CHAPTER FOUR

4. RESULTS AND DISCUSSION

4.1 Results
The characteristics of Isiala Oparanadim clay determined in this study are shown in
Table 4.1.

Table 4.1 Physical Characteristics of Isiala Oparanadim Clay

Parameters Value
pH 7.66
Oil absorption 42.6
Specific gravity 1.06
refractive index 1.63

4.1.1 pH Test

The pH of Isiala Oparanadim clay used in formulating alkyd paints was determined

to be 7.66; an indication that the clay is slightly basic. The pH of some extenders

are Okposi clay 7.46, fly ash 8.15, talc 9 – 9.50, and Okigwe-mbano clay 6.0 (Igwe

et al, 2016).

4.1.2 Specific Gravity

The specific gravity of Isiala Oparanadim clay was determined to be 1.06. This

study shows that the specific gravity of the extender used in this present study is
lower than that of titanium dioxide, TiO2 (4.26), which is the prime pigment. The

specific gravity of some extenders are China clay 2.6, whiting 2.7, talc 2.65, and

mica 2.8 – 2.85 (Chukwujike et al., 20). Generally, pigments that have low specific

gravity exhibit low settling tendencies, and high tinting strengths in paints (Boxall

and von Fraunhofer, 1986).

4.1.3 Refractive Index

The refractive index of Isiala Oparanadim clay was determined to be 1.63. This

property has great influence on the scattering power of paints. Generally, extenders

do not enhance the opacity or colours of paint films. The refractive indices of some

extenders are talc 1.40, barytes 1.64, and commercial whiting 1.58 (Igwe et al, 20).

The poor opacity exhibited in solvent paints by some extenders is attributed to their

low refractive indices (Boxall and Von Fraunhofer, 1986).

4.1.4 Oil Absorption

Oil absorption is the ratio of the amount of oil by weight needed to form a stiff but

spreadable paste from a quantity of pigment, and is usually expressed as the

number of grams of oil needed for 100 grams of pigment. The oil absorption of

Isiala Oparanadim clay was determined to be 42.60 g/100g clay as shown in table

4.1. Less oil absorption by an extender indicates less resin demand without

compromising other coating properties. The oil absorption by some extenders and
pigments are barium sulphate (blanc fixed) 18.5, China clay 30, Calcium carbonate

17.50, and talc 25 – 35 (Igwe et al, 2020).

4.1.5 Chemical Stability of the Extenders

The effect of heat on the colour and solubility of the extender used in this study in

different chemicals are as shown in Table 4.3. The table shows that the extender

was stable in hydrochloric acid, acetic acid, methanol, chloroform, xylene. There

was no colour change, or solubility in the chemical media, even when heated. The

stability of the clay is attributed to the large presence of inert oxides, SiO 2, and

Al2O3 and which have high melting points (SiO2,1713oC and Al2O3, 2054oC).

Table 4.2 Chemical Stability of Isiala Oparanadim Clay

Chemicals Solubility Colour change

used Cold Hot Cold Hot
HCl Nil Nil Nil Nil
Acetic acid Nil Nil Nil Nil
Methanol Nil Nil Nil Nil
Chloroform Nil Nil Nil Nil
Toulene Nil Nil Nil Nil

4.1.6 Chemical Composition

The chemical composition of the calcined clay, 1M HCl treated clay, and 3M HCl

treated clay was determined using an Atomic Adsorption Spectrophotometer (2000

series Agilent Technology) as shown in Table 4.3. The results show an appreciable
presence of silica (SiO2), which is then followed by Aluminum oxide (Al 2O3), iron

(iii) oxide (Fe2O3), and titanium dioxide (TiO2) in that order while the other oxides

are present in very small proportions.

Table 4.3 Chemical Composition of Isiala Oparanadim Clay

Constituent Calcined clay HCl treated (1M) HCl treated (3M)

(wt. %) (850oC)
PbO 0.02 0.01 0.12
ZnO 0.31 0.24 0.21
CuO 0.05 0.03 0.02
Fe2O3 9.63 9.29 9.33
Mn2O3 0.02 0.01 0.01
MgO 0.29 0.05 0.01
N2O 0.54 0.48 0.27
SiO2 61.35 54.11 53.01
Al2O3 24.01 21.67 20.95
TiO2 2.49 2.44 2.17
K2O 0.53 0.42 0.44
C2O 0.70 0.63 0.53
Total 99.94 99.98 100.07

The presence of the unreactive oxides in the clay is indicative that paints

formulated with the clays will function as anti-corrosive paints since the unreactive

oxides will slow down the diffusion of corrosive species thereby slowing

(delaying) the phenomenon of corrosion in painted surfaces (Tiwari and Saxena,

1999). The metal oxide contents of the calcined clay are generally higher than
those of hydrochloric acid treated clays with the exception of aluminum oxide

(Al2O3) contents where the reversed was observed. The Al 2O3 content of the clays

are in this order: Calcined clay < HCl treated (1M) < HCl treated (3M) and this is

attributed to the removal of metallic oxides during the treatment with HCl (Eze et

al, 2012). The table shows that the table removed increases with the concentration

of HCl

4.2 Properties of Prepared Paint Samples

4.2.1 Surface – Dry Times

The surface dry times of the formulated alkyd paints of calcined and hydrochloric

acid treated clays, shown on Table 4.3 and illustrated graphically in Figure 4.1

were within 20 – 50 minutes.

Table 4.4 Surface Drying Properties of Prepared Alkyd Paint Samples

Surface dry time (min)

HCl Treated HCl Treated
clay content calcined clay Clay (1M) Clay (3M)
100/0 13 13 13
80/20 30 22 15
60/40 35 26 19
50/50 41 30 28
40/60 37 27 22
20/80 32 25 17
 45
40
35
30
25
Axis Title

Calc Clay
20 1M HCl
15 3M HCl
10
5
0
0 10 20 30 40 50 60 70 80 90
Axis Title

Figure 4.1 Effect of Extender Content on Surface Dry Time of Formulated Alkyd
Paints

The surface dry times of the paint sample containing only TiO2 without an extender

pigment is 13 minutes. Technically, the incorporation of Isiala Oparanadim clay

increased the surface dry time as the quantity of the extender pigment increased, it

attained a highest surface dry time with the clay with 50 % clay content, and then it

decreased. The surface dry times of the formulated paint samples satisfied the

Nigerian Industrial Standard (NIS) requirement that the surface dry time of a gloss

paint shall not exceed 6 hours from the time of application. The incorporation of

Isiala Oparanadim clay into alkyd paints did not adversely affect the paints surface

drying times. Generally, the calcined formulated paints exhibited higher surface
dry time than the acid treated clays. The observed order of surface dry time of the

paint samples is

Calcined clay > HCl treated clay (1M) > HCl treated clay (3M). Thus, acid

treatment of the clay greatly reduced the surface dry time of the formulated paint

samples. The best surface dry time of 15 minutes was recorded for HCl (3M)

treated clay at

20 wt% clay content and which was very close to 13 minutes observed for the paint

sample without clay.

4.2.2 Through – Dry Times

The through dry times of the formulated paint samples is shown in Table 4.4 and

illustrated graphically in Figure 4.2.

Table 4.5 Through Drying Properties of Prepared Alkyd Paint Samples

Through - Dry Time (min)

HCl treated HCl treated
Clay content Calcined clay clay (1M) Clay (3M)
0 210 210 210
20 317 252 225
40 325 260 232
50 334 269 247
60 320 267 240
80 306 261 229
 400

350

300 Calcinaed
Clay
250
Treated
200 Clay 1M
3M HCl
150

100

50

0
0 10 20 30 40 50 60 70 80 90

Figure 4.2 Effect of Extender Content on Through Dry Time of Formulated

Alkyd Paints

paint formulation without the extender pigment had a through dry time of 210

minutes. An increase in the through dry time of the formulated paint sample was

noticed with increasing extender pigment. The paint formulation containing 50 wt

% extender pigment and 50 wt% Titanium dioxide has the highest through dry time

for both the calcined clay, 1M treated clay, and 3M treated clay. There was a

decline in the through dry time of the paint formulations. All paint samples had a

good through dry sample since according to Nigerian Industrial Standards (NIS),

the through dry time of a gloss paint should not exceed 23 hours. The least through

dry time of 225 minutes was recorded at 20 wt% content was recorded for HCl

(3M) treated clay.

4.2.3 Thickness of Dry Paint Films

The variation of prepared dry paint film thicknesses with clay content, and

treatments are shown in Table 4.6. The TiO 2 formulated paint sample had dry paint

film thickness of 1.25mm. The dry film thicknesses of the paint samples ranged

from 0.70 – 1.40mm. Generally, a film thickness of more than 20µm performs well

on a barrier resistant to weathering (Titan Aik, 1995). The film thicknesses

obtained in this study is in this range, an indication that the formulated paints will

function as anti-corrosive paints. Paint samples containing 50 wt. % HCl (1M)

treated clay, exhibited the highest film thickness of 1.41mm while the sample

containing 40 wt. % calcined clay had the least film thickness of 0.70mm. There is

no general order of variation of paint film thicknesses of the treated clays with clay

contents.

Table 4.6 Film Thicknesses of Formulated Alkyd Paint Samples

Film Thickness (mm)

Calcined clay HCl treated HCl treated

Formulation clay (1M) clay (3M)
100/0 1.25 1.25 1.25
80/20 0.8 0.76 0.79
60/40 0.7 1.37 0.77
50/50 0.91 1.41 0.82
40/60 0.75 0.83 0.91
 20/80 0.81 0.9 1.16

1.6

1.4

1.2
Calcined
Paint Film Thickness

clay
1
Treated
0.8 clay 1M
0.6 Treated
clay 3M
0.4

0.2

0
0 10 20 30 40 50 60 70 80 90
Clay content (wt. %)

Figure 4.3 Effect of Extender Content on Paint Film Thickness

4.2.5 Adherence of Paint Films to Steel Surfaces

The dry paint films exhibited good adherence properties to mild steel as evident

from Table 4.7. An oil (gloss) paint shall not exhibit more than 50% removal

Table 4.7. Percentage Adhesion of Formulated Alkyd Paint Samples

Percentage Adhesion (%)

Formulation
HCl treated clay HCl treated clay
Calcined clay (1M) (3M)
100/0 1.88 1.88 1.88
80/20 11.25 9.37 11.56
60/40 10.0 11.87 5.0
50/50 5.0 11.25 30.0
40/60 3.75 15.62 11.25
 20/80 6.87 6.25 5.62

35

30

25
Cal-
cined
% Adhesion

20 clay
Treated
15 clay 1M
Treated
10 clay 3M

0
0 10 20 30 40 50 60 70 80 90
Clay content (wt. %)

Figure 4.4 Effect of Extender Content on Adhesion of Formulated Paint Samples

of the dried paint film. The TiO 2 formulated paint had 1.88% removal of paint dry

film. The paint sample containing calcined clay (50 wt. %), and HCl (1M) treated

clay (40 wt. %) exhibited the least dry paint film removal of 5.0 % while the HCl

(3M) treated clay (50.0 wt. %) has the highest dry paint film removal of 30.0%.

The good adherence property recorded for the paint samples is an indication that

the paint samples should function as anti-corrosive paints.

4.2.4 Hardness of Dry Paint Films

The hardness of the formulated paint samples are shown in Table 4.7. Paint

samples containing calcined clay (60, and 80 wt. % and HCl (1M) (80 wt. %)
treated paints had maximum dry film hardness of 5H, followed by HCl (3M)

treated clay containing 80 and 40 wt. % clays that had pencil hardness of 4H. The

least film hardness of 2B was recorded for TiO2 formulated paint without clay. The

hardness of paint films for calcined clay generally increased with clay content. The

formulated paint samples had good hardness property, an indication that the paint

films will protect the painted substrate from mechanical damages, and

subsequently, prevent corrosion of the substrate from environmental damage.

Table 4.8 Pencil Hardness of Formulated Paint Film Samples

Formulation Pencil Hardness

HCl treated HCl treated

Calcined clay clay (1M) clay (3M)
100/0 2B 2B 2B
80/20 H 2H H
60/40 3H H 4H
50/50 3H 3H B
40/60 5H 3H 2H
20/80 5H 5H 4H

4.2.6 Impact Strength of Dry Paint Films

The impact strength of the formulated paint samples were determined using

Charpy Impact Tester. All the formulated paint samples passed the impact test.

This attests to the good quality of the paints

4.2.7 Chalking Test

None of the formulated paint samples chalked when rubbed with hand which

indicates a good quality.

4.2.8 Chemical Resistance of Dry Paint Films

The resistance of the dry paint films to 2% NaCl, 2% NH 3, 2% H2SO4, and 2%

Na2CO3 are shown in table 4.8. No blistering or other film defects was observed on

immersion of the dry paint films in NaCl. This indicates that the formulated paint

samples will function as anti-corrosive paints for the protection of steel in salty

environments. This occurs because of the presence of unreactive metallic oxides in

the clay samples which will slow down the diffusion of corrosive species into the

film substrate thereby slowing down the corrosion of mild steel. From table 4.8.

The paint dry films also performed well on immersion in 2% H 2SO4. The

performances in 2% Na2CO3 and 2% NH3 were not generally good except for slight

wrinkling or colour change observed for some formulations. From table 4.8. It is

apparent that calcined clay formulated paints exhibited fairly better resistance to

2% Na2CO3, 2% Na2CO3 and 2% NH3 than HCl treated formulated paints.

Table 4.9 Chemical Resistance of Dry Formulated Paint Samples

Resistance to Chemicals
Formulation NaCl
HCl Treated HCl treated
Calcined clay Clay (1M) clay (3M)
100/0 0 0 0
80/20 0 0 0
60/40 0 0 0
50/50 0 0 0
40/60 0 0 0
20/80 0 0 0
Na2CO3
100/0 0 0 0
80/20 2 3 3
60/40 2 4 4
50/50 2 4 4
40/60 2 3 3
20/80 1 3 4
H2SO4
100/0 0 1 1
80/20 0 0 0
60/40 0 0 0
50/50 0 1 0
40/60 0 1 0
20/80 0 1 0
NH3
100/0 1 1 1
80/20 0 3 4
60/40 4 2 3
50/50 3 3 4
40/60 2 1 2
20/80 1 4 1
 CHAPTER FIVE

5. CONCLUSION AND RECOMMENDATIONS

5.1 Conclusions

Calcined and hydrochloric acid treated Isiala Oparanadim clays have been used to

prepare alkyd paints possessing anti-corrosive property on mild steel. The clay

which consisted predominantly of silica (SiO2), aluminum oxide (Al2O3), iron (iii)

oxide (Fe2O3), and titanium dioxide (TiO2) was sieved to 75µm particle size and

incorporated into alkyd paints at extender contents, 0 to 80.0 wt. %

a) The surface- , and through - dry times of the formulated paints were within

acceptable limits, an indication that incorporating treated Isiala Oparanadim

clay into alkyd paints had no adverse effects on drying paint properties. The

HCl formulated paints had both dry times than those of calcined clays.

ii) The film thickness, hardness, impact strength, and adhesion properties of the

paint dry films were generally good, and contributed to the observed anti-

corrosive properties of the paint samples on mild steel.

iii) The dry paint films exhibited no blistering or any other film defects on

immersion in 2% NaCl, an indication of the anti-corrosive properties of the

paints on application in salty environment.

iv) The performance of the paint dry films were good in 2% H 2SO4, fairly good

for calcined clays formulated paints in 2% Na 2CO3, and 2% NH3, but

generally poor for HCl treated clays formulated paints in 2% Na2CO3 and

2% NH3.

v) The calcined clays formulated paints exhibited fairly better resistance to 2%

Na2CO3, 2% NH3, and 2% H2SO4 than the HCl formulated paints.

The present study has highlighted the utility of Isiala Oparanadim clay in

formulating anti-corrosive alkyd paints. The clay which is stable to heat, chemical,

easy to process, and indigenously available will generally provide a cheap source

of paint extender, and a source of economic empowerment for the rural populace

where the clay deposits are located.

5.2 Recommendations

The Isiala Oparanadim clay has been used to formulate alkyd paints with improved

paint properties. Further study should be carried out to improve the film resistance

of HCl treated clays formulated paints to 2% NH3 and 2% Na2CO3.