J. Phys. Chem.

1994, 98, 1695-1703 1695

The Reaction of Hexamethyldisilazane and Subsequent Oxidation of Trimethylsilyl Groups on

Silica Studied by Solid-State NMR and FTIR

Suvi Haukka' i t and Andrew Root§

Microchemistry Ltd., P.O. Box 45, 02151 Espoo, Finland, Department of Chemistry, Analytical Chemistry
Division, University of Helsinki, Vuorikatu 20, 00014 Helsinki, Finland, and Scientific Services, Analytical
Research, Neste Oy, P.O. Box 310, 06101 Porvoo, Finland
Received: August 26, 1993; In Final Form: November 1, 1993®

The reactions of hexamethyldisilazane (HMDS) on silica preheated at 200-820 °C were carried out using
atomic layer epitaxy (ALE), a technique based on saturating gas-solid reactions. This led to highly reproducible
numbers of trimethylsilyl groups bonded to the silica surface. The trimethylsilyl groups produced were
subsequently oxidized in air with and without bound chromium acetylacetonate complex (SiOCr(acac)2) present.
Downloaded via DEUTSCHES ELEKTRONEN-SYNCHROTRON on September 13, 2023 at 17:29:03 (UTC).

The silica surface at different reaction stages was characterized by carbon determination, **H MAS NMR, 29Si
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

CPMAS NMR, 13C CPMAS NMR, and FTIR. The reaction with the terminal H-bonded OH groups, in
addition to isolated OH groups, on silica preheated at lower temperatures (<450 °C) was confirmed, and the
number of these species on 200 °C preheated silica was found to be around 0.4 OH/nm2. The secondary
reaction by dissociative chemisorption of ammonia was observed to occur on highly dehydroxylated silica. On
pure oxidized silylated silica samples, in addition to a significant amount of geminols, silanetriol groups (OSi-
(OH)3) were also produced. Their number could be increased even further by adsorbing Cr(acac)3 prior to
oxidation to create “hot spots”. This made it possible to use a lower decomposition temperature, thus preventing
the formation of siloxane bridges. The results suggest that the use of large samples (5-8 g) of silylated preheated
silica, with and without an additional compound for total or partial oxidation, can lead to a stabilized modified
silica surface.

Introduction
The interest in the reaction of hexamethyldisilazane (HMDS)
with the OH groups of silica is based on its use as a selective
poison for Bronsted acid sites, which is important in some catalyst
applications and in chromatography,1-3 and its suitability for
probing the surface structure of silica.4-7 The overall reaction
of HMDS with silica occurs in the following way:
2SiOH + (CH3)3SiNHSi(CH3)3 2SiOSi(CH3)3 + NH3
—
somewhat lower value than that usually reported (1.7-2.5) (ref
5 and references therein). Thus, the higher values may reflect
the fact that the reaction has proceeded to the point where the
so-called crowded surface is already produced.
Sindorf and Maciel6 studied the effect of dehydration tem-
perature of silica on the fraction of the OH groups occupied by
TMS groups. They observed that the fraction increases with
increasing dehydration temperature of silica up to 560 °C and
then decreases at higher dehydration temperatures. The decrease

was explained by the decreasing reactivity of the residual OH

HMDS, either in the gas phase or in the liquid phase in solution,
can be reacted with silica to give trimethylsilyl (TMS) groups
bound to the surface.5·7 Spectral information on the HMDS-
modified silica surface has been obtained by 29Si CPMAS NMR,5·6
IR,4·8·9 and NIR reflectance spectroscopy10 and by using the
radiochemical tracer technique.11 From the observed weight gain
or carbon elemental analysis of the silylated product, the TMS
coverage can be calculated, and thus the number of occupied OH
groups can be deduced. Despite the high reactivity of HMDS
toward silica, the maximum surface coverage attainable, with
respect to the number of OH groups present on the surface, cannot
be achieved.5 This has been attributed to steric hindrance of the
TMS groups. On the basis of molecular geometry and packing
considerations, Sindorf and Maciel5 have calculated the maximum
coverage to be 2.2-2.8 TMS groups/nm2, depending on the model
used. Furthermore, the coverage seems to be dependent on how
the silica is reacted with HMDS. Initially the reaction is expected
to be rapid, resulting in a random distribution of well-separated
TMS groups.5 Subsequent reactions occur at a reduced rate
because of steric hindrance leading to a crowded surface.
According to Snyder and Ward7 and more recently Sindorf and
Maciel,5 the number of attached TMS groups attributable to the
fast reaction (100% uptake of loaded HMDS) is 1.5/nm2, a
t Microchemistry Ltd.
*
University of Helsinki,
t Neste Oy.
•Abstract published in Advance ACS Abstracts, December 15, 1993.
groups of 800 °C dehydrated silica.
Hertl and Hair8 proposed that the reaction of HMDS occurs
almost exclusively with isolated OH groups, leaving the H-bonded
OH groups unoccupied. This property of HMDS has been applied
successfully to study the bifunctional reactivity of TiCl4 toward
H-bonded OH groups on silica in both the vapor phase12 and
organic solution.13 No change in HMDS coverage was observed
after reacting TiCl4 at 175 °C with HMDS-modified silica.12
Instead, the number of titanium atoms was half of that reacted
without silylation, and the reaction led exclusively to the doubly
bonded titanium species. Therefore, the attainable TMS surface
coverage is not only determined by the steric hindrance, but also
by the lower reactivity of HMDS toward H-bonded OH groups.
Recently, Morrow and McFarlan9 concluded that HMDS also
reacts partly with H-bonded OH groups, while 29Si CPMAS
NMR studies have revealed that HMDS is more reactive toward
geminal OH groups than single ones.5
Ammonia evolved during the HMDS reaction can also interact
with silica. Two possible effects of ammonia have been proposed,
depending on the dehydration temperature of silica. Studies with
NIR reflectance spectroscopy have revealed the presence of
physisorbed ammonia on fully hydroxylated silica after the HMDS
reaction.10 The adsorbed ammonia was totally removed from
the silica surface by evacuating at 170 °C. Separate studies on
reactions carried out using an excess of ammonia have shown
that in the reaction with highly dehydroxylated silica the siloxane
bridges are broken, resulting in the formation of a bound NH2

0022-3654/94/2098-1695S04.50/0 &copy; 1994 American Chemical Society

1696 The Journal of Physical Chemistry, Vol. 98, No. 6, 1994
group and a new OH group.14·15 On the basis of studies with
heterogeneous gas-solid chromatography (HGSC), the reaction
of ammonia with siloxane bridges was also proposed to take place
during HMDS reaction with highly dehydroxylated silica, since
the basicity of the silica increased after the silylation.3 No spectral
evidence for the secondary reaction of ammonia by dissociative
chemisorption in the case of the HMDS reactions has been
reported.
The silylated silica surface has been found to be stable up to
650 °C in the absence of oxygen,16 whereas a thermogravimetric
study17 has shown that the highest weight decrease in the presence
of oxygen occurs at 500 °C, leading to the reappearance of SiOH
groups. The various surface species produced on partly oxidized
surfaces have been studied by 29Si CPMAS NMR and secondary
ion mass spectrometry (SIMS).17
In this paper we study the HMDS reaction and the subsequent
oxidation of the produced TMS groups on silica with the aim of
precisely modifying the silica surface. The TMS groups were
bound to silica from HMDS using atomic layer epitaxy (ALE).18
This technique is based on saturating gas-solid reactions, in which
physisorption is avoided by elevated growth temperatures. The
silylated and subsequently oxidized silica surface was charac-
terized by 29Si CPMAS NMR, MAS NMR, 13C CPMAS
NMR, FTIR, and carbon determinations.
Experimental Section
Reagents. Hexamethyldisilazane (HMDS), used without
further purification, was vaporized at 50 °C. Chromium
acetylacetonate was vaporized at 190-200 °C. Silica (EP10,
Crosfield Ltd.) with a surface area of 300 m2/g, pore volume of
1.75 cm3/g, and mean particle size of 100 urn was used as support.
Nitrogen (99.999%) was used as carrier gas in the ALE reactor.
ALE Procedure. The ALE equipment has been described
previously.19 Silica (5-8 g) preheated at 200,300,450,560,650,
750, and 820 °C was used in the HMDS reactions at 175 °C.
The HMDS reactions at 250 °C were carried out with silica
preheated at 450 and 820 °C. Silica used in this work has been
characterized in more detail earlier.12 An excess of HMDS (5
g) was led through the silica bed in a flow of nitrogen to ensure
surface saturation. Each reaction was followed by a nitrogen
purge for 2 h at the same temperature as the HMDS-binding
reaction to remove unreacted HMDS from the silica bed. To
confirm that surface saturation had been achieved, the carbon
concentration in the top was compared with that in the bottom
layers of the fixed silica bed. The concentrations were the same
to within ±3%.
Two sets of oxidized samples were prepared. The first set of
samples was prepared by treating a silylated 560 °C silica in the
ALE equipment in air at temperatures of 400,420,450, and 500
°C for 4 h. The second set of samples was prepared from silylated
450, 560, and 650 °C silica samples that were further reacted
with chromium acetylacetonate Cr(acac)3 at 200 °C.20 The
chromium is present as SiOCr(acac)2 species, and the amount
is below 0.05 Cr atom/nm2. The air treatment was then carried
out in the ALE equipment at 400 °C for 4 h. Chromium(III)
was simultaneously oxidized to chromium(VI), which was
observed by the distinctive color change from green to yellow.
While the Cr(VI) species is not paramagnetic, residual Cr(III)
can interfere with the NMR signal due to the interaction of the
unpaired electron with the proton. Although the level of Cr in
these samples was low, the effect of this on the NMR intensity
was checked for one HMDS sample before and after the addition
of the Cr(acac)3, but before oxidation. The difference in overall
H content was within experimental error (±5%). We conclude
that for the samples examined here after oxidation, when at least
60% is converted to Cr(VI), there is no significant effect on the
NMR measurements. All samples were cooled in a nitrogen
flow and transferred inertly to NMR and IR measurement sample
holders. Carbon elemental analysis was carried out with a Leco
Haukka and Root
8.00 6.00 4.00 2.00 0.00
10.00 -2.00 -4.00
PPM
Figure 1. MAS NMR spectrum of untreated, dried silica EP10.12
carbon CR 12 analyzer (treatment at 1370 °C in oxygen) before
and after air treatment. To avoid exposure to the air moisture,
the sample for carbon determination was taken inertly after cooling
the silylated sample in a flow of nitrogen.
FTIR Measurements. An FTIR spectrometer (Galaxy Series
6020) equipped with a diffuse reflectance accessory was installed
in a glovebox, into which the samples were inertly transferred.
The samples were measured as loosly packed powders using a
spectral resolution of 2 cm-1. The accumulation time was about
4.5 min, corresponding to 1000 scans. Spectra are presented in
a diffuse transmittance format.
NMR Measurements. MAS NMR measurements were
carried out with a JEOL GSX 270-MHz NMR spectrometer
using a home-built, double-resonance probe with a low NMR
background signal. One hundred transients were acquired using
a 2-us (45°) pulse, 10-20-s recycle delay, and a 100-kHz spectral
width. At low silica preheat temperatures a 10-s recycle delay
was used, while a preheat temperatures above 450 °C, a 20-s
delay was used. All experiments were carried out using a spinning
speed of 6.5 kHz, with dry nitrogen as the drive and bearing gas.
A background signal run under identical conditions with an empty
rotor was subtracted from all spectra.
The samples were loaded under a dry nitrogen atmosphere
into 7-mm-o.d. zirconia rotors with push on caps. Leaving a
sample in the probe overnight and running the spectrum again
did not give any detectable increase in signal intensity within the
limits of experimental accuracy (±5%). The number of H’s in
the sample was determined from a reference sample of EP10
silica as described previously.12 In all the spectra the intensity
of the spinning sidebands was also included in the measurement
of the total peak area.
In cases where the SiOH resonances were dominant in the
MAS NMR spectra, these were deconvoluted into four gaussian
resonances, as described earlier,12 in order to separate the isolated
and H-bonded OH groups. An example of this taken from ref
12 is shown in Figure 1. The two narrower peaks are assigned
to the isolated OH groups while the two broader ones to the
H-bonded OH groups.
29Si CPMAS NMR experiments were carried out using the
same probe as above on dried samples using a 5-10-ms contact
time (50-kHz 29Si and radio frequency fields), 5-s delay, and
between 20 000 and 50 000 transients. The spinning speeds used
were around 4 kHz.
The 13C CPMAS spectra were recorded with a 3-s recycle
delay, a 3-ms contact time (50-kHz rf fields), and 20 000
transients. The spinning speeds used were around 4 kHz.
Solid-State NMR and FTIR Studies The Journal of Physical Chemistry, Vol. 98, No. 6, 1994 1697

"e

Preheat temperature of silioa/°C

Figure 2. The number of trimethylsilyl (TMS) groups bound/nm2 (O),
the original number of isolated OH groups/nm2 (+), and the total number
of OH groups/nm2 ( ) determined by 'H MAS NMR as a function of
preheat temperature of silica.

Results
Reaction of HMDS on 200-820 °C Silica. Figure 2 presents
the number of TMS groups on the silica surface as a function of
the preheat temperature of silica. Itvariedfrom 1.6TMSgroups/
nm2 on 200 °C silica to 0.9 TMS groups/nm2 on 820 °C silica.
Wavenumbers/crrr1
The saturating gas-solid reactions of HMDS with differently
Figure 3. FTIR spectra of (A) 200, (B) 300, (C) 450, (D) 560, and (E)
preheated silica samples were highly reproducible. This was
650 eC silica after the reaction of HMDS at 175 °C, and (F) 820 °C
confirmed by carrying out four separate reactions on 450 °C
silica after the reaction of HMDS at 250 eC.
silica, six on 560 °C silica, and four on 820 °C silica. The
reproducibility of the TMS determination was found to be ±4.8,
±2.3, and ±3.5%, respectively. In addition, the reactions carried
out at 250 °C gave similar results to the reactions carried out at
175 °C. Since it has been shown previously12 that HMDS reacts
only with isolated OH groups and leaves the strongly and weakly
(bulk hydroxyls) H-bonded OH groups unoccupied, the number
of bound TMS groups in Figure 2 is compared to that of isolated
OH groups, in addition to the total number of OH groups measured
by MAS NMR.12 As shown in Figure 2, the number of TMS
groups bound shows the same trend as the number of the isolated
OH groups, i.e. remains fairly constant up to 450 °C but decreases
thereafter with increasing dehydroxylation temperature.
The FTIR spectra of the silylated silica samples are shown in
Figure 3. When silica is preheated at lower temperatures (200-
560 °C), only a broad peak due to H-bonded OH groups is seen
together with the peaks due to the C-H stretching vibrations. On
the highly dehydroxylated silica samples (650-820 °C), the
HMDS reaction gave rise to new low-intensity IR peaks that
appeared at 3815, 3720, 3660, 3595 cnr1, and a broad one that
appeared at about 3500 cm-1. The peaks at 3815, 3720, and
3660 cm-1 can be attributed to the combination of C-H (2909
and 2965 cnr1) and Si-C stretching vibrations and CH3 rocking
(752 and 82CT-840 cnr1), respectively, as proposed by Van
Roosmalen and Mol,4 whereas the peaks at 3595 and 3500 cm-1
seen in the FTIR spectra could bedue to chemisorbed ammonia14-15 Figure 4. 29Si CPMAS NMR spectra of (A) 200, (B) 300, (C) 450, (D)
(Figure 3, spectra E and F). 560, and (E) 650 °C silica after the reaction of HMDS at 175 °C, and
29Si CPMAS NMR spectra of the HMDS-modified silica (F) 820 °C silica after the reaction of HMDS at 250 °C.
samples show peaks at 13 ppm due to the Si(CH3)3 groups and
at —93, -101, and -110 ppm due to 02Si(0H)2, 03SiOH, and residual groups. However, at high preheat temperatures, at least,
O4S1, respectively (Figure 4). In the 29Si NMR spectra of silylated the presence of SiOH or SiNH2 is implied by the presence of a
200-300 °C silica, a shoulder at 17 ppm is clearly observed. This peak at -102 ppm in the 29Si CPMAS NMR spectrum. Therefore
implies the presence of a TMS group on the surface which has it seems possible that the interaction between the residual OH
a somewhat different structural environment. This extra peak groups and CH3 groups is responsible for the nonobservation of
in the 29Si spectrum at +17 ppm disappears when the HMDS is peaks due to residual isolated SiOH groups.
reacted with silica preheated at 450 °C and higher and is probably Evidence for the interaction between the CH3 groups and
connected with the H-bonded OH groups in some way. isolated OH groups was found in the reaction of silylated 450 °C
The number of TMS groups on the silylated silica is less than silica with T1CI4 at 450 °C (see Figure 6). When the silylated
the number of isolated OH groups measured (Figure 2). silica is reacted with T1CI4 at 175 °C, the number of TMS groups
Therefore it might be expected that residual isolated OH groups remains unchanged,12 whereas at a higher reaction temperature
would be observed after silylation. In both the FTIR (Figure 3) of 450 °C, T1CI4 has sufficient energy to remove the TMS groups
and MAS NMR (Figure 5), there is no evidence for these as a volatile compound through direct chlorination of the site
1698 The Journal of Physical Chemistry, Vol. 98, No. 6, 1994
Figure 5. MAS NMR spectra of (A) the original 200 eC silica and
(B) after the reaction of HMDS at 175 °C.
Wavenumbers/cm''
Figure 6. FTIR spectra of silylated 450 °C silica (A) and after the
reaction of TiCl4 at 450 °C (B).
where the TMS group is bound.21 In the spectrum (Figure 6B),
the presence of the peaks due to C-H stretching vibrations
indicates that not all the TMS groups have been removed.
According to carbon determination, 0.25 TMS/nm2 are still left,
the original number being 1.5 TMS group/nm2. In the spectrum
recorded prior to the TiCl4 reaction, no peak due to isolated OH
groups was seen, whereas after the incomplete TiCl4 reaction the
peak is seen. In this case the appearance of the peak due to
isolated OH groups could mean either that isolated OH groups
were formed or that the disturbing effect of the CH3 groups were
diminished.
Quantitative Determination of Surface Groups. As shown by
Maciel et al.,5 from a combination of weight gain analysis and
29Si CPMAS NMR, both the number of TMS groups on the
surface of silica after reaction of HMDS, and the number of OH
groups before reaction can be determined. It has been shown5
that using a contact time of around 8-10 ms, the areas of the
TMS, 02Si(0H)2, and 03Si0H peaks, at +13, -93, and -101
ppm, respectively, are quantitative. In this work, carbon elemental
analysis was used to determine the number of TMS groups present
on the surface of the silica and then the number of OH groups
was calculated from the relative peak areas of the TMS, 03Si-
OH, and 02Si(OH)2 peaks in the 29Si spectra. For three samples
both 5- and 10-ms contact times were used to check the effect
of this on the number of OH groups measured. In all cases the
number was the same to within ±5%. Therefore, these mea-
surements did not seem to be sensitive to the contact time used
if between 5 and 10 ms.
The total number of H’s present can be measured in two ways.
The first which we denote method I, is from the carbon
determination and 29Si spectra, as shown above. The second,
method II, is to record the MAS NMR spectra quantitatively
and measure it directly. The *H MAS NMR spectrum of 200
°C silica treated with HMDS is shown in Figure 5. The spectrum
is dominated by a peak at 0 ppm, due to the Me groups with some
residual OH groups from 1 to 6 ppm. The intensity of the first-
Haukka and Root
Total H's/nm2 from 1H MAS
of protons in the silylated silica samples
Figure 7. The total number
measured by MAS NMR versus the number measured by a
combination of 29Si CPMAS NMR and carbon determination. The
straight line indicates the ideal correlation.
TABLE I: Comparison between the Number of OH Groups
of Silica Determined by MAS NMR and That Determined
by 29Si CPMAS NMR Using the Number of TMS Groups
Obtained from Carbon Determination
total number of OH groups/nm2
preheat temperature from 29Si from >H MAS
of silica (°C) (method I) (method II)
200 7.6 6.5
300 6.3 5.6
450 4.1 3.4
560 3.0 2.2
650 2.3 1.8
750 1.7 1.3
820 1.6 1.2
order sidebands for the CH3 groups was small, around 12% of
the central resonance intensity, due to the averaging of the H-H
dipolar interaction by fast rotation of the TMS group about the
C3 axis of the Si-O bond. Since the number of CH3 groups is
so large relative to any residual OH groups and the line shapes
somewhat ill defined due to partial averaging of the interactions
present, no attempt was made to separate out the components by
deconvolution.
Figure 7 shows the total number of H’s measured by this direct
method II versus the number measured by method I. The values
range from 10 H/nm2 for the lowest TMS coverage to around
23 H/nm2 for the highest TMS coverage. The data points should
lie on the straight line shown in Figure 7. The agreement between
the two methods is within ±10%. Although the total number of
H’s measured is in reasonable agreement, the number of OH
groups measured using method I is consistently higher than the
number of OH groups measured before reaction on the untreated,
dried silica by method II. A comparison of the two values for
each sample is shown in Table 1. The difference varies from 15
to 30%. The possible reason for the difference is the secondary
reactions of NH3 as discussed below.
Oxidation of Silylated 560 °C Silica. The silylated 560 °C
silica was oxidized in air at 400, 420, 450, and 500 °C for 4 h.
The amount of carbon removed was 15, 45, 70, and 85%,
respectively. The 560 °C silica was used to avoid any continuous
release of water from the silica surface upon oxidation.
Figure 8 shows the 29Si CPMAS NMR spectra of the silylated
560 °C silica oxidized at 420, 450, and 500 °C. After oxidation
new resonances are seen between 0 and -70 ppm. The possible
species present on the surface after oxidation are shown in Figure
9. As expected, there is a gradual decrease in the nSim species
for large n with a concomitant increase in the "Sim with small «
and eventual production of 03Si0H groups. In addition, the
formation of the silanetriol group OSi(OH)3 (°Sii) can be seen
clearly in the 450 and 500 °C oxidized samples. The 13C CPMAS
spectra of the 420 and 450 °C oxidized samples are shown in
Figure 10. There are three peaks observable at -1.3, -2.8, and
-7.6 ppm, and the lowest frequency peak increases in intensity
Solid-State NMR and FTIR Studies The Journal of Physical Chemistry, Vol. 98, No. 6, 1994 1699

3Si„

Figure 10. 13C CPMAS NMR spectra of silylated 560 °C silica after
oxidation in air at the indicated temperatures for 4 h (see Figure 9 for
assignments).

Si-OH
Figure 8. 29Si CPMAS NMR spectra of the silylated 560 °C silica after
oxidation at (A) 420, (B) 450, and (C) 500 °C in air for 4 h and (D)
after a second reaction cycle of HMDS on sample C (see Figure 9 for
assignments).
Me
I
Me—Si —
Me
3S.1

mu Si//////

Me
l
Me —
Si —OH
2Si1 I
0
I

u m Si/
Me Me Me X
2Si, I
Me—Si*—0 Si-
I
0 0
I I

1111 Si TTTTTTTTJ
,,
1 “' 77777
Si

OH
Si —OH Figure 11. MAS NMR spectra of the silylated 560 °C silica after
’Si, Me —

0
oxidation in air at the indicated temperatures for 4 h.
Si-_
um °'//m bridges can now also be quantified by using the results from
MAS NMR and carbon determination. When silylated silica is
Me OH OH X
1Si2 \ / 1 1 oxidized, the methyl groups are converted to OH groups, which
Me—Si*-O— Si-Y
x \ 1 1
in turn dehydroxylate to give siloxane bridges if a sufficiently
O 0 0 0
high oxidation temperature is used. This process can be studied
u ~ti um -m iii /11111 s'iiiii in more detail using the results from MAS NMR spectra of
silylated 560 °C silica oxidized in air at 420, 450, and 560 °C
1Si, Me Me X
(Figure 11). As can be seen, the SiMe peak at 0 ppm gradually
Si Si*-O -si—y
decreases, while the SiOH peaks between 2 and 6 ppm increase.
—

X i \ X | 1

O O O 0 0
Since the SiMe peak is still relatively large, it is quite difficult
i—Si—Si- Sl Sl m m Sl
to deconvolute the two areas, due to the problems associated with
'

i iii 11 II Mill
the choice of line shape to be used. For that reason we chose to
X Me X
use the total H content measured by NMR in combination with
-si-O -Si* O— Si —Y
the carbon determination. We define several experimental
—

O O O
parameters as follows:
i /11
“' 111 ii
77T “'7777777 “'ll III

Figure 9. The possible surface species produced upon oxidation of the CA

=
C/nm2 after oxidation
silylated 560 eC silica at various temperatures in air.
CB
=
C/nm2 before oxidation
at the higher oxidation temperature. Since more of the single
methyl species is produced at the higher temperature, we assign Hh =
H/nm2 from CH3 after oxidation
these three peaks to the methyl groups of the 3Si„, 2Si„, and *Si„
f/Nmr = tota* H/nm2 after oxidation
species, respectively.
When silica is heated at high temperature an increasing amount
OHSi
= total SiOH/nm2 on original silica
of siloxane bridges are formed. The same is observed in the case
of oxidized silylated silica samples, and the formation of siloxane From these experimental parameters, the following can be
1700 The Journal of Physical Chemistry, Vol. 98, No. 6, 1994 Haukka and Root

TABLE 2: Number of Siloxane Bridges Formed on Silylated OjSiOH

560 °C Silica Oxidized at Different Temperatures for 4 h
total H/nm2
oxidation total H/nm2 measured by
temperature calculated after >H MAS NMR SiOSi
(°C) oxidation after oxidation produced/;
420 10.8 10.2 0.3
450 8.6 7.0 0.8
500 7.3 3.8 1.8

calculated:

S' II
OHSi-CB/3
II
OHx
1

where OHy is the number of SiOH groups left after silylation and
OHx is the number of SiOH produced by the oxidation of methyl
groups SiMe -*· SiOH, assuming no siloxane bridges are formed.
Finally the total number of H/nm2 can be calculated, assuming
that no siloxane bridges are produced, as:
Figure 12. 29Si CPMAS NMR spectra of (A) 450, (B) 560, and (C)
=
A+ OHy + OHx silylated 650 °C silica after oxidation in air at 400 eC for 4 h. The
The difference between this number and that measured exper- samples contained bound chromium acetylacetonate complexes prior to
oxidation (<0.05 surface groups/nm2).
imentally (H^mr) is a measure of the number of siloxane bridges
formed. This data is summarized in Table 2. In these calculations
the number of OHs, used was that measured from the carbon
determination and the 29Si CPMAS NMR spectra. This was to
take into account any extra species produced on the surface by
undefined secondary reactions. As can be seen, and as expected,
the number of siloxane bridges produced increases with increasing
oxidation temperature. It is possible that the water released by
the oxidation of the methyl groups could rehydrate the siloxane
bridges, and this would mean that the values for the number of
siloxane bridges given here are underestimated. However, the
oxidation temperature is so high here that we assume this effect
to be negligible.
The partly oxidized silylated silica samples were further reacted
with HMDS; 20,40, and 80% of the OH groups present on 420, 5 0 -90 -120
450, and 500 °C oxidized surface were silylated. Thus, the less
PPM
complete the oxidation the smaller the fraction of the OH groups
that were silylated. This was most probably due to the steric Figure 13. Original and simulated 29Si CPMAS NMR and MAS
hindrance caused by the presence of the large number of CH3 NMR spectra of the silylated, Cr(acac)3-treated 560 °C silica after
oxidation at 400 °C for 4 h.
groups on the less oxidized surface or to the H-bonded nature of
these new OH groups, i.e. interaction between the CH3 and OH
to calculate the total number of OH groups/nm2. From the 29Si
groups. In addition, after oxidation a peak due to isolated OH
NMR the proportion of OSi(OH)3, 02Si(0H)2, and 03SiOH
groups was seen in the FTIR spectra, but after the second cycle
can be found. From this the absolute number of different OH
of HMDS the peak disappeared again. The 29Si CPMAS NMR
spectrum of the 500 °C oxidized silylated silica surface that was groups on the surface can be found. This is summarized in Table
further reacted with HMDS is shown in Figure 8D. The number 3. Note that in the 29Si spectra of oxidized silylated 450 °C silica
of TMS groups/nm2 determined after the second cycle of HMDS and 650 °C silica (Figure 12, spectra A and C), the 650 °C silica
was 1.3, a somewhat lower number than determined after the seems to give more OSi(OH)3 than the 450 °C silica. However,
first reaction cycle (1.5 TMS/nm2). the absolute number of OSi(OH)3 groups on 450 °C silica is the
Oxidation of Silylated Silica Samples Containing Bound same within experimental error (Table 3).

Chromium Acetylacetonate Complex (SiOCr(acac)2). The 29Si
CPMAS NMR spectra of the oxidized silylated samples prepared
from 450, 560, and 650 eC silica and containing chromium
complex are shown in Figure 12. The samples were air treated
at 400 °C for 4 h and only 0.1 wt % carbon was left on the surface.
Here the carbon was removed at a much lower temperature than
in the case of the pure silylated silica samples. For these samples
we can apply a different method to get information about the
surface groups, which are now mainly SiOH groups. The SiOH
and SiMe peaks in the MAS NMR spectra are now easier
to separate because the amount of SiMe is so small that the
intensity in the wings of the SiMe peak is small relative to the
SiOH peaks. An example of the deconvolution of the 29Si CPMAS
and MAS spectrum of the sample oxidized at 400 °C is shown
in Figure 13. The same Gaussian lines are used to simulate the
SiOH peaks, and a combination of two gaussian lines are used
for the SiMe peak. Since the relative proportion of SiOH and
SiMe can be determined, the total number of H/nm2 can be used
The presence of silanetriol groups on the silica surface was
reported for the first time by Severin and Vankan.22 They reacted
700 °C treated silica with SiCl4 in the liquid phase and then
exposed the silylated surface to air moisture to remove the chlorine.
They found a small peak due to silanetriol groups, and the peak
due to geminols was increased significantly. In our case an even
more enhanced peak due to silanetriol groups after oxidation of
trimethyl groups was observed. After exposing the samples to
air moisture for 12 months, a small peak due to silanetriols was
still observed, although reduced in intensity.
The FTIR and MAS NMR spectra of the original 450 °C
silica and the oxidized silylated Cr/450°C silica are compared
inFigure 14. ThetotalnumberofOHgroups/nm2inthesamples
agreed, being 3.4 in the original silica and 3.3 in the oxidized
sample, which still contained 0.2 CH3 groups/nm2. In the FTIR
spectrum of the oxidized sample, an even more broadened
absorption within the H-bonded OH group region is seen. This
means that in the oxidized sample the OH groups produced are
Solid-State NMR and FTIR Studies The Journal of Physical Chemistry, Vol. 98, No. 6, 1994 1701

TABLE 3: Number of CH3 Groups, Isolated and -Bonded OH Groups, and OH Groups/nm2 in the OsSiOH, 02Si(0H)2, and
OSi(OH)3 Surface Groups on Silylated 450, 560, and 650 °C Silica Samples after Oxidation at 400 °C for 4 h*
total number of OH split into
preheat T number of CH3 isolated OH H-bonded OH OH groups in OH groups in OH groups in
of silica (°C) groups/nm2 groups/nm2 groups/nm2 03Si0H/nm2 02Si(OH)2/nm2 OSi(OH)3/nm2
450 0.2 1.7 1.6 2.2 0.9 0.3
560 0.1 1.6 1.1 1.5 1.0 0.2
650 0.2 1.4 0.7 1.1 0.8 0.2
“
The samples contained a small number of supported chromium acetylacetonate complexes (<0.05/nm2 surface groups).

(A) (B) corresponded to that obtained by Morrow and McFarlan.9 They

Wavanumbers/cm·1 Wavenumbers/cnv1
PPM PPM
Figure 14. Comparison of the FTIR, MAS NMR and simulated ‘H
MAS NMR spectra of the original 450 °C silica and the silylated 450
eC silica, with chromium acetylacetonate complex, after oxidation. In
both samples the total number of OH groups/nm2 as determined by
MAS NMR was 3.3-3A
more close to each other and thus show more H-bonded character.
A similar increase in the relative amount of H-bonded OH groups
was revealed in the simulations of the *H MAS NMR spectra.
In the original 450 °C silica the number of isolated and H-bonded
OH groups was 2.1 and 1.3, respectively.12 In the oxidized
silylated silica the simulations gave 1.7 and 1.6, respectively.
Discussion
Most of the isolated OH groups present on silica could be
silylated by HMDS independent of the preheat temperature of
silica. Thus, contrary to previous observations6 we found a
substantial proportion of the isolated OH groups on highly
dehydroxylated silica surfaces to be reactive as well. The number
of TMS groups bonded to 200-450 °C silica corresponded to the
fast reaction proposed by Snyder and Ward.7 Thus, no crowded
surface was produced. Furthermore, because the number of TMS
groups stayed constant on 200-450 °C silica, it can be assumed
that when silica is dehydroxylated at 200-450 0 C the only change
that occurs during heat treatment is the removal of strongly
H-bonded OH groups and partial removal of the so-called
inaccesible bulk OH groups. These bulk OH groups do not
participate in the reactions to any great extent as shown
previously.12
Discrepancy in OH Groups Determinations. The surface
coverage of 1.6 TMS groups/nm2 obtained on 200-450 °C silica
determined 1.5 TMS groups/nm2 for 150 °C heat treated silica
and 1.6 for 450 °C silica after the reaction of HMDS at 150 °C.
In addition, the total number of OH groups of porous silica EP10
(6.5 OH/nm2) determined earlier12 corresponds to the number
of OH groups on nonporous precipitated silica (6.8 OH/nm2)
determined by Morrow and McFarlan using a thermogravimetric
method.9 However, there is a large difference in the number of
isolated OH groups determined being in their case 1.1 OH/nm2
for 150 °C treated silica and in our case 1.9 OH/nm2 for 200 °C
treated silica and 1.6 and 2.0-2.1 OH/nm2 for 450 °C treated
silica, respectively. They determined the number of isolated OH
groups by combining the HMDS reaction and FTIR spectra.
The inconsistency in the number of isolated OH groups could
be due to the different silicas used but is more likely due to the
different definitions of isolated OH groups. The assignment of
the isolated OH groups by MAS NMR is rather arbitrary and
may not necessarily correspond exactly with that for the IR
spectra. The reaction of a probe molecule would also not be
expected to match the spectroscopic definitions since the number
reacted may depend on many factors, the most important of which
in this case is probably the steric effect. The theoretical
justification for the fitting of four gaussian line shapes to the
silica MAS NMR spectra is unknown. Dilute dipolar coupled
spin systems observed without MAS should have Lorentzian line
shapes and high-speed MAS NMR line shapes of these systems
tend to be more Lorentzian.23 In practice the experimental line
shapes observed could not be fitted with Lorentzian line shapes.
In reality, there is probably a distribution of sites and possibly
line shapes. However, the simulations for silica preheated at
various temperatures12 show that this is a good ad hoc model,
with the populations of the four components gradually moving
to the narrowest component at high preheat temperatures. The
definition of the isolated SiOH groups by this method also closely
follows the trend in the TMS population for different preheated
silicas reacted here. In the IR spectra the isolated OH groups
as defined by the NMR simulation may come under the definition
of H-bonded OH groups, and an exact corresondence is difficult
to achieve.
It was partly shown by the reaction of T1CI4 at 450 °C with
the silylated 450 °C silica that not all the isolated OH groups
were occupied by TMS groups. The IR spectrum recorded after
the reaction (Figure 6B) was similar to the IR spectrum recorded
after T1CI4 reaction at 175 °C with pure 450 °C silica, i.e. the
peak due to isolated OH groups was observed.12 The peak was
not seen after the complete reaction of T1CI4 at 450 °C with
unsilylated 450 °C silica.12 The formation of completely new
isolated OH groups on the silica surface is unlikely due to the
preheat temperature of 450 °C used. However, the TMS groups
in the absence of oxygen can decompose slowly at high temper-
atures producing OH groups and free carbon and silicon on the
surface.1 The decomposition rate given was 0.02 TMS groups/
nm2.1 In our case it would correspond to less than 0.1 OH/
(nm2/h_1) produced during the reaction. In addition, no free
carbon was seen in the sample, and even in the presence of oxygen
at 400 °C no significant loss in the methyl groups was observed.
Therefore, we assume that the “unobserved” isolated OH groups
are now seen due to the removal of the influence of the TMS
groups. This means that in the NMR spectra the reason for not
1702 The Journal of Physical Chemistry,
seeing the residual isolated OH groups may be because of an
increase in the line widths due to the increased dipolar interaction
by the presence of the close CH3 groups, so that they are now
partially under the H-bonded OH group area. Thus, in the IR
spectra it is possible that the IR stretching frequencies of the
residual isolated OH groups are perturbed by the presence of the
CH3 groups shifting the peak due to isolated OH groups toward
lower wavenumbers. In the case of silylated 200-450 °C silica
the possible shift was about 25 cm-’ (see Figure 3). A similar
shift toward lower wavenumbers was observed in the case of Cr-
(acac)3 reactions with pure 200 °C silica, although the number
of chromium atoms bound was only 0.8/nm2.20 This perturbation
was also observed by Burneau et al.24 when recording FTIR spectra
from silica which was grafted with n-hexadecyl chains. Morrow
and McFarlan9 used the number of bound TMS groups to quantify
the number of isolated OH groups on 450 °C silica. Therefore,
if this interaction in their case had also been responsible for the
disappearance of the peak due to the isolated OH groups, it would
have resulted in too low value for the number of the isolated OH
groups on 450 °C silica.
Reaction with -Bonded Terminal OH Groups. It has been
observed previously8·12 and now also in this study that HMDS
reacts mostly with the isolated OH groups. However, let us
consider the reaction of HMDS with SiOH groups, either isolated
or H-bonded, which could then proceed
(I)
TMS
u
Me
\
'N/
H H-v
Me—si*' \
Me/ \ / ,-H
0 O'
1 1
1
7777s'//////
.
77777~si77777T
As can be seen the intermediate II is unfavorable since both H
and O of the OH group under reaction are already coordinated.
This would explain the selective reaction with the isolated OH
groups. We propose that the shoulder observed at +17 ppm in
the 29Si CPMAS NMR spectra of silylated 200 and 300 °C is
due to a TMS group produced by the reaction of HMDS with
a terminal H-bonded OH groups where the H is uncoordinated
as follows:
TMS
Me
Mes\
Me-sr \
, ..
1 1 1 1
1
^ ^in
_ _
111 m 77 Si
After heating above 450 °C, these groups are no longer present
due to dehydroxylation (see Figure 4). The terminal OH group
can be considered more “acidic" than the isolated OH groups and
should be more reactive than isolated OH groups. These types
of reactive OH groups have been proposed earlier.7 The shoulder
at +17 ppm is also evident in previous work on silylated silica,5·6
although it was not commented on. There is evidence for the
more reactive nature of these OH groups in some earlier work
by Sindorf and Maciel.5 In that work, a comparison of partially
and maximally reacted silica with HMDS seemed to indicate
that the shoulder at low preheat temperatures contributed more
to the overall intensity than the maximally reacted silica. This
is also supported by the work of Hertl and Hair,8 who proposed
that the slight reaction with H-bonded OH groups takes place
only during the initial stage of the reaction.
Recently, Morrow and McFarlan9 concluded that the terminal
OH groups are more accessible than the H-bonded OH groups
and proposed that the small number of H-bonded and/or some
terminal H-bonded OH groups that react with HMDS on 150
°C silica are the same ones that become transformed into isolated
Vol. 98, No. 6, 1994 Haukka and Root
OH groups upon preheating at 450 °C. These terminal OH
groups absorb at 3720 cm-1 on 150 °C silica9 and after
dehydroxylation at about 3745 cm-1 on 450 °C silica, and in both
cases in terms of MAS NMR probably come under the
definition of isolated OH groups.
From a deconvolution of the peak at 12-18 ppm, the number
of terminal OH groups can be determined. In the 200 °C
preheated silica, the area of this shoulder is around 25% of the
total and therefore represents about 0.4 OH/nm2. This number
is close to the difference (0.5 OH/nm2) between the number of
isolated OH groups on 150 °C and 450 °C silica determined by
Morrow and McFarlan9 using FTIR spectroscopy.
Secondary Reaction of Ammonia. The secondary reaction of
ammonia with silica heat treated at elevated temperatures cannot
be fully verified by the IR spectra (see Figure 3, spectra E and
F). However, the peaks observed at 3500 and 3595 cm-1 could
indicate the chemisorption of ammonia. Although, the absorption
at 3595 cm-1 could originate from the TMS groups, it is also
possible that in the reaction of ammonia with a siloxane bridge,
the support silicon atoms are so close that the adsorbed groups
are H-bonded as follows:
H
O ^
Si' 'Si + NH3 — H—N—H—O
as follows: I I
Si Si
(II) The NH3 reaction proceeds slowly because of the competition
between the tendency to coordinate or to dissociate.15 Therefore
TMS
the produced OH group could be H-bonded to the NH2 group,
/ Me
/ Me thus absorbing at a lower wavenumber of 3595 cm-1.
/ Si-Me
The difference between the total number of OH groups of
O' 0 silica determined by 29Si CPMAS NMR using the carbon
1
s'77777777s'/7777i
1
determination (method I) and by *H MAS NMR (method II)
can be partly related to the chemisorbed ammonia. The higher
value for the OH groups present at high preheat temperatures
for method I can be explained by the reaction of evolved ammonia
with siloxane bridges. Each siloxane bridge produces one 03-
SiOH and one 03SiNH2 group. These give intensity in the 29Si
spectra at the position of the 03SiOH peak at -102 ppm but do
not originate from the original OH groups of silica. The reason
for the high value at low preheat temperatures is not clear. It
seems unlikely that there are significant numbers of strained
siloxane bridges and since the OH group intensity is determined
from the 29Si spectrum, any explanation should involve the
Me production of some type of O3S1X group (where X is O or N).
Mxe
For example, physisorbed ammonia can be discounted since it
/
< would not give rise to an extra peak in the 29Si spectrum. If the
''
1 1
1
ammonia molecule is very strongly associated with some type of
l_
siloxane bridge, then it is conceivable that this could shift the
11 ®'7777
siloxane resonance to the SiOH group area, but this seems unlikely.
Oxidation of Silylated Silica Samples. According to the
thermogravimetric studies of Severin et al.,17 the temperature of
the most rapid weight loss for the trimethylsilyl silica surface is
515 °C in oxygen. In our case, however, 85% of carbon was
already removed at 500 °C in air. It was concluded17 that from
larger samples the heat evolved in the exothermic reaction cannot
be removed efficiently, causing a local temperature rise, and thus
an increase in reaction rate. In those experiments only a few
milligrams of silylated silica were used, whereas here 5-8 g of
sample was oxidized in air. It is possible that in our case this
proposed autoignition occurred, leading to the more complete
removal of carbon from the silylated silica surface even in air.
The surface species produced here differ somewhat from those
shown by Severin et al.17 In our case the formation of geminols
and silanetriols was enhanced, probably because of the low
oxidation temperature needed for the removal of carbon, which
also prevented the formation of siloxane bridges. In the samples
containing chromium, the peak due to the silanetriol group is
even more enhanced due to the lower oxidation temperature of
400 °C. According to thermogravimetric studies, Zmijewski et
Solid-State NMR and FTIR Studies
al.25 have concluded that SiCH3 and =Si(CH3)2 groups which
decompose at 650 and 600 °C are the most resistive toward air
treatment. This was also verified by 29Si CPMAS NMR spectra
of partly oxidized silylated silica by Severin et al.,17 who observed
the remaining surface species after oxidation in air at 650 °C to
be mainly the ones above. In our case the same trend in the
production of different methylated surface species was observed,
but due to the different experimental conditions (larger samples
of silylated silica) the decomposition temperature of the TMS
groups was lower.
Severin et al.17 concluded that it is not useful to assign a
decomposition temperature of the silylated silica to a certain
modification. Our results suggest, however, that when a large
amount of silylated silica powder is applied, a controlled surface
species can be generated. The oxidation time used in the case
of partly oxidized surfaces was as long as 4 h, which could have
led to stabilized surfaces. Severin et al.17 used untreated silica.
This means that water was released from silica during oxidation,
which complicates the oxidation, whereas in our case, the
continuous release of water was prevented by preheating the silica.
The silylated Cr/silica samples were prepared by the reaction
of Cr(acac)3 with the silylated silica surface.20 After chemi-
sorption two acetylacetonate ligands remain bonded to chromium.
A thermogravimetric study on the pure Cr/silica sample showed
that the ligands are removed in two stages in air.20 During the
first stage at around 230-280 °C, half of the ligands are removed
as acetylacetonate with the assistance of the OH groups of silica.
In the second stage a sudden weight decrease occurs at about 315
°C, reflecting the destruction of the remaining ligands. In the
case of silylated silica samples this decomposition of the
acetylacetonate ligands can create “hot spots” on the surface,
which could explain the removal of the methyl groups at the
lower temperature. The overall temperature was also low enough
to prevent the formation of siloxane bridges. This may be the
reason for the presence of such a large number of silanetriol
groups on the silica surface and the increased relative amount of
geminols with respect to the original silica samples.
Summary
The combined use of >H MAS NMR, 29Si CPMAS NMR, 13C
CPMAS NMR, and carbon determination can give a detailed
picture of the surface groups on silica after reaction with HMDS
and subsequent oxidation. When used in conjunction with FTIR,
these complementary techniques can enhance each other sub-
stantially. In terms of NMR, the reaction of HMDS with silica
is an extremely good system since there are three active NMR
nuclei present. The main points from this work can be summarized
as follows:
(1) A comparison of MAS NMR with 29Si CPMAS NMR
in combination with carbon determination showed that extra
surface groups, other than the TMS groups, are present after
HMDS reaction with silica. This was also supported by FTIR
spectra. These groups are due to the secondary reaction of the
released ammonia with strained siloxane bridges at high preheat
temperature but are unknown for the low-temperature preheated
silica. The reaction with the terminal H-bonded OH groups in
addition to the isolated OH groups on the low-temperature
preheated silica (<450 °C) was verified by 29Si CPMAS NMR,
the number of these groups on 200 °C silica being around 0.4
OH/nm2.
(2) The combination of MAS NMR and carbon deter-
mination was used for the pure oxidized HMDS samples to show
the number of OH groups and siloxane bridges produced at
different oxidation temperatures. In principle the number of
different methylated silicon groups on the surface can be
determined from 29Si CPMAS NMR but requires a higher signal
to noise ratio by, for example, the use of a larger volume MAS
rotor. The use of a large amount (5-8 g) of the silylated silica
sample for oxidation leads to a lower decomposition temperature
and partly stabilized modified surface.
The Journal of Physical Chemistry, Vol. 98, No. 6, 1994 1703
(3) On the pure oxidized silylated silica samples, a silanetriol
group (OSi(OH)3) was produced. Its number could even be
increased by using an additional compound to create “hot spots”.
This allowed the use of the lower decomposition temperature,
which prevented the formation of siloxane bridges. For opti-
mization of surface groups, the combination of MAS NMR
and 29Si CPMAS NMR is very important in order to characterize
the number and type of SiOH groups present, as well as residual
SiMe groups, on the silica surface. In addition, when comparing
the FTIR spectra and the simulated MAS NMR spectra of
the pure preheated silica with the spectra of the modified silica,
similar changes in the surface groups can be seen. A relative
increase in the number of H-bonded OH groups in both NMR
and IR spectra was observed, while the number of these groups
could be quantified by using the simulations of the MAS
NMR spectra.
Using these techniques the surface of silica can be characterized
in great detail and consequently modified in a very specific manner.
Solid-state NMR combined with FTIR and element determination
seems to be very useful for characterizing amorphous systems
such as high surface area silicas.
Acknowledgment. The authors thank Mirja Rissanen of
Microchemistry Ltd. for the ALE processing and Ari Saasta-
moinen of Neste Oy for the carbon determinations. The valuable
discussions with Dr. Eeva-Liisa Lakomaa of Microchemistry Ltd.
and Dr. Thomas Garoff of Neste Oy are gratefully acknowledged.
Dr. Tapani Venalainen of the Department of Chemistry, Uni-
versity of Joensuu, is thanked for helping with the use of the
FTIR equipment. This work was funded in part by the Academy
of Finland. We would also like to thank Tiit Tuherm, Ants
Salumae, and Priit Sarv at the Estonian Academy of Sciencies,
Tallinn, Estonia, for the design and manufacture of the low
background double-resonance MAS NMR probe.
References and Notes
(1) Van Roosmalen, A. J.; Hartmann, M. C. G.; Mol. J. C. J. Catal.
1980, 66, 112.
(2) Rosenthal, D. J.; White, M. G.; Paxis, G. D. AIChE J. 1987,3, 336.
(3) Boudreau, S. P.; Cooper, W. T. Anal. Chem. 1989, 61, 41.
(4) Van Roosmalen, A. J.; Mol, J. C. J. Phys. Chem. 1978, 82, 2748.
(5) Sindorf, D. W.; Maciel, G. E. J. Phys. Chem. 1982, 86, 5208.
(6) Sindorf, D. W.; Maciel, G. E. J. Phys. Chem. 1983, 87, 5516.
(7) Snyder, L. R.; Ward, J. W. J. Phys. Chem. 1966, 70, 3941.
(8) Hertl, W.; Hair, M. L. J. Phys. Chem. 1971, 7J, 2181.
Morrow, B. A.; McFarlan, A. J. Langmuir 1991, 7, 1695.
(9)
(10) Zettlemoyer, A. C.; Hsing, . H. J. Colloid Interface Sci. 1977, 58,
263.
(11) Stark, F. O.; Johansson, . K.; Vogel, G. E.; Chaffee, R. G.; Lacefield,
R. M. J. Phys. Chem. 1968, 72, 2750.
(12) Haukka, S.; Lakomaa, E.-L.; Root, A. J. Phys. Chem. 1993, 97,
5085.
(13) Blitz, J. P. Colloids Surf. 1990, 63, 11.
(14) Peri, J. B. J. Phys. Chem. 1966, 70, 2937.
(15) Morrow, B. A.; Coody, I. A.; Lee, L. S. M. J. Phys. Chem. 1976,80,
2761.
(16) Fripiat, J. J.; Uytterhoeven, J.; Schobinger, U.; Deuel, H.Helv. Chim.
Acta 1960, 43, 176.
(17) Severin, J. W.; van der Wei, H.; Camps, I. G. J.; Baken, J. . E.;
Vankan, J. M. J. Surf Interface Anal. 1992, 19, 133.
(18) Suntola, T. Mater. Sci. Rep. 1989, 4, 261.
(19) Haukka, S.; Lakomaa, E.-L.; Suntola, T. Thin Solid Films 1993,
225, 280.
(20) Haukka, S.; Lakomaa, E.-L.; Suntola, T. Appl. Surf. Sci., In press.
(21) Haukka, S.; Lakomaa, E.-L.; Jylha, O.; Vilhunen, J.; Homytzkyj, S.
Langmuir, In press.
(22) Severin, J. W.; Vankan, J. M. J. Philips J. Res. 1990, 45, 35.
(23) Brunner, E.; Fenzke, D.; Freude, D.; Pfeifer, H. Chem. Phys. Lett.
1990, 169, 591.
(24) Burneau, A.; Barr£s, O.; Vidal, A.; Balard, H.; Ligner, G.; Papier,
E. Langmuir 1990, 6, 1389.
(25) Zmijewski, T.; Mioduska, M.; Pacewska, B. J. Ther. Anal. 1987,32,
1755.