2D Metal Carbides and Nitrides MXenes

Structure Properties and Applications

Babak Anasori
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Babak Anasori
Yury Gogotsi Editors

2D Metal Carbides
and Nitrides (MXenes)
Structure, Properties
and Applications
2D Metal Carbides and Nitrides (MXenes)
Babak Anasori • Yury Gogotsi
Editors

2D Metal Carbides and

Nitrides (MXenes)
Structure, Properties and Applications

123
Editors
Babak Anasori Yury Gogotsi
Department of Mechanical and Energy Department of Materials Science
Engineering and Engineering and A.J. Drexel
Purdue School of Engineering and Nanomaterials Institute
Technology Drexel University,
Indiana University-Purdue University Philadelphia, PA, USA
Indianapolis (IUPUI)
Indianapolis, IN, USA

ISBN 978-3-030-19025-5 ISBN 978-3-030-19026-2 (eBook)

https://doi.org/10.1007/978-3-030-19026-2

© Springer Nature Switzerland AG 2019

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
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Cover illustration: Babak Anasori, Indiana University-Purdue University Indianapolis

This Springer imprint is published by the registered company Springer Nature Switzerland AG.
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Dedicated to our wives, Bita and Larissa, for
their love and support in our scientific
journey
Babak and Yury
Preface

The Beginning of MXenes: The Story of the Discovery as Told

by the Inventors

Over the 8 years that have passed since the discovery of MXenes [1], there have
been more over 1000 papers published by scientists from around the world on the
topic. These papers have been cited more than 25,000 times, with more than 1300
citations of our first paper reporting on the first discovered MXene, Ti3 C2 . The
1st International Conference on MXenes for Energy Applications was held at Jilin
University in China on May 25–26 2018 and the second in Beijing in 2019. With
this continuous explosive growth of interest in MXenes and the fast increase in the
number of research groups working on these fascinating materials, we believe that
it is time to document the story of discovery of MXenes by answering the question
we have been asked frequently in conferences and meetings: “How did it all start?”
And we think that the first book on MXenes is an ideal venue for this story (Fig. 1).
Albert Einstein said: “If we knew what it was we were doing, it would not be
called research, would it?” which is usually very true. The story started at Drexel
University where Professor Michel Barsoum’s group has been studying a unique
family of machinable layered transition metal carbides and nitrides ceramics called
MAX phases for about two decades [2, 3]. The MAX phases are unique in that
they combine some of the best attributes of ceramics and metals. For example, they
are metallically conductive and machinable. Some, e.g., Ti2 AlC, have high elastic
moduli, are relatively light, and are creep, fatigue, and oxidation resistant, like
ceramics. The MAX phases are comprised blocks of transition metal carbide/nitride
“Mn+1 Xn ” octahedra bonded together by an atomically thin “A” metal layer (e.g.,
Al, Si, Sn, In, Ga).
At the same Materials Science and Engineering Department, Professor Yury
Gogotsi’s group has been studying the synthesis of carbon [4] and carbides [5] for
electrochemical energy storage and other applications. Many of these nanomaterials
were produced by selective etching (extraction) of metals from carbides, including

vii
viii Preface

Fig. 1 Photograph of the inventors of MXenes (from left to right: Yury Gogotsi, Michael Naguib,
and Michel W. Barsoum) taken at the 1st International Conference on MXenes for Energy
Applications that was held at Jilin University in China on May 25–26 2018

MAX phases, forming silicon carbide (SiC) nanoplatelets [6], carbide-derived

carbons [7, 8], and graphene and carbon nanotubes [9].
In responding to a call for proposals from the US Department of Energy
searching for alternative Li-ion battery (LIB) anode materials beyond graphite,
particularly Si-based ones, Gogotsi and Barsoum decided to work together on a
proposal to use MAX phases to replace graphite. The rationale behind this idea
was that many A elements present in MAX phases (e.g., Si or Sn) are known
to alloy with Li to yield in high gravimetric capacity anode. The fact that the
MAX phases were layered, were excellent conductors of electricity, and were more
oxidation-resistant than graphite were also important considerations. What limits
the utilization of these metals in LIBs is mainly their significant volume change
during electrochemical cycling, leading to anode pulverization and loss of contact
between the active materials and the current collectors, which usually leads to
rapid electrode degradation. In the MAX phases, which are layered compounds
like graphite, the monoatomic A element layers are sandwiched between stiff and
electrically conductive MX blocks. Thus, they were expected to be more stable
for a larger number of cycles than when pure A elements used. Density functional
theory calculations conducted by one of Gogotsi’s PhD students, Murat Kurtoglu,
suggested that the energy barrier for Li insertion into Ti3 SiC2 was sufficiently low
to make the Li insertion process feasible, and the proposal was funded for 4 years.
At that time, Michael Naguib was a first-year PhD student in Barsoum’s group, and
he was assigned to work on this project under the co-supervision of Barsoum and
Gogotsi.
During the initial screening of a large number of MAX phase powders as battery
anodes, Naguib found that any measured Li-ion capacity could be attributed to the
metallic impurities in the MAX phase samples, which vanish after purification (e.g.,
Preface ix

etching the samples in hydrochloric acid) decreasing the MAX phase capacity to
negligible values. There were a couple of hypotheses for why the MAX phases did
not meet the high expectations as anodes for LIBs. The first hypothesis was the
large particle size with an average in the tens of microns range – very large for Si-
or Sn-based anode materials which are known to show good performance only at
the nanoscale. Thus, the team decided that reducing the particle size of MAX phase
might be necessary to unlock its capability for hosting Li. The second hypothesis
was that the A element occupying the gallery between the MX blocks hinders Li
insertion at the potentials achievable in conventional battery electrolytes. To address
the first hypothesis, high-energy milling was conducted to reduce the particle size
from more than 10 microns to around 1 micron. However, the performance was not
significantly improved at that time. To investigate the second hypothesis, a series of
experiments were conducted to create vacancies in the A layer of MAX phases. The
team brainstormed and tried a variety of chemistries that could be used to selectively
remove Si and other A elements from MAX phases. For example, it was known that
treating MAX phase in molten salts (e.g., cryolite) created vacancies in the A layer
[10], but since the treatment was carried out at higher temperatures, the removal of
the A atoms was accompanied by reorganization of the carbide layers to form rock
salt structure [11], which didn’t show any measurable electrochemical activity for
Li.
One of the techniques used for synthesis of fully dense MAX phase is hot
isostatic pressing, and the product of this synthesis is encapsulated in glass. A
hydrofluoric acid (HF) solution was typically used to dissolve this glassy phase.
As part of the inherited knowhow within Barsoum’s group, students were warned
from soaking the pressed parts longer than what was needed to dissolve the glass,
because sometimes the dense parts could disintegrate into powder. In an attempt to
achieve both, size reduction of the MAX phase particles down to single grains and
partial/full etching of the A layers, Naguib suggested and used HF. The rationale
behind the HF selection was that it could etch the grain boundaries of the MAX
phases and disintegrate the large multi-grain particles into smaller grains. Also, HF
is one of few etchants that can etch titanium oxide, which is usually present as a thin
protective layer on the surface of Ti-containing MAX phases. Etching or breaking
through that oxide layer is necessary to react the A layers in the MAX phases.
Since initial attempts to etch Ti3 SiC2 in various etchants were unsuccessful, the
second MAX phase powder immersed in HF was Ti2 SnC. During the reaction of this
powder (−400 mesh) with 50% HF at room temperature for ≈ 12 h, a strange sound
was heard emanating from the reaction vessel. Upon closer inspection, the noise was
traced to the sound of metal beads hitting each other, a sound not unlike the cabasa
instrument. After 24 h, the reaction was stopped, and the products were washed.
Large metallic beads (~1–3 mm), in addition to a small amount of powder, were
observed. As shown in Fig. 2a, X-ray diffraction (XRD) analysis of this mixture
showed the presence of metallic tin, in addition to unreacted Ti2 SnC. The weight
loss after the reaction was ~ 40%. Considering that the Sn content in Ti2 SnC is
∼52 wt.%, it was reasonable to conclude that both Ti and C dissolved in the acid,
and the free Sn agglomerated forming metal beads.
x Preface

Fig. 2 XRD patterns of (a) Ti2 SnC before and after treatment with 50% HF at room temperature
for 24 h. (b) Ti2 AlC before and after treatments with 50% HF at RT for 5 min, the top XRD patterns
is for cold-pressed (CP) sample after HF treatment. The black squares represent the peak position
of Si that was used as an internal reference; the red circles in a represent the peak position for Sn
[PDF# 04-0673]

Immersion of commercial Ti2 AlC powder from Kanthal, Sweden, which had
licensed the MAX technology from Drexel University, in 50% HF at room
temperature, resulted in an exothermic reaction accompanied with large amounts
of gas evolved. When the reaction was stopped after 5 minutes by adding 300 mL of
DI water to the reaction vessel, the color of the resulting powder after washing and
drying turned much darker (the color turned from dark gray to black). The weight
loss reached ~ 90%. Energy-dispersive X-ray spectroscopy (EDS) analysis of the
powder after the reaction showed significantly less Al than in the stoichiometric
Ti2 AlC. In addition to Ti, Al, and C, O and F were detected with the following the
atomic ratios: Ti:Al:C:O: F were ~ 1.0:0.06:0.6:0.6:1.2, respectively. Also, the C to
Ti ratio was higher than in the stoichiometric Ti2 AlC. However, quantitative EDS
analysis of carbon is tricky, because C may come from sources other than the sample
itself. The first TEM images of this powders were taken by Gogotsi’s postdoctoral
researcher, Dr. Junjie Niu, who used to study graphene, and his first reaction was
“this is graphene, not a MAX phase” as the powder exhibited a graphene-like 2D
morphology, while EDS analysis confirmed that the 2D sheets consisted of Ti, C, O,
and F.
Figure 2b shows that all the XRD peaks related to Ti2 AlC vanished after the
HF treatment. Only peaks of TiC, present as an impurity in the as-received MAX
phases, were identified at 2θ = 35.98◦ , 41.8◦ , and 60.6◦ . Those low-intensity
peaks can be observed in the XRD pattern of the as-received powder (bottom
pattern in Fig. 2b). The post-etching weak TiC peaks seen in XRD diffraction
patterns belonged to the TiC present in the starting material. It was only after
cold pressing of the etched powder at 1 GPa, that new, broad XRD peaks at
2θ ~ 8.49◦ , 17.96◦ , 27.56◦ , and 36.43◦ appeared (top pattern in Fig. 2b). Since
Preface xi

those peaks appeared only after pressing, it was reasonable to conclude that this
phase had a certain preferred orientation. Assuming a hexagonal structure (the
same as the MAX phase), the preferred orientation would be along the {000l}
plane, which implied those peaks would correspond to (0002), (0004), (0006), and
(0008) reflections. The calculated average c-lattice parameter, c-LP, based on this
assumption is 19.92 Å. This c-LP value is closer to the c-LPs of the Ti3 AlC2
(18.487 Å) [12] rather than Ti2 AlC (13.364 Å) [13]. This observation, together
with the fact that only 10 wt.% of the material remained after the reaction, which
is close to the amount of Ti3 AlC2 that existed as a secondary impurity phase in
the as-received Ti2 AlC powder, directed Naguib’s attention toward the former. In
other words, it was assumed that under those conditions, all the Ti2 AlC dissolved
and the leftover was the product of reacting Ti3 AlC2 with HF. To prove this
conjecture, we decided to start with Ti3 AlC2 instead of Ti2 AlC. When −400 mesh
Ti3 AlC2 powder was immersed in 50% HF, the reaction was less exothermic than
in the case of Ti2 AlC. Bubbles, presumed to be H2 , were observed during the
etching, suggesting a chemical reaction. After 2 h, the reaction was stopped, and the
powder was washed using DI water. The weight loss was negligible. EDS analysis
of the resulting powders showed a significant reduction in the Al content and a
concomitant increase in the O and F concentrations. The Ti:Al:C:O:F atomic ratio
was ~ 3.0:0.1:1.4:1.7:1.9. This implies that the Al was selectively etched; the Ti3 C2
layers were released and terminated by oxygen (i.e., O and OH) and/or fluorine,
F, as confirmed by X-ray photoelectron spectroscopy by Gogotsi’s student, Min
Heon. Raman analysis conducted by Dr. Volker Presser, Gogotsi’s postdoc, and
high-resolution transmission electron microscopy performed by Swedish colleagues
of Barsoum, Dr. Jun Lu and Prof. Lars Hultman, completed the characterization of
this 2D material, and the first paper announcing the discovery was written [1].
When it was discovered that the A element from MAX phase was removed, it
was suggested to label the produced material as MXene to emphasize the loss of
the A element from the MAX phase and its 2D morphology, similar to graphene.
This moniker has since been universally accepted, and MXenes are now full-fledged
members of the 2D material world. Soon thereafter, we showed that by tuning the
etching conditions, other MXenes (viz., Ti2 C, Ta4 C3 , TiNbC, V1.5 Cr1.5 C2 , Ti3 CN)
could be produced. In other words, we showed that MXenes are actually a large –
and growing – family of 2D materials [14–16]. The current number is more than 30.
After etching the Al layers to form MXenes, electrodes made with the etched
material showed promise as anodes for LIBs especially at high cycling rates. Finally,
we would like to express our gratitude to the US DOE BATT program that supported
the first few years of MXene research. This project resulted in an entire family of
2D materials which, as this book shows, exhibit unique properties and promising
performances in numerous applications.

Drexel University, Philadelphia, PA, USA Michel W. Barsoum

Drexel University, Philadelphia, PA, USA Yury Gogotsi
Tulane University, New Orleans, LA, USA Michael Naguib
xii Preface

References

1. Naguib, M., Kurtoglu, M., Presser, V., Lu, J., Niu, J., Heon, M., Hultman,
L., Gogotsi, Y., & Barsoum, M. W. (2011). Two-dimensional nanocrystals
produced by exfoliation of Ti3 AlC2 . Advanced Materials, 23(37), 4248–4253.
2. Barsoum, M. W. (2000). The MN+1 AXN phases: A new class of solids:
Thermodynamically stable nanolaminates. Progress in Solid State Chemistry,
28(1–4), 201–281.
3. Barsoum, M. W. (2013). MAX phases: properties of machinable ternary
carbides and nitrides. Hoboken: Wiley.
4. Gogotsi, Y. (2006). Carbon nanomaterials. Weinheim: CRC Press.
5. Gogotsi, Y., & Andrievski, R. A. (1999). Materials science of carbides, nitrides
and borides (Vol. 68). Springer Science & Business Media.
6. Cambaz, G. Z., Yushin, G. N., Gogotsi, Y., & Lutsenko, V. G. (2006).
Anisotropic etching of SiC whiskers. Nano Letters, 6(3), 548–551.
7. Gogotsi, Y., Nikitin, A., Ye, H., Zhou, W., Fischer, J. E., Yi, B., Foley, H. C., &
Barsoum, M. W. (2003). Nanoporous carbide-derived carbon with tunable pore
size. Nature Materials, 2, 591.
8. Presser, V., Heon, M., & Gogotsi, Y. (2011). Carbide-derived carbons – From
porous networks to nanotubes and graphene. Advanced Functional Materials,
21(5), 810–833.
9. Cambaz, Z. G., Yushin, G., Osswald, S., Mochalin, V., & Gogotsi, Y. (2008).
Noncatalytic synthesis of carbon nanotubes, graphene and graphite on SiC.
Carbon, 46(6), 841–849.
10. Barsoum, M. W., El-Raghy, T., Farber, L., Amer, M., Christini, R., & Adams,
A. (1999). The topotaxial transformation of Ti3 SiC2 to form a partially ordered
cubic TiC0.67 phase by the diffusion of Si into molten cryolite. Journal of the
Electrochemical Society, 146(10), 3919–3923.
11. Naguib, M., Presser, V., Tallman, D., Lu, J., Hultman, L., Gogotsi, Y., &
Barsoum, M. W. (2011). On topotactic transformation of Ti2 AlC into a Ti-C-
O-F cubic phase by heating in molten lithium fluoride in air. Journal of the
American Ceramic Society, 94(12), 4556–4561.
12. Tzenov, N. V., & Barsoum, M. W. (2008). Synthesis and characterization of
Ti3 AlC2 . Journal of the American Ceramic Society, 83(4), 825–832.
13. Schuster, J. C., Nowotny, H., & Vaccaro, C. (1980). The ternary systems:
CrAlC, VAlC, and TiAlC and the behavior of H-phases (M2 AlC). Journal of
Solid State Chemistry, 32(2), 213–219.
14. Naguib, M., Mashtalir, O., Carle, J., Presser, V., Lu, J., Hultman, L., Gogotsi,
Y., & Barsoum, M. W. (2012). Two-dimensional transition metal carbides. ACS
Nano, 6(2), 1322–1331.
15. Abdelmalak, M. N. (2014). MXenes: A new family of two-dimensional mate-
rials and its application as electrodes for Li-ion batteries. PhD thesis, Drexel
University, Philadelphia, PA, USA.
16. Barsoum, M. W., Gogotsi, Y., Abdelmalak, M. N., & Mashtalair, O. Com-
positions comprising free standing two dimensional nanocrystals. US Patent
9,193,595 issued 24 Nov 2015.
Acknowledgements

We would like to acknowledge many colleagues, collaborators, and students who

contributed excellent chapters, which provide a comprehensive overview of their
research on MXenes. We are also thankful to many students, post-docs, collab-
orators, and researchers ranging from undergraduate students to senior scientists
and professors at Drexel University and in many countries of the world who
worked with us exploring MXenes. Y.G. would like to thank the U.S. Department
of Energy for continuous funding of his research on MXenes from the initial
discovery (Assistant Secretary for Energy Efficiency and Renewable Energy, Office
of Vehicle Technologies under Contract No. DE-AC02-05CH11231, subcontract
6951370 under the Batteries for Advanced Transportation Technologies (BATT)
Program) to the exploration of energy-related applications via the Fluid Interface
Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research
Center funded by the Office of Science, Office of Basic Energy Sciences. Research
of Y.G. and B.A. on fundamental properties of MXenes is currently supported by
the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences,
under Grant No. DESC0018618. Support from many other US and international
funding sources is also greatly appreciated.

xiii
Contents

Part I Introduction
1 Introduction to 2D Transition Metal Carbides and Nitrides
(MXenes) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Babak Anasori and Yury Gogotsi

Part II Synthesis, Compositions and Structure

2 The Mn+1 AXn Phases: The Precursors for MXenes . . . . . . . . . . . . . . . . . . . . 15
Michel W. Barsoum and Per Eklund
3 In- and Out-of-Plane Ordered MAX Phases and Their MXene
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Johanna Rosen, Martin Dahlqvist, Quanzheng Tao, and Lars Hultman
4 Non-MAX Phase Precursors for MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Xian-Hu Zha, Jie Zhou, Per Eklund, Xiaojing Bai, Shiyu Du,
and Qing Huang
5 Top-Down MXene Synthesis (Selective Etching) . . . . . . . . . . . . . . . . . . . . . . . . 69
Kathleen Maleski and Mohamed Alhabeb
6 Bottom-Up Synthesis of 2D Transition Metal Carbides
and Nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Chuan Xu, Long Chen, Zhibo Liu, Hui-Ming Cheng, and Wencai Ren
7 Effect of Synthesis Methods on the Structure and Defects
of Two-Dimensional MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Xiahan Sang, Michael Naguib, Mohamed Alhabeb,
and Raymond R. Unocic
8 MXene Surface Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Per O. Å. Persson

xv
xvi Contents

9 Molecular Dynamics Simulations of MXenes: Ab Initio,

Reactive, and Non-reactive Empirical Force Fields. . . . . . . . . . . . . . . . . . . . . 137
Roghayyeh Lotfi, Dundar E. Yilmaz, Lukas Vlcek, and Adri van Duin

Part III Processing

10 Chemical and Electrochemical Intercalation of Ions
and Molecules into MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Michael Ghidiu, Michael Naguib, and Michel W. Barsoum
11 Techniques for MXene Delamination into Single-Layer Flakes . . . . . . . 177
Armin VahidMohammadi, Emre Kayali, Jafar Orangi,
and Majid Beidaghi
12 MXene Films, Coatings, and Bulk Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Guo-Ming Weng, Marina Mariano, Jason Lipton, and André D. Taylor
13 MXene–Organic Hybrid Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Muhammad Boota

Part IV Properties
14 Electronic Properties and Applications of MXenes from Ab
Initio Calculations Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
Mohammad Khazaei, Ahmad Ranjbar, Yunye Liang, and Seiji Yunoki
15 Predicted Magnetic Properties of MXenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Nathan C. Frey, Christopher C. Price, Arkamita Bandyopadhyay,
Hemant Kumar, and Vivek B. Shenoy
16 Electronic and Mechanical Properties of MXenes Derived
from Single-Flake Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Alexey Lipatov and Alexander Sinitskii
17 Optical Properties of MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Krishnakali Chaudhuri, Zhuoxian Wang, Mohamed Alhabeb,
Kathleen Maleski, Yury Gogotsi, Vladimir Shalaev,
and Alexandra Boltasseva

Part V Applications
18 MXenes for Supercapacitor Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Zifeng Lin and Patrice Simon
19 MXenes for Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
Masashi Okubo and Atsuo Yamada
20 MXene Materials as Electrodes for Lithium-Sulfur Batteries . . . . . . . . . 381
Xiao Liang and Linda F. Nazar
Contents xvii

21 Electromagnetic Interference Shielding Using MXenes

and Their Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Chong Min Koo, Faisal Shahzad, Aamir Iqbal, and Hyerim Kim
22 MXenes for Environmental and Water Treatment Applications . . . . . . 417
Kashif Rasool, Ravi P. Pandey, P. Abdul Rasheed,
Golibjon R. Berdiyorov, and Khaled A. Mahmoud
23 Chemistry and Catalysis of MXenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Luke R. Johnson and Aleksandra Vojvodic
24 MXenes for Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
Seon Joon Kim and Hee-Tae Jung
25 MXenes for Transparent Conductive Electrodes
and Transparent Energy Storage Devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Chuanfang (John) Zhang and Valeria Nicolosi
26 Biomedical Applications of MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Flavia Vitale, Nicolette Driscoll, and Brendan Murphy

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
 Part I
Introduction
Chapter 1
Introduction to 2D Transition Metal
Carbides and Nitrides (MXenes)

Babak Anasori and Yury Gogotsi

Group 4–6 transition metal carbides and nitrides were explored in the twentieth
century as high-temperature, hard, chemically stable, and wear-resistant materials
[1]. Exploration of their energy storage applications started with the discovery
of their catalytic behavior in the 1970s [2], and since then several nanostructure
designs have been proposed, taking small steps to enhance the surface area and
performance of transition metal carbides and nitrides [3, 4]. The breakthrough in the
field happened in 2011 by the discovery of the first two-dimensional (2D) titanium
carbide (Ti3 C2 Tx ) that led to a family of 2D transition metal carbides and nitrides,
named MXenes (pronounced “maxines”) [5, 6]. Since then, MXenes have become
a large and quickly growing family of 2D materials.
MXene materials have a formula of Mn+1 Xn Tx , where M is an early transition
metal (Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W), X is carbon or nitrogen, and
n = 1–3 [7, 8]. The transition metals are marked in blue in Fig. 1.1 (periodic table).
T represents the surface termination groups that are mostly = O, −F, and −OH, and
x in Tx represents the number of surface functionalities. There are also few reports
on Ti3 C2 Tx MXene with surface termination of −Cl [9, 10]. The experimentally
reported surface terminations are marked in yellow in Fig. 1.1. The 2D sheets have
a thickness in the range of 1 nm, which can be controlled by changing the n in
MXenes from M2 XTx , to M3 X2 Tx , and M4 X3 Tx .
To date, most MXenes (25 out of 29 of the published ones) have been made by
selective etching of the Al layers from MAX phases (Fig. 1.2). MAX phases are

B. Anasori ()
Department of Mechanical and Energy Engineering, Purdue School of Engineering and
Technology, Indiana University-Purdue University Indianapolis (IUPUI), Indianapolis, IN, USA
e-mail: banasori@iupui.edu
Y. Gogotsi ()
Department of Materials Science and Engineering and A.J. Drexel Nanomaterials Institute,
Drexel University, Philadelphia, PA, USA
e-mail: gogotsi@drexel.edu

© Springer Nature Switzerland AG 2019 3

B. Anasori, Y. Gogotsi (eds.), 2D Metal Carbides and Nitrides (MXenes),
https://doi.org/10.1007/978-3-030-19026-2_1
4 B. Anasori and Y. Gogotsi

Fig. 1.1 Periodic table showing the elements in MAX phases and MXenes, surface terminations,
and intercalant cations, based on experimental studies. Transition metals (TMs) reported for MAX
and MXenes are marked in solid blue, and TMs that are only reported in MAX phases are marked
in blue with horizontal stripes (Sc, Lu, and Mn). MXenes’ surface terminations are marked in
yellow, and MAX phases’ A elements are marked in red. The green background shows the cations
that have been intercalated into MXenes to date. 1M and 1A indicate the possibility of a single
(pure) TM and A-element MAX phase (and MXene) formation for those specific elements. SS
indicates the existence of solid solutions in TM atomic planes (blue) or A-element planes (red).
2M shows the formation possibility of an ordered double TM MAX phase (either in-plane or out-
of-plane). This periodic table does not include elements that have only been explored via first
principle calculations

layered ternary carbides and nitrides in which Mn+1 Xn layers are bonded together
with layers of an A element [11]. The A elements are groups 13–16 of the periodic
table. Recent studies have shown transition metals of groups 8–12 of the periodic
table (Fe, Cu, Zn, Cd, Ir, and Au) can also become the A layer of MAX phases, either
in the form of solid solutions (marked with a red “SS” box) or as pure A elements
(marked with a red “1A” box). All experimentally explored A elements in MAX
phases are marked in red in Fig. 1.1. In MAX phases, which were first reported in
the 1930s to the 1960s and then were rediscovered in the late 1990s and labeled
as MAX phases [11], metallic bonding between the M-A layers keeps the Mn+1 Xn
layers together and is usually weaker than the M-X bonds, which makes the selective
etching of the A layers possible (read Chap. 2). Figure 1.1 shows the M, X, A, and T
elements reported to date for the MAX phases and MXenes. Mn-containing MAX
phases have been reported [12, 13]; however, MXene with pure Mn as the M has
not been synthesized from a MAX phase yet. A lutetium-containing MAX phase
(Lu2 SnC) has been synthesized adding the possibility of lanthanides as MAX phase
components [14].
The rapid development of MXene chemistry and interest in synthesizing new
MXenes has excited the MAX community and led to the discovery of the new
subfamilies of MAX phases, namely, in-plane and out-of-plane ordered double
transition metal carbides, which will be discussed in Chap. 3. When two transition
metals combined (mostly a heavy transition metal with a light one), ordered
structures of MAX phases form instead of solid solutions. In the out-of-plane
1 Introduction to 2D Transition Metal Carbides and Nitrides (MXenes) 5

Fig. 1.2 Top-down synthesis of MXenes from its MAX and non-MAX precursors by selective
etching. Three types of M2 XTx , M3 X2 Tx , and M4 X3 Tx can be synthesized in the forms of 2D
multilayer powders (labeled as multilayer 2Ds) and 2D sheets. 2D multilayer powders have surface
terminations similar to 2D sheets. However, surface terminations are not shown for multilayer 2D
powders for simplicity

ordered structure, two layers of a transition metal are sandwiching one or two layers
of another M in the carbide structure, for example, Mo2 TiAlC2 and Mo2 Ti2 AlC3 .
By selective etching the Al atomic layers, ordered double transition metal MXenes
have been made (marked in red in Fig. 1.3). In the M2 AC structure, where only
two layers of M are available, in-plane ordering has been reported, in which the
basal planes consist of separate rows of two types of M elements, for example,
(Mo2/3 Sc1/3 )2 AlC, (Mo2/3 Y1/3 )2 AlC, and (W2/3 Y1/3 )2 AlC (read Chap. 3). The in-
plane MAX phases can be selectively etched to become two different types of
MXenes: by selective etching of the Al layers, in-plane ordered double transition
metal MXenes can form, such as (Mo2/3 Y1/3 )2 CTx (marked in red in Fig. 1.3); or by
selective etching of the lighter transition metal (e.g., Sc or Y) with Al layers, ordered
divacancy MXenes can be synthesized, such as Mo1.33 CTx and W1.33 CTx (marked
in pink in Fig. 1.3). The latter MXene phases do not follow the general formula of
Mn+1 Xn Tx since they contain about 33% atomic vacancies in the transition metal
layers and have a M1.33 XTx formula. These phases and their resulting MXenes
will be discussed in Chap. 3. Beyond MAX phases, other layered ternary carbides
have been also selectively etched to make MXenes. In such carbides, either two
layers of an A element (Mo2 Ga2 C) or layers of A-element carbides (e.g., Al3 C3 in
Zr3 Al3 C5 and (Al,Si)4 C4 in Hf3 (Al,Si)4 C6 ) separate the Mn+1 Xn layers. The latter
carbides are members of a large family of (MC)n [Al(A)]m Cm−1 with more than 30
6 B. Anasori and Y. Gogotsi

Fig. 1.3 MXene compositions reported to date. The top row of the structures shows mono-M
MXenes (marked as 1M in Fig. 1.1); the second row shows double-M solid solutions (SS). The
double-M SS compositions are marked in green. The third row shows ordered double-M MXenes,
and their compositions are marked in red. The fourth row shows ordered divacancy MXenes which
is only reported for the M2 C MXenes, making a M1.33 C composition due to ~ 33 at.% vacancy in
the M layers, and their compositions are marked in pink. This table includes both experimentally
(marked in blue) and theoretically (marked in gray) explored compositions of MXenes. Surface
terminations are not shown. (Anasori et al. [8])

compounds. Mo2 CTx , Zr3 C2 Tx , and Hf3 C2 Tx MXenes have been made from these
non-MAX precursors as discussed in Chap. 4.
Unlike most of the 2D materials precursors, in which van der Waals bonding
holds the 2D sheets together, the 3D layered MXene precursors of ternary carbides
and nitrides, including MAX phases, have primary bonding between the layers
either by the A-element or Am Cm−1 layers. Consequently, only chemical exfoliation
methods have been used to make MXenes. Figure 1.2 shows a schematic of MXene
precursors and the top-down selective etching to synthesize M2 XTx , M3 X2 Tx ,
and M4 X3 Tx MXenes. To date, primarily fluoride-containing acidic solutions have
been used for MXene synthesis, such as hydrofluoric acid (HF) or a mix of
lithium fluoride and hydrochloric acid (HCl). Fluoride-free etching routes are also
possible via electrochemical selective etching, for example, etching Ti2 AlC in
chloride-containing solutions [9, 10]. A computational analysis of the possibility of
exfoliation of different MXenes is presented in Chap. 14. The selective chemical
1 Introduction to 2D Transition Metal Carbides and Nitrides (MXenes) 7

etching makes the large-scale production of MXenes easily feasible, which is

a significant advantage over several other 2D materials. All top-down selective
etching methods and etchants, as well as large-scale production of MXenes, are
discussed in Chap. 5. To date, 28 out of 29 MXenes (except for Mo2 N) have been
synthesized via the top-down method as shown in Fig. 1.2. There are more than
60 possible stoichiometric MXene compositions (Fig. 1.3), as well as an infinite
number of solid solutions. Their stability and properties have been explored via
computational studies as discussed in Chap. 14.
Bottom-up methods are also available to make surface-termination-free 2D
transition metal carbides and nitrides, and these methods have been the least
explored for MXenes. The main issue is the formation of bulk and non-2D carbides.
Very thin (down to 2–3-nm-thick) Mo2 C and W2 C have been deposited via chemical
vapor deposition, as well as pulsed laser deposition. The salt-templating method that
is used to form transition metal oxides and transform them to nitrides and carbides
is another bottom-up route as discussed in Chap. 6.
Because the top-down selective chemical etching is the main method of MXene
synthesis [8, 15], MXene properties are significantly synthesis- and processing-
dependent. In Ti3 C2 Tx , the most studied MXene, surface termination (Tx ) consists
of OH, O, and F in different ratios, depending on the etching processing (e.g.,
etchant composition and temperature) as well as processing conditions such as
washing steps and delamination, and even post-synthesis steps and storage con-
ditions (temperature and environment), as discussed in Chaps. 7, 8, and 11. In
general, an etchant with a higher concentration of HF leads to a higher fluorine
content on MXene surfaces. Additionally, a more aggressive etchant increases the
number of defects in MXene flakes. Etching conditions even change the morphology
of the etched multilayered powder. For example, concentrated HF usually leads
to accordion-like shape of particles, which is not observed under milder etching
conditions. The surface terminations also depend on the M (transition metal). For
example, Mo2 CTx has minimal fluorine terminations compared to Ti3 C2 Tx , despite
the fact that a higher concentration of HF is needed to produce Mo2 CTx [16].
After selective etching of the A-group element layers (Al, Si) or Al/Si carbide
layers from the precursor (Fig. 1.2), MXene multilayered powder is made. While the
multilayered powder particles have been used for applications in adsorption and Li-
ion batteries (Chaps. 19, 20 and 22), to fully benefit from the 2D nature of MXenes,
delamination to single-layered flakes is a required step. Intercalation is needed
to separate and delaminate MXene sheets. Different metal cations and organic
molecules have been used as intercalants either via chemical or electrochemical
reactions. The reported intercalated metal cations, such as Li+ , Na+ , Ca2+ , and
Al3+ , are marked in green in the periodic table in Fig. 1.1. MXenes have been
also used to adsorb heavy metal ions, such as Pb and Pd, as these ions can
intercalate MXenes. Many other metal cations can be intercalated into MXenes.
Because the M-X bonds are strong and short, ions can only penetrate between
the MXene sheets and not in MXene flakes. The interlayer spacing of MXenes
and their properties, including electrical, electrochemical, and mechanical, can be
controlled by the intercalated cation sizes and charges, as discussed in Chaps. 9 and
10. MXene delamination can be done in different solutions using various cation
8 B. Anasori and Y. Gogotsi

intercalants. For example, by the use of a mixture of HCl with lithium fluoride
(LiF), it is possible to etch the precursor and delaminate MXene by raising the
pH during the washing steps. In other words, no additional intercalant is needed
for delamination. When pure HF is used, however, organic molecules such as
tertiary amines (tetrabutyl- and tetramethyl-amonium hydroxides) are mixed with
multilayer MXene for intercalation and delamination. Recently, mixed acids such
as HF-HCl have been used for etching, followed by addition of salts such as lithium
chloride (LiCl) for easier intercalation and delamination [20]. A full description of
MXenes delamination process is available in Chap. 11.
MXenes have a unique combination of properties that make them promising
materials for a variety of applications as shown in Fig. 1.4. The as-synthesized
MXenes are hydrophilic and can be dispersed in water and a variety of organic
solvents such as ethanol, dimethyl sulfoxide, N,N-dimethylformamide, and propy-
lene carbonate [17]. MXene zeta potentials are negative in the range of −30 to
−80 mV, which is a function of solution pH and MXene compositions as discussed
in Chap. 10. The high negative zeta potential makes MXene colloidal solutions
stable and gives the opportunity to fabricate MXene films and patterns using almost
any method applicable to inks. MXene films have been made via filtration, spray
coating, spin coating, dip coating, and printing. Additionally, MXene colloids can
be mixed with different nanomaterials and polymer solutions to fabricate hybrid
and composite structures. Ti3 C2 Tx can be mixed with functionalized positively
charged carbon nanotubes or graphene to fabricate self-assembled hybrid films.
These structures, their fabrication methods, and properties are discussed in Chap.
12. There are a few studies that showed MXene can initiate polymerization when
in contact with certain monomers, such as pyrrole and 3,4-ethylenedioxythiophene
(EDOT). The organic-MXene interactions and hybrid structures are discussed in
more details in Chap. 13.
The oxidation stability of MXenes depends on their composition, structure (flake
size and concentration of defects), morphology (e.g., single- or multilayered flakes,
powder, or films), and storage conditions (e.g., colloidal solution, dried films, in
vacuum or air). Since MXenes are made via solution processing, it is common
to store the 2D flakes in water or organic solvents as colloidal solution (ink)
[17]. When stored as solutions, MXene flake size as well as liquid medium type,
dissolved oxygen, and temperature has large impacts on the oxidation rate [18].
It has been shown recently that water and MXene hydrolysis play a major role in
MXene degradation. For example, when Ti3 C2 Tx is stored in anhydrous isopropanol
in ambient conditions (with dissolved oxygen), it shows almost no degradation
up to 30 days [19]. However, if Ti3 C2 Tx is stored in aqueous solution, dissolved
oxygen leads to its oxidation in a few days. In the case of aqueous solution storage,
MXene degradation can be delayed by storing under argon with minimum dissolved
oxygen in the water and lower temperatures as discussed in Chap. 16. Removal
of MXene from water by deposition methods, such as spray or spin coating or
filtration, significantly improves its stability in air for up to months. For example,
a 5-μm-thick filtered film of Ti3 C2 Tx was stable up to 30 days of storage at room
temperature in air [18].
1 Introduction to 2D Transition Metal Carbides and Nitrides (MXenes) 9

MXenes have a unique combination of properties, and although over the past
8 years we have learned a lot about them, there is still a significant amount of
work needed to fully understand MXene properties. All bare MXenes are metallic
similar to their MAX precursors. However, upon surface terminations, MXenes have
been predicted to be either metals or semiconductors. So far, all the experimental
measurements suggested metallic behavior. Some MXenes have been predicted
to be topological insulators. In general, MXene chemistry (M, X, and T), their
structure (M2 XTx , M3 X2 Tx , M4 X3 Tx ), and the position of the surface termination
can affect the electronic properties, which are explored in detail in Chaps. 14 and
16. At ~ 10,000 S/cm, the electrical conductivity of Ti3 C2 Tx film is one of the
highest among the solution-processed nanomaterials, making it the best material
for electromagnetic interference shielding (Chap. 21) and antenna applications
[20]. Experimental electrical conductivity values of different MXenes are presented
in Chap. 16. Additionally, there are several predictions about room temperature
magnetic MXenes, such as Cr2 COx F2−x and Ti2 MnC2 Tx , as discussed in Chap.
15.
Mechanical properties of MXenes are outstanding but have not been explored
enough. The measured 2D elastic modulus of single-layer Ti3 C2 Tx measured via
atomic force microscopy indentation is 326 ± 29 N/m, which corresponds to a
Young’s modulus of 330 ± 30 GPa and makes Ti3 C2 Tx MXene the third strongest
2D sheet characterized to date, after perfect graphene and hexagonal boron nitride
[21]. Additionally, Ti3 C2 Tx Young’s modulus is the highest among the solution-
processed 2D materials, exceeding those of transition metal dichalcogenides and
graphene oxide as discussed in Chap. 16. The measured values are from etched
and delaminated MXene, which contains defects (such as titanium vacancies) in the
individual MXene sheets. Density functional theory and molecular dynamic (MD)
studies have suggested that the elastic properties in MXene basal planes should be
quite high (c11 in the range of 500–800 GPa). Recent MD simulation has shown
that changing the number of M layers (e.g., M2 C to M4 C3 ) significantly changes
the bending rigidity of the 2D flakes [22]. These values suggest a great potential of
2D MXenes for fabrication of multifunctional nacre-like composites for a variety of
applications including structural composites, coatings, and wearables.
Optical properties of MXene flakes have been explored since 2016, and several
applications, such as mode-locked lasers, surface-enhanced Raman spectroscopy,
and photothermal therapy, have emerged. A ~ 1-nm-thick Ti3 C2 Tx MXene absorbs
about 3% of visible light (at 550 nm wavelength). There is a significant optical
tunability of MXenes by changing their chemistry (e.g., from Ti2 CTx to V2 CTx )
that changes the absorption spectra as discussed in Chap. 17.
Electrochemical properties of MXenes have been extensively studied. Almost
50% of MXene publications to date are on energy-related topics (Fig. 1.4) as
discussed in Chaps. 18, 19, 20, 23 and 25. MXenes have a unique combination
of properties that make them desirable for energy storage applications:
(i) The surface terminations, more specifically −O, create transition metal oxide-
like surfaces, which are redox active.
10 B. Anasori and Y. Gogotsi

Fig. 1.4 Explored applications and properties of MXenes to date. The center pie chart shows the
ratio of publications in each explored applications/properties of MXenes with respect to the total
number of publications on the “MXene” topic from 2011 to August 2019 on Web of Science. The
middle pie chart ring, with similar color to the center one, shows the starting year for exploration
of each application/property of MXenes. There might be one or two papers published before some
of the mentioned years; we considered a year with a few important publications as the starting year
for each slice. The outer ring shows the ratio of publications only on Ti3 C2 Tx MXene versus the
publications on all MXene compositions (M2 XTx , M3 X2 Tx , M4 X3 Tx )

(ii) MXenes possess high electrical conductivity. This conductivity provides fast
transport of electrons to the electrochemically active sites.
(iii) MXene 2D nature and the ease of cation intercalation lead to fast ion transport.
The nature of charge storage changes depending on the electrolyte. MXenes
show primary double-layer capacitive behavior in aqueous neutral and alkaline
electrolytes, while it becomes pseudocapacitive in acidic electrolytes, resulting in
ultrahigh capacitance values up to 450 F g−1 (1500 F cm−3 ) as presented in Chap.
18. Because of the 2D nature of MXenes, they tend to restack and make access
1 Introduction to 2D Transition Metal Carbides and Nitrides (MXenes) 11

of ions to the surfaces of 2D sheets difficult, particularly in electrodes beyond few

μm thickness. Various methods have been explored to overcome this challenge. For
example, at 0.2 mm thickness, electrodes made of vertically aligned Ti3 C2 Tx kept
their high capacitance of >200 F g−1 up to 2 V s−1 scan rate in 3 M sulfuric acid
electrolyte. As discussed earlier, MXenes can accommodate various metal cations,
which led to the exploration of Li-, Na-, K-, Mg-, and Al-ion batteries, as discussed
in Chaps. 19 and 20.
Beyond energy-related topics, several new applications of MXenes have
emerged, including electromagnetic interference and antennas (Chap. 21) and
environmental (Chap. 22.), sensor (Chap. 24), optical (Chaps. 17 and 25), and
biomedical (Chap. 26) ones. The starting years for each application of MXenes
are shown in the second ring of the pie chart in Fig. 1.4. Because of the promising
performance in these applications, MXenes have become key materials in many
areas. For example, the first studies on electromagnetic interference shielding were
published in the second half of 2016, and since then Ti3 C2 Tx is known as the
best 2D material for EMI shielding [23, 24]. Electronic and mechanical/structural
properties and applications are among the very first that were explored for MXenes.
However, most of the published studies are computational, and very little has been
done experimentally. Additionally, about 70% of publications on MXenes deal with
Ti3 C2 Tx , shown in the third ring of the pie chart in Fig. 1.4. Even though there
are more than 60 MXene compositions known to date and about half of them have
been synthesized, only ~30% of publications have been dedicated to them. These
numbers show a great potential of MXenes for numerous applications.

Acknowledgments We are thankful to various programs at the U.S. Department of Energy (DOE)
and U.S. National Science Foundation, Division of Materials Research (DMR), Ceramics Program
for their support of MXenes research throughout the years.

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24. Shahzad, F., Alhabeb, M., Hatter, C. B., Anasori, B., Hong, S. M., Koo, C. M., & Gogotsi, Y.
(2016). Electromagnetic interference shielding with 2D transition metal carbides (MXenes).
Science, 353(6304), 1137–1140.
 Part II
Synthesis, Compositions and Structure
Chapter 2
The Mn+1 AXn Phases: The Precursors
for MXenes

Michel W. Barsoum and Per Eklund

Introduction and History

In the 1960s, Hans Nowotny’s group in Vienna discovered [1] more than 100
new carbides and nitrides, including the so-called H phases and their relatives,
Ti3 SiC2 and Ti3 GeC2 . These phases remained largely unexplored with only spo-
radic work until the mid-1990s, when Barsoum and El-Raghy [2] synthesized
relatively phase-pure samples of Ti3 SiC2 and revealed it to be a material with a
remarkable combination of metallic and ceramic properties: good electrical and
thermal conductivity, machinablility, and resistance to thermal shock and oxidation.
They later discovered Ti4 AlN3 , making it clear that these phases shared a basic
structure and leading to the introduction of the nomenclature “Mn+1 AXn phases”
(n = 1, 2, or 3) or “MAX phases,” where M is a transition metal, A is an A-group
element, and X is C and/or N [3, 4].
The remarkable properties of the MAX phases originate from their layered struc-
ture and the mixed metallic-covalent nature of the strong M-X bonds together with
M-A bonds that are relatively weak. Because of this unusual property combination,
the MAX phases are being considered for a wide range of applications, such as high-
temperature structural applications, protective coatings, sensors, electrical contacts,
microelectromechanical systems, and many more. Currently, pantographs for some
of the high-speed trains in China are made with a MAX phase.

M. W. Barsoum ()
Department of Materials Science & Engineering, Drexel University, Philadelphia, PA, USA
e-mail: barsoumw@drexel.edu
P. Eklund ()
Thin Film Physics Division, Linköping University, IFM, Linköping, Sweden
e-mail: per.eklund@liu.se

© Springer Nature Switzerland AG 2019 15

B. Anasori, Y. Gogotsi (eds.), 2D Metal Carbides and Nitrides (MXenes),
https://doi.org/10.1007/978-3-030-19026-2_2
16 M. W. Barsoum and P. Eklund

In 2011, it was demonstrated that the A layers can be selectively etched from the
MAX phases [5] to form a new type of 2D material, named MXene, to emphasize
the relation to the MAX phases and the parallel with graphene. Within a couple
of years of the first report, MXenes have already become established as a class of
2D materials with remarkable possibilities for composition variations and property
tuning.
This chapter introduces the MAX phases, making the connection as precursors
to MXene. The chapter is largely based on – and summarizes – previous reviews [3,
6, 7] and a book [8]; we refer the reader to these sources for an in-depth treatment
of the fundamentals of the MAX phases. Quite recently, Sokol et al. catalogued
all MAX phases known to date and showed that they number over 150 (including
solid solutions and ordered quaternary phases). The interested reader is referred to
that paper for the list [9]. Furthermore, good introductory treatments of the MAX
phases are given in several brief overviews [4, 9–11]. Specific subtopics are treated
in a number of focused reviews, for example, the relation to related layered phases
[12–14], summaries Ti2 AlC and Ti3 AlC2 [15–17], tribology [18], magnetism [19],
spectroscopy and electronic structure [20], elastic and mechanical properties [21],
and oxidation [22].

Crystal Structure, Definitions, and Terminology

Crystal Structure of the MAX Phases

As defined by Barsoum [3], the MAX phases have the general formula Mn+1 AXn
(n = 1, 2, or 3). The different MAX stoichiometries are often referred to as 211
(n = 1), 312 (n = 2), and 413 (n = 3). The M elements are transition metals mainly
from groups 3 (Sc), 4 (Ti, Zr, Hf), 5 (V, Nb, Ta), and 6 (Cr and Mo). The A element
is primarily from groups 13 to 16 of the periodic table (Al, Ga, In, Si, Ge, Sn,

Fig. 2.1 Periodic table of the elements highlighting the M, A, and X elements – denoted by yellow,
blue, and black, respectively – that have been reported in the MAX phases (non-exhaustive).
Half-filled squares denote M (yellow) or A (blue) elements that have only been reported in solid
solutions or ordered quaternary MAX phases
Another random document with
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 —Sssjesjjtig, siste ze even uit, met ’n wenk van ’r
magere knokels, sluw, schuchter toch.—

Nijdige snauwhoera’s gierden ’r hoon-scherp

tegemoet.

—Je man kaikt mi sain skele lampies noa je hain!,

sarde ’n tuinder achter ’r rug, haar telkens porrend
tegen de schouers, dat ze schokte.

—Nouw sssjjoà.… nouw sssjjoa.… aa’s.. aa’s …

tongsleepte ze, in wanhoop opgejaagd om hooger te
bieden. Haar naar voren gestomd, geel kakement
sidderde van zenuwschokjes, ’r apige lippen trilden,
en ’r ingedrukten neus, wijd opgewipt bij de reukgaten,
bewreef ze onder ’t lispen.. nouw.. sssjjoà.. jullie gunt
t’r main gain sssjjpòg woàter!

—Wa’ mò je tug mi die peene veur sestig uitvoere

waif?.. je koop hullie pattekelier veur vaiftig bai
ònster.… lolde een weer in hoontoon.

—Nouw sssjjoà … nouw sssjjoà … brabbelde ze

verlegener terug, òpstarend in oogenangst naar den
Bode, met zenuwsnel wimpergetril, als hing ’n
slingerend mes boven ’r hoofd,—De vrouwen grolden,
konkelden en schaterden vinnig jaloersch, lol-woest,
dat ze’r zoo hoog opgedreven hadden, in hun gejaagd
bieden.

—Nou mag sai d’r biertje loàte werrike?.. Bi-jai-’t-Hain!

—Sestig, eenmoal, veur de derde moal, hakte de

Bode droog door, vrouw Joapeke! [145]
 Ze beefde als ’n riet, vrouw Jaapeke! Ze voelde, in ’r
zenuwangst, dat ze toch te hoog was gegaan. Bang
graaiden ’r gele, breed-bemouwde, slobberige armen,
naar de penen die de Bode tegen ’r platte borst
smakte. Geel-rooiïg vervlekt, dampte ’r tronie, dat
monsterlijker rimpelde als oudwijverig apenbakkes, in
glimmig zweetvet. Niemand durfde ze aankijken, als
had ze een gemeene streek uitgehaald. Tegen ’r
hardgeel, verkaald kort manteltje, knelde ze
zenuwachtig de peenen, en banger loerde ’r
monsterlijk verdroogde begijntjes-kop ùit, tusschen
den fellen daver van ’r wortelen-oranje en ’t fijn-
kartelig uitgeknipt donker groen loof.—

—Nog twai koopies, dan is de skaft dur, lachte de

Bode, ’n bittertje weer met smaktong wegklapperend
en opzuigend z’n adem.

—Nou he’k nog ’n sak mit laifende woar.… gain

f’rklikker in de buurt?.… niks nergens peliesie?.… wel-
nou-dan!.. dan he’k hier spring-laifende woar.… twee
prêchtige kenaintjes!.… kaik hullie tippele!.. kaik hullie
tippele!.. la’ main in gos noam niet langert proate..
beste minse!

De grauwe zak had ie opengefrommeld en er met één

hand, bij de ooren, ’n donzig blond konijntje
uitgegrabbeld, dat angstig spartelde en voorpootjes
kramperig tegen wit-bevlekt borstje òptrok.—

Schater barstte òp naar ’t hangende diertje, kerels

gierden, vrouwen gilden.
 —Sou ’t d’r ’n broertje.… of ’n sussie van sain, moar
dur sit dur nog een percies-eender in de sak.. wie blief
dur hullie!

In rauwen humor, de twee ooren in één hand

saamgeknoopt, keerde ie konijntje naar zich toe,
ruggetje naar de koopers, vroeg ’t, venijnig tikkend
met vingertop op beweeglijk zenuw-trillend neusje:

—Hoe vint ùfus de f’rgoadering.… die ùfus broàde

sel? ouë jonge?.…

Heet gegier raasde uit den troep en konijntje draaide

ie rond aan z’n ooren, dat dierke als ’n spiraalwrong,
weer duizel-snel terug-schroefde.—Kramperiger
spartelden opgetrokken voorpootjes; [146]suf bleef
staren ’t stomme kopje tusschen engen oorenknel;
sneller en verbluft trilde angstiger ’t blanke neusje.—

Vrouw Jaapeke was er weer ’t eerst bij met ’r bod.—

—F’rvloekt, die komp nou altait op ’t lest! stiekem uit ’t

hoekie.… snauwde de brei-vrouw weer, giftig
doorwriemelend d’r steken, bij webbende
vingertoppen.

—Is juffer luiwoàge weer an ’t woord? spotte ’n

groenboer naast ’r.

—Nouw sssjòa … nouw sssjjoà … kauwden ’r dikke

lippen weer, en zweeterig, met rooie vlekken,
rondgetrokken als doffe bloedvinnen, glom ’r gele
begijnentronie. Angstig loerden ’r oogen òp naar ’t
zacht nog nàschommelende konijntje, dat de Bode
 telkens kleine draai-duwetjes gaf. Droeverig-gebluft
staarde ’t kopje, de oogjes trilden, keken wijs, als
voelde ’t deernis, dat ze ’m zoo plots uit z’n stik-
donkeren, duffen aardappelenzak, in ’t felle zonlicht
daar te kijk hingen. Z’n spichtige steilgrijze
snorhaartjes beefden en z’n weeke angst-bekje
mummelde wat, als verkauwde ’t z’n eigen angst.—

—Veertig éenmoal.…

—Sestig, ’n rauwe stem van tuinder klonk achteruit.

—Ksjt! ksjt! katjes.… siste ’n kerel, sloan jullie de gaile

medam veur de sokke.…

Weer trok weduwe Jaapeke beverig aan ’n grooten

knoop van ’r hard-geel manteltje; sterker beefden ’r
oogwimpers.

—An joù juffer luiwoàge!.. veur aige bik!.…

—Wa’ mot dur medam mi’ knaine van doen? sai frait
d’r puur kalkoene!.…

—Nouw sssjjoà … nouw sssjjoà … sleeptongde en

lispte ze angstig terug, afwerend duwen en
grapstooten in rug en zij, jullie gunt dur.… gunt dur.. ’n
minssjch nikssjch.

Angstiger loerde ze naar Bode òp, of hooger bod

inviel.

—Sestig één.… sestig anderr.…

—Vaif en sestig!.…
 —Mooi soo!.… gooit de boel òp waife;.… aa’s alles
brandt brandt woater ook.. la’ jullie je aige nie troefe..
van die gele sloerie-ekster,—stootte ’n venter uit,
grinnekend tegen ’n buurman. [147]

Weer had vrouw Jaapeke den Bode stiekem gewenkt,

vlak op z’n schoenen, schuwtjes-snel ’n knauw met ’r
beverige handen àfdrukkend.—

—Aaj! vrouw Joapeke! main eksterooge! krijschte de

Bode een arm en been lawaaiig-komiek de lucht
insliertend, ’t konijntje meeslingerend bij z’n ooren.

Joelende hoongier schaterde los. Vrouw Jaapeke

stond bedremmeld, nu Bode ’r in z’n lol verraden ging,
dat zìj aan ’t bod was; dat zìj op z’n schoenen gedrukt
had. Weer hooger ging tegenbod;.… angstiglijker rilde
gedachtetje door ’r heen, dat ze de beesjes niet kreeg.
—

—Sien jullie, de gele medam waa’s ’t weer!.…

—Anme huppla!.… nou kraig sai twee fraiers thuis!..

—Tachtig, hakte weer door de Bode, en weer voelde

ie ’n half verborgen druk van vrouw Jaapeke’s
beverige knokels op z’n schoen.—

—Vaif en tachtig eenmoal.… andermoal.… veur de

dèrde moal!.. vrouw Joapeke!

Weer barstte ’n rauw hoera los, rond de gele medam.

Ribbe-stootend bonkten ze’r, gilden en hoonden de
jaloerschen om ’r heen.—Want ze wisten wel, dat zij
dingen plaatste, die anderen nooit gebruiken konden,
 bij wijven in de Nes. Daarom durfden ze niet nòg
hooger tegen ’r opbieden, bang dat ze ’r misschien
aan hangen bleven.—Bode had konijntje weer in den
zak gesmakt en rolde de levende waar vrouw Jaapeke
tegen ’r platte borst, boven wortelenstapel, waarmee
ze nog onder de armen, tusschen de mensch-kluw
ingepropt knelde.

—Saa’k f’rbrande aa’s ’k snap wá’ ’t waif d’r mee

uithoale mot.… verleje.… mi Juni hep sai ook.. die vaif
prêchtige leeuwerikkies kocht.… die hassebas.…
woar hoalt ’t murmel de sinte van wèg!.…

—Van beroep is d’r man tug stroat-oàrm, hoonde ’n

ander.. hee! gele medam, koop jai d’rais ’n nuwt
stelletje kiese hee?.…

—Trek jai d’r veere van ’n kikker! schaterde valsch

mee de vrouw met d’r rooie kap en woelige sierseltjes,
boven ’r voorhoofd.… [148]se is t’r moager aa’s ’n tang!
en ’t laikt dâ se koopt veur aige bik!

—Nou, grinnikte de brei-vrouw,—in de stad … loopt ’t

mins.… soo ver aa’s de hemel blauw is.… en roakt
t’met nooit niks kwait van d’r kar.

—De leste koop!.… luistert wèl, goê-liën, schalde

hoogklaar de Bode weer,.… om te beginne en an te
vange mit ’t begin, he’k hier ’n prèchtige takrooie
maidoorn.… wie blieft.. wie-sait!

Van vier kanten raasde áán, dooreengolvend

stemgekletter.
 —Tien! vaiftien!.… achttien!.…

—Mit je àlle achttien, lachte Bode, mit je àlle twintig.…

wie mot!

Dat was blomgoed, waar de hééle stoet op loerde.—

—F’rfloekt.… de fint snait d’r ieder dag ’n takkie van

sain boom.… aa’s tie dit joar.. gain tachtig pop veur s’n
boom moak, hiet ik puur gain Teun Stainders meer.…

De eerste bloemenkoop was weggerùkt. Langzaam

achter ’n stapel aardbeikisten, wrong groenboer nog
twee kleinere takjes. Maar nòg schreeuweriger, voor
hooger prijs, kochten ze die in. Ze wachten er op, en
hurrieden alle tegelijk er om.—

—Op is de boel!… gelukkig, kwam d’r aêrs nog

muiterai an board.… Moandag weer ’n handje!.…
lachte de Bode, en nou he’k hier nog prèchtige
lelies.… wie mot dur.. wie?..

Nauwelijks had ie de vormfijne lang-stengelige

bloemen in de handen of ze smakten op ’m neer.
Twee vrouwen rukten ’n heel bosje uit z’n warme
knuist.

—Ikke ook, ikke mot d’r òòk.…

—Hier.… doar hai je vast màin.. vrachie sinte!.… Ikke

hep d’r tien!.…

—Màin.… main!.… daa’s gemàin, gilde ’n ander.…

ikke hep d’r eerst sait!.…
—Krikf’rdorie.… die blomme luchte lèkker, snoof Dirk
verbaasd-loom òp.. die mo’k hebbe veur main
klante!.…

De vrouw met de stuipige breikousstomp was plots

òver de hurriënde en dringende kerels heengebukt, ’r
vat-breed achterwerk [149]’n groenboer langs ’t gezicht
schurend. In woesten ruk, had ze vrouw Jaapeke de
lelies uit ’r hand gescheurd, de bloemen haastig in d’r
schort beschermend.—Vier andere vrouwen, met
verkoop van veiling, zwaarlijvig bijeengeklonterd,
sprongen bijzij op gele madam af, om te zien of ze
nog meer blommen bergde.—Maar in één ruk had de
breivrouw ’r leeggeplukt. Grienerige woedetrekken
groefden om schrei-mond van gele medam, en
sputterend spoog-lispte ze vloeken uit, naar de
woeststerke wijven. ’n Endje van vrouw Jaapeke af,
waren nu wat groenboeren op de brei-vrouw
losgesprongen, om die den blommeboel te
ontfutselen, bonkend en haar bekrijschend dat ze niet
had laten uitveilen. Maar breivrouw weerde zich heftig,
trapte naar achter, beukte opzij, in den knellenden
warrel van graaiende en rukkende handen, stampen
van beenen en lijven. Bodestem schalde plots bòven ’t
warme stoeigewoel uit, in lach van z’n frisschen kop.

—Nou nog wa’ prêchtige pioene, wie-se-hep kraigt de

staikels.… ikke hou de blomme—.. In wat tellen
hadden de venters ’m afgekocht.—Broeierige woeling
gistte los in den veiling-prop.—Snikhitte dampte om
hun zweethoofden. Zon priemde fellere lichtlansen
neer op de boot. Elk plekje braadde en kookte.—
Spraakloos buiten ’t gewoel, stond kapitein voor zich
 uit te staren, ’t vonkwater in, en hoorbaarder nu,
achter veilingstilte uit, klotste de golfjeskabbel tegen
schipwanden òp in schuimende koeling en week
ruischgestroom.—

Hunkering naar ochtendschaft ging rond. Om den

Bode klonterde de menschenkluit los. Twee dikke
groenboeren kankaneerden in nauw gangetje van
hangende manden en kisten, naar de kajuit. De dikste,
achteruit dansend, met kwabbige schommeling van
z’n vet lijf en spanning van dans-dijen, strompelde
gladkoperen traprichel af. Springend met
kromgebogen armen, ’n zwaai de lucht in, plof-bonsde
de andere op z’n borst en buik. Achter hen ààn,
trampelde ’n heele bende naar beneden, de kajuit in,
waar al wat kerels, mistig berookt in halflicht hoekje,
saamgebroeid hurkten achter hun manden.

Als ’n laag-bezolderde ark, spitsig toeloopend en

hellend bij [150]den boeg, dampigde de kajuit,
volgesmookt van pijp- en sigarendamp, snikheet.
Groòter en ruwer dan in ’t fel deklicht, onder half
schaduw nù, lijfloom neergesmakt op de rooiige ruw-
bekwaste banken,—leken de vrouwen- en
manskoppen in de kajuitsdiepte. Achter enkele half-
verduisterde hoofden, wangbrokken en kleurig haar,
stroomde zonnelichtspuiing, door hooge ronde
kijkgaten, beomtrekkend èven wat tronies in zoom van
goud, fijn vloeiende lijn, die gloeide soms als
electrische lichtdraad. Schuwere glansen schoten
door morsig beruite kijkgaten, hoog ingeboord boven
boeg, scheemrig vervloeiend in de halfdonkre kajuits-
sombering.—Langs de wanden en midden in, plankten
 de ruw-rooiige banken, breed, waarop neergesmakt
dromden in stomme hurrie van punten en brokkelige
kanten, kisten, pakken en manden.—In de kajuit stonk
’t duffer, vunzer nog dan op ’t dek, waar dòòr de
groenteluchten heen, soms nog ziltig zoute lucht van
zee-windstroom aanwoei. De hooge kijkgaten, ’t heele
schip langs, brandden in reflexvuur van kanaalwater
en zonnegloed, tusschen ’t opkruipende half-duister in
de stik-heete kajuit, als gloei-gouên oogen. Tegen de
grijs-grauwe morsige zoldering zonden wat
lichtkrinkels, die trillerig door elkaar heenspiraalden.—
Vlak onder de gloei-gouden licht-oogenrij van
kijkgaten, doorzond en fel-verblindend, kropen
schaduwtinten langs verdonkerde wanden, zonk de
kajuit in, vaag-kleurig van paarsen rook, even
doorneveld van zwakke glanzen.—In al òpgeknelder
drom trampelden de vensters van ’t dek, smakten zich
neer op de banken, tusschen hun pakken en kisten.—
In roodbruine somberheid plankten de banken, en
heel de kajuit, met de oppropping van koopwaar, leek
’n groef, roodsteenig en duister, waarin
schipbreukelingen saamgevlucht stumperden, bàng
omknellend hun laatste rijkdommen.

’n Lange kerel, met heel kleine oogjes, z’n hoofd de

zoldering rakend, waaronder z’n gebaren reuzigden,
holde heen en weer te bedienen, stapte telkens op ’n
vrouw af, die op bankpunt koffie schonk uit ’n bruin
beschilderden koffie-stoomketel. Tegen muur van
kajuitstrap, donkerde inhammend buffetje, waarin
opgedrongen bijéén hinkten, diendertjes, manke
jeneverglaasjes; [151]tegen elkaar leunden, flesschen,
koppen, broodbonken, kaas, steenen bordjes en
 sigaren. Van alle kanten, uit de half duistere kajuit,
tusschen het triestige roodbruin van banken en morsig
grijs van zoldering, roezemoesden zeurige, teemende
en krijschend-jolige, hakkelende en sputterende
stemmen. Uit elken hoek warrelde geraas, gekakel en
boerenwoest geschater. Gretig pakten de venters hun
stukkenzak met halve broodhompen en mikkies uit;
hàpten, hàpten.

—Koffie main!

—’n Bakkie g’laik!

De heele bende verdonkerd en ver-reuzigd onder lage

zoldering en balken, slurpte koffie. Overal, ingebukte
nekken en gezichten, de warme lippen op de groote
kopranden platgeperst, vuile handen rond de kom
gekneld.—In anderen klauw, de halve mikkies
gegrepen, hapten dierlijk de geile ruwe monden,
slurpten de tongen, grepen en persten de morsig
levend-beweeglijke vingers, groen en bruin vervuild
van smeer. Op verhoogd boeg-end, druk
roezemoesde ’n gierend troepje, de beschaduwde
koppen naar elkaar toegebukt, in raaskallende lol,
omwolkt van paarsblauwigen rookmist.—

Soms even schampte òp, achter nevel-paars, ’n

pijpekop, ’n kiel, rooiig-donker, grimmig-gebarende
hand, ’n wangkant, ’n harige achterkop, met even
lichtbeflitste oorrand, plots weer wegduisterend in
zwaarder rookgewolk. Naar alle kanten liep de lange
kerel met z’n dampende koffiekoppen, zonder schotels
rondgediend, oorloos en gloeiheet, de klef’rige
greepklare ventershanden induwend. Al meer reuzige
 schoenen, beenen en lijven zakten de loom nauwe
kajuitstrap af, waar ’n ruitje even licht sloeg, voor ààn,
in ’t rookige hol. De vrouwen bijeengegroept kakelden
en kuchten, op d’r hooge banken saamgedromd,
tegenover de woeste rookers, aan spitsig-hellende
boeg. Telkens moesten ze inschuiven, opschuiven
voor al meer instrompelend volk, dat tusschen
vrachten en meegesjouwde bakken, als onder ’n lagen
hemel van zoldering-morsigheid bijeen kwam broeien.
De balken met donkere reten en vuile flodders verf,
kruisten vlak boven hun scheemrige tronies. Aan ’t
eind van middenbank stond [152]de schenkvrouw,
breed ingebukt ’r oer-ketel te hellen. Telkens bracht de
lange bediende, klefferig bevuilde koppen áán, hield
éven schoongeplaste ònder den ketel-slurf, inmiddels
vlug uit grooten suikerzak,—als overvloedhoorn blank-
open neergetuit op bank-end,—’n schep opvisschend,
en in zwierige vlucht afplonsend, in ieder kop ’n
hoosje. Naast de ingebukte vrouw, die geen tijd had
om ’r lijf te rekken, stond ’n vuil emmertje, van binnen
bleek-rood uitgekleurd, met smoezel water, waarin ze
luchtigjes,—toch doorschenkend uit ’r koffieslurf,—
rond-spoelde de aangedragen, klodderig bestroopte
koppen. Even ’t bruin-bestroopte van buiten
wegplassend, druipend nog van vieze straaltjes
grondig vocht, grabbelde ze met ’r natte handen de
kommen weer òp, uit den emmer. En ’r zoon bleef
bedienen, hield de reuzige koppen weer voor de tuit,
die stroef stond, beklept-harig als ’n levende slurf,
waarop vuiligheid bakte. En vlug, de eeuwig-gebukte
schenkster rookte de kommen weer vol geurig
koffiebaksel.—
 Walgelijke stanken, duf en vuns rotbroeiden de
groenten uit, de jenever, koffie en tabak. Tegen ’t
roodbruine ruwe gebank, en den zwartmorsigen
grond, zogen de stanken vast. Wilder, woester, in
vergrootende donkering, slurpten, verhapten de
koppen, met apig-dierlijke rukken ’t brood, in geilen
slurp en zuig, smakkend zich gevend aan vroege
vraatzucht en drank.

Dirk lag met z’n arm op ’n stapel duf-stinkende

manden, en achter z’n hoofd, op tusschenplank van
middenbank, tweekants bezet, stapelden bossen
groenten en bloemen, zoet-zwoele lelies, tusschen
voos-luchtende aardappels en kool, bruidsgeur en
blankte, vermolmend onder gronderige stanken van
benauwing. Elk ding wasemde stank uit. De kleeren
van venters stonken als verrotte beenderen. Verhitte
kroegasem en bloemengeur zogen door elkaar heen.
—Naast Dirk, hurkten met beenen onder kin
opgehaakt, Klaas Grint en Rink van den polder,
happend en smakkerend in scharren en poonen,
ronkend van vreetgenot. Dirk had z’n derde kop koffie
al heet ingeslurpt, luisterde nu, dwars door leuter-
geratel en handengeklakker van nasjacherende
vrouwen en kerels om hem, naar [153]Grint, moeilijk
verstaand, z’n oor geheven als luistertrechter, tegen
den heeten herrieraas van stemmen in. Grint
bepeuterde voorzichtiglijk z’n poonen, smakkerde bij
brokken de vet-glimmige blanke visch z’n mond in,
sprak en vergierde schunnige moppen, dat z’n
uitkauwsel, telkens tusschen z’n snaterende kaken
opschemerde. Als ’n zaal, waarin rumoerige kakatoes
op eigen houtje krijschend konverseeren, dazelde
 stemmesnater rond. In al gamma’s brulden, lolden,
lachten menschenkelen, schorre, rauwe, zachte en
weeke timbres dooréén.—Soms klonken er als schrei-
geluid, kermende klanken; dàn bulderde en donderde
woordkrijsch uit, hevig en verhit in de mist-rookige
kajuit.—Rink van den polder, slobberde jenever, door
z’n scharrenmaal hèèn. Van uit z’n apigen knie-hurk,
rookmistig omdampt, keek ie telkens flikker-scherpe
kajuitsoogen in, die trilrige zonnekringen, wazig-
vloeiend verspuiden tegen zoldergrauw. Eén balk-brok
kreeg felsten stroom, waarop, in krinkelige rilling, als
’n zwabberende kurketrekker, ’t licht invrat als wit vuur.
Naast Rink, ingedrukt en bekneld van twee kanten,
met mandwerk, stumperde ’n bochel, door z’n puntbult
’n end van bankwand afgeduwd.—Peinzend telde hij
eiertjes. Zacht schuifelde z’n hand in ’t strooien bed,
en koelblank tusschen z’n groenig-vuile vingers,
marmerden de eitjes, telkens teederlijk door ’m
weggekoesterd in ’t gouden stroo. Na koffieslurp
voelden de kerels zich bijna in de stad, furiede
zuiphartstocht òp. Overal rinkelden jeneverglaasjes,
zogen de rooie dorstige kelen ’t vocht in, vol wellust.

—Màin segoàr.… moàr hardstikke swoàr! schreeuwde

Dirk.

—Enne main nog ’n kats, veur sain sinte, grinnikte

Grint op Rink wijzend.

Met acht kommen tegelijk, in balans-behendigheid

deinde zacht de lange bediende door den rookmist
heen, naar stijgenden boeghoek, al hooger onder de
zoldering uitreuzend, in bukhouding z’n kop op borst
 gedrongen, om zich niet te stooten.—Zwier-vlug
deelde ie de kommen rond, tusschen de gretig-
uitgestoken handen.—Sterker klonk weer gelebber,
smakking en dof eetgeronk. Klaterende roezemoes,
gillerig en hoog, onder [154]voortgonzenden toon van
mannenbassen, gromde door de kajuit. Levende
walvisch, leek ze menschen in angstlawaai opgehapt
te hebben, die daar verwilderd in d’r half duisteren
muil zaten te schreeuwen, te stampen en te reutelen
tegen elkaar van kreupelen angst.—

Stooten van machinekamer bonkten trillingen door de

wanden, bracht sidder in de koppen, handen en
beenen. Door manden en bakken ging lèvende
beefstroom. Alles zat in trilling; de tronies die raasden,
de monden die zopen en vloekten, pruimden en
kwebbelden; de handen, die vastklemden bevende
kommen; de beenen, die trampelden of hurkten. Een
flakkerende wiegel van schaduw en lichtvegen
schemerde tonig en diep door de rook-paarse kajuit,
rooïig-blauw verdampend in hel-lichtende òogenrij van
kijkgaten, die loerden met zengenden vuur-blik.—Diep
daarònder, de ingezonken lijven op banken, de
handen op knieën, beverig doorschokt van
machinedreun, de hoofden en oogen vertemperd in
kleurigen wasem, tusschen den dof morsigen grom
van roodbruin plankwerk en wandgrijs. Daar, midden
in de broeihitte, sloegen, walmden en braakten de
stanken òp, vunziger, uit half-open kelen van manden,
uit zak-strotten, uit gaten en spleten van kisten.
Zweet-rook van lijven dampte van kleeren; van
barokke klompschoenen, enkele scheef en vergroeid
als paardevoeten; van pilow-broeken en baaien
 rokken.—Uit alle hoeken wasemde rottende stank
rond.—Schemervegen van schaduwzware tinten
versluierden soms plòts groen-zwartig de kajuit. Rooie
sigaarpunten gloeiden áán, in donkering van hoeken
en de rondzonnige kajuitsoogen bleven loeren in fel
vuur. Prachtige glansjes, smeltend en wiegelend,
zwierden op menie-rooie randjes van drie gesloten
venstertjes. Licht van waterkabbel wiegde méé met
warrel van zonnespel daar in golfjes, àchter
morsigblauw paarlmoerig-benevelde ruitjes. En wat
trillerig geschijn deinde áán en af en om de kijkertjes.
Als ’n diepe hangmat, waarin rookige schaduwen
kwijnden en weer wazig-grillig verkleurden, in wiegel
van gesmoord licht, hing de kajuit, plots weer in
zachten schommel van boot; hangmat van rook en
stank, waarin de menschlijven, opgepropt verduisterd
in [155]grauwig paars en dampig gesmoord zonlicht,
bewogen in nachtmerrie-realiteit. Uit pracht van diepe
donkerdroomrige tonen, stemmige diepte van
zachtflakkrenden kleurmist, zwaarbefloersd in grillig
verstaltigenden groenen rook, doken telkens ànders
de boerenkoppen òp. Roodbruin de banken, angstiger
verdoffend den getemperden kleurenstoei der mans-
en vrouwkleeren; in rooknevels de groentebakken en
manden, dwars en stapelend uitgestald op den
donkeren vloer, vóór sprookjes-reuzige voeten, òp
schootbrokken, tusschen glazen, vuile kommen en
rommelzooi van stronken en afval. Daar, door dàt
hangmatleven, zogen en walmden de helsch-
gemengde stanken, tusschen gebeuk, getril en
geraas; broeiden de koppen bijéén; lekte ’t zonnevuur
door de naven en ’t dek naar kajuit, waar de
snikkende hittedag verduisterd en gesmoord lag te
 reutelen tusschen engte van duffe wanden.—Ènkele
menschkoppen bewogen in glansgouïgen zoom.
Wangbrokken gloeiden beschminkt van goudpoeierig
schijnsel. Pet-vormpjes vergrilden in zacht-kleurig dof-
duister.—Praat en slok, deinde òp uit diepe tinttonen.
—Eetmonden vervaagden omrookt onder nevels,
snorre-baardig, in harige ruwheid. En de golfjes in
schroeienden zonnedoop, verspoelden kabbelig-
speels, ruischend tegen de lichtoogen bòven hun
tronies.—In paarsigen waas, de groote werkhanden
woelden en gebaarden in en uit lichtvegen, rumoerend
méé met hun zuip, hun krijsch, lol en ironie.—Handen,
breed en geweldig als levende wezens, op zichzelf,
hevig gekromd, verbronsd in aardewroet, in rauwe
energie van beweeg en passie, tusschen den rookmist
en rood-groenen damp, in wilde gebaar-woeling
wègslingerend scheemrige vegen en tint-grillige
schaduwen. Handen van bronzen reuzen, graaiend in
smoor van zonnevuur.—

—Dà waa’s d’r main ’n sjouw Dirk, schreeuwde Klaas

Grint, met beverige stem, doorschokt van dreun,—nou
he’k tug puur naitig bakke oarbei op de boot—hee
annaime!—main nog ’n bakkie leut!.…—

—Daa’s f’rduufeld achste bak, lachte de bediende.

—Nou wà’ sel ’t?.… betoàl ’k hullie nie? houw tot soo
[156]langest je snoater,.… nou hoor-je Dirk? daa’s tug
puur naitig bakke, allain van main rechterhoek!.…

—F’rek jai, viel Dirk met vollen mond in, zich

verslikkend in hoestschokken, onder opslurping van
koffie, dat z’n kop bloedrood te barsten dreigde.…
—Kaik nou, die wil d’r babbele aa’s tie te slikkebikke
sit,.. wà noù f’rek?.. der kenne.. kenne hier op dek,
puur.. dertienhonderd bakke oarebai!.… en f’middag
komp ’r nog ’n nuute anvoer.… nou, dan wee’k daa’k
goar bin!.…

—’t Is d’r dan ook duufels mit hoàst gonge hee?.. zei
met diepe stem, zangerig, ’n venter vlak bij Dirk.
Achter middenschot van bank zat ie, met verdraaid lijf,
alleen neusbrok en oogen er boven uitloenschend
naar de kerels.

Dirk, Grint en Rink draaiden zich half om.

—Hoe most da’ maint? vroeg stug Dirk.

—Wel nou, ’t is d’r nog gain drie weuke hee!.…

t’met … daa’k … toe he’k de soete fransies sien hep
hee?.… Wa’ màin dat d’r toen teugesloegte.… de
vrucht wou nie sette.… alles d’r nog groen en half
raip.. de grond uit!

—Daa’s net … veur drie weuke he’k niks aa’s rooie

vlekkies in main tuin had, lachte Grint.

—Wel nou, zangde de diepe stem achter beschot

weer, met halve tronie er boven uit, en een hand
stumperig meebetoogend in beknelde gebaren,—de
boel is d’r nou overstroomd hee?—

Met andere hand achter schot verscholen bonkte ie

hevig op z’n weggedoken been, greep ie gretig naar ’n
borrel, dien de lange kerel ’m brengen kwam.
 Achterover z’n kop, smeet ie z’n hapje donker
mondgat in, bestelde smakkerend en likkend nog een.

—Nou, moar de haire hebbe d’r puur wâ inpalmt an ’t

stêtjon en in de hoàfe hee?.… da stong t’met nie
stil.… Van màin drie duusend kilo.. van sàin
tweeduusend.. van Klaas, van Gijs, van Joap, van
Dirk, sooveul aa’s sullie d’r hadde,—of aa’s je kèrtak
veurskreef.…

—Wa?.… sooveul?… soo veul aa’s ’k f’rkoope wil

hee? barstte smadelijk Rink uit,—buite da’ f’koop ikke
tug òòk.. da kroak je ommirs? [157]

—Nou daa’s nie net, onthutst zei Grint, moar nou mo’
je.. mó’ je ook segge dâ je van ’t winter.… al kèrtak
moakt hep.. van hoeveul je laif’re mot.—’n Màn, ’n
man,… ’n woord, ’n woord.… hee?.… wa’ jou Dirk?.…
wá’ jou Staine, wa jou.… Gais?.… je hoef d’r ommers
nie veur de heule mikmak te f’rkertakteere?.…

—Daa’s klesseneere, lolde Rink, woest verrollend z’n

gemeengroene oogen,—màin nog ’n bakkie leut
hee!.… moar ikke f’rkoop wa’ kwait kèn … aa’s d’r
beteder martpraise binne, al hè’k kertak veur vaif
joàr!.… vat je!.…

—Nou seg, vergoelijkte weer sluwig Grint, de groote

afnaimpers hebbe d’r tog ook hoarlie rissieko? daa’s
net nie?.… en dá’ jòar.… f’rdomd.… sullie betoale d’r
bestig hoog! da mô sait! Daa’s tog moar ordentelik!
Velaije joar stong de mart vol van oarebai.… nie te
f’rkoope.… hee?.… doar stonge wullie.… mit de pet in
de ooge hee?.… en op haide?.… op haide?.…
 —Nou, giftte plots ’n rooie driftkop uit rookwolk
òpduikend, z’n beenen met gestommel van de bank
afsullend,—dà tuig f’rdient d’r g’nog!.… wa’ doene die
likkebaire.… niks gedoan hoor!.… sai b’toale d’r
lootjes feuruit bai de swoager van dokter Troost …
komme hullie d’r effetjes kaike hee?.. de kontreleur
doen d’r ommirs alles!.. enne.… dan.… dan hebbe
hullie.… allain mit de oarbaie opsende.… allainig mit
d’r oarbaie.… sien je!.… ’n duusend pop f’rdiend.… in
’n weuk of soo, hee?.…

—Joà, moar de rissieko, teemde Klaas Grint.—

—Je suster rissieko.… soake aa’s piere.… soo staif.…

om dà sullie de loodpot hebbe om vèur te skiete.…
sende sullie ònster goed.… deur Duitschland …
Enggeland.. en moake sullie d’r joartje wel goed hee?
O die diefe.… die sloeries! schreeuwde Rink.

—Nou moar.. wa’ há’ je f’rlaije joar dan?… basstemde

weer Steyne achter z’n schot, met z’n mondlijn even ’r
boven,.. toen hâ je Beijens.… da’ rooide noa niks
hee?.… die kaèrel.. hep toen ònster goed afnome
hee? al wat wullie niet kwait kenne [158]hee?.… ’n sint
’n mandje hee?.… mit ’n straip of’r de bakke!.… je was
d’r blai da’ se hullie d’r nog veur ’n sint kwait kwam!.…
Moar die skevuit heb f’rdiend … die hep d’r waite … dá’
wai gain uitweg hadde hee?.… mit al ’t goed.… die
hep d’r van màin.… van joù.… van jan en alleman
kocht.… hee?.…

—Of daa’n skurk was, ’n geep.…. tromboneerde de

woedestem van Rink, daa’s Beijens van de Skans
hee?.… die skoelje hep d’r ’n achthonderd pop, in één