Middle East Technical University

Department of Metallurgical and Materials Engineering

MetE-215 Materials Processing Laboratory

Experiment 3: Sol-Gel Processing

Instructor: Prof. Dr. C. Durucan

Assistant: H. E. Sever

Experiment Date: 23.12.2021

Submission Date: 02.01.2022

Group 7: SERDAR GÜLER, TANER GÖKTUĞ TEKİN, YİĞİT FURKAN

YENİAY, BİLGESU KARABACAK, TOPRAK ÇAKAL, İREMNUR KELEŞ,

KORAY BÜYÜKYILDIZ, MUHAMMED KAĞAN KUŞDEMİR, KARDELEN

POLAT, ELİF EREN, KÜBRA KARABULUT, UYGAR ERSOY

İremnur
KELEŞ
2447662
ABSTRACT
In this experiment, the sol-gel method was processed by using TEOS alkoxide, HCl,
NaOH catalysts. Gel formation in the use of acid catalyst only, gel formation in the use of
acid and base catalysts together was compared. The effect of pH on hydrolysis and
condensation is discussed in the experiment.

INTRODUCTION
The sol-gel method performs hydrolysis and condensation reactions to mix raw
materials homogeneously and form a stable, transparent sol using a chemically
active compound. The sol-gel method is a widely used method for preparing
ceramic materials such as metal oxides, nitrides, carbides. The reaction occurs by
hydrolysis and condensing an inorganic or metal-organic precursor to form a sol. It
turns into calcined gel after chemical reactions and thermal processes.[5]

The most significant advantage of the sol-gel method is that it obtains high surface
area and stable surfaces. Other advantages;

 Producing a thick coating for corrosion protection

 Having sintering capacity at low temperatures between 200 and 600 degrees
 An economical and efficient method to produce high-quality coverage [6].

Disadvantages;

 Contraction during the procedure

 Residual hydroxyl and carbonyl groups
 Long process
 Fine pores
 The use of organic solutions that may have a toxic effect [6].

The process begins with metal oxides. Metal oxides form sols and gels by
hydrolysis and condensation reactions. The most important alkoxides are
alkoxysilanes such as tetraethoxysilane (TMOS) and tetraethoxysilane (TEOS) [3].
Sol-gel transformation reactions can be explained as in Figure 1.
Figure 1. Hydrolysis and condensation reactions in sol-gel processes [3]

Hydrolysis of alkoxy groups precedes the condensation reaction and produces

silanol groups (Si-OH). These then condense into alcohol or Si-O-Si bonds.

Alkosilicans are generally insoluble in water. Therefore, common solvents such as

alcohol are added.

Processing of monolithic sol-gel derived products

Drying: removes liquids such as water and solvent.

Sintering: It thickens the gel by removing the pores formed after drying.

Coating of sol-gel products

The coating is simply the process of coating any surface. The coating can be used to
produce materials with features such as easy cleaning, anti-fog, anti-scratch, IR
reflective.

Spin coating: In this coating method, the solution of the material rotates on an axis
perpendicular to the coating area. The thickness of the coating varies depending on
the rotation speed and solution properties.

Coating by dipping: This process takes place by immersing the substance in the
tank containing the coating material and filtering it. Thanks to this technique, it can
create materials that are resistant to heat and electric current.[4]
EXPERIMENTAL
Materials
 TEOS (Tetra ethyl orthosilicate)
 Polycarbonate substrates
 Ethanol and DI-water
 HCl(aq) and NaOH(aq)

Equipment

 Borosilicate glass beakers (20x-50 mL)

 Magnetic bars (10x)
 Polystyrene test tubes and tube holders
 Parafilm
 Volumetric measuring cylinders
 Laboratory Hood with adequate bench space
 Spin Coater
 Hot-plate (2x)
 pH-meter and thermometer
 Volumetric (Micropipettors) or weight-based measuring (Balance) units

Procedure

12 ml of TEOS, 24 ml of ethanol and 15 ml of distilled water are mixed with a spin

coater on the hot plate at 260 Rpm. The pH is measured with a pH meter, and notes
are taken. HCl is gradually dropped in drops as an acid catalyst until the pH value
reaches 1.5-2. The sample obtained is taken into a test tube. The lid of the test tube
is covered with parafilm to prevent evaporation. The basic catalyst NaOH is
gradually dropped into the remaining mixture. The dripping process continues until
the pH value reaches between 5-5.5. The 2nd sample from the obtained mixture is
transferred to the test tube. The lid is covered with parafilm. Mixing continues
during all operations. After the samples are kept for three days, their viscosity status
is observed.
RESULT

As a result of the mixture of TEOS, ethanol and distilled water, the pH value was
3.94. The Color of the mix was blurred. After adding the acid catalyst, the pH of the
mixture was measured at 1.81. The color has become clear. It was observed that the
viscosity of the sample taken from this mixture and kept for three days was low.
Afterwards, the pH of the mix, in which the basic catalyst was dropped, was
measured at 5.33. While the color was expected to be clear, turbidity was observed
due to the old age of the materials. It was observed that white particles were formed
and precipitated. It was observed that the viscosity of the second sample, which was
taken from this mixture and kept for three days, was high. In addition, when the
samples were taken, it was observed that the viscosity of the second sample was
higher than the first. These data are given in Table 1.

Table 1. The results of the experiment

1. sample 2. sample
pH 1.81 5.33
Gelation after the Not observed A little
experiment
Gelation after 3 Not observed Observed
days

DISCUSSION
By looking at the experiment results and the hydrolysis-condensation versus pH graph, we

can say that the viscosity of the first sample is low and the second is high because the

condensation is high in the range where the approximate pH values are 4 and 10. In the

first example, there also will be condensation, but three days is not enough time because

the reaction rate is low. Due to the alcohol-water mixture, the mixture color was cloudy at

first. Since the water was used in the hydrolysis reaction after the acid was added, ethyl

alcohol remained in the system. This situation caused the color to become transparent.

Then, the acid-base reaction took place due to the base that was dropped, and as a result,

precipitation occurred. The base was dropped on the acidic solution because we wanted

the hydrolysis reaction to occur first and then the condensation reaction.

Figure 2. Reaction rate versus pH diagram for both hydrolysis and condensation reactions

(Gutiérrez-Climente et al., Sol–Gel Process: The inorganic approach in protein imprinting

2021)

CONCLUSION
This experiment studied the effect of pH on opacity and viscosity in the sol-gel method.

Acid and base catalysts were used in the experiment. It was concluded that the

condensation rate is quite low at low pH. It was observed that the other sample, which

underwent a condensation reaction as a result of the effect of higher pH, turned into gel

form. It has also been proven that the hydrolysis reaction occurs with the clarification of

the TEOS, ethanol-water mixture.

APPENDIXE

Figure 3. (a) Spin-coating and (b) dip-coating, both processes of deposition of thin film.

(Boratto, Miguel. 2018).

REFERENCES
1. Gutiérrez-Climente, R., Clavié, M., Dumy, P., Mehdi, A., & Subra, G. (2021, January

15). Sol–Gel Process: The inorganic approach in protein imprinting. Journal of

Materials Chemistry B. Retrieved January 2, 2022, from

https://pubs.rsc.org/en/content/articlelanding/2021/tb/d0tb02941f

2. Boratto, Miguel. (2018). Semiconducting and Insulating oxides applied to electronic

devices. 10.13140/RG.2.2.30070.29762.

3. Polymer properties database. Sol-Gel Chemistry. (n.d.). Retrieved January 2, 2022,

from https://polymerdatabase.com/polymer%20chemistry/Sol-Gel%20Chemistry.html

4. Dip coating technology. Apex Instruments. (n.d.). Retrieved January 2, 2022, from

http://www.apexicindia.com/technologies/dip-coating-technology

5. D'Arienzo, M., Scotti, R., Di Credico, B., & Redaelli, M. (2017). Synthesis and

characterization of morphology-controlled tio 2 nanocrystals. Studies in Surface

Science and Catalysis, 477–540. https://doi.org/10.1016/b978-0-12-805090-3.00013-9

6. MODAN, E. M., & PLĂIAȘU, A. G. (2020). Advantages and disadvantages of

chemical methods in the elaboration of nanomaterials. The Annals of “Dunarea De

Jos” University of Galati. Fascicle IX, Metallurgy and Materials Science, 43(1), 53–

60. https://doi.org/10.35219/mms.2020.1.08