Utilization of modified copper slag activated by Na2SO4 and CaO for unclassified lead/zinc mine tailings based cemented paste backfill.

Serious heavy metals pollution was characterized in the lead/zinc mine tailings dam and surrounding soils, as well as copper slag disposal sites. This study investigates the efficacy of modified granulated copper slag (MGCS) as a partial replacement of ordinary Portland cement (OPC) for lead/zinc mine tailings-based cemented paste backfill (CPB) application using Na2SO4 (CSN) and CaO (CSC) as alkali-activated materials. The effect of different scenarios was ascertained by unconfined compressive strength (UCS). Also, the correlated microstructural evolution and mineralogical phase generation were obtained by scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and X-ray diffraction (XRD). The main findings proved that CSN was more effective in improving mechanical performance. Na2SO4 was found associated with C-S-H gel formation accompanied by a compact microstructure and better pore distribution with lower porosity. However, deposition of chloride compound was found in the surface layer of CSN samples, which could bring deterioration to the mechanical properties. Results above extend the knowledge of reusing MGCS as supplementary material to CPB, promoting the concept of a circular economy demand for both lead/zinc mine extraction and copper industries.

Direct three-dimensional observation of the microstructure and chemistry of C3S hydration.

Disagreements about the mechanisms of cement hydration remain despite the fact that portland cement has been studied extensively for over 100 years. One reason for this is that direct observation of the change in microstructure and chemistry are challenging for many experimental techniques. This paper presents results from synchrotron nano X-ray tomography and fluorescence imaging. The data show unprecedented direct observations of small collections of C3S particles before and after different periods of hydration in 15 mmol/L lime solution. X-ray absorption contrast is used to make three dimensional maps of the changes of these materials with time. The chemical compositions of hydration products are then identified with X-ray fluorescence mapping and scanning electron microscopy. These experiments are used to provide insight into the rate and morphology of the microstructure formation.

Preparation and property studies of ferric sulfoaluminate cement based on Bayer red mud and phosphogypsum.

The Bayer red mud (RM) and phosphogypsum (PG) accumulation have caused significant environmental contamination. However, practical and effective resource utilization technologies are still lacking currently. This work aims to develop ferric sulfoaluminate cement (FSAC) employing low-cost materials including Bayer red mud, phosphogypsum, and other materials. This method effectively improves the utilization rate of Bayer red mud and phosphogypsum. Under the premise of ensuring the performance of FSAC, the utilization rate of solid waste can reach up to 48.56%. The effects of different red mud dosages on cement mineral formation, workability, and mechanical properties are investigated. Then, untreated phosphogypsum is adopted as a retarder for FSAC, and the hydration process, working properties, mechanical properties, types of hydration products, and morphology of FSAC are explored. The results suggest that the crystal transformation of Ye'elemite C 4 A 3 S ¯  is promoted with the increase of Bayer red mud content. Cubic crystal system Ye'elemite C 4 A 3 S ¯ - c  with higher hydration activity is generated, which increases the early strength of cement but greatly reduces the setting time, hindering the later strength growth. Untreated phosphogypsum can effectively delay the early hydration process of FSAC, prolong the setting time of cement, and increase the strength of FSAC in the later stage. When the dosage of Bayer red mud and phosphogypsum is 17.64% and 9.21%, respectively, with phosphogypsum dosage of 20%, the prepared FSAC has satisfactory mechanical properties, and the 3-day and 90-day compressive strengths are 34.6 MPa and 57.1 MPa, respectively. In addition, the study of heavy metal leaching indicates that the FSAC prepared by Bayer red mud, phosphogypsum, and other raw materials will generate no environment pollution, and the solidification of heavy metal elements in the cement slurry is superior.

Evaluation of Polycaprolactone Applicability for Manufacturing High-Performance Cellulose Nanocrystal Cement Composites.

This experimental study examined the aplication effect of polycaprolactone (PCL), an organic resin material with excellent elasticity and ductility, on improving the mechanical performance of cellulose nanocrystal (CNC) cement composites. PCL was compared according to its shape, and in the case of Granules, which is the basic shape, interfacial adhesion with cement was not achieved, so a dichloromethane (DCM) solution was used to dissolve and use the Granules form. As a method for bonding PCL to the CNC surface, the CNC surface was modified using 3-aminopropyltriethoxysilane (APTES), and surface silylation was confirmed through Fourier transform infrared spectroscopy (FT-IR) analysis. In order to evaluate the dispersibility according to the application of PCL to the modified CNC, particle size analysis (PSA) and zeta potential analysis were performed according to the PCL mixing ratio. Through the PSA and zeta potential values, the highest dispersion stability was shown at 1 vol.%, the cohesive force of CNC was low, and the dispersion stability was high according to the application of PCL. According to the results of the dispersion stability evaluation, the degree of hydration of the dissolved PCL 1 vol.%, CNC-only specimens, and plain specimens were analyzed. CNC acted as a water channel inside the cement to accelerate hydration in the non-hydrated area, resulting in an increased degree of hydration. However, the incorporation of PCL showed a low degree of hydration, and the analysis of strength characteristics also showed a decrease of approximately 27% compared with that of plain specimens. This was because the bonding with SiO2 was not smooth owing to the solvent, thus affecting internal hydration. In order to investigate the effect of the PCL shape, the compressive and flexural strength characteristics were compared using PCL powder as an additional parameter. The compressive strength and flexural strength were improved by about 54% and 26%, respectively, in the PCL powder 15 wt% specimen compared to the general specimen. Scanning electron microscopy (SEM) analysis confirmed that the filler effect, which made the microporous structure denser, affects the mechanical performance improvement.

Experimental Study on the Strength and Hydration Products of Cement Mortar with Hybrid Recycled Powders Based Industrial-Construction Residue Cement Stabilization of Crushed Aggregate.

The strength-formation mechanism for industrial-construction residue cement stabilization of crushed aggregate (IRCSCA) is not clear. To expand the application range for recycled micro-powders in road engineering, the dosages of eco-friendly hybrid recycled powders (HRPs) with different proportions of RBP and RCP affecting the strengths of cement-fly ash mortar at different ages, and the strength-formation mechanism, were studied with X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that the early strength of the mortar was 2.62 times higher than that of the reference specimen when a 3/2 mass ratio of brick powder and concrete powder was mixed to form the HRP and replace some of the cement. With increasing HRP content substituted for fly ash, the strength of the cement mortar first increased and then decreased. When the HRP content was 35%, the compressive strength of the mortar was 1.56 times higher than that of the reference specimen, and the flexural strength was 1.51 times higher; XRD and SEM studies of the hydrated cement mixed with HRP showed that the amount of CH in the cement paste was reduced by the pozzolanic reaction of HRP at later hydration ages, and it was very useful in improving the compactness of the mortar. The XRD spectrum of the cement paste made with HRP indicated that the CH crystal plane orientation index R, with a diffraction angle peak of approximately 34.0, was consistent with the cement slurry strength evolution law, and this research provides a reference for the application of HRP to produce IRCSCA.

Hydration and Mechanical Properties of Blended Cement with Copper Slag Pretreated by Thermochemical Modification.

The application of granulated copper slag (GCS) to partially replace cement is limited due to its low pozzolanic activity. In this paper, reconstituted granulated copper slag (RGCS) was obtained by adding alumina oxide (Al2O3) to liquid copper slag. Blended cement pastes were formulated by a partial substitute for ordinary Portland cement (OPC) with the RGCS (30 wt%). The pozzolanic activity, mechanical development, and the microstructure were characterized. The results show that 5-10 wt% Al2O3 contributes to the increase in magnetite precipitation in RGCS. The addition of Al2O3 alleviates the inhibition of C3S by RGCS and accelerates the dissociation of RGCS active molecules, thus increasing the exothermic rate and cumulative heat release of the blended cement pastes, which are the highest in the CSA10 paste with the highest Al2O3 content (10 wt%) in RGCS. The unconfined compressive strength (UCS) values of blended cement mortar with 10 wt% Al2O3 added to RGCS reach 27.3, 47.4, and 51.3 MPa after curing for 7, 28 and 90 d, respectively, which are the highest than other blended cement mortars, and even exceed that of OPC mortar at 90 d of curing. The pozzolanic activity of RGCS is enhanced with the increase in Al2O3 addition, as evidenced by more portlandite being consumed in the CSA10 paste, forming more C-S-H (II) gel with a higher Ca/Si ratio, and a more compact microstructure with fewer pores than other pastes. This work provided a novel, feasible, and clean way to enhance the pozzolanic activity of GCS when it was used as a supplementary cementitious material.

Influence of Phosphorus Sources on the Compressive Strength and Microstructure of Ferronickel Slag-Based Magnesium Phosphate Cement.

Electric furnace ferronickel slag (EFS) is a typical magnesium-rich industrial by-product discharged from the manufacture of nickel and iron-nickel alloys. The approach to use it as the raw material for the preparation of magnesium phosphate cement (MPC) has potential and proves effective. In this study, three different phosphorus sources (PS) including phosphoric acid (H3PO4, PA), sodium dihydrogen phosphate (NaH2PO4, SDP) and potassium dihydrogen phosphate (KH2PO4, PDP) were used to react with EFS to prepare the EFS-based MPC (EMPC), and the effects of raw material mass ratio (EFS/PA, EFS/SDP, EFS/PDP) on the compressive strength, early hydration temperature and microstructure of EMPC pastes were investigated. Results showed that the compressive strength of EMPC paste is significantly impacted by the type of phosphorus source and the raw materials mass ratio. When the EFS/PDP ratio is 4.0, the compressive strength of the MPC paste reaches up to 18.8, 22.8 and 27.5 MPa at 3, 7 and 28 d, respectively. Cattiite (Mg3(PO4)2·22H2O), K-struvite (KMgPO4·6H2O) and/or Na-struvite (NaMgPO4·6H2O) were identified as the main hydration products of EMPC. The development of EMPC mainly involves the dissolution of a phosphorus source, MgO and Mg2SiO4, formation of hydration product as binder, and combination of the unreacted raw materials together by binders to build a compact form.

Microstructure and Key Properties of Phosphogypsum-Red Mud-Slag Composite Cementitious Materials.

Due to the low content of silicon and aluminum in red mud and the low reaction activity of red mud, when it was used to prepare composite cementitious materials, it was necessary to assist other aluminosilicates and improve their activity by certain methods. In this study, it was proposed to add slag to increase the percentage of silicon and aluminum in the system, and to improve the reactivity of the system through the activation effect of sulfate in phosphogypsum. The effects of slag and phosphogypsum contents on the mechanical properties and microstructures of composite cementitious materials were studied. X-ray diffraction analysis (XRD), thermogravimetric analysis (TG-DTG), and scanning electron microscopy (SEM) were used to analyze the effects of slag and phosphogypsum contents on the hydration products, microstructure, and strength formation mechanism of composite cementitious materials. The results show that with the increase of slag, the strength of the composite cementitious material increases gradually. When the slag content is 50%, the 28-day compressive strength reaches a maximum of about 14 MPa. Compared with the composite material without phosphogypsum, the composite cementitious material with 10-20% phosphogypsum showed higher strength properties, in which the 28-day compressive strength exceeds 24 MPa. The main reason for this is that the sulfate in phosphogypsum can cause the composite cementitious material to generate a large amount of ettringite and accelerate the dissolution of red mud and slag, increasing the release of aluminates, silicates, and Ca2+ to form more C-(A)-S-H and ettringite. In addition, a large amount of C-(A)-S-H makes ettringite and unreacted particles combine into a uniform and compact structure, thus improving the strength. When the content of phosphogypsum exceeds 40%, the 28-day compressive strength of the composite cementitious material drops below 12 MPa due to the presence of fewer hydration products and the expansion of ettringite.

Study on the Hydration Reaction of Typical Clay Minerals under Alkali and Sulfate Compound Activation.

Sand, stone, tailings and other aggregates often contain a small amount of clay mineral and their hydration activity is low, thereby lowering concrete performance indexes while negatively affecting their resource utilisation. In this study, clay minerals, calcium hydroxide and desulfurised gypsum were used to prepare cementitious materials to examine kaolinite, montmorillonite, illite and chlorite clay mineral contents under compound activation. The effects of curing temperature and water reducer on clay samples were analysed. The results showed that the compressive strength of kaolinite samples cured at 25 °C and 55 °C reached 1.09 and 4.93 MPa in 28 days and increased by 43% and 12%, respectively, after adding a 0.3% water reducer. Montmorillonite was activated and its compressive strength reached 5.33 MPa after curing at 55 °C in 28 days. Illite exhibited some activity and its compressive strength reached 1.43 MPa after curing at 55 °C in 28 days and the strength increased slightly after adding a water reducer. The chlorite sample had no strength after activation under the same conditions. Furthermore, X-ray diffraction and scanning electron microscope and energy-dispersive spectroscopy microstructure analyses showed that after alkali and sulfate activation, the hydration products of activated clay minerals mainly included ettringite, hydrated calcium aluminate and hydrated calcium silicate. The increase in curing temperature accelerated the reaction speed and improved the early strength. However, the effect on chlorite minerals was not obvious.

Study on the Strength and Hydration Behavior of Sulfate-Resistant Cement in High Geothermal Environment.

The hydration process and compressive strength and flexural strength development of sulphate-resistant Portland cement (SRPC) curing at 20 °C, 40 °C, 50 °C, and 60 °C were studied. In addition, MIP, XRD, SEM, and a thermodynamic simulation (using Gibbs Energy Minimization Software (GEMS)) were used to study the pore structure, the types, contents, and transformations of hydration products, and the changes in the internal micro-morphology. The results indicate that, compared with normal-temperature curing (20 °C), the early compressive strength (1, 3, and 7 d) of SRPC cured at 40~60 °C increased by 10.1~57.4%, and the flexural strength increased by 1.8~21.3%. However, high-temperature curing was unfavorable for the development of compressive strength and flexural strength in the later period (28~90 d), as they were reduced by 1.5~14.6% and 1.1~25.5%, respectively. With the increase in the curing temperature and curing age, the internal pores of the SRPC changed from small pores to large pores, and the number of harmful pores (>50 nm) increased significantly. In addition, the pore structure was further coarsened after curing at 60 °C for 90 d, and the number of multiple harmful pores (>200 nm) increased by 17.9%. High-temperature curing had no effect on the types of hydration products of the SRPC but accelerated the formation rate of hydration products. The production of the hydration products C-S-H increased by 13.5%, 18.6%, and 22.8% after curing at 40, 50, and 60 °C for 3 d, respectively. The stability of ettringite (AFt) reduced under high-temperature curing, and its diffraction peak was not observed in the XRD patterns. When the curing temperature was higher than 50 °C, AFt began to transform into monosulfate, which consumed more tricalcium aluminate hydrate and inhibited the formation of "delayed ettringite". Under high-temperature curing, the compactness of the internal microstructure of the SRPC decreased, and the distribution of hydration products was not uniform, which affected the growth in its strength during the later period.