Plasma processing for surface modification of trivalent chromium as alternative to hexavalent chromium layer

Plasma source ion implantation (PSII) treatment was undertaken to improve the mechanical properties of electrodeposited trivalent chromium layers. Nitrogen ions were implanted, with energies of − 15 to − 25 keV and doses of 1, 5 and 10 × 10¹⁷ atoms cm^− 2, to modify the surface properties of Cr plating layer. The surface properties of the films were characterized by XRD, SEM, ruby-ball on disk type tribometer and nanoindenter. Polycrystalline CrN films with (200), (220) and (222) orientations were preferentially grown and numbers of surface cracks were increased by N⁺-PSII onto trivalent chromium layers. The surface hardness of the Cr³⁺ plating layer was increased from 16 to 25 GPa by N⁺-PSII. Severe wear and higher friction was observed on N⁺-PSII treated trivalent Cr plating. It seemed that the wear debris from hardened and cracked surface of the N⁺-PSII treated specimen prompted abrasive wear in the wear test. Roughness of the Cr³⁺ plating layers was smoothed with increasing implantation doses.     

Study of an alternative phosphate sealer for replacement of hexavalent chromium

This study evaluates the possibility of replacing the hexavalent chromium passivation treatment used as a sealer after phosphating of carbon steel (SAE 1010) by a treatment with niobium ammonium oxalate (Ox). Samples of carbon steel (SAE 1010) after being phosphated in a zinc phosphate bath (PZn + Ni) were immersed in solution of niobium ammonium oxalate (250 mg L⁻¹ of Nb) either at pH 3.0 or pH 8.0. A passivation treatment with a solution with CrO₃ (200 mg L⁻¹ of Cr⁶⁺) was also used for reference.The corrosion resistance of the phosphated samples after passivation treatments was analyzed in a NaCl 0.5 mol L⁻¹ solution using electrochemical impedance spectroscopy (EIS) and anodic polarization curves. Salt spray tests were also performed to evaluate their corrosion resistance. The results showed that the highest corrosion resistance was obtained by passivation in a solution with (250 mg L⁻¹ of Nb) at pH 8.0.     

Comparative study of Cr3C2-NiCr coatings obtained by HVOF and hard chromium coatings

In the present work the corrosion resistance of micro-cracked hard chromium and Cr₃C₂-NiCr (HVOF) coatings applied on a steel substrate have been compared using open-circuit potential (E_OC) measurements, electrochemical impedance spectroscopy (EIS) and polarization curves. The coatings surfaces and cross-section were characterized before and after corrosion tests using optical microscopy (OM) and scanning electron microscopy (SEM). After 18 h of immersion, the open-circuit potential values were around −0.50 and −0.25 V/(Ag∣AgCl∣KCl_sat) for hard chromium and Cr₃C₂-NiCr, respectively. The surface analysis done after 12 h of immersion showed iron on the hard chromium surface inside/near surface cracks, while iron was not detected on the Cr₃C₂-NiCr surface even after 18 h. For longer immersion time hard chromium was more degraded than thermal sprayed coating. For hard chromium coating a total resistance values between 50 and 80 kΩ cm² were measured and two well-defined time constants were observed, without significant change with the immersion time. For Cr₃C₂-NiCr coating the total impedance diminished from around 750 to 25 kΩ cm² as the immersion time increased from 17 up to 132 h and two overlapped time constants were also observed. Polarization curves recorded after 18 h of immersion showed a lower current and higher corrosion potential for Cr₃C₂-NiCr coating than other samples studied.     

Pourbaix diagrams for chromium in concentrated aqueous lithium bromide solutions at 25 °C

Pourbaix diagrams (electrode potential-pH diagrams) for Cr-Br⁻-H₂O system at 25 °C were developed in 400, 700, 850, and 992 g/L (4.61, 8.06, 9.79, and 11.42 M) LiBr solutions, common concentrations in different parts of absorption devices. The diagrams were compared with the simple Cr-H₂O system at 25 °C. Equilibria for the Cr-Br⁻-H₂O system at 25 °C were determined for bromide ion activities of 15.61, 194.77, 650.06, and 2042.65, which corresponded to the 400, 700, 850, and 992 g/L LiBr solutions, respectively. Activities of all the dissolved species containing chromium were plotted for 10⁻⁶, 10⁻⁴, 10⁻², and 10⁰. Comparison of the simple Cr-H₂O system at 25 °C with the diagrams for Cr-Br⁻-H₂O system at 25 °C showed that the dominant aqueous Cr(III) species in acid solutions was Cr⁺³ for Br⁻ activities of 15.61, 194.77, and 650.06, whereas it was CrBr⁺² for Br^- activity of 2042.65. Aqueous CrBr⁺² formed at a Br⁻ activity higher than 943.05. The chromium solubility range in the acid area of the diagrams extended slightly to higher pH values with increasing Br⁻ activity and decreasing water activity, as a result of destabilization of Cr₂O₃.     

Electrochemical assessment of chromium in passivation films on tinplate

Abstract

When tinplate, passivated in chromate solutions, is anodically polarised either with current measurement at steadily increasing potential or with potential measurement at constant current, an indication of the oxidation of Cr^III to Cr^VI in the surface film is obtained. The indication can be made quantitative for the estimation of Cr^III. The constant-current method is preferred as permitting an easy measure of the charge passed during the oxidation which is indicated as an arrest on the potential/time curve. The preferred conditions are a chloride-free neutral phosphate solution and a current density of 25 μA/cm².

For most commercial tinplates the estimated Cr^III is similar to the total chromium but the few exceptions and others giving unusual potential/time curves may help in relating treatment td performance in laboratory cathodic-anodic passivation treatments, the chromium was wholly oxidised to Cr^VI by passage of a sufficient charge in the anodic period.     

Synthesis of chromium carbide (Cr3C2) nanopowders by the carbonization of the precursor

The solution-derived precursor method was used to synthesize chromium carbide (Cr₃C₂) nanopowders, ammonium dichromate ((NH₄)₂Cr₂O₇) and nanometer carbon black were used as raw materials. The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the single phase Cr₃C₂ can be synthesized under the conditions of 21 wt.% C, 1100 °C and 30 min, and the average crystallite size is 27.2 nm. The powders show good dispersion and are mainly composed of spherical or near- spherical particles with a mean diameter of ~ 30 nm. The surface of the specimen mainly consists of Cr, C and O three species elements. The XPS spectrum of Cr2p consists of two peaks with the binding energies of 577.5 eV and 575.3 eV, which are assigned to the Cr2p_3/2 species of Cr₂O₃ and Cr₃C_2 − x (0 ≤ x ≤ 0.5), respectively. The XPS spectrum of O1s energy region for chromium carbide contains three peaks (Oa, Oh and Od), which are considered to be due to O⁻, OH⁻ and Cr₂O₃, respectively.     

Influence of chromium substitution on structural and magnetic properties of BaFe12O19 powder prepared by sol-gel auto combustion method

The nanocrystalline Cr³⁺ substituted barium hexaferrite having generic formula BaFe_12−xCr_xO₁₉ (where x = 0.00, 0.25, 0.50, 0.75, and 1.00) samples were synthesized by sol-gel auto-combustion technique. The precursors were prepared by using stoichiometric amounts of Ba²⁺, Fe³⁺ and Cr³⁺ nitrate solutions with citric acid as a chelating agent. The metal nitrate to citric acid ratio was taken as 1:2 while pH of the solution was kept at 8. The thermal decomposition of nitrate-citrate gels of as-prepared powder was investigated by TG/DTA. The as-prepared powder of BaFe_12−xCr_xO₁₉ was sintered at 900 °C for 8 h. The sintered powder was characterized by XRD, EDAX, SEM and VSM technique. The pure barium hexaferrite shows only single phase hexagonal structure, while for the samples at x = 0.25, 0.50, 0.75 and 1.00 shows α-Fe₂O₃ peaks with M-phase of barium hexaferrite. The lattice parameters (a and c) decreases with increase in chromium content x. The particle size obtained from XRD data is in the range of 30-40 nm which confirms the nanocrystalline nature of the samples. The magnetic properties were investigated by means of vibrating sample magnetometer (VSM) technique. The saturation magnetization (M_s), remanence magnetization (M_r), coercivity (H_c) and magneton number (n_B) decreases with increase in chromium content x.     

Electrodeposition of black chromium from environmentally electrolyte based on trivalent chromium salt

Thin films of black chromium have been prepared by electrodeposition technique on steel substrates. Deposition of 1 µm thickness is conducted in a solution of chromium trivalent salt and oxidizing agent fluorosilicic acid (H₂SiF₆) operated at a current density 350 mA cm^− 2 at 25 °C and 1 min. The influence of H₂SiF₆ concentrations on the trivalent chromium electrodeposition was studied by the potentiodynamic technique. The phase structure and surface morphology of the deposited films were examined by using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The chemical composition of these thin films was determined by energy dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS) analysis. The spectral reflectance in the visible light, for films coating was characterized. From the SEM analysis, it was found that the black chromium has nano lamellar morphology that leads to a strong dispersion level. The XRD results showed that chromium, chromium oxide and cobalt oxide are the main bulk chemical compounds in the films. However, from XPS analysis of these surfaces, it was possible to determine that the most external layers of the films are made of different kinds of chromium and cobalt compounds. The black chromium-cobalt alloy thin film has better optical properties to transform solar energy into thermal energy, and these properties remain practically constant even when heat treated to a high temperature, 400 °C for 24 h.     

Synthesis and morphological study of chromium substituted Zn-Mn ferrites nanostructures via sol-gel method

Nanocrystalline ZnMn_1−xCr_xFeO₄ (1.0 ≥ x ≥ 0) ferrites were prepared by sol-gel route. X-ray diffraction (XRD) method was used to confirm the formation of single phase cubic spinel lattice for all the composition. The lattice parameter (a) shows a decreasing trend with the increase in Cr content. In all the studied compositions, spherical crystalline nanoparticles of about 30 nm size were observed by transmission electron microscopy (TEM) technique. The elemental analysis as obtained from EDAX is in close agreement with the expected composition from the stoichiometry of reactant solutions used. Infrared spectroscopic studies revealed two main absorption bands in the range of 400-800 cm⁻¹ arising due to tetrahedral (A) and octahedral (B) stretching vibrations. On substitution of Cr³⁺ in Mn³⁺ site, the stretching frequency of the octahedral site increases smoothly but that of the tetrahedral site is seen to be unaltered. The detailed results of XRD, SAED and infrared spectroscopy have been discussed so as to bring out the role of chromium substitution in determining structural properties of Zn-Mn ferrites.     

Distinctions between the Activating Effects of Sulfuric and Phosphoric Acids on the Process of Zinc Chromating

Activating effect of anions of sulfuric and phosphoric acids (both in the range from 0.025 to 0.200 mol/l) on the process of zinc chromating in acid (pH 1.1) 0.2 M CrO₃ solution is studied by analytical methods. A general balance of oxidized zinc (Zn²⁺) and reduced chromium (Cr³⁺) and their distribution between the solution and chromate film for different solution compositions, as well as the elemental composition throughout the film's depth, are determined. It is found that the zinc oxidation and Cr⁶⁺ reduction reactions do not proceed in the absence of SO^2– ₄ ions (that is, when only PO^3– ₄ ions are present), so that the chromate film cannot form. However, the PO^3– ₄ ions combined with SO^2– ₄ ions increase the Zn²⁺ and Cr³⁺ ions concentration in the solution significantly, while their concentrations in the film correspondingly decrease. SO^2– ₄ ions activate the zinc surface because they form soluble complex compounds with Zn²⁺ and Cr³⁺ ions and increase the part of the surface, on which the cathodic reduction of Cr⁶⁺ to Cr³⁺ occurs. The activating action of phosphoric acid is caused by the increase in the total (analytical) concentration of H⁺ ion in the solution; hence, the deposition of the Cr³⁺ and Zn²⁺ hydroxide compounds onto zinc is retarded, due to the increased near-surface concentration of H⁺ ion.     

Nature of the Oxide Film Present on Iron after Inhibition in 0·05 M Chromate Solutions

Abstract

Chemical and microprobe analyses have been used to study the composition of the oxide films formed on iron by 0·05 M potassium chromate, pH 4–8.

Chemical analyses have shown that the air-formed oxide film was thinned and evenly reinforced with a normal iron chromium spinel having a composition in the range Fe²⁺ (Fe³⁺_0·5 Cr³⁺_1·5)O₄ — Fe³⁺ Cr³⁺ O₃

Microprobe analyses indicated enrichment of chromium at scratch lines, but the effect was small compared with the overall thickening of the films.     

Synthesis of chromium carbide by reduction of chromium oxide with methane

In the present work, production of the chromium carbide was investigated by reduction of chromium oxide with methane-containing gas mixture. The experiments were conducted on the chromium oxide powder and methane gas at different temperatures, times, and gas mixtures. X-ray diffraction (XRD) analysis was used to characterize the products at different stages of reduction. The morphology of the starting chromium oxide powder and Cr₃C₂ were studied by electron microscopy technique. The results showed that the minimum temperature and time for carbide formation in 30%-methane gas mixture is about 850 °C and 20 min, respectively. X-ray diffraction analysis showed that Cr₃C₂ is the only carbide product. The formation of chromium carbide in 30%-methane gas mixture was completed at 1000 °C and 60 min.     

Composition analysis of the plating on electrolytically treated steel sheets in chromic acid solution

The structure and composition of the chromium plating on Tin Free Steel (TFS) were investigated and analyzed with scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDS), X-ray photoelectron spectroscopy (XPS) and coulometric electrolysis method. The plating under investigation was manufactured by a two-step electrolytic reduction from a chromic acid solution. Experimental results showed that the plating on TFS had a two-layer structure. Moreover, two valences of chromium, three and zero, were detected in the plating and no hexavalent chromium was found in it. Correspondingly, all chromium in the outer layer was trivalent and existed as the form of Cr₂O₃ and Cr(OH)₃, the content of which was about 6.62 mg/m², while the pure metallic chromium was the only form of chromium found in the inner layer with the content of about 57.75 mg/m². In addition, the amount of O existed as M-OH was twice as that of M-O in the above-mentioned hydrated chromium oxide layer.     

The effects of molybdate and dichromate anions on pit propagation of mild steel in bicarbonate solution containing Cl

The effects of molybdate and dichromate anions on pit propagation of mild steel in bicarbonate solution containing Cl⁻ were investigated by electrochemical measurements. MoO₄²⁻ ion suppressed both pit nucleation and propagation. Cr₂O₇²⁻ ion suppressed pit nucleation, but stimulated pit growth. The different effects of the two anions on pit propagation were explained by the opposite effects on pH value within pits. The pH value in molybdate-containing solution increased as a result of polymerization of MoO₄²⁻, while in dichromate-containing solution, pH value decreased due to hydrolysis of Fe³⁺ and Cr³⁺ which are the products of oxido-reducing reactions between Cr₂O₇²⁻ and Fe²⁺ ions.     

Synthesis and structure screening of nanostructured chromium oxide powders

The evolution with calcinations of chromium oxide (Cr₂O₃) nanocrystals of catalytic interest, prepared from reduction of K₂Cr₂O₇ with maleic acid has been studied. The characterization of the materials was confirmed by X-ray diffraction (XRD), Fourier transformation infrared (FT-IR), transmission electron microscope (TEM), N₂ adsorption–desorption isotherms, and thermo-analytical methods. The influence of the operating variables such as molar ratio, pH, gelation time and specific surface area was investigated and discussed. The results showed that the K₂Cr₂O₇/maleic acid of 1:1.7 molar ratio at pH 7 and 15 days gelation time were considered to be the best conditions for producing Cr₂O₃ of the pore diameter distribution in the range of 2–6 nm and specific surface area of 123 m²/g. The particle size and phases of chromium oxide were affected by the ratio of K₂Cr₂O₇ to maleic acid, temperature, and time of calcination. The amorphous phase appeared at room temperature, whereas it turned to crystalline phase when the calcination temperature increased to about 400 °C.     

Why the decorative chromium coating electrodeposited from trivalent chromium electrolyte containing formic acid is darker

The color of the decorative chromium coatings electrodeposited from trivalent chromium electrolytes containing formic acid or formate is usually darker than that from conventional hexavalent chromium electrolytes. For the purpose of clarifying the reason for this situation, X-ray diffraction (XRD), selected area electron diffraction (SAED), electron probe microanalyzer (EPMA) and high-resolution transmission electron microscopy (HRTEM) were employed to investigate the phases and fine microstructure of the typical decorative chromium coating produced from a typical trivalent chromium electrolyte containing formic acid. The results show that the coating is amorphous embedded with the nanocrystals of graphite, Cr₂₃C₆ and body-centered cubic structure chromium (bcc Cr). The presence of the nanocrystal graphite with strong infrared emission performance is the main reason for the darker color of the coating.     

Roles of aluminium and chromium in sulfidation and oxidation of sputter-deposited Al- and Cr-refractory metal alloys

Our recent results of the sulfidation and oxidation behavior of sputter-deposited Al- and Cr-refractory metal alloys at high temperatures are reviewed, and the roles of the aluminum and chromium in sulfidation and oxidation of these alloys are discussed in this paper. Niobium, molybdenum and tantalum are highly resistant to sulfide corrosion. Their sulfidation resistance is further enhanced by alloying with aluminum. Although Cr-refractory metal alloys also reveal high sulfidation resistance, their sulfidation rates do not become lower than those of the corresponding refractory metals. The sulfide scales formed on the Al-refractory metal and Cr-refractory metal alloys consist of two layers, comprising an outer Al₂S₃ or Cr₂S₃ layer and an inner refractory metal disulfide layer. The inner layer has a columnar structure, and the growth direction of the refractory metal disulfides is perpendicular to 0 0 1 direction. Intercalation of Al³⁺ ions into NbS₂ and a decrease in the sulfur activity at the outer layer/inner layer interface by the presence of the Al₂S₃ layer are probably responsible for the improvement of the sulfidation resistance by the addition of aluminum. The oxidation resistance of niobium and tantalum is improved more effectively by the addition of chromium rather than aluminum. Although preferential oxidation of chromium does not occur, an outer protective Cr₂O₃ layer in the oxide scales is formed on Cr-rich Cr-Nb and Cr-Ta alloys due to outward diffusion of Cr³⁺ ions. In contrast, continuous alumina layer cannot be formed on the Al-Nb and Al-Ta alloys, and the alloys reveal a pest phenomenon at 1073 K, and at higher temperatures rapid oxidation occurs. Concerning the oxidation of molybdenum, the addition of aluminum, which has higher activity for oxidation than chromium, is more effective in improving the oxidation resistance of molybdenum than chromium addition, since preferential oxidation of aluminum suppresses the formation of volatile molybdenum oxide.     

The conversion of chromium oxide to chromium carbide

The thermodynamic equilibria between chromium oxide, chromium carbide, and a CO-CO₂ mixture was calculated for various conditions. Experimental results on the rate of the Cr₂O₃ conversion to chromium carbide in CO-CO₂ mixtures at 1200°C are reported. The conversion rate was low and was strongly dependent on the carbon activity.     

Pulse-reverse electroplating of chromium from Sargent baths: Influence of anodic time on physical and electrochemical properties of electroplated Cr

Herein, chromium film was successfully synthesized by pulse-reverse (PR) electrodeposition using various anodic current time in a Sargent bath which is mainly composed of hexavalent chromium (Cr⁶⁺) and sulfuric acid (H₂SO₄). The correlation between anodic time during electroplating and various physical properties was investigated. The crack density, hardness, and thickness of electrodeposited chromium was decreased with an increase in anodic time for PR electroplating. The chromium prepared by PR electroplating showed higher corrosion resistance than that prepared by direct current (DC) electroplating owing to low crack density. Consequently, the optimal anodic time for PR electroplating was found to be 0.001 s based on the crack density, hardness, current efficiency, and film thickness. The results obtained suggest that this optimized process is a promising route for electroplating chromium film with low crack density and high corrosion resistance.     

The electronic, mechanical properties and theoretical hardness of chromium carbides by first-principles calculations

In the present study, the ground state properties of chromium carbides (h-CrC, c-CrC, Cr₃C, Cr₃C₂, Cr₇C₃, and Cr₂₃C₆) are calculated by means of the first-principles pseudopotential method using the CASTEP code. The equilibrium crystal structures and thermodynamical stability of the six chromium carbide phases are discussed. Moreover, the chemical bonding in these carbides are interpreted by calculating the density of states, electron density distribution and Mulliken analysis; all the six chromium carbides have a combination of metallic, ionic and covalent bonding characteristic, while Cr₇C₃ exhibits the strongest metallic character. The elastic constants, elastic anisotropies and theoretical hardness of the carbides are also presented, which are important parameters for the structural materials and surface coatings.