Volume 10, number 1,2 MATERIALS LETTERS September 1990

Glycine-nitrate combustion synthesis of oxide ceramic powders

L.A. Chick, L.R. Pederson, G.D. Maupin, J.L. Bates, L.E. Thomas and G. J. Exarhos
Pacific Northwest Laboratory, Richland, WA 99352, USA

Received 23 May 1990

A new combustion synthesis method, the glycine-nitrate process, has been used to prepare oxide ceramic powders, including
substituted chromite and manganite powders of high quality. A precursor was prepared by combining glycine with metal nitrates
in their appropriate stoichiometric ratios in an aqueous solution. The precursor was heated to evaporate excess water, yielding a
viscous liquid. Further heating to about 180°C caused the precursor liquid to autoignite. Combustion was rapid and self-sustain-
ing, with flame temperatures ranging from 1100 to 1450°C. The chromite product was compositionally homogeneous with a
specific surface area of 32 mr/g, while the manganite product was composed of two distinct phases with a 23 m2/g surface area
after calcination. When compared to similar compositions made using the amorphous citrate process, glycine-nitrate-produced
powders had greater compositional uniformity, lower residual carbon levels and smaller particle sizes.

1. Introduction were the preferred initial reagents to be used in the

Lanthanum strontium chromite, I_a(Sr)CiQ, and
lanthanum strontium manganite, La(Sr)Mn03, both
having the generalized perovskite structure, are of
considerable technological interest because of their
electrical ,conductivity and catalytic properties. These
materials have been investigated for use in high-tem-
perature furnace electrodes, solid oxide fuel cells,
magnetohydrodynamic reactors, and as catalysts for
the treatment of automobile exhaust.
Currently, the most commonly used method to
prepare substituted chromites and manganites is the
amorphous citrate process, pioneered by Pechini in
1967 [ 11. With various modifications, the amor-
phous citrate process has been utilized to produce a
wide variety of ceramic powders [ 2-81. In this
method, metal ions are complexed in an aqueous so-
lution with a-hydroxycarboxylic acids such as citric
acid. These chelates can undergo polyesterification
when heated with a polyhydroxy alcohol such as eth-
ylene glycol. On removal of the excess solvent, a
transparent solid resin containing the metals in solid
solution is formed. The resin is then decomposed by
heating to remove the organic constituents, leaving
the desired ceramic composition as a residue. Metal
alkoxides, oxides, hydrated oxides, and carbonates
preparation of the solid resin by Pechini. Metal ox-
alates, tartrates, sulphates, nitrates, chlorides, and
acetates were avoided because of potentially low sol-
ubilities of these compounds in either the liquid or
the solid resin, which could lead to phase separation
in the final product. The amorphous citrate process
was modified to include the use of metal nitrates to
prepare the precursor [ 5-71; polyacrylic acid has
been used in place of citric acid to prepare substi-
tuted lanthanum chromites [ 8 1.
For the past two years, the authors have been us-
ing a new combustion synthesis method, termed the
“glycine-nitrate process” (GNP), to synthesize
complex chromites [ 9 1, manganites, zirconates, fer-
rites, and oxide superconductors, among other com-
pounds. Others have used combustion synthesis
methods to prepare a variety of oxide ceramic pow-
ders with good success [ 1O-141, using carboxylate
azides or urea as the complexant/fuel. This paper
describes the new process and discusses the prop-
erties of the chromites and manganites synthesized
by GNP. Contrasting physical properties between the
powders derived from the GNP process and those
obtained from the amorphous citrate technique are
observed. The GNP powders exhibit superior prop-
erties for ceramic processing applications.

6 0167-577x/90/$03.50 0 Elsevier Science Publishers B.V. (North-Holland)

Volume IO, number I,2 MATERIALS LETTERS September 1990

2. Experimental

The glycine/nitrate powder synthesis technique

H
2
N-CH
2
--Cf’ \-.-
Sr2+
0
used in this study consisted of the following steps.
Metal nitrates and glycine, a low molecular weight (a)
amino acid, were dissolved in water. The solution
was then boiled to evaporate excess water. The re-
sulting viscous liquid ignited and underwent
sustaining combustion, producing an ash composed
self- tiH
4-CH2 --C,
No
,I
I

of the oxide product. ‘OH

Reagent-grade metal nitrates and glycine were used. 3+”
(H20J5Cr
Stock solutions at approximately one molar (cation

(H20
basis) concentration were prepared by dissolving the 3+

1
metal nitrates in deionized water. These stock so-
lutions, one for each cation, were analyzed by EDTA
/p
titration [ 15 ] to determine the cation concentration H2N-CH2 -C,
to a precision of better than 0.5%, relative. Based on OH
X
the analyzed cation concentrations, the stock solu-
tions were then mixed by weight at the appropriate
proportions to make the desired compound. Glycine
2 gly/Cr W x=1
was added in granular form.
Combustion was carried out in a hood in 4 II stain- 5 gly/Cr ~~~~-) x=2
less-steel beakers on a hot plate. Approximately 40
ml of the precursor solution (0.02 moles of perov- (b)
skite product) was burned at a time. Combustion of
Fig. 1. Initial stages of glycine-metal complexation in an aqueous
larger quantities should be undertaken with extreme
solution. Complexation can involve either the( a) carboxylate or
caution because of the vigor of the reaction. The hot
(b) amine end of the glycine molecule.
plate was set on “high”, and the solution was simply
allowed to boil until it thickened and ignited. The
beaker was covered with a 230 mesh stainless-steel and alkaline-earth cations are most effectively com-
sieve to contain the ash. plexed by the carboxylic acid group, while many
transition metals are most effectively complexed by
the amine group. Fig. 1 schematically illustrates ex-
3. Results and discussion pected structures at the onset of chelation. For the
substituted lanthanum chromites, the metal nitrate/
3.1. Complexation glycine solutions were boiled until the solutions
reached a honey-like consistency; no evidence of se-
The amino acid, glycine, serves two principal pur- lective precipitation was apparent. The concentrated
poses: first, complexes with metal cations are formed, solutions were homogeneous, with the cations mixed
which increases their solubility and prevents selec- on a molecular scale.
tive precipitation as water is evaporated; and sec-
ond, it serves as fuel for the combustion reaction,
being oxidized by the nitrate ions. The glycine mol-
3.2. Combustion
ecule has a carboxylic acid group at one end and an
amine group at the other end, both of which can par- The metal nitratelglycinelwater solution was con-
ticipate in the complexation of metal ions. This verted to a ceramic powder by thermal evaporation
“zwitterionic” character allows effective complexa- of the water to the point of autoignition of the pre-
tion with metal cations of varying ionic size. Alkali cursor. In fig. 2, the boiling temperature of the so-

l
Volume 10, number 1,2 MATEBIALS LETTERS September 1990

1001
0 20 40 60 60 100
PEFMXNTWATEREVAPORATED

Fig. 2. Boiling temperature as a function of weight fraction of
water evaporated for the glycine-nitrate precursor solution of
La,,76Sr0.2,Cr01.The broken line is an estimate of the last por-
tion of the curve, prior to ignition, which occurs at approxi-
mately 180°C.
Fig. 3. Photograph of a typical glycine-nitrate combustion for
the chromites. Ash particles are seen rising through the combus-
tion plume.

3. The peak flame temperature, about 1450” C, was

lution is given as a function of the weight fraction of obtained at a glycine/nitrate ratio of 0.552. This ra-
water remaining for a mixture of lanthanum nitrate, tio corresponds to combustion reactions which pro-
strontium nitrate, chromium nitrate, and glycine. duce H20, C02, and Nz with no atmospheric oxygen
Glycine was present at a concentration of two moles required. Flame temperatures have not been mea-
per mole metal cation; the target composition of the
final product was La,,7aSro.24CrG~. As the weight
fraction of water dropped below approximately 0.20,
the boiling temperature rose rapidly. During the fi-
nal stages of evaporation, the solution began to swell, 1400.
forming a viscous foam. Spontaneous combustion of
the precursor began at approximately 180” C. Unlike
the “charring” reaction for the Pechini and amor-
phous-citrate processes, the combustion reaction for
the GNP was rapid, self-sustaining, and essentially
complete when the fuel/oxidant ratio was properly
adjusted. A typical bum of 40 ml of the GNP so-
lution was completed within a few seconds. Fig. 3 is
a photograph of a chromite material being burned in
an open dish. The chromite ash can be seen rising in
the flame and settling in the surrounding air.
1606~
Fig. 4 shows flame temperature as a function of 0.3 0.4 0.5 0.6 0.7 0.6 0.9

glycine/nitrate ratio for &&r0.24CrG~. Flame GLYCINE / NITRATE RATIO

temperatures were measured by a two-color optical Fig. 4. Flame temperatures measured by two-color optical py-
pyrometer focused on the glowing ash during com- rometry for the combustion of glycine-nitrate chromite precur-
bustion in an open petri dish, such as shown in fig. sors prepared at various glycine/nitrate ratios.

8
Volume 10, number 1,2 MATERIALS LETTERS September 1990

sured for the manganites, but visual observation m-

dicates these compounds bum at a lower tempera-
ture, about 1100 to 1200” C, when the stoichiometry
is adjusted to yield H20, COz, and NZ.
For the refractory chromite powders, the best
properties were obtained at glycine/nitrate ratios in
the range 0.5 to 0.7, corresponding to flame tem-
peratures above 1300” C. In general, optimum prop-
erties (lowest residual carbon, smallest particle sizes,
best crystallized) were obtained when the glycine/
nitrate ratio was adjusted to yield the peak flame
temperature, since combustion was more rapid and
complete at higher temperatures. Exceptions are
those materials that suffer excessive sintering or
melting at high temperatures, such as the high-tem-
perature superconductors YBazCu30,, Bi2Sr2Ca2-
Cu30i0, and related compounds. For these mate-
rials, the glycine-to-metal cation ratio was increased 100 nm
beyond that for which the maximum flame temper-
ature occurs, to typically 3 moles glycine per mole Fig. 5. Bright-field transmission electron micrograph of
metal cation. Combustion, though still spontaneous La&30.,,$-303 ash particles prepared by the glycine-nitrate
and self-sustaining, occurred at a much slower rate. technique. The particles have an approximate average diameter
Another reason for adjusting the stoichiometry to the of 20 nm.
fuel-rich (glycine-rich) side was to avoid the for-
mation of intermediate nitrate phases in the ash, as vealed that the LSC ash was composed of very tine
discussed in section 3.3 below. (5 to 40 nm diameter) lanthanum chromite parti-
Some materials produce comparatively dense, low- cles linked together in chains. TEM bright-field and
surface-area ash when formed using the metal ni- dark-field images indicated that the particles were
trates and glycine alone. One example of this is a two- individual crystals, joined at grain boundaries with
phase composite material, 2ZrG,*NiO. We have no indication of an intervening amorphous phase.
found that the bulk density of the ash can be lowered Fig. 6 is an X-ray diffraction pattern for the LSC
and the surface area increased substantially by add-
ing extra oxidant and fuel in the form of NH,NOJ
and additional glycine. Excess combustion gases pro-
duced have the effect of expanding the structure of
the ash beyond that obtained with the metal nitrates
alone. The stoichiometry still can be adjusted to pro-
duce H20, Cot, and NZ, or to be fuel- or oxidant-
rich.

3.3. Product characterization

Two perovskite compositions were prepared by

GNP for characterization and comparison to pow-
ders produced by the amorphous-citrate process.
These compositions are La,&+,,. , &IQ ( LSC ) and 20 30 40 50 60 0
Degrees26
Lao.&o.5MnG~ (LSM).
In fig. 5, transmission electron microscopy re- Fig. 6. X-ray diffraction pattern for the ash shown in fig. 5.

9
Volume 10, number 1,2 MATERIALS LETTERS September 1990

ash. This pattern is a good match to rhombohedral 120

La(Sr)CrQ, although substantial peak-broadening
was present due to the small particle sizes so that it
100 -
was difficult to determine whether some of the lower-
temperature La(Sr)CtQ orthorhombic phase was
present. These two phases are polymorphs, involving %
80 -
a displacive structural transformation with no change 2
2 _
4
in composition. Electron diffraction analysis did not
3
differentiate between the structurally similar high- ,060 Synthesized
B byAmorphous
and low-temperature La( Sr)CtQ phases in the ash, E
but confirmed the absence of other phases. $
a" 40 -
EDS microanalysis was performed on 20 individ-
ual LSC ash particles using a transmission electron
microscope with a focused 10 pm convergent elec- 20 -
tron probe. The accuracy of this technique was rel-
atively poor because sensitivity (“V) factors were
0
calculated, not measured from a known standard. For 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
this reason, we have multiplied the results by a con- X (inLax Sq., 003)
stant factor to bring the mean atomic percent of lan-
Fig. 7. Histograms of chromite particle compositions measured
thanum into agreement with a standardized analysis by energy dispersive spectroscopy on a transmission microscope.
performed by inductively coupled plasma atomic Open bars correspond to material produced by the amorphous-
emission spectroscopy. The precision expected from citrate process after calcination at 1060°C (adapted from Ander-
EDS measurements was calculated as the square root ton and Sate [ 61). The shaded bar corresponds to ash produced
by the glycine-nitrate process.
of the background-subtracted counts divided by the
background-subtracted counts, giving an expected
precision of 4.62%, relative. The relative standard of the amorphous-citrate process [ 6 ] in fig. 8. The
deviation of the atomic percent lanthanum detected GNP material was composed of two distinct phases,
in the EDS measurements was 4.66%. Therefore, one strontium-rich, and the other lanthanum-rich.
within measurement uncertainty, there was no de- An indication of the same two phases can be seen in
tectable particle-to-particle variation in composition the histogram for the amorphous-citrate LSM, pro-
for the LSC ash. duced by Baythoun and Sale [ 7 1, and calcined at
The above EDS results are contrasted to those ob- 1200°C. Again, the GNP product, containing two
tained for LSC produced by the amorphous-citrate distinct phases, showed less extensive variability than
process by Anderton and Sale [6] in fig. 7. The the amorphous-citrate product.
amorphous-citrate product showed extensive com- The appearance of two phases in the LSM prod-
positional variability, even after 1 h of calcination at ucts of both processes was due to the formation of
1060 ’ C. X-ray diffraction [ 6 ] detected Sr ( NO3 ) 2 in intermediate compounds during synthesis. In the case
the precursor prior to combustion, and four inter- of the amorphous-citrate process, based on XRD
mediate phases in the material after calcination up patterns, Baythoun and Sale [ 71 reported that both
to 880” C: SrC03, LaCrO,, SrCr04, and Sr3 ( Cr04)2. Sr(N03)* and SrCO, appeared in the precursor at
To form a compositionally homogeneous, single- room temperature, and persisted until after calci-
phase product from such powders, intermediate nation at 400 and 900°C respectively.
phases must decompose and their products diffuse In the case of the GNP process, no intermediate
into the major LSC perovskite phase during thermal products were detectable in the precursor prior to
treatment, a relatively slow process requiring high combustion. This is based on the lack of diffraction
temperatures to attain completion. lines in XRD patterns of the viscous foam that forms
EDS was also performed on the LSM ash, pro- just prior to ignition. Under certain conditions, how-
duced by GNP. Results are again compared to those ever, Sr(N03)z was detected in the ash. Use of ad-

10
Volume 10, number I ,2 MATERIALS LETTERS September 1990

tinal product is substantially reduced. For example,

a LSM powder, produced by GNP, was calcined at
Synihesizeci
by Amorphous 650°C for 4 h (in order to decrease residual carbon
Citrate
from a few percent to 0.77%). Even after this cal-
cination, the specific surface area was 23 m2/g. In
contrast, Baythoun and Sale [7] found it necessary
to calcine LSM at 1000°C to reduce total carbon to
a comparable level. After this treatment, their amor-
phous-citrate product had a specific surface area of
6.3 m*/g. Furthermore, their material required cal-
cination at 1400°C in order to achieve composi-
tional homogeneity comparable to that of the GNP
powder. After the 1400°C treatment, the surface area
of the amorphous citrate-produced powder was less
than 1.0 m2/g. The GNP-produced LSC ash has a
low residual carbon content (0.36%), and so does
n -I

0.6 0 7 0 8 0.9 1.0 not require calcination. This ash has a specific sur-
X (in La,%, xMnO,) face area of 32 m”/g.

Fig. 8. Histograms of man~ite particle com~sitions. Open bars

correspond to material produced by the amorphous-citrate pro-
cess after calcination at 1200°C (adapted from Baythoun and 4. Conclusions
Sale [ 71). The shaded bars correspond to ash produced by the
glycine-nitrate process. The glycine-nitrate process offers several distinct
advantages over the current methods of synthesizing
manganites and chromites. Single- or multi-compo-
ditional oxidant and fuel in the form of NH4N03 and nent oxide powders can be prepared rapidly and
additional glycine, as discussed above, and the ad- simply using the GNP. The method immediately
justment of the stoichiometry to moderately fuel-rich produces high-surface-area, compositionally homo-
conditions eliminated the Sr(NOX)* from the ash. geneous powders, usually with low levels of residual
These conditions produced the composition which is carbon. When the stoichiometry is properly ad-
shown in fig. 8, containing a minor, strontium-rich justed, gaseous combustion products are environ-
oxide phase as well as the major phase. No SrC03 mentally attractive, being composed of HzO, COZ.
was detected for any of the stoichiometries tested. and N2. These advantages are mainly due to the na-
These examples illustrate some important differ- ture of the glycine-nitrate combustion reaction,
ences between the two processes. Under properly ad- which is rapid and self-sustaining, and occurs at high
justed stoichiometric conditions, the GNP combus- temperatures.
tion occurs extremely rapidly, at high temperatures.
The material is rapidly transformed from a homo-
geneous liquid to a crystalline, oxide powder. Acknowledgement
In contrast, the amorphous-citrate combustion is
sluggish and must be sustained by long periods of ex- The authors wish to thank C.W. Frerichs. H.E.
ternal heating. Strontium nitrate precipitates prior Kissinger and M.C. Burt for their technical assis-
to combustion and several intermediate phases form tance on this project. We also gratefully acknowledge
during the subsequent thermal treatment. Extensive support from the U.S. Department of Energy under
thermal treatment, necessary to burn off the residual Contract DE-AC06-76RLO 1830.
carbon as well as to obtain a homogeneous product,
results in substantial grain-growth, so that the spe-
cific surface area (and therefore the activity) of the

11
Volume 10, number 1,2 MATERIALS LETTERS
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