离子色谱法测定萘系复合外加剂中4种阴离子的含量

<正>混凝土外加剂主要有减水剂、缓凝剂、早强剂、引气剂、膨胀剂和防冻剂等。混凝土外加剂的方向是高效能、多功能复合外加剂,只有复合化才能具有高效能和多功能,并且可以促使新型混凝土和新型工艺的发展,实践证明,减水剂与其他外加剂复合,是减水剂应用技术的又一个趋势,无论是无机或者有机单一品种难以满足要求。复合外加剂是以高效减水剂为母料,复合其他性能的材料,该材料可适应多种水泥的外加剂。减水剂通常是一种阴离子型表     

混凝土的第五组分——化学外加剂

混凝土化学外加剂在混凝土施工中已得到越来越广泛的应用,已被称为混凝土的第五组分。本文介绍了混凝土化学外加剂的主要种类、作用机理和使用过程中注意的问题。     

混凝土外加剂的综合分析

混凝土外加剂的综合分析吴玉蓉龚宓曹雪峰艾克蕙（四川大学化学系成都６１００６４）关键词混凝土外加剂综合分析中图分类号Ｏ６５５．４前言混凝土外加剂是：“掺入量较少；其本身容积混凝土的配合比计算中可忽略不计的外加材料。”是一种能赋予混凝土以高流动性、高耐久...     

水基聚合物在混凝土中的应用

随着人们对材料结构与性能关系的深入认识，越来越多的水基聚合物被广泛用于混凝土行业中。本文主要介绍了水基聚合物在混凝土外加剂，主要是混凝土减水剂、引气剂、增粘剂、减缩剂中的应用情况，以及在聚合物混凝土中的应用现状，以期引导更多的化学和材料工作者投入到混凝土材料的研究中来，促进砼技术的快速发展。     

聚羧酸类高效减水剂分子结构类型及改性研究进展

聚羧酸类高效减水剂(PCEs)因其优异的减水性能已成为现今混凝土外加剂最热门的课题之一。本文按发展历程对四类不同分子结构的PCEs进行了介绍,对比了此四类PCEs的合成方法及性能,综合国内外研究探讨了PCEs在保坍、减缩、早强、引气、敏感性等方面问题,提出了多种切实可行的解决方法,并结合材料的构效关系从绿色环保、材料性价比及市场需求等方面对其研究进行了展望。     

ICP-AES法测定混凝土外加剂中微量氯离子

由于Cl^-过量引起混凝土钢筋锈蚀而过早的破坏，已成为世界性问题。混凝土外加剂中微量Cl^-是一个重要指标，准确测定氯离子的含量直接关系到混凝土配比的确定及浇灌后的质量。部颁及行业标准中是采用电化学滴定法和蒸馏法来测定混凝土外加剂的微量Cl^-[1,2]，电化学滴定法对测定干扰大。本文采用电感耦合等离子体原子发射光谱法间接测定与微量Cl^-定量反应后剩余的Ag^ 含量，从而换算出Cl^-的含量，经回收验证及比较，证明本法简便、灵敏、快速，切实可行。     

自动电位滴定法测定磺酸盐合成及产品中硫酸钠

石油系磺酸盐合成及产品 (如凝土外加剂 )中硫酸盐的测定 ,对控制磺酸盐质量具有重要意义。目前 ,磺酸盐产品中硫酸盐测定多采用“混凝土外加剂匀质性试验方法”中硫酸钡重量法或离子交换重量法[1 ] ,此法手续繁琐 ,尤其是费时 ,周期约 48ｈ ,难以满足生产特别是工艺开发阶段条件试验时调整工艺参数的要求。用铅离子作滴定剂 ,铅离子选择性电极为指示电极 ,电位滴定法测定硫酸盐是一种比较可靠的方法 ;用于磺酸盐中硫酸盐的分析 ,目前尚未见报道。作者运用计算机控制的自动电位滴定法[2 ] ,选择了适合在磺酸盐中进行测定的滴定介质、酸度、…     

离子色谱法测定混凝土外加剂中硫酸钠含量

建立了一种离子色谱法测定混凝土外加剂中硫酸钠含量的方法,外加剂试样溶于水中,采用反相柱去除溶液中有机物,进样量25μL。经Dionex IonPac AS18色谱柱分离,用30 mmol·L~(-1)氢氧化钾溶液作流动相,以1.0 mL·min~(-1)流量进行洗脱,按峰面积定量。方法的检出限(3S/N)为3μg·L~(-1)。该方法可实现硫酸钠与氯离子同时测定的优点。在3个浓度水平上对方法的精密度作了考核,测得其相对标准偏差(n=6)均小于1%。用标准加入法,以实样为基体作回收试验,测得回收率在98.7%～100.5%之间。     

Mg2+和Na+对高熔点煤灰熔融性的影响

以山西阳泉固庄高熔点煤灰为研究对象,通过向煤灰中添加不同量的MgO与Na₂CO₃,研究了Mg²⁺与Na⁺在高温下对煤灰熔融性的影响。研究结果表明,煤灰熔融温度随氧化镁的添加(5%~25%)单调下降;而随氧化钠添加(5%~25%)出现先降后升现象,在氧化钠添加量为15% 时,灰熔点达到最低。XRD分析表明,阳泉固庄煤灰熔融温度高(大于1 750℃)的原因是高温条件下耐熔矿物莫来石、方英石的存在。添加外加剂后,高温时外加剂与硅酸盐矿物反应,生成了更多的低共熔矿物霞石、堇青石等。同时,Mg²⁺和Na⁺的加入会使得非桥氧数量增多,高温煤灰低聚物增多,降低了煤灰的熔融温度。通过三元相图以及SEM分析,高温条件下煤灰中部分元素的富集以及团聚现象是导致Mg²⁺和Na⁺对煤灰熔融温度影响不同的原因。     

新型混凝土外加剂的制备和性能分析

聚羧酸减水剂已成为当今世界综合性能最优的外加剂,但较高的生产成本阻碍了它的迅速发展。通过研究,使用硬脂酸盐代替部分聚羧酸主体原料,可以解决此问题。首先,利用相似相容原理,依据HLB值选出一种表面活性剂,将其与硬脂酸盐按不同比例混合,用以改善后者同聚羧酸母液的相容性,通过实验,结合聚羧酸的固含量及生产成本,找到最优配比。然后,添加其他原料,分别复配制出20组不同比例的新型减水剂。依照国家标准测定该减水剂的主要化学成分指标,同时对各化学物质产生的原因进行了分析,并对其形成机理进行了探讨。依据相关标准,参照实验配合比要求,将减水剂掺入混凝土拌合物中,对混凝土主要物理力学性能进行了测定,并综合考虑各项因素,得出最优配方。     

A new method to analyze copolymer based superplasticizer traces in cement leachates

Enhancing the flowing properties of fresh concrete is a crucial step for cement based materials users. This is done by adding polymeric admixtures. Such additives have enabled to improve final mechanicals properties and the development of new materials like high performance or self compacting concrete. Like this, the superplasticizers are used in almost cement based materials, in particular for concrete structures that can have a potential interaction with drinking water. It is then essential to have suitable detection techniques to assess whether these organic compounds are dissolved in water after a leaching process or not. The main constituent of the last generation superplasticizer is a PolyCarboxylate-Ester copolymer (PCE), in addition this organic admixture contains polyethylene oxide (free PEO) which constitutes a synthesis residue. Numerous analytical methods are available to characterize superplasticizer content. Although these techniques work well, they do not bring suitable detection threshold to analyze superplasticizer traces in solution with high mineral content such as leachates of hardened cement based materials formulated with superplasticizers. Moreover those techniques do not enable to distinguish free PEO from PCE in the superplasticizer.Here we discuss two highly sensitive analytical methods based on mass spectrometry suitable to perform a rapid detection of superplasticizer compounds traces in CEM I cement paste leachates: MALDI-TOF mass spectrometry, is used to determine the free PEO content in the leachate. However, industrial copolymers (such as PCE) are characterized by high molecular weight and polymolecular index. These two parameters lead to limitation concerning analysis of copolymers by MALDI-TOFMS. In this study, we demonstrate how pyrolysis and a Thermally assisted Hydrolysis/Methylation coupled with a triple-quadrupole mass spectrometer, provides good results for the detection of PCE copolymer traces in CEM I cement paste leachates.     

Choice of polymer-bitumen binders for cast asphalt concrete mixes

Modification of bitumen with Kraton D1101 and D1192, Luprene LG 411 and 501, and DST-30-01 polymeric additives and the effect of these additives on the properties of cast asphalt concrete mixes were studied.     

Studying the physico-chemical properties of commercially available oil-well cement additives using calorimetry

Cement additives are typically used to modify the behavior of oil-well cement and to control its fluidity under well conditions. In this study, the retardation effect on cement hydration is investigated for a commercially available lignosulfonate and an NSF condensate at seven different concentrations. Additive solutions at 0.1% and 0.2% each by weight of cement (bwoc) with a ratio of (1:1) are also studied. The retardation of cement hydration process is monitored via isothermal calorimetry. Rheological studies are conducted to study the plasticizing effect induced by these additives. The mechanisms accompanying this process are better understood by studying the morphology of cement/additives systems using environmental scanning electron microscopy. The results show clearly that NSF has a retardation effect on cement hydration reflected on crystal growth. In addition, rheological measurements show that sodium lignosulfonate is more effective than NSF. The rheological effect alters with different cement/additive systems. This article provides recommendations for applying the most effective additive dosages in drilling and well-completion operations as well as enhancing the well-cementing quality.     

Adsorption Mechanism of Comb Polymer Dispersants at the Cement/Water Interface

Comb polymers are commonly used as dispersants to stabilize highly concentrated cement suspensions. The effectiveness of such polymeric additives to stabilize these suspensions is determined to a large extent by the amount adsorbed. In this study we investigated the adsorption characteristics of various comb dispersant containing different graft densities on surfaces of cement particle. The effect of inorganic salts on their adsorption was also examined in order to elucidate their adsorption mechanism. The results show that the adsorption of comb polymer dispersants on cement surface conforms approximately to Langmuir's adsorption isotherm and the characteristic plateau A _s and adsorption free energy ΔG_ads are largely dependent on the anionic group content of the comb polymers. The A _s and ΔG_ads increase with increasing anionic group content. This information suggests that the adsorption of comb polymers on cement surfaces is dominated by electrostatic interaction between COO-groups on the comb polymers and the positive surface of the cement. This conclusion is supported by effects of inorganics such as calcium and sulfate ions, and diffuse reflectance FTIR spectroscopy. The implication of results for tuning polymers for the required performance in cement manufacture should be noted.     

Study of γ‐Fast Neutron Attenuation and Mechanical Characteristics of Modified Concretes for Shielding and Sheltering Purposes

The study of γ‐neutrons attenuation and mechanical characteristics of modified concrete are vital and crucial parameters for the construction of civilian radiological, nuclear shielding, and/or shelters. In this work, fifteen samples of ordinary concretes with five different additives; steel fibers, polypropylene, silica fume, and fly ash, with variation of cement percentages, were prepared and used for performing the mechanical and radiation attenuation investigations. The compressive strength, tensile strength, slump test, bulk density, and water permeability were also carried out for the prepared concrete mixes. Collimated coherent beams from ⁶⁰Co and Pu‐Be fast neutron sources were used to check the radiation penetrability through the syntheized mixed concrete‐additives. Very sensitive and well calibrated gamma‐neutron pulse shape discriminating spectrometer with its electronic componenets and stilbene organic detector and 3′′ × 3′′ NaI scintillation crystal was used to measure the radiation before and after attenuation and transmission. The integrated fast neutron removal macroscopic cross section (Σ_r) and linear attenuation coefficient of total gamma rays (μ) were calculated for all the analysed concrete mixes. The results of measurements, tests, analyses and calculations are given and explained. The investigated modified concrete mixes show good workability and properties from the view point of mechanical loads and γ‐fast neutrons penetrability and resistance. These results can be used for shielding and sheltering design.     

Controlling the cohesion of cement paste

The main source of cohesion in cement paste is the nanoparticles of calcium silicate hydrate (C-S-H), which are formed upon the dissolution of the original tricalcium silicate (C(3)S). The interaction between highly charged C-S-H particles in the presence of divalent calcium counterions is strongly attractive because of ion-ion correlations and a negligible entropic repulsion. Traditional double-layer theory based on the Poisson-Boltzmann equation becomes qualitatively incorrect in these systems. Monte Carlo (MC) simulations in the framework of the primitive model of electrolyte solution is then an alternative, where ion-ion correlations are properly included. In addition to divalent calcium counterions, commercial Portland cement contains a variety of other ions (sodium, potassium, sulfate, etc.). The influence of high concentrations of these ionic additives as well as pH on the stability of the final concrete construction is investigated through MC simulations in a grand canonical ensemble. The results show that calcium ions have a strong physical affinity (in opposition to specific chemical adsorption) to the negatively charged silicate particles of interest (C-S-H, C(3)S). This gives concrete surprisingly robust properties, and the cement cohesion is unaffected by the addition of a large variety of additives provided that the calcium concentration and the C-S-H surface charge are high enough. This general phenomenon is also semiquantitatively reproduced from a simple analytical model. The simulations also predict that the affinity of divalent counterions for a highly and oppositely charged surface sometimes is high enough to cause a "charge reversal" of the apparent surface charge in agreement with electrophoretic measurements on both C(3)S and C-S-H particles.     

Investigation of ageing of alumina cement-based mixtures using thermal analysis and calorimetry

The shelf life of cement and cement-based dry mixtures is often determined by ageing of such materials. The ageing is the result of interactions between cement and other components of cementitious mixtures with moisture as well as with CO₂ from the atmosphere. In this work, the ageing behaviour of calcium aluminate cement and its mixtures with additives of microsilica, fluidized catalytic cracking catalyst waste and ground quartz sand were investigated. The ageing was achieved by storing cement and its mixtures in a climatic chamber for 7 and 14 days at 95% relative humidity and 20 ± 1 °C temperature. Applying thermal analysis, XRD analysis as well as scanning electronic microscopy, it was established that hydration of the cement minerals takes place along with carbonation during the ageing process of cement and its mixtures. The quantities of the products formed during ageing and their crystallinity depend on the nature of additives and the duration of ageing. When applying the method of calorimetric analysis, the influence of ageing on the kinetics of hydration of cement and as well as of its mixtures with the additives used in the work has been established.     

The use of thermal analysis in the approximate determination of the cement content in concrete

Thermal analysis was first used to investigate the pattern of dissociation of hydrated ordinary Portland cement. Portlandite (Ca(OH)₂) decomposes at about 500°C. This was confirmed by kinetic calculations. Thermal analysis was then performed to establish the effect of varying the cement content on the percent mass loss associated with the decomposition of Ca(OH)₂ in cement mortar cured for 28 days. An increasing relation was obtained. Standard concrete cubes were then prepared with cement contents ranging from 200 to 450 kg m^-3. The loss in mass on heating, up to 750°C, of concrete samples cured for 28 days was then related to the cement content in concrete. The relation obtained was tested for concrete cubes of known cement content and found to be in better agreement than the results obtained by conventional chemical analysis. This method can be used for an approximate determination of the cement content in concrete. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies on the influence of different fly ashes and Portland cement on early hydration of calcium aluminate cement

The influence of three mineral additives, i.e. fly ashes from pulverized combustion and from fluidized combustion of hard coal as well as Portland cement, on early hydration (up to 28th day) of calcium aluminate cement was investigated. Cement pastes containing 0, 5 and 25 wt% of additives were studied by the use of calorimetry, thermal analysis and infrared spectroscopy methods. It was confirmed that hydration of calcium aluminate cement is closely dependent on the type of addition and its amount. The influence of additives of different properties on cement hydration was discussed basing on received results and other literature reports.     

Conversion of silica-containing additives upon testing of cement compositions for alkali expansion

The peculiar features of the conversion processes proceeding upon the mortar-bar tests [GOST(State Standard) 8269.0] of high-dispersion silica-containing additives (silica fume, metakaolin, and precipitated silica) in the composition of a cement stone and sand-cement mortars at 20 and 80°C were studied. According to the solid-state NMR spectroscopy at 80°C, the additives rapidly loss phase individuality by reacting with Ca(OH)₂ to form calcium silica hydrogel (C-S-H), with Portland cement hydration in the presence of mineral additives proceeding slower than in the initial stone. Compared to Portland cement gel, the C-S-H product formed by the additives is characterized by lower Ca/Si ratio, longer aluminum-silicon-oxygen structural chains, and by higher content of aluminum in them.