JOURNAL OF MATERIALS SCIENCE 8 (1973) 423-426

Wetting of refractory materials by

molten metallides
d. A. C H A M P I O N , B. d. KEENE, S. A L L E N
Division of Inorganic and Metallic Structure, National Physical Laboratory,
Teddington, Middlesex, UK

The sessile-drop technique has been used to investigate the wetting in vacuo by a series
of intermetallic compounds (TiAI3, TiSi,, TiNi, TiNi3, TiCr~, Cr3Si2, Fe2AIs, FeSi, Fe=Sis,
CoSi, "CoSi3", Ni3AI, Ni2Si), by silicon and by a nickel alloy (713LC), of single-crystal
AI203, single-crystal SiC, polycrystalline Si,N,, pyrolytic BN, and in some cases only,
tungsten. Measurements of contact angle were made at fixed temperatures within the
range 1200 to 1600~ Qualitative observations were made of the interaction and degree
of bonding between the constituents. The results of the various experiments are
compared and contrasted.

1. Introduction appeared in the literature on the wettability of

In previous communications from this Labora- refractory materials by molten intermetallic
tory [1, 21 the results of experiments have been compounds.
described in which the sessile-drop technique has
been used to investigate the wetting of aluminium 2, Experimental
oxide by molten aluminium and certain other The intermetaUic compounds used in these
metals. The same technique has now been used experiments were prepared in our laboratory,
for an investigation of the wetting by a series of with the exception of TiSi2 and Cr~Si~ which
metallides, by silicon and by the nickel alloy were obtained from Alfa Inorganics Inc,
713LC of single-crystal alumina, single-crystal Beverly, Mass, USA, and of TiNi which was
silicon carbide, polycrystalline silicon nitride, obtained from Mond Nickel Co. The nickel
pyrolytic boron nitride and tungsten. This work alloy 713LCt was supplied by N G T E Pye-
formed part of an investigation into the feasibi- stock.
lity of producing composite materials consisting All the ceramic plaque materials were cut arid
of intermetallic compounds reinforced with polished by Agate Products Limited. The single-
fibres. The metallides investigated consisted of crystal A12Oa samples were 18 mm square x
silicides and aluminides of metals in the first 1.5 mm thick, cut from Verneuil boules supplied
transition group together with a few inter- by H. Djevahirdjian, Switzerland, and with both
metallic compounds of elements within this principal faces optically polished. Plaques 12 mm
group; those investigated were: TiAI~, TiSi2, square x 3 mm thick were cut from large plates
TiNi, TiNi 3, TiCr2, Cr3Si2, F%A15, FeSi, of polycrystalline SiaN~ (supplied by Hoffmann
F%Sis, CoSi, "CoSi3",* Ni3A1 and Ni~Si. Manufacturing Co) and of pyrolytic BN (sup-
The present investigations have been less plied by Union Carbide Corporation). The SiC
detailed than the earlier ones [1, 2] and have been material was obtained as large masses of single-
limited to a single temperature in each instance. crystal platelets from Arendat Smeltwerk,
However, the experiments covered a wide range Norway, through Tennant Trading Ltd, London.
of materials and the results are reported here Individual crystals of irregular profile were cut
since very little previous work seems to have from lumps and one principal face polished. The
*The phase diagram given by Smithells [3] indicates a compound with this formula melting at 1306~C, but Hanson [4]
points out that there is evidence which casts doubt on its existence. X-ray analysis showed the material produced at
NPL to be a mixture of CoSi2 and Si.
-'Nominal analysis: 12.5% Cr, 6.1 ~ AI, 0.8 % Ti, 4.2 % Mo, 2.2 % Nb, 0.1% C, 0.1 ~ Zr, 2.5 % max Fe, balance Ni.
9 1973 Chapman and Hall Ltd. 423
 J. A. CHAMPION, B. J. KEENE, S. ALLEN

t u n g s t e n was in the f o r m of discs 12 m m dia- at the interface w o u l d n o t necessarily have been

meter x 3 m m thick cut f r o m bars.
The wetting experiments were carried o u t
u n d e r v a c u u m in the sessile-drop a p p a r a t u s as
described previously [1 ]. T o be consistent within
the present experiments, however, n o n e of the
samples was etched prior to placing i n the
furnace since m a n y of the materials were p o r o u s
so that it w o u l d have been difficult to remove all
traces of the etchant.
The profiles of the m o l t e n liquid drops were
p h o t o g r a p h i c a l l y recorded o n 35 m m film a n d
c o n t a c t angles d e t e r m i n e d by m e a s u r i n g pro-
jected images of the negatives. I n systems which
gave good wetting the liquid drop often spread
over the surface in a r a n d o m m a n n e r so that
truly m e a n i n g f u l values for c o n t a c t angles could
n o t be measured. Consequently, c o n t a c t angles
below 40 ~ were simply recorded as "less t h a n
40 ~ with the i m p l i c a t i o n that very good wetting
occurred in these instances. Visual observation
o f the p l a q u e after the experiment gave a
qualitative i n d i c a t i o n of chemical reaction a n d
c o m p a t i b i l i t y between the materials. Severe
interactions were manifestly a p p a r e n t in some
instances b u t m i n o r d e g r a d a t i o n of the substrate
observable.
3. Results
The results, except for the wetting experiments
with t u n g s t e n discs, are s u m m a r i z e d in Table I.
R e a c t i o n rings were observed o n some of the
a l u m i n a plaques: these were similar to those
observed previously with a l u m i n i u m a n d alu-
m i n i u m alloys o n a l u m i n a a n d m a y indicate the
f o r m a t i o n of a volatile reaction p r o d u c t [1 ]. The
b o n d strength of the solidified drop to the p l a q u e
was assessed by twisting one relative to the
other. Sometimes failure occurred within the
plaque, leaving the drop with a layer of plaque
material firmly adhering to the base. These
samples were classified as being b o n d e d , b u t this
merely m e a n s that the interfacial b o n d strength
was greater t h a n the shear strength of the plaque
materials.
The experiments in which the wetting pro-
perties of a limited n u m b e r c f the intermetallic
c o m p o u n d s (TiNi, Ni3A1, TiAI~, FeSi, F%A15,
TiSi2 a n d Ni~Si) to t u n g s t e n discs were investi-
gated at temperatures i n the range 1200 to
1500~ all resulted in very good wetting being
o b t a i n e d (contact angle less t h a n 40~

TABLE I Wetting of single-crystal A1203, single-crystal SiC, polycrystalline SiaN4 and pyrolytic BN by various
materials
Plaque
material AlsO3 SiC Si3N4 BN

Drop Temp. 0 Com- Temp. 0 Com- Temp. 0 Corn- Temp. 0 Corn-

material ( ~C) ( d e g ) merit ( ~C) ( d e g ) ment ( ~C) ( d e g ) ment ( ~C) ( d e g ) ment
TiA13 1500 82 wcf 1 4 5 0 <40 bd 1400 50 bc 1450 45 bd
TiSi~ 1560 80 xcn 1500 <40 bc 1500 <40 bc 1515 <40 wc
TiNi 1300 <40 bcn 1500 82 wc 1300 <40 bc 1300 <40 xc
TiNiz 1500 60 xcn 1500 50 bc 1450 66 bc 1500 96 wc
TiCrz 1500 <40 xcn 1500 <40 xc 1500 <40 xc 1500 <40 xc
Cr3Si2 1550 100 xcm 1 4 6 0 <40 bc 1500 80 bc 1460 118 wc
F%A15 1400 67 wcn 1300 58 bc 1300 66 bc 1300 45 wc
FeSi 1500 85 xcn 1420 < 40 wc 1500 76 xc 1550 66 xc
FezSi5 1450 90 xcf 1350 <40 wc 1450 66 bc 1500 82 bc
CoSi 1600 99 scf 1500 <40 bc 1470 62 bc 1500 63 xc
"CoSi3" 1500 80 scn 1400 60 xc 1400 <40 bc 1450 116 xc
Ni3AI 1550 83 xcf 1550 <40 bc 1550 75 bc 1600 <40 xc
Ni2Si 1400 87 xcn 1320 90 xc 1450 108 bc 1600 97 xc
Si 1550 94 bcm 1 4 5 0 <40 bc 1500 <40 bc 1500 105 bc
713LC 1500 90 xcn 1350 <40 bc 1400 <40 bd 1500 54 wc

Key to comments: x: no bond, w: weak bond, b: bonded, s: bulk of drop did not adhere to plaque but small areas
at periphery firmly bonded, c: apparent compatibility, d: doubtful compatibility, n: no reaction
rings, f: few reaction rings, m: many reaction rings.
424
 W E T T I N G OF R E F R A C T O R Y M A T E R I A L S BY M O L T E N M E T A L L I D E S
4. Discussion
It was found that in general, alumina was
unreactive with, and not well wetted by, silicides,
silicon or aluminides. Only compounds which
contain titanium were found to wet alumina to
any extent. These results may perhaps be com-
pared with those of Kurkjian and Kingery [5],
of Ritter and Burton [6] and of Sutton and
Feingold [7] who found that additions of
titanium promoted the wetting of alumina by
nickel. The observed decrease in metal-alumina
interracial energy was assumed to be due to a
selective adsorption of titanium atoms at the
interface, the process being of a chemisorptive
nature, resulting in the formation of strong
metal-oxygen bonds. Armstrong et al [8] de-
tected an interfacial reaction product c~-Ti~Oa in
similar experiments and it was found that
titanium diffused into the bulk alumina. The
results obtained with the intermetallics contain-
ing iron may be compared with thoae of Kingery
[9] who studied the effect on the wettability of
alumina by iron with additions of silicon.
Kingery found that the interfacial energy de-
creased with increasing amount of solute (con-
tact angles range from 137 ~ for 0 . 0 6 ~ Si down
to 115 ~ for 8 . 7 ~ Si). This he attributed to the
greater stability of Si-O bonds compared with
Fe-O. In general, electropositive solute bonds,
which form more stable metal-oxygen bonds
than the solvent, tend to be surface-active,
resulting in a decrease in contact angle.
In the present experiments it was found that
silicon and the silicides investigated, except
possibly Ni~Si, wetted silicon carbide. Alu-
minides gave low contact angles but aluminium
carbide (A14Ca), which is unstable in the presence
of water, may be formed at the interface.
Titanium compounds, with the exception of
TiNi, gave low contact angles.
With silicon nitride the effects of silicides were
varied. Very low contact angles were given by
"CoSia", TiSi~ and Si while the remaining
silicides wetted to a lesser extent and NizSi did
not wet at all. Aluminides gave moderate wetting
while titanium-containing compounds gave
moderate to good wetting. These results may be
compared with those of Calow and Barclay [10]
who found that silicon nitride whiskers showed
degradation after short periods at 1200~ in
nickel and iron matrices, (although this degrada-
tion was found to be due to physical changes in
the ceramic whiskers rather than chemical
reaction), and those of Ginsberg and Krock [11 ]
who patented an alloy comprising 9 0 ~ Ni,
7 . 5 ~ Ti and 2 . 5 ~ Si which has good wetting
characteristics with silicon nitride. In the latter
instance titanium was chosen because of its
ability to lower the surface energy between the
liquid and solid phase and the silicon was added
to slake the affinity of titanium for silicon, thus
reducing the degree of reaction on the silicon
nitride.
With boron nitride, silicon and the silicides
(except TiSiz) did not give good wetting. Com-
pounds of both aluminium and titanium (except
TiNia) yielded low contact angles.
The compound TiCr 2 is interesting in that it
gives low contact angles with all four ceramics,
does not bond to any and also appears to be
unreactive. With silicon carbide and silicon
nitride, it is the only titanium compound that
does not bond. This lack of b~nding could be
due to physical changes brought about by the
solid state transformation which occurs at the
ordering temperature (1370~
The nickel alloy 713LC shows good wetting
with silicon carbide, silicon nitride and boron
nitride but not with alumina, even though it
contains elements such as Ti, Cr and A1 which
have been reported to promote wetting with
nickel [12]. The series of experiments with
tungsten plaques demonstrated that this metal is
readily wetted by all the intermetallic compounds
which were tried.
Acknowledgement
The work described above was carried out at the
National Physical Laboratory as part of the
General Research Programme.
References
1. J. A. C H A M P I O N , B. J. KEENE, and J. M. SILL-
WOOD, J. Mater. Sci. 4 (1969) 39.
2. Idem, ibid 4 (1969) II11.
3. C. J. S M I T H E L L S , " M e t a l s R e f e r e n c e Book", 4th
edn. (Butterworths, London, 1967).
4. M. H A N S E N a n d K. A N D E R K O , " C o n s t i t u t i o n of
Binary Alloys", 2nd edn. (McGraw-Hill, New York,
1958).
5. c. a. KURKJ~AN and w. D. KINGERY, J. Phys.
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6. J. E. R I T T E R J U N . and M. S. B U R T O N , Trans. Met.
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7. W. H. S U T T O N and E. F E I N G O L D , "Materials
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8. W. M. ARMSTRONG~ A. C. D. C H A K L A D E R ~ and
J. F. CLARKE,Y. Amer. Ceram. Soe. 45 0962) 115.
9. W. D. K I N G E R Y , ibid 37 (1954) 42.
425
 J. A. C H A M P I O N , B. J. K E E N E , S. A L L E N

10. c . A, CALOW a n d R. B. BARCLAY, J. Mater. Sei. ] 2. B. W I L M S H U R S T, private c o m m u n i c a t i o n .

2 (1967) 404.
1t. M. [. C[NSBERG a n d R. H. K R O e K , U S Patent No. Received 1 A u g u s t a n d accepted 11 September 1972.
3 399 076 (1968).

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