"

Technical Applications and Theoretical Backgrounds of Secondary Electrolysis of Anodized Aluminum

By T. SAT0 and K. KAMINAGA

OF
Summary
Electrolytic coloring, electrodeposition coating and several other surface finishing techniques for aluminum h a w been carried out by secondary electrolysis of anodized aluminum. The theoretical backgrounds of these surface finishing techniques are usuiilly based on the "pore filling theory",
"fliiw

of Secondary Electrolysis of Anodized

Aluminum Several surface finishing techniques for the secondary and tertiary electrolysis of anodized aluminum have been known. These techniques using the multistage electrolysis are typically shown in Fig.1. There techniques are three for the surface secondary finishing anodic

theory"

and

"current

recovery

phenomena".
1. I n t r o d u c t i o n

electrolysis of anodized aluminum as shown

in the following:

(1)Thc secondary anodic electrolysis of anodized aluminum in an anionic water soluble coating material leads to the formation of a film layer over anodized aluminum. This surface finishing is called electrodeposition coating, and has been widely applied to materials. (2)The secondary anodic electrolysis of anodized aluminum in aqueous sodium oleic acid solution results in the deposition of oleic acid in the pores of anodized aluminum, lubricative. which This thereby method becomes has been aluminum building

Electrolytic coloring, electrodeposition coating and several other surface finishing techniques for anodized aluminum have been performed by applying secondary and sometimes tertiary electrolysis to anodized aluminum. Upon applying secondary electrolysis to anodized aluminum, thc understanding of (1) the pore filling theory,
(2) flaw theory and (3) current recovery

phenomena is essential. technical applications

Accordingly, the and theorctic:rl

backgrounds of the secondary electrolysis

of anodized iiluminum ;ire reported in the

succeeding sections.
2. Examples of Technical Applications

employed for the surface finishing of industrial aluminum parts. (3)Application of high voltage to the

367

PRIMARY ELECTROLYSIS

SECONDARY & TERNARY ELECTROLYSIS

TECHNICAL APPLICATIONS

(1)ELECTRO DEPOSITION COATING (2)DEPOSITION OF OLEIC ACID (3)SPECIAL ELECTROLYSIS CAPACITORS

(1)ELECTROLYTIC COLORING

BY CATHODIC CURRENT

(1)ELECTROLYTIC COLORING BY ALTERNATING CURRENT

ANODIZING

HZSO4 BATH

r@i

+
r81
3
M E
I
J I

(1)MULTI-ELECTROLYTIC COLORlNG( 1)

r@i

(1)MULTI-ELECTROLYTIC COLORING(2)

Fig1 Secondary and ternary electrolysis of anodized aluminum.

368

secondary

electrolysis

of

anodized

and it is important from the industrial point of view to prevent spalling from occurring. Another phenomenon to be paid attention to during the secondary electrolysis of anodized aluminum is its "chemical dissolution". Whether o r not voltage is applied to anodized aluminum in its secondary electrolysis, part of anodized aluminum is dissolved by the chemical dissolution power of an electrolytic bath, resulting in the degradation of the film performance of anodized aluminum. This means that chemical dissolution of anodized aluminum should be inhibited on its secondary electrolysis.

aluminum in neutral aqueous solutions leads to the formation of thick barrier

layers at the pore bottoms of anodized

aluminum; accordingly, these films have been used for electrolytic capacitors for the special use. When anodized aluminum is subjected to cathodic electrolysis in an aqueous metallic salt solution, the metal is deposited in the pores of anodized aluminum, which is thereby colored. This surface finishing technique has been adopted by part of companies for coloring aluminum building materials since 20 years before. The AC electrolytic coloring of anodized aluminum in aqueous metallic salt solutions has been more nidely employed
in

3. Theoretical Background Common

companies worldwide than the abovementioned c;ithodic electrolytic coloring method. If anodized ;iluminum undergoes secondary anodic electrolysis or secondary AC electrolysis and is followed by tertiary AC electrolytic coloring in
i\

Structures of A n o d i z e d A l u m i n u m and All the T y p e s of

to Film
Secondary Electrolysis
As to the film structures of anodized

aluminum, the Keller, Murphy and Wood models have been proposed, but the changes in anodized aluminum have often been discussed by using the Keller model. These film structure models are shown in Fig. 2. Quantitative investigation has also been carried out on the film structures of anodized aluminum. The thickness of the barrier layer of anodized aluminum depends on anodic oxidation voltage. Since the barrier formation rate of sulfuric acid film is 10 AN. Then, 15-volt anodizing voltage ciin produce the barrier thickness

nickel biith,

then anodized aluminum is electrolytically colored into various kinds such as blue, green and red. The commercialization of this surface finishing technique has been investigated in a pilot plant sciile. While these various electrolytic coloring techniques a r e being applied, spotty pealing off of anodized aluminum sometimes takes place. This phenomenon is ciilled "spalling",

3
369

Fig.2 Models of film structures of anodized aluminum. of 15O&lOhi x 15 volt). Moreover, since the pore wall thickness of anodized aluminum is two times the barrier layer thickness, the former anodically oxidized at
15 volt becomes 300A (150A A: 2).

The

result of observation with an electron microscope shows that the pore size of anodized aluminum range from 100 to 150

with the number of pores of anodized

aluminum is about 76 billion/cm2. These values are given in Fig. 3. The thickness of a porous layer depends on time of electrolysis. Figure 4 shows the differences of film structures by different anodizing voltages. When anodic oxidation voltage is lower, the barrier layer and pore wall of Fig.4 Different film structures by different anodizing voltages

370

anodized aluminum a r e thinner and its number of pores is greater. On the contrary, when anodic oxidation voltage is higher, the barrier layer and pore wall of anodized aluminum a r e thicker and the number of pores is smaller. If these kinds of anodized aluminum are subjected to secondary electrolysis, then the film structures of anodized aluminum change the state of secondary electrolysis. Upon performing secondary anodic electrolysis o r secondary A C electrolysis, if secondary anodic voltage is higher than primary anodic voltage, the thicker barrier layer shown in Fig. 5 (A) is formed at the pore bottom of anodized aluminum.
I

phenomena will be explained in Section 4. The effect of barrier layer thickness on cathodic electrolysis appears in the electrodeposition of metal ions into the pores of anodized aluminum. When the barrier layer is thicker, metal deposition into the pores is uneven as shown in Fig. 6, but even when the barrier layer is thinner. This problem will be discussed in detail in Section 6.
(61
(3)

Fig6

Metal depositions on thicker and

thinner barrier layers

The difference in the thickness of porous layers of anodized the aluminum secondary gives anodic influence on all the types of secondary electrolysis. In Fig.5 Formations of thicker barrier layers electrolysis of thicker anodized aluminum, the insides of anodized aluminum pores Conversely, if secondary anodic voltage is lower than primary anodic voltage, the state of secondary electrolysis varies with the kind of a n electrolytic b:ith. In neutral baths, no change occurs due to secondary anodic electrolysis. In acidic baths, This however, the special change called "current recovery phenomena" takes place. become partially acidic, but partially alkaline in cathodic o r A C electrolysis. For thinner porous layers, the pH value of bulk solutions and anodized aluminum pores a r e neirrly identical. Other problems common to all the types of secondary electrolysis are (1) both ionic and electronic conductions in barrier layers,

5
371

(2) the existence of "flaws" on the barrier

the electronic current flowing in the barrier layer occurs due to "flaw" existing in it. Various phenomena associated with the secondary electrolysis of anodized aluminum can not be properly explained unless the concept - "The site of an oxide film where electronic current flows is called flaw." - is introduced. When anodized aluminum

layers and (3) the chemical dissolution of pore walls. Anodized aluminum is an oxide film consisting mainly of alumina, which is an insulating material having greater band
gaps for electronic conduction. Therefore,

the current flows through the barrier layer

, is of anodized aluminum, as shown in Fig. 7

ionic, and not electronic. Since the film

is

left

immersed in sulfuric acid, its pore walls begins to dissolve as shown in Fig. 8, and anodized aluminum finally disappears.

Fig.7 Ionic current through barrier layer

formation of anodized aluminum is carried out by the ionic current due to AI3+ and
02-, no problem occurs even if electronic

Fig.8

"Chemical dissolusion" and "field

assisted dissolusion" of anodized aluminum This phenomenon is called the "chemical dissolution" of anodized aluminum. In chemical dissolution, the pores of anodized aluminum are widened and dissolved, so this way of thinking is called the "pore widening theory". Although the degree of chemici~ldissolution of anodized aluminum is low in both weakly acidic and neutral baths, it takes places in all kinds of secondary electrolysis in all the electrolytic baths.

current does not flow.

However, if

electronic current does not flow in the barrier layer of anodized aluminum, then electrolytic deposition of metal ions into the pores of anodized aluminum does not take place. technique Practically, a surface finishing by which metal ions arc

electrolytically deposited into the pore of anodized aluminum has been commercially estiiblished as the "electrolytic coloring method". In other words, electronic current does not flow in the barrier layer of anodized aluminum theoretically, but it
flows practically. According to Vermilyeal),

The chemical

dissolution

of

anodized aluminum is affected by the kind of electrolytic bath, bath concentration and

372

bath temperature.

If the degree of the

of anodized aluminum,
(8)

chemical dissolution of anodized aluminum is high, then its corrosion resistance, wear resistance and hardness decrease, and thereby the film performance of anodized aluminum degrades. electrolysis inhibited. Table of
1

the difference between the "field dissolution" and "chemical

assisted

dissolution" of anodized aluminum,

(9) the formation of new porous films, and

In the secondary
aluminum,

(10) the "current recovery phenomenon"

of

anodized

found by Murphy.

therefore, its chemical dissolution must be gives the of theoretical anodized

If secondary anodic voltage higher than

primary anodic voltage is applied to anodized aluminum, then thick barrier layers are formed in every electrolytic bath. In particular, the application of high voltage to anodized aluminum in neutral baths causes special changes. The secondary anodic electrolysis of anodized

backgrounds for performing various kinds secondary electrolysis aluminum in a variety of baths. These are explained in Sections 4 , 5 and 6.

4.Theoretical Background Secondary Anodic Electrolysis.

for

aluminum in the neutral baths under constant current density gives the voltagetime curve shown by the polygonal line (A)
in Fig. 9. Vertical voltage rise originates

On performing the secondary anodic electrolysis of anodized aluminum, it is useful to understand the following facts and theories:
(1) formation of thick barrier layers at the

pore bottoms of anodized aluminum,

(2) the "pore filling theory" developed by

u c1
0

5 4

Dekker and Middelhock,

(3) the anodic decomposition reaction of

water,
(4) the generation of "flaw",

Fig.9

Voltage vs. time curves during

anodizing aluminum and oxide films

(5)

the effect of difference between from the electrical resistance of the barrier layer of anodized aluminum, and the subsequent voltage rise shown by the oblique line originates from the formation
of thick barrier layers at the pore bottoms

"monoprotic acid" and "polyprotic ;icid" on the formation of oxide films,

(6)

acidification due to anodic reactions

within the pores of anodized aluminum, (7) neutralization reaction within the pores

373

Table 1
Theoretical Backgrounds of Secondary Electrolysis of Anodized Aluminum

Anodic Electrolysis

Cathodic Electrolysis

AC Electrolysis

All Bathes

(1)Effects of Thicknesses of Barrier Layer and Porous Layer (2)Ionic Conductance and Electronic Conductance Through Barrier Layer (3)Existance of "Flaw" on Barrier 12ayer (4)"Chemical Dissolusion" of Oxide Film (2)"Pore Filling Theory" (3)Anodic Decomposition of Water (4)Generation of "Flaw" (5)Hurmful Ions for Anodizing (6)Acidification in the Pores (7)Neutralization Reaction i n the Pores (1)Formation of Thicker

Neutral Bathes (pH2-pH9

Acidic Bathes (PH<2)

(8)"Field Assisted Dissolution" of Barrier Layer (9)Formation of New Porous Layer ( 10)"Current Recovery Phenomena"

(1)Cathodic Reduction of H ' Ions (2)Cathodic Reduction of Dissolved oxygen (3)Electrodeposition of Metal (4)Alkalinization i n the Pores (5)Formation of Metal Hydroxide in the Pores (6)Destroy of Barrier Layer (7)"Spalling" of Oxide Film (8)Spalling with Na' ,K* , NH; . and etc.

(1)"Faradic Current" and Non- Faradic Current (2)Changes of Anodic Peak Current and Cathodic Peak Current with the Lapse of Time (3)Impeadance Equivalent Circuit of AC Eletrolysis
" "

(4)Formation of "AC Oxide Film" (5)Different Characteristics of "DC oxide Film" and "AC Oxide Film" (6)Recovery Phenomena of Alternating Current

of rinodized aluminum. These thick barrier layers are formed by the ionic conduction of AI3+ and 02-ions through the existing barrier layer, and can be written as the chemical reaction formula (1): 2AI + 302- -> AI203 + 6e

layers are formed at the pore bottoms of anodized aluminum up to lOOV anodic voltage in accordance with the pore filling theory proposed by Dekket et al.; however,
when anodic voltage exceeds lOOV, "flaw"

is generated in the pore bottoms of

.....(1)

anodized aluminum, and thereby anodic voltage rises slowly. Generally, the current flowing through the barrier layer of anodized aluminum i s an ionic one due to 02-and AI3+ ions, but electronic current sometimes flows through the barrier layer.

On the other hand, the primary anodic

electrolysis of aluminum metal in the neutral baths under constat current density results in the voltage-time curve shown by
t h e linear line (B)in Fig. 9. The state of

The site where this

barrier-type film formation in this case can be represented by Fig. 5 (B). The difference in gradients between the lines (A) and (B) in Fig. 9 stems from that in the areas of the barrier Iilyers. ancl From the difference in pore size of ilnodized gradients, the tronsport numbers of 02-

electronic current flows is named "flaw" by Vermilyeaf.). If electronic current flows through the barrier, the anodic reaction represented by Formula (2) takes place in the pore bottoms of anodized aluminum. 2H20 -> 02+ 4H'

AP+ ions,

+ 4e

.....(2)

aluminum and thickness of the porous layer can be calculated. The rese:irch method of this type was proposed by Deklcer and MiddeIhock2) about 25 years ago, and hns been called the "pore filling theory" or "pore filling phenomena". Lately, however, Baizuldin3) has insisted that the pore filling theory could be applied only to thin oxide films. He reported that the secondary anodic electrolysis of thick anodized aluminum in the neutral baths under constant current density led to the polygonal line shown in Fig. 9 (C). For thick anodized aluminum, thick harrier The reaction given by Formula (2) is said to be the anodic decomposition of Ivilter, by which oxygen gas and hydrogen ions are generated from the pore bottoms of anodized aluminum; the generation of hydrogen ions makes the aqueous solutions

in the pores of anodized aluminum acidic.

The secondary anodized anodic electrolysis therefore, of aluminum, leads

sometimes to the occurrence of the chemical reaction (1) only, and sometimes to the occurrence of (1) followed by (2). The difference between these two types can

375

be easily distinguished on the basis of difference between the voltage-time curves shown in Fig. 9. When anodized aluminum undergoes constant-current anodic electrolysis in an electrodeposition paint bath, the resulted anodic voltage-time curve becomes polygonal as shown by Fig. 9 (C)4).

the surface of anodized aluminum, it is necessary that flaws are formed at the pore bottoms of anodized aluminum and that the anodic decomposition reaction of water by electronic conduction takes place in the barrier layers. Further, the electrodeposition paint is neutralized by hydrogen ions generated by the anodic decomposition reaction

In

other words, when anodized aluminum is subjected to anodic electrolysis in the electrodeposition paint bath, thick barrier laycrs are first formed in accordance with the pore tilling theory, and then the electrodeposition paint molecules are neutralized by hydrogen ions generated due to the anodic decomposition reaction of water, forming finally paint films. represented by Formulii (3): R(COO-), The chemical reaction i n this c:iw can be

of

water;

accordingly, electrodeposition coating is not an anodic reaction, but a neutralization reaction.

To
of

cause water

the in

anodic anodized

decomposition

aluminum pores, an anodic voltage of lOOV or more should be applied; consequently, applied voltage for electrodeposition coating is as high as 150V. When anodized aluminum undergoes anodic electrolysis in sodium oleic acid aqueous solution, the resultant voltage-time

+ nH+ -> R(CO0H)n

.....(3)

curve is polygonal as shown in Fig. 9 (C). In this case, oleate anion is also neutralized by hydrogen ions generated by the anodic decomposition reaction of water, with the chemical reaction being as Formula ( 4 ) .

The chemicnl reaction given by Formula

(3) is schematically shown in Fig. 10.

Nitmelv, for electrodeposition coating over

The authors reported in SUIUFIN '94 that the anodic electrolysis of anodized iiluminum at +200V in 0.lgll tartaric acid made it a opaque gray film. The voltagetime curve obtained in this case also Fig.10 Mechanism
of electrophoretic

showed a polygonal line given in Fig. 9 (C).

deposition coating

10

376

This

is

because

secondary

anodic

anodic electrolysis of aluminum in aqueous monoprotic acid solutions does not form anodic oxide films. This is because anodic electrolysis does not form proton space charge in the barrier layer of anodized aluminum as shown in Fig. 11. In HNO3,

electrolysis at high voltage caused the anodic decomposition of water, making the solutions within the pores of anodized aluminum acidic, and because this acid formed new porous oxide films between anodized aluminum and aluminum metal. Photograph 1 shows the cross section of this opaque grey film taken by the electron microscope.

- .

(A 1

Fig.11 Formations of proton space charge in barrier layers

for example, it dissociates into NOS- and H+ ions in water. Since NO3- ion does not have H+ ion which can be emitted into the barrier layer, no proton space charge is formed in the barrier layer, resulting in no Photo.1 Cross section of opaque grey film formation of anodic oxide films. In H2SO4 and H3P04, on the other hand, they The reason why anodized aluminum must undergo hot water rinsing and pure water rinsing prior to the electrodeposition coilting of anodized aluminum can be explained on the basis of the "difference of monoprotic and polyprotic acids for anodic electrolysis". HNO3 Monoprotic acid means one
its

dissociate into HSO4- and H+, and H2PO4and H+ ions, respectively. As shown in Fig.
11, HSO4- and H2PO4- emit H+ into the

barrier layers and form proton space charges. Therefore, the anodic electrolysis of aluminum in H2SO4 and H3PO4 baths can form anodic oxide films. One thing to which attention should be paid is that anodized aluminum can be formed by the anodic electrolysis of aluminum in sulfuric acid baths, but that it can not be formed by the anodic electrolysis of aluminum in

having only one hydrogen ion such CH3(COOH) etc.,

HCI,

whereas as H2S04,

yolyprotic acid means one having two or more hydrogen ions such H3PO4, (COOH)2 etc. It is said that

11

377

N q S O 4 baths.

This is because Na2SOj

electrodeposition concentration of

coating Na2S04

in

the the

dissociates in water into Na+ and S042-. The latter ion, S042-, does not have the H+ ion to be emitted into the barrier layer; accordingly, anodic oxide films can not be formed. barrier The S042- ion destroys the layer, causing thereby pitting

electrodeposition paint baths.

When the in

electrodeposition paint bath becomes about 20 ppm, the barrier layer of anodized aluminum is destroyed, and so bath voltage does not become higher, but abnormal deposition of electrodeposition paint takes place, instead. The same is true for oxalic acid and oxalates. Oxalic acid dissociates into Sodium oxalate, C2O4H- and H+ ions, and C2O4H' anions can form oxide films. however, dissoocate into 2Na' and C2042ions. Because c ~ O 4 ~ anions have no protons, they destroy oxide films. Not only sulfates and oxalates but also sulfuric acid and oxalic acid in their extremely low concentration baths cause two-stage ionic dissociation, generating S042- and c ~ O 4 ions; ~ - accordingly, the barrier layers are destroyed at the time of anodic electrolysis. The reason why pitting corrosion occurs during the anodic electrolysis of aluminum in extremely lowconcentration sulfuric acid and oxalic acid baths can be ascribed to S042- and C2042ions generated by two-stage dissociation. The same is true for extremely lowconcentration tartaric acid baths, where tartaric acid undergoes two-stage

corrosion. Although HSO4- ions generally form the anodized aluminum films, it should be noted that S042- ions destroy the barrier layer. Therefore, the hot water rinsing of anodized aluminum followed by pure water rinsing prior to the electrodeposition coating of it is performed to remove S 0 j 2 ions contained within the pores of anodized aluminum. If a great amount of ~ 0 4 2 -ions iirc l d t
11

ittiin the pores of' i\nodizcd

aluminum, then the abnormal deposition of electrodeposition paint takes place. Figure 12 gives the voltage-time curves when anodized aluminum is subiected to

Fig.12 solution

Effects of Na2SO4 on secondarj

anodizing of oxide film in neutral aqueou!

dissociation and form harmful ions that can not emit protons. Therefore, if anodized

12

370

aluminum

is

subjected

to

secondary

time flaws are generated due to SOq2' anions etc. which hinder the formation of oxide films. These flaws may be the sites for the cathodic reduction of metal ions. In the case of tin baths, anions generated from stannous sulfate consist of the great amount of HSO4- ions and the small amount of
Sod2- ions. Consequently, the destruction

electrolysis in 0.1 - g/I tartaric acid bath (at

60C ), a great number of flaws occur in

the barrier layer, making the anodic decomposition reaction of water vivid. As

a result, solutions in the pores of anodized

aluminum become acidic, forming new porous oxide layers as shown in Photo. 1. In 10 - g/i tartaric acid hath, however, its ionic dissociation takes place in one stage,

of the barrier layers by Sod2- ions is minor, but the field assisted dissolution of the harrier layers by the great amount of H+
ions is large.

so the secondary anodic electrolysis of

anodized aluminum forms only thick barrier layers at the pore bottoms of anodized aluminum without any change in the appearance of anodized aluminum. Therefore, even if baths itre neutral, the pore filling phenomenon does not occur in neutral baths containing ;inions generated from monoprotic acids, those from twostiige-dissociated diprotic iicicis (Sod2-, O d i c acid and tartaric acid ions etc.) and those from three-stage dissoci;ited triprotic acids (Pod3- etc.), but flaws ;ire generated in the barrier layers. Owing to these flaws
the anodic decomposition reaction of \viiter

Baizuldin3) reported that flaws were generated in the secondary anodic electrolysis of thick anodized aluminum, iind in this case these flaws may also be generated due to ~ 0 4 2 - ions remaining in the pores of anodized aluminum. Remarkable flaw generation makes the corrosion resistance of anodized aluminum lower. Therefore, the expectation that the high- \rOltiige secondary anodic electrolysis
of iinodized aluminum in neutral baths

makes the barrier layers thicker and improves its corrosion resistance is not ;ilw:rys correct. The commentaries described above relates to the secondary anodic electrolysis
of anodized aluminum in the weakly acidic,

takes place. Anions destroying the biirrier layers

also affect A C electrolytic coloring in

nickel baths. If AC voltage higher than the primary anodic voltage of iinodized aluminum is applied to anodized aluminum in weakly acidic electrolytic coloring baths, the barrier layers of anodized aluminum become a little thicker, iind at the same

neutral or weakly alkaline baths.

The

results of the secondary anodic electrolysis

of iinodized aluminum in acidic bath are

different

from

those

obtained

above.

Neither the pore filling phenomenon nor

13

379

anodic decomposition reaction of water takes place. In acidic baths, the secondary anodic electrolysis forms the secondary porous layers. For example, the secondary anodic electrolysis of sulfuric acid film in oxalic acid baths leads to the formation of oxalic acid film between the sulfuric acid film and aluminum metal; namely, a double-layer film consisting of sulfuric acid film and oxalic acid film is formed on the aluminum metal. In the same manner, the secondary anodic electrolysis of sulfuric acid film in phosphoric acid baths lead to the formation of the double-layer films consisting of sulfuric acid film and phosphoric acid film. The latter doublelayer films have been industrially used as the interference coloring method. Upon performing the secondary anodic electrolysis of anodized nluminum in acidic baths, if secondary anodic electrolyzing voltage (V2) is lower than primary anodic electrolyzing voltage (Vl), then the famous "current recovery phenomena" take place. Figure 13 shows the crplunation of the current recovery phenomena which is given by MurphyS). If anodic voltage is reduced

to V2 volt while aluminum undergoes electrolysis with anodic voltage being V1 volt, then anodic current does not flow for some time, and after T min. anodic current (i2) begins to flow. The time T shown in Fig.
13 is called current recovery time, which is

a transient time required for changes in the film structure of anodized aluminum. The changes a r e shown schematically in Fig. 14. The thickness of the barrier layer and pore

Fig.14

Changes of film structures of

anodized aluminum by "current recovery I)henomena". size of anodized aluminum depend on anodic voltage during anodic electrolysis. The coating ratio of the barrier is 10hilv. Therefore, higher anodic voltage results in oxide films with thicker barrier layers, thicker pore walls and greater pore sizes, whereas lower anodic voltage leads to oxide films with thinner barrier layers, thinner pore walls and smaller pore sizes. Accordingly, if anodic voltage is reduced to V2 volt while anodic electrolysis proceeds

Fig.13 "Current recovery phenomena" by Murphy

14

380

at VI volt, then "anodized aluminum with thicker barrier layers and greater pore sizes" must change "anodized aluminum with thin barrier layers and smaller pore sizes". The transient time required for the changes in the film structures of anodized aluminum is current recovery time T. Conversely speaking, current recovery for modized aluminum enables its barrier layers and pore sizes to be thin and small, reslmtively.

anodic decomposition of water take place. However, when anodized aluminum is subjected to secondary anodic electrolysis
in strongly acidic baths, the dissolution of

the barrier layers is accelerated on account of the effect of electric field, and thereby new anodized aluminum films are formed. The high-speed dissolution of the barrier layers due to the effect of electric field is called the field assisted dissolution of anodized aluminum.

The

current

recovery

On the other hand,

phenomena have been industrially applied to multi-electrolytic coloring of anodized aluminum. If the barrier layers of anodized aluminum are made thin by utilizing the current recovery phenomena, metal is deposited uniformly in the pores of anodized aluminum during electrolytic coloring, so that anodized aluminum is multicolored with blue, green, red etc. Attention should be paid to the "field :issisted is dissolution" to and secondary "chemical anodic dissolution" of anodized aluminum when it subjected electrolysis. "Field assisted dissolution"

whether or not voltage is applied to anodized aluminum, it is dissolved by the chemical dissolving forces of electrolytic baths as long as anodized aluminum is immcrsed in them. The difference between the field assisted dissolution and chemical dissolution
of

anodized

aluminum

is

schematically shown in Fig. 15. The theoretical backgrounds of the secondary anodic electrolysis of anodized

should be taken into account only in secondary anodic electrolysis in acidic baths, but attention should be paid to ''chemical dissolution" when anodized aluminum is immersed in electrolytic baths

.I

..

as ivell as during all secondary electrolysis.

When anodized aluminum undergoes
1

secondary anodic electrolysis in neutral baths, the pore filling phenomenii and

Fig.15 "Chemical dissolution" and "field assisted dissolution"

15
381

aluminum explained in this section are summarized in the left column of Table 1. 2H+ + 2e -> H2

..... ( 5 )

5.

Theoretical Compared with

Background anodic

of

The cathodic reduction reaction of H+ ions which occurs on metal plates such as platinum is a simple electrochemical reaction as shown in Fig. 16 (A), but that taking place within the pores of anodized aluminum, as shown in Fig. 16 (B)and (C), is not simple. The first problem lies in surfaces of anodized whether H+ ions are cathodically reduced on the barrier aluminum or they undergo ionic conduction through the barrier layers and cathodically reduced in the interface between the
I

S e c o n d a r y C a t h o d i c Electrolysis electrolysis explained in the preceding Section, the number of papers regarding the basic researches of the cathodic and

AC

electrolysis of anodized aluminum itre so small that there exist few famous theories. On performing the secondary cathodic electrolysis of anodized aluminum, the understanding of the following items is important:They are (1)two hypotheses on the cathodic reduction of H+ ions, (2)two cathodic reactions taking 1)lilce in sulfuric acid baths, (3)the alkalification of solutions contained within the pores of anodized aluminum due to the cathodic reactions, (4)the deposition of metals and formation of metal hydroxides in metallic salt baths due to the cathodic reactions, (5)difference between the destruction of barrier layers and spalling of anodized aluminum, iind (6)the effect of the thickness of anodized aluminum on the cathodic reactions. The cathodic reduction reaction of H+ ions is the simplest electrochemical reaction in the field of electrochemistry, and ciin he written by the Formulil ( 5 ) .

Fig.16 Cathodic reduction of H+ ions and formation of AI(OH3)

barrier confirm

layers

and

aluminum of

metal.

Unfortunately, there is no way at present to the adequacy above two hypotheses. The second problem is the fact that the impedance of the barrier layer of anodized aluminum changes remarkably. Figure 17 shows the voltage-time curves

16

382

when

l o p

anodized to

aluminum

is

barrier layer surfaces are not always fast. The fourth problem concerns the formation of aluminum hydroxide colloid within the pores of anodized aluminum as shown in Fig. 16 (D). The pores of anodized aluminum immersed in the sulfuric acid bath contains , ' H this anodized OH- and AI3+ ions. If aluminum undergoes

subjected

secondary

cathodic

electrolysis in 0.01 -mol/l H2SO4 bath at 2.5 to - 0.25 A/dm2. Cathodic voltage

secondary cathodic electrolysis, H+ ions become H2 gas, making thereby the insides of anodized aluminum pore alkaline. As a Fig.17 Cathodic electrolysis of anodized result, AI3+ and OH- ions existing in the pores of anodized aluminum cause a neutralization reaction, leading t o the formation of colloidal AI(OH)3. ranges from minus several 10V to minus 1OOV. In addition, over voltage in the cathodic reduction of H+ ions on the metill plate is minus several V. In the cathodic reduction of H' ions within the pores of anodized aluminum, cathodic voltage is extremely high, and this arises from the high impedance of the barrier layers of anodized aluminum. The third problem relates to the diffusion of H+ ions on the surfaces of the barrier layers at the pore bottoms of anodized aluminum. plate, H' In the citthodic reduction of H+ ions on the metal ions in the bulk solution diffuse fast on the surface of the cathode; however, in the case of the anodic aluminum electrode with its pore size and length being 1SOA and l o p respectively, the diffusion
of H+ ions on and their supply to the

aluminum in 0.01 moUl H2SO4 bath at variou current densities

Further,

the continuation of the cathodic reaction changes the colloid layer of AI(OH)3 into i1n electrically resistant gel layer. The increase in cathodic voltage in Fig. 17 partly stems from the formation of the gel layer consisting of aluminum hydroxide. The fifth problem is the destruction of the barrier layers and spalling of anodized aluminum due to the cathodic reaction. As shown in Fig. 17, cathodic voltage reaches a maximum, and then drops because of the destruction of oxide films and occurrence of spalling. The elucidation of the mechanism of these phenomena is still in the hypothetical stage.
As to the cathodic reduction reactions of

anodized aluminum in the sulfuric acid baths, the cathodic reaction of H+ ions shown in Formula ( 5 ) illone has been

17

383

discussed in this Section, but there exists another reaction; it is the cathodic reduction reaction o f dissolved oxygen in electrolytic baths, and can be represented by Chemical Formula (6). 0 2 + 4 H + + 4 e -> 2 H 2 0

when l O p n thick anodized aluminum was subjected to secondary cathodic electrolysis in 1.0- and 0.01- mol/l H2SO4 baths. In both cases current density was
0.5 A/dm2.

In 0.01- mol/l H2SO4 bath,

cathodic voltage reaches -9OV, followed by

.....(6)

rapid decrease. Many spotty peelings with about I-mm diameter were observed on the surface of anodized aluminum. The peeling of the oxide film is called "spnlling". The generation of spalling is explnined in the Brace's book

The above cathodic reaction does not generate hydrogen gas, and takes place at higher cathodic voltage than that of the cathodic reaction 2H+ + 2e -> H2. Accordingly in the cathodic electrolysis of anodized aluminum shown in Fig. 17, the cathodic reactions of ( 5 ) and (6) take place simultaneously. When anodized aluminum undergoes secondary spalling of cathodic anodized electrolysis, aluminum the occur. destruction of the barrier layers and Figure 18 shows the voltage-time curves,

"ANODIC COATING

DEFECTStf6). However, when anodized

aluminum underwent secondary cathodic electrolysis in 1.0- moM H2SO4 bath, resultant cathodic voltage was about -5V, and no spnlling of the oxide films was observed. The observation of this anodized aluminum with an electron microscope revealed the destruction of the barrier. layers of about 1 O O p n from the results given in Fig. 18, it was found 'that the secondary cathodic electrolysis of anodized aluminum sometimes causes spalling, and sometimes the fine destruction of the barrier layers. The fine destruction of the barrier layers may arise from the concentration of cathodic current to flaws

or from hydrogen gas bubbles cathodically

reduced in the interface between the barrier layers of anodized aluminum and Fig.18 Cathodic electrolysis in 0.01 M &
1.0 M H2SO4 bath

aluminum metal. In the case of spalling, on the other hand, the size of a peeled oxide

film is about 1 mm in diameter, so that the

18

384

mechanism of spatting differs from that of fine peeling. This can be understood from the difference in cathodic voltage shown in Fig. 18. Spalling is considered not to occur in irccordance with the cathodic reaction 2H+ + 2e -> H2, hut to occur in accordance with the cathodic reaction 0 2 + 4H+ +4e higher cathodic voltage. molecules in the

anodized aluminum. The cations such as AI3+ and Mg2+ are not reduced to metals by cathodic electrolysis in aqueous solutions. This is the reason why aluminum and magnesium a r e produced by molten salt electrolysis. aluminum the form The cations AI3+ and hydroxides such as Mg2+ existing in the pores of anodized AI(OH)3 and Mg(OH)2 within the pores by cathodic electrolysis

>2H20. Spalling, therefore, takes place at Since the 0 2 layers are barrier

of

anodized

consumed by the cathodic reaction 0 2

aluminum.

Since these metal hydroxides

4H+ +2e ->2H20, anodized aluminum miry peel off in a spotty state. Moreover, if the cations such as Na+, K+ and NH4+ coexist in electrolytic baths, spiilling takes place more easily, hut the reason in unknown. The results of experiments shown in Fig.
18 endorse the empiriciil filct thiit spiilling

a r e electrically resistant, they tend to decrease cathodic current during cathodic electrolysis. Three kinds of anodized aluminum with the thickness of 2, 10 and 20pm unclerncnt cathodic electrolysis under the same conditions, but the Stiites of ciIthotlic electrolysis varied with film thickness. I n other words, the secondary electrolysis of iinodized irluminum is affected not only by the conditions of liquid phases hut iilso by those of solid phases. The reason is that when iinodized aluminum is thin, the supply of H+ ions from hulk solutions is fast despite the decrciise in H+ ions within the pores of nnodizetl irluminum due to the cathodic reaction, and that thereby the solutions within the pores do not become iilkdine. When modized aluminum is thick. however, the supply of H+ ions from the bulk solutions is not fast, so that the solutions within the pores of anodized iiluminum become locally alkiilinc. In

is ciis\. to occur in the weakly acidic nickel bath but difficult in the strongly acidic tin bath. The secondiiry ciithotlic clcctrolysis of iinodized aluminum in the aqueous solutions of metallic salts leiids to the deposition of the metals in the pores of iinodized irluminum, resulting thereby in coloring of irnodized iiluminum. This technique is ciilled the cathodic electrolytic coloring method or DC electrolytic coloring method, iind has been industrially used since 20 years before. However, the secondiiry cathodic electrolysis of anodized aluminum in the aqueous solutions of metallic salts
iilSO

forms metal hydroxides in the pores of

19

385

addition, in secondary anodic electrolysis and secondary AC electrolysis, the thickness of anodized aluminum affects electrochemical reactions. The explanations given to secondary cathodic electrolysis in Section 5 can be summarized as shown in the middle column of Table 1. Similar to secondary anodic electrolysis shown in Table 1, in the secondary cathodic electrolysis of anodized aluminum, different electrolytic conditions result
in different

decreases and the case where they do not decrease, (5)difference in film structures and film compositions between oxide films obtained by AC electrolysis and those by DC electrolysis, (6)formation of colloid and gel layers, (7)AC current recovery phenomena, and @)impedance equivalent circuits for AC electrolysis. If sine-wave AC voltage is applied to anodized aluminum in electrolytic baths, three kinds of alternating current wave forms, depending on the differences in pHs and bath compositions, are observed on the oscilloscope as shown in Fig. 19. The application of low AC voltage to anodized aluminum often leads to the current wave form shown in Fig. 19 (A). Although a phase appears between AC voltage a n d .

states of cathodic

reactions.

6.

Theoretical Background Secondary AC Electrolysis

of

Upon performing the secondary AC electrolysis of ilnodized itluminum, the understanding on the following items is important: (1)tlifference between the case where no electrochemical reaction takes place while AC is flowing and the case where it takes place; difference between "Faradic current" and "non-Faradic current", (2)tlistinction between "the Case where cathodic reactions alone take place" and "the case where both the anodic and ciithodic reactions take place", (3)distinction between the case where porous oxide films are formed nnd the CilSe where they a r e not formed, (4)distinction between the case where either anodic nor cathodic peak current

Fig.19

Current

wave

forms

by

AC

electrolysis of anodized aluminum

20

current, t h e current wave form is also sinusoidal in this case. This sine-wave current is charged and discharged by oxide films, and is non-Faradic. This means that although sine-wave A C voltage is applied to anodized aluminum, no electrochemical reaction takes place on it when the altcrnating current wave form is sinusoidal. In ttnodic and cathodic electrolysis, current
flow

wave non-Faradic current, this alternating distorted current wave form includes The anodic and cathodic peak currents.

anodic peak current in this case is one of Faradic currents caused by the formation of new oxide films and the decomposition of water. anodic Consequently,

when anodized aluminum is subjected to secondary AC electrolysis, the following three phenomena can be clearly judged by the observation of alternate current wave forms with the oscilloscope : (1) whether o r not ,electrochemical reactions are taking place, (2) whether cathodic reactions alone or combined cathodic and anodic reactions are occurring, and (3) whether o r not new oxide films are being formed. For measuring alternate current wave forms, the Lissajours' figure and differential Lissajous' figure are also available. These . alternate current measurement methods :ire shown in Fig. 20.

causes

electrochemical
in

reactions electrolysis,

without

fail, but

AC

alternating current flowing through the systems of electrolysis docs not always cause electrochemical reactions. The electrolytic current of this kind is called "non-Faradic current" meaning "current which does not always accompany On the other The aluminum electrochemical reactions". electrochemical electrolysis of reactions. anodized

hand, "Faradic current" accompanies the

AC
in

\ve:iMy acidic electrolytic baths results in the alternate current have form shown in Fig. 19 (B). This current wave form consists of sine-wave non-Fradic current and cathodic peak current, which serves the cathodic reduction of hydrogen ions
and metal ions.

I
SCOPE

: SYNCHROSCOPE
( ~ Ollferrniiri 1 currant wave

Cathodic peak current, serving

SCOPE
( b l Lissajou's ligurr
(0)

therefore, is Faradic (current

electrochemical reactions). When anodized aluminum undergoes AC electrolysis in strongly acidic baths, a It ern at i n g distorted current wave form shown in Fig. 19 (C) is observed on the oscilloscope. Besides sinecurrent

Oillereiiol Lirsajour' liguro

Fig.20 Meagurment methods of alternating

21

387

Oxide films formed hy anodic peak current as shown in Fig. 19 (C) are called
"AC anodized oxide films", and have

different properties from those of anodized aluminum formed by ordinary

DC

electrolysis; namely, the pore sizes of AC oxide films a r e small, and the number of pores per unit area is great. films sulfide. often contain sulfur,
AC oxide

so

they

sometimes give off the smell of hydrogen Therefore, if normal anodized Fig.21 Equivalent circuits
of
AC

aluminum is prepared in a sulfuric acid bath by DC electrolysis and then followed by secondary AC electrolysis, then "AC oxide films" are formed under "DC oxide films". The appeariince of the double-lapoxide films is opaque, and they are colored green when coloring in they the undergo electrolytic copper bath. This

electrolysis of anodized aluminum were very complicated. However, the

utilization of an analog circuit simulator used recently in the field of the electronic engineering enables the calculation o f the impedance equivalent circuits to be performed easily. Figure 22 shows the

electrolytic green coloring technique has already got a patent.') Since eilrly times AC electrolysis hns been studied by using impedance equivalent circuits, and this research method is called "Faraday Impedance Method". Figure 21 gives the impedance equivalent circuits for each current wave form shown in Fig. 19.

results of calculations authors conducted on

Ventura8) studied electrolytic coloring re;ictions by using the Faraday impedance method, and the results were presented in

SUR/FIN '94.
Although the impedance circuits were assumed for AC electrolytic reactions, the calculations for these impedance circuits Fig.22 Deformed wave forms of AC electrolytic coloring by analog circuit

simul at o r

22
388

thc impedance equivalent circuits for

current disappears after several second (the peak current at t2 in Fig. 23 (B)). This Pact indicates the formation of thick barrier layer on anodized aluminum due to anodic voltage. After the completion of thick barrier formation, anodic peak current stopped flowing. In the case of Fig. 23 (B), cathodic peak current also continues to decrease with AC electrolyzing time, and finally disappears. anodized aluminum The reason undergoes why AC cathodic peak current decreases when electrolytic coloring in the nickel bath is that nickel is deposited in the pores of anodized aluminum and that sol - gel layers of itluminum hydroxide itrc also formed in the pores. The mechanism of these reactions is del)ictcd in Fig. 24'O). In the

electrolytic coloring by using the analog circuit simulatorg) I'P Spice". When anodized aluminum undergoes AC electrolysis, A C current wave form sometimes changes with electrolyzing time, but sometimes does not,as shown in Fig.23. Figure 23 (A) showns the A C current wave form when anodized aluminum is subjected to AC electrolysis in 1.0-molh H2SO4 bath.

FIg.23

Changes of current wave forms

.-.,
fAl

with the lapse of electrolyzing time

The AC current wave form does not change even if electrolyzing time is made longer. This means that the formation of AC anodized aluminum and the under given conditions. cathodic reduction reaction of H+ ions continue Figure 23 (B) AC electrolytic coloring of anodized :tluminum in the tin bath, decrease in cathodic peak current with electrolyzing time is slow as shown in Fig. 23 (C). This is because the strongly acidic tin bath makes difficult the formation of the gel layer of shows the change in AC current wave form when anodized aluminum is subjected to AC electrolytic coloring in a nickel bath. Although in the early stage of AC electrolysis both anodic and cathodic peak currents itre observed, the anodic peak Fig.24 coloring Formation of AI(OH)3 gel in the pores of anodized aluminum by electrolytic

23
389

aluminum hydroxide shown in Fig. 24. When the p H value of the tin bath is low, both anodic and cathodic peak currents are sometimes observed in the AC current wave form during electrolytic coloring. In this case, the cathodic reduction reaction of tin proceeds simultaneously with the formation of AC anodized aluminum in the tin bath. As explained in Section 4, Murphy found that anodic current did not flow for some time if anodic voltage is decreased while aluminum is being anodically electrolyzed. He named this the "current recovery phenomena" (See Fig. 13) not the current recovery The authors phenomena made a series of experiments on whether or :ipl)ear when low AC yoltage (AC JV) is applied to anodized aluminum. The results are depicted in Fig. 25. A C current did not

low immediately after applying 4-V AC voltage to anodized aluminum. After 30 sec. smaller sine- wave AC current began to flow, followed by greater alternating distorted current after 2 min. Thereafter, the value of alternating current was constant. Like the current recovery phenomena found by Murphy, the existence of alternating current recovery phenomena was confirmed. The phenomena made the barrier layers of anodized aluminum thin. If this anodized aluminum undergoes AC electrolytic coloring in the tin bath, then it colors into blue, green, red etc.

multi-

color electrolytic coloring. The reason is that since the barrier layers of anodized aluminum become thin, tin was uniformly deposited within its pores. This multi-color electrolytic coloring technique has been made public as Benitez's patent1 l). When, DC 6 or 5V is applied to anodize aluminum instead of AC 4V, no ;inodic current

recovery was observed even after 30 min. This means that to make the barrier layers of anodized aluminum thin by using the current recovery method, application of low AC voltage is better than that of low anodic voltage. However, the reason why the application of low AC voltage is better than that of low anodic voltage for shortening unknown. The contents
of

In *..TIME

current

recovery the

time

is

discussions

Fig.25 Recovery of alternating current

described in Scction 6 :ire summarized in

24

390

the right column of Table 1. in the case of secondary

Like in

backgrounds of the secondiiry electrolysis

secondary anodic and cathodic electrolyses,

of anodized aluminum explirinetf in this

paper. References
1)

AC electrolysis,

the different electrolyzing conditions result in the different phenomena, which take
place on the different grounds. The means

D.

A.

Vermilyea;

Journal

of

for inyestigating these differences is the me;tsurement of alternating current wave forms by the oscilloscope. The me;rsurement of current with an AC meter can not clarify the rezrction mechanism of A C electrolysis.

Electrochemical
(1963).

Society, vol.1 IO,

p250

2) A. Dekker, A. Middellhack; Journal of Electrochemical

(1970).

Society, vol.117,

p440

3) B. M. Baizuldin; Metal Finishing, 1127, December (1993).

4) K. Kaminaga, T. Sato; Proceedings of

7. Conclusions
'The anodic electrolysis of aluminum hiis
been performed for iibout 70 yenrs; accordingly, miiny themes have been studied, ;rncl thereby se\rerirl import:int theories hwe been m:ide public. On the other hand, I);isic researches regirrtling thc seconclary scctjndiir! the cathodic electrolysis itnd
.A<' elect rolysis of ;inotlizcd

SUIUFIN '95, Session E, plX9 (1994).

5)

J.

F.

Murphy;

Proceedings

of

International

Symposium on Anodizing

(Aluminium Federation, UK), p3 (1967).

6) A. W. Brace; "Anodic Coirting Defects

--- Their Couses and

( 1 992).

Curc"

(book),

Technicopy Books, Stonehouse, Ghs., UK 7) Jiipanesc open patent H3-207895 (1991).

8) X. A. Ventura; Proceedings of SUWFIN
'95, Session H, 11363 (1994).

irluininum itre small i n number. Ho~vever, electrolytic coloring and electrotleposition coitting methods, both of which are rcliitivdy new surface finishing tecliniques, htrvc been carried out hy the second:tr> nluminum. coloring tertiary Therefore, underst:rntl electrolysis method, or it
in

9) P. W. Tuinenga; "SPICE - A Guide to Circuit Simulation and Aniilysis Using 'Spice

(1988).
10) T. Sitto; Plating and Surfiicc Finishing,
"

of is

i\nodized
;i

(book), Prenticc Hall, SJ. USA

The multi-color electrolytic

which

hot

tecllnologiciil topic today, has :idoptecl quaternary is very tlcpth the electrolysis. important to theoretic:il

~ 1 . 7 8 M;rrch, , p70 (1991)

1 1 ) European patent 0413589A1 (1990).

25
391