Chalmers University of Technology and AkzoNobel Pulp and ... · Chemicals, Sweden; de Lame Céline...

Chalmers University of Technology

and

AkzoNobel Pulp and Performance Chemicals

organize

Frontiers of silica research 2013

A workshop focusing on recent research

within the field of silica chemistry

March 25-26, 2013 (lunch-to-lunch)

Lecture hall KE in Chemical and Biological Engineering building

Chalmers University of Technology, Gothenburg, Sweden

1

Content

Program

Session 1 2 - 3

Session 2 3 - 4

Session 3 5

Session 4 6

Abstracts invited speakers 7 - 15

Abstracts other oral contributions 16 - 30

Abstracts poster presentations 31 - 43

List of participants 44 - 45

2

Program Monday, March 25, 2013

11.00 -12.00 Registration

12.00 -13.00 Lunch

13.00 -13.10 Welcome Krister Holmberg

13.10-15.00 Session 1 – Chairman Michael Persson

13.10-13.40 Invited speaker

“Silica particles at air-water, oil-water and air-oil surfaces” Bernard P. Binks, Anaïs Rocher and Andrew T. Tyowua, Surfactant & Colloid Group, Department of Chemistry, University of Hull, Hull. HU6 7RX. U.K. 13.40 - 14.10 Invited speaker

“Drying films of aqueous silica dispersions” Bernard Cabane, Lucas Goehring*, PMMH, ESPCI, Paris, France, *MPI-DS, Göttingen, Germany 14.10 – 14.30

“Raspberry-like silica particles for superhydrophobicity“ C.C.M.C. Carcouët, A.C.C. Esteves, R.A.T.M. van Benthem and G. de With; Laboratory of Materials and Interface Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands

3

14.30 – 14.50

“Modified Colloidal Silica for Enhancement of Dirt Pick-up Resistance in Deco Paints.” Greenwood Peter and Lagnemo Hans, AkzoNobel Pulp and Performance Chemicals, Sweden; de Lame Céline and Claeys Jean-Marie, CoRI, Belgium

14.50 – 15.20 Coffee

15.20 - 17.40 Session 2 – Chairman Aleksandar Matic

15.20 – 15.50 Invited speaker

“Molecular design and some properties of nanostructured porous silicates and hybrid silicates” Clément Sanchez, Collège de France : Laboratoire de Chimie de la Matière Condensée de Paris, CNRS, Université Pierre et Marie Curie. Collège de France, 11 Place Marcelin Berthelot, Bâtiment D. 75231, Paris, France. 15.50 – 16.20 Invited speaker

“Aligning Silica” Brad Chmelka, Department.of Chemical Engineering, University of California, Santa Barbara, California, U.S.A. 16.20 – 16.40

“Biomimetic synthesis of silica hollow spheres” M.W.P. van de Put , E.R.H. van Eck*, G. de With, N.A.J.M. Sommerdijk; Eindhoven University of Technology, *Radbout University Nijmegen

4

16.40 – 17.00

“A study of the structural evolution in ionogels by in situ SAXS- Raman spectroscopy” Moheb Nayeri, Anna Martinelli; Applied Surface Chemistry, Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden 17.00 – 17.20

“Silica/alkali ratio dependence of the microscopic structure of sodium silicate solutions” Jonas Nordströma, Andreas Sundblomb,c, Grethe Vestergaard Jensend, Jan Skov Pedersend, Anders Palmqvistc and Aleksandar Matica, aDepartment of Applied Physics, Chalmers University of Technology, Gothenburg, Sweden, bAkzoNobel Pulp and Performance Chemicals, Bohus, Sweden, cDepartment of Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden, dDepartment of Chemistry & Interdisciplinary Nanoscience Center (iNANO), Faculty of Science and Technology, Aarhus University, Aarhus, Denmark 17.20 – 17.40

“Silica nanoparticle – lipid membrane interaction studies: a contribution to the development of nano(Q)SAR” Laura De Battice, Rickard Frost, Andreas Sundblom*, Michael Persson*, Margareta Wallin**, Joachim Sturve** and Sofia Svedhem; Dept. of Applied Physics, Chalmers University of Technology, *AkzoNobel, Bohus, ** Dept. of Biological and Environmental Sciences, University of Gothenburg

17.45 – 18.30 Poster session with refreshments

18.30 Buffet dinner

5

Tuesday, March 26, 2013

08.30-10.10 Session 3 – Chairman Andreas Sundblom


“Intracellular Drug Release Using Spin-Coated Films of Mesoporous Silica Nanoparticles for Tissue Engineering Applications” Mika Lindén,* Dominique Böcking,* Oliver Wiltschka,* Cecilia Sahlgren**; Department of Inorganic Chemistry, University of Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany* Department of Biomedical Engineering, Technical University of Eindhoven, P.O.Box 513, 5600 NV, Eindhoven, The Netherlands** 09.00 – 09.30 Invited speaker

“Structure and order in mesoporous materials from small-angle x-ray scattering investigations” Jan Skov Pedersen; iNANO Interdisciplinary Nanoscience Center and Department of Chemistry, University of Aarhus, DK-8000 Aarhus, Denmark 09.30 – 09.50

”Spectroscopic probing of enzymes immobilized in mesoporous silica” Nils Carlsson, Christian Thörn, Hanna Gustafsson, Krister Holmberg, Lisbeth Olsson, Björn Åkerman; Department of Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden. 09.50 – 10.10

“A solvent-free photochemical route for the synthesis of hybrid coatings, self-organized or mesoporous hybrid silica films” Céline Croutxé-Barghorn, Abraham Chemtob, Cindy Belon, Lingli Ni, Héloïse De Paz; Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3, rue Alfred Werner 68093 Mulhouse Cedex, France

10.10 – 10.40 Coffee

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10.40-12.30 Session 4 – Chairman Anders Palmqvist


“Porous silica-based particles and monoliths for controlled uptake, delivery and separation” Lennart Bergström; Department of Materials and Environmental Chemistry, Stockholm University, Sweden 11.10 – 11.30

“Attaching particles with unusually wide and short pores on substrates – a new type of mesoporous silica films” Emma M. Björk, Fredrik Söderlind and Magnus Odén; Nanostructured Materials, Dept. of Physics, Chemistry and Biology, Linköping University, SE-58183, Sweden 11.30 – 11.50

“Core-shell silica cubes” Sonja I.R. Castillo*, Dominique M.E. Thies-Weesie, Samia Ouhajji, Janne-Mieke Meijer, Vera Meester, Andrei V. Petukov and Albert P. Philipse; Van `t Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute, Utrecht University, The Netherlands 11.50 – 12.10

“Transient colloidal stability controls particle formation of SBA-15” Tomas Kjellman, Juanfang Ruan, Yasuhiro Sakamoto* and Viveka Alfredsson; Physical Chemistry, Lund University, Lund, Sweden, *Department of Materials and Environmental Chemistry, Stockholm, Sweden 12.10 – 12.30

“Different approaches to obtain self-cleaning paints and coatings” Anders Törncrona; AkzoNobel Pulp and Performance Chemicals, Bohus, Sweden

12.30 Concluding remarks + Lunch

7

Abstracts invited speakers

(in alphabethical order)

8

Porous silica-based particles and monoliths for controlled uptake, delivery and separation

Lennart Bergström

Department of Materials and Environmental Chemistry, Stockholm University, Sweden Abstract This talk will present recent research on the synthesis, functionalization and processing of porous silica-based particles with tuneable external and internal surface properties for controlled uptake, release and separation.

After a brief description how surfactant-templated mesoporous silica spheres can be synthesised a detailed account will be given how these carriers can be used for controlled release and delivery. Confocal laser scanning microscopy (CLSM) has been used to follow the time-dependent transport of charged fluorescent dyes and fluorescently tagged macromolecules within mesoporous silica spheres with a well-defined pore size. Relating bulk release to the local molecular transport within the mesopores provides an important step toward the design of new concepts in controlled drug delivery and chromatography.

We will also report a robust and versatile membrane protein based system for selective uptake and release of ions from nanoporous particles sealed with ion-tight lipid bilayers of various compositions that is driven by the addition of ATP or a chemical potential gradient. We have successfully incorporated both a passive ion channel–type peptide (gramicidin A) and a more complex primary sodium ion transporter (ATP synthase) into the supported lipid bilayers on solid nanoporous silica particles. Outlooks for durable carriers with membrane-protein containing lipid membranes for functional studies of single or cascading membrane protein systems and as delivery vehicles and biomimetic micro-reactors will be discussed. Pending time, we will also introduce a novel and facile powder processing approach for the rapid production of mechanically stable hierarchically porous materials from porous particles, e.g. mesoporous silica particles, diatomite powders and zeolites. Examples on how the pore size distribution can be engineered will be shown and efforts on shape control will be demonstrated together with gas separation performance. References: 1. J. Boon Sing Ng, P. Kamali-Zare, H. Brismar, and L. Bergström, Langmuir, 24, 11096, (2008) 2. G. Nordlund, J. Boon Sing Ng, L. Bergström, and P. Brzezinski, ACS Nano, 3, 2639 (2009) 3. J. Boon Sing Ng, P. Kamali-Zare, M. Sörensen, P. Alberius, H. Brismar, N. Hedin and L. Bergström, Langmuir, 26, 466 (2010) 4. P.O. Vasiliev, Z. Shen, R.P. Hodgkins, and L. Bergström, Chem. Mater. 18, 4933 (2006) 5. P. Vasiliev, F. Akhtar, J. Grins, J. Mouzon, C. Andersson, J. Hedlund and L. Bergström,”, ACS Appl. Mater. Interfaces, 2, 732 (2010) 6. F. Akhtar, Q. Liu, N. Hedin, L. Bergström, Energy & Environmental Science, 5, 7664 (2012)

9

Silica particles at air-water, oil-water and air-oil surfaces

Bernard P. Binks, Anaïs Rocher and Andrew T. Tyowua

Surfactant & Colloid Group, Department of Chemistry, University of Hull, Hull. HU6 7RX. U.K.

Colloidal particles may adsorb at a range of fluid-fluid interfaces including air-water, oil-water

and air-oil. As a result, they are responsible for the stabilisation of foams (aqueous and non-

aqueous) and emulsions (simple and multiple). Such dispersed systems may be stable

indefinitely to disproportionation and coalescence due to a close-packed layer of particles around

bubbles or drops. The controlled assembly of particles at liquid interfaces also enables the

preparation of novel materials, including dry water. The lecture will discuss our recent findings

using silica particles in the following three areas:

(i) Preparation of powdered emulsions using particle mixtures.

(ii) Oil powders and oil gels from Pickering emulsions.

(iii) Oil foams and oil marbles stabilised solely by particles of low surface energy.

10

Drying films of aqueous silica dispersions

Bernard Cabane , Lucas Goehring*

PMMH, ESPCI, Paris, France, *MPI-DS, Göttingen, Germany

We present results from small angle neutron and X-ray Scattering of evaporating colloidal films. A liquid film (10 µm thick) is cast by dip-coating a mica sheet with a concentrated aqueous silica dispersion (particle radius 8 nm). During evaporation, a drying front sweeps across the film, from the leading edge to the bottom. A beam is focused on a selected spot of the film, and interference patterns are recorded at regular time intervals. As the film evaporates, the patterns measure the ordering of particles, their volume fraction, the film thickness and the water content. At first, particles are pushed closer together by the evaporation, and the dispersion crosses over to a jammed state where flow is blocked by the lack of free volume. This happens at silica volume fractions in the range s = 0.3 to 0.5, depending on pH and ionic strength. When the distances between particle surfaces become shorter than about 1 nm, the particles jump to contact and the dispersion becomes a wet aggregated solid. For nanometric silica particles, this jump to contact takes place at a volume faction of about s = 0.6, while the volume fraction of the wet solid is 10% higher. Cracks propagate in this solid all the way to the aggregation front. If water is further removed, air invades the dispersion and becomes a continuous phase throughout the material. The amount of residual water is w =0.14. The whole drying process is completed in two minutes. An important finding is that, in any spot (away from boundaries), the number of particles is conserved throughout this drying process, leading to the formation of a homogeneous deposit. This implies that no flow of particles occurs in our films during drying, a behaviour distinct to that encountered in the iconic coffee stain drying.

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Silica Workshop 2013, Chalmers March, 2013

Aligning Silica

Brad Chmelka

Department.of Chemical Engineering

University of California, Santa Barbara, California, U.S.A. Crystalline materials have inherently anisotropic crystal planes that impart directional characters to their local structures and usually their long-range particle morphologies. By comparison, amorphous materials do not, resulting in local and bulk structures that are essentially isotropic in character. This, of course, has significant consequences for the macroscopic properties of the materials, among them, being the extent to which anisotropic properties can be introduced. Whereas crystalline solids can be processed into forms that exhibit long-range orientational order, this is often challenging for amorphous or disordered systems. Nevertheless, it is possible to introduce macroscopic orientational order into amorphous materials, including silica, by exploiting their interactions with commingled or co-assembled species. In particular, anisotropic liquid-crystal or block-copolymer phases can be used to induce long-range orientational ordering of silica nanocomposites by taking advantage of their responses to anisotropic fields or surfaces. Upon removal of the organic (or other) structure-directing species, nanoscale silica frameworks can be produced with high and stable extents of macroscopic alignment which manifest the directionality of the vestigial anisotropic liquid-crystal phase. Recent progress will be presented in measuring, understanding, and controlling the preparation and anisotropic properties of silica (or other inorganic oxides) with high degrees of macroscopic alignment.

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INTRACELLULAR DRUG RELEASE USING SPIN-COATED FILMS OF MESOPOROUS SILICA NANOPARTICLES FOR

TISSUE ENGINEERING APPLICATIONS

Mika Lindén,* Dominique Böcking,* Oliver Wiltschka,* Cecilia Sahlgren**

Department of Inorganic Chemistry, University of Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany* Department of Biomedical Engineering, Technical University of Eindhoven, P.O.Box 513, 5600 NV, Eindhoven,

The Netherlands**

Mesoporous silica nanoparticles have proven to be promising nanoparticulate carriers suitable for cell-specific delivery of drugs in vitro and in vivo. The high specific surface area and pore volume of mesoporous silica together with their inherent biodegradability and controllable narrow particle size distribution make this class of carriers especially suitable for the delivery of small molecular hydrophobic drugs. Most of the work to date has been focused on cancer therapy, where mesoporous silica nanoparticles have been administered either by intravenous or peritumoral injection or by oral delivery. Furthermore, mesoporous silica nanoparticles have been shown to have a high degree of biocompatibility at moderate doses, suggesting that the silica nanoparticles exhibit a low, albeit concentration dependent, toxicity. However, local drug delivery from particulate coatings of these nanocarriers or local depot delivery has attracted much less attention. Advantages of such systems include high local drug concentration, and possibilities for spatial and temporal control of the drug release profile. Here, the delivery geometry is fairly different as compared to for example i.v. administration, as the cells are in direct contact with a large number of particles. The high local silica concentration, time-dependent changes in the morphology and the mechanical properties of the surface can be expected to have important influences on cellular responses. Hence biocompatibility, cell attachment, proliferation, and drug delivery kinetics will be different from that observed for other administration routes. The presentation will cover these aspects as a function of film thickness and particle size and shape. Three different cell lines have been used for in vitro evaluation of biocompatibility, stem cell attachment and proliferation, as well as cellular uptake kinetics of bioactive cues. The stem cell differentiation could be greatly enhanced through intracellular release of the cues. The results are discussed based on the morphological and mechanical parameters of the films as compared to the preferred substrate properties of the different cells used in the study. The work represents a first step towards multifunctional bioactive films for tissue engineering utilizing the broad spectrum of controllable parameters available on the micro- and macrolevel when using particulate films based on mesoporous silica as local delivery systems.

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Structure and order in mesoporous materials from small-angle x-ray scattering investigations

Jan Skov Pedersen

iNANO Interdisciplinary Nanoscience Center and Department of Chemistry, University of Aarhus, DK-8000 Aarhus, Denmark

In-situ small-angle scattering measurements during synthesis of mesoporous silica can be used for obtaining quantitative information on the development of the structure and the hexagonal order. A model based on the work by Förster et al.1 has been developed and implemented. It employs a factorization of the scattering intensity into contributions from a form factor describing the cylindrical structure and a structure factor describing the ordering of the cylinders. The cylinders are modelled as core-shell structures with graded interfaces. The structure factor describes the ordering into the hexagonal arrangement in a liquid-crystalline arrangement and takes into account disorder and finite domain size of the ordered regions. The model also includes a contribution from separate cylindrical structures that are not ordered. The model can be used for describing the scattering data from the entire synthesis from the first aggregation between the silica and surfactant to the formation of the final well-ordered material. The model has been used for analysing data from laboratory2,3,4 and synchrotron small-angle x-ray scattering (SAXS)5 ,6 ,7 and from small-angle neutron scattering (SANS)5. The model will be outlined and the detailed information on the kinetics that it can provide will be presented and discussed for selected examples. The general picture that emerges is that first cylindrical silica containing micelles are formed, then particle/domain formation is induced by micelle-micelle association caused by the surfactant-silica interaction, and finally rearrangement of the internal particle structure into a hexagonal arrangement occurs.

1 Förster, S.; Timmann, A.; Konrad, M.; Schellbach, C.; Meyer, A.; Funari, S. S.; Mulvaney, P.; Knott, R., J. Phys. Chem. B 2005, 109, 1347-1360. 2 Sundblom, Andreas; Oliveira, Cristiano L. P.; Palmqvist, Anders E. C.; Pedersen, Jan Skov., Journal of Physical Chemistry C 2009, 113, 7706-7713.

3 Sundblom, Andreas; Oliveira, Cristiano L. P.; Pedersen, Jan Skov; Palmqvist, Anders E. C., Journal of Physical Chemistry C 2010, 114, 3483-3492.

4 Sundblom, Andreas; Oliveira, Cristiano L. P.; Pedersen, Jan Skov; Palmqvist, Anders E. C. Microporous and Mesoporous Materials 2011, 145(1-3), 59-64.

5 Manet, Sabine; Schmitt, Julien; Imperor-Clerc, Marianne; Zholobenko, Vladimir; Durand, Dominique; Oliveira, Cristiano Luis Pinto; Pedersen, Jan Skov; Gervais, Christel; Baccile, Niki; Babonneau, Florence; Grillo, Isabelle; Meneau, Florian; Rochas, Cyrille (2011Journal of Physical Chemistry B 2011, 115(39), 11330-11344. 6 Michaux, Florentin; Baccile, Niki; Imperor-Clerc, Marianne; Malfatti, Luca; Folliet, Nicolas; Gervais, Christel; Manet, Sabine; Meneau, Florian; Pedersen, Jan Skov; Babonneau, Florence. Langmuir 2012, 28(50), 17477-17493. 7 Schmitt, Julien; Imperor-Clerc, Marianne; Michaux, Florentin; Blin, Jean-Luc; Stebe, Marie-Jose; Pedersen, Jan Skov; Meneau, Florian. Langmuir 2013, 29(6), 2007-2023.

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Molecular design and some properties of nanostructured porous silicates and hybrid silicates

Clément Sanchez

Collège de France : Laboratoire de Chimie de la Matière Condensée de Paris, CNRS, Université Pierre et

Marie Curie. Collège de France, 11 Place Marcelin Berthelot, Bâtiment D. 75231, Paris, France. [email protected]

Hybrid inorganic-organic materials can be broadly defined as synthetic materials with organic and inorganic components which are intimately mixed. They can be either homogeneous systems derived from monomers and miscible organic and inorganic components, or heterogeneous and phase-separated systems where at least one of the components’ domains has a dimension ranging from a few Å to several nanometers. Hybrid phases can also be used to nanostructure or texture new inorganic nanomaterials (porous or non porous). Research on hybrids has experienced an explosive growth since the 1980s, with the expansion of soft inorganic chemistry processes. The mild synthetic conditions provided by the sol-gel process such as metallo-organic precursors, low processing temperatures and the versatility of the colloidal state allow for the mixing of the organic and inorganic components at the nanometer scale in virtually any ratio. These features, and the advancement of organometallic chemistry and polymer and sol-gel processing, make possible a high degree of control over both composition and structure (including nanostructure) of these materials, which present tunable structure-property relationships. This, in turn, makes it possible to tailor and fine-tune properties (mechanical, optical, electronic, thermal, chemical…) in very broad ranges, and to design specific systems for applications. Hybrid materials can be processed as gels, monoliths, thin films, fibers, particles or powders or can be intermediates to design materials having complex shapes or hierarchical structures. The seemingly unlimited variety, unique structure-property control, and the compositional and shaping flexibility give these materials a high potential. Indeed, some hybrid materials are already commercial. This lecture will describe some recent advances on the molecular design. Some properties of resulting nanostructured porous silicates and hybrid silicates will be discussed. Some specific examples will be described such as new crystalline mesoporous materials and hierarchically structured porous systems made by coupling self-assembly and various processes such as ink-jet printing, aerosol, electrospinning, foaming ...

A few recent reviews :

Aerosol Route to Functional Nanostructured Inorganic and Hybrid Porous Materials Boissiere, Cedric; Grosso, David; Chaumonnot, Alexandra; et al. ADVANCED MATERIALS Volume: 23 Issue: 5 Pages: 599-623 , 2011 Applications of advanced hybrid organic-inorganic nanomaterials: from laboratory to market Sanchez, Clement; Belleville, Philippe; Popall, Michael; et al. CHEMICAL SOCIETY REVIEWS Volume: 40 Issue: 2 Pages: 696-753, 2011 Molecular and supramolecular dynamics of hybrid organic-inorganic interfaces for the rational construction of advanced hybrid nanomaterials Grosso, David; Ribot, Francois; Boissiere, Cedric; et al.CHEMICAL SOCIETY REVIEWS Volume: 40 Issue: 2 Pages: 829-848 2011 Design and properties of functional hybrid organic-inorganic membranes for fuel cells Laberty-Robert, C.; Valle, K.; Pereira, F.; et al. CHEMICAL SOCIETY REVIEWS Volume: 40 Issue: 2 Pages: 961-1005 2011 Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials , Rozes, Laurence; Sanchez, Clement CHEMICAL SOCIETY REVIEWS Volume: 40 Issue: 2 Pages: 1006-1030 2011 Bio-inspired synthetic pathways and beyond: integrative chemistry Prouzet, Eric; Ravaine, Serge; Sanchez, Clement; et al. NEW JOURNAL OF CHEMISTRY Volume: 32 Issue: 8 Pages: 1284-1299 2008 Design, synthesis, and properties of inorganic and hybrid thin films having periodically organized nanoporosity Sanchez, Clement; Boissiere, Cedric; Grosso, David; et al. CHEMISTRY OF MATERIALS Volume: 20 Issue: 3 Pages: 682-737 2008 Inorganic and hybrid nanofibrous materials templated with organogelators

mailto:[email protected]

http://apps.webofknowledge.com.chimie.gate.inist.fr/full_record.do?product=WOS&search_mode=Refine&qid=3&SID=W1AODgle6pgcCdajPC7&page=1&doc=1









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Llusar, Mario; Sanchez, Clement CHEMISTRY OF MATERIALS Volume: 20 Issue: 3 Pages: 782-820 2008 Photonic and nanobiophotonic properties of luminescent lanthanide-doped hybrid organic- inorganic materials Escribano, Purificacion; Julian-Lopez, Beatriz; Planelles-Arago, Jose; et al.OURNAL OF MATERIALS CHEMISTRY Volume: 18 Issue: 1 Pages: 23-40 2008 Biomimetism and bioinspiration as tools for the design of innovative materials and systems Sanchez, C; Arribart, H; Guille, MMG Source: NATURE MATERIALS Volume: 4 Issue: 4 Pages: 277-288 2005



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Abstracts other oral contributions


17

Spectroscopic probing of enzymes immobilized in mesoporous silica

Nils Carlsson, Christian Thörn, Hanna Gustafsson, Krister Holmberg, Lisbeth Olsson, Björn Åkerman

Department of Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden.

Abstract Immobilization of enzymes in mesoporous silica particles is a useful approach to facilitate product purification and enhance enzyme recovery. An important question is how the environment in the silica pores affects the enzymatic activity. We use UV/vis absorption and fluorescence spectroscopy of dye-labelled proteins to measure the enzyme concentration in the particles directly (as opposed to the conventional indirect Bradford method), and secondly probe the environment the immobilized proteins experience in terms of an effective pH. Thörn C, Carlsson N, Gustafsson H, Holmberg K, Åkerman B, Olsson L. Microporous and Mesoporous Materials 165 (2013) 240-246.

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Attaching particles with unusually wide and short pores on substrates – a new type of mesoporous silica films

Emma M. Björk, Fredrik Söderlind and Magnus Odén

Nanostructured Materials, Dept. of Physics, Chemistry and Biology, Linköping University, SE-58183, Sweden

A new type of mesoporous silica films consisting of SBA-15 particles, with extra wide and short pores, attached to silicon wafers have been fabricated in a simple one pot synthesis, and the formation mechanism of the films has been studied. All pores are open and easy to access, making them suitable for applications such as catalyst hosts and diffusion controlling membranes. Slightly modified recipes for synthesizing mesoporous silica rods and platelets at low temperature with additions of heptane and NH4F [1] was used, and substrates were added to the synthesis solution during the reaction. This yields porous films with unusually short (100-400 nm) and wide (10-14 nm) pores, see Figure 1, which are easy to access compared to the pores in films synthesized by the commonly used Evaporation-Induced Self-Assembly method [2]. The pore orientation can be tuned by for example variations in the surface functionalization of the substrate. The particles in the shape of rods or platelets are attached to the substrate by a foamy structure, as seen in Figure 1(a) and (b). The films’ growth behavior is closely correlated to the evolution of the mesoporous silica particles. Here, we have studied the time for adding substrates to the synthesis solution, the evolution of the films with time during formation, and the effect of hydrothermal treatment. For example, we found that the films are formed within 10 min after substrate addition to the synthesis solution when the rods are grown, that the pore sizes can be controlled by the hydrothermal treatment (see Figure 1), and that the substrate addition time is crucial for the formation of the films. The study has yielded a new route for synthesizing mesoporous silica films with a unique morphology consisting of separated particles with unusually large pores attached to a substrate.

Figure 1. Films synthesized with (a) rods and (b) platelets, and pore size distributions for films synthesized with various hydrothermal treatment temperatures.

[1] E.M. Johansson, M.A. Ballem, J.M. Córdoba, M. Odén, Langmuir, 2011, 27, 4994 [2] C.J. Brinker, Y. Lu, A. Sellinger, H. Fan, Advanced Materials, 1999, 11, 579

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Raspberry-like silica particles for superhydrophobicity

C.C.M.C. Carcouët, A.C.C. Esteves, R.A.T.M. van Benthem and G. de With

Laboratory of Materials and Interface Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands

Over the last decade, superhydrophobic surfaces have attracted much interest for both fundamental research and practical applications, mostly driven by the promise of self-cleaning properties of these coatings1. Mother Nature has delivered some of her secrets and research has revealed that the self-cleaning property of the Lotus leaf originates from a peculiar topology based on micro- and nanoscopic surface roughness combined with the hydrophobic properties of its epicuticular wax2. In a previous cooperation between DSM and TU/e, a nature-inspired approach – christened the ’raspberry’ approach – has been developed, leading to man-made superhydrophobic surfaces3. In this method, the key to introducing well-controlled dual-size (70/700 nm) roughness involved the synthesis of raspberry-like silica particles. Nowadays, superhydrophobicity is not sufficient for practical applications, and the trend is driving research to the development of multifunctional coatings. Therefore, tuning the size of the raspberry-like particles to appropriate dimensions would lead to new applications. Herein, we study the preparation of raspberry-like silica particles within the targeted range and the dependance of superhydrophobic properties on films originated from different sizes ratio of particles (Figure 1). The silica particles used here were prepared according to the Stöber method and a lysine based approach that will also be discussed. The synthesized particles were characterized by solid-state NMR and their morphology was evaluated by SEM and cryo-TEM.

Figure 1. Preparation of superhydrophobic films from raspberry-like particles (left) and cryo-TEM images of raspberry-like particles. Inset: water contact angle of a film made from the raspberry-like particles.

This work is financially supported by DSM Ahead, the Netherlands. 1 B. Bhushan, Y.C. Jung, K. Koch, Langmuir, 2009, 25, 3240-3248. 2 C. Neinhuis, W. Barthlott, Annals of Botany, 1997, 79, 667-677. 3 W. Ming, D. Wu, R. van Benthem, G. de With, Nano Lett., 2005, 5, 2298-2301. 4 T. Yokoi, J. Wakabayashi, Y. Otsuka, et. al., Chem. Mater., 2009, 21, 3719-3729.

NH2

NH2

NH2

NH2

S i2- Si H3

Si H3

SiH 3

Si H3S iH 3

S iH 3

O

O

O

OO

O

Substrate

Surface Hydrophobization

Superhydrophobic surface 50 nm

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Core-shell silica cubes Sonja I.R. Castillo*, Dominique M.E. Thies-Weesie, Samia Ouhajji, Janne-Mieke Meijer, Vera Meester, Andrei V. Petukov and Albert P. Philipse Van `t Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute, Utrecht University, The Netherlands *e-mail: [email protected] Although extensive research on colloidal silica has provided us a large body of literature, little is known about the behavior and properties of cubic-like colloidal silica particles. We present hollow silica cubes (Fig. 1a), which are easily prepared by a three-step colloidal synthesis procedure: template iron oxide cubic colloids are coated with a layer of amorphous and porous silica, after which the iron oxide core is removed by acid yielding hollow silica cubes [1]. The properties of these silica cubes can be adapted to the desired application by modifying the edge length of the cubes, the thickness and the porosity of the silica coating. The size of the cubes can be tuned between 500 and 1500 nm, while still maintaining the cubic-like shape. These cubes assemble readily into larger structures with varying degrees of order, depending on the assembly method [1-3]. We intend to employ assembled cubes to demonstrate a proof-of-principle of Cubicle Membranes; separation membranes built from hollow silica cubes packed on an appropriate substrate (Fig. 2). Convective assembly methods can yield assemblies with long-range order, but the conditions are not easily controlled and the covered surface is not sufficient for practical applications. Assembly by means of forced sedimentation using an excess pressure, on the other hand, is well controllable but does not yield as long-range ordered structures (compare Figs. 1B and 1C). However, the latter method seems most suitable for the preparation of Cubicle Membranes and also enables us to investigate the permeation properties of the formed dense-packed assemblies.

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Fig 2. Schematic illustration of a Cubicle Membrane. Hollow silica cubic colloids pack into a layer on top of a substrate. The cubes have a porous silica layer with thickness d and an edge length L larger than the pore size of the substrate.

References [1] Rossi, L.; Sacanna, S.; Irvine, W.T.M.; Chaikin, P.M.; Pine, D.J.; Philipse, A.P. Soft Matter 2011, 7, 4139-4142 [2] Meijer, J.M.; Hagemans, F.; Rossi, L.; Byelov, D.V.; Castillo, S.I.R.; Snigirev, A.; Snigireva, I.; Philipse, A.P.; Petukhov, A.V. Langmuir 2012, 28, 7631 7638 [3] Jiang, L.; de Folter, J.W.J.; Huang, J.B.; Philipse, A.P.; Kegel, W.K.; Petukhov, A.V. Angewandte Chemie Int. Ed. 2013, accepted

22

A solvent-free photochemical route for the synthesis of hybrid coatings, self-organized or mesoporous hybrid silica films

Céline Croutxé-Barghorn,

Abraham Chemtob, Cindy Belon, Lingli Ni, Héloïse De Paz

Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3,

rue Alfred Werner 68093 Mulhouse Cedex, France [email protected]

The silicon-based sol-gel process has been an outstanding stimulus in hybrid materials research. It has initiated a number of novel synthetic methodologies whereas composite chemistry was traditionally limited to a building block approach based on preformed inorganic particles or clusters. Either performed in presence of an organic polymer or simultaneously with an organic (radical) polymerization, the sol-gel synthesis implies in most instances the identification of an adequate solvent in which all the organic and inorganic components are compatible. Another limitation is the restricted range of organic monomers or macromolecules, which must comply with the specific reaction conditions of the sol-gel process. A flexible solvent-free sol-gel approach that would be easily suitable to an extended choice of polymers or polymerization processes would be highly profitable. This will open up the opportunity to convert many high utility polymers into hybrid materials by simply reinforcing their organic microstructure with an additional interpenetrated silica or metal oxide network. Therefore, the presentation will question the interest of sol-gel photopolymerization as a novel and simple route for hybrid coatings with reinforced mechanical properties, the synthesis of self-organized or macroporous and mesoporous (organo)silica films. For the first topic, an organic oligomer was mixed with a variable amount of a alkyltrimethoxysilane precursor bearing a reactive function in presence of photoinitiators. Upon UV irradiation, a type II polymer-polysiloxane nanocomposite film is achieved. Particular attention will be paid in investigating the competitive kinetics of both organic and inorganic reactions and characterizing the silica-based photocured films. This solvent and water-free sol-gel process was also implemented for the generation of self-organized hybrid films. Driven by hydrophobic van der Waals interactions, a photoinduced self-assemby process occurs to afford a long range ordered lamellar mesostructures films derived from a series of n-alkyltrimethoxysilane precursors.

Finally, we will prensent an alternative to the Evaporation Induced Self Assembly (EISA) method as a fast and simplified approach towards mesoporous silica films. The sol-gel process is photochemically triggered, thereby making mesostructuration independent of film deposition conditions, solvent evaporation and complex chemistry associated with a silica sol. The peculiarity of the photoinduced pathway is the opportunity to control the reaction kinetics. In addition, the absence of solvent, the photolatency of the formulations and the one-step process are major advantages for industrial applications.


23

1. Chemtob, C. Belon, D.L. Versace, C. Croutxé-Barghorn, S. Rigolet, Macromolecules, 41(20), 7390–98 (2008). 2. Belon, A. Chemtob, C. Croutxé-Barghorn, S. Rigolet, V. Le Houérou, C. Gauthier, Macromol. Mater. Eng., 296 (3-4), 506-516 (2011). 3. L. Ni, A. Chemtob, C. Croutxé-Barghorn, J., L. Vidal, S. Rigolet, J. Mater. Chem., 2012, 22 (2), 643 - 652. 4. H. De Paz, A. Chemtob, C. Croutxé-Barghorn, S. Rigolet, B. Lebeau, Microporous and Mesoporous Materials, 2012, 151(15), 88-92.

24

MODIFIED COLLOIDAL SILICA FOR ENHANCEMENT OF

DIRT PICK-UP RESISTANCE IN DECO PAINTS.

Authors: GREENWOOD Peter and LAGNEMO Hans, AkzoNobel Pulp&Performance Chemicals, Sweden

de LAME Céline and CLAEYS Jean-Marie, CoRI, Belgium

SUMMARY

For several years, the interest for nanotechnologies in the paint and coating industry is growing. Several researches carried out in CoRI have shown that by the use of nanoparticles such as colloidal silica, nanoTiO2, nanoceria, the mechanical and protective properties of water based systems (epoxy 2K, acrylics, UV) are strongly improved. Moreover, at that time, an important demand exists for multifunctional coatings e.g. protective and decorative coatings with anti-soiling and self-healing properties. In the past, it has been proved that the anti-soiling properties of some mineral paints could be modified by the use of modified colloidal silica in place of a part of the silicate binder.

In this study, the effect of the addition of silane modified colloidal silica dispersions in white deco paints has been investigated regarding to their dirt pick-up resistances (iron oxide and carbon black contaminations), their hiding powers and their behavior regarding open time.

It has been highlighted that the use of Bindzil CC301 to improve the dirt pick-up resistance or the anti-soiling properties of water based white deco paints is successful and finally the extent of DPU improvement depends on the nanoparticles content. The action of colloidal silica on the anti-soiling properties is resin and PVC dependent. The reduced dirt pick-up of the paints with nanoSiO2 is probably related to surface modification. It has been observed that the wetting of the dirtying solutions is less pronounced when nanosilica has been added to the paint. Moreover, the hiding powers of these paints are affected by the addition of colloidal silica. Very surprisingly, the paint opacity tends to increase with the nanosilica content. It can be assumed that the addition of Bindzil CC301 could change or modify the degree of dispersion of TiO2 and then affect positively the paint opacity. Finally and unexpectedly, the enhancement of the Open Time, in some cases doubled, without affecting surface tension during paint drying process was also observed.

25

Transient colloidal stability controls particle formation of SBA-15

Tomas Kjellman, Juanfang Ruan, Yasuhiro Sakamoto* and Viveka Alfredsson

Physical Chemistry, Lund University, Lund, Sweden, *Department of Materials and Environmental Chemistry, Stockholm, Sweden

In a recent publication we have studied the formation of mesoporous silica SBA-15 with cryo-TEM and HRSEM. We observe the formation of flocs (aggregates of silica, water and Pluronic micelles) that grow via random aggregation (figure 1, left). Nevertheless the particles in the final material have uniform size. A hypothesis of a transient colloidal stability as a controlling mechanism for the formation of particles is presented. Amphiphilic Pluronic polymers located at the interface of the flocs provide sterical stabilization and colloidal stability. Once a certain floc size is reached the surface coverage of stabilizing polymers is sufficient to obtain stability. This is shown schematically in figure 1 (right). The hypothesis is tested by introducing changes, aimed at influencing the properties of the Pluronic polymers, during the synthesis. The altered morphologies of the acquired particles are in accordance with predictions based of the hypothesis.

Figure 1. Left: Floc formation during the synthesis of SBA-15 taken 6 (a), 9 (b), 11 (c) and 13 (d) min after initiation via addition of the silica source, observed using cryo-TEM. The black arrows indicate growth via merging of two or more flocs. Right: The schematic representation of polymers at the floc interface. As the flocs grow in size the surface coverage of polymers increase with concomitant increase in colloidal stability. Scalebar 500 nm. [1] J. Ruan, T. Kjellman, Y. Sakamoto and V. Alfredsson, Langmuir, 2012, 28, 11567. [2] D. Zhao, Q. Huo, J. Feng, B. F. Chmelka and G. D. Stucky, Journal of the American Chemical Society, 1998, 120, 6024.

26

A study of the structural evolution in ionogels by in situ SAXS- Raman spectroscopy

Moheb Nayeri, Anna Martinelli

Applied Surface Chemistry, Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden

In this study we follow in situ the sol-gel synthesis of silica gels containing ionic liquid using time resolved Small Angle X-ray Scattering (SAXS) and -Raman spectroscopy simultaneously. The silica gel is formed by reacting silica precursor (tetramethyl orthosilicate, TMOS) with formic acid, mixed together with different concentrations of an imidazolium ionic liquid.1 The final materials with the ionic liquid nanoconfined in the silica network are also known as ionogels, a new material concept. The main focus is to elucidate the role of the ionic liquid in the sol-gel synthesis, with respect to network formation and local porosity, where the resulting materials are of interest for applications in diverse areas such as chemical separation, heterogeneous catalysis, and electrochemical devices (e.g. fuel cells). The ionic liquid used is 1-hexyl-3-methylimidazolium bis-(trifluoromethanesulfonyl)-imide (C6C1TFSI), which intrinsically forms nanoscale heterogeneities as proved by previous SAXS studies.2,3 The transport properties in the resulting ionogels have been further investigated by NMR diffusometry, to elucidate the effect of confinement on the self-diffusion of individual ions and on the ion-ion association.

Figure: The sol-gel synthesis using ionic liquid as solvent studied with -Raman spectroscopy and time resolved SAXS. The right graph shows the SAXS results for one of the measurement series.

[1] A. Martinelli, L. Nordstierna, Physical Chemistry Chemical Physics, 2012, 14, 13216. [2] O. Russina, A. Triolo, et. al., Journal of Physics: Condensed Matter, 2009, 21, 424121. [3] A. Martinelli, M. Maréchal, et. al., Physical Chemistry Chemical Physics, 2013, doi: C3CP00097D.

ID 13 @ ESRF

27

Silica/alkali ratio dependence of the microscopic structure of sodium silicate solutions

Jonas Nordströma, Andreas Sundblomb,c, Grethe Vestergaard Jensend, Jan Skov Pedersend,

Anders Palmqvistc and Aleksandar Matica

aDepartment of Applied Physics, Chalmers University of Technology, SE-412 96 Gothenburg, Sweden

bEka Chemicals AB, SE-445 80 Bohus, Sweden cDepartment of Chemical and Biological Engineering, Chalmers University of

Technology, SE-412 96 Gothenburg, Sweden dDepartment of Chemistry & Interdisciplinary Nanoscience Center (iNANO), Faculty of

Science and Technology, Aarhus University, DK-8000 Aarhus C, Denmark Abstract Alkaline sodium silicate solutions with SiO2:Na2O molar ratios in the range 4-10 are known to be colloidally unstable typically manifested in phase separation or gelation. The mechanistic understanding of this instability is generally poor. To improve this situation the microscopic structure of a series of solutions with ratios in the range 3.3-8.9 has been characterised using Small-angle x-ray scattering, Dynamic light scattering, Fourier transformed infrared spectroscopy, and 29Si Nuclear magnetic resonance spectroscopy to cover the relevant length scales related to silica clusters, aggregates, and particles present. In the starting solution, with ratio 3.3, there is silica present in three fractions. The main part is present as small silica clusters with a radius of 0.7 nm. There are also a significant portion of monomers/small oligomeric silica species as well as a minute amount of larger colloidal silica particles. At a higher SiO2:Na2O ratio, above approximately 4, smaller spherical colloidal particles are formed due to condensation reactions. However, as a result of a too high ionic strength the suspension is not stable and the particles aggregate to fractal structures with a size that depends on ratio and ageing time. At the highest SiO2:Na2O ratio, fractals are not formed because of the lower ionic strength and the smaller colloidal particles are stable in the solution. By carefully adding small amounts of NaCl to the high ratio solution it is possible to induce gelation of the solution confirming the hypothesis that the instability region is due to too high electrolyte concentration for the silica species present under those conditions.

28

Biomimetic synthesis of silica hollow spheres

M.W.P. van de Put , E.R.H. van Eck*, G. de With, N.A.J.M. Sommerdijk

Eindhoven University of Technology, *Radbout University Nijmegen

In Nature several examples of biosilica can be found but probably the most well-known examples are the diatom algae, see figure 1. These eukaryotic species are able to form nano-structured silica-based exoskeletons at relatively moderate conditions in terms of pH and temperature [1]. Additionally, it is most interesting that these species are able to obtain a highly cross-linked network, were de crosslink density remains almost constantly high upon growth [2]. The combination of proteins enriched in (phosphorylated) serines and lysines, long chain poly amines (LCPAs) and fully anionic peptides are believed to play a key role in the network formation process via electrostatic interactions [3-5]. Recently, it has been shown that charge interplay significantly increases nucleation rates [7] and that differences in condensation rates may result in similar network densities [8]. However, the mechanism and the role of other interactions are poorly understood.

Figure 1: SEM image of the highly ordered T. Pseudonana frustule. Image taken from ref 5. We have found an experimental procedure which allows us to control the silica formation kinetics of a water-soluble silica precursor at biomimetic pH. With this procedure, the assembly of formed nanoparticles can be studied with cryoTEM. We will use a range of different randomly sequenced poly(amino acid)s with different compositions in terms of hydrophilicity/hydrophobicity and positive/negative charges in order to study the role of charge distribution on the biomimetic silicification process. In order to get insight on the molecular level we will use solid-state 29Si-NMR combined with (in situ) FTIR spectroscopy to determine the degree of cross-linking. [1] M. Hildebrand et al., J. Mater. Res. 2006, 21, 2689. [2] C. Groger et al., J. of Struct. Biol. 2008, 161, 55. [3] N.Kroger et al., PNAS 2000, 97, 14133 [4] N. Kroger et al., Science 2002, 298, 584. [5] S. Wenzl et al., Angew. Chem.-Int. Edit. 2008, 47, 1729. [6] A. F. Wallace et al., JACS 2009, 131, 5244. [7] K. Spinde et al., Chem. of Mater. 2011, 23, 2973.

29

Silica nanoparticle – lipid membrane interaction studies: a contribution to the development of nano(Q)SAR

Laura De Battice, Rickard Frost, Andreas Sundblom*, Michael Persson*, Margareta Wallin**, Joachim Sturve** and Sofia Svedhem

Dept. of Applied Physics, Chalmers University of Technology, *AkzoNobel, Bohus, ** Dept. of Biological and Environmental Sciences, University of Gothenburg

To improve on the performance of silica-based nanomaterials, and to reduce environmental and health risks related to this development, it is important to learn about how engineered nanomaterials interact with e.g. biomolecules and biological barriers. We are also interested in the development of a generic screening methodology for nanoparticles, and to identify nanoparticle features which are likely to lead to effects in cells.

The present results have been obtained with a set of five silica nanoparticles, four of which were spherical (about 20 nm in diameter) and one of which had an elongated shape (roughly 4 x 20 nm). Size and zeta potential measurements were performed, and the adsorption profiles for the nanoparticles when interacting with each of four model lipid membranes of different composition and net charge were monitored in real time using the quartz crystal microbalance with dissipation monitoring (QCM-D). We found clear differences in adsorption profile on the model membranes with respect to surface coating, and particle shape. These results were compared to the results obtained when exposing frog cells to the same particles, using a conventional assay detecting cellular damage and cytotoxicity (through cell lactate dehydrogenase (LDH) release) and as well in experiments where the function of frog cells cultured on QCM-D sensors was studied by QCM-D (the method is published in Frost et al., Analytical Biochemistry, in press). In general, there were small effects on the cells.

The results will be discussed in the perspective of establishing (Q)SAR for nanoparticles.

30

Different approaches to obtain self-cleaning paints and coatings

Anders Törncrona

AkzoNobel Pulp&Performance Chemicals, Bohus, Sweden

Abstract

There are a number of existing approaches to try to accomplish self-cleaning paints and coatings. Both paints and coatings represent applications which are demanding. Depending on application, the willingness to pay for technical solutions that provide self-cleaning properties to paints and coatings differs enormously.

In this presentation the concepts of superhydrophobicity and superhydrophilicity will be described briefly. Examples of applications where these two concepts are put into practice will be presented. Further, aspects on production costs and sustainability of technologies to accomplish self-cleaning paints and coatings will be discussed in general. Decorative paints represent one application in which the technical solutions must be very cost efficient in order to be of interest. Coatings on sport optics represent another application where the focus is technical performance rather than cost efficiency.

A general remark is that the technical solutions to self-cleaning have to be as cost efficient and sustainable from an environmental perspective as the application in question requires. Hereby, there are obvious differences between publications in this field of science emanating from academia versus publications from industry. Whereas publications from industry often emphasize both cost efficiency and sustainability aspects, these aspects are seldom reflected in publications from academia. The final part of the presentation will account for a number of parameters that are crucial to address when developing new cost efficient and sustainable concepts for self-cleaning paints and coatings.

31

Poster Abstracts


32

Gels with anisotropic nano-structure made of colloid silica spheres and clay plates and its effect on diffusion and pressure driven permeability

Christoffer Abrahamsson,*a, Lars Nordstiernaa, Johan Bergenholtzb, Annika Altskär c and Magnus Nydénd

a Applied Surface Chemistry, Department of Chemical and Biological Engineering, Chalmers University of Technology b Physical Chemistry, Department of Chemistry and Molecular Biology, University of Gothenburg

c Structure and Material Design, SIK - Swedish Institute for Food and Biotechnology d Ian Wark Research Institute, University of South Australia

We report on the anisotropic liquid permeability characteristics of a new type of colloid hydrogel. These gels are synthesised by self-assemble from aqueous sol mixtures of colloidal silica and nontronite clay particles. Magnetic fields are used to align the clays in the composite before gelation, resulting in uniaxial alignment of clays on the centimetre scale, where the silica particles acted as a matrix, fixing the clay sheets into position after the magnetic field is removed. Clay orientation and thereby permeability and diffusion coefficient was varied by gelling the dispersions either in a magnetic field, causing uniaxial orientation of clays parallel to the flow direction, or without a field, resulting in random orientation. When keeping silica concentration fixed at 4.1 vol% and varying the clay concentration between 0-0.7 vol%, and comparing gels with uniaxially aligned versus randomly aligned clays, the maximum difference in permeability was found in the 0.7 vol% samples. In this case, the alignment of clays resulted in a doubled permeability. Likewise, the self diffusion coefficient was larger in the aligned samples, where the biggest difference in coefficient was 10%, found at a clay concentration of 0.5 vol%. Our findings show that the presence of clays in colloid silica gels have significant effect on silica gel liquid permeability, which is worth considering when colloid silica is used in, for example, petroleum well engineering or ground stabilization applications. Furthermore, such results could also be used to improve current battery and fuel cell technology.

TEM image of embedded section from a silica/clay gel Birefringence of clay gel aligned in magnetic field seen between optical polarizers

http://www.cmb.gu.se/english/

http://w3.unisa.edu.au/iwri/staffpages/magnusnyden.asp

33

Ionic liquid gel electrolytes for lithium-ion batteries

Luis Aguilera1, Jonas Nordström1, Ida Meschini2, Fausto Croce2, Per Jacobsson1, and Aleksandar Matic1

1Deparment of Applied Physics, Chalmers University of Technology, Göteborg, Sweden 2Dip. Di Scienze del Farmaco, Universita G. D’Annunzio Chieti-Pescara, Chieti, Italy

Lithium ion batteries are currently state of art technology used in portable devices. Nevertheless, due to the inherent hazard of their components, the scaling up of this technology into the electric vehicle market has been slow. An interesting approach is to replace the electrolyte, which is the most flammable component and decomposes into hazardous gasses, with an ionic liquid based gel electrolyte. The use of gel electrolytes has the advantage of suppressing both, the use of separators and the leakage characteristic of liquid electrolytes. Furthermore, due to the low vapor pressure, non-flammability, wide electrochemical window, among other interesting properties of ionic liquids, ionic liquids gels are of great interest for high power battery applications. In this work we focus on the characterization of two different gel electrolyte systems by means of vibrational spectroscopy, dielectric spectroscopy and differential scanning calorimetry. In one hand, the colloidal stability of a fumed silica-ionic liquid system is studied, as well as the effect of different anions. In the other hand, a polyvinylidene fluoride based electrospun membrane swelled by ionic liquids is examined. Both systems lead to stable gels with ionic conductivities comparable to those of the pure liquid electrolytes. Furthermore, only week interactions were found between the liquid component and the network, which accounts for the liquid-like conductivity. Moreover, the colloidal stability is strongly affected by the choice of ionic liquid and the addition of Lithium salt[1].

Figure 1. a) Fumed silica-Ionic liquid gels, b) FT-Raman showing BF4 stretching vibration and c) colloidal stabilization model based in solvation layers.

[1] J. Nordström, L. Aguilera, and A. Matic, Langmuir 28, 4080 (2012).

34

Synthesis of High Silica SSZ-13 Chabazite with Controllable Particle Sizes Zebastian Bohström, Bjørnar Arstad, Karl-Petter Lillerud

Department of Chemistry, University of Oslo, PO Box 1033, 0315 Oslo, Norway. ([email protected])

Abstract

ka

k-a

kb kc

k-c

i. aggregation

kd

ii. densification iii . aggregation iv. densification

amorphous

crystalline

Scheme 1. CHA SSZ-13 mechanism describing aggregation, densification and crystallization steps.

The chabazite (CHA) type zeolite have been and remains to be of high interest both for academia and industry [1-8]. The unique CHA topology and framework have made it useful as a high selectivity catalyst in e.g., the methanol-to-olefin (MTO) process [9,10]. The objective of this study was to find a method for controlling the particle size of high silica CHA SSZ-13 zeolite. Study the importance and morphological effects of the hydrothermal synthetic variables and gel compositions. By monitoring the CHA SSZ-13 particle size growth and crystallisation process we have been able to formulate a mechanism for the synthesis system (see Scheme 1). A Chevron patent from 2001 by S. I. Zones et al. describes how to prepare 0.5-1.0 µm SSZ-62 Si/Al 25-40 [11]. We have optimized synthesis conditions and are thus able to prepare smaller CHA SSZ-13 zeolites at Si/Al 100. We can prepare CHA SSZ-13 zeolites with an average particle size distribution ranging from 0.25 – 4.5 µm in adequate yields. To a certain extent we are also able to control particle shape.

References

[1] Micropor. Mesopor. Mater., 153 (2012) 94. [2] Zeolites, 1 (1981) 130. [3] J. Chem. Soc. Faraday Trans., 87 (1991) 3709. [4] Chem. Commun., (1998) 1881. [5] Top. Catal., 52 (2009) 1272. [6] Micropor. Mesopor. Mater., 112 (2008) 153. [7] Stud. Surf. Sci. Catal., 174 (2008) 265. [8] Top. Catal., 9 (1999) 59. [9] J. Cryst. Growth, 50 (1980) 498. [10] J. Chem. Soc. Faraday Trans., 87 (1991) 3709. [11] U.S. Patent 6,709,644 B2, 2001.

stirring at room temperature hydrothermal treatment


35

Amphiphilic Silica Sols

Linda Ström1, Albin Klint2, Andreas Sundblom1,2, Krister Holmberg1, Romain Bordes1

1Chalmers University of Technology, Dpt. of Chemical and Biological Engineering, Applied Surface Chemistry, 412 96 Gothenburg, Sweden

2 AkzoNobel Pulp and Performance Chemicals, 445 80 Bohus, Gothenburg, Sweden

Hydrophobically (isobutyl/isopropyl groups) and hydrophilically (polyethylene glycol groups, PEG) modified silica sols have been prepared using a recently developed strategy, resulting in surface active silica sols. The surface activity of the sols has been studied with surface tension measurements at the air-water interface. In comparison, the interfacial activity of non-modified and solely hydrophobically modified silica particles mixed with PEG have been evaluated, showing the important role of the interaction of the PEG chain with the silica particles on the surface activity.

The modified particles have been used for emulsification tests on a model system based on dodecane or toluene as oil and water. The texture of the emulsions and the size of the droplets were characterized by optical microscopy. Independently of the ratio oil/water, oil-in-water emulsions were obtained. It was also found that the ratio hydrophobic/hydrophilic moiety was important to achieve a good stability of the emulsion.

This project is run in collaboration with AkzoNobel Pulp and Performance Chemicals (formerly known as EKA Chemicals).

36

Catalysis from a silica box Sonja I.R. Castillo*, C.E. (Lisette) Pompe and Albert P. Philipse Van `t Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute, Utrecht University, The Netherlands *e-mail: [email protected] Catalytic nanoparticles often have to be immobilized or confined so as to avoid flocculation or to enhance the possibility of recovery [1-3]. Additionally, confining the catalyst in a well-defined structure enables the formation of larger complexes with preserved catalytic functionality. We demonstrate that an iron oxide colloid inside a hollow silica box [4] in the presence of hydrogen peroxide can greatly promote the degradation of an organic molecule in a Fenton-like reaction [5]. The surface area of the iron oxide colloid and consequently, the catalytic properties, can conveniently be modified without changing the silica box (Fig. 1). We relate the accelerated degradation of the organic dye methylene blue as a function of various parameters, e.g., the amount of catalysts, using UV-vis spectroscopy. These catalytically active silica boxes distinguish themselves by their unique cubic-like shape, which makes a dense packing of nearly 100% possible. This feature is appealing for amongst others functionalized separation membranes with these silica boxes as building blocks (Fig. 2).

References [1] Jiang, Z.J.; Liu, C.Y.; Sun. L.W. J. Phys. Chem. B 2005, 109, 1730-1735 [2] Yang, Y.; Liu, X.; Li, X.; Zhao, J.; Bai, S.; Liu, J.; Yang, Q. Angew. Chem. Int. Ed. 2012, 51, 1–6 [3] Deng, Y.; Cai, Y.; Sun, Z.; Liu, J.; Liu, C.; Wei, J.; Li, W; Liu, C.; Wang, Y.; Zhao, D.; J. AM. CHEM. SOC. 2010, 132, 8466–8473 [4] Rossi, L.; Sacanna, S.; Irvine, W.T.M.; Chaikin, P.M.; Pine, D.J.; Philipse, A.P. Soft Matter 2011, 7, 4139-4142 [5] Lee, S.; Oh, J.; Park, Y. Bull. Korean Chem. Soc. 2006, 27, 489-494

37

Nano-Particle Reinforced Latex Dispersions with Modified Colloidal Silica

Peter GREENWOOD, Akzo Nobel Pulp and Performance Chemicals

SUMMARY

The effect of epoxysilane-modified colloidal silica, added to water-based coating formulations, on the mechanical properties of resin films was studied. In general, the effect of the silica particles depended strongly on the resin and other components of the coating formulation but very significant improvements of hardness could be observed. The effect on the abrasion resistance of the coatings was less clear but still noticeable in many coating systems. Also the modification ensures good compatibility with the resins and that the aesthetic properties of the coating (gloss and haze) are not compromised.

38

QCM-D as a method for monitoring enzyme immobilization in mesoporous silica particles

Hanna Gustafsson*, Christian Thörn**, Lisbeth Olsson** and Krister Holmberg*

*Applied Surface Chemistry, Chalmers University of Technology, Gothenburg, Sweden **Industrial Biotechnology, Chalmers University of Technology, Gothenburg, Sweden

Enzyme immobilization in mesoporous materials is a field of great interest, with applications in biocatalysis and biosensing. However, the immobilization process is not well understood and has mainly been studied by indirect measurements. This work demonstrates a direct method for real time study of enzyme immobilization in mesoporous silica particles using quartz crystal microbalance with dissipation (QCM-D). Prior to the enzyme immobilization silica-coated crystals were grafted with amine groups followed by adsorption of small (40 nm), spherical mesoporous silica particles. The influence of pH on the immobilization were studied using two different enzymes; lipase from Rhizopus oryzae and feruloyl esterase FoFAEC. Additionally, the enzyme immobilization into mesoporous particles was compared to a flat surface, non-porous silica particles and rehydroxylated mesoporus particles. The results show that the silica particles adsorbed readily to the amine-grafted surface and no desorption was observed at pH 5-6 whereas a minor continuous desorption occurred at pH 7-8. The frequency shift was extensively larger for the two enzymes in the mesoporous particles, implying a larger loading compared to both a flat silica surface and non-porous particles. The enzymes were also more stably immobilized in the porous particles and the results indicate that the enzymes are situated inside the pores and not only on the outer surface. QCM-D is a promising method for studying enzyme immobilization in mesoporous silica particles in real time and may be used to study other interactions with porous particles.

Figure 1. Typical QCM-D frequency and dissipation shifts during the process of particle binding and enzyme adsorption.

39

Nanodiamonds as Novel Optical Probes in Bioimaging I: Fabrication

Eva von Haartman, Neeraj Prabhakar, Hua Jiang*, Jixi Zhang, Tatiana A. Dolenko**, Olga A. Shenderova***, Igor I. Vlasov**** and Jessica M. Rosenholm

Center for Functional Materials, Laboratory of Physical Chemistry, Åbo Akademi University, Turku, Finland, *Nanomicroscopy Center, Aalto University, Espoo, Finland, **International Technology Center, Raleigh, USA,

***General Physics Institute, Russian Academy of Sciences, Moscow, Russia, ****Moscow State University, Russia

In situ imaging techniques have revolutionizing the area of biological and medical sciences by allowing detailed studies of biological systems. Especially fluorescence microscopy has proven to be a fast and reliable method for studying cellular events both in vitro and in vivo. Organic fluorescent dyes are typically used as imaging agents, despite drawbacks such as photobleaching and cytotoxicity. Thus, there is a demand for bright, stable, and non-toxic fluorescent markers. One such promising candidate is nanodiamond (ND), i.e. diamond structures of nanoscopic dimensions produced by detonation of carbon-containing explosives or by the high-pressure high-temperature methodi. NDs are non-cytotoxic, have excellent sorption properties to different biological and non-biological compounds for which reason they can be used as adsorbents as well as drug carriers. To expand this capability, we have coated irregularly shaped ND cores (Fig 1a) with silica creating highly monodisperse mesoporous silica nanocomposites (Fig 1b) for combined targeting, diagnostic and therapeutic actions.ii The silica layer drastically increases the amount of biologically active agents that can be attached or incorporated to the particles simultaneously creating a homogeneous and easily modifiable particle surface. The loading degree, as compared to pure ND, increased with two orders of magnitude from 1 wt-% for the ND to 110 wt-% for the composite particles. By further modification of the particle surface with functional groups the particles containing model drug could successfully be delivered into cells (Fig 1c), thus also demonstrating the bioimageable nanocomposites’ potential use as drug delivery vehicles.

Figure 1. High Resolution Transmission Electron Microscopy images of a) an irregularly shaped, nanodiamond core where twinning occurs on a {111} twin plane, and it’s electron diffraction ring pattern (bottom left corner), which is typical for ND samples and clear evidence of the cubic diamond crystal structure and b) mesoporous silica-coated nanodiamond cores. C) Live cell image of HeLa cells incubated for 48 h with b) dye-loaded, copolymer-coated composite nanoparticles.

5 nm [011] a) b) c)

40

Nanodiamonds as novel optical probes in bioimaging II: Application

Neeraj Prabhakar ,*, Tuomas Näreoja**,Eva von Haartman, Didem en Karaman, Tatiana Dolenko***, Satoru Hosomi****, Igor I.

Vlasov*****, Cecilia Sahlgren*,******, Jessica M. Rosenholm

Center for Functional Materials, Laboratory of Physical Chemistry, Åbo Akademi University, Finland, *Turku Centre for Biotechnology, University of Turku and Åbo Akademi University,

Finland, **Laboratory of Biophysics, Cell Biology and Anatomy, Institute of Biomedicine, University of Turku, Finland, ****Moscow State University, Russia, ****Tomei Diamond Co.

Ltd., Japan, *****General Physics Institute, Russian Academy of Sciences, Russia, ******Department of Biosciences, Åbo Akademi University, Finland

Nanodiamond (ND) is a novel nanomaterial possessing fluorescent properties that could be useful for applications in biology and optical imaging. NDs are photostable, non-toxic, biocompatible and have a high refractive index, making them highly suitable for bioimaging. NDs can emit bright internal fluorescence from unique nitrogen vacancy defects in the crystal lattice. Silica nanoparticles have been studied extensively as drug carriers. In this study we exploited the advantages of both ND and silica by integrating them into a new composite material, ND@SiO2, comprising a core of NDs coated with mesoporous silica. The novel composite nanomaterial was intended as a multifunctional nanosized theranostic probe for combined biomedical imaging and drug delivery. Our results demonstrate that the produced ND@SiO2 composites were not cytotoxic, microscopically detectable and suitable as drug carriers. The optical properties of the ND@SiO2 composites were evaluated as such and in a biological environment (cells). The microscopy results also showed the uptake of NDs in different cells lines. The large surface-to-volume ratio of the silica coating significantly enhanced the drug loading capability of the composite particle. High-resolution imaging such as STED was used for studying various protein interactions and specific targeting. Whereas the silica coating protected the loaded cargo from the physiological environment, an additional organic surface coating was shown to increase the cellular uptake and enhance the release of drugs with poor bioavailability.

Figure 1. a) Surface functionalized novel ND@SiO2 composites with copolymer (PEG-PEI) are efficient for intracellular delivery. b) High resolution STED imaging of ND. c) Photoluminescence from ND@SiO2 in HeLa cells.

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Hydrothermal stability of iron-exchanged zeolite BEA as NH3-SCR catalyst – Experimental and Modeling study

S.Shwan1*, J.Jansson2, L.Olsson1 and M.Skoglundh1

1) Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Gothenburg, Sweden 2) Volvo Group Trucks Technology, SE-40508 Gothenburg, Sweden

* corresponding author: [email protected], Tel: +46-(0)-31-7722943

1 Introduction

Understanding the fundamental deactivation mechanisms is very important for designing new catalysts and operation conditions for optimization of catalytic processes. For mobile applications of NH3-SCR catalysts, aging is a practical concern in terms of sizing the catalyst for the lifetime of the vehicle and in accounting for performance loss over time.

The objective of this work was to create a kinetic deactivation model of Fe-BEA as NH3-SCR catalyst with focus on the dynamics of the active iron sites before and after hydrothermal treatment.

2 Methods

Based on extensive experimental data of hydrothermally treated Fe-BEA at different temperatures and times [1], a 1D kinetic model was developed using the software AVL BOOST in combination with user defined files in FORTRAN to describe the kinetics and the fundamental deactivation mechanisms for Fe-BEA after hydrothermal treatment with focus on the dynamics of the active iron sites [2].

3 Results and Discussion

The kinetic ageing model describes the experiments well before and after aging. To simulate the deactivation process the number of active sites is decreased in the model to predict the effect of hydrothermal treatment of the samples. Our experimental study and kinetic modeling contribute to the understanding of the fundamental deactivation mechanisms of hydrothermally treated Fe-BEA as NH3-SCR catalyst with focus on the active sites. The results show how the dynamics of the different active sites together with activity studies can be used to create kinetic deactivation models.

Figure 1. Experimental and simulated NOX reduction during NH3-SCR. Fresh samples compared to hydrothermally treated sample at 7000C for 3h.

References [1]S. Shwan, R. Nedyalkova, J. Jansson, J. Korsgren, L. Olsson, M. Skoglundh, “Hydrothermal Stability of Fe-BEA as an NH3-SCR Catalyst”, Industrial & Engineering Chemistry Research 51 (2012) 12762 12772. [2]S. Shwan, J. Jansson, J. Korsgren, L. Olsson, M. Skoglundh, ”Kinetic modeling of H-BEA as NH3-SCR catalyst – Effect of hydrothermal treatment”, Catal. Today 197 (2012) 24-37.


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”Portfolio of Sympatec (System-Partikel-Technik)” Sjoerd Sluimer Sympatec Nordic

Sympatec as a renowned manufacturer of equipment for the characterisation of size, shape, distribution and concentration of particulate and disperse products and matters has based the development of its diverse instruments on the expertise of experts in particle technology and physics. The development of the now available instruments has always been based upon the guideline that specific physical principals have limitations, which have to be respected in order to achieve results of highest quality and reliability. All of the instruments are of modular design and realisation so that optimum technical solutions can be suggested to our customers for their specific demands. Our basic guideline has always been that the determination of the requested parameters (size, shape, distribution) for dry products and materials made in dry processes, dry analysis is the preferred method. Consequently, if the particulate matters are made in suspension or emulsion based processes, wet analysis is the preferred method: Dry powders should be analysed dry Compared to wet analysis where products are suspended in liquid first, the amount of sample analysed is significantly higher giving the user a more reliable result. No solvent is required and hence the sample is not affected by any solvent at all. Moreover the analysis time decreases into the second to millisecond range. Wet Dispersion for Suspensions or Emulsions Suspensions and emulsions are analysed with wet dispersing modules. Even if dry powders should be analysed dry using dry dispersers, those powders can be measured in suspension using wet dispersing modules as well. The choice of the suitable wet dispersion module is dependent on the particle size and material density, the chemical properties of the suspension liquid and the grade of desired automation.

Instruments Based upon above criteria Sympatec have made available an Assortment of instruments using Laser Diffraction (LD), Ultrasonic Extinction (USE), Image Analysis (IA) and Photon Cross-correlation Spectroscopy (PCCS) principles for the characterisation of size, shape, distribution and concentration. This assortment covers particles from diameters as small as on nanometre and as large as several centimetres. Instruments are available for applications in R&D environments, for standard lab control as well as for installations in process environments.

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Colloidal silica in gel batteries

Anders Törncrona, Peter Greenwood, Erika Stoltz

AkzoNobel Pulp and Performance Chemicals

Abstract

Colloidal silica can be used in gel batteries which is one type of sealed batteries, which are lead-acid rechargeable batteries. Sealed batteries are also called VRLA (valve-regulated lead-acid) battery. Sealed batteries comprise both AGM (absorbed glass mat) and gel batteries. Both types do not require regular addition of water to the cells and vent less gas compared with flooded lead-acid batteries. Gel batteries are characterized by a porous silica gel structure in which the electrolyte liquid is confined.

Colloidal silica can be used in the production of gel batteries. In this presentation, different types of colloidal silica, Bindzil GB, have been used to prepare gel electrolytes by mixing them with sulphuric acid. When using Bindzil GB in the production of gel batteries, the colloidal silica can be mixed in-line with sulphuric acid without any pre-treatment. The effect of different Bindzil GB grades on gel time and gel strength will be presented. i J.-P. Boudou, P. A. Curmi, F. Jelezko, J. Wrachtrup, P. Aubert, M. Sennour, G. Balasubramanian, R. Reuter, A. Thorel and E. Gaffet, Nanotechnology, 2009, 20, 235602. ii J.M. Rosenholm, C. Sahlgren and M. Lindén, Curr. Drug Targets 2011, 12, 1166.

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List of participants Aleksandar Matic Chalmers University of Technology [email protected] Anders Palmqvist Chalmers University of Technology [email protected] Anders Törncrona AkzoNobel PPC [email protected] Andreas Sundblom AkzoNobel PPC/Chalmers [email protected] Andrew Burgess AkzoNobel Corporate Research, UK [email protected] Ann Lindgärde AkzoNobel PPC [email protected] Anna Bergstrand Chalmers Innovationsteknik [email protected]

Anna Larsson Kron AkzoNobel PPC [email protected] Anna Martinelli Chalmers University of Technology [email protected] Ann-Cathrin Hellsén Höganäs AB [email protected] Aylin Atakan Linköping University, Sweden [email protected] Bernard Binks University of Hull, UK [email protected] Bernard Cabane ESPCI, Paris, France [email protected] Björn Åkerman Chalmers University of Technology [email protected] Bo Andreasson AkzoNobel PPC [email protected] Bo Larsson AkzoNobel PPC [email protected] Brad Chmelka Univ of California, Santa Barbara, Cal, USA [email protected]

Camille Carcouët Eindhoven Univ of Technology, the Netherlands [email protected]

Catarina Petersen AkzoNobel PPC [email protected] Céline Croutxé-Barghorn University of Haute-Alsace, ENSCMu, France [email protected] Christian Thörn Chalmers University of Technology [email protected] Christoffer Abrahamsson Chalmers University of Technology [email protected] Clément Sanchez Univ Pierre et Marie Curie. Collège de France [email protected] Cordula Weiss Chalmers University of Technology [email protected] Du-Hyun Lim Chalmers University of Technology [email protected] Emilia Liljeström Chalmers University of Technology [email protected] Emma Björk Linköping University, Sweden [email protected] Eva von Haartman Åbo Akademi University, Turku, Finland, [email protected] Freddie Hansson AkzoNobel PPC [email protected] Fredrik Solhage AkzoNobel PPC [email protected] Fredrik Söderling Linköping University, Sweden [email protected] Frida Iselau AkzoNobel PPC/Chalmers [email protected] Hanna Gustafsson Chalmers University of Technology [email protected] Hansi Rosenthal Bim Kemi Sweden AB [email protected] Hans-Åke Baltsen AkzoNobel PPC [email protected] Helena Wassenius BIM Kemi Sweden AB [email protected] Jae-Kwang Kim Chalmers University of Technology [email protected] Jan Skov Pedersen University of Aarhus, Denmark [email protected] Johan Pettersson AkzoNobel PPC [email protected] Johanna Dombrovskis Chalmers University of Technology [email protected] Johanna Eckardt Chalmers University of Technology [email protected] John Sandström AkzoNobel PPC [email protected] Jonas Engström AkzoNobel PPC [email protected] Kjell Andersson AkzoNobel PPC [email protected] Krister Holmberg Chalmers University of Technology [email protected] Lars Andersson AkzoNobel PPC [email protected] Lars Lindahl AkzoNobel PPC [email protected] Lars Nordstierna Chalmers University of Technology [email protected] Lene Schack AkzoNobel PPC [email protected]

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Lennart Bergström Stockholm University, Sweden [email protected] Luis Aguilera Chalmers University of Technology [email protected] Magnus Hagström AkzoNobel PPC [email protected] Magnus Jonsson AkzoNobel PPC [email protected] Magnus Odén Linköping University [email protected] Magnus Skoglundh Chalmers University of Technology [email protected]

Marcel van de Put Eindhoven Univ of Technology, the Netherlands [email protected]

Mats Halvarsson Chalmers University of Technology [email protected] Michael Persson AkzoNobel PPC/Chalmers [email protected] Mika Lindén University of Ulm, Germany [email protected] Mikael Rasmusson Bim Kemi Sweden AB [email protected] Moheb Nayeri Chalmers University of Technology [email protected] Per Restorp AkzoNobel PPC [email protected] Peter Greenwood AkzoNobel PPC [email protected] Peter Hell AkzoNobel PPC [email protected] Peter Norberg University of Gävle, Sweden [email protected] Peter Westbye AkzoNobel Surface Chemistry [email protected] Romain Bordes Chalmers University of Technology [email protected] Roy Hammer-Olsen AkzoNobel PPC [email protected] Samia Ouhajji Lund University, Sweden [email protected] Sanna Björkegren Chalmers University of Technology [email protected] Simon Isaksson Chalmers University of Technology [email protected] Sjoerd Sluimer Sympatec Nordic [email protected] Sofia Svedhem Chalmers University of Technology [email protected] Sonja Castillo Utrecht University, The Netherlands [email protected] Soran Shwan Chalmers University of Technology [email protected] Tomas Kjellman Lund University, Sweden [email protected] Yi-Guan Tsai AkzoNobel PPC, USA [email protected] Zareen Abbas University of Gothenburg [email protected] Zebastian Bohström University of Oslo, Norway. [email protected] Zhou Ye Höganäs AB [email protected]

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