聚羧酸系高效减水剂PC的合成及性能研究

以甲基丙烯酸、聚乙二醇1000、对甲苯磺酸、对苯二酚、过硫酸铵和甲基丙烯磺酸钠为原料,采用两步法合成出新型聚羧酸系高效减水剂(简称PC)。将合成的PC与目前广泛使用的萘系高效减水剂(简称FDN)相比,具有更加优异的性能,具体表现为:在掺量很少情况下,水泥净浆就具有较高的流动度;当掺量相同时,其对水泥净浆流动度远超FDN。此外,它与水泥的相容性好,具有缓凝及明显抑制水泥净浆流动度经时损失性能,对混凝土也能表现出显著的减水增强性,是一种性能优良,适合于配制高强、超高强混凝土的高效减水剂。     

水泥基材料中高效减水剂应用效果的检测方法

采用水泥浆体流动度、混凝土减水率、坍落度及强度增长率等指标确定了2种萘系高效减水剂的掺量，研究了二者在此掺量下对相同配比砂浆的流动度及经时损失、开裂敏感性及干湿变形的影响。结果表明：与水泥适应性均较好的2种萘系高效减水剂在各自掺量下，所配制的砂浆具有相同的初始流动度及流动度经时损失变化，但其初始开裂时间与干湿变形却存在差异，说明在评价高效减水剂的应用效果时除了检测与水泥的相容性外还应考虑其对水泥基材料收缩变形性能的影响；不同外加剂对水泥基材料体系碱度的适应能力不同，较高的碱度会增加材料的开裂敏感性。     

减水剂对高掺量粉煤灰砂浆性能的影响

研究了萘系高效减水剂（FDN）和木质素磺酸钙（LS）对高掺量粉煤灰砂浆性能的影响,测定了减水剂在胶凝颗粒表面的吸附、对水泥颗粒表面zeta电位等方面的影响。结果表明,和FDN相比,LS对砂浆的减水率较低,而对砂浆流动度保持能力较优;当掺量为0.4 wt%时,两者对砂浆稳定性的影响几乎一样。当掺量低于0.4 %时,LS的减水率和FDN接近是因为其具有较强的引气作用和FDN在胶凝颗粒表面吸附不完全;LS保持砂浆流动性能力较好是由于它的缓凝作用以及吸附LS的水泥颗粒表面zeta电位较稳定导致的。为了更好地将LS应用在高掺量粉煤灰砂浆中,可以从提高其减水率方面对其进行改性。     

粉煤灰、减水剂对水泥浆体相容性影响的试验研究

通过调整萘系和聚羧酸系减水剂的含量,观察水泥浆体的流动性和流动性经时损失的变化,由此确定减水剂的饱和点和减水剂对水泥相容性影响;减水剂在饱和点掺量时,调整粉煤灰掺量,研究粉煤灰掺量对水泥相容性的影响.结果表明:水泥浆体的流动度随减水剂掺量的增加而增大;萘系减水剂的饱和点掺量为0.8%,聚羧酸系减水剂的饱和点掺量为1.4%;在减水剂饱和点附近,静置35 min、60 min,萘系、聚系减水剂流动度经时损失分别为65%和39%,且聚羧酸系减水剂具有滞后性;聚系减水剂与水泥的相容性优于萘系高效减水剂;在减水剂饱和点掺量处,随着粉煤灰含量的增加,水泥浆体的流动度增大.     

脂肪族高效减水剂的吸附特征与作用机理

对比研究了脂肪族磺酸盐和萘系高效减水剂水溶液的表面张力、水泥-水-高效减水荆系统中水泥颗粒表面的动电电位及随时问的变化规律，以及2种高效减水荆在水泥颗粒表面的吸附量和吸附特征等物理化学现象，测定了脂肪族磺酸盐高效减水剂分子量分布和分子结构的官能团特征。在试验结果分析的基础上，提出了包括萘系高效减水剂在内的高分子表面活性剂在水泥颗粒上的吸附特征是多分子层吸附。在低浓度下，吸附曲线表现出Langiur吸附特征，但总的来说，高效减水剂在水泥颗粒上的吸附曲线更接近于双平台型（LS）曲线。     

氧化-醚化淀粉作水泥减水剂的制备及性能(二)

考察氧化-醚化淀粉对水泥水化凝结时间影响,通过XRD、TAMair等温微热量热仪进行水化性能表征。结果表明:与萘系高效减水剂相比在掺量0.6%时减水作用优于萘系,流动度经30 min反而增加22.4%,2 h内基本无损失,但有明显缓凝作用,水化放热峰出现在75 h,但不影响后期水化,7 d时抗压强度已达国家标准,28 d时抗压强度比可达127%,可作为水泥的一种优良缓凝型高效减水剂使用。     

葡萄糖酸钠与高效减水剂复合使用对水泥水化历程的影响

用直接测温法及X射线衍射技术,系统研究了葡萄糖酸钠与萘系、氨基磺酸盐系及聚羧酸盐系3种高效减水剂复合使用对水泥水化热、水化温峰、温峰出现时间及不同水化龄期Ca(OH)2和钙矾石(AFt)生成量等方面的影响.结果表明:与糖钙和三聚磷酸钠相比,葡萄糖酸钠及其与高效减水剂复合对水泥水化历程的影响规律明显不同.单掺葡萄糖酸钠使水泥水化第2放热峰出现时间延迟,但温峰值及水化热与空白样基本持平,温峰时的Ca(OH)2生成量增大.复合使用葡萄糖酸钠与高效减水剂时,与不同品种高效减水剂复合使用对水泥水化历程的影响不同.     

矿物掺合料对水泥与高效减水剂相容性影响的试验研究

采用萘系高效减水剂与掺有粉煤灰、矿粉、复合粉等矿物掺合料的水泥,在不同温度下进行水泥流动度试验,测定水泥净浆流动度,分析粉煤灰、矿粉、复合粉、温度等因素对水泥与萘系减水剂相容性的影响,研究结果表明:粉煤灰、矿粉、复合粉可以改善水泥净浆流动度;温度升高抑制水泥净浆流动度;复合粉中的粉煤灰、矿粉对水泥净浆流动度促进作用不是简单的叠加关系,而是相互影响的;在改善萘系减水剂与水泥相容性方面,粉煤灰矿粉复合粉空白.     

粉煤灰与矿粉改进减水剂与水泥相容性的研究

采用萘系、聚羧酸系减水剂与粉煤灰、矿粉双掺法,进行水泥流动性的试验,测定净浆流动度损失,研究粉煤灰、矿粉对减水剂与水泥相容性影响,研究发现,粉煤灰、矿粉能有效改进萘系、聚羧酸系减水剂与水泥的相容性;而聚羧酸系减水剂与水泥的相容性比萘系减水剂好．     

用外加剂控制泵送混凝土坍落度经时损失

在泵送混凝土中掺外加剂，能增加拌合物的流动性并降低泵送混凝土坍落度经时损失。本文通过对泵送混凝土坍落度经时损失的成因分析，研究了高效减水剂FDN、缓凝剂糖蜜及复台使用FDN和糖蜜对泵送混凝土坍落度经时损失的影响，及它们与水泥适应性。试验结果表明，复合使用高效减水剂和缓凝剂，能有效控制混凝土坍落度经时损失。     

Effect of superplasticizers on the early age hydration of sulfoaluminate cement

The effects of two types of superplasticizers on the properties of CSA cement pastes during early hydration were studied. The influences of two types of superplasticizers on the properties of cement pastes, including the normal consistency, setting time, fl uidity, and compressive strength, were investigated by using various methods. The hydration products of the cement pastes cured for 1 day and 3 days were studied by X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The results show that the PCE type superplasticizer retards the early age hydration while the FDN type superplasticizer accelerates the early age hydration of the CSA cement. Both types of superplasticizers have no infl uence on the further hydration of CSA cement, confi rmed by the calorimeter tests as well. The ultrasonic pulse velocity measurements were used to probe the influence of two types of superplasticizers on the hydration of CSA cement pastes at a high water-cement ratio（0.45）. The results show that the PCE type superplasticizer retards the early age hydration of the CSA cement while the FDN type superplasticizer has little infl uence on the early age hydration of the CSA cement.     

Effect of competitive adsorption between sodium tripolyphosphate and naphthalene superplasticizer on fluidity of cement paste

The adsorption amount, ζ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer(FDN) and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g(about 72.5%). The adsorption amount of FDN was reduced by STPP, but ζ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca2+ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ζ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.     

改性聚羧酸减水剂与C30自密实混凝土性能的关系

研究了一种改性过的聚羧酸系减水剂对不同原材料组成的C30自密实混凝土l小时内的保坍性能、不同龄期的强度变化及抗碳化性能,并与萘系减水剂配置的大流动度混凝土的相同性能进行了对比．结果表明,改性聚羧酸减水剂拌制的混凝土保坍性能优越,对低于50％机制砂替代率有较好的适应性;这种混凝土与用萘系减水剂配制出的自密实混凝土的抗碳化性能相当．     

一种高精准水泥浆体流动性测定装置

针对传统净浆流动度测试方法灵敏度不高、测试范围窄的问题,设计了一系列不同口径的玻璃管(H管)。通过对不同水灰比、不同掺量减水剂条件下水泥浆体的流变特点的对比分析,得到不同H管对应净浆流动度测试范围和减水剂最佳掺量测试方法。H管不仅灵敏度高、测试范围广,而且还可以反映浆体粘度,是一套比较全面准确的水泥浆体流动性测试方法。     

Adsorption of superplasticizers in fly ash blended cement pastes and its rheological effects

The adsorption of superplasticizers in fly ash blended cement paste and its rheological effects were investigated.It is shown that the absorption of superplasticizer on portland cement particles is very different from that on fly ash particles.The fly ash particles have smooth surfaces and are negatively charged,so its adsorption capacity is weaker than the portland cement particles.The amount of adsorbed SP in the fly ash blended cement paste depends highly on the replacement proportion of portland cement with fly ash,and to a much less extent on the nature of the fly ash.However,the amount of adsorbed superplasticizer does not correspond well the ζ-potential of the solid particles,due the strong adsorbing capacities of the Portland cement particles.When fly ash replaces portland cement in the paste,the rheological behavior is radically changed,which is closely related to the fineness and density of the ash.The packing and agglomeration of the solid particles are the controlling factors on the rheological parameters of the fresh paste,instead of the amount and type of adsorbed superplasticizer.     

不同种类减水剂对砂浆力学性能的影响 及模糊数学法综合评价

研究了木素磺酸钙(CLS) 、改性木素磺酸钙（GCL1-6A）、氨基磺酸甲醛缩合物(ASP) 、萘磺酸甲醛缩合物(FDN) 和三聚氰胺脲醛树脂(SMUF)5种减水剂对砂浆抗压强度和抗折强度的影响。并通过模糊数学法综合评价不同种类减水剂对砂浆力学性能的影响。模糊数学法综合评价表明：掺入FDN的水工建筑物和道路路面或机场道面用的混凝土力学性能最优,其次是掺入SMUF和GCL1-6A的;掺入SMUF的民用建筑用梁、柱等棱柱体构件用混凝土力学性能最优,其次是掺入FDN和GCL1-6A的。综合考虑价格和环保等因素,在混凝土工程中使用GCL1-6A具有很大的经济和环境效益。     

水泥沥青浆体中减水剂与乳化沥青的竞争吸附行为

为揭示水泥沥青砂浆(CA砂浆)中水泥对乳化沥青和减水剂的吸附规律,采用微量热仪分析了减水剂、乳化沥青(单掺及同掺)对水泥水化诱导期的延迟作用.采用"固含法"研究了减水剂种类对水泥-乳化沥青经时吸附规律的影响,以及减水剂在不同添加顺序时对水泥-乳化沥青经时吸附规律的影响.采用偏光显微镜对减水剂作用下水泥-乳化沥青的吸附行为进行了原位观测.结果表明:CA砂浆中的乳化沥青和减水剂均能显著延迟水泥的水化诱导期,两者同掺使延迟作用产生了明显的协同效应;聚羧酸减水剂与乳化沥青对水泥的吸附作用存在明显的竞争关系,两者同掺时水泥优先吸附减水剂分子,减水剂耗尽后,水泥再吸附乳化沥青.减水剂后掺时可使部分吸附的乳化沥青发生解吸附.     

Rheological behaviors of fresh cement pastes with polycarboxylate superplasticizer

The rheologicalbehaviors of fresh cement paste with polycarboxylate superplasticizer were systematically investigated.Influentialfactors including superplasticizer to cement ratio(Sp/C),water to cement ratio(w/c),temperature,and time were discussed.Fresh cement pastes with Sp/Cs in the range of 0 to 2.0% and varied W/Cs from 0.25 to 0.5 were prepared and tested at 0,20 and 40 °C,respectively.Flowability and rheologicaltests on cement pastes were conducted to characterize the development of the rheologicalbehavior of fresh cement pastes over time.The exprimentalresults indicate that the initialflowability and flowability retention over shelf time increase with the growth in superplasticizer dosage due to the plasticizing effect and retardation effect of superplasticizer.Higher temperature usually leads to a sharper drop in initialflowability and flowability retention.However,for the cement paste with high Sp/C or w/c,the flowability is slightly affected by temperature.Yield stress and plastic viscosity show similar variation trends to the flowability under the abovementioned influentialfactors at low Sp/C.In the case of high Sp/C,yield stress and plastic viscosity start to decline over shelf time and the decreasing rate descends at elevated temperature.Moreover,two equations to roughly predict yield stress and plastic viscosity of the fresh cement pastes incorporating Sp/C,w/c,temperature and time are developed on the basis of the existing models,in which experimentalconstants can be extracted from a database created by the rheologicaltest results.