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title :

Foundations of Vacuum Science and Technology

author :

Lafferty, J. M.

publisher :

John Wiley & Sons, Inc. (US)

isbn10 | asin :

0471175935

print isbn13 :

9780471175933

ebook isbn13 :

9780585339368

language :

English

1998

subject publication date :

Vacuum, Kinetic theory of gases.

lcc :

QC166.F68 1998eb

ddc :

621.5/5

subject :

Vacuum, Kinetic theory of gases.

cover

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Page iii

Foundations of Vacuum Science and Technology

Edited By James M. Lafferty

Foundations of Vacuum Science and Technology Edited By James M. Lafferty < previous page page_iii next

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This book is printed on acid-free paper.

next page > This book is printed on acid-free paper. Copyright © 1998 by John Wiley

Copyright © 1998 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada.

Page iv

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (508) 750-8400, fax (508) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-mail: PERMREQ @ WILEY.COM.

Library of Congress Cataloging in Publication Data:

Foundations of vacuum science and technology/edited by J. M. Lafferty. p. cm. "A Wiley-Interscience publication." Includes bibliographical references and index. ISBN 0-471-17593-5 1. Vacuum. 2. Kinetic theory of gases. I. Lafferty, J. M. (James Martin), 1916. QC166.F68 1997

621.5

5dc21

96-29895

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

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Preface

Page v

The industrial and scientific importance of vacuum technique has continued to grow during the past 30 years, even with the demise of television and radio receiving tubes and many gas-filled tubes. The replacement of vacuum and low- pressure gas discharge tubes by semiconductors and integrated circuits has placed an even greater demand and more stringent conditions on vacuum technique for the processing and manufacture of these devices. This has led to the development of a number of "dry" vacuum pumps to produce a "clean vacuum" free of hydrocarbons. The space programs, high-energy accelerators, analytical instruments, freeze-drying of foods and drugs, and the manufacture of color television picture tubes, incandescent and metal vapor lamps, high-power vacuum, and x-ray tubes all continue to require the need for vacuum technique.

While the material in this book is totally new, it follows in the tradition set by Scientific Foundations of Vacuum Technique by Saul Dushman, published in 1949. That book enjoyed unprecedented success and is now a classic in its field. By 1960 it was badly in need of revision. This editor had the privilege of participating as editor of the revised edition, which was published in 1962. This second edition was brought up to date by a number of contributors with specialized knowledge in the disciplines involved. An attempt was made to introduce the new developments made in vacuum technique but keep the original plan of the book and retain much of the material that was still of current interest.

The editor was encouraged by Leonard Beavis of the American Vacuum Society Education Committee and the publishers of the previous editions to undertake the publication of the present volume. The advances made in vacuum science and technology during the past three decades has required a complete reworking of the material in the previous volume. However, every effort has been made to follow the unique style of the original bookthat is, to present a survey of fundamental ideas in physics and chemistry that would be useful to both scientists and engineers dealing with problems associated with the use, production, and measurement of high vacuums. This volume is a critical survey of important developments in vacuum technique with many references for those who seek a better understanding and more detailed information in the field. It is not a vacuum handbook, many of which are listed in the Appendix of this book.

Every effort was made to select on a worldwide basis a number of outstanding vacuum specialists who were willing to take time to contribute to this volume. With

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Page vi

the curtailment of vacuum research in the major industrial laboratories, one now only finds vacuum experts as independent consultants or in companies manufacturing vaccum systems and components, a few educational institutions, and government laboratories.

While the basic laws of kinetic theory of gases have not changed over the years, a better understanding of gas flow over

a wide range of pressures has necessitated an expanded chapter on the subject. It now encompasses all flow regimes

from free molecular flow to atmospheric pressure. It treats compressible flow through tubes and orifices under choked and nonchoked conditions as well as turbulent flow in ducts of any cross section.

Many topics that were only mentioned in the second edition of Scientific Foundations of Vacuum Technique now have full chapters devoted to them. The progress made in vacuum pumps over the past three decades, for example, is remarkable. Three chapters are now devoted to this subject. Detailed information is given for the first time on liquid ring pumps, dry pumps, turbo pumps, getter pumps, and cryopumps.

The subject of leak detection, which had only a few paragraphs devoted to it in the old edition, now has a full chapter describing leak detectors as a rugged industrial tool for everyday use capable of quantitative measurements.

Information on the design of high-vacuum systems has been expanded to help the reader in selecting pump sets for various system applications and in predicting their performance.

Pressure measurements continue to be important on every vacuum system. This subject is fully covered in the chapter on vacuum gauges. While the ionization gauge continues to be the principal pressure sensor for measuring total pressure in high- and ultrahigh-vacuum systems, modern solid-state electronics has simplified its use. The accuracy of this device in measuring pressure depends on a knowledge of the composition of the gas being measured. The partial pressure analyzer has become a far more sophisticated way to measure pressure and give the vacuum system operator an insight of what is occurring within the system. The invention of the quadrupole mass spectrometer with solid-state electronics has done much to make partial pressure measurements relatively simple and inexpensive. A full chapter is devoted to this subject.

In discussing pressure measurements, a word about pressure units seems appropriate. While use of the pascal, the ISO unit of pressure, has been encouraged in this book, many of the European contributors strongly preferred using the millibar (mbar). The mbar falls in a class of units that are temporarily accepted for use by the ISO. You will find both units in this book. The advantage of the mbar is that it is nearly equal in magnitude to the Torr or mmHg found in earlier publications and is familiar to many readers (1 mbar = 0.75 Torr). When several orders of magnitude of pressure are plotted on a log scale, the mbar and Torr plots are nearly indistinguishable. Some of the figures in this book that have been copied from earlier publications may still have the pressure plotted in Torr.

Ultrahigh-vacuum technique had its infancy in midcentury. Today it is a matured procedure used in a great variety of applications and in commercially available equipment. Researchers do not appear to have reached a limit yet in their

quest to produce and measure a perfect vacuum. This work is described in the chapter devoted to ultrahigh and extreme high vacuum. Considerable progress has been made in this area by pushing vacuum techniques to their limit and gaining

a better

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understanding of the gassurface interactions and diffusion in solids as described in the chapter on this subject. While pressures as low as 1011 Pa have been measured in the laboratory, this is still at least three orders of magnitude higher than that in interstellar space.

The final chapter is devoted to calibration and standards. It describes the physical background and state of the art of today's primary vacuum standards in the various national laboratories. It should be useful reading not only for those involved in calibration and quality control but for those interested in the accuracy limitations of various vacuum instruments.

The editor is indebted to several people for suggestions concerning this volume. Special mention is made of the late Hermann Adam for helpful discussions and for suggesting a number of German contributors for the book. John Weed, a member of the American Vacuum Society Education Committee, solicited suggestions for the volume from a number of A.V.S. members. Nigel Dennis coordinated chapters three and four on vacuum pumps, and Benjamin Dayton and Paul Redhead have made many helpful suggestions.

J. M. LAFFERTY SCHENECTADY, NEW YORK

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Contributors

Helmut Bannwarth, LEDERLE GmbH, Gundelfingen, Germany

Page ix

Benjamin B. Dayton, Consultant, East Flatrock, North Carolina, USA

Nigel T. M. Dennis, Edwards High Vacuum International, Crawley, West Sussex, England

Johan E. de Rijke, Vacuum Technical Services, Morgan Hill, California, USA

Robert E. Ellefson, Leybold Inficon, Inc., East Syracuse, New York, USA

Bruno Ferrario, SAES Getters S.p.A., Lainate (Milano), Italy

Werner Grosse Bley, Leybold Vakuum GmbH, Cologne, Germany

Hinrich Henning, Leybold Vakuum GmbH, Cologne, Germany

Jörgen Henning, intervac Henning, GmbH, Kreuzwertheim, Germany

John B. Hudson, Materials Science and Engineering Department, Rensselaer Polytechnic Institute, Troy, New York, USA

Karl Jousten, Physikalisch-Technische Bundesanstalt, Berlin, Germany

R.

Gordon Livesey, Edwards High Vacuum International, Crawley, West Sussex, England

R.

Norman Peacock, MKS Instruments, HPS Division, Boulder, Colorado, USA

Paul A. Redhead, Institute for Microstructural Sciences, National Research Council, Ottawa, Ontario, Canada

Wolfgang Schwarz, Leybold Systems GmbH, Hanau, Germany

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Contents

Preface

v

Contributors

ix

Acronyms

xxiii

1. Kinetic Theory of Gases Benjamin B. Dayton

1

2

1.1. Ideal Gas Law

1.2. Avogadro's Number

6

1.3. Molecular Collisions; Mean Free Path; MaxwellBoltzmann Distribution Laws

8

1.3.1. Relation Between Molecular Velocities and Velocity of Sound

16

1.3.2. Determination of Avogadro's Constant from Distribution of Particles in Brownian Motion

17

1.4. Gas Pressure and Rate at Which Molecules Strike a Surface

18

1.5. Rate of Evaporation and Vapor Pressure

22

1.6. Free Paths of Molecules

26

1.7. Relation Between Coefficient of Viscosity, Mean Free Path, and Molecular Diameter

29

1.7.1. Viscosity at Low Pressures

37

1.7.2. Molecular Diameters

39

1.7.3. Application of the van der Waals Equation

39

1.7.4. From the Density of the Solid or Liquid

40

1.7.5. Cross Section for Collision with Electrons

41

41

1.8. Heat Conductivity of Gases

1.9. Thermal Conductivity at Low Pressures

44

1.9.1. Free-Molecule Conductivity (Knudsen)

46

1.9.2. Temperature Discontinuity (Smoluchowski)

50

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1.10. Thermal Transpiration (Thermomolecular Flow)

53

1.11. Thermal Diffusion

57

1.12. Theory of Diffusion of Gases

62

1.12.1. MaxwellLoschmidt Method for Determination of Diffusion Coefficients

65

1.12.2. Effect of Pressure of Gas on Rates of Evaporation of Metals

67

1.13. Random Motions and Fluctuations

69

1.14. Scattering of Particle Beams at Low Gas Pressures

71

References and Notes

73

2. Flow of Gases Through Tubes and Orifices R. Gordon Livesey

81

2.1. Flow Conductance, Impedance, and Gas Throughput

83

2.2. Molecular Flow

85

2.2.1. Conductance of an Aperture

86

2.2.2. General Considerations for Long Ducts

87

2.2.3. General Considerations for Short Ducts

87

2.2.4. Uniform Circular Cross Section

88

2.2.5. Duct of Uniform Rectangular Cross Section

90

2.2.6. Tube of Uniform Elliptical Cross Section

92

2.2.7. Cylindrical Annulus (Flow Between Concentric Cylinders)

93

2.2.8. Uniform Triangular Section (Equilateral)

94

2.2.9. Other Shapes

94

2.2.10. Combinations of Components

96

2.2.11. Cases of Unsteady Flow

102

2.3. Continuum Flow

105

2.3.1. Viscous Laminar Flow

108

2.3.2. Turbulent Flow

112

2.3.3. Compressible Flow

116

2.3.3.1. Flow through an Aperture or Short Duct

119

2.3.3.2. Approximation for Flow Through an Aperture

121

2.3.4. Corrections for Flow Obstructions

121

2.3.5. ApproximationsEntrance Correction Model

122

2.3.6. ApproximationsKinetic Energy Model

124

2.3.7. Long Duct Criteria

126

2.4. Transitional Flow

128

2.4.1.

Transitional Flow in Long Ducts

129

2.4.2.

Long Duct Criterion in Transitional Flow

134

2.4.3.

Transitional Flow through Apertures and Short Ducts

135

Symbols

137

References

139

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3. Positive Displacement Vacuum Pumps

141

Part I. Oil-Sealed Vacuum Pumps Nigel T. M. Dennis

143

3.1.

Oil-Sealed Vacuum Pumps

143

3.1.1. Pump Design

143

 

144

 

3.1.2. Gas Ballast

3.1.3. Pump Oil

147

3.1.4. Oil Suckback

148

3.1.5. Power Requirements and System Protection

148

3.1.6. Accessories

149

Part II. Liquid Ring Pumps Helmut Bannwarth

151

3.2.

Liquid Ring Pumps

151

3.2.1. Mechanism

151

3.2.2. Single-Stage Liquid Ring Vacuum Pumps

152

3.2.3. Two-Stage Liquid Ring Vacuum Pumps

153

3.2.4. The Operating Liquid

154

3.2.5. Operating Ranges of Liquid Ring Gas Pumps

154

 

3.2.6. Cavitation and Protection Against Cavitation

154

3.2.7. Types of Operation; Conveyance of Operating Liquid

156

3.2.8. Materials of Construction

157

 

3.2.9. Sealing

157

3.2.10. Drives

157

 

3.2.11. Accessories

158

Part III. Dry Vacuum Pumps Nigel T. M. Dennis

159

3.3.

Dry Vaccum Pumps

159

3.3.1.

Roots Pump

159

3.3.2.

Claw Pump

162

3.3.3.

Screw Pump

164

3.3.4.

Scroll Pump

167

3.3.5.

Piston and Diaphragm Pumps

169

References

170

General References

171

4. Kinetic Vacuum Pumps

173

Part I. Diffusion and Diffusion-Ejector Pumps Benjamin B. Dayton

175

4.1.

Diffusion Pumps

176

4.1.1. History of Development

176

4.1.2. Diffusion Pump Design

181

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4.2. Diffusion-Ejector Pumps

183

4.3. Performance of Vapor-Jet Pumps

185

 

4.3.1. Pumping Speed

185

4.3.2. Limiting Forepressure for Maximum Speed

187

4.3.3. Influence of Nozzle and Entrance Chamber Design on Speed

190

4.3.4. Ultimate Pressure

192

4.3.5. Backstreaming and Back Migration of Pump Fluid

194

4.3.6. Throughput

198

4.4. Theory of Pump Performance

202

 

4.4.1. Speed

202

4.4.2. Limiting Forepressure

204

4.4.3. Vapor-Jet Flow Pattern

205

4.4.4. Ultimate Pressure

221

Part II. Molecular Drag and Turbomolecular Pumps Jörgen Henning

233

4.5.

Molecular Drag Pumps

233

4.5.1.

Theoretical Considerations and Performance Data

234

4.5.2. Design Considerations

237

4.5.3. Typical Performance Data of Commerical Pumps

237

4.5.3.1. Compression

238

4.5.3.2. Pumping Speed

238

4.5.3.3. Ultimate Pressure

238

4.6. Turbomolecular Pumps

238

4.6.1. Theoretical Considerations and Performance Data

239

4.6.2. Design Considerations

241

4.6.2.1. Rotor and Stator Geometry

241

4.6.2.2. Rotor Suspension

242

4.6.2.3. Lubrication of Mechanical Bearings

242

4.6.2.4. Magnetic Rotor Suspension

242

4.6.2.5. Balancing and Vibration

243

4.6.2.6. Rotor Materials

243

4.6.2.7. Drive Systems

243

4.6.3.

Applicational Considerations

243

4.6.3.1. Venting

243

4.6.3.2. Baking

244

4.6.3.3. Cooling

244

244

4.6.3.4. Operation in Magnetic Fields

4.6.3.5. Pumping Corrosive Gases

245

4.6.3.6. Pumping Toxic or Radioactive Gases

245

4.6.3.7. Turbomolecular Pumps in Combination with Other Pumps

245

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4.6.4.

Performance Data of Commercial Pumps

245

 

4.6.4.1. Compression

246

4.6.4.2. Pumping Speed

246

4.6.4.3. Ultimate Pressure

247

4.7.

Combined Molecular Drag and Turbomolecular Pumps

247

4.7.1. Design Considerations

248

4.7.2. Typical Performance Data for Commericial Combined Molecular Drag and Turbomolecular

248

Pumps

 

4.7.2.1. Compression

248

4.7.2.2. Pumping Speed

248

4.7.2.3. Ultimate Pressure

248

4.8.

Backing Pumps

248

Part III. Regenerative Drag Pumps Nigel T. M. Dennis

251

4.9.

Regenerative Drag Pumps

251

4.9.1.

Mechanism

251

References

254

Part I. Getters and Getter Pumps Bruno Ferrario

261

5.1. Types of Gas Surface Interactions

261

5.2. Basic Concepts of Getter Materials

262

5.3. Adsorption and Desorption

263

5.4. Bulk Phenomena

265

 

5.4.1. Diffusion

265

5.4.2. Solubility

267

5.5. Equilibrium Pressures

268

5.6. Getter Materials

269

5.6.1. Basic Characteristics of Getter Materials

269

5.6.2. Sorption Speed and Sorption Capacity

269

5.6.3. Principal Types of Getter Materials and Their General Working Conditions

271

5.6.4. Interaction of Getters with Common Residual Gases

275

5.6.5. Evaporable Getters

275

5.6.5.1. Ba Getters

276

5.6.5.2. Titanium Sublimation Getter Pumps

291

5.6.6.

Nonevaporable Getters

297

5.6.6.1. Ternary Alloys

305

5.6.6.2. Other Ternary and Multicomponent Alloys

310

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5.7. Getter Configurations

310

5.8. Getter Applications

313

 

5.8.1. Nonevaporable getters Versus evaporable getters

314

5.8.2. Start-up and Working Conditions of Getters

315

Part II. Sputter Ion Pumps Hinrich Henning

 

317

5.9.

Gas Discharge Vacuum Pumps

317

5.10. The Penning Discharge

319

 

5.10.1. Pump Sensitivity

321

5.10.2. Ion Motion

323

5.10.3. Electron Cloud

324

5.10.4. Secondary Electrons

326

5.10.5. Transition from HMF Mode to HP Mode

327

5.10.6. Transition from LMF Mode to HMF Mode

328

5.10.7. Sputtering

329

5.11. SIP Characteristics

329

 

5.11.1.

Gettering

329

5.11.2. Ion Burial

330

5.11.3. Volume Throughput

331

5.11.4. Pumping Mechanism

335

5.11.5. Bakeout

338

5.11.6. Types of SIPs

338

5.11.7. Starting Properties

342

5.11.8. Memory Effect

343

5.11.9. Ultimate Pressure

343

5.11.10. Magnets

345

Part III. Cryopumps Johan E. de Rijke

347

5.12. AdsorptionDesorption

348

5.13. Cryotrapping

352

5.14. Pumping Speed and Ultimate Pressure

353

5.15. Capacity

355

5.16. Refrigeration Technology

357

5.17. Pump Configuration

359

5.18. Regeneration

363

5.19. Partial Regeneration

364

5.20. Sorption Roughing Pumps

364

References

368

General References

373

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6. Vacuum Gauges R. Norman Peacock

375

6.1. Pressure Units Used in Vacuum Measurements

377

6.2. Liquid Manometers

378

6.3. McLeod Gauge

379

6.4. Piston Pressure Balance Gauge

381

6.5. Bourdon Gauge

382

6.6. Capacitance Diaphragm Gauges

384

6.6.1. Sensitivity of the Capacitance Method

385

6.6.2. Deflection of a Thin Tensioned Membrane

386

6.6.3. Accuracy of Commercial Gauges

387

6.6.4. Thermal Transpiration

388

6.6.5. Conclusions

388

6.7. Viscosity Gauges

389

6.7.1.

Spinning Rotor Gauge

391

6.7.1.1. Theory

391

6.7.1.2. Commercial Gauges

394

 

6.7.1.3. Stability

397

6.7.1.4. Secondary or Transfer Standard

399

6.7.1.5. Use Precautions

401

6.7.1.6. Advantages and Disadvantages

401

6.7.2.

Oscillating Quartz Crystal Viscosity Gauge

402

6.7.2.1.

Advantages and Disadvantages

402

6.8. Thermal Conductivity Gauges

403

6.8.1. Theory

404

6.8.2. Calibration

406

6.8.3. Lowest Useful Pressure

408

6.8.4. Constant Pressure Pirani

409

6.8.5. Calibration Dependence Upon the Gas

410

6.8.6. Upper Pressure Limit

410

6.8.7. Ambient Temperature Compensation

411

6.8.8. Comparison of Pirani and Thermocouple Gauges

412

6.8.9. Stability

412

412

6.8.10. Thermistor Pirani Gauges and Integrated Transducers

6.8.11. Commercial Gauges and Applications

413

6.9. Ionization Gauges

414

414

6.9.1. Hot-Cathode Gauge Equation

6.9.2. Geometric Variations in the BayardAlpert Gauge

419

421

6.9.3. Modulated BayardAlpert Gauge

 

422

6.9.4. Extractor Gauge

6.9.5. Helmer Gauge

423

6.9.6. Long Electron Path Length Gauges

424

6.9.7. Secondary Standard Hot-Cathode Gauges

425

6.9.8. High-Pressure Ionization Gauges

426

6.9.9. Cold-Cathode Gauges

427

6.9.10. Ionization Gauge Accuracy

435

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6.9.11.

Gauge Constant Ratios for Different Gases

438

6.9.12.

Ionization Gauge Controllers

439

References

441

7. Partial Pressure Analysis Robert E. Ellefson

447

7.1. Ion Sources

447

7.1.1. Electron-Impact Ionization Process

448

7.1.2. Open Ion Source

449

7.1.3. Closed Ion Source

452

7.2. Ion Detection

454

7.2.1. Faraday Cup Ion Detection

454

7.2.2. Secondary Electron Multiplier Detection

454

7.2.3. Microchannel Plate Detector

456

7.3. Mass Analysis

456

7.3.1. Quadrupole Mass Analyzer

456

7.3.2. Magnetic Sector Analyzer

460

7.3.3. Time-of-Flight Mass Analyzer

464

 

7.3.4. Trochoidal (Cycloid) Mass Analyzer

465

7.3.5. Omegatron

466

7.4.

Optical Measurement of Partial Pressures

467

7.4.1. Photoionization Measurement of Partial Pressure

468

7.4.2. Infrared Absorption Measurement of Partial Pressure

469

7.5. Computer Control, Data Acquisition, and Presentation

470

7.6. Residual Gas Analysis

471

7.7. Pressure Reduction Sampling Methods for Vacuum Process Analysis

474

7.8. Calibration of Partial Pressure Analyzers

475

References

 

477

8. Leak Detection and Leak Detectors Werner Grosse Bley

481

8.1. Principles of Vacuum Leak Detection

482

 

8.1.1.

Types of Leaks and Leak Rate Units

482

8.2. Total Pressure Measurements

484

8.3. Partial Pressure Measurements

486

8.4. Measurement of Leakage Rates with Helium Leak Detectors

486

8.5. Helium Leak Detection of Vacuum Components

487

8.6. Helium Leak Detection of Vacuum Systems

490

8.7. Special Methods and Other Tracer Gases

493

8.8. Mass Spectrometer Leak Detectors

493

8.8.1. Mass Spectrometer System for Helium Leak Detection

494

8.8.2. Direct-Flow Helium Leak Detectors

494

8.8.3. Simple Counterflow Helium Leak Detectors

496

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8.8.4. Advanced Counterflow Helium Leak Detectors

498

8.8.5. Oil-Free and Dry Helium Leak Detectors

499

8.9.

Specifications of Mass Spectrometer Leak Detectors

500

8.10. Quantitive Leakage Rate Measurements

502

8.11. Mass Spectrometer Leak Detectors for Other Tracer Gases and Future Developments in Leak

504

 

Detection

References

505

9. High-Vacuum System Design Wolfgang Schwarz

507

9.1. Calculations of Vacuum Systems

507

 

9.1.1. Basic Pumpdown Equations

508

9.1.2. Process Pressure

511

9.2. Gas Loads in High-Vacuum Systems

513

 

9.2.1. Outgassing

513

9.2.2. Leaks

516

9.2.3. Permeation

516

9.2.4. Process Gas

518

9.3. Design of High-Vacuum Pump Sets

519

9.3.1.

Forepump sets

519

9.3.1.1. Fore-Vacuum Pumps

519

9.3.1.2. Roots Combinations

520

9.3.2.

High-Vacuum Pump Sets

524

9.3.2.1. Turbomolecular Pump Sets

526

9.3.2.2. Diffusion Pump Sets

528

9.3.2.3. Pump Sets with Cryosurfaces

531

9.3.2.4. Cryopump Sets

535

9.4. Calculation Methods for Vacuum Systems

537

9.4.1. Analytical Approximations

538

9.4.2. Numerical Methods

541

 

9.4.2.1. Dedicated Software

541

9.4.2.2. Network Approach

542

General References

546

10. GasSurface Interactions and Diffusion John B. Hudson

547

10.1. Adsorption

548

10.1.1. Basic Equations

548

10.1.2. Adsorption Isotherms

551

10.1.3. Heat of Adsorption

567

10.1.4. Observed Behavior

568

10.1.5. Adsorption Kinetics

572

10.1.6. Chemisorption Kinetics

575

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10.1.7. Kinetic Measurements

582

10.1.8. Capillarity Effects

584

10.2. Absorption

589

10.2.1. Equilibrium Solubility

590

10.2.2. Diffusion Rates

590

10.2.3. Kinetics of Absorption and Permeation

591

10.2.4. Steady-State Permeation

592

10.2.5. Transient Permeation

595

10.2.6. Effect of Desorption Kinetics on Permeation

600

10.3. Surface Chemical Reactions

606

10.4. Outgassing Behavior

614

10.4.1. Desorption of Adsorbed Gases

614

10.4.2. Dissolved Gases

616

10.4.3. Overall Pumpdown Curves

616

10.4.4. Mitigation of Outgassing

619

10.4.5. Surface Treatments During Construction

619

10.4.6.

In Situ Surface Treatments

620

10.4.7.

Bakeout Processes

620

References

622

11. Ultrahigh and Extreme High Vacuum Paul A. Redhead

625

11.1. Limits to the Measurement of UHV/XHV

628

11.1.1. Residual Currents

629

11.1.2. Effects at Hot Cathodes

636

11.1.3. Gauges with Long Electron Paths

639

11.1.4. Comparison of UHV/XHV Gauges

641

11.2. Limits to Pumps at UHV/XHV

642

11.2.1. Kinetic Pumps

642

11.2.2. Capture Pumps

643

11.2.3. Comparisons of Pumps for UHV/XHV

646

11.3. Leak Detection at UHV/XHV

647

11.4. Outgassing

648

11.4.1.

Reduction of Outgassing Rates

648

11.5. UHV/XHV Hardware

652

References

652

12. Calibration and Standards Karl Jousten

657

12.1. Primary Standards

658

12.1.1. Liquid Manometers and Piston Gauges

659

12.1.2. Static Expansion

661

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Page xxi

12.1.3. Continuous Expansion

665

12.1.4. Molecular Beam Expansion

670

12.2. Calibration by the Comparison Method

673

12.3. Calibration of Vacuum Gauges and Mass Spectrometers

676

12.3.1. Capacitance Diaphragm Gauges

676

12.3.2. Spinning Rotor Gauges

680

12.3.3. Ionization Gauges

683

12.3.4. Mass Spectrometers

686

12.4. Calibration of Test Leaks

689

12.5. Measurement of Pumping Speeds

692

References

695

Appendix

701

Graphic Symbols for Vacuum Components

701

Conversion Factors for Pressure Units

708

Vapor Pressure of Common Gases

709

Vapor Pressure of Solid and Liquid Elements

711

General Reference Books on Vacuum Science and Technology

714

Index

715

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Acronyms

Page xxiii

Acronyms used in the text are listed under the chapter where they occur.

Chapter 5 Part I. Getters and Getter Pumps

bcc

Body-centered cubic (crystal structure)

CCRT

Color cathode ray tube

CRT

Cathode ray tube

fcc

Face-centered cubic (crystal structure)

FED

Field emission display

hcp

Hexagonal close-packed (crystal structure)

HPTF

High-porosity thick film (getter)

HT

High temperature

HV

High vacuum

LN2

Liquid nitrogen

PDP

Plasma display panel

rf

Radio frequency

RT

Room temperature

SEM

Scanning electron microscope

UHV

Ultrahigh vacuum

Chapter 5 Part II. Sputter Ion Pumps

BA

BayardAlpert (gauge)

DI

Diode sputter ion pump with two cathode materials

FEM

Finite element method

HMF

High magnetic field (mode)

HP

High pressure (mode)

LMF

Low magnetic field (mode)

SIP

Sputter ion pump

TM

Transition (mode)

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UHV

Ultrahigh vacuum

VTP

Volume throughput

Chapter 5 Part III. Cryopumps

BET

BrunauerEmmettTeller (adsorption model)

GM

GiffordMcMahon (thermodynamic cycle)

Chapter 6

Vacuum Gauges

BAG

BayardAlpert gauge

CCD

Cold-cathode gauge

CDG

Capacitance diaphragm gauge

ESD

Electron-stimulated desorption

FS

Full scale

HCG

Hot-cathode gauge

JHP

Jauge haut pression (Choumoff gauge)

NIST

National Institute of Standards and Technology (USA)

PTB

Physikalisch-Technische Bundesanstalt (Germany)

QBG

Quartz helix Bourdon gauge

SCR

Silicon controlled rectifier

SRG

Spinning rotor gauge

UHV

Ultrahigh vacuum

XHV

Extreme high vacuum

Chapter 7 Partial Pressure Analysis

Page xxiv

AP

Appearance potential

CRDS

Cavity ringdown spectroscope

IP

Ionization potential

IR

Infrared

MCP

Microchannel plate

MS

Mass spectrometer

PPA

Partial pressure analyzer

QMS

Quadrupole mass spectrometer

rf

Radio frequency

RGA

Residual gas analyzer

SEM

Secondary electron multiplier

TOF

Time of flight

TOFMS

Time-of-flight mass spectrometer

UHV

Ultrahigh vacuum

XHV

Extreme high vacuum

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Chapter 11 Ultrahigh and Extreme High Vacuum

BA

BayardAlpert (gauge)

BAG

BayardAlpert gauge

ESD

Electron stimulated descorption

EXB

Cycloidal mass spectrometer

GIP

Getter-ion pump

MG

Magnetron gauge

IMG

Inverted magnetron gauge

MS

Mass spectrometer

MBAG

Modulated BayardAlpert gauge

NEG

Nonevaporable getter

RGA

Residual gas analyzer

SIP

Sputter-ion pump

TMP

Turbomolecular pump

TSP

Titanium sublimation pump

UHV

Ultrahigh vacuum

XHV

Extreme high vacuum

Chapter 12 Calibration and Standards

Page xxv

AVS

American Vacuum Society

CDG

Capacitance diaphragm gauge

DIN

German industry standard

DKG

German calibration service

IG

Ionization gauge

IMGC

Institutodi Metrologia ''G. Colonnetti" (Italy)

ISO

International Organization for Standards

NIST

National Institute of Standards and Technology (USA)

NPL

National Physical Laboratory (England)

NPL

National Physical Laboratory (India)

PTB

Physikalisch-Technische Bundesanstalt (Germany)

QBS

Quartz Bourdon spiral manometer

SI

Système Internationale

SRG

Spinning rotor gauge

UHV

Ultrahigh vacuum

XHV

Extreme high vacuum

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Page 1

1

Kinetic Theory of Gases

Benjamin B. Dayton

For a proper understanding of phenomena in gases, more especially at low pressures, it is essential to consider these phenomena from the point of view of the kinetic theory of gases [1]. This theory rests essentially upon two fundamental assumptions. The first of these postulates is that matter is made up of extremely small particles, which in the gaseous state at moderate temperatures are monatomic or polyatomic molecules and at higher temperatures may be entirely dissociated into atoms or even into positive ions and electrons to form a "plasma." The second postulate is that the molecules of a gas are in constant motion, and this motion is intimately related to macroscopic properties known as the temperature and pressure, which characterize the state of the gas in a given small region.

The center of mass of the molecule is assumed to move in a straight line (neglecting the force of gravity) with a constant velocity between collisions with other molecules, and the forces between molecules are negligible except when the molecular centers approach within a distance known as the mean molecular diameter. Velocity is a vector which must be measured with respect to some "fixed" reference frame. The magnitude of the velocity vector is called the speed of the molecule. In the "laboratory reference frame" the motion of the particles may be divided into bulk or fluid motion due to pressure or concentration gradients which generate mass flow or diffusive flow and the random velocity components associated with the concept of temperature as measured in a reference frame moving with the fluid flow velocity. Kinetic energy is proportional to the square of the molecular velocity and is a scalar quantity.

Foundations of Vacuum Science and Technology, Edited by James M. Lafferty. ISBN 0-471-17593-5 © 1998 John Wiley & Sons, Inc.

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Temperature is defined as a quantity proportional to the average (kinetic) energy of translation of the particles in a reference frame moving with any fluid flow at a given small region. In the case of monatomic molecules (such as those of the rare gases and the vapors of most metals), the effect of increased temperature is evidenced by increased translational energy of the molecules. In the case of diatomic and polyatomic molecules, an increase in temperature also increases through intermolecular collisions the rotational energy of the molecule about one or more axes, as well as vibrational energy of the constituent atoms with respect to mean positions of equilibrium. However, in the following discussion, only the effect on translational energy will be considered.

1.1

Ideal Gas Law

According to the kinetic theory, a gas exerts pressure on the enclosing walls because of the impact of molecules on these walls. Since the gas suffers no loss of energy through exerting pressure on the stationary solid wall of its enclosure, it follows that each molecule is thrown back from the wall with the same speed as that with which it impinges, but in the reverse direction with respect to the normal; that is, the impacts are perfectly elastic.

Suppose a molecule of mass m to approach a flat wall surface lying in the x, y plane with velocity component vz perpendicular to the wall. Since the molecule rebounds with the same speed, the change of momentum per impact is 2mvz. If molecules strike unit area in unit time with velocity component vz, the total impulse exerted on the unit area per unit time is 2mvz . But the pressure, P, on a wall is defined as the rate at which momentum is imparted to a unit area of surface. Hence,

which momentum is imparted to a unit area of surface. Hence, where the summation is over

where the summation is over all values of vz and it is assumed that all molecules have the same mass m.

It now remains to calculate . Of all the molecules within a volume V extending outward from a small area, x y, of the wall by a distance |vzdt|, where dt is a short interval of time, at equilibrium only one half of the molecules will be moving with velocity components vz toward the wall. Let nz denote the number of molecules per unit volume in the gas within V that have a velocity component of either vz or vz. Then the flux rate against the wall will be = nz z/2, and Eq. (1.1) becomes

the wall will be = nz z /2, and Eq. (1.1) becomes The total speed of

The total speed of a molecule with velocity components vx, vy, and vz is the square root of the quantity

vx , vy , and vz is the square root of the quantity Defining the averages

Defining the averages

, vy , and vz is the square root of the quantity Defining the averages <

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Page 3

where n is the total number of molecules per unit volume regardless of velocity components, we have by symmetry

regardless of velocity components, we have by symmetry and Then from Eq. (1.2) the basic equation

and

regardless of velocity components, we have by symmetry and Then from Eq. (1.2) the basic equation

Then from Eq. (1.2) the basic equation for the pressure is

Then from Eq. (1.2) the basic equation for the pressure is where denotes the gas density,

where denotes the gas density, Eq. (1.6) can be expressed in the form

the gas density, Eq. (1.6) can be expressed in the form which shows that, at constant

which shows that, at constant temperature, the pressure varies directly as the density, or inversely as the volume. This is known as Boyle's law.

Now it is a fact that no change in temperature occurs if two different gases, originally at the same temperature, are mixed. This result is valid independently of the relative volumes. Consequently, the average kinetic energy of the molecules must be the same for all gases at any given temperature, and the rate of increase with temperature must be the same for all gases. We may therefore define temperature in terms of the average kinetic energy per molecule, and this suggestion leads to the relation

per molecule, and this suggestion leads to the relation for each of the three degrees of

for each of the three degrees of freedom of translational motion, where T is the absolute temperature (degrees Kelvin), defined by the relation T = 273.15 + t (t = degrees Centigrade), and k is a universal constant, known as the Boltzmann constant. The total mean translational energy is then

constant . The total mean translational energy is then where r is known as the root-mean-square

where r is known as the root-mean-square velocity. The total kinetic energy of the molecules in a volume V will be

kinetic energy of the molecules in a volume V will be Combining Eq. (1.8) with (1.5)

Combining Eq. (1.8) with (1.5) it follows that Boyle's law can be expressed in the form

it follows that Boyle's law can be expressed in the form where the units chosen must

where the units chosen must be consistent with either the cgs system or the SI system. When n is expressed as molecules/cm3 and k is in erg/K, then P will be the pressure in

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dyne/cm2. Also, from Eq. (1.6) and Eq. (1.11), it follows that

Page 4

Also, from Eq. (1.6) and Eq. (1.11), it follows that Page 4 which is known as

which is known as Charles' law or Gay-Lussac's law.

Lastly, let us consider equal volumes of any two different gases at the same values of P and T. Since P and V are

at the same values of P and T . Since P and V are respectively the

respectively the same for each gas, and

that n must be the same for both gases. That is, equal volumes of all gases at any given values of temperature and pressure contain an equal number of molecules. This was enunciated as a fundamental principle by Avogadro in 1811, but it took about 50 years for chemists to understand its full significance.

is constant at constant value of T, it follows from Eqs. (1.10) and (1.11)

On the basis of Avogadro's law the molecular mass, M, of any gas or vapor is defined as that mass in grams, calculated for an ideal gas, which occupies, at 0°C and 1 atmosphere, a volume [2]

V0 = 22,414.10 cm3.

This is therefore designated the molar volume, and the equation of state for an ideal gas can be written in the form

of state for an ideal gas can be written in the form where W is the

where W is the mass in grams, M is the molecular mass in grams, and R0 is a universal constant in units which depend on the choice of units for the volume V, the pressure P, and the absolute temperature T. It is then convenient to express Eq. (1.14) in the form

T . It is then convenient to express Eq. (1.14) in the form where nM denotes

where nM denotes the number of moles (corresponding to M in grams) in the volume V under the given conditions of temperature and pressure.

Excellent summaries of the various proposals prior to 1967 regarding the unit of pressure to be used in vacuum science and technology have been given by Thomas and Leyniers [3]. When the units of length [l], mass [m], and time [t] are chosen for the three basic units of a coherent system, the pressure unit is expressed by

[p] = [l]1 [m][t]2

or by

[p] = [F][l]2,

where F is the force with dimensions [l][m][t]2. In the cgs system the unit of force is the dyne and the pressure unit is 1 dyne/cm2. In the MKS or SI system the unit of

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Page 5

force is the newton (abbreviated N), defined as 1 kg · m · s2 and the pressure unit is 1 N · m2. In 1962 the French government approved the term "pascal" (abbreviated Pa) for the newton per square meter [4], and this term was officially adopted by the International Standards Organization in 1978 while deprecating the use of older pressure units such as mmHg and the torr (or Torr) [5]. Decimal multiples and submultiples of the Pa are accepted, and some have special nomenclature such as

1 bar = 105 Pa,

1 millibar (mbar) = 100 Pa.

The previously used unit of 1 microbar (µbar) = 106 bar for the dyne/cm2 equals 101 Pa or 7.5 × 104 Torr. The main reason for now using the mbar in vacuum technology is that its value is close to that of the Torr and the mmHg, which were used for many years in the vacuum industry and the scientific literature. In 1954 both the British [6] and American Committees on Vacuum Nomenclature [7] recommended replacing the mmHg by the Torr, defined as exactly 1,013,250/760 dyne/cm2, thus making it independent of the changing values for the measured density of mercury and the acceleration of gravity. The term torr had previously been used in the German literature as a substitute for mmHg, and at the First International Congress on Vacuum Techniques in Belgium in 1958 the newly defined Torr was favored by the Germans and the Americans while the pascal was favored by the Belgians and the French representatives [8]. The Torr then became widely used throughout the world except in France until 1978, when the International Standards Organization deprecated the use of Torr and defined the standard atmosphere as exactly 101,325 Pa and recommended the pascal. Thus

as exactly 101,325 Pa and recommended the pascal. Thus In practical use the conventions of 1

In practical use the conventions of 1 Torr = 133.322 Pa and 1 Torr = 1333.22 µbar are sufficient. It may be noted that the Torr is not identical to the unit mmHg used prior to 1955 which is based on the equation

unit mmHg used prior to 1955 which is based on the equation where = 13.5951 g/cm3

where = 13.5951 g/cm3 (at 0°C) is the density of mercury, g = 980.665 cm/s2 was the standard acceleration of gravity accepted at that time, and h is the height (in mm) of a mercury column in a tube above some reference point such as the surface of the mercury in the reference tube of a U-tube manometer or a McLeod gauge. One bar = 750.06 mmHg. Another unit no longer used is the micron = 103 mmHg.

The basic unit of volume in the cgs system is 1 cm3, and that in the MKS or SI system is 1 m3. Following the Twelfth Conférence Général des Poids et Mesures in 1964 the liter (or litre) is defined as 1 dm3 or 103 cm3 or 103 m3. The preferred abbreviation for the liter is L, but l and the script l have been used. In the United States the volume unit associated with industrial vacuum chambers and gas flow through mechanical pumps is commonly the cubic foot, which equals 28.316847 liter. The basic unit of mass in the cgs system is the gram (g), and that in the MKS system is

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Page 6

the kilogram (kg). The pound avoirdupois is seldom used for mass, but the pound force (poundf) is used in industrial engineering in connection with the pressure unit pound per square inch (lb/in2.). 1 lb/in2. = 0.0689476 bar or 6.89476 kPa.

Units of temperature are the Celsius degree (°C) (also known as the degree centigrade) and the degree Kelvin (K) on the absolute or thermodynamic scale. The zero of the Kelvin scale is 273.15°C, so that temperature T (in K) = temperature t (in °C) + 273.15. The Fahrenheit temperature scale is seldom used in vacuum physics.

From the equation of state for an ideal gas we obtain the following values for the universal gas constant R0:

R0

= 760 · 22.41383/273.15 = 62.3632 Torr · L · K1 · mol1

= 1013250 · 22414.10/273.15 = 8.314511 · 107 erg · K1 · mol1

= 8.314511 joule · K1 · mol1

= 8.314511/4.1840 = 1.9872 cal (thermochemical) K1 · mol1.

In dealing with gases at low pressures, it is convenient to express the quantity of gas (Q = PV) in Pa · m3 at standard room temperature 23°C. Note that 1 Torr · L = 0.133322 Pa · m3. The quantity of gas thus defined flowing per unit time through a given cross section of a pipe has been called the throughput in the British and American Glossaries of terms used in vacuum technology [9].

The unit of throughput is then

1 Pa · m3 · s1 = 1 N · m · s1 = 1 J · s1 = 1 W.

Objections have been raised against the use of pressurevolume products for quantity of gas on the basis that the temperature of the walls of a vacuum system is not always clearly specified, and the suggestion is made that flow of gas should preferably be expressed in mol/s to avoid any ambiguity due to unspecified temperatures [10]. The term throughput should be reserved for flow in Pa · m3 · s1 at some specified temperature, such as a "standard" room temperature of 23°C, and a term such as molar flow rate should be used for flow in mol · s1. Then

1 mol · s1 = 8.31451 × 296.15 Pa · m3 · s1 = 2462.342 Pa · m3 · s1 at 23°C.

1.2

Avogadro's Number

Avogadro's law states that the number of molecules per gram-molecular mass is a constant, which is designated NA. Although a number of different methods have been used for the determination of this constant, the most accurate method depends upon the determination of both the Faraday (F) and the charge of the electron (e).

For the deposition of one gram-equivalent the most accurate value [2] is

F = 96,485.309 absolute coulombs.

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Page 7

Assuming that each univalent ion has a charge equal in magnitude to that of one electron,

NA = F/e.

The value of the charge of the electron is

e

= 4.8032068 · 1010 absolute esu

= 1.60217733 · 1019 absolute Coulomb

since 1 absolute Coulomb = 1/10c times the charge in esu absolute coulombs, where c = velocity of light = 2.99792458 · 108 m · s1. Hence

NA = 6.0221367 × 1023 mol1.

From Eqs. (1.11) and (1.15) it follows that for one mole of gas in the volume V, nM = 1 and n = NA/V so that

of gas in the volume V , nM = 1 and n = NA/V so that

From Eq. (1.9) it also follows that the average kinetic energy per molecule is given by

that the average kinetic energy per molecule is given by The mass per molecule is evidently

The mass per molecule is evidently

per molecule is given by The mass per molecule is evidently From Eq. (1.11) it follows

From Eq. (1.11) it follows that the number of molecules per cubic centimeter is given by

the number of molecules per cubic centimeter is given by where P µb is the pressure

where Pµb is the pressure in microbars and PPa is the pressure in pascal units, while

microbars and P Pa is the pressure in pascal units, while where P is the pressure

where P is the pressure in Torr.

Table 1.1 gives values of n for a series of values of T, Pµb, PPa and P (Torr). The value n = 2.687 × 1019 cm3 is known as the Loschmidt number.

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Table 1.1. Number of Molecules per Cubic Centimeter

Page 8

T(°K)

Pµb

PPa

P

n

273.15

 

1.01325 × 106

1.01325 × 105

760

2.687 × 1019

298.15

 

1.01325 × 106

1.01325 × 105

760

2.461 × 1019

273.15

 

1.333 × 103

1.333 × 102

1

3.535 × 1016

298.15

 

1.333 × 103

1.333 × 102

1

3.239 × 1016

273.15

 

10

1

7.50 × 103

2.652 × 1014

298.15

 

10

1

7.50 × 103

2.429 × 1014

273.15

 

1

0.1

7.50 × 104

2.652 × 1013

298.15

 

1

0.1

7.50 × 104

2.429 × 1013

1.3

Molecular Collisions; Mean Free Path; MaxwellBoltzmann Distribution Laws

It is evident that there must be a nonuniform distribution of velocities among all the molecules in a given volume because of the constant occurrence of collisions. In an elementary treatment of the collision process the two molecules are assumed to be solid spheres of mass m1 and a well-defined diameter 1 for one molecule and m2 and 2 for the second molecule. The collisions are assumed to be elastic; that is, no translational kinetic energy is lost by excitation of molecular rotation or atomic vibrations or by excitation of molecular vibrations when one of the molecules is part of the wall of the enclosure. While the molecular diameters on impact can only be defined in terms of the fields of attractive and repulsive force around each molecule and the relative momenta, it is assumed for simplicity that 1 and 2 have fixed values. The distance between centers on impact will then be

values. The distance between centers on impact will then be and the mutual collision cross section

and the mutual collision cross section is defined as

be and the mutual collision cross section is defined as If we consider a single molecule

If we consider a single molecule of diameter 1 (cm) moving at high speed, v, through a gas composed only of molecules of diameter 2 (cm) moving relatively slowly and having a concentration of n molecules per cm3, then it is obvious that the average distance (in cm) between collisions, known as the mean free path, will be given by

collisions, known as the mean free path , will be given by and the collision rate

and the collision rate will be v/Lc = n cv.

In an actual gas at equilibrium where all molecules have random velocities with an average speed va, the mean speed of a first molecule relative to one of the other molecules depends on the angle between their respective directions of motion and the distribution law for molecular velocities and will be equal to 21/2va in a homogeneous

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gas as calculated by Maxwell [11]. The collision rate is therefore

calculated by Maxwell [11]. The collision rate is therefore and the mean free path in a

and the mean free path in a homogeneous maxwellian gas is

Page 9

mean free path in a homogeneous maxwellian gas is Page 9 where in this case 1

where in this case 1 = 2 = and c = 2. This quantity is of fundamental importance in vacuum physics since the Knudsen number defined by the ratio

physics since the Knudsen number defined by the ratio where Dc is a characteristic length in

where Dc is a characteristic length in the vacuum system, such as the diameter of a cylindrical tube, determines the physics of the gas flow through tubes and ducts. From Eq. (1.11) and Eq. (1.26) in cgs units we obtain

ducts. From Eq. (1.11) and Eq. (1.26) in cgs units we obtain and for nitrogen [12]

and for nitrogen [12] we have = 3.78 × 108 cm, giving

and for nitrogen [12] we have = 3.78 × 108 cm, giving At T = 298

At T = 298 K and P = 103 Torr, this gives a mean free path for nitrogen L = 4.92 cm. At this temperature and Pµb = 1 µbar = 0.1 Pa = 7.5 × 104 Torr, L = 6.56 cm. This pressure is regarded as the upper limit of the high vacuum region [13] in which the molecules may collide with the walls of the vacuum device more frequently than with other molecules in the gas phase. We therefore must also consider the case in which a molecule of the gas collides with a molecule which is part of the wall.

In the laboratory reference frame the velocity vector for the first molecule before the collision may be represented as

first molecule before the collision may be represented as and for the second molecule it may

and for the second molecule it may be expressed as

as and for the second molecule it may be expressed as where u 1 and u

where u1 and u2 are the velocity components perpendicular to the line of centers at the time of impact while v1 and v2 are the velocity components along this line of centers before collision as shown in Fig. 1.1.

Similarly, after the collision the velocity vectors for the first and second molecules, respectively, may be represented by

after the collision the velocity vectors for the first and second molecules, respectively, may be represented

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< previous page page_10 next page > Fig. 1.1 Velocity components in elastic collision between spheres.

Fig. 1.1 Velocity components in elastic collision between spheres.

Page 10

where V1 and V2 are the respective velocity components along this line of centers after the collision, while U1 and U2 are the respective velocity components perpendicular to this line of centers after the moment of collision. For a collision to take place, v1 and v2 must be antiparallel with vectors directed toward each other; but if they are parallel, one velocity component must be greater than the other, and the relative positions, must be such that the molecule with the larger component overtakes the other molecule in this direction.

The conservation of linear momentum in elastic collisions requires

of linear momentum in elastic collisions requires Also, for the momentum components we require The

Also, for the momentum components we require

elastic collisions requires Also, for the momentum components we require The conservation of translational energy requires

The conservation of translational energy requires

elastic collisions requires Also, for the momentum components we require The conservation of translational energy requires

since u1 and v1 are orthogonal components. Similarly,

since u 1 and v 1 are orthogonal components. Similarly, < previous page page_10 next page

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From Eqs. (1.36), (1.37), (1.38), and (1.39) we have

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From Eqs. (1.36), (1.37), (1.38), and (1.39) we have Page 11 Also, from Eqs. (1.34) and

Also, from Eqs. (1.34) and (1.36) we obtain

we have Page 11 Also, from Eqs. (1.34) and (1.36) we obtain Dividing Eq. (1.40) by

Dividing Eq. (1.40) by Eq. (1.41) gives

and (1.36) we obtain Dividing Eq. (1.40) by Eq. (1.41) gives Combining Eq. (1.42) and Eq.

Combining Eq. (1.42) and Eq. (1.43), we obtain

(1.41) gives Combining Eq. (1.42) and Eq. (1.43), we obtain and similar calculations give Equations (1.44)

and similar calculations give

and Eq. (1.43), we obtain and similar calculations give Equations (1.44) and (1.45) together with Eq.

Equations (1.44) and (1.45) together with Eq. (1.36) give the vector components after the collision in terms of the components before the collision. If m1 = m2, then V1 = v2 and V2 = v1 so that the velocity components along the line of centers are interchanged. The resultant speeds after the collision are then

The resultant speeds after the collision are then If the initial velocity component v 2 was

If the initial velocity component v2 was greater than v1, then the collision will cause the first molecule to increase in velocity and the second molecule will suffer a decrease in velocity.

To illustrate how some molecules can acquire very high velocities while others are brought to near zero velocity as a result of collisions, we consider a special class of orthogonal collisions between like molecules in which the first molecule has an initial velocity u1 orthogonal to the line of centers at impact while the second molecule has an initial velocity v2 parallel to this line of centers. In this special case we have v1 = 0, u2 = 0, V1 = v2, V2 = 0, U2 = 0 and the resultant velocity of the second molecule is zero while the speed of the first molecule after the collision has been increased from u1 to W1 as given by Eq. (1.46). Note that we could have assumed the second molecule to have any value of a velocity component u2 other than zero orthogonal to

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the line of centers, but this component would have no effect on the final velocity of the first molecule as given by Eq.

(1.46).

If we consider only orthogonal collisions in which the first molecule is repeatedly struck in successive collisions by one of the other molecules with a velocity component v2 which is a constant equal to the most probable velocity, vm, and assume that the initial u1 = vm also, then N successive orthogonal collisions would give a final speed

N successive orthogonal collisions would give a final speed By a process of reasoning similar to

By a process of reasoning similar to that for calculating the rate of absorbtion of a molecular beam by scattering in a gas [14], it can be shown that the probability of N + 1 or more successive orthogonal collisions, without collisions of another type, is

collisions, without collisions of another type, is which is the probability that the speed of m

which is the probability that the speed of m1 is equal to or greater than W1(0 < W1 < ), where b is a constant to be determined. When N is large, the velocity W1 can be much greater than vm but the probability is quite small. This resembles the actual distribution law for molecular speeds as determined by J. C. Maxwell and L. Boltzmann.

The form of the distribution law differs according to the particular type of velocity distribution of interest. If we let

type of velocity distribution of interest. If we let designate the components, along the three coordinate

designate the components, along the three coordinate axes, of the randomly directed velocity v, then

coordinate axes, of the randomly directed velocity v , then and the distribution function, with respect

and the distribution function,

directed velocity v , then and the distribution function, with respect to, say, is given by

with respect to, say,

, then and the distribution function, with respect to, say, is given by the relation where

is given by the relation

function, with respect to, say, is given by the relation where N = number of molecules

where N = number of molecules in the volume under consideration.

The distribution function for all three components of v has the form

function for all three components of v has the form With respect to the polar coordinates

With respect to the polar coordinates and , we have

With respect to the polar coordinates and , we have The most important distribution function is

The most important distribution function is that with respect to v in a random direction, which is given by the relation

Differentiating fv with respect to v , it is observed that the maximum value occurs

Differentiating fv with respect to v, it is observed that the maximum value occurs for

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< previous page page_13 next page > Page 13 Hence corresponds to the value of the

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Hence corresponds to the value of the most probable velocity, which is given by the relation

the most probable velocity , which is given by the relation In terms of c =

In terms of c = v/ , we can express Eq. (1.53) in the form

of c = v / , we can express Eq. (1.53) in the form where c

where c varies from 0 to , and dy (= fcdc) corresponds to the fraction of the total number of molecules which have values of c ranging between c and c + dc. Hence

have values of c ranging between c and c + dc . Hence From Eq. (1.57)

From Eq. (1.57) we derive the value of the arithmetical average velocity, va = ca, where

of the arithmetical average velocity , va = ca , where and, using Eq. (1.55), we

and, using Eq. (1.55), we obtain

, va = ca , where and, using Eq. (1.55), we obtain The root-mean-square velocity ,

The root-mean-square velocity, vr, corresponds to the square root of the average value of v2 as derived from Eq. (1.9) and is therefore given by the relation

from Eq. (1.9) and is therefore given by the relation The second column in Table 1.2

The second column in Table 1.2 gives values of fc for a series of values of c, and Fig. 1.2 shows a plot of these data, on which the values of fc are indicated for the values c = 1, 1.1284, and 1.2247, respectively.

a plot of these data, on which the values of fc are indicated for the values

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< previous page page_14 next page > Page 14 Fig. 1.2 Plots illustrating Maxwell-Boltzmann distribution laws.

Fig. 1.2 Plots illustrating Maxwell-Boltzmann distribution laws. Plot fc shows distribution function for random velocity, c expressed in terms of the most probable velocity ; plot fx shows distribution function for energy, E, in terms of x = E/(kT); y corresponds to the fraction of the total number of molecules for which the random velocity (expressed in terms of ) is less than or equal to a given value c.

gives the fraction of the total number of molecules which have a random velocity equal to or less than that corresponding to the value c, or to v = c. The third and fourth columns in Table 1.2 show values of y and of y, where y gives the fraction of the total number which have velocities (in terms of