Polymer bonding and adhesion on aluminium and magnesium alloys

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(1)Polymer bonding and adhesion on aluminium and magnesium alloys - F.M. de Wit. ISBN 978-90-77172-84-1. Polymer bonding and adhesion on aluminium and magnesium alloys. Uitnodiging voor het bijwonen van de openbare verdediging van mijn proefschrift:. Polymer bonding and adhesion on aluminium and magnesium alloys. op maandag 5 november 2012 om 15.00 uur. De promotie zal plaatsvinden in de Senaatszaal van de Aula van de Technische Universiteit Delft aan de Mekelweg 5, Delft. F.M. de Wit. Aansluitend op de promotieplechtigheid wordt een receptie gehouden, ook in de Aula.. Frederik de Wit.

(2) Propositions, part of the thesis: Polymer bonding and adhesion on aluminium and magnesium alloys 1. Without chemical bonding, adhesion cannot exist. 2. Contrary to what is usually assumed, the quality of adhesion of coatings on metal substrates is mainly determined by the local (oxide) composition of the substrates. 3. Improving adhesion on metals through roughening is not due to “mechanical interlocking”, but mainly because removing the top layer creates a fresh oxide and removes organic contamination. A.F. Harris, A. Beevers, International Journal of Adhesion and Adhesives 1999, 19, 445. 4. It is wrong to assume bonding of PET molecules on aluminium is through molecular end-groups only since saponification of the ester groups can also lead to bonding possibilities. F.M. De Wit, Ö. Özkanat, J.M.C. Mol, H. Terryn, J.H.W. De Wit, Surface and Interface Analysis 2010, 42, 316. 5. It is not possible to measure delamination with Scanning Kelvin Probe (SKP) for systems where the delamination mechanism is dominated by displacement of polymer-metal bonds by water. 6. Rights are not social privileges but objective facts, identifying the freedoms we need to live our lives - whether a majority in society agrees or not. Thomas A. Bowden in “Supreme Disappointments”, Ayn Rand Center for Individual Rights, November 3rd, 2008, http://tinyurl.com/9fr3lga 7. Persuasion is clearly a sort of demonstration, since we are most fully persuaded when we consider a thing to have been demonstrated. Aristoteleʼs Rethoric, Book 1, 1355a (translation by W. Rhys Roberts).

(3) 8. Since mobile phone use by children increases the chances of brain tumors, more public information on the risks in the Netherlands is urgently needed. F. Soderqvist, M. Carlberg, K.H. Mild, L. Hardell, Environmental Health 2011, 10. 9. “Green” subsidies on electric cars are misplaced, because “electrifying” all cars would result in a worldwide depletion of lithium or nickel resources in around 15 years if the number of new cars stays at the level of 2010. H. Wouters and D. Bol in Material Scarcity An M2i study 2009 10. The importance of adhesion is usually only noticed, when it is not present. These propositions are regarded as opposable and defendable, and have been approved as such by the supervisors prof. dr. R. Boom and prof. dr. ir. H. Terryn.

(4) Stellingen behorende bij het proefschrift: Polymer bonding and adhesion on aluminium and magnesium alloys 1. Zonder chemische binding kan er geen hechting zijn. 2. In tegenstelling tot wat doorgaans gedacht wordt, wordt de kwaliteit van hechting van organische deklagen op metalen wordt hoofdzakelijk bepaald door de lokale samenstelling van de substraten 3. Het verbeteren van hechting op metalen door opruwen kan niet worden toegeschreven aan “mechanische interlocking”, maar is voornamelijk het gevolg van het verwijderen van de oppervlaktelaag, wat een vers oxide creëert en organische vervuiling verwijdert. 4. Het is verkeerd om aan te nemen dat binding van PET moleculen op aluminium alleen door moleculaire eindgroepen tot stand komt, omdat verzeping van de ester groepen ook kan leiden tot bindingsmogelijkheden. F.M. De Wit, Ö. Özkanat, J.M.C. Mol, H. Terryn, J.H.W. De Wit, Surface and Interface Analysis 2010, 42, 316. 5. De kwaliteit van de hechting van organische deklagen op metalen substraten wordt hoofdzakelijk bepaald door de locale samenstelling van de substraten. 6. Rechten zijn geen sociale privileges maar objectieve feiten, die de vrijheden definiëren die we nodig hebben om onze levens te leven - of de meerderheid het daar nou mee eens is of niet. Thomas A. Bowden in “Supreme Disappointments”, Ayn Rand Center for Individual Rights, November 3rd, 2008, http://tinyurl.com/9fr3lga 7. Overtuiging is een soort bewijs, want we zijn het meest overtuigd als we aannemen dat iets bewezen is Aristotelesʼ Rethoric Book 1 1355a, 11.

(5) 8. “Groene” subsidies op elektrische autoʼs zijn misplaatst, omdat het elektrisch maken van alle autoʼs tot gevolg zou hebben dat de wereldwijde voorraden lithium of nikkel binnen circa 15 jaar uitgeput zijn als het aantal nieuwe autoʼs gelijk zou blijven aan het niveau van 2010. H. Wouters and D. Bol in Material Scarcity An M2i study 2009 9. Omdat het gebruik van mobiele telefoons bij kinderen de kans op hersentumoren vergroot, is er dringend meer openbare informatie over de risicoʼs in Nederland nodig. F. Soderqvist, M. Carlberg, K.H. Mild, L. Hardell, Environmental Health 2011, 10. 10. Het belang van hechting wordt meestal pas opgemerkt bij het ontbreken ervan. Deze stellingen worden opponeerbaar en verdedigbaar geacht en zijn als zodanig goedgekeurd door de promotoren prof. dr. R. Boom en prof. dr. ir. H. Terryn.

(6) Polymer bonding and adhesion on aluminium and magnesium alloys. Proefschrift ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, KLCAV=CR=J@A2A?PKN-=CJEj?QOLNKBEN+#!-,QU>AJ RKKNVEPPANR=JDAP#KHHACARKKN0NKIKPEAO EJDAPKLAJ>==NPARAN@A@ECAJ KLI==J@=CJKRAI>ANKIQQN. door. Frederik Mathijs DE WIT I=PANE==HGQJ@ECEJCAJEAQN CA>KNAJPA5PNA?DP.

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(8) Table of contents Chapter 1 - Introduction. 7. Chapter 2 - Background. 13. 2.1 Introduction and scope. 15. 2.2 Materials used. 15. !HQIEJEQI I=CJAOEQI=J@=HHKUO. . !LLHE?=PEKJOKB=HQIEJEQII=CJAOEQI=J@I=CJAOEQI=HQIEJEQI =HHKUO. . 0NKPA?PEKJ BNKI?KNNKOEKJ KB=HQIEJEQII=CJAOEQI=J@I=CJAOEQI =HQIEJEQI=HHKUO. . 2.3 Aluminium and magnesium oxides. 23. #KILKOEPEKJKB=HQIEJEQI=J@I=CJAOEQI=HHKUKTE@AO. . #DAIE?=HLNKLANPEAOKB=HQIEJEQII=CJAOEQIKTE@AOQNB=?AO. . )JkQAJ?AOKBLNAPNA=PIAJPOKJPDAKTE@AOKB=HQIEJEQI=J@I=CJAOEQI =HHKUO. . 2.4 Theories of bonding and adhesion of organic molecules and coatings on metals $AjJEPEKJO. 32 . "KJ@EJCLDUOE?O=J@?DAIEOPNUKBLKHUIANOKJIAP=HOEJPAN=?PEKJ=P KTE@AO. . /NC=JE??K=PEJCO=J@NALNAOAJP=PERAIKHA?QHAO. . -=?NKO?KLE?=HIA?D=JE?=H=@DAOEKJPAOPEJC. . &=EHQNA. . 2AH=PEKJ>APSAAJ>KJ@EJC=J@=@DAOEKJ. . Chapter 3 - Experimental. 51. 3.1 Introduction. 53. 3.2 Materials. 53. 3Q>OPN=PAO. . 0NAL=N=PEKJ. . -KHA?QHAO. .

(9) 0%4'?K=PEJCO 3.3 Pre-treatments and application methods. 57. 0NAPNA=PIAJPOKB=HHKUO. . !LLHE?=PEKJKBIKHA?QHAO. . 3.4 Experimental equipment and methods !QCAN%HA?PNKJ3LA?PNKO?KLU !%3 @ALPDLNKjHEJC. 59 . &KQNEAN4N=JOBKNI)JBN=NA@2AkA?PEKJ!>OKN>PEKJ3LA?PNKO?KLU &4)22!3. . !OUIIAPNE?=H$KQ>HA#=JPEHARAN"A=I. . 0KPAJPEK@UJ=IE?IA=OQNAIAJPO. . Chapter 4 - Analysis of the surface composition of pre-treated aluminium alloys. 63. 4.1 Introduction. 65. 4.2 Results…. 65. !%3=J=HUOEOKB?DAIE?=HHULNAPNA=PA@O=ILHAO. . !%3=J=HUOEOKBDA=PLNAPNA=PA@O=ILHAO. . 4.3 Discussion. 73. !%3=J=HUOEOKB?DAIE?=HHULNAPNA=PA@O=ILHAO. . !%3=J=HUOEOKBDA=PLNAPNA=PA@O=ILHAO. . 4.4 Conclusions. 76. Chapter 5 - Electrochemical behavior of pre-treated aluminium and -8A95:5A99-3:1?5A9-88;E5::1A@>-8-:0-/505K10?-85:1 environments. 79. 5.1 Introduction and background. 81. 5.2 Results. 85. 5.3 Discussion. 89. 5.4 Conclusions. 91. Chapter 6 - Bonding of succinic acid and di-methyl terephthalate. 95. 6.1 Introduction. 97. 6.2 Results. 99.

(10) &4)22!3=J=HUOEOKB>KJ@EJCKBOQ??EJE?=?E@PK?DAIE?=HHULNAPNA=PA@ =HQIEJEQI=HHKUOQNB=?AO. . &4)22!3=J=HUOEOKB>KJ@EJCKBOQ??EJE?=?E@KJDA=PPNA=PA@=HQIEJEQI =HHKUOQNB=?AO R=?QQIAR=LKN=PA@I=CJAOEQI=J@!:. . &4)22!3=J=HUOEOKB>KJ@EJCKB@EIAPDUHPANALDPD=H=PA $-4 KJ LNAPNA=PA@=HQIEJEQI=HHKUOQNB=?AO 6.3 Discussion. 107. "KJ@EJCKBOQ??EJE?=?E@KJDA=PPNA=PA@=HQIEJEQI=HHKUOQNB=?AO R=?QQI AR=LKN=PA@I=CJAOEQI=J@!:. . "KJ@EJCKB@EIAPDUHPANALDPD=H=PA $-4 KJLNAPNA=PA@=HQIEJEQI=HHKU OQNB=?AO 6.4 Conclusions. 112. "KJ@EJCKBOQ??EJE?=?E@KJLNAOAJPA@OQNB=?AO. . "KJ@EJCKB$-4KJLNAOAJPA@OQNB=?AO. . Chapter 7 - Bonding and stability of succinic acid on magnesium alloy. 115. 7.1 Introduction. 117. 7.2 Results. 117. &4)22!3=J=HUOEOKB>KJ@EJCKBOQ??EJE?=?E@PK?DAIE?=HHU LNAPNA=PA@I=CJAOEQI=HHKUOQNB=?AO. . !MQAKQOOP=>EHEPUKBOQ??EJE?=?E@KJPDA@EBBANAJPHULNAL=NA@ OQ>OPN=PAO. . )JkQAJ?AKB=CEJCEJ=EN. . "KJ@EJCKBOQ??EJE?=?E@IKHA?QHAOKJ=CA@O=ILHAO. . -KNLDKHKCE?=H?D=N=?PANEV=PEKJ. . 7.3 Discussion. 128. "KJ@EJCKBOQ??EJE?=?E@KJ!:. . "KJ@EJCOP=>EHEPUKBOQ??EJE?=?E@KJLNAPNA=PA@!:. . )JkQAJ?AKB=CEJCKJ>KJ@EJC. . 7.4 Conclusions. 130.

(11) Chapter 8 - Adhesion of PETG. 133. 8.1 Introduction. 135. 8.2 Results. 136. %JANCUNAHA=OAN=PAOBNKI!$#". . -KNLDKHKCE?=H=J=HUOEOKB@AH=IEJ=PEKJKJ=HQIEJEQIOQNB=?AO. . 8.3 Discussion. 141. )JPANLNAP=PEKJKB!$#"NAOQHPO. . -KNLDKHKCE?=H=J=HUOEOKB@AH=IEJ=PEKJKJ=HQIEJEQIOQNB=?AO. . #KIL=NEOKJPK&4)22!3NAOQHPOBNKI?D=LPAN. . 8.4 Conclusions. 145. Chapter 9 - Summarizing conclusions. 149. Introductory chapters. 151. Surface Characterization (chapters 4 and 5). 151. Nanoscopic/molecular interactions at the interface (chapters 6 and 7). 154. Macroscopical/mechanical testing of adhesion (chapter 8). 156. Epilogue and outlook. 159. Summary. 161. Samenvatting. 163. Publications related to this work. 165. Dankwoord. 167. Curriculum Vitae . 169.

(12) Chapter 1 - Introduction.

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(16) )JPNK@Q?PEKJ. 4N=JOBKNI)JBN=NA@2AkA?PEKJ!>OKNLPEKJ3LA?PNKO?KLU &4)22!3 KBOQ??EJE? =?E@ =J@ $-4 KJ PDA =HQIEJEQII=CJAOEQI =HHKU #D=LPAN ODKSO PDA >AD=REKN KB I=CJAOEQI=HQIEJEQI =HHKUO=O SAHH =OPDAOP=>EHEPU KBOQ??EJE? =?E@IKHA?QHAOKJ PDA OQNB=?AOKB PDAOA=HHKUOEJ PDALNAOAJ?AKBS=PAN!HOK= ?KIL=NEOKJ EO I=@A SEPDPDALNA@E?PEKJEJ?D=LPANKJS=PAN@EOLH=?AIAJP 4DAH=OP L=NP jJ=HHU ?KJP=EJO PDAPDEN@=J@H=OP OPAL KBPDA=LLNK=?D BKHHKSA@ )J ?D=LPAN PDAI=?NKO?KLE? =@DAOEKJ>AD=REKNKB=LKHUIANjHIS=OPAOPA@0%4 ' S=O>KJ@A@PKPDALNAPNA=PA@=HHKUO=J@PDAjHIO SANAOQ>OAMQAJPHU @AH=IEJ=PA@ SEPD PDAJKRAHIAPDK@KB=OUIIAPNE?=H@KQ>HA?=JPEHARAN>A=I !$#" 4DANAOQHPO =NA ?KQLHA@ PK PDA ?DAIE?=H @=P= ?KHHA?PA@ EJ ?D=LPAN =J@ ?KIL=NA@ SEPD PDA PDAKNAPE?=H R=HQAO =O ?=H?QH=PA@ EJ #D=LPAN &EJ=HHU EJ ?D=LPAN = OQII=NU EO CERAJ=J@?KJ?HQOEKJO=NA@N=SJBKHHKSEJCBNKIPDALNAREKQO?D=LPANOSEPD= DKHEOPE? REASKJPDABQPQNAKB=@DAOEKJO?EAJ?A References ;<. + , -EPP=H ! 0EVVE !@DAOEKJ LNKIKPEKJ PA?DJEMQAO PA?DJKHKCE?=H =LLHE?=PEKJO $AGGAN .AS9KNG 1999. ;<. !! :=@LKKN *3EJGA 2 "AJA@E?PQO International Journal of Adhesion and Adhesives 2009, 29 . ;<. . 7 "QEFO Voorkomen corrosie kan miljoenen euro schade besparen -AP==HI=C=VEJA %EOI=)J@QOPNE=HIA@E="6 $KAPEJ?DAI 2007. ;<. *R=J @AJ "N=J@ 0#3JEF@ANO 7 '3HKKB (4ANNUJ *(7@A7EP . ;<. Journal of Physical Chemistry B 2004, 108 *R=J @AJ "N=J@ /"H=FEAR 0#*"AAJPFAO (4ANNUJ *(7@A7EP . ;<. Langmuir 2004, 20 *R=J @AJ "N=J@ /"H=FEAR 0#*"AAJPFAO (4ANNUJ *(7@A7EP Langmuir 2004, 20 . ;<. *R=J@AJ"N=J@ 36=J'EHO 0#*"AAJPFAO (4ANNUJ 63ERAH *(7 @A7EP Progress in Organic Coatings 2004, 51 . ;<. %-?#=BBANPU Journal of the Electrochemical Society 2003, 150 ". .

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(18) Chapter 2 - Background .

(19) #D=LPAN. .

(20) "=?GCNKQJ@. 2.1 Introduction and scope 4DAjNOPL=NPKBPDEO?D=LPANCERAO=JKRANREASKBLNKLANPEAOKBPDAQOA@I=PANE=HOEJ PDEOPDAOEO=HQIEJEQI =J@I=CJAOEQI)POP=NPOSEPD = >NK=@=J@>NEABKRANREAS KB PDA LNKLANPEAO =J@=LLHE?=PEKJOKB=HQIEJEQI =J@I=CJAOEQI =J@ PDAEN =HHKUO=J@ @EO?QOOAO PDA LKOOE>HA LNKPA?PEKJ IA=OQNAO =C=EJOP ?KNNKOEKJ )J PDA OA?KJ@ L=N=CN=LD PDA?KILKOEPEKJ =J@PDALNKLANPEAO KBKTE@AOKJ =HQIEJEQI I=CJAOEQI =J@ PDAEN =HHKUO =NA @EO?QOOA@ !HOK IKOP ?KIIKJ LNAPNA=PIAJPO BKN =HQIEJEQI =HHKUO=NA>NEAkU@EO?QOOA@ 4DA PDEN@ L=N=CN=LD BK?QOAO KJ =@DAOEKJ =J@ >KJ@EJC KB KNC=JE? IKHA?QHAO LKHUIANO KJ =HQIEJEQI =HHKUO EJ CAJAN=H =J@ KJ =HQIEJEQII=CJAOEQI =HHKUO OLA?Ej?=HHU !HOK PDA LKOOE>HA EJkQAJ?A KB LNAPNA=PIAJPO KJ =@DAOEKJ KJ PDAOA =HHKUO =OP=GAJBNKIHEPAN=PQNA EO@EO?QOOA@ !@AO?NELPEKJ KBPDAPDAKNUKB=@DAOEKJ =J@>KJ@EJC >QEH@EJCKJPDALNAREKQOSKNG KB6=J @AJ "N=J@;< EOCERAJ!HOKOARAN=HPA?DJEMQAOPKIA=OQNA>KPD >KJ@EJC=J@ =@DAOEKJ @ENA?PHU=J@EJ@ENA?PHUKJ =HQIEJEQI =HHKUO=NANAREOEPA@!J@jJ=HHU EJPDA H=OP L=N=CN=LD OKIA IA?D=JE?=H PAOPEJC IAPDK@O QOA@ BKN @AH=IEJ=PEKJ OPQ@EAO =HOK@AHERANEJC=OOK?E=PA@=@DAOEKJAJANCEAO=NAAR=HQ=PA@BKNPDAENQOABQHJAOOBKN PDEJ?K=PEJCO 2.2 Materials used 2.2.1 Aluminium, magnesium and alloys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m KB OPAAH LNK@Q?PEKJ EJ PKJJ=CA )J P=>HA PDA LNK@Q?PEKJ MQ=JPEPEAOEJ PKJJAOKBKPDANIAP=HO SDE?D=NAAEPDAN QOA@=O =HHKUEJCAHAIAJPOKN BKN ?KILHAPAHU @EBBANAJP OPNQ?PQN=H =J@ AJCEJAANEJCLQNLKOAO =NA=HOK CERAJ PKLQP PDA =>QJ@=J?A KB I=PANE=HO EJPK LANOLA?PERA &KN EJOP=J?A PDA PKP=H =IKQJP KB HEPDEQI QOA@ EJ NA?D=NCA=>HA >=PPANEAO ATLA?PA@ ARAN PK >A IEJA@ SKNH@SE@A EO =>KQPPDAO=IA=OPDAPKP=HSKNH@SE@A=JJQ=HLNK@Q?PEKJ KB=HQIEJEQI/J =OEIEH=N HARAH=NALH=PEJQICNKQLIAP=HO 0'- SDE?D =NA?QNNAJPHU=>QJ@=JPHUQOA@EJBQAH .

(21) #D=LPAN. ?AHHO3KIAKBPDAOAAHAIAJPO HEGAHEPDEQI =J@O?=J@EQI=NA=HOKQOA@BKN=HHKUEJC =HQIEJEQI4DA BQPQNA=R=EH=>EHEPU EO DKSARAN QJ?ANP=EJ >A?=QOA KBA?KJKIE? =J@ geopolitical reasons;< )P EO DECDHU MQAOPEKJ=>HA EB PDA IEJEJC KB PDA IEJAN=HO PD=P ?KJP=EJPDAOAAHAIAJPOPEHHPDAH=OPCN=IPKLNK@Q?APDA=BKNAIAJPEKJA@=LLHE?=PEKJO EJ AJANCU OPKN=CAKN ?KJRANOEKJ OUOPAIO EO A?KJKIE?=HHU BA=OE>HA 2A?U?HEJC=J@ KLPEIEVEJCPDAI=PANE=HQOAEJ =LLHE?=PEKJO OAAIO HEGA= IQ?D IKNAOAJOE>HANKQPA PKBKHHKS4DANABKNAPDALNKPA?PEKJ=C=EJOP?KNNKOEKJBKNOPNQ?PQN=HHUQOA@HECDPIAP=HO HEGA=HQIEJEQI=J@I=CJAOEQIEOIKNAQNCAJPPD=JARAN Table 2.1 2KQCD AOPEI=PAOKB=JJQ=H LNK@Q?PEKJ =J@AOPEI=PA@SKNH@SE@ANAOANRA UA=NO=Ph?QNNAJPN=PAi KBOAHA?PA@AJCEJAANEJCIAP=HO&NKI7KQPANOAP=H;< and KPDANOKQN?AO Metal Steel !HQIEJEQI :EJ?. Annual worldwide production (tonnes) l l l. -=CJAOEQI ,EPDEQI. l l. #KLLAN 0H=PEJQI. l . .E?GAH. l. Estimated worldwide reserve UA=NO UA=NO l tonnes UA=NO UA=NO l* tonnes UA=NO UA=NO l** tonnes UA=NO l tonnes UA=NO. -=TEIQI EJ?HQ@EJClPKJJAO=HNA=@UBKQJ@ 0H=PEJQICNKQLIAP=HO 0'- EA0@ 2Q 2DAP? &KN =HQIEJEQI PDA LNK@Q?PEKJ =J@ QOA EJ R=NEKQO =LLHE?=PEKJO D=O >AAJ ?KIIKJLH=?ABKNIKNAPD=J OARAJ @A?=@AO4DA JAA@BKN = HECDP BKNI=>HAIAP=H D=O >AAJ DECD OEJ?A 7KNH@ 7=N )) SDAJ =HQIEJEQI =HHKUO SANA QOA@ IKOPHU EJ =EN?N=BP OPNQ?PQNAO =J@ OKIA ?KKGS=NA )PO LNK@Q?PEKJ D=O EJ?NA=OA@ ATLHKOERAHU OEJ?APDAJ3AAjCQNABKN=DEOPKNE?KRANREAS 3KIABA=PQNAO D=RA C=EJA@EILKNP=J?A OQ?D =O DECDAN UEAH@=J@QHPEI=PAPAJOEHA OPNAJCPD SDEHAI=EJP=EJEJCKN EILNKREJCBKNI=>EHEPULNKLANPEAO DECD B=PECQAHEBA=J@ >APPAN ?KNNKOEKJLNKLANPEAO)J PAJUA=NOPEIA PDA=JJQ=H LNK@Q?PEKJ KB LNEI=NU=HQIEJEQID=O=HIKOP@KQ>HA@BNKIPKJJAOPK PKJJAO&NKI PDA ?KNNA?PA@ LNE?A BKN N=S =HQIEJEQI D=O OPA=@EHU NEOAJ BNKI PK LAN PKJJA EJ PDA OA?KJ@ MQ=NPAN KB !BPAN PDA ?NEOEO EJ PDA OA?KJ@ MQ=NPAN KB PDALNE?AD=@@NKLLA@PK LANPKJJASDEHAEPEJ?NA=OA@=C=EJ .

(22) "=?GCNKQJ@. PK=>KQP JKRAI>AN 3A?KJ@=NU NA?U?HA@=HQIEJEQI =HHKUO I=EJHU EO ?DA=LANPD=JLQNALNEI=NU=HQIEJEQI>U=>KQP4DANABKNA EPEORANUEJPANAOPEJC BKN =HQIEJEQI I=JQB=?PQNANO PK ATLANEIAJPSEPD ?KILKOEPEKJO PK CAP PDANAMQENA@ LNKLANPEAO BKN PDA EJPAJ@A@ =LLHE?=PEKJO #QNNAJPHU BNKI PDA PKP=H =IKQJP KB =HQIEJEQI EJ ?EN?QH=PEKJ =NKQJ@ ?KJOEOPO KB NA?U?HA@=HQIEJEQI-=CJAOEQI LNE?AOD=RABKHHKSA@PDAPNAJ@KB=HQIEJEQILNE?AO. Figure 2.1. 7KNH@LNK@Q?PEKJKB=HQIEJEQI 53CAKHKCE?=HOQNRAU;< 4DAEJkQAJ?A KB =HHKUEJC AHAIAJPO KJ @EBBANAJP LNKLANPEAO KB PDA NAOQHPEJC =HHKU EO ?KJOE@AN=>HA;<4DANA=NAI=JU@EBBANAJP=HQIEJEQI=HHKUO SNKQCDP=HHKUO?H=OOEjA@ >UPDA)JPANJ=PEKJ=H!HHKU$AOECJ=PEKJ 3UOPAI =O!!TTTT SDANATTTTEO= JQI>AN 4=>HA CERAO=J KRANREAS KB PDA?KILKOEPEKJO KB PDAI=FKN =HHKUEJC OANEAO=J@ UEAH@ OPNAJCPDO 4DA IKOP ?KIIKJ =HHKUEJC AHAIAJPO =NA ?KLLAN I=CJAOEQI ?DNKIEQI OEHE?KJ ENKJ JE?GAH VEJ? =J@ HEPDEQI %RANU AHAIAJP =@@O OLA?Ej? LNKLANPEAOPKPDA=HHKU-=CJAOEQIBKNEJOP=J?AEJ?NA=OAOPDASAH@=>EHEPUKBPDA=HHKU 3EHE?KJHKSANOPDAIAHPEJCLKEJP=J@I=GAO?=OPEJCA=OEAN#KLLAN=@@OOPNAJCPD PK PDA=HHKU!HOK?=@IEQI I=JC=JAOA=J@ PEP=JEQI ?=J >A =@@A@ >QP EJ =HH ?=OAO PDAPKP=H=IKQJPKB=HHKUEJCAHAIAJPOEOHAOOPD=J KBPDAPKP=H=HHKU3LA?Ej?=HHU BKN PDAATLANEIAJPO@EO?QOOA@PDEO PDAOEO =J =HHKUKBPDA!!TTTOANEAOS=O QOA@ SDE?D ?KJP=EJO I=CJAOEQI=O PDAI=FKN =HHKUEJCAHAIAJP EILNKREJCPDA?KNNKOEKJ LNKLANPEAO =J@ NAOQHPEJC EJ = DECD BKNI=>EHEPU =J@ UEAH@ OPNAJCPD 4DANA =NA I=JU .

(23) #D=LPAN. =LLHE?=PEKJO SDANA !!TTT OANEAO EO QOA@ SDE?D SEHH >A @EO?QOOA@ EJ PDA JATP L=N=CN=LD. Table 2.2 !HQIEJEQIOANEAO@AO?NELPEKJ ?KIIKJ=HHKUO=J@QOAO Series name. System. !!TTT !!TTT !!TTT !!TTT. !HSP !H#Q !H-J !H-C. Common alloys !! !! !! !!. Used in &KEH !ANKOL=?A 0=?G=CEJC #=JAJ@O . Yield strength (MPa), alloy !!(. !!(. !!(. !!(. !!TTT. !H-C3E. !!. =QPKIKPERA #KJOPNQ?PEKJ . !!4. !!TTT. !H:J-C. !!. transportation !ANKOL=?A . !!4. personal transportation. -=CJAOEQI EO =HHKUA@ SEPD =HQIEJEQI VEJ? OEHE?KJ VEN?KJEQI OEHRAN =J@ I=JC=JAOA !HHKUO =NA QOQ=HHU J=IA@ SEPD PDA jNOP HAPPANO KB PDA I=EJ =HHKUEJC ?KILKJAJPO 3AAP=>HA BKN PDAIKOP?KIIKJHUQOA@J=IAO-=CJAOEQI =HHKU LNE?AO=NA=>KQPPSE?A=O DECD =O=HQIEJEQI=HHKUO!HQIEJEQI EOQOA@PKEJ?NA=OA PDAUEAH@OPNAJCPD KBI=CJAOEQI!: BKN AT=ILHAD=OPSE?APDAUEAH@OPNAJCPD KB LQNA I=CJAOEQI;< #KI>EJEJC>KPD =HQIEJEQI =J@VEJ? EJ =J =HHKU EJ?NA=OAO PDA I=TEIQI@ABKNI=PEKJ OKLNK@Q?PO@KJʼPNQLPQNAA=OEHUSDAJATPNQ@A@-=JC=JAOA BKN EJOP=J?A EO =@@A@PKEILNKRA ?KNNKOEKJ LNKLANPEAO!J KRANREASKB PDA!!TTT =HQIEJEQII=CJAOEQIB=IEHUKB=HHKUOSEPDOAHA?PA@LNKLANPEAOEOCERAJEJ4=>HA Table 2.3 -=CJAOEQIOANEAO@AO?NELPEKJ=J@?KIIKJ=HHKUO Series name. System. Common alloys. !-TT. -C!H-J. !-. !3TT. -C!H3E. !3. !:TT. -C!H:J. !: !:. 7%TT. -C2% :N9. 7%. :%TT. -C:J2%:N. :%. :+TT. -C:J:N. :+. :-TT. -C:J-J. :-. * 2%N=NAA=NPDAHAIAJPO. .

(24) "=?GCNKQJ@. Table 2.4 !!TTT=HQIEJEQII=CJAOEQIB=IEHUKB=HHKUOSEPDOAHA?PA@LNKLANPEAO Series name. System. Applications. !!. -C. !!. -C -J Transport containers. !!. -C. !!. QOAO=OLH=PAO=J@LELAO -C2% :N9 7AH@A@ LNAOOQNA RAOOAHO I=NEJA =QPK =EN?N=BP. !!. -C:J2%:N ?NUKCAJE?O 46 PKSANO @NEHHEJC NECO PN=JOLKNP=PEKJ. !!!. -C:J:N. AMQELIAJP IEOOEHA?KILKJAJPO 7AH@A@ OPNQ?PQNA OPKN=CA P=JGO LNAOOQNA RAOOAHO . !!. -C:J-J. salt water service !QPKIK>EHA>K@UODAAPO ?=JAJ@O. !!. 0ELEJC PQ>EJC I=NEJA=J@KBBODKNAOQLANOPNQ?PQNAO 0NAOOQNA RAOOAHO NERAPO EJ@QOPNE=H =J@ =N?DEPA?PQN=H. 7AH@EJC AHA?PNK@AO SAH@A@ OPNQ?PQNAO OPKN=CA -C. P=JGO BKN DA=PA@ LNK@Q?PO LNAOOQNA RAOOAHO PNQ?G >K@EAOBKNDKPKEHKN=OLD=HP=LLHE?=PEKJO. 2%N=NAA=NPDAHAIAJPO 2.2.2 Applications of aluminium-magnesium and magnesium-aluminium alloys 3KIAPEIAO =HQIEJEQI EO JKP REOE>HA EJ AJ@LNK@Q?PO KN JKP ?KIIKJHUNA?KCJEVA@ %T=ILHAO EJ?HQ@A LNEJPEJC LH=PA I=PANE=H QOA@ BKN LNEJPEJCPKLH=PA BKN >KKGO !JKPDAN AT=ILHA KB hDE@@AJi QOA EO EJ L=?G=CEJC I=PANE=H HEGA ?DELO >=CO =J@ NA?AJPHUBKK@=J@>ARAN=CALKQ?DAO -KNA K>REKQO AT=ILHAO =HPDKQCD JKP =HS=UO PK PDA LQ>HE? KB =HQIEJEQI QOA EJ?HQ@A L=NPO KB >ARAN=CA ?=JO PK PN=JOLKNP=PEKJ OUOPAIO >EGAO =ENLH=JAO =J@ L=NPOKB?=NO 3KIAL=NPOEJPN=JOLKNP=PEKJ D=RAhI=CE?=HHU?D=JCA@i PK=HQIEJEQI KNIKNANA?AJPHU j>AN IAP=H H=IEJ=PAOHEGA'H=NA` SDE?D?KI>EJAHKSSAECDPSEPD DECD EIL=?P OPNAJCPD !HQIEJEQII=CJAOEQI =HHKUO =NA QOA@ KBPAJ EJ @=EHU HEBA 4DA IKOP ?KIIKJ >QP B=ENHUSAHHDE@@AJ=LLHE?=PEKJ KB!! EOEJ PDAAJ@OKB>ARAN=CA?=JO7DEHAPDA P=>O =NA I=@A BNKI !! KN !! !! ?KJP=EJEJC =LLNKTEI=PAHU I=CJAOEQI=J@ I=JC=JAOAD=ORANUDECDOPNAJCPD=J@OQBj?EAJPBKNI=>EHEPU PKLANIEP I=GEJCPDAEJPACN=H NERAP EJ PDAA=OU KLAJ AJ@;< 4DA=HHKUS=O=?PQ=HHU @AOECJA@OLA?Ej?=HHUSEPD PD=P LQNLKOAEJ IEJ@;< NAMQENEJCI=TEIQI OPNAJCPD SEPD IEJEIQIPDE?GJAOO>A?=QOAKB?KOP=J@>A?=QOAPDA?KJOQIANJAA@OPK>A=>HAPK KLAJ PDA O?KNA 7EPD = OPAAH HE@ = ?KILHAPAHU@EBBANAJP@AOECJ EO NAMQENA@ =OS=O .

(25) #D=LPAN. @KJABKN PDAhA=OU KLAJAJ@iOPAAH ?=J;</PDAN QOAOEJ?HQ@AOKIAEJJAN ?=N @KKN BN=IAO >A?=QOA KB PDA CKK@ BKNI=>EHEPU )J ODEL>QEH@EJC =J@ =N?DEPA?PQNA!!TTT OANEAO=HHKUO =NALKLQH=N >A?=QOA KBPDAEN CKK@ SAH@=>EHEPU B=PECQALNKLANPEAO=J@ EJDANAJP?KNNKOEKJNAOEOP=J?A =O?KIL=NA@PKKPDAN=R=EH=>HA=HHKUO;< -=CJAOEQI =HHKUOD=RAARAJ HKSAN @AJOEPEAOPD=J=HQIEJEQI=HHKUO RO GCI 5OQ=HHU I=CJAOEQI =HHKUO =LLA=N EJ ?KJOQIAN AHA?PNKJE?O HEGA ?=IAN= >K@EAO=J@LANOKJ=H=Q@EK OAAjC N=?A ?=NL=NPO NEIO AJCEJA>HK?GO >K@U L=NPO EJ & =J@ IEHEP=NU =LLHE?=PEKJO !HOK >A?=QOA KB EPO HKS @AJOEPU =J@ OPEHH NAH=PERAHU DECD IAHPEJCLKEJPEPEOQOA@EJ =ANK OL=?A=LLHE?=PEKJO HEGAIEOOEHAO=J@ NK?GAPO=J@=HOKEJJQ?HA=NB=?EHEPEAO. Figure 2.20DEHELO!8LKNP=>HA#$LH=UANSEPD@EA?=OPI=CJAOEQIHE@ 2.2.3 Protection (from corrosion) of aluminium-magnesium and magnesiumaluminium alloys -KOPKBPDAOAIAJPEKJA@OPNQ?PQN=H =LLHE?=PEKJO?KQH@JKP>A=?DEARA@EB=HQIEJEQI KN I=CJAOEQI =HHKUO SKQH@ >A QOA@ =O?=OP KN KJHU NKHHA@ -QHPELHA ?KNNKOEKJ LNK>HAIOK??QNSEPDQJLNKPA?PA@=HHKUO ARAJ EJIEH@AJRENKJIAJPO!HQIEJEQI=J@ I=CJAOEQI =HHKUO SANA LNAREKQOHU OPQ@EA@ ATPAJOERAHU =J@ =NA LNKJA PK R=NEKQO BKNIO KB ?KNNKOEKJ ARAJ EJ IEH@ AJRENKJIAJPO HKS O=HEJEPU L( JAQPN=H EJPANCN=JQH=N LEPPEJC ?NARE?A;< 4DANABKNA EJ IKOP ?=OAO =HQIEJEQI =J@ I=CJAOEQI=HHKUOQNB=?AO=NALNKPA?PA@>UH=UANOSDE?D =NAJKP KNHAOO=BBA?PA@>U PDA AJRENKJIAJP /JA KB PDA ?KIIKJ S=UO KB LNKPA?PEKJ EO PK ?H=@ DECDOPNAJCPD =HHKUOSEPD NAH=PERAHULKKN?KNNKOEKJ LNKLANPEAOSEPD =J =HQIEJEQI =HHKU SDE?D EOJKP OKLNKJAPK?KNNKOEKJ/JAKBPDAAT=ILHAOEO!! SDE?D EOQOA@EJ=ANKOL=?A .

(26) "=?GCNKQJ@. EJ@QOPNU=J@EO?KIIKJHU?H=@SEPD !! =J=HHKUSEPD =HQIEJEQI!! @KAOJKPD=RAB=RKN=>HAIA?D=JE?=H LNKLANPEAO NAH=PERAHU QJEILKNP=JPBKN ?H=@@EJC =LLHE?=PEKJO >QP@QAPKEPODECDLQNEPUEPSEHHJKPOQBBANBNKILEPPEJC?KNNKOEKJ>A?=QOA PDANAEOKJHU= RANUOI=HHJQI>AN KBLNA?ELEP=PAOPD=P?=J =?P=O EJEPE=PEKJ OEPAOBKN PD=PPULAKB=PP=?G&KN!!TTT DKSARAN PDEOEOJKP=HS=UO@AAIA@JA?AOO=NU =O OKIA=HHKUOEJODEL>QEH@EJC=J@=N?DEPA?PQNA=NAQOA@SEPDKQPLNKPA?PEKJ SEPD OKIA BKNAOAA=>HA?KNNKOEKJLNK>HAIO;< !JKPDAN S=U KB LNKPA?PEKJ EO PK =LLHU =JKPDAN H=UAN PK PDA OQNB=?A SDE?D D=O LNKPA?PERALNKLANPEAO PKPDA=HHKU QJ@ANJA=PD 4DEO ?=J AEPDAN >A=J KNC=JE? KN =J EJKNC=JE? H=UAN )JKNC=JE? H=UANO =NA QOQ=HHU LNK@Q?A@ >U ?NA=PEJC = PDE?GAN =J@ @AJOAN=HQIEJEQIKTE@AH=UAN>U=JK@EVEJC!JK@EVEJCEJRKHRAO=J AHA?PNKHUPASDE?D SEHHB=?EHEP=PAPDA>QEH@QL KBPDAH=UAN#DNKIE?=?E@=JK@EVEJC #!! D=O>AAJQOA@ BKN @A?=@AOEJPDA=ANKOL=?AEJ@QOPNU >QPEOQJ@ANO?NQPEJU>A?=QOAPDA=JK@EVEJC >=PDO PD=P =NA QOA@ ?KJP=EJ #N 6) ?DNKI=PA EKJO 4DAOA EKJO =NA ?KJOE@ANA@ = DA=HPD LNK>HAI =J@PDANABKNA=NAPK>A>=JJA@EJ PDAJA=N BQPQNA#!!HA=@O PK= LKNKQO OPNQ?PQNA SDANAPDA>KPPKI KB PDA LKNAO EO OA=HA@ KBB >U = @AJOA>=NNEAN H=UAN0KNAOKB=>KQP JISE@A=J@=JKTE@APDE?GJAOOKBeI=NAPULE?=HHUQOA@ EJ PDA =ANKOL=?A EJ@QOPNU LNKRE@EJC =J ATPNAIAHU OP=>HA OQNB=?A PK >A =@DAOERAHU >KJ@A@ PK = ?DNKI=PA ?KJP=EJEJC KNC=JE? LNEIAN /PDAN PA?DJEMQAO ?=J ?NA=PA PDE?GAN H=UANO KB KTE@AO SDE?D ?=J >A AEPDAN OA=HA@ EJ >KEHEJC S=PAN BKNIEJC LOAQ@K>KADIEPAEJOE@APDALKNAO KN>UEJPNK@Q?EJCLECIAJPOEJ>KEHEJCS=PAN@QNEJC OA=HEJC -KNA NA?AJPHU >A?=QOA KB PDA LAJ@EJC >=J KJ ?DNKI=PAO EJ EJ@QOPNE=H LNK?AOOAO =HPANJ=PERAOPK#!!D=RA>AAJATLHKNA@ SDE?D SANADEOPKNE?=HHU=?PQ=HHU =HNA=@U =R=EH=>HA4DAOA EJ?HQ@A =JK@EVEJC EJ LDKOLDKNE? 0!! OQHLDQNE? 3!! >KNE? =?E@KN = ?KI>EJ=PEKJ PDANAKB ACLDKOLDKNE?OQHBQNE? =?E@ 03! !HPDKQCD PDAOA=HPANJ=PERAO =NARE=>HAEJ@QOPNE=HO?=HALKOOE>EHEPEAO PDA?KNNKOEKJ LNKPA?PEKJ KNN=PDANLNARAJPEKJ EOIQ?DSKNOAPD=JPD=PKB#!!2A?AJPHU :D=JCAP=H;< have ODKSJ PD=PEJ = LKPAJPEK@UJ=IE? ATLANEIAJPKB!! EJ =J .=#H OKHQPEKJ =JK@E? ?QNNAJP@AJOEPEAO KBH=UANOLNK@Q?A@>U#!!SANA= B=?PKN PK HKSAN PD=J PDKOALNK@Q?A@ >U =HH PDAKPDAN LNK?AOOAO!HOK PDA ?QNNAJP @AJOEPU @E@JKP NEOA=>KRA!?I ARAJ =P6RO3#%)PS=O=NCQA@PD=PPDA@AJOEPUKBPDA >=NNEANH=UAN=J@PDAKRAN=HHDECDAN@AJOEPU KBPDAKTE@ASANAPDAI=EJ?KJPNE>QPEJC B=?PKNO 4DEO L=NPE?QH=N EJANPJAOO EO KJA KB PDA NA=OKJO PDEO LNK?AOO EO OK SAHH AI>A@@A@ EJ PDA LNK@Q?PEKJ KB =ANKOL=?A I=PANE=HO 4DANA =NA KPDAN S=UO KB LNKPA?PEKJ KB=HQIEJEQISEPDEJKNC=JE? H=UANO SDE?D =NAJKPBQNPDAN @EO?QOOA@DANA >QPNABANAJ?AEOI=@APK3DA=O>U;<. .

(27) #D=LPAN. 4DA KPDAN S=U KB LNKPA?PEKJ KB =HQIEJEQI =J@ I=CJAOEQI SEPD KN SEPDKQP =JK@EVEJC EOPDNKQCD PDAQOAKBKNC=JE??K=PEJCO4DAOAD=RAOEJ?AHKJC>AAJQOA@ =J@ @ALAJ@EJC KJ PDA =LLHE?=PEKJ = SE@A R=NEAPU KB LNKLANPEAO ?=J >A ?DKOAJ -QHPELHA H=UANO ?=J >A =LLHEA@ SDANA A=?D H=UAN D=O OLA?Ej? LNKLANPEAO AC = DU@NKLDK>E? PKL H=UANPKLNKPA?PS=PANBNKI AJPANEJCEJPKPDAOUOPAI4DAOQNB=?AO KBPDA =HHKUO ?=J >A P=EHKNA@ PK LNKRE@A PDALNKLAN ?EN?QIOP=J?AO BKN PDAKNC=JE? ?K=PEJCO PK >KJ@ PK )J CAJAN=H EP EO = LNKLAN h?KJjCQN=PEKJi KB PDA KTE@A EJ ?KI>EJ=PEKJ SEPDSAHHOAHA?PA@KNC=JE?IKHA?QHAOPD=PCERAOPDA>AOP?KI>EJ=PEKJKB LNKLANPEAO 4DA KTE@A IECDP DKSARAN JKP D=RA PDA LNKLAN ?KJjCQN=PEKJ KN PDANA IECDP>AKEHO KN KH@KTE@AOGEJO NKHHA@EJPK PDA OQNB=?A;<4DANABKNA PDAOQNB=?AO JAA@PK >Ah?HA=JA@i 4DEO ?=J >A@KJA SEPD =?E@ KN =HG=HEJA ?HA=JANO KN AP?DEJC >=PDO4DANA=NAI=JUEJ@QOPNE=HLNK?AOOAOSDANA>KPD =NA=LLHEA@)JCAJAN=HPDA =@R=JP=CAKB=HG=HEJA?HA=JANOEOPD=PPDAPNA=PIAJPO=NAIKNAPDKNKQCD4DEOSEHH>A BQNPDAN@EO?QOOA@EJ 4DAOLA?Ej? =LLHE?=PEKJ KB!! EJ ?=J AJ@O NAMQENAO = ?K=PEJC SEPD = OA=H=JP PKL ?K=P4DAOA=NAIK@EjA@ALKTUKN= REJUHKNC=JKOKH?K=PEJCO;< >QP>A?=QOAKB AJRENKJIAJP=HEJPANAOPOEILNKRAIAJPKBPDAOA?K=PEJCO?KJPEJQAO. .

(28) "=?GCNKQJ@. 2.3 Aluminium and magnesium oxides "A?=QOA>KJ@EJCKBKNC=JE? ?K=PEJCOP=GAOLH=?AKJ PDAKTE@AH=UANOLNAOAJP PDA ?KILKOEPEKJKBPDAOAKTE@AH=UANOEORANUNAHAR=JPBKN=@DAOEKJ4DA?KILKOEPEKJ KB PDA =HQIEJEQII=CJAOEQI KTE@AO SDE?D =NA=HS=UO LNAOAJP =PPDAOQNB=?AKBPDA !H-C=HHKUO EOPDANABKNA@EO?QOOA@ .ATP PDA ?DAIE?=H LNKLANPEAO KB PDAOAKTE@AH=UANO =NA ODKNPHU @EO?QOOA@=J@PDA ATLA?PA@EJkQAJ?AKB@EBBANAJPOQNB=?ALNAPNA=PIAJPOEOAT=IEJA@ 2.3.1 Composition of aluminium and magnesium alloy oxides 4DAI=EJ CK=H KBPDAEJRAOPEC=PEKJO S=O PK?KIL=NA= N=JCA KBI=PANE=HO R=NUEJC BNKILQNA=HQIEJEQIPK!Hg-C -Cg!H=J@jJ=HHULQNAI=CJAOEQI4DANABKNA EPEO JA?AOO=NUPKQJ@ANOP=J@PDA>AD=REKNKB=HHKTE@AOQNB=?AOSDE?D=NALKOOE>HA Aluminium alloys /TE@AOQNB=?AOKB?KIIAN?E=H =HQIEJEQI =HHKUO AC!!; < !!;< and !!;< D=RA @EBBANAJP ?KILKOEPEKJO @QAPKEJ?KNLKN=PEKJ KB =HHKUEJC AHAIAJPO HEGA?KLLAN VEJ? =J@I=CJAOEQI0NABANAJPE=H @EOOKHQPEKJ KN OQNB=?AAJNE?DIAJPKB =HHKUEJC AHAIAJPO ?=J >A EJ@Q?A@ >U ?DAIE?=HHU LNAPNA=PEJC PDA OQNB=?AO KN >U anodizing; < EJ =?E@=J@=HG=HEJAOKHQPEKJO 0NABANAJPE=H OQNB=?AAJNE?DIAJP ?=J =HOK>A=?DEARA@SEPDDA=PPNA=PIAJPO;< .=PQN=HKTE@AjHIKJ!H-C=HHKUOSDE?D =NABKNIA@>AHKS_#D=RA=PDE?GJAOO KB JI SDEHA PDAOA ?=J >A OECJEj?=JPHU PDE?GAN =>KRA _# QL PK eI @ALAJ@EJC KJ PAILAN=PQNA =J@ >QHG -C ?KJPAJP;< -=CJAOEQI ?=J JKP KJHU OACNAC=PA KJ CN=EJ >KQJ@=NEAO =J@ BKNI LNA?ELEP=PAO -C!H);< >QP EP ?=J =HOK @EBBQOAEJPKPDAOQNB=?AKTE@A=PAHAR=PA@PAILAN=PQNAO;< SDE?D AEPDANK??QNO=BPAN ?=OPEJC KN @QNEJC PDA PAILANEJC OPAL PK EJkQAJ?A IA?D=JE?=H LNKLANPEAO !P PAILAN=PQNAO =>KRA_# I=CJAOEQI @EBBQOAO BNKI PDA>QHG KB PDA =HHKU PKPDA OQNB=?A 4DANA EO = ?KILAPEPERA KTE@=PEKJ NA=?PEKJ >APSAAJ I=CJAOEQI =J@ =HQIEJEQI @QA PK KQPS=N@ @EBBQOEKJ KB I=CJAOEQI =J@ KTUCAJ @EBBQOEKJ EJS=N@O ARAJ =PHARAHOHAOOPD=J LLI I=CJAOEQI3ARAN=H=QPDKNO; < D=RAODKSJ >U IA=JOKB!%3=J@803PD=PPDAKTE@AH=UANKB=J!H-C=HHKU?=J >AAJNE?DA@EJ-C >U OQ>FA?PEJC PDA I=PANE=H PK = LNKHKJCA@ DA=P PNA=PIAJP ARAJ =P PAILAN=PQNAO >AHKS _# EBPDA=HHKU?KJP=EJO IKNAPD=J SP I=CJAOEQI!PPDAOADECDAN HARAHOKB>QHG I=CJAOEQI OKIAPEIAO= @QLHATjHIKB=HQIEJEQIKTE@A?HKOAPKPDA IAP=H =J@=J KQPAN H=UAN KB-C/ NAOQHPO7ABANO;< =J@&EAH@;< D=RAOQII=NEVA@ PDAKTE@=PEKJKB=HQIEJEQII=CJAOEQI=HHKUO=PDECDANPAILAN=PQNAOLNAREKQOHU .

(29) #D=LPAN. ,A= =J@ -KHEJ=NE;< D=RA =HOK ATPAJOERAHU OPQ@EA@ PDA @EBBQOEKJ KB I=CJAOEQI EJ =HQIEJEQI!! =J@!!=HHKUO HKSAN =HHKUA@ =J@ SP I=CJAOEQI =J@D=RABKQJ@PD=P?KJOE@AN=>HUDECDANPAILAN=PQNAO QL PK_# =NAJAA@A@BKN I=CJAOEQIOQNB=?AAJNE?DIAJPKBPDAOA=HHKUO Magnesium alloys 3ARAN=H OPQ@EAO SANA LANBKNIA@ PK QJ@ANOP=J@ PDA IA?D=JEOI KB jHI CNKSPD KJ I=CJAOEQI=J@EPO=HHKUOEJ@EBBANAJPAJRENKJIAJPO.KN@HEAJAP=H;<BKQJ@=JKTE@A jHIIKNLDKHKCUKJLQNAI=CJAOEQI?KJOEOPEJCKBPDNAAH=UANO OAA=HOKjCQNA. Figure 2.3 4DNAAH=UAN KTE@AOPNQ?PQNAKJ I=CJAOEQI O?DAI=PE? .KN@HEAJ AP =H ;<. 0QNA I=CJAOEQI EO LNKPA?PA@ >U = OP=>HA =ENBKNIA@ @AJOA KTE@A EJ @NU AJRENKJIAJPO )J DQIE@ =EN =J@ =MQAKQO AJRENKJIAJPO PDA =ENBKNIA@ jHI EO QJ@ANIEJA@ >U BKNI=PEKJ KB = HAOO OP=>HA DU@N=PA@ ?AHHQH=N KTE@A NAOQHPEJC BNKI AHA?PNK?DAIE?=HIAP=HKTE@=PEKJ!LH=PAHAPHEGAKQPANH=UANEOBKNIA@PKCERA=PDNAA .

(30) "=?GCNKQJ@. H=UAN jHIIKNLDKHKCUEJ S=PAN >ULNA?ELEP=PEKJ KBKTE@AOKJ PDA=ENBKNIA@jHI4DA =ENBKNIA@jHI =HPDKQCD ?D=N=?PANEVA@>U=@AJOAIKNLDKHKCU LH=UO=JEILKNP=JP NKHA EJ PDABKNI=PEKJ KB PDA EJJAN =J@KQPAN H=UANO >U =HHKSEJC S=PAN EJCNAOO=J@ @EOOKHQPEKJKB-C )J CAJAN=H OEIEH=N H=UANO SANABKQJ@ KJ -C!H=HHKUO >QP PDAOA SANAOECJEj?=JPHU PDEJJAN PD=J H=UANOKJ LQNAI=CJAOEQI I=EJHU@QAPK= OI=HHAN LH=PAHAPPDE?GJAOO KBPDA=HHKUO)J?NA=OEJCPDA=HQIEJEQI?KJPAJPKB>EJ=NUI=CJAOEQI=HHKUO?=QOA@ = OECJEj?=JPNA@Q?PEKJ KBPDAKRAN=HHPDE?GJAOO=J@KBPDALH=PAHAPH=UAN EJ L=NPE?QH=N 4DALNAOAJ?AKBVEJ? EJ =HHKUOSEPD IKNA PD=J =HQIEJEQI ?=QOA@= OECJEj?=JP EJ?NA=OA EJ PDE?GJAOO KB PDA EJJAN H=UAN =O ?KIL=NA@ PK =HHKUO ?KJP=EJEJC I=JC=JAOA4DALH=PAHAPH=UANOKJ PDA!:OANEAO=HHKUO=NA=LLNA?E=>HUPDEJJANPD=J PDA LH=PAHAPH=UANO KJ !-KN !3 OANEAO SEPD OEIEH=N =IKQJPO KB !H SDEHA PDA EJJAN H=UANO =NA PDE?GAN ! OECJEj?=JP AJNE?DIAJP KB =HQIEJEQI KTE@A EJ PDA EJJAN IKOP H=UAN K??QNO AOLA?E=HHU KJ =HHKUO?KJP=EJEJCIKNA PD=J =HQIEJEQI!HQIEJEQI ?KJ?AJPN=PEKJO EJ PDA KN@AN KB SANA @APA?PA@ EJ PDA EJJAN H=UAN BKN =HHKUO AT?AA@EJCPDA PDNAODKH@?KJ?AJPN=PEKJ4DEONAOQHPA@EJEJ?NA=OA@OP=>EHEPUKBPDA KTE@A =J@ ?KJOAMQAJPHU =J EILNKRA@?KNNKOEKJ NAOEOP=J?A )P S=OOQCCAOPA@ PD=P PDA HEIEPBKNPDA=HHKUCEREJC=>KQP KB=HQIEJEQIEJPDAKTE@A?KNNAOLKJ@A@ PKOKIAOKNP KB LAN?KH=PEKJ PDNAODKH@ BKN PDAL=OOER=PEJC!H/ ?KILKJAJP KB PDA KTE@A;< 2.3.2 Chemical properties of aluminium-magnesium oxide surfaces "A?=QOA=HQIEJEQIEO=ILDKPANE? =HQIEJEQI KTE@A@EOOKHRAO EJ =MQAKQO OKHQPEKJO >AHKSL(=J@=>KRAL( SDANAPDA!H

(31) EKJO=?P=O=?E@=J@!H/=O>=OA OAA0KQN>=ET@E=CN=IEJjC . .

(32) #D=LPAN. Figure 2.4 0KPAJPE=HL( @E=CN=I BKN PDA OUOPAI !H S=PAN =P _# =?PEREPU 0KQN>=ET;< $EOOKHQPEKJ I=U >A OHKS EB = SAHH =@DANEJC KTE@A H=UAN EO LNAOAJP L=OOEREPU "NA=G@KSJ KBPDAKTE@AjHI ?=J NAOQHPBNKI IA?D=JE?=H NQLPQNA KN BNKI ?DAIE?=H =PP=?G >U=JEKJOOQ?D =O?DHKNE@AEKJO)J IKOP?=OAONAL=EN EOEJOP=JP=JAKQO =J@ @ALAJ@EJCKJPDAIKEOPQNA?KJPAJPKBPDAAJRENKJIAJP ?=J AEPDAN>A=??KIL=JEA@ >UPDAKTUCAJNA@Q?PEKJNA=?PEKJKNPDADU@NKCAJARKHQPEKJNA=?PEKJ 4 Al -> 4 Al3+ + 12 e- 3 O2 + 12 2 H 2O +. . (2.1). 6. O2-. (2.2). -> 2. OH-. + H2. (2.3). e- ->. 2e-.

(33) "=?GCNKQJ@. "KPD !H/ =J@ !H /( ?=J >A BKNIA@ =O SAHH =O I=JU KPDAN ?KILHAT KTU DU@NKTE@AOLA?EAO;< -=CJAOEQI KJ PDAKPDAN D=J@KJHU BKNIO = OP=>HADU@NKTE@A=>KRAL( OAA jCQNA 5J@AN JKNI=H =PIKOLDANE? ?EN?QIOP=J?AO I=CJAOEQIPDANABKNAJAA@O PK>A?KRANA@ EJ = OP=>HA KTE@AH=UAN)P EO OQCCAOPA@PD=P PDEOEO = ?KILHATKTE@A I=@AQL KBI=CJAOEQIDU@NKTE@AO=J@?=N>KJ=PAO;<-=CJAOEQI DU@NKTE@AO=J@ ?=N>KJ=PAO LNKPA?P PDA IAP=H QL PK = ?ANP=EJ HARAH >QP SDAJ PDAOA H=UANO =NA @=I=CA@ ?KNNKOEKJ SEHHK??QN RANUN=LE@HU OEJ?AI=CJAOEQI ?KNNKOEKJ EOATPNAIA B=OP(ECDAN PAILAN=PQNAO=??AHAN=PAPDEOARAJ BQNPDAN;<.ATPPKPDAjHIBKNI=PEKJ =O@AO?NE>A@>U.KN@HEAJ=J@CERAJ=>KRAEJjCQNA +KLLANOAP=H;< developed =J AHA?PNK?DAIE?=H IK@AH BKN PDA BKNI=PEKJ KB @EBBANAJP H=UANO KJ -C EJ =EN =J@ water;<)J@NU=EN=PDEJKTE@AH=UANEOBKNIA@KJI=CJAOEQI 2 Mg + O2 -> 2 MgO. (2.4). )J ?KJP=?P SEPD S=PAN I=CJAOEQI KTE@A NA=?PO SEPD S=PAN PK BKNI I=CJAOEQI DU@NKTE@A SDEHAPDARKHQIAKBPDAH=UANEOCNKSEJC MgO + H2O -> Mg(OH)2 . (2.5). )JS=PANSEPDKQP?DHKNEJA -CNA=?POPK-C

(34) =J@S=PAN EONA@Q?A@PKDU@NKCAJ=J@ DU@NKTE@AEKJO Mg + 2 H2O -> Mg2+ + 2 OH- + H2 . (2.6). (2.7). Mg

(35) =J@/(PDAJNA?KI>EJAPK-C /( Mg2+ + 2 OH- -> Mg(OH)2. )J &ECQNA PDAKNAPE?=H @KI=EJO KB ?KNNKOEKJ -C

(36) EIIQJEPU -C =J@ L=OOER=PEKJ -C /( KBI=CJAOEQI=P_#=NACERAJEJPDA0KQN>=ET@E=CN=I. .

(37) #D=LPAN. Figure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

(38) "=?GCNKQJ@. CO2 (aq) + OH- -> HCO3-. (2.8). HCO3- + OH- -> CO32- + H2O. (2.9). 4DA=PIKOLDANE??KNNKOEKJ KBLQNAI=CJAOEQIEONALKNPA@PK>AEJDE>EPA@>U?=N>KJ @EKTE@A4DEOS=O=PPNE>QPA@PKPDAOHECDPHULNKPA?PERAJ=PQNAKBI=CJAOEQIDU@NKTUH ?=N>KJ=PA PD=P PAJ@O PK =??QIQH=PAKJ PDA OQNB=?A -C /( NA=?PO SEPD #/ to BKNII=CJAOEQIDU@NKTUH?=N>KJ=PA=??KN@EJCPKPDABKHHKSEJCNA=?PEKJ 5 Mg(OH)2 + 4 CO2 -> Mg5(CO3)4(OH)2 + 4H2O. (2.10). )PEOOQCCAOPA@PD=P PDEO ABBA?P?KJPNE>QPAO PKPDAOHKS ?KNNKOEKJ KB PDAI=CJAOEQI =HQIEJEQIIK@AH=HHKUQOA@>U"H^?DANAP=H;<!OEIEH=N IA?D=JEOIEOOQCCAOPA@ BKN !:$ OAA=HOK&ECQNA #=N>KJ @EKTE@AJAQPN=HEVAOPDAOQNB=?AAHA?PNKHUPA =J@BKNIO?KILHATDU@NKTU?=N>KJ=PAOAC-C #/) /( ; <. Figure 2.63QCCAOPA@?KNNKOEKJIA?D=JEOIKB!:$EJDQIE@=EN=P=I>EAJP HARAHOKB#/"H^?DANAP=H;< !HHKUEJCAHAIAJPO QOQ=HHU EJ?NA=OAPDA?KNNKOEKJ N=PA OEJ?AHK?=H ?KNNKOEKJ K??QNO SDAJC=HR=JE? ?KQLHEJCP=GAOLH=?A>APSAAJPDALNA?ELEP=PAOKNKPDAN@EO?KJPEJQEPEAO =J@PDAI=PNETI=PANE=H4DAKTE@AOKJPDAOALNA?ELEP=PAO=NAQOQ=HHUJKP?HKOA@KN SAHH=@DANEJC PDANABKNA HA=REJC PDA>=NA IAP=H =J@ OQNNKQJ@EJCO ATLKOA@PKPDA =CCNAOOERA =MQAKQOAJRENKJIAJP!JKPDAN LNK>HAI?KJOEOPOKBPDAEJPANBANAJ?AKB =JEKJO AOLA?E=HHU#HEKJO SDE?D>HK?G KNDEJ@ANPDANAKTE@=PEKJ KBPDAIAP=HEBPDA J=PERAKTE@AOD=RA@EO=LLA=NA@;< .

(39) #D=LPAN.

(40) :LA1:/1?;2<>1@>1-@91:@?;:@41;D501?;2-8A95:5A9-:09-3:1?5A9 alloys. !HQIEJEQI =HHKUOEJ CAJAN=H =NAATPAJOERAHU?DAIE?=HHU ?HA=JA@=J@AP?DA@>ABKNA ?K=PEJCKN =@DAOERA>KJ@EJC3DA=O>U;< D=OCERAJ =J ATPAJOERAKRANREAS KBPDAOA LNAPNA=PIAJPOEJ ?D=LPAN KBPDAIAJPEKJA@ NABANAJ?A -KOPKB PDALNAPNA=PIAJPO =NA=LLHEA@PKAJOQNA = IKNA @QN=>HA>KJ@KB?K=PEJCO =J@=@DAOERAOEJ LN=?PE?=H =LLHE?=PEKJO )J HEPAN=PQNA OKIA LNAPNA=PIAJPO BKN PDA !!TTT OANEAO =HHKUO SANA @AO?NE>A@ EJ IKNA @AP=EH .ATP PK IA?D=JE?=H LNAPNA=PIAJPO SDE?D NAIKRA PDA PKL H=UAN KB ?KJP=IEJ=PA@ KTE@AO PDANA =NA OARAN=H IA?D=JEOIO >U SDE?D PDA KTE@A ?KILKOEPEKJ?=J >A=HPANA@#KIIKJHUQOA@LNAPNA=PIAJPOEJ?HQ@A=HG=HEJAKN =?E@ ?HA=JEJCLHQOAP?DEJC=J@PDA=LLHE?=PEKJ KBOARAN=H ?KJRANOEKJ?K=PEJCO%OLA?E=HHU EJ PDA H=OPPULA PDANA D=O >AAJ LNKCNAOO EJ NA?AJPUA=NO PKNALH=?APDA?DNKI=PA ?KJRANOEKJ ?K=PEJCO =O IAJPEKJA@QJ@AN 3ARAN=H NAOA=N?DANO D=RA HKKGA@ EJPKLNKLANPEAOKBJKJ?DNKI=PA?KJP=EJEJCOAHB=OOAI>HEJCIKJKH=UANO 3!-O SEPD @EBBANAJPBQJ?PEKJ=HEPEAO EJ CAJAN=H;< PK=?P=O?KNNKOEKJ LNKPA?PEKJ KNBKN EILNKREJC PDA>KJ@EJCKB?K=PEJCOKN =@DAOERAO&KNA=?D ?=PACKNUKBPDAOAPNA=PIAJPOPDANA =NAI=JU?KIIAN?E=HLNK@Q?PO=R=EH=>HA SDE?D SKNG SEPD OP=J@=N@;< or patented;< NA?ELAO 4DAOA QOQ=HHU ?KJP=EJ ATPN= ?DAIE?=HO PK BKNI ?KILHATAO SEPD PDA ?KJP=IEJ=PEKJKNNA=?PEKJ LNK@Q?PO PKEJkQAJ?APDAGEJAPE?O ACSAPPEJC=CAJPO KB PDA NA=?PEKJO KN PK OP=>EHEVA PDA LNAPNA=PIAJP >=PDO #KIIKJHU =BPAN = LNA PNA=PIAJP OPAL PDA OQ>OPN=PAO =NA NEJOA@ PDKNKQCDHU SEPD @AEKJEVA@ S=PAN PK LNARAJPPDANA=?PEKJOBNKI?KJPEJQEJC=J@LNK@Q?EJCKRANAP?DA@OQNB=?AO;< 4K ?HA=J PDA =ONKHHA@ =HHKUO KB KEH =J@ CNA=OA =HG=HEJA LNAPNA=PIAJPO =NA QOA@ 4DAOA D=RA PDA =@R=JP=CAPD=P AOLA?E=HHU =P AHAR=PA@ PAILAN=PQNAO;<, etching is RANU N=LE@ !O @EO=@R=JP=CA PDAOA LNAPNA=PIAJPO IECDPHA=RA = OIQPH=UAN SDAJ H=NCAN =IKQJPO KB =HQIEJEQI =NA AP?DA@ AC =P HKJCAN AP?DEJC PEIAO 4ULE?=HHU OK@EQIDU@NKTE@A .=/( EOQOA@PK?NA=PA=J =MQAKQOOKHQPEKJ KBDECD L( !O=@AOIQPPEJCPNA=PIAJP=BPAN=HG=HEJA?HA=JEJC OARAN=H=?E@OKHQPEKJO=NAQOA@ 4DAOA ?=J ?KJP=EJ LDKOLDKNE? JEPNE? DU@NKkQKNE? ?DNKIE? =?E@ KN ?KI>EJ=PEKJO PDANAKB !?E@LNAPNA=PIAJPO=NA=HOK>AEJCQOA@OAL=N=PAHUSEPD =OEIEH=N?KILKOEPEKJ KBPDA >=PDO )JPDA>ACEJJEJCKBPDAO +EJHK?D=J@?KSKNGANO D=RAATPAJOERAHU OPQ@EA@PDA NAH=PEKJ >APSAAJ LNAPNA=PIAJPO =J@ PDA KTE@A ?KILKOEPEKJ KB R=NEKQO =HQIEJEQI .

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jP=J@?KSKNGANO;< OPQ@EA@!!4 SP -C =J@BKQJ@PD=P =J =HG=HEJA ?KIIAN?E=H ?=QOPE? LNAPNA=PIAJP NAIKRA@ = H=NCA L=NP KB I=CJAOEQI BNKIPDAOQNB=?A!HOK =HG=HEJA=J@=?E@ h@AKTE@EOANi PNA=PIAJPO?KI>EJA@=OSAHH =O=HH KPDAN =?E@LNAPNA=PIAJPO ?KILHAPAHU NAIKRA@I=CJAOEQI BNKI PDA OQNB=?A 4DAU =PPNE>QPA@ PDA KNECEJ=H EJ?NA=OA@ I=CJAOEQI OQNB=?A ?KJ?AJPN=PEKJ PK PDA LNK?AOOEJC KB PDA ODAAPO #KI>EJEJC PDAOA L=LANO EP ?=J >A ?KJ?HQ@A@ PD=P >A?=QOA I=CJAOEQI ?=J HA=@ PK LKKNAN @QN=>EHEPU KB PDA =@DAOERAHU >KJ@A@ OUOPAI EPODKQH@ >ANAIKRA@>U=J =?E@LNAPNA=PIAJP!O S=O @EO?QOOA@>ABKNA DECDAN PAILAN=PQNAO ?=J HA=@ PK=J EJ?NA=OA@ HARAH KB I=CJAOEQI =P PDA OQNB=?A .ARANPDAHAOO = =HNA=@U BKQN PEIAO EJ?NA=OA KB I=CJAOEQI ?KJPAJP=P PDAOQNB=?A S=O ODKSJ >U 3QJ AP =H;< =BPAN >KJ@EJC D=@ P=GAJ LH=?A =P NAH=PERAHU HKS PAILAN=PQNAO =J@ ODKNP PEIAO W _# DKQNO 4DEO K??QNNA@ BKN &0,AP?DA@ =?E@ !!4 O=ILHAO.ATPPK PDAEJ?NA=OAEJ -C?KJPAJP =HOK= #Q ?KJPAJP EJ?NA=OA S=O BKQJ@ SDE?D EO =HOK @APNEIAJP=H PK PDA @QN=>EHEPU KB PDA =@DAOERA >KJ@O. .

(42) #D=LPAN. 2.4 Theories of bonding and adhesion of organic molecules and coatings on metals

(43) 1K:5@5;:? !HHAJ;< OQII=NEVA@EJ DEO KRANREAS PDA LDAJKIAJKJ KB =@DAOEKJ SEPD PDA BKHHKSEJC OP=PAIAJPO hEP D=O >AAJ OQCCAOPA@ PD=P PDANA EO JKP =J =??ALPA@ ATLH=J=PEKJKB=@DAOEKJ >A?=QOALAKLHAD=RAJKPNA?KCJEVA@PDAIQHPE?KILKJAJP J=PQNAKBPDALNK>HAIi=J@h&KNPDAOAR=NEKQOIA?D=JEOIO of adhesiong&@7 PDA NAH=PERAEILKNP=J?A=J@PDALNKLAN S=UEJ SDE?D PDAUODKQH@>A?KI>EJA@SEHHR=NU BNKI KJA AT=ILHA PK =JKPDAN >QP JKJA ODKQH@ >A AT?HQ@A@SEPDKQP RANU ?=NABQH ?KJOE@AN=PEKJ=J@ATLHKN=PEKJi "KJ@EJC =J@ =@DAOEKJ =NA OKIAPEIAO QOA@ EJPAN?D=JCA=>HU )J CAJAN=H PDA @EOPEJ?PEKJ EOI=@A>APSAAJ PDAPSKQOEJC PDABKHHKSEJC@AjJEPEKJO >KJ@EJCEOPDA LDAJKIAJKJ SDANAPSKIKHA?QHAO KN =PKIO =NA OAIE LANI=JAJPHU =PP=?DA@ PK A=?D KPDAN>U LDUOE?=HKN ?DAIE?=H EJPAN=?PEKJ !@DAOEKJ KJPDAKPDAND=J@@A=HO SEPD PDA I=?NKO?KLE?=H EJPAN=?PEKJ >APSAAJ LD=OAO SDANA =HOK @EOOEL=PEKJ KB AJANCU=J@IK>EHEPUKB=PKIO=J@IKHA?QHAO=NAEJRKHRA@)JHEPAN=PQNA IKOP=NPE?HAO AEPDAN=@@NAOOKJAKNPDAKPDAN &KNPDEO PDAOEOPDABKHHKSEJC@AjJEPEKJOKB>KJ@EJC=J@=@DAOEKJ KBKNC=JE? CNKQLO PKIAP=HOSEHH>AQOA@ Bonding EO PDAEJPAN=?PEKJ KB=J KNC=JE? IKHA?QHASEPD PDAOQNB=?AOLA?EAOKJ PDA IAP=H AC KTE@AO DU@NKTE@AO ?=N>KJ=PAO AP? 4DEO EO >U @AjJEPEKJ = OEJCHA =PP=?DIAJP SDEHA PDA >KJ@ OPNAJCPD EO QOQ=HHU =RAN=CA@ KQP KRAN I=JU >KJ@O 4DANA=NASA=G =J@OPNKJC>KJ@O SDE?D SEHH>A@EO?QOOA@>AHKS=J@=J KRANREAS EOCERAJEJ4=>HA"KJ@EJCEOATLNAOOA@EJ*IKH Adhesion EOPDAI=?NKO?KLE? >AD=REKNKB=J KNC=JE? ?K=PEJC=@DANEJCPK= IAP=H !@DAOEKJ I=JEBAOPOEPOAHB >U @AjJEPEKJ =O = JQI>AN KB=PP=?DIAJPO =RAN=CA@KQP KRAN=H=NCANOQNB=?A=NA=SDAJHK=@A@I=?NKO?KLE?=HHU7EPDKQP>KJ@EJC =@DAOEKJ ?=JJKPATEOP)PEJ?HQ@AO IE?NK I=PANE=HLNKLANPEAO=J@>AD=REKN?KIL=N=>HAPK>QHG I=PANE=HO AC%IK@QHE PAJOEHAOPNAJCPD JA?GEJC AP? =J@ PDANABKNA =@DAOEKJ EO ATLNAOOA@=OAJANCUKNBKN?ALANOMQ=NAOQNB=?A=NA= AC*IKN.I 4DAO?EAJPEj? jAH@EO PDANABKNAOLHEPEJPSKKJA?KJOEOPOKBPDAPDAKNUKB>KJ@EJCKB IKHA?QHAO =J@ PDA KPDAN KB PDA IA?D=JE?=H LNKLANPEAO KB PDA SDKHA OUOPAI 4DA .

(44) "=?GCNKQJ@. H=PPAN QOQ=HHU EJ?HQ@AOOPQ@EAO KBPDA@QN=>EHEPU KBPDAOUOPAIO ATLKOA@PK IKNAKN HAOO OARANA =J@ LN=?PE?=H AJRENKJIAJPO HEGA DECD KN HKS PAILAN=PQNAO DQIE@EPU ?KI>EJA@SEPDIA?D=JE?=H B=PECQA BKN?AO 4DA JATP PSK OA?PEKJO ?KJP=EJ AT=ILHAO KB >KPD jAH@O =@@NAOOAO PDA PDAKNAPE?=H KB >KJ@EJC=J@=@DAOEKJ KJ IAP=HO SDEHA @A=HO SEPD IA?D=JE?=H =@DAOEKJ3EJ?A@QNEJCPDEOPDAOEO SKNG JK@QN=>EHEPUOPQ@EAOD=RA>AAJ LANBKNIA@ PDAOA D=RA >AAJ KIEPPA@ BNKI PDEO ?D=LPAN =HPDKQCD PDAU =NA AOOAJPE=H SDAJ looking at practical coating adhesion; <&EJ=HHUCERAO=J KRANREASKBPDABAS OPQ@EAO PD=P D=RA ?KI>EJA@ IKHA?QH=N >KJ@EJC =J@ IA?D=JE?=H =@DAOEKJ MQ=JPEP=PERAHU Table 2.5/RANREASKB>KJ@O=J@PDAENOPNAJCPD Type Primary bonds. Donor-acceptor bonds. $<1/5K/. From [44]. From [58]. From [46]. Ionic #KR=HAJP Metallic "NfJOPA@=?E@>=OA. kcal/mol* .=. kJ/mol QLPK. kcal/mole .=. interactions ,ASEO=?E@>=OAEJPAN=?PEKJO. QLPK. Secondary Bonds Hydrogen bonds. (U@NKCAJ>KJ@OEJRKHREJC. . kQKNEJA (U@NKCAJ>KJ@OAT?HQ@EJC Van der Waals bonds. kQKNEJA 0ANI=JAJP@ELKHA@ELKHA $ELKHAEJ@Q?A@@ELKHA $EOLANOEKJ ,KJ@KJ BKN?AO. . QLPK. 5LPK. . . HAOOPD=J . G?=H G*. 2.4.2 Bonding physics and chemistry of polymers on metals: interaction at oxides -K@AHOBKNEJPAN=?PEKJ >APSAAJ PSKLD=OAOEJ HEPAN=PQNA BNKI =HIKOP=HH NABANAJ?AO B=HHEJPKPDNAA?=PACKNEAO. -A?D=JE?=H =J?DKN=CAI=?NKO?KLE? KN IE?NKO?KLE? EJPANPSEJEJCKBPSK LD=OAO @QAPKNKQCDJAOO .

(45) #D=LPAN. #DAIE?=H=@OKNLPEKJ KN?DAIEOKNLPEKJ?KR=HAJPKNEKJE?>KJ@O 0DUOE?=H =@OKNLPEKJ KN LDUOEOKNLPEKJ LDUOE?=H =PPN=?PERABKN?AO6=J @AN 7==HO BKN?AO EJ?HQ@EJC LANI=JAJP @ELKHA@ELKHAEJPAN=?PEKJO +AAOKI @ELKHAEJ@Q?A@ @ELKHA $A>UA =J@ @EOLANOEKJ BKN?AO ,KJ@KJ (U@NKCAJ >KJ@O B=HH EJ PDA ?=PACKNUKB6=J@AN7==HO>KJ@O OAA=HOKP=>HA -A?D=JE?=H=J?DKN=CAKNIA?D=JE?=HEJPANHK?GEJCATEOPOOQLLKOA@HUSDANA?K=PEJCO =PP=?DSAHHPKNKQCD OQNB=?AO!HHAJ;< =NCQA@PD=P= J=ERA>AHEABEJ PDEOATLH=J=PEKJ LANOEOPO ARAJ EJ PDA B=?A KB ?HA=N ARE@AJ?A PD=P OQNB=?A NKQCDJAOO =J@ >KJ@ OPNAJCPD ?KNNAH=PA JAC=PERAHU EJ I=JU AT=ILHAO )J OKIA OLA?Ej? ?=OAO =HPDKQCD DA IAJPEKJO JK IAP=HLKHUIAN OUOPAIO KJ PDEO I=?NKO?KLE?=H O?=HA PDA EJPANLAJAPN=PEKJ @E@ I=GA = LKOEPERA @EBBANAJ?A KJ PDA =@DAOEKJ (KSARAN IKNA NA?AJPHU (=NNEO AP =H D=RAJKPBKQJ@ =JU ?KNNAH=PEKJ >APSAAJ PDANKQCDJAOO KB = OQNB=?A=J@PDAPKP=HAJANCUBKN@AH=IEJ=PEKJ;</J= IE?NKO?KLE? KN ARAJKJ =JI O?=HA EJPANPSEJEJC PDNKQCD KTE@A hSDEOGANOi LAJAPN=PEJC PDA ?K=PEJC ?=J LNKKB >AJAj?E=H PK =@DAOEKJ >QP KJHU EB PDA EJ?NA=OA@ ABBA?PERA EJPANB=?E=H =NA= EO OQ>OP=JPE=H !HOK KTE@AO D=RA PK D=RA OPNKJC >KJ@O SEPD PDA QJ@ANHUEJC IAP=H =@DAOERA =J@DECD EJPANJ=H ?KDAOERA OPNAJCPD )J PDA NAOPKB PDEO L=N=CN=LD PDEO ?KJPNE>QPEKJKJ=@DAOERABKN?AOEOJACHA?PA@ OEJ?AEPEOJKNI=HHURANUOI=HH 4DAPKP=H SKNG KB=@DAOEKJ EJ?KNLKN=PAO=HHPULAOKBEJPAN=?PEKJ =PPDAEJPANB=?A=J@ P=GAO =@DAOEKJ PK PDA HARAH KB IKHA?QHAO EJPAN=?PEJC SEPD PDA OQNB=?A KB PDA IAP=H KTE@A (=NA;< OP=PAO PD=P SDAJ IKHA?QH=N >KJ@EJCLNA@KIEJ=PAO EP NAOQHPO BNKI ?DAIE?=H HEJG=CAO LNEI=NU R=HAJ?A >KJ@EJC >APSAAJ NA=?PERA OLA?EAO KJ >EJ@AN =J@OQ>OPN=PA KN BNKIIKHA?QH=N=OOK?E=PEKJO OA?KJ@=NUR=HAJ?A>KJ@EJC >APSAAJ PDA PSK 3Q?D BKN?AO KLAN=PA KJHU =?NKOO RANU HEIEPA@ @EOP=J?AO &KN =@DAOEKJ KB =JU GEJ@ PDA ?K=PEJC =J@ PDA OQ>OPN=PA IQOP =LLNK=?D A=?D KPDAN ATPNAIAHU?HKOAHU3AL=N=PEKJ IQOPNA=?D HAOOPD=J X PDNAAPEIAOPDA@E=IAPAN KB =JKTUCAJEKJ4DAOA=PPN=?PEJCBKN?AO=HOK@EIEJEOD EJLNKLKNPEKJPKPDAOETPDLKSAN KB PDA @EOP=J?A 4K =?DEARA PDEO HARAH KB =LLNK=?D PDA ?K=PEJC IQOP SAP PDA OQ>OPN=PA=J@OLNA=@=?NKOOEP7APPEJCEOPDANAOQHPKBPDAOQNB=?AEJPANB=?AAJANCU PD=PEONAH=PA@PKPDANAH=PERAR=HQAOKBPDAOQNB=?ABNAAAJANCUKBPDA?K=PEJC=J@PDA OQ>OPN=PA &KN =JU CERAJ ?K=PEJC =J@ OQ>OPN=PA OUOPAI PDA ?K=PEJC SEHH SAP PDA OQ>OPN=PAKJHUSDAJ PDAEJPANB=?E=H AJANCEAO I=P?D -KHA?QHAO =PPDAOQNB=?AKB = HEMQE@PAJ@PK KNEAJP PDAIOAHRAO PK IEJEIEVA PDA OQNB=?A AJANCU KBPDA HEMQE@ &KN MQ=JPEBUEJCPDEOLNKLANPU KJAIQOPPQNJPK. WA = γ 1 + γ 2 − γ 12 (+π e ) . $QLN[AMQ=PEKJ. .

(46) "=?GCNKQJ@. WA = γ 2 (1 + cosθ12 ) . 9KQJC$QLN[AMQ=PEKJ . . EJ SDE?D 7! SKNG KB =@DAOEKJ ODKSO PDA AJANCU KB =@DAOEKJ >APSAAJ = OKHE@ OQ>OPN=PA =J@ = SAPPEJC HEMQE@ SDE?D BKHHKSO BNKI PDA OQNB=?A AJANCEAO EJ I*lI) γ and γ =J@PDAENEJPANB=?E=HAJANCUγ%MQ=PEKJATLNAOOAOPDEOBNKI PDALKEJPKBREASKBIA=OQN=>HA?KJP=?P=JCHAO7!CERAOPDAI=?NKO?KLE?IA=OQNA KB PDA AJANCU NAMQENA@ PK NARANOE>HU NAIKRA PDA PSK LD=OAO EJPK OAL=N=PA AJ?HKOQNAO!@DAOEKJ >A?KIAO?KDAOEKJ SDAJ PDALDUOE?=H?DAIE?=H LNKLANPEAO KB PDA EJPAN=?PEJCIKHA?QHAO >A?KIA E@AJPE?=H =J@AMQEHE>NEQI ?KJ@EPEKJO BKN >KJ@EJC ATEOP4DAB=?PKNπe=??KQJPOBKNPDANA@Q?PEKJKBPDAOQNB=?ABNAAAJANCUKBPDAOKHE@ EJ R=?QQI KJ EIIANOEKJ EJ PDA O=PQN=PA@ R=LKN KB PDA HEMQE@ &KN HKSAJANCU OQNB=?AO πe 4DA=?PQ=H IA=OQNA@=@DAOEKJ BKN?AKBPAJ AT?AA@O PDA?=H?QH=PA@R=HQA>=OA@KJ PDA ?KJP=?P =JCHAO >APSAAJ PSK LD=OAO I=EJHU @QAPK AJANCU @EOOEL=PEKJ EJ PDA ?K=PEJC@QNEJCIA?D=JE?=HPAOPEJC (KSARAN PDA?=H?QH=PA@SKNG KB=@DAOEKJ?=JCERAQOABQHEJBKNI=PEKJ =HPDKQCDJKP JA?AOO=NEHU=??QN=PA KJ PDANAH=PERA=@DAOERAOPNAJCPD7DAJPDA?=H?QH=PEKJ KB7! NAOQHPOEJJAC=PERAR=HQAO OAL=N=PEKJODKQH@K??QN &KSGAO;< EJ =CNAAIAJP SEPD (=NA =O OP=PA@ =>KRA ODKSA@ PD=P = R=NEAPU KB ?KJPNE>QPEKJOBNKI=JQI>ANKBEJPAN=?PEKJONAOQHPOEJPDASKNGKB=@DAOEKJ. WA = W d + W h + W ab + W p + W i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d + W ab . . .

(47) #D=LPAN. (A ?KJ?HQ@AO PD=P PDA @AIKJOPN=PEKJ KB NA?KCJEV=>HA ?DAIE?=H >KJ@EJC =O = OECJEj?=JP?KILKJAJPKB =@DAOEKJ BKNIO KJAKBPDAI=FKN =@R=J?AOEJ PDAKNAPE?=H @EO?QOOEKJOEJPDAH=OPBKQN@A?=@AO 4DQO PDASKNG KB=@DAOEKJEOJKS PK>A?KJOE@ANA@=O ABBA?PERAHU=NEOEJCBNKI PSK ?KILKJAJPO PDA@EOLANOEKJ BKN?AO=J@PDALKH=N BKN?AOPK >A ?KJOE@ANA@ =O =?E@ >=OA EJPAN=?PEKJO )J OQLLKNP KB PDA LNAREKQO "KHCAN =J@ -E?D=AHO;< OQCCAOPA@ PD=P ?KJOE@ANEJCPDA?=OAKB =?E@E? LKH=NLKHUIANO=J@ >=OE? IAP=HHE? KTE@AO PDA KJHUBKN?AOKPDANPD=J@EOLANOEKJBKN?AO?=IABNKIDU@NKCAJ>KJ@O4DAUNAC=N@A@ PDAOAQOEJCPDA"NfJOPA@LNKPKJ @AjJEPEKJ =J@PDAKNEAO KB =?E@>=OANAH=PEKJODELO SDE?D C=RA O=PEOB=?PKNU NAOQHPO BKN PDAOA L=NPE?QH=N AT=ILHAO KB =@DAOEKJ 4DAU NA?KCJEVA@ PD=P PDEO OKNPKB PNA=PIAJP IECDP ATPAJ@PK= SE@AN jAH@ >U QOA KBPDA ,ASEO =?E@>=OA @AjJEPEKJO =J@ PDAKNEAO PD=P ?KJOE@AN AHA?PNKJ @KJKN=??ALPKN EJPAN=?PEKJO /NC=JE? LKH=NCNKQLO?=JEJPAN=?PSEPDKTE@AOQNB=?AOEJ R=NEKQOS=UO;<%EPDANPDA OQNB=?ADU@NKTUHKNPDAKNC=JE?CNKQL ?=J =?P=OPDA=?E@ =OPDALNKPKJ@KJKNEJPDA "NfJOPA@OAJOAKNPDAAHA?PNKJ =??ALPKNEJPDA,ASEOOAJOA KN=OPDA>=OA LNKPKJ =??ALPKN KNAHA?PNKJ @KJKN 4DA>KJ@>APSAAJ PDAOQNB=?ACNKQL=J@PDAKNC=JE? CNKQL?=JN=JCA=JUSDANABNKIBQHHUEKJE?PKRANUSA=GHUEKJE? =OEHHQOPN=PA@EJ. A − H ⋅⋅⋅ B → A − H + − B. . . 4K jJ@ = CAJAN=H NAH=PEKJODEL PD=P ?=J LNA@E?P SDE?D KB PDA I=JU LKOOE>HA SEHH LNA@KIEJ=PA EJ =JU CERAJ OQNB=?AKNC=JE? CNKQL ?KI>EJ=PEKJ "KHCAN =J@ Michaels;< D=RA@EOPEJCQEODA@ >APSAAJ PSKCAJAN=H EJPAN=?PEKJ PULAO &KN PULA! EJPAN=?PEKJO PDAOQNB=?A LNKRE@AO PDA >=OE? CNKQL SDE?D EJPAN=?PO SEPD =J KNC=JE? =?E@ =OEJ. O. H. R. . |. |. −MOH + R − C − R → − M O⋅ ⋅ ⋅ C = O. |. . R &KN PULA PULA " EJPAN=?PEKJOPDAOQNB=?ALNKRE@AO PDA =?E@E? CNKQL SDE?D EJPAN=?PO SEPD=JKNC=JE?>=OA. R / −MOH + R − C − R → −MOH ⋅ ⋅ ⋅ O = C \ R O . . .

(48) "=?GCNKQJ@. 7EPDEJ A=?D PULA "KHCAN =J@ -E?D=AHO BQNPDAN @EOPEJCQEOD PSK ATPNAIA?KJ@EPEKJO SDANAEJPDAEJPAN=?PEKJ=LLA=NOLNA@KIEJ=JPHUEKJE?KNJKJEKJE? 4ULA!$ELKHAEJPAN=?PEKJSEPD=JKNC=JE?=?E@ ,ASEO . H |. −MOH + HXR → −M O ···HXR . . . . . 4ULA!)KJE?EJPAN=?PEKJSEPD=JKNC=JE?=?E@ "NfJOPA@ +. _. −MOH + HXR → − M O H 2 X R . 4ULA"$ELKHAEJPAN=?PEKJSEPD=JKNC=JE?>=OA ,ASEO . −MOH + XR → − MOH ⋅ ⋅ ⋅ XR . 4ULA")KJE?EJPAN=?PEKJSEPD=JKNC=JE?>=OA "NfJOPA@ . − + −MOH + XR → − M O H X R . 8 NALNAOAJPO =J AHA?PNKJAC=PERA =PKI QOQ=HHU KTUCAJ KN JEPNKCAJ OKIAPEIAO ?DHKNEJA 0=NGO;< NAREASA@ PDA EOKAHA?PNE? LKEJPO KB OKHE@ KTE@AO )%03 DU@NKTE@AO =J@ =MQAKQO DU@NKTK ?KILHAT OUOPAIO (A OP=PA@ PD=P OKHE@ KTE@AO EJ =MQAKQO OQOLAJOEKJOCAJAN=HHUD=RA=JAHA?PNE?=H?D=NCA&KN PDEODAC=RAPSKATLH=J=PEKJO BNKIHEPAN=PQNA ==ILDKPANE?@EOOK?E=PEKJKBOQNB=?A-/(CNKQLO >=@OKNLPEKJKBPDAIAP=HDU@NKTK?KILHATAO@EOOKHRA@BNKIPDAOKHE@ "KPD IA?D=JEOIOATLH=EJMQ=JPEP=PERAHUPDAL(@ALAJ@AJ?AKBOQNB=?A?D=NCA=J@ PDAATEOPAJ?AKB=L(NAOQHPEJCEJ VANKJAP?D=NCA ?=HHA@PDAEOKAHA?PNE? LKEJP )%0 KNVANKLKEJPKB?D=NCA :0# 4DAPANIEOKAHA?PNE? LKEJPNALNAOAJPO>KPDPDAL(=P SDE?D=J EIIANOA@OKHE@KTE@AOQNB=?AD=OVANKJAP?D=NCA=J@PDAL(NAOQHPEJCEJ AHA?PNE?=HHU AMQER=HAJP ?KJ?AJPN=PEKJO KB LKOEPERA =J@ JAC=PERA ?KILHATAO &KN OKHE@OPDA)%0 >A?KIAOPDA)%03&NKI PDEO@=P= KJA?=J MQ=HEP=PERAHUKN@AN >KJ@ OPNAJCPDO HEGA "KHCAN =J@ -E?D=AHO;< OAA jCQNA BKN PDAOA >KJ@O KJ I=CJAOEQI)J PDEOjCQNAPDAEJPAN=?PEKJPULAO=J@@ELKHAKNEAJP=PEKJOBKNS=PAN=J@ KPDAN LKH=N ?KILKQJ@OLNA@E?PA@BNKI PDAP=>HAOBKNOARAN=HKNC=JE? IKHA?QHAO KJ 3E/ !H/ =J@ -C/ OQNB=?AO =NA ODKSJ O?DAI=PE?=HHU 4K LNA@E?P PDA .

(49) #D=LPAN. EJPAN=?PEKJ BKN = CERAJ KTE@AOQNB=?ALKH=N CNKQL ?KI>EJ=PEKJ PDAU ATLNAOOA@PDA AMQEHE>NEQI?KJOP=JPBKNPULA!KNPULA"EJPAN=?PEKJO=O. [MOH +2 ][X- ] Δ A ≡ logκ A = log = IEPS - pK A(A) [MOH][HX]. . [MO − ][HX + ] = pK A(B) - IEPS [MOH][X]. . Δ B ≡ logκ B = log. 7DANAL+! ! =J@L+! " NALNAOAJP=?E@>=OA?KJOP=JPO @AjJA@=O. [H + ][X − ] pK A(A) = -log. [HX]. =. >. and. [X][H + ] pK A(B) = -log. [HX + ]. If Δ! KN Δ" D=RA H=NCA LKOEPERA R=HQAO PDA EKJE? NA=?PEKJO PULA ! KN " LNA@KIEJ=PA SDANA=O EB Δ!KN Δ" D=RA JAC=PERA R=HQAO PDA @ELKHAPULA ODKQH@ LNA@KIEJ=PA!JKRANREASKBΔ!=J@Δ"R=HQAOEOCERAJEJP=>HAO !P RANU JAC=PERA Δ R=HQAO EKJE? BKN?AO >A?KIA JACHECE>HA =J@@ELKHA BKN?AO =NA SA=G .KJLKH=N LKHUIANO OQ?D =O LKHUAPDUHAJA D=RA RANU SA=G =?E@ LNKLANPEAO L+! ! H=NCA =J@ LKOEPERA =J@ SA=G >=OA LNKLANPEAO L+! " large and negative) CEREJCH=NCAJAC=PERAR=HQAOKBΔ! and Δ" SEPD OQNB=?AOKB=JU)%03=J@HA=@EJCPK PDALNA@E?PEKJPD=P,KJ@KJBKN?AO KJHU ODKQH@ATEOP=?NKOOOQ?DEJPANB=?AO. .

(50) "=?GCNKQJ@. Figure 2.7 4DAKNAPE?=H ?KJjCQN=PEKJ KB OARAN=H KNC=JE? IKHA?QHAO KJ =J =?E@ 3E KTE@AOQNB=?A=J@=J=HG=HEJA-CKTE@AOQNB=?A "KHCAN=J@-E?D=AHO;< 4DA=>EHEPU KB=HH OQ?D >KJ@OPKNAOEOPS=PAN @EOLH=?AIAJP@ALAJ@O OPNKJCHUKJ PDA L( EJ PDA =MQAKQO LD=OA )B PDA L( =P PDA EJPANB=?A ?D=JCAO >U PDA =@@EPEKJ KB ATPN=JAKQO LKPAJPE=H@APANIEJEJCEKJO OQ?D =O (

(51) KN /( PDAPDAKNU LNA@E?POPD=P I=TEIQI NAOEOP=J?A PK @EOLH=?AIAJP >U S=PAN ODKQH@ K??QN KJHU KRAN PDA L( ranges;< &KNPULA!EJPAN=?PEKJO)%03L(L+! ! &KNPULA"EJPAN=?PEKJOL+! " L()%03. =. >. 4NQA?KR=HAJP>KJ@O?=J KJHUBKNIKJ = OQNB=?ASDAJ=LNAPNA=PIAJPSEPD OEH=JAO has taken place; <"KHCAN=J@-E?D=AHO;<OP=PA@PD=P PULE?=HHU PDAI=CJEPQ@AKB PDAEJPAN=?PEKJPANI=PPNE>QP=>HAOKHAHUPK,KJ@KJ@EOLANOEKJBKN?AEJPAN=?PEKJ ?KIAO ?HKOAPK=>KQP .?I BKN AEPDAN S=PAN LKH=N KN JKJLKH=N KNC=JE? I=PANE=HOEJ ?KJP=?P SEPD = H=NCA JQI>AN KB IAP=HO KTE@AO =J@ OEHE?=PA OQNB=?AO &KN OQ?D OQNB=?AO EJ ?KJP=?P SEPD = JKJLKH=N KNC=JE? BKN AT=ILHA LKHUKHAjJO KJHU PDA ,KJ@KJBKN?AEJPAN=?PEKJOATEOP=J@PDAPKP=HEJPANB=?E=HEJPAN=?PEKJ PANINAI=EJO .?I 4DAPKP=HBNAAAJANCUKBEJPAN=?PEKJ BKN OQ?D OQNB=?AOSEPD S=PAN DKSARAN CAJAN=HHU NA=?DAO .?I 4DEO IA=JO PD=P PDA OQNB=?A EJPAN=?PEKJO @QA PK DU@NKCAJ >KJ@EJC=J@KPDAN@ELKHAEJPAN=?PEKJO SEHH BKNI LNABANAJPE=HHU PKPDAOEILHA,KJ@KJ .

(52) #D=LPAN. BKN?A EJPAN=?PEKJO 4DQO SDEHA JKJLKH=N LKHUIANO OQ?D =O LKHUAPDUHAJA LKHULNKLUHAJA=J@LKHUPAPN=kQKNKAPDUHAJA?=J=@DANANAH=PERAHUSAHHPKDECDAJANCU OQNB=?AO OQ?D JKJLKH=N LKHUIANO @K JKP GAAL PDAEN =@DAOEKJ PK IAP=HO =BPAN ATPAJ@A@EIIANOEKJEJS=PAN &KN OPNKJCAN >KJ@O HEGA,ASEO =?E@>=OAEJPAN=?PEKJO G*IKH PDAPKP=H AJANCU BKN @A=@DAOEKJ ?=J >A ?=H?QH=PA@ >U QOEJC PDA PDAKNAPE?=H I=TEIQI @AJOEPU KB >KJ@O=PPDAOQNB=?A KJ=J=RAN=CAKB DU@NKTUHCNKQLOLANJIBKN=HQIEJEQI; <4DEONAOQHPO SEPDPDAQOAKB!RKC=@NKʼOJQI>AN EJ=@A=@DAOEKJAJANCUKB*. I4DEO SEHH LNKRAPK >AIQ?D HKSAN OAAQJ@AN PD=J PDAPKP=H @A=@DAOEKJ AJANCUKB=LN=?PE?=HOUOPAI 2.4.3 Organic coatings and representative molecules 6=NEKQOKNC=JE??K=PEJCO=NAQOA@PKLNKPA?P=HQIEJEQI=HHKUO =OIAJPEKJA@>ABKNA )JPDAJATPL=N=CN=LD PDA?KJjCQN=PEKJOKBPDAIK@AHOUOPAIO =OPDAUSEHH>AQOA@ EJ PDANAOPKBPDEOPDAOEO SEHH>A@EO?QOOA@3EJ?A=@DAOEKJ KB?K=PEJCOP=GAOLH=?A =PPDAEJPANB=?APDNKQCDIKHA?QH=N>KJ@EJC PDA>KJ@EJC>AD=REKNKB?K=PEJCO?=J>A EJPANLNAP=PA@>UQOEJCKNC=JE?IKHA?QHAO 4DA=LLNK=?D BKN PDEOPDAOEO S=OPKAT=IEJAKNC=JE? ?K=PEJCOKJ PDA>=OEOKBPDAEN =R=EH=>EHEPU=J@PDALKOOE>HAQOAKBIKHA?QHAONALNAOAJPEJCPDABQJ?PEKJ=HCNKQLOKB PDA ?K=PEJCO!J =LLNK=?D OEIEH=N PK 6=J @AJ "N=J@;< S=OP=GAJ PKQOA OQ??EJE? =?E@ IKHA?QHAO PKNALNAOAJP PDA CN=BPEJC IKHA?QHAO QOA@ BKN KPDANSEOA JKJLKH=N ?K=PEJCO =J@ =@DAOERA AC LKHULNKLUHAJA !@@EPEKJ=HHU = LKHUAPDUHAJA PANALDPD=H=PA 0%4' jHI S=OQOA@=O = IK@AH OUOPAI PKOPQ@U ?K=PEJC=@DAOEKJ KJ PDALNAL=NA@ =HQIEJEQII=CJAOEQI O=ILHAO!O NALNAOAJP=PERAIKHA?QHAO BKN 0%4' @EIAPDUHPANALDPD=H=PA $-4 S=OQOA@ &KHHKSEJCAMQ=PEKJO=J@P=>HA= =PPDAAJ@KBPDA?D=LPAN PDEOIA=JOPD=P BKN OQ??EJE? =?E@ LHA=OANABAN PK#D=LPAN=J@BKNPDAATLANEIAJP=HNAOQHPO SEPD L+a AMQ=H PK>AJVKE? =?E@ =LNA@KIEJ=JPEKJE? EJPAN=?PEKJSEHH P=GALH=?ASEPD CKK@ =@DAOEKJ =O = LKOOE>HA NAOQHP KJ =HQIEJEQI =J@ I=CJAOEQI =HHKUO &KN $-4 BKHHKSEJCAMQ=PEKJ =J@ P=>HA> (at the end of the chapter) (please refer to #D=LPAN BKN PDAATLANEIAJP=H NAOQHPO KJ PDAKPDAND=J@SEPD RANUJAC=PERAΔ" KB PKBKN NAOLA?PERAHU!H/ =J@-C/=OOQ>OPN=PA JKOPNKJC>KJ@EJCI=U>A ATLA?PA@ 7DAJBKHHKSEJCAMQ=PEKJO==J@> EJ ?KILAPEPEKJSEPDS=PAN=PPDAOQNB=?A BKN OQ??EJE? =?E@ KJ !H/ PDEO IA=JO PD=P NAOEOP=J?A PK S=PAN @EOLH=?AIAJP =P PDA EJPANB=?AEOHEIEPA@PKPDAL(N=JCAKB=J@BKN-C /( KB PK/B?KQNOAEJ LN=?PE?A-C /( EOJKPOP=>HA>AHKSL( PDANABKNA>KJ@EJCSEHH>AQJ@ANIEJA@ .

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