Enhancement of the thermal conductivity of stearic acid by adding expanded graphite as filler material

Lourens Petrus Swart

CSC 411 2012-05-29

Enhancement of the thermal conductivity of stearic acid by adding expanded graphite as filler material

Lourens Petrus Swart 29033455 Department of Chemical Engineering University of Pretoria

CSC 411 2012-05-29

Enhancement of the thermal conductivity of stearic acid by adding expanded graphite as filler material
Synopsis
The thermal conductivity of stearic acid was significantly improved with the addition of 6.9 wt% expanded graphite. This yields a composite with a fast thermal response (compared to pure stearic acid), homogenous phase and high latent heat capacity of 179.6 J/g. KEYWORDS: stearic acid, expanded graphite, thermal energy storage, thermal conductivity improvement

Contents
Synopsis...................................................................................................................... i 1. 2. Introduction ......................................................................................................... 1 Literature ............................................................................................................. 2 2.1 2.2 2.3 2.4 3. Characteristics and classification .................................................................. 2 Selection criteria............................................................................................ 2 Applications ................................................................................................... 3 Stearic Acid and Expanded Graphite ............................................................ 4

Experimental ....................................................................................................... 6 3.1. Planning ........................................................................................................ 6 3.2. Apparatus ...................................................................................................... 6 3.3. Method .......................................................................................................... 7 3.1.1. Composite Preparation ........................................................................... 7 3.1.2. Thermal testing ....................................................................................... 9

4. 5. 6. 7.

Results and Discussion ..................................................................................... 11 Conclusions and Recommendations ................................................................. 17 Acknowledgements ........................................................................................... 17 References ........................................................................................................ 18

1. Introduction
Increasing global warming and fuel prices has ignited bright minds across the globe to explore alternative energy sources. One promising alternative energy source is solar energy. Solar energy is free, renewable, has no waste products and is suitable for energy generation in many parts of the world. (According to measurements made by NASA the solar radiance during 2008 was 1360.80.5 W/m2 (Kopp & Lean, 2011)). The problem with solar energy is that it is readily available during the day, but not at night and during bad weather conditions. If this energy can be efficiently stored during the day it can be used during these conditions, causing a shift in the domestic energy demand cycle. This energy only needs to be stored for a few hours until solar energy can be collected again. Solar thermal energy storage systems have been developed on industrial scale in the form of solar collectors and molten salt energy storage systems. These systems are too large and expensive for domestic use. One possibility that has been considered for domestic energy storage is phase change materials. These methods use the latent energy of PCM to store thermal energy for later use (Sagara & Sharma, 2005). A number of researchers have done work on these materials and this is the basis of this study. Stearic acid (SA) has been identified as a possible PCM. A problem with stearic acid is that it has a low thermal conductivity. The thermal conductivity of stearic acid can be drastically improved by using expanded graphite (EG) as filler material. In this investigation the thermal response of SA/EG composites with different mass ratios were tested. Different mass ratios were tested in order to determine the optimum amount of expanded graphite in the composite in order to increase the thermal conductivity, without compromising the latent energy storage of stearic acid.

2. Literature
2.1

Characteristics and classification

Phase change materials can be classified in a number of subcategories. Each category has its own advantages and disadvantages. Our focus for the rest of this paper would be on a fatty acid, stearic acid. Parrafin Compounds Organic Non-Paraffin Compounds Salt Hydrates Phase Change Materials Fatty acids Esters Alcohols Glycols

Inorganic
Metalics Organic/ Organic Eutectic Inorganic /Inorganic Inorganic/ Organic

Figure 1: Classification of PCM (Buddhi et al, 2009) 2.2

Selection criteria

Although operating temperature is an important factor when choosing a PCM, it does not necessarily meet the requirements for the application intended. Criteria that has to be kept in mind when choosing a PCM is listed below (Gawron & Schrder, 2007; Buddhi et al, 2009):

chemical stability throughout many heating and cooling cycles, congruent melting and freezing, high density, high heat capacity, high heat of fusion, high thermal conductivity, low cost, lo o p ool n no mo 2 n C ),

low thermal expansion, low vapour pressure (<100 kPa) at the operating temperature, melting point suitable for its application, should not be toxic, flammable, corrosive or poisonous, sufficient crystallization rate, abundant and cost effective (Kenisarin & Mahkamov, 2006).

There is no single material that has all of these properties. Therefore methods must be found to improve materials properties. Property improvement methods include composites (this includes eutectics), adding fillers, adding fins to the heat exchange surface and introducing nucleating agents (Buddhi et al, 2009). If a PCM has a high heat capacity and density the specific energy capacity of the material will also be higher (White, 2002). 2.3

Applications

PCM technology has been used for various applications which include: Temperature regulation in buildings (Hariri & Ward, 1988), Thermal energy storage (Kaygusuz & Sari, 2001), Heat pump systems (Omer, 2008), Greenhouses (Buddhi et al, 2009), Solar cooking (Sagara and Sharma, 2005), Computer and portable electronic device cooling (Wang & Yang, 2012), Solar engineering (Buddhi et al, 2009), Spacecraft thermal control (Buddhi et al, 2009), Waste heat recovery, where waste heat supply and demand cycles differ (Sagara & Sharma, 2005), Textiles (Mondal, 2008), Telecom shelter cooling in tropical climates and desserts (Seeniraj, Shanmuga Sundaram & Velraj, 2010).

2.4

Stearic Acid and Expanded Graphite

Stearic acid is the trivial name of octadecanoic acid (CH3(CH2)16COOH). It is a saturated fatty acid found as a glycerol ester in animal and plant fats and oils (BeareRogers, Dieffenbacher & Holm, 2001). It is extracted from theses oils and fats by treating it with water at high a temperature C) and pressure. This cause hydrolyses of triglycerides. The mixture is then separated using distillation (Anneken et al, 2006). According to Hasan and Sayigh (1994) stearic acid is a good candidate for use in domestic water heating systems, because of its high heat of fusion (287.94 kJ/kg according to Green & Perry, 2007), appropriate n on mp o C

and its good chemical stability over large melting and solidification cycles. They have exposed stearic acid to 450 melting and solidification cycles n l l mp n C) and observed n C n

an insignificant amount of reduction in latent heat. They also noted that after only a

C) the latent heat was reduced by up to one third. Other properties of stearic acid that makes it a good PCM are that fatty acids have good congruent melting and freezing (Kaygusuz & Sari, 2006), it freezes without supercooling (Glew and Lane, 1975), it has a low vapour pressure (1 mmH C (Green & Perry, 2007), which will be significantly less than 100 kPa at the application temperature). Properties that make stearic acid less appropriate for use as a PCM is that it has low thermal conductivity (Kaygusuz & Sari, 2001) and moderate thermal expansion. According to Buddhi et al (2009) the major drawback of stearic acid is that is expensive (2 2.5 times as expensive as technical grade paraffin) and it is slightly corrosive. One method of improving stearic acid is to add a filler material to improve thermal conductivity. Various materials have been considered as fillers which include carbon fibre (Karaipekli, Kaygusuz & Sari, 2007), expanded perlite (Fang, Ji & Jiao, 2012) and expanded graphite. Expanded graphite is an excellent filler because it has a porous structure onto which the stearic acid can be impregnated to (Karaipekli & Sari, 2007), there is no chemical 4

reaction between stearic acid and expanded graphite (Chen et al, 2010), it has a specific surface area (30.4 m2/g) and most importantly, it has a high thermal conductivity (Wang, Zhang & Xia, 2010). Chen et al (2010) determined that the maximum amount of stearic acid in expanded graphite is 83 %. At this composition there was no leakage of stearic acid from the expanded graphite. According to Karaipekli & Sari (2007) the latent heat of the composite (consisting of expanded graphite and paraffin) is practically equivalent to the latent heat value based on the mass percentage of paraffin in the composite. The application of this SA/EG composite will be in water heating systems. The idea is to encapsulate this material and insert it into domestic geysers. Water will then be heated by solar power during the day. The heated water will melt the composite. The melted composite will then help maintain the water temperature during the night.

3. Experimental
3.1. Planning

Samples of different mass rations of stearic acid and expanded graphite were prepared. These ratios stayed the same for each sample throughout the test so that the thermal response of each can be compared to that of pure stearic acid. The primary temperature range that had to be measured was that close to the transition temperature of stearic acid. This range is important because of the latent heat storage application. For further comparison of thermal response, the mp n om C o C was measured.

It was assumed that energy loss to the environment is negligible because the baths were sufficiently large. Loss from the top was also ignored because the air in the top of the test tube was stagnant.

3.2.

Apparatus

All of the apparatus used in the experiment is available in most laboratories. These include test tubes, rubber plugs, thermocouples, computer (for temperature logging with Labview), ice bath and a warm water bath (beaker and a hot plate stirrer). A differential scanning calorimeter was also used.

3.3.

Method

3.1.1. Composite Preparation Two materials were used during the experiment, i.e. expanded graphite and stearic acid. Expandable graphite (ES 250 B5) was expanded in an oven for 10 minutes at 400 C. The stearic acid that was used was supplied by Pan Century Oleochemicals sdn bhd. The composition of the stearic acid used is shown in table 1. Composition (Weight %) 1 (max) 3 (max) 50-60 40-50

Fatty Acid Lauric acid (C12) Myristic acid (C14) Palmitic acid (C16) Stearic acid (C18) Table 1: Stearic acid composition

The samples were prepared by first marking off a certain volume on a test tube. This was done to ensure that each sample has the same heat transfer area. Sample A contained only stearic acid. It was used as a control against which the other samples could be compared. For sample B, the test tube was filled with expanded graphite up to the mark. The expanded graphite was weighed and molten stearic acid was added until the stearic acid covered all of the expanded graphite. The test tube was weighed again to determine the mass of stearic acid in the sample. Sample C was prepared by using one and a half times the mass of expanded graphite of sample B and compressing it down to the mark on the test tube. Holes were punched into the expanded graphite to make it easier for the molten stearic acid to seep into the pores between the expanded graphite particles. The same was done for the sample C, but with twice the mass of expanded graphite. These samples were then weighed to determine the mass of stearic acid in each sample.

Samples E and F were prepared by weighing off the desired amounts of expanded graphite and stearic acid to obtain a 2.5 and 5 weight percentage of expanded graphite in each sample respectively. The mixture was the melted and poured into the test tubes up to the desired volume. Expanded graphite (Weight %) 0 4.3 6.9 9.1 2.5 5

Sample A B C D E F

Homogenous Yes No Yes Yes No Yes

Table 2: Properties of prepared samples Table 2 shows the weight percentage of expanded graphite in the separate samples and if the samples formed a homogenous phase of expanded graphite and stearic acid. Sample C is roughly the limit between homogenous and non-homogenous.

Figure 2: Homogenous (left) and non-homogenous (right) samples An example of a homogenous and non-homogenous sample is shown in figure 2. The bottom phase of the non-homogenous sample is the stearic acid without the expanded graphite.

3.1.2. Thermal testing Heating phase 1: The sample was heated on the hot plate stirrer from room mp n l pp o m mp T mp

of the sample and bath was logged in one second intervals using Labview. The thermocouple in the sample was held in place by inserting it through a rubber plug that fits into the test tube with a hole drilled through the top. Cooling phase 2: The sample was then immersed in the ice bath until the sample mp pp o C. The same temperature measurements were made

as for phase 1. Each sample was put through three heating/cooling cycles. Identical testing procedures were followed for all of the samples. The experimental setup is shown in figure 3. DSC was done (by Mrs I van der Westhuizen) on a pure sample of stearic acid to determine its phase transition temperatures and to determine the heat of fusion. The mp atmosphere. mp om C o C o C/min in a nitrogen

Comp

mp

lo

T R

mo o pl pl

S mpl I /W m

Figure 3: Experimental Setup 10

4. Results and Discussion

The results of the heating and cooling phases are shown in figure 4 and figure 5 respectively. Each line represents the average of three heating/cooling cycles. The horizontal section represents phase transition. When the pure stearic acid sample and the non-homogenous samples where melted, the stearic acid adjacent to the thermocouple were the last to melt. The piece of stearic acid around the thermocouple then slipped of and caused a spike in the temperature. This is why some of the samples do not have a distinct horizontal section and display artefacts. According to Hasan (1994), initially heat transfer is dominated by conduction, but as the stearic acid starts to melt, convection starts to play a role. This might play a role in sample A and the non-homogenous samples, but not as much in the homogenous samples because the expanded graphite stays solid. Slight variations in the warm and cold baths have a slight influence on the thermal response of the samples. The average bath temperature for each sample is shown in table 3. Average warm bath Temperature ( C) 76.2 76.7 77.9 77.3 77.9 77.8 Average cold bath Temperature ( C) 2.0 1.9 0.6 0.3 0.0 -0.1

Sample A B C D E F

Table 3: Average bath temperature for each sample. Stearic acid has a significant amount of thermal expansion. Because the mass of stearic acid in each sample differs, the amount of thermal expansion will also differ slightly. This causes the heat transfer area to increase.

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If it is assumed that the specific latent heat for each sample can be calculated as done by Karaipekli & Sari (2007) with their expanded graphite/paraffin composite, the specific latent heat of each sample will be as shown in table 4. The pure stearic acid specific latent heat is taken as the average of the results obtained with the DSC. Sample A B C D E F Table 4: Specific latent heat of each sample Specific latent heat (J/g) 193.0 184.7 179.6 175.4 188.1 183.3

12

65.0

60.0
55.0 50.0 Sample A 45.0 40.0 35.0 30.0 25.0 20.0 Sample B Sample C Sample D Sample E Sample F

Temperature (C)

0.0

50.0

100.0

150.0

200.0 250.0 Time (s)

300.0

350.0

400.0

450.0

Figure 4: Heating phase

13

70.0
65.0 60.0 55.0 Temperature (C) 50.0 45.0 40.0 35.0 30.0 25.0 20.0 0.0 100.0 200.0 300.0 400.0 Time (s) 500.0 600.0 700.0 800.0 Sample A

Sample B
Sample C Sample D Sample E Sample F

Figure 5: Cooling phase

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Figure 6: DSC results

15

400 Time to phase change (s)

300

200

100

0 0 2 4 6 wt% Expanded graphite in sample 8 10

Figure 7: Weight percentage expanded graphite in the sample vs. time until the sample has melted

500
Time to phase change (s) 400 300 200 100 0 0 2 4 6 wt% Expanded graphite in sample 8 10

Figure 8: Weight percentage expanded graphite in the sample vs. time until the sample has solidified Figure 7 and 8 shows the time it took from the onset of the experiment up to the point where the phase transition has completed vs. the weight percentage in the sample.

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5. Conclusions and Recommendations

It was proven that the thermal conductivity (thermal response) of stearic acid is significantly improved by the addition of expanded graphite. This can be seen in figure 4 and 5 by comparing the time it takes the pure stearic acid sample to change phase and that of the samples with expanded graphite. It is recommended a homogenous composite be used. This will prevent leakage of stearic acid from the composite and ensure optimal performance of the composite. It can be seen from figure 7 and 8 that the thermal response of the samples increase with an increase in mass percentage of expanded graphite up to a point and then it levels out. Thus expanded graphite only increases the thermal conductivity up to a point. After this point the addition of expanded graphite only replaces stearic acid, reducing the latent heat capacity of the composite. Sample C would thus be the best choice for this application. It is homogenous, lies within the horizontal section of figure 7 and 8 and only has a 6.9 % loss in latent heat capacity compared to pure stearic acid.

6. Acknowledgements
Special thanks to Dr Johan Labuschagn, Prof Walter Focke and Heinrich Badenhorst for their contributions. Thanks to Mrs Isbe van der Westhuizen for her help the DSC. Thanks to Paul Sonnendecker for his help with the experimental setup and to The Department of Chemical Engineering at The University of Pretoria for use of their laboratory facilities.

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7. References
Anneken, DJ, Both, S, Christoph, R, Fieg, G, Steinberner, U and Westfechtel A (2006) Ullmann's Encyclopedia of Industrial Chemistry 2006, Willey Online Library. Beare-Rogers, J, Dieffenbacher, A and Holm, JV Lexicon of lipid nutrition (IUPAC Technical Report) Pure and Applied Chemistry, 73(4), 685-744. Benabdelkarim, M, Goetz, V, Haillot, D and Py, X (2011) H m B o l n D C p on Solar Energy, 85(5), 1021-1027. n CR S n m m A n l T n ppl ) VV R on m l n p om n o

composite for the enhancement of solar domestic hot water systems: Part 1: Storage

on Renewable and Sustainable

Energy Reviews, 13(2), 318-345. Chen, Z, Fang, G, Li, H and Liu, X (2010) Preparation and characterization of stearic acid/expanded graphite composites as t 4622-4626. F n D J B n J o C ) Preparation and properties of lauric acidstearic m l n o m l Energy, 35(12),

acid/expanded perlite composite as phase change materials for thermal energy storage Materials Letters, 67(1), 352-354. G on K n S J ) L n o International Journal of Energy

Research, 5(2), 103-109. Gl DN n L n GA ) H o on m o ol n o paper

presented at The workshop on solar energy storage subsystems for the heating and cooling of buildings, sa, 1975, Charlothensville, United Stated of America. Green, DW and Perry, RH (2007), Perrys Chemical Engineering Handbook, 8th Edition, McGraw-Hill, New York. H ppl H m AS n W IC ) A o m l o m n l n

on Building and Environmental, 23(1), 1-10. n A ) Thermal energy storage system with stearic acid as phase change

l Energy Conversion and Management, 35(10), 843-856.

18

H so K

n A m

AA

) Som

-change thermal energy

l Renewable Energy, 4(1), 69-76. n S A ) Thermal conductivity and latent heat thermal energy

p kl A

storage characteristics of paraffin/expanded graphite composite as phase change material Applied Thermal Engineering, 27(8-9), 1271-1277. K p kl A K z K n S A ) T m l on mp o m n o

stearic acid using expanded graphite and carbon fibre for energy storage applications Renewable Energy, 32(13), 2201-2210. K p K z K n S n m A ) T m l n o m n

l Solar Energy, 71(6), 365-376. A mx ) T o lo m l nergy storage characteristics of myristic and mp n ppl on Chinese Journal

z K n S

of Chemical Engineering, 14(2), 270-275. Kopp G n L lm Mondal, S n n n JL ) A n lo l o o l ol n :E n e and

Geophysical research letter, 38(1). ) Phase change materials for smart textiles An overview Applied

Thermal Engineering, 28(11-12), 1536-1550. Om ol S AB ) Renewable building energy systems and passive human comfort

on Renewable and Sustainable Energy Reviews, 12(6), 1562-1587. K n S m SD ) Latent heat storage materials and m :A

International Journal of Green Energy, 2(1), 1-56. Seeniraj, RV, Shanmuga Sundaram, A n V l j R ) An experimental

investigation on passive cooling system comprising phase change material and twophase closed thermo syphon for telecom shelters in tropical and desert regions Energy and Buildings, 42(10), 1726-1735. W n xp n 2548. RZ X p L n /p Z n n P ompo ) Preparation and thermal characterization of p n m l Carbon, 48(9), 2538-

19

Wan ool n

n ppl

Y n

Y po

) Numerical simulation of three-dimensional transient l l on n p n m l

on on

International Journal of Thermal Sciences, 51, 155-162.

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