Recycling of harmful waste lead-zinc mine tailings and fly ash for preparation of inorganic porous ceramics

The porous ceramics were prepared by directly sintering of lead-zinc mine tailings and fly ash as the raw materials without any additional sintering and foaming agent. The effects of fly ash addition on the crystalline phases, pore structure, physical–chemical porosities and mechanical strength were investigated. The results showed that the bulk density decreased firstly and then increased while the porosity and water absorption presented the opposite tendency with the increase of fly ash content. Meanwhile, the chemical stability improved and the flexural strength had the same variation tendency of the bulk density. The phase evolution of sample with 60 wt% fly ash addition indicated that anorthite phase was formed at low temperature (1000 °C). The thermal behavior illustrated that the foaming process was initiated by the reaction of internal constituents in the lead-zinc mine tailings. Different pore structures indicated different foaming mechanisms that probably occurred at different temperatures. The porous ceramics with 60 wt% fly ash addition exhibited excellent properties, including bulk density of 0.93 g/cm³, porosity of 65.6%, and flexural strength of 11.9 MPa.     

Post-treated incinerator bottom ash as alternative raw material for ceramic manufacturing

New ceramics based on 60 wt% of alternative raw material derived from post-treated municipal solid waste incinerator bottom ashes and 40 wt% of refractory clay were studied. The chemical analysis of the compositions was evaluated by ICP. The thermal and densification behavior of the ceramic batches were evaluated by DTA-TG and dilatometry techniques, respectively. After that, the degree of sintering at different temperatures and soaking times was evaluated in detail, measuring open and closed porosities, linear shrinkage and water absorption. The crystallinity at different temperatures (during heating and after cooling) and microstructure of the obtained samples were evaluated by high-temperature X-ray diffraction (HTXRD) and scanning electron microscopy (SEM), respectively. For these new ceramics, the experimental results highlighted sintering range between 1190–1240 °C. In addition, the specimens demonstrated low water absorption and high crystallinity (with anorthite as main crystalline phase), leading to mechanical characteristics comparable to those of commercial ceramic products (bending strength > 40 MPa).     

Preparation and characterization of porous anorthite ceramics from red mud and fly ash

The porous anorthite ceramics with high porosity, good mechanical strength and low heat conductivity were prepared using red mud and fly ash as raw materials via the pore forming method. The effects of sintering temperature and fly ash on phase evolution, densification, compressive strength, thermal conductivity and microstructure of the ceramic materials were investigated. The results showed that the compressive strength of the porous ceramics had an obvious improvement with the increase in fly ash, and the densification and heat conductivity decreased firstly and then increased. In particular, specimen S2 containing 30 wt% red mud and 40 wt% fly ash sintered at 1150°C had the better performances. It had the water absorption of 18.18%, open porosity of 38.52%, bulk density of 1.29 g/cm³, compressive strength of 42.46 MPa, and heat conductivity of 1.24 W/m·K. X-ray diffraction analysis indicated that mullite, anorthite, α-quartz, and diopside ferrian were the dominant phases in the specimens. Scanning electron microscopy micrographs illustrated that plenty of open pores with strip shape and closed pores with axiolitic shape existed in the specimens. Furthermore, the existence of mullite could prevent crack propagation to enhance the energy of inter-granular fracture. It endowed the porous anorthite ceramics with high porosity, good compressive strength, and low heat conductivity.     

Ceramic tiles derived from coal fly ash: Preparation and mechanical characterization

Coal fly ash (CFA) accounts for a large fraction of the solid waste produced in China. Hence, there is an urgent need for the effective utilization of CFA, for example, as a raw material for ceramics production. In this study, clay- and feldspar-like materials fabricated by alkali activation pre-treatment of CFA were mixed with untreated CFA (regarded as a quartz-like material) and sintered to prepare fully ash-based ceramic tiles. The obtained tiles exhibited excellent sintering properties, e.g., low firing temperature and a wide sintering range; further, they showed better green strength (due to hydrogen bonding) and post-sintering performance (due to fluxing and mullite skeleton effects) than ceramic tiles produced exclusively from untreated CFA. The fully ash-based ceramic tiles sintered at 1100 °C exhibited optimal post-sintering properties (bulk density, 2.5 g/cm³; rupture modulus, 50.1 MPa; and water absorption, 0%). Thus, the proposed method is well suited for preparing a novel kind of ceramic tiles completely derived from CFA, highlighting its importance in the field of fly ash ceramics.     

Preparation and characterization of the one-piece wall ceramic board by using solid wastes

For the purpose of building energy-saving, a novel one-piece wall ceramic board was prepared by using fly ash and ceramic waste as the main raw materials for its matrix part and foam part, respectively. The effects of raw material composition, sintering temperature on the macro and micro properties were systematically investigated. The optimum parameter for the matrix part was obtained at 1220 °C with 70 wt% fly ash and 4 wt% quartz, while that for the foam part was 1220 °C with 97 wt% ceramic waste and 3 wt% silicon carbide. For the matrix sample, the highest rupture modulus reaches 53.97 MPa, and the corresponding water absorption capacity and thermal conductivity are 1.08% and 0.54396 W/(m K), respectively. For the foam part, the best bulk density and thermal conductivity are 443 kg/m³ and 0.10528 W/(m K), respectively. Subsequently, the optimal matrix and foam samples were introduced into the co-fired process (1220 °C), and the results show that the new method for the preparation of one-piece wall ceramic board was fully acceptable. Furthermore, the simulated results indicate that the proposed one-piece wall ceramic board can efficiently reduce the thermal bridges and exerts excellent energy conservation effect.     

Preparation and properties of anorthite-based ceramics by using metallurgical solid waste and fly ash

A large amount of metallurgical solid waste accumulation poses a serious threat to the environment. Study on synergistic reinforcement of synthetic process of metallurgical solid waste-based ceramics with fly ash is of great significance in reducing environmental pollution and resource utilization. A metallurgical solid waste-based ceramic used as building ceramic was developed with the erosion part of used MgO–C bricks and fly ash as main raw materials, and the amount of solid waste added to the prepared ceramics was at least 60 wt% and up to 90 wt%. The effects of fly ash content and sintering temperature on the crystalline phase transitions, morphologies, and the main physical and mechanical properties of ceramics were investigated by X-ray diffraction, scanning electron microscopy, and mechanical testing. The results show that the obtained ceramics presented maximum bending strength and minimum water absorption, 80.14 MPa and 5.04%, respectively, when the raw material proportions were the erosion part of used refractories accounted for 60 wt%, fly ash 20 wt%, pyrophyllite 10 wt%, and quartz sands 10 wt%, and the process parameters were the sintering temperature 1150°C, sintering time 120 min, and molding pressure 15 MPa.     

Fabrication and characterization of anorthite-based ceramic using mineral raw materials

The purpose of this study is to design a novel single crystalline phase ceramic based on anorthite whose properties fulfill the tableware market requirements such as high appearance quality, strength and thermal shock resistance. To obtain the single phase anorthite ceramic, ball clay, quartz, calcite, feldspar and alumina were used as raw materials. The single phase anorthite ceramic was fabricated by slip casting and sintering at 1230 °C for 1 h. It has a high flexural strength of 103 MPa, which is higher than that of the conventional porcelain. The single phase anorthite ceramic had relatively low (4.9 × 10^?6 K^?1) thermal expansion coefficient which can be matched with applicable glaze easily. Furthermore, the single phase anorthite ceramic had high degree of whiteness (L* = 94) and excellent translucency behavior which could achieve a high-quality decorative effect.     

Dry pressed ceramic tiles based on fly ash–clay body: Influence of fly ash granulometry and pentasodium triphosphate addition

Fly ash from brown coal (70 wt.%) and stoneware clay (30 wt.%) were used for the dry pressed ceramic tiles (according to EN 14411) raw materials mixture. The effects of fly ash milling and pentasodium triphosphate addition as a deflocculant and fluxing agent on the properties of green body (flexural strength, bulk density) and fired body (EN ISO 10545—water absorption, bulk density, true density, apparent porosity, flexural strength, frost resistance) were studied and explained as a function of the firing temperature (1000–1150 °C). Fly ash milling (corresponding to 5 wt.% residue of fly ash grains on 0.063 mm sieve) increased the sintering abilities of the fly ash–clay body. A similar effect was achieved by 1.3 wt.% pentasodium triphosphate (PST) addition with an increase in green body flexural strength and a decrease in water content of the granulate. Fly ash–clay bodies can be frost resistant with water absorption above 10% due to positive pore size distribution, which were examined using the high-pressure mercury porosimetry method.     

Porous anorthite ceramics with ultra-low thermal conductivity

Porous anorthite ceramics with an ultra-low thermal conductivity of 0.018 W/m K have been fabricated by hydrous foam-gelcasting process and pressureless sintering method using γ-alumina, calcium carbonate and silica powders as raw materials. Microstructure and phase composition were analyzed by SEM and XRD respectively. Properties such as porosity, pore size distribution and thermal conductivity were measured. High porosity (69–91%) and low thermal conductivity (0.018–0.13 W/m K) were obtained after sintering samples with different catalyst additions at 1300–1450 °C. Porosity, pore size, pore structure and grain size had obvious effect on heat conduction, resulting in the low thermal conductivity. The experimental thermal conductivity data of porous anorthite ceramics were found to be fit well with the computed values derived from a universal model.     

Ba0.6Sr0.4TiO3–MgO ceramics from ceramic powders prepared by improved aqueous gelcasting-assisted solid-state method

Based on aqueous gelcasting-assisted solid-state method (AGASSM), improved aqueous gelcasting-assisted solid-state method (IAGASSM) was proposed to prepare the 45 wt% Ba_0.6Sr_0.4TiO₃–55 wt% MgO (BSTM) ceramic powders. It is found that the BSTM ceramic powders prepared by IAGASSM are the most uniform with the smallest particles (D_av = 0.83 μm) than those prepared by solid-state method (SSM) and AGASSM. The phase compositions of the BSTM ceramic powders and ceramics from the prepared ceramic powders are the same whatever ceramic powder preparation method is adopted. Compared with SSM and AGASSM, the BSTM green samples and ceramics from ceramic powders prepared by IAGASSM are the most uniform. Furthermore, it is found that adopting IAGASSM to prepare ceramic powders could not only improve the dielectric properties of the BSTM ceramics considerably, but also decrease their sintering temperature.     

Microwave dielectric properties of Pb2MoO5 ceramic with ultra-low sintering temperature

Ultra-low firing microwave dielectric ceramic Pb₂MoO₅ with monoclinic structure was prepared via a conventional solid state reaction method. The sintering temperature ranged from 530 °C to 650 °C. The relative densities of the ceramic samples were about 97% when the sintering temperature was greater than 570 °C. The best microwave dielectric properties were obtained in the ceramic sintered at 610 °C for 2 h with a permittivity ∼19.1, a Q × f value about 21,960 GHz (at 7.461 GHz) and a temperature coefficient value of −60 ppm/°C. From the X-ray diffraction, backscattered electron image results of the co-fired samples with 30 wt% silver and aluminum additive, the Pb₂MoO₅ ceramics were found not to react with Ag and Al at 610 °C for 4 h. The microwave dielectric properties and ultra-low sintering temperature of Pb₂MoO₅ ceramic make it a promising candidate for low temperature co-fired ceramic applications.     

Co-precipitation synthesis route to yttrium aluminum garnet (YAG) transparent ceramics

Yttrium aluminum garnet (YAG) precursor was synthesized via a coprecipitation method with aluminum nitrate and yttrium nitrate as raw materials, using ammonium hydrogen carbonate (AHC) as the precipitant. Fine and low-agglomerated YAG powder was obtained by calcining the precursor at 1200 °C. The primary crystallites were measured to be ～120 nm in size and weakly agglomerated to a particle size of ～500 nm, indicating a high degree of sinterability. With 0.5 wt% tetraethyl orthosilicate (TEOS) and 0.1 wt% magnesia as sintering aids, transparent YAG ceramics were fabricated by vacuum sintering at 1730–1790 °C for various hours. The influences of sintering temperature and holding time on the microstructure and transmittance of YAG ceramics were discussed.     

Fabrication and characterization of anorthite–mullite–corundum porous ceramics from construction waste

In this work, anorthite–mullite–corundum porous ceramics were prepared from construction waste and Al₂O₃ powders by adding AlF₃ and MoO₃ as mineralizer and crystallization catalyst, respectively. The effects of the sintering temperature and time on open porosity, mechanical properties, pore size distribution, microstructure, and phase composition were characterized in detail. The results showed that the formation of the mullite whiskers and the properties of the anorthite–mullite–corundum porous ceramics depended more on the sintering temperature than the holding time. By co-adding 12 wt% AlF₃ and 4 wt% MoO₃, mullite whiskers were successfully obtained at sintering temperatures upon 1350 °C for 1 h. Furthermore, the resultant specimens exhibited excellent properties, including open porosity of 66.1±0.7%, biaxial flexural strength of 23.8±0.9 MPa, and average pore size of 1.32 µm (the corresponding cumulative volume percent was 37.29%).     

Utilization of recycled paper processing residues and clay of different sources for the production of porous anorthite ceramics

Production of porous anorthite ceramics from mixtures of paper processing residues and three different clays are investigated. Suitability of three different clays such as enriched clay, commercial clay and fireclay for manufacturing of anorthite based lightweight refractory bricks was studied. Porous character to the ceramic was provided by addition of paper processing residues (PPR). Samples with 30–40 wt% PPR fired at 1200–1400 °C contained anorthite (CaO·Al₂O₃·2SiO₂) as major phase and some minor secondary phases such as mullite (3Al₂O₃·2SiO₂) or gehlenite (2CaO·Al₂O₃·SiO₂), depending on the calcite to clay ratio. Anorthite formation for all clay types was quite successful in samples with 30–40 wt% of paper residues fired at 1300 °C. A higher firing temperature of 1400 °C was needed for the fireclay added samples to produce a well sintered product with large pores. Gehlenite phase occurred mostly at lower temperatures and in samples containing higher amount of calcium (50 wt% PPR). Compressive strength of compacted and fired pellets consisting of mainly anorthite ranged from 8 to 43 MPa.     

Sintering behavior of ZrB2–SiC composites doped with Si3N4: A fractographical approach

ZrB₂–SiC composite ceramics were doped with 0, 1, 3 and 5 wt% Si₃N₄ plus 1.6 wt% carbon (pyrolized phenolic resin) as sintering aids and fabricated by hot pressing process under a relatively low pressure of 10 MPa at 1900 °C for 2 h. For a comparative study, similar ceramic compositions were also prepared by pressureless sintering route in the same processing conditions, with no applied external pressure. The effect of silicon nitride dopant on the microstructural evolution and sintering process of such ceramic composites was investigated by a fractographical approach as well as a thermodynamical analysis. The relative density increased by the addition of Si₃N₄ in hot pressed samples as a fully dense composite was achieved by adding 5 wt% silicon nitride. A reverse trend was observed in pressureless sintered composites and the relative density values decreased by further addition of Si₃N₄, due to the formation of gaseous products which resulted in the entrapment of more porosities in the final structure. The formation of ZrC phases in pressureless sintered samples and layered BN structures in hot pressed ceramics was detected by HRXRD method and discussed by fractographical SEM-EDS as well as thermodynamical analyses.     

Foam-gelcasting preparation,microstructure and thermal insulation performance of porous diatomite ceramics with hierarchical pore structures

Hierarchically pore-structured porous diatomite ceramics containing 82.9∼84.5% porosity were successfully prepared for the first time via foam-gelcasting using diatomite powder as the main raw material. Sizes of mesopores derived from the raw material and macropores formed mainly from foaming were 0.02∼0.1 μm and 109.7∼130.5 μm, respectively. The effect of sintering temperature, additive content and solid loading of slurry on pore size and distribution, and mechanical and thermal properties of as-prepared porous ceramics were investigated. Compressive strength of as-prepared porous ceramics increased with sintering temperature, and the one containing 82.9% porosity showed the highest compressive strength of 2.1 ± 0.14 MPa. In addition, the one containing 84.5% porosity and having compressive strength of 1.1 ± 0.07 MPa showed the lowest thermal conductivity of 0.097 ± 0.001 W/(m·K) at a test temperature of 200 ̊C, suggesting that as-prepared porous ceramics could be potentially used as good thermal insulation materials.     

Recycling of industrial wastes in ceramic manufacturing: State of art and glass case studies

Nowadays, ceramic tile are manufactured at zero emissions permitting to recycle all by-products and part of residues derived from depuration treatments (exhausted lime, glazing sludge and polishing sludge). In addition to this environmentally friendly tendency, in the last years an increasing number of scientific studies demonstrated the feasibility to use alternative raw materials in substitution of different component of the ternary clay-feldspar-quartz system. In the first part of the paper is reported the state of the art of industrial waste recycling in the ceramic sector, with the focus on review studies related to both ceramic tiles and bricks..In the second part of the work are reported two case studies conducted by the authors with the aim to formulate ceramic bodies using alternative raw materials. New tailored compositions were obtained replacing clays, flux and/or inert compounds (higher than 60 wt%) by scraps from packaging waste glass in tiles, and cathode ray tube glasses and packaging waste glass up to 20 wt% in the brick compositions.     

Synthesis and characterization of high-density B2O3-added forsterite ceramics

Boria (B₂O₃)-added forsterite (Mg₂SiO₄) ceramics were synthesized and their properties were characterized. The addition of B₂O₃ was aimed to produce high density forsterite ceramics at a low sintering temperature. The raw materials were purified silica sand and commercial magnesia powders. Fosterite powder was produced from a solid reaction between the raw powders at 1100 °C prior to addition of B₂O₃, uniaxial pressing and sintering at 1200 °C. The amount of added B₂O₃ varied between 0%, 4%, and 8% by weight. Elemental analysis was performed by X-ray fluorescence (XRF) spectroscopy on the purified silica powder, whereas phase analyses were obtained from X-ray diffraction (XRD) data. Characterization of the ceramics included diameter shrinkage, density-porosity, thermal expansion, Vickers hardness, and dielectric constant. The results showed that the silica powder contained 98.7 at% Si with minor impurities, including 0.5 at% Ti, but the only identified crystalline phase was quartz. Further phase analysis of the ceramics showed that the addition of B₂O₃ reduced the amount of formed forsterite and increased the amount of cristobalite, proto- and clino-enstatite (MgSiO₃) as well as suanite (Mg₂B₂O₅). The highest forsterite content was found in B₂O₃-free ceramics, approximately 88.1 wt%. Moreover, the addition of B₂O₃ also reduced the diameter of the sample by more than 21%, resulting in a very dense ceramic with an apparent porosity of only 0.3%. The Vickers hardness significantly increased from 0.3 GPa for the B₂O₃-free ceramic to 10.9 GPa for the 4% B₂O₃ sample. The dielectric constant of the B₂O₃-added forsterite ceramics was improved by approximately 2–6 times that of the B₂O₃-free ceramic, which was primarily attributed to the loss of porosity in the samples.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.