Journal of Non-Crystalline Solids 225 1998.

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Section 7. Properties. A. Thermal

Aerogel-based thermal insulation

Douglas M. Smith
a b

a, )

, Alok Maskara a , Ulrich Boes

NanoPore, 2501 Alamo SE, Albuquerque, NM 87106, USA Cabot, CAB-O-SIL Diision, D-63457 Hanau, Germany

Abstract Commercial development of aerogel granules, produced via ambient pressure processing, for advanced thermal insulation is discussed. By employing modeling and experimental verification, the thermal performance of granule compacts was studied. The application of a novel approach for surface modifying carbon black to the problem of adding opacifiers to silica aerogels is shown and improved thermal and mechanical properties were obtained. When opacified granules are produced with the correct densityrstrength, the application of a 1 bar load as is naturally applied in vacuum panels. results in deformationrrearrangement such that a packing fraction approaching one is achieved. The thermal performance of these granule compacts, at ambient pressure and vacuum, is similar to that of aerogel monoliths without the cost and processing problems of monoliths. q 1998 Elsevier Science B.V. All rights reserved.
Keywords: Aerogel; Granules; Thermal insulation

1. Introduction Aerogels offer some of the lowest reported thermal conductivity values for any solid. The scientific basis for aerogel commercialization as advanced insulation has been established over the last decade w13x. Increasing energy costrconsumption and increased environmental concerns, mandate utilization of advanced thermal insulation. Despite their obvious technical advantages, aerogel production is not yet commercially practiced. It is often reported that large-scale commercialization of aerogels has not been attempted; however, Monsanto produced silica aerogels in granular and powder forms using the

Corresponding author. Tel.: q1-505 247 4041; fax: q1-505 247 4046; e-mail: smith@nanopore.com.

Kistler high temperature, high pressure. process for many years under the tradename Santocel w . Production was approximately 3 = 10 6 kgryr and the silica source was sodium silicate waterglass.. Production ended because of the high costs associated with the batch, high pressure process and the inability to lower costs by scaling up the plant to larger volumes wW. Patton, private communication, 1996x. Many patents from the 1950s through 1970s exist on the use of aerogelrSantocel w in various insulation forms such as vacuum panels, polymeraerogel composites, and fiberglassaerogel composites. Other commercialization efforts were attempted using supercritical technology but none resulted in the establishment of a commercial-scale facility. The lack of success is a result of relatively high costs on a costrinsulating performance basis. as compared to other insulation. Production of aerogels at ambient pressure has been demonstrated w4x and raises the

0022-3093r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved. PII S 0 0 2 2 - 3 0 9 3 9 8 . 0 0 1 2 5 - 2

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possibility of continuous production with lower capital and operating costs. There are five main routes to producing aerogels which may be used either alone or in combination to reducereliminate drying shrinkage. The high temperature, high pressure, supercritical process employed by Monsanto and Airglass has alcohol or alcoholrwater mixtures in the gel which is heated so that drying occurs under supercritical conditions. Safety concerns add expense and both companies suffered major explosions. The low temperature process avoids those concerns by replacing the fluid with liquid carbon dioxide but that step adds cost. The exchange step can be avoided by using an alkoxide instead of sodium silicate but at the expense of higher raw material cost. Ambient pressure routes employ either surface modification before drying to cap reactive silanols and enable springback during drying w5x, reinforcement after gelation by infiltration of sodium silicate or TEOS to increase strength w6,7x, or direct drying from low surface tension solvents w5x. However, those suffer from potential problems such as 1. higher material costs, 2. excessive solvent use, 3. undesirable by-products, 4. excessive processing times, andror 5. density limitations. In an effort to eliminaterminimize these problems, Cabot and NanoPore have recently developed two new ambient pressure processes w8x. In order to become a commercial success, aerogels must achieve not only thermal performance which provides value to the customer but must also meet other specific criteria which are application dependent. Examples are 1. operating temperature, 2. insulation shape and form, 3. mechanical strength, 4. flammability and smoke, 5. ease of installation, 6. water sensitivity, 7. weight, 8. recycle, 9. durability, 10. optical properties, and 11. lifetime. Rarely will the end-user directly use aerogel granules but rather, an insulation solution. This implies that an ability to tailor aerogel properties and a knowledge of insulation applications is necessary to achieve commercial success.

known modeling techniques with product development. Thermal properties are affected by density, pore sizerdistribution, opacification, and form. Operating pressure, temperature and filler gas also affect performance. The optimum product is therefore dependent on the insulation operating conditions. In this paper, we employ modeling to attack a specific problem how to achieve the thermal performance of an aerogel monolith while employing aerogel granules. Our modeling approach directly follows that of Hrubesh and Pekala with three changes. An additional gas phase conduction term is used for intergranular heat transfer. The pore size used for the intergranular region is calculated as the hydraulic diameter using the granule diameter and the packing fraction f .. f is defined as the volume fraction of granules in the compact. For the intragranular pore size, we fix density and surface area since those are the properties that can be controlled during synthesis. The average pore size, which we take as the hydraulic diameter, for a given density is bounded by the surface area range which is practical 1001000 m2rg.. The addition of carbon black opacifier is accounted for by; a. varying the specific extinction coefficient and b. either a series or parallel model addition of the carbon solid phase thermal conductivity.

3. Experimental Aerogels were produced by reacting sodium silicate with sulfuric acid in an excess of water to reach the desired gelation pH of 35. Solids content of the sol was varied between 5 and 7% solids SiO 2 and carbon.. Sodium sulfate was removed by repeated washing with deionized water and the gels were dried with an ambient pressure drying technique. After drying, granules were ground to the desired size using a mechanical grinder. Low surface area carbon black ; 20 m2rg. was added using three different approaches. For some samples, carbon black was simply blended with aerogel. For others, carbon black was added to the sol as an aqueous slurry after the pH had been adjusted to near the final gelation pH but before gelation. The third approach used a novel method of modifying the surface chemistry of the carbon with a diazonium salt. This yields a

2. Thermal modeling The framework for thermal transport modeling in aerogels is well-established and our aim is to couple

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carbon black that is readily dispersible in water and forms a stable aqueous dispersion w9x. The modified carbon black was simply dispersed in water and added before gelation. Aerogels with modified carbon black exhibited a dramatic difference in mechanical properties less friable., optical appearance, and generation of carbon fines. These properties are related to better dispersion and reactions between the modified carbon and silica w10x. The thermal conductivity of compacts at ambient temperature and as a function of pressure was determined using a hot plate method.

4. Results A major problem with the use of aerogel granule insulation, has been that thermal performance is worse than that of a monolith because of gas phase conduction in intergranular regions. Only at very low pressures does thermal performance of granules and monoliths become similar. This is illustrated in Fig. 1 which shows the simulated variation of l with pressure as a function of packing fraction. The modeling assumes 100 m m granules with a surface area of 800 m2rg, 15 wt% carbon, and the total compact density is fixed at 100 kgrm3. As f is decreased, the density of the individual granules is increased to keep the total density constant. Reducing granule size can eliminate intergranular gas phase conduction

Fig. 2. Simulated effect of granule size on the change in l with pressure for a granule compact with f equal to 1.

at a higher pressure. Fig. 2 shows the simulated l values vs. pressure for granule sizes which span the range from the smallest obtainable by jet-milling 1 m m. to the largest which might be produced economically 10 mm.. The packing fraction is fixed at 0.7 which is reasonable for a compact under a small load e.g., the 1 bar load in a vacuum panel.. As part of our effort to optimize aerogel granules for use in vacuum panels at moderate pressures, we produced a series of aerogel granules with granule density of 90100 kgrm3, granule size in the 90250

Fig. 1. Simulated thermal conductivity variation as a function of gas pressure and packing fraction for 100 m m diameter granules.

Fig. 3. l variation with gas pressure for granule compacts under a 1 bar load containing different carbon levels lines for guidance only..

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Fig. 4. Effect of the type of carbon black addition to the thermal performance of granule compacts Under a 1 bar load lines for guidance only..

Fig. 6. Comparison of thermal performance for aerogel granule compacts and an opacified, aerogel monolith lines for guidance only..

m m range and various carbon contents. The carbon was added to the sol before gelation. When the granules were compacted to 1 bar the densities were ; 100 kgrm3. The thermal performance was measured and is shown in Fig. 3. In order to understand if the form of carbon addition was the reason for the performance, we compared four samples of the same density containing no carbon vs. 15 wt% carbon added by mixing aerogel granules and carbon black, or by adding either unmodified conventional. carbon black or surface modified carbon black to the sol

before gelation. The thermal performance of these is given in Fig. 4. To ascertain why the thermal performance exhibited such a dramatic decrease in l at moderate pressures, we measured l vs. P for a wide range of granule densities and particle sizes. Fig. 5 illustrates the key results. Fig. 6 shows l vs. P curves for three different particle sizes of the same granules. Also shown is l vs. P for an opacified monolith with excellent thermal performance w11x.

5. Discussion In Fig. 1, at ambient pressures and f equal to 1 corresponding to a monolith., l is dramatically lower than that of air because of the Knudsen effect in the intragranular pores since the pore size and gas mean free path at ambient pressure are of the same order. Reducing the pressure to 110% of ambient pressure results in almost complete elimination of gas phase conduction Fig. 1.. We note that the predicted l, at ambient pressure, for the monolith is lower than experimental values. This is because real aerogels have a distribution of pore sizes rather than the unimodal pore size distribution assumed here and the presence of a few large pores can dramatically degrade thermal performance. As f is decreased from that of a monolith f s 1. to the value for a

Fig. 5. Change in l P behavior with compact density lines for guidance only..

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loose-fill application f ; 0.5., the ambient pressure performance degrades because of intergranular conduction. The decrease in l from 10 5 to 10 3 Pa is small because of the smaller pore size in those granules corresponding to their higher granule density and the fact that 1r2 of the volume is filled with gas in larger pores. For the lower f values, l exhibits a significant decrease only when the pressure is sufficiently low and the mean free path of the gas is similar to the intergranular pore size. To further improve the performance of aerogel-based insulation, they can be packaged under a moderate vacuum by sealing in a plastic barrier. However, the lower gas pressure limit of that approach is ; 10 3 Pa. Only by using a metal enclosure can lower pressures be employed but that dramatically increases costs and introduces significant thermal bridging problems. In Fig. 2, for the smallest particle size, the thermal performance approaches that of a monolith. Jet-milling an aerogel to small size is expensive and might result in porosity loss. The other problem is that handling of low density powders becomes quite difficult when the particle size is below 100 m m. Another approach is to use several different particle sizes in an effort to increase f . By using two particle sizes, Herrmann et al. w12x were able to lower the ambient thermal conductivity of aerogel granules from 0.0185 to 0.016 Wrm K but at the expense of increasing the compact density from 135 to 160 kgrm3. As previously predicted w13x, the thermal performance improves as carbon content is increased from 0 to 15% in Fig. 3. What was not expected for granule compacts is the excellent thermal insulation performance at both ambient pressure and at moderate vacuum levels. Also, the type of carbon addition has a dramatic affect on thermal performance as shown in Fig. 4. The sample which was physically mixed exhibits a slightly higher density as a result of relatively dense carbon black filling intergranular spaces. All samples exhibit unanticipated low l at ambient pressure and rapid decrease in l at moderate pressures. When a modified carbon black is employed, the thermal performance is significantly better than dispersing conventional carbon black in the sol before gelation. This is presumably the result of better carbon dispersion on 110 m m length

scales. We note that the use of modified carbon is a much lower cost solution US$12rkg of carbon. than either CVI w11x or organosilane w14x pyrolysis approaches. As shown in Fig. 5, when the density is above a certain value, typical granule thermal performance as predicted in Fig. 1 is observed. Changing the size of the higher density granules only shifts the l drop observed at 1010 4 Pa to higher or lower pressures. We postulate that the reasons for the low l is a result of rearrangement, deformation and fracture which yields f close to 1 when a load of 1 bar is applied w15x. Further evidence that f is ; 1 is that the granule size see Fig. 6. has a very small affect on l vs. P. For compacts backfilled with gases such as argon, the measured l is independent of gas for a pressure of 10 2 10 3 Pa providing further evidence that f ; 1. It is interesting to note that the same thermal performance, at both ambient pressure and moderate pressures, can be obtained with granule compacts as with a monolith. Thermal conductivity of these compacts at ambient temperature and pressure is within 10% of the best value reported for monoliths w1,16x. Processing time for granules is significantly less, and granules can be easily formed into a range of insulation sizes and shapes.

6. Conclusion By employing a novel approach for surface modifying carbon black, improved aerogel properties thermal and mechanical. are obtained. When opacified granules are produced with the optimum densityrstrength, the application of a 1 bar load results in rearrangement of the granules such that a packing fraction approaching one is achieved. Thermal performance at ambient pressure and vacuum is similar to aerogel monoliths.

Acknowledgements The authors thank William Ackerman and Tina Hansen of NanoPore and Dr John Ross of Cabot for many helpful discussions.

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