Preparation of Well-Defined Colloidal Particles by Thermal

Decomposition of Metal Chelates

I. I r o n O x i d e s ~

RONALD S. S A P I E S Z K O ANO E G O N MATIJEVII2

Institute of Colloid and Surface Science and Department of Chemistry, Clarkson College of Technology,
Potsdam, New York 13676
Received June 14, 1979; accepted August 15, 1979

Well-defined hematite and magnetite colloidal particles of different morphologies were pre-
pared by hydrothermal aging of strongly alkaline solutions of ferric salts and triethanolamine (TEA)
at 250°C. The oxidation state of iron in the final products was controlled by the addition of either
hydrazine (N~H4) or hydrogen peroxide (H20~) to the reaction mixtures, as well as by the type and
concentration of anions present in the systems. Rapid recrystallization of hematite to magnetite
was also accomplished by hydrothermal aging of a-Fe20z dispersions in highly alkaline media con-
taining hydrazine. The transformation appeared to proceed via a dissolution-reprecipitation
mechanism. The relevance of these systems to the study of the formation of colloidal corrosion
products is discussed with special reference to the crude materials produced in the cooling circuits
of light water nuclear reactors.

INTRODUCTION hydrous oxides, consisting of either amor-

For any study of the properties of finely
dispersed matter, it is highly desirable to
have systems consisting of partiCles uniform
in size and shape. Much effort has been
directed toward developing experimental
procedures that will yield monodispersed
colloidal sols. The best known and most
extensively investigated systems have been
the polymer latices which can be produced
as spheres of exceedingly narrow size
distributions.
From the point of view of various practi-
cal applications, metal and metal hydrous
oxide dispersions are of considerable inter-
est. However, relatively few such systems
have been obtained in a uniform state. The
classical example in this respect is colloidal
gold (1), although monodispersed hydrosols
of other materials have also been prepared
(2, 3). Recently, various colloidal metal
1 Supported by the Electric Power Research In-
stitute, Contract RP-966-1.
phous or crystalline particles of well-
defined morphologies and of narrow size
distributions, have been generated by forced
hydrolysis of acidified metal salt solutions
at elevated temperatures (4, 5). While this
procedure has been successful in producing
a number of uniform systems, its limita-
tions are determined by the specific chemi-
cal complexes which precede particle
nucleation and subsequent growth (6, 7).
In this paper, a novel technique will be
described which allows the preparation of
ferric oxide colloidal particles of a variety
of morphologies. The method is based upon
the decomposition of soluble metal chelate
complexes in strongly alkaline media under
hydrothermal conditions. The addition of
oxidizing or reducing agents to the growth
solutions permits control of the chemical
processes that occur upon degradation of
the metal chelate complexes. Thus, the
oxidation state of the metal in the final
product can be affected and, as a con-

405
0021-9797/80/040405-18502.00/0
Copyright © 1980 by Academic Press, Inc.
Journal of Colloid and lnterjace Science, Vol. 74, No. 2, April 1980 All rights of reproduction in any form reserved.
 406
sequence, a transformation of the solid
phase can be achieved.
The uniformity and variety of the metal
oxide particles that can be obtained by this
hydrothermal aging technique will now
make feasible a number of fundamental
studies. These materials should also find
numerous practical applications in the areas
of catalysis, pigments, magnetic coatings,
etc. Specifically, this method of dispersion
formation is of interest to nuclear reactor
technology. Chemical decontamination of
water-cooled nuclear reactors makes ex-
tensive use of chelating agents. Indications
are that residual metal complexes formed
during the cleaning treatments may greatly
affect postdecontamination corrosion proc-
esses and radiation field buildup (8). In
particular, radioisotope enrichment in fer-
rite type corrosion films has been noted (9).
An understanding of the precipitation reac-
tions involving decomposition of metal
chelates is essential to the development of
appropriate chemical decontamination for-
mulations which could reduce or eliminate
deleterious aftereffects.
EXPERIMENTAL
Materials. All ferric salts, with the excep-
tion of Fez(SO4)a, were dissolved at room
temperature in order to minimize hydrolysis.
Preparation of the ferric sulfate stock solu-
tion required gradual heating of an aqueous
slurry of the salt to 40°C with rapid agita-
tion to promote dissolution.
All chemicals were of reagent grade
quality and were used without further purifi-
cation. Solutions were made up with twice
distilled water from an all-Pyrex apparatus.
Stock solutions of aqueous triethanolamine
(TEA, N(CH2CH2OH)3) were obtained by
dilution of the pure liquid reagent (density
1.120 g/cm3 at 25°C). Hydrogen peroxide
(30%), hydrazine hydrate (85%), and sodium
hydroxide (50%) solutions were used as ob-
tained from the suppliers. All stock solu-
tions (0.5 to 1.0 M) were filtered through
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
SAPIESZKO AND MATIJEVIC
0.45-~m Millipore membranes to remove
possible fine particulate contaminants and
none exhibited any visible evidence of
change upon storage at room temperature
for periods of up to 4 months.
Sample preparation. Extensive prelimi-
nary experimentation was carried out with a
variety of chelating agents [nitrilotriacetic
acid (NTA); (ethylenedinitrilo)tetraacetic
acid (EDTA); trans-l,2-diaminocyclohexane,
N,N,N',N'-tetraacetic acid (CDTA); N-
(2 - hydroxyethyl)ethylenediaminetriacetic
acid (HEDTA); triethanolamine (TEA);
gluconic acid; EDTA-citric acid mixtures;
CDTA-citric acid mixtures; etc.] in efforts
to find chelated ferric species which re-
mained soluble under strongly alkaline con-
ditions up to 100°C but which decomposed
at still higher temperatures. Only the ferric
salt-triethanolamine samples met these
criteria; ill-defined hydrous ferric oxide
precipitates formed in all other chelate sys-
tems examined.
The following order of reagent additions
was established for the preparation of all
samples: ferric salt solution, TEA solution,
sodium salt solution (if any), approximately
5 crn 3 water, and 50 wt% sodium hydroxide
solution. These systems were kept for 24 hr
at room temperature and monitored for
visible changes. Sample preparation was
completed by the addition of the oxidizing
or reducing components (hydrogen peroxide
or hydrazine hydrate) followed by water as
required to achieve the desired final volume.
Vigorous stirring was applied during the
mixing of various reacting components in
order to prevent local inhomogeneities.
Individual systems were 0.04 M in Fe(III)
salt (0.02 M Fe2(SO4)~), 0.2 M in TEA (5:1
chelate to metal ion ratio), and 1.2 M in
NaOH, while the concentration of other
additives varied as required for specific
purposes.
Systems were prepared from the nitrate,
sulfate, perchlorate, or chloride salts of
Fe(III). The redox condition of each sample
was either left unaltered (mildly oxidizing
 PREPARATION OF COLLOIDALPARTICLES 407

due to saturation with air) or it was ad- 146A-1) preheated to 250 _+ 5°C, and finally,
justed by the addition of hydrogen peroxide after the requisite aging period, the bomb
to give a final concentration of 0.5 M H~Oz was quenched in cold water. In some ex-
or hydrazine to yield a 0.85 M solution in periments, the reaction bombs were placed
NzH4. Electrolytes, when included, were in the oven at 25°C, gradually heated to
1.0 M NaNO3, NaC104, NaC1, and CH3- 250°C (approximately 45 rain), and then
COONa, respectively, or 0.5 M Na2SO4. aged at 250°C for 45 rain. The bombs were
On a more limited basis, modifications opened immediately after cooling and the
were made to the ferric-TEA systems prior solids collected by filtration through a Milli-
to hydrothermal aging. Thus, various con- pore membrane (0.45 /xm). Following
centrations of either boric acid (H3BO3) or thorough washing on the filter with twice
borax (Na2B400 were added, KOH was distilled water, the solid were desiccated
substituted for NaOH, or sodium boro- over silica gel for 2-24 hr.
hydride (NaBH4) was used as the reducing Some preliminary stability studies were
agent instead of hydrazine. conducted at 100°C using screw capped
Some samples were also prepared in Pyrex culture tubes (25 x 150 mm) in which
which the ferric salt was replaced by a the solutions were prepared.
known quantity of a uniform c~-Fe203 col- Analysis. The dried powders were ce-
loidal dispersion consisting of spherical mented directly to aluminum specimen
particles having a modal diameter of either blocks with silver conducting paint and
0.16 or 0.54/xm. The generation and char- subsequently examined in an International
acterization of these monodispersed hematite Scientific Instruments model SMS-2 scan-
hydrosols has been described earlier (5). ning electron microscope at a 0° tilt angle.
All other aspects of the composition, prep- X-Ray analysis of some of the solids was
aration, and hydrothermal aging of the sys- done at General Electric Company, Cor-
tems initially containing hematite were as porate Research and Development Center,
given above. Schenectady, New York.
Aging. Hydrothermal aging was con- The magnetic properties of the pre-
ducted using either type 303 stainless steel cipitates were qualitatively determined with
or Inconel 600 alloy reaction bombs of 45 a permanent magnet.
cm 3 internal volume (1.2 in. in diameter and Elemental analyses for iron, carbon, and
4.5 in. in overall length) obtained from Parr nitrogen were performed by a commercial
Instrument Company, Moline, Illinois. Seal- laboratory on the solid material which pre-
ing was accomplished by means of Teflon cipitated from the Fe(NO3)a- T E A - N a O H -
gasketed caps secured by a two piece screw Nell4 system upon hydrothermal treatment
closure. In order to prevent corrosive attack at 250°C.
on the inner surfaces of the reaction bombs, The extent of conversion of soluble ferric
these were lined with Teflon cup inserts species to precipitated oxides was deter-
of 1/16in. wall thickness. After each use the mined in several cases by weight analysis.
Teflon containers were cleaned by immer- The yield varied between 40 and 90%. One
sion in concentrated HCI for 12-48 hr fol- may expect quantitative precipitation after
lowed by thorough rinsing with distilled longer aging times.
water.
A typical aging experiment proceeded as RESULTS
follows: a 20-cm 3 aliquot of each sample
was pipetted into a Teflon liner, the reaction After mixing the ferric salt, TEA, and
bomb was sealed and placed into a mechani- NaOH solutions at room temperature, the
cal convection oven (Blue M Model POM- samples displayed no turbidity and were
Journal of Colloid and Interface Science, Vol. 74, No, 2, April 1980
408 SAPIESZKO AND MATIJEVIC

TABLE I
Results of Hydrothermal Aging at 250°C for 1 hr

Appearance and Characteristics of the

Redox
System condition Supernatant solution Solid X-ray analysis

Fe(IlI) salts- H202 Pale yellow or Black, granular, nonmagnetic C104 system: a-Fe20z
TEA orange
Fe(III) salts- H~O~ Brown or orange SO~- and CI systems: black
Na salts- or dark red, granular,
TEA magnetic
NOy, CIO~, and acetate- C104 system: cr-Fe203
systems: black or dark red,
granular, nonmagnetic
Fe(III) salts- Air Colorless CI- system: black, granular, SO4z- and C1- systems:
TEA magnetic a-Fe~O~ + trace
FezO4
NOff, SOl-, CIO~ systems: NO~ and C10~- systems:
black, granular, a-Fe~03
nonmagnetic
Fe(III) salts- Air Colorless or pale Dark red or black, granular,
Na salts- yellow nonmagnetic
TEA
Fe(llI) salts- N~H4 Colorless Black, granular, magnetica C1Oi system: F e 3 0 4
TEA
Fe(III) salts- N2H4 NO~, SO~-, C1- SO~- and C1- systems: black,
Na salts- systems: colorless magnetic
TEA C10~ and acetate- NOy, CIO¥, and acetate- NO~ system: a-Fe203
systems: pale systems: black or dark red,
yellow-orange large grained, nonmagnetic

a Chemical analysis of the solid from the Fe(NO3h-TEA-NaOH-NzH4 system: 72.3% Fe, 0.10% C,
<0.1% N.

either colorless (in the presence of NO~-,
C10~-. and C1- anions) or pale green (in the
presence of SO~-). Systems containing
hydrazine or those saturated with air re-
mained unchanged upon storage at r o o m
temperature for at least 90 days after prep-
aration. The addition of H202 resulted in
effervescence (greatest in the presence of
S O l - and CI-) and precipitate formation
after 3 to 5 days of aging at r o o m tempera-
ture. The addition of sodium salts had no
effect on any samples during their prepara-
tion or storage.
The stabilities of the Fe(C104)3 (or FeC13)-
T E A - N a O H systems in the presence of
H202, air, and N2H4, respectively, were
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
also determined at 100°C. Individual sam-
ples prepared with N2H4 or saturated with
air appeared unchanged after 8 hr of aging
at 100°C, but did contain a small quantity
of precipitate after 24 hr. In contrast, the
addition of H202 to these systems caused a
dark red coloration and precipitation after
less than 8 hr at 100°C.
The Fe(III) s a l t - T E A - N a O H systems
containing either air or N2H4 were reacted
hydrothermally at 250°C within 3 weeks
after preparation. To prevent peroxide de-
composition, samples with H2Oz were aged
within 0.5 hr after mixing. Crystalline par-
ticles formed in all samples kept at 250°C
for >1 hr. Due to the size, density, and/or
 PREPARATION OF COLLOIDAL
magnetic characteristics of the solid matter,
most of it settled to the bottom of the Teflon
liners. The precipitates were aggregated;
they could be readily dispersed by ultra-
sonic treatment, but upon standing the par-
ticles reagglomerated.
Different anions in the growth media in-
fluenced both the morphology and the size
of the particulates produced under other-
wise identical conditions. The results of the
aging studies are summarized in Table I
and will be illustrated by the scanning elec-
tron micrographs shown in the next sections.
System: Fe(III) Salt-TEA-NaOH-H202
The morphology of solids which pre-
cipitated in solutions containing hydrogen
peroxide depended on the length of aging
at 250°C. At shorter times ( l - 2 hr) non-
magnetic, disc-like particles (some with
faceted edges) were formed as illustrated in
the scanning electron micrographs in Figs.
la and c. After 10 hr of aging the particles
were nearly spherical (Fig. lb) and were
magnetic.
Analogous systems were obtained using
different ferric salts; whereas the particle
shape was consistent (Fig. ld), the particle
size varied depending on the type of anion
present. As a rule, solutions containing
SOl- yielded smaller crystals than systems
with other anions. The presence of addi-
tional salts with corresponding negative ions
did not alter the disc-like morphology of
the precipitates.
Although the X-ray analysis of these solids
showed ~-Fe2Oa (hematite) to be the princi-
pal component, some samples were weakly
magnetic (Table I), indicating the presence
of small amounts of Fe304.
System: Fe(III) Salt-TEA-NaOH-Air
In this mildly oxidizing environment the
particle morphology was different than that
obtained in the presence of H202. Further-
more, the anions influenced both the com-
PARTICLES 409
position and the shape of the solids formed
on hydrothermal aging.
The scanning electron micrograph (Fig.
2a) shows that the majority of the particles
precipitated in a Fe(C104)3-TEA-NaOH
solution are nearly spherical, although a few
disc-like and octahedral crystals are also in
evidence. Figure 2b illustrates the solids
which resulted when Fe(NO3)3 was sub-
stituted for the perchlorate salt; the higher
magnification reveals the composite struc-
ture of the particles.
The pronounced effect of additional elec-
trolyte in the precipitation medium is demon-
strated in Figs. 2c and d. The platelets were
formed in the same system as described in
the legend of Fig. 2b, except that the solu-
tions were made 1 M in NaOOCCH3 (Fig.
2c) and 1 M in NaNOz (Fig. 2d), respec-
tively, prior to aging. Similar results were
obtained on addition of other electrolytes
to the Fe(III) salt-TEA mixtures.
X-Ray analysis indicated that the dried
powders from the F e ( N Q ) 3 - or Fe(C10~)a-
T E A - N a O H systems consisted of pure
c~-Fe203, while those precipitated from the
SO~- or C1- containing solutions showed
the presence of traces of magnetite in ad-
dition to hematite. Although no X-ray data
are available for the powders produced with
added sodium salts, the appearance and the
nonmagnetic behavior of these solids in-
dicated them to be pure hematite.
System: Fe(III) Salt-TEA-NaOH-N2H4
(or NaBH~)
Both the composition and the morphology
of the hydrothermally formed precipitates
were altered when strong reducing agents
(i.e., hydrazine or sodium borohydride)
were included in the aging solutions. Mag-
netic solids, as illustrated in Figs. 3a and b,
consisting of crystalline particles of octa-
hedral symmetry resulted in all systems,
regardless of the anions present. Although
the particles were polydisperse, their aver-
age size was found to decrease as the con-
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 410 SAPIESZKO AND MATIJEVIC

E
tO

13

E
I
tO
zL

Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 >

Z
o

<
I I I I
2 C 10/~m D 10/~m
Z
P
Flo. l. (a) c~-Fe20.~ particles precipitated from a solution initially 0.04 M in Fe(C10~)~, 0.2 M in TEA, 1.2 M in NaOH, and 0.5 M in H202 upon hydro-
thermal aging at 250°C for 1 hr. (b) Magnetic solid precipitated from a solution identical to that described in (a). The sample was aged at 250°C for 10 hr.
(c) c~-Fe2Oa particles precipitated from a solution identical to that described in (a), except Fe(NO3)3 salt was used. The sample was aged at 250°C for 1 hr.
(d) Nonmagnetic solid precipitated from a solution identical to that described in (c). The sample was aged at 250°C for 10 hr.
 412 SAPIESZKO AND MATIJEVIQ

cn

Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 5
Z
©

/
0

o
C5

r~

r~

-< I I I I
e C 14Fro D 1411m
P FIG. 2. (a) ~-Fe203 particles precipitated from a solution initially 0.04 M in Fe(CIO4):~, 0.2 M in TEA, 1.2 M in NaOH, and air saturated upon hydro-
thermal aging at 250°C for 1 hr. (b) a-Fe203 particles precipitated from a solution identical to that described in (a), except Fe(NO3)3 salt was used. The sample
was aged at 250°C for 1 hr. (c) Nonmagnetic solid precipitated from a solution initially 0.04 M in Fe(NO3)z, 1.0 M in NaOOCCH3, 0.2 M in TEA, 1.2 M in
NaOH, and air saturated upon hydrothermal aging at 250°C for 1 hr. (d) Nonmagnetic solid precipitated from a solution identical to that described in (c),
ta~
except 1.0 M NaNO3 salt was used. The sample was aged at 250°C for 1 hr.
414 SAPIESZKO AND MATIJEVIt2

tn

Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 Z
o

('5 ¸
>

ra~

I,, I I
C 5~rn D lO~m
Z
9 Fro. 3. (a) FeaO4 particles precipitated from a solution initially 0.04 M in Fe(C104)~, 0.2 M in TEA, 1.2 M in NaOH, and 0.85 M in N2H4 upon hydro-
~o
thermal aging at 250°C for 1 hr. (b) FeaO4 particles precipitated from a solution initially 0.01 M in Fe2(SO4)a,.0.4 M in TEA, 2.4 M in NaOH, and 0.85 M in
% N2H4 upon hydrothermal aging at 250°C for 2 hr. (c) Weakly magnetic solid precipitated from a solution identical to that described in (a), except 0.8 M NaBH4
4~
was used as the reducing agent. This sample was aged at 250°C for I hr. (d) c~-F%O3 particles precipitated from a solution initially 0.4 M in Fe(N 0)3)2. 1.0 M in
t.~
NaNOa, 0.2 M in TEA, 1.2 M in NaOH, and 0.85 M in N~H4 upon hydrothermal aging at 250°C for 1 hr.
416
centration of hydrazine was increased from
0.85 to 4.55 M. The products seemed to be
little affected by altering the solution com-
position (Fig. 3b) or by extending the aging
time.
Magnetic crystals also formed on keeping
at elevated temperatures solutions in which
NaBH4 was substituted for N2H4, but the
resulting particles were of a less well-defined
morphology (Fig. 3c).
The addition of sodium salts to the pre-
cipitating media had a marked effect on the
hydrothermally formed solids. Solutions
containing 1 M NaNO3 yielded hematite
rather than magnetite and the particle shape
was also changed (Fig, 3d). Similar results
were obtained with an excess of NaC104
or NaOOCCH3. However, the inclusion of
N a 2 S O 4 o r NaC1 resulted in the formation
of materials of weak magnetic properties.
X-Ray diffraction patterns of the solids
from Fe(C104)3-TEA-NaOH-N2H4 solu-
tions were consistent with pure magnetite,
Fe304. Chemical analysis of the powder
obtained from the Fe(NO3)3-TEA-NaOH-
NzH4 system gave 72.3% Fe, 0.10% C, and
<0.1% N (Table I) in agreement with the
theoretical percentage of Fe in pure mag-
netite (72,36%). The result also indicates
the presence of a minor organic contami-
nant, obviously a residue of TEA or its de-
composition products. X-Ray data on par-
ticles formed in the Fe(NO3)z-NaNO3-
TEA-NaOH-N2H4 system (Fig. 3d) showed
these to be hematite.
Further variations in solution composi-
tion and aging procedures were carried out
with systems containing hydrazine. For
example, the substitution of KOH for
NaOH had no effect on the nature of the
final solid phase. Solutions of Fe(III)
s a l t - T E A - N a O H - N 2 H 4 gradually heated
from 25 to 250°C over a 45-rain period, fol-
lowed by isothermal treatment at 250°C
for an additional 45 min, yielded mixed
solids consisting of magnetite and platelet-
like hematite particles. The addition of 0.05
to 0.4 M boric acid to otherwise identical
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
SAPIESZKO AND MATIJEVI~
systems as described in this section exerted
little influence on the nature of the pre-
cipitated particles. However, the inclusion
of 0.04 to 0.2 M borax (Na~B4OT) resulted
in the formation of large crystals, similar
to those shown in Figs. 3c and d, inter-
spersed with much smaller magnetic par-
ticles. At still higher borax concentration
(0.4 M), the solids resembled the material
produced in the absence of NaeB40r with all
other components being the same.
System: ~-Fe203 Dispersions-
(TEA)-NaOH-N2H4 or H20e
In a series of experiments hematite par-
ticles of different morphologies were sus-
pended in highly alkaline solutions contain-
ing either N~H4 or H202 in the presence or
in the absence of TEA, and these systems
were then aged at 250°C as previously
described. This work was conducted in
order to establish if phase transformations
could be induced.
Preliminary experiments were carried
out with 50-mg quantities of commercially
available Fe304 (Fisher) and ~-Fe~O3 (Alfa-
Ventron) solids suspended in solutions 0.2 M
in TEA; 1.2 M in NaOH; and either 0.5 M
in H202, air saturated, or 0.85 M in N2H4.
Hydrothermal aging at 250°C for 1 hr left the
solids unchanged except for the hematite
sample in the hydrazine-containing medium.
In the latter case the dispersed material
became black and magnetic. Electron mi-
croscopy showed that this solid consisted of
large octahedral crystals embedded in a
mass of the irregularly shaped hematite
used as the starting material.
Further investigations were conducted
using a-Fe~O3 dispersions of uniform
spheres having modal diameters of 0.16 and
0.54/xm, respectively (5). The latter system
is illustrated in Fig. 4a. Five cubic centi-
meters of a sol containing the smaller
hematite particles was added to an alkaline
TEA-hydrazine solution. After aging for
1 hr at 250°C the solid dissolved. However,
 PREPARATION OF COLLOIDALPARTICLES 417

a sample initially containing twice as much solved hematite particles, whereas in Fig. 5b
~-Fe203 yielded on heating a small quantity only octahedral magnetite crystals are in
of magnetite. evidence.
The larger hematite particles (0.54 /zm
diameter) proved to be a more convenient DISCUSSION
starting material for the intended study. A
sample initially containing 26 mg of this Originally, the decomposition of metal
solid (in 10 cm 3 of the hydrosol) added to chelates at elevated temperatures was used
the same TEA-NaOH-N2H4 medium as by analytical chemists as a "cation release
above on heating at 250°C for either 1 or method" for controlled precipitation from
12 hr, resulted in the systems illustrated in homogeneous solution (10-12). Specifically,
Figs. 4b and c. Obviously, a fraction of ferric oxide was precipitated by slow deg-
ot-Fe203 particles remained unchanged, but radation of ferric EDTA complexes with
also a new phase consisting of octahedral H2Oz (13). Only in a very few cases was
crystals, characteristic of Fe304, was this procedure utilized to prepare colloidal
present. The extent of conversion increased dispersions. Very stable gold sols and less
with the time of aging; after several hours stable silver sols were obtained from EDTA
no hematite spheres could be found. Sys- complexes of the respective metals (14) and
tems of identical composition but contain- monodispersed spindle-shaped BaSO4 parti-
ing 0.5 M H202 instead of 0.85 M NzH4, cles of different modal diameters were
when hydrothermally aged at 250°C for 4 to generated by the decomposition of the
6 hr, also produced Fe304. The scanning barium-EDTA complex with H20~ in the
electron micrographs of these solids looked presence of the sulfate ion (15).
very much like the mixture of the two iron This work represents the first comprehen-
oxides illustrated in Fig. 4b. sive effort to utilize the hydrothermal de-
The presence of TEA was not necessary composition of metal chelates in mixture
for the recrystallization of hematite to mag- with different additives in order to produce
netite. Figure 4d shows Fe304 particles ob- colloidal solids of different chemical com-
tained from the same spherical oz-Fe203 positions and morphologies.
(Fig. 4a) on aging at 250°C for 6 hr in a Triethanolamine (TEA) has the advantage
medium which was 1.2 M in NaOH and of being a rather stable compound over a
0.85 M in N2H4. However, a highly alkaline broad pH range (16) and at elevated temper-
solution of Nell4 was essential to induce ature. This chelating agent is not affected
transformation of hematite to magnetite, by hydrazine or hydrogen peroxide at room
i.e., the presence of base or of N2H4 alone temperature, although the extent of any
caused no change in the spherical o~-Fe203 possible interactions of these compounds
particles. with TEA at elevated temperatures is not
The recrystallization of hematite to mag- known with certainty. While TEA binds
netite was also accomplished by using the ferric ions at room temperature into exceed-
disc-like c~-Fe2Oz particles as starting ma- ingly stable complexes (particularly at pH
terial. Scanning electron micrographs in > 12) (17), these species decompose on
Figs. 5a and b represent the same system as heating and release ferric ions.
shown in Fig. lc which was subjected to Solids which precipitated in oxidizing
aging at 250°C for 2 and 6 hr, respectively, environments (H202, air) on hydrothermal
after the original particles were suspended aging of the Fe(NO3)3-TEA solutions ap-
in a basic hydrazine solution (!.2 M NaOH peared as pure hematite. Other ferric salts
+ 0.85 M N2H4). It is noteworthy that Fig. yielded some magnetic solids in addition to
5a still shows a number of partially dis- o~-Fe203, particularly upon prolonged aging.
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 418 SAPIESZKO AND MATIJEVI(~

rn

Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
 ~0
>
>

Z
O

>

>
,.-.]

< I I I I
o
C 5~m D 5~m
e
z
P FIG. 4. (a) a-Fe20.~ hydrosol with particles having a modal diameter of 0.54 tzm used in the hydrothermal aging studies. The preparation and characteriza-
tion of these particles has been described in Ref. (5). (b) Mixture of ~-Fe203 and Fe304 particles precipitated from a suspension of c~-Fe203 particles (as illus-
trated in a) in a medium initially 0.2 M in TEA, 1.2 M in NaOH, and 0.85 M in HzH4 upon hydrothermal aging at 250°C for 1 hr. (c) Mixture of c~-Fe2Oz and
FesO4 particles precipitated from a system identical to that described in (b). The aging time at 250°C was 2 hr. (d) Fe304 particles precipitated from a system 4~
c~ 7z
similar to that described in (b), except TEA was omitted from the reaction medium. The sample was aged at 250°C for 6 hr.
 4~
b~

a,

<
g

>
>

N
©
>
Z

FIG. 5. (a) Mixture of a-Fe2Oa and FeaO4 particles prepared from a suspension of a-Fe203 particles (as illustrated in Fig. lc) in a medium initially 1.2 M
in NaOH and 0.85 M in N2H4 upon bydrothermal aging at 250°C for 2 hr. (b) FeaO4 particles prepared from a system identical to that described in (a).
The sample was aged at 250°C for 6 hr.
 PREPARATION OF COLLOIDAL PARTICLES
The appearance of magnetite was accom;:.,
panied by a change in particle size and
shape (Figs. la and b), which indicated that
on extended heating the initially formed
solid dissolved and then reprecipitated as a
new phase. The actual reducing agent is not
known at this time, but it could be a de-
composition product of TEA. The role of
TEA in the reduction of hematite to mag-
netite at high temperatures is further in-
dicated by the observation that this phase
transformation also occurred in the presence
of H202.
When hydrazine or sodium borohydride
was introduced into the systems, the solid
phase was predominantly magnetite. Only
in the presence of high concentrations of
certain anions (in particular NO;- and C1Oi-)
was the precipitated phase hematite. Obvi-
ously, the reducing power of Nell4 (or
NaBH4) was suppressed by the oxidizing
effect of these oxyanions.
The rapid phase transformation of pre-
formed hematite to magnetite proceeded
through a dissolution stage. This was best
documented in examples involving the disc-
like a-Fe203; electron micrographs (Fig. 5a)
leave no doubt that the original solids dis-
solved. The solutions became supersaturated
(at least locally) with respect to magnetite,
which then nucleated and grew into well-
defined crystals. It is noteworthy that the
presence of a reducing agent (N2H4) in
strongly alkaline solutions was essential for
such recrystallization. TEA was not neces-
sary for the phase transition to take place,
but the process was accelerated when this
chelating agent was added. Obviously, TEA
promoted the dissolution of hematite.
Finally, a comment with respect to the
relevance of this work to corrosion of iron
may be in order. It was found that hydro-
thermal decomposition of iron chelates in
boilers may produce corrosion-resistant
coatings of magnetite on steel surfaces (18,
19). The corrosion products generated in
the cooling circuits of light water nuclear
reactors consist predominantly of a-Fe203
421
and:~Fe304 ( o r related nonstoichiometric
nickel- and cobalt-substituted ferrite-type
materials). In particular, it was shown that
after chemical cleaning with chelating agents
the newly formed corrosion crud is com-
posed of such iron oxide deposits.
This work indeed shows that hematite
and magnetite are the products of hydro-
thermal decomposition of ferric chelates
and that under specific conditions, phase
transformation from hematite to magnetite
can readily occur. In any attempt to com-
pare the results of this work to actual cor-
roding systems one must consider the con-
ditions which exist in interfacial regions
where the electrolyte concentrations and
the pH are vastly different than in the bulk
solution. For example, it has been suggested
that caustic concentrations may reach high
levels in crevices in steam generators where
superheat conditions exist (20). The denting
phenomena observed in steam generator
tubes has also been attributed to chloride
enrichment in the support plate crevices
(20-22). Thus, the experiments described
in this work may closely resemble certain
situations encountered at steel/solution
interfaces.
It is not intended to imply that these are
the only possible reactions that lead to cor-
rosion crud formation. Indeed, there are
numerous other mechanisms which would
correspond to different conditions. One
such process which yields well defined mag-
netite by oxidation of ferrous hydroxide
gels is discussed elsewhere (23).
ACKNOWLEDGMENT
The authors are greatly indebted to Dr. Rodney E.
Hanneman of the General Electric Company, Corpo-
rate Research and Development Center, Schenectady,
N. Y., for the X-ray diffraction analyses presented
in this work.
REFERENCES
1. Thiele, H., and yon Levern, H. S., J. Colloid Sci.
20, 679 (1965); EniistOn, B. V., and Turkevich,
J., J. Am e r . Chem. Soc. 85, 3317 (1963).
Journal of Colloidand Interface Science, Vol.74, No. 2, April 1980
422 SAPIESZKO AND MATIJEVI~
2. Watillon, A., and Dauchot, J., J. Colloid Interface
Sci. 27, 507 (1968).
3. Watson, J. H. L., Heller, W., and Wojtowicz, W.,
J. Chem. Phys. 16,997 (1948); Watson, J. H. L.,
Cardell, R. R., and Heller, W., J. Phys. Chem.
66, 1757 (1962).
4. Matijevi6, E., Progr. Colloid Polym. Sci. 61, 24
(1976).
5. Matijevi6, E., and Scheiner, P., J. Colloid Inter-
face Sci. 63, 509 (1978).
6. Bell, A., and Matijevi6, E., J. lnorg. Nucl. Chem.
37, 907 (1975).
7. Sapieszko, R. S., Patel, R. C., and Matijevi6, E.,
J. Phys. Chem. 81, 1061 (1977).
8. Report by Battelle Pacific Northwest Laboratories,
"Literature Review of Dilute Chemical Decon-
tamination Processes for Water-Cooled Nuclear
Reactors," Electric Power Research Institute
no. NP-1033, March, 1979.
9. DeHollander, W. R., Paper presented at the 1978
meeting of the National Association of Corrosion
Engineers, Houston, Texas, March 1978.
10. Gordon, L., Salutsky, M. L., and Willard, H. H.,
"Precipitation from Homogeneous Solution,"
Wiley, New York, 1959.
11. Heyn, A. H. A., and Schupak, E., Anal. Chem.
26, 1243 (1954).
12. Willard, H. H., and.Yu, S. T., Anal. Chem. 25,
1754 (1953).
Journal of Colloid and Interface Science, Vol. 74, No. 2, April 1980
13. MacNevin, W. M., and Dunton, M. L., Anal.
Chem. 26, 1246 (1954).
14. Fabrikanos, A., Athanassiou, S., and Lieser,
K. H., Z. Naturforsch. 18b, 612 (1963).
15. Takiyama, K., Bull. Chem. Soc. Japan 31, 950
(1958).
16. Chaberek, S., and Martell, A. E., "Sequestering
Agents." Wiley, New York, 1959.
17. Kunaszewska, M., Roczniki Chem. 47,683 (1973).
18. Margulova, T., Bursuk, L., Tevlin, S., Bogatyreva,
S., and Trosckin, V., Paper presented at the
International Corrosion Conference, The Univ.
of Surrey, England, January 7-12, 1973.
19. Booy, M., and Swaddle, T. W., Canad. J. Chem.
55, 1762, 1770 (1977).
20. Berry, W. E., Paper presented at the 1979 meet-
ing of the National Association of Corrosion
Engineers, Atlanta, Georgia, March 1979.
21. Wootten, M. J., Economy, G., Pebler, A. R., and
Lindsay, W. T., Jr., Paper presented at the 1978
meeting of the National Association of Cor-
rosion Engineers, Houston, Texas, March 1978.
22. Pettit, P. J., and McTigue, P. F., Paper presented
at the 1978 meeting of the National Association
of Corrosion Engineers, Houston, Texas, March
1978.
23. Sugimoto, T., and Matijevi6, E., J. Colloid Inter-
face Sci. 74, 227 (1980).