Thin Solid Films, 127 (1985) 181-189

ELECTRONICS AND OPTICS 181

E L E C T R O D E P O S I T I O N O F B L A C K C H R O M E S E L E C T I V E SOLAR
ABSORBER COATINGS WITH IMPROVED THERMAL STABILITY*

KARTIK SHANKERt AND PAUL H. HOLLOWAY

Department o f Materials Science and Eng&eering, University of Florida, Gainesville, FL 32611 (U.S.A.)
(Received April 20, 1983; accepted September 7, 1984)

Auger electron spectroscopy was used to study the oxidation behavior of

electrodeposited black chrome selective solar absorber films. The volume fraction of
C r 2 0 3 increased rapidly initially, and the films then exhibited an increasingly slower
rate of oxidation. The C r 2 0 3 formed during electrodeposition does not passivate the
film; it is only the C r 2 0 3 formed during the initial thermal exposure that forms a
passivating layer. Thus the optical properties of the as-deposited films change
rapidly with heating. The deposition of larger agglomerates results in better thermal
~tability of the optical properties.

1. INTRODUCTION

Eiectrodeposited black chrome selective solar absorbers are used in both low
temperature fiat plate and medium temperature concentrating collectors. Although
they are stable in low temperature systems, their optical properties undergo
significant changes on thermal aging in air at temperatures above 250°C1
Undesirable degradation of optical properties has also been observed in solar
thermal conversion demonstration projects at numerous locations.
Black chrome coatings consist principally of metallic chromium particles,
C r 2 0 3 and voids 2-11. The values of their optical properties, i.e. solar absorptance
and thermal emittance, are related to the amount of Cr203 in the films. They are also
related to the morphology of these films 11,12.
In this paper the oxidation behavior of electrodeposited black chrome (from
a C h r o m O n y x 13 type of bath) on thermal aging in air at 395 and 460 °C is dis-
cussed. The oxidation varies logarithmically with time, similar to the behavior of
mechanically roughened pure (bulk) chromium.

* Paper presented at the International Conference on Metallurgical Coatings, San Diego, CA, U.S.A.,
April 18-22, 1983.
t Present address: Department of Physics, University of Guelph, Guelph, Ontario N 1G 2W1, Canada.

0040-6090/85/$3.30 © ElsevierSequoia/Printed in The Netherlands

182 K. SHANKER, P. H. H O L L O W A Y

2. EXPERIMENTAL P R O C E D U R E

Nickel-plated plain carbon steel substrates were electroplated with black

chrome films from a C h r o m O n y x 13 type of bath maintained at a temperature of
20 26 °C. The bath composition, current density and deposition time were varied;
the deposition conditions for the films discussed in this paper are listed in Table I.
The details of the plating procedure have been explained elsewhere11,14,15. Thermal
aging tests were conducted in an open tube furnace at 395 and 460 °C ( + 10 °C).

TABLE I
ELECTRODEPOSITION CONDITIONS FOR THE BLACK CHROME FILMS

Sample Bath composition Current Time

density (min)
[ C r 3 +] [ F e 3 +] [ C r O a] Additional agent (mA cm - 2)
(gl 1) (gl 1) (gl x) (vol.~o)

A 6.2 0.36 181.1 25.3 178.6 8

B 5.2 3.57 287.7 28.2 183.7 5
C 8.5 6.92 306.2 26.8 183.7 5

Auger electron spectroscopy (AES) was accomplished with a Perkin-Elmer

thin film analyzer using a primary electron beam of energy of 3 keV and modulation
voltage of 5 eV peak to peak and a beam current of 301aA. Depth profiles were
obtained by simultaneous sputtering with 2 keV Ar ÷ ions using a P e r k i n - E l m e r ion
gun. The residual pressure was less than 5 × 1 0 - S T o r r during analysis. During
sputtering, the system was backfilled with pure argon to a pressure of 4 × 10-5 Torr.

3. RESULTS

The deposition conditions listed in Table I are for the films that are discussed in
this paper. However, they are representative of a group of samples deposited over a
large range of "deposition conditions 'ql. AES depth profiles for films A and B
(Table I) in the as-deposited and thermally treated conditions are plotted in Figs.1
and 2 respectively. The changes in AES peak-to-peak height for chromium, oxygen
and nickel as a function of the sputtering time are shown. (The sputtering rate was
not calibrated on these films. It was determined to be about 80/~, min-1 on pure
C r 2 0 3 films 11.) The chlorine Auger sputter profile is also plotted for film A; chlorine
was also observed in film C in the as-deposited state, but even 1 h at 460°C
eliminated it from these films 11. The chlorine present is believed to result from
adsorption during the cleaning after deposition; data discussed elsewhere ~1 show
that it had no effect on the optical properties or their stability when present in this
form. The other impurities found by AES were carbon and, occasionally, sulfur. Both
were detected only on the surface and a few minutes of sputtering removed them.
The volume fraction o f C r 2 0 3 in the black chrome films was calculated from the
AES depth profiles using a method described elsewhere 2'11. Briefly, this involved
measuring the areas under the chromium and oxygen profiles and then calculating
ELECTRODEPOSITION OF BLACK C r SOLAR COATINGS 183

NI

e-

e.

a
0

\
< \

"" ~. CI

20 40 60
(a) Sputtering time (min)

Y:
~0

t~

O
_ f / / - ~ "/'~""X~"x-N.X.
/ "~
/ \N
r,
<

~I ~-

Cr
I I 1 I I I I
0 40 80 120
(b) Sputtering time (min)
Fig. 1. Auger peak-to-peak height as a function of the sputtering time for black chrome film A (a) in the
as-deposited condition and (b) after thermal aging for 45 h at 460 °C.

the volume fraction of the (solid) film that is C r 2 0 3 . The assumptions, implicit and
explicit to this procedure, have been discussed 2' 11. Some of the calculated C r z O a
contents are listed in Table II. Included for c o m p a r i s o n in this table are data on
184 K. SHANKER, P. H. HOLLOWAY

NI

"z
\

k
\
e~ \
\\
,<

\
N
\\
'~_Cr
\.%
I I I I I I
40 80 120

(a) Sputtering time (min)

6
"7 /,/^,,,I ~"~.,.

I
.<

~x
-\J~c,
0 40 80 120
(b) Sputtering time (rain)
Fig. 2. Auger peak-to-peak height as a function of the sputtering time of black chrome film B (a) in the as.
deposited condition and (b) after thermal aging at 460 °C for 4 h.
ELECTRODEPOSITION OF BLACK Cr SOLAR COATINGS 185

TABLE II
VOLUMEFRACTIONOF CI'20 3 IN BLACKCHROMEFILMSAS A FUNCTIONOF THERMALAGINGIN AIR

Sample Thermal exposure Volume fraction

Cr203

A As deposited 0.50
45 h at 460 °C 0.94
240h at 395 °C 0.91
B As deposited 0.53
1 h at 460 °C 0.87
4h at 460 °C 0.91
50 h at 460 °C 0.92
67 h at 460 °C 0.96
C As deposited 0.33
4 h at 460 °C 0.65
50h at 460 °C 0.79
Da As deposited 0.40
136 h at 400 °C 0.77
3682 h at 400 °C 0.84
Eb As deposited 0.30
136h at 400 °C 0.64
3682h at 400 °C 0.68
F~ As deposited 0.11
I h at 395 °C 0.27
4 h at 395 °C 0.30
25 h at 395 °C 0.27
501 h at 395 °C 0.34

a Film B in ref. 2.
b Film C in ref. 2.
c Film GR-2 in ref. 11.

b l a c k c h r o m e films d e p o s t e d at S a n d i a N a t i o n a l L a b o r a t o r y , A l b u q u e r q u e , N M ,
f r o m b a t h s o f the C h r o m O n y x t y p e 2' 11,13

4. DISCUSSION

D a t a f r o m the l i t e r a t u r e h a v e s h o w n a s t r o n g c o r r e l a t i o n b e t w e e n the o x i d e
c o n t e n t a n d the o p t i c a l p r o p e r t i e s 1'2'7'a'11,16 18. H o l l o w a Y e t al. 2 a n d S h a n k e r 11
h a v e s h o w n t h a t the h i g h e s t ( a n d m o s t stable) s o l a r a b s o r p t a n c e is a c h i e v e d in b l a c k
c h r o m e films w i t h 4 0 ~ o - 7 5 % C r 2 0 3 ; h i g h e r o r l o w e r o x i d e c o n t e n t s result in a r a p i d
d e c r e a s e in t h e s o l a r a b s o r p t a n c e . In this o p t i m u m o x i d e r a n g e , the t h e r m a l
e m i t t a n c e s h o w e d a l i n e a r d e c r e a s e w i t h i n c r e a s i n g o x i d e 2'11. S m i t h e t al. 8'12
s h o w e d t h a t the o p t i m u m o x i d e r a n g e is e x t e n d a b l e b y c h a n g i n g the m o r p h o l o g y o f
t h e films. I n s o m e i n s t a n c e s t h e r m a l a g i n g c a u s e d c h a n g e s in t h e m o r p h o l o g y o f
b l a c k c h r o m e films 8-12'19 d e p e n d i n g o n the m e t h o d o f d e p o s i t i o n a n d , for
e l e c t r o c h e m i c a l l y d e p o s i t e d films, the d e p o s i t i o n b a t h c o n d i t i o n s .
T h e o x i d a t i o n b e h a v i o r o f b l a c k c h r o m e films d e p o s i t e d f r o m the C h r o m O n y x
186 K. SHANKER, P. H, HOLLOWAY

bath is largely independent of the deposition conditions. This is illustrated by the

data in Table II and Fig. 3. All the films show rapid oxidation within the first 2 h
followed by a continued slow oxidation (Fig. 3(a)). The same data, replotted in
Fig. 3(b), show the logarithmic nature of the oxidation. For example, film B, which
had 53~ Cr20 3 in the as-deposited condition, rapidly oxidized to 87~o Cr203 in 1 h
at 460°C. Continued aging at 460 °C caused only a small increase in the oxide
content. This behavior was observed on all the black chrome films irrespective of the
as-deposited oxide content; the difference was in the oxide level at which they
stabilized. The important conclusion that can be drawn from such behavior is that it
is only the oxide formed during thermal aging that protects the metallic chromium
particles from further oxidation. This is true despite the significant amount o f C r 2 0 3
(typically 30~o or more) in the as-deposited films. Thus, for the oxide content in black
chrome films to remain in the optimum range during service, it is necessary for the
as-deposited films to contain only about 30~o-40~o C r 2 0 3. The logarithmic
oxidation results in rapid oxidation into the optimum range (50~o-70~o Cr203 for
the morphology of our films) in about 2 h or less at 400 °C. Further oxidation is very
slow, resulting in stable and optimum optical properties. The optimum oxide

"tOO f~
.~_-- -o- B

8 0 ~ ~ C

60

p---.O F
L - - -- --C:) -
2

O0 2 0l 4 0I 6 0I 8 0I 1 0 ~/ )'n,~.-~-~-~--R
n n0
(a) Aging time (h)

t , o ~ I
[ ~ I ...,.o ,,,,

}
g
0.4

¢ 0.2
I
I
I
I I I I I
0.2 0.4 0.6 0.8 1.0
(b) Normalized Sputter Time
Fig. 3. Volume fraction of oxide in black chrome films B, C and F (Table II) as a function of the thermal
aging time at 460 °C in air: (a) linear time scale (note change in scale); (b) logarithmic time scale.
ELECTRODEPOSITION OF BLACK C r SOLAR COATINGS 187

content may vary somewhat with the deposition procedures but was relatively
independent of the bath conditions in the present study.
To obtain data on the oxide thickness necessary for passivation for any given
combination of temperature and time, oxidation of black chrome can be compared
with that of pure chromium. Results on pure chromium 11'2°-23 indicate that
mechanically polished bulk chromium follows logarithmic oxidation kinetics
whereas electropolished bulk chromium and thin films of chromium follow
parabolic oxidation behavior 2°. The change in oxidation behavior is probably
caused by changes in surface roughness; the rougher samples formed a passivating
Cr203 layer. Smith e t al. 12 observed that black chrome films, irrespective of the
smoothness of the substrate, had a roughness comparable with their thickness
(which is comparable with that of the mechanically polished pure chromium TM20).
Therefore, the logarithmic oxidation kinetics of black chrome films is not
unexpected. The similarity in the oxidation behavior indicates that data obtained on
mechanically polished pure chromium can be extended to black chrome. For
example, pure chromium formed an oxide layer of about 325/~ or less on thermal
exposure for 10000h at 350°C and of about 800/~ or more after about 100h at
460 °C 11.2o. Extending these values to black chrome films indicates that they must
be sufficiently thick to have large agglomerates (chromium particles interspersed in
oxide and voids) which permit the formation of the passivating oxide layer between
the metallic chromium particles and the air. The passivating oxide must be formed
without consuming too much of the metal, i.e. before the total oxide content
becomes greater than the optimum amount (about 50~o-70~/o). Scanning electron
microscope studies 9 ~ have revealed agglomerates of sizes ranging from 400 to
2000,~ depending on the deposition conditions, with the more stable coatings
generally having agglomerate sizes of 1000/~ or greater. This is consistent with the
oxide thickness data obtained on chromium (approximately 325,&) which suggest
that the chromium particles must be about 650/~ or greater to retain a metallic
center after oxidation. The mean chromium grain size of 139 ,~ reported by Lampert
and Washburn z4 is not necessarily incompatible with this conclusion since each
metallic particle contains a number of chromium grains. The necessity is for a
passivating oxide layer between the metallic chromium particles and the environ-
ment and not around each chromium particle or grain. AES results in Fig. 4 indicate
that the increase in oxide content during thermal aging is non-uniform, being greatest
near the surface and least at the film-substrate interface (in stable films). Thus a
thicker outer Cr203 layer results in increased surface passivation on thermal aging.
Data on mechanically polished pure chromium, however, suggest that the thermal
stability of a thick surface oxide layer may be limited in time. A shift was observed to
a much faster oxide growth rate after about 1500,~ of oxide had formed at
temperatures of 450 °C or above ~1,20. Kubaschewski and Hopkins 2s have suggested
that this change is due to recrystallization of the Cr203. Such recrystallization effects
have been suggested by Muehlratzer e t al. 16 to explain the degradation of the solar
absorptance of black chrome films exposed at 400 °C. Thus recrystallization may
have more than one effect.
Although the passivation of black chrome films occurs as a result of the
thermally formed oxide, there are other methods by which passivation can be
188 K. SHANKER, P. H. HOLLOWAY

100,

80

60
x
o

"~ 40
>
---0
( ._U.__O___. . . . . . . . . . . . . . . . . . . F
20

I I I ~ 1
5 10 50 100 500

A g i n g t i m e (h)

Fig. 4. Fraction of Cr203 in black chrome films as a function of the normalized sputter time. Increasing
sputter time crudely correlates with increasing depth. It should be noted that the Cr203 fraction is
greatest in the outer regions of the black chrome and decreases as the black chrome nickel interface is
approached.

introduced such as formation of protective coatings t 1,26, u s e of different deposition

baths 9 or otherwise modifying the structure to extend the compositional range over
which the optical properties are optimal 12.

5. SUMMARIZING REMARKS

Black chrome films electrodeposited from a ChromOnyx bath may be

degraded with regard to their selective solar absorptive properties by oxidation at
elevated temperatures. The formation of oxide follows logarithmic kinetics during
thermal aging in air. This shows that the as-deposited oxide in black chrome is non-
passivating and only the oxide formed during the early stages of thermal aging
protects the deposited metallic chromium particles from further oxidation. Com-
parisons with the oxidation behavior of pure chromium show that the behavior of
electrodeposited black chrome is similar to that of mechanically polished pure
chromium. The thermal stability of the optical properties for black chrome films
with agglomerate sizes of 1000,~ or greater (compared with films with a smaller
agglomerate size) is consistent with the oxide thicknesses required to passivate pure
chromium surfaces.

ACKNOWLEDGMENTS

The authors wish to thank Susan K. Hofmeister for assistance with the AES
measurements•
This research was supported by the U.S. Department of Energy by Grant
DE-FG02-79ER.
ELECTRODEPOSITION OF BLACK Cr SOLAR COATINGS 189

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