Surface Improvement of Halloysite Nanotubes

A novel development on halloysite-polyvinyl alcohol (HNTs-PVA) nanocomposites has been conducted using malonic acid (MA) by crosslinking PVA and HNTs. PVA-MA crosslinking produces smooth surfaces, which play an important role in enhancing the properties of HNTs-PVA nanocomposite. The crystallographic structures of crosslinked HNTs-PVA show almost no change as depicted by the X-ray diffraction (XRD)-2θ-peak, suggesting that MA has no or little influence on the crystallographic structure of the HNTs-PVA. Images taken by field emission scanning electron microscope (FESEM) suggest possible effects of MA on the morphology and internal features of HNTs-PVA by reducing the agglomeration of HNTs, which is considered a decisive step in improving the surface qualities of HNTs. Investigating the samples using the Brunauer–Emmelt–Teller (BET) technique showed that the surface area was increased by about 10 times, reaching the second highest recorded results compared to the HNTs, which could be considered a breakthrough step in enhancing the properties of HNTs-PVA due to MA crosslinking.

[1]  P. Zhu,et al.  Crosslinking reaction of poly(vinyl alcohol) with glyoxal , 2010 .

[2]  Kaiyan Qiu Biobased and biodegradable polymer nanocomposites , 2012 .

[3]  G. Cavallaro,et al.  Hydrophobically Modified Halloysite Nanotubes as Reverse Micelles for Water-in-Oil Emulsion. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[4]  Kenan Song,et al.  Enhanced Wear Resistance of Transparent Epoxy Composite Coatings with Vertically Aligned Halloysite Nanotubes. , 2016, ACS applied materials & interfaces.

[5]  B. Adhikari,et al.  Polyvinyl alcohol : A taste sensing material , 2006 .

[6]  Yanjun Tang,et al.  Novel polyvinyl alcohol/styrene butadiene rubber latex/carboxymethyl cellulose nanocomposites reinforced with modified halloysite nanotubes , 2013 .

[7]  A. Mohamad,et al.  Properties and Applications of Polyvinyl Alcohol, Halloysite Nanotubes and Their Nanocomposites , 2015, Molecules.

[8]  B. Guo,et al.  Carboxylated butadiene-styrene rubber/halloysite nanotube nanocomposites : Interfacial interaction and performance , 2008 .

[9]  V. Bertolino,et al.  Effect of the Biopolymer Charge and the Nanoclay Morphology on Nanocomposite Materials , 2016 .

[10]  Kenan Song,et al.  Spray-Coated Halloysite-Epoxy Composites: A Means To Create Mechanically Robust, Vertically Aligned Nanotube Composites. , 2016, ACS applied materials & interfaces.

[11]  A. Netravali,et al.  Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol , 2013 .

[12]  G. Cavallaro,et al.  Halloysite nanotubes loaded with peppermint essential oil as filler for functional biopolymer film. , 2016, Carbohydrate polymers.

[13]  Shen Jian,et al.  Crosslinked PVA-PS thin-film composite membrane for reverse osmosis , 1987 .

[14]  K. Sing,et al.  Adsorption by Powders and Porous Solids: Principles, Methodology and Applications , 1998 .

[15]  Filippo Parisi,et al.  Modified halloysite nanotubes: nanoarchitectures for enhancing the capture of oils from vapor and liquid phases. , 2014, ACS applied materials & interfaces.

[16]  Y. Lvov,et al.  Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide. , 2012, ACS nano.

[17]  Bruno Delvaux,et al.  Halloysite clay minerals – a review , 2005, Clay Minerals.

[18]  G. Cavallaro,et al.  Thermal and dynamic mechanical properties of beeswax-halloysite nanocomposites for consolidating waterlogged archaeological woods , 2015 .

[19]  Roberto Solaro,et al.  Biodegradation of poly(vinyl alcohol) based materials , 2003 .

[20]  C. Yeom,et al.  Pervaporation separation of water-acetic acid mixtures through poly(vinyl alcohol) membranes crosslinked with glutaraldehyde , 1996 .

[21]  C. Chan,et al.  High-impact polystyrene/halloysite nanocomposites prepared by emulsion polymerization using sodium dodecyl sulfate as surfactant. , 2011, Journal of colloid and interface science.

[22]  P. Yuan,et al.  Properties and applications of halloysite nanotubes: recent research advances and future prospects , 2015 .

[23]  V. Vergaro,et al.  Cytocompatibility and uptake of halloysite clay nanotubes. , 2010, Biomacromolecules.

[24]  A. Sulong,et al.  Impact of Sulfuric Acid Treatment of Halloysite on Physico-Chemic Property Modification , 2016, Materials.

[25]  Hélio A. Duarte,et al.  Structural, Electronic, and Mechanical Properties of Single-Walled Halloysite Nanotube Models , 2010 .

[26]  A. Sulong,et al.  Effect of halloysite nanotubes loading on thermo-mechanical and morphological properties of polyurethane nanocomposites , 2017 .

[27]  Demin Jia,et al.  Drying induced aggregation of halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes solution and its effect on properties of composite film , 2007 .

[28]  T. Brill,et al.  Spectroscopy of Hydrothermal Reactions 13. Kinetics and Mechanisms of Decarboxylation of Acetic Acid Derivatives at 100−260 °C under 275 bar , 1999 .

[29]  T. Rousakis,et al.  Effects of carbon nanotube enrichment of epoxy resins on hybrid FRP–FR confinement of concrete , 2014 .

[30]  G. Cavallaro,et al.  Exploiting the Colloidal Stability and Solubilization Ability of Clay Nanotubes/Ionic Surfactant Hybrid Nanomaterials , 2012 .

[31]  B. Guo,et al.  Poly(vinyl alcohol)/halloysite nanotubes bionanocomposite films: Properties and in vitro osteoblasts and fibroblasts response. , 2009, Journal of biomedical materials research. Part A.

[32]  E. Chiellini,et al.  Biodegradation of poly(vinyl alcohol) with different molecular weights and degree of hydrolysis , 2000 .

[33]  Y. Ye,et al.  Effects of acid treatment on the physico-chemical and pore characteristics of halloysite , 2012 .

[34]  Yan-Xing Wang,et al.  Preparation of halloysite-derived mesoporous silica nanotube with enlarged specific surface area for enhanced dye adsorption , 2016 .