Solar Energy Materials 7 (1982) 153-170 153

North-Holland Publishing Company

BLACK CHROME SOLAR SELECTIVE COATINGS OPTIMIZED

FOR HIGH TEMPERATURE APPLICATIONS*

R. B. PETTIT, R. R. SOWELL and I. J. HALL

Sandia National Laboratories,
Albuquerque, N M 87185, USA

Received 12 March 1982; in revised form 27 May 1982

A statistical design approach has been used on a specified set of plating parameters to optimize
the thermal stability of electrodeposited black chrome solar coatings. Plating parameters studied
included the bath composition (chromic acid, acetic acid, trivalent chromium and iron), current
density, plating time, substrate and bath temperature. The optimization procedure consisted of
maximizing the solar absorptance values after thermal aging at high temperatures (up to 450° C in
air). The estimated functional dependence of the thermally aged solar absorptance values on the
four bath constituents was determined in the region of most stable coatings. This relationship was
used to specify a range of bath compositions that provide coatings with optimum thermal stability.
It was also found that chloride ion contamination of the black chrome plating solution significantly
degraded the thermal stability of plated coatings. Fortunately, the chloride ions could be effectively
removed through the addition of silver oxide, which precipitates silver chloride. When the plating
variables were properly controlled, electrodeposited black chrome coatings were obtained which
should maintain solar absorptance values of 0.96 or higher during years of operation at 300°C in air.

1. Introduction

Electrodeposited black chrome solar selective coatings have been utilized in high
temperature (approx. 300°C) parabolic trough solar collector systems for several
years [-1]. Initial research indicated that the coating would maintain the desired high
solar absorptance and low emittance values during extended operation at 300°C in
air [-2]. However, coatings utilized in actual collector systems exhibited degraded
optical properties after only tens of hours operation at 300°C [-3]. The discrepancy
between the initial laboratory studies and the later field experience appeared to be
resolved when test results showed that the trivalent chromium concentration played a
significant role in the thermal stability of the coatings [-4]. In these studies it was
found that lowering the trivalent chromium concentration from 16 to 8 g/l markedly
improved the thermal stability of plated coatings. However, an attempt to duplicate
these results in a commercial plating facility again met with failure [1]. Therefore, a
complete and systematic study of the role of all plating variables was undertaken;
the results of this investigation are reported here.

*This work performed at Sandia National Laboratories supported by the US Department of Energy
under contract number DE-AC04-76DP00789.

0165-1633/82/00(0)O000/$02.75 © 1982 North-Holland

154 R. B. Pettit et al. / Black chrome coatingsJor high temperatures

The goal of this study was to specify a plating procedure that would ensure the
production of thermally stable electrodeposited black chrome coatings for parabolic
trough collector applications. This was accomplished by utilizing statistical experi-
mental design techniques [5]. These techniques attempt to maximize the information
on a system response variable obtained from a limited set of experiments and are
particularly suited to situations in which there are a large number of experimental
variables. In the case of black chrome coatings, the variables studied include the
bath composition (described by four variables), plating current density, bath temper-
ature, substrate and plating time. The design strategy used in our experiments is
discussed below.
Because the coating thermal stability was of utmost importance, concurrently
with the above study, the thermal aging behavior of the coating was investigated
with two goals in mind: First, by determining the temperature dependence of the
degradation, a prediction of the lifetime of the coating at the intended use temper-
ature could be obtained from studies carried out at higher temperatures. Secondly,
an accelerated aging test could be developed and used to monitor the quality of
coatings obtained from the plating process. The details of the thermal aging study
will be published elsewhere [6]; however, some of the results will be used here in
order to justify the thermal aging tests used for the process optimization.
In solar collector applications, there are two optical properties of importance:
The solar absorptance (as) and the total hemispherical emittance (e(T)) at the operating
temperature (T). The relative importance of these two properties depends upon the
detailed solar collector design parameters, such as operating temperature, receiver
size and solar flux concentration. Sandia's experience with moderate concentration
(i.e., 25 x ) parabolic trough systems operating at 300°C indicates that the solar absorp-
tance is much more important than the emittance [7]. Therefore, our optimization
strategy maximized the solar absorptance values while keeping the emittance values
as low as possible. This strategy may not be appropriate in optimizing other selective
coating processes, but it proved adequate for these studies.
In the next section, the experimental design strategy is outlined. Then the experi-
mental techniques are discussed followed by the experimental results. Finally, the
recommended plating procedure is described.

2. Experimental design strategy

Although all experiments should be carefully planned so that the maximum amount
of information is obtained with a minimum number of experiments, this is particularly
important in situations that involve many variables (usually greater than four).
Typically, two strategies can be employed where the object is to determine the values
of the independent variables that yield the best response: First, a large range of each
variable can be explored in order to determine the maximum effect that each variable
can produce. Using this approach, all significant regions are explored first, with the
"best" region contained somewhere inside. The second approach involves initially
investigating a limited range of each variable and determining the direction, or the
 R. B. Pettit et al. / Black chrome coatinos for high temperatures 155

change in each variable, that leads to the best improvement in the response. Because
of our previous experience with black chrome plating and the limited amount of
time and resources available, it was decided that the second approach would be the
most productive. Our strategy therefore involved first investigating a small region
of plating variables using a factorial design [5]. For the initial experiments, the four
bath composition variables were varied as shown in table 1. Since each variable is
set at two end values, this normally leads to 24 or 16 separate bath compositions to be
tested. Because of time limitations, a 1/2 replication, using only 8 bath compositions,
was substituted (see table 1) [5]. The thermal stability of coatings produced by each
bath was determined by measuring the solar absorptance of several samples after
they were thermally aged at a high temperature. From these results, the "direction"
of bath compositions which would produce the highest solar absorptance values was
determined. Several bath compositions were studied along this direction until an
optimum or best solar absorptance value after thermal aging was found. At this point,
a second factorial design was carried out in the optimum region. Using this procedure,
the range of bath composition variables that produced coatings with the best thermal
stability was located. This technique is frequently called "path of steepest ascent" [5].
In the experimental results presented below, only the resulting picture that emerged
from this analysis is presented.
Finally, several variables were treated as "primary" variables while other variables
were considered as "secondary" variables. This was done in order to reduce the
number of variables that was needed to be studied at one time. Based on our previous
experience, primary variables were identified as the four bath constituents, while the
secondary variables included the current density, bath temperature and substrate.
In addition, for each set of primary variables, several coatings were plated at a con-
stant current density but for varying times. This was done since the time required to
deposit a coating with a high solar absorptance value was not critical. It was found
that acceptable coatings could usually be obtained with less than six minutes plating
at 140 mA/cm 2. After varying the primary variables and determining the region that

Table I
Nominal bath compositions chosen for the first factorial design
study of bath composition variables. This design is a one-half replica-
tion of a full 2'* factorial design (see ref. [5])

Trivalent
Chromic acid Add. agent chromium Iron
Bath no. (g/l) (vol"/o) (g/l) (g/l)

6 320 25 9 6.3
7 320 25 11 10.3
8 320 29 9 10.3
9 320 29 11 6.3
10 340 25 11 6.3
11 340 25 9 10.3
12 340 29 9 6.3
13 340 29 11 10.3
156 R. B. Pettit et al. / Black chrome coatinys ]br high temperatures

produced the most thermally stable coatings, the effects of the secondary variables
in this region were studied.

3. Experimental technique

All black chrome coatings were prepared from the Harshaw Chemical Co.,
Chromonyx plating bath [8]. Samples were plated from a five liter plating cell with a
specially designed sample/anode holder that provided a uniform current density at
the sample location [9]. The bath temperature was regulated to within + I°C by
combining active cooling coils and agitation of the plating solution during deposition.
Each plating solution was first electrolyzed at nine volts for 45 rain following makeup
before any samples were plated. The primary substrate used for this study was nickel
foil (99.5~ purity), which was cleaned and activated prior to black chrome plating [8].
The chemical composition of each black chrome bath was determined immediately
after makeup using standard techniques as described in ref. [10]. The measurement
accuracy of each bath constituent is listed in table 2.
The solar absorptance was determined by appropriately averaging hemispherical
reflectance data obtained using a Beckman Model DK-2A spectroreflectometer
over the wavelength range 350 to 2500 nm. The reference material used for these
measurements was packed Halon powder [11]. The 300°C emittance values (e(300°C))
were measured using a Gier-Dunkle infrared reflectometer, model DB-100, as
described in ref. [12].

Table 2
Accuracy of chemical procedures utilized to
analyze the black chrome plating solutions

Bath component Accuracy

Chromic acid + I g/I

Addition agent +0~4 vol"~
Trivalent chromium +_0.2 g/I
Iron ±0.4 g/l

4. Experimental results

4.1. Reproducibility

Before beginning the optimization procedure, the combined reproducibility of the

bath preparation, the plating procedure and the optical measurement procedures was
determined. To estimate this variability, four separate baths were prepared which
had the same nominal composition. Samples were plated in random order for current
densities of 186 and 140 mA/cm 2 with the current density time product equal to 560,
740, 930 and 1115 mA min/cm< The solar absorptance and emittance values were
 R. B. Pettit et al. / Black chrome coatinqs for high temperatures 157

Table 3
Standard deviation in optical properties for black chrome
samples plated from different baths (A) and plated from
the same bath (B). Results are presented for samples
both as-plated and after thermal aging at 400°C for 100 h

c(300°C)

A: Bath-to-bath variations
As-plated +_0.003 +0.009
100 hr/400"C : +_0.014 +_0.006
B: Panel-to-panel variations
As-plated ±0.001 ±0.008
1O0 h/400' C + 0.004 ± 0.002

measured both before and after aging at 350 and 400°C for 24 and 100 h. The above
sequence was repeated for each bath giving two replications per bath (repl. # 1 and
repl. # 2).
The standard deviations of solar absorptance and emittance values both as plated
and after aging 100 h at 400 ° C are listed in table 3. Comparisons of similar panels were
made both from bath to bath and from panel to panel within the same bath. The
largest standard deviation of 0.014 absorptance units in solar absorptance was from
bath to bath after thermal aging. The other standard deviations in solar absorptance
values indicate variations that are less than the estimated variability associated with
the optical measurement itself. For the emittance values, the largest variation occurred
for the as-plated panels, while the variation after thermal aging was much less than
that of the emittance measurement itself.
Analysis of the results indicated that there was no significant difference between the
two current densities, as long as the current-density time product was identical. This
agreed with previous results [13]. The current density was fixed at 140 mA/cm z for
the remaining experiments. For all baths, the coatings obtained from the second
replication (repl. # 2) were slightly more stable (higher solar absorptance values after
thermal aging) than the coatings obtained from the first replication. This indicated
that the deposited coating changed slightly after continued plating (working). This
effect was observed with several other baths in this study. Because the increase in
solar absorptance was very small (less than 0.006 absorptance units) and the change
was in the direction of increased stability, this effect was not considered significant.
The variability in optical properties determined for the other aging times and temper-
atures was identical. Since a higher temperature produced a larger change in the solar
absorptance for the same aging time, the aging time/temperature was increased to
450°C for 40 h for most of the remaining studies. Long term aging results indicate that
no change in the aging mechanism occurred when increasing the temperature from
350 to 450°C [6].
In summary, these results indicate that if carefully controlled, the plating bath,
plating process and optical measurements are reproducible. In addition, there
appeared to be no "hidden" variables that were not being properly controlled.
158 R. B. Pettit et al. / Black chrotne coatin,qs lbr high temperatures

4.2. Gray coatings

In varying the bath composition, a region was found that produced thermally
stable coatings (e.g., the solar absorptance did not change upon thermal aging) but
the initial and final solar absorptance values were both less than 0.90. Because of the
importance of the solar absorptance in determining the collector efficiency, coatings
produced in this region were considered unacceptable.
Since these coatings have a dull metallic gray appearance (rather than black) they
were termed "gray" coatings. Typical hemispherical reflectance properties for a gray
coating are shown in fig. 1 both before and after thermal aging. Note that the reflec-
tance of the as-deposited coating does not show a rapid rise for wavelengths above
approx. 1500 nm, which is typical of black chrome coatings [2]. In addition, as some
of the metallic chromium in the coating oxidizes during thermal aging, the solar

0.60 I I I I _ ~
Z
,,:£ p

w
0.40 m
After 8 h r / 4 5 0 0 C
a::

n
.::C
C.)
m
c:c
0.20 p

:]2
0.0
As_e~~t_.__.~.._
d I I 1--
500 1000 1500 2000 2500

WAVELENGTH , nm
Fig, 1. Hemispherical reflectance properties of a "'gray" black chrome coating both before and after aging.

Table 4
Compositions of black chrome baths that produced gray coatings
(see text)

Trivalent
Chromic acid Add. agent chromium Iron
Bath no. (g/l) (vol '!~,) (g/l) (g/I)

14 323 22.7 9.4 6.3

17 338 23.7 6.5 4.9
17' 338 24.7 6.5 4.9
18 331 24.4 7.9 9.9
19" 327 24.4 11.0 5.4
28* 326 25.2 10.2 8.2
30 322 21.9 9.0 7.8
33 330 24.5 6.0 7.5

*Coatings became black after continued working of bath.

 R. B. Pettit et al. / Black chrome coatings for high temperatures 159

absorptance can increase slightly but typically remains below 0.90. Bath compositions
that produced only gray coatings are listed in table 4.
It was also observed that some baths would first produce gray coatings, but after
continued working they would eventually produce black coatings. The reason for
this change of behavior is not known. These baths are particularly important since
they locate the borderline between "gray" and "black" regions. Coatings obtained
from baths 19 and 28 listed in table 4 were observed to change from gray to black
after continued working. The black coatings obtained from these baths were some of
the most thermally stable coatings produced.
From these results, it was evident that reducing the addition agent concentration
below 24 to 25 volvo resulted in gray coatings. In addition, reducing the trivalent
chromium concentration below 7 to 8 g/l also produced gray coatings. These values
therefore set limits on the region where highly absorbing black chrome coatings
could be obtained.
Analysis of the gray coating microstructure, which has been previously reported in
ref. [14], indicated that these coatings consist of large particles (typically 200 nm in
diameter). This particle size is larger than the average particle size found in optically
black coatings. In addition, coatings obtained near the region that produces gray
coatings have a slightly higher volume fraction of metallic chromium as de-
posited [15].

4.3. Optimum plating region

During the course of this study, a total of 33 separate black chrome plating baths
were evaluated. Samples were electroplated from each bath at a current density of
140 mA/cm 2 for times of 3, 4, 5~, 62 and 8 min. The solar absorptance and emittance
values after thermally aging for 40 h at 450°C for several of these baths are listed in
table 5. Our analysis was limited to coatings that had high solar absorptance values
as plated.
Using the results shown in table 5, a response surface for the aged solar absorptance
values as a function of the four bath constituents was determined [16]. The initial
functional equation for the response surface included all linear and quadratic terms
in a power series expansion in each bath constituent. If the variables X1, X2, X3 and
X 4 are assigned to the concentration of chromic acid (in g/l) addition agent (in volvo),
trivalent chromium (in g/l), and iron (in g/l), then the following polynomial was used:
4 4 4.
= Co + Z c . x . + Z Z 8.,.x.x., (1)
n=l n=l ra=n

where the C's and B's are constants to be determined. The constants were determined
using a least squares computer program [16]. A best fit was determined from the
data by varying the constants C, and B,,,. After each fit, the least significant term
was eliminated and a new fit was obtained until all remaining terms were significant
at the 0.05 level. This iterative procedure was concluded when 11 terms remained
resulting in the following polynomial.
160 R. B. Pettit et al. / Black chrome coatings for high temperatures

Table 5
Optical properties and composition of black chrome baths that produced black coatings. Aged data
are after 40 h at 450°C in air

Chromic Addition Trivalent

0q ~(300°C) acid agent chromium Iron
Bath no. initial aged initial aged (g/l) (vol%) (g/l) (g/l)

6 0.970 0.958 0.31 0.18 3ll 25.0 8.9 6.2

7 0.976 0.932 0.26 0.15 320 25.0 10.0 10.3
8 0.974 0.898 0.23 0.14 319 28.0 8.9 10.1
9 0.968 0.908 0.22 0.14 315 28.8 11.2 6.0
10 0.967 0.949 0.29 0.17 339 25.9 11.1 6.4
ll 0.978 0.946 0.29 0.16 333 26. l 9.1 10.6
12 0.971 0.916 0.23 0.14 330 29.4 8.8 6.3
13 0.961 0.840 0.17 0.12 334 29.3 10.8 10.4
19 0.954 0.950 0.28 0.18 327 24.4 11.0 5.4
20 0.973 0.933 0.27 0.16 328 24.1 11.0 10.2
21 0.961 0.932 0.25 0.16 328 27.1 8.4 5.1
22 0.974 0.920 0.28 0.16 331 27.0 7.9 10.4
23 0.969 0.904 0.22 0.14 324 27.1 12.5 5.1
24 0.969 0.889 0.22 0.14 328 26.7 11.2 10.2
25 0.973 0.868 0.24 0.13 324 30.0 8.3 7.3
26 0.974 0.922 0.27 0.15 326 28.3 7.1 7.9
27 0.970 0.954 0.31 0.18 325 24.4 l 1.5 7.7
28 0.969 0.947 0.30 0.17 331 26.5 9.5 7.8

0q = 13.7084 - 0 . 1 1 5 7 8 X 1 + 0.18536X2 + 0.74681X3 + 0.01982 I X 4

+2.0499 × 1 0 - 4 X 2 -2.8535 × 1 0 - 3 X 2 -2.6505 × 10-3X 2
- 1 . 5 6 3 8 × 1 0 - 3 X 2 - 1.7568 × [0-3X1X3-4.7539 × 1 0 - 3 X 2 X 3 . (2)

T h e m u l t i p l e c o r r e l a t i o n coefficient, R z, associated with this e q u a t i o n was 0.963.

R 2 is a m e a s u r e of h o w well the e q u a t i o n fits the data. If R 2 = 1, the fit w o u l d be
perfect. N o t e that eq. (2) c o n t a i n s t e r m s w h i c h are a p r o d u c t of the i n d e p e n d e n t
variables. T h e presence o f these t e r m s indicates an i n t e r a c t i o n b e t w e e n s o m e o f the
variables. T h e d a t a in table 5 used to g e n e r a t e this e q u a t i o n were l i m i t ed to the
f o l l o w i n g ranges:
334~>X1~>315g/1, 30.0>~X2>~24.1g/1,
12.5~>X3~>7.1g/l, 10.6~>X4~>5.1g/l. (3)

T h e r e f o r e eq. (2) s h o u l d be a p p l i e d with c a u t i o n outside this region.

T h e solar a b s o r p t a n c e values c a l c u l a t e d using eq. (2) are c o m p a r e d with the
e x p e r i m e n t a l values in table 6. N o t e t h a t the largest difference b e t w e e n the two
values is only 0.012 a b s o r p t a n c e units. If the e x p e r i m e n t a l values o f X1, X z , X3, X4
at each d a t a p o i n t are v a r i e d by their m e a s u r e m e n t er r o r (see table 2), t h e n all of the
c a l c u l a t e d solar a b s o r p t a n c e values can be m a d e to agree with the e x p e r i m e n t a l
values. T h u s discrepancies in the fit are n o t significant within m e a s u r e m e n t errors.
O v e r the range of b a t h c o m p o s i t i o n s studied (see above), the a d d i t i o n agent an d
 R. B. Pettit et al. / Black chrome coatings.for high temperatures 161

Table 6
Experimental solar absorptance values and the
values calculated using eq. (2) in the text

Bath no. exp. calc. A~

6 0.958 0.956 -0.002

7 0.932 0.930 - 0.002
8 0.898 0.891 - 0.007
9 0.908 0.910 ~ + 0.002
10 0.949 0.950 + 0.001
11 0.946 0.934 - 0.012
12 0.916 0.904 -0.012
13 0.840 0.838 -0.002
19 0.950 0.951 + 0.001
20 0.933 0.930 - 0.003
21 0.932 0.935 + 0.003
22 0.920 0.930 + 0.010
23 0.904 0.898 - 0.006
24 0.889 0.896 + 0.007
25 0.868 0.875 + 0.007
26 0.922 0.915 - 0.007
27 0.954 0.953 -0.001
28 0.947 0.945 - 0.002

trivalent chromium constituents have the most affect on the aged solar absorptance
values. Much less change in solar absorptance occurs when varying the chromic
acid and iron concentrations. Contour plots of the solar absorptance as a function
of the trivalent chromium and addition agent concentration with the chromic acid
concentration fixed at 330 g/1 and the iron concentration equal to 10.3, 8.0 and 6.3 g/l
are shown in figs. 2, 3 and 4, respectively. Note that the contours with the iron con-
centrations at 8.0 and 6.3 g/1 are nearly identical while increasing the iron concentra-
tion to 10.3 g/1 decreases the solar absorptance values dramatically. These figures
give evidence of the interaction between the trivalent chromium and addition agent
since the contours are not everywhere parallel. Note also that the same thermal
stability (solar absorptance values) can be obtained for high trivalent chromium and
low addition agent as for low trivalent chromium and high addition agent. The
optimum conditions occur when both variables are at their lower ranges (e.g., trivalent
chromium near 7 to 8 g/1 and addition agent near 24.5 to 25 volvo ). Thus the beneficial
effect of lowering the trivalent chromium concentration that was determined in
earlier studies [-4] was confirmed. However, because of the interaction between the
trivalent chromium and the addition agent, maintaining a low addition agent con-
centration is also important in order to obtain the most thermally stable coatings.
Defining an acceptable region for obtaining thermally stable coatings must take
into account both the desired coating optical properties and bath composition
control requirements. For example, in fig. 3 two plating regions are defined that
maintain the solar absorptance greater than or equal to 0.94 after thermal aging for
162 R. B. Penit et al. / Black chrome coatings.Jbr high temperatures

12

Chromi[cAcid- 330glII-'~
-- 11 Iron - I0.3gll

~E I

= I0
:E
O
c~
I

9
F--
z
L.u
-J
.,:Z

>
m
mgc
8

6
23 24 25 26 2l 28 29 30
ADDITION AGENT ( v01% )

Fig. 2. Contours of constant solar absorptance as a function of the trivalent chromium and addition agent
concentration for the chromic acid fixed at 330 g/1 and the iron fixed at 10.3 g/1. Contours were calculated
from eq. (2) in text. The shaded region indicates where gray coatings are obtained.

omic Acid - 330 gfl

-~
. . . . . R e g i o n # l -/- 7 \ \ n n.\ \
O.~ 93~0.92
93N0.92 N0.9!
:~ 1O

m 9

< 8

6
23 24 25 26 2? 28 29 30
ADDITION AGENT ( vol % )
Fig. 3. Same as fig. 2 but the iron is fixed at 8.0 g/l. Regions #1 and #2 represent "equivalent" plating
areas as defined in the text.
 R. B. Pettit et al. / Black chrome coatings for high temperatures 163

12
~romic Aci~-330g/l[
• NN~- 6..3g/I_~
10
O

:I:

9
t.u

>
i 8

23 24 25 26 2"I 28 29 30
ADDITION AGENT ( vol % )

Fig. 4. Same as fig. 2 but iron fixed at 6.3 g/l.

40 h at 450°C in air. In region # 1, the trivalent chromium concentration is allowed

to vary from 7.0 to 10.0 g/l while the addition agent concentration varies from 24.5
to 26.0 volvo. Since it is difficult to maintain the addition agent within this range and
the trivalent chromium level does not vary appreciably during prolonged plating
[18], the addition agent range can be expanded from 24.5 to 27.0 volvo provided that
the trivalent chromium range is reduced to 7.0 to 9.0 g/1 (region # 2 in fig. 3). In
both cases, the best coatings are still obtained when the trivalent chromium and
addition agent concentrations are at their lowest values while the most unstable
coatings are obtained when these parameters are at their highest values.
As can be seen from table 5, increasing the coating stability also leads to an increase
in the 300°C emittance values both as-plated and after thermal aging• For example,
the most stable coatings (obtained from baths #6, 10, 19, 27 and 28) have emittance
values from 0.28-0.31 as-plated and from 0.17-0.18 after thermal aging. This is
compared to the emittance values for the least stable coatings (from baths # 13, 24
and 25) which varied from 0.17-0.24 as-plated and from 0.12-0.14 after thermal aging.
At 300°C, 65~o of the eventual decrease in the emittance occurs within 24 h. The
decrease in emittance with thermal aging has been previously reported [1, 2, 4].
Although the emittance values are higher for the stable coatings, these higher values
(0.18 vs. 0.12) should have little effect on the collector operating efficiency as pre-
viously explained [7].
In summary, this analysis has shown that coatings with the best thermal stability
are obtained by lowering both the trivalent chromium and addition agent concentra-
tions to values near 7.0 g/1 and 24.5 volvo, respectively. Further reduction in these
164 R. B. Pettit et al. / Black chrome coatings lbr hi,qh temperatures

constituents results in the deposition of gray coatings that suffer from low initial
solar absorptance values. The functional dependence of the solar absorptance on all
bath constituents is adequately described by eq. (2). This equation can be used to
determine an acceptable plating region once the required thermal stability and
process control requirements are set. A recommended range for the bath composition
that has been successfully maintained in practice is described in a later section.

4.4. Chloride and nickel bath contamination

In addition to the bath composition effects, it was also determined that trace levels
of chloride ions (C1 -) in the black chrome bath had a detrimental effect on the thermal
stability of plated coatings. This effect was demonstrated by adding controlled
amounts of chloride ions to a bath. Samples were plated after each chloride addition
and the optical properties measured both before and after thermal aging for 40 h at
450°C in air. The results are tabulated in table 7. As the chloride ion concentration
was increased, both the solar absorptance and emittance values decreased after
thermal aging. Note that the as-prepared black chrome bath contained approx.
10 mg/i of chloride ions, which were traced to chloride contaminants in the chromic
acid used to make up the bath. (The chloride ion level in all baths used in this study
was 8 I0 mg/l.)
Several procedures were investigated to reduce the chloride ion concentration in
the plating solution. These included (1) electrolyzing the bath using platinum anode
and cathodes; and (2) adding silver oxide to precipitate silver chloride. The electrolysis
did reduce the chloride ion concentration, but long times were required (hours)
and the bath composition was significantly changed in the process (some Cr VI was
reduced to Cr Ili).
The addition of silver oxide to the black chrome bath was effective in reducing the
chloride ion concentration. Note in table 7 that the thermal stability was improved
after the second silver oxide addition when the chloride ion concentration was
reduced below that of the as-prepared bath. A plot of the solar absorptance values
from table 8 as a function of the chloride ion concentration shown in fig. 5 indicates

l-able 7
Results of varying chloride ion concentration on the optical
properties of plated black chrome coatings after aging at 450 C
for 40 h

Chloride
Bath condition conc. (mg/l) :t~ ~:(30f)"C)

As-prepared 10 0.92 0.15

Chloride added 15 0.90 O. 14
Chloride added 26 0.89 O, 14
Chloride added 36 0.88 O. 14
First silver oxide added 15 (/.92 0.16
Second silver oxide added < 1.5 0.94 0.18
 R. B. Pettit et al. / Black chrome coatings for high temperatures 165

Table 8
Results of adding sulfamate nickel plating solution to a
black chrome bath after aging at 400°C for 177 h. All
samples were electroplated for 4 min at 140 mA/cm 2

Ni bath as
Bath condition added 0h 117 h/400°C

As-prepared 0'~/o 0.98 0.95

Nickel bath added 1''/ 0.97 0.95
Nickel bath added 2'!~ 0.97 0.95
Nickel bath added 4" 0 0.97 0.95

1. O0 I I I
• As-prepared
• CI addition
0.95 - .. -

0.90

0.85 I I I
0 10 20 30 40
CI 10N CONC. I mg/f )
Fig. 5. Solar absorptance values after thermal aging for 40 h at 450°C as a function of the chloride ion
concentration.

approximately a linear effect over the range studied. The solar absorptance decreases
approx. 0.01 absorptance units for every 6 mg/l increase in chloride ion concentration.
It was also observed that when enough silver oxide was added to completely remove
all of the chloride ions (assuming complete reaction), the chloride ion concentration
only decreased by about 50~o within 24 h. The remaining chloride ions were, however,
slowly removed over a period of many days. Excess silver oxide added to a bath
appeared to act as a getter and continued to remove chloride ions while not adversely
affecting the plating process.
In addition to the chloride ion concentration, the effect of a sulfamate nickel
plating solution [-17] on the stability of the plating coatings was studied. In this case,
samples of the nickel plating solution were added to the black chrome bath as listed
in table 8. The solar absorptance values after thermal aging for 117 h at 400°C in air
were identical to the control samples. Thus contamination from a sulfamate nickel
bath does not adversely affect the thermal stability.

4.5. Other bath variables

After determining the bath composition range that produced thermally stable
coatings, the effect of the secondary variables was investigated. These variables
166 R. B. Pettit et al. / Black chrome coatings fi~r hioh temperatures

included the bath temperature, substrate material and plating current density. For
these tests, a single bath was chosen (bath #28). Ideally, a matrix of baths should be
used to explore the region of interest to determine if any interactions exist between
the secondary variables and the primary bath composition variables. However, time
and manpower limitations precluded a complete investigation. Therefore, the assump-
tion must be made that the effects determined for the secondary variables from a single
bath will not change appreciably as the bath composition is varied. Samples were
plated from this bath for varying parameters in a random sequence. Similar samples
plated at the beginning, middle and end of the sequence all exhibited identical optical
properties.
The bath temperature was varied from 10 to 25°C, in steps of 5°C. The solar absorp-
tance and emittance values after aging for 40 h at 450°C are shown in fig. 6. At bath
temperatures above 20°C, the solar absorptance begins to drop indicating lower
thermal stability. However, over the range 10-20°C there appears to be little effect
of bath temperature on the thermal stability of plated coatings. Note again the trend
of decreasing emittance values with the decreasing thermal stability of the plated
coatings.
The plating current density was varied from 70 to 230 mA/cm 2 while the current
density time product was held fixed at 745 mA min/cm 2. Solar absorptance and
emittance values in fig. 7 are shown after thermal aging at 450°C for 40 h. In this case,
current density values below 115 mA/cm 2 reduced the thermal stability of the plated

0.96
I I I
-- 0.19 0.18
0.94 -

0.92 -

0.14 i
0.90 I I I
10 20 30 40
TEMPERATURE , °C

Fig. 6. Solar absorptance values after thermal aging as a function of the temperature of the black chrome
bath. The values listed at each point represent the measured 300°C emittance value of each sample.

0.96
I I I I

0.17 0.17 0.17

0.94 -- 0.16 ..,4_ e ~.
ff -- 0.15J1¢ ' ' ~
/
0.92
-
-- O. l
, y/ --
0.90 I I I
50 100 150 200 250
CURRENT DENSITY , mAlcm 2

Fig. 7. Solar absorptance values after thermal aging as a function of the plating current density. The 300" C
emittance values are listed at each point.
 R. B. Pettit et al. / Black chrome coatings for high temperatures 167

coatings while no significant effect was observed from 115 to 230 mA/cm 2. Again
note the trend of lower emittance values with decreasing thermal stability.
F o u r substrates were tested: (1) nickel foil (which was our standard substrate);
(2) sulfamate nickel [17] (25/~m thick) deposited on a mild steel substrate; (3) 302
stainless steel; and (4) sulfamate nickel overcoated with a metallic chromium flash
(which produced a metallic chromium layer approx. 2 /am thick). The sulfamate
nickel/mild steel substrate simulated a typical receiver tube used in a parabolic
trough collector [1]. The stainless steel was chosen because previous results had
shown that coatings deposited on stainless steel were slightly more stable than similar
coatings deposited on a nickel substrate [4]. The chrome flash was applied to the
sulfamate nickel substrate to determine if the increased stability of coatings applied
to a stainless steel substrate was due primarily to the high metallic chromium content
of the stainless steel surface.
Both solar absorptance and emittance values are listed in table 9 for plating times
of 55, 6~3 and 8 min at 140 mA/cm 2. C o m p a r e d to the nickel foil, both the sulfamate
nickel and 302 stainless steel exhibited slightly improved stability, with the 302
stainless steel being the best substrate tested. The chrome flash did not improve the
thermal stability as c o m p a r e d to the nickel foil, and in fact the stability decreased
somewhat. Therefore the improved stability of the stainless steel substrate does not
appear related to the metallic c h r o m i u m content of that substrate.

Table 9
Results of substrate variation on the thermal stability of
black chrome coatings. All panels were plated at a current
density of 140 mA/cm2 and aged at 450°C for 40 h

Plating
Substrate time (min) ~ e(300°C)

Ni foil 5~ 0.94 0.17

6~3 0.94 0.18
8 0.95 0.17
Sulfamate nickel 5~ 0.95 0.24
6~3 0.95 0.20
8 0.95 0.23
302 Stainless steel 52 0.97 0.23
0.96 0.22
8 0.97 0.23
Chromium flash over 52 0.93 0.23
sulfamate nickel 62 0.93 0.17
8 0.92 0.18

5. Recommended plating procedure

A recommended plating procedure is briefly outlined in table 10; a more detailed

description of the plating process is contained in Sandia Process Specification
 168 R. B. Pettit et al. / Black chrome coatings for high temperatures

Table 10
Recommended plating procedure for obtaining thermally stable black chrome coatings. More details are
contained in Sandia Process Specification SS-$34732

1. Vapor degrease and fine bead blast substrate

2. AnodicaUy clean in 50'I/ocaustic soda bath for I -2 rain
3. Water immersion rinse for 2 rain
4. Cathodic acid clean in sulfuric acid bath for I-3 min
5. Water rinse (same as ~ 3)
6. Repeat anodic clean
7. Water rinse (same as ~31
8. Mild acid rinse
9. Water rinse (same as #:3)
10. Nickel plate using sulfamate nickel bath to 25-37 /~m (25 #m minimum). Note: No copper strike
between nickel and substrate
11. Water immersion rinse in deionized water (minimum resistivity 250 kf~)
12. Spray rinse deionized water
13. Repeat ~ 11 and g 12
14. Black chrome plate at 140 to 190 mA/cm 2 for 3 to 5 min at 15 20°C with the bath composition as
follows:
chromic acid: 327-337 g/1
addition agent: 24.5-26.0 vol",,
trivalent chromium: 8.0-10.0 g/I
iron: 6.5-8.5 g/l
The anode should be mild steel with an anode/cathode area ratio of 2/1
15. Repeat steps ~ 13 and ~ 12 and then air dry

SS-34732 " E l e c t r o p l a t i n g M i l d Steel Receivers for C o n c e n t r a t i n g S o l a r Collectors".

Steps 1 t h r o u g h 9 clean a n d p r e p a r e the m i l d steel s u b s t r a t e for the nickel p l a t i n g
process (step 10). T h e t h o r o u g h rinsing (steps l l t h r o u g h 13) before e n t e r i n g the
b l a c k c h r o m e b a t h ensures m i n i m u m c o n t a m i n a t i o n of the solution. T h e p l a t i n g time
in the b l a c k c h r o m e b a t h m u s t be a d j u s t e d in o r d e r to o b t a i n the desired o p t i c a l
properties. T y p i c a l o p t i c a l p r o p e r t i e s for a s - p l a t e d p a r t s w o u l d be solar a b s o r p t a n c e
values greater t h a n o r equal to 0.96 a n d e(300°C) values between 0.25 a n d 0.35. After
h e a t i n g at 450°C for 8 h, the solar a b s o r p t a n c e s h o u l d decrease by less t h a n 2~o,
while the e m i t t a n c e s h o u l d decrease to 0.15-0.25.
This p l a t i n g process was first d e m o n s t r a t e d at S a n d i a using a 7501 tank. A series of
nickel foil panels a n d 2.5 cm O D by 76 cm l o n g nickel p l a t e d m i l d steel tubes were
b l a c k c h r o m e plated. T h e t h e r m a l stability of these c o a t i n g s were similar to the m o s t
stable c o a t i n g s that were o b t a i n e d d u r i n g the previously d e s c r i b e d statistical study.
Finally, the p l a t i n g p r o c e d u r e was successfully d e m o n s t r a t e d in a c o m m e r c i a l electro-
plating facility using a 3000 1 tank. O v e r 200 3.7 m l o n g nickel p l a t e d steel receiver
tubes were e l e c t r o p l a t e d with stable b l a c k c h r o m e coating. T h e results of this in-
vestigation are s u m m a r i z e d in a f o r t h c o m i n g S a n d i a r e p o r t [18].

6. Conclusions and summary

A c o m p l e t e investigation of the effect of the b l a c k c h r o m e b a t h c o m p o s i t i o n o n the

t h e r m a l stability of d e p o s i t e d c o a t i n g s was c o m p l e t e d using a statistical design a n d
 R. B. Pettit et al. / Black chrome coatings for high temperatures 169

analysis approach. Two regions of bath composition were found that produced
unacceptable coatings. In one region, coatings had solar absorptance values below
0.90 both as-plated and after thermal aging. Because of their visual appearance,
these coatings were termed gray. In the second region, as-plated coatings initially
had high solar absorptance values (greater than 0.96) but the solar absorptance
decreased rapidly upon thermal aging. Between these two regions, thermally stable
coatings were obtained with the best stability occurring next to the region that pro-
duced the gray coatings.
The primary bath constituents affecting the stable region were the trivalent
chromium concentration and the addition agent concentration. The most stable
coatings were obtained when each constituent was at a low value. The 300°C emit-
tance values for thermally stable coatings were higher than the emittance values
typically obtained for unstable coatings (0.28 vs. 0.20). However, after heating for a
short time at 300°C or higher, the emittance values for the stable coatings decreased
rapidly to the range 0.174).18.
In addition to the influence of the bath composition, trace levels of chloride ions
in the black chrome bath reduced the thermal stability of plated coatings. While this
effect appeared to be linear in the chloride ion concentration, chloride levels below
l0 mg/l cause a reduction in the solar absorptance of less than 1.5% after heating.
Through the addition of silver oxide to the plating bath the chloride ion concentration
can be reduced to values below 1-2 mg/l.
Several other variables were also studied, including the current density, bath
temperature and substrate. From these results, it was concluded that the bath temper-
ature should be maintained between 15-20°C and the current density from 140-
230 mA/cm 2. Of the substrates tested, slightly more stable coatings were obtained
on 302 stainless steel, while coatings deposited on nickel foil and electrodeposited
sulfamate nickel produced identical aging behavior.
For the best coatings obtained in this study, the solar absorptance decreased less
than 1% after 40 h at 450°C in air. Heating the same coating at 350°C in air, over
5600 h were required to reduce the solar absorptance to the same value. This repre-
sents a factor of 140 times longer at 350°C compared to 450°C. Projecting these
results to 300°C (the typical operating temperature of a parabolic trough collector
system) it appears that years of operation will not significantly degrade the optical
properties of these coatings. More details of the thermal aging behavior of these
coatings will be published [6].
These studies resulted in a detailed process specification that is outlined in table 10.
The specification includes the necessary sample surface preparation and careful
rinsing procedures required in order to ensure negligible contamination of the black
chrome plating bath. This process has been successfully demonstrated in a com-
mercial plating facility where over 200 solar receiver tubes were successfully plated.

Acknowledgements

The authors gratefully acknowledge the assistance of F. E. Martinez for bath

170 R. B. Pettit et al. / Black chrome coatings ]br high temperatures

preparation and plating, A. R. Mahoney for optical measurements and S. L. Erickson

for bath analysis.

References

[1] See Proc. Line-Focus Solar Thermal Energy Technology Development Conf., Albuquerque, NM
(9 I1 Sept. 1980)(Sandia Nat. Labs. Report SAND 80-1666)*,
[2] R. B. Pettit and R. R. Sowell, J. Vac. Sci. Technol. 13 (1976) 596.
[3] R. R. Sowell and R. B. Pettit, Sandia Nat. Labs. Report SAND 78-0554 (April 1978)*.
[4] R. R. Sowell and R. B. Pettit, Plating and Surface Finishing 65 (19781 42.
R. B. Pettit and R. R. Sowell, Proc. 1979 Intern. Solar Energy Society Congr., Atlanta, GA (28 May
1 June 1979) p. 1897.
[5] See G. E. P. Box, W. D. Hunter and J. S. Hunter, Statistics for Experimenters (John Wiley, New
York, 1978).
[6] R. B. Pettit, to be published.
[7] G. W. Treadwell, Sandia National Labs. Report SAND 76-0082 (July 19761*.
[8] See Harshaw Chromonyx Plating Process Instructions SOL CRX 0979, HT SOL CRX 1079 and
CRX 3CR-0180. Process covered by US Patent No. 3 620 935, Harshaw Chemical Co., Cleveland, OH.
[9] J. B. Mohler, Monthly Review Am. Electroplaters' Soc. 1361 (Dec. 19471.
[10] S. L. Erickson, Sandia Nat. Labs. Report SAND 82-0467 (March 1982)*.
[11] V. R. Weidner and J. J. Hsia, J. Opt. Soc. Am. 71 (19811 856.
[12] R. B. Pettit, J. Eng. Power 100 (1978) 489.
[13] R. B. Pettit and B. L. Butler, Sandia Nat. Labs. Report SAND 77-0111 (Feb. 1977)*.
[14] R. B. Pettit, J. N. Sweet and R. R. Sowell, Proc. 1982 MiCON Syrup., Houston, TX (18-19 Jan. 1982).
[15] P. H. Holloway, K. Shanker, R. B. Pettit and R. R. Sowell, Thin Solid Films 72 (1980) 121.
[16] R. L. lman, J. M. Davenport, E. L. Frost and M. J. Shortencarier, Sandia Nat. Labs. Report SAND
79-1472 (Jan. 1980)*.
[17] Sulfamate Nickel Plating SN, Barrett Chem. Products, Div. of Allied Research Prod., Inc. Baltimore,
MD, US Patent 2 318 592 (June 1959).
[18] R. R. Sowell and R. B. Pettit, Sandia Nat. Labs. Report (to be publishedl*.

*Available from NTIS, U.S. Department of Commerce, 5285 Port Royal Rd., Springfield, VA 22161, U.S.A.