~ Solzd State Comanunzcatlons, Vol.50,No 6, pp.497-499, 1984 0038-1098/84 $3.

00 + 00
Prlnted zn Great Brltaln. Pergamon Press Ltd

MAGNETIC PROPERTIES ~ CRYSTAL STRUCTURE OF Nd2Fel4 B

D. G1vord +, H.S Lz + and J.M. Moreau*

+Laboratozre Louzs N~el, C.N.R.S , 166X, 38042 Grenoble-c~dex, Prance

*Laboratozre de Structure de la Matz~re, Unzverszt~ de Savoze,

9, rue de l'Arc-en-Czel, 74019 Annecy-le-V1eux, Prance

(Neceived 16 February 1984 by E.F. Bertaut}

Outstandlng permanent magnet propertzes have recently been reported to

occur zn ternary compound Nd-Fe-B I . The tetragonal crystallographlc
structure of thls compound Nd2FeI4B zs determzned (space group P42/mran) .
This structure zs related to the hexagonal CaCu5-type structure whzch
is the fundamental basis for the crystal structure of many rare earth-
transztlon metal compounds.

Des proprz~t~s d'almant permanent exceptzonnelles ont ~t~ r~cemment

observ~es dans un compos~ ternazre Nd-Fe-BI. La structure crzstallogra-
phzque de ce eompos~, Nd2FeI4B, de sym~trze quadratlque a ~t~ d~termz-
n~e (groupe d'espace P42/mnm) Cette structure est relz~e ~ la struc-
ture hexagonale de type CaCu5 quz est la base fondamentale de la
structure crzstallographzque de nombreux compos~s terre rare-m~taux de
transltlon.

Introductlon compounds would be very meanzngful We report

The magnetzc behav~ours, observed zn rare
earth-transltzon metal-rzch compounds, are the
basis for the understandzng of the outstandzng
permanent magnet propertzes encountered zn
SmCo 5 and Sm(Co-Fe) 7 alloys. In these systems,
the large 3d magnetzc znteractzons determzne
orderzng temperatures well above room tempera-
ture. The magnetzc couplzng, between transztzon
metal and rare-earth atoms, allows the large
anlsotropy, cbmracterlstlc of 4f ions, to
perslst at room temperature. Most of these
binary alloys crystallzze zn structures whzch
are derzved from the CaCus-type structure. It
turns out that very generally Co atoms exhlbzt
unzaxzal anzsotropy whereas Fe atoms have
basal plane anzsotropy. S1mzlarly, rare-earth
ions for whzch the Stevens ~ coeffzclent zs
posztlve (Sm,...), have unlaxlal anzsotropy,
unlzke zons for which ~ zs negatzve (Pr, Nd,..),
wnere the anzsotropy favours the basal plane
These characterzstzc propertzes explazn that,
despzte numerous attempts, Sm and Co are
necessary baszc elements zn order to obtazn
permanent magnet propertzes zn thzs famzly of
alloys. Yet, it would be very attractzve to
substztute Pr or Nd to Sm whose magnetzc
moment zs fazrly small and Fe to Co whzch zs
very expenslve. Thzs zs preczsely what achzeved
recently Sagawa et al I . In the ternary system
Nd-Fe-B, they observed a quadratzc phase zn
whzch both Nd and Fe atoms exhzbzt unzaxzal
anzsotropy. Permanent magnets wzth energy
product as hzgh as 38 MGOe were obtazned by
powder metallurgy. For a better understandzng
of the above magnetic propertzes, the knowledge
of the exact crystal structure of these new
the atomzc structure of thzs compound whose
composztzon zs determlned to be Nd2FeI4B
Experlmental
The alloys were prepared from commerczally
avazlable elements of hzgh purzty (Nd 99.9 %,
Fe : 99.99 %, B : 99.99 %). Samples were
obtazned by znduction meltzng in a so-called
cold cruclble. Small crystals were observed to
grow zn shrznkage cavztzes obtazned after slow
coollng of the melt under vacuum. A crystal
wzth approxlmately the shape of a sphere of
0.3 mm dzameter was zsolated Laue photographs
revealed the tetragonal symmetry
Single crystal zntenszties were measured
wlth gra~hlte monocnromated Mo K~ (~ =
0.71069 ~) radzatlon on a CAD-4 ENRAF-NONIUS
dzffractometer zn the @/2@ scan mode , accurate
cell dlmenslons determzned by leastTsquares
analyszs of 25 0 values (a = 8.792 A,
c = 12 190 A). Three standard reflectzons were
monztored at zntervals of 3600 s wzth zntenszty
varzatzon durzng the data collectzon < 1 % .
Intensztzes of 1153 zD~ependent reflectzons, to
a izmzt of @ = 35 °, were measured and corrected
for background, Lorentz and polarzzatzon fac-
tors wzth the program START 2. Systematzc
extznctzon (0kl k+l = 2n) revealed the space
group to be P42/mnm zf centrosymmetric, the
crystal structure was solved by dzrect methods
wzth the program MULTAN 3. The posltzons of the
Nd, Fe and B atoms were revealed from E map
and dzfference Fourzer maps. The szngle crystal
bezng a p p r o x m a t e l y spherzcal, spherical
absorptzon correctlons (SAC) were applzed wzth
~R = 4.5 (31.1 < SAC < 122.). Full matrzx

497
498 MAGNETIC PROPERTIES AND CRYSTAL STRUCTURE OF Nd2Fel4 B Vol 50, No. 6

least-squares refznement of posztzonal and Table I

zsotropzc thermal parameters converged after a
few cycles uszng F values of 874 reflectzons Posztzonal parameters and standard devlatlons
wzth I > 3~ (I) (Rw = 0.098) There was a zero
shzft/error in the fznal least-squares cycle.
All calculatzons were performed on a PDP 11/23 Atom szte x y z
computer uszng the SDP program system2 Atomzc
posztzons are izsted zn Table I, znteratomzc Nd I 4f 0.3572(3) 0.3572(3) 0.000
dzstances are zn Table 2 The chemzcal compo-
sztlon deduced from the refznement zs Nd2FeI4B. Nd 2 4g 0.7698 0.2302(3) 0.000
The calculated denszty zs 7.62 g/cm 3 zn Fe I 4e 0.000 0.000 0 116 (I)
excellent agreement wzth dzrect measurement on
large szngle crystals Fe 2 4c 0.000 0.500 0.000
Fe 3 83 0 0978(5) 0.0978(5) 0.2942(9)
Fe 4 8] 0.3184(5) 0.3184(5) 0.255 (I)
Dlscusslon
Fe 5 16k 0.5670(5) 0.2245(5) 0.3735(6)
A schematzc representatzon of the crystal- Fe 6 16k 0.1397(5) 0.5370(4) 0.1759(8)
lographzc structure zn z = I/2 zs presented on
B 4f 0.124 (8) 0.124 (8) 0.000
Fzgure I. Nd atoms form alternate arrangements
of large and small nearly regular rhombus zn
z = 0 and z = I/2. In z ~ 0 13, 0.37, 0.63 and Table 2
0.87, Fe atoms are arranged in an almost planar o

net of slzghtly deformed hexagones and Interatomzc dlstances zn Nd2Fel4 B (zn A).
trzangles The planar arrangements zn z = 0.13
and 0.87 are superzmposed, as well as those zn Nd I = INd I 3.552 Fe 4 = INd. 3.143
0.37 and 0.63. The arrangement zn z = 0.13 can 2Nd 2 3 795 INd~ 3.049
be deduced by a rotatlon of 30 ° from that zn 2Fe 2 3 382 IFe I 2.754
z = 0.37 In z = 0 25 and 0.75, the Fe 4 atoms 4Fe 3 3.306 2Fe 3 2.633
are practzcally superlmposed to Nd atoms zn 2Fe 4 3.143 lFe 3 2,784
z = 0 and 0.5 Fe 2 atoms are at the center of a 4Fe 5 3 066 2Fe 5 2.748
double trzgonal przsm. Fznally the boron atoms 4Fe 6 3.279 2Fe 5 2.734
are approxnnately at I/3 and 2/3 along the IB 2 894 2Fe 6 2.640
dzagonal of the large Nd rhombus. 2Fe 6 2.662
Conszderzng the large rhombus of Nd atoms
(Fzgure I) the slmzlarlty wzth the CaCu5-type Nd 2 = 2Nd I 3.795 Fe 5 = INd. 3.066
structure zn whzch crystallzze RCo 5 and RNz 5 2Fe I 3 192 lNd~ 3.060
compounds is very strzkzng The Nd-Nd znter- 2Fe 2 3.118 1Fe 1 2.496
atomzc dzstance reaches 5.2 ~ to be compared to 2Fe 3 3. 296 IFe 2 2.573
5 A in NdCo 5 Boron atoms occupy the same 2Fe 4 3. 049 IFe 3 2.587
posztlon zn the rhombus of R atoms as zn 4Fe 5 3.060 IFe 4 2.734
RCo3B24 and related compounds, they replace Co 4Fe 6 3 069 IFe 4 2.748
atoms of the szte 2c zn RCo 5 The Fe atoms zn 2B 3 254 IFe 5 2.592
z = 0.37 and 0.63 form s lmllar hexagonal prlsms IFe 6 2.527
as transztzon metal atoms of the szte 3g zn Fe I = 2Nd 2 3 192 IFe 6 2.462
RCo 5 compounds The center of these prlsms zs IFe I 2.826 IFe 6 2.536
occupzed by Nd atoms. It can be conszdered that 2Fe 3 2.491 IB 2.096
Fe 4 atoms zn z = 0 25 and 0.75 are substztuted 2Fe 4 2.754
to Nd atoms zn the RCo 5 structure These Fe 4 4Fe 5 2 496 Fe 6 = 1 Nd. 3.279
atoms are at the center of a hexagonal antz- 2B 2 095 1 Nd~ 3 069
przsm Such a polynedron is smaller than the IFe 2 2.492
regular hexagonal przsm observed around the Fe 2 = 2Nd 1 3.382 IFe 3 2.396
bzgger Nd atoms. 2Nd 2 3.118 IFe 4 2.662
In concluszon, the tetragonal structure of 4F e 5 2.573 IFe 4 2.640
thzs new ternary compounds Nd2Fel4 B zs closely 4Fe 6 2 492 IFe 5 2.527
related to the CaCu5-type structure Yet, the IFe 5 2.462
easy dzrect~on of magnetzzatzon zs along the Fe 3 = 2Nd 1 3.306 IFe 5 2 536
c-axzs unlzke the other blnary compounds where 1Nd 2 3 296 IFe 6 2.542
sd exhzbzts planar anlsotropy. Thzs behavzour IFe 1 2.491 2F e 6 2.549
whzch zs essentzal for tne permanent magnet IFe 3 2.433
propertzes observed zn Nd2Fel4 B must be 2F e 4 2.633 B = INd I 2.894
attrzbuted to the change zn envzronment of Nd IFe 4 2 784 2Nd 2 3.254
atoms whzch results from the substztutzon of Fe 2Fe 5 2.587 2Fe 1 2 095
atoms to half the Nd ones 2Fe 6 2.396 4Fe 5 2.096
Vol. 50, No. 6 MAGNETIC PROPERTIES AND CRYSTAL STRUCTURE OF Nd2FeI4B 499

F1$ure l : Schematlc representatlon of the

crystal structure of Nd2FeI4B. Nd atoms, B
atoms and Fe 2 atoms are at z = I/2. For all the
other Fe atoms, there is one atom above and one
atom below the plane z = 1/2 whlch appear at
the same posltlon on the flgure. The assoclated
couples of z values are iD~icated in unit of c.
A same couple holds for all atoms of the same
slte and is indlcated only once for clarlty
The square, in heavy llne, represents the unlt
cell of the quadratlc structure. The rhombus,
In heavy llne, schematlzes the unlt cell of the
CaCu5-type structure.

References

I. M. Sagawa, S. Fu31mura, M. Togawa, G. Germaln, J.P. Declercq and M.M. Woolfsen,

H. Yamamoto and Y. Matsuura, J. Appl. Phys.
March 1984 (to appear).
2. B.A. Frenz, Structure determlnatlon package,
Enraf-Nonlus, Delft, Holland (1983).
3. P. Maln, S. Flske, S.E. Hull, L Lesslnger,
Multan 80, Unlv of York, England and
Louvaln, Belglum (]980)
4. Y.B. Kuz'ma and N S. B11onlshko,
Krlstallograflya, 18, 710 (]973)