Scaling-Free Cathodes: Enabling Electrochemical Extraction of High-Purity Nano-CaCO3 and -Mg(OH)2 in Seawater.

For electrochemical application in seawater or brine, continuous scaling on cathodes will form insulation layers, making it nearly impossible to run an electrochemical reaction continuously. Herein, we report our discovery that a cathode consisting of conical nanobundle arrays with hydrophobic surfaces exhibits a unique scaling-free function. The hydrophobic surfaces will be covered with microbubbles created by electrolytic water splitting, which limits scale crystals from standing only on nanotips of conical nanobundles, and the bursting of large bubbles formed by the accumulation of microbubbles will cause a violent disturbance, removing scale crystals automatically from nanotips. Benefiting from the scaling-free properties of the cathode, high-purity nano-CaCO3 (98.9%) and nano-Mg(OH)2 (99.5%) were extracted from seawater. This novel scaling-free cathode is expected to eliminate the inherent limitations of electrochemical technology and open up a new route to seawater mining.

Ultrasonic Preparation of Nano-CaCO3 Templates and Hollow Mesoporous SiO2 Nanoparticles for Voriconazole Loading.

CaCO3 nanoparticles (nano-CaCO3) as nano-templates were prepared using CaCl2 and Na2CO3 solutions under controlled sonication (19.5 kHz). Using the same ultrasonic device, subsequently, hollow mesoporous silica nanoparticles (HMSNs) were obtained by the hard template of nano-CaCO3. HMSNs were selected as carriers for the antifungal drug voriconazole (VOR) loading to overcome poor water solubility. Three-dimensional CaCO3 nanosheets HMSNs were obtained under gentle sonication. Three-dimensional CaCO3 nanosheets of 24.5 nm (hydrodynamic diameter) were obtained under 17.6 W for 3 min. HMSNs were synthesized by double-template method with nano-CaCO3 as the hard template. Transmission electron microscopy measurements showed that the prepared HMSNs possess hollow structures with particle size between 110 and 120 nm. Nitrogen physisorption at -196 °C revealed that the HMSNs had high surface area (401.57 m2/g), high pore volume (0.11 cm3/g), and uniform pore size (2.22 nm) that facilitated the effective encapsulation of VOR in the HMSNs. The loading capacity of VOR (wt%) on the HMSNs was 7.96%, and the total VOR release amount of VOR-HMSNs material was 71.40% at 480 min. The kinetic model confirmed that the release mechanism of HMSNs nanoparticles followed Fickian diffusion at pH = 7.4 and 37 °C. Moreover, the cumulative VOR release at 42 °C (86.05%) was higher than that at 37 °C (71.40%). The cumulative release amount of VOR from the VOR-HMSNs material was 92.37% at pH = 5.8 at the same temperature. Both nano-CaCO3 templates and HMSNs were prepared by sonication at 19.5 kHz. The as-prepared HMSNs can effectively encapsulate VOR and released drug by Fickian diffusion.

Biomass-Derived Anion-Anchoring Nano-CaCO3 Coating for Regulating Ion Transport on Li Metal Surface.

The free transport of anions in a Li metal battery can cause multiple issues, including a high anion transference number, space charge, and concentration polarization, eventually leading to uncontrolled dendrite formation and decreased performance. Herein, we report an anion-anchoring nano-CaCO3 (NC) coating derived from eggshell biowaste for stabilizing Li metal anodes. As the adsorption of local TFSI- anions onto the NC adsorbent can undermine the anion concentration gradient and promote rapid Li-ion diffusion, it can effectively inhibit the proliferation of Li dendrites assisted by the NC coating. Consequently, Li/Cu cells with NC@Cu electrode can achieve a high Coulombic efficiency of ∼98.4% for more than 420 cycles and can even reach ∼99.1% at an ultrahigh areal capacity of 20 mAh cm-2. In particular, full cells with NC/Li@Cu electrodes show a stable lifespan of over 240 cycles with an average efficiency of ∼99.8% at a low N/P ratio of ∼3.3.

Effect of fortification with CaCO3 nanoparticles obtained from eggshell on the physical and sensory characteristics of three food matrices.

Food fortification has attracted interest in recent years, due to the understanding that micronutrient deficiency is one of the causes of the global burden of disease, and that food fortification aims to prevent or correct a demonstrated deficiency of one or more nutrients in a specific population or population groups. Nutritional value is an important concern regarding fortification and new product development. However, people are not willing to sacrifice the organoleptic characteristics of food products. Therefore, the effect of CaCO3 nanoparticles (NPs-CaCO3) and commercial CaCO3 on the physical and sensory properties of three food matrices (cookies, fruit rolls and dairy desserts) was evaluated. A texture analysis was performed on cookies and fruit rolls; a viscosity analysis on dairy desserts; and a color analysis and sensory profile on the three matrices. The results showed that both types of calcium increase hardness in fortified biscuits and fruit rolls but, in the latter case, commercial calcium caused a higher increase in hardness (p < 0.05). Viscosity was higher in the desserts with NPs. Color presented significant changes in all the fortified matrices. These findings demonstrated that Ca-NPs are a good strategy for food fortification compared to commercial calcium carbonate, as fortification with high levels of calcium is a challenge for the food industry due to its effects on the product. The results showed that, in the matrices with commercial calcium, the changes were more evident, while the matrices fortified with Ca-NP have a better sensory response than commercial Ca, with a higher level of acceptance by the judges. Therefore Ca-NPs can be considered to be a good source of calcium for food product fortification that causes a slight effect on physical and sensory properties.

Exploring the Effects of Nano-CaCO3 on the Core-Shell Structure and Properties of HDPE/POE/Nano-CaCO3 Ternary Nanocomposites.

To address the dilemma of the stiffness and toughness properties of high-density polyethylene (HDPE) composites, titanate coupling agent-treated CaCO3 nanoparticles (nano-CaCO3) and ethylene-octene copolymer (POE) were utilized to blend with HDPE to prepare ternary nanocomposites via a two-sequence-step process. Meanwhile, a one-step process was also studied as a control. The obtained ternary nanocomposites were characterized by scanning electron microscopy (SEM), Advanced Rheometrics Expansion System (ARES), Dynamic Mechanical Analysis (DMA), wide-angle X-ray diffraction analysis (WXRD), and mechanical test. The SEM results showed one or two CaCO3 nanoparticles were well-encapsulated by POE and were uniformly dispersed into the HDPE matrix to form a core-shell structure of 100-200 nm in size by the two-step process, while CaCO3 nanoparticles were aggregated in the HDPE matrix by the one-step method. The result of the XRD showed that the nano-CaCO3 particle played a role in promoting crystallization in HDPE nanocomposites. Mechanical tests showed that the synergistic effect of both the POE elastomer and CaCO3 nanoparticles should account for the balanced performance of the ternary composites. In comparison with neat HDPE, the notched impact toughness of the ternary nanocomposites of HDPE/POE/nano-CaCO3 was significantly increased. In addition, the core-shell structure absorbed the fracture impact energy and prevent further propagation of micro-cracks, thus obtaining a higher notched Izod impact strength.

A Critical Review Examining the Characteristics of Modified Concretes with Different Nanomaterials.

The movement of the construction industry towards sustainable development has drawn attention to the revision of concrete. In addition to reducing pollution, the use of nano-materials should lead to the provision of higher quality concrete in terms of regulatory items (workability, resistance characteristics, durability characteristics, microstructure). The present study investigates 15 key characteristics of concrete modified with nano-CaCO3, nano-clay, nano-TiO2, and nano-SiO2. The results of the study showed that nanomaterials significantly have a positive effect on the hydration mechanism and the production of more C-S-H gel. The evaluation of resistance characteristics also indicates the promising results of these valuable materials. The durability characteristics of nano-containing concrete showed significant improvement despite high dispersion. Concrete in coastal areas (such as bridges or platforms), concrete exposed to radiation (such as hospitals), concrete exposed to impact load (such as nuclear power plants), and concrete containing recycled aggregate (such as bricks, tiles, ceramics) can be effectively improved by using nanomaterials. It is hoped that the current review paper can provide an effective image and idea for future applied studies by other researchers.

Study on Effect of Nano-CaCO3 on Properties of Phosphorus Building Gypsum.

Phosphogypsum is an industrial by-product from the wet preparation of phosphoric acid. Phosphorus building gypsum (PBG) can be obtained from phosphogypsum after high-thermal dehydration. Improving the mechanical properties of PBG is of great significance to extending its application range. In this paper, PBG was modified by adding nano-CaCO3. Specifically, this study, conducted on 0.25-2% nano-CaCO3-doped PBG, tested effects on the fluidity, setting time, absolute dry flexural strength, absolute dry compressive strength, water absorption and softening coefficient of PBG, followed by its microscopic analysis with SEM and XRD. The experimental results showed that, with an increase in nano-CaCO3 content, the fluidity and setting time of PBG-based mixes were decreased. When the content was 2%, the fluidity was 120 mm, which was 33% lower than that of the blank group; the initial setting time was 485 s, which was 38% lower than that in the blank group; the final setting time was 1321 s, which was reduced by 29%. Nano-CaCO3 evidently improved the absolute dry flexural strength, absolute dry compressive strength, water absorption and softening coefficient of PBG to a certain extent. When the content was 1%, the strengthening effect reached the optimum, with the absolute dry flexural strength and absolute dry compressive strength being increased to 8.1 MPa and 20.5 MPa, respectively, which were 50% and 24% higher than those of the blank group; when the content was 1.5%, the water absorption was 0.22, which was 33% lower than that of the blank group; when the content approached 0.75%, the softening coefficient reached the peak of 0.63, which was 66% higher than that of the blank group. Doping with nano-CaCO3 could significantly improve the performance of PBG, which provides a new scheme for its modification.

Activation behavior of the novel CO2 foaming agent for mining on fly ash.

Although there have been many research results on the chemical activation of fly ash (FA) as a supplementary cementitious material (SCM) in cementitious materials. However, there is a lack of research on the use of CO2 foaming agent (sodium bicarbonate and potassium aluminum sulfate) to activate fly ash. In this experiment, the effects of CO2 foaming agent, sodium bicarbonate, and potassium aluminum sulfate on the activity of FA mixed paste were investigated. The mechanism of FA activation by activator was revealed by selective acid dissolution, QXRD, BSE-EDS statistical analysis, and quantitative analysis of TGA. The results showed that the remaining fly ash amounts of MG, SBG, and PASG after 28 days were 17.5%, 25.9%, and 43.3% lower than those of the control group, respectively. In addition, potassium aluminium sulphate promoted hydration to generate more CH to activate the FA. Sodium bicarbonate promoted hydration and produces more CH to activate FA by generating nano-CaCO3. The mixture of sodium bicarbonate and potassium aluminum sulfate took advantage of both nano-CaCO3 and potassium aluminum sulfate to promote silicate hydration to provide CH. As a result, the two synergistically activate FA. The above results show that CO2 foaming agents can be used not only as foaming agents to prepare lightweight materials, but also as chemical activators to activate solid waste. This will have a high practical application value.

Hollow nano-CaCO3's VOC sensing properties: A DFT calculation and experimental assessments.

Air is the most critical and necessary for life, and air quality significantly impacts people's health. Both indoor and outdoor pollution frequently contain volatile organic compounds (VOCs). Such contaminants provide immediate or long-term health risks to the living system. The present study investigates sorption characteristics of VOCs on hollow nano calcite (CaCO3) particles with 250 nm and 40 nm pore sizes to remove from the air ambient using the quartz crystal microbalance (QCM) technique at room temperature both experimentally and theoretically. The results were supported by density functional theory (DFT), and adsorption-desorption characteristics were studied with Langmuir adsorption isotherms. The QCM measurements showed a stable signal without having hysteresis, and the response of polar VOCs on hollow nano-CaCO3 particles such as ethanol, propanol, and humidity with higher polarity was less compared to solvents such as chloroform and dichloromethane, which revealed that the surfaces of CaCO3 particles have mostly non-polar properties. CaCO3 surface and VOC molecule interactions overlap with the Langmuir model. With DFT calculations, VOC and water molecule adsorption changes the CaCO3 Egap. Our findings show that the ΔEgap values increase as chloroform > dichloromethane > propanol > ethanol > water. This order suggests that the sensing response of the hollow CaCO3 structure is linearly proportional to the adsorption energies of VOC and water. The linear adsorption characteristics, high sensing response, and short recovery time illustrated that the newly synthesized nano-CaCO3 could be implemented as a new VOC adsorbent material for health, environmental sustainability, and in vitro microbiome cultures.

Bagasse Cellulose Composite Superabsorbent Material with Double-Crosslinking Network Using Chemical Modified Nano-CaCO3 Reinforcing Strategy.

To improve the salt resistance of superabsorbent materials and the gel strength of superabsorbent materials after water absorption, a bagasse cellulose-based network structure composite superabsorbent (CAAMC) was prepared via graft copolymerization of acrylamide/acrylic acid (AM/AA) onto bagasse cellulose using silane coupling agent modified nano-CaCO3 (MNC) and N,N'-methylene bisacrylamide (MBA) as a double crosslinker. The acrylamide/acrylic acid was chemically crosslinked with modified nano-CaCO3 by C-N, and a stable double crosslinked (DC) network CAAMC was formed under the joint crosslinking of N,N'-methylene bisacrylamide and modified nano-CaCO3. Modified nano-CaCO3 plays a dual role of crosslinking agent and the filler, and the gel strength of composite superabsorbent is two times higher than that of N,N'-methylene bisacrylamide single crosslinking. The maximum absorbency of CAAMC reached 712 g/g for deionized water and 72 g/g for 0.9 wt% NaCl solution. The adsorption process of CAAMC was simulated by materials studio, and the maximum adsorption energy of amino and carboxyl groups for water molecules is -2.413 kJ/mol and -2.240 kJ/mol, respectively. According to the results of CAAMC soil water retention, a small amount of CAAMC can greatly improve the soil water retention effect.

Preparation and Characterization of Nano-CaCO3/Ceresine Wax Composite Shell Microcapsules Containing E-44 Epoxy Resin for Self-Healing of Cement-Based Materials.

As an intelligent material, microcapsules can efficiently self-heal internal microcracks and microdefects formed in cement-based materials during service and improve their durability. In this paper, microcapsules of nano-CaCO3/ceresine wax composite shell encapsulated with E-44 epoxy resin were prepared via the melt condensation method. The core content, compactness, particle size distribution, morphologies, chemical structure and micromechanical properties of microcapsules were characterized. The results showed that the encapsulation ability, mechanical properties and compactness of microcapsules were further improved by adding nano-CaCO3 to ceresine wax. The core content, elastic modulus, hardness and weight loss rate (60 days) of nano-CaCO3/ceresine wax composite shell microcapsules (WM2) were 80.6%, 2.02 GPA, 72.54 MPa and 1.6%, respectively. SEM showed that WM2 was regularly spherical with a rough surface and sufficient space inside the microcapsules to store the healing agent. The incorporation of WM2 to mortar can greatly improve the self-healing ability of mortar after pre-damage. After 14 days of self-healing, the compressive strength recovery rate, proportion of harmful pores and chloride ion diffusion coefficient recovery rate increased to 90.1%, 45.54% and 79.8%, respectively. In addition, WM2 also has good self-healing ability for mortar surface cracks, and cracks with initial width of less than 0.35 mm on the mortar surface can completely self-heal within 3 days.

The Generation Process, Impurity Removal and High-Value Utilization of Phosphogypsum Material.

As phosphogypsum constitutes a large amount of solid waste material, its purification treatment and comprehensive utilization have close connection with economic development and ecological environmental protection. For the moment, the storage quantity of phosphogypsum is still rising as a result of the increasing phosphate fertilizer production to meet the food demand in China. This paper summarizes the generation process, impurity removal treatment (physical method, chemical method, heat method), high-value utilization (nanometer calcium sulfate whisker, nanometer calcium carbonate) of phosphogypsum material and some existing problems. It puts forward some views on the challenges in this field and the direction of future development. It is hoped that the investigation and summary in this paper could supply some significant information for the impurity removal and high-value utilization of phosphogypsum material as a contribution to sustainability.

In situ carbon dioxide capture to co-produce 1,3-propanediol, biohydrogen and micro-nano calcium carbonate from crude glycerol by Clostridium butyricum.

BACKGROUND: Climate change caused by greenhouse gas emission has become a global hot topic. Although biotechnology is considered as an environmentally friendly method to produce chemicals, almost all biochemicals face carbon dioxide emission from inevitable respiration and energy metabolism of most microorganisms. To cater for the broad prospect of biochemicals, bioprocess optimization of diverse valuable products is becoming increasingly important for environmental sustainability and cleaner production. Based on Ca(OH)2 as a CO2 capture agent and pH regulator, a bioprocess was proposed for co-production of 1,3-propanediol (1,3-PDO), biohydrogen and micro-nano CaCO3 by Clostridium butyricum DL07. RESULTS: In fed-batch fermentation, the maximum concentration of 1,3-PDO reached up to 88.6 g/L with an overall productivity of 5.54 g/L/h. This productivity is 31.9% higher than the highest value previously reports (4.20 g/L/h). In addition, the ratio of H2 to CO2 in exhaust gas showed a remarkable 152-fold increase in the 5 M Ca(OH)2 group compared to 5 M NaOH as the CO2 capture agent. Green hydrogen in exhaust gas ranged between 17.2% and 20.2%, with the remainder being N2 with negligible CO2 emissions. During CO2 capture in situ, micro-nano calcite particles of CaCO3 with sizes in the range of 300 nm to 20 µm were formed simultaneously. Moreover, when compared with 5M NaOH group, the concentrations of soluble salts and proteins in the fermentation broth of 5 M Ca(OH)2 group were notably reduced by 53.6% and 44.1%, respectively. The remarkable reduction of soluble salts and proteins would contribute to the separation of 1,3-PDO. CONCLUSIONS: Ca(OH)2 was used as a CO2 capture agent and pH regulator in this study to promote the production of 1,3-PDO. Meanwhile, micro-nano CaCO3 and green H2 were co-produced. In addition, the soluble salts and proteins in the fermentation broth were significantly reduced.

CO2 Sequestration in the Production of Portland Cement Mortars with Calcium Carbonate Additions.

The paper presents the obtention and characterization of Portland cement mortars with limestone filler and nano-calcite additions. The nano-calcite was obtained by the injection of CO2 in a nano-Ca(OH)2 suspension. The resulted nano-CaCO3 presents different morphologies, i.e., polyhedral and needle like crystals, depending on the initial Ca(OH)2 concentration of the suspension. The formation of calcium carbonate in suspensions was confirmed by X-ray diffraction (XRD), complex thermal analysis (DTA-TG), scanning electron microscopy (SEM) and transmission electron microscopy (TEM and HRTEM). This demonstrates the viability of this method to successfully sequestrate CO2 in cement-based materials. The use of this type of nano-CaCO3 in mortar formulations based on PC does not adversely modify the initial and final setting time of cements; for all studied pastes, the setting time decreases with increase of calcium carbonate content (irrespective of the particle size). Specific hydrated phases formed by Portland cement hydration were observed in all mortars, with limestone filler additions or nano-CaCO3, irrespective of curing time. The hardened mortars with calcium carbonate additions (in adequate amounts) can reach the same mechanical strengths as reference (Portland cement mortar). The addition of nano-CaCO3 in the raw mix increases the mechanical strengths, especially at shorter hardening periods (3 days).

The Influence of Nano CaCO3 on Nucleation and Interface of PP Nano Composite: Matrix Processability and Impact Resistance.

Polypropylene (PP) is a commodity material that has been increasingly used in different industries in the past two decades due to its versatile properties when enhanced with additives. Homo polypropylene, in general, has weak mechanical properties and limited chemical resistance; thus, using a different type of fillers to adjust such properties to fit the required applications opened a large market for this commodity. Understanding the interface constituent between the polymer matrix and the added filler and the nucleation behavior is a key to fine control of the enhancement of PP properties. In this study, PP was incorporated with nano calcium carbonate (CaCO3) at 2 and 5 wt% in the presence of maleic anhydride (MAH) to overcome the weak interface due to low polymer polarity. The mix was compounded in a twin screws extruder at a temperature range of 180-200 °C ; then, the prepared samples were left to dry for 24 h at 25 °C. Nuclear Magnetic Resonance (NMR) was used to study the interface adhesion of the nanofiller and the curved revealed that at 2% of nano CaCO3 PP structure remained the same and the nano experienced good adhesion to the polymer matrix. The mechanical impact resistance results showed a real enhancement to the polymer matrix of the nanocomposite by 37%. Moreover, DSC results showed a faster crystallinity rate due to the nanofiller acting as a nucleating agent and rheology tests indicated that low content of nano additive (2%) has better processability behavior, with suitable viscosity complex values at high frequencies.

Mechanical and Durability Properties of Portland Limestone Cement (PLC) Incorporated with Nano Calcium Carbonate (CaCO3).

Despite lower environmental impacts, the use of Portland Limestone Cement (PLC) concrete has been limited due to its reduced later age strength and compromised durability properties. This research evaluates the effects of nano calcium carbonate (CaCO3) on the performance of PLC concrete. The study follows a series of experiments on the fresh, hardened, and durability properties of PLC concrete with different replacement rates of nano CaCO3. Incorporation of 1% nano CaCO3 into PLC concrete provided the optimal performance, where the 56 days compressive strength was increased by approximately 7%, and the permeability was reduced by approximately 13% as compared to Ordinary Portland Cement (OPC) concrete. Further, improvements were observed in other durability aspects such as Alkali-Silica Reaction (ASR) and scaling resistance. Additionally, nano CaCO3 has the potential to be produced within the cement plant while utilizing the CO2 emissions from the cement industries. The integration of nanotechnology in PLC concrete thus will help produce a more environment-friendly concrete with enhanced performance. More in-depth study on commercial production of nano CaCO3 thus has the potential to offer a new generation cement-sustainable, economical, and durable cement-leading towards green infrastructure and global environmental sustainability.

Interface interaction between high-siliceous/calcareous mineral granules and model cell membranes dominated by electrostatic force.

High-siliceous/calcareous mineral granules may cause cytotoxicity by attaching to cell membranes. In this research, giant (GUVs) and small unilamellar vesicles (SUVs) were used as model membranes for studying the interaction between high-siliceous/calcareous mineral granules (micro calcite, micro quartz, nano calcium carbonate, and nano silica) and artificial membranes. Confocal laser scanning microscopy (CLSM) and fluorescence labeling experiments suggest that nano calcium carbonate (nano CaCO3) and nano silica (nano SiO2) induce gelation by disrupting the oppositely charged membranes, indicating the important role of electrostatic forces. Thereby, the mineral granule size affects the electrostatic interactions and thus leading to the damage of the membranes. FTIR spectra and molecular dynamics reveal that mineral granules mainly interact with -PO2-, -OH, and -C-N(CH3)3+ groups in phospholipids. The electrostatic force between nano minerals and phospholipids is greater in the case SiO2 when compared to CaCO3. Moreover, nano SiO2 forms the strongest hydrogen bond with the -PO2- group as confirmed by FTIR. Thus, nano SiO2 causes the greatest damage to membranes. This research provides a deeper understanding of the mechanism regarding the interaction between inhalable mineral granules and cell membranes.

Nano Calcium Carbonate (CaCO3) as a Reliable, Durable, and Environment-Friendly Alternative to Diminishing Fly Ash.

Fly ash is widely used in the cement industry to improve the performance and durability of concrete. The future availability of fly ash, however, is a concern, as most countries are inclining towards renewable energy sources as opposed to fossil fuels. Additional concerns have been raised regarding the impact of strict environmental regulations on fly ash quality and variability. This paper, therefore, evaluates if nano calcium carbonate (nano CaCO3) can be used as an alternative to fly ash. This paper presents comprehensive testing results (fresh, hardened, and durability) for OPC (Ordinary Portland Cement) and PLC (Portland Limestone Cement) concretes with 1% nano CaCO3 and compares them to those for concretes with fly ash (both Class F and C). Compared to concretes with fly ash, OPC and PLC with nano CaCO3 presented improved testing results in most cases, including later age strength, permeability, and scaling resistance. As nanotechnology in concrete is a relatively new topic, more research on the efficient use of nanotechnology, such as for proper dispersion of nano CaCO3 in the concrete, has potential to offer increased benefits. Further, nano CaCO3 is environmentally and economically viable, as it has the potential to be produced within the cement plant while utilizing waste CO2 and generating economic revenue to the industry. Thus, nano CaCO3 has the potential to serve as an alternative to fly ash in all beneficial aspects-economic, environmental, and technical.

Influence of Nano-SiO2, Nano-CaCO3 and Nano-Al2O3 on Rheological Properties of Cement-Fly Ash Paste.

Rheological curves of cement-fly ash (C-FA) paste incorporating nanomaterials including nano-SiO2 (NS), nano-CaCO3 (NC) and nano-Al2O3 (NA) at different resting times (hydration time of 5 min, 60 min, and 120 min) were tested with a rheometer. The rheological behaviors were described by the Herschel-Bulkley (H-B) model, and the influences of these nanomaterials on rheological properties of C-FA paste were compared. Results show that the types, content of nanomaterials and resting time have great influences on the rheological properties of C-FA paste. Incorporating NS and NA increases yield stress and plastic viscosity, and decreases the rheological index of C-FA paste. When the content of NS and NA were 2 wt%, the rheological index of C-FA paste was less than 1, indicating rheological behavior changes from shear thickening to shear thinning. Meanwhile, with rising resting time, yield stress and plastic viscosity increased significantly, but the rheological index decreased evidently, showing paste takes on shear thinning due to the rise of resting time. However, incorporating 3 wt% NC and the rising of resting time did not change the rheological properties of C-FA paste. These differences are mainly that the specific surface area (SSA) of NS (150 m2/g) and NA (120 m2/g) are much larger than that of NC (40 m2/g). The huge SSA of NS and NA consume lots of free water and these tiny particles accelerate the hydration process during resting time.

Pulmonary hypofunction due to calcium carbonate nanomaterial exposure in occupational workers: a cross-sectional study.

Calcium carbonate nanomaterials (nano-CaCO3) are widely used in both manufacturing and consumer products, but their potential health hazards remain unclear. The objective of this study was to survey workplace exposure levels and health effects of workers exposed to nano-CaCO3. Personal and area sampling, as well as real-time and dust monitoring, were performed to characterize mass exposure, particle size distribution, and particle number exposure. A total of 56 workers (28 exposed workers and 28 unexposed controls) were studied in a cross-sectional study. They completed physical examinations, spirometry, and digital radiography. The results showed that the gravimetric nano-CaCO3 concentration was 5.264 ± 6.987 mg/m3 (0.037-22.192 mg/m3) at the workplace, and 3.577 ± 2.065 mg/m3 (2.042-8.161 mg/m3) in the breathing zone of the exposed workers. The particle number concentrations ranged from 8193 to 39 621 particles/cm3 with a size range of 30-150 nm. The process of packing had the highest gravimetric and particle number concentrations. The particle number concentration positively correlated with gravimetric concentrations of nano-CaCO3. The levels of hemoglobin, creatine phosphokinase (CK), lactate dehydrogenase, and high-density lipoprotein cholesterol (HDL-C) in the nano-CaCO3 exposure group increased significantly, but the white blood cell count (WBC), Complement 3 (C3), total protein (TP), uric acid, and creatinine (CREA) all decreased significantly. The prevalence rate of pulmonary hypofunction was significantly higher (p = 0.037), and the levels of vital capacity (VC), forced vital capacity (FVC), forced expiratory volume in one second (FEV1), FEV1/FVC, peak expiratory flow and forced expiratory flow 25% (FEF 25%), FEF 25-75% were negatively correlated with gravimetric concentrations of nano-CaCO3 (p < 0.05). Logistic analysis showed that nano-CaCO3 exposure level was associated with pulmonary hypofunction (p = 0.005). Meanwhile, a dose-effect relationship was found between the accumulated gravimetric concentrations of nano-CaCO3 and the prevalence rate of pulmonary hypofunction (p = 0.048). In conclusion, long-term and high-level nano-CaCO3 exposure can induce pulmonary hypofunction in workers. Thus, lung function examination is suggested for occupational populations with nano-CaCO3 exposure. Furthermore, future health protection efforts should focus on senior workers with accumulation effects of nano-CaCO3 exposure.