Microporous and Mesoporous Materials 78 (2005) 151157 www.elsevier.

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Control of the growth processes of the silica sols colloidal particles

S.S. Hayrapetyan, H.G. Khachatryan
*
Department of Chemistry, Yerevan State University, 1, Alek Manoukian Street, 375025 Yerevan, Armenia Received 11 November 2003; received in revised form 6 October 2004; accepted 7 October 2004 Available online 10 December 2004

Abstract Solubility of the silica depends mainly on medium pH values. Owing to this pH factor becomes denitive when carrying processes connected with the silica dissolving. The growth of the silica colloidal particles during the obtaining stabilized silica sols is one of such processes. The inuence of other factors on the silica solubility in the SiO2H2O system is not so essential. A possibility to control the growth of the silica colloidal particles during the preparation of the stabilized silica sols by means of regulating medium pH values has been studied. Seed formation processes are decisive when obtaining silica sols and silica gels with beforehand requested characteristics. It is necessary to realize growth processes in the meta-stable range of the SiO2H2O system (pH 8.59.5) to obtain silica sols with reproducible particle sizes. Inuence of the pre-history of obtained stabilized silica sols on porous characteristics of silica gels prepared on their base has been studied. For evaluation of the quality of these sols porous characteristics of the silica gels have been determined by means of BET method. Pore size distribution has been also determined for the obtained silica gels. 2004 Elsevier Inc. All rights reserved.
Keywords: Seed formation; Colloidal particles growth; Silica; Pore size distribution; BET method

1. Introduction Despite the fact that colloidal silica as investigation object was studied for many years the interest towards this system does not only weaken but on the contrary becomes stronger. Particularly in the recent years with appearing of the nanotechnology during the preparation of materials on the base of silica the role of the colloidal silica as well as the problems of its stabilization increases [17]. Synthesis of highly transparent hybrid lms containing nanosized silica domain from acrylic polymer and aqueous monodispersed colloidal silica with a coupling agent 3-(trimethyloxysilyl)propyl methacrylate (MSMA) was described in [1,2]. The silica content in the hybrid thin lms was varied from 0 to 50 wt.%.

Corresponding author. Tel.: +374 1 570663; fax: +374 1 576421. E-mail address: gold@ysu.am (H.G. Khachatryan).

The experimental results showed that the silica particle size in the precursor solution and the hybrid lms was varied from 20 to 40 nm. It could be controlled by the mole ratio of MSMA to silica. Preparation and thermal properties of epoxy-silica nanocomposites from nanoscale colloidal silica was discussed in [3]. Nanocomposites were obtained fromdirectly blending diglycidylether of bis-phenol-A and nanoscale colloidal silica and then curing 4,4diaminophenylmethane. Properties of poly(N-isopropylacrilamide)-grafted colloidal silica were studied in [4]. Poly(N-isopropylacrilamide-co-3-trimethoxysilylpropylmethacrylate) was prepared by radical polymerization and was grafted onto the surface of spherical colloidal silica. The copolymer, which had on average one silyl group per chain, condensed on the silica dispersed in tetrahydrofuran at 60 C. The inuence of cationic polyelectrolytes on the stability and occulation of dispersed particles, the poly-

1387-1811/$ - see front matter 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2004.10.011

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mer adsorption on colloidal silica and quartz powder was investigated in [5]. Preparation and characterization of polypyrrolesilica colloidal nanocomposites in watermethanol mixtures was discussed in [6]. The eect of methanol cosolvent on the synthesis of polypyrrolesilica colloidal nanocomposites using ultra ne silica sols in combination with both iron(III) chloride and oxidants has been investigated. Two protocols were valuated: the addition of methanol to an aqueous silica sol and the addition of water to methanolic silica sol. The latter proved to be more robust, since it allowed colloidally stable dispersions to be prepared at higher methanol content. This allowed greater control over the particle size of the nanocomposites particles. Surface chemistry and trimethylsilyl functionalization of Sto ber silica sols were investigated in [7]. Various silica sols, with dierent surface chemistries, were reacted in solvent dispersions with hexamethyldisilazane or ethoxytrimethylsilane to produce hydrophobic trimethylsilane trimethylsilyl functionalized sols. Manufacturing of silica sorbents for liquid chromatography, especially high performance liquid chromatography (HPLC) is one more important area in which colloidal silica is used. Total control of the whole technological processes is necessary to provide manufacturing the packing materials for HPLC with reproducible physicalchemical properties [8,9]. One of the ways to secure the control of porous characteristics of the silica sorbents is the using of stabilized silicas as initial raw materials. Recently works dedicated to the obtaining and stabilization of colloidal silica were appeared [10 12]. Inuence of the process parameters on the morphological evolution and fractal dimension of sol-gel colloidal silica particles have been studied in [10]. Colloidal silica particles were synthesized from tetraethoxysilane (TEOS), ammonium hydroxide, ethanol, and deionized water. Obtaining dierent structures was possible due to the variation of molar ratios of ammonium hydroxide, ethanol and water with respect to the precursor. Pore structure was characterized by nitrogen gas sorptiondesorption, showing colloidal silica particles with solid-pores surface areas varying from 0.48 up to 567 m2/g, pore volume varying from 0.0013 up to 0.88 cm3/g, and average pore radii varying between 14 and 36 nm. The process parameters of the formation colloidal silica via sodium silicate have been investigated in [11]. Sodium ion of delicate was removed by ion-exchanging to obtain the active silicic acid which was titrated to the solution of potassium hydroxide to form the colloidal silica. The results showed the mean particles size of colloidal silica was inuenced by the KOH concentration, formation temperature and low titration rate of active silicic acid would help the particle growth to form the

larger particle size of colloidal silica. Unfortunately, the colloidal silicas formed at theses conditions were unstable. Preparation of colloidal silica from sodium metasilicate solution and sulfuric acid in emulsion medium was described in [12]. The problem of the synthesis of the silica sols with colloidal particles of denite xed sizes is very important during the process of obtaining silica gels with reproducible porous characteristics on the base of stabilized silica sols. Control of the particles growth processes is necessary in this case in order to secure reproducibility of the porous characteristics of the obtained silica sols. The obtaining of silica gels on the base of stabilized silica sols has the following advantages as compared with the classical method for obtaining silica gels by means of the precipitation by acids from the liquid glass: possibility of the control of the porous characteristics of the obtained silica gels; reproducibility of the porous characteristics; the absence of the necessity of the silica hydrogels rinsing [8]. Medium acidity (pH-factor) is the main, and it can be said decisive factor during the carrying processes in the SiO2H2O system so far as solubility of the silica depends on the highest level from the medium pH values. The growth of the silica colloidal particles during the obtaining of the stabilized silicas is one of such processes. Series of methods for obtaining silica sols was described [1315]. Method of BechtoldSnyders [14] is most frequently used in which silica sols with particles 10130 nm in size are usually obtained regulating colloidal particles growth processes. Colloidal particles growth process is provided by adding the active silica (silica sol with particles diameter less than 24 nm) to the main silica. Preparation of the active silica is realized by passing the sodium silicate solution with silicate module M = 3.25 (M = SiO2/Na2O molar ratio) through the ion-exchange columns in H+-form after which pH value of the solution rises up to 7.0. The main silica sol is prepared by heating the part of active silica up to 100 C when colloidal particles more than 10 nm in size are formed as a result. Grafting is carried by heating the system at the temperatures lower than 60 C maintaining volume constant (that is the rate of adding active silica must be equal to the rate of water removing from the system owing to evaporation). Seed formation (nucleation) processes in this case occurs spontaneously. As a point of fact, the silicon dioxide colloidal particles growth takes place on the centers already formed by the non-regulated, fortuitous way. At pH 7.0 also new seeds appear side by side with growth of

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the main nucleation centers that leads to the widening of the distribution by sizes curve for seed particles. It is expedient to carry grafting process by polysilicic acid (PSA) acidic sol without obtaining the active silica with particles of denite size so far as such particles may dissolve not completely and thus will become new growth seeds increasing correspondingly the deviation in the nucleation centers sizes. Excessively intensive seeds formation may be avoided when over-saturation will be kept in the meta-stability range broads. The number of forming seeds can be lowered also if carrying the grafting process in conditions of periodically oscillating temperature, concentration and/ or other factors. As was mentioned above, medium acidity is the most acting factor in the SiO2H2O system. During periodical increasing-decreasing of the pH values within the denite range it becomes possible to realize the growth of the germ centers without formation of the secondary (new) nucleation centers.

10 -2 V/ d
0.5

0.4

b a

0.3

0.2

0.1

10

d, nm

2. Experimental The growth of the silica colloidal particles was realized according to the following procedure: freshly prepared polysilicic acid (PSA) was added to the initial aqueous solution of the alkali under intensive stirring at 8090 C. During the whole PSA adding period the solution was boiled and PSA was added with the rate equal to the liquid evaporation rate from the obtained mixture. That is the solution volume remains constant during the whole growth stage. Above-mentioned processes are presented schematically in Figs. 1 and 3.

Fig. 2. Pore size distribution for the silica obtained on the base of the silica sols with nal pH values: (a) 7.0; (b) 7.5; (c) 8.0 (according to Scheme 1).

pH
14

Final pH value serves as a criterion for growth processes according to the rst scheme and it must to be not less than 6.5 otherwise gelling of the system may occur. In this case pH control of the colloidal particles growth do not carried, i.e. feeding processes were stopped after adding some quantity of the PSA and establishing pH in the 7.07.5 range. Silica sols with SiO2 content not more than 7.5 mass% are usually obtained as result. PSA solutions containing 34 mass% SiO2 was used, obtained by means of the Bird method [13]. Aiming to prevent secondary nucleation processes it is necessary to carry grafting process strictly in meta-stable range. Therefore alkali was added periodically to the

pH
14

12
12

10
10
9.5

1 2 3
8

S i O2-H2O system solubility meta-stable range

8.5

6 0 1 2

6 0 1 2 3 4 5 6 n

Feeding divisibility
Fig. 1. Scheme for colloidal silica sol preparation.

Fig. 3. General scheme for silica sol preparation.

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system for increase pH values and keeping it within the denite range. Sharp periodical increases of the pH values not only prevent secondary nucleation processes but also lead to the dissolving of the nest germ centers. During such grafting propitious conditions are created for growth of the already formed seeds. It is possible to vary the sizes of the obtained colloidal particles depending on the grafting level and this secure purposeful synthesis of the silica sols with required particle sizes. During the formation of the porous structure of silicas silica sol gel formation is one of the most signicant stages. Silica sols gelling process was realized by means of decrease of the medium pH values to 5.86.2 units using 0.1 mol/l nitric acid. In case of neutralization coagulation homogeneous gels were formed, i.e. gelling processes cannot inuence on the pore size distribution. Such structures reect maximally size distribution of the colloidal particles. After ageing during two days hydrogels were dried at 150 C during 2 h and then baked at 600 C during 4 h. Porous characteristics have been determined on the Accusorb 2300A instrument (Micromeritics, USA) by means of the BET method. Silica colloid particles sizes have been determined by Sears method [8]. All experiments and measurements were repeated vefold. Standard deviations of the measured values are given in Table 1.

3. Results and discussion Preparation of silica sols according to the rst scheme (Fig. 1) by means of adding some PSA quantity is carried already out of the meta-stable range since pH value of the system becomes less than 8.5 when added PSA quantity increases. And in this case new growth centers appear together with growth of the main (initial) particles. The intensity of the secondary seeds formation increases when pH decreases lower than 8.5 and the system exits from the meta-stable range of growth (pH 8.59.5) where preferably only the growth of the existing particles occurs without formation of the new centers. New seeds formation and irregular growth of the existing particles takes place at comparatively lower pH values (8.57.0) which leads to the obtaining of the silica with higher dispersion of the colloidal particles size. Sil-

ica gels obtained on the base of such silica sols possesses comparatively wider pore size distribution (Fig. 2b). It follows from Fig. 2 that when the growth of the silica colloidal particles is completed at comparatively higher pH values then silica gel obtained on the base of such silica sol has narrower pore size distribution (curve 2c). At lower pH values (7.07.5) preferably secondary seed formation occurs. And as a result widening of the PSD curves is observed for silica gels obtained (curves 2a and b). Alkali quantity in the initial aqueous-alkaline medium which determines pH value of the system is one of the denitive factors when carrying colloidal silica particles growth. It is known [8] that seed formation in the SiO2H2O system begins at pH near 10.26. It means that the growth processes will not start until pH value of the initial aqueous-alkaline solution does not lowered by adding PSA up to this value, i.e. added PSA transforms into the polysilicate varieties which do not create growth centers, since their sizes do not reach those critical values allowing them to become seeds. Higher pH values prevent it and cause higher solubility of the SiO2H2O system. So, higher is alkali content in the initial solution higher will be PSA quantity added (to lower pH up to 10.26) and smaller will be seeds number, and nally smaller will be colloidal particles size in the obtained silica sol. At equal quantities of the added PSA nal size of the silica colloidal particles will be larger for those sols for which growth processes were started with minimal alkali amounts. It is necessary to carry out particles growth in the meta-stable range of solubility for the SiO2H2O system (pH 8.59.5) to obtain larger and uniform silica colloidal particles. And in this case it becomes possible to realize only the growth of the existing particles without formation of the new growth centers. We provide keeping pH in the meta-stable range by adding periodically alkali (1.0 mol/l NaOH) (see Fig. 3). The schemes of obtaining of dierent silica sols and pores distribution by sizes curves for silica gels obtained on their base are presented in Figs. 47. Colloidal particles sizes of the given silica sols as well as porous characteristics of the silica gels are given in Table 1. The processes of seed formation (nucleation) are the main subject of consideration in this article. We account conditionally that nucleation processes cease when adding the rst portion of the alkali solution. And four

Table 1 Colloidal particles sizes of the given silica sols and porous characteristics of the silica gels Sample Specic surface area (m2/g) By BET method a b c d 230 20 215 15 140 10 132 8 By Sears 260 10 235 10 175 10 164 7 Average size of particles (nm) 10.5 0.6 11.6 0.6 15.2 0.5 16.0 0.7 Pore volume (cm3/g) 0.60 0.01 0.58 0.01 0.56 0.01 0.56 0.01 Pores average diameter (nm) 12 2 11 1 16 1 17 1 pH value for silica sol 8.0 0.15 8.5 0.15 9.0 0.1 9.25 0.1

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pH
14

pH

(a)
14

(a)

12

12

10
9.0 9.0 9.0 9.0 9.0

10
9.6 9.6 9.3 9.1

8
7.5 7.5 7.5 7.5 7.5 7.5

8
7.8

8.0 8.2

6 0 1 2 3 4 5 6 n

10-2 V/ d
2.5

(b)

10-2 V/ d 5

(b)

4
1.5

3
1

2
0.5

1
0 0 4 8 12 16 20 d. nm

Fig. 4. (a) Scheme for silica sol preparation. Seeds formation at pH 7.58.0; colloidal particles growth at the same conditions. (b) Pore size distribution for the silica obtained on the base of the sol above.

0 0 4 8 12 16 20 d, nm

cases of seeds formation and colloidal particles growth are considered: seeds formation at comparatively low pH values (7.5 8.0) and colloidal particles growth at the same pH values; seeds formation at comparatively low pH values (7.5 8.0) and colloidal particles growth at higher pH values (9.010.0); seeds formation at higher pH values (9.09.5) and colloidal particles growth at comparatively low pH values (8.09.0); seeds formation at higher pH values (9.09.5) and colloidal particles growth at the same pH values. One can see from Fig. 4b that before adding the rst portion of alkali medium pH value decreases till 7.5.

Fig. 5. (a) Scheme for silica sol preparation. Seeds formation at pH 7.58.0; colloidal particles growth at pH 9.010.0. (b) Pore size distribution for the silica obtained on the base of the sol above.

And then pH value decreases till 7.5 before adding each portion of alkali during the whole particles growth process. As a result silica sols with comparatively wide pore size distribution are obtained (Fig. 4a). Final size of the colloidal particles reaches 12.0 nm despite the fact that grafting or feeding divisibility equals to 6. As it was mentioned above growth centers conception in the SiO2H2O system begins already at pH 10.26 [8] and the growth of these centers without secondary nucleation can be carried in pH range till 9.0. Further lowering of the pH values (in the given case till 7.5) leads to the situation when appearance of the new nucleation centers takes place simultaneously with growing of the particles already existing in the system. In the

156
pH

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pH

(a)
14

14

(a)

12

12

10
9.3 9.3 9.4 9.36 9.36

10 9.25 8 9.3 9.25 9.25 9.25 9.2

8.0

6 0
-2 10 V/ d

(b)

10 -2V/d
2.5

(b)

1.5

3
1

0.5

0 0 5 10 15 20 25 d. nm

0 0 4 8 12 16 20 d, nm

Fig. 7. (a) Scheme for silica sol preparation. Seeds formation at pH 9.09.5; colloidal particles growth at the same conditions. (b) Pore size distribution for the silica obtained on the base of the sol above.

Fig. 6. (a) Scheme for silica sol preparation. Seeds formation at pH 9.0-9.5; colloidal particles growth at pH 8.09.0. (b) Pore size distribution for the silica obtained on the base of the sol above.

pH < 8.0 range primary formation of the new growth centers occurs. So formation of comparatively more polydispersed silica sol can be explained by this. And as a resultsilica gel obtained on the base of such silica sol is also characterized by comparatively wider pores distribution by size. Silica sol obtaining scheme and pore size distribution for silica gel obtained on the base of this silica sol are presented in Fig. 5a. One can see that nucleation process took place at pH values not less than 9.6 that is seed formation process and initial growth of the forming particles took place in meta-stable range of solubility of the SiO2H2O system (pH 8.59.5). The rst portion of alkali was added at pH 9.6 that is the nucleation centers

conception process took place in ideal conditions without secondary seed formation. However during the process of the particles growth at separate stages of the grafting were lowered till 7.8. The main grafting process was carried at pH 7.88.5 and almost the half of the given PSA was added just in this pH range. Average size of the colloidal particles reaches 12.0 nm. Pores size distribution curve for this sample obtained on the base of this silica sol is suciently narrow (Fig. 5b). Nevertheless, as it is evident from Fig. 5b frontal part of the pore size distribution curve is widened a little which witnesses that during the growth process (when pH value decreases till 7.8) apparently secondary nucleation occurs and newly forming particles have time for growth up to those sizes when sharp increasing of the pH values do not lead already to their complete dissolving. They become a cause for appearance of the small-porous sections in the struc-

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ture of the obtained silica (widening on the frontal part of the pores distribution by sizes curve). A part of the PSA which must to be spent for the main particles growing creates new nucleation centers which leads to that silica sol particles average size does not exceed 12.0 nm. However, it is necessary to mark that comparatively small pores are being formed in insignicant quantity. It is conditioned by that nucleation centers conception processes occurs mainly in meta-stable range and pH values of the system does not decreased lower than 7.8. Less than one third of this quantity of the PSA was added at pH < 8.5 and only a little part of this quantity can become a cause of formation of small-porous parts in the obtained silica. The tail on the frontal part of the pore size distribution curve for silica gel synthesized according to the scheme presented in Fig. 7 can be explained by that seed formation in this case took place at comparatively lower pH values (8.9). Apparently in this pH range (<10.3) seeds of dierent sizes are formed in the very beginning of the process of the formation of the growth centers. Moreover, further the deviation in particles sizes are not smoothed although during the growth process pH values do not lowered less tan 9.3 (when possibility of the new nucleation centers formation is practically excluded). All the more medium pH is periodically increased by means of adding sodium hydroxide solution. For obtaining more homogeneous silica sols it is necessary to carry out the nucleation and particles growing processes at pH values not less than 8.59.0. Silica sol obtaining scheme and pore size distribution for silica gel obtained on the base of the given silica sol are presented at Fig. 5. Nucleation process and the seeds growing in this case take place at pH values not less than 9.5 that tell upon the nal sizes of the colloidal particles which are 17.0 nm. Insignicant tail at the pore size distribution curve is observed now on its rear part that witnesses that growing process took place without secondary germ formation. Exactly this scheme of the silica sol preparing secures reproducibility of the porous characteristics of the silica gels obtained on the base of the preliminary synthesized silica sols.

4. Conclusion The use of stabilized silica sols as initial raw for obtaining silica gels secures the reproducibility of the porous characteristics of latter. It is necessary to carry the synthesis of silica sols in the strictly meta-stable range of solubility (pH 8.5 9.0). Otherwise it will be dicult to control the processes of the colloidal particles growth so far as out of this range (pH < 8.5) irregular seeds formation occurs which could becomes the main cause of the non-reproducibility of the porous characteristics of the silica gels obtained on the base of silica sols.

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