Copper Corrosion Inhibitor Review

Int. J. Electrochem. Sci., 3 (2008) 1 - 28

https://www.wendangku.net/doc/2f11680240.html, Review

Copper Corrosion Inhibitors. A review

M. M. Antonijevic* and M. B. Petrovic

University of Belgrade, Technical Faculty Bor 19210 Bor, P. Box 50, VJ 12, Serbia

*E-mail: mantonijevic@tf.bor.ac.yu

Received: 5 October 2007/ Accepted: 25 October 2007 / Online published: 20 November 2007

The literature dealing with the electrochemical corrosion of copper and possibility of its prevention using inhibitors is examined. Inorganic compounds are investigated as well, but organic compounds and their derivatives in much greater numbers. Researches are directed to influence of compounds structure, concentration, method of application as well as media that inhibitor is used in on inhibition efficiency. Moreover, action mechanisms are studied. The attempts to find models, which can enable prediction of possibilities of newly synthesized compounds to act as corrosion inhibitors, combining theory and practical investigations of substances with similar structure are also significant.

Keywords: Copper, corrosion, inhibitors

1. INTRODUCTION

Copper is metal that has a wide range of applications due to its good properties. It is used in electronics, for production of wires, sheets, tubes, and also to form alloys. Copper is resistant toward the influence of atmosphere and many chemicals, however, it is known that in aggressive media it is susceptible to corrosion. The use of copper corrosion inhibitors in such conditions is necessary since no protective passive layer can be expected. The possibility of the copper corrosion prevention has attracted many researchers so until now numerous possible inhibitors have been investigated. Amongst them there are inorganic inhibitors [1], but in much greater numbers there are organic compounds and their derivatives such as azoles [2-49], amines [50-56], amino acids [57, 58] and many others. It is noticed that presence of heteroatoms such as nitrogen, sulphur, phosphorous in the organic compound molecule improves its action as copper corrosion inhibitor. This is explained by the presence of vacant d orbitals in copper atom that form coordinative bonds with atoms able to donate electrons. Interaction with rings containing conjugated bonds, electrons, is also present. Based on these results more and more compounds containing numerous heteroatoms and functional groups are developed synthesized since it is noticed they are responsible for good properties regarding corrosion inhibition because they

enable chemisorption. Also molecular weight is larger due to its beneficial effect on physical adsorption.

There are attempts to combine theory and practical experience from investigations of some substances having similar structure in order to find models that would enable prediction of possibilities of newly synthesized compounds to act as corrosion inhibitors.

These are the reasons for espying the need to make up a review that would sum the results published by now and serve as a guidance for the future research.

2. INORGANIC COPPER CORROSION INHIBITORS

The use of inorganic inhibitors as an alternative to organic compounds is based on the possibility of degradation of organic compounds with time and temperature. Three different inorganic inhibitors are investigated: chromate CrO42-, molybdate MoO42- and tetraborate B4O72- in concentration of 0,033M in solution containing 850g/l LiBr and has pH 6,9. Chromate is generally accapted as efficient corrosion inhibitor that can passivate metals by forming a monoatomic or polyatomic oxide film at the electrode surface, but it is also known that it can promote corrosion acting as a cathodic reactive. Possible process for chromates is the reduction or decomposition of the inhibitor on the metal surface, followed by precipitation. Chromates are reduced to Cr(III)hydroxide or oxyhidrixide on the metal surface that results in corrosion current density decrease. However, the main disadvantage is the toxicity of chromium (VI) oxidation state. This is the reason for search for less toxic alternatives.The logical alternative can be analogue of hexavalent chromium the molybdate species that is an environmentaly friendly inhibitor. Nevertheless, molybdate and tetraborate showed no significant inhibition. The corrosion resistance is not improved because the film formation is not favorised in the electrolyte containing very aggressive anions such as bromides. Inhibion efficiency increases in the following order: molibdate (1.56%)< tetraborate (51.0%)< chromate (78.6%). [1]

3. THE ORGANIC COPPER CORROSION INHIBITORS

3.1. Azoles

Azoles are organic compounds containing nitrogen atoms with free electron pairs that are potential sites for bonding with copper and that enable inhibiting action. Also, there is a possibility of introduction of other heteroatoms and groups in molecules of these compounds so there is a wide range of derivatives that exhibit good inhibition characteristics.

El-Sayed M.Sherif [2-5] investigated the influence of 2-amino-5-ethylthio-1,3,4-thiadiazole (AETD) on copper corrosion in aerated HCl solution [2] as well as the influence of 2-amino-5-ethylthio-1,3,4-thiadiazole (AETD) [3], 2-amino-5-ethyl-1,3,4-thiadiazole (AETDA) [4] and 5-(phenyl)-4H-1,2,4-triazole-3-thiole (PTAT) [5] in NaCl solution. It is expected that these compounds show high inhibition efficiency since they are heterocyclic compounds containing more donor atoms, besides that they are non-toxic and cheap. AETD, AETDA and PTAT proved to be good mixed type copper corrosion inhibitors and the inhibition efficiency increased with concentration [2-5], exposure

period [2,4,5] and oxygen content [3,4]. AETD, AETDA and PTAT molecules strongly adsorb on copper forming complexes with copper ions and prevent forming of Cu chloride and oxychloride complexes. The obtained values of inhibition efficiency are presented in Table 1.

Table 1. The results of the study of the efficiency of copper corrosion inhibition by AETD, AETDA and PTAT solution AETD concetration IE (%) references 1.0mM

40.00 5.0mM 59.00 0,5M HCl ?after 12h exposure 10.0mM 77.00 [2] 1.0mM 83.00 3% NaCl 5.0mm

94.00 [3] IE (%) Method; 3% NaCl solution AETDA concentration immediately after 10 days 1?10-3 M 60.00 60.00-62.00 Weight loss 5?10-3M 97.00 97.00-100.00 deaerated aerated oxygenated solution Potenciodynamic polarization; 5?10-3M AETDA 41.00 71.40

87.40 [4] surface coverage PTAT concetration of 1500ppm; 3.5% NaCl after immersion after 100h steady solution 0.87 0.97 stirred solution 0.71 1.00 [5]

In his work Gy.Vastag [6] investigated thiazole derivatives: 5-benzylidene-2,4-dioxotetrahydro-1,3-thiazole (BDT); 5-(4’-isopropylbenzylidene)-2,4-dioxotetrahydro-1,3-thiazole (IPBDT); 5-(3’-thenylidene)-2,4-dioxotetrahydro-1,3-thiazole (TDT) and 5-(3’,4’-dimetoxybenzylidene)-2,4-dioxotetrahydro-1,3-thiazole (MBDT) as copper corrosion inhibitors in 0.1M sodium sulphate solution, pH=2.94. Results are shown in table 2. The best protection is achieved by IPBDT as expected based on the structural analyses i.e. the presence of isopropyl group. It is shown that the investigated thiazole derivatives (especially IPBDT) have potential to replace toxic inhibitors (such as triazoles) that are used in closed systems.

Table 2. The efficiency of inhibition in the presence of thiazole derivatives [6] inhibitor

method IPBDT BDT TDT MBDT weight loss 89.00 86.00 65.00 73.00 IE (%) EIS 93.00 86.00 80.00 71.00

F.Zucchi et al. [7] studied the inhibiting action of tetrazole derivatives in 0.1M NaCl solution. Following compounds are tested: tetrazole (T), 5-mercapto-1-methyl-tetrazole (5Mc-1Me-T), 5-mercapto(Na salt)-1-methyl-tetrazole (5NaMc-1Me-T), 5-mercapto-1-acetic acid (Na salt)-tetrazole (5Mc-1Ac-T), 5-mercapto-1-phenyl-tetrazole (5Mc-1Ph-T), 5-phenyl-tetrazole (5Ph-T) and 5-amino-

tetrazole (5NH2-T) in the range of pH from 4 to 8 and at temperatures of 40 and 80°C. Recorded data are presented in table 3. All the inhibitors except 5Mc-1Ac-T that promotes which stimulates corrosion show an inhibition efficiency (IE) between 50 and 99%. IE increases with increasing pH and concentration while the temperature has a different influence on various derivatives. The best protective characteristics are shown by 5Mc-1Ph-T and 5Ph-T. IE decreases in the following order: 5Ph-T>5Mc-1Ph-T>5Mc-1Me-T>5NH2-T>5NaMc-1Me-T>T. The prefilming treatment is efficient only with 5Mc-1Ph-T, while at longer exposure time only 5Ph-T prevents corrosion attack. The inhibiting action is explained by adsorption of the inhibitor on the copper surface and formation of complex with copper.

Table 3. Tetrazole derivatives inhibition efficiency (temperature of 40°C, pH of the inhibitor solution without adjustments) [7]

inhibitor concentration IE%

T

10-3M in solution 53.50

exposure in 10-3M solution for 1h and measured after 1h in NaCl 36.80

5Ph-T

10-3M in solution 99.40

exposure in 10-3M solution for 1h and measured after 1h in NaCl 1.30

5Mc-1Ph-T

10-3M in solution 98.40

exposure in 10-3M solution for 1h and measured after 1h in NaCl 93.00

5Mc-1Me-T

10-3M in solution 93.40

exposure in 10-3M solution for 1h and measured after 1h in NaCl 25.90

5NH2-T

10-3M in solution 85.30

exposure in 10-3M solution for 1h and measured after 1h in NaCl -4.10

5NaMc-1Me-

10-3M in solution 66.20

T exposure in 10-3M solution for 1h and measured after 1h in NaCl 28.00

5-Mc-1Ac-T

10-3M in solution -110.00

exposure in 10-3M solution for 1h and measured after 1h in NaCl -25.70

The influence of 1-phenyl-5-mercapto-1,2,3,4-tetrazole (PMT) on the corrosion resistance of Cu in 0.1M HNO3 is also studied. The action effect of PMT is compared with the influence action of other organic compounds of this type the same family such as 1,2,3,4-tetrazole (TTZ), 5-amino-1,2,3,4-tetrazole (AT) and 1-phenyl-1,2,3,4-tetrazole (PT). The results are shown in table 4. They behave as mixed type inhibitors. The mechanism of action is chemisorption on the copper surface that follows Langmuir isotherm. Inhibition efficiency increases in the following order: TTZ

E.Sz cs [9] in his research investigated the inhibitor 5-mercapto-1phenyl-tetrazole (5-MPhTT) in 1mM H2SO4 solution. The results show reveal that the anodic current density and mass loss are two times twice less lower in the presence of 5-MPhTT. The investigated concentration is 0.5mM. Measuremens are conducted in three intervals where the first is in blank solution, the second in the solution containing inhibitor while the third is again in the blank solution. The mass change is observed in the first interval while in the 2. and the 3. mass didn’t change. The inhibition efficiencies for the second and the third interval are 99.93% and 99.8% respectively. It is concluded that inhibitor

forms a protective film chemisorbed on the surface. The structure of the protective film is further investigated by X.R.Ye [10] and the following conclusion is reached. The film contains a layer of inert, insoluble and long-lasting polymeric Cu(I) complex. These films are probably built over Cu2O layer through surface reaction of PMT and Cu(I) ions. The copper surface treated with PMTA can be described as composite structure Cu-PMTA/Cu2O/Cu. Each molecule of PMTA bridges two or more Cu(I) ions via N and S atoms. The hydrophobic backbone on PMTA ligand in Cu-PMTA prevents contact between hydrated corrosive ions and the metal surface and thus inhibit substrate corrosion. The optimum conditions for PMTA treatment are: 0.005mol/l PMTA solution, pH=3, temperature 20-50°C and 30min of treatment time. It is noticed that the films of coordination compounds formed by reaction of PMTA with copper surface are more efficient in corrrosion inhibition (under the influence of atmosphere, sulphide and chloride media) than those formed with TTA (tetrazole), BTA (benzotriazole), HBTA (hydroxybenzotriazole), MBT (2-mercaptobenzothiazole), MBI (2-mercaptobenzoimidazole), 2-AP (2-aminopyrimidine), IBM (imidazole) and chromates.

Table 4. The efficiency of inhibition in the presence of 10-3M tetrazole [8]

inhibitor method IE%

TTZ

weight loss after 72h exposure to 0.1M HNO331.50

polarization 29.80

AT

weight loss after 72h exposure to 0.1M HNO356.40

polarization 59.60

PT

weight loss after 72h exposure to 0.1M HNO394.50

polarization 93.70

PMT

weight loss after 72h exposure to 0.1M HNO397.50

polarization 95.40

J.C.Marconato [11] investigated the effect of 2-mercaptobenzothiazole in the ethanol solution. The solution contains 10-2M HClO4 in ethanol. When MBT is added the inhibition of anodic copper dissolution and cathodic reaction of hydrogen evolution is observed. The concentration of MBT of 0.001M lead to reduction of current density 4 times that is associated with formation of complex between metal ions and inhibitor. MBT is oxidized to 2,2’-dithiobis(benzothiazole) and/or 2,2’-thiobis(benzothiazole) and forms a complex involving its ionized thiol form and Cu(II) ions. The characteristics of adsorption and the influence of MBT and tetrazole (TTA) on the growth of oxide film on copper in 0.1M NaOH are also investigated [12]. The inhibition efficiency is strongly dependent on the structure and chemical properties of the species formed under the specific experimental conditions. MBT contains three atoms available for coordination i.e. N and S atoms in the ring and S atom of the thiocarbonyl group. The S atom of the thiocarbonyl group (C=S) that is ionized in alkaline medium can react with Cu and form thick polymeric film. The surface coverage is 0.89 which is the highest value recorded among all the investigated compounds. TTA does not act as a copper corrosion inhibitor in 0.1M NaOH.

The effect of 3-benzylidene amino 1,2,4-triazole phosphonate (BATP), 3-cinnamyledene amino 1,2,4-triazole phosphonate (CATP), 3-salicylalidene amino 1,2,4-triazole phosphonate (SATP), 3-para nitro benzylidene amino 1,2,4-triazole phosphonate (PBATP) in the neutral environment and its

interference with biocides is studied. The synthesized triazo phosphonates are used as inhibitors together with molybdate and cetyl trimethyl ammonium bromide (CTAB) as biocide. SATP is the most efficient due to the presence of electron releasing character of OH group, PBATP is the least effective due to the coplanarity of p-NO 2 group with the phenyl ring which imparts maximum electron withdrawal. Molybdate act as corrosion inhibitors in neutral and alkaline solutions. There is synergism between molybdate and inhibitor which may be related either to interaction between the inhibitor compounds or to interaction between the inhibitor and ions present in the aqueous media. The reason for selecting CTAB as biocide is that CTAB is not only the cationic surfactant but is also a quaternary ammonium salt with a long hydrocarbon chain whose homologues are used as inhibitors and biocides. The halides are the most effective derivatives since they increase inhibiting tendency of the positive quaternary ammonium ions through a synergistic effect. Inhibitor and biocide are added to the system at the same time as well with the 24h time difference in order to evaluate interference between them. The most effective treatment is the application of 15ppmCTAB+4ppmSATP+5ppmMo. Maximum efficiency is noticed for the compounds with the methoxy phenyl substituents, since the basicity of the coordinating atoms are increased by electron donating groups. The electron withdrawing groups such as p-nitro group retards this electron transfer process, which results in decreased inhibition efficiency. Regarding the protective films structure the following can be said: there is P-O-Cu bond, polymeric 5- and 6-membered copper-inhibitor ring complex is formed on the copper surface via reaction between the triazole ring and the metal surface, and in addition the CTAB-Cu 2+ complex can be deposited as a layer and as a part of the protective film. [13] Table 5. The results of the treatment with triazo phosphonates [13] inhibitor media concentration IE (%)

71.25 +Mo 5ppm 72.50 73.12 BATP lake water +CTAB 15ppm 81.25 4ppm

73.12 +Mo 5ppm 74.37 inhibitor added at the same time

75.62 CATP lake water +CTAB 15ppm inhibitor added after 24h 82.50 4ppm

75.00 +Mo 5ppm 76.25 inhibitor added at the same time 78.12 SATP lake water +CTAB 15ppm inhibitor added after 24h 83.75

62.50 +Mo 5ppm 65.62 inhibitor added at the same time 71.25 PBATP lake water +CTAB 15ppm inhibitor added after 24h 76.25 CTAB lake water 15ppm 77.50 Mo

lake water 5ppm 50.40 El-Sayed M.Sherif [14,15] investigated the effect of 3-amino-1,2,4-triazole (ATA) on the copper corrosion in 0.5M HCl [14] and in 3.5% NaCl [15]. It is found that ATA strongly adsorbs on the Cu surface in chloride solution, forms a complex with Cu + and inhibits copper corrosion by

preventing the formation of CuCl 2- through which Cu dissolution occurs. The maximum inhibition efficiency in the HCl solution in the presence of 5?10-4M ATA is achieved after 48h and it is ~60% that increases to ~67% and ~72% when the concentration is 1?10-3M and 5?10-3M ATA, in the NaCl solution in the presence of 1mM it is 94.4%, and after 50h it is 96.1%. The effect is long-term and the maximum inhibition efficiency after 24days is 83% for 0.5mM ATA, and increases to 90% in the presence of 1.0mM ATA.

In the paper published by https://www.wendangku.net/doc/2f11680240.html,litha et al. [16] the influence of derivatives of 1,2,4-triazole and surfactants in the aqueous solution containing potassium hydrogen phthalate and hydrochloric acid (pH

2) is examined. The inhibitors are 3-amino 1,2,4-triazole (ATA), 3-amino mercapto 1,2,4-triazole (AMT), 3-amino 5-methylthio 1,2,4-triazole (AMTT) and cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS). The performance can be ranged as ATA

medium concentration EI (%) weight loss EI (%) potentiodynamic polarisation synergism parameter 100ppm 62.50 63.08 +CTAB 10ppm 89.71 90.00 1.42 ATA

+SDS 2500ppm 92.36 93.08 1.72 100ppm 68.91 70.00 +CTAB 10ppm 91.17 92.31 1.50 AMT

+SDS 2500ppm 92.48 94.31 1.70 100ppm 78.40 79.23 +CTAB 10ppm 91.50 94.62 1.48 AMTT

KH phthalate +HCl pH=2 +SDS 2500ppm 93.32 96.15 1.74 CTAB

10ppm 61.22 61.54 SDS 2500ppm 66.35 67.69

The efficiency of two newly developed triazole type organic compounds: bis [4-amino-5-hydroxy-1,2,4-triazol-3-yl]methane (D 1) and bis[4-amino-5-hydroxy-1,2,4-triazol-3-yl]butane (D 2) as copper corrosion inhibitors in 4.0M HNO 3 solution at 25°C is investigated. It is noticed that they act predominantly as cathodic inhibitors with long-term effectiveness whereat the inhibition efficiency is over 99%. D 1 is more efficient than D 2 and that is attributed to the screening effect of the –CH 2- chain of compound D 2, the efficiency increases with concentration and the mechanism is different at lower and at higher concentration. The adherent film of low solubility is formed which prevents the components of solution to reach the metal and ensures optimum protection. [17]

The most commonly used copper corrosion inhibitor of azole type is benzotriazole. There are numerous investigations of inhibitive action of BTA on copper corrosion in various media such as solutions containing chloride ions [18-22], nearly neutral solutions [23,24], strongly acidic [21,25-27]

and strongly alkaline media [12] and atmosphere [28,29]. Besides the common applications it is shown that BTA is the only inhibitor that provides effective protection of copper archeological artifacts during preservation process [24,29], although it is not the most efficient it exhibit some protection of electrodeposited copper powder [28]. However, it is noticed that BTA action is weaker in highly acidic and highly alkaline media as well as in media containing aggressive ions, so the investigation of its derivatives action is also conducted.

Benzotriazole is an organic compound consisting of benzene and triazole ring, which formula is C6H5N3. The presence of nitrogen atoms in triazole ring enables bonding with copper and is a basis for inhibitive effect of BTA. Generally about BTA action it can be said that it is anodic [21,23,30,31] copper corrosion inhibitor which action mechanism includes chemisorption [12,23,31-34], rearly physisorption [27,35] on the copper surface that follows Langmuire isotherm [12,23,26,27,32,35] followed by the formation of complex Cu(I)BTA[12,18-20,22,23,25,26,32,36-38]. Coordination between BTA molecule and Cu electrode surface occurs via nitrogen atom of triazole ring [12,23,27,32,38]. BTA molecules can be oriented parallel [12,23] or vertical [33,34] regarding surface. The orientation of inhibitor molecule is important because of the possibility of formation of stronger bond if the orientation is parallel due to interaction of π electrons of the ring with vacant d orbitals of copper. [12]

The mechanism of complex formation is proposed and described by the following reactions [18]:

Cu(s) + BTAH(aq) = Cu:BTAH(ads) + H+(aq)

where Cu:BTAH(ads)stands for BTAH adsorbed on Cu surface. In the presence of oxidants or by anodic polarization it can be oxidised to protective complex:

Cu:BTAH ads = Cu(I)BTA(s) + H+(aq) + e-

From this reaction it can be seen that increase of BTA concentration shifts the reaction towards formation of larger amount of protective complex Cu(I)BTA, that is confirmed in numerous experiments [12,18,22-24,27,29,30,35-38]. Also it can be observed that pH increase favours complex formation. [12]

Based on the characteristics of BTA itself the inhibition efficiency in the specific media can be explained. BTA can be found in three forms dependently on pH value of solution [36]. In strongly acidic media it has protonated form BTAH2+, in weakly acidic, neutral and weakly alkaline media its form is BTAH, while in strongly alkaline media it is BTA-. Considering that Cu surface is positively charged in the solution it can easily be concluded which form is more, and which is less favorable. Tromans [37] constructed the E-pH diagrams for systems containing Cu and BTA that provide an indication when the protective action can be expected, and when not, dependently on pH, potential and inhibitor concentration. The action mechanism is adsorption on Cu surface that is an exothermic process so it is obvious that temperature increase has an adverse effect on the inhibition efficiency [23,33,34].

Int. J. Electrochem. Sci., Vol. 3, 20089 The behavior of BTA derivatives is very similar. The introduction of the substituent groups has no effect on the mechanism of the inhibitive action while it has influence on inhibition efficiency [23,27,30,32,35,39].

P.Yu [23] and B.H.Loo [32] investigated influence of benzotriazole (BTA) and tolytriazole (TTA) on copper corrosion inhibition in deionized water [23] and in chloride solutions [32]. TTA has three isomers with the methyl group substituted in 4-, 5- or 6-position on the benzene ring. Both compounds exhibit inhibiting action, but TTA is more efficient. It can be concluded that the introduction of nonpolar methyl group increases the film hydrophobicity hence improving the copper corrosion prevention. A.Frignani [30] evaluated the effect of the introduction of alkyl chains of various lengths on the efficacy of the copper corrosion inhibition in 0.1M Na2SO4 and 0.1M NaCl solutions, pH=2.5. 1,2,3-benzotriazole (BTAH) and 5-alkyl-derivatives of benzotriazole, methyl-benzotriazole (C1-BTAH), butyl-benzotriazole (C4-BTAH), hexyl-benzotriazole (C6-BTAH), octyl-benzotriazole (C8-BTAH) and dodecyl-benzotriazole (C12-BTAH) are used. In Na2SO4solution the inhibition efficiency increases with introduction of alkyl groups from BTAH to C6-BTAH while C8-BTAH has almost the same effect as C6-, and C12-BTAH does not have remarkable influence because of low sollubility. More aggressive media, such as NaCl solution, hinders the action of the less effective inhibitors thus only C4-BTAH and C6-BTAH act as highly effective inhibitors while C6-BTAH is the most efficient. It can be concluded that introduction of the alkyl chain in the 5- position of benzotriazole improves the action of the base molecule mostly towards the anodic reaction. Positive effects are more significant as the chain length increases up to 6 C atoms.

A.Arancibia [35] conducted a research of the effect of BTA and its derivatives 5-methyl BTA and 5-chloro BTA on the copper corrosion inhibition in aerated 0.1M HCl solution. BTA and 5-methyl BTA act as cathodic inhibitors and their action is associated with adsorption of BTAH2+on Cu. 5-chloro BTA dependently on concentration has mixed, and at higher concentration anodic action mechanism associated with passivation and CuBTA formation. Chloro in 5-position enables formation of the partially protonated species BTAH while nitrogen is responsible for bonding with copper. It is noticed that the interaction between inhibitor and metal surface enhances with substituents in 5- position of inhibitor molecule, while electron acceptor groups have better effect that electron donor.

V.Otieno-Alego [38] studied the inhibiting action of 4- and 5-carboxybenzotriazole (4- and 5-CBT) and BTAH on copper corrosion in 0.1M Na2SO4 solutions (pH 0 and 4) as well as in Na2S?9H2O solution. It is noticed that the inhibition efficiency is lower in pH=4 solution compared to that in pH=0 solution, but it increases with exposure time. The optimum concentration is approximately 7,5?10-4M, and in mixture of 4- and 5-CBT the component having the inhibiting properties is 5-CBT. The mechanism of action is the same as for BTAH and includes adsorption and coordination with copper through N atom of triazole ring. It is found that the introduction of the electron withdrawing group (-COOH) in 4- position decreases the strength of coordination while in the 5- position the electrophilic effect is less effective and leads to stronger chemisorption and better corrosion inhibition. J.Bartley [27] conducted a research on the series of alkyl esters (methyl, butyl, hexyl and octyl) synthesised from the mixture of 4-CBTAH and 5-CBTAH in aerated pH~0 solution. It is observed that the inhibition efficiency increases with hydrocarbon chain length. This is attributed to increased physisorption of the alkyl chain as more methyl groups are introduced and chemisorption through

azole ring N. In order to obtain the same degree of surface coverage concentration of inhibitor required becomes progressively less as the molecule is larger due to more efficient surface blocking. Based on the presented data it can be said that esterification of BATH particularly with the introduction of the longer hydrocarbon chains is beneficial. The same results were reached by N.Huynh et al. [40] investigated the inhibition action of coatings formed dipping copper in solutions of alkyl esters (methyl, butyl, hexyl and octyl) of carboxybenzotriazole (mixture of 4- and 5-CBTAH, and separately 4- and 5-CBTAH-OE) in 0.5M Na2SO4 solutions with pH 0 and 8. The inhibition efficiency depends on type of solvent used in the coating solution (water, alcohol, acetone), temperature (30-100°C) and period of immersion (5min-6h). Pretreatment by immersing copper in hot (70°C) aqueous solution (1?10-4M) for aproximately 2-3h gave a film with the highest degree of corrosion protection. Film formed in aqueous solutions of inhibitors can be stable in acidic solution (pH~0) for up to three days, and in near-neutral sulphate solution (pH~8) for up to 10 days. In both acidic and neutral solution the inhibition efficiencies of the protective film increase with the length of the alkyl ester chain in the order: methyl

Guo-Ding Zhou [20] investigated the effect of 1-(2,3-dicarboxypropyl)benzotriazole (BT-250) which is a derivative of BTA but is less efficient as copper corrosion inhibitor in NaCl solution. Da-quan Zhang [41] investigated the effect of a novel corrosion inhibitor bis-(1-benzotriazolymethylene)-(2,5-thiadiazoly)-disulfide (BBTD) on copper corrosion in 3% NaCl and 0.5M HCl solutions. BBTD contains two BTA moieties and one thiadiazole moiety. It is found that BBTD is a good inhibitor for copper in both neutral and acidic solution, but it has greater influence in 3% NaCl then in 0.5M HCl solution. This can be attributed to the stability of cuprous oxide in neutral solution. BBTD adsorbs on the Cu surface and forms protective complex with Cu(I) ion. The complex is identified as BBTD-Cu(I) and protects copper surface from aggressive Cl-ions. BBTD is more efficient then BTA under this conditions, that can be seen based on data from table 7. M.A.Elmorsi et al. [42] investigated copper corrosion inhibition in aerated 0.5M H2SO4solution in the presence of two classes of heterocyclic compounds, namely phenylazo-pyrazolones (PAP) or hydroxy quinoline and bromobenzyl-carboxy-1,2,3 triazole (BCT) derivatives. Inhibition efficiency (IE) of BCT is 75-97%, and IE of PAP 90-97% while there is no regular change of IE with inhibitor concentration. The influence of temperature was investigated in the range form 300 to 343K and negative influence of high temperature is observed. Influence of PAP is attributed to adsorption, followed by Cu-chelates precipitation on copper surface via the interaction of C=O and N=N groups of the inhibitor molecule with the Cu ions of polarized surface. Effect of BCT can be a result of -complex formation between adsorbed triazole ring of inhibitor and Cu ions. Both PAP and BCT are cathodic inhibitors with significant difference in adsorption degree or protective Cu-complex formation.

The existence of a synergistic effect on copper corrosion inhibition in sulphuric acid solution in the presence of BTA and iodide ions is observed by D-Q.Zhang [25] and Y-C.Wu [43]. Synergistic effect is assumed to be a result of initial contact adsorption of iodide anions on copper, followed by a decrease in positive in the metal that facilitates the adsorption of protonated BTA on Cu surface [25] or Cu(IBTA) complex polymer film formation [43]. R.F.V.Villamil [26] also noticed synergistic effect on

inhibition of copper corrosion in sulphuric acid solution in the presence of BTA and sodium dodecylsulfate (SDS).

When considering the data presented above, the following conclusion is imposed, the introduction of substituent groups into the BTA molecule leads to improvement of its inhibition properties and protective action. Withal, the synergistic action of BTA with some compounds or ions, that significantly improves BTA efficiency, is perceived to be of great importance. The results of the research are summarised in table 7. Table 7. The values of the inhibition efficiency obtained by using BTAH and its derivatives inhibitor concentration media IE % references BTAH 10ppm 84.48 TTA 10ppm Deionized water 95.48 [23] BTAH 10-5M 83.30 C1-BTAH

10-5M 83.30 C4-BTAH 10-5M 97.30 C6-BTAH 10-5M 99.30 C8-BTAH saturated solution 0.1M Na 2SO 4; pH 2.5; exposure time 3h 99.00 [30] BTAH 10-2M 90.80 5-methyl-BTAH 10-2M 97.87 5-chloro-BTAH

10-2M 0.1M HCl 99.79 [35] 4-CBT 7?10-4M 20.00 5-CBT

7?10-4M 70.00 BTAH 7?10-4M 0.1M Na 2SO 4; pH 0; 3 days 40.00 4-CBT 5?10-4M 10.00 5-CBT 5?10-4M 0.1M Na 2SO 4; pH 4; 10 days 55.00 [39] BTAH

10-4M 58.00 CBTAH-ME 10-4M 57.00 CBTAH-BU 10-4M 67.50 CBTAH-HE 10-4M 85.00 CBTAH-OE

10-4M pH 0 98.00 [27] 0.5M Na 2SO 4 pH 0 45.10 BTAH

10-4M 0.5M Na 2SO 4 pH 8 63.40 0.5M Na 2SO 4 pH 0 30.20 CBTAH-ME

10-4M 0.5M Na 2SO 4 pH 8 60.20 0.5M Na 2SO 4 pH 0 58.20 CBTAH-BU

10-4M 0.5M Na 2SO 4 pH 8 76.20 0.5M Na 2SO 4 pH 0 63.60 CBTAH-HE

10-4M 0.5M Na 2SO 4 pH 8 86.80 0.5M Na 2SO 4 pH 0 95.10 CBTAH-OE

10-4M 0.5M Na 2SO 4 pH 8 99.00 0.5M Na 2SO 4 pH 0 94.80 4-CBTAH-OE

10-4M 0.5M Na 2SO 4 pH 8 99.10 0.5M Na 2SO 4 pH 0 95.10 5-CBTAH-OE

10-4M 0.5M Na 2SO 4 pH 8 99.10 [40] BTAH 0.1M atmosphere 99.00 [29] BTAH 10-3M 0.5M HCl 26.20 [21] BTAH 0.1M 1M HCl; pH0 99.73 [38] BTAH 10-3M 58.20 BTAH + KJ 5?10-4M+5?10-4M 0.5M H 2SO 4 67.60 [25] BBTD

10-3M 3% NaCl 87.60 BBTD 10-3M 0.5M HCl 79.20 [41]

Another azole type compound that also received plenty of attention is imidazole as well as its derivatives. Imidazole is a planar, aromatic heterocyclic organic compound containing two nitrogen atoms that form fivemembered ring. One of the nitrogen atoms is a pyrole type, and the other of pyridine type. Based on the structure it can be seen that imidazole molecule has two places convinient for bonding with surface: N atom with lone sp2 electron pair and aromatic ring. It is favourable due to its non-toxicity and high inhibition efficiency.

Action mechanism is the same as for other azole compounds, adsorption of molecules on copper surface and formation of protective complex with copper. The efficiency increases with concetration increase, while the temperature increase has a negative effect. Introduction of groups influences the efficiency but not the inhibition mechanism. Following groups showed to be especially favourable phenyl group, mercapto group, presence of more heteroatoms as potential centres for bonding with copper as well as benzene ring.

They are revealed to be efficient copper corrosion inhibitors in various media such as: nitric acid [44], sulphuric acid [25,45], hydrochloric acid [21,46], sodium chloride [47], atmosphere [48], sodium hydroxide [12].

Synergism has become one of the most important effects in the inhibition processes and it serves as the basis for all modern corrosion inhibitor formulations. D-Q.Zhang [25] investigated the influence of 2-mercapto benzimidazole (MBI) and KI on copper corrosion in 0.5M sulphuric acid. The results indicate that MBI and KI have a synergistic effect to prevent copper corrosion. This effect is atributed to formation of couprous iodide (CuI2) complex that is relatively stable and cuprous ions can react with protonated MBI and form (Cu+MBI) film that is the best protection against corrosion. Based on that the inhibitor film (Cu+MBI) formation may be acomplished through the following steps: Cu + I- (CuI)ads + e-

(CuI)ads + I- CuI2- + e-

CuI2- + p-MBI+ (CuMBI) + 2I- + p+

Iodide is not incorporated into the MBI inhibitive film on the copper surface. Synergistic effect is a result of initial contact adsorption of iodide anions on copper, followed by a decrease in the positive in the metal that improves the adsorption of protonated MBI on Cu surface. Organic molecule MBI has better inhibition effect on copper corrosion in comparison to BTAH in aerated sulphuric acid solution, it is about 20% more efficient.

The coordination property of imidazole derivatives with metals is used to construct higher-ordered hierarchical mesostructures in large scale [49]. In this order 4,5-diphenylimidazole (DPI) is used. Different characteristics can be obtained by changing the assembly conditions. The mesostructures can endow the copper surface with superhydrophobic property and significantly inhibit copper corrosion. The stucture is influenced by the solvent, time and concentration of DPI. It is shown that complex formed by the coordination of DPI with Cu plays a decisive role in providing a centre of layer nucleation and growth.

Int. J. Electrochem. Sci., Vol. 3, 2008 13Table 8. The results of imidazole application as the copper corrosion inhibitior inhibitor media concentration IE% references 1-(p-tolyl)-4-methylimidazole

0.05M 86.00 1-phenyl-4-methylimidazole 0.50M 94.30 4-methyl-5-hydroxymethylimidazole 0.30M 65.40 Imidazole 0.5M H 2SO 4 0.50M 44.00 [45] MBI 1mM 74.20 MBI + KJ 0.5M H 2SO 4 0.75mM+0.25mM 95.30 [25] MBI

0.5M HCl 1mM 91.60 [21] IM (imidazole) 10-3M 33.00 TMI (1-(p-tolyl-4-methylimidazole)) 10-3M 54.00 MMI (2-mercapto-1-methylimidazole) 1M HCl 10-3M 87.50 [46] Imidazole 10-4M 49.79 4-methylimidazole 10-4M 63.31 4-methyl-5-imidazolecarbaldehyde

3?10-4M 71.24 ethyl-4-methyl-imidazolecarboxylate 10-3M 80.50 4-methyl-1(4-methoxyphenyl)imidazole

2?10-4M 83.95 1-(p-tolyl)-4-methylimidazole 7?10-4M 93.03 1-phenyl-4-methylimidazole 3% NaCl 5?10-3M 94.31 [47] imidazole

1M HNO 3 0.1M 94.93 [44] BIMD (benzimidazole) 2.0mM 82.00 MBIMD (mercaptobenzimidazole) 2.0mM 74.00 IMD (imidazole) 0.1M NaOH 2.0mM 46.00 [12]

3.2. Amines

Copper corrosion inhibition in de-aerated, aerated, and oxygenated HCl [50] and NaCl [51] solutions by N-phenyl-1,4-phenylenediamine (NPPD) is investigated. The NPPD adsorbs on the copper surface whereat Cu undergoes oxidation to Cu + and form insoluble complex Cu +-NPPD on the surface. The efficiency increases with time and inhibitor concentration. The inhibition efficiency (IE) values are shown in table and reveal that NPPD is a good copper corrosion inhibitor in HCl though the IE is somewhat lower than in NaCl solution. The results are presented in table 9. Table 9. Copper corrosion inhibition efficiency in the presence of 10mM NPPD in 0.5M HCl solution [50] deaerated aerated oxygenated

IE(%), polarization curves 81.70 83.75 68.42 IE(%), Nyquist plots 79.80 73.60 83.00

The behavior of secondary amines as copper corrosion inhibitors in acid media, 0.5M hydrochloric acid and 0.5M sulphuric acid, is studied. [52] The homologous series of aromatic secondary amines with various substituents is investigated. All the investigated compounds contain amino group that has the ability of adsorption and co-ordination with metal as well as the polar and unsaturated bonds such as heterocyclic ring with oxygen (furan) substituted in 5- position and aromatic ring with methyl group in p-position. The nonsubstituted secondary amine (N-(2-furfuryl)-p-toluidine)

is the least efficient while the substitution of a hydrogen atom (-Cl, -Br, -NO2, -CH3) in the 5-position by either the electrophilic -Cl, -Br, -NO2, or the nucleophilic CH3substituent increases protective effect. In hydrochloric acid all the substituted secondary amines have good inhibiting characteristics while in sulphuric acid only the halide substituted ones show significant inhibition efficiencies as can be seen in table 10.

Table 10. The efficiency of copper corrosion inhibition in the presence of secondary amines [52]

Inhibitor 0.01M N-2-furfuryl-p-

toluidine

N-5-chloro-2-

furfuryl-p-toluidine

N-5-bromo-2-

furfuryl-p-toluidine

N-5-nitro-2-

furfuryl-p-toluidine

N-5-methyl-2-

furfuryl-p-toluidine

IE%, 0.5M

HCl 36.00 78.00 62.00 84.00 86.00

IE%, 0.5M

H2SO4

/ 81.00 84.00 31.00 /

Schiff bases are condensation products of an amine and a ketone or aldehyde, with R2C=NR’as their general formula. They contain heteroatoms and electrons that enable bonding with copper.

H.Ma [53] investigated copper corrosion inhibition in 0.5M NaCl and NaBr solutions by three Schiff bases N,N’-o-phenylen-bis(3-methoxysalicylidenimine) (V-o-Ph-V), N,N’-p-phenylen-bis (3- methoxysalicylidenimine) (V-p-Ph-V) and N-[(2-hydroxy-3-methoxyphenyl) methylene]-histidine (V-His). The inhibition efficiency is strongly dependent on the geometric structure and it decreases in the following order: V-o-Ph-V(around 90%); V-p-Ph-V(around 80%); V-His(around 40%). The inhibition action is a result of adsorption on the copper surface followed by complexation with Cu(I) or Cu(II) ions forming a blocking barrier to copper corrosion. It is noticed that these compounds strongy inhibit copper corrosion in chloride solutions of variuos pH values and they are environmentaly friendly. V-o-Ph-V is a compound with a planar structure and there are large conjugate bonds among the three aromatic rings and the two –CH=N- groups so it is inferred that it adsobs rapidly on the copper surface and forms a thin protective layer via the formation of a N-Cu coordinate bond or electron interactions. Cu(I)-(V-o-Ph-V) chelate forms, and afterwards also Cu(II)-(V-o-Ph-V). A crystal of the chelate precipitates on the surface from the solution resulting in a thick protective film and the anodic dissolution is inhibited. Long immersion and high concentration favoure the inhibition effect.

Cu+V-o-Ph-V Cu-(V-o-pH-V)ads

Cu(I)+V-o-Ph-V Cu(I)-(V-o-Ph-V)ads

CuX2-+V-o-Ph-V Cu(I)-(V-o-Ph-V)ads+2H++2X-

V-p-Ph-V is also a planar compound with a big conjugate bond. The difference is in the arrangement of –C=N- groups. V-His is a non-planar compound so no big conjugate bond can be formed. All the three Schiff bases can form chelates with Cu(I) or Cu(II), but Cu complexes with V-p-Ph-V and V-His are less compact. V-o-Ph-V and V-p-Ph-V in the halide solutions change the Cu dissolution mechanism or hinder the diffusion of dissolved oxygen towards Cu surface, they behave as mixed inhibitors but cathodic reaction is more influenced.

Maryam Ehteshamzadeh et al. [54,55] investigated the effect of novel the new series of Schiff base molecules on copper corrosion. The effect of N,N’-ethylen-bis(salicylidenimine) (S1), N,N’-isopropylen-bis(salicylidenimine) (S2) and N,N’-ortho-phenylen acetyl acetone imine (2-hydroxy benzophenone imine) (S3) on copper corrosion during treatment with 1M HCl solution is investigated

[54]. It is shown that they are good inhibitors with inhibition efficiency up to 92%. The differences in the efficiency among molecules are correlated with their structure. S2 may assume a coplanar conformation which would provide optimal interaction of aromatic electrons with the metal surface and thus show an advantage over S1 and S3. They act as cathodic inhibitors. They obay Langmuir isotherm while the adsorption energies indicate mixture of physical and chemical adsorption. The inhibitive action of Schiff bases N,N’-ethylen-bis(salicylidenimine) (S-E-S) and N,N’-ortho-phenylen-bis(salicylidenimine) (S-o-ph-S) self-assembled films on copper surface in chloride (0.88M NaCl) and acid (0.5M H 2SO 4) solutions is investigated [55]. It is found that S-o-ph-S is more efficient then S-E-S. When the concentration is increased the inhibition efficiency increases but that kind of application is not economical in industrial conditions, however film modification with propanethiol and 1-dodecanethiol significantly improves corrosion resistance at lower concentrations. C 12H 25SH SAMs are better then C 3H 7SH SAMs. Synergetic parameter obtained in the presence of 25ppm Schiff bases and 5mM dodecanethiol is 1.92 for S-o-ph-S and 5.6 for S-E-S. Results are presented in table 11. Table 11. Copper corrosion inhibition efficiency in the presence of Schiff bases [55] inhibitor concentration, ppm media method exposure time, min IE,% 25 0.88M NaCl EIS 30 87.00 300 0.88M NaCl

EIS 30 96.00 25 0.5M H 2SO 4 EIS 30 65.00 300 0.5M H 2SO 4 EIS 30 92.00 S-E-S 300 0.5M H 2SO 4 polarization 30 78.00 25 0.88M NaCl EIS 30 88.00 300 0.88M NaCl EIS 30 99.00 25 0.5M H 2SO 4

EIS 30 69.00 300 0.5M H 2SO 4 EIS 30 96.00 S-o-ph-S 300 0.88M NaCl polarization 30 92.00

A.A.El Warraky [56] investigated the influence of ethylene diamine (EDA) on Cu in 0.01M HCl pH= 1.8-2 with and without presence of Na 2S additive. Inhibitor is added after the sample was immersed for 2h in the different Na 2S additive concentrations. In the presence of 2ppm Na 2S pits appeare because CuHS film is unable to protect Cu surface from attack. In the presence of higher concentrations there is no pitting. Complete surface coverage with strongly adsorbed HS - is achieved at concentration of 10ppm Na 2S, that points out that S 2- ions concentration increase facilitates HS - adsorption on copper surface that prevents pitting corrosion occurrance. The addition of various concentrations of ethylene diamine (EDA) increase promote the corrosion rate of copper due to autocatalytic dissolution process at the Cu surface. However there is a synergistic effect between EDA and Na 2S resulting from HS - adsorption on Cu that facilitates EDA adsorption. It is noticed that different organic inhibitors become protonated in acid solution:

EDA+H + EDAH +

Adsorption of (EDAH)+ is facilitated in the presence of adsorbed HS- thus the inhibitor film can be copper hydrogen sulphide EDA complex (CuHSEDA).

3.3. Amino acids

Amino acids form a class of non-toxic organic compounds that are completely soluble in aqueous media and produced with high purity at low cost. These properties would justify their use as corrosion inhibitors.

J.B.Matos [57] studied the effect of cysteine (Cys) on the anodic dissolution of copper in sulfuric acid, at room temperature using electrochemical methods. Cys (HSCH2CHNH2COOH) contains three dissociable protons, and in aqueous solutions ionization depends upon pH. Acording to the copper dissolution mechanism proposed for sulfate media in the absence of cys the main species present on the copper surface at low overpotentials is the intermediate Cu(I)ads. This indicates that the inhibitory effect of cys originates from this intermediate and suggests that film formed at higher cys concentrations (0.001 and 0.01mol/l) is Cu(I)-cys complex. Film has inhibition effect since current density is aproximately 20 times lower in the presence of cys. At low cys concentration, cys is adsorbed on surface but complex can not be formed. Influence of cys is not significant at higher overpotentials where the main species present on copper surface is Cu(II)ads. G.Moretti [58] investigated possibility to use tryptophan (Trp) as a copper corrosion inhibitor in 0.5M sulfuric acid in the 20-50°C temperature range. Trp has good inhibiting effect in the short-term tests and at the highest concentrations. Temperature increase has a negative effect on its efficiency.

Table 12. Inhibition efficiency values in the presence of 0.01M tryptophan at different temperatures calculated from potenciodynamicpolarization curves [58]

T(°C) 20 30 40 50

IE(%) 86.90 93.40 77.90 84.90

Trp adsorbs on copper surface maintaining a certain contact angle with the metal surface and it can be physisorption or chemisorption and obays Bockris-Swinkels’ isotherm where x=2 that means that Trp is at least in short time adsorbed on copper surface by displacing two water molecules. In the presence of inhibitor copper dissolution mechanism is changed so Cu is primarely oxidized to Cu+ and is able to form slightly soluble [Cu-Trp n]+ads complex as the main product of electrooxidation in the presence of a “clean” surface (Cu/Cu2O system). This complex lowers the Cu+ concentration making the successive oxidation to Cu2+negligible. In the presence of inhibitor this may participate in the intermediate formation [Cu+(ads)] depending on the chemical stability and oxidative property of the adsorbed [Cu-Trp n]+ads complex:

Cu+ads+nTrp [CuTrp n]+ads

The inhibition sustaines until the compex is adsorbed. Even if Trp suffers a certain photodegradation process at least for those Trp molecules present in the solution, the molecules of

inhibitor adsorb well on active sites of the metal and/or the passivation layer at 20°C that is proved by inhibition percentage (IP) that is 80% for the solutions kept in dark as well as those kept in light.

3.4. Triphenylmethane derivatives

Two nitrogen containing organic compounds which are triphenylmethane ((C6H5)3CH) derivatives, fuchsin basic FB(rosaniline chloride)(C20H19N3?HCl) and fuchsin acid sodium salt FA (C20H17N3O9S3Na2), are tested as new copper corrosion inhibitors. [33,34] These compounds are thought to be good candidates due to the presence of chloride ion in FB and the polar or charged nature of the more complex FA surfactant molecule. Investigation is performed in sulphuric acid [33] and hydrochloric acid [34] solutions at various concentrations and temperatures in the presence of different inhibitor concentrations. FB is more efficient than FA that can be attributed to different molecular structures. The Frumkin isotherm gives the best fit while inhibitor ocupies more then one active spot. The inhibition mechanism of FB and FA can be explained by the Cu(inhibitor)ads reaction intermediates:

Cu+inhibitor Cu(inhibitor)ads Cu n++ne-+inhibitor

inhibitor aqu+ H2O ads inhibitor ads+ H2O aqu

At first, when there is not enough Cu(inhibitor)ads to cover Cu surface, because the inhibitor concentration is low or because the adsorption rate is slow, metal dissolution takes place at sites on the Cu surface free of Cu(inhibitor)ads. With a high inhibitor concentration a compact and coherent inhibitor overlayer is formed on the copper, which reduces chemical attacks on the metal. FB addition introduces chloride ions that are primarely adsorbed so afterwards by synergetic effect FB cations are electrostaticaly adsorbed on the Cu surface covered with primarily chemisorbed chloride ions. The inhibition action of FA in an H2SO4 acid solution may result from the blocking effect due to physical adsorption of the negatively charged C20H17N3O9S32- to the positively charged copper surface by the electrostatic attraction force. Temperature negatively effects inhibition efficiency. Comparison of these results with those obtained using BTA under the same conditions reveals that in sulphuric acid solution BTA is the most efficient, while in hydrochloric acid solution FB is the most efficient and the inhibition efficiency of BTA is close.

3.5. Thiole group compounds

H.Baeza [59] studied copper corrosion inhibition by 1,3,4-thiadiazole-2,5-dithiol (bismuthiol) in 0.5M HCl at 25°C. The efficiency is increased as the inhibitor concentration is increased reaching maximum value of 84,1% at 80?10-5M. The inhibitor is chemisorbed on the copper surface obaying Langmuir isotherm, and since the peaks corresponding to the formation of complexes bismuthiol-Cu(I) and bismuthiol-Cu(II) are observed, it is concluded that inhibition mechanism originates from these complexes on metal surface.

Y.S.Tan [60] studied the effect of self-assembled monolayers (SAM) of a series of substituted benzenethiol (BT) X-C6H4-SH (where X=meta-NH23-aminobenzenethiol 3-A-BT,ortho-NH22-aminobenzenethiol 2-A-BT,para-NH24-aminobenzenethiol 4-A-BT, para-NHCOCH34-acetamidobenzenethiol 4-AA-BT,para-F4-fluorobenzenethiol 4-F-BT, para-CH34-methylbenzenethiol 4-M-BT and para-CH(CH3)24-isopropylbenzenethiol 4-IP-BT) molecules. SAMs are prepeared by adsorption from 5mM solution in ethanol, during 1h at room temperature, onto a fresh copper surface. The hydrophilic mercapto group (-SH) in the BT molecule has a strong affinity for copper and the inhibitor molecules anchor on the copper surface via the thiolate bond, while the hydrophobic benzene ring with different substituents constitutes the ultra thin protective monolayer. The formation of the benzenethiolate-Cu complex requires the loss of the –SH hydrogen though it is not yet determined whether this proton is lost as H2 or H2O:

X-C6H4-SH + Cu0 X-C6H4-S—Cu+ + 1/2H2

X-C6H4-SH + Cu0 +oxidant X-C6H4-S—Cu+ + 1/2H2O

The loss of the –SH hydrogen is enchanced by the electron withdrawing groups though according to the results it can be inferred that any substitution in the BT benzene ring regardeless of whether electron-donating or electron-withdrawing, improves the corrosion inhibiting properties of the chemisorbed films. Self-assembled monolayers of benzenethiols chemisorbed on Cu surface are good copper corrosion inhibitors in 0.5M sulphuric acid. The structure of the inhibitors influences their inhibition efficiency and is strongly affected by the type and the position of the substituent functional group on BT. The results indicate that the inhibition efficiencies (IE) of the para substituted BT molecules increase in the following order: –CH(CH3)2>–CH3>–F> –NHCOCH3>–NH2. The effect of the ring position of the substituent on IE is ortho > meta > para, relative to the –SH position. These results are important in providing the rationale for the selection and the molecular design of inhibitors against Cu corrosion in aqueous media.

Table 13. The effect of benzenethiol SAMs on copper corrosion in 0.5M sulphuric acid [60] inhibitor BT 4-IP-BT 4-M-BT 4-F-BT 4-AA-BT 4-A-BT 3-A-BT 2-A-BT

IE%,polarization curves 74.39 86.47 82.53 80.53 66.01 53.51 60.25 72.30

IE%, EIS 74.10 90.60 89.10 87.10 82.60 76.80 78.00 80.40

The inhibition of copper corrosion in 1.5% NaCl solution is studied at 25, 35 and 45°C using three inhibitors: thiosemicarbazide (inh 1), phenyl isothiocyanate (inh 2) and their condensation product 1-phenyl-2,5-dithiohydrazodicarbonamide (inh 3). [61] It is concluded that all the three compounds are efficient corrosion inhibitors whereat the inhibition efficiencies follow the sequence: inh3>inh1>inh2. The enhanced effectiveness of the inh 3 can be correlated with the structure and size of molecule, inh 3 has four nitrogen atoms, two sulphur atoms and delocalised e electron density acting as active centres and the largest surface area. Mechanism of inhibition is proposed as adsorption only in case of inh 2; inh 1 at lower concentrations inhibits corrosion through adsorption

while at higher concentrations Cu(I) complex is formed that gradualy oxidises into Cu(II) complex. Complex films are responsible for corrosion inhibition. Inh 3 follows both the mechanisms simultaneously. It can be noticed that inhibition efficiency increases with temperature. Table 14. Inhibitive action of thiosemicarbazide (inh 1), phenyl isothiocyanate (inh 2) and 1-phenyl-2,5-dithio hydrazodicarbonamide (inh 3) on copper corrosion in 1.5% NaCl [61] IE (%) Inhibitor

concentration (ppm) Method 25°C 35°C 45°C weight loss 72.00 76.00 84.00 Inh 1

100 polarization 69.00 74.00 83.00 weight loss 62.00 66.00 70.00 Inh 2

100 polarization 60.00 63.00 67.00 weight loss 82.00 88.00 93.00 Inh 3 100 polarization 80.00 85.00 92.00

3.6. Phosphates as copper corrosion inhibitors

Copper corrosion by-product release to potable water is a complex function of pipe age, water quality, stagnation time and phosphate inhibitor type. Phosphates can be phosphoric acid, combination of orthophosphoric acid and zink orthophosphate, polyphosphate or blend of orthophosphoric acid and polyphosphate. It is noticed [62] that dosing of 1mg/l orthophosphate led to reductions in copper release ranging from 43-90% when compared to the same condition without inhibitor regardless of pipe age, water quality or stagnation period. Ortophosphate and hexametaphosphate have beneficial effects on copper release, but ortophosphate leads to greater reductions in copper release when compared to hexametaphosphate. Shiyin Li [63] investigated the adverse effect of organic matter on orthophosphate corrosion inhibition for copper pipe in simulated soft water. Sodium alginate and fulvic acid are selected to simulate extracellular polymeric substance produced by bacteria and natural organic matter in potable water. It is observed that organic matter markedly influence orthophosphate corrosion inhibition efficiency for copper pipes of various age (1mg/l as P), sodium alginate of low concentrations increases Cu dissolution but it decreases at concentration of 16mg/l, fulvic acid in concentration of 16mg/l strongly influences soluble Cu release (release increases and more from new pipes), at higher pH copper dissolution decreases.

Two kinds of phosphates, triethyl phosphate (TEP) and triphenyl phosphate (TPP), are used to form self-assembled monolayers, in 1?10-3M ethanolic solution, for the inhibition of the copper corrosion in 0.2M NaCl solution. [64] The results showed that their inhibition ability first increases with increasing immersion time in ethanolic solutions of the corresponding compounds. However, when the immersion time is increased over some critical point, the inhibition effect decreases. The best effect is achieved after 12h immersion whereat the surface coverage is 93.80% for TEP, and 96.50% for TPP. Therefore, for the same immersion time the inhibition effect of TPP monolayer is more pronounced than that of TEP monolayer. The influence, on copper corrosion in 0.2M NaCl aqueous solution, of self-assembled monolayers (SAMs) of triethyl phosphate (TEP – (C 2H 5O)3PO) and mixed SAMs of TEP with cetyltrimethyl ammonium bromide (CTAB – (CH 3(CH 2)15(CH 3)3N +Br -)) formed on copper surface is studied. [65] Films are formed from 1?10-3M TEP ethanol solution, and

1?10-3M CTAB aqueous solution. It is noticed that inhibition efficiency (IE) increases with an increase in the immersion time of copper in TEP-containing solution. When the TEP film is modified with CTAB, the efficiency improves markedly. External magnetic field improves the inhibition effect of SAMs and the inhibition efficiency increases with the increase in the field strength. TEP molecule reacts with copper surface via oxygen atom at the end of molecule.

Table 15. The results of the investigation of TEP self-assembled layers [65]

Inhibitor exposure time (h) magnetic field strength (mT) IE (%)

TEP 1 0 81.00

TEP 20 0 95.00

TEP 1 160 97.60

TEP + CTAB 1 + 24 0 99.40

Inositol hexaphosphate (IP6) also known as phytic acid and its salts, is suggested to be used as an environmentally friendly reagent to prevent metal surface from corrosion through a self-assembled monolayers (SAMs) method. [66] It is cheap and available as naturally polyphosphorylated carbohydrate widely occurring in beans, brown rice, corn, sesame seeds, wheat bran. For monolayer formation 10-2M IP6aqueous solution was used. Polarization is conducted in 0.1M KCl solution at room temperature. Monolayers on the copper surface improve its corrosion resistance, but the efficiency is only 41.20% due to water co-adsorption.

3.7. Other organic compounds

The effect of potassium ethyl xanthate on the anodic dissolution of copper in 1.0M NaCl acidic solutions pH=1-3 is investigated. [67] Increasing the concentration and pH of the solution increases inhibition efficiency (IE) therefore in pH=3 solution in the presence of 5?10-3M KEtX IE is 83%. Inhibitor action can be related to formation of an adherent and compact film of the Cu(I) complex on the copper surface:

EtX-(aq) + Cu0 Cu(I)EtX(ad) + e-

Cu(I)EtX(ad) represents the surface dipol formed by chemisorption of EtX- ion on Cu electrode or growth of multilayer Cu(I)EtX film. Considering that the first step in copper dissolution in presence of inhibitor is formation of CuCl2- the process may follow the steps presented below:

Cu + 2Cl- CuCl2- + e-

CuCl2-+ EtX- Cu(I)EtX + 2Cl-

Soluble CuCl2- can either diffuse to the bulk solution or react with EtX- to form a protective film. The restrained inhibition efficiency is probably caused by the formation of an untight Cu(I)EtX

铜铟镓硒(CIGS)薄膜太阳能电池研究

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105cm-1，转化效率是所有薄膜太阳能电池中最高的，已成为全球光伏领域研究热点之一，即将成为新一代有竞争力的商业化薄膜太阳能电池。 1、铜铟镓硒薄膜太阳能电池的特性和竞争优势 太阳能电池的材料一般要求主要包括：半导体材料的禁带宽度适中;光电转化效率比较高;材料制备过程和电池使用过程中，不存在环境污染;材料适合规模化、工业化生产，且性能稳定。经过数十年电子工业的研究发展，作为半导体材料硅的提炼、掺杂和加工等技术已经非常成熟，所以，现在的商品太阳能电池主要硅基的。但是，硅是间接带隙半导体材料，在保证电池一定转化效率前提下，其吸收层厚度一般要求150～300微米以上，理论极限效率为29%，按目前技术路线，提升效率的难度已经非常巨大。同时考虑到加工过程近40%的材料损耗，材料成本是硅太阳能电池的最主要构成。另外，其材料生产过程的高温提炼、高温扩散导致其制备过程能耗高，这使其能量偿还周期长，整体成本高。尽管经过近几年的规模化发展，市场价格得到大幅下降，其每瓦成本仍高于2美元。如果再考虑到其制备过程的高污染，更增加了其环境治理社会成本，这些都严重制约了其竞争优势。相比较，薄膜太阳能电池具有较大的成本下降空间，同时它能够以多种方式嵌入屋顶和墙壁，非常适合光电一体化建筑和大型并网电站项目。在这种情况下，薄膜太阳能电池引起了人们的重视，近几年成了科技工作者的研究重点。从全球范围来看，光伏产业近期仍将以

中国铜铟镓硒(CIGS)薄膜太阳能电池未来发展趋势报告

2010-2012年中国铜铟镓硒（CIGS）薄膜太阳能电池市场全景调查及未来发展趋势报告 报告简介 报告目录、图表部份 目录 第一章铜铟镓硒（CIGS）薄膜太阳能电池概述 1 第一节太阳能电池的分类 1 一、硅系太阳能电池 1 二、多元化合物薄膜太阳能电池 3 三、聚合物多层修饰电极型太阳能电池 3 四、纳米晶化学太阳能电池 5 第二节铜铟硒（CIS）薄膜太阳能电池介绍7 一、CIS太阳电池的结构7 二、CIS太阳电池的特点7 三、生产高效CIS太阳电池的难点8 第三节铜铟镓硒（CIGS）薄膜太阳能电池介绍8 一、CIGS太阳能电池基本概念8 二、CIGS太阳电池的结构9 三、CIGS薄膜太阳电池的优势9 四、CIGS薄膜三种制备技术的特点10 第二章2008-2009年世界CIGS薄膜太阳能电池产业发展状况分析12 第一节2008-2009年世界薄膜太阳能电池的发展分析12 一、全球薄膜太阳能电池产业迅速发展12 二、三种薄膜太阳能电池进入规模生产12 三、薄膜太阳能电池企业纷纷布局14 第二节2008-2009年世界CIGS薄膜太阳能发展概况14

二、全球CIGS电池发展现状16 三、全球铜铟镓硒太阳能电池领导厂商发展概况19 第三节2009-2012年世界CIGS薄膜太阳能电池产业发展趋势分析21 第三章2008-2009年世界主要国家CIGS薄膜太阳能电池发展分析23 第一节2008-2009年世界CIGS薄膜太阳能企业发展动态23 一、IBM与TOK将共同开发新型CIGS太阳能电池23 二、德国SOLIBRO开始提供CIGS太阳能电池23 三、IBM涂布法CIGS太阳能电池转换效率突破12.8％24 四、VEECO公司CIGS薄膜太阳能电池设备获得订单24 五、亚化宣布进军CIGS薄膜太阳能领域25 第二节2008-2009年美国CIGS薄膜太阳能电池发展分析25 一、美国化合物太阳能电池专利权人分析25 二、美国CIGS化合物太阳能电池研发状况26 三、美国CIGS化合物太阳能电池厂商商业化动向27 四、2008年美国CIGS电池转换效率再创历史新高28 第三节2008-2009年日本CIGS薄膜太阳能研发状况28 一、日本研制成功CIGS太阳电池新制法28 二、日本采用CIGS太阳电池技术成功试制图像传感器29 三、日本量产型CIGS型太阳电池模块光电转换率实现15.9% 30 四、日本柔性CIGS太阳能电池单元转换率达全球之首31 第四章2008-2009年国外CIGS太阳电池主要生产企业运营透析32 第一节美国GLOBAL SOLAR ENERGY INC.（GSE）32 一、公司概况32 二、2008年GSE美国CGIS太阳能电池生产厂投产32 三、世界最大CIGS薄膜太阳能电池阵在GSE投入使用32 第二节日本的HONDA SOLTEC CO.，LTD 33 一、公司概况33 二、本田SOLTEC开发出CIGS型太阳能电池33

专家评审意见

深圳市宝安区防洪（潮）排涝工程规划评审会评审意见 xx水务局于 2007年1月23日 ~24日在银湖会议中心八角亭会议室主持召开《宝安区防洪（潮）排涝工程规划》（以下简称“规划”）评审会。市发改局、市财政局、市规划局、市国土局、市环保局、宝安区政府、区规划分局、区水务局、区环保局等单位的代表出席了会议，会议邀请了广东省及本市相关专业的九位专家组成专家评审组。（名单附后） 1、“规划”做了大量的资料收集、调查和整理工作，对宝安区的洪（潮）涝状况进行了较全面的分析研究。“规划”内容全面，依据充分，资料翔实，指导思想和技术路线正确，规范、标准、法律、法规的运用合理，设计原则和任务明确，与相关城市规划基本协调一致，规划深度基本满足相关规定的要求，请根据本次的评审意见，协调相关规划，经过补充、修改完善以后可以供展开下阶段工作的参照依据。 2、洪（潮）涝灾害给宝安地区的经济、社会发展和人民生命财产已造成了很大的危害和严重的影响，从根本上治理洪（潮）涝灾害已刻不容缓，这是弘扬“以人为本”、“和谐社会”、“和谐深圳”最基 本的出发点和落脚点，是经济社会全面协调可持续发展的基础，应全力推进这项工作的展开。 3、治理洪（潮）涝灾害坚持全面规划、综合治理、加强管理的规划原则是正确的，要做好全流域治理，系统布局、统筹兼顾，要坚持因地制宜，讲求实效，突出重点，近远期结合的基本原则。近期应先解决流域中比较紧迫，与百姓密切相关的工程项目，使老百姓早日摆脱水涝之苦。 4、根据《深圳市防洪（潮）规划修编报告（2002

~2010年）》提出宝安地区城市防洪标准为100年一遇的洪水标准，防潮标准为200年一遇潮位是合理和正确的。 排涝标准按： 有调蓄能力时，10年一遇24小时设计暴雨1天排完的标准；无调蓄能力时，按市政室外排水暴雨重现期1 ~3年的标准是合适和可行的。建议采用P＝2设计标准。 鉴于计算所得50年与100年一遇的水位差和相遇洪水时的淹没范围均不大，因而工程所有设防标准建议均按标准值一步到位，不再分期。 5、对于茅洲河、观澜河及西部沿海流域的各主要支流防洪标准，以及防洪体系相结合的河道治理标准，按照支流保护对象的重要性，不降低现有支流堤防标准以及洪灾经济损失的定量对比分析等因素提出的设防标准基本上是合理和可行的。 6、根据地理特征分列茅洲河流域、观澜河流域和西部沿海三大水系的水文资料，推算所得两岸潮位、洪峰流量等计算方法基本合理 的。 7、关于防洪（潮）排涝工程规划： 7- 1、对防洪排涝提出的泄、蓄、渗三种方式即通过大力清除河道内违法建筑和其它河道障碍以及河道清淤加大河道泄洪能力。充分挖掘现有水库、利用有条件的地形兴建水库，保留现有河道已有的鱼塘、低洼地兴建滞洪区或人工湿地等实施滞洪、削减洪峰、以及结合城区内雨水利用及城市建设等，修复下垫面，增大地面下渗能力，增加地面地下滞蓄能力的措施和理念是合理和行之有效的好方法。应予以肯定。 7-

培养计划专家评审意见表修订稿

培养计划专家评审意见 表 WEIHUA system office room 【WEIHUA 16H-WEIHUA WEIHUA8Q8-

（二）人才培养方案专家评审意见表 南京工程学院人才培养方案专业指导委员会评审意见表组织评审单位名称：南京工程学院 (部门盖章)

是否进行了实践性教学体系设计其合理性如何 实践性教学体系设计全面、丰富，课程设计面较宽，体现了本专业注重理论知识与实践应用的合理配置，并注重强化学生动手能力的培养。 从培养方案能否看出明显的专业特色该专业应具有的特色是什么 从课程设计和实践教学环节看，能体现本专业的特色，机械工程、机械制造、机械设计、控制工程等多门学科知识交融，适用范围很广。 本专业是机械设计与制造及其自动化，强调现代设计方法，特色在于机械基础理论知识扎实，各种实用的软件知识掌握的较好，适应面广。对机械工程学院而言，因具有扎实的基础理论，因此在各类机械行业中适应性强。 结论性意见： 本培养方案的目标定位准确，培养要求全面，理论课程体系设计合理，实践教学体系设计全面、实用性较强，符合工程应用型人才的培养方向。 存在的问题及建议（可另加附页）： 1、适当减少公共基础课程的学时，增加专业主干课程的教学学时，以使学生具 有较宽厚、扎实的专业技能。 2、建议增加“控制工程”实践性环节。 3、建议在四年级开设本专业有关国家标准选修课。 专业教学委员会主任（签字）： 2007年 6月 20日

专业人才培养方案评审人员名单 姓名最终学历职称工作单位（校外专家填写）所学专业评审专家签字备注序 号 1 汤文成博士教授东南大学机械学院机械制造 2 楼佩煌硕士教授/副院长南京航空航天大学机电学院机械电子 3 韩向东硕士教授南京财经大学管理科学与工程学院机械/工业工程 4 顾宗平大学本科高工南汽装备公司汽车拖拉机设计 5 熊宁硕士高工/总经理南京压缩机股份有限公司机械制造 6 姜卫忠研究生教授级高工南京扬子检修安装有限责任公司化工机械、工商管理 7 黄振仁大学本科教授南京工业大学过程装备与控制工程（原化 工机械） 8 吴中江硕士教授南京工程学院计算机 9 翟俊霞博士后副教授南京工程学院化工过程机械 10 汪木兰硕士副教授南京工程学院/自动化学院数控技术 11 李建启硕士教授南京工程学院流体传动

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铜铟镓硒薄膜太阳能电池项目可行性研究报告 编制单位：北京中投信德国际信息咨询有限公司编制时间：https://www.wendangku.net/doc/2f11680240.html, 高级工程师：高建

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目录 第一章总论 (1) 1.1项目概要 (1) 1.1.1项目名称 (1) 1.1.2项目建设单位 (1) 1.1.3项目建设性质 (1) 1.1.4项目建设地点 (1) 1.1.5项目主管部门 (1) 1.1.6项目投资规模 (2) 1.1.7项目建设规模 (2) 1.1.8项目资金来源 (3) 1.1.9项目建设期限 (3) 1.2项目建设单位介绍 (3) 1.3编制依据 (3) 1.4编制原则 (4) 1.5研究范围 (5) 1.6主要经济技术指标 (5) 1.7综合评价 (6) 第二章项目背景及必要性可行性分析 (8) 2.1项目提出背景 (8) 2.2本次建设项目发起缘由 (8) 2.3项目建设必要性分析 (8) 2.3.1促进我国铜铟镓硒薄膜太阳能电池产业快速发展的需要 (9) 2.3.2加快当地高新技术产业发展的重要举措 (9) 2.3.3满足我国的工业发展需求的需要 (9) 2.3.4符合现行产业政策及清洁生产要求 (9) 2.3.5提升企业竞争力水平，有助于企业长远战略发展的需要 (10) 2.3.6增加就业带动相关产业链发展的需要 (10) 2.3.7促进项目建设地经济发展进程的的需要 (11) 2.4项目可行性分析 (11) 2.4.1政策可行性 (11) 2.4.2市场可行性 (11) 2.4.3技术可行性 (12) 2.4.4管理可行性 (12) 2.4.5财务可行性 (13) 2.5铜铟镓硒薄膜太阳能电池项目发展概况 (13)

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