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J . Chem. SOC.,Faraday Trans. I, 1984, 80, 1903-1913

Aluminas Modified with Silica

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Part 1 .-An X-Ray Diffraction and Secondary-ion Mass-spectrometry

Study of the Influence of Preparation and Thermal Treatment on
Structure and Surface Composition

BY ALANW. ESPIEAND JOHNC. VICKERMAN*

Department of Chemistry, UMIST, P.O. Box 88, Manchester M60 1QD

Received 12th September, 1983

The surface composition and crystal structure of three series of aluminas, containing 5, 10
and 30 wt % silica, have been studied as a function of preparation and subsequent thermal
treatment using secondary-ion mass spectrometry (SIMS) and X-ray diffraction (X.r.d.). A
number of modes ofpreparation have been studied, ranging from various aqueous coprecipitation
procedures to mechanical mixtures of silica and alumina. It is shown that the formation of a
silica coating is a controlling feature in the thermal reactions of silica and alumina.

This paper is part of an extensive study of aluminas containing &30% silica. Several
physical techniques have been used to try to determine the effect of silica on the
mechanism of thermal transformations in modified aluminas. In future papers, tracer
spectroscopy (luminescence and e.s.r.) of doped CrIII and FeIII will be described and
an overall mechanism will be proposed. However, the present paper presents the
results of a study using a modern surface-specific technique, secondary-ion mass
spectrometry (SIMS), allied with the standard crystallographic characterisation of
powder X-ray diffraction (X.r.d.),
Industrial interest in silica-aluminas extends from the field of catalysis to ceramics.
Depending on their composition, silica-aluminas find application as cracking catalysts
in the petroleum industry,' or as inert, highly porous noble-metal catalyst supports.2
The technologically important mixed-oxide mullite (ca. 3Al,O, - 2Si0,) is found in this
system. It is a characteristic component in all aluminosilicate ceramics. Good thermal
shock resistance has led to the extensive use of mullite for investment castings and
recently as an inexpensive base for silicon solar cells.3 Corundum (a-Al,O,) is also
of great interest to ceramists and its incorporation in oxide fibres has recently
stimulated research into the modifying effect of small amounts of silica on its
refractory proper tie^.^
Iler5 was the first to suggest that surface reactions could be important modifying
and perhaps controlling factors in the thermal chemistry of silica-aluminas. Additions
of colloidal silica to boehmite (A 1 OOH) radically altered the conversion temperatures
and the sequence of transition aluminas obtained upon calcination of the mixture.
Corundum formation was suppressed by silica and a mechanism was proposed in
which silica reacted with alumina to form a highly viscous, glassy phase which coated
particles and prevented further ionic diffusion. Evidence of non-crystalline materials
in sub-solidus reactions at this interface has since been obtained from reaction couples
of silica-alumina pellets at 1500 oC.6However, the amorphous silica component in
all such materials is undetectable by diffraction methods until mullite or cristobalite
(SiO,) are formed,
1903
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1904 ALUMINAS MODIFIED WITH SILICA

To obtain new information on surface reactions in this system, calcined powders

have been studied using SIMS. The technique of SIMS and fast-atom bombardment
(FAB-SIMS) is a rapidly expanding method for surface analysis of inorganic solids.
The quantitative basis of SIMS is very complex since many experimental and chemical
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factors can affect the sputtering rates and secondary-ion yields.8 On the other hand,
X-ray photoelectron spectroscopy (X.P.S.) is an accepted, semi-quantitative surface
analytical t e ~ h n i q u eTherefore,
.~ surface silica concentrations (s.s.c.) were determined
for one calcination sequence by both SIMS and X.P.S.Similar semi-quantitative X.P.S.
data on the kaolinite calcination sequence have already been documented.1° Close
similarities in the results from both techniques gave increased confidence in the SIMS
work. Both techniques were allied to argon-ion etching, to reveal sub-surface
composition.
Parallel information was obtained by powder X.r.d. for comparison with existing
crystallographic studies of silica-alurninas.ll

EXPERIMENTAL
Silica-aluminas were prepared by several aqueous precipitation procedures. Aluminium
nitrate was neutralised with ammonia solution, in the presence of silica sol or partially
hydrolysed tetraethoxysilane (TEOS), in either a batch, slow neutralisation to pH 7, or
immediate precipitation at pH 7 in a buffered reactor from which product was continuously
removed. To give a further degree of potential dispersion of silica in alumina, separately
precipitated silica and alumina were mixed in an agate ball mill.
After extraction and drying, all samples were fired in air at the temperatures of interest for
a standard time of 18 h in alumina crucibles.
Phase analysis of the calcined materials was obtained with a Philips Guinier focussing camera,
using Cu Ka1 radiation.
SIMS spectra were obtained using the instrument described by Barber and Vickerman.12
Sample charging was overcome by flooding the sample surface with low-energy electrons (ca.
200 eV). Spectra were recorded before and after a standard etching procedure (2 min at 3 kV
per 20 ,uA Ar+ with spot size ca. 1 cm), which removed approximately the top 60 A. For
semi-quantitative measurements of s.s.c., spectra of 27Aland 28Siwere recorded several times
using an expanded scale. Values of s.s.c. were obtained by conversion of the Si+:Al+ peak height
ratios to weight % silica. Other details of operational procedure have been published
e l ~ e w h e r e12,
. ~l~3
X.P.S. measurements were carried out on an AEI ES300 instrument (by ICI Mond Division),
using a Mg target, before and after Ar+ etching which removed ca. 20 A. An A1:Si ratio and
thus a value of wt % SiO, was obtained from standard measurements of Si and A1 2p
photoelectrons, with binding energies of 1100 and 1130 eV, respectively.

RESULTS AND DISCUSSION

SIMS SPECTRA
THE
A typical SIMS spectrum for mullite is shown in fig. 1. The most intense secondary
ions were always the M+ ions (M = A1 or Si). As shown in fig. 2, these peaks closely
followed the surface composition of the solid and were used in the semi-quantitative
work described later. In common with all other oxide and catalyst systems investigated,
fairly intense peaks due to the alkali-metal cations Na+ and K+ were observed. The
intensity of these impurity signals is due to the high secondary-ion yields of these
species.
Significant cluster ion peaks were also obtained in the MOH+ region at mass 43-46.
Interpretation of this region was complicated due to spectral overlap, e.g. mass 44
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A. W. ESPIE A N D J. C. VICKERMAN
1905

27
At
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lo4

39
'
t

MOH+

20 I45
23
Na' 56 +
Fe
lo3

d
I

10
I I
41

40
K+
-
mle
50 70

Fig. 1. SIMS spectrum of mullite, calcined at 1300 "C. There are also low-resolution
peaks centred on: 71, M,O+; 86, M,Ot; 91, MOZ; 103, M,Ot; 119, M,OZ; 151, M,O;
(M = A1 or Si).

could be AlOH+ or SiO+. These peaks were not measured with sufficient accuracy to
merit analysis of mixed peaks into component ion intensities.
Extensive surface hydroxylation could be seen in the pure alumina and silica
spectra, with the MOH+ peak always more intense than that from MO+ and the
MOH+ :MO+ ratio the same (3.3 : 1.O) for both materials. Crystallinity had little effect
on this ratio with a value of 3.3: 1.0 for two precipitated silica powders fired to
80 "C (amorphous) and 1370 "C (cristobalite). Amorphous alumina and corundum
powders showed very similar results. Etching partially removed surface hydroxyls and
for mineral quartz the ratio MOH+:MO+ decreased from 5.0: 1.0 to 3.3: 1.0. These
results would suggest that all the powders, exposed to atmospheric humidity during
handling, had a similar degree of surface hydroxylation, even under the ultra-high
vacuum conditions of measurement.
Evidence of surface segregation of silica was also obtained from peaks in the MOH+
region, recorded before and after etching. An extreme example is given in fig. 3.
Semi-quantitative calculations on the M+ peaks showed surface silica levels of 41 and
18 wt % SO,, before and after the standard 2 min etch. The peak heights of the MOH+
region gave a pictorial confirmation of this result, with AlOH+ (44) replacing S O H +
(45) as the most intense secondary ion.
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1906 ALUMINAS MODIFIED WITH SILICA

27
Al
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23
Na
(a>

28
I
Si

27
Al

Fig. 2. SIMS for M+ region for silica-aluminas. (a) Corundum, (b) Saffil, (c) mullite and (d)
cristobalite.

1
( b)

45

Fig. 3. SIMS for MOH+ region of mechanically mixed silica-alumina, containing 10 wt % SO,,
calcined at 1400 "C, (a) before and (b) after etching.
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A. W. ESPIE AND J. C. VICKERMAN 1907

0.3
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0.2

SIMS

0-1

0
0 0.1 0.2
k-I QA
0'3
0.4

Fig. 4. Atomic ratios for silica-aluminas from SIMS and quantitative analysis.
Gradient = 0.5.

Peaks due to higher-mass fragments were poorly resolved due to the elemental
composition of the solids under study. Sample charging due to incomplete neutra-
lisation by the electron flood gun, necessary to prevent charge build-up on these
insulating solids, also contributed to poor mass resolution. FAB-SIMS avoids this
problem with bombardment by a neutral Ar-atom beam' and subsequent applications
have demonstrated its superiority for insulator analysis in terms of ease of use. Several
broad peaks were recorded which could be attributed to members of the series MO;
and M,Oi and their hydroxylated derivations.
Several authors have shown that the identity of the sputtered ion can be dependent
on the geometry and bonding of the host 1 a t t i ~ e .l4
l ~This
~ allows the surface structure
of a solid to be investigated from an analysis of the polyatomic secondary ions. This
met with only limited success in the present study because of the lack of mass
resolution mentioned above. More useful information was obtained, however, from
a semi-quantitative study of the variation in surface silica concentration, through the
calcination sequence of a silica-alumina. Several sequences were studied using SIMS.
Evidence of surface segregation was documented and step changes in S.S.C. were related
to other parameters such as phase composition.
CALIBRATION OF SIMS
Fig. 4 shows the Si: A1 ratio obtained from quantitative analysis plotted against the
average value of Si+:Al+ obtained from SIMS spectra of each sample, in each
calcination sequence, after the standard etching procedure. It was assumed that the
etching procedure removed any segregated material and the observed Si+:Al+ ratio
represented the bulk composition. Thus a calibration plot was obtained relating the
observed Si+:Al+ ratio to the acutal composition determined by chemical analysis of
the bulk material. The observed gradient was 0.5 and this plot could then be used
to obtain a surface atomic ratio from SIMS measurements, which were converted into
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1908 ALUMINAS MODIFIED WITH SILICA

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O I
0 50 0 I000 1500
TI" C
Fig. 5. Comparison of X.P.S.(-) and SIMS (---) measurements of plotted SAC. against
calcination temperature for a coprecipitated silica-alumina containing 5 wt % SiO, (hydrolysed
TEOS).

S.S.C.in wt % SiO,. The straight-line fit for the calibration plot is not ideal, but this
is perhaps not surprising from powders where extensive surface segregation was
the rule. Further complications can arise in the use of argon etching to measure
the composition from surface-analysis measurements of inhomogenous powdered
mate~ia1s.l~ Different amounts of particle skin and core are exposed as a function of
etching time and one particle can shade another from the analysing beam.
The gradient of the calibration plot is lower than that obtained from the silicate
glasses or zeolite^.^ This probably reflects a matrix effect, where sputtered-ion
intensities are dependent on different bonding in predominantly alumina or silica
lattices. Such an effect is not unreasonable since in the present materials the
proportions of alumina and silica are almost the inverse of those found in zeolites.
A comparison between X.P.S. and SIMS measurements gave support to the
assumptions in the above calculation and suggested that S.S.C. was a valid means of
following surface reactions in these materials. Surface silica concentrations as
measured by SIMS and X.P.S. are compared for a calcined coprecipitate containing
5 % SiO, in fig. 5. In general, both diagrams show dramatic changes in S.S.C. at the
same temperature. The lack of a 1050 "C sample for X.P.S. makes the agreement
slightly incomplete. Measurements made before etching could differ because of the
different effective analysis depth of the two techniques, ca. 10 A for X.P.S. but ca. 4 A
for SIMS. After etching the measurements are not directly comparable since 60 A was
removed in the SIMS experiment but only ca. 2 0 A during X.P.S. Therefore both
X.P.S. measurements were obtained from material removed before a second SIMS
experiment. Further discussion of this diagram will be given later.
Thus the X.P.S. and SIMS diagrams from this calcination sequence are sufficiently
similar to give confidence that significant data concerning the change in S.S.C.can be
obtained from the following SIMS routine. This can then be correlated with other
structural parameters, such as phase composition, to add to the structural information
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A. W. ESPIE A N D J . C. VICKERMAN 1909

on the thermal reactivity of these materials. Only semi-quantitative evidence will be
extracted from these changes in s.s.c., since surface-sensitive techniques are to some
extent affected by the mechanisms and procedure of the analysis itself.
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CALCINATION SEQUENCES - SURFACE SILICA CONTENT

Several different calcination sequences were studied using SIMS and the S.S.C.before
and after etching was calculated as described above. First, details of powders
containing 10 wt % SiO, will be described, to contrast the physical behaviour of silica
in a mechanical mixture with crystallographic interactions of silica in a coprecipitate.
Then coprecipitates resulting in modified aluminas ( 5 wt % SO,) and mullite
(30 wt % SO,) will be discussed. All the results are given in diagrammatic form with
the phase composition obtained from X.r.d. included below each graph. The silica
level obtained from quantitative bulk analysis is indicated on the S.S.C.axis by the
abbreviation QA.

10% SiO,
The simplest behaviour was recorded from a mechanical mixture of separately
precipitated silica and alumina. This is shown in fig. 6(a). Calcination of this material
resulted in an increase in S.S.C.on corundum formation, which required considerable
etching to regain the approximate baseline silica level. A further large increase in S.S.C.
was noted upon the formation of cristobalite. X.r.d. gave no information concerning
the silica component until the appearance of a crystalline silica phase. However, these
events as monitored by SIMS follow well established ceramic ground rules,16that in
mixed-oxide systems the more surface-active component (the one with the lower
melting point, in this case silica) will coat particles of the other oxide. SIMS
measurements of this sequence would suggest that the high-temperature product is
a composite material of cristobalite-coated corundum particles.
Different behaviour was shown by the coprecipitate containing 10% silica derived
from silica sol [fig. 6(b)].In this sequence, the extension of transition alumina phases
from silica addition was paralleled by an increase in S.S.C.at the formation of E- and
&A1,0,. The drop in S.S.C. at high temperatures can be attributed to the secondary
reaction of expelled silica with surrounding alumina to form mullite. This would result
in an aluminosilicate surface for the particle, whereas at lower temperatures it would
consist of amorphous silica.

5 % SiO,
A similar description can be given to the material used for the SIMS-X.p.s.
comparison (fig. 7), a coprecipitate containing 5 % silica obtained from hydrolysed
TEOS. Here again an increase in S.S.C. is noted during the ordering process in the defect
spinel transition aluminas. This can be attributed to the formation of alumina
structures with less tolerance for combined silica. The process reaches a maximum
upon corundum formation, since no tetrahedral silicon cations can be accommodated
in this structure.
The baseline obtained after etching this sequence is much more regular than in the
previously discussed materials. This could be due to the lower silica concentration,
resulting in a thinner silica-rich surface which would be efficiently removed by the
etching process.
Polycrystalline alumina fibres containing 4 wt % SiO, (Saffil, ICI Mond Division),
although of radically different morphology, gave a very similar result to the
high-temperature samples in this sequence. The final calcination temperature and
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1910 ALUMINAS MODIFIED WITH SILICA

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30

s.s.c

20

10

0
0 500 Tpc lob0 1sbo

30-

n
S.S.C.

QA
10 -

0-
0 500 U0C 1000 1500
I N N EE E DD f A+M~
I
M+A+D
Fig. 6. SIMS measurement of S.S.C.plotted against calcination temperature for silica-aluminas
containing 10 wt % SO,: (a) mechanical mixture, (6) coprecipitate with silica sol. (-) No
etch, (---) 2 min etch and (- --) 12 min etch. Key to phase composition: N, non-crystalline;
E, E - and y-A1203;D, 6- and 8-Al,03; A, a-Al,O,; Mt, tetragonal mullite; M, orthorhombic
mullite; C, cristobalite.
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A. W. ESPIE AND J . C. VICKERMAN 191I

30-
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20.

S.S.C.

10

0 1 I I I
0 500 TI0C 1000 IS00
I N N N E E E E E D+A+M I
1
Saffil (A+ M+D)
Fig. 7. SIMS measurement of S.S.C.plotted against calcination temperature for a coprecipitated
silica-alumina containing 5 wt % SiO, (hydrolysed TEOS). (-) No etch, (---) 2 min etch
and 0, Saffil. Key to phase composition as fig. 6.

thermal history of this material was not known, but it was inserted into the diagram
after consideration of its phase composition.
At the highest temperatures used in this study, every alumina modified with silica
can be seen as a silica-coated two-phase material. Porosity is no longer a significant
variable, but the silica enrichment must reduce bulk reactivity. This has consequences
for corundum, a thermodynamically stable high-temperature product of great interest
to the ceramics industry. A silica-rich coating will inhibit the energetic nucleation and
growth step required for corundum formation. Silica is in fact added as a crystal
growth inhibitor in a-Al,O, ceramics.17
30% SiO,
Fig. 8 details sequences of materials containing 30% silica where mullite is the
high-temperature end product. Fig. 8 (a)is the diagram from such a coprecipitate with
the silica derived from hydrolysed TEOS. An increase in S.S.C.is first recorded during
the formation of tetragonal mullite, a preliminary mullite phase only noted previously
from reactive silica-alumina gels.ls S.S.C.decreases to that expected from the bulk
composition as particles with a silica-rich surface are transformed into a homogeneous
mullite.
Several interesting features are shown in fig. 8 (b), a silica-sol-derived mullite
sequence. Extended etching of this coprecipitate strongly suggested that solids made
from silica sol consisted of silica-centred particles. This was suggested by the 10%silica
sol material discussed earlier [fig. 6 (b)]and confirms the accepted colloid chemistry
of this mixture.lg
Perhaps the inhomogeneity in this coprecipitate was the cause of the absence of
tetragonal mullite in the calcination sequence. As in other 30% silica sequences, an
increase in S.S.C. was noted between 800 and 1000 "C,but in this case the only crystal-
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1912 ALUMINAS MODIFIED WITH SILICA

30.
m QA
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20.

S.S.C.

10.

0.
0 500 T/OC 1000 1500
N E M t Mt M M I

0 500 T/oc 1000 1500

N N EE E E M M I
Fig. 8. SIMS measurement of s.s.c plotted against calcination temperature for coprecipitated
silica-aluminas containing 30 wt % SiO,: (a) hydrolysed TEOS, (b) silica sol. (-) No etch,
(---I 2 min etch and ( - - - I 4 min etch. Key to nhase comnosition as fie. 6 .
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A. W. ESPIE A N D J . C. VICKERMAN 1913

line material present was &-Al,O,. A sharp drop in S.S.C.was seen when mullite
finally formed, before a further increase at the highest temperature. From this it would
appear that extensive surface reorganisation is still occurring after orthorhombic
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mullite has formed. In comparison, the other mullite sequence had formed a homo-
genous solid by this temperature. In the production of refactory mullite, any such
separation of components must retard the formation of a homogenous product until
the thermal energy is sufficient for thorough mixing.

CONCLUSIONS
These semi-quantitative SIMS results can be seen to give important new information
on the thermal chemistry of silica-modified aluminas. Useful comparisons have been
made with phase compositions obtained from diffraction studies.
The initial dispersion of the silica component has been shown to be crucial in
determining subsequent thermal chemistry. Mechanical mixtures resulted in little
interaction of silica and alumina. However, SIMS did show silica movement before
X.r.d. revealed any crystalline transformations.
An intermediate degree of dispersion, possibly the result of silica-centred precipitates,
was noted with materials containing silica sol. This unique thermal reactivity was
monitored by both SIMS and X.r.d.
The most extensive dispersion of silica was suggested by the thermal behaviour of
materials prepared from hydrolysed TEOS. This resulted in the observation of a
preliminary tetragonal mullite phase. Also, the completion of reaction resulted in a
homogeneous product within the temperature range of the experiments.
Thus Iler’s original suggestion of a silica coating as a controlling feature in the
thermal reactions of silica and alumina has been shown to be correct by the application
of SIMS. Its part in the overall mechanism of reactions in silica-modified aluminas
will be discussed in a later publication.

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(PAPER 3/1602)