Potential Role of GGBS and ACBFS Blast Furnace Slag at 90 Days for Application in Rigid Concrete Pavements.

Incorporating blast furnace slag into the composition of paving concrete can be one of the cost-effective ways to completely eliminate by-products from the pig iron production process (approximately 70% granulated slag and 30% air-cooled slag). The possibility to reintroduce blast furnace slag back into the life cycle will provide significant support to current environmental concerns and the clearance of tailings landfills. Especially in recent years, granulated and ground blast furnace slag (GGBS) as a substitute for cement and air-cooled blast furnace slag (ACBFS) aggregates as a substitute for natural aggregates in the composition of concretes have been studied by many researchers. But concrete compositions with large amounts of incorporated blast furnace slag affect the mechanical and durability properties through the interaction between the slag, cement and water depending on the curing times. This study focuses on identifying the optimal proportions of GGBS as a supplementary cementitious material (SCM) and ACBFS aggregates as a substitute to natural sand such that the performance at 90 days of curing the concrete is similar to that of the control concrete. In addition, to minimize the costs associated with grinding GGBS, the hydration activity index (HAI) of the GGBS, the surface morphology, and the mineral components were analyzed via X-ray diffraction, scanning electron microscopy (SEM), energy dispersive spectrometry (EDX), and nuclear magnetic resonance relaxometry (NMR). The flexural strength, the basic mechanical property of road concretes, increased from 28 to 90 days by 20.72% and 20.26% for the slag concrete but by 18.58% for the reference concrete. The composite with 15% GGBS and 25% ACBFS achieved results similar to the reference concrete at 90 days; therefore, they are considered optimal percentages to replace cement and natural sand in ecological pavement concretes. The HAI of the slag powder with a specific surface area equivalent to that of Portland cement fell into strength class 80 at the age of 28 days, but at the age of 90 days, the strength class was 100. The results of this research present three important benefits: the first is the protection of the environment through the recycling of two steel industry wastes that complies with European circular economy regulations, and the second is linked to the consequent savings in the disposal costs associated with wastefully occupied warehouses and the savings in slag grinding.

Analysis of Pore Structure in Cement Pastes with Micronized Natural Zeolite.

The continuous development of urban areas around the world led to an increase in construction material use and demand, with concrete seeing significant market uptake. Although significant progress has been made to reduce the environmental impact of concrete, there is still a stringent need for improvement. One of the most widely used methods to reduce the environmental impact of the cement industry and the construction industry alike is the replacement of ordinary Portland cement (OPC) by supplementary cementitious materials (SCM). Aside from by-products of industry, SCMs could also come from natural sources. Taking into account the porous structure of zeolites and their contribution to the improvement of the mechanical and durability properties of cement-based materials, the analysis of pore structure in cement pastes incorporating micronized natural zeolite is deemed necessary. In this research, the OPC was replaced by zeolite in three different percentages: 10%, 20%, and 30% by mass. The evolution of pore structure was investigated by means of nuclear magnetic resonance relaxometry at the curing ages of 1, 7, and 28 days. The microstructure of cement pastes was assessed by scanning electron microscopy investigations at 1, 7, 14, 21, and 28 days. The obtained results show that smaller pore sizes are present in cement pastes containing zeolites during the first 7 days. However, at the age of 28 days, the reference mix exhibits a similar pore structure to the mix containing 10% micronized zeolite due to the presence of larger amounts of hydration products. Increasing the replacement percentage to 30% results in larger pores, as indicated by larger values of the relaxation time.

Structural Characterization of Several Cement-Based Materials Containing Chemical Additives with Potential Application in Additive Manufacturing.

The rapid increase in additive manufacturing applications in all industries has highlighted the lack of innovative technologies and processes in the construction industry. Several European and international policies are in place to guide the development of the technological processes involved in the construction industry toward a sustainable future. Considering the global concerns regarding this industry, the purpose of this study was to develop new cement-based materials that are capable of accelerated hydration and early strength development for use in additive manufacturing. Ca(NO3)2·4H2O, Al2(SO4)3·18H2O and Na2S2O3·5H2O were used to obtain the accelerating effect in the hydration of Portland cement. Based on results obtained from X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDX) techniques, as well as low-field nuclear magnetic resonance relaxometry (LF-NMR) techniques, it was demonstrated that all accelerators used have a quickening effect on cement hydration. The addition of Na2S2O3·5H2O or combined Na2S2O3·5H2O and Ca(NO3)2·4H2O led to obtaining new cement-based materials with early strength development and fast hydration of microorganized internal structures, critical characteristics for 3D printing.

Monitoring the Effect of Calcium Nitrate on the Induction Period of Cement Hydration via Low-Field NMR Relaxometry.

The hydration process of Portland cement is still not completely understood. For instance, it is not clear what produces the induction period, which follows the initial period of fast reaction, and is characterized by a reduced reactivity. To contribute to such understanding, we compare here the hydration process of two cement samples, the simple cement paste and the cement paste containing calcium nitrate as an accelerator. The hydration of these samples is monitored during the induction period using two different low-field nuclear magnetic resonance (NMR) relaxometry techniques. The transverse relaxation measurements of the 1H nuclei at 20 MHz resonance frequency show that the capillary pore water is not consumed during the induction period and that this stage is shortened in the presence of calcium nitrate. The longitudinal relaxation measurements, performed at variable Larmor frequency of the 1H nuclei, reveal a continuous increase in the surface-to-volume ratio of the capillary pores, even during the induction period, and this increase is faster in the presence of calcium nitrate. The desorption time of water molecules from the surface was also evaluated, and it increases in the presence of calcium nitrate.

Chitosan Effect on Hardening Dynamics of Calcium Phosphate Cement: Low-Field NMR Relaxometry Investigations.

Calcium phosphate cements are used in dentistry and orthopedics to repair and reconstruct bone defects. The properties of these bone cements can be improved by introducing additives into their composition. One favorable additive is chitosan, which can be beneficial but can also cause considerable damage if it has a high load, thus, limiting its clinical applicability and performance. That is why understanding chitosan's role in cement composition is an important issue when developing new materials. The present work uses low-field nuclear magnetic resonance (NMR) relaxometry to investigate the effect introduced by the addition of chitosan on the hardening process of calcium phosphate cement. Two samples, prepared with and without chitosan, were comparatively investigated during the first six minutes of hardening. The liquid evolution inside these samples was monitored using transverse relaxation time distributions. It demonstrated an acceleration effect on the hardening dynamics introduced by the presence of chitosan. Furthermore, it was shown that even after one hour of hardening, there were still unreacted monomers inside the bone cement and their amount was reduced in the presence of chitosan.

Use of magic sandwich echo and fast field cycling NMR relaxometry on honey adulteration with corn syrup.

BACKGROUND: Adulteration is defined as the intentional addition of a material that is not a part of the nature. In this study, a non-conventional time domain nuclear magnetic resonance (TD-NMR) pulse sequence: magic sandwich echo (MSE) was used to detect the adulteration of honey by glucose syrup (GS) and high fructose corn syrup (HFCS) accompanied with T1 and T2 relaxation times. Also, fast field cycling NMR (FFC-NMR) relaxometry and multivariate analysis were performed to investigate the adulteration. RESULTS: Higher maltose in GS and changing glucose to water ratio of HFCS gave high correlation with the crystal content values. In HFCS adulteration, two separate populations of protons having different T2 values were detected and T1 times were also used to determine GS adulteration. Addition of GS increased T1 while addition of HFCS increased T2 , significantly. CONCLUSION: The results showed that it is possible to differentiate the unadulterated and adulterated honey samples by using TD-NMR relaxation times and crystal content values obtained by the MSE sequence. By FFC-NMR relaxometry, not only GS addition but also the amount of GS was examined. The multivariate analysis technique of principal component analysis was able to distinguish the types of adulterants. © 2021 Society of Chemical Industry.

Analyzing the Effects of Calcium Nitrate over White Portland Cement: A Multi-Scale Approach.

Calcium nitrate is considered a promising accelerator in cement-based composites, with high potential in 3D printing and cold cement concreting. The effect induced by the composition of calcium nitrate tetrahydrate (CN) accelerator into white Portland cement is evaluated here from three perspectives: (1) Fresh cement paste properties in terms of setting time and slump, (2) mechanical properties of hardened cement samples at 7 and 28 days and (3) material characteristics in terms of structure and porosity that further link the presence of the accelerator with the macroscopic performances. The compressive and flexural strength of the hardened samples, evaluated after 7 and 28 days of hydration, indicate a non-monotonous trend with CN concentration. Crystalline phase composition is investigated using X-ray diffraction (XRD). The morphology and texture are analyzed at the flexure interface by visual inspection and electron microscopy. Complementary, the porous features are investigated by NMR-relaxometry on dry and cyclohexane-filled samples. The studies confirm that CN promotes changes in the composition and morphology of hydrates, while a trend of increase in capillary porosity is outlined as well. This competition between multiscale effects may be quantified by NMR and complementary techniques to further clarify the mechanical behavior of such composites.

The Effect of an Accelerator on Cement Paste Capillary Pores: NMR Relaxometry Investigations.

Nuclear Magnetic Resonance (NMR) relaxometry is a valuable tool for investigating cement-based materials. It allows monitoring of pore evolution and water consumption even during the hydration process. The approach relies on the proportionality between the relaxation time and the pore size. Note, however, that this approach inherently assumes that the pores are saturated with water during the hydration process. In the present work, this assumption is eliminated, and the pore evolution is discussed on a more general basis. The new approach is implemented here to extract information on surface evolution of capillary pores in a simple cement paste and a cement paste containing calcium nitrate as accelerator. The experiments revealed an increase of the pore surface even during the dormant stage for both samples with a faster evolution in the presence of the accelerator. Moreover, water consumption arises from the beginning of the hydration process for the sample containing the accelerator while no water is consumed during dormant stage in the case of simple cement paste. It was also observed that the pore volume fractal dimension is higher in the case of cement paste containing the accelerator.

Freeze-Thaw Effect on Road Concrete Containing Blast Furnace Slag: NMR Relaxometry Investigations.

The present work investigates the effect of freeze-thaw cycles on the porosity of three mixtures of road concrete containing blast furnace slag in comparison with two mixtures made with conventional materials. The main technique used in our investigations is nuclear magnetic resonance (NMR) relaxometry. This permitted the extraction of information with respect to the freeze-thaw effect on pore-size distribution, which influences both the mechanical strength and the molecular transport through the material. Moreover, by using this technique, the structure of the air voids was analyzed for the entire pore system in the cement paste and the aggregate particles. The samples under study were first dried in a vacuum oven and then saturated with water or cyclohexane where the distribution of the transverse relaxation times of the protons was recorded. The NMR relaxation measurements were performed on samples extracted from specimens maintained at 300 freeze-thaw cycles and on control samples extracted from specimens kept in water during the freeze-thaw period. Scanning Electron Microscopy (SEM) was used to analyze the microstructure of concrete samples in order to obtain information about the pore sizes and the distance between them. The results from the NMR relaxation measurements were consistent with those obtained by using standard techniques for determining the porosity and the freeze-thaw resistances. The investigations made it possible to establish the optimal composition of blast furnace slag that can be incorporated into road concrete compositions. This non-invasive technique can also complete standard techniques for assessing the porosity and the progress of internal cracks during the freeze-thaw test.

Beyond Nitrogen in the Oxygen Reduction Reaction on Nitrogen-Doped Carbons: A NEXAFS Investigation.

Polymer electrolyte membrane fuel cells require cheap and active electrocatalysts to drive the oxygen reduction reaction. Nitrogen-doped carbons have been extensively studied regarding their oxygen reduction reaction. The work at hand looks beyond the nitrogen chemistry and brings to light the role of oxygen. Nitrogen-doped nanocarbons were obtained by a radio-frequency plasma route at 0, 100, 250, and 350 W. The lateral size of the graphitic domain, determined from Raman spectroscopy, showed that the nitrogen plasma treatment decreased the crystallite size. Synchrotron radiation photoelectron spectroscopy showed a similar nitrogen chemistry, albeit the nitrogen concentration increased with the plasma power. Lateral crystallite size and several nitrogen moieties were plotted against the onset potential determined from oxygen reduction reaction curves. There was no correlation between the electrochemical activity and the sample structure, as determine from Raman and synchrotron radiation photoelectron spectroscopy. Near-edge X-ray absorption fine structure (NEXAFS) was performed to unravel the carbon and nitrogen local structure. A difference analysis of the NEXAFS spectra showed that the oxygen surrounding the pyridinic nitrogen was critical in achieving high onset potentials. The work shows that there were more factors at play, other than carbon organization and nitrogen chemistry.

Molecular self-diffusion in internal magnetic fields of porous medium investigated by NMR MGSE method.

Inhomogeneous magnetic fields generated in porous media due to differences in magnetic susceptibility at solid/liquid interfaces and due to intrinsic or artificially doped magnetic impurities can be used to gain insight into the molecular dynamics of fluid in the structure of a porous medium using the concept of NMR modulated gradient spin echo method. We extended the theory of this method to the case of an inhomogeneous magnetic field that cannot be approximated by an uniform gradient, in order to explain the CPMG measurements of self-diffusion in water soaked ceramics, which are doped with magnetic impurities of different contents. The new interpretation provides the spin relaxation times, the average pore size and their distribution, as well as the strength of the internal magnetic gradient fields in the doped ceramics.

Interplay of Aging and Lot-to-Lot Variability on the Physical and Chemical Properties of Excipients: A Case Study of Mono- and Diglycerides.

The present study investigates the chemical composition governing the physical properties of mono- and diglycerides (MDGs) at the microstructural level, as a function of aging and lot-to-lot variability. The physical structure of the MDG plays a vital role in ameliorating the emulsion stability and is widely explored in diverse research horizons related to the pharmaceutical, cosmetic, and food industries. In an effort to understand the mechanism of emulsion stabilization, physical properties were extensively evaluated in selective commercial lots to determine if there is a correlation between the chemical composition of MDG and physical properties. The solid state of the MDG samples with different aging profiles was characterized using X-ray scattering, differential scanning calorimetry, attenuated total reflection-Fourier transform infrared spectroscopy, and NMR relaxometry. Moreover, the kinetic aspect of solid-state transformation was also evaluated via treating MDG samples with a heat-cool cycle. The chemical composition of MDGs was quantified using a quantitative NMR (qNMR) method. Interestingly, the X-ray scattering results demonstrated a change in the MDG polymorphic form and an increase in the %ß content as a function of aging. The increase in the %ß content led to the formation of rigid crystal structures of MDG, as evident from the NMR relaxometry. Chemical quantification of isomeric composition revealed chemical composition change as a potentially critical factor responsible for the altered physical structures of MDG with respect to aging and lot-to-lot variability. The findings correlated the solid-state transformation with the change in the chemical composition of the MDG as a combined effect of aging and lot-to-lot variability. This work serves as a basis to better understand the interdependency of the physicochemical properties of MDG. Furthermore, the present work can also be used as guidance for setting up the specifications of MDG, as per the required polymorphic form for a multitude of applications.

Geochemical investigations of noble metal-bearing ores: Synchrotron-based micro-analyses and microcosm bioleaching studies.

Auriferous sulphide ores often incorporate micro-fine (or invisible) gold and silver particles in a manner making their extraction difficult. Nobel metals are lost in the tailings due to the refractory nature of these ores. Bioleaching is an environment-friendly alternative to the commonly used and toxic cyanidation protocols for gold extraction from refractory ores. In this paper, we investigate gold and silver bioleaching from porphyry and epithermal mineralisation systems, using iron-oxidizing bacteria Acidithiobacillus ferrooxidans. The invisible Au, sequestered in refractory ores, was characterised in situ by synchrotron micro X-Ray Fluorescence (SR-µ-XRF) and X-ray Absorption Spectroscopy (XAS), offering information on Au unaltered speciation at the atomistic level within the ore matrices and at a micro-scale spatial resolution. The SR-µ-XRF and XAS results showed that 10-20 µm sized elemental Au(0) nuggets are sequestered in pyrite, chalcopyrite, arsenopyrite matrices and at the interface of a mixture of pyrite and chalcopyrite. Moreover, the preliminary bioleaching experiments of the two types of ores, showed that Acidithiobacillus ferrooxidans can catalyse the dissolution of natural heterogeneous Fe-rich geo-matrices, sequestering Au and Ag and releasing particulate phases or partially solubilising them within 60 days. These results provide an understanding of noble metal sequestration and speciation within natural ores and a demonstration of the application of synchrotron-based micro-analysis in characterizing economic trace metals in major mineral structures. This work is a contribution to the ongoing efforts towards finding feasible and greener solutions of noble metal extraction protocols.

Revealing the Influence of Microparticles on Geopolymers' Synthesis and Porosity.

Geopolymers are zeolites like structures based on hydrated aluminosilicates units of SiO4 and AlO4. These units, known as poly(sialate), poly(sialate)-siloxo or poly(sialate)-disiloxo are chemically balanced by the group I cations of K+, Li+, or Na+. Simultaneously, the chemical reaction of formation, known as geopolymerization, governs the orientation of the unit, generating mesoporous structures. Multiple methods can be used for pore structure and porosity characterization. Among them, nuclear magnetic resonance (NMR) relaxometry allows the detection of the porous structure in a completely nonperturbative manner. NMR relaxometry may be used to monitor the relaxation of protons belonging to the liquid molecules confined inside the porous structure and, thus, to get access to the pore size distribution. This monitoring can take place even during the polymerization process. The present study implements transverse relaxation measurements to monitor the influence introduced by the curing time on the residual liquid phase of geopolymers prepared with two different types of reinforcing particles. According to our results, the obtained geopolymers contain three types of pores formed by the arrangement of the OH- and Si groups (Si-OH), Si-O-Si groups, Si-O-Al groups, and Si-O rings. After 48 days, the samples cured for 8 h show a high percentage of all three types of pores, however, by increasing the curing time and the percentage of reinforcing particle, the percent of pores decrease, especially, the gel pores.

The Effect of Silica Fume and Organosilane Addition on the Porosity of Cement Paste.

The present work systematically investigates the influence of silica fume and organosilane addition on the hydration dynamics and the capillary pore formation of a cement paste. The cement samples were prepared with two water-to-cement ratios with increasing amounts of silica fume and of (3-Aminopropyl)triethoxysilane (APTES) organosilane. Low-field 1H nuclear magnetic resonance (NMR) relaxation measurements were performed during the hydration of the samples and after hydration, in order to reveal the dynamics of water molecules and the pore distribution. Increasing concentrations of silica fume impact the perceived hydration dynamics through the addition of magnetic impurities to the pore solution. However, there is a systematic change in the capillary pore size distribution with an increase in silica fume concentration. The results also show that the addition of APTES majorly affects the hydration dynamics, by prolonging the dormancy and hardening stages. While it does not influence the pore size distribution of capillary pores, it prevents cyclohexane from saturating the capillary pores.

Evolution of the microstructure and the drug release upon annealing the drug loaded lipid-surfactant microspheres.

The present study investigates the drug release-governing microstructural properties of melt spray congealed microspheres encapsulating the drug crystals in the matrix of glyceryl behenate and poloxamer (pore former). The solid-state, morphology, and micromeritics of the microspheres were characterized, before and after annealing, using calorimetry, X-ray scattering, porosimetry, scanning electron microscopy, and, NMR diffusometry. The in vitro drug release from and water uptake by the microspheres were obtained. The extent and the rate of drug release from the microspheres increased with a high poloxamer content and at higher annealing temperature and RH. All the drug release profiles were describable using the Higuchi release kinetics pointing towards the diffusion controlled release, both before and after annealing. The annealing process led to the polymorphic conversion of lipid and the increase in the pore size, predominantly at a higher temperature and humidity and for a high poloxamer content. The poloxamer domain increased from an initial 300 nm, up to 2000 nm upon annealing. The water diffusion rate inside the annealed microsphere was twice as fast as for unannealed counterparts. The findings relate the overall phase and pore structure change of the microsphere to the increased drug release induced by annealing. This work serves as a basis for the rational understanding of the modification of the in vitro performance by annealing, a widely used post-process for solid lipid products.

Imbibition and dewetting of silica colloidal crystals: An NMR relaxometry study.

HYPOTHESIS: The wettability of the inner surfaces in a porous network is challenging to be accessed but essential to understand the complex performance of e.g. particulate systems. EXPERIMENTS: Here we investigate the water behavior in the macroporous (50-100 nm) voids of dense particle packings by performing low-field 1H NMR relaxometry in solid silica colloid crystals. The systems chosen guarantee a regular, known void size distribution with controllable water affinity (through thermal annealing), where the NMR experiment clearly discriminates the void water from micropore or bound water contributions, allowing separate monitoring. FINDINGS: Analysis of the saturated state indicates that the interparticle voids are completely filled after imbibition, even for less hydrophilic spheres. Due to the interaction with the silica surface, proton relaxation in void water is up to 100 times faster than that in bulk water, serving for assessment of the hydrophilicity within the sample. The relaxation time evolution upon dewetting provides an empirical measurement of the wettability inside the ensemble, revealing a progressively inhomogeneous wetting of increasingly hydrophobic surfaces. Our results provide insight into the imbibition state and dewetting performance in meso- and macroporous systems, with emphasis in the marked influence of the surface nature on the pore wetting distribution.

Surface influence on the rotational and translational dynamics of molecules confined inside a mesoporous carbon xerogel.

Low-field nuclear magnetic resonance techniques are employed to extract information about the effects introduced by the interaction with the surface on the rotational and translational dynamics of molecules confined inside a mesoporous carbon xerogel. The molecules under study were water, cyclohexane, and hexane. They were chosen due to their different interaction strength with the carbonaceous matrix. Frequency dependent longitudinal relaxation measurements, using the fast field cycling technique, allowed extraction of the fractal dimension of the carbon xerogel surface. It was observed that the measured value is influenced by the molecule affinity to the surface. Diffusion measurements, using the pulse field gradient technique, have revealed that the stronger interaction with the surface of cyclohexane and hexane molecules leads to an increased diffusive tortuosity, as compared with water.

Usage of internal magnetic fields to study the early hydration process of cement paste by MGSE method.

Internal magnetic field gradients, arising within the porous media due to susceptibility differences at the interfaces of solid and liquid as well as due to the contained magnetic impurities, can be employed by the method of modulated gradient spin echo to get insight into the velocity autocorrelation spectrum of liquid confined in the porous structure. New theoretical treatment of spin interaction with the radio-frequency field and the simultaneously applied static non-uniform magnetic field provides the formula that match well with the measurement of restricted diffusion of water in pores of cement paste. Its fitting to the experimental data gives the changes in the mean size of capillary pores, the spin relaxation and the magnitude of mean internal magnetic field gradients during the induction period and early acceleration stage of hydration processes at different temperatures.

The effect and role of environmental conditions on magnetosome synthesis.

Magnetotactic bacteria (MTB) are considered the model species for the controlled biomineralization of magnetic Fe oxide (magnetite, Fe3O4) or Fe sulfide (greigite, Fe3S4) nanocrystals in living organisms. In MTB, magnetic minerals form as membrane-bound, single-magnetic domain crystals known as magnetosomes and the synthesis of magnetosomes by MTB is a highly controlled process at the genetic level. Magnetosome crystals reveal highest purity and highest quality magnetic properties and are therefore increasingly sought after as novel nanoparticulate biomaterials for industrial and medical applications. In addition, "magnetofossils," have been used as both past terrestrial and potential Martian life biosignature. However, until recently, the general belief was that the morphology of mature magnetite crystals formed by MTB was largely unaffected by environmental conditions. Here we review a series of studies that showed how changes in environmental factors such as temperature, pH, external Fe concentration, external magnetic fields, static or dynamic fluid conditions, and nutrient availability or concentrations can all affect the biomineralization of magnetite magnetosomes in MTB. The resulting variations in magnetic nanocrystals characteristics can have consequence both for their commercial value but also for their use as indicators for ancient life. In this paper we will review the recent findings regarding the influence of variable chemical and physical environmental control factors on the synthesis of magnetosome by MTB, and address the role of MTB in the global biogeochemical cycling of iron.