Electrodeposition Coating Process for Automobile Bodies‘

By Vochiañi OTABU,*• Nobuo FURi7NO,••• *1*‘ IRASAWA•••

and Hiroshi OMORI••••

technology in automobile bodies industry

the earlier electrodeposition process was mainly pursuited for the quality commenced around 1964 in J apan. In those days,
control in terms of mass production. However, the coating effciency was dip coating of water-borne paint was applied to
picked up to be a serial problem from a standpoint of the harmony
automobile parts after metal pretreatment, and it was
âetws«ri natural circumstances and human’s /ieirtp-/ e conditions and
the recovery usage of the joint was earnestly searched. This trend led to
confirmed when
the develop- ment in various technical fields. voltage was applied, the vehicle was deposited at the
electrode. This was the beginning of electrodeposi-
t he srcond im§etm oa further improvement of electrodeposition paint tion coating. However, the essential point of this
mas due to oil crisis in 1973. TA new tethnolog y relating to sane-e yg p y technology was not properly comprehended, while the
was developed. In the paint industries, the further improved anti-corrosiu unpublished work was progressing.
performance was strongly demanded. 77iii demand also incolued the de- Before 1963, the small products to which latex
velopment of new materials for automobile badies and even the design of emulsion was mainly applied had been produced in-
bodies strutture.
dustrially. In Great Britain, the first major industrial
In this report, the introduction off electrodeposition process into auto-
mobt’le indizstrisi '• J apan 1s hystrically reuiemed and the electrodeposition
use of electrodeposition coating system was in 1963
mechanism and the mechanism which deposited tnofrrtnii /rorn the coating
when the Pressed Steel Company commenced priming
film are briefly explained. As the demand for anti-corrosive usr/ormnnce petrol tanks at their Oxford Works. In U.S.A., the
is increased, the coating system in which the anodic oxidation and the dis- patent on electrodeposition system for automobile
solution from the object metal can not ot0ur, was aimed and recently it was bOdies and parts such as wheels was published in 1963
rapidly accepted as the superior system. On the other hand, there is an fI'Om the Ford Motor Company.
opposite opinion for this trend on the basis of the metal analysis detected tn And when patents emerged, all the automobile in-
the deposited film. The characteristics of cationit electrodeposition, in dustries aimed at them. As the research was going
particular, tke superior corrosion resistance with regard h• **t"! d'’ S on, the coating technology was proved to attract us
to solution in the whole electrodeposition process is with peculiar interests such as high corrosion resist-
explained.
In Clliapter III, thronging power which ti charatteristic for
ance of coating and the superior adaptability to mass
electrodeposi- tion process is described. It tJ referred that throwing
power is not neces- sarily determied by the paint performance. Even the
production.
electrodeposition coating system, the areas into uihich the paint liquid dace The paint industries in J apan made a great effort
not intrude can
not be coated. And it is pointed out that the design of bodies structu!! i to develop this coating technology, while they intro-
inevitably necessary as well as the improvement of paint performance›. duced it from the developed countries which it was
In Chapter IV, the role of the mots component, vehicle resin, is intro- attained in a higher level. The j apanese industries,
duced. the devices which disperse resin into solvent ’ water ’, and factors in particular, automobile industries were in rapid
which determine the polarity o.f electrodeposition are explained. And the progress, and they invested in the installation for the
typical resin structure is shown. the paint performance is greatly new coating system. Owing to this days trend, the
effected
electrodeposition was satisfactorily accepted by most
by the vehicle resin, but it is also related how the paint is
produced and how it is coated. therefore, ii is inferred that the paint
of automobile industries. And in a short period of
performances are relatively estimated. time, J apan got ahead of Europe and then U.S.A. in
in Chaf›ter 7, the zohole system of eIestrodef›osition coating f›rocess i\ its distribution.
gieert. The so-called ’ cloud-food system ’ which is remarkably charac-
teristic in electradepositiaii process, and which is suitably fitted %r mass In the beginning of electrodeposition paint which
production of automobile 6odiei ts explaitted. Besides, the pH contras was mainly composed of natural oils, the film per-
technalog y of paint bath and the possibility on its future development are formance as a primer itself was inferior to that of
referred. The further improvement of the recycle usage technolog y o/poiat solvent-type polyester primer modified with epoxy res-
is pointed out and the possibility to reply %r the social needs such as sane- in by spray coating, but the electrodeposition coating
e ergy and less solution is explained. system was not followed in terms of throwing power
In Chapter VI, the present status of electrodeposition process and and the coating efficiency.
various
ter/tnicof f›roblems ore exf›lained.
Around 1971, natural circumstances grew worse in
the summary of this review and authors’ utemi %r future proportion to the rapid progress of industrial products
development are given in the fuial chapter. and people became sensitive to the recovery of the
nature in Jap an. The electrodeposition coating sys-
t• If2 roduct$Of2 tern does not emit an organic solvent in the air
and The development of the electrodeposition coating in this point of view it fitted the days’ demand. How-

* Received April 11, 1983. 1983 ISU

** Director of Research Department, Nippon Paint Go., Ltd., Minami-shinagawa, Shinagawa-ku, Tokyo 140.
*** Technical Center, Nippon Paint Co., Ltd., Ikeda-nakamachi, Neyagawa 572.
**** Industrial & Marine Coatings Division, Nippon Paint Co., Ltd., Fukushima, Fukushima-ku, Osaka 553.
(994) Review
 Transactions ISII, Vol. 23, 1983 ( 995 )

ever, the great mass of water was utilized for rinsing

world accepted it. Consequently, the anti-corrosive
after electrodeposition and it caused the problem of
performance of the precoated steel for automobile
waste treatment. In response to this problem, the
bodies came to be evaluated by applying electrodep-
treatment of rinsed water was studied, leading to the
development of the closed system. osition coating to it.
Even the steel industries were involved in the world
In 1969, PPG (the Pittsburgh Plate Glass Com-
trend from mass production to the development of the
pany, U.S.A.) published the patent on ultrafiltration
functional materials. The steel industries commenced
closed-loop system for electrodeposition coating. The
earnestly the development of precoated metal possess-
waste treatment of rinsed water after electrodeposi-
ing the corrosion resistance, while producing steel by
tion was remarkably improved and coating efficiency
continuous annealing pickling line system. With the
reached 100 %. This progressed the improvement of
development of precoated metal, papers on the analy-
the quality and the preparation of large size of ultra-
sis and its interpretation on steel surface have begun
filter and facilitated the industrialization with use of
to appear. (The development of the instrument of
it.
chemical analysis has given a big help to them.) And
Since the oil crisis in 1973, the textile industries the technology of the phosphate coating has progressed
were chased up closely by the developing countries in combination with the technical reports on steel sur-
which manufactured products cheaply and they were face.
not allowed to keep the technology for mass produc- At present, the electrodeposition system are mainly
tion. They were demanded to develop the new tech- from PPG’s patent. The distribution of primers for
nological product being provided specific properties automobile bodies in each region is shown in Table 1.
by utilizing their fine chemical technology. It can At present it is impossible to decide with technical
be said that this trend in the textile industries accel- investigations what sort of steels are suitable for auto-
erated the development of ultrafilter. mobile bodies. Though one side and both side gal-
In 1975, it happened that an automobile engine vanized steels have been utilized for automobile
was dropped off from the body by severe corrosion of bodies, the development of corrosion protection would
supporting panels which was caused by the salt dis- progress as a total technology while giving answers
persed on the road in Canada. This led to the big how to select the precoated steel and how to use it.
compensation and with a help of its impetus the cor- The authors inferred that the essential technology
rosion protection of automobile bodies were taken as for electrodeposition coating system could be throwing
the serial problem which had been prone to be neg- power and the control of deposition bath paint, and
lected and the design of automobile bodies were begun carried out the analysis of throwing power and the
tO study in terms of corrosion protection. deposition mechanism in 1969. In the references pub-
Around that time, in order to decrease the weight lished in the 1960’s, electrodeposition coating is de-
of au tomobile bodies, inorganic and organic materials scribed as ‘ electrophoretic coating ’. The authors
were started to be investigated in response to the days’ reported that the film forming reaction was due to
demand of saving labor and energy and cationic elec- water electrolysis, water removal by electroosmosis,
trodeposition coating attracted remarkable attention. aggregation of colloidal particles and their melting by
PPG’s patented cathodic electrodeposition system was ,Joules heat.
introduced in 1972. Its first commercial use was In this review, the technology of the electrodeposi-
for applying the primer on household appliances to tion coating system is discussed on the basis of
gain the advantages of increased detergent resistance authors’ work and views referring to many papers and
and outstanding corrosion resistance. patents.
The corrosion resistance of cationic electrodeposi-
tion coating was far superior to that of anionic one II. Mechanisms of Electrodeposition Coating
and the former was substituted for the latter in a few
years in Japan. 2. Significance of Electrodeposition Coating Process of Auto-
In those days, there had been reported only several mobile Bodies
papers on the steel surface. In the industrial metal As structural materials for automobile bodies, steels
pretreatment line which the phosphating bath was have been widely utilized as they are supplied cheaply
controlled in the proper treatment values, even if the and in large quantities besides their strength. The
satisfied phosphate coating was not obtained due to main purposes of the coating are to protect the sub-
the variation of steel surface, the phosphating bath strate from the corrosive attack and to provide it with
was changed to fit the varied steel surface. a good appearance.
Around the time cationic electrodeposition coating
was examined to apply to the industrial line, there had Table 1. Distribution of primers in each region.
been technological competition to protect automobile (investigated in 1982, autumn) (%)
bodies against corrosion either by the improvement of
U.S.A. &
primer paint or by the development of precoated steel Canada Europe Japan World
plated with Zn, Ni, or Al. However, the cationic elec-
trodeposition paint of PPG was proved to be far ahead Cationic primer 80 53 76 56
Nonionic primer 19 21 0 24
of others and most of the automobile industries in the Anionic primer 1 26 2t 20

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( 996 ) Transactions ISII, Vol. 23, 1983

Themethod of applying primers using the electro- electrodepositing vehicle is represented by fiA, where
deposition coating process has become quite common fi* is the macrocation, then fi* will be deposited at
in the automobile industry, since it was introduced the cathode (cathodic electrodeposition). Conversely,
during the 1960’s because of its inherent processing with macroanion fi , deposition will take place at the
advantages. anode (anodic electrodeposition). The anodic elec-
The electrodeposition coating method fits well into trodeposition relies on carboxyl groups and the cath-
the coating process in the automobile industry either odic on amine groups. Thus electrodeposition resins
as an in-line processing method or as an off-line sys- are designed and prepared like other coating polymers
tem. The coating time is short, 2 to 3 min full im- but are required to carry ion-forming groups, c.p.,
mersion, for complete bodies or parts, and it coats the
—NH or —COOH. These resins are utilized in elec-
exterior, interior, and recessed areas in a single dip trodeposition as indicated in Table 2.
application. One technician normally operates the
When the voltage is applied, the main reactions at
processing system.
the electrode are electrolysis of water and the deposi-
Bodies or parts to be coated are fully immersed in
tion of macroion.
the electrodeposition bath. The electrodeposition
1) Electrolysis of water
paint formulated proper materials provides a uniform
coating over all electrically conductive surfaces in the Anode
given coating time. 2HiO 4H+ + 0,+ 4r
The paint is water-borne. There are also small
amounts of solvent present, approximately 5 % or less. 4OH — 0,+ 2HiO +4e
This composition and the process efhciency are very Cathode
compatible with goals to minimize air pollution. 4H,O +4e —• 4OH* + 2Ht
When the electrodeposition coating process is used 4H+ + 4e —• 2Ht
with a ‘ closed-loop ’ system, it results in high utiliza-
tion of the paint. Properly designed systems have a 2) Polymer deposition
paint utilization efficiency approaching 100 %. Most
systems are designed to achieve this high efhciency. Anionic electrodeposition
There are numerous other characteristics of the ACOO* + H* ACOOH
electrodeposition process, such as non-flammability. Cationic electrodeposition
Various reactions relating to electrodeposition in con- AtNH“+ OH —• A N + HCO
nection with the object are reviewed in this chapter.
As shown in Fig. 1, anionic electrodeposition and
2. Mechanism of Electrodeposition cationic electrodeposition are similarly symmetry. The
In anionic electrodeposition developed in the begin- mechanism of electrodeposition and others would be
ning, it was assumed that the deposition was due to substantially considered to be the same phenomena.°
the following reaction, where charged water-soluble or
water-dispersible macroion fi‘ was changed to fi at
the anode. Table 2. Electrodepositable resins and mode of deposi-
tion.°'

Film-forming Type electro-

Resin particles stabilized by macroion is called hy- Resin° Neutralizer macroion deposition
drophobic colloid. The deposition mechanism was
SNH Acid (HA aq.) SNH, Cathodic
assumed to be electrophoretic deposition of hydro- fiCOOH Base (BOH aq.) fiCOO Anodic
phobic colloidal particles and its coating process was
called ‘ electrophoretic coating process ’. But, it was ny = resin
failed to explain characteristics of electrodeposition
such as superior throwing power and high produc-
tivity by the above electrode reaction with an electron
transfer.
Many reports including the authors’ research l were
published and it was clarified that the deposition
mechanism was due to the coagulation of hydrophobic
colloidal particles by H* generated by water electroly-
sis. This result greatly contributed to the develop-
ment of the cationic electrodeposition coating process.
And by the industrial utilization of anionic and catio-
nic electrodeposition, the above mechanism based on
electrolysis was widely accepted.
In electrodeposition, charged water-soluble or wa-
ter-dispersible macroions are attracted by the elec-
trode of the opposite polarity where they undergo Fig. 1. Comparison of anionic electrodeposition with ca-
electrochemical reactions and are deposited. If the tionic one.

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 Transactions ISU, Vol. 23, 1 983 ( 997 )

3. Mechanism of Film Formation

water after electrodeposition. As the applied poten-
When the constant potential difference (100 V) was tial difference is increased, the melting process occurs
applied, the logarithm of the current was linear to faster. Materials formed by this melting process get
time as shown in Fig. 2. This relationship is called increased the electric resistance. But it is not allowed
the law of logarithm in the film formation, and indi- to increase beyond a certain value. The film conduc-
cates that the current decreases due to insulation of the tion depends on ionic species in the pin holes which
electrode. When the electrodeposition period was are built up by releasing the bubbles. These bubbles
longer than 6 sec, this relationship deviated from the and pin holes are visible although they are very small.
linear shape and the square of the reciprocal of the The colloidal particles precipitate in the pin holes as
current density became linear to time as shown in shown in Fig. 4, the growing point of the film is no
Fig. 3. This relationship is called the law of parabola longer adjacent to the electrode but within a diffusion
in the film formation, and demonstrates that the mech- layer a finite distance away from the electrode. When
anism of electroconduction of the electrodeposited film the applied potential difference is too high, the ran-
is ionic, controlling the rate of the film formation. dom growing ruptures the uniformity of the film.
From these results the mechanism of the electro- The film rupture voltage is believed to depend on the
deposition film formation is discussed using the model rheological properties of the film and the rate of elec-
shown in Fig. 4. When the applied potential differ- trolysis.
ence is low, the melting process of the electrodeposited
particles cannot occur. In this case, the particles of Metal Dissolution
rinsed off from the electrode by washing with tap When the potential difference is applied in an elec-
trolyte solution, the following metal dissolution may
occur at the anode.
Current

The redox potential of the metal affects the possibility

of the above reaction, and as the potential becomes
higher, the reaction possibility becomes larger. But
this does not imply the continuous reaction progress.
0 5 10 When anionic species such as Cl are presented too
Time(sec) much in the electrolyte, the dissolution reaction occurs
Fig. 2. The relation between the logarithm of current and easily and CrO2 *, SO*‘ and CO,* disturb the
time during the early period at a constant applied above reaction.
potential of 100 V. In anionic electrodeposition, the object is anodized
and the following polymer deposition occurs; that is
4
In other words, at the anode the dissolution reac-
E • tion is decreased by the polymer deposition. These
reactions would not occur evenly over the automobile
bodies, because of their complex-shaped structure.
Since the potential difference is not the same in all
the locations of automobile bodies, the electrodeposi-
0 10 20
Time(sec) tion coating process provides an uneven coating. This
Fig. 3. The relation between the square of reciprocal cur- would deteriorate the performance of coating such as
rent and time (— • —), and that between the pa- corrosion resistance and appearance. The dissolved
rameter p and time ( ). amounts of the metal during reactions differ largely in
electrodeposition bath compositions. And they are
affected by the surface treatment of the steel. The
20’%p adaptability of the newly developed metal materials
Film
should be strictly examined.
O OO
O O O O In cationic electrodeposition the object is the cath-
O
ode, and the above mentioned anodic dissolution re-
O OO action does not occur at the object, This point was
O
«
O .
O
O O O aimed at and the cationic electrodeposition coating
O O process has been developed which gives an excellent
O
Bubble corrosion resistance.
Growing point Anderson‘ analyzed the metal in cationic electro-
White circles: Dispersed colloidal particles deposition films and characterized the peculiar rela-
Black circles: Coagulated colloidal tions of cationic electrodeposition against anionic one
particles Hatched area: Insulator (Fig. 5). He presumed that the following reaction
Fig. 4. A model of the electrodeposited film. would occur at the cathode.
( 998 ) Tranaaotiona ISU, Vol. 23, 1983

ñf°+4OH [MOV] + 2H,O+(4— a)r

2400

Since then, his data have been cited by many re-

2000
searchers with a little discussion. Being based on the
results electrodeposition film weight increases with an 1600
increase of the deposition time. The authors can not
agree with the following approach. The metal de- n 1200
tected in electrodeposition film is assumed to be due
to the electrode reaction by a flow of current. 800
Metallic substrate dissolves chemically without cur-
rent flow. For example, corrosion with hydrogen 400
evolution is illustrated as follows.

2Fe -}- 3HtO FetOs + 3Ht } 102030405060708090

Zn -l-HCO ZnO +Ht

Voltage= 90 (constant)
2A1-j-3HtO — AltO -j-3Ht }
90 % neutralization
These reactions do not participate in electron transfer Fig. 5. Changes in iron content of electrodeposited films on
and they are not related to current flow. These cor- cold-rolled steel with deposition time.
rosion reactions differ in electrodeposition bath com-
positions, electrodeposition process conditions, metal
materials and their surface conditions. Therefore,
the analysis of corrosion reactions are quite difficult.
However, the practical difficulties arising from the
above mentioned factors have been clarified.
In cationic electrodeposition, the working electrode
is the anode and anodic dissolution causes a contami- 11
nation of electrodeposition bath paint. Care must
be taken in cationic electrodeposition being different primary Secondary
from anionic electrodeposition. In order to prevent Anode Anode

the contamination by dissolved ion, the working elec- (a) Bar test (plan)
trode is settled inside diaphragm which ion-exchange (b) Multiple plate test (elevation)
membrane is preferably used. (c) Wedge test (plan)
(d) Tube test (elevation)
(e) Cell test (plan) [1]
ZIP. Z’ftrOcriri,g Pocrer
of throwing Power in Protective Coating
In coating applications for complex-shaped auto-
mobile bodies, throwing power, the ability to extend Fig. 6. Types of throwing cells (diagrammatic).
paint films into highly recessed areas, as well as the
corrosion resistance of coating are greatly demanded.
These two specifications have been parallely taken as For the first purpose it is recommended to make a
the index for the improvement and development of model on the characteristics of the bodies structure.
the electrodeposition coating process. The modeling of the bodies structure generally arises
Recently, the materials such as the cold-rolled steel, from the know-how on the design for corrosion protec-
galvanized steel and other steels have been widely tion of the automobile industry. There have been
utilized for automobile bodies, and the estimation for proposed the following devices for measuring throwing
two specifications (corrosion resistance of coating and power of the electrodeposition paint since it was de-
throwing power) become complexed and varied. In veloped. The most simple device is a comparative
order to improve the protective performance of auto- test. Many possible methods were described briefly
mobile bodies, they should be examined particularly by Tawn and Berry, 5 and are illustrated diagram-
in the throwing power. In this chapter, we review in matically in Fig. 6. This diagram enables one to ap-
throwing power. preciate the meaning of throwing power.
(1 ) Bar test (Fig. 6(a))
2. throwing Power test In this type of test, either or both of two functions
In case of the design for corrosion protection of can be measured: the length of the anode coated under
automobile bodies, there are two following purposes given conditions, and the gradient of film thickness
to estimate throwing power. down the anode.
1) To design the structure of automobile bodies and (2) Multiple plate test (Fig. 6(b))
materials’ adaptability In this form of test, the efficiency, that is the weight or
2) To design electrodeposition paint and deposition film thickness of coating on the inside plates, can be
coating process compared with that of coating on the outside plates.

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 Transactions ISU, Vol. 23, 1983 ( 999 )

(3) Wedge test (Fig. 6(c))

In this test, it is only possible to estimate the per-
centage of the total area not coated with the paint.
Mathematical expression of the result is difficult, due
to difficulties of measuring areas accurately and de-
fining the boundary between coated and uncoated
areas.
(4) Tube test (Fig. 6(d))
Several methods of this type exist, one of which is
illustrated in Fig. 6(d), but in essence this is similar to
the bar test, except for the restriction applied to the
electrical bath by the non-conductive tube itself.
(5) Cell test (Fig. 6(e))
Particular conditions may be applied to the anode
in the cathode compartment, and the deposition on
the anode in the separate compartment may be deter-
mined separately.
Another purpose to estimate throwing power is to
detect quantitatively the inherent ability of the used Glass tube
paint. In these several measuring methods, the tube
test (Fig. 6) has been recognized to be mostly accepted Steel panel
method. The size of this test tube is defined fully by
automobile industries. For examples, Ford Cell and
0 1 2 3 cm
GM Cell are popularly accepted in U.S.A.

3. Analysis of throwing Pou›er

III
The electrodeposition paint industries have ana-
lyzed the mechanism of throwing power as correspond- Fig. 8. The sectional view of anodes in the glass tubes
ing to the different size of each automobile industry. used for the throwing power measurement. Cases I
yabu and Furuno6‘ showed that throwing power to III show the three different combinations of the
could be related to the geometry of the test cell and diameter r of the glass tube and the width / of steel
coating properties by the following equation : panel.

a E................................. These panels were electrocoated and the longitu-

(1)
dinal length of coated surface, that is throwing power,
was measured. These results are shown in Fig. 9.
where, a : the cross-sectional area of the cell To estimate the value of throwing power of coating
the perimeter of the cell liquids, the steel tube containing a steel panel was
the bath conductivity coated, and the length of the coated surface of panel,
E: the applied voltage namely the throwing power (77z) was measured. This
the current density at the coated surface process is called the tube test method. In Ford Cell,
of the tube at the end of the deposition the diameter of the tube 2r= 1.75 cm, the width l ——
experiment 1.60 cm, and the thickness d ——0.03 cm, and the value
The equipotential surfaces at the start of the elec- of a|L is calculated to be 0.28 cm.
trodeposition process are shown at the left, and those Table 3 is a comparison of some calculated and ob-
in progress at the right of Fig. 7. The dense distribu- served Ford Cell throwing power results. The cal-
tion of equipotential surfaces along to the anode cor- culated values were obtained using data obtained from
responds to the electrodeposited film. In this area flat panel experiments. Throwing power was deter-
the current density is approximately uniform. mined at the point which the film thickness was 1.7
To verify the relationships between a and th, and pm. The agreement between the calculated and ob-
between L and Th in the above equations, three kinds served value is reasonably good.
of experiments were carried out. A steel panel was Besides providing good estimates of throwing
inserted into a glass tube. If the thickness of the panel power, the described equations provide a guide to the
is expressed by d and the width by 1(d 1), 6 repre- factors that must be varied to increase throwing power.
senting the circumference length of the panel is equal Throwing power can be increased by an increase in
to 2(d+/). If the radius of the glass tube is expressed the bath conductivity and the applied voltage or by
by r, o in the equation is equal to zr°. Panels of dif- an inherent decrease of the final current density.
ferent length and pipes of different radius r were Pierce and Furuno discussed throwing power tests
prepared and combined as shown in Fig. 8. and the geometric and electrochemical factors which
Case I: 1 Tñ° should be in proportion to L influence those tests in 1975. The results of those
Case II: Th should be in proportion to r analysis permit the calculation of throwing power from
Case III: Th should be in proportion to rl '° electrochemical data obtained on flat panels provided

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 ( 1000 ) Transactions ISU, Vol. 23, 1983

1O‘/Th* Th Th(cm)
20
O
10!

25 m 20 m

Fig. 9. L The relation between the square reciprocal of

the throwing power IQ Th* and the circumference
length L of the panel.
II. The relation between the throwing power 77i Fig. 10. Halling cell test.
and the diameter r of the tube.
III. The relation between th and the square root
of the diameter, r'>°. should be evaluated by the length of paint film pos-
I, II, and III corresponding to each case in Fig. sessing a certain level of corrosion protection ability.
8. He proposed that the length of paint film could be
measured after being exposed to the corrosion environ-
Table S. Comparison of calculated and observed Ford ment such as salt spray test.
Cell at 17 km for a pigmented cathodic
primer.
• Electrodeposition Coating Resins for Auto-
Voltage Calculated Observed mobile Bodies
Time
(V) (sec) throwing power throwing power
1. Outlin
50 90 8. 6 8. 9 The resins for electrodeposition coating are classi-
100 90 13. 0 12.4 fied in water-borne resins. By the balance of hydro-
200 90 17.8 19. 0
philic and hydrophobic groups, resins are varied to
250 90 the water soluble type, the colloidal type and the
19. 2 20.6
dispersive type. When hydrophilic groups in main
chains of macromolecular resins remain in paint films
the geometry, dimensions, voltage, and time of the without reaction, the film performance of water re-
throwing power experiment are known.°' l ° sistance would deteriorate. To prevent this deteriora-
The progress of this analysis enabled to design the tion, hydrophilic groups which help to solubilize resins
size of the opening space of the body, so as to paint in water, should be introduced in main chains in
smoothly in recessed areas. And this leads to the de- minimum quantities.
sign of the automobile structure in terms of corrosion Generally speaking, the average molecular weight
resistance. On the other hand the values of throwing of water-borne resins is smaller than that of solvent
power obtained by different size became possible to type resins. Therefore the reaction, by which the
compare and this promoted the improvement and de- higher macromolecules may be formed, should be
velopment of electrodeposition paint. adapted. It is very important how the reactions are
In Eq. (1), a|L (cm) means a constant relating to selected to give the excellent film performance. The
the shape of cell. And when aJL—— 0.28 cm, the elec- particles of resin should be ionized in water to give
trodeposition paint possesses 25 cm throwing power. the electrodepositable properties. And the higher the
The value of E• •!J (cm) is calculated to be 25° molecular weight of macromolecular ion is, in other
0.28= 2 232 cm. An experimental result of electro- words, the higher the average molecular weight per
deposition using Halling Cell is given in Fig. 10. It unit ion is, and the larger the deposited film weight
may be understood that the uniform current density per unit electroquantity is.
is supplied over 20 m. When throwing power over There are two methods to ionize resins in water.
30 cm (5 cm increase) is expected, the A• x/J value In one method the macromolecules with the acid
reaches 3 214 cm, indicating 50 % increase (1.5 times groups or basic groups are synthesized first, and then,
of 2 232 cm). It would be a limit to expect a further the resin is dispersed in colloidal state or in nearly
increase of throwing power.° transparent soluble state by an addition of low molec-
ular basic materials or acid materials. As the macro-
4. throwing Power Based on Corrosion Protection molecules acid groups is anionic, it is called anionic
As shown in Table 3, the calculated throwing power electrodeposition resin, and as the ones with basic
does not well consist with the observed one precisely. groups is cationic, it is called cationic one.
This is explained as follows; the calculated value is In the other method, resins being not designed
the length of paint film detected theoretically, on the for electrodeposition coating are colloidally dispersed
other hand the observed one is the length recognized in water chemically or physically by aids of ionic
by naked eyes. And these two values are from dif- low molecular chemicals such as ionic surface active
ferent basis. agents. The resin particles obtained by this method
F.M. Loopl i * thought that corrosion resistance have ionic low molecular groups adsorbed on the sur-

Raview
 Transactions ISU, Vol. 23, 1 983 ( 1001 )

face of its particles. These particles have the ionic

1) ) Polymer design which the deposition
properties. The resin particles with anion are called
compositions are controlled easily
anionic electrodeposition resin, and the ones with cat-
2) Selection of cure reactions
ion are called cationic one. The latter type of resin
PPG could develop superior resins for cationic elec-
has been partially applied for the automobile bodies.
trodeposition due to the good knowledge about the
The reason mainly belongs to the unstabilities of resins
automobile line in terms of operating conditions by
in the continuous running of industrial coating line.
the past experiences in the anionic electrodeposition
2. Resins for Anionic Electrodeposition Coating system.
Recently resins for cationic electrodeposition coat-
Resins for anionic electrodeposition coating have
ing were reviewed by Wismer ef a/.*' and Kordomenos
carboxylic groups (fi—COOH) and are neutralized by
and Nordstorm.'°
bases (B) to make dispersible in water.
Resins for cationic electrodeposition coating contain
RGOOH -j-B — ACOO MBH* the cationic groups as indicated in Table 4.*' They
were disclosed in many patents.
fiCOO is macroanion. Resins for anionic electro- Acids (NA) are generally organic such as acetic,
deposition coating used for automobile industries in lactic, etc. The typical crosslinking mechanisms are
the beginning were prepared from vegetable oils, indicated in Table S. Usually a trifunctional blocked
thereafter they were partially substituted for synthetic isocyanate or isocyanate prepolymer was mixed with
resins such as polybutadiene. Bases (B) were pri- a hydroxyl or amine functional polymer and then
marily low molecular weight amines such as triethyl- codispersed in water/acid solution. In many cases, half-
amine and diethylamine, however in cases potassium blocked diisocyanates react with hydroxyl func- tional
hydroxide has been used. back bones resulting in a self-crossling system.
The cure of coating is carried out by oxidation re- 1. r.poxy Resins
action of unsaturated bonds mainly and by crosslink- The most frequently used epoxy groups resins were
ing reaction between melamine or phenol resin and the well known polyglycidyl ethers of polyphenols such
maleinized resin partially. as Bisphenol ,A l °
1• O1eoeesxocous ¥teszns In many cases the epoxy resins were modified by
Oleoresionous resins have a good adhesive perform- the introduction of certain groups or chain extenders
ance, pigment dispersibility and storage stability in to incorporate additional properties which must exist
the paint compositions. When they are used for auto- in electrodeposition coating such as high throwing
mobile bodies, strontium chromate is commonly for- power, flexibility, fast curing, cfc.
mulated in the primer paint as anti-corrosive pigment.
And oleoresionous resins are modified with phenol Table 4. Cationic groups of cationic electrodeposition
resin, epoxy resin or styrene—allylalcohol copolymer resins.
in order to improve corrosion resistance and throwing
Cationic groups for water dispersib ility
power. Chemical structure
2. Polybutadiezne Resins
The characteristics of liquid polybutadine are good 1. Primary and secondary amines solubilized withA—NHt•A—
acids
water resistance, storage stability in the paint com- At—NH,• -
positions. The paint film obtained by using it is
tough owing to its highly content of unsaturated 2. Tertiary amine solubilized with acids
bonds. There are two kind of commercial products
At—NH+ •J-
of liquid polybutadiene, in which the polymerization
occurs mainly at 1,2 (1,2-polybutadiene) or 1,4 un-
saturated bonds (1,4-polybutadiene). When they are 3. Q_uaternary ammonium acid salts
applied for electrodeposition paint, they give different A,—N+—A •J-
advantages. 1,2-polybutadiene has good leveling pro-
perty and throwing power, but poor corrosion resist-
4. Quaternary ammonium hydroxides
ance in comparison to 1,4-poIybutadiene.

3. Resins for Cationic Electrodeposition Coating

The resin synthesis for cationic electrodeposition 5. Quaternary phosphonium acid salts
coating will not be difficult at present. The tech-
nologist majored in organic synthesis could prepare
various kinds of resins. From the beginning of the 6. Tertiary sulfonium acid salts
1970’s when the electrodeposition coating system was
predicted to occupy a large market in the industry,
many patents on cationic resins have been claimed.
7. Quaternary ammonium-
In the design of resins for electrodeposition coating, carboxylate
the following points should be taken into considera-
tion.

Review
1002 ) Transactions ISU, Vol. 23, 1 983

Table S. Crosslinking mechanisms of cationic electro- reaction of dialkylaminoalkyl amines to form amine
deposition coating. functional malemides.'
Crosslinking
An epoxidized polybutadiene was reacted with an
mechanism Chemical reaction
amine acidi’ to yield an oxidizable resin system
which was deposited at the cathode.
1. Crosslinking SCH,—CH—
with epoxy
groups OH OCHzCH — 4. Film Performances of Electrodeposition Coating
OH In Table 6 are the typical properties of the anionic
2. Crosslinking +A—O-C—NH— and cationic electrodeposition paints produced.
with blocked
isocyanates OH O
5. Corrosion Resistance of Electrodeposition Coating
+ROH}
1. lorrosioxc o/ Automobzte Bodiee
O-C—NH—
The paint film of cationic electrodeposition coating
for automobile bodies provides the superior anti-cor-
rosive performance. In corrosive environments rusts
of following four types are sometimes observed on the
-PP,OH{ coating surface and the steel surface of automobile
N—C—NH—
bodies.
O 1) Uniform corrosion
3. Crosslinking -j-fiOCHt— 2) Crevice corrosion
with melamine/
formaldehyde OH 3) Pitting corrosion
or phenolic 4) Galvanic corrosion
resin Uniform corrosion is observed on the outside of
O —CH,—+AOH }
automobile bodies and the inside of closed parts such
4. Crosslinking —O— C —CHtCHtNHA
rim Michael as doors or rocker panels. The corrosion generated
reaction on the coated outside of bodies are due to the decrease
—CH-CH, -J- HtNn } of the isolation ability of films from corrosive environ-
O ment, that is the increase of permeability of oxygen
—• —(—CH—CHP—)—-j-HON I and water. The electrodeposition film in the inside
C-O of closed parts can not extend beyond the limit of
O throwing power, and moreover paint is not accessible
to complete closed parts.
5. Thermal poly-
meriz ation with —CH=GHg —› —(CH—CHP)— Crevice corrosion is observed on the uncoated parts
unsaturated (the hemming parts of hoods, doors and trunk lids,
bonds
etc.), in which steel plates are twofold. The paint can
not give access to steel surface of these closed parts.
One such modification was described by Jerabek Pitting corrosion is observed on the defect part of
ct aJ., 14 in which diepoxides react with polymeric diols filrrt. (The damaged area caused by the impact of
to obtain chain extended epoxy resins. pebbles or scratched area reached to steel surface.)
Both polyester and polyether diols were used as the The rust generated around the defect part becomes
chain extenders. The improvements claimed for these often scabbed. This rust is sometimes called scab
extended epoxy resins were higher rupture voltage, corrosion.
improved flow, coalescence, and flexibility. Galvanic corrosion is observed at the contact part
Polycondensation products of epoxy resins synthe- of two different metals. (e.g., the part being fixed
sized by Marx and Gulbins'^ using 9-hydroxyaceto- embrame)
phenone were further reacted with formaldehyde and 2• Improvement of Corrosion Protection of Electrodepo-
a secondary amine. sktnon Coating
It was claimed that these polycondensation prod- The concept of corrosion protection by electrode-
ucts had superior adhesion and corrosion protection position coating is shown in Fig. 11.
properties in comparison to conventional epoxy resins.
2. Marmich Bases V. Engineerin,g Process of Electrodeposition
A series of patents1® describe the resin systems suit- Cootift,g
able for cationic electrodeposition which are Man-
nich bases derived from the reaction of condensed 1. Metal Pretreatment
phenolic compounds with hydroxyl containing secon- The metal pretreatment prior to electrodeposition
dary amines and formaldehyde. coating is inevitable to enhance the paint film per-
3. methane Resins formance. The metal of the object is in general easy
Matsunaga r/ al.!*! was the first to synthesize catio- to form oxide compounds and deoxidizing treatment
nic thermosettable urethane resins. is essential. When the metal is covered by oil, the
g. Reeizce Gozstaizxizsg Uxxaafurated Bozsds first process of the metal pretreatment is degreasing.
Unsaturated fatty materials, such as linseed oil or The main purpose of priming is to protect the sub-
polybutadienes have been maleinized followed by the strate metal against corrosion. The primer intercepts

Reyiew
 Transactions ISU, Vol. 23, 1 983 ( 1003 )

Table 6. Properties of anionic and cationic electrodeposition paints.

Cationic electro- Anionic electro-

Performances Test items deposition coating* deposition coating** Note

Total solids (% ) 18 20 12- 14

pH 6. 2-6.7 8. 5 9. 0
Liquid conductivity (yS/cm) 900 - 1 500 1 800-2 100
Bath paint properties Applied voltage (V) 250 250
Applied time (min) 3 3
Coulomb efficiency (mg/C) 35 23
Film thickness (pm) 20 20

Baking schedule 30 min at 170 °C 30 min at 170 °C

Pencil hardness 3H H
Cross cut i00/i00 100/ i00 1 mm width
Impact resistance pass 50 cm pass 50 cm 1/2" Q, 500 g
Water resistance pass 500 h pass 500 h dipping at 40 °G
Electrodeposition film Alkali resistance pass 240 h pass 48 h 0 . 1 N NaOH
peformance
Chip resistance Good Good Gravelometer

35 °C, 5 % NaCl
(Degrease) pass 240 h (10 pm) 24 48 h (10 pm) (Film thickness)
Salt spray
resistance within S mm
(Zn-phosphate) pass 1 000 h (20 pm) pass 400 h (20 pm) Scribe creep

Cross cut 100/100 100/100 1 mm width

Impact resistance pass 30 cm pass 30 cm I/2" Q, 50 cm
System film pass 240 h dipping at 40 °C
performances*** Water resistance pass 240 h
Chip resistance Good Good
Salt spray resistance pass 1 000 h pass 400 h 35 °C. % NaCl

* Powertop U—30
** Powercoat No. 9000
*** Zincphosphating -J- Electrodeposition + Surfacer -]- Top coat

Improvement of corrosion protection of electrodeposition coating

Improvement of film performance Improvement of bath paint . properties

Resistance against impact Resistance against corrosion

Decrease in uncoated area .

High build Toughness Decreased in permeation Reduction of chemical High throwing

of hydrated ion and oxygen reaction rate power

High tension High crosslinking Functional Groups Anti-corrosive Electro— Dehydration by

pigments conductivity electroosmosis

Fig. 11. Concept of corrosion protection by electrodeposition coating.

to contact the metal with corrosive materials. The performance of electrodeposition coating should
After phosphating, the excess phosphate solution be evaluated as the hybrid coating containing the
must be rinsed off with enough water in order to pre- metal pretreatment. An example of the total coating
vent the electrodeposition tank from contaminations. process is given schematically in Fig. 12.

Review
( 1004 ) Transactions ISII, Vol. 23, 1983

2. Paint Recovery from Rinsed Water

the quality of rinsing water at the final rinsing process
In electrodeposition coating, the excess paint which is solvent ‘ water ’ itself. In the condensation process,
does not contribute the film forming should be rinsed reverse osmosis which allows to pass only water and
off to give a good film appearance. If the rinsed low molecular weight solvent in the theoretical basis
water is discarded, it may cause water pollution. In is superior to ultrafiltration.
order to prevent this, the automobile bodies after elec- However, in the industrial electrodeposition coating
trodeposition are rinsed off by multiple water rinsing line, the paint varies during electrodeposition and is
process and the rinsed water is returned to the prior involved in contaminations, leading to the deteriora-
rinsing water tank in regular order. Some of the tion of the film performances. To prevent this, the
rinsed water containing the highest content of paint paint is expected to renew as early as possible either
(just after electrodeposition) is returned to the elec- by the continuous discard of the rinsed water or by
trodeposition tank. This process enhanced the effi- the utilization of the paint at the earliest time. This
ciency of its water utilization and decreased the is why the electrodeposition system has been indus-
purged water. Here, the electrodeposition tank is not trially utilized for the mass production.
permitted to be diluted by the rinsed water. There In the closed system mentioned above, it can be
fore, the water amount corresponding to the evapora- said that the closed system is allowed to fit the tech-
tion is allowed to supply. If the paint is condensed nology to keep the film performance at a certain level.
by some device, it is permitted to supply water cor- As shown in Fig. 13, the drain pipes are installed at
responding to the condensation amount. Hence, the tank to remove undesirable materials.'° The perfect
ultrafiltration technology was introduced. And the closed system implies the perfect control of the main-
system utilizing the ultrafiltrate as rinsing water was tenance of the paint relating to the film performance
developed and the problem mentioned above was dis- and the possibility of the infinite utilization of the
solved. In the perfect closed system, it is ideal that paint. If this is accomplished, the electrodeposition

Spray

Fig. 12. Dip

An example of coating process.

D.I. WATER

DIP TANK RINSE TANK 2 RINSE TANK 3

FILTER

PAlNT SUPPLY DRéfN

PAINT RETURN

HEAT EXCHANGER
ULTRAFILTRATION
tJLTRAFILTRATE
D.I. WATER

HOLDING
ELECTROLYTE TANK Fig. 13.
TANKDRAINDRAIN
Typical commercial automobile cathodic
electrodeposition installation.

Review
 Transactions ISU, Vol. 23, 1983 ( l OO i )

coating system will be applied to the small production Table 7. An example of ultrafiltrate composition.°°*
line in addition to the mass production line such as
Anionic Cationic
automobile bodies one.
Solid (%, ) 0 .40 050
3. pH Control of Electrode.position Bath
When macroion to form the electrodeposition film 2.50 0.90
is removed from the paint bath, counter ionic species Solvent AlCOhO 050 1 . 80
remain in the deposition tank. This leads to the 1%) Ester 1 . 20
change of pH and electrodeposition coating can not Total 3 .00 -3 .50 4. 00
be continued. Therefore, the status that the electro-
Organic amine Organic acid
deposition coating process has succeeded in the indus-
Neutralizes (%) 0. 40 0. J9
trial line relies on the development of pH control
Water l%) 96.20 95 .3t
methods. The following methods have been develop-
ed up to date. COD Mn (mg//) 25 000 30 000 30 000 45 000
(1) Neutralizer deficient resin feed system
BOD (mg/I) 10 000 - 20 000 20 000 35 000
The limited resins are used for cationic electro-
deposition. This has been widely accepted in anionic
electrodeposition coating system. nal function recovers. However, if the paint is not
(2) Diaphragm system treated suitably, there will cause the following dam-
Counter ionic species is accumulated in the dia- ages.
phragm cell installed the counter electrode. And (I ) If ionic species possessing the same polarity as
neutralizer is removed from the electrodeposition paint the counter ion is removed in excess, the paint aggre-
by pumping out this liquid in the diaphragm cell. gates. This treatment failure can not be absolutely
This has been widely accepted in cationic electrode- permitted.
position coating system. (2) Ionic species possessing opposite polarity (the
(3) Ion exchange method same polarity as macromolecular ion) are allowed to
Counter ionic species is removed from the paint contain in comparatively excess, and they play a key
liquid by using ‘ ion exchange resin ’ This has been role of paint materials. Under some limited condi-
applied to a few automobile bodies line. tions, undesirable ionic species contribute to increase
(4) Dialysis or electrodialysis method the conductivity of the paint which is essential for
This has been only accepted as a subsidiary method. throwing power. If they are removed, throwing pow-
(5) Ultrafiltration system er lowers.
This method is very useful because of the possibility (3) If ionic species such as CrOi‘ which are
of the continuous running, but the cost of the waste added to improve the corroszon protection of the film
treatment is high. are removed, the film performance against corrosion
In any method mentioned above, the actual con- deteriorates.
trol of the bath is based on the chemical analysis to If throwing power is high enough and the resin
keep the paint suitable compositions. The further possesses high corrosion resistance without anticorro-
improvement will be expected to enhance its rational sive pigment, it is allowed to remove ionic species
control. com- pletely. The removal of ionic species by ion
exchange method is easy. It is possible to remain
4. Renewal of Electrodeposition Bath desirable ionic species in the deposition tank by
The application of ultrafilter for the renewal of the utilizing ion selectivity of exchange resin; therefore, it
electrodeposition bath has been rapidly accepted in will be ex- pected to develop the utility of ion exchange
the industrial line. Ultrafiltrate will not be colored, method for electrodeposition coating system.
but it has a high biochemical oxygen demand (BOD) Ultrafiltration is popularly known as the method
and chemical oxygen demand (COD), therefore waste to measure the size of colloidal particles. Ultrafiltra-
treatment is inevitable before discard. (Table 7) tion collects the colloidal particles while passing
Ultrafiltrate contains some non-electrolytes such as through low molecular weight compound, solvent and
additives which are essential for the film forming; ionic species. The pore size of ultrafilter is various
therefore, the filtrate will not be discarded from a and it is selected properly corresr onding to the size of
standpoint to remove undesirable ionic species. the colloidal particles. Ultrafilter does not work to
Ionic species which are brought from the prior segregate the counter ion for macroion. The counter
tank, and decomposition compounds in the resin ionic species under the chemical equivalent amount
which are inevitably involved during the resin pre- of neutralisation can not pass through itself. As the
paration accumulate in the deposition tank. They ultrafilter does not have the ion selectivity, the
deteriorate the deposition efficiency and provide a filtrate keeps an equivalent balance of cation and
poor film appearance. They also lower the effect of anion. This indicates that various low molecular
counter ions which help colloidal particles composed weight materials other than inherent ionic species
of film forming materials to stabilize. In the worst pass ultrafilter.
case, they lead to the aggregation of the paint. When On the other hand reverse osmosis collects the par-
the paint is treated by ion exchange method, its origi- ticles, which results in osmotic pressure. In contrast
to ultrafilter which pass dissolved inorganic salts, re-
(1 006 ) Transactions ISU, Vol. 23, 1983

verse osmosis reject the passage of ionic species.

Proper Supply Paint
It is recommended to use various combinations of
Film
systems mentioned below as corresponding to the pur-
pose. The proper supply of the paint is shown in (1)
of Fig. 14 and the combination among (2) (6) will
be selected. Rinsing
! Diaphragm
Via Themes on fffectrodspositiori Coatfri,g Process
for Automobile Bodies
The reasons of industrial use of the electrodeposi-
AE CE RO
tion process are its economical and mass production
UF
besides its film performance. When the real figure
of the electrodeposition coating process is to be con-
sidered, the anti-corrosive design of automobile bodies (1) Neutralizes deficient resin feed system (proper
must be involved. The anti-corrosive design is the supply)
key technology. The present status and the possible (2) Diaphragm system
future development is described below. The per- (3) Ultrafiltration system
formance of the primer obtained by the present elec- (4) Anion exchange method
trodeposition technology for automobile bodies would (5) Cation exchange method
not be dully satisfactory with. In order to discuss (6) Revers osmosis system
this essential theme logically, film performances, en- Fig. 14. Various renewal systems.
gineering process and coating methods are referred to.
1. Film Performances
Though film performances being demanded differ
in the location of automobile bodies, the following
STRENGTH

three items would be future themes.

(1) Prevention of steel parts constructing engine
room from oxidation reaction
(g) Corrosion protection of skirt parts with the de-
fect area in the film STEELONL
(3) Film adhesion to precoated steel in particular
TIME
film adhesion under wet-dry cycle test
In theme (l ), organic materials would not fit for Fig. 16. A model of the strength deterioration of steel mate-
coating, even if the ones containing silicon compounds rials due to corrosion.
are developed. They will not put up with the high
temperature because of the limited thermal stability combination with characteristics of precoated steel
of chemical carbon bonds, therefore the application of and corrosion environment under primer.
inorganic materials would approach to steel parts. In the steel containing minor elements, minor ele-
In theme (2), corrosion types must be considered. ments affect the core of phosphating growth and its
The corrosion arises from the defect part (local corro- crystal form. They would be also essential to be
sion) due to the drop in a penetrating coefficient of analyzed in combination with characteristics of steel
water and corrosive gas through film and due to the surface.
increase of film adhesion. The real life of the con-
structed steel is the power, which maintains the initial 2. Primer Coating Process f0Y Automobile Bodies
strength steel constructs as long as possible. By film At present, the coating process has been generally
performances, it is essential to prevent the rapid drop accomplished. However, the following themes from
in the strength caused by local corrosion, though it electrodeposition coating process would be necessary
goes without saying that the film prevents the steel to be dissolved.
from uniform corrosion. This concept is shown in 1. Thrownng Power and Coating Thiclrness
Fig. 15. Electrodeposition coating has established in a large
In theme (3), the precoated steels plated with vari- place as a primer for automobile bodies relying mainly
ous metals have been produced by the demand for the on the superiority of throwing power.
design of automobile bodies. The steel produced by However, the recessed parts (e.,g., the inside of door
Continuous Annealing and Pickling Line is different part) remain unpainted virtually by the present elec-
from Batch Process in terms of the quantity of minor trodeposition coating process. As described in Chapter
elements added into the steel. In the precoated steel, III, the increase in film thickness is tend to the de-
as the plated metal is usually more active than iron, crease in throwing power. It would be attained to
its oxidation reaction under priming conditions affects enhance remarkably their both performances (that is,
the nascence and rate of corrosion reaction. Accord- the ability to increase in film thickness and the ability
ingly, the role of phosphate coating and its crystal to coat fully up to the united parts) either by utilizing
composition would be necessary to be analyzed in the mixture of more than two paints which they differ

Review
 Transactions ISU, Vol. 23, 1983 ( 1007 )

largely in the film formation mechanism each other or

sess it owing to the cost decrease of micro computer,
by some devices relating to the deposition method
through every industrial coating lines possess the dif-
(this implies the method of power supply and the de-
ferent characters.
sign of the deposition tank).
2• Azzxbaeazt @oatz'o1 izt Balcizxg E'urnace
According to the present technology, we believe
The problem that the tar arised from evaporated
that the methods mentioned above cause negative
material from paint in the baking furnace dropped to
factors in any of mass production, process control and
the automobile bodies has happened. This essential-
film performance. It is rather important to approach
ly belongs to the theme relating to the devices such as
from standpoints how the design of automobile bodies
furnace structure (implies thermal efficiency) and pro-
would be improved in terms of corrosion resistance
cess engineering. On the other hand, this also be-
and how the expected film performance could be
longs to the theme on paint compositions subsidiary.
achieved. In cases, the use of pre-coat metal for auto-
mobile bodies will be partially realized. 4. Theme on the Materials for Automobile Bodies
2. Theme Amusing fronn Catnon Process
The cationic electrodeposition process holds many The new materials such as plastics and precoated
advantages in a point of corrosion protection in com- metal may be taken up from the view point of corro-
parison to anionic one. That is, sion protection of bodies. As more than two different
metals are contracted at the welding areas, the corro-
(1 ) The metal does not dissolve from the cathode
sion reaction is promoted there. It will be necessary
(the object) when the voltage is applied.
to coat the substrate with the high electric resistance
(2) The film has the anion selective permeability
film and superior adhesive paint.
and it prevents the permeation of cationic species when
it is exposed to corrosive environment. KfZ. Concftzsion
Surfaces and top coat possessing plenty of carboxyl
In this review on the electrodeposition coating pro-
groups are usually anion selective film, so both anion
cess technology for automobile bodies, its short
and cation species are prevented to permeate three-
history, mechanism, throwing power, resins and
coat film. And it affects the lowering of electric re-
process were described in Chapters I to V, respectively
sistance of film and accc rdingly it affects corrosion
and in Chapter VI, themes on problems on the basis of
resistance. On the other hand, cation electrodeposi-
the authors’ views were described. When the
tion process holds following disadvantages.
automobiles pro- duced in the largest mass industrially
(l ) The deposition tank acts as the anode during
are viewed from a standpoint of corrosion protection,
electrodeposition. This causes the dissolution of the
it is quite right to say that this theme should be solved
metal from the tank (the deposition voltage applied
by the total technology of the substrate steel, phosphate
is over decomposition one of iron). Therefore, some
coating, electrodeposition coating. As long as the steel
engineering devices such as the lining of the tank and
is uti- lized and the commercial value of automobiles is
the installation of the stainless steel electrode are
large- ly occupied by hue and appearance, the coating
neces- sary.
is inevitably essential. The electrodeposition coating
(2) The paint is acidic, causing corrosion of the
plays a key role for durable years of automobile bodies.
whole installations of the process, therefore the corro-
Electrodeposition process will be continued to be used
sion protection in any of installations are essential.
for automobile bodies on the basis of many advantages
(3) Hydrogen emits from the cathode (the object).
such as economical value, easy quality control and
Since the cold-rolled steel is utilized now, the deterio-
easy automation control.
lation by hydrogen embrittlement is negligille. If
Paradoxically, if the electrodeposition coating pro-
high tensile steel is utilized, various devices to prevent
cess could not be improved to cover up to the fine
hydrogen embrittlement may be inevitable.
performance in a point of total corrosion protection
3. theme on Coating Process design, it may be possibly substituted for other pro-
cess. The trigger of substitution will be pushed by
1. Paint Supply and Concro1 of Paint Tank
the problems from relatively sober spheres such as the
In the present industrial coating line, the paint
answer to the recessed parts and to the welding areas.
supply and the control of paint tank are performed
From a large point of view, it will rely on the logical
efficiently. But there would be left some means to
rationalize. thinking of the protection role of precoated metal and
The rate limiting factors of the use of automation coating against corrosion. In other words, it will rely
control by a computer would be analyses in the rela- on whether they will perform differently their func-
tion between chemical informations of the paint and tions based on their guide principles of corrosion pro-
physical ones of the electrodeposition coating process. tection or not.
By clarification of the mechanism of throwing power
and it is believed that this would be an analysis in
REFERENCES
factors including geometrical conditions besides paint
1) N. Furuno, H. Kawai and Y. Oyabu: S£ikizoi Kyokaishi
conditions in the industrial line. The automation
control could be realized from the viewpoint of the NJ J apan Soc. C!olour Material) 45 (1972), 564.
2) A. M. Usami: Polyin. Plast. Tech. Eng., 15 (1980), 115.
investment needed to do it in contrast to the cost de-
3) Y. Oyabu: ,;f. Metal Finishing Soc. J apan, 28 (1977), 306.
crease by saving labor. It would be valuable to reas-
4) D. G. Anderson, E. J Murphy and,J. Tucci: J- <••!- >•«!-

Review
( 1008 ) Transactions ISU, Vol. 23, 1983

50 (1978), No. 646, 38.

11) F. M. Loop: Corrosion ’80, Assoc. Corro. Eng., Chicago,
5) A.R.H. Tawn and J R. Berry : J- Oil Clolour them. Assoc., March (1980), Paper No. 125.
48 (1965), 790.
12) P. I. Kordomenos and ,J. D. Nordstorm : J boat Tech., 54
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NJ- J•é an Doc. Colour 3foterioi), 42 (1969), 362. 13) U.S. Patent No. 3853803, (1974).
7) N. Furuno, H. Kawai and Y. Oyabu: J-c olloid Interface 14) U.S. Patent No. 4148772, (1979).
Sc‹., 55 (1976), 297. 15) U.S. Patent No. 4172193, (1979).
8) N. Puruno and Y. Oyabu: Prog. Org. boat., S (1977), 201. 16) U.S. Patent No. 4134832, (1979).
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