Zhongzi Xu

Immersion tests with 5 wt.% Na₂SO₄ solution were carried out to investigate the deterioration of calcium silicate hydrate (C-S-H) gel in a sulfate environment. C-S-H gels with different Ca/(Si + Al) molar ratios were used for comparison. Particular attention was paid to the changes in element composition and Si-O-Si chain structure of the C-S-H gel. The results show that the C-S-H gels with a low Ca/(Si + Al) ratio (0.8–1.0) and appropriate Si-O-Si chain length (14.8) presented better stability in a severe sulfate environment. The C-S-H gels with a higher Ca/(Si + Al) ratio (>2.0) were more sensitive to the attack of sulfate ions. Calcium ions dissolved rapidly during the immersion process, causing the loss of cohesive strength of the C-S-H gel, and then decomposed into fine particles. The C-S-H gel with a lower Ca/(Si + Al) ratio (about 1.1) rarely leached out calcium ions and maintained good micromorphology. The ²⁹Si MAS-NMR results indicate that the Si-O-Si chains with too short or too long chain lengths will break and recombine under the attack of sulfate ions. The Si-O-Si chains with an appropriate chain length (14.8) maintained the stability of the structure of the C-S-H gel in a sulfate environment. These changes are closely related to the asymmetric layered structure of amorphous C-S-H gel. Partial calcium ions between the layers of the main chain structure of Si-O-Si are easily taken away by sulfate ions, leading to the structural instability of the C-S-H gel.

Although photothermally induced self-bending films based on nonuniform thermal expansion are created, heat transfer and shape-deformation procedures are not investigated very well, limiting the understanding of such complicated behavior and the achievement of precise shape control. Here, thermally expanded microspheres (TEMs) were added into polydimethylsiloxane (PDMS) to create active layers as PDMS-TEM single-layer films that were attached onto pure PDMS passive layer to create PDMS/PDMS-TEM bi-layer films subsequently. After heating, TEMs in the film undergo phase transition and present irreversible thermal expansion, driving deformation of films. Combined with steady-state (uniform heating) deformation simulations and experiments, a deformation model was established before a non-steady state (light irradiation) heat transfer model was set up to simulate the heat transfer process of films under light irradiation. Then the temperature distribution was coupled with the deformation model to simulate the photothermally induced deformation of the samples. The PDMS-TEM single-layer films also presented bending deformation under illumination due to the non-uniform thermal expansion caused by temperature gradient. For bi-layer films, different degrees of thermal expansion between two layers lead to bending deformation. The films with TEM concentration of 30 wt% can achieve great deformation, and the bending curvature was 0.07 mm ⁻¹ . The geometric parameters including thickness, layer thickness ratio and aspect ratio had little effect on deformation degrees of the films. Deformation mode was varied with aspect ratio. A long side bending and diagonal bending were achieved in bi-layer films at aspect ratios of 7:1 and 1:1. In combination with experimental results, the heat transfer model and deformation model were constructed to demonstrate the complex deformation process, which provides guidance for the structural design of the photothermally induced shape-changing films in practical applications.

There is a need to create next-generation polymer composites having high property, unique function, and intelligent behaviors, such as shape memory effect (SME) and self-healing (SH) capability. Rare earth complexes can provide luminescence for polymers, and their dispersion is highly affected by ligand structures. Here, we created three different REOCs with different ligands before studying the effects of ligands on REOC dispersion in polyurea–urethane (PUU) with disulfide bonds in main chains. In addition, the effects of different REOCs on mechanical properties, luminescent functions, and intelligent behaviors of PUU composites were studied. The results showed that REOC I (Sm(TTA)₃phen: TTA, thenoyltrifluoroacetone; phen, 1,10-phenanthroline) has incompatible ligands with the PUU matrix. REOC I and REOC III (Sm(BUBA)₃phen: BUBA, 4-benzylurea-benzoic acid) with amine and urea groups facilitate their dispersion. It was REOC III that helped the maintenance of mechanical properties of PUU composites due to the good dispersion and the needle-like morphologies. Due to more organic ligands of REOC III, the fluorescence intensity of composite materials is reduced. The shape recovery ratio of the composite was not as good as that of pure PUU when a large amount of fillers was added. Besides, REOC I reduced the self-healing efficiency of PUU composites due to poor dispersion, and the other two REOCs increased the self-healing efficiency. The results showed that ligands in REOCs are important for their dispersion in the PUU matrix. The poor dispersion of REOC I is unbeneficial for mechanical properties and intelligent behavior. The high miscibility of REOC II (Sm(PABA)₃phen: PABA, 4-aminobenzoic acid) decreases mechanical properties as well but ensures the good shape recovery ratio and self-healing efficiency. The mediate miscibility and needle-like morphology of REOC III are good for mechanical properties. The shape recovery ratio, however, was decreased.

Polyvinylidene fluoride (PVDF) and poly(methyl methacrylate) (PMMA) blend films were prepared using biaxial stretching. The effects of PMMA content and stretching ratio on the crystallinity and β phase fraction of PVDF in blend films were investigated. The distributions of crystallinity and β phase fraction on variable locations were also studied. The results of FTIR and XRD showed that β phase appeared in PVDF/PMMA blends after extrusion and casting procedures. Although β phase fraction decreased after preheating, there was still an increasing trend during following biaxial stretching. More importantly, the increase in PMMA content improved β phase fraction, and the highest β phase fraction of 93% was achieved at PMMA content of 30 wt% and stretching ratio of 2×2. Besides, the reduction in PMMA content and the increase in stretching ratio improved the crystallinity of PVDF. The mechanical properties of the stretched films were significantly improved by increasing the stretching ratio as well. The uniform stress distribution on different regions of biaxial stretching films contributed to the uniform distribution of β phase fraction and crystallinity of PVDF with the aid of simulation. This work confirmed that biaxial stretching can be a candidate method to prepare PVDF/PMMA blend films with uniform distributions of comparable β phase and crystallinity of PVDF.

Radiative cooling is a passive cooling technology that can cool a space without any external energy by reflecting sunlight and radiating heat to the universe. Current reported radiative cooling techniques can present good outside test results, however, manufacturing an efficient radiative material which can be applied to the market for large-scale application is still a huge challenge. Here, an effective radiative cooling coating with a near-ideal selective emissive spectrum is prepared based on the molecular vibrations of SiO_x, mica, rare earth silicate, and molybdate functional nanoparticles. The radiative cooling coating can theoretically cool 45 °C below the ambient temperature in the nighttime. Polyethylene terephthalate (PET) aluminized film was selected as the coating substrate for its flexibility, low cost, and extensive production. As opposed to the usual investigations that measure the substrate temperature, the radiative cooling coating was made into a cubic box to test its space cooling performance on a rooftop. Results showed that a temperature reduction of 4 ± 0.5 °C was obtained in the nighttime and 1 ± 0.2 °C was achieved in the daytime. Furthermore, the radiative cooling coating is resistant to weathering, fouling, and ultraviolet radiation, and is capable of self-cleaning due to its hydrophobicity. This practical coating may have a significant impact on global energy consumption.

Tobermorite and Al-substituted tobermorite with varying Al/(Si + Al) molar ratios were synthesized via the static hydrothermal method. The effect of different Al substitution ratios on the structure of tobermorite was investigated by XRD, SEM–EDS, TG–DSC, FT–IR, ²⁹Si, and ²⁷Al MAS–NMR. The interplanar crystal spacing of (002) increased with the increment of the Al substitution ratio. The maximum ratio of the Al substitution for Si in the structure of tobermorite was about 15 at %, which was limited by the compositions of tobermorite and the electrostatic repulsive forces caused by Al substitution. The DSC curve of the tobermorite with an Al/(Al + Si) molar ratio of 0.15 showed a larger exothermic peak area at 850 °C, indicating that the Al-O-Si bond was formed in the structure of tobermorite and the Al participated in the recrystallization. The ²⁹Si and ²⁷Al MAS–NMR results confirmed that tetrahedral Al was introduced into the structure of the tobermorite. New silicon sites, Q²(1Al) and Q³(1Al), formed by the Al substitution for Si in bridging and non-bridging sites, were detected. Compared to the tobermorite without Al substitution, the adsorption capacity of Al-substituted tobermorite with Al/(Al + Si) = 0.15 to Na⁺ was improved by 44%.

Radiative cooling can make the selective emitter cool below ambient temperature without any external energy. Recent advances in photonic crystal and metamaterial technology made a high-efficiency selective emitter achievable by precisely controlling the emitter’s Infrared emission spectrum. However, the high cost of the photonic crystals and meta-materials limit their application. Herein, an efficient bilayer selective emitter is prepared based on the molecular vibrations of functional nanoparticles. By optimizing the volume fraction of the functional nanoparticles, the bilayer selective emitter can theoretically cool 36.7 °C and 25.5 °C below the ambient temperature in the nighttime and daytime, respectively. Such an efficient cooling performance is comparable with the published photonic crystal and metamaterial selective emitters. The rooftop measurements show that the bilayer selective emitter is effective in the ambient air even under direct sunlight. The relatively low cost and excellent cooling performance enable the bilayer selective emitter to have great potential for a practical purpose.

Nanomaterials have been widely used in cement-based materials. Graphene has excellent properties for improving the durability of cement-based materials. Given its high production budget, it has limited its wide potential for application in the field of engineering. Hence, it is very meaningful to obtain low cost nanoplatelets from natural materials that can replace graphene nanoplatelets (GNPs) The purpose of this paper is to improve the resistance to chloride ion penetration by optimizing the pore structure of cement-based materials, and another point is to reduce investment costs. The results illustrated that low cost CaCO₃ nanoplatelets (CCNPs) were successfully obtained under alkali treatment of seashell powder, and the chloride ion permeability of cement-based materials significantly decreased by 15.7% compared to that of the control samples when CCNPs were incorporated. Furthermore, the compressive strength of cement pastes at the age of 28 days increased by 37.9% than that of the plain sample. Improvement of performance of cement-based materials can be partly attributed to the refinement of the pore structure. In addition, AFM was employed to characterize the nanoplatelet thickness of CCNPs and the pore structures of the cement-based composites were analyzed by MIP, respectively. CCNPs composite cement best performance could lay the foundation for further study of the durability of cement-based materials and the application of decontaminated seashells.

Two issues are required to be solved to bring intrinsically self-healing polymer coatings into real applications: remote activation and satisfied practical properties. Here, we used MXene, a newly reported two-dimensional material, to provide an epoxy coating with light-induced self-healing capabilities and we worked to enhance the properties of that coating. The self-healing coatings had a reversible crosslinking network based on the Diels-Alder reaction among maleimide groups from bis(4-maleimidopheny)methane and dangling furan groups in oligomers that were prepared through the condensation polymerization of diglycidylether of bisphenol A and furfurylamine. The results showed that the delaminated MXene flakes were small in size, around 900 nm, and dispersed well in self-healing coatings. The MXene flakes of only 2.80 wt % improved greatly the pencil hardness of the coating hardness from HB to 5H and the polarization resistance from 4.3 to 428.3 MΩ cm⁻². The self-healing behavior, however, was retarded by MXene flakes. Leveling agent acted a key part here to facilitate the gap closure driven by reverse plasticity to compensate for the limitation of macromolecular mobility resulting from the MXene flakes. The self-healing of coatings was achieved in 30 s by thermal treatment at 150 °C. The efficient self-healing was also demonstrated based on the recovery of the anti-corrosion capability. MXene flakes also played an evident photothermal role in generating heat via irradiation of near-infrared light at 808 nm and focused sunlight. The healing can be quickly obtained in 10 s under irradiation of near-infrared light at 808 nm having a power density of 6.28 W cm⁻² or in 10 min under irradiation of focused sunlight having a power density of 4.0 W cm⁻².