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A Short Course by Reza Toossi, Ph.D., P.E. California State University, Long Beach 1

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Phase Change Materials Applications Properties Modeling Melting and Solidification Boiling and Condensation Evaporation Aerosol Jet Impingement 2

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3 Abhat, A., “Low temperature latent heat thermal energy storage: heat energy storage materials,” Solar Energy, 30 (1983) 313-332.

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4 Exothermic (warming processes) Condensation ▪ Steam radiators Freezing ▪ Orange growers spray oranges with iced water Deposition ▪ Snowy days are warmer than clear days in the winter Endothermic (cooling processes) Evaporation/Boiling ▪ Sweat ▪ Alcohol is “cool” Melting ▪ Melting ice in drinks Sublimation ▪ Cooling with dry ice Melting Point ( o C) Latent Heat (kJ/kg) Density (kg/m 3 ) Steel 14002477800 Copper 10862068900 Ice 0335917 Sodium Sulfate 322521495

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Solid-Liquid Temperature control Ablation Coating Liquid-Vapor Evaporative cooling 5

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Energy Storage in Buildings Thermal Inertia and Thermal protection Passive heating and cooling Thermoelectric Refrigeration Transport of temperature sensitive materials Thermal Control Industrial Forming (casting, laser drilling) Food and Pharmaceutical Processing Telecom Shelters Human-comfort footwear and clothes Thermos and coolers Electrical Generation Cogeneration Thermoelectric Power Generation Security of Energy Supply Flow-through heat exchangers Microencapsulated PCMs 6

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Thermodynamic Criteria A melting point at the desired operating temperature A high latent heat of fusion per unit mass A high density A high specific heat A high thermal conductivity Congruent melting Small density differences between phases Little supercooling during freezing 7

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Chemical Criteria Chemical stability Non-corrosive, non-flammable, non-toxic Others Long shelf-life Applicability Reliability Commercial availability Low cost 8

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Without encapsulation (container shape and material) Encapsulation Building materials (PCM 50-80%, unsaturated polyester matrix 45-10%, and water 5-10%) 9

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Availability of small number of materials in the temperature range of interest Useful life Maintenance Stability Water loss 10

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Organic Compounds Paraffins Fatty Acids Salt-Based Compounds Salt Hydrates Eutectics Others Ice and water Zeolite 11

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Advantages A wide range of melting points Non-toxic, non-corrosive Chemically stable Compatible with most building materials High latent heat per unit mass Melting congruity Negligible supercooling Are available for wide range of temperatures Disadvantages Expensive Low density Low thermal conductivity (compared to inorganic compounds) Large coefficient of thermal expansion Flammable Do not have a well-defined melting temperatures. 12

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Advantages Lower cost High latent heat per unit mass and volume High thermal conductivity Wide range of melting points (7-117 o C) Disadvantages High rate of water loss Corrosive Phase separation Substantial Subcooling Phase segregation (lack of thermal stability) 15

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Cooling (5-15 o C) Temper diurnal swings Heat pumps Solar hot-water heating systems Absorption air conditioner 22

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23 Roof Wall Window Velraj, R., and Pasupathy, A., “PHASE CHANGE MATERIAL BASED THERMAL STORAGE FOR ENERGY CONSERVATION IN BUILDING ARCHITECTURE “Institute for Energy Studies, CEG, Anna University, Chennai - 600 025. INDIA.

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24 Based on 9 m 2 of solar collector area TES SystemsCost ($)Volume (m 3 ) Water540.72 Rock217 @ $8/ton2.46 Glauber’s Salt1460.18

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Conventional CD (read only) CD-R (recordable) CD-RW (read and write) 26

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Sodium acetate (trihydrate) T sl = 54 o C ∆h sl = 1.86x10 5 J/kg 27

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Melting of Solids Surface Evaporation Boiling Film Boiling Pool Boiling Condensation Film Condensation Dropwise Condensation Aerosol Jet Spray Nucleation Impingement 28

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One-region Multiple-region Two-region 30

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Contact Melting (melting of a solid under its own weight) 31

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Solid Liquid B.C 33 Scale analysis

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34 Governing Equations (Neumann problem ): Boundary Conditions Solution:

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Analytical 1D and some 2D conduction-controlled Numerical Strong (Classical ) numerical solution ▪ Velocity u and pressure p satisfy Navier-Stokes equations pointwise in space-time. Weak (Fixed-Grid) solution ▪ Enthalpy Method (Shamsunder and Sparrow, 1975) ▪ The Equivalent Heat Capacity Method ( Bonacina et al., 1973) ▪ The Temperature-Transforming Model ( Cao and Faghri, 1990) 36

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Two-Region Melting of a Slab Assume densities of the liquid and solid phase are equal. 37

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1. Choose ∆t and ∆x to meet Neumann’s stability criterion 2. Determine the initial enthalpy at every node h j o (j = 1) 3. Calculate the enthalpy after the first time step at nodes (j = 2,..., N -1) by using equation (1). 4. Determine the temperature after the first time step at node (j = 1,..., N) by using equations (2) and (3). 5. Find a control volume in which the enthalpy falls between 0 and h sl, and determine the location of the solid-liquid interface by using equation (4). 6. Solve the phase-change problem at the next time step with the same procedure. 39

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Unconditionally stable but is more complex because two unknown variables enthalpy and temperature are involved. [See Alexiades, A., and Solomon, A. D., 1993, Mathematical Modeling of Melting and Freezing Processes, Hemisphere, Washington, DC.] Transform the energy equation into a nonlinear equation with a single variable h. [See Cao, Y., and Faghri, A., 1989, " A Numerical Analysis of Stefan Problem of Generalized Multi- Dimensional Phase-Change Structures Using the Enthalpy Transforming Model," International Journal of Heat and Mass Transfer, Vol. 32, pp. 1289-1298.] 40

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3-D Conduction controlled melting/solidification Heat capacity during the phase change is infinite. Assume C p and k change linearly from liquid to solid Advantage: Simplicity Disadvantage: Unstable if right choices for ∆x, ∆t, and ∆T are not made. 41

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Combination of the two methods [Cao, Y., and Faghri, A., 1990a, " A Numerical Analysis of Phase Change Problem including Natural Convection," ASME Journal of Heat Transfer, Vol. 112, pp. 812- 815.] Use finite volume approach by Patankar to solve the diffusion equation. 42

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Assumptions “Enthalpy Method” approach is considered Newtonian incompressible fluid with constant properties, except the density that is evaluated s linear function of temperature (Bousinessq approximation) Effective conductivity in the mushy zone Isotropic Heat transfer by conduction, convection and phase change 43 CARLOS HERNÁN SALINAS LIRA1, SOLIDIFICATION IN SQUARE SECTION, Theoria, Vol. 10: 47-56, 2001.

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Eulerian Averaging Averaged over space, time, or both within the domain of integration ▪ Based on time-space description of physical phenomena ▪ Consistent with the c.v. analysis used to develop governing equations. ▪ Eulerian time-averaging ▪ Eulerian volume-averaging Phase-averages: ▪ Intrinsic phase average ▪ Extrinsic phase average Lagrangian Averaging Follow a particle and average its properties during the flight Molecular Statistical Averaging Boltzmann statistical distribution rather than individual particle is the independent variable. 46

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Jany, P., and Bejan, 1988, " Scaling Theory of Melting with Natural Convection in an Enclosure," International Journal of Heat and Mass Transfer, Vol. 31, pp. 1221-1235. 47 Governing Equations:

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Nucleation Homogeneous Heterogeneous ▪ Filmwise ▪ Dropwise 50

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52 Liquid and gas properties Latent heat of vaporization, h lg Surface tension at the interface, Phase density difference, ( l - g ) Surface roughness and orientation Contact angle, θ c

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53 Inspired by Namib desert beetle Mimics wing with a microscopic pattern of water-attracting and water-repelling areas Also seen on lotus leaves Applications include Self-decontaminating surfaces Antifogging surfaces Microfluidic chips Harvesting dews as drinkable water Pocket-sized chemical testing devices Rubner and Cohen, Nano Letters 6(6), 1213-1217 (2006)

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Nano-structured film made of alternating layers of positively and negatively charged polymers and silica nanoparticles Dual quality material can be patterned to repel water in some areas (spherical droplets) and attract it in others (flattened ones). 54

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The type of boiling depends on Pool Boiling (water in a pan on top of a stove) ▪ Subcooled (local) T liq < T sat ▪ Saturated (bulk) T liq = T sat Film Boiling (flow in a heated pipe) Surface Superheat ∆T = T s -T sat Surface roughness 55

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56 Tap water on a stove Natural Convection Boiling A-B Air bubbles burst (Subcooled boiling) Nucleate Boiling B-C Saturated boiling (T bulk = 100 o C) –no bubbles yet! C -D Quenching - unstable, insulating bubble blanket Film Boiling D-E Bulk motion (convection and radiation)

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62 Effect of substrate (Layered structure of an electric heater)

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Two-layer model with enhanced wall function Macroscale (jet flow) Microscale (droplet dynamics) Impact of single droplet Impact of multiple droplets Garbero, et al., “Gas/surface heat transfer in spray deposition processes,” Intl. J. Heat and Fluid Flow, Vol. 27, Issue 1, Feb 2006, pp. 105-122 68

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Single round jet: Multiple jets: 69

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Single Droplet We D < 30 Bouncing without breakup 30< We D < 80 Deformation with recoil We D >80 Spreading followed by breakup Droplet Spray 70

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BCorrelation number D jet/nozzle diameter d droplet diameter K droplet splashing criterion n number of droplets number flux of droplets NuNusselt number, hD/k Nu 0 Nusselt number in absence of particles ω mass loading σ surface tension 74

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Comparison with parallel flow Example: Substrate cooling of a plastic sheet L = 20 cm, T s = 95 O C, T f, ∞ = 20 O C, U f, ∞ = 5 m/s for parallel flow; = 25 m/s in nozzle Fluid: water 76

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Droplet deformation (spreading) during impact (d p = 200 μm, U p = 10 m/s). Before impact After impact 77

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Contours of total surface heat flux (seen from below) Velocity vectors during the impact of three droplets: three-droplet Garbero, Vanni, and Fritscling, “Gas/surface heat transfer in spray deposition processes,” Int’l J. Heat and Fluid Flow, Vol. 27, Issue 1. Feb 2006, pp. 105-122. 78

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Park, K., and Watkins, A. P., “Comparison of wall spray impaction models with experimental data on drop velocities and sizes,” Int. J. Heat and Fluid Flow, Vol. 17, No. 4, August 1996. Bai and Gosman (1995): Drop collision model (Stick, Spread, Rebound, Rebound with breakup, Boiling- induced breakup, Random breakup, Splash) Wang and Watkins (1990) We 80 Where, C wb = 1/3 79

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Rebound, Rebound with breakup, Break-up, and Splash (Park and Watkins, 1996) Spreading velocity Film thickness Splashing Criteria (Bussmann, 2000) K

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81 For additional questions, Please email rtoossi@csulb.edu.rtoossi@csulb.edu

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82 Finned tubes [1] A. Abhat, S. Aboul-Enein, N. Malatidis, Heat of fusion storage systems for solar heating applications, in: C. Den Quden (Ed.), Thermal Storage of Solar Energy, Martinus Nijhoff, 1981. [2] V.H. Morcos, Investigation of a latent heat thermal energy storage system, Solar Wind Technol. 7 (2/3) (1990) 197–202. [3] M. Costa, D. Buddhi, A. Oliva, Numerical Simulation of a latent heat thermal energy storage system with enhanced heat conduction, Energy Convers. Mgmt. 39 (3/4) (1998) 319–330. [4] P.V. Padmanabhan, M.V. Krishna Murthy, Outward phase change in a cylindrical annulus with axial fins on the inner tube, Int. J. Heat Mass Transfer 29 (1986) 1855–1868. [5] R. Velraj, R.V. Seeniraj, B. Hafner, C. Faber, K. Schwarzer, Experimental analysis and numerical modelling of inward solidification on a finned vertical tube for a latent heat storage unit, Solar Energy 60 (1997) 281– 290. [6] R. Velraj, R.V. Seeniraj, B. Hafner, C. Faber, K. Schwarzer, Heat transfer enhancement in a latent heat storage system, Solar Energy 65 (1999) 171–180. Embedding in Graphite Matrices [7] P. Satzger, B. Exka, F. Ziegler, Matrix-heat-exchanger for a latent-heat cold-storage, Proceedings of Megastock 98, Sapporo (Japan), 1998. [8] H. Mehling, S. Hiebler, F. Ziegler, Latent heat storage using a PCM-graphite composite material: advantages and potential applications, Proceedings of the 4th Workshop of IEA ECES IA Annex 10, Bendiktbeuern (Germany), 1999. [9] X. Py, R. Olives, S. Mauran, Paraffin/porous-graphite-matrix composite as a high and constant power thermal storage material, Int. J. Heat Mass Transfer 44 (2001) 2727–2737.

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