synergistic corrosion inhibition effect of carbon steel in ...

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INTERNATIONAL JOURNAL OF NANO CORROSION SCIENCE AND ENGINEERING Volume 3 ; Issue 1 ; April 2016

Volume 3(1) 2016 S.No 1.

2.

TITLE AND AUTHORS CORROSION INHIBITION BY PHENOLS – AN OVERVIEW D.Lakshmi 1*,S.Rajendran 1, and J.Sathiyabama 2 CORROSION RESISTANCE OF COMMERCIAL ALUMINIUM IN SIMULATED CONCRETE PORE SOLUTION IN PRESENCE OF CURCUMIN EXTRACT 1 Susai Rajendran , Duraiselvi2 , M.Pandiarajan3, S Shanmugapriya4,

PAGE NO 1-18

19-33

T Umasankareswari5 and P Prabhakar6

3.

4.

5.

6

7

8

BIODIESEL PRODUCTION FROM MAHUA (MADHUCA INDICA) S. Guharaja, S. DhakshinaMoorthy, Z. Inamul Hasan*, B. Arun, J. Irshad Ahamed and J. Azarudheen CORROSION RESISTANCE OF METALLIC GLASSES S.Dhasneem1, S.Seerin Farhana2, Susai Rajendran1, T.Umasankareswari3, S Shanmugapriya4 and D. Renita5 OPTIMIZATION OF MAHUA OIL METHYL ESTER USING RESPONSE SURFACE METHODOLOGY TO PRODUCTION BIODIESEL FROM MADHUCA OIL OVER MGO / ZRO2 CATALYST S. DhakshinaMoorthy1, S. Thulasiram2*, Z. Inamul Hasan1 SYNERGISTIC CORROSION INHIBITION EFFECT OF CARBON STEEL IN SEA WATER BY PROPYL PHOSPHONIC ACID - Zn2+ SYSTEM S. K. Selvaraj[a], A. John Amalraj[b]*, V. Dharmalingam[b], J. Wilson Sahayaraj[c] INHIBITION OF CORROSION OF CARBON STEEL IN SEA WATER BY THIOMALIC ACID - Zn2+ SYSTEM S. K. Selvaraj[a], A. John Amalraj[b]*, V. Dharmalingam[b], J. Wilson Sahayaraj[c] AN INVESTIGATION OF FRICTION WELDING PROCESS ON SA213 TUBE TO SA387 TUBE PLATE USING EXTERNAL TOOL A Daniel Das [a]*, Dr. S Senthil Kumaran [b]

34-47

48-59

60-78

79-95

96-109

110-122

ANNEXURE I

ISOTHERM MODELS FOR THE ADSORPTION OF CRYSTAL VIOLET DYE ONTO ZINC CHLORIDE ACTIVATED CARBON V. Nandhakumar[a] *, A.Rajathi [a], K. Ramesh[b] and A. Elavarasan[c]

ANNEXURE II

SYNTHESIS, CHARACTERIZATION AND ANTIMICROBIAL STUDIES OF 2,6-BIS(PYRIDINE2-YL)3,5-DIPHENYL-PIPERIDIN-4-ONE M. Seeni Mubarak*, R. Kathirvel , M. Sathyanarayanan and M. Mohamed Rabeek ANNEXURE I and II are revised version of Papers which have already been published in the Proceedings of “Jamal Conference”, Tiruchirapalli, India

Corrosion Inhibition by Phenols – An Overview

Lakshmi et al.,

Available Online http://www.ijncse.com

ISSN Online: 2395-7018 3(1)(2016)1-18

CORROSION INHIBITION BY PHENOLS – AN OVERVIEW D.Lakshmi 1*,S.Rajendran 1, and J.Sathiyabama 2 1*Department of Chemistry, ,M.V.Muthiah Government Arts College for Women, Dindigul-624001 , Tamilnadu, INDIA 1 Department of Chemistry, R.V.S. College of Engineering,Kulathur-, Tamilnadu, INDIA 2 Department of Chemistry, G.T.N.Arts College, Dindigul-Tamilnadu, INDIA ABSTRACT Corrosion Inhibition of Phenols and its derivatives on different types of metals, medium has been reviewed. Deterioration of metals is controlled or minimized by the use of inhibitors. There is a continuous search for better corrosion inhibitors to meet the need of the industrial expectations. The inhibition’s efficiency strongly depend on the structure and the chemical properties of the film formed on the metal surface. The adsorption of inhibitors on the metal surface especially organic compounds containing –NH2 , -OH groups retards the corrosion action of metal. The efficiency of inhibition is analyzed by many technologies such as weight loss, Potentiodynamic Polarization, Electrochemical Impedance Spectra (EIS), surface examination techniques like FTIR spectroscopy, luminescence spectroscopy, Atomic force microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction spectroscopy (XRD),Energy Dispersive X-ray Spectroscopy (EDX), Scanning Electron Microscope (SEM), , UV-Visible spectra. Keywords: Metal, Different medium, Phenol derivatives, Electrochemical methods 1

Int J Nano Corr Sci and Engg 3(1) (2016) 1-18

Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi


Lakshmi et al.,

INTRODUCTION Corrosion is a very common phenomenon that has wide ranging effects in industrial, municipal and private settings. The method for corrosion protection of metals based on the use of corrosion inhibitors, i.e., chemical compounds or their compositions which when present in a corrosive system at a sufficient concentrations, decrease the corrosion rate of metals In the present study phenol and its derivatives were studied as corrosion inhibitors. The references indicates that organic compounds containing –NH2 , OH groups retards the corrosion action of metal, by pumping the electron to the metal surface. This may be due to the formation of surface layer also may be due to retardation of oxidation. The various organic compounds containing –NH2 , and -OH group are used to study the inhibition efficiency of organic compounds . The results are very interesting. Metals:Phenols and its derivatives have been used as corrosion inhibitors to prevent corrosion of metals such as Mild Steel (1,2,3,4,8,9,10,11,12,13,16,24,34) Carbon steel (15,20,21,22,27) Aluminum and its alloy (4,5,6,14,19,23,26,28,30,32,33,42,46,47,49) Steel (30,44,47 ) Zinc (7,37) Stainless steel (17,31,39,40) CuNi10Fe alloy(18) N80 Steel (25,29,35,36,38,45) Iron (41,43,44) Rh,Pd,Ir,Pt,(48) Medium: Phenols have been used as corrosion inhibitors to prevent corrosion of metals and alloys in various mediums such as hydrochloric acid 1,2,5,6,7,9,10,11,12,14,15,16,17,19,23,26,29,31,32,34,35,36,38, 41,42, 43,44,45) Sulfuric acid (3,4,8,13,24,25,37) Nitric acid (25) Phosphoric acid (39,40) Sodium chloride (18,28,30) well water (22) Sodium hydroxide (23,32,33,46,47,49), Inhibitors:Different forms of phenols such as Schif’s base (1,4,14,16,24,26,34,37) Drug (2) Chalcone (5),Catechin(12)are used as corrosion inhibitors Additives: phenols have been used as corrosion inhibitor alone or combination with additive such as Zinc (20,21,22,27,37) KSCN (31) 2




Lakshmi et al.,

Methods: Different methods have been used to determine the inhibition efficiency of different inhibitors by WL-Weight loss (1,3,4,5,6,7,10,11,12,13,16,19,20,21,22,25,27,29,31,34,35,37,40,45,46,49)

Potentio

dynamic

Polarization

(1,5,8,9,10,11,12,13,15,16,17,18,19,20,22,26,29,30,32,34,35,36,37,39,40,41,42,43,45,46,49), Galvanostatic Polarization (6,7,31) , LPR-Linear Polarization (2,8,9,16,18,30),Tafel Polarization(14,24), Hydrogen evolution (3,6) Gasometry (4,47),Electrochemical Impedance Spectroscopy (1,5,6,8,9,10,12,13 14,15,16,20,22, 24,26,30,32,34,39,40,42,43,44), Rotation disc method( 28),and Linear sweep Voltametry (33) EFM-Electrochemical Frequency Modulation( 5,26 ),Quantum Electrochemical Study based on Density Functional theory (DFT) and cluster polarized continuum model CM/PCM-DFT(23) has been analyzed. Surface Analysis: A protective film is confirmed by various surface examination techniques such as SEM- Scanning Electron Microscope (1,8,9,13,14,27,39) FTIR(20,21,22,27,29,33,35,36) XPS- X-ray Photoelectron Spectroscopy (48) EDX-Energy Dispersive X-ray Spectroscopy(10,33) U-Visible spectroscopy(15)and AFM-Atomic force microscopy (27). Adsorption Study The adsorption behavior of different inhibitors on the adsorption

isotherms

have

been

obeyed

such

as

Langmuir

metal surface has been investigated. The following

(1,2,5,6,8,9,11,12

16,34,37.43)

Frumkin

(10,35,42),

Freundlich(18,26,28,30) and Tempkin (3,7,13,14,15,17,19,24,31,36,45) A list of corrosion inhibition studies of phenols and its derivatives on different type of metals is shown in table–1.

3




Lakshmi et al.,

TABLE-1 List of Corrosion inhibition studies on phenols and its derivatives No 1

Metal Mild steel

Medium HCl

Inhibitor Schiff base

2

Mild steel

HCl

3

Mild steel

H2SO4

Amodiaquin (4-[(7- chloro quinolin-4yl)amino]-2[(diethylamino)methyl]phenol) 2,4-di-tert-butyl-6-(1hphenantro[9,10-d]imidazol-2yl) phenol (PIP)

4

Mildsteel and Al

H2SO4

Schiff base

5

Aluminum

HCl

6

Aluminum

HCl

Chalcone derivatives [3-(4hydroxy phenyl)-1phenylprop-2-en-1-one and 3(4-hydroxyphenyl)-1-(4-nitro phenyl)prop-2-en-1-one ] 4-(3,6,9,12tetraoxa tetra cosyloxy) phenol,4(3,6,9,12,15,18-hexaoxa tria contyloxy)phenol,4(3,6,9,12,15,18,21,24-octa oxahexatriacontyloxy)phenol

7

Zinc

HCl

Coumarin derivatives

Additive

Method Potentiodynamic polarization, EIS , Weight loss measurements and SEM

Findings Mixed type inhibitors ,obeying the Langmuir adsorption isotherm.and the existence of an adsorbed film Linear polarization Monolayer chemisorption It resistance (LPR) obeyed the Langmuir adsorption Electrochemical method. isotherm. Weight loss and Described by Temkin adsorption Hydrogen evolution isotherm.Physical adsorption is techniques at 303 – 333 K. proposed for PIP

Ref 1

year 2015

2

2015

3

2015

Weight loss and Gasometric First order reaction 4 methods mechanism,. an endothermic reaction follows physisorption reaction mechanism. Potentiodynamic polarization, They act as mixed type 5 EIS ,Electrochemical inhibitors The surface coverage frequency modulation (EFM) of the inhibitors obeyed and Weight loss Langmuir adsorption isotherm. measurements Hydrogen evolution reaction, The adsorption process follows 6 Weight loss, Galvanostatic Langmuir isotherm. Inhibitors polarization and are acting as mixed inhibitors Electrochemical impedance spectroscopy techniques.

2015

Weight loss and Galvanostatic Physically adsorbed on the zinc 7 polarization techniques. surface. Temkin’s adsorption isotherm fits the experimental data Act as a mixed type inhibitors

2014

2014

2014

4



Corrosion Inhibition by Phenols – An Overview 8

Mild steel

H2SO4

glycolic

acid

Lakshmi et al.,

ethoxylate

4-

nonylphenyl ether (GAENE)

9

Mild steel

HCl

4-amino-3hydroxynaphthalene-1sulphonic acid (4A3H1S) 4-(5-(4-dimethylamino) phenyl)-1 H-pyrazol-5yl)phenol and 4-(5-(4nitrophenyl)-1 H-pyrazol-5yl)phenol 2-[(E)-{(1S,2R)-1-hydroxy-1phenylpropan2ylimino}methyl]phenol

10

Mild steel

HCl

11

Mild steel

HCl

12

Mild steel

HCl

catechin monomers

13

Mild steel

H 2SO4

14

Al

HCl

Nonyl phenol (NPH) with 2, 4 dimethyl aniline (DMA) and 2 ethyl aniline (EA) Schiff base

15

Low carbon steel

16

Mild steel

HCl

HCl

benzothiazole derivatives (2[(1,3-benzothiazol-2-y l amino) methyl]-1-naphthol (1) , 2-{[(6methyl-1,3-benzothiazol-2-yl) amino]methyl}-1-naphthol) (2) Schiff base

Potentiodynamic polarization curves,Linear polarization resistance (LPR) and Electro chemical impedance spectros copy (EIS) techniques (SEM) EIS LPR and Potentio dynamic measurements Scanning electron microscopy (SEM)

Mixed type inhibitor with 8 predominant inhibition at anodic site. This inhibitor functions through adsorption following Langmuir isotherm. The adsorption of 4A3H1S on the 9

2014

2014

surface of MS obeyed the isotherm of Langmuir adsorption.

EIS, Potentio dynamic The adsorption follows the 10 polarization, (SEM–EDX) Frumkin adsorption isotherm. and Weight loss methods Phenolic derivatives are mixedtype inhibitors.

2013

Weight loss and. Potentio It follows Langmuir adsorption dynamic polarization studies isotherm. It is a mixed type .UV-Visible spectroscopy inhibitor with cathodic inhibition Weight loss, potentiodynamic Physisorption follow Langmuir polarization, and EIS adsorption isotherm Weight loss ,Potentio dynamic The adsorption follow Temkin polarization method. Electro adsorption isotherm. Mixed chemical impedance ,SEM type inhibitor EIS, Tafel polarisation and Adsorption obeys Temkin Scanning electron microscopy adsorption isotherm. Schiff techniques. bases were cathodic inhibitor . Potentiodynamic polarization Acting as anodic inhibitor. The technique, and adsorptions were found to obey electrochemical impedance Temkin adsorption isotherm. spectroscopy (EIS).

11

2012

12

2012

13

2012

14

2012

15

2011

Potentiodynamic polarization Mixed type corrosion inhibitor . 16 , Weight loss , EIS, LPR The adsorption obeys Langmuir adsorption isotherm.

2011

5




Lakshmi et al.,

AISI304 Stainless steel CuNi10Fe ALLOY

HCl

N - (2-mercaptophenyl) -N' phenyl Thiourea

Potentio dynamic polarisation and adsorption study

NaCl

p-hydroxybenzoic acid (HBA) and protocatechuic acid (PCA),

19

Al6061SiCp

HCl

Propanoyl(1Z)-N-(2-hydoxy phenyl)-2-oxopropane hydrazo noate (PHOH)

Open circuit potential measure ments, Potentio dynamic polarization measurements, and the linear polarization method Potentiostatic polarization techniques and Weight loss method.

20

Carbon steel

Catechol

Zinc

21

Carbon steel

o-nitrophenol (ONP)

Zinc

22

Carbon steel

well water

Phenolphthalein(Pn)

Zinc

23

Aluminum

HCl NaOH

Phenol

24

Mild steel

H2SO4

Schiff bases

25

Steel

26

Aluminum

H 2SO4,, p-nitroaniline, m-nitroaniline HNO3 , -Napthol , catechol ptoludine and Resocinol, HCl Schiff bases

18

Weightloss method Polarization studies and AC impedance spectra FTIR Weight loss method, FTIR spectra Mass loss method, FTIR spectra Polarization study AC impedance spectra quantum electrochemical approaches based on density functional theory and cluster/polarized continuum model, using Tafel plots Tafel polarization and EIS methods. Mass loss method

Potentiodynamic polarization, EIS and Electrochemical frequency modulation (EFM) techniques.

Mxed type of inhibitors. Obeys Temkin adsorption isotherm, Physisorption mechanism. Cathodic inhibitors Obeys Freundlich adsorption isotherm. physical adsorption on the electrode surface cathodic inhibitor obey Temkins’ adsorption isotherm. Protective film is Fe2+ catechol complex. synergistic effect existing between the inhibitors. Protective film is Fe2+ catechol complex. synergistic effect existing between the inhibitors A synergistic effect exists between Pn and Zn 2+. Mixed inhibitor . Protective film is Fe 2+ -PN complex and Zn(OH)2. The rate of corrosion in alkaline solution is greater than in HCl media. Phenol is a potentialmolecule having mixed-type inhibition mechanism. Mixed corrosion inhibitors. It obeys Temkin isotherm Inhibition efficiency of catechol is very high . The inhibition efficiency of Resorcinol is low The adsorption obeys Freundlich adsorption isotherm.

17

2011

18

2011

19

2011

20

2011

21

2011

22

2010

23

2010

24

2010

25

2010

26

2010

6




Carbon steel

28

Al-2.5Mg alloy

NaCl

29

N80 steel

HCl

30

Al-0.8Mg alloy

31

Lakshmi et al., Weight loss method FTIR spectra, SEM and AFM

Protective film is Fe2+ - 27 resorcinol complex and Zn(OH)2

2010

Gentisic acid

Rotating disc electrode

Cathodic type inhibitor. 28 The adsorption follows Freundlich adsorption isotherm.

2010

AISI 304 Stainless steel Aluminum alloy 5083 AZ61 Mg alloy

HCl

4-phenylthiazole

Weight loss and Potentio dynamic polarization , (FTIR) Potentiodynamic polarization method, Linear polarization method, and Electrochemical impedance spectroscopy Weight loss, Galvanostatic Polarisation and adsorption study.

Protective surface film l . 29 Exhibited synergistic effect Act as cathodic corrosion 30 inhibitors Physical adsorption is proposed Adsorption obeys Freundlich adsorption isotherm. Synergistic role existing between 31 the inhibitors and it obeys Temkin’s adsorption isotherm

2009

NaCl

Mixtures of aniline and phenol Sinapinic and Gentisic acid

8-hydroxyquinoline is a cathodic 32 inhibitor . organic conversion film formed 33 on the surface Enhance film adhesion by the covalent bonds of Mg {single bond}O{single bond}N linkage.

2009

34

Mild steel

HCl

Schiff bases

N80 steel

HC1

36

N80 steel

HCl

Mixtures (TVE-3A, TVE-3B and TVE-3C) containing formaldehyde in combination with phenol or cresol Methoxy phenol (MPH) and Nonyl phenol (NPH)

Mixed inhibitor. Adsorption 34 follows the Langmuir adsorption isotherm. Maximum inhibition shown by 35 TVE-3A> TVE-3B > TVE-3C Adsorption Obeys Frumkin isotherm Protective chemisorbed film on 36 the metal surface, Adsorption follow Temkin isotherm Mixed type inhibitors.

2008

35

Polarization and (EIS) methods Electrochemical techniques energy dispersive spectrometer (EDS) analysis and Fourier transform infrared spectros copy,Linear sweep voltammetry Weight loss measurements, Polarization and EIS methods. Weight loss , Potcntiostatic polarization technique FTIR study

32 33

Resorcinol

Zinc

KSCN

pH (2 8- Hydroxyquinoline) and l2) NaOH p-nitro-benzene-azo-resorcinol (PNBAR)

Polarization studies The FTIR spectra

7



2009

2009

2008

2008

2007


Lakshmi et al.,

37

Zinc

H 2SO4

Schiff bases

38

Steel

39

Stainless steel

aerated HCl solution H3PO4

Flavanoid monomers catechin, epicatechin, epigallo catechin and epicatechingallate Methoxy-2-Allyl4 Phenol (MAP)

40

Stainless steel Iron

H3PO4

Eugenol (methoxy-2-allyl-4phenol) Reduction of N,N′-bis (salicylal dehyde) -1,3-diamino propane, Dodecyl phenol ethoxidate as a non-ionic surfactant (NS)

41 42

43

HCl

Al, (Al + HCl Cu), (Al +Si) alloys HCI Iron

p-aminophenol and poly (pamino phenol)

44

Iron

HCl

45

N80 steel

HCl

46

Al, Cu, NaOH and Al-Cu alloys

Phenols (Phenol, and Pyrogallol)

47

Al and NaOH Zinc pigments Rh, Pd, Ir, Pt, and Au)

2-hydroxy-oximes,

48

Zinc

2-aminothiophenol (ATP) and 2-aminophenyl disulfide (APDS) Phenol, o-Cresol and p-Cresol

Derivatives alcohols, phenols,

Resorcinol,

Weight loss and Polarization Inhibitors obey the Langmuir 37 measurements adsorption isotherm..

2005

Electrochemical methods

The monomers were found to be 38 mainly cathodic inhibitors .

2004

Potentiodynamic polarization, Electrochemical impedance spectroscopy and SEM. Weight loss ,polarization methods, and EIS Electrochemical polarization methods Potentiodynamic polarization and EIS

The most inhibition efficiency is 39 obtained with polymerized form.

2004

Formation of a protective layer 40 on the metal surface. They act as anodic type 41 inhibitors. Anodic inhibitor. I.E decreases : 42 (Al + Si) > (Al + Cu) > Al. Frumkin adsorption isotherm 43 Obeys Langmuir adsorption isotherm.. Formation of a protective layer,. 44 A pitting phenomena observed on the iron electrode surface, The adsorption follow Temkin 45 adsorption isotherm. All the inhibitors are mostly anodic types. Affected both the anodic and 46 cathodic reactions,. Adsorption of phenols on the electrode surface. Better for aluminium (protection 47 factors up to 99.9%) than for the zinc pigment, The more reactive the metal 48 towards surface-oxide formation, the greater the extent

2004

Polarization and Electrochemical impedance spect-roscopy methods Electrochemical impedance spectroscopy (EIS). Weight loss Potentiostatic method.

method and polarization

Potential-time, polarisation, and Weight loss measurements. Gas-volumtric method

aromatics,

Thin-layer methods; X-ray

electrochemical photoelectron

8



2004 2004

2004

2002

2002

1999

1998

1991


Lakshmi et al., spectroscopy (XPS).

49

A1-4% Cu NaOH alloy (Al B26 S)

o-substituted phenols

Weight loss Potentiostatic method.

of organic chemisorptioninduced passivation. method and General order of efficiency is as 49 polarization follows: 0-allylphenol < guiacol < o-nitrophenol < phenol ≤ ocresol ≤ o-aminophenol < catechol < o-chlorophenol < salicylaldehyde,

CONCLUSION Corrosion inhibition study on various metals in different environment with various inhibitors and additives at room temperature has been reviewed. They behave as Cathodic , Anodic, Mixed type inhibitors and shows synergistic effect

ACKNOWLEDGEMENT I would like to extend my heartiest gratitude to my Teacher, friends and my family for providing moral support.

9



1977


Lakshmi et al.,

REFERENCES [1].Adsorption and corrosion inhibition effect of Schiff base molecules on the mild steel surface in 1M HCl medium:a combined experimental and theoretical approach Sourav Kr. Saha, Alokdut Dutta Pritam Ghosh, Dipankar Sukul and

Priyabrata

Banerjee Phys. Chem. Chem. Phys., 2015,17, 5679-5690. [2]. Electrochemical Linear Polarization Studies of Amodiaquine Drug as a Corrosion Inhibitor for Mild Steel in 0.1M HCL Solution I. A. Akpan N. O. Offiong 2015 Chemistry and Materials Research Vol.7 (.1,) pp17-20.

[3]. Imidazole derivative as novel effective inhibitor of mild steel corrosion in aqueous sulphuric acid Nnenna Winifred Odozi, Jonathan Oyebamiji Babalola, Ekemini Bassey Ituen , Abiodun Omokehinde Eseola 2015 American Journal of Physical Chemistry 4(1-1):pp 1-9.

[4]. 2-{(3-nitrobenzylidene)amino}phenol (SBNAP) as Inhibitor of Aluminium and Mild Steel Corrosion in Sulphuric acid media Echem O. G, James A. O 2015 International Journal of Applied Research; 1(8): pp 353-359.

[5].Corrosion Inhibition of Aluminum inHydrochloric Acid Solutions Using Some Chalcone Derivatives A. S. Fouda*, K.shalabi, N. H. Mohamed (2014) International Journal of Innovative Research in Science,Engineering and Technology 3 (3) pp9861-9873.

[6]. Non ionic surfactants derived from phenol compounds as inhibitors for corrosion of aluminum in hydrochloric acid solution Dr. Ishaq Zaafarany Posted on Thursday, July 10, 2014 JEPT – Journal for Electrochemistry and Plating Technology pp3453. 10




Lakshmi et al.,

[7]. Coumarin Derivatives as Corrosion Inhibitors for Zinc in HCl Solutions Prof. Dr. M. Abdallah, Dr. Ishaq Zaafarany,

Prof. Dr.

A. S. Fouda and W. El-Nagar Posted on Friday, April 11, 2014JEPT – Journal for Electrochemistry and Plating Technology pp3190.

[8]. Inhibitive Performance of Glycolic Acid Ethoxylate 4-Nonylphenyl Ether in Acid Solution for Corrosion of Mild Steel emel bayol a. Ali gürten yavuz sürme 2014 El-Cezerî Journal of Science and Engineering Vol: 1, No: 3, pp(30-39).

[9]. Evaluation of corrosion inhibition of mild steel in 0.1 M HCl by 4-amino-3-hydroxynaphthalene-1-sulphonic acid

Res_it Yıldız ,

Turgut Dog˘an _Ilyas Dehri 2014 Corrosion Science 85 pp 215–221.

[10]. New Eco-Friendly Corrosion Inhibitors Based on Phenolic Derivatives for Protection Mild Steel Corrosion A.S.Fouda1,*, A.M.Eldesoky2, M.A.Elmorsi3, T.A.Fayed3and M.F.Atia3 Int. J. Electrochem. Sci., 8 (2013) 10219 – 10238.

[11]. 2-[(E)-{(1S,2R)-1-hydroxy-1-phenylpropan-2- ylimino}methyl]phenol for inhibition of acid corrosion of mild steel Kesavan, D., Tamizh, M.M.,Sulochana, N., Karvembu, R. (2012) Journal of Surfactants and Detergents 15(6) pp751-756.

[12]. Elucidation of the corrosion inhibition of mild steel in 1.0 M HCl by catechin monomers from commercial green tea extracts Nofrizal, S., Rahim, A.A., Saad, B., (...), Shah, A.M., Yahya, S. ( 2012 ) Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science vol43 (4) pp 1382-1393.

11




Lakshmi et al.,

[13]. Binary mixtures of nonyl phenol with alkyl substituted anilines as corrosion inhibitors for mild steel in acidic medium Shukla, H.S., Haldar, N., Udaybhanu, G. (2012) E-Journal of Chemistry 9(1),pp149-160. [14]. Schiff bases

as corrosion inhibitor for aluminium in HCl solution

Serpil Şafak, Berrin Duran, Aysel Yurt, Gülşen

Türkoğlu 2012 Corrosion Science 54 , pp251-259. [15]. Inhibition of acidic corrosion of low carbon steel by novel synthesized benzothiazole derivatives Hür, E., Varol, G.A., Görgün, K.,Sakarya, H.C. (2011) Gazi University Journal of Science vol 24 (4) pp699-707. [16]. Adsorption and corrosion inhibition effect of 2-((5-mercapto-1,3,4- thiadiazol-2-ylimino)methyl)phenol Schiff base on mild steel Solmaz, R., Altunba, E., Karda, G. (2011) Materials Chemistry and Physics 125 (3) pp 796-801. [17]. Corrosion Inhibition of Stainless Steel in Hydrochloric Acid by N - (2-mercaptophenyl) -N' –phenyl Thiourea, Ramadev Herle, Prakash Shetty, Divakara Shetty. S,AchuthaKini. U, (2011) International J. Chemistry and Applications, 3, pp151-158. [18].Corrosion inhibition of CuNi10Fe alloy with phenolic acids L. Vrsalović, e. Oguziem. Kliškićs. Gudić Chemical Engineering Communications vol. 198, no. 11, pp. 1380-1393, 2011.

[19]. Corrosion Inhibition of Al6061- SiCp Composite in 0.5 M Hydrochloric Acid U Achutha Kini Prakasha Shetty S Divakara Shetty and M Arun Isloor 2011 International Conference on Chemistry and Chemical Process IPCBEE vol.10 (2011) © (2011) IACSIT Press, Singapore pp127-132.

[20]. Inhibitive action of the catechol-zinc system in controlling the corrosion of carbon steel H. Benita Sherine S. Felci Sagaya Mary S. Rajendran 2011Bulgarian Chemical Communications, 43( 4) pp 544 – 551. 12




Lakshmi et al.,

[21]. O-Nitro Phenol as a Corrosion Inhibitor for Carbon Steel BenitaSherine, H.; Jency Angela, A.; Rajendran, 2011 Asian Journal of Research in Chemistry;, Vol. 4 (4), p629. [22]. The effect of Zn 2+ ion in promoting inhibitive property of phenolphthalein Sathiyabama, J., Rajendran, S.,Jeyasundari, J., Shyamaladevi, B. (2010 ) Journal of Engineering Science and Technology Review 3 (1) pp27-31. [23]. Fundamental studies of aluminum corrosion in acidic and basic environments: Theoretical predictions and experimental observations , Malek, A.M. (2010) Electrochimica Acta 55 pp 5253-5257. [24]. Protection of mild steel corrosion with new thia-derivative Salens in 0.5 M H2SO4 solution Hosseini, M.G., Khalilpur, H., Ershad,

S., Saghatforoush,L.

(2010)

Journal

of

Applied

Electrochemistry(7)

40(2)

pp215.

[25].Organic compounds containing-NH2,-OHgroups as corrosion inhibitors S.M. BHAGAT, T.M. BHAGAT*, A.R. UNCHADKAR and M.N. DESHPANDE (2010) Oriental Journal of Chemistry. 26(4), pp1545-1548. [26] Inhibition of aluminum corrosion in hydrochloric acid media by three schiff base compounds Fouda A.S., Elewady

G.Y., El-

Askalany A., Shalabi K.2010, Zaštita materijala vol. 51, ( 4) pp 205-219.

[27] Inhibition of Corrosion of Carbon Steel by Resorcinol-Zn2+ System in Well Water Benita Sherine1 A. Jamal Abdul Nasser and S. Rajendran 2010 S-JPSET,. 1 ( 2) pp115-123. Nasser and S. Rajendran 2010 S-JPSET,. 1 ( 2) pp115-123.

[28] Corrosion

Inhibition of Aluminum- Magnesium alloy by gentisic acid.L.Vrsalovic, M.Kliskic, S.Gudic and I.Smoljko. 2010

Indian Journal Of Chemical Technology vol17 pp89-94.

13




Lakshmi et al.,

[29]. Corrosion protection of N80 steel in HCl by condensation products of aniline and phenol Vishwanatham, S., Sinha, P.K. (2009 ) Anti-Corrosion Methods and Materials 56 ( 3) pp 139-144. [30]. Aplication of Phenolic Acids in the Corrosion Protection of Al- 0.8Mg Alloy in Chloride Solution L. Vrsalovic*, M. Kliškic and S. Gudic In t(2009) . J. Electrochem. Sci., 4 pp 1568 – 1582 [31]. Inhibition effect of 4-phenylthiazole derivatives on corrosion of 304L stainless steel in HCl solution, Fouda. A.S, Ellithy. A. S (2009) J. Corros. Sci. 51,pp 868–875

[32]. Corrosion Inhibition of Aluminum Alloy 5083 prael S. Yaro" and Huda A. Dahyool (2009) lraqi Journaol of Chemical and Petroleum Engineering Vol.10 (.4) pp 9-25. [33]. Interfacial chemistry of organic conversion film on AZ61 magnesium alloy surface Yang, X., Pan, F., Zhang, D. (2008) Applied Surface Science 255 (5) pp1782-1789. [34]. Electrochemical and theoretical investigation on the corrosion inhibition of mild steel by thiosalicylaldehyde derivatives in hydrochloric acid solution Behpour, M., Ghoreishi, S.M., Soltani, N., (...), Hamadanian, M., Gandomi, A. (2008 ) Corrosion Science 50(8) pp2172-2181. [35]. Study on corrosion control of N80 steel in acid medium using mixed organic inhibitors Kumar, T., Vishwanatham, S.,Emranuzzaman (2008 ) Indian Journal of Chemical Technology 15 (3), pp. 221-227. [36]. Corrosion inhibition of N80 steel in hydrochloric acid by phenol derivatives Vishwanatham, S., Haldar, N. (2007 ) Indian Journal of Chemical Technology 14 (5) pp501-506.

14




Lakshmi et al.,

[37]. Ortho-, meta-, and para-aminophenol-N-salicylidenes as corrosion inhibitors of zinc in sulfuric acid

Talati, J.D., Desai,

M.N., Shah, N.K. (2005) Anti-Corrosion Methods and Materials 52 (2) pp108-117. [38]. Mangrove tannins as corrosion inhibitors in acidic medium- Study of flavanoid monomers

Abdul Rahim, A., Rocca,

E.,Steinmetz, J., Adnan, R., Kassim, M.J. (2004) EUROCORR 2004 - European Corrosion Conference: Long Term Prediction and Modelling of Corrosion (0). [39]. Electrochemical study of corrosion inhibition of stainless steel in phosphoric medium

Hnini, K., Chtaini, A., Khouili,

M.,Elbouadili, A. (2004 ) EUROCORR 2004 - European Corrosion Conference: Long Term Prediction and Modelling of Corrosion (0) edn (1) pp523. [40]. Inhibition of metallic corrosion with eugenol Hnini, K., Chtaini, A.Elbouadili, A. (2004) Bulletin of Electrochemistry 20 (11). [41]. Corrosion inhibition of iron in 1 M HCl solution with Schiff base compounds and derivatives Emregül, K.C., Atakol, O. (2004) Materials Chemistry and Physics 83 (2-3) pp373-379. [42]. Corrosion inhibition study of pure Al and some of its alloys in 1.0 M HCl solution by impedance technique Abd El Rehim, S.S., Hassan, H.H.,Amin, M.A. (2004 ) Corrosion Science Volume 46, Issue 1, January 2004, Pages 5-25.

[43]. Investigation on the inhibitive effect of poly (p-aminophenol) on corrosion of iron in 1M HCL solutions Manivel, P and Venkatachari, G (2004) Journal of Metallurgy and Materials Science, 46 (4). pp. 263-270. [44]. Inhibition de la corrosion du fer dans HCl 1 M. Partie II. Etude des propriétés inhibitrices du 2-aminothiophénol et du 2aminophényl disulfure, par spectroscopie d'impédance | [Inhibition of iron corrosion in 1 M HCl. Part II. Study of the protective 15




Lakshmi et al.,

properties of 2-aminothiophenol and 2-aminophenyl disulfide by impedance spectroscopy] Benchekroun, K., Dalard, F.,Rameau, J.J., El Ghazali, A. (2002) New Journal of Chemistry 26 (7)pp( 946-952). [45].

Ortho

and

para

substituted

phenol

as

corrosion

inhibitors

for

N80

steel

in

hydrochloric

acid

vishwanatham s. ; kumar t. ; emranuzzaman ; Bulletin of electrochemistry 2002, vol. 18, no8, pp. 377-382. [46]. Effect of some phenols on corrosion of Al, Cu, and Al-Cu alloys in NaOH solutions Shayeb, H.A.E.L., Abd El Wahab, F.M., Zein El Abedin, S. (1999) British Corrosion Journal 34 (2)pp( 145-150). [47]. Aromatic 2-hydroxy-oximes as corrosion inhibitors For aluminium and zinc pigments B. Müller, g. Kub itzki and g . Kinet 1998 Corrosion Science, Vol. 40, No. 9, pp. 1469-1477. [48]. Influence of chemisorbed organic monolayers on electrode surface oxidation Michelhaugh, S.L., Bhardwaj, C.,Cali, G.J., (...), Berry, G.M., Soriaga, M.P. (1991) Corrosion 47 (5), pp. 322-328 (17). [49].O-Substituted Phenols as Corrosion Inhibitors for Aluminium-Copper Alloy in Sodium Hydroxide J. D. Talati; R. M. Modi British Corrosion Journal Volume 12, Issue 3 (01 January 1977), pp. 180-184.

:1

16




Lakshmi et al.,

: 18

Received: : 1818-12-2015 Accepted: 20-12-2015

17




Lakshmi et al.,

18



Corrosion resistance of Commercial Al in SCPS------

S.Rajendran et al.,


ISSN Online: 2395-7018 3(1)(2016)19-33

Corrosion Resistance of Commercial Aluminium in simulated Concrete Pore Solution in presence of curcumin extract Susai Rajendran1, Duraiselvi2 , M.Pandiarajan3, S Shanmugapriya4, T Umasankareswari5 and P Prabhakar6 1

Department of Chemistry, Corrosion Research centre,RVS School of Engineering and Technology,Dindigul 624005, India. E.mail: [email protected] 2 3

Karpagam University, Coimbatore, India

Corrosion Research Centre, PG and ResearchDepartment of Chemistry, GTN Arts College, Dindigul- 624005,India. E.mail:[email protected],

4

Department of Chemistry , Madha Engineering College, Kundrathur, Chennai, India. Email: [email protected] 5

6

Department of Chemistry, Rajapalayam Rajus College, Rajapalayam, India

PG and Research Department of Chemistry, APA College of Arts and Culture, Palani, India

Abstract The corrosion resistance of commercial aluminium (95% pure) in simulated concrete pore solution (SCPS) prepared in natural sea water has been evaluated in the absence and presence of curcumin extract and Zn2+. It is observed that Aluminium is more corrosion resistance in SCPS than in sea water. When curcumin extract is added to SCPS, the corrosion resistance of Al increases. However, in the presence of curcumin –Zn2+ system, the corrosion resistance of Al in SCPS decreases. Key words: Concrete Corrosion, aluminium, Simulated Concrete Pore Solution, Curcumin, Green Inhibitor 19

Int J Nano Corr Sci and Engg 3(1) (2016) 19-37 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi


S.Rajendran et al.,

1. Introduction The long time necessary for chlorides to penetrate the concrete cover can be avoided by testing the steel in concrete simulated pore solution, which is mainly consisted of saturated calcium hydroxide [Ca(OH)2], sodium hydroxide (NaOH) and potassium hydroxide (KOH) with the pH ~13.5 [1, 2]. However, in numerous studies of rebar corrosion, saturated Ca(OH)2 has been used as a substitute for pore solution [3-9]. The pH of saturated calcium hydroxide solution is about 12.6 [10]. The capability of the passive film to protect the steel against corrosion increases with pH [11]. Consequently, the passive layer induced by saturated calcium hydroxide does induce passivation but not to the degree encountered by steel in good quality concrete. Moreover, the other ions present in pore solution, particularly, sodium and potassium, may also play a role in the passivation and corrosion processes. However, the nature of the passive film due to using saturated Ca(OH)2 and simulated pore solution was not compared together in the previous studies. The required time of passivation of steel in concrete was determined for steel in pore solution [12] but not in saturated calcium hydroxide.

The degradation of reinforcing steel due to corrosion is predominant in concrete structures. Generally, most structures are contaminated with chloride as a result of deicing during the winter and also in chloride laden environment such as marine for offshore and coastal structures [13]. Corrosion damage causes the weakening and quickens the aging of high way structures [14]. Environmental modification by means of inhibitors is one of the most effective measures for corrosion control in rebar embedded in concrete. Cost of inorganic inhibitor is low, however some of them are very toxic (harmful toboth human and environment) such as chromate, mercride, arsenate etc. Corrosion inhibitors are chemical substances which can prevent or reduce corrosion rate when present in adequate proportion. The use of inhibitors seems to be more promising due to their simplicity in application, and relatively less expensive. Generally, inhibitors are classified according to which electrode reaction they influence. They can be identified as anodic, cathodic or mixed inhibitors [15]. So far many investigations have been carried out on the effect of inorganic inhibitors on the corrosion of carbon steel in concrete. Calcium nitrite was able to reduce or inhibit initiated localized corrosion of rebar steel chloride contaminated concrete as reported in previous study [16]. Calcium nitrite can inhibit the initiated, localized corrosion of reinforcing steel in solutions 20



S.Rajendran et al.,

simulating chloride contaminated concrete, if it is present in sufficient concentration in early stages of the corrosion process. Nitrites (calcium or sodium salt) are anodic inhibitors, they compete with chloride ions for the ferrous ions at the anode to form a film of ferric oxide (Fe2O3) [17]. Sodium nitrite inhibitor was found to be effective in reducing corrosion rate in reinforced steel concrete at 4%wt dosage [18]. However, efficiency decreases as chloride content increases [19]. The inhibitive mechanism of sodium nitrite on carbon steel is similar to that of calcium nitrite. Moreover, the effect of plant extracts as corrosion inhibitor in mild steel in acidic medium have been studied. It has been reported that vernonia amygdalina (bitter leaf) and Azadirachita (Nee leaf) extracts performed optimally in acidic solution and that inhibition efficiency increases with increase in dosage. The inhibition mechanism of vernonia amygdalina is related to their physical adsorption properties due to the presence of tannin, alkaloid and saponnins [20, 21, 22]. The use of organic compound to reduce the corrosion of carbon steel has great importance due to their applications in prevent corrosion in different aggressive environments [23]. However, no study of vernonia amygdalina inhibition potency in reinforcing steel bar in concrete exposed to chloride laden environment has been reported. Based on the background of knowledge of vernonia amygdalina (bitter leaf), sodium nitrite and the traditional calcium nitrite inhibitors, the present study was designed to identify and evaluate the behaviour of sodium nitrite, vernonia amygdalina and calcium nitrite inhibitors on corrosion performance of carbon steel reinforced in concrete exposed to simulated seawater. The present work is undertaken (i)

To evaluate the corrosion resistance of commercial aluminium (95 % pure) in natural sea water (Table 1) and

(ii)

to evaluate the corrosion resistance of aluminium in simulated concrete pore solution (SCPS) prepared in natural sea water in the absence and presence curcumin extract and Zn2+

The outcome of the present study will be useful to the concrete corrosion technologists. 2. MATERIALS AND METHODS Metal specimens Aluminium: Commercial aluminium (95% pure) was used in the present study.

21



S.Rajendran et al.,

Preparation of curcumin extract 10 g of turmeric powder was boiled with 50 ml of distilled water. The suspended impurities were removed by filtration .The filtrate was made up to 100 ml .It was used as inhibitor in the presence of curcumin is shown in Scheme 1.

Scheme 1. Structure of curcumin

Preparation of

Simulated concrete pore solution (SCPS)

A Saturated Solution of Ca(OH)2 is considered as simulated concrete pore solution. SCPS was prepared in natural sea water .Simulated concrete pore solution is mainly consisted of saturated calcium hydroxide (Ca(OH)2, sodium hydroxide(NaOH) and potassium hydroxide (KOH) with the pH ~ 13.5[24-25]. However in numerous studies of rebar corrosion, saturated Ca(OH)2 has been used as a substitute for pore solution[26]. A saturated calcium hydroxide solution is used in present study, as SCP solution with the pH ~ 12.5. Table 1.Physico – Chemical Parameters of sea water Parameters Value pH Conductivity

7.66 44200 μmhos/cm

Chloride

6050 ppm

Sulphate

2616 ppm

TDS

30940 ppm

Total Hardness

2800 ppm

Calcium

120ppm

Sodium

6300 ppm

Magnesium

600 ppm

Potassium

400 ppm

AC impedance spectra 22



S.Rajendran et al.,

AC impedance spectral studies were carried out in a CHI – Electrochemical workstation with impedance, Model 660A. A three-electrode cell assembly was used. The working electrode was one of the three metals. A saturated calomel electrode (SCE) was the reference electrode and platinum was the counter electrode. The real part (Z’) and imaginary part (Z”) of the cell impedance were measured in ohms at various frequencies. Values of the charge transfer resistance (Rt) and the double layer capacitance (Cdl) were calculated.

Result and Discussion Analysis of AC Impedance Spectra AC impedance spectra have been used to detect the formation of protective film on the metal surface. If a protective film formed on the metal surface, the charge transfer resistance increases and double layer capacitance value decreases [27-31]. The AC impedance spectra of Aluminium immersed in simulated concrete pore solution Table 2. AC impedance parameters of Aluminium immersed in simulated concrete pore solution prepared in sea water (SCPS) in the absence and presence of curcumin extract. Nyquist plot

Bode plot

Systems Rt ohmcm2

Cdl Fcm-2

Impedance

Phase

log(Z/ohm)

angle degree

Sea water

107.07

4.76x10-8

1.959

50

SCPS

146.02

3.49x10-8

2.316

54

SCPS + Curcumin 6 ml

160.58

3.18x10-8

2.363

55

SCPS + Curcumin 6 ml 131.06

3.89x10-8

2.269

53

+ Zn2+ 23



S.Rajendran et al.,

Fig 1. AC impedance spectrum of aluminium steel immersed in Sea water (Nyquist plots)

Fig 2. AC impedance spectrum of aluminium steel immersed in SCPS (Nyquist plots)

24



S.Rajendran et al.,

Fig 3. AC impedance spectrum of aluminium steel immersed in SCPS + Curcumin (Nyquist plots)

Fig 4. AC impedance spectrum of aluminium steel immersed in Sea water (Nyquist plots)

25



S.Rajendran et al.,

Fig 5. AC impedance spectrum of aluminium steel immersed in Sea water (Bode plots)

Fig 6. AC impedance spectrum of aluminium steel immersed in SCPS prepared in Sea water (Bode plots)

26



S.Rajendran et al.,

Fig 7.AC impedance spectrum of aluminium steel immersed in SCPS + Curcumin (Bode plots)

Fig 8.AC impedance spectrum of aluminium steel immersed in SCPS + Curcumin+ Zn2+ (Bode plots) Prepared in sea water (SCPS), in the absence and presence of curcumin extract and Zn2+ are shown in Figs 1 to 8. The Nyquist plots are shown in figs 1 to 4 and the bode plots are shown in figs 5 to 8.

27



S.Rajendran et al.,

The AC impedance parameters, namely charge transfer resistance (Rct) and double layer capacitance (cdl) are given in Table 2.(derived from Nyquist plot). The impedance value and phase angle values are derived from bode plots. When aluminium is immersed in sea water (fig 1) the charge transfer resistance is 107.07 ohmcm2 and the double layer capacitance is 4.76 x10-8 Fcm-2. When aluminium is immersed in simulated concrete pore solution prepared in sea water (SCPS), the Rct value increases from 107.07 to 146.02 ohmcm2; the Cdl value decreases from 4.76x10-8 to 3.49x10-8Fcm-2. These observations indicate that aluminium is more corrosion resistant in SCPS than in sea water. This is due to the fact that in presence of SCPS (a saturated solution of calcium hydroxide), Aluminium hydroxide is formed on aluminium surface, which may be converted insoluble Al2O3. This acts as a barrier on the metal. This is further supported by the fact that the impedance value increases from 1.959 to 2.3160 increase phase angle is also noticed, that is from 50◦ to 54◦,(figs 5 and 6). In the frequency is impedance plot (fig 5) it is observed that a peak appears around 1.8[log(freq/Hz)]. This peak is attributed to the formation of corroding metal surface and various ions present in sea water. In Fig 6 two peaks are observed one around 1.0 and the other around 3.5[log(freq/Hz)]. The peak at 1.0 is due to the film formed on the metal surface, due to the interaction of Fe2+ ions and the various anions present in sea water. In fig 1 and fig 2 inductive loops are observed in the low frequency region. They are attributed to the relaxation process obtained by adsorption of inhibitors on the electrode surface. The inhibitors in sea water are the anions in sea water and in the case of SCPS, the inhibitors are the anions and OH- combine with Al3+ generated on the metal surface, resulting in the formation of Al (OH)3 first and Al2O3 finaly. When curcumin is added to SCPS, the Rct value further increases and double layer capacitance value further decreases. That is addition of curcumin extract to SCPS increases the corrosion resistance of Aluminium. This is due to formation of Al3+ curcumin complex on the metal surface in addition to formation of Al2O3. The increases are corrosion resistance is also supported by the increases in impedance value (2.363) and increases in phase angle (55◦) 28



S.Rajendran et al.,

(fig 7).These peaks are observed in the log freq vs log z plot (fig 7). The middle peak may be due to Al3+- curcumin complex on metal surface. The peaks in the low frequency region results from the interaction of anion present in sea water with the metal surface. The prominent peak in the high frequency region is due to formation of Al2O3 observed from the Nyquist plot for this system (Fig 3), that a capacity loop appears (fig 3), that a capacity loop appears in the low frequency region .This is due to the formation of film on the metal surface. The increase is corrosion resistance of aluminium in this system is due to the formation of Al3+ curcumin complex on the metal surface. When Zn2+ is added to the SCPS curcumin system, the corrosion resistance of aluminium decreases. This is due to the fact that when Zn2+ is added, it is precipitated as Zn(OH)2 in the bulk of the solution. Curcumin may form complex with Zn2+ under the experimental conditions. Thus addition of Zn2+ to the simulated concrete pore solution decreases the transport of

OH- and curcumin towards aluminium surface from the bulk of the saturated

similar observation have been made in other cases also. When Zn2+ is added to the SCPS+ inhibitor system, the corrosion resistance of the metal in SCPS+ inhibitor decreases. However it must note that the corrosion resistance of Aluminium in SCPS + Curcumin + Zn2+ system is better than sea water only. A inductive loop in the low frequency region of fig 3 reveals the formation of a film formed on the metal surface. But the film is not complex and stable. And hence its protective nature is less when compared with SCPS or SCPS+ curcumin systems. Conclusion The corrosion resistance of aluminium of sea water, simulated concrete pore solution prepared in sea water (SCPS), SCPS+ Curcumin system and SCPS + Curcumin + Zn2+ system has been evaluated by Electrochemical Impedance Spectroscopy. It is observed that the corrosion resistance of Aluminium decreases in the following order SCPS+ Curcumin> SCPS > SCPS+ Curcumin +Zn2+ > Sea water This study cautions the addition of metal ions to the concrete admixtures References [1] Andrade C., Merino P., Novoa X. R., Perez M. C., Solar L. Passivation of reinforcing 29



S.Rajendran et al.,

steel in concrete. Materials Science Forum 1995;192-194:861. [2] Hansson C. M. Comments on electrochemical measurements of the rate of corrosion of steel in concrete. Cement and Concrete Research 1984;14:574. [3] Ramirez E., Gonzalez J. A., Bautista A. The protective efficiency of galvanizing against corrosion of steel in mortar and in Ca(OH)2 saturated solutions containing chlorides. Cement and Concrete Research 1996;26:1525. [4] Hou J., Chung D. D. L. Effect of admixtures in concrete on the corrosion resistance of steel reinforced concrete. Corrosion Science 2000;42:1489. [5] Gonzalez J. A., Miranda J. M., Otero E., Feliu S. Effect of electrochemically reactive rust layers on the corrosion of steel in a Ca(OH)2 solution. Corrosion Science 2007;49:436. [6] Nakayama N. Inhibitory effects of nitrilotris (methylenephosphonic acid) on cathodic reactions of steels in saturated Ca(OH)2 solutions. Corrosion Science 2000;42:1897. [7] Nakayama N., Obuchi A. Inhibitory effects of 5-aminouracil on cathodic reactions of steels in saturated Ca(OH)2 solutions. Corrosion Science 2003;45:2075.

[8] Gonzalez J. A., Cobo A., Gonzaalez M. N., Otero E. On the effectiveness of realkalisation as a rehabilitation method for corroded reinforced concrete structures. Materials and Corrosion 2000;51:97. [9] G. Blanco, A. Bautista, H. Takenouti. EIS study of passivation of austenitic and duplex stainless steels reinforcements in simulated pore solutions. Cement & Concrete Composites 2006;28:212.

[10] Lide D. R. CRC Handbook of chemistry and physics. New York, NY: CRC Press, 1999.

[11] Verink E. D., Pourbaix M. Pitting potentials versus pH. Corrosion 1971;27:495.

[12] Poursaee A., Hansson C. M. Reinforcing steel passivation in mortar and pore solution. Cement and Concrete Research 2007;37:1127.

[13] Tang Y., Zhang G. and Zuo V. 2012. Inhibition effects of several inhibitors on rebar in acidified concrete pore solution. Construction and Building Materials. 28: 327-332.

30



S.Rajendran et al.,

[14] Nguyen T.N., B, Hubbard J and McFadden G.B. 1991.Mathematical model for the cathodic blistering of organic coatings on steel immersed in electrolytes. International Journal Coating Technology. 63: 43-52.

[15] Fontana M.G. and Greene N.D. 1982. Corrosion Engineering. (2nd Ed.) McGraw-Hill. Inc.

[16] Krolikowski A. and Kuziak J. 2011. Impedance study of calcium nitrite as a penetrating corrosion inhibitor for steel in concrete. Electrochimica Acta. 56:7845- 7853.

[17] Soylev T.A. and Richardson M.G. 2006. Corrosion inhibitors for steel in concrete: State of the art report. Construction and Building materials.

[18] Gu P, Elliott S., Hristova R., Beaudoin J.J., Brousseau R and Baldock B. 1997. A study of corrosion inhibition performance in chloride contaminated concrete by electrochemical impedance spectroscopy. ACI Materials Journal. 5: 385-395.

[19] Dhouibi L, Triki E and Raharinaivo A. 1988. Laboratory experiments for assessing the effectiveness of inhibitors against steel corrosion in concrete.Proceedings of the sixth international symposium on advances in electrochemical science and technology. Chennai, Indian.

[20] Loto C.A., Loto R.T. and Popoola A.P.I. 2011. Effect of Nee leaf (Azadirachita indica) extract on the corrosion inhibition of mild steel in dilute acid. International Journal of Physical Science. 6(9): 2249- 2257.

[21] Ayeni F.A., Madugu I.A., Sukop P., Ihom A.P., Alabi O., Okara R. and Abdulwahab M. 2012. Effect of aqueous extracts of bitter leaf powder on the corrosion inhibition of AlSi Alloy in 0.5M caustic soda solution. Materials Characterization and Engineering. 11: 667-670. [22] Loto C.A. 2003.The effect of bitter leaf on the inhibition of mild steel in HCl and 31



S.Rajendran et al.,

H2SO4. Corrosion Prevention and Control Journal. 50: 43-49. [23] Ali S.A., Al-Muallem H.A., Rahman S.U. and Saeed M.T. 2008. Bis-isoxazolidines: A new class of corrosion inhibitors of mild steel in acidic media. Corrosion Science. 50(11): 3070-3077. [24] Pandiarajan M. et al (2014), “Corrosion Inhibition by Potassium Chromate-Zn2+ System for Mild Steel in Simulated Concrete Pore Solution”, Res. J. Chem. Sci., Vol. 4(2), pp 49-55. [25] M. Pandiarajan et al (2013), “Corrosion resistance of Mild steel in Simulated concrete Pore solution”, Chem. Sci. Trans.,2(2), 605-613. [26] Abdulrasoul Salih Mahdi “ Urea as a Corrosion inhibitors for Reinforced Steel in Simulated Chloride Contaminated Concrete Pore Solution, IJARET, Vol 5(5) 2014 3039. [27]

R.Epshiba, A.Peter Pascal Regis and S.Rajendran, Int. J. Nano. Corr. Sci. Engg. 1(1) (2014) 1-11.

[28] N. Kavitha and P. Manjula , Int. J. Nano. Corr. Sci. Engg. 1(1) (2014) 31-38. [29] R. Nagalakshmi , L. Nagarajan , R.Joseph Rathish , S. Santhana Prabha , N. Vijaya , J. Jeyasundari and S. Rajendran , Int. J. Nano. Corr. Sci. Engg. 1(1) (2014) 39-49. [30] J. Angelin Thangakani, S. Rajendran ,J. Sathiabama , R M Joany , R Joseph Rathis , S Santhana Prabha , Int. J. Nano. Corr. Sci. Engg. 1(1) (2014) 50-62. [31] A. Nithya , P.Shanthy, N.Vijaya, R.Joseph Rathish, S.Santhana Prabha, RM Joany and S. Rajendran, Int. J. Nano Corr. Sci. Engg. 2(1) (2015)1-11. [32] J. Sathiabama, Susai Rajendran, and J. Arockia Selvi, “Eriochrome Black T as Corrosion Inhibitor for Carbon Steel in Well Water”, Bulletin of Electrochemistry, 22 (2006) 363. [33] Susai Rajendran, M. Manivannan, J. Wilson Sahayaraj, J. Arockia Selvi, J. Sathiabama, A. John Amalraj, and N. Palaniswamy, “Corrosion Behavior of Aluminium in Methyl Orange Solution at pH 11”, Trans. SAEST, 41 (2006) 63.

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S.Rajendran et al.,

Received: 10-02-2016 Accepted: 20-03-2016

33


Available Online http://www.ijncse.com ISSN Online: 2395-7018

3(1) (2016) 34-47

BIODIESEL PRODUCTION FROM MAHUA (MADHUCA INDICA) S. Guharaja, S. DhakshinaMoorthy, Z. Inamul Hasan*, B. Arun, J. Irshad Ahamed and J. Azarudheen Department of Mechanical Engineering, M.I.E.T Engineering College, Tiruchirappalli, Tamil Nadu, India. Corresponding author: Z. Inamul Hasan Email- [email protected]

ABSTRACT The present day internal combustion engines are operating essentially on petroleum based fuels, which are non- renewable in nature and lead to depletion in short period due to its indiscriminate use in different fuels. Renewable agriculture based, non- edible oils like pongamia, mahua (Maduca Indica), neem, jatropha oils etc. can be used as an alternative fuel in CI engines. Biodiesel production from Mahua seed was experimentally investigated in the present study. Expeller method was employed to extract mahua oil from its seed and was subjected to two stage transesterification due to the presence of more than 18% of free fatty acid content. In the primary stage, the FFA content was reduced to less than 2% by acid esterification using concentrated H2SO4 and methanol and followed by base catalyzed transesterification to convert the mahua oil into biodiesel. The properties like density, viscosity, and Calorific value, flash and fire point were analyzed and compared with other prominent biodiesel. GC/MS and FT-IR analysis were also studied to identify and confirm the presence of fatty acid methyl esters. Keywords: Maduca Indica, Transesterification, Free Fatty Acid. 34


INTRODUCTION Biodiesel fuel can be made from new or used vegetable, non edible oils and animal fats which are nontoxic, biodegradable, renewable resources. Fats and oils are chemically reacted with an alcohol (methanol is the usual choice) to produce chemical compounds known as Fatty Acid Methyl Esters. Biodiesel is the name given to these esters when they are intended for use as fuel. Glycerol is produced as a co-product which is used in pharmaceuticals and cosmetics, among other markets. There are three basic routes to ester production from oils and fats: i. ii. iii.

Base catalyzed transesterification of the oil with alcohol. Direct acid catalyzed esterification of the oil with methanol. Conversion of the oil to fatty acids, and then to alkyl esters with acid catalysis.

The majority of the alkyl esters produced today is done with the base catalyzed reactor because it is the most economic for several reasons: i. ii. iii. iv.

Low temperature (150˚F) and pressure (20 psi) processing. High conversion (98%) with minimal side reactions and reaction time. Direct conversion to methyl ester with no intermediate steps. Exotic materials of construction are not necessary.

Biodiesel is produced from oils by converting the triglyceride oils to methyl or ethyl esters with a process known as transesterification. The transesterification process reacts alcohol with the oil to release three “ester chains” from the glycerine backbone of each triglyceride. The reaction requires heat and a strong base catalyst (e.g., sodium or potassium hydroxide which has already been mixed with the methanol), to achieve complete conversion of the oil into the separated esters and glycerine.

35


Figure 1. Production of Biodiesel The methanol is charged in excess to assist in quick conversion and recovered for reuse. The glycerine can be further purified for scale to the pharmaceutical and cosmetic industries. The mono-alkyl esters become the Biodiesel, with one-eighth the viscosity of the original oil. Each ester chain, usually 18 carbons in length for soy esters, retains two oxygen atoms forming the “ester” and giving the product its unique combustion qualities as an oxygenated based fuel. Biodiesel is nearly 10% oxygen by weight. Use of biodiesel in a conventional diesel engine will result in substantial reduction of unburnt hydrocarbons, carbon monoxide and particulate matter. Biodiesel reduces emission of carbon monoxide (CO) by approximately 50% and carbon dioxide by 78.8% on a net lifecycle basis because the carbon in biodiesel emissions is recycled from carbon that was already in the atmosphere, rather than being new carbon from petroleum that was sequestered in the earth crust. Since biodiesel is made entirely from edible and non edible oils, it does not contain any sulphur, aromatic hydrocarbon, metals or crude oil residues. The absence of sulphur means a reduction in the formation of acid rain by sulphate emissions which generate sulphuric acid in our atmosphere. The reduced sulphur in the blend will also decrease the levels of corrosive sulphuric acid accumulating in the engine crankcase oil over time [1]. About Mahua oil seed The general morphology of the oil plant and their seeds, the availability and combustion characteristics like density, viscosity, flash point and fire point, cetane number and calorific value of mahua oil and its blends with diesel oil under test are presented. The world’s rapidly dwindling petroleum supply, their raising cost and the growing danger of environmental 36


pollution from these fuels have led to an intensive search of alternative fuels. The use of Mahua oil (Madhuca Indica) as diesel substitute in compression ignition engine has now gained greater importance because of their large population and phenomenal growth rate. Mahua oil can easily be substituted for hydrocarbons which are scarce worldwide, and save the countries cores of rupees in foreign exchange. It is therefore necessary to develop some means for improving the fuel economy of compression ignition engines and also to investigate the suitability of Mahua oil for diesel engine operations. If the diesel engine could be fuelled on a cleaner fuel such as honge oil, Mahua oil, it may well be the most desirable engine of the future. The present researchers considered among several non edible seed oils, Mahua oil is considered because of following reasons [2, 3], a) These are non edible type oils. b) These trees are indigenous to India, grow even in drought prone area and found abundantly in all parts of India. c) These oils can be easily substituted for petroleum based Hydro Carbon fuels that are becoming extinct. They have assured greater importance because of their large availability and potential growth with age. In India at present theoretical potential of oils is estimated to 4, 00,000 tons per year for Mahua oil [4]. .

Figure 2. Mahua flowers, tree and seeds.

Mahua oil is obtained from the kernel of mahua seed (Madhuca Indica) and contains 50-55% oil.

37


TABLE 1

Kingdom Division Class Order Family Genus Species

Scientific Classification Of Mahua Plantae Mangnoliaphyta Magnoliopsida Ericolos Sapotaceae Madhuca Indica, Longifolia

To reduce the viscosity, various methods can be employed namely heating, thermal cracking, pyrolysis, dilution and Transesterification [5]. Generally Mahua oil biodiesel was obtained by employing two stage transesterification with Acid/base catalyst, biocatalyst and supercritical Methanolysis process. The two stage transesterification process comprises of primarily Acid esterification to reduce the Free Fatty Acid contents and base catalyzed esterification to convert the vegetable oil into Fatty Acid Methyl ester [6, 7]. In the present study, mahua seed was used to extract mahua oil by expeller process. A two step transesterification process was employed comprising of acid catalyzed esterification and base catalyzed esterification to convert mahua oil with higher FFA content into its corresponding biodiesel. During the transesterification reaction, Sodium hydroxide and methanol were mixed to form sodium methoxide for the production of Mahua Oil Methyl Esters. The fatty acid methyl esters were subjected to Gas chromatography/Mass Spectrometry analysis and Fourier Transform Infrared technique to identify the various FAMEs present in it. The physio chemical properties of mahua oil biodiesel was also analyzed and found within ASTM standards. An optimization study was also conducted by varying parameters like Molar ratio, reaction time, Reaction temperature and quantity of Methanol and Sodium hydroxide [8]. MATERIALS AND METHODS The Mahua seeds were collected and maintained with less than 6% of moisture. Expeller process was used to extract mahua oil at the quantity of 350 ml per kg of mahua seed. It was found that the free fatty acid content was about 18% by titration method. The properties of raw Mahua oil and Mahua biodiesel were determined and can be seen in Table 2 and 3 and the pictorial view of raw Mahua oil extracted and Mahua biodiesel can be seen in Fig (4). A two stage esterification process was employed with Acid esterification followed by base catalyzed esterification. The pretreatment and Transesterification experiments were conducted in laboratory conditions which consisted of 1000 cc inverted neck flask with air tight conditions. The reaction environment was maintained between room temperature and 65°C with 5% Concentrated Sulphuric acid and 0.36 v/v methanol to oil ratio. The reactant 38


mixture was continuously stirred at 450 rpm for about 90 minutes with an interval of 15 minutes. The acid value was continuously monitored at these intervals by titration method till the optimum value was achieved. The pre-treatment process was followed by base catalyzed reaction in which a molar ratio of 1:6 (oil to methanol molar ratio) was employed.0.8% (w/w of Sodium hydroxide to oil) was used as a catalyst to treat and neutralize the fatty acids [9, 10].

Figure 3. Transesterification reaction of Mahua oil Biodiesel

Figure4. Comparison of Raw Mahua oil (A) with transesterified Mahua oil biodiesel (B)

39


Table 2: Comparison of Physio-Chemical Properties of Raw Mahua oil with diesel and vegetable oil Properties Density at 15oC(Kg/m3) Kinematic viscosity at 40oC (mm2/s) Calorific value (MJ/Kg) Flash point (oC)

ASTM D6751

Straight Diesel

Mahua Oil

Jatropha Oil

Rubber Seed Oil

860-900

839

955

912

910

1.9-6.0

3.18

24.58

8.72

66.2

---

44.8

36

40

37.5

Min 130

68

232

125

198

0.1

3.7

---

---

Carbon residue (%) Ash content (%)

1 suggest a synergistic effect. SI approaches 1 when no interaction exists between the inhibitor compounds. In case of SI < 1, the negative interaction of inhibitors prevails (i.e., corrosion rate increases). Synergism parameter is calculated using the relation. SI = (1-I1+2)/(1-I'1+2) where I1 is the surface coverage of inhibitor (PPA), I2is the surface coverage of inhibitor (Zn2+) and I'1+2is the combined surface coverage of inhibitors (PPA) and (Zn2+).

3.2. Potentiodynamic Polarization Study Polarization study has been used to detect the formation of protective film on the metal surface [21,22]. The polarization curves of carbon steel immersed in various test solutions are shown in Fig 1. It shows that there is a clear reduction of both anodic and cathodic currents in the presence of PPA Zn2+compared with those for the blank solution. Hence, it is clear that the cathodic reaction (oxygen reduction) and the anodic reaction (iron dissolution) were inhibited. The electrochemical parameters such as corrosion potential (Ecorr), Tafel slopes (anodic slope ba and cathodic slope bc), linear polarization resistance (LPR) and corrosion current (Icorr) values are given in Table 6.

Table 6.Analysis of potentiodynamic polarization study

System Sea water Sea water + 250 ppm PPA + 50 ppm Zn2+

Ecorr

bc

(mV vs SCE) (mV/dec)

ba

LPR

Icorr

(mV/dec)

(Ω cm2)

(A/cm2)

– 726

125.5

162.3

1.0756 × 10-4

3.80 × 10-4

– 789

156.7

183.0

1.6086 × 10-4

2.90 × 10-4

Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 86

Synergistic corrosion inhibition ….by propyl phosphonic acid - Zn2+ system

SK Selvaraj et al.,

When carbon steel is immersed in seawater, the corrosion potential is -726 mV vs SCE. The formulation consisting of 250 ppm PPA + 50 ppm Zn2+ shifts the corrosion potential to -789 mV Vs SCE. It shows that the corrosion potential is shifted to more negative side. This indicates that the cathodic reaction is controlled predominantly.

Fig.1.Polarization curves of carbon steel immersed in various test solutions (a). Sea water

(b). Sea water + 250 ppm PPA + 50 ppm Zn2+

The corrosion current density value and LPR value for seawater are 1.0756×10-4 Ω cm2 and 1.6086×10-4 Ωcm2. For the formulation of 250 ppm PPA and 50 ppm Zn2+, the corrosion current density value has decreased to 2.90×10-4 A/cm2 and the LPR value has increased to 1.6086×10-4 Ωcm2. The fact that the LPR value increases with decrease in corrosion current density indicates adsorption of the inhibitor on the metal surface to block the active sites and inhibit corrosion and reduce the corrosion rate with the formation of a protective film on the metal surface.

3.3. Fourier Transform Infrared Spectra (FT-IR) FT-IR spectra have been used to analyze the protective film found on the metal surface [25,26]. The FTIR spectrum (KBr) of pure PPA is shown in Fig.2a. The P-O stretching frequency appears at 1148 cm-1. The FTIR spectrum of the film formed on the Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 87


SK Selvaraj et al.,

metal surface after immersion in seawater containing 250 ppm of PPA and 50 ppm of Zn2+is shown in Fig. 2b. The P-O stretching frequency has shifted from 1148 to 1190 cm-1. It is inferred that oxygen atom of the phosphonate group has coordinated with Fe2+ resulting in the formation of Fe2+ - PPA complex formed on the anodic sites of the metal surface. The peak at 3432 cm-1 is due to OH stretching. The band due to ZnO appears at 1369 cm-1. These results confirm the presence of Zn(OH)2 deposited on the cathodic sites of the metal surface. Thus, FT-IR spectral study leads to the conclusion that the protective film consists of Fe2+ - PPA complex and Zn(OH)2.

Fig.2. FT-IR spectra of (a). Pure PPA (b). Surface film 3.4. Scanning electron microscopy (SEM) The scanning electron micrographs of carbon steel are shown in Fig 3. The SEM micrograph of polished carbon steel surface (control) is shown in Fig 3a. This shows the smoothness of the metal surface. This implies the absence of any corrosion product formed on the metal surface. The SEM micrograph of carbon steel immersed in seawater is shown in Fig 3b. This shows the roughness of the metal surface by the corrosive environment and the porous layer of corrosion product is present. Pits are observed on the metal surface. Fig 4c shows that the presence of 250 ppm of PPA and 50 ppm of Zn2+ in seawater gives the formation of thick films on the carbon steel surface. This may be interpreted as due to the adsorption of the inhibitor on the metal surface incorporating into the passive film in order to Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 88


SK Selvaraj et al.,

block the active site present on the carbon steel surface.[27-28]

Fig.3. SEM images of carbon steel surface (a). Polished metal (b). Sea water (c) Sea water+ 50 ppm of Zn2+ + 250 ppm PPA

3.5. Energy Dispersive X-ray Analysis (EDAX) The energy dispersive spectroscopy (EDAX) of polished carbon steel (control) in figure 4a shows its composition. The EDAX spectrum of sea water environment is shown in figure 4b. This indicates the presence of C, Co, Mn and Fe along with Chloride on the metal surface The EDAX spectrum of film formed on the surface of carbon steel after immersion in sea water environment containing 250 pm of PPA and 50 pm of Zn2+ is shown in figure 4c. This proves that the presence of phosphorous, Zinc and oxygen atom of above mentioned Inhibitor system along with compositon of carbon steel. This indicates that oxygen atom of functional group of PPA has cordinated with Fe2+, resulting in the formation of Fe2+ - PPA complex on the anodic sites of metal surface and Zn(OH)2 formed on the cathodic sites of metal surface[29].



SK Selvaraj et al.,

Fig.4. EDAX images of carbon steel surface (a). Polished carbon steel

(b). Sea water

(c). Sea water + 50 ppm Zn2+ + 250 ppm PPA

3.6. Atomic Force Microscopy (AFM) The value of Ra , Rq and P-V height for the polished carbon steel surface (reference sample) are 3.99 nm, 3.26 nm and 34.23 nm respectively, which shows a more homogeneous surface, with some places in where the height is lower than the average depth. Figure 5a display the non-corroded metal surface. The slight roughness observed on the polished carbon steel surface is due to atmospheric corrosion. The average roughness, rms roughness and P-V height values for the carbon steel surface immersed in sea water environment are 38.9 nm, 28.8 nm and 181.8 respectively. These data suggests that carbon steel surface immersed in sea water environment has a greater surface roughness than the polished metal surface, which shows that the unprotected carbon steel surface is rougher and was due to the corrosion of carbon steel. Figure 5b displays corroded metal surface with few pits. The presence of 250 ppm of PPA, 50 ppm of Zn2+ in sea water environment in figure 5c reduces the Rq from 38.9 Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 90


SK Selvaraj et al.,

nm to 30 nm and the average roughness is significantly reduced to 28.8 nm when compared with 3.26 nm of carbon steel surface immersed in sea water[30].

Fig.5. 2D &3D AFM images of carbon steel surface (a).Polished carbon steel (b) Sea water ( c). Sea water + 50 ppm Zn2+ + 250 ppm PPA

Table.8. AFM parameters in different environments Root-mean- square

Average

Maximum peak-to

Roughness (nm)

Roughness (nm)

valley height (nm)

a) Polished carbon steel

3.99

3.26

34.23

b) Sea water

38.9

28.8

181.8

30

19.21

69.52

Environment

c) Sea water+ 50 ppm Zn2+ + 250 ppm PPA



SK Selvaraj et al.,

3.7. Mechanism of corrosion inhibition In order to explain the above results, the following mechanism of corrosion inhibition is proposed: When carbon steel is immersed in sea water, the anodic reaction is, Fe → Fe2+ + 2eThe corresponding cathodic reaction is reduction of oxygen to hydroxyl ions, O2 + 2H2O + 4e- → 4OHWhen the formulation consists of 250 ppm of PPA and 50 ppm Zn2+ in seawater, there is formation of PPA – Zn2+ complex in solution. When carbon steel is immersed in this environment, the PPA – Zn2+ complex diffuses from the bulk of the solution to the metal surface. The PPA – Zn2+ complex is converted into PPA Fe2+ complex on the anodic sites of the metal surface, the stability of Fe2+ – PPA complex is higher than the corresponding Zinc complex. Zn2+ – PPA + Fe2+ → Fe2+ – PPA + Zn2+ The released Zn2+ combines with OH- to form Zn(OH)2 on the cathodic sites of the metal surface. Zn2+ + 2OH- → Zn(OH)2 The protective nature of the film is due to the presence of metal inhibitor complex and Zinc hydroxide. Formation of the metal inhibitor complex fills the pores of the otherwise porous film and makes it a protective film. Thus, the protective film consists of Fe2+ – PPA complex and Zn(OH)2. 4. CONCLUSION Synergistic effect exists between the propyl phosphonic acid - Zn2+ system in controlling the corrosion of carbon steel immersed in sea water in the absence and presence of Zn2+. The formulation consisting of 250 ppm propyl phosphonic acid, 50 ppm of Zn2+ have 98% inhibition efficiency, A more stable and compact protective film formed on the metal surface. Polarization study reveals that the propyl phosphonic acid - Zn2+ system function as cathodic inhibitor and there is increase in LPR value and decrease in corrosion current [ 3137]. The FT-IR, SEM, EDAX and AFM analysis reveal that the protective film is formed on the metal surface. Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 92


SK Selvaraj et al.,

REFERENCES [1] D. Pletcher, F.C. Walsh, “Industrial Electrochemistry”, Chapman and Hall (1993). [2] L.L. Shreeir, R.A. Jarman, G.T. Burstein, “Corrosion and Corrosion control”, Vol. I, II, Butterworth-Heinemann, London (1976). [3] R. Winston Revie, “Uhlig’s Corrosion Hand Book”, 2nd Edition, John Wiley & Sons, INC (2000). [4] O. Riggs Jr., “Theoretical Aspects of Corrosion Inhibitors and Inhibition”, NACE, Houston, Texas (1974). [5] M.G. Fontana and N.D. Greene, “Corrosion Engineering”, McGraw Hill, New York (1978). [6] G. Wranglen, “An Introduction to Corrosion and Protection of Metals” Chapman and Hall, New York (1985). [7] L.L. Shreir, R.A. Jarman, G.T. Burstein, Butterworth-Heinemann. Corrosion 3rd Edition, Vol. 1, p. 6 (1994). [8] S.S. Dara, A Text book in Engineering Chemistry, John Wiley and Sons, New York, pp.183-220, 4th Ed., (1986). [9] Rajnarayan. An Introduction to metallic corrosion and its prevention, Oxford and IBH Publishing Co. Pvt. Ltd., New Delhi, pp.436-612, (1988). [10] H.H. Uhlig and R. Winston, “Corrosion and Corrosion Control” John Wiley and Sons, (1985). [11] M. Yamashita, H. Konishi, T. Kozakura, J. Mizuki and H. Uchidak, Corrosion Science, 47 (2000) 2492 [12] S. Rajendran, B.V. Apparao and N. Palaniswamy, Bulletin of Electrochemistry, 17 (2001) 171. [13] J.M. Yeh, C.L. Chen, Y.C. Chen, C.Y. Ma, K.M. Lee, Y. Wei and S.X. Li, Polymer, 43 (2002) 2729. [14] J.J. Olaya, S.E. Rodil, S. Muhl and E. Sanchez, Journal of Thin Solid Films, 474 (2005) 119. Int J Nano Corr Sci and Engg 3(1) (2016) 79-95 Editors: Prof S Rajendran , M Pandiarajan and P Nithya Devi 93


SK Selvaraj et al.,

[15] J.N. Putilova, S.A. Belezin and V.P. Barannik, “Metallic Corrosion Inhibitors”, Pergamon Press, London (1960). [16] J.R. Deans, S.Q. Richard Derby, V.D. Burrche, Materials Performance, 20 (1981) 47. [17] K.C. Sharma, Proceedings of Second National Conference on Corrosion and its Control, Organised by SAEST, Calcutta, India, 19-21 Dec. (1979) 2. [18] F.N. Spellar, Discussion, Proc. ASTM, 36(2), 695, 1936. [19] W.G.Y. Palmer, Corrosion, 7 (1957) 10. [20] Y.J. Qian, S. Turgoose, Br. Corros. J., 22 (1987) 268 [21] S. Syed Azim, S. Muralidharan, S. Venkatakrishna Iyer, J. Appl. Electrochem, 25 (1995) 495. [22] S. Rajendran, B. V. Appa Rao and N. Palaniswamy, Anti-Corros. Methods and Mater. 45 (1998) 397 [23] S. Ramesh, S. Rajeswari, Electrochimica Acta, 49 (2004) 811. [24] S. Rajendran, B.V. Appa Rao, N. Palaniswamy, V. Perisamy, G. Karthikeyan, Corrosion Science, 43 (2001) 1345 [25] B.V. Appa Rao, S. Srinivasa Rao, Res. J1 (20. Recent. Sci, 12) 93. [26] M. R. Laamari, J. Benzakour, F. Berrekhis, M. Bakasse, D. Villemini, J. Mater. Environ. Sci, 3 (3) (2012) 485. [27] B.V. Appa Rao, M. Venkateswara Rao, S. Srinivasa Rao, B. Sreedhar, Journal of Surface Engineered Materials and Advanced Technology, 3 (2013) 28. [28] A. Sahaya Raja, S. Rajendran, R. Nagalakshmi, J. AngelinThangakani, M. Pandiarajan, Eur. Chem. Bull, 2(3) (2013) 130 [29] S. Gowri, J. Sathiyabama, P. Prabhakar, S. Rajendran, International Journal of Research in Chemistry and Environment, 3 (2013) 156. [30] A. R. Hoseinzadeh, I. Danaee, M. H. Maddahy, M. Rashvand Avei, Chemical Engineering Communications, 201 (2014) 380 [31] Angelin Thangakani, J.; Rajendran, S.; Sathiabama, J.; Joany,R M.; Joseph Rathis, R.; Santhana Prabha, S., Int. J. Nano. Corr. Sci. Engg., 2014, 1(1), 50 .



SK Selvaraj et al.,

[32] Christy Catherine Mary, A.; Maria Joany, R.; Rajendran, S.; Hameed Al-Hashem, Krishnaveni, A.; Vikasini, S.; Int. J. Nano. Corr. Sci. Engg., 2 (4) (2015) 50e57. [33] Nithya Devi, P.; Sathiyabama, J.; Rajendran, S.; Joseph Rathish, R., Santhana Prabha, S., Int. J. Nano. Corr. Sci. Engg., 2015, 2(3), 1. [34] Namita, K.; Johar Bhrara Epshiba, K.; Singh, G.; Int. J. Nano. Corr. Sci. Eng. 2015, 2(1). [35] Sahaya

Raja,

A.;

Rajendran,S.;

Sathiyabama,

J.;

Prathipa,V.;

Anuradha,

S.;Krishnaveni, A.; Jeyasundari, J.; Int. J. Nano. Corr. Sci. Engg. 2015, 2(2), 31. [36] Johnsirani.V.;

Rajendran, S.; Christy Catherine Mary, A.; Joseph Rathish,

R.;Umasankareswari, T.; Jeyasundari, J.; Int. JNano.Corr. Sci. Engg., 2015, 2 (3), 22. [37] Sangeetha, M., Rajendran, S.; Sathiyabama , J.; Umasankareswari,T.; Krishnaveni, A.; Joany, R.M.; Int. J. Nano. Corr. Sci. Engg., 2015, 2(3), 14. Received: 25-03- 2016 Accepted: 30-03-2016


Inhibition of corrosion … thiomalic acid - Zn2+ system

SK Selvaraj et al.,


ISSN Online: 2395-7018 3(1)(2016)96-109

INHIBITION OF CORROSION OF CARBON STEEL IN SEA WATER BY THIOMALIC ACID - Zn2+ SYSTEM S. K. Selvaraj[a], A. John Amalraj[b]*, V. Dharmalingam[b], J. Wilson Sahayaraj[c]

[a] PG and Research Department of Chemistry, G.T.N Arts. College, Dindigul - 624005, Tamil Nadu, India. [b] PG and Research Department of Chemistry, Periyar E.V.R College (A), Tiruchirappalli - 620023, Tamil Nadu, India . [c] Department of Chemistry, Jepiar Enginering College, Chennai- 600019, Tamil Nadu, India. ABSTRACT The synergistic effect has been studied in the presence of a dicarboxylic acid inhibitor with or without bivalent cation like zinc ions. A protective film has been formed on the carbon steel surface in aqueous solution using a synergistic combination of an environmentally friendly dicarboxylic acid (thiomalic acid) and zinc ions. The corrosion inhibition effect of thiomalic acid with zinc ions on carbon steel has been carried out by weightloss studies and electrochemical techniques. Potentiodynamic polarization studies reveal that the inhibitor system is of an anodic type. . Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to investigate the nature of protective film formed on the carbon steel surface and for explaining the mechanistic aspects of the inhibition process. Keywords: Thiomalic acid, corrosion inhibition, carbon steel, FT-IR and SEM.

96



SK Selvaraj et al.,

1. INTRODUCTION Because of its good mechanical properties, availability and relatively reasonable cost carbon steel is the most worldwide used material for industrial and domestic applications. Several techniques have been applied in order to reduce the corrosion of metals. The use of inhibitors was one of the most practical and efficient methods for protection against corrosion[1]. Corrosion inhibitors are substances added in very small concentrations that they effectively reduce the corrosion rate[2]. Generally, organic compounds having heteroatom O, N, P and S are

found

to

have

basicity

and

electron

density,

thus

assist

in

corrosion

inhibition[3].Compounds with functional groups containing hetero-atoms which can donate a lone pair of electrons are found to be useful as corrosion inhibitors for metals[4-5]. These compounds are still continuously investigated as inhibitors for corrosion of metals in industry. The selection criteria for various inhibitors include low concentration, more adherence to environmental regulations, environmental friendliness and cost effectiveness. Carboxylic and dicarboxylic acids and salts thereof are very widely used as corrosion inhibiting agents and has been the subject of variousworkers[6]. An inexpensive way to protect the metals from corrosion is by using carboxylic acids. Carboxylic acid derivatives alone or both with other additives can effectively inhibit the corrosion of metals. One of the most important effects in inhibition process that serves as the basis for most of the modern corrosion inhibiting formulations is synergism[7].Synergistic effect existing among dicarboxylic acids and Zn2+on the inhibition of corrosion of metals has been studied by various workers[8-9].

An organic compound namely dicarboxylic acid was investigated as a corrosion inhibitor for carbon steel in this study. The inhibitive properties and synergistic effect with an organic compound viz., Thiomalic acid (TMA) and Zn2+ ions in controlling the corrosion of carbon steel was studied in sea water using weightloss method and electrochemical methods viz., potentiodynamic polarization. Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM)were used to analyse the protective film formed on the carbon steel surface and a suitable mechanism of corrosion inhibition is proposed[10-14].

97



SK Selvaraj et al.,

2. EXPERIMENTAL 2.1. Preparation of Specimen Carbon steel (0.026%S, 0.06%P, 0.4%Mn, 0.1% C, and the rest Fe) specimen of dimension 1cm × 4cm × 0.2cm were used for weight loss study. Carbon steel rod of the same composition, encapsulated in Teflon was polished to a mirror finish and degreased with trichloroethylene. Preparation of Stock solution is given in Table1. Table: 1 Preparation of Stock Solution CTAB Solution Sl. No.

ml

Thiomalic acid (TMA)

ZnSO4 solution

Total Volume made up with distilled water

ppm

ml

ppm

ml

Zn2+ (ppm)

ml

1.

1

100

0.5

50

1

10

100

2.

2

200

1

100

5

50

100

3.

3

300

2

200

10

100

100

4.

4

400

3

300

15

150

100

5.

5

500

4

400

20

200

-

2.2 Preparation of Thiomalic acid 1g of Thiomalic acid (TMA) was dissolved in distilled water and made up to 100 ml.

Figure 1. Structure of Thiomalic acid

2.3. Weight-Loss Method

98



SK Selvaraj et al.,

Two carbon steel specimens were immersed in 100 ml of test solution containing various concentrations of the inhibitors in the absence and presence of Zn2+ ions, for a period of three days. After exposure corrosion product were removed with Clarke’s solution, and the weight of the specimens before and after immersion were determined using a metler balance. 2.4. Corrosion Inhibition Efficiency Corrosion inhibition efficiency was calculated using the equation:

where W1= Corrosion rate in the absence of inhibitor, W2= Corrosion rate in the presence of inhibitor. 2.5. Surface Examination The carbon steel specimens were immersed in various test solutions for a period of one day, taken out and dried. The nature of the film formed on the surface of metal specimens was analysed by FTIR spectroscopic study. 2.6. FT-IR Spectra FT-IR spectra were recorded in a Perkin – Elmer 1600 spectrophotometer. The film was carefully removed, mixed thoroughly with KBr made in to pellets and FTIR spectra were recorded. 2.7. Potentiodyanmic Polarization Polarization studies were carried out in an H&CH electrochemical work station impedance analyser model CHI 660A. a three electrode cell assembly was used. The working electrode was carbon steel. A saturated calomel electrode (SCE) was used as the reference electrode and a rectangular platinum foil was used as the counter electrode. 3. RESULTS AND DISCUSSION 3.1. Weight Loss Study The corrosion rates of carbon steel immersed in various test solution for a period of one day are presented in the table 2. Synergistic Effect of Thiomalic Acid – Zn2+ System

99



SK Selvaraj et al.,

Table 2 Inhibition Efficiencies (IE%) and corrosion rates (CR) Obtained from TMA-Zn2+ systems when carbon steel immersed in Sea water. Inhibitor system: TMA-Zn2+

Immersion period: 1 day

Zn2+= 0 ppm CR IE% (mmpy) 0.1136

TMA (ppm) 0

Zn2+ = 25 ppm CR IE% (mmpy) 18 0.0996

Zn2+ = 50 ppm CR IE% (mmpy) 22 0.0897

50

13

0.0987

57

0.0779

65

0.0710

100

15

0.0964

68

0.0692

74

0.0586

150

17

0.0933

74

0.0586

79

0.0501

200

26

0.0836

78

0.0510

88

0.0192

250

33

0.0762

80

0.0486

96

0.0035

The calculated inhibition efficiencies of carbon steel immersed in Sea water, for a period of one day in the absence and presence of Zn2+ ion are given in table 2. the calculated value indicates the ability of TMA to be a good corrosion inhibitor. the IE is found to be enhanced in the presence of Zn2+ ion. TMA alone shows some IE. But the combination of 250 ppm TMA and 50 ppm Zn2+ shows 96% IE. this suggests a synergistic effect exists between TMA and Zn2+[15-16]. Influence of Immersion Period on IE of TMA-Zn2+ System Table 3 Influence of immersion period (IP) on IE of TMA (250ppm) - Zn2+ (50ppm) system System Sea water CR (mmpy) Sea water 2+ Zn (50ppm); CR (mmpy)

+

TMA(250ppm)

IE %

Immersion period (days) 1 3 5 7 0.1030 0.1124 0.1197 0.1247 + 0.0035

96

0.0189

0.0224

0.0486

89

84

80

100



SK Selvaraj et al.,

The influence of immersion period on the IE of TMA (250ppm) – Zn2+ (50ppm) system is given in table 3 is found that as the IP increases, the IE decreases. This due to the fact as the IP increases the protective film formed on the metal surface is unable to withstand the continuous attack of corrosive ions such as chloride present in Sea water.

There is a

competition between two processes, namely, formation of FeCl2 (and also FeCl2) and Fe2+TMA complex on the anodic sites of the metal surface. It appears that the formation of iron chlorides is more favoured than the formation of Fe2+-TMA complex film formed on the metal surface is converted into iron chlorides which go into solution and hence, the IE decreases as the IP increases. Influence of N-cetyl-N,N,N-trimethyl ammonium bromide(CTAB) on Inhibition Efficiency of TMA-Zn2+ System Table 4 Influence of CTAB on inhibition efficiency (IE%) of carbon steel immersed in Sea water TMA Zn2+ CTAB Ppm ppm ppm 0 0 0 250 50 0 250 50 50 250 50 100 250 50 150 250 50 200 250 50 250 CTAB is a cationic surfactant. It is a biocide. The IE

CR IE% mmpy 0.1136 0.0045 94 0.0035 96 0.0035 96 0.0033 100 0.0031 100 0.0032 100 and biocidal efficiency (BE) of TMA-

Zn2+ CTAB system is given here it is observed from the results that 50 ppm of CTAB in combination with TMA-Zn2+ system has increased IE from 94% to 96%. However, a decrease in IE of TMA-Zn2+ System is noticed when the CTAB concentration increases from 100 ppm to 250 ppm. This is due to the formation of micelles at higher concentration of surfactant. 3.2. Analysis of Polarization Curves for TMA-Zn2+ System Table 5 The potentiodynamic polarization curves of carbon steel immersed in sea water in the absence and presence of inhibitor system obtained from potentiodynamic polarization study.

101



Ecorr

ba

SK Selvaraj et al.,

bc

Icorr

mV/decade mV/decade mV/decade

LPR ohm cm2

A/cm2

Description Sea Water

-962

156

253

1.070 x 105

1.561 x 10-4

Sea Water + 50 ppm Zn2+ + 250 ppm TMA

-630

961

953

1.514 x 106

7.481x 10-6

Fig. 2. Potentiodynamic polarization curves of carbon steel in various test solution a) Sea Water b) Sea Water + 50 ppm Zn2+ + 250 ppm TMA

The calculated corrosion parameters such as corrosion potential (Ecorr), Tafel slopes (anodic slope ba and cathodic slope bc), linear polarization resistance (LPR) and corrosion current (Icorr) values are given in Table 5. When carbon steel is immersed in Sea water the corrosion potential is -962 mV vs saturated calomel electrode (SCE).

The corrosion current is

1.561×10-4 A/cm2. When TMA (250 ppm) and Zn2+ (50 ppm) are added to the above system the corrosion potential is shifted to the anodic side from -962 mV to -630 mV. This suggests that the anodic reaction is controlled predominantly. Moreover, in presence of the inhibitor system, the corrosion current decreases from 1.561×10-7 A/cm2 to 7.481×10-6 A/cm2 and 102



SK Selvaraj et al.,

LPR value increases from 1.070×105 ohm cm2 to 1.514×106 ohm cm2. These observations indicate the formation of protective film on the metal surface [17-20].

3.4. Surface Analysis The structure of Thiomalic acid is shown in fig 3. It contains C=O and O-H stretching vibrations. The protective film formed on the surface of the metal in the presence of Thiomalic acid system and Thiomalic acid–Zn2+ system in sea water has been analysed by FT-IR spectroscopy.

3.4.1. Analysis of FT-IR Spectra FTIR spectrum (KBr) of pure Thiomalic acid (TMA) is shown in Fig 3 . T he C=O stretching frequency of carboxyl group appears at 1700 cm-1. The O-H stretching frequency of TMA appears at 3180 cm-1and the othe peak S-H at 2559.46 cm-1 . The FTIR spectrum (KBr) of film formed on the surface of metal after immersion in Sea water containing 250 ppm of TMA and 50 ppm of Zn2+ is shown in Fig. 4. The C=O stretching frequency of carboxyl group has shifted from 1700 cm-1 to 1594 cm-1. The O-H stretching frequency of TMA has shifted from 3180 cm-1 to 3425 cm-1. The S-H stretching frequency of TMA has shifted from 2559.46 cm-1 to 2403.32 cm-1 . This indicates that these groups have coordinated with Fe2+, resulting in the formation of Fe2+ -TMA complex on the anodic sites of the metal surface. The peak at 1402 cm-1 is due to Zn(OH)2 formed on the cathodic sites of the metal surface. Thus FTIR spectra study lead to the conclusion that the Fe2+ - TMA complex formed on anodic sites of the metal surface controlled the anodic reaction and Zn(OH)2 formed on the cathodic

sites

of

the

metal

surface

controlling

the

cathodic

reaction[21-24]

103



SK Selvaraj et al.,

Fig.3. FT-IR Spectrum of Pure TMA

Fig. 4. FT-IR Spectrum of Sea Water+250ppm of TMA+50ppm of Zn2+ 3.4.2. Scanning electron microscopy (SEM) The scanning electron micrographs of carbon steel are shown in Fig 5. The SEM micrograph of polished carbon steel surface (control) is shown in Fig 5a. This shows the smoothness of the metal surface. This implies the absence of any corrosion product formed on the metal surface. The SEM micrograph of carbon steel immersed in seawater is shown in Fig 5b. This shows the roughness of the metal surface by the corrosive environment and the porous layer of corrosion product is present. Pits are observed on the metal surface. Fig 5c shows that the presence of 250 ppm of TMA and 50 ppm of Zn2+ in seawater gives the formation of thick films on the carbon steel surface. This may be interpreted as due to the adsorption of the inhibitor on the metal surface incorporating into the passive film in order to block the active site present on the carbon steel surface[25-28]. 104



SK Selvaraj et al.,

Fig. 5. SEM images of carbon steel surface (a). Polished metal (b). Sea water (c) Sea water + 50 ppm of Zn2+ + 250 ppm TMA

3.5. Mechanism of corrosion inhibition The results of weight loss study show that the formulation consists of 250 ppm TMA and 50 ppm Zn2+ has 96% IE, in controlling corrosion of carbon steel in sea water. A synergistic effect exists between TMA and Zn2+. Polarization study reveals that TMA – Zn2+ system functions as anodic inhibitor controlling anodic reaction predominantly and controls anodic reaction to some extent. FTIR spectra reveal that the protective film consists of Fe2+ TMA complex and Zn(OH)2. SEM studies confirm the formation of protective film on the metal surface. The effective synergistic formulation consists of 250 ppm of TMA, 50 ppm of Zn2+ and 50 ppm of CTAB shows IE 98% and 100 % BE. Also the effective synergistic formulation consists of 250 ppm of TMA, 50 ppm of Zn2+ and 50 ppm of CTAB shows IE 96% and 100 % BE. The addition of TMA reduces metal dissolution in an aqueous environment and this may be due to adsorption and complex formation at the metal surface with the combined application of TMA and Zn2+ . Hence the corrosion process is inhibited.

The mechanism can be generalized as follows. When the formulation consists of TMA (250 ppm) and Zn2+ (50 ppm) is added in Sea water there is a formation of TMA – Zn2+ complex in solution. When carbon steel is immersed in this solution, TMA – Zn2+ complex diffuses from 105



SK Selvaraj et al.,

the bulk of the solution towards the metal surface. TMA – Zn2+ complex is converted into TMA – Fe2+ complex on the anodic sites of the metal surface with the release of Zn2+ ion. TMA – Zn2+ + Fe2+ → TMA – Fe2+ + Zn2+ The released Zn2+ combined with OH

–

to form Zn(OH)2 on the cathodic sites of the metal

surface. Zn2+ + 2 OH – → Zn(OH)2 ↓ Thus the protective film consists of TMA – Fe2+ complex and Zn(OH)2. In near neutral aqueous solution, the anodic reaction is the formation of Fe2+. This anodic reaction is controlled by the formation of TMA – Fe2+ on the anodic sites of the metal surface. The cathodic reaction is the generation of OH –. It is controlled by the formation of Zn(OH)2 on the cathodic sites of the metal surface. Fe → Fe2+ + 2 e– (anodic reaction) H2O + ½ O2 + 2 e– → 2 OH– (cathodic reaction) Fe2+ + TMA → TMA – Fe2+ complex Zn2+ + 2 OH– → Zn(OH)2 ↓ This accounts for the synergistic effect of TMA – Zn2+ system. 4. CONCLUSION  The Weight–loss study reveals that the formulation consisting of 50ppm of Zn2+ and 250ppm of TMA has 96% inhibition efficiency, for one-day system and explains the Synergistic effect between TMA and Zn2+ complexes.  The protective film consists of Fe2+ -TMA and Zn(OH)2 is explained by FT-IR spectroscopy.  The results of polarization study show that the anodic reaction is controlled predominantly indicating the reduction of dissolution metal as more Thiomalic acid molecules are transported to the cathodic sites in the presence of Zn2+ ions, which results in increase in LPR values and decrease in corrosion current [29-35].  SEM confirm the presence of a protective film on the metal surface

106



SK Selvaraj et al.,

REFERENCES [1] Kumar S., Sharma D., Yadav P. and Yadav M., Ind. Eng. Chem. Res., 52 (39), 14019– 14029 (2013). [2] Gerengi H., Ind. Eng. Chem. Res., 51, 12835−12843 (2012). [3] Quraishi M.A., Ansari F.A. and Jamal D., Mater. Chem. Phys., 77 (3), 687-690 (2002). [4] Deng S. Li X. and Fu H., Corros. Sci., 53, 822-828 (2011). [5] Labriti B. Dkhireche N. Touir R. Ebn Touhami M. Sfaira M. El Hallaoui A., Hammouti B. and Alami A., Arab. J. Sci. Eng., 37, 1293-1303 (2012). [6] Yoo S.H. Kim Y.W. Chung K. Kim N.K. and Kim J. S., Ind. Eng. Chem. Res., 52 (32), 10880–10889 (2013). [7] Ghareba S. and Omanovic S., Electrochim. Acta., 56, 3890–3898 (2011). [8] Rammelt U. Koehler S. and Reinhard G., Corros. Sci., 53, 3515-3520 (2011). [9] Demadis K.D., Mantzaridis C. and Lykoudis P., Ind. Eng. Chem. Res., 45, 7795-7800 (2006). [10] F. El-Taib Heakal, A.S. Fouda and M.S. Radwan, Mater. Che. and Phy., 125 (2011) 26. [11] F. Zhang, J. Pan and P.M. Claesson, Electrochimica Acta, 56 (2011) 1636. [12] X. Zhou, H. Yang and F. Wang, Electrochimica Acta, 56 (2011) 4268. [13] D.M. Ortega-Toledo, J.G. Gonzalez-Rodriguez, M. Casales, M.A. Neri-Florez and A. Martinez-Villafane, Mater. Che. and Phy., 122 (2010) 485. [14] K. Anuradha, R. Vimala, B. Narayanasamy, J.A. Selvi and S. Rajendran, Chem. Engg. Communi., 195 (2008) 352. [15] C. Thangavelu, M. Umarani, P. Patric Raymond and M. Sekar, Proc. 15thNational Cong. Corr. Control, Chennai, (2010) 59. [16] H. S. Awad and S. Turgoose, British Corr. J., 37 (2002) 147. [17] ATSDR. Toxicological Profile for Chromium (update). U.S. Dept. Healthand Human services, Public Health Service, Atlanta, GA, (2000). [18] S. Ramesh, S. Rajeswari and S. Maruthamuthu, Mater. Lett., 57 (2003) 4547. [19] J.G.N. Thomas, Some New Fundamental Aspects in Corrosion Inhibition: Proc. 5th Euro. Symp. Corr. Inhibitors, Italy, Univ. Ferrara, (1981) 453. [20] B.D. Donnelly, T.C. Downie, R. Grzeskowaik, H.R. Hamburg and D. Short, Corr. Sci., 38 (1997) 109. 107



SK Selvaraj et al.,

[21] A.B. Tadros and Y. Abdel-Naby, J. Electroanal. Chem., 224 (1988) 433. [22] M.A. Pech-Canul and P. Bartolo-Perez, Surf. and Coat.Tech., 184 (2004) 133. [23] A. Alagta, I. Felhosi, J. Telegdi, I. Bertoti and E. Kalman, Corr. Sci., 49 (2007) 2754. [24] J.W. Sahayaraj, P. Raymond, S. Rajendran and

A.J.Amalraj, J. Electrochem. Soc,

56 (2007) 14. [25] T. Umamathi, J.A. Selvi, S.A. Kanimozhi, S. Rajendran and A.J. Amalraj, Indian J. Chem. Tech., 15 (2008) 560. [26] M. R. Laamari, J. Benzakour, F. Berrekhis, M. Bakasse, D. Villemini, J. Mater. Environ. Sci, 3 (3) (2012) 485. [27] B.V. Appa Rao, M. Venkateswara Rao, S. Srinivasa Rao, B. Sreedhar, Journal of Surface Engineered Materials and Advanced Technology, 3 (2013) 28. [28] A. Sahaya Raja, S. Rajendran, R. Nagalakshmi, J. AngelinThangakani, M. Pandiarajan, Eur. Chem. Bull, 2(3) (2013) 130 [29] S. Gowri, J. Sathiyabama, P. Prabhakar, S. Rajendran, International Journal of Research in Chemistry and Environment, 3 (2013) 156. [30] A. R. Hoseinzadeh, I. Danaee, M. H. Maddahy, M. Rashvand Avei, Chemical Engineering Communications, 201 (2014) 380 [31] Angelin Thangakani, J.; Rajendran, S.; Sathiabama, J.; Joany,R M.; Joseph Rathis, R.; Santhana Prabha, S., Int. J. Nano. Corr. Sci. Engg., 2014, 1(1), 50 . [32] Christy Catherine Mary, A.; Maria Joany, R.; Rajendran, S.; Hameed Al-Hashem, Krishnaveni, A.; Vikasini, S.; Int. J. Nano. Corr. Sci. Engg., 2 (4) (2015) 50e57. [33] Nithya Devi, P.;

Sathiyabama, J.; Rajendran, S.; Joseph Rathish, R., Santhana

Prabha, S., Int. J. Nano. Corr. Sci. Engg., 2015, 2(3), 1. [34] Namita, K.; Johar Bhrara Epshiba, K.; Singh, G.; Int. J. Nano. Corr. Sci. Eng. 2015,2 (1) [35] Sahaya Raja, A.; Rajendran,S.; Sathiyabama, J.; Prathipa,V.; Anuradha, S.;Krishnaveni, A.; Jeyasundari, J.; Int. J. Nano. Corr. Sci. Engg. 2015, 2(2), 31.

Received: 25-03-2016 Accepted: 29-03-2016 108



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109



3(1) (2016) 110- 122

AN INVESTIGATION OF FRICTION WELDING PROCESS OF SA213 TUBE TO SA387 TUBE PLATE USING EXTERNAL TOOL A Daniel Das*, Dr. S. Senthil Kumaran 1

PG Scholar, Department of Mechanical Engineering, RVS School of Engineering and Technology, Dindigul - 624005, Tamilnadu, India. 2 Professor & Head, Department of Mechanical Engineering, RVS School of Engineering and Technology, Dindigul - 624005, Tamilnadu, India. Corresponding author: A Daniel Das Email- [email protected] ABSTRACT In this research work, an experimental investigation of Friction Welding of Tube to Tube Plate with External Tool (FWTPET) has been carried out using backing block arrangement with interference fit. The Materials have been used in this research of SA213 tube and SA387 tube plate. The results of the experimental investigation revealed that by employing backing block, FWTPET is capable of producing defect free welds. The Welding sample has been conducted several characteristics such as Compression test, radiographic test and Microscopic Test. Further Taguchi L 9 orthogonal array was utilized to find the most significant control factors which will yield better joint strength. Besides, the contribution of each process parameter has been determined using statistical analysis of variance (ANOVA). The Input and Output values are 1320rpm Speed, 0mm projection, 0.1mm Depth of cut and 3086.90 Mpa optimal joint strength respectively. Keywords: FWTPET, WHO, Interference fit, Taguchi, Anova

110


INTRODUCTION Friction welding is a solid-state joining process and one of the most effective processes for joining similar and dissimilar materials with high joint integrity. The unique feature of friction welding process is that the material that is being welded does not melt and recast. Owing to the intensive heat generated at the interface, the material reaches the softened state which interacts with each other and produces good quality weld .Welding is an important metal fabrication process that has several industrial applications. Friction welding is a solid-state welding process that produces weld due to combined work pieces moving relative to one another so as to generate heat by means of controlled rubbing of faying surfaces. Fusion welding is a generic term for welding processes that rely upon melting to join materials of similar compositions and melting points. Due to the high-temperature phase transitions inherent to these processes, a heat-affected zone is created in the material. Non fusion welding processes accomplish welding by bringing the atoms (or ions or molecules) of the materials to be joined to equilibrium spacing principally, but not exclusively, through plastic deformation due to the application of pressure at temperatures below the melting point of the base material and without the addition of any filler that melts. Friction Welding Tube to Tube Plate using External Tool (FWTPET) is an innovative solid-state joining process in which the material that is being welded does not melt and recast. Due to the absence of parent metal melting, the FWTPET process is observed to offer several advantages over fusion welding such as the absence of solidification crack sand porosity [13]. This was first developed by Dr. S. Senthil Kumaran. He describes that by producing heat using an external tool this welding process will be done. In this research study, FWTPET process has been carried to achieve high-quality leak-proof joints. Major advantages of this process include capability to join dissimilar metals that may not be possible using fusion welding techniques. Joints made by FWTPET process exhibit enhanced mechanical, metallurgical properties with lesser energy consumption the potential application of FWTPET joints includes catch cans in automobile engines, box type heat exchangers, collector with aluminum absorber, aluminum evaporator used in household air conditioners, and solar panel backing. Friction Welding (FRW) is a solid state welding process which produces welds due to the compressive force contact of work pieces which are either rotating or moving relative to one another. Heat is produced due to the friction which displaces material plastically from the faying surfaces. Friction welding of tube to tube plate using an external tool (FWTPET) was invented in the year 2006 and patented by one of the present authors the prime advantage of this process is to weld similar and dissimilar materials which can be of any dimension. The joint produced by this process exhibits enhanced mechanical properties with lesser energy consumption[1-3]. Further we had explained throughout this project. OBJECTIVE Normally conventional friction welding process has been used to join symmetrical shapes and in general friction welding is not suitable to weld tube to tube plate joints. The 111


axial force may either bend the tube or push the tube out of the tube plate and hence it is difficult to achieve required temperature and pressure at the bond interface.   

To study the feasibility of dissimilar material of SA213 tube and SA387 tube plate of FWTPET process by using interference fit with backing block. To Study the behaviour of weld by using different characteristics such as Speed, Projection and Depth of cut To optimize most influencing process parameter by Taguchi method and contribution of each parameters such as speed, projection and depth of cut by ANOVA method

EXPERIMENTAL PROCEDURE An in-house developed FWTPET arrangement used in the present study is shown in Fig. 1. The FWTPET machine configuration consists of a motor, spindle, tool holder, table and supporting structure. We can albe to predefine the rpm of the spindle with our machine.

Fig. 1. FWTPET Machine (Developed Inhouse) The tool used for this process is Tungsten carbide. The tool we used in this research work is Tungsten carbide. The dimension of this tool was 27 m diameter and 170mm in length. Table 1 Tungsten Carbide Configuration E

C

H

Fe

O

Ni

Mo

Ti

V

Pd

Wt%

0.08

0.015

0.25

0.13

0.75

4.31

0.4

4.5

0.20

Initially facing operation is done to make the surface of the tool smooth and then turning is done to remove material to get the desired tool shape. The Fig. 2 reveals the 112


dimensions of the Tungsten carbide tool used in this work. Table 1 reveals the chemical composition of the tungsten carbide tool used in this work.

Fig. 2. Tool Design Here we are going to use SA213 Tube and SA387 Tube Plate shown in Fig 3 for this type of welding process. The Chemical Composition was revealed in Table 2 and Table 3 respectively. Table 2 Chemical composition of SA 387 Tube Plate E

Mn

Cr

Mo

Va

Ti

Fe

Wt%

0.75

1.55

0.38

0.041

0.087

96.7

Table 3 Chemical composition of SA 213 Tube E

Mn

Cr

Mo

Ni

Cop

Ti

Fe

Wt%

0.51

1.46

0.42

0.046

0.044

0.090

97.1

Fig. 3. Tube, Tube Plate Dimensions 113


Fig. 4. Projection of Tube before welding process Fig 4 reveals that the projection of the tube on plate as per orthogonal array. The table 4 shows the factors and levels of L9 Orthogonal array. Table 4 Factors and Levels of L9 Orthogonal Array Levels Factors 1

2

3

Rotational speed (rpm)

730

950

1320

Depth (mm)

0.2

0.4

0.6

Tube projection (mm)

0

1

2

The tool is lowered during rotation and heat is generated due to friction when the shoulder touches the plate. The plate metal gets plasticized and the plastic flow of metal takes place towards the center of the tool axis and flows through the holes in the tube and fills the gap, forming a bond between the tube and plate. The tool is withdrawn after a predetermined time. The role of cylindrical pin is to restrict the material movement and apply pressure between the tube and plate. The bonding takes place between surfaces which are subjected to both high pressure and temperature. In case of FWTPET, both the work pieces are kept stationary and the tool is rotating in axial direction during welding [3]. Friction welding is carried out by translating or rotating one component comparative to another along a mutual boundary, whereas smearing a compressive force through the joint. 114


Fig. 5. Friction welding process The work piece is placed under the condition of without hole with backing block shown in Fig 6. There are different rpm used for welding process such as 730, 950, 1320 rpm with respect to the depth of cut and projections. There are three types of projections 0mm, 1mm and 2mm and three types of depths 0.2mm, 0.4mm and 0.6mm. The Depth and Projection are arranged with Speeds as per L9 Orthogonal Array. Each work piece indicates different values with respect to rpm and depth of cut are tabulated.

Fig. 6. After Friction welding Then the project sample conducted the following test to yield better joining strength   

Radiography Test Compression Test Microscopic Test

The Radiography test emits Gamma Rays on this film in a dark room to find the cracks at the welding joints. As per L9 orthogonal array compressive strength for 9 samples will be taken. 115


Microscopic images supports to prove about better joining strength. Further optimization technics is used to discuss with the tests. RESULTS AND DISCUSSIONS Radiography Test Radiography image of weld made by FWTPET process is shown in Fig. 7. From the result it is clearly evident that there must no more flaws. Due to the axial movement of the tool, heat is generated by the shoulder and the metal reaches the plastic condition. Experiments are repeated for various conditions. From radiography test, it also observed that the weld joints are free from defects such as crack, porosity etc.

Fig. 7. Radiography Test Sample Compression Test UTM has been used for compression test as a Load is gradually applied until the specimen fractures. A fractured compression test sample of nine samples were tested in each combination of process parameters and the average value is chosen for optimization using Taguchi method. The input parameters and the output characteristics of L9 orthogonal array are presented in Table 5. Joint strength is the main characteristic considered in this investigation describing the quality of FWTPET joints. Signal-to-Noise [S/N] ratio In this study, the joint strength is the main characteristics considered in this investigation describing the quality of FWTPET joints. Joint strength is the main characteristic considered in this investigation describing the quality of FWTPET joints. The decisive factor - Larger than better is used for choosing the S/N ratio. S/N ratio terms is used to achieve better joining strength. Here the conditions 1320rpm rotational speed, 0mm projection of tube and 0.6mm depth of cut yields better joining strength of 3036.80 MPa compressive strength. The most significant parameter is calculated as depth of cut.

116


Table 5 Input and Output Parameters of L9 Orthogonal Array Input Constraints

Output Compression

Speed

Projection

Depth

(rpm)

(mm)

(mm)

730

0

0.2

2748.35

730

1

0.4

2980.45

730

2

0.6

2669.45

950

0

0.4

2979.45

950

1

0.6

2711.45

950

2

0.2

2665.65

1320

0

0.6

3086.90

1320

1

0.2

2881.23

1320

2

0.4

2733.22

Strength (MPa)

Analysis of Variance [ANOVA] This statistical treatment most commonly applied to the results of experiments to determine the percentage contribution of each parameter. MINITAB software is used to find the most significant parameter and the contribution of each process parameter.

. Fig. 8. Interaction plot – data means for compression test 117


Fig. 9. Percentage contribution of process parameters In this investigation, the results acquired from the ANOVA process, which implies the depth has majority of percentage contribution for the joint strength of about 57.28 %. This is due to the friction produced by the tool on the upper surface of the plate is main due to the projection of the tool. The tool rotational speed and projection of the tube has percentage contribution of about 18.18% and 24.53% respectively. Fig. 8 represents the interaction plot for the means and the Fig. 9 represents the percentage of contribution by each factor in a pie chart. Regression Analysis The regression analysis is a numerical means for the examination of interaction between various parameters. In this study, the optimal joint strength is obtained by means of regression analysis using MINI TAB. The feature is the regression equation is formed by providing input and output parameters in the Taguchi L9 orthogonal array. This helps to determine the cause result of one variable upon another. The two different equations are formed based on the value of three factors and compressive strength. In this study, the regression equations for tube without hole are obtained by the input parameters such as speed, projection and depth of cut and compressive strength. The regression equation for without hole is shown below in the equation. Regression Equation = 2528 + 0.175(Speed) – 60.6(Projection) + 463(Depth) The corresponding value of input factors are considered for calculating the optimal joint strength of work piece by using regression equation based on the maximum value obtained in the output parameter compression strength. The maximum compressive strength for without hole is 3036.80 MPa and corresponding values for each factor speed, projection, depth are 1320 rpm, 0 mm and 0.6 mm respectively. The values are substituted in the equation provided. The attained value is joint strength for the particular input and output factor which have been considered in the Taguchi L9 orthogonal array factors and levels.

118


Sample Calculations: Compression Strength = 2528 + 0.175 (Speed) – 60.6 (Projection) + 463(Depth) = 2528 + 0.175(730) – 60.6(0) + 463(0.2) = 2748.35 Mpa The different values can be substituted to find the optimal strength which depends upon the input and out parameters. It can be confirmed by subtitling the various values for each factor. The optimal joint strength for SA213 tube to SA387 tube plate by FWTPET process was 3036.80 MPa for tube without holes and the value obtained by this process was in the positive interval of the expected optimal joint strength. Microscopic Studies The friction welded joints have been sectioned perpendicular to the bond line and observed using an optical microscope. Typical micrographs showing different morphology of microstructure at different zones of the friction welded joints have been presented and analyzed. Compared to base metal, the changes in microstructures are observed obviously at weld zone interface. The grains at base metal (plate and tube) are relatively coarser. Fine grain structure has been observed in the weld zone interface. In solid-state welding, especially in friction welding, due to severe deformation, the refined grain structure is observed at the weld zone which resulted in improved properties.

Fig 10. Microscopic Image 1320 rpm speed, 1mm projection and 0.2mm depth (with defect) The Conditions Carried out at 1320 rpm rotating speed of the external tool. Thus, We known that heat discipates from the tool to tube which is fitted perpundicular to a plate. And more over due to the interference fit conditions the welding strength is more compares the welding done with clearance fit. Let we known that the above Fig 10. and Fig 11. microscopic images at 1320rpm speed, 0mm projection and 0.6mm depth and 1320rpm speed, 1mm projection and 0.2mm respectively. By the compression test result this condition 1320rpm, 0mm, 0.6mm gives the optimal strength 3086.90 Mpa and condition 1320rpm, 1mm, 0.2mm gives the optimal strength 2881.23 Mpa as per the Table 5. Fig 10. found some 119


defects at the welding interface. The crack is little big higher. Fig 10. Bondage is very less compared to Fig 10. Hence the strength is lesser compared to Fig 11. There are fine grain structure in the visual. Because fine grain structure reveals good bonding between two metals.

Fig 11. Microscopic Image 1320 rpm speed, 0mm projection and 0.6mm depth (without defect) In the present study, the interface is continuous and appears as a distinct line even at better enlargement and a fusion zone is also observed on the welded part of the bond interface in the work piece. Both micro structure shows the fine grained ferrites near the bonding line and this is due to combined effect of rigorous plastic deformation and higher nucleation pace. The continuous layer is essentially an alloy composed of the two parent materials. It is thought to be caused because of the instantaneous heat generated by the severe plastic deformation encountered at the interface. Hence, the condition 1320rpm speed, 0mm projection and 0.6mm depth of cut possess better weld strength between tube-to-tube plates. CONCLUSIONS In this study, FWTPET process has been used to join tube to tube plate which is a new and innovative process and has wider appli-cations. In order to reduce fabrication cost, researchers have been exploring the newer welding process to improve the joint properties. The tube-to-tube plate samples were successfully weldedby FWTPET process without hole codition employing without backing block arangement at Intereference fit. This process produced a high-quality and defect-free weld joint FWTPET is an innovative process which has been used to join tube to tube plate which has potential industrial potential. This process is capable of producing high quality leak proof joints with enhanced mechanical and metallurgical properties and less energy consumption. Taguchi L9 orthogonal array was used in this study, and the tube projection is found to be the most influen-tial process parameter in deciding the joint strength for FWTPET without hole condition with backing block arangement. The joint strength is maximum for the work piece has no holes on its inner edges value of about 3086.90 MPa and optimized process parameters are tool rotation speed 1320 rpm, depth of cut 0.6 mm and projection 0 mm. 120


This is achieved due to the absence of holes in the work pieces. The percentage of contribution of each process parameter has been found by ANOVA, without hole condition with the tool tube depth leading with the highest contribution (57.29%) followed by tool rotational speed (18.18%) and projection (24.53%). So the present study may help the engineers to predict the kind of weld condition that is capable of producing high-quality weld joints in industries. Microscopic images once again concludes that if the joining of tube and plate is fine then the optimal strength is also high. REFERENCES [1] Muthukumaran S, A process for friction welding tube to a tube sheet or plate by adopting an external tool, Indian patent Application No. 189/ KOL/ 06 filed on 07-03-2006, patent No.21744 , granted on 26/03/2008. 2006 [2] Muthukumaran S and Saket Kumar, Friction welding of Cu tubeto Al tube plate using an external tool, International WeldingSymposium 2k10 proceeding, (2010) 229 [3] Muthukumaran S. Senthil Kumaran · S. · S. Vinodh Optimization of friction welding of tube to tube plate using an external tool Struct Multidisc Optim (2010) 42:449–457 [4] Muthukumaran.S Senthil Kumar an & S Effect of projection on joint properties of friction welding of tube-to-tube plate using an external tool IntJ AdvM anuf Technology 119127[2009] [5] Muthukumaran.S and S.Vinodh. Experimental and numerical investigation of weld joints produced by friction welding of tube to tube plate using an external tool. International journal of Engineering, Science and Technology, 2,109-117[2010] [6] Muthukumaran.S C.V.Kumar, A.Pradeep, S.S.Kumaran. Optimization study of friction welding of steel tube to aluminium tube plate using an external tool process. International Journal of Mechanical and Materials Engineering [IJMME], vol.6 (2011), No.2, 300-306. [7] Senthilkumaran.S, S.Muthukumaran, S.Vinodh. Optimization of Friction welding of tube to tube plate using an external tool by taguchi method and Genetic algorithm. Int JAdvManufTechnol [2011] 57:167-182. [8] S. SenthilKumaran, S. Muthukumaran, and C. Chandrasekhar Reddy Effect of Tube Preparations on Joint Strength in Friction Welding of Tube-to-Tube Plate Using an External Tool ProcessExperimental Techniques 37(2013) 24 – 32 [9] S. Muthukumaran, C. Vijaya Kumar, S. Senthil Kumaran, A. Pradeep Interfacial Microstructure and Strength of Friction Welding of Steel Tube to Aluminium Tube Plate using an External Tool Advanced Materials Research Vols. 383-390 (2012) pp 877-881. [10] Senthil Kumaran.S & S. Muthukumaran Effect of projection on joint properties of friction welding of tube-to-tube plate using an external tool In t J Ad v Manuf Technol (2009) 507–514. [11] Muthukumaran S, A process for friction welding tube to a tube sheet or plate by adopting an external tool, Indian patent Application No. 189/ KOL/ 06 filed on 07-032006, patent No.21744 , granted on 26/03/2008. 2006 [12] Muthukumaran S and Saket Kumar, Friction welding of Cu tubeto Al tube plate using an external tool, International WeldingSymposium 2k10 proceeding, (2010) 229 [13] Muthukumaran S. Senthil Kumaran · S. · S. Vinodh Optimization of friction welding of tube to tube plate using an external tool Struct Multidisc Optim (2010) 42:449–457

121


[14] Muthukumaran.S Senthil Kumar an & S Effect of projection on joint properties of friction welding of tube-to-tube plate using an external tool IntJ AdvM anuf Technology 119-127[2009] [15] MINITABTM [2008] MINITABTM Statistical Software, Release 17, State College.

A. Daniel Das

Dr. S. Senthil Kumaran

Mr A. Daniel Das is a PG Scholar at RVS School of Engineering and Technology, Dindigul, Tamilnadu, India. His research interest in Friction Welding Process, Engineering Optimization, Product Design and Analysis. He has Published 5 International Journals in Various fields in Engineering. He receives Professional in Product Design and Analysis in May 2013. (Master of Computer Aided Drafting and Design). Dr. S. Senthil Kumaran received Ph.D (FWTPET- Friction Welding) in 2012 at National Institute of Technology. Trichirappalli. India. Currently he is working in RVS School of Engineering and Technology, Dindigul, India, as Professor and Head of the Mechanical department. His research interests focus on Advanced welding Process, Optimization, physical metallurgy, composite materials. He is an active life member of Indian Welding Society and International Association of Engineers. He published more than 30 research papers in various International journals and conferences and presently guiding three research scholars.


122


Available Online http://www.ijncse.com ISSN Online: 2395-7018 2(5) (2015) 375-391

Isotherm models for the adsorption of Crystal violet dye onto Zinc chloride activated carbon V. Nandhakumar[a] *, A.Rajathi [a], K. Ramesh[b] and A. Elavarasan[c] [a] Department of Chemistry, A.V.V.M Sri Pushpam College, Poondi. [b] Department of Chemistry, Arasu Engineering College, Kumbakonam. [c] Department of Chemistry, Sengunthar College of Engineering College, Thiruchengodu. Corresponding Author: E- mail id: [email protected] ABSTRACT An effective adsorbent was prepared from Terminalia catappa Linn fruit shell by Zinc chloride activation method and its adsorption characteristic was studied for the removal of a cationic Crystal violet (CV) dye from aqueous solution. pHzpc of the adsorbent was found to be 7.Batch mode adsorption experiments were adopted. Maximum dye removal capacity was observed at a pH of 9. Equilibrium data were obtained at 303, 313, 323, 333 and 343K for the initial concentrations of 16, 18, 20, 22 and 24 mg/L. Adsorption isotherm models such as Langmuir, Freundlich, Temkin and Dubinin – Radus-Kevich isotherms were used to correlate the equilibrium data. Parameters obtained from the isotherm models were discussed in detail. Keywords: Crystal violet dye, adsorption, Terminalia catappa fruit shell, activated carbon pHzpc, Langmuir, Freundlich, Temkin, and Dubinin–Radus-Kevich isotherms. INTRODUCTION Various types of synthetic dyestuffs appear in the effluents of industries such as textiles, printing, plastics, leather and food. The removal of synthetic dyes is of great concern

375 Int J Nano Corr Sci and Engg 2(5) (2015) 375-391 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Nandhakumar et al., because most of them and their degradation products cause serious environmental problems due to their high stability and complex aromatic structures. Crystal violet (CV) dye belongs to the tri phenyl methane class and is used largely as histological stain in veterinary medicine, as bacteriostatic agent and skin disinfectant in the medical community. CV is harmful and can cause life-threatening injury to the conjunctiva, skin irritation and permanent blindness. Hence it is necessary to remove the dye from effluent prior to discharge into water sources. There are several methods used for the treatment of dye containing wastewater. Some of them involve reverse osmosis, chemical oxidation, photo degradation and adsorption [1]. Among these methods, adsorption is proved to be superior to other techniques. Adsorption using activated carbon gave fruitful results for the removal of dyes from wastewater. Preparation of activated carbon from waste plant bio masses and evaluating its adsorbing potential is the recent trend of research. Fruit shell of T. catappa is a waste plant bio mass which is chosen as precursor for the present investigation [2] and the Zinc chloride activation method is adopted as it has the advantage of producing excellent activated carbons as reported in earlier literatures [3]. MATERIALS AND METHODS Adsorbate Crystal violet dye (Molecular formula: C25H30N3Cl, M.W: 407.979, C.I.no. 42555,CAS: 548-62-9, mp: 2050C) of Analar grade purchased from Merck company was used as such without further purification. Stock solution of 1000 mg/L was prepared by dissolving 1 gm of dye in 1000 mL.

Required initial concentrations of the solution say 16,18,20,22 and 24 mg/L were

prepared from the stock solution by proper dilution [4,5].

Fig. 1 Structure of Crystal violet dye Maximum wavelength (λmax) of this dye is 590nm


Nandhakumar et al.,

Preparation of Adsorbents The Terminalia catappa fruit shell were collected from A.V.V.M Sri pushpam college campus, Thanjavur Dt., washed with distilled water to remove the surface adhered particles, dried in sun light for 4 days, chopped into small pieces and powdered in a pulveriser. 50g of the powder was mixed with 100 ml of 60% ZnCl2 solution. The slurry was kept at room temperature for 24 h to ensure the complete access of the ZnCl2 to the T. catappa shell powder. Excess solution was decanted and the slurry was heated in muffle furnace at 723K for 3 h. Thus carbonized samples were washed with 0.5M HCl followed with distilled water until the pH of the washings attain 7.0. Then it was dried in a hot air oven at 383K for 1 h. The dried material was ground and sieved to get particle size in between 73 µm and 150 µm. It was designated as T. catappa Zinc chloride Activated carbon (TCZAC).[6,7].

Fig. 2 Terminalia catappa fruit shell Batch equilibrium method Experiments were carried out various temperatures such as 303, 313,323,333 and 343K in an orbital shaker at a constant speed of 130 rpm using 250 mL conical flasks containing predetermined dose of TCZAC with 50 mL of dye solution. Samples were agitated for predetermined time and the adsorbent were separated from the solution by centrifugation at 1000 rpm for 10 min. The absorbance of the centrifugate was estimated to determine the residual dye concentration. The absorbance of the dye solution was measured at λmax 590 nm using Systronics Double Beam UV-visible Spectrophotometer: 2202 [8]. The percentage of removal dye was calculated using the following equation V q t = (Ci − Ct ) W (%) of removal = ((Ci-Ct)/Ci) X 100 (1)


Nandhakumar et al., Where; Ci and Ct are the concentration of adsorbate (mg/L) at initial stage and at time‘t’ respectively V is the volume of solution (L) W is the mass of adsorbent (g). Experimental result obtained from the effect of initial concentration and contact times were employed in testing the applicability of isotherm and kinetic models. RESULTS AND DISCUSSION Determination of Zero Point Charge In solution, the presence of a net charge on a particle affects the distribution of ions surrounding it, resulting in an increase in the concentration of counter ions. At pH

zpc,

the

total sum of positive charges and the negative charges on the adsorbent is zero that is the adsorbent is in neutral charge. When the solution pH is below the pH

zpc

of the adsorbent, surface

of the adsorbent will possess positive charge. On the other hand the surface of the adsorbent will possess negative charge when the solution pH is above the pH The pH of the zero point charge (pH

ZPC)

zpc of

the adsorbent.

was determined using pH drift method [9], by

placing 0.2 g of adsorbent in glass stopper bottle containing 50 ml of 0.1M NaCl solutions. The initial pH of these solutions was adjusted to 2 to 12 by either adding 0.1 M NaOH or 0.1M HCl [10]. The bottles were placed in an incubator shaker at 298 K for 24 h, and the final pH of supernatant has been measured. A graph was plotted between final pH and initial pH of the solution. A straight line was drawn connecting the same pH values of horizontal axis and vertical axis [11]. The point of intersection of the straight line and the graph was taken as the pHzpc

of

the

TCZAC

which

was

found

to

be

7

as

shown

in

the

Fig.

3.


Nandhakumar et al.,

Fig. 3 pHzpc of the carbon Effect of pH pH is one of the most important factors controlling the adsorption of dye onto adsorbent particles, which affects the surface charge of the adsorbents as well as speciation of the solutes [12]. The hydrogen ion and hydroxyl ions are adsorbed quite strongly and therefore the adsorption of other ions is affected by the pH of the solution. It is usually expected that increase of cationic dye adsorption with the increase of pH due to the increase of the negative surface charge on the adsorbents [13]. The effect of solution pH was studied between initial pH range of 2 to 10, initial pH of the solution was maintained by the addition of 0.1M HCl and 0.1M NaOH solutions and agitated with 40 mg of adsorbent for 130 min at 303K. The results of effect of initial

pH

of

dye

solution

on

the

adsorption

of

CV

for

initial

dye

concentration of 16 mg/L is presented in Fig. 4


Nandhakumar et al.,

Fig. 4 Effect of pH The lower adsorption at acidic pH is probably due to the presence of excess H+ ions in the solution which compete with the cationic dye for adsorption sites. As surface positive charge density decreases with an increase in the solution pH, the electrostatic repulsion between the positively charged dye and the surface of the adsorbent is lowered, which results in an increase in the extent of dye adsorption. Higher percentage removal was occurred at pH 9.0 .But still at an alkaline medium; percentage of removal was not good. This might be due to the interionic attraction between the OH‒ ions which present in the solution in excess and dye cations. Hence the remaining experiments were conducted at pH 9 ± 0.5. Equilibrium studies Adsorption of dye is considered to be a fast physical/chemical process; it is a collective term for a number of passive accumulation processes which include ion exchange, co-ordination, complexation, chelation, Vander Waal’s attraction and micro precipitation. Proper analysis and design of adsorption separation processes require relevant adsorption equilibria as one of the vital information. In equilibrium, certain relationship prevails between solute concentration in solution and in adsorbed state .Equilibrium concentrations are the function of temperature. Therefore, the adsorption equilibrium relationship at a given temperature is referred to as adsorption isotherm. The concentration of dye solution at equilibrium (Ce) and the quantity adsorbed at equilibrium (qe)

at

different

temperatures

are

collected

in

Table

1.


Nandhakumar et al., Table 1 Equilibrium parameters [pH: 9, [Ci ]:16,18,20,22 and 24 mg/L, Dose: 40 mg/ 50 mL] [CV] (mg/L)

Ce (mg/L)

qe (mg/g)

Temperatures

Temperatures

303

313

323

333

343

303

313

323

333

343

16

1.176

0.980

0.784

0.588

0.392

18.52

18.77

19.01

19.26

19.50

18

2.156

1.764

1.568

1.176

0.784

19.80

20.29

20.53

21.02

21.51

20

2.941

2.549

2.156

1.764

1.176

21.32

21.81

22.30

22.79

23.52

22

3.921

3.529

2.941

2.352

1.764

22.59

23.08

23.82

24.55

25.29

24

4.901

4.313

3.529

3.137

2.549

23.87

24.60

25.58

26.07

26.81

Isotherm studies The presence of equilibrium between two phases (liquid and solid phase) is rationalized by adsorption isotherm. The equilibrium data obtained from the experiments were processed with the following isotherm equations such as Langmuir, Freundlich, Temkin, and DubininRaduskevich. Inference obtained from each isotherm is discussed in detail one by one Langmuir isotherm It is a widespread-used model for describing dye sorption onto adsorbent. Langmuir equation relates to the coverage of molecules on a solid surface and the concentration of contacting solution at a fixed temperature. This isotherm is based on the following assumptions such as adsorption limited to monolayer coverage, all surface sites being a like; one site accommodates one species of the adsorbates and the ability of a molecule to be adsorbed on a given site independent of its neighboring sites occupancy. Linear form of Langmuir equation is written in the followingform [14] C e/q e = 1/qmb + Ce /qm

(2)

Where qe is the amount of solute adsorbed per unit weight of adsorbent (mg/g), C e the equilibrium concentration of solute in the bulk solution (mg/L), qm is the maximum monolayer adsorption capacity or saturation capacity (mg/g) and b is the adsorption energy, b is the reciprocal of the concentration at which half saturation of the adsorbent is reached. The essential characteristics of Langmuir isotherm can be described by a separation factor, R L, which is defined

by

the

following

equation


Nandhakumar et al.,

RL = 1 / (1+ bC0)

(3)

where C0 is the initial concentration of the adsorbate solution. The separation factor RL indicates the nature of the adsorption process as given below: RL value

Nature of the process

RL> 1

Unfavourable

RL = 1

Linear

0 < RL< 1

Favourable

RL = 0

Irreversible

The results obtained from Langmuir isotherm model for the adsorption of dye are presented in Table 2. Concerned isotherm plots are shown in Fig. 5 Table 2 Langmuir isotherm constants for the adsorption of dye [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] Temperature

qm

b

(K)

(mg/g)

(L/mg)

303

27.0

1.608696

0.995

313

27.0

1.947368

0.995

323

28.5

2.058824

0.990

333

29.4

2.615385

0.994

343

29.4

4.250000

0.997

R2


Nandhakumar et al.,

The regression coefficient (R2) values are ranged from 0.990 to 0.997 for the five studied temperatures viz. 303, 313,323,333 and 343 K. These results show the best fitting of the equilibrium data in the Langmuir isotherms. The adsorption capacity is the most important characteristic of an adsorbent. It is defined as the amount of adsorbate taken up by adsorbent per unit mass of adsorbent. This variable is governed by a series of properties such as pore size and its size distribution, specific surface area, cation exchange capacity, pH, surface functional groups and also temperature. The mono layer adsorption capacity qm values (mg/g) for adsorption of CV dye ranged from 27.0270 to 29.4117.

Fig. 5 [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] Further it is noticed that adsorption capacities are slightly increased with the increase of temperature. The dimensionless separation factor R L values calculated for various initial concentrations at different temperatures are given in Table 3 for the adsorption of dye. These values are lie between 0 and 1 which indicate the favourable adsorption of dye onto TCZAC.


Nandhakumar et al., Table 3: RL values Temperature 0K

[CV] mg/L

303

313

323

333

343

16

0.037

0.031

0.029

0.023

0.014

18

0.033

0.027

0.026

0.020

0.012

20

0.031

0.025

0.023

0.018

0.011

22

0.027

0.022

0.021

0.017

0.011

24

0.025

0.020

0.019

0.015

0.009

Freundlich Isotherm Freundlich isotherm is an empirical equation. It is the most popular model for a single solute system based on the distribution of solute between the solid phase and aqueous phase at equilibrium. It suggests that sorption energy exponentially decreases on completion of the sorptional centers of an adsorbent. The Freundlich model describes the adsorption with in a restricted range only. It is capable of describing the adsorption of organic and inorganic compounds on a wide variety of adsorbents [15]. The linear form of the equation has the following form: ln qe = ln Kf + 1/n lnCe (4) where qe is the amount of adsorbate adsorbed (mg/g) at equilibrium, Ce is the equilibrium concentration of adsorbate in solution (mg/L) and Kf and n are the constants incorporating all factors affecting the adsorption capacity and intensity of adsorption respectively As a robust equation, Freundlich isotherm has the ability to fit into nearly all experimental adsorption–desorption data and is especially excellent for fitting data from highly heterogeneous sorbent systems. 1/n is the heterogeneity factor and it is a measure of deviation from linearity of adsorption. A favourable adsorption tends to have n value between1 and 10. The larger value implies a stronger interaction between the adsorbent and adsorbate while 1/n equal to 1 indicates linear adsorption leading to identical adsorption energies for all sites. Sorption of solute on any sorbent can occur either by physical bonding, ion exchange, complexation, chelation or through a combination of these interactions. In the first case of physical bonding, as the solute is loosely bound, it can easily be desorbed using distilled water. Different mechanisms as mentioned can be involved as the interaction between sorbent and solute molecules depending upon the functional groups such as hydroxyl, carbonyl and carboxyl 384 Int J Nano Corr Sci and Engg 2(5) (2015) 375-391 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Nandhakumar et al., can present within the structure of adsorbent. The parameter ‘n’ value of Freundlich equation expresses these phenomena. The results obtained from Freundlich isotherm model are given in Table 4. The concerned isotherm plots are shown in Fig. 6. Table 4 Freundlich isotherm results [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] kf Temperature n R2 (K) (mg/g) 303

5.6

18.6

0.980

313

5.6

17.7

0.971

323

5.2

19.5

0.950

333

5.5

20.9

0.978

343

5.7

22.8

0.994

The regression coefficient (R2) for Freundlich isotherms are ranged from 0.950 to 994 for all the studied temperatures viz. 303, 313, 323,333 and 343 K. It indicates that the experimental data fit well into Freundlich model. Freundlich constant adsorption capacity Kf (mg/g) values for adsorption of CV dye ranged from 17.68 to 22.76 respectively. Further it is noticed that the adsorption capacity increased with the increase of temperature.

Fig. 6 [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL]


Nandhakumar et al., The adsorption intensity constant ‘n’ values are ranged from 5.2 to 5.7 for all the studied temperatures, i.e., between 1 and 10, which indicate the favourable physical adsorption. In general Freundlich constant values infer a better performance of TCZAC. Temkin isotherm The Temkin isotherm assumes that the heat of sorption in the layer would decrease linearly with coverage due to sorbate-sorbent interactions. Further the fall in the heat of adsorption is not logarithmic as stated in Freundlich expression [16]. The linear form of Temkin equation is. qe = RT/bT ln aT + RT/bT ln Ce (5) Where, bT is the Temkin constant related to the heat of sorption (J/mg) and aT the equilibrium binding constant corresponding to the maximum binding energy (L/g). The Temkin constants aT and bT were calculated from the slopes and intercepts of qe versus ln Ce. The results obtained from Temkin model for the removal of CV dye are represented in Table 5. Concerned isotherm plots are shown in Fig. 7. The regression coefficient (R2) values ar e ranged from 0.931 to 0.990 for the five studied temperatures viz. 303,313, 323, 333 and 343 K. These results show the best fitting of the equilibrium data with Temkin isotherm. Table 5 Temkin isotherm results [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] Temperature bT aT R2 (K) (kJ/mg) (L/g) 303

6.721

1.238

0.959

313

6.807

1.229

0.968

323

6.357

1.242

0.931

333

6.776

1.215

0.965

343

7.154

1.189

0.990

Equilibrium binding constant ‘aT’ values (L/g) for adsorption of CV dye are ranged from 1.1897 to 1.2425.The Temkin constant related to heat of sorption, b T values (kJ/mg)for adsorption of CV dye are ranged from 6.3579 to 7.1547. Low values of heat of adsorption, supports he physisorption mechanism. Both the binding constant ‘aT’ values and heat of sorption, bT values found to increase with the increase of temperatures.


Nandhakumar et al.,

Fig. 7 [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] Dubinin – Radus-Kevich isotherm The Linear form of Dubinin-Radushkevich isotherm is. ln qe = ln qD - Bε2

(6)

where, qD is the theoretical saturation capacity (mg/g) B is a constant related to the mean free energy of adsorption per mole of the adsorbate (mol 2/J2) and ε is Polanyi potential which is related to the equilibrium as given below [17] ε = RT ln (1+1/Ce)

(7)

The constants qD and B were calculated from the slope and intercept of straight line obtained from the plot of ln qe versus ε2. The mean free energy of adsorption E calculated from B using the following equation. E = 1/ (2B)1/2

(8)

E is a parameter used in predicting the type of adsorption. An E value less than ‘8’ kJ/mol is an indication of physisorption. Concerned isotherm plots were shown in Fig. 8


Nandhakumar et al., Table 6 Dubinin – Radus-Kevich isotherm results [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL] Temperature

qD

E

(K)

(mg/g)

(kJ/mol)

303

23.6

0.2357

0.819

313

23.6

0.2673

0.835

323

24.3

0.2887

0.774

333

25.0

0.3536

0.823

343

26.0

0.4082

0.883

R2

The regression coefficient (R2) values are ranged from 0.774 to 0.883 for the five studied temperatures viz. 303, 313,323,333 and 343 K. These values reveal that fitting of equilibrium data with D-R isotherm are not as good as other isotherms studied earlier. The mono layer adsorption capacity qD values (mg/g) for adsorption of CV dye are ranged from 25.0136 and 26.0342 respectively. Further it is noticed that adsorption capacity increased with an increase in temperature. Values of the mean free energy E(kJ/mol) for the adsorption of CV dye are ranged from 0.2357 and 0.4082. The very low values of E infer the physisorption interaction.

Fig. 8 [pH :9, [Ci ]:16,18,20,22 and 24 mg/L, Dose = 40 mg/ 50 mL]


Nandhakumar et al., CONCLUSION Activated carbon prepared from T. catappa Linn fruit shell by Zinc chloride activation method (TCZAC) found to have pH

zpc

7.But the maximum adsorption of Crystal Violet dye was

observed at the initial solution pH 9.Equlibrium data were well fitted into Langmuir, Freundlich, Temkin isotherms having regression coefficient values (R2) around0.9.The regression coefficient values (R2) for Dubinin – Radus-Kevich isotherm ranged from 0.774 to 0.883 only. ‘RL’ values obtained from Langmuir isotherm and ‘n’ values obtained from Freundlich isotherm reveal the favourability adsorption of Crystal Violet dye onto TCZAC. Equilibrium binding constant ‘aT’ values and the heat of sorption, bT values obtained from the Temkin isotherm supports the physisorption mechanism and endothermic nature of adsorption. The very low mean free energy values ‘E’ obtained from the Dubinin – Radushkevich isotherm infer the physisorption interaction. The adsorption capacities obtained from the isotherms show the feasibility of TCZAC as an effective adsorbent for the removal of Crystal violet dye from aqueous solution. REFERENCES [1] Akinola, LK; Umar, AM, Adsorption of Crystal Violet onto Adsorbents Derived from Agricultural Wastes: Kinetic and Equilibrium Studies, J. Appl. Sci. Environ. Manage., 2015 19(2), 279- 288 [2] B. Stephen Inbaraj, N.Sulochana, Mercury adsorption on carbon sorbent derived from fruit

shell

of

Terminalia

cattapa,

J.

Hazard.

Mater.

B,

133

(2006)

283-290


Nandhakumar et al., [3] K.Ramesh, A.Rajappa and V.Nandhakumar, Adsorption of Methylene Blue onto Microwave Assisted Zinc Chloride Activated carbon prepared from Delonix regia podsisotherm and Thermodynamic Studies. [4]Theivarasu Chinniagounder, Mylsamy Shanker and Sivakumar Nageswaran , Adsorptive Removal of Crystal Violet Dye Using Agricultural Waste Cocoa (theobroma cacao) Shell, Research Journal of Chemical Sciences ,ISSN 2231-606X Vol. 1(7), 38-45, Oct. (2011) [5] Luyi Zhang, Huayong Zhang, Wei Guo, Yonglan Tian, Removal of malachite green and crystal violet cationic dyes from aqueous solution using activated sintering process red mud, Applied Clay Science 93-94 (2014) 85-93 [6] Namasivayam C. and Sangeetha D., Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon, J. Colloid and Interface Science, 280, 359365 (2004) [7] Makeswari M., Santhi D., Optimization of preparation of activated carbon from Ricinus communis leaves by microwave-Assisted Zinc Chloride chemical activation: Competitive adsorption of Ni2+ ions from aqueous solution, Journal of chemistry, 2013, 1-12 (2013) [8] T.V. Ramakrishna, G. Aravamudan, M. Vijayakumar, Spectrophotometric determination of mercury (II) as the ternary complex with rhodamine 6g and iodide, Anal. Chim. Acta 84 (1976) 369-375. [9] M. Nasiruddin Khan and Anila Sarwar, “Determination of points of zero charge of natural and treated adsorbents” Surface Review and Letters, Vol. 14, No. 3 (2007) 461–469 [10] M. Nasiruddin Khan and Anila Sarwar, Determination of points of Zero charge of Natural and treated Adsorbents Surface Review and Letters, Vol.14, No.3 (2007) 461-469 [11] Ho Y.s., Porte RJ.F. and Mc kay G., Equilibrium isotherm studies for the sorption of divalent metal ions onto peat: copper, nickel and lead single component system. Water, Air, and Soil pollution. 141, 1-33 9 (2002) [12] Minguang Dai, Mechanism of Adsorption for Dyes on Activated Carbon, J . Colloid Interface Sci., 198, 6-10 (1998)


Nandhakumar et al., [13] Do˘gan M., Ozdemir Y. and Alkan M., Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite, Dyes Pigments, 75, 701–713 (2007) [14] Yanyan pei, Man Wang, Di Tian, Xuefeng Xu, Liangjie Yuan., Synthesis of core-shell SiO2@MgO with flower like morphology for removal of crystal violet in water. Journal of colloid and Interface Science 453 (2015) 194-201. [15] Xiao-Yi Huang, Jian-Ping Bin, Huai-Tian Bu, Gang-Biao Jiang, Removal of anionic dye eosin Y from aqueous solution using ethylenediamine modified chitosan, Carbohydrate Polymers 84(2011) 1350-1356 [16] Basar, C.A., Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel: Adsorption equilibrium and kinetics, J. Harzard. Mater., B135, 232-241 (2006) [17] Teles de Vasconcelos L.A., Gonzalez Beca, C.G., Adsorption equilibrium between pin bark and several ions in aqueous solution Cd(II), Cr(III) and Hg(II), Eur.,water pollut. Control., 3(6), 29-39 (1993)


Note: This paper is a revised version of the paper already published in the conference proceedings- Editor-in-Chief



2(5) (2015) 360-367

Synthesis, Characterization and Antimicrobial Studies of 2,6-Bis(pyridine2-yl)3,5-diphenyl-piperidin-4-one M. Seeni Mubarak*, R. Kathirvel , M. Sathyanarayanan and M. Mohamed Rabeek PG and Research Department of Physics, Jamal Mohamed College(Affiliated to Bharathidasan University), Trichy-20, Tamilnadu, India. ABSTRACT Piperidin is an important class of heterocyclic compounds which play a vital role in the field of medicinal chemistry. Several 2,6-disubstituted derivatives of these compounds are found to posses biological activities such as herbicidal, fungicidal, anticancer, anaesthetic etc. The synthesis of substituted piperidin-4-one derivatives using 1,3-diphenyl acetone, variously substituted aldehydes and ammonium acetate or ammonium formate (amine) in ethanol medium under reflux-free condition is described. The characterized by FT-IR, 1HNMR, 13

CNMR and Biological studies.

Keywords: FT-IR, 1HNMR, 13CNMR and Biological studies. INTRODUCTION The synthesis and structures of Mannich Bases have attracted much attention in biology and chemistry due to their model character and practical application. Mannich base piperidin-4-one have remained an important and popular area of research due to simple 360 Int J Nano Corr Sci and Engg 2(5) (2015) 360-367 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

SeeniMubarak et al.,

synthesis, adaptability, and diverse range of applications. Heterocyclic compound with a piperidone skeleton are attractive target for organic synthesis and there is found to be significant in compound possessing aromatic substitution in 2 and 6th position in the piperidone rings[1-3]. Literature reports show that a wide range of 2,6 disubstituted piperidin-4-one[4-8]. Amoung the piperidin derivatives, piperidones are important intermediates in several synthetic sections[9-14]. Due to the known therapeutic properities of piperidones and the presence of keto functional group that facilitates the introduction of other substituted derivatives of this class compounds have been found the posses biological activities such as herbicidal insecticidal, fungicidal, anti inflammatory, anesthetic, anticancer activity. The antimicrobial activity was performed by the Disc diffusion technique method, using different concentrations (50μg, 100 μg, 500μg and 1000μg). The sterile Muller hinton agar and Sabouraud dextrose agar were used for bacteria and fungi respectively. Two Gram positive, two Gram negative and two fungal strains were used to study the antimicrobial activity. All these strains were obtained from Pune. (NCIM-National collection of Industrial microbes) The watt-man Number 2 filter paper of 6mm diameter was loaded with 100μl of the diluted sample placed at equal intervals over the uniformly inoculated plate along with a standard disc Ciprofloxacin 5mcg/disc for bacteria and Nystatin 100units/disc for fungi were also placed along with sample to maintain quality control[15-18].

Int J Nano Corr Sci and Engg 2(5) (2015) 360-367 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

361


O

+

C CH2

CH2

OHC

2 N

Et-OH NH4OFa

-2H2O

O Ph

Ph

N H N

N

2,6-Bis(pyridine-2-yl)3,5-diphenyl-piperidin-4-one Scheme-1 MATERIALS AND METHODS 1,3-Diphenyl acetone(1.3g; 0.1mol), ammonium formate (4g; 0.1mol) and pyridine-2-carbaldehyde (2.1.ml; 0.02mol) were taken in a RB flask containing ethanol (10ml). The mixture was refluxed in a water bath with occasional shaking until the colour changed into red orange. The solution was cooled, and then ether (50ml) was added. The filtered solution was transferred into conical flask and Con.HCl (5ml) was added. A white precipitate was formed. The precipitate was washed with 5:1 ethanol:ether mixture and dried. Acetone (10ml), liquid ammonia (5ml), and excess of coldwater were added. The precipitate formed was filtered and dried. Then the product was recrystallised with acetonitril. The product was dried, m.p 222-2240C. RESULTS AND DISCUSSION Spectral characterization 2,6-Bis(pyridine-2-yl)3,5diphenyl-piperidin-4-one Yield: 86-92%; mp: 222-224ºC . FT-IR (KBr): 3392 (ʋ N-H), 3023(υaromatic-CH), 2901 (υaliphatic-CH), 1704 (υC=O), 1588, 1430 (υC

C)cm-

1 1

, H NMR (300MHz, DMSO-d6, δ in ppm); 8.562-8.555 (d, 2H, pyridine –H); 7.51-7.45(t,

6H, pyridine-H); 7.16-6.87(m, 12H, aromatic-H); 4.77-4.69(t, 2H, benzylic-H (C3 and C5 protons); 4.40-4.36(d, 2H, benzylic-H (C2 and C6 protons); 3.37(hump,1H,NH).

13

CNMR


362


(100MHz, DMSO-d6, δ in ppm): 206.2(>C=O), 158.9, 149.1, 136.2,

129.7,127.5, 126.2,

123.0, 122.4, 66.9, 63.4.

Table:I S.N o 1 2 3 4 5 6

Name of the Microorganisms Staphylococcus aureus (NCIM2079) Basillus subtilis (NCIM2063) Klebsiella aerogenes (NCIM2098) E.coli (NCIM2065) Aspergillus niger (NCIM2105) Candida albicans (NCIM3102)

Zone of inhibition in mm 50mcg 16

100mc g 18

500mc g 20

1000mcg Solvent control 20 -

standar d 35

18

20

20

21

-

40

12

16

18

19

-

30

16

18

20

24

-

38

16

18

18

20

-

35

16

16

17

20

-

32

Standard-Ciprofloxacin 5μg/disc for bacteria: Nystatin 100units/disc for fungi. Solvent-DMSO


363


Figure-1: Graphical chart of Inhibition

Fig-a: S.aureus

Fig-b: B. subtilis


364


Fig-c: K.aerogenes

Fig-d: E.coli

Fig-e: A. niger

Fig-f: C.albicans Figure-2: Zone of Inhibition

Followed by incubation at 37ºC for 24hrs and 25ºC for two days for bacteria and fungi were observed for zone of inhibition. The zone of inhibition was measured by using a standard scale. The diameter of the zone of inhibition directly proportional to the amount of active constituent present in the sample. The compound were found to be effective against Gram positive (Staphylococcus aureus and Basillus subtilis). Among these two Gram positive the effect was found to be remarkable at low concentration (100μl) towards Basillus subtilis and more effective against Gram negative E.coli and Klebsiella aerogenes. In the compound showed better response towards fungal strains Aspergillus niger and Candida albicans. CONCLUSION


365


A simple and elegant method for the synthesis of the compound described in this work. Nitrogen containing piperidine-4-ones are obtained, when more convenient ammonium formate is employed instead of the deliquescent ammonium acetate. The synthesized compound was characterized by FT-IR, 1H NMR, 13C NMR and biological activity. ACKNOWLEDGEMENT The Authers thanks the Principal and Management committee members, Jamal Mohamed College, Trichy-20 for providing necessary facilities. REFERENCES [1] Finer. I. L, “Organic Chemistry” ELBS., 1975; Vol 2. [2 ]C.Noller ;V.Baliah, J. Am. Chem. Soc.1948,70,3853. [3] Baliah V, Ekambaram A, Govindarajan T. S, Curr. Sci,1954; 23: 264. [4] Baliah V, Jeyaraman R, Chandrasekaran L. J. Am. Chem. Soc, Rev.1983, Vol.83, 379-423. 5. Baliah V, J.Chandrasekaran, Indian Journal of chemistry,15B, 55S(1977). 6. Baliah V, Gopalakrishnan V, Jeyaraman R, Indian.J.Chem,Soc.,Sec.B, 1978; 6B: 1065. 7.V.Baliah;V.Gopalakrishnan;R.Jeyaraman,IndianJournalOfChemicalSociety,Sec.B,1978,16 B,1065. 8. Fazal Mohamed M. I, Krishnapillay M, Indian.Chem.Soc., 1993; 70: 258. 9. Fazal Mohamed M. I, Krishna Pillay M, Indian. J. Chem., 1997; 36B: 50. 10. R.Jeyaraman and S.Avila, Chem. Rev., 81, 1499(1981). 11. V.Baliah and T.S.Govindarajan, Curr. Sce., 23, 91(1954). 12. V.Baliah and A.Ekambaram, J. Indian. Chem. Soc., 33, 274(1955). 13. Silverstein, Bassler and Morrill, Spectrometric Idendification of Organic Compounds.4th Edn. John Wiley & Sons. 14. Seeni Mubarak M, et al., Oriental J. Chem.,2011; 27(1): 333. 15. Ramani Devi R, Kathirvel R, Seeni Mubarak M, Mohamed Rabeek S, Fazal Mohamed M.I; International J.ITEE., 2014; vol 3: 1-4. Int J Nano Corr Sci and Engg 2(5) (2015) 360-367 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

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16. Indian pharmacopeia 1996, vol11,A-105. 17. Kathirvel R, Sathyanarayanan M, Seeni Mubarak M, International J.WJPPS, Vol.4,854862, 2015. 18. C.Mannich, Arch. Pharm. (Weinhei, Ger.), 255, 261(1971).



367

EDITORIAL BOARD INTERNATIONAL JOURNAL OF NANO CORROSION SCIENCE AND ENGINEERING

Editors

International Advisory Board

Dr.A.Peter Pascal Regis PhD, St.Josephs College, Trichy, India

Dr.Nworie, Felix Sunday, Dept of Industrial Chemistry, EBSU, Ai, 08034813342

Dr. P.Manjula Ph.D, APA College for Women, CK Pudur,Palani, India.

Dr. Olushola Sunday AYANDA, Department of Chemistry, Faculty of Applied Sciences, Cape Peninsula University of Technology, P.O. Box 1906, Bellville, South Africa

Dr.J.Jeyasundari PhD, SVN College, Madurai, India. Dr.A.Krishnaveni Yadava College, Madurai, India. Dr.C.Thangavelu PhD, EVR College, Trichy, India Dr.A.John Amal Raj, PhD, EVR College, Trichy, India Dr.P.Prabhakar, PhD, APA College of Arts and Culture, Palani, India Dr.B.Narayanasamy PhD, Professor & Head, Dept. of Science & Humanities, Maamallan Institute of Technology, Sriperumbudur, CHENNAI-601 208, India Dr.M.Manivannan PhD Chettinadu College of Engineering and Technology Dr C Mary Anbarasi Department of Chemistry Jayaraj Annapackiam College for women (Autonomous), Periyakualm, India

Dr. Geta CARAC, Professor, Department of Materials Science and Engineering Faculty of Metallurgy, Materials Science and Environment, Dunarea de Jos University of Galati, 47 Domneasca Street, 800008 Galati, Romania Dr. Viswanathan S. Saji (V.S. Saji), Visiting Research Fellow (Endeavour Research Fellow) School of Chemical Engineering, University of Adelaide North Engineering Building, N 126, Adelaide SA 5005, Australia Dr. ABD al-Aziz EL-SAYED FOUDA, Prof of Physical Chemistry, Faculty of Science Mansoura University Mansoura-3551, Egypt Dr. Abdulhameed al-hashem Corrosion, Scientist, Kuwait Institute for Scientific Research (KISR) P.O Box 24885 Safat 13109, Kuwait


Dr. Lidia benea Professor, Department of Materials Science and Engineering Faculty of Metallurgy, Materials Science and Environment, Dunarea de Jos University of Galati, 47 Domneasca Street, 800008 Galati, Romania Prof. O.Lahodny Sarc, Institute for corrosion protection of Materials and Desalination Croatian Academy of Science and Arts, Dubrovnik, Croatia Manickam Sivakumar University of Nattingham, UK

National Advisory Board

Dr.D.Sarala Thambavani Meenakshi Government Arts College for women, Madurai, India Dr.N.Muthumani, Sri Meenakshi Government Arts College for women, Madurai, India Dr.Elango, Thiagarajar College, Madurai, India. Dr.A.Suganthi, Thiagarajar College, Madurai, India. Dr.A.Jamal Abdul Nasser Jamal Mohamed College, Trichy,India R.Maria Joany, Sathyabama University, Chennai, India

Dr.V.S.Vasantha PhD, School of Chemistry, MK University, Madurai, India.

Dr. Felicia Rajammal Selvarani, Holy Cross College, Trichy,India.

Dr. V.Murugesan PhD BS Abdur Rahman University, Chennai, India.

Dr.A. Noreen, Holy Cross College, Trichy,India.

Dr.D.Easwara moorthy PhD BS Abdur Rahman University, Chennai, India.

Dr.Leema rose, Holy Cross College, Trichy,India.

Dr.A.Sahaya Raja,PhD, GTN Arts College, Dindigul, india.

Dr.H. Benita Sherine Holy Cross College, Trichy, India.

Dr.J.Sathiyabama,PhD GTN Arts College, Dindigul, india. North Engineering Building, N 126, Adelaide SA 5005, Australia

Dr. Felicita Florence, Holy Cross College, Trichy,India. Dr. P.Thillai Arasu, Kalasalingam University, Srivilli puthur, India.


Dr.M.Ganesan, Vivekananda College, Thiruvedagam west, Madurai,India. Dr.K.Siva Subramanian, Vivekananda College, Thiruvedagam west, Madurai,India. Ms. V.R. Naseera banu, RVS College of Engineering and Technology, Dindigul,India. Dr.Syed Abuthahir, RVS School of Engineering and Technology, Dindigul, India. Ms.P.Satyabama, University College of Engineering and Technology, Dindigul, India. Dr.K. Mythili, N.S.N College of Engineering and Technology, Karur,India. Dr. Gurmeet singh Professor, Department of Chemistry, University of Delhi, Delhi-110 007. Dr. Kalpana bhrara Professor, Department of Chemistry, Aditi Mahavidyalaya,Bawana,University of Delhi,Delhi- 110 003, India Dr. S.M.A. Shibli Professor, Dept. of Chemsitry,University of Kerala, Kariavattom,Thiruvananthapuram 695 581,Kerala. Dr. C. Joseph kennedy Professor of Chemistry, Karunya University,Karunya Nagar, Coimbatore, India

Dr. A. Sheik mideen, Professor, Department of Chemistry,Sathyabama University, Jeppiaar Nagar, Chennai 600 119., India Dr. M.A. Quraishi Professor, Dept.of Applied Chemistry, Indian Institute of Technology Banarus Hindu University, Varanasi 221 005, Uttar Pradesh. R.Joseph Rathish, PSNA College of Engineering and Technology, Dindigul, India S.Santhana Prabha, PSNA College of Engineering and Technology, Dindigul, India R.Dorothy, St Joseph's College of Engineering and Technology, Chennai, India P.Jayakrishnan.,M.E Chennai-600069. R.Epshiba., M.Sc., M.Ed., M.Phil., M.C.A., (Ph.D) Assistant Professor Department of Chemistry Sri Muthukumaran Institute of Technology Chennai-600069. Dr.George Johnson, Deparatment of Chemistry,Loyola College, Chennai, India Dr.S.Johnmary, Deparatment of Chemistry,Loyola College, Chennai,India


Dr.Arul Maximus Rabel, Centre for Nano Science and Nano Technology, Sathyabama University, Chennai, India Dr.Viswanathan, Centre for Nano Science and Nano Technology, Sathyabama University, Chennai, India Mr.R.Sathish, Department of Mechanical Engineering, St Joseph's College of Engineering, Chennai-119, India CECRI, Karaikudi, India Mr.GS.Nixon, Department of Mechanical Engineering, St Joseph's College of Engineering, Chennai-119, India Dr.Anbukulandainathan, CECRI, Karaikudi, India Dr.R.Selvaraj, CECRI, Karaikudi, India Mr.A.Daniel Das, M.E.,M.CADD Department of Mechanical Engineering, RVS School of Engineering & Technology, Dindigul. Prof Dr N Raman VHNSN College Virudunagar