Materials Letters 17 (1993) 309-31 I

North-Holland

On the solid phase transformation goethite-, hematite

L. Diamandescu, D. MihBilA-TArBbAganu
Institute ofAtomic Physics, P.O. Box MG-6, Bucharest, Romania

and

M. Feder
SC. AFERO, Calea Floreasca 169, Bucharest, Romania

Received 7 April 1993; in final form 2 1 June 1993; accepted 24 June 1993

Miissbauer spectroscopy has been used to investigate the solid phase transformation of goethite into hematite at 250°C. An
Avrami-Erofeyev-type relation was found to describe the thermal conversion of alpha oxihydroxide to the alpha iron oxide. No
intermediate phase was observed in the analyzed samples. The reaction constant was determined. A possible nucleation mecha-
nism is also discussed.

1. Introduction been done with a standard a-Fe203 absorber in a ve-

locity range of + 12 mm/s. By using a least-squares
The transformation goethite (a-FeOOH) + he- fitting program the Miissbauer spectra of the ob-
matite (a-Fe,O,) is currently a subject of consid- tained samples were computed and the weighted
erable interest [ l-51 due to the various technolog- amount of a-FezO, was evaluated.
ical applications of alpha iron oxide. The shape, The goethite was prepared by air oxidation of
average particle size, porosity and homogeneity of Fe (OH), at room temperature. The ferrous hydrox-
alpha iron oxide determine the characteristics of ide was obtained by ammonia precipitation in a fer-
some magnetic recording oxides and ferrite mate- rous sulphate solution. Samples of powder acicular
rials, such as saturation magnetization, coercive force, goethite with particle size between 0.5 and 1 pm and
magnetic density and dispersibility. acicular ratio 1: 8 to 1 : 10 were introduced in a fur-
In previous work [ 51 the reaction kinetics of the nace which was heated at a rate of = 6”C/min, kept
hydrothermal transformation goethite-hematite has at treating temperature for different times up to 4 h
been studied by means of MSssbauer transmission and finally cooled to room temperature. The tem-
spectroscopy. It was found that a monomolecular, perature was controlled by an electronic thermocon-
first-order reaction characterizes the reaction process. troller with an accuracy of ? 2°C.
This note reports preliminary Miissbauer spec-
troscopy data on the kinetic properties of the solid
state transformation goethite+hematite. 3. Results and discussion

The obtained goethite presents a characteristic non-

2. Experimental Lorentzian six-line MSssbauer spectrum. Fig. 1 dis-
plays both the goethite and hematite (standard)
Standard transmission MGssbauer spectroscopy MSssbauer spectra together with the computed sub-
was used with both source and absorber at room spectra. The spectrum of goethite can be mainly re-
temperature. The calibration of the spectrometer has solved in eight Lorentzian subspectra but can be cal-

0167-577x/93/$ 06.00 0 1993 Elsevier Science Publishers B.V. All rights reserved. 309
 Volume 17, number $6 MATERIALS LETTERS September 1993

0 I

.$0.96-
5
2 0.92 -

0.88- f :

0.84 , I
; IIIIIIII
-10-i -6-G-2 0 2 4 6 810
Velocity(mm/s)
Fig. 1. Miissbauer spectra of goethite and hematite (standard)
together with the computed curves.

culated also in terms of electronic relaxation effects

[6-81.
In fig. 2 some representative Mijssbauer spectra of
the samples during the transformation at 250’ C are 0.08 -:
presented. One can observe the simultaneous pres- t
ence of iron hydroxide and iron oxide with accom-
panying decrease of a-FeOOH with treatment time.
The computer processing revealed a distribution of
hyperfine magnetic fields in both phases suggesting
the presence of iron in different inequivalent posi-
tions in the lattice during thermal treatment at
250°C. The effective magnetic field at the iron nu-
cleus changes from H,,s 521 kOe to 410 kOe (+4
kOe) in hematite and from Hen= 398 kOe to 300 kOe
( + 4 kOe) in goethite.
In all the analyzed spectra only a-FeOOH and a- II IIIIIIIII
Fez03 phases were identified, in good agreement with -10-8-6-b-2 0 2 4 6 810
the results of Watari and co-workers [ 3 1. The MSss- Velocity(mm/s)
bauer areas of these phases were used to calculate the
Fig. 2. The computed Mtissbauer spectra of goethite after ther-
mal treatment at 250°C for different times.
310
Volume 17, number 5,6 MATERIALS LETTERS September 1993

weighted amount of a-FezOX formed at a given time The equations which have been found to corre-
by assuming equal recoil-free fraction fgoethite and spond to the deceleratory reaction are the “contract-
fhematite(table 1). Because no third phase was de- ing cube” equation and the first-order equation (or
tected in the spectra the studied transformation can unimolecular decay law) [ 9 1. The first-order equa-
be represented as tion can be written as follows:

2a-FeOOH+a-Fe,03 +H,O , (1) -log(l-y)=kt, (2)

suggesting a direct transformation of goethite into where k is the rate constant and t the reaction time.
hematite. With this consideration and by using the By plotting -log ( 1 - ‘J) versus t, a straight line is ob-
Massbauer areas of the two species the degree of tained whose slope determines the reaction constant
transformation y into iron oxide as a function of re- k. From this behaviour we conclude that the solid
action time (reaction isotherm) was obtained. In fig. phase transformation goethite+hematite (in pow-
3, the reaction isotherm at 250°C is presented. The der form) obeys first-order kinetics. So the thermal
shape of the isotherm indicates a deceleratory re- decomposition of powder goethite at 25O’C seems
action throughout; that means the rate is progres- to be controlled by a nucleation process and each in-
sively decreasing as the reactant is consumed. dividual particle in the assemblage may be nucleated
with equal probability [ 91. The reaction of each in-
Table 1 dividual crystal results from the formation of a sin-
The relative area and the degree of transformation y from the gle nucleus on the surface of the particular particle.
room-temperature MGssbauer spectra of a-FeOOH heated at
The determined value of the rate constant at 250°C
250°C for different times t
is k,,, z 1.2x 1o-4 s-l.
Sample t Relative area Y (%) The activation energy, which represents the energy
(min) barrier to reaction, can be evaluated from M&s-
a-Fez03 a-FeOOH bauer date [ 51 knowing the rate constants in the
a I 0.50 0.50 67.11 temperature range of interest. Further studies are in
b 3 0.51 0.49 67.72 progress.
c 5 0.52 0.48 68.68
d I5 0.65 0.35 78.71
Acknowledgement
; 60
30 0.75 0.25 85.76
0.94 0.06 93.45 The authors are greatly indebted to Professor J.
g 120 0.95 0.05 97.44 Wolf and Dr. C. Masson from ENSSAT - Lannion,
h 240 0.99 0.01 99.50
University of Rennes, France for their aid in the
error +0.03 f0.03 & 0.05 computing part of this work.

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