IAN WARK RESEARCH INSTITUTE ANNUAL

REPORT 2007

The

TM 2 Advisory Board Report 3 Director’s Report 4 Management Structure 6 Staff 8 Postgraduate Students 12 Major Research Sponsors 13 Research Funding 14 Research Highlights 45 Research Projects 50 Honours and Awards 53 Seminar Program 56 Visitors to the Institute 58 Conference Attendance and Invited Lectures 62 Publications 66 Graduates 68 International Collaborators

Ian Wark Research Institute ARC Special Research Centre for Particle and Material Interfaces

University of South Australia Mawson Lakes Campus Mawson Lakes Blvd Mawson Lakes South Australia 5095 Australia

T +61 8 8302 3694 F + 61 8 8302 3683 E [email protected] W www.unisa.edu.au/iwri

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Dr Tim Barnes using the Quartz Crystal Microbalance with Dissipation (QCM-D). This allows us to determine the kinetics of adsorption at a solid-liquid interface by monitoring changes in the sensor crystal oscillation frequency. For example, we are investigating PEG surface coatings to understand their resistance to protein adsorption, of interest for applications such as medical imaging and biodiagnostic devices

Ian Wark Research Institute Annual Report 2007  Advisory Board Report

The Advisory Board commends the thirteenth The membership of the Advisory Board will Annual Report of the Ian Wark Research Institute go through significant change in the coming (The WarkTM) to the Council of the University of year. Departing members - Prof Tom Healy, Dr South Australia. Brian Hickman, Dr Ray Shaw, Dr Megan Clark and Dr Jurgen Michaelis – all made outstanding Mineral processing research remains one of the contributions to The Wark’s progress. We gratefully mainstays of The Wark, and its outstanding quality acknowledge the support by them and their was highlighted in the fifth review of research by employers. Excellent replacements have agreed to the Research and Technology Advisory Committee join us. (RTAC). Our basic and applied research in other areas is also growing very strongly. The Wark has The Advisory Board continues to appreciate its developed a major strategic plan to 2016, with the constructive relationship with the Director. full support of RTAC and the Advisory Board. Issues concerning future scientific leadership, the stability Our warmest congratulations go to the recipient of of funding, the necessity for senior appointments the IWRI Medal for 2007, Dr Alan Kanta. and the formation of a substantial stabilization fund, are very important elements. Dr S M Richards, AM FTSE The Wark is a vital, even critical element in the Chair standing of the University of South Australia. The relationship is mutually beneficial, but both are June 2008 affected by any funding adversity. The annual revenue for 2007 was $17.5M. The Wark generated the bulk from external sources (43.4% from State/Federal Governments, 21.5% from industry). The cessation of major funding blocks (such as the Special Research Centre) without immediate replacement provides a significant challenge. Clearly we need the further support of the University, and our principal sponsors, to ensure the uninterrupted progress of The Wark. At another level, The Wark Fund is established under the chairmanship of Antony Simpson; it will take time to have a serious impact.

 Director’s Report

It is a great pleasure to present my report for 2007, the part of a national facility in nanofabrication and is thirteenth in the series. funded with contributions from the Federal and State Governments as well as from the University (see page In our complement of 151 staff and students, thirty 17 for further details). Excellent collaboration with seven different nationalities are represented. The the University of Tokyo enhances our capabilities in Wark attracts excellent postgraduate students and, in microfluidics in particular. addition, some twenty international visiting students spend periods of six to twelve months with us as part The second year of research under the Australian of their formal education. Some of these visitors return Mineral Science Research Institute (AMSRI) umbrella for formal PhD studies. We have many international has been excellent. The Wark is the headquarters researchers spending time with us and our research for AMSRI, a partnership with the Universities of staff frequently work in international laboratories and Melbourne, Newcastle and Queensland, with funding industrial operations. Our staff and students continue from the Australian Research Council, AMIRA to receive national and international recognition International, the four universities and the state for their efforts. Our immensely strong network of governments of South Australia and Victoria (for colleagues, scattered over all continents is a wonderful further information see page 14). resource. From an application perspective, our P260 project During 2007 we welcomed the following new staff: funded since 1988 and continuing even more strongly Mr Paul Byrne, Research Degrees/Project Officer; Mr today, has made a significant contribution to the Dom Davda, IT Officer; Mr Louie Del Castillo and efficiency of mineral sulphide flotation worldwide. Ms Maria Sinche Gonzalez who are both Research The Wark has been involved in this project since its Assistants within our Mineral Processing Sector; Dr inception. In 2007, an evaluation study of the P260 Renate Fetzer from Saarland University, Germany, Ms series of projects was conducted by RMDSTEM Ltd, Tracy Greeneklee, Dr Marta Krasowska from the Polish a specialist management consulting group with Academy of Sciences and Dr Mihail Popescu from the capabilities in the evaluation of R&D predominately Max Planck Institute of Metals Research Stuttgart, in the resources sector. Results show $436 million who will all be working within AMSRI (for further has been added to the minerals industry through the information see page 14); Ms Kim Gauci, who will give research outcomes of P260. Our ARC SRC research much needed administrative support to our Mineral in soft and hard interfaces provides the intellectual Processing Sector; Mr Colin Hall from Advanced underpinning to allow our research across The Wark Manufacturing and Mechanical Engineering within to continue to blossom and be enriched. Our insights UniSA; Dr Dusan Losic, ARC Australian Research Fellow into antibacterial coatings, using nanoparticles for from Flinders University; Dr Hui Tan from the University immunotargetting, developing nanotube membranes of Melbourne; Dr Su Nee Tan a former PhD student for molecular separations, probing the colloid stability who rejoins us from BASF, France; Dr Eric Tavenner a of nanoparticles of gold, exploring the limits of fine recent graduate of University of Queensland and native and coarse particle flotation, understanding the slip of the USA and Ms Tosha Tichy who has joined us after conditions for liquid flow over surfaces, and exploring working in industry for many years. the composition of fuel cell membranes and studying liquid structure at interfaces all owe their impetus to We also acknowledge the fine contributions from our our Special Research Centre support. departing staff: Dr Holly Aiqun to industry; Dr Kristen Bremmell to the University of Adelaide, Dr Andrew We are now engaged in setting firm plans in place Lewis and Prof Peter Majewski to the Division of ITEE that will ensure a bright future for The Wark in the in UniSA; Mr Frank Peddie to the Division of Health decades to come. The University, Advisory Board and Sciences within UniSA; Dr Damyanti Sharma to the the Research and Technology Advisory Committee are University of Wollongong; Dr Krasimir Vasilev to the all playing a splendid role in ensuring that the future is Mawson Institute and Dr Marek Zbik to QUT. indeed a bright one.

Our infrastructure base has expanded in 2007 with the John Ralston opening of a new suite of laboratories (600 m2) and Director offices (130m2) to accommodate our new research thrusts. We now occupy two and a half buildings, June 2008 including our highly sophisticated pilot plant and a joint surface engineering laboratory, the latter shared with the new Mawson Institute. We are constructing a new, state-of-the-art nanofabrication and microfluidics facility which will be completed in 2008. This forms

Ian Wark Research Institute Annual Report 2007  Management Structure

The Ian Wark Research Institute’s management structure draws together four core research sectors along with a scientific services sector which supports all research activities. The Wark’s activities are overseen by an Advisory Board having strong industry representation and being responsible to the Council of the University of South Australia.

The Research and Technology Advisory Committee is created by the Advisory Board and comprises internationally recognized academic researchers with strong industry experience and credibility. The Advisory Board reports directly to the University of South Australia Council and advises the Director on research activities and directions. l)

University of South Australia Council

Office of the Reseach and Deputy Vice-Chancellor Advisory Technology (Research Board Advisory Committee and Innovation)

Director Laureate Professor John Ralston

Corporate Services Executive Scientific Services

Bio and Polymer Colloids and Materials and Mineral Processing Interfaces Nanostructures Environmental Sector Sector Sector Surface Science Co-ordinator Co-ordinator Co-ordinator Sector Co-ordinator A/Prof Stephen Grano Prof Clive Prestidge A/Prof Daniel Fornasiero A/Prof Bill Skinner

 Advisory Board The Advisory Board convened on two occasions during 2007. Members are:

Dr Max Richards (Chair) FTSE Chair, School of Botany Foundation, University of Melbourne Dr Megan Clark Vice President, Technology, BHP-Billiton Ltd Dr Matthew Cuthbertson Chief Executive Officer, CRC for Advanced Automotive Technology Prof Tom Healy Particulate Fluids Processing Centre, Dept of Chemical and Biomolecular Engineering, University of Melbourne Dr Brian Hickman (Deputy Chair) Company Director and Past Chief Executive Officer, Amdel Ltd Dr Rachel Lucas Principal, Heidrick & Struggles Australia Dr Jim May Former Chief Executive, AMIRA Ltd Prof Caroline McMillen Deputy Vice Chancellor and Vice President: Research & Innovation, University of South Australia Dr Jurgen Michaelis Chief Executive, Bio Innovation SA Laureate Prof John Ralston Director, Ian Wark Research Institute, University of South Australia Dr Leanna Read Managing Director and CEO, TGR BioSciences Pty Ltd Dr Ray Shaw General Manager Technology Support, Rio Tinto Technology Mr Antony Simpson Past Chair, Mason & Cox Pty Ltd Mr Keith Smith Managing Director, Oncaidia Pty Ltd Ms Madelene Pierce Ian Wark Research Institute, University of South Australia (Executive Officer)

Research and Technology Advisory Committee The Research and Technology Advisory Committee met in February 2007. Prior to this meeting, international members visit the Institute for several days to meet with staff and students. Members are:

Prof Brian Vincent (Chair) Leverhulme Professor of Physical Chemistry and Director, Bristol Colloid Centre, University of Bristol, UK Dr Terry Blake Visiting Professor, University of Mons and Head (retired) Surface Science Kodak, UK Dr Matthew Cuthbertson Chief Executive Officer, CRC for Advanced Automotive Technology Prof Cyril O’Connor Dean, Faculty of Engineering and Built Environment, University of Cape Town, South Africa Prof Marcus Textor Head, Biointerfaces Group, Laboratory for Surface Science, ETH Zurich, Switzerland Ms Madelene Pierce Ian Wark Research Institute, University of South Australia (Executive Officer)

Executive The Executive met on a monthly basis:

Laureate Prof John Ralston (Chair) Director Dr David Beattie Academic Staff Representative Prof Hans Griesser Deputy Director (Industry) Mr Craig Hackney Coordinator: IT and Building Services Prof Roger Horn Deputy Director (Academic) Mr Paul Luppino Professional Staff Representative Prof Peter Majewski Research Professor Mr Santanu Ray Postgraduate Student Representative Mr Philip Moore Manager: Scientific Services Ms Sandy Ray Operations Manager A/Prof Bill Skinner Academic Staff Representative Dr Terry Wilks Institute Manager Mr Paul Byrne (Executive Officer)

Ian Wark Research Institute Annual Report 2007  Staff

Director Laureate Professor John Ralston, BSc(Hons) MSc DipEd PhD Melbourne DIC London, UK, FAA FTSE

Deputy Directors Professor Hans Griesser, DipChem SciTeachingCert PhD ETH Zurich, Switzerland Professor Roger Horn, BSc(Hons) Monash PhD Cambridge, UK

Institute Manager Terry Wilks, BSc(Hons) MSc PhD Newcastle, UK

Research Professors Peter Majewski, DipGeology PhD Hannover, Germany Clive Prestidge, BSc(Hons) Loughborough, UK PhD Bristol, UK Namita Roy Choudhury, BSc(Hons) BTech MTech(Hons) Calcutta, India PhD Kharagpur, India

Associate Research Professors Jonas Addai-Mensah, BEng(Hons) UST, Ghana MSc TIIT, Israel PhD Queensland Daniel Fornasiero, Maitre es Science Grenoble, France PhD Adelaide Stephen Grano, BMetEng(Hons) Queensland MAppSc SAIT PhD UniSA Sunil Kumar, BSc(Hons) MSc(Hons) GNDU, India PhD IIT, Delhi, India William Skinner, BSc Melbourne BAppSc PhD RMIT

Senior Research Fellows David Beattie, BSc(Hons) PhD Edinburgh, UK Naba Dutta, BSc(Hons) BTech Calcutta, India PhD Kharagpur, India Dusan Losic, BSc Novi Sad, Serbia PhD Flinders Peter Murphy, BSc(Hons) PhD Flinders Satomi Onishi, BSc Tokyo University of Science, Japan MSc Ibaraki, Japan PhD Saitama, Japan Rossen Sedev, MSc Sofia, Bulgaria PhD Bulgarian Academy of Sciences, Bulgaria

Research Fellows Holly Aiqun, BSc MSc PhD Tianjin, PR China Leanne Britcher, BAppSc(Hons) PhD UniSA Rick Fabretto, BSc(Hons) Flinders BEd PhD UniSA Colin Hall, BAppSc(Hons) UniSA Sarah Harmer, BAppSc(Hons) PhD UniSA Ivan Kempson, BAppSc(Hons) PhD UniSA Hamid Manouchehri, BSc MSc(Hons) Tehran, Iran PhD Lulea, Sweden Mihail Popescu, MSc Bucharest, Romania PhD Emory, USA Catherine Whitby, BSc(Hons) UNSW PhD Melbourne Vassili Yaminsky, DipSc PhD Moscow State, Russia Massimiliano Zanin, BEng Trieste, Italy PhD Cagliari, Italy

Research Associates Igor Ametov, BSc PhD Moscow State, Russia BEng Adelaide Timothy Barnes, BAppSc(Hons) UniSA GradDipEd Adelaide PhD UniSA Artem Borysenko, MSc Kharkiv State, Ukraine, PhD National Academy of Sciences, Ukraine Liping Ding, BEng(Hons) MEng Northeastern, PR China, PhD Queensland Renate Fetzer, Dip Physics Ulm, Germany PhD Saarland, Germany Sabina Gredelj, BEng(Hons) PhD UniSA Shuhua He, BSc MEng University of Science and Technology Beijing, PR China PhD UniSA Tatiana Khmeleva, MEng Ural Polytechnic, Russia PhD UniSA Marta Krasowska, MSc Maria Curie Sklodowska, Poland PhD Polish Academy of Sciences, Poland Vera Lockett, MSc Ural State, Russia PhD Russian Academy of Science, Russia Agnieszka Mierczynska-Vasilev, MSc PhD Lodz, Poland Craig Priest, BAppSc(Hons) PhD UniSA Rada Pushkarova, BEng Kiev, Ukraine PhD UniSA Damyanti Sharma, BSc Agra, India MSc Ambedkar, India PhD AMU, India Spomenka Simovic, BSc MSc Belgrade, Yugoslavia PhD UniSA Surya Subianto, BAppSc(Hons) PhD QUT Hui Tan, BEng Hunan, PR China DipChemEng, MSc Stellenbosch, South Africa PhD Melbourne Su Nee Tan, BSc Tulane, USA MSc Minnesota, USA PhD UniSA Benjamin Thierry, BEng INP Grenoble, France, MSc Montreal, Canada PhD McGill, Canada Nguyen-Duc Tran, BAppSc(Hons) PhD UniSA Krasimir Vasilev, MSc Prof Dr A Zlatarov University, Bulgaria PhD Martin Luther University, Germany

 Research Assistants Louie Del Castillo, BSc Unciano Medical College, Philippines Maria Sinche Gonzalez, BEng(Hons) Universidad Nacional San Agustin, Peru MSc Universidad Politecnica de Madrid, Peru Endre Szili, BBiotech Flinders Jingfang Zhou, BSc(Hons) Xiamen, PR China MSc Henan, PR China

Scientific Services Scott Abbott, BAppSc(Hons) PhD UniSA Chris Bassell, BAppSc BEng UniSA Aleksandr Kaplun, BSc Kiev State, Ukraine Andrew Lewis, BSc(Hons) Wales, UK PhD Bristol, UK Philip Moore, Advanced Chem Plant Operation Poole Tech College, UK, DipOH&S Management NSC, Adelaide Ray Newell, BSc MSc Newcastle PhD UniSA Dennis Palms, MSc PhD Johannes-Gutenberg, Germany Maria Provatas, BSc Flinders BAppSc UniSA Keith Quast, BAppSc MAppSc SAIT Andrew Robinson, BAppSc SAIT Eric Tavenner, BSc Missouri-Rolla, USA MSc Southwest Missouri State, USA PhD Queensland Tosha Tichy, DipAppSc UniSA

Research and Technology Support Dom Davda, CertHECompStudies Southampton Institute of HE, UK HND Graphic Design Middlesex, UK Darren Faulkner, Fitting & Machining App, Adv Cert Engineering TAFE Peter Gray, Electrical Mechanic App TAFE Craig Hackney, ScTechCert SAIT BBus UniSA Marek Jasieniak, BSc(Hons) Cracow, Poland Czeslaw Poprawski, DipMechEng TUW, Poland ScTechCert SAIT Nicola Sleep, BTech BSc(Hons) Flinders Phil Souter, Post-trade Certificate TAFE

Administration Paul Byrne, BA(Hons) Adelaide Julie Freytag Kim Gauci Tracy Greeneklee, Cert IV Business (Admin) TAFE Cert IV Info Tech TAFE Christina Koutlakis Paul Luppino, AssDipAcc TAFE Madelene Pierce, BA(Hons) Flinders Kathryn Prohaska Sandra Ray, GradDipMgmt MBA UniSA Baden Smith, AssDipAdvGraphicDes TAFE Maureen Terry Paul Wotley, BSc(Hons) Adelaide Kerry Zweck, Cert IV Business (Admin) Jobs Statewide

Adjunct Research Professors Dr Terry Blake Visiting Professor, University of Mons and Head (retired) Surface Science Kodak, UK Dr Bart Follink, Chief of Division, CSIRO Minerals, Victoria, Australia Prof Ron Martin, Department of Chemistry, University of Western Ontario, Canada Prof Jordan Petrov, Institute of Biophysics, Bulgarian Academy of Sciences, Sofia, Bulgaria Dr Allan Pring, South Australian Museum, Adelaide, Australia Prof Jarl Rosenholm, Physical Chemistry, Abo Akademi, Turku, Finland

Adjunct Associate Research Professor Dr Natalia Mischuk, Institute of Colloid and Water Chemistry, National Academy of Sciences, Kiev, Ukraine

Adjunct Senior Research Fellows Mr George Levay, Levay & Co Environmental Services, Adelaide, Australia Dr Marek Zbik, Queensland University of Technology, Queensland, Australia

Adjunct Research Fellows Dr Kristen Bremmell, Department of Chemical Engineering, University of Adelaide, Australia Dr Geoffrey Reynolds (retired) School of Pharmacy and Medical Science, UniSA Dr Joan Thomas, Jefferson Lab,(The College of William and Mary), Virginia, USA

Adjunct Research Associate Dr Nicola Lake, Madderns Patent and Trade Mark Attorneys, Adelaide, Australia

Ian Wark Research Institute Annual Report 2007  Postgraduate Students EDUCATING PROFESSIONALS

Degrees Awarded Jarred Clasohm PhD in Applied Science Linh Cuba-Chiem PhD in Applied Science John Denman PhD in Applied Science Kate McLeod PhD in Applied Science Tatu Miettinen PhD in Engineering Ana Pereira Duarte PhD in Applied Science Thi Phuong-Cac Nguyen PhD in Applied Science Kim Shyong Siow PhD in Engineering

PhD Candidates Victor Absolon AssocMet Kalgoorlie School of Mines, MSc University of London, UK MBA Melbourne Nick Absalom BSc(Hons) Flinders Robert Acres BSc(Hons) Flinders Heramb Bal BEng Pune, India MEng UniSA Audrey Beaussart MEng European School of Materials Science and Engineering Nancy, France Chiu Ping Chan BSc(Hons) UniSA Joseph Chan BSc(Hons) Flinders Daniel Chipfunhu BSc(Hons) MSc, University of Zimbabwe Martin Cole BSc(Hons) Flinders

Dr Renate Fetzer (left) and PhD candidate Mr Luke Parkinson

 Mark Coppola BSc(Hons) Flinders Lorena Del Castillo BSc MSc University of the Philippines Massey De los Reyes BSc(Hons) UniSA Terry Dermis BSc(Hons) UniSA Ivan Djordjevic BAppSc BSc(Hons) UniSA Mariya Foundas BProcessEng(Hons) Moscow State Institute of Food, Russia Jairo Garnica Rodriguez BEng Universidad Nacional de Colombia, MEng MPhil Queensland Nasrin Ghouchi Eskandar BSc(Hons) Tabriz University of Medical Sciences, Iran Carlos Gontijo Eng de Ninas Universidad Federal do Minas Gerais, Brazil Aravind Govindaraj Kannan BTech, Central Electrochemical Research Institute, India Colin Hall BAppSc(Hons) UniSA Gary Hanly BSc(Hons) Newcastle Mingzhao He MSc Northeastern, PR China LICEng Lulea, Sweden Allister Henderson BSc(Hons) Adelaide Karyn Jarvis BAppSc BSc(Hons) UniSA Li Jiang BSc Ludong, PR China MSc Tianjin, PR China Jessica Kinal BEng(Hons) Curtin Huixin Li BEng Hebei Chemical Engineering Institute, PR China Shibin Joey Liang BEng Dalian University of Technology, PR China MEng Dalian Marine University, PR China Sundar Mayavan BTech Central Electrochemical Research Institute, India, MSc Anna, India Melanie McGuire BSc(Hons) Adelaide Mayur Mistry BAppSc BSc(Hons) UniSA Solomon Muganda BSc(Hons) University of Zimbabwe Ataollah Nosrati BSc Petroleum University of Technology, Iran MSc Tarbiat Modarres University, Iran Matthew Oaten BAppSc(Hons) UniSA Mani Paneru MTech IIT Bombay, India Srinivas Parimi BSc Andhra, India MSc Griffith Luke Parkinson BSc Adelaide BSc(Hons) Queensland Anuttam Patra BSc(Hons) Calcutta, India MSc IIS Bangalore, India Thiru Ponnusamy Meenakshisundaram BEng(Hons) Regional Engineering College Trichy, India, MAppSc UniSA Lee San Puah BEng(Hons) University of Science, Malaysia Andry (Laza) Randriamanjatosoa BEng Polytechnic University of Antananarivo, Madagascar MSc Tuebingen, Germany Santanu Ray BSc MSc Jadavpur, India Evgueni Resnianski BSc MSc Novosibirsk State, Russia Iliana Sedeva MSc Sofia, Bulgaria, GradDipEd Adelaide Kinnari Shelat BSc MSc Maharaja Sayajirao, Baroda, India Michael Sheridan BAppSc(Hons) UniSA Yunyu Shi BChemEng East China University of Science and Technology, PR China, MChemEng Adelaide Sin Ying Tan BEng(Hons) Curtin Sandra Thompson BAppSc(Hons) UniSA Diana Tran BChemEng(Hons) Adelaide Minh-Uyen Trinh BAppSc(Hons) UniSA My Yung Truong BEng Adelaide Mohanraj Vellore Janarthanan BPharm JSS College of Pharmacy, India MPharm Curtin University of Technology Feng Wang BMed Guangxi College of TC Medicine, PR China MSc Waikato, New Zealand Wenbo Wang BMinProc Southern Institute of Metallurgy, PR China, MSc University of Science and Technology Beijing, PR China Danfeng Xu BSc Northeastern, PR China MSc Tianjin, PR China Jingwu (Fabio) Yang BSc Peking, PR China MEng Tianjin, PR China Xiangfei Ye BEng Tianjin, PR China MSc Nanyang, Singapore/Technical University of Munich, Germany Kai Ying Yeap BChemEng(Hons) Adelaide Hardi Ys BSc Syiah Kuala Indonesia MSc Andalas, Indonesia Jingfang Zhou BSc Xiamen, PR China MSc Henan, PR China Lin Zhou BChemEng Daqing Petroleum Institute, PR China, MSc Tianjin University, PR China

MAppSc Candidates Djoko Julianto BEng, Institute of Technology Bandung, Indonesia Joseph Putubu BSc PNG Yoo Hyun (Daniel) Sung BSc MSc Korea

Ian Wark Research Institute Annual Report 2007  Education and Training All HDR students are required to participate in The Wark’s Student Seminar Program which is currently Higher degree by research (HDR) students are coordinated by Dr Satomi Onishi. These seminars directly enrolled in The Wark in either doctoral or provide a forum to disseminate information on masters degree programs. The Wark has a special research being carried out at the Institute, whilst style of blending fundamental and applied research also giving students valuable practice in presenting in an interactive, constructively critical environment. their work and fielding the obligatory, and often This facilitates students’ learning, gives them an gruelling questions regarding their research. An appreciation of real world problems and enhances annual award is presented for the best seminar. The their employment prospects. recipient of this award for 2007 was Ms Karyn Jarvis (see page 50 for details). Our students are a major strength of the Institute. Sixteen new Australian and international students Seven students were awarded Wark Student Travel commenced HDR programs during 2007. All of Grants for attendance at conferences in Australia these students were awarded scholarships - three and overseas. They were: Martin Cole, Nasrin Australian Postgraduate Award (Industry), two Ghouchi Eskandar, Karyn Jarvis, Rob Acres, Ivan ARC/industry funded scholarships, one UniSA Djordjevic, Srinivas Parimi and Frank Wang. Postgraduate Award, one Endeavour International Postgraduate Research Scholarship and nine The Wark encourages its HDR students to spend UniSA President’s Scholarships. Ten students were time in other key national and international research recruited from overseas, specifically India, Indonesia, laboratories and/or industrial environments. PR China, The Philippines and Zimbabwe.

PhD candidate Mr Wenbo Wang (left) and A/Prof Daniel Fornasiero

10 Commensurate with this philosophy: Fifty four students were enrolled in HDR programs in the first half year 2007, and eight students • Robert Acres visited the NSRRC Synchrotron, successfully completed all the requirements for Taipei, Taiwan, from 1-7 April and the Cheiron completion of their degrees. These students Synchrotron School, Tokyo, Japan from 8-21 accepted many varied appointments across September academia and industry, both within Australia and • My-Yung Truong visited the University of overseas (see page 66 for details). Montpellier, Paris, France from 31 May to 3 November Whilst not formally involved with undergraduate • Martin Cole visited ETH Zurich, Switzerland from teaching, The Wark delivers a Nano- and Bio- 29 August to 21 September and the University materials stream in the BSc (Honours) program of Sheffield, England from 22 September to 5 that is coordinated by the School of Mathematics October and Statistics. Student numbers are small but the • Karyn Jarvis visited the NSRRC Synchrotron, stream fulfils a useful role in introducing students Taipei, Taiwan from 4-19 October to, and training them for, research work in the • Chiu Ping Chan visited the University of Poitius, Institute. Seven students completed the program Paris, France from 9 November to 16 December in 2007. • Heramb Bal visited Inco Limited, Toronto, Canada from 17 November to 3 December A number of other education and training programs • Terry Dermis visited BHP Billiton Newcastle were undertaken during 2007: a traineeship Technology Centre, Newcastle, Australia from program for overseas student visitors; a vacation 18-21 November. program for undergraduate students; and a voluntary work experience program for mature age, undergraduate and high school students.

Ian Wark Research Institute Annual Report 2007 11 Major Research Sponsors ENGAGING OUR COMMUNITIES

AMIRA International Lundin Mining Corporation Anglo Platinum Corporation Ltd Magotteaux Australia Pty Ltd ANSTO Metso Minerals Australian Antarctic Program MinProcesSer Pty Ltd Australian Research Council Nalco Australia Pty Ltd BHP Billiton Ltd National Collaborative Research Infrastructure BHP Billiton Nickel West Ltd Strategy (NCRIS) – Australian Government BHP Billiton (Olympic Dam Corporation) Pty Ltd Ok Tedi Mining Ltd Bio Innovation SA Outotec BioSignal Ltd Oxiana Resources NL Boliden Minerals AB Phelps Dodge Mining Co Cancer Council of South Australia Poly Products Co Pty Ltd Carl Zeiss Vision Australia Premiers Science Fund Companhia Vale do Rio Doce – South Australian Government COREM pSivida CRC for Intelligent Manufacturing Systems and Rio Tinto Ltd Technologies Soniclean CRC for Polymers Sons of Gwalia CSIRO Minerals Starpharma CSIRO Petroleum Teck Cominco Ltd Cytec Australia Holdings Pty Ltd Tiwest Joint Venture Eurozinc Mining Corporation United Water Huntsman Corporation Australia Pty Ltd Vale Inco Intellection Visiocorp Australia Pty Ltd ITEK Visy Plastics Julius Kruttschnitt Mineral Research Centre Xstrata Copper (JKMRC) Xstrata Technology Labtech Systems Ltd Zinifex Ltd

12 Research Funding

Funding Division 2007

Industry 35.1%

Federal/State Government 43.4%

University of South Australia 21.5%

Operating Revenue for the period 1997 - 2007

16, 000, 000 14, 000, 000 12, 000, 000 10, 000, 000 8, 000, 000 6, 000, 000 4, 000, 000 2, 000, 000 0 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007

Ian Wark Research Institute Annual Report 2007 13 Research Highlights CREATING AND APPLYING KNOWLEDGE

Australian Mineral Science Research Institute network of particle science and engineering (AMSRI) research, attracting the best researchers from around the world, and incorporates and applies the 2007 represented the second year of operation of discipline strengths of other industry sectors and the the Australian Mineral Science Research Institute minerals sector. (AMSRI), which runs from 2006 – 2010. The three remaining research staff appointed under The following are a few highlights across the AMSRI AMSRI commenced at The Wark early in the programs during 2007: year: Dr Renate Fetzer, Dr Marta Krasowska and Dr Mihail Popescu. They joined existing staff Dr • New information on mineral liberation, especially Sarah Harmer, Dr Craig Priest, Dr Catherine Whitby breakage modes and modelling; and Ms Tracy Greeneklee, AMSRI’s administrative • A potential control strategy for swelling clays; officer. Two HDR students also commenced within • Novel technique for studying bubble-bubble the AMSRI research programs during the year, Ms interactions developed; Sin Ying Tan and Ms Kai Ying Yeap. They joined • Using specific polymers for dewatering; existing students Mr Robert Acres, Mr Shibin Joey • Improved understanding of isotropic turbulence; Liang, Mr Luke Parkinson and Ms Diana Tran. • A theory of sliding contact and frictional tribocharging; The focus of AMSRI is to strengthen Australian • New methods for controlling selective fine technological and scientific leadership in particle particle separation; science and engineering, supporting innovation • New theory for understanding dynamic liquid which will sustain the present and future flow through patterned capillaries; contributions that the minerals and related • Novel microfluidic applications; industries make to Australia. Energy efficient • Instruments for determining particle wettability liberation, frugal water use and waste management, and turbulent energy dissipation developed and innovative processing, material and interface commercialization now being pursued; science, advanced analysis, and mathematics in • Novel technique for determining the interaction minerals processing are of great significance to of a free bubble with a solid surface developed, the nation’s mineral industry, its primary export complemented by AFM force studies; earner. The minerals industry will be transformed • Novel use of SPEM (Scanning Photoemission through new technologies, helping to create an Electron Microscopy) for assessing the chemistry environmentally sustainable nation. of "patches" on sulphide mineral surfaces; • Fine modelling work on fluid droplet- solid Left to right: Dr Renate Fetzer, AMSRI is generating new knowledge, thus providing surface interactions. Dr Mihail Popescu, Dr Sarah the science platform for a new paradigm of high Harmer, Ms Diana Tran, Dr Craig efficiency, low-impact particle science technology. The sponsor companies are pleased with progress Priest, Dr Marta Krasowska, It also attracts and educates outstanding graduate in the AMSRI research programs and planning Dr Catherine Whitby, Mr Luke students from both Australia and overseas for for AMSRI II, which will run from 2011, has now Parkinson, Ms Tracy Greeneklee research and industry careers in Australia. It acts commenced. and Mr Robert Acres as the core centre for a national and international

14 Memorandum of Understanding –University International Collaboration – The Wark and of South Australia and the University of Mines Tianjin University, PR China and Technology, Ghana During 2007, a further two General International On 12 July, UniSA signed a Memorandum of Agreements were signed between the Ian Wark Understanding with the University of Mines and Research Institute and schools within Tianjin Technology (UMaT), Ghana (West Africa). The University, PR China. The purpose of these initiative followed from a series discussions and Agreements is to promote cooperation in education negotiations between UniSA’s senior management and research which involves collaborative research headed by the current and former Vice Chancellors, projects, the exchange of academic information and Prof Peter Høj and Prof Denise Bradley, Dr Anna staff and student reciprocal visits. Ciccarelli (Pro Vice Chancellor: International & Development), Laureate Prof John Ralston (Director, The Wark now has Agreements with three schools The Wark), A/Prof Jonas Addai-Mensah, (The Wark) within Tianjin University – Chemical Engineering, and Mr Stephen Parsons (Manager, International Environmental Science & Engineering and Materials Relations & Market Development) and the Vice Science & Engineering. To further these ties, on Chancellor of UMaT, Prof Mireku-Gyimah. The 3 August, five delegates from Tianjin University final exchange of the MoU took place in Ghana visited The Wark and gave a series of presentations between Prof Mireku-Gyimah and A/Prof Jonas to inform Wark staff of some of the current work Addai-Mensah who acted on behalf of UniSA’s being carried out at Tianjin. Vice Chancellor, Prof Peter Høj. The Memorandum records the understanding of the two parties The visiting delegates from Tianjin were: Prof Cui in relation to the cooperative activities. It also Zhenduo (Dean, School of Materials Science & enunciates both parties shared interests and intent Engineering), Prof Jiang Zhongyi (Vice-Dean, School to undertake cooperative activities to their mutual of Chemical Engineering), A/Prof Yuan Xubo (Vice- benefits within the field of research, education Dean, School of Materials Science & Engineering), and training in the areas of minerals, mining and Prof Zhao Naiqin (School of Materials Science & materials processing, science and engineering. Engineering) and Prof Yuan Xiaoyan (School of Materials Science & Engineering). Far left: A/Prof Jonas Addai- The cooperative activities to be undertaken by the Mensah (left), Prof Daniel parties may include: A visit by Wark staff to Tianjin University is planned Mireku-Gyimah and Prof Elias • exchange of staff and students; for September 2008 to coincide with the XXIV Aslam at the official signing • exchange of information for education and International Mineral Processing Congress to ceremony in Ghana research purposes; be held in Beijing where the Ian Wark Research • joint education and training; Institute will have an exhibition booth. Below left to right: A/Prof Yuan • joint research, publication and symposia; Xiaoyan, Prof Cui Zhenduo, • other activities considered by the parties to be of Laureate Prof John Ralston, Prof benefit to each party’s education and research Jiang Zhongyi, Prof Zhao Naiqin programs. and A/Prof Yuan Xubo

Ian Wark Research Institute Annual Report 2007 15 Above left to right: Dr Dennis UniSA Open Day Palms, A/Prof Bill Skinner, Mr John Denman, Mr Robert At the annual UniSA Open Day on 26 August, The Acres, Ms Karyn Jarvis and Wark information booth aimed to highlight the Dr Shuhua He diversity of research carried out at the Institute – from forensics, implants and pharmaceuticals to the numerous applications to the minerals industry.

Special acknowledgement to Robert Acres, John Denman, Shuhua He, Karyn Jarvis, Dennis Palms, Santanu Ray and Bill Skinner who operated The Wark booth throughout the day.

2006 Ian Wark Research Institute Medal Presentation

The presentation of the Ian Wark Research Institute Medal was made on 16 November to Dr Alan Kanta by the Chair of The Wark’s Advisory Board, Dr Max Richards (pictured right) . Alan’s thesis was titled, “Titania and silica surfaces, wettability studies and applications” and his principal supervisor was Laureate Prof John Ralston.

After completing his theses, Alan took up a position at Monash University in Victoria, Australia.

16 At the funding handover (from left to right) Mr David Klingberg, Chancellor of UniSA, The Hon Paul Caica, Laureate Prof John Ralston and Prof Peter Høj, Vice Chancellor & President of UniSA

Left to right: Dr Dennis Palms, Dr Peter Murphy and Dr Craig Priest

Microfluidics and Nano-Fabrication Facility The Facility, which will open in late 2008, will enable the prototyping and replication of channels On 12 December, the South Australian Minister and networks at the micro-scale. This new for Science, the Hon Paul Caica, presented a capability will fit closely with the already extensive “microscopic” cheque for $2 million to Wark minerals processing and interfacial science research Director, John Ralston for the new Microfluidics infrastructure in place at The Wark. and Nano-Fabrication Facility at UniSA which will be housed at The Wark. This was a novel way to The Facility at The Wark will form part of the highlight the role this new Facility will have in the Australian National Fabrication Facility (ANFF) which design and manufacture of microchips for chemical, links seven complementary university-based nodes biological and clinical applications. The South to provide researchers with access to state-of-the- Australian Government’s contribution formed part art fabrication facilities. Further information about of the total $8 million in funding for the Facility, ANFF can be found at: www.anff.org.au with $2 million funded through the National Collaborative Research Infrastructure Strategy (NCRIS) and a $4 million investment by UniSA.

Ian Wark Research Institute Annual Report 2007 17 Mineral Processing Research - Around the World and in Our Backyard Project Profiles by Dr Sabina Gredelj

Around the World: Anglo Platinum Ltd, PPL In our Backyard: BHP – Billiton Olympic Dam Mineral Processing Plant, South Africa Operations, Roxby Downs, South Australia

Over a period of three weeks during June-July, Over a period of two weeks during August- research staff from the Ian Wark Research Institute September, research staff from The Wark visited visited the Anglo Platinum Ltd mining and mineral BHP – Billiton Olympic Dam Operations (ODO). processing site, Potgietersrust Platinum Limited Olympic Dam is the world’s largest uranium (PPL). Anglo Platinum Ltd is the world’s largest deposit, fifth largest gold deposit and the fourth producer of platinum group metals (PGM) which largest copper deposit. ODO is an impressive site besides platinum, includes palladium, rhodium, encompassing an underground mine (the largest in ruthenium, iridium and osmium. Nickel and Australia), crushing, grinding, flotation, leaching, copper are also recovered as by-products of PGM solvent extraction, smelting and electro-refining operations. operations. Copper cathodes, uranium oxide, gold and silver bullion are produced on site and besides At PPL, platinum group elements are associated the Australian market, are exported to numerous with sulphide minerals and recovered using the countries in Asia, Europe and North America. flotation process. Anglo Platinum Ltd is one of the sponsors of the AMIRA International P260E BHP – Billiton Olympic Dam Operations is one of project which focuses on improving sulphide the sponsors of the AMIRA International P541B mineral flotation. Anglo recognise the need and project on optimising of froth zone performance in envisages potential benefits from studies conducted mineral flotation. The main objective of the project on mineral processing plants or pilot plants at is to increase the recovery of valuable mineral in their sites. For this particular study, metallurgical the flotation circuit, by increasing froth stability and surveys were conducted on a pilot plant flotation froth recovery, while keeping recovery of gangue circuit consisting of five 10 m3 flotation cells. This minerals through entrainment at a low level. Two study was mainly concerned with hydrodynamic major metallurgical surveys were conducted during conditions within the flotation cells however, the visit resulting in a metallurgical mass balance Research related to pulp chemistry is also a crucial for the whole flotation circuit, as well as size by part of the P260E project. The effect of impeller size analysis on the rougher and scavenger banks. speed on recovery of valuable minerals was Froth characterisation with respect to froth stability, investigated, while other hydrodynamics parameters velocity and bubble size on top of the froth, such as gas holdup, superficial gas velocity and was performed at the same time. Screening of bubble size were monitored. Laboratory flotation commercial frothers and their comparison with the studies were conducted in parallel with pilot plant current plant frother was carried out at laboratory metallurgical surveys. scale using an instrument developed at The Wark.

PPL is situated about one hours drive from a small For the duration of the field trip we stayed in Roxby town, Mokopane. Opposite our hotel was a wildlife Downs which has a population of approximately game park which we visited as soon as free time 4,000 and is situated about 16km from the site and allowed. Giraffes gracefully grazed alongside 560km north of Adelaide. It was spring time and impalas and zebras in the African bush and were the weather was becoming warmer and drier. The not overly concerned with the sight of intrepid terrain was covered in the beautiful, vivid red colour researchers from Australia! of the Sturt’s Desert Pea which was in full bloom.

Resulting from our work on the plant, further Positive feedback with respect to our work and discussions with Anglo Platinum Ltd about specific conduct has been received from BHP – Billiton laboratory work are under way. Olympic Dam Operations.

18 A Materials Research & Engineering Facility for Conducting Polymer Devices Premiers Science Research Fund, The Wark and the Mawson Institute for Advanced Manufacturing Project Profile by Dr Peter Murphy

As a result of a successful application to the in between, creating the potential for applications Premiers Science Research Fund (PSRF) the Ian Wark requiring a variable tint, such as architectural glass, Research Institute and the Mawson Institute were aircraft windows, sunglass lenses and automotive jointly awarded $380,000 in order to establish windows. Working with our industry based a unique facility to investigate process scale-up collaborative partners at Visiocorp Australia Pty Ltd methodologies for a new type of electrochromic and Carl Zeiss Vision, we intend to investigate and device using conducting polymers. develop several of these applications. The materials research and engineering facility will permit us to This project will create a unique facility within South develop and demonstrate methods of technology Australia to investigate advanced manufacturing scale-up, a vital step in demonstrating the methods for the development of electrochromic robustness of the technology to potential industry technologies. The project is a joint partnership partners. between The Wark and the Mawson Institute for Advanced Manufacturing and aims to create a Benefits to South Australia arising from this project unique capability to investigate and demonstrate will include: technology scale-up methodologies. Operating out of a newly refurbished 150m2 laboratory, • The development of intellectual property that the scale-up facility will house state or the art is South Australian owned (two PCT patent equipment designed to enable the development applications have already been filed and more of robust pre-manufacturing methods with direct will follow). relevance to the manufacturing sector. The facility • The potential for local investment in new will also accommodate environmental test and manufacturing facilities to produce high value evaluation equipment for proving the robustness added product (already under consideration by of devices and technology prior to manufacturing one of our collaborative partners). implementation. • The possibility of manufacturing high technology product in local facilities for world-wide export. Electrochromic materials are able to alter their • Establishment of a show case facility within optical characteristics to switch between either a UniSA for attracting new industry and academic dark state or a clear state as shown in the images partners both nationally and internationally. below. The transition can be stopped at any point

Ian Wark Research Institute Annual Report 2007 19 Bio and Polymer Interfaces Sector Coordinator: Prof Clive Prestidge

Overview hydroxyapatite coatings for bone implants and plasma coatings containing sulphur and In 2007 The Wark’s Bio and Polymer Interfaces phosphorus and protein interactions, respectively. Sector has increased its profile on the national and international stages. Examples of significant • The Wark’s LipoceramicTM technology for research project progress, achievements and encapsulation and delivery of poorly soluble outcomes are detailed below and specific research drugs has continued to develop, as indicated highlights follow. by the filing of a number of new patents and successful completion of 2 Commercial • ARC Special Research Centre funding on hard Development Initiative Projects funded by interfaces Bioinnovation SA and Itek Ltd. Dermal applications of nanoparticle encapsulated • Over 20 fully refereed journal articles were emulsions are shown on page 28. published across the Sector’s major research themes of Bio-Interface Science, Nanostructured • Research into bio-medical and pharmaceutical Drug Delivery Systems and Polymer Interfaces applications of functional nanoparticles continues to strengthen; systems under • 3 major national competitive grant were investigation include inorganic oxides, metals, awarded across the areas of biointerfaces, polymers including dendrimers and hybrid biodiagnostics and biodelivery: particles. Immunotargeting is an area showing considerable progress (see page 24). - A 4 year ARC Discovery grant “Advanced Nanostructured Biointerfaces for Cell Capture: • Our fundamental investigations aimed at Mechanistic Understanding of Binding Events understanding the in vivo performance of to the Development of a New Generation of surface functionalised biomaterials are facilitating Biodiagnostic Tools”, Prof Hans Griesser, Dr the design and development of a number of bio- Benjamin Thierry and Prof Clive Prestidge, in medical devices. The activities of Prof Griesser’s collaboration with Dr Michael Brown (Royal team in the field of antibacterial coatings are Adelaide Hospital) and Dr Maryam Tabrizian shown on page 22. (Magill University, Canada). (Total funding: $535,000) • A number of novel materials have been developed based on elastomeric gels, biomimetic - A 3 year ARC Linkage project with Citech polymers and hybrid nanoparticle-polymer Holdings Ltd, “Novel Biodiagnostic Platforms composites. This area is summarized in Dr for Human Metabolites”, Prof Clive Prestidge, Naba Dutta and Prof Namita Roy Choudhury’s Prof Hans Griesser in collaboration with Dr book chapter on “Functional Nanostructures: Tharshan Vaithianathan (Mawson Institute). Synthesis, Characterization and Applications” in (Total funding: $695,000) “Self Assembly in Nanostructured Polymer and Thin Films” (ed., S. Seal, Springer, 2007, p.220- - A 3 year NH & MRC project granted 304). Examples include: “Immunotargeted Nanoparticles to Improve Tumour Delivery of Chemosensitising - A new class of ultrahydrophobic fluoro- Cytotoxics and B-Radiation”, Prof Hans silsesquioxane-urethane hybrids for thin film Griesser, Dr Benjamin Thierry and Prof Peter application, with low surface energy and Majewski, in collaboration with Dr Michael nanometer scale roughness. This is suitable Brown (Royal Adelaide Hospital). (Total for dirt repellent and anti fouling applications. funding: $520,500) - A unique stimuli-sensitive polymer hydrogel • Dr Dusan Losic joined The Wark as an ARC based on the biomimetic polymer rec-1 resilin funded Australian Research Fellow (5 years). His that exhibits both thermo-reversible upper research in the field of Nanoporous Materials is critical solution temperature (UCST) and highly complementary to current academic staff kinetically controlled lower critical solution and is leading to a number of fruitful internal temperature (LCST). Strategies have been and external collaborations (see page 26). developed to manipulate this self-assembling process to create 'smart' biomaterials and • PhDs were awarded to Kate McLeod and Kim guide synthesis of functional nanoparticles. Siow for theses concerned with functionalised

20 Prof Clive Prestidge and Dr Spomenka Simovic with the Buchi-290 spray dry system which converts liquid Pickering emulsions into microcapsules with porous matrix internal structure. Internal matrix structure enables superior delivery of poorly soluble drugs via fast lipolysis and supersaturation effect

Ian Wark Research Institute Annual Report 2007 21 Antibacterial Coatings for Biomedical Devices

Research Sponsors (partial) Aims and Background whether they will also be active when anchored ARC Special Research Centre for onto biomaterials. Our current research focuses on Particle and Material Interfaces The colonization of biomedical devices and implants the development of coatings, their characterization and Biosignal Ltd by bacteria can cause infections that pose a health by spectroscopic methods, and assessment of in risk to patients, often require re-operation and vitro models of biomedical interactions such as Research Staff replacement of the infected device, and incur protein adsorption onto the coatings at The Wark, Prof Hans Griesser considerable costs to the health care system. Thus, and antibacterial testing is performed by our Dr Leanne Britcher we are pursuing the development of thin coatings collaborators at the Sansom Institute. Dr Krasimir Vasilev that can be applied to biomedical devices with the Mr Marek Jasieniak aim of providing resistance to bacterial colonization. Achievements Ms Stefani Griesser One approach comprises the covalent coupling, Dr Susan Semple (Sansom onto biomaterials surfaces, of molecular layers Serrulatane diterpene compounds extracted from Institute, UniSA) of novel antibacterial compounds isolated from Eremophila plants have been covalently linked Australian native plants in the genus Eremophila onto polymer and ceramic substrates via adhesive Research Students [1]. Work at the Sansom Institute has extracted interlayers. The resultant coatings have been Mr Hardi Ys diterpenes of the serrulatane class from these characterized by XPS and ToF-SIMS; features such Mr Chi P Ndi (Sansom Institute, plants and shown them to be active in solution as an aromatic shake-up satellite in the XPS C1s UniSA) form against multi-drug resistant strains of key spectrum, arising from the aromatic ring in the bacteria causing hospital infections [2,3]. Another diterpene structure, and characteristic ToF-SIMS Eremophila denticulata subsp approach involves the use of silver nanoparticles fragments have enabled verification of the presence trisulcata, one of the plants dispersed within thin polymer films. A third of the serrulatanes on the surface and the success whose extracts have shown high approach comprises the covalent immobilization of of the intended linking chemistry. The coatings antibacterial activity thin layers of antibacterial molecules whose activity have been tested for their ability to deter bacterial has been established in solution; the aim is to study adhesion in an in vitro model with Staphylococcus epidermidis. Of several coating variants, the best produced >98% reduction in bacterial colonization over 4 hours compared with a polyallylamine graft coating. The in vitro results to date indicate considerable promise for in vivo and clinical studies with these coatings. A provisional patent application has been lodged to protect the novel coatings and their commercial application. Interest has been expressed by companies in this technology.

The approach of using silver nanoparticles in combination with a thin polymeric carrier film has also produced successful results. By incorporating the silver nanoparticles inside a polymer film, direct exposure of the biological environment to solid silver can be avoided; the surface of the polymeric film is conducive to colonization by human cell lines and tissue, and antibacterial action is controlled by out-diffusing sliver ions. By adjustment of the polymeric carrier film properties and thickness, the rate of delivery of silver ions can be tailored. Tests involving bacterial colonization in vitro likewise have shown that this strategy also leads to considerable reductions in bacterial colonization.

Experiments have also shown that some commercially available, established or experimental antibiotics can be covalently linked to polymer surfaces as molecular layers and in this manner provide protection against bacterial colonization in vitro. We have developed several strategies for the covalent anchoring of furanone compounds onto silicone hydrogel extended wear contact lenses, and coated lenses have been tested by collaborators

22 Images of bacteria colonizing materials surfaces. The bacteria were stained to show up in fluorescent green if alive. Top left: amine plasma polymer surface; bottom left: polyallylamine graft surface; right hand side: two different serrulatane coatings

at the University of NSW on guinea pigs, which be used to set up and apply additional biological demonstrated marked reductions in infection [4]. testing methodologies in order to test the various coatings in more sophisticated and comprehensive The availability of several alternative antibacterial ways, to acquire the information packages required coating strategies is a great asset because no for regulatory approval and clinical testing. single coating will be suitable for all applications; with further biological testing, we will establish a Publications data base for the rational selection of antibacterial coatings for specific applications. 1. C.P. Ndi, S.J. Semple, H.J. Griesser and M.D. Barton Antimicrobial activity of some plant Next Steps species from the Australian genus Eremophila Journal of Basic Microbiology, 47, 158-164 Work will continue on making, characterizing, and (2007). testing coatings, in order to elucidate optimally 2. C.P. Ndi, S.J. Semple, H.J. Griesser, S.M. Pyke, efficient coatings. In addition, the project work M.D. Barton Antimicrobial compounds from will be expanded in 2008 thanks to a newly the Australian desert plant Eremophila neglecta awarded NHMRC Development Grant. To date, Journal of Natural Products, 70, 1439-1443 antibacterial serrulatane compounds have been (2007). sourced by extraction from plant material collected 3. C.P. Ndi, S.J. Semple, H.J. Griesser, S.M. Pyke, from gardens or from the wild (with permits). It is M.D. Barton Antimicrobial compounds from essential for commercial viability of the technology Eremophila serrulata Phytochemistry, 68, 2684- to investigate the reliability and costs of procuring 2690 (2007). larger amounts of the compounds. One scenario is 4. H. Zhu, A. Kumar, J. Ozkan, R. Bandara, A, Ding, the cultivation in plantations of Eremophila species I. Perera, P. Steinberg, N. Kumar, W. Lao, S.S. that have high loadings of antibacterial compounds, Griesser, L. Britcher, H.J. Griesser, M.D.P. Willcox coupled with extraction. It will be assessed how Fimbrolide-coated antimicrobial lenses: their in readily the plants can be propagated and grown vitro and in vivo effects. Optometry & Vision using established methods, and, more importantly, Science, 85, 292-300 (2008). how efficient the extraction can be made. The other scenario is the total chemical synthesis of compounds. A new sub-project will commence in 2008 involving synthesis studies of serrulatane diterpenes and naphthoquinone-serrulatanes, by adding the synthetic expertise of A/Prof.M. Perkins (Flinders University). NHMRC funding will also

Ian Wark Research Institute Annual Report 2007 23 Design and Immunotargeting of Functional Nanoparticles

Research Sponsors Nanomedicine, the medical application of The emergence of medical nanomaterials and NHMRC nanotechnology, has emerged as a “disruptive nanodevices may also be a cornerstone toward the ARC Discovery technology” which will drive a new generation once elusive concept of personalized medicine, i.e. Cancer Council of South Australia of medical diagnostic and therapeutic products. treatments tailored individually to patients. “Nano”materials differ drastically from Research Staff “macro”materials: their small size - 1 nm to 100 nm A wide range of functional colloidal nanomaterials Dr Benjamin Thierry - confers unique physical properties that, if tuned are being investigated at The Wark (Figure 1). Prof Hans Griesser properly, can be exploited to design new classes A major research area is the development Prof Peter Majewski of intelligent materials in medical applications. of nanoparticulate-contrast agents for Nanotechnology therefore offers innovative magnetic resonance imaging (MRI), such as External Collaborators solutions to some of the most common medical superparamagnetic iron oxide nanoparticles and Dr Michael Brown challenges, including lack of early disease detection, ultrasmall gadolinium oxide nanoparticles, which (Royal Adelaide Hospital) non-specific systemic distribution and inadequate are synthesized using green chemistry principles. Dr Chris Barbé (ANSTO) concentrations of therapeutic/diagnostic agents, In collaboration with ANSTO, porous silica and the inability to monitor therapeutic responses. nanoparticles carrying a payload of bioactive or fluorescent agents are investigated for targeted in vivo drug delivery or diagnostic applications1. In addition, the spontaneous self-assembly of amphiphilic diblock copolymers onto a core-forming hydrophobic optically active gold nanoparticle has been developed towards the preparation of multimodal therapeutic hybrid nanostructures.

The fine control and application of nanomaterials such as nanoparticles in complex biological environments, however, remains a formidable

Figure 1: Functional Nanoparticle Research at The Wark. Towards a new generation of diagnostic and therapeutic nanomaterials

24 “Standard” PEG interface “Dense” PEG interface Figure 2

Non-specific binding to cell membrane of fluorescently labelled silica nanoparticles

Dense PEG brush providing resistance to biologically non- specific binding events

challenge. Understanding and controlling apoptotic cells. Although apoptosis is the most interactions of biological-entities such as cells frequently described mode of tumor cell death and proteins with nanoparticles is of paramount resulting from the action of most anticancer drugs, importance in the design of advanced biosensing, the need for accurate, robust and clinically relevant diagnostic and therapeutic applications. Extending methods for the detection of tumor cell apoptosis in the expertise gained on the study of biointerfaces vivo remains unmet. In vitro studies demonstrated at the macroscopic level (e.g. implants), we are that these novel immunotargeted nanoprobes actively developing dedicated surface engineering were able to bind to post-apoptotic permeable procedures designed to control the bio-interfacial cells in vitro with high specificity. Supported by a properties of functional nanoparticles prepared NHMRC project grant, the research team is currently at The Wark. A major focus of this research is the investigating these MRI nanoprobes in an animal control of biologically non-specific binding events model to fully assess their potential to image and that occur at the nanoparticles biointerface in detect intratumoral apoptosis in vivo. physiological environment. Dense polyethylene glycol (PEG) nanoparticles coatings have been References developed and shown to drastically reduce these non-specific interactions with proteins and cells 1. Thierry B, Zimmer L, McNiven S, Finnie K, Barbé (Figure 2). C, Griesser HJ Design of a new stealth drug delivery system:Electrostatic self-assembly of PEG Building on these novel biointerfaces, copolymers onto silica nanoparticles. Langmuir, immunotargeted MRI nanoprobes have been in press developed in collaboration with the Royal 2. Thierry B, Al-Ejah F, Brown M, Majewski P, Adelaide Hospital2. PEGylated superparamagnetic Griesser HJ Immunotargeting of advanced nanoparticles were conjugated with a monoclonal functional nanostructures for cancer diagnosis antibody specific for the La ribonucleoprotein, and treatment. Accepted for Advanced Materials which is overexpressed at both mRNA and protein level in malignant cells and which becomes available for binding in the cytoplasm of permeable post-

Ian Wark Research Institute Annual Report 2007 25 Engineered Nanotube Membranes for Molecular Separation and Biosensing

Research Sponsors Aims and Background Fabrications ARC Discovery, ARF Fellowship Aims of this project are directed toward Porous alumina (PA) electrochemically etched UniSA Fellowship development of advanced nanotube membranes for from aluminium foil is one of the major templates AINSE molecular separation and biosensing. In comparison used for fabrication of nanotube membranes in with other porous membranes, advantages of this project. A highly flexible, computer controlled Research Staff nanotube membranes is their low cost fabrication, electrochemical system for advanced fabrication of Dr Dusan Losic ability to control channel dimensions with nano PA membranes has been developed. The system size precission (diameter, length, shape), flexibility allows for routine fabrication of PA membranes with Research Student in using different materials (alumina, gold, silica, desired pore size (30 nm to 500 nm), pore distance Ms Leonora Velleman carbon, polymers), ability to apply desired surface (60 nm to 1000 nm), and membrane thickness functionalisation, flexibility in applying a variety of (1 um to 200 um). (Figure 1) selectivity approaches in separation process (size, sterics, electrostatics, electrophoretic, interfacial, Protocols for electroless deposition of gold and chemical, biorecognition) and capacity to combine fabrication of gold nanotube membranes using separation with biosensing and microfluidic devices PA and polymer templates were developed, and (lab on a chip). The project adapts broad research membranes and gold nanotubes with controlled activities including nanofabrication, surface pore size were fabricated (min. 5nm). (Figure 2) Figure1 Fabricated PA membranes modification and functionalisation, separation with different pore size studies, nanofluidics and biosensing. Engineered Nanotube Membranes

To optimise transport and selectivity properties of nanotube membranes several strategies have been explored including: the geometry (shape) of pores, the diameter of pores, and surface chemistry.

• A series of new nanotube membranes with hierarchical pore structures, nanobrushes, asymmetrical shape (bottle-neck), pores in channels, and various modulated geometries have been developed. (Figure 3)

• Structural modification of PA membranes by silica is demonstrated by atomic layer deposition (ALD) to achieve the controlled reduction of pore size to < 5 nm (with ANSTO research group).

• Chemical and structural modification of PA membranes by plasma polymerisation of n- heptylamine to improve membrane separation properties and bio-compatibility is demonstrated.

Figure 2 Gold nanotube membranes fabricated by gold deposition on porous template b-c) gold nanotubes

Au

Gold Nanotube Membrane Gold nanotube

26 • A variety of organic modification approaches Figure 3 Advanced nanotube were applied for surface functionalisation of gold membranes with nanotube membranes including: self-assembled a-b) modulated internal shape, monolayers (SAMs) and electrochemical methods c) brushes on the top, (polymerisation and anodic deposition). New d) hierarchical and SAMs and polymer functionalised gold nanotube e) asymmetrical pores

membranes with different interfacial properties (modified with SiO2 and selectivity were prepared.

Separation Studies

Transport and selectivity properties of thiol Membrane functionalised gold membranes were investigated Hydrophobic by monitoring the diffusion of a series of molecules 8 with different sizes, charge, and interfacial properties across a membrane. The selectivity toward hydrophobic and hydrophilic molecules 6 and using SAMs terminated with COOH and CH3 groups is achieved and their successful separation is demonstrated. (Figure 4) 4 Dye transported Dye References Moles transported (nmol) 1. D.Losic, M. A. Cole, B. Dollmann, K. Vasilev, H. 2 J. Griesser, Surface modifications of nanoporous Hydrophilic alumina membranes by plasma polymerisation,

Nanotechnology, 2008 19, 245704 (7pp) 0 2. L. Velleman, J. G. Shapter, D. Losic, Template 0 2 4 6 fabricated gold nanotube membranes: a Time (h) nucleation and growth study, 15 th Australian Conference on Nuclear and Complementary Figure 4 Transport of hydrophobic techniques of Analysis, Nov 21-23 2007, and hydropilic dye through Melbourne, Proceedings Book of Papers, 2007, a gold nanotube membrane 15, 161-165 functionalised with the 3. M. A. Cole, B. Dollmann, K. Vasilev, H. J. hydrophobic thiol 1H,1H,2H,2H- Griesser, D. Losic, Surface modifications of Perfluorodecanethiol nanoporous alumina membranes by plasma polymerisation, 15 th Australian Conference on Nuclear and Complementary techniques of Analysis, Nov 21-23 2007, Melbourne, Proceedings Book of Papers, 15, 2007, 161-165 4. L. Velleman, J. G. Shapter, D. Losic, Fabrication of functionalised nanopore membranes for use in molecular separations, Proceedings ARNAM 2007, July 8-11 2007, ANU Kioloa Campus

Ian Wark Research Institute Annual Report 2007 27 Nanoparticle Encapsulated Emulsions for Improved Dermal Delivery of Retinol (Vitamin A)

Research Funding Background and Aims Achievements Bioinnovation South Australia (Commercial Development Grant) Retinoids (natural and synthetic derivatives of Hydrophilic silica nanoparticles and charged Itek Pty Ltd retinol) are a homologous series of lipophilic surfactants show synergistic effects in facilitating compounds with great importance in modern the formation and stability of submicron triglyceride Research Staff therapeutic and cosmetic dermatological emulsions1. Furthermore, the formation of Prof Clive Prestidge preparations. Vitamin A (all trans retinol) is a colloidosomes from submicron triglyceride Dr Spomenka Simovic bioactive retinoid that induces skin epidermis emulsions and silica nanoparticles is critically thickening and thinning of the stratum corneum; it controlled by the emulsifier charge, nanoparticle Research Student is more active and displays lower skin irritation and level and emulsion volume fraction2. Ms Nasrin G Eskandar toxicity compared to other retinoids (e.g. retinoic acid). However, retinol has a number of instability The photo-chemical stability of vitamin A in pathways and is challenging to formulate and emulsions is significantly increased by silica deliver. nanoparticle encapsulation. Membrane (cellulose acetate) transport studies using Franz diffusion cells Oil-in-water emulsions are excellent carriers of have confirmed that nanoparticle layers facilitate lipophilic molecules and are commonly used sustained release of vitamin A. This is in agreement as cosmetic and pharmaceutical formulations. with our observed controlled release from silicone However, emulsions are far from ideal in their emulsions3. stability and delivery characteristics. Our aims are to form layers of silica nanoparticles at the sub- Porcine skin uptake of vitamin A from emulsions micron oil droplet-water interface and investigate is significantly increased by the inclusion of silica the stability, release and skin delivery (penetration nanoparticle layers4 (Figure 1). and distribution) behaviour of retinol (and other probe molecules) from nanoparticle encapsulated The presence of silica nanoparticle layers also emulsions. triggered the delivery of Vitamin A (and other lipophilic agents) to the viable skin layers, i.e. epidermis and upper dermis – see Figures 2 and 3. Such targeted delivery with minimal trans-dermal delivery is highly desired for topical pharmaceutical and cosmetic preparations.

The mechanisms for improved dermal bioavailability of Vitamin A from nanoparticle encapsulated emulsions are under further investigation.

Figure 1. Skin uptake and 35 Skin retention transport to receptor phase of Transport to the receptor phase vitamin A from control and silica 30 nanoparticle coated emulsions 25 * 20

15

10 * 5 * Normailsed concentration of vitamin A 0 Control Silica-included Control Silica-included Lecithin Oil Water Oleylamine Oil Water

28 References 3. S. Simovic and C. A. Prestidge, “Nanoparticle Layers Controlling Drug Release from 1. N. Ghouchi Eskandar, S. Simovic and C. Emulsions”, European J. of Pharmaceutics and A. Prestidge, “Synergistic Effect of Silica Biopharmaceutics, 66, 39-47, 2007. Nanoparticles and Charged Surfactants in the 4. N. Ghouchi Eskandar, S. Simovic and C. A. Formation and Stability of Submicron Oil-in- Prestidge, “In-vitro Release Kinetics and Dermal Water Emulsions”, Physical Chemistry and Delivery of All-trans Retinol from Nanoparticle Chemical Physics, 9 (48), 6426-6434, 2007 Encapsulated Emulsions ”, under review 2. S. Simovic and C. A. Prestidge, “Colloidosomes 7061-70. from the Controlled Interaction of Submicron Triglyceride Droplets and Hydrophilic Silica Nanoparticles”, Langmuir, 24, 7132-7137, 2008 Figure 2. Confocal images (orange 10-nonyl bromide is the lipophilic probe) of vertical sections of skin treated with control and silica-included emulsions (first layer from the top: stratum corneum)

Lecithin Stabilised Emulsion Lecithin Stabilised Emulsion Oleylamine Stabilised Emulsion Oleylamine Stabilised Emulsion Encapsulated with Encapsulated with silica silica nanoparticles nanoparticles

Figure 3. Depth profile of skin Control oleylamine distribution of Vitamin A from 0.5 Silica included from the oil phase control and silica-included oleylamine emulsions Silica included from the aqueous phase

0.4

0.3

0.2 Vitamin A concentration (mcg) Vitamin 0.1

0.0

0 50 100 150 200 250 300 350 400 450 Skin Depth (µm)

Ian Wark Research Institute Annual Report 2007 29 Colloids and Nanostructures Sector Coordinator: A/Prof Daniel Fornasiero

Major Research Themes • Friction and capillary forces with condensed liquids (QEII Fellowship: Satomi Onishi). Stability of colloidal particles, including their aggregation, dispersion and adsorption on solid or • Nano and Bio-Materials Centre funded by the gas surfaces. Federal Government grant to work with overseas researchers to develop new products and Manipulation of surface chemical and physical materials using nano and bio technology nano-heterogeneities to influence the properties of these surfaces with simple and complex fluids. • Interfacial Properties of Ionic Liquids and their Electrochemical Manipulation (CSIRO - Minerals) Current Research • Particle-Bubble Interaction (CSIRO - Minerals) • ARC Special Research Centre funding on static and dynamic wetting • Australian Mineral Science Research Institute (AMSRI) involving the Universities of Melbourne, • Polymers at mineral interfaces (AMIRA P498B) Newcastle and Queensland and funded by an (ARC Linkage and Cytec Australia, Penford ARC Linkage with industry partners of BHP Australia, Rio Tinto, Anglo Platinum, Xstrata, CP Billiton, Rio Tinto, Anglo Platinum, Phelps Dodge, Kelco Oy) Xstrata Technology and Orica Mining. The • Control of aggregate structure settling and Wark is involved in all the research programs dewatering in mineral tailings processing (ARC but particularly in the topics of ‘Material and Linkage and Rio Tinto) Interface Science’ and ‘Advanced in- and ex-situ Analysis’. There were two sponsor meetings, one • Model studies of the wettability of resevoir and in Adelaide and the other in Newcastle. seal rocks as recovered and after treatments to alter surface properties (ARC Linkage) A strong collaboration exists between Sectors, especially with the Mineral Processing Sector in • Integrated predictive evaluation of traps and seals the application of the IWRI flotation model to (CSIRO Petroleum) predict mineral flotation in plant ores and with the Materials & Environmental Surface Science Sector in • Stabilisation of titania pigment slurrries during the surface and bulk characterisation of minerals. processing (ARC Linkage and Tiwest Joint Venture) Completion of PhD Candidature Three students completed their PhD for research • Development of a new type of large area robust involving Colloids and Nanostructures: Jarred super hydrophobic surfaces (ARC Linkage Clasohm, Linh Cuba-Chiem and Kate McLeod. A/Prof Jonas Addai-Mensah and International with the University of Suny- Ms Nicola Sleep Binghampton, USA) Colloid Stability of

30 Thymine-Functionalized Gold Nanoparticle

The purpose of this work is to study the aggregation and pH-sensitive. Previous studies have shown that Research Sponsor and dispersion behaviour of gold nanoparticles the surface pKa of thyminethiol derivatives with ARC Special Research Centre coated by thyminethiol derivatives containing long long hydrocarbon chains is 11.24. When the pH hydrocarbon chains. We focus on the influence of value is above this pKa, the thymine molecules are Research Staff solution pH, salt type and concentration, and on the deprotonated and therefore negatively charged Laureate Prof John Ralston role of the thymine end group in controlling colloid (Figure 3), which results in strong electrostatic Dr Rossen Sedev stability. repulsion between particles, and a stable particle Dr David Beattie

dispersion. At pH value below the pKa the thymine The aggregation and dispersion properties of molecules are protonated and therefore non- Research Student nanosized colloid particles are essential for their charged; as a result electrostatic repulsive forces are Ms Jingfang Zhou optical, electronic, and catalytic application1,2. In small compared to van der Waals attractive forces most cases, however, nanoparticles are surrounded and particles aggregate. by an organic layer. For colloids whose surfaces are coated by surfactants, polymers, or biomolecules, Non-DLVO forces may have also a strong influence the nature and chemistry of the organic layer play on stability, especially for small particle sizes3. In an important role in stabilizing the particle3. particular, it was found that the dispersions were unstable at pH 12.5 in the presence of concentrated Gold nanoparticles surface-coated with thyminethiol LiCl and CsCl solution but remain stable with derivatives containing long hydrocarbon chains concentrated NaCl and KCl solutions (Figure 4). (1-(10-mercaptodecyl)-5-methylpyrimidine-2,4- At high salt concentrations, electrostatic repulsion dione) have been prepared. The diameter of the forces are too weak to disperse the particles as it is particles is around 5 nm, with a relatively narrow the case with LiCl and CsCl. The observed colloid size distribution. The colloid stability of these gold stability in the presence of NaCl or KCl is attributed nanoparticles was monitored in aqueous solutions to strong hydration repulsion5. using UV-visible absorption spectroscopy (Figure 1). References The solution pH influences the colloid stability of 1. Hu, Y.; Dai, J. Miner. Eng. 16 (2003) 1167-72. the gold particles as shown in Figure 2. At pH 12.5 2. Snoswell, D. R. E.; Duan, J.; Fornasiero, D.; or above, the gold particles were dispersed and Ralston, J. J. Colloid Interface Sci. 286 (2005) transparent dispersions were formed but when 526-35. the pH was reduced, the particles coagulated 3. Lyklema, J. H. Fundamentals of Interface and and sedimented. This process was reversible. The Colloid Science; Vol IV: Particulate Colloids; stability of the gold particles in aqueous solutions Elsevier Academic Press: New York, 2005. is controlled by the balance of van der Waals 4. Jang, Y. H.; Sowers, L. C.; Cagin, T.; Goddard, W. attractive forces and electrostatic repulsive forces A. J. Phys. Chem. A 105 (2001) 274-80. (DLVO theory). Thymine molecules are ionizable 5. Manciu, M.; Ruckenstein, E. Langmuir 17 (2001)

Figure 1. Influence of CsCl 2.0 CsCl no salt 1.0 0.01M concentration on the colloidal 0.05M 0.10M 0.8 stability of thymine-coated 1.5 0.25M 0.5M gold particles in pH 12.5 0.75M 0.6 1.0 1.00M water. 1.25M 0.4 0.5 1.50M Absorption 0.2 Figure 2. Influence of pH on 2.2 nm nanoAu the colloid stability of the 2.2 0.0 0.0 7.0 nm nanoAu Normalized Absorbance and 7.0 nm diameter thymine- 250 300 350 400 450 500 550 600 650 700 11.0 11.2 11.4 11.6 11.8 12.0 12.2 12.4 12.6 12.8 13.0 coated gold particles without Figure 1 Figure 2 pH value Wavelength (nm) salt addition. 1.0 Figure 3. Surface properties of 0.8 thymine-coated gold particles 0.6 at different pH values. - H+

S S Au Au N O O N 0.4 Figure 4. Influence of + H+ LiCl N N 0.2 NaCl monovalent salt concentration KCl O H 1 O 0.0 CsCl on the colloidal stability of Normalized Absorbance pH < pKa pH > pKa thymine-coated gold particles 0 1 2 3 4 5 in pH 12.5 water. Figure 3 Figure 4 Salt Concentration (M)

Ian Wark Research Institute Annual Report 2007 31 The Terminal Rise Velocity of 10-100 µm Diameter Bubbles in Water

Research Sponsor The dynamics of a bubble moving in a fluid medium freely in ultra-clean water. The sizes and terminal ARC has crucial ramifications in research, industrial rise velocities of these bubbles were measured by AMIRA International processing and in many natural processes. A high-speed video microscopy, and compared with gas bubble released in a liquid medium will rise, terminal velocity values predicted by Stokes’ Law Research Staff accelerating to a point where its buoyancy force, a and the Hadamard and Rybczynski equation. Figure Laureate Prof John Ralston function of its size and density, is balanced by the 1 shows bubble velocity versus diameter curves A/Prof Daniel Fornasiero drag force retarding its motion. The dissipation of for each of the four gases tested. The terminal

Dr Rossen Sedev inertial and viscous energy within the fluid, which velocities for He, N2 and air bubbles showed accounts for the drag force, varies significantly, excellent agreement with those predicted by the Research Student depending on the flow regime about the bubble. In Hadamard–Rybczynski equation. This indicates that Mr Luke Parkinson turn, this is influenced by its diameter and velocity, in sufficiently clean liquids, the bubble surface is as well as by the state of the bubble surface, fully mobile, that is, there is slip at the gas–liquid

that is, whether it is mobile, immobile or at some interface. The terminal velocities of very small CO2 intermediate condition. bubbles were greater than those predicted by the Hadamard–Rybczynski equation, behaviour which is The terminal velocity for a solid sphere (immobile particularly evident below a diameter of 60 μm. This surface) moving in a viscous liquid is described effect was attributed to the enhanced solubility of 1 by the well-known Stokes’ Law , which has been CO2 causing the formation of a diffusion boundary extensively validated at low Reynolds number layer around small bubbles, enhancing their

(Re). However, Stokes’ Law does not hold as Re terminal velocities (CO2 is approximately two orders approaches unity which, for an air bubble rising of magnitude more soluble than the other three in water, coincides with a bubble radius (r) of gases). approximately 50 µm. In these conditions, the terminal velocity can be described by the Hadamard References and Rybczynski equation2, 3, 1. Stokes, G.G., On the Effect of Internal Friction Figure 1. Terminal rise velocity 2$R r g 3 of Fluids on the Motion of Pendulums. Camb. versus bubble diameter plots Ut(H - R) = = Ut(ST) 3µ 2 Philos. Trans, 1851. 9: p. 8. for air, nitrogen, helium and where Dr, g, µ and U are the difference in 2. Hadamard, J.S., Mouvement Permanent Lent carbon dioxide bubbles in water. t(ST) density between the sphere and the surrounding d’une Sphere Liquide et Visqueuse dans un Comparisons with Stokes’ (solid fluid, the gravitational acceleration, fluid viscosity Liquide Visqueux. Compte-Rendus de l’ Acad. lines ——) and Hadamard- and terminal velocity calculated with Stokes’ Law, des Sci., 1911. 152: p. 1735-1752. Rybczynski´ (broken lines – – –) respectively. 3. Rybczynski, W., On Translatory Motion of a Fluid terminal velocity predictions are Sphere in a Viscous Medium. Bulletin of the shown. Data points represent Single bubbles of air, air, nitrogen (N ), helium (He) Academy of Sciences, Cracow, 1911. Series A: single bubbles. 2 and carbon dioxide (CO2) were allowed to rise p. 40.

12000 12000

) Air Nitrogen

-1 10000 10000 8000 8000 6000 6000 4000 4000 2000 2000 Rise Velocity (µm.s Rise Velocity 0 0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 12000 12000 )

-1 10000 Helium 10000 Carbon Dioxide 8000 8000

6000 6000

4000 4000

2000 2000 Rise Velocity (µm.s Rise Velocity 0 0 0 20 40 60 80 100 120 0 20 40 60 80 100 120 Bubble Diameter (µm) Bubble Diameter (µm)

32 Materials and Environmental Surface Science Sector Coordinator: A/Prof Bill Skinner

Overview ARC Linkage Grant in New Membrane Synthesis for Energy Storage The major focus of the Materials and Environmental Surface Science Sector is the structure and chemistry A new project, headed by Prof Namita Roy of solid surfaces and interfaces. Particular emphasis Choudhury and A/Prof Bill Skinner, with funding is given to the study surface reaction, transport and from the ZBB Energy Corporation and support from exchange at the atomic scale. an ARC Linkage Project came to fruition in late 2007. The project is entitled Novel Nanostructured The application and development of surface Polymeric Membranes for Energy Storage science techniques, including surface analysis and Applications and will focus on developing a new synchrotron science, has been a core strength of membrane for the zinc bromine battery (ZBB). the Sector’s activities, has contributed widely to projects in other Sectors, programs of the ARC The zinc-bromine battery (ZBB) is an attractive Special Research Centre for Particle and Materials candidate for stationary and vehicle energy storage Interfaces, the Australian Mineral Science Research due to its high energy density, efficiency, the use Institute (AMSRI) and its partners, and has facilitated of abundant low-cost materials and ambient research across the The Wark in general. temperature operation. It is also able to be discharged completely without detrimental effects The Sector also provides expertise in the application to its operation and has much less “embodied and development of a range of instrumental energy” in its manufacture. techniques in fundamental, strategic-basic and industrial research. Our research areas include: The research project will bring significant benefit to • Deposition, processing and characterization of the Australian community and economy, providing coatings and thin films the nation with renewable energy storage solutions, • Mineral Surface Chemistry and Reactivity with zero emission and urban pollution, will – oxidation, adsorption, dissolution position Australia as a global leader in sustainable • Quantum Chemical Modelling of solids and energy storage technology through ZBB’s novel surfaces correlated with spectroscopy battery system development and will deliver a • Forensic Analysis strong intellectual property (IP) position in frontier • Materials Surface Science technologies. • Optical materials (e.g. oxide pigments) • Photo- and electro-catalysis New ToF-SIMS Instrument to be Funded by • Renewable energy materials NCRIS • Leaching, crystallisation and precipitation • Metallurgical joining and corrosion The first funding round of the National • Environmental Surface Chemistry Collaborative Research Infrastructure Scheme • Application and development of advanced (NCRIS) saw great gains for The Wark and South analytical techniques Australia in general. The Wark has received significant funding as NCRIS Nodes under two At The Wark strategic areas - Characterisation and Fabrication. X-ray Photoelectron Spectroscopy (XPS) Under Fabrication, The Wark received funding for Time-of-Flight Secondary Ion Mass Spectrometry laboratory and equipment infrastructure for nano- (ToF-SIMS) scale patterning and micro-fluidic device fabrication Raman spectroscopy and microscopy (see page 17 for details).

At Synchrotron Facilities Around The World Characterisation infrastructure forms part of the Synchrotron Radiation X-ray Photoelectron Australian Microscopy and Microanalysis Facility Spectroscopy (SR-XPS) (AMMRF) which incorporates the local node, X-ray Absorption Spectroscopies (XAS) including the South Australian Regional Facility (SARF) run XANES, EXAFS and NEXAFS jointly by UniSA, Flinders University, the University X-ray Fluorescence microprobe imaging and micro- of Adelaide. The Wark will gain a new, state-of- XANES (μXRF, μXANES) the-art ToF-SIMS instrument while a Focussed-Ion Scanning Photoemission Microscopy (SPEM) Beam instrument (FIB) will be situated at Adelaide Photo-Emission Electron Microscopy (PEEM) Microscopy, University of Adelaide. Micro-X-ray Computer-aided Tomography (μCT) IR spectroscopy and imaging Towards a Greener X-ray Reflectivity X-ray microscopy and Diffraction Energy – Synthesis of

Ian Wark Research Institute Annual Report 2007 33 Novel Membranes and Catalyst for Hydrogen Fuel Cells

Research Sponsors The aim of our research is to develop novel In the case of NafionTM, its high proton conductivity ARC Discovery Grant materials for Proton Exchange Membrane Fuel Cells is partly due to its phase separated morphology (PEMFC) that enables higher operating temperature creating ionic domains (Figure 2) which provide Research Staff and efficiency. This project studies two main aspects a pathway for proton conduction. This phase Dr Naba Dutta of the Membrane Electrode Assembly (MEA), separation can also be achieved using block Prof Namita Roy Choudhury namely the Proton Exchange Membrane (PEM) and copolymers, and we have prepared a series of Dr Surya Subianto the metallic catalyst. proton exchange membranes by sulfonation or phosphonation of block copolymers. These Research Students PEMFCs have attracted significant research attention functionalized block copolymers show comparable Mr Mayur Mistry as an alternative energy source, particularly in conductivity to literature values for linear Mr Sundar Mayavan portable application such as transport where it is polymers despite significantly lower degree of seen as a possible long-term alternative to fossil functionalization, showing that the phase-separated fuels. Unlike internal combustion engines, fuel morphology of block copolymer is advantageous for cells convert chemical energy into electrical energy, proton conduction as it is capable of concentrating possessing greater efficiency and very low to the acidic functionalities in the ionic domains. zero emission. At the heart of the PEMFC is the Membrane Electrode Assembly (MEA) (Figure 1), In order to increase high temperature performance, where the chemical reactions and power generation hydrophilic inorganic fillers (Figure 2) such as silica occur. are often incorporated within PEMs to improve water retention. However, its use results in lower Electric Circuit conductivity due to the reduction of free volume (40% - 60% efficiency) within the polymer, resulting in a lower water e - e - e - e - uptake and hence a decrease in conductivity. In Fuel Gas Catalyst Catalyst Gas this project, this has been overcome by using input O2 diffusion electrode PEM electrode diffusion e - (from air) backing layer layer backing Qxygen gas functionalized molecular silicas, which possess (H2) e - H + from air finds Hydrogen a pathway to small size and high surface area, resulting in better H + gas finds a the catalyst pathway to layer the catalyst dispersion and increased conductivity especially e - Heat layer Pathways of - water from Cathode Anode e H + catalyst layer at low humidity where there is an order of + Carbon Platinum Pathways of Unused H Output nanoparticles catalyst electron magnitude increase in conductivity compared to conduction TM H2 (Air + H2O)) Nafion . Mechanical analysis showed increased (recirculated) glass transition temperature with incorporation of Figure 1. Schematic of a PEMFC inorganic component, showing strong interaction and the MEA (adapted from Despite the attractiveness of fuel cells, their between the filler and the matrix which improved its http://physics.nist.gov, 2006) practical application still faces some important mechanical properties at higher temperatures. technical challenges1. One of these is to create new membrane materials that can operate In order to achieve conductivity under completely at temperatures above 100°C, as this greatly anhydrous conditions, alternative charge carriers are increases the CO tolerance of the catalyst and needed in place of water. Ionic liquids have excellent improves electrode kinetics, leading to greater thermal stability and conductivity, and we have efficiency and removes the need to eliminate CO incorporated such ionic liquids in supported liquid from the feed gas. However, current PEMFCs still membranes (SLM), resulting in good conductivity uses perfluorosulfonic acid membranes such as at high temperature and anhydrous conditions as NafionTM, a sulfonated tetrafluorosulfonic acid proton conduction occurs through the ionic liquid. Figure 2. Incorporation of copolymer discovered in the 1960s. Despite their These new membranes show good conductivity hydrophilic particles in ionic high conductivity and excellent chemical stability, at high temperatures where NafionTM membranes domains of proton exchange they lose conductivity at high temperature and a became non-conducting due to dehydration, with membrane different type of membrane material is needed for the SLM’s conductivity increasing significantly with this application. temperature above 120ºC (Figure 3).

Ionic Cluster Semicrystalline Another aspect of the PEMFC is the catalytic 30 - 50 nm Hydrophobic Region nanoparticles, which is utilized in the splitting and recombination of hydrogen and oxygen into water. However, an approximately five-fold reduction in the amount of platinum loading in current PEMFC is required in order to meet the cost requirement of large scale automotive applications2, and thus a Inorganic better synthetic method is required to create catalyst Nanoparticles with greater effective surface area and efficiency.

34 The block copolymers used in our PEM studies • S. Subianto, N. Roy Choudhury and N.K. Dutta possess ionic domains capable of stabilizing such “Palladium-catalysed phosphonation of SEBS nanoparticles, and the solvent-driven morphology block copolymer” Journal of Polymer Science of the block copolymer can act as a template, Part A: Polymer Chemistry (2008), (46), 5431. where the ionic domains act as a nanoreactor • M.K. Mistry, N. Roy Choudhury, N. K.Dutta, for the synthesis of catalyst nanoparticles. In S. Holdcroft, Inorganic modification of ionic this investigation, self-assembled structures of block copolymers for high temperature PEM functionalized block copolymer were created by application, Abstracts of Papers, 234th ACS controlling its environment and this was utilized to National Meeting, Boston, MA, United States, direct the deposition of metallic nanoparticles. This August 19-23, 2007 (2007). template mediated deposition was used to generate • M.K. Mistry, N. Roy Choudhury, N. K. Dutta, highly dispersed nanosized Pt (2-3.5 nm) and Pt- S. Holdcroft, Inorganic modification of ionic Co (1.5-2.5 nm) particles for catalytic applications block copolymers for high temperature PEM (Figure 4) . application. PMSE Preprints (2007), 97, 17-18. • S. Mayavan, N. Roy Choudhury and N.K. Dutta Furthermore, a novel nanoscale platinum decorated “Ionomer stabilized noble metal colloids for Multi-Walled Carbon Nanotube (MWCNT) catalytic applications”. PMSE Preprints (2007), Figure 3. Increase in conductivity hybrid material has been synthesized by taking 97, 910-911. with temperature for ionic liquid advantage of functionalized CNT interaction with membranes under anhydrous functionalized self-assembled block copolymer conditions structures. The use of MWCNT will provide better pathway for electron conduction, while at the same time alleviate problems such as platinum Conventional hiding and sintering that occurs with conventional Supported Liquid Membranes carbon support. In this study, the in-situ synthesis Membranes of Pt on the functionalized MWCNT was carried out by taking advantage of fn. MWCNT interaction with functionalized, self-assembled block copolymer structures. The key parameters in our

work (involving Pt and Pt/MWCNT hybrids) are Conductivity the combination of self assembly and charged block interaction with counter ions (Pt ions, polar groups on the side wall of MWCNT) to efficiently immobilize metal nanoparticles besides stabilizing and homogenously dispersing the carbon Temperature nanotubes. We demonstrate that this method can result in high quality Pt (111) catalysts of uniformly dispersed Pt nanoparticles with size less than 3 - 4.0 nm in diameter, ideal for use as PEMFC catalysts, resulting in a large surface area as shown by cyclic voltammetry which would be beneficial to its performance. 1 References Block copolymer Self-assembly Metallic Metallic precursor loading 1. Steele, B.C.H.; Heinzel, A; Nature 2001 (414) Functional 345-352. Block Copolymer n 2. Stamenkovic, V.R.; Fowler, B.; Mun, B.S.; Wang, PO(OH)2 G.; Ross, P.N.; Lucas, C.A.; Markovic, N.M.; 2 3 Science 2007 (315) 493-497.

Catalyst Reduction Publications from this Work Nanoparticle

• S. Mayavan, N. Roy Choudhury and N.K. Nano-structured metal colloid Dutta “Pt-catalyst nanoparticles from directed deposition in functional block copolymer”. Adv Mat. 2008 (20) 1819. Figure 4. Synthesis of catalytic nanoparticles for fuel cell

Ian Wark Research Institute Annual Report 2007 35 Mineral Processing Sector Coordinator: A/Prof Stephen Grano

Overview which A/Professors Daniel Fornasiero and Stephen Grano are the Chief Investigators. It is also noted A major undertaking in 2007 was the successful that Dr Igor Ametov was promoted to Research recruitment of all PhD candidates required for the Fellow in 2007 for which we resoundly congratulate P260E project titled ‘Improving Sulphide Mineral him and thank him for his excellent work. Flotation’. The following PhD candidates were successfully recruited into the P260E project: Mr A major contributing factor in the success of the Solomon Muganda, Mr Xiangfei Ye, Mr Heramb Mineral Processing Sector is a close relationship with Bal, Mr Wenbo Wang, Mr Lin Zhou, Mr Daniel AMIRA International and key international minerals The IsaMill is a horizontal stirred Chipfunhu, Ms Dangfu Xu, Mr Yunyu Shi, and Ms companies. Research is also underpinned by the mill manufactured by Xstrata Susana Abreu – who will all commence by early ARC Special Research Centre activities and the Technology, a sponsor of the 2008. A selected highlight of the precursor project, Australian Mineral Science Research Institute. P260E project. Internal rotating P260D, is discussed further below. discs agitate the grinding media Research Highlights and ore slurry which is continually The current sponsors of the P260E project include fed into the mill. The breakage Anglo, Vale Inco, Freeport McMoRan Copper & A highlight of the research in the P260D and of the particles occurs by attrition Gold Inc., Rio Tinto (Kennecott), and Somincor P260E projects is the study of the particle size producing fine particles which (Lundin Mining Corporation) as Case Study limits in flotation, for both the coarse and fine end is controlled by the speed of Sponsors; BHP Billiton – Nickel West, BHP Billiton of the particle size spectrum. Typical plant data the rotating discs, flow of slurry – Escondida, Boliden, Vale, Magotteaux, Ok Tedi show that, for the case of porphyry copper ores, and media size. The IsaMill is Mining, Outotec, Oxiana, Teck Cominco and Xstrata rougher recovery of copper bearing minerals is at currently used by PhD candidate Technology as Generic Sponsors; and COREM and a maximum in the size range of 10 to 100 microns Mr Xiangfei Ye (far right) in the Intellection as Technology Supplier Sponsors. The (90-98%), and then decreases to the range of 30 to project “Optimising Grinding and Wark gratefully acknowledges these sponsors of 50% for the +150-300 micron particle size range, Regrinding Chemistry” supervised the P260E project. Furthermore, The Wark was and to less than 20% for the +300-450 micron by A/Prof Stephen Grano and Dr successful in obtaining an ARC Linkage Award with particle size range. Quantitative liberation analysis Sabina Gredelj the P260E project, announced in July 2006, and for has revealed that, in at least the case of Freeport

36 Freeport Indonesia case principally due to oxidation Mr Louie Del Castillo (left) and in the mine. The decreased contact angle of the Dr Max Zanin conducting a free surface of the copper mineral, brought about laboratory flotation experiment by oxidation, increases the liberation class necessary on a chalcopyrite ore. The to achieve recovery for a given coarse particle size hydrophobic copper bearing range. In this particular survey at Ok Tedi, there particles are recovered in the is lower recovery of the +150-300 micron particle froth phase size range even for fully liberated copper bearing particles (Figure 1). The lower hydrophobicity of the free surface of the copper bearing mineral in this Ok Tedi survey is also reflected in the lower recovery of fully liberated copper bearing particles in the sub 10 Indonesia, rougher recovery of copper bearing micron particle size range (Figure 1). It is important minerals in the +150-300 micron size range can to note that the recovery of coarse composite be greater than 90% for liberation classes from particles is very important in plant practice as it is 100% (i.e., fully liberated) down to 30% by free this size range that is often the most significant surface area of the copper bearing mineral in the form of loss in value mineral recovery. Furthermore, composite particle. Below this liberation class, the ability to recover poorly liberated composite recovery steadily declines. At Freeport Indonesia, it particles opens the opportunity to increase the feed is noted that the free surface of the copper bearing particle size distribution by treating an increased mineral is strongly hydrophobic, characteristic of tonnage of ore feed. Thus concentrate production the maximum contact angle attainable with the may be increased if means can be identified to collector chain length used (75-80o)1. increase composite particle recovery in roughing flotation. Reduced energy consumption in Another example is a particular survey of the Ok comminution is another benefit of being able to Tedi Mining Limited rougher circuit (Figure 1). In recover value bearing particles in coarse size ranges, this particular case, the overall hydrophobicity of the and as value mineral contained within composite copper mineral surfaces is much lower than in the particles.

Ian Wark Research Institute Annual Report 2007 37 Figure 1. Copper recovery as 100 a function of particle size for Mineral liberation class (%) different liberation classes in a 0-20 survey of the Ok Tedi Mining 80 20-50 Limited Rougher circuit. Low fine 50-100 copper recovery suggests that the 100 copper mineral free surface is not 60 strongly hydrophobic. Decreasing liberation causes lower recovery, particularly in coarse particle size fractions. Recovery (%) 40

20

0 1 10 100 1000 Particle Size (microns)

Figure 2. Quartz recovery after 8 100 minutes of flotation obtained in a Rushton turbine cell as a function of particle size and advancing 80 water contact angle of ( ) 40º; ( ) 57º; ( ) 75º; ( ) 83º). 3 rp = 2650 kg/m ; 60 d50 = 353 ± 8 µm; [DF250] = 20 mg/l; d = 0.7 ± 0.3 mm; b 40 rotational speed = 650 ± 4 rpm, Recovery (%) turbulent energy dissipation = 6.46 m2/s3.; 20 Ref = 26063; gas flow rate = 4.5 l/min).

0 0 200 400 600 800 1000 Particle Diameter (µm)

The Wark has undertaken a thorough study on attention was paid to ensuring that adequate the limits of coarse particle recovery in flotation particle suspension occurred for these very coarse in the work by Carlos Gontijo in P260D2. In this particles. Remarkably, very large particles (>900 work, the flotation behaviour of quartz particles up microns) could be recovered provided the advancing to 1000 microns in diameter and with advancing contact angle was 83o or greater (Figure 2). When water contact angles of 0o to 83o has been the flotation recovery versus contact angle for each studied. Flotation was performed in a column or particle size is separately considered (Figure 3) it Rushton turbine cell. The particle contact angle was observed that there was a critical contact angle threshold values, below which the particles could below which flotation did not occur. This effect was not be floated, were identified under different first reported by Blake and Ralston3 and confirmed hydrodynamic conditions. Gontijo2 found that by Crawford and Ralston4. For a 115 micron the flotation recovery increases as the particle particle, a critical contact angle of 34o is observed, contact angle increases, and that 100% recovery whilst for a coarse 714 micron particle, a critical was obtained for particles having a contact angle contact angle of 74o is observed (Figure 3). For very of 83o across the particle size range studied in a coarse particles, the transition from non-floating Rushton turbine flotation cell (Figure 2). Particular to floating regime is very abrupt, reflecting the

38 often observed “knife-edged” flotation behaviour of coarse particles noted in plant practice. Small 100 dp = 115µm decreases in value mineral hydrophobicity can have 80 a dramatic and detrimental effect on coarse particle recovery. 60

40 A flotation domain is evident, within which flotation Q = 34˚ occurs, and outside of which there is no flotation 20 critical (Figure 4). For comparison the results of Crawford and Ralston4 are also shown. The critical contact 0 angle / particle size threshold for flotation was dp = 421µm affected by the particle size distribution of the 80 quartz feed sample used (Figure 4). For coarse particles, the transition from floating to non- 60 floating domains is controlled by the bubble-particle aggregate stability5. Stability is controlled by the 40 energy required to detach the particle from the Recovery (%) 20 Q = 55˚ bubble and the kinetic energy of the particle5. The critical most important attaching forces, which influence 0 the required detachment energy, are the capillary force at the three phase line of contact, buoyancy dp = 714µm force of the immersed part of the particle, and the 80 hydrostatic pressure, while the important detaching forces are gravity, bubble capillary pressure, and 60 in the case of a turbulent system the acceleration provided by the mechanical impeller5. For bubble- 40 Qcritical = 72˚ particle aggregates rising at a certain velocity, 20 the particle will have a kinetic energy which can be equated to the critical energy required for 0 detachment which is specific for a particular particle 0 20 40 60 80 100 size, contact angle, bubble size and velocity. The Contact Angle (˚) results of these calculations on the kinetic limits of flotation show that as the bubble velocity decreases acceleration introduced by turbulence and also by Figure 3. Critical contact angle the critical contact angle required for flotation also decreasing the bubble velocity. determination. Quartz recovery decreases (Figure 4). In the velocity limit of a static after 8 minutes of flotation, bubble, the so called gravitational limit of flotation At the other end of the particle size spectrum, obtained in a Rushton turbine cell is found (Figure 4). In this limiting case, it is possible important studies on the critical contact angle for at a fixed particle size. to have a stable bubble-particle union above 1000 fine particles, less than 5 microns, were undertaken (r = 2650 kg/m3, o p microns for contact angles greater than 50 . 6 by Tatu Miettinen . For 1 micron particles, the d50 = 353 ± 8 µm, experimental data for a bubble swarm in a Ruston [DF250] = 20 mg/l, These experiments on coarse particle recovery turbine flotation cell is shown in Figure 5. A d = 0.7 ± 0.3 mm, are being further advanced in the current P260E b critical contact angle for flotation is indicated of rotational speed = 650 ± 4 rpm, project in the work of the PhD candidates, Wenbo 55-60o. Remarkably, similar critical contact angle turbulent energy dissipation = Wang and Danfeng Xu. In the former study, the values was found in the case of flotation with 6.46 m2/s3. flotation behaviour of model composite particles single bubbles and bubble swarms in a column cell Re = 26063, of known size, hydrophobic surface exposure and f and for the same particle size. The existence of a gas flow rate = 4.5 l/min.) distribution are being examined under well defined critical contact angle, necessary for the flotation of hydrodynamic conditions. Of particular interest, is fine particles, is based on the hypothesis that the the effect of the hydrophilic regions at the particle kinetic energy of the fine particles must be larger surface on the attainment of the equilibrium than the energy required to disrupt the intervening contact angle, an important parameter in particle- liquid films and form a three-phase line of contact, bubble aggregate stability. In the later study, the enabling bubble-particle attachment to occur7. For stability of the particle-bubble union is being probed particles above 5 microns, there is sufficient kinetic by subjecting the aggregate to known velocities and energy and the critical contact angle for flotation accelerating forces, and also by controlling the fluid is much lower. The research by Miettinen6 showed rheology. The latter approach may be an avenue satisfactory agreement between the experimental to increase recovery of low grade composite, data and theory in the flotation of fine particles7 coarse particles by damping the bubble-particle (Figure 4). The practical implication is that fine

Ian Wark Research Institute Annual Report 2007 39 Figure 4. Critical contact 10000 angle/particle size at which flotation commences, obtained 3 for quartz, (rp = 2650 kg/m ), 1 under quiescent and turbulent 1000 5 10 conditions for ( ). 20 Sample B in a flotation column, 30 d50 = 153 ± 4 µm, db = 0.8 ± 0.7 Nb mm, rotational speed = 547 ± 4 100 (cm/s) flotation rpm, Ref = 1573, gas flow rate = 3 4.3 ± 0.4 cm /min; ( ). no Sample C in a flotation column, flotation particle diameter (µm) 10 d50 = 262 ± 10 µm, db = 0.9 ± 0.7 mm, rotational speed = 560 ± 10 rpm, Ref = 1582, gas flow rate = 4.6 ± 0.4 cm3/min.; ( ). Sample D in a Rushton turbine 1 cell, d = 353 ± 8 µm, [DF250] 0 20 40 60 80 50 Critical contact angle (˚) = 20 mg/l, db = 0.7 ± 0.3 mm, rotational speed = 650 ± 4 rpm, turbulent energy dissipation = particles require a higher degree of hydrophobicity References 6.5 m2/s3, Re = 26063, gas flow f to affect their flotation compared with intermediate rate = 4.5 l/min.; Sample A in a particles (+5-50 microns). As fine value particles are 1. Grano, S., Akroyd, T., and Mular, M., 2007. flotation column and in single prone to oxidation and interaction with hydrophilic A model study of copper rougher recovery bubble capture experiments (d = b particles and hydroxides, the decreased recovery optimisation at PT Freeport Indonesia, Aust. 400 µm, pH = 5.8, 0.1 M KNO3); of fine value particles noted in some systems is Inst. Min. Metall. Publ., Ninth Mill Operators ( ) data obtained by Crawford credited to their lower hydrophobicity as well as Conference, pp. 25-38. and Ralston4 in a flotation to lower particle bubble collision efficiency. An 2. Gontijo, C., Fornasiero, F., and Ralston, J., 2007. column;. (- - -). Gravitational example of such a situation is apparent in the survey The limits of fine and coarse particle flotation, limit, dpmax,g, calculated for no at Ok Tedi (Figure 1), where the recovery of fine Canadian Journal of Chemical Engineering, 85, acceleration; ( ) experimental particles is apparently not limited by the residence 739. d , d = 1.8 mm, u = 20 pmax,g b b time in the rougher cells. 3. Blake, P., and Ralston, J., 1985. Particle size, µm/s; (- -) Kinetic limit for surface coverage and flotation response, Colloids flotation, d , as a function pmax,K and Surfaces, 16, 41. of contact angle for various 4. Crawford, R., and Ralston, J., 1988. The bubble velocities, u , given in the b influence of particle size and contact angle in figure.(2) mineral flotation, Int. J. Miner. Process., 23, 1. 5. Schulze, H. J., 1977. New theoretical and experimental investigations on Stability of bubble/particle aggregates in flotation: A theory on the upper particle size of floatability, Int. J. Miner. Process., 4, 241.

Figure 5. Recovery of methylated 80 quartz particles (0.5-5 µm) in a Rushton flotation cell after 8 minutes of flotation as a function 60 of particle advancing water contact angle (800 rpm; 30 ppm MIBC; 4.5 dm3/min gas flow rate; 40 pH = 6.0).(2) Recovery (%) 20

0 40 50 60 70 80 Advancing Contact Angle (˚)

40 6. Miettinen, T., 2007. Ultrafine particle-bubble • Dr Shuhua He and Dr Hamid Manouchehri Ms Maria Sinche Gonzalez interactions, PhD Thesis, University of South Somincor Lundin Mining Corporation, Neves collaborating electrodes for Australia. Corvo, Portugal, 22 July – 5 August the measurement of the 7. Scheludko, A., Toshev, B.V. and Bojadjiev, D.T., • Dr Sabina Gredelj and Dr Massimiliano Zanin electrochemical parameters in a 1976. Attachment of particles to a liquid surface BHP Billiton Olympic Dam, Australia, 27 August mineral flotation experiment. (capillary theory of flotation),J. Chem. Soc. – 7 September Faraday Transactions I, 12, 2815. • Dr Igor Ametov and Ms Maria Sinche Gonzalez BHP Billiton Olympic Dam, Australia, 27 Visits to Industrial Sites for Experimental Work November – 7 December

• Dr Hamid Manouchehri Visits to Industrial Clients, Sponsors and Anglo Platinum, South Africa, 21-27 January Collaborators • A/Prof Stephen Grano, Dr Hamid Manouchehri and Mr Czeslaw Poprawski • A/Prof Stephen Grano Anglo Platinum, South Africa; Vale Inco, Xstrata JKMRC, Australia, 12-14 August Nickel, Sudbury, Canada; Corem, Quebec, • A/Prof Stephen Grano Canada; Rio Tinto Kennecott Utah Copperton Teck Cominco, Vancouver, Canada; Vale Inco, Concentrator, Salt Lake City, USA; Freeport Thompson, Canada, 25 October – 2 November McMoRan Copper and Gold Inc, Phoenix, USA; • A/Prof Stephen Grano Metso Minerals, Xstrata Copper, Brisbane, 10-28 Dr Darsh Wasan, Motorola Chair Professor April of Chemical Engineering, Illinois Institute of • Dr Shuhua He Technology, Chicago, USA, 30 November CVRD Inco, Sudbury, Canada, 4-12 June • A/Prof Daniel Fornasiero, A/Prof Stephen Grano, • Dr Igor Ametov and Dr Massimiliano Zanin A/Prof Bill Skinner and Dr Massimiliano Zanin Rio Tinto Kennecott Utah Copperton P260E Sponsors Meeting, Salt Lake City, USA, Concentrator, Salt Lake City, USA and Phelps 3-10 December Dodge, Bagdad Concentrator, Arizona, USA, 17 June – 20 July

Ian Wark Research Institute Annual Report 2007 41 Scientific Services Sector Manager: Mr Philip Moore

Overview A major Mini Pilot Plant project was undertaken. 2007 was a year of great reward and challenge This presented a significant challenge for the staff for Scientific Services. The number of short term concerned, as it was necessary to handle much consulting projects increased by 21%, which larger sample amounts and operate the equipment resulted in an income of more than 50% above for extended periods to replicate actual plant 2006. 89 companies took advantage of the conditions. specialised service on offer and 229 consulting projects were completed during the year, indicating The Surface Analysis Team was significantly a high number of satisfied clients. A number of strengthened through the appointments of Eric significant appointments occurred throughout the Tavenner having recently completed a PhD at year, adding 5 new members of staff. UQ and John Denman who recently completed his PhD at The Wark. Tosha Tichy joined the At the end of 2007 Scientific Services had 15 full Minerals Processing Team bringing a significant time staff and provided services to over 300 clients wealth of industrial experience to the position. during the period from 2004 to 2007. The overall The appointment of Daniel Weissmann brought feedback from clients has been positive, with some further strength and experience to the Mineral indicating that there has been significant savings Processing Team. Dennis Palms was appointed resulting from the work performed. to a newly created position of Nanofabrication Technologist with the responsibility of overseeing In addition to industrial consulting projects, the construction of a clean room, purchase of Scientific Services continued to underpin the equipment and the operation of the NCRIS facility research activity of The Wark by conducting a once constructed. Andrew Lewis departed to take further 282 focussed short term work programs. up a research position elsewhere within UniSA. These included the provision of instrument or technical training for staff and students on an 55% of consulting income was derived from individual or group basis and analysis of samples interstate and internationally in 2007, compared with interpretation of the data in some cases. The to 36% in 2006. Income sourced from South Left to right: Mr Chris Bassell, income from research support represented 21% of Australian industry decreased to 45% of the total Mr John Denman, Dr Dennis the income generated from short term consulting. consulting income in 2007, although the actual Palms and Mr Philip Moore dollar amount only decreased by 8.5%. In 2006 income from South Australian industry provided

42 Left to right: Dr Ray Newell, Ms 120 2007 Tosha Tichy and Mr Keith Quast 100 2006 80

60 Figure 1. Distribution of clients by geographic location, shown as 40 a percentage of total consulting 20 income for 2006 – 2007.

0 SA Clients Interstate Clients International Clients

Metals 1% Figure 2. Distribution of projects Health and Pharmaceuticals 1% for all industry sectors serviced Government 2% during 2007, shown as a Energy 1% percentage of total consulting Electronics 1% income Education 6% Consumer Products 12% Construction 1% Biotech 2% Plastics 3% Other 4% Minerals and Mining 66%

Ian Wark Research Institute Annual Report 2007 43 250 Education sector is mainly analytical support for research projects at the University of South Australia 200 and other Australian universities. The Education sector has also remained relatively stable, but when 150 compared to the Mining and Minerals sector it averages less than 15% of income over the four 100 year period.

50 A review of the type of work undertaken by Scientific Services over the last four years (Figure 4) 0 indicates a decline in the problem solving activities. Consumer Eduation Mining and Other Plastics Problem solving is a category of work that includes Products Minerals material and contaminant characterisation, 100 surface and failure analysis, verification testing Access and corrosion and wear studies. There has been 80 Advise a corresponding increase in short term projects that draw upon the significant experience of Consult 60 the staff working within the sector, providing Explore additional benefits for our clients. Scientific Services 40 Solve has increasingly worked on projects involving materials selection, product development, process 20 development & optimisation, expert opinion and litigation, specifying and/or sourcing technology or 0 equipment, literature review and technology audits. 2004 2005 2006 2007 Income % Income % Income % Income % New Major Items of Equipment 65% of the total funding. The main reason for this Figure 3 (above). Distribution of The Wark was awarded funding through NCRIS significant change was a large consulting project projects for our top five Industry (National Collaborative Research Infrastructure involving the Mini Pilot Plant for an international Sectors, shown as a percentage Strategy) and the South Australian Government for company in 2007. Income sourced from interstate of total consulting income for two major initiatives. The first was for construction clients increased by 53% in 2007 compared to 2004 to 2007 of a Nanofabrication Facility which includes purpose interstate income from the previous year. Figure 1 built cleanrooms and specialised equipment. The compares data from 2006 and 2007 to illustrate the second funding initiative was granted through Figure 4. Distribution of projects above observations. NCRIS Characterisation for a new ToF-SIMS (Time by type, shown as a percentage of Flight Secondary Ion Mass Spectrometer) to be of total consulting income for It is not surprising to see that the Mining and installed at The Wark. This instrument will be 2004 to 2007 Minerals sector contributed 66% of Scientific ordered during 2008 and it will be available to Services funding for 2007. The growth of funding Australian researchers through AMMRF (Australian from the Minerals and Mining sector was over 37% Microscopy and Microanalysis Research Facility). compared to 2006. The funding contribution from the Consumer Products sector was 12%, which In collaboration with Flinders University and the exceeded expectations, increasing almost 54% from University of New South Wales, funding was 2006. This was mainly due to a number of related awarded through an ARC LIEF Grant for a Kelvin small projects focussing on implementing new Probe. The Kelvin Probe is a non-contact, non- technology into manufacturing. Although 78% of destructive measurement device used to investigate funding came from two industry sectors, Scientific properties of materials. It is based on a vibrating Services was sufficiently diverse to derive the capacitor and measures the work function remaining 22% from 12 industry sectors as shown difference, or for non-metals, the surface potential, in Figure 2. between a conducting specimen and a vibrating tip. The work function is an extremely sensitive indicator A review of four years of historical data (Figure 3) of surface condition and is affected by adsorbed or clearly shows the Mining and Minerals Industry evaporated layers, surface reconstruction, surface increasing its domination of funding for Scientific charging, oxide layer imperfections, surface and Services. The contribution of each year is shown bulk contamination, etc. The Kelvin Probe will be as a different colour on the stacked column chart. purchased and installed at The Wark during 2008. Although funding from the Consumer Products sector has remained relatively stable, it averages less than 25% of Mining and Minerals income over the four year period. The work done for the

44 Research Projects CREATING AND APPLYING KNOWLEDGE * Total funding over $50,0000

BIO AND POLYMER INTERFACES A novel approach for colour and degradation control in post consumer polyethylene terephthalate during recycling Research Sponsors: Australian Research Council Linkage Grant and Visy Plastics Chief Investigators: N Roy Choudhury and N Dutta

*A physicochemical approach for optimizing drug delivery from BioSilicon Research Sponsors: Australian Research Council Linkage Grant and pSivida Chief Investigators: C Prestidge, A Evans (Pharmacy and Medical Sciences) and P Pendleton (PMS)

*Development of multilayered packaging with controlled barrier properties Research Sponsor: Poly Products Co Pty Ltd Chief Investigators: N Dutta and N Roy Choudhury

*Engineered nanotube membranes for molecular separation and biosensing Research Sponsor: Australian Research Council Discovery Grant Chief Investigator: D Losic

*Improved oral delivery of poorly soluble drugs using nanoparticulate encapsulation technologies Research Sponsors: ITEK and BioInnovation SA Chief Investigators: C Prestidge and S Simovic

*Interfacial studies of nanoparticulate dendrimers for improved biopharmaceutical application Research Sponsors: Australian Research Council Linkage Grant and Starpharma Chief Investigators: C Prestidge and H Griesser

*Integrated approach to the development of advanced nanostructures as cancer diagnostics and therapeutic agents Research Sponsor: Cancer Council of South Australia Chief Investigator: H Griesser

*Investigation of surface properties of biomedical materials and devices cleaned by a hybrid (ultrasonic- electrolytic) system Research Sponsor: Soniclean Chief Investigators: S Kumar, P Majewski and P Kentish (Natural & Built Environments)

*Novel biomimetic nanosprings: protein-based elastomer for engineering applicants Research Sponsor: Australian Research Council Discovery Grant Chief Investigators: N Dutta and N Roy Choudhury

*Physio-chemical and biopharmaceutical investigations of novel drug delivery systems for oral administration of lipophilic drugs Research Sponsor: Australian Research Council Discovery Grant Chief Investigators: C Prestidge and A Evans (PMS)

Poly(ethylene glycol) interlayers for furanone coatings on contact lenses) Research Sponsors: BioSignal Ltd Chief Investigators: L Britcher and H Griesser

*Surface for tissue engineering Research Sponsor: CRC for Polymers Chief Investigator: H Griesser

*Synthesis and characterisation of functionalised mesoporous materials Research Sponsor: ANSTO Chief Investigator: P Majewski

*Test systems for microstreak equipment Research Sponsor: Labtech Systems Ltd Chief Investigator: H Griesser

Ian Wark Research Institute Annual Report 2007 45 COLLOIDS AND NANOSTRUCTURES *Control of aggregate structure settling and dewatering in mineral tailings processing Research Sponsors: Australian Research Council Linkage Grant and Rio Tinto Chief Investigators: R Smart (ACeSSS), M Zbik and G Morris (Victoria University)

*Development of a new type of large area robust super hydrophobic surfaces Research Sponsors: MWN - Australian Research Council International Linkage Grant Chief Investigators: D Fornasiero, R Sedev, N Dimitrov (Suny-Binghampton) and J Ralston

*Electrical double layer and electron transfer in ionic liquids Research Sponsor: CSIRO Minerals Chief Investigators: J Ralston, R Sedev and M Horne (CSIRO Minerals)

*Friction and capillary forces Research Sponsor: QEII Fellowship Chief Investigators: S Onishi

*Interfacial chemistry and particle interactions in tailings consolidation (P523A) Research Sponsors: Australian Research Council Linkage Grant and AMIRA International Chief Investigators: J Addai-Mensah and K Bremmell

*Model studies of the wettability of reservoir and seal rocks as recovered and after treatments to alter surface properties Research Sponsors: Australian Research Council Linkage Grant and CSIRO Petroleum Chief Investigators: R Sedev, J Ralston and J Kaldi (University of Adelaide)

Online capsule formation by consecutive adsorption of fluorescent polyelectrolyte in a microfluidic network Research Sponsors: ARC/NHMRC FABLS Network Chief Investigator: C Priest

Optical detection of nanoparticles as markers for biosensor applications Research Sponsor: Australia China Special Fund Chief Investigator: R Horn

*Particle-bubble interactions Research Sponsor: CSIRO Minerals Chief Investigators: J Ralston, D Fornasiero and P Koh (CSIRO Minerals)

*Polymers at mineral interfaces (P498B) Research Sponsors: Australian Research Council Linkage Grant and AMIRA International Chief Investigators: D Beattie, D Fornasiero, J Addai-Mensah and J Ralston

MATERIALS AND ENVIROMENTAL SURFACE SCIENCE *Characterization of metal contaminants in Antarctic sediments Research Sponsor: Australian Antarctic Program Chief Investigator: I Kempson

Characterisation of particle surface and interfacial chemistry of copper-uranium pulps in tails solidification process Research Sponsor: BHP Billiton Chief Investigator: J Addai-Mensah

*Development of novel nanostructured electro-optical systems Research Sponsors: Australian Research Council Linkage Grant and Visiocorp Australia Pty Ltd Chief Investigators: H Griesser, P Murphy, G Wallace (University of Wollongong), P Innis (University of Wollongong) and S Edwards (Visiocorp Australia Pty Ltd)

46 *Improved fouling mitigation: The properties and mechanisms of action of sodium aluminosilicate scale inhibition polymers Research Sponsor: Cytec Australia Chief Investigator: J Addai-Mensah

*Improving aqueous processing and control of copper-uranium leach tails behaviour Research Sponsors: Australian Research Council Linkage Grant and BHP Billiton Chief Investigators: J Addai-Mensah and W Skinner

*Materials research and engineering facility for conducting polymer devices Research Sponsors: Premier Science Research Fund, Visiocorp Australia Pty Ltd and Carl Zeiss Vision Australia Chief Investigators: P Murphy and R Short (Mawson Institute)

*New high temperature proton conducting polymer electrolyte for sustainable energy conversion applications Research Sponsor: Australian Research Council Discovery Grant Chief Investigators: N Dutta and N Roy Choudhury

*Rapid optical switching technologies Research Sponsor: CRC for Intelligent Manufacturing Systems & Technologies Chief Investigator: H Griesser

*Steel surface passivation with Nalco polymers: A novel approach to sodium aluminosilicate fouling mitigation Research Sponsor: Nalco Australia Pty Ltd Chief Investigator: J Addai-Mensah

*Uranium-copper tails characterization, leach and thickening behaviour Research Sponsor: BHP Billiton Chief Investigators: J Addai-Mensah and W Skinner

*Water treatment by functionalised silica Research Sponsor: United Water Chief Investigator: P Majewski

MINERAL PROCESSING *Characterizing and controlling the surface properties of fine mineral particles generated during grinding and the effect on flotation properties Research Sponsor: Magotteaux Australia Chief Investigators: S Grano and S Gredelj

*Distinguishing and quantifying the relative contributions of oxidized iron from grinding media and mineral sources Research Sponsor: Magotteaux Australia Chief Investigators: S Grano and S Gredelj

*Improving sulphide mineral flotation (P260E) Research Sponsors: Australian Research Council Linkage Grant and AMIRA International Chief Investigators: S Grano, D Fornasiero and W Skinner

*Increasing copper and molybdenum recovery from low recovery ores Research Sponsor: Rio Tinto – Kennecott Utah Copper Chief Investigator: M Zanin

*Increasing PGM recovery in the Western Limb tailings retreatment plant deslime circuit Research Sponsor: Anglo Platinum Chief Investigators: S Grano and H Manouchehri

Ian Wark Research Institute Annual Report 2007 47 PhD candidate Mr Solomon Muganda (left) and Dr Hamid Manouchehri monitor and measure air bubbles in a laboratory flotation cell using a bubble viewer Inset: Air bubbles in mineral flotation, laboratory scale bubble viewer and bubble size measurement apparatus to monitor and measure air bubbles within flotation cell

48 *Investigation of Tantalum recovery from pegmatite and plant tailings Research Sponsor: Sons of Gwalia Chief Investigators: R Newell, K Quast, S Grano and P Moore

*Mineral flotation – Integrating science and practice Research Sponsor: JKMRC Chief Investigators: P Moore and W Skinner

* Optimising froth zone performance in mineral floatation (P541B) Research Sponsors: Australian Research Council Linkage Grant and AMIRA International Chief Investigators: S Grano, R Horn and J P Franzidis (University of Queensland)

*Optimisation of coal flotation performance Research Sponsors: Australian Research Council Linkage Grant and BHP Billiton Mitsubishi Alliance Chief Investigators: J Ralston, D Fornasiero and D Weedon (ACeSSS)

* Optimising the recovery of fine and course particles in mineral flotation Research Sponsors: Australian Research Council Linkage Grant and AMIRA International Chief Investigators: S Grano and D Fornasiero

*Separation of minerals in final concentrate at Olympic Dam Research Sponsor: BHP Billiton Chief Investigators: S Grano and S He

SCIENTIFIC SERVICES *Facility for advanced materials surfaces engineering Research Sponsor: Premiers Science Research Fund Chief Investigator: H Griesser

*Integrated electrochemical facility Research Sponsor: Australian Research Council LIEF Grant Chief Investigators: N Roy Choudhury, N Dutta, N Voelcker (Flinders University) and S Bandyopadhyay (University of NSW)

CORPORATE *Australian Mineral Science Research Institute (AMSRI) Research Sponsors: AMIRA International, Australian Research Council Linkage Grant, South Australian Government and UniSA Chief Investigator: J Ralston

*Centre for particle and material interfaces Research Sponsor: Australian Research Council Special Research Centre Chief Investigator: J Ralston

*Fabrication of advanced materials Research Sponsors: NCRIS, UniSA and South Australian Government Chief Investigator: J Ralston

*SA Regional facility for microscopy Research Sponsors: NCRIS, UniSA and South Australian Government Chief Investigator: H Griesser

Ian Wark Research Institute Annual Report 2007 49 Honours and Awards

Dr David Beattie Dr Sarah Harmer Dr Beattie was one of twenty UniSA research staff Dr Harmer was awarded an Australian Academy competitively selected as part of the University’s of Science Travel Fellowship through the Scientific inaugural Research Leadership Program, an initiative Visits to North America, Canada and Mexico designed to develop the next generation of Program. As a result, Sarah spent one month research leaders. The Program, which commenced working with Prof Wayne Nesbitt and Dr Allen Pratt in February, runs over 18 months and focuses on at the University of Western Ontario on a research building the practical leadership and management project investigating the effects of impurities on capabilities of the researchers. Each participant the copper activation of sphalerite using X-ray receives individual and group mentoring and Photoelectron Spectroscopy (XPS). financial support for their research over the life of the Program. During the Fellowship, Sarah and Prof Nesbitt received the Lumdsen Award to continue their research on weathering of sulfide minerals and interpretation of XPS spectra collected from silicate glasses.

Dr Naba Dutta As the recipient of an Ian Wark Research Institute Travel Fellowship, Dr Dutta (pictured far right) visited Simon Fraser University, Canada during April and Ms Karyn Jarvis May. This enabled collaboration with Prof Steven Best Wark student seminar - ‘The interactions Holdcroft and Dr Ken Shi on novel materials for and surface modification of BioSilicon’. Karyn is energy and their electrochemistry, particularly in the second year of her PhD and works within polymer electrolyte membrane fuel cells. Naba also the Bio and Polymer Interfaces Sector using a visited the National Research Council Institute for combination of physical chemistry, interfacial and Fuel Cell Innovation in Vancouver which focuses material sciences to establish the effect of surface TM on the research, development, demonstration and modification on BioSilicon structure, surface testing of hydrogen and fuel cell systems. chemistry and probe molecule interactions. Her thesis is titled, “Investigation of the interfacial and porous properties of BioSiliconTM” and her principal supervisor is Prof Clive Prestidge.

50 Laureate Professor John Ralston 2007 Ian Wark Research Institute Medal During a visit to Tianjin University, PR China on 15 Mr Jarred Clasohm was awarded the Ian Wark June, Laureate Prof John Ralston was awarded the Research Institute Medal for 2007. Jarred’s thesis title of Honorary Professor of Tianjin University by was entitled, ‘Investigation of hydrodynamic the Vice President of the University, Professor Xianjin boundary conditions at liquid-solid interfaces” and Yang (pictured above). his principal supervisor was Prof Roger Horn. After completing his thesis, Jarred took up a position at A General International Agreement between The the Laboratory for Surface Science and Technology, Wark and the Schools of Chemical Engineering, ETH Zurich, Switzerland. Materials Science & Engineering and Environmental Science & Engineering at Tianjin University is The Ian Wark Research Institute Medal is awarded now in place. This will enable co-supervision of annually to the graduate or graduand from The PhD students between the two institutions and Wark with the most outstanding PhD thesis. collaboration on research and teaching programs. The Medal is awarded based on the creativity Laureate Professor John Ralston and originality of the research, the student’s At the 2007 South Australian Excellence Awards comprehension of the field and the significance and held on 22 August, John Ralston was named as the utility of the research as a contribution to, or as an South Australian Scientist of the Year. This was the application of knowledge. first year this category has been awarded which recognises outstanding achievement in the area of “scientific research that significantly advances knowledge and has produced or has the potential to produce a commercial outcome and/or benefit to the community”.

Ian Wark Research Institute Annual Report 2007 51 Doctor of Philosophy Theses Jarred Clasohm (2007) Investigation of hydrodynamic boundary conditions at liquid-solid interfaces

Linh Cuba-Chiem (2007) Probing polymer adsorption at the solid-liquid interface with particle film ATR-FTIR spectroscopy

John Denman (2007) The application of Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to forensic glass analysis and questioned document examination

Kate McLeod (2007) Bisphosphonate-loaded hydroxyapatite-coated 2007 South Australian of the Year implant surfaces: physico-chemical characterisation Following on from the award of South Australian and bone cell culture studies Scientist of the Year, John Ralston was named 2007 South Australian of the Year at the annual SA Great Tatu Miettinen (2007) Awards held on 28 November. The award was Fine particle flotation presented to John by His Excellency the Governor of South Australia, Rear Admiral Kevin Scarce. Ana Pereira Duarte (2007) The interaction of sphalerite and silica at very fine The South Australian of the Year is selected from particle sizes and its influence on flotation selectivity both peer and public nominations and aims to celebrate the individual who has demonstrated a Thi Phuong-Cac Nguyen (2007) consistent record of excellence and outstanding Oligonucleotide immobilisation via a patterned achievement in their field of expertise and who propanal plasma polymer coating: A potential can be regarded as a role model for other South surface chemistry for DNA microarray fabrication Australians. Kim Shyong Siow (2007) John was the recipient for his outstanding Plasma based methods for producing controlled contribution to scientific research. SA Great sulphur and phosphorus containing chemical Chairperson, Nigel McBride noted, “Here is a person groups and interactions between such surfaces and who has achieved so much in so many ways but proteins what’s so relevant right now is that his work adds significantly to our fast growing mining industry and it is this industry that will play a major part in driving this state forward”.

Laureate Prof John Ralston with South Australian Premier, The Hon Mike Rann

52 Seminar Program

Visiting Speakers Queensland University of Technology, Australia Can we tissue engineer grafts for the femur or tibia Dr Gunther Andersson School of Chemistry, Physics and Earth Sciences, Dr Ingo Köper Flinders University of South Australia, Australia Max Planck Institute for Polymer Research Mainz, Investigation of the molecular structure of soft Germany matter surfaces Tethered bilayer lipid membranes: A versatile model membrane platform Dr Werner Baschong Structural Biology and Biophysics, Biozentrum Prof Frederick Lange University of Basel, Switzerland Materials Department, University of California Santa Elasticity of articular cartilage measured by atomic Barbara, USA force microscopy with a nanosized ‘indenter’ – An Superhydrophobicity and making silicon early indicator for functional degeneration? superhydrophobic

Dr Ben Boyd Dr Sally McArthur Victorian College of Pharmacy, Monash University, Centre for Biomaterials and Tissue Engineering, Australia University of Sheffield, United Kingdom Dendrimers as carriers for anticancer compounds Surface modification for microfluidics and bioarrays and liquid crystalline nanostructured particles (structure and delivery) Prof Willem Norde Laboratory of Physical Chemistry and Colloid Dr Wuge Briscoe Science, Wageningen University, The Netherlands Department of Chemistry, Oxford University, United Proteins in aqueous solution and at interfaces Kingdom Soft matter at interfaces: Towards understanding Dr Nikolay Novozhilov and Dr Sergey Pushko some fundamental aspects of biolubrication Coherent Scientific, Adelaide, Australia NTEGRA scanning probe microscope Mr Leonard Carter Chemical Engineer/Geostatistician, Australia Dr Orivaldo Savassi Metallurgical and geostatistical experiences in SGS-Lakefield, Toronto, Canada Southern Africa A standardised laboratory procedure for reliable scale-u of batch flotation results: The MFT-FLEET Mr Tony Fischer-Cripps method Fischer-Cripps Laboratories Pty Ltd, Sydney, Australia Overview of nanoindenation Emeritus Prof Ross Smith Department of Chemical and Metallurgical Dr Amanda Ellis Engineering, University of Nevada Reno, USA School of Chemistry, Physics and Earth Sciences, Flotation of metal oxides using long chain collectors Flinders University of South Australia, Australia Defects induced in carbon nanotubes and novel Dr Helmut Thissen composite formation using nanotubes as chain CSIRO Molecular and Health Technologies, Australia transfer agents in RAFT polymerizations The role of surface chemistry in biomaterials and regenerative medicine Prof Gil Garnier Department of Chemical Engineering, Monash Prof Lee White University, Australia Department of Chemical Engineering, Carnegie Surface engineering and papermaking: Synergy or Mellon University, USA oxymoron? The role and measurement of disjoining pressure in lubricant nano-films Prof Michael Grunze Applied Physical Chemistry, University of Heidelberg, Dr Bjorn Winther-Jensen Germany ARC Centre of Excellence for Electromaterials Biological surface science and chemical Science, Monash University, Australia nanolithography Order – disorder transition in Poly(3,4- dioxythiophene) (PEDOT) provide new insights into Prof Dietmar Hutmacher conduction mechanisms Institute for Health and Biomedical Innovation,

Ian Wark Research Institute Annual Report 2007 53 Dr Hailong Zhang Prof Hans Griesser Centre for Green Chemistry, Monash University, Bio-Interfaces – Some whys and wherefores Australia AFM study on the attachment of bacteria to a Dr Sarah Harmer patterned surface with a particular hydrophobicity/ Sulphides, surfaces and synchrotrons hydrophilicity Dr Shuhua He Staff Seminars Depression of pyrite in the flotation of copper ores

A/Prof Jonas Addai-Mensah Prof Roger Horn Improving the dewatering behaviour of mineral Measuring forces between fluid drops waste dispersions for sustainable mineral processing Dr Ivan Kempson Dr Igor Ametov Material characterisation utilising a tunable x-ray Copper and molybdenite recovery in plant and source batch laboratory tests in porphyry copper flotation Dr Marta Krasowska Dr Tim Barnes Stability of thin liquid film during bubble collision Surface modification of Biosilicon™ for improved with hydrophobic solid surface therapeutic delivery A/Prof Sunil Kumar Dr David Beattie Strategies for improving the fixation of bone Fundamentals of polymer depression in flotation implants

Dr Artem Borysenko Dr Vera Lockett Application of wettability and surface Electrochemistry in ionic liquids characterisation methods to study liquid distribution and displacement in porous space of model and real Dr Dusan Losic minerals (shales) Nanotube membranes for molecular separation and biosensing Dr Leanne Britcher Hydrophilic platforms for biomolecules Prof Peter Majewski Superparamagnetic nanoparticles Dr Liping Ding Characterisation of coal hydrophobicity and its Dr Hamid Manouchehri effect on flotation Physical separation in minerals and waste processing

Dr Naba Dutta Dr Agnieszka Mierczynska-Vasilev Polymers at interfaces and polymer interfaces: Polymers at mineral interfaces Molecular dynamics and macromolecular assemblies Dr Peter Murphy Dr Rick Fabretto Microwave plasma polymerisation - grow coatings Electrochromics: Combining science with profits at up to 200 nm/sec & Dr Renate Fetzer An update of recent progress in electrochromic Slip-controlled dewetting dynamics device development using conducting polymers

A/Prof Daniel Fornasiero Dr Satomi Onishi Stabilisation study of nucleic acid transfection Studies on friction in nano-scale with SFA and AFM complexes Dr Dennis Palms A/Prof Stephen Grano Moving contact lines: Where have all the Pas gone Studies on the froth phase in flotation Dr Mihail Popescu Dr Sabina Gredelj Short notes on a) Washburn’s equation, b) Diffusion My year at The Wark and attachment in a drop and c) Confinement effects of diffusion-based self-propellers

54 Prof Clive Prestidge Dr Hui Tan Left to right: Dr Benjamin Thierry, Nanostructured carriers: Improving the delivery of Effect of carbonaceous matter on gold extraction Prof Hans Griesser and Honours pharmaceutical actives candidate Mr Ben Demchenko Dr Benjamin Thierry Dr Craig Priest Bio-Interface and functional nanoparticles Droplet-based microfluidics Dr Peter Tran Dr Rada Pushkarova Resilin: Rubber like biomaterial characterisation Air bubble-solid interactions in water and electrolyte solutions Dr Krasimir Vasilev Interactions of lipids and PEG modified surfaces Laureate Prof John Ralston & Why things float and how things get wet Nanoengineered plasma polymer films

Prof Namita Roy Choudhury Dr Catherine Whitby Nanostructure control in ionic polymers Particle-stabilised emulsions - Aspects of emulsification Dr Rossen Sedev Surface and interfacial tension of ionic liquids Dr Vassili Yaminsky Hydrophobic interactions in disperse systems Dr Damyanti Sharma Biosynthesis of metal nanoparticles Dr Massimiliano Zanin Understanding the froth phase performance in Dr Spomenka Simovic minerals flotation Lipoceramic capsules in drug delivery

Dr Surya Subianto Overview of conducting polymers - from electron to proton conductors

Ian Wark Research Institute Annual Report 2007 55 Visitors to the Institute

Extended Visits

Prof Nigel Cook Natural History Museum, University of Oslo, Norway

Dr Amiya Kumar Panda Department of Chemistry, Behala College, Kolkata, India

Prof Willem Norde Laboratory of Physical Chemistry and Colloid Science, Wageningen University, The Netherlands

Emeritus Prof Ross Smith Department of Chemical and Metallurgical Engineering, University of Nevada Reno, USA

Dr Zehong Wang Department of Mineral Engineering, Northeastern University, PR China

Short Term Visits

A/Prof Yasuhisa Adachi Graduate School of Life and Environmental Sciences, Tsukuba University, Japan

Prof Ben Adair and Prof Tim Napier-Munn Julius Kruttschnitt Mineral Research Centre, University of Queensland, Australia

Mr Chris Anderson, Mr Paul Dempsey, Dr Neville Plint and Mr Jan Smits Anglo Platinum, South Africa

Dr Megan Becker and Dr Jenny Wiese Centre for Minerals Research, University of Cape Town, South Africa

Mr Rob Berger and Mr Craig Dick Norilsk Process Technology, Perth, Australia

Dr Terry Blake Visiting Professor, University of Mons and Head (retired) Surface Science Kodak, UK

Dr Bart Follink CSIRO Minerals, Clayton South, Australia

Dr Chris Greet Magotteaux, Perth, Australia

Mr Paul Heithersay Department of Primary Industries and Resources SA, Australia

56 Dr Richard Hillis Prof Brian Vincent Australian School of Petroleum, University of Leverhulme Professor of Physical Chemistry and Adelaide, Australia Director, Bristol Colloid Centre, University of Bristol, UK Dr Naoyuki Ishida and Dr Takao Ishida National Institute of Advanced Industrial Science Dr Denis Weaire and Technology, Japan Physics Department, Trinity College Dublin, United Kingdom Prof Karin Jacobs and Dr Ralf Seemans Department of Experimental Physics, University of Mr Michael Young Saarland, Germany Xstrata Technology, Brisbane, Australia

Dr Shigeyuki Kaji and Dr Kuniaki Masuoka Overseas Student Visits Institute of Microchemical Technology, Japan Mr Bjorn Dollman Dr Nag Nagaraj Max Planck Institute for Polymer Research Mainz, Cytec Industries, Stamford, USA Germany

Prof Zhao Naiqin, Prof Yuan Xiaoyan, A/Prof Yuan Mr Martin Dwork and Mr Kai Hofen Xubo, Prof Cui Zhenduo and Prof Jiang Zhongyi Mannheim University of Applied Sciences, Germany School of Chemical Engineering/School of Materials Science and Engineering, Tianjin University, Mr Padmal Epitawela PR China University of Moratuwa, Sri Lanka

A/Prof Toshiyuki Nomura Mr Abhinav Grover Department of Chemical Engineering, Osaka Indian Institute of Technology, India Prefecture University, Japan Ms Qiushi Huang Prof Cyril O’Connor Dalian University of Technology, PR China Faculty of Engineering and Built Environment, University of Cape Town, South Africa Mr Stefan Klink Ruhr University Bochum, Germany Mr Kevin O’Keefe Talison Minerals Pty Ltd, Perth, Australia Ms Amelie Le Minoux and Ms Cecile Masse CPE Lyon, France Prof Robert Pelton Interfacial Technologies Group, McMaster University, Ms Puck Moll Canada Wageningen University, The Netherlands

Dr Orivaldo Savassi Mr Philipp Muff SGS-Lakefield, Toronto, Canada ETH Zurich, Switzerland

Prof Mitsuo Sawamoto Mr Kamil Zuber Department of Polymer Chemistry, Kyoto University, AGH University of Science and Technology, Poland Japan

A/Prof Hiroyuki Shinto Department of Chemical Engineering, Kyoto University, Japan

Dr Gillian Sparkes and Mr Robert Trenberth Australian Sustainable Industry Research Centre Ltd, Monash University, Australia

Prof Marcus Textor Laboratory for Surface Science, ETH Zurich, Left to right Ms Sandy Ray, Mr Paul Luppino and Switzerland Ms Kerry Zweck

Ian Wark Research Institute Annual Report 2007 57 Conference Attendance and Invited Lectures *oral presentation †poster presentation

Mr Robert Acres Clive Prestidge (session co-chair), †Dr Craig Priest, Asia-Oceania Forum for Synchrotron Radiation Laureate Prof John Ralston, Dr Rossen Sedev, Ms Research, Cheiron Synchrotron Summer School, Iliana Sedeva, Dr Krasimir Vasilev, Dr Catherine Himeji, Japan, 10-20 September, 2007 Whitby and *Dr Vassili Yaminsky Australian Colloid and Interface Science Conference *A/Prof Jonas Addai-Mensah (invited keynote (ACIS), Sydney, Australia, 4-8 February, 2007 speaker) US Department of Energy Al/Cr Nuclear Waste *Mr Heramb Bal, *A/Prof Daniel Fornasiero, *Dr Workshop, Atlanta, USA, 22-24 January, 2007 Shuhua He, *Ms Karyn Jarvis, *†Mr Keith Quast, Mr Laza Randriamanjatosoa and Dr Massimiliano Zanin *A/Prof Jonas Addai-Mensah Chemeca 2007, Melbourne, Australia, 23-26 Heat Exchanger Fouling and Cleaning VII, Tomar, September, 2007 Portugal, 1-6 July, 2007 *Dr Tim Barnes (invited speaker), *Ms Nasrin *A/Prof Jonas Addai-Mensah (invited speaker) Ghouchi Eskandar, *Prof Clive Prestidge (invited Recent Developments in Improved Dewatering of speaker) and †Mr Mohanraj Vellore Janarthanan Mineral Waste Tailings, International Lecture Series, Australasian Pharmaceutical Sciences Association, University of Mines and Technology, Tarkwa, Ghana, Sydney, Australia, 8-11 December, 2007 11-13 July, 2007 *Dr David Beattie, *†A/Prof Daniel Fornasiero, *A/Prof Addai-Mensah *A/Prof Stephen Grano and *Dr Sarah Harmer 46th Conference of Metallurgists (COM 2007), Flotation 2007, Cape Town, South Africa, 5-9 Toronto, Canada, 25-30 August, 2007 November, 2007

Left to right: Dr Rossen Sedev, *A/Prof Jonas Addai-Mensah, *Dr Tim Barnes, *Dr †Ms Audrey Beaussart and Dr Rossen Sedev Dr Sarah Harmer, Dr Marta David Beattie, †Ms Audrey Beaussart, *Dr Sarah 21st Conference of the European Colloid and Krasowska, Ms Iliana Sedeva Harmer, Prof Roger Horn (conference chair), *Dr Interface Society, Geneva, Switzerland, 10-14 and Dr Tim Barnes at the ACIS Marta Krasowska, *Dr Agnieszka Mierczynska- September, 2007 Conference dinner Vasilev, *Dr Satomi Onishi, †Dr Dennis Palms, *Prof

58 *†Dr Artem Borysenko *A/Prof Daniel Fornasiero Society of Core Analysts Symposium, Calgary, Round Table on Effect of Water Quality on the Canada, 9-14 September, 2007 Performance of Mineral Processing, Quebec City, Canada, 18-19 September, 2007 *Dr Naba Dutta 233rd American Chemical Society National Meeting, *Ms Nasrin Ghouchi Eskandar Chicago, USA, 25-29 March, 2007 5th International Postgraduate Research Symposium on Pharmaceutics, Istanbul, Turkey, 13-15 *Dr Naba Dutta September, 2007 International Symposium on Polymeric Materials for Regenerative Medicine (PMRM 2007), Montreal, A/Prof Stephen Grano Canada, 2-4 April, 2007 Northern Manitoba Canadian Mineral Processors Conference, Thompson, Canada, 31 October- ? *Dr Naba Dutta November, 2007 Nanotech 2007, Santa Clara, USA, 20-24 May, 2007 A/Prof Stephen Grano and Dr Ray Newell *Dr Naba Dutta AusIMM 9th Mill Operators Conference, Fremantle, Pushing Small-angle Neutron Scattering at OPAL Australia, 19-21 March, 2007 to Smaller Q, ANSTO Workshop, Lucas Heights, Australia, 15-16 November, 2007 A/Prof Stephen Grano and *Laureate Prof John Ralston (invited lecture) Dr Naba Dutta (invited speaker) 57th Canadian Chemical Engineering Conference, Les Internationales 2nd International Symposium of Edmonton, Canada, 28-31 October, 2007 Polytech Montpellier, Montpellier, France, 19-23 December, 2007 Prof Hans Griesser Indo Australian Conference on Biomaterials, Left to right: Ms Audrey Beaussart, *A/Prof Daniel Fornasiero Implants, Tissue Engineering and Regenerative Dr Krasimir Vasilev, Dr Agnieszka Automated Mineralogy 2007, Brisbane, Australia, Medicine, Thiruvananthanpuram, India, 10-12 Mierczynska-Vasilev and Dr David 1-2 September, 2007 January, 2007 Beattie

Ian Wark Research Institute Annual Report 2007 59 Prof Hans Griesser †Dr Mihail Popescu 6th Discovery Science and Biotechnology Meeting, 23rd International Conference on Statistical Physics Brisbane, Australia, 30 May-1 June, 2007 of the International Union for Pure and Applied Physics, Genoa, Italy, 9-13 July, 2007 Prof Hans Griesser Surface Analysis 2007, Minneapolis, USA, 11-13 †Dr Mihail Popescu June, 2007 Soft, Complex and Biological Matter Conference, Palermo, Italy, 15-19 July, 2007 Prof Hans Griesser International Conference on Materials for Advanced †Prof Clive Prestidge Technologies (ICMAT07), Singapore, 1-4 July, 2007 Pharmaceutical Science World Congress, Amsterdam, The Netherlands, 22-26 April, 2007 Prof Hans Griesser BASF Conference on Nanomaterials, Singapore, 21- Prof Clive Prestidge (invited lecture) 23 October, 2007 Nanoparticles and the Droplet-Water Interface, University of Bordeaux, France, May, 2007 Prof Hans Griesser and *A/Prof Sunil Kumar 17th Australasian Society for Biomaterials †Prof Clive Prestidge Conference, Mt Elisa, Australia, 11-13 April, 2007 Controlled Release Society Meeting, Long Beach, California, USA, 7-11 July, 2007 Prof Roger Horn (invited speaker) International Mini-Symposium of Surface Science Prof Clive Prestidge (invited lecture) Forces, Matsushima, Japan, 4-8 March, 2007 Nano-Structured Carriers as Pharmaceutical Delivery Systems, University of Adelaide, Australia, 10 Prof Roger Horn (invited speaker) September, 2007 International Nanotribology Forum, Ho Chi Minh, Vietnam, 24-31 March, 2007 Prof Clive Prestidge (invited lecture) Nano-Structured Drug Delivery Systems: Insight Prof Roger Horn (invited speaker) and Mr Keith from Studies on Supported Lipid Bilayers and Quast (invited delegate) Liposomes, Sansom Institute, UniSA, 28 September, Australian Colloid and Surface Science Student 2007 Conference (40 Years), Melbourne, Australia, 8-11 June, 2007 †Dr Craig Priest 11th International Conference on Miniaturized *A/Prof Sunil Kumar Systems for Chemistry and Life Sciences, Paris, 34th International Conference on Metallurgical France, 7-11 October, 2007 Coatings and Thin Films, San Diego, USA, 23-27 April, 2007 Laureate Prof John Ralston (invited lecture) Electrowetting in Aqueous and Non-aqueous Dr Andrew Lewis and A/Prof Bill Skinner (invited Systems: Saturation and Other Non-Lippmann workshop) Behaviour, CSIRO Minerals, Melbourne, Australia, Surface Spectroscopy and Synchrotron Analysis 20 April; University of Mons, Belgium, 11 June and in Minerals Processing, Julius Kruttschnitt Mineral Tianjin University, China, 15 June, 2007 Research Centre, QUT, Australia, 25 May 2007 Laureate Prof John Ralston (invited lectures) Dr Dusan Losic Extreme Flotation & Why Things Float and How Advanced Materials and Nanotechnology, Things Get Wet, University of Cape Town, South Wellington, New Zealand, 11-16 February, 2007 Africa, 1-4 October, 2007

Prof Peter Majewski (keynote speaker) Laureate Prof John Ralston (invited lecture) International Conference on Nano and Bio-Science Interparticle Forces and Colloid Stability, University (ICONBS 2007), Taipei, Taiwan, 4 – 7 December, of Tokyo, Japan, 15 November, 2007 2007 *Prof Namita Roy Choudhury Dr Peter Murphy 234th American Chemical Society National Meeting, Inkjet Printing Technology in Materials Science Boston, USA, 19-23 August, 2007 Applications, University of Wollongong, Australia, 6-7 December, 2007

60 *Prof Namita Roy Choudhury Dr Benjamin Thierry (invited speaker) International Dendrimer Symposium, Toulouse, Controlling Nanoparticle Bio-interfaces: A France, 28 August-1 September, 2007 Requirement to Nanobiotechnology?, McGill Institute for Advanced Materials Seminars, *Prof Namita Roy Choudhury Montreal, Canada, 4 May, 2007 International Conference on Sol-Gel (Sol-Gel 2007), Montpellier, France, 2-7 September, 2007 Dr Benjamin Thierry Functional Nanoparticles: Lessons from Surface. Prof Namita Roy Choudhury (invited speaker) BioInterfaces Workshop, Adelaide, Australia, 27 International Fire Retardant Society Symposium, June, 2007 Tokyo, Japan, 14 September, 2007

Dr Rossen Sedev (keynote speaker) International Bouyoucos Conference on the Origin of Water Repellency in Soils, Sanible Island Florida, USA, 29 April-3 May, 2007

Dr Rossen Sedev (invited lecture) International Workshop on Nanoscale Phenomena in Colloid and Interface Science, Plovdiv, Bulgaria, 20-22 September, 2007

A/Prof Bill Skinner Surface Electron Spectroscopy and Ion Spectrometry in Mineral Analysis, Instrumental Applications on Surface Science Workshop, Minneapolis, USA, 12 December, 2007

Ian Wark Research Institute Annual Report 2007 61 Publications

Book Chapters Datta, P, Majewski, P & Aldinger, F, (2007), ‘Synthesis and microstructural characterization of Sr Griesser, H & Kingshott, P, (2007), ‘Surface and Mg doped LaGaO3 solid electrolyte’, Materials Matrix-Assisted Laser Desorption Ionization’, The Chemistry and Physics, 102, 240-244, (0254-0584), Encyclopedia of Mass Spectrometry, Elsevier, 2007 Amsterdam & Oxford, 713-722, (9-7800-8043- 8016), (Micael L. Gross, Richard M. Caprioli Eds), Dotti, C, Gambassi, A, Popescu, M & Dietrich, S, 2007 (2007), ‘Spreading in narrow channels’, Physical Review E (Statistical, Nonlinear and Soft Matter Ralston, J, Fornasiero, D & Grano, S, (2007), ‘Pulp Physics), 041127-1-041127-14, (1539-3755), 2007 and Solution Chemistry’, Froth Flotation: A Century of Innovation, Society for Mining, Metallurgy and Dutta, N, Tran, N D, Truong, M Y, Choudhury, Exploration Inc., USA, 227-258, (9-7808-7335- N, Hill, A J & Elvin, C, (2007), ‘Novel biomimetic 2529), (Maureen Fuerstenau, Graeme Jameson & protein-based hydrogel with superior elasticity’, Roe-Hoan Yoon Eds), 2007 Polymer Preprints, 48, (1), 609-610, (0032-3934), 2007 Refereed Journal Articles Fabretto, M, Vaithianathan, T, Hall, C, Murphy, Addai-Mensah, J, (2007), ‘Enhanced flocculation P, Innis, P C, Mazurkiewicz, J & Wallace, G G, and dewatering of clay mineral dispersions’, Powder (2007), ‘Colouration efficiency measurements in Technology, 179, 73-78, (0032-5910), 2007 electrochromic polymers: The importance of charge density’, Electrochemistry Communications, 9, (8), Addai-Mensah, J, Yeap, K Y & McFarlane, A J, 2032-2036, (1388-2481), 2007 (2007), ‘The influential role of pulp chemistry, flocculant structure type and shear rate on Ghouchi Eskandar, N, Simovic, S & Prestidge, C, dewaterability of kaolinite and smectite clay (2007), ‘Synergistic effect of silica nanoparticles and dispersions under couette Taylor flow conditions’, charged surfactants in the formation and stability Powder Technology, 179, 79-83, (0032-5910), 2007 of submicron oil-in-water emulsions’, Physical Chemistry Chemical Physics, 9, (48), 6426-6434, Bertrand, E, Blake, T, Ledauphin, V, Ogonowski, G, (1463-9076), 2007 de Coninck, J, Fornasiero, D & Ralston, J, (2007), ‘Dynamics of dewetting at the nanoscale using Gontijo, C, Fornasiero, D & Ralston, J, (2007), ‘The molecular dynamics’, Langmuir, 23, 3774-3785, limits of fine and coarse particle flotation’,Canadian (0743-7463), 2007 Journal of Chemical Engineering, 85, 739-747, (0008-4034), 2007 Buckley, A, Skinner, W, Harmer-Bassell, S, Pring, A, Lamb, R N, Fan, L J & Yang, Y W, (2007), Govindaraj Kannan, A, Choudhury, N & Dutta, N, ‘Examination of the proposition that Cu(II) can be (2007), ‘Fluoropolyurethane hybrid for thin film required for charge neutrality in a sulfide lattice - Cu application’, Polymer Preprints, 48, (1), 685-686, in tetrahedrite and sphalerite’, Canadian Journal of (0032-3934), 2007 Chemistry, 85, 767-781, (1480-3291), 2007 Govindaraj Kannan, A, Choudhury, N & Dutta, Chen, M & Horn, R, (2007), ‘Refractive index of N, (2007), ‘Synthesis and charaterization of sparse layers of adsorbed gold nanoparticles’, methacrylate phospho-silcate hybrid for thin film Journal of Colloid and Interface Science, 315, 814- applications’, Polymer, 48, 7078-7086, (0032- 817, (0021-9797), 2007 3861), 2007

Kanta, A, Sedev, R & Ralston, J, (2007), Datta, P, Majewski, P & Aldinger, F, (2007), ‘Fabrication of silica-on-titania and titania-on-silica ‘Structural studies of Sr- and Mg-doped LaGaO3’, nanoparticle assemblies’, Colloids and Surfaces A: Journal of Alloys and Compounds, 438, 232-237, Physicochemical and Engineering Aspects, 292, 1-7, (0925-8388), 2007 (0927-7757), 2007

Datta, P, Majewski, P & Aldinger, F, (2007), Kempson, I, Skinner, W & Kirkbride, K, (2007), ‘The ‘Synthesis and characterization of strontium and occurrence and incorporation of copper and zinc magnesium substituted lanthanu gallate-nickel in hair and their potential role as bioindicators: A cermet anode for solid oxide fuel cells’, Materials review’, Journal of Toxicology and Environmental Chemistry and Physics, 102, 125-131, (0254-0584), Health. Part B: Critical Reviews, 10, 611-622, (1093- 2007 7404), 2007

62 Krasowska, M, Kolasinska, M, Warszynski, P & bio-applications’, Critical Reviews in Solid State & Malysa, K, (2007), ‘Influence of polyelectrolyte Materials Sciences, 32, 203-215, (1040-8436), 2007 layers deposited on mica surface on wetting film stability and bubble attachment’, Journal of Physical Manica, R, Connor, J, Carnie, S L, Horn, R & Chan, Chemistry C, 111, (15), 5743-5749, (1932-7447), D Y, (2007), ‘Dynamics of interactions involving 2007 deformable drops: Hydrodynamic dimpling under attractive and repulsive electrical double layer Krasowska, M, Krastev, R, Rogalski, M & Malysa, interactions’, Langmuir, 23, (1), 626-637, (0743- K, (2007), ‘Air-facilitated three-phase contact 7463), 2007 formation at hydrophobic solid surfaces under dynamic conditions’, Langmuir, 23, (2), 549-557, Math, S, Horn, R, Jayaram, V & Biswas, S K, (0743-7463), 2007 (2007), ‘A general contact mechanical formulation of multilayered structures and its application to Krasowska, M & Malysa, K, (2007), ‘Kinetics of deconvolute thickness/mechanical properties of glue bubble collision and attachment to hydrophobic used in surface force apparatus’, Journal of Colloid solids: I. Effect of surface roughness’, International and Interface Science, 308, (2), 551-561, (0021- Journal of Mineral Processing, 81, 205-216, (0301- 9797), 2007 7516), 2007 Mayavan, S, Choudhury, N & Dutta, N, (2007), Krasowska, M & Malysa, K, (2007), ‘Wetting films ‘Ionomer stabilized noble metal colloids for catalytic in attachment of the colliding bubble’, Advances in applications’, PMSE Preprints, 97, 1-2, (1550-6703), Colloid and Interface Science, 134-135, 138-150, 2007 (0001-8686), 2007 Mistry, M K, Choudhury, N, Dutta, N & Holdcroft, Kumar, S, Simpson, D & Smart, R, (2007), ‘Plasma S, (2007), ‘Inorganic modification of ionic block processing for including bioactivity in stainless steel copolymer for high temperature PEM applications’, orthopaedic screws’, Surface and Coatings and PMSE Preprints, 97, 17-18, (1550-6703), 2007 Technology, 202, 1242-1246, (0257-8972), 2007 Ndi, C P, Semple, S J, Griesser, H & Barton, M, Ladasiu Ciolacu, F C, Choudhury, N, Dutta, N & (2007), ‘Antimicrobial Activity of Some Plant Cosior, E, (2007), ‘Molecular level stabilization of Species from the Australian Genus’, Journal of Basic poly(ethylene terephthalate) with nanostructured Microbiology, 47, 158-164, (0233-111X), 2007 open cage trisilanolisobutyl-POSS’, Macromolecules, 40, 265-272, (0024-9297), 2007 Newell, R & Grano, S, (2007), ‘Hydrodynamics and scale up in Rushton turbine flotation cells: Part Lockett, V, Rukavishnikova, I V & Stephanov, V P, 1 - Cell hydrodynamics’, International Journal of (2007), ‘Phase densities of molten binary mixtures Mineral Processing, 81, 224-236, (0301-7516), of alkali halgenides with limited mutual solubility’, 2007 Journal of Physical Sciences, 62, (5), 303-308, (0932-0784), 2007 Newell, R & Grano, S, (2007), ‘Model and experimental study of the effect of impeller Lockett, V, Tkachev, N K, Rukavishnikova, I V & rotational speed on the flotation rate from a Stephanov, V P, (2007), ‘Density of stratified ionic small-scale flotation cell-implications for the effect melts: Experiment and theory’, Russian Journal of of bubble velocity’, Minerals and Metallurgical Electrochemistry, 43, (8), 955-960, (1023-1935), Processing, 24, (3), 157-169, (0747-9182), 2007 2007 Newell, A, Skinner, W & Bradshaw, D J, (2007), Majewski, P, (2007), ‘Removal of organic matter in ‘Restoring the flotation of oxidised sulfides using water by functionalised self-assembled monolayers sulfidisation’, International Journal of Mineral on silica’, Separation and Purification Technology, Processing, 88, 108-117, (0301-7516), 2007 57, 283-288, (1383-5866), 2007 Onishi, S, Kaneko, D, Gong, J, Osada, Y, Stewart, A Majewski, P & Fuchs, T, (2007), ‘Variation of the M & Yaminsky, V, (2007), ‘Influence of cyclohexane surface charge of silica particles by functionalised vapor on stick-slip friction between mica surfaces’, self-assembled monolayers’, Advanced Powder Langmuir, 23, (13), 7032-7038, (0743-7463), 2007 Technology, 18, 303-310, (0921-8831), 2007 Palms, D, Norwig, J & Wegner, G, (2007), Majewski, P & Thierry, B, (2007), ‘Functionalised ‘Electrochemically induced growth of zinc oxide’, magnetite nanoparticles - synthesis properties, and

Ian Wark Research Institute Annual Report 2007 63 ChemPhysChem: A European journal of chemical surface composed of beta-cyclodextrin monolayer’, physics and physical chemistry, 8, (15), 2260-2264, Japanese Journal of Applied Physics, 46, (12), 7838- (1439-4235), 2007 7845, (0021-4922), 2007

Peng, P, Voelcker, N H, Kumar, S & Griesser, H, Saiki, Y, Prestidge, C & Horn, R, (2007), ‘Effects (2007), ‘Nanoscale eluting coatings based on of droplet deformability on emulsion rheology’, alginate/chitosan hydrogels’, Biointerphases, 2, 94- Colloids and Surfaces A: Physicochemical and 104, (1559-4106), 2007 Engineering Aspects, 299, 65-72, (0927-7757), 2007 Pereira Duarte, A C & Grano, S, (2007), ‘Mechanism for the recovery of silicate gangue minerals in Simovic, S & Prestidge, C, (2007), ‘Nanoparticle the flotation of ultrafine sphalerite’, Minerals layers controlling drug release from emulsions’, Engineering, 20, 766-775, (0892-6875), 2007 European Journal of Pharmaceutics and Biopharmaceutics, 67, 39-47, (0939-6411), 2007 Popescu, M, Dietrich, S & Oshanin, G, (2007), ‘Binary reactive adsorbate on a random catalytic Sung, D, Ciobanu, C L, Pring, A, Brugger, J, Skinner, substrate’, Journal of Physics: Condensed Matter, W, Nugus, M & Cook, N J, (2007), ‘Tellurides 19, 1-12, (0953-8984), 2007 from Sunrise Dam gold deposit, Yilgarn Craton, Western Australia: A new occurrence of nagyagite’, Pratt, A R, Zuin, L, Yiu, Y & Harmer-Bassell, S, Mineralogy and Petrology, 91, (3-4), 249-270,

(2007), ‘High-resolution XANES S L3,2 edge spectra (0930-0708), 2007 collected from a series of iron-bearing spharlerite (Zn,Fe) S minerals’, 85, 761-766, (0008-4042), 2007 Thierry, B, Majewski, P, Ngothai, Y & Shi, Y, (2007), ‘Preparation of monodisperse functionalized Prestidge, C, Barnes, T, Lau, C-H, Barnett, C, Loni, nanoparticles’, International Journal of A & Canham, L, (2007), ‘Mesoporous silicon: A Nanotechnology, 4, (5), 523-530, (1475-7435), platform for the delivery of therapeutics’, Expert 2007 Opinion on Drug Delivery, 4, (2), 101-110, (1742- 5247), 2007 von Oertzen, G & Gerson, A, (2007), ‘The effects of O deficiency on the electronic structure of rutile Prestidge, C, Barnes, T, Mierczynska-Vasilev, A, TiO2’, Journal of Physics and Chemistry of Solids, Skinner, W, Peddie, F & Barnett, C, (2007), ‘Loading 20, 324-330, (0022-3697), 2007 and release of a model protein from porous silicon powders’, Physica Status Solidi. A: Applications and von Oertzen, G, Skinner, W, Nesbitt, H, Pratt, A R & Materials Science, 204, (10), 3361-3366, (1862- Buckley, A, (2007), ‘Cu adsorption on pyrite (100): 6300), 2007 Abinitio and spectroscopic studies’, Surface Science, 601, 5794-5799, (0039-6028), 2007 Prestidge, C, Barnes, T & Skinner, W, (2007), ‘Time-of-flight secondary-ion mass spectrometry Yang, J, Duan, J, Fornasiero, D & Ralston, J, (2007), for the surface characterization of solid-state ‘Kinetics of Co2 nanobubble formation at the pharmaceuticals’, Journal of Pharmacy and solid/water interface’, Physical Chemistry Chemical Pharmacology, 59, 251-259, (0022-3573), 2007 Physics, 9, (48), 6327-6332, (1463-9076), 2007

Priest, C, Sedev, R & Ralston, J, (2007), ‘Asymmetric Yu, J, Shapter, J, Quinton, J, Johnston, M R & wetting hysteresis on chemical defects’, Physical Beattie, D, (2007), ‘Direct attachment of well- Review Letters, 99, (2), 026103-1-026103-4, (0031- aligned single-walled carbon nanotube architectures 9007), 2007 to silicon (100) surfaces: A simple approach for device assembly’, Physical Chemistry Chemical Ralston, J, Fornasiero, D, Grano, S, Duan, J & Physics, 9, (4), 510-520, (1463-9076), 2007 Akroyd, T, (2007), ‘Reducing uncertainty in mineral flotation - flotation rate constant prediction for Zawala, J, Krasowska, M, Dabros, J & Malysa, K, particles in an operating plant ore’, International (2007), ‘Influence of bubble kinetic energy on its Journal of Mineral Processing, 84, 89-98, (0301- bouncing during collisions with various interfaces’, 7516), 2007 Canadian Journal of Chemical Engineering, 85, 669- 678, (0008-4034), 2007 Sadaie, M, Nishikawak, N, Kumashiro, Y, Ikezawa, Y, Kumagai, Y, Makino, K, Onishi, S, Tamada, K Zhou, J, Beattie, D, Ralston, J & Sedev, R, (2007), & Hara, M, (2007), ‘Quantitative friction map on ‘Colloid stability of thymine-functionalized gold

64 nanoparticles’, Langmuir, 23, (24), 12096-12103, Proceedings, Engineers Australia, 22-27, (0743-7463), 2007 Melbourne, Australia, 2007 Chemeca, (CMS Australia Eds), 2007 Zhou, J, Beattie, D, Sedev, R & Ralston, J, (2007), ‘Synthesis and surface structure of thymine- Grano, S, Akroyd, T & Mular, M, (2007), ‘A model functionalized self-assembled monolayer-protected study of copper rougher recovery optimisation gold’, Langmuir, 23, 9170-9177, (0743-7463), at PT Freeport Indonesia’, Ninth Mill Operators’ 2007 Conference Proceedings, Australasian Institute of Mining & Metallurgy, 25-37, Western Australia, Refereed Conference Papers Australasian Institute of Mining & Metallurgy (AUSIMM), (Mike Nelson & Rod Smith Eds), 2007 Bal, H M, Wijenayaka, A K & Fornasiero, D, (2007), ‘Triethylenetetriamine in the depression of He, S & Fornasiero, D, (2007), ‘Depression of iron pyrrhotite Flotation’, 2007 Chemeca: Conference sulphide minerals in the flotation of copper ores’, Proceedings, Engineers Australia, 1381-1386, 2007 Chemeca: Conference Proceedings, Engineers Melbourne, Australia, 2007 Chemeca, (CMS Australia, 344-349, Melbourne, Australia, 2007 Australia Eds), 2007 Chemeca, (CMS Australia Eds), 2007

Clennell, B, Borysenko, A, Burgar, I, Sedev, R Jarvis, K L, Barnes, T & Prestidge, C, (2007), ‘The & Ralston, J, (2007), ‘Dielectric and combined influence of thermal oxidation on the surface NMR/capillary pressure methods for monitoring chemical and adsorbent properties of porous liquid/air and liquid/liquid interface evolution: silicon’, 2007 Chemeca: Conference Proceedings, Application to rock and mineral wettability studies’, Engineers Australia, 374-381, Melbourne, Australia, Proceedings: 2007 International Symposium of 2007 Chemeca, (CMS Australia Eds), 2007 the Society of Core Analysis: Core Analysis for Improved Petrophysical Appraisals, SCA: Society of Quast, K, Ding, L, Fornasiero, D & Ralston, J, (2007), Core Analysis, 1-12, Canada, 2007 International ‘Effects of particle size on coal flotation’,2007 Symposium of the Society of Core Analysis, (David Chemeca: Conference Proceedings, Engineers Potter Eds), 2007 Australia, 332-337, Melbourne, Australia, 2007 Chemeca, (CMS Australia Eds), 2007 Clennell, B, Borysenko, A, Dewhurst, D, Sedev, R, Ralston, J & Liu, K, (2007), ‘Wettability Quast, K, Ding, L, Ralston, J & Fornasiero, D, (2007), characterization and noninvasive monitoring of ‘Hydrophobicity of coal particles’, 2007 Chemeca: the effect of crude oil treatment on cap-rock Conference Proceedings, Engineers Australia, 1903- shale minerals’, Proceedings: 2007 International 1908, Melbourne, Australia, 2007 Chemeca, (cms Symposium of the Society of Core Analysis: Core Australia Eds), 2007 Analysis for Improved Petrophysical Appraisals, SCA: Society of Core Analysis, 1-12, Canada, 2007 Randriamanjatosoa, A L & Grano, S, (2007), ‘Use International Symposium of the Society of Core of the foam drainage equation to model water Analysis, (David Potter Eds), 2007 flow in flotation froth’, 2007 Chemeca: Conference Proceedings, Engineers Australia, 300-306, Dermis, T, Mayavan, S, Dutta, N, Choudhury, N Melbourne, Australia, 2007 Chemeca, (Engineers & Holdcroft, S, (2007), ‘Block copolymer directed Australia Eds), 2007 nanoparticle for fuel cell applications’, Technical Proceedings of the 2007 NSTI Nanotechnology Wightman, E M, Zanin, M, Franzidis, J-P & Grano, Conference and Trade Show, Nano Science & S, (2007), ‘Relating froth vision to cell operating Technology Institute, 724-727, Santa Clara, performance in industrial flotation plants’,2007 California, Nanotech-2007, (NSTI Eds), 2007 Chemeca: Conference Proceedings, Engineers Australia, 1629-1634, Melbourne, Australia, 2007 Fornasiero, D & Henderson, A M, (2007), ‘Effect Chemeca, (CMS Australia Eds), 2007 of oxidation on the flotation of copper sulphide minerals’, 2007 Chemeca: Conference Proceedings, Zanin, M, Wightman, E M, Grano, S & Franzidis, J-P, Engineers Australia, 338-343, Melbourne, Australia, (2007), ‘Froth stability as a performance indicator in 2007 Chemeca, (CMS Australia Eds), 2007 sulphide minerals flotation plants’,2007 Chemeca: Conference Proceedings, Engineers Australia, 350- Fornasiero, D, Trinh, M-U & Ralston, J, (2007), 357, Melbourne, Australia, 2007 Chemeca, (CMS ‘Stabilisation studies of nucleic acid transfection Australia Eds), 2007 complexes’, 2007 Chemeca: Conference

Ian Wark Research Institute Annual Report 2007 65 Graduates 2007

Jarred Clasohm Linh Cuba-Chiem John Denman Kate McLeod BSc(Hons) PhD UniSA BAppSc(Hons) PhD UniSA BTech BSc(Hons) Flinders, PhD BSc BEng(Hons), Flinders, PhD UniSA UniSA Investigation of hydrodynamic Probing polymer adsorption at the boundary conditions at liquid- solid-liquid interface with particle The application of Time-of-Flight Bisphosphonate-loaded solid interfaces film ATR-FTIR spectroscopy Secondary Ion Mass Spectrometry hydroxyapatite-coated implant (ToF-SIMS) to forensic glass surfaces: Physico-chemical For more than a century it Polymeric depressant adsorption analysis and questioned characterisation and bone cell has been a central tenet of on the surface of talc was document examination culture studies hydrodynamics that liquids do investigated using in situ not slide over solid surfaces. Attenuated Total Reflectance- The combination of analytical The adsorption and loading Recent experiments have raised Fourier Transform Infrared (ATR- sensitivity and selectivity provided of a drug (pamidronate, a doubts about the correctness FTIR) Spectroscopy. The polymeric by Time-of-Flight Secondary bisphosphonate used for of this assumption. In a careful depressants investigated were Ion Mass Spectormetry (ToF- treating bone diseases) onto re-examination, this thesis an unmodified polyacrylamide SIMS), with advanced statistical and into hydroxyapatite coatings demonstrates that some of those (Polymer-N) and a hydroxyl interrogation by Principal have been investigated. This experiments are flawed and the substituted polyacrylamide Component Analysis (PCA), investigation, aimed at improving classical no-slip picture is probably (Polymer-H), an unmodified has allowed a significant the quality of orthopaedic correct. dextrin (Dextrin WY) and a advancement in the forensic implants, has confirmed the hydroxylpropyl substituted dextrin discrimination of pen, pencil and biological effectiveness of the Graduate Position: Postdoctoral (HP Dextrin), and carboxymethyl glass materials based on trace drug, as revealed by bone cell Researcher, Laboratory for Surface cellulose (CMC). The main characterisation. studies. Science and Technology, ETH objectives of this study were to Zurich, Switzerland evaluation the thermodynamic Graduate Position: ToF-SIMS Graduate Position: Madderns properties of adsorption, the Technologist, The Wark Patent and Trade Mark Attorneys, kinetics of adsorption and Adelaide, Australia desorption and the mechanisms driving adsorption.

66 Tatu Miettinen Thi Phuong-Cac Nguyen Ana Pereira Duarte Kim Shyong Siow BChemEng MSc Helsinki BSc BSc (Maths and BChemEng MSc Universidade BAppSc(Hons) Nanyang University of Technology, Finland, Computational Science) Adelaide, Federale Do Rio De Janeiro, Brazil, Technology University, Singapore, PhD UniSA BAppSc(Hons) PhD UniSA PhD UniSA PhD UniSA

Fine particle flotation Oligonucleotide immobilisation The interaction of sphalerite and Plasma based methods for via a patterned propanal plasma silica at very fine particle sizes producing controlled polymer In this thesis, bubble-particle polymer coating: A potential and its influence on flotation surfaces with sulfur and interactions were investigated surface chemistry for DNA selectivity phosphorus containing chemical using bubble diameters microarray fabrication groups and interactions between between 100 and 1500 μm This research focused on such surfaces and proteins and particle diameters below This research demonstrates a investigating interactions between 5 μm. Experiments were novel method of producing valuable and gangue minerals and Phosphate and sulfate groups performed using single bubbles patterned surfaces to immobilise the effect of these interactions on are important parts of biological and bubble swarms in quiescent synthetic DNA and preserves selectivity in flotation. Rheology molecules and as such take and turbulent conditions. A their ability to interact with was applied as a diagnostic tool part in defining bio-interfacial new theory was developed biomolecules. These types to investigate silica-sphalertie interactions. However their and validated for attachment of surfaces have potential particle interactions. It was roles and contributions are efficiency. application in a wide range of observed that the flotation insufficiently understood. In this high throughput diagnostic tests performance decreased when thesis, plasma based techniques Graduate Position: Outotec, based on microarray technology. interaction between silica and were used to produce polymeric Finland sphalerite increased. coatings with such groups for Graduate Position: Postdoctoral surface characterization and Research Scientist, University of Graduate Position: BHP Billiton, protein adsorption studies. Washington, Seattle, USA Roxby Downs, Australia Graduate Position: Exploit Technologies Pty Ltd, Singapore

Ian Wark Research Institute Annual Report 2007 67 International Collaborators AUSTRALIA Canada South Australia COREM BHP Billiton (Olympic Dam Corporation) Pty Ltd Eurozinc Mining Corporation BioInnovation SA Lundin Mining Corporation Cancer Council of South Australia Teck Cominco Ltd Carl Zeiss Vision Australia McGill University ITEK University of Alberta Labtech Systems Ltd University of Western Ontario MinProcesSer Pty Ltd Vale Inco Premiers Science Fund - South Australian Government Finland Soniclean Abo Akademi United Water Metso Minerals Visiocorp Australia Pty Ltd Outotec

ACT France Australian Research Council CPE Lyon National Health and Medical CPE Montpellier Research Council College de France National Collaborative Research Infrastructure Strategy (NCRIS) – Australian Government Germany Max-Planck-Insistute for Colloid Victoria and Interface Science AMIRA International Max-Planck-Institute for Australian Antarctic Program Metals Research CRC for Intelligent Manufacturing Systems and Max-Planck-Institute for Technologies Polymer Research CRC for Polymers CSIRO Minerals India Oxiana Resources NL Indian Institute of Science, Poly Products Co Pty Ltd Bangalore Rio Tinto Ltd Starpharma Japan Visy Plastics University of Tokyo Zinifex Ltd Papua New Guinea New South Wales Ok Tedi Mining Ltd Australian Nuclear Science and Technology Organisation PR China BHP Billiton Ltd Lanzhou Insitute of Physical BioSignal Ltd Chemistry, Chinese Academy of Huntsman Corporation Australia Pty Ltd Science Nalco Australia Pty Ltd Shanghai Insitute of Microsystems and Information Technology, Western Australia Chinese Academy of Science BHP Billiton Nickel West Ltd Tianjin University CSIRO Petroleum Cytec Australia Holdings Pty Ltd South Africa Magotteaux Australia Pty Ltd Anglo Platinum Corporation Ltd pSivida University of Cape Town Sons of Gwalia TiWest Joint Venture Sweden Boliden Minerals AB Queensland Lulea University of Technology Intellection KYTH (Royal Institute of Technology) Julius Kruttschnitt Mineral Research Centre Xstrata Copper Switzerland Xstrata Technology ETH Zurich

Belgium United Kingdom University of Mons-Hainaut Bristol University University of Leeds Brazil University of Nottingham Companhia Vale do Rio Doce Unilever Research Universidade Federal do Rio Grande do Sol Port Sunlight University of Sao Paolo USA Phelps Dodge Mining Co University of Florida University of Utah The

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Editorial/Production Madelene Pierce/Baden Smith Visual Productions 08 8302 3442 Photography Sam Noonan