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Gum arabic as a potential corrosion inhibitor for aluminium in alkaline medium and its adsorption characteristics

S.A. Umoren and I.B. Obot


Department of Chemistry, Faculty of Science, University of Uyo, Uyo, Nigeria

E.E. Ebenso and P .C. Okafor


Physical Chemistry Unit, Department of Pure and Applied Chemistry, University of Calabar, Calabar, Nigeria, and

O. Ogbobe and E.E. Oguzie


Department of Polymer and Textile Engineering and Electrochemistry/Materials Science Research Laboratory, Federal University of Technology, Owerri, Nigeria
Abstract Purpose To investigate the inhibitive effect of gum arabic (GA) for the corrosion of aluminium in alkaline (NaOH) medium and determine its adsorption characteristics. The present work is another trial to nd a cheap and environmentally safe inhibitor for aluminium corrosion. Design/methodology/approach The inhibition efciency (%I) has been evaluated using the hydrogen evolution (via the gasometric assembly) and the thermometric methods at 30 and 408C. The concentrations of GA (inhibitor) used were 0.1-0.5 g/l and the concentrations of NaOH (the corrodent) were 0.1-2.5 M. The mechanism of adsorption inhibition and type of adsorption isotherms were proposed from the trend of inhibition efciency with temperature, Ea, DGads and Qads values. Findings GA inhibited the corrosion of aluminium in NaOH solutions. The inhibition efciency increased with increase in GA concentration and with increase in temperature. Phenomenon of chemical adsorption is proposed for the inhibition and the process followed the Langmuir and Freundlich adsorption isotherms. The results obtained in this study for the %I were comparable for the two methods used and were corroborated by kinetic and thermodynamic parameters evaluated from the experimental data. Research limitations/implications Further investigations involving electrochemical studies such as polarization method will enlighten more on the mechanistic aspect of the corrosion inhibition. Originality/value This paper provides new information on the possible application of GA as an environmentally friendly corrosion inhibitor even in highly aggressive alkaline environments. It has not been published elsewhere. Keywords Alkalinity, Corrosion inhibitors, Metals Paper type Research paper

1. Introduction
Some investigations have been made recently into the use of naturally occurring substances to inhibit corrosion of metals in acidic environments. Plant extracts including their leaves and tubers and their corrosion inhibitive properties have been widely examined (Loto, 1990; Zakvi and Mehta, 1988; Kar et al., 1998; Verma and Mehta, 1998, 1999; Ebenso et al., 1996, 2004; Ekpe et al., 1994; Sakthievel et al., 1999; Ramesh et al., 2001; Avwiri and Igho, 2003; El-Etre, 2001, 2003; Muller, 2004). It has been shown that the inhibitive effect of some plants solution extract has been attributed to the presence of tannin in their chemical constituents (Martinez, 2002). Investigation of natural substances as corrosion
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Anti-Corrosion Methods and Materials 53/5 (2006) 277 282 q Emerald Group Publishing Limited [ISSN 0003-5599] [DOI 10.1108/00035590610692554]

inhibitors has attracted considerable attention because they have been shown to be low cost, ecologically friendly and possess no threat to the environment. Gum arabic (GA) which is the subject of the present investigation is a dried, gummy exudate obtained from various species of Acacia trees of the leguminosae family. It is water soluble and a complex mixture of arabinogalactan, oligosaccharides, polysaccharides and glucoproteins (Chaplin, 2003; Abdallah, 2004). In practical terms, gums are dened as molecular structures, tending to high molecular mass, usually with colloidal properties, that, in an appropriate solvent produce gels or suspensions of high viscosity or solutions of low matter content that can absorb water at ten times their weight. GA is a useful hydrocolloid, emulsier, texturizer, lm former and stabilizer. Investigations into the use of natural substances as corrosion inhibitors have been conducted in acidic medium and there seem to be scanty reports on corrosion inhibition of metals in alkaline environments using natural substances. In this present work, the corrosion inhibition of aluminium in NaOH using GA at 30 and 408C using hydrogen evolution and thermometric methods has been investigated. 277

Gum arabic as a potential corrosion inhibitor S.A. Umoren et al.

Anti-Corrosion Methods and Materials Volume 53 Number 5 2006 277 282

2. Experimental
2.1 Materials preparation The sheets of aluminium, AA 1060 type and purity of 98.5 per cent used for this study were obtained from the System Metal industries limited, Calabar, Nigeria. Each sheet was 0.8 mm in thickness and were mechanically pressed cut into 5 4 cm coupons. These coupons were used as cut without further polishing. However, they were degreased in ethanol, dried in acetone and stored in a moisture free desiccator before their use in corrosion studies. Coupons of the same dimension (5 4 0.8 cm) were used for both hydrogen evolution and thermometric methods. The concentrations of inhibitor (GA) (BDH supplies chemicals, England) prepared and used in the study were 0.1-0.5 g/l. The concentrations of NaOH (BDH laboratory supplies, England) (the corrodent) used were 0.1-2.5 M. 2.2 Hydrogen evolution technique The volume of hydrogen evolved was determined following the procedures previously described elsewhere (Ebenso et al., 1996, 1999, 2001, 2003, 2004; Ebenso, 1998, 2003; Ekpe et al., 2001). A 100 ml solution of 0.1-2.5 M solution of NaOH was introduced into the reaction vessel connected to a burette through a delivery tube. The initial volume of air in the burette was recorded. An aluminium coupon of weight 2 g was dropped into the solution of NaOH and the reaction vessel quickly closed to prevent any escape of H2 gas. However, the volume of H2 evolved from the corrosion reaction was monitored by the depression (in ml) in the parafn oil level. The depression in parafn oil level was monitored every 10 s for 300 s. The same experiment was repeated in the presence of inhibitor (GA) having the concentration range 0.1-0.5 g/l with a corrodent (NaOH) concentration of 1 M. The inhibition efciency (%I) was calculated using the equation:   Vi Ipercent 1 2 H 100 1 Vo H where V iH is the volume of H2 gas evolved at time t in the presence of inhibitor (GA) and V o H for the blank (absence of GA) (Ebenso et al., 2004). 2.3 Thermometric method The reaction vessel and procedure for determining the corrosion behaviour by this method has been described elsewhere by other authors (Mylius, 1922; Shams Eldin and Khedr, 1992; El-Etre, 2001). The volume of the test solution was kept at 50 ml. The initial temperature in all experiments was kept at 308C. The temperature was measured to ^ 0.058C on a calibrated thermometer (0-1008C). This method allowed for the evaluation of the reaction number (RN). The RN is dened as: RN8C min21 Tm 2 Ti t 2

The inhibition efciency (%I) was evaluated from percentage reduction in the RN namely: Ipercent RNaq 2 RNwi 100 RNaq 3

where RNaq is the RN in the absence of inhibitor (GA), i.e. blank (2 M NaOH) and RNwi the RN of aqueous 2 M NaOH in the presence of the inhibitor (GA) (Abd-El Nabey et al., 1985; Ebenso et al., 2004).

3. Results
Results obtained in this study are presented in Tables I-III and Figures 1-7. Figure 1 shows the variation of volume of hydrogen evolved with time for aluminium in different concentrations of NaOH without GA at 30 and 408C. Inspection of Figure 1 shows that the hydrogen evolution starts after a certain time from the immersion of the aluminium coupon in the test solution. It may be expected that this time corresponded to the period/time needed by the base to destroy the pre-immersion oxide lm and is known as incubation period. Figure 2 shows the volume of hydrogen evolved during the corrosion reaction of aluminium in 1 M NaOH containing different concentrations of GA measured as a function of reaction time at 30 and 408C. Figure 3 shows the temperature time curves for the dissolution of aluminium in 1 M NaOH containing different concentrations of the inhibitor (GA). Inspection of Figure 3 shows that as the concentration of the inhibitor increased, the time required to reach maximum temperature (Tm) increased and the rate of temperature rise decreased, that is, the inhibition efciency increased with the increase in the concentration of the inhibitor. Figure 4 shows the relationship between the RN, RN and the logarithm of inhibitor concentration. The curve consists of an initial decreasing portion along which the RN decreased with increasing concentration of GA and then the rate of decrease became smaller. As the concentration of GA increased further, the value of RN decreased with concentration. This seems to suggest that the inhibitor formed a monolayer on the surface of aluminium (Mousa et al., 1988). Table I shows the calculated values of inhibition efciency (%I), degree of surface coverage (u) and corrosion rate (mdd) for GA. From Table I, it is clearly seen that the corrosion rate of aluminium in NaOH decreased with addition of inhibitor compared to the blank. Also, the corrosion rate decreased with increase in the concentration of the inhibitor. This is an indication that the GA showed a signicant inhibitive effect on aluminium corrosion in the alkaline environment. Table II compares the inhibition efciency for GA obtained from the thermometric and hydrogen evolution methods. The two methods are comparable within limits of the concentration studied. Figure 5 shows the plot of inhibition efciency against inhibitor concentration at both temperatures. Nonlinear plots were obtained. Table III shows calculated values of activation energy (Ea) and heat of adsorption (Qads) for GA for aluminium corrosion in NaOH. A plot of logarithm of %I versus logarithm of inhibitor concentration is shown in Figure 6 (Freundlich adsorption isotherm) while that of Langmuir adsorption isotherm is shown in Figure 7 (plot of C/u against C). 278

where Tm and Ti are the maximum and initial temperatures, respectively, of the system studied when put into reaction vessel and t is the time (min) taken to reach the maximum temperature.

Gum arabic as a potential corrosion inhibitor S.A. Umoren et al.

Anti-Corrosion Methods and Materials Volume 53 Number 5 2006 277 282

Table I Calculated values of corrosion rate (mdd), inhibition efciency and degree of surface coverage (u) for GA from hydrogen evolution data
Corrosion rate (mdd) 3 102 3 Concentration of GA (g/l) Blank 0.1 0.2 0.3 0.4 0.5 308C 4.0 3.6 3.4 3.3 3.1 3.0 408C 8.1 6.1 5.7 5.4 5.1 5.0 Inhibition efciency (%I) 308C 408C 19.09 35.23 44.34 47.14 50.24 28.41 45.22 55.41 61.41 74.16 Degree of surface coverage (u) 308C 408C 0.19 0.35 0.44 0.47 0.50 0.28 0.28 0.45 0.55 0.61 0.74

Table II Comparison of inhibition efciency (%I) from hydrogen evolution at 408C and thermometric method
Concentration of GA (g/l) 0.1 0.2 0.3 0.4 0.5 Inhibition efciency (%I) Hydrogen evolutiona Thermometricb 28.41 45.22 55.41 61.23 74.16 31.34 49.14 60.99 62.83 75.86

Notes: a obtained using Equation (1); b obtained using Equation (3)

Table III Calculated values of activation energy, Ea (kJ mol2 1) and heat of adsorption, Qads (kJ mol2 ) for GA for aluminium corrosion in NaOH
Concentration of GA (g/l) Blank 0.1 0.2 0.3 0.4 0.5 Activation energy, Ea(kJ mol2 1) 30-408C 130.17 125.59 82.64 86.63 80.43 Heat of adsorption, Qads (kJ mol2 1) 30-408C 39.86 32.98 34.85 44.76 82.50

From Figure 1, it could be seen that the volume of hydrogen evolved increased with increase in the concentration of the corrodent (NaOH) at 308C. A similar trend was observed at 408C but with rather higher values. This could be attributed to the fact that an increase in concentration increased the rate of chemical reaction. Figure 2 also shows that the volume of H2 evolved was markedly reduced in the presence of the inhibitor (GA) compared to the blank which is an indication that GA actually inhibited the corrosion of aluminium in the alkaline environment. Also as could be shown from Figure 2, the volume of H2 evolved decreased with increase in concentration of the inhibitor. The volume of H2 evolved at 408C was higher than at 308C. In all cases, the inhibition efciency and degree of surface coverage (u) were found to increase with increase in the concentration of inhibitor (GA) and with increase in temperature. The highest inhibition efciency (74.16 per cent) was obtained with 0.5 g/l and at 408C (Table I). The increase in inhibition efciency with increase in temperature is suggestive of chemical adsorption mechanism. A similar trend was reported by Abdallah (2004), which studied guar gum as a corrosion inhibitor and attributed this behaviour to the increase of surface coverage (u) by the adsorption of the inhibitor on the metal surface. El-Etre (2003) also reported a similar observation for the inhibitive action of Opuntia extract. 4.1 Adsorption/thermodynamic considerations In discussing the adsorption characteristics for this study, the surface coverage (u) data was very useful. A linear relationship was obtained at all concentrations studied at both 30 and 408C which indicates that the experimental data ts the Freundlich adsorption isotherm (Figure 6). All the isotherm plots indicate that plot of lower temperature (308C) are under the plot of higher temperature (408C) studied which further indicates chemical adsorption proposed. The adsorption isotherm of Langmuir was tested for its t to the experimental data. Linear plots were obtained at 30 and 408C (Figure 7) which also indicates that the experimental data ts Langmiur adsorption isotherm given by: C 1 c 6 u b where C is the inhibitor concentration and u is the degree of surface coverage. Similar observations have also been reported (Abdallah, 2004) that the adsorption of guar gum follows Langmiur adsorption isotherm. El-Etre (2003) also reported that the adsorption of Opuntia extract follows the Langmiur adsorption isotherm. It is worthy of mention here that, the u values obtained with the thermometric method also obey the Langmiur adsorption isotherm. 279

4. Discussion
The dissolution of aluminium in NaOH starts from the moment the metal is introduced into the corrodent. Aluminium dissolves in NaOH according to the chemical reaction: 3 Al OH2 H2 O ! AlO22 H2 4 2 The mechanism of the process takes into consideration the inuence of the passivating surface oxide lm. Introduction of aluminium into NaOH leads to adsorption of the OH2 ions primarily on the surface oxide lm. Owing to the acidic property of the oxide lm, it is chemically attacked and this leads to subsequent dissolution of the oxide lm as shown in the reaction below (Mousa et al., 1988): Al2 O3 2OH2 ! 2AlO2 5 2 H2 O The heat generated from the above reaction accelerates further dissolution of the oxide and activates the dissolution of aluminium exposed to the aggressive medium.

Gum arabic as a potential corrosion inhibitor S.A. Umoren et al.

Anti-Corrosion Methods and Materials Volume 53 Number 5 2006 277 282

Figure 1 Variation of volume of hydrogen, VH, with time for the dissolution of aluminium in different concentrations of NaOH at (a) 308C and (b) 408C

Figure 2 Variation of volume of Hydrogen, VH with time (secs) for the dissolution of aluminium in 1.0 M NaOH in the presence of GA of different concentrations at (a) 308C and (b) 408C

The inhibition of aluminium corrosion by GA may be attributed to the presence of arabinogalactan, oligosaccharides, polysaccharides and glucoproteins since these compounds contain oxygen and nitrogen atoms which are the centres of adsorption. Furthermore, GA is a polysaccharide compound containing repeated heterocyclic pyrane moiety (Abdallah, 2004). The presence of hetero oxygen atoms in the structure makes possible its adsorption by co-ordinate type linkage through the transfer of lone pairs of oxygen atoms. The values of the activation energy, Ea (Table III) were calculated with the help of the Arrhenius equation:   r2 Ea 1 1 log 2 7 r1 2:303R T 1 T 2 where r1 and r2 are the corrosion rates at temperatures T1 and T2, respectively. The values of Ea decreased with increase in the concentration of GA. The values were greater than 80 kJ mol2 1 which goes further to support the assertion that chemical adsorption is proposed. The values of heat of adsorption (Qads) were calculated using the following equation:      u2 u1 2 log Qads 2:303R log 1 2 u2 1 2 u1   T1 T2 kJ mol21 8 T2 2 T1 where u1 and u2 are degree of surface coverage at temperatures T1 and T2, respectively. It is clearly seen that in all cases, the Qads 280

Figure 3 Temperature time curves for the dissolution of aluminium in blank and different concentration of GA

values were positive and ranged from 32.98 to 82.50 kJ mol2 1 (Table III). The positive Qads values show that the adsorption and hence inhibition efciency increased with rise in temperature also supporting chemical adsorption. The values of free energy of adsorption, DGo ads were obtained from the intercept of the Freundlich adsorption

Gum arabic as a potential corrosion inhibitor S.A. Umoren et al.

Anti-Corrosion Methods and Materials Volume 53 Number 5 2006 277 282

Figure 4 Plot of RN against Log of inhibitor concentration

Figure 7 Langmuir adsorption isotherm plot of C/u versus C (V 308C B 408C)

Figure 5 Plot of inhibition efciency (%I) against inhibitor concentration (V308C B 408C)

Figure 6 Freundlich adsorption isotherm plot of log %I versus log C (V 308C B 408C)

values obtained are an indication that the inhibitor (GA) was spontaneously adsorbed on the metal surface. Generally, values 21 of DGo are consistent with electrostatic ads up to 2 20 kJ mol interactions between the charged metal which signies physical adsorption while values more negative than 2 40 kJ mol2 1 (obtained in this study) involved charge sharing or transfer from the inhibitor molecules to the metal surface to form coordinate type of bond which signies chemical adsorption (Bilgic and Sahin, 2001). It is seen in the study that the inhibition efciency for the corrosion of aluminium in the presence of GA increased with increase in concentration. This also implies that adsorption of GA increases with increase in GA concentration. The adsorbed intermediate formed at the aluminium surface by the interaction with GA is probably a complex. At lower concentration of GA, the adsorption intermediate formed may be soluble complex, giving rise to low inhibition efciency. At higher concentration, the complex formed is insoluble and the higher values of inhibition efciency due to complex arise from the blocking of most of the activities on the aluminium surface due to the increased surface coverage.

5. Conclusions
.

isotherm plot and calculated with the help of the following equation (Abdel and Saed, 1981):   u 2 log B 9 log C log 12u where log B 21:74 2 DGads =2:303RT and C is the inhibitor concentration. 21 DGo at 408C. ads at 308C was 2 162.69 and 2 213.49 kJ mol 21 The mean value of DGo was 2 188.09 kJ mol . The negative ads 281

GA shows signicant inhibitive effect on aluminium corrosion in alkaline environment. Inhibition efciency increased with increase in inhibitor concentration. Inhibition was probably brought about by the adsorption of the inhibitor on the metal surface of oligosaccharides, polysaccharides, glucoproteins and arabinoglactan constituents of GA on the surface of the aluminium. Phenomenon of chemical adsorption is proposed for the calculated values of Ea, Qads and DGo ads obtained. The increase in temperature increased the inhibition efciency of GA which further conrmed that the adsorption process was chemical in nature. The mean DGo ads value was negative which suggest that GA was strongly adsorbed on the metal surface. The values of DGo ads at both temperatures studied indicated spontaneous adsorption of the inhibitor, and this is usually characteristic of strong adsorption with the metal surface. The adsorption process for GA followed the Langmuir and Freundlich adsorption isotherms.

Gum arabic as a potential corrosion inhibitor S.A. Umoren et al.

Anti-Corrosion Methods and Materials Volume 53 Number 5 2006 277 282

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Corresponding author
E.E. Ebenso can be contacted at: eno_ebenso@yahoo.com

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