Article

Cite This: ACS Nano 2017, 11, 11513-11520 www.acsnano.org

Three-Dimensional Printed Thermal

Regulation Textiles
Tingting Gao,† Zhi Yang,‡ Chaoji Chen,† Yiju Li,† Kun Fu,† Jiaqi Dai,† Emily M. Hitz,† Hua Xie,†
Boyang Liu,† Jianwei Song,† Bao Yang,‡ and Liangbing Hu*,†
†
Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, University of Maryland, College
Park, Maryland 20742, United States
*
S Supporting Information
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ABSTRACT: Space cooling is a predominant part of energy consumption in

people’s daily life. Although cooling the whole building is an effective way to
provide personal comfort in hot weather, it is energy-consuming and high-
Downloaded via TUFTS UNIV on June 29, 2018 at 14:33:04 (UTC).

cost. Personal cooling technology, being able to provide personal thermal

comfort by directing local heat to the thermally regulated environment, has
been regarded as one of the most promising technologies for cooling energy
and cost savings. Here, we demonstrate a personal thermal regulated textile
using thermally conductive and highly aligned boron nitride (BN)/poly(vinyl
alcohol) (PVA) composite (denoted as a-BN/PVA) fibers to improve the
thermal transport properties of textiles for personal cooling. The a-BN/PVA
composite fibers are fabricated through a fast and scalable three-dimensional
(3D) printing method. Uniform dispersion and high alignment of BN
nanosheets (BNNSs) can be achieved during the processing of fiber
fabrication, leading to a combination of high mechanical strength (355 MPa) and favorable heat dispersion. Due to the
improved thermal transport property imparted by the thermally conductive and highly aligned BNNSs, better cooling effect
(55% improvement over the commercial cotton fiber) can be realized in the a-BN/PVA textile. The wearable a-BN/PVA
textiles containing the 3D-printed a-BN/PVA fibers offer a promising selection for meeting the personal cooling
requirement, which can significantly reduce the energy consumption and cost for cooling the whole building.
KEYWORDS: 3D printing, thermal regulation textiles, thermally conductive fiber, aligned BN nanosheets, energy efficiency

P ersonal cooling technologies have attracted increasing

attention due to their capability of providing thermal
comfort by locally controlling the temperature of an
individual in a low-cost and energy-saving way.1−3 The
combination of personal cooling with wearable textiles has
been regarded as one of the most promising strategies to bring
personal cooling into daily life.4,5 Wearable textiles with cooling
function can provide the building occupants thermal comfort in
hot weather via the localized cooling in wearable structure
textiles and relax the temperature setting of the air conditioning
system in buildings, resulting in an efficient reduction of the
cost for cooling the whole building.6 These textiles have driven
researchers in textile science and industry to devote continuous
efforts to improve the thermal regulation properties of textiles,
thus providing a comfortable and safe thermal microclimate to
satisfy the cooling needs of the human body. Nowadays, there
are several commercially available textiles which can provide
different levels of personal thermal regulation. Moisture
management textiles, as the most common thermal regulation
technology in the industry, are able to cool the human body by
removing excessive moisture.7,8 However, the thermal regu-
lation mechanism in such textiles can only be triggered when
the microclimate between body and fabric is at a high humidity
level, which will limit its practical applications where the
humidity level is low. Other technologies including cold pack
textiles with phase change materials,9 air-cooled textiles,10 and
liquid cooling textiles11 have their limitations, such as
inconvenience from the bulky size of the cold pack, massive
consumption of power, and high cost.
To address these limitations, considerable efforts of
developing thermal regulation textiles have been undertaken
recently.12−17 Cui and co-workers reported on a mid-infrared
transparent nanoporous polyethylene for efficient human body
cooling.2 The same group further developed a wearable face
mask based on a nanofiber/nanoporous polyethylene system
with high infrared transparency of 92.1%, enabling an efficient
radiative cooling.3 Yang and co-workers demonstrated a
scalable manufactured randomized glass−polymer hybrid
metamaterial that has excellent daytime radiative cooling
effects.18 These versatile findings have inspired incredible
approaches to incorporate thermal management materials into
Received: September 4, 2017
Accepted: October 26, 2017
Published: October 26, 2017

© 2017 American Chemical Society 11513 DOI: 10.1021/acsnano.7b06295

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Figure 1. Schematic illustration of the thermal regulation textile. The thermal regulation textile is made of thermally conductive composite
fibers with well-aligned and interconnected BNNSs embedded in the PVA polymer matrix. The a-BN/PVA textile can release the extra heat
produced by the human body along the fiber into the ambient environment, thus providing a thermally comfortable microclimate to the
human body for personal cooling. The highly aligned BNNSs in the microfibers act as efficient heat transfer pathways.

Figure 2. Processing of a-BN/PVA nanocomposite fiber. (a) Schematic of the fabrication process of a-BN/PVA composite fiber. (b) Photo
image of DMSO/BNNS dispersion and PVA/DMSO/BNNS dispersion after standing for 1 week, suggesting that the addition of PVA helps to
homogeneously disperse the BNNSs in DMSO solution. (c) Photo image showing the a-BN/PVA fiber was prepared by printing the uniform
dispersion into cooled methanol through a 3D printing machine. (d) Photo image showing the a-BN/PVA fiber winding on a yarn bobbin,
indicating the scalability of the a-BN/PVA fiber preparation. (e) Photo image showing the textile woven by the a-BN/PVA composite fibers.
Optical images of the a-BN/PVA fabrics with different structures: (f) plain woven and (g) knitted fabric. Insets are the structure diagrams of
fabric construction.

textiles for effective personal cooling. Despite the tremendous
efforts dedicated to developing personal cooling textiles
through infrared thermal radiation as mentioned above, limited
success has been achieved with personal cooling textiles that
use direct thermal conduction from the hot body to the
ambient environment. Among the three main ways (con-
duction, convection, and radiation) for thermal transmission in
thermal regulated textiles, heat conduction is as significant as
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the other two ways. When the heat is transferred by
conduction, the energy is dissipated outward from the human
body through clothing to the external environment.19−21
Therefore, thermally conductive textiles can be attractive for
personal cooling. Nevertheless, conventional textile fibers
usually have a low thermal conductivity, which hinders the
body-generated heat from escaping to the environment, leading
to an unsatisfactory cooling effect.
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Figure 3. Morphological characterizations of the a-BN/PVA composite. (a) Optical image of a-BN/PVA fiber shows the diameter of the
finished fiber is about 95 μm (scale bar is 500 μm). (b−d) SEM images of the a-BN/PVA fiber show the alignment of the BNNSs along the
fiber direction after the hot-drawing. (e,f) Low- and high-resolution TEM images of the BNNSs. In (e), inset is the SAED pattern of the
BNNS. (g) TEM image of a slice peeled from a-BN/PVA fiber. 2D small-angle X-ray diffraction patterns of the as-printed fiber before (h) and
after hot-stretching (i). (j) Profiles of the scattering intensity as a function of azimuthal angle (φ).

Here, we demonstrate a thermal regulation textile based on
thermally conductive and highly aligned boron nitride (BN)/
poly(vinyl alcohol) (PVA) composite fibers synthesized by 3D
printing for efficient personal cooling (Figure 1). 3D printing,
as an efficient additive manufacturing technique, can fast and
accurately fabricate an arbitrary and complicated structure that
is desired for optimizing its performance by successive
printing.22−27 BN has been traditionally considered as an
effective material in thermal management applications due to its
high thermal conductivity yet electrical insulation.28−30 With a
two-dimensional structure, the BN nanosheets (BNNSs) have a
high in-plane thermal conductivity of up to 2000 W/(m·K).31,32
To take advantage of the in-plane thermal performance of
BNNSs, the sheets must be well oriented and uniformly
dispersed.33−35 Because BNNSs can be sterically stabilized by
absorbed polymer during ultrasonication in a solution of PVA, a
homogeneous dispersion can be achieved.36 Meanwhile, a good
orientation of BNNSs in nanocomposite fiber was introduced
by uniaxial elongational flow during fiber printing and further
hot-drawing processing, which can form energetic pathways for
phonon conduction. Highly orientated BNNSs effectively
enhance the thermal performance of the a-BN/PVA composite
fiber by providing numerous thermally conductive pathways
along the aligned and interconnected BNNSs. A wearable
textile based on the a-BN/PVA composite fibers thus can
effectively direct the body-generated heat away from the skin to
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the cool ambient environment, resulting in an attractive cooling
effect for personal cooling (Figure 1). The personal cooling
technique using the wearable cooling textile is an effective way
to promote the thermal comfort for building occupants in hot
weather, which can significantly reduce the energy required to
cool the building itself.
RESULTS AND DISCUSSION
Figure 2a briefly illustrates the 3D printing fabrication process
of the a-BN/PVA composite fibers. Liquid-phase exfoliated
BNNSs were first prepared by sonicating the raw hexagonal
boron nitride (h-BN) powders in isopropyl alcohol solution.
The raw h-BN bulk powders with a size of over 30 μm can be
exfoliated to BN flakes with a size of less than 1 μm (Figure
S1). Figure S2a shows a typical Raman spectrum of h-BN. After
exfoliation, the (100), (101), and (102) peaks of h-BN bulk
disappear, which is attributed to the decrease of the thickness-
to-size ratio (Figure S2b).35 In other words, the h-BN
micropowders were successfully exfoliated to thin BN nano-
sheets. The uniform BN/PVA suspensions were then obtained
by dispersing the liquid-phase exfoliated BNNSs into PVA/
dimethyl sulfoxide (DMSO) solution using sonication. The
above-prepared homogeneous BN/PVA dispersion solution
was injected into a coagulation bath from a needle through the
3D printer to fabricate the continuous as-printed fibers. The as-
printed fibers were then hot-drawn under high temperature
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Figure 4. Mechanical and thermal properties of the a-BN/PVA composite fiber. (a) Typical stress−strain curves of the prepared a-BN (45 wt
%)/PVA fiber and pure PVA; the tensile strength of 350 MPa was achieved by incorporation of 45 wt % BNNS loading. (b) Stiffness (Young’s
modulus) of the pure PVA and a-BN/PVA fibers are 216 MPa and 12.38 GPa, respectively. (c) Comparison of our data of tensile strength
with results reported elsewhere. Our a-BN/PVA fiber even with high loading of BNNSs exhibits a tensile strength better than that of other
polymer-based composites. (d) Schematic illustration of the proposed thermal conduction model of the a-BN/PVA fiber. The aligned BNNSs
form continuous thermally conductive pathways along the fiber direction. The red lines indicate heat transfer paths. (e) Temperature
distribution on the cotton yarn, PVA fiber, as-printed BN/PVA fiber without BNNS alignment, and a-BN/PVA fiber.

(200 °C) until a draw ratio of 4 was reached. The PVA fibers
were condensed, and the randomly dispersed BNNSs inside the
fibers became highly aligned under hot-drawing. Note that the
well-dispersed BNNSs’ ink can guarantee a fiber with a uniform
distribution of BNNSs during 3D printing. Photographs of the
dispersions containing 0.5 wt % BNNSs with and without 5 wt
% PVA are shown in Figure 2b. With the addition of 5 wt %
PVA, BNNSs can be well-dispersed in the printing ink without
aggregation for a long time. In contrast, aggregation of BNNSs
occurs in a short time without the addition of PVA, indicating
the poor dispersion of BNNSs in pure DMSO solution. The
uniform and stable dispersion of BNNSs in the PVA/DMSO
solution can be ascribed to the steric stabilization of BNNSs by
the absorbed polymer molecules through hydrogen bonding
during the ultrasonication process. The well-dispersed BN/
PVA solution has a suitable viscosity to be easily printed from a
metal needle into a cooled methanol solution by a program-
controlled 3D printing machine (Figure 2c). By using the 3D
printing fabrication method, scalable fibers can be quickly and
cost-effectively produced (Figure 2d). The prepared a-BN/PVA
composite fibers can be woven into fabrics with different
structures, which makes the cooling textile based on the a-BN/
PVA fibers possible (Figure 2e−g).
To understand the orientation of BNNSs in fibers, we
investigated the microscale morphology of the a-BN/PVA
composite fiber. Figure 3a and Figure S3a show that the
diameter of the stretched fiber is 3 times smaller than that of as-
printed fiber before hot-drawing. The as-printed BN/PVA
composite fiber before hot-drawing is about 300 μm in
diameter (Figure S3a). Meanwhile, the BNNSs in the fiber
are disorderedly embedded in the polymer matrix (Figure
S3b,c). Further hot-drawing dramatically decreases the
diameter of the BN/PVA fiber from 300 to 95 μm, resulting
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in a much denser structure than the as-printed fiber without
stretching (Figure 3a,b). Figure 3c,d shows that a high
alignment of BNNSs along the length direction of fiber is
obtained after the hot-drawing process. The element mapping
results indicate that BNNSs are uniformly embedded in the
polymer matrix (Figure S4). The microstructure, phase
structure, and orientation of the BNNSs are further
characterized by transmission electron microscopy (TEM)
and small-angle X-ray scattering (SAXS). Figure 3e shows the
TEM image of the BNNSs, which reveals the two-dimensional
morphology and thin thickness of the BNNSs. The inset of
selected area electron diffraction (SAED) pattern in Figure 3e
shows the single-crystal structure of the BNNS.37,38 Figure 3f
reveals that the thickness of the BNNS is around 3 nm, which
corresponds to 9 layers of single BNNSs. The TEM image on
the edge of the composite fiber displays the alignment of
BNNSs, in good agreement with the scanning electron
microscopy (SEM) observation of the cross section of the a-
BN/PVA composite fiber (Figure 3g). Enhanced alignment of
the BNNSs after hot-drawing treatment is further confirmed
using SAXS. Due to the weak X-ray scattering of PVA, the
diffraction peaks mainly originated from the BNNSs.39 For the
as-printed fiber before hot-stretching, no sharp scattering peak
is observed in the elliptical two-dimensional small-angle X-ray
scattering (2D-SAXS) pattern, indicating a poor alignment of
BNNSs (Figure 3h,j). For the a-BN/PVA fiber after hot-
drawing, a sharp scattering peak can be clearly observed,
suggesting the well-aligned BNNSs along the length direction
of the fiber (Figure 3i,j).40−42 Moreover, the monotonic
intensity drop with no visible peak also indicates the uniform
dispersion of BNNSs in the fiber after hot-stretching (Figure
S5).
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Figure 5. Thermal properties and cooling effects of various fabrics. (a) IR images showing the temperature distributions of various textiles. (b)
Maximum surface temperature of the cotton, PVA, and a-BN/PVA fabrics under different input laser powers. (c) Measurements of the
thermal conductivities of the cotton, PVA, and a-BN/PVA fabrics, which are sandwiched between two aluminum (Al) blocks. Same laser
intensity was applied on the top surface of an Al block. (d) Modeling and calculation of the maximum temperature of various fabrics above the
human skin (the temperature of human skin is set to be 37 °C). The a-BN/PVA fabric displays the highest surface temperature, indicating the
best cooling effect among the three fabrics.

The dense structure and well-aligned BNNSs are expected to
improve the mechanical properties of the a-BN/PVA composite
fiber. Typical stress−strain curves for the pure PVA fiber and a-
BN/PVA composite fiber are shown in Figure 4a. A high tensile
strength of 355 MPa is achieved for the a-BN/PVA composite
fiber with 45 wt % BNNS loading, which is ∼3 times higher
than that of pure PVA fiber (122 MPa). The a-BN/PVA
composite fiber also demonstrates a significantly improved
stiffness of 12.38 GPa, ∼57 times higher than that of pure PVA
fiber (Figure 4b). The high mechanical tensile strength of the a-
BN/PVA composite fiber surpasses most of the existing BN-
based fibers, demonstrating superior mechanical properties for
wearable textile applications (Figure 4c).43−49 The enhanced
mechanical tensile strength should be ascribed to the structure
of the aligned BNNSs, where efficient load transfer across the
filler−matrix interface may occur during the tensile process.
Meanwhile, the great interfacial compatibility between PVA and
BNNSs may also contribute to the enhanced mechanical
strength.36 As shown in Figure S6, the fractured BNNSs linked
with PVA bridges can be observed in the fracture surface area
after tensile test, confirming the strong interaction between the
PVA molecules and BNNSs. After the force loading, the
BNNSs first slide against each other, and subsequently, the
PVA long chains acting as bridges between BNNSs are
stretched along the sliding direction to dissipate a large amount
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of the loading energy.36,50 With a further increase of the loading
strength, the link between PVA and BNNSs is broken, resulting
in the pulling out of BNNSs.
Another benefit of the dense composite fiber with aligned
BNNSs is the enhanced thermal conductivity and heat
spreading along the fiber.51 As illustrated in Figure 4d, the
alignment of BNNSs can facilitate the in-plane heat transfer by
forming a rapid thermal path along the fiber. The thermal
properties of various fiber samples with the same diameter were
qualitatively characterized by a laser-IR camera system. Under
the same laser input power (1 mm diameter spot size), different
maximum local temperature of the fiber samples can
qualitatively reveal different heat conduction properties. Fiber
with higher thermal conductivity conducts the heat more
effective from the heat spot generated by a laser, resulting in a
lower maximum temperature at the heat source. On the
contrary, the fiber with low thermal conductivity will lead to the
heat accumulation around the heat spot due to insufficient heat
dissipation from a hot source to surroundings. The maximum
temperature of the a-BN/PVA composite fiber (39.8 °C) is
much lower than those of the commercial cotton yarn (55.9
°C), pure PVA fiber (48 °C), and BN/PVA composite fiber
without BNNS alignment (43.6 °C), suggesting highest thermal
conductivity of the a-BN/PVA composite fiber (Figure 4e).
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Laser-IR camera test systems were built to investigate the
thermal properties of the a-BN/PVA, PVA, and cotton fabrics.
The measurement details (temperature distribution on fabrics)
are shown in the supplementary methods S1 and Figure S7. For
the same fabric sample, when the laser power input to the fabric
increased, a higher maximum temperature was observed on the
fabric. From the comparison of three different fabric samples,
the a-BN/PVA composite fabric has the lowest maximum
temperature at all laser power inputs of P = 0.047, 0.079, and
0.096 W, indicating the best heat dissipation property (Figure
5a,b). We further measured the thermal conductivities of the a-
BN/PVA, pure PVA, and cotton fabrics. Figure 5c shows the
measurement device of the thermal conductivity of fabric in our
work. The fabrics were sandwiched between two Al blocks, and
the laser was applied on the top surface of Al block. The
generated heat from the top Al block conducts to the bottom
Al block through the fabrics in the middle. We can clearly
observe that, under the same laser power, the Al block on the a-
BN/PVA fabric has the lowest temperature, which indicates the
best thermal conductivity of the a-BN/PVA fabric. Through
simulation on ANSYS and calculation (supplementary methods
S2 and Figure S8), we can conclude that the a-BN/PVA fabric
possesses a high thermal conductivity of 0.078 W/(m·K), which
is ∼2.2 and ∼1.6 times higher than that of the cotton fabric and
PVA fabric, respectively (Figure 5c) and superior than many
commercial fabircs (Table S1).
A finite element model in ANSYS was built to demonstrate
the cooling effect of the three fabrics with different thermal
properties for personal cooling applications. In the simulation
model, fabric is exposed to ambient conditions on the top
surface (skin) of a human body, which is considered a thermal
barrier between the human body and the ambient environment.
The temperature of skin and ambient environment was set to
37 and 25 °C, respectively. The heat generated by the human
body is transferred through the fabric to the environment.
During the heat transfer process from the body to the
environment, the thermal conductivity of the fabric plays a vital
role to maintain thermal comfort of the human body. High
thermal conductivity of fabrics contributes to unimpeded heat
dissipation from the body to the environment (high heat flux).
From the results of simulation, the a-BN/PVA composite fabric
yields the highest fabric outer temperature of 36.2 °C and heat
flux of 58.4 W/m2. For the pure PVA and cotton fabric, the
fabric outer temperature and heat fluxes are 35.7 °C and 55.99
W/m2, 35.2 °C and 53.35 W/m2, respectively. The cooling
effect of the a-BN/PVA composite fabric is 55% greater than
the commercial cotton fabric, which displays a better thermal
management capacity for personal cooling.
Note that in real applications, the cooling textile contacts the
human body with different angles between the skin and the
fibers, causing a temperature nonuniformity along the fabric,
which will cause heat transfer along the fiber-length direction
and radial direction (Figure 1). Overall, the cooling mechanism
for such a thermal regulation textile modulates the heat transfer
path from the human body directly to the environment by
changing its properties, such as thermal conductivity for heat
conduction, porosity for convection, radiation, and moisture
transfer.
CONCLUSION
In our work, we demonstrated a personal thermal regulation
textile based on thermally conductive and highly aligned BN/
PVA fibers for personal cooling applications. The a-BN/PVA
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composite fibers are fabricated through the low-cost, fast, and
scalable 3D printing technique followed by a hot-drawing
treatment. The dense structure of fibers and uniform dispersion
and high alignment of BNNSs can be achieved during the
process of fiber fabrication, leading to excellent mechanical
strength (355 MPa), uniform heat dispersion, and high thermal
conductivity. As a result, the fabric based on the a-BN/PVA
fibers has a high thermal conductivity of 0.078 W/(m·K), which
is 1.56 and 2.22 times higher than those of PVA fabrics and
cotton fabrics, respectively. Through the finite element thermal
simulation, we found that the cooling effect of a-BN/PVA fabric
is 55% higher than that of commercial cotton fabric, further
confirming the excellent cooling ability of the a-BN/PVA fabric.
The wearable cooling textile consisting of 3D-printed a-BN/
PVA fibers provides an effective choice for personal cooling of
the building occupants in hot weather, thus decreasing the
demand for indoor temperature regulation and significantly
reducing the energy and cost for cooling the building itself.
METHODS
Preparation of BNNSs. In brief, commercial h-BN micropowder
(2 g, 30 μm in size, Momentive Inc.) was dispersed in isopropyl
alcohol (IPA) (300 mL, purity ≥99.5%). The dispersion was sonicated
for 48 h in a sonic bath and then centrifuged at 2000 rpm for 20 min.
After centrifugation of the dispersions, the supernatant was decanted.
The supernatant of the BN/IPA solution from the centrifugation
process was then filtered via vacuum filtration. After filtration, the
obtained BN cake was dried for 4 h in an oven at 60 °C, and this dried
powder was used as the filler material for composite fiber formation.
Suspension Preparation and Fiber Printing. PVA solution with
5 wt % PVA concentration was used as surfactant to obtain uniformly
dispersed BNNS powders. First, the 0.5 g PVA chip was dissolved into
the 9.5 g of DMSO at 100 °C with agitation. Then, the prepared
BNNSs were dispersed in the PVA solution by sonication for 4 h and
high energy probe sonication for 1 h. During the sonication process,
sonication bath temperature was maintained close to room temper-
ature. After that, PVA chips (lab grade, Fisher Scientific, USA) with
desired weight were gradually added into the prepared solution. This
mixture was subjected to sonication and further stirring for 8 h by
heated to 95 °C. The optically homogeneous BN/PVA dispersion thus
obtained was ready for fiber printing. 3D printing fabrication was
conducted using a 3D printer (Fisnar F4200n), which is controlled by
programmed procedures. The BN/PVA ink was injected at 1 mL/min
using a 20 gauge needle into a cooled methanol bath at a temperature
of 0 °C. The as-printed fibers were then collected and kept rotating in
methanol at room temperature for more than 24 h and subsequently
dried at ambient conditions. The hot-drawn process of the fiber was
subsequently conducted by heating and stretching the as-printed fiber
through a hot zone at a temperature of 200 °C (on a hot plate). The
stretching ratio was controlled by a feeding roll with a low speed and a
stretching reel with a high speed (Figure S9). The drawn ratio of the
samples was 4.
Characterization. The morphology was studied via SEM and
TEM using Hitachi SU-70 field emission scanning electron
microscopy and a JEOL JEM 2100 TEM, respectively. To determine
the thickness, BN nanosheets were spin-coated on Si wafers for atomic
force microscopy (AFM) measurement. AFM data were taken and
analyzed by Veeco Multimode AFM with a Nanoscope III controller,
180 × 180 μm scanner, Nanoscope and Gwyddion software. The
Raman spectra of the h-BN surface were measured by a Horiba Jobin-
Yvon Raman spectrometer with laser wavelength of 532 nm. The X-ray
diffraction pattern was collected by D8 Advanced (Bruker AXS, WI,
USA) using a Cu Kα radiation source. SAXS was performed to
characterize the fiber alignment with an X-ray wavelength of λ = 0.957
Å and sample-to-detector distance of 8.422 mm. The beam size was 24
× 11 mm (horizontal × vertical), and a single-photon counting
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detector (Pilatus 1 M, Dectris) having a pixel size of 172 × 172 μm2
was used to record the scattering patterns.
Mechanical Property Characterization. The tensile strength of
the fibers was tested using a dynamic mechanical analysis machine
(Q800, TA Instruments, USA) in tension mode. Each fiber was 20 mm
long, and the strain ramp was set at 5% min−1. All tests were
conducted under laboratory environment at room temperature (25 ±
0.2 °C). Twenty specimens were tested for each type of the fibers. The
forces obtained by DMA were converted into stress values, dividing by
the cross-sectional area of the fiber. The average diameters of fibers for
tensile testing were measured by optical microscopy.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b06295.
SEM images and X-ray diffraction profiles of the h-BN
powders and BNNSs; Raman spectra of the BNNSs,
morphological structure of the BN/PVA fiber before hot-
stretching; elemental mappings of the cross section of the
a-BN/PVA composite fiber, profiles of scattering
intensity (I × q2) as a function of scattering; SEM
images of the tensile fractured surface of the a-BN/PVA
fiber; thermal conductivity comparison of our a-BN/PVA
composite textile with other commercial fabrics;
schematic illustration of the device for temperature
distribution measurement, of the setup for thermal
conductivity measurement, and of hot-drawn process of
the fiber (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: binghu@umd.edu.
ORCID
Yiju Li: 0000-0001-9240-5686
Liangbing Hu: 0000-0002-9456-9315
Author Contributions
L.H., T.G., and C.C. designed the experiments. Z.Y. and B.Y.
measured the thermal conductivity and conducted IR measure-
ments. J.D. created the 3D illustrations. Y.L. provided
characterization via SEM and TEM. C.C. performed mechan-
ical measurements and the corresponding analysis. K.F., J.S.,
E.H., H.X., and B.L. contributed material characterizations. Z.Y.
and B.Y. were responsible for the thermal modeling. L.H., T.G.,
Y.L., and C.C. collectively wrote the paper. All authors
commented on the final manuscript. T.G., Z.Y., and C.C.
contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
L.H. acknowledges the financial support from the Office of
Naval Research Young Investigator Program (ONR YIP,
Prougram Manager: Sarwat Chappell) and the Advanced
Research Projects Agency-Energy (ARPA-E), U.S. Department
of Energy. Z.Y. and B.Y. acknowledge the financial support
from the Advanced Research Projects Agency-Energy (ARPA-
E), U.S. Department of Energy. We acknowledge the support
of the Maryland Nanocenter, its Surface Analysis Center and
AIMLab. T.G. and Y.L. acknowledge the financial support by
China Scholarship Council (CSC).
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Article
REFERENCES
(1) Law, T. The Future of Thermal Comfort in an Energy-Constrained
World; Springer International Publishing; Heidelberg, 2013; pp 1−4.
(2) Hsu, P.-C.; Song, A. Y.; Catrysse, P. B.; Liu, C.; Peng, Y.; Xie, J.;
Fan, S.; Cui, Y. Radiative Human Body Cooling by Nanoporous
Polyethylene Textile. Science 2016, 353, 1019−1023.
(3) Yang, A.; Cai, L.; Zhang, R.; Wang, J.; Hsu, P.-C.; Wang, H.;
Zhou, G.; Xu, J.; Cui, Y. Thermal Management in Nanofiber-Based
Face Mask. Nano Lett. 2017, 17, 3506−3510.
(4) Mokhtari Yazdi, M.; Sheikhzadeh, M. Personal Cooling
Garments: a Review. J. Text. Inst. 2014, 105, 1231−1250.
(5) Hu, J.; Meng, H.; Li, G.; Ibekwe, S. I. A Review of Stimuli-
Responsive Polymers for Smart Textile Applications. Smart Mater.
Struct. 2012, 21, 053001.
(6) Catrysse, P. B.; Song, A. Y.; Fan, S. Photonic Structure Textile
Design for Localized Thermal Cooling Based on a Fiber Blending
Scheme. ACS Photonics 2016, 3, 2420−2426.
(7) Das, B.; Das, A.; Kothari, V.; Fanguiero, R.; De Araújo, M. Effect
of Fibre Diameter and Cross-Sectional Shape on Moisture Trans-
mission through Fabrics. Fibers Polym. 2008, 9, 225−231.
(8) Kaplan, S.; Okur, A. Thermal Comfort Performance of Sports
Garments with Objective and Subjective Measurements. Indian J. Fibre
Text. Res. 2012, 37, 46−54.
(9) Gao, C.; Kuklane, K.; Wang, F.; Holmér, I. Personal Cooling with
Phase Change Materials to Improve Thermal Comfort from a Heat
Wave Perspective. Indoor Air 2012, 22, 523−530.
(10) Yang, J.-H.; Kato, S.; Seok, H.-T. Measurement of Airflow
around the Human Body with Wide-Cover Type Personal Air-
Conditioning with PIV. Indoor Built Environ. 2009, 18, 301−312.
(11) Bartkowiak, G.; Dabrowska, A.; Marszalek, A. Assessment of an
Active Liquid Cooling Garment Intended for Use in a Hot
Environment. Appl. Ergon. 2017, 58, 182−189.
(12) Yanilmaz, M.; Dirican, M.; Zhang, X. Evaluation of Electrospun
SiO2/Nylon 6, 6 Nanofiber Membranes as a Thermally-Stable
Separator for Lithium-Ion Batteries. Electrochim. Electrochim. Acta
2014, 133, 501−508.
(13) Li, Y.; Zhang, Z.; Li, X.; Zhang, J.; Lou, H.; Shi, X.; Cheng, X.;
Peng, H. A Smart, Stretchable Resistive Heater Textile. J. Mater. Chem.
C 2017, 5, 41−46.
(14) Misra, V.; Bozkurt, A.; Calhoun, B.; Jackson, T.; Jur, J. S.; Lach,
J.; Lee, B.; Muth, J.; Oralkan, Ö .; Ö ztürk, M.; et al. Flexible
Technologies for Self-Powered Wearable Health and Environmental
Sensing. Proc. IEEE 2015, 103, 665−681.
(15) Li, Z.; Xu, Z.; Liu, Y.; Wang, R.; Gao, C. Multifunctional non-
Woven Fabrics of Interfused Graphene Fibres. Nat. Commun. 2016, 7,
13684.
(16) Zeng, W.; Shu, L.; Li, Q.; Chen, S.; Wang, F.; Tao, X. M. Fiber-
based Wearable Electronics: a Review of Materials, Fabrication,
Devices, and Applications. Adv. Mater. 2014, 26, 5310−5336.
(17) Chen, Z.; Zhu, L.; Raman, A.; Fan, S. Radiative Cooling to Deep
Sub-Freezing Temperatures through a 24-h Day−Night Cycle. Nat.
Commun. 2016, 7, 13729.
(18) Zhai, Y.; Ma, Y.; David, S. N.; Zhao, D.; Lou, R.; Tan, G.; Yang,
R.; Yin, X. Scalable-Manufactured Randomized Glass-Polymer Hybrid
Metamaterial for Daytime Radiative Cooling. Science 2017, 355, 1062−
1066.
(19) Speakman, J.; Chamberlain, N. 3The Thermal Conductivity
of Textile Materials and Fabrics. J. Text. Inst., Trans. 1930, 21, T29−
T56.
(20) Fan, J.; Luo, Z.; Li, Y. Heat and Moisture Transfer with Sorption
and Condensation in Porous Clothing Assemblies and Numerical
Simulation. Int. J. Heat Mass Transfer 2000, 43, 2989−3000.
(21) Fan, J.; Chen, Y. Measurement of Clothing Thermal Insulation
and Moisture Vapour Resistance Using a Novel Perspiring Fabric
Thermal Manikin. Meas. Sci. Technol. 2002, 13, 1115.
(22) Zhu, C.; Han, T. Y.-J.; Duoss, E. B.; Golobic, A. M.; Kuntz, J. D.;
Spadaccini, C. M.; Worsley, M. A. Highly Compressible 3D Periodic
Graphene Aerogel Microlattices. Nat. Commun. 2015, 6, 6962.
DOI: 10.1021/acsnano.7b06295
ACS Nano 2017, 11, 11513−11520
ACS Nano Article

(23) Jakus, A. E.; Secor, E. B.; Rutz, A. L.; Jordan, S. W.; Hersam, M. (43) Li, Y.; Zhu, H.; Shen, F.; Wan, J.; Lacey, S.; Fang, Z.; Dai, H.;
C.; Shah, R. N. Three-Dimensional Printing of High-Content Hu, L. Nanocellulose as Green Dispersant for Two-Dimensional
Graphene Scaffolds for Electronic and Biomedical Applications. ACS Energy Materials. Nano Energy 2015, 13, 346−354.
Nano 2015, 9, 4636−4648. (44) Boland, C. S.; Barwich, S.; Khan, U.; Coleman, J. N. High
(24) Wang, X.; Jiang, M.; Zhou, Z.; Gou, J.; Hui, D. 3D Printing of Stiffness Nano-Composite Fibres from Polyvinylalcohol Filled with
Polymer Matrix Composites: a Review and Prospective. Composites, Graphene and Boron Nitride. Carbon 2016, 99, 280−288.
Part B 2017, 110, 442−458. (45) Tajaddod, N.; Song, K.; Green, E. C.; Zhang, Y.; Minus, M. L.
(25) Li, Y.; Gao, T.; Yang, Z.; Chen, C.; Luo, W.; Song, J.; Hitz, E.; Exfoliation of Boron Nitride Platelets by Enhanced Interfacial
Jia, C.; Zhou, Y.; Liu, B.; Yang, B.; Hu, L. 3D-Printed, All-in-One Interaction with Polyethylene. Macromol. Mater. Eng. 2016, 301,
Evaporator for High-Efficiency Solar Steam Generation under 1 Sun 315−327.
Illumination. Adv. Mater. 2017, 29, 1700981. (46) Wang, X.; Zhi, C.; Li, L.; Zeng, H.; Li, C.; Mitome, M.; Golberg,
(26) Wang, Y.; Chen, C.; Xie, H.; Gao, T.; Yao, Y.; Pastel, G.; Han, D.; Bando, Y. Chemical Blowing” of Thin-Walled Bubbles: High-
Throughput Fabrication of Large-Area, Few-Layered BN and Cx-BN
X.; Li, Y.; Zhao, J.; Fu, K.; Hu, L. 3D-Printed All-Fiber Li-Ion Battery
Nanosheets. Adv. Mater. 2011, 23, 4072−4076.
toward Wearable Energy Storage. Adv. Funct. Mater. 2017, 1703140. (47) Coleman, J. N.; Lotya, M.; O’Neill, A.; Bergin, S. D.; King, P. J.;
(27) Li, Y.; Zhu, H.; Wang, Y.; Ray, U.; Zhu, S.; Dai, J.; Chen, C.; Fu, Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith, R. J.; et al. Two-
K.; Jang, S.-H.; Henderson, D.; Li, T.; Hu, L. Cellulose-Nanofiber- Dimensional Nanosheets Produced by Liquid Exfoliation of Layered
Enabled 3D Printing of a Carbon-Nanotube Microfiber Network. Materials. Science 2011, 331, 568−571.
Small Methods 2017, 1, 1700222. (48) Zhi, C.; Bando, Y.; Tang, C.; Kuwahara, H.; Golberg, D. Large-
(28) Jiang, X.-F.; Weng, Q.; Wang, X.-B.; Li, X.; Zhang, J.; Golberg, Scale Fabrication of Boron Nitride Nanosheets and Their Utilization
D.; Bando, Y. Recent Progress on Fabrications and Applications of in Polymeric Composites with Improved Thermal and Mechanical
Boron Nitride Nanomaterials: a review. J. Mater. Sci. Technol. 2015, 31, Properties. Adv. Mater. 2009, 21, 2889−2893.
589−598. (49) Zhu, H.; Li, Y.; Fang, Z.; Xu, J.; Cao, F.; Wan, J.; Preston, C.;
(29) Weng, Q.; Wang, X.; Wang, X.; Bando, Y.; Golberg, D. Yang, B.; Hu, L. Highly Thermally Conductive Papers with Percolative
Functionalized Hexagonal Boron Nitride Nanomaterials: Emerging Layered Boron Nitride Nanosheets. ACS Nano 2014, 8, 3606−3613.
Properties and Applications. Chem. Soc. Rev. 2016, 45, 3989−4012. (50) Zeng, X.; Ye, L.; Yu, S.; Li, H.; Sun, R.; Xu, J.; Wong, C.-P.
(30) Chen, J.; Huang, X.; Zhu, Y.; Jiang, P. Cellulose Nanofiber Artificial Nacre-Like Papers Based on Noncovalent Functionalized
Supported 3D Interconnected BN Nanosheets for Epoxy Nano- Boron Nitride Nanosheets with Excellent Mechanical and Thermally
composites with Ultrahigh Thermal Management Capability. Adv. Conductive Properties. Nanoscale 2015, 7, 6774−6781.
Funct. Mater. 2017, 27, 1604754. (51) Xie, B.-H.; Huang, X.; Zhang, G.-J. High Thermal Conductive
(31) Wang, Y.; Xu, N.; Li, D.; Zhu, J. Thermal Properties of Two Polyvinyl Alcohol Composites with Hexagonal Boron Nitride
Dimensional Layered Materials. Adv. Funct. Mater. 2017, 27, 1604134. Microplatelets as Fillers. Compos. Sci. Technol. 2013, 85, 98−103.
(32) Wu, J.; Wang, B.; Wei, Y.; Yang, R.; Dresselhaus, M. Mechanics
and Mechanically Tunable Band Gap in Single-Layer Hexagonal
Boron-Nitride. Mater. Res. Lett. 2013, 1, 200−206.
(33) Kuang, Z.; Chen, Y.; Lu, Y.; Liu, L.; Hu, S.; Wen, S.; Mao, Y.;
Zhang, L. Fabrication of Highly Oriented Hexagonal Boron Nitride
Nanosheet/Elastomer Nanocomposites with High Thermal Con-
ductivity. Small 2015, 11, 1655−1659.
(34) Song, W. L.; Wang, P.; Cao, L.; Anderson, A.; Meziani, M. J.;
Farr, A. J.; Sun, Y. P. Polymer/Boron Nitride Nanocomposite
Materials for Superior Thermal Transport Performance. Angew.
Chem., Int. Ed. 2012, 51, 6498−6501.
(35) Lin, Y.; Connell, J. W. Advances in 2D Boron Nitride
Nanostructures: Nanosheets, Nanoribbons, Nanomeshes, and Hybrids
with Graphene. Nanoscale 2012, 4, 6908−6939.
(36) Khan, U.; May, P.; O’Neill, A.; Bell, A. P.; Boussac, E.; Martin,
A.; Semple, J.; Coleman, J. N. Polymer Reinforcement Using Liquid-
Exfoliated Boron Nitride Nanosheets. Nanoscale 2013, 5, 581−587.
(37) Lin, Y.; Williams, T. V.; Connell, J. W. Soluble, Exfoliated
Hexagonal Boron Nitride Nanosheets. J. Phys. Chem. Lett. 2010, 1,
277−283.
(38) Lin, Y.; Williams, T. V.; Xu, T.-B.; Cao, W.; Elsayed-Ali, H. E.;
Connell, J. W. Aqueous Dispersions of Few-lLyered and Monolayered
Hexagonal Boron Nitride Nanosheets from Sonication-Assisted
Hydrolysis: Critical Role of Water. J. Phys. Chem. C 2011, 115,
2679−2685.
(39) Zhang, J.; Feng, W.; Zhang, H.; Wang, Z.; Calcaterra, H. A.;
Yeom, B.; Hu, P. A.; Kotov, N. A. Multiscale Deformations Lead to
High Toughness and Circularly Polarized Emission in Helical Nacre-
like Fibres. Nat. Commun. 2016, 7, 10701.
(40) Xu, Z.; Gao, C. Graphene Chiral Liquid Crystals and
Macroscopic Assembled Fibres. Nat. Commun. 2011, 2, 571.
(41) Xu, Z.; Sun, H.; Zhao, X.; Gao, C. Ultrastrong Fibers Assembled
from Giant Graphene Oxide Sheets. Adv. Mater. 2013, 25, 188−193.
(42) Liu, Y.; Xu, Z.; Gao, W.; Cheng, Z.; Gao, C. Graphene and other
2D Colloids: Liquid Crystals and Macroscopic Fibers. Adv. Mater.
2017, 29, 1606794.

11520 DOI: 10.1021/acsnano.7b06295

ACS Nano 2017, 11, 11513−11520