Journal Pre-proof

Hard chromium composite electroplating on high-strength

stainless steel from a Cr(III)-ionic liquid solution

Hadi Khani, Joan F. Brennecke

PII: S1388-2481(19)30200-0
DOI: https://doi.org/10.1016/j.elecom.2019.106537
Reference: ELECOM 106537

To appear in: Electrochemistry Communications

Received date: 17 August 2019

Revised date: 1 September 2019
Accepted date: 2 September 2019

Please cite this article as: H. Khani and J.F. Brennecke, Hard chromium composite
electroplating on high-strength stainless steel from a Cr(III)-ionic liquid solution,
Electrochemistry Communications (2018), https://doi.org/10.1016/j.elecom.2019.106537

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© 2018 Published by Elsevier.

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Hard chromium composite electroplating on high-strength stainless steel from a Cr(III)-

ionic liquid solution

Hadi Khani and Joan F. Brennecke*

McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712-

1589, United States

Abstract: A composite chromium coating has been potentiostatically electroplated on high-strength

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stainless steel substrates from a trivalent chromium bath. The electrolyte solvent consists of 1-butyl-3-

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methylimidazolium chloride ([Bmim][Cl]) to which water, hexadecyltrimethylammonium bromide

(CTAB), poly(diallyldimethylammonium chloride) (PDDA), and Al2O3 particles (≈ 3–4 µm) were added

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to improve the ion transport properties, the wettability at the electrolyte–substrate interface, the metallic
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chromium content, and the microhardness of the coating, respectively. The X-ray photoelectron spectrum
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of the coating reveals 85% metallic chromium and 15% chromium oxides and chromium hydroxide.

Characterization of the coating shows the existence of chromium carbide-type bonds, resulting from the
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incorporation of carbon atoms into the chromium crystal lattice, leading to a high degree of amorphization

of the coating. Optimization of electroplating conditions yielded a uniform chromium composite coating
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with a Vicker’s microhardness of 860 (±10) HV and a thickness of 42 µm (±4), which is comparable to a
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chromium coating obtained from conventional chromic acid baths.

Keywords: trivalent chromium, electroplating, XPS, high-strength stainless steel, ionic liquid

1. Introduction

Electroplated chromium coatings provide excellent corrosion and mechanical properties, but require the

use of highly oxidative and toxic traditional hexavalent chromium baths. This has motivated the scientific

and industrial communities to develop technologies that make use of much less toxic trivalent chromium

solutions. This transition has accelerated since February 2003, when the Restriction of Hazardous

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Substances Directive (RoHS) was announced by the European Union, which restricts the use of

hexavalent chromium baths in the manufacture of electrical and electronic products [1]. To that end, there

have been many efforts to electroplate chromium from both aqueous and non-aqueous electrolyte

solutions of trivalent chromium salts. In an aqueous electrolyte, the reduction of electrochemically stable

[Cr(H2O)6]3+ ions requires a high overpotential which eventually leads to the unwanted hydrogen

evolution reaction (HER) at the substrate of interest, resulting in a low current efficiency and poor coating

properties [2]. This issue is much more challenging when stainless-steel substrates are subject to

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chromium electroplating since these substrates are known to have high electrocatalytic activity for the

HER due to the presence of transition metals (e.g. Mn, Cr, Ni, and Fe) [3, 4]. On the other hand, the use

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of imidazolium-based ionic liquids (ILs), as non-aqueous solvents, has enabled the electrodeposition of

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crystalline chromium with high current efficiency on some substrates [5, 6]. While the use of water-free
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ILs and chromium salts is inconvenient because they require a glovebox or dry room, the most serious

drawback is that dry ILs have not shown promising coating results on technologically important metals
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like stainless steel. However, recent studies have shown that the presence of water in an IL-based
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electrolyte (i.e. water-in-IL) can significantly improve mass transport properties, conductivity, and

nucleation characteristics, without sacrificing corrosion and mechanical properties or current efficiency
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[7, 8]. Here, we show successful chromium composite electroplating on stainless steel substrates from a
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water-in-IL electrolyte. The issues associated with surface roughness, wettability, interfacial tension,

metallic chromium content, and HER have been resolved to achieve mechanical properties comparable to

those of coatings obtained from conventional chromic acid baths.

2. Experimental procedure

The electrochemical bath contains chromium(III) chloride hexahydrate (Sigma-Aldrich, ≥ 98%), 1-butyl-

3-methylimidazolium chloride ([Bmim][Cl]) (Tokyo Chemical Industry Co., Ltd., ≥ 98.0%), and Milli-Q

water (Millipore-Sigma, 18.2 MΩ-cm) in a mole ratio of 1:2:12, respectively (CrBH electrolyte

hereafter). The optimized electrolyte also contains CTAB (Sigma-Aldrich, ≥ 99%),

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poly(diallyldimethylammonium chloride) (PDDA, MW = 400,000−500,000, methanol:water solution

95:5 vol %, Sigma-Aldrich), and Al2O3 particles (Industrial Supply, Inc., ≈ 3–4 µm size). The

electrochemical cell consists of a 4130 high strength stainless steel (McMaster, HSS) working electrode

(6 mm × 12 mm), a platinum gauze (AMETEK, Inc., Pt, 4 cm2 area) as an auxiliary electrode, and a

platinum wire (BASi, 99.9%) as a pseudo-reference electrode. The electroplating bath was kept at

52(±1)°C using an oil bath. The potentiostatic method (−2.2 V vs Pt) was used to perform the chromium

electroplating for 20 min under stagnant conditions. The coatings were washed with methanol and

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deionized water and finally dried with air flow. The same electrochemical parameters were used for all

electroplating experiments.

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3. Results and discussion

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The cyclic voltammogram in Fig. 1a shows the electrochemical behavior of Cr(III) in the CrBH
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electrolyte at a glassy carbon electrode when the potential is scanned from +0.8 to ‒2.0 V (vs Pt) and
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swept positively back to +0.8 V. Two broad reduction peaks are observed at ‒1.17 and ‒1.7 V, implying

that the reduction of Cr(III) to metallic chromium occurs in two steps. Previously, we have shown that
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predominantly [Cr(III)(H2O)4Cl2]+ is present in the CrBH electrolyte [8], which undergoes electrochemical

reduction to [CrII(H2O)4Cl2] at a potential of ‒1.17 vs Pt (Eq. 1). The electrodeposition route proceeds via
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the reduction of intermediate complex adsorption, apparently bivalent chromium chloride-hydroxide

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[CrII(H2O)4(OH)Cl], as an electroactive complex, to metallic chromium or Cr(OH)2 (Eq. 3 and 4); the

latter will subsequently reduce to metallic chromium according to (Eq. 5) [9-11].

[CrIII(H2O)4Cl2]+ + e– → [CrII(H2O)4Cl2] (1)

[CrII(H2O)4Cl2] + OH– ↔ [CrII(H2O)4(OH)Cl] + Cl– (2)

[CrII(H2O)4(OH)Cl] + 2e– → Cr0 + 4H2O + Cl– + OH– (3)

[CrII(H2O)4(OH)Cl]+ OH– ↔ [CrII(OH)2] + 4H2O + Cl– (4)

[CrII(OH)2] + 2e– ↔ Cr0 + 2OH– (5)

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In parallel, HERs (Eq. 6 and 7) proceed at the cathode at less negative potentials.

2H2O + 2e− → H2(g) + 2OH− Eo = −0.83 vs NHE (6)

2H+ + 2e− → H2(g) Eo = 0.00 vs NHE (7)

While our chromium electroplating method has shown promising coating results on glassy

carbon, copper, and brass electrodes [8], it shows almost no deposition on HSS substrates due to the

predominant HER [3, 4]. This effect can be seen in Fig. 1a, where the HER at HSS has almost completely

eliminated the two-step Cr(III) reduction peaks. The severe HER is expected in the CrBH electrolyte

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since the pH of the electrolyte is highly acidic (pH > 1) due to the hydrolysis of hydrated CrCl3 salt.

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The surface morphology of HSS substrates strongly influences the extent of the HER.

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Unfortunately, various chemical and electrochemical surface polishing/treatments of the HSS substrates
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[12] either roughen the HSS substrates and provide more “active” sites for HER, or deactivate the HSS

substrate surface through adsorption of etchant reagents and/or products. Mechanical polishing of the
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substrates using silicon carbide (SiC) paper provides a finished substrate on which chromium can be
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electroplated reproducibly from the CrBH electrolyte. To that end, the HSS substrates were hand polished

with 600 and then 1200 grit size SiC in the presence of isopropanol as a lubricant, followed by bath
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sonication in methanol for 10 min to dislodge remaining silicon carbide particles. As can be seen from
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Fig. 1d, a uniform coating with a network of micro-cracks is achieved on HSS substrates that had been

mechanically polished. An XPS (Kratos Axis Ultra DLD, Manchester, U.K.) analysis of the coating (Fig.

1b) shows a chemical composition of 49%, 30%, and 21% for metallic chromium, chromium hydroxide

(Cr(OH)3), and chromium oxides (Cr2O3), respectively. Each Cr 2p3/2 and Cr 2p1/2 peak of Cr2O3 is

deconvoluted into five small peaks at 575.9 to 579.3 eV and 584.5 to 588.5 eV, respectively, due to

multiple splitting of the 3p6d3 configuration. The Cr 2p3/2 components observed at 574.1 and 577.3 eV

correspond to metallic chromium and Cr(OH)3 species, while their corresponding Cr 2p1/2 bands appear at

583.4 and 587.0 eV, respectively. The metallic chromium, Cr(OH)3 and Cr2O3 contents should be

representative of the bulk coating since the surface was mechanically scraped prior to XPS analysis. The

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average microhardness of the coating was 340 (±35) HV using a Vicker’s hardness tester (Leco, Model

M-400) at a loading of 10 gf.

Although we were able to electroplate chromium on the polished HSS substrates from the CrBH

electrolyte, the coating was not uniform (e.g. thicker coating on the edges and almost no coating in the

center), and the thickness was just 4–7 µm and did not increase with electroplating time. Hydrogen

bubbles from the HER are significantly reduced on the polished substrate compared to chemically or

electrochemically treated substrates. However, the inevitable accumulation of hydrogen bubbles on the

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polished HSS cathode prevents the growth of the chromium coating. This problem was ameliorated by

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adjusting the wettability at the electrolyte/substrate interface by the addition of CTAB surfactant. CTAB

decreases the surface tension of the electrolyte, which lowers the interfacial tension and facilitates the

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easy release of the gas bubbles from the cathode surface [13]. This allows chromium ions from the bulk
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electrolyte solution to reach the HSS substrate, resulting in a faster rate of chromium deposition. The
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CTAB surfactant was added to the CrBH electrolyte (new electrolyte named C-CrBH hereafter) at

concentrations between 0.1 and 10 g L‒1. The addition of CTAB significantly improves the coating
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uniformity, as well as the coating thickness (≈ 65 µm) (Fig. 1 e and f). The optimized concentration of

CTAB was found to be 0.2 g L‒1 in CrBH electrolyte; higher concentrations did not show any
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improvement in performance. XPS (Fig. 1c) indicates that the coating on HSS is 62% metallic chromium,
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21% Cr(OH)3, and 17% Cr2O3. The coating shows good adhesion and an enhanced Vickers

microhardness (≈ 415±20 HV) compared to the sample produced from the CrBH electrolyte. Nonetheless,

the hardness is lower than chromium plated from conventional chromic acid baths and this can be

attributed to internal stress and/or lower metallic chromium content. In particular, we observed a network

of micro-cracks (1–3 µm width) throughout the coating (Fig. 1d-f), which is apparently due to (i) the

relieving of the internal stress of the coating, originating from HER and known as hydrogen

embrittlement relief, and/or (ii) the adsorption of chromium hydroxides/oxides on the coating surface

[14].

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It has been emphasized by previous researchers that the formation of the intermediate layer,

[CrII(H2O)4(OH)Cl]ads, is important in controlling the quality of the electroplated chromium layer [9-11].

Since the formation of this intermediate layer is a pH-dependent process (see Eq. 2), the local surface pH

has a significant influence on the formation of metallic chromium. To address this issue, we added the

cationic polymer, PDDA, to the C-CrBH electrolyte. This resulted in the formation of adherent films with

considerably fewer cracks (Fig. 2 a and b) and a higher metallic chromium content. PDDA is believed to

adsorb on the growing film, which reduces both the hydrogen evolution rate and the critical reduction

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potential. This leads preferentially to the formation of an intermediate CrII layer (which later reduces to

metallic chromium, see Eqs. 3–5), rather than chromium hydroxide/oxide. PDDA may adsorb on HER

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active sites and prevent the HER from taking place and, hence, inhibits a pH rise at the cathode surface

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during electroplating. The optimized PDDA concentration was 1.2 g L‒1 in C-CrBH electrolyte (new
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electrolyte named CP-CrBH hereafter). The large adsorption of PDDA at higher concentrations reduces

the electrodeposition rate, apparently due to a lower electron-transfer rate of chromium ions, leading to
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thin coatings. The XPS result for the sample obtained from CP-CrBH shows 85% metallic chromium, 5%
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Cr(OH)3, and 10% Cr2O3 (Fig. 3a). Deconvolution of the C 1s spectrum (Fig. 3b) shows two peaks at

282.6 eV and 823.0 eV, which are attributed to Cr–C carbide-type bonds. The peaks at higher binding
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energies correspond to hydrocarbon (285.2 eV) and C-O/C=O bonds (285.2, 285.2 eV, and 285.2 eV).
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The presence of carbon chains in the coating is expected since both the electrolyte ([Bmim][Cl]) and the

additives (CTAB and PDDA) are carbon-rich species, with the carbide carbon (Cr‒C) species mainly

originating from the reduction of electrochemically active [Bmim] cations [5, 15]. The XRD (XRD,

Rigaku Miniflex 600) pattern of the coating shows a broad diffraction peak centered at 2θ = 44°, which is

indexed with the standard peak for the Cr(110) plane (Fig. 3c). The high degree of amorphization is

attributed to the incorporation of metalloid carbon atoms into the chromium crystal lattice, which disturbs

the setting order of the chromium atoms [16]. The coating has a Vickers microhardness value of ≈ 575

HV (±15); however, this is still lower than that of chromium coatings electroplated from conventional

Cr(VI) aqueous baths (≈ 800−900 HV).

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To further increase the hardness of the coating, we performed composite electroplating of

chromium with 3–4 µm Al2O3 particles. 2–25 g L‒1 of Al2O3 particles were added to the CP-CrBH

electrolyte, followed by sonication at 40 °C for 15 min to disperse the particles in the solution prior to

electroplating. As seen in Fig. 2c-f, the Al2O3 particles (the light-colored pieces) were uniformly

distributed throughout the coating on the HSS surface. The addition of Al2O3 to the CP-CrBH electrolyte

bath reduced the crack width to < 200 nm and increased the microhardness of the coating. As shown in

Fig. 3d, microhardness increased with increasing Al2O3 concentration, but the thickness of the composite

coating decreased. At the optimum 10 g L‒1 Al2O3 concentration, the coating had 860 (±10) HV hardness,

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42 (±4) µm thickness, and good adhesion to the HSS substrate. This hardness is equivalent to that of

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chromium deposits from conventional Cr(VI) chromic acid baths. The composite chromium/Al2O3

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coating has the same chromium composition as the samples electroplated from CP-CrBH (see Fig. 2b).
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We postulate that the co-deposited Al2O3 particles reduce stress levels in the coating by interrupting the

metal grain growth which causes tensile stress [17], resulting in the remarkable hardness values. The high
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hardness of the Al2O3 particles themselves might also contribute to the enhanced hardness values of the
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composite. The reduction in the thickness of the coating compared with the sample obtained from the CP-

CrBH electrolyte is likely due to Al2O3 particles blocking the diffusion of chromium ion species from the
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electrolyte to the substrate, as well as reducing the local conductivity of the coating.
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4. Conclusion

Chromium was successfully electroplated on steel substrates from a Cr(III) water-in-[Bmim][Cl]

electrolyte after mechanical polishing of the 4130 HSS substrates. Unfortunately, the coating was

thin and not uniform. Dramatic improvements in coating chromium metal content, uniformity,

thickness and hardness were achieved through the addition of CTAB surfactant, cation PPDA

polymer, and Al2O3 particles. The final electrolyte solution (Figure 3e) contained chromium(III)

chloride hexahydrate, 1-butyl-3-methylimidazolium chloride and water in a mole ratio of 1:2:12,

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with 0.2 g L‒1 CTAB, 1.2 g L‒1 PDDA and 10 g L‒1 3–4 µm Al2O3 particles. The metallic

chromium composition of the composite coating was 85% and it had a hardness of 860 (±10)

HV. Thus, electroplating from a Cr(III) water-in-[Bmim][Cl] electrolyte (with appropriately

chosen additives) can produce coatings on steel with a hardness comparable to coatings produced

by electroplating from conventional Cr(VI) aqueous baths. Unfortunately, the electrolyte

reusability was poor due to the contamination produced by the anodic reactions at the platinum

counter electrode. We noticed that chloride and water oxidation are the predominant anodic

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reactions in our electroplating bath. Unfortunately, our various attempts to minimize chloride

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oxidation through electrolyte optimization resulted in very poor coating performance. We believe

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that the solution to increasing the reusability of our electrolyte lies in the composition of the
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anode itself, with the aim of increasing the overpotential of chloride oxidation as well as

suppressing the undesired anodic reactions.

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Funding: This work was supported by the American Lightweight Materials Manufacturing

Innovation Institute (cooperative agreement N00014-14-2-0002).

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References:

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restriction of the use of certain hazardous substances in electrical and electronic equipment (RoHS) and

amendments.

[2] Z. Zhixiang, L. Aiming, Z. Junyan, A review of recent patents on trivalent chromium plating, Recent

Patents on Materials Science, 2 (2009) 50-57.

[3] A.A. El-Meligi, N. Ismail, Hydrogen evolution reaction of low carbon steel electrode in hydrochloric

acid as a source for hydrogen production, ‎Int. J. Hydrog. Energy, 34 (2009) 91-97.

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[4] J.M. Olivares-Ramírez, M.L. Campos-Cornelio, J. Uribe Godínez, E. Borja-Arco, R.H. Castellanos,

Studies on the hydrogen evolution reaction on different stainless steels, ‎Int. J. Hydrog. Energy, 32 (2007)

3170-3173.

[5] X. He, C. Li, Q. Zhu, B. Hou, Y. Jiang, L. Wu, Electrochemical mechanism of Cr(III) reduction for

preparing crystalline chromium coatings based on 1-butyl-3-methylimidazolium hydrogen sulfate ionic

liquid, RSC Adv., 4 (2014) 64174-64182.

[6] X. He, B. Hou, C. Li, Q. Zhu, Y. Jiang, L. Wu, Electrochemical mechanism of trivalent chromium

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reduction in 1-butyl-3-methylimidazolium bromide ionic liquid, Electrochimica Acta, 130 (2014) 245-

252.

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[7] A.P. Abbott, K.J. McKenzie, Application of ionic liquids to the electrodeposition of metals, PCCP, 8

(2006) 4265-4279.
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[8] L. Sun, J.F. Brennecke, Characterization of imidazolium chloride ionic liquids plus trivalent

chromium chloride for chromium electroplating, Ind. Eng. Chem. Res., 54 (2015) 4879-4890.
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[9] N.V. Phuong, S.-C. Kwon, J.-Y. Lee, J. Shin, B.T. Huy, Y.-I. Lee, Mechanistic study on the effect of
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PEG molecules in a trivalent chromium electrodeposition process, Microchem. J., 99 (2011) 7-14.

[10] N.V. Phuong, S.C. Kwon, J.Y. Lee, J.H. Lee, K.H. Lee, The effects of pH and polyethylene glycol
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on the Cr(III) solution chemistry and electrodeposition of chromium, Surf. Coat. Technol., 206 (2012)
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4349-4355.

[11] Y. Yao, Q. Wei, M. Sun, Y. Chen, X. Ren, Environmentally friendly chromium electrodeposition:

effect of pre-electrolysis on a Cr(III) bath in an anion-exchange membrane reactor, RSC Adv., 3 (2013)

13131-13136.

[12] Metals Handbook: Metallography and Microstructures, Volume 9, 9th edition, ASM International,

The Materials Information Society, 1985.

[13] K.S.A. Gnanasekaran, K.C. Narasimham, H.V.K. Udupa, The effect of the additive cetyl trimethyl

ammonium bromide on the electrodeposition of lead dioxide, J. Appl. Electrochem., 6 (1976) 189-198.

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[14] H.A. Ramezani-Varzaneh, S.R. Allahkaram, M. Isakhani-Zakaria, Effects of phosphorus content on

corrosion behavior of trivalent chromium coatings in 3.5 wt.% NaCl solution, Surf. Coat. Technol., 244

(2014) 158-165.

[15] B. Gorodetsky, T. Ramnial, N.R. Branda, J.A.C. Clyburne, Electrochemical reduction of an

imidazolium cation: a convenient preparation of imidazol-2-ylidenes and their observation in an ionic

liquid, Chem. Commun., (2004) 1972-1973.

[16] Z. Zeng, L. Wang, A. Liang, L. Chen, J. Zhang, Fabrication of a nanocrystalline Cr–C layer with

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excellent anti-wear performance, Mater. Lett., 61 (2007) 4107-4109.

[17] I. Garcia, A. Conde, G. Langelaan, J. Fransaer, J.P. Celis, Improved corrosion resistance through

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microstructural modifications induced by codepositing SiC-particles with electrolytic nickel, Corros. Sci.,

45 (2003) 1173-1189.
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Fig. 1. (a) CV curve of GC and HSS electrodes in CrBH electrolyte; XPS spectra of Cr 2p peaks for the

coating electroplated on HSS from (b) CrBH and (c) C-CrBH electrolyte; SEM images of coating
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electroplated on HSS from (d) CrBH and (e and f) C-CrBH electrolyte. Some increase in the number of

cracks was observed when the samples were placed in the SEM chamber, consistent with hydrogen
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embrittlement. Note that this did not occur for the optimized coatings (Fig. 2).
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Fig. 2. SEM images of coating electroplated from (a and b) CP-CrBH and (c-f) Al2O3/CP-CrBH
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electrolyte.
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Cr0
Cr 2p3/2 (a) C 1s (b)
Cr(OH)3
Cr2O3

Intensity (CPS)
Intensity (CPS)

Cr 2p1/2

590 588 586 584 582 580 578 576 574 572 570 291 290 289 288 287 286 285 284 283 282 281
Binding energy (eV) Binding energy (eV)

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(c) 900 (d) 70

850
60

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Microhardness (HV) 800
Intensity (a.u.)

Thickness (mm)
50
750

700

650
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30
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20
600

10
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550

20 30 40 50 60 70 80 0 5 10 15 20
2-theta (degrees) Al2O3 concentration (g L-1)
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(e) Optimized electrolyte bath

Bath Electroplating
[Bmim][Cl H2 O CrCl3 CTAB PDDA Al2O3
temperature time
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2 mol 12 mol 1 mol 0.2 g L‒1 1.2 g L‒1 10 g L‒1 52 (±1) oC 20 min
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Coating properties

%Cr0 %Cr2O3 %Cr(OH)3 %Al2O3 Hardness Thickness

85 (atm.%)1 10 (atm.%) 5 (atm.%) 16 (wt. %)2 860 ( 10) HV 42 ( 4) µm

1Percentages are based on the total amount of chromium content 2Percentage is based on the total weight of the coating

Fig. 3. XPS spectra of (a) Cr 2p peaks and (b) C 1s peaks for the coating electroplated on HSS from CP-

CrBH electrolyte; (c) XRD pattern of samples obtained from CP-CrBH electrolyte; (d) the microhardness

and coating thickness for different concentrations of Al2O3 particles; (e) optimized electrolyte

composition and coating properties.

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Graphical abstract
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Highlights

 Toxic and carcinogenic Cr(VI) is no longer required for plating hard chromium

 Electroplating from a Cr(III) bath has been successfully performed on stainless steel substrates

 The coating properties are comparable to those obtained from traditional Cr(VI) baths

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