tailoring surfaces : modifying surface composition and ... · msc centenary lecture series...

MSc Centenary Lecture Series

Tailoring SurfacesModifying Surface Composition and Structure for

Applications in Tribology, Biology and Catalysis

Nicholas D SpencerETH Zurich, Switzerland

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NEW JERSEY • LONDON • SINGAPORE BEIJING • SHANGHAI • HONG KONG TAIPEI • CHENNAI

xiii

Contents

Preface vii

Biography of Professor Nicholas D. Spencer ix

Acknowledgments xi

1. Introduction 1

la. Self-assembled monolayers 2

lb. Functionalizing surfaces with polymer brushes 5

lc. Using additives to modify surfaces in a self-repairing way 9

Id. Structure: a new dimension to surface tailoring 10

le. Spatial distributions on surfaces: from patterns to gradients 13

2. Chemical Modification of Surfaces 17

2a. Self-assembled monolayers: new approaches 17

Commentary

2.1. Self-Assembled Hexasaccharides: Surface Characterization of 19

Thiol-Terminated Sugars Adsorbed on a Gold Surface

M.C Fritz, G. Hahner, N.D. Spencer, R. Burli, A. Vasella

Langmuir, 1996; 12(25) pp 6074-6082

2.2. Highly Oriented, Self-Assembled Alkanephosphate Monolayers on Tantalum 28

(V) Oxide Surfaces

D. Brovelli, G. Hahner, L. Ruiz, R. Hofer, G. Kraus, A. Waldner,J. Schlosser, P. Oroszlan, M. Ehrat, N.D. Spencer

Langmuir, 1999; 15(13) pp 4324-4327

xiv Tailoring Surfaces

2.3. Structural Chemistry of Self-Assembled Monolayers of Octadecylphosphoric 32

Acid on Tantalum Oxide Surfaces

M. Textor, L. Ruiz, R. Hofer, A. Rossi, K. Feldman, G. Hahner, N.D. SpencerLangmuir, 2000; 16(7) pp 3257-3271

2.4. Alkyl Phosphate Monolayers, Self-Assembled from Aqueous Solution onto 47

Metal Oxide Surfaces

R. Hofer, M. Textor, N.D. Spencer,Langmuir, 2001; 17(13) pp 4014-4020

2.5. Self-Assembled Monolayers of Dodecyl and Hydroxy-Dodecyl Phosphates on 54

Both Smooth and Rough Titanium and Titanium Oxide Surfaces

S. Tosatti, R. Michel, M. Textor, N.D. Spencer

Langmuir, 2002; 18(9) pp 3537-3548

2.6. Influence of Alkyl Chain Length on Phosphate Self-Assembled Monolayers 66

Doris M. Spori, Nagaiyanallur V. Venkataraman, Samuele G. P. Tosatti,Firat Durmaz, Nicholas D. Spencer, Stefan Zurcher

Langmuir, 2007; 23(15) pp 8053-8060

2.7. Macroscopic Tribological Testing of Alkanethiol Self-Assembled Monolayers 74

(SAMs): Pin-on-Disk Tribometry with Elastomeric Sliding Contacts

Seunghwan Lee, Raphael Heeb, Nagaiyanallur V. Venkataraman,Nicholas D. Spencer

Tribology Letters; 2007; 28(3) pp 229-239

2.8. Fabricating Chemical Gradients on Oxide Surfaces by Means of Fluorinated, 85

Catechol-Based, Self-Assembled MonolayersMathias Rodenstein, Stefan Zurcher, Samuele G.P. Tosatti, Nicholas D. SpencerLangmuir, 2010; 26(21) pp 16211-16220

2b. Surfaces functionalized with polymer brushes for lubrication 95

Commentary

2.9. Boundary Lubrication of Oxide Surfaces by Poly(L-lysine)-g-Poly(Ethylene 97

Glycol) (PLL-g-PEG) in Aqueous Media

Seunghwan Lee, Markus Miiller, Monica Ratoi-Salagean, Janos Voros,Stephanie Pasche, Susan M. De Paul, Hugh A. Spikes, Marcus Textor,Nicholas D. Spencer


2.10. The Influence of Molecular Architecture on the Macroscopic Lubrication 106

Properties of the Brush-like Co-Polyelectrolyte Poly(L-Lysine)-g-Poly (EthyleneGlycol) (PLL-g-PEG) Adsorbed on Oxide Surfaces

M. Miiller, S. Lee, H.A. Spikes, N.D. Spencer


Contents xv

2.11. Lubrication Properties of a Brush-Like Copolymer as a Function of the 117

Amount of Solvent Absorbed Within the Brush

M. Miiller, X. Yan, S. Lee, S. Perry, N.D. Spencer

Macromolecules; 2005; 38(13) pp 5706-5713

2.12. Aqueous Lubrication of Polymers: Influence of Surface Modification 125S. Lee, N.D. Spencer

Tribology International; 2005; 38, pp 922-930

2.13. Self-Healing Behavior of a Polyelectrolyte-Based Lubricant Additive for 134

Aqueous Lubrication of Oxide Materials

Seunghwan Lee, Markus Miiller, Raphael Heeb, Stefan Ziircher,Samuele Tosatti, Michael Heinrich, Fabian Amstad, Sebastian Pechmann,Nicholas D. Spencer


2.14. Poly(L-lysine)-g-Poly(Ethylene Glycol) (PLL-g-PEG): A Versatile Aqueous 141

Lubricant Additive for Tribosystems Involving ThermoplasticsSeunghwan Lee, Nicholas D. SpencerLubrication Science; 2008; 20 pp 21-34

2.15. Sweet, Hairy, Soft, and Slippery 155

Seunghwan Lee, Nicholas D. Spencer

Science; 2008; 319 pp 575-576

2.16. Nanotribology of Surface-Grafted PEG Layers in an Aqueous Environment 157

Tanja Drobek, Nicholas D. Spencer

Langmuir, 2008 24(4) pp 1484-1488

2.17. End-grafted Sugar Chains as Aqueous Lubricant Additives: 162

Synthesis and Macrotribological Tests of Poly(L-Lysine)-graft-Dextran(PLL-g-dex) CopolymersChiara Perrino, Seunghwan Lee, Nicholas D. Spencer


2.18. Aqueous Lubrication of SiC and SisN4 Ceramics, Aided by a Brush-Like 176

Copolymer Additive, Poly(L-lysine)-g-Poly(Ethylene Glycol) (PLL-g-PEG)Whitney Hartung, Antonella Rossi, Seunghwan Lee, Nicholas D. Spencer


2.19. Room-Temperature, Aqueous-Phase Fabrication of Poly(Methacrylic acid) 186

Brushes by UV-LED-Induced, Controlled Radical Polymerization with High

Selectivity for Surface-bound Species

Raphael Heeb, Robert M. Bielecki, Seunghwan Lee, Nicholas D. SpencerMacromolecules; 2009; 42(22) pp 9124-9132

xvi Tailoring Surfaces

2.20 Macrotribological Studies of Poly(L-lysine)~graft-Poly(Ethylene Glycol) in 195

Aqueous Glycerol Mixtures

Prathima C Nalam, Jarred N Clasohm, Alireza Mashaghi, Nicholas D. Spencer


2.21. Tribological Properties of Poly(L-lysine)-g-Poly(Ethylene Glycol) films: 207

Influence of Polymer Architecture and Adsorbed Conformation

Scott S. Perry, X. Yan, F. T. Limpoco, Markus Muller, Seunghwan Lee,Nicholas D. Spencer

ACS Applied Materials and Interfaces; 2009; 1(6) pp 1224-1230

2c. Surface modification with biomolecules and its control 214

Commentary

2.22. Covalent Attachment of Cell-Adhesive, (Arg-Gly-Asp)-Containing Peptides 215

to Titanium Surfaces

S.J. Xiao, M. Textor, N.D. Spencer, H. Sigrist

Langmuir, 1998; 14(19) pp 5507-5516

2.23. Microstructured Bioreactive Surfaces: Covalent Immobilization of Proteins 225

on Au(lll)/Silicon via Aminoreactive Alkanethiolate Self-Assembled MonolayersF. G. Zaugg, P. Wagner, P. Kernen, A. Vinckier, P. Groscurth, N.D. Spencer,G. Semenza

J. Mater. Sci: Mater, in Med.; 1999; 10(5) pp 255-263

2.24. Poly(L-lysine)-g-Poly(Ethylene Glycol) Layers on Metal Oxide Surfaces: 234

Attachment Mechanism and Effects of Polymer Architecture on Resistance to

Protein AdsorptionG.L. Kenausis, J. Voros, D.L. Elbert, N.P. Huang, R. Hofer, L. Ruiz,M. Textor, J.A. Hubbell, N.D. SpencerJ. Phys. Chem. B; 2000; 104(14) pp 3298-3309

2.25. Poly(L-lysine)-g-Poly(Ethylene Glycol) Layers on Metal Oxide Surfaces: 246

Surface Analytical Characterization and Resistance to Serum and

Fibrinogen AdsorptionN.P. Huang, R. Michel, J. Voros, M. Textor, R. Hofer, A. Rossi, D.L. Elbert,J.A. Hubbell, N.D. Spencer

Langmuir, 2001; 17(2) pp 489-498

2.26. Biotin-Derivatized Poly(L-lysine)-g-Poly(Ethylene Glycol): A Novel 256

Polymeric Interface for Bioaffinity SensingN.P. Huang, J. Voros, S.M. De Paul, M. Textor, N.D. SpencerLangmuir, 2002; 18(1) pp 220-230

Contents xvii

2.27. Poly(L-lysine)-g-Poly(Ethylene Glycol) Assembled Monolayers on Niobium 267

Oxide Surfaces: a Quantitative Study of the Influence of Polymer Interfacial

Architecture on Resistance to Protein Adsorption by ToF-SIMS and in situ OWLS

S. Pasche, S. M. De Paul, J. Voros, N. D. Spencer, M. Textor

Langmuir, 2003; 19(22) pp 9216-9225

2.28. Interaction Forces and Morphology of a Protein-Resistant Poly(ethylene 277

glycol) Layer

M. Heuberger, T. Drobek, N.D. SpencerBiophysical Journal; 2005; 88 pp 495-504

2.29. Relationship Between Interfacial Forces Measured by Colloid-Probe Atomic 287

Force Microscopy and Protein Resistance of Poly(L-lysine)-g-Poly(EthyleneGlycol) Co-PolymersS. Pasche, L. Meagher, N.D. Spencer, M. Textor, H.J. Griesser

Langmuir; 2005; 21, pp 6508-6520

2.30. Effects of Ionic Strength and Surface Charge on Protein Adsorption at 300

PEGylated Surfaces

S. Pasche, J. Voros, H. J. Griesser, N. D. Spencer, M. Textor

J. Phys. Chem B; 2005; 109(37) pp 17545-17552

2.31. Nitrilotriacetic Acid Functionalized Graft Copolymers: A Polymeric 308

Interface for Selective and Reversible Binding of Histidine-Tagged Proteins

G. Zhen, D. Falconnet, E. Kuennemann, J. Voros, N. D. Spencer,M. Textor, S. Ziircher

Adv. Func. Materials; 2006; 16(2), pp 243-251

2.32. A Biomimetic Alternative to PEG as an Antifouling Coating: Resistance to 317

Non-Specific Protein Adsorption of Poly(L-Lysine)-Graft-DextranChiara Perrino, Seunghwan Lee, Sung Won Choi, Atsushi Maruyama,Nicholas D. Spencer

Langmuir, 2008; 24 pp 8850-8856

2d. Lubricant additives as surface modifiers 324

Commentary

2.33. Growth of Tribological Films: in situ Characterization Based on 325

Attenuated Total Reflection Infrared SpectroscopyF.M. Piras, A. Rossi, N.D. Spencer

Langmuir, 2002; 18(17) pp 6606-6613

2.34. A Combinatorial Approach to Elucidating Tribochemical Mechanisms 333

Michael Eglin, Antonella Rossi, Nicholas D. Spencer


xviii Tailoring Surfaces

2.35. X-Ray Photoelectron Spectroscopy Analysis of Tribostressed Samples in the 339

Presence of ZnDTP: A Combinatorial Approach

Michael Eglin, Antonella Rossi, Nicholas D. Spencer


2.36. Combined in situ (ATR FT-IR) and ex situ (XPS) Study of the 350ZnDTP-Iron Surface Interaction

F. Piras, A. Rossi, Nicholas D. Spencer


2.37. Surface Analytical Studies of Surface-Additive Interactions, by Means of 361

in situ and Combinatorial ApproachesA. Rossi, M. Eglin, P.M. Piras, K. Matsumoto, N.D. SpencerWear, 2004; 256(6) pp 578-584

2.38. Pressure Dependence of ZnDTP Tribochemical Film Formation: A 368

Combinatorial ApproachRoman Heuberger, Antonella Rossi, Nicholas D. Spencer

Tribology Letters; 2007; 28(2) 209

2.39. Reactivity of Triphenyl Phosphorothionate in Lubricant Oil Solution 382

Filippo Mangolini, Antonella Rossi, Nicholas D. Spencer


2e. Surface Modification for Lubrication of implants 395

Commentary

2.40. Protein-Mediated Boundary Lubrication in Arthroplasty 396

M. Heuberger, M. R. Widmer, E. Zobeley, R. Glockshuber, N.D. Spencer

Biomaterials; 2005; 26 pp 1165-1173

2.41. The Adsorption and Lubrication Behavior of Synovial Fluid Proteins and 405

Glycoproteins on the Bearing Surface Materials of Hip ReplacementsMarcella Roba, Marco Naka, Emanuel Gautier, Nicholas D. Spencer,Rowena Crockett


2.42. Friction, Lubrication, and Polymer Transfer Between UHMWPE and 412

CoCrMo Hip-Implant Materials: A Fluorescence Microscopy StudyRowena Crockett, Marcella Roba, Marco Naka, Beat Gasser, Daniel Delfosse,Vinzenz Frauchiger, Nicholas D. SpencerJ. Biomed. Mat. Res. A; 2009; 89A(4) pp 1011-1018

Contents xix

2.43. A Novel Low-Friction Surface For Biomedical Applications: Modification of 420

Poly(Dimethyl-Siloxane) (PDMS) with Polyethylene Glycol(PEG)-Dopa-LysineKanika Chawla, Seunghwan Lee, Bruce P. Lee, Jeffrey L. Dalsin,Phillip B. Messersmith, Nicholas D. SpencerJ. Biomed. Mat. Res.; 2009; 90A(3) pp 742-749

3. Effects of Surface Morphology and Structure 428

3a. The influence of atomic-scale structure on catalytic activity 428

Commentary

3.1. Structure Sensitivity in the Iron Single Crystal Catalyzed Synthesis 429

of Ammonia

N.D. Spencer, R.C. Schoonmaker, G.A. SomorjaiNature; 1981; 294 pp 643-644

3.2. Iron Single Crystals as Ammonia Synthesis Catalysts: Effect of Surface 431

Structure on Catalyst ActivityN.D. Spencer, R.C. Schoonmaker, G.A. SomorjaiJ. Catalysis; 1982; 74 pp 129-135

3b. Surface structure and wetting 438

Commentary

3.3. Beyond the Lotus Effect: Roughness Influences on Wetting Over a Wide 439

Surface-Energy RangeDoris M. Spori, Tanja Drobek, Stefan Ziircher, Mirjam Ochsner,

Christoph Sprecher, Andreas Miihlebach, Nicholas D. Spencer

Langmuir, 2008; 24(10) pp 5411-5417

3.4. Cassie-State Wetting Investigated by Means of a Hole-to-Pillar-Density 446

Gradient

Doris M. Spori, Tanja Drobek, Stefan Ziircher, Nicholas D. Spencer

Langmuir, 2010; 26(12) pp 9465-9473

3c. Surface structural effects on cells 455

Commentary

3.5. Systematic Study of Osteoblast and Fibroblast Response to Roughness by 456

Means of Surface-Morphology Gradients

Tobias P. Kunzler, Tanja Drobek, Martin Schuler, Nicholas D. Spencer

Biomaterials; 2007; 28, pp 2175-2182

XX Tailoring Surfaces

3.6. Systematic Study of Osteoblast Response to Nanotopography by Means of 464

Nanoparticle-Density Gradients

Tobias P. Kunzler, Christoph Huwiler, Tanja Drobek, Janos Voros,Nicholas D. Spencer


4. Spatial Control of Surface Modification 471

4a. Surface gradients 471

Commentary

4.1. A Simple, Reproducible Approach to the Preparation of Surface-Chemical 473

Gradients

5. Morgenthaler, S. Lee, S. Zurcher, N. D. Spencer

Langmuir, 2003; 19(25) pp 10459-10462

4.2. Submicron Structure of Surface-Chemical Gradients Prepared by a 477

Two-Step Immersion Method

S. M. Morgenthaler, S. Lee, N. D. Spencer

Langmuir, 2006; 22(6) pp 2706-2711

4.3. Order and Composition of Methyl-Carboxyl and Methyl-Hydroxyl 483

Surface-Chemical Gradients

Nagaiyanallur V. Venkataraman, Stefan Zurcher, Nicholas D. Spencer

Langmuir, 2006; 22(9) pp 4184-4189

4.4. Fabrication of Material-Independent Morphology Gradients for 489

High-Throughput Applications

Tobias P. Kunzler, Tanja Drobek, Christoph M. Sprecher, Martin Schuler,Nicholas D. Spencer

Applied Surface Science; 2006; 253 pp 2148-2153

4.5. Poly(L-lysine)-g-Poly(Ethylene Glycol) Based Surface Chemical 495

Gradients — Preparation, Characterization and First ApplicationsSara Morgenthaler, Christian Zink, Brigitte Stadler, Janos Voros,Seunghwan Lee, Nicholas D. Spencer, Samuele G.P. Tosatti

Biointerphases; 2007; 1(4) pp 156-165

4.6. Fabrication of Multiscale, Surface-Chemical Gradients by Means of 505

Photocatalytic LithographyNicolas Blondiaux, Stefan Zurcher, Martha Liley, Nicholas D. Spencer

Langmuir, 2007; 23(7) pp 3489-3494

Contents xxi

4.7. Punctionalizable Nano-Morphology Gradients via Colloidal Self-Assembly 511

Christoph Huwiler, Tobias Kiinzler, Marcus Textor, Janos Voros,Nicholas D. Spencer

Langmuir, 2007; 23(11) pp 5929-5935

4.8. Surface-Chemical and -Morphological Gradients (Review Article) 518Sara Morgenthaler, Christian Zink, Nicholas D. Spencer

Soft Matter, 2008; 4 pp 419-434

4.9. Spatial Tuning of Metal Work Function by Means of Alkanethiol and 534

Fluorinated Alkanethiol Gradients

Nagaiyanallur V. Venkataraman, Stefan Ziircher, Antonella Rossi,Seunghwan Lee, Nicola Naujoks, Nicholas D. SpencerJournal of Physical Chemistry C; 2009; 113(14) pp 5620-5628

4.10. Orthogonal, Three-Component, Alkanethiol-based, Surface-Chemical 543

Gradients on Gold

Eva Beurer, Nagaiyanallur V. Venkataraman, Antonella Rossi,Florian Bachmann, Roman Engeli, Nicholas D. Spencer

Langmuir, 2010; 26(11) pp 8392-8399

4b. Surface patterns 551

Commentary

4.11. Selective Molecular Assembly Patterning: A New Approach to 553

Micro- and Nanochemical Patterning of Surfaces for Biological ApplicationsR. Michel, J.W. Lussi, G. Csiics, I. Reviakine, G. Danuser, B. Ketterer,J.A. Hubbell, M. Textor, N.D. Spencer

Langmuir, 2002; 18(8) pp 3281-3287

4.12. Microcontact Printing of Macromolecules with Submicrometer Resolution 560

by Means of Polyolefin StampsGabor Csiics, Tobias Kiinzler, Kirill Feldman, Franck Robin,Nicholas D. Spencer

Langmuir, 2003; 19(15) pp 6104-6109

4.13. Diffusion of Alkanethiols in PDMS and its Implications on Microcontact 566

Printing (/iCP)T. Balmer, H. Schmid, R. Stutz, E. Delamarche, B. Michel, N.D. Spencer,H. Wolf

Langmuir, 2005; 21(2) pp 622-632

4.14. Closing the Gap Between Self-Assembly and Microsystems Using 577

Self-Assembly, Transfer, and Integration (SATI) of Particles

T. Kraus, L. Malaquin, E. Delamarche, H. Schmid, N. D. Spencer, H. Wolf

Adv. Materials; 2005; 17 pp 2438-2442

xxii Tailoring Surfaces

4.15. Nanoparticle Printing with Single-Particle Resolution 582

Tobias Kraus, Laurent Malaquin, Heinz Schmid, Walter Riess,Nicholas D. Spencer, Heiko Wolf

Nature Nanotechnology; 2007; 2 pp 570-576

4.16. Selective Assembly of Sub-Micron Polymer Particles 589

Cyrill Kuemin, K. Cathrein Hiickstadt, Emanuel Lortscher, Antje Rey,Andrea Decker, Nicholas D. Spencer, Heiko Wolf

Advanced Materials; 2010; 22(25) pp 2804-2808

5. Methods for Characterizing Surface Modifications 594

5a. Roughness characterization 594

Commentary

5.1. Wavelength-Dependent Measurement and Evaluation of Surface 595

Topographies: Application of a New Concept of Window Roughness and

Surface Transfer Function

M. Wieland, P. Hanggi, W. Hotz, M. Textor, B.A. Keller, N.D. SpencerWear, 2000; 237(2) pp 231-252

5b. Chemical characterization by scanning-probe methods 617

Commentary

5.2. The Sensitivity of Frictional Forces to pH on a Nanometer Scale — A 618

Lateral Force Microscopy StudyA. Marti, G. Hahner, N.D. SpencerLangmuir, 1995; 11 pp 4632-4635

5.3. The Influence of pH on Friction between Oxide Surfaces in Electrolytes, 622

Studied with Lateral Force Microscopy: Application as a Nanochemical

Imaging TechniqueG. Hahner, A. Marti, N.D. Spencer

THbology Letters; 1997; 3(4) pp 359-365

5.4. Towards a Force Spectroscopy of Polymer Surfaces 629

K. Feldman, T. Tervoort, P. Smith, N.D. Spencer

Langmuir, 1998; 14(2) pp 372-378

5.5. Probing Resistance to Protein Adsorption of Oligo(Ethylene 636

Glycol)-Terminated Self-Assembled Monolayers by Scanning Force MicroscopyK. Feldman, G. Haehner, N.D. Spencer, P. Harder, M. Grunze

J. Amer. Chem. Soc.; 1999; 121(43) pp 10134-10141

Contents xxiii

5c. Following surface reactions in a UHV chamber 644

Commentary

5.6. Improved Instrumentation to Carry Out Surface Analysis and to Monitor 645

Chemical Surface Reactions in situ on Small Area Catalysts over a Wide

Range of Pressures (10~8 - 105 torr)A.L. Cabrera, N.D. Spencer, E. Kozak, P.W. Davies, G.A. SomorjaiRev. Sci. Instr.; 1982; 53(12) pp 1888-1893

5.7. A Simple, Controllable Source for Dosing Molecular Halogens in UHV 651

N.D. Spencer, P.J. Goddard, P.W. Davies, M. Kitson, R.M. Lambert

J. Vac. Sci. TechnoL; 1983; 1(3) pp 1554-1555

5.8. Molecular Beam Reactive Scattering of Br2 from Pd(lll) Using an 653

Electrochemical Effusive Source

W.T. Tysoe, N.D. Spencer, R.M. Lambert

Surface Sci.; 1982; 120(2) pp 413-426

tailoring surfaces : modifying surface composition and ... · msc centenary lecture series...

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