Effect of partial replacement of geopolymer binder materials on the fresh and mechanical properties: A review

The growth of demand for concrete raises concerns about the consumption of natural resources and ordinary Portland cement. Geopolymer composites show promise as a sustainable alternative for conventional cement concrete. Considering the wide range of potential geopolymer composites applications (including suitability for transportation infrastructure, underwater applications, repair and rehabilitation of structures as well as recent developments in 3D printing), the desired fresh and mechanical properties of the geopolymer composite may vary between applications: for example, rapid setting can be a merit for certain applications and a demerit for others. Therefore, the desired fresh and mechanical properties (e.g., workability, setting time, compressive strength, etc.) can be controlled for a given geopolymer source material through its partial substitution by natural or by-product materials. Recognizing the critical role of various replacement materials in enhancing the potential applications of geopolymer composites, the present review was undertaken to quantify and understand the effect of partial replacement by fly ash, metakaolin, kaolin, red mud, slag, ordinary Portland cement, and silica fume on the setting time, workability, compressive strength and flexural strength of various source materials addressed in the literature. The review also provides insights into research gaps in the field to promote future research.     

对“垃圾衍生燃料”RDF之探析

当前,我国水泥工业在可燃废弃物应用技术方面都还处于一家一户、自制自用、效率极低的初级阶段。发达国家的替代燃料:“垃圾衍生燃料”RDF、“固体回收燃料”SRF、“次煤”Subcoal和“纸塑垃圾衍生燃料”RPF制成的原材料都是可燃废弃物,只是处理工艺技术不同或者由垃圾中分拣出的可燃废弃物不同,制成颗粒状衍生燃料的品质不同,这些都可以替代部分甚或替代全部化石燃料在水泥窑炉中应用。我国大力发展“替代燃料”产业,有助于水泥工业消纳更多的“可燃废弃物”,为改善环境尤其是城镇环境和面貌,为我国的节能减排和绿色高质量发展发挥更大的作用。     

Hydraulic reactivity and cement formation of baghdadite

In this study, the hydraulic reactivity and cement formation of baghdadite (Ca₃ZrSi₂O₉) was investigated. The material was synthesized by sintering a mixture of CaCO₃, SiO₂, and ZrO₂ and then mechanically activated using a planetary mill. This leads to a decrease in particle and crystallite size and a partial amorphization of baghdadite as shown by X-ray powder diffraction (XRD) and laser diffraction measurements. Baghdadite cements were formed by the addition of water at a powder to liquid ratio of 2.0 g/ml. Maximum compressive strengths were found to be ~2 MPa after 3-day setting for a 24-h ground material. Inductively coupled plasma mass spectrometry (ICP-MS) measurements showed an incongruent dissolution profile of set cements with a preferred dissolution of calcium and only marginal release of zirconium ions. Cement formation occurs under alkaline conditions, whereas the unground raw powder leads to a pH of 11.9 during setting, while prolonged grinding increased pH values to approximately 12.3.     

Enhancement in the osteogenesis and angiogenesis of calcium phosphate cement by incorporating magnesium-containing silicates

Based on the good osteogenic and angiogenic effects of silicon and magnesium elements, three types of micro-nano magnesium-containing silicates (MS), including akermanite (Ake, Ca₂MgSi₂O₇), diopside (Dio, CaMgSi₂O₆) and forsterite (For, Mg₂SiO₄), were incorporated into calcium phosphate cement (CPC) to improve its osteogenic and angiogenic performances for clinical application. In this present work, the physicochemical properties, osteogenesis and angiogenesis of MS/CPCs (Ake/CPCs, Dio/CPCs and For/CPCs) were investigated systematically and comparatively. The results showed that all MS/CPCs had good biomineralization and significantly stimulated the osteogenic differentiation of mBMSCs and angiogenic differentiation of HUVECs, respectively. Besides, the stimulating effects were related to not only the category of MS, but also the content of MS. The For/CPCs had a good angiogenic property but their initial setting times were beyond 60 min. The Dio/CPCs showed the lowest biological performance among the three groups of MS/CPCs due to the lower ion release (Si and Mg). The Ake was the ideal modifier that could provide CPC with appropriate physicochemical properties, better osteogenesis and angiogenesis. Simultaneously, a higher addition (10 wt%) of akermanite resulted in the best potential to bone regeneration. Taken together, this research provides an effective approach to improve the overall performance of CPC, and 10Ake/CPC is of great promising prospect in bone repair.     

Effect of nanosilica addition on bioactivity and in vivo properties of calcium aluminate cement

This study aims at assessing the influence of nanosilica on the bioactivity and mechanical properties of calcium aluminate cement. For this purpose, nanosilica was applied as a replacement for calcium aluminate cement at 0, 2, 5 and 8 wt%. The main components were analyzed by scanning electron microscope coupled with surface imaging and elemental analysis, fourier transform infrared spectroscopy and X-ray diffraction analysis. To estimate the bioactivity of specimens, hydroxyapatite formation on the surface of cement paste was investigated in the simulated body fluid solution. In addition, in vivo evaluation of calcium aluminate cement was performed in subcutaneous tissue of rats. To investigate the mechanical properties, both compressive and flexural strengths were also measured. The results revealed that by increasing nanosilica up to 8 wt%, the strength enhanced. Moreover all cement paste samples with various amounts of nanosilica represented good bioactivity because of formation of bonelike apatite layer on the surface of specimens within 28 days after soaking in simulated body fluid. In vivo experiments indicated that the cement sample was absorbed by the tissue and there was no infection at the implant site. Based on the in vitro and in vivo results, the specimen with 2 wt% nanosilica represented the highest bioactivity.     

Preparation and characterization of calcium phosphate cement with enhanced tissue adhesion for bone defect repair

Anti-washout and tissue adhesion properties are essential for the clinical application of injectable bone materials. In this study, we prepared calcium phosphate cement (CPC) with anti-washout and tissue adhesion properties and attempted to build covalent bonds between CPC and the amino groups in bone tissue under a self-regulating pH system in the CPC (acidic to basic). The results of push-out tests demonstrated that a significant enhancement (from 6.42 ± 0.76 N to 61.5 ± 4.09 N) in tissue adhesion was obtained with the addition of 6% (w/w) oxidized sodium alginate (OSA) in CPC. The FTIR, XRD, anti-washout test, XPS, pH test, and SEM results suggested that the synergistic effect of OSA-citric acid (CA) led to the formation of a three-dimensional gel network structure in the CPC, and the Schiff base reaction between aldehyde and amino groups induced adhesion between CPC and the bone tissue. Further, the addition of less OSA had no significant negative effect on the hydration properties of CPC. Our work aims to promote the development of injectable bone material in clinical applications.     

Probing the degenerate pattern growth of {100}<011> orientation in a directionally solidified Al-4.5 wt% Cu alloy

Degenerate pattern is a seemingly disordered morphology but it exhibits the inherently ordered crystal connected with tip-splitting and limited stability which makes it difficult to observe in the metallic system. Here we employ (100)[011] orientated planar-front seeds using directional solidification and reveal the fundamental origins of the degenerate pattern growth in an Al-4.5 wt% Cu alloy. We find that the spacing of the tip-splitting (λ) in the degenerate of the alloys followed a power law, λ∝V^−0.5, and the frequency (f) of the splitting was related to the growth velocity (V) by ƒ∝V^1.5. The dimensionless growth direction (θ/θ₀) increased monotonously and approached 0.6 with faster velocity, attributed to its anisotropy in the interface kinetics. Once growth velocity exceeded a threshold, two types of pattern transitions from degenerate to regular dendrites were proposed. One of them exhibited a random and chaotic mode and the other underwent a rotation in growth direction.     

Structure and phase-composition of Ti-doped gas atomized Raney-type Ni catalyst precursor alloys

Raney-type Ni precursor alloys containing 75 at.% Al and doped with 0, 0.75, 1.5 and 3.0 at.% Ti have been produced by a gas atomization process. The resulting powders have been classified by size fraction with subsequent investigation by powder XRD, SEM and EDX analysis. The undoped powders contain, as expected, the phases Ni₂Al₃, NiAl₃ and an Al-eutectic. The Ti-doped powders contain an additional phase with the TiAl₃ DO₂₂ crystal structure. However, quantitative analysis of the XRD results indicate a far greater fraction of the TiAl₃ phase is present than could be accounted for by a simple mass balance on Ti. This appears to be a (Ti_xNi_1−x)Al₃ phase in which higher cooling rates favour small x (low Ti-site occupancy by Ti atoms). SEM and EDX analysis reveal that virtually all the available Ti is contained within the TiAl₃ phase, with negligible Ti dissolved in either the Ni₂Al₃ or NiAl₃ phases.     

Effect of an abrupt change in pulling rate on microstructures of directionally solidified Al2O3-Er3Al5O12 eutectic and off-eutectic composite ceramics

Directionally solidified microstructures of Al₂O₃-Er₃Al₅O₁₂ eutectic and off-eutectic in situ composite ceramics were explored under abrupt-change pulling rate conditions. Corresponding temperature distributions and interface locations were studied. In eutectic composition, fluctuation of eutectic spacing occurred when the pulling rate increased abruptly. A gradually increase or abrupt increase in eutectic spacing was observed when the pulling rate decreased abruptly. In hypoeutectic and hypereutectic compositions, formation of the primary phases were suppressed when the pulling rate increased abruptly from 10?µm/s to 100?µm/s, while primary phases precipitated when the pulling rate decreased abruptly from 100?µm/s to 10?µm/s. The interface altitude decreased after the pulling rate increased abruptly, but increased after the pulling rate decreased abruptly. The liquid composition restriction (around the eutectic composition) at the eutectic interface plays an important role in the suppression of the primary dendrite and coupled eutectic oxides can be obtained in off-eutectic compositions even under higher solidification rate conditions.     

Solidification morphology and phase selection in drop-tube processed Ni–Fe–Si intermetallics

Drop-tube processing was used to rapidly solidify droplets of Ni_64.7Fe₁₀Si_25.3 and Ni_59.7Fe₁₅Si_25.3 alloys. In the larger droplets, and therefore at low cooling rates, only two phases, γ-Ni₃₁Si₁₂ and β₁-Ni₃Si were observed. Conversely, in the smaller droplets, and therefore at higher cooling rates, the metastable phase Ni₂₅Si₉ was also observed. The critical cooling rate for the formation of Ni₂₅Si₉ was estimated as 5 × 10³ K s⁻¹. SEM and TEM analysis reveals three typical microstructures: (I) a regular structure, comprising single-phase γ-Ni₃₁Si₁₂ and a eutectic structure between γ-Ni₃₁Si₁₂ and β₁-Ni₃Si; (II) a refined lamellar structure with a lamellar spacing <50 nm comprising γ-Ni₃₁Si₁₂ and β₁-Ni₃Si; (III) an anomalous structure with a matrix of Ni₂₅Si₉ and only a very small proportion of a second, and as yet unidentified, phase. These results indicate that there is an extended stability field for Ni₂₅Si₉ in the Ni-rich part of the Ni–Fe–Si ternary system in comparison to the Ni–Si binary system. With an increase of cooling rate, an increasing fraction of small droplets experience high undercoolings and, therefore, can be undercooled into the Ni₂₅Si₉ stability field forming droplets consisting of only the anomalous structure (III). The Fe atoms are found to occupy different substitutional sites in different phase, i.e. Fe substitutes for Ni in the γ phase and Si in the L1₂ (β₁) phase respectively.