FAST ANODIZING OF ALUMINUM PISTON HEADS

8-F *
/

b y JS. Safrany, Pechiney CRV, Voreppe, France

and M. Santarini, ALUMiNlUM Pechiney, Voreppe, France

Abstract
Hard anodizing of aluminum piston heads
for internal combustion engines Is usually
performed by immersion, with a time ran-
ging from 40 to 50 minutes. This paper wiii
present a new process, based on specially
adapted hydrodynamics of the electrolyte,
applying electrolysis parameter values out-
side the usual range and which greatly re-
duce the treatment time. In addition t o ap-
plications t o other components, it has been
tested with Industrial partners on thermal
fatigue test pieces and on pistons, with
and without a precombustion chamber.The
influence of anodizing parameters (pre-
treatment, electrolyte temperature, current
density, bath composition) will be discus-
sed in relationship with the practical proper-
ties of the coating layer such as thickness
hardness and thermal fatigue resistance.
Introduction
Among the 37 million passenger cars and 14
million trucks manufactured in the world in 1994,
a substantial part is equipped with diesel engines
(23 YOof passenger cars in Europe, 50 Yoin France).
Hard anodizing and its limits
PrinciDle
Hardcoat anodizing, which finds many applications in
various industrial fields, provides a thick, abrasion-
resistant oxide film on the aluminum surface.
Comparedwith standard anodic layers, hard films are
obtained in specific conditions :
- lower temperature : between 0 and 10 "C (32 to
50 OF) against 20 to 25 "C (70to 75 OF),
- higher current densities : between 2 and 3.5 Ndm2
(19 to 33 Nft2)against 1 to 1.2 Ndm2 (9 to 11 A/ft2),
- special electrolytes, usually based on sulfuric acid.
However, the growth mechanism of the oxide layer is
quite similar to classical anodic films (Figure 1) :
- initially, a barrier layer is formed when the current is
applied,
- an evolution to a porous and hexagonal structure
then occurs with competition between the oxide
formation by the current and its chemical dissolu-
tion by the electrolyte.
I formation of the pores on
the barrier laver surface initiation of the cells

The proportion is particularly high with the trucks

(80 Yoin France for example).
Compared with the gas engine, the piston of the
diesel car is submitted to a higher working tempera-
ture, between 250 and 350 OC (480 and 660 OF),
which is going to become higher, due to the increa-
sing power developed by engines. The aluminum
piston, generally in cast alloy AI Si 12 Cu Ni Mg,
I growth of the hexagonal cells

sustains important sollicitations in terms of thermal

fatigue. For many years, the solution to minimize the
effect of temperature has been to build a thick oxide
layer on the piston head by hardcoat anodizing. Due
to the low thermal conductivity of alumina (30 times
less than the metal conductivity) this layer acts as a
thermal barrier during the piston life. The process
described in this paper enables the obtention of Figure 7 :growth mechanism of a porous oxide layer
such layers with operating times significantly shor-
ther than with classical treatments. The oxide structure itself will depend on the opera-
ting conditions. In particular, the pore-wall thickness
will increase with the voltage.
269
1
 In the case of hard anodizing, the low temperature of
the electrolyte reduces chemical dissolution of the
oxide. Coupled with a strong agitation it removes the
heat produced by the electric current in the bottom
of the pore (Joule's effect) and allows the use of high
current densities. The resulting high voltage involves
the formation of a more compact structure, a thicker,
harder and more abrasion-resistant layer.
Moreover, hard anodizing is less sensitive to alloy
composition. The reason is the lower dissolution rate
of intermetallic compounds which usually give some
porosity in the oxides formed at room temperature.
I ~imifsm r d A nodizing
The use of high current densities accelerates oxide
formation. However, the growth of the film will in-
crease the voltage during the anodizing operation
(Figure 2).
time
+ This system does not require a piston masking ope-
Figure 2 :Voltage vs time for Hard Anodizing
Icounter-electrode & 9
11 - .+ I-, ------
1
Figure 3 :fast Anodizing process
270
There are two limits :
- the power supply capacity,
- the "burning" phenomenon.
The latter is due to a local heating in the pore, invol-
ving a rapid chemical dissolution of the oxide. The
current lines distribution is then completely modified,
with, as a consequence, a complete stop of the ano-
dizing process.
The control of the agitation plays a major role but,
when the geometry and the operating conditons are
fixed, there is a limit for the current density and the
anodizing time.
Concerning the treatment of aluminum piston head,
anodic oxidation is usually performed by an immersion
of 40-50 minutes for oxide layers 60 to 90 pm thick.
That is why we developed a specific process where
the aim was to retain the same properties for the oxide
film while significantly reducing the operating time.
Description of the process - Characterization
of the samples
General orincble
The process, as shown in Figure 3, is based on a con-
centric circulation of the electrolyte on the piston sur-
face, allowing quick removal of the heat produced by
the treatment.
Electrolyte circulation is performed by a centrifugal
pump. The acid is injected through a counter-electro-
de specially designed for that purpose. The jet strikes
perpendicularly the piston head, then is recycled into
the tank by a curved-shape baffle. A cooling system
is used to maintain the electrolyte at low temperature.
ration prior to anodizing treatment.
piston
,
.- AI
&- Hardness : microhardness measurements have
Several sets of samples have been tested on this pilot been performed on cross-sections in order to avoid
device : any influence of the substrate. Micro-indentations
- thermal fatigue test pieces, were conducted with a KNOOP diamond tool under a
- pistons with and without a precombustionchamber. load of 10 g during 15 seconds (Figure 5)
(Figure 4)

Operation

4 *
diameter = 45mm (1.77 in)

Piston
\

i
\
J

1I3 c

anodic film chamber

\
Figure 5 :Micro-indentation with a Knoop diamond
Figure 4 :Example of samples tool

Each type of sample needed a specific setting in order Thermal fatigue : this property has been controlled
to obtain a uniform thickness of the coating, particularly by a piston manufacturer, with following conditions
for pistons with a deep combustion chamber. for one thermal cycle :
However, each setting can easily be modified simply - temperature step from 20 to 350 "C (70 to 660 O F )
by changing the counter-electrode configuration. in 15 seconds,
- air cooling during 15 seconds,
Characterization of the samDles - water cooling during 15 seconds,
Three properties have been studied : the oxide thick- - air drying during 15 seconds.
ness and hardness and the resistance of the piston to Trials have been achieved during 6 000 cycles maxi-
thermal fatigue. mum.
Thickness : the oxide thickness has been control-
led by Eddy current measurements. However, for Results and discussion
non-flat parts of the piston, cross sections have been
made followed by Scanning Electron Microscopy Optimization of the process has been performed on
observations. It should be pointed out that measu- thermal fatigue pieces. Initially, the following goals
rement of voltage versus time allows a good control had to be achieved :
of the oxide thickness as well as the detection of - minimal thickness of 60 pm,
burning phenomenon. - microhardness of 400 50 HV
_+

271
3
 ..
eo-f
When mixed with sulfuric acid, oxalic acid is said to 400
increase film hardness as well as coating abrasion-
resistance '. Figure 6 clearly shows the result of
an oxalic acid addition to the sulfuric acid solution on 300

on the loss of thickness as a result of abrasive wear '.

200

100

0
A 0

/
x / a
Figure 7 :Micro-hardness of oxide layers obtained in
sulfuric acid 180 g/l (A) and sulfuric acid 180 g/l +
oxalic acid 15 g/I(B) (temperature c 5 "C,current

'IL/ A / density 50 Ndm2)

Influence of the electrolytic temperature

Two temperature conditions were tested :
.A/$ . 1 OC<t<2OC(34"F<t<36OF)
/ O
. 4°C<t<50C(390F<t<41OF)
with a sulfuric-oxalic acid electrolyte at 50 Ndm2.
-- No particular effect has been detected in this range
100 zoo 300 coo S O ~
Humber of double movements of temperature on the oxide microhardness. More-
over, we had a strong dispersion of experimental
values, probably due to the high current density as
Thicknesr reduction Lrm) Number of double movements
is explained in the following section.
x --170g/l
170 g/l
HISO,
H,SO, + 5 g/l oxalic acid
Oxide thickness was correct in both cases (> 60 pm).
= 170 gfi H, SO, + 1 0 g/l oxalic acid
0 = 170 g/l H, SO, + 15 g/1 oxalic acid jnfluence of current densitv
Hard anodizing is usually conducted at constant cur-
rent density. The oxidation time will depend on the
Figure 6 :Thickness reduction as a result of abrasive final voltage, fixed here at 90-110 V.
wear in the abrasive wheel test with coatings produced The samples were treated in the following conditions :
in sulfuric acid electrolytes (24 OC,1.5 Ndm2, 20 pm) - electrolyte : sulfuric + oxalic acids
with and without oxalic acid additions - temperature : 2 OC < t < 5 "C (36 OF < t < 41 OF)
- current density : between 20 and 50 Ndm2
Two types of bath have been tested : (between 186 and 465 Nft2)
- sulfuric acid 180 g/l Duration of the anodizing process was calculated to
- sulfuric acid 180 g/l + oxalic acid 15 g/l give an oxide thickness of 55-65 pm.

Figure 7 shows that the oxalic acid gives a significant in- Figure 8 shows that the higher the current density,
crease of the oxide microhardness, but is still far from the lower the microhardness. This can be explained
the objective (400 HV). On the other hand, the thick- as follows : higher current densities induce more
ness was quite uniform in both cases (60 to 70 pm). intense heating in the bottom of the oxide pores.

272 A
Increased chemical dissolution of the pore walls occurs,
leading to a higher overall porosity of the oxide and
here resultingto a lower hardness of the coating. The
growth of the oxide at higher speed and temperature
will probably change its structure as well.
500
- the oxide layer thickness varies from 60 to 80 pm,
- silicon precipitates are included in the oxide, with
a mean size of 10 pm,
- some micro-cracks are present on the oxide surface
but they only affect the external part of the layer.
No structural defect has been detected which could
prevent the thermal barrier effect of the layer.

400
z
n
>
300
m
0
C
?
;
?
*0°

-
E 100

0
19 23 50
current denslty (Aldm2)

Figure 8 :microhardness vs current density electro-

I
lyte :sulfuric acid (180 911) + oxalic acid (15 @I),
temperature :- 2 "C c t c 0 "C, oxide mean thickness : Figure 9 :Cross-section of the oxide layer
55-60 pm

For a lower current density (19 Ndm2 - 175 A/ft2),

a microhardness of 450 HV is reached, fulfilling the
objective.

ORtimization of the oDeratina conditions

To make the process profitable, a compromise had to
be found between mechanical properties of oxide
and anodizing time. That is why we eventually chose
to test the thermal fatigue of samples treated with
following operating conditions :
- electrolyte composition : sulfuric acid (180 g/I) +
oxalic acid (15 s/)
- bath temperature : 2 to 5 "C (28 to 41 O F )
- current density : 22 Ndm2 (205 Mt2)
- treating time : 6 to 7 min figure 10 :Surface of the oxide layer
After 5 000 cycles, no defect was detected on the
thermal fatigue pieces. After 6 000 cycles, cracks Trials on pistons
depth was not exceeding 2 mm which was accep- Once the process operating conditions had been
table according to our industrial partner. defined, some pistons have been treated by fast
anodizing, then tested by the piston manufacturer
Oxide mecphology in terms of thermal fatigue. Results after 6 000
Scanning Electron Microscopy observations of cycles are presented in Table 1.
cross-sections (Figure 9) and of the piston head
surface (Figure 10) show that :

273
5
 Simplification of the process due to the lack of piston
Type of Crack length Crack depth masking, etching and desmutting and reduction of the
treatment "(1 (") anodizing time result in a cost reduction for each pis-
ton produced. Moreover, if we consider an existing
Not treated 55 2.4 industrial unit, the production capacity can be increa-
sed. On the other hand, for a new installation with a __
fixed capacity, the area occupied by a production
Industrial standard 9 1.5
unit can be dramatically reduced.
treatment (40 min) ~

References
~

PECHINEY 16 1.35
treatment (7 min) 1. Bharat Bhushan, Gupta B.K., Handbook of Tribo-
logy, 15-34, Mc Graw-Hill Inc. (1991)

Table 1 2. Brace A.W. and Sheasby P.G., The Technology

They clearly show that compared with the classical
treatment the fast anodizing process gives a
higher crack length while the crack depth is slightly
lower. According to the industrial piston manufac-
turer, these differences were not significant and the
overall quality of the coating was good.
Conclusion
A new fast anodizing process for piston heads has
been developed. It has been patented in Europe,
USA and Brazil 5-7.
In less than 7 min (against 40-50 min for the classical
treatment) the piston can be anodized. The resulting
oxide layer properties are as required : microhardness
of 400 k 50 HV, thickness greater than 60 pm, thermal
fatigue similar to the standard process.
of Anodizing Aluminium, 2nd Edition, 129, Tech-
nicopy Ltd (1979)
3. Wernick S. Pinner R. and Sheasby P.G., The Sur-
face Treatment and Finishing of Aluminium and its
Alloys, 5th Edition, Vol 1, 429
4. Gimenez P., Unpublished results
5. Bommier C., Gimenez P., Laslaz G., Pechiney, US
Patent no 5032244
6. Bommier C., Gimenez P., Laslaz G., Pechiney,
European Patent no 0402287
7. Bommier C. Gimenez P. Laslaz G., Pechiney,
Brasilian Patent 9002666

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