People's Democratic Republic of Algeria

Ministry of Higher Education and Scientific Research

August 20, 1955 University of Skikda

Faculty of Sciences
Department of Chemistry
Master 2: Chemistry of Materials

METHODS OF SYNTHESIS SOLIDS MATERIALS

Submitted by:
Settara Khaoula Supervised by:
Karoui Khouloud Miss I.Attia
Djaghroud Fella

2017/2018
 Abstract

Chemical methods of synthesis of materials play an important role in designing

and discovering new materials and also in providing better and less methods for
preparing known materials. In this work, we shall discuss the chemical synthesis of
inorganic solids materials. We shall first briefly examine the different four methods of
preparing solids and then discuss each of them with giving a sample from our
previous syntheses in the preparation of material’s module.

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 Table of Contents

1. Introduction……………………………………………...…….…………………..4
2. Methods of synthesis of inorganic materials……….....……….…………………..5
2.1. Solid-State or Ceramic Method……………....……………………………….5
2.2. Co-precipitation……………………………....……………………………….6
2.3. Sol–gel processing ……..…….........…………………………………......…..6
2.4. High Pressure Method...................................................................................7
3. Synthesis of BaTiO3 by Reaction in solid state.......................................................8
3.1. Methods.........................................................................................................8
3.2. Results and discussion...................................................................................9

Works Cited................................................................................................................10

Appendices.................................................................................................................11

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 1. Introduction

The preparation process of inorganic materials is one of the most important aspects
of material science. Not only the chemical composition of a particular material plays a
crucial role for many applications but also its structure. The proper choice of the
chemical precursors and the preparation technique to obtain a material with the
desired chemical and physical properties is a challenge for both material scientists and
inorganic chemists. This work was made to give a comprehensive overview of the
current methods for chemical synthesis of inorganic materials. With giving an
example.

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 2. Methods of synthesis of inorganic materials
2.1. Solid-State or Ceramic Method

The easiest way to make many solid state materials is direct reaction of their
components at high temperatures. The synthesis of oxides (perovskites) by reaction in
the solid state is one of the most widely used methods in solid chemistry. At the base
of this method is the reaction by heat treatment between two or more substances in
solid form which are intimately mixed. The reactants, oxides and / or carbonates in
the form of powders, are weighed in stoichiometric quantities and thoroughly mixed
by grinding in a mortar. [1]

Obtaining a homogeneous mixture composed of small particles will then facilitate

the kinetics of the reaction. The powder is then subjected to successive heat
treatments until a single phase is obtained. The temperature chosen is close to, in
general, 1000 ° C. The advantage of this technique is that it is fairly easy and fast to
master. because it does not require any previous preparation of the precursors. Particle
size plays a very important role in the reaction rate and in the homogeneity of the
compound obtained, since the diffusion in the solid state is slow. [1]

Raw materials:

They consist of oxides, carbonates, nitrates, etc. An ideal powder can be described
as being formed of grains of small size (of the order of 1 μm), of regular shape, with a
very narrow size distribution. The purity as well as that of possible additions are
controlled. The main problem concerning basic raw materials, which are in the form
of powders, is the difficulty of evaluating the fundamental parameters reflecting the
reactivity of the material vis-à-vis the others with which it is reacted, the thermal
history material plays a very important role. [2]

Mixing, grinding:

This is one of the essential phases of the production cycle of a solid with
perovskite structure. It is also during this operation that a uniform distribution of the
precursors is obtained. The powders are weighed according to the stoichiometric
quantities provided by the reaction equation. [2]

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 2.2. Co-precipitation

Co-precipitation makes it possible to obtain precursor products by simultaneous

precipitation of two M and M 'cations (M being an alkaline or an alkaline earth metal
and a transition metal).

Generally after the mixing of the two solutions containing the metal cations, the
measurement of the pH is necessary to be able to follow the evolution of the
precipitation, after dissolution of the adequate masses of metal oxides, the solutions
are mixed progressively and then diluted. The precipitation takes place cold or hot at a
given pH. The heat activates the co-precipitation and the pH of the reaction medium is
of great importance for the majority of the co-precipitation reactions since it
determines the nature and the stoichiometry of the precipitate. This dependence of the
mechanism of the reaction with the pH makes it very difficult to obtain a given
stoichiometry and constitutes a major drawback during the synthesis. [3]

2.3. Sol–gel processing

A very interesting solution-based synthetic technique for the low-temperature

preparation of both noncrystalline solids (glass and glasslike materials) and crystalline
ceramics is the sol-gel process. The process (figure1) gets its name from the two
major stages involved: formation of a sol (a colloidal suspension of solid particles in a
liquid phase) through hydrolysis and polymerization reactions of appropriate
precursors; and subsequent attainment of a semirigid porous gel. [4]

Figure 1: The process of sol-gel methode

The gelation point is generally accepted as that point at which the sol’s viscosity
reaches a plateau, where it is able to support stress elasticity. The crystallinity of the
final product, which is obtained after removal of solvent and residuals from the pores
by aging, drying, and annealing, is highly dependent on the experimental conditions

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used. Moreover, sol–gels have been used as templates for directing microand nano-
scale materials morphology, which will be explained further shortly. [5]

2.4. High Pressure Method

The hydrothermal method consists in heating the reagents in the presence of water
in a closed container, an autoclave. In the latter, the pressure and the superheated
water remain above the normal boiling point and the pressure in the atmospheric
pressure. Hydrothermal conditions are produced in nature and many minerals,
including natural zeolites, have been formed as well. Synthetic emeralds are obtained
under hydrothermal conditions. The use of more low temperatures is the advantage of
the advantages of this method. [6]

Figure 2: An autoclave for hydrothermal réactions

The (Figure2) is showing:

•an autoclave is constructed from thick stainless steel and fitted with safety valves.

•typically lined with a non-reactive material such as teflon.

•the autoclave is heated to above its normal boiling point, the pressure is increased
and is called ‘super heated water’.

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 3. Synthesis of BaTiO3 by Reaction in solid state:
3.1. Methods

Products of departure:

The synthesis of the solid solution of the studied system is carried out in the form
of solid state powders of BaCO3 and TiO2, according to the following reaction:

BaCO3 + TiO2 900°C à 1100°C BaTiO3 + CO2

Molar mass:
MBaCO3 = 197.149 g/mol
MTiO2 = 79.898 g/mol

Mixing powders:

The powders are weighed to 8.4774 g of BaCO3 and 3.4356 g of TiO2 near whose
stoichiometric proportions to obtain the desired composition to obtain 10 g of BaTiO3.
In our case:

BaTiO3 BaCO3 TiO2

1M 1M 1M
233.192 g/mol 197.149 g/mol 79.898 g/mol
10 g 8.4774 g 3.4356 g
0.043 M 0.043 M 0.043 M

The mixture is made in an agate mortar in the presence of ethanol, and then
kneaded in an agate ball planetary mill for one hour. This operation aims to reduce the
size of the particles and to promote the homogeneity of the mixture. The assembly is
then put in an oven at 60°C in order to eliminate the ethanol.

After homogenization and grinding in a porcelain or agate mortar, the BaCO3 +

TiO2 mixture is calcined either at 900°C or at 1100°C for several hours in an alumina
or platinum capsule.

The major disadvantage of this traditional method is the difficulty of controlling

stoichiometry and size.

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 3.2. Results and discussion

In this study, BaTiO3 have been prepared via solid-state reaction method. The
powders were calcined for 2 hours at different temperatures ranging from 600°C to
1200°C. Using X-ray diffraction with a Rietveld analysis, the phase formation and
crystal structure of the BaTiO3BaTiO3 powders were studied and the results of X-ray
diffraction are shown in (Figure3).

Figure 3: The specter of X-Ray diffraction of BaTiO3

The results show that the sample at calcinations temperature of 800⁰C and above
has relatively sharp and narrow peaks refer to the existence of BaTiO3’s phase.

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 Work Cited

[1] Schwartz, M. M. Handbook of Structural Ceramics, McGraw-Hill, New York,

1992.

[2] Randle, V. In Encyclopedia of Materials: Science and Technology,Vol. 10,K.H. J.

Buschow,

[3] Rice, R. W. Mechanical Properties of Ceramics and Composites: Grain and

Particle Effects, Marcel Dekker, New York, 2000.

[4] Hosford, W. F.; Caddell, R. M. Metal Forming: Mechanics and Metallurgy,

Prentice Hall, Englewood Cliffs, NJ, 1993.

[5] Randle, V.; Engler, O. Introduction to Texture Analysis: Macrotexture,

Microtexture and Orientation Mapping, Gordon and Breach, Amsterdam, 2000.

[6] Richerson, D. W. Modern Ceramic Engineering, Marcel Dekker, New York, 1992.

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 Appendices

Table 1: The lattice parameter, crystallite size and tetragonality of BaTiO3 powders at
different calcination temperatures.

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