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Chem. C, 2017, DOI: 10.1039/C7TC03669H.

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Journal of Materials Chemistry C Accepted Manuscript

ARTICLE

All Inkjet-printed Graphene-based Conductive Pattern for

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Wearable E-textiles Application

Received 00th January 20xx, a,d, † a,b, † b b
Accepted 00th January 20xx Nazmul Karim,* Shaila Afroj, Andromachi Malandraki, Sean Butterworth, Christopher
c d a c b
Beach , Muriel Rigout , Kostya S Novoselov, Alexander J Casson and Stephen G Yeates
DOI: 10.1039/x0xx00000x
Inkjet printing of graphene inks are considered to be very promising for wearable e-textiles applications as benefits of both
www.rsc.org/
inkjet printing and extra-ordinary electronic, optical and mechanical properties of graphene can be exploited. However,
the common problem associated with inkjet printing of conductive ink on textiles is the difficulty to print continuous
conductive path on a rough and porous textiles surface. Here we report inkjet printing of an organic nanoparticles based
surface pre-treat onto textiles to enable all inkjet-printed graphene e-textiles for the first time. The functionalized organic
nanoparticles present a hydrophobic breathable coating on textiles. Subsequent inkjet printing of continuous conductive
electrical path onto the pre-treat coating reduced the sheet resistance of graphene-based printed e-textiles by three
orders of magnitude from 1.09 × 106 Ω/sq. to 2.14 × 103 Ω/sq compared with untreated textile. We present several
examples how this finding opens up opportunities for real world applications of printed, low cost and environmentally
friendly graphene wearable e-textiles.

Recent studies have highlighted the potential of graphene for

22-28
1. Introduction the fabrication of the next generation e-textiles . However,
26
current technologies, based on multiple dip and dry or
Wearable electronic textiles (e-textiles) have become a focus 28
vacuum filtration methods , are extremely slow. Also the use
of significant research interest due to their potential 23
of graphene/metal composite inks requires higher post
applications in sportswear, military uniforms, environmental reduction temperature
27-29
. In addition, reduced graphene
1-3
monitoring and health care . There have been enormous oxide (rGO) inks have the potential to produce durable and
efforts in incorporating electronic components to make e- washable conductive e-textiles due to the hydrogen bonding
textiles for various applications such as sensors4-7, energy between hydroxyl groups in cotton
9, 30
and residual oxygen
8, 9 10 11, 12 31
storage devices , transistors and photovoltaic devices . containing groups in rGO . Recent studies on the reduction of
13 14 15
Metal inks based on Ag , Cu or Au are currently most graphene oxide (GO) on textiles have however used toxic
32
commonly used materials due to their higher electrical reducing agents such as hydriodic acid , sodium borohydride
26
conductivity (σ), typically ∼ 10 S/m . However, metal inks are
5 16
and hydrazine . Therefore, there remains a growing interest
17 18 to develop a quick, scalable and low temperature processing of
expensive , environmentally unfriendly , not-
19
biocompatible , and often require higher sintering environmentally friendly e-textiles.
20
temperature , which is incompatible with heat sensitive
textile fabrics. Thus there exists a need for a low-cost, For e-textiles fabrication, inkjet printing offers a number of
environmentally friendly and low temperature processing advantages over conventional manufacturing techniques
including weaving of conductive yarn such as: the ability to
conductive material for wearable e-textiles application. This is
deposit controlled quantities of materials at precise locations
timely, as consultation in the Waste Electrical and Electronics
at and in the fabric, combined with a reduction in both
Equipment Directive (WEEE)21 is currently determining the 33
material waste and water utilisation . However, the key
future regulation of printed electronics disposal.
challenge with inkjet printing of e-textiles is the ability to
achieve continuous highly conductive electrical tracks on a
rough and porous textile substrate. Textile fabrics demonstrate
an intrinsic planar anisotropy of general properties due to the
34
orientation of fibres or yarns . In addition, the morphology of
the fibre changes constantly due to the exchange of water
molecules with surroundings, making it extremely difficult to
produce uniform and continuously conductive paths using low
35
viscosity inkjet inks .

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Journal of Material Chemistry C ARTICLE

Journal of Materials Chemistry C Accepted Manuscript

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Fig. 1 Schematic diagram of all inkjet-printed graphene e-textiles manufacturing process

Previous study has suggested using a screen-printed

polyurethane acrylate-based 200 µm thick interface layer, 2. Experimental
which reduces both the surface roughness and porosity of
standard 65/35 polyester/cotton fabric35, enabling inkjet 2.1 Materials
printing of a continuous conductive track with a suitable silver Styrene (St), divinylbenzene (DVB), hydroxyethyl methacrylate
inks on pre-treated areas. However the deposition of the (HEMA), sodium dodecyl sulphate (SDS), ammonium persulfate
interface layer by traditional screen printing constrains the (APS), glycerol, Polyvinyl Alcohol (PVA, Mw ~ 31,000-50,000,
potential feature resolution, is not compatible with the 98-99%), L- ascorbic acid (99%), ammonia, silver nanoparticle
deposition of low quantities of material and is not compatible inks (30-35 wt. %, Sigma Aldrich Product No: 736473) and
with future roll to roll manufacturing36. Triton X-100 were purchased from Sigma-Aldrich, UK and used
as received. Flake graphite (Grade 3061) was kindly donated by
Here we report an organic nanoparticle based inkjet printable Asbury Graphite Mills, USA. 100% Cotton, 100% Polyester and
textiles surface pre-treat which enables all inkjet-printed 65/35 Cotton-polyester blend (65% Cotton, 35% Polyester)
graphene-based wearable e-textiles that are breathable, fabrics were provided by Royal TenCate, Netherlands.
comfortable and environmentally friendly. The primary
advantage of inkjet deposition of the surface pre-treat over 2.2 Nanoparticle Synthesis (NP1)
techniques such as screen printing and curtain coating is the Hydroxyl functionalised cross-linked styrene/divinylbenzene
ability to deposit only where required on the article and to nanoparticles were synthesized using conventional emulsion
personalise at an item by item level. Such a pre-treat acts as polymerisation containing 1 wt.- % HEMA (NP1) on total
receptor layer for water-based rGO inks, which can
monomer. 250 mL of deionised water and 20 mL of a 3.38
subsequently be dried at low temperature (100 °C); thus
mmol, solution of SDS were added to 500 mL flange flask fitted
reducing the chance of damaging heat-sensitive fabrics. As
with a condenser, nitrogen flow, a 5 blade impeller mechanical
illustrated in Fig 1, an organic nanoparticle textile pre-treat is
stirrer and a thermometer; stirred for 15 min at 600 rpm under
inkjet-printed onto the textile fabric, followed by a rGO water-
based ink prepared using a green non-toxic reducing agent, L- nitrogen flow. St (21 g, 216 mmol), DVB (2.1 g, 16.1 mmol) and
ascorbic acid in the presence of polyvinyl alcohol (PVA). The HEMA were then added and stirred at 600 rpm whilst being
resultant conductive tracks have sufficient conductivity for degassed for 1 hour and heated to 80 °C. APS (1g, 11.6 mmol),
uses in wearable power delivery systems and non-invasive dissolved in 10 mL of deionised water and degassed for 30 min
heart monitoring. in a vial, added to the reaction flask. The reaction was run for
24 hours; stopped and run another 2 hours for cooling. The
resultant suspension was passed through 50 μm nylon gauze

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to remove any coagulant and nanoparticles were used without every 5 min. A Jandel four-point probe system (Jandel
any further treatment. Engineering Ltd, Leighton, UK) was employed to measure the
resistivity of the conductive pattern; sheet resistance was
2.2 Synthesis of Graphene Oxide and Reduced Graphene Oxide calculated from the average of six measurements. For SEM,
Graphene oxide (GO) was prepared using modified Hummers

Journal of Materials Chemistry C Accepted Manuscript

AFM and Raman, the rGO dispersion were diluted 1000 times
37
method as described elsewhere . A 80 mg amount of GO was and drop casted on Si/SiO2 (290 nm oxide on plain silicon).
added to 160 mL of deionized (DI) water and sonicated for 30 Philips XL 30 Field Emission Gun Scanning Electron Microscope
min to form a brown dispersion of graphene oxide (0.5 (SEM) was used to analyse the surface topography of the
mg/mL). Further, 500 mg of PVA was mixed to the graphene untreated and printed cotton fabrics, and also the flake size of
GO and rGO. A Dimension Icon (Bruker) Atomic Force
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oxide dispersion with rigorous stirring. This was transferred to

a round-bottom flask placed in an oil bath. L-ascorbic acid (1.2 Microscopy (AFM) was used to determine the flake thickness.
gm) and NH3 (as required to adjust pH 9-10) were added to the For each sample, images were taken at 10 different locations
dispersion with rigorous stirring. This mixture was heated at 90 on the sample and a statistical analysis of 100 flakes was done.
Raman spectra were captured using a Renishaw Raman System
°C for 24 hours under closed conditions to obtain a black
equipped with 633 nm laser. A Kratos Axis system
dispersion. Sufficient DI water was added to this dispersion in
spectrophotometer was used to perform the XPS analysis.
order to make a total volume of 200 mL. The resulted rGO was
washed with deionised water several times to remove any
The breathability of the printed and untreated cotton fabrics
residues present and finally dispersed into water at desired
was assessed by adding known amount of water in a pre-
concentration. weighed vial using printed and untreated fabric as a lid. The
vials were left idle on the bench and the weight loss was
2.3 Inkjet Ink Formulation and Inkjet Printing
measured frequently for 14 days. Zwick/Roell Tensile Tester
The viscosity and surface tension of NP1 were corrected
(Zwick Roell Group, Germany) was used to control the cord
adding glycerol (19.8 wt.-%) as rheology modifier and
length of NP1 and rGO inkjet-printed conductive fabric
humectant, and Triton X-100 (1.2 wt.-%) as no-ionic surfactant
(Length: 28 mm) during bending test. A National Instrument
to achieve 2.55±0.05 mPa.s and 31 mN/m, respectively. All
9219 data acquisition card (NI, American) was used to capture
inks were filtered through a 2.0 µm filter to remove any
the change of sheet resistance of printed fabric (Length: 28
impurities and large particles that could block Dimatix nozzles.
mm) during bending in both forward and reverse direction.
The wash stability of NP1 and rGO inkjet-printed fabric was
The viscosity and surface tension of rGO ink was found to be
performed by following EN ISO 105 C06 A1S standard.
1.35 mPa.s and 65 mN/m, respectively. rGO ink was printed
without any modification by increasing the firing voltage in the
2.5 Electrocardiography (ECG) Measurements
first segment of drop generation to enable rapid pressure build
Measurements of electrocardiography (ECG) were performed
up for drop ejection. The voltage was decreased slowly in the
on four male subjects for five minute recording periods. Each
second segment to cut off droplet tails; thus forms spherical
38 subject placed one finger from each hand on a printed
droplets .
graphene patch with both patches also connected to a
standard two electrodes wire ECG recording unit (CamNtech,
A Dimatix DMP-2800 inkjet printer (Fujifilm Dimatix Inc., Santa
Cambridge, UK). Signals were acquired at 10 bit resolution and
Clara, USA) was used in this study, equipped with a disposable
1024 Hz sampling rate, downsampled to 256 Hz prior to
piezo “inkjet” cartridge. This printer can create and define
analysis in Matlab (The MathWorks, Natick, USA). All signals
patterns over an area of about 200 × 300 mm and handle
were filtered (Butterworth, second order) to remove mains
substrates up to 25 mm thick, being adjustable in the Z
interference. On one hand, selected by the participant for
direction. The nozzle plate consists of a single row of 16
comfort, subjects also wore a photoplesmography (PPG) heart
nozzles of 21.5 µm diameter spaced 254 µm with typical drop
rate monitor (Empatica, Boston, USA) as a reference device.
diameter of 27 µm and 10 pL drop size. Print head height was
PPG is the method of heart monitoring commonly used in
adjusted to 0.75 mm; formulated inks were jetted reliably and
smart watches and is used as the reference here as it does not
reproducibly at 24 V and ambient temperature. It was
introduce any interference to a simultaneous ECG recording.
important however to use the primed-head within 48 hours to
avoid non recoverable nozzle dry out.
Heart rate estimates were extracted by taking the Continuous
Wavelet Transform (CWT) at scale 0.025 using the Mexican hat
2.4 Characterisation
mother wavelet and thresholding the CWT power coefficients
The surface wettability of untreated and nanoparticles (NP1)
to identify candidate peaks in the ECG trace (R peaks)
printed textile substrates was assessed by measuring the
corresponding to each heart-beat. From each candidate beat
contact angle (CA) using droplets of distilled water and rGO ink
detection in the CWT domain, the actual R peak location was
on the untreated and printed substrates, and the change of CA
selected as the signal point in the time domain with the
with time was also measured using a Kruss Dynamic Shape
maximum amplitude within 10 samples of the CWT peak
Analyser DSA100. The CA readings were taken approximately
location. Spurious low (<50 µV) and high (>1000 µV) amplitude

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candidate peaks were rejected. The heart rate in beats per of 31 mN/m, respectively, which is suitable for stable inkjet
minute (bpm) was then calculated as 60 divided by the time printing using a Dimatix DMP inkjet printer. The formulations
between each pair of detected heart beats. As a final were inkjettable and forming stable drops without satellites,
processing step, a simple tracking filter was applied which although 12 multiple passes were required to achieve the

Journal of Materials Chemistry C Accepted Manuscript

would reject heart rate estimates that were more than 10 bpm required surface properties whilst retaining mechanical
39
away from the previous estimate, with the rejected samples properties without impairing the breathability of textiles .
replaced with a zero order hold of the previous rate. The
Signal-to-Noise Ratio was calculated for each detected heart Graphene oxide (GO) has previously been used in several
beat by detrending the ECG trace and taking the resulting R studies to coat textiles and reduced to rGO by
40-42 43-46 47 26,
peak amplitude as the Signal (S), and Root Mean Square of the electrochemical , thermal , UV or chemical process
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48-50
middle third of the ECG trace between consecutive pairs of R to make conductive e-textiles. Here, we use a chemical
51, 52
peaks as the Noise (N), in the equation: reduction of GO prepared by Hummers method to rGO
using a green and efficient reducing agent, vitamin C53 and

Signal-to-Noise Ratio  20 log
 stabilised by polyvinyl alcohol (PVA). The resultant fluids are
stable to sedimentation for over six months at ambient
conditions. The structure and properties of graphene are
partially restored by reducing GO to rGO; however full
reduction or restoration of graphene properties is difficult to
achieve54. Therefore, it leaves some oxygen containing
functional groups in rGO. The presence of these residual
oxygen functional groups however is beneficial as it helps to
create hydrogen bonding with hydroxyl groups of cotton fibres
30
, which enables uniform and durable coatings on textile
fibres32.

Statistical analysis of 100 flakes by Scanning Electron

Microscopy (SEM) shows that the mean lateral dimension of
GO is 5.85 µm and that of rGO is 4.86 µm (Fig. 2a). Atomic
Force Microscopy (AFM) was used to measure the thickness
(height =h) of GO and rGO flakes, which shows that the mean
thickness for GO is 2.07 nm and rGO is 2.26 nm, confirming the
presence of single to few layers of graphene flakes in the
dispersion. The statistical analysis in Fig. 2b reveals that the
distribution is shifted towards higher h for rGO, may be due
the presence of cross-linking polymer (PVA) covering graphene
flakes, which is in agreement with a previous study55. Raman
spectra of GO and rGO displays characteristic peaks at 1344.78
cm-1 and 1605.95 cm−1, corresponding to D and G band
(supporting information Fig S1). These two peaks were shifted
to lower wavenumber 1327.4 cm-1 (D) and 1596.82 cm-1 (G)
after reduction of GO to rGO, which may be due to the
recovery of hexagonal carbon atom56. In addition, the intensity
ratio of D to G band (ID/IG) was increased from 0.98 for GO to
Fig. 2 a) Particle size distribution of NP1; b) Flake size distribution of GO and rGO; c)
1.73 for rGO, which suggests the generation of large number
Flake thickness distribution of GO and rGO; of sp2 domain in rGO.

The wide scan XPS spectra in Fig 3a also provides the evidence
3. Results and Discussion of the reduction process as C/O ratio increased from 2.41 (GO)
to 4.18 (rGO). C1s spectra of GO, Fig 3b, demonstrates two
The organic nanoparticle pre-treat is based upon a hydroxyl main peaks which can be fitted into three components
functional polystyrene emulsion polymer (NP1) having a Z- emerged from C-C/C=C bond in aromatic rings (~284.6 eV), C-O
average particle size of 63.12nm (polydispersity index = 0.05), epoxy and alkoxy groups (~286.4 eV) and C=O carbonyl groups
Fig. 2a. NP1 as made has a %-solids= 40.86 wt.-% giving a (288 eV)31, 57. This provides proof of higher number of oxygen
viscosity of 0.5 mPa.s and a surface tension of 70 mN/m at 25 containing functional group present on the surface of GO.
o
C. The viscosity and surface tension were subsequently After reduction to rGO, the peaks associated with oxygen
modified by adding glycerol (19.8 wt.-%) and Triton X-100 (1.2 functional groups sharply decreased, with small amount of
wt.-%) to achieve a viscosity of 2.5 mPa.s and surface tension residual oxygen functional groups left around 288.5 eV, Fig. 3b.

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Journal of Materials Chemistry C Accepted Manuscript

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Fig. 3 a) Wide scan XPS spectra of graphite, GO and rGO; and b) High resolution C1s spectra of GO and rGO

In general, C1s spectrum of rGO exhibits similar shape to Moreover, textile surfaces are not only rough but also porous
graphene or natural graphite, which indicates remarkable which allows the liquid penetration, controlled by kinetics of
58
restoration of graphitic structure through chemical wetting .
56
reduction .
Coating with NP1 results in larger interface area and produces
58
The inkjet printing of NP1 onto a range of textile materials mechanical locking , thus stopping liquid penetration through
such as cotton (Fig. 4a), cotton-polyester fabrics (Fig. 4b), and the fibres and holds water-based liquid on the surface. In
polyester (Fig. 4c) substantially increased water contact angle contrast to cotton, the cotton-polyester (65/35) and polyester
(WCA), for example with 100% cotton fabrics up to 132.9°. fabrics imparted a relatively higher WCA 144.8° (Fig. 4b) and
During contact angle measurement, the water droplets falling 143.3° (Fig. 4c), respectively. The superior WCA onto NP1
onto an untreated control cotton fabric were absorbed almost printed cotton-polyester and polyester fabrics is attributed to
immediately after hitting the surface, Fig. 4a, as the cotton the inherent hydrophobicity of synthetic fibres in particular
59
fibres provide higher polarity, hydrogen-bonding and polyester . The non-wettability of hydrophobic polyester
wettability in their natural form. In addition, untreated cotton fibres is further enhanced by nanoparticle treatment; thus
fibres are extremely hydrophilic due to the presence of resulting in an increased surface roughness and imparted
abundant hydroxyl groups in their cellulosic molecules [39]. higher WCA.

Fig. 4 Contact angle (CA) of distilled water and rGO versus time at 25 °C on inkjet-printed a) cotton, b) cotton-polyester (65/35) and c) polyester fabrics with nanoparticles NP1: (■)
control fabric (water and rGO), (●) WCA on NP1 printed fabric and (▲) CA of rGO on NP1 printed fabric; d) The water evaporated through NP1 printed (12 layers) and untreated
cotton fabrics: (■) inkjet printed with NP1 and (●) control fabrics;

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Fig 4(a-c) shows that the contact angle of the rGO ink is almost nanoparticles on the fibre surface and the formation of
similar on fabrics of all types, 131.9° for cotton, 131.7° for continuous film onto NP1 printed textiles. The inter-fibre
cotton-polyester and 128.6° for polyester. For 100% cotton bonding achieved through printing and curing of NP1 polymer
fabric, the contact angle of the rGO ink decreased slightly provided continuous conductive film, Fig. 5c; however no such

Journal of Materials Chemistry C Accepted Manuscript

compared with water; whereas that of cotton-polyester and continuous film was observed for the fabrics without
polyester decreased significantly (by ~12-15°) may be due to nanoparticle prints, Fig. 5a.
38
the lower surface tension . Inkjet printing enables deposition
Table 1 Sheet resistance achieved on pre-treated and untreated textile
of functional materials in a precise and controlled manner on
desired locations (pattern), depositing functional materials Formu Fabrication and surface treatment Rs (Ω/sq) Standard
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only on the printed side. Fig. 4d illustrates that the weight of lation deviation
the water evaporated through inkjet nanoparticles (NP1) rGO Inkjet-printed (6 Layers) onto 100% 1.09 × 106 0.51
printed and untreated cotton fabrics. The results from the cotton fabric without NP1 surface
breathability test show that the permeability of water vapour pre-treatment
through textiles was not obstructed due to the inkjet rGO Inkjet-printed (6 Layers) onto 100% 2.14 × 103 0.91
deposition of nanoparticles (NP1) onto textiles, as the water cotton fabric with printed NP1 (12
Layers) surface pre-treatment
evaporation through both types of fabric was found to be
similar. The unprinted side remains hydrophilic, thus providing SA-Ag Inkjet-printed (6 Layers) onto 100% Not -
60
additional comfort by regulating the moisture . cotton fabric without NP1 surface conductive
pre-treatment
A commercial silver inkjet inks (30-35 wt.-%, Sigma Aldrich SA-Ag Inkjet-printed (6 Layers) onto 100% 1.18 0.25
Product No: 736473) was used first to evaluate the cotton fabric with printed NP1 (12
performance of NP1 printed surface pre-treatment on cotton Layers) surface pre-treatment
for e-textiles application. The viscosity (10-18 cP) and surface
tension (35-40 mN/m) of silver inkjet inks were well within In order to inkjet print rGO, the ink concentration was adjusted
required the range for DMP. Conductive patterns were inkjet- with water to ~1 mg/mL after post reduction washing cycles
printed onto NP1 printed area and the untreated area of the giving a viscosity and surface tension of the rGO composite ink
fabric. NP1 printed surface provides very good conductivity, 1.35 mPa.s and 65 mN/m, respectively. This formulation was
Fig. 5b (2), although a few layers (6 layers) of silver inks were inkjet-printed by manipulating the firing voltage of the
38
required to achieve lower sheet resistance. However, the piezoelectric nozzles as a function of time . We inkjet print
untreated area of the cotton fabrics, Fig. 5b (3), results in no rGO ink onto NP1 printed area and untreated area of the
conductivity even with multi-layers of silver ink. The sheet cotton fabric. The sheet resistance of NP1 printed textiles with
3
resistance on the NP1 printed surface with 6 layers of 6L of rGO ink was found to be 2.14 × 10 Ω/sq.; whereas
commercially available silver inkjet ink was found to be 1.18 untreated textiles provide much higher sheet resistance 1.09 ×
6
Ω/sq. SEM images, Fig. 5 (a, c), of inkjet-printed cotton fabrics 10 Ω/sq., Table 1.
with silver demonstrate the deposition of conductive silver

Fig. 5 a) SEM images of inkjet printed silver ink (6 layers) onto untreated cotton (×2000); b): (1) NP1 (12 Layers) printed area; (2) inkjet-printed conductive pattern onto NP1
printed area with silver ink (6 Layers) and (3) inkjet-printed silver ink onto untreated area (6 Layers); c) SEM images of inkjet printed silver ink (6 Layers) onto NP1 (12 layers)
printed cotton fabrics (×1000); d) SEM images of inkjet printed rGO ink (6 layers) onto untreated cotton (×1000); e) Inkjet-printed conductive pattern with rGO onto NP1 printed
and untreated area of cotton; f) SEM images of inkjet printed rGO ink (6 Layers) onto NP1 (12 layers) printed cotton fabrics (×500);

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Table 2 Quantified performance of graphene-based e-textiles heart monitoring on four objects

Subject Mean heart rate Standard deviation of heart rate Mean Signal-to-Noise Ratio of Standard deviation Signal-to-Noise
estimation error (bpm) estimation error (bpm) collected signal (dB) Ratio of collected signal (dB)

Journal of Materials Chemistry C Accepted Manuscript

1 2.1 3.5 21.4 5.2
2 5.2 6.1 27.0 2.6
3 1.1 1.1 15.5 3.3
4 6.0 6.7 15.1 3.4
Avg. 3.6 4.4 22.3 3.6
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demonstrate functional sensing, multiple patches of the rGO

As the rGO ink contain residual hydroxyl or carboxyl groups ink were inkjet-printed onto a 100% cotton substrate with NP1
which may form hydrogen bonding with abundant hydroxyl surface pre-treatment and used to perform
groups of cellulosic fibres, Fig 5d. Therefore, it helped to electrocardiography (ECG) sensing of the heart. Each patch of
provide some electrical conductivity even onto untreated pre-treated material and rGO ink were electrically isolated by
textiles; however electrical conductivity significantly improved the cotton substrate and so act as separate electrodes. When
by three orders of magnitude with NP1 surface pre-treatment. these electrodes are placed on either side of the body, they
The inkjet printing of hydrophobic NP1 onto cotton fabrics measure the electrical activity due to the pumping action of
provided inter-fibre bonding, Fig. 5f, which helped to produce the heart, which allows heart rate and heart rate variability
a continuous conductive path and imparted very good inter- information to be extracted, of significant use in a number of
61, 62
connections between graphene sheets. Therefore, the sheet clinical and fitness applications of wearable technologies .
resistances of the conductive patterns onto NP1 printed cotton Fig. 6 illustrates an example collected signal showing that high
were found to be much lower. quality heart recordings can be obtained, with the average
Signal-to-Noise Ratio maintained over 21 dB, and compared to
In order to demonstrate a potential application of all inkjet- a reference heart rate monitor the estimated heart rate is
printed graphene e-textiles, an LED light was illuminated by accurate to within 2.1 beats per minute (bpm). This
connecting it with a power supply and conductive e-textiles as performance is quantified with data from four different
shown in Fig. S4, requiring the delivery of milliamps current. To subjects in Table 2.

Fig. 6 Heart rate monitoring example using Graphene e-textiles: a) experimental methods with two fingers placed on printed graphene patches; b) illustrative section of signal
collected shows clear peaks due to each heart beat; c) estimated heart rate using the collected signal compared to a reference device and d) quanitifed quality of the collected
signal over time.

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electronics application. The surface pre-treatment with inkjet-

printed NP1 significantly improved the electrical conductivity.
All inkjet printing of surface pre-treatment enabled layer by
layer deposition of exact amount of materials at predefined

Journal of Materials Chemistry C Accepted Manuscript

locations. Moreover, inkjet printing of water-based and bio-
compatible graphene inks could potentially open up
opportunities to manufacture environmentally friendly next
generation e-textiles for sports, healthcare and military
applications.
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Conflicts of interest
Fig. 7 The variation in resistance in forward (bending) and reverse (bending back)
direction (inset: flexible all inkjet-printed graphene ECG electrode). There are no conflicts to declare. The institutional review board
To our knowledge, only a very limited number of papers have in Manchester have approved Dr Casson to perform ECG
demonstrated graphene, in any form, for enabling heart rate measurements.
63
monitoring. Celic et al. coated conventional Ag/AgCl metal
electrodes with Graphene to improve the quality of collected
signals, but not in a manner suitable for textile wearable Acknowledgements
64
applications. Lou et al. used a polyethylene terephthalate
(PET) substrate and secured the electrodes in place securely Authors kindly acknowledge the University of Manchester
using bandages, unsuitable for wearable textile applications Research Impact Scholarship and Knowledge Exchange
and forcing contact with the skin by using an adhesive bandage Fellowship (Graphene) for Dr Nazmul Karim and the
substantially improves signal quality regardless of the Government of Bangladesh for PhD Scholarship of Shaila Afroj.
65
electrode formulation. Yapici et al. used a textile substrate, Authors would like to thank Dr Paul Wiper and Daniel Wand
but specially selected Nylon due to its minimum surface for the help with LED demo and graphics, respectively.
roughness. In contrast our all inkjet-printed pre-treatment
overcomes this and allows that deposition of material on to
Notes
cotton fabrics.
Nazmul Karim and Shaila Afroj contributed equally to this
Fig. 7 shows the change in the resistance of NP1 and rGO paper as joint first author.
printed cotton fabrics (Length: 28mm) under bending with
concave down at various cord lengths. The resistance
increased with the increase of cord lengths. The change in the
resistance is repeatable in both forward (bending) and reverse
(bending back) direction. Moreover, there was no observable
crack on the printed pattern, which demonstrates the
suitability of the device to be used as flexible wearable e-
29
textiles . The inset picture in Fig. S7 shows excellent
mechanical flexibility of NP1 and rGO printed conductive
fabrics. It also demonstrates good drapability as conductive
fabric can hang under its own weight and goes back to its
original position once bending force is removed. The
washability test of NP1 and rGO inkjet-printed cotton fabric
shows that the fabric resistance increased with the increase of
number of washing cycles (supporting information Fig. S5);
however it survived 10 home laundry washing cycles. The wash
stability NP1 treatment and rGO printed conductive track
could further be improved by incorporating additional
functionality on the fabric surface and coating with a
encapsulation polymer layer, respectively.

4. Conclusions
We report all inkjet-printed graphene-based e-textiles for the
first time and demonstrated two potential wearable

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Journal of Material Chemistry C ARTICLE

References 26. M. Shateri-Khalilabad and M. E. Yazdanshenas,

Carbohydrate Polymers, 2013, 96, 190-195.
1. K. Jost, G. Dion and Y. Gogotsi, Journal of Materials 27. Y. Zhu, M. D. Stoller, W. Cai, A. Velamakanni, R. D. Piner,
Chemistry A, 2014, 2, 10776-10787. D. Chen and R. S. Ruoff, ACS Nano, 2010, 4, 1227-1233.
2. Z. L. Wang and W. Wu, Angewandte Chemie International 28. J. Ren, C. Wang, X. Zhang, T. Carey, K. Chen, Y. Yin and F.

Journal of Materials Chemistry C Accepted Manuscript

Edition, 2012, 51, 11700-11721. Torrisi, Carbon, 2017, 111, 622-630.
3. W. Zeng, L. Shu, Q. Li, S. Chen, F. Wang and X.-M. Tao, 29. L. Huang, Y. Huang, J. Liang, X. Wan and Y. Chen, Nano
Advanced Materials, 2014, 26, 5310-5336. Research, 2011, 4, 675-684.
4. Y. Cheng, R. Wang, J. Sun and L. Gao, Advanced Materials, 30. L. Hu, M. Pasta, F. La Mantia, L. Cui, S. Jeong, H. D.
2015, 27, 7365-7371. Deshazer, J. W. Choi, S. M. Han and Y. Cui, Nano Letters,
2010, 10, 708-714.
Published on 06 October 2017. Downloaded by University of Newcastle on 06/10/2017 23:07:56.

5. Y. Wang, L. Wang, T. Yang, X. Li, X. Zang, M. Zhu, K. Wang,

D. Wu and H. Zhu, Advanced Functional Materials, 2014, 31. D. R. Dreyer, S. Park, C. W. Bielawski and R. S. Ruoff,
24, 4666-4670. Chemical Society Reviews, 2010, 39, 228-240.
6. J. J. Park, W. J. Hyun, S. C. Mun, Y. T. Park and O. O. Park, 32. Y. J. Yun, W. G. Hong, W.-J. Kim, Y. Jun and B. H. Kim,
ACS Applied Materials & Interfaces, 2015, 7, 6317-6324. Advanced Materials, 2013, 25, 5701-5705.
7. C. S. Boland, U. Khan, C. Backes, A. O’Neill, J. McCauley, S. 33. E. B. Secor, P. L. Prabhumirashi, K. Puntambekar, M. L.
Duane, R. Shanker, Y. Liu, I. Jurewicz, A. B. Dalton and J. N. Geier and M. C. Hersam, The Journal of Physical Chemistry
Coleman, ACS Nano, 2014, 8, 8819-8830. Letters, 2013, 4, 1347-1351.
8. L. Liu, Y. Yu, C. Yan, K. Li and Z. Zheng, 2015, 6, 7260. 34. R. Salvado, C. Loss, R. Gonçalves and P. Pinho, Sensors
9. A. M. Abdelkader, N. Karim, C. Vallés, S. Afroj, K. S. (Basel, Switzerland), 2012, 12, 15841-15857.
Novoselov and S. G. Yeates, 2D Materials, 2017, 4, 35. A. Chauraya, W. G. Whittow, J. Y. C. Vardaxoglou, Y. Li, R.
035016. Torah, K. Yang, S. Beeby and J. Tudor, IET Microwaves,
10. T. H. Yoo, B.-I. Sang and D. K. Hwang, Journal of the Antennas & Propagation, 2013, 7, 760-767.
Korean Physical Society, 2016, 68, 599-603. 36. D. J. Tyler, Textile Progress, 2005, 37, 1-65.
11. Z. Yang, in Pure and Applied Chemistry, Editon edn., 2016, 37. J. P. Rourke, P. A. Pandey, J. J. Moore, M. Bates, I. A.
vol. 88, p. 113. Kinloch, R. J. Young and N. R. Wilson, Angewandte Chemie
12. N. Zhang, J. Chen, Y. Huang, W. Guo, J. Yang, J. Du, X. Fan International Edition, 2011, 50, 3173-3177.
and C. Tao, Advanced Materials, 2016, 28, 263-269. 38. L. T. Le, M. H. Ervin, H. Qiu, B. E. Fuchs and W. Y. Lee,
13. Y. Bayram, Y. Zhou, B. S. Shim, S. Xu, J. Zhu, N. A. Kotov Electrochemistry Communications, 2011, 13, 355-358.
and J. L. Volakis, IEEE Transactions on Antennas and 39. A. Malandraki, S. R. Butterworth and S. G. Yeates, NIP &
Propagation, 2010, 58, 2732-2736. Digital Fabrication Conference, 2010.
14. J.-W. Han and M. Meyyappan, AIP Advances, 2011, 1, 40. J. Liu, Y. Qiao, C. X. Guo, S. Lim, H. Song and C. M. Li,
032162. Bioresource technology, 2012, 114, 275-280.
15. A. Schwarz, J. Hakuzimana, A. Kaczynska, J. Banaszczyk, P. 41. Y. Cao, M. Zhu, P. Li, R. Zhang, X. Li, Q. Gong, K. Wang, M.
Westbroek, E. McAdams, G. Moody, Y. Chronis, G. Zhong, D. Wu, F. Lin and H. Zhu, Physical Chemistry
Priniotakis, G. De Mey, D. Tseles and L. Van Langenhove, Chemical Physics, 2013, 15, 19550-19556.
Surface and Coatings Technology, 2010, 204, 1412-1418. 42. L. Liu, Y. Yu, C. Yan, K. Li and Z. Zheng, Nature
16. S. Jeong, K. Woo, D. Kim, S. Lim, J. S. Kim, H. Shin, Y. Xia communications, 2015, 6.
and J. Moon, Advanced Functional Materials, 2008, 18, 43. J. Xu, D. Wang, Y. Yuan, W. Wei, L. Duan, L. Wang, H. Bao
679-686. and W. Xu, Organic Electronics, 2015, 24, 153-159.
17. L. Xu, G. Yang, H. Jing, J. Wei and Y. Han, Nanotechnology, 44. Q. Zhou, X. Ye, Z. Wan and C. Jia, Journal of Power
2014, 25, 055201. Sources, 2015, 296, 186-196.
18. R. R. Sondergaard, N. Espinosa, M. Jorgensen and F. C. 45. W. W. Liu, X. B. Yan, J. W. Lang, C. Peng and Q. J. Xue,
Krebs, Energy & Environmental Science, 2014, 7, 1006- Journal of Materials Chemistry, 2012, 22, 17245-17253.
1012. 46. A. Ramadoss, B. Saravanakumar and S. J. Kim, Nano
19. M. Irimia-Vladu, E. D. Głowacki, G. Voss, S. Bauer and N. S. Energy, 2015, 15, 587-597.
Sariciftci, Materials Today, 2012, 15, 340-346. 47. K. Javed, C. Galib, F. Yang, C. M. Chen and C. Wang,
20. A. Kamyshny and S. Magdassi, Small, 2014, 10, 3515-3535. Synthetic Metals, 2014, 193, 41-47.
21. E. Directive, Official Journal of the European Union L, 48. M. Shateri-Khalilabad and M. E. Yazdanshenas, Cellulose,
2012, 197, 38-71. 2013, 20, 963-972.
22. Z. Yang, H. Sun, T. Chen, L. Qiu, Y. Luo and H. Peng, 49. B. Liang, L. Fang, Y. Hu, G. Yang, Q. Zhu and X. Ye,
Angewandte Chemie International Edition, 2013, 52, Nanoscale, 2014, 6, 4264-4274.
7545-7548. 50. C. Zhao, K. Shu, C. Wang, S. Gambhir and G. G. Wallace,
23. S. S. Yoon, K. E. Lee, H.-J. Cha, D. G. Seong, M.-K. Um, J.-H. Electrochimica Acta, 2015, 172, 12-19.
Byun, Y. Oh, J. H. Oh, W. Lee and J. U. Lee, Scientific 51. W. S. Hummers and R. E. Offeman, Journal of the
Reports, 2015, 5, 16366. American Chemical Society, 1958, 80, 1339-1339.
24. G. Yu, L. Hu, M. Vosgueritchian, H. Wang, X. Xie, J. R. 52. J. P. Rourke, P. A. Pandey, J. J. Moore, M. Bates, I. A.
McDonough, X. Cui, Y. Cui and Z. Bao, Nano Letters, 2011, Kinloch, R. J. Young and N. R. Wilson, Angewandte
11, 2905-2911. Chemie, 2011, 123, 3231-3235.
25. L. Liu, Y. Yu, C. Yan, K. Li and Z. Zheng, Nat Commun, 2015, 53. D. He, L. Shen, X. Zhang, Y. Wang, N. Bao and H. H. Kung,
6. AIChE Journal, 2014, 60, 2757-2764.
54. S. Pei and H. M. Cheng, Carbon, 2012, 50, 3210-3228.

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 9

Please do not adjust margins

 Please
Journal ofdo not adjustChemistry
Materials margins C Page 10 of 11
View Article Online
DOI: 10.1039/C7TC03669H
Journal of Material Chemistry C ARTICLE

55. S. Stankovich, R. D. Piner, X. Chen, N. Wu, S. T. Nguyen 61. A. Pantelopoulos and N. G. Bourbakis, IEEE Transactions
and R. S. Ruoff, Journal of Materials Chemistry, 2006, 16, on Systems, Man, and Cybernetics, Part C (Applications
155-158. and Reviews), 2010, 40, 1-12.
56. T. Wang, Y. Li, S. Geng, C. Zhou, X. Jia, F. Yang, L. Zhang, X. 62. S. Patel, H. Park, P. Bonato, L. Chan and M. Rodgers,
Ren and H. Yang, RSC Advances, 2015, 5, 88958-88964. Journal of NeuroEngineering and Rehabilitation, 2012, 9,

Journal of Materials Chemistry C Accepted Manuscript

57. H. Ha, K. Shanmuganathan and C. J. Ellison, ACS Applied 21.
Materials & Interfaces, 2015, 7, 6220-6229. 63. N. Celik, N. Manivannan, A. Strudwick and W.
58. W. C. Smith, Smart textile coatings and laminates, Balachandran, Nanomaterials, 2016, 6, 156.
Elsevier, 2010. 64. C. Lou, R. Li, Z. Li, T. Liang, Z. Wei, M. Run, X. Yan and X.
59. A. J. East, in Synthetic Fibres, ed. J. E. McIntyre, Liu, Sensors, 2016, 16, 1833.
Woodhead Publishing, Editon edn., 2005, pp. 95-166, 65. M. K. Yapici, T. Alkhidir, Y. A. Samad and K. Liao, Sensors
Published on 06 October 2017. Downloaded by University of Newcastle on 06/10/2017 23:07:56.

ISBN No 9781855735880. and Actuators B: Chemical, 2015, 221, 1469-1474.

60. K. Ali, J. Van Der Veen, K. Nossent and U. Amrit, NIP &
Digital Fabrication Conference, Austin, Texas, USA, 2010.

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A table of contents entry

Journal of Materials Chemistry C Accepted Manuscript

Published on 06 October 2017. Downloaded by University of Newcastle on 06/10/2017 23:07:56.

We report inkjet printing of an organic nanoparticles-based surface pre-treat onto textiles to

enable all inkjet-printed graphene e-textiles