Inorganic nanotubes of tungsten disulfide （INTs-WS2） are insoluble in common solvents and practically inert, hindering their usefulness in both research and commercial applications. The covalent attachment of functi...Inorganic nanotubes of tungsten disulfide （INTs-WS2） are insoluble in common solvents and practically inert, hindering their usefulness in both research and commercial applications. The covalent attachment of functional species onto the surface of INT-WS2 is a critical first step in realizing the potential that INT-WS2 offer for high-performance materials and products. Although a few attempts have been reported regarding preparing modified nanotubes, only a limited range of surface functionalities is possible with these methods. We have developed a versatile method, based on a modified, highly electrophilic acidic Vilsmeier- Haack reagent, to produce covalently bonded, polycarboxylated functional WS2 nanotubes that are dispersible in polar liquids, including water. The surface polycarboxylated shell provides a means for additional derivatization, enabling matching compatibility of derivatized nanotubes to both hydrophobic and hydrophilic materials. Nanocomposites incorporating derivatized INT-WS2 are expected to show improved properties as a result of enhanced interfacial compatibility, made possible by the large number of classes of functionalization available through the initial polycarboxylation step.展开更多
The mechanochemical synthesis of polycarboxylate superplasticizers(PCEs)was achieved using a planetary ball mill at ambient temperature.The effects of ball milling parameters,including speed,time,and stop method,on PC...The mechanochemical synthesis of polycarboxylate superplasticizers(PCEs)was achieved using a planetary ball mill at ambient temperature.The effects of ball milling parameters,including speed,time,and stop method,on PCE performance,molecular weight,and distribution were investigated to optimize conditions.The experimental results suggest that ball milling impacts PCE molecular weight and distribution,striking a balance between polymerization and mechanical degradation during synthesis.The optimal parameters were found to be 400 rpm,120 minutes total time,and 30 minutes milling plus 3 minutes rest cycles.Under these conditions,the PCE exhibits excellent dispersibility with a cement paste fluidity of 260 mm.The mechanochemical approach eliminates heating requirements,and also reduces the reaction time from 300 to 120 minutes compared to traditional aqueous synthesis.The optimized PCE demonstrates an increased density of long-side chains,leading to enhanced early strength,heightens adsorption,and diminished zeta potential in cement systems.These characteristics are comparable to traditionally synthesized PCEs.Moreover,at higher dosages,further augmentation of PCE adsorption and increased cement paste fluidity were noted here.展开更多
This article presents a preparation method for a tailing sand-specific polycarboxylate superplasticizer(AT9)containing multifunctional adsorption groups.By designing multifunctional adsorption groups(-COOH)as side cha...This article presents a preparation method for a tailing sand-specific polycarboxylate superplasticizer(AT9)containing multifunctional adsorption groups.By designing multifunctional adsorption groups(-COOH)as side chains grafted onto the main chain of conventional polycarboxylate ether,the antiadsorption effect is achieved.AT9 was characterized by gel permeation chromatography,and its performance was systematically evaluated in various tailings sand-cement mortar systems.A comparison was made between AT9 and traditional PCE in terms of their effects on the workability of concrete,and the interaction mechanism between AT9 and clay in cementitious systems was discussed.The results indicate that AT9 enhances the adsorption and dispersion effects of polycarboxylate superplasticizers on cement particles,and increases steric hindrance,thereby avoids intercalation adsorption of tailings sand,improves its water-reducing and slump-retaining performance,and also contributes to the strength enhancement of concrete in later stages.展开更多
To address the dual challenges of resource utilization of mining solid waste(e.g.,coal gangue)and performance enhancement of cemented rockfill,this study systematically investigates the mechanisms of ultrasonic disper...To address the dual challenges of resource utilization of mining solid waste(e.g.,coal gangue)and performance enhancement of cemented rockfill,this study systematically investigates the mechanisms of ultrasonic dispersion time and polycarboxylate superplasti-cizer(PCE)on the properties of cellulose nanofiber(CNF)-modified cemented rockfill.A series of comparative experiments were de-signed with varying ultrasonic dispersion times(0-60 min)and PCE dosages(0.1wt%-0.4wt%).Through mechanical testing,hydration product analysis,and microstructural characterization,the study revealed the advantages of PCE in promoting CNF dispersion to enhance the engineering applicability of cemented rockfill.The results demonstrate that:(1)Ultrasonic dispersion for 30 min increases the com-pressive strength by 37.7%compared to the untreated group;however,excessive ultrasonication(60 min)induces hydrolysis of CNF,re-leasing reducing sugars that retard hydration.(2)PCE facilitates CNF dispersion,achieving a 29.1%increase in compressive strength at a dosage of 0.4wt%,while simultaneously improving hydration products and microstructural development.(3)While ultrasonic dispersion yields slightly higher strength improvements,PCE demonstrates superior cost-effectiveness and operational convenience,rendering it more viable for industrial adoption.This study provides a theoretical foundation for the nano-enhanced modification of cemented rockfill,offering new insights into the recycling of solid waste and the development of high-performance materials.展开更多
Effects of polycarboxylate-type superplasticizer（PC） molecular structure on the hydration heat of tricalcium silicate（C3S） paste and polymerization degree of hydration products（C-S-H gel） were researched by usin...Effects of polycarboxylate-type superplasticizer（PC） molecular structure on the hydration heat of tricalcium silicate（C3S） paste and polymerization degree of hydration products（C-S-H gel） were researched by using TAM AIR isothermal microcalorimetry（TA） and 29Si nuclear magnetic resonance（NMR）.Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.展开更多
Bridge polycarboxylate superplasticizers（PCs） with crosslink structure were synthesized by using polyethyleneglycol di-acrylate（PEGdA）, replacing partial polyethyleneglycol mono-acrylate （PEGmA） as crosslinking ...Bridge polycarboxylate superplasticizers（PCs） with crosslink structure were synthesized by using polyethyleneglycol di-acrylate（PEGdA）, replacing partial polyethyleneglycol mono-acrylate （PEGmA） as crosslinking agent. Structures of bridge PCs were analyzed by gel permeation chromatography, and dispersion ability was evaluated by cement paste dispersity variation on time and rheology test. The experimental results showed that, molecular weight（MW） of bridge PCs increased with increase of PEGdA proportion, and MW distribution curve changed from Gaussian to fiat like, which meant notable increase of highly crosslinked copolymer. Bridge PCs led to decreased initial cement paste dispersity and better dispersity retention due to slow releasing. Further research showed that, PEGdA proportion had slight effect on polymerization degree of backbone, MW distribution of backbone deviated from Gaussian distribution and shoulder peaks appeared on distribution curve when PEGdA increased.展开更多
The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular str...The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount(when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.展开更多
Circulating fluidized bed combustion （CFBC） ash exhibits the desirable pozzolanic activity which makes it a potential supplementary cementitious material to replace cement for concrete production. However, the high ...Circulating fluidized bed combustion （CFBC） ash exhibits the desirable pozzolanic activity which makes it a potential supplementary cementitious material to replace cement for concrete production. However, the high unburnt carbon content and porous surface structure of CFBC ash may adsorb water reducer and thereby significantly reduce the efficiency of water-reducing agents. The adsorption mechanism of polycarboxylate superplasticizer in CFBC ash-Portland cement paste was investigated by ultraviolet-visible spectrophotometer, and the conception of ＂invalid adsorption site＂ of CFBC ash was presented. The results show that the adsorption behavior of polycarboxylate superplasticizer in coal ash-Portland cement paste can be described by Langmuir isothermal adsorption equation. The adsorption capacity of CFBC ash-Portland cement paste is higher than that of pulverized coal combustion （PCC） fly ash-Portland cement paste. Moreover, the adsorption amount of polycarboxylate superplasticizer increases with the ratio of ash-to-cement in the paste. At last, the fluidity of CFBC ash-Portland cement paste is lower than that of the PCC fly ash paste. This work suggests that when CFBC ash is used as concrete admixture, the poor flowability of the cementitious system due to the high adsorption of water and water-reducing agent should be taken into consideration.展开更多
A low adsorption clay-resistant polycarboxylate superplasticizer(KN-PC)was synthesized using acrylic acid and isopentenol polyoxyethylene ether as the main reaction materials.The structural characterization and clay-r...A low adsorption clay-resistant polycarboxylate superplasticizer(KN-PC)was synthesized using acrylic acid and isopentenol polyoxyethylene ether as the main reaction materials.The structural characterization and clay-resistant mechanism of the KN-PC were explored using Fourier transform infrared spectroscopy and X-ray diffraction,and the effect of the KN-PC on the performance of composite paste with various montmorillonite(MMT)contents was analyzed.Compared with ordinary polycarboxylate superplasticizer(PC),the KN-PC has a low sensitivity to the MMT.By the action of the MMT,the adsorption dosage of the KN-PC on the MMT is much smaller than that of the PC.展开更多
Molecular structures of polycarboxylate（PCE） superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic dens...Molecular structures of polycarboxylate（PCE） superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P（PEG1-AA6） possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.展开更多
A new kind of nano-rod shaped polycarboxylic acid slump-retaining agent was synthesized.Transmission electron microscope(TEM) experiment showed that the nano-rod was bound together as macromolecular aggregates in solu...A new kind of nano-rod shaped polycarboxylic acid slump-retaining agent was synthesized.Transmission electron microscope(TEM) experiment showed that the nano-rod was bound together as macromolecular aggregates in solution.Application performance studying suggested that this kind nano-sized polymer material had excellently plasticity-retaining performance in cement-based materials and could improve endurance performance of hardened cement-based materials distinctly.The concrete with an initial slump of 2-9 cm could achieve 3 h plasticity-retaining performance with the help of this kind nano-rod.The product had extremely wide application value in the market.展开更多
The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the ...The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result,the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.展开更多
The dispersion ability of polycarboxylate superplasticizer（PCE） in fresh concrete was much impeded by clay impurities. To improve the dispersion of PCE in the clay-contained concrete, a novel PCE with carboxyl as a ...The dispersion ability of polycarboxylate superplasticizer（PCE） in fresh concrete was much impeded by clay impurities. To improve the dispersion of PCE in the clay-contained concrete, a novel PCE with carboxyl as a specific branched chain terminal group was synthesized, using modified polyether as the raw material which was prepared through esterification between hexahydrophthalic anhydride（HHPA） and isobutenyl polyoxyethylene ether（IPEG） with hydroxy as the terminal group. The esterification product and PCE molecular structure were characterized by infrared spectroscopy and ~1HNMR resonance. The results confirmed that the product molecular structure was a comb-type copolymer with long-chain terminal carboxyl group and PEO attached directly to the backbone chain. The as-synthesized PCEs had favorable dispersibility in cement than conventional PCE in the presence of montmorillonite（Mmt） clay. This can be attributed to the introduction of electronegative carboxyl to PCE long-chain terminal group, which reduces the adsorption of PCE on Mmt, and thus improves the tolerance of PCE to the Mmt.展开更多
The infl uence law of clay on mortar fluidity mixed with polycarboxylate superplasticizer was studied. Several methods of inhibiting clay adsorption of polycarboxylate superplasticizer were discussed. The experimental...The infl uence law of clay on mortar fluidity mixed with polycarboxylate superplasticizer was studied. Several methods of inhibiting clay adsorption of polycarboxylate superplasticizer were discussed. The experimental results show that clay has signifi cant effect on the dispersion of polycarboxylate superplasticizer and montmorillonite clay has more signifi cant impact on mortar fluidity than other clays. The pH value and the salts of the solution can affect the adsorption of clay to polycarboxylate superplasticizer. The incorporation of a small amount of sodium hydroxide solution, sodium silicate or cationic surfactants can improve the effect of the clay on the dispersion of polycarboxylate superplasticizer.展开更多
For investigating the accelerated blood clearance(ABC) phenomenon of polyglycerin modified nanoemulsions upon cross administration with polyethylene glycol(PEG) covered nanoemulsion, we used the 1,2-distea-royl-sn-gly...For investigating the accelerated blood clearance(ABC) phenomenon of polyglycerin modified nanoemulsions upon cross administration with polyethylene glycol(PEG) covered nanoemulsion, we used the 1,2-distea-royl-sn-glycero-3-phosphoethanolamine-npolyglycerine-610 and the 1,2-distearoyl-n-glycero-3-phosphoethanolamine-n-[methoxy(polyethylene glycol)-2000] as modify materials, the dialkylcarbocyanines as fluorescence indicator. Exhausted macrophages rat model was established and new material containing polycarboxyl structure was synthesized. The microplate reader and the in vivo optical imaging system were applied to measure the concentration of nanoemulsions in tissues.The results show that the first dose of polyglycerin modified nanoemulsion can induce the ABC phenomenon of the second dose of PEGylated nanoemulsion. With the increase in the amount of the surface polyglycerin, the extent of the ABC phenomenon decreases. Liver accumulation has positive relationship with the ABC phenomenon. Furthermore, kupffer cells in liver can get more immune information from polyhydroxy structure than polycarboxyl group in the modify compound. The results of our work imply that the polycarboxyl structure has advantages to eliminate the ABC phenomenon.展开更多
A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride（PMA） with 3-methyl-1-（4- sulfonylphenyl）-4-（4-aminophenylazo）-2-pyrazoline-5-one.The structure of the novel dye wa...A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride（PMA） with 3-methyl-1-（4- sulfonylphenyl）-4-（4-aminophenylazo）-2-pyrazoline-5-one.The structure of the novel dye was characterized by FTIR,UV-vis and ^（13）C NMR spectra.The dyeing properties of dye on cotton were tested,and the novel dye possessed high fixation and good fastness.展开更多
To achieve higher strength and better durability,ultra-high performance concrete(UHPC)typically employs a relatively small water-binder ratio.However,this generally leads to an undesired increase in the paste viscosit...To achieve higher strength and better durability,ultra-high performance concrete(UHPC)typically employs a relatively small water-binder ratio.However,this generally leads to an undesired increase in the paste viscosity.In this study,the effects of liquid and powder polycarboxylate superplasticizers(PCE)on UHPC are compared and critically discussed.Moreover,the following influential factors are considered:air-entraining agents(AE),slump retaining agents(SA),and defoaming agents(DF)and the resulting flow characteristics,mechanical properties,and hydration properties are evaluated assuming UHPC containing 8‰powder PCE(PCE-based UHPC).It is found that the spread diameter of powder PCE is 5%higher than that of liquid PCE.Among the chemical admixtures studied,AEs have the best effect on improving UHPC workability,while DFs have the worst effect.When the addition of AE and SA is 1.25‰and 14.7%of PCE,paste viscosity reduces by 35%and 19%,respectively compared to the paste with only 8‰PCE.A low AE dosage(1.25‰)decreases compressive strength by 4.1%,while SA(8.1%)increases UHPC compressive strength by 9.1%.Both AE and SA significantly delay the UHPC hydration process,reducing the hydration heat release peaks by 76%and 27%,respectively.展开更多
The reaction of AgNO3 , 4,4′-bipyridine （bpy） and 2,2′-bipyridine-3,3′-dicarboxylic acid （H2bpdc）/2,2′-biquinoline-4,4′-dicarboxylic acid （H2bqdc）/1,3-benzenedicarboxylic acid （H2bdc） gave rise to block-l...The reaction of AgNO3 , 4,4′-bipyridine （bpy） and 2,2′-bipyridine-3,3′-dicarboxylic acid （H2bpdc）/2,2′-biquinoline-4,4′-dicarboxylic acid （H2bqdc）/1,3-benzenedicarboxylic acid （H2bdc） gave rise to block-like crystals of [Ag4（bpy）2（bpdc）2]·13H2O（1）, [Ag2（bpy）（bqdc）（H2O）]·4.5H2O（2） and [Ag2（bpy）2（H2O）2]（bdc）·3H2O（3） by slow evaporation. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions （bpdc2- , bqdc2- and bdc2- ） and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complex layers, and the abundant Ag···Ag, Ag···N and π-π stacking interactions further strengthen the 3D frameworks. The lattice water molecules are situated among the framework of crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of organic anions in the crystal packing. Additionally, the thermal properties of 1, 2 and 3 were also discussed in detail.展开更多
A procedure was developed for the determination of residual monomers in polycarboxylate superplasticizer （PCs） by reversed-phase high performance liquid chromatography （RP-HPLC）.Four kinds of residual monomers wer...A procedure was developed for the determination of residual monomers in polycarboxylate superplasticizer （PCs） by reversed-phase high performance liquid chromatography （RP-HPLC）.Four kinds of residual monomers were well separated and determined on a SinoChrom ODS-BP （C18） column with mobile phases composed of acetonitrile and phosphate buffer solution.The monomers were detected by UV detector at 205 nm and quantitatively analyzed with an external standard method.For those residual monomers,the linear response ranged from 4.0×10-6 mol·L-1 to 2.0×10-3 mol·L-1.The determination limit of acrylic acid,sodium methylallyl sulfonate and 2-Acrylamido-2-methylpropane sulfonic acid was 0.02×10-5 mol·L-1,while that of methoxy-polyethylene glycol monoacrylate was 0.1×10-5 mol·L-1.The relative standard deviation （RSD） of high concentration samples was less than 1%,while that of the low concentration samples was between 1%-4%.The standard （additional） recovery ratio was 97.4% -104.2%.展开更多
The reactivity ratio of monomer and the microstructure of copolymer as polycarboxylate ether(PCE)superplasticizer were investigated.Polycarboxylate ethers(PCEs)were synthesized from methyl allyl polyethylene glycol(MA...The reactivity ratio of monomer and the microstructure of copolymer as polycarboxylate ether(PCE)superplasticizer were investigated.Polycarboxylate ethers(PCEs)were synthesized from methyl allyl polyethylene glycol(MAPEG,Mw=2400 g/mol)and methacrylic acid(MAA)via aqueous free radical copolymerization in low conversion(P<20%).Gel permeation chromatography(GPC)and high performance liquid chromatography(HPLC)were used to track the residual concentration of the reactants and the amount of copolymer formed during the copolymerization.The reactivity ratios of monomers,MAPEG and MAA,were determined as r1(MAPEG)=0.0489 and r2(MAA)=1.6173,respectively,by employing the K-T and YBR methods.According to the obtained monomer reactivity results,the sequence distribution of the copolymer,the number average length of MAA in the polymerisate were found to decline with the decrease of the mole fraction of MAA in the polymerization system.As a result,the distribution of chain segments becomes narrower and the copolymer structure becomes more uniform.Therefore,uniform polymers could be obtained by slowly adding MAA monomer during copolymerization process.展开更多
文摘Inorganic nanotubes of tungsten disulfide （INTs-WS2） are insoluble in common solvents and practically inert, hindering their usefulness in both research and commercial applications. The covalent attachment of functional species onto the surface of INT-WS2 is a critical first step in realizing the potential that INT-WS2 offer for high-performance materials and products. Although a few attempts have been reported regarding preparing modified nanotubes, only a limited range of surface functionalities is possible with these methods. We have developed a versatile method, based on a modified, highly electrophilic acidic Vilsmeier- Haack reagent, to produce covalently bonded, polycarboxylated functional WS2 nanotubes that are dispersible in polar liquids, including water. The surface polycarboxylated shell provides a means for additional derivatization, enabling matching compatibility of derivatized nanotubes to both hydrophobic and hydrophilic materials. Nanocomposites incorporating derivatized INT-WS2 are expected to show improved properties as a result of enhanced interfacial compatibility, made possible by the large number of classes of functionalization available through the initial polycarboxylation step.
基金Funded by the National Natural Science Foundation of China(Nos.U1905216 and 52108208)the Henan Provincial Science and Technology Research Project(No.212102310559)。
文摘The mechanochemical synthesis of polycarboxylate superplasticizers(PCEs)was achieved using a planetary ball mill at ambient temperature.The effects of ball milling parameters,including speed,time,and stop method,on PCE performance,molecular weight,and distribution were investigated to optimize conditions.The experimental results suggest that ball milling impacts PCE molecular weight and distribution,striking a balance between polymerization and mechanical degradation during synthesis.The optimal parameters were found to be 400 rpm,120 minutes total time,and 30 minutes milling plus 3 minutes rest cycles.Under these conditions,the PCE exhibits excellent dispersibility with a cement paste fluidity of 260 mm.The mechanochemical approach eliminates heating requirements,and also reduces the reaction time from 300 to 120 minutes compared to traditional aqueous synthesis.The optimized PCE demonstrates an increased density of long-side chains,leading to enhanced early strength,heightens adsorption,and diminished zeta potential in cement systems.These characteristics are comparable to traditionally synthesized PCEs.Moreover,at higher dosages,further augmentation of PCE adsorption and increased cement paste fluidity were noted here.
文摘This article presents a preparation method for a tailing sand-specific polycarboxylate superplasticizer(AT9)containing multifunctional adsorption groups.By designing multifunctional adsorption groups(-COOH)as side chains grafted onto the main chain of conventional polycarboxylate ether,the antiadsorption effect is achieved.AT9 was characterized by gel permeation chromatography,and its performance was systematically evaluated in various tailings sand-cement mortar systems.A comparison was made between AT9 and traditional PCE in terms of their effects on the workability of concrete,and the interaction mechanism between AT9 and clay in cementitious systems was discussed.The results indicate that AT9 enhances the adsorption and dispersion effects of polycarboxylate superplasticizers on cement particles,and increases steric hindrance,thereby avoids intercalation adsorption of tailings sand,improves its water-reducing and slump-retaining performance,and also contributes to the strength enhancement of concrete in later stages.
基金support from the National Natural Science Foundation of China(Nos.42372328,U23B2091,52478253,and 52374147)Natural Science Foundation of Jiangsu Province,China(No.BK20240209).
文摘To address the dual challenges of resource utilization of mining solid waste(e.g.,coal gangue)and performance enhancement of cemented rockfill,this study systematically investigates the mechanisms of ultrasonic dispersion time and polycarboxylate superplasti-cizer(PCE)on the properties of cellulose nanofiber(CNF)-modified cemented rockfill.A series of comparative experiments were de-signed with varying ultrasonic dispersion times(0-60 min)and PCE dosages(0.1wt%-0.4wt%).Through mechanical testing,hydration product analysis,and microstructural characterization,the study revealed the advantages of PCE in promoting CNF dispersion to enhance the engineering applicability of cemented rockfill.The results demonstrate that:(1)Ultrasonic dispersion for 30 min increases the com-pressive strength by 37.7%compared to the untreated group;however,excessive ultrasonication(60 min)induces hydrolysis of CNF,re-leasing reducing sugars that retard hydration.(2)PCE facilitates CNF dispersion,achieving a 29.1%increase in compressive strength at a dosage of 0.4wt%,while simultaneously improving hydration products and microstructural development.(3)While ultrasonic dispersion yields slightly higher strength improvements,PCE demonstrates superior cost-effectiveness and operational convenience,rendering it more viable for industrial adoption.This study provides a theoretical foundation for the nano-enhanced modification of cemented rockfill,offering new insights into the recycling of solid waste and the development of high-performance materials.
基金Funded by the National Basic Research Program of China(973 Program)(No.2009CB623201)
文摘Effects of polycarboxylate-type superplasticizer（PC） molecular structure on the hydration heat of tricalcium silicate（C3S） paste and polymerization degree of hydration products（C-S-H gel） were researched by using TAM AIR isothermal microcalorimetry（TA） and 29Si nuclear magnetic resonance（NMR）.Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.
基金Funded by the Western Region Traffic Construction Technology Program of the Ministry of Transport of China(No.2007319811130)
文摘Bridge polycarboxylate superplasticizers（PCs） with crosslink structure were synthesized by using polyethyleneglycol di-acrylate（PEGdA）, replacing partial polyethyleneglycol mono-acrylate （PEGmA） as crosslinking agent. Structures of bridge PCs were analyzed by gel permeation chromatography, and dispersion ability was evaluated by cement paste dispersity variation on time and rheology test. The experimental results showed that, molecular weight（MW） of bridge PCs increased with increase of PEGdA proportion, and MW distribution curve changed from Gaussian to fiat like, which meant notable increase of highly crosslinked copolymer. Bridge PCs led to decreased initial cement paste dispersity and better dispersity retention due to slow releasing. Further research showed that, PEGdA proportion had slight effect on polymerization degree of backbone, MW distribution of backbone deviated from Gaussian distribution and shoulder peaks appeared on distribution curve when PEGdA increased.
基金Funded by the National Natural Science Foundation of China(No.51808369)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.18KJB560016)+3 种基金the Opening Project of State Key Laboratory of Green Building Materials(No.YA-615)the State Key Laboratory of Silicate Materials for Architectures(No.SYSJJ2018-09)Science and Technology Project of Jiangsu Provincal Department of Housing and Urban-Rural Construction(No.2018ZD049)the Natural Science Foundation of Suzhou University of Science and Technology(No.XKQ2018009)
文摘The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount(when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.
基金Funded by the National Natural Science Foundation of China(Nos.51132010 and 51272222)the Programs for Science and Technology Development of Yantai City,Shandong Province,China(No.2012ZH249)
文摘Circulating fluidized bed combustion （CFBC） ash exhibits the desirable pozzolanic activity which makes it a potential supplementary cementitious material to replace cement for concrete production. However, the high unburnt carbon content and porous surface structure of CFBC ash may adsorb water reducer and thereby significantly reduce the efficiency of water-reducing agents. The adsorption mechanism of polycarboxylate superplasticizer in CFBC ash-Portland cement paste was investigated by ultraviolet-visible spectrophotometer, and the conception of ＂invalid adsorption site＂ of CFBC ash was presented. The results show that the adsorption behavior of polycarboxylate superplasticizer in coal ash-Portland cement paste can be described by Langmuir isothermal adsorption equation. The adsorption capacity of CFBC ash-Portland cement paste is higher than that of pulverized coal combustion （PCC） fly ash-Portland cement paste. Moreover, the adsorption amount of polycarboxylate superplasticizer increases with the ratio of ash-to-cement in the paste. At last, the fluidity of CFBC ash-Portland cement paste is lower than that of the PCC fly ash paste. This work suggests that when CFBC ash is used as concrete admixture, the poor flowability of the cementitious system due to the high adsorption of water and water-reducing agent should be taken into consideration.
基金Funded by National Natural Science Foundation of China(No.51778378)。
文摘A low adsorption clay-resistant polycarboxylate superplasticizer(KN-PC)was synthesized using acrylic acid and isopentenol polyoxyethylene ether as the main reaction materials.The structural characterization and clay-resistant mechanism of the KN-PC were explored using Fourier transform infrared spectroscopy and X-ray diffraction,and the effect of the KN-PC on the performance of composite paste with various montmorillonite(MMT)contents was analyzed.Compared with ordinary polycarboxylate superplasticizer(PC),the KN-PC has a low sensitivity to the MMT.By the action of the MMT,the adsorption dosage of the KN-PC on the MMT is much smaller than that of the PC.
基金the State Key Laboratory of Silicate Materials for Architectures(SYSJJ2018-09)the Shaanxi Provincial High Performance Concrete Engineering Laboratory(SHPC201701)
文摘Molecular structures of polycarboxylate（PCE） superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P（PEG1-AA6） possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.
基金the Jiangsu Province Natural Science Foundation(No.BK2008520)the Jiangsu Postdoctoral Research Funds(No.0901008C)the China Postdoctoral Science Foundation(No.20090461120)
文摘A new kind of nano-rod shaped polycarboxylic acid slump-retaining agent was synthesized.Transmission electron microscope(TEM) experiment showed that the nano-rod was bound together as macromolecular aggregates in solution.Application performance studying suggested that this kind nano-sized polymer material had excellently plasticity-retaining performance in cement-based materials and could improve endurance performance of hardened cement-based materials distinctly.The concrete with an initial slump of 2-9 cm could achieve 3 h plasticity-retaining performance with the help of this kind nano-rod.The product had extremely wide application value in the market.
基金Funded by the National Natural Science Foundation of China(No.50972170)
文摘The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result,the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.
文摘The dispersion ability of polycarboxylate superplasticizer（PCE） in fresh concrete was much impeded by clay impurities. To improve the dispersion of PCE in the clay-contained concrete, a novel PCE with carboxyl as a specific branched chain terminal group was synthesized, using modified polyether as the raw material which was prepared through esterification between hexahydrophthalic anhydride（HHPA） and isobutenyl polyoxyethylene ether（IPEG） with hydroxy as the terminal group. The esterification product and PCE molecular structure were characterized by infrared spectroscopy and ~1HNMR resonance. The results confirmed that the product molecular structure was a comb-type copolymer with long-chain terminal carboxyl group and PEO attached directly to the backbone chain. The as-synthesized PCEs had favorable dispersibility in cement than conventional PCE in the presence of montmorillonite（Mmt） clay. This can be attributed to the introduction of electronegative carboxyl to PCE long-chain terminal group, which reduces the adsorption of PCE on Mmt, and thus improves the tolerance of PCE to the Mmt.
基金Funded by the National Natural Science Foundation of China(50872151)the Beijing Municipal Education Commission Program Projects and Beijing University of Civil Engineering and Architecture,Dr.Fund
文摘The infl uence law of clay on mortar fluidity mixed with polycarboxylate superplasticizer was studied. Several methods of inhibiting clay adsorption of polycarboxylate superplasticizer were discussed. The experimental results show that clay has signifi cant effect on the dispersion of polycarboxylate superplasticizer and montmorillonite clay has more signifi cant impact on mortar fluidity than other clays. The pH value and the salts of the solution can affect the adsorption of clay to polycarboxylate superplasticizer. The incorporation of a small amount of sodium hydroxide solution, sodium silicate or cationic surfactants can improve the effect of the clay on the dispersion of polycarboxylate superplasticizer.
基金supported by the National Natural Science Foundation of China (Grant Nos.81072602,81373334)
文摘For investigating the accelerated blood clearance(ABC) phenomenon of polyglycerin modified nanoemulsions upon cross administration with polyethylene glycol(PEG) covered nanoemulsion, we used the 1,2-distea-royl-sn-glycero-3-phosphoethanolamine-npolyglycerine-610 and the 1,2-distearoyl-n-glycero-3-phosphoethanolamine-n-[methoxy(polyethylene glycol)-2000] as modify materials, the dialkylcarbocyanines as fluorescence indicator. Exhausted macrophages rat model was established and new material containing polycarboxyl structure was synthesized. The microplate reader and the in vivo optical imaging system were applied to measure the concentration of nanoemulsions in tissues.The results show that the first dose of polyglycerin modified nanoemulsion can induce the ABC phenomenon of the second dose of PEGylated nanoemulsion. With the increase in the amount of the surface polyglycerin, the extent of the ABC phenomenon decreases. Liver accumulation has positive relationship with the ABC phenomenon. Furthermore, kupffer cells in liver can get more immune information from polyhydroxy structure than polycarboxyl group in the modify compound. The results of our work imply that the polycarboxyl structure has advantages to eliminate the ABC phenomenon.
基金supported by the State Key Program of National Natural Science Foundation of China(No. 20836001)the Program for Changjiang Scholars and Innovative Research Team in the University(No.IRT0711)
文摘A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride（PMA） with 3-methyl-1-（4- sulfonylphenyl）-4-（4-aminophenylazo）-2-pyrazoline-5-one.The structure of the novel dye was characterized by FTIR,UV-vis and ^（13）C NMR spectra.The dyeing properties of dye on cotton were tested,and the novel dye possessed high fixation and good fastness.
基金Key Research and Development Program of Hubei Province(2022BCA082 and 2022BCA077).
文摘To achieve higher strength and better durability,ultra-high performance concrete(UHPC)typically employs a relatively small water-binder ratio.However,this generally leads to an undesired increase in the paste viscosity.In this study,the effects of liquid and powder polycarboxylate superplasticizers(PCE)on UHPC are compared and critically discussed.Moreover,the following influential factors are considered:air-entraining agents(AE),slump retaining agents(SA),and defoaming agents(DF)and the resulting flow characteristics,mechanical properties,and hydration properties are evaluated assuming UHPC containing 8‰powder PCE(PCE-based UHPC).It is found that the spread diameter of powder PCE is 5%higher than that of liquid PCE.Among the chemical admixtures studied,AEs have the best effect on improving UHPC workability,while DFs have the worst effect.When the addition of AE and SA is 1.25‰and 14.7%of PCE,paste viscosity reduces by 35%and 19%,respectively compared to the paste with only 8‰PCE.A low AE dosage(1.25‰)decreases compressive strength by 4.1%,while SA(8.1%)increases UHPC compressive strength by 9.1%.Both AE and SA significantly delay the UHPC hydration process,reducing the hydration heat release peaks by 76%and 27%,respectively.
基金Supported by Funding Project forAcademic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (No.PHR201008372 and PHR201106124)Open Research Fund Program of Key Laboratory of Urban Stormwater System and Water Environment (Ministry of Education),Beijing University of Civil Engineering and Architecture (No.YH201101003)
文摘The reaction of AgNO3 , 4,4′-bipyridine （bpy） and 2,2′-bipyridine-3,3′-dicarboxylic acid （H2bpdc）/2,2′-biquinoline-4,4′-dicarboxylic acid （H2bqdc）/1,3-benzenedicarboxylic acid （H2bdc） gave rise to block-like crystals of [Ag4（bpy）2（bpdc）2]·13H2O（1）, [Ag2（bpy）（bqdc）（H2O）]·4.5H2O（2） and [Ag2（bpy）2（H2O）2]（bdc）·3H2O（3） by slow evaporation. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions （bpdc2- , bqdc2- and bdc2- ） and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complex layers, and the abundant Ag···Ag, Ag···N and π-π stacking interactions further strengthen the 3D frameworks. The lattice water molecules are situated among the framework of crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of organic anions in the crystal packing. Additionally, the thermal properties of 1, 2 and 3 were also discussed in detail.
基金Funded by the Western Region Traffic Construction Technology Program of the Ministry of Communications of China(No.2007319811130)
文摘A procedure was developed for the determination of residual monomers in polycarboxylate superplasticizer （PCs） by reversed-phase high performance liquid chromatography （RP-HPLC）.Four kinds of residual monomers were well separated and determined on a SinoChrom ODS-BP （C18） column with mobile phases composed of acetonitrile and phosphate buffer solution.The monomers were detected by UV detector at 205 nm and quantitatively analyzed with an external standard method.For those residual monomers,the linear response ranged from 4.0×10-6 mol·L-1 to 2.0×10-3 mol·L-1.The determination limit of acrylic acid,sodium methylallyl sulfonate and 2-Acrylamido-2-methylpropane sulfonic acid was 0.02×10-5 mol·L-1,while that of methoxy-polyethylene glycol monoacrylate was 0.1×10-5 mol·L-1.The relative standard deviation （RSD） of high concentration samples was less than 1%,while that of the low concentration samples was between 1%-4%.The standard （additional） recovery ratio was 97.4% -104.2%.
基金Funded by the Key Materials and Preparation Technology of Long-life Concrete Products Project(No.2017YFB0310002)through the National Key R&D Program。
文摘The reactivity ratio of monomer and the microstructure of copolymer as polycarboxylate ether(PCE)superplasticizer were investigated.Polycarboxylate ethers(PCEs)were synthesized from methyl allyl polyethylene glycol(MAPEG,Mw=2400 g/mol)and methacrylic acid(MAA)via aqueous free radical copolymerization in low conversion(P<20%).Gel permeation chromatography(GPC)and high performance liquid chromatography(HPLC)were used to track the residual concentration of the reactants and the amount of copolymer formed during the copolymerization.The reactivity ratios of monomers,MAPEG and MAA,were determined as r1(MAPEG)=0.0489 and r2(MAA)=1.6173,respectively,by employing the K-T and YBR methods.According to the obtained monomer reactivity results,the sequence distribution of the copolymer,the number average length of MAA in the polymerisate were found to decline with the decrease of the mole fraction of MAA in the polymerization system.As a result,the distribution of chain segments becomes narrower and the copolymer structure becomes more uniform.Therefore,uniform polymers could be obtained by slowly adding MAA monomer during copolymerization process.
