The synthesis and adsorption-dispersion properties of PPEGMA-PVPA copolymers in cement paste.

This study reports the synthesis of a novel superplasticizer, poly(poly(ethylene glycol)methacrylate)-poly(vinylphosphonic acid) (PPEGMA-PVPA), containing phosphate moieties via solution radical polymerization. By adjusting the feed ratios of monomers, PPEGMA-PVPA copolymers with different phosphate group densities were obtained, and their chemical structure was characterized via FT-IR, 1H NMR spectroscopy and ICP-OES. The results demonstrated that about 70% of the VPA monomer was polymerized. The thermostability of PPEGMA-PVPA was also determined through DSC and TGA. The adsorption-dispersion performance onto cement pastes was investigated using mini-slump test, TOC and zeta potential analysis. It was demonstrated that the adsorption capacity of PPEGMA-PVPA onto cement paste was about 1.4 times stronger than that of the reference polycarboxylate superplasticizer and exhibited excellent adsorption-dispersion performance.

Computational Simulations of Adsorption Behavior of Anionic Surfactants at the Portlandite-Water Interface under Sulfate and Calcium Ions.

The adsorption behaviors of two kinds of anionic surfactants (called HSO4 and HPO4, respectively) with different negatively charged hydrophilic head groups (sulfate and phosphate groups) under different concentrations of sulfate and calcium ions at the portlandite-water interface are investigated by molecular dynamics simulations. Although the adsorption strength of HPO4 is much greater than that of HSO4, the desorption energy of HSO4 is slightly greater at an early stage of desorption due to a more perpendicular orientation and denser packing of hydrophobic tail chains. After adding ions, the sulfate ion has a significant weakening effect due to competitive adsorption, and the negative influence of the calcium ion is weaker, and it even slightly promotes the adsorption at low concentration. Due to the stronger electrostatic interaction of phosphate head groups with the portlandite surface, adsorption strength and adsorption stability for HPO4 are always greater than that of HSO4 under the interference of sulfate ions. The competitive adsorption of the sulfate ion significantly weakens the interaction of hydrophilic head groups with portlandite and the dense packing of two surfactants. The calcium ion with low concentration approaches the portlandite surface and acts as an ion bridge to slightly enhance the adsorption of the surfactant. The ion bridging effect is stronger in the HPO4 system than in the HSO4 system.

One Novel Hybrid Flexible Piezoresistive/Piezoelectric Double-Mode Sensor Design for Water Leakage Monitoring.

Water leakage is a significant issue in infrastructure, such as submarine tunnels, which can lead to major disasters and property losses. Therefore, it is of great significance to develop a water leakage detection sensor with simple preparation process, low cost, and small limitation of applicable location. In this study, a novel hybrid flexible piezoresistive/piezoelectric double-mode sensor with a sandpaper negative microstructure is proposed. A unique dual-path perception structure is designed that can simultaneously and independently detect two signals of water leakage frequency and water leakage volume. The piezoresistive layer is formed by polydimethylsiloxane (PDMS) coated with multiwalled carbon nanotubes (MWCNTs), which is molded by sandpaper molding. By sensing the deformation caused by the swelling of superabsorbent polymers (SAPs), the water leakage volume can be detected as low as 0.5 mL. The piezoelectric layer is a polyvinylidene fluoride-trifluoroethylene copolymer (PVDF-TrFE) film prepared by the spin-coating method, and the water leakage frequency (0.5-4 Hz) is detected by direct contact with water droplets. This work also studied the performance of the double-mode sensor under low temperature and seawater leakage conditions and further verified its reliability in different environments. The design of the new hybrid flexible piezoresistive/piezoelectric double-mode sensor provides a new possibility for water leakage monitoring, such as in submarine tunnels.

Robust All-Waterborne Superhydrophobic Coating with Photothermal Deicing and Passive Anti-icing Properties.

The compelling integration of superhydrophobic coatings with light-to-heat conversion capabilities has garnered substantial interest due to their dual functionality encompassing passive anti-icing and deicing attributes. However, the insufficient mechanical stability and the environmental and human health concerns stemming from the extensive use of organic solvents limit their practical application. In this study, an all-waterborne superhydrophobic photothermal coating (PCPAS) was prepared through the synergy of composite micro-nanoparticles derived from carbon nanotubes (CNT), polydopamine (PDA), and Ag particles with fluorine-containing polyacrylic emulsion (PFA). The PDA provided active sites for Ag+ reduction reaction and enhanced the interfacial interaction between CNT and Ag particles. The interfacial enhancement enabled the coating to maintain stable superhydrophobicity after 260 times sandpaper abrasion and 240 times tape peeling. Simultaneously, the composite micro-nanoparticle's light-to-heat conversion ability gave the coating excellent anti-icing/deicing capabilities. Under the condition of -20 °C, the freezing time of 30 µL of water droplets was extended to 392 s, and 2 × 2 × 2 cm ice cubes placed on the surface of the coating could completely melt after only 1142 s under simulated sunlight irradiation with a 1 kW/m2 intensity. In addition, the coating also had suitable self-cleaning properties and substrate applicability. The comprehensive attributes of this all-waterborne photothermal superhydrophobic coating render it a promising contender for anti-icing and deicing applications in challenging outdoor environments.

Ultra-purification of heavy metals and robustness of calcium silicate hydrate (C-S-H) nanocomposites.

For the sake of remediating the contamination of heavy metal ions (HMs) that poses high risk to the global environment, a novel inorganic nanocomposite with excellent robustness, calcium silicate hydrate (C-S-H), is synthesized at extremely low cost yet presents rapid adsorption rate and superhigh adsorption capacity. High concentrations of Cu(Ⅱ), Cd(Ⅱ), Co(Ⅱ) and Cr(Ⅲ) in wastewater can be purified to ultra-low level (∼0.008 mg L-1) within 60 min at low C-S-H dosage, the concentration and pH indexes of which meet the standard for direct discharge in China. The adsorption processes are spontaneous, following the Langmuir adsorption isotherm model, and its kinetics conforms to pseudo-second order model. Meanwhile, C-S-H presents excellent anti-interference performance during the ultra-purification of HMs when exposed to the acid environments, solutions with various HMs as well as high salinity. The ultra-purification of HMs and robustness of C-S-H is realized through multiple mechanisms based on adsorption, involving hydrolysis of HMs, electrostatic interaction, chemical microprecipitation, surface complexation and interlayer complexation, among which interlayer complexation is dominant. All these verify the robust performance and broad applicability of C-S-H to complex aqueous systems.

Effects of an Amphiphilic Micelle of Diblock Copolymer on Water Adsorption of Cement Paste.

To reduce the inhibiting effects of polystyrene-based emulsion on the hydration process and strength development of cementitious materials, an amphiphilic diblock copolymer polystyrene-block-poly(acrylic acid) (PS-b-PAA) was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization and demonstrated in cement paste system for improving the resistance to water absorption without significantly reducing 28-day compressive strength. Firstly, the dissolved PS-b-PAA was added into water, and it quickly self-assembled into amphiphilic 80 nm-sized micelles with hydrophobic polystyrene-based core and hydrophilic poly(acrylic acid)-based shell. The improved dispersion compared to that of polystyrene emulsion may minimize the inhibiting effects on strength development, as the effects of PS-b-PAA micelle as hydrophobic admixtures on rheological properties, compressive strength, water absorption, hydration process, and pore structure of 28-day cement pastes were subsequently investigated. In comparison with the control sample, the saturated water absorption amount of cement pastes with 0.4% PS-b-PAA was reduced by 20%, and the 28-day compressive strength was merely reduced by 2.5%. Besides, the significantly increased hydrophobicity instead of slightly decreased porosity of cement paste with PS-b-PAA may contribute more to the reduced water adsorption characteristics. The study based on prepared PS-b-PAA micelle suggested a promising alternative strategy for fabricating polystyrene-modified concrete with reduced water absorption and unaffected compressive strength.

The Preparation of a Novel Hyperbranched Antifouling Material and Application in the Protection of Marine Concrete.

Marine fouling on concrete has become one of the severest problems that damage the surface and even cause internal corrosion of marine concrete. Dissimilarly to the previous abuse of toxic antifoulants, developing hydrophobic waterborne antifouling materials could be regarded as one of the most environment-friendly and potential directions to protect marine concrete. However, the insufficient hydrophobicity, antifouling, and mechanical properties limit their application. Herein, we reported a series of hybrid coatings combining hyperbranched polyglycerol (HPG) decorated waterborne fluoro silicone polyurethane (H) and HPG-grafted graphene oxide (G-HPG) that improve the hydrophobicity, antifouling, and mechanical properties. The hybrid materials were modified by the hyperbranched polyglycerol synthesized based on the anionic-ring-opening reaction between glycerol and ethylene glycol or polyethylene glycol. Remarkably, the hydrophobicity (115.19°) and antifouling properties (BSA absorption of 2.33 µg/cm2 and P. tricornutum attachment of 1.289 × 104 CFU/cm2) of the materials could be developed by the modification of HPG with higher generation numbers and backbone molecular weights. Moreover, the mechanical properties negligibly decreased (tensile strength decreased from 11.29 MPa to 10.49 MPa, same pencil hardness and adhesion grade as H of 2H and grade 2). The results revealed that the HPG of higher generation numbers and backbone molecular weights could benefit materials with enhanced antifouling properties and hydrophobicity. The method of hyperbranched modification can be regarded as potentially effective in developing the durability and antifouling properties of marine antifouling materials.

Novel Slow-Release Defoamers for Concrete Using Porous Nanoparticles as Carriers.

Excess large and unstable air bubbles can reduce the compressive strength of hardened concrete, and traditional defoamers always fail because of adsorption and encapsulation on cement with the progress of cement hydration in later stages. It is necessary to develop a novel defoamer that shows a sustained defoaming ability in fresh concrete. A novel slow-release defoamer for concrete using porous nanoparticles as carriers is reported for the first time. The porous nanoparticles/polyether defoamer composite (SiO2-Def) was prepared via sol-gel method. SiO2-Def is a spherical composite nanoparticle with a size range of 160-200 nm and a uniform pore size distribution. SiO2-Def shows a high load rate of about 16.4% and an excellent release under an alkali and salt environment. It has a weak initial defoaming ability but shows a sustained defoaming ability with time, so that it can avoid the failures of defoamers and eliminate harmful bubbles entrained during the processes of pumping and transportation. Moreover, SiO2-Def produced a higher compressive strength of the hardened cement mortars.

Anionic Copolymers with Different Charge Densities for Regulating the Properties of Cement Pastes.

Self-compacting concrete (SCC) is an extremely flowable concrete, which increases the probability of segregation and bleeding. Viscosity-modifying admixtures (VMAs) have been developed to improve the stability of SCC. Synthetic polymer VMAs have excellent water solubility and stability, and can be easily chemically prepared and modified. In this work, a series of copolymers based on anionic 2-acrylamido-2-methyl-propanesulfonic acid (AMPS) and nonionic N, N-dimethyl acrylamide (DMAA), with similar molecular weights but different charge densities, were prepared. The effect of the charge density of the anionic polymers on the fluidity, rheological property, and adsorption behavior of the cement pastes was investigated. The action mechanism of the polymers was discussed. The results indicate that the charge density of anionic polymer VMAs is of great significance for the development of cost-effective SCCs with good rheological properties.

Tuning the Hydration Acceleration Efficiency of Calcium Carbonate by Pre-Seeding with Calcium Silicate Hydrate.

Nanomaterials are promising candidates for refined performance optimization of cementitious materials. In recent years, numerous studies about the performance improvement of nanomaterials using polymers have been conducted, but the modification of cement-oriented nanomaterials with inorganic modifiers is seldom assessed. In this study, we explored the performance tuning and optimization of nanomaterials by inorganic modification. In this work, hydration acceleration efficiency of calcium carbonate (CaCO3, CC) was tuned via surface deposition with calcium silicate hydrate (C-S-H) nanogel through seeding. Multiple calcium carbonate-calcium silicate hydrate (CC-CSH) samples with varying degrees of surface modification were prepared via dosage control. According to characterizations, the degree of C-S-H modification on the CaCO3 surface has a maximum that is controlled by available surface space. Once the available space is depleted, excessive C-S-H turns into free form and causes adhesion between CC-CSH particles. The resultant CC-CSH samples in this work showed enhanced hydration acceleration efficiency that is tuned by the actual degree of C-S-H modification. Elevated C-S-H modification causes CC-CSH's acceleration behavior to shift to enhanced early-age acceleration. According to mortar strength tests, CC-CSH with 5% C-S-H modification showed the most balanced performance, while CC-CSH with higher C-S-H modification showed faster early-age strength development at the cost of lower later-age strength. The inferior later-age strength of highly C-S-H-modified CC-CSH samples may be due to the coarsening of hydration products and stiffening of their network, as well as agglomeration caused by C-S-H adhesion. This study may offer a novel route for performance tuning of cement-oriented nanomaterials.

Influence of a Nano-Hydrophobic Admixture on Concrete Durability and Steel Corrosion.

Steel corrosion is major reason of the deterioration of reinforced concrete structures. Decreasing the transportation of erosion ions in concrete is one of effective methods to protect the steel from corrosion. In the present work, a novel nano-hydrophobic admixture is introduced to improve the ion-diffusion properties and the corrosion resistance of reinforced steel. Compared with unmodified concrete, the nano-hydrophobic admixture effectively decreases the water adsorption, water evaporation, and chloride ions transport in a concrete structure, and then improved the concrete's durability. The concrete's water adsorption decreased more than 78%, and the initial corrosion time of reinforced steel is prolonged more than one time by treatment with the nano-hydrophobic admixture. The inhibition penetration of the medium in concrete modified by hydrophobic nanoparticles is the key to provide the protective properties of steel reinforcement from chloride erosion.

Influence of Sulfates on Formation of Ettringite during Early C3A Hydration.

The hydration of C3A-gypsum systems was studied in the presence of various types of sulfates such as gypsum, hemihydrate and Na2SO4 in the first hour. The BET method combined with a DSC analysis enabled us to quantitatively characterize the amount of precipitated ettringite and its specific surface area along the hydration. It was found that sulfates not only affected the formation rate of ettringite, but also had a significant impact on the morphology of ettringite. For all the C3A-gypsum systems, a large part of the ettringite precipitated within the first 20 min and the specific surface area of the hydrated sample strongly increased within the first 5 min, whereas the specific surface area of ettringite gradually decreased along the C3A hydration reaction. Incorporating a small amount of Na2SO4 in the C3A-gypsum system could greatly promote the formation rate of ettringite in the first 20 min, and significantly decrease the specific surface area of ettringite. As hemihydrate was added to the C3A-gypsum system, two processes of ettringite precipitation and gypsum precipitation occurred. The nucleation and growth process of ettringite and gypsum resulted in the complex changes in the specific surface area of the hydrated sample, which first increased at the very beginning, then decreased and, finally, increased.

Investigation of the Effect of Particle Surface Charge and Dispersion Stability on Latex Behavior in Cement Using Non-Ionic and Traditional Latexes.

In this work, a novel total non-ionic polystyrene-polyurethane (PS-PU) composite latex was synthesized with polymerizable polyethylene glycol ether. Contrary to traditional styrene-butyl acrylate latex (St-BA), PS-PU has a smaller size and superior dispersion stability, and it is stable in saturated Ca(OH)2 even after 72 h. In fresh-mixed mortars, PS-PU showed a little adverse effect on workability and insignificant air entrainment, with little defoamer consumption. The retardation effect of PS-PU is also much milder than traditional St-BA. As for strength, PS-PU showed a less adverse effect on early and late age compressive strength, but its effect on flexural strength is not as pronounced as St-BA at high dosages (4% and 6%). The different behavior in cementitious materials between PS-PU and St-BA can be reasoned from their different adsorption behavior and surface charge properties, as the results from characterizations suggest. The non-ionic nature of PS-PU made it less prone to destabilization and adsorption, which turned out as the aforementioned behavior in cementitious systems. The difference can further be ascribed to the difference in their polymeric structure and properties.

Investigation on the Effect of Hydroxyapatite Nanorod on Cement Hydration and Strength Development.

This work investigated the effect of hydroxyapatite (HA) nanorods on the strength development and hydration of cement. Undispersed HA nanorods (HA-UD) and dispersed HA nanorods (HA-DN) were prepared by atom-efficient neutralization. The strength of mortars modified by HA nanorods was tested, as well as their compatibility with supplementary cementitious material. The hydration of HA-modified cement pastes was characterized via in situ X-ray diffraction, isothermal calorimetry and scanning electron microscopy. As the results suggest, the undispersed HA-DN caused a considerable increase in superplasticizer demand to achieve the same level of flow. Both HA nanorods showed a significant accelerating effect on early hydration, with approximately 100% strength enhancement at 12 h at 2.0% dosage. The effect on early strength of the nanorods is retained in systems with up to 30% fly ash in the binder mass. According to the characterizations, the rate of the hydration reaction in the acceleration period was enhanced by HA nanorods, and C3S consumption was also increased. In all of the testing situations, HA-DN showed superior performance, likely due to improved spatial distribution of the hydroxyapatites. The results suggest that proper dispersion of the nanorods is necessary to optimize its performance.

Site-selective, reversible, pH-induced N-terminal maleylation and its application for proteomics research.

RATIONALE: Compared with traditional labelling reagents used in proteomics, maleic anhydride is milder and can be easily removed under certain conditions, thus simplifying chemical derivatization. METHODS: The proposed strategy combined a site-specific chemical labelling reaction with mass spectrometry. Site-selective, reversible N-terminal maleylation was controlled by pH. RESULTS: Selective maleyl N-terminal labelling was achieved with high efficiency under the optimized reaction conditions. The demaleylation conditions were also optimized. The sequence coverage of histone H4 increased from 77% to 95% after the maleyl labels were removed, and the number of maleylated peptides was five times that of the unlabelled peptides. We further verified the reversible and selective N-terminal labelling properties of maleic anhydride through propionylation labelling at the peptide/protein level. CONCLUSIONS: A new method for site-selective maleylation of the N-terminal amino groups of a peptide was explored. Through the optimization experiment, good efficiency was achieved for this labelling reaction. The reversibility of maleylation labelling was also explored and applied for the identification of post-translational modifications of histones. Thus, site-selective, reversible, pH-induced N-terminal labelling using maleic anhydride has greater potential for application in proteomics than any other labelling methods.

Binding of calcium cations with three different types of oxygen-based functional groups of superplasticizers studied by atomistic simulations.

This work investigated interactions between calcium cations (Ca2+) and three common types of oxygen-based functional groups of concrete superplasticizers using density functional theory (DFT) calculations and all-atom molecular dynamics (MD) simulations. The three common types of oxygen-based functional groups were modeled as three hypothetical, low-molecular-weight organic molecules, each containing a methyl-terminated oxyethylene dimer and an adsorbing head of two oxygen-based functional groups, and are referred to as carboxylate, sulfonate, and phosphate groups, respectively, following the usual terminology in the field of concrete admixtures. Our DFT results show that the binding strength of the three groups with calcium cations follows (from high to low) phosphate>carboxylate>sulfonate, and both the electrophilic attack and the chemical reactivity of the three groups contribute significantly to the binding strength. The MD simulation results indicate that the adsorption of the three small molecules on the calcite (1 0 4) surface in aqueous solution shares a similar pattern in the sense that just two oxygen atoms of two adjacent anchor groups adsorb on the calcium atoms on the top layer of the crystal. The adsorption strength among the three types of functional groups follows the same order as the binding strength obtained from DFT calculations; both results corroborate a similar rule-of-thumb established by experiments. Furthermore, interactions of the three types of groups with water molecules suggest that strong hydrogen-bonding interactions exist in those systems. Graphical abstract Binding of calcium cations with three different types of oxygen-based functional groups of superplasticizersᅟ.

Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products.

Conformational properties and the entropic barrier in the "head-on" adsorption of a single polymer chain towards a flat surface.

This work investigates the change in conformations and the entropic free energy barrier in the "head-on" adsorption process of a flexible polymer chain towards a flat surface in the framework of the Gaussian chain model. Analytical expressions are reported for the distribution of chain end, the mean square end-to-end distance, the entropic free energy barrier and the adsorption equilibrium constant at low surface coverage (the "mushroom" regime). Theoretical results are discussed in the context of polyoxyethylene-phosphonate-type polymer dispersants, possessing a non-adsorbing polyoxyethylene chain and an adsorbing head-group.

Effect of methyl groups on conformational properties of small ionized comb-like polyelectrolytes at the atomic level.

Comb-like polycarboxylate ether (PCE) molecules with different content of methyl groups substituted on backbone and different location of methyl groups substituted on the side chains, respectively, were designed and were studied in explicit salt solutions by all-atom molecular dynamics simulations. Methyl groups substituted on the backbone of PCE have a great effect on the conformation of PCE. Stiffness of charged backbone was not only affected by the rotational freedom but also the electrostatic repulsion between the charged COO- groups. The interaction of counterions (Na+) with COO- groups for PCE3 (with part of AA substituted by MAA on the backbone) was stronger and the screen effect was great, which decided the smaller size of PCE3. The interaction between water and COO- groups was strong regardless of the content of AA substituted by MAA on the backbone. The effect of methyl groups substituted on the different location of side chains on the conformation of PCE was less than that of methyl groups substituted on the backbone. The equilibrium sizes of the four PCE molecules with methyl groups substituted on the side chains were similar. Graphical Abstract Effect of methyl groups on conformational properties of small ionized comb-like polyelectrolytes at the atomic level.

Effect of the length of the side chains of comb-like copolymer dispersants on dispersion and rheological properties of concentrated cement suspensions.

Two different groups of comb-like copolymer dispersants with side chain lengths ranging from 8 to 48 were synthesized and characterized: one group with the carboxylic content per mole molecule constant and the other group with the carboxylic contents per gram polymer constant. The effects of side chain length on comb-like copolymers on adsorption, dispersion, rheological behavior, and zeta potential for cement suspensions were investigated systematically to elucidate the governing dispersing mechanism. The adsorption of comb-like copolymer on the cement surfaces, controlled by COO(-) content in copolymer backbones, side chain length, and also polymer conformation in solution, governs the dispersion and rheological behavior of the cementitious system. The dispersion effect increases with the adsorbed amount; especially the adsorbed side chain density increases. But the dispersion power of comb-like copolymers varies depending on the side chain length in comb-like copolymer. The long side chain polymer has higher dispersion power than the shorter ones due to the stronger steric hindrance effect of the former; for the short side chain polymer with high ionic content, the electrostatic repulsion and steric hindrance together should be responsible for its dispersion effect. Such information also suggests that their exists the geometrical balance between the main chain and the side chains in comb-like copolymer dispersants which should be very useful in designing optimum molecular structures of high efficient dispersants.