J. Am. Ceram. Soc.

, 83 [4] 983 85 (2000)

journal
Production of Functionally Graded Materials from
Electrochemically Modified Carbon Preforms
Ralf Jedamzik, Achim Neubrand, and Juergen Rodel*
Department of Materials Science, Darmstadt University of Technology, 64287 Darmstadt, Germany
of the pore structure of graded polyurethane foams.9 Electrochemical processing is another possible method to avoid sintering
problems: an ungraded electrically conducting preform is produced, and a porosity gradient is introduced via an electrochemical
reaction.10 This process has been used successfully to produce
fully dense tungsten/copper materials with adjustable and predictable gradients.11

A new process based on carbon as a precursor material has

been applied successfully to the production of graded Al2O3/Al
composites. For this purpose, distinct porosity gradients were
introduced into carbon materials via anodic oxidation. The
graded structure of the carbon preforms was replicated using
two subsequent infiltration steps to yield fully dense Al2O3/Al
functionally graded materials with an interpenetrating network microstructure and a continuous variation of metal
content.

II.
I.

Background

In the present work, this electrochemical method was modified

in such a way that nonconducting graded preforms also could be
produced. As a first step, a porosity gradient is introduced into
porous carbon using anodic oxidation. In alkaline solution, carbon
can be oxidized electrochemically, according to the reaction

Introduction

ECENTLY, functionally graded materials (FGMs) have attracted

considerable interest, because of their potential in many
applications where severe operating conditions prevail.1 Ceramic
metal FGMs are particularly attractive for high-temperature applications, because they combine corrosion resistance and toughness.
Several processing methods for such materials have been established, including powder processing, thermal spraying, and infiltration processing; an overview can be found in the work of
Neubrand and Rodel1 or Mortensen and Suresh.2 In many cases,
the gradient forms layer by layer, which results in a stepwise
gradient. However, continuous gradients have an advantage in that
there are no jumps in the material properties and, thus, stress
singularities at interfaces can be avoided completely. Such materials have been produced via centrifugal powder metallurgy3 or via
slip casting with a variable slip composition.4,5 If only a thin
graded interlayer is required and the shape of the gradient is not
very important, continuous gradients can be produced using
diffusion bonding.6 For material combinations with very different
melting points, infiltration of a melt into a porous preform is a
suitable method to produce FGMs with continuous gradients, a
high density, and a high degree of microstructural control. The
main challenge in the infiltration processing of ceramicmetal
FGMs is the production of suitable ceramic preforms with the
desired porosity gradient, minimum closed porosity, and sufficient
mechanical stability.
Methods proposed in the literature to produce such preforms
include sintering of powder compacts with a graded grain size7 and
sintering of graded compacts with various amounts of admixed
short fibers.8 However, the above-mentioned processes often result
in uneven shrinkage and deformation of the preforms during
sintering. Furthermore, the maximum porosity differences achievable are limited, and only stepped porosity gradients are retained.
More recently, a method was presented that is based on replication

C6OH 3 CO2
3 3H2O 4e

(1)

Side reactions include the formation of carbon monoxide, oxygen,

and humic acids.12 Other than oxygen evolution, all these processes lead to the dissolution of carbon and the growth of existing
pores in the coal. A potential gradient develops in the electrolyte
and the electrode material during cell operation, according to
Ohms law. In the simplest case, the current density j is dependent
on the overpotential (the potential difference between the solid
and the electrolyte, minus the equilibrium potential), according to
the Tafel relation:
j j 0 expk

(2)
1

where k is a constant, typically 550 V , depending on the type

of electrode reaction. This observation means that a change of on
the order of 100 mV causes the reaction rate to increase by a factor
of 10. Such potential differences occur in the electrolyte within a
distance of a few millimeters at current densities of a few mA/cm2,
which are easy to realize for the above-mentioned electrode
reaction. As a result, the regions closer to the cathode are oxidized
more rapidly and a porosity gradient develops in the carbon
electrode after prolonged cell operation.
Subsequently, the pores of the graded carbon preform are filled
with submicrometer-sized ceramic particles via infiltration with a
ceramic slurry. After burnout of the carbon, a green body with two
different pore populations is retained: an interparticle porosity in
the nanometer size range, which is eliminated during sintering, and
a graded porosity (which remains after the burnout of carbon) in
the micrometer size range, which prevails after sintering. Therefore, no uneven shrinkage is observed in the subsequent sintering
step, and the resulting graded preform can be infiltrated with a
metal melt. An overview of the process is shown in Fig. 1.

R. H. Dauskardtcontributing editor

III.
Manuscript No. 189570. Received February 10, 1999; approved December 28,
1999.
Supported by the Deutsche Forschungsgemeinschaft (DFG), under Contract No.
Ne599/1.
*Member, American Ceramic Society.

Experimental Procedure

An electrolytic process was used to prepare a carbon preform

with a porosity gradient. For the purpose of electrochemical
gradation, hard coal (Type 97A and Type 97B, Conradty GmbH,
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Communications of the American Ceramic Society

Fig. 1. Schematic representation of the sample-processing principle.

Rothenbach, Germany; see Table I for properties) was used as the

anode of an electrolytic cell and the electrolyte (diluted aqueous
NaOH, Roth KG, Karlsruhe, Germany) was heated to 60C and
pumped through the coal at a rate of 10 mL/min per square
centimeter of outer electrode surface. A detailed description of the
apparatus can be found in previous work that described graded
metals10 and metal/metal composites.11 After anodization, the coal
was washed thoroughly with distilled water and then infiltrated
with a slip that contained 5 vol% of a high-purity alumina powder
(Taimei TM-DAR, mean particle size of 150 nm; Taimei, Tokyo,
Japan), using vacuum filtration. The apparatus used for the
infiltration has been described in an earlier paper.13 The pH of the
slips was adjusted to 10; 1.5 wt% of a surfactant that was based on
carboxylic acid (Dolapix CE64, Zschimmer & Schwarz,
Lahnstein, Germany) was added to promote dispersion of the
alumina and 0.2 g/100 mL of a polyglycol ether (Glydol N109,
Zschimmer & Schwarz) was added to promote wetting of carbon.
The infiltrated coal was dried at a relative humidity of 95% until
a constant weight was attained (after 7 d), and then the sample
was stored at 70C for 1 d. Subsequently, the alumina preform was
presintered at 850C for 1 h in an argon atmosphere to facilitate
handling, and the coal was burned out at 800C for 6 h in air. After
cooling to room temperature, the preforms were sintered at 1450C
for 0.5 h and infiltrated with molten aluminum (99.5% pure) at
1050C during 2 h. An argon-gas pressure of 10 MPa was applied
to promote infiltration of the melt into the alumina preforms. After
cooling at a rate of 15 K/min, the resulting alumina/aluminum
FGMs were ground and polished, and the volume fraction of the
two phases was determined using an image-analysis system
(QUANTIMET, Leica, Wetzlar, Germany).
IV.

Vol. 83, No. 4

mass loss of the carbon anode was observed. Substantially increased oxidation of the carbon itself was achieved at elevated
temperatures. Therefore, the electrolyte was maintained at 60C in
all the experiments that have been reported here. Even under these
conditions, highly graphitized materials still did not show high
current yields. However, use of a hard coal (Type 97) that was
composed of a binder and coke particles with a moderate degree of
graphitization made it possible to achieve an appropriate carbon
dissolution and the graded pore structure that was required for this
work.
Complete infiltration of the graded pore space of the coal with
ceramic particles (dispersed in a slip) could be achieved only if the
following conditions were met:
(1) The slurry was fully dispersed.
(2) The size of the particles in the slip was at least 10 times
smaller than the pore size of the coal, as determined via mercury
porosimetry.
(3) The solids loading of the slip was low (10 vol%).
(4) The slip wetted the coal.
(5) The preform was evacuated before slurry infiltration.
(6) The preform was ultrasonicated during the entire infiltration process.
The resulting graded green bodies were sintered after carbon
burnout. No deformation or inhomogeneous shrinkage of the
graded body during sintering was observed. Obviously, the sintering shrinkage of the large pores in the green body that were created
by the carbon burnout was the same as the overall sintering
shrinkage. After the infiltration of molten aluminum, an Al/Al2O3
FGM with an interpenetrating network microstructure was retained. The microstructure of an Al/Al2O3 FGM that was produced
from Type 97B coal is shown in the scanning electron microscopy

Results and Discussion

In contrast to previous gradation experiments with copper and

tungsten preforms,10,11 the electrochemical gradation step required
careful selection of the experimental conditions. Graphite forms
intercalation compounds with many anions upon anodic oxidation
in acidic media. Anodization in aqueous sulfuric, nitric, or hydrochloric acid results in a mass increase of the anode in the early
stages of the electrolysis, in addition to its disintegration, because
of swelling in the later stages. Therefore, these media were deemed
unsuitable for the gradation process. In sodium hydroxide solutions, no such effects were observed; however, at room temperature, the main reaction was oxygen evolution and only a moderate

Table I.

Properties of Conradty Type 97A and Type 97B

Hard Coal
Value

Property

Type 97A

Type 97B

Density
Open porosity
Median pore diameter
Ash content

1.5 g/mL
20%
2.9 m
0.35

1.47 g/mL
21%
5.6 m
0.35

Fig. 2. Micrographs showing graded Al2O3/Al microstructures based on

various hard coals ((a) Type 97B and (b) Type 97A). Dark areas represent
Al2O3, and light areas are aluminum.

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Communications of the American Ceramic Society

(SEM) micrograph in Fig. 2(a). The FGM morphology reflects the

microstructure of the carbon that was used: it has rounded metal
ligaments and a finely structured Al2O3 phase. In the replication
process, the pores of the coal are filled with Al2O3 particles.
Therefore, an FGM that is produced from coal with smaller pores
(Type 97A) will have a smaller-sized ceramic phase (Fig. 2(b)).
Porosity could not be detected in any of the samples, using optical
microscopy or SEM.
Using the Tafel relation (Eq. (2)) and Ohms law, the distribution of the current inside the anode (and, thus, the positiondependent dissolution rate of carbon) can be calculated analytically for simple geometries.10 In the present paper, a refined
numerical model (which also has been described by Neubrand10)
was used to calculate the dissolution rate; this model can use
experimentally determined currentpotential relations and considers the change of pore radius during the dissolution process. The
model shows that the current distribution and, thus, the gradation
profile are controlled by many experimental parameters, such as
the initial porosity, current density, conductivity of the electrolyte
and electrode materials, kinetics of the electrode reaction, and
temperature. A variety of different gradation profiles can be
produced by changing these parameters and the shape of the
electrodes that are used.
An example gradation profile is shown in Fig. 3. A current
potential relation of the Tafel type (Eq. (2)) was used for the
calculations; values of k 49 V1 and j0 2 104 mA/cm2
were used. The current yield of the reaction was set at 160%, as
observed experimentally. The gradation profile was varied by
changing the total current density from 4.4 mA/cm2 for 261 h to
7.2 mA/cm2 for 120 h. Sodium hydroxide (2M) was used as the
electrolyte. Gradients with a larger spatial extension were retained
via reduction of the current density at the expense of increasing the

Fig. 3. Experimental determination of two different graded Al2O3/Al

composites (conditions of () 7.2 mA/cm2, 120 h, and () 4.4 mA/cm2,
261 h). Solid lines represent the theoretical predictions.

985

processing times. The gradient that was produced could be

predicted acceptably by the model. Differences at positions close
to the anode (at x 0) were caused by chemical attack of the seals
in which the electrodes were embedded. This condition allowed a
portion of the cell current to bypass the front layer of the electrode
and remove electrode material at the back side.
V.

Conclusion

The method presented here can be readily applied to produce

different types of functionally graded materials if aluminum is
replaced by other metals (or glasses or polymers) that have melting
points below the sintering temperature of Al2O3. The ceramic
phase can be changed, using different slurries for the first infiltration process. Thus, the method presented here allows one to
produce stepless gradients of 1 cm in the gradient dimension for
a wide range of ceramic composites.
Acknowledgment
The authors thank Mr. Hofmockel (Conradty GmbH) for kindly supplying the
hard-coal preforms.

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