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Communication
ZnO–MXene Nanocomposites www.advmat.de

Cold Sintered Ceramic Nanocomposites of 2D MXene and

Zinc Oxide
Jing Guo, Benjamin Legum, Babak Anasori, Ke Wang, Pavel Lelyukh, Yury Gogotsi,*
and Clive A. Randall*

the densification of ceramics.[6–10] Pres-

Nanocomposites containing 2D materials have attracted much attention ently, the integration of nanomaterials
due to their potential for enhancing electrical, magnetic, optical, mechanical, into composites is limited to the nanoma-
and thermal properties. However, it has been a challenge to integrate 2D terials that are compatible and thermally
materials into ceramic matrices due to interdiffusion and chemical reac- stable at relatively high temperatures
(>800 °C under argon) or the integration
tions at high temperatures. A recently reported sintering technique, the
into systems that do not require high
cold sintering process (CSP), which densifies ceramics with the assistance temperatures.[6–10]
of transient aqueous solutions, provides a means to circumvent the afore- The cold sintering process (CSP), a low
mentioned problems. The efficacious co-sintering of Ti3C2Tx (MXene), a 2D temperature sintering process (≤300 °C)
transition carbide, with ZnO, an oxide matrix, is reported. Using CSP, the for the densification of ceramics,[11–15]
provides a processing environment com-
ZnO–Ti3C2Tx nanocomposites can be sintered to 92–98% of the theoretical
patible with nanomaterials and 2D mate-
density at 300 °C, while avoiding oxidation or interdiffusion and showing rials. CSP is a pressure-assisted transient
homogeneous distribution of the 2D materials along the ZnO grain bounda- liquid phase sintering process, where the
ries. The electrical conductivity is improved by 1–2 orders of magnitude due aqueous phase undergoes evaporation
to the addition of up to 5 wt% MXene. The hardness and elastic modulus during sintering.[11] With the applica-
show an increase of 40–50% with 0.5 wt% MXene, and over 150% with tion of locally applied force in conjunc-
tion with capillary forces, a dissolution–
5 wt% of MXene. The successful densification of ZnO–MXene nanocom-
precipitation process occurs, leading to
posite demonstrates that the cold sintering of ceramics with 2D materials the mass transport of the ceramic par-
is a promising processing route for designing new nanocomposites with a ticles, which concurrently minimizes
diverse range of applications. the surface free energy while removing
porosity.[11,13,16] The relatively low sin-
tering temperatures of CSP are optimal
for the compaction of thermodynamically
2D materials possess excellent mechanical, electrical, and incompatible materials. It has been demonstrated that many
chemical properties, showing promise for a magnitude of appli- ceramics can be successfully co-sintered with polymers and
cations when integrated into nanocomposites.[1–3] The addition metals using CSP with holding times ranging from minutes to
of just a few percent of 2D materials can dramatically modify several hours.[12,15,17,18] To date, no work has been reported on
the properties of matrix materials, such as strength, hardness, the cold co-sintering of ceramics with 2D materials.
and conductivity.[4,5] However, 2D materials are typically not Recently, many 2D materials have been developed, such as
thermodynamically compatible with the high-temperature and/ graphene, silicene, germanene, phosphorene, chalcogenides,
or high-pressure processing techniques, which are needed for MXenes, etc.[19–22] Among these, MXenes are high-strength,
conductive 2D materials that show promise as reinforcements
for ceramics. MXenes are 2D transition metal carbides and
Dr. J. Guo, Dr. K. Wang, Prof. C. A. Randall nitrides with a unit formula of Mn+1XnTx layers; where M is an
Materials Research Institute and Department early transition metal (Ti, V, Nb, Ta, Cr, Mo, etc.), X is carbon
of Materials Science & Engineering or nitrogen, and n  = 1–3. Tx refers to surface-terminating
The Pennsylvania State University
functional groups such as oxygen (O), hydroxyl (OH), or
University Park, PA 16802, USA
E-mail: [email protected] fluorine (F). MXenes are mostly made by selective etching
B. Legum, Prof. B. Anasori, P. Lelyukh, Prof. Y. Gogotsi of certain atomic layers from their layered precursors (usually
Department of Materials Science and Engineering MAX phases) in aqueous fluoride–containing acids.[19,23] This
and A.J. Drexel Nanomaterials Institute synthesis method adds surface terminations to MXene flakes,
Drexel University which in turn make MXene surfaces hydrophilic. Most of the
Philadelphia, PA 19104, USA
E-mail: [email protected] MXenes synthesized to date have metallic conductivity.[19] For
example, 2D titanium carbide, Ti3C2Tx, which is the mostly
DOI: 10.1002/adma.201801846 studied MXene, has conductivity in the range of 103–104 S cm−1

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for both individual flakes as well as in the stacked films.[24,25] functionalization and without the need for high-energy, costly
MXenes have shown great promise for a variety of applica- processing conditions.
tions, including energy storage, electromagnetic interference The fabrication method of dense ZnO–Ti3C2Tx nanocompos-
shielding, sensors, water purifications, and medicine.[19] To ites is shown in Scheme 1b. To obtain a homogeneous disper-
date, MXenes have only been used as the reinforcement for sion, the prepared MXene solution was mixed and sonicated
polymer composites,[26–28] and no studies are available on with the ZnO, flash frozen, and then freeze-dried for 72 h.
MXene–metal or MXene–ceramic nanocomposites. Afterward, 17–20 wt% 1.5 M acetic acid was added into the
MXenes are ≈1 nm thick sheets of transition metal carbides, ZnO–Ti3C2Tx mixture and homogenized. Finally, the wetted
which are susceptible to oxidation in air. Furthermore, oxida- ZnO–Ti3C2Tx powders were pressed in a die under a pressure
tion has been shown to be accelerated at temperatures higher of 250 MPa at a temperature of 300 °C for 1 h. More details can
than 350 °C.[29,30] Therefore, traditional high temperature pro- be found in the Experimental Section.
cesses are not the best route for fabrication of MXene com- As shown in Figure 1a, the relative densities of the cold sin-
posites. However, this issue can be avoided through the CSP tered (1-y)ZnO–yTi3C2Tx composites (y  = 0, 0.5, 1, 3, 5 wt%)
because of sintering temperatures ≤300 °C. Additionally, the are all higher than 90%,demonstrating that CSP is a promi­
oxide-like surfaces of MXenes provide potential for compatible sing technique to sinter composite materials with MXenes.
integration in the oxide matrix of a ceramic, like ZnO. The X-ray diffraction (XRD) peaks of ZnO can be indexed to a
Among the cold sintered oxide ceramics, ZnO is an impor- wurtzite/zincite structure with the space group of P63mc, and
tant semiconducting material, which has the potential for a the MXene shows a broad (002) peak in the range of 8°–9° due
broad range of applications, such as varistors, thermoelectrics, to some multilayer flakes (Figure S1, Supporting Information),
optoelectronics, piezoelectric transducers, photocatalysts, and indicating that there is no reaction between ZnO and Ti3C2Tx
gas sensors.[31–33] ZnO is also a model system for the funda- under the cold sintering condition.
mental study of most sintering processes. Typically, ZnO is Figure 1b–e presents the SEM images of powders and
sintered to >90% of theoretical density at a temperature higher cold sintered samples of ZnO and 99ZnO–1Ti3C2Tx. In the
than 1000 °C with a holding time of several hours, using the case of cold sintered ZnO at 300 °C for 1 h, the grains grow
conventional thermal sintering.[34,35] By using the CSP, ZnO from nanometers (100–900 nm) to micrometers (1–4 µm)
has been shown to densify at temperatures ≤300 °C with (Figure 1b,d). In contrast, the grain growth of ZnO is sup-
a holding time of 1 h (total time of 2–3 h including heating, pressed in the cold sintered 99ZnO–1Ti3C2Tx composites
holding, and cooling).[14] The densification and grain growth (Figure 1c,e). The Ti3C2Tx located at the grain boundaries of
of the CSP sintered ZnO are controlled by the addition of an ZnO minimizes the coarsening of ZnO but does not prevent
acetic acid aqueous solution where the acetic acid dissolves the densification demonstrating that dense ZnO–Ti3C2Tx nano-
some of the exterior Zn ions from the surface of the powdered composites can be obtained by CSP. The cold sintered ZnO and
ceramic. This liquid phase coats each particle of the ceramic, 99ZnO–1Ti3C2Tx have highly compacted grain structures with a
assisting mass transport throughout each of the sintering steps, low porosity, which is in agreement with the measured density
including the rearrangement of particles, densification, and the data.
grain growth.[14] To further study the detailed microstructures of cold sintered
As a potential candidate in thermoelectric energy conversion, (1-y)ZnO–yTi3C2Tx nanocomposites, high-resolution TEM and
ZnO shows advantages of abundance, low cost, nontoxicity, STEM EDS mapping were employed, as shown in Figure 1f–l
and thermal stability.[36,37] However, the low electrical conduc- and Figures S2, S3 (Supporting Information). Figure 1f pre-
tivity limits its application.[37] The dispersion of 2D MXene sents the microstructural overview of the cold sintered 99ZnO–
along grain boundaries of ZnO, as shown in Scheme 1a, can 1Ti3C2Tx nanocomposite. The Ti3C2Tx nanosheets are shown
improve the electrical conductivity as well as the mechanical to be distributed around ZnO grains, which is further con-
properties. In this study, we report the cold co-sintering of firmed in the images with a higher magnification (Figure 1g,h;
ZnO with Ti3C2Tx in air to form ZnO–Ti3C2Tx nanocomposites, Figure S2, Supporting Information), where several Ti3C2Tx
demonstrating the feasibility of CSP as an effective fabrication nanosheets with thicknesses of a few nanometers can be
method to develop functional ceramic–matrix nanocomposites. found in the grain boundaries. Another proof of the Ti3C2Tx
We believe this is the first report of a 2D material being densi- distribution is shown in the STEM EDS mapping (Figure 1i–l;
fied into a ceramic without altering its structure or chemical Figure S3, Supporting Information), where a homogeneous

Scheme 1.  Schematic illustration showing: a) the grain boundary of (1-y)ZnO–yTi3C2Tx nanocomposites and b) the fabrication process via cold sintering.

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Figure 1.  The density and microstructure of ZnO–Ti3C2Tx nanocomposites cold sintered at 300 °C for 1 h. a) The densities of cold sintered ZnO–Ti3C2Tx
nanocomposites. SEM images of: b) ZnO and c) 99ZnO–1Ti3C2Tx raw powders, and the cross sections of cold sintered: d) ZnO and e) 99ZnO–1Ti3C2Tx
ceramics. f–h) TEM, i) HAADF-STEM images and j–l) energy dispersive spectroscopy (EDS) elemental mapping of cold sintered 99ZnO–1Ti3C2Tx
nanocomposite. The red circles in TEM and HAADF-STEM images show one example of the Ti3C2Tx region. In the HAADF image, the bright areas
belong to ZnO and the dark areas belong to Ti3C2Tx. EDS maps, where elemental Zn is shown in red and Ti is shown in cyan, show the presence of
Ti3C2Tx at the ZnO grain boundaries.

dispersion of Ti3C2Tx is observed in the 99ZnO–1Ti3C2Tx nano- Figure 2a–c plots the temperature-dependent electrical
composites cold sintered at 300 °C. The sintering of pure ZnO conductivities, Seebeck coefficients, and power factors of
leads to formation of micron-size grains even at 300 °C. How- (1-y)ZnO–yTi3C2Tx nanocomposites cold sintered at 300 °C for
ever, in the case of ZnO–Ti3C2Tx composites, the 2D Ti3C2Tx 1 h. ZnO ceramics prepared by conventional thermal sintering
nanosheets located at the grain boundaries of ZnO inhibit in air at 1550 °C for 2 h,[34] 1400 °C for 10 h,[35] and 950 °C[38]
the final grain growth of ZnO, and thus, ZnO–Ti3C2Tx nano­ for 3 h have a conductivity of 0.17 S cm−1 at 250 °C, ≈0.2 S cm−1
composites can be obtained by CSP at 300 °C for 1 h. at ≈120 °C, and 10−3 to 10−2 S cm−1 at room temperature,

Figure 2.  The temperature-dependent: a) electrical conductivities, b) Seebeck coefficients, and c) power factors (PF) of ZnO–Ti3C2Tx nanocomposites
cold sintered at 300 °C for 1 h. 300: Heat treatment in inert atmosphere at 300 °C. 750: Heat treatment in inert atmosphere at 750 °C. All figures share
the same legend.

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Figure 3.  The mechanical properties of ZnO–Ti3C2Tx nanocomposites cold sintered at 300 °C for 1 h: a) hardness; b) elastic modulus.

respectively. When sintered in vacuum at 950 °C under a pres- a metallic conductivity of 312 S cm−1, a Seebeck coefficient
sure of 100 MPa, ZnO shows a conductivity of 4–5 S cm−1 at of −120 µV K−1, and a power-factor of ≈4.5 × 10−4 W mK−2 at
100 °C.[39] In the case of sintering in Ar atmosphere at 900 °C 750 °C, which is promising for the thermoelectric applications,
under a pressure of 75 MPa, the reported conductivity of ZnO outperforming pure ZnO[43] (as seen in Figure S5, Supporting
reached 21.6 S cm−1 at room temperature; this is probably due Information) or MXenes[44] studied to date.
to oxygen vacancies or Zn interstitial.[37] As shown in Figure 2a Figure 3 presents the room temperature mechanical prop-
and Figure S4 (Supporting Information), our cold sintered pure erties of ZnO–Ti3C2Tx nanocomposites cold sintered at
ZnO shows an electrical conductivity of ≈0.08 S cm−1 at 100 °C 300 °C for 1 h. Polycrystalline ZnO ceramic prepared by con-
without further heat treatment and 2–5 S cm−1 with heat treat- ventional thermal sintering at 1300 °C shows a hardness of
ment, which is within the range reported in the literature. The 1.5–1.83 GPa.[45] Microwave sintering and hot pressing of ZnO
increase of electrical conductivity with heat treatment in inert produce hardness values of 0.49–1.72[46] and 2 GPa,[47] respec-
atmosphere may result from the change of the concentration of tively. With hot pressing in vacuum at 1200 °C, ZnO ceramic
dominant native donors in ZnO.[40–42] (7 wt% impurity, ZnAl2O4) has a higher hardness of ≈3.4 GPa.[48]
In the case of ZnO–Ti3C2Tx nanocomposites, most of The hardness of ZnO ceramic fabricated by CSP at 300 °C falls
Ti3C2Tx nanosheets are distributed around the grain bounda- within the range of other ZnO ceramics, but the hardness of
ries of ZnO, providing an efficient pathway for the electron ZnO–Ti3C2Tx nanocomposites increases dramatically as the
transport. Increasing the amount of 2D Ti3C2Tx improved the amount of Ti3C2Tx is increased (Figure 3a). The hardness can
electrical conductivity of the ZnO–Ti3C2Tx nanocomposites by be increased by 40–50% with 0.5 wt% Ti3C2Tx, and more than
1–2 orders of magnitude as plotted in Figure 2a and Figure S4 doubled with 5 wt% of Ti3C2Tx, which results from the micro-
(Supporting Information), confirming that the overall electrical structure of ZnO–Ti3C2Tx nanocomposites and the outstanding
conductivity is improved with the addition of Ti3C2Tx. The mechanical properties of Ti3C2Tx.[49] The elastic modulus of
95ZnO–5Ti3C2Tx nanocomposites cold sintered in air without cold sintered ZnO also falls in the range in the literature[33,50,51]
further heat treatment shows a conductivity of 24 S cm−1 at and was increased with the addition of Ti3C2Tx, as shown in
100 °C (ZnO: 0.08 S cm−1) whereas 99ZnO–1Ti3C2Tx heat- Figure 3b.
treated at 750 °C shows an increased conductivity of 544 S cm−1 In conclusion, this work introduces the CSP to densify
at 100 °C (ZnO: 5 S cm−1). This may result from the interface ZnO nanocomposites with Ti3C2Tx. The 2D Ti3C2Tx was evenly
and interdiffusion changing the defects and band bending with dispersed at the grain boundaries of the ZnO and minimized
heat treatment. the coarsening of ZnO under the CSP conditions. With the
Considering the temperature dependence, ZnO and addition of up to 5 wt% Ti3C2Tx, the electrical conductivity was
99.5ZnO–0.5Ti3C2Tx have a semiconducting behavior while increased by 1–2 orders of magnitude, and the overall power-
the ZnO–Ti3C2Tx nanocomposites with larger amounts of factor improved dramatically. The Seebeck coefficients of all
Ti3C2Tx have a metallic behavior, which results from the the ZnO–Ti3C2Tx nanocomposites were negative, indicating
metallic properties of Ti3C2Tx (Figure 2). The Seebeck coef- n-type charge carrier. The 99ZnO–1Ti3C2Tx nanocomposite
ficients of all the ZnO–Ti3C2Tx nanocomposites are negative, showed a metallic conductivity of 312 S cm−1, a Seebeck coef-
demonstrating that electrons are dominating charge carriers ficient of −120 µV K−1 and a power-factor of ≈4.5 × 10−4 W mK−2
(n-type). It has also been seen that the absolute value of See- at 750 °C. The hardness and elastic modulus of ZnO–Ti3C2Tx
beck coefficient of the ZnO–Ti3C2Tx nanocomposites slightly nanocomposites were enhanced dramatically, increasing by
decreases with increasing the amount of Ti3C2Tx; however, the 40–50% with only 0.5 wt% Ti3C2Tx and more than doubling
overall power-factor is improved dramatically. The 99.5ZnO– with 5 wt% of Ti3C2Tx. This investigation has demonstrated the
0.5Ti3C2Tx nanocomposite without further annealing has con- successful integration of a 2D material into an oxide ceramic,
ductivity, Seebeck coefficient, and power-factor of 16 S cm−1, suggesting that CSP is a promising new processing route
−270 µV K−1, and 1.2 × 10−4 W mK−2 at 300 °C, respectively. for electrically functional nanoceramics utilizing the innate
The 99ZnO−1Ti3C2Tx nanocomposite annealed at 750 °C shows properties of 2D materials.

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Experimental Section Acknowledgements

Powder Preparation: ZnO powder (99.9%, Alfa Aesar) was used as the J. G. and B. L. contributed equally to this work. The work at Penn
oxide matrix. The Ti3AlC2 MAX phase and Ti3C2Tx MXene were synthesized State was supported by the Air Force Research Laboratory (AFRL)
in house in accordance with Alhabeb et al.[52] Ti3C2Tx was produced by under Grant No. FA9550-16-1-0429. Research at Drexel University was
adding Ti3AlC2 powder into a 7.5 M LiF–6.0 M HCl solution maintaining supported by the U.S. National Science Foundation under grant number
the molar ratio of LiF to MAX equal to 7.5:1. After the Ti3AlC2 was slowly DMR-1310245.
added to the acid solution, the temperature was brought to 35 °C for 24 h.
The resulting MXene slurry was repeatedly washed with DI water until a pH
≥6. Vacuum-assisted filtration was used to collect the MXene. It was then
dried in a vacuum desiccator at room temperature for 24 h. Delamination Conflict of Interest
was performed through sonication of the MXene in DI water for 1 h under
The authors declare no conflict of interest.
Argon. The MXene solution was repeatedly centrifuged at 3500 rpm
for 1 h and the colloidal supernatant collected. MXene was verified via
size distribution, SEM, UV–vis, and Raman. MXene distribution was
mixed and sonicated with ZnO for 15 min based on the composition Keywords
(1-y)ZnO–yTi3C2Tx (x  = 0.5, 1, 3, 5 wt%). The mixture would then be
manually agitated, immediately flash frozen and freeze-dried for 72 h. 2D, low temperature sintering, MXene, nanocomposite, thermoelectric,
Cold Sintering of ZnO–MXene composites: The (1-y)ZnO–yTi3C2Tx ZnO
powders were mixed with 17–20 wt% 1.5 M acetic acid using a pipette
in a fume hood. Specifically, 0.2–0.25 g 1.5 M acetic acid was added into Received: March 22, 2018
1 g (1-y)ZnO–yTi3C2Tx powders and homogenized with a pestle and Revised: May 11, 2018
mortar for several minutes. The wetted powders were placed in a steel Published online: June 26, 2018
die with a diameter of 12.7 mm and pressed under a uniaxial pressure
of 250 MPa. Then, the die under the pressure condition was heated
up to 300 °C with a ramp of 5–6 °C min−1, and held at 300 °C for 1 h.
Afterward, the die was cooled down in air and the samples were taken [1] A. Gupta, T. Sakthivel, S. Seal, Prog. Mater. Sci. 2015, 73, 44.
out after the temperature was lower than 80 °C. Prior to the electrical [2] S. Komarneni, J. Mater. Chem. 1992, 2, 1219.
characterization, some of the cold sintered samples were annealed at [3] R. Mas-Balleste, C. Gomez-Navarro, J. Gomez-Herrero, F. Zamora,
300 or 750 °C for 1 h in Ar atmosphere.
Nanoscale 2011, 3, 20.
Characterization: The densities of (1-y)ZnO–yTi3C2Tx nanocomposites
[4] J. N. Coleman, U. Khan, W. J. Blau, Y. K. Gun’ko, Carbon 2006, 44,
cold sintered at 300 °C under a pressure of 250 MPa were determined by
1624.
Archimedes method (ethanol as the medium) and verified by geometry
method. The XRD data were collected using the PANalytical Empyrean [5] Q. Zhang, J. Q. Huang, W. Z. Qian, Y. Y. Zhang, F. Wei, Small 2013,
system. The XRD system was operated at 45 kV and 40 mA using a step 9, 1237.
size of 0.026° with Cu Kα radiation and fixed incident slit of 0.5°. The grain [6] F. A. Khalid, O. Beffort, U. E. Klotz, B. A. Keller, P. Gasser, Diam.
morphology, grain size, and grain boundary were observed with a field Relat. Mater. 2004, 13, 393.
emission scanning electron microscope (FESEM, FEI, NanoSEM 630) [7] B. S. Xu, New Carbon Mater. 2008, 23, 289.
and a high resolution transmission electron microscope (TEM, FEI, [8] D. Mattia, M. P. Rossi, B. M. Kim, G. Korneva, H. H. Bau,
Titan3 @ 200 kV). TEM specimens were polished by a Focused Ion Beam Y. Gogotsi, J. Phys. Chem. B 2006, 110, 9850.
(FIB, FEI, Helios NanoLab 660). Prior to FIB milling, a protective carbon [9] V. N. Mochalin, O. Shenderova, D. Ho, Y. Gogotsi, Nat. Nano-
layer was deposited over the region of interest by electron beam. After technol. 2012, 7, 11.
the specimen became electron transparent, the final cleaning was applied [10] G. N. Yushin, S. Osswald, P. VI, G. P. Bogatyreva, Y. Gogotsi, Diam.
to both sample surfaces by using 1 kV ion beam to remove the damage Relat. Mater. 2005, 14, 1721.
layer during the FIB milling. The energy dispersive spectroscopy (EDS) [11] J. Guo, H. Z. Guo, A. L. Baker, M. T. Lanagan, E. R. Kupp,
mapping was performed by using a SuperX EDS system with four silicon G. L. Messing, C. A. Randall, Angew. Chem., Int. Ed. 2016, 55,
drift detectors surrounding the sample and under scanning transmission 11457.
electron microscopy (STEM) mode using a high angle annular dark field [12] J. Guo, S. S. Berbano, H. Z. Guo, A. L. Baker, M. T. Lanagan,
(HAADF) detector. Before the electrical characterization, the cold sintered C. A. Randall, Adv. Funct. Mater. 2016, 26, 7115.
samples were cut into bars with a dimension of (8–10) × 2 × 1 mm and
[13] H. Z. Guo, A. Baker, J. Guo, C. A. Randall, J. Am. Ceram. Soc. 2016,
polished. The temperature-dependent electrical conductivity and Seebeck
99, 3489.
coefficient were collected using an LSR-3 system (LINSEIS Messgeräte
[14] S. Funahashi, J. Guo, H. Z. Guo, K. Wang, A. L. Baker, K. Shiratsuyu,
GmbH) under He atmosphere and a pressure of 1 bar. The Seebeck
coefficients were calculated using the slope of Seebeck voltage (ΔV) and C. A. Randall, J. Am. Ceram. Soc. 2017, 100, 546.
temperature gradient (ΔT). The thermoelectric power factor (PF) was [15] J. Guo, A. L. Baker, H. Z. Guo, M. Lanagan, C. A. Randall, J. Am.
calculated as follows: PF = S2σ. Before the mechanical characterization, Ceram. Soc. 2017, 100, 669.
the cold sintered samples were polished with sandpaper (600, 800, and [16] M. N. Rahaman, Sintering of Ceramics, CRC Press, Boca Raton, FL,
1200 grit), Al2O3 polishing powder (6, 3, 1, 0.5, and 0.05 µm), and ion- USA 2008.
mill in turn. The indentation load vs. depth curves were obtained with [17] X. Zhao, J. Guo, K. Wang, T. Herisson De Beauvoir, B. Li,
a nanoindenter (Hysitron TI-980 TriboIndenter) using XPM (Accelerated C. A. Randall, Adv. Eng. Mater. 2018, accepted, https://doi.
Property Mapping) and a 10 mN load at room temperature. The hardness org/10.1002/adem.201700902.
and elastic modulus were determined from the load-depth curves and [18] J.-H. Seo, K. Verlinde, J. Guo, D. Sohrabi Baba Heidary, R. Rajagopalan,
the average data were calculated from 20–25 indentations. T. E. Mallouk, C. A. Randall, Scr. Mater. 2018, 146, 267.
[19] B. Anasori, M. R. Lukatskaya, Y. Gogotsi, Nat. Rev. Mater. 2017, 2,
16098.
Supporting Information [20] K. Olszowska, J. B. Pang, P. S. Wrobel, L. Zhao, H. Q. Ta, Z. F. Liu,
Supporting Information is available from the Wiley Online Library or B. Trzebicka, A. Bachmatiuk, M. H. Rummeli, Synthetic Met. 2017,
from the author. 234, 53.

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[21] J. B. Pang, A. Bachmatiuk, Y. Yin, B. Trzebicka, L. Zhao, L. Fu, [36] W. H. Nam, Y. S. Lim, S. M. Choi, W. S. Seo, J. Y. Lee, J. Mater.
R. G. Mendes, T. Gemming, Z. F. Liu, M. H. Rummeli, Adv. Energy. Chem. 2012, 22, 14633.
Mater. 2018, 8, 1702093. [37] D. S. Chen, Y. Zhao, Y. N. Chen, B. A. Wang, H. Y. Chen, J. Zhou,
[22] Q. Hao, J. B. Pang, Y. Zhang, J. W. Wang, L. B. Ma, O. G. Schmidt, Z. Q. Liang, ACS Appl. Mater. Inter. 2015, 7, 3224.
Adv. Opt. Mater. 2018, 6, 1700984. [38] P. Jood, R. J. Mehta, Y. L. Zhang, G. Peleckis, X. L. Wang,
[23] M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. J. Niu, M. Heon, R. W. Siegel, T. Borca-Tasciuc, S. X. Dou, G. Ramanath, Nano Lett.
L. Hultman, Y. Gogotsi, M. W. Barsoum, Adv. Mater. 2011, 23, 4248. 2011, 11, 4337.
[24] A. Lipatov, M. Alhabeb, M. R. Lukatskaya, A. Boson, Y. Gogotsi, [39] K. F. Cai, E. Muller, C. Drasar, A. Mrotzek, Mat. Sci. Eng. B-Solid
A. Sinitskii, Adv. Electron. Mater. 2016, 2, 1600255. 2003, 104, 45.
[25] C. F. Zhang, B. Anasori, A. Seral-Ascaso, S. H. Park, N. McEvoy, [40] D. C. Look, D. C. Reynolds, J. R. Sizelove, R. L. Jones, C. W. Litton,
A. Shmeliov, G. S. Duesberg, J. N. Coleman, Y. Gogotsi, V. Nicolosi, G. Cantwell, W. C. Harsch, Solid State Commun. 1998, 105, 399.
Adv. Mater. 2017, 29, 1702678. [41] D. C. Look, J. W. Hemsky, J. R. Sizelove, Phys. Rev. Lett. 1999, 82,
[26] Z. Ling, C. E. Ren, M. Q. Zhao, J. Yang, J. M. Giammarco, J. S. Qiu, 2552.
M. W. Barsoum, Y. Gogotsi, P. Natl. Acad. Sci. USA 2014, 111, [42] C. G. Van de Walle, Phys. Rev. Lett. 2000, 85, 1012.
16676. [43] B. Zhu, D. Li, T. Zhang, Y. Luo, R. Donelson, T. Zhang, Y. Zheng,
[27] H. Zhang, L. B. Wang, Q. Chen, P. Li, A. G. Zhou, X. X. Cao, C. Du, L. Wei, H. Hng, Ceram. Int. 2018, 44, 6461.
Q. K. Hu, Mater. Design 2016, 92, 682. [44] H. Kim, B. Anasori, Y. Gogotsi, H. N. Alshareef, Chem. Mat. 2017,
[28] F. Shahzad, M. Alhabeb, C. B. Hatter, B. Anasori, S. M. Hong, 29, 6472.
C. M. Koo, Y. Gogotsi, Science 2016, 353, 1137. [45] T. K. Roy, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process.
[29] C. F. J. Zhang, S. Pinilla, N. McEyoy, C. P. Cullen, B. Anasori, 2015, 640, 267.
E. Long, S. H. Park, A. Seral-Ascaso, A. Shmeliov, D. Krishnan, [46] A. K. Mukhopadhyay, M. R. Chaudhuri, A. Seal, S. K. Dalui,
C. Morant, X. H. Liu, G. S. Duesberg, Y. Gogotsi, V. Nicolosi, Chem. M. Banerjee, K. K. Phani, Bull. Mat. Sci. 2001, 24, 125.
Mat. 2017, 29, 4848. [47] D. B. Marshall, T. Noma, A. G. Evans, J. Am. Ceram. Soc. 1982, 65,
[30] Z. Y. Li, L. B. Wang, D. D. Sun, Y. D. Zhang, B. Z. Liu, Q. K. Hu, C175.
A. G. Zhou, Mater. Sci. Eng. B-Adv. 2015, 191, 33. [48] H. Ruf, A. G. Evans, J. Am. Ceram. Soc. 1983, 66, 328.
[31] D. C. Look, Mat. Sci. Eng. B-Solid 2001, 80, 383. [49] V. N. Borysiuk, V. N. Mochalin, Y. Gogotsi, Comp. Mater. Sci. 2018,
[32] L. Vayssieres, Adv. Mater. 2003, 15, 464. 143, 418.
[33] U. Ozgur, Y. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Dogan, [50] S. O. Kucheyev, J. E. Bradby, J. S. Williams, C. Jagadish, M. V. Swain,
V. Avrutin, S. J. Cho, H. Morkoc, J. Appl. Phys. 2005, 98, 041301. Appl. Phys. Lett. 2002, 80, 956.
[34] H. Ohta, W. S. Seo, K. Koumoto, J. Am. Ceram. Soc. 1996, 79, [51] S. Basu, M. W. Barsoum, J. Mater. Res. 2007, 22, 2470.
2193. [52] M. Alhabeb, K. Maleski, B. Anasori, P. Lelyukh, L. Clark, S. Sin,
[35] T. Tsubota, M. Ohtaki, K. Eguchi, H. Arai, J. Mater. Chem. 1997, 7, 85. Y. Gogotsi, Chem. Mat. 2017, 29, 7633.

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