948

Acta Cryst. (1961). 14, 948

Gadolinium and D y s p r o s i u m Intermetallic Phases. II. Laves P h a s e s

and Other Structure Types
BY N. C. BAENZIGER AND J . L. IV[ORIARTY, JR.
Department of Chemistry, University of Iowa, Iowa City, Iowa, U . S . A .

(Received 17 June 1960 and in revised form 21 November 1960)

Unit-cell dimensions a n d interatomic distances are given for the following phases: MgCu 2 t y p e :
GdX~ and ]:)yX2 where X - - P t , Mn, Fe, Co, Ni and A1; CsC1 t y p e : G d X and D y X where X = Ag,
Cu, In, T1 and A1; AuCu 3 t y p e : G d I n 3, D y I n 3, DyTI3, D y P t 3 ; MoSi~ t y p e : GdAge, DyAg~, GdAu2,
DyAu2 ; CuTi 3 t y p e : D y z I n ; CaZn 5 t y p e : GdNi 5, D y N i 5, GdCo 5, D y C % ; A1B 2 t y p e : GdGa 2, DyGa2;
SnNi3 t y p e : GdA13.

Introduction arc f u r n a c e consisting of a r e m o v a b l e w a t e r - c o o l e d

h e a r t h a n d t u n g s t e n electrode w i t h p o w e r s u p p l i e d b y
T h e r a r e - e a r t h m e t a l s p r o v i d e a n o p p o r t u n i t y to t e s t
a 400 a m p . d.c. welder. E a c h s p e c i m e n was r e m e l t e d
t h e effect of a t o m i c size in t h e s t r u c t u r e s of inter-
r e p e a t e d l y to i m p r o v e h o m o g e n e i t y . If t h e f i n a l w e i g h t
m e t a l l i c phases. R e a s o n a b l e q u a n t i t i e s of g a d o l i n i u m
differed s i g n i f i c a n t l y from t h e i n i t i a l w e i g h t of t h e
a n d d y s p r o s i u m m e t a l s are n o w available, so t h a t a
a l l o y i n g m e t a l s , a chemical a n a l y s i s was p e r f o r m e d
f a i r l y e x t e n s i v e i n v e s t i g a t i o n of t h e i r a l l o y i n g b e h a v i o r
is possible. As a r e s u l t t h e b i n a r y a l l o y s y s t e m s of
gadolinium and dysprosium with twenty-one metallic
Table 2. MgCu2 structure type(1)
e l e m e n t s h a v e b e e n studied. F o r purposes of r e p o r t i n g , Interatomic distances: Gd has 12M at (D), 4Gd at (E)
M has 6M at (F), 6Gd at (D)
t h e e l e m e n t s h a v e been d i v i d e d i n t o four g r o u p s :
g r o u p A : Ti, V, Cr, Zr, Nb, Mo, Ta, W ; g r o u p B : a a(a) Vol. D E .F
(h) (h) (Az) (h) (h) (A)
Mn, Fe, Co, N i ; g r o u p C: Cu, Ag, Au, P t ; g r o u p D :
GdPt~ 7"6349 0-0008 445"05 3"165 3"306 2"699
A1, Ga, I n , T1, Ge. T h e r e a d i l y i d e n t i f i e d i n t e r m e t a l l i c (3) 7.637 0.001
p h a s e s a r e r e p o r t e d in t h i s paper. A d d i t i o n a l p h a s e s (3) 7.577
h a v e b e e n f o u n d , b u t t h e i r s t r u c t u r e s are y e t to be GGMn2 7.732 0.001 462-2 3.205 3-348 2.733
confirmed. (4) 7.751
(5) 7.724 0.005
Experimental methods
GdF% 7.389 0.003 403.4 3.063 3.200 2.612
Alloys were first prepared from pure metals (analyses, (4) 7.445
Table 1) with stoichiometries corresponding to alloys (5) 7.39 0.01
previously reported in the analogous systems with GdC% 7.258 0.003 382-3 3.009 3.143 2.566
La, Ce, Pr, or Nd. In addition, alloys were prepared (5) 7.255 0.005
with stoichiometries intermediate between these single GdNi 2 7.2056 0.0009 374.12 2.987 3.120 2-547
p h a s e regions a n d a n y o t h e r single p h a s e region sub- (5) 7.202 0.005
s e q u e n t l y recognized. GdA1.z 7.9020 0.0005 493.41 3.276 3.422 2.793
(5) 7.900 0.005
Table 1. Alloy materials DyPt 2 7.5966 0.0007 438.39 3.149 3-289 2.685
Metal ~/oMetal Metal % Metal DyMn~ 7.5731 0.0008 434.33 3-139 3-279 2.677
Gadolinium RI07 99-8+ Cobalt 99-4 (5) 7.564 0.005
Gadolinium **Subl. 98.2 Nickel 99.5 DyFe~ 7.321 0.001 392.4 3.035 3.170 2.588
Gadolinium *R160 99.14 Copper 99.9+ (5) 7.325 0.01
Dysprosium R159 99-9+ Silver 99.9+
Titanium 99"5 Gold 99"99 DyC% 7.190 0.004 371.7 2.980 3.113 2.542
Chromium 99.95 Germanium 99.9999999 (5) 7.187 0.005
Zirconium 99-0+ Platinum 98.5 to 99.0 DyNi 2 7.142 0.004 364.3 2.961 3-093 2.525
Niobium 99.4 Gallium 99.99 7.155 0.005
Molybdenum 99-966 Aluminum 99"9+ (5)
Tantalum 99.8 Indium 99.0 + DyA12 7.835 0.001 481.0 3.248 3-393 2.770
Tungsten 99.9 Thallium 99.95 (5) 7.840 0-005
Manganese 99.9 + Iron 99.8 (1) Strukturbericht, 1,490 (1931).
Vanadium 99- 5 + (3) Compton & Matthias (1959).
(a) Dwight (1961).
The alloy specimens, 10 to 15 g. in size, were melted (4) Endter & Klemm (1944).
under half an atmosphere of argon in a small electric (5) Wernick & Geller (1960).
 N . C. B A E N Z I G E R AND J. L. M O R I A R T Y , JR. 949

u s i n g e i t h e r s t a n d a r d w e t c h e m i c a l p r o c e d u r e s or f l a m e T h e d i f f r a c t i o n p a t t e r n s of t h e a l l o y s of Gd a n d D y
spectrophotometry. w i t h t h e m e t a l s of g r o u p A s h o w e d lines o n l y of t h e
X - r a y d i f f r a c t i o n p o w d e r p h o t o g r a p h s were m a d e m e t a l s a n d n o n e c o r r e s p o n d i n g to i n t e r m e d i a t e phases.
of t h e a l l o y s p e c i m e n s i n e i t h e r t h e ' a s - m e l t e d ' or T h e b a c k - r e f l e c t i o n regions of t h e s e X - r a y d i a g r a m s
a n n e a l e d condition. F i l i n g s were a n n e a l e d in v y c o r were c o m p a r e d v i s u a l l y w i t h s i m i l a r regions of dia-
capillaries ' g e t t e r e d ' w i t h z i r c o n i u m wire. T h e X - r a y g r a m s of t h e p u r e m e t a l s p r e p a r e d w i t h t h e s a m e
p h o t o g r a p h s were m a d e w i t h a 57-3 m m . r a d i u s D e b y e - camera. S i g n i f i c a n t c h a n g e s in t h e line p o s i t i o n s
Scherrer camera with Fe K s radiation. Metallographic o c c u r r e d o n l y for Gd in t h e G d - Z r s y s t e m a n d for D y
e x a m i n a t i o n was carried o u t on t h e m a c r o s p e c i m e n s i n t h e D y - Z r s y s t e m . T h e lines d u e to t h e r a r e - e a r t h
to d e t e r m i n e t h e h o m o g e n e i t y a n d to i d e n t i f y t h e m e t a l s h i f t e d in a d i r e c t i o n i n d i c a t i n g a s m a l l e r cell
p h a s e s p r e s e n t . ~Sicrohardness m e a s u r e m e n t s (Eber- d i m e n s i o n s . Since t h e size of t h e Zr a t o m is s m a l l e r
bach) were also u s e d to help i d e n t i f y t h e p h a s e s p r e s e n t t h a n t h a t of t h e r a r e - e a r t h m e t a l s , it a p p e a r s t h a t
in t h e m i c r o s t r u c t u r e s . s o l u b i l i t y is v e r y s m a l l in t h e r a r e - e a r t h m e t a l s e x c e p t
for Zr, a n d t h a t t h e r a r e - e a r t h m e t a l s do n o t dissolve
T a b l e 3. CsC1 structure type(l) a p p r e c i a b l y in t h e g r o u p A m e t a l s . H o w e v e r , since
Interatomic distances: Gd has 8M at (D), 6Gd at (a) e x t e n d e d a n n e a l i n g t r e a t m e n t s a n d p r e c i s i o n cell
M has 8 Gd at (D), 6M at (a) d i m e n s i o n d e t e r m i n a t i o n s h a v e n o t y e t b e e n per-
a (h) a(a) (A) Vol. (~3) D (A) formed, d e f i n i t e s o l u b i l i t y l i m i t s c a n n o t be given.
GdAg 3.6476 0.0008 48.53 3-157
GdCu 3.503 0.001 43.0 3.034 T a b l e 6. A1B2 structure type (hexagonal)(1)
GdIn 3.830 0-001 56-18 3.317 Interatomic distances: Gd has 12Ga at (D)
GdT1 3.7797 0.0009 54.00 3.274 Ga has 3Ga at (E), 6Gd at (D)
GdAI(2) 3.7208 0.0002 51.51 3-222
DyAg 3.608 0-001 46.97 3.125 a a(a) c a(c) Vol. D E
DyCu 3.461 0-001 41.46 2.997 (A) (h) (A) (A) (A~) (A) (A)
DyIn 3.7866 0.0009 54.29 3.281 GdGaz 4.221 0.001 4.141 0.002 63.89 3.197 2.437
DyT1 3.743 0.002 52.44 3.242 DyGa 2 4.2011 0.0003 4.0655 0.0005 62.14 3.165 2.426
DyAI(2) 3.6826 0.0004 49.94 3.190
(1) Strukturbericht, 3, 28 (1937).
(1) Strukturbericht, 1 74 (1931).
(2) Not the major constituent of powder photograph and
not all other lines of the pattern identified. T a b l e 7. SnNi3 structure type (hexagonal)(1)
Interatomic distances: Gd has 6A1 at 3.154, 6A1 at 2.929
T a b l e 4. AuCu8 structure type(l), (2) A1 has 2Ge at 3.154, 2Gd at 2.929
4A1 at 3.154, 4A1 at 2.929
Interatomic distances: Each atom is surrounded by 12 others
at (D). The number and type of neighbors depends on GdA1a a-----6.308+_0.003 /~, c=4.589+_0.009 A, Vol.---- 158.1 /~a
the degree of ordering (I) Strukturbericht, 5, 7 (1940).
a (A) a(a) (A) Vol. (A~) D (A)
Gdln 3 4.6103 0.0002 97-99 3.260 T h e u n i t - c e l l d i m e n s i o n s of t h e i n t e r m e t a l l i c p h a s e s
GdT1a 4.696 0.001 103.6 3.321 f o u n d in g r o u p s B, C a n d D are p r e s e n t e d i n T a b l e s 2
DyIn~ 4.5762 0.0009 95.83 3.236 t h r o u g h 9. T h e u n i t cell d i m e n s i o n s were c a l c u l a t e d
DyT1a 4.6720 0.0009 101.98 3.304
DyPt a 4.072 0.001 67-52 2.879 f r o m b a c k - r e f l e c t i o n d a t a b y a l e a s t - s q u a r e s f i t t i n g of
sin 2 0o = sin ~ 0c + K ~ sin ~, w h e r e ~ is = ~ / 2 - 0, a n d
(1) Strukturbericht, 1,486 (1931).
(2) Due to the relative values of the scattering factors, the K is a c o n s t a n t . F o r e a c h s t r u c t u r e t y p e , i n t e n s i t y
existence of ordering could not be detected. c a l c u l a t i o n s were m a d e for a r e p r e s e n t a t i v e c o m p o u n d

T a b l e 5. CaZn5 structure type (hexagonal)(1)

Interatomie distances: Gd has 6MI at (D), 12MII at (E)
MI has 3 Gd at (D), 6MII at (F)
MII has 4Gd at (E), 4MI at (F), 4MII at (G)
a (~) a(a) (A) c (h) a(c) (h) Vol. (h~) D (h) E (h) ~' (h) a (h)
GdN~ 4.9129 0-0008 3.9640 0.0005 82.86 2.836 3"156 2.437 2.456
(2) 4.899 0-005 3-973 0.005
(a) 4.910 -- 3.988
DyNi 5 4.8756 0-0002 3.9673 0-0001 81.67 2-815 3.143 2.432 2.438
(2) 4-869 0-005 3.969 0.005
GdCo s 4.978 0.005 3.973 0.002 85"26 2.874 3"185 2.452 2.489
(2) 4-974 0-005 3.973 0.005
(4) 4.984 -- 3.967
DyC% 4.933 0.002 3.989 0.001 84.07 2-848 3.172 2.451 2.466
(3) 4.926 0.005 3.988 0.005
(1) Structure Reports, 11, 59. (2) Wernick & Geller (1959). (3) Endter & Klemm (1944). (4) Dwight (1961).
AC 14--61
950 GADOLINIUM AND DYSPROSIUM INTERMETALLIC PHASES. II

Table 8. MoSie structure type (tetragonal)(1) The a u t h o r s are i n d e b t e d to Dr J. R. Doyle for

Interatomic distances: Gd has 2M at (D), 8M at (E) preparing t h e computer programs for t h e LGP-30 for
M has 1Gd at (D), 1M at (D), t h e e v a l u a t i o n of t h e cell dimensions. The r a r e - e a r t h
4Gd at (E), 4M at (E) metals were furnished t h r o u g h t h e courtesy of t h e
a a(a) c a(c) Vol. D E L u n e x Company, P l e a s a n t Valley, I o w a ; American
(h) (h) (h) (h) (h a) (h) (h) Metal Climax, Inc. d o n a t e d the g e r m a n i u m , a n d t h e
GdAg~. 3 . 7 2 8 0.001 9.296 0.006 129.2 3.099 3.057 Climax M o l y b d e n u m C o m p a n y furnished t h e molyb-
DyAg~ 3-6957 0.0002 9.213 0.001 125.8 3.071 3.031
GdAu~ 3.7320 0.0006 9.014 0.003 125.5 3.004 3.036 denum. The research was supported b y a N a t i o n a l
DyAu2 3.6940 0.0006 8.956 0.003 122.2 2.985 3.009 Science F o u n d a t i o n G r a n t G6225. The c o m p u t a t i o n s
(1) Strukturbericht, 1,741 (1931). were made possible by a n o t h e r N S F Grant, G6085.

Table 9. CuTi3 structure type (tetragonal)(1), (2) References

I)yaIn a=4.602-+0-004 A, c--4.945-+0.004/~, Vol.= 104-7 Aa
(1) Pearson, (1958), p. 618.
(2) Due to the relative values of the scattering factors,
the existence of ordering could not be detected.
in order to verify the choice of the structure. Powder
diagrams of alloys i n t e r m e d i a t e to t h e single phase
regions gave evidence t h a t if a n y h o m o g e n e i t y ranges
exist, t h e y m u s t be quite narrow.
CO~eTON, V. B. & M~TTmAS, B. T. (1959). Acta Cryst.
12, 651.
DWIGHT, A. E. (1961). Trans. Amer. Soc. Met. 53, 477.
ENDTER, F. & KLEMM, W. (1944). Z. anorg. Chem. 252,
377.
PEARSON, W. B. (1958). Handbool of Lattice Spacings and
Structures of Metals. London: Pergamon Press.
WERNICK, J. ~-I. & GELLER, S. (1959). Acta Cryst. 12, 662.
WERNICK, J. H. & GELLER, S. (1960). Trans. Amer. Inst.
Min. Met. Engrs. 218, 866.

Acta Cryst. (1961). 14, 950

T h e H y d r o g e n P o s i t i o n s in P o r t l a n d i t e , Ca(OH)2, as I n d i c a t e d
by the E l e c t r o n D i s t r i b u t i o n
BY HOWARD E. PETCIt
Crystallographic Laboratory, Cavendish Laboratory, Cambridge, England,
and Department of Metallurgy and Metallurgical Engineering, McMaster University, Hamilton, Ontario, Canada

(Received 28 September 1960)

X-ray diffraction and Fourier synthesis techniques have been used to determine the electron
distribution in a crystal of portlandite with sufficient accuracy to establish the hydrogen posi-
tions. The atoms have been found to occupy the following positions:
Ca (0, 0, 0)
O +(,_~,2 u)
H _+(, ~,2 v)
with u=0-2330 +__0-0004 and v =0"395 +0"008. Independent anisotropic temperature factors were
introduced for the calcium and oxygen ions. Also, in the final stages of refinement, systematic
differences between the observed and calculated structure factors became apparent and their
causes were traced to the Hartree scattering curves ~or Ca ++ a n d 0 - - which were ~irst used in the
determination of the calculated structure factors. Semi-empirical scattering curves were derived
and their use leads to an excellent agreement between the observed and calculated structure factors.
After this work was completed new theoretical values for the scattering factors Ca ++ and O- became
available and these have been compared with the derived semi-empirical values.

Introduction These o c t a h e d r a m a y be t h o u g h t of as joined t o g e t h e r

P o r t l a n d i t e , Ca(0H)2, a n d brucite, Mg(0H)2, are iso-
m o r p h e u s and their structures have been k n o w n for
m a n y years. T h e y possess a simple layer structure
in which each cation is at t h e centre of an o c t a h e d r o n
which is defined by h y d r o x y l ions, one at each corner.
in sheets perpendicular to t h e three-fold axis of t h e
trigonal crystal b y h a v i n g h y d r o x y l ions in common.
The sheets are stacked vertically one above the other.
The brucite structure was d e t e r m i n e d b y Aminoff
(1919). Megaw (1933) obtained accurate values for t h e