Inside Materials

Inside Materials
Newsletter - December 2011
A Water-stable Metal Organic Framework for
Hydrogen Storage Applications
In this issue
A Water-stable Metal Organic
Framework for Hydrogen
Storage Applications
Young Wild Idea: Graphene
Microheaters Based Flexible
and Stretchable Display
p1
p2
IOP Conference Self Healing Materials
‘Cruising at Full Speed’:
Farewell to Joris Vogelaar and
Richard van den Hof
p3
Correction: Interfacial Bonding
of Polymer Coatings on
Metal Substrates
p5
Publications Self Healing Materials
2010 (and late 2009) TU Delft
p5
Jie Yang and Theo Dingemans
Faculty of Aerospace Engineering,
Chair Novel Aerospace materials
Contact information:
Jie.Yang@tudelft.nl,
T.J.Dingemans@tudelft.nl
Metal organic frameworks such
as MOF-5 are a promising class
of materials for hydrogen storage
devices. They are light-weight,
safe, cheap to produce and it has
been demonstrated that MOFs
show fully reversible hydrogen
sorption and desorption behavior.
One concern, however, is their
sensitivity towards moisture. In
this article, we will show that the
stability of MOF-5 towards the
presence of H2O can be improved
dramatically when one or more
-CH3 units are introduced directly
adjacent (ortho) to the carboxylate metal binding site [1].
Metal organic frameworks (MOFs) are
a class of porous inorganic-organic
hybrid materials, which can adsorb and
desorb hydrogen molecules fast and
reversibly. The tunable structure and
excellent hydrogen storage capability make MOFs promising hydrogen
storage materials.
>>
Colophon
Postal adress
P.O. Box 5058
2600 GB Delft
Visiting adress
Kluyverweg 1
2629 HS Delft
http://www.dcmat.tudelft.nl
Editorial Team
Eduardo Mendes
Henk Jonkers
Marcel Sluiter
Barbara Lubelli
Santiago Garcia Espallargas
Menno Jager
Contributions
Jie Yang
T.J. Dingemans
Shou-En Zhu
P. Taheri MSc.
Alexander Schmets
Deadline contributions for next issue:
15 February 2012
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Disclaimer
Although the information in this newsletter
has been prepared with care, the editorial
team and DCMat cannot be held responsible
for mistakes or any consequences thereof.
Figure 1. The MOF-5 structure shown as ZnO4 tetrahedra (blue polyhedra) bridged by benzene
dicarboxylate linkers (gray, C and red, O) to give an extended 3D cubic framework. The yellow
sphere represents the largest sphere that can occupy the pores without penetrating the van
der Waals space of the framework.
Inside Materials - Newsletter Delft Centre for Materials - December 2011
Page 2
Figure 2. The hydrogen uptake capacities of standard MOF-5 (black), methyl- (red) and dimethyl-modified (blue) MOF-5.
Unfortunately, the sensitivity of MOFs
towards moisture has limited their
practical application. Moisture from
ambient air or trace amounts of water
from the electrolysis (H2 generation)
process would destroy most MOFs in a
matter of hours. From a practical point
of view, a stable MOF is desired. To
this end, we prepared a water-stable
MOF by introducing methyl (-CH3)
groups into a well-known water-sensitive MOF, namely MOF-5, which is one
of the most promising MOFs for future
hydrogen storage applications to date
(Figure 1).
Unmodified MOF-5 is able to store 1.44
wt% of hydrogen at 77 K and 1 bar.
Our methyl modified MOF-5 exhibits a
similar crystal structure and hydrogen
uptake capacity as MOF-5. Both MOF-5
and methyl modified MOF-5 were
exposed to ambient air with a relative
humidity of 32-37%. After 1 day, the
structure of MOF-5 was completely destroyed and no hydrogen uptake was
observed because the crystal structure
had collapsed. In contrast, the structure of the methyl modified MOF-5
remained stable and even after 4 days
exposure to ambient air the structure
remained largely intact exhibiting a
hydrogen uptake capacity of 1.0 wt%,
which constitutes a 30% decrease in
H2 uptake capacity.
Interestingly, when a second -CH3
group was introduced into the MOF-5
framework, the hydrogen uptake
capability of this dimethyl modified
MOF-5 is able to recover completely
after being exposed to said ambient
air conditions, as shown in Figure 2.
Note that the dimethyl modified MOF-5
retains 65% of its hydrogen storage
capacity even after being exposed
to moist ambient air for 8 days. The
remarkable improvement in moisture
stability of MOF-5 can be explained
by the hydrophobic nature of the -CH3
group. The methyl group effectively
shields the carboxylate-metal sites and
prevents water molecules from protonating the carboxylate functionalities.
The hydrogen uptake capability of
unmodified MOF-5, methyl-MOF-5 and
dimethyl-MOF-5, after being exposed
to air with a relative humidity of 3237%, is summarized in Figure 2.
This approach seems to be an effective and commercially attractive route
towards the synthesis of water-stable
MOFs for hydrogen storage applications. Tuning the hydrophobicity of
MOFs will also have implications on
the ability of MOFs to separate gas
mixtures and this is currently under
investigation in our laboratory.
Literature:
[1] Yang, J.; Grzech, A.; Mulder, F.M.; Dingemans, T.J. Chem. Comm., 2011, 47, 5244.
Young Wild Idea:
Graphene Microheaters Based Flexible and Stretchable Display
Shou-En Zhu
shouen.zhu@tudelft.nl
http://sites.google.com/site/shouenzhu/
Flexible electronics hold a big
promise for future applications.
There are many factors that
contribute to the allure of flexible electronics; they are typically
more rugged, lighter, portable,
and less expensive to manufacture compared to their rigid
substrate counterparts. Therefore
it is believed that electronics on
rigid and brittle substrate will be
replaced by high performance
flexible and stretchable electronics plus substrates in the future.
I am very interested in this fantastic
scientific field. From Aug. 2009, I went
to Sungkyunkwan University in South
Korea, where the chemical vapor
deposition synthesis graphene on
nickel films had just been developed
[1]. I chose flexible and stretchable
electronics as my research topic. In the
first year, I gained the basis skills for
the wafer scale synthesis and transfer
of graphene films and exploited the
potential application in field effect transistor (FET) and strain gauge sensor
[2]. In the second year, I developed a
novel graphene-on-organic film fabrication method compatible with a batch
micro-fabrication process for electromechanically driven micro-actuators
[3]. The unique material characteristics
of graphene including negative
>>
Page 3
Inside Materials - Newsletter Delft Centre for Materials - December 2011
thermal expansion and high electrical
conductivity were first time exploited
to produce a bimorph actuation with
large displacement and rapid response,
however maintaining low power consumption. A special report “Microactuators: Graphene on dragonfly wings”
highlighted [4], “The integration of
graphene with organic films is an
effective strategy for creating nimble
electrical micro-actuators. This demonstration of the monolithic integration
of graphene as an active component
in micro-actuators opens the door to
various electro-mechanical and biomimetic applications of graphene–organic
hybrid structures.”
A possibly important application of
graphene that has not been studied
so far, is the application of graphene
in microscale or macroscale heaters.
The graphene film possesses excellent
properties that are required for heater
materials, such as medium resistance
(few hundred ohms per square),
extremely high working-temperature
(up to few thousand degree centigrade), and good processability. These
properties make graphene films a
suitable candidate for heater materials.
Furthermore, the flexibility and stretchability of graphene makes it wonderful to be used as interconnect and
resistance type microheater pixel unit
in display field. However, there is still
no work on graphene published in this
field. Therefore it is highly required to
make the first demonstration product
to attract the scientific attention. As
shown in Figure 1, even tiny electrical
power can drive the graphene microheater to generate heat.
The present proposal is in line with his
the PhD research on “Chemical vapor
deposition of graphene, a route to
wafer scale integration” that I work on
from Jan. 2011 in Prof. G.C.A.M. Janssen’s group.
The future…
I have the ambition to exploit this idea
in a new scientific research field for
graphene microheater.
Literature:
[1] Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.;
Kim, J. M.; Kim, K. S.; Ahn, J.-H.; Kim, P.;
Choi, J.-Y.; Hong, B. H. Large-scale pattern
growth of graphene films for stretchable
transparent electrodes. Nature 2009, 457,
706-710.
[2] Lee, Y.; Bae, S.; Jang, H.; Jang, S.; Zhu,
S. -E.; Sim, S. H.; Song, Y. I.; Hong, B. H.;
Ahn, J.-H. Wafer-Scale Synthesis and Transfer of Graphene Films. Nano Lett. 2010, 10,
490-493.
[3] Zhu, S. -E.; Shabani, R.; Rho, J.; Kim,
Y.; Hong, B. H.; Ahn, J.-H.; Cho, H. J.
Graphene-Based Bimorph Microactuators.
Nano Lett. 2011, 11, 977-981.
[4] Microactuators: Graphene on dragonfly
wings. NPG Asia Materials featured highlight
| doi:10.1038/asiamat.2011.57
Figure 1. Infrared microscope image of graphene microheater
for various electrical power settings.
IOP Conference Self Healing Materials ‘Cruising at Full Speed’:
Farewell to Joris Vogelaar and Richard van den Hof
The successful IOP Conference series
on Self healing Materials featured
its already 6th annual meeting at
the Goudse Schouwburg, Gouda, on
27 October 2011. The full program
covered 14 presentations and a
poster session on recent research
developments in metals, concrete,
asphalt, coatings, polymers and
functional self healing materials. A
special session featuring a spectacular
laser show finalized the program
(see http://www.agentschapnl.nl/
programmas-regelingen/6th-annualsymposium-iop-self-healing-materialscruising-full-speed-27-october for
the video clip). The laser show was
specifically dedicated to retiring
Richard van den Hof and Joris
Vogelaar who both played a major
role in the development of the self
healing materials research field in
the Netherlands. Furthermore, two
special and witty posters, prepared by
Alexander Schmets, covering Joris’ and
Richards’ achievements were displayed
during the farewell reception. As the
editorial team of the DCMat Newsletter
could get hold of these posters we
would herewith also like to thank
Joris and Richard for their great work
and contributions to the self healing
materials research field.
Self-Healing Materials: show case for implementing
the Lisbon Strategy
Introduction:
Initially as the manager of all IOP
Programs (SenterNovem), Joris
Vogelaar has been involved with the
IOP Self Healing Materials from the
very start in 2005. He was instrumental
for establishing the program, knowing
the Ministry and Policies inside-out.
In 2008 he chose as his last public
commitment to manage and mentor
the IOP Self Healing Materials. The
program progressed during his
>>
Inside Materials - Newsletter Delft Centre for Materials - December 2011
Page 4
(presentation course, Vlieland
Conference)
- Many publications to disseminate the
program to the public at large
Lisbon goals achieved:
The Lisbon Agenda intended to
make the European Union ‘the most
competitive and dynamic knowledgebased economy in the world’ by
2010: a partial failure. However, the
SHM-program, coordinated by Joris
Vogelaar, did achieve the Lisbon Goals.
Joris Vogelaar
Programma manager IOP Self Healing
Materials
NL Innovatie, Agentschap NL, Ministerie van
Economische Zaken, Landbouw & Innovatie
Juliana van Stolberglaan 148, 2595 CL Den
Haag
service from a pioneering stage into
a successful and well-known line of
research and innovation.
Leadership by experience:
- ‘Ain’t no mountain high enough’, that
requires an experienced cyclist.
- Great initiatives for the SHMresearchers are established
Conclusions:
A new successful Dutch program
on Self Healing Materials has been
established since 2005, involving
many (PhD)researchers, and industrial
companies. Internationally the broad
approach is being followed, but
Netherlands has become (per capita)
the leading nation in the field of SHM.
Joris Vogelaar has contributed greatly
to this through his coaching and
leadership skills.
Future Plans:
We expect that this strong-willed
person will also in the future, just as
he did during his entire career, make
the most of all opportunities he will
spot. Being more at home will, at least,
give him time for keeping up with the
ever increasing number of newspaper
articles on breakthrough developments
in the application of self healing
materials he helped to develop.
Self-Healing by Vision and Commitment
Introduction:
Representing the Dutch Polymer
Institute (DPI), Richard van den
Hof has been involved with the IOP
Self Healing Materials from the very
start in 2005. He supported from the
beginning the unique ‘multi-material’
approach. He was a prominent
member of the team who defended the
approach and convinced the officials at
the Ministry of Economic Affairs.
People, planet, polymers:
- Polymers are the most investigated
material class for self healing (Web of
Science).
- Composites of Polymers are second.
- Many new healing mechanisms and
chemistries for polymers have emerged
over the last 5 years
Growing a field to prominence:
As Self-Healing has been a topic in
medical and computer sciences for a
long time, the prominence of the topic
within the field of Materials Science
‘quantum leaped’ from the moment
Richard got involved.
Conclusions:
A new successful Dutch program
on Self Healing Materials has been
established since 2005, involving
many (PhD)researchers, and industrial
companies. Internationally the broad
approach is being followed, but
Netherlands has become (per capita)
the leading nation in the field of Self
Healing Materials.
Future Plans:
Further studies in astronomy and
active pursuit of leisure activities for
many years to come. Being more at
home will allow time for keeping up
with the ever increasing number of
professional publications in the field.
Richard van den Hof
Scientific Chairman, Performance Polymers,
Dutch Polymer Institute
Kennispoort , John F. Kennedylaan 2, 5612
AB Eindhoven, The Netherlands
Vice-chairman IOP Self-Healing Materials
Page 5
Inside Materials - Newsletter Delft Centre for Materials - December 2011
Correction: Interfacial Bonding of Polymer Coatings on Metal Substrates
In the last Inside Materials Newsletter of June 2011 there was an incorrect figure in the article of P. Taheri MSc.
‘Interfacial Bonding of Polymer Coatings on Metal Substrates’.
Figure 4 was supposed to contain three seperate graphs, but accidentaly ended up with three identical graphs.
Displayed below is the correct ‘figure 4’ for the article.
Figure 4. Infrared spectra of the adsorbed (a) succinic acid, (b) myristic acid, and (c) succinic anhydride molecules on pure zinc substrates.
Publications Self Healing Materials 2010 (and late 2009) TU Delft
Title: In situ determination of aging precipitation in deformed Fe-Cu and Fe-Cu-B-N alloys by time-resolved small-angle neutron scattering
Author(s): He SM, van Dijk NH, Paladugu M, et al.
Source: PHYSICAL REVIEW B Volume: 82 Issue: 17 Article Number: 174111 Published: NOV 12 2010
Title: The Mechanical Properties of AA2024 as Function of the Interrupted Ageing Conditions
Author(s): Risanti DD, Yin M, Chen JH, et al.
Conference Information: 6th International Conference on Processing and Manufacturing of Advanced Materials, AUG 25-29, 2009 Berlin,
GERMANY
Source: THERMEC 2009, PTS 1-4 Book Series: Materials Science Forum Volume: 638-642 Pages: 449-454 Part: Part 1-4 Published: 2010
Title: Autonomous damage initiated healing in a thermo-responsive ionomer
Author(s): Varley RJ, van der Zwaag S
Source: POLYMER INTERNATIONAL Volume: 59 Issue: 8 Pages: 1031-1038 Published: AUG 2010
Title: Routes and mechanisms towards self healing behaviour in engineering materials
Author(s): van der Zwaag S
Source: BULLETIN OF THE POLISH ACADEMY OF SCIENCES-TECHNICAL SCIENCES Volume: 58 Issue: 2 Special Issue: Sp. Iss. SI Pages:
227-236 Published: JUN 2010
Title: Applying SEM-Based X-ray Microtomography to Observe Self-Healing in Solvent Encapsulated Thermoplastic Materials
Author(s): Mookhoek SD, Mayo SC, Hughes AE, et al.
Source: ADVANCED ENGINEERING MATERIALS Volume: 12 Issue: 3 Pages: 228-234 Published: MAR 2010
Title: Thermally activated precipitation at deformation-induced defects in Fe-Cu and Fe-Cu-B-N alloys studied by positron annihilation
spectroscopy
Author(s): He SM, van Dijk NH, Schut H, et al.
Source: PHYSICAL REVIEW B Volume: 81 Issue: 9 Article Number: 094103 Published: MAR 1 2010
Title: The effect of cluster plasticisation on the self healing behaviour of ionomers
Author(s): Varley RJ, Shen S, van der Zwaag S
Source: POLYMER Volume: 51 Issue: 3 Pages: 679-686 Published: FEB 5 2010
Title: A numerical study into the effects of elongated capsules on the healing efficiency of liquid-based systems
Author(s): Mookhoek SD, Fischer HR, van der Zwaag S
Source: COMPUTATIONAL MATERIALS SCIENCE Volume: 47 Issue: 2 Pages: 506-511 Published: DEC 2009
Title: Preparation of capsules containing rejuvenators for their use in asphalt concrete
Author(s): Garcia A, Schlangen E, van de Ven M, et al.
Source: JOURNAL OF HAZARDOUS MATERIALS Volume: 184 Issue: 1-3 Pages: 603-611 Published: DEC 15 2010
Title: Influence of curing condition and precracking time on the self-healing behavior of Engineered Cementitious Composites
Author(s): Qian SZ, Zhou J, Schlangen E
Source: CEMENT & CONCRETE COMPOSITES Volume: 32 Issue: 9 Pages: 686-693 Published: OCT 2010
Title: Healing of Porous Asphalt Concrete via Induction Heating
Author(s): Liu QT, Schlangen E, van de Ven M, et al.
Conference Information: 4th Conference of the European-Asphalt-Technology-Association (EATA), JUN 14-15, 2010 Parma, ITALY
Source: ROAD MATERIALS AND PAVEMENT DESIGN Volume: 11 Special Issue: Sp. Iss. SI Pages: 527-542 Published: 2010
Title: Induction heating of electrically conductive porous asphalt concrete
Author(s): Liu QT, Schlangen E, Garcia A, et al.
Source: CONSTRUCTION AND BUILDING MATERIALS Volume: 24 Issue: 7 Pages: 1207-1213 Published: JUL 2010
Title: Self-healing behavior of strain hardening cementitious composites incorporating local waste materials
Author(s): Qian S, Zhou J, de Rooij MR, et al.
Source: CEMENT & CONCRETE COMPOSITES Volume: 31 Issue: 9 Pages: 613-621 Published: 2009
Title: An Analytical Model for the Probability Characteristics of a Crack Hitting an Encapsulated Self-healing Agent in Concrete
Author(s): Zemskov SV, Jonkers HM, Vermolen FJ
Conference Information: 12th CASC International Workshop, SEP 06-12, 2010 Tsakhkadzor, ARMENIA
Source: COMPUTER ALGEBRA IN SCIENTIFIC COMPUTING Book Series: Lecture Notes in Computer Science Volume: 6244 Pages: 280-292
Published: 2010
Title: BioGeoCivil Engineering
Author(s): Jonkers HM, van Loosdrecht MCM
Source: ECOLOGICAL ENGINEERING Volume: 36 Issue: 2 Special Issue: Sp. Iss. SI Pages: 97-98 Published: FEB 2010
Title: Application of bacteria as self-healing agent for the development of sustainable concrete
Author(s): Jonkers HM, Thijssen A, Muyzer G, et al.
Conference Information: 1st international Conference on BioGeoCivil Engineering, JUN 23-25, 2008 Delft Univ Technol, Delft, NETHERLANDS
Source: ECOLOGICAL ENGINEERING Volume: 36 Issue: 2 Special Issue: Sp. Iss. SI Pages: 230-235 Published: FEB 2010
Title: A mathematical analysis of physiological and morphological aspects of wound closure
Author(s): Javierre E, Vermolen FJ, Vuik C, et al.
Source: JOURNAL OF MATHEMATICAL BIOLOGY Volume: 59 Issue: 5 Pages: 605-630 Published: NOV 2009
Title: Validation of a fast scanning technique for corrosion inhibitor selection: influence of cross-contamination on AA2024-T3
Author(s): Garcia SJ, Muster TH, Hughes AE, et al.
Conference Information: 5th Symposium on Aluminium Surface Science and Technology, MAY 10-14, 2009 Leiden, NETHERLANDS
Source: SURFACE AND INTERFACE ANALYSIS Volume: 42 Issue: 4 Pages: 205-210 Supplement: Suppl. SI Published: APR 2010
Title: Adhesion at Al-hydroxide-polymer interfaces: Influence of chemistry and evidence for microscopic self-pinning
Author(s): Vellinga WP, Eising G, de Wit FM, et al.
Source: MATERIALS SCIENCE AND ENGINEERING A-STRUCTURAL MATERIALS PROPERTIES MICROSTRUCTURE AND PROCESSING Volume:
527 Issue: 21-22 Pages: 5637-5647 Published: AUG 20 2010
Title: A thermodynamic approach to healing in bitumen
Author(s): Kringos N, Scarpas A, Pauli T, et al.
Conference Information: 7th International RILEM Symposium on Advanced Testing and Characterisation of Bituminous Materials, MAY 27-29,
2009 Rhodes, GREECE
Source: ADVANCED TESTING AND CHARACTERISATION OF BITUMINOUS MATERIALS, VOLS 1 AND 2 Pages: 123-132 Published: 2009