Abstract
Halloysite is a naturally occurring nanometer scale tube that is capable of both enhancing the physical properties of a material and functionalizing the material. The addition of halloysite into polymeric materials increases the composite physical strength because of the shape and stability of these 50-nm diameter and ca. 1,500 nm length tubes. Whereas the unique chemical and physical characteristics of halloysite allow for loading drugs, biomacromolecules, anti-corrosion agents, flame-retardant agents, and metal nanoparticles followed by their controlled release. Therefore, by loading a chemical of interest inside of the tubes and then mixing the modified halloysite with various materials one will not only be able to make stronger materials but make them smarter and provide sustained functionality that would otherwise not be possible.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Joussein E, Petit S, Churchman J, Theng B, Righi D, Delvaux B (2005) Halloysite clay minerals – a reviewer. Clay Miner 40:383–426
Lvov Y, Abdullayev E (2013) Functional polymer – clay nanotube composites with sustained release of chemical agents. Prog Polym Sci 38:1690–1719
Du M, Guo B, Jia D (2010) Newly emerging applications of halloysite nanotubes: a review. Polym Int 59:574–595
Lvov Y, Shchukin D, Möhwald H, Price R (2008) Clay nanotubes for controlled release of protective agents – perspectives. ACS Nano 2:814–820
Price R, Gaber B, Lvov Y (2001) In-vitro release characteristics of tetracycline, khellin and nicotinamide adenine dinucleotide from halloysite; a cylindrical mineral for delivery of biologically active agents. J Microencapsul 18:713–723
Lvov Y, Aerov A, Fakhrullin R (2014) Clay nanotubes encapsulation for functional biocomposites. Adv Colloid Interface Sci 207:189–198. doi:10.1016/j.cis.2013.10.006
Abdullayev E, Lvov Y (2011) Clay nanotubes for controlled release of protective agents – a review. J Nanosci Nanotech 11:10007–10026
Yelleswarapu C, Gu G, Abdullayev E, Lvov Y, Rao D (2010) Nonlinear optics of nontoxic nanomaterials. Opt Commun 283:438–441
Abdullayev E, Price R, Shchukin D, Lvov Y (2009) Halloysite tubes as nanocontainers for anticorrosion coating with benzotriazole. Appl Mater Interfaces 2:1437–1442
Kirkman JH (1981) Morphology and structure of halloysite in New Zealand tephras. Clays Clay Miner 29:1–9
Lu D, Chen H, Wu J, Chan C (2011) Direct measurements of the Young’s modulus of a single halloysite nanotube using a transmission electron microscope with a bending stage. J Nanosci Nanotechnol 11:7789–7793
Singh B (1996) Why does halloysite roll? A new model. Clays Clay Miner 44:191–196
Singh B, Mackinnon I (1996) Experimental transformation of kaolinite to halloysite. Clays Clay Miner 44:825–834
Abdullayev E, Shchukin D, Lvov Y (2008) Halloysite clay nanotubes as a reservoir for corrosion inhibitors and template for layer-by-layer encapsulation. Polym Mater Sci Eng 99:331–342
Churchman GJ, Carr RM (1975) The definition and nomenclature of halloysites. Clays Clay Miner 23:382–388
Bergaya F, Theng BKG, Lagaly G (2006) Handbook of clay science. Elsevier, Amsterdam
Vergaro V, Abdullayev E, Cingolani R, Lvov Y, Leporatti S (2010) Halloysite clay nanotubes: characterization and biocompatibility study. Biomacromolecules 11:820–828
Tazaki K (2005) Microbial formation of a halloysite-like mineral. Clays Clay Miner 53:224–233
Carr RM, Chaikum N, Patterson N (1978) Intercalation of salts in halloysite. Clays Clay Miner 26:144–152
Liu M, Guo B, Du M, Cai X, Jia D (2007) Properties of halloysite nanotube–epoxy resin hybrids and the interfacial reactions in the systems. Nanotechnology 18:455703
Suh Y, Kil D, Chung K, Abdullayev E, Lvov Y, Mongayt D (2011) Natural nanocontainer for the controlled delivery of glycerol as a moisturizing agent. J Nanosci Nanotechol 11:661–665
Veerabadran N, Price R, Lvov Y (2007) Clay nanotubes for encapsulation and sustained release of drugs. NANO 2:215–222
Lai X, Agarwal M, Lvov Y, Pachpande C, Varahramyan K, Witzmann F (2013) Proteomic profiling of halloysite clay nanotube exposure in intestinal cell co-culture. J Appl Toxicol 33:1316–1329
Lvov Y, Price R (2008) Halloysite nanotubules a novel substrate for the controlled delivery of bioactive molecules. In: Ruiz-Hitzky E, Ariga K, Lvov Y (eds) Bio-inorganic hybrid nanomaterials. Wiley, London/Berlin, pp 440–478
Lvov Y, Price R, Gaber B, Ichinose I (2002) Thin film nanofabrication via layer-by-layer adsorption of tubule halloysite, spherical silica, proteins and polycations. Coll Surf Eng 198–200:375–382
Liu M, Guo B, Du M, Jia D (2007) Drying induced aggregation of halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes solution and its effect on properties of composite films. Appl Phys A: Mater Sci Process 88:391–395
Wei W, Abdullayev E, Hollister A, Mills D, Lvov Y (2012) Clay nanotube/poly(methyl methacrylate) bone cement composite with sustained antibiotic release. Macromol Mater Eng 297:645–653
Zhao M, Liu P (2008) Adsorption behavior of methylene blue on halloysite nanotubes. Microporous Mesoporous Mater 112:419–424
Luo P, Zhao Y, Zhang B, Liu J, Yang Y, Liu J (2010) Study on the adsorption of Neutral Red from aqueous solution onto halloysite nanotubes. Water Res 44:1489–1497
Yah W-O, Takahara A, Lvov Y (2012) Selective modification of halloysite lumen with octadecyl phosphonic acid: new inorganic tubular micelle. J Am Chem Soc 134:1853–1859
Shchukin D, Price R, Lvov Y (2005) Biomimetic synthesis of Vaterite in the interior of clay nanotubules. Small 1:510–513
Zhao Y, Abdullayev E, Vasiliev A, Lvov Y (2013) Halloysite nanotubule clay for efficient water purification. J Coll Interface 406:121–129
Veerabadran N, Price R, Lvov Y (2008) Tubule clay nanoreactor for template synthesis of silver nanoparticles. Polym Mater Sci Eng 99:566–577
Abdullayev E, Sakakibara K, Okamoto K, Wei W, Ariga K, Lvov Y (2011) Natural tubule clay template synthesis of silver nanorods for antibacterial composite coating. ACS Appl Mater Interfaces 3:4040–4048
Abdullayev E, Joshi A, Wei W, Lvov Y (2012) Selective lumen etching for clay nanotubes: enhanced loading capacity. ACS Nano 6:7216–7226
Yah W-O, Xu H, Soejima H, Ma W, Takahara T, Lvov Y (2012) Biomimetic dopamine derivative for selective polymer modification of halloysite nanotube lumen. J Am Chem Soc 134:12134–12137
Wei W, Minullina R, Fakhrullin R, Abdullayev E, Mills D, Lvov Y (2014) Enhanced efficiency of antiseptics with sustained release from clay nanotubes. RCS Adv 4:488–495
Cavallaro G, Lazzara G, Milioto S (2011) Dispersions of nanoclays of different shapes into aqueous and solid biopolymeric matrices. Ext Phys-Chem Stud Langmuir 27:1158–1163
Kommireddy D, Sriram S, Lvov Y, Mills D (2006) Layer-by-layer assembled nanoparticle thin films – a new surface modification approach for stem cell attachment. Biomaterials 27:4296–4303
Du M, Guo B, Liu M, Jia D (2007) Thermal decomposition and oxidation ageing behaviour of polypropylene/halloysite nanotube nanocomposites. Polym Polym Compos 15:321–328
Lecouvet B, Gutierrez J, Sclavons M, Bailly C (2011) Structure property relationships in polyamide 12/halloysite nanotube nanocomposites. Polym Degrad Stab 96:226–235
Voon H, Bhat R, Easa A, Liong M, Karim A (2012) Effect of addition of halloysite nanoclay and SiO2 nanoparticles on barrier and mechanical properties of bovine gelatin films. Food Bioprocess Technol 5:1766–1774
Ruiz-Hitzky E, Darder M, Aranda P, Ariga K (2010) Advances in biomimetic and nanostructured biohybrid materials. Adv Mater 22:323–336
Hua F, Cui T, Lvov Y (2004) Ultrathin cantilevers based on polymer-ceramic nanocomposite assembled through layer-by-layer adsorption. Nano Lett 4:823–825
Cavallaro G, Donato D, Lazzara G, Milioto S (2011) Films of halloysite nanotubes sandwiched between two layers of biopolymer: from the morphology to the dielectric, thermal, transparency, and wettability properties. J Phys Chem C 115:20491–20498
Zheng Y, Wang A (2010) Enhanced adsorption of ammonium using hydrogel composites based on chitosan and halloysite. J Macromol Sci A: Pure Appl Chem 47:33–38
Shchukin D, Moehwald H (2007) Self-repairing coating containing active nanoreservoirs. Small 3:926–943
Veerabadran N, Lvov Y, Price R (2009) Organized shells on clay nanotubes for controlled release of macromolecules. Macromol Rapid Commun 24:99–103
Levis S, Deasy P (2003) Use of coated microtubular halloysite for the sustained release of diltiazem hydrochloride and propranolol hydrochloride. Int J Pharm 253:145–157
Kelly H, Deasy P, Ziaka E, Claffey N (2004) Formulation and preliminary in vivo dog studies of a novel drug delivery system for the treatment of periodontitis. Int J Pharm 274:167–183
Levis S, Deasy P (2002) Characterization of halloysite for use as a microtubular drug delivery system. Int J Pharm 243:125–134
Abdullayev E, Lvov Y (2013) Polymeric composites with ceramic nanotube endoskeleton loaded with functional chemical agents. J Mater Chem B 1:2894–2903
Shamsi M, Geckeler K (2008) The first biopolymer-wrapped non carbon nanotubes. Nanotechnology 19:075604
Ward C, Song S, Davis E (2010) Controlled release of tetracycline–HCl from halloysite–polymer composite films. J Nanosci Nanotechnol 10:6641–6649
Forsgren J, Jämstorp E, Bredenberg S, Engqvist H, Strømme M (2010) A ceramic drug delivery vehicle for oral administration of highly potent opioids. J Pharm Sci 99:219–226
Zhou W, Guo B, Liu M, Liao R, Bakr A, Rabie M, Jia D (2009) Poly(vinyl alcohol)/halloysite nanotubes bio nanocomposite films: properties and in vitro osteoblasts and fibroblasts response. J Biomed Mater Res A 93:1574–1581
Abdullayev E, Lvov Y (2010) Clay nanotubes for corrosion inhibitor encapsulation: release control with end stoppers. J Mater Chem 20:6681–6687
Zhai R, Zhang B, Liu L, Xie Y, Zhang H, Liu J (2010) Immobilization of enzyme biocatalyst on natural halloysite nanotubes. Catal Commun 12:259–263
Datta S, Christena LR, Rajaram YRS (2012) Enzyme immobilization: an overview on techniques and support materials. 3 Biotech 3:1–9
Chao C, Zhang B, Zhai R, Xiang X, Liu J, Chen R (2013) Natural nanotube-based biomimetic porous microspheres for significantly enhanced biomolecule immobilization. ACS Sustain Chem Eng 1:1145
Konnova S, Sharipova I, Ilinskaya O, Lvov Y, Fakhrullin R (2013) Cell-mediated three-dimensional assembly of halloysite nanotubes. Chem Commun 49:4208–4210
Fakhrullin R, Lvov Y (2012) “Face-lifting and make-up” for microorganisms (layer-by-layer polyelectrolyte nanocoating). ACS Nano 6:4557–4564
Abdullayev E, Price R, Shchukin D, Lvov Y (2009) Halloysite tubes as nanocontainers for anticorrosion coating with benzotriazole. ACS Appl Mater Interf 1:1437–1443
Joshi A, Abdullayev E, Vasiliev A, Volkova O, Lvov Y (2013) Interfacial modification of clay nanotubes for the sustained release of corrosion. Langmuir 29:7439–7445
Schomburg I, Chang A, Placzek S, Söhngen C, Rother M, Lang M, Munaretto C, Ulas S, Stelzer M, Grote A, Scheer M, Schomburg D (2013) Interfacial Modification of Clay Nanotubes for the Sustained Release of Corrosion Inhibitors. BRENDA in 2013: integrated reactions, kinetic data, enzyme function data, improved disease classification: new options and contents in BRENDA. Nucleic Acids Res 41(Database issue):D764–D772
Acknowledgements
This work was performed according to the Russian Government Program of Competitive Growth of Kazan Federal University. This work was partially funded by Russian Scientific Fund grant no. 14-14-00924.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer Science+Business Media Dordrecht
About this paper
Cite this paper
Tully, J., Fakhrullin, R., Lvov, Y. (2015). Halloysite Clay Nanotube Composites with Sustained Release of Chemicals. In: Bardosova, M., Wagner, T. (eds) Nanomaterials and Nanoarchitectures. NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-9921-8_5
Download citation
DOI: https://doi.org/10.1007/978-94-017-9921-8_5
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-017-9920-1
Online ISBN: 978-94-017-9921-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)