2Research Scholar, Department of Chemistry, Jagdam College, J P University, Chapra-841301, India
3Research Scholar, Department of Chemistry, Jagdam College, J P University, Chapra-841301, India
DOI: http://dx.doi.org/10.15226/sojmse.2018.00154
Keywords: Hostile environment; corrosion; nanocoating; filler; thermal parameters; composite film barrier;
Abrasive blasting is a common method of preparing a metal surface for application of an organic coating [1]. The performance of an organic coating/metal [2] substrate system in a corrosive environment depends on the nature of the coating, substrate, and interface [3] between them. The properties of the interfacial region [4] are influenced by the abrasive blasting process. The corrosion behavior of coated stainless steel [5] is significantly affected by the choice of blasting abrasive and the parameters of the blasting process. They investigate the adhesion of polymer coating [6] systems of the following types: alkyd, acrylic, latex, vinyl, epoxy, coal tar epoxy [7] and a zinc-filled vinyl [8]. For every case zinc-filled vinyl, steel grit abrasive produced the lowest adhesion when compared with based abrasive. The resistance to blistering of both coal tar epoxy and urethane coatings [10] on underground steel storage tanks is more severe for tanks blasted with steel grit than for those blasted with silica sand. The effect of abrasive type on the corrosion rate and catholic delaminating performance of bare and coated pipeline steel. They found a reduction in the corrosion rate in distilled water and delamination rate of an epoxy powder coating [11] in Clions solution when the steel was abrasively blasted with alumina [12] compared to steel blasted with steel grit. They interpreted the results in terms of a reduction in catalytic efficiency [13] for the operative catholic reaction for the alumina-blasted surface, and hypothesized doping of the oxide layer on the steel with aluminum. Cathodic delamination of organic coatings [14] on steel has been widely studied. It is generally believed that the high pH generated by the oxygen reduction reaction at the delaminating front is responsible for the loss of coating adhesion [15]. There are several techniques like metallic and nonmetallic coating, inhibitors action, polymeric coating and paint coating [16] used to control the corrosion. Metallic coating did not provide good protection in presence of atmospheric pollutants. Polymeric coating [17] used in corrosive environment but this coating did not control attack pollutants. They penetrate polymeric barrier and corrode base metal. Its bonding and bond connective disintegrate in this environment. The nitrogen, oxygen and sulphur containing alkane, alkene, alkyne, aromatic and heterocyclic organic compounds [18] applied as inhibitors against pollutants but they are not protecting materials. These corrosion protection techniques did not shave material by attack of biological micro and macroorganism [19]. Particulates are also increasing corrosion of materials for their protection [20] above mention methods is used but they do not give suitable results. Effluents and biowastes corrode materials but their protection above mentioned protection techniques used which do not mitigate corrosion. Mixed types of organic inhibitors used which work as anodic and catholic protection in ambient environment but these inhibitors become passive in aggressive medium. The purpose of this study is to examine composite thin film formation on the surface epoxy-coated stainless steel by nanocoating compound decahydrobenzo [8] annulene-5, 10-disemicarbazone and filler Tin.
1-Chlorocyclohexane (57g) was dissolved in THF and potassium t-butoxide (BuO-K+) was added (75g) at room temperature then after cyclohexene (70ml) was mixed into reaction mixture as trapping agent. After completion of reaction water was poured then it quenched with brine solution and reaction mixture was extracted from ether. Finally, the compound was dried with sodium sulphate. Solvent was removed by rotator vapor and target product was purified by silica gel column chromatograph. After purification 83% yield of 1,2,3,4,4a,5,6,7,8,8b-decahydrobiphthalene was obtained.
Cyclohexene solution poured into cyclohexyne and reaction mixture was stirred one hours then cyclohexene trapped with cyclohexyne to form an adduct of decahydrobiphenylene.
1,2,3,4,4a,5,6,7,8,8b-decahydrobiphthalene (78g) was taken and was dissolved with carbon tetrachloride. Sodium periodate (NaIO4) (58g) was added into reaction mixture, then after methylnitrile and water was added. The reaction mixture was stirred 24hours at room temperature. The product was quenched with brine solution then adding sodium bicarbonate workup was completed with ether and ethereal solution dried with sodium sulphate. The target product was purified by silica gel column chromatograph and 76% yield of decahydrobenzo [8] annulene-5, 10-dione was obtained.
35g of semicarbazide hydrochloride and 45g of crystallized sodium acetate in 70ml of water was dissolved then 60g of decahydrobenzo [8] annulene- 5, 10-dione added and shacked. When the mixture was turbid, alcohol or water was added until clear solution is obtained and again the mixture was shaken for a few minutes and allowed standing. The mixture was warmed on a water bath for 20 minutes and then cooled in ice water. Filtered crystals were washed off with a little cold water and again recrystallized from water or from methanol and got 86% of decahydrobenzo[8] annulene-5,10-disemicarbazone.
NC |
Temp(0K) |
2780K |
2830K |
2880K |
2930K |
2980K |
C(mM) |
Times (hrs.) |
24 |
48 |
72 |
96 |
120 |
||
NC(0) |
Ko |
425 |
628 |
738 |
977 |
1021 |
0 |
logKo |
2.628 |
2.797 |
2.868 |
2.989 |
3.001 |
||
NC(4) |
K |
148 |
74 |
49 |
37 |
27 |
50 |
logK |
2.17 |
1.869 |
1.69 |
1.568 |
1.431 |
||
log(K/T) |
1.615 |
1.321 |
1.149 |
1.035 |
0.906 |
||
θ |
0.65 |
0.88 |
0.93 |
0.96 |
0.97 |
||
log(θ/1-θ) |
0.268 |
0.865 |
1.12 |
1.38 |
1.509 |
||
%CE |
65 |
88 |
93 |
96 |
97 |
||
NC(TiN) |
K |
119 |
59 |
39 |
29 |
24 |
20 |
logK |
2.075 |
1.771 |
1.591 |
1.462 |
1.38 |
||
log(K/T) |
1.52 |
1.223 |
1.051 |
0.929 |
0.855 |
||
θ |
0.72 |
0.91 |
0.95 |
0.97 |
0.98 |
||
log(θ/1-θ) |
0.41 |
1.004 |
1.278 |
1.509 |
1.69 |
||
%CE |
72 |
91 |
95 |
97 |
98 |
(Figure3) plotted between log (θ/1-θ) versus 1/T for nanocoated decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler. The values of both the compounds log (θ/1-θ) at 278 to 2980K were mentioned in (Table1). The results of (Table1) and (Figure 3,4,5) indicate that nanocoating and filler compounds increased the values of log (θ/1-θ) at different temperatures in H2O, O2 (moist), CO2, NO2 and SO2 environment.
(Figure 5) plotted between percentages coating efficiency (%CE) versus temperature (T) at different temperatures for nanocoating and filler compounds. The nature of graph shows that nanocoating decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler rising % coating efficiency at different temperatures. The % coating efficiency at different intervals of temperatures were calculated by equation %CE = (1-K/Ko) X 100 and their values were mentioned in (Table1).
(Figure 2) is a straight line Arrhenius plot between logK versus 1/T with help of this figure and Arrhenius equation d/ dT(lnK) = A e-Ea/RT were calculated activation energy of epoxycoated stainless steel and nanocoating of decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler and their values were written in (Table 2,4,5) In all case activation energy found to be positive sign. It was observed that without coating activation energy increased but their values reduced after nanocoating and filler compounds. Both compounds occupied on the surface of epoxy-coated stainless steel by chemical bonding.
(Figure 3) indicated straight line plot between log (θ/1-θ) versus 1/T for nanocoating of decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler and it is a plot of Langmuir isotherm. Heat of adsorption of both nanocoating and filler compounds were determined by equation log (θ/1-θ) = log (AC) – (q/2.303 R T) and (Figure 3). The values of heat of adsorption are mentioned in (Table 2). Both compounds produced negative sign of energy which confirmed that nanocoating and filler compound formed thin film on the surface of epoxy-coated stainless steel by chemical bonding.
Free energy of nanocoating of decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler were calculated by equation -ΔG = 2.303 log RT and their results were expressed in (Table 2). The negative values of free energy express that nanocating and filler compounds were adhered with base material by chemical bonding. Free energy results show that coating is an exothermic process.
Enthalpy and entropy of nanocoating of decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin filler were calculated by transition state equation K = R T / N h log (ΔS# / R) X log (-ΔH #/ R T) and (Figure 6) and their values are recorded in (Table 2). These thermal parameters indicated that nanocoating and filler compounds were attached with base material by chemical bonding. Entropy of both the compounds show that nanocoating and filler compounds arranged on the surface of base material in ordered matrix. Thermal values of activation energy, heat of adsorption, free energy, enthalpy and entropy were confirmed
(Figure 7) draws graph between enthalpy (ΔE), entropy (ΔS) and surface coverage area (θ) versus temperatures (T) for decahydrobenzo [8] annulene-5, 10-disemicarbazone and Tin in H2O, O2 (moist), CO2 and SO2 environment. The nature of plot indicate that the values of enthalpy and entropy decreased as temperatures rise which enhanced surface coverage area such results trend were observed in (Table 2).
Thermal parameters |
2780K |
2830K |
2880K |
2930K |
2980K |
NC(0)Ea |
180 |
191 |
192 |
197 |
195 |
NC(4) Ea |
160 |
137 |
122 |
112 |
105 |
NC(4)q |
-10.03 |
-52.74 |
-70.96 |
-87.86 |
-95.42 |
NC(4)∆G |
-258 |
-234 |
-218 |
-205 |
-194 |
NC(4)∆H |
-116 |
-95 |
-81 |
-71 |
-63 |
NC(4)∆S |
-104 |
-93 |
-86 |
-81 |
-77 |
θ NC(4) |
0.65 |
0.88 |
0.93 |
0.96 |
0.97 |
NC(TiN)Ea |
159 |
135 |
121 |
111 |
103 |
NC(TiN)q |
-24.79 |
-63.27 |
-79.45 |
-93.21 |
-101.38 |
NC(TiN)∆G |
-249 |
-225 |
-210 |
-201 |
-188 |
NC(TiN)∆H |
-107 |
-85 |
-73 |
-65 |
-57 |
NC(TiN)∆S |
-99 |
-88 |
-82 |
-78 |
-73 |
θNC(TiN) |
0.72 |
0.91 |
0.95 |
0.97 |
0.98 |
NC |
ΔE(mV) |
ΔI |
βa |
βc |
Icorr(mA/cm2) |
K(mmpy) |
θ |
%CE |
C (mM) |
NC(0) |
-704 |
187 |
295 |
197 |
13.64 |
417 |
0 |
0 |
0 |
NC(4) |
-251 |
24 |
35 |
315 |
1.31 |
39 |
0.91 |
91 |
50 |
NC(TiN) |
-244 |
21 |
31 |
320 |
1.05 |
31 |
0.93 |
93 |
20 |
- Bhadra S, Singha N, Khastgir D. Polyaniline based anticorrosive and anti-molding coating. Journal of Chemical Engineering and Materials Science. 2011;2(1):1-11.
- Szabo T, Molnar-Nagy L, Telegdi J, Bognár J, Nyikos L. Self-healing microcapsules and slow release microspheres in paints. Progress in Organic Coatings. 2011;72(1-2):52-57.
- Wen NT, Lin CS, Bai CY, Ger MD. Structures and characteristics of Cr (III) based conversion coatings on electro galvanized steels. Surface and Coatings Technology. 2008;203(3-4):317-323.
- Boerio FJ, Shah P. Adhesion of injection molded PVC to steel substrates. J of Adhesion. 2005;81(6):645-675.
- Deveci H, Ahmetti G, Ersoz M, Kurbanli R. Modified Poly styrenes: Corrosion physico-mechanical and thermal properties evaluation. Prog Org Coat. 2012;73(1):1-7.
- Genzer J. Templating Surfaces with Gradient Assemblies. J of Adhesion. 2005;81(3-4):417-435.
- Leon-Silva U, Nicho ME. Poly (3-octylthiophhene) and polystyrene blends thermally treated as coating for corrosion protection of stainless steel 304. Journal of Solid State Electrochemistry. 2010;14(8):1487-1497.
- Baier RE. Surface behaviour of biomaterials: the theta Surface for biocompatibility. J Mater Sci Mater Med. 2006;17(11):1057-1062.
- Rao BVA, Iqbal MY, Sreehar B. Electrochemical and surface analytical studies of the self assembled monolayer of 5-methoxy-2-(octadeclthiol) benzimidazole in corrosion protection of copper. Electrochimica Acta. 2010;55(3):620-631.
- Liu XY, Ma HY, Zhou M. Self-assembled monolayers of stearic imidazoline on copper electrodes detected using electro chemical measurement, XPS, molecular simulation and FTIR. Chinese Sci Bull. 2009;54(3):374-381.
- Liao QQ, Yue ZW, ZHU ZW, WANG Y, ZHANG YZ, Guo-Ding ZQ. Corrosion inhibition effect of self-assembled monolayers of ammonium pyrrolidine dithiocarbamate on copper. Acta Phys Chin Sin. 2009;25(8):1655-1661.
- Zhang DQ, He XM, Cai QR, Gao LX, Kim GS. Arginine self-assembled monolayers against copper corrosion and synergetic effect of iodide ion. Journal of Applied Electrochemistry. 2009;39(8):1193-1198.
- Sahoo RR, Biswas SK. Frictional response of fatty acids on steel. J Colloid Interface Sci. 2009;333(2):707-718.
- Raman A, Gawalt ES. Self-assembled monolayers of alkanoic acid on the native oxide surface of SS316L by solution deposition. Langmuir. 2007;23(5):2284-2288.
- Li D, Chen S, Zhao S, Ma H. The corrosion Inhibition of the self-assembled Au and Ag nanoparticles films on the surface of copper. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2006;273(1-3):16-23.
- Cristiani P, Perboni G, Debenedetti A. Effect of chlorination on the corrosion of Cu/Ni 70/30 condenser tubing. Electrochimica Acta. 2008;54(1):100-107.
- Cristiani P. Solutions to fouling in power station condensers. Applied Thermal Engineering. 2005;25(16):2630-2640.
- Videla HA, Herrera LK. Understanding microbial inhibition of corrosion. A comprehensive overview. International Biodeterioration & Biodegradation. 2009;63(7):896-900.
- Bibber JW. Chromium frees conversion coating for zinc and its alloys. Journal of Applied Surface Finishing. 2009;2(4):273-275.
- Ghareba S, Omanovic S. Interaction of 12-aminododecanoic acid with a carbon steel surface: Towards the development of ‘green’ corrosion inhibitors. Corrosion Science. 2010;52(6):2104-2113.