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Surface & Coatings Technology 201 (2006) 855 – 862

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Studies on ultra high solar absorber black electroless nickel coatings


on aluminum alloys for space application
Vishal Saxena, R. Uma Rani, A.K. Sharma ⁎
Thermal Process Section, ISRO Satellite Centre, Vimanapura Post, Bangalore-560 017, India
Received 4 October 2005; accepted in revised form 29 December 2005
Available online 7 March 2006

Abstract

A simple process of blackening of electroless nickel is investigated to produce ultra high solar absorber coating on the aluminum alloys. Process
optimization was carried out by investigating the influence of various operating conditions, viz., pH of electroless nickel solution, thickness of
electroless nickel deposit, formulation, concentration, temperature and processing time of etching solutions on the physico-optical properties of the
black coating. The nature of the coating was evaluated by the thickness measurement, micro hardness evaluation and EDX studies. The
microstructure of the deposits was examined under scanning electron and optical microscope. The space worthiness of the coating was evaluated by
the environmental tests, viz., humidity, corrosion resistance, thermal cycling, thermo-vacuum performance and thermal stability tests. Optical
properties of the coating were measured before and after each environmental test to ascertain its stability. The blackened electroless nickel provides
high solar absorber in the order of 0.995. The results of these studies clearly indicate that the coating process described herein is extremely suitable as
a solar absorber coating for space and allied application.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Electroless nickel; Black electroless nickel; Blackening; High solar absorber coating

1. Introduction in a longer spacecraft life. Among the conventional structural


material used in space application aluminum alloys are front-
The inherent lightness and high strength to weight ratio of runners [6]. Aluminum is a strongly electronegative metal and
aluminum alloys has focused attention on their increasing ap- possesses a strong affinity for oxygen forming a very thin
plication in aerospace and allied fields [1,2]. In addition to low- tenacious oxide film [7]. Aluminum and its alloys therefore
density, aluminum alloys possess high mechanical strength, require special surface preparation for successful use in aero-
excellent thermal and electrical conductance, good reflectivity space industry.
and low working cost [3,4]. However, severe operating Electroless nickel plating is an autocatalytic process that
conditions such as high specific pressure, high temperature, a produces a nickel deposit on certain catalytically active substrate
corrosive environment or abrasive wear often limit the pos- using a controlled chemical reaction [8,9]. The ability of hypo-
sibility of using aluminum alloys directly [5]. phosphite to reduce metal ions from their salt solution is in
To reduce the structural mass of machine and equipments, the principle utilized in electroless nickel plating. The necessary
use of light alloys is widely recommended. Mass reduction is an electrons are delivered by the hypophosphite, which is oxidized
important criterion in spacecraft design because the cost of a to its ions.
spacecraft launch is enormous. Reduction in structural mass The unique combination of properties of electroless nickel
leads to higher payload capability and higher fuel mass, resulting coating such as corrosion and wear resistance, hardness, lu-
bricity, bondability and uniformity of deposit regardless of ge-
ometry of the substrate makes it ideal for a wide spread
application in metal finishing industries [10]. Versatile magnetic
⁎ Corresponding author. Tel.: +91 080 2508 3106; fax: +91 080 2508 3203. properties have led to the applications in the computer industries
E-mail address: aks@isac.gov.in (A.K. Sharma). as a coating for aluminum hard disk. The electroless nickel
0257-8972/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.12.050
856 V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862

coating is completely non-magnetic if it contains phosphorous 2.2. Electroless nickel blackening process
content more then 10% [11]. Electroless nickel coatings are also
frequently applied on aluminum to provide a solderable surface Electroless nickel deposition on aluminum alloys was carried
and used with molds and dies to improve lubricity and part out as per our previous publication [2] and this was followed by
release. the blackening process. The specimens were processed for black
The electroless nickel deposition in the presence of hypopho- electroless nickel coating using the following sequence of
sphite in aqueous solution consists phosphorous contents operations:
ranging from 2% to 15%, depending upon the formulation of
plating solution and operating conditions [12]. Due to the pres- 1. Solvent degreasing using tri-chloroethylene in an ultrasonic
ence of phosphorous electroless nickel deposits are easy to etch bath at room temperature (25 ± 5 °C) for 5–10 min.
by the oxidizing acids to obtain the ultra black high solar 2. Alkaline cleaning in a solution containing sodium carbonate
absorptance surface. The high absorptance of these coatings is (Na2CO3), 20 g/L and trisodiumorthophosphate (Na3PO4·
associated with unique surface morphology consisting of a dense 12H2O), 25 g/L operating at 60 ± 5 °C for 2–3 min. Water rinse.
array of microscopic, conical pores perpendicular to the surface. 3. Acid cleaning for 2–3 min in a solution of sulphuric acid
This structure produced by selective etching traps the light (SG 1.83) 10 ml/L, hydrofluoric acid (40%) 12.5 ml/L and
and is capable of absorbing over 99% light in solar region nitric acid (SG 1.42) 25 ml/L operating at room temperature
(300–2000 nm) [13]. (25 ± 5 °C). Water rinse.
Ultra high absorptance black coatings are of paramount 4. Zincating (alloy zincating) by immersion with agitation for
importance in the design of terrestrial and space-borne optical 1 minute in a solution containing nickel sulphate, NiSO4·
instruments and sensors used for measurements in ultra-violet, 7H2O, 30 g/L; zinc sulphate, ZnSO4·7H2O, 40 g/L; sodium
visible and infrared spectral regions [14]. These coatings are hydroxide, NaOH, 106 g/L; potassium cyanide, KCN, 10 g/
extremely useful to improve the absorptance of thermal detectors L; potassium bitartarate, KC4H5O6, 40 g/L; copper sulphate,
and to suppress the unwanted reflections or scattered light in CuSO4·5H2O, 5 g/L and ferric chloride, FeCl3, 2 g/L at room
optical systems, like telescope housing and baffles where stray temperature (25 ± 5 °C). Alternatively, to above formulation a
light reduction is vital. The later is of significance when it is proprietary solution ALZINCATE, an alkaline zinc prepara-
necessary to reduce the physical size of the instrument whilest tion manufactured by M/s. Grauer and Weil (India), Mumbai
not compromising performance. These coatings have been suc- may also be employed. Water rinse.
cessfully employed in the baffle instruments of many spacecrafts 5. Stripping the first zincating layer as obtained in previous step
such as Laser Interferometric Gravitational Wave Observatory by immersion in 50% nitric acid solution at room
(LIGO), Cosmic Background Explorer (COBE), Hubble Space temperature for 20–30 s. The relatively loose zinc layer is
Telescope (HST) and Extreme Ultraviolet Explorer (EUVE). In removed in this step. Water rinse.
addition, some black surfaces have been used as space-borne 6. Re-zincating in a solution by repeating the step 4 but for 30 s.
calibration reference sources and as calibration standard due to Water rinse. This step provides a zinc coating that consists of
their stable, ultra high absorptive properties [15]. a large number of fine grains that are uniform and compact.
In the present communication, a simple chemical immersion 7. Electroless nickel plating in a solution
process of blackening of electroless nickel to provide ultra high
absorptance coating is described. As these coatings consist of Nickel sulphate, NiSO4·7H2O 30 g/L
metal/metal oxide/phosphate composite, these are extremely Sodium hypophosphite, NaH2PO2 10g/L
Sodium citrate, Na3C6H5O7·2H2O 12.5 g/L
stable in space environment. Black paints with organic binders Sodium acetate, CH3COONa 5.0 g/L
are not recommended for optical instruments in space applica- Thiourea, NH2CSNH2 1 mg/L
tions due to their high total mass loss (TML) and condensable pH 4.7
volatile condensed material (CVCM) percentage. The volatile Temperature 88–90 °C
materials released from these materials may deposit on the Filtration Continuous
Time 3h
optical mirrors, which are at low temperatures affecting their Coating thickness 30 ± 2 μm
performance [16]. The black electroless nickel being an in- Water rinse
organic coating with negligible weight loss in space conditions is
an ideal choice in such applications. The pH was adjusted by the addition of dilute sulphuric acid
or ammonia solution. Continuous filtration of plating
2. Experimental details solution and mechanical agitation of job is mandatory to
obtain good electroless nickel deposits. Continuous filtra-
2.1. Materials and chemicals tion of the plating solution was carried out at 300 rpm with
Serfilco filter pump, Model-space saver CL1B5, Manche-
Aluminum alloy test specimens of AA-6061 (Al-97.9%, ster, England.
Mg-1.0%, Si-0.6%, Cu-0.25%, Cr-0.25%) and AA-1100 (99.0% Al) 8. Blackening of electroless nickel
of the size of 30 × 30 × 2 mm were used for obtaining ultra high Blackening of electroless nickel was carried out by
solar absorber black electroless nickel coating. All the chemicals immersing in the oxidizing acid solutions. Three different
used for solution preparation were of laboratory reagent grade. acid formulations were investigated.
V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862 857

Solution-1 Nitric acid (9 M) using a solar reflectometer version 50, model SSR-ER and an
Solution-2 Sulphuric(6 M) + Nitric acid (4 M) emissometer model RDI, respectively, from Devices and
Solution-3 Nitricacid (1.1 M) + Sulphuric acid (0.3 M) + Services Co. (USA). Both these instruments provide an average
Potassium permanganate (0.1 M) value of solar absorptance and infrared emittance digitally over
the entire solar and infrared region. The solar spectrum of the
After etching, the specimens were rinsed quickly and nickel black coating was recorded on a Varian spectrophotom-
thoroughly in the water. eter (Australia), in the 200 to 2300 nm-wavelength region.

2.3. Instrumentation and measurement techniques 3. Results and discussion

The morphological studies of the electroless and black nickel Although electroless nickel can be deposited directly on
coating were carried out with JEOL JSM-840-A scanning elec- aluminum alloys, however, in practice it is sometimes non-
tron microscope, Japan. This electron microscope was equip- reproducible and results in to non-uniform surfaces. The surface
ped with an energy dispersive X-ray spectroscopic (EDX) of aluminum is always covered with a highly protective in-
micro analyzer, Model TN 5500, Noran instruments, USA, for sulating natural oxide film, which hinders the formation of
elemental analysis of the electroless and black nickel coating. further coating. Methods such as zincating are used to remove
Adhesion of black electroless nickel coating was evaluated by this nascent oxide and cover the aluminum with a thin layer of
Scotch tape peel-off test as per American standard MIL-C- zinc and protect the formation of passive oxide layer. Zincating
81706. This test consists of scribing through the deposit to the acts as an activation coating. It not only provides uniform
base metal 11 parallel lines with a sharp tool approximately 2 mm electroless nickel deposit but also accelerates the rate of
apart. Another 11 lines were scribed perpendicular to the first deposition reaction [17].
11 lines. The resulting pattern was 100 squares of 4 mm2 each.
Masking tape of 1 in. width, type 3 M-500 (pressure 500 g/in. width) 3.1. Mechanism of film formation
was then applied over this pattern by passing a 2 kg rubber-
covered roller over the tape two times. The tape was then When the clean aluminum sample is immersed in the alkaline
removed quickly at a right angle to the surface. zincating solution, the tenacious oxide film present on the
Thickness of both the black coating and electroless nickel surface of aluminum is dissolved along with aluminum, and a
plating was measured by micro sectioning. The samples were zinc film is deposited [18]. The overall process can be rep-
mounted using Epo-Kwick resin and Epo-Kwick hardner resented by the following reaction.
(Buehler Ltd., USA) in a 5 : 1 ratio, cured for 4–5 h at room
temperature and polished. The thickness of the black nickel and 2Al þ 2OH− þ ZnðOHÞ4 →2½H2 AlO3 − þ Zn0 þ H2↑
electroless nickel deposits was measured on a graduated scale
optical microscope (480×). This zincating layer acts as a good base and activator for
The micro hardness of the coating was measured with a subsequent electroless nickel deposition.
Shimadzu micro hardness tester Model HMV 2000, Kyoto, The electroless nickel is deposited by an autocatalytic chem-
Japan, using a diamond indenter. Vickers Hardness numbers ical reaction between the job surface and plating solution. The
were obtained by averaging five measurements on each spec- metal ion and reducer (hypophosphite) concentration must be
imen with a load of 50 g for 10 s indentation. monitored and controlled closely to maintain the correct ratios
The optical properties, namely solar reflectance and infrared and the overall chemical balance of the plating bath. The de-
emittance of the electroless nickel black coating were measured position rate of electroless nickel is controlled by the

Fig. 1. EDX spectra of electroless nickel coating (a) before and (b) after etching.
858 V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862

Fig. 2. SEM of electroless nickel–phosphorous coating after etching.

temperature, pH and metal ion/reducer concentration of the with below 12% phosphorous are metastable solid solutions
plating solution. Several mechanisms have been proposed for within which high phosphorous species such as Ni3P or Ni5P2
the chemical reactions that occur in hypophosphite reduced exist extensively, or as inclusion in low P content alloys [14].
electroless nickel-plating solutions. The overall chemical re- The surface morphology plays a crucial role in obtaining the
action can be represented as follows— high absorptance coating. The scanning electron micrograph of
etched electroless nickel–phosphorous given in Fig. 2 (a) and
2½H2 PO2 − þ Ni2þ þ H2 O→½HPO3 2− þ Ni0 þ P þ 1=2H2 ↑ (b) at 2000× and at 4000×, respectively. The micrographs show
þ 2H2 O the ‘stalagmite-like’ structure. The morphology of black nickel
depends on the phosphorous contents. The coating with low
The electroless nickel due to the presence of phosphorous phosphorous produces a very pronounced ‘crater’ morphology
can be easily etched by the oxidizing acids to obtain the high and with high phosphorous a ‘stalagmite-like’ morphology.
absorptance black surface. This ultra black Ni–P coating that Ni–P alloys with a lower phosphorous content are etched more
acts as a very efficient absorber consists of nickel oxides (NiO, completely, with large crater formation as large portions of the
Ni2O3) and some nickel phosphate. alloy are dissolved [14]. As the P content increases, it is more
The EDX spectra of electroless nickel coating before and difficult for large swaths of Ni–P to be etched and hence narrow
after etching is shown in Fig. 1. There is slight reduction in the sharper features are observed.
peak height of nickel and phosphorous that shows that both the The high absorptance of present coatings is associated with
nickel and phosphorous are selectively etched during blacken- unique surface morphology consisting of a dense array of mi-
ing process. The electroless nickel obtained under optimal croscopic, conical pores perpendicular to the surface. This
conditions showed nickel contents 93.15% and phosphorous structure produce by selective etching of Ni–P acts as light traps
6.81% by weight. The etched coating showed lower nickel and and is capable of absorbing 99.5% light in solar region (300–
phosphorous contents (nickel 90.06%, phosphorous 5.75% and 2300 nm). The pore diameter, pore depth and pore spacing range
oxygen 4.19% by weight). from a fraction of micrometer to a few micrometers or about a
fraction to several wavelengths of light. Consequently, the pores
3.2. Morphological studies trap any incident light in wide spectral range. The black color of
Ni–P coating is due to this unique surface morphology as well to
The autocatalytic electroless nickel–phosphorous deposits the formation of nickel oxides (NiO, Ni2O3) and some nickel
with above 12% P, are amorphous. However, the coatings phosphate [19,20].

Fig. 3. Cross section of as electroless nickel sample (a) before (b) after etching.
V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862 859

1.00
Cross sectional views of the electroless nickel coating as
obtained and after etching presented in Fig. 3. The electroless
nickel as obtained shows very uniform deposition. The coating
after etching shows a peak to trough height of 6–7 μm, with a top

Absorptance
0.96
layer of Ni–P black oxide being ∼0.7 μm. However, the thick-
ness of this top layer in excess of 1.0 μm is powdery and non-
adherent.
0.92

Table 1
Effect of process conditions on the optical properties of black electroless nickel 0.88
4 5 6 7 8 9 10 11
Variable Infrared emittance Solar absorptance
Molar Concentration
Solution-1
1. Effect of conc. of blackening solution (Time: 40 s, temperature: 40 °C) Fig. 4. Influence of conc. of nitric acid on the solar absorptance of the coating.
10 M 0.77 0.993
9M 0.76 0.995
8M 0.59 0.965
7M 0.40 0.950 3.3. Process optimization
6M 0.30 0.915
5M 0.26 0.900 Process optimization was carried out by the investigation of
2. Effect of solution temperature (Concentration 9 M, time: 40 s) the influence of process parameters on the physico-optical prop-
30 °C 0.48 0.957
erties of the coating. The effects of process conditions on the
40 °C 0.76 0.995
50 °C 0.82 0.992 optical properties of black electroless nickel are presented in
60 °C 0.74 0.985 Table 1. The values obtained under optimum conditions are
70 °C 0.75 0.976 shown in bold italics.
3. Effect of etching time (Conc.: 9 M, temperature: 40 °C)
10 s 0.39 0.925
3.3.1. Effect of concentration of blackening solutions
20 s 0.62 0.962
30 s 0.72 0.987 Initial experiments were carried out with number of etching/
40 s 0.76 0.995 blackening formulations. Thereafter based on the good results
50–180 s 0.76 0.990 the following three etching solutions were selected for study in
detail. The optimal concentration of these solutions is given in
Solution-2
the brackets.
1. Effect of solution temperature
30 °C 0.34 0.825
40 °C 0.60 0.836 Solution-1 Nitric acid (9 M)
50 °C 0.54 0.876 Solution-2 Sulphuric (6 M) + nitric acid (4 M)
60 °C 0.43 0.971 Solution-3 Nitric acid (1.1 M) + sulphuric acid (0.3 M) +
70 °C 0.36 0.971
potassium permanganate (0.1 M)
2. Effect of etching time (Conc.: 6 M sulphuric acid + 4 M nitric acid,
temperature: 40 °C)
10 s 0.32 0.896 Experiments with solution-1 were carried out at different
20 s 0.43 0.971 concentrations of nitric acid ranging from 5 to 10 M and the
30 s 0.61 0.964 absorptance values were measured. Fig. 4 shows the plots of
40 s 0.59 0.867
solar absorptance of coating vs. concentration of nitric acid used
50 s 0.59 0.865
for etching. It is noted that the solar absorptance of coating
Solution-3 increases as the concentration of nitric acid increases and the
1. Effect of etching solution temperature (Conc.: nitric acid − 1.1 M + blackening is completed in the lesser time. The optimum con-
sulphuric acid −0.3 M + potassium permanganate −0.1 M, time: 50 s) centration of nitric acid to get uniform black coating with high
30 °C 0.37 0.827
solar absorptance is 9 M.
40 °C 0.38 0.878
50 °C 0.41 0.833 In solution 2, the concentration of sulphuric acid N 6 M is not
60 °C 0.46 0.815 found to influence the absorptance value of electroless nickel
70 °C 0.49 0.805 black coating. However, the solar absorptance of the resulting
2. Effect of etching time (Conc.: nitric acid − 1.1 M + sulphuric acid −0.3 M + black coating increases with increase in the concentration of
potassium permanganate − 0.1 M, temperature: 40 °C)
nitric acid up to 4 M. thereafter, the reaction becomes too fast
10 s 0.24 0.812
20 s 0.26 0.820 and the patchy deposits are formed. The optimum concentration
30 s 0.33 0.848 of solution-2 (6 M sulphuric acid and 4 M nitric acid) provides
40 s 0.38 0.865 good uniform black coating with solar absorptance value of 0.97.
50 s 0.38 0.878 Solution-3 provides slow blackening of electroless nickel
60 s 0.46 0.857
with a solar absorptance value of the order of 0.88. The optimum
860 V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862

results are obtained at a concentration of nitric acid (1.1 M) + Table 2


sulphuric acid (0.3 M) + potassium permanganate (0.1 M). At the Mass reduction of coating during etching process under optimized condition
(surface area: 20 cm2, coating density: 8 g/cm3)
higher concentration of potassium permanganate a powdery
deposits are formed and no improvement in the solar ab- Etching Coating Mass Percent Mass loss mg Thickness loss
solution/ mass loss mass loss (cm− 2/s− 1) under optimal
sorptance value was observed with the sulphuric acid concen- time (mg) (mg) conditions (μm)
tration beyond 0.3 M.
Solution 538 83 15.4 0.103 5.19
Out of above three solutions, nitric acid (9 M) was found to
1/40 s
provide highest solar absorptance value of the order of 0.995. Solution 526 79 15.0 0.197 4.94
As the high solar absorptance values under optimum conditions 2/20 s
were obtained with solution-1, it was selected for further studies. Solution 272 12 4.4 0.012 0.75
3/50 s
3.3.2. Effect of pH of Electroless nickel solution
The pH of the solution should be regulated to obtain the most 3.3.3. Effect of thickness of electroless nickel deposit
favorable results. The phosphorous contents of the electroless The thickness of nickel deposit plays a significant role in
nickel deposits depend upon the pH value of the solution. At achieving the higher absorptance value of coating after
high pH, phosphorous content decreases, but the solution may blackening. Strong oxidizing acids are used for etching of elec-
decompose and at low pH value phosphorous contents are higher troless nickel to get the high solar absorptance coating. During
and the resultant coating has high stress [14]. The influence of blackening process, the thickness of electroless nickel decreases
electroless nickel plating solution pH on the solar absorptance due to etching. Hence, higher thickness of electroless nickel
value of subsequent blackening process was investigated. Ex- coating is required. At lower coating thickness b 15 μm, the
periments were conducted in the pH range 4.0–5.5. The results black coating formed are non-uniform. The optimum coating
are shown in Fig. 5. At lower pH of 4.0, solar absorptance of thickness of electroless nickel is 30 ± 2 μm to achieve the ultra
black coating was lower (0.98) and at pH 5.5 and above the high solar absorptance after etching.
electroless nickel plating solution starts decomposing. The The data on mass reduction of electroless nickel coating
optimum results were obtained at a solution pH value of 4.7. during etching process with different solutions is presented in
Phosphorous contents affect the etching behavior and prop- Table 2. About 5 μm average thickness of electroless nickel is
erties of nickel black coating. As the phosphorous contents in reduced during etching with solution-1 and solution-2. While the
the electroless coating increases higher concentration of reduction in average thickness with solution-3 is negligible
oxidizing acids are required for blackening to achieve a high when compared with other two solutions. It may, however, be
solar absorptance. Further, higher is the phosphorous content in noted that the etching process is not uniform, formation of
electroless nickel more is its resistant to acid etching. Higher notches and valley with average height of notches ∼6.6 μm is
phosphorous Ni–P alloys are not suitable for blackening due to observed during etching with solution-1. The thickness of
their high resistance to etching solutions. When the phospho- electroless nickel should therefore have margins in addition to
rous contents in the electroless nickel exceeds 14%, it becomes thickness reduction and notches formation during etching.
extremely difficult to etch the coating even with high con-
centration of oxidizing acids. Further, the solar absorptance 3.3.4. Effect of temperature of etching solution
value of the black coating decreases with increase in the phos- The etching solution temperature plays an important role in
phorous contents in electroless nickel. Lower the initial phos- blackening of electroless nickel coating. Experiments were
phorous content in the electroless nickel, the greater the extent conducted at the operating temperature range of 30–80 °C for
of the etching and lower the reflectance of the resulting surface. different etching solutions. The influence of operating temper-
ature on the solar absorptance value of the resultant coating is
1.00
0.99
Absorptance

0.94
Absorptance

0.99

0.89

0.98 0.84

0.79
20 30 40 50 60 70 80
0.97
3.8 4.0 4.2 4.4 4.6 4.8 5.0 Temperature (°C)
pH Solution 1 Solution 2 Solution 3

Fig. 5. Influence of pH of Electroless nickel solution on the solar absorptance of Fig. 6. Influence of operating temperature of different etching solutions on the
the coating. absorptance value of the coating.
V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862 861

1.00 uniform without patches or discoloration. The black electroless


nickel was found to have excellent adhesion in the scotch tape
0.95 peel test. No detachment of coating was observed from any
Absorptance

point.
0.90 The average thickness of blackened electroless nickel and
electroless nickel obtained at optimum conditions was measured
0.85
as 25 and 30 μm, respectively.
Micro hardness of the coating shows a minor drop of about
10–15 VHN in micro hardness of electroless nickel after black-
0.80
0 10 20 30 40 50 60 ening. The average micro hardness for black electroless nickel
Time (Seconds) was 575 VHN.
Solution 1 Solution 2 Solution 3
4.2. Corrosion resistance test
Fig. 7. Influence of etching time of different solutions on the absorptance value
of the coating.
To evaluate the resistance of black electroless nickel coating
against the corrosive ground atmosphere, an accelerated cor-
shown in Fig. 6. At the low operating temperatures the etching rosion test was conducted. The test coupons were immersed in a
rate of coating is slow and the solar absorptance of resultant 5% solution of sodium chloride at pH 7.0, and the time taken for
coatings is lower. As the operating temperature of etching discoloration of the coating or formation of corrosion spots was
solution increases the process time to obtain high solar carefully observed. The test indicated adequate stability because
absorptance coating decreases. However, at higher temperatures no discoloration, corrosion spots or degradation in the ab-
the rate of etching reaction becomes too high to control the sorptance value of coating was noticed after 7 days of im-
process. The powdery deposits of black coating obtained due to mersion. However a minor drop of 3.5% in absorptance value of
heavy dissolution of electroless nickel. A moderate etching the coating was observed after 15 days of immersion.
temperature has to be selected to achieve uniform blackening of
coating. The optimum operating temperatures of solution-1, 2 4.3. Thermal stability test
and 3 for obtaining high absorptance coating are 40, 60 and
40 °C, respectively. The black electroless nickel coatings are used in some of the
high heat dissipating parts where the temperature is likely to go
3.3.5. Effect of blackening time around 200 °C for an extended period. The thermal stability test
Because very strong acid solutions are used for blackening consists of heating of black electroless nickel test coupons in an
of electroless nickel, the etching time is an important oven for 48 h. The temperature of the oven was maintained at
parameter to control the quality of electroless nickel 200 ± 2 °C. The test specimens were then examined visually for
blackening. The etching time affects the appearance, unifor- any degradation and their optical properties were measured. No
mity and optical properties of electroless nickel black coating. degradation in physical appearance and no change in optical
The etching time range for different solutions are given properties before and after test were noticed.
below:
4.4. Humidity test
Solution-1 40–50 s
Solution-2 20–30 s The humidity test was carried out to examine the resistance of
Solution-3 40–50 s the coating to the corrosive pre-launch atmosphere. The test was
conducted in a thermostatically controlled humidity chamber for
At the lower etching time non-uniform black coating with 48 h. A relative humidity of 95% ± 0.5% was maintained in the
low solar absorptance value is obtained. The etching beyond the chamber at 50 ± 1 °C. The test specimens were then examined
given range of time results into powdery coating or peeling from visually, and their optical properties were measured. No change
the edges due to excessive dissolution of coating. Etching time is in visual and optical properties was observed after the test.
however, more tolerable for solution-1 and this solution can be
operated up to 180 s without significant drop in the solar 4.5. Thermal cycling test
absorptance (Table 1). The effect of etching time on absorptance
value of nickel black coating is shown in Fig. 7. A satellite in orbit becomes hot when exposed to direct sun
light and experiences low temperature when it dives in to earth's
4. Testing and evaluation shadow. The thermal cycling test is designed to evaluate the
effect of cycling temperature on the deposit that is likely to be
4.1. Visual inspection and mechanical characterization encountered throughout the life span of a spacecraft. The test
was conducted in thermostatically controlled hot and cold
All the black nickel coated specimens were examined vi- chambers. A total of 100 cycles was applied. A cycle consists of
sually with 4× magnification for any defect. The coatings were placing the samples into a chamber operating at − 45 °C for
862 V. Saxena et al. / Surface & Coatings Technology 201 (2006) 855–862

0.8
5. Conclusion

0.6 A process of ultra black electroless nickel black coating on


aluminum substrate is described. The ultra high absorptance of
Reflectance

the coatings is associated with unique surface morphology and


0.4
formation of nickel oxides (NiO, Ni2O3) and some nickel
phosphate. The surface morphology consisting of a dense array
0.2 of microscopic, conical pores perpendicular to the surface. This
structure produce by selective etch act as light traps, is capable
of absorbing over 99.5% light in solar region. The coating has
0 excellent adhesion and stability in adverse space conditions.
200 700 1200 1700 2200
These surfaces are extremely suitable in improving the ab-
Wavelength (nm)
sorptance of thermal detectors and to minimize the effect of
Fig. 8. Solar reflectance spectra of black electroless nickel. stray and scattered light in optical instruments and sensors.
The process of surface blackening and the relationship of
chemical composition and physical characteristics of the etched
5 min, bringing them to an ambient temperature with a dwell of surface to the original plating condition and the etching para-
15 min and shifting them to a hot chamber at 80 °C for 5 min. meters have been investigated. Lower the initial phosphorous
After thermal cycling, the test specimens were inspected visually content in the electroless nickel, the greater the extent of the
and their optical properties were measured. No degradation in etching and higher absorptance of the resulting surface. The
physical appearance and optical properties was noticed after the test. coating formed below 6% phosphorous show poor corrosion
resistance without any appreciable improvement in absorptance
4.6. Thermo-vacuum performance test value.

To further examine the effect of cycling temperature in the References


simulated space environment, the electroless nickel black-coated
specimens were subjected to a thermo-vacuum hot and cold soak [1] A.K. Sharma, A. Rajendra, R.L. Gayathri, Alum. Trans. 1 (No.1) (1999)
test. The test consists of lowering the temperature of the −45 °C 155.
[2] A.K. Sharma, Trans. Inst. Met. Finish. 67 (1989) 87.
for 2 h and then rising the temperature to 80 °C for another 2 h. A [3] E.A. Stark Jr., J.T. Staley, Prog. Aerosp. Sci. 32 (1995) 131.
total of 10 cycles of hot and cold soak were applied. A vacuum [4] A.K. Mukhopadhyay, A.K. Sharma, Surf. Coat. Technol. 92 (1997) 212.
level of 10− 5 Torr was maintained inside the chamber during the [5] J.P. Celis, D. Drees, M.Z. Huq, P.Q. Wu, M. De bonte, Surf. Coat. Technol.
entire period of testing. After the test, coupons were examined 113 (1999) 165.
under 4× magnification and their optical properties were [6] A.K. Sharma, Surf. Eng. 21 (No. 3) (2005) 249.
[7] S. Wernick, R. Pinner, The Surface Treatment and Finishing of Aluminum
measured. No degradation of any kind was noticed. and its Alloys, 4th edition, vol. 1, Robert Draper Ltd., Teddington, UK,
1972, p. 3.
4.7. Measurement of optical properties [8] C. Kerr, D. Barker, F.C. Walsh, Trans. Inst. Met. Finish. 79 (2001) 41.
[9] J.K. Dennis, T.E. Such, Nickel and Chromium Plating, 3rd edition,
The present studies herein undertaken to develop ultra high Woodhead Publishing Ltd., Cambridge, England, 1993, p. 280.
[10] S.S. Tulsi, Trans. Inst. Met. Finish. 64 (1996) 73.
absorptance electroless nickel black coating. The measurement [11] S.W. Court, B.D. Barker, F.C. Walsh, Trans. Inst. Met. Finish. 78 (2000)
of optical properties viz., solar absorptance and infrared emit- 157.
tance, of the present coating developed is of paramount im- [12] G. Gawrilov, Chemical (Electroless) Nickel Plating, Portcullis Press,
portance. The optical properties of the black electroless nickel Redhill, Surrey, England, 1979, p. 28.
were measured before and after all the environment tests (hu- [13] C.E. Johnson, Met. Finish. 78 (1980) 21.
[14] R.J.C. Brown, P.J. Brewer, M.J.T. Milton, J. Mater. Chem. 12 (2002) 2749.
midity, thermal cycling, thermo vacuum performance and ther- [15] S.R. Meier, Proc. of SPIC, Bellingham, WA, vol. 5526, 2004, p. 164.
mal stability tests). A solar reflectometer and emissometer provides [16] A.K. Sharma, H. Bhojaraj, V.K. Kaila, H. Narayanamurthy, Met. Finish. 95
average value digitally in the entire solar and infrared region. (No. 12) (1997) 14.
The solar reflectance spectra of the coating in 200–2300 nm region [17] K.P. Thurlow, Trans. Inst. Met. Finish. 67 (1989) 82.
[18] R. Uma Rani, A.K. Sharma, S.M. Mayanna, H. Bhojraj, D.R. Bhandari,
is shown in Fig. 8.
Surf. Eng. 21 (No.3) (2005) 198.
The influence of various operating parameters on the optical [19] S.N. Kumar, L.K. Malhotra, K.L. Chopra, Sol. Energy Mater. 3 (1980)
properties of the coating has been discussed under process 519.
optimization. No change in optical properties of the black elec- [20] M. Wicerzbicka, A. Malecki, J. Therm. Anal. Calorim. 55 (1999) 981.
troless nickel obtained under optimum conditions was observed
after environment tests.