synthesis of a novel gemini cationic surfactant and its...

Research ArticleSynthesis of a Novel Gemini Cationic Surfactant andIts Inhibition Behaviour and Mechanism Study on 2024Al-Cu-Mg Alloy in Acid Solution

Juan Du Qiaochu Chen Qingmao Liu and Xuelan Hu

Sino-European Institute of Aviation Engineering Civil Aviation University of China Tianjin China

Correspondence should be addressed to Juan Du dujuan247163com

Received 10 August 2017 Revised 31 December 2017 Accepted 22 January 2018 Published 1 March 2018

Academic Editor Ramazan Solmaz

Copyright copy 2018 Juan Du et al This is an open access article distributed under the Creative Commons Attribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Isopropylamine was taken as a raw material to synthesize a new multi-alkyl multiple quaternary-ammonium salts geminisurfactant bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]-isopropylamine dichlorideThe structure of the synthetic productwas characterized by 1HNMR and FTIRThe surface activity was investigated the inhibition efficiencies and inhibitionmechanismof the synthetic product were studied by weight loss method electrochemical method microscopic morphology observation andadsorption model calculation The results indicate that cmc of synthetic product was 9204 times10minus4molL when the concentrationswere lower than cmc the inhibition efficiencies rose substantially which was up to 893 with the concentration of 9204times 10minus4molL when they were higher than cmc inhibition efficiencies were basically unchanged polarization tests showed that thesynthesis product could restrain both anodic and cathodic reactions when the concentrations were lower than cmc the adsorptionof the synthetic product conformed to the Langmuir model which formed monolayer on the 2024 Al-Cu-Mg alloy surface whenthey were higher than cmc it formed bilayer so the adsorption of the synthetic product did not conform to the Langmuir modelanymore

1 Introduction

Aluminium and aluminium alloys have been widely usedin aerospace transportation and construction industriesbecause of their goodmechanical properties low density andhigh corrosion resistance [1] In the process of metal acidpickling corrosion inhibitors are usually added to reducethe corrosion of acid to metallic matrix During this processsurfactants are often selected as the corrosion inhibitorsbecause of their good corrosion inhibition performance [2ndash5] Unlike traditional surfactants gemini surfactant has novelstructure and excellent performance using the spacer itcan connect two hydrophilic groups by chemical bonds toform a structure with double hydrophilic groups and doublehydrophobic chains This structure owns more advantagessuch as higher surface tension highermicelle forming abilityand better water solubility [6ndash8] At present gemini sur-factant has been widely used in metal corrosion inhibitiontransportation medicine and other industries which plays

a huge role in improving production process enhancingproduct quality reducing the cost and increasing the addedvalue [8ndash13] Therefore it is of great significance to study thesynthesis process of gemini surfactant with novel structureand excellent properties and to apply it to pickling process ofaluminium alloy for aviation

In recent times the studies of the corrosion inhibitionperformance of gemini surfactants are getting more andmore in particular multiple quaternary-ammonium saltsgemini surfactants have been reported [14ndash22] Kim et al[15] synthesized a series of new alkyl based quaternary-ammonium cationic surfactants by inserting a methylim-ino group (gtNCH3) a dodecylimino group (gtNC12H25) adimethylammonium group (gtN+(CH3)2) and a dodecyl-methylimmonio group (gtN+(CH3)C12H25) into two dode-cyldimethyl quaternary-ammonium salts respectively andtheir properties were studied The result showed that themulti-alkyl hydrophobic group was the main reason leadingto the decrease of the critical micelle concentration even

HindawiInternational Journal of CorrosionVolume 2018 Article ID 9890504 12 pageshttpsdoiorg10115520189890504

2 International Journal of Corrosion

（3

（2 （2

（3

（3

（3

（

N（2 （2

（（

（2

2 Cl O

2（5（

2（5（

Cl

OH

（

OH

（

OH

OH

CH Cl

（3

（3

（

N

（3

212（25(（3)2

(（2)9(（2)9

（2

（2（2 （2

（2 （2

（2

（3

（2

（3（3

（3+

+ （3middot2Ｆminus

Figure 1 Synthetic route of bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]-isopropylamine dichloride

with long carbon chains spacers did not play the roleof hydrophobic groups Lim et al [17] synthesized singledouble triple quaternary-ammonium salts gemini surfactantby using condensation reactions Surface tension test showedthat the lowest surfactant tension was 2888mNm whichmeant these gemini surfactants could be used to reducethe surface tension of the aqueous solution and to actas emulsifiers foaming performance tests showed that thefoam volumersquos decline rate increased when the number ofammonium and hydroxyl groups increased In recent timesthe studies of the corrosion inhibition performance of geminisurfactants are getting more and more [23ndash29] Xu et al[23] synthesized a new amide gemini inhibitor (OPDO) andstudied its corrosion inhibition performance to Q235 carbonsteel in hydrochloric acid solution The results showed thatOPDO had excellent corrosion inhibition effect for carbonsteel and it was a mixed inhibitor its maximum inhibi-tion rate was up to 99 the results also showed that theadsorption on the surface of carbon steel conformed tothe Langmuir isothermal adsorption model Hegazy et al[24] synthesized three kinds of gemini surfactants with longchains containing benzene rings as spacers results showedthat in acidic solution those three kinds of surfactants couldbe used as mixed-type inhibitors with both physical andchemical adsorption models and its corrosion inhibition ratefor carbon steel decreased firstly and then increased withtemperaturersquos increase

The studies on corrosion inhibition performance forcarbon steel are quite a lot now while there are still fewstudies on corrosion inhibition performance of gemini sur-factants for aviation used aluminium alloys at the sametime the corrosion inhibition studies of multi-alkyl multiplequaternary-ammonium salts cationic gemini surfactants withimino groups as spacers are more focused on using straightchain imino groups as spacers those using branched chainimino groups as spacers are rarely reported In this paperisopropylimino (gtNCH(CH3)2) is used as the spacer to

connect two dodecyldimethyl quaternary-ammonium saltsto finally synthesize a novelmulti-alkyl bisquaternary ammo-nium cationic gemini surfactant then its surface propertiesand its corrosion inhibition efficiency and the inhibitionmechanism for aviation used Al-Cu-Mg 2024 alloy in HClsolution (1molL) are studied

2 Experimental

21 Reagents and Instruments

Reagents The reagents were isopropylamine epichloro-hydrin dodecyldimethylamine hexane acetone absoluteethanol and hydrochloric acid (mass fraction 36ndash38) Allthe chemicals were of analytical reagent grade and were usedwithout further purification

Instruments Bruker-400 NMR Spectrometer BS 224S Elec-tronic Analytical Balance (degree of accuracy plusmn01mg) Par-Stat 2273 Electrochemical Workstation HITACHI S-3400NScanning Electron Microscope 79-1 Magnetic HeatingStirrer DSA25 Drop Shape Analyzer Avatar 300 FourierInfrared Spectrometric Analyzer ZDHW Electric HeatingJacket RE-25 Rotary Evaporator iron stand 150mL round-bottom flask Allihn condenser separating funnel 150mLconical flask and 250mL beaker were used

Al-Cu-Mg alloy for aviation with composition (in wt)Cu 38ndash49 Mg 12ndash18 Mn 03ndash10 Cr 01 Zn 025 and Al(balance) was used as the subject investigated

22 Synthesis of Bis[2-hydroxy-3-(dodecyldimethylammo-nio)propyl]-isopropylamine Dichloride The preparation pro-cedure of bis[2-hydroxy-3-(dodecyldimethylammonio)pro-pyl]-lsopropylamine dichloride is shown as Figure 1

Preparation of Middle Product In a beaker of 250mlepichlorohydrin (93ml) was added at the speed of 10 seconds

International Journal of Corrosion 3

per drop to a mixture of absolute ethanol and isopropamide(5ml) under icewater bath After that themixturewas stirredat indoor temperature for 10 hThen rotatory evaporator wasused to remove solvent and redundant epichlorohydrin inthe 40∘C water bath for 1 h from which the transparent vis-cous liquid bis(2-hydroxy-3-chloropropyl) isopropylaminewas obtained as the middle product

Preparation of Final Product The middle product (122 g)dodecyldimethylamine (27ml) and absolute ethanol weremixed and heated to reflux for 10 h From reduced pressuredistillation at 60∘C for 1 h and being washed three times byhexane the white waxy product (326 g) bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]-isopropylamine dichlo-ride was finally extracted

23 Surface Tension Measurement At 25∘C the DSA25 DropShape Analyzer was applied to measure surface tensioncurves of the mixed solution of 1molL HCl and differentconcentrations of synthetic product In addition the criticalmicelle concentration (cmc) and its corresponding surfacetension can be ensured by the intersection point of the curves

24 Weight Loss Measurement The 2024 Al-Cu-Mg alloyspecimens were applied with dimensions 50mm times 25mmtimes 2mm The surface was abraded in sequence by abrasivepapers ranging from 800 to 2000 and then washed bydeionized water acetone and absolute ethanol in order toremove the grease and impurities of the surface Cold-blastair was used to dry the specimens and then initial weightsof specimens were measured and recorded After that speci-mens were immersed in different corrosion solutions for 4 hand then a soft brush was dipped in acetone and absoluteethanol to remove the corrosion products on the metalsurface Finally the specimens were cleaned ultrasonically indeionized water and ultimate weights were measured andrecorded again

The average corrosion rate (119881) and the inhibition effi-ciency (IE) the synthetic product were calculated asfollows

119881 = 1198980 minus 119898119878 times 119905

IE () = 1198810 minus 1198811198810 times 100(1)

where 1198980 and 1198981 are respectively the initial and ultimateweight 119878 is the immersed surface 119905 is the corrosion duration119881 and 1198810 are respectively the average corrosion rate inpresence and absence on synthetic product

25 Electrochemical Measurement Electrochemical mea-surement was carried out by using ParStat 2273 Electrochem-ical workstation at room temperature 25∘C In the three-electrode assembly 2024Al-Cu-Mg alloywork electrodewithworking surface 1 cm2 Pt wire auxiliary electrode with area3 cm2 and AgAgCl reference electrode filled with saturatedKCl solution (01981 V versus NHE) were used Among themthe distance between work electrode and auxiliary electrode

minus07 minus06 minus05 minus04 minus03 minus02 minus01

00 01 02 03 04

E (V

)

1500 1000 3000 500 2500 2000 T (s)

Figure 2 OCP test result

was about 12 cm and the distance between work electrodeand reference electrode was about 2 cm

Before the impedance test open circuit potential (OCP)test was carried out to ensure that the follow-up experimentswere tested in a stable state The OCP plot of 2024 Al-Cu-Mgalloy in 1molL HCl solution with 9 times 10minus4molL syntheticproduct was shown in Figure 2

It can be seen that after soaking for about 15 minutes thecurve reaches a stable stage and the OCP is basically stable atminus048V Therefore impedance tests were carried out after 15minutes of immersion in the specimensThe results obtainedby adding other concentrations of the synthetic product arebasically the same

In order to make an approximate equilibrium of thesystem potentiodynamic polarization curves were measuredunder scanning range of plusmn250mV relative to the OCP andscanning rate of 0166mVsThe following equation was usedto compute the inhibition efficiency as

IE () = 1198680 minus 1198681198680 times 100 (2)

where 1198680 and 119868 are respectively the corrosion current inten-sity in absence and presence of synthetic product

The impedance measurements were carried out underfrequency range of 10mHzsim100 kHz and amplitude of 10mVEquivalent circuits were simulated from ZsimpWin softwareThe inhibition efficiency of synthetic product was calculatedas follows

IE () = 119877119901 minus 1198771015840119901

119877119901 times 100(3)

where 1198771015840119901 and 119877119901 are respectively the polarization resistancein absence and presence of synthetic product

26 Corrosion Surface Observation HITACHI S-3400Nscanning electronic microscope (SEM) was applied toobserve the corrode surface in absence and presence ofsynthetic product in order to determine their corrosion stateand degree


27 Adsorption Isothermal Model The adsorption mecha-nism of inhibitor can be justified by the adsorption isother-mal model where a classic Langmuir adsorptionmodel obeysthe following assumption every adsorption site on the metalsurface shares the same properties and can only adsorb onemolecule at best the molecules onside exert no acting forceon each other The adsorption isothermal formula is

119862120579 = 119862 +

1119870 (4)

where119862 is the concentration of inhibitor119870 is the adsorptionequilibrium constant 120579 is the fraction of coverage which canbe attained from

120579 = IEIE119898 (5)

where IE is the inhibition efficiency of correspondinginhibitor concentration IE119898 is the maximum inhibitionefficiency Besides the Langmuirmodel can be also presentedas follows [30]

1119881 = 119870

10158401015840 + 1198701015840119862 (6)

where 119881 is the corrosion rate 11987010158401015840 is the reciprocal of theuninhibited corrosion rate 1198701015840 is a constant which resultedfrom the weight loss method

28 Adsorption Thermodynamics Parameters The adsorp-tion equilibrium constant 119870 could be concluded from Lang-muir simulated curve The relation between 119870 and theadsorption free energy Δ1198660ads can be expressed as

119870 = ( 1555) expminusΔ1198660ads119877119879 (7)

where 119877 is molar gas constant 8314 Jsdotmolminus1sdotKminus1 T is theenvironmental temperature 298K Δ1198660ads is used to justifyfurthermore the adsorption mechanism

29 FTIR Tests The absorption peaks in FTIR curves can beused to determine whether a new chemical bond occurs ordisappears on the metal surface FTIR curves of corrosionproducts on the surface of 2024 Al-Cu-Mg alloy in 1molLHCl solution withwithout the synthetic product have beenplotted to determine the adsorption type of the syntheticproduct

3 Results and Discussion

31 Structure Characterization of Bis[2-hydroxy-3-(dodec-yldimethylammonio)propyl]-isopropylamine Dichloride TheFTIR test result is shown in Figure 3 It can be seen that3371 cmminus1 is the vibration peak of -OH the two adsorptionpeaks at 2923 cmminus1 and 2853 cmminus1 are characteristic vibrationpeaks of long carbon chains [31] 1462 cmminus1 is the flexuralvibration peak of C-H [32] peaks between 1050sim1200 cmminus1and 500sim700 cmminus1 are the characteristic peaks of C-C C-N

3500 3000 2500 2000 1500 1000 500

(＝Ｇminus1)

0

50

100

T (

)

Figure 3 Infrared spectra of synthetic product

and C-Cl [32] Based on the analysis it can be concluded thatthe synthetic product is the target product1H NMR test result of the synthetic product is shown

in Figure 4 Specific analysis is as follows 1H NMR(CDCl3)120575 0806ndash0840 (t 6H (CH3)2) 1017ndash1033 (m 6HCH3(CH)CH3) 1200ndash1289 (m 36H (CH3(CH2)9)2)1687 (s 4H (CH3(CH2)9CH2)2) 2686ndash2745 (m1H CH3(CH)CH3) 2956ndash3056 (m 4H (CH2CH)2)3252ndash3312 (m 12H (N+(CH3)2)2) 3542ndash3554 (m 8H(N+(CH2)2)2) 3870ndash3901 (m 2H (CH2CH)2) 4293ndash4309(m 2H (OH)2) By analyzing the peak positions of relativehydrogen atoms and the relative areas of absorption peaksit can be concluded again that the synthetic product is thetarget product

32 Surface Tension Test Surface tension (120574) was plottedversus the logarithm of concentration of synthetic product asshown in Figure 5 As seen in Figure 5 at low concentrations120574 drops sharply with the increase of log119862 while at higherconcentrations 120574 keeps essentially constant The surfacetensions of these two states are fitted linearly respectivelyand the intersection point is approximately the criticalmicelleconcentration (cmc) of the synthetic product [33] Thus itcan be seen that the cmc of the synthetic product is 9204times 10minus4molL which is 1sim2 orders of magnitude lower thanthat of conventional single-chain quaternary-ammonium saltsurfactant cmc of a range of conventional and geminisurfactants are given in Table 1

The cause of the decrease of cmc may be that thesynthetic product connects two long carbon chains replaced-ammonium cations by using its spacer group thus greatlyincreases the number of carbon atoms of the hydrophobicgroup [15] and finally reduces the cmc Meanwhile thehydrophilic group is connected with the spacer group by achemical bond thus could arrange closely in adsorption layerof the solution surface and the hydrophobic groups arrangevertically in solid-liquid interface thereby the surface activityis increased and it is easier to form micelles


43094293

3901388938803870

35543542

33123276325230563024300729732956274527242686

1687

12891281120010331017184018241806

320

331

827

115

4

317

115

312

361

5

647

600

350 300 250 200 150 100400ppm (t1)

0

10000

20000

30000

40000

50000

60000

Figure 4 1H NMR spectra of synthetic product

Table 1 cmc of conventional and gemini surfactants

Surfactants cmcmmolsdotLminus1 ReferencesC12H25N

+(CH3)3 Clminus 22 [34]

C12H25N+(CH3)3 Br

minus 16 [34]C4H8(C12H25N

+Me2 Brminus)2 109 [35]

C6H12(C12H25N+Me2 Br

minus)2 101 [35]C12H25N

+(CH3)2-CH2-CH(OH)-CH2-N(CH3)-CH2-CH(OH)-CH2-(CH3)2N+C12H25 2Cl

minus 099 [15]C12H25N

+(CH3)2-CH2-CH(OH)-CH2-N(CH(CH3)2)-CH2-CH(OH)-CH2-(CH3)2N+C12H25

2Clminus (synthetic product) 092

C12H25N+(CH3)2-CH2-CH(OH)-CH2-N(C12H25)-CH2-CH(OH)-CH2-(CH3)2N

+C12H25 2Clminus 00062 [15]

33 Inhibition Properties of Bis[2-hydroxy-3-(dodecyldimeth-ylammonio)propyl]-isopropylamine Dichloride

331 Weight Loss Test The influence of the concentration ofsynthetic product on corrosion rate (V) and inhibition effi-ciency (IE) of 2024 Al-Cu-Mg alloy in 1molL HCl solutionhas been studied by static weight loss method as shown inFigure 6 It can be seen that with the concentration increasingfrom 5 times 10minus5molL to 9 times 10minus4molL V decreases from72401 times 10minus5 g∙mmminus2∙hminus1 to 13759 times 10minus5 g∙mmminus2∙hminus1 whileIE is doubled from435 to 893However with the concen-tration increasing from 9 times 10minus4molL to 24 times 10minus3molL V

declines slightly from 13759 times 10minus5 g∙mmminus2∙hminus1 to 10123 times10minus5 g∙mmminus2∙hminus1 similarly IE increases slightly from 893to 921

Combined with surface tension test result it can beanalyzed that corrosion rate first decreases rapidly with theincrease of the concentration of synthetic product whenthe concentration is near to cmc (9204 times 10minus4molL) thecorrosion rate decreases from a rapid decline to a slowdecline and eventually almost no change occurs the ruleof inhibition efficiency is just the opposite The reason maybe that when the concentration is low the ammoniumcation of the synthetic product is easy to be adsorbed to


minus26minus28minus30minus32minus34minus36

ＦＩＡ C (molmiddotminus1)

cmc30

40

50

(m

NmiddotＧ

minus1)

Figure 5 Surface tension (120574)-logarithm of concentration (log119862) curve of synthetic product

Corrosion rateInhibition efficiency

cmc

5 10 15 20 250C (10minus4 molmiddotminus1)

1

2

3

4

5

6

7

8

V(10minus5gmiddotＧＧ

minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)

Figure 6 Static weight loss curve of 2024 Al-Cu-Mg alloy in 1molL HCl solution with different concentrations of synthetic product

the surface of 2024 Al-Cu-Mg alloy at the same time thelong carbon chains arrange orientated and orderly whichform a protective film on the surface of the alloy and play arole in corrosion inhibition when the concentration reachesto cmc the adsorption of the surfactant molecules on themetal surface is approximately saturated therefore with theincrease of concentration the corrosion rate and corrosionefficiency change slowly or almost remain unchanged

332 Potentiodynamic Polarization Measurements Figure 7represents the cathodic and anodic curves measured byadding different concentrations of synthetic product (05sim9 times10minus4molL) into 1molL HCl related parameters of polariza-tionmeasurements are shown in Table 2 It could be observedthat 119868corr decreases with the increase of synthetic productrsquosconcentrationWhen the concentration is 9times 10minus4molL 119868corrhas reduced by an order of magnitude over the blank solutionand reaches 707 times 10minus4 A Meanwhile both cathodic and

anodic curvesmove in the direction of decreasing the currentdensity 119864corr changes little compared with blank solutionit suggests that both cathodic and anodic reactions aresuppressed with the addition of synthetic product besidesthe synthetic product is amixed-type inhibitor which reducesanodic dissolution and also retards the hydrogen evolutionreaction The corrosion efficiencies (IE) are calculated byusing (2) results show that IE increases monotonously withthe increase of synthetic product and is up to 886 whichmeans the synthetic product has a good inhibiting effect onmetal corrosion This result is consistent with the weight lossmethod

333 Electrochemical Impedance Spectroscopy Nyquist plotsof 2024 Al-Cu-Mg alloy in absence and presence of dif-ferent concentrations of the synthetic product are shownin Figure 8 The inspection of Figure 8 reveals that all theNyquist plots are composed of capacitive arcs in the high


Blank5 times 10minus5 (molL)1 times 10minus4 (molL)

3 times 10minus4 (molL)6 times 10minus4 (molL)9 times 10minus4 (molL)

minus7 minus6 minus5 minus2minus3 minus1minus8 minus4ＦＩＡ l (AmiddotcＧminus2)

minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)

Figure 7 Tafel polarization curves with different concentrations of synthetic product added

blank5 times 10minus5 molL1 times 10minus4 molL

3 times 10minus4 molL6 times 10minus4 molL9 times 10minus4 molL

100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＬ (Ωmiddot＝Ｇ2)


Figure 8 Nyquist diagrams with different concentrations of synthetic product added


WERE

CPE

RＭ

RＪ

Figure 9 Equivalent circuit of Nyquist diagrams

Table 2 Test parameters obtained from Tafel polarization curves

11986210minus4molsdotLminus1 119868corr10minus3A 119864corrV IE0 6198 minus0470 05 3564 minus0479 4251 2386 minus0475 6153 1382 minus0477 7776 1004 minus0476 8389 0707 minus0481 886Note 119862 concentration of synthetic product 119868corr corrosion current 119864corrcorrosion potential IE inhibition efficiency

frequency zone which are related to double-layer capacitanceas well as the charge transfer resistance The capacitive arcsare depressed in nature it is due to the micro roughness ofthe surface of metal formed during corrosion

The proposed equivalent circuit by ZsimpWin software isshown in Figure 9 related parameters are listed in Table 3It can be analyzed that 119877119901 increases and 1198840 decreases withincreasing in the concentration of the synthetic productwhich indicates the formation of adsorption layer on thesurface of the alloy It can be calculated through (3) thatthe inhibition efficiency increases with increasing in theconcentration of the synthetic product and is up to 946 at 9times 10minus4molL Compared with the weight loss test results theinhibition efficiencies obtained by impedance test are slightlyhigher but the overall trend is the same so the results are stillconsistent

334 Surface Topography Analysis Figure 10 demonstratesthe damage caused by exposure of 2024 Al-Cu-Mg alloyto 1molL HCl in absence and presence of the syntheticproduct for 4 hours It is evident that the surface becomesvery rough and a large amount of corrosion pits can befound after being corroded in 1molL HCl without anysynthetic product which means that a severe corrosion hashappened when the synthetic product is added the surfacebecomes smoother and no big corrosion pits could be foundFigure 10(b) clearly shows that the synthetic product couldform a smooth adsorption layer on the surface to inhibit thecorrosion of 2024 Al-Cu-Mg alloy

335 Adsorption Isotherms andThermodynamic CalculationsFigure 11 shows the adsorption isotherms of the syntheticproduct on Al-Cu-Mg alloy in 1molL HCl solution In

(a)

(b)

Figure 10 Corrosion surface morphology of 2024 Al-Cu-Mg alloy(a) 1molL HCl (b) 1molL HCl + synthetic product

y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)

Figure 11 Langmuir fitting curve of synthetic product

this case the line has a slope of 0936 and the correlationcoefficient (1198772) is 09998 The linear relationship of c120579versus c shows that the synthetic product obeys Langmuiradsorption isotherm whichmeans that the synthetic productforms a dense monomolecular film on the surface of 2024 Al-Cu-Mg alloy [37] effectively blocks corrosion ions near themetal surface and slows down the corrosion of alloy surface

The adsorption equilibrium constant 119870 could be cal-culated by using the fitted line above and K = 1789 times104 Lmol Through (7) adsorption free energy Δ1198660ads can be


Table 3 Fitting parameters of equivalent circuit

119862 (10minus4molsdotLminus1) 119877119904 (Ωsdotcm2) 119877119901 (Ωsdotcm2) 1198840 (10minus5Ωminus1sdotcmminus2sdotsminus1) 119899dl IE0 072 2359 1170 090 05 051 3271 1060 096 2791 073 3891 1050 092 3943 082 7705 846 087 6946 063 42320 662 081 9449 098 43690 600 096 946Note119862concentration of synthetic product 119877119904solution resistance 119877119901 polarization resistance 1198840capacitive admittance of CPE capacitance 119899dlempiricalexponent of CPE capacitance [36] IE inhibition efficiency

Surface of 2024 AI-Cu-Mg Alloy

(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3

+ (（3)2middot2Ｆminus +(（3)2middot2Ｆminus +(（3)2middot2Ｆminus(（3)2+

OH OHN

OH OHN

OH OHN

Adsorptionfilm

Figure 12 Physisorption between synthetic product and surface of 2024 Al-Mg-Cu alloy

(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ

Ｇ2middotＢmiddotＡ

minus1)

05 10 15 20 2500Ccmc

Figure 13 Vminus1-Ccmc curve of 2024 Al-Cu-Mg alloy

calculated and equals minus342 kJmol Δ1198660ads lt 0 illustratesthe adsorption process is spontaneous A value of Δ1198660ads =minus40 kJmol is usually adopted as the threshold value betweenchemisorption and physisorption [38] Thus it indicates thatthe adsorption of the synthetic product is more inclinedto physisorption where ammonium cations are attractedto the negative charge of the metal surface by electrostaticinteraction and are adsorbed to the metal surface as shownin Figure 12

Fit again the weight loss test results through (6) fittedlines are shown in Figure 13 where the ratio of the concentra-tion of synthetic product to the concentration of the criticalmicelle concentration cmc was set up as abscissa in order toexplain the influence of cmc on the corrosion rate

1 molL HCl + synthetic product1 molL HCl

3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)

Figure 14 FTIR plots of corrosion products on metal surface inabsencepresence of synthetic product

It shows that the two fitted lines intersect when Ccmcnearly equals 1 Thus it can be deduced that when theconcentration is higher than cmc the adsorption behaviourof synthetic product on the metal surface changes

34 Study on Corrosion Inhibition Mechanism FTIR resultsof corrosion products on the surface of 2024 Al-Cu-Mg alloyin 1molL HCl solution withwithout the synthetic productare shown in Figure 14 It can be analyzed that 3401 cmminus1 isthe vibration peak of -OH [31] 1626 cmminus1 is the vibrationpeak of AlCl3 [39] 1397 cm

minus1 and 946 cmminus1 are the vibrationpeaks of Al2O3 andMgO [40] 618 cmminus1 is the vibration peak


Figure 15 Adsorption principle of synthetic product on 2024 Al-Cu-Mg alloy surface

of Cu2O [39] It can be indicated that no chemical bondappears or disappears by comparing two curves As a resultit can be verified again that the adsorption of the syntheticproduct is physisorption

In order to better explain the corrosion inhibition processand mechanism of the synthetic product on the surfaceof the alloy the schematic diagram of the adsorption anddesorption process is shown in Figure 15

As seen in Figure 15 there might be two adsorptionmodes when the concentration of synthetic product is lowerthan cmc as shown in (a) and (b) At low concentration twohydrophilic groups are adsorbed on the metal surface thatis each hydrophilic group occupies one adsorption site asshown in (a) at higher concentration one of two hydrophilicgroups of gemini surfactant may be adsorbed on the metalsurface adsorption site while another cannot adsorb ontoit as shown in (b) In actual situation the adsorption modeis more inclined to (a) (b) coexistence and this adsorptionmode still meets the Langmuir adsorption model that ismonolayer adsorption

When the concentration of synthetic product is higherthan cmc its adsorption on the metal surface is saturatedWhen keeping increasing the concentration similar to theconventional surfactants which form micelles with innerhydrophobic groups and outer hydrophilic groups the syn-thetic product molecules will form a bilayer adsorption filmwith hydrophobic groups at the middle and hydrophilicgroups at both ends as shown in (c) Therefore the adsorp-tion pattern does not accord with the monolayer adsorptionfilm of Langmuir model assumed which is a good explana-tion of the intersection point in Figure 13

As a new environmental friendly inhibitor the syn-thetic product has many advantages one of which is its

physisorption onmetal surfaceThe synthetic product can bedesorbed naturally without any extra process when the metalsurface is dried Hence compared with chemical absorp-tiondesorption physical absorptiondesorption ismore con-cise efficient and environmentally friendly

4 Conclusions

(1) Two-stepmethod has been taken to synthesize a novelgreen inhibitor bis[2-hydroxy-3-(dodecyldimethyl-ammonio)propyl]-isopropylamine dichloride FTIRand 1H NMR tests show that target product is thesynthetic product

(2) Critical micelle concentration cmc of the syntheticproduct is 9204 times 10minus4molL when the concentra-tion is lower than cmc inhibition efficiency of thesynthetic product to 2024 Al-Cu-Mg alloy increasesmonotonously and is up to 893 at 9 times 10minus4molLwhen it is higher than cmc inhibition efficiency of thesynthetic product keeps basically unchanged

(3) The Tafel polarization studies indicate that the syn-thetic product is of mixed anodic-cathodic type eachNyquist plots is composed of a depressed capacitivearc in the high frequency zone the electrochemicaltest results are consistent with theweight lossmethod

(4) The adsorption type of synthetic product is phy-sisorption When the concentration is lower thancmc the adsorption mode of the synthetic productconforms to the Langmuir adsorption model andforms a monolayer adsorption film on 2024 Al-Cu-Mg alloy surface when it is higher than cmc it forms


bilayer adsorption film on metal surface and thusdoes not conform to the Langmuir adsorption modelanymore

Conflicts of Interest

The authors declare that they have no conflicts of interest

Acknowledgments

This work was supported by supporting funds for disciplineconstruction of Civil Aviation University of China underGrant no 000032041110

References

[1] B Wang Z Y Wang G W Cao Y J Liu and W Ke ldquoLocal-ized corrosion of aluminum alloy 2024 exposed to salt lakeatmospheric environment in western Chinardquo Acta MetallurgicaSinica vol 50 no 1 pp 49ndash56 2014

[2] H M Abd El-Lateef M A Abo-Riya and A H TantawyldquoEmpirical and quantum chemical studies on the corrosioninhibition performance of some novel synthesized cationicgemini surfactants on carbon steel pipelines in acid picklingprocessesrdquo Corrosion Science vol 108 pp 94ndash110 2016

[3] M A Hegazy A A Nazeer and K Shalabi ldquoElectrochemicalstudies on the inhibition behavior of copper corrosion inpickling acid using quaternary ammonium saltsrdquo Journal ofMolecular Liquids vol 209 pp 419ndash427 2015

[4] M A Hegazy A M Badawi S S Abd El Rehim and W MKamel ldquoCorrosion inhibition of carbon steel using novel N-(2-(2-mercaptoacetoxy)ethyl)-NN-dimethyl dodecan-1-aminiumbromide during acid picklingrdquo Corrosion Science vol 69 pp110ndash122 2013

[5] P Singh M A Quraishi E E Ebenso and C B VermaldquoUltrasound assisted synthesis of chalcones as green corrosioninhibitors for mild steel in 1M hydrochloric solutionrdquo Interna-tional Journal of Electrochemical Science vol 9 no 12 pp 7446ndash7459 2014

[6] B Gao andMM Sharma ldquoA new family of anionic surfactantsfor enhanced-oil-recovery applicationsrdquo Society of PetroleumEngineers Journal vol 18 no 5 pp 829ndash840 2013

[7] R Zana ldquoDimeric and oligomeric surfactants Behavior atinterfaces and in aqueous solution A reviewrdquo Advances inColloid and Interface Science vol 97 no 1-3 pp 205ndash253 2002

[8] M S Kamal ldquoA review of gemini surfactants potential appli-cation in enhanced oil recoveryrdquo Journal of Surfactants ampDetergents vol 19 no 2 pp 223ndash236 2016

[9] W Chen B Shao Y Liu X Li M Zheng and L TianldquoApplication of gemini surfactants in the development of oil andgas fieldsrdquo Journal of Yangtze University vol 13 no 34 pp 66ndash70 2016

[10] J Liu D Zhao S and J LiHu J J and Ren P B Corrosion Protec-tion 2016

[11] K Cao H Y Sun and B R Hou ldquoCorrosion inhibition ofgemini surfactant for copper in 35NaClrdquoAdvancedMaterialsResearch vol 936 pp 1125ndash1131 2014

[12] J Zhao H Duan and R Jiang ldquoSynergistic corrosion inhibitioneffect of quinoline quaternary ammonium salt and Geminisurfactant in H2S and CO2 saturated brine solutionrdquo CorrosionScience vol 91 pp 108ndash119 2015

[13] AGautam andNKamboUpadhyay SK andRP Singh ColloidsSurfaces A Physicochemical Engineering Aspects pp 195ndash2022008

[14] E Kang K B Lee M H A Hwang and J C Lim ldquoA novelcationic surfactant having two quaternary ammonium ionsrdquoJournal of Industrial and Engineering Chemistry pp 845ndash8522011

[15] T-S Kim T Kida Y Nakatsuji and I Ikeda ldquoPreparationand properties of multiple ammonium salts quaternized byepichlorohydrinrdquo Langmuir vol 12 no 26 pp 6304ndash63081996

[16] J C Lim J M Park J P Chan and M B Lee ldquoSynthesis andsurface active properties of a gemini-type surfactant linked by aquaternary ammonium grouprdquo Colloid amp Polymer Science vol291 no 4 pp 855ndash866 2013

[17] C J Lim K E Kang M J Park H C Kang and B Mand Lee ldquoSyntheses and surface active properties of cationicsurfactants having multi ammonium and hydroxyl groupsrdquoJournal of Industrial amp Engineering Chemistry vol 18 no 4 pp1406ndash1411 2012

[18] X P Liu J Feng L Zhang and Q T Gong ldquoSynthesis andproperties of a novel class of anionic gemini surfactants withpolyoxyethylene spacersrdquoColloidsamp Surfaces APhysicochemicalEngineering Aspects vol 362 no 1 pp 39ndash46 2010

[19] X M Pei Y You J X Zhao Y S Deng E J Li and Z X LildquoAdsorption and aggregation of 2-hydroxyl-propanediyl-120572120596-bis(dimethyldodecyl ammonium bromide) in aqueous solu-tion Effect of intermolecular hydrogen-bondingrdquo Journal ofColloid and Interface Science vol 351 no 2 pp 457ndash465 2010

[20] Z Miao F Wang D Deng Y Zhang X Huo and LWang ldquoPreparation of novel gemini quaternary ammonium saltcationic surfactantrdquo Applied Mechanics and Materials vol 174-177 pp 1433ndash1436 2012

[21] F H Abdel-Salam and A G El-Said ldquoSynthesis and surfaceactive properties of gemini cationic surfactants and interactionwith anionic azo dye (AR52)rdquo Journal of Surfactants andDetergents vol 14 no 3 pp 371ndash379 2011

[22] N A Negm and A S Mohamed ldquoSynthesis characteriza-tion and biological activity of sugar-based gemini cationicamphiphilesrdquo Journal of Surfactants and Detergents vol 11 no3 pp 215ndash221 2008

[23] J Z Xu M Li H Xue R Li and T Ye Corrosion Science ampProtection Technology 2013

[24] M A Hegazy M Abdallah and H Ahmed ldquoNovel cationicgemini surfactants as corrosion inhibitors for carbon steelpipelinesrdquo Corrosion Science vol 52 no 9 pp 2897ndash2904 2010

[25] D Asefi M Arami and N M Mahmoodi ldquoElectrochemicaleffect of cationic gemini surfactant and halide salts on corrosioninhibition of low carbon steel in acid mediumrdquo CorrosionScience vol 52 no 3 pp 794ndash800 2010

[26] D Asefi N M Mahmoodi and M Arami ldquoEffect of nonionicco-surfactants on corrosion inhibition effect of cationic Geminisurfactantrdquo Colloids amp Surfaces A Physicochemical amp Engineer-ing Aspects vol 355 no 1-3 pp 183ndash186 2010

[27] A Adewuyi A Gopfert and T Wolff ldquoSuccinyl amide Geminisurfactant from Adenopus breviflorus seed oil A potentialcorrosion inhibitor ofmild steel in acidicmediumrdquo in IndustrialCropsamp Products vol 52 pp 439ndash449 Products 1 edition 2014

[28] MMobin and SMasroor ldquoCationic gemini surfactants as novelcorrosion inhibitor for mild steel in 1M HClrdquo InternationalJournal of Electrochemical Science vol 7 no 8 pp 6920ndash69402012


[29] F A Ansari and M A Quraishi ldquoInhibitive performance ofgemini surfactants as corrosion inhibitors for mild steel informic acidrdquo Portugaliae Electrochimica Acta vol 28 no 5 pp321ndash335 2010

[30] Z Y Wu The research on the corrosion inhibition metal in acidmedium by some gemini surfactants Central South UniversityChangsha China 2011

[31] B H Yan P Mei Wu X M L Lai and X Yang ldquoSynthesisand rheological properties of multiple-quaternary ammoniumsurfactantsrdquo China Surfactant Detergent amp Cosmetics vol 6 pp301ndash305 2015

[32] R G Ge L Zhao L Lai and P Mei ldquoSynthesis of three basedbis quaternary ammonium salt Gemini surfactantrdquo Journal ofYangtze University (Nat Sci Edit) no 2 pp 17ndash20+405 2010

[33] T G Chi and Z G Cui ldquoSynthesis and properties of novelGemini cationic surfactants (2)mdashmultiple quaternary ammo-nium salts from dodecylamine and epichlorohydrinrdquo ChinaSurfactant Detergent Cosmetics vol 4 pp 36ndash38 2001

[34] FMMenger and J S Keiper ldquoGemini surfactantsrdquoAngewandteChemie International Edition vol 39 no 11 pp 1906ndash19202000

[35] R Atkin V S J Craig E J Wanless and S Biggs ldquoAdsorptionof 12-s-12 gemini surfactants at the silica-aqueous solutioninterfacerdquo The Journal of Physical Chemistry B vol 107 no 13pp 2978ndash2985 2003

[36] Y C Qing Z W Yang J Xian et al ldquoCorrosion behaviorof Q235 steel under the interaction of alternating current andmicroorganismsrdquo Acta Metallurgica Sinica vol 52 no 9 pp1142ndash1152 2016

[37] X K He B L Hou Y M Jiang C Li and L Y Wu ldquoInhibitionproperty and adsorption behavior of imidazole and 2-phenyl-2-imidazoline onCu inH2SO4 solutionrdquoActaMetallurgica Sinicavol 49 no 8 pp 1017ndash1024 2013

[38] S Taghi Y Alireza andHMirghasem ldquoInhibition behaviour of2-butinel 4diol and tartrate salt and their synergistic effects oncorrosion of AA3003 aluminium alloy in 05 NaCl SolutionrdquoJournal ofMaterials ScienceampTechnology vol 24 no 3 pp 427ndash432 2008

[39] J J Liu ldquoIR analysis of corrosion products on aluminum alloyin simulate island environmentsrdquo Equipment EnvironmentalEngineering vol 4 pp 124ndash128 2015

[40] J P Lin X Wang X J Yang and H L Wan ldquoEffects ofatmospheric pressure air plasma treatment on static strength ofadhesive-bonded aluminum alloyrdquo China Surface Engineeringvol 3 pp 110ndash121 2017

CorrosionInternational Journal of

Hindawiwwwhindawicom Volume 2018

Advances in

Materials Science and EngineeringHindawiwwwhindawicom Volume 2018


Journal of

Chemistry

Analytical ChemistryInternational Journal of


ScienticaHindawiwwwhindawicom Volume 2018

Polymer ScienceInternational Journal of



Advances in Condensed Matter Physics


International Journal of

BiomaterialsHindawiwwwhindawicom

Journal ofEngineeringVolume 2018

Applied ChemistryJournal of


NanotechnologyHindawiwwwhindawicom Volume 2018

Journal of


High Energy PhysicsAdvances in

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom

The Scientific World Journal

Volume 2018

TribologyAdvances in



ChemistryAdvances in


Advances inPhysical Chemistry


BioMed Research InternationalMaterials

Journal of


Na

nom

ate

ria

ls


Journal ofNanomaterials

Submit your manuscripts atwwwhindawicom


（3

（2 （2

（3

（3

（3

（

N（2 （2

（（

（2

2 Cl O

2（5（

2（5（

Cl

OH

（

OH

（

OH

OH

CH Cl

（3

（3

（

N

（3

212（25(（3)2

(（2)9(（2)9

（2

（2（2 （2

（2 （2

（2

（3

（2

（3（3

（3+

+ （3middot2Ｆminus

Figure 1 Synthetic route of bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]-isopropylamine dichloride

with long carbon chains spacers did not play the roleof hydrophobic groups Lim et al [17] synthesized singledouble triple quaternary-ammonium salts gemini surfactantby using condensation reactions Surface tension test showedthat the lowest surfactant tension was 2888mNm whichmeant these gemini surfactants could be used to reducethe surface tension of the aqueous solution and to actas emulsifiers foaming performance tests showed that thefoam volumersquos decline rate increased when the number ofammonium and hydroxyl groups increased In recent timesthe studies of the corrosion inhibition performance of geminisurfactants are getting more and more [23ndash29] Xu et al[23] synthesized a new amide gemini inhibitor (OPDO) andstudied its corrosion inhibition performance to Q235 carbonsteel in hydrochloric acid solution The results showed thatOPDO had excellent corrosion inhibition effect for carbonsteel and it was a mixed inhibitor its maximum inhibi-tion rate was up to 99 the results also showed that theadsorption on the surface of carbon steel conformed tothe Langmuir isothermal adsorption model Hegazy et al[24] synthesized three kinds of gemini surfactants with longchains containing benzene rings as spacers results showedthat in acidic solution those three kinds of surfactants couldbe used as mixed-type inhibitors with both physical andchemical adsorption models and its corrosion inhibition ratefor carbon steel decreased firstly and then increased withtemperaturersquos increase

The studies on corrosion inhibition performance forcarbon steel are quite a lot now while there are still fewstudies on corrosion inhibition performance of gemini sur-factants for aviation used aluminium alloys at the sametime the corrosion inhibition studies of multi-alkyl multiplequaternary-ammonium salts cationic gemini surfactants withimino groups as spacers are more focused on using straightchain imino groups as spacers those using branched chainimino groups as spacers are rarely reported In this paperisopropylimino (gtNCH(CH3)2) is used as the spacer to

connect two dodecyldimethyl quaternary-ammonium saltsto finally synthesize a novelmulti-alkyl bisquaternary ammo-nium cationic gemini surfactant then its surface propertiesand its corrosion inhibition efficiency and the inhibitionmechanism for aviation used Al-Cu-Mg 2024 alloy in HClsolution (1molL) are studied

2 Experimental

21 Reagents and Instruments

Reagents The reagents were isopropylamine epichloro-hydrin dodecyldimethylamine hexane acetone absoluteethanol and hydrochloric acid (mass fraction 36ndash38) Allthe chemicals were of analytical reagent grade and were usedwithout further purification

Instruments Bruker-400 NMR Spectrometer BS 224S Elec-tronic Analytical Balance (degree of accuracy plusmn01mg) Par-Stat 2273 Electrochemical Workstation HITACHI S-3400NScanning Electron Microscope 79-1 Magnetic HeatingStirrer DSA25 Drop Shape Analyzer Avatar 300 FourierInfrared Spectrometric Analyzer ZDHW Electric HeatingJacket RE-25 Rotary Evaporator iron stand 150mL round-bottom flask Allihn condenser separating funnel 150mLconical flask and 250mL beaker were used

Al-Cu-Mg alloy for aviation with composition (in wt)Cu 38ndash49 Mg 12ndash18 Mn 03ndash10 Cr 01 Zn 025 and Al(balance) was used as the subject investigated

22 Synthesis of Bis[2-hydroxy-3-(dodecyldimethylammo-nio)propyl]-isopropylamine Dichloride The preparation pro-cedure of bis[2-hydroxy-3-(dodecyldimethylammonio)pro-pyl]-lsopropylamine dichloride is shown as Figure 1

Preparation of Middle Product In a beaker of 250mlepichlorohydrin (93ml) was added at the speed of 10 seconds







119881 = 1198980 minus 119898119878 times 119905

IE () = 1198810 minus 1198811198810 times 100(1)




00 01 02 03 04

E (V

)

1500 1000 3000 500 2500 2000 T (s)






IE () = 1198680 minus 1198681198680 times 100 (2)



IE () = 119877119901 minus 1198771015840119901

119877119901 times 100(3)





119862120579 = 119862 +

1119870 (4)


120579 = IEIE119898 (5)


1119881 = 119870

10158401015840 + 1198701015840119862 (6)



119870 = ( 1555) expminusΔ1198660ads119877119879 (7)





3500 3000 2500 2000 1500 1000 500

(＝Ｇminus1)

0

50

100

T (

)







43094293

3901388938803870

35543542

33123276325230563024300729732956274527242686

1687

12891281120010331017184018241806

320

331

827

115

4

317

115

312

361

5

647

600

350 300 250 200 150 100400ppm (t1)

0

10000

20000

30000

40000

50000

60000




+(CH3)3 Clminus 22 [34]

C12H25N+(CH3)3 Br


+Me2 Brminus)2 109 [35]


minus)2 101 [35]C12H25N


minus 099 [15]C12H25N




+C12H25 2Clminus 00062 [15]








cmc30

40

50

(m

NmiddotＧ

minus1)



cmc


1

2

3

4

5

6

7

8


minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)










minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls










119881 = 1198980 minus 119898119878 times 119905

IE () = 1198810 minus 1198811198810 times 100(1)




00 01 02 03 04

E (V

)

1500 1000 3000 500 2500 2000 T (s)






IE () = 1198680 minus 1198681198680 times 100 (2)



IE () = 119877119901 minus 1198771015840119901

119877119901 times 100(3)





119862120579 = 119862 +

1119870 (4)


120579 = IEIE119898 (5)


1119881 = 119870

10158401015840 + 1198701015840119862 (6)



119870 = ( 1555) expminusΔ1198660ads119877119879 (7)





3500 3000 2500 2000 1500 1000 500

(＝Ｇminus1)

0

50

100

T (

)







43094293

3901388938803870

35543542

33123276325230563024300729732956274527242686

1687

12891281120010331017184018241806

320

331

827

115

4

317

115

312

361

5

647

600

350 300 250 200 150 100400ppm (t1)

0

10000

20000

30000

40000

50000

60000




+(CH3)3 Clminus 22 [34]

C12H25N+(CH3)3 Br


+Me2 Brminus)2 109 [35]


minus)2 101 [35]C12H25N


minus 099 [15]C12H25N




+C12H25 2Clminus 00062 [15]








cmc30

40

50

(m

NmiddotＧ

minus1)



cmc


1

2

3

4

5

6

7

8


minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)










minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls






119862120579 = 119862 +

1119870 (4)


120579 = IEIE119898 (5)


1119881 = 119870

10158401015840 + 1198701015840119862 (6)



119870 = ( 1555) expminusΔ1198660ads119877119879 (7)





3500 3000 2500 2000 1500 1000 500

(＝Ｇminus1)

0

50

100

T (

)







43094293

3901388938803870

35543542

33123276325230563024300729732956274527242686

1687

12891281120010331017184018241806

320

331

827

115

4

317

115

312

361

5

647

600

350 300 250 200 150 100400ppm (t1)

0

10000

20000

30000

40000

50000

60000




+(CH3)3 Clminus 22 [34]

C12H25N+(CH3)3 Br


+Me2 Brminus)2 109 [35]


minus)2 101 [35]C12H25N


minus 099 [15]C12H25N




+C12H25 2Clminus 00062 [15]








cmc30

40

50

(m

NmiddotＧ

minus1)



cmc


1

2

3

4

5

6

7

8


minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)










minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls





43094293

3901388938803870

35543542

33123276325230563024300729732956274527242686

1687

12891281120010331017184018241806

320

331

827

115

4

317

115

312

361

5

647

600

350 300 250 200 150 100400ppm (t1)

0

10000

20000

30000

40000

50000

60000




+(CH3)3 Clminus 22 [34]

C12H25N+(CH3)3 Br


+Me2 Brminus)2 109 [35]


minus)2 101 [35]C12H25N


minus 099 [15]C12H25N




+C12H25 2Clminus 00062 [15]








cmc30

40

50

(m

NmiddotＧ

minus1)



cmc


1

2

3

4

5

6

7

8


minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)










minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls







cmc30

40

50

(m

NmiddotＧ

minus1)



cmc


1

2

3

4

5

6

7

8


minus2middotＢ

minus1)

40

50

60

70

80

90

100

IE (

)










minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls








minus08

minus07

minus06

minus05

minus04

minus03

minus02

minus01

E (V

)




100

200

300

400

200 400 60000

0

10

20

30

40

50

60

20 40 60 80 1000

ZＣＧ

(Ωmiddot＝Ｇ

2)

ZＣＧ

(Ωmiddot＝Ｇ

2)





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls





WERE

CPE

RＭ

RＪ








(a)

(b)


y = 093581x + 055894

R2 = 099983

2 4 6 80C (10minus4ＧＩＦ)

2

4

6

8

C

(10minus4ＧＩＦ)








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls








(（3)2+ (（3)2

+

（3（（3 （3（（3 （3（（3


OH OHN

OH OHN

OH OHN

Adsorptionfilm


(099324 07835)

00

02

04

06

08

10

Vminus1(Ｇ


minus1)

05 10 15 20 2500Ccmc





3000 2500 2000 1500 1000 5003500 (cＧminus1)

40

60

80

100

T (

)













4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls












4 Conclusions









Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls








Acknowledgments


References












































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls



















Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls




synthesis of a novel gemini cationic surfactant and its...

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