Construction of 1,3,5-Triazine-Based Prisms and Their Enhanced Solid-State Emissions.

In this study, two trigonal prisms based on the 1,3,5-triazine motif (SA and SB), distinguished by hydrophobic groups, were prepared by the self-assembly of tritopic terpyridine ligands and Zn(II) ions. SA and SB exhibited high luminescence efficiencies in the solid state, overcoming the fluorescence quenching of the 1,3,5-triazine group caused by π-π interactions. Notably, SA and SB exhibited different luminescence behaviors in the solution state and aggregation state. SB with 12 alkyl chains exhibited extremely weak fluorescence in a dilute solution, but its fluorescence intensity and photoluminescence quantum yield (PLQY) were significantly enhanced in the aggregated state (with the increase in the water fraction), especially in the solid state. Different from the gradually enhanced efficiency of SB, the PLQY of SA gradually decreased with the increase in aggregation but still maintained a high luminescence efficiency. These two complexes exhibited different modes to solve the fluorescence quenching of 1,3,5-triazine in the solid state. The hierarchical self-assembly of SB exhibited nanorods owing to the hydrophobic interactions of alky chains, while SA aggregated into spheres under the influence of π-π interactions.

Multi-Decker Emissive Supramolecular Architectures Based on Shape-Complementary Ligands Pair.

Dye aggregates have attracted a great deal of attention due to their widespread applications in organic light-emitting devices, light-harvesting systems, etc. However, the strategies to precisely control chromophores with specific spatial arrangements still remain a great challenge. In this work, a series of double- and triple-decker supramolecular complexes are successfully constructed by coordination-driven self-assembly of carefully designed shape-complementary ligands, one claw-like tetraphenylethylene (TPE)-based host ligand and three tetratopic or ditopic guest ligands. The spatial configurations of these assemblies (one double-decker and three "S-shaped" or "X-shaped" triple-decker structures) depend on the angles of these TPE-derived ligands. Notably, the three triple-decker structures are geometric isomers. Furthermore, photophysical studies show that these complexes exhibit different ratios of radiative (kr ) and non-radiative (knr ) rate constant due to the different spatial arrangements of TPE moieties. This study provides not only a unique strategy for the construction of multi-stacks with specific spatial arrangement, but also a promising platform for investigating the aggregation behavior of fluorescent chromophores.

Cement-Based Piezoelectric Ceramic Composites for Sensing Elements: A Comprehensive State-of-the-Art Review.

Compatibility, a critical issue between sensing material and host structure, significantly influences the detecting performance (e.g., sensitive, signal-to-noise ratio) of the embedded sensor. To address this issue in concrete-based infrastructural health monitoring, cement-based piezoelectric composites (piezoelectric ceramic particles as a function phase and cementitious materials as a matrix) have attracted continuous attention in the past two decades, dramatically exhibiting superior durability, sensitivity, and compatibility. This review paper performs a synthetical overview of recent advances in theoretical analysis, characterization and simulation, materials selection, the fabrication process, and application of the cement-based piezoelectric composites. The critical issues of each part are also presented. The influencing factors of the materials and fabrication process on the final performance of composites are further discussed. Meanwhile, the application of the composite as a sensing element for various monitoring techniques is summarized. Further study on the experiment and simulation, materials, fabrication technique, and application are also pointed out purposefully.

Enhanced calcite precipitation for crack healing by bacteria isolated under low-nitrogen conditions.

A nitrogen-starving isolation strategy was developed for the first time to screen bacteria with high calcium-precipitating activity (CPA) for bioremediation of damage in porous media. Meanwhile, a novel mini-tube method based on the detection of insoluble Ca2+ was established to evaluate the CPA of the isolates. A low-nitrogen-demanding strain B6, identified as Bacillus sp., was screened to exhibit the highest CPA (55 mM insoluble Ca2+). Furthermore, the effects of environmental factors and nutrient availability on B6-induced calcium precipitation were evaluated. The results show that nitrate and starch are the best nitrogen source and carbon source with optimal concentration being 4 and 2 g L-1, respectively. The suitable pH range for B6 to precipitate calcium is from 8.5 to 10.5. B6 can maintain the highest CPA at an initial spore concentration of 1.0 × 108 spores·mL-1. The optimal CaO2 dosage is 10 g L-1. Finally, the calcite precipitation is confirmed by ESEM, EDS, and XRD analysis.

Nitrogen Atom Induced Contrast Effect on the Mechanofluorochromic Characteristics of Anthracene-Based Acceptor-Donor-Acceptor Fluorescent Molecules.

The mechanofluorochromic (MFC) characteristics of anthracene-based acceptor-donor-acceptor (A-D-A) fluorescent molecules are explored through a comprehensive investigation of their photophysical behaviors. Six 9,10-diheteroarylanthracene derivatives with varying acceptor groups (pyridin-4-yl, pyridin-3-yl, pyridin-2-yl, pyrimidin-5-yl, pyrazinyl and quinoxalinyl) are synthesized and systematically characterized. The photophysical properties in both solution and solid-state are examined, revealing subtle yet significant influences of the spatial arrangement and number of nitrogen atoms within the acceptor group on fluorescence emission. Single-crystal structures of these compounds provide insights into their steric configurations and intermolecular packing modes, offering valuable insights into the fundamental mechanisms that underlie the observed MFC properties. This study illuminates the intricate interplay between MFC properties and the refined molecular structure, thus presenting promising avenues for the design and advancement of novel MFC materials.

Construction of metallo-triangles with cis-TPE motifs and fluorescence properties.

Two metallo-triangles, SA and SB, with cis-TPE motifs were constructed, and their fluorescence properties were explored. Compared with the dilute solution, both triangles SA and SB exhibited significant AIE behavior in the aggregated states. Moreover, the shorter version SA showed higher quantum yields than SB in the aggregated states.

Molecular Dynamics Study on Mechanical Properties of Interface between Urea-Formaldehyde Resin and Calcium-Silicate-Hydrates.

Microcapsule based self-healing concrete can automatically repair damage and improve the durability of concrete structures, the performance of which depends on the binding behavior between the microcapsule wall and cement matrix. However, conventional experimental methods could not provide detailed information on a microscopic level. In this paper, through molecular dynamics simulation, three composite models of Tobermorite (Tobermorite 9 Å, Tobermorite 11 Å, Tobermorite 14 Å), a mineral similar to Calcium-Silicate-Hydrate (C-S-H) gel, with the linear urea-formaldehyde (UF), the shell of the microcapsule, were established to investigate the mechanical properties and interface binding behaviour of the Tobermorite/UF composite. The results showed that the Young's modulus, shear modulus and bulk modulus of Tobermorite/UF were lower than that of 'pure' Tobermorite, whereas the tensile strength and failure strain of Tobermorite/UF were higher than that of 'pure' Tobermorite. Moreover, through radial distribution function (RDF) analysis, the connection between Tobermorite and UF found a strong interaction between Ca, N, and O, whereas Si from Tobermorite and N from UF did not contribute to the interface binding strength. Finally, high binding energy between the Tobermorite and UF was observed. The research results should provide insights into the interface behavior between the microcapsule wall and the cement matrix.

Microstructure and Thermal Reliability of Microcapsules Containing Phase Change Material with Self-Assembled Graphene/Organic Nano-Hybrid Shells.

In recent decades, microcapsules containing phase change materials (microPCMs) have been the center of much attention in the field of latent thermal energy storage. The aim of this work was to prepare and investigate the microstructure and thermal conductivity of microPCMs containing self-assembled graphene/organic hybrid shells. Paraffin was used as a phase change material, which was successfully microencapsulated by graphene and polymer forming hybrid composite shells. The physicochemical characters of microPCM samples were investigated including mean size, shell thickness, and chemical structure. Scanning electron microscope (SEM) results showed that the microPCMs were spherical particles and graphene enhanced the degree of smoothness of the shell surface. The existence of graphene in the shells was proved by using the methods of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). It was found that graphene hybrid shells were constructed by forces of electric charge absorption and long-molecular entanglement. MicroPCMs with graphene had a higher degradation temperature of 300 °C. Graphene greatly enhanced the thermal stability of microPCMs. The thermal conductivity tests indicated that the phase change temperature of microPCMs was regulated by the graphene additive because of enhancement of the thermal barrier of the hybrid shells. Differential scanning calorimetry (DSC) tests proved that the latent thermal energy capability of microPCMs had been improved with a higher heat conduction rate. In addition, infrared thermograph observations implied that the microPCMs had a sensitivity response to heat during the phase change cycling process because of the excellent thermal conductivity of graphene.

Experimental Study on Mechanical Properties and Porosity of Organic Microcapsules Based Self-Healing Cementitious Composite.

Encapsulation of healing agents embedded in a material matrix has become one of the major approaches for achieving self-healing function in cementitious materials in recent years. A novel type of microcapsules based self-healing cementitious composite was developed in Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, Shenzhen University. In this study, both macro performance and the microstructure of the composite are investigated. The macro performance was evaluated by employing the compressive strength and the dynamic modulus, whereas the microstructure was represented by the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter, which are significantly correlated to the pore-size distribution and the compressive strength. The results showed that both the compressive strength and the dynamic modulus, as well as the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter of the specimen decrease to some extent with the amount of microcapsules. However, the self-healing rate and the recovery rate of the specimen performance and the pore-structure parameters increase with the amount of microcapsules. The results should confirm the self-healing function of microcapsules in the cementitious composite from macroscopic and microscopic viewpoints.

Optimization of a Binary Concrete Crack Self-Healing System Containing Bacteria and Oxygen.

An optimized strategy for the enhancement of microbially induced calcium precipitation including spore viability ensurance, nutrient selection and O2 supply was developed. Firstly, an optimal yeast extract concentration of 5 g/l in sporulation medium was determined based on viable spore yield and spore viability. Furthermore, the effects of certain influential factors on microbial calcium precipitation process of H4 in the presence of oxygen releasing tablet (ORT) were evaluated. The results showed that CaO2 is preferable to other peroxides in improving the calcium precipitation by H4. H4 strain is able to precipitate a highly insoluble calcium at the CaO2 dosage range of 7.5-12.5 g/l, and the most suitable spore concentration is 6 × 108 spores/ml when the spore viability (viable spore ratio) is approximately 50%. Lactate is the best carbon source and nitrate is the best nitrogen source for aerobic incubation. This work has laid a foundation of ternary self-healing system containing bacteria, ORT, and nutrients, which will be promising for the self-healing of cracks deep inside the concrete structure.

A Comprehensive Review of the Study and Development of Microcapsule Based Self-Resilience Systems for Concrete Structures at Shenzhen University.

A review of the research activities and achievements at Shenzhen University is conducted in this paper concerning the creation and further development of novel microcapsule based self-resilience systems for their application in concrete structures. After a brief description of pioneering works in the field starting about 10 years ago, the principles raised in the relevant research are examined, where fundamental terms related to the concept of resilience are discussed. Several breakthrough points are highlighted concerning the three adopted comprehensive self-resilience systems, namely physical, chemical and microbial systems. The major challenges regarding evaluation are emphasized and further development concerning self-resilience in concrete structures will be addressed.

Evaluating and Modeling the Internal Diffusion Behaviors of Microencapsulated Rejuvenator in Aged Bitumen by FTIR-ATR Tests.

Microencapsulated rejuvenator has been attracted much attention for self-healing bitumen. The diffusion coefficient is one of the key parameters to estimate the feasibility of rejuvenator to age bitumen. The objective of this research was to evaluate diffusion behaviors of microencapsulated rejuvenator in aged bitumen by a FTIR-ATR method. Various microcapsule samples were mixed in bitumen to form thin films. The core material of microcapsules used as rejuvenator was diphenylsilane (DPS), its fairly specific absorption band at 843 cm-1 was selected as a marker band to calculate the diffusion coefficient (D). The microstructure parameters, including contents, mean size and mean shell thickness of microcapsules, were considered to understand the diffusion behaviors under different temperatures (20, 30, 40 and 50 °C) in bitumen. The results showed that a larger mean size of microcapsules did not greatly affect the D values under the same temperature. In contrast, a higher mean shell thickness decreased the D values because of the decrement of damage probability of microcapsules under the same content. With the same microcapsule sample in bitumen, the D values presented a trend of linear increase when the content of microcapsules was increased. All these results indicated that the microstructure affected the diffusion behaviors based on the concentration of released rejuvenator. A preliminary model of diffusion behaviors of microencapsulated rejuvenator in bitumen was given based on the Arrhenius equation considering the microstructure of microcapsules, the amount of released rejuvenator and the age degree of bitumen. This model may be a guide to the construction and application of self-healing bitumen using microcapsules.

Investigation of the Self-Healing Behaviors of Microcapsules/Bitumen Composites by a Repetitive Direct Tension Test.

The aim of this work was to evaluate the self-healing behaviors of bitumen using microcapsules containing rejuvenator by a modified fracture healing-refracture method through a repetitive tension test. Microcapsules had mean size values of 10, 20 and 30 µm with a same core/shell ratio of 1/1. Various microcapsules/bitumen samples were fabricated with microcapsule contents of 1.0, 3.0 and 5.0 wt. %, respectively. Tension strength values of microcapsules/bitumen samples were measured by a reparative fracture-healing process under different temperatures. It was found that these samples had tensile strength values larger than the data of pure bitumen samples under the same conditions after the four tensile fracture-healing cycles. Fracture morphology investigation and mechanism analysis indicated that the self-healing process was a process consisting of microcapsules being broken, penetrated and diffused. Moreover, the crack healing of bitumen can be considered as a viscosity driven process. The self-healing ability partly repaired the damage of bitumen during service life by comparing the properties of virgin and rejuvenated bitumen.

Self-immunity microcapsules for corrosion protection of steel bar in reinforced concrete.

A novel microcapsule-based self-immunity system for reinforced concrete is proposed. Its feasibility for hindering the corrosion of steel rebar by means of lifting the threshold value of [Cl(-)]/[OH(-)] is discussed. Precisely controlled release behavior enables corrosion protection in the case of depassivation. The release process is characterized over a designated range of pH values, and its release characteristics of the microcapsules, triggered by decreasing pH value, are captured by observing that the core crystals are released when exposed to a signal (stimulus). The aim of corrosion protection of steel bar is achieved through the constantly-stabilized passive film, and its stability is promoted using continuous calcium hydroxide released from the microcapsule, restoring alkaline conditions. The test results exhibited that the release process of the microcapsules is a function of time. Moreover, the release rate of core materials could interact with environmental pH value, in which the release rate is found to increase remarkably with decreasing pH value, but is inhibited by high pH levels.

A novel capsule-based self-recovery system with a chloride ion trigger.

Steel is prone to corrosion induced by chloride ions, which is a serious threat to reinforced concrete structures, especially in marine environments. In this work, we report a novel capsule-based self-recovery system that utilizes chloride ions as a trigger. These capsules, which are functionalized via a smart response to chloride ions, are fabricated using a silver alginate hydrogel that disintegrates upon contact with chloride ions, and thereby releases the activated core materials. The experimental results show that the smart capsules respond to a very low concentration of chloride ions (0.1 wt%). Therefore, we believe that this novel capsule-based self-recovery system will exhibit a promising prospect for self-healing or corrosion inhibition applications.

Electrical and Mechanical Performance of Carbon Fiber-Reinforced Polymer Used as the Impressed Current Anode Material.

An investigation was performed by using carbon fiber-reinforced polymer (CFRP) as the anode material in the impressed current cathodic protection (ICCP) system of steel reinforced concrete structures. The service life and performance of CFRP were investigated in simulated ICCP systems with various configurations. Constant current densities were maintained during the tests. No significant degradation in electrical and mechanical properties was found for CFRP subjected to anodic polarization with the selected applied current densities. The service life of the CFRP-based ICCP system was discussed based on the practical reinforced concrete structure layout.

Study on the Carbonation Behavior of Cement Mortar by Electrochemical Impedance Spectroscopy.

A new electrochemical model has been carefully established to explain the carbonation behavior of cement mortar, and the model has been validated by the experimental results. In fact, it is shown by this study that the electrochemical impedance behavior of mortars varies in the process of carbonation. With the cement/sand ratio reduced, the carbonation rate reveals more remarkable. The carbonation process can be quantitatively accessed by a parameter, which can be obtained by means of the electrochemical impedance spectroscopy (EIS)-based electrochemical model. It has been found that the parameter is a function of carbonation depth and of carbonation time. Thereby, prediction of carbonation depth can be achieved.

Performance-Based Specifications of Workability Characteristics of Prestressed, Precast Self-Consolidating Concrete-A North American Prospective.

Adequate selection of material constituents and test methods are necessary for workability specifications and performance of hardened concrete. An experimental program was performed to evaluate the suitability of various test methods for workability assessment and to propose performance specifications of prestressed concrete. In total, 33 self-consolidating concrete (SCC) mixtures made with various mixture proportioning parameters, including maximum size and type of aggregate, type and content of binder, and w/cm were evaluated. Correlations among various test results used in evaluating the workability responses are established. It is recommended that SCC should have slump flow values of 635-760 mm. To ensure proper filling capacity greater than 80%, such concrete should have a passing ability that corresponds to L-box blocking ratio (h2/h1) ≥ 0.5, J-Ring flow of 570-685 mm, slump flow minus J-Ring flow diameter ≤75 mm. Moreover, Stable SCC should develop a column segregation index lower than 5%, and rate of settlement at 30 min of 0.27%/h for SCC proportioned with 12.5 or 9.5 mm MSA. It is recommended that SCC should have a plastic viscosity of 100-225 Pa·s and 100-400 Pa·s for concrete made with crushed aggregate and gravel, respectively, to ensure proper workability.

Experimental Study on Cementitious Composites Embedded with Organic Microcapsules.

The recovery behavior for strength and impermeability of cementitious composites embedded with organic microcapsules was investigated in this study. Mortar specimens were formed by mixing the organic microcapsules and a catalyst with cement and sand. The mechanical behaviors of flexural and compression strength were tested. The results showed that strength could increase by up to nine percent with the addition of a small amount of microcapsules and then decrease with an increasing amount of microcapsules. An orthogonal test for investigating the strength recovery rate was designed and implemented for bending and compression using the factors of water/cement ratio, amount of microcapsules, and preloading rate. It is shown that the amount of microcapsules plays a key role in the strength recovery rate. Chloride ion permeability tests were also carried out to investigate the recovery rate and healing effect. The initial damage was obtained by subjecting the specimens to compression. Both the recovery rate and the healing effect were nearly proportional to the amount of microcapsules. The obtained cementitious composites can be seen as self-healing owing to their recovery behavior for both strength and permeability.