Passivation of micro-discontinuous chromium deposited from a trivalent electrolyte

Abstract

A method of treating a substrate, wherein the substrate comprises a layer deposited from a trivalent chromium electrolyte, is described. The method includes the steps of providing an anode and the chromium(III) plated substrate as a cathode in an electrolyte comprising (i) a trivalent chromium salt; and (ii) a complexant; and passing an electrical current between the anode and the cathode to passivate the chromium(III) plated substrate. The substrate may be first plated with a plated nickel layer so that the chromium(III) plated layer is deposited over the nickel plated layer.

Claims

1. A method of treating a substrate to provide improved corrosion protection thereof, wherein the substrate comprises a plated nickel layer and a chromium (III) plated layer, deposited above the nickel plated layer, from a trivalent chromium electrolyte, the method comprising the steps of: (a) providing an anode and the substrate comprising the chromium (III) plated layer as a cathode in a passivate solution comprising (i) a trivalent chromium salt; and (ii) a complexant; and (iii) a pH adjuster to adjust pH to between 2 and 5; and (b) passing an electrical current between the anode and the cathode to deposit a passivate film over the chromium (III) plated layer on the substrate, said passivate film comprising hydrated chromium compounds; wherein the electrical current is between about 0.1 and about 2.0 A/dm.sup.2; wherein the molar ratio of chromium salt to complexant is from 0.3:1 to 0.7:1 based on chromium content; and wherein the substrate after steps (a) and (b) has a polarization resistance of at least 4.010.sup.5 /cm.sup.2.

2. The method according to claim 1, wherein the trivalent chromium salt is selected from the group consisting of chromium sulfate, basic chromium sulfate, chromium chloride, and combinations of one or more of the foregoing.

3. The method according to claim 2, wherein the trivalent chromium salt is basic chromium sulfate.

4. The method according to claim 1, wherein the passivate solution comprises between about 0.01M and about 0.5M of the trivalent chromium salt.

5. The method according to claim 4, wherein the passivate solution comprises between about 0.02M and about 0.2M of the trivalent chromium salt.

6. The method according to claim 1, wherein the complexant is a hydroxy organic acid.

7. The method according to claim 6, wherein the hydroxy organic acid is selected from the group consisting of malic acid, citric acid, tartaric acid, glycolic acid, lactic acid, gluconic acid and salts of any of the foregoing.

8. The method according to claim 7, wherein the hydroxy organic acid is selected from the group consisting of malic acid, tartaric acid, lactic acid and gluconic acid and salts of any of the foregoing.

9. The method according to claim 1 wherein the passivate solution further comprises a conductivity salt.

10. The method according to claim 9, wherein the conductivity salt is selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and combinations of one or more of the foregoing.

11. The method according to claim 1, wherein the passivate solution is maintained at a temperature of between about 20 and about 40 degrees C.

12. The method according to claim 1 wherein the substrate is contacted with the passivate solution for between about 20 seconds and 5 minutes.

13. The method according to claim 12, wherein the substrate is contacted with the passivate solution for between about 40 and about 240 seconds.

14. The method according to claim 1, wherein the electrical current is between about 0.5 and about 1.0 A/dm.sup.2.

15. The method according to claim 1, wherein the pH of the passivate solution is about 3.5.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 depicts a Nyquist plot obtained from the results of Comparative Example 1.

(2) FIG. 2 depicts a Bode plot obtained from the results of Comparative Example 1.

(3) FIG. 3 depicts a Nyquist plot obtained from the results of Example 1.

(4) FIG. 4 depicts a Bode plot obtained from the results of Example 1.

(5) FIG. 5 depicts a comparison of the corrosion of an unpassivated panel, a panel passivated with hexavalent chromium and a panel passivated with the trivalent chromium electrolyte of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The present invention relates generally to a method of providing improved corrosion protection to trivalent chromium plated substrates. In one embodiment, the present invention is used to improve the corrosion resistance of trivalent chromium plated articles having a nickel plating layer underlying the chromium plated layer. Thus, the present invention may be used to improve the corrosion resistance of nickel plated substrates having a chromium layer deposited from a trivalent chromium electrolyte thereon.

(7) The inventors of the present invention have discovered a remarkable and unexpected synergy between chromium alloy coatings produced from trivalent electrolytes and the coatings produced by treating such chromium alloy plated items cathodically in a solution containing trivalent chromium salts and a suitable complexant.

(8) The present invention comprises a method of processing components plated with a chromium alloy deposit in a solution comprising a trivalent chromium salt and a complexant.

(9) More specifically, in one embodiment, the present invention relates generally to a method of treating a substrate, wherein the substrate comprises a plated layer deposited from a trivalent chromium electrolyte, the method comprising the steps of:

(10) (a) providing an anode and the substrate as a cathode in an electrolyte comprising (i) a trivalent chromium salt; and (ii) a complexant;

(11) (b) passing an electrical current between the anode and the cathode to deposit a passivate film on the substrate.

(12) As described herein, in one preferred embodiment the substrate is first plated with a nickel plating layer and the plated layer is deposited using a trivalent chromium electrolyte, over the nickel plated layer.

(13) The electrolyte solution typically comprises between about 0.01 and about 0.5 M, more preferably between about 0.02 and about 0.2 M of the chromium(III) salt. The trivalent chromium salt is preferably selected from the group consisting of chromium sulfate, basic chromium sulfate (chrometan), and chromium chloride, although other similar chromium salts may also be used in the practice of the invention. The complexant is preferably a hydroxy organic acid, including, for example, malic acid, citric acid, tartaric acid, glycolic acid, lactic acid, gluconic acid, and salts of any of the foregoing. More preferably, the hydroxy organic acid is selected from the group consisting of malic acid, tartaric acid, lactic acid and gluconic acid and salts thereof.

(14) The chromium salt and the complexant are preferably present in the solution at a molar ratio of between about 0.3:1 to about 0.7:1.

(15) The solution may also optionally include conductivity salts, including, for example, sodium chloride, potassium chloride, sodium sulfate and potassium sulfate, by way of example and not limitation.

(16) The substrates to be processed are immersed in the passivate solution preferably at a temperature of between about 10 and about 40 C. and a pH of between about 2 and about 5 and most preferably at about 3.5. The substrates are made cathodic at a current density of between about 0.1 and about 2 A/dm.sup.2 for a period of time between about 20 seconds and about 5 minutes, more preferably for about 40 to about 240 seconds. Following this, the components are rinsed and dried. This treatment produces a remarkable improvement in the corrosion performance of the plated components.

(17) The process described herein works by depositing a thin layer of hydrated chromium compounds on the surface of the components. Making the components cathodic in an electrolyte of moderate pH liberates hydrogen ions at the surface which rapidly leads to a local increase in pH. This in turn leads to the precipitation of basic chromium compounds at the surface.

(18) In another embodiment, the present invention relates generally to a substrate comprising a plated layer deposited from a trivalent chromium electrolyte passivated according to the process described herein, wherein the passivated chromium(III) plated layer exhibits a polarization resistance of at least about 4.010.sup.5 /cm.sup.2, more preferably a polarization resistance of at least about 8.010.sup.5 /cm.sup.2, and most preferably a polarization resistance of at least about 9.010.sup.5 /cm.sup.2.

(19) The exact nature of the coating is not known, but examination by X-ray photo-electron spectroscopy (XPS) reveals the presence of trivalent chromium and oxygen. It is well known that chromium(III) ions can form polymeric species at high pH (by a process known as olation) and it is likely that it is these compounds that form the passivate layer because chromium(III) hydroxide forms a flocculent precipitate that is adherent to surfaces.

(20) The inventors have found that the best results are obtained using chrometan as a source of chromium ions and sodium gluconate as the complexant. The inventors have also found that above a concentration of about 0.5 M, the coating produced is dark in color and detracts from the visual appearance of the component. Regarding the complexant, above a ratio of about 0.7:1 complexant to chromium, the chromium is too strongly complexed and the corrosion performance is compromised. Below a ratio of about 0.3:1, the chromium tends to precipitate from solution. The inventors have also found that a pH of about 3.5 is optimum for the process. Below a pH of about 2.0, the hydrogen ion concentration is too high for the pH to increase sufficiently to form the coating and no protective film is formed. Above a pH of about 5, chromium ions tend to precipitate from solution as chromium(III) hydroxide. The temperature of the process solution is not critical. However, temperatures above about 40 C. require a much higher current density in order to produce a coating. This is probably due to the increased rates of hydrogen ion diffusion at the higher temperature.

(21) The inventors have found that the optimum current density is in the range of about 0.5 to 1.0 A/dm.sup.2. Below this value, there is insufficient pH rise to form the coating effectively and above this value, the coatings tend to become too thin because of high scrubbing/agitation of released hydrogen that detracts from the visual appearance of the coatings. At the optimum current density, the preferred processing time is about 40 to about 240 seconds. Shorter times produce thinner coatings so that the corrosion performance is not optimum and longer times tend to produce coatings that darken the visual appearance of the processed components.

(22) The present invention will now be illustrated by reference to the following non-limiting examples:

Comparative Example 1

(23) Four steel panels were plated with 5 microns of bright nickel solution and 0.3 microns of chromium deposited from a solution containing 250 g/L of chromic acid and 2.5 g/L of sulfate ions. The low thickness of nickel was chosen so that there would be some porosity and exposure of the underlying steel substrate. This type of plating quickly shows substrate corrosion.

(24) Two of the panels were left untreated and two of the panels were coated with a passivate of the invention described above having the following composition:

(25) Chrometan 10 g/L (giving a chromium concentration of 1.8 g/L or 0.03 M)

(26) Sodium gluconate 3.8 g/L (giving a molar concentration of 0.017 M)

(27) Sodium hydroxide to adjust the pH to 3.5

(28) The coating process was carried out at a temperature of 25 C. and an average current density of 0.5 A/dm2 for 120 seconds. The panels were then rinsed and dried. The corrosion performance of the panels was evaluated in a 5% sodium chloride solution by electrochemical impedance spectroscopy (EIS) using an EG&G model 263A potentiostat and a Solartron frequency response analyzer (FRA). This technique can be used to measure the polarization resistance of the test panel which is in turn related to the overall rate of corrosion of the surface, the higher the polarization resistance, the more corrosion resistant the coating.

(29) In order to determine this value, a frequency scan was carried out from 60,000 Hz to 0.01 Hz at the corrosion potential +/10 mV. The polarization resistance was determined by plotting the real impedance versus the imaginary impedance at every point on the frequency scan. This is called a Nyquist plot and for a normal charge transfer process yields a semicircular plot from which the polarization resistance can be calculated. Plots of frequency versus impedance and frequency versus phase angle were also plotted (these are called Bode plots and can generate more detailed information about the nature of the corrosion process). FIGS. 1 and 2 show the Nyquist and Bode plots obtained from an average of 5 results from each of the panels.

(30) It can be seen from the Nyquist plot that the semi-circle formed from the unpassivated panel is much larger that than from the passivated panel. Calculation of the polarization resistance in each case gives a value of 9.210.sup.5 /cm.sup.2 for the unpassivated panel and 2.910.sup.5 /cm2 for the passivated panel. Thus, the corrosion resistance is less for the passivated panel than the unpassivated panel by a factor of about 3. The bode plot of frequency versus phase angle clearly shows the effect of passivation. The red line shows 2 time constants for the passivated panel and just one for the unpassivated panel. This clearly indicates formation of a coating.

Example 1

(31) Test panels were prepared in the same manner as in Comparative Example 1 except that the chromium coating was applied from a trivalent electrolyte (Trimac III, available from MacDermid, Inc.). This produces a chromium coating containing up to 2% sulfur and also having up to 0.5% carbon codeposited with the chromium, effectively making it an alloy. Again, two panels were left unpassivated and two were passivated using the same process as described in Comparative Example 1. Again, EIS was used to examine the panels to determine the polarization resistance.

(32) The results of these tests are shown in FIGS. 3 and 4 (Nyquist and Bode plots).

(33) Here, it can be seen that the situation is reversed and that the passivated panel has the higher polarization resistance. This is supported by the bode plot which again shows the two time constants for the passivated panel and only one for the unpassivated panel. In this case, the calculated values of the polarization resistance are 1.810.sup.5 /cm.sup.2 for the unpassivated panel and 8.810.sup.5 /cm.sup.2 for the passivated panel. This represents an improvement in corrosion resistance of a factor of about 4.

Example 2

(34) Test panels were prepared in the same manner as in Comparative Example 1 except that the chromium coating was applied from a trivalent electrolyte (Trimac III, available from MacDermid, Inc.). One of the panels was left unpassivated, one was cathodically passivated in a solution of potassium dichromate and one was passivated using the process solution as described in Comparative Example 1.

(35) The panels were exposed to a neutral salt spray accelerated corrosion test (ASTM B117) for 72 hours and the results were compared as shown in FIG. 5. As seen in FIG. 5, the unpassivated panel (left panel) showed major red rust corrosion and some red rust was also evident on the panel passivated in hexavalent chromium (center panel). By comparison, there was no corrosion evident on the panel passivated in accordance with the compositions described herein.