Halloysite clay nanotubes are safe and biocompatible nanomaterials and their application in biomaterials is very promising. The microencapsulation of yeast cells in the shell of clay nanotubes modifying their properties was demonstrated here. Each cell was coated with a 200–300 nm-thick tube shell and this coating was not harmful for these cells’ reproduction. Synthesis of magnetic nanoparticles on the surfaces of the nanotubes allowed for magnetic-field manipulation of the coated cells, including their separation. Providing nano-designed shells for biological cells is a step forward in development of ‘cyborg’ microorganisms combining their intrinsic properties with functions added through nano-engineering.

A compilation of Fe3+-bearing chlorite analyses is used: (1) to investigate the Alfree di-trioctahedral (AFDT) substitution 2Fe3+ +□= 3(Mg,Fe2+) in chlorite; and (2) to estimate the composition of a ferri-sudoite end-member (Si3Al)[(Fe2+,Mg)2□Al]O10(OH)8 within the chlorite solid-solution domain. According to our observations, up to two Fe3+ cations might be allocated in the M2-M3 chlorite sites by the substitution AFDT, which does not involve Al. These unexpected observations were made possible by the development of μXANES techniques allowing in situ measurements of XFe3+ (Fe3+/(Fe2+ + Fe3+)) in heterogeneous chlorite. Although further studies are required to confirm the crystallographic position of Fe3+ and refine its ionic/ magnetic behaviour in chlorite, this development creates opportunities for developing new geothermometers.

Concrete and bentonite are being considered as engineered barriers for the deep geological disposal of high-level radioactive waste in argillaceous rocks. Three hydrothermal laboratory experiments of different scalable complexity were performed to improve our knowledge of the formation of calcium aluminate silicate hydrates (C-A-S-H) at the interface between the two materials: concretebentonite transport columns, lime mortar-bentonite transport columns and a portlandite- (bentonite and montmorillonite) batch experiment. Precipitation of C-A-S-H was observed in all experiments. Acicular and fibrous morphologies with certain laminar characteristics were observed which had smaller Ca/Si and larger Al/Si ratios with increasing temperature and lack of accessory minerals. The compositional fields of these C-A-S-H phases formed in the experiments are consistent with Al/(Si+Al) ratios of 0.2– 0.3 described in the literature. The most representative calcium silicate hydrate (C-S-H) phase from the montmorillonite–cement interface is Al-tobermorite. Structural analyses revealed a potential intercalation or association of montmorillonite and C-A-S-H phases at the pore scale.

The present study explores the effect of a magnetically modified halloysite (mHNT) surface on the structure and properties of biodegradable polymer nanocomposites based on poly ɛ-caprolactone (PCL). Halloysite nanotubes (HNTs) have been modified by a scalable and tunable procedure using magnetic Fe oxide particles prepared by microwave-assisted synthesis fromferrous sulfate at high pH. The HNT content in composites prepared in melt varied from 5 to 30 wt.%. Application of magnetically modified HNT to PCL resulted in the formation of soft magnetic materials. Analyses of the nanocomposite structure revealed that both natural and magnetized HNTs, as well as free magnetite particles are dispersed uniformly in the polymer matrix. Investigation of the mechanical and physical properties confirmed that the reinforcing ability of HNTs was not affected by magnetic modification.

The MH-2B borehole, a part of Project HOTSPOT, was drilled to a depth of 1821 m in late Cenozoic basalts, hyaloclastites and interbedded lake sediments, on the Mountain Home Air Force Base in southern Idaho, USA. Drillers encountered hot water (145°C) under artesian pressure at 1745 m in a narrow zone of highly fractured rock associated with a major sub-surface fault. X-ray diffraction (XRD) analysis identified corrensite (with and without smectite) between 1700 and 1800 m, but only smectite above 1700 m and below 1800 m. This corrensite horizon contains a relatively narrow zone of fracturing and hot artesian water near its centre but for the most part occurs in relatively massive basalt flows. No evidence was found for randomly interstratified chlorite-smectite.

Concepts for geological disposal of high-level radioactive waste usually include bentonite buffer materials. Numerous studies have been performed with most usingWyoming bentonite. Gaomiaozi (GMZ) bentonite has been selected as a potential buffer/backfill material for the deep geological repository of high-level radioactive waste in China. In this context, the highly alkaline environment induced by cementitious materials in the repository is likely to alter montmorillonite, the main clay mineral in GMZ bentonite. This alteration may result in deterioration of the physical and/or chemical properties of the buffer material. To acquire quantitative data which would allow us to assess the dissolution of montmorillonite and changes in the diffusivity of hydroxide ions as well as their effects on the swelling pressure and permeability of the compacted GMZ bentonite, an experimental study was conducted under highly alkaline (NaOH solutions with various pH values were used), simulated groundwater conditions. The GMZ bentonite also contains cristobalite which may also have been dissolved. The microstructure of the compacted bentonite samples after the experiments was determined by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Energy dispersive spectroscopy (EDX) was carried out to identify mineralogical changes. At pH >13, the permeability of specimens increased significantly; the swelling potential decreased with increasing pH. Furthermore, the pore volume and pore size of GMZ bentonite changed when exposed to alkaline solution, resulting in an increase in porosity and permeability. The main alteration mechanisms of compacted GMZ bentonite undergoing infiltration by highly alkaline solution are likely to be dissolution and modifications in terms of the microstructure and mineralogy.

Hybrid material based on halloysite nanotubes (HNTs) and sodium perfluorooctanoate (NaPF8) was used as a consolidant for paper treatment. The consolidation efficiency was determined by thermogravimetry as well as by paper grammage determination. Morphological analysis of the treated paper was performed by means of scanning electron microscopy while the effect of modified HNTs on the thermal behaviour of the cellulose fibres was investigated by differential scanning calorimetry which determined the combustion enthalpy of the paper.Water contact angle measurements were performed to study the paper wettability. The physico-chemical properties investigated (mesoscopic structure, thermal stability and wettability) of the treated paper were correlated successfully with the consolidation loading and, consequently, to the affinity between the fluorinated modified HNTs and the fibrous cellulose structure. This study proposes a new green protocol for paper consolidation based on natural tubular nanoparticles with a flame retardant effect.

The intercalation of Tb(III) into layered magadiite is achieved by three-step ion exchanges with H+/Na+, TBA+ (tetra-n-butylammonium ions)/H+ and Tb(EDTA)3+/TBA+. Various techniques, including powder X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), thermogravimetric and differential thermogravimetry (TG-DTG), Fourier transform infrared (FTIR) spectroscopy, and photoluminescent spectroscopy (PL), were employed to characterize the Tb-intercalated magadiites. The XRD results revealed that the basal spacing of the Tb-intercalated magadiites was obviously larger than that of the Na-magadiite, confirming the intercalation. The IR spectra showed no bands attributable to EDTA in the Tb-intercalated magadiites, indicating that the EDTA has broken away from Tb(III)-ETDA complexes during ion exchange. Moreover, the basal spacing of Tb-intercalated magadiite tends to increase slightly with the increase in water content in the Tb-intercalated magadiite. The PL spectra show weak emissions, attributed to 5D4-7FJ (J = 3, 4, 5, 6) transitions of Tb3+.

The Swedish and Finnish nuclear waste repository design, KBS-3H, foresees horizontal emplacement of copper canisters-bentonite modules surrounded by a titanium shell. The interaction of titanium with bentonite was studied here using a combination of wet chemistry and a spectroscopic approach to evaluate the potential impact of Ti corrosion on the clay. For natural analogue clays with high Ti contents, spectroscopic investigations showed that titanium occurs as crystalline TiO2. In contrast, the Ti in the MX-80 bentonite occurs in the clay structure, presumably in the octahedral sheet. Hydrothermal tests conducted at 200°C using synthetic montmorillonite showed little if any change in the montmorillonite structure at near-neutral and acidic conditions. Under alkaline conditions, limited alteration was observed, including the formation of trioctahedral clay minerals and zeolite. These changes, however, occurred independently of the addition of Ti. In the batch tests conducted at 80°C, Ti did not occur as separate TiO2 particles. The comparison of experimental data with spectroscopic simulations provides sound evidence that Ti was incorporated in a neoformed phyllosilicate structure.

The highly alkaline environment induced by cementitious materials in a deep geological disposal system of high-level radioactive waste is likely to alter montmorillonite, the main constituent of bentonite buffer materials. Over long time periods, the alteration may cause the physical and/or chemical barrier functions of the buffer materials to deteriorate. In order to evaluate the long-term alteration behaviour, the dissolution rate, RA (kgm−3 s−1), of compacted pure montmorillonite (Kunipia-F) was investigated experimentally under conditions of hydroxide ion concentration of 0.10—1.0 mol dm−3 at temperatures of 50—90°C. The dissolution rate data, including those from a previous study at 130°C, were formulated as a function of the activity of hydroxide ions, aOH− (mol dm−3), and temperature, T (K), and expressed as RA = 104.5·(aOH−)1.3·e−55000/RT by multiple regression analysis, where R is the gas constant. The dissolution rate of montmorillonite was greater in the compacted montmorillonite than in the compacted sand-bentonite mixtures. The difference can be explained by considering the decrease in aOH− in the mixtures accompanied by dissolution of accessory minerals such as quartz and chalcedony. The dissolution rate model developed for pure montmorillonite is expected to be applied to bentonite mixtures if quantification of the decrease in aOH− is achieved somehow.

As a unique tubular nanoclay, halloysite nanotubes (HNTs) have recently attracted significant research attention. The HNTs have outer diameters of ∼50 nm, inner lumens of ∼20 nm and are 200–1000 nm long. They are biocompatible nanomaterials and widely available in nature, which makes them good candidates for application in biomedicine. Compared with other types of nanoparticles such as polymer nanoparticles and carbon nanotubes, the drawbacks associated with HNTs include brittleness, difficulty with fabrication, low fracture strength, high density and inadequate biocompatibility. Preparation of polysaccharide-HNT composites offer a means to overcome these shortcomings. Halloysite nanotubes can be incorporated easily into polysaccharides via solution mixing, such as with chitosan (CS), sodium alginate, cellulose, pectin and amylose, for forming composite films, porous scaffolds or hydrogels. The interfacial interactions, such as electrostatic attraction and hydrogen bonding, between HNTs and the polysaccharides are critical for improvement of the properties. Morphology results show that HNTs are dispersed uniformly in the composites. The mechanical strength and Young's modulus of the composites in both the dry and wet states are enhanced by HNTs and the HNTs can also increase the storage modulus, glass-transition temperature and thermal stability of the composites. Cytocompatibility results demonstrate that the polysaccharide-HNT composites have low cytotoxicity even for HNT loading >80%. Therefore, the polysaccharide-HNT composites show great potential for biomedical applications, e.g. as tissue engineering scaffold materials, wound-dressing materials, drug-delivery carriers, and cell-isolation surfaces.

New drug-delivery systems have remained a challenge for pharmaceutical scientists due to the use of expensive polymers and the low loading capacity of prepared nanoparticles. There is pressure to develop formulations that contain not only cheaper materials but also have controlled-release properties. Halloysite nanotubes (HNTs) are a naturally occurring clay mineral similar to kaolin, possessing a special particle shape in the form of an ultramicroscopic multilayered hollow cylinder. Its uses encompass a wide range in anticancer therapy, sustained- and controlled-release drug-delivery systems, cosmetics, delivery of proteins, vaccines and genes. These advantages are due to its biocompatibility, significant mechanical strength and natural availability. The surfaces of the tubules can be modified by coating different polymers for application in the drug-delivery system. This review is focused on the various aspects of HNTs such as structure, properties, loading methods, applications and characterizations.

Alteration of cement–bentonite interfaces and accompanying changes in diffusivity of tritiated water (HTO) was investigated experimentally using intact, hardened cement-paste specimens. The alteration by carbonate solution was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼70 ± 7%of the initial value after a 180-day period. Another alteration in contact with compacted bentonite was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼71 ± 10% of the initial value after a 600-day period. The changes in the diffusivity were considerably less than those observed for mixed specimens of ground, granulated hardened cement paste and bentonite where the diffusivity decreased to 20% of the initial value over 180 days. The results were extrapolated to 15 y under simple assumptions and showed good agreement with those observed in the cement–argillite interface at Tournemire URL (France). Such an explanation enhances confidence in the assessment of the alteration of cement-bentonite systems and might be a basis for using the data and models obtained in the long-term assessment of radioactive waste disposal.

One of today's big challenges is to store safely the increasing amount of high-level radioactive waste (HLRW) in the world. In some of the concepts devised for this challenge, bentonite, a natural swelling clay, plays a key role in encasing the canisters containing the waste. The use of bentonite as a geotechnical barrier in HLRWrepositories is a new venture; specifications to ensure either optimum performance or that a minimum standard is reached at least do not exist yet. The present study summarizes relevant research and discusses possible HLRW-bentonite specifications. The importance of these specifications for any given repositories has to be assessed on a case by case basis, depending on the concept being employed and any special circumstances for the individual repositories.

Ten key issues were identified which were used to discuss bentonite specifications. In some of these key issues the optimum bentonite performance depended more on processing and production (compaction) than on the bentonite type (e.g. swelling pressure and thermal conductivity). In contrast, in some of the other key issues, the type of bentonite was found to influence possible specifications: the bentonite should not alter its mineral composition or its geotechnical parameters such as the swellability. Therefore, the bentonite should contain neither soluble nor reactive phases (e.g. organic matter, pyrite, gypsum). The structural Fe content of the smectites should be small because of the lesser stability and greater reactivity of the Fe-rich bentonites. Also, a large layer-charge density of the swelling clay minerals leads to less corrosion at the iron–bentonite interface (relevant if iron canisters are used). The hydraulic conductivity and swelling pressure can be tailored by compaction of the bentonite resulting in different dry densities. From an engineering point of view, a bentonite with least dependence of the hydraulic conductivity/swelling pressure on the dry density would be best. Using a bentonite which has been investigated extensively over many years means less uncertainty compared to unknown materials.

There is increasing research interest in potential applications of halloysite as fillers for polymer composites, controlled drug delivery, carriers for the supply and sustained release of active agents for anticorrosion coatings, in nanoreactors or nanotemplates, and for the uptake of contaminants or pollutants and support for catalysts. In this review, recent findings in terms of the prospects and challenges of using halloysite nanotubes (HNTs) in different polymeric matrices targeting a range of old and new applications are discussed and evaluated. The compositions include chitosan/halloysite membranes as bone-tissue scaffolds, polylactic acid (PLA)/halloysite membranes for food-packaging applications and their antimicrobial activities, instrumented impact properties of epoxy/halloysite nanocomposites and the role of halloysite in the self-healing of epoxy composites, polyacryronitrile (PAN)/halloysite membranes for use in water filtration as well as a review of some recent applications of halloysite/alginate beads in the adsorption of contaminants such as lead.

The effects of increasing nickel contamination of soil on the update of selected microelements by Brassica juncea L. in the presence of raw halloysite (RH) and halloysite modified by thermal treatment (calcination) at 650°C (MH) were investigated experimentally. Such treatment causes partial dehydroxylation and enhances mineral-adsorption properties towards cations. In a vegetative-pot experiment, four different levels of Ni contamination, i.e. 0 (control), 80, 160, 240 and 320 mg kg−1 were applied in the form of an analytical-grade NiSO4·7H2O solution mixed thoroughly with the soil. Among the minerals which were added to soil to alleviate the negative impact of Ni on plant biomass, MH had a particularly beneficial effect on the growth of B. juncea L. The amount of Ni, Zn, Cu, Mn, Pb and Cr in Indian mustard depended on the Ni dose and type of accompanying mineral structure. The average accumulation of trace elements in B. juncea L. grown in Ni-contaminated soil follow the decreasing order Mn > Zn > Cu > Ni > Pb > Cr.

Ka Loko Dam, in Kauai, Hawaii, failed suddenly and catastrophically on March 14, 2006. The resulting breachwas marked by three topographic benches, the lowest of which exposed native volcanic deposits once resident in the dam foundation. These deposits were found to contain outcrops of a waxy, gel-like material that appeared to result from in situ weathering processes. This unusual material was found to be highly enriched in halloysite. Gravel-size pieces in the hydraulic fill of the embankment derived from these materials also exhibited significant in situ weathering and significant halloysite content. Engineers and geologists generally recognize that bedrock materials weather progressively into soil constituents over ‘geological time’, and that this process is accelerated in tropical environments. Still, the strength, stiffness and durability of bedrock, earth and embankment materials are not expected to vary significantly over the geologically short life of a dam. In the case of Ka Loko Dam, however, the volcaniclastic sediments that comprise the local bedrock experienced substantial in situ weathering over its geologically brief 115-year operational lifetime. Prolonged exposure to seepage of anoxic water weathered the sediments completely to saprolite, including weak, sensitive, fine, spherical halloysite.

Halloysite-rich soils derived from in situ weathering of volcanic materials support steep stable slopes, but commonly fail under triggers of earthquakes or rainfall. Resulting landslides are slideflow processes, ranging from small translational slides to larger rotational failures with scarps characteristic of sensitive soils. Remoulding of failed materials results in high-mobility flows with apparent friction angles of 10–16°. The materials characteristically have high peak-friction angles (∼25– 37°), low cohesion (∼12–60 kN m−2) and plasticity ( plasticity index ∼10–48%), and low dry bulk density (∼480–1,080 kg m−3) with small pores due to the small size of the halloysite minerals. They remain saturated under most field conditions, with liquidity indexes frequently >1. Remoulded materials have limited cohesion (<5 kN m−2) and variable residual friction angles (15°–35°). Halloysite mineral morphology affects the rheology of remoulded suspensions: tubular minerals have greater viscosity and undrained shear strength than spherical morphologies.