Influence of High-Robustness Polycarboxylate Superplasticizer on the Performances of Concrete Incorporating Fly Ash and Manufactured Sand

Using ethylene glycol monovinyl polyoxyethylene ether,2-acrylamido-2-methylpropane sulfonic acid(AMPS)and acrylic acid as the main synthetic monomers,a high robustness polycarboxylate superplasticizer was prepared.The effects of initial temperature,ratio of acid to ether,amount of chain transfer agent,and synthesis process on the properties of the superplasticizer were studied.The molecular structure was characterized by GPC(Gel Permeation Chromatography)and IR(Infrared Spectrometer).As shown by the results,when the initial reaction temperature is 15℃,the ratio of acid to ether is 3.4:1 and the acrylic acid pre-neutralization is 15%,The AMPS substitution is 10%,the amount of chain transfer agent is 8%,and the performance of the synthesized superplasticizer is the best.Compared with commercially available ordinary polycarboxylate superplasticizer in C30 concrete prepared with manufactured sand and fly ash,the bleeding rate decreases by 52%,T50 decreases by 1.2 s,and the slump time decreases by 1.1 s.In C60 concrete prepared with fly ash and river sand,the bleeding rate decreases by 46%,T50 decreases by 0.8 s,and the slump time decreases by 3.2 s.

Study on the Hydration and Physical Properties of Cement by M18 Polycarboxylate Superplasticizer Modified Graphene Oxide

Graphene oxide(GO)as a new nano-enhancer in cement-based materials has gained wide attention.However,GO is easy to aggregate in alkaline cement mortar with poor dispersibility.This hinders its application in practical infrastructure construction.In this work,GO-M18 polycarboxylate compound superplasticizer(GM)were obtained by compounding the M18 polycarboxylate superplasticizer with GO solution at different mass ratios.The dispersion of GM in alkaline solution was systematically studied.The phases and functional groups of GM were characterized by XRD and FTIR.The effects of GM on the cement mortar hydration and the formation of microstructure were investigated by measuring the heat of hydration,MIP,TG/DSC,and SEM.The results show that the long-chain structure of the M18 polycarboxylate superplasticizer can increase the interlayer spacing of GO and weaken the force between GO sheets.The modified GO can be uniformly dispersed in the cement slurry.GM can accelerate the early hydration process of cement,which can increase the content of Ca(OH)2 and decrease the grain size.It can optimize the pore size distribution of cement-based materials,increase the density of harmless and less harmful pores,thereby improving mechanical properties.Such methods can transform traditional cement-based materials into stronger,more durable composites,which prolong the life of cement-based materials and reduce the amount of cement used for later maintenance.This provides an idea for achieving sustainability goals in civil engineering.

Effects of Molecular Structure of Polycarboxylate-type Superplasticizer on the Hydration Properties of C_3S

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.

Effect of Crosslink Structure of Bridge Polycarboxylate Superplasticizers on Dispersion Ability

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.

Adsorption Mechanism of Polycarboxylate-Based Superplasticizer in CFBC Ash-Portland Cement Paste

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.

Influence of Polycarboxylate Superplasticizer on Rheological Behavior in Cement Paste

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.

Synthesis of New Polyether Polycarboxylate Superplasticizer

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.

Synthesis and Performance Characterization of a Low Adsorption Clay-resistant Polycarboxylate Superplasticizer

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.

Effects of Clay on Properties of Polycarboxylate Superplasticizer and Solutions

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.

Preparation of Polycarboxylate-based Superplasticizer and Its Effects on Zeta Potential and Rheological Property of Cement Paste

A series of polycarboxylate-based superplasticizers(PCs) with different structures were synthesized and the effects of chemical structure on zeta potential and rheological property of cement paste were studied. Residual monomers in each sample of PCs were quantitatively determined. The property of the polymers in cement was tested by micro-electrophoresis apparatus and R/S rheometer. Results showed that the zeta potential and its rheological properties are related with the side-chain length and density of PCs. The PCs having shorter side chain and lower side chain density exhibit higher anionic charge density, thus resulting in higher zeta potential. The effect of side chain density on zeta potential is more notable compared with that of side-chain length, and thus affecting the initial shear yield stress and apparent viscosity of the cement paste. In addition, although increasing the side chain length will result in reduction of the anionic charge density, the steric hindrance effect is obvious, which can effectively improve the dispersion of the cement particles, and reduce the viscosity and shear yield stress of slurry.

Determination of Residual Monomers in Polycarboxylate Superplasticizer Using High Performance Liquid Chromatography

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%.

Influences of Polycarboxylate Superplasticizers on Rheological Behavior of Low-cement Castables

Influences of different superplasticizers （ STP. KSJSTO and LMS-P） on rheological behavior of low-cement castables and the mechanisms were analyzed. The shear stress and viscosity under different shear rates of matrix slurry were determined using a NXS-I IA rotary viscometer. Effects of different admixtures on the rheological properties of slurry was analyzed theoretically. Sodium tripolyphosphate and poly＇carboxylate superplasticizers KS-JSTO and LMS-P） can improve the fluidity and initial setting time. With STP. the slurry is plastic flow. With KS-JS70 or LMS-P increasing, the slurrv changes from plastic.flow, pseudoplastic flow to dilatant flow successively. Th, e optimum dosages of STP. KS-JSTO and LMS-P are 0. 15%. 0. 25% and 0. 40%, respectively. KS-JS70 and LMS-P can significantly reduce the slurry viscosity and shear stress to improve the workability of construction. Both shear stress and viscosity shall be taken into account for on-site construction.

Effect of molecular structure and slump loss resistance of polycarboxylate superplasticizers on self-compacting concrete

A new kind of polycarboxylate superplasticizer with high slump loss resistance was obtained by designing scheduled molecular structure.The number average molecular mass of the polymer was characterized by the gel permeation chromatography measurements.And chemical structure of the polymer was observed by the Fourier transform infrared spectroscopy(FT-IR).The results show that the good workable maintaining of self-compacting concrete could be achieved through direct adjustment of number average molecular mass and different unsaturated monomer in synthetic process.The FT-IR analysis illustrated that the high slump loss resistance of polycarboxylate superplasticizers with ester and carboxyl group and expectations of molecular structure were designed.

Influences of Soluble Salts on Adsorption Properties of Polycarboxylate Superplasticizers

Polycarboxylate（PC） superplasticizers with different chemical structures were synthesized through free radical co-polymerization reaction.A total organic carbon analyzer was used to investigate adsorption behaviors of PCs,and to evaluate influences of soluble salts on absorption properties of PCs.It is found that adsorption ratios of PCs on cement particles decrease greatly with the addition of Na2SO4;the adsorption ratio of ethers PC with Hydroxyethyl methacrylate（HEMA） group first increases then decreases with the addition of NaCl;the adsorption ratio of esters PC with short side chains first decreases then increases,while the adsorption ratio of ethers PC with HEMA group decreases with the addition of CaCl2;the adsorption ratio of esters PC with short side chains decreases with the addition of Ca（NO3）2;AlCl3 causes the decrease of the adsorption ratio of ethers PC with HEMA group.

减水剂改性固废基蒸压加气混凝土的制备与性能研究

以花岗岩石粉、黄河特细砂为硅质材料,以电石渣为钙质材料,以聚羧酸减水剂为改性剂,制备固废基蒸压加气混凝土(AAC)。研究了聚羧酸减水剂掺量对AAC料浆流动性、发气过程、抗压强度、干密度、孔隙率和孔径分布的影响。结果表明,减水剂掺量由0.15%增大到0.30%,料浆初始流动度、发气速率、发气量和孔隙率逐渐增大,制品抗压强度和干密度逐渐降低。减水剂掺量为0.25时,料浆初始流动性270 mm,发气量208 mL,孔隙率82.54%,抗压强度2.9 MPa,干密度509 kg/m^(3),AAC综合性能最优。减水剂掺量大于0.2%时,2 mm以上的大孔基本消失,孔隙率和孔壁无害孔含量对AAC抗压强度影响更明显。

CeO_(2)可见光催化合成APEG保坍抗泥型聚羧酸减水剂

可见光异相催化合成聚羧酸系减水剂是进一步提高单体活性种生成率和减水剂性能的有效手段。本文以CeO_(2)为催化剂,(NH_(4))_(2)S_(2)O_(8)为引发剂,烯丙基聚氧乙烯醚(APGE-1000)、2-丙烯酰胺基-2-甲基丙磺酸和马来酸酐为单体,可见光催化聚合制备出APEG保坍抗泥型聚羧酸减水剂,初始及含泥净浆流动度分别为295 mm和275 mm,30min后经时损失均为零,展现出良好的分散性、保坍性和抗泥性,性能优于相同条件下热聚合制备的同种减水剂。系统表征发现,两者性能存在差距的原因是分子量不同,但两种减水剂具有相同的水化和抗泥机理,均能延缓水泥水化进程并使蒙脱土层出现不完全的剥离或分叉,与聚合方式无关;并且CeO_(2)具有吸收可见光的能力,在可见光照射下可产生的·OH和·O_(2)^(-)参与聚合反应,促进单体活性种的生成,提高了聚羧酸减水剂的分子量和应用性能。

减水剂对固化土强度影响的研究

为了探究聚羧酸、木质磺酸钙(木钙)两种减水剂对固化土强度的影响规律,在不同养护龄期下,对添加不同掺量减水剂的固化土开展了一系列无侧限抗压强度试验,从水化产物角度阐述了固化土强度随两种减水剂掺量的演变机理。试验结果表明:掺有两种减水剂的固化土强度均随着龄期的增加而增加,前期强度增长速度快,后期强度增长缓慢。固化土的强度随着聚羧酸掺量的增加呈现先增加后缓慢减小的趋势,当聚羧酸掺量为0.4%时,固化土强度达到最大值;固化土的强度随木钙掺量的增加逐渐减小,木钙减水剂提升强度的效果弱于聚羧酸减水剂。

缓凝型水泥浆液配合比优化及锚孔浆岩界面特性影响研究

针对预应力锚杆后张法施工中自由段浆液流动性和缓凝效果差的工程难题,提出使用标准型聚羧酸减水剂作为掺加剂以实现水泥浆液缓凝并提高其工作性能,探究其对锚孔浆岩界面特性的影响。采用室内试验、SEM电镜扫描等手段,结合Matlab多目标优化等方法,对掺加减水剂的缓凝型水泥浆液的锚固性能及配合比优化展开研究,得出适用于预应力锚杆自由段的注浆材料及其最优配合比,并与现行规范推荐配合比进行锚孔横断面结石特性对比试验。研究结果表明:1)随着水灰比增大,水泥浆液的流动度和凝结时间增大,体积结石率和抗压强度减小;随着减水剂掺量的增大,水泥浆液的流动度和凝结时间增大,体积结石率减小,减水剂对浆液抗压强度影响较小;2)未掺加减水剂时,浆液结石体致密性随着水灰比的增大而降低,掺加减水剂使得浆液结石体表面局部存在相对较大尺度的孔或孔隙,对宏观结石体强度有一定影响;3)通过Matlab多目标优化方法推荐了缓凝型水泥浆液最优配合比为水灰比0.3,减水剂掺量1.85%,相关性能参数符合规范要求,且流动度与抗压强度较规范推荐配合比分别提升了72.3%和107%;4)浸水围岩会弱化浆岩界面的抗剪强度,因此在锚杆灌浆过程中保证横断面结石率有利于提高浆岩界面的抗剪强度,本文提出的最优配合比浆液抗剪强度优于规范推荐配合比浆液。

磷酸酯缓释型聚羧酸减水剂的制备及性能研究

本文通过在30℃合成温度、过硫酸铵(APS)作还原剂作用下,使用乙烯基聚乙二醇醚(EPEG)、丙烯酸(AA)与乙二醇甲基丙烯酸磷酸酯(HEMAP)反应合成得到磷酸酯缓释型聚羧酸减水剂。文中对该减水剂进行水泥净浆及混凝土实验测试,实验表明,该产品具有良好的缓释效果,能极大满足混凝土企业远距离施工的需求,并对该减水剂进行了FT-IR与GPC结构表征。

基于竞聚率设计制备组成均匀的聚羧酸减水剂

基于实验得到的聚羧酸减水剂(PCE)共聚单体的竞聚率数据,采用控制转化率和补加活泼单体相结合的方法,结合理论计算和实际测定结果,确定了活泼单体丙烯酸(AA)补加时间及补加量,使其在共聚过程中始终与大单体异丁烯基聚乙二醇醚(MAPEG)组成保持基本不变,以保证聚合反应不同时间段生成的共聚物组成和结构与设计值一致。为系统研究控制工艺的准确性和可靠性,将其与传统投料工艺反应过程中所得产物的组成对比,考察了控制共聚物组成对分散性能的影响。结果表明,基于竞聚率的控制工艺制备PCE过程中,分段补加消耗较快的AA抑制了AA和MAPEG在共聚物瞬时组成的变化幅度,共聚物的平均酸醚比[n(AA)/n(MAPEG)]分别为2.8、3.8、4.8,基本接近设计酸醚比(3.0、4.0、5.0);其制备的PCE平均主链长度及主链上羧基含量、大单体含量较高,使PCE覆盖面积和吸附层厚度增大,从而提升了水泥净浆初始流动度和流动保持性能。