A Short Course by

Reza Toossi, Ph.D., P.E.

California State University, Long Beach

Phase Change Materials

Applications Properties

Modeling
Melting and Solidification Boiling and Condensation

Evaporation
Aerosol Jet Impingement

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

Exothermic (warming processes)

Melting Point (oC)

Condensation
Steam radiators Orange growers spray oranges with iced water Snowy days are warmer than clear days in the winter

Latent Heat (kJ/kg)

Density (kg/m3)

Steel Copper

1400 1086

247 206

7800 8900

Freezing Deposition

Ice
Sodium Sulfate

0 32

335 252

917 1495

Endothermic (cooling processes)

Evaporation/Boiling
Sweat Alcohol is cool Melting ice in drinks Cooling with dry ice

Melting

Sublimation

Solid-Liquid
Temperature control Ablation

Coating

Liquid-Vapor
Evaporative cooling

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
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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
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Chemical Criteria
Chemical stability Non-corrosive, non-flammable, non-toxic

Others

Long shelf-life Applicability Reliability Commercial availability Low cost

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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%)

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

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Organic Compounds
Paraffins Fatty Acids

Salt-Based Compounds
Salt Hydrates

Eutectics Others
Ice and water

Zeolite

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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.
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Advantages

Lower cost High latent heat per unit mass and volume High thermal conductivity Wide range of melting points (7-117oC)

Disadvantages

High rate of water loss Corrosive Phase separation Substantial Subcooling Phase segregation (lack of thermal stability)

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

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Wall Roof

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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Based on 9 m2 of solar collector area

TES Systems Water Rock Glaubers Salt 54 217 @ $8/ton 146 Cost ($) Volume (m3) 0.72 2.46 0.18

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

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Sodium acetate (trihydrate)

Tsl = 54oC hsl = 1.86x105 J/kg

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Melting of Solids Surface Evaporation Boiling

Film Boiling Pool Boiling

Condensation
Film Condensation Dropwise Condensation

Aerosol Jet Spray

Nucleation Impingement

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One-region

Multiple-region

Two-region

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

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Solid

Scale analysis

Liquid

B.C

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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)

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Two-Region Melting of a Slab

Assume densities of the liquid and solid phase are equal.

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1.

Choose t and x to meet Neumanns stability criterion

2. 3. 4. 5. 6.

Determine the initial enthalpy at every node hjo (j = 1) Calculate the enthalpy after the first time step at nodes (j = 2 ,..., N -1) by using equation (1). Determine the temperature after the first time step at node (j = 1 ,..., N) by using equations (2) and (3). Find a control volume in which the enthalpy falls between 0 and hsl , and determine the location of the solid-liquid interface by using equation (4). Solve the phase-change problem at the next time step with the same procedure.

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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 MultiDimensional Phase-Change Structures Using the Enthalpy Transforming Model ," International Journal of Heat and Mass Transfer , Vol . 32 , pp . 1289-1298.]

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3-D Conduction controlled melting/solidification

Heat capacity during the phase change is infinite. Assume Cp and k change linearly from liquid to solid

Advantage: Simplicity Disadvantage: Unstable if right choices for x, t, and T are not made.

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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 . 812815.]

Use finite volume approach by Patankar to solve the diffusion equation.

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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

CARLOS HERNN 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.
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Governing Equations:

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.

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Nucleation
Homogeneous

Heterogeneous Filmwise Dropwise

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Liquid and gas properties Latent heat of vaporization, Dhlg Surface tension at the interface, s Phase density difference, (rl - rg) Surface roughness and orientation Contact angle, c

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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).

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The type of boiling depends on

Pool Boiling (water in a pan on top of a stove) Subcooled (local) Tliq < Tsat Saturated (bulk) Tliq = Tsat Film Boiling (flow in a heated pipe)

Surface Superheat T = Ts-Tsat Surface roughness

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Tap water on a stove

Natural Convection Boiling
A-B B-C C -D D-E Air bubbles burst (Subcooled boiling) Saturated boiling (Tbulk = 100oC) no bubbles yet! Quenching - unstable, insulating bubble blanket Bulk motion (convection and radiation)

Nucleate Boiling

Film Boiling

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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

Single round jet:

Multiple jets:

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Single Droplet

WeD < 30 30< WeD < 80 WeD >80

Bouncing without breakup Deformation with recoil Spreading followed by breakup

Droplet Spray

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Correlation number jet/nozzle diameter droplet diameter droplet splashing criterion number of droplets number flux of droplets Nu Nusselt number, hD/k Nu0 Nusselt number in absence of particles mass loading surface tension

B D d K n

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Comparison with parallel flow

Example: Substrate cooling of a plastic sheet
L = 20 cm, Ts = 95OC, Tf,= 20OC, Uf,= 5 m/s for parallel flow; <uf> = 25 m/s in nozzle Fluid: water

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Before impact

After impact

Droplet deformation (spreading) during impact (dp = 200 m, Up = 10 m/s).

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Contours of total surface heat flux (seen from below)

Velocity vectors during the impact of three droplets: three-droplet

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Garbero, Vanni, and Fritscling, Gas/surface heat transfer in spray deposition processes, Intl J. Heat and Fluid Flow, Vol. 27, Issue 1. Feb 2006, pp. 105-122.

Bai and Gosman (1995): Drop collision model

(Stick, Spread, Rebound, Rebound with breakup, Boilinginduced breakup, Random breakup, Splash)

Wang and Watkins (1990)

We < 80

We > 80

Where,

Cwb = 1/3
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.

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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<Kcrit ,
where:

K = WeD Ohd-0.4 K -0.63 crit = 649 + 3.76 ReD

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

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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) 197202. [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) 319330. [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) 18551868. [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) 171180. 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) 27272737.

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