Chemistry and Technology of Lubricants

318 Pages·1994·8.606 MB·English

by  R. J. Prince (auth.), Dr. R. M. Mortier, Dr. S. T. Orszulik (eds.)

Chemistry and TechnologyofLubricants
Chemistry and Technology of
Lubricants
Edited by
R.M. MORTIER
Technology Development Manager
and
S.T.ORSZULlK
Senior Technologist
Castrol Ltd
Reading
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
First edition 1992
Reprinted 1993, 1994
(t) 1994 Springer Science+Business Media Dordrecht
Originally published by Chapman & HaU in 1994
Softcover reprint of the hardcover 1s t edition 1994
ISBN 978-1-4613-6578-5 ISBN 978-1-4615-3554-6 (eBook)
DOI 10.1007/978-1-4615-3554-6
Apan from any fair dealing for the purposes of research or private study, or
criticism or review, as permitted under the UK Copyright Designs and Patents
Act, 1988, this publication may not be reproduced, stored, or transmitted, in
any form or by any means, without the prior permission in writing of the
publishers, or in the case of reprographic reproduction only in accordance with
the terms of the licences issued by the Copyright Licensing Agency in the UK,
or in accordance with the terms of licences issued by the appropriate
Reproduction Rights Organization outside the UK. Enquiries conceming
reproduction outside the terms stated here should be sent to the publishers at
the Glasgow address printed on this page.
The publisher makes no representation, express or implied, with regard to
the accuracy of the information contained in this book and cannot accept any
legal responsibility or Iiability for any errors or omissions that may be made.
A catalogue record for this book is available from the British Library
Library of Congress Cataloging-in-Publication data available
Preface
The use oflubricants began inancient times and hasdeveloped into amajor
international business through the need to lubricate machines ofincreasing
complexity. The impetus for lubricantdevelopment has arisen from need, so
lubricatingpracticehasprecededanunderstandingofthescientificprinciples.
This is not surprising as the scientific basis ofthe technology is, by nature,
highly complex and interdisciplinary. However, we believe that the under
standing of lubricant phenomena will continue to be developed at a mol
ecular level to meet future challenges. These challenges will include the
control of emissions from internal combustion engines, the reduction of
friction and wear in machinery, and continuing improvements to lubricant
performanceand life-time.
More recently, there has been an increased understanding ofthe chemical
aspects oflubrication, which has complemented the knowledge and under
standing gained through studies dealing with physics and engineering. This
book aims to bring together this chemical information and present it in a
practical way. It is written by chemists who are authorities in the various
specialisations within the lubricating industry, and is intended to be of
interest to chemists who may already be working in the lubricatingindustry
or in academia, and who are seeking a chemist's view oflubrication. It will
also be of benefit to engineers and technologists familiar with the industry
who requireamorefundamental understandingoflubricants.
Throughout the book the range ofuses ofliquid lubricants, the base fluid
types, and the various classes of additives available are covered. In the
chaptersonlubricanttechnology, theauthorshavebeengiven the opportun
itytodraw on theirextensiveindustrialexperience. Although ithas not been
possibleto coverallaspectsofsucha broad subject,theaim is to providean
insight into the more important aspects of the chemistry of lubricants,
together with an indication of how lubricants are formulated to meet the
needsoflubricationtechnology.
We wouldlike toexpressourthanks to theauthorsfor theircontributions
andfor theirpatienceduringtheeditingprocess.Theadditionalcontribution
by Tony Lansdown after the very late withdrawal ofone ofour authors is
particularlyappreciated.Thanksarealsodueto thepublishersfor thelayout
of the book and for guiding us through the editing. Finally, we would
welcomecomments,criticismsandsuggestions.
R.M.M.
S.T.a.
Contributors
MrC.I.Betton Castrol Research Laboratories, Whitchurch Hill,
Pangbourne, ReadingRG8 7QR,UK
MrM.Brown ICI Chemicals and Polymers Ltd, Wilton, Cleveland
TS68JE,UK
MrB.H.Carter Castrol Research Laboratories, Whitchurch Hill,
Pangbourne,ReadingRG8 7QR, UK
Mre.e.Colyer The Lubrizoi Corporation, 29400 Lakeland Blvd,
Wickliffe,Ohio,44092,USA
DrJ.Crawford Adibis, 36/44High Street, Redhill, Surrey RHI lRW,
UK
ProfessorD.Dowson DepartmentofMechanicalEngineering,Universityof
Leeds,Leeds LS29JT,UK
MrW.e.Gergel The Lubrizol Corporation, 29400 Lakeland Blvd,
Wickliffe,Ohio,44092,USA
MrG.Gow AB Axel Christiernsson, PO Box 19, S-44041 Nol,
Sweden
MrT.J.Hoyes Castrol Research Laboratories, Whitchurch Hill.
Pangbourne,ReadingRG8 7QR,UK
ProfessorC.Kajdas Technical University of Radom, ul. Malczewskiego
29,26-600Radom, Poland
DrA.R.Lansdown 10HavergalClose,Caswell,SwanseaSA)4RL,UK
Dre.M.Lindsay Castrol Research Laboratories, Whitchurch Hill,
Pangbourne,ReadingRG8 7QR,UK
viii CONTRIBUTORS
MrA.J.Mills Castrol Research Laboratories, Whitchurch Hill,
Pangbourne,Reading RG8 7QR,UK
DrR.M.Mortier Castrol Research Laboratories, Whitchurch Hill,
Pangbourne,Reading RG8 7QR,UK
DrS.T.Orszulik Castrol Research Laboratories, Whitchurch Hill,
Pangbourne,Reading RG8 7QR,UK
MrR.J.Prince . Castrol Ltd,SwindonSN3 1RE, UK
DrA.Psaila OIS Research Laboratory, Adibis, Saltend, Hedon,
HullHUl28DS,UK
DrS.J.Randles ICI Chemicals and Polymers Ltd, Wilton, Cleveland
TS68JE, UK
DrM. Rasberger Ciba-Geigy Ltd, Additives Division AD7.1, Building
R-I032.4.58,CH-4002,Basle,Switzerland
MrR.L.Stambaugh Rohm and Haas, Research Laboratories, 727 Norris
town Road,Springhouse,Philadelphia, 19477,USA
DrP.M.Stroud ICI Chemicals and Polymers Ltd, Wilton, Cleveland
TS68JE, UK
Contents
Introduction xv
D. DaWSON
1 Baseoilsfrom petroleum 1
R.J. PRINCE
1.1 Introduction 1
1.2 Baseoilcomposition 2
1.2.1 Componentsofcrudeoil 2
1.2.2 Characteristicsofthehydrocarbonsforlubricantperformance 4
1.2.3 Crudeoilselectionforbaseoilmanufacture 5
1.3 Productsandspecifications 6
1.3.1 Physicalproperties 7
1.3.2 Chemicalproperties 11
1.3.3 Baseoilcategories 12
1.4 Conventionalbaseoilmanufacturingmethods 13
1.4.1 Historicmethods 13
1.4.2 Baseoilmanufactureinamodernrefinery 14
1.4.3 Baseoilproductioneconomics 16
1.4.4 Distillation 17
1.4.5 De-asphalting 19
1.4.6 Solventextraction 20
1.4.7 Solventde-waxing 22
1.4.8 Finishing 23
1.5 Moderncatalyticprocesses 25
1.5.1 Severehydrotreatment 25
1.5.2 Specialbaseoilsfromhydrocracking 26
1.5.3 Specialbaseoilsbywaxisomerisation 28
1.5.4 Catalyticde-waxing 29
1.6 Futuredevelopments 30
References 31
2 Syntheticbasefluids 32
S.J. RANDLES, P.M. STROUD, R.M. MORTIER, S.T. ORSZULIK,
T.J. HaYESand M. BROWN
2.1 Introduction 32
2.2 Polyalphaolefins 33
2.2.1 Freeradicaloligomerisation 33
2.2.2 Zieglercatalysedoligomerisation 33
2.2.3 Friedel-eraftscatalysedoligomerisation 34
2.3 Alkylatedaromatics 37
2.3.1 Introduction 37
2.3.2 Productionandgeneralproperties 37
2.3.3 Applications 38
x CONTENTS
2.4 Polybutenes 39
2.4.1 Introduction 39
2.4.2 Productionandgeneralchemicalproperties 39
2.4.3 ApplicationofPIBfluids 40
2.5 Syntheticesters 40
2.5.1 Introduction 40
2.5.2 Estertypes 40
2.5.3 Manufactureofesters 41
2.5.4 Physicochemicalpropertiesofesterlubricants 41
2.5.5 Applicationareas 48
2.5.6 Futuretrends 50
2.6 Polyalkyleneglycols 51
2.6.1 Introduction 51
2.6.2 Production 51
2.6.3 Chemistry 52
2.6.4 Keyproperties 53
2.6.5 Applications 54
2.7 Phosphateesters 58
2.7.1 Introduction 58
2.7.2 Manufacture 58
2.7.3 Physicalandchemicalproperties 59
2.7.4 Applications 60
References 60
3 Detergents/dispersants 62
C.c. COLYER and w.e. GERGEL
3.1 Introduction 62
3.2 Detergents 63
3.2.1 Sulfonates 64
3.2.2 Phenates/salicylates/phosphonates 68
3.2.3 Detergentclassification 70
3.3 Dispersants 72
3.4 Otherlubricants 77
3.4.1 Automatictransmissionfluids(ATFs) 77
3.4.2 Gearlubricants 78
3.4.3 Tractorhydraulicoils 78
3.5 Performanceevaluation 78
References 80
Furtherreading 80
4 Oxidativedegradationandstabilisationofmineraloilbased
lubricants 83
M. RASBERGER
4.1 Introduction 83
4.2 Autoxidationofhydrocarbons 83
4.2.1 Oxidationofhydrocarbonsatlowtemperature(30-120°C) 83
4.2.2 Oxidationofhydrocarbonsathightemperature(>120°C) 88
4.2.3 Metalcatalysedautoxidationofhydrocarbons 91
4.3 Oxidationstabilityofbaseoils 93
4.4 Inhibitionofoxidativedegradationoflubricants 94
4.4.1 Radicalscavengers 94
4.4.2 Hydroperoxidedecomposers 100
4.4.3 Multifunctionaladditives 104
4.4.4 Synergismbetweenantioxidants 108
CONTENTS xi
4.5 Applicationofantioxidants 109
4.5.1 Industriallubricants 109
4.5.2 Engineoil 114
4.6 Futureantioxidanttechnology 120
4.6.1 Antioxidantsforindustriallubricants 120
4.6.2 Antioxidantsforengineoils 121
Acknowledgements 121
References 122
5 Viscosityindeximproversandthickeners 124
R.L. STAMBAUGH
5.1 Introduction 124
5.2 OverviewofVIimproverchemistry 125
5.3 ChemistryandmanufactureofcommercialVIimprovers 126
5.3.1 Polymethacrylates 126
5.3.2 Olefincopolymers 128
5.3.3 Hydrogenatedstyrene-dienecopolymers 132
5.3.4 Styrenepolyester 134
5.3.5 Concentrate-compatiblePMAjOCPblends 134
5.4 Functionandproperties 135
5.4.1 Solutionproperties 135
5.4.2 Mechanismoffunction 138
5.4.3 Shearstability 140
5.4.4 Thermal-oxidativestability 147
5.5 Performance 149
5.5.1 Lowtemperatureviscosity 150
5.5.2 Hightemperatureviscosity 151
5.5.3 Deposits 154
5.6 Prognosisforfuturedevelopments 155
References 156
6 Miscellaneousadditives 160
J. eRAWFORDandA. PSAILA
6.1 Frictionmodifiers 160
6.1.1 Introduction 160
6.1.2 Frictionandlubricatingregimes 160
6.1.3 Frictionmodifiermechanisms 161
6.1.4 Chemicalaspectsoffrictionmodifiers 165
6.2 Pourpointdepressants 165
6.2.1 Lowtemperatureoperations 165
6.2.2 Mechanismofpourpointdepressants 166
6.2.3 Pourpointdepressantadditives 166
6.3 Demulsifiersandantifoams 168
6.3.1 Introduction 168
6.3.2 Emulsionstabilisation 168
6.3.3 Demulsification 168
6.3.4 Demulsifiers 169
6.3.5 Foamstability 169
6.3.6 Antifoams 170
6.3.7 Foamstudies 170
6.4 Corrosioninhibitors 170
6.4.1 Theprocessofcorrosion 171
6.4.2 Corrosioninhibitors 171
6.4.3 Corrosiontesting 173
Reference 173