CHAPTER THREE

MATERIALS AND METHODS

3.1 Introduction

This chapter presents the materials, experimental procedures, and analytical techniques

employed in the extraction and characterization of titanium dioxide (TiO₂) from paint sludge and

expired paint samples. The methodology integrates thermal treatment, physicochemical

separation, and advanced characterization techniques to ensure efficient recovery and analysis of

the target material.

3.2 Materials and Reagents

All reagents used in this study were of analytical grade and were applied without further

purification. Distilled water was used throughout all experimental procedures to avoid

contamination from dissolved ions.

The principal reagents included hydrochloric acid (HCl, 37%), nitric acid (HNO₃, 65%), sodium

silicate (Na₂SiO₃), oleic acid (as a collector), and methyl isobutyl carbinol (MIBC) as a frothing

agent during flotation. These reagents were selected based on their effectiveness in mineral

processing and impurity removal.

3.3 Apparatus and Equipment

The experimental work was carried out using standard laboratory and analytical equipment.

These included a laboratory-scale microwave pyrolysis unit, a muffle furnace, a vacuum

filtration apparatus, a drying oven, an analytical balance, a mechanical stirrer, a flotation cell,

and a pH meter.
For material characterization, advanced analytical instruments were employed, including

scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM–EDS),

X-ray diffraction (XRD) equipment, and Fourier transform infrared (FTIR) spectroscopy.

3.4 Sample Collection and Preparation

Paint sludge and expired paint samples were collected from Myer Paint PLC, Lagos, Nigeria, in

October 2025. Upon collection, the samples were dewatered using a vacuum filtration system to

remove excess liquid content. The dewatered samples were subsequently dried in a laboratory

oven at 105 °C for 24 hours to eliminate residual moisture. After drying, the samples were

ground in a mortar and pestle and sieved to obtain particles less than 250 µm.

This homogenization process was necessary to improve the efficiency of subsequent thermal

treatment and separation processes. The prepared samples were stored in airtight polyethylene

bags to prevent moisture absorption prior to further experimental procedures (Khezri and

Bloorchian, 2009).

3.5 Thermal Treatment via Microwave Pyrolysis

The thermal decomposition of the prepared samples was carried out using a laboratory-scale

microwave pyrolysis system (Stena Metall AB, Göteborg). The reactor chamber had dimensions

of 390 × 430 × 950 mm and a total capacity of 10 L.

Microwave radiation was generated using three Samsung OM75P magnetrons operating at a

fixed frequency of 2465 MHz, each delivering 1.5 kW of power. Approximately 100 g of dried

sample was placed in a microwave-transparent mica container. Prior to each experiment, the

reactor was purged with nitrogen gas at a flow rate of 5.6 L min ⁻¹ for 4 minutes to establish an

inert atmosphere and prevent oxidation.

procedures. The temperature was increased at a heating rate of 10 °C min ⁻¹ up to 400 °C and

maintained for 60 minutes. Temperature monitoring was performed continuously at multiple

points within the system.

After completion, the samples were allowed to cool to room temperature in a desiccator. The

resulting solid residue (ash), which contained predominantly inorganic components such as TiO₂

and mineral fillers, was collected for further processing. Gaseous products were estimated by

mass balance, although the primary focus of this study was on the solid fraction (Karlsson et al.,

2015).

3.6 Ash Conditioning

The pyrolyzed ash was conditioned to remove soluble impurities and improve mineral liberation.

This process involved dispersing the ash in distilled water at a solid-to-liquid ratio of 1:5, then

agitating for 10 minutes. The resulting suspension was filtered, and the recovered solids were

dried at 80 °C. The dried material was subsequently reground to enhance particle liberation,

thereby improving flotation efficiency (Karlsson et al., 2015).

3.7 Froth Flotation Process

Froth flotation was employed as the primary separation technique to concentrate TiO₂ from the

conditioned ash. A slurry was prepared by mixing 50 g of conditioned ash with 500 mL of

distilled water. The pH of the slurry was adjusted to 5–6 using dilute acid or base. Oleic acid (1.0

g) was added as a collector to selectively render TiO₂ particles hydrophobic. Sodium silicate (0.5

g) was introduced as a depressant to inhibit the flotation of siliceous impurities. A few drops of

methyl isobutyl carbinol (MIBC) were added as a frothing agent.

reagents and particles. Air was then introduced into the system for 10–15 minutes, allowing

hydrophobic particles to attach to air bubbles and rise to the surface as froth. The froth fraction,

enriched in titanium dioxide, was skimmed off, filtered, and dried at 80 °C for further

purification and analysis.

3.8 Acid Leaching of Concentrate

To remove residual impurities, particularly calcium-based compounds, the flotation concentrate

was subjected to acid leaching. Approximately 20 g of the concentrate was treated with 200 mL

of 1–2 M hydrochloric acid and heated at 70–80 °C under continuous stirring for 1–2 hours.

CaC O3 +2 HCl → CaC l 2+C O2+ H 2 O

Following the leaching process, the mixture was filtered to separate the solid residue from the

liquid phase. The solid fraction was washed repeatedly with distilled water until the pH was

neutral, then dried at 80 °C.

3.9 Scanning Electron Microscopy (SEM–EDS) Analysis

The morphology and elemental composition of the samples were analyzed using scanning

electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS). Prior to

analysis, samples were centrifuged at high speed (120,000 rpm for 10 minutes) using a Hitachi

S150NX centrifuge. The recovered solids were mounted on sample holders using carbon tape

and sputter-coated with a thin layer of gold to enhance conductivity. The analysis was performed

using a JEOL IT300 SEM instrument at an accelerating voltage of 30 kV, with magnification

ranging from 1,000× to 30,000× (Pratiwi et al., 2019).

X-ray diffraction (XRD) analysis was conducted to determine the crystalline phases present in

the extracted material. This technique is based on the diffraction of X-rays by periodic atomic

planes, as described by Bragg’s Law. Powdered samples with fine particle size (0.5–3 g) were

analyzed, and the diffraction patterns obtained were used for both qualitative and quantitative

phase identification (Bhadeshia, 2004).

3.11 Fourier Transform Infrared (FTIR) Spectroscopy

Fourier transform infrared spectroscopy (FTIR) was used to identify functional groups present in

the extracted TiO₂. The analysis was performed using a Shimadzu IR-Prestige 21 FTIR

spectrophotometer equipped with an attenuated total reflectance (ATR) accessory. Spectra were

recorded over 400–4000 cm⁻¹ at a resolution of 4 cm⁻¹. Each spectrum was obtained as an

average of 30 scans to ensure accurate, reproducible results (Tamanna et al., 2024).

3.12 Data Analysis

Experimental data obtained from the characterization techniques were analyzed using standard

analytical methods. SEM–EDS results were used to evaluate morphology and elemental

composition, XRD patterns were interpreted for phase identification, and FTIR spectra were

analyzed to determine functional groups.

Quantitative results were presented in graphical and tabular forms where appropriate, and

comparisons were made with standard reference materials to validate the findings.
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