Thermal transformation of chrysotile from Uruaçu District, state of Goiás, Brazil, heated in dry conditions at temperatures from 600°C to 1300°C was studied by high resolution electron microscopy and selected area electron diffraction (SAD). Up to 600°C, no morphological or SAD pattern changes were observed. At 600°C, the fibrils were still crystalline with the characteristics of the clinochrysotile. In addition, a new fringe system of 10–15 Å spacings appeared sporadically parallel to the 7.3 Å fringes of chrysotile. Areas of these extra fringes seem to constitute favorable sites for the nucleation of forsterite. At 650°C, forsterite nuclei appeared inside the nearly amorphous fibrils in the shape of patches consisting of flaky crystallites. At 700°C the chrysotile structure had disappeared; the new spots present in the SAD pattern were indexed as those of forsterite. Between 800–900°C the crystallinity of the patches was clearly demonstrated. From the lattice images in the patches, topotactic relations between chrysotile and forsterite were analyzed. At 1000°C very tiny grains of enstatite were formed mixed with forsterite grains. The SAD pattern is complex due to the coexistence of forsterite, enstatite, and silica-rich amorphous areas. From 1100°C to 1300°C the tridimensional growth of enstatite was promoted. The present results support the topotactic relations between chrysotile and forsterite found by X-ray analysis although differences up to several degrees may exist when these phases are observed microscopically. Evidence suggesting a topotactic growth between forsterite and enstatite was also obtained.

The change of the properties of chrysotile after ball milling in organic liquids (aromatics, alcohols, silicone oils) or water was studied by gas adsorption, electron microscopy, X-ray powder diffraction, infrared spectroscopy, differential thermal analysis, zeta potential measurements, and chemical analysis. Grinding in low viscosity organic solvents leads initially to a rapid defiberization of the asbestos bundles and to a fragmentation of the isolated fibrils. Finally, amorphization and agglomeration occur causing a drastic decrease of the specific surface area of the ground material. Grinding in water brings about a defiberization, but much more slowly than in organic solvents. Moreover, prolonged grinding in water does not significantly alter the structure of chrysotile. The efficiencies of the organic solvents, considered as grinding aids that induce fracture of the fibrils, are related to the environmental stress cracking of brittle solids (Rehbinder theory). Hence, the pertinent properties of the organic liquids are their viscosity and their cohesion energy (solubility parameter). Solvents chemisorbed on the surface of the ground chrysotile reduce the surface energy of the fracture surface and prevent aggregation. Water does not react according to Rehbinder's theory, but appears to form a protective layer around the fibrils. This hypothesis was verified by dry grinding defiberized asbestos (rapid amorphization) or by disturbing the stability of the water coating by coadsorbing alcohol on the solid surface. Alternatively, the resistance of the fibrils to fracture may be explained by Westwood's theory that grinding in water is equivalent to grinding in an alkali medium, wherein the surface charge of the chrysotile becomes negligible, and the mechanical stability of the fiber reaches a maximum.

By using a transmission electron microscope equipped with an energy dispersive spectrometer, it was possible to detect the morphological, structural, and chemical characteristics of individual asbestos fibers and clay minerals without any realignment of the equipment. A rapid and convenient procedure for semiquantitative analysis is proposed. Analyses are given for 21 hydrous silicates, asbestos and clay minerals, by both ordinary chemical and energy dispersive methods. The energy dispersive results were comparable to those obtained by chemical analysis. Application of this procedure to asbestos fibers proved this method to be practical and valid for characterization of asbestos in environmental and tissue samples.

The thermal transformation of a Brazilian antigorite heated dry from 600° to 1300°C, was studied by high resolution electron microscopy and selected area electron diffraction (SAD). Below 600°C, the antigorite particles did not change morphologically or crystallographically, as evidence by the presence of the superlattice in the SAD patterns and lattice images. At 650°C, traces of antigorite remained, although the superlattice structure had disappeared and the first indications of forsterite formation were observed in the same SAD. Diffraction patterns of the transition phases showed various topotactical relationships between antigorite and forsterite. At 800°C, the crystallization to forsterite was much more pronounced. At 900°C, the individual particles retained their original shapes, but they were actually pseudomorphs, for their SAD patterns showed only forsterite. Between 1000° and 1300°C various topotactical relationships were observed. Although the overall transformation to forsterite appears to be similar for both chrysotile and antigorite, the transformation of antigorite took place at a slightly higher temperature (~50°C) with a larger number of topotactical relationships than for chrysotile. Enstatite was formed at 1300°C, but it was impossible to determine the topotactic relations between enstatite and forsterite, which was possible with chrysotile.

The structural damage produced by dry grinding and acid leaching of chrysotile was studied by transmission and scanning electron microscopy, infrared spectroscopy, X-ray powder diffraction, and thermogravimetric analysis. Severe dry grinding converted the chrysotile fibers into fragments having strong potential basic reaction sites. These sites were immediately neutralized by molecules present in the atmosphere (e.g., H2O, CO2). Acid leaching transformed the chrysotile fibers into very porous, non-crystalline silica, which was easily fractured into short fragments. The damage produced in the chrysotile structure by grinding or leaching was assessed by monitoring the intensity of various infrared absorption bands.

Quaternary debris flows derived from ophiolite melange in northern Southland, New Zealand, are locally cemented and veined by cross-fiber and fine-grained chrysotile. Chrysotile was identified by optical, X-ray powder diffraction, electron microprobe, differential thermal (DTA), and infrared analysis methods. Microprobe and DTA also suggested the presence of as much as 6% of sub-microscopic, noncrystalline alumina, probably in the form of pseudoboehmite. Cavity fillings and irregular veins containing chrysotile are as thick as 40 cm and commonly contain lizardite clasts. Calcite commonly accompanies chrysotile as a vein mineral. Magnetite and pyrite are found near and adjacent to chrysotile veins. These accessory minerals imply that the chrysotile formed under alkaline, reducing conditions. Surface water seepages have pH = 9. Remnant debris-flow topography, Holocene radiocarbon dates, and the absence of hot spring activity confirms that chrysotile can form under near-surface, low-temperature conditions. Growth of chrysotile fibers on a lizardite substrate suggests that the chrysotile formed by solution of detrital lizardite and subsequent precipitation in cavities within the debris flow.

Reaction of mixtures of cobalt nitrate, colloidal silica, and a metal hydroxide (MOH) under hydrothermal conditions produced a range of cobalt hydroxysilicates, the components of which depended upon the identity of M, temperature, and reactant ratios. At 250°C, if M = Na, a smectite of composition Na0.06Co3.07Si3.95O10(OH)2 (I) was produced. If M = K, either a mica, KCo2.5Si4O10(OH)2 (II), intermediate between di- and trioctahedral, or a Si-deficient mica, KCo3Si3.75O10(OH)2 (III), was formed depending upon the reactant ratios. Similarly, if M = Cs, either a vermiculite or a 2:1 layer silicate intermediate between a mica and a brittle mica was produced. If M = Li, only the non-clay mineral Li2CoSiO4 was formed. Tetraalkylammonium hydroxides (NR4OH, R = methyl, ethyl, or propyl) yielded chrysotile. All phases were characterized by elemental analysis, transmission electron microscopy, and X-ray powder diffraction. Further characterization of smectite I was undertaken by diffuse reflectance, infrared, and X-ray photoelectron spectroscopy. The layer charge in these clays appears to stem from cation vacancies within an almost trioctahedral sheet and, possibly, within the tetrahedral sheets. Some of the cobalt present had tetrahedral coordination geometry, but its location was not determined.

Stearic acid adsorption by chrysotile asbestos in hexane was shown to occur by the formation of a Mg-stearate complex on the mineral surface. Infrared spectroscopy showed no evidence of physically adsorbed stearic acid over the range of concentration employed. Absorption bands at 1560 and 1410 cm−1 in the spectrum of the chrysotile-stearic acid complex correspond with band positions in the spectrum of a synthesized Mg-stearate complex. No evidence of the acid form, which produces a band at 1713 cm−1, was present in the spectrum of the chrysotile complexes. At an equilibrium concentration of 0.8 mg stearic acid/ml, the mineral adsorbed 42 mg stearic acid/g. By heating the mineral in molten stearic acid, additional stearic acid beyond that observed by adsorption from solution was adsorbed in the carboxylate form. Calculations based on the molecular dimensions of stearic acid and the crystal structure of chrysotile indicate that the limiting factor in possible surface occupancy is the molecular size of stearic acid rather than the surface density of Mg-OH adsorption sites.

In vitro studies of the destruction (lysis) of bovine red blood cells (erythrocytes) by some silicate minerals showed the reaction to be complete in less than 1 hr and very destructive to the cell membrane. The activity as lysing agents was found to be in the order smectites > silica > palygorskite ≃ sepiolite > chrysotile > kaolinite. Different compositions (Fe, Al, Mg, Li, vacancy) of the octahedral sheet of the smectite and fibrous clay minerals did not appreciably alter their hemolytic activity. The most active particle size range for kaolinite and montmorillonite was 0.2-2 μm. Structural folding of palygorskite reduced lysis suggesting that edge surfaces and silanol groups are important in this process. Aluminum oxides and hydroxides caused no lysis, and coatings of positively charged aluminum-hydroxy polymers on montmorillonite, silica, palygorskite, and kaolinite significantly reduced lysis.

The production and industrial use of asbestos cement and other asbestos-containing materials have been restricted in most countries because of the potential detrimental effects on human health and the environment. Chrysotile is the most common form of asbestos and investigations into how to recycle this serpentine phyllosilicate mineral have attracted extensive attention. Chrysotile asbestos tailings can be transformed thermally, at high temperature, by in situ carbothermal reduction (CR). The CR method aims to maximize use of the chrysotile available and uses high temperatures and carbon to change the mineral form and structure of the chrysotile asbestos tailings. When chrysotile asbestos is employed as the raw material and coke (carbon) powder is used as the reducing agent for CR transformation, stable, high-temperature composites consisting of forsterite, stishovite, and silicon carbide are formed. Forsterite (Mg2SiO4) was the most abundant crystalline phase formed in samples heat treated below 1500ºC. At 1600ºC, forsterite was exhausted through decomposition and β-SiC formed by reduction of stishovite. A larger proportion of β-SiC was generated as the carbon content was increased. This research revealed that both temperature and carbon addition play key roles in the transformation of chrysotile asbestos tailings.

The present study considered the problem of halloysite nanoscroll synthesis by energy modeling of the formation of chrysotile and halloysite particles. The main aim of the study was to reveal an energy preference between scrolled and platy morphologies of the particles. Both hydrosilicates possess the ability to scroll spontaneously but relatively facile hydrothermal synthesis of the nanoscrolls is available only to the former, whereas halloysite forms mainly plates under the same conditions. This issue was investigated by a phenomenological energy model, taking into account: (1) strain energy due to the size difference between metal oxide and silica sheets; (2) surface-energy difference on the opposite sides of the layer; and (3) adhesion energy. Calculations showed that the halloysite layer had a significant scrolling potential due to the first energy component, but the surface-energy difference acted in the opposite direction and tried to unbend the layer. In contrast, these two actions were co-directional in chrysotile layers. In both cases, the formation of multi-layered plates became more energy favorable when the specific surface energy of the edges decreased. In the range 0.5–3 J/m2 for the specific surface energy, only halloysite layers showed an energy preference for platy particles over nanoscrolls, especially at small layer sizes. Certain processes, such as hydration, could reduce the corresponding specific surface energy value and, as a result, could stabilize the platy morphology of halloysite at the earliest stages of particle growth under hydrothermal conditions.

Numerous occurrences of asbestos minerals, notably chrysotile and tremolite, are to be found on fracture surfaces in thrust fault deformation zones of Cretaceous dunite-harzburgite and pyroxenite in the Çankırı and Ankara regions, central Anatolia, Turkey. Consequently, potential exists for the development of regional malignant mesothelioma. The means of serpentinization, such as reaction of seawater during accretion of the upper ophiolitic mantle crust in a subduction zone and/or following uplift of ophiolitic units and the influence of hydrothermal/meteoric fluids along fractures, were investigated. Cretaceous dunite-harzburgite and localized pyroxenite rocks are mainly composed of serpentinized olivine and pyroxene associated with opaque minerals and Fe-(oxyhydr)oxide phases. Smectite, chlorite, illite, kaolinite, hydromagnesite, goethite, quartz, and opal-CT are also present. Chrysotile and localized tremolite occur either as a mesh, a suboriented to oriented long-fiber bundle, or as fiber-filling millimetric micro-vein textures on relicts of olivine and pyroxene (enstatite, augite). The chrysotile and tremolite have non-pseudomorphic textures developed under high pressure and temperature. The textures suggest authigenic formation of chrysotile and tremolite via a dissolution and precipitation mechanism. Additionally, spherical structures of opal-CT and locally platy hydromagnesite crystals either enclose or are developed within chrysotile/tremolite fiber bundles. The leaching of MgO, Fe2O3, Al2O3, Ni, Cr, and Nb, an increase in the LREE/HREE ratio, and negative Eu anomalies in the dunite-harzburgite and pyroxenite, and asbestos samples suggest that the chrysotile and tremolite were derived from the serpentinization of olivine and pyroxene. The chrysotile and tremolite were developed along fractures by hydrothermal fluid alteration during accretion and/or following the uplift of ophiolitic units of the region under high pressure and temperature conditions. This interpretation is also supported by isotope data and the calculated formation temperature of 170–555°C for chrysotile and tremolite. The average structural formulae for chrysotile and tremolite are (NanK0.03)(Mg5.54Fe0.09Al0.05Ca0.01Mn0.001) (Si3.96Al0.03)O10(OH)8 and (Na0.17K0.07)(Ca1.59Mg0.19Mn0.002)(Mg4.72Fe0.28)(Si7.86Al0.1Fe0.06)O22(OH)2, respectively.

Chrysotile from Thetford Mines in Quebec, Canada was treated first with mild formic or oxalic acid at concentrations of 0.5 to 2.0 N at 200°C in Teflon-lined 12.0 mL Parr bombs. The reaction products were identified by X-ray diffraction as a poorly crystalline Fe-bearing kerolite-like 2:1 layer silicate (which will be described as a kerolitic precipitate or a kerolitic mesophase in this report). Electron microscopic examination showed a thin foily morphology for this kerolitic mesophase that may have formed by the following reaction:(1)

$\mathop {{\rm{M}}{{\rm{g}}_{\rm{6}}}{\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{{8_{\left( {\rm{s}} \right)}}}}}\limits_{{\rm{chrysotile}}} + 6.02{{\rm{H}}^{\rm{ + }}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{F}}{{\rm{e}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} \to \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}} \cdot n}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} {{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{3}}{\rm{.55M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)}$

The magnetite impurity in the initial chrysotile asbestos served as the source of Fe in the above reactions. Subsequently, this kerolitic precipitate was reacted with 0.2 N NaOH for 48–96 h at 200°C and a highly crystalline smectite was formed with the same foily morphology as the kerolitic precipitate. X-ray spectral analyses of the kerolitic mesophase and smectite suggest the following reaction to have taken place:(2)

$\eqalign{ & \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}}}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} \cdot n{{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{0}}{\rm{.53M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{NaO}}{{\rm{H}}_{\left( {{\rm{aq}}} \right)}} + 0.01{\rm{F}}{{\rm{e}}^{{\rm{3 + }}}}_{\left( {{\rm{aq}}} \right)} \to \cr & \;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\mathop {\;\;{\rm{N}}{{\rm{a}}_{0.54}}\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.99}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.01}}}^{{\rm{2 + }}}} \right)\left( {{\rm{S}}{{\rm{i}}_{{\rm{3}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{3 + }}}} \right){{\rm{O}}_{10}}{{\left( {{\rm{OH}}} \right)}_{{\rm{2}}\;\left( {\rm{s}} \right)}}}\limits_{{\rm{saponite}}} + 0.54{\rm{S}}{{\rm{i}}^{{\rm{4 + }}}}_{\left( {{\rm{aq}}} \right)} \cr} $

The reaction products, a kerolitic mesophase and smectite, possess a non-fibrous habit in contrast to the fibrous (asbestiform) morphology of chrysotile.

Transmission electron microscopy shows that normal chrysotile and polygonal serpentine occur together and in parallel association with balangeroite, within the slip-veins of the Balangero serpentinite. Chrysotile substitutes for balangeroite and it is later replaced by the polygonal serpentine.

The chrysotile fibres are packed together according to a rod close-packing scheme, with defects. Lattice images of the polygonal serpentine confirm the structure model proposed by Middleton and Whittaker (1976), consisting of polygonally arranged fiat layers. This structural type is probably common for serpentine minerals and constitutes a fourth main type of layer configuration in 1:1 layer silicates.

The structure of chrysotile, an important asbestos mineral, consists of layers curled concentrically or spirally into tubes. Published transmission electron microscope (TEM) images suggest that successive layers are generally stacked out of register with one another. However, a lattice model can be constructed in such a way that each layer can be stacked in register with the next, five times around the circumference, so that the structure exhibits a global 5-fold symmetry. We report here TEM observations confirming that chrysotile asbestos can form crystals with this structure, the first observation of five-fold symmetry in a natural crystalline material.

A chrysotile disc is proposed as the fundamental seed structure for the formation of chrysotile asbestos fibres, polygonal serpentine fibres and polyhedral lizardite spheres. The curvature, fivefold symmetry and hydrogen-bonding alignment of the layers in the seed disc control the formation of the 15 or 30 sectors in polygonal serpentine and the orientations of the planar arrays of 15 or 30 radial crystals in polyhedral serpentine. A polygonized disc precursor to polygonal fibre formation has been observed at an arrested stage of growth in a synthesis experiment.

The nitric-acid dissolution of chrysotile was investigated with the aim of revealing the effect of pH on its structure. Chrysotile becomes more soluble at lower pH, with the octahedral, brucite sheet more readily dissolved than the tetrahedral sheet. The dissolution of the brucite sheet increases the pH of the solvent, because of the release of OH− groups along with the Mg2+ ions. At pH 2.00, the characteristic cylindrical fibre bundle structure of chrysotile is retained after dissolution, although the outside surface of each fibre becomes rough. Chrysotile remains fibrous upon dissolution at pH 1.08, but the fibres are no longer crystalline and their cylindrical structure collapses. The nitric-acid treatments result in an increase in both the specific surface area and the pore volume of chrysotile.

Because of widespread tremolite and chrysotile minerals in Palaeozoic-Mesozoic metamorphic and Triassic ophiolitic units, respectively, in the Eskişehir region, Turkey, there is significant potential for development of cases of mesothelioma. Such occurrences in the Eskişehir region show a positive correlation with the concentration and dimension of tremolite crystals compared with those of chrysotile crystals. A detailed assessment of the mineralogy, geochemistry and genesis of these materials has not been carried out to date; the present study was undertaken to fill that gap. The sharp diagnostic basal reflections at 8.14 Å, 3.09 Å and at 7.30 Å, 3.63 Å, well defined fibrous crystallinity, and ideal differential thermal analysis-thermal gravimetric and Raman curves suggest the development of well crystallized fibrous/acicular tremolite and chrysotile with the average structural formulae of: (Na0.07K0.03)(Ca1.68Mg0.18Mn0.01)(Fe0.42Mg4.55Ti0.01)(Si7.60Al0.24Fe0.16)O22(OH)2, and (Mg5.55Fe0.41 Mn0.006)(Si3.79Al0.13)O10(OH)8, respectively.

Enrichment of light rare earth elements relative to medium rare earth elements and heavy rare earth elements in tremolite compared to that of chrysotile which exhibits no anomaly and negative anomalies for Ba, Sr, Ce, Nb, Yand Zr in the tremolite samples and chrysotile, are responses to the fractionation of feldspar, glaucophane, pyroxene and olivine under the high temperatures of hydrothermal-alteration processes during serpentinization and the high-pressure conditions of metamorphism. Based on H and O isotope data, the tremolite and chrysotile are thought to have developed from tectonically controlled magmatic and meteoric hydrothermal systems and the formation temperatures of the tremolite are higher than those of chrysotile.