Sol-gel Synthesis of Nanomaterials

Yu-Guo Guo

Synthesis of Nanomaterials through Sol-gel Method

Contents Part I Part II Part III Introduction to the sol-gel method Basic principles in the sol-gel synthesis Synthesis of nanomaterials by sol-gel method

Introduction to the sol-gel method

Introduction Development of the sol-gel synthesis Several conceptions & definitions in sol-gel synthesis Synthetic process in the sol-gel method Apparatus used in sol-gel synthesis Technical process of sol-gel method Advantages & Disadvantages of sol-gel synthesis

Introduction

The sol-gel process is a wet-chemical technique (also known as Chemical Solution Deposition) widely used recently in the fields of materials science and ceramic engineering. Such methods are used primarily for the fabrication of materials (typically a metal oxide) starting from a chemical solution (sol, short for solution) which acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers.

Development of the sol-gel synthesis

In the 1930s, W.Geffcken used metal alkoxides to prepare oxide films In 1846, Ebelmen found the gelation phenomenon

In 1971, Dislich prepared the SiO2-B2O-Al2O3-Na2OK2O multicomponent glass

After the 1980s, the preparation of functional ceramic materials with glass and oxide coatings, composite oxide ceramic materials

In 1975, Yoldas and Yamane prepared monolithic ceramic and transparent alumina membrane

Several conceptions & definitions in solgel synthesis

Colloid: A colloid is a type of mixture in which one substance is dispersed evenly throughout another. A colloidal system consists of two separate phases: a dispersed phase (or internal phase) and a continuous phase (or dispersion medium). Generally, the gravity of the dispersed phase is negligible, and the interaction between particles is always a short-range interaction. Sol: A sol is a colloidal suspension of solid or macromolecular particles (1 - 1000 nm in size) in a liquid. Gel: A gel a colloidal system of solid properties, in which the dispersed substances form continuous and crosslinked networks within liquid or gas. The content of dispersed phase in the gel is very low (between 1% to 3%).

Several conceptions & definitions in solgel synthesis

Comparison between sol and gel:
Sol Unfixed shape Particles in the solid phase can move freely

Gel

Particles in the solid phase are fixed in Fixed shape accordance with certain network structure and cannot move freely

* The special network structure gives the gel extremely high specific surface area *

Synthetic process in the sol-gel method

1) Use the compound containing components of high chemical activities as the precursor; 2) Uniformly mix the raw materials in the liquid phase; 3) Carry out hydrolysis and polycondensation reactions so as to form stable and transparent sol system; 4) Colloidal particles slowly aggregate after the aging of sols to form gels with three-dimensional network structures, meanwhile, the solvent without fluidity is filled in the gel network; 5) After various processes such as drying and sintering, materials with microstructures even nanostructures can be prepared.
Dissolve Precursor

Hydrolysis

Polycondensation

Aging

Solution

Sol

Gel

Aged gel

Synthetic process in the sol-gel method

Typical precursors: Metal alkoxides & Metal chlorides (which undergo various forms of hydrolysis and polycondensation reactions). Formation of the gel: The formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves towards the formation of a gel-like biphasic system containing both a liquid phase and a solid phase whose morphologies range from discrete particles to continuous polymer networks.

Synthetic process in the sol-gel method

Removal of the liquid phase The volume fraction of particles (or particle density) in the colloid may be so low that a significant amount of fluid may need to be removed initially for the gel-like properties to be recognized. Approaches: Sedimentation or Centrifugation (more efficient) After that, a drying process is required to remove the remaining liquid (solvent) phase, which is typically accompanied by a significant amount of shrinkage and densification. Finally, a thermal treatment, or firing process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via sintering, densification and grain growth.

Apparatus used in sol-gel synthesis

2 2 1 3 4 4 5 1 3

7 5
6

Schematic drawing of the electric stirring sol-gel synthesis

1.Reflux device 2.Motor stirrer 3.Thermometer 4.Container 5.Hydrothermal equipment

Schematic drawing of the magetic stirring sol-gel synthesis

1.Container 2.Cover plate for sealing 3.Reaction solution 4.Stirrer 5.Heater plate of the magnetic stirrer 6.Temperature regulator 7.Rotating speed regulator

Technical process of sol-gel method

Sol-gel Synthetic Materials

Solution - Solation

Gelation - Shaping

Curing process

Mechanical mixing of ultrafines and solution to form the glue solution

Hydrolysis of metallic inorganic compounds or metal alkoxides

Hydrolysis of organometallic compounds Drying Heat treatment

Technical process of sol-gel method

Technical process of sol-gel method

Precursor solution
Water and catalyst

Transparent sol
Pulverization and collection

Film forming process Fiber forming process

Wet gel

Film

Fiber

Powder

Dried gel

Curing process Final product

Gel-casting process

Advantages of sol-gel synthesis

Starting materials are in molecular level, and final products prepared are homogeneous; Products are relatively higher in purity; Have rheological behavior, which may be used in the preparation of products with different applications; Controllable degree of porosity; Easy to prepare various shapes; Cheap and convenient to carry out; Enable synthesis at a low temperature; Allow for fine control of the products chemical composition, especially suitable for preparing multicomponent materials; Enable small quantities of dopants to be introduced in the sol and end up uniformly dispersed in the final product;

Disadvantages of sol-gel synthesis

Relatively higher in the cost of raw materials; Micropores may be left after the synthesis; Relatively longer in reaction times; Organic solvents may be harmful to the human body.

Basic principles in the sol-gel synthesis

Stability principle of colloids - DLVO Theory The DLVO theory is named after Derjaguin and Landau, Verwey and Overbeek. Stability mechanism of sols Basic principles of the sol-gel synthetic method

Stability principle of colloids - DLVO Theory

Electric double layer & potential

In the sol system, the existence of electrostatic attraction will force the counterions in solution move close to the particle surface, and repel homo-ions; solid surface charges and coutercharges in solution may together form the structure of electric double layer. The adsorbed ions may firmly bind to the solid surface, therefore, when relative movement happens between solid and liquid, a small portion of counterions may slip with the solid, AB plane is the practical sliding plane at the occurrence of electrokinetic phenomena, and potential is the potential on the sliding plane. When potential equals to zero, the pH value becomes the isoelectric point.
+
A

+ + + + + + + +

+ - +- + - - + - + + liquid -

+ + +

+ + + +

Particle Surface charge

Distance x from surface

Stability principle of colloids - DLVO Theory

Interparticle Van der Waals force Electric double layer electrostatic repulsive energy

Interparticle total interaction energy

VT = V A + VR

A sol is a colloidal system in which solid or macromolecular particles disperse in the liquid phase, and there exists a considerable large interface in the sol; therefore, the Gibbs free energy of interfacial atoms is higher than that of internal atoms, and particles have a tendency of agglomeration to lower the surface energy. During the integration of particles, increase the energy barrier required to overcome in the system may make them stable in kinetics. Generally, there are three basic ways to increase the energy barrier between particles: (1) surfacely charged the colloidal particles; (2) utilize the steric effect; (3) utilize the solvent effect.

Stability mechanism of sols

The surface charge of colloidal particles comes from the selective ionization of lattice ions in the colloidal particle, or the selective adsorption of ions in the solvent. For metal oxide hydrosols, H+ or OH- will be preferentially adsorbed. When pH > PZC (point of zero charge), the surface of colloidal particles will be negatively charged; otherwise it will be positively charged. According to the DLVO theory, colloidal particles will be affected by both the repulsion force from the electric double layer and the long range Van der Waals force, besides, interactions between colloidal particles may also include intermolecular Van der Waals force and short range Bonn repulsion force, which is caused by the overlapping of surface valence electrons.

64n0 Tr02 nx A e n 12H 2

Basic principles of the sol-gel synthetic method

1. Hydrolysis - condensation reaction of alkoxides

Hydrolysis reaction: M(OR)n + xH2O M(OH)x(OR)n-x + xR-OH

Polycondensation reaction: (OR)n-1M-OH + HO-M(OR)n-1 (OR)n-1M-O-M(OR)n-1 + H2O m(OR)n-2 M(OH)2 [(OR) n-2M-O]m + mH2O m(OR)n-3 M(OH)3 [(OR) n-3M-O]m + mH2O + mH+

Condensation reaction may be also observed between hydroxyl groups and alkoxyl groups: (OR)n-x(HO)x-lM-OH + ROM(OR)n-x-l (OH)x (OR)n-x(OH)x-1M-O-M(OR)n-x-l (OH)x + R-OH

Basic principles of the sol-gel synthetic method

1. Hydrolysis - condensation reaction of alkoxides
Conventional alkoxides in sol-gel synthesis

Cation
Si Al

M(OR)n
Si(OCH3)4 Si(OC2H5)4 Al(O-iC3H7)3 Al(O-sC4H9)3 Ti (O-iC3H7)4 Ti(OC4H9)4 Ti(OC5H7)4 B(OCH3)3

Anion
Ge Zr

M(OR)n
Ge(OC2H5)4 Zr(O-iC3H7)4

Ti B

Y Ca

Y(OC2H5)3 Ca(OC2H5)2

Basic principles of the sol-gel synthetic method

2. Hydrolysis - condensation reaction of inorganic salts

Hydrolysis reaction: Mn+ nH2O M(OH)n nH+

Dehydrated gelation

Gelation
Alkalic gelation

Colloidal particles dehydrate, electrolyte concentration in the diffusion layer increases, energy barrier in gelation gradually decreases

xM(H2O)nz+ + yOH- + aA- MxOu(OH)y-2u(H2O)nAa(xz-y-a)+ + (xn+u-n)H2O A- acid ions added during the gelation process. When x=1, mononuclear polymer will form; When x>1, multinuclear polymer will form; Mz+ can bridge with ligands by O2-, OH-, H2 or A-.

Basic principles of the sol-gel synthetic method

2. Hydrolysis - condensation reaction of inorganic salts: Concentration method & Dispersion method

Sols can be prepared at relatively higher temperatures through controllable nucleation effect and crystal growth.

The metal salts hydrolyzed quickly to form gelatinous precipitates, and excessive electrolytes may be washed off, then strong acid may be added at relatively higher temperatures to form the sol.

Synthesis of nanomaterials by Sol-gel method

Synthesis of nanoparticles (e.g.,spheres) through sol-gel method Synthesis of nanofibers through sol-gel method Synthesis of nanofilms through sol-gel method Synthesis of aerogels through sol-gel method Synthesis of nanoporous carbon containing LiFePO4 nanoparticles through sol-gel method

Monodisperse silica spheres prepared from hydrolysis of tetraethyl orthosilicate (TEOS)

SiO2 prepared in Guos group

Synthesis of nanopowders through sol-gel method

Lithium orthosilicate (Li4SiO4) and its solid solution are known as fast Li-ion conductors. As a CO2 catalytic/sorbent, Li4SiO4 also exhibits excellent performance. Recently, Li4SiO4 has been selected as one of the most promising candidates for solid tritium breeding materials in fusion reactors because of its high lithium atom density and favorable tritium release behaviors. In the synthesis of Li4SiO4, traditional solid state reaction or precipitation methods require high temperature (usually 900 C) and lead to many problems including volatilization and lack of control of the microstructure and composition. Also, the combustion method could hardly produce pure Li4SiO4 because of the deficiency of oxygen or the formation of Li2CO3. The sol-gel method is a preferred choice to synthesize ceramic powders, since it offers an opportunity for not only synthesizing a material at low temperatures but also the possibility to control its morphology and microstructure.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

With LiOHH2O and aerosil SiO2 as the starting materials and citric acid (C6H8O7H2O) as the chelating agent, Li4SiO4 powders with particle size as small as 100 nm were successfully synthesized at the temperature as low as 675 C.
DSC/TG analysis results of the gel precursors

The sol-gel procedure for the preparation of Li4SiO4 powders

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

SEM images of the Li4SiO4 powders synthesized by (a) solid state reaction and (b) the water-based solgel method.
As seen, the samples obtained by solid state reaction (900 C for 4 h) show irregular grains. The grain size had a wide distribution, mainly ranging from 10 to 20 m with a few grains as large as 30 m. The samples prepared by the water-based sol-gel method (675 C for 4 h) displayed different morphology. The grains were spherical and the grain size had a homogeneous distribution. The average grain size was about 100 nm, which was much smaller than that of the samples obtained by solid state reaction.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

The experimental results showed that the powders obtained by the water-based sol-gel process (SG) possessed excellent sinterability, exhibiting a linear shrinkage of 5.2% while sintered to 900 C, more than 3 times that of the powders obtained by solid state reaction (SSR). The higher sinterability was attributed to the smaller particle size and higher specific surface area of the powders. The high sinterability was beneficial to obtain dense Li4SiO4 ceramics, which was an important aspect of the tritium breeding materials.

Thermal shrinkage behaviors of Li4SiO4 powders fabricated by (a) solid state reaction and (b) the water-based solgel method.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

The equivalent circuit was composed of a resistance R1 in series with a component consisting of another resistance R2 in parallel to a CPE element. As seen from Fig. (a), the grain interior resistance was comparable for SSR and SG samples, but the bulk resistance was much lower for the SG samples. The conductivity values of the bulk conductivity (b) can be calculated with b = d/SRb, where d is the sample thickness, S, the area of the electrode and Rb, the bulk resistance. From Fig. (b), it is clear that The bulk conductivity of the SG sintered bodies was much higher than that of the SSR samples at the same testing temperature, and the bulk conductivity enhanced significantly with the increase of temperature, the conductivity data are found to be linear and well fit the Arrhenius equation, bT = Aexp(-E/kT).

(a) Cole-Cole-Diagram of Li4SiO4 ceramics at 300 C, (b) Arrhenius plots of the bulk conductivity for the Li4SiO4 samples. X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475