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Temperature effect on crack density and crystalline phase of electrodeposited

chromium

Article in OPTOELECTRONICS AND ADVANCED MATERIALS-RAPID COMMUNICATIONS · January 2016

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OPTOELECTRONICS AND ADVANCED MATERIALS – RAPID COMMUNICATIONS Vol. 10, Iss. 1 - 2, January - February 2016, p. 123 - 126

Temperature effect on crack density and crystalline phase

of electrodeposited chromium
JUN-GANG ZHENGa, XU-DONG ZUOb, CHENG-WEI WUb, WEI ZHANGb,*
a
School of Science, Shenyang Jianzhu University, Shenyang 110168, China
b
State Key Laboratory of Structural Analysis for Industrial Equipment, Department of Engineering Mechanics, Dalian
University of Technology, Dalian 116024, China

o
Homogeneous, crystallized and crack-free chromium (Cr) coating was electrodeposited on stainless steel at 85 C with a
2
current density of 80 A/dm , evidenced by the surface and cross section metallographs of the coating. X-ray diffraction
analyses indicate the coating is largely composed of body centred cubic -Cr. The effect of temperature on the generation of
cracks, surface hardness and cathodic current efficiency were also investigated. The reduction in crack density with
increasing temperature may be interpreted in terms of the decreasing inhibition of lateral grain growth.

(Received October 21, 2013; accepted February 10, 2016)

Keywords: Electro deposition, Chromium, Crack, Metallograph, Grain growth

1. Introduction chromic anhydride solution can also contribute to the

reduction of crack density [8]. However, in these cases, the
Hard chromium (Cr) deposition is widely used as a deposits are mainly composed of amorphous Cr which
surface modification method to improve the hardness, usually possess lower hardness than crystallized chromium
wear resistance, erosion resistance and shiny appearance and are not suitable as an inner layer to enhance corrosion
of engineering tools and components such as internal resistance [9,10]. Clearly, a technique that can be used to
combustion engine components, hydraulic cylinders, rolls prepare crack-free and crystallized Cr deposits is still
and surgical tools. These modifications can find their highly desirable. In recent years, many studies have shown
applications in modern industry including automotive, that the temperature of electro deposition could influence
aerospace, mining and petrochemistry etc. [1-4]. Quite the structure and composition of the deposits in a large
often, if not always, the Cr deposits contain macro and/or extent [11-13]. As such, in this paper, we investigated the
micro cracks. The presence of these defects may decrease effects of deposition temperature on the deposited Cr, and
internal stresses and thereby the brittleness, however, as by optimizing the deposition temperature, the crystalline
the initiator of the propagation of further cracks and severe phase Cr with low crack density could be successfully
corrosion, their emergence may compromise the obtained. It is likely that this will enrich our understanding
mechanical and corrosion resistance of deposits. No need on the mechanism of generation of cracks and crystallized
to emphasize more that, in many aspects, it will offer Cr, which may lead to the design and manufacture of Cr
benefits if the crack density in deposits can be reduced deposits with improved service performance.
effectively. As such, many approaches have been
developed.
The most common method is the utilization of a duplex 2. Experimental
system, where a plate of bright crack-free Cr is first
deposited, and following this, an ordinary cracked or Cr coatings were electrochemically deposited from
micro-cracked Cr deposition is carried out. But in practice, hexavalent Cr bath consisting of 250 g/L CrO3 and 2.5 g/L
it is not easy to produce this system consistently [2,5]. H2SO4. Analytical grade chemicals and distilled water
Another way to reduce crack density is the application of were used to prepare the solution. The coatings were
pulse current. During reverse period in pulse current, stress deposited on polished and electro-cleaned substrate of
relief and/or anodic reaction takes place on the sample AISI 304 stainless steel. The electro deposition was
surface, resulting in less hydrogen adsorption and hence performed at a current density of 80 A/dm2 for 1 h with the
less chromium hydride formation, which are thought to be stainless steel acting as the cathode and lead being the
the possible initiators of internal stress. Nonetheless, the anode.
deposits obtained by this method usually have less hardness Metallurgical observations were carried out on a
and poor wear resistance [6, 7]. The addition of organic LEICA MEF4A Metallurgical Microscope. X-ray
additives containing carboxylic or aldehyde groups into diffraction pattern was recorded on an XRD-6000X
124 Jun-gang Zheng, Xu-Dong Zuo, Cheng-Wei Wu, Wei Zhang

(Shimadzu Corporation, Japan). Micro Vicker hardness of small fraction of face centred cubic-Cr. The emergence
was measured on the surface with a load of 50 g and dwell of Cr2H (101) and (110) reflections at 42.9 o and 67.8 o
time of 15 s on an HXD-1000TM Microscopic Hardness respectively is indicative of the presence of hexagonal
Meter (Shanghai Taiming Optical Instrument Co., China). Cr2H. By sharp contrast, XRD profiles of coatings obtained
Current efficiency was evaluated on the mass variation of at 55 oC and 70 oC resemble the characteristics of
stainless steel before and after deposition. amorphous Cr. The results above reveal that the coating
changes from amorphous phase to -Cr one when the
temperature is increased from 55 oC to 85 oC.
3. Results and discussion

To examine the effect of temperature on the

deposition of Cr, electro depositions were conducted at 55
o
C, 60 oC, 65 oC, 70 oC, 75 oC and 85 oC using Sargent
solution, i.e. using chromic acid as Cr source. When
temperature is lower than 70 oC, bluish silver Cr coatings
with higher density of cracks was obtained, as evidenced
by the metallographs (Fig. 1 d, e and f). While grey Cr
coatings with marginal cracks were obtained if the
deposition temperature is over 70 oC, see Fig. 1a and b. It
is clear that the increase of deposition temperature yields a
considerable reduction in the crack density of coating.
Cross section observations (Fig. 1 g and h) reveal a
homogeneous coating with the thickness of a few tens of
microns was deposited on stainless steel, demonstrating
reasonable throwing power.

Fig. 2. XRD patterns of Cr coatings deposited at

different temperatures

The rationale for the generation of crack is still a topic

open for discussion. Snavely [14] argued that the
successive deposition of hexagonal Cr hybrids and their
decomposition to b.c.c. Cr and hydrogen cause the
shrinkage in volume, yielding stress and subsequently
cracks in coating. In Nielsen’s view [15], a possible source
of residual tensile stresses in electrodeposits can be
understood as a result of grains accommodating boundary
misfit at grain coalescence. The higher the inhibition of
lateral grain growth, the higher the nucleation rate and so
the higher number of grains that coalesce thereby leading to
higher residual tensile stresses. It seems not impossible, but
Fig. 1. Metallographs of surfaces of coatings deposited quite unlikely, that the phase transformation can be
at 85℃(a), 75℃(b), 70℃(c), 65℃(d), 60℃(e), 55℃(f), provoked to account for the drop of crack density at higher
and cross section of coatings deposited at 85 oC (g) and temperature. As for the cracked coatings, i.e. deposited at
55oC (h). lower temperatures, the expected b.c.c. Cr which usually
possesses low porosity and could form a protective surface
coating and slower the corrosion rate of the substrate
To study the underlying mechanism, X-ray diffraction [16,17] is virtually not the prevailing phase, instead
patterns of coating were recorded and are depicted in Fig. 2. amorphous Cr governs. This implies that the phase
For the coating obtained at 85 oC, the strong peaks at 44.3 o, transformation may not be the main cause for the
64.6 o, 81.7 o and 98.0o are distinguishable, which can be generation of cracks here. The drop of crack density with
ascribed to the -Cr (110), (200), (211) and (220) increasing temperature may be explained using Nielsen’s
reflections, respectively, suggesting that the coating is theory. At high temperatures, the inhibition of lateral grain
mainly composed of body centred cubic (b.c.c.) -Cr. In growth decreases and the residual tensile stresses are not
addition, weak peaks at 43.6 o, 50.9 o and 74.4 o are high enough to initiate the generation of cracks, but this
identifiable, which may stem from the reflections of -Cr needs further investigation.
(111), (200) and (220) respectively, implying the presence
 Temperature effect on crack density and crystalline phase of electrodeposited chromium 125

The hardness of coating is another concern pertaining Apparently, at the present current density, cathodic
to engineering applications, since hardness is directly current efficiency decreases substantially when temperature
related with the wear resistance property. A coating with is increased from 55 oC to 75 oC and then diminishes
high hardness is more difficult to deform under high loads, slowly, which may be explained using the deposition theory
giving rise to a delay in plastic deformation [18]. The of Cr, i.e. the alternate formation and dissolution of
surface hardness of coatings is plotted in Fig. 3, wherein it cathodic colloidal membrane Cr(OH)3·Cr(OH)CrO4 [19].
can be observed that the hardness value varies marginally
when temperature was increased from 55 oC to 65 oC, but
decreases precipitously with further increase of 4. Conclusions
temperature. A combination of these results enables one to
propose that it is not easy to obtain a crack-free Cr coating A simple and economic method is described for the
without sacrificing the hardness property. electro deposition of homogeneous, crack-free and b.c.c.
-Cr coatings from a bath containing chromic acid and
sulfuric acid with a current density of 80 A/dm2 at high
temperatures (> 70 oC). By contrast, electro depositions
conducted at low temperature (from 55 oC to 70 oC) yield
cracked amorphous Cr coatings. But it needs to be
mentioned that this reduction of crack density is
accomplished at the sacrifice of surface hardness and
cathodic current efficiency by up to 370 HV 0.05 and 8%,
respectively.

Acknowledgements

The National Natural Science Foundation of China

(51105051), the Scientific Research Foundation for the
Fig. 3. Surface hardness of coatings deposited at different Returned Overseas Chinese Scholars and the Fundamental
temperatures Research Funds for the Central Universities of China
(DUT11RC(3)79) were acknowledged for the financial
For economic and ecological considerations, the support.
cathodic current efficiency () is calculated using Eq. 1 and
shown in Fig. 4.
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______________________
*
Corresponding author: wei.zhang@dlut.edu.cn

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