•OURNAL

OFGEOPHYSICAL
RESEARCH VOL.73, No. 18, SEPTEMBER
15, 1968

Magnetic Studieson Specimensof Intergrown

Maghemite and Hematite
H. PORATH x

Department o• Geophysicsand Geochemistry

Australian National University, Canberra, Australia

The direction and intensity of remanent magnetizationof intergrownmaghemiteand hema-

tite have been studied as a function of the hematite content by heating artificial specimensof
maghemiteunderan astaticmagnetometerat temperauresof 549 and 580øCin a field of 1.08oe.
The remanencevector during the inversionfrom maghemiteto hematite is directedalong the
appliedfield and is not controlledby the magnetization of the host mineral,maghemite.An
anomalously high remanenceis observedfor hematitecontentsof 92 to 95.%.Thermal demag-
netization showsthis magnetizationto be primarily due to the residualmaghemite.It is sug-
gestedthat spinexchange interactions
across
the interfaceof intergrownmaghemiteandhema-
tite are the causeof the high remanencebecausethey are responsiblefor aligningthe moments
of the residualmaghemitefraction along the direction of magnetizationof hematite. The
experimental
evidencefurthersuggeststhat the chemicalremanence
of hematiteobtainedby
invertingmaghemiteat 540øCis not due to a spin-cantedmomentbut originatesfrom un-
compensated
antiferromagnetic
sublattices.
Resultsfrom torquemeasurements
showa high-
field rotationalhysteresisfor the maghemite-hematite
specimens.
The rotationalhysteresis
increases,
however,with the hematitecontentand attainsa maximumfor pure hematite,
indicatingthat the magnetichardness of hematiteratherthan exchange interactions
between
thetwomagnetic minerals
isprimarilyresponsible
for therotationalhysteresis.

INTRODUCTION of the host minerals,magnetiteand maghemite,

might controlthe directionof magnetizationof
Exchange
coupling
of spinsystems
across
the the hematite with little influence from the
interfaceof two magneticphasessimilarto the
ambientmagneticfield.
onefoundby MeiklejohnandBean [1956] for
Banerice [1966] found a nonvanishinghigh-
intergrowncobaltand cobaltoxidehas been
field rotational hysteresisin natural specimens
suggestedby Gorter[1957]andStacey[1963]
of intergrown maghemite and hematite and
to providea possible mechanism of a stable
suggestedthat the two magnetic phaseswere
alignmentof the momentsof two intergrown
coupledby exchangeanisotropy.The senseof
magneticmineralsin rocks.The exchangeinter-
the coupling between the two minerals was
action,or exchangeanisotropy,manifestsitself
not shown, however, and we have therefore
in a nonvanishingrotational hysteresisand,
carried out experimentson artificial specimens
providedthat thereis a preferreddirection
of
of maghemiteto observethe direction and in-
coupling,in a unidirectional
anisotropyand a
tensity of magnetizationof intergrownmaghe-
nonsymmetrical hysteresis
loop(seeMeiklejohn
mite and hematite during the transition.
[_1962]for review). Dependingupon the sense
of the couplingbetweenthe two magneticmate- EXPERIMENTAL PROCEDURES
rials,the exchange
interactioncanleadto self-
reversal in the remanence of rocks. Commercially available maghemite powder
Possible
processes anisot- (MO 4526), which was obtained from C. K.
for whichexchange
ropy mightbe of importancein rockmagne- Williams & Co., New York, was used in the
tism are the oxidationfrom magnetiteto hema- experiments described in this paper. The
tite and the inversion from maghemite to powderconsistsof fine-grainedacicularmaghe-
hematite.In theseprocesses the magnetization mite particles (average size • 0.4 /•; dimen-
sion ratio • 8'1) which carry a stable mag-
• Now at Southwest Center for Advanced Stud- netic moment because of their high shape
ies, Dallas, Texas 75230. anisotropy.
5959
5960 tI. PORATIt
Several specimenswere preparedby mixing
maghemitewith plaster of Paris. The plaster
did not show any remanent magnetization,
even after heatingto 600øCand coolingin the
earth's magnetic field. The approximatestart-
ing concentrationof maghemitein the speci-
mens was obtainedby comparingthe magnetic
susceptibilities
of the pure maghemitepowder
(K -- 5.9 X 10-2 emu/g) and the plasterspeci-
mens (K-- 2.25 to 3.45 X 10-2 emu/g). During
the consolidationthe specimensacquireda de-
trital magnetizationdirected along the earth's
field of about 10-•' emu/g.
A few specimens that were heated for 1
hour at 750øC were completelyinverted from
maghemiteto hematite, the susceptibilityof
hematitebeingabout 90 X 10-• emu/g. Several
specimenswere then heated at various tem-
peraturesin order to find the lowest temper-
ature at which maghemiteinverts to hematite
in heating periods possiblein the laboratory.
Below 500øC only a small portion of maghe-
mite inverts to hematite in heating periodsof
several hours, and temperaturesabove 500øC
were therefore chosen for the experiments.
To study in detail the remanent magnetiza-
tion during the transition,we heatedthe speci-
mens at either 540 ø or 680øC in a furnace lo-
cated under an astatic magnetometer. The
temperaturecould be controlledto within 5øC.
Details of this instrument are described else-
where [Chamalaun and Porath, 1968]. The
specimenswere heated quickly to the required
temperaturein zero field, the field of the lower
magnet at the specimenbeing negligiblefor
the distance of 8.5 cm between the specimen
and the magnet. When the temperature is
reached,a vertical field of 1.08 oe is applied,
the original remanencevector making an angle
of about 60ø with the applied field. The
direction and intensity of the remanent mag-
netization of the specimenis measuredby the
off-centermethodin regulartime intervals; dur-
ing the measurement of the remanencethe mag-
netic field at the specimenis cancelled.
The susceptibilityof the specimenas a func-
tion of temperatureand time is obtainedfrom
the differencein the vertical componentsof
magnetizationmeasuredin zero field (rema-
nence) and in H -- 1.08 oe (remanence +
induced magnetization), respectively.As the
susceptibilityof hematite is very small com-
pared with that of maghemite,the suscepti-
bility of partially inverted maghemitespeci-
menswill be roughlyproportionalto their mag-
hemire content.
RESULTS
Intensity and direction o• the remanent mag-
netization during the transition. A thermal
demagnetizationcurve of a maghemite speci-
men obtained by heating under the astatic
magnetometeris shownin Figure 1. The rema-
nence has a Curie point of 570øC, but suscep-
tibility measurementsafter rapid cooling to
room temperature show that only 75% of
maghemitehas inverted to hematite. A small
remanenceof maghemiteof about 0.5 to 1.0 X
10-8 emu/g is left at 540øC, whereas580øC,
the other temperature chosenfor the detailed
experiments, lies beyond the Curie tempera-
ture of the remanenceof maghemite.The sus-
ceptibility of maghemiteincreaseswith temper-
ature and at 540øC exceedsthe room temper-
ature value by about 20%. This behavior is
usually attributed to the fact that the rate of
decreaseof the coerciveforce Ho(T) is larger
than that of the spontaneousmagnetization
I8 (T) [Hopkinson effect; see Nagata, 1961,
p. 98].
The intensity of the remanent magnetiza-
tion as a function of time and maghemitecon-
tent is shown in Figure 2. The first measure-
ment of remanent magnetizationtaken after
].0
.5
100 200 300 400 500 600
TEMPERATURE øC
Fig. 1. Normalized thermal demagnetization
curve of maghemite specimen measured under
the astarte magnetometer.
 MAGNETISM OF INTERGROWN MAGHEMITE AND HEMATITE 5961

10 Ix
INTENSITY \

emu) x•-- -•7

(•ø•
• I
I
i

•10 •• 7 *"•'" -..--..... 7

40 I

540oC

• _ .1 -• MINUTES
-5-•ooc
I I I I I I
0 30 60 90 120 150 180
Fig. 2. Remanentmagnetizationof intergrownmaghemiteandhematiteduringthe inversion.
Numbers on curvesdenote approximatemaghemite content.

5 min of heating at 540øC showsthat about peratures.About 5 to 7% of maghemiteis left

50% of the maghemitehas inverted to hema- after heating at 540øC for 3 hours, whereas
tite, and after 5 min at 580øC, 92% has in- specimenscontain only 1% of residualmaghe-
verted.The magnetizationdirectionis perfectly mite after heating for 1• hours at 580øC.
alignedalongthe appliedfield. I-Ieating samplesunder the astatic magne-
All three curves show similar features in the tometer longer than 3 hours causesconsider-
dependenceof the remanent magnetizationas able drift due to inadequateshieldingof the
a function of time. Two maxima are observed copper dampingpot and the magnet system.
which occur after 10 min and 30 to 50 min To obtain completetransformationof maghe-
for heating at 540øC and after 5 and 25 min mite to hematite at the temperaturesused in
for heating at 580øC. The secondmaximum in the experiments,we heatedsomespecimens for
the remanent magnetization is related to a 6 hoursin the large furnaceusedfor stepwise
maghemite content of about 5 to 8%. Subse- thermal demagnetization. Again specimensare
quently, the remanent magnetization decreases heatedquicklyin zerofield to 540øCand kept
gradually,but a completeinversionof maghe- at this temperature in a field of 1.08 oe. The
mite to hematite is not achieved at these tern- specimens
are then cooledin zero field, so that
5962 H. PORATH

the magnetization is again only a chemical

remanent magnetization due to the inversion
of maghemiteto hematite.
A comparisonof the intensitiesof magneti-
zation and susceptibilitiesfor heating periods
of 3 hours at 540øC under the magnetometer
and 6 hours in the large furnace is shown in
Table 1. Heating for 6 hours resultsin an
most completeinversionof maghemiteto hema-
tite, and the intensitiesof magnetizationare
considerablysmaller than those of specimens
heatedfor only 3 hours.
TRM o/ hematite. To comparethe inten-
sitiesof TRM and CRM of hematite,we heated
somespecimens
abovethe Curie point of hema-
tite and cooled them in a field of 1.08 oe. These
intensities are also listed in Table 1. The TRM
is considerablysmaller than the remanenceof
partially inverted maghemitespecimens heated
for 3 hours at 540øC. The TRM is, however,
substantiallylarger than the remanent mag-
netization of specimensheated for 6 hours at
540øC.
Thermal demagnetizationcurves of TRM
and CRM. Figure 3 shows the thermal de- 100 200 300 400 500 600 700
magnetizationcurves of the TRM and CRM TEMPERATURE øC
of hematite which were obtained by heating
Fig. 3. Stepwise (top) and continuous (bot-
the specimensunder the astatic magnetometer tom) thermal demagnetization curves of TRM
and by stepwisedemagnetizationin zero field. and CRM of hematite produced by inversion of
The remanent magnetizationproducedby heat- maghemite. Curve A = CRM produced by heat-
ing the maghemite specimensfor 3 hours at ing maghemitefor 6 hours at 540øC; curve B
= CRM produced by heating maghemite for 3
540øC under the magnetometer shows a de- hours at 540øC.
magnetization curve similar to the curve of

TABLE 1. CRM and-TRM of the pure maghemite specimen of Figure 1.

Maghemite-Hematite Specimens Maghemite appears therefore to be responsi-
ble for the large remanentmagnetizationthat
Susceptibility Intensity is observedfor a maghemitecontentof 5 to 8%.
Specimen ( X 10-2emu/g) ( X 10-3emu/cc) On the other hand, the small CRM obtained
Before Heating After Heating
by heating maghemitespecimensfor 6 hours
in the large furnace has continuousand step-
wise demagnetizationcurves which are similar
a) CRM after heating for 3 hours at 540øC in H
= 1.08 oersteds to that of the TRM of hematite and therefore
I 2.45 0.12 27.5 probably representsthe proper CRM of hema-
2 2.25 0.14 17.5 tite producedby inversionof maghemitein a
b) CRM after heating for 6 hours at 540øC in H weak magneticfield. Although this CRM in-
-- 1.08 oersteds
I 3.45 0.016 0.46 cludes only hematite grains having blocking
2 2.30 0.014 0.72 temperaturesabove the inversiontemperature
c) TRM of hematite in H - 1.08 oersteds of 540øC, thermal demagnetizationcurves of
I 3.40 0.010 8.4, hematite show blocking temperatures above
2 3.45 0.012 9.3
3 3.45 0.0085 10.6
600øC (e.g., Figure 3). Thus a large fraction
of the hematite grains will contribute to the
 MAGNETISM OF INTERGROWN MAGHEMITE AND HEMATITE 5963
4
magnetizationwas demonstratedby Kobayashi
[1961] by isothermalagingof a ferromagnetic
precipitate of Cu-Co alloy. I-Iis results could
be explainedby the singleand multidomain
theories.The remanentmagnetization increased
as the particlesgrewfrom a superparamagnetic
to a single-domainsize and decreasedagain
after the formation of domain walls.
The hematiteparticlesproducedfrom inver-
sion of maghemite in our experiments are
smallerthan i /x and are, therefore,singledo-
mains.The intensityof CRM duringthe trans-
formation from maghemite to hematite in a
1 2 3 4 5 6

11H(10'40.'1)
Fig. 4. Rotational hysteresisas a function of
reciprocal field for maghemite-hematite speci-
mens. Approximate maghemite content of speci-
mens: S1 -- none; S2 • 2%; S3 • 8%.
observedCRM, except for those grains that
were formed when the applied field was can-
celled to measure the remanence. The CRM
of hematite constitutesonly about 5 to 10%
of the TRM, which is similar to the intensity
weak magneticfield shouldthereforedepend
only on the hematite content and should reach
a saturation value once the inversion is com-
plete.
Our experimentalresults,however,showtwo
maxima in the remanence that are related to
differentcontentsof maghemitein the speci-
men. The first maximum and subsequentde-
creasein the remanencemight possiblybe ex-
plainedby a modificationof the single-domain
theory by grain interactions,which cause a
suddendrop in the magnetizationfor a certain ,

ratio of CRM to TRM found by Haigh [1958] concentration,as magnetostaticinteractionswill

for the reductionprocessof hematite to mag- tend to orient newly formed grainswith their
netite. momentsto produceflux closurein groupsand
Consideringthe concentrationof hematite in pairs of grains.
the specimens,the absolutevaluesof the CRM The secondmaximumin the remanentmag-
and TRM intensitiesare small. This might be netization occursfor a maghemitecontent of
due to the small grain size, with part of the about 5 to 8%. A similar anomalouslyhigh
particlesbeingsuperparamagnetie. remanencein partially invertedmaghemitehas
Rotational hysteresis. The torque curves of beenreportedby Gustardand Schuele[1966]
severalspecimensof partially inverted maghe- in a differenttype of experiment.They meas-
mite were measured in fields of up to 12,400 ured the isothermal remanence of acicular
oe. The constant term of the torque curves maghemitepowderspartially invertedto hema-
representsthe rotational hysteresisand has tite after magnetization
to saturationand par-
beenplotted in Figure 4 versusreciprocalfield. tial ac demagnetizationusing a vibration
The rotational hysteresisstill increasesat the magnetometer. The remanence increases as a
highest available field and is largest for a function of hematite content and reaches a
specimenin which maghemite has been com- maximum for 90% hematite.
pletely inverted to hematite. The high-field GustardandSchuele[1966and personalcom-
rotational hysteresis in partially inverted munication] suggestas an explanationof the
maghemite therefore appears to be primarily anomalouslyhigh remanencethat the magneti-
due to the extreme magnetichardnessof hema- zation of the hematite fraction controls the
tite, which masksany rotational hysteresisdue directionof magnetization of the residualmag-
to exchangeanisotropythat might be present. hemirefractionby someform of spinexchange
I)ISCUSSION
interactionsimilar to the one discoveredby
Meiklejohn and Bean [1956]. Our thermal de-
Intensity o/ magnetizationduring the transi- magnetizationexperimentsindicate that mag-
tion. The production of chemical remanent hemireis indeedchieflyresponsible for the high
5964 H. PORATH

remanenceat these compositions.If magneto- rite originatesfrom local departuresfrom the

static interactions between hematite and mag- antiferromagneticlattice.
hemitc were responsiblefor aligningthe resid-
CONCLUSIONS
ual maghemite to produce the anomalously
high remshence,the remshencedirections of The chemical remanence of hematite ob-
hematite and maghemiteshouldbe antiparallel. tained by inverting maghemite at 540 and
The thermal demagnetizationexperiments,how- 580øC, respectively,is not controlledby the
ever, showthe remshencevectorsof maghemite magnetizationof the host mineral. On the con-
and hematite to be parallel, and exchange trary, the experimentalresultsindicatethat the
isotropy is suggestedas the causeof the align- residualmaghemiteis alignedby exchangein-
ment of the residualmaghemiteand therefore teractionsalong the magnetizationdirectionof
as the cause of large intensities of remanent hematite, leading to a maximum in the rema-
magnetization. The exchangeanisotropy field nence for a hematite content of 92 to 95%.
is assumedto be sufficientlylarge in compar- The chemicaltransformationthat is primar-
ison with the crystalline anisotropy field in ily of interest in rock magnetismis the oxida-
maghemiteto overcomeany incoherencyin the tion of magnetitedirectly to hematite,but this
spin planes at the interface between the two is difficult to perform in the laboratory at
minerals. Because exchange anisotropy acts temperaturesbelowthe Curie point of magne-
acrossthe interface of two magnetic materials, tite. Maghemite appears as an intermediate
the maximum in the remanence at a hematite
product in the oxidation of some magnetites
compositionof 92 to 95% probably signifies [Elder, 1965], however,and our resultswould
a maximum in the interaction area between then be applicable.Furthermore,magnetitehas
maghemite and hematite. a spinel structure similar to maghemite and
The exchangecouplingbetweenhematite and one would therefore expect spin interactionsto
maghemitedoesnot appear to producea sub- be similarto thosewithin the maghemite-hema-
stantial high-field rotational hysteresis, how- tire system.
ever, as the results from high-field torque ex-
Aclcnowledgments. This work was done dur-
perimentsindicatethat the rotationalhysteresis ing the tenure of an Australian National Univer-
is primarily causedby the magnetic hardness sity scholarship. I wish to thank Dr. F.
of hematite. Chamalaun for encouragement and Dr. $. W.
Origin o/ the remanenceo/ hematite. The Graham for critically reading the manuscript.
weak spontaneousmoment of hematite is gen-
REFERENCES
erally assumedto originatefrom a slight cant-
ing of the antiferromagneticspins [Dzyalo- Banerjee, S. K., Exchange anisotropy in inter-
shinskij,1958; Moriya, 1960], whichmeansthat grown maghemite and hematite, Geophys.J.,
the remanence vector of hematite should be 10, 449, 1966.
Chamalaun, F. YI., and H. Porath, A continuous
perpendicularto the spin direction. Exchange thermal demagnitizerfor rock magnetism,Pure
interactionsbetweenthe spin.systemsof mag- Appl. Geophys.,in press,1968.
hemitc and hematite should therefore cause Dzyaloshinskij, I., A thermodynamic theory of
the remanence vectors of these minerals to be weak ferromagnetismof antiferromagnetics,J.
Phys. Chem. Solids, 4, 241, 1958.
perpendicularto each other. Our experiments Elder, T., Particle size effect in oxidation of
indicate, however, that spin exchangeinterac- magnetite, J. Appl. Phys., $6, 1012, 1965.
tions align the momentsof the residualmaghe- Gorter, E. W., Chemistry and magnetic prop-
mite along the hematite direction.This suggests erties of some ferrimagnetic oxides like those
that the chemical remanenceof hematite pro- occurringin nature, Advan. Phys., 6, 336, 1957.
Gustard, B., and W. J. Schuele, Anomalously
ducedby inversionof acicularmaghemitepar- high remanencein ('•-Fe203) ß (a-Fe203), par-
ticles is not primarily due to a spin-canted ticles, J. Appl. Phys., 37, 1168, 1966.
moment but arises from uncompensatedanti- YIaigh, G., Processof magnetization by chemical
ferromagneticsublatticesgiving rise to ferri- change,Phil. Mag., $, 267, 1958.
Kobayashi, K., An experimental demonstration
magnetism. Similar conclusionshave been
of the production of chemical remanent mag-
reached recently by Smith and Fuller [1967], netization with Cu-Co alloy, J. Geomagnet.
who suggestthat the stableremanenceof hema- Geoelec., 12, 148, 1961.
 MAGNETISM OF INTERGROWN
Meikle•ohn, W. A., Exchange anisotropy; A re-
view, J. Appl. Phys., 33, 1328, 1962.
Meikle•ohn, W. A., and C. P. Bean, New mag-
netic anisotropy, Phys. Rev., 102, 1413, 1956.
Moriya, T., Anisotropic superexchangeinterac-
tion and weak ferromagnetism, Phys. Rev., 120,
91, 1960.
Nagata, T., Rock Magnetism, Maruzen Com-
pany, Tokyo, 1961.
MAGHEMITE AND ttEMATITE 5965
Smith, R. W., and M. Fuller, Alpha-hematite:
Stable remanence and memory, Science, 156,
1130, 1967.
Stacey, F. D., The physical theory of rock mag-
netism, Advan. Phys., 12, 46, 1963.
(Received February 28, 1968;
revised May 20, 1968.)