Characterization of a Novel CaCO3-Forming Alkali-Tolerant Rhodococcus erythreus S26 as a Filling Agent for Repairing Concrete Cracks

Biomineralization, a well-known natural phenomenon associated with various microbial species, is being studied to protect and strengthen building materials such as concrete. We characterized Rhodococcus erythreus S26, a novel urease-producing bacterium exhibiting CaCO₃-forming activity, and investigated its ability in repairing concrete cracks for the development of environment-friendly sealants. Strain S26 grown in solid medium formed spherical and polygonal CaCO₃ crystals. The S26 cells grown in a urea-containing liquid medium caused culture fluid alkalinization and increased CaCO₃ levels, indicating that ureolysis was responsible for CaCO₃ formation. Urease activity and CaCO₃ formation increased with incubation time, reaching a maximum of 2054 U/min/mL and 3.83 g/L, respectively, at day four. The maximum CaCO₃ formation was achieved when calcium lactate was used as the calcium source, followed by calcium gluconate. Although cell growth was observed after the induction period at pH 10.5, strain S26 could grow at a wide range of pH 4–10.5, showing its high alkali tolerance. FESEM showed rhombohedral crystals of 20–60 µm in size. EDX analysis indicated the presence of calcium, carbon, and oxygen in the crystals. XRD confirmed these crystals as CaCO₃ containing calcite and vaterite. Furthermore, R. erythreus S26 successfully repaired the artificially induced large cracks of 0.4–0.6 mm width.     

LDPE Transformation by Exposure to Sequential Low-Pressure Plasma and TiO2/UV Photocatalysis

Low-density polyethylene (LDPE) sheets (3.0 ± 0.1 cm) received sequential treatment, first by the action of direct-current low-pressure plasma (DC-LPP) with a 100% oxygen partial pressure, 3.0 × 10⁻² mbar pressure, 600 V DC tension, 5.6 cm distance, 6-min treatment. Then, sheets were submitted to TiO₂ photocatalysis at UV radiation at 254 nm (TiO₂/UV) with a pH value of 4.5 ± 0.2 and a TiO₂ concentration of 1 gL⁻¹. We achieved a complementary effect on the transformation of LDPE films. With the first treatment, ablation was generated, which increased hydrophilicity. With the second treatment, the cavities appeared. The changes in the LDPE sheets’ hydrophobicity were measured using the static contact angle (SCA) technique. The photocatalytic degradation curve at 400 h revealed that the DC-LPP photocatalysis sequential process decreased SCA by 82°. This was achieved by the incorporation of polar groups, which increased hydrophilicity, roughness, and rigidity by 12 and 38%, respectively. These sequential processes could be employed for LDPE and other material biodegradation pretreatment.     

Synthesis of Zn2+-Pre-Intercalated V2O5·nH2O/rGO Composite with Boosted Electrochemical Properties for Aqueous Zn-Ion Batteries

Layered vanadium-based materials are considered to be great potential electrode materials for aqueous Zn-ion batteries (AZIBs). The improvement of the electrochemical properties of vanadium-based materials is a hot research topic but still a challenge. Herein, a composite of Zn-ion pre-intercalated V₂O₅·nH₂O combined with reduced graphene oxide (ZnVOH/rGO) is synthesized by a facile hydrothermal method and it shows improved Zn-ion storage. ZnVOH/rGO delivers a capacity of 325 mAh·g⁻¹ at 0.1 A·g⁻¹, and this value can still reach 210 mAh·g⁻¹ after 100 cycles. Additionally, it exhibits 196 mAh·g⁻¹ and keeps 161 mAh·g⁻¹ after 1200 cycles at 4 A·g⁻¹. The achieved performances are much higher than that of ZnVOH and VOH. All results reveal that Zn²⁺ as “pillars” expands the interlayer distance of VOH and facilitates the fast kinetics, and rGO improves the electron flow. They both stabilize the structure and enhance efficient Zn²⁺ migration. All findings demonstrate ZnVOH/rGO’s potential as a perspective cathode material for AZIBs.     

Stability of Manganese(II)–Pyrazine, –Quinoxaline or –Phenazine Complexes and Their Potential as Carbonate Sequestration Agents

Carbonate sequestration technology is a complement of CO₂ sequestration technology, which might assure its long-term viability. In this work, in order to explore the interactions between Mn²⁺ ion with several ligands and carbonate ion, we reported a spectrophotometric equilibrium study of complexes of Mn²⁺ with pyrazine, quinoxaline or phenazine and its carbonate species at 298 K. For the complexes of manganese(II)–pyrazine, manganese(II)–quinoxaline and manganese(II)–phenazine, the formation constants obtained were log β₁₁₀ = 4.6 ± 0.1, log β₁₁₀ = 5.9 ± 0.1 and log β₁₁₀ = 6.0 ± 0.1, respectively. The formation constants for the carbonated species manganese(II)–carbonate, manganese(II)–pyrazine–carbonate, manganese(II)–quinoxaline–carbonate and manganese(II)–phenazine–carbonate complexes were log β₁₁₀ = 5.1 ± 0.1, log β₁₁₀ = 9.8 ± 0.1, log β₁₁₀ = 11.7 ± 0.1 and log β₁₁₀ = 12.7 ± 0.1, respectively. Finally, the individual calculated electronic spectra and its distribution diagram of these species are also reported. The use of N-donor ligand with π-electron-attracting activity in a manganese(II) complex might increase its interaction with carbonate ions.     

Response Surface Optimisation of Polydimethylsiloxane (PDMS) on Borosilicate Glass and Stainless Steel (SS316) to Increase Hydrophobicity

Particle deposition on the surface of a drying chamber is the main drawback in the spray drying process, reducing product recovery and affecting the quality of the product. In view of this, the potential application of chemical surface modification to produce a hydrophobic surface that reduces the powder adhesion (biofouling) on the wall of the drying chamber is investigated in this study. A hydrophobic polydimethylsiloxane (PDMS) solution was used in the vertical dipping method at room temperature to determine the optimum coating parameters on borosilicate glass and stainless steel substrates, which were used to mimic the wall surface of the drying chamber, to achieve highly hydrophobic surfaces. A single-factor experiment was used to define the range of the PDMS concentration and treatment duration using the Response Surface Methodology (RSM). The Central Composite Rotatable Design (CCRD) was used to study the effects of the concentration of the PDMS solution (X₁, %) and the treatment duration (X₂, h) on the contact angle of the substrates (°), which reflected the hydrophobicity of the surface. A three-dimensional response surface was constructed to examine the influence of the PDMS concentration and treatment duration on contact angle readings, which serve as an indicator of the surface’s hydrophobic characteristics. Based on the optimisation study, the PDMS coating for the borosilicate glass achieved an optimum contact angle of 99.33° through the combination of a PDMS concentration of X₁ = 1% (w/v) and treatment time of X₂ = 4.94 h, while the PDMS coating for the stainless steel substrate achieved an optimum contact angle of 98.31° with a PDMS concentration of X₁ = 1% (w/v) and treatment time of X₂ = 1 h. Additionally, the infrared spectra identified several new peaks that appeared on the PDMS-treated surfaces, which represented the presence of Si-O-Si, Si-CH₃, CH₂, and CH₃ functional groups for the substrates coated with PDMS. Furthermore, the surface morphology analysis using the Field Emission Scanning Electron Microscopy (FESEM) showed the presence of significant roughness and a uniform nanostructure on the surface of the PDMS-treated substrates, which indicates the reduction in wettability and the potential effect of unwanted biofouling on the spray drying chamber. The application of PDMS and PTFE on the optimally coated substrates successfully reduced the amount of full cream milk particles that adhered to the surface. The low surface energy of the treated surface (19–27 mJ/m²) and the slightly higher surface tension of the full cream milk (54–59 mJ/m²) resulted in a high contact angle (102–103°) and reduced the adhesion work on the treated substrates (41–46 mJ/m²) as compared to the native substrates.     

Negating Na‖Na3Zr2Si2PO12 interfacial resistance for dendrite-free and “Na-less” solid-state batteries

Solid electrolytes hold promise in safely enabling high-energy metallic sodium (Na) anodes. However, the poor Na‖solid electrolyte interfacial contact can induce Na dendrite growth and limit Na utilization, plaguing the rate performance and energy density of current solid-state Na-metal batteries (SSSMBs). Herein, a simple and scalable Pb/C interlayer strategy is introduced to regulate the surface chemistry and improve Na wettability of Na₃Zr₂Si₂PO₁₂ (NZSP) solid electrolyte. The resulting NZSP exhibits a perfect Na wettability (0° contact angle) at a record-low temperature of 120 °C, a negligible room-temperature Na‖NZSP interfacial resistance of 1.5 Ω cm², along with an ultralong cycle life of over 1800 h under 0.5 mA cm⁻²/0.5 mA h cm⁻² symmetric cell cycling at 55 °C. Furthermore, we unprecedentedly demonstrate in situ fabrication of weight-controlled Na anodes and explore the effect of the negative/positive capacity (N/P) ratio on the cyclability of SSSMBs. Both solid-state Na₃V₂(PO₄)₃ and S full cells show superior electrochemical performance at an optimal N/P ratio of 40.0. The Pb/C interlayer modification demonstrates dual functions of stabilizing the anode interface and improving Na utilization, making it a general strategy for implementing Na metal anodes in practical SSSMBs.

A novel Pb/C interlayer is introduced on Na₃Zr₂Si₂PO₁₂ solid electrolyte, which offers perfect Na wettability, negates interfacial resistance, and allows in situ fabrication of “Na-less” anodes for stable solid-state Na-metal batteries.     

Development and characterization of poly ethyl metha acrylate–iron oxide(III) based hydrophobic liquid nanocomposite films

Select applications of hydrophobic nanocomposites include preparation of robust self-cleaning surfaces, water-repellent glass surfaces, and waterproofing textiles. Various nanocomposites have been reported in the literature; however, the relationship between the nanocomposite surface morphology and its hydrophobicity needs to be understood better. In the present work Fe₂O₃ nanoparticles and poly ethyl metha acrylate (PEMA) were used in varying proportions to obtain a series of model hydrophobic surfaces (spin-coated on glass substrate). The hydrophobicity of these surfaces was measured by static contact angle; a maximum of 103° was obtained at highest loading of iron oxide nanoparticles. These surfaces were also characterized using AFM. The contact angle and characterization data were used to test some of the models which have been proposed in the recent literature on prediction of contact angle for composite surfaces. It is proposed that the hydrophobicity of the iron oxide–PEMA surface is due to the physical roughness causing air entrapment as well as the chemical heterogeneity. Based on the experimental studies and the simulations using the recent models on contact angle, some general features of relationship between a composite surface morphology and its hydrophobicity is proposed.     

Biomimetic synthesis of calcium carbonate with different morphologies under the direction of different amino acids

Using three different amino acids (AAs) as organic matrices, including the highly nonpolar hydrophobic l-valine, the positively charged l-arginine and the less polar uncharged l-serine, calcium carbonate (CaCO₃) with different morphologies and polymorphs were synthesized by a facile gas diffusion reaction based on biomimetic strategy. Compared with the control cubic calcite obtained in the absence of AAs, the product from l-valine was cubic calcite aggregates assembled by nano-platelets. The product from l-arginine was spherical vaterite aggregates assembled by spherical nanoparticles. The product from l-serine was the mixture of cubic calcite and spherical vaterite. The structures and properties of the side chains of the AAs exerted the significant effects on the nucleation and growth of the CaCO₃. The formation mechanisms of the CaCO₃ in the presence of AAs are preliminarily discussed. The results suggest that the polymorphs and morphologies of the inorganic nanomaterials might be easily adjusted through the careful selection of the organic matrices.     

Fabrication of Fe3O4@SiO2 nanocomposites to enhance anticorrosion performance of epoxy coatings

SiO₂‐coated Fe₃O₄ (Fe₃O₄@SiO₂) nanocomposites were prepared by sol–gel method, and the anticorrosion performance of composite coatings was discussed. The structure of the Fe₃O₄@SiO₂ nanocomposites was verified through Fourier transform infrared, X‐ray diffraction, and scanning electron microscopy. Composite epoxy coatings with same concentrations of Fe₃O₄ and Fe₃O₄@SiO₂ were measured by scanning electron microscopy contact angle meter. More importantly, the Fe₃O₄@SiO₂ nanocomposites not only obtained a homogeneous dispersion and compatibility in epoxy resin but also exhibited an obvious superiority in enhancing the anticorrosion performance of epoxy coatings. Furthermore, the anticorrosion mechanism of Fe₃O₄@SiO₂/epoxy composite coating was tentatively discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Membrane distillation operated at high seawater concentration factors: Role of the membrane on CaCO3 scaling in presence of humic acid

This study aims at investigating the kinetics of calcium carbonate precipitation (scaling), that occurs in the form of vaterite, when treating seawater by direct contact membrane distillation (DCMD) operated at high concentration factors (from 4 to 6). Induction time measurements carried out by dynamic light scattering (DLS) allowed to identify the shifting between homogeneous and heterogeneous nucleation mechanisms as a function of supersaturation. CaCO₃ interfacial energy, evaluated for concentrated seawater solutions as 45 mJ/m², increased by 7% as a consequence of the inhibition effect of humic acid, and it was reduced to 32 mJ/m² in correspondence of heterogeneous nucleation occurring on microporous polypropylene membranes. Gibbs free energy barrier to the formation of critical nuclei was predicted with good accuracy as a function of physico-chemical properties of the membrane (porosity: 0.70, contact angle: 115 ± 2°).     

In-site mineralization of amorphous calcium carbonate particles: A facile and efficient approach to fabricate poly(l-lactic acid) based hybrids

The aim of this investigation is to obtain a polymer-based hybrid material with biodegradability, biocompatibility, and good mechanical properties and this object was realized via. in-situ introduction of the unmodified calcium carbonate (CaCO₃) into a poly(l-lactic acid) (PLLA) matrix. As verified by the measurements from scanning electron microscopy (SEM), optical microscopy, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), the hybrid films which possesses a uniform dispersion of calcium carbonate CaCO₃ in nano-meter scale, mechanically robustness and thermal stability could be fabricated by a mineralization-alike process. For example, the storage modulus increases from 441 MPa of neat PLLA to 1034 MPa of hybrid film containing 2% (w/w) CaCO₃. In addition, the hybrid films display a significant improvement in its UV-exposure resistance.     

Thermal Preparation and Application of a Novel Silicon Fertilizer Using Talc and Calcium Carbonate as Starting Materials

The deficiency of available silicon (Si) incurred by year-round agricultural and horticultural practices highlights the significance of Si fertilization for soil replenishment. This study focuses on a novel and economical route for the synthesis of Si fertilizer via the calcination method using talc and calcium carbonate (CaCO₃) as starting materials. The molar ratio of talc to CaCO₃ of 1:2.0, calcination temperature of 1150 °C and calcination time of 120 min were identified as the optimal conditions to maximize the available Si content of the prepared Si fertilizer. X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) characterizations elucidate the principles of the calcination temperature-dependent microstructure evolution of Si fertilizers, and the akermanite Ca₂Mg(Si₂O₇) and merwinite Ca₃Mg(SiO₄)₂ were identified as the primary silicates products. The results of release and solubility experiments suggest the content of available metallic element and slow-release property of the Si fertilizer obtained at the optimum preparation condition (Si-OPC). The surface morphology and properties of Si-OPC were illuminated by the results of scanning electron microscope (SEM), surface area and nitrogen adsorption analysis. The acceleration action of CaCO₃ in the decomposition process of talc was demonstrated by the thermogravimetry-differential scanning calorimetry (TG-DSC) test. The pot experiment corroborates that 5 g kg⁻¹ soil Si-OPC application sufficed to facilitate the pakchoi growth by providing nutrient elements. This evidence indicates the prepared Si fertilizer as a promising candidate for Si-deficient soil replenishment.     

Investigation into the Structural,Chemical and High Mechanical Reforms in B4C with Graphene Composite Material Substitution for Potential Shielding Frame Applications

In this work, boron carbide and graphene nanoparticle composite material (B₄C–G) was investigated using an experimental approach. The composite material prepared with the two-step stir casting method showed significant hardness and high melting point attributes. Scanning electron microscopy (SEM), along with energy dispersive X-ray spectroscopy (EDS) analysis, indicated 83.65%, 17.32%, and 97.00% of boron carbide + 0% graphene nanoparticles chemical compositions for the C-atom, Al-atom, and B₄C in the compound studied, respectively. The physical properties of all samples’ B₄C–G like density and melting point were 2.4 g/cm³ density and 2450 °C, respectively, while the grain size of B₄C–G was in the range of 0.8 ± 0.2 µm. XRD, FTIR, and Raman spectroscopic analysis was also performed to investigate the chemical compositions of the B₄C–G composite. The molding press composite machine was a fabrication procedure that resulted in the formation of outstanding materials by utilizing the sintering process, including heating and pressing the materials. For mechanical properties, high fracture toughness and tensile strength of B₄C–G composites were analyzed according to ASTM standard designs. The detailed analysis has shown that with 6% graphene content in B₄C, the composite material portrays a high strength of 134 MPa and outstanding hardness properties. Based on these findings, it is suggested that the composite materials studied exhibit novel features suitable for use in the application of shielding frames.     

In-Situ Synthesis and Characterization of Nanocomposites in the Si-Ti-N and Si-Ti-C Systems

The pyrolysis (1000 °C) of a liquid poly(vinylmethyl-co-methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000–1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere. Then, the structural evolution of the amorphous network of ammonia-, nitrogen- and argon-treated ceramics has been studied above 1000 °C under nitrogen and argon by X-ray diffraction and electron microscopy. HRTEM images coupled with XRD confirm the formation of nanocomposites after annealing at 1400 °C. Their unique nanostructural feature appears to be the result of both the molecular origin of the materials and the nature of the atmosphere used during pyrolysis. Samples are composed of an amorphous Si-based ceramic matrix in which TiN_xC_y nanocrystals (x + y = 1) are homogeneously formed “in situ” in the matrix during the process and evolve toward fully crystallized compounds as TiN/Si₃N₄, TiN_xC_y (x + y = 1)/SiC and TiC/SiC nanocomposites after annealing to 1800 °C as a function of the atmosphere.     

碳酸岩矿化菌诱导碳酸钙晶体形成机理研究

选用碳酸盐矿化菌(芽孢杆菌系), 分别研究了不同浓度细菌液、细菌体及其分泌物对碳酸钙晶体形成的影响. 研究表明, 细菌液浓度越高, 控制碳酸钙晶体形貌作用越显著; 细菌体为碳酸钙结晶提供异相成核点而对形貌并没有实质影响; 细菌分泌物可诱导出球形、纺锤形等多种形态亚稳态球霰石; 在微生物环境的长期作用下可形成有机-无机复合碳酸钙硬质膜. 通过对电导率测定结果和碳酸钙红外图谱分析得出, 生物有机质分子链的极性基团(COOH, C＝O等)与Ca^2＋产生静电、配位等一系列作用, 调控晶体的生长. 本研究对于微生物诱导碳酸钙的工程性应用, 如混凝土微裂缝修复、古建筑表面防护处理、微纳米碳酸钙颗粒制备等具有一定指导意义.     

Design and synthesis of optically transparent calcium‐incorporated polymer complexes

Transparent thin films of calcium‐ion‐incorporated polymer composites were synthesized with calcium carbonate (CaCO₃) and polymers such as poly(acrylic acid) (PAA), poly(ethylene glycol) (PEG), and methylcellulose. The homogeneous distribution of Ca²⁺ in the composite films was observed because of the high concentration of COO^? groups along the PAA backbone for the complexation of Ca²⁺ ions. The optical transparency of the composites depends on the weight percentages of the three polymers and the molar concentration of CaCO₃ in the composites. Maximum transparency was obtained for a composite film with a PAA/CaCO₃ ratio of 9:1. The results indicated that methylcellulose improved the film‐forming capabilities and that PEG improved the transparency of the composites. All polymer complexes were characterized with X‐ray diffraction, fourier transfer infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, dynamic mechanical analysis, and optical transparency measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4459–4465, 2004     

Supramolecular Diiodine-Bromostannate(IV) Complexes: Narrow Bandgap Semiconductors

Three supramolecular bromostannates(IV) with “trapped” diiodine molecules, Cat₂{[SnBr₆](I₂)} (Cat = Me₄N⁺ (1), 1-MePy⁺ (2) and 4-MePyH (3)), were synthesized. In all cases, I₂ linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles 1–3 were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The latter indicates that 1–3 are narrow band gap semiconductors.     

Ultrasound-Assisted Water Extraction of Gentiopicroside,Isogentisin, and Polyphenols from Willow Gentian “Dust” Supported by Hydroxypropyl-β-Cyclodextrin as Cage Molecules

The residue after sieving (“dust”) from the willow gentian underground parts is an unexploited herbal tea by-product, although it contains valuable bioactive compounds. Cyclodextrins as efficient green co-solvents, cage molecules, and multifunctional excipients could improve the extraction and contribute to the added value of the resulting extracts. The objective of this study was to determine the optimal conditions for the extraction of gentiopicroside, isogentisin, and total phenolics (TPC) from willow gentian “dust” using ultrasound-assisted water extraction coupled with hydroxypropyl-β-cyclodextrin (HPβCD). The influence of extraction temperature (X₁: 20–80 °C), time (X₂: 20–50 min), and HPβCD concentration (X₃: 2–4% w/v) was analyzed employing the response surface methodology (RSM). The optimal extraction conditions for simultaneously maximizing the extraction yield of all monitored responses were X₁: 74.89 °C, X₂: 32.57 min, and X₃: 3.01% w/v. The experimentally obtained response values under these conditions (46.96 mg/g DW for gentiopicroside, 0.51 mg/g DW for isogentisin, and 12.99 mg GAE/g DW for TPC) were in close agreement with those predicted, thus confirming the suitability and good predictive accuracy of the developed RSM models. Overall, the developed extraction system could be an applicable alternative strategy to improve the extraction of bioactive compounds from the underutilized “dust” of willow gentian underground parts.     

<Emphasis Type="Italic">In situ</Emphasis> synthesis and modification of calcium carbonate nanoparticles via a bobbling method

Modified calcium carbonate (CaCO₃) nanoparticles with cubic- and spindle-like configuration were synthesized in situ by the typical bobbling (gas-liquid-solid) method. The modifiers, such as sodium stearate, octadecyl dihydrogen phosphate (ODP) and oleic acid (OA), were used to obtain hydrophobic nanoparticles. The different modification effects of the modifiers were investigated by measuring the active ratio, whiteness and the contact angle. Moreover, transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetry analysis (TGA analysis) were employed to characterize the obtained products. A preliminary reaction mechanism was discussed. According to the results, the active ratio of CaCO₃ modified by ODP was ca. 99.9% and the value of whiteness was 97.3% when the dosage of modifiers reached 2%. The contact angle was 122.25° for the CaCO₃ modified in the presence of sodium stearate, ODP and OA. When modified CaCO₃ was filled into PVC, the mechanical properties of products were improved greatly such as rupture intensity, pull intensity and fuse temperature. The compatibility and affinity between the modified CaCO₃ nanoparticles and the organic matrixes were greatly improved. Supported by the National Natural Science Foundation of China (Grant No. 50372025)