ElECTRODEPOSITION OF CHROMIUM-NICKEL-IRON AllOY solution

burning
COATINGS FROM NON-TOXIC ELECTROLYTES been pre

N. V. Shanmugam a and S. John b A proces

giL of 0
Central Electorchemical Research Institute, Karaidudi 630 006, India. giL of bc
a) nvshartmuqam@cecri.res.in b) sjohnimf@cecri.res.in claimed I
by heat t
ABSTRACT
Typical il
Maximum corrosion resistance among iron group alloys has been observed for 50Ni50Fe chloride
and 70C030Ni binary alloys depending upon deposit composition and microstructure, which around a
are controlled by solution composition and deposition variables. Renewed interest has
been shown on the development of environment-friendly electroplating baths enabling The mec
one to apply chromium-nickel coatings. those of J
of thin ar
Chromium-nickel-iron alloy plating from non-toxic acetate based trivalent electrolyte, has [17J, 'Rec
been examined under different Hull cell current values. The resulting deposits were been rep
examined for their elemental content, micro hardness and their surface topography with alloys WE
5EM. This alloy contains chromium 3%, nickel 65% and iron being 32%. these Fe­
in this ca
KEYWORDS: Alloy electrodeposition, Cr-Ni-Fe This phe
plating cc
INTRODUCT10N
Alloys co,
Chromium-nickel-iron alloy electrode posits have gained great importance [1-4J in recent solutions
years as they provide an economical substitute for stainless steel without prejudice to the current e:
functional advantages. The Fe-Ni-Cr samples electrodeposited using a chloride bath along temperat
with DMF [5,6J, resulted in deposits with an average composition of 25% Crt 25% Ni and described
50% Fe. Electrodeposited iron alloy film (8-10% Ni and 17-19% Cr) corresponding to [25] .
55303 stainless steel from a bath containing chromium sulfamate, nickel sulfamate and
ferrous sulfamate in a specified molar ratio 'has been claimed by a Japanese patent [7]. EXPERIM

Alloys containing 20 % iron in addition to chromium are produced by co-depositing The pater
chromium carbide from a nickel-iron based solution and heat treating in hydrogen to for using Hull
nickel-iron-chromium alloys. Hardness after heat treatment is 215 HV. Approximately at temper,
0.8% C remains in the nickel iron-chromium alloy, which may account for its higher
hardness of 332 HV.[8J To study tI
size 25 xl
Inconel 600 is a standard engineering alloy for use in severely corrosive environments at 60mA/cm"
elevated temperatures [9]. It is a Ni-Cr-Fe alloy containing 15,5% Crt and 8% Fe. Further, of 50 g w­
an American patent [10] discloses an aqueous plating solution containing a trivalent HMV, Japa
chromium salt, formic and I or acetic acid salt, a bromide, borate and ammonium ions.
The advantages of the trivalent chromium processes over the hexavalent chromium process The topogl
are fewer ~nvironmental concerns due to the lower toxicity of trivalent chromium, higher were also'
productivity, and lower operating costs. Use of trivalent chromium also reduces waste Scanning
disposal problems and costs.
Surface c
Despite frequent claims to the contrary, especially in the patent literature, all these attempts and Horib
have proved unacceptable in commercial practice. A commercially acceptable plating

Vol 3, Issue 3 - 4 368 July - December 2006 Vol 3, Issu

 solution must provide a more or less even deposit over the whole work piece. To overcome
LLOY
burning at high current density areas and inability to plate into recessed areas, it has
been proposed to form complexes.

A process and bath for electroplating Ni-Cr alloys from an electrolyte containing 50-125
g/L of Chromium chloride, 10-125 g/L of nickel chloride, 10-115 g/L of formic acid, 25-50
g/L of boric acid; and 50-100 g/L of sodium citrate at pH of 1-5 and at 20- 60°C has been
claimed by Lashmore [ 13, 14]. Co-deposition of Cr particles during Fe-Ni plating, followed
by heat treatment, is mentioned.

Typical iron group alloy plating solutions are operated using sulfate or mixed sulfate­
SONi50Fe chloride baths containing stress reducing and grain refining agents, at room temperature
lre, which around a pH of 3 [15].
erest has
; enabling The mechanical properties of electroformed Ni-Fe microstructures [16], are superior to
those of microstructures formed by casting or powder metallurgy. The potential properties
of thin and thick deposits of nickel-chromium-iron alloys are discussed by Sitnikova et.al
'olyte, has [17]. Recently, residual stresses in electrodeposits of nickel and nickel-iron alloys have
lsits were been reported by Hadian and Gabe [18]. Structure-property relationships of iron group
'aphy with alloys were studied in detail by Myung and his team [19-22]. The electrodeposition of
these Fe-Ni alloys is characterized by so called anomalous behavior; the less noble metal,
in this case iron, deposits more readily out of the plating bath than the more noble nickel.
This phenomenon is not yet fully understood and requires a more rigid control of the
plating conditions [23].

Alloys containing 20-40% Cr, balance Fe were deposited at 100-300 mA/cm 2 in formate
I] in recent solutions containing chromium chloride, ferrous chloride, glycine and boric acid with a
dice to the current efficiency of 55-65%, that is kept at a pH of 2.8. The influence of current density
bath along temperature and pH on the composition and characteristics of the alloy deposits is
!S% Ni and described [24]. Effect of aluminum chloride in chloride bats has been studied by Domnikov
ponding to [25] .
amate and
patent [7]. EXPERIMENTAL PROCEDURE

depositing The potential properties of thin deposits of nickel-chromium-iron alloys are discussed
gen to for using Hull cell studies. The operating parameters were studied clt 1,2 & 5 A for 5 minutes
roximately at temperature of 50°C and Hull cell patterns were recorded.
its higher
To study the hard~ess of the alloy deposits, coatings were prepared on copper panels of
size 25 x 100 x 3mm 3 after proper pretreatment. The hardness of alloy plated at a CD of
nments at GOmA/cm" for a period of 60 minutes on copper substrates (20-25 pm thick) under a load
e, Further, of 50 g was measured, using a conventional Vickers micro hardness tester SHIMADZU
trivalent HMV, Japan and an average of three readings was taken from this experimental test.
nium ions.
m process The topography of samples plated from the electrolytes used for hardness measurements,
m, higher were also examined for their secondary electron image at 1000x using HITACHI 3000H,
ces waste Scanning Electron Microscope.

Surface composition was studied using X-ray analytical microscope, XGT 2700 model,
attempts and Horiba make, Japan. The surface composition of various elements present in the
ble plating

Vol. 3. Issue 3 - 4 369 July - December 2006

 LEGENDS FOR RECORDING HULL CELL PATIERNS

• •
pitted black black

m
chocklate
II
chocklate brown

Streaky satin semi bright •II

blistered

•0
powdery grayeish white
EJill
b1uiesh white

II
grayeish black

II
no coating grayeish blue pitted gray

W
----
bluish yellow
~
bright yellowish • •
bright blueish yellowish brown

1A

2A

SA

Fig. 1 : Appearance of Hull cel panels obtained at different cell currents

for 5 minutes from solution containing ickel acetate 10 giL,
Chrominum acetate, 24 giL, Ferrous ammonium sulfate, 80 giL, Boric
acid, 30 giL, Ascorbic acid, 60 giL, Temperature 50'C

Fig. 2: II
obtaine
alloy deposits, obtained from these electrolytes are examined and the results are recorded.
Nickel
RESULTS AND DISCUSSION
24 giL, ferrol
Fig 1. Shows the appearances Cr-Ni-Fe deposits obtained over Hull cell panels plated at temperature ~
different cell curr-::nts of 1,2 & SA for S minutes from Cr-Ni-Fe plating solution having
higher iron salt along with ascorbic acid containing nickel acetate 10 giL, chromium acetate 1 A Hull cell pc
values namel)
Vol. 3, Issue 3 - 4 370 July - December 2006
Vol. 3, Issue 3 ­
 pitted black
II
chocklate
II
chocklate brown

Streaky satin
m
semi bright blistered

•D
powdery grayeilh white
llilliill
bluiesh white

II
fII
grayeish black

II
no coating pitted gray

~ ------
-_. ---­--
bluish yellow
mJ
bright yellowish bright blueish •
yellowish brown

A
=;
~5A
~:., 1 1 : = 1 2. HCl4n1

SA
HC18m1

I currents
gIL,
IL, Boric

Fig. 2 : Influence of Hydrochloric acid on the appearance of Hull cell panels

obtained at different cell currents for 5 minutes from solution containing
are recorded. Nickel acetate, 10 g/I, Chromium acetate, 24 g/I, Ferrous ammonium

24 giL, ferrous ammonium sulfate, 80 giL, boric aCid 30 giL, ascorbic acid 60 giL,
nels plated at temperature 50°C.
lution having
mium acetate 1A Hull cell panels indicate that bright Cr-Ni-Fe alloy deposit could be obtained at low CD
values namely 0-4 mA/cm 2 region. Yellowish bright coatings are obtained between 4-15

Vol. 3, Issue 3 - 4 371 July - December 2006

atings

at low
1 a CO
A/em'.
)atings

low CD
;n a CD
2en ~O­
75 mAl
sh blue
btained Fig. 3 : Secondary electron image of Cr-Ni-Fe deposit at 1000 x plated at a CD
of 60mA/cm2 for 15 minutes, from Acetate based Nickel - Chromium - Iron
bath containing Nickel acetate 12 gIl, Chromium acetate 100 gIL, Ferrous
currents ammonium sulfate 12g/l, Boric acid 30g/l, Ascorbic acid 60g/l, at50'C
acetate
60 gil,

mA/cm 2
:hocolate
(ellowish
~ coatings
nd above

~amely 0­
Fig. 4 : Effect of chloride addition 0 the Secondary electron image of Cr-Ni-Fe
11 2. Bright
deposit at 1000 X, plated for 15 minutes duration at a CD of 60 mA/cm2, from
solution containing Nickel acetate 10 gIl, Chromium acetate 24 gIl, Ferrus
ish brown
atings are
ammounium sulfate, 80 gIl, Boric acid 30 gIl, Ascorbic acid 60 gIl,
lbove 150
Hydrochloric acid 4, 8& 12 mill respectively, at 50<

Effect of Hel addition - 12 mill at 3A cell current

3A Hull cell panel indicate that bright Cr-Ni-Fe alloy deposit could be obtained at low CD
lamely 0­ values namely 0-75 mA/cm2 region. Streaky and satin like deposits are obtained between
Blistered a CD range of 75-120 mA/cm2. Grayish blue coatings are obtained at and above 120 mAl
ish brown cm i .
; coatings
md above STUDIES ON HARDNESS

The hardness of tile deposits from acetate and acetate-chloride electrolyte electrolytes
are shown in Table 1, and 2 respectively.

~mber 2006 Vol. 3, Issue 3 - 4 373 July - December 2006

 Table 1- The elemental analysis and hardness of the deposits obtained from toxic tri aler
acetate based electrolytes at different CD values plated for 5 minutes. The resultinl
Thick depos
Acetate bath Current Den~ity, 0/0of element Hardness the micro he
mA/cm 2 in deposits Kg/mm 2
Based on thi
Cr Ni Fe VHNsog of hydro chi
60 1.75 66.08 32.17 Not measurable and other 51
65% and iro
12 1.64 65.17 33.19
300 3.92 69 27.08 IBIUOGfUI

Table 2 : The effect of chloride addition on hardness of the deposits from acetate­ 1. S.Gow
chloride electrolytes at a Current Density of 60 mA/cm2 plated for 5 minutes 2. W. Mact
3. L.A. Zyt
Acetate bath Current Density, 0/0of element Hardness 4. L. Szira'
+HCI mA/cm 2 in deposits Kg/mm2
Electroc
Cr Ni Fe VHNsog 5. M. EI-SI
6. M. EI-SI
4mljL 300 3.09 65.77 31.14 183 7. Ishiguro
8mljL 300 3.21 65.53 31.26
8. S.Alec \
www.pf<
12mL/L 300 3.2 65.5 31.3 9. http://w
12mL/L 180 3.19 65.82 30.99 10. Gyllens~
11. Bride J.E
12. J. C. Sail
STUDIES ON TOPOGRAPHY USING SEM 13. Lashmor
14. ASM Har
The topography of samples plated for hardness measurements, were examined for their 15. A.Brenne
secondary electron image (sei) at 1000X using Hitachi 3000H, Scanning Electron Microscope, New Yorl
Canada and are shown in Fig 3 -4 respectively, 16. J.T.Ravnl
electropl
Acetate based nickel - chromium - iron bath produced fine grained deposits as shown in 17. Sitnikova
Fig 3 whereas the addition of chloride resulted in fine grained deposits with agglomeration 18. S. E. Hac
of grains as seen in Fig 4, probably owing to the increased iron content of 22%. 118-135
19. N. V. My
STUDIES ON ELEMENTAL ANALYSIS OF SURFACE COMPOSmON 20. D. Kim.
819-830,
The surface composition of various elements present in the alloy deposits, obtained from 21. N.V.My
XRF analysis produced in various electrolyte are shown in Table 1-2. 22. K. M Yin,
23. Metal Fin
The percentage of chromium remains around 1-2% for acetate based solutions under Science
study, whereas the addition of chloride resulted in an slightly increased value of 3%. 24. T. Haya
Similarly the iron content in the deposit gets increased from 10-20% to 31 % at a CD Sept. 19
values of 300 mA/cm 2 • The percentage content of Ni & Fe do not show any regular trend 25. Larissa D
with CD values.

CONa.usrON

Chromium - nickel - iron alloy plating bath has been examined for the production of alloy
deposit and their operating condition under different Hull cell current values from a non-

Vol. 3. Issue 3 - 4 374 July - December 2006 Vol. 3, Issue 3­

 toxic trivalent electrolyte from acetate based electrolytes and with the addition of chloride.
I from The resulting deposits were examined for their elemental content from these electrolytes.
:es. Thick deposits were produced when plated at a cathode CD of 60 mA/cm 2 for 60 minutes:
the micro hardness and their surface topography were analyzed with SEM.

Based on the above experimental results, a mixed acetate electrolyte with little addition
of hydro chloric acid was formulated and their operating characteristics ar'tJ hardness
and other surface properties were reported. This alloy contains chromium 3%, nickel
Jrable
65% and iron being 32% and exhibit a hardness value of 183 VHN SOg

BIBIUOGRAPHY

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ction of alloy
from a non­
Vol 3, Issue 3 - 4 375 July - December 2006
ecember 2006