Cements obtained from rice hull: encapsulation of heavy metals

Rice hull is an agricultural residue containing organic materials (carbohydrates, cellulose, etc.) and about 10% of silica, as inorganic component. Usually rice hull is burned at the fields generating small silica particles that may cause respiratory and environmental damage. On the other hand, beta-Ca2SiO4 is the second most important component of commercial portland cement. The utilization of beta-Ca2SiO4 brings many environmental benefits, such as reduction of carbon dioxide emissions and the saving of raw materials and energy. This work describes the synthesis of beta-Ca2SiO4 and related cements prepared from rice hull and the insertion of heavy metals (copper and cadmium). The insertion of these metals, chemically bounded to dicalcium silicate may represent a useful method to permanent encapsulation of hazardous chemicals. Silica was obtained from burning rice hull at 600 degrees C. The synthesis was carried out by a combination of sonochemical and solid-state chemical reactions and is completed at 800 degrees C. It was found that copper and cadmium can be inserted into beta-Ca2SiO4 structure in proportions up to 10%.     

常压干燥制备疏水性SiO_2-玻璃纤维复合气凝胶及表征

以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为复合硅源,玻璃纤维为增强体,采用溶胶-凝胶和常压干燥工艺制备出疏水性SiO2-玻璃纤维复合气凝胶。利用N2吸附脱附、扫描电镜、高分辨透射电镜、红外光谱、接触角、热重-差热分析及力学测试等手段表征复合气凝胶,并分析预处理玻璃纤维时的盐酸浓度及浸泡时间对复合气凝胶密度的影响。结果表明:当玻璃纤维的预处理条件为2.5mol/L盐酸浸泡0.5h时,制备得到的SiO2-玻璃纤维复合气凝胶表观密度最低,为0.12g/cm3,孔径主要分布在2~50nm,疏水角为142°,热稳定性温度高达500℃,抗压强度为0.05MPa,弹性模量为0.5MPa。     

High temperature capture of CO2 on lithium-based sorbents from rice husk ash

Highly efficient Li(4)SiO(4) (lithium orthosilicate)-based sorbents for CO(2) capture at high temperature, was developed using waste materials (rice husk ash). Two treated rice husk ash (RHA) samples (RHA1 and RHA2) were prepared and calcined at 800°C in the presence of Li(2)CO(3). Pure Li(4)SiO(4) and RHA-based sorbents were characterized by X-ray fluorescence, X-ray diffraction, scanning electron microscopy, nitrogen adsorption, and thermogravimetry. CO(2) sorption was tested through 15 carbonation/calcination cycles in a fixed bed reactor. The metals of RHA were doped with Li(4)SiO(4) resulting to inhibited growth of the particles and increased pore volume and surface area. Thermal analyses indicated a much better CO(2) absorption in Li(4)SiO(4)-based sorbent prepared from RHA1 (higher metal content sample) because the activation energies for the chemisorption process and diffusion process were smaller than that of pure Li(4)SiO(4). RHA1-based sorbent also maintained higher capacities during the multiple cycles.     

疏水型醇酸树脂/SiO2有机无机杂化材料的制备与性能

基于溶胶凝胶(sol-gel)工艺,采用两步法,以正硅酸乙酯(TEOS)、甲基三乙氧基硅烷(MTES)、己二酸、聚乙二醇400(PEG 400)为原料,制备了疏水型醇酸树脂/SiO2有机无机杂化材料。MTES的Si-CH3基团赋予材料的疏水性能,随着MTES含量的提高,接触角θ增大,当MTES(质量分数,下同)超过15%时,接触角θ增大不明显,并最终稳定在126°左右。红外图谱(FT-IR)和X射线光电子能谱(XPS)分析结果显示,硅溶胶与醇酸树脂间发生了的杂化反应,形成了Si-O-C键。DSC分析结果显示,随SiO2%的提高,杂化材料的耐热性能提高。     

The fluid transport properties of HCWA–DSF hybrid supplementary binder mortar

It has been demonstrated in several past studies that high calcium wood ash (HCWA) can be effectively used in combination with densified silica fume (DSF) as supplementary binder material to enhance the mechanical performance of concrete. The experimental investigation was conducted to study the effect of the inclusion of HCWA and DSF on the durability properties of high strength cement mortar produced. A total of twelve different mix designs of mortar were fabricated with the use of HCWA at various cement replacement levels of 0–20% in combination with 7.5% densified silica fume (DSF) and subjected to various durability tests. The durability assessments performed include tests on water absorption, air permeability, porosity and degree of carbonation. A significantly lower degree of water absorption, porosity and carbonation was observed for cement mortars with HCWA contents of 2–8% used in combination with 7.5% DSF by weight of binder as compared to an equivalent pure cement mortar.     

Chromium behavior during cement-production processes: a clinkerization, hydration, and leaching study

The behavior of chromium during the production of cement clinker, during the hydration of cement and during the leaching of cement mortars was investigated. The microstructures of clinker and mortar properties were investigated using free lime, XRD, SEM/EDS, and TG/DTA techniques. Chromium was found to be incorporated in the clinker phase. The formation of new chromium compounds such as Ca(6)Al(4)Cr(2)O(15), Ca(5)Cr(3)O(12), Ca(5)Cr(2)SiO(12), and CaCr(2)O(7), with chromium oxidation states of +3, +4.6, +5, and +6, respectively, was detected. After the hydration process, additional chromium compounds were identified in the mortar matrix, including Ca(5)(CrO(4))(3)OH, CaCrO(4)·2H(2)O, and Al(2)(OH)(4)CrO(4), with chromium oxidation states of +4.6, +6, and +6, respectively. Additionally, some species of chromium, such as Cr(3+) from Ca(6)Al(4)Cr(2)O(15) and Cr(6+) from CaCr(2)O(7), CaCrO(4)·2H(2)O, and Al(2)(OH)(4)CrO(4), were leached during leaching tests, whereas other species remained in the mortar. The concentrations of chromium that leached from the mortar following U.S. EPA Method 1311 and EA NEN 7375:2004 leaching tests were higher than limits set by the U.S. EPA and the Environment Agency of England and Wales related to hazardous waste disposal in landfills. Thus, waste containing chromium should not be allowed to mix with raw materials in the cement manufacturing process.     

Development of vegetable fibre–mortar composites of improved durability

The primary concern for vegetable fibre reinforced mortar composites (VFRMC) is the durability of the fibres in the alkaline environment of cement. The composites may undergo a reduction in strength and toughness as a result of weakening of the fibres by a combination of alkali attack and mineralisation through the migration of hydration products to lumens and spaces. This paper presents several approaches used to improve the durability performance of VFRMCs incorporating sisal and coconut fibres. These include carbonation of the matrix in a CO₂-rich environment; the immersion of fibres in slurried silica fume prior to incorporation in the ordinary Portland cement (OPC) matrix; partial replacement of OPC matrix by undensified silica fume or blast-furnace slag and a combination of fibre immersion in slurried silica fume and cement replacement. The durability of the modified VFRMC was studied by determining the effects of ageing in water, exposure to cycles of wetting and drying and open air weathering on the microstructures and flexural behaviour of the composites. Immersion of natural fibres in a silica fume slurry before their addition to cement-based composites was found to be an effective means of reducing embrittlement of the composite in the environments studied. Early cure of composites in a CO2-rich environment and the partial replacement of OPC by undensified silica fume were also efficient approaches in obtaining a composite of improved durability. The use of slag as a partial cement replacement had no effect on reducing the embrittlement of the composite.     

无机溶胶粒子的有机高分子胶囊化研究EI

采用一种水溶性聚合物—羟丙基甲基纤维素(HPMC)处理硅溶胶粒子(SiO_2);并以这样的粒子作核,制得了SiO_2/PMMA复合胶囊化粒子;通过电泳实验对其胶囊化效果进行了表征。     

Evaluation of normal-weight and light-weight fillers in extruded cellulose fiber cement products

Extruded fiber cement products offer advantages in terms of the versatility of section profiles, end product performance characteristics, and production throughput. Wood fibers offer a desirable balance of performance and cost as reinforcement in extruded wood fiber cement products. The research reported herein assessed the effects of normal-weight (silica sand) and light-weight (expanded shale) fillers on mechanical, physical and durability characteristics of extruded cement products reinforced with softwood, hardwood, and recycled fibers. Fillers caused improvements in moisture resistance and durability of extruded wood fiber cement products. Their presence, however, lowered the flexural strength and nailability of fiber cement boards.     

β-Belite cements (β-dicalcium silicate) obtained from calcined lime sludge and silica fume

The utilization of lime sludge (LS), a pulp and paper industry residue, and silica fume (SF), a ferrosilicon industry by-product, as raw materials for the preparation of β-dicalcium silicate (β-C₂S or β-belite) is investigated. β-phase belite is synthesized in a molar ratio of calcined LS/SF at 2.0 by hydrothermal method followed by calcination at 1000 °C for 2 h, which is lower temperature than conventional production temperature of about 1200 °C, and importantly without any chemical stabilizers. The produced belite cements containing 89.3% of β-belite, the rest being α-belite (5.93%), tobermorite (C–S–H, 1.71%), cristobolite (SiO₂, 1.83%) and free lime (CaO, 1.24%). The micro analytical characteristic of the raw materials and formed belite are examined by means of TG-DTA-DTG, XRF, XRD, SEM with EDAX, FT-IR, BET techniques and isothermal conduction calorimetry. The hydration of pastes and compressive strength of mortars of the formed β-belite blended with ordinary Portland cement are studied with a partial replacement of cement by 10%, 20% and 30%. The reaction of β-belite in combination with Portland cement is comparable up to 10% replacement of cement to the pozzolanic reactions of other materials used in similar ways. However, it is observed that the premature stiffening of belite incorporated cement pastes takes place with low heat of hydration because of higher reactivity of belite cement incorporation.     

Mechanical and durability properties of ternary concretes containing silica fume and low reactivity blast furnace slag

In this study, the effect of incorporation of silica fume in enhancing strength development rate and durability characteristics of binary concretes containing a low reactivity slag has been investigated. Binary concretes studied included mixes containing slag at cement replacement levels of 15%, 30% and 50% and mixes containing silica fume at cement replacement levels of 2.5%, 5%, 7.5% and 10%. Ternary concretes included combinations of silica fume and slag at various cement replacement levels. The w/b ratio and total cementitious materials content were kept constant for all mixes at 0.38 and 420 kg/m³ respectively. Concrete mixes were evaluated for compressive strength, electrical resistance, chloride permeability (ASTM C1202 RCPT test) and chloride migration (AASHTO TP64 RCMT test), at various ages up to 180 days.The results show that simultaneous use of silica fume has only a moderate effect in improving the slow rate of strength gain of binary mixes containing low reactivity slag. However it improves their durability considerably. Using appropriate combination of low reactivity slag and silica fume, it is possible to obtain ternary mixes with 28 day strength comparable to the control mix and improve durability particularly in the long term. Ternary mixes also have the added advantage of reduced water demand.     

Influence of curing conditions on durability of alkali-resistant glass fibres in cement matrix

Glass fibres in concrete material often increase the flexural strength. However, these fibres when in contact with cement are altered by alkali reactions due to the presence of portlandite. This study presents the results of investigation to show the effect of curing conditions on the durability of alkali-resistant glass fibres in cement matrix. Test results show that even alkali resistant fibres treated with zirconium oxide present the same degradation phenomenon. They also show that the nature of the cement has a large influence on the protection of the fibres: the Portland CEM II is less damaging than the CEM I. The substitutions of a part of cement by silica fume gave no substantial improvements to the mechanical strength of the glass fibre reinforced cement (GFRC). However, the observed microstructures in the samples show that the degradation is weakened with the addition of silica fumes. The analytical techniques used in this study are scanning electron microscope (SEM) and X-ray diffraction.     

Investigation of the stability of hardened slag paste for the stabilization/solidification of wastes containing heavy metal ions

We have studied the effect of chromium ions and lead ions on the chemical stability of hardened slag paste with toxic wastes during the stabilization/solidification process. The influences of Cr and Pb ions on the hydration of slag were also investigated. Sodium silicate (Na(2)SiO(3)), 5 wt.% of slag, was used as an alkali activator for slag hydration. The physical stability of hardened paste containing partial replacement of slag with fly ash and gypsum was also examined.When gypsum was added to slag, the compressive strength of hardened slag paste developed, accompanying the activation of alumino-ferrite-tricalciumsulfate (Al(2)O(3)-Fe(2)O(3)-3CaSO(4), AFt) and alumino-ferrite-monocalciumsulfate (Al(2)O(3)-Fe(2)O(3)-CaSO(4), AFm) phase generation. Those phases caused densification of the microstructure. Concurrently, the leaching amount of heavy metal ions was decreased. When fly ash was added to slag, the compressive strength increased and the leaching amount decreased with both active formation of aluminate hydrates and ion substitution. Lead ions were mostly stabilized through physical encapsulation by the hardened slag paste's hydrate matrix. In the case of chromium ions, we observed that it was mainly solidified through the formation of a substitutional solid solution with aluminum atoms in the structure of aluminate hydrates.     

Performance of silica fume-calcium hydroxide mixture as a repair material

The aim of this experimental work was to investigate the performance of a special concrete repair material. The use of silica fume (SF)-Ca(OH)₂ mixture, with and without cement addition in reinforced mortars has been studied. The examination of the hydration reaction progress by X-Ray Diffraction (XRD), Differential Thermal Analysis-Thermogravimetry (DTA-TG), and Scanning Electron Microscopy (SEM) analysis of SF-Ca(OH)₂ mixture with various cement ratios, shows that calcium silicate hydrate is formed in a desired extent. Damaged specimens repaired by the above-mentioned materials also showed low carbonation depth and the lowest corrosion rate, close to of undamaged specimens. This is attributed to the formation of C–S–H compounds at the interface between these mixtures and cement mortar, resulting in the creation of good binding properties of the repair materials.     

SiO2/C/M气凝胶纳米复合材料的结构及吸波性能

本文在SiO2/M(M=Fe,Co,i)复合气凝胶骨架上采用气相催化裂解乙炔的方法合成出SiO2/C/M气凝胶纳米复合材料,用扫描电镜、比表面分析仪、激光导热仪等对材料的结构和物理性能进行了表征,并初步测试了其电磁吸波性能.结果表明,在SiO2/C/M气凝胶纳米复合材料中,碳元素一般以纤维形式均匀分布于气凝胶骨架中,该材料具有低密度,低热导率().05～0.2W/mk),在2mm厚度,8-18GHz的范围内有一定的吸波性能,且吸波性能随频率升高而增加.     

Durability of alkali-activated fly ash cementitious materials

The study described in the present paper addresses the durability of alkali-activated fly ash (AAFA) cement under different conditions: specifically, cement performance is measured in a number of aggressive environments (deionized water, ASTM seawater, sodium sulphate and acidic solutions) and with respect to alkali–silica reaction-induced expansion. The chief parameters studied are: weight loss, compressive strength, variations in volume, presence of the products of degradation and microstructural changes. The results show that AAFA pastes perform satisfactorily in aggressive environments and that degradation in these materials is distinctly different from such processes in OPC paste. These mortars are also compliant with the 16-day expansion limit stipulated in ASTM standard C1260-94 on potential alkali–silica reactivity.     

Superhydrophobic films on glass surface derived from trimethylsilanized silica gel nanoparticles

The paper deals with the fabrication of sol-gel-derived superhydrophobic films on glass based on the macroscopic silica network with surface modification. The fabricated transparent films were composed of a hybrid -Si(CH(3))(3)-functionalized SiO(2) nanospheres exhibiting the desired micro/nanostructure, water repellency, and antireflection (AR) property. The wavelength selective AR property can be tuned by controlling the physical thickness of the films. Small-angle X-ray scattering (SAXS) studies revealed the existence of SiO(2) nanoparticles of average size ～9.4 nm in the sols. TEM studies showed presence of interconnected SiO(2) NPs of ～10 nm in size. The films were formed with uniformly packed SiO(2) aggregates as observed by FESEM of film surface. FTIR of the films confirmed presence of glasslike Si-O-Si bonding and methyl functionalization. The hydrophobicity of the surface was depended on the thickness of the deposited films. A critical film thickness (>115 nm) was necessary to obtain the air push effect for superhydrophobicity. Trimethylsilyl functionalization of SiO(2) and the surface roughness (rms ≈30 nm as observed by AFM) of the films were also contributed toward the high water contact angle (WCA). The coated glass surface showed WCA value of the droplet as high as 168 ± 3° with 6 μL of water. These superhydrophobic films were found to be stable up to about 230-240 °C as confirmed by TG/DTA studies, and WCA measurements of the films with respect to the heat-treatment temperatures. These high water repellant films can be deposited on relatively large glass surfaces to remove water droplets immediately without any mechanical assistance.     

Erbium-doped silica fibers for intrinsic fiber-optic temperature sensors

The variation in the green intensity ratio ((2)H(11/2) and (4)S(3/2) energy levels to the ground state) of Er ions in silica fibers has been studied as a function of temperature. The different processes that are used to determine the population of these levels are investigated, in particular 800-nm excited-state absorption in Er-doped fibers and 980-nm energy transfer, in Yb-Er-codoped fibers. The invariance of the intensity ratio at a fixed temperature with respect to power, wavelength, and doped fiber length has been investigated and shown to permit the realization of a high-dynamic-range (greater than 600 °C), autocalibrated fiber-optic temperature sensor.     

Evaluation of the role of Au in improving catalytic activity of Ni nanoparticles for the formation of one-dimensional carbon nanostructures

In situ dynamic imaging, using an environmental transmission electron microscope, was employed to evaluate the catalytic activity of Au/SiO(2), Ni/SiO(2), and Au-Ni/SiO(2) nanoparticles for the formation of one-dimensional (1-D) carbon nanostructures such as carbon nanofibers (CNFs) and nanotubes (CNTs). While pure-Au thin-film samples were inactive for carbon deposition at 520 °C in 0.4 Pa of C(2)H(2), multiwalled CNTs formed from Ni thin films samples under these conditions. The number of nanoparticles active for CNF and CNT formation increased for thin films containing 0.1 mol fraction and 0.2 mol fraction of Au but decreased as the overall Au content in thin films was increased above 0.5 mol fraction. Multiwalled CNTs formed with a root growth mechanism for pure Ni samples, while with the addition of 0.1 mol fraction or 0.2 mol fraction of Au, CNFs were formed via a tip growth mechanism at 520 °C. Single-walled CNTs formed at temperatures above 600 °C in samples doped with less than 0.2 mol fraction of Au. Ex situ analysis via high-resolution scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS) revealed that catalytically active particles exhibit a heterogeneous distribution of Au and Ni, where only a small fraction of the overall Au content was found in the portion of each particle actively involved in the nucleation of graphitic layers. Instead, the majority of the Au was found to be segregated to an inactive capping structure at one the end of the particles. Using density-functional theory calculations, we show that the activation energy for bulk diffusion of carbon in Ni reduces from ≈1.62 eV for pure Ni to 0.07 eV with the addition of small amounts (≈0.06 mol fraction) of Au. This suggests that the enhancement of C diffusion through the bulk of the particles may be responsible for improving the number of particles active for nucleating the 1-D carbon nanostructures and thereby the yield.     

Decoupling the physical and chemical effects of supplementary cementitious materials on strength and permeability: A multi-level approach

Supplementary cementitious materials (SCMs) represent an alternative for the industry to achieve sustainability by reducing cement contents without significant compromises of the mechanical properties and enhancing durability. SCMs play a dual role during hydration: a physical effect promoting nucleation and cement hydration and a chemical effect through pozzolanic activity. Rice husk ash (RHA) and natural pozzolans (NP) were evaluated using compressive strength and durability tests in a multi-level experimental program. RHA increased the strength more than NP, which is well explained by its prominent chemical effect (78%) assessed by isothermal calorimetry and its high amorphous silica content. Both RHA and NP produced significant reductions in the permeability of the concrete, which is mostly explained by the chemical effect. Decoupling the physical and chemical effects of a SCM allows for optimisation of its manufacturing process.