26

Electrodeposition

of Chromium

Alloys

26.1 Introduction

CAST OR WROUGHT chromium alloys, containing the iron-group metals, have

numerous uses in the the home and in technology. These applications are based
on following properties of the alloys: good corrosion resistance; high strength
and hardness; and low rate of oxidation and retention of strength at elevated
temperatures. Chromium alloys, if they could be electrodeposited, would have
many uses as protective coatings for steel and as electroformed objects. Investigations have been made of the deposition of chromium alloys, but thus far no
process has been developed to the point of commercial feasibility. The electrodeposition of chromium-iron alloys comes the nearest to being a successful
process.
A priori, the deposition of chromium alloys would not seem too difficult,
since chromium can be deposited alone from two types of baths, the trivalent
bath and the chromic acid bath ; and the metals with which it is most frequently
alloyediron, nickel, and cobaltcan be readily deposited individually.
Furthermore, chromium forms solid solutions with these metals and, therefore,
the alloys should be depositable at a potential more noble (more positive) than
that of chromium deposited alone. However, as the discussion in Section 7.6*
showed, a close relation between the crystal structures and the lattice parameters
of two metals alone is not adequate to ensure successful codeposition.
The difficulty in depositing chromium alloys from the trivalent bath is mainly
chemical, rather than electrochemical. It is probably related to the ease with
which basic chromium salts precipitate in the cathode diffusion layer. Since
chromium deposits with a rather low cathode current efficiency, the pH of the
cathode diffusion layer increases on electrolysis and causes precipitation of
basic compounds. The inclusion of the latter in the deposits causes them to be
powdery, stressed, or exfoliated.
The low efficiency of chromium deposition from the trivalent bath is attributable to the negative (unnoble) potential of chromium with respect to hydrogen:
3

Cr + + 3e -> Cr

E = - 0 . 7 4

Measures aimed at preventing the above-mentioned precipitation of basic corncomplex poundsmeasures, such as increasing the acidity of the bath or forming
complex chromium ionsstill further lower the efficiency of chromium
deposition or may prevent the deposition entirely. Thus, we have the dilemma
that those conditions which should lead to a better quality of deposit are inimical
to the current efficiency.
* See V o l u m e I of this treatise for Chapters 1 to 2 1 .

no-