:

1385

-1

1-1-1

1-1-2

1-1-3

1-1-4

10

1-2
-2

11
12

2-1

12

2-2

14

2-2-1

24

2-2-2

26

2-3

27

2-4

31

2-4-1

32

2-4-2

33

2-4-3

34

-3

37

-4

39

41

-5
5-1

41

5-2

41

5-3

41

5-4

42

5-5

42

5-6

42

5-7

43

5-8

44

5-9

45

-6 Cosmetic

46

6-1

47

6-2

47

6-3

48

6-4

49

6-5

51

-7 Cosmetic

53

7-1

53

7-2

56

7-3

59

7-4 -

60

7-5

65

7-6

69

 -8

73

8-1

73

8-2

74

8-3 ) (Pigmentation

76

8-4

78
82

-9
9-1

83

9-2

86

9-3

88

9-4

91
96

:

.
1975 16
1987 9
.


) (Perforation .

.
Cosmetic
.
Perforation
Cosmetic .
Cosmetic Perforation
:
:Red rust .i
.

 :Paint creep .ii

:Chipping .iii
.

10-5-2 10
5 Perforation Cosmetic 2

.
:
.i : .
.ii :


.
.iii :

. PH


.

%40 1/3 2/3
. 10-12 %
. %25
. 300 kg 22 kg
.
2/5 kg.

-1

-1-1-1 (uniform corrosion) :

.

.
:
(1

(2

(3

-1-1-2 (Galvanic or two metal corrosion) :

.



.

.

... .
.

 -1-1-3 )(crevice corrosion

.
.
.

.
:
(1 .
.
(2

(3
.

 -1-1-4 )(pitting corrosion

.

. PH
.

.
.

.
.

10

 -1-2


.
:
(i

(ii

(iii

.
(iv

....

11

 -2 :

5


) (filler .
.

:2-1 :

substrate

12

 30
.
70 71
15 4
10 .

.
.
.

50
.
.
%20 .

.

13


.
.
Acura- Nsx .
.

.

:2-2 :

metallic coating

%7
1980 %50 1990 .
%40 2/3 1/3
.
1991 350000 %11
.

7 10
10 20 .

14


.
%3
.

.
%40
.

) (HDG ) (GA )(EG
(ZiNi) Zn-Ni - )(Zn Fe
.

(HDG): ) (HDG

m
) 6-20

m2

(40 140 gr .

15

 %20
.
HDG





.
.

16


.
%100
.

.
.

17

 . Chipping
10 .

Perforation . Perforation
.

HDG



HDG .

18

 (GA) :
.
.

.
6 ) 11 m

m2

(40 80 gr.

.
HDG
HDG .

(EG) : .
%40 .

4 ) 14 m

m2

(30 100gr

.
.

19

 EG
HDG
.

HDG



.

20

 EG

.
EG
HDG
EG HDG
A .
EG


HDG.

-(Zn- Ni) : 10 % 14 .

-
. 3 ) 6 m

m2

(20 40 gr.

-
.

21


.
-(Zn Fe) : .

- .
15 % 25
) 7 m

m2

(50 gr EG

- .
.
(Aluminized) : -
8 12

.
: 3
8

22

 .

.
:%55 Al-Zn %1/6 Si %43/4 Zn %55 Al
.
Al-Zn
.
%55 Al
.
.
.

MPa

262-365

38000-53000

345-448

50000-65000

in 2

Ib

%20-%36

23

 10
.


.

%55 Al-Zn
.

-2-2-1 :

:
:
550 .
1250
1300 .

24

 1500

.
:


.

.

- .

: ...

. .
CQ DQ

25

 DQSK
.


.

.

-2-2-2 :

Cosmetic Perforation

)
(
.

.

.

26

 Zn- Co- Cr
Al2o3 .
Zn-Mn
-
) 2 m (1
.

-2-3 :


.

.

.
SEM
.

27

 .

.

.

Po4-3
PH
. PH
.


.


.


.

28



.



.



)

m2

(2 5 g

.
] hopeite[Zn3 ( Po4 )2 .4H 2o
] Phosphophylite[Zn2 Fe( Po4 )2 .4H 2o .

.


. PH

29

 12 PHosPHoPHylite
hopeite.
) Zn- Fe (Zn- Ni- Co


.
30
200c
PHosPHoPHylite hopeite 4 .


PH - Po42 Zn
Nacl
.

30



.
.

2-4 :
: )(
.


.

31

 2-4-1 Primers
.
.

.
.
2 .
.
-
170c
- .

32

 .
( a
( b
( c
( d

-



.

2-4-2
.

.
.

.

33

 .

.
.
.
.

(1
(2
(3
(4
(5

2-4-3

.
.

.
(1

34

 (2
(3
(4
(5

100 m.
.
) (20 m - ) (40 m
) (20 m )(40 m

35

 -3 :

.
.
.

) (Scab

.


.
.
.

.

36

 ) (AISI

GM 9540P
.
Schumacher Davidson

GM- 9450B .
%1

.

37

 Cosmetic
%40 Perforation
%50.

Cl
So2 Nox
.
. Hoogovens
.
.

38

 -4 :

. :
:

Zn + 2 H 2 o Zn(oH ) 2 + 2 H + + 2e

)(1

Zn(oH )2 Zno + H 2o

)(2
:

O2 + 2H 2o + 4e 4oH

)(3

Zn(oH)2 1
Zn(oH)2
) (3 1
Zn(oH)2 . 2 Zno
Zno . n
3 .
2 .
Co, Ni, Mg, Al Mn 2
.


] Smithsonite[ZnCo3 ] hydrozincite[Zn5 (Co3 )2 (oH )6 .

39

 .
So2 .
] [HSo3

. ] naumwite[( ZnCu )4 So4 (oH )6 .4H 2o
.


4Zn(oH )2 .ZnCl2 Salt Spray
.
PH

6 Zn(oH )2 .ZnCl2

. NaZn4Cl (oH )6 So4 .6 H 2o

Zn4Cl2 (oH )4 So4 .5 H 2o

.

40

 -5 :
Granata
:

:Anodic undermining -5-1

.

. :
Zn 2 + + H 2o Zno + 2H +

)(4

-5-2 (Thermal cycling) :

.

-5-3 )(Cathodic blistering

.

41

 ) (
.
.
.
- .

-5-4 )(Gas blistering

. H2.

.

-5-5 (Swelling of polymer) :

.

-5-6 )(Osmotic blistering

.

42

 -5-7 )(Cathodic delamination

:
O2 + 2H 2o + 4e 4oH

)(5

. -
.

PH 14
.

Fe Zn .
.


.

.

43

 -5-8 )(Mechanical delamination

.
) Zn2+ (Fe2+
.

PH .

Fe2+ Fe3+ .

44


.
.

.

-5-9 (Combined Effects) :

-


.

45

 -6 Cosmetic :
)
(
.

.

.

-6-1 :

.
) (SEM/ EDAX
) (TEM .
XPS SIMS .
SIMS SEM/ EDAX
XPS
- SEM/ EDAX
XPS .

46

 SIMS XPS (XRD) x ) (AES

) (EPMA x
.

) (EIS .
.

-6-2 :
Van Ooij
.


.
) (


.
.

47

 - )(
.
.
.
.

-6-3 :

.

48


.
- .
.

/

.
Leidheiser

- .
.

PH . .
.
.

49

 -6-4 :

.
.

50

-6-5 :

.

/ -
) (
.

51


)( .

.

- - .
Cl-

.
PH PH
PH PH
. PH
PH . PH
. PH
- -
.

.

52

 -7 Cosmetic :


:
.
.
Cosmetic
:
-7-1 :
Townsend et la

.
HDG EG
. Zn-Fe

HDG.
Zn-Fe Zn
.
Fe2 + + 2oH Fe(oH )2

)(6

53

 .
Zn-Ni Zn
.

.



.
.
GA Lee et La
.
.
) (Salt-Spray HDG EG
.
.
Cosmetic
.

54

 Zn-Fe Zn-Ni

) ( .
15 Zn-Ni
. )
( Zn-Fe Zn-Ni .
.

.

Zn-Ni
11-15 % Ni

. ) +( Zn-
Ni 9 % Ni
.


.

55


.
-
.
-7-2 :
Frank
) Chipping
(Paint Creep, Red rust .
)( Perforation
.

m2

20 gr Perforation

56

 )( Perforation

m2

45 gr

Zn Ni
red rust Zn Fe Paint Creep
Chipping
.
EG Ronda
bush .

57

m2

27 98 g

) (
Zn Cosmetic
.
Volvo Uss Highway

m2

60 g

.
Zn Ni Zn Fe Zn-Co-
Cr Al2o3 Yasnda et La

m2

30 g

m2

20 g .

Zn-Co-Cr Zn Ni .
Robins EG

m2

m2

m2

60 65 g

60 g

65 g .

58

 -7-3 :

Jossic et La


.

Shastry and Townsend
) (Zn2+ , Ni2+ , Mn2+

.


.
.

.

Zn-Ni .

59




.

.

-7-4 -:
) (SIMS
Ooij et La
.

.
HDG

.

) (
.

60


(NMP) N-methyl pyrrolidone
60c .

.
Zno
4Zn(oH ) 2 .ZnCl2
Zno .
4Zn(oH ) 2 .ZnCl2
Zno.

61



.

.
62


) (
.
.
.


PH .

.
Miyoshi et La
.

.

.
Odoshima et La
Zn-Ni Ni2+

63

 . Zn-Ni
.
Zno 0/ 01 0/ 02m
Ni2+ .

: Zn3 ( Po4 )2.4H 2o
Zn3 ( Po4 )2 .2H 2o
. Zn3 ( Po4 )2 .2H 2o
Zn3 ( Po4 )2.4H 2o . Zn3 ( Po4 )2 .2H 2o
Zn3 ( Po4 )2.4H 2o .


Zn3 ( Po4 )2 .2H 2o Zn (oH)2
Zn (H2po4)2 Zn (oH)2 . Zno
Zno . .

.
Zn3 ( Po4 )2.4H 2o
.

64

 Ni Zno


Zn3 ( Po4 )2.4H 2o .
.
.

-7-5 :

.
:
.


.
Lambert et La

.

65


.
Blekkenhorst
Nacl
X-ray

.


XRD .


.



.
XPS EG HDG
) 18 m 43 m 22 m 37 m

66

 (120 m Van Ooij et la

6Zn(oH )2 .Zncl2
4Zn(oH )2 .Zncl2
.
.
) (96% ) PH (5% Nacl


.

.
.
Amir udin et la
5% Nacl
0/5% Nacl IR

Blekkenhorst . 5% Nacl

67


0/5% Nacl .
Robbins

.

Cosmetic
.

m2

95,120 g

Cosmetic
.
Shastry and Townsend
) (Chipping
Chipping
.
Chipping 13% Ni-Zn .
So2 Nox
.
-7-6 :

68


.




) (Anodic Undermining .




) (Top coat HDG EG
GA ZnFe .
HDG

.


.

69

 Van Ooij et la Cosmetic

XRD, EDAX, SEM SIMS 15
30
.


.

.
So42- .

.

.

Cl- Zn2+ So42- .

70


.

Cl- oH-.


.

.



.
.


.

71



.

.

72

 -8
)(

.


.
.

-8-1


)( .



.

73

-8-2
)
(
) ( .
.

) (Technology
3 6
.

.

.
4
.

74

) (Homopolymeric
.

.
) (
.
.
.

)(cm2. mil/ 100- inch 2.24 hrs. atm
100
0/01

2/5

(Coal
) Tar . )
( . Funke carfagna

75

 ) (Glass Transition=Tg): 86 F0
(30C0

) 100 (Tg=71C0 : 160 F0

.
) (cure
.

.


Tg .

.

-8-3 ) (Pigmentation
.
) (SPHerical ) (Nodular
) (lamellar
. ) (Pigmentation
/

76

)/( ) (PVC/CPVC
.
PVC ) (non_platy .


.
.


.

.
.
) ( .
scheller
SO
.

-8-4

77



.

Kittelber . Elm

.

.
.


. .
)
( .


.

78


.


.
)
(
.

.
/ ) (
.
. Julien
.
.
Julien
.
) (
.

79

)

(.
.
Leidheiser
.
) (180 mv .

. Cs+> K+>Li+ .
Kumins London
) K+> Na+>Li+ . Leidheiser (.



.
Mcleod Sykes )
(
.
.

80

) ms-1 1 volt.cm-1
(. Li )
(
Na +

vm1

vm1

3 / 4 108 ms

4/ 6 108 ms K +

1
1

vm

6 / 6 108 ms
1

vm1

7 / 1108 ms

) Sr++ Ba++ Ca++ (Mg++

.

.

) ( .
PH
.
Mcloed . Sykes
.
) ( .
Mg Ca K Na.
- 9

81

 .

.

.

.

.
.


.




.

82


.


.
.
.

.

-9-1
.
1930

.

.

83

 . .
.

.

.

.
Red Lead

.
9,10 .

) ( ) ( Mill
) Scale ( .
9

Mill
Scale .

84

 9,11 .
. .
White blast .
Mill Scale .
9 .
. 9,10
.

85

 -9-2
.
cohesion failures (1
.
.

) .(9,2

(2 adhesion failure

86

 .
) . (9,1
(3 substrate failure .
. .
.
) . (9,3

87

 -9-3
.
(1 : (2 (3


.
.
N S
.

.

.


.

.

88

 .

.
.

89

 .

.
anchor pattern .

.

.

.

anchor pattern
.
1 anchor pattern 2
.
.
.
.

90

 .
.

.

-9-4
.


.
.

.
.
. :
.


.

91

 .
: anchor pattern
. .

.
.
.

. .

92

 .
.
.

.

.

.

93

 .
.
.
.

.
.
.

.

.

94


.


) ( . .
.
.

.

95

1) Corrosion mechanisms of phosphated zinc layers on steel as substrates

for automotive coatings (A.Amirudin, D.Thierry)

2) Corrosion of the vehicles used in North America:

Anti-corrosion performance of galvanized steel sheet in several parts of a
vehicle (Katsuhei Kikuchi, Makoto Isobe, Chiaki Kato, Morishige
Uchida)

3) Corrosion prevention by protective coatings (National Association of

Corrosion Engineers) (Charles G.Munger)

4) Organic coating technology Volume 2- Pigments and pigmented

coatings (Henry Fleming Payne)

5) Metals Handbook volume 13, 9th

6) Corrosion Engineering (Mars G.Fontana)

7) Trouble with Paint (Clive H.Hore, Coating System Design Inc)

96