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Corrosion Protection of Stainless Steel by Organic Inhibitors in Phosphate Industries in 15% H<sub>2</sub>SO<sub>4</sub> | OMICS International
ISSN: 2168-9806
Journal of Powder Metallurgy & Mining
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Corrosion Protection of Stainless Steel by Organic Inhibitors in Phosphate Industries in 15% H2SO4

Singh RK* and Kumar R

Department of Chemistry, Jagdam College, J P University, Chapra, India

*Corresponding Author:
Singh RK
Department of Chemistry
Jagdam College
J P University, Chapra, India
Tel: 06152-232407
E-mail: [email protected]

Received Date: September 09, 2014; Accepted Date: September 29, 2014; Published Date: October 10, 2014

Citation: Singh RK, Kumar R (2014) Corrosion Protection of Stainless Steel by Organic Inhibitors in Phosphate Industries in 15% H2SO4. J Powder Metall Min 3:124. doi: 10.4172/2168-9806.1000124

Copyright: © 2014 Singh RK, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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Abstract

Phosphate industries use sulphuric acid during the manufacturing of fertilizers. This acid interacts with stainless steel to develop corrosion cell and it corrodes metal. Organic inhibitors 2-(aminomethyl) phenol and 2-(aminomethyl) benzenethiol were taken for corrosion control in 15% H2SO4 medium. Inhibitors anticorrosive effect studied at different temperatures and 10 mM concentration. The corrosion rate of metal absence and presence of inhibitors were determined gravimetric methods. The corrosion current density and inhibitors polarization effect was studied by potentiostat. Inhibitors’ corrosion protection activities like physisorption-chemisorption adsorption, thermal stability and surface films formation analysis can be done by activation energy, heat of adsorption, free energy, enthalpy and entropy. The experimental results of inhibitors surface coverage area and inhibition efficiency were exhibited strong bonding between inhibitors and base metal.

Keywords

Stainless steel; H2SO4; Inhibitors; Potentiostat; Surface adsorption

Introduction

Stainless steel is a very important metal for phosphate industry whereas H2SO4 produces hostile environment for surrounding material and it produces several forms of corrosion like galvanic, pitting, crevice, stress, intergranular embrittlment and blistering. Scientists and researchers were used different techniques for corrosion mitigation of materials like organic and inorganic coatings, use organic and inorganic inhibitors, composite materials coating, nanocoating and plasma coatings. Inorganic nanocoating of aluminum phosphate [1], zinc phosphate [2] and magnesium phosphate [3] in presence of DLC (diamond like carbon) filler were used as nanocoating materials in high temperature and acidic environment. Aliphatic and aromatic compounds [3-5] containing amino, hydroxyl and thiol functional groups were applied as corrosion protector in acidic medium. Polymeric coating [6-8] saved material for corrosion but this coating did not produce good results in long duration. Mixed types of organic inhibitors having cathodic [9-11] and anodic [12-15] polarization power used as an inhibitor in acidic condition. Plasma coating [16,17] provided corrosion resistance of metal at high temperature and strong acidic medium. Natural products [18,19] used as inhibitor which is ecofriendly with environment and these products has good inhibition properties.

Experimentals

Stainless steel (5×3×0.01) square meter size of coupons made for experimental work. Its surface was sharpened with emery paper and samples were washed with double distilled water. Finally it was rinsed with acetone and dried with air dryer and kept into desiccator. Inhibition effect of 2-(aminomethyl)phenol and 2-(aminomethyl) benzenethiol were studied at 50°C, 60°C and 70°C temperatures and 10mM concentration. The corrosion rate was calculated absence and presence of inhibitors by gravimetric method. Stainless steel (316) was used for this and its chemical composition analyzed in Bokaro Steel Plant Jharkhand, India.

The corrosion current and corrosion potential was determined with potentiostatic polarization by using an EG & G Princeton Applied Research Model 173 Potentiostat. A platinum electrode was used as an auxiliary electrode and a calomel electrode was used as reference electrode with stainless steel coupons.

Equation

Results and Discussion

The corrosion rates of stainless steel was calculated at 50°C, 60°C and 70°C temperatures and 10 mM concentration of inhibitors by equation 1 in presence of 15% H2SO4 solution absence and presence of inhibitors 2-(aminomethyl)phenol and 2-(aminomethyl) benzenethiol

K (mmpy) = 13.56 W / D A t (1)

Where W = weight loss of test coupon expressed in kg, A = Area of test coupon in square meter, D = Density of the material in kg/m3.

The corrosion rates of stainless steel without and with inhibitors mentioned in Table 1. The result of Table noticed that corrosion rate of metal is increasing without inhibitors and its values are decreasing with inhibitor as above recorded temperatures and concentration. The graph between log K versus 1/T was looked in Figure 1 shown that the rate of corrosion enhanced at lower temperature to higher temperature and its values suppressed after addition of inhibitors.

Inhibitors Temperature 50°C 60°C 70°C C (mM)
IH(0) Ko 0.139 0.208 0.241 0
  log Ko -0.856 -0.681 -0.617  
IH(I) K 0.073 0.086 0.108 10mM
  logK -1.136 -1.065 -0.966  
  θ 0.474 0.586 0.551  
  log(θ/1- θ) 0.046 0.15 0.088  
  IE (%) 47.4 58.6 55.1  
IH(II) K 0.037 0.043 0.078 10mM
  logK -1.431 -1.366 -1.107  
  θ 0.733 0.793 0.676  
  log(θ/1- θ) 0.317 0.583 0.438  
  IE (%) 73.3 79.3 67.8  

Table 1: The Corrosion of stainless steel in 15% H2SO4 at different temperatures and 10 mM concentration of inhibitors.

metallurgy-mining-temperatures

Figure 1: log K versus 1/T at different temperatures with 10 mM of inhibitors.

The percentage inhibition efficiency and surface coverage area of inhibitors were determined using 2 and equation3.

IE (%) = (1- K / Ko) 100  (2)

Where Ko is the corrosion rate without coating, K = corrosion rate with coating.

θ = (1 – K / Ko)   (3)

where θ = Surface coverage area, Ko = corrosion rate without coating, K = corrosion rate with coating,

The percentage inhibition efficiency and surface coverage area values recorded in Table 1 at different temperatures and 10 mM concentration of inhibitors. It depicted that these values were increased with both inhibitors but good results observed with (2-aminomethyl) benzenethiol. The surface coverage area (θ) versus temperatures (T) for both inhibitors plotted in Figure 2. It found that 2-(amino-methyl) benzenethiol occupied more surface area than that of 2-(aminomethyl) phenol. Inhibition efficiency (IE) of both inhibitors versus temperature (T) was represented in Figure 3. This graph indicated that second inhibitor had more inhibition efficiency than that of first.

metallurgy-mining-Surface-coverage

Figure 2: θ(Surface coverage area) versus T (°K) at different temperatures with 10 mM concentration of inhibitors.

metallurgy-mining-concentation

Figure 3: IE (%) versus T °K different temperatures with 10 mM concentation of inhibitors.

The activation energy of inhibitors was determined by equation 4 and Figure 1 and its values were recorded in Table 2. Activation energy increased without inhibitors and its values decreased with inhibitors.

Inhibitor Thermodynamical 50°C 60°C 70°C
IH((0) Ea(o) 51.24 49.41 34.22
IH(I) Ea 67.36 61.12 53.59
  Qads -2.72 -8.61 -4.88
  ΔG -22.87 -26.22 -30.83
  ΔH -96.54 -88.53 -79.27
  ΔS -38.51 -38.25 -37.96
IH(II) Ea 83.67 78.39 61.41
  Qads -18.79 -33.45 -24.99
  ΔG -5.37 -8.94 -22.99
  ΔH -111.04 -105.8 -87.11
  ΔS -37.55 -38.24 -37.96

Table 2: Thermodynamical values inhibitors at different temperatures and 10 mM concentration.

These results were shown that inhibitors adhered with surface of base metal.

d /dt (logK) = Ea / R T2 (4)

where T is temperature in Kelvin and Ea is the activation energy of the reaction.

The heat of adsorption was calculated with help equation 5 and their values were mentioned in Table 2. The graph plotted between log (θ/1- θ) vs. 1/T was shown straight line in Figure 4 and its negative values indicated that inhibitors bind with metal by physical forces.

log (θ/1-θ) = log (A .C) - (Qads. / R T) (5)

metallurgy-mining-concentation-inhibitors

Figure 4: log (θ/1-θ) versus1/T at different temperatures with 10 mM concentration of inhibitors.

where T is temperature in Kelvin and Qads heat of adsorption

Free energy was determined by equation 6 and its values were recorded in Table 3. Its values mentioned in Table 2 depicted that after addition of inhibitor exothermic reaction occurred.

ΔG = -2.303RT [log C - log (θ/1-θ) + 1.72] (6)

Inhibitors ΔE ΔI βa βc Icorr.cur(mA) K(mmpy) C(mM)
IH(0) -725 72 111 63 2.14 0.561 0
IH(I) -674 64 68 94 1.45 0.435 10
IH(II) -521 51 44 75 1.01 0.305 10

Table 3: Potentiostatic Polarization values of stainless steel with inhibitors at 10 mM concentration.

The energy of enthalpy and entropy were calculated by transition state equation 7 and it values were recorded in Table 2. These values noticed that inhibitors were produced an exothermic reaction and they bonded with metal chemical adsorption. Thermodynamical values of Ea, Qads. , ΔG, ΔH and ΔS versus surface coverage area (θ) plotted in Figure 5 indicated that inhibitors adsorbed with metal by physisorptionchemisorption.

K = R T / N h log (ΔS# / R) X log (-ΔH #/ R T) (7)

metallurgy-mining-Thermodynamical

Figure 5: Thermodynamical values of inhibitors versus θ (Surface coverage area).

where N is Avogadro’s constant, h is Planck’s constant, ΔS# is the change of entropy activation and ΔH# is the change of enthalpy activation.

The corrosion current density is determined in the absence and presence of inhibitors the help of equation 8 and their values are recorded in Table 3.

ΔE/ΔI = βa βc / 2.303 Icorra + βc) (8)

where ΔE/ΔI is the slope which linear polarization resistance (Rp), βa and βc are anodic and cathodic Tafel slope respectively and Icorr is the corrosion current density in mA/cm2.

The metal penetration rate (mmpy) was calculated by equation 9 in absence and presence of inhibitors.

C.R (mmpy) = 0.1288 Icorr (mA/cm2) × Eq .Wt (g)/ρ (g/cm3) (9)

where Icorr is the corrosion current density ρ is specimen density and Eq.Wt is specimen equivalent weight.

The observation of the results of Table 3, it was noticed that corrosion current increased without inhibitors and it reduced after addition of inhibitors. Figure 6 indicated that Tafel graph has plotted between electrode potential and corrosion current density in the absence and presence of inhibitors and this figure was shown that anodic potential, corrosion current density and corrosion rate increased without inhibitors but after addition of inhibitors these values decreased and inhibition efficiency increased.

metallurgy-mining-corrosion-current

Figure 6: Plot of E (mV) Vs. I corrosion current (mA) for stainless steel at 10 mM concentration of inhibitors.

Conclusion

Observation of results of inhibitors 2-(aminomethyl) phenol and 2-(aminomethyl) benzenethiol indicated that inhibition efficiency and surface coverage area at different temperatures in H2SO4 medium produced corrosion resistance effect for stainless steel. The inhibitors adhered with metal surface by physisorption-chemisorption adsorption. This adsorption phenomenon confirmed by activation energy, heat of adsorption, free energy, enthalpy and entropy. Potentiostat results for both inhibitors indicated that these inhibitors produced high polarization current and nullify the attack of H+ ions.

Acknowledgements

I am thankful to UGC, New Delhi for providing me financial support. I am also thankful to the department of chemistry, Ranchi University, Ranchi and the department of applied Chemistry Indian school of Mines, Dhanbad for providing laboratory facilities.

References

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