C Journal of

Carbon Research

Article
Electrodeposition of Cu–SWCNT Composites
Pavan M. V. Raja 1 , Gibran L. Esquenazi 1 , Cathren E. Gowenlock 2 , Daniel R. Jones 2 ,
Jianhua Li 3 , Bruce Brinson 1 and Andrew R. Barron 1,2,4, *
1 Department of Chemistry, Rice University, Houston, TX 77005, USA
2 Energy Safety Research Institute, Swansea University, Bay Campus, Swansea SA1 8EN, UK
3 Shared Equipment Authority, Rice University, Houston, TX 77005, USA
4 Department of Materials Science and Nanoengineering, Rice University, Houston, TX 77005, USA
* Correspondence: a.r.barron@swansea.ac.uk; Tel.: +44-01792-606930




Received: 23 May 2019; Accepted: 11 July 2019; Published: 13 July 2019


Abstract: Single walled carbon nanotubes (SWCNTs) are used as a component of a plating solution
of CuSO4 for direct current electrodeposition of Cu–SWCNT composites with varying nanotube
proportions without the use of either a surfactant, a dispersing agent, or functionalization of the
SWCNTs. The Cu–SWCNT composites are characterized by scanning electron microscopy (SEM),
energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction
(XRD), and Raman spectroscopy. The composites are comprised of metallic Cu and SWCNTs with
minor oxide impurities, as well as the residual (Fe) catalyst from the unpurified SWCNTs, in addition
to displaying nanotube-mediated morphological differences. EDX analysis of carbon (wt%) is close to
quantitative with respect to the wt% of SWCNTs added to the electrolysis solution. The presence
of SWCNTs decreases the oxidation of the copper, as well as changing the identity of the oxide
from CuO, for electrolysis of Cu, to Cu2 O. Hard adherent Cu–SWCNT coatings are prepared by the
addition of Cu powder to the electrolysis solution. The approach described in this paper will enable
controlled synthesis of metal-nanomaterial composites that can potentially be processed further into
high ampacity electrical conductors.

Keywords: single walled carbon nanotube; SWCNT; copper; electrodeposition; coating

1. Introduction
The potential of carbon nanotubes (CNTs), especially single walled carbon nanotubes (SWCNTs),
for high-ampacity, low weight, electrically conducting cables, as a replacement to traditional copper
wires, has garnered significant research attention [1]. Unfortunately, despite much hype, the realization
of CNT-based transmission cables has to overcome significant technical hurdles. One stopgap solution
involves the admixing of small amounts of CNTs to enhance the electrical properties of copper [2–5].
The fabrication of such Cu–CNT composite material, termed “ultra-conductive copper”, can be achieved
by a variety of different methods, including electrolytic co-deposition [6,7], electroless plating [8,9], and
powder metallurgy [10]. Being malleable, copper offers an excellent composite matrix, which can be
processed into a desired shape, with potential orientation of the fillers, through extrusion, densification,
and hot-pressing. Thus, routes to prepare precursor composites with a controlled Cu–CNT composition
could provide potential precursors to extruded wires.
Prior studies have evaluated electrodeposition of copper–carbon material composites under various
experimental conditions. One of the challenges pertains to improving the interface between copper and
the highly hydrophobic surface of carbon substrates [11]. Arai et al. have reported the fabrication and
characterization of Cu–CNT composite films using an electrodeposition technique [12,13]. In particular,
they have reported the synthesis of copper–multiwalled carbon nanofiber and multi walled carbon

C 2019, 5, 38; doi:10.3390/c5030038 www.mdpi.com/journal/carbon

C 2019, 5, 38 2 of 14

nanotube (MWCNT) composite powder materials [7,14]. Such studies give impetus to progress further
in terms of obtaining a deeper understanding of the interface between copper and carbon nanotubes.
In this regard the electrodeposition of copper single walled carbon nanotube (SWCNT) coatings
in an ultrasonic field [15], and the synthesis of Cu–MWCNT and Cu–SWCNT composite films via
electrodeposition where a dispersing agent was used to homogenize the hydrophobic CNTs have been
reported [16,17]. Fen et al. have reported the use of nano diamond as dispersing/seed agents [18].
However, there is a paucity of studies focused on Cu–SWCNT composite formation in electroplating
bath conditions free of dispersing agents, which will likely contribute to contamination of the resulting
composites and will be hard to eliminate.
We have previously reported the electromigration behavior of raw and acid purified SWCNTs in
dilute aqueous systems, in the absence of surfactant, with the addition of either acetic acid or CuSO4 [19].
The results showed that the electromigration of raw SWCNTs (with catalyst residue) in the presence of
CuSO4 resulted in the formation of a Cu–SWCNT composite material at the cathode. In contrast, acid
purified SWCNTs were observed to diffuse to the anode, creating fibrils agglomerates [19]. With the
addition of CuSO4 the direction of electromigration reversed back towards the cathode resulting in
the co-deposition of SWCNTs and Cu metal on the cathode. In this study, we report the effects of
reaction conditions and varying the proportion of added SWCNTs studied in relation to characteristic
properties of the related composites in terms of morphology and composition. The electroplating
process (using two electrodes) was kept the same as in our prior paper on electromigration [19] for the
sake of simplicity and consistency, and keeping practical applications in mind. Further experiments
utilizing reference electrodes are reported elsewhere [20]. A control study based on admixing copper
microparticles into the electroplating bath and the resulting composite morphologies will also be
presented in this report.

2. Materials and Methods

Commercial grade copper (16 or 18 gauge) and platinum (18 gauge) wire (Sigma Aldrich, St Louis,
MO, USA) were cleaned by wiping their surfaces with acetone, to remove any loosely bound or
dissolvable surface impurities. Unpurified raw HiPCO SWCNTs (SWCNTs) were obtained from
Tubes@Rice (Houston, TX, USA) batch 09-HiPco-0093 (batch No. 188.4) and used without further
purification. Aqueous acetic acid (0.8 M) was used as supplied. CuSO4 .5H2 O, concentrated sulfuric
acid, acetone, and ethanol were obtained from Fisher Scientific (St. Louis, MO, USA) and used as is.
The electroplating bath was comprised of 0.1 M copper sulfate solution fortified with 5% by
volume dilute acetic acid solution (0.8 M) to improve the bath’s electrical conductivity. Raw CNTs
were added to the 0.1 M CuSO4 baths (with 5% 0.8 M acetic acid added) and sonicated for 10 min
before commencement of the electroplating reactions. The plating baths were initially heated to 60 ◦ C
over 10 min with 700 rpm stirring in the case of CNT-containing baths. No stirring was conducted for
CNT-free control. Then heat was turned off after 10 min of reaction, as the bath heated up due to the
externally supplied current, and the reactions were continued without further heating. The anode
was a 1.25 cm section of 18-gauge platinum wire (Sigma Aldrich, St Louis, MO, USA) and the cathode
was a 5 cm section of 18-gauge copper wire (Sigma). All baths were subjected to 14.7 V DC (Elenco
Precision Inc. (Wheeling, IL, USA) Model XP-85 variable DC power supply) during the electroplating
reaction. No surfactants were used. The Cu–CNT composite was deposited on the copper cathode and
sloughed off the cathode frequently. After the reactions, the deposit from each sample was collected
on 0.2 µm polyvinylidene difluoride (PVDF) membranes (Millipore), washed thoroughly in DI water,
followed by acetone (to remove water), and air-dried over 3 days to obtain porous, powdery deposits.
The samples were weighed and saved for characterization. Table 1 summarizes the reaction conditions
used to obtain the various Cu–SWCNT electroplated samples (and SWCNT-free control).
Visual evidence for SWCNT entrapment in copper-based composite matrix was obtained by the
dispersion of 230 mg of the sample with 2.3% SWCNTs, in a mixture of concentrated H2 SO4 (3 mL)
and DI water (5 mL) heated to 200 ◦ C for 1 h with 350 rpm stirring. The sulfuric acid was added to
C 2019, 5, 38 3 of 14

dissolve some of the copper and release embedded CNT aggregates. The dispersion was allowed to
cool and the particles were allowed to settle overnight. The association of the black aggregates with the
magnetic stir bar visually indicated the presence of the SWCNTs incorporating iron catalyst impurities
(Figure S1).

Table 1. Composition of electrolysis bath, electrodeposition time, and yield of products.

Reaction Volume SWCNT Electrodeposition Air-Dried Product SWCNT

(mL) (mg) Time (min) (mg) (wt%)
75 0 90 350 0.0
150 17 210 753 2.3
100 17 90 450 3.8
60 17 90 274 6.2

In a parallel experiment, micron-sized copper powder (3.2 g, Sigma, St. Louis, MO, USA) was
added to 0.1 M CuSO4 (400 mL) in a 500-mL plating bath incorporating acetic acid (5 mL), with SWCNTs
(17 mg, 0.004 wt%), to yield a combination of hard coatings on four 10 cm copper cathodes. The bath
was sonicated 20 min before commencement of the electroplating reaction. The bath was stirred at all
times at 1000–1200 rpm to facilitate thorough mixing of dispersed fillers in the bath, and the reaction
was allowed to proceed for 8.5 h. Temperature was maintained at 70 ◦ C. Care was taken to ensure that
the cathode and anode (1.25 cm platinum wire electrode, Sigma Aldrich, St Louis, MO, USA) were
fully immersed at the periphery of the mixing vortex in the bath. If needed, DI water was added to the
bath to sustain plating bath volume at the starting level, to account for water evaporation during the
plating process. After the reaction, the copper wire cathode with hardened copper/composite coating
was thoroughly washed under running DI water before being further washed in ethanol or acetone
(to accelerate the sample drying process) and air-dried overnight. In addition, sludge was collected
from the bath and washed over a 0.2 µm PVDF filter membrane (Millipore) using copious amounts
of water followed by acetone or ethanol to quickly dry out moisture. The filter cake was air-dried
overnight and subsequently stored in closed containers. The coated copper wires were stored in Ziploc
bags for further characterization, alongside corresponding powdery dried deposit obtained on the
filter membrane. The fraction of SWCNTs in the composite material was estimated approximately by
assuming that SWCNTs had distributed themselves proportionally between the hard coatings, and the
powdery deposit.
All raw materials and composite samples were characterized using a variety of material
characterization techniques to obtain a detailed understanding of their composition and morphology.
X-ray photoelectron spectroscopy (XPS) measurements were obtained over a 700 µm × 300 µm sample
area using a Kratos Axis Supra system with an Al-Kα X-ray source (1486.7 eV) operated at emission
current 15.00 mA and pass energy 20 eV, with charge neutralization applied to each sample using
a filament bias of 1 V, filament current 0.4 A and charge balance 3.3 V. Spectra were recorded using
a dwell time of 250 ms over a single sweep. Data was analyzed with CasaXPS software (Version
2.3.12.8). A spectrum energy calibration was performed with respect to the C 1s peak with binding
energy set to 284.8 eV (NIST XPS database). The speciation and composition variation were obtained
by recording the multiplex spectra for C 1s, O 1s, and Cu 2p elemental energy levels. X-ray diffraction
(XRD) measurements were conducted on a Rigaku D/MAX 2100 diffractometer with Cu-Kα radiation
and a graphite monochromator. Zero-background sample holders made of (511) Silicon single crystal
wafers were used for all samples. Data analysis was performed using Rigaku PDXL2 data analysis
software. The amount of Cu (PDF 04-009-2090), Cu2 O (PDF 04-002-3214) or CuO (PDF 04-007-1375) in
the samples was determined by Rietveld refinement of the measured XRD patterns. Scanning electron
microscopy (SEM) was carried out using a FEI Quanta 400 ESEM FEG equipped with an EDS detector
(FEI, Hillsboro, OR, USA). Images were acquired by placing samples on double-sided carbon tape
C 2019, 5, 38 4 of 14

that is fixed to aluminum SEM stubs, used as received. Images were acquired with a typical operating
voltage of 20 kV, with a working distance of 10 mm, spot size 3, under high vacuum. Energy dispersive
X-ray (EDX) analysis was performed and analyzed using EDAX TEAM™ software using 3 sample
areas. Thermogravimetric analyses (TGA) were conducted using a TA instruments (New Castle, DE,
USA) Q-600 simultaneous TGA/DSC with air as a carrier medium. Samples (5–10 mg) were then
placed in alumina pans and heated with a ramp rate of 3 ◦ C/min under 70 mL/min of the carrier gas.
Raman spectra were obtained using Renishaw inVia Raman Microscope (Wotton-under-Edge, UK),
at 514.5 nm wavelength, using a 50× LWD lens, data was acquired with 3 or more accumulations
between 100 cm−1 and 3300 cm−1 with cosmic-ray background removal applied.

3. Results and Discussion

SEM analysis of the raw HiPCO SWCNTs indicates a highly bundled fibrous structure.
The associated EDX data indicates iron catalyst impurity of ~47 wt%, while TGA data coupled
with EDX analysis of the residue revealed a ~20 wt% iron impurity [21]. This discrepancy is due to
local variations of iron content in the sample [22]. SEM analysis of the copper wire cathode showed
scratches due to handling, while EDX surprisingly revealed ~4 wt% iron content by weight probably
due to native impurities, since the material was commercial grade.

3.1. Electrolysis of SWCNTs in CuSO4 Solution

Several copper composite formulations bearing a range of calculated SWCNT percentages were
prepared using the electroplating method by varying the SWCNT concentration in the electroplating
bath, while maintaining a [CuSO4 ] of 0.1 M. Based upon our previous work it is likely that a fraction
of the copper ions from the bath were complexed to the SWCNT [9,19], forming nuclei for growth of
electroplated copper grains among the bundles [23]. Prior studies have reported on the benefits of
seeding copper moieties among SWCNT aggregates via chemical deposition methods, especially via
organic media that exfoliate nanomaterial aggregates to promote improved adhesion of electroplated
copper coatings on CNT surfaces [3]. Vortexing in the bath, caused by rapid stirring, and the applied
potential difference between the electrodes likely caused migration of copper ions along with SWCNT
aggregates (and their metallic catalyst impurities) toward the cathode. This was also observed in our
prior study on electromigration [19].
The mixed deposit of copper and SWCNT grew as a layer on the surface of the copper cathode
until it visually reached a thickness of 2–3 mm, at which point it sloughed off and fell to the bottom of
the bath. This process was repeated for the durations stated in Table 1 for each sample. The contents of
the plating bath, and any remaining deposit adhering loosely to the copper cathode were collected,
washed in DI water and acetone, and air-dried (Figure S4). This deposit could be easily removed
from the electrode surface, washed with DI water and acetone, and dried for further characterization.
Literature reports that higher voltages can speed up electrochemical reactions [24]. Hence, the choice
of 14.7 V, which was the highest setting in the DC voltage apparatus used for the study. The enhanced
rate of reaction coupled with agitation used to disperse the hydrophobic nanotubes in the plating
bath also likely resulted in non-adherent coatings on the cathode, but this was not of major concern
as the intention was to first collect any cathodic deposits for subsequent analysis and processing.
The cathodic sludge can be collected and processed further into compacts through compression and/or
extrusion. Ongoing experiments in our group are attempting to optimize the electroplating process
wherein copper is deposited as a smooth layer onto the CNT fiber/cable surfaces directly, rather
than onto individual CNT bundles dispersed in the plating bath. Several approaches to preparing
copper–nanotube composites are possible and the approach outlined in this paper is one of them,
with the uniqueness centered on the avoidance of surfactants despite the fact that the nanotubes
are hydrophobic.
Figure 1 shows representative SEM images (at two magnifications) of Cu–SCWNT composites
containing varying proportions of SWCNTs produced by direct current electroplating using the chosen
C 2019, 5, 38 5 of 14

constant voltage (14 V) power supply. Based on calculations, composites containing 0, 2.3, 3.8, and
6.2% SWCNTs were obtained. In the absence of SWCNTs (Figure 1a) the Cu deposited as a dendritic
(“fern-like”) structure comprising of individual crystallites of 0.25–0.5 µm in size (Figure 1b). A similar
morphology has been observed previously for Cu electrolysis under conditions of high concentration
and
C high
2019, overpotential
5, x FOR [25].
PEER REVIEW 5 of 13

Figure 1.1. Representative

Representative SEM
SEM images of electroplated
images of electroplatedcopper single
copper walled
single carbon
walled nanotube
carbon (Cu–
nanotube
SWCNT)
(Cu–SWCNT) composites electrodeposited
composites (at a(at
electrodeposited bath temperature
a bath of 60of°C)
temperature ◦ C) using
60 using 0 wt% SWCNT
0 wt% SWCNT(a,b), 2.3
(a,b),
wt% SWCNT
2.3 wt% SWCNT (c,d), 3.8 wt%
(c,d), SWCNT
3.8 wt% (e,f),(e,f),
SWCNT andand
6.2 wt% SWCNT
6.2 wt% SWCNT (g,h). ScaleScale
(g,h). 100=μm
bar =bar 100(a,c,e,g) and
µm (a,c,e,g)
1and
μm1 (b,d,f,h).
µm (b,d,f,h).

With the
With theaddition
additionof of 2.3 2.3
wt%wt% SWCNTsSWCNTs to thetoelectrolysis solution,
the electrolysis the dendritic
solution, nature appeared
the dendritic nature
to visuallyto
appeared decline
visuallywhile the structure
decline while the became more porous
structure became(Figure more 1c).porous At this concentration
(Figure 1c). At this the
SWCNT bundles appear to be coating the Cu crystallites in a highly heterogeneous
concentration the SWCNT bundles appear to be coating the Cu crystallites in a highly heterogeneous manner (Figure 1d).
The approach
manner (Figure postulated previously,postulated
1d). The approach where CNT aggregates
previously, are first
where CNT exfoliated
aggregates in anareorganic medium
first exfoliated
followed
in an organicby medium
reacting followed
with copper species,with
by reacting cancopper
potentially
species,be canused to overcome
potentially be usedthetoproblem
overcome of
heterogeneous nature of Cu–CNT composites [3]. Further increasing
the problem of heterogeneous nature of Cu–CNT composites [3]. Further increasing the SWCNT the SWCNT concentration results
in the completeresults
concentration loss ofinthethe
dendritic
complete structure
loss of(Figure 1e,g), and
the dendritic the resulting
structure (Figurematerial
1e,g), and is heterogeneous
the resulting
but uniform
material mix of Cu particles
is heterogeneous but uniform and SWCNTs
mix of Cu(Figure particles1f).andFinally,
SWCNTs at the highest
(Figure 1f).concentrations
Finally, at the
studied herein,
highest the individual
concentrations studied Cuherein,
crystallites have SWCNTs
the individual encapsulating
Cu crystallites have them (Figureencapsulating
SWCNTs 1h). A similar
morphology
them (Figure was
1h). observed
A similar in the electrodeposition
morphology was observed of Cuin and surfactant dispersed
the electrodeposition of CuMWCNTs [26,27].
and surfactant
Irrespectively, it is clear that the SWCNTs have altered the nucleation
dispersed MWCNTs [26,27]. Irrespectively, it is clear that the SWCNTs have altered the nucleation of of copper particles during
the electroplating
copper process.
particles during Unfortunately,process.
the electroplating as in previous work, itasisinclear
Unfortunately, that without
previous work, it subsequent
is clear that
densification
without the resulting
subsequent composites
densification will remain
the resulting heterogeneous
composites [27]. heterogeneous [27].
will remain
The EDX
EDXelemental
elementalanalysis
analysis of of
thethe
Cu–SWCNT
Cu–SWCNT composites
composites is shown in Table
is shown in 2.Table
Table2. 2 isTable
intended
2 is
to show a trend
intended to showin terms of carbon
a trend in terms content for the sake
of carbon contentof discussion
for the sake only,ofand not to present
discussion only,a andstatistically
not to
validateda observation.
present As wouldobservation.
statistically validated be expected the As copper
would be composition
expected is theinversely
copper proportional
composition to is
carbon content (Figure S5), and the EDX analysis of carbon (wt%) is close
inversely proportional to carbon content (Figure S5), and the EDX analysis of carbon (wt%) is close to quantitative with respect
the wt% of SWCNTs
to quantitative with respectadded to the(Figure
wt% of 2) SWCNTs
suggesting that all
added the SWCNTs
(Figure 2) suggesting are incorporated
that all the SWCNTsinto the
composite. This is possible considering that all dispersed solids (including
are incorporated into the composite. This is possible considering that all dispersed solids (including any CNTs unbound to the
copper
any CNTsduring the plating
unbound to theprocess)
copper in the plating
during bath were
the plating collected
process) in the(after
platingphysical
bath mixing) onto a
were collected
filter membrane
(after and dried.
physical mixing) ontoThe presence
a filter of oxygen
membrane andcan be due
dried. Thetopresence
native oxide layers can
of oxygen on the be copper
due to
formedoxide
native by self-passivation,
layers on the copper along withformed oxygen-containing
by self-passivation, defect groups
along with on nanotube surfaces
oxygen-containing [28].
defect
It is alsoonlikely
groups that copper
nanotube surfacesoxides
[28]. Itmay have
is also formed
likely in the plating
that copper oxides may bathhave priorformed
to deposition in the
in the plating
cathode,
bath priorand prior researchers
to deposition have reported
in the cathode, and prior on the electrodeposition
researchers have reported of copper
on theoxides [29,30]. It is
electrodeposition
interesting
of copper to note, [29,30].
oxides however,Itthat the oxygen to
is interesting content
note,decreases
however,dramatically
that the oxygen with addition
content ofdecreases
SWCNT
(Table 2), suggesting
dramatically that theof
with addition presence
SWCNT of (Table
the hydrophobic
2), suggesting SWCNTs decreases
that the presence the of oxidation of Cu (see
the hydrophobic
SWCNTs decreases the oxidation of Cu (see below). However, increased SWCNT content beyond 2.3
wt% did not result in further decrease in oxygen content. The observed trends could likely be due to
passivation [31,32], increased corrosion potential [33], or reduction [20] of the Cu; however, we note
that under non-electolysis conditions CuO is the preferred composition when copper is deposited on
CNTs [34].
C 2019, 5, 38 6 of 14

below). However, increased SWCNT content beyond 2.3 wt% did not result in further decrease in
oxygen content. The observed trends could likely be due to passivation [31,32], increased corrosion
potential [33], or reduction [20] of the Cu; however, we note that under non-electolysis conditions CuO
is the preferred composition when copper is deposited on CNTs [34].
C 2019, 5, x FOR PEER REVIEW 6 of 13

Table 2. EDX analysis of electroplated Cu–SWCNT composites electrodeposited at a bath temperature

Table 2. EDX analysis of electroplated Cu–SWCNT composites electrodeposited at a bath
of 60 ◦ C.
temperature of 60 °C.
SWCNT (wt%) C (at%) O (at%) Cu (at%) Fe (at%)
SWCNT (wt%) C (at%) O (at%) Cu (at%) Fe (at%)
0.0 0.0 1.11.1± ± 0.4
0.4 ± 0.6
8.48.4 ± 0.6 90.0 ± 1.7 0.7 ± 0.7
90.0 ± 1.7 0.7 ± 0.7
2.3 2.3 18.3± ±
18.3 2.3
2.3 ± 0.3
1.31.3 ± 0.3 77.6 ± 4.0 1.5 ± 0.5
77.6 ± 4.0 1.5 ± 0.5
3.8 3.8 20.0
20.0± ± 2.4
2.4 2.02.0 ± 0.2
± 0.2 76.5 ± 2.5
76.5 ± 2.5 1.3 ± 0.5 1.3 ± 0.5
6.2 6.2 30.6 ± 7.0
30.6 ± 7.0 1.5 ± 0.3
1.5 ± 0.3 65.7
65.7 ± 7.2 ± 7.2
2.2 ± 0.1 2.2 ± 0.1

Figure 2. Plot
Figure2. Plot of
of carbon
carbon (wt%)
(wt%) determined
determined by
by EDX
EDX analysis
analysis versus
versus carbon
carbon(wt%)
(wt%)added
addedin
inthe
theform
formof
of
SWCNTs to the electrolysis (R2 = 0.95). EDX shown as an average of 5 independent measurements
SWCNTs to the electrolysis (R = 0.95). EDX shown as an average of 5 independent measurements
2

per
persample.
sample.

The presence of Fe is associated with the catalyst residue present in the SWCNTs [22,35], and hence
The presence of Fe is associated with the catalyst residue present in the SWCNTs [22,35], and
the iron content is generally proportional to carbon (Figure S6). Surprisingly, even the SWCNT-free
hence the iron content is generally proportional to carbon (Figure S6). Surprisingly, even the
control copper deposit was found to contain iron. EDX characterization of copper wire electrode
SWCNT-free control copper deposit was found to contain iron. EDX characterization of copper wire
material confirmed the presence of up to 4 wt% of iron. It is likely that some of this iron could have
electrode material confirmed the presence of up to 4 wt% of iron. It is likely that some of this iron
leached into the deposit during the electroplating process.
could have leached into the deposit during the electroplating process.
The surface composition of the composites may be verified by XPS analysis (Table 3); Cu 2p spectra
The surface composition of the composites may be verified by XPS analysis (Table 3); Cu 2p
corresponding to electrodeposited copper and Cu–SWCNT composite deposited with 4 wt% SWCNTs
spectra corresponding to electrodeposited copper and Cu–SWCNT composite deposited with 4 wt%
are displayed in Figure 3a,b, respectively. Whilst it is difficult to separate the contributions from Cu2 O
SWCNTs are displayed in Figure 3a,b, respectively. Whilst it is difficult to separate the contributions
and metallic Cu due to the close proximity of their components, each of which appear at a binding
from Cu2O and metallic Cu due to the close proximity of their components, each of which appear at
energy of ca. 932.7 eV, the presence of a component at ca. 933.2 eV in Figure 3a is consistent with the
a binding energy of ca. 932.7 eV, the presence of a component at ca. 933.2 eV in Figure 3a is
CuO chemical environment [36–38]. Conversely, no CuO component was observed in the case of the
consistent with the CuO chemical environment [36–38]. Conversely, no CuO component was
Cu–SWCNT composite, indicating that co-deposition with SWCNTs yielded a higher degree of copper
observed in the case of the Cu–SWCNT composite, indicating that co-deposition with SWCNTs
reduction than electrodeposition of copper alone. Our hypothesizes is that the possible inhibition of
yielded a higher degree of copper reduction than electrodeposition of copper alone. Our
oxidation of copper in the presence of the SWCNTs due to their acting as potential reducing agents
hypothesizes is that the possible inhibition of oxidation of copper in the presence of the SWCNTs
or redox catalysts [39,40]. The presence of hydroxides in the samples was likely due to the partial
due to their acting as potential reducing agents or redox catalysts [39,40]. The presence of
reaction of copper oxide with water from either the bath, or from atmospheric humidity. In both cases,
hydroxides in the samples was likely due to the partial reaction of copper oxide with water from
a large component measured at a binding energy of ca. 934.7 eV may be attributed to the presence
either the bath, or from atmospheric humidity. In both cases, a large component measured at a
of Cu(OH)
binding 2 in the
energy of samples
ca. 934.7 [36,38].
eV may Itbeshould be noted
attributed to thethat due toofsmall
presence chemical
Cu(OH) shifts between the
2 in the samples [36,38]. It
Cu/Cu O and CuO environments, it is difficult to accurately determine the position
should2 be noted that due to small chemical shifts between the Cu/Cu2O and CuO environments, and relative area
it is
of the CuO component in Figure 3a; for this reason, the estimated atomic percentage of
difficult to accurately determine the position and relative area of the CuO component in Figure 3a; CuO given in
Table 3 should be treated as approximate.
for this reason, the estimated atomic percentage of CuO given in Table 3 should be treated as
approximate.
C 2019, 5, 38 7 of 14
C 2019, 5, x FOR PEER REVIEW 7 of 13

Figure3.3. High
Figure High resolution
resolution Cu Cu 2p2p XPS
XPS showing
showing the
the presence
presence ofof copper
copper oxidation
oxidation states
states inin(a)
(a)
electrodeposited
electrodepositedcopper
copperand and(b)
(b)Cu–SWCNT
Cu–SWCNTcomposite
compositedeposited
depositedwith
with3.8
3.8wt%
wt%SWCNTs
SWCNTsinin CuSO
CuSO 4 4
(0.1 ◦ C.
(0.1M)
M)solution
solutionatata abath
bathtemperature
temperature ofof
6060 °C.

Table 3. Chemical composition of copper estimated from the relative areas of components within the
Table 3. Chemical composition of copper estimated from the relative areas of components within the
Cu 2p XPS spectra of Cu–SWCNT composites electrodeposited at a bath temperature of 60 ◦ C. 1 . 1
Cu 2p XPS spectra of Cu–SWCNT composites electrodeposited at a bath temperature of 60 °C. .
SWCNT (wt%)
SWCNT (wt%)Cu and Cu2 O (at%)
Cu and Cu2O (at%) CuO
CuO(at%)
(at%) Cu(OH)2 (at%)
Cu(OH) 2 (at%)
0.0 0.0 43.9 43.9 12.9
12.9 43.243.2
3.8 3.8 62.7 62.7 −− 37.337.3
1 Contributions
1 Contributions
fromfrom CuCu
Cu and and
2O Cunot
are 2O are not
easily easily distinguished
distinguished from
from each other each
due other
to the closedue to theofclose
proximity the
associated components.
proximity of the associated components.

X-ray
X-raydiffraction
diffraction(XRD)
(XRD)ofofall allthe
theelectroplated
electroplatedsamples
samples(Table (Table4)4)reveals
revealscrystalline
crystallineCuCuasasthe
the
major
majorcomponent
componentininall allcases.
cases.As
Asisissuggested
suggestedby byEDX
EDXand andXPSXPSthere
thereisisa aminor
minorcomponent
componentofofoxide
oxide
inineach
eachsample;
sample;however,
however,the thepercentage
percentageofofoxide
oxidewaswasnot notproportional
proportionaltotopercentage
percentageofofSWCNT
SWCNT
added
added(consistent
(consistent with EDXEDX
with measurements,
measurements,see Table
see 2), it is possibly
Table 2), it isdue changesdue
possibly in the morphology
changes in the
(Figure 1) and(Figure
morphology hence surface area ofsurface
1) and hence the samples.
area ofAlternatively, Liu et al. haveLiu
the samples. Alternatively, shown
et al.that
haveduring
shown
electrodeposition, the thicker thethe
that during electrodeposition, copper plated
thicker the layer,
copper the thicker
plated was the
layer, the thicker
oxide filmwas[41].
the An alternative
oxide film [41].
explanation
An alternativewould be that thewould
explanation presence of SWCNTs
be that altersofthe
the presence plating alters
SWCNTs current density,
the platingthat is known
current to
density,
affect
that the concentrations
is known to affect of impurities
the [42]. We
concentrations of note that unlike
impurities [42].XPS
We (Figure
note that 3) unlike
no Cu(OH) is observed
XPS2(Figure 3) no
inCu(OH)
the XRD 2 is(Figure 4) [43];
observed in thehowever, given the
XRD (Figure surface
4) [43]; naturegiven
however, of XPS,
thethis would
surface suggest
nature that the
of XPS, this
Cu(OH) is formed
would 2suggest thatbythe
surface
Cu(OH) hydrolysis
2 is formedrather than ashydrolysis
by surface a bulk material.
rather than as a bulk material.

Table
Table4. Chemical composition
4. Chemical and crystal
composition grain size
and crystal as determined
grain by XRD of by
size as determined Cu–SWCNT composites
XRD of Cu–SWCNT
electrodeposited at a bath temperature of 60 ◦ C. 1 .
composites electrodeposited at a bath temperature of 60 °C. . 1

Composition
Composition CrystalGrain
Crystal Grain Size
Size
SWCNT
SWCNT (wt%) (wt%) Cu
Cu (wt%) (wt%) Cu 2 O
Cu2 O (wt%)(wt%) CuO
CuO (wt%) (wt%) Cu
Cu (Å) (Å) Cu 2 O
Cu2 O (Å)(Å) CuO
CuO (Å)
(Å)
0.0 0.0 70.0
70.0 (4) (4) − − 30.0(4)
30.0(4) 244 (15)
244 (15) − − 64 (11)
64 (11)
2.3 98.7 (2) 1.3 (2) − 201 (3) 117 −
2.3 98.7 (2) 1.3 (2) − 201 (3) 117 −
3.8 97.5 (2) 2.5 (2) − 254 (17) 306 −
3.8 97.5 (2) 2.5 (2) − 254 (17) 306 −
6.2 99.2 (2) 0.8 (2) − 202 (10) 145 −
1 6.2 values given
Error 99.2 (2) 0.8 (2)Weak signals
in parentheses. − pertaining202 to(10)
Cu2O enabled −
145 to the analytics
1 Error values
software togiven
yieldinonly
parentheses.
singularWeak
datasignals
withoutpertaining to Cu2 O enabled to the analytics software to yield only
error determination.
singular data without error determination.

The most interesting observation is that, as suggested by XPS, the identity of the oxide is
The
dependentmost oninteresting observation
the presence is that, asThe
of the SWCNTs. suggested by XPS,control
SWCNT-free the identity of thethe
displayed oxide is dependent
presence of CuO
on
(ICDD #04-007-1375), but the oxide in all the samples containing SWCNTs is CuO
the presence of the SWCNTs. The SWCNT-free control displayed the presence of Cu2O(ICDD(ICDD
#04-007-1375), but the oxide in all the samples containing SWCNTs is Cu O (ICDD
#04-002-3214), see Figure 4. This change suggests that the presence of added SWCNTs modifies the
2 #04-002-3214),
see Figure
nature of 4.
theThis change
native suggests
oxide that the presence
layers formed. Additivesofsuch
added
as SWCNTs
water andmodifies the nature
acids promote the of theof
rate
native oxide of
formation layers
Cu2O formed.
by theAdditives
oxidation such
of as
Cuwater andasacids
metal, wellpromote the rate oxidation
as the further of formation to of Cu2 O
CuO. So
presumably, under the present conditions the SWCNTs inhibit the subsequent conversion of Cu2O
C 2019, 5, 38 8 of 14

by the5,oxidation
C 2019, x FOR PEERof Cu metal, as well as the further oxidation to CuO. So presumably, under
REVIEW the
8 of 13
present conditions the SWCNTs inhibit the subsequent conversion of Cu2 O to CuO; however, we have
to CuO; however,
previously observedwethe
have previously
opposite underobserved the opposite
higher energy under
conditions higher
[34]. energy conditions
An alternative [34].
explanation
An alternative
could explanation
involve the thickness could
of the involve the thickness of the Cu coating.
Cu coating.

Figure
Figure 4. XRDofof(a)
4. XRD (a)electrodeposited
electrodeposited copper
copper and
and (b)(b) Cu–SWCNT
Cu–SWCNT composite
composite deposited
deposited withwith 4.0
4.0 wt%
wt% SWCNTs in CuSO solution at a bath temperature of 60 ◦ C, showing the presence of Cu (ICDD
SWCNTs in CuSO4 solution at a bath temperature of 60 °C, showing the presence of Cu (ICDD
4
#04-009-2090),
#04-009-2090), CuO
CuO (ICDD
(ICDD #04-007-1375),
#04-007-1375), and
and Cu
Cu22O
O (ICDD
(ICDD #04-002-3214).
#04-002-3214).

It
It was
was observed
observed previously
previously [42] [42] that
that when
when Cu Cu coating
coating isis less
less than
than 0.165
0.165 µmμm the the oxide
oxide is is CuO
CuO
(with a Cu O interface to Cu); however, when the coating is thicker than 0.165
(with a Cu2O interface to Cu); however, when the coating is thicker than 0.165 μm the oxide is Cu22O.
2 µm the oxide is Cu O.
Based
Based upon this observation,
upon this observation,ititwould wouldsuggest
suggestthat
thatthe
thepresence
presence ofofthethe SWCNTs
SWCNTs actsacts
as as a seed
a seed for for
Cu
Cu growth. Seeding usually occurs at native or induced defect sites on the
growth. Seeding usually occurs at native or induced defect sites on the nanotube surfaces [44,45]. nanotube surfaces [44,45].
The
The crystal
crystal grain
grain sizesize for
for the
the Cu
Cu and
and the
the oxides
oxides showed
showed no no correlation
correlation between
between crystallite
crystallite size
size and
and
SWCNT content
SWCNT content (Table 4).(Table 4).
The
The Raman
Raman spectra
spectra of of the
the Cu–SWCNTs
Cu–SWCNTs composites
composites showshow thethe presence
presence D D and
and G G bands
bands andand thethe
radial breathing modes associated with SWCNTs (e.g., Figure 5a). The
radial breathing modes associated with SWCNTs (e.g., Figure 5a). The D band represents the D band represents the presence
of sp3 carbon
presence of spcenters
3 carbon (as opposed
centers to sp2 carbon
(as opposed to sp2of a pristine
carbon SWCNT),
of a pristine thus, the
SWCNT), IG :Ithe
thus, D ratio
IG:IDisratio
oftenis
used as a good indicator of quality in bulk samples [46]. As seen in Table 5,
often used as a good indicator of quality in bulk samples [46]. As seen in Table 5, the IG:ID ratios the IG :ID ratios appeared
consistent
appeared in the samples
consistent in the containing
samplesadded SWCNTs,
containing addedbut SWCNTs,
were lowerbut than for the
were lowerSWCNTs
than for before
the
electrolysis
SWCNTs before (I :I = 15.52 ± 1.52, Figure 5b). This observation suggests that the
G D electrolysis (IG:ID = 15.52 ± 1.52, Figure 5b). This observation suggests that the structure of the SWCNTs
underwent
structure ofa the consistent
SWCNTs change during athe
underwent electroplating
consistent change process,
duringpossibly due to the presence
the electroplating of acetic
process, possibly
acid in the plating bath. Prior research has suggested that nanotubes with
due to the presence of acetic acid in the plating bath. Prior research has suggested that nanotubes low diameters and initial
Iwith
:I > 1 are significantly susceptible to structural modification during acid treatment
G D low diameters and initial IG:ID > 1 are significantly susceptible to structural modification during [47].
acid treatment [47].
Table 5. The IG :ID ratio determined from the Raman spectrum (514 nm) of Cu–SWCNT composites
electrodeposited at a bath temperature of 60 ◦ C.

SWCNT (wt%) IG :ID 1

0.0 N/A
2.3 11.43 (0.75)
3.8 12.43 (1.46)
6.2 10.18 (1.93)
1 All samples averaged from 3 regions of the sample and standard deviations are given in parenthesis.
 appeared consistent in the samples containing added SWCNTs, but were lower than for the
SWCNTs before electrolysis (IG:ID = 15.52 ± 1.52, Figure 5b). This observation suggests that the
structure of the SWCNTs underwent a consistent change during the electroplating process, possibly
due to the presence of acetic acid in the plating bath. Prior research has suggested that nanotubes
with low diameters and initial IG:ID > 1 are significantly susceptible to structural modification during
C 2019, 5, 38 9 of 14
acid treatment [47].

C 2019, 5, x FOR PEER REVIEW 9 of 13

Figure 5. Raman spectra (514 nm) of (a) HiPCO SWCNTs before electrolysis, (b) Cu–SWCNT
composite deposited with 6.2 wt% SWCNTs in CuSO4 solution at a bath temperature of 60 °C, (c) Cu
deposited from CuSO4 solution at a bath temperature of 60 °C showing the peak for CuO, and (d) the
hard adherent Cu–SWCNT coatings formed from electrolysis in the presence of Cu micropowder.

Table 5. The IG:ID ratio determined from the Raman spectrum (514 nm) of Cu–SWCNT composites
electrodeposited at a bath temperature of 60 °C.

SWCNT (wt%) IG:ID 1

0.0 N/A
2.3 11.43 (0.75) composite
Figure 5. Raman spectra (514 nm) of (a) HiPCO SWCNTs before electrolysis, (b) Cu–SWCNT
deposited with 6.2 wt% 3.8
SWCNTs in CuSO4 solution at a bath temperature of12.4360 ◦ C,(1.46)
(c) Cu deposited
from CuSO4 solution at a bath temperature of 60 C showing the peak for CuO,(1.93)
6.2 ◦ 10.18 and (d) the hard
1 All samples
adherent averaged coatings
Cu–SWCNT from 3 regions
formedoffrom
the sample and in
electrolysis standard deviations
the presence of Cuare given in parenthesis.
micropowder.

3.2. Electrolysis
3.2. Electrolysis in
in the
the Presence
Presence of
of Cu
Cu Micropowder
Micropowder
The Cu–SWCNT
The Cu–SWCNTcomposites
compositesgenerated
generatedconsisted of porous
consisted deposit
of porous that sloughed
deposit off the cathode
that sloughed off the
into the bath, and had to be filtered, washed, and dried, yielding a powdery residue.
cathode into the bath, and had to be filtered, washed, and dried, yielding a powdery residue. In an attempt to
In an
induce harder,
attempt to induceadherent
harder,coatings
adherent oncoatings
the cathode surface,
on the microscale
cathode surface, copper particles
microscale were
copper suspended
particles were
suspended in the bath in addition to SWCNTs. Addition of such metal particles has been foundthe
in the bath in addition to SWCNTs. Addition of such metal particles has been found to promote to
formation of hard coatings through a combination of mechanisms: impact adhesion
promote the formation of hard coatings through a combination of mechanisms: impact adhesion on on electrode
surface, followed
electrode surface, by nucleation
followed of electroplated
by nucleation coatings on
of electroplated the surfaces
coatings on theof the impacted
surfaces particles,
of the impacted
cementing them onto the electrode surface [48,49]. Hence the addition of Cu powder
particles, cementing them onto the electrode surface [48,49]. Hence the addition of Cu powder (<425 was
µm)(<425
investigated
μm) in an attempt
was investigated in antoattempt
create denser, more
to create adherent
denser, more coatings.
adherent coatings.
Figure 6 illustrates an SEM image of Cu micropowder(Sigma
Figure 6 illustrates an SEM image of Cu micropowder (SigmaAldrich,
Aldrich,StStLouis,
Louis,MO,MO,USA) USA)and
anda
physical mixture with SWCNTs. The Cu micropowder comprises aggregates
a physical mixture with SWCNTs. The Cu micropowder comprises aggregates (50–300 μm) of (50–300 µm) of individual
crystallites crystallites
individual (263 (14) Å),(263
while(14)inÅ),
thewhile
physically
in themixed sample,
physically the SWCNTs
mixed sample, theare SWCNTs
highly bundled and
are highly
existed as physically separate domains surrounded by copper particles (Figure 6a,b).
bundled and existed as physically separate domains surrounded by copper particles (Figure 6b,c).

Figure 6. SEM
SEM images
images of (a) copper
copper micropowder
micropowder and (b) a physical mixture of copper micropowder
with HiPCO SWCNTs. SWCNTs are seen in (b) as highlyhighly bundled species segregated into domains
= 100
(indicated by the arrows) among the copper particles suggesting poor mixing. Scale bar = 100 μm
µm (a)
(a)
and 10 μm
µm (b).

Electrolysis of SWCNTs/CuSO4 was performed in the presence of microscale copper powder

dispersed in the stirring plating bath. A hard adherent coating thickness of 0.20 ± 0.05 mm was
achieved over 2.75” coated lengths of the 16-gauge copper wire cathode (Figure 7). This is likely due
to grain stabilization and dispersion hardening of copper grains by dispersed copper microparticles
C 2019, 5, 38 10 of 14

Electrolysis of SWCNTs/CuSO4 was performed in the presence of microscale copper powder

dispersed in the stirring plating bath. A hard adherent coating thickness of 0.20 ± 0.05 mm was achieved
over 2.75” coated lengths of the 16-gauge copper wire cathode (Figure 7). This is likely due to grain
stabilization and dispersion hardening of copper grains by dispersed copper microparticles [48,49].
The adherent coatings held on to the electrode surface despite manual abrasion between fingers, or
mild abrasion using tissue paper. Multiple cathodes were coated simultaneously (Figure S7), and on
average, 0.11 ± 0.03 g of coating was deposited per wire cathode, translating to a total hard deposit of
about 0.444 g over 27.5 cm of cathode surface (for the 4 copper wire cathodes combined). In addition, a
C 2019, 5, x FOR PEER REVIEW 10 of 13
porous
C 2019, 5,deposit wasREVIEW
x FOR PEER also obtained, which appeared to contain the majority of the Cu micro powder.
10 of 13

Figure 7. Examples of dried copper wire cathodes with a hard adherent Cu–SWCNT composite
Figure
coating.7.7. Examples
Figure Examplesofofdried
dried copper
copper wirewire cathodes
cathodes with with
a harda adherent
hard adherent Cu–SWCNT
Cu–SWCNT composite
composite coating.
coating.
SEM
SEM images
images of of the
the hard
hard coatings
coatings (Figure
(Figure 8a)
8a) revealed
revealed large
large features
features formed
formed fromfrom fused
fused particles
particles
(10–50SEM
µm),images
on of
which the hard
were coatings
smaller (1–2(Figure
µm) 8a) revealed
particles large
(Figure features
(10–50 μm), on which were smaller (1–2 μm) particles (Figure 8b). It is unclear from the SEM
8b). It is formed
unclear from
from thefused
SEMparticles
images
images
(10–50
if
if the μm), on are
the SWCNTs
SWCNTs which were smaller
are incorporated;
incorporated; (1–2 μm)
however,
however, theparticles
the fine (Figure
fine deposit
deposit 8b). It is
obtained
obtained unclear
during
during the
thefrom the SEM
plating
plating processimages
process was
was
if the SWCNTs
comprised more are
of incorporated;
fibrous bundles however,
of SWCNTs the fine
(Figuredeposit
8c). obtained
The associated
comprised more of fibrous bundles of SWCNTs (Figure 8c). The associated EDX data (Table 6) during
EDX the plating
data (Tableprocess
6) was
confirms
comprised
the presence
confirms more
the of C of
(and
presence fibrous
theC Fe
of bundles
(andassociated
the Fe ofassociated
SWCNTs (Figure
with the catalyst
with 8c).
theresidue Theinresidue
catalyst associated
the SWCNTs)
in theEDX indata
both(Table
SWCNTs) samples.6)
in both
confirms
The
samples. thecontent
carbon
The presence
carbon (12.3of C±(and
content 7.4 the
at%)
(12.3 Fefor
± 7.4 associated
thefor
at%) hardthewith
hardthe
coating catalyst
is higher
coating residue
is higher in samples
than than
in the
in SWCNTs)
samples in both
prepared by
prepared
samples. The
electrolysis in carbon
the content
absence of (12.3
added ± 7.4
Cu at%) for
micropowder.the hard coating
However, is
the
by electrolysis in the absence of added Cu micropowder. However, the porous deposit has higher
porous than in
deposit samples
has prepared
significantly
by electrolysis
greater oxygen
significantly in the
content
greater absence
than
oxygen of added
previously
content than Cu micropowder.
observed
previously(c.f.,observed However,
Table 2; Table
(c.f., 6). 2;the
Table Tableporous
6). deposit has
significantly greater oxygen content than previously observed (c.f., Table 2; Table 6).

Figure 8.
Figure 8. SEM images of hard adherent coatings (a,b) and related porous deposit deposit (c) as
as obtained
obtained
Figure
through8.the
through SEM
the imageselectrochemical
modified
modified of hard adherent
electrochemical coatings
plating
plating (a,b)
process
process onand
on related
copper
copper wireporous
wire deposit (c) as obtained
cathodes.
cathodes.
through the modified electrochemical plating process on copper wire cathodes.
Table 6. EDX analysis of electroplated Cu–SWCNT composites electrodeposited at a bath temperature
Table 6. EDX analysis of electroplated Cu–SWCNT composites electrodeposited at a bath
of 60 ◦ C6.in EDX
Table the presence of micropowder copper.
temperature of 60analysis
°C in theofpresence
electroplated Cu–SWCNT
of micropowder composites electrodeposited at a bath
copper.
temperature of 60 °C in the presence of micropowder copper.
SWCNTSWCNT (wt%) (wt%) CC(at%)
(at%) O (at%)
O (at%) Cu (at%) Cu (at%) Fe (at%) Fe (at%)
SWCNT (wt%)
Hard coating
Hard coating C (at%)
12.3
12.3 ±±7.4
7.4 7.7 ±O (at%)
4.0
7.7 ± 4.0 76 ± 12 Cu 76(at%)
± 123.7 ± 0.5 Fe
3.7(at%)
± 0.5
Hard coating
Porous deposit
Porous deposit 12.3
10.1 ± 7.4
10.1±±2.5
2.5 ± 7.9± 7.9 65.7 ± 4.4 65.7 ±12
7.7
20.6 20.6± 4.0 76 ± 4.4
3.4 ± 1.0 3.7
3.4 ±± 0.5
1.0
Porous deposit 10.1 ± 2.5 20.6 ± 7.9 65.7 ± 4.4 3.4 ± 1.0
4. Conclusions
4. Conclusions
4. Conclusions
Copper–carbon nanotube
Copper–carbon nanotube composites
composites possess
possess several
several interesting
interesting mechanical
mechanical andand electrical
electrical
Copper–carbon
properties and can benanotube
prepared composites
through possesstechniques.
numerous several interesting mechanical
Electroplating is one and technique
such electrical
properties and can be prepared through numerous techniques. Electroplating is one such technique and
properties
and was usedand can be prepared
to generate boththrough numerous
soft deposits techniques.
containing Electroplating
controllable is one
amounts of such technique
SWCNTs, and
and was used to generate both soft deposits containing controllable amounts
hard/adherent coatings of Cu–SWCNTs composites on copper wire cathodes. The morphology of SWCNTs, and
of
hard/adherent
the compositescoatings
appearedoftoCu–SWCNTs
demonstrate composites
a dependenceon on
copper
SWCNT wirecontent:
cathodes.
theThe morphology
higher the SWCNT of
the composites
content, the lessappeared to demonstrate
the dendritic a dependence
nature of the on SWCNT
electrodeposited copper. content: the higher
The presence the SWCNT
of SWCNTs alters
content, the less the dendritic nature of the electrodeposited copper. The presence
the nature of the native oxide on copper from CuO to Cu2O, while the presence of copper of SWCNTs alters
C 2019, 5, 38 11 of 14

was used to generate both soft deposits containing controllable amounts of SWCNTs, and hard/adherent
coatings of Cu–SWCNTs composites on copper wire cathodes. The morphology of the composites
appeared to demonstrate a dependence on SWCNT content: the higher the SWCNT content, the less the
dendritic nature of the electrodeposited copper. The presence of SWCNTs alters the nature of the native
oxide on copper from CuO to Cu2 O, while the presence of copper microparticles in the plating bath
promoted the deposition of hard copper composite coatings on cathode surfaces. Importantly, despite
their low dispersion, it is not necessary to employ a surfactant, a dispersing agent, or functionalization
of the SWCNTs. This is a preliminary study aimed at generating composite sludge comprising mainly
copper and added SWCNTs. Further follow-up studies are being planned in our research group with
respect to optimizing the process, and subsequent steps to produce high ampacity electrical conductors.

Supplementary Materials: The following are available online at http://www.mdpi.com/2311-5629/5/3/38/s1:

Figure S1: Image showing the association of the aggregates with the magnetic stir bar indicating the presence of
the SWCNTs containing iron catalyst impurities; Figure S2: SEM images of HiPCO SWCNTs; Figure S3: SEM of
copper wire cathode showing scratches likely produced during manufacture and subsequent handling; Figure S4.
Photographic image of Cu–SWCNT composite deposited on the surface of the copper cathode after electrolysis
using constant voltage (14 V) power supply: [Cu2+ ] = ~0.095 M, [SWCNT] = 2.3 wt%; Figure S5. Plot of copper
(at%) versus carbon (at%) composition as determined by EDX analysis (R2 = 0.98). EDX shown as an average
of 5 independent measurements per sample; Figure S6. Plot of iron (at%) versus carbon (at%) composition as
determined by EDX analysis (R2 = 0.92). EDX shown as an average of 5 independent measurements per sample;
Figure S7. Copper wire cathodes with hard coatings (Cu–SWCNT) before rinsing and drying.
Author Contributions: P.M.V.R. and A.R.B. conceptualized the study and developed the related methodology.
Both authors co-wrote, reviewed, and edited the manuscript. C.E.G. and D.R.J. contributed in terms of XPS
characterization and discussion of data. P.M.V.R. performed all electroplating experiments and all sample
preparations for material characterization studies. SEM and EDX and related analyses were performed by G.L.E.
and B.B. TGA and Raman analysis were performed by P.M.V.R. XRD analysis was conducted by J.L. A.R.B.
contributed in terms of funding acquisition, project management, supervision, and overall guidance in the study.
Funding: Funding for this work was provided by the Office of Naval Research (N00014-15-2717), the Robert A
Welch Foundation (C-0002), the Sêr Cymru National Research Network in Advanced Engineering and Materials
(NRN-150) (A.R.B.), a Sêr Cymru II Welsh Fellowship (C.E.G.) part-funded by the European Regional Development
Fund (ERDF), and Flexible Integrated Energy Systems (FLEXIS) operations funded by the Welsh European Funding
Office (WEFO) through the Welsh Government.
Acknowledgments: The authors would like to acknowledge the assistance provided by Swansea University
College of Engineering AIM Facility, which was funded in part by the EPSRC (EP/M028267/1), and the European
Regional Development Fund through the Welsh Government (80708). Ewa Kazimierska of Swansea University
is acknowledged for her insights into the theory of electroplating. Thanks are extended to John Marsh of Rice
University for administration support and help with project management.
Conflicts of Interest: The authors declare no conflict of interest.

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