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ASSESSMENT OF THE ADHESION OF POWDERS TO A METAL SURFACE by KWOK KAI LAM Thesis submitted for the degree of DOCTOR OF PHILOSOPHY in the Faculty of Medicine of the UNIVERSITY OF LONDON Department of Pharmaceutics, The School of Pharmacy, University of London, 29-39 Brunswick Square, London WC1N 1AX. November, 1991. 1 ProQuest Number: U055663 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest U055663 Published by ProQuest LLC(2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ABSTRACT A centrifuge method has been employed to study, statistically, the adhesion of individual particles of some pharmaceutical powder excipients to stainless steel. The surface of the steel substrate was characterized by profilometry, which was defined by the various surface roughness parameters. By altering the relative position of the steel disk in a specially designed rotor tube, the centrifugal force can act both as a compression force as well as a detachment force. Preliminary pressing of powder particles on to the steel surface was found to increase the strength of particle adhesion. The relative adhesiveness of different solid excipient materials was compared quantitatively by means of the adhesion ratio derived in this study, which allows a more objective means of assessment. In general, adhesion to stainless steel was stronger for soft materials than hard ones, on the basis that plastic deformation has occurred. Moreover, the strengths of adhesion bonds were appreciably affected by the duration that the adhering particles were initially under a compression force before separation. Particulate materials having an inherent weak solid structure was particularly sensitive to such effect. Variation of particle adhesion forces to stainless steel was shown to be due partly to the non-uniformity of particle size in a powder sieve fraction. Though bigger particles exhibited greater forces of adhesion, due to their larger masses, they were more easily dislodged than the smaller particles by centrifugation. Investigations into two powder-steel adhesive systems indicated a considerable role played by the molecular van der Waals forces in the particle adhesion. Adhesive interactions were examined in terms of surface energetics, from which an apparent energy of adhesion was calculated for either system, which may provide an alternative means of evaluating particles-substrate adhesion. 2 A form of Arrhenius relationship was found between temperature and the median adhesion force or the amount of median adhesion force established per unit of the preliminary press-on force, from which the apparent activation energy for an adhesion process was obtained. With less energy of activation was required for a soft material, as found, an implication of this is that, adhesion bond formation would be energetically more favourable for a soft solid. 3 For my parents For my brothers and sister 4 CONTENTS Page Title P a g e................................................................................................................. 1 A bstract................................................................................................................... 2 List of Figures...................................................................................................... 10 List of T ab les...................................................................................................... 14 List of Plates........................................................................................................ 16 List of Symbols .................................................................................................... 17 Acknowledgements .............................................................................................. 21 CHAPTER 1: GENERAL INTRODUCTION ................................................... 22 1.1 Concepts of Adhesion ............................................................................... 23 1.2 Adhesion and Fracture Mechanics ............................................................ 24 1.3 Adhesion and Tribology ............................................................................ 25 1.4 Deformation of M aterials .......................................................................... 27 1.4.1 Elastic Deformation ........................................................................ 27 1.4.2 Plastic Deformation ........................................................................ 28 1.5 True Contact A rea ..................................................................................... 32 1.5.1 Measurement of Real Area of Contact ......................................... 35 1.6 Mechanisms of A dhesion .......................................................................... 37 1.6.1 Contact Interaction Forces ............................................................ 37 1.6.1.1 Molecular van der Waals Forces ................................. 38 1.6.1.2 Electrical Forces of Adhesion ...................................... 48 1.6.1.3 Capillary Forces ............................................................. 50 1.6.2 Relative Contributions of the Different Components of Adhesive F o rces............................................................................................ 52 1.6.3 Other Reactions at the Particle-Substrate Interface ..................... 54 1.7 Influence of Solid Surface Condition on Adhesion................................... 55 5 Page 1.8 Kinetics of Particle-Substrate Adhesion ................................................... 56 1.8.1 Hertz’s Theory of Elastic C ontact ............................................... 57 1.8.2 Particle Roughness on an Elastic Contact ................................... 59 1.9 Kinetics of Particle Detachment from a Plane Surface ............................. 62 1.9.1 The Thermodynamic Force and Energy Approaches ................ 62 1.9.2 The Contact Mechanics Approach .............................................. 66 1.9.3 Field of Applicability of the JKR and DMT M odels ................ 68 1.10 Measurement of Particle-Substrate Adhesion ............................................ 72 1.10.1 Experimental Methods for Measuring Adhesion Fo rc es 72 1.10.1.1 The Aerodynamic and HydrodynamicTechniques . 74 1.10.1.2 The Weighing Technique ........................................... 75 1.10.1.3 The Pendulum Technique ........................................... 77 1.10.1.4 The Inclined Plane Technique .................................... 77 1.10.1.5 The Centrifuge Technique ........................................... 78 1.10.1.6 Some other Specific Techniques ................................. 79 1.10.2 Merits of the Centrifuge Technique ............................................ 80 1.11 Objectives of this W o rk............................................................................ 83 CHAPTER 2: PREPARATION AND CHARACTERIZATION OF EXPERIMENTAL MATERIALS...................................... 84 2.1 Characterization of Powder Materials ....................................................... 85 2.1.1 Choice of Powder M aterials ........................................................ 85 2.1.2 Description and Pharmaceutical Usages of the Pow ders 85 2.1.3 Sources of Materials ................................................................... 86 2.1.4 Size Separation of the Powders ................................................... 86 2.1.5 Apparent Particle Densities .......................................................... 88 2.1.6 Single Particle Mass Determination ............................................ 88 2.1.7 Particle Microscopical Morphology............................................ 91 2.1.8 Storage of Materials ................................................................... 91 2.2 Surface Characterization of the Substrate M aterial .................................. 95 2.2.1 Substrate M aterial ........................................................................ 95 6 Page 2.2.2 Surface Topography Analysis of the Stainless Steel Disks .... 95 2.2.2.1 Introduction .................................................................... 95 2.2.2.2 Experimental ................................................................. 99 2.2.2.3 Results and Discussion .................................................. 99 2.2.3 Surface Texture Parameters ....................................................... 102 2.2.3.1 Introduction ............................................................... 102 2.2.3.2 Results and Discussion ............................................... 105 2.2.4 Conclusions ................................................................................ 105 CHAPTER 3: TECHNIQUE FOR MEASUREMENT OF ADHESIVE FORCES BETWEEN PARTICLES AND A SUBSTRATE SURFACE ...................................................... 107 3.1 Determination of Particle-Substrate Adhesion Forces ............................. 108 3.1.1 Introduction ...............................................................................