June 2012

Ben-Gurion University of the Negev

Faculty of Engineering Sciences
Faculty Unit of Energy Engineering

By: Oleg Shkolnik
Supervisor: Prof. Daniel Feuermann

Photothermal coatings based on functional
nanomaterials for the efficient conversion of solar
energy


Supported by: Ministry of Energy and Water Resources

Outline



Theoretical short introduction and motivation
Project description
Review of different types of coatings
Experimental setup and methodology
Current results and future experiments







-

=

= (

)














Thermal conductivity of various
materials at 0 C
Material k ( W/ m C )
Copper 385
Aluminum 202
Carbon steel 1% C 43
Glass wool 0.0038
Air 0.024

= according to Kirchhoffs law
=
1

1
(
1
4

2
4
)

0
Boltzmann law
+ + = 1 according to energy balance
Net heat transfer
from surface
1

What is selective coating


A selective absorber coating or material is a thin layer (of
the order of m) on the surface, or a material which exhibits
optical properties that drastically vary from one spectral
region to another


The solar spectrum and the re-radiated spectrum of the hot
absorber are separated at relatively low temperature of the
absorber. However, the higher the temperature of the
surface the more the absorbed solar radiation and the
emitted spectra overlap



Selective coating was pioneered by Tabor in 1956 in Israel



0.0
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0.9
1.0
0 1000 2000 3000 4000 5000
e
f
f
i
c
i
e
n
c
y
(
%
)

wavelength(nm)
C=100
T=550 C
0.0
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0.9
1.0
0 1000 2000 3000 4000 5000
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f
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i
c
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c
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(
%
)

wavelength(nm)
C=25
T=800 C
0 0
( ) (0.95) (0.07) (0.95) (0.07)
cr cr
cr cr
cr sun sun bb bb
q C I d C I d I d I d


o c c c

= +
} } } }
Evaluation of critical wavelength and efficiency estimation

Selective coating the complete project

This work is a part of a collaborative project of
developing thin nanocomposite layers for high
temperature (above 500 C)

The samples are prepared at Hebrew University
at chemical department by two groups of
researchers (Mandler and Magasi et al.,)




The Electro-Dynamic analysis of particles mixture is
performed at TAU Electrical Engineering department by
Steinberg et al.


The optical properties measured at Sede Boqer and TAU
( Feuermann and Kribus et al.,)

`
Goals of the project
The global purpose of this research is to construct a spectrally selective
ceramic matrix with embedded nanoparticles for photo thermal conversion,
stable at high temperature applications.

Each group has its specific requirements to meet.
Hebrew University group :
Solar absorption at 300-2500 nm range (AM 1.5),
above 95% of the total energy.
Low thermal emittance < 0.1
The coating will be designed for continuous
use at a temp >500 C (in air)



Optical properties of selective coatings
BGU :
Detailed measurements of spectral and angular reflectance at ambient
and elevated temperatures
Measurements of solar absorptance at high solar concentration
TAU:
Prof. Kribus Group
Measuring the of emissivity
IR Camera 214 m

Pyroelectric sensor 0.316 m

Prof. Steiberg group
Theoretical calculations based on use
Maxwell equations in order to evaluate
the by knowing the dielectric
constant of the absorbing particles
Basics assumptions:
Homogeneous distribution
particles should be one 0.1-0.2 of
the wavelength
Spherical, ellipsoidal, or needle
like particles


Types of absorbers

1. Intrinsic absorbers- e.g., HfC(Hafnium Carbide ): two
categories of materials fall into this group : transition metals
and semiconductors. Unfortunately most selective metals
exhibit the cutting edge, of good absorber to pore emitter
too earlier at the solar spectrum and therefore not suitable
for solar applications


Carl M. Lampert Solar Enegy materials 1( 1979)






2. Multilayer absorbers (e.g., Al
2
0
3
/Mo/ Al
2
0
3
):

Multilayer thin films are dielectric-metal combinations which act
like a selective filter for energy absorption
Particular wavelengths of solar energy are absorbed by multiple
reflections in the dielectric-metal layers
Such coatings are commonly produced by sputter deposition
technologies with AR layer on the top
N. Selvakumar, Harish C. Barshilia, Materials & Solar Cells (2011)



3. Optical trapping: it is possible to produce a
surface with a such roughness that will absorb
the visible part of the solar spectrum by pure
geometrical means while being opaque
to the infrared spectrum













4. Metal dielectric (cermet): highly
absorbing metal dielectric
composites consisting of nano or
micro scale particles embedded in a
dielectric or ceramic matrix






Structure of cermet:

thin protective layer to prevent diffusion

single layer with uniform particles distribution

single layer with graded particles distribution

double layer - according to fundamental modeling it has higher photo-thermal
conversion efficiency


Cermet types and structures


Offers high degree of flexibility , solar selectivity can be optimized by proper
choice of coating thickness

Particle size- it is possible to shift the absorbing and scattering cutoffs to higher
wavelengths when the particle radius increases

Possible to predict optical properties using effective medium theories for example
the optimum pore diameter d
p
=0.08 m of nickel pigmented alumina coatings
have been determined

Usage at broad range of temperatures

In addition solar absorbance can be boosted with a proper choice of substrates and
AR layer.

After a long research and development in solar materials, the cermet remains one of
the best and promising candidates for high temperature application
Advantages of cermets over other candidates for
high temperature applications



International Energy Agency (IEA) performance criterion (PC) developed for a flat-plate
collector selective absorber testing.

=

+ 0.25 0.05
lifetime of at least 25 years and decrease in the annual solar fraction of 5%

Service lifetime testing for this criterion is performed by exposing the absorber coating for
200 h at 250C
If the material survives , it is then exposed for 75 h at 300 C hand roll followed by 600 h at
40 C and 95 %relative humidity

No similar criterion has been developed for testing the service lifetime of high temperature
absorbers for CSP.

Degradation of the high temperature absorbers usually causes increasing emittance ; in
addition while the emittance of many materials after exposure to high temperature does
not return to the original emittance measured ( e.g., paint), for some materials the
emittance changes at high temperature and returns to the original value






Long term stability


Different matrices were investigated for CERMET layers, more exactly 2 categories
of matrices (silica and alumina). Both alumina and silica matrices are transparent
to IR and are stable at high temperature.


Black coatings were prepared by dispersing black pigment (black 26) in the
different matrices, adding dispersant and additives. The coatings were dried at
750C during 1 hour under air.








SEM of alumina film with Black 26

First set of experiments:

Solar irradiation one sun

Ambient temperature

Measurements of 4 samples


s
i


wet thickness 40 m

wet thickness 6 m
achieve
1000K
experimental setup

4 side faces
of furnace
back face of
furnace
Front face Total loss
heat loss by convection
5.7 W 2 W 23.9 W 31.6 W
heat loss by radiation
6.6 W 2.4 W 13.6 W 22.6 W
Results for HU samples

s
Azimuthal effects inside the specular region
rotating the sample
to observe any difference
in surface structure

s
The structure of the surface has obviously a strong effect

s
rotating the sample
to observe any difference
in surface structure
Azimuthal effects outside the specular region

s
polar angle effect around specular direction
B-CZ-10.1A ferro 8m
0
10
20
30
40
50
60
70
0 10 20 30 40 50 60 70
polar angle s(deg)
r
e
f
l
e
c
t
a
n
c
e

(
%
)
i=30 s=0
i=45 s=0
here

i
=
s
Specular effects in polar direction (
s
) at two
incidence angles
We simply average the directional reflectance over
the wavelengths. This is of course not a correct
measure but should give some qualitative indication
of a relative specularity of the different samples.
all the results on one graph
polar angle effect at i=30 s=0
0
50
100
150
200
250
0 10 20 30 40 50 60 70
polar angle s (deg)
r
e
f
l
e
c
t
a
n
c
e
(
%
)
B-CZ-STS-10.2 4.7m
B-CZ-STS-10.2A 6m
B-CZ-10.2B 5.9m
B-CZ-STS-9.2 2.6m
B-CZ-10.1 4m
B-CZ-10.1A 8m

s
15
45

s
=60
30
MS 1.3 (two layers) at elevated temperature of 600K
we had to cut off at 1100nm because thermal radiation was too
large at the longer wavelengths.
0
200
400
600
800
1000
1200
1400
1600
1800
900 1000 1100 1200 1300 1400 1500 1600 1700
r
e
l
.

i
n
t
e
n
s
i
t
y

(
%
)

wavelength (nm)
relative intensity from MS13 sample in the dark
compared to gray reference under illumination
we get 10 times the intensity from thermal
radiation than from light reflected
MS 1.3 at 600K
attempt to increase signal to noise ratio by
optics
better means of measuring temperature
measurement in the solar furnace (to obtain
directly) and will be closer to realistic
conditions.
at high temperatures measurements
even a very bright lamp is not sufficient
while dealing with very absorbing samples

ultimately will
be used in solar
furnace
Sample inside solar furnace
The next day photos after heating to max temperature 430 C
Experimental setup using a PCX Condenser Lens 125mm Diam x
500mm Focal Length
A) we have considered using a lens and the sun
Lens position
Problem:
Stability of direct beam solar radiation.
Ephemeral nature of solarradiation.






Region that the sensor
sees
Light spot that sensor
sees
Placing the sample at focal plane
Sample position
What did we achieve?

much higher intensity
light spot completely in the measured region
experiments at wide angles
Hopefully solved uniformity problem

sample
holder
sample
holder
Region that the sensor
sees
Light spot that sensor
sees

s

0
5
10
15
20
25
30
35
40
45
400 600 800 1000 1200 1400 1600 1800
r
e
f
l
e
c
t
a
n
c
e
(
%
)

wavelength(nm)
polar angle effect i=30 s=0
MS-CZ- 17C 8.7m
s=-10
s=0
s=10
s=20
s=30
s=40
s=50
s=60

s
0
5
10
15
20
25
30
35
40
-10 0 10 20 30 40 50 60 70
r
e
f
l
e
c
t
a
n
c
e
(
%
)

polar angle s (deg)
polar angle effect i=30 s=0-corrected by solar spectrum
17A17F 2.5 15.7m
17B - 2.5m
17F - 4.8m
17A - 5.16m
17C - 8.7m
17E - 9.1m
17D - 15.7m
sample
reflectance in non-
specular region
reflectance in specular
region
weighted average
reflectance over both regions
absorbtance
(
i
=30)
17A -5.16m 0.050 0.198 0.053 0.9470.004
17B-2.5m 0.067 0.223 0.070 0.9300.005
17C-8.7m 0.050 0.161 0.053 0.9470.004
17D-15.7m 0.043 0.158 0.045 0.9550.003
17E-9.1m 0.043 0.170 0.046 0.9540.003
17F-4.8m 0.044 0.183 0.046 0.9540.003
Acknowledgments

This research is supported by the Ministry of energy
and water within the framework of the program of
scholarships in the field of renewable energy.

I would like to acknowledge my supervisor Prof. Daniel
Feuermann for invaluable support, guidance and
scientific assistance.
Thank you


for your attention