Leached Surface Research Articles

Two-phase Hybrid Thermal Interface Alkali-treated E-Glass Fiber/MWCNT/Graphene/Copper Oxide Nanocomposites for Electronic Gadgets.

Two-phase hybrid mode thermal interface materials were created and characterized for mechanical properties, thermal conductivity, and wear behaviour. Therefore, the ultimate goal of this current research was to use alkali-treated glass fibre and other allotropes to produce high-performance two-phase thermal interface materials. Three different polymer composites were prepared to contain 20 vol.% alkalies [NaOH] treated e-glass fibre [E] and epoxy as a matrix with varying proportions of multi-walled carbon nanotube [MWCNT], graphene [G], copper oxide [C]. The one-phase material contained epoxy+20%e-glass+1%MWCNT [EMGC1], the two-phase hybrid composite contained epoxy+20%e-glass+1%MWCNT+1%graphene+1%CuO [EMGC2], and two-phase material contained epoxy+20%e-glass+1%graphene+1%CuO [EMGC3]. Vacuum bagging method was used for fabricating the composites. The higher thermal conductivity observed was 0.3466 W/mK for EMGC2, the alkali-treated glass fibre/hybrid mode nanofillers epoxy matrix composite was mechanically tougher than the other two composites [EMGC1 & EMGC3]. Scanning electron microscopy analysis revealed the fine filler dispersion and homogenous interaction with the glass fibre/epoxy resin composite of the upper and lower zone, which also revealed the defective zone, fibre elongation, fibre/filler breakages, and filler leached surfaces. Finally, it was concluded that the hybrid mode two-phased structure EMGC2 epoxy matrix composite replicated the maximum thermal conductivity, mechanical properties, and wear properties of the other two specimens.

Effects of open circuit immersion and vertex potential on potentiodynamic polarization scans of metallic biomaterials

Electrodes made of commercially pure titanium (CP-Ti) and a CoCrMo alloy are immersed at an open circuit in a phosphate buffer saline electrolyte at room temperature for different durations prior to electrochemical analyses. Open circuit potential measurements, electrochemical impedance spectroscopy measurements, and cyclic potentiodynamic polarization (CPP) scans are used to assess the impact of the immersion time on derived property values. Stable passivation layers formed on both materials during immersion. The corrosion potentials determined from the anodic legs of CPP scans become more cathodic, and the corrosion currents decrease to lower values after longer immersion times. Measured currents indicate the layers formed on CP-Ti stabilize during forward anodic scans and persist to the vertex potential, whereas passivation breakdown occurs during anodic scans with CoCrMo with active corrosion at voltages up to the vertex potential. The characteristics of the return cathodic legs of CPP scans represent the surface conditions at the vertex potential: characteristic corrosion property values derived from the test responses represent passive surfaces on CP-Ti and leached surfaces on CoCrMo rather than intrinsic properties of those materials.

New perspective on the depassivation mechanism of chalcopyrite by ethylene thiourea

The catalytic effect of ethylene thiourea (ETU) during the acidic ferric sulfate leaching of chalcopyrite was studied through various approaches. Bioleaching experiments showed that the addition of ETU rapidly dissolved the Cu-rich passivation layer on chalcopyrite, bringing the dissolved Cu/Fe mole ratio back to 1. Continuation of the leaching experiment shows that ETU also enhances copper extraction from depassivated chalcopyrite. Bioleaching tests carried out on pure covellite showed a similar catalytic effect from ETU. Chemical leaching tests conducted on chalcopyrite in acidic ferric/ferrous sulfate solution confirmed that the catalytic effect of ETU does not originate from changes in solution potential. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the leached chalcopyrite surfaces showed that ETU can supress the formation of a copper polysulfide phase during leaching. Ex-situ I-V analysis proved that the product layer is a p-type semiconductor and forms a diode with the n-type bulk mineral. ETU helped dissolve the p-type surface product layer and therefore transitioned the passivated chalcopyrite from a diode back to its native resistor form. Electrochemical impedance spectroscopy (EIS) analysis further demonstrated that the catalytic effect of ETU is more pronounced for passivated chalcopyrite than for a fresh surface. Combined, the results prove that ETU is an excellent remedy for passivated chalcopyrite as it readily catalyzes the dissolution of the passive layer and then continues to catalyze the leaching of native chalcopyrite.

Role of foreign ions in the thiourea leaching of gold

Thiourea, as an environmentally friendly gold lixiviant, has the potential to replace highly toxic cyanide. The effect of foreign ions including Cu2+, Ag+, Pb2+, Zn2+, AsO33− and AsO43− on gold leaching in an acidic thiourea solution was investigated in this paper. Leaching results showed that the foreign ions had an adverse effect on thiourea leaching of gold. The gold dissolution (except low Pb2+ concentrations, i.e., < 20 mg/L) and thiourea stability both were in order of no foreign ions ≈ Zn2+ > Pb2+ > AsO33− > AsO43− > Ag+ > Cu2+. The thiourea dissolution of gold could be improved at low concentrations of Pb2+ (<20 mg/L), although the thiourea consumption was also increased. The thermodynamic analysis and the scanning electron microscope (SEM) and X-ray photon spectroscopy (XPS) analyses suggested that the foreign ions resulted in insignificant changes in the corrosion characteristics of leached gold surface and the quantity and chemical state of surface species. The possible mechanism for the effect of foreign ions on thiourea leaching of gold was proposed that the thiourea consumption in the presence of foreign ions was significantly increased, leading to the marked deterioration of thiourea dissolution of gold.

Trace Element Geochemistry in the Earliest Terrestrial Ecosystem, the Rhynie Chert

AbstractThe symbiotic partnership of plants and fungi was a critical means of nutrient uptake during colonization of the terrestrial surface. The Lower Devonian Rhynie Chert shows evidence for extensive phosphorus mobilization in plant debris that was pervasively colonized by fungi. Sandy sediment entrapped with fungi‐rich phytodebris contains grains of the phosphate mineral monazite which exhibit alteration to highly porous and leached surfaces. Mixed manganese‐iron oxide precipitates contain up to 2% P2O5. The mobilization of Mn, Fe, and P are all features of mycorrhizal nutrient concentration. However, the ecosystem was also exposed to toxic elements from hot spring hydrothermal activity. The oxide precipitates include titanium and iron‐titanium oxide which sequestered potentially toxic tungsten and antimony. Abundant pyrite framboids in the Rhynie Chert indicate that plant decomposition included microbial sulfate reduction. This caused the removal of some of the arsenic from the groundwaters into the pyrite, which reduced toxicity while leaving enough for putative arsenic metabolism. These relationships show the mineral component of the ecosystem modified the geochemistry of ambient waters.

The overlooked mechanism of chalcopyrite passivation

Chalcopyrite (CuFeS₂) is the world's main source of copper. Electrification of the global economy will rely on economically viable Cu dissolution from low grade chalcopyrite ores, but this process is particularly slow. The reason for this slow reaction has been in dispute for over 50 years. In this study, electrochemical analysis showed that n-type chalcopyrite is in an accumulation state when immersed in electrolyte, not in a depletion state as is commonly assumed. A leaching test and surface analysis confirmed the formation of a Cu-rich surface layer during oxidative leaching. In addition, a similar leaching test on covellite (CuS) showed leaching kinetics that were as slow as chalcopyrite. Ex-situ current-voltage analysis showed that the Cu-rich (covellite-like) product layer on the surface of chalcopyrite was a p-type semiconductor. Therefore, as leaching progresses, chalcopyrite transitions from a resistor to a diode. Three mechanisms for slow dissolution of chalcopyrite in acidic ferric media are proposed based on these tests: 1. The dielectric breakdown potential of chalcopyrite (0.7 V vs Ag/AgCl) is higher than what the ferric/ferrous redox couple can provide (0.5 V). 2. A chemically stable covellite-like surface layer prevents further Cu dissolution. 3. Rapid formation of a p-n junction on the leached chalcopyrite surface hinders the electrochemical process. We hypothesize that all three mechanisms together prevent the full dissolution of chalcopyrite under oxidative conditions at ambient temperature.

Enrichment and distribution of elements in the middle Miocene coal seams in the Orhaneli coalfield (NW Turkey)

This study focuses on ascertaining controlling factors and differences on mineralogical and elemental contents for reconstructing palaeoenvironmental conditions of both seams applying standard coal characteristics, mineralogical, coal-petrologic, and elemental data of the Orhaneli coalfield. The studied coalfield, one of the important coalfields in NW Turkey, includes two workable coal seams, the lower with 0.5–2 m and the upper with 5–6 m in thickness, which are separated by 2–5 m thick, grayish-green limnic claystone. The floor rocks of the both seams are limnic claystones, whereas the roof rock of the upper seam is the tuffite layers-bearing lacustrine marls. Matrix and xylite-rich lithotypes are common in the upper seam, while alternations of xylite-clayey bands (detro-xylite and xylo-detritic) are common in the lower seam. The lower seam is also characterized with the presence of altered tuff layers, while freshwater gastropod shell-bearing bands were identified from the upper seam. Even though the banding character and maceral composition of the coals were invariant between the seams, there are distinct differences in mineralogy and elemental composition, that can be related to the nature of the clastic sediment influx and contemporary volcanic inputs into freshwater forested mires.The lower seam is characterized by high ash yields (%44.2–64.3, d) and relatively high concentrations of aluminosilicate-affiliated elements and REY (rare earth elements and Y). In contrast, the upper seam has relatively low ash yield, and is slightly enriched B concentration. The B enrichment in the upper seam is presumably controlled by the presence of clay mineral (e.g., illite) and clastic volcanogenic accessory minerals (e.g., apatite). Arsenic is the only enriched element in both seams due to development of anoxic conditions. Although no traceable As was detected from syngenetic framboidal pyrite grains, the contemporary volcanic inputs (e.g., air-fall ash/tephra) along with leached surface waters into palaeomires might be source for As, while the development of anoxic conditions palaeomires could cause formation of syngenetic pyrite grains. Thus, the As concentrations of the studied samples are elevated. Nevertheless, the difference on ash yields and mineralogical compositions between studied seams might be related with different clastic influx ratios and contemporary volcanic inputs, in turn, aluminosilicate affiliated elements display different concentration coefficients (CC) values in the studied seams, and high B concentrations that are not expectable for a limnic coal Besides, enrichment of Cr, V and Ni in the upper seam are controlled by clastic V-bearing chromite grains from Orhaneli chromite deposit in the adjacent area. Furthermore, the contemporary volcanic inputs into the palaeomire of the lower seam, and their alteration under anoxic conditions caused REY enrichment and the formation of kaolinite and smectite matrices of clay aggregates in coal and altered tuff layers in this seam.

Synthesis of fine skeletal structure on Al–Cu–Co decagonal quasicrystals for hydrogen production through steam reforming of methanol

In the present investigation, we have reported the surface-microstructure, chemical composition and structural characteristics of the conventionally solidified Al65Cu15Co20 and Al65Cu20Co15 decagonal quasicrystals before and after chemical leaching treatment. The surface of the polycrystalline Al–Cu–Co decagonal phase was leached with 2.5 mol of Na2CO3 solution for the duration of 0.5 h, 2 h and 8 h. The leached surface was characterized by x-ray diffraction, scanning and transmission electron microscopy techniques. The energy dispersive x-ray analysis was employed to determine the chemical composition of the leached surface. After leaching treatment, the crystallographic structure of the leached surface was found to change from the quasicrystalline phase to the crystalline phases of Cu, Co and their oxides. The formation of the skeletal structure observed at the surface was attributed to the removal of Al atoms from the lattice points of the concerned decagonal quasilattice. This skeletal structure was found to contain porosities coexisting with finely distributed nano-particles of Cu, Co and Cu2O with sizes ranging from 10 to 28 nm. The 8 h leached surface containing these skeletal features has demonstrated excellent catalytic activity for steam reforming of methanol and it has led to hydrogen production at the rate of ~200 ml/g min at the reaction temperature of 580 K.

Influence of acid leaching surface treatment on indentation cracking of soda lime silicate glass

Past work has shown that water or acid soaking treatments can increase the mechanical strength of soda lime silicate (SLS) glasses. In this work, we show that acid leaching treatments result in an increase in the apparent crack resistance of the acid-leached surface of SLS glass during indentation. Vickers indentation tests in controlled environments show a humidity dependence of radial cracking, suggesting that the transport of water through the leached layer plays a critical role in the propagation of cracks to the glass surface. Molecular dynamics simulations with reactive force fields indicate that the leached surface layer can undergo pressure-induced mechanochemical reactions during indentation, which increases the bridging oxygen connectivity in the silica network of the leached layer. Such structural changes can hinder transport of water molecules from the environment to the subsurface crack tip. Based on experimental observations and simulation results, a new hypothesis is proposed that mechanochemical restructuring in the leached layer in response to the applied load may lower the transport kinetics of molecular water to critical flaws, resulting in an apparent enhancement in the crack resistance of the acid-leached surface of SLS glass.

Effect of solution chemistry on the iodine release from iodoapatite in aqueous environments

To ensure the safe disposal of nuclear waste, understanding the release process of radionuclides retained in the nuclear waste forms is of vital importance. Iodoapatite Pb9.85(VO4)6I1.7, a potential waste form for iodine-129, was selected as a model system for ceramic waste forms in this study to understand the effect of aqueous species on iodine release. Semi-dynamic leaching tests were conducted on bulk samples in cap-sealed Teflon vessels with 0.1 mol/L NaCl, Na2CO3, Na3PO4, and Na2SO4 solutions under 90 °C, fixed sample surface area to solution volume ratio of 5/m, and periodic replacement of leaching solutions. The reacted solutions were then analyzed by Inductively Coupled Plasma-Mass Spectrometry and Inductively Coupled Plasma-Optical Emission Spectrometry; the leached surfaces were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The result shows that, compared to deionized water, the ion-rich solutions enhanced the iodine release as a result of the increased ionic strength, reduced activity coefficient of dissolved species, and increased solution pH. Surface reactions can lead to the formations of secondary phases by ion-exchange and precipitation. These findings suggest that an ion-rich environment in the geological repository can be detrimental to the disposal safety of the nuclear waste form.

Two-stage leaching of zinc and copper from arsenic-rich copper smelting hazardous dusts after alkali leaching of arsenic

In order to efficiently recover zinc and copper from arsenic-rich copper smelting hazardous dusts after alkali leaching of arsenic, an optimum two-stage leaching process by using sulfuric acid media was developed in this study. The leaching behaviors of zinc, copper, arsenic and iron under different experimental conditions (such as: leaching time, temperature, sulfuric acid concentration and oxidant addition), were studied systematically. The results indicated that 98.4% zinc and 96.01% copper were leached using the first-stage of neutral leaching under conditions including final pH 5.0 ± 0.1, time 1 h, temperature 90 °C and the second-stage of sulfuric acid leaching under conditions including initial sulfuric acid concentration 190 g/L, leaching time 2 h, temperature 90 °C and 1.4 times oxidant addition. Meanwhile, 99.58% lead and 98.93% bismuth were remained in the sulfuric acid leaching residues which can be recovered by pyrometallurgical processes. The leaching behavior relationships among copper, zinc, arsenic and iron were also modeled. Results indicated that the ferric ion improved copper and zinc leaching. SEM study demonstrated that the leached surface was corroded, and EDS and XRD results indicated that zinc and copper oxides were disappeared during leaching while lead oxide was transformed into anglesite, and tin oxide was remained in the residues.

Morphological instability of aqueous dissolution of silicate glasses and minerals

Understanding of aqueous dissolution of silicate glasses and minerals is of great importance to both Earth and materials sciences. Silicate dissolution exhibits complex temporal evolution and rich pattern formations. Recently, we showed how observed complexity could emerge from a simple self-organizational mechanism: dissolution of the silica framework in a material could be catalyzed by the cations released from the reaction itself. This mechanism enables us to systematically predict many key features of a silicate dissolution process including the occurrence of a sharp corrosion front (vs. a leached surface layer), oscillatory dissolution and multiple stages of the alteration process (e.g., an alteration rate resumption at a late stage of glass dissolution). Here, through a linear stability analysis, we show that the same mechanism can also lead to morphological instability of an alteration front, which, in combination with oscillatory dissolution, can potentially lead to a whole suite of patterning phenomena, as observed on archaeological glass samples as well as in laboratory experiments, including wavy dissolution fronts, growth rings, incoherent bandings of alteration products, and corrosion pitting. The result thus further demonstrates the importance of the proposed self-accelerating mechanism in silicate material degradation.

Influence of chemical leaching on Al-Cu-Co decagonal quasicrystals

In the present investigation, the chemical leaching of the poly-grain Al65Cu15Co20 and Al65Cu20Co15 decagonal quasicrystalline alloys have been studied. The polished surfaces of as-cast Al65Cu15Co20 and Al65Cu20Co15 alloys have been leached by 10 mol/litre (mol/L) concentrated NaOH alkaline solutions. The X-ray diffraction, Scanning electron microscopy and Transmission electron microscopy techniques have been used for the structural and microstructural characterization of the samples and the chemical composition were characterized using Energy-dispersive X-ray spectroscopy. Chemical leaching exclusively removes the Al from the surfaces of the Al65Cu15Co20 and Al65Cu20Co15 decagonal quasicrystalline alloys, consequentially the formation of porous structure containing nano size particles of Cu, Co and Co3O4 have been observed on the leached surface. The leached surface of Al65Cu15Co20was more porous compared to Al65Cu20Co15 alloy, however the size of the precipitated nano-particles i.e. Cu, Co and Co3O4 were smaller in the case of Al65Cu20Co15 alloy. The elemental mapping through energy dispersive X-ray spectroscopy suggests that the distribution of Cu and Co were formed on the leached surface, however in some regions the oxygen was also detected.

Effects of fictive temperature on the leaching of soda lime silica glass surfaces

AbstractThe fictive temperature of glass characterizes the glass network structure and its thermal history, and thereby can influence ion and water transport in the glass surface. In this study, IR specular reflectance (SR), refractive index, and density measurements were used to characterize and confirm the effects of glass sample processing, especially the fictive temperature/thermal‐history variations. The subsequent acid leaching of these glasses created leached surface layers due to interdiffusion and reaction of hydrous species in the surface; the hydrogen depth profiles obtained with secondary ion mass spectrometry (SIMS) confirmed enhanced leaching with increasing fictive temperature. Attenuated total reflectance (ATR) in the mid‐ and near‐IR indicated increases in both SiOH and H2O species with increasing fictive temperature. The relative intensities and shapes of the ATR peaks were found to vary between the samples suggesting that speciation of the hydrous reaction products (eg, strong and weakly hydrogen‐bonded OH) is also influenced by the original fictive temperature of the glass, but could not be quantitatively determined.

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

The influence of diesel-truck exhaust particles on the kinetics of the atmospheric oxidation of dissolved sulfur dioxide by oxygen.

The automobile exhausts are one of the major sources of particulate matter in urban areas and these particles are known to influence the atmospheric chemistry in a variety of ways. Because of this, the oxidation of dissolved sulfur dioxide by oxygen was studied in aqueous suspensions of particulates, obtained by scraping the particles deposited inside a diesel truck exhaust pipe (DEP). A variation in pH showed the rate to increase with increase in pH from 5.22 to about ∼6.3 and to decrease thereafter becoming very slow at pH = 8.2. In acetate-buffered medium, the reaction rate was higher than the rate in unbuffered medium at the same pH. Further, the rate was found to be higher in suspension than in the leachate under otherwise identical conditions. And, the reaction rate in the blank reaction was the slowest. This appears to be due to catalysis by leached metal ions in leachate and due to catalysis by leached metal ions and particulate surface both in suspensions. The kinetics of dissolved SO2 oxidation in acetate-buffered medium as well as in unbuffered medium at pH = 5.22 were defined by rate law: k obs = k 0 + k cat [DEP], where k obs and k 0 are observed rate constants in the presence and the absence of DEP and k cat is the rate constant for DEP-catalyzed pathway. At pH = 8.2, the reaction rate was strongly inhibited by DEP in buffered and unbuffered media. Results suggest that the DEP would have an inhibiting effect in those areas where rainwater pH is 7 or more. These results at high pH are of particular significance to the Indian subcontinent, because of high rainwater pH. Conversely, it indicates the DEP to retard the oxidation of dissolved SO2 and control rainwater acidification.

The leaching characteristics and changes in the leached layer of antimony-bearing ores from China

China has the most abundant antimony (Sb) resources of any country in the world. Large quantities of Sb have been released from mining and smelting processes, causing serious Sb contamination in the mine or nearby areas. To understand the leaching characteristics of hazardous Sb, As, Pb and Cr from antimony minerals, 12 samples of antimony-bearing ores from eight large mines from China distributed in Hunan, Yunnan, Guizhou and Guangxi provinces were studied. The main compositions of these minerals are Sb2S3, SiO2 or CaCO3. The pH changes during the leaching indicated that some minerals themselves are alkaline, providing sufficient acid neutralizing capacity during leaching. However, some alkaline minerals release much more Sb, As, Pb and Cr than others. Inconsistencies between totals amounts and the released content of Sb, As, Pb and Cr were also found. The surface topography of an antimony sulfide mineral and the species changes of Sb and sulfur (S) on its leached surface were also characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. It is the oxidation dissolution of Sb2S3 that releases Sb. Sb(III) and S2− on the surface of the fresh mineral were oxidized to Sb(V) and S2O32− and SO42−, respectively, and finally, an equilibrium of dissolution was reached over time. The release of Sb, As, Pb and Cr from typical antimony ores is a source of Sb, As, Pb and Cr in the weathering zone; with this in mind, it is easier to understand the geochemical processes and the pollution accidents involving Sb and As within the mining areas and their surroundings.

Non-invasive methodology for the identification of plastic pieces in museum environment — a novel approach

The preservation of modern and contemporary art and costume collections in museums requires a complete understanding of their constituent materials which are often synthetic or semi-synthetic polymers. An extraordinary amount of quality information can be gained from instrumental techniques, but some of them have the disadvantage of being destructive.This paper presents a new totally integrated non-invasive methodology, for the identification of polymers and their additives, on plastic artefacts in museums. NMR (nuclear magnetic resonance) and in-situ FTIR-ATR (attenuated total reflection infrared spectroscopy) combination allowed the full characterization of the structure of these materials and correct identification of each one. The NMR technique applied to leached surface exudates identified unequivocally a great number of additives, exceeding the Py–GC–MS analysis of micro-fragments in number and efficiency. Additionally, in-situ FTIR-ATR provided exactly the same information of the destructive μ-FTIR about the polymer structure and confirmed the presence of some additives.Eight costume pieces (cosmetic boxes and purses), dating to the beginning of the 20th century and belonging to the Portuguese National Museum of Costume and Fashion, were correctly identified with this new integrated methodology, as being made of plastics derived from cellulose acetate or cellulose nitrate polymers, contradicting the initial information that these pieces were made of Bakelite. The identification of a surprisingly large number of different additives forms an added value of this methodology and opens a perspective of a quick and better characterization of plastic artefacts in museum environments.

Dissolution of glass wool, rock wool and alkaline earth silicate wool: Morphological and chemical changes in fibers

The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis.

Dissolution reaction and surface iron speciation of UICC crocidolite in buffered solution at pH 7.4: A combined ICP-OES, XPS and TEM investigation

The dissolution reaction and the surface modifications of crocidolite asbestos fibres incubated for 0.5, 1, 24, 48, 168 and 1440h in a phosphate buffered solution at pH 7.4 with and without hydrogen peroxide were investigated. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) was used to monitor the ion release into solution, X-ray Photoelectron Spectroscopy (XPS) was performed to unveil the chemistry of the leached surface, and High Resolution Transmission Electron Microscopy (HR-TEM) was carried out to monitor the structural modifications of the fibres. No significant differences were observed between dissolution experiments carried out with and without H2O2 with the exception of results after the first hour, from which it may be inferred that the dissolution proceeds faster in the presence of H2O2 but only in its very early steps. Congruent mobilization of Si and Mg from crocidolite was observed, increasing with time especially in the range between 1 and 48h, while Ca decreased after 48h and Fe was not detected at any incubation time. In the undersaturated conditions (0–48h), dissolution rate of UICC crocidolite fibres has been estimated to be d(Si)/dt=0.079μmolh−1. The fibre surface modification is continuous with time: XPS results showed a regular depletion of Si and Mg and enrichment of Fe along dissolution. The Fe2p3/2 signal on the surface was fitted with four components at 709.0, 710.5, 711.6 and 712.8eV binding energy values corresponding to: (i) Fe(II)–O and (ii) Fe(III)–O surrounded by oxygen atoms in the silicate structure, (iii) Fe(III)–OOH as a product of the dissolution process, and (iv) Fe in a phosphate precipitate (Fe–P), respectively. The evolution of Fe speciation on the crocidolite surface was followed by integrating the four photoemission peaks, and results showed that the oxidative environment promotes the formation of Fe(III)–O (up to 37% Fetot) and of Fe–P species (up to 16% Fetot), which are found on the fibre surface at the end of the dissolution experiment. HR-TEM showed that the crocidolite lattice structure, the fibrous habit and the high aspect ratio are preserved upon leaching, while Fe-bearing nanoparticles, likely amorphous and possibly displaced on top of the fibres, become clearly visible. As a conclusion, coating of the crocidolite fibres was demonstrated to occur due to precipitation of Fe-rich phases (both phosphates and oxide-hydroxides). The occurrence of such iron armouring may modulate asbestos toxicity and possibly be the initial step in the formation of asbestos ferruginous bodies.