Delft Centre for Materials Touching the future today Newsletter March 2007 issue 9 L A B O R AT O R Y P R O F I L E FROM ALUMINIUM ALLOYING TO V E R M E E R In this issue FROM ALUMINIUM ALLOYING TO VERMEER 1 PREDICTING THE TRAJECTORY OF CRACKS 2 DECISION STRATEGIES IN DESIGN 4 SBIR WORKSHOP SELF HEALING MATERIALS 5 IMPROVING POLYELECTROLYTE FUEL CELL MEMBRANES 6 MECHANICAL SPECTROSCOPY 7 ALERTS / AGENDA 8 Deadline contributions for next issue: 20th of April 2007 Delft University of Technology The work carried out by the Structure and Change in Materials research group, one of the 22 groups in the Delft Centre for Materials (DCMat), is extremely diverse, explains Prof. Barend Thijsse. The group’s work ranges from step-by-step improvement of alloys to researching suits of armour from the Middle Ages. By Peter Baeten On a scale between less than one picometre and approximately 0.1 micrometre, the group Structure and Change in Materials works on the research and improvement of the structure of mostly metals, alloys and semiconductors (no polymers). The group researches the materials under realistic ‘dirty’ conditions. This means, for example, even researching materials that are not in equilibrium (hence the term ‘Change’ in the group’s name). Prof. Barend Thijsse, leader of the group: 'Computer simulations make up a large part of the work. These allow us to design new materials, as it were. For example, in improving aluminium alloys we can substitute a certain element virtually with another element. This means that the work we do actually precedes the experimental research.' Therefore, one of the important research areas is the ‘design’ of materials, for example of alloys. This is an example of the work carried out in the Virtual Materials Laboratory, one of the four sections within the Structure and Change in Materials group. The other three are Solid State Trans- Jan Vermeer, Young Woman at a Virginal, ca. 1670, oil on canvas, private collection. formations, Materials in Art and Archaeology, and the X-ray Laboratory. The categorisation of these sections is a clear indication of just how diverse the research carried out by Barend Thijsse’s group is. This is also reflected in the research portfolio and the application area of the diverse research lines: they range from research into material defects to solid state transformations, thin films, hydrogen filters and the stability of semiconductors, to name but a few. Important experimental research methods for Barend Thijsse’s group are X-ray diffraction and X-ray fluorescence, carried out at the X-ray Laboratory. With these facilities, Structure and Change in Materials also fulfils an important function for other researchers from inside and outside TU Delft. In terms of public profile, however, the most striking in Barend Thijsse’s group is the group led by Joris Dik, Materials in Art and Archaeology. Subjects continued on page 2 Delft Centre for Materials WAARDE PROMOVENDUS PREDICTING THE TRAJECTORY One of the challenges in the development of finite element models for the prediction of crack growth is the creation and propagation of cracks in a truly mesh-independent way. The partition of unity method provides an elegant solution. By Joris Remmers The failure behaviour of materials can be studied using numerical techniques based on the finite element method. From a historical point of view, a distinction can be made between two techniques: smeared approaches and the discrete fracture models. In the smeared approach, failure in a material is modelled by decreasing the stiffness of the continuum elements according to a damage law to dissipate the correct amount of energy. Instead of creating a true crack in the model, the effects of the failure OF CRACKS process are smeared out over a specific width. The smeared approach fails to hold when the process zone, the area in the vicinity of the crack tip in which the material is undergoing irreversible deformations, is relatively small. The alternative in this case is a discrete failure approach, such as the cohesive surface formulation. Instead of smearing, the fracture processes are lumped into a single plane in front of the crack, the cohesive surface. The failure characteristics of the material are determined by an independent constitutive relation that describes the separation of the cohesive surface. The positions of traction free cohesive surfaces in the model mark the presence of a crack in the material. Conventionally, cohesive surfaces can be inserted in the finite element mesh as interface elements, which are placed be- Figure 2: Simulation of dynamic shear failure using the partition of unity approach. Left: trajectory of the crack at low impact velocities; Right: trajectory at high velocities. Figure 1:Cohesive surface model for the simulation of fast crack growth. In this model, cohesive surfaces are inserted as interfaces at all inter-element boundaries (Xu and Needleman, Journal of the Mechanics and Physics of Solids 42, 1994). tween two continuum elements. Unfortunately, this approach is problematic when the trajectory of the crack is not known beforehand. A possible solution is to add interfaces between all elements, as demonstrated in Figure 1. In this simulation, crack growth in arbitrary directions has been captured, but the approach is still meshdependent. First, the trajectory is constrained to a selected number of angles, which prevents small deviations to be captured. In addition, since the cohesive zones have a non-zero compliance continued on page 4 L A B O R AT O R Y P R O F I L E ( C O N T I N U E D ) at the interface of art, archaeology and technology are regularly the focus points of the group’s work. An example of this is Sylvia Leever, a student at TU Delft, who came up with the idea of researching old suits of armour to find out if they were really ‘bullet proof’ (for which she won the Young Wild Ideas Award of the Delft Centre for Materials). Leever researched the materials properties of 17th Century armour breastplates. Her research proposal was rather unconventional in the sense that she carried out destructive research on two breastplates specially purchased for the experiment (while many of such armour pieces can be found in museum). With the aid of rifle tests at TNO-PML, Leever was able to obtain a clear indication of the properties of these harnesses, and she came up with a model that will avoid destructive tests on such pieces of ‘cultural’ heritage in future. Another notable research project to come out of Joris Dik’s group concerned a controversial painting by Vermeer entitled Young Woman Standing at Virginal. The materials science researchers ascertained that the woman’s coat had probably been reworked. TU Delft was able to use this to pursue an important technical argument that supports the earlier findings of art historians (that the painting is quite definitely a Vermeer). With the help of modern electron microscopy from the Kavli Institute of Nanoscience at TU Delft, the researchers were able to determine that the yellow top layer of paint on the coat does not match the layer beneath. The white lead in the upper layer has a completely different struccontinued on next page Page 2 Newsletter ture. The grain size of the paint particles is larger and much more irregular than those in the layer of paint beneath. Moreover, small particles of aluminosilicate were discovered at the interface of the two layers, which were missing elsewhere in the layer of paint. The most probable explanation for this is dust pollution of the bottom layer of paint before the top layer was added. The weaker stylistic finish of the yellow coat can, therefore, be seen as a reworking, which is one of the important art historical arguments for attributing the canvas to Vermeer. But Dik’s research is not merely of public relations value only. Last year for example, an archaeological research project carried out with Leiden University resulted in the publication of an article in Nature. Materials science research at TU Delft into 3,200 year old glazed ceramics from the Middle East showed that an innovative embellishing technology had been developed there but was then later lost. Researchers examined ceramic pieces from 1200 BC that had been found in a ruined temple in what is now Jordan. They analysed the composition of a bowl made of faience (a type of Two identical nanowires: the copper nanowire (upper) and silicon nanowire (lower) have different fracture behaviour upon horizontal movement of the upper plateau. Computer simulations help to analyse the brittle fracture (lower, silicon) and ductile fracture (upper, copper) into fine detail. This research is important for future generation chips. glazed ceramic) and discovered small particles of the mineral chromite in the glazed coating. The discovery threw new light on the technology history of the Middle East. Chromite had never before been found in glazes from the Middle East before Roman times. It would appear that this remarkable technology sank into oblivion after the Late Bronze Age and has remained there until today. Another striking element of Barend Thijsse’s field of research is the forthcoming launch of the sports materials specialisation in the Materials Engineering Master’s programme, where Barend Thijsse’s group will play a prominent role. And not only in the area of education. According to Barend Thijsse, apart from offering courses, there will also be serious scientific research carried out in the field of sports materials. “A prominent source of research questions for Janssen’s field is the automotive industry, one of the biggest users of coating systems and surface treatments” In addition to these activities, Barend Thijsse ardently supports the DCMat overarching theme, self-healing materials. 'The subject is a little bit of a hype, but why not let it be a hype? The fact is, you have to create a lot of ideas in order to create good ones.' Cross section of the paint of the ’yellow coat’ at Vermeers ’Young woman at a virginal’. The upper left figure is an optical image. Proceeding clockwise mappings of the elemental distribution of the same cross section for various elements are shown. The upper and lower layers of the paint differ significantly in composition and structure. Moreover, the interface between the two paint layers is contaminated by large grains of feldspar (Al, Si). This suggests the upper paint layer was not by Vermeer, but an addition of later times. Apart from Barend Thijsse, the group Structure and Change in Materials comprises three associate professors, approximately fourteen post-docs and PhD students, and three technician support staff. Contact Information: Prof. Barend Thijsse: b.j.thijsse@tudelft.nl DCMat Page 3 WAARDE prior to cracking, the overall stiffness of the material is slightly smaller than expected, which may influence the results. “We developed finite element models for the prediction of crack growth and propagation in a truly mesh-independent way.” The alternative is to incorporate the cohesive zones as discontinuities in the continuum elements by employing the partition of unity property of finite element shape functions. The magnitude of this discontinuity is set by an additional set of degrees of freedom, which are added to the existing nodes of the finite element mesh. The discontinuities can be added and extended in the finite element mesh during a simulation, which allows for the simulation of crack propagation in arbitrary directions, irrespective of the structure of the finite element mesh. In addition, since a cohesive zone is only extended when needed, the use of a dummy stiffness prior to cracking is avoided and the number of additional degrees of freedom remains small. PROMOVENDUS (CONTINUED) In this thesis, the partition of unity approach has been used to investigate a number of fracture problems on different levels of observation. The method has been implemented in a solid-like shell element to analyse delamination buckling on a structural level. In an alternative Figure 3: Crack branching at the interface of a bimodel, the material specimen under tensile load. method is used to study been extended to analyse the the fast crack propagation in nucleation growth and coalessolids due to an impact load. cence of multiple cracks, as It can be seen in Figure 2 that demonstrated in Figure 3. the direction of the crack depends on the impact velocMore information ity, which is in agreement Joris Remmers with experimental observaJ.J.C.Remmers@TUDelft.nl tions. Finally, the method has MATERIALS HIGHLIGHT DECISION STRATEGIES IN DESIGN In the third week of January 2007 prof. Ashby from Cambridge taught at the Faculty of Architecture and concluded his visit as key-note speaker at the seminar Decision Strategies in Design. these various aspects bring in their alternative design suggestions in the stage of the amalgamation of the ideas: the stage where the ultimate design decisions have to be taken. By Fred Veer & Alexander Schmets The aspect of knowledge and how to use it in the design process was treated by Henri Christiaans of the Faculty of Industrial Design Engineering. He shed his light on the category of knowledge that is required by the designer, and to which extent decision tools, like CES, provide the designer with this knowledge. Closely related were the presentations of Wim Poelman of the Faculty of Architecture, who dedicated his presentation to the diffusion of technical knowledge in industrial design and of Rob Nijsse, who gave numerous Design is often considered as merely a creative process. However, at many stages in the design process decisions are taken, either intuitive or as a result of carefully considering various technical, aesthetic or psychological aspects. The ever increasing complexity of products as well as the environment in which these products are being used/applied asks for a concurrent and multidisciplinary approach of the design process, where experts on Page 4 examples from his experience as a structural designer, while Ilse van Kesteren focused on how materials are selected by designers, and the effect of this selection on the interaction with the user. It is clear that for making proper decisions, a classification of the important properties, faceted classification, plays an important role. Researchers from the unicontinued on page 5 Newsletter versity of Bath presented a software system that helps browsing through faceted schemes. The software is based on his own standard work ‘Materials Selection in Mechanical Design’, now in it’s third edition. Finally, the key note speaker Mike Ashby presented another design tool. This software, CES, provides the user withtools to help making design decisions quickly by providing information varying from Ecodesign to production costs. The faculty of architecture has introduced the Cambridge Engineering Selector software from Granta Design this academic year. To introduce the staff of the faculty of Architecture to the CES tool a series of courses was arranged on the 16th to 18th of januari where 58 staf members, varying form PhD students to full professors, were taught by Prof. Ashby personally how to use the software. The course was a great success and should contribute significantly to the successful use of the CES software, facilitating the use of materials science knowledge in the design curriculum. This software provides the user with tools to help making design decisions quickly by providing information varying from Ecodesign to production costs. VALORISING MATERIAL KNOWLEDGE SMALL BUSINESS INNOVATION RESEARCH (SBIR) WORKSHOP One of the many differences between the USA and the Netherlands is the speed with which new knowledge is transferred from the university to industry, where the application of this knowledge adds value. Such a difference is of course the result of a lot of factors but, according to the Dutch Ministry of Economical Affairs, an important factor could be the American Small Business Innovation Research programme (SBIR). We are very delighted that the departmental SBIR working group of the ministry has selected the area of Self Healing Materials as one of the areas were a future SBIR programme MATERIAL could become a success. Therefore, a special workshop on SBIR in relation to the area of self healing materials is being organized on 17 April, 09.0014.00, at the Ministry of Economical Affairs (Ministerie van Economische Zaken, Bezuidenhoutseweg 30, Den Haag). The programme will start of with a presentation on the Dutch SBIR initiative. Next two renowned guest speakers will share their views. Prof. Les Lee from the Airforce Office of Scientific Research (AFOSR) will present the new business development in the USA, where he is responsible for the funding of various research programmes in self healing materials, and Prof. Klaas van Breugel (TU Delft) will discuss the possibilities for commercializing self healing concrete. You are cordially invited to attend this workshop. For up-to-date information concerning the pilots and SBIR visit www.sbir.nl. For more information on this workshop contact: Patrick van Veenendaal (P.vanVeenendaal@senternovem.nl), SenterNovem, or Gerrit Linssen (G.J.M.Linssen@minez.nl), Min. van Economische Zaken FRIEND FRANK NUIJENS, PRESS OFFICER OF TU DELFT The ‘WTC-team’ (Science and Technology Communication) is part of the department of Corporate Communication at TU Delft. Our department has three science information officers who consult the Delft Research Centres (DRC’s) on their external communication and act as their press officers. The science information officer for the Delft Centre for Materials is Frank Nuijens. What’s our role? We are the communication consultants for the DRC’s, institutes and themes. Furthermore, we are the “press officers” for the DRC’s towards international, national, regional and specialized meDCMat Newsletter dia. We can also put you in touch with our communication consultant of the Valorization Centre if you have valorisation questions, or our public affairs officer who maintains and elaborates TU Delft connections in The Hague and Brussels. We are the ambassadors of the research within the DRC’s for the corporate communication of TU Delft. We try to incorporate this research into TU communication activities, like student recruitment, staff recruitment, internal communication, public affairs, valorization etc. We are the science communication officers for all the re- search within TU Delft. What can I do for you? I am your communication consultant, working mainly with the DRC management on strategic plans and the execution of them. I am also your science information officer and ambassador. Please keep in mind that my role as information officer and ambassador can only be successful if I am aware of your research activities. This approach works both ways: I will stay in touch with you to stay updated on research, to connect you to journalists who approach us with questions about your research subject and by informing you about communication initiatives at TU Delft which we can use to promote DRC research. On the other hand I need you to keep me updated on new developments. That way I can find the best way to communicate your information to the target audience. So please get in touch! How can you reach me? Frank Nuijens Prometheusplein 1, Delft (TU Delft Library) T: 015 - 278 4259 F: 015 - 278 1855 M: 06 - 140 151 18 E: F.W.Nuijens@tudelft.nl W: http://www.drc.tudelft.nl Page 5 MASTERING MATERIALS IMPROVING The 2006 Shell Bachelor Prize has been won by Leen van der Ham of the DelftChemTech section Nanostructured Materials, TU Delft. Van der Ham received the prize (2,500 euros) during the finals on February 13, for his Bachelor’s thesis on the possibilities of converting hydrogen to electricity. Shell Nederland and the technical universities of Delft, Eindhoven and Twente award the prize annually to motivate young talent to focus on sustainable development. DCMat congratulates Leen and his supervisors with this very honourable achievement. “At the moment the mass-application of fuel cells is still limited by the high costs involved with the membranes that are used, typically a perfluorinated sulphonic acid polymer known as Nafion. ” POLY-ELECTROLYTE FUEL CELL MEMBRANES eH+ Anode O2 in H+ + H+ H H+ Membrane Cathode H2O out Typical configuration of a hydrogen fed fuel cell A fuel cell is an energy conversion device, taking hydrogen and converting it into protons and electricity. The efficiency of the fuel cell is strongly dependent on the polymer electrolyte membrane and its ability to transport protons through the cell. At the moment the mass-application of fuel cells is still limited by the high costs involved with the membranes that are used, typically a perfluorinated sulphonic acid polymer known as Nafion. Also the properties of Nafion are not yet optimal for some operating conditions. A potential alternative for Nafion is a liquid crystalline polymer based on sulphonated polyaramid that has been developed by the NSM group. First tests have already shown that most of the properties of this material are suitable for use in a fuel cell, but unfortunately the mechanical properties proved to be insufficient. The main problem was that the membranes were too brittle, making them break very easily and therefore difficult to handle. Recently, I discovered that research on materials pays. On February the 13th I received the Shell Bachelor Award 2006 for my research project on a polymer fuel cell membrane, and was rewarded with the prize of 2500 euros. The Shell Bachelor Master Award is a relatively new annual prize presented to the best Bachelor and Masters students who have conducted a research project in the field of energy and sustainability. My Bachelor’s project, which I completed at the NanoStructured Materials (NSM) group at the Delft University of Technology, was about improving the mechanical properties of a new potential fuel cell membrane material. * H+ H2 in By Leen van der Ham H e- SO3H O N N * O H n During my research project, I investigated the possibilities for improving the mechanical properties by adding a second polymer to the sulphonated polyaramid. It was expected that adding a small amount of a flexible cationic polymer could result into a stronger material. The cationic polymer forms ionic bonds with the anionic sulphonic group of the rigid polyaramid. In this way it essentially glues the material together. However, the proton conduction properties of the material, which are introduced to the material by the sulphonic groups, may also decrease because of this ionic interaction. After analysing several mechanical and conducting properties of membranes with varying polymer ratios, I concluded that indeed the mechanical properties are improved by adding the second polymer. A good illustration of the result is the fact that it was possible to fold the membranes in two without breaking them. The conducting properties of the membranes were also affected by the ionic interaction; it resulted in a very slight but acceptable decrease. Although the conductivity at room temperature was found to be lower compared to Nafion, it was comparable at a temperature of 90 °C because of a strong dependence on the water content in the membrane that The structure of a sulphonated polyaramid polymer continued on page 7 Page 6 Newsletter INSTRUMENT OF THE MONTH MECHANICAL SPECTROSCOPY: USING INTERNAL FRICTION TO CHARACTERISE MICROSTRUCTURE Recently a new set up has been installed at the Reactor Institute Delft: an internal friction spectrometer for characterisation of the microstructure in metals. By David San Martin Mechanical Spectroscopy, also known as internal friction, is a spectroscopic technique in which a mechanical oscillating stress (applied by torsioning) at a certain frequency is applied on a solid. The stress applied has to be below the elastic limit of the material. Under this condition, the deformation will be recovered upon release of the applied stress. Deformation is composed of two contributions; the elastic (linearly proportional to the applied stress with an instantaneous response) and an anelastic contribution (much lower in magnitude and showing delayed response, which is due to dissipative, i.e. frictional, losses in the material). The anelastic response is related to the motion of defects (dislocations, interstitials, vacancies … etc.) and results in dissipation of energy. The internal friction is a measure of the mechanical energy dissipated and depends on the frequency and temperature applied during the experiment. This energy absorbed is directly related to the number and kind of mobile defects present inside the solid, as well as to the characteristic motion that they undergo. Therefore, the measurement of internal friction can be used to obtain information about the microstructure of the material in a nondestructive way. Instrument Specifications: - Temperature range:100-1200 K - Strain amplitude range:10-4 - 10-6 - Frequency range: 0.1–10 Hz - Sample dimensions: (L x W x T) 58 x 4 x 1 mm3 Contact information: David San Martin D.SanMartin@TUDelft.nl www.dcmat-is.tudelft.nl Schematic representation of a typical Me- The Mechanical Spectroscopy set-up at chanical Spectroscopy set-up. the Reactor Institute Delft The measurement of internal friction can be used to obtain information about the microstructure of a material in a nondestructive way. MASTERING MATERIALS (CONTINUED) IMPROVING POLY-ELECTROLYTE FUEL CELL MEMBRANES assists with proton transport. Altogether, this new material seems to be a good alternative for Nafion. According to the jury of the Shell Award, my research project was considered to have the best potential. For more details about the development of new polymeric materials for fuel cell membranes, contact Dr. Hayley Every (h.a.every@tudelft.nl), DCMat Newsletter Dr. Eduardo Mendes (e.mendes@tudelft.nl) , Prof. Stephen Picken (s.j.picken@tudelft.nl), or visit the NSM website (www.dct.tudelft.nl/nsm). Contact information: Leen van der Ham Chemical Engineering student l.v.vanderham@student.tudelft.nl Picture of a mechanically improved membrane Page 7 Delft Centre for Materials Visiting Adress Delft Centre for Materials P.O. 5058 2600 GB Delft Kluyverweg 1 2629 HS Delft Editorial Team Peter Baeten Eduardo Mendes Frank Nuijens Wim Poelman Joris Remmers Mario de Rooij Alexander Schmets Geeta van der Zaken Contributions Leen van der Ham David San Martin Barend Thijsse Fred Veer Contributions to the newsletter can be send to info.dcmat@tudelft.nl. Online You can find the online version of the newsletter in the Newsletter section of www.dcmat.tudelft.nl . Disclaimer The information in this Newsletter has been thoroughly checked by the editorial team. We can, however, not prevent that mistakes might occur. The Delft Centre for Materials does not take responsibility for these mistakes or any consequences there of. M AT E R I A L S A L E R T : DEADLINES AND MORE First International Conference on Self Healing Materials Young Wild Ideas International Lustrum Symposium, ‘SUSTAINABLE SOLUTIONS, Focus on Africa’ In about two weeks time the First International Conference on Self Healing materials will take place. By now, more than 170 delegates have registered. The conference will have a strong international character, and covers all major materials classes. The opportunity to register is still open. Please, if you don’t want to miss it, register online via www.selfhealingmaterials.nl By the end of May, beginning of June, the Young Wild Idea Committee will gather again and select from the newly received young wild ideas. If you have a good idea that has a connection with materials, please do not hesitate, but submit. Details about submission and proposal format can be found on the DCMat website. We invite you to submit an abstract on technological solutions to the social, ecological, and economic aspects of sustainable development. The scope includes research, educational and consultancy projects on one or more of the themes that can be found on the symposium website, that can be reached by clicking the banner on the TU Delft homepage. AGENDA UPCOMING EVENTS 4 April 2007, 15:00-16:30h Reactor Institute Delft, TU Delft Colloquium ‘Trans-disciplinary Research in the Bio- and Material Cultures at Qumran, the Site of the Dead Sea scrolls’, by Jan Gunneweg (CAAS) 17 April 2007, 09:00h, Ministry of Economical Affairs Workshop Small Business Innovation Research 18-20 April 2007, Noordwijk aan Zee, The Netherlands First International Conference on Self Healing Materials 7 May 2007, 15:00h, Aula TU Delft ‘A computational framework for uncertainty quantification in fibre-reinforced composites.’, thesis defence by D.B. Chung 8 May 2007, 10:00h, Aula TU Delft ‘3D Analysis of Fracture Processes in Concrete ’, thesis defence by G. Lilliu 9-10 May 2007, Eindhoven Vakbeurs Materials Engineering. Special theme: materials selection. 4 June 2007, 15:00h, Aula TU Delft ‘Modeling of Combined Physical-Mechanical Moisture Induced Damage of Asphaltic Mixes ’, thesis defence by N. Kringos 5 June 2007, 15:00h, Aula TU Delft ‘Reeling of Tight Fit Pipe ’, thesis defence by E.S. Focke 5 June 2007, 10:00h, Aula TU Delft ‘Permanent deformation of asphalt mixtures ’, thesis defence by P.M. Muraya 11 June 2007, 10:00h, Aula TU Delft ‘Pulse Cathodic Protection ’, thesis defence by D.A. Koleva 3-8 June 2007, Faculty of Civil Engineering, TU Delft Concrete Microscopy: a yearly course on the characterisation of the microstructure of cement based materials for MSC and PhD students as well as professionals from industry 2-5 July 2007, City Hall, Delft Workshop “Instabilities across the scales” 23-28 July 2007, Eifel Mountains, Germany The Second IDEA League Summer School on ‘Multiscale Modelling in Materials Science and Engineering’ Page 8