Tailoring Surfaces: Modifying Surface Composition and Structure for Applications in Tribology, Biology and Catalysis (IISC Centenary Lecture Series)

Contents......Page 14
Preface......Page 8
Biography of Professor Nicholas D. Spencer......Page 10
Acknowledgments......Page 12
1. Introduction......Page 25
1a. Self-assembled monolayers......Page 26
1b. Functionalizing surfaces with polymer brushes......Page 29
1c. Using additives to modify surfaces in a self-repairing way......Page 33
1d. Structure: a new dimension to surface tailoring......Page 34
1e. Spatial distributions on surfaces: from patterns to gradients......Page 37
Commentary......Page 41
Introduction......Page 43
Experimental Section......Page 44
Results......Page 45
Discussion......Page 48
Conclusion......Page 51
Experimental Section......Page 52
Results and Discussion......Page 53
Conclusions......Page 55
2. Material and Methods......Page 56
3. Results......Page 57
4. Discussion......Page 63
1. Introduction......Page 71
3. Results and Discussion......Page 72
4. Conclusion and Outlook......Page 76
1. Introduction......Page 78
3. Results......Page 79
4. Discussion......Page 86
5. Conclusion......Page 89
1. Introduction......Page 90
3. Results......Page 91
4. Discussion and Conclusions......Page 96
1 Introduction......Page 98
2.1 Self-assembled Monolayers (SAMs)......Page 99
2.5 Polarization–Modulation Infrared Reflection–Absorption Spectroscopy (PM-IRRAS)......Page 100
3.1 Initial Characterization of the SAM Films......Page 101
3.2 Nanotribological Properties of the SAM Films by Means of AFM......Page 102
3.3 Elastomeric Sliding Contact on the SAM Films on a Macroscopic Scale......Page 103
3.4 PM-IRRAS Studies on the Sliding Track......Page 104
3.5 Lubrication Mechanisms: The Transition from Boundary Lubrication to Soft EHL......Page 105
3.6 Lubrication Mechanisms: the Role of Surface Chemistry......Page 106
References......Page 107
Introduction......Page 109
Materials and Methods......Page 110
Results......Page 112
Discussion......Page 116
Conclusion and Perspectives......Page 117
Commentary......Page 119
1. Introduction......Page 121
2.2. Optical waveguides lightmode spectroscopy (OWLS)......Page 122
2.4. Mini traction machine (MTM)......Page 123
2.6. Cleaning of the tribo-pairs......Page 124
3.2. Lubrication properties in rolling contact......Page 125
3.3. Lubrication properties in mixed sliding/rolling contact......Page 126
3.4. Lubrication properties in sliding contact......Page 127
4. Summary......Page 128
References......Page 129
1. Introduction......Page 130
2.2 Ultra-thin-ìlm interferometry......Page 131
2.5. Cleaning of the tribo-pairs......Page 132
3.2. The inîuence of the PLL-g-PEG architecture on the tribological properties......Page 133
4. Discussion......Page 136
4.2. Film formation by HEPES and polymer solutions......Page 137
4.3. Mechanism of ìlm formation by PLL-g-PEG......Page 138
4.4. Inîuence of PLL-g-PEG architecture......Page 139
References......Page 140
Introduction......Page 141
Materials and Methods......Page 142
Results......Page 143
Discussion......Page 146
References and Notes......Page 147
1. Introduction......Page 149
2.2. Pin-on-disk tribometry......Page 150
3.1. Theoretically predicted  lm thickness......Page 151
3.2. In uence of oxygen-plasma treatment for PDMS sliding......Page 152
3.4. Oxygen-plasma-treatment vs. amphiphilic copolymers......Page 154
4. Summary......Page 156
References......Page 157
1. Introduction......Page 158
2.2. Preparation of substrates and polymer coating......Page 159
3.1. Characterization of polymer .lm thickness......Page 160
3.2. Pin-on-disk tribometry: poly(L-lysine)-graft-poly (ethylene glycol)......Page 161
3.3. Fluorescence microscopy: poly(L-lysine)-graft-poly (ethylene glycol)......Page 162
3.4. Pin-on-disk tribometry: methoxy-poly(ethylene glycol)-trimethylsilylether......Page 163
References......Page 164
INTRODUCTION......Page 165
MATERIALS AND METHODS......Page 166
RESULTS AND DISCUSSION......Page 170
REFERENCES......Page 177
2.15. Sweet, Hairy, Soft, and Slippery Seunghwan Lee, Nicholas D. Spencer Science; 2008; 319 pp 575-576......Page 179
Experimental Section......Page 181
Results......Page 182
Discussion......Page 184
Conclusions......Page 185
1 Introduction......Page 186
2.1 Poly(L-lysine)-graft-dextran (PLL-g-dex)......Page 187
2.4 Mini-traction Machine......Page 188
3.1 Synthesis and Structural Features of PLL-g-dex Copolymers......Page 189
3.2 Adsorption Behavior of PLL-g-dex: OWLS......Page 190
3.3 Lubrication Properties of the Copolymers: General Considerations......Page 192
References......Page 197
1 Introduction......Page 200
2.2 Experimental Procedures......Page 201
3.1 Adsorption Measurements......Page 203
3.2 Pin-on-Disc......Page 205
4 Discussion......Page 206
References......Page 208
Introduction......Page 210
Experimental Section......Page 211
Results and Discussion......Page 212
Conclusions......Page 217
References and Notes......Page 218
1 Introduction......Page 219
2.1 Materials Used......Page 220
2.5 Quartz Crystal Microbalance......Page 221
3.1 Tribological Studies of PLL-g-PEG in Aqueous Glycerol Solutions......Page 222
3.2 ‘‘Rehealing’’ Studies of PLL-g-PEG in Aqueous Glycerol Mixtures......Page 225
3.3 Film-thickness Calculations for Lubricants Consisting of PLL-g-PEG in Aqueous Glycerol Mixtures......Page 227
4 Conclusions......Page 228
References......Page 229
1. INTRODUCTION......Page 231
2.1. Synthesis of PLL-g-PEG.......Page 232
3. RESULTS......Page 233
4. DISCUSSION......Page 234
REFERENCES AND NOTES......Page 237
Commentary......Page 238
1. Introduction......Page 239
2. Materials and Methods......Page 240
3. Results and Discussion......Page 242
Conclusions......Page 247
1. Introduction......Page 249
2.2. Chemically patterned surfaces......Page 250
3. Results and discussion......Page 251
3.1. Immobilization of biomolecules on chemically patterned TSG surfaces......Page 252
3.2. Generation of etch-patterned surfaces with immobilized biomolecules......Page 254
4. Conclusions and outlook......Page 255
References......Page 256
1. Introduction......Page 258
2. Materials and Methods......Page 260
3. Results......Page 262
4. Discussion......Page 267
5. Conclusions......Page 268
References and Notes......Page 269
1. Introduction......Page 270
2. Materials and Methods......Page 271
3. Results and Discussion......Page 272
4. Conclusions......Page 279
1. Introduction......Page 280
2. Materials and Methods......Page 281
3. Results and Discussion......Page 284
4. Summary and Conclusions......Page 289
1. Introduction......Page 291
2. Materials and Methods......Page 293
3. Results......Page 294
4. Discussion......Page 296
5. Conclusions......Page 300
INTRODUCTION......Page 301
The extended surface-forces apparatus......Page 302
Refractive index and adsorbed mass......Page 303
Comparison with theory......Page 304
Embedded ìne structure......Page 305
DISCUSSION......Page 306
REFERENCES......Page 308
1. Introduction......Page 311
2. Materials and Methods......Page 313
3. Results and Analysis......Page 314
4. Discussion......Page 320
5. Conclusions......Page 323
1. Introduction......Page 324
2. Materials and Methods......Page 325
3. Results and Discussion......Page 326
4. Conclusions......Page 330
References and Notes......Page 331
1. Introduction......Page 332
2. Synthesis of the Nitrilotriacetic-Acid- Functionalized Copolymer, PLL-g-PEG......Page 334
3. Surface Preparation and Sensing by OWLS......Page 335
4. Microarray Using the MAPL Technique......Page 337
6. Experimental......Page 338
Introduction......Page 341
Materials and Methods......Page 342
Results and Discussion......Page 344
Conclusions......Page 346
Commentary......Page 348
Introduction......Page 349
Experimental Section......Page 350
Results......Page 351
Discussion......Page 354
Conclusions......Page 355
1. Introduction......Page 357
2. Experimental......Page 358
3. Results......Page 359
4. Discussion......Page 360
References......Page 361
1. Introduction......Page 363
2.1. Sample preparation......Page 364
2.3. XPS......Page 365
3.3. Chemical states of the studied elements......Page 366
4. Discussion......Page 369
4.2. The surface chemistry of the triboìlm......Page 370
References......Page 372
1. Introduction......Page 374
2.2. Methods......Page 375
3.1. Reference material: ZnDTP frozen on gold......Page 376
3.3. Thermal tests......Page 378
3.4. Tribological tests......Page 380
4.1. Chemical composition of commercially pure ZnDTP......Page 381
4.2. Chemical composition of thermal reaction products......Page 382
Acknowledgments......Page 383
References......Page 384
2.1. Materials......Page 385
2.2. Methods......Page 386
3.2. Imaging X-ray photoelectron spectroscopy (i-XPS) and SAXPS......Page 387
3.3. Time-of-fl ight secondary ion mass spectroscopy......Page 388
4.2. Effect of load......Page 389
5. Conclusions......Page 390
References......Page 391
1 Introduction......Page 392
2.1 Tribological Testing......Page 393
2.3 X-Ray Photoelectron Spectroscopy......Page 394
3.2 Wear......Page 395
3.3 XPS Results......Page 396
4.1 Comparison of the Constant-Load and Oscillating- Load Approaches......Page 401
4.2 Influence of Contact Pressure on Thickness and Composition of the Tribological Films......Page 402
5 Conclusion......Page 403
References......Page 404
1 Introduction......Page 406
2.1 Materials......Page 407
3.1 Characterization of Purified TPPT......Page 408
3.2 Heating Experiments......Page 409
4.1 Oxidation of the Base Oil......Page 413
4.3 Proposed Reaction Mechanism......Page 415
References......Page 416
Commentary......Page 419
1. Introduction......Page 420
2.2. Polymer and ceramic materials......Page 421
2.7. Protein adsorption......Page 422
3.2. Thermal protein unfolding......Page 423
3.3. Protein adsorption and boundary lubrication......Page 424
4. Discussion......Page 426
References......Page 427
1. Introduction......Page 429
2.7. Evaluation of synovial îuid protein composition by means of 2D gel electrophoresis......Page 430
3.2. Protein adsorption analysis with SDS-PAGE and OWLS......Page 431
4. Discussion......Page 432
References......Page 435
INTRODUCTION......Page 436
MATERIALS AND METHODS......Page 437
RESULTS......Page 438
DISCUSSION......Page 440
References......Page 442
INTRODUCTION......Page 444
MATERIALS AND METHODS......Page 445
RESULTS......Page 446
DISCUSSION......Page 448
References......Page 451
Commentary......Page 452
3.1. Structure Sensitivity in the Iron Single Crystal Catalyzed Synthesis of Ammonia N.D. Spencer, R.C. Schoonmaker, G.A. Somorjai Nature; 1981; 294 pp 643-644......Page 453
INTRODUCTION......Page 455
METHODS......Page 456
RESULTS......Page 457
DISCUSSION......Page 459
REFERENCES......Page 461
Commentary......Page 462
Introduction......Page 463
Methods......Page 464
Results and Discussion......Page 465
Conclusions......Page 468
Introduction......Page 470
Materials and Methods......Page 471
Results and Discussion......Page 473
Conclusions......Page 477
Commentary......Page 479
1. Introduction......Page 480
2.3. Experimental design......Page 481
3.2. Cell response......Page 482
4. Discussion......Page 485
References......Page 486
1. Introduction......Page 488
2.3. Experimental design......Page 489
3.2. Cell response......Page 490
4. Discussion......Page 491
References......Page 494
Commentary......Page 495
1. Introduction......Page 497
3. Results and Discussion......Page 498
1. Introduction......Page 501
2. Experimental Section......Page 502
3. Results and Discussion......Page 503
4. Conclusions......Page 505
Introduction......Page 507
Results and Discussion......Page 508
Conclusions......Page 512
1. Introduction......Page 513
3. Results and discussion......Page 514
4. Conclusion......Page 517
References......Page 518
I. INTRODUCTION......Page 519
II. EXPERIMENTAL SECTION......Page 521
III. RESULTS AND DISCUSSION......Page 523
IV. CONCLUSIONS......Page 526
ACKNOWLEDGMENT......Page 527
Introduction......Page 529
Materials and Methods......Page 530
Results and Discussion......Page 531
Conclusions and Outlook......Page 534
Introduction......Page 535
Results and Discussion......Page 536
Conclusion......Page 540
1. Introduction......Page 542
2.1. Surface-chemical gradients......Page 543
2.2. Morphological gradients......Page 547
3.1. Protein adsorption......Page 550
3.2. Cell adhesion......Page 552
3.3. Wettability effects......Page 553
3.4. Other applications......Page 554
References......Page 556
Introduction......Page 558
Experimental Section......Page 559
Results and Discussion......Page 560
Conclusions......Page 565
References and Notes......Page 566
Introduction......Page 567
Results and Discussion......Page 568
Conclusions......Page 574
Commentary......Page 575
1. Introduction......Page 577
2. Materials and Methods......Page 578
3. Results......Page 579
4. Discussion and Conclusions......Page 582
1. Introduction......Page 584
3. Results and Discussion......Page 585
Conclusions......Page 588
1. Introduction......Page 590
2. Setup for Diffusion Experiments......Page 591
3. Mathematical Modeling of Diffusion Experiments......Page 592
4. Results and Discussion......Page 594
5. Multiple Printing......Page 597
6. Conclusions and Outlook......Page 599
4.14. Closing the Gap Between Self-Assembly and Microsystems Using 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......Page 601
Experimental......Page 604
HIGH-PRECISION INKING......Page 606
PARTICLE TRANSFER......Page 609
METHODS......Page 611
References......Page 612
4.16. Selective Assembly of Sub-Micron Polymer Particles Cyrill Kuemin, K. Cathrein H uckst adt, Emanuel L ortscher, Antje Rey, Andrea Decker, Nicholas D. Spencer, Heiko Wolf Advanced Materials; 2010; 22(25) pp 2804-2808......Page 613
Supporting Information......Page 617
Commentary......Page 618
1. Introduction......Page 619
2.1. Material surfaces......Page 621
3.1. Fourier transformation procedure......Page 622
3.2. Relation between coefficients C and roughness pa- n rameter Rq......Page 624
3.3. COF techniques......Page 627
3.4. EÕaluation of 3-D profiles......Page 629
3.5. Surface treatment transfer functions......Page 630
4.1. Micromachined reference steel surface......Page 632
4.2. Lacquered car body surfaces......Page 633
4.3. Titanium implant surfaces......Page 635
References......Page 639
Commentary......Page 641
Experimental Section......Page 642
Results and Discussion......Page 643
2. Experimental......Page 646
3.Results and discussion......Page 647
3.3. Interaction between two oxide surfaces in an electrolyte......Page 648
References......Page 651
Introduction......Page 653
Experimental Section......Page 654
Results and Discussion......Page 655
Conclusions......Page 659
Introduction......Page 660
Experimental Section......Page 661
Results......Page 662
Discussion......Page 665
Conclusions......Page 667
Commentary......Page 668
I. ONE-TIER-HPLP SYSTEM......Page 669
III. SURFACE ANALYSIS......Page 671
V. APPLICATION OF THE HIGH-PRESSURE-LOW-PRESSURE APPARATUS TO CATALYTIC SYSTEMS......Page 672
5.7. A Simple, Controllable Source for Dosing Molecular Halogens in UHV N.D. Spencer, P.J. Goddard, P.W. Davies, M. Kitson, R.M. Lambert J. Vac. Sci. Technol.; 1983; 1(3) pp 1554-1555......Page 675
1. Introduction......Page 677
2. Experimental......Page 678
3.1. Beam spurce characteristics......Page 680
3.2. Reactive Scattering of bromine from Pd(111)......Page 682
3.3. Atomic bromine desorption......Page 683
3.4. Molecular bromine desorption......Page 684
3.5. Analysis of results......Page 685
3.6. Intensity data......Page 686
3.7. Phase shift data......Page 687
References......Page 689