In this investiAation, an attempt has been made to use electrochemical impedance spectroscopy as a tool for monitoring the phosphate coating formation, especially the involvment of hase metal in the coating fornlation. Results of the studies have been presented in the foml of Nyquist plot.. of various immersion time which shows a depressed semicircle and the diameter and degree of depression increase with time. Charge transfer resistance and the int~rfacial capacitance of steel in phosphatin~ solution are parameters of impedance study which helps in assessing and optimizing the conditions of phosphating. The result.. also show that presence of crystal refiner and/or accelerator accelerate the base metal dissolution at the initial stJlge of coating formation and the crystal refiner modifies the coating properties hy lowering tbe porosity by redissolution and deposition

Balakrishnan, K.

Marikkannu, C.

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Bulletin ofElectrochemistry 15 (3-4) M~rch-April I QQ9, pp 156-159 0256-1654jQ9f$ 3-50 © I Q99 CECRI INVESTIGATION OF PHOSPHATE COATING FORMATION BY ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY C MARIKKANNU AND K BALAKRISHNAN" Central Eleclroche,llIical Rescarch Institute, Karaikudi 630 000. INDIA * AJagappa University, Karaikudi 630 003. INDIA In this investiAation, an attempt has been made to use electrochemical impedance spectroscopy as a tool for monitoring the phosphate coating formation, especially the involvment of hase metal in the coating fornlation. Results of the studies have been presented in the foml of Nyquist plot.. of various immersion time which shows a depressed semicircle and the diameter and degree of depression increase with time. Chaq~e transfer resistance and the int~rfacial capacitance of steel in phosphatin~ solution are parameters of impedance study which helps in assessing and optimizing the conditions of phosphating. The result.. also show that presence of crystal refiner and/or accelerator accelerate the base metal dissolution at the initial stJlge of coating fnrmation and the crystal refiner modifies the coating properties hy lowering tbe porosity by redissolution and deposition. Keywords: Impedance technique, phosphate coaUn~. conversion coatin~ sh~el. Primary Phosphat ~ Tertiary PhosphateINTRODUCTION (Soluble) (Insoluble) Rise of temperature and/or pH, shift the equilihrium to the Phospating proccss has very early origin and it is widely right, favouring the precipitation of i.nsoluble tertiary use,d for all tbe engineering materials to improve paint phosphate as coating on lhl~ metal surface. adhesion, corrosion resistance, luhrication and to provide The electrochemical nature of the process proceeding during electrical insulation, Inspitc of its wide usage, search of coating fonnation has been used to follow 1lle overall surface literature reveals only very little information concerning the process. TIIUS, potential-time measureme,nts have been uSl'd fundamental mechanism of phospating while extensive to monitor the completion of phosphate coating [41. Though reviews are available on varions applications and theore,tical by this method, it is possible to follow as well as to identify aspects of phosphate coating [1-3J. various stages of phosphate ('oating formation, Ii tile information can be obtained on 1lle involvement of baseProcess proceeding during phospating of mdals involve metal during tbe oating formation. One of the promisingsusbtrate, corrosion (dissolution) in the acidic hath 14-51 and ways to ge,t such information is by tbe use of sophisticatedtbis associates witb an increase of interfacial pH whicb instrumentation such as electrochemical impe,danceaccekrates the predpitation of insoluble tertiary phosphate spl~ctroscopy (EIS). Such infonnation is esscntial inon the metal surface to form thl' so calkd phospbate coating. ellginl'uing coatings for particular application andIn order to achieve the process of thl~ previous kind, it is dde,rlll ining the pfl',ise role of additivl~s present in the bath, essential that the phosphating bath sbould contain free i,c accekrators.phosphoric acid, a primary metal phosphate of type MIl 11 U 1I 11,H2P04 (Wbl'rt' M , Fe , Zn or Mn ) WIth an accelerator tn this investigation, attempt has bcen madc to study tbe typically an oxidant sucb as nitrate or chlorate. The general corrosion bl~haviour of sleel in phosphating solution by EIS. view is thai the lllrchani m of pbosphatt' coating formation Potential-time measurrn1l'nl" have also brcn studil'd in is complex, and it depends on the following equilibrium support of the earlier study. 156 MARIKKANNU et al.-Invesligation of phosphate coating formation by electrochemical impetlance spectroscopy TABLE.I: Results of impedance study Immersion Polan- Corrosion Capaci­Bath time zation current tance type resistance min QCmz I.l Ncmz 2.5% H3P04 60 216 1.25 X 10-4 Bath I 5 100 130 6.10 X 10-5 Batb I 10 520 25 2.30 X 10-5 Bath I 20 3200 4 1.80 X 10--6 Bath I 30 3600 3.6 1.60 X 10-6 Batb II 5 50 260 4.20 X 10-4 Bath II 10 3800 3.42 1.76 X 10--6 Bath II 20 4200 3.095 1.62 X 10-6 Bath LI 30 4600 2.8 1.48 X 10-6 Bath HI 5 60 216 1.42 X 10-4 Bath III 10 3950 3.29 1.81 X 10-6 Bath III 20 4000 2.83 1.40 X 10-6 Bath In 30 5000 2.5 1.32 X 10-6 EXPERIMENTAL Mild sleel specimen of size 10 x 50 nUll we·re mechanically polished, degreased with acetonl'.. Before phosphating, the samples were immersed in 10% oxalic acid at room temperature for 10 minutes, followed by washing in distilk~ water. For impedance measurl~mcnts the samplrs were lacquered so as to expose 1 cm 2 area. The phospbating bath used in this iuvestigation has the composition as in Table I. For potential-timc measurements the samples were immcrsed in the batb with and without additive at room temperature. Potenlials were monitored with rcspect to saturated calomel electrode (reference ekctrode) using a digital multimeter. Impedance measurements during the coating fonnation were made with conventional three electrode cell arrangement whi b has mild steel as working electrode, platinum foil as counter electrode and saturated calomel electrode as reference electrode. Impedance measurements were made at corrosion potential by superimposing a sine wav('. of amplitude 10 mY in tbe frcquency range of 10 kHz to 1 Hz. The results have he,en r ported in the fmm of Nyquist plot. RESULTS ANU D1SClfSSION Fig. I shows the potential-time behaviour of mild strel in phosphating bath. Initially the potclltial value bas been found to sbift cathodically (in the ne.gative direction) and then rises progressive.ly with time and attains a steady state potential value approximately after 25 minutes of imlllersion. In phosphating batb with additives A and A+B, tbe potential behaviour is similar to thaI dl'~lTib d previously but the time for attaining minimum value and steady statt' potential is mucb less wlle.n compared to that of atlditivc free bath. Potential-time behaviour of slrel suggests tbat initial dissolution of :te.el is followl'd by the development of pbosphate coating. Moreover, in pre.sence of additive, hoth tbe. dissolution of the base metal as well as coating [onnation rate have been acceleratl~d. Howcve,r, the extent of suhstrate corrosion or coating fonnation rate can not be predicted from this behaviour. :r pical imprdance spectra llH'asure.ment as obtained for steel in bath I as a function of lime are presented in Fig. 2 wbicb also includes that of sh'eI in 2.5'* phospboric acid for comparison. The impedancr diagrams obtained at the corrosion potential for sll'd in phospbating bath II, III are also similar. But a clear difference is observed betw cn these diagrams obtained for different immersion times in the same bath. TIle impedance diagram is characterised by a single caparilive loop. The. value of charge lransfr.r resistan('e RCI ohlail\l~d as a function of time [or dille.rent baths arc summarised in Tahle II. As the immersion time increases, the capacitive loop becomes more depressed, rather flattened loop. The degree of depression changes wiUt immersion time. Such behaviour could he attrihuted to the illcrcaSl~ micro-roughness caused hy the deposition of lbe coating (chemic<ll or structural bl'laogcnity) or by corrosion products. TIle corrosion rate of the sted substrate from the Rei value of the impedance expn~ssed as current density can be calculated using the Stem-Grary relationship Icor-r :;: 0.013 / ReI where Ute value of 0.013 corresponds to the anodic and cathodic Tafel slope values of 0.04 and 0.12 Y/dec respcctivl'1y. TABLE D: Composition of tbe phosphating bath ln~redients Bath I Bath n Hath III % % % Pbosphoric acid 2.0 2.0 2.0 Trisodium Pho phate 1.5 1.5 1.5 Zinc oxide 1 1 1 HN03 0.5 0.5 0.5 Additive A-Accelerator 0.05 0.05 Additive B-Crystal renner 0.05 157 MARIKKANNU et al.-Investigation of phosphate coating fonnalion ny electrochemical impedance. pectroscopy • -440 c • g...-.- - ..- [1-. ~ '-.i ~ -460 :> > /)' ..... --. ...E -480 ro :j'§ ,2 0 0­-500 ·520 -----,--~'--,i~~1 i I , i o 5 ~,) 15 ?O 25 30 Fig. 1: Potential time behaviour of mild steel in phosphating solution ( 0 ) Acid (.) Hath 1 (0) Hath l/ (.) Bath 11l Tbus calculated corrosion ratc values are also given in Table 1. The results reveal tbat the corrosion rate is higber initially, and decreases relatively rapidly, achieving a steady state value after immersion for 20 minutes. Presence of additive A and A + B accelt"rates the initial metal dissolution and the steady state is achieved in rdatively lesser time and tbe magnitude of corrosion rate is mucb less indicating the less porous nature of the coating. The residual sleady state current may hc due to tbe dissolution of the substrate througb pores of tbe coating. Rcsults of tbe studies by potential-time measurements, and EIS indicates tbat there are four distinct stages in phosphate coating fonnation viz i) the induction stage, ii) the C01l1mencclllnt· of film growth or nucleation stage, iii) the main exponential stage. or film growth stage and iv) the steady state stage or crystal re-organisation stage. Potvin and Ahali (4) have utilized the potential-time measurements not only to indicate the. different stages of phosphating but also to loc.ate when the effe(·tivc phosphating has ceased. In the author's opinion, much information on the kinetics and 1I1ecbanism of phosphating process can be inferred from tbe potential-time measurements. When following the potential-time measurements for all the baths cbose.n for tbe present study, though the. nature of the curves appears to be different, the following points are of great importance in all the curves (Fig. 1) i) potential measured at the instant of immersion, ii) time taken for the potential maximum, iii) the time taken for the stabilised potential and iv) extent of change in potential between tbe maximum and the st.abiliSt'Al potential. He.lIce it is possible to interpret the obtained data based on the above ohservations to reveal the kinetics and mechanism of pbosphating which is difficult from the coating weight dctenn ina tion. Tog ther potential-time hchaviour and impedance measurement provide much infomlation tban tbe potential-time behaviour alone. Moreover, assessing the resultant coating quality is not possible hy the potential-time measurements. The impedance spectroscopy cmploye.d in this study is capahle of monitoring the in situ progress of the coating formation on stt~d. Importantly, the impedance behaviour of stcd in phosphating bath allow insight to be gained into the solution chemistry and inlcrfacial conditions during the course of phosphating pw('(·ss. Basic reactions in zinc phosphating of steel The acidic zinc phosphating solution reacts with the metal surface. In a solution containing only acid and zinc iOIlS, the reaction Oil an oxide fret' stt'l'l surface is (1) hll!llediatdy after the imlllersion, this dissolution of the base metal takes place which is indicated ~n the rise iu potential­time measurements and low Ret in the impedance. measurements. Presence.' of additives increase the rate of tbe real'lion by consuming the hydrogcn at the metal surface. This enhanced dissolulion is evident from low Ret' By the reaction (1), the pH value is increased in the metal/solution interface rcsulting to the de.'position of the zinc phosphate of hopeite structure. as iJldic.atcd below: '""'~-l I·~~i ::'~':.~I'\. \- 2Clm...... n _ I. ]0 ITIln o~o---''-!;IO~O-~100;;;--O-''*'OO;---;-'OO::::-~500~~6::-;1;:oo~·7?M.l 800 Fig. 2: Impedance behaviour of steel in phospJmtinl: solution as a functioin of time 158 MARIKKANNU et al.-Investigation of phosphate coating formation by electrochemical im .dance spectroscopy On steel, phosphophylite can be precipitated as Fe2 + 2Zn2 + + 2H2PO~ + 4H20 - Fe Zn2 (P04) 2' 4H20 + 4H+ (3) The most imporlant reat'tion in the phosphating process is the lIucleation of zinc phosphate crystals. The number of nuclei fomled detenniues the property of the zinc phosphate coating. A large number of nuclei rl~sults in a fine-grained coating where as smalI number of nuclei results in a coarse coating that takes longer time to complete (6-81. If nuclei arc to be fonned, the solution has to be supersaturate.d with zinc phosphate. Hence, if the hydrogen consuming reactions on steel surface can be speedl'd up by the additives, this results in a faster increase of pH and this r(~sults in a more supersaturated solution. In addition to the enhanccment of nucleation, the higher dissolution rate of Utc. steel by the additives also result in a faster growth of the zinc phosphate crystals and there.by shortens the phosphating time. This can be seen in the impedance results which show large change immediately after immersion. The results correlate Wt~1I with the observed changes in the potential-time be-.baviour. It also demonstrates clearly the effect of acceleration, which decreases by morc than 50% the time. taken to foml the coating by accelerating the initial me.lal dissolution rate. Conversely, tbe marked difference in the slable Ret 'value of coating from different baths (residual corrosion difference in physical properties of the films fonned, for example, the degree of surface coverage or porosity and structural changes. Unlike potential monitoring, impedance studies provide an insight into the behaviour of coatings after its completion. Significant residual metal corrosion rates suggest a larger extent of porosity in tbe film or dissolution of the substrate in the bath through the pores. Thus, hy the addition of accelerators, highly corrosion n'sistanl coatings aTl~ fonne.d in shorter time by the acceleration of initial phase me.tal dissolution step. By this, the solution at the nH'tal/solution interface becomes saturated with zinc phosphate crystals in shorter time and due to its hydrogen consuming nature, the pH increases at the metal sol ution interface. Both these conditions favour the quick deposition of phosphate crystals on the surface. Moreover, due to its accelerating efft'ct, more number of nuclei are fonned which results in a compact (low porous) coating. In addition, this additive oxidises Fe2+ to ferricphospbate which dc'creases the diffusion of Fe2 + outwards and thus the bighe.r concentration of Fc2+ nece.ssary for the fonnation of phosphophyllite is achieved wbich is more corrosion resistant than bopeite Conn. CONCLUSION Potential-time as well as impedance spectroscopy can be used to follow the phosphate ,oating formation and provide an indication of the completion of the pro,es!;. Impedance measurement also indicates residual base metal corrosion after the completion of coating formation and it is due to the dissolution of the substrate metal through pores. PreSt',nce of additive A alone or witb additive B in the bath accelr.rate the rate of coating fonnation. In addition, it changes the porosity and composition of the resultant coating which makes then more (orro ion resistant Acknowledgement: The authors thank Or M Raghavan, Director, and Dr N S Rengaswamy, Scientist, C'entml Electrochemical Research Institute, Karaikudi for their keen interest and support in publishing this paper. REFERENCES 1.	 G Lorin, The Phosphating of Metals, Finishing Publication Ltd, Teddington, Middleses, England (1974) 2.	 D B Freeman, PhmpllOting and metal pre-treatment, Woodhead Faulkner Camhridge (1986) 3.	 W Rausch, The phosphating of metals, Finishi ng publiC<ltions Ltd., Middless (1990) 4.	 E L Ghali and R J A POlvin, Carr Sci, 12 (1972) 583 5,	 J Blakeman, R R (jahe and MOW Richardson, Trans IMF, 55 (1977) 117 6.	 C Marikkannu, l'h D Thesis, Alagappa University, Karaikudi. India (11)96) 7.	 C Marikkannu, P Suhramanian and K Ralakrishnan, Bull E!eetroc/rem, 5 No 9 (I 9RI) 578 8.	 P E Tegchall and P E Augusisson, Proe Gth Scnndinavian C-orr Cong, Copenhagen, ()1)87) 365 159 

Investigation of phosphate coating formation by electrochemical impedance spectroscopy

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