Biomorphic Cellular Ceramics**

RESEARCH NEWS
By Heino Sieber,* Christiane Hoffmann,
Annette Kaindl, and Peter Greil

BiotemplatingÐa new concept for preparation of ceramic compos-

ite materials with biomorphic microstructures will be described.
Biological carbon preforms (CB-templates) were derived from dif-
ferent wood structures by high-temperature pyrolysis at tempera-
tures between 800 and 1800 C and used as templates for infiltra-
tion with gaseous or liquid Si to form SiC- and SiSiC-ceramics. During high-temperature processing,
the microstructural details of the bioorganic preforms were retained. Cellular ceramic composites with
unidirectional porous morphologies and anisotrophic mechanical properties were obtained. The cellular
composites show low density, but high specific strength and excellent high temperature stability.

1. Introduction
In contrast to engineering materials, biological structures
exhibit a hierarchically built anatomy, developed and opti-
mized in a long-term genetic evolution process. They are
characterized by a complex shape, with structural features
ranging from the micro (cell walls) to the macro scale (skele-
tons). Due to their hierarchically designed composite mor-
phology, biological materials exhibit unique structure-me-
chanical property relationships on a micro as well as on a
macro scale and have become of interest for advanced
processing concepts of engineering materials in the recent
years.[1,2]
Wood is a natural composite and exhibits an anisotropic,
porous morphology with excellent strength at low density,
high stiffness, elasticity, and damage tolerance.[3] The mircos-
tructural features of wood range from mm (growth ring pat-
terns) via mm (tracheidal cell patterns, macro- and microfibril
cell wall textures) down to nm scale (molecular cellulose fiber
and membrane structures of cell walls). The most distinct fea-
ture of the wood structure, however, is the open porous sys-
tem of the tracheidal cells which provide the transportation
path for water in the living wood and yield an uniaxial pore
structure with anisotropic mechanical properties.
The cell walls of wood are formed by biopolymers such as
cellulose, hemicellulose, pectin, and proteins. Several cellu-
lose macromolecules are bundled to fibrils. Lignin serves as a
binder between the cellulose microfibrils and increases the
mechanical strength.[4] Different cell types form the heteroge-
neous tissue of wood. The morphology and the arrangement
of the different cells vary between deciduous and coniferous
wood. Coniferous wood has a very uniform structure
(Fig. 1a), it consists of 90±95 % tracheids, which are long and
slender cells tapered at the ends. The size of the tracheids (di-
ameter up to 50 mm, length up to few mm) depends on the
growth conditions, such as changing temperatures or water
supply. Deciduous wood is less homogeneous (Fig. 1b).
Tracheary elements (diameter up to 500 mm, length less than
1 mm) form long tubes of a few cm. Tracheids and tracheary
elements are oriented in the direction of the trunk axis. They
form the transportation paths for water and minerals within
the living tree. Cells arranged in radial direction (rays) and
pores in the cell walls create a three-dimensional pore net-
work for transportation.
The tracheary and tracheid cells in wood form directed
pore structures at the micrometer level, which can not be pre-
pared easily by technical (foam, extrusion or substitution)
processing. Such microstructural morphologies are of interest
for technical applications for example as micro filters in food
processing or catalyst carriers in exhaust gas purification.
However, while in biological growth and mineralization pro-
cesses only very slow material synthesis rates (about mm/h[5])
occur, for technical applications much faster rates have to be
obtained. One processing technology to overcome this time
rate problem is the biotemplating technique, where natural
±
[*] Dr. H. Sieber, C. Hoffmann, A. Kaindl, Prof. P. Greil
University of Erlangen±Nuernberg
Department of Materials Science, Glass and Ceramics
Martensstr. 5, D-91058 Erlangen (Germany)
[**] Financial support from the Volkswagen Foundation under con-
tract I/73 043 is gratefully acknowledged.

ADVANCED ENGINEERING MATERIALS 2000, 2, No. 3 1438-1656/00/0303-0105 $ 17.50+.50/0 105

 Sieber et al./Biomorphic Cellular Ceramics

grown structures are used as bulk

RESEARCH NEWS

a) b)
templates for high-temperature con-
version into technical ceramic and
composite materials. Carbonized
wood can be used directly as a tem-
plate structure to process ceramics
with tailored micro- as well as meso-
porosity. The inherent open porosity
in the natural plant structures is ac-
cessible for gaseous or liquid infiltra- 40 µm 40 µm
tion and subsequent high-tempera-
ture ceramic phase formation. Fig. 1. Scanning electron micrographs (SEM) of pyrolyzed wood: a) beech (deciduous wood), b) pine (coniferous wood).
Processing of ceramic composites Section perpendicular to the stem axis (axial direction).
from biologically derived materials
like wood or organic fibers has recently attained particular in- 2. Processing of Biomorphic Ceramics
terest. In the last years, various biotemplating high-tempera-
ture techniques were developed to convert biological derived 2.1. Pyrolysis of Wood
materials into ceramic and composite materials. Biological
plant materials containing silicon such as rice husk or coconut Different kinds of natural wood (oak, maple, pine, balsa,
shells were annealed in inert atmosphere to yield SiO2 and ebony, and beech) with various fractional densities and po-
SiC whiskers or particles. [6,7]
Further investigations were con- rosity structures were used to produce biomorphic SiC-ce-
[20]
ducted by using biological materials as carbon and/or struc- ramics. The wood specimens were dried (70 C, 15 h) and
tural templates to produce ceramic fibres. Si coated cellulose in a first step pyrolyzed in N2-atmosphere in a carbon heated
[8] [9]
fibers and Si3N4 coated cotton fibers could be converted furnace. A slow heating rate of 1 K/min was applied up to
into SiC fibers by annealing in Ar-atmosphere at 1200± 500 C where the polyaromatic hydrocarbon polymers (cellu-
1600 C. Ohzawa et al. [10,11]
infiltrated paper and cotton wool lose, hemicellulose, lignin) were completely decomposed to
preforms with SiC by pressure-pulsed chemical vapor infil- carbon followed by a higher rate of 5 K/min up to the peak
tration for high-temperature filter applications. Padel and temperature. The specimens were hold at the peak tempera-
Padhi [12,13]
used natural fibers such as sisal, jute and hemp for ture in the range from 800±1800 C for 4 h. The processing
infiltration with AlCl3 and TiCl4 and subsequently transfor- scheme is summarized in Figure 2.
mation into oxidic Al2O3 and TiO2 fibers by annealing in air. The major biopolymeric constituents in wood are cellulose,
Similar, Bohne et al. [14]
infiltrated cellulose fiber with boron hemicellulose, and lignin with some additional macromolecu-
acid (H3BO3) and yielded B4C-fibres by annealing in Ar-at- lar compounds like different kinds of fat, oil, wax, resin su-
mosphere at 1750 C. gar, minerals, alcaloides, etc. as minor constituents. A typical
More recent activities were directed to the question how to composition of softwood is 48 wt.-% cellulose, 19 wt.-%
transform bulk morphologies like hierarchical and cellular hemicellulose, and 30 wt.-% lignin which differs only slightly
structures of wood into inorganic materials with specific from hardwood which is 45 wt.-%, 27 wt.-%, and 22 wt.-%,
functional properties. Ota et al.[15,16] produced biomorphic ce-
ramics by infiltration of charcoal with metal-organic solu-
tions, e.g., TEOS (tetraethyl orthosilicate) or TTiP (titanium
tetra-isopropoxide). After high-temperature pyrolysis the
wood structures were converted into porous SiC or TiO2 ce- Shaping Shaping
ramics. Greil et al.[17] converted different kinds of wood by in-
filtration of pyrolyzed wood preforms with liquid Si into cel-
lular SiSiC composites, similar, Shin and Park[18] used
Wood C-Preform SiC-Ceramic
charcoal for fabrication of biomorphic SiSiC-composites.
In addition to the direct conversion of natural grown plant
structures, preprocessed materials derived from natural fiber
Drying Si-Infiltration
composites like papers and cardboard structures can be used
(70 °C, 15 h) (1600 °C, vac., 4 h)
as structural preforms for conversion into ceramic compo-
liquid → SiSiC
Pyrolysis
sites.[19] After infiltration with preceramic polymers and dif- gaseous → SiC
(800-1800 °C, N2, 4 h)
ferent reactive/inert filler materials, the paper preforms were
pyrolyzed at temperatures of about 1400 C. During process-
ing, the carbon of the paper reacted with the Si-filler and Fig. 2. Processing scheme of manufacturing cellular SiC and SiSiC-ceramics from
formed SiC-based composite material. wood.

106 ADVANCED ENGINEERING MATERIALS 2000, 2, No. 3

Sieber et al./Biomorphic Cellular Ceramics

respectively. The average elemental compo- Table 1. Microstructural characteristics of different kinds of wood after pyrolysis at 1800 C and subsequent

RESEARCH NEWS
Si-melt infiltration at 1600 C (after [17]).
sition of wood is 50 wt.-% C, 43.4 wt.-% O,
6.1 wt.-% H, 0.2 wt.-% N, and 0.3 wt.-%
Wood Balsa Pine Oak Maple Beech Ebony
ash.[21]
Pyrolysis weight loss (wt.-%) 73.5 73.8 70.4 74.9 74.2 64.6
During pyrolysis of the major biopoly-
Pyrolysis Axial 21 23 17 20 22 14
meric wood components, lignin and cellu-
shrinkage (%) radial 22 28 28 30 32 25
lose, in an inert atmosphere, the weight loss
tangential 22 31 33 40 38 30
starts below 200 C. At 600 C a total weight
Density (g/cm3) pyrolyzed 0.06 0.31 0.50 0.51 0.55 0.87
loss of about 80 wt.-% for cellulose and of
Si-infiltrated 2.02 2.22 2.16 2.58 2.57 ±
about 50 wt.-% for lignin is observed. The Porosity (%) pyrolyzed 22/70 21/57 30/40 43/22 42/21 23/20
thermal degradation reaction of the cellulose (open/closed) Si-infiltrated 11/14 11/14 8/5 3/5 3/2 3/±
can be separated in two steps:[22] Si-Content (wt.-%) 67 50 27 23 37 ±
Pyrolysis at low temperatures: Release of
water, that results in ªdehydrocelluloseº, fol-
lowed by the elimination of small molecules like CO and CO2 2.2. Liquid Si Infiltration
above 260 C.
Carbonization at temperatures above 600 C: break down Spontaneous wetting and infiltration of the porous carbon
of the carbon chains in the biopolymer structures and the for- preform occurred when brought into contact with the liquid
mation of graphitic structures (turbostratic carbon). Si. Concurrently the reaction to form b-SiC
During heating of the composite wood, the biopolymer de-
composition yields a final weight loss between 70±80 wt.-%, C(s) + Si(l) ±? b-SiC (1)
depending on the kind and composition of the wood (Ta-
ble 1). While the theoretical carbon content of wood is ap- takes place.
proximately 50 wt.-%, significantly higher weight losses oc- Figure 3 shows the morphology of a pyrolyzed and Si-in-
curred due to evolution of H2O, CO2, and volatile filtrated maple wood (the unreacted Si was etched out with
hydrocarbon species from fragmentation reactions of the HF/HNO3). It can be seen, that the biological features like the
polyaromatic constituents.[23] The thermal decomposition of porous morphologies of the natural grown wood are retained
the polyaromatic biopolymers during the pyrolysis is finished in the SiSiC-ceramic. At the carbon±silicon interface b-SiC
at about 600 C and yields an amorphous carbon structure of grains with a mean particle size of 5 mm are formed.
the CB-template. Further heating up to 1800 C increases the After Si-melt infiltration the pores are filled up with the sil-
amount and size of the graphitic structures in the turbostratic icon melt up to a maximum pore channel diameter of ap-
carbon.[17] proximately 30 mm. Larger pores did not contain residual sili-
Pyrolysis of wood involves an anisotropic shrinkage of con, although the carbon template has completely
approximately 40 % in tangential, 30 % in radial, and 20 % in transformed to b-SiC. The residual Si-content depends on the
axial direction, depending on the composition of the different total porosity of the carbon preforms and the pore channel di-
cells in the tissue and the different orientation of the cellulose
fibers in the cell walls. Different kinds of wood exhibit a wide
range of weight loss depending on the variation of the
cellular and molecular composition (e.g., balsa exhibits a
weight loss of 73.5 wt.-%, pine of 73.8 wt.-%, and ebony of
64.6 wt.-%).
Despite the high weight loss and anisotropic shrinkage of
the wood during the high-temperature pyrolysis, the micro-
structural details of the initial wood structure were trans-
formed with high precision into the carbon preform. After py-
rolysis the open porosity (tracheids and vessels) of the CB-
templates was used for Si-infiltration. The Si-infiltration was
performed by two different processing routes at 1600 C over
a period of 4 h: Infiltration with liquid Si without pressure ac-
20 µm
cording to the conventional processing of SiSiC-materials,[24]
and infiltration with gaseous Si to form highly porous SiC-ce-
ramics. Fig. 3. SEM micrograph of Si-melt infiltrated maple (pyrolysis at 1800 C, Si-etched).

ADVANCED ENGINEERING MATERIALS 2000, 2, No. 3 107


ameter distribution (between 23 wt.-% (maple) and 67 wt.-%
RESEARCH NEWS
(balsa)). It can be removed afterwards by chemical etching to
increase the porosity.
Due to the large tracheidal pores, the final SiSiC-ceramic
contains a residual porosity up to 25 % depending on the in-
itial cellular structure of the wood. Coniferous wood yields
SiSiC-ceramics with a high density, high strength and high
stiffness in axial direction. Deciduous wood exhibits larger
pore structures after Si-melt infiltration and is more interest-
ing for acoustic or heat insulation structures.
2.3. Gaseous Si Infiltration
The reaction of the carbonized wood templates with gas-
eous Si at a temperature of 1600 C result in the formation of
b-SiC grains with a mean particle size of about 5 mm, similar
to the SiC-grains formed by Si-melt infiltration at 1600 C.
However, in contrast to the melt infiltration process, Si-gas-
eous infiltration of the CB-templates yield single phase SiC-
ceramics without residual Si and thus a much higher porosity
(20±50 % open porosity) of the ceramic material, Figure 4. The
resulting material exhibits an unique cellular morphology
with pore diameters of about 30 mm and may be of interest
for micro filter and catalyst carriers applications at high tem-
peratures.
Fig. 4. SEM micrograph of Si-gas infiltrated pine (pyrolysis at 1800 C).
2.4. Macroscopic Properties of Biomorphic Ceramic
After pyrolysis, the carbonized preforms show a multimo-
dal pore size distribution with pore diameters ranging from a
few mm for the initial tracheid cells up to more than 100 mm
for the tracheary elements. Table 1 shows, that the porosity of
the CB-templates is 20±25 % higher than of dried wood. As ex-
pected from the mechanical behavior of wood, the pyrolyzed
carbon preforms exhibit a distinct anisotropy of the mechani-
cal properties. Young's modulus and strength are signifi-
cantly higher in the axial direction compared to perpendicu-
108
Sieber et al./Biomorphic Cellular Ceramics
lar loading orientations.[17] While pyrolyzed ebony (density of
0.82 g/cm3) attains a Young's modulus of 22 GPa and a bend-
ing strength of about 40 MPa, pyrolyzed balsa has a density
of only 0.07 g/cm3 and hence a very low Young's modulus of
2 GPa and a modulus of rupture of 2.5 MPa.
The mechanical properties of the wood derived SiSiC-ce-
ramics (Si-melt infiltrated CB-templates) mainly depend on
porosity microstructure, i.e., anisotropic orientation and di-
ameter of the tracheidal pore structures. The differences be-
tween the growth directions can still be found even though
they are less pronounced compared to the carbon preform
materials. Figure 5 shows the bending strength of wood de-
rived SiSiC-ceramics as a function of density. In contrast to
conventional, isotropic SiSiC-composites derived from pow-
der mixtures,[25] a distinct anisotropy of the mechanical prop-
erties in different loading directions can be found. Strength,
toughness, and Young's modulus in axial direction are signif-
icantly higher than in radial or tangential direction. For exam-
ple, maple with a density of 2.5 g/cm3 (porosity 8 %) exhibits
a strength of only 120 MPa perpendicular but 200 MPa paral-
lel to the axial direction. In contrast, commercially prepared
SiSiC-materials of same porosity exhibits a bending strength
of 150 MPa.[25]
AR&AT
200 TA&TR
pyrolyzed
Bending strength [Mpa]
AR & AT
TA & TR
150
Si-melt infiltrated
AR & AT
100 TA & TR
SiSiC [25]
50
0 20 40 60 8 100
0
Porosity [Vol.%]
Fig. 5. Bending strength of pyrolyzed and Si-melt infiltrated wood structures as a
function of density for two different orientations parallel (AT and AR) and perpendicu-
lar (TA and TR) to the axial direction. For comparison, the fracture strength of com-
mercially available SiSiC material is given [25].
3. Conclusions
Carbon preforms derived from natural grown materials
can serve as template structures for preparation of micro-
structural designed materials by infiltration and chemical re-
action processes. Natural, regenerating materials like wood,
fibers, paper or cardboard structures are available on a com-
mercial scale, less expensive and exhibit excellent forming
abilities.
Novel SiC-based, light-weight, high-temperature ceramics
with uniaxial pore structures and anisotropic mechanical
properties were produced by infiltration of liquid or gaseous
Si into carbonized wood templates. The biodiversity of the
ADVANCED ENGINEERING MATERIALS 2000, 2, No. 3
Sieber et al./Biomorphic Cellular Ceramics
natural grown wood structures offer a large variety of differ-
ent porosity and morphologies microstructures in the formed
ceramics. Depending on the processing conditions, porosity
and strength of the converted SiC-ceramics can be designed.
While the liquid infiltration with reacting Si-melts yield car-
bide/metal composites where most of the residual porosity is
filled up with excessive metal, the reaction with gaseous Si-
infiltrants results in single phase SiC-ceramics with 20±50 %
open porosity.
Anisotropic cellular ceramics could be of interest for tech-
nical applications such as heat insulation structures, sub-
strates, filter and catalyst carriers at high temperatures, ther-
mally and mechanically loaded lightweight structures, as
well as for medical implant structures (e.g., porous materials
for bone-substitution).
± 1961.
[1] Mater. Res. Soc. Symp. Proc. 1992, 255.
[2] H. Okamoto, Mater. Sci. Eng. 1994, C2, 1.
[3] L. J. Gibson, Met. Mater. 1992, 8, 333.
[4] P. W. Lucas, B. W. Darvell, P. K. Lee, T. D. B. Yuen,
M. F. Choong, Philos. Trans. R. Soc. London 1995, B348,
363.
[5] BiomineralizationÐChemical and Biochemical Perspectives
(Eds: S. Mann, J. Webb, R. P. Williams), VCH, Wein-
heim 1989.
[6] R. V. Krishnarao, Y. R. Mahajan, T. J. Kumar, J. Eur. Ce-
ram. Soc. 1998, 18, 147.
[7] A. Selvan, N. G. Nair, P. Singh, J. Mater. Sci. Lett. 1998,
17, 57.
[8] H. Sieber, A. Kaindl, H. Friedrich, P. Greil, Crystallizati-
on of SiC on biological carbon precursors, in Proc. of the
101st Annual Meeting of the American Ceramic Society,
Symposium A: Bioceramics: Materials and Applications
1999, in print.
[9] R. V. Krishnaro, Y. R. Mahajan, J. Mater. Sci. Lett. 1996,
15, 232.
[10] Y. Ohzawa, A. Sadanaka, K. Sugiyama, J. Mater. Sci.
1998, 33, 1211.
______________________
ADVANCED ENGINEERING MATERIALS 2000, 2, No. 3
[11] Y. Ohzawa, H. Hshino, M. Fujikawa, K. Nakane, K. Su-
RESEARCH NEWS
giyama, J. Mater. Sci. 1998, 33, 5259.
[12] M. Patel, B. K. Padhi, J. Mater. Sci. 1990, 25, 1335.
[13] M. Patel, B. K. Padhi, J. Mater. Sci. Lett. 1993, 12, 1234.
[14] Y. Bohne, H.-P. Martin, E. Müller, in Werkstoffwoche
'98, Band VIIÐKeramik, (Ed: J. Heinrich, G. Ziegler, W.
Hermel, H. Riedel), WILEY-VCH, Weinheim 1998,
p. 571.
[15] T. Ota, M. Takahashi, T. Hibi, M. Ozawa, S. Suzuki, Y.
Hikichi, H. Suzuki, J. Am. Ceram. Soc. 1995, 78, 3409.
[16] T. Ota, M. Kobayashi, M. Imaeda, N. Kinoshita, Y. Hiki-
chi, H. Unuma, M. Takahashi, H. Suzuki, Porous Titania
Ceramics prepared by mimicking silicified woods, in Proc. of
the 101st Annual Meeting of the American Ceramic Society,
Symposium A: Bioceramics: Materials and Applications
1999, in print.
[17] P. Greil, T. Lifka, A. Kaindl, J. Eur. Ceram. Soc. 1998, 18,
[18] D.-W. Shin, S. S. Park, J. Am. Ceram. Soc. 1999, 82, 3251.
[19] H. Sieber, D. Schwarze, H. Friedrich, A. Kaindl, P. Greil,
Ceramic lightweight structures from paper derived composi-
tes, in Proc. of the 101st Annual Meeting of the American
Ceramic Society, Symposium N: Innovative Processing
and Synthesis of Ceramics, Glasses and Composites
1999, in print.
[20] A. Kaindl, PhD Thesis, University of Erlangen±Nurem-
berg 1999.
[21] R. Wagenführ, Anatomie des Holzes, 2. Aufl., VEB Fach-
buchverlag, Leipzig 1980.
[22] D. Klemm, B. Philipp, T. Heinze, U. Heinze, W. Wagen-
knecht, Comprehensive Cellulose Chemistry, Vol. I, Wiley-
VCH, Weinheim 1998, p. 107.
[23] F. F. Byrne, H. Marsh, in Porosity in Carbons (Ed: J. W.
Patrick), Edward Arnold, Sevenoaks, UK 1995.
[24] W. B. Hillig, J. Am. Ceram. Soc. 1988, 71, C96.
[25] H. Osada, A. Kanj, S. Katayama, T. Koga, Ceram. Trans.
1993, 31, 243.
109