J. Inorg. Nucl. Chem., 1959, Vol. 9, pp. 113 to 123. Pergamon Press Ltd.

Printed in Northern Ireland

TOPOTACTICAL REACTIONS WITH FERRIMAGNETIC

OXIDES HAVING HEXAGONAL CRYSTAL
STRUCTURES--I
F. K. LOTGERING
Philips ResearchLaboratories, N. V. Philips' Gloeilampenfabrieken,Eindhoven,Netherlands
(Received 18 June 1958)

Abstract--A new method is described for the preparation of polycrystalline materials with oriented
crystals by reaction of the oriented grains of a strongly anisotropic fenimagnetic with non-oriented
grains of usually non-magnetic components. Using this type of reaction, for which the name
"topotactical (or "topotaxial") reaction" is proposed, oriented samples of BasCooZn~_~Fet40~l,
BaCo~Zn~_,sFe46027, Ba2Zn2Fet~O~2 and BaCo~Ti~Fe~2_~Ox0, which have related hexagonal crystal
structures, have been prepared as well as some ferrites having the cubic spinel structures.

THE present investigation deals with reactions between oxides of the system BaO-
MeO-Fe90 a in which Me represents a divalent metal like Mn, FeII, Co, Zn etc. In
this system ferrimagnetic compounds occur. We will briefly review some crystallo-
graphic and magnetic properties of these materials, which are described by JoN~:rg
e t al. (1)

BaO ,'V/eO
Fro. 1.--Composition diagram of the system BaO-MeO-FeTOa. BaFe12Olg(M), BaaMe2Fe24041(Z),
Ba2MezFelzO~2(Y), BaMezFe16Ozv(W), MeFe204(S) and BaFezO4(B ).

The most important compounds in the BaO-MeO-FezO 3 system (Fig. 1) are

BaFe12019 (denoted by M), BazMe2Fe2404x (MezZ), Ba~Me~Fel~Oz2 (MezY)
BaMe~Fe16027(Me2W), MeFe~O4 (S) and BaFe~O~ (B). M, MeeZ, Mez Y and MeoW
have closely related hexagonal crystal structures, C1,z) which can be considered to be
composed of layers with spinel structure (a cubic [111] direction of spinel being
parallel to the hexagonal axis) and of layers (with a characteristic structure) that
IX) G. l-[. JONKER,H, P. J. WIJN and P. B. BRAUN,Philips Techn. Rev. lg, 145 (1956); Proc. Instn. Electr.
Engrs. B 104, Supplement, 249-254 (1957).
(21 p. B. BRAUN,Philips Res. Rep. 12, 491 (1957).
113
114 F . K . LOTGERING

contain the Ba ~- ions. The two types of layers lie perpendicular to the hexagonal
axis and alternate in the c-direction. Combinations of spinel layers with a thickness
of 6.9 and 11.5 A with two types of layers containing Ba (with a thickness of.4,6 and
6.9 A) give a series of structures to which M, Me,Z, Me 2 Y and MezW belong. The
hexagonal unit cells of all these lattices have approximately equal a-edges' whereas
the c-edges are different. S has the well-known spinel structure; the crystal structure
of B is not known.
The most important magnetic property of the hexagonal ferrimagnetic compounds
is the fact that the crystalline anisotropy energy E~ is mainly determined by, and
strongly dependent on, the angle 0 between the direction of the magnetization and
the c-axis. To a first approximation the equation:
E K -~- K 1 sin 2 0
holds. If Ka is positive, the minimum of E~ occurs for 0 = 0 or 180°, i.e. a preferen-
tial direction for the magnetization is present. In the case of a negative K1, the
minimum occurs for 0 = 90 ° and the material has a "preferential plane" for the
magnetization. M, Me~Z and Me2 W, except for M e = C o , have a preferential direction,
Co,Z, Co~W and M% Y have a preferential plane for the magnetization, at room
temperature.
A complete series of mixed crystals ConMez_~Z between a compound with a
preferential direction (e.g. ZnzZ) and CozZ exist. In such a series Ka changes from a
positive value for 6 . = 0 to a negative value for ~ -= 1. For a certain value of 6, K1 is
zero and for a range of compositions around this 6 value K1 is small. A similar
behaviour occurs for Co~Znz_oW because K1 is positive for Zn~W and negative for
CozW.
In this laboratory GORTER~z) found a series of materials BaCooTi~Fe1~_2oO19
(up to ~ = 6), which will be denoted by Co~Ti~M. They are isomorphous with
BaFea2019 and can be derived from the latter compound by a substitution of Ti ~v q-
Co II for 2Fe m. For increasing 6, KI decreases and passes through zero so that for a
certain range of 6 the materials have a preferential plane for the magnetization
(at room temperature).
For certain purposes polycrystalline materials with crystals of which the c-axes
are oriented parallel to each other are desired in order to take the full advantage of
the characteristic anisotropy. ~4) Samples with such a texture have the same type of
magnetic anisotropy as the composing crystals, e.g. for negative K1 the material has a
preferential plane for the magnetization perpendicular to the e-axes. Crystals for
which K1 > 0 can be oriented in a static magnetic field, crystals for which K~ < 0,
in a rotating magnetic field. ~4) (The rotating field has the tendency to orient the
preferential planes of the crystals parallel to the plane in which the field rotates.)
Well-oriented samples can be obtained by orienting finely ground powders of, e.g.,
M, Zn2Z and ZnzW in static fields and of CozZ, Co~W and Me2Y in rotating fields
higher than approximately 2000 oersteds.
The present work is based on the following experiment, which was performed by
Dr. G. H. JONKERin this laboratory. A pellet was pressed from a mixture of BaFel20~9
and FezO 4 in the presence of a static magnetic field. Then the strongly anisotropic M
13~ E. W. GORTER, Proceedings Grenoble Conference on Ferromagnetism (1958).
~4~ A. L. STUYTS and H. P. J. WUN, Philips Techn. Rev. 19, 209 (1957).
 Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures--I 115

crystals are oriented with their c-axes parallel to the field whereas the weakly aniso-
tropic FeaO4 crystals are not oriented. By heating the mixture in a suitable gas
atmosphere the reaction
BaFea2019 q- 2FeHFe204 ----*BaFezIIFe160~(Fe2 u I41)
takes place. Dr. JONr,~R made the interesting observation that the hexagonal Fe~IIw
crystals of the polycrystalline reaction product were oriented more or less parallel to
the hexagonal M crystals in the initial mixture. In other words, the texture of the
M crystals in the initial mixture was retained in the Fe~I~W crystals.
Such reactions of a strongly anisotropic ferrimagnetic component, whose crystals
are oriented in a magnetic field, with other components, whose crystals are not
oriented in the field, open up the possibility of a fundamentally new method for the
preparation of oriented materials. For these reactions the name "topotactical
reactions" or "topotaxial reactions" is proposed (cf. Section 5). As Dr. E. W.
GORTER in this laboratory suggested, this new method, in which the anisotropy of
the final product plays no part, may be especially important for orienting materials
with such a low anisotropy that they cannot be oriented directly in a field.
Thi s paper describes an investigation of the preparation of oriented Co~Zn2_~Z,
CoaZn~_~W, Co~Ti~M and Ni~Znl_~Fe~O~using topotactical reactions.

1. C O M P O S I T I O N O F T H E I N I T I A L M I X T U R E AND
PREPARATION TECHNIQUE
The composition of the initial mixture for a topotactical reaction was chosen in
the following ways.
(a) The initial mixture contains one or-more ferrimagnetic components (like
M, Zn2Z, etc.) that are oriented in a field, and non-orientable components in such
quantities that the gross composition is equal to the composition of the desired
final product.
For the composition of Me,Z, Me2W or Me2 Y numerous compositions of initial
mixtures can be chosen with the aid of the BaO-MeO-Fe203 diagram (Fig. 1). A
mixture of M, BaO and MeO can have all gross compositions within the triangle
M-BaO-MeO, which contains the compositions of Me~Z and Me 2 Y. For example
Co~Zn2_aZ can be prepared from M, BaO, CoO and ZnO:

2BaFel~O19 ~' q- BaO q- ~CoO ~- (2 -- ~)ZnO ~ Ba3Co~Zn2_~Fe~4041

(Materials oriented by a static or by a rotating field are denoted by the symbols

or A_, respectively.)
For the preparation Of CoaTi,M, mixtures of M, Me2Z, Me2W or Me 2 Y with
additions containing TiO 2 can be used, e.g.

(~/2)BasCo~Fe24041_L q- (1 -- 3~/2)BaO q- 6TiOz -~ (6 -- 76)Fe20 3 --*

BaCo~Ti~Fe1~_2~O19 (for ~ ~ ])
(b) In the starting mixture a component containing Fe u is present and oxidation
takes place during the reaction, e.g.
~BaFe2IIFex~O27 ~ -q- ~BaCOz -k 2CoCO3 q- ] 0 3 --+ BazCo2Fe2~O41 + x3~CO2
116 F.K. LOTGERING

Method (a) is the more general and more practical method. Method (b) has the
disadvantage that the preparation of a material containing Fe xr is often laborious.
The preparation of the materials was carried out as follows. The initial mixture
was ground for 8 hr under ethanol in a vibration mill. From a wet slurry of the
powder a pellet was pressed in the presence of a static field of 8000 oersteds or a
rotating field of 3000 oersteds. The pellet was heated slowly in an oxygen atmo-
sphere, kept at 1250°C for a certain time and furnace cooled.

2. THE ESTABLISHMENT OF A TEXTURE AND THE ESTIMATION OF

THE DEGREE OF ORIENTATION
The texture of an oriented, polycrystalline material is defined exactly by a distri-
bution function giving the fraction of material with crystals having c-axes that make
a certain angle with the direction of orientation, as a function of the angle. The
texture cannot be described exactly by a single parameter because in general such a
distribution function will be determined by more than one constant. Since the
measurements of distribution functions for a series of samples is too cumbersome,
we have confined ourselves to establishing a texture and estimating the degree of
orientation semi-quantitatively in the following ways.
(a) X-ray diagram. When X-ray beams are reflected from the planes parallel to
the basal plane of an ideally oriented sample, then all (hkl) reflections except the
(001) reflections disappear from the X-ray diagram. In the X-ray diagrams of incom-
pletely oriented materials the (hkl) reflections still occur. The ratio of the intensities
of the (00/) and (hkl) reflections increases with improving orientation. The degree of
orientation was estimated by comparing the X-ray diagrams of the samples with that
of non-oriented material with the same crystal structure in the following way. (The
influence of the metal chosen for Me in Me,Z, Me~V and Me~ Y on the X-ray inten-
sities is very weak and can be neglected.)
From the X-ray diagrams the sum of the intensities of the (00/) reflections and the
sum of the intensities of all (hkl) and (00l) reflections (which occur in a certain range
of 0 values) were obtained and the ratio of the two sums was calculated for an oriented
sample (value p) and for the non-oriented material (value Po). For an increasing
degree of orientation p increase~ from the value P0 for the non-oriented sample to
the value 1.0 for an ideally oriented sample so that the quantity f---- (p -- p0)/(1 -- Po)
increases from 0 (non-oriented) to 1.0 (ideally oriented). The quantity f, which may
be considered as a measure of the degree of orientation (although of course f d o e s not.
describe the orientation distribution), was taken as a quality factor for the orientation.
The X-ray diagrams of the non-oriented samples were obtained with the aid of a high-angle
Norelco spectrometer. By this means sufficientresolution of the lines was obtained to enable/7o to
be determined with reasonable accuracy. Thep values for the oriented samples were estimated t'rom
X-ray diagrams in which the (001) reflections were partially overlapped by (hkl) reflections; This
procedure, however, is increasingly inaccurate for decreasing degree of orientation so that low
values of f are correspondingly inaccurate. Therefore, the ~ values are tabulated to one or two
decimal places for f smaller or larger than 0.8, respectively.
The orientation was further qualified as "very good" if the reflections (1.0.16) for
Me,Z, (1.0.11) for M e o w and (1.0.7) for M were absent or weak. (These being the
reflections that vanish last of all non-basal reflections for increasing degree of orien-
tation.) The term "good" was used if the non-basal reflections apart from the (hOl)
 Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures--I I 17

reflections mentioned above, arc weak, and the terms "moderate" and "poor" if the
(00l) reflections are respectively, considerably or only slightly stronger, than those for
non-oriented materials whereas several strong non-basal reflections are present.
(b) Initial permeabilities/~, and/z I. /~lt and/~1 are defined as the initial permea-
bilities at low frequency measured in fields Hll and Hi, parallel or perpendicular to
the direction of the c-axes of an oriented sample. If the magnetization is caused by
rotation processes then the following behaviour is expected for ideally oriented
material.
For large and positive values of K 1, the spontaneous magnetization vectors lie in
directions parallel or anti-parallel to the c-axes which are both preferential directions
for the magnetization. A weak field H i (perpendicular to the magnetization) causes
rotations of the magnetization vectors, but only over small angles because the vectors
are tightly bound to the preferential direction. Therefore #± differs only slightly
from unity. A field Ht~ parallel to the magnetization causes no rotation at all so that
u~ = 1 .
For large and negative values of K1, the magnetization vectors point in directions
lying in the preferential plane, which is perpendicular to the c-axes. H~l causes
rotations of the vectors out of the plane, but only over small angles as a consequence
of tight binding of the magnetization in the plane. Therefore /~tt is small. In the
plane, however, the rotation of the magnetization is practically free m so that a field
H. causes rotations over relatively large angles. Then #± is large.
It is evident that for non-oriented materials/~, and/~tJ are equal. For incompletely
oriented materials with a positive K1 the difference between #± and #, is small, #±
and #+l being both small. For incompletely oriented materials with a negative K1,
# . can be considerably larger than/~rl, the difference becoming larger for an increasing
degree of orientation.
/~_t and #~ were calculated from the self-induction of a coil with a cube-shaped
core of the oriented material, which was placed in a yoke of material with a permea-
bility larger than 1000. The self induction was measured at 2 Kc/s with the aid of a
Maxwell bridge.
(c) Orientation of a sample in a magnetic field. A field exercises on an oriented
sample a torque that has the tendency to orientate the sample with a preferential
direction of magnetization parallel to the field. From the behaviour of a sample in a
field the presence of a texture can be shown and the sign of K1 can be found.
(d) Microscopic investigation. Since the hexagonal crystals in the polycrystalline
samples usually have the shape of flat plates, which are parallel to the basal planes,
photomicrographs of surfaces parallel and perpendicular to the c-axes of oriented
material give an impression of the texture. The crystal boundaries were observed on
polished surfaces that were etched with hydrochloric acid.
(e) Shrinkage. During sintering, oriented samples show a greater shrinkage in
the direction of the c-axes than in the direction perpendicular to it.

3. EXPERIMENTAL RESULTS
CooZn2_+Z. Five different reactions I-V, Table 1, were carried out for the pre-
paration of Co+Zn2_0Z. The samples were fired 3 or 16 hr at 1250°C in an oxygen
atmosphere. From the X-ray diagrams it was concluded that the materials prepared
by the reactions II, lII and IV, were pure (i.e. contained at most traces of a second
118 F . K . LOTGERING

TABLE I. To TOPOTACTICAL REACTIONS CARRIED OUT FOR THE PREPARATION OF C o d Z n s _ d

Ba0Co~Zn~_eFe~,O~I, CoeZn~_eW = BaCoeZn~_eFeIoO~, CoeTieM = BaCoeTieFe~_~eOI. and
MeFe~O,
M~ANINO OF SrMEOtS: M = BaFe~O~0; Me, Y = Ba~Me~Fe~Om; t' and .I. oriented in a static
or rotating magnetic field, respectively

Orientation con-
eluded from the
No. Reaction equation
X-ray diagram
(see Section 2a)

I 2M 1' + BaCOs + ~CoCO0 + (2 -- 6)ZnO -+ CoeZn,_eZ + (1 + ~)CO2 poor

(6 = 0.5, 0.6, 0.7) ( f = 0.1)

II 6M~ + (1 -- 6/2)Zn°Z'f + zX-~BaCO3+ 6CoCO3

Co~Znz_0Z + ~ C O z moderate-good
(6 = 0"5, 0'6, 0-7, 1"0) 0'3 < f < 0"7

III (1 ---"6/2)Zn~Zt + -~BaCOs + tSCoCOs + 6~Fe~O°

Co0Zn°_eZ + z-~Co, good-very good
(6 = 0"5, 0"6, 0"7, 1"0) 0"6 < f < 0"91

IV (6/2)Co2ZJ. + (1 -- 6/2)ZnzYJ. + (1 -- ~/2)BaCO8 + (6 -- 36)FesOs

--,-CoeZn~_oZ + (1 -- 6/2)C0~ good
(6 = 0.5, 0.6, 0.7, 1.0) 0.7 < f < 0.8

V ~Fe,IZWt + ~BaCO0 + 2COCO0 + ~O,--+ C o , Z + tz-~CO, moderate ( f =

0.2)

V1 M~ + ~CoCOs + (2 -- 6)ZnO + 2Fe~O8 --+ Co0Zn°_a W + 6CO~ good-very good

(6 = 0.6, 0'7, 0-8, 1.0) 0"5 < f < 0"89

VII ~Zn,ZJ" + ~CoCOs + (~ -- ~)ZnO + 4Fe°O0 ~ CoeZn°_eW + 6CO2 good

(6 = 0"6, 0.7, 0.8, 1.0) 0.5 < f < 0.84

VIII ~Co~Z.I. + (6 -- §)CoCOs'+ (2 -- 6)ZnO + 4Fe,O,

CoeZn~_eW + (6 -- §)CO, good-very good
(6 = 0.7, 0'8) 0-8 < f < 0"98

IX (1 -- 6/6)M'f + 6/6BaCOa + 6CoCOs + 6TiO~ -+ CoeTi~M + 67-~CO2 good-very good

(6 = 1.1, 1.3, 1.5) 0.5 < f < 0.97

X ~'CoaZ.I. + a~o3CoCOs + ~TiO2 + t-~TiFe~O5 ~ Col.xTit.tM + ~ C O 2 moderate ( f =

0.3)

XI ~X~Fe~rl.0TiI.0M?+ ~rBaCO0 + COCO° + a~rTiO, + C-d3,

Col.0Til.0M + -~CO° good ( f = 0.5)

XII ½Zn~Zt + ½BaCO3 + ZnO ~ Zn2 Y + CO~ poor ( f = 0.2)

XIII Co°Wt + 5CoCOs--* 7CoFe°O4 + BaFe,O4 + 5CO,

XIV Nit Wt -F 5ZnO--+ 7Ni,/vZnu~FesO° + BaFe°O4

XV Z n j W t + 5NiCO° ~ 7Zn,t~Bi°nFe,O4 + BaFe~O~ + 5CO2

 Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures--I 119

phase) and well oriented. The X-ray diagram of one of the best oriented preparations
is given in Fig. 2. Reaction 1 gave materials that contained contaminations of other
phases (M and Me~ Y) and were oriented poorly. Reaction V gave a pure product
with a moderate orientation.
In Table 2 the values of/~e and F± and other data of some preparations are given.

z ~ W
non -oriented non-oriented

' ;A£r A
I

d~3 46
i 50 3~ 12 25 sb
eo
-----~3e -----~ 2 e

Co~ Znl~ Z Coi~Zn~oW

topotacticaUy topotocticatly
oriented oriented

¢.

.~ ~ . . j
34 38 ~2 1,6
---~ 2e
SO 3'o 3~ 3e ,2 ,6 ~o',
FIG. 2.--X-ray diffraction diagrams of non- FIG. 3.--X-ray diffraction diagrams of non-
oriented and "very well" oriented Me=Z oriented and "very well" oriented Me=W
(CoK= radiation). (CoK= radiation).

The small values of/trr and F.t for a low Co content (~ ---- 0.5) are explained by a
positive K1; the small/zl= and much higher/~± values for higher Co contents (dt =
0.7 or larger) are consistent with a negative K1 (see Section 2b). The considerable
difference between/~, and #.t in the cases of a negative K are on indication of a
good orientation. The change from a positive to a negative value of K1 occurs between
(~ ---- 0.5 and (~ --~ 0-7; thus K1 passes zero for (~ in the neighbourhood of 0.6.
For some samples the texture was microscopically investigated (see Section 2d).
Fig. 5 shows the photomicrographics of surfaces parallel and perpendicular to the
120 F.K. LOTGERING

c-axes. These pictures confirm the presence of a good orientation, as was concluded
from the X-ray diagrams.
CooZn2_~IV. These materials were prepared by the three reactions VI, VII and
VIII, Table 1. All samples were pure and well or very well oriented (see Fig. 3).
F r o m the #x and #, values (Table 2) it is seen that K1 is positive for 8 = 0"6 and
negative for 0.7. Titus K 1 passes through zero for 0.6 < ~ < 0.7.

~1 t4
I ~ non-oriented

?l .111 2,

"llllo
31" 38 43 1.6
,~3e $0

a?

topotocti
orientedcotly

FIG. 4.--X-ray diffraction diagrams

of non-oriented M and "very well"
oriented CoTiM (CoK~ radiation).

i i i I
3~ 3# 42 /.6 ~0
3e

Co~TioM. The 'reactions IX and XI gave pure and well or very well oriented
materials (see Table 1 and Fig. 4). The final product of reaction X was pure, but
moderately oriented. F o r ~ = 1"1, #± is considerably larger than #~ (Table 2), from
which it is clear that the material has a preferential plane of magnetization.
Zn2 Y. Reaction XII gave pure, but poorly oriented Zn~ Y.
Me2Z, Mes W and Co~Ti~Mare formed more easily from mixtures that contain M, MezZ or MezW
as a component than from mixtures of BaO, MeO, Fe~O8 and TiO~. This was shown as follows.
Samples of CoZnZ and CoZnW were prepared from BaCOs, ZnO and FeaO3 and by reactions
 Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures~I 121

11, 111, IV, VI and VII without applying a magnetic field. All samples were fired during 3 hr in
oxygen. The reaction products of BaCOn, CoC% etc. contained considerable amounts of foreign
phases whereas for reactions II, III, IV and VII no second phase and for reaction VIa small amount
of foreign phase was found in the final product.
Dr. GORTER found that CooTi~M prepared from BaCOz, CoCO~, TiO~ and F%O~ is always
contaminated by a small amount of CoFe204. This was concluded from the shape of the magnetiza-
tion vs. temperature curves, which show a tail between the Curie temperatures of Co~Ti0M and
CoF%O4 (520°C). This tail is practically absent for Co~TioM prepared by reaction IX.

TABLE 2.--SPECIFIC WEIGHTd, d.c. SPECIFICRESISTIVITYr, #± AND ~11 FOR SOME TOPOTACTICALLY
ORIENTEDCod7~n2_~Z, CodZn2_8 W AND Co~TioM PREPARATIONS
I
Orientation con-
Reaction Heat cluded from the
r
Composition (see treatment d ,tll. ttll X-ray diagram (see
(f2 cm)
Table I) (hr--'C) Section 2a) f values
between brackets

Co0.sZnl.aZ !} }i 5.2 102 5 8 - - - -

Co0.6Znl.4Z i 5'2 102 7 10 good (0.7)

Co0.7Zn1.3z 1I 16-1250° 5.2 102 40 14 moderate (0'5)
Co Zn Z 3-1250 ° 5'1 10a 32 5 good (0'5)
102 5 9 good (0'6)
Coo.6Znl.aZ III i 16-1250 ° 5.2 102 8 12 very good (0.91)
Co0.7Znl.aZ I 5'2 102 41 10
Co Zn Z I ~ 3-1250 '~ 5.1 103 55 4 good (0'7)
Co0.sZnl.sZ } }~ 5'1 10a 4 9 good (0'75)
Co0.7Znl.zZ IV 3-1250 ° 4.8 10~ 23 10 good (0"75)
Co Zn Z ~ 5.2 10a 35 5 good (0.7)

C°°6Zn14WI1
C°°TZnl'3 W
Co O.sZn~.~W
Co Zn W
V1 3-1250 ~
4"3
__
4"3
4'3
107
lOs
108
108
22
20
12
35 75
7
7
5
good (0"6)
good (0.7)
good (0'7s)
good (0'89)
C°o.8Znl.2 W /
Co Zn W I
VII }! !
3-1250 ° 3'7
2'8
108
108
21
85
5
3
good (0'6)
good (0'84)
Co0.7Zn1.3 W 4"6 108 15 23 good (0'80)
VIII !! 3-1250 °
C°o.sZn~.2W / 3'3 10s 19 5,~ very good (0"86)

C°IITilIM } ) 4.5 l0 s 47 75 very good (0.97,)

Co 1.3Til.3M IX 3-1250 ° 4.4 108 9 2 good (0'75)
COl.sTil.5M 4.2 108 7! 15 very good (0'89)
i

M e F e 2 0 a. A mixture o f 84 wt. per cent ferrimagnetic M e F e 2 0 a a n d 16 wt. per

cent n o n - m a g n e t i c B a F e 2 0 4 was p r e p a r e d a c c o r d i n g to the reactions X I I I , X I V a n d
XV, T a b l e I, b y firing the samples for 2 hr at 1250 °.
The M e F e z O 4 crystals show an o r i e n t a t i o n o f cubic [111] axes p a r a l l e l to the c-axes
o f M % W in the initial mixture, i.e. the same c o r r e l a t i o n as exists in the M % W struc-
ture between the c-axes a n d one cubic [111] axis o f the spinel layers (see i n t r o d u c t i o n ) .
The presence o f such a texture was cot, eluded f r o m X - r a y d i a g r a m s o b t a i n e d with
X - r a y b e a m s reflected f r o m the plane p e r p e n d i c u l a r to the c-axes o f the o r i e n t e d
M % W crystals in the initial mixture. The ratio o f intensities Ihhh/Ihk t o f a (hhh) a n d
a (hkl) reflection is larger t h a n this ratio I°hhJI°hk ~ for n o n - o r i e n t e d material. I f
122 F.K. LOTGERING

lhhJ°hkJlhkJ°hhh is larger than unity the above-mentioned texture is present and the
orientation is the better, the larger the ratio. From the values found for this ratio
it was concluded that reactions XIII and XIV gave a better oriented product than
reaction XV.
The presence of such a texture was confirmed from the orientation in a magnetic
field of a sample cut in the shape of a disk parallel to the [111] axes (cf. Section 2c).
The NiZn-ferrite samples had uniaxial anisotropy. The CoFe204 sample showed
two equilibrium positions making an angle of 110°.
This behaviour is expected from the well-known preferential directions of magneti-
zation for NiZn-ferrite and CoFe204, which are parallel to the cubic [111] and [100]
axes, respectively. For the oriented NiZn-ferrite the direction of the oriented [111]
axes is thus also the preferential direction of magnetization, and the disk has an
uniaxial magnetic anisotropy. In the CoFe20 4 sample, the cubic [100] directions of
the oriented crystals make angles of 55 ° with the direction of the oriented [111] axes
so that these preferential [100] directions of magnetization lie on the surface of a cone.
Thus there are two preferential directions which make an angle of 2 × 55 = 110°
with each other in a plane that contains the axis of the cone.

4. D I S C U S S I O N
From the fact that in, for example, reaction VI, the CooZn2_~W crystals have the
same orientation as the M crystals and that in the initial mixture only the M crystals
are oriented, it is evident that the orientation of the Co~Zn2_oW crystals is caused by
chemical reactions that take place inside or on the M crystals. Such reactions are
called topochemical reactions. (s) Since the formation of a new phase starts with
nucleation, we propose the following picture. At first small Co~Zn~_~W crystals
(nuclei) originate inside the M crystals with the e-axes (and perhaps also the a-axes)
of the two crystals parallel to each other, i.e. the M crystals act as a substrate for the
epitaxial (6) growth of oriented Co~Znz_~W nuclei. The crystals present in the final
product are then formed by further growth of W on these nuclei.
If a strong preference exists for nucleation of the final product on the crystals of
the oriented component, which is only a fraction of the mixture, the amount of
oriented material may increase considerably during a topotactical reaction. This is
found for example in reaction VIII, which gives a well-oriented reaction product
although the initial mixture contains only 53 wt. per cent magnetically orientable
component (for 6 ----- 1). If, however, a non-oriented crystal phase of the mixture acts
preferentially as a substrate for the final product, considerable amounts of a non-
oriented final product are formed. This may be the case for the reactions 1 and Xll,
which give poorly oriented final products although the percentages of the magnetically
orientable components (viz. 89 wt. per cent) are much higher than for reaction VIII.
From these examples it is seen that the amount of oriented component in the initial
mixture does not seem to be the determining factor in the orientation of the final
product. This is an indication that certain crystal phases act preferentially as a"
substrate for the nucleation of a new phase during topotactical reactions.
Although a topotactical reaction is assumed to be initially an epitaxial process,
~) F o r a definition of t o p o c h e m i s t r y see: H. REMY, Treatise on hwrganic Chemistry Vol. I l, p. 756. Elsevier,
A m s t e r d a m (1956).
(07 F o r a definition o f epitaxy see: A. NEUHAUS, Fortschr. Min. 29/30, 129 (1950151).
 Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures--I 123

the reactions described show an essential difference from epitaxy. The final product
of an epitaxial process is an intergrowth of the new phase and the substrate whereas
the substrates disappear completely during the reactions described above and the
final products consist of only one phase (as in reactions I-XIII). In some cases--
e.g. in reaction XIIl--the final product of a topotactical reaction contains two phases,
but the crystal orientations in one phase (e.g. the S phase) bear no correlation to
those in the other phase (e.g. the B phase), so that the epitaxial intergrowth of two
crystal phases does not occur.
The term topochemistry covers the reactions described but also a great number
of different phenomena. Therefore we propose the term "topotaxy" for all chemical
solid state reactions that lead to a material with crystal orientations which are corre-
lated with crystal orientations in the initial product.
The results of further investigations of topotactical reactions will be published
shortly.

Acknowledgement--The author is greatly indebted to Mr. J. VERBERKTfor carrying out the experi-
ments.