Microcracks in Hard Chromium Electrodeposits

By A.R. Jones

Microcracking in thick chromium deposits varies over a chromium or chromic oxide. Figure 2 shows an etched
broad range depending on plating bath composition. cross section of a microcracked chromium deposit. The
Observations during electroplating indicated that formation of microcracks and how they are affected by the
microcracking occurred periodically with copious plating conditions are discussed in this paper, which also
evolution of hydrogen gas. A correlation between examines the correlation of the number of microcracks with
microcrack density and microhardness was established, the brightness and hardness of the deposits.
but no correlation was found between microcrack density
and appearance, using data derived from four different Microcrack Formation
baths. The formation of microcracks was observed and recorded
by videotaping during electrodeposition at 48 A/dm2 in a
conventional chromium plating solution at 55° C containing
ard chromium is a term used to describe chro- 250 g/L of chromic acid and 2.5 g/L of sulfuric acid.

H mium electrodeposits thicker than about 2.5 µm

(0.1 roil). In this paper, the term microcrack refers
to a crack that does not extend from the basis
metal to the surface of the deposit; the term “micro” does
not imply a high crack count. A macrocrack extends
Observations commenced 30 min after plating was started.
The sample was a l-cm rod located approximately 1 mm
from the side of a 1-L beaker. The plated area was 0.4 cm
wide and 1.0 cm high. A magnetic stirrer was turned off
during recording to eliminate vibrations. A projection
throughout the entire thickness of the chromium deposit, microscope! with a magnification of 100 was focused on an
from the substrate to the surface. area at the bottom of the sample to reduce interference
Microcracks are networks of cracks visible with the aid of from hydrogen bubbles. An image of the plated surface on
magnification, after development, and are desirable in hard the projection microscope screen was videotaped and the
chromium deposits. Microcracks form during deposition tape was then observed on a 62-cm (25-in.) television
when the tensile stress exceeds the cohesive strength of the screen, which provided a total magnification of 650. The
chromium. As chromium thickness increases, tensile stress area under observation was 1.2 percent of the total plated
increases until microracking occurs, which relieves stress area.
in the deposit. At a thickness of about 125 µm (5 mils) The plated surface was clearly visible, but there were
internal stress reaches a constant value. 1,2 Deposits free of some out-of-focus gas bubbles in the foreground. Although
microcracks are not as hard as microcracked chromium. gassing appeared to be uniform to the unaided eye,
Deposits thicker than about 10 µm (0.4 mil) electro- microscopic observations at 100X showed that gassing
deposited from a “crack-free” process tend to form occurred almost exclusively at surface discontinuities such
macrocracks, and may not be mechanically sound. as pits, microcracks and edges adjacent to (or under) the
The pattern of interconnecting microcracks in Fig. 1 has masking material. Very few bubbles occurred at smooth
about 900 cracks/cm (2200 cracks/in.). Before development
4
by reverse-current etching, the cracks are filled with Monoscopic Dynascope, Vision Engineering Inc., New Milford, CT.

62 PLATING AND SURFACE FINISHING

 surfaces. Copious amounts of hydrogen gas evolved from
microcracks. Although the microcracks were barely visible,
the gassing made them appear dark. Microcracks formed
rapidly and appeared to grow in length. As microcracks
were plated over, gassing became restricted to line
segments and then to single points.
The frequency and duration of microcracking episodes
are reported in Table 1. Nine episodes of microcracking
were observed during a 44-min plating period. Episode
cycles ranged from about 2.5 to 11 min and time intervals
between gassing up to about 10 min. However, the duration
of gassing periods was more consistent and much shorter,
lasting about 0.6 to 1.2 min. Periodic microcracking has
recently been detected by acoustic monitoring of chromium
plating. 3 Microcrack patterns traced onto transparent films
are shown in Figs. 3, 4 and 5. Each figure shows three
patterns, as designated in Table 1. Figure 6 is a composite
1
of all nine episodes. Although appearing to be continuous Fig. 3—Microcracks transferred from video tape; see Table 1, episodes 1 to 3.
on a macro scale, microcracking is discontinuous on a
microscopic scale.
The depth of microcracks can be estimated from the
gassing duration data in Table 1 and the etched cross
section in Fig. 1. Table 1 data indicating that gassing
persists for about 1 min while a microcrack is plated over
would correspond to a chromium thickness of about 0.33
µm (0.01 mil) at the deposition rate forth is sample. Figure 2
shows that microcracks range in depth from 5 to 10 µm (0.2
to 0.4 mil), however. The plating rate in a microcrack is
greater than on the surface, therefore the microcracks are
deeper than 0.33 µm. A shorter reverse etch will produce a
microcrack that is shallower than 5 to 10 µm.
The Fig. 6 composite obtained during a 44-min plating
period shows a density of 200 microcracks/cm by com-
parison with a pattern of 170 microcracks/cm for this plated
sample. These densities are considered to be statistically
equivalent. Thus the reverse-current etch used evidently
developed all of the microcracks formed during 44 min of
plating. About 15 µm (0.6 mil) of chromium was deposited
in 44 min of plating and about 10 µm (0.4 mil) was dissolved
during the development of the microcracks. Microcrack
patterns are imprinted downward as chromium is etched.
Fig. 4—Microcracks transferred from video tape; see Table 1, episodes 4 to 6.
Microcrack episode No. 7 covered the field of view in less
than 33 msec. Thus the microcrack pattern was fully
developed in this single video tape frame.

Fig. 5—Microcracks transferred from video tape; see Table 1, episodes 7 to 9.

APRIL 1989
63
 In any single video tape frame, the microcracks that containing catalyst in addition to sulfate ions. Seven
formed most recently were the most evident, but micro- samples were plated in each of the four solutions, using the
cracks from previous episodes were visible as lighter lines. sulfate concentrations, temperatures and current densities
When the plating current was momentarily turned off indicated in Table 2.
during episode No. 4, gassing stopped and the microcracks The substrate was a 1.O-cm rod of AISI 1085 steel with a
disappeared. When the current was turned on, the same surface finish of 0.4 µm, rms, and a sample area of 5.1 cm2.
microcracks started gassing. Brittain and Smith’ observed Before plating, samples were cleaned, rinsed in cold water
this same behavior when they interrupted the current for and reverse-current etched in chromic acid solution. Weight
several hours. gain by plating was used to calculate deposition efficiency.
Microcracks were developed by boiling the samples for 30
Bath Composition, Current Density min in water followed by anodic etching at 46 A/dm2 for 2
And Temperature Effects min in a 100 g/L sodium hydroxide solution at room
Microcracking in three proprietary baths was compared temperature.
with data obtained by plating in the conventional, non- Microcracks were counted at six different locations on
etching bath prepared with a single (sulfuric acid) catalyst. the surface of each sample; 10 measurements with a 100-g
The three proprietary solutions included a mixed-catalyst load were made with a Knoop indenter to determine
(etching) bath’ an etch-free solution with an efficiency of 25 microhardness. Appearance was classified as bright,
percent’ and an etch-free bath with an efficiency of 40 semi bright or frosty. A scale from 1 (dull) to 10 (bright) also
percent.” The mixed catalyst bath contained a fluoride- was adopted.
Table 2 shows that microcrack density ranged from less
b
HCR 840 chromium plating process, M&T Chemicals, Inc., Rahway, NJ. than 4 to about 3200 cracks/cm. Although the density
c
HEEF 25 chromium plating process. M&T Chemicals, Inc., Rahway, NJ.
d
HEEF 400 chromium plating process, M&T Chemicals, Inc., Rahway, NJ. cannot be determined with a high degree of precision, the

64 PLATING AND SURFACE FINISHING

Fig. 6—Composite of microcracks from Figs. 3105.

data indicate that deposits from the conventional bath have

the lowest number of cracks, whereas chromium deposited
in the solution giving an efficiency of 25 percentb had the
highest crack count—about twice as many as the deposits
from any other bath. Figure 7 shows that increasing the
sulfate concentration resulted in an increase in microcrack
density, especially for the mixed catalyst and 25-percent
baths.
Figure 8 shows the effects of changing the temperature
on the density of microcracks; Fig. 9 reports the results of
increasing the current density. The microcrack density in
deposits from the conventional bath increased from less
than 4 to 300 microcracks/cm as the current density Fig. 7—Microcrack density as a function of sulfate concentration; al
deposits are identified in Table 2.
increased from 8 to 16 A/dm2 .

Fig. 8—Microcrack density as a function of bath temperature; deposits are

identified in Table 2.

APRIL 1989
 Corrosion and Post Finishing
Microcracks are filled in and are not voids. The corrosion
protection provided by deposits with a thickness of more
than about 25 µm (1.0 mil) does not change when
microcrack density ranges from 100 to 800/cm (250 to
2000/in.). However, if microcrack density is too low,
macrocracks may expose the basis metal.
Finishing processes such as machining and lapping
increase the microcrack density by a factor of two to three.
The number of cracks/cm before and after finishing typical
deposits increased as follows: 390 to 910; 630 to 1700; 710
to 1700; 750 to 1500; 790 to 1300 and 870 to 2100. Finishing
or baking electrodeposited chromium either increases the
number of microcracks or makes them more detectable.

Fig. 10— Microhardness as a function of microcrack density; deposits from

Conclusions
conventional bath shown by solid circles; squares show deposits from the
mixed catalyst bath; triangles designate deposits from the 25 percent bath From microcracks that form rapidly during plating,
and hexagonals show deposits from the 40 percent bath. hydrogen gas is evolved until the cracks are sealed with
more chromium. Microcrack density varies from less than 4
to 3,200/cm depending on the composition of the bath. An
increase in the sulfate concentration increased microcrack
density in each of four baths studied. Temperature and
current density changes in some baths had some influence
Microcrack Density, on the microcrack density. Microhardness of the deposits
Microhardness and Appearance increased as the microcrack density increased.
The data in Fig. 10 shows a general trend of increasing
microhardness with an increasing microcrack density.
However, the increases in both microhardness and micro- References
crack density relate to the chemistry of the solutions. 1 J.E. Stareck, E.J. Seyb and A.C. Tulumello, P/sting, 41,
Chromium deposited in the conventional bath was relatively 1171 (1954).
low in both microcrack count and microhardness, whereas 2 A. Brenner, P. Burkhead and C. Jennings, J. Res. Nat/.
deposits from the 25-percent bath were high in both cases. Bur. Standards, 40,31 (1948).
The scatter of points in Fig. 11 indicates that there was no 3 M.T. Todaro, G.P. Caosimales and E.S. Chen, Report
correlation between microcrack density and brightness. Number AR CC B-T R-87007, U.S. Army Armament
Deposits from the mixed catalyst bath appeared con- Research, Development & Engineering Center, Benet
sistently bright, whereas chromium deposited in the con- Weapons Laboratory, Watervliet, NY (Mar. 1987).
ventional and 40-percent baths had varied in appearance 4 C.P. Brittain and G.C. Smith, Trans. Inst. Metal Finishing,
depending upon plating conditions. 33, 289 (1 956).

About the Author

Dr. Allen R. Jones, CEF, is a senior research chemist and group
leader in the plating division of M&T Chemicals, P.O. Box 1104,
Rahway, NJ 07065. His research interests are high efficiency and
improved performance of hard chromium electrodeposits, as
well as tribology and corrosion of advanced coatings. Dr. Jones
earned his PhD degree in physical chemistry at Rensselaer
Polytechnic Institute and his BA in chemistry at Linfield College.
Fig. 11 —Data points for brightness and microcrack density; symbols are He is a member of the AESF Garden State Branch, the
described in the Fig. 10 caption. Electrochemical Society, and the American Chemical Society.
66 PLATING AND SURFACE FINISHING