Advertisement

Elastic superhydrophobic and water glass-based silica aerogels and applications

  • Amirisetty Venkateswara RaoEmail author
Original Paper: Nano- and macroporous materials (aerogels, xerogels, cryogels, etc.)
First Online:
  • 140 Downloads

Abstract

Silica aerogels with high elasticity and superhydrophobicity have several scientific and technological applications such as in multidisciplinary subjects dealing with liquid/solid interfacial energies, long-range attractive interactions, frictionless flow of liquids through nano and microchannels, pipes, and storage of mechanical energy. In addition, the aerogels are being used as light weight super thermal, acoustic and electrical insulating materials especially in microelectronics, aeronautics, Space, in high-energy physics; as bandages for leaks in oil supply pipes, and underwater pressure sensitive devices. The present paper describes the preparation, physicochemical properties along with applications of elastic superhydrophobic silica aerogels with a water contact angle as high as 175o and Young’s modulus as low as 3 × 104 N/m2 with one of the highest reverse compressibility of around 60% known for any solid state material. The Young’s modulus is measured by uniaxial compression. The water droplets placed on surfaces coated with the superhydrophobic aerogel powder at 55° of angle of inclination showed velocities as high as 1.44 m s−1 (free fall velocity ≈ 1.5 m s−1). Water intrusion into the superhydrophobic aerogels at pressures greater than the Laplace pressure exhibited hysteresis resulting in the storage of water in the aerogels, and indicating the sizes of the pores. It has been shown that the elastic superhydrophobic aerogels are very efficient adsorbents of oil and organic compounds and hence useful for oil-spill clean-up applications, in addition to their potential use as laser induced X-ray and plasma emission sources. Moreover, the recent developments in the field of aerogels have shown a great potential for the combination of ambient pressure drying and a low-cost inorganic, and easily available precursor such as sodium silicate, which is also called as water–glass, for the production of hydrophobic silica aerogels on a large industrial scale for commercial applications. The properties of such aerogels are comparable to those obtained by the conventional supercritical drying methods. So far, only powders and translucent and transparent grains of sizes 2–4 mm, are being produced. The experimental results on the preparation and properties along with various applications of elastic superhydrophobic and sodium silicate-based silica aerogels, are presented in this paper. Several sol–gel and drying parameters affecting the quality of the aerogels, in terms of low-density (<0.05 g/cm3), high-optical transmission (> 90% in the visible range), are also presented and discussed.

This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

Professor Jean Phalippou was very kind in arranging my visit to his Aerogel laboratory during the year 1995 and provided me excellent hospitality, and had spent his very valuable time with me. Professor Jean Phalippou is a great friend and colleague and we always remember him and his work. The author is highly thankful to the editors for having been given me an opportunity to work in preparing this paper in the memory of Prof. Jean Phalippou. The author is most grateful to Professor George W. Scherer, Princeton University, USA, for the kind help regarding some references and other aspects of the present paper.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Kistler SS (1931) Coherent expanded aerogels and jellies. Nature 127:741Google Scholar
  2. 2.
    Fricke J (1988) Aerogels. Sci Am 258:68–73Google Scholar
  3. 3.
    Fricke J, Tillotson T (1997) Aerogels: production, characterization and applications Thin Solid Films 297:212–223Google Scholar
  4. 4.
    Hrubesh LW (1990) Aerogels: the world’s lightest solids. Chem Ind 24:824–827Google Scholar
  5. 5.
    Reyness J, Woignier T, Phalippou J (2001) Permeability measurement in composite aerogels: applications to nuclear waste storage. J Noncryst Solids 285:323–327Google Scholar
  6. 6.
    Poelz G, Riethmuller R (1982) Preparation of silica aerogel for Cherenkov counters. J Nucl Instrum Methods 195:491–503Google Scholar
  7. 7.
    Adachi I et al. (2005) Study of highly transperent silica aerogel as a RICH radiator. Nucl Instrum Methods Phys Res A553:146–151Google Scholar
  8. 8.
    Sumiyoshi T, Adechi I, Enomoto R, Iijime T, Sude R, Yokoyame M, Yokogawa H (1998) Silica aerogels in high-energy physics. J Noncryst Solids 225:369–374Google Scholar
  9. 9.
    Jang KY, Kim K, Upadhye RS (1990) Study of sol–gel processing for fabrication of hollow silica–aerogel spheres. J Vac Sci Technol A8:1732–1735Google Scholar
  10. 10.
    Fricke J, Hummer E, Morper H-J, Scheuerpflug P (1989) Thermal properties of silica aerogels. Rev Phys Appl C4:87–97Google Scholar
  11. 11.
    Schlief T, Gross J, Fricke J (1992) Ultrasonic attenuation in silica aerogels. J Noncryst Solids 145:223–226Google Scholar
  12. 12.
    Venkateswara Rao A, Hegde ND, Hirashima H (2007) Adsorption and desorption of organic liquids in elastic superhydrophobic silica aerogels. J Colloid Interface Sci 305:124–132Google Scholar
  13. 13.
    Venkateswara Rao (2017). Air Glass Laboratory, Department of Physics, Shivaji University, Kolhapur (Unpublished Results, 2018)Google Scholar
  14. 14.
    Venkateswara Rao, Kaur C, Pisal AA, Chaurasia S, Deo MN & Sharma SM, MRS (Proceedings) Advances, 2017, Vol. 2, Issue 57 (Nanomaterials), 498–503Google Scholar
  15. 15.
    Phalippou J, Vacher R, editors (1998), Aerogels 5, Proceedings of the Fifth International Symposium on Aerogels (ISA-5), J Noncryst Solids. 225Google Scholar
  16. 16.
    Gesser HD, Goswami PC (1989) Aerogels and related porous materials. Chem Rev 89:765–788Google Scholar
  17. 17.
    Fricke J, Emmerling A (1992). Aerogels—Preparation, Properties, Applications, Structure and Bonding 77, Springer-Verlag, Berlin, p 37–87Google Scholar
  18. 18.
    Husing N, Schubert U (1998) Aerogels—airy materials: chemistry, structure, and properties. Angew Chem Int Ed 37:22–45Google Scholar
  19. 19.
    Pierre AC, Pajonk GM (2002) Aerogels and their applications. Chem Rev 102:4243–4265Google Scholar
  20. 20.
    Pajonk GM (2003) Some applications of silica aerogels. Colloid Polym Sci 281:637–651Google Scholar
  21. 21.
    Scherer George W (1994) Measuring permeability by the thermal expansion method for rigid or highly permeable gels. J Sol Gel Sci Technol 3:31–40Google Scholar
  22. 22.
    Gross J, Scherer GW (2003) Dynamic pressurization: novel method for measuring fluid permeability. J Noncryst Solids 325:34–47Google Scholar
  23. 23.
    Scherer GW, Gross J, Hrubesh LW, Coronado PR (2002) Optimization of the rapid supercritical extraction process for aerogels. J Noncryst Solids 311:259–272Google Scholar
  24. 24.
    Scherer GW, Hdach H, Phalippou J (1991) Thermal expansion of gels: a novel method for measuring permeability. J Noncryst Solids 130:157–170. [errata: J Noncryst Solids (1996) 194, 326]Google Scholar
  25. 25.
    Kistler SS (1932) Coherent expanded aerogels. J Phys Chem 36:52–64Google Scholar
  26. 26.
    Kistler SS, Caldwell AG (1934) Thermal conductivity of silica aerogel. Ind Eng Chem 26:658–662Google Scholar
  27. 27.
    Kistler SS (1942) The calculation of the surface area of microporous solids from measurements of heat conductivity. J Phys Chem 46:19–31Google Scholar
  28. 28.
    Kistler SS, Fischer EA, Freeman IR (1943). Sorption and surface area in silica aerogel. J Phys Chem 1909–1919Google Scholar
  29. 29.
    White JF (1939) Silica aerogel: effects of variables on its thermal conductivity. Ind Eng Chem 31:827–831Google Scholar
  30. 30.
    Peri John B (1966) Infrared study of OH and NH2 groups on the surface of a dry silica aerogel. J Phys Chem 70:2937–2945Google Scholar
  31. 31.
    Ebelmen M (1846) Recherches sur les combinaisons des acides borique at Silicique avec les ethers. Ann Chime Phys 16:129–166Google Scholar
  32. 32.
    Nicolaon GA, Teichner SJ (1968). Preparation of silica aerogels from methyl orthosilicate in alcoholic medium, and their properties. Bull Soc Chem. 1900Google Scholar
  33. 33.
    Schwertfeger F, Glaubitt W, Schubert U (1992) Hydrophobic aerogels from Si (O Me)4/Me Si (O Me)3 mixtures. J Noncryst Solids 145:85–89Google Scholar
  34. 34.
    Schwertfeger F, Emmerling A, Gross J, Schubert U, Fricke J (1994). Organically modified silica aerogels. In: Attia YA (ed) Sol–Gel Processing and Applications, Plenum Press, New York, p 343–349Google Scholar
  35. 35.
    Reynolds JP, Coronado PR, Hrubesh LW (2001) Hydrophobic aerogels for oil- spill clean up - systems and characterization J. Non-Cryst. Solids 292:127–137Google Scholar
  36. 36.
    Hrubesh LW, Coronado Satcher Jr. JH (2001) Solvent removal from water with hydrophobic aerogels J. Non-Cryst. Solids 285:328–332Google Scholar
  37. 37.
    Yokogawa H, Yokayama M (1995) Hydrophobic silica aerogels. J Noncryst Solids 186:23–29Google Scholar
  38. 38.
    Venkateswara Rao A, Haranath D (1999) Effect of methyltrimethoxysilane as a synthesis component on the hydrophobicity and some physical properties of Silica aerogels. Microporous Mesoporous Mater 30:267–273Google Scholar
  39. 39.
    Venkateswara Rao A, Pajonk GM (2001) Effect of methyltrimethoxysilane as a coprecursor on the optical properties of silica aerogels. J Noncryst Solids 285:202–209Google Scholar
  40. 40.
    Venkateswara Rao A, Pajonk GM, Bhagat SD (2004) Philippe Barboux, Comparative studies on the surface chemical modification of silica aerogels based on various organosilane compounds of the type RnSiX4−n. J Noncryst Solids 350:216–223Google Scholar
  41. 41.
    Venkateswara Rao A, Kalesh RR, Pajonk GM (2003) Hydrophobic and physical properties of TEOS-based silica aerogels using phenyltriethoxysilane as a synthesis component. J Mater Sci 38:4407–4413Google Scholar
  42. 42.
    Venkateswara Rao A, Kalesh RR (2003) Comparative studies of the physical and hydrophobic properties of TEOS-based silica aerogels using different coprecursors. Sci Tech Adv Mater 4:509–515Google Scholar
  43. 43.
    Venkateswara Rao A, Kulkarni MM, Amalmerkar DP (2003) Surface chemical modification of silica aerogels using various alkyl-alkoxy/chloro silanes. Appl Surf Sci 206:262–270Google Scholar
  44. 44.
    Venkateswara Rao A, Kalesh RR (2004) Organic surface modification of TEOS-based silica aerogels synthesized by coprecursor and derivatization methods. J Sol Gel Sci Technol 30:141–147Google Scholar
  45. 45.
    Venkateswara Rao A, Kulkarni MM (2002) Hydrophobic properties of TMOS/TMES-based silica aerogels. Mat Res Bull 37:1667–1677Google Scholar
  46. 46.
    Venkateswara Rao A, Kulkarni MM, Amalnerkar DP, Seth T (2003) Superhydrophobic silica aerogels based on methyltrimethoxysilane precursor. J Noncryst Solids 330:187–195Google Scholar
  47. 47.
    Wenzel RN (1936). Resistance of solid surfaces to wetting by water. Ind Eng Chem 28, 288–994.Google Scholar
  48. 48.
    Cassie ABD, Baxter S (1944) Wettability of porous surfaces. Trans Faraday Soc 28:546–551Google Scholar
  49. 49.
    Richard D, Quere D (1999) Drops rolling on a tilted nonwettable solid, D. Quere Europhys Lett 48(3):286–291Google Scholar
  50. 50.
    Dussan VEB, Chow RTP (1983) On the ability of drops or bubbles to stick to non-horizontal surfaces of solids. J Fluid Mech 137:1–29Google Scholar
  51. 51.
    Mahadevan L, Pomeall Y (1999) Rolling droplets. Phys Fluids 11(9):2449–2453Google Scholar
  52. 52.
    Venkateswara Rao A, Kulkarni MM, Bhagat SD (2005) Transport of liquids using superhydrophobic aerogels. J Colloid Interface Sci 285:413–418Google Scholar
  53. 53.
    Onda T, Shibuichi S, Satoh N, Tsuji K (1996) Super-water-repellent fractal surfaces. Langmuir 12(9):2125–2127Google Scholar
  54. 54.
    Oner D, McCarthy TJ (2000) Ultrahydrophobic surfaces. Effects of topography length scales on wettability. Langmuir 16:7777–7782Google Scholar
  55. 55.
    Yoshimistu Z, Nakajime A, Watanabe T, Hashimoto K (2002) Effects of surface structure on the hydrophobicity and sliding behavior of water droplets. Langmuir 18:5818–5822Google Scholar
  56. 56.
    Mahadevan L (2001) Non-stick water. Nature 411:895–896Google Scholar
  57. 57.
    Brinker CJ, Scherer GW (1990) Sol–Gel Science. Academic Press, San Diego, CAGoogle Scholar
  58. 58.
    Venkateswara Rao A, Bhagat SD, Hiroshima H, Pajonk GM (2006) Synthesis of flexible silica aerogels using methyltrimethoxysilane (MTMS) precursor. J Colloid Interface Sci 300:279–285Google Scholar
  59. 59.
    Chaput F, Lecomte A, Dauger A, Boilot JP (1989) Preparation and structure of aluminosilicate aerogels. Chem Mater 1:199–201Google Scholar
  60. 60.
    Henning S, Svensson L (1981) Production of silica aerogel. Phys Scr 23:697–702Google Scholar
  61. 61.
    Prassas M, Phalippou J, Zarzycki J (1984) Synthesis of monolithic silica gels by hypercritical solvent evacuation J Mater Sci 19:1656–1665Google Scholar
  62. 62.
    Van Lierop JG, Huizing A, Meerman WCPM, Mulder CAM (1986) Preparation of dried monolithic SiO2 gel bodies by an autoclave process. J Noncryst Solids 82:265–270Google Scholar
  63. 63.
    Venkateswara Rao A, Parvathy Rao A (1993) Effect of gel parameters on monolithicity and density of silica aerogels. J Mat Sci 28:3021–3026Google Scholar
  64. 64.
    Venkateswara Rao A, Pajonk GM, Parvathy NN, Elaloui E (1994). Influence of sol–gel parameters on transparency and monolithicity of silica aerogels. In: Attia YA (ed) Sol–Gel Processing and Applications, Plenum Press, New York, p 237–256Google Scholar
  65. 65.
    Venkateswara Rao A, Pajonk GM, Nadargi DY, Koebel MM (2003). Superhydrophobic and Flexible Aerogels, Chapter 4, Aerogels Handbook, Aegerter MA, et al. (Eds), p 79–101Google Scholar
  66. 66.
    Laplace Simon P. 10th Book Supplement: On Capillary Attraction, 1806Google Scholar
  67. 67.
    Smith DM, Deshpande R, Brinker CJ (1992) Preparation of low density aerogels at ambient pressure. Mater Res Soc Symp Proc 271:567–572Google Scholar
  68. 68.
    Prakash SS, Brinker CJ, Hurd CJ, Rao AJ (1995) Silica aerogel films prepared at ambient pressure, by using surface derivatization to induce reversible drying shrinkage. Nature 374:439–443Google Scholar
  69. 69.
    Schwertfeger F, Frank D, Schmidt M (1998) Hydrophobic waterglass-based aerogels without solvent exchange or supercritical drying. J Non-Cryst Solids 225:24–29Google Scholar
  70. 70.
    Venkateswara Rao A, Nelson E, Einarsurd M-A (2001) Effect of precursors, methylation agents and solvents on the physicochemical properties of silica aerogels prepared by atmospheric pressure drying method. J Non-Cryst Solids 296:165–171Google Scholar
  71. 71.
    Shewale PM, Venkateswara Rao A, Parvathy Rao A (2008) Effect of different trimethyl silylating agents on the hydrophobic and physical properties of silica aerogels. Appl Surf Sci 254:6902–6907Google Scholar
  72. 72.
    Venkateswara Rao A, Air Glass Laboratory, Department of Physics, Shivaji University, Kolhapur (Unpublished Results, 2018)Google Scholar
  73. 73.
    Venkateswara Rao A, Parvathy Rao A, Kulkarni MM (2004) Influence of gel gaining and Na2SiO3/H2O molar ratio on monolithicity and physical properties of water–glass-based aerogels dried at atmospheric pressure. J Non-Cryst Solids 350:224–229Google Scholar
  74. 74.
    Parvathy Rao A, Venkateswara Rao A (2008) Microstructural and physical properties of the ambient pressure-dried hydrophobic silica aerogels with various solvent mixtures. J Non-Cryst Solids 354:10–18Google Scholar
  75. 75.
    Parvathy Rao A, Venkateswara Rao A, Gurav JL (2008) Effect of protic solvents on the physical properties of the ambient pressure-dried hydrophobic silica aerogels using sodium silicate precursor. J Porous Mater 15:507–512Google Scholar
  76. 76.
    Venkateswara Rao, Pajonk GM, Bangi UKH, Rao AP, Koebel MM (2011). Chapter 5, Sodium silicate-based aerogels via ambient pressure drying. In: Aegerter MA (Eds) Aerogels Handbook, p 103–124Google Scholar
  77. 77.
    Parvathy Rao A, Venkateswara Rao A (2009) Improvement in optical transmission of the ambient pressure-dried hydrophobic nanostructured silica aerogels with mixed silylating agents. J Noncryst Solids 355:2260–2271Google Scholar
  78. 78.
    Schaefer DW, Keefer KD (1986) Structure of random porous materials. Phys Rev Lett 56:2199–2206Google Scholar
  79. 79.
    Woignier T, Phalippou J, Vacher R, Pelous J, Courtens E (1990) Fractal studies of silica aerogels by small angle nautron scattering. J Noncryst Solids 121:198–206Google Scholar
  80. 80.
    Vacher R, Woigner T, Pelous J, Courtens E (1998) Phys Rev B 37:6500–6508Google Scholar
  81. 81.
    Schaefer DW (1989) What factors control the structure of silica aerogels. Rev Phys Appl C4:121–126Google Scholar
  82. 82.
    Venkateswara Rao A et al. (2010) Reduction in the processing time of doped sodium silicate-based ambient pressure-dried aerogels using shaker. Microporous Mesoporous Mater 134:93–99Google Scholar
  83. 83.
    De Gennes PG (1985) Wetting: statics and dynamics. Rev Mod Phys 57:827–863Google Scholar
  84. 84.
    Young Thomas (1805) An essay on the cohesion of fluids. Philos Trans R Soc Lond 95:65–87Google Scholar
  85. 85.
    Singh S, Houston J, Swol FV, Brinker CJ (2006) Superhydrophobicity: drying transition of confined water. Nature 442:526–530Google Scholar
  86. 86.
    Joyce SA, Houston JE (1991) Interfacial-force microscopy of superhydrophobic surfaces. Rev Sci Instr 62:710–715Google Scholar
  87. 87.
    Smirnov BM (1991) Energetic process in macroscopic fractal structures. Sov Phys Usp 34(6):526–541Google Scholar
  88. 88.
    Smirnov BM (1991) A tangle of fractal fibers as a new state of matter. Sov Phys Usp 34(8):711–716Google Scholar
  89. 89.
    Phalippou J, Scherer GW, Woignier T, Bourret D, Sempere R (1995) Ultraporous materials with low permeability. J Noncryst Solids 186:64–72Google Scholar
  90. 90.
    Karatum O, Steiner III SA, Griffin JS, Shi W, Plata DL (2016) Flexible, mechanically durable aerogel composites for oil capture and recovery. ACS Appl Mater Interfaces 8:215–224Google Scholar
  91. 91.
    He Song, Chen X (2017) Flexible silica aerogel based on methyltrimethoxysilane with improved mechanical property. J Noncryst Solids 463:6–11Google Scholar
  92. 92.
    Mahadik DB, Jung H-N-R, Cho HH, Park H–H (2017) Flexible, elastic and superhydrophobic silica–polymer composite aerogels by high internal phase emulsion process. Compos Sci Tech 147:45–51Google Scholar
  93. 93.
    Yu. Y, Wu. X, Guo D, Fang J (2014) Preparation of flexible, hydrophobic, and oleophilic silica aerogels based on methyltrimethoxysilane precursor. J Mater Sci 49:7715–7722Google Scholar
  94. 94.
    Bhagat SD, Kim Y–H, Ahn Y-Soo, Yeo J–G (2006) Textural properties of ambient pressure-dried water–glass-based silica aerogel beads: one day synthesis Microporous Mesoporous Mater 96:237–244Google Scholar
  95. 95.
    Saho. Z, He X, Niu Z, Huang T, Cheng X, Zhang Y (2015) Ambient pressure-dried shape-controllable sodium silicate-based composite silica aerogel monoliths. Mater Chem Phys 5:1–8Google Scholar
  96. 96.
    Nah H–Y, Parale VG, Jung H–N–R, Lee K–Y, Lim C–H, Ku YS, Park H–H (2018) Role of oxalic acid in structural formation of sodium silicate-based silica aerogel by ambient pressure drying J Sol Gel Sci Technol 85:382–312Google Scholar
  97. 97.
    Hrubesh LW, Tillotson TM, Poco JF (1990) Charactarization of ultralow-density silica aerogels made from a condensed silica precursor. Mat Res Soc Symp Proc 180:315–323Google Scholar
  98. 98.
    Tillotson TM, Hrubesh LW (1990) Charactarization of partially condensed silica formed from the partial hydrolysis of TMOS. Mat Res Soc Symp Proc 180:309–313Google Scholar
  99. 99.
    Ishino M et al. (2001) Mass production of hydrophobic silica aerogel and read out opitics of Chernkov light. Nucl Instrum Methods Phys Res A, 57:581–587Google Scholar
  100. 100.
    Beghi, Chiurlo P, Cogliati G, Costa L, Dughi, Palledino M, Pirini MF, Rota F (1991) Sol–gel technology and the frontiers of optical materials, Chapter 2. In: Cerofolini CF, Mininni RM, Schwarz P (Eds). Chemistry for Innovative Materials, Eni Chem (Italy), pp 31–42Google Scholar
  101. 101.
    Cerofolini GF, Re N (1991) Chapteraerogels with various solvent 3. Chemistry for Innovative Materials. In: Cerofolini GF, Mininni, P Schwarz RM (Eds). Exploiting aerogel properties, Eni Chem (Italy), p 43–53Google Scholar
  102. 102.
    Venkateswara Rao (2009) Synthesis and applications of superhydrophobic silica aerogels. In Proceedings of the Intenational Conference on Sol–Gel Processing and Applications, Kalpakam, India, 129–134Google Scholar
  103. 103.
    Graham T (1864) Exchange of various solvents in silica hydrogels. J Chem Soc 17:318Google Scholar
  104. 104.
    Andrews T (1869) Presence of critical points in liquids. Philos Trans 159:575–590Google Scholar
  105. 105.
    Venkateswara Rao A. (2003) In: Chidambaram R., Banerjee S (eds) Aerogels: A novel class of solids with mesoscopic pores, in Materials Research : Current Scenario and Future Projections. Allied Publishers Pvt. Limited, New Delhi, pp 170–189Google Scholar
  106. 106.
    Parvathy Rao A., Venkateswara Rao A., Bangi Uzma K.H (2008) Low thermal conductive transparent and hydrophobic ambient pressure dried silica aerogels with various preparation conditions using sodium silicate solutions J. Sol- Gel Sci. and Tech. 47:85–94Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018
corrected publication 2018

Authors and Affiliations

  1. 1.Air Glass Laboratory, Department of PhysicsShivaji UniversityKolhapurIndia

Personalised recommendations

Cite article

Buy options