Research Proposed:

Ben-Gurion University of the Negev Faculty of Engineering Sciences Faculty Unit of Energy Engineering
Thesis title: Photothermal coatings based on functional nanomaterials for the efficient conversion of solar energy

Department: Engineering Student : Oleg Shkolnik Supervisor: Prof. Daniel Feuermann

Unit: Energy Engineering I.D.: 312874266 Address:

February 2012 Supervisor: Dept. Graduate Committee, Head: 1 Date: Date:

Introduction
Solar energy is not a stable source during seasons of the year, due to atmospheric changes and due to nonuniformity during the day hours [1] mainly influenced by the cosine of incidence angle effect. Nevertheless, it still remains most abundant energy source in the word, while most other of renewable energy sources wind, wave and geothermal energies are characterized by either limited capacity or by significant difficulties in widespread use. In the field of solar-to-thermal energy conversion the motivation is to absorb the maximum fraction of electromagnetic radiation in the visible and near infrared (NIR) parts of solar spectrum, while keeping the thermal losses, the Infra-red (IR) part of spectrum to minimum amount. This can be achieved by selective absorbers. 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. Generally, the absorption (,T) and thermal emittance (,T) at a given wavelength and fixed temperature is a surface property ,which is a function of the material structure, particle sizes, interaction between them and their spatial distribution, as well as pigments. The solar spectrum and the re-radiated spectrum of the hot absorber (Plancks law) are separated due to the 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, and low emissivity of the surface causes low absorption of part of the solar spectrum. A trade off should be found in terms of gain vs. loss capability. Ordinary black paints in comparison with spectrally selective surfaces will exhibit good absorption characteristic over the whole spectrum. Unfortunately such black paint is unable to retain the absorbed energy loosing a big fraction by radiation to the environment. Since radiation heat loss rates are proportional to the forth power of surface temperature in most cases it can not be neglected or prevented by insulation, especially at high temperature applications. Selective coating was pioneered by Tabor [2] in 1956 in Israel, and since then enormous research had been done in that field. Already in the early 80s Niklasson and Grannqvist [3] constructed not grated Co-Al203 ceramic metal (cermet) spectrally selective coating with an Al203 anti reflecting (AR) coating deposited on the top. The results based on the experiments and optimization in terms of thickness and substrate showed 95% absorptance and 10% emittance at 100C; in addition, the measured values were in a good agreement with theoretical results computed using Maxwell-Garnet theory for spherical particles[4].

Scientific Background and reviewing the existing technologies

Existing thermal solar technology is working quite well mostly at a mid temperature range up to 400 C. Scientists and engineers are constantly trying to increase the total efficiency of a system and to decrease the price. The maximum theoretical thermodynamic efficiency (Carnot cycle) is governed by the temperature of the heat transfer fluid (HTF). With regard to the solar-to-thermal industry, in particular concentrating power systems (CSP), the basic process in its simplest way may be divided into three parts. At first solar flux is collected by a receiver and redirected towards the absorber, where the coating insures maximum amount of light capturing and converting to thermal energy to second heat up the HTF while losing the minimum to the environment. Thirdly, the HTF exchanges heat with compressed air, steam or gas to drive a turbine and generator to generate electricity. Nowadays in the power generation field and at industrial scales there exist two major types of collectors: parabolic troughs with one axis tracking the sun (about 90% of CSP total fields installed all over the word) and two axis of tracking flat plate heliostat field and solar tower. In parabolic trough collectors the receiver is a tube coated with a spectrally selective surface of the cermet type. The tube is evacuated via an external glass sleeve to reduce heat losses by convection which are proportional to temperature differences of a collector and the surrounding. The heat transfer fluid used in most generation fields is a synthetic oil. In the case of the heliostat field the collector is mounted at the top of the solar tower. The surface temperatures of the collector may reach 1000 C and molten may be are used as HTF [5].

Absorbers types
Solar absorber coatings (SAC) are divided into several categories and reviewed in details by Lampert [6] and more recently by Kennedy [7] both for low mid and high temperature applications. 1. Intrinsic absorbers (e.g., HfC, MoO3): 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 Seraphin[8]. 2. Multilayer absorbers (e.g., Al203/Mo/ Al203): multilayer thin films are dielectric-metal combinations which act like a selective filter for energy absorption. The desired effect of an interference stack is to trap energy between semi-transparent metal, dielectric and metal alterations. Particular wavelengths of solar energy are absorbed by multiple reflections in the dielectric-metal layers, while other wavelengths not corresponding to the absorption frequency are reflected. Such coatings are commonly produced by sputter deposition technologies with AR layer on the top. 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. 3

4. Metal dielectric (cermet): highly absorbing metal dielectric composites consisting of nano or microscale particles embedded in a dielectric or ceramic matrix. After a long research and development in solar materials, the cermet remains one of the best and promising candidates for high temperature application. Several types of cermets exist: single layer with uniform particles distribution, single layer with graded (maximum at the bottom) particles distribution, or two layer designs where each layer has a different metal volume fraction (of the particles). The feature common to all cermet coatings is that they are deposited on a thin protected layer to prevent diffusion of the substrate into the cermet which may lead to undesired optical properties. Moreover, material type, thickness and type of deposition all of them influence the cermet optical properties [9]. The second common feature of the coating is anti reflecting (AR) coating, often Al203, on the top to increase the absorptivity and in some cases to prevent oxidation. To summarize the existing technology and selective surface and according to Kennedys report [10] at 14th Biennial CSP Solar PACES( Solar power and Chemical Systems ) symposium in Las Vegas in 2008 "none of the existing coatings have proven to be stable at air at 400 C".According to current data published by Selvajumar , Harish and Barshilia [11] the maximum values of absorptivity achieved today is 0.96 and the minimum value of emissivity is 0.07.

Thesis work objectives:

The project "Photothermal coatings based on functional nanomaterials for the efficient conversion of solar energy" is a part of a collaborative activity of developing thin high temperature (above 500 C) nanocomposite layers for CSP systems. The samples are prepared at Hebrew University by Mandler and Magasi et al., while the optical properties measured at BGU Sede Boqer campus and TAU by Feuermann and Kribus et al. The final and main purpose of this research is to construct spectrally selective ceramic matrix with embedded nanoparticles stable at high temperature applications. During the construction and by collaboration between groups the aim is to study the interaction between solar energy and the proposed selective absorber.

The current thesis proposal has the following goals: 1. Detailed spectral and angular absorptivity and emissivity at elevated temperatures At CSP system the higher the concentration of solar flux the broader the incident angle on the receiver. It is physically impossible to concentrate the solar power and still keep collimated light. While standard tests methods use collimated light, and measure emissivity at or near 100 C, here an experimental set up will be designed and constructed which permits measurements at high temperatures and also at large incident angles. By building ( constructing ) of the system capable to measure directional spectral reflectance of light we will be able to supply much more precise absorbance and emittance at close to real operating conditions . Eventually we built such a system which enables us to vary the angle of incidence and to measure spectral reflectivity using two spectrometers (for visible and near infrared) at different azimuthal and angular directions. By integrating the measured values over the whole spectrum we will be able to supply realistic values for absorbance and emittance. For this purpose we constructed and tested a ceramic electrical furnace which enables us to heat the sample up to 1000 C. By varying the power supply we are able to control the temperature of a sample. Moreover, to eliminate the weather dependence (especially in winter months) we built up an additional system using a xenon lamp instead irradiating the sample by the sun. Several experiments were performed; the experimental results will be included and discussed in the thesis work. 2. Measurements of solar absorptance at high solar concentration Using a solar furnace constructed by Feuermann et al., [12] we are able to test the samples at different concentrations of solar flux. 3. Modeling of thermal performance The optimum tradeoff between gaining a losing energy has to be found. Namely by optimization the spectral selectivity coating in terms of gain/loss it is possible to increase the overall system efficiency and to decrease the Levelized Energy Cost (LEC). A system can benefit from properly handpicked selective coating for a specific usage (e.g., given concentration and desired temperature).there is a trade off between selectivity of the material concentration ratio and temperature. For example, it is possible to use less accurate tracking system and to use simpler CSP optical design and still gain the same temperature accurate tracking and good optics are expensive. Or at the same concentration, to obtain higher temperatures.

References: [1] H. Suehrcke, P.G. McCormick, The Distribution of average instantaneous terrestrial solar radiation over the day, Solar Energy (1989) Vol.42.No. 4. 303-309 [2] H. Tabor, Bull. Res. Counc. Isr. 5A (2) (1956) 119 [3] G.A. Niklasson, C.G. Grainqvist, Solar absorptance and thermal emittance of coevaporated Al203 cermet films, Solar Energy Materials 7(1983) 501-510 [4] J.C.M. Garnet-Garnett, Philos. Trans. R. Soc. London, 203 (1904) 385 p [5] Reilly, H.E., and G.J. Kolb, An evaluation of molten-salt power towers including the results of the solar two project, (2001), Sandia National Laboratories, SAND2001-367 [6] C. M. Lampert, Coatings for enhanced energy collection, Solar Energy Materials 1 (1979) 319-341 [7] C. E. Kennedy NREL/TP-520-31267, July 2002 [8]B.O Seraphin, in: topics in Applied Physics, ed. B.O Seraphin( Springer Verlag, Berlin, Germany, (1979) p.5. [9] M. Faroq, Ifrichar A. Raja, Optimisation of metal Sputtered and electroplated substrates for solar selective coating, Renewable Energy 33( 2008) 1275-1285. [10]C. E. Kennedy, Progress to develop an advanced solar-selective coating, NREL/CD-550-42709, March2008 [11] N. Selvakumar, Harish C. Barshilia, Review of physical vapor deposited (PVD) spectrally selective for mid and high-temperature solar thermal application, J. Sol. Materials & Solar Cells, Review( 20 oct 2011) [12] J.M. Gordon, D.Babai, D. Feuermann, A high- irradiance solar furnace for photovoltaic characterization and nanomaterial synthesis, Solar Energy and Solar Cells, (2010) Vol.95, No.3, pp. 951956 Co-