Mineral phases formation on the pozzolan/lime/water system

In Spain, the paper industry recycles large amounts of waste paper in the new paper production process. Paper sludge thermal activation (calcination at 700 °C for 2 h) is an environment-friendly alternative source for metakaolinite (MK) to be used for the manufacture of blended cements or cement based materials.This paper could contribute to standardization of the use of new pozzolanic products in cement based materials and its use mixed with saturated lime dissolution. In this process are obtained zeolite, CSH gel, hydrotalcite-like compounds, hydrated aluminate tetracalcium and stratlingite.These materials are formed in different times of pozzolanic reaction.     

Effect of activation conditions of a kaolinite based waste on rheology of blended cement pastes

This paper reports the influence of calcining temperature on the rheology of blended cement pastes with 10 and 20% of thermally activated paper sludge as pozzolan at water/binder ratio of 0.5 and 0.4. The kaolinite based waste was activated at different activation temperatures (700–800 °C) and retention times of 2 and 5 h. The yield stress of the blended pastes increased when the activation intensity increased as a result of the increased calcite and free lime content. Due to the stiffness of the blended pastes, a superplasticiser (sodium lignosulfonate) was used in order to reduce the yield stress. The best results could be obtained using the lower calcining temperature (700 °C and 2 h).     

Mn-kaolinite synthesis under low-temperature hydrothermal conditions

Mn-kaolinite was hydrothermally synthesized, for the first time, using silicic acid, Mn-carbonate and aluminum nitrate mixed with aqueous solutions of KOH at 100–200 °C for 24–96 h. Without the addition of Mn-carbonate to silicic acid and aluminum nitrate mixture, no crystalline material could be synthesized by hydrothermal treatment up to 200 °C for 6 days. However, by the addition of Mn-carbonate to the above precursors, Mn-kaolinite was synthesized at both 100 and 200 °C for 1 or 2 days, indicating that Mn played an important role in the formation of kaolinite. At a reaction temperature of 100 °C, the Mn-kaolinite peaks became sharper with increasing reaction duration, as expected.     

Effects of sand addition on production of lightweight aggregates from Tunisian smectite-rich clayey rocks

Smectite-rich claystone–marlstone samples from 12 outcrops located in the Southern Atlas domain of Tunisia were investigated with regard to manufacture of lightweight aggregates (LWAs). The clayey materials mainly consist of smectite, kaolinite and illite, together with quartz, calcite, dolomite and feldspars as accessory components. 10–12 mm pellets were prepared from wet paste and initially heated to 600 °C, 700 °C or 800 °C (depending on the raw material) for at least 2 h in order to avoid any explosion of the aggregate. The pellets were then subjected to a quick firing process at 1180 °C. The addition of 15% of quartz sand (< 250 μm grain size) to the raw materials was found to improve some required pre-treatments and give better expansion properties to some of the aggregates. The addition of 1% used automobile oil to the clay and quartz sand mixtures caused the formation of more gas and a drop in bloating temperature. The obtained LWAs were characterized by physical properties such as apparent density, mechanical resistance, water absorption and expansion. The laboratory results were comparable to those of two commercial LWAs from France (Argidécor®) and Portugal (LECA®) and provide new openings for the utilization of Tunisian claystone in civil engineering work or in agricultural applications.     

Effect of the crystallinity of kaolinite precursors on the properties of mesoporous silicas

Mesoporous silicas (MesoPSs) were hydrothermally synthesized from calcined and selectively acid-leached kaolinites with a range of crystallinity, using cetyltrimethyl ammonium bromide (CTABr), to investigate the effect of the kaolinite crystallinity on the porous properties of the resulting MesoPSs. Four kaolinites were used, with Hinckley indices ranging from 0.51 to 1.20 and (001) crystallite sizes ranging from 20 to 37 nm. After calcination at 600 °C for 24 h they were selectively leached with 2.5 M H₂SO₄ at 90 °C for 2 h to prepare microporous silica (MicroPSs). The Si/Al ratios of these MicroPSs varied from 21 to 82 and their specific surface areas (S_BET) ranged from 169 to 370 m²/g, these parameters tending to increase with decreasing Hinckley index of the kaolinite. MesoPSs were synthesized by reacting the resulting MicroPSs with CTABr in NaOH solution under hydrothermal conditions. The MicroPS was mixed with CTABr, NaOH and water in the molar ratio (MicroPS):CTABr:NaOH:H₂O = 1:0.1:0.3:150. The synthesis was carried out by stirring the suspension at room temperature for 24 h, aging for 24 h, hydrothermal treatment at 110 °C for 24 h and calcination at 560 °C for 6 h to remove the surfactants. The S_BET values of the resulting MesoPSs ranged from 932 to 1240 m²/g, correlating with the S_BET values of the precursor MicroPS and the crystallinity of the kaolinite starting materials.     

Algerian kaolinite used for mullite formation

In the present study, mullite was synthesized through reaction sintering of Algerian kaolinite and high purity alumina. The raw powders were wet ball milled in a planetary ball mill. Powders' morphology and the microstructure of the sintered samples were characterized by means of a scanning electron microscope. An X-ray diffractometer equipped with a heating facility and a differential thermal analyzer were used to follow mullite formation. Cylindrical specimens were produced by uniaxial cold compaction at a pressure of 75 MPa and sintered at different sintering temperatures for different sintering times. The heating rate was 10 °C/min. It was found that Algerian kaolinite was suitable for mullite production through reaction sintering with pure Al₂O₃. Formation of complete mullite occurred at 1550 °C. A relative density of 94% (of the theoretical density) was achieved at a relatively low sintering temperature of 1600 °C and a sintering time of 4 h.     

Hydrothermal reaction between CSH and kaolinite for the formation of tobermorite at 180°C

11 Å tobermorites were made from C---S---H (Ca/Si = 1.14) and kaolinite with Ca/(Si+Al) = 0.8 and Al/(Si+Al)= 0.15 at 180°C. The C---S---H was prepared from colloidal silica and lime at 130°C and 180°C for 2 h. Reaction gives in succession C---S---H, poorly crystalline Al-substituted tobermorite, and highly crystalline Al-substituted tobermorite. The addition of kaolinite markedly accelerates the formation of tobermorite within 4 h, more effectively with C---S---H prepared at 130°C than with that prepared at 180°C. X-ray fluorescence diffractometry shows that the Al coordination number is a mixture of 4 and 6 in the initial products and shifts to 4 with an increase in processing time. This agrees with the results for the degree of reaction of the kaolinite.     

Rheology and conduction calorimetry of cement modified with calcined paper sludge

This paper considers calcined paper sludge as an alternative source of metakaolin, an established supplementary cementitious material. Calcination of the sludge generated in the recycling of newsprint paper at 700 °C yields a product with pozzolanic properties. The effects of this recycled metakaolin on the rheology and conduction calorimetry of cement pastes have been studied and compared to the effects of commercial metakaolin. The effects are similar and the results show that calcined paper sludge has the potential to be used as a supplementary cementitious material. This offers a route for utilising this waste material, as an alternative to the increased environmental burden associated with the production of metakaolin from natural kaolinite resources.     

Clay content of argillites: Influence on cement based mortars

The pozzolanic activity of four heated powders containing different clays has been tested. Mineral transformations during calcination from 20 to 900 °C have been followed by X-ray diffraction (XRD) and Differential Scanning Calorimetry (DSC). Compressive strength tests were performed at 1, 7 and 28 days on cement–clay mortars using 30% of pozzolanic material as a replacement by mass for cement. Calcination temperatures corresponded to the stages of potentially high reactivity identified by XRD. Results indicated that there exists incompatibility between clay minerals which can not be activated at the same temperatures. Products of recrystallisation of the earlier activated clay were already formed when the second clay type was activated. Concerning the type and the abundance of clay minerals in the raw material, this study evidences that the compressive strength is, at first approximation, correlated with the percentage of activated clay and less with the nature of the clay assemblage.     

The origin of the pozzolanic activity of calcined clay minerals: A comparison between kaolinite, illite and montmorillonite

This paper investigates the decomposition of three clayey structures (kaolinite, illite and montmorillonite) when thermally treated at 600 °C and 800 °C and the effect of this treatment on their pozzolanic activity in cementitious materials. Raw and calcined clay minerals were characterized by the XRF, XRD, ²⁷Al NMR, DTG and BET techniques. Cement pastes and mortars were produced with a 30% substitution by calcined clay minerals. The pozzolanic activity and the degree of hydration of the clinker component were monitored on pastes using DTG and BSE-IA, respectively. Compressive strength and sorptivity properties were assessed on standard mortars. It was shown that kaolinite, due to the amount and location of OH groups in its structure, has a different decomposition process than illite or montmorillonite, which results in an important loss of crystallinity. This explains its enhanced pozzolanic activity compared to other calcined clay–cement blends.     

A comparison of diamonds irradiated by high fluence neutrons or electrons, before and after annealing

Neutron- and electron-irradiated type Ia “black” diamonds were analyzed: three near colorless type Ia diamonds were treated in a nuclear reactor with a dose of 1.8 × 10¹⁷ neutrons/cm² and three equivalent samples were irradiated in an electron accelerator with a dose of approximately 0.5 GGy 10 MeV electrons. The diamonds were then annealed and analyzed after the different steps of the treatment. The samples turned from near colorless to very dark green to opaque black upon irradiation and deep greenish yellow to deep orangy brown upon annealing (Fig. 1). The amount of brown color developed during the treatment was found to relate to the type of irradiation used and likely to the total dose of irradiation. The absorption and photoluminescence features as well as the color changes that were observed were found to be unusual and characteristic for diamonds treated with such high irradiation doses. Certain spectral features such as the 644/649 nm, the 724/734/738 nm, the 920 nm and the 967 nm absorptions were only detected in the neutron-irradiated diamonds while others such as the 6165 cm^− 1 and the 805 nm absorptions were only found in the spectra of the electron-irradiated stones.In addition to these treatment experiments some neutron-irradiated very dark green (appearing black) diamonds were heated from 300 to 1100 °C in increments of 50 °C to get a precise idea of the temperature at which color changes occur and the various absorption peaks form. All diamonds turned yellowish to orangy brown after annealing above 700 °C and most of them exhibited unusually strong H1b and/or H1c absorptions after annealing at > 900 °C.     

Hydrothermal synthesis (200 °C) of Co–kaolinite and Al–Co–serpentine

In the systems CoO–Al₂O₃–SiO₂–H₂O and CoO–Al₂O₃–SiO₂–HCl–H₂O, at initial pH between 5.5 and 8.1 and temperature of 200 °C, kaolinite is unstable and the following phases form through a dissolution-precipitation process: a) kaolinite and Co-bearing kaolinite; b) Al–Co–serpentine; and c) poorly crystalline phases. Identification of the several phases was carried out from a combination of X-ray diffraction and transmission/analytical electron microscopy.Co–kaolinite shows variable morphologies: a) Platy lath-shaped particles with very low Co content; b) Spherical particles, with relatively constant Co contents (in the order of 0.10 apfu); c) Kaolinite stacks with very variable Co contents (up to 0.25 apfu). Analytical data indicate that the presence of Co(OH)₂ in the system favors the dissolution process as well as serpentine formation but it leads to the parallel formation of abundant poorly crystalline phases. The Co-content in kaolinite increased as a function of the Co(OH)₂/CoCl₂ ratio in the initial systems, and it is reflected by a parallel increase of the b-cell parameter of kaolinite. The average composition of the coexisting Al–Co–serpentine is: (Al_1.20Fe_0.11Co_1.27)(Si_1.64Al_0.36)O₅(OH,Cl)₂, with Cl contents in the order of 0.14 apfu.The assemblage Co–kaolinite + Al–Co–serpentine, which appears to be stable at 200 °C, has not been described in natural environments, probably because it requires unusual Al- and Co-rich chemical systems.     

Preparation of decolorizing ceramsites for printing and dyeing wastewater with acid and base treated clay

A new type of decolorizing ceramsites for printing and dyeing wastewater were prepared, by means of acid activation, base neutralization, granulation and heating treatment, by using palygorskite, Hangjin2# clay, bentonite or sepiolite as raw materials. The experimental results show that, the decolorizing ceramsites made of palygorskite have the best performances among different clay minerals in treating printing and dyeing wastewater. Its decolorizing amount is 635 mL g^− 1 and the reduction in COD is 81%, after 5 min static treatment at normal temperature. After calcined at 700 °C for 1 h, the loss ratio of decolorizing ceramsites made of palygorskite is less than 5%. Treated with saturated (NH₄)₂SO₄ solution for 10 min, and then calcined at 300 °C for 10 min, the used decolorizing ceramsites can be reused for more than 15 times. The decolorizing effect of the decolorizing ceramsites is mainly attributed to the combined chemical flocculation reaction of various metal ions in the material, with minor physical adsorption involved.     

Mineralogical Evolution of Kaolin‐Based Drinking Water Treatment Waste for Use as Pozzolanic Material. The Effect of Activation Temperature

This study reports on exhaustive scientific research into the influence of the activation temperature of inert waste from drinking water treatment plants for use as supplementary cementing material in cements. The effect of activation temperature on the mineralogy of the reactive products resulting from pozzolanic activity and on the evolution of the hydrated phases formed during the pozzolanic reaction at 28 d of curing was analyzed with the assistance of different instrumental techniques such as X‐ray fluorescence, X‐ray diffraction, thermogravimetric analysis, infrared spectroscopy, and scanning electron microscopy. The results show that all the activated products (based on metakaolinite) presented high pozzolanic activity at all ages of the reaction (up to 90 d), although 600°C at 2 h are the recommended ideal activation conditions from an energetic and economic viewpoint. The activation temperature (600°C–900°C for 2 h of retention) plays an important role in the reaction kinetics in activated drinking water waste/Ca(OH)₂ systems. The hydrated phases identified under these activation conditions were very similar, but with important differences in the crystalline aluminates phases content. Thus, the formation of stratlingite (C₂ASH₈) is favored at low temperatures (<800°C); whereas at higher temperatures (at 900°C), tetra calcium aluminate hydrate (C₄AH₁₃) appears as the only crystalline phase. Finally, this type of treatment of drinking water waste (based on kaolinite) is ideal to obtain future pozzolans based on recycled metakaoline, a product that is currently listed in international standards for the manufacture of commercial cements.     

Pakistani bentonite in mortars and concrete as low cost construction material

A Pakistani bentonite, in “as is” (21 °C) and “heated” (150 °C, 250 °C, 500 °C, 750 °C and 950 °C) conditions, was incorporated in mortar cubes, concrete cylinders and concrete beams as a partial substitute for Ordinary Portland cement (OPC) and studied in detail. Results showed that OPC mortars and concrete containing 20% “as is” and 25% “heated to 150 °C” bentonite could be used as low-cost construction materials. They will also reduce energy consumption, preserve natural resources and solve environmental problems related to cement production as well as augment the durability and life cycle of the concrete structures.The X-ray diffraction patterns showed that bentonite possessed both crystalline and amorphous phases. The strength activity indices (SAI) after 7 and 28 days were higher than 75% for “as is” and “heated” bentonite, except for the 950 °C samples, which was below the ASTM C618 specified limit of 75%. The maximum SAI was shown by “150 °C heated” bentonite. The compressive strength data also showed similar results for OPC mortar cubes and concrete cylinders containing “150 °C heated” bentonite. When compared with the control mixture, the compressive strength values were the same as for mortar containing 25% bentonite as replacement of OPC. However, these values decreased in concrete initially and started to gain strength remarkably after 28 days. Resistance to sulphate attack and water absorption tests on mortar cubes soaked in 2% magnesium sulphate and 5% sodium sulphate solutions demonstrated consistent improvement as the bentonite content in them was increased. The modulus of rupture of all concrete beams decreased as the OPC substitution level by bentonite increased from 20% to 40%. Bond strength of OPC mortar containing 20% “as is” and 25% “heated to 150 °C” bentonite in brick prisms was almost the same as that of control mixture.     

Thermal activation and alkali dissolution of silicon from illite

TGA, DTA, FTIR, XRD and 29Si MAS NMR were used to investigate the thermal activation of illite. Illite experiences a series of thermal solid-state phase transformations. Dehydroxylation at 400700 °C forms dehydrated illite, which remains the layered framework of illite. From 700 °C to 1093 °C, Si–O tetrahedral framework remains unchanged. When heated above 1093 °C, the layered structure is destroyed and an amorphous silica-rich glass phase is formed. The mullitization occurs when the temperature exceeds 1100 °C.XRD and FTIR studies show that the silica in silica-rich glass phase dissolves in soda liquor, which indicates that silicon can be removed from illite after thermochemical activation (TCA) followed by alkali leaching. The formation of sodium aluminosilicates of Na₉₆Al₉₆Si₉₆O₃₈₄ and 0.95Na₂O · Al₂O₃ · 3.25SiO₂ · 4.79H₂O during alkali leaching may reduce the desilication to a great extent.Desilication tests after TCA show that the suitable activation conditions for illite are 11001150°C and 9060 min. A desilication of 45% was obtained under the conditions for an ore sample bearing about 85% illite, 9% quartz and 5% muscovite.     

Hydration reaction and hardening of calcined clays and related minerals III. Influence of calcination process of kaolinite on mechanical strengths of hardened metakaolinite

Compressive strengths of calcium hydroxide-activated metakaolinite cements have been studied versus both calcination process of kaolinite (use of fixed-bed and stirredbed - or rotary kiln- Laboratory reactors) and calcination temperature. Whatever the curing time from 7 days to 90 days, a maximum of strength is observed for calcination in the 700–850°C temperature range, but metakaolinite obtained in rotary kiln (process which realizes the dehydration of kaolinite in a shorter time, but can lead to a phenomenon of particle aggregation on the furnace wall) is less disordered and strengths of cements derived there from are some weaker than in the case of cements made with metakaolinite from fixed-bed calcination.     

Enzyme immobilization: Part 2: Immobilization of alkaline phosphatase on Na-bentonite and modified bentonite

Alkaline phosphatase from calf intestinal mucous membrane was immobilized on unmodified and modified bentonites. The activity of the immobilized enzyme was examined under varying experimental conditions. The effects of various factors such as concentration of enzyme solution, pH and temperature, stirring and various thermodynamic parameters were evaluated. The highest enzyme activity, for free and immobilized enzyme, was obtained in 0.1 M phosphate buffer at pH 7. Optimal enzyme activity of both free and adsorbed enzyme was reached at pH = 10. The best time period of magnetic stirring was 2 h at 4 °C. The adsorption isotherm was modeled by Langmuir equation. The effect of substrate concentration on enzymatic activity of the free and immobilized enzymes showed a good fit to the Michaelis–Menten plots. The immobilized enzyme exhibited activity comparable to the soluble enzyme after storage at 30 °C. Thermal stability and resistance against proteolytic attack were also evaluated.     

Removal of the persistent pollutant chlorobenzene by adsorption onto activated montmorillonite

The potential of activated bentonite was assessed for adsorption of chlorobenzene from aqueous solution. The bentonite used was treated by chemical and thermal activation over 100–500 °C. The thermal activation increased the adsorption capacity more strongly than chemical activation which consists to acid and hydrogen peroxide treatment. The removal is dominated by adsorption at low initial concentrations and low temperatures and favourable in acidic media. The dependence of the adsorption on pH appears to be related to the solubility of chlorobenzene. Thermodynamic parameters such as ΔH°, ΔS°, ΔG° and Ea have been calculated. The adsorption process is spontaneous and exothermic in nature. The Freundlich isotherm described the adsorption data over the concentration range (20–270 °C).