ELSEVIER Journal of Non-Crystalline Solids 189 (1995) 90-100

J OURNA L O F
Structural characterization of silica xerogels
M. J. Muf i oz- A guad o a, *, M. Gregork i ewi tz a,1, F.J. B ermej o b
a Instituto de Ciencia de Materiales, Consejo Superior de Investigaciones Cientificas, Serrano 115 bis, E-28006 Madrid, Spain
b lnstituto de Estructura de la Materia, Consejo Superior de lnvestigaciones Cientificas, Serrano 123, E-28006 Madrid, Spain
Received 5 May 1994; revised manuscript received 25 October 1994
Ab stract
The structure of silica xerogels prepared following a fully inorganic route was investigated by means of the concurrent
use of gas-adsorption, solid-state nuclear magnetic resonance and neutron diffraction techniques. Such an approach enables
consistent estimates for the particle and pore sizes to be derived which show the existence of microporous structures of radii
ranging from 8 to 28 A depending upon the pH during gel formation. The microscopic, intra-particle structure was
investigated by comparison of the experimental interference functions derived from diffraction measurements with those
calculated from models starting from the structure of well known silica polymorphs.
1. I nt r o d uc t i o n
The past decade has wi t nessed substantial i ndus-
trial and research effort t owar ds the preparat i on of
i nor gani c- based membr anes mai nl y devot ed to sepa-
rat i on pur poses under condi t i ons wher e or gani c- based
mat eri al s become unst abl e [1]. Such appl i cat i ons re-
quire preparat i on of a por ous mat eri al wi t h wel l
defi ned pore size. In the search f or mat eri al s capabl e
of f or mi ng por ous substrates wi t h pore sizes wel l
bel ow t hose commer ci al l y available, as requi red f or
gas separat i on purposes, silica appeared as an opti-
mal candi dat e because of its l arge speci fi c surface
and small pore sizes ( = 20 A). Such a pr ospect l ed
us t o prepare mi cr opor ous silica membr anes ai mi ng
f or possi bl e industrial uses [2]. Resul t s r egar di ng the
structural charact eri st i cs of silica xerogel s able to
f or m membr anous mat eri al s whi ch have been pre-
pared by means of s ol - ge l procedures starting f r om
col l oi dal silica are presented. The macr oscopi c char-
act eri zat i on in t erms of free surface and vol ume has
been carri ed out by means of the anal ysi s of gas-ad-
sorpt i on i sot herms, f r om wher e est i mat es for the
pore sizes coul d be derived. At mi cr oscopi c scales,
bot h solid-state nucl ear magnet i c resonance ( NMR)
and neut ron di ffract i on experi ment s have been used
to pr ovi de compl ement ar y data.
Apar t f r om its t echnol ogi cal rel evance, the avail-
ability of por ous mat eri al s wi t h small and wel l de-
fi ned pore sizes wi l l enable the st udy of a vast range
of interfacial phenomena (liquid dynami cs in con-
fi ned geomet ri es, wet t i ng transitions, etc. ) free f r om
bul k cont ri but i ons.
* Corresponding author. E-mail: immmgl8@cc.csic.es.
l Present address: Dipartimento de Science della Terra, Univer-
sitfi di Siena, Via delle Cerchia 3, 1-53100 Siena, Italy.
2. Ex p e r i m e nt a l
Silica xerogel s wer e obt ai ned f r om i norgani c gel s
synt hesi zed by mi xi ng aqueous sodi um silicate (6
0022-3093/95/$09.50 1995 Elsevier Science B.V. All rights reserved
SSDI 0022- 3093( 95) 00186- 7
M.1. Muhoz-Aguado et al. /Journal of Non-Crystalline Solids 189 (1995) 90-100 91
mo l / 1 SiO 2 and Si O2/ / Na20 = 3.3 by weight) solu-
tions with hydrochloric acid HCI under controlled
pH without maki ng recourse to any other additive,
fol l owi ng the procedures described in more detail in
Ref. [2]. Precursor sols were formed in a pol ypropy-
lene beaker, where HC1 (2M) and the sodi um silicate
solution were simultaneously added and mi xed under
vi gorous stirring taking special care so that the pH of
the mixture was constant during sol formation. Such
conditions were achi eved by means of a peristaltic
pump operating at 0.5 c m3/ mi n which served to
dispense the silicate solution whereas the acid was
added by an aut omat i c buret connected to a pH- me-
ter so that the acid was released stepwise to keep pH
close to the value required. Once sol format i on was
achieved, the contents of the vessel were transferred
to pol yuret hane containers whi ch were hermetically
closed until gelation.
Aft er gelation, the gels were t horoughl y washed
with distilled wat er in order to eliminate C1- ions as
well as monomers, and allowed to dry at ambient
conditions in order to obtain xerogels. The H2 0
content whi ch could not be eliminated was estimated
to be --~ 10 wt % for all xerogels.
Xerogel s prepared under different pH conditions
will be referred to with a digit indicating the pH
value kept during the pol ycondensat i on reactions,
i.e., xerogel 3 will correspond to a sampl e prepared
at pH = 3.
The measurement s of nitrogen adsor pt i on- desor p-
tion isotherms were carried out using Mi cromeri t i s
2000 and Carlo Erba equipment. Thermal pre-treat-
ment consisted of vacuum annealing of sampl es at
443 K for 18 h. The calculation of the specific
surface was carried out by Brunauer, Emmet t and
Teller (BET) established met hods [3], and estimates
of surface area are referred to as SBE T. Reproducibil-
ity of results was a maxi mum difference of about
three parts per thousand (i.e., differences bet ween
runs of ~ 2 m2 / g for total surfaces of 650 m2/ g;
see Tabl e 1 below).
Solid-state NMR 29Si spectra were measured, at
r oom temperature, at 79.5 MHz on a spect romet er
(Bruker MSL-400) equipped with a magi c-angl e
spinning (MAS) device. Si chemi cal shifts were
measured with respect to a tetramethylsilane (TMS)
standard.
Neutron diffraction measurement s were carried
out using the DN5 powder di ffract omet er located at
one of the neutron lines of the Silo6 reactor hosted
by the CEN, Grenobl e (France). The sampl e (about 5
g) was placed inside a cylindrical vanadi um con-
tainer (internal di amet er 10 mm), and runs using two
different incident wavel engt hs of A = 1.425 and 2.49
.~ were carried out. The multidetector bank spans an
angular range of 0.5 < 20 < 80.4 . Under such con-
ditions, the average neutron flux at the s ampl e table
was of 2500 ne ut r ons / c m 2 s for h = 1.425 A and
4500 ne ut r ons / c m 2 s for A = 2.49 ,~. The relatively
long wavel engt hs were dictated by the need to reach
moment um-t ransfers as low as Q = 0.05 , ~- i in
order to explore regions well bel ow Q = 0.5 ,~-1
where the intensity showed a strong rise in previous
X-ray [4] and neutron [26] results. Some exampl es of
di ffract ograms after correction for container scatter-
ing are shown in Fig. 1 for three different xerogels
(pH 1, 3 and 6). All sampl es present a sharp and
intense small-angle peak fol l owed by smoot h oscilla-
tions characteristic of amorphous structures. The po-
sition of the first peak vari es appreciably with pH,
and its shape can be gauged from inspection of the
inset of Fig. 1, where some results correspondi ng to
longer wavel engt h are displayed. The existence of
such a small-angle peak was also confi rmed by
preliminary X-ray measurement s [4], where the ob-
served diffraction pattern consisted in a strong
small-angle peak fol l owed by a far less intense and
broader peak located at = 1.7 , ~-1 which became
visible in wi de-angl e X-ray measurement s [5].
In order to derive I ( Q) = S( Q) - 1 interference
functions, the data were normal i zed and the correct-
ness of such a procedure was tested by means of the
l ow-r slopes of the reduced pair correlations as
described below.
The intensity scattered by the sample, /sample(Q),
can be decomposed into contributions from nuclear
scattering not gi vi ng rise to interference effects, nor-
mal l y referred to as ' sel f - t er ms' , S~(Q), and those,
I( Q) or ' di st i nct ' , which are due to interference
bet ween waves scattered by different at oms and con-
tain the structural information sought. An exampl e of
the function QI( Q) correspondi ng to xerogel 3 is
shown in Fig. 2. A substantial droop at high Q is
noticeable upon inspection of the figure. Such a
fal l -off may well be due to an inelastic contribution
arising from the presence of OH groups bound to the
92 M.I. Muhoz-Aguado et al. /Journal of Non-Crystalline Solids 189 (1995) 90-100
4.0 1
s.s 1
3.0 1
_ 2~ 1
~
2.0 10 4
- " 1.5 1
1.0 1
s.o 1
3.5 1 -
3.0 10 4.
2.5 1 .
~
2.0 l -
l.~ 1
LO 1
s.o 1
s.o 1
4.0 1 -
3.o l -
u
[
- : 2.0 1 -
1.0 1 -
0.0 lOSi
^ I
" e l / \ I
" e l I \ I
" * - I I " , , , _ J
" e l I - 7
' ' " 1 ~ I
. t , e l . . . . I
pH = 3
I I F I I
i i J
Q ( ~. t)
part i cl e surfaces. To account f or such an effect , we
have de c ompos e d t he t ot al i nt ensi t y in t er ms of ' s e l f '
and ' i nt er f er ence' cont r i but i ons as wel l as a cor r ec-
t i on t er m, P ( Q) , t o l ump t oget her all possi bl e causes
of i nel ast i ci t y, t hus l eadi ng to [6]
/sample(0) ~ Ss ( O ) + I ( O ) + P ( O )
-= -b2 + ~_, bi bj Si j ( O ) + P ( O ) , ( 1)
i i ~ j
wher e bi is the aver age coher ent scat t eri ng l engt h of
nucl ei i and Sij(Q) are the part i al st ruct ure f act or s
def i ned in t er ms of l ocal at omi c densi t i es, pij(r) (the
number densi t y of j - t ype at oms l ocat ed at a di st ance
r f r om at om i), and an aver age densi t y, p0:
s i n ( 0 r )
SiJ(Q) = fo 4' r r r 2[ P i j ( r) - p0] Q--------~ d r .
(2)
The cor r ect i on t er m was model l ed in t er ms of a
s i mpl e pol ynomi al expr essi on, P ( Q) = B ( Q) +
C( Q2) , whi ch is nor mal l y used f or the anal ysi s of
mol ecul ar mat er i al s [7], and the t wo coef f i ci ent s
wer e l eft as adj ust abl e par amet er s in order to r e move
the dropout . The resul t i ng QI(Q) i nt er f er ence func-
t i ons, aft er account i ng f or such an ef f ect so that the
f unct i on osci l l at es about the absci ssa, can be seen in
Fig. 2.
3 . R e s ul t s
The mai n char act er i st i cs of the adsor pt i on
i sot her ms of Si O 2 are known to depend upon the
pol ycondens at i on pH. As s hown f r om dat a di spl ayed
in Fig. 3, the i sot her ms of si l i ca s ampl es f or 1 < pH
< 5 are of t ype I [8], whi ch is charact eri st i c of
mi cr opor ous mat er i al s ( r p < 10 ,A [9]), wher eas f or
6 < pH < 8 t hey under go a dr amat i c change to t ype
IV, exhi bi t i ng a hyst er esi s l oop ori gi nat ed by capi l -
l ar y condensat i on wi t hi n the mesopores (rp > 10 ~k).
Fig. 1. Neutron diffractograms after correction for container scat-
tering of xerogels 1, 3 and 6. The main plots correspond to
experiments performed with A = 1.425 ,A. The inset depicts the
low-Q region of xerogel 3 as measured with A = 2.49 A.
M.I. Muhoz-Aguado et al. /Journal of Non-Crystalline Solids 189 (1995) 90-100 93
l 1 0 4
s l 0 ~
o]o'
~
- 5 1 0 j
~ - 1 1 0 4
- 2 1 0 4
.2 1
- 3 1 0 4
0
4 ,

I I I I I
1 2 3 4 5
Q (.~. l)
Fi g. 2. I nt er f er ence f unct i on, QI(Q), of xer ogel 3, bef or e ( - - - )
and aft er ( ) el i mi nat i on of P(Q) i nel ast i c cont r i but i on t o
t he st r uct ur e fact or.
The determination of the surface and the pore
vol ume distribution for mi croporous sampl es was
accompl i shed by use of the mi cropore (MP) met hod
[10] (based upon standard t-curves and on the down-
ward deviations of the straight line in the de Boer
vl-t plot [11]), whereas a model -free approach usu-
ally referred to as corrected model l ess met hods [12]
was used for determinations in the mesoporous sam-
ples (based on a standard isotherm and capillary
condensation). As shown in Fig. 4, the distributions
of pore vol umes present a somewhat compl i cat ed
shape with a mai n peak and some (one or two)
subsidiary maxi ma. Pore vol umes inferred f r om ad-
sorption data for gels obtained in the range of 1 <
pH < 5 as defined by the ext rema of the distributions
correspond to radii of about 8 ,~ and 11 ,~, bei ng the
abundance ratio of pore sizes as est i mat ed f r om the
areas of the peaks of = 0. 7/ 0. 3. Such distributions
are substantially broadened for pH > 5 as a conse-
quence of the mesoporous structure, and subsidiary
maxi ma appear clearly in the distributions, although
they account for only about 30% of the total area.
The curve correspondi ng to pH = 7 shown in Fig. 4
indicates that, although most of the area corresponds
to a peak indicating a pore radius of = 17 A, small
pore sizes are still apparent. Far f r om bei ng a unique
feature, the appearance of mul t i modal distributions
of pore vol umes in silica was also evident in small-
angle neutron scattering studies of silica-supported
50 0 :-
Xerogel- 7
--~ 300 Xerogel- 2
200
too
0 0. 2 0 . 4 0. 6 0. 8 1
P/Po
Fig. 3. Ads or pt i on- de s or pt i on i s ot her ms of ni t r ogen on si l i ca
xer ogel s 2 and 7 at 77. 3 K. Ads or pt i on ( O) and desor pt i on ( O) .
Val ues i n t he abs ci s s a r epr esent rel at i ve pr es s ur es .
catalysts [13] although, as expected, far smaller pore
sizes are found in the present work. With the above-
referred provi sos in mind, Tabl e 1 gives results
obtained f r om analysis of mi cropores of sampl es
prepared at 1 ~< pH ~< 5, using the standard isotherm
due to Carruthers et al. [14] as a reference. Spore and
Vpore represent the surface area of the pore walls and
the porous vol ume, respect i vel y and S t is the total
surface. The close proxi mi t y of the Spore values to
those for S t strongly suggests that there is little outer
surface and the mi cropores observed must be either
within large particles or in interstitial space. In the
latter case, the pore size woul d be controlled by the
silica particle size.
Representative MAS 2 9 5 i NMR spectra for the
silica xerogel s in the pH range 1 - 8 are shown in Fig.
5. The common multiplet structure of those spectra
can be described in t erms of three well resolved lines
with chemi cal shifts of = - 1 1 1 , - 1 0 2 and - 9 2
ppm. This contrasts with the case of other silica
sampl es [13], where only a broad line of = 700 Hz
0 . 3 0 , " " ".
Xe r o g e l - 7 "
0. 20 ,." ,
~" 0A0 " ' " " " " . . . . ',
a
o.o0 _. ," ' ~ ~ , , o g e l 3 ,
0 5 10 15 20 25
r (A)
Fi g. 4. Di s t r i but i ons of por e vol ume f or si l i ca xer ogel s 3 ( )
and 7 ( - - - ) , as obt ai ned f r om t he MP and cor r ect ed mode l l e s s
me t hods r espect i vel y. The s t andar d t - cur ve of Car r ut her s et al.
[14] wa s used.
94 M.L Muhoz-Aguado et al. / Journal of Non-Crystalline Solids 189 (1995) 90-100
in width centered at - 1 0 6 ( - 1 1 2 ) ppm depending
upon the specific sampl e has been found, but agrees
with Brinker et al. [15] for xerogels prepared f r om
metal alkoxide precursors. The spectra for all the
sampl es studied can be approxi mat ed by a sum of
three Gaussian functions, and the accepted assign-
ment of these three peaks [15,17] port rays t hem as
arising from Si in different chemi cal environments,
so that the line with the largest absolute shift corre-
sponds to Si in 4-connected Q4 units, Si(OSi)4; the
intermediate one, referred to as Q3, to Si(OSi)3OH
groups; and the one with the l owest shift, Q2, arises
from Si(OSi)2(OH) 2 groups, where Si is bonded to
only two neighbouring Si O 4 tetrahedra. Additional
support for such an assi gnment comes f r om analysis
of the NMR spectra of the starting materials as well
as those recorded during condensation [2]. Spectra
recorded at several times within a period of 72 h
after the reaction initiation reveal a decrease in inte-
grated intensity of the Q2 and Q3 lines with an
increase in that for Q4. Both the relative intensity of
the lines and their evolution with time are strongly
dependent on the pol ycondensat i on pH. Such a de-
pendence is evident as a decrease in intensity of the
Q2 line concomi t ant with an increase in the intensity
of the Q4 line as the pH is increased. The same trend
is also recogni zed in Fig. 5 regarding xerogels 1- 8:
notice that the relative (percentage) intensity of the
0 4 line increases continuously f r om a value of 0.56
for pH 1 to 0.78 for pH 8, concomitant with a
somewhat less syst emat i c reduction in intensity of
Q3 which goes f r om 0.40 to 0.22 for xerogels 1 and
8, respectively, and a continuous decrease for Q2.
3 /
2j
1 /
t I I
Q4
I
A
a
Ill
I I I I I i i I I I I I
- 7 0 - 100 - 130 - 7 0 - 100 - 130
~ ) ( p p m ) ~ ( p p m }
Fig. 5. 29Si NMR spectra of silica xerogels 1-8. The spectrum
number indicates the pH of sol formation.
Table 1
Comparison of results from adsorption isotherms for total, S t and
Vt, and pore, Spore and Vp . . . . surfaces and volume, respectively, as
obtained by the MP method using the Sing standard t-curve, for
silica xerogels formed within the range 1 < pH < 5
pH SBE v V t Sing t-curve
(m2/ g) (cma/ g) Spore Vpore St
(m2/ g) (cm3/g) (m2/ g)
1 693(2) 0.39(1) 693 0.38 697
2 683(2) 0.35(1) 680 0.33 685
3 654(2) 0.35(1) 641 0.33 645
4 6 3 4 ( 2 ) 0.38(1) 633 0.36 639
5 699(3) 0.44(2) 701 0.43 705
Numbers in parentheses correspond to standard errors.
These findings also suggest that the ratio of line
intensities reflects the particle size so that an esti-
mat e of this quantity could be derived from the
NMR data, at least for the purpose to contrast the
above-ment i oned results about the distribution of
voi d space. A schemat i c model such as that drawn in
Fig. 6 has been empl oyed to relate the intensity
ratios with the particle sizes. Such a model which
portrays a rather simplified picture of the particles
will be validated at further steps by means of com-
parison with results arising from independent tech-
niques, and considers the particle as a sphere con-
M.J. Muhoz-Aguado et al./Journal of Non-Crystalline Solids 189 (1995) 90-100 95
t ai ni ng a dense st r uct ur e ma de up f r om SiO4 uni t s,
wi t h a cor e of r adi us rcore s ur r ounded by a shel l of
o
t hi cknes s E = 2. 7 A, i . e. , equal to t he si de of a Si O 4
t et r ahedr on ( t wi ce t he oxyge n i oni c r adi us [18]). The
cor e i s t her ef or e a s s ume d to be c ompos e d by Si in
t et r ahedr al l y coor di nat ed Q4 si t es, wher eas t he shel l
i s r egar ded, f r om cons i der at i ons about t he f eas i bl e
connect i vi t i es of t he Si O 4 t et r ahedr a at t he i nt er f ace,
as c o mp o s e d of Q3 and Q2 s peci es onl y. The vol ume
r at i o be t we e n t he shel l and cor e woul d t hus be gi ven
by t he r at i o of t he c or r e s pondi ng i nt egr at ed i nt ensi -
t i es, and coul d be us ed to es t i mat e t he r adi us of t he
par t i cl e t hr ough t he r el at i on
0 2 + Q3 V s h e l l R 3 _ r3ore
Q4 Vcor e r3ore
( r . . . . + E) 3 - rc3ore
= F3or e ( 3 )
Once rcore has been eval uat ed, t he t ot al par t i cl e
r adi us, R w, is cal cul at ed by addi ng t he shel l t hi ck-
ness, E, and t he i oni c r adi us of oxyge n ( see Fi g. 6).
The mor e r el evant r esul t s ar e gi ven in t he s econd
col umn of Tabl e 2 and s how t hat t he par t i cl e si ze is
of t he s ame or der of ma gni t ude as t he por e si ze, bot h
s howi ng a s i gni f i cant i ncr eas e wi t h pH.
The cal cul at i on of par t i cl e si zes f r om t he NMR
i nt ensi t i es r est s on t he as s umpt i on t hat such par t i cl es
Rw = R 1 + 1.35,A
i
z 3 1 . 3 5 A
Fig. 6. Schematic illustration of a spherical dense silica particle.
The particle radius, Rw, is obtained by the sum of rcore, the shell
thickness, E, and the oxygen ionic radius (1.35 A).
Table 2
Pore size, particle diameters and interparticle distances.
pH of Pore diam- D (.~) d (A)
forma- eter,
tion Dp NMR Bl6try d 1 = 2w d2(G(r))
(ND) / Q1
1 22.4(3) 34(3) 2 6 ( 2 ) 33(2) 28
2 20.4(2) 36(4)
3 21.4(2) 37(4) 3 1 ( 3 ) 37(1) 32
4 24.0(3) 35(4) 3 5 ( 2 ) 42(2) 40
5 25.3(4) 39(4) 3 0 ( 5 ) 37(4) 42
6 43.6(7) 44(6) 5 8 ( 7 ) 70(5) 57
7 54.8(9) 59(8)
8 56.2(8) 67(8) > 53 > 70 60
Pore diameters are derived from nitrogen adsorption data (Dp =
2%) assuming a cylindrical geometry and particle diameters, D,
are calculated from NMR (2R w) results and neutron diffraction
(ND) measurements (see text). Interparticle distances, dl.2, are
calculated from the wave number of the first peak in the neutron
diffraction pattern, a l , or from the crossover in the G(r) radial
distribution function (see text). Numbers in parentheses corre-
spond to standard errors.
are dense and s pher i cal in shape. The f ol l owi ng set
of cal cul at i ons wer e car r i ed out t o ascer t ai n t he
val i di t y of t hat as s umpt i on usi ng neut r on di f f r act i on
dat a.
Apa r t f r om t he gener al shape of t he di f f r ac-
t ogr ams , whi ch has been br i ef l y des cr i bed above, t he
obs e r ve d i nt ensi t i es wer e i nt er pr et ed in t wo di f f er ent
ways. The fi rst one concer ns t he r educed r adi al
di st r i but i on f unct i on, G(r), whi c h i s cal cul at ed by
Four i er i nver s i on of t he i nt er f er ence f unct i on, QI(Q),
G( r ) =4" t rrp [ g( r) - 1]
2
f QI ( Q) M( Q) si n Qr dQ, ( 4 )
' /T
Jo
and i s r el at ed t o t he convent i onal g( r) used f or t he
des cr i pt i on of t he st at i c st r uct ur e of l i qui ds and
a mor phous mat er i al s. Becaus e of t he r el at i vel y s mal l
r ange of mome nt um t r ansf er s acces s i bl e t o t hi s ex-
per i ment , t he i nt r oduct i on o f a Lor ch modi f i cat i on
f unct i on [19], M( Q) = (Qmax/~rQ) sin(,rrQ/Qmax),
to r educe t he t er mi nat i on r i ppl es in t he Four i er t r ans-
f or m wa s i mper at i ve. Such a f i l t er act s degr adi ng t he
r eal space r es ol ut i on whi ch, t oget her wi t h t he l ow
val ues of Qmax r eached in t he pr esent set of exper i -
ment s, i mpl i es t hat t he at t ai nabl e r es ol ut i on in r eal
o
space cannot be bet t er t han 1 A, so t hat it wi l l not be
96 M.J. Muhoz-Aguado et al. /Journal of Non-Crystalline Solids 189 (1995) 90-100
possi bl e t o di scri mi nat e whet her any substantial
change in the l ow- r part of G( r) , cont ai ni ng infor-
mat i on about the short -range structure, takes pl ace
al ong wi t h the change of pH. Such experi ment al
condi t i ons wer e mot i vat ed by the need to access ver y
l ow mome nt um t ransfers as descri bed above, and,
because our interest r egar di ng this is f ocussed on a
mes os copi c scale, l ooki ng f or trends in G( r ) associ -
ated wi t h di st ances of the or der of a f ew nanomet ers.
An exampl e of t he cal cul at ed G( r ) compr i si ng
the most represent at i ve xerogel s is shown in Fig. 7.
As expect ed, no changes in the structure bel ow 10 ,~
can be inferred, and the onl y r ecogni zabl e feat ures
can be a s s i gne d t o short -range structure, wi t h peaks
at 1.6 and 2.6 A cor r espondi ng t o tetrahedral dsi _ o
and do_ o di st ances as wel l as di st ances to next-
nearest nei ghbours. The i mport ant t hi ng to not e re-
gards the appearance of a wel l defi ned mi ni mum
l ocat ed at 1 0 - 2 5 A, dependi ng upon sampl e prepara-
t i on (pH). Such a mi ni mum, whi ch is obvi ousl y
associ at ed wi t h regi ons of ver y l ow densi t y, coul d
arise f r om por e- par t i cl e and p o r e - p o r e correl at i ons,
i f the same ideas sket ched by Elliott [20] in the
di scussi on of the first sharp di ffract i on peak ( FSDP)
in vi t reous silica are applied at these l engt h-scal es.
Fr om such consi derat i ons and i nspect i on of Fig. 7, a
charact eri st i c distance, d 2, can be defi ned as that
wher e the G( r ) static pai r correl at i on returns to zero
after the mi ni mum, and it can be associ at ed wi t h
est i mat es of interparticle distances. Some rel evant
number s for such a quant i t y are gi ven in the last
col umn of Tabl e 2.
The next quest i on posed by the anal ysi s of NMR
data regards veri fi cat i on that the silica part i cl es are
const i t ut ed by dense structures. I n this case, and
even i f t he al l owed range of Q is restricted, the
i nf or mat i on sought is cont ai ned in the smoot h oscil-
lations appeari ng f r om Q = 1 . ~- 1 onwar ds (see Fig.
1), whi ch must arise f r om at omi c short -range correla-
tions.
The pr ocedur e f ol l owed f or t he anal ysi s of these
osci l l at i ons is basi cal l y the same as that empl oyed
for the separat i on of t he i nt ramol ecul ar part f r om the
total structure fact or in liquid or amor phous mol ecu-
lar mat eri al s [21], wher e the total st ruct ure f act or is
decompos ed into intra- and inter-particle ( mol ecul e)
correl at i ons. The f or mer cont ri but i on can be cal cu-
lated i f model s for t he intra-particle structure are
:., erogel4
' : ! IV' w ~ A, . / s
i~,i~/~/ X ~ ~ " '" ~t
[ Xerogel-5
. ~,,A,,n,
" -
~ Xerogel-4
' ~
. 17
3 2 1
Xerogel-I
0 20 4 0 60 80 10 0
r ~)
Fig. 7. Reduced radial distribution functions, G(r), of silica
xerogels 1, 3, 4, 5, 6 and 8. The line labelled as 1 displays the
values of the particle diameter, D, obtained from 29Si NMR
spectra. Line 2 shows the interparticle distance, dl, calculated
from the momentum transfer corresponding to the maxima of the
first diffraction peak (d 1 = 2~r/Q 1) and line 3 shows the corre-
sponding particle diameter obtained from the Bl6try approxima-
tion (see text).
M.J. Muhoz-Aguado et aL /Journal of Non-Crystalline Solids 189 (1995) 90-100 97
brought forward, so that a compari son bet ween the
calculated and measured QI( Q) interference func-
tions becomes possible. Such quantities are calcu-
lated accordi ng to
cubic vol ume of a variable size so that both form and
size could be opt i mi zed by compari son with experi-
ment.
QI(Q) E b ,b j s i n( Qr , j ) exp( ,h--~o2~
= I , ( 5 )
iv~j rij
where u 2 is the mean square at omi c di spl acement
due to thermal vibrations, an estimate of whi ch can
be obtained f r om the knowl edge of the De bye - Wa l l e r
fact or in vitreous silica (an average val ue of 0.01 ,~2
was used), and the summat i on runs over all at om
pairs within the particle under consideration and
separated by the distance rij. In order to build mod-
els to be compar ed with the experi ment al intensities,
several approaches can be followed. One well known
approach, whi ch was previ ousl y used for the analysis
of the QI( Q) curves in vitreous silica [22], consists
of generating model s by packi ng the basic structural
units (tetrahedra) following some prespecified rules
(as allowing or not for some amount of t hree-mem-
nered rings), which in one si mpl e case reduces to the
continuous random network. Alternatively, and in
order to test a greater vari et y of possible structures
for our sol - gel - der i ved material, we chose to com-
pare experi ment al intensities with si mpl e model s
consisting of a core cluster generated from the crys-
tal structures of the most common silica pol ymorphs,
truncating the structures at some distance and ac-
counting for surface effects. Several alternatives for
the shape and size of such clusters were expl ored for
each pol ymorph. Our choice of procedure was moti-
vat ed mor e by the need to provi de an answer to the
question posed by the analysis of the NMR signals
than by the ai m to establish the detailed mi croscopi c
structure whi ch is beyond the aim of the present
contribution. To proceed with specification of the
calculated interference function, QI(Q), the follow-
ing steps were taken.
(1) The initial structures considered were those of
cristobalite Fd3m, high cristobalite and l ow cristo-
halite [23], tridymite P 63/ mmc , tridymite C2222
[24] and quartz [25].
(2) A supercell was generated by repetition of
unit-cell structures for the six pol ymorphs under
consideration. Subsequently, clusters were cut leav-
ing onl y at oms within a spherical, octahedral or
2.0
1.5
1.0
--~ 0.5
C~
0.0
- 0 . 5
2 . 0
Oct ahed ron
. . . . i . . . . i . . . . i . . . . i . . . . i . . ~ , ,
1.5
1.0
0.5
0.0
-0.5
2 . 0
Sphere
, ' , , i 4
~ t
1 . 5 Cub e
1 . o
0 j ~ ~ ' ~ ' ,
0 . 0
- 1. 0 . . . . , . . . . , . . . . , . . . . , . . . . , . . . . .
0 1 2 3 4 5 6
rl (~,' b
Fig. 8. Comparison between the observed QI(Q) interference
function for xerogel 3 (vertical bars) with that calculated ( )
for clusters with the Fd3m cristobalitc structure. For the calcu-
lated curves, three different shapes (see insets) were tested, keep-
ing constant a particle volume of 2304 ,~3.
98 M.J. Muhoz-Aguado et al. / Journal of Non-Crystalline Solids 189 (1995) 90-100
(3) The calculation according to Eq. (5) was then
carried out. The number of atom pairs i nvol ved in
such calculations vari ed bet ween 200 and 300 de-
pending upon the structure under consideration.
As an illustration of the shape dependence, some
calculated QI(Q) interference functions correspond-
ing to Fd3m cristobalite, the optimal structure be-
tween the six pol ymorphs explored, are gi ven in Fig.
8, showi ng that a sphere gives the best agreement
with measurement . As can be seen, the calculated
peaks are substantially narrower than the observed
ones. To account for this, a structure relaxation
function, ~ ( r ) = 1 - (r/2R) n, with R bei ng the
particle radius, was introduced in Eq. (5). Such a
function, similar to the one empl oyed by Wada et al.
[26], has a smoot hi ng effect over the surface of the
silica particles which depends strongly on the expo-
nent. The best agreement bet ween calculation and
experi ment is shown in Fig. 9, which corresponds to
a structure generated from the pol ymor ph referred to
above with the truncation carried out for a sphere of
radius R = 8.19 ,~ and exponent n = 2.
In consequence, the assumpt i on that the particles
were dense and spherical, which is needed to guaran-
2.0
1 . 5
1.0
. . . . .
" 0 . 5
0 . 0
. 0 . 5
- 1. 0 . . . . I . . . . I . . . . I . . . . I . . . .
0 1 2 3 4 5 6
Q (~. t )
Fig. 9. The observed interference function of xerogel 3 () and its
comparison with that calculated for a spherical silica particle of
radius 8.19 A with an Fd3m cristobalite structure in its core
accounted for structure relaxation (see text) for the static correla-
tions near the particle surface by means of the relaxation function
~ ( r ) with n = 2.
tee the validity of Eq. (3) is validated by the diffrac-
tion results. It is wort h emphasi zi ng that both the
G(r) pair correlation functions (see Fig. 7) and the
calculations on model structure factors consistently
predict the same particle dimensions (within experi-
ment al error), whi ch can be favourabl y compared
with results f r om NMR data and adsorption isotherms
(see Tabl e 2), provi ded that, in this latter case, the
distributions are regarded as approxi mat el y uni-
modal.
4 . Di s c u s s i o n
The possible existence of spatial correlations be-
tween particles and voids, normal l y referred to as
chemical short- or medi um-range order, has attracted
substantial attention in recent years, mai nl y within
the context of the current discussions regarding the
origin of the FSDP [20]. The Bl&ry [27] model
deserves special consideration. Following Ref. [27],
the particle diameters can be inferred from
Ol=3' rr(1-e/2)/2h; ( l + e) =D/ h, ( 6)
where Q1 is the position of the first diffraction peak,
D is the particle diameter and h is the pore diameter.
Values for h are available from analysis of adsorp-
tion isotherms; thus Eq. (6) provi des a means to
estimate the particle size under the assumpt i on that
there exists a non-random arrangement of voids and
dense matter, and the numerical val ues for different
xerogel s are gi ven in Tabl e 2. From compari son of
the different col umns of Tabl e 2, it is clear that the
estimates for the particle sizes derived from Eq. (6)
are close to those obtained from NMR and also to
the interparticle distance, d I = 2~/Q1, calculated
under the assumpt i on that the position of the first
peak in I(Q) can be interpreted in terms of the
thermal equilibrium distance bet ween compact parti-
cles. Notice also that the particle size increases with
pH for all three techniques.
As a means to provi de a graphical compari son
bet ween the particle sizes and distances as derived
from the three afore-ment i oned techniques, Fig. 7
displays a set of curves corresponding to: the particle
diameters, D = 2R w, as derived f r om an analysis of
the NMR spectra; the equilibrium (thermal average)
M.J. Muhoz-Aguado et al. /Journal of Non-Crystalline Solids 189 (1995) 90-100 99
i nt er par t i cl e di st ances, d 1, as der i ved f r om t he mo-
ment um t r ansf er val ue cor r es pondi ng to t he fi rst
pe a k in t he obs e r ve d I ( Q) pat t er n; and t he par t i cl e
di amet er s der i ved f r om t he Bl &r y r el at i ons hi p (cf.
Eq. (6)), s upe r i mpos e d to t he G( r ) r educed r adi al
di s t r i but i on f unct i ons. As can be seen f r om t he gr aph,
a cor r el at i on bet ween t he par t i cl e di amet er s est i -
mat ed f r om s pect r os copi c means and t he di st ance at
whi c h G( r ) r et ur ns to zer o aft er t he fi rst br oad
mi n i mu m appear i ng at 15 A< r < 25 ~, can be
es t abl i s hed on empi r i cal gr ounds. The f act t hat t he
cr os s over c ome s cl ose to t he par t i cl e di s t ances est i -
mat ed f r om t he pos i t i on of Q1 suggest s t hat t he
par t i cl es are es s ent i al l y in cont act and t her ef or e t he
por es ar e f or med as i nt er st i ces of par t i cl e packi ng.
Sma l l - a ngl e neut r on scat t er i ng ( SANS) dat a con-
cer ni ng Vyc or por ous gl ass have been r epor t ed [28]
wher e t he pr es ence of a wel l r es ol ved al bei t br oad
pe a k seen at Q = 0. 02 . &- I was i nt er pr et ed in t er ms
of par t i cl e si zes of t he or der of 280 A cor r es pondi ng
t o a s ampl e wi t h a nomi nal por e r adi us of rp = 40 A.
Such a f eat ur e was al so obs e r ve d in SANS pat t er ns
f r om i nor gani c s i l i ca sol s at pH > 7 [29], whi ch
s how a peak at about 0 . 0 2 - 0 . 0 4 . &- i whos e shape
and pos i t i on depend on concent r at i on. By cont r ast ,
onl y a br oad peak, i f any, has been r epor t ed f r om
s mal l - angl e st udi es on mor e t enuous st r uct ur es such
as s i l i ca aer ogel s [30]. The pr es ence of a wel l de-
f i ned and r at her i nt ense di f f r act i on peak at ver y l ow
mome nt um t r ansf er s i n t he xe r oge l s s t udi ed in t hi s
wor k and t he l es s er pr omi ne nc e of such a f eat ur e ( or
i t s abs ence) in ot her mat er i al s can t hus be as s oci at ed
wi t h t he e xc e pt i ona l l y wel l def i ned par t i cl e shapes
and an or der ed packi ng achi eved as a cons equence
of t he f ul l y i nor gani c pr epar at i on pr ocedur e, whi ch
does not i nvol ve an addi t i ve.
The s i mi l ar i t y of s hor t - r ange at omi c st r uct ur e in
gel s pr epar ed by a r at her di f f er ent r out e ( aci d cat al y-
si s f r om t et r aet hoxys i l ane) to t hat of vi t r eous si l i ca
was al so poi nt ed out by Wa d a et al. [26] f r om a
l ar ge- Q pul s ed neut r on di f f r act i on exper i ment , wher e
t he r epor t ed st r uct ur e f act or s a bove s ome 4 ,&-1 ar e
s t r ongl y r emi ni s cent of t hat of vi t r eous si l i ca, t hus
l endi ng addi t i onal suppor t to t he f i ndi ng t hat t he
i nner st r uct ur e of t he gel par t i cl es cor r es ponds to a
dense ar r angement of cor ner - s har i ng Si O 4 t et r ahedr a.
The mos t not i ceabl e di f f er ence wi t h pr evi ous
st udi es on r el at ed mat er i al s such as s i l i ca- s uppor t ed
cat al ys t s [13] or ot her f or ms of si l i ca [16] concer ns
t he abs ence of any cl ear hi nt in t he MAS - NMR
spect r a r egar di ng peaks wi t h chemi cal shi f t s bet ween
- 102 and - 112 ppm, whi ch are us ual l y i nt er pr et ed
as evi dence of t he exi s t ence of t hr e e - me mbe r e d
s i l oxane r i ngs [15]. Such st r uct ur es t hus s eem to be
far l ess pr omi nent in t he pr esent s ampl es t han in
s ome ot her f or ms of si l i ca, wher e an abundance up
to f i ve per cent has been r epor t ed [13].
5. Concl us i ons
Fr om t he agr eement bet ween t he val ues f or t he
par t i cl e si ze der i ved f r om NMR and neut r on di f f r ac-
t i on, it is i nf er r ed t hat t he par t i cl e di amet er s wi t hi n
t he pH r ange 1 < pH < 5, wher e si l i ca be c ome s mi -
o
cr opor ous wi t h por e r adi us rp < 10 A, are of about
35 A, i ncr eas i ng wi t h pH up to rp = 25 A and a
par t i cl e si ze of 65 A f or pH = 8. Mor eover , f or pH
val ues be l ow 5, t he por e si ze di s t r i but i ons are r el a-
t i vel y nar r ow so t hat t hey can be r oughl y cons i der ed
as monodi s per s e.
The aut hor s t hank I. Sobr a dos and J. A. Al ons o,
I CM CSI C, Madr i d, who per f or med t he NMR and
neut r on di f f r act i on exper i ment s . Fi nanci al suppor t
f r om DGI CYT, Ma dr i d ( MAT91- 394) , as wel l as a
pr edoct or al gr ant ( MEC, Ma dr i d) to M. J . M. A. and
t r avel ai d f r om Ac t i on Int 6gr6e ( 91- 107A) are gr at e-
f ul l y acknowl edged.
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peak at 0.1 ~- 1 for xerogel 8 which went up to = 0.16 ~- 1
for xerogel 3. The position of such peaks is somewhat
smaller than that found from the neutron spectra, where the
values for the two quoted samples were of 0.125 and 0.20
100 M.J. Muhoz-Aguado et al. / Journal of Non-Crystalline Solids 189 (1995) 90-100
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