Professional Documents
Culture Documents
Solar Energy
Solar Energy
Solar Energy Materials and Solar Cells 30 (1993) 285-290 and Solar Cells
North-Holland
W a n Taixin a, Z h a o Q i n h u a a a n d C h e n g Xiaoxi b
" Gansu Natural Energy Research Institute (GNERI), Gansu Academy of science, Lanzhou,
Gansu, P.R. China
b The Research Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou, Gansu,
P.R. China
A solar selective absorbing surface is introduced processed by the alternating current oxida-
tion method on cold-rolled milled steel plate. T h e performance of the surface, such as the solar
absorptance a, the thermal infrared emittance e, the durability aging and the humidity
resistance was tested and evaluated. Furthermore, the morphology and constitution of the solar
absorbing surface were analyzed by transmission electron microscopy (TEM), A u g e r electron
spectroscopy (AES), and M6ssbauer spectroscopy. The results showed that the alternating
current oxidation method can prepare solar selective absorbing surfaces that meet the require-
ments for use in low temperature solar applications.
I. I n t r o d u c t i o n
In China, a black paint coating was often used for absorber plates for domestic
solar thermal collectors. This painted coating was not a selective surface, and the
solar absorptance a and the thermal emittance • were almost equal. An ideal
selective absorbing surface would be one that completely absorbes the incident
solar energy with wavelength < 2 ~m ( a = 1), it should not emit radiation in the
infrared region (wavelength > 2 Ixm) and the total hemispherical emittance at the
operating temperature would equal zero, • = 0 [1,2]. Of course, such an ideal
surface coating was not achievable, but it was possible to produce selective
surfaces having high solar absorptance and low long-wave emittance [3,4]. In
conventional practice one attempted to maximize a, minimize •, and obtained a
high ale ratio. However, in practical systems, it was shown that the collector
efficiency at relatively low temperature was generally more sensitive to a than to
• , which was not only to enhance a but also reduced •. The preparation process to
achieve these selective surfaces was expensive and complicated. This work presents
an alternating current oxidation method for a preparing selective surface, the
procedure was simple and the cost was low. Yet the results show that this basic
preparation meets the needs for low temperature solar utilization.
Table 1
Effect of substrate surface roughness on a and
Roughness a
Cold-rolled (about 10 txm) 0.93 0.31
Grinding surface on
180# paper ( < 10 ~zm) 0.90 0.32
Grinding surface on
240# paper ( < 6 ~zm) 0.87 0.32
The constitution analysis was carried out using a model CEMS M6ssbauer
spectroscope. The internal conversion electron M6ssbauer spectrum (CEMS) at
room temperature was observed on a constant acceleration drive spectrometer
using a 15 mCi 57Co(Pd) radioactive source and graduating by cx-Fe of thickness 25
txm. The CEMS measurement was performed with a gas-flow proportional counter,
with the flow about 4-5 bubbles/minutes. The working gas was a mixture of 95%
helium and 5% methane. The range of channels was 512. The spectrum was
analyzed by the A W M I (algorithm without matrix inversion) program, on an IBM
P C / X T microcomputer.
The chemical composition of the surface film was measured with a model
PHI & SIMS 3500 system. AIES depth profiling was made using a differentially
pumped ion gun with an Ar + ion beam at 3 keV and 0.5 A / c m z current density in
2.5 × 10 -8 Torr argon. The system pressure was 1 × 10 - l ° Torr.
Any oil contamination and rust on the substrate can cause discoloration or
reduce adhesiveness of the oxide layer to the substrate surface. Therefore, it was
important to clean the substrate thoroughly before the oxidation step.
Table 1 showed that a was increased by increasing the surface roughness in the
range 5-10 Ixm, but it did not cause a significant difference in E. If the roughness
was decreased, it would be difficult to obtain the result in blackening. Therefore,
the cold-rolled substrate surface of the steel can meet the needs of the oxidized
blackening, not perform to finish treatment again.
The effect of the oxidation medium concentration, temperature, current density,
and time on performance of the oxide surface was determined by the experiments
in the following.
It was difficult to obtain a black surface through oxidation when the medium
concentration was less than 8%. But if it was above 12%, the adhesiveness of the
oxide to the substrate surface would be less.
The experimental results showed that temperature had a large effect on the
performance of the oxide surface. For example, at room temperature, it was
possible to obtain an oxidized surface with a = 0.94 and • = 0.31. But when the
temperature was below 20°C, the oxidizing process needed a longer time and
288 Wan Taixin et al. / A solar selectit'e absorbing surf hoe
surface blackening was not easy. If the temperature was up to 50°C, the absorp-
tance cr equals 0.92 which was the same as at the room temperature, but the
thermal emittance had sharply increased to E = 0.60. The rising temperature can
accelerate the rate of metallic ion oxidation, so as to make the oxidized surface
thick and rough, which led to the emittance E rising at last.
The oxidizing process required a longer time when current density was below 10
A / d m 2. However, for a density above 15 A / d i n 2, it led to a rise in bath
temperature because of electrode heating. The results was a poor oxide surface.
If the oxidizing time was less than 30 minutes, the oxide surface had a brown
appearance and the absorptance a was lower. The oxide film thickness was about
2.0 ~zm and it did not increase even though the oxidizing time was continued for 50
minutes. There was no further effect on the optical performance of the oxide
surface.
The samples for oxidation were switched alternately as anode and cathode.
Therefore, the desired oxide surface could be achieved on both samples simultane-
ously. It was aggressive and lost metallic ions when the sample was the anode. And
vice versa, when it was converted to the cathode, the metallic ions were oxidized
and deposited on the surface of the samples to form an oxide film. While the
sample was switched to anode again, the next corrosion circulations started in the
thinnest part of the oxide film. By repeating the above cycle, there was a dense and
rough oxide film formed on both substrate surfaces. The resulting film was able to
absorb solar radiation efficiently. The efficient absorption resulted from the
multi-reflected and scattered sunlight which came from the rough features of the
oxidized surface. The oxidation speed slowed and the film growth stopped when
the film thickness reached about 2.0 ~m. The whole procedure took about 40
minutes. The oxide film appeared black brown and the thickness was about 2.0 ixm
with a = 0.92-0.94, E = 0.30-0.32.
As shown in fig. 1, the morphology of the film was observed under high
magnification with transmission electron micrography (TEM). A spherical particle
structure was apparent with particles about 0.25 ~ m in diameter, compactly and
uniformly distributed on the surface. Auger electron spectroscopy (AES) and
M6ssbauer spectroscopy (CEMS) analysis showed that the structure was 46.93%
Fe and 47.22% O. The main phase included F e O O H , r-Fe203, Fe304 and ferrite.
The TEM analysis showed that the size of particle in the oxide film constitution
was of the same order of magnitude as the solar spectral wavelength. This will
increase the reflection of the solar radiation and increase the absorption of the
solar energy. In addition, the structure, which consisted of the uniform size and
rank compactly spherical particles, made the longer wavelength to be easy trans-
mitted and the thermal infrared emission was decreased as a result.
The experimental results showed that the oxide surface still appeared as black
brown after ultraviolet light accelerated aging for 240 hours, the absorptance a
was in the range of 0.92-0.93, and the emittance • was in the range of 0.30-0.32.
The results are near those that were not aged. After undergoing the temperature
aging treatment ( - 30°C to + 100°C for 720 hours), the absorptance only degraded
from cr = 0.93 to cr = 0.91. However, the emittance dropped from • = 0.40 to
Wan Taixin et al. / A solar selective absorbing surface 289
E = 0.26. It should be noted that this drop in emittance can make the ratio of
absorption a to emittance E more favorable for solar heat utilization. This oxide
surface has an excellent aging-resistance that may well be related to their morphol-
ogy with spherical particles on the oxidized surface. The structure in thermody-
namics and energy distribution was well placed to balance and stability.
The oxide surface did not corrode even after exposure to a humidity experiment
for 720 hours. The M6ssbauer spectrum analysis showed that the oxide surface was
made up of Fe304, Fe203, Ferrite and F e O O H . These substances, which were
insoluble in water, would protect the substrate. The compact structure of uniform
spherical particles could act as protecting barrier from corrosion for the surface.
This would increase the moisture resistance of the oxide surface.
6. Conclusion
The selective solar absorbing surface can be prepared on a cold rolled steel
plate by an alternating current oxidation method in the agent with chromium
trioxide. This oxide surface has an excellent aging resistance and humidity resis-
tance. The T E M and CEMS analysis showed that the optical properties and
durability of the oxide surface were related to their composition and morphology.
In addition, the principal advantage over electrode deposited, sputtering, CVD
and spray pyrolysis and so on was the simple produced and the low cost. The
290 Wan Taixin et al. / A solar selectice absorbing sarJace
Acknowledgements
T h e a u t h o r gratefully a c k n o w l e d g e s Ms. F u L i a n d i a n d E n g i n e e r C a o G u i x u n
for p e r f o r m i n g t h e optical testing a n d T E M analysis d o n e in s u p p o r t of this work.
References