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Polycarboxylate ether (PCE) superplasticizers are widely used in concrete, but in some cases, PCE aggravates the occurrence of cracks. This study evaluates the shrinkage reduction and plasticizing properties of a newly synthesized shrink-reducing polycarboxylate polymer (KH-SRPC) modified with ester and silane groups. When the KH-SRPC was implemented at a dosage of 0.3% by weight of cement, the adsorption capacity on the surface of the cement particles and the spreading diameter of the cement improved with respect to traditional PCE. Furthermore, the autogenous shrinkage and drying shrinkage of the mortar containing KH-SRPC were also investigated. When the KH-SRPC content was 0.2% of the weight of the cementitious material, the autogenous shrinkage of the KH-SRPC mortars at 3 and 7 days was reduced by 72.6% and 43.5%, respectively. The drying shrinkage of KH-SRPC mortars decreased by 38.3% at 3 days, 39.0% at 7 days, 39.1% at 14 days, and 35.7% at 28 days. It was found that KH-SRPC changed the pore structure of the solidified mortar, reduced the surface tension of the pore solution, and slowed down the rate of hydration, thereby reducing the total shrinkage of the mortar system. [ABSTRACT FROM AUTHOR]

Reducing or eliminating cracks caused by shrinkage of cementitious materials remains a daunting challenge for construction engineers. Drying shrinkage and autogenous shrinkage are the main shrinkage types in the service process of cement-based materials, which have a great impact on engineering applications. If cracks in concrete generate by drying or autogenous shrinkage, the mechanical properties, water resistance and durability of concrete will be also affected. It is an effective method to use chemical admixtures to inhibit the shrinkage of cement-based materials. Polycarboxylate plasticizer (PCE) is an important chemical admixture in cement-based materials and is widely used in practical engineering. It can bring great value by reducing the shrinkage effect through molecular design. Through our innovative design, a series of shrinkage-reducing polycarboxylate superplasticizers (SRPs) were synthesized, their molecular structures were confirmed by Fourier transform infrared spectroscopy (FTIR) and their molecular properties were determined by gel permeation chromatography (GPC). Furthermore, the shrinkage performances at different ages of the mortars containing the synthesized SRPs with different structures were systematically evaluated. The results showed that compared with the blank sample, the dry shrinkage rate and free shrinkage rate of the mortars containing SRP decreased by over 20% and 15%, respectively. Additionally, the shrinkage rates of the mortars containing SRP were significantly lower than that of the mortar containing conventional PCE, and moreover, the water-reducing performance was improved compared to conventional PCE. Based on the experimental results of surface tension and evaporation rate of different SRP solutions, the mechanism of the shrinkage-reducing effect was probed, as expected to provide guidance for the design and development of new shrinkage-reducing admixtures. [ABSTRACT FROM AUTHOR]

A series of polycarboxylate superplasticizer (PCE) polymers were synthesized from acrylic acid (AA) and isoprenyloxy polyethylene glycol ether (IPEG) at the mole ratios of 3.0, 4.2, 5.0 and 6.0. In this study, the molecular weight properties of PCE polymers were recorded by size exclusion chromatography with the time interval of 1 h. Mini slump test was used to detect the dispersing effectiveness of PCE polymer in cement paste. The results indicated that the reaction rate of monomers, conversion of 52IPEG macromonomer and molecular weight of PCE polymers increased with the general adding ratio of AA to IPEG macromonomers while the side chain density of PCE polymers decreased. PCE polymers possessed molecular weight around 30,000 g/mol with low side chain density, and long main chain length presented high initial dispersing effectiveness at the low dosage around 0.12%. The majority of effective PCE polymers were formed during the adding period of acrylic acid in the first 3 h. [ABSTRACT FROM AUTHOR]

Although the side chain ionizability (the adsorption group density and adsorption space are changed) of polycarboxylate superplasticizer (PCE) serve as the key structural parameter in affecting the cement hydration, its effect on cement hydration is unclear. Based on PCE with nonionizable side chain (NSC-PCE) and the PCE with ionizable side chain (ISC-PCE), the influence of the side chain ionizability of PCE on the hydration behavior of cement was studied. Compared with NSC-PCE, ISC-PCE has a stronger ability to change the migration of water and ions, thus delaying the crystal nucleation and growth of cement hydration (better morphology and distribution, the crystal size was reduced by more than 20 %), increasing the crystal growth index (tendency toward spherical growth), prolonging the phase boundary reaction (reduce micro-cracks), which was conducive to the formation of more uniform and dense crystals (good strength, ISC-PCE: 50.0 MPa > NSC-PCE: 49.2 MPa > Blank: 48.7 MPa). These findings provide the design basis and theoretical guidance for the innovative development of PCE. [Display omitted] • ISC-PCE decreases the hydration rate and hydration degree of cement. • The effect of PCE on the hydration process was studied by the hydration kinetics model. • ISC-PCE has a stronger ability to change the migration of water and ions. • Proposes working mechanism in viewpoints of dissolution-precipitation equilibrium. • Tailoring the side chain ionizability was a new strategy to tune the performance of PCE. [ABSTRACT FROM AUTHOR]

In the synthesis of functional polycarboxylate superplasticizers (PCEs), ester monomer was usually used as small monomer or macromonomer. However, there were few studies on the co-introduction of small ester monomer and ester macromonomer into one PCE molecule and its effects. In this study, it was found an interesting behavior of competitive hydrolysis between these two ester monomers in diester PCE, which performed higher fluidity of cement paste, greater adsorption amount and shorter prolongation of the induction period of cement hydration due to the competitive hydrolysis. Furthermore, the kinetics of hydrolysis and adsorption of the diester PCE were probed, and the rate order was: ester macromonomer < small ester monomer < diester monomers. This study aims to innovatively reveal the special behavior and mechanism of competitive hydrolysis of PCE using diester monomers in cement-based materials and to provide a theoretical basis for enriching molecular design and innovative application of functional PCEs. [Display omitted] • First study on the competitive hydrolysis behavior of PCE having complex diester. • Competitive hydrolysis occurred between small ester monomer and ester macromonomer. • The kinetics of hydrolysis and adsorption of the diester PCE were established. • Better performances in adsorption and dispersibility of diester PCE in cement paste. • Competitive hydrolysis helped reduce the prolongation of hydration induction period. [ABSTRACT FROM AUTHOR]

To solve the problem of high viscosity for fresh concrete especially high-grade concrete, a novel viscosity-reducing type of polycarboxylate superplasticizer (PCE) was synthesized based on innovative design of molecular structure, and also was characterized to confirm the designed molecular structure. The rheological performances of cement paste and fresh concrete containing synthesized PCE were probed, which were analyzed by means of surface tension, adsorption behavior and zeta potential. The plastic viscosity showed a good correlation with T50 and V-funnel time according to mesomechanics process model. Moreover, the investigation of working mechanism interestingly showed that lowering molecular weight and side chain length and introducing hydrophobic groups can achieve improved dispersion capacity and viscosity-reduction effectiveness. The aim of this study is to provide a promising avenue to synthesize PCE with superior workability and viscosity-reducing performance in fresh concrete. This new type of PCE can be used as a viscosity-reducing agent in concrete engineering. [ABSTRACT FROM AUTHOR]

A novel star-shaped polycarboxylate superplasticizer (SPCE) was synthesized through a simple two-step method. 1 H Nuclear Magnetic Resonance ( 1 H NMR) and Infrared Spectroscopy (IR) measurements were used for structural characterization. SPCE and comb-shaped polycarboxylate superplasticizer (CPCE) with same molecular weights were designed and synthesized. The cement paste containing SPCE exhibited better fluidity, fluidity retention, water reduction, 25% lower saturated dosage of PCE, 10% longer setting time, lower hydration heat, more delayed hydration heat evolution and lower amount of hydration products at early ages. Furthermore, the adsorption behavior of SPCE and CPCE in cement pastes and the zeta potential were investigated, and then the working mechanism of SPCE was theoretically explained. It is interesting that changing topological structure from comb-shape to star-shape can achieve the optimization of dispersion effect, and further improve the working effectiveness. The aims of this study are to provide a new avenue to synthesize superplasticizer with novel structure achieving the chemical diversity of superplasticizer structure, and to verify the contribution of optimizing molecular shape. This new type of superplasticizer can be used as a rheology modifying agent in fresh cement-based materials. [ABSTRACT FROM AUTHOR]

• A novel sulfonate-modified PCE was synthesized based on innovative molecular design. • Sulfonate modification on the side chains of PCE can enhance the sulfate tolerance. • Effects of competitive adsorption, ionic strength and conformation were studied. • Good performance retention and stability were shown for solving compatibility problem. • Many quantitative evaluation indexes for sulfate tolerance of PCE were established. A novel polycarboxylate superplasticizer (PCE) was synthesized by graft copolymerization between acrylic acid (AA) and end-functionalized poly (allyl sulfonate) (PALS) to produce comb polymer, i.e. PAA-g-PALS. The molecular structure was confirmed by Infrared Spectroscopy (IR) and 1H Nuclear Magnetic Resonance (1H NMR), and the molecular properties were characterized by Gel Permeation Chromatography (GPC). The conventional PCE with comb structure using isobutenyl polyethylene glycol (IPEG) as side chains (i.e. PAA-g-IPEG) was also synthesized to explore the effect of the side chain on the PCE performances. The fluidity and its retention, rheological properties, hydrodynamic radii (R h), adsorption behavior and zeta potential of the cement pastes containing PAA-g-PALS or PAA-g-IPEG were comparatively tested. It was found that this designed "sulfonate modified PCE" exhibited stronger dispersing stability and sulfate tolerance to cement paste and less sensitive to the sulfate competitive adsorption and the increase in ionic strength. Based on the above results, the evaluation method (the sulfate resistance index of PAA-g-PALS was increased by 24% as compared to that of PAA-g-IPEG) was innovatively established and the mechanism of sulfate resistance was clarified in detail. The purpose of this research is to offer an avenue with great potentials to synthesize a novel PCE with excellent workability retention and sulfate tolerance in fresh cement pastes. This sulfonate-modified polycarboxylate superplasticizer has great potentials as a viable alternative to conventional PCE, especially in some harsh cement systems. [ABSTRACT FROM AUTHOR]