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ISSN 1023 1935, Russian Journal of Electrochemistry, 2013, Vol. 49, No. 5, pp. 475482. Pleiades Publishing, Ltd.

., 2013. Original Russian Text F.I. Danilov, V.S. Protsenko, V.O. Gordiienko, 2013, published in Elektrokhimiya, 2013, Vol. 49, No. 5, pp. 536545.

Electrode Processes Occurring during the Electrodeposition of ChromiumCarbon Coatings from Solutions of Cr(III) Salts with Carbamide and Formic Acid Additions
F. I. Danilovz, V. S. Protsenko, and V. O. Gordiienko
Ukrainian State University of Chemical Technology, Dnepropetrovsk, Ukraine
Received February 15, 2012

AbstractThe regularities and possible mechanisms of electrode processes occurring during the elec trodeposition of the CrC alloy from an electrolyte based on Cr(III) sulfate with carbamide and formic acid as organic components were analyzed. The chromium electrodeposition was found to impose its kinetics on carbon inclusion in the alloy. The mechanism of carbon incorporation in the deposit was assumed to be the chemical interaction of the adsorbed organic particles with highly active chromium adatoms. During the stage discharge of Cr(III) ions to the metal, the rate of the limiting stage Cr(II) + 2e Cr(0) increased when OH or F ions were included in the structure of the electrochemically active complex. Keywords: trivalent chromium, electrodeposition, chromiumcarbon coating, kinetics and mechanism, stage discharge DOI: 10.1134/S1023193513050054

INTRODUCTION Electrolytes for the deposition of chromium based coatings have actively been developed during recent decades. They generally contain various organic com ponents [19] as carbon source in the coating [10]. Thus we actually deal with the electrodeposition of the chromiumcarbon alloy [1123]. The attention of researchers mainly focused on the peculiarities of the microstructure of CrC coatings and their physico chemical and mechanical properties and perfor mance. The kinetics and mechanism of chromium and carbon codeposition, however, remained almost undefined. Thus it was noted [10, 24, 25] that for the electrodeposition of chromium alloys with metalloids (phosphorus, carbon, etc.), it was necessary to take into account the parallel electroreduction of the ligand environment of chromium ions, leading to the inclu sion of metalloids in the deposit, along with the dis charge of metal ions and hydrogen evolution. This idea evidently requires further elaboration and detailing. Therefore, this study is devoted to investigation of the kinetics and mechanism of chromium and carbon codeposition from formatecarbamide electrolytes based on Cr(III) compounds [9, 22, 23]. EXPERIMENTAL The coatings were electrodeposited from electro lytes containing (mol/dm3): 0.5 Cr2(SO4)3 6H2O (i.e., 1 M Cr(III)), 01.0 HCOOH, 01.0 CO(NH2)2,
z

0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 of sodium lauryl sulfate [9]; 0.4 M NaF was occasionally added to the electrolyte. The procedure for the preparation of electrolytes and the role of their components were described in detail in [9, 22, 23, 26]. To obtain steady state partial voltammograms, electrolysis was conducted in a potentiostatic mode. (Reference 3000 (Gamry) potentiostat) in a thermo statted three electrode cell. The working electrode was a gold disc placed in a plexiglas cartridge with a diameter of 7 mm. Before each experiment, the work ing electrode was subjected to cathode degreasing in an alkaline solution and then activated in a hydrochlo ric acid solution, thoroughly washed with bidistillate, dried, and weighed. The auxiliary electrode was a tita niummanganese dioxide anode separated from the catholyte by a porous glass diaphragm [27, 28]. The electrode potentials were measured relative to a satu rated silver chloride reference electrode at the same temperature as the working electrode. The resistive component was compensated automatically using an iR compensation system built in the potentiostat. The electrodeposition time was = 10 min. The current remaining almost constant during the electrolysis (except the first 1530 s after the start of polarization), the average current density was calcu lated by the equation

Corresponding author: fdanilov@optima.com.ua (F.I. Danilov).

i =
475

Q ,

(1)

476 Carbon content, wt % 12 1

DANILOV et al.

2 8

The algorithm for calculations of the partial cur rent densities of the reactions occurring during chro miumcarbon codeposition is described below. The influence of the electrolyte composition and dep osition conditions on the composition of the CrC alloy was studied on coatings obtained in a galvanostatic mode. RESULTS AND DISCUSSION

0.2

0.4

0.6

0.8

1.0

1.2

[CO(NH2)2, M 0 0.2 0.4 0.6 0.8 1.0

[HCOOH], M
Fig. 1. Dependence of the carbon content on the concen tration of (1) CO(NH2)2 (with 0.5 M formic acid) and (2) HCOOH (with 0.5 M carbamide). The composition of electrolytes (mol/dm3): 0.5 Cr2(SO4)3 6H2O, 0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 sodium lauryl sulfate. Current density 35 A/dm2, pH 1.5, temperature 35.

where Q is the charge that passed through the cell within the time (determined automatically using the potentiostat software). After the electrolysis was completed, the working electrode was washed, dried, and weighed. The com position of the deposit was determined by X ray pho toelectron spectroscopy (XPS) [22] and chemical analysis. In the latter analysis, the deposited CrC coating was dissolved in a hydrochloric acid solution after weighing; after adding EDTA solutions and for mation of the corresponding deep colored Cr(III) complex ions, the optical density of the solution was measured by the standard procedure at = 540 nm [29]. The chromium and carbon contents in the deposit were determined from these data. The results of XPS and chemical analysis completely coincided. It should be emphasized that the contents of other ele ments (except chromium and carbon) in the deposit were negligibly small [22]. Hydrogen escaped during the electrodeposition of CrC was collected over the electrolyte and its volume was measured after the electrolysis was completed. After the hydrogen volume was recalculated for the normal conditions applying a correction for the pres ence of saturated water vapors at the temperature of experiment, the partial current density of hydrogen evolution iH 2 was calculated.

According to the data of the majority of studies cited above, the electrodeposition of the CrC alloy involves the following partial electrode processes: electroreduction of Cr(III) to Cr(II), formation of Cr(0), hydrogen evolution, and transition of carbon to the alloy. The former three reactions were widely cov ered, both theoretically and experimentally, in the lit erature. The latter reaction can only be judged from the previously discovered dependences of the total composition of coatings on various factors, taking into account [10, 24, 25] Faraday processes involving the organic components of the electrolyte. Hence to con struct the voltammograms corresponding to the partial process of carbon inclusion in the coating, we should primarily determine the nature of the starting reagents and reaction products. As organic ligands we chose formic acid and carba mide because, according to [3, 4, 9, 12, 22, 23], using this system can afford high quality thick coatings with high carbon contents. In a series of experiments (Fig. 1), the carbon con tent in the deposit was almost independent of the for mic acid concentration in the electrolyte, all other parameters being constant, but increased linearly as the CO(NH2)2 concentration increased to 0.5 M. Fur ther increase in the amount of carbamide in the elec trolyte did not lead to any changes in the carbon con tent in the coating. The experiments were subsequently performed in an electrolyte containing 0.5 M CO(NH2)2, 0.5 M HCOOH, and other components necessary for form ing compact high quality shiny coatings [9, 22]. According to XPS studies [22], carbon is in carbide form in the deposits. As is known, the chemical bond in chromium carbides cannot be regarded as a pure metal, ionic, or covalent bond, but is a combination of these three types of bond [30, 31]; i.e., in chromium carbides with different compositions, the chromium and carbon atoms have a small electric charge (table). Taking into account the tabulated data in calcula tions of the partial current densities of electrodeposi tion of the components of the CrC alloy, the conven tional degree of oxidation of chromium and carbon in the deposit is assumed to be zero in a first approxima tion. If we assume (based on the analysis of the data of Fig. 1) that the hypothetical electrodeposition of car
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bide carbon in the alloy involves only carbamide, the corresponding equation is recorded as
+ CO(NH 2 )2 + 6H + + 4e = C(0) + 2NH 4 + H 2O. (2) According to [3238], chromium electrodeposi tion in Cr(III) based aqueous electrolytes is stepwise and forms relatively stable intermediate Cr(II) com plexes:

Electron density distribution in chromium carbides (ac cording to the data of [30]) Carbide Cr3C2 Cr7C3 Cr23C6 Atom C Cr C Cr C Cr Charge (e) 0.50 +0.33 0.53 +0.23 0.59 +0.15

+e(i1) +2e(i2 ) Cr(III) Cr(II) Cr(0), (3) 0 0 E =0.61 V E =1.11 V

where i1 and i2 are the partial current densities at the corresponding stages. Simultaneously with (2) and (3), hydrogen evolu tion reaction occurs on the cathode. For kinetic anal ysis of partial reactions, we used the electric balance condition whereby the overall current i that passes through the electrode is the sum of the partial currents of all electrode processes:
i = i1 + i2 + iH2 + iC.

Note that the reduction of carbon containing compounds can in principle occur by the mechanism of their direct interaction with atomic hydrogen [39, 40]:
C(IV) + 4H C(0) + 4H + .
2

(7)

(4)

It can readily be shown that in this case, the results of calculations will be similar. That is, both suggested reaction schemes (2) and (7) are evidently not ade quate to the mechanism of the transformations of car bon containing compounds on the cathode. To obtain consistent material and electric balances, we took into account that, according to the data of [12], a so called secondary ligand can be formed in a chromium plating electrolyte containing both for mic acid and carbamide. This ligand is formed by a chemical reaction, as a result of which free CO(NH2)2 molecules are absent in the electrolyte:
O H O H H C OH + H N C N H + OH C H O

The average partial current densities of the two electron Cr(II) discharge reaction (i2 ) and four elec tron reaction (2) (iC ) can be calculated by the Faraday law using the data of the deposit composition analysis; iH 2 can be calculated from the volume of hydrogen escaped during the electrolysis. The partial current density of the partial one electron discharge of Cr(III) ions (i1) was calculated by Eq. (4). The partial currents at separate stages in the chain of sequential electrochemical transformations (3) under steady state conditions should evidently also obey the material balance equation for Cr(II) ions [3436]:

i1 i (5) =+ 2 , F 2F where is the flow of bivalent chromium ions from the near electrode layer to bulk solution ( > 0 in this case) or, vice versa, from solution to the electrode surface ( < 0).
Under the conditions of our experiments, 0 . In view of this, (5) is transformed into (6) 2i1 i2. However, calculations performed in accordance with the suggested mechanism of CrC alloy forma tion (Eqs. (2) and (3)) showed that condition (6) was not satisfied. This formally means that the number of Cr(II) ions consumed at the second stage of discharge in the chain of transformations (3) was higher than the number of ions formed at the first stage of Cr(III) elec troreduction. This obviously contradicts the physical sense. Therefore, we conclude that (2) is not adequate to the real process.
1 In

(8)

O H O H O H C N C N C H + 2H2O.

The formation of a secondary ligand was found [12, 13] by FTIR spectroscopy; the spectra of aque ous Cr(III) electrolyte containing both CO(NH2)2 and HCOOH had absorption bands characteristic of an amido group (NHCO). The formed species with the molecular formula C3N2O3H4 can be directly bonded with tri and biva lent chromium ions into complexes [12]. In this case, the codeposition of carbon with chromium can occur as a result of a cathode reaction

1 C N O H + 20 H + + 8 e = C(0) + 2 NH + + H O. (9) 3 2 3 4 4 2 3 6 3 3
2 Indeed,

this study, we did not preliminarily treat the electrolyte to accumulate a certain amount of bivalent chromium in it. RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 49

when calculating i1 in this case, we should exclude the subtrahend iC from (4), but iH2 will increase by the same value. The calculated partial currents i1 and i2 will thus be the same as those determined for mechanism (2) and conditions (5) and (6) will not be satisfied. No. 5 2013

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The formation of one carbide carbon atom by this reaction takes 8/3 electrons, i.e., 1.5 times less than by reaction (2). The calculated iC value decreases by the respective value. It should be emphasized that (9) was recorded by implicitly assuming that all the three carbon atoms (originating from both formic acid and carbamide) in the ligand of C3N2O3H4 undergo a complete discharge (to C(0)). In addition, it was assumed for simplicity that the carbamide and formic acid molecules not bonded into C3N2O3H4 did not contribute to the pro cess of carbon inclusion in the coating. Calculation of the partial components of the total cathode current using (9) shows that the material bal ance conditions (5) and (6) are completely satisfied. The corresponding partial polarization curves are ana lyzed below. Although the suggested reaction scheme formally satisfies the material and electric balance conditions, a more detailed analysis of the results revealed a number of inexplicable effects. Thus the carbon content in the coating was almost independent of the content of fluoride ions, tempera ture, and electrolysis time and slightly increased at lower current density and higher pH (Fig. 2). Remarkably, the rates of chromium and carbide carbon deposition in the deposit changed symbati cally when the current density, temperature, and pH changed and fluoride ions were introduced (Fig. 3). It is also noteworthy that the chromium deposi tion kinetics changed substantially and the corre sponding partial polarization curves were rather complex (Fig. 4a) after the change in the electrode potential, but the ratio of the mole fractions of chro mium and carbon in the deposit remained constant (Fig. 4b). Similar phenomena were observed when pH of electrolyte changed and fluoride ions were introduced in it. This means that, for some reason, the partial polarization curve of the hypothetical Faraday electrodeposition of carbide carbon (9) approximates well the i2,E curve for chromium depo sition in all of its segments. An analysis of these results suggests that the rate of carbon codeposition in the alloy is determined by the deposition rate of metallic chromium. In other words, the electrochemical chromium deposition imposes its kinetics on carbon inclusion in the deposit.
3 It is not excluded that in electrolytes containing only CO(NH ) 2 2

This can be explained if we assume that the destruction of organic compounds, leading to carbon inclusion in the CrC alloy, is not an electrochemical stage. The formation of carbide carbon during the for mation of the chromiumcarbon deposit can result from the fact that some of the active chromium ada toms that formed after the discharge of Cr(II) ions are involved in chemical interaction with the carbon liber ated from the coordination bond of the C3N2O3H4 secondary ligand adsorbed on the cathode surface:
0 8Crad + 2C3N 2O3H 4 + 20H +

(10) + = 8Cr 2+ + 6C(0) + 4NH 4 + 6H 2O. The resulting carbon is included in the structure of the deposit and Cr2+ ions can again take part in the electrochemical chromium deposition process. Note that carbon inclusion in the coating hinders the sur face diffusion of chromium adatoms and growth of the crystal phase nucleus, obviously forming the nanoc rystalline structure of the coatings [22, 23]. From the viewpoint of the suggested mechanism, the rate of carbide carbon inclusion in the deposit mainly depends on the degree of cathode surface occupation with the adsorbed organic particles and on the concentration of chromium adatoms. The carbon codeposition rate then depends on rate of formation of metal adatoms (i.e., on the i2 value) and should not directly depend on the electrode potential, volume pH, the presence of fluorides in solution, etc., which agrees well with the experimental data. The suggested mechanism is consistent with previ ously formulated ideas about the high electrocatalytic activity of deposited chromium in processes involving the organic components of solution [10, 24, 25]. It should be noted that the bivalent chromium ions involved in reaction (10) play the role of electron car riers (mediators) to carbon atoms. To derive an equa tion for the partial current iC formally spent on carbon electroreduction (actually on the formation of bivalent chromium ions as electron carriers), we should alge 2+ braically sum (10) with the equation 8Cr + 16e 0 8Crad . This results in (9), meaning that the material and electrical balance conditions are satisfied. Figure 5 presents the partial polarization curves for four electrode processes occurring on the electrode during the deposition of the chromiumcarbon alloy according to (9), (10). It can be seen that the partial
5A

(not containing HCOOH), carbon can be incorporated in the deposit by reaction (2). These electrolytes were not studied here because of the unsatisfactory quality of coatings obtained in this case. 4 Except the range of high negative electrode potentials, in which hydroxo formation on the electrode becomes pronounced due to active electroevolution of hydrogen and the local decrease in pH in the near electrode layer.

similar mechanism was suggested in [41]. Here we amplified the ideas formulated in our previous studies. we took a simpler equation 2Crad + C(IV) 2Cr + C(0) instead of (10), we would obtain C(IV) + 4e C(0) after the algebraic summation of this simpler equation with 2Cr
0 2Crad,
2+

6 If

2+

+ 4e

i.e., actually we would obtain (2), which, as mentioned above, contradicts the material balance requirements for bivalent chromium ions. Vol. 49 No. 5 2013

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Electrolyte without fluorides Electrolyte with a 0.4 M NaF addition

479

(b) Carbon content, % 10 9.53 9.48 9.14

10.310.2 10

9.84 9.9

9.48 9.4

8.85 8.6

5 5

0 25 Carbon content, % 15 30 () (c) 35 i, 40 A/dm2

0 25

30

35 (d)

40

45

Temperature, C Carbon content, % 10 9.43 9.48 9.38 9.41

Electrolyte without fluorides Electrolyte with a 0.4 M NaF addition

10.3 10.2 10 7.9 7.3 5 5 9.48 9.4

0 1.2

1.3

1.4

1.5

1.6

1.7

1.8

10

20

50 30 40 Electrolysis time, min

Fig. 2. Dependence of the carbon content in the deposit on (a) current density and the presence of fluoride ions, (b) temperature, (c) pH, and (d) electrolysis time. The composition of electrolytes (mol/dm3): 0.5 Cr2(SO4)3 6H2O, 0.5 CO(NH2)2, 0.5 HCOOH, 0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 sodium lauryl sulfate. Current density 35 A/dm2, temperature 35, pH 1.5 (unless stated otherwise).

reduction of Cr(III) ions starts in the range of poten tials in which the deposition of metallic chromium is thermodynamically yet impossible. When cathode polarization increases, the potential of the start of the discharge of bivalent chromium ions, formed at the first stage of the discharge in the chain of transforma tions (3), is reached. The chromium electrodeposition then occurs already under the conditions of diffusion rate control of the partial discharge of Cr(III). The partial hydrogen evolution reaction curve resembles a polarographic wave in shape because of the discharge of hydrogen ions under the kinetic control at the stage of dissociation of weak acids (proton donors) present in the electrolyte in large amounts. At negative cath ode potentials higher than ~1.45 V, the partial cur
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rent of hydrogen evolution reaction significantly increases probably because of the start of the discharge of solvent molecules. The latter effect is accompanied by abrupt alkalinization of the near electrode layer, leading to a binding of a considerable portion of chro mium(III) ions into not readily soluble and electro chemically inactive hydroxide compounds. This hin ders the deposition of metallic chromium almost com pletely, the cathode deposit consisting only of dark green films of Cr(III) hydroxide compounds, which are readily removed during washing. The inequality 2i1 i2 (equivalent to > 0) is valid in all cases; that is, not all bivalent chromium ions formed at the first stage in the chain of transformations (3) are involved in subsequent discharge, some part of them
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Fig. 3. Dependences of the partial densities of the deposi tion current of (1, 1') chromium and (2, 2') carbon, (b) temperature, and (c) pH. The composition of electro lytes (mol/dm3): 0.5 Cr2(SO4)3 6H2O, 0.5 CO(NH2)2, 0.5 HCOOH, 0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 sodium lauryl sulfate; (1 ') and (2 ') the electrolytes additionally contain 0.4 M NaF. Cur rent density 35 A/dm2, temperature 35, pH 1.5 (unless stated otherwise).

(a)

15

1' 2' 1

0 25 i2(), A/dm2 15 35 45 i, A/dm2 (b)

diffusing in solution. The electroreduction of Cr(III) to the metallic state is thus the limiting stage in (3) [3436]. The rate of electrochemical chromium elec trodeposition Cr(II) + 2e Cr(0) increased substan tially at higher pH (cf. curves 1 and 2 in Fig. 4a or curves 3 in Figs. 5a and 5b). This effect was previously found for formate, glycinate, and formatecarbamide
i2, A/dm2 12

(a)

15 1

3 2 1 1.30 1.50 1.70 E, V

0 2 5 3 25 i2(), A/dm2 20 30 35 40 45 t, C (c) 1' 15 2' 10 1 2 5 0 1.0 1.2 1.4 1.6 E, V 1 2 1.10 [Cr]/[C] (b) 3 1 2

0 1.3 1.4 1.5 1.6

1.7 pH

Fig. 4. (a) Partial polarization curves of chromium deposi tion and (b) the ratio of the mole fractions of chromium and carbon in the deposit depending on the electrode potential. The composition of electrolytes (mol/dm3): 0.5 Cr2(SO4)3 6H2O, 0.5 CO(NH2)2, 0.5 HCOOH, 0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 sodium lauryl sulfate; (3) the electrolyte addi tionally contains 0.4 M NaF. pH (1, 3) 1.5 and (2) 1.7; temperature 35. Vol. 49 No. 5 2013

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electrolytes based on Cr(III) salts [4, 7, 3437] and is related to the catalytic action of OH ions on chro mium electrodeposition. In the deposition of the Cr C alloy from the electrolytes under study, the elec troactive compounds are evidently the Cr(II) hydroxo complexes formed on the electrode surface as a result of the dissociation of innerspherically coordinated water molecules preceding the discharge. The mecha nism of the discharge of bivalent chromium complex ions can be represented by the following reaction scheme:

i, A/dm2 50 (a) 1

30

(12) 0 + + H + 2e Cr + mK + nH 2O, where K are the organic ligands (for example, the sec ondary ligand C3N2O3H4). The total number of electrons transferred at the stage of the discharge (12) is two. These two electrons can be transfered to the chromium(II) ion in sequence or simultaneously, in one elementary act [42, 43]. The available experimental data are insufficient for strict application of known criteria for stages of electro chemical reactions [44]. It is noteworthy that the introduction of fluoride ions in the chromium plating electrolyte led to a shift of the partial polarization curve of chromium elec trodeposition toward higher positive potentials (cf. curves 1 and 3 in Fig. 4a or curves 3 in Figs. 5a and 5c), i.e., to substantial acceleration of the process. This effect allows us to explain the previously found high current efficiencies in chromium electrodeposition from Cr(III) based fluoride containing electrolytes [2, 14, 26]. Recently, it was assumed that the catalytic action of fluoride ions at the bivalent chromium dis charge stage is the result of their incorporation in the inner sphere of the complex, which decreases the pos itive charge on the central atom, accelerates the ligand exchange, and diminishes the energy consumption at the stage of the transition from the electrochemically inactive intermediate [Cr2+L6] to the electroactive form [Cr2+L2] (where L is the fluoride ion) [45]. According to quantum chemical calculations, the dis charge of [Cr2+L2] linear biligand complexes requires much smaller activation energy than the discharge of [Cr2+L6].
Fig. 5. (1) Total and (25) partial polarization curves: (2) hydrogen evolution reaction, (3) chromium deposition Cr(II) + 2e Cr(0), (4) carbide carbon deposition, and (5) partial discharge of Cr(III) + e Cr(II). The compo sition of electrolytes (mol/dm3): 0.5 Cr2(SO4)3 6H2O, 0.5 CO(NH2)2, 0.5 HCOOH, 0.15 Al2(SO4)3 18H2O, 0.3 Na2SO4, 0.5 H3BO3, and 0.1 g/dm3 sodium lauryl sul fate; (c) the electrolyte additionally contains 0.4 M NaF. pH (a, c) 1.5 and (b) 1.7; temperature 35. RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 49

[Cr(II)K m (H 2O) n ]ads [Cr(II)K m (H 2O) n1 OH]ads + H +, [Cr(II)K m (H 2O) n1 OH]ads

(11)

10

4 1.7 E, V

1.1

1.3

1.5

i, A/dm2 50 (b) 1

30 2

10

3 4

1.05

1.25

1.45

1.65 E, V

i, A/dm2 50 (c) 1

30

10

3 5 4 1.2 1.4 1.6 E, V

1.0

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Translated by L. Smolina
Vol. 49 No. 5 2013

RUSSIAN JOURNAL OF ELECTROCHEMISTRY