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Electrochemical behavior of aluminized steel type 2 in scale-forming waters

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Material Information

Title:
Electrochemical behavior of aluminized steel type 2 in scale-forming waters
Physical Description:
Book
Language:
English
Creator:
Caseres, Leonardo
Publisher:
University of South Florida
Place of Publication:
Tampa, Fla.
Publication Date:

Subjects

Subjects / Keywords:
Cathodic behavior
Modeling
EIS
Galvanic corrosion
Durability
Dissertations, Academic -- Civil Engineering -- Doctoral -- USF   ( lcsh )
Genre:
bibliography   ( marcgt )
theses   ( marcgt )
non-fiction   ( marcgt )

Notes

Summary:
ABSTRACT: Aluminized steel Type 2 (AST2), often used for culvert pipes, is subject to corrosion which is the most important durability limitation factor. It was desired to determine if the outer aluminized layer will retain passivity and if protective galvanic action will develop. Thus, corrosion of unblemished and blemished AST2 surfaces was investigated in simulated natural waters. Experiments with unblemished specimens showed passive corrosion rates (~0.06 μm/yr) in scale-forming, 0.01 M Cl- solutions but sustained corrosion in other less protective media (with rates 3~10 μm/yr). Corrosion was manifested macroscopically by discoloration and few macro pits, but it likely proceeded also microscopically at the Fe-rich inclusion space scale. For blemished specimens, the aluminized coating galvanically protected to some extent the steel in all solutions. However, in 0.01 M Cl- solutions, protection was delayed until after some steel corrosion had occurred.In some solutions, complete consumption of the outer aluminized coating around exposed steel was noted. Elsewhere, coating appearance was similar to that of the unblemished condition. Nominal durability projections made for 16-gage AST2 ranged from >100 yr for unblemished AST2 to ~10 yr for the blemished condition. The present findings were used as a first step in proposing refinements of presently used durability guidelines of AST2 culvert pipe. Cyclic cathodic polarization tests to examine O2 and H2 reduction at the Fe-rich inclusions showed significant hysteresis, more pronounced with decreasing scan rate. The effect was tentatively associated to the amount of Fe+2 being deposited during the downward scan, a hypothesis supported by results from a physical model. A static polarization model was formulated for the blemished configuration. Results matched experimental trends and permitted evaluating the effect of solution conductivity σ beyond the experimental range.Exposed steel corrosion rates at the steel were increasingly large for decreasing σ. For the lowest σ, corrosion rates at the exposed steel center were distinctly larger than at the edge, consistent with experiments. An impedance behavior model was also formulated. Results showed frequency dependent current distribution and predicted relatively small artifacts that were and not evident experimentally, but should be considered when exploring other system conditions.
Thesis:
Dissertation (Ph.D.)--University of South Florida, 2007.
Bibliography:
Includes bibliographical references.
System Details:
System requirements: World Wide Web browser and PDF reader.
System Details:
Mode of access: World Wide Web.
Statement of Responsibility:
by Leonardo Caseres.
General Note:
Title from PDF of title page.
General Note:
Document formatted into pages; contains 258 pages.
General Note:
Includes vita.

Record Information

Source Institution:
University of South Florida Library
Holding Location:
University of South Florida
Rights Management:
All applicable rights reserved by the source institution and holding location.
Resource Identifier:
aleph - 001920220
oclc - 187955152
usfldc doi - E14-SFE0002103
usfldc handle - e14.2103
System ID:
SFS0026421:00001


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Full Text

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3 ,

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B =,=(.!n n =B>!1@ 9+=DDD?=, =n+n:n nn 4,& n=B,

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9 >707+=DB2?,$ 5n!!;9,:4+ 5n :, r8 +r>=DBD? nn nn n 8> 8>5?O7 >?:>:?n!;>!??I 4n,:4+ nn n n7, 8n+$: >=DA9?nn4n 4, !+4 8n 8nn 4 nn nn+ n 4 n n,,8n$ nn n7 n&DD+n4> ,=? =1>K=,ADnn7? nn

PAGE 55

99 nn,n>,=? 4,n n n K=APn7>,?+ 8nnnA> ,+229?n n>&?4 8 >#?+KA92Pn7,n n8n4 nnn4 K,@4F1==4F+,n n 4>&& :7+=D3?, !nDAnn4n 7+4 + nn,n8 4@ >,9,@?4 +8n ,nn8 nnK1nn n4 +44n n 2,9nnAn> !,+=DD1?4 K=nnn n>!?, !4, n4 n4 4 nn8 ,4 4A22n 4

PAGE 56

9@ 8n,n nLn 44 44+ 4 4+n n, >$?+n7 >/$?+: 7>!?+ 4>? &#==@=D2 ,,4 n+nn n 4T=21Wn,!n/;: /!>!?+/:!;9+/!+:!>/$?+/:!;9+/!+:!+!>;:?>$?+ nnnn4 >?4, nn + n+4,9,n7 ;+ 492K2,2 9n9L4 !;>!?n> /$+$+? n8n ,707+=DB2?( 9A ,1 :=2 =2 >,=?

PAGE 57

9A !/$ 5OA,D2,1+ $ 5OU=,AU2,@+ ,5+$ !!;9K2,Ann74 n 8,8n 7n $+=2 n!!;9444 9=@B2nKAnn KDnn7+ ,5+ nn,n 48 n!!;9!!;94&>;:? 4>&,+=DD?, +&>;:? : n :TD,9>r,+229?, $4 4, nn4K9+=22 \[! !+/$+ $,: + >;!?n 4nn,n5 n >5?nn4;!4Cn]$!5@922 "n=227: =n: =2n<.&n,nn+ n 4n+444 + 8n,n $/$

PAGE 58

91 4&7>&?>#C ,+=D3A?n n4 =12L=B3 Ln n2922n<, ;!=2nn8 !? 4n8n 4,5 n8+ @,!@4 nnn;!, ,9,=;!#;! ,A,B8n;!n, 5nnnn+;!4K192n<+K1A2n<+KB22 n<+K3A2n,A? KD2KDA2n<,K9=2 >K==A nG?+>4 n?n

PAGE 59

93 74nKH2,=nn4 n7 ,&# nG=4 4 nn8, 4 4nn: 8, 4+;!n44n KB92n<, 5/$>,1?+;!KD=2n,3?+ 8!!;9n G=Gn ;!8KB2 n<44n;!K332n<+ 8!!;9,nG9>48!!;9?4 ;!KA2n,B?+;!nG= nn8KD22n
PAGE 60

9B n4;!K1A44 KB@2n4n? 7,+n 4 n4;!, +n n 4n, 5+n8n> !@?4 +n4nn + nn+ n ,,9,!n ,D4nnnn+ 7: 4 ,,:4+ "n44 +7: /$+$+48 47 ,5$+ 7:n"8 K3,B K3,D+,5/$+4+ 7:KB,A @KB,3 ,5!+7:

PAGE 61

9D 4K3,39+222n8nnKD,2 K9=2,: 4 n, 7+n 4 & 8n 4>=DD?+4 ,, U+nn K+222nn+4H2,2 =n, ,9,95nr +n $+/$+" nn 4" 8nn!$ n>!$?9 "nnK=22:,# "4n> +n ># +=D13? 4?4" n >,=2?, n/$>,==? 4n n4=n:nn 4n+ 9!$nZ!$O=LE>'_?4_O`+Enn nW=n>n?+>n? >:&+22=+ += DDD?,

PAGE 62

@2 4 n,=n:n n n+ n4 >K9B27 an?K9+2228, n n4n 5$>,=?+=n:nn nG=>G4?4>T1+2227a n?4 4n,:4+!!;9=n: nn4nn K=+@A27a n4K=2+2227a nK9+222, nG9$>,=9?+= n:nn 44K=2+2227a nK9+222+ 4 n8 n, "+nn4 4+ ,& ,@,,=7 n n>,=@? 4n n4=n:nn 4n K91A7anKA2@84 K327an+4 ,4+ =n:nn

PAGE 63

@= n, nn 4+ 444+!n n n4n ", +!nn 4 4!$n 4 8n/$+$+ n,n 4">,=A?4 nn /$+$++ 44 ,n8n=n: n n>K1B7an?+4 +4 n4 =n:n n,n44 ,$ "n+ "n n /$+$+,,@#,@,=#!$n n nnn4 ,<8n n $>4 n ?

PAGE 64

@ 8+ n n,84!!;9$ n"nn n 84,4n 4 n4n/$ >4 74 n ?, 4n4n 4!+4 47+ !!;9+n ,4 n 8+n7 + +L4 4 8n nn8n, nnn n "8n @,+!@, ,@,!&n5n 5!=+ nnn 4,5+ n 4 n 4,

PAGE 65

@9 n4 n n >/+=DD2+0+=D3=?, 8nn4 4 nn bU9U94U9,78nn nn7 n+ n4nn>$ +=DDD?, !=+n74 :n n8KB,A>$8+=D3@?,5 + nnnn n> nn>;:?9nnn n?n8 n7 n;:4nn >;:?@ >#+=DDD?, nn n nn>+22=++222?, %7n +7"nn &#>=DBB? !>=DD=? 4(

PAGE 66

@@ >;:? ;: >,? >;:? ;: >;:? >,r? 9 >;:? ;: >;:? >,!? @ 9>;:? ;: >;:? >,#? 4nnnn +" nnn+ n n,5 7 + 78nn + 8 n >77n47+=DDD+7+22= ?, 4 48 nn7>75+22@+ n:+=DD=+ /+=D3D?,n!=+ nn n n >&!+229++=DB1+&!+=DDA?, nnn n 7,n +:U n+4+ :4 nn+ > n+22+7+=DDB+<7+ 222?,n nn nn+L n

PAGE 67

@A 4>$7 +229?,5 8nn7, nn44 n5 8n,; +5" nnn8 n>& +=DD2+229?,nn 4 + 8nnn n nnnn># 7+=DD1+ +22=+n7+222+ $7+22A+ 75+=DD2?,5 nn n n"+ nn"n8 "4 n,5+ nn "48 4+ 4nn n nn" 4,=1+4 4n n n 8,

PAGE 68

@1 5nn n+n >&5!?+ 7 n n, 7++&5! n nn ,@,,=$/$# 4$ 8n /$n nn ,5+ n;!4" 44 nn n+nnn8 84 4n n n 4"4 ,=1,. n@,47nn nn>4 n n?+4n4:n !:+ nn n!$,n 7 @n,=18 nn Lnn n>DAn?,

PAGE 69

@3 4+n + 4n n, n+n ;!8 n>/+=DD2+0 +=D3=? 4, 8 ;:n :nn 8, 4"n n+ 4 n 8>r ,+=DD+ 7+=DD1+n n+=D39+ -n+=D32?, + >8nn!$ ?4"n =+4"n. =U. >n n+=D39?,!"+ n!$ 4,8 nn nn4 8!, ",=14 5n ,@,An n +4 ,== ,=A,!$4+ 4+ n

PAGE 70

@B ,nn T=4 !$,5+4 4nn O=4n44 T2,D9>7n ,=1?, ,=3,=B48nn nnn > /$n n 4+ ?, +. =$4 >K,A=21anK=,A=23an+?+7 8n+74 n ,n 4 /$4. =+K9=21an n, E 4n 4n E+4n!$ n ,5$+E 4K@=2A LWn4 nnK=,9=2@ LWn 84!!;9nG=G nK,=2A LWn,E 4 >K9,9=2A LWn?nG9$+4 4 !!;9,E n/$ 4

PAGE 71

@D K@,1=2A LWnK=,@=2A LWn n !$4n 4,E4n >K9,@=21K==2ALWn?4 8n,54+ 4 !$4"n!nn nn!$"/, n4&+/4=2:,5+ !/48n ,+ n r ` ` E = / >,9? 4!nK,1K3,DRLn+nE K=,n nn>$+=DDD+r7-+=DD3?,5 n 7 c+n !4( c c !2 >,@? 4c2nn,n KAn cKD> 74nn n>r,+=DB9+ #+=D3?nn 8+?

PAGE 72

A2 !K=,12PLn,n!:>r7 -+=DD3?n K!+4 8n44!, 8n 4 4! n",,@,n nn > $+=DDD? n, !n n n8 n 7 >n7 ?+ !H ,&8n nn 8n;!,5+ 4+n 8n", ,@ 4!44,8n+ n n nn>r7 -+=DD3+22@? "+!K>cc2"=>?/ =?2,A+4"+/ >n n?+>&+=DB2?,

PAGE 73

A= n!>?HH!:+!>?4nn=2:& nnn=22n<( =2: Zd ` 7 K !/ >,A? 4Zd>=2:?nnn 7!>? ,7!>? =+44>4. =n? Zd>=2:?n44 n nA, ,=D4& /$$ K9928 ,n+ 4 n,4 4>nK9 ,@KA,DPLn?+4 n7, ,@,,!++/$ # n n nn4 nnn A7!>?+nnn=22 :=:4 4n &, nn E44 !>?",,9, 7!>?O!>?`/Zd>=2:?,<7!>?n4 n,

PAGE 74

A 4nn,+8 n4 nn, :4+ n n>n/$ !?nn n78 n,:: 7 !>8? /$>?,: !48n ,: /$4 n4 "n4 4n +4n7 n>4 ?+ n,+>4 n>;:?@ ",,#?nn8n 7 n,5 7+ !4+78 4n n :n; ,+4nn+ n nn+ ,n+ >;:?@ nn nn n>;:?9+ >;:?@ b>;:?9U;:+8>/ :+=D3D?,48

PAGE 75

A9 "n /$,54n n "nn n, nnn 4 n4 n>; -n+=DBB?,5n +8n +n n,5+ n 4+ 8!@+4 n :7 n, /$!4 44 4n+7 +4, 8 nn >K2+222n K932 nn47?,nn n 4, +4 +n8 4" n,nn+

PAGE 76

A@ n-> =D1? r%>=D1D?n( 2,3@A 2,=@ !? >< >,1? +;!4 n nn>K3A2n<2+222n? 4n,5+nn n +n4 nn>+=DD2? 8,5 n 7 "nn n >/+=DB=+ .+=DD@+<<-n+=D31? ,nnn n ,%n+ ;!nn 4 n8nn7 8>+n ?, 8 n nn8>8 n?,% nn n+n 4,

PAGE 77

AA +nnn 4 7n n 78,5 +K932n + nnK1A2n<,4 n >n ?+ n;!/$!4n4>D22n< B92n n?4n ,=14.!$nn ,:4+nn 4" n 88,$+ nnn n,! nn n, + n8n n +4 n8

PAGE 78

A1 n+n8n ,$ n+ n n4 nn+ OI=L@$+4$>;-n + =DBB?,". 4++ nn "+n 8n nn(. =eOI=>@ ?=f$/$U$ /$ g= >,3? 4 nn+/$nn >nn$?n+/$ n >n$ ?n,n n"n n ,:4+n =+ ,A,3!+/$++ n4. =eI4 ,+$KRn+$ K=22Rnn +/$ HALn+n/$K=29Ln,8n n+/$ 4+ > &7+=DBA?, "+nn n. =n!$

PAGE 79

A3 ,n 4n ,n nn n+ n n !$ !n >K2,BDK9,7an?. =,+. 4nn>K1B7an+K@DA7an ?,rnEE "( K2,A32,19>4 ",=A? K2,1D2,B2,E4 K@,1=21K,D=23Lan+ "+! 44 n + E >K1,D=2AK=,3=2A Lan?4 n$/$ nK=397anK=@97an ?+. =nK=127anKAA7an 8,nEE >K2,D= K2,DB?4,=@,E

PAGE 80

AB nK=,@=2AK=,3=2ALan,n !",,"/O=2:4K=2,A PLn4nn $n, n+ . =/$K=2Aan8,r nEE nK=2A LanK=2@ Lan++4" >K2,D@ K=,22?, ,@,9!n/n!! # 4n n 4nn ",,= 8n,!n4 n48, n$8 n/$ n +47nn "n >. =?8nn + h!K22n<, h!7 nn>nrn+=DD1?n n4!9 nn

PAGE 81

AD 8$, 4 + n+ n n C >C+=DA3?( Kh!>,9. =?= >,B? n !+/$ n+n47 n4n n n h!Oh"22n<,+ > &+=DB =?( K2,Ah!>,9. ?= >,D? 48nn$>K2,29PLn K2,22BPLn8?,:4+ 8 !!;9nG=Gnn K2,= PLn8!!;9,n+ nG9$>8!!;9?48nnK2,21 K2,22=PLn, n/$n 4K2,=A PLn+K2,29PL nK=+@22, $/$ n44 n,

PAGE 82

12 /$ n + n4 n K2,PLn+n4 nnn, !+ n nK=,2APLnK2,=9PLn K9+222,8+ 4 n ,n !n4 : 7nn, n44 nK2,9PLn 8+n4 0/>=DB@?n 8 4nn 5nn n+ 8n, n 48n nn ,A5n. 4' n7@A Pn>92Pn=APn ?n=+A22 Pn78n

PAGE 83

1= =17+ nn 4 ,5n' n n8n4 n .4 n +74 n7 n n+ n47 +7 4, r+ 4 :+' n n + n n8, + nnn8 ",+ n 7"n nn 7, 8n 8nnn,@ ,3, 4n n

PAGE 84

1 8nO24n >?n n 5nn4O= 5nn,+ n( = = = = = = = !. 92 i 92 >,=2? 4nnn4+O9LU9+i nn+n7 nn !. $+4n7 n4 +:+ n+ 8nn!. >H2,@PnL? 4n T=22 +4' n nn 8n nn $>r+=DBD?,8!!;9n4 nK= PnL+ n n, #'nn nn ,+ /$4n n47 4+:+ n+!. 4n>K=,2@PnL?,5

PAGE 85

19 n+4n K92, n :7 nnn 4 nn 8 n4:TD>$74 +=DB3?,!+ 4n7n4 47 +:+n+! 4K9,=1PnL+4 4n K=2+ 4n 8, n4n+ !. 4n >K9,APnL?n KD, '+ nn +4"7 n n8n n,n4 $7 >=DB?>=DB@?+4 n8 nn4 nn, nn + 8 K=RLnK=2 RLnn!@, n4&! >=D3@?+;>=DDD?+

PAGE 86

1@ >=DD1?,' 4K1KB n, ,Bnn n> ? n!=+ n n n,/+ n n+,, -+!+55+#;n ,n nn+, B+4n n4, =1n ,!n4 'n 8n nn 8 4+n + :>$?+ n n#;55 n4n4> -!n? n ,47 L4+n +:>/$?+ nn #;n4n4 ,;+55+! +-n n n4 ,4n +47

PAGE 87

1A +:>!?+ 4n4 n-+!+ #;n n' 55n,5 8n4+ + :>?+55n nn +4 !n ',5 n+ #;n n48 KB22n, r+nn 4#; n4n 4 >,,KA22 nK=+222 n?n7 >,,K3,AH:HKD,2?, 8 55n n48n >,,HA2 n?:, 8 n n ,5 +&5!+ n n 4 ,7&5!n nnn+ n n,

PAGE 88

11 5 n4 nn,5n n" +n n>,,? nnn +8 n,#n n n!@,,1! =,5T9+222+nn 48n 4n>HK2,22BRLn? n4n >$?+ ,57+n nn4n >/$?+n n 44Lnn>HK2,=2 RLn?n 8,:4+nn nn n>K2,RL n? 84n + nn :, 9,8n 7 >!? n

PAGE 89

13 n 4n +4n :7 ,+n 4 >K=RLn?K2,=ARLn+4 :, @,8 >?n4nn 4 nn4 n K2,9RLn8, A,& n nnn 8n ,n4n n !/$nn nnn n n n, 1,5nn n /$!n7 nn :7> /$?+44nn n n+ +

PAGE 90

1B nn+ n+ 4n 3,$n /$ n+n 4 n 4n 8, B,!+/$ n+n 4n n" n nnn nn8 n+4" n D,'nn =1n 4T=22 n>$?+4=A91 n n,5n n n 8n, 4 n n nn,

PAGE 91

1D =2,4 #; nn n4n 4 >,,KA22 nK=+222 n? n7>,,K3,AH:HKD,2?, 8 55n n48n >,,HA2 n?:,8 nn

PAGE 92

32 ,=(!nn >F4?,!&$!!/!/& 2,2A2,22,2212,2=2,2=2,292,2@2,222,2=32, 292,222,22@2,229r, &!!$ 5, ,(n ,:!r5 : >::? !UnL nL I RnLn !>?12B K3,@ >KD,2? 2=+=@2 /$> ? @B2==@3= K3,B >KB,3? 2=+BA2 $>?=B@A=99 K3,@ >K3,B? 22 93 =+9D2 > ? =2B+B2=B+@B2 K3,9 >K3,D? jj@2+222 ((78nL !!;9+:( 8nL !!;9+I(+: +::(4 :+,j,9n4 n, ,9(!nnn 4 n,5!/U;@ &U!U-U:!;9 rUrU9 !Ln=D+B@1==+2@+31B=+91@=D@22 =@A13,==9,B@,3 ,@(<"n ,=1n n5nG=8 $,n W = 7W E LW 7W E LW Pn @B=3,B3,29,=D2@2,D@3,29,B929=,222,29@ =1=3,3AA,A9,@D2@2,D@93,19,B929=,222,2= 1 9==B,93D,19,A=2@2,D@@3,B9,@29=,222,2= = 991=3,==2,=@,222@2,D@3,1=,A2=,222,2D= @B2=D,A=B,@@,==2@2,D@=1,A3,3A29=,222,2A 2 A2@2,=2,3@,B2@2,D@D,DD,3B29=,222,2BA 1@2,3=3,@,912@2,D@=A,D1,9=29=,222,2A 9 =@B,=,AA,2D2@2,D@2,3,3A292,DB2,2 @= 9312,D3@,BA,@=2@2,D99,A=,B@29=,222,2 = 923=,1==2,@A,9D2@2,D9A,@,2B29=,222, 22B /nn ODAn,

PAGE 93

3= ,A(<"n ,=1n n5nG=8 /$,n W = 7W E LW 7W E LW PLn @=@,B1,19,1D2@2,DAD,1@,@29=,222,=@ =@@=A,9=9,D@,22@2,DA=3,A,@@29=,222,23 912=@,DB,3@,BA2@2,D@=9,1,B1292,DD2,=2 1@=A,22,@@,DB2@2,D@92,A=,=@292,DA2,2@ B1@=@,D@,@A,212@2,D@3,D=,9=292,DD2,2@ =91B=A,9B,=A,AD2@2,D@9=,=,D292,DD2,2 9 931=@,33,D3,292@2,D@1,1,3@29=,222,23 92@B=@,A,=D,12@2,D@,2D,D29=,222, /nn ODAn,,1(<"n ,=1n n5nG=8 ,n W = 7W E LW 7W E LW Pn 9B@2,@B=,3=,92292,D=,B,@122,D32,A A2@2,A=,=,9A292,D,=,@322,DB2,= 1@B2,@B,2=,93292,D,2,A@22,DB2,9 B1@2,@B=,3=,A9292,D=,@9,=222,DB2,9@ =222,@D=,3=,1@292,D==,99,2322,D32,9A =@1@2,A=,9=,19292,D==,19,2122,DD2,B =1B22,A2=,D=,13292,D==,99,2=22,DB2,9A =BD12,A=,@=,1A292,D==,A,DB22,DD2,92 @@2,@D,@=,1@292,D==,A,3922,D32,92 3122,A=,1=,1292,D==,A,D122,DD2,92 92D12,A=,3=,19292,D==,A9,2922,DD2,92 /nn ODAn,,3(<"n ,=1n n5nG=8 !,n W = 7W E LW 7W E LW PLn @=D,A=A2@,912@2,D9@,D=,D@292,D92,2D 912=3,1D,@D,AD2A2,A32,31,AD292,1D2,19 A2@=B,1=,=1,A32A2,12=,9@,D292,32,9@ 1@B=B,@=9,AA,@2A2,1=,B9,@9292,3@2,1 B1@=D,2=A,D@,@2A2,19,@,32292,312,=D D12=B,==A,1@,222A2,1@,,1A292,312,= =9D=1,D=D,=9,3B2A2,1,D,=292,332,=1 @22=3,AB,D,BD2A2,19@,==,B=292,3D2,== 92@B=3,19A,,3@2A2,19A,=,1A292,B22,2D /nn ODAn,

PAGE 94

3 ,B(!nn+ + n !, -!55#;! $H2DA3A1T=22>T=22? /$H2AA29991>9B? /3=A/=A>=D? !H29213=D>9? /n nn, ,=(! =1>K=,AD nn?7n 4F/ 4 &#

PAGE 95

39 =,U2= =,U2 =,U29 =,U2@ =,U2A =,U21 =,U23 22@212B2=22 #n+ n .! & ,(& n >?4 n ,9(nn, C7 $
PAGE 96

3@ ,@($, = 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22 nL;!L<,! !>G=? !>G?,A(;!n!, 8 n,

PAGE 97

3A = 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22 nL;!L<,! /$>G=? /$>G? ,1(;!n/$, 8 n, = 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22 nL;!L<,! $>G=? $>G? $>G9?/8!!;9G9 8!!;9G=G ,3(;!n$, 4 4!!;9G=G,8 n,

PAGE 98

31 = 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22 nL;!L<,! >G=? >G? ,B(;!n8 8n, 1 3 B D =2 2A22=222=A22222A2292229A22 nL: !>G=? !>G? /$>G=? /$>G? $>G=? $>G? >G=? >G?,D(7:4 8n,

PAGE 99

33 =2222 B2221222@222222 2 2222@2221222B222=2222.>Z?L n5n>Z?L n /$@ /$912 $@B $9= 9B@ A2@=22: =2: =2: =22: ,=2(5" n/$+$+, 9,U21,U21=,U21 2,U22 2,U22=,U21,U219,U21@,U21A,U21 .>Z?L n5n>Z?L n @ =@@ 912 1@ B1@ =91B 931 92@B ,==(5nG= /$>=22-:=n: AL4?, =2L

PAGE 100

3B 1,U21@,U21,U21 2,U22 2,2U22,2U21@,2U211,2U21B,2U21=,2U23 =,U23 .>Z?L n5n>Z?L n @B =1 9= 991 @B2 A2@ 1@ =@B 931 923 ,=(5nG= $>=22-:=n:A L?, ,AU23,2U23=,AU23=,2U23A,2U21 2,2U22 2,2U22A,2U21=,2U23=,AU23.>Z?L n5n>Z?L n @2B 1D1 BBB 92D1 9=2 ,=9(5nG9 $>=22-:=n:A L?,

PAGE 101

3D ,2U2A =,AU2A=,2U2AA,2U2@ 2,2U22 2,2U22A,2U2@=,2U2A=,AU2A,2U2A,AU2A9,2U2A9, AU2A@,2U2A .>Z?L n5n>Z?L n 9B@ A2@ 1@B B1@ =22 =@1@ =BD1 92D1 ,=@(5nG= >=22-:=n: AL?, 9,2U2A,2U2A=,2U2A 2,2U22=,2U2A,2U2A 2,U22=,U2A,U2A9,U2A@,U2AA,U2A1,U2A3,U2A.>Z?L n5n>Z?L n @ 912 A2@ 1@B B1@ =9D @22 92@B 222=222 2 =2222229222@222A2221222 =2L ,=A(5nG= !>=22-:=n:A L4?,

PAGE 102

B2 ,=1("n 5, =,23 =,21 =,2A =,2@ =,29 2A22=222=A22222A2292229A22 nLE+E L =n ,=3(nn n nG=/$>?+$>"? +!>?+ >n?>E+E ?,4!!;9$>G=?, !$ >E + ? . = !$>E+? /!!;9 $ >G9?

PAGE 103

B= =,U2 =,U29 =,U2@ =,U2A =,U21 =,U23 =,U2B 2A22=222=A22222A2292229A22nL. =+. L n ,=B(n 8n nG=/$>?+$> "?+!>?+ >n?>. =+M. ?,4!!;9$>G=?, 2,2U22 @,2U=2 B,2U=2 =,U== =,=,==,22,D2,B2,3L<,!! Ln@ /$>=? /$>? /$>9? /$>@? $>=? $>? $>9? $>@? ,=D(&78n /$ $n>nG9G@?K9928 ,! 5;!nG=Gn 8 4>nG ?, /!!;9$>G9? >G9?

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B 2,22= 2,2= 2,= = =2 2A22=222=A22222A2292229A22nL L n $ /$ $>G9? ,2(/n nG= n,/84!!;94n $>G9?,

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PAGE 170

=@B n4n4 >,,KA22 nK=+222 n?n7 >,,K3,AH:HKD,2?,:4+n 4 8+ -n nn n, 48 55nn 48n >,,HA2 n?:+4 !n ,+ nn n nn Ln+ 8 n n, 5+ nn n+ nn n,n n4 4 44+ 4 ,5 nnn" 4, n+n n 4n 4n+

PAGE 171

=@D 48K9F2,2 9F,5 nn" +n n>,,? + 4n8, 8 n2,29F, nnn +4 n8n @,1!=,C4 n 87 n, :4+n>,, $? 4 4K32K3A2n<>n ?+4n 7 , +n n48>8n 4n. $?4n n 4 n, 9,4 nn>/$+ !+?+4n

PAGE 172

=A2 ,$44 8n4, @,5nn n n !r >Ln?4K92PnL $/$+ K=,APnL,!r> nLn ?+n n 4K=APnL/$+K2,29PnL $+K=PnL+ 2,@PnL!,n48n 4 nn7,/+ nn n A,nLnn 8 nnn !>Ln?,5 n+ n4 nn>$?9+222,:4+ nnn n nn nn 4n>K9=2@?, n 4K9APnL, 1,!+n4 n" n

PAGE 173

=A= !+/$+$+nn ,nn nnn n n, 3,nnn n 7n > 4!?+44 nn nn n,7n 8 ;+4 n 8 B,$>n nn8 Ln 8? nn n + 44 >!?, D,'4n= 1n nnn nn n+ nn5nn 4,n+

PAGE 174

=A 4T=22n>$ ?n 7+47 4K=2 ,n+'4 4=199, !nn8 +! +4, =2,n48 + -nnn n4n 4>, ,KA22 nK=+222 n?n7>,, K3,AH:HKD,2?, 48 55 nn48n >,, HA2 n?:,+ nnn n nL n+ 8 nn

PAGE 175

=A9 @,=(7nn+n 7 +n n n, 7LPn n r 8 8 8 n /n PnL !r>?@A,3@A,A+B22 !r/$>? @A,2@2,D 9+@22=2 !r/$>=?@3,B9B,=+12299 !r/$>9?@3,2@2,D+122= !r$>=?A=,B@D,B+1A23 !r$>? @D,2@3,A +1A21 &n$>=? A,9@B,9 +322=9 &n$>? A2,B@A,2 =+D22A &n/$>=?@B,A@9,@+322=1 &n/$>? @B,B@9, +A222 7nn ,7nn4n4 3,1 Pn,

PAGE 176

=A@ @,(nnn;!,%n>.O2?!r>.K9=2@? !r>.K2,29?&n>.K2,29? ;!>nnnn=+22?, 4n =(2=12(K32 (2(K3A2 =Yn(KD22 (n(KD22 %n n, K=+292 >KBD2?,KA2 Pn n 4n =(2=122(K3A (2=22(K3A 9(2A22(K39A =(n(KD92 (n(K3A 9(n(KD92 %n n, K@12 $ G=G9 K32Pn n ,/ G, 4n G=G9,/ G, =(2B22(K3=2 (2=@22(K3=2 9(2BA2(K3=2 =(n(KB=2 (n(KB92 9(n(KDA %n n, K@22 $ , 4n !=(2=3A(K192 (2B(K1@A =(n(KB@2 (n(KB92 K9=2 >K==A?, 4 =(2=(K1=A (2D2(K192 9(22(K1=2 =(n(K1DA (n(K392 9(n(K32 %n n G=, / GG9, KA@A >K1@B? >>K1@??, KA2Pn n 4 %7,#%7 ,# =(29(K3B2 (2=2(K392 =(n(KB2A (n(KB9A KAA >KABA?, 4 ,=(2=(K3A2(2=(K3A2 =(n(KB@2 (n(KBA2 / K3A >@=A?, 4 =(2@B(K3A2(292(K3A2 =(n(KBA2 (n(KBA2 /,< K9B2 >K912?, 4 %7,# .O8Ln, n4 ;! !rn nn/$$+ !rn!,5+n 4n, + +47+4n n, =A@

PAGE 177

=AA @,9(n !r nG=8/$+$+, n n"4 @,@=, 5nn84n 4n;! HB22n<,$ n4 n4n44 ,/$>G=?Nr;! n W = W .!= W .= W Ee eW= e Rn Rn 3B,92@@,@1B,A=93B=,1A292,1B=,=9 1@B,@B3D,@2=,=19==,13292,32=3,2 @2BB,@AA,1D@,A=191=,3=292,32,=D @A11,====,=9AB,1=1BD,2@292,1@=B,3 323,2==2,D9@A,9=AA1=,B9292,1B=D,12 =22BB,3A=@,@29,=@92=,A2292,3A9=,=9 $ /$>G=?N;! n W = W .!= W W Eee eeW= ee Rn Rn =3AD,2AD,2@DD==9,91292,B=2,@ 2BBD,29B,B@32D2,9@292,B92,A @@D,2AB,3@A1=3,@,=9292,B1 5nn ,3A !r$>G=?Nr;! n W = W .!= W .= W Ee eW= e Rn Rn @B1,B3@,A9A2BB2B=,2A292,3BB,@@ =D3,AAA,1B9B39D,332@2,B2B,92 AA3,9A,2=19@DB2=,=9292,33D,2@ D123,@@,B@=B=@D1=,2=292,3BA,DD =@3,39,99=33=B2AB,DD2@2,B2@,B= $ !r$>G=?N;! n W = W .!=W W Eee eeW= ee Rn Rn =D2B,=9,9A@1B@99,9292,BA2,A1 @22B,=9,9@91=193,292,B1 5nn ,D=

PAGE 178

=A1 @,9(>!? !r>G=? n W = W .!= W W Eee eeW= ee Rn Rn =1B2,9=D,A12@@A=,9D292,D22,== =D2,999,13D1@=2B,2292,B32,= 9122,9=B,1B@@2B2=,@=292,D2,= AB2,=9,1A2D3=B=,A@292,D2,=3 322,9=@,2BB11D=,1=292,D2,=B B@22,@=@,=9@@BDBB=,11292,D2,=1 =22B2,@=@,1@=DD9@DD=,1B292,D2,=@ =@B2,@==,D9D9992==,32292,D2,=1 =A912,A=,AA@9B=D=,1B292,D2,= =3A2,@=,1@@A2913=,32292,D2,=@ A12,@=9,BAA9@931==,13292,D2,=9 3B@2,@=@,3=A@32@=,1@292,D= 5nn 2,=2 @,@(n !r nG=8/$+$++!, n n"4 @,@=, 5nn84n 4n;! HB22n<,$ n4 n4n44 ,!r/$>G=? n W = W .!= W W Eee eeW= ee Rn Rn D11,B3@@2B2A1D@A,D32@2,D=2,2B =1B1,3==9913=AD1,9D2@2,D=2,21 BB1,B@A13@@=AA21,3B2@2,D=2,29 @93,29999BDBBD93,32@2,D=2,21 1@B1,DD3@==A32=11A23,B=2@2,D=2,29 B@23,==D1=1A2=@12B,=12@2,D=2,2 =293,9=B=D93129BD92B,=A2@2,D=2,2= =33,2=2@1=B2=2B2B,D=2@2,D=2,2@ =@@23,3B2=2A=2B@AAD,92@2,D2,2A =D@@3,B@1=9=9@9=,92292,D9 5nn =,99

PAGE 179

=A3 @,@(>!?!r$>G=? n W = W .!= 7W 7W Eee eeW= ee Rn Rn D13,=3@,A@@,AAA,@9,AD2@2,D2,2=3 =1B3,A1,=1,==A,B@,A2@2,D2,2AB BB3,D==,=9B,39A,=@,132@2,D92,21 @93,D1@,33,2,9A,292@2,D2,2@A 1@BB,=22,13D,3@9,1A,=A2@2,D=2,2= B@2B,==32,@BB,D3=,DA,=B2@2,D2,2=9 =22BB,==A3,@A99,@B1,DA,2D2@2,D2,2== =3B,9D=,9D===,AA,212@2,D2,22B =@@2B,AA9D,==,AA=BD,=@,D@2@2,D2,22A =32@3,DD,1=,3A=A1,@@,DB2@2,D2,221 =12B,99A,=,DA93,@,B92@2,D9 5nn 2,22 !r>G=? n W = W .!= W W Eee eeW= ee Rn Rn D12,9=B,==19=@@B,D2@2,D2,=A =1B2,9A==,193=B1=@@D,32@2,D2,23 BB2,9AA,D@A=9BDA=,2292,D=2,= @92,9A1,A29=9@=D=,9D292,D22,=9 1@2,9A1,BAA192B=,@D292,D22,=@ B@22,933,B3@AA@2=,A=292,D22,== =32,93D,2D@22@1DB=,@B292,D22,=2 =@@22,9DD,@=2@2@D23=,@A292,D22,2D =A912,9AD,=BBA1@=@B=,@3292,D22,== =1B22,9AB,DBB9B@A9D=,@A292,D22,=2 =D@@2,93D,1=2AD2@B3==,@2292,D22,2D ==2,93D,3=2A12@B=1=,@2292,D22,=2 @D12,93D,3=@@A2ABB==,93292,D22,2B 1BB2,93@,3==9A2A21=,9B292,D2 5nn 2,2D

PAGE 180

=AB @,@(>!?!r!>G=? n W = W .!= W W Eee eeW= ee Rn =2==,9B3,=B2==D=29,132@2,D=2,2@ =1B=2,1AA9,===@@2BA1D@,=@2@2,D=2,2A BB=2,@3B,39@BDA3D1,2A2@2,D=2,2B @9=2,=B,A=939A=DB,1@2@2,D2,=9 1@B=2,==2,=D2=3=A=,D292,D92,3 B@2=2,9A@,D112BAB=,B2292,D@2,A9 =D1=2,@3=,2=BA9=BD,1=292,D22,@ =@@2=2,@==9,3@A21@B,9A292,D=2,== =12B=2,3=2B,1B@D@3=1,=292,D=2,21 =32@=2,932,A313@A@@@,A292,D=2,2B =D1B=2,D=32,@=9B12D1D,=B292,D=2,2A =12=2,1=B=,B=9=B2==212,=1292,D=2,2@ @D1=2,D1,9=13B2=A@A2,2D292,D=2,29 11@=2,A=D,D=11@2=@@32,2D292,D=2,29 @,A(5nn" @,@2 nn n nn,n n W .= 7W .!= 7W = W2,A E= LW = PLn D22$=3A,=2,D2,1=3,D9,292,3A =1,= r ;! D22/$AD,B=,2,9A=,=A,2292,AA @, =3B2 $=2,19,B2,=A,=1,@292,3A n ;! =3B2 /$A2,=9,92,A@,@=,=292,AA 5nn n n W = 7W E LW 7W E LW PLn D22$A3,@D,DD,B2@2,DB 3=,A,2@2,D@ 2,2D r ;! D22/$=1,A1,D9,@292,DD @,13,D2@2,D@ 2,=9 =3B2 $AA,32,9,22,B@ =,2=,929=,22 2,@1 n n ;! =3B2 /$=1,32,2A=,92=2,B2 2,2D=,22,BA A,2B

PAGE 181

=AD @,1(!nn+ + nnn -!55#; .O2.K9=2@.K2,29 $H2DA3A1 T=22 >T=22? T=22 >T=22? =2 >==+==? /$H2AA299 91 >9B? =1 >=A? =2 >=2? /3=A/ =A >=D? 99 >B? 3 >92? !H29213 =D >9? 3 >B+@? /n nn, @,=($n nnn n,

PAGE 182

=12 @,(nn, 1,2 1,A 3,2 3,A B,2 B,A D,2 D,A 2A22=222=A22222A2292229A22nL: !r/$>G=? !r/$>G? !r$>G=? !r$>G? !r>G=? !r>G?@,9(7: !r, n An 4>,,? 9n n>9,=@n? C7 %nnn>DAn? K=&W 5 ', r, 5

PAGE 183

=1= 1,2 1,A 3,2 3,A B,2 B,A D,2 D,A 2A22=222=A22222A229222nL: !r/$>G=? !r/$>G? !r$>G=? !r$>G? !r!>G=? !r!>G? !r!>G9? !r>G=? !r>G? @,@(7: !r, =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A229222nL ;! L<,! !r$>G=? !r$>G? !r$>G9? @,A(;! !rn$, 8 nn7,

PAGE 184

=1 =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A229222 nL ;!L<,! !r/$>G=? !r/$>G? !r/$>G9? $nn @,1(;! !rn/$, 8 nn7, =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A229222 nL ;! L<,! !rG= !rG @,3(;! !rn, 8 nn7,

PAGE 185

=19 =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A229222nL;!L<,! !r$>G=? !r$>G? @,B(;!!rn$, 8 4nK@A2n, =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22@222nL;!L<,! !r/$>G=? !r/$>G? @,D(;!n!rn 8 /$,8n n,

PAGE 186

=1@ =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A229222 nL ;! L<,! !r>G=? !r>G? @,=2(;!n!rn 8 ,8 nn, =,2 2,D 2,B 2,3 2,1 2,A 2A22=222=A22222A2292229A22@222nL;!L<,! !r!>G=? !r!>G? !r!>G9? @,==(;!n!rn 8 !,8 nn,

PAGE 187

=1A 2,B 2,3 2,1 2,A 2,@ 2,9 2=2222922@22A22122 nL;!LG=?! >G?! >G=?/$ >G?/$ >G=?$ >G?$@,=(;!n n,8n n, @,=9(! !rnG= 8/$ 4n 8, A2Pn

PAGE 188

=11 @,=@(&n(>=?=2228n >?A2228n n !rnG= /$7 8, >=? >?

PAGE 189

=13 @,=A(&# n !rnG=/$,

PAGE 190

=1B @,=1(! !rnG= 8 8, @,=3(!!rnG= 8! 4K2,Annn =22Pn =22Pn

PAGE 191

=1D @,=B(!!rnG= 8/$ 4n 8, @,=D(!!rnG= 8 8, A2Pn A2Pn

PAGE 192

=32 @,2(! !rnG= 8/$ 4n 8, =22Pn

PAGE 193

=3= @,=($8 nn, !n 7 n !rn>G=? !rn>G?! !rn>G?$ !rn>G=? !rn>G=?/$ !rn>G=?$ !rn>G=?/$ 4n,!44K=9nn7

PAGE 194

=3 =222 A22 2 2A22=222=A22 222 .>Z?L 5n>Z?L 3 1@ @2B @A1 =22B ==31 =@=1 2BB @@ 12@22 2 22@212B2=22=2=@2=12@,(/"n !rnG= /$>=22-:=n:AL?, =222 B22122@2222 2 222@22122B22=222=22=@22=122 .>Z?L 5n>Z?L @B =D 912 AA D12 =D1 =D2 @22 @,9(/"n !rnG= $>=22-:=n:AL?,

PAGE 195

=39 222=222 2 2=2222229222@222A222.>Z?L 5n>Z?L =D @2 912 AB 32 B@2 =22B =A91 A1 3B@ @,@(/"n !rnG= >=22-:=n:AL?, 2222=A222=2222 A222 2 2A222=2222=A2222222A222922229A222@2222.>Z?L 5n>Z?L D1 =1B BB 1@B B@2 =29 =3 =@@2 =D@@ 22=22 2 222@22122 @,A(/"n !rnG= /$>=22-:=n:AL?,

PAGE 196

=3@ @222222222=12222=2222 B2222@2222 2 2@2222B2222=2222=1222222222.>Z?L 5n>Z?L D1 BB 1@B =22B =@@2 =32@ =12 @D1 @,1(/"n !rnG= $>=22-:=n:AL?, 222=222 2 2=2222229222@222A222 1222 .>Z?L 5n>Z?L BB @9 1@ B@2 =3 =@@2 =1B2 =D@@ 1BB @,3(/"n !rnG= >=22-:=n:AL?,

PAGE 197

=3A =2222 B2221222@222222 2 2222@2221222B222=2222=222=@222.>Z?L 5n>Z?L =2 =1B @9 1@B B@2 =29 =@@2 =32@ =12 @D1 11@ =222 A22 2 2A22=222 @,B(/"n !rnG= !>=22-:=n:AL?,

PAGE 198

=31 A2222@2222922222222=2222 2 2=2222222292222@2222A2222 12222 .>Z?L 5n>Z?L =2 BB 1@B B@2 =29 =@@2 =32@ =D1B =12 @D1 1BB 222=222 2 2=2222229222@222 @,D(/"n !rnG !>=22-:=n:AL?, 2,= = =2 =22 2A22=222=A22222A229222 nL5L =,2 2,B 2,1 2,@ 2, 2,2 ;! L?/$ >"?, n44,

PAGE 199

=33 A2222@2222922222222=2222 2 2=2222222292222@2222A22221222232222B2222 .>Z?L 5n>Z? !nr;!$ n!nr;!$ !nr;!$ 322122A22@2292222=22 2 222@22122B22=222=22 @,9=(/"n nn n8$ >=227:N=n:+A L?>KD22?;!, 322 122A22@2292222=22 2 222@22122B22=222=22 .>Z?L 5n>Z? !n;!$ n!n;!$ !n;!$ @,9(/"n nn n8$ >=227:N=n:+A L?>K=+3B2?;!,

PAGE 200

=3B =A222=2222 A222 2 2A222=2222=A2222222 .>Z?L 5n>Z? !nr;!$ n!nr;!$ !nr;!$ A22A2 2 222@22122B22=222=22=@22 @,99(/"n nn n8/ $>=227:N=n:+A L?>KD22?;!,

PAGE 201

=3D 222 =A22=222 A22 2 2A22=222=A22222A2292229A22 .>Z?L 5n>Z? !n;!$ n!n;!$ !n;!$ =22 B212@22 2 2A2=22=A222 @,9@(/"n nn n8/ $>=227:N=n:+A L?>K=+3B2?;!, A222=A2=22 A2 2 2=2222922@22A22122322 B22 .>Z?L 5n>Z?L >G=?/$ >G?/$ >G=?$ >G?$@,9A(/"n n8/$$>=22 7:N=n:+A L?,

PAGE 202

=B2 @,91(nn !r nG=8/$,@,93(n;!4@,A@,==, n >? r K@3,BPn>8? K1,BPn K9B,=Pn>8? %! !r! 2 =+222 +222 =,2 2,1 2,3 2,B 2,D L ;!L< !r !r %n 9+222 !r$ %$ !r!r% !r/$ !r$ !r/$ %/$

PAGE 203

=B= @,9B(n nnn n(>? n: + >r?n n8 4"n +>!?n nnn n8+>#? n +>?n :><7n ,>22??, :: ; : U ;: : ;8 ;n 7 ; ; : U ;: : ; : U ;: : U ; ;: ;: $ ; r #

PAGE 204

=B = =2 =22 =222 =2222 = 9 @ AnL .O2,29 .O9=2@ .O2 /$ $ @,9D(n n .,..O2.O9=2@$nnn 4,@,@2("n n nn/$$ n ;!, = !$ . = .!= !$ = !$= n nn

PAGE 205

=B9 @,@=(n" nn !r!rn, >?4n !rn8/$$ ;!, >r?4;!, = =2 =22 222@22122B22=222=22=@22 nLL n !r/$ !r$ &$ &/$ @,@(8 !r n>G=?/$$ 4@,@=>?n nn @,@2, .!= !$ee = .!= .= !$e = >? >r?

PAGE 206

=B@ 2,2= 2,= = =2 2A22=222=A22222A229222 nL L n !r/$ !r$ !r &$ &/$@,@9( n !rn >G=?" 4@,@=>r? nnnn 4 "4@,@2, 2,22= 2,2= 2,= = =2 2A22=222=A22222A229222 nL L n !r! !r/$ !r$ !r @,@@( n!rn >G=?" 4@,@=>r?,

PAGE 207

=BA 2,= = =2 =22 2,===2=22/nL n>7&n?5L n>5? @,@A(!4 5 n7nn 7 nnn4 @,=,

PAGE 208

=B1 @,@1(! !rnG= 8/$, 7n K=2=APn7, A2Pn !7

PAGE 209

=B3 !A !n!$#n 4!r7 A,=5 !+nn 4 +n nn+: 44,:4+ !@4 n8 n 7+nnn 8+ n, 8 n+n4 8 +4 n 48n +44 8, +n 4nn 8 n+4n4 !n >?8 4n 8 n 4n+L n+ n nn

PAGE 210

=BB 8n8n+8 n n + n,nn4 !rn>!@?+ 4n nnn n, n4 n, !n nn ,4!+5 8n nn n,:4+5nn n n 4n+ + 5, +n "nn ," 4 @,@=!@+n n n+7 n, n +4n >nn4,!n4 n

PAGE 211

=BD n8n5 !rn>!@? A,&n nn+ ,9>!?+ 4nn8 47n n8OAnDAn+ 4nK@APn7>n !?, n 7 2O=n>n7 !r ?+8 ,4 nnn :O1,An n,!I 4n 4n 7, n+ 4+74 OAn+ n,n 44 n 474 A,,=& 4488 n !rn! @,

PAGE 212

=D2 ;!322n<8n+ 488n n4 >,,/$ $?, ;! >KHBA2n4;#?+n 7k,;44 nn> ?"n4 ;$;O2,=n> )*+=DD9?,5;:4

PAGE 213

=D= KHBA2n<+n !9,7n+n ;! n;7n8 nn, +;n ( =2 ! r 2!8 !8!8 h "8 >A,=? 48O=8 8On +2!88 +!!r ;8 7+ +h!8+"8"n ;+o' "n,$n +!L!r" n ;!, $!@+ 4 nnbUU8+ nn $,4n n+4nr
PAGE 214

=D +8 ;! ( 8 "8 h 28 8=2 >A,? 48O=8+h8+28 8 +"8 "nLU8, >;!?+nn nbU9U948 ;!+4n n 8n, nn +4nn n+ +4n 4n r/4n+=DD?( 2 = >A,9? 4nn nn,

PAGE 215

=D9 +8n nn n, +( != "= = "= h r 2!= h 2= 2 =2 ! =2 I >A,@? n( " h 2! h 2 2 =2 =2 I >A,@r? 4n ",A,@r"$ >;!?, n 4 74 ( 2 : +2 >A,A? >;!?;8 "n;n ( != # >A,Ar? O@>;U:;U@b@;:?OD1+A22!Ln> ?,

PAGE 216

=D@ A,,=,=5nn& no ",> A,9A,1? n,A,=4nnn n nnA,,nn n 4+4 n 474Q nQ4 4;7>=DD@?,; n4 47-)*>=DD9?!> 229?,$8nn+ T24n,nn !rnn+QO2,=n A2QO2,= n1A4, nnn 44, n4 4 > ;!? ( = = =+ = =+ ==2 =2 2= 2+ 2!= =+ 2+ n n r n n n >A,1? n( 2! =+ 2+ =+ =2 n nn n >A,1r? 4p+2!+2;n ++p+=!+2;

PAGE 217

=DA 8n, >;!?+n ( = = =+ = =+ = 2= 2!= =+ 2+=2 =2 >A,3? n( =+ =+ =2 =2 2 2! =+ 2+ n n n n >A,3r? nn+; 84n4n 4 kOQO2,=n> -+=DBA?,+ n+;8( # @ =2 ! # @ != 2+ = r 2!= =+ 2+ >A,B? 8 4 n8 ,nn 447 p2+'Op=+'4p2+'47 nn p=+' 8p2+','

PAGE 218

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PAGE 238

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PAGE 246

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92 !$>=D3 3?+$n !&!C,&8n 4>=DD?, ,0,>=DB@?+Cn!$ ($nnn, &,+C, ,>=DA3?+n$ +5, +0n=2@+ ,A1, 0,$,+#.,C,+r0,!,+,#,+ &/,+r.,C, >222?+=93+n& +222=+ ;+!,,+7.,!,>22=?+&n $5 52@9+0 n=@B+,r91 r@,75,>=DBD?+!.! +M+5,+ /4E7,77n47Z,>=DDD?+$! nn+! @=+,=3@9=313,4:,,+Z0,!,>=D3D?+n! .AAF NZ!(=9E.+& $n=B+, =92,4:,,+r,.,>=DB3?+4E n! :!+&$n 1+,93@=, <<,$,C,,+-n:,>=D31?+! nn+0n=9+,=@9, <&,+7.,!,>222?+8n& !$$nn:==/! 55,$+0 n=@3+,=9AD=91A,=D3=?+!!$ $+0 n==B+,ADA9=,<',-,>=D39?+$$&+! =9+,B2AB21, <7n&,r,+#n/,+7-,>22?+ #! 2@9+0n= @D+,r@Br@9D,

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9= ,!,+/4n0,>=DD?+& n+9+r,, !4,+$n$+/4E7,nr,0,+:-,.,>=DD=?+; $!nn+0 n=9B+,@B, C,!,+.0,,+&,,+& ,&,+ ,:,>=D3B?+ $&+(.,$,7+0,>,?+$ 5nn$+ n+ $+/0,-,$,+7.,!,>=DD2?+ !n C4! $nn+0n =93+,92=292=A, E,E,+;VC,,+.n7#,,+/$,&, >222?+5 !5nn4^ +0n=@3+,DAD AB,

PAGE 254

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PAGE 257

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91 8(>!? 2,22= 2,2= 2,= = 2A22=222=A22222A2292229A22nLL n $ /$ ,3(/n n nG,

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93 8(>!?,=(<"n ,=1n n5nnG 8$,n W = 7W E LW 7W E LW Pn @B=B,D=,99,=32@ 2,D@@,=1,93292,D32,2@9 =1=B,BA,@9,@B2@ 2,D@=B,91,9D29=,222,291 9==D,93=,19,AA2@ 2,D@1A,D,3292,B12,2=9 9122,@=,@,22@ 2,D@==,B=,=92=,222,23A @B22,2=3,1@,D2@ 2,D@=,DA,@292,D32,2A A2@2,1=2,B@,@=2@ 2,D@D,2B,@129=,222,2BA 1@=,3=A,D@,AB2@ 2,D@=A,D1,93292,DD2,2A3 =@=,19,9A,@2@ 2,D9@,=,A2292,D32,29D @22@,B==A,@A,@A2@ 2,D9@3,@=,@@29=,222,22B 9=@@A,2=A1,BA,@A2@ 2,D93,A,2A29=,222,221 /nn ODAn,(<"n ,=1n n5nnG 8,n W = 7W E LW 7W E LW Pn @B2,@D,1A,232@2,D2,B=,2D2=,222,=1 1@2,@99,=1,A92@2,D=,@3,2=29=,222,=D 1@B2,@@,1B,D12@2,D,BA,B129=,222,=1 =9@@2,A,A=,2A292,D=,33,9D29=,222,=3 =1B22,A@,3=,2292,D,=1,D29=,222, @@B2,A=,1=,9292,D9=,B=,1D2=,222,1 B2B2,A2,1=,3292,D=,A,1A2=,222,92 /nn ODAn,9(<"n ,=1n n5nnG 8/$,n W = 7W E LW 7W E LW PLn @B=@,=A,3@,@B2@2,D@D,D@,99292,D2,=1 =D=9,@3,1@,332@2,D9=3,3=,D292,D92,= 912=9,==3,AA,9B2@2,D993,D3,3B2@2,BA2,2A 1@=,D,1A,@2@2,D91,BA,2@2@2,BA2,2@ 2 D12=9,=9,DA,@D2@2,D919,B3,2A2@2,D@2,29 B =@=9,A=9,11,=A2@2,D9=1,D=,3A29=,222,2 13 931=9,==@,3,@92@2,D@==,9=,1D29=,222,2 1@ 923=,1,3=,=A292,D@,@B,@B29=,222,=D /nn ODAn

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9B 8(>!?,@(<"n ,=1n n5nnG 8!,n W = 7W E LW 7W E LW PLn @=3,1=,3@,A92@2,D=A,D=,A3292,D=2,2B 912=A,92,22 =,@2@2,1=2,@91,2=292,3==,2A A2@=1,@2,21 =,9A2@2,1=,2A,=A292,392,@@ 1@B=3,A2,292 =,9@2@2,1=,9@,1B292,392,93 B1@=B,@2,291 =,12@2,1A=,A@,22292,3A2,9= D12=B,2,291 =,2@2,11=,19,A@292,312,D =9D=3,D2,2@ =,2D2@2,1@,29,=292,332, @22=3,@2,2@9 D,9B2A2,1A9,@,13292,B22,=@ 92@B=3,B2,2@ 1,3A2A2,119,1,D292,B=2,=9 /nn ODAn

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9D 8r(..rn n 222=A22=222 A22 2 2A22=222=A22222.>Z?L 5n>Z?L =2 =1 @2B 1@ D12 =D1 r,=(/"5 !rnG /$>=22-:=n:AL?,

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@2 8r(>!? 222=A22=222 A22 2 2A22=222=A22222A22.>Z?L 5n>Z?L @ D1 =@@ 991 AA B=1 =29 =A12 2@2 22=A2=22 A2 2 2=2222922r,(/"5 !rnG9 /$>=22-:=n:AL?,

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@= 8r(>!? A22222=A22=222 A22 2 2A22=222=A22222A22 .>Z?L 5n>Z?L 3 =1 9B@ 1@ D12 =D1 =D2 @22 r,9(/"5 !rnG $>=22-:=n:AL?,

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@ 8r(>!? =222 B22122@2222 2 222@22122B22=222=22=@22=122 .>Z?L 5n>Z?L @ D1 =@@ 991 A31 B=1 =29 =A12 21@ A@@r,@(/"5 !rnG9 $>=22-:=n:AL?, 222=222 2 2=2222229222@222A222 .>Z?L 5n>Z?L =D @2 912 AB 32 B@2 =22B =@B =A91 =3A A1r,A(/"5 !rnG >=22-:=n:AL?,

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@9 8r(>!?r,=(n n !rn 8$, nn" 4@,@= ,5nn84 n4n ;!HB22n<,$ n4 n4n44 ,n W = W .!= W .= W Ee eW= e Rn Rn 3B,B@D,B9+A@2BA1D,2=2@2,3BB,2 =1D,22A,19+=BBDB3B,A2@2,B23,@ D12D,91,3+1@=+39=3,3B2@2,B2A,9 =D1D,3=@=,D1+11@+DB@1,1B2@2,B9,3 <$>G?;!,n W = W .!= W W Eee eeW= ee Rn Rn =D2D,D9,91=,DB2=,@9,1=292,BA2,1 @22=2,=9,=@3,=A2,=1,3=292,B3 nn 9, <$>G?;!,n W = W .!= W .= W Ee eW= e Rn Rn @=2,9,1+@@B1DD,A32@2,3A=2,9 D1=2,B3,A9+932B@1=,2292,31B, =@@=2,3AA,2+@9DB@==,23292,31B,D A31==,D9A@,=A9==+=D=B,=A2@2,B9=A,= =9@@==,BD,9AA3=+@A=,2292,B9=9,B <$>G9?;!,n W = W .!= W W Eee eeW= ee Rn Rn 21@=,D9,91=,D=+223=,A292,BD2,A A@@=9,==,1=@3,BB@,AA292,BB nn =,3 <$>G9?;!,

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@@ 8r(>!?r,(n n !rn 8/$, nn" 4@,@= ,5nn84 n4n ;!HB22n<,$ n4 n4n44 ,n W = W .!= W .= W Ee eW= e Rn Rn =2==,=D,2=+29=+9@9=,A@292,3=B,3 =1=2,AB,D=+=@=+D=,39292,32D,@ D12=2,D9,92B,@=+2=,12292,39,@ =D1D,A,999,9=+1@2,2292,132,2 G?;!,n W = W .!= W .= W Ee eW= e Rn Rn @1,B=A,@39,919=,2=292,BB,3 D13,=92,3D=9,D@D,3=,@@292,B==B,D =@@1,B1B,D9BB,3AAA,A=,@=292,B@, AA1,A@B,=A99,1+@99,=B292,1D=,B G9?;!,n W = W .!= W W Eee eeW= ee Rn Rn B=13,2A,1+D@2,3292,3B2, =293,B,9=+B=3,DA292,B22,9 =A123,1A,3=11@22,BA,=3292,B9=, 2@23,DD,@=2=A=,9=22,3B nn 9,B G9?;!,

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@A 8r(>!?r,9(n n !rn8 ,n n"4 @,@=, 5nn84n 4n;! HB22n<,n W = W .!= W W Eee eeW= ee Rn Rn =D2,9B1,D@+D=2@+1139,9B292,B=2,=2 @22,9BA,A9+2B@+,93292,B@2,== 9122,9BA,99+==@+21==,AD292,D22,= AB2,91A,@+DB2+DB==,11292,D=2,=1 322,9BA,B9+1@19+B=,1A292,D=2,=@ B@22,9B=B,B9+D199+BD=,11292,D=2,=@ =22B2,@2=A,2A+2@@+33=,19292,D=2,== =@B2,9BD,A@+BA2@+@1=,1A292,D=2,== =A912,9D=2,2A+@=2@+=@B=,11292,D=2,== =3A2,9B=2,9A+A9@@+=1B=,13292,D=2,== A12,9B==,91+B1=@+3B=,1292,D= nn 2,=2 <>G?;!,

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@1 8r(>!? 1222@222222 2 2@222B222=222 .>Z?L 5n>Z?L =1B 912 1@ BBB =2B2 =@1@ 2BB =222 A22 2 2A22=222r,1(/"5 !rnG /$>=22-:=n:AL?,

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@3 8r(>!? 22222=12222=2222 B2222@2222 2 2@2222B2222=2222=1222222222.>Z?L 5n>Z?L D1 BB 1@B B@2 =22B =@@2 =32@ =D1B =12 @D1r,3(/"5 !rnG $>=22-:=n:AL?,

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@B 8r(>!? 9222222=222 2 2=2222229222@222A2221222.>Z?L 5n>Z?L =1B BB @9 1@ B@2 =22B =3 =@@2 =D@@ 1BBr,B(/"5 !rnG >=22-:=n:AL?,

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@D 8r(>!? A2222@2222922222222=2222 2 2=2222222292222@2222A22221222232222 B2222 .>Z?L 5n>Z?L =D 912 1@ BBB =2B2 =@1@ 2BB =A22=222 A22 2 2=2222229222@222 r,D(/"5 !rnG9 !>=22-:=n:AL?,

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A2 8r(>!?r,@(n n !rn8 /$,n n"4 @,@=, 5nn84n 4n;! HB22n<,n W = W .!= W W Eee eeW= ee Rn Rn 31,1=32A+9191+A@A,92@2,D2,23 =1B1,@@9+@=2@+D3@3,292@2,D2,2D 9121,AD9+DD9+1=93,D=2@2,D2,=9 1@1,A=3@D+32B+B9AB,22@2,D2,2A BBB1,1A@==+=@2B+@2BB,D92@2,D2,2A =2B21,AD1+B3BA+A2BD,312@2,D2,2B =@1@1,1113B=,A3292,D2,A1 2BB1,D9B@9AA9,2@292,BD nn 2,BB G?;!,r,A(n n !rn8 $,n n"4 @,@=, 5nn84n 4n;! HB22n<,n W = W .!= 7W W Eee eeW= ee Rn Rn D13,=3@,A@@,AAA+9A29,AD2@2,D2,2=3 =1B3,A1,=1,==A+B22@,A2@2,D2,2AB BB3,D==,=9B,39A+2B2@,132@2,D92,21 @93,D1@,33,2+B2A,292@2,D2,2@A 1@BB,=22,13D,3@9+1@2A,=A2@2,D=2,2= B@2B,==32,@BB,D3=+DD2A,=B2@2,D2,2=9 =22BB,==A3,@A99,@B1+D2A,2D2@2,D2,2== =3B,9D=,99==+A22A,212@2,D2,22B =@@2B,AA9D,=9=BD+=22@,D@2@2,D2,22A =32@3,DD,199=A1+@22@,DB2@2,D2,221 =12B,99A,A993+22@,B92@2,D9 nn 2,22 <$>G?;!,

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A= 8r(>!?r,1(n n !rn8 nn" 4@,@= ,5nn84 n4n ;!HB22n<,n W = W .!= W W Eee eeW= ee Rn Rn D12,D9,99+DA9+3@11,AA2@2,D=2,= =1B2,9=9,99+DA1+=B3,1@2@2,D=2,23 BB2,D,B9+3311+9@@D,DA2@2,D=2,23 @92,D=,3@+@3@9+9@@=,99292,D22,=@ 1@2,D=,@+@B+D29=,A9292,D22,=1 B@22,92=,3A+B329+@D=,19292,BD2,=9 =22B2,92,DA+11A9+=2=,1A292,BD2,=@ =32,92,A3+2=9+1B9=,1A292,D22,= =@@22,929,23+A299+33=,1@292,BD2,= =A912,92=,11+A39+=9=,1A292,D22,=@ =1B22,92=,B1+A9B9+@==,19292,D22,=9 ==2,92,=3+1A@9+1=3=,AB292,D22,=9 @D12,9=9,9=2+B2@+@D1=,A9292,D22,=2 1BB2,92=,DB+ADB9+D1=,A@292,D2 nn 2,= <>G?;!,r,3(n n !rn8 !,n n"4 @,@=, 5nn84n 4n;! HB22n<,n W = W .!= W W Eee eeW= ee Rn Rn =DD,9@9,=D2+A9231+1=29,BB2@2,BD2,2= 912B,==@9,B99+=32@=+2A2@,22@2,D22,2= 1@B,311,@3+@@@=2+D2A,1D2@2,D=2,2@ BBBB,B@,@+==DA+A3@B,922@2,D2,2B =2B2B,@=A,29+2D29+A32=,2=292,D92,=9 =@1@B,A=B,2=+31=+9@9=,AA292,D@2,9@ 2BBD,B=1,@=+3DB=+==,@2292,D= nn 2,@=

PAGE 274

A 8r(>!? 2,2= 2,= = =2 2A22=222=A22222A229222 nL L n !r/$ !r$ !r &$ &/$ r,=2( n !r nn, 2,22= 2,2= 2,= = 2A22=222=A22222A2292229A22@222 nL L n !r! !r/$ !r$ !r r,==( n!r n,

PAGE 275

A9 8r(>!? = =2 =22 222@22122B22=222=22=@22=122 nLL n !r/$ !r$ &$ &/$ r,=(8 !r n/$$" 4 @,@=,

PAGE 276

A@ 8!(54. &n 84n4 n n8, nn)*>221?4 4 >=D32?, nn4, n nr r n 4 >=r?,r n !+4nn n;!+nn r+ n nn 2 nr 2+( Ur >!,=? rUr! >!,? 4r, n (O=7=>=r? >!,9? rO7r >!,@?

PAGE 277

AA 8!(>!?47=7>!,=? >!,? n7O728>,9>2?Lh?+8nn += n 4+ nn r, n72h> 2Or2? +, 4r" >=?OnLOrLO=7=>=r?N7rs4nnn r,> ? r(5!O>=7=>=r?Ur7r? >!,A? 7 ",>!,A?+( >5!?O>q5!Lqr?rU>q5!Lq?r >!,1? #+ nE (EO>q5!Lqr?rL>q5!Lq?r >!,3? /4+7",>!,A?5!4r2+ n",>!,3?(>q5!Lqr?2O>7=2=Nr72? >!,B? 47=272

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A1 8!(>!?n>q5!Lq?r",>!,A?4 ( >q5!Lq?rO>=>=r?q7=2LqNrrq72Lq?>!,D? .7O728>,9>2?Lh?+4 (>q7Lq?rO728>,9>2?Lh?>,9Lh?O,97Lh>!,=2? .",>!,=2?",>!,D?+(>q5!Lq?rO>,9=>=r?h= =U,9rrh =?>!,==? r2O=7=2L>=7=2U72?", >!,==?4(>q5!Lq?r2O,9=7=272>h= =Urh =?L>=7=2U72?>!,=? 5nn+nn n48"_+ rnr24n8, +rNr2O28>'_? >!,=9? 42n8n 4 >rsr2?8,:+ >rNr2?LOrLO'_>rNr2? >!,=@? .rLO=L7=>=r?N7rs",>!,=@?+ ('_>rNr2?O>=L?7=>=r?N7r >!,=A?

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A3 8!(>!?74 ( '_rLO>rL?>=L7=U7?r>=L7=LU7L?U=L7=L>!,=1? 4r2(>rL?r2O>,9=7=272L>=7=2U72??>h= =h =?L>'_U>=7=2U72??>!,=3? .",>!,B?+>!,=?+>!,=3?", >!,3?+ n82(EO,95!>Ur?=>h= =Urh =U>r55=?>h= =h =?L>'_>Ur?U5=U5? >!,=B? 45=O=7=2>Ur?5O72>Ur?, 5nh=OhOh=7=2Or72+n >.!Oh>,95!?=?nn,%+ rn 4>rsr2? 88 "n n8 h=th>h=h?>r5 5=?+nn 4 "n8 n .$n( .$O>,95!>Ur?=>h= =Urh =U>r55=?>h= =h =?L>5=U5??=>!,=D? >h=h?>r55=?+.!H.$ +n ,; 4+n,

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AB 8!(>!?5h=+h+r+5++5=++.!.$4 K=21Wnn8n nn/$$,

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AD !r,,!n =DDBn%/! $r >;n?+r+,n= DD3=DDB+47 '%/ !$ r47#,& r, :n%=DDD&,, n% ,:n &,,!n 22n7 $,#,n229,n=DDD223+4 7 #,)* ,: ++ n+ n+nn ,#4 +' ++ ,:$& n /!5#+22,: nn/! 5n,


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TA145 (ONLINE)
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Caseres, Leonardo.
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Electrochemical behavior of aluminized steel type 2 in scale-forming waters
h [electronic resource] /
by Leonardo Caseres.
260
[Tampa, Fla.] :
b University of South Florida,
2007.
502
Dissertation (Ph.D.)--University of South Florida, 2007.
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Includes bibliographical references.
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Text (Electronic dissertation) in PDF format.
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System requirements: World Wide Web browser and PDF reader.
Mode of access: World Wide Web.
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Title from PDF of title page.
Document formatted into pages; contains 258 pages.
Includes vita.
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Advisor: Alberto Sagues, Ph.D.
520
ABSTRACT: Aluminized steel Type 2 (AST2), often used for culvert pipes, is subject to corrosion which is the most important durability limitation factor. It was desired to determine if the outer aluminized layer will retain passivity and if protective galvanic action will develop. Thus, corrosion of unblemished and blemished AST2 surfaces was investigated in simulated natural waters. Experiments with unblemished specimens showed passive corrosion rates (~0.06 m/yr) in scale-forming, 0.01 M Cl- solutions but sustained corrosion in other less protective media (with rates 3~10 m/yr). Corrosion was manifested macroscopically by discoloration and few macro pits, but it likely proceeded also microscopically at the Fe-rich inclusion space scale. For blemished specimens, the aluminized coating galvanically protected to some extent the steel in all solutions. However, in 0.01 M Cl- solutions, protection was delayed until after some steel corrosion had occurred.In some solutions, complete consumption of the outer aluminized coating around exposed steel was noted. Elsewhere, coating appearance was similar to that of the unblemished condition. Nominal durability projections made for 16-gage AST2 ranged from >100 yr for unblemished AST2 to ~10 yr for the blemished condition. The present findings were used as a first step in proposing refinements of presently used durability guidelines of AST2 culvert pipe. Cyclic cathodic polarization tests to examine O2 and H2 reduction at the Fe-rich inclusions showed significant hysteresis, more pronounced with decreasing scan rate. The effect was tentatively associated to the amount of Fe+2 being deposited during the downward scan, a hypothesis supported by results from a physical model. A static polarization model was formulated for the blemished configuration. Results matched experimental trends and permitted evaluating the effect of solution conductivity beyond the experimental range.Exposed steel corrosion rates at the steel were increasingly large for decreasing . For the lowest , corrosion rates at the exposed steel center were distinctly larger than at the edge, consistent with experiments. An impedance behavior model was also formulated. Results showed frequency dependent current distribution and predicted relatively small artifacts that were and not evident experimentally, but should be considered when exploring other system conditions.
653
Cathodic behavior.
Modeling.
EIS.
Galvanic corrosion.
Durability.
690
Dissertations, Academic
z USF
x Civil Engineering
Doctoral.
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t USF Electronic Theses and Dissertations.
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FTS
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