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Department of Chemistry

Portrait of sc10015

Our research interests cover a wide range of problems in colloid and interface science from adsorption of molecules to solid surfaces from liquids to the structure and behaviour of particles in complex fluids.

Adsorption from solution

The adsorption of molecules from liquids and solutions to solid surfaces is central to many areas of academic and industrial importance such as colloidal stability, lubrication, protein biofilms and making icecream. We have recently developed a combination of experimental methods, including coherent and incoherent neutron scattering and STM, that can provide details of the state, absolute composition and crystallographic structure of the adsorbed layers. Currently projects are available to investigate formation of crystalline layers for a number of interesting materials and also to probe their surface mixing behaviour. In particular, we are investigating a novel 'non-covalent' interaction - 'halogen-bonding' as a way of organising molecules on a surface. Halogen bonds can be thought of as the new hydrogen bond: the are relatively strong, directional and can be controlled by playing with the chemistry of nearby constituents. We have been successful in preparing co-crystals on a surface using these special interactions and now are using computer calculations (DFT) to understand in detail the roles of different interactions on controlling the monolayer structure. These layers form very stable mono and multilayers, materials with important industrial and biological relevance.



Figure illustrating a monolayer co-crystal held together by a halogen bond. The sigma hole is the site on the halogen (Iodine in this case) that accepts the electrons from the adjacent nitrogen on the neighbouring molecule. The halogen bonds give rise to characteristic chains of molecules in this case.

Adsorption to metal surfaces

We have recently developed a number of novel approaches (polarised neutron reflection, sum frequency generation non-linear optics, sensitive calorimetry etc) to investigate adsorption of particular species to the surfaces of metals and metal oxides in oils and water. These systems have major importance industrially in lubrication, wear, friction modification, implant rejection etc.. hence we have an important role to play in energy efficiency, corrosion and biomedical areas. We have been able to identify what is adsorbed at these surfaces, how much is present, what the structure of the layer is, the strength and nature of surface binding, even to the level of the conformational order of the alkyl chains of the adsorbed species. Recently we have extended this work to include the study of these interfaces under external fields such as elevated temperature and imposed shear flow. We already have some interesting results that indicate that thin (20A) molecular layers are largely unaffected by a shear flow up to 1000s-1. In contrast, much thicker(1500A) layers are strongly effected by imposed shear flow. This has important implications for our understanding of lubrication.

Figure (left) showing neutron reflection data from the mica water interface. The 'double critical edge' in the D2O sample is a characteristic of this interface. 

Adsorption to minerals

We have recently succeeded in making neutron reflection measurements from the surface of mica. Mica is a key mineral in many surface studies as it is atomically flat and smooth and has very interesting surface charge behaviour. However, it is very difficult to study by the usual neutron reflection methods. Recently we have been able to perform these experiments by preparing a very thin supported mica substrate and have used this to probe surfactant adsorption as a representative example of the technique.We have recently been able to study other important minerals including silica and calcite important in many commercial areas such as oil recovery and as overbase agents in fuel.

Figure illustrating neutron reflection from the calcite oil inteface with a schematic illustration of the adsorbed monolayer.

Orientation and deformation of Colloidal Particles

Many industrially useful materials are dispersions of tiny particles suspended in another medium, called a 'colloidal dispersion'. These particles may be rod or plate shaped; for example, pigments in inks and clay particles in paper coatings. The orientation of the particles can have a big effect on the flow behaviour of the material. We have been developing approaches that allow the orientation distribution of particle to be fully characterised. In addition, we have also developed synthetic approaches for novel shape changing particles. We are also interested in 'deformable' particles that can change shape under an external influence, like applied pressure. One of the projects currently available is to study assemblies of deformable particles, with particularly important applications in energy production.

Much of the work is at international facilities including: Institute Laue-Langevin, Grenoble, France, ISIS, Rutherford Appleton Laboratory, Oxon, UK, and ESRF, Grenoble, France.

BP Institute

My appointment is joint between the Department of Chemistry and the BP Institute at the University of Cambridge.

The group welcomes approaches from prospective M. Phil and Ph D. students at any time. Applications for 10-12 week summer fellowships are also welcomed.


New insights into the solid-liquid interface exploiting neutron reflectivity
RJL Welbourn, SM Clarke
– Current Opinion in Colloid and Interface Science
Potassium, Calcium, and Magnesium Bridging of AOT to Mica at Constant Ionic Strength
FJ Allen, CL Truscott, P Gutfreund, RJL Welbourn, SM Clarke
– Langmuir
Competitive Adsorption of a Multifunctional Amine and Phenol Surfactant with Ethanol on Hematite from Nonaqueous Solution.
C-L Chia, RM Alloway, I Jephson, SM Clarke, SV Filip, FR Siperstein, C Avendaño
– J Phys Chem B
Anionic surfactant induced desorption of a cationic surfactant from mica
FJ Allen, CL Truscott, RJL Welbourn, SM Clarke
– Applied Clay Science
Characterising Surfaces of Garnet and Steel, and Adsorption of Organic Additives
J Poon, DC Madden, MH Wood, SM Clarke
– Langmuir
An X-ray and neutron reflectometry study of iron corrosion in seawater
MH Wood, TJ Wood, RJL Welbourn, J Poon, DC Madden, SM Clarke
– Langmuir
Synthesis of transparent dispersions of aluminium hydroxide nanoparticles.
B Chen, J-X Wang, D Wang, X-F Zeng, SM Clarke, J-F Chen
– Nanotechnology
Preparing macromolecular systems on surfaces: general discussion
D Amabilino, I Bâldea, O Barykina, J Batteas, P Besenius, P Beton, N Bilbao, M Buck, L Chi, S Clarke, G Costantini, J Davidson, P Davies, S De Feyter, Y Diaz Fernandez, D Dwivedi, K-H Ernst, A Flood, J Gautrot, A Jabbarzadeh, V Korolkov, A Kühnle, M Lackinger, C-M Pradier, T Rahman, R Raval, S Schwaminger, J Seibel, SL Tait, J Teyssandier, H Zuilhof
– Faraday discussions
Supramolecular systems at liquid-solid interfaces: General discussion
D Amabilino, I Bâldea, P Besenius, P Beton, M Blunt, M Buck, NR Champness, L Chi, S Clarke, G Costantini, S De Feyter, Y Diaz Fernandez, D Dwivedi, K-H Ernst, A Flood, B Hirsch, R Jones, A Kühnle, M Lackinger, TR Linderoth, N Martsinovich, A Mount, M Nalbach, C-M Pradier, T Rahman, R Raval, N Robinson, M Sacchi, S Schwaminger, SL Tait, P Woodruff, H Zuilhof
– Faraday Discuss
SFG Study of the Potential-Dependent Adsorption of the p-Toluenesulfonate Anion at an Activated Carbon/Propylene Carbonate Interface
EK Humphreys, MTL Casford, PK Allan, CP Grey, SM Clarke
– Journal of Physical Chemistry C
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01223 336469

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