The use of solid residues derived from different industrial activities to obtain calcium silicates for use as insulating construction materials

Calcium silicates have obtained through solid state reaction of the different residues generated in various industrial activities. As a source of calcium oxide: marble, mussel shells, and the reagent commercial calcium hydroxide were used. The source of silica was biomass ash and fired ceramic residue formed by crushing pieces of broken and defective ceramic products from a brick factory (chamotte). From the raw materials, biomass ash and marble, biomass ash and commercial calcium hydroxide, and chamotte and crushed mussel shell dust, mixed in a molar ratio CaO:SiO₂ 1:1 and sintered at 1100 °C (24 h), calcium silicates such as wollastonite, gehlenite and larnite were obtained. Both the raw materials and the synthesized material were characterized by XRD, XRF and TGA-DTA. In order to use the calcium silicates obtained as low temperature thermal insulating ceramic materials, the materials obtained were compressed under uniaxial loading at 81.7 MPa to obtain bricks measuring 60 mm × 30 mm × 10 mm. The properties of the bricks were studied. The ceramic materials present conductivity values between 0.10 W/m² K and 0.18 W/m² K and compressive strength of 29.8-59.3 MPa, respectively. The bricks met the UNE guidelines for use as low-temperature structural insulation ceramics.     

Characterization of basaltic tuffs and their applications for the production of ceramic and glass–ceramic materials

Alkaline basaltic tuffs, from Southern Turkey were characterized and employed to obtain ceramic and glass–ceramic materials by combined sintering and crystallization process. The chemical and mineralogical compositions were analyzed by X-ray fluorescence spectrometry and X-ray diffraction analyses, respectively. The phase formation and the sintering behaviour were investigated by DTA, differential dilatometer and hot-stage microscopy. The micro-structure and residual porosity of the sintered samples were observed by SEM and evaluated by pycnometric techniques. Ceramic material, based on 50% basaltic tuff and 50% clay, was obtained at 1150 °C with 13% total porosity and 4% water absorption. Glass–ceramic materials were synthesized directly using the milled basaltic tuff by mean of the sinter-crystallization technique, in the range 900–1150 °C. The investigation has showed that, due to the high porosity and low crystallinity, alkaline tuffs could be a suitable raw material for ceramic application.     

工业固废制备低碳胶凝材料的研究进展

以工业固废制备水泥熟料、全固废无熟料胶凝材料以及固废基碱激发胶凝材料是当前水泥行业节能减排与碳达峰的主要研究方向,是我国绿色循环发展的大势所趋。本文从固废制备水泥熟料、固废制备全固废胶凝材料以及固废基碱激发胶凝材料3个方面介绍目前的研究进展,具体分析了其制备工艺、原材料的选择以及种类的情况,以期为固废利用和水泥行业的节能减排提供参考。     

回收废旧电池制备功能材料研究进展

废旧电池中含有大量的金属物质,如果不妥善处理,会造成严重的环境污染和资源浪费。而将废旧电池回收之后用于制备功能材料,既能有效解决废旧电池难处置、危害大的问题,又可以减少功能材料的制备成本。文章首先概述了电池的组成及种类、废旧电池的回收意义与回收和处理现状;其次重点介绍了回收废旧电池制备功能材料的研究现状和最新进展,根据废旧电池制备功能材料所采用回收工艺的不同对废旧电池的回收利用进行了分类;最后探讨了目前回收废旧电池制备功能材料所存在的一些问题,并指出简单处理废旧电池制备功能材料将会是未来的主要发展趋势。     

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 ferrimagnetic glass‐ceramic frit from waste

The large amount of generated waste determines the importance of their valorization. Red mud is the residue of the Bayer process, which stored cumulative value raises 2.7 Bt. This paper describes an easy way to produce a ferrimagnetic glass‐ceramic frit, using bauxite residue, fly ash and glass cullet as raw materials. The synthesized frit consists of faceted and dendritic agglomerated crystals of magnetite and titanomagnetite embedded in a glass matrix, which exhibits a saturation magnetization (M_S) of 6.3 emu/g, a remanent magnetization (M_R) of 2.7 emu/g and a coercive field (H_C) of 347 Oe. Furthermore, it presents Vickers hardness value of H_V = 5.55 ± 0.16 GPa and fracture toughness value of K_IC = 1.64 ± 0.34 MPa·m^1/2.     

Electromagnetic absorption, reflection and interference shielding in X-band frequency range of low cost ceramic building bricks and sandwich type ceramic tiles using mill scale waste as an admixture

General concern for potential health effects of 24 h electromagnetic fields (EMF) exposure has increased over the recent years. This has led to the necessity of developing low cost electromagnetic interference (EMI) shielding and especially absorbing building materials. In the present study the utilization of steel mill scale waste in ceramic bricks for this purpose was investigated, while the development of an improved, regarding mainly absorption performance, building material also occurred. Both ceramic bricks and sandwich type ceramic tiles were found to have good shielding efficiency and absorption performances in the same X-band frequency range (8-12 GHz) while technological and environmental requirements as building materials were also established.     

Sintering mechanism of high-intensity and low-density ceramic proppants prepared by recycling of waste ceramic sands

Waste ceramic sands were effectively used to prepare the high-intensity and low-density ceramic proppants, realising the recycling of the waste ceramic sands. The technology involved the pelletising in an intensive mixer, in which the waste ceramic sands and other starting materials were added, and followed by heat-treatment under different sintering conditions. The sintering temperature, holding time and heating rate were optimised by investigating the crystalline phase, microstructure, density and breakage ratio of the obtained proppants. The results showed that the proppants sintered at 1260°C for 2?h with a heating rate of 5°C?min^–1 under air atmosphere exhibited high crush resistance and low density, with the breakage ratio of 8.5% under 52?MPa closure pressure and bulk density of 1.65?g?cm^–3. The proppants prepared by bauxite, waste ceramic sands and sintering aids are promising candidates as high-intensity and low-density fracturing proppants in future applications.     

Minimization of Pb content in a ceramic glaze by reformulation the composition with secondary raw materials

In this study a commercial ceramic glaze composed by both olivine (magnesium iron silicate, (Mg,Fe)₂SiO₄) and commercial frits, rich in lead (about 30 wt%), was reformulated by using secondary raw materials (CRT cone glass and municipal solid incinerator post-treatment bottom ashes before and after vitrification). The waste-based products were characterized and, compared to the standard glaze, showed better acid resistance, comparable aesthetic characteristics and slightly lower stainless resistance. Environmental benefits were obtained by saving natural raw material (olivine), by reducing lead percentage in the proposed formulations (from around 30 to 5 wt%), by energy saving (for the avoided use of commercial frits) and by reducing lead content in the new compositions.     

Fabrication and characterization of a mullite-foamed ceramic reinforced by in-situ SiC whiskers

In this study, a new mullite-foamed ceramic, reinforced with in-situ SiC whiskers (MCS) and applied as the insulating lining of thermal equipment used in cement production, was investigated. Compared with a conventional mullite-foamed ceramic (MC), the MCS phase composition, microstructure, compressive strength, thermal conductivity and alkali corrosion resistance were investigated by using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and Factsage® software. The results showed that after being fired in granular coke, the SiC whiskers formed into MCS struts and were distributed in the pores between the interconnected needle-like mullite. Although the formation of SiC with higher conduction slightly increased MCS thermal conductivity, it significantly enhanced the compressive strength and alkali corrosion resistance of the foamed ceramic. Compared with the MC, although the MCS had higher bulk density (3.9%), and higher thermal conductivity (9.5% at 800 °C), it was more important that greatly improved compressive strength (by 60%) and better alkali corrosion resistance was achieved.     

Egg shell waste as an activation agent for the manufacture of porous carbon

Egg shell waste was used as an activation agent directly for the manufacture of a biomass-derived porous carbon,which possessed a surface area of 626 m~2·g~(-1) and was rich in nitrogen, sulfur and oxygen functionalities. The activation mechanism was proposed, and the carbon showed its potential to act as an adsorbent for the adsorptive removal of various contaminants from both aqueous and non-aqueous solutions, possessing maximum adsorption capacities of 195.9, 185.1, 125.5 and 44.6 mg·g~(-1) for sulfamethoxazole, methyl orange, diclofenac sodium and dibenzothiophene, respectively. Through the utilization of egg shell waste as a sustainable activation agent, this work may help to make the widely applied biomass-derived porous carbons more economical and ecological.     

Firing behavior of argillites from northern Tunisia as raw materials for ceramic applications

This study reports the firing properties of clayey materials from northern Tunisia to evaluate their possible use as raw material in ceramic. Physical, chemical, and mineralogical characterization and thermal behavior were carried out by inductively coupled plasma atomic emission, X-ray diffraction, Fourier transform infrared spectroscopy, differential thermal analysis, particle size distribution, and Atterberg limits tests. Firing properties were evaluated by color, firing shrinkage, water absorption, bulk density, apparent porosity, and flexural strength. Studied clayey materials are made up mainly by kaolinite and illite and are rich in iron. The main transformations after thermal analysis were identified from 500°C to 1000°C subsequent to the dehydroxylation of clay minerals, calcite decomposition, and the recrystallization process. Fired samples up to 1100°C showed better physical and mechanical properties related with a great densification resulting in a significant increase in linear shrinkage, bulk density, and flexural strength and a decrease in apparent porosity and water absorption up to 1100°C. This behavior is due to a crystalline and liquid phases formed at low firing temperature associated with a high content of fluxing agents. The fired ceramic materials exhibited low water absorption up to 2.26% and high flexural strength up to 32.6 MPa, which makes their potential use for some earthenware and stoneware products.     

Thermo-mechanical simulation of ultrahigh temperature ceramic composites as alternative materials for gas turbine stator blades

The efficiency of the Bryton cycle strongly depends on the maximum temperature of the cycle. However, restrictions on metallurgical problems deprive engineers from the benefit of high temperatures. Ultrahigh temperature ceramics can be considered in such cases, instead of traditional materials like M152 superalloy. In this study, SiC reinforced HfB₂ and ZrB₂ ultrahigh temperature ceramics were proposed as gas turbine stator blades. The heat transfer and stress-strain equations were solved numerically by the finite element method to obtain temperature and stress distributions. The results showed that the maximum thermal stress occurs in vicinity of the cooling ducts where the temperature gradient is maximum. The maximum displacements of 1.2 mm (for HfB₂–SiC) and 1.14 mm (for ZrB₂–SiC) occur in the upper wall. It can be noticed that the ZrB₂–SiC made blade showed lower maximum stress and displacement than those for the HfB₂–SiC made one, as a result of lower expansion coefficient of ZrB₂–SiC system. The addition of SiC to monolithic HfB₂ and ZrB₂ ceramics decreases their thermal conductivity and following that, the temperature uniformity in blades reduces. Although the thermal stresses and the probability of failure in these stator blades enhance, the ZrB₂–SiC material presented the best performance among the other investigated samples. Both Coulomb-Mohr and Von Mises failure analyses were employed. It was understood that both blades made of HfB₂–SiC and ZrB₂–SiC composites simply withstand the applied stresses with the safety factors of about 1.5.     

Use of ceramic industry milling and glazing waste as an active addition in cement

The beneficial effects of pozzolans on cement manufacture have encouraged their use in that industry. Traditional natural pozzolan have become less available of late, however, due to a decline in quarrying intensity aimed at minimizing the impact on the landscape. At the same time, environmental policies pursue the reduction or elimination of spoil heaps by valorizing industrial waste and by‐products as raw materials, in keeping with the principles of the circular economy. The quest for new types of waste and by‐products with pozzolanic properties has consequently become a priority line of research. This study explored the valorization of one such by‐product, the ceramic sludge resulting from fired clay industry milling and glazing, as a component in new, more eco‐sustainable cements. The sludge was characterized physically, chemically, morphologically, and mineralogically to determine its suitability as a pozzolanic addition in cement. The findings showed that ceramic sludge consists in clustered particles ranging in size from 100 μm to 1 μm. SiO₂, Al₂O₃, and Fe₂O₃ together comprise over 70% of the total composition, while the reactive silica content is greater than the 25% required by the existing legislation. The predominant minerals are quartz, kaolinite, and muscovite, with some zircon. A study of pozzolanic reaction kinetics in the ceramic sludge/lime system revealed that over time this waste can fix lime, generating products such as calcium aluminate hydrates and C–S–H gels. The cements made with ceramic sludge proved to be standard‐compliant in terms of water demand, setting, drying shrinkage and mechanical strength.     

Polymer‐derived ceramic aerogels as sorbent materials for the removal of organic dyes from aqueous solutions

Polymer‐derived SiC and SiOC aerogels have been synthesized and characterized both from the microstructural point of view and as sorbent materials for removing organic dyes (Methylene Blue, MB, and Rhodamine B, RB) from water solutions. Their adsorbent behavior has been compared with a polymer‐derived SiC foam and a commercial mesoporous silica. The aerogels can efficiently remove MB and RB from water solution and their capacity is higher compared to the SiC foams due to the higher surface area. The SiOC aerogel remains monolithic after the water treatment (allowing for an easy removal without the need of a filtration step) and its maximum capacity for removing MB is 42.2 mg/g, which is higher compared to the studied mesoporous silica and many C‐based porous adsorbents reported in the literature. The reason for this high adsorption capacity has been related to the unique structure of the polymer‐derived SiOC, which consists of an amorphous silicon oxycarbide network and a free carbon phase.     

Effects of waste glass as a sand replacement on the strength and durability of fly ash/GGBS based alkali activated mortar

This study incorporates fine waste glass (GS) as a replacement for natural sand (NS) in fly ash (FA) and/or ground granulated blast furnace slag (GGBS) based alkali activated mortar (AAm). Tests were conducted on the AAm to determine the mechanical properties, water absorption, apparent porosity and the durability based on its resistance to Na₂SO₄ 5% and H₂SO₄ 2% concentrated solutions. Whereas the microstructure and chemical composition of AAm was analyzed by SEM-EDX to support results obtained from the experimental tests. The study revealed that the effects of GS depends on the ratio of binders used to synthesize the mortar. For high FA/GGBS mortar, an increase in strength and reduction of porosity was observed with increasing GS up to 50 wt%. For lower FA/GGBS mortar, increasing GS up to 100 wt%, increased strength and decreased porosity. The lower porosity attained with the incorporation of GS, improved the resistance of mortar to Na₂SO₄ solution thus increasing durability. The resistance of mortar to H₂SO₄ was also improved with lower porosity due to incorporation of GS. However, the durability of mortar was negatively impacted with the further reduction of porosity observed with increasing GS and GGBS above 50 wt% believed to be caused by the stress induced as a result of expansive reaction products created when the mortar reacted with acid.     

Coloring effect of iron oxide content on ceramic glazes and their comparison with the similar waste containing materials

The effects of adding iron oxide to ceramic glaze formulations were studied in this study. Iron oxide was added in different weight ratios into the reactive transparent glaze, reactive opaque glaze, and transparent glaze formulations. The iron oxide content in the glaze composition, the coloring mechanisms, the phase distributions, and surface properties at temperatures of 950–1000-1050-1200 °C in the oxidation firing medium were investigated. Scanning Electron Microscopy (SEM) to determine the microstructural and morphological characterizations of the test glazes, X-Ray Diffractometry (XRD) to determine the crystallographic properties and phases, and X-Ray Fluorescence (XRF) analyses to determine the elemental and chemical composition were performed. In addition to these, surface images were examined with Digital Microscope (DM) and Commission Internationale de l'Eclairage (CIE) L*a*b, and water absorption values were compared. In addition, taking into account environmental factors, a comparison of ceramic glazes with the same amount of waste iron oxide was also performed for same purpose. As a result of the studies, it was observed that the addition of iron oxide and/or waste iron oxide did not have a negative effect, and coloring effects on the glaze layer were observed at different rates and firing temperatures.     

A method for fast and contactless control of raw materials

A technique for quality control of ceramic materials is proposed based on the surface photo-charge effect. The method is demonstrated and studied in the case of controlling the chemical composition of bricks. Presented experimental results show that samples with different compositions invoke distinctly different electronic signals specific to sample's composition. In particular, it is revealed that the response signal is a function of the percentage of coal slurries added to the brick raw material for energy efficiency. The quality measurements using the proposed technique are express and contactless, and can be performed under the production conditions of brick firing. The obtained results indicate that the described technology could be extended to control the production quality of other raw materials.     

Evaluation of locally available amorphous waste materials as a source for alternative alkali activators

The production of alkali-activated materials with excellent mechanical performance requires the use of water glass, which has a significant carbon footprint. Such materials can have a lower carbon footprint if we replace water glass with alternative activators sourced from waste. In this study, we assessed the suitability of locally available amorphous waste materials (stone wool, glass wool, bottle glass and cathode-ray tube glass) as a source for the preparation of alternative alkali activators. We quantified the amount of silicon and aluminium dissolved in the activator solutions via inductively coupled plasma-optical emission spectrometry. The alternative activators were then used to produce alkali-activated fly ash and slag. The compressive strength values of alkali-activated fly ash specimens upon the addition of NaOH, water glass and the most promising alternative activator were 38.98 MPa, 31.34 MPa and 40.37 MPa, respectively. The compressive strength of slag specimens activated with alternative activators with the highest concentration of dissolved silicon (21 g/L) was, however, 70% higher than the compressive strength of slag specimens activated with only 10 M sodium hydroxide. The compressive strength of slag specimens with the addition of the most promising alternative activator was significantly lower (3.5 MPa) than the compressive strength of those that had been activated by commercial water glass (34.3 MPa).