. The “white” zone in the tail underwent severe deformation and
received a large amount of released heat when the intermetallic compound was formed by Ni-Al.
The exothermic heat of Ni-Al is enough to cause the self-propagating high-temperature synthesis
(SHS) reaction, and the SICR also can be caused when shock wave passed through Ni-Al mixtures [10].
A critical question is whether these reactions are initiated only by the shock wave and proceed to their
endings. After the shock wave passes through the material, the material may react further due to the
combined action of shock and reaction exotherm. The wider “white” zone is absorbed by the tail due
to more heat. Thus, the exothermic stage of the reactive jet can also occur at a later stage of penetration.
Although at the microstructural level, the reaction is very complex and depends on a number of factors
such as the porosity of material and size and shape of particles, at this condition of the powders, Ni-Al
jet has not only a specific penetrating ability but also the ability to radiate heat inside the target.
 Table 4. The thickness parameters of the affected zones penetrated by two kinds of RSCLs.

Part of Crater Residual Jet “White” Zone Deformation Total Affected

SCL Materials
Wall Zone (μm) (μm) Zone (μm) Zone (μm)
Ni-Al head 10–90 40–80 120–170 170–240
Ni-Al tail 30–130 230–300 - 250–300
Materials 2018, 11, 2267
Cu-Ni-Al head 50–220 80–150 200–270 330–410 6 of 11
Cu-Ni-Al tail 80–350 100–200 200–300 380–500

Figure 7. The microstructure

Figure of the
7. The microstructure crater
of the crater walls penetrated
walls penetrated byreactive
by Ni-Al Ni-Alshaped
reactive
chargeshaped
liner. (a) charge liner.
thethe
(a) the head of headcrater
of the crater
wallswalls
(100(100×);
×); (b)(b) the
the tail
tailofofthethe
crater wallswalls
crater (100×);(100
(c) the head
×); (c)ofthe
thehead
crater of the crater
walls (200×); (d) the tail of the crater walls (200×).
walls (200×); (d) the tail of the crater walls (200×).

Table 4. The thickness parameters of the affected zones penetrated by two kinds of RSCLs.

Part of Crater Residual Jet “White” Deformation Total Affected

SCL Materials
Wall Zone (µm) Zone (µm) Zone (µm) Zone (µm)
Ni-Al head 10–90 40–80 120–170 170–240
Ni-Al tail 30–130 230–300 - 250–300
Cu-Ni-Al head 50–220 80–150 200–270 330–410
Cu-Ni-Al tail 80–350 100–200 200–300 380–500

The point EDS results in the residual zone are shown in Figure 9, while Figure 10 shows the EDS
line analysis results between the residual and “white” zone. The percentage of Fe in Ni-Al residual jet
was much higher than that in Cu-Ni-Al residual jet. The percentage of oxygen was low in both of the
residual jets. Nickel and Al signal intensities in Ni-Al residual jets were similar and stable, while the
strength transition of Fe signal was rapid, demonstrating a large shift in the magnitude. The signal
intensities of Ni and Al in Cu-Ni-Al residual jets were quite different, and the transition of Fe signal
intensity was gentle, experiencing a very weak change in intensity.
 and proceed to their endings. After the shock wave passes through the material, the material may
react further due to the combined action of shock and reaction exotherm. The wider “white” zone is
absorbed by the tail due to more heat. Thus, the exothermic stage of the reactive jet can also occur at
a later stage of penetration. Although at the microstructural level, the reaction is very complex and
depends on a number of factors such as the porosity of material and size and shape of particles, at
Materials this
2018,condition
11, 2267 of the powders, Ni-Al jet has not only a specific penetrating ability but also the ability 7 of 11
to radiate heat inside the target.

Materials 2018, 11, x FOR PEER REVIEW 8 of 12

The point EDS results in the residual zone are shown in Figure 9, while Figure 10 shows the
EDS line analysis results between the residual and “white” zone. The percentage of Fe in Ni-Al
residual jet was much higher than that in Cu-Ni-Al residual jet. The percentage of oxygen was low
in both of the residual jets. Nickel and Al signal intensities in Ni-Al residual jets were similar and
Figure 8. The 8.
microstructure
Figurewhile Thethe
of the
microstructure
crater walls
of the crater
penetrated
walls penetrated
bybyCu-Ni-Al
Cu-Ni-Al
reactive-shaped
reactive-shaped
charge liner.
stable, strength transition of Fe signal was rapid, demonstrating a largecharge
shift in the
(a) themagnitude.
head of the crater
liner. (a) theThe
head walls (100
of theintensities
signal × );
crater wallsof (b) the
(100×);
Ni and tail of
(b) the
Al in the crater
tailCu-Ni-Al walls
of the crater (100 × );
walls (100×);
residual (c) the
(c) the
jets were head of the crater
headdifferent,
quite of the and
walls the
(200 ×
crater);walls
(d) (200×);
the tail(d)
of the
thetail of
crater the crater
walls (200 ×
walls (200×).
).
transition of Fe signal intensity was gentle, experiencing a very weak change in intensity.

9. The
FigureFigure point
9. The EDS
point results
EDS resultsof
ofNi-Al andCu-Ni-Al
Ni-Al and Cu-Ni-Al residual
residual jet zone.
jet zone.
Materials 2018, 11, 2267 8 of 11
Figure 9. The point EDS results of Ni-Al and Cu-Ni-Al residual jet zone.

Materials 2018, 11, x FOR PEER REVIEW 9 of 12

Materials 2018, 11, x FOR PEER REVIEW 9 of 12

Figure 10. The EDS10.line

Figure The analysis at theatinterface
EDS line analysis between
the interface between (a) Ni-Alresidual
(a) Ni-Al residual
zonezone and “white”
and “white” zone zone and
and (b) Cu-Ni-Al residual zone and “white” zone.
(b) Cu-Ni-Al residual zone and “white” zone.
Figure 10. The EDS line analysis at the interface between (a) Ni-Al residual zone and “white” zone
and (b) Cu-Ni-Al residual zone and “white” zone.
The Vickers microhardness results are shown in Figure 11. In the homogeneous residual jet
The Vickers
zone, microhardness
the microhardness results
values inare
the shown
head werein similar
Figureto11.
thatIn in the
the homogeneous residual jet zone,
tail. The microhardness
The Vickers microhardness results are shown in Figure 11. InInthe homogeneous residual jet
the microhardness values in the head were similar to that in the tail. The microhardness values of
values of Ni-Al residual jet zone were doubled than that of Cu-Ni-Al. the homogeneous “white”
zone, zone
the ofmicrohardness values
target penetrated by twoinRSCL,
the headmicrohardness
were similar to that in theweretail.greater
The microhardness
Ni-Al residual
valuesinof
jet zone were jetdoubled thanthethat than
of Cu-Ni-Al. values in the
In thetail
homogeneous than that
“white” zone of
theNi-Al
head. residual zone were
The microhardness valuesdoubled that
of Ni-Al “white” of in
zone Cu-Ni-Al. In the
the tail were homogeneous
increased 150 HV than“white”
target penetrated
thattarget
zone of bypenetrated by two RSCL, the microhardness values in the tail were greater than that in the
two
of Cu-Ni-Al. RSCL, the microhardness values in the tail were greater than that
head. The microhardness
in the values ofvalues
head. The microhardness Ni-Alof“white” zonezone
Ni-Al “white” in the tailtail
in the were
wereincreased
increased 150 150HVHV than that
than
that of Cu-Ni-Al.
of Cu-Ni-Al.

Figure 11. The Vickers hardness values for all zones.

4. Discussion
The particle size matching principle is helpful to reduce the porosity of the powder material,
although the optimal porosity
Figure for Vickers
11. The
The the inert jet (Cu values
or W-Cu) is zones.
advantageous to improve the
Figure 11. Vickershardness
hardness for all
values for all zones.
cohesiveness of the liner forming the jet, thereby improving the penetration performance of the
liners [11]. However, when the porosity is too large, high-energy storing capacity could easily
4. Discussion
induce the shock-induced chemical reaction of the reactive powder material; thus, high porosity
The
mayparticle size matching
cause irreversible principle
bursting of jetsis[12]
helpful to reduce
and reduce theirthe porosity
ability of the powder
to penetrate material,
the target.
although the optimal porosity for the inert jet (Cu or W-Cu) is advantageous to improve the
cohesiveness of the liner forming the jet, thereby improving the penetration performance of the
liners [11]. However, when the porosity is too large, high-energy storing capacity could easily
induce the shock-induced chemical reaction of the reactive powder material; thus, high porosity
Materials 2018, 11, 2267 9 of 11

4. Discussion
The particle size matching principle is helpful to reduce the porosity of the powder material,
although the optimal porosity for the inert jet (Cu or W-Cu) is advantageous to improve the
cohesiveness of the liner forming the jet, thereby improving the penetration performance of the
liners [11]. However, when the porosity is too large, high-energy storing capacity could easily induce
the shock-induced chemical reaction of the reactive powder material; thus, high porosity may cause
irreversible bursting of jets [12] and reduce their ability to penetrate the target. Therefore, compared
with the porosity of Ni-Al and Cu-Ni-Al RSCLs, the addition of large Cu particles can effectively
reduce the porosity of the liners, thereby enhancing the penetrating performance of the reactive jets.
The comparison of the penetrating properties suggests that, Cu provided an apparent increase in
the average crater size and penetration depth of Ni-Al reactive liner. From a conventional point of view,
ρ 1
the depth of penetration is dominated by the density of the liner and target, P = L( ρj ) 2 , where ρj is the
t
density of the jet, ρt is the density of the target, and L is the length of the jet that is mostly decided by
stand-off when the stand-off is very short. The densities of two reactive liners and target materials were
the same, and the same stand-off was used in the penetration experiments. Thus, it can be inferred
that Cu enhanced the penetration properties of Ni-Al reactive liners. Compared with the previous
W and W-Cu jet penetration experiments [13], the addition of Cu effectively reduced the interaction
between the jet and target, decreased the formation of a hard phase of the target, and thus improve the
penetration depth. The crater size is also an important indicator of penetration performance since it
is the reflection of the total energy of the jet. Although Cu increased the penetration depth of Ni-Al
reactive jet, it had no adverse effect on the crater size; thus, Cu could serve as a tool to engineer the
properties of Ni-Al ESM for the applications in shaped charge materials.
By comparing the microscopic images of the head and tail of the ballistics, the speed of the jet
rapidly decreased with the penetration depth. As shown in Figure 3, the jet adhered to the surface
of crater walls finally due to the low speed, so the residual jet width of the tail was higher than
that of the head. It is known that the deformation process at high strain rates is adiabatic, and for
most metals, 90% of the deformation is converted into heat. Steel undergoes a phase transition from
α (Body-Centered Cubic) to γ (Faced-Centered Cubic) at 912 ◦ C [14]. If the temperature within
the crater walls reaches this value, then the phase transformation occurs, and this phase can be
retained at room temperature, since the material within the crater walls is much smaller than the
entire target, and is rapidly quenched by the surrounding material once plastic deformation ceases.
Therefore, it is reasonable that the “white” zone, which contacts with residual jet have undergone
phase transformation. The martensitic transformation is generally unlike for the surrounding material.
The EDS analysis results and the hardness measurements confirm the martensitic transformation took
place. The EDS results shown that Ni, Al, and Cu in the residual jet maintained their initial percentage.
The percentage of Fe in the residual jet indicates the intensity of the interaction with the target [15].
Cu reduces the interaction between the jet and target and decreases the degree of Ni-Al reaction that is
evident from the signal strengths of the elements. This outcome is in agreement with other studies by
Homan [5] and Xiong [7].
The hardness values of the zones in the target can explain the microstructural phenomenon better.
Yin [16] proved that due to the extremely high temperature on the crater walls and the high cooling
rate, the “white” zone comprises a mixture of martensite and retained austenite. This microstructure
is the reason why the “white” zone is not as hard as untampered martensite of steel. In this study,
because of the further reaction of Ni-Al, the residual austenite in the “white” zone of the tail was
transformed into martensite. The hardness of the “white” zone was greatly enhanced due to the
increase of the martensitic phase. This result indirectly proves that the Ni-Al reaction occurred after the
penetration was complete. The hardness of the Cu-Ni-Al residual jet zone was much lower than that of
Ni-Al and even smaller than the hardness of the matrix. In other words, Ni-Al jet forms intermetallic
compounds that increase the hardness, while Cu weakens the reaction between Ni-Al and reduces the
number of intermetallic compounds.
Materials 2018, 11, 2267 10 of 11

5. Conclusions
The penetration experiments were performed on two kinds of shaped charge liners, Ni-Al and
Cu-Ni-Al. The average penetration depth of Cu-Ni-Al jet was increased by 42% compared to the
average penetration depth of Ni-Al jet. The microstructures of the targets were analyzed to investigate
Ni-Al reactive jet on SICR behaviors and the effect of Cu on SICR behaviors of Ni-Al jet. Although
many issues, including the mesoscale characteristics of powders or the structures of shaped charge
could affect the SICR behaviors of Ni-Al jet, our results demonstrate that Ni-Al reactive jet did not
completely react after the shock wave, and could release heat energy after penetration. Little oxidation
occurred at 60 mm standoff in Ni-Al and Cu-Ni-Al reactive jet, and the energy that caused the
microstructural change of the targets was mainly provided by plastic deformation and exothermicity
when the intermetallic compounds were formed. The results of the penetration experiments, EDS,
and Vickers microhardness measurements indicate that the addition of Cu not only reduces the initial
SICR behavior of the Ni-Al jet but also enhances the penetration performance and subsequent release
behavior of Ni-Al reactive jet. The purpose of using RSM in shaped charge liners is to keep little or no
reaction while the explosive is driving the liners, have specific penetration capability, and have enough
reactivity when the jet penetrates the target and then releases more energy to the target. Based on
our analysis, Cu enables Ni-Al to have these characteristics that could provide new insight into novel
warhead design.
Changing standoff distance may increase the length of the jet or break up the jet since the
penetration performance would vary widely. The reaction of Ni-Al and the interaction between the jet
and target will not be similar based on the different mass fraction of Cu. In future work, we aim to
vary the standoff and mass fraction of Cu for the reactive jet to understand the influence of standoff
and mass fraction of Cu on RSCL penetration performance.

Author Contributions: Conceptualization, Y.L. and M.S.; methodology, Y.L.; validation, C.L. and M.S.;
formal analysis, X.Z.; investigation, M.S.; resources, X.H. (Xiaomin Hu); data curation, X.H. (Xiaoyan Hu);
writing—original draft preparation, M.S.; writing—review and editing, M.S.; visualization, X.H. (Xiaoyan Hu);
supervision, X.H. (Xiaoyan Hu); project administration, Y.L.; funding acquisition, Y.L.
Funding: The National Natural Science Foundation for Young Scientists of China (No. 11802274) and Key
Laboratory Open Research Foundation of North University of China (DXMBJJ2018-01).
Acknowledgments: The authors thank Professor Tiansheng Liu for technical guidance, Qiang Yang for conducting
the Vickers microhardness measurements as well as assistance during their evaluation. The support of Sining Li is
also gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Hastings, D.L.; Dreizin, E.L. Reactive Structural Materials: Preparation and Characterization. Adv. Eng. Mater.
2017, 20, 1700631. [CrossRef]
2. Zhang, X.F.; Shi, A.S.; Qiao, L.; Zhang, J. Experimental study on impact-initiated characters of multifunctional
energetic structural materials. J. Appl. Phys. 2013, 113, 083508. [CrossRef]
3. Tao, Y.Q.; Bai, S.X.; Yang, S.Q.; Li, S. Research status of preparation technology for reactive material structures.
Chin. J. Nonferrous Met. Nonferrous Met. 2017, 27, 2079–2090. (In Chinese)
4. Thadhani, N.N. Shock-induced chemical reactions and synthesis of materials. Prog. Mater. Sci. 1993, 37, 117–226.
[CrossRef]
5. Zhang, D.; Tao, W.; Yu, Y.; Pan, J.; Wei, W. Impact Energy Release Behaviors of Ni-Al Energetic Structural
Material. Chin. J. Rare Met. 2017, 41, 40–44. [CrossRef]
6. Homan, B.E.; Mcnesby, K.L.; Ritter, J.; Colburn, J.; Brant, A.; Pandey, R. Investigations of the Energy Release
Mechanisms of Aluminum-Nickel Reactive Material System. In Proceedings of the 26th Army Science
Conference, Orlando, FL, USA, 1–8 December 2008.
7. Xiong, W.; Zhang, X.; Tan, M.; Liu, C.; Wu, X. The Energy Release Characteristics of Shock-Induced Chemical
Reaction of Al/Ni Composites. J. Phys. Chem. C 2016, 120, 24551–24559. [CrossRef]
Materials 2018, 11, 2267 11 of 11

8. Walters, W.P.; Kecskes, L.J.; Pritchett, J.E. Investigation of a Bulk Metallic Glass As a Shaped Charge Liner
Material. In Proceedings of the 23rd International Symposium on Ballistics, Tarragona, Spain, 16–20 April
2007; pp. 269–274.
9. Church, P. Investigation of a Nickel-Aluminum Reactive Shaped Charge Liner. J. Appl. Mech. 2013, 80, 031701.
[CrossRef]
10. Song, I.; Thadhani, N.N. Shock-induced chemical reactions and synthesis of nickel aluminides. Met. Trans. A
1992, 23, 41–48. [CrossRef]
11. Li, R.J.; Liu, T.S.; Shen, Z.W.; Fan, Z.J. On stability of jet produced by shaped charge with porous liner.
Explos. Shock Waves 2009, 29, 217–220. (In Chinese)
12. Babkin, A.V.; Ladov, S.V.; Fedorov, S.V. Analysis of Influence of the Sintered Liner Composition on the
Shaped-Charge Jet Free Flight Behavior and Its Penetration Capacity. In Proceedings of the 25th International
Symposium on Ballistics, Beijing, China, 17–21 May 2010.
13. Xi, B.; Liu, J.; Li, S.; Lv, C.; Guo, W.; Wu, T. Effect of interaction mechanism between jet and target on
penetration performance of shaped charge liner. Mater. Sci. Eng. A 2012, 553, 142–148. [CrossRef]
14. Meyers, M.A.; Gray, G.T.; Thadhani, N.N. The dynamic behavior of materials: An introduction. JOM
2010, 62, 14–15. [CrossRef]
15. Zhao, Z.; Liu, J.; Guo, W.; Li, S.; Wang, G. Effect of Zn and Ni added in W–Cu alloy on penetration performance
and penetration mechanism of shaped charge liner. Int. J. Refract. Met. Hard Mater. 2016, 54, 90–97. [CrossRef]
16. Yin, Z.X.; Ma, C.M.; Li, S.X.; Cheng, G.Q. Perforation of an ultra-high strength steel penetrated by shaped
charge jet. Mater. Sci. Eng. A 2004, 379, 443–447. [CrossRef]

© 2018 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/).