Chapter 2: Experimental Techniques
2.1. Growth techniques for the synthesis of TiO 2 nanostructures
We have used two different growth techniques for the fabrication of undoped and doped TiO2 nanostructures. One dimensional (1D) nanostructures, i.e., NTs, NRs, NWs and NRbs are grown using hydrothermal/ solvothermal techniques. For the hydrothermal/ solvothermal techniques, we used a stainless steel high pressure reactor, known as autoclave with Teflon- liner (Bergof-100, Germany). Several growth parameters such as solvents, reaction temperatures and reaction durations were varied for the growth of wide variety of nanostructures and their formation mechanisms are described in Chapter 3. Planetary ball- milling machine (Retsch, PM 100) is used for the growth of Co doped TiO2 NPs.
2.1.1. High pressure reactor for the Hydrothermal/ Solvothermal growth
The hydrothermal set-up used in our laboratory consists of three parts, i.e., Teflon-lined stainless steel autoclave (reaction vessel), rectangular hot box (prevent for heat radiation) and hot plate (provide heat for a particular set temperature) with stirring facility. The photograph of the complete hydrothermal set-up used in this study is shown in Fig. 2.1. The autoclave consists of a stainless steel vessel (outer) with stainless steel cap and clamp. A Teflon inner
vessel (capacity 100 ml) is lined inside the stainless steel vessel and this is used as the container for the precursor solutions to avoid the unwanted mixing of impurities during reaction. An O-ring is placed on the mouth of the Teflon vessel. The stainless steel cap mounted with Teflon in the inner part is used as lid to close the vessels. The autoclave has a thermal sensor with immersion tube inside the Teflon vessel, which is connected to a PID controller to measure the exact internal temperature of the reaction solution. A monometer is in-built with the autoclave to measure the pressure inside the autoclave during the reaction.
The autoclave has also gas feeding and liquid samples extraction facility during the reaction.
The rectangular hot box is placed on the top of the hot plate with stirring facility which is placed on a table. The hot plate has two knobs, one for setting the required temperatures and the other for stirring. The hot box is used to prevent the heat radiation to the outside of the autoclave. After filling the precursor mixed solutions inside the autoclave, the system is closed with the stainless steel clamp. Then the autoclave is placed inside the rectangular hot box which is placed on the top of the hot plate. The thermal sensor is connected with a PID controller through a connecting wire which display the inside temperature of the autoclave.
This allows a precise measurement of the reaction temperature. Finally, the hot plate is connected to the main power supply to heat the hot plate and carry out the hydrothermal reaction at a particular set temperature and stirring condition.
Fig. 2.1. Photograph of high pressure reactor (autoclave) (Berghof, BR-100; Germany).
2.1.2. High temperature furnace for calcinations and vacuum annealing
A High temperature split type furnace (Indfurr, India) is used for the calcinations of the samples obtained from hydrothermal method. It consists of a horizontal muffle furnace, a cylindrical quartz/ alumina tube (placed inside the muffle furnace). The furnace is connected to programmable controller to control the set temperature, the heating rate and tune duration of heating at a particular temperature. For vacuum annealing, we designed the vacuum system in our laboratory. The photograph of vacuum annealing system is shown in Fig. 2.2.
The one end of the alumina tube is closed. The other end of the alumina tube is connected to a rotary pump for evacuation of the tube chamber. The pressure inside the tube is monitored by a pirani gauge connected to the exhaust side of the rotary pump. We achieved a pressure of 1.2 × 10-2 mbar inside the tube, which was displayed in the pirani gauge.
Fig. 2.2. Photograph of high temperature furnace with vacuum system.
2.1.3. Hydrothermal/ Solvothermal technique for the growth of TiO2 nanostructures For the hydrothermal/ solvothermal growth of TiO2 nanostructures, four parameters are usually controlled i.e., precursors, solvents, reaction temperatures and reaction durations. We used commercial TiO2 anatase powders (Merck), titanium butoxide, Ti(OC4H9)4 (Sigma Aldrich) as precursors and alkaline water, alkaline water-ethanol, water-ethylene glycol as base solvents and water-HCl as acid solvent. The reaction temperatures are maintained at
130, 155, 180, 205 °C with autogeneous pressure inside the autoclave throughout the reaction and reaction durations are varied as 12, 16, 24, and 48 hours. At first, we prepared the precursor solution by mixing the TiO2 precursor (anatase TiO2 powder/ titanium butoxide) in alkaline (10M NaOH) aqueous or non-aqueous solvent for the base-mediated growth and water-HCl mixed solvent for the acid-mediated growth. The mixed solution is stirred for 30 minutes in a conical flax and then transferred to the autoclave for hydrothermal/ solvothermal reactions. Next the precipitates are taken out of the autoclave and further processed such as ion-exchange reaction and calcinations (for base-mediated preparation only) to obtain the final samples. The as-obtained precipitate from the base-mediated reaction after washing several times with de-ionized (DI) water is allowed to react with 0.1M HCl for ion exchange between Na+ and H+. After ion-exchange reaction and several times washing is hydrogen- titanate, the product is calcined at different temperatures (500, 700 and 900 °C) for dehydration and to remove the residual organic impurities. Finally, depending upon the calcinations temperatures, TiO2 nanostructure samples with different phases are obtained.
The ion exchange reaction was not needed for acid-mediated precipitates; several times washing with DI water and heat treatment were needed for better crystallinity.
2.1.4. Ball milling method for Co doped TiO2 nanoparticles
Planetary Ball milling is used to grow Co doped TiO2 nanoparticles. In our laboratory, we have a programmable ball milling machine (Retsch, PM 100) that is shown in Fig. 2.3. It consists of vial, balls and a planetary platform with a certain rotation speed. The important precaution is the use of non-corrosive vial and balls and their cleanliness. For example, to study the magnetic properties, one should avoid the use of metal vial and balls because these may add impurity to the sample that may cause a change in magnetic property of the sample.
For the present study, we used contamination free zirconia (ZrO2) balls and vial for the growth of Co doped TiO2 nanoparticles. At first, the required amount of Co powder and TiO2 powder are mixed in a ceramic mortar and ground for 10 minutes. Then the mixed powder is put inside the vial with required amount of balls (powder: ball = 1:10) and set at 350 rpm for 5 h duration.
Fig. 2.3. Photographs of the p Zirconia balls.