Influence of superplasticizer type and dosage on the slump loss of Portland cement mortars—Part II

Fluidity and slump loss are cardinal features responsible for the quality of concrete. These are related to the dispersion of cement particles and the hydration process, which are greatly influenced by superplasticizers (SPs). A variety of SPs are commercially available. Their influence on the fluidity and slump loss differs considerably. In this work, SPs based on lignosulfonic acid (LS), melamine formaldehyde sulfonic acid (SMF), naphthalene formaldehyde sulfonic acid (SNF), and polyacrylic acid polymer (CE) are tested with ordinary Portland cement (OPC) at different water-to-cement ratio. The results reveal that not only SPs of different base groups behave differently but even the SP of the same base group SMF behave differently. Fluidity increased with increase in the dosage of SP. CE was most effective followed by LS, SNF, and SMF SP.     

Adsorption characteristics of superplasticizers on cement component minerals

Adsorption characteristics of various superplasticizers on portland cement component minerals were investigated. Adsorption isotherms of various types of superplasticizers and ζ-potentials of cement component minerals at the maximum adsorption of the superplasticizers were measured. The value of the adsorption isotherm was calculated from the amount of the superplasticizer adsorbed on a cement component mineral in an equilibrated solution. The maximum amounts of adsorption and the adsorption isotherms varied with types of component mineral and superplasticizer. For all types of superplasticizers, a larger amount of superplasticizer was adsorbed on C₃A and C₄AF than C₃S and C₂S. However, the equilibrated concentration of each superplasticizer at the maximum adsorption was not influenced by types of superplasticizer. Without superplasticizer, C₃S and C₂S had negative ζ-potential. On the contrary, C₃A and C₄AF had positive ζ-potential. Therefore, accelerated coagulation of cement particles might occur due to their electrostatic potentials that are opposite each other. However, all component minerals of cement had negative ζ-potential when they were mixed with any superplasticizer. Fluidity of fresh cement paste is improved due to electrostatic repulsion acting between particles.     

A water‐soluble acrylate/sulfonate copolymer. I. Its synthesis and dispersing ability on cement

A new water‐soluble methacrylate/2‐acrylamido‐2‐methylpropane sulfonate copolymer (PMAMP) was synthesized and evaluated as a dispersion agent for cement particles. PMAMP was prepared from methacrylic acid and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMP). The structure of the prepared polymer was verified by its NMR and IR spectra. The dispersing properties of PMAMP were evaluated by a minislump test on cement pastes. The test results indicated that this copolymer could disperse the cement particles and improve the minislump of cement pastes. Compared with a commercial superplasticizer (sulfonated naphthalene formaldehyde condensates), PMAMP performed better in enhancing the fluidity of the cement pastes. The polymer with about 40–50% AMP and a weight‐average molecular weight of about 5 × 10⁴ was most effective in dispersing cement particles and promoting the fluidity of cement pastes. Nevertheless, PMAMP with a higher AMP content or a higher molecular weight appeared to cause less slump loss. This was related to the interaction of this admixture with the cement particles and its adsorption behavior onto the cement particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2490–2496, 2006     

Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C₃S, β-C₂S, C₃A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, ²⁹Si and ²⁷Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.     

Effect of cross‐linked polycarboxylate‐type superplasticizers on the properties in cementitious system

Fluidity and slump loss are main technical indicators for the quality of concrete. They are related to the dispersion of cement and hydration process, and are greatly affected by the structure of superplasticizers (SPs). For the purpose of obtaining SPs with excellent fluidity and slump retention, water‐soluble cross‐linked polycarboxylate ether copolymers (CLPCs) of acrylic acid and alkenyl alcohol type polyoxyethylene ether were synthesized. In order to gain full understanding of the effect of cross‐linked SPs on the properties in cementitious system, properties of the new SPs in cement paste were compared to those of traditional ones without cross‐linking agents. Mortar tests showed that CLPC performed obvious slow‐release function and kept about 10 mm higher than its initial paste flow after 150 min, while PC incurred loss of 15 mm after 150 min. Adsorption of CLPC on cement resulted in zeta potential being roughly the same as that in the case of PC, and enabled more effective slump retention to cement suspensions by rheological property tests. Ettringite peaks disappeared for CLPC on 1‐day curve and reappeared after 35 days, and the intensity of CH peaks for CLPC appeared weaker than Blank and PC after 1 day. The microstructure of CLPC after 1 day showed a very dense structure of smaller and thinner crystallites, which indicated that the early hydration was greatly delayed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40856.     

Influence of hydration on the fluidity of normal Portland cement pastes

The rheological properties of cement paste strongly influence the workability of concrete. It is known that early hydration processes alter phase composition and microstructure of cement pastes. These processes affect fluidity and setting behaviour of cement paste. While many studies tried to measure and model rheological properties of cement pastes, only a few studies assessed the influence of the hydrate morphology on the fluidity of cement pastes.Results of the present study compare the influence of long prismatic hydrates (i.e. syngenite, secondary gypsum) on the fluidity of cement pastes with the effect of other hydrates (AFm).To induce the formation of certain hydration products the cement composition was modified by addition of set regulators and alkali sulphates. Furthermore a combination of various analytical methods such as fluidity (viscometric) testing and microstructural analysis (phase quantification by XRD-Rietveld analysis, investigation by Environmental SEM, BET analysis etc.) was performed. Results are implemented into a fundamental discussion on the influence of various hydration products on the fluidity of the paste.     

Microstructure of tricalcium silicate and Portland cement systems at middle periods of hydration-development of Hadley grains

The development of the microstructure of C₃S paste and a Portland cement paste was studied between 7 and 24 h by means of backscattered electrons in a field-emission SEM. The course of hydration was measured by isothermal calorimetry. While the abundant occurrence of Hadley grains (hollow-shells) in Portland cement systems is well documented from a number of SEM and other microscopy studies, some earlier reports have noted that Hadley grains do not form in C₃S or alite paste alone. This report shows evidence of Hadley grains in C₃S paste, and follows their development from middle to late hydration stages. At around 10 h the microstructure with respect to Hadley grains were seen to develop in a very similar manner in C₃S and cement. In both systems, a narrow gap often developed between the receding anhydrous cores and layer of reaction product enveloping the cores. By 1 day, Hadley grains had continued to develop only in the cement paste, where they became a prominent feature. Only small ‘hollowed-out’ hydration shells were observed in the C₃S paste by 1 day. These were presumably reminiscences of the small gapped Hadley grains seen at the earlier hydration stages.     

Contribution of non-adsorbing polymers to cement dispersion

It has been noticed recently that at low w/c ratios (≤ 0.30), non-adsorbed polycarboxylate (PCE) polymers can contribute as well to cement dispersion. This study aimed at defining more specifically the structural requirement for such non-adsorbing polymers. For this purpose, a cement paste (w/c = 0.30) containing a conventional MPEG PCE superplasticizer was admixed with additional quantities of a polyester polymer prepared via homopolymerization of MPEG methacrylate ester macromonomer, the macromonomer used in the homopolymerization, and the polyethylene glycol contained in the macromonomer. It was found that when admixed individually, all three polymers do not adsorb on cement and cannot fluidize the paste but enhance dispersion and fluidity significantly when combined with the PCE superplasticizer. A potential explanation is that the non-adsorbing polymers act as lubricants between cement, which are particularly densely packed at low w/c ratios. The pore fluid loaded with non-adsorbed polymer exhibits superior lubrication compared to pristine cement pore solution.     

Effect of both grafting and blending modifications on the performance of lignosulphonate-modified sulphanilic acid–phenol–formaldehyde condensates

Modifying sulphanilic acid–phenol–formaldehyde condensates (SPF) with sodium lignosulphonate (LS) allows for both the grafting (GSPF) and blending (BSPF) of a series of products from SPF and LS with different LS content. The grafted macromolecule SPF-g-LS was confirmed to exist in GSPF by low-angle laser light scattering (LALLS) and Fourier-Transform infrared (FTIR) spectroscopy. GSPF formed different adsorption configurations on cement particles than BSPF, which ultimately affected their dispersive properties, because of the high charge density and large steric hindrance of the SPF-g-LS macromolecule. Both the absolute value of the ζ potential and the paste fluidity of the cement particles were greater for GSPF than BSPF at identical LS contents. GSPF and BSPF both significantly inhibited cement bleeding relative to SPF; however, this inhibition was greater for GSPF than BSPF at identical LS contents.     

木钠接枝磺化三聚氰胺树脂高效减水剂的合成及性能

针对传统的磺化三聚氰胺树脂减水剂(SMF)塌落度损失大、泌水性大的缺陷,以过硫酸铵引发自由基接枝合成了木钠接枝磺化三聚氰胺甲醛树脂高效减水剂(SLMF),获得了优化的合成工艺。红外谱图和SLMF的性能表明木钠成功接枝于SMF结构中。合成的SLMF具有良好的分散性和保水性能。在水灰比为0.29(质量比)时,掺0.6%(质量分数)的SLMF高效减水剂的水泥净浆流动度为253 mm,掺SLMF的水泥净浆在90 min内的流动度损失从100%降低为61.8%,而140 min内静态泌水率从4.84%降低到1.61%。结果表明,SLMF高效减水剂能有效克服传统三聚氰胺高效减水剂的缺陷,具有良好的应用前景。     

The theoretical maximum achievable dispersion of nanoinclusions in cement paste

A major challenge of successfully incorporating nanometric inclusions (nanoinclusions) within cement paste is achieving a uniform distribution of the nanoinclusions. Cement particles have a larger diameter than the average spacing between nanoinclusions when the nanoinclusions are fully dispersed, which means that the presence of cement particles in the fresh paste degrades the maximum achievable dispersion of the nanoinclusions in the hardened paste. To determine the significance of this effect, a novel method for dispersion quantification was implemented to calculate the theoretical maximum achievable dispersion of nanoinclusions in fresh cement paste. Three-dimensional simulations were performed for cement pastes with common values of water to cement ratio, nanoinclusion to cement ratio, and cement fineness. The results show that for cementitious nanocomposites simulated in this study, degradation of the maximum theoretical achievable dispersion of nanoinclusions due to the presence of cement particles is negligible as long as the cement particles are not agglomerated.     

Effects of β-cyclodextrin side chains on the dispersing and retarding properties of polycarboxylate superplasticizers

A modified polycarboxylate (MPC) superplasticizer was synthesized by the copolymerization of acrylic acid, methallyl sulfonic acid, allyl poly(ethylene glycol)s, and β-cyclodextrin (β-CD) grafted maleic anhydride. The molecular structure of the MPC was characterized by Fourier transform infrared spectroscopy and gel permeation chromatography. The effects of the content of β-CD on the application performance of MPC were investigated with measurements of the cement paste fluidity, setting time, amount of adsorption of MPC on the cement particles, and ζ potentials of the cement particles and differential scanning calorimetry–thermogravimetric analysis of different hydration ages of the cement pastes. The results indicate that the initial fluidities and setting times of the cement pastes increased with increasing number of β-CD side chains. The dispersion capacity of MPC on the cement particles mainly came from a steric hindrance effect and an air-entraining effect of the β-CD side chains. The better retarding performance of MPC was attributed to the solvation water film formed by the polyoxyethylene side chains and chelates formed by  OH groups on the β-CD structure combined with Ca²⁺ ions on the surface of the cement particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

锂渣和钢渣对水泥浆体力学性能与微观结构的影响

利用锂渣粉和钢渣粉替代部分P·O 42.5水泥制备了复合水泥净浆试样。通过SEM、XRD、FT-IR等测试方法分析了二者对试样的影响及作用机制。结果表明,锂渣替代部分水泥会降低浆体的流动性,钢渣替代部分水泥有利于提高浆体流动性。锂渣具有促凝效果,而钢渣在浆体中可发挥缓凝作用。锂渣、钢渣复合掺入时可调控浆体的流动性和凝结时间。锂渣对浆体力学性能的提高相比钢渣具有更明显的优势,当水胶比为0.4时,掺入20%(质量分数)锂渣的试样28 d抗压强度可达62.3 MPa,相比空白样可提高23%左右。SEM结果显示掺20%锂渣可使试样28 d微观结构更致密。XRD结果显示试样的水化产物主要为C-S-H凝胶和Ca(OH)₂。FT-IR结果显示Si—O键峰位发生了一定的红移,H—O—H键发生了蓝移。     

Characterization by solid-state NMR and selective dissolution techniques of anhydrous and hydrated CEM V cement pastes

The long term behaviour of cement based materials is strongly dependent on the paste microstructure and also on the internal chemistry. A CEM V blended cement containing pulverised fly ash (PFA) and blastfurnace slag (BFS) has been studied in order to understand hydration processes which influence the paste microstructure. Solid-state NMR spectroscopy with complementary X-ray diffraction analysis and selective dissolution techniques have been used for the characterization of the various phases (C₃S, C₂S, C₃A and C₄AF) of the clinker and additives and then for estimation of the degree of hydration of these same phases. Their quantification after simulation of experimental ²⁹Si and ²⁷Al MAS NMR spectra has allowed us to follow the hydration of recent (28 days) and old (10 years) samples that constitutes a basis of experimental data for the prediction of hydration model.     

Early performances of cement paste in the presence of triethanolamine: Rheology,setting and microstructural development

The effect of triethanolamine (TEA) at various dosages on the early performance of cement paste was systematically evaluated through the techniques of rheological measurements, penetration tests, and ultrasonic pulse velocity. The correlation of early performance to the chemical hydration process was analyzed by calorimetry, zeta potential, in situ XRD, and pore solution analysis. It is found that the effect of TEA on the early performance of cement paste is strongly dependent on its dosage. With the TEA dosage below 0.1 wt%, the setting and microstructural development of cement paste are retarded. Meanwhile, the yield stress of fresh paste is decreased due to the increasing zeta potential of cement grains. The promoted formation of ettringite (AFt) and monosulfate (AFm) caused by TEA decreases the rheological retention ability. At dosages ≥0.2 wt%, the reaction of aluminate-containing phases is greatly accelerated and a flash setting is observed. Besides, the importance of ferric phase on the reaction of cement with TEA is highlighted. At a low dosage, TEA prefers to accelerate the dissolution of tetracalcium aluminoferrite (C₄AF) first and increases the [Fe] in the pore solution of cement paste. In cement without C₄AF, the retardation of TEA on silicate phase hydration is significantly alleviated.     

Regulating the arm structure of star‐shaped polycarboxylate superplasticizers as a means to enhance cement paste workability

Star‐shaped superplasticizers, which incorporated polyol ester with unsaturated bond at their cores and bore comb‐type structures as their arms were synthesized via esterification‐copolymerization in aqueous phase from pentaerythritol, acrylic acid (AA), and isopentenyl oxy poly(ethylene glycol ether) (TPEG). The monomer ratios of AA and TPEG were varied and comonomer sodium methallyl sulfonate (SMAS) bearing short side chains was added to regulate the arm structure of star‐shaped polycarboxylate superplasticizers (SPCEs). The effects of the SPCEs on cement paste were investigated and the cement dispersion as well as early hydration mechanism were explored. As a main result, SPCEs with SMAS and certain molar ratios for anchoring groups and PEO side‐chains in their arm structure exhibited good paste dispersion and fluidity retention, which also delayed the early hydration process and prolonged both the initial and the final setting time. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46312.     

The contact zone between portland cement paste and glass “aggregate” surfaces

The morphology of the contact zone developed between Portland cement paste and glass slide “aggregates” has been explored using SEM and other techniques. A duplex film of about 1 μm total thickness is rapidly deposited on the glass surface. This is a continuous film of Ca(OH)₂ overlain by a parallel array of rod-shaped CSH gel particles projecting normal to the interface. The nearby cement paste exhibits high porosity, but after a few days becomes partly filled with a secondary deposit of stacked platelets of relatively pure Ca(OH)₂. Cement particles near the interface hydrate in a peculiar manner. A hydration product shell is quickly formed, but the encapsulated cement particles dissolve away to leave partly or completely empty shells. This behavior occurs with various Portland cement types and presumably occurs near aggregate surfaces in concrete.     

Marsh筒法和净浆流动度法用于水泥与减水剂适应性测试的比较

通过Marsh筒法和净浆流动度法用于水泥与减水剂适应性测试比较发现,采用Marsh筒法无论在测定减水剂饱和掺量点、对经时损失的敏感性上,还是与水泥标准稠度用水量和胶砂流动度的相关性上都优于净浆流动度法。     

Evaluation of the wettability of spherical cement particle surfaces using penetration rate method

The wettability of cement particles is related to the fluidity of cement paste. This paper describes the mechanism of the higher fluidity imparted by the spherical cement particles in light of their wettability. In addition, the effects of gypsum on the wettability were also studied. This study has shown the following: (1) The weight of water and water-reducing agent solution penetrating the spherical cement powder bed is 24-150% higher than that for the ordinary Portland cement powder bed. This results in the improvement of the wettability of the particle surfaces of spherical cement. The high wettability of spherical cement contributes to its high fluidity. (2) The presence of many fine gypsum particles on the spherical cement particle surface reduces the wettability. (3) To prepare spherical cement, the optimum amount of gypsum added is determined by the acceleration of the formation of spherical particles and the wettability of particle surfaces.     

Examination of 136 years old Portland cement concrete

A piece of Portland cement concrete, cast in England in 1847 was examined by advanced petrographic methods. The concrete was found to be dense, well preserved and air entrained. Unhydrated and hydrating fragments of the clinker components C₃S and C₂S are present in the cement paste. Residual ferrite phases seem to have remained unhydrated.