KEVIN JOHN ROBERTSBSc, PhD, CEng, FIChemE, CChem, FRSC, CPhys, FInstP

Published by Strathclyde University Press,University of Strathclyde, Glasgow, United Kingdom.

ISBN 0 947649 14 X

© Professor Kevin J Roberts, 2004.

The copyright of this thesis belongs to the author under the terms of the United Kingdom Copyright Acts

as qualified by University of Strathclyde Regulation 3.51. Due acknowledgement must always be made of

the use of any material contained in, or derived from, this thesis.

Note on the Abridged Version

This publication provides an abridged version of the full DSc thesis (ca, 2094 pages in total) submitted to

the University of Strathclyde in September 2003 (awarded November 2004), i.e. without all the re-printed

publications and associated thesis appendicies. As such it provides the full framework of the original

thesis from which the reader can identify the thesis vision and locate any associated publications. The full

version of the thesis is available from the Andersonian Library at the University of Strathclyde in Glasgow, UK.

Dedication

To my parents

Betty Winifred Roberts (1909 – 1964)Frederick Richard Roberts (1904 – 1986)

who encouraged me to study and not to fear failure in this endeavour, all this

despite the lack of any real evidence for any inherent academic potential.

To my partner Ulrike

who encouraged me to take my first academic job in 1984 and who has

been wondering whether she made the right decision ever since!

To my children Anders and Maisie

for so many things

not the least for their forbearance in having to live through

so much anecdotal engineering science in their everyday lives.

To my in-laws

Ruth AufderhorstHerbert Aufderhorst (1909 – 1998)

for the warm Westfalian welcome they provided on that cold Sylvester Abend

of 1978 and for unreservedly including me in their family.

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Contents

Page 1 Acknowledgements 3 Abstract 5 A Note on Authorship 6 Chapter 1 Studies of crystal lattice defects in nearly perfect single crystals and their role in solid-state, surface and interfacial processes using X-ray topography and other related techniques. 10 Chapter 2 Application of molecular and solid-state modelling techniques using the atom-atom approximation to the prediction of crystal morphology, habit modification and other physical properties. 13 Chapter 3 Structural characterisation of surfaces and condensed interfaces, when operating under realistic thermodynamic conditions of temperature and pressure, via the application of synchrotron X-ray techniques. 17 Chapter 4 Experimental studies of industrial crystallisation processes related to subsequent product form together with the reactor monitoring and control through the application of advanced in-process measurement techniques. 20 Chapter 5 Determination of the crystal structures of some industrial organic compounds through the use of high-resolution X-ray powder diffraction, molecular and solid state modelling, and associated analytical techniques.

22 Postscript

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Acknowledgements

I grew up in the 1960s in the White Heat of Technology when to be a scientist or an engineer was really something rather

extra special. Along with so many post-Robbins kids, I was the first in my family to graduate from university. Gaining

my doctorate in 1978 and being allowed to carry out research with so many talented people as well as being given the

opportunity to teach at university has been enormously exciting for me. Submitting this, my DSc thesis, following 25

great years of post-doctoral research is something way beyond my dreams as a child.

My own academic career has drawn down so very much on the sound foundation I gained as both an undergraduate

and postgraduate student at the then Department of Physics at Portsmouth Polytechnic from 1971-1977. For my

undergraduate studies (BSc (Hons) in Applied Physics via a thin sandwich course), I am enormously grateful to the

staff both at Portmouth and at Admiralty Materials Laboratory, AWRE Aldermaston and GEC Hirst Research Centre

who hosted my periods of industrial training. I would, in particular, like to mention: David Nixon who, as my final year

project supervisor, stimulated my interest in research; Ruth Fenn who taught me the beauty and utility of crystallography

through learning that has been of so much use all through my academic life; and Ken Martin who, as my course director,

supported me though my studies through many ups and downs towards graduation with a good honours degree. Similarly,

as a (then) SRC CASE student I am most grateful to Dennis Elwell at Portsmouth and Brian Isherwood at the GEC Hirst

Research Centre both for their excellent supervision of my PhD studies and for their help in developing the breadth and

depth of my research skill base.

Whilst successful research relies on single-minded drive and vision it is also very much a team game. The latter has

become more and more important nowadays as the current scientific and engineering challenges have become much

more demanding. In my own case readers will note the tiny number of single authored papers, which reflects not

only this point but also the central fact that my research ethos and strategy is essentially collaborative in nature. This

reflects the two factors: firstly my work seeks to be holistic, i.e. to integrate concepts and is hence multi-disciplinary in

nature; secondly my work is strategic in context, i.e. fundamental work underpinning an area of scientific or industrial

application. Striking a balance between the individual and team components is often critical to success. In my own

case, and particularly with respect to this submission, none of what follows in this thesis would have been possible with

the friendship and collaboration of academic colleagues, research assistants and students. However, rather than add a

very long list here I have indicated the collaborations in the individual thesis chapters and provided a full glossary of all

publications in the appendix.

A stimulating and creative scientific environment is also critical and in this respect I am enormously grateful to the

University of Strathclyde, Technical University of Aachen, Heriot-Watt University and the University of Leeds for my

employment and for excellent facilities they have made available to me without which I would not have been able to

complete this work. The stimulation of my interest in the physical chemistry, crystallography and engineering of organic

solids owes everything to my employment as a research assistant in the Department of Pure and Applied Chemistry and

my mentoring by John Sherwood in 1977 and in subsequent years. I am also most grateful to Helmut Klapper for hosting

me as Royal Society Fellow for two great years at the Institut für Kristallographie in Aachen and for his friendship and

collaboration since. A good proportion of my work has made use of synchrotron radiation facilities available in the

national laboratories including VEPP-31 in Russia (then USSR), Synchrotron Radiation Source at Daresbury Laboratory2

in the UK and more recently at the National Synchrotron Light Source at Brookhaven National Laboratory in the USA. I

am most grateful to the staff and funding agencies associated with these facilities for this. In particular, I would like to

acknowledge Neville Greaves who I collaborated with on a number of synchrotron projects during my secondment period

1. My synchrotron radiation experience begun with two stimulating visits to VEPP-3 led by Keith Bowen (then at the University of Warwick) at the Institute of Nuclear Physics at Academgorodok in Novosibirsk in the (then) USSR which was undertaken in summers of 1979 and 1980 via the Anglo-Soviet Exchange Scheme.2. In the late 1970s, I worked as one of the first SERC (later EPSRC) funded research assistants at the (then) new Synchrotron Radiation Source at Daresbury Laboratory being involved in commissioning the X-ray topography facility on station 7.6.

1

to Daresbury Laboratory. The development of my engineering science base owes much to Brian Scarlett3 who hosted me

as a visiting professor at the Technical University of Delft in the Netherlands from 1994 to 1995 and for his mentoring

since.

I want to acknowledge my extreme good fortune in having my research work supported through funding from both

government agencies and industry. The former includes: British Council, Brookhaven National Laboratory, CCLRC

Daresbury Laboratory, SERC and EPSRC (research and travel grants, and a Senior Fellowship), EU, Leverhulme Foundation,

Petroleum Research Fund of the American Chemical Society, Royal Society (research and travel grants, and a European

Fellowship), University of Leeds, Heriot-Watt University, University of Strathclyde. Industrial funding (research grants

and consultancy) has come from: AEA Technology, A H Marks Ltd, AstraZeneca, BASF, Bede Scientific Instruments, BNFL,

BP Exploration, Cadbury Trebor Basset, Clairet, DuPont de Nemours, Eli Lilly, Exxon Chemical, GlaxoSmithKline, HEL Ltd,

ICI, Infinium, Malvern Instruments, MSI, Mitsubishi Chemical, Nippon Oils and Fats, Novartis, Pfizer, Reckitt-Benckisser,

Sanofi, Shell, Syngenta and Unilever. In particular, I would like to acknowledge at ICI Chemicals and Polymers in Runcorn

(Roger Davey and Richard Oldman) and Exxon Chemical at Abingdon (Bob Tack and Ken Lewtas) who supported and

mentored much of my early research work following my academic appointment in 1984.

Also, any presentation such as this is bound to represent a snap shot of research activity, which does not represent the

complete and accurate representation of my group’s work over the complete assessment period. A significant proportion

of my research is either in progress or completed but awaiting publication (either being in preparation, submitted for

publication or accepted but awaiting journal publication date). Also some work is currently embargoed due to commercial

sensitivity and so full publication may be delayed for a numbers of years yet. In this respect readers are directed to the

original thesis presentations detailed in the appendix (if available) of the following PhD students: James Evans, Amber

Geddes, Richard van Gelder, Susan Girdwood, Stephen Hastings, Alison Hennessy, Christos Ioakimidis, Xiaojun Lai, Jessica

Kangping Liang, Siobhan MacSweeney, Carol Peacock, Branka Radovic, Alessandra Rossi, Audrey Taggart, Elaine Walker,

where a significant proportion of their research work is not given here.

No acknowledgements can be complete without mention of a large number of supporting administration and technical

staff who facilitate so much of my research group’s environment and activities. Someone described, perhaps unkindly,

academic management as a contradiction in terms or, more humorously, as something akin to herding cats. Whatever the

truth, this process would be so much harder without our often unsung support staff in the case of this cat notably: Ulrike

Aufderhorst, Rolf Becker, Ann Blyth, Andrew Brown, Shari Bull, Steven Caddick, John Clark, Cathy Goundry, Bob Fabian,

Kirn Jutlla, Colin MacLuckie, Jim MacKenzie and Debbie Sowden.

I would also like to warmly acknowledge my good friend Terry Bambrook (Creative Concepts, Graphic Design:

terry@bambrook.com) who provided graphic support not only for this submission, but also for the inaugural lecture

given in Appendix A.

Finally, 25 years is a long time in research and my sincere apologies to anyone who I have inadvertently missed out in the

above list.

3. Sadly, Brian Scarlett died on Thursday September 2nd 2004, whilst this abridged version was in preparation.

2

Abstract

Condensed chemical interfaces of a wide variety of types play a significant part in mediating the operation of a wide range of

fundamental and industrial processes.

In solid/liquid interfacial structures electrochemical potential control underpins corrosion protection, fuels cells and sensor technology

whilst solid/liquid chromatographic methods are important in synthesis, polymer science and process analysis. Crystallisation and

crystal surface engineering impacts upon bio-mineralisation in living systems, minerals separation and conveying, advanced materials

purification as well as on the industrial manufacturing of high value-added fine chemicals such as pharmaceuticals.

Liquid/liquid interfaces play an important part in separation processes underpinning chemical engineering unit operations such as

solvent extraction, scrubbing and multi-component distillation as well as facilitating the action of surfactants and mediating and

directing reactivity in synthetic chemical processes. Such interfaces also play an important role in colloid and formulation technology

where interfacial modification by polymers controls the dispersion of paints and improves the sensitivity of photographic emulsions as

well as defining the rheological performance of structured food products.

Solid/solid interfaces are important in optimisation surface coating and paint technology and in semiconductor manufacture where the

precise atomic-scale structural control of multi-layer structures is vital to the successful operation of devices such as high performance

CMOS memory, CCD video sensor technology and hetero-epitaxial lasers. Such interfaces are also important in composite materials

through providing optimal strength to structural engineering materials as well as through their role in engineering the performance of

a wide range of formulated products ranging from propellants to pharmaceutical tablets.

Finally, the gaseous/solid interfaces have applications in catalysis used in both chemical synthesis and on the industrial scale through

processes such as in petroleum cracking, alkylation and reforming. Such interfaces also play an important role in areas such as gas

filtration and adsorption providing the critical underpinning science in areas such as the gas sensor technology used for mine, chemical

and fire safety. They are also important in the environmental domain area through processes such as atmospheric surface oxidation

and tarnishing.

In all these domain areas an intimate knowledge of the often subtle interplay between interface structure and processing kinetics as

linked to resultant material properties is bound to be important and arguably a pre-requisite for effecting the optimal performance of

the interfacial structure in question. Key to the delivery of the above is the development and application of characterisation techniques

using both molecular-scale modelling- and measurement-based techniques particularly the validation of the former by the latter. In

this, the modelling techniques draw down on molecular scale phenomena linking these to the same when mediated in the varied inter-

molecular environments provided in supra-molecular and crystallographic structures. The measurement techniques presented here link

to the modelling techniques via the development and use of in-process analytical methods to assess the kinetics of interface formation

together with molecular-scale structural characterisation, often carried out in-situ, via a number of characterisation techniques notably

those involving the use of X-rays and synchrotron radiation.

Hence, drawing down upon and inverting this scenario reveals the important point that a broad knowledge of the structure/property

inter-relationship can provide, in principle, the basis for the a priori prediction of the performance of condensed interfacial structures.

Such a scenario has strategic implications in that it could, in principle, enable the development of molecular-scale tools and approaches

capable of designing and manufacturing tailor-made advanced chemical products.

Although lacking in the multidisciplinary spirit of my work I have, for the convenience of the reader and for the purpose of this DSc

submission, corralled the publications into a series of chapters of work. These comprise a collection of the submitted component of the

publications submitted being laid out as follows:

3

Chapter 1. The use of high-resolution X-ray diffraction associated techniques to examine nearly perfect single crystals and

through this probe the role played by lattice defects and micro-crystallographic variation in the solid-state, surface

and interfacial properties associated with materials processes.

Chapter 2. The application of molecular and crystallographic modelling using quantum chemical and inter-molecular force

calculations for the prediction and control of the physical properties of crystalline solids notably their morphology

and surface properties.

Chapter 3. Experimental studies realistic interfacial systems of industrial relevance through the use of surface sensitive

synchrotron radiation and related techniques, notably grazing incidence EXAFS, surface X-ray diffraction and

environmental NEXAFS spectroscopy.

Chapter 4. Studies aimed at understanding the, often complex, inter-relationships between structure, kinetics and properties via

the development of advanced multi-technique on-line process analytical techniques together with their use for the

manipulation and control of industrial batch-wise crystallisation processes.

Chapter 5. Application of high resolution powder diffraction, often using synchrotron radiation, for the analysis of molecular

materials not amenable to conventional single crystal crystallographic analysis together with the integration of this

work with other experimental data and linked to molecular and crystallographic modelling methods.

Whilst most of these chapters focus on one generic theme, the boundaries between these can be diffuse and in addition I have written

a number of review or overview papers which span several chapter focus areas. Overall some of the sets of papers are measurement

technique based, some are molecular modelling based and some involve both approaches with the latter often attempting to draw

inter-relationships between these two contrasting approaches.

In summary, the research contained in this DSc submission has been directed towards understanding, predicting and manipulating

the properties of solid-form chemical products, and the interfaces associated with their formation, when operating under realistic

thermodynamic conditions of temperature and pressure. This generically-based perspective has encompassed both theoretical and

experimental studies, integrated synergistically within a strong molecular engineering underpinning framework, associated with both

fundamental and strategic research programmes with the latter involving substantial industrial collaboration.

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A Note on Authorship

The work presented here in this thesis draws down on my 25 years of post-doctoral academic life following the award of my PhD from

Portsmouth Polytechnic (now University of Portsmouth) in 1978 through to the present in 2003. The research presented involved

work carried out in 4 academic institutions (Strathclyde4, Aachen5, Heriot-Watt6 and Leeds7) with the first institution representing the

dominant fraction of the research work presented here.

The submission, which draws down on the vision presented in my inaugural lecture, Engineering at the Molecular Scale, presented at

Leeds in November 2001 (see appendix A), forms a selection of my published work (see list of graduated PhD students in appendix B

together with my CV and publications given in appendices C and D, respectively). Mostly, I have omitted duplicate, e.g. conference,

versions of the journal papers presented. However, I have included some conference papers and a few technical reports in cases where

full journal publication has not been made and where I believe the results to be significant either in detail or in context. Overall, the

submission forms a natural academic progression, I believe, from my PhD studies (see appendix E).

Usually, the work involves collaboration with supervised research students and research assistants as well as through collaboration with

academic colleagues either in one of the host institutions or with a collaborating institution (industry, another university or a national

laboratory). A short statement preceding the collation of publications provided at the start of each chapter indicates the strategic

context for the work, i.e. funding sources and collaboration involved. In this, the lead authors the papers cited are identified in bold.

Readers will note that I have not claimed senior authorship for much of my post-doctoral work but have chosen to include it and I

believe my contribution to be significant, drawing down as it does on my earlier PhD work. A full route map for all co-authors listed

in the publications is given in appendix F.

A detailed profile of the research funding associated with my research following permanent academic appointment is provided in

Appendix G. In the latter case the principle investigators for the research grants are given in bold for cases where the applicant is not

the principle investigator.

[Note all appendices are provided in the full published version, available from the University of Strathclyde in Glasgow].

4. Physical Chemistry Section, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland, UK.5. Institut für Kristallographie, Technical University of Aachen, Aachen, Germany.6. Centre for Molecular and Interface Engineering, Department of Mechanical and Chemical Engineering, Heriot-Watt University, Riccarton, Edinburgh, Scotland, UK.7. Institute of Particle Science and Engineering, Department of Chemical Engineering, University of Leeds, Leeds, UK.

5

Chapter 1

Studies of crystal lattice defects in nearly perfect single crystals and their role in solid-state, surface and interfacial processes using X-ray topography and other related techniques

Summary: - This work represents the development of work initiated in my PhD studies in the growth and perfection of

nearly perfect single crystals and their subsequent processing.

The first set of papers [1-5] result from my PhD work supervised by Denis Elwell (now retired) at Portsmouth Polytechnic (now University

of Portsmouth) associated with a CASE collaboration with Brian Isherwood (now retired) at the then GEC Hirst Research Centre in

Wembley. These are provided for context rather than assessment for this DSc submission.

The next set of papers [6-17] relates to my PDRA work with John Sherwood at Strathclyde and are associated with crystal growth, defect

characterisation via X-ray topography and theoretical calculation of dislocation energetics and was associated with the PhD work of Ian

Begg (not submitted) and Peter Halfpenny.

In the next set of papers [18-23] the work was extended via collaboration with Keith Bowen at the University of Warwick (now with

Bede Scientific Instruments) into the use of white beam topographic techniques using synchrotron radiation. This work was associated

with the development of facilities on station 7.6 at the then new Daresbury SRS.

The next group of papers [24-35] describes my work on the application of the above methods to studies of phase transformations

which was initiated via the Royal Society exchange programme associated with my collaboration with Professor Helmut Klapper at the

Technical University of Aachen. This work was continued when I returned to Strathclyde via EPSRC grant support also involving PhD

work of Amer El Korashy and collaboration with Richard Pethrick at Strathclyde for the ultrasonic studies described in paper [34].

The next two groups of papers which involve collaboration with John Sherwood at Strathclyde and Roger Davey at ICI (now UMIST) [36-

43] and [44-46], involving the PhD works of Derek Cunningham and Xiaojun Lai. The research describes the application of synchrotron

radiation surface diffraction and spectroscopy (EXAFS and standing waves) respectively to studies of crystal surface structure during

growth and to the structural environment of crystal habit modifiers on surfaces. The latter work also involves complementary molecular

modelling studies developed through collaboration with Dr David Armstrong at Strathclyde in paper [45].

The final groups of papers [47-53] and [54-55] reflects a long-standing collaboration with Lisandro Cardoso at Campinas in Brasil

drawing down on my earlier PhD work with Brian Isherwood at GEC, as described in papers [3,5] and further developed via paper

[47]. The work was associated, respectively, with the development of X-ray multiple diffraction using synchrotron radiation initially

examining semiconductor and ionic crystals involing the PhD work of Luiz Humberto Avanci and Xiaojun Lai but latterly molecular

crystals as part of the PhD work of Susan Girdwood.

1. Crystal habit and surface morphology of flux grown yttrium aluminium garnet, K J Roberts and D Elwell, Journal

of Crystal Growth 53 (1981) 249-260

2. Dislocations in Y3Al5O12, K J Roberts, Journal of Material Science 16 (1981) 2517-2520

3. Surface and bulk growth induced strains in flux grown yttrium aluminium garnet, K J Roberts and B J Isherwood,

Journal of Material Science Letters 1 (1982) 1-3

4. Correlation between growth hillocks and dislocations on the {110} faces of yttrium aluminium garnet, K J Roberts

and D Elwell, Journal of Crystal Growth 62 (1983) 449-457

5. Useful reflection sets for the analysis of lattice strains in cubic crystals using the X-ray multiple

diffraction technique, K J Roberts and B J Isherwood, Journal of Materials Science Letters 3 (1984) 29-32

6. X-ray topographic studies of the perfection of crystals of the organic metal tetrathiofulvalene

tetracyanoquino-dimethane (TTF-TCNQ), I D Begg, R S Narang, K J Roberts and J N Sherwood, Journal of Crystal

Growth 49 (1980) 735-738

6

7. Influence of crystal perfection on the conductivity of tetrathiofulvalene-tetracyanoquino-dimethane, I D Begg, K

J Roberts, J N Sherwood, I Groth-Anderson and C S Jacobsen, Chemical Physics Letters 79 (1981) 513-516

8. X-ray topographic investigations of dislocations in sodium chlorate, R M Hooper, K J Roberts and J N Sherwood,

Journal of Materials Science 18 (1982) 81-88

9. The growth and perfection of crystals of ammonium dihydrogen orthophosphate, L Bhat, K J Roberts and J N

Sherwood, Journal of Applied Crystallography 16 (1983) 390-398

10. X-ray topographic investigations of solid-state reactions. 1. Changes in surface and bulk sub-structure during

incipient thermal decomposition in sodium chlorate monocrystals, I D Begg, P J Halfpenny, R M Hooper,

R S Narang, K J Roberts and J N Sherwood, Proc Royal Soc A 386 (1983) 431-442

11. A computer programme generating parameters useful in X-ray topographic studies, K J Roberts, J Applied

Crystallography 16 (1983) 577-578

12. Dislocation configurations in single crystals of pentaerythritol tetranitrate and cyclotrimethylene trinitramine,

P J Halfpenny, K J Roberts and J N Sherwood, J Crystal Growth 65 (1983) 524-529

13. Dislocations in energetic materials. 1. The crystal growth and perfection of pentaerythritol tetranitrate (PETN),

P J Halfpenny, K J Roberts and J N Sherwood, Journal of Crystal Growth 67 (1984) 202-212

14. Dislocations in energetic materials. 2. Characterisation of the growth-induced dislocation structure of

pentaerythritol tetranitrate (PETN), P J Halfpenny, K J Roberts and J N Sherwood, Journal of Applied

Crystallography 17 (1984) 320-327

15. Dislocations in energetic materials. 3. Etching and microhardness studies of pentaerythritol tetranitrate and

cyclotrimethylene trinitramine, P J Halfpenny, K J Roberts and J N Sherwood, Journal of Material Science 19

(1984) 1629-1637

16. Dislocations in energetic materials. 4. The crystal growth and perfection of cyclotrimethylene trinitramine (RDX),

P J Halfpenny, K J Roberts and J N Sherwood, Journal of Crystal Growth 69 (1984) 73-81

17. Dislocations in energetic materials. 5. Dislocation characterisation and post-growth motion in single crystals of

cyclotrimethylene trinitramine, P J Halfpenny, K J Roberts and J N Sherwood, Philosophical Magazine A 53 (1986)

531-542

18. The X-ray topography station at Daresbury Laboratory, D K Bowen, G F C Clark, S T Davies, J R S Nicholson,

K J Roberts, J N Sherwood and B K Tanner, Nuclear Instruments and Methods 192 (1982) 277-284

19. Synchrotron radiation induced polymerization of TCDU, K J Roberts, J N Sherwood, D K Bowen, S T Davies and

R Baughman, SERC Daresbury Laboratory Report (1983) Dl/SCI/435ABN

20. The perfection of polybis (p-toluene sulphonate) diacetylene crystals, D Bloor, D K Bowen, S T Davies, K J Roberts

and J N Sherwood, Journal of Material Science Letters 1 (1982) 150-152

21. Synchrotron radiation damage in sodium bromate, K J Roberts, J N Sherwood, D K Bowen and S T Davies, Journal

of Material Science Letters 1 (1982) 300-302

22. Synchrotron radiation X-ray topographic study of the beam stability and perfection of some organic single

crystals, K J Roberts, J N Sherwood, D K Bowen and S T Davies, Materials Letters 2 (1983) 104-110

23. Environmental facility for synchrotron radiation topography, K Gillespie, A Littlejohn, K J Roberts, D B Sheen and

J N Sherwood, Review of Scientific Instruments 60 (1989) 2498-2501

24. X-ray topographic investigations of phase transitions in crystals, H Klapper, K J Roberts, D Götz and N Herres,

Journal of Crystal Growth 65 (1983) 621-636

25. A synchrotron radiation study of modulated ((CH3)4N)2ZnCl4 crystals, A El Korashy, K J Roberts,

T Scheffen-Lauenroth and B Dam, Journal of Applied Crystallography 20 (1987) 512-516

26. Synchrotron Laue topography studies of pseudo-hexagonal twinning, R Docherty, A El- Korashy, H-D Jennisson,

H Klapper, K J Roberts and T Scheffen-Lauenroth, Journal of Applied Crystallography 21 (1988) 406-415

27. An EXAFS investigation of the Zn-environment in K2ZnCl4 during solid-to-solid phase transformations, H L Bhat,

K J Roberts and M Sacchi, Journal of Physics Condensed Matter 2 (1990) 8557-8565

28. A furnace for in situ synchrotron Laue diffraction and its application to studies of solid- state phase

transformations, H L Bhat, S M Clark, A El Korashy and K J Roberts, Journal of Applied Crystallography 23 (1990)

545-549

7

29. Synchrotron X-ray topographic studies of para-ferroelectric transition in ammonium sulphate crystal, H L Bhat,

H Klapper and K J Roberts, In “Synchrotron Radiation Sources” (Eds. S S Ramamurthi, G Singh and D Angal),

Proceedings of the Conference on Synchrotron Radiation Sources, Indore, India 3-6/02/92, Centre for Advanced

Technology, Indore-452013 (1992) 342-344

30. An examination of the 140°C phase transition in triammonium hydrogen sulphate (NH4)3H(SO4)2 using

synchrotron radiation white-beam topography, R A Becker, R Docherty, A El Korashy, H-D Jennissen, H Klapper and

K J Roberts, Phase Transitions 39 (1992) 171-183

31. An X-ray topographic study of the paraelectric to ferroelectric phase transformation in nearly perfect single

crystals of ammonium sulphate, H L Bhat, H Klapper and K J Roberts, Journal of Applied Crystallography 28 (1995)

168-188

32. Real-time synchrotron X-ray topography of the paraelectric to ferroelectric phase transition in ammonium

sulphate, H L Bhat, G F Clark, H Klapper and K J Roberts, Journal of Physics: Applied Physics 28A (1995) 23-26

33. Slit-collimated Laue diffraction using synchrotron radiation: an examination of the paraelectric to ferroelectric

phase transformation in ammonium sulfate, H L Bhat, H Klapper and K J Roberts, Journal of Applied

Crystallography 28 (1995) 827-829

34. Ultrasonic measurements of the elastic constants and their temperature dependence for nearly perfect single

crystals of potassium tetrachlorozincate (K2ZnCl4), A El Korashy, S Gilmour, R A Pethrick and K J Roberts, Journal

of Applied Crystallography 29 (1996) 700-706

35. Studies of electrical; properties for K2ZnCl4 single crystals during commensurate incommensurate paraelectric

phase transitions, A El Korashy and K J Roberts, Journal of Physics and Chemistry of Solids 64 (2003) 2133-2139

36. Structural studies of the crystal/solution interface using synchrotron radiation, D Cunningham, R J Davey,

K J Roberts, J N Sherwood and T Shripathi, Journal of Crystal Growth 99 (1990) 1065-1069

37. Crystallisation from the liquid phase: Recent in situ diffraction experiments using syn¬chrotron radiation at the

Daresbury SRS, D Cunningham, R J Davey, S E Doyle, A R Gerson, D Hauserman, M Herron, K J Roberts, J Robinson,

J N Sherwood, T Shripathi and F C Walsh, In “Synchrotron Light: Applications and Related Instrumentation II”,

World Scientific Press, (1990) 230-244

38. Quantifying some of the structural aspects of crystallisation processes: Experiments using synchrotron radiation,

D A H Cunningham, A R Gerson, K J Roberts, J N Sherwood and K Wojciechowski, In “Advances in Industrial

Crystallisation” (Eds. J Garside, R J Davey and A G Jones), Butterworths, London, 1991, 105-130

39. The use of synchrotron radiation in the study of structural and kinetic aspects of crystallisation, R J Davey,

D A Cunningham, A R Gerson, R Ristic, K J Roberts and J N Sherwood, In “Particle Design via Crystallisation” (Eds.

R Ramanarayanan, W Kern, M Larson and S Sikdar), American Institution of Chemical Engineers Symposium Series

284 87 (1991) 104-113

40. Synchrotron X-radiation: Its application to the structural characterisation of crystal growth processes, K J Roberts

and J N Sherwood, In “Synchrotron Radiation Sources” (Eds. S S Ramamurthi, G Singh and D Angal), Proceedings

of the conference on synchrotron radiation sources, Indore, India 3-6/02/92, Centre for Advanced Technology,

Indore-452013 (1992) 303-308

41. In situ surface X-ray diffraction using high energy synchrotron radiation: Studies of the ADP (100) and (101)

growth interfaces under aqueous solution flow conditions, K J Roberts, J N Sherwood, K Wojciechowski, A A

Chernov, Yu G Kuznetsov and R J Davey, Journal of Physics: Applied Physics 26A (1993) 107-114

42. The application of synchrotron X-ray techniques to problems in crystal science and engineering, K J Roberts, J

Crystal Growth 130 (1993) 657-681

43. Characterisation of crystal growth processes using synchrotron X-ray techniques, K J Roberts, In “Science and

Technology of Crystal Growth” (Eds. J P van der Eerden and O S L Bruinsma), Kluwer academic publishers,

Dordrecht, The Netherlands, 1995, 367-382

44. Glancing angle EXAFS investigation of the habit modification of ADP by the incorporation of iron, N T Barrett, G

M Lamble, K J Roberts, J N Sherwood, G N Greaves, R J Davey, R J Oldman and D Jones, Journal of Crystal Growth

94 (1989) 689-696

8

45. Investigation into the structural chemistry of Cu2+ ions in doped nearly perfect single crystals of ammonium

sulphate with reference to their role in habit modification, D A H Cunningham, D R Armstrong, G Clydesdale and

K J Roberts, Journal of the Chemical Society: Faraday Discussions 95 (1993) 347-365

46. Understanding the habit modification of ammonium dihydrogen phosphate by chromium ions using a dopant-

induced charge compensation model, D A H Cunningham, R B Hammond, X Lai and K J Roberts, Chemistry of

Materials 7 (1995) 1690-1695

47. The application of synchrotron radiation to X-ray multiple-diffraction studies, B Brown, G F Clark, C Dineen,

B J Isherwood, E Pantos, K J Roberts and T Scheffen-Lauenroth, Journal of Applied Crystallography 22 (1989)

201-204

48. Experimental facilities for high resolution X-ray multiple diffraction using the Daresbury synchrotron radiation

source, C Campos, G F Clark, E Pantos, K J Roberts and J M Sasaki, Proceedings of the 2nd European conference

on progress in X-ray synchrotron radiation research (Eds. A Balerna, E Bernieri and S Mobilio), Società Italiana di

Fisica, Conference Proceedings 25 (1990) 425-429

49. High resolution Renninger scan obtained on InGaAs/AlGaInAs/InP layered material with synchrotron radiation,

J M Sasaki, L P Cardoso, C Campos, K J Roberts, G F Clark, J Decobert and M A Sacilotti, Proceedings 5th Brazilian

school semiconductor physics (Eds. J R Leite, A Fazzio and A S Chaves) World Scientific, Singapore (1991) 262-265

50. Using synchrotron radiation X-ray multiple diffraction to examine the lattice coherency of semiconductor

surfaces and epitaxial layers, J.M. Sasaki, L.P. Cardoso, C. Campos, K.J. Roberts, G F Clark, E Pantos and

M A Sacilotti, Journal of Applied Physics 79 (1996) 3494-3498

51. X -Ray multiple diffraction in Renninger scanning mode: simulation of data using synchrotron radiation,

J M Sasaki, L P Cardoso, C Campos, K J Roberts, G F Clark, E Pantos and M A Sacilotti, Journal of Applied

Crystallography 29 (1996) 325-330

52. Synchrotron radiation multiple diffraction study of Al0.304Ga0.172In0.524As MOVPE grown onto InP(001),

J M Sasaki, L P Cardoso, C Campos, K J Roberts, G F Clark, E Pantos and M A Sacilotti, Journal of Crystal Growth

172 (1997) 284-290

53. An examination into the habit modification of nearly perfect single crystals of potassium dihydrogen phosphate

(KDP) by trivalent manganese ions as studied using synchrotron radiation X-ray multiple diffraction in Renninger

scanning mode. X. Lai, K. J. Roberts, J. M. Sasaki, L. H. Avanci and L. P. Cardoso, Journal of Applied Crystallography

36 (2003) 1230-1235

54. Piezoelectric coefficients of mNA organic nonlinear optical material using synchrotron X-ray multiple diffraction,

L H Avanci, L P Cardoso, S Girdwood, D Pugh, J N Sherwood, J M Sasaki and K J Roberts, Physical Review Letters 81

(1998) 5426-5429

55. Synchrotron radiation X-ray multiple diffraction applied to the study of electric field induced strain in MBANP

organic nonlinear optical material, L.H. Avanci, L.P. Cardoso, S.E. Girdwood, J.M. Sasaki, K.J. Roberts, D.Pugh and

J.N. Sherwood, Physical Review B 61 (2000) 6507-6514

9

Chapter 2.

Application of molecular and solid-state modelling techniques using, the atom-atom approximation, to the prediction of crystal morphology, habit modification and other physical properties

Summary: - This work draws down on work started in my PhD and PDRA work associated with the wish to be able to predict crystal

shape using crystallographic methods.

The first set of papers [56-86] describe studies on organic crystals and was developed after I returned to Strathclyde via the research

of two PhD students (Robert Docherty and Graham Clydesdale) through which the HABIT programme was developed and used in the

PhD work of Lorna Smith and Elaine Walker. This research was supported financially by Exxon Chemical, ICI, MSI, Unilever and EPSRC.

Four papers [54, 57, 61, 62] in this set involve collaboration with Professor Pieter Bennema’s group at the University of Nijmegen in the

Netherlands whilst papers [79], [82] and [82, 85, 86] involved collaboration, respectively, with David Grant at Minnesota, Peter York at

Bradford and Robert Hammond at Leeds.

The next papers [87-89] describe collaborative work with Dr David Pugh at Strathclyde in which the basic methodology is extended to

the prediction of elastic properties of crystals.

The final group of papers [90-97] extends the methodology to studies of inorganic molecular ionic materials involving some experimental

crystallisation studies together with detailed work on potential development and morphological simulation. This work area was initiated

through the PhD work of Paul Meenan and Gillian Thomson (Telfer), developed through collaboration with Robert Jackson at the

University of Keele and funded by the Unilever, DuPont and the EPSRC.

56. A theoretical analysis of the morphology of benzophenone, K J Roberts, L A M J Jetten, and P Bennema,

Institution of Chemical Engineers, North Western Branch Papers 3 (1985) 201-214

57. Modelling the morphology of molecular crystals; Applications to anthracene, biphenyl and ß-succinic acid,

R Docherty and K J Roberts, Journal of Crystal Crowth 88 (1988) 159-168

58. MORANG - A computer programme designed to aid in the determinations of crystal morphology, R Docherty,

K J Roberts and E Dowty, Computer Physics Communications 51 (1989) 423-430

59. Application of the Bravais-Friedel-Donnay-Harker, attachment energy and Ising models to predicting and

understanding the morpholgy of molecular crystals, R Docherty, G Clydesdale, K J Roberts and P Bennema, Journal

of Physics: Applied Physics Physics 24 (1991) 89-99

60. HABIT - A computer program to predict the morphology of molecular crystals, G Clydesdale, R Docherty and

K J Roberts, Computer Physics Communications 64 (1991) 311-328

61. The structural stability and crystal morphology of even number n-alkanes crystallising in the homologous series

series C18H38 to C28H58, G Clydesdale and K J Roberts, In “Particle Design via Crystallisation” (Eds. R Ramanarayanan,

W Kern, M Larson and S Sikdar), American Institution of Chemical Engineers Symposium Series 284 87 (1991)

130-137

62. A predictive approach to modelling the morphology of organic crystals based on crystal structure using the atom-

atom method, G Clydesdale, R Docherty and K J Roberts, In “Crystal Growth - 3rd European Conference” (

Ed. A Lörinczy), Trans Tech Pub, Zurich, Crystal Properties and Preparation 36-38 (1991) 234-243

63. Morphology of orthorhombic long chain normal alkanes: Theory and observations, P Bennema, Xiang Yang Liu,

K Lewtas, R D Tack, J J M Rijpkema and K J Roberts, Journal of Crystal Growth 121 (1992) 679-696

64. The importance of considering growth-induced conformational change in predicting the morphology of

benzophenone, K J Roberts, R Docherty, P Bennema and L A M J Jetten, Journal of Physics: Applied Physics 26B

(1993) 7-21

10

65. Morphological studies of single n-alkanes crystallising in the homologous series C16H38 - C38H78, G Clydesdale,

K Lewtas and K J Roberts, In “Industrial Crystallisation 93” (Ed. Z Rojkowski), Proceedings of the 12th Symposium

on Industrial Crystallisation, Warsaw, Poland, (1993) 3057-3062

66. Computational studies of the morphology of molecular crystals through solid-state intermolecular force

calculations using the atom-atom method, G Clydesdale, K J Roberts and R Docherty, In

“Colloid and Surface Engineering: Controlled Particle, Droplet and Bubble Formation” (Ed. D Wedlock),

Butterworths Heineman, London, 1993, 95-135

67. Theoretical analysis of the polar morphology and absolute polarity of crystalline urea, R Docherty, K J Roberts,

V Saunders, S Black and R J Davey, Journal of the Chemical Society: Faraday Discussions 95 (1993) 11-25

68. Modelling the morphology of molecular crystals in the presence of disruptive tailor-made additives, G Clydesdale,

K J Roberts and R Docherty, Journal of Crystal Growth 135 (1994) 331-340

69. Computational modelling study of the growth morphology of the normal alkane docosane and its mediation by

“tailor-made” additives, G Clydesdale, K J Roberts and K Lewtas, Molecular Crystals Liquid Crystals 248 (1994)

243-276

70. Understanding the solvent-induced habit modification of benzophenone in terms of molecular recognition at the

crystal/solution interface, K J Roberts, J N Sherwood, C S Yoon and R Docherty, Chemistry of Materials 6 (1994)

1099-1102

71. Modelling the morphology of molecular crystals in the presence of blocking tailor-made additives, G Clydesdale,

K J Roberts, K Lewtas and R Docherty, Journal of Crystal Growth 141 (1994) 443-450

72. Modelling the habit modification of molecular crystals by the action of “tailor-made” additives, G Clydesdale and

K J Roberts, In “Science and Technology of Crystal Growth” (Eds. J P van der Eerden and O S L Bruinsma), Kluwer

academic publishers, Dordrecht, The Netherlands, 1995, 179-192

73. The effect of solvent in the determination of morphology: a study of ε-caprolactam, K J Roberts, E M Walker and

S J Maginn, Molecular Crystals and Liquid Crystals 279 (1996) 233-240

74. HABIT95 - A program for predicting the morphology of molecular crystals as a function of growth environment,

G Clydesdale, K J Roberts and R Docherty, Journal of Crystal Growth 166 (1996) 78-83

75. HABIT95 - A program for predicting the morphology of molecular crystals as a function of growth environment,

G Clydesdale, K J Roberts and R Docherty, Quantum Chemistry Program Exchange 16 (1996) 1-1

76. Modelling the morphology and habit modification of molecular crystals on a structural basis, G Clydesdale,

K J Roberts and E M Walker, Proceedings of the 5th World Congress of Chemical Engineering (1996) 723-737

77. Predicting particle morphology on the basis of the root molecular and crystal structure, K J Roberts and

E M Walker, Current Opinion in Solid State and Materials 1 (1996) 506-523

78. The crystal habit of molecular materials: A structural perspective, G Clydesdale, K J Roberts and E M Walker,

In “Molecular Solid State: Syntheses, Structure, Reactions, Applications” Volume 2, “Theoretical Aspects and

Computer Modelling” (Ed. A Gavezzotti), chapter 7 (1996), 203-232

79. Modelling the morphology of α-lactose monohydrate, G B Telfer, G Clydesdale, K J Roberts and D J W Grant,

Journal of Pharmaceutical Science 86 (1997) 135-141

80. A theoretical examination of the molecular packing, intermolecular bonding and crystal morphology of

2,4,6-trinitrotoluene in relation to polymorphic structural stability, H G Gallagher, K J Roberts, J N Sherwood and

L A Smith, Journal of Materials Chemistry 7 (1997) 229-235

81. A structural approach to predicting the effect of growth environment on crystal shape, G Clydesdale, K J Roberts

and E M Walker, Proceedings of the Fourth International Workshop on the Crystal Growth of Organic Materials

(CGOM-4), Bremen, Germany, (1997), 45-52

82. Polymorphism in chlordiazepoxide: Crystal chemistry, particle morphology and structural aspects of phase

interconversion, R B Hammond, K J Roberts, D Singh, P York and L Shields, submitted to the proceedings of the

Forth International Workshop on the Crystal Growth of Organic Materials (CGOM-4), Bremen, Germany (edited J

Ulrich), Shaker Verlag, Aachen, Germany (1997), 76-83

83. Modelling impurity-mediated crystal growth interfaces: A molecular dynamics study of the crystal habit surfaces

of ε-caprolactam, E M Walker, K J Roberts and S J Maginn, Langmuir 14 (1998) 5620-5630

11

84. Modelling the influence of succinic acid on the morphology of adipic acid, G B Thomson, E M Walker,

G Clydesdale, K J Roberts, P Meenan and R Docherty, Proceedings of the 4th World Congress on Particle

Technology (WCPT4), Sydney, Australia, 21-25 July 2002, CD publication (ISBN 085 825 7947), paper 94 (8 pages)

85. Molecular modelling of bulk impurity segregation and impurity-mediated crystal habit modification of

naphthalene and phenanthrene in the presence of heterogeneous species, G Clydesdale, R B Hammond and

K J Roberts, J Physical Chemistry 107 (2003) 4826-4833

86. Molecular and solid-state modelling of the crystal purity and morphology of ε-caprolactam in the presence of

synthesis impurities and the imino tautomeric species caprolactim, P. Mougin, G Clydesdale, R B Hammond and

K J Roberts, J Physical Chemistry 107 (2003) 13262-13272

87. Elastic tensor atom-atom potential calculations for molecular crystals: Carbon dioxide (CO2), P Pavlides,

D Pugh and K J Roberts, Journal of Physics D: Applied Physics 24 (1991) 100-104

88. Elastic constants of molecular crystals in the pair potential rigid molecule approximation, P Pavlides, D Pugh and

K J Roberts, Molecular Physics 72 (1991) 121-131

89. Elastic tensor atom-atom potential calculations for molecular crystals: C6H6 and CO(NH2)2, P Pavlides, D Pugh

and K J Roberts, Acta Crystallographica A 47 (1991) 846-850

90. Understanding and controlling the crystal morphology of some ionic crystals, P Meenan, K J Roberts,

J N Sherwood and K Yurrigar, Powder Technology 65 (1991) 219-225

91. The determination of a transferable potential for modelling intra- and inter-ionic interactions in alkali sulphates,

P Meenan, R Jackson and K J Roberts, SERC Daresbury Laboratory Report (1993) DL/SCI/866T

92. Deriving empirical potentials for molecular ionic materials, R A Jackson, P Meenan, G D Price, K J Roberts, G B

Telfer and P J Wilde, Mineralogical Magazine 59 (1995) 617-622

93. Determination of a transferable inter atomic potential for alkali perchlorates and its application to morphological

modelling, R A Jackson, P Meenan, K J Roberts, G B Telfer and P J Wilde, Journal of the Chemical Society: Faraday

Transactions 91 (1995) 4133-4138

94. Potential fitting to molecular ionic materials, G B Telfer, P J Wilde, R A Jackson, P Meenan and K J Roberts,

Philosophical Magazine B 73(1) (1996) 147-152

95. A transferable potential for alkali chorates and bromates, G B Telfer, J D Gale, K J Roberts, R A Jackson, P J Wilde

and P Meenan, Acta Crystallographica A 53 (1997) 415-420

96. An analysis of the crystal morphology of sodium chlorate using a polar attachment energy model, G Clydesdale,

K J Roberts, G Telfer, V Saunders, D Pugh, R A Jackson and P Meenan, J Physical Chemistry B 102 (1998) 7044-

7049

97. Interatomic potential parameters for potassium tetrachlorozinate and their application to modelling phase

transitions, E S Ferrari, K J Roberts, G B Thomson, J D Gale and C R A Catlow, Acta Crystallographica A57 (2001)

264-271

12

Chapter 3

Structural characterisation of surfaces and condensed interfaces, when operating under realistic thermodynamic conditions of temperature and pressure, via the application of synchrotron X-ray techniques

Summary: This work describes work directed to the use of synchrotron radiation in the study of condensed interfaces, of potential

industrial significance, when operating under representative thermodynamic conditions of temperature and pressure. This work

was mostly carried out at CCLRC Daresbury Laboratory during my period as a joint appointee there associated with a variety of

research programmes. The later work, on NEXAFS spectroscopy, was carried out National Synchrotron Light Source at Brookhaven

National Laboratory.

The first group of papers [98-107] describes collaborative work with Neville Greaves from Daresbury (now at Aberystwyth) and Richard

Oldman from ICI (now retired), funded by ICI and EPSRC, associated with the PhD work of Stefania Pizzini and involving the development

of grazing incidence EXAFS and reflectivity techniques for surface characterisation.

The next groups of papers [108] and [109-114] relate closely to the above but involve collaborations with Peter Halfpenny from

the University of Southampton (now at Strathclyde) and Neil Gibson at the European Union Joint Research Centre at Ispra in Italy.

Additional funding from the EPSRC and EU was provided with in the latter case the work involving my appointment as a visiting scientist

at Ispra associated with the PhD work of Tess Crabb.

The next group of papers [115-124] represents the extension of the work into the area of in-situ electrochemical interface characterisation

associated with collaborations with Frank Walsh at Strathclyde (now at Bath) and Jim Robinson at the University of Warwick funded by

the EPSRC and Johnsson Matthey and involving the PhD work of Maura Herron.

The next group of papers [125-131] form a natural progression from the previous groups extending the work to examine tribo- and

thermo-chemical processes at additive-mediated metal/oil interfaces through work funded by Exxon Chemical (now Infinium) and

EPSRC. This work also involves complementary molecular modelling studies with the latter involving collaboration with Dr David

Armstrong at Strathclyde.

The next set of papers [132-143] reflects my involvement in the development of material science station 9.3 at the Daresbury

SRS comprising a number of isolated case studies together with an instrumentation paper and a useful review. In this, additional

collaborations to those already mentioned involved Professor Stefan Enzo from the University of Venice, Ted Davies from the University

of Exeter, Brian Edwards from the University of Southampton, David Garner from the University of Manchester (now at Nottingham)

and Will Phythian at AEA Technology in Harwell.

The final set of papers [144-152] reflects my work as a visiting scientist at the National Synchrotron Light Source at Brookhaven

National Laboratory where I have extended the surface EXAFS studies into the soft X-ray region, via the development of environmental

NEXAFS spectroscopy, thus permitting examination of organic surfaces and interfaces. Funding was provided by the European Union

Joint Research Centre, EPSRC, SERC Daresbury Laboratory, ICI, Exxon Chemical, Johnsson Matthey and AEA Technology.

98. The surface sensitivity of fluorescence EXAFS at reflection conditions, S Affrossman, S Doyle, G M Lamble,

M A Morris, K J Roberts, D B Sheen, J N Sherwood, R J Oldman, D Hall, R J Davey, and G N Greaves, Journal de

Physique C8, suppl. 12 (1986) 167-171

99. Instrumentation for glancing angle X-ray absorption spectroscopy on the synchrotron radiation source, S Pizzini,

K J Roberts, G N Greaves, N Harris, P Moore, E Pantos and R J Oldman, Review of Scientific Instruments 60 (1989)

2525-2528

100. Applications of glancing-angle X-ray absorption spectroscopy to the structural characterisation of copper film

surfaces, S Pizzini, K J Roberts, I S Dring, R J Oldman and G N Greaves, Physica B 158 (1989) 676-678

13

101. Some industrial applications of grazing incident EXAFS techniques, I S Dring, R J Oldman, A Stocks, D J Walbridge,

N Falla, K J Roberts and S Pizzini, Mat Res Soc Symp Proc 143 (1989) 169-174

102. Characterisation of polyphenylene thin films using synchrotron radiation X-ray reflectivity, K J Roberts,

J N Sherwood, T Shripathi, R J Oldman, P A Holmes and A Nevin, Journal of Physics: Applied Physics 23 (1990)

255-257

103. The local atomic structure of the oxide coating on polished GaAs (100), N T Barrett, G N Greaves, S Pizzini and

K J Roberts, Surface Science 227 (1990) 337-346

104. X-ray absorption spectroscopy under conditions of total external reflection: Applications to the structural

characterisation of the Cu/GaAs(100) interface, S Pizzini, K J Roberts, G N Greaves, N T Barrett, I D Dring and

R J Oldman, Journal of the Chemical Society: Faraday Discussions 89 (1990) 51-63

105. Glancing angle X-ray absorption spectroscopy: Applications to the structural characterisation of condensed

interfaces, S Pizzini, K J Roberts, G N Greaves, N T Barrett, I D Dring and R J Oldman, In “Synchrotron Light:

Applications and Related Instrumentation II”, World Scientific Press, (1990) 67-107

106. Investigation of the local structure around iron dispersed in vinyl chloride-vinylidene chloride (VC-VdC) copolymer

coatings on mild steel using glancing-angle X-ray absorption spectroscopy, S Pizzini, K J Roberts, I Dring, P J

Moreland, R J Oldman and J Robinson, Journal of Materials Chemistry 2 (1992) 49-55

107. Application of X-ray absorption spectroscopy to the structural characterisation of mono-dispersed benzotriazole

coatings on partly oxidised copper thin films, S Pizzini, K J Roberts, I S Dring, R J Oldman and D C Cupertino,

Journal of Materials Chemistry 3 (1993) 811-819

108. The structural environment of Te dopants in GaAs using EXAFS in fluorescence mode, G N Greaves, P J Halfpenny,

G M Lamble and K J Roberts, Journal de Physique C8, suppl. 12 (1986) 901-904

109. ReflEXAFS investigation of the local atomic structure around Fe during the oxidation of stainless steel, N T Barrett,

P N Gibson, G N Greaves, P Mackle, K J Roberts and M Saachi, Journal of Physics: Applied Physics 22 (1989)

542-546

110. Glancing angle X-ray spectroscopy of oxidised stainless steel surfaces, N Barret, N Gibson, G N Greaves,

K J Roberts and M Saachi, Physica B 158 (1989) 690-691

111. Characterisation of sulphidised steel surfaces using synchrotron radiation, N T Barrett, D Cunningham,

M Dos Santos, R A H Edwards, P N Gibson, A Manara and K J Roberts, Proceedings of the 2nd European conference

on progress in X-ray synchrotron radiation research (Eds. A Balerna, E Bernieri and S Mobilio),

Società Italiana di Fisica, Conference Proceedings 25 (1990) 489-493

112. Application of X-ray absorption near edge spectroscopy at the S K-edge to the structural characterisation of

surface reacted metallic alloys, T A Crabb, K J Roberts and P N Gibson, Japanese Journal of Applied Physics 32-2

(1993) 428-430

113. REX - a program for the analysis of X-ray reflectivity data: User guide and programmer manual, T A Crabb,

P N Gibson and K J Roberts, SERC Daresbury Laboratory Technical Memorandum (1992) DL/SCI/TM88E

114. REX - A least-squares fitting program for the simulation and analysis of X-ray reflectivity data, T A Crabb,

P N Gibson and K J Roberts, Computer Physics Communications 77 (1993) 441-449

115. Instrumentation and data acquisition for in situ electrochemistry on the SRS, N Barlow, C Brennan, S Doyle,

G N Greaves, M Miller, A Nahle, K J Roberts, J Robinson, J N Sherwood, F C Walsh, Review of Scientific Instruments

60 (1989) 2386-2389

116. An in situ energy dispersive EXAFS study of the platinum fuel cell electrode, S E Doyle, M E Herron, K J Roberts,

J Robinson and F C Walsh, Proceedings 6th International Conference on X-ray Absorption Fine Structure (XAFS VI),

Ellis Horwood (1991) 279-281

117. In situ X-ray scattering techniques for the study of electrode reactions: Experiments at the Daresbury SRS,

S E Doyle, G N Greaves, M E Herron, K J Roberts, J Robinson and F C Walsh, Proceedings of the 2nd

European conference on progress in X-ray synchrotron radiation research (Eds. A Balerna, E Bernieri and S

Mobilio), Società Italiana di Fisica, Conference Proceedings 25 (1990) 497-501

118. Instrumentation and cell design for in situ studies of electrode surfaces using X-ray synchrotron radiation,

M E Herron, S E Doyle, K J Roberts, J Robinson and F C Walsh, Review of Scientific Instruments 63 (1992) 950-955

14

119. In situ studies of a dispersed platinum on carbon electrode using X-ray absorption spectroscopy, M E Herron,

F C Walsh, S E Doyle, S Pizzini, K J Roberts, J Robinson and G Hards, Journal of Electroanalytical Chemistry 324

(1992) 234-258

120. In situ X-ray diffraction studies of lead dioxide in sulphuric acid during potential cycling, M E Herron, S E Doyle,

K J Roberts, J Robinson and F C Walsh, Phase Transitions 39 (1992) 135-144

121. An in situ investigation into structural ordering on Ag surfaces during the underpotential deposition of

Pb monolayers using X-ray absorption spectroscopy under conditions of total external reflection, A Balut,

J Robinson, K J Roberts, M E Herron and F C Walsh, Japanese Journal of Applied Physics 32-2 (1993) 422-424

122. Synchrotron X-ray studies of potentiostatically formed phosphate layers on steel, S E Doyle, A H Nahle,

K J Roberts, J Robinson and F C Walsh, Transactions of the Institute of Metal Finishing 72 (1994) 63-65

123. In situ potential modulation difference diffraction studies of platinum in sulphuric acid using synchrotron X-ray

radiation, M E Herron, D Pletcher, J Robinson, S E Doyle, K J Roberts, R J Potter and F C Walsh, Journal of

Electroanalytical Chemistry 384 (1995) 39-46

124. X-ray design constraints for in-situ electrochemical cells: consideration of window materials, electrolyte and X-ray

wavelength, A H Nahle, F C Walsh, C Brennan and K J Roberts, Journal of Applied Crystallography 32 (1999)

369-372

125. Investigating the structural chemistry at the interface formed between zinc dialkyldithiophosphate (ZDDP)

and mild steel using ultra-soft X-ray absorption spectroscopy, G P Hastie, K J Roberts, D Adams, D Fischer and

G Meitzner, Japanese Journal of Applied Physics 32-2 (1993) 407-409

126. Combining X-ray absorption spectroscopy and differential scanning calorimetry: A potential technique for inter-

relating the kinetics and energetics of phase transformations in lube oils with changes to the local atomic

structure of the constituent molecular components, K J Roberts and D Adams, SERC Daresbury Laboratory

Technical Memorandum (1993) DL/SCI/TM97E

127. An investigation of the molecular stability of zinc dialkyl dithiophosphates (ZDDP) in relation to their use as anti-

wear and anti-corrosion additives in lubrication oils, D Armstrong, E Ferrari, K J Roberts and D Adams, Wear 208

(1997) 138-146

128. An examination of the reactivity of dithiophosphate (ZDDP) in relation to its use as an anti-wear and anti-

corrosion additives in lubrication oils, D Armstrong, E Ferrari, K J Roberts and D Adams, Wear 217 (1998) 276-287

129. A multi-edge X-ray absorption spectroscopy study of the reactivity of zinc di-alkyl dithiophosphate (ZDDP)

additives: 1. An examination of representative model compounds, E Ferrari, K J Roberts and D Adams, Wear 236

(1999) 246-258

130. A multi-edge X-ray absorption spectroscopy study of the reactivity of zinc di-alkyl dithiophosphate (ZDDP)

additives: 2. In-situ studies of steel oil/interfaces, E Ferrari, K J Roberts, D Adams and M Sansome, Wear 236

(1999) 259-275

131. An X-ray absorption spectroscopy examination of structural changes to zinc di-alkyl-dithiophosphate (ZDDP)

following milling in the presence of iron oxides and subsequent thermal processing, E S Ferrari, K J Roberts and

D Adams, Wear 253 (2002) 759-767.

132. Integrated materials science facility on the SRS, G Derbyshire, B Dobson, N Harris, G N Greaves, P Mackle,

P R Moore, K J Roberts, N A Allinson, J K Nicoll, S Doyle and R J Oldman, Review of Scientific Instruments 60

(1989) 1897-1900

133. Structural investigation of the amorphization reaction by mechanical alloying of the Mo50Ni50 system, G Cocco,

S Enzo, N Barrett and K J Roberts, Journal of Less-Common Metals 154 (1989) 177-186

134. X-ray analysis of changes to the atomic structure around Ni associated with the interdifffusion and mechanical

alloying of pure Ni and Mo powders, G Cocco, S Enzo, N T Barrett and K J Roberts, Physical Review B 45 (1992)

7066-7076

135. An X-ray absorption spectroscopy investigation of surface redox transformations of thallium and chromium on

colloidal mineral oxides, G Bidoglio, P N Gibson, M O’Gorman and K J Roberts, Geochim Cosmochim Acta 57

(1993) 2389-2394

15

136. Using soft X-ray absorption spectroscopy to examine the structural changes taking place around Si and Al atoms

in kaolinite following flash calcination, K J Roberts, J Robinson, T W Davies and R M Hooper, Japanese Journal of

Applied Physics 32-2 (1993) 652-654

137. Using X-ray absorption spectroscopy to probe structural change in the chemical solid- state, K J Roberts,

Molecular Crystals and Liquid Crystals 248 (1994) 207-242

138. Applications of synchrotron X-radiation to problems in material science, A R Gerson, P J Halfpenny, S Pizzini,

R Ristic, K J Roberts, D B Sheen and J N Sherwood, In “X-ray Characterisation of Materials” (Ed. E Lifshin),

Wiley-VCH Verlag (ISBN 3-527-29657-3), Weinheim (1999) 105-170

139. An in situ examination of the pyrolytic decomposition of nickel formate dihydrate using quick scanning X-ray

absorption fine structure (QXAFS) spectroscopy at the nickel K-edge, A B Edwards, C D Garner and K J Roberts,

Journal of Physical Chemistry 101 (1997) 20-26

140. A fluorescence EXAFS study of the structure of copper-rich precipitates in Fe-Cu and Fe-Cu-Ni alloys, S Pizzini,

K J Roberts, W Phythian, C English and G N Greaves, Philosophical Magazine Letters 61 (1990) 223-229

141. An investigation of the structure of copper-rich precipitates in model α-iron alloys, S Pizzini, K J Roberts,

W J Phythian and C A English, Proceedings 6th International Conference on X-ray Absorption Fine Structure

(XAFS VI), Ellis Horwood (1991) 530-532

142. The structure and hardening mechanism of copper precipitation in thermally aged or irradiated Fe-Cu and

Fe-Cu-Ni model alloys, W J Phythian, A J E Foreman, C A English, J T Buswell, M Hetherington, K J Roberts and

S Pizzini, In “Effects of Radiation on Materials: 15th Int Symp” ASTM SPP 1125 (Ed. R E Stoller, A S Kumar and

D S Gelles) American Society for the Testing and Materials, Philadelphia (1992) 131-150

143. The local atomic environment of Cu and Ni in Cu/Ni/Fe alloys following thermal ageing and neutron irradiation:

A study using fluorsecence mode X-ray absorption fine structure spectroscopy (XAFS) spectroscopy, A B Edwards,

K J Roberts and S Pizzini and W J Phythian, Philosophical Magazine A 79 (1999) 1295-1319

144. Structural characterisation of long-chain hydrocarbon thin films using ultra-soft polarised near-edge X-ray

absorption spectroscopy, G P Hastie and K J Roberts, Langmuir 11 (1995) 4170-4172

145. Examination of the structure and melting behaviour of thin film normal alkanes using ultra-soft polarised near-

edge X-ray absorption spectroscopy G P Hastie, J Johnstone, K J Roberts and D Fischer, Journal of the Chemical

Society: Faraday Transactions 92 (1996) 783-791

146. Using polarised, ultra-soft X-ray absorption spectroscopy to probe molecular orientation in benzotriazole films

adsorbed on partly oxidised copper, J Johnstone and K J Roberts, Molecular Crystals Liquid Crystals 278

(1996) 27-36

147. Investigating the orientations of Langmuir Blodgett films of copper tetra-t-butyl phthalocyanine using polarised,

ultra-soft XANES spectroscopy, J Johnstone, C A Peacock, K J Roberts, R A Hann, R J Oldman and S K Gupta,

Molecular Crystals Liquid Crystals 278 (1996) 157-164

148. Direct evidence for surface reconstruction on organic solid surfaces: Benzil 0001, G P Hastie, J Johnstone,

E M Walker and K J Roberts, Journal of the Chemical Society: Perkin Transactions 2 (1996) 2049-2050

149. Structural characterisation of condensed molecular materials using polarised NEXAFS spectroscopy, J Johnstone

and K J Roberts, Molecular Crystals Liquid Crystals 313 (1998) 39-54

150. A NEXAFS spectroscopic examination of the supramolecular organisation of a red reactive azo dye adsorbed onto

cellulose substrates, G P Hastie, J Johnstone and K J Roberts, Journal of Material Science Letters 17

(1998) 1223-1225

151. Application of polarised NEXAFS spectroscopy to the structural characterisation of condensed molecular surfaces

and interfaces, J Johnstone, C Peacock and K J Roberts, Journal of Crystal Growth 198/199 (1999) 275-281

152. Study of molecular interfaces using environmental NEXAFS spectroscopy via combined electron and fluorescence

detection, A Hennessy, C A Peacock, K J Roberts and R H Wardman, Proceedings of the 4th World Congress on

Particle Technology (WCPT4), Sydney, Australia, 21-25 July 2002, CD publication (ISBN 085 825 7947), paper 405 (8 pages).

16

Chapter 4

Experimental studies of industrial crystallisation processes related to subsequent product form together with the reactor monitoring and control through the application of advanced in-process measurement techniques

Summary: - This work describes the monitoring and resultant control of crystallisation processes via the development and use of

in-process analytical techniques.

The first group of papers [153-171], which involved the PhD studies of James Evans, Andrea Gerson, Alison Hennessy, Lesley MacCalman,

Paul Meenan, Lorna Smith, Alison Stewart, Audrey Taggart and Richard van Gelder, describes the use of optical turbidometric and

microscopy and related techniques to monitor crystallisation processes, solution solubility and metastable zone width as well as to assess

the crystal structure of the resulting crystal products.

The next group of papers describes the application of X-ray diffraction to monitor crystal phase [172-180] through work that involved

the PhD studies of Lesley MacCalman, Scott MacMillan, Paul Meenan, Ale Rossi, Lorna Smith and Richard van Gelder and which was

funded by A H Marks, Exxon Chemical, EliLilly, Unilever, BP Exploration, Cadbury and EPSRC.

The last group of papers [181-194] presents some of the output from the Chemicals Behaving Badly project sponsored by the EPSRC,

Astra Charnwood, BASF, Glaxo-Wellcome, Malvern Instruments, ICI, Pfizer, SmithKline Beecham and Zeneca and which draws together the

approaches of the first two groups of papers in this chapter with new work using UVvis and ultrasonic spectroscopy to the measurement

of particle size, ATR-FTIR spectroscopy for the measurement of solution supersaturation as well as providing some general reviews of the

process analytical domain area. The work involved the PhD works of Jessica Liang, Patricia Mougin and Heidi Grön.

153. The nucleation of n-eicosane crystals from solution in n-dodecane in the presence of homologous impurities,

K J Roberts, J N Sherwood and A Stewart, Journal of Crystal Growth 102 (1990) 419-426

154. An instrument for the examination of nucleation from solution and its application to the study of precipitation

from diesel fuels and solutions of n-alkanes, A R Gerson, K J Roberts and J N Sherwood, Powder Technology 65

(1991) 243-249

155. Phase composition and morphology of particulates crystallised within the Na2CO3-Na2SO4-H2O system,

P Meenan, K J Roberts and J N Sherwood, In “Crystal Growth - 3rd European Conference” (Ed. A Lörinczy), Trans

Tech Pub, Zurich, Crystal Properties and Preparation 36-38 (1991) 63-72

156. The influence of growth environment on the crystallisation of nortriptyline hydrochloride, a tricyclic

antidepressant, M L MacCalman, K J Roberts and B A Hendriksen, Journal of Crystal Growth 128 (1993) 1218-1224

157. An investigation of the nucleation and crystallisation kinetics of Na2SO4.10H2O and NaCO3.10H20, P Meenan

and K J Roberts, In “Industrial Crystallisation 93” (Ed. Z Rojkowski), Proceedings of the 12th Symposium on

Industrial Crystallisation, Warsaw, Poland, (1993) 5069-5074

158. The role of growth environment on the crystallisation of normal alkanes in the homologous series from C18H38

to C29H60, A R Gerson, K J Roberts, J N Sherwood, A M Taggart and G Jackson, Journal of Crystal Growth 128

(1993) 1176-1181

159. The application of an automated crystallisation cell used to study the nucleation kinetics of potash alum,

P Meenan and K J Roberts, Journal of Material Science Letters 12 (1993) 1741-1744

160. The influence of batch processing on the particulate properties of Burkeite NaCO3(Na2SO4)2, P Meenan,

K J Roberts, K R Yuregir and P C Knight, Journal of Material Science 30 (1995) 3115-3122

161. Nucleation of single and mixed straight chain surfactants from dilute aqueous solutions, R N M R van Gelder,

K J Roberts, J Chambers and T Instone, Journal of Crystal Growth 166 (1996) 189-194

162. An examination of the nucleation kinetics of n-alkanes in the homologous series C13H28 to C32H66, and their

relationship to structural type, associated with crystallisation from stagnant melts, A M Taggart, F Voogt,

G Clydesdale and K J Roberts, Langmuir 12 (1996) 5722-5728

17

163. The influence of spray drying conditions on the particle properties of re-crystallised burkeit NaCO3(Na2SO4)2,

P Meenan, K J Roberts, K Yurrigar and P Knight, Powder Technology 90 (1997) 125-130

164. An examination of additive-mediated wax nucleation in oil pipeline environments, A Hennessy, A Neville and

K J Roberts, Journal of Crystal Growth 198/199 (1999) 830-837

165. In-situ observation of the crystallisation of sodium dodecylsulfate, L. A Smith, A Duncan, K J Roberts,

G B Thomson, D. Machin and G. McLeod, Proceedings of the 5th International Workshop on the Crystal Growth of

Organic Materials (CGOM-5), Cambridge, IChemE, ISBN 0 85295 4247, paper number 203 (1999) 10 pages

166. Sodium hydrogen bis(phenoxyacetate), J Evans, A Kapitan, G Rosair, K.J.Roberts and G White,

Acta Crystallographica C: Crystal Structure Communications 57 (2001) 250-251

167. Hemi-hydrate sodium phenoxyacetate, J Evans, A Kapitan, G Rosair, K.J.Roberts and G White,

Acta Crystallographica C: Crystal Structure Communications 57 (2001) 1277-1278

168. Online measurement of solids distribution in stirred tanks and crystallizers using electrical computed tomography,

R A Williams, X Jia, R M West and K J Roberts, In mixing and crystallisation (edited B S Gupta and S Ibrahim),

Kluwar Academic publishers, Dordrecht/Boston/London (2000) pp113-123

169. An examination of the solution phase and nucleation properties of sodium, potassium and rubidium dodecyl

sulphates, L A Smith, K J Roberts, D Machin and G McLeod, Journal of Crystal Growth 226 (2001) 158-167

170. Application of solid-state NMR for the determination of filter cake moisture contents associated with the filter/

drying of organic mother liquor slurries, A Geddes, K J Roberts, A Brough and D O Morgan, Proceedings of the 4th

World Congress on Particle Technology (WCPT4), Sydney, Australia, 21-25 July 2002, CD publication

(ISBN 085 825 7947), paper 409 (8 pages)

171. Structuro-kinetic studies on additive mediated wax crystallisation from organic solvent, A Hennessy, K J Roberts

and A Neville, Proceedings of the 4th World Congress on Particle Technology (WCPT4), Sydney, Australia,

21-25 July 2002, CD publication (ISBN 085 825 7947), paper 321 (11 pages)

172. Synchrotron energy dispersive powder diffraction, P Barnes, S M Clark, S E Tarling, E Polack, D Hauserman,

C Brennan, S Doyle, K J Roberts, J N Sherwood and R J Cernik, SERC Daresbury Laboratory Technical Memorandum

(1987) DL/SCI/TM55E

173. Application of synchrotron radiation energy dispersive diffraction to the in situ observation of wax crystallisation

from solution, S Doyle, K J Roberts and J N Sherwood, S M Clark and D Hauserman, Journal of Crystal Growth 88

(1988) 306-310

174. Novel kinetic and structural studies of wax crystallisation, A Gerson, J N Sherwood, K J Roberts and D Hauserman,

Journal of Crystal Growth 99 (1990) 145-149

175. Probing the structure of solids in a liquid environment: A recent in situ crystallisation experiment using high

energy wavelength scanning X-ray diffraction, S E Doyle, A R Gerson, K J Roberts, J N Sherwood and T Wroblewski,

Journal of Crystal Growth 112 (1991) 302-307

176. On-line processing of pharmaceutical materials using in-situ X-ray diffraction, M L MacCalman, K J Roberts, C

Kerr and B Hendriksen, Journal of Applied Crystallography 28 (1995) 620-623

177. Using synchrotron radiation diffraction for the online monitoring and control of industrial crystallisation

reactions, M L MacCalman K J Roberts and B Hendriksen, Proceedings of the 5th World Congress of Chemical

Engineering (1996) 698-703

178. Crystallisation and polymorphism of cocoa butter fat: in situ studies using synchrotron radiation X-ray diffraction,

R N M R van Gelder, N Hodgson, K J Roberts, A Rossi, M Wells, M Polgreen, and I Smith, proceedings of the Third

International Workshop on the Crystal Growth of Organic Materials, Washington DC, USA, ACS conference

proceedings series (Eds. A S Myerson, D A Green and P Meenan) (1996) 209-215

179. In-situ small angle X-ray scattering (SAXS) studies of polymorphism with the associated crystallisation of cocoa

butter fat using shearing conditions, S D MacMillan, K J Roberts, A Rossi, M A Wells, M C Polgreen and I H Smith,

Crystal Growth and Design 2 (2002) 221-226

180. Identification of the initial nucleating form involved in the thermal processing of cocoa butter fat

as examined using wide-angle x-ray scattering (WAXS), S. D. MacMillan, K. J. Roberts, M. A. Wells, M. C. Polgreen

and I. H. Smith, Crystal Growth and Design 3 (2003) 117-119

18

181. A new on-line batch process engineering facility for examining the crystallisation of organic speciality chemical

products, H Groen, R B Hammond, X Lai, P Mougin, K J Roberts, N Savelli, A Thomas, G White, H L Williams,

D Wilkinson, M Baker, D Dale, P Erk, D Latham, D Merrifield, R Oliver, D Roberts, W Wood and L Ford, In Pilot

plants and Scale-Up II (edited W Hoyle), Special Publication 236, Royal Society of Chemistry, 1999, 40-62

182. On-line analytical techniques for monitoring the crystallisation processes of organic speciality chemicals,

M Baker, Z Cao,D Dale, P Erk, L J Ford, H C Groen, D Latham, R B Hammond, X Lai, K Liang, D Merrifield, P Mougin,

R Oliver, D Roberts, K J Roberts, N Savelli, A Thomas, G White, D Wilkinson and W Wood, Molecular Crystals Liquid

Crystals 356 (2001) 273-287

183. An examination of the batch crystallisation behaviour of citric acid as monitored in-situ by ATR-FTIR

spectroscopy, H C Gron and K J Roberts, Journal of Physical Chemistry 105 (2001) 10723-10730

184. In process particle characterisation by spectral extinction, S Gordon, R B Hammond, K J Roberts, N Savelli and D

Wilkinson, Chemical Engineering Research and Design 78 (2000) 1147-1152

185. Characterisation of particle size and its distribution during the crystallisation of organic fine chemical products

as measured in-situ using ultrasonic attenuation spectroscopy, P. Mougin, K.J.Roberts, D Wilkinson and R Tweedie,

Journal of the Acoustic Society of America 109 (2001) 274-282

186. In-situ measurement of particle size during the crystallisation of (L) glutamic acid under two polymorphic forms:

Influence of crystal habit on ultrasonic attenuation measurements, P Mougin, D Wilkinson and K J Roberts, Crystal

Growth and Design 2 (2002) 227-234

187. Application of process analytical techniques to monitoring the crystallisation of organic fine chemical products,

K.J.Roberts, Chemical Engineering Transactions 1 (2002) 773-778.

188. In process ATR-FTIR spectroscopy for closed-loop supersaturation control of a batch crystalliser producing

monosodium glutamate crystals of defined size, H Groen, A Borissova and K J Roberts, Industrial Engineering

Chemistry Research 42 (2003) 198-206

189. An examination of the effect of reactor hydrodynamics and scale on the nucleation of batch crystallised

L-glutamic acid from aqueous solution, K. Liang, D Wilkinson, G White, K J Roberts, L J Ford and W Wood,

Chemical Engineering Transactions 1 (2002) 497-502.

190. The influence of reactor hydrodynamics and scale on nucleation during the batch cooling crystallisation of L-

glutamic acid from aqueous solution, K Liang, D Wilkinson, G White, K J Roberts, L J Ford and W Wood,

Proceedings of the 4th World Congress on Particle Technology (WCPT4), Sydney, Australia, 21-25 July 2002, CD

publication (ISBN 085 825 7947), paper 332 (8 pages).

191. In-situ ultrasonic spectroscopic study of the dynamic evolution of particle size during solution phase

crystallisation of urea, P Mougin, D Wilkinson and K J Roberts, Crystal Growth and Design 3 (2003) 67-72

192. On-line monitoring of a crystallisation process, P Mougin, A Thomas, D Wilkinson, G White, K J Roberts,

N Herrmann, R Jack and R Tweedie, AIChemE Journal 49 (2003) 373-378

193. Sensitivity to particle sizing by ultrasonic spectroscopy to materials properties, P Mougin, D Wilkinson and

K J Roberts, Powder Technology 134 (2003) 243-248

194. Dynamic in-process examination of particle size and crystallographic form under defined conditions of reactant

supersaturation as associated with the batch crystallisation of monosodium glutamate from aqueous solution,

H Groen, P Mougin, A Thomas, G White, D Wilkinson, R B Hammond, X Lai and K J Roberts, Industrial Engineering

Chemistry Research 42 (2003) 4888-4898

19

Chapter 5

Determination of the crystal structures of some industrial organic compounds through the use of high resolution X-ray powder diffraction, molecular and solid state modelling, and associated analytical techniques

Summary: - This work describes the use of high resolution X-ray diffraction (often using synchrotron radiation), molecular and

solid-state modelling and other complementary techniques such as FTIR, differential scanning calorimetry and solid-state NMR to

probe the crystallographic structures of industrial materials which are not readily amenable to examination by conventional single

crystal techniques.

The first batch of papers [195-205] focuses mainly upon normal alkanes and mixtures of close homologous associated with the PhD

work of Andrea Gerson and Steven Craig and the MPhil work of Gerry Hastie.

The second set of papers [206-209], associated with the PhD work of Paul Fagan funded by Zeneca Specialities, draws down on this base

linking it to molecular modelling to solve crystal structures.

The final set of papers [210-220] links this work to the molecular modelling approaches developed via the HABIT programme described

in Chapter 2 resulting in the development of a new integrated method for structure solution from powders. This work has involved

the PhD work of Lorna Smith, Elaine Smith and Sarah Murphy as part of a substantial collaboration with Robert Hammond at Leeds,

which has also involved additional collaborative work with Professor Robin Harris at the University of Durham, Sally Price at University

College London and Helmut Klapper at the University of Bonn in Germany. Funding for this work was provided by EPSRC, AstraZeneca,

GlaxoSmithKline, Pfizer, Sanofi and Unilever.

195. High resolution powder diffraction using synchrotron radiation: Application to the structural investigation of

n-alkanes and their homologues mixtures, A R Gerson, K J Roberts, J N Sherwood, R Cernik, P Pattison and A Fitch,

In “Synchrotron Light: Applications and Related Instrumentation II”, World Scientific Press, (1990) 210-229

196. X-ray powder diffraction studies of alkanes: Unit cell parameters of the homologous series C18H38 to C28H58,

A R Gerson, K J Roberts and J N Sherwood, Acta Crystallographica B47 (1991) 280-284

197. X-ray diffraction studies of single and mixed n-alkanes in the homologous series C18H38 to C28H58, A R Gerson,

K J Roberts and J N Sherwood, In “Particle Design via Crystallisation” (Eds. R Ramanarayanan, W Kern, M Larson

and S Sikdar), American Institution of Chemical Engineers Symposium Series 284 87 (1991) 138-142

198. X-ray Powder diffraction Studies of n-alkanes: a re-examination of the unit-cell parameters of C26H54,

A R Gerson, K J Roberts and J N Sherwood, Acta Crystallographica B48 (1992) 746

199. Using in situ synchrotron radiation powder diffraction to characterise growth-related structural polymorphic

phase transformations in cis-9-ω-octadecenoic acid, S R Craig, K J Roberts, J N Sherwood, K Sato, Y Hayashi,

M Iwahashi and R J Cernik, Journal of Crystal Growth 128 (1993) 1263-1267

200. An investigation into the inter- and intra-molecular packing in the solid state for crystals of the normal alkanes

and homologous mixtures using FTIR spectroscopy, G P Hastie and K J Roberts, Journal of Material Science 29

(1994) 1915-1919

201. Investigation into the structures of some normal alkanes within the homologous series C13H28 to C60H122 using high

resolution synchrotron X-ray powder diffraction, S R Craig, G P Hastie, K J Roberts and J N Sherwood, Journal of

Materials Chemistry 4 (1994) 977-982

202. A near-ambient-temperature-control cell for use with synchrotron X-ray powder diffraction, R J Cernik, S R Craig,

K J Roberts and J N Sherwood, Journal of Applied Crystallography 28 (1995) 651-653

203. Chain length dependent polymorphism in even number n-alkanes: line profile analysis of synchrotron radiation

powder X-ray diffraction data, S R Craig, G P Hastie and K J Roberts, Journal of Material Science Letters 15 (1996)

1193-1196

20

204. Investigation into the structures of binary-, ternary-, and quinternary mixtures of n-alkanes and real diesel waxes

using high resolution synchrotron X-ray powder diffraction, S R Craig, G P Hastie, A R Gerson, K J Roberts,

J N Sherwood and R D Tack, Journal of Materials Chemistry 8 (1997) 859-869

205. In-situ study of the solid-solid phase transitions occurring in real diesel wax crystalline systems using differential

scanning calorimetry and high-resolution synchrotron X-ray powder diffraction, S R Craig, G P Hastie, K J Roberts,

J N Sherwood, R D Tack and R J Cernik, Journal of Materials Chemistry 9 (1999) 2385-2392

206. The crystallisation of highly perfect metal-free phthalocyanine powders for ab initio structure solution by

diffraction methods, P G Fagan, K J Roberts and R Docherty, Journal of Crystal Growth 128 (1993) 1257-1262

207. The crystal structure of triphendioxazine as solved by a new ab initio technique utilising high resolution powder

diffraction and computational chemistry techniques, P G Fagan, K J Roberts, R Docherty, A P Chorlton, W Jones

and G D Potts, Molecular Crystals and Liquid Crystals 248 (1994) 277-289

208. An ab initio approach to crystal structure determination using high resolution powder diffraction and

computational chemistry techniques: Application to 6,13-dichlorotriphendioxazine, P G Fagan, K J Roberts,

R Docherty, A P Chorlton, W Jones and G D Potts, Chemistry of Materials 7 (1995) 2322-2326

209. An ab initio approach to crystal structure determination using high resolution powder diffraction and

computational chemistry techniques, P G Fagan, R B Hammond, K J Roberts, R Docherty and M Edmondson,

proceedings of the Third International Workshop on the Crystal Growth of Organic Materials, Washington DC,

USA, ACS conference proceedings series (Eds. A S Myerson, D A Green and P Meenan) (1996) 22-27

210. X-form metal free phthalocyanine: Crystal structure determination using a combination of high resolution X-ray

diffraction and molecular modelling techniques, R B Hammond, K J Roberts, R Docherty, M Edmondson and

R Gairns, Journal of the Chemical Society: Perkin Transactions 2 (1996) 1527-1528

211. Crystal structure determination from powder X-ray data using a systematic molecular packing search algorithm,

R B Hammond, K J Roberts, R Docherty and M Edmonstone, Proceedings of the Fourth International Workshop on

the Crystal Growth of Organic Materials (CGOM-4), Bremen, Germany (edited J Ulrich), Shaker Verlag, Aachen,

Germany (1997), 53-60

212. Computationally assisted structure determination for molecular materials from X-ray powder diffraction data,

R B Hammond, K J Roberts, R Docherty and M Edmondson, Journal of Physical Chemistry 101 (1997) 6532-6536

213. Application of a computational systematic search strategy to study polymorphism in phenazine and perylene,

R B Hammond, K J Roberts, E D L Smith and R Docherty, Journal of Physical Chemistry B 103 (1999) 7762-7770

214. The meta-stable β-Phase of benzophenone as independently determined via two different methodologies: powder

diffraction and single crystal X-ray studies, H Kutzke, H Klapper, R B Hammond, K J Roberts,

Acta Crystallographica B 56 (2000) 486-496

215. Determination of the crystal structure of anhydrous sodium dodecyl sulphate using a combination of synchrotron

radiation powder diffraction and molecular modelling techniques, L. A Smith, R B Hammond, K J Roberts,

D. Machin and G. McLeod, Journal of Molecular Structure 554 (2000) 173-184

216. Determining the crystal structures of organic molecular materials using X-ray powder diffraction together with molecular and

solid-state modelling techniques, R B Hammond, M J Jones, S Murphy, K J Roberts, E. D L. Smith, H Klapper, H Kutzke,

R Docherty, J Cherryman, R Roberts and P G Fagan, Molecular Crystals Liquid Crystals 356 (2001) 389-406

217. The determination of the crystal structure of anhydrous theophylline by X-ray powder diffraction with a

systematic search algorithm, lattice energy calculations and 13C and 15N solid-state NMR: a question of

polymorphism in a given unit cell, E D. L. Smith, R B. Hammond, M J. Jones, K J. Roberts, J B. O. Mitchell, S L. Price,

J Cherryman and R K Harris, Journal of Physical Chemistry B 105 (2001) 5818-5826

218. Evaluation of a systematic search strategy for complex asymmetric units through application to the co-crystal

catechol/urea, R B Hammond, C Ma and K J Roberts, Chemical Engineering Transactions 1 (2002) 773-778.

219. A structural study of polymorphism in phenyl salicylate: determination of a metastable phase from powder X-ray diffraction

data, R B Hammond, M J Jones, K J Roberts, H Kutzke and H Klapper, Zeitschrift fur Kristalloagraphie 217 (2002) 484-491

220. Application of systematic search methods to studies of the structures of urea - dihydroxy benzene cocrystals,

R B Hammond, C Ma, K J Roberts, P Y. Ghi, R K. Harris, Journal of Physical Chemistry (2003), 107, 11820-11826.

21

Postscript:

Graduation Day, Monday 1st November 2004.

Professor Kevin J Roberts with Principal and Vice Chancellor Professor Andrew Hamnett prior to the graduation ceremony at the Barony

Hall at the University of Strathclyde (above); Professor Roberts with Emeritus Professor John N Sherwood and Professor Richard A

Pethrick from the Department of Pure and Applied Chemistry at the post-graduation reception (below).

22

23

Published by Strathclyde University Press,University of Strathclyde, Glasgow, United Kingdom.

ISBN 0 947649 14 X