油溶性引发剂引发反相乳液聚合制备P(DMDAAC-AM)及其性能

用油溶性的引发剂引发,通过反相乳液聚合制备了二甲基二烯丙基氯化铵(DMDAAC)-丙烯酰胺(AM)共聚物P(DMDAAC-AM)(PDA),聚合反应中V(水)∶V(油)=1∶1.2,w(单体)=33%,n(DMDAAC)∶n(AM)=1∶9。研究了不同引发剂用量对聚合动力学的影响。结果表明:引发剂最佳加入量为m(引发剂)∶m(单体)=0.5∶100。探讨了PDA在纯水中的黏度特性,所制备的PDA呈典型的高分子电解质特性,稀溶液的比浓黏度随质量浓度变稀而增大。对PDA的应用性能也进行了初步研究。     

AM/DMDAAC/AA型两性聚丙烯酰胺的制备及应用研究

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酸(AA)为单体,用溶液共聚法制备两性聚丙烯酰胺(AMPAM),研究了反应条件对两性聚丙烯酰胺分子量及絮凝性能的影响。结果表明,采用K2S2O8-NaHSO3(质量比1∶1)氧化还原复合引发体系,引发剂用量为0.88%,单体用量为24.5%,聚合温度为55℃,溶液pH值为6,单体摩尔比为n(AM)∶n(DMDAAC)∶n(AA)=1∶0.3∶0.5,聚合时间为4 h,得到的产品综合性能最佳,且具有良好的絮凝脱色效果。     

新型超高相对分子质量两性聚丙烯酰胺的合成

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)及顺丁烯二酸(MA)为聚合单体,偶氮二异丁咪唑啉盐酸盐为引发剂,采用水溶液聚合法合成了超高相对分子质量两性聚丙烯酰胺(APAM),研究了单体浓度、单体摩尔比、引发剂用量、聚合温度以及反应体系pH值对聚合的影响,并通过傅里叶变换红外光谱仪对APAM结构进行了表征。结果表明:当总单体质量分数为20%,n(AM)/n(DMDAAC)/n(MA)为10∶80∶10,引发剂质量分数为0.05%,温度为50℃,反应体系pH值为7时,APAM的相对分子质量最高达到4.28×107。当用于处理模拟废水时,在pH值为3~10的环境中,APAM均能产生絮凝效果,说明产品适应的pH值范围较宽。     

光引发合成两性离子型聚丙烯酰胺的工艺优化

以丙烯酰胺(AM)、阴离子单体丙烯酸钠(AANa)和阳离子单体二甲基二烯丙基氯化铵(DMDAAC)为原料,采用光引发聚合方式合成了两性离子型聚丙烯酰胺P(AM-DMDAAC-AANa);探讨了合成P(AM-DMDAAC-AANa)的最佳条件。结果表明:在n(AM)∶n(AANa)∶n(DMDAAC)=1∶0.65∶0.16,单体质量分数为32%,引发剂用量为0.08%,光照时间为2.5 h,反应温度为30℃,p H=6.5的条件下,得到产物的特性黏数为887 m L/g。红外光谱分析表明:所得产物符合P(AM-DMDAAC-AANa)的结构特征。     

新型酸液稠化剂的制备与性能评价

酸化处理是油气井增产增注的重要措施之一,而其中稠化剂是酸液中一种重要的酸性添加剂.文章中以二甲基二烯丙基氯化铵（DMDAAC）和丙烯酰胺（AM）为原料,过硫酸铵-亚硫酸氢钠为引发剂,采用水溶液聚合制备共聚物PDA（（Poly DMDAAC-AM）.实验考察了单体配比、总单体质量分数和引发剂用量等反应条件对共聚物特性粘数和单体转化率的影响.结果表明,经红外检测AM和DMDAAC发生了聚合,单体配比n（AM）∶n（DMDAAC）=8∶2,单体总质量分数为20％,引发剂用量为过硫酸铵和亚硫酸氢钠各占单体总质量的0.04％,最高单体转化率为67.70％,最佳特性粘数为505.59 mL/g.实验采用石油工业标准（SY/T6214-1996）对产品性能进行了评价,结果表明产品性能优良,可用作酸液稠化剂.     

甲基丙烯酰氧乙基三甲基氯化铵与丙烯酰胺的合成研究

丙烯酰胺(AM)与甲基丙烯酰氧乙基三甲基氯化铵(DMC)进行水溶液聚合,考察了引发剂浓度、温度、单体配比、pH值、引发剂等因素对共聚物的阳离子度、特性黏度以及相对分子质量的影响。结果表明,制备高相对分子质量的阳离子型聚丙烯酰胺的最佳工艺条件为:pH为8,温度为50℃,引发剂的用量为0.8 mmol/L,DMC∶AM(摩尔比)=1∶3。     

高聚合度阳离子型聚丙烯酰胺的合成研究

采用丙烯酰胺(AM)与阳离子单体二甲基二烯丙基氯化铵(DMDAAC)共聚制备高分子量的CPAM。研究了影响AM与DMDAAC共聚物的平均分子量的因素,得到了优化条件为:单体浓度为30%,DMDAAC与AM摩尔比为5∶95,聚合温度为30℃,低温段引发剂用量为0.05‰(占单体质量分数,下同),K2S2O8与NaHSO3质量比为1∶1,偶氮二异丁基脒盐酸盐(V-50)用量为0.025‰,尿素用量为40‰,乙二胺四乙酸二钠(EDTA-2Na)用量为0.05‰,在此优化条件下聚合反应16 h后得到分子量为1.217×107的阳离子型聚丙烯酰胺(CPAM)。CPAM被广泛应用在各种水处理和固液分离过程中。     

光引发合成两性聚丙烯酰胺的影响因素

以丙烯酰胺(AM)、阴离子单体丙烯酸纳(AANa)、阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)为原料,采用光引发聚合方式合成两性聚丙烯酰胺P(AM-DAC-AANa),探讨了合成P(AM-DAC-AANa)的最佳条件。结果表明:在n(AM)∶n(AANa)∶n(DAC)=1∶0.7∶0.2,单体质量分数为30%,引发剂用量为0.08%,光照时间为2.5h,引发温度为30℃,溶液p H为7.0条件下,得到产物的特性粘数为976m L/g。红外光谱分析表明:所得产物符合P(AM-DAC-AANa)的结构特征。     

两性聚丙烯酰胺“水包水”乳液的制备

以丙烯酰胺(AM)和两性单体N,N-二甲基(甲基丙烯酰氧乙基)氨基丙磺酸内盐(DMAPS)为聚合单体,聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC)为分散稳定剂,2,2'-偶氮(2-脒基丙烷)二盐酸盐(V-50)为引发剂,在硫酸铵水溶液中通过分散聚合制备两性聚丙烯酰胺(AmPAM)"水包水"乳液。考察了分散剂用量、无机盐用量、单体质量分数及其摩尔比和引发剂用量等对分散聚合的影响,其最佳反应条件为:硫酸铵质量分数22.3%～27.4%、分散剂用量为0.195～0.248 g/g(monomer)、单体摩尔比n(AM)∶n(DMAPS)=9∶1、单体质量分数为14%、引发剂用量为4.5×10-4g/g(monomer)。采用红外光谱(FTIR)和核磁共振氢谱(1HNMR)对聚合物结构进行了表征。     

PDA的合成及其对污泥深度脱水作用

采用水溶液聚合法合成聚二甲基二烯丙基氯化铵-丙烯酰胺(Poly-DMDAAC-AM,PDA),研究了体系溶液的pH、n(AM)∶n(DMDAAC)、引发剂投加量等因素对合成PDA的影响,当pH=3、n(AM)∶n(DMDAAC)=4∶1、引发剂浓度为1.0×10-4 mol/L时,合成的PDA产品相对分子质量和阳离子离子度最高。采用合成的PDA与无机盐对城市污泥进行调理后顺利达到国家环保部关于加强城镇污水处理厂污泥污染防治的要求,成功实现污泥深度脱水。     

Quantification of Phospholipids Classes in Human Milk

Phospholipids are integral constituents of the milk fat globule membranes and they play a central role in infants’ immune and inflammatory responses. A methodology employing liquid chromatography coupled with evaporative light scattering detector has been optimized and validated to quantify the major phospholipids classes in human milk. Phospholipids were extracted using chloroform and methanol and separated on C18 column. Repeatability, intermediate reproducibility, and recovery values were calculated and a large sample set of human milk analyzed. In human milk, phospholipid classes were quantified at concentrations of 0.6 mg/100 g for phosphatidylinositol; 4.2 mg/100 g for phosphatidylethanolamine, 0.4 mg/100 g for phosphatidylserine, 2.8 mg/100 g for phosphatidylcholine, and 4.6 mg/100 g for sphingomyelin. Their relative standard deviation of repeatability and intermediate reproducibility values ranging between 0.8 and 13.4 % and between 2.4 and 25.7 %, respectively. The recovery values ranged between 67 and 112 %. Finally, the validated method was used to quantify phospholipid classes in human milk collected from 50 volunteers 4 weeks postpartum providing absolute content of these lipids in a relatively large cohort. The average content of total phospholipids was 23.8 mg/100 g that corresponds to an estimated mean intake of 140 mg phospholipids/day in a 4-week old infant when exclusively breast-fed.     

The hydration of reactive cement-in-polymer dispersions studied by nuclear magnetic resonance

The behaviour of two novel cement-in-polymer (c/p) dispersions, namely cement-in-poly(vinyl acetate) and cement-in-poly(vinyl alcohol) upon exposure to water at room temperature was investigated by a combination of various NMR methods. The swelling, cracking, and the water ingress were monitored non-destructively using ¹H single point imaging. The hydration of the cement matrix was investigated using ²⁹Si NMR whilst ¹³C CPMAS NMR spectra allowed the quantification of the kinetics of the hydrolysis reaction of poly(vinyl acetate) into poly(vinyl alcohol). The polymer controls the rate of water ingress and swelling which in turn determines the behaviour of the c/p dispersions upon exposure to water. For the cement-in-poly(vinyl alcohol), the rates of water ingress and swelling are much faster than the hydration of the clinker whilst for the cement-in-poly(vinyl acetate) the slow rates of the two processes allow the formation of a cementious matrix which assures the stability of the sample.     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Design and function of novel superplasticizers for more durable high performance concrete (superplast project)

In this article we shall describe our quest and ultimate success in furthering our understanding of the action of superplasticizers on the rheology of cement and concrete. By specifically producing superplasticizers with varied architectures, we have been able to show the important structural features of the macromolecules that lead to a successful superplasticizer or water reducing agent. Both polycarboxylate and lignosulfonate polymers have been investigated. Using both non-reactive model MgO powders, three different types of cement blends, the adsorption behaviour and the effect on the rheological properties of these two important superplasticizer families have been used to further develop a conceptual model for superplasticizer — cement behaviour. This paper will deal mainly with the conceptual model, the materials and methods used to asses the polymer adsorption behaviour and rheological properties of the systems studied. We shall briefly describe the adsorption of the polymers onto the different surfaces and their influence on surface charge and rheology and the influence of the various ionic species found in cement pore solutions that may influence polymer-cement affinity. The key factors are shown to be the effective adsorbed polymer thickness and the induced surface charge which can be influenced by the polymer architecture, the pore solution composition and the initial particle surface charge.     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Study of the hydration of CaO powder by gas–solid reaction

Hydration of CaO powders by reaction with water vapor has been studied in isothermal and isobaric conditions. Experimental tests were performed within the temperature range of 70 °C–420 °C and with a water vapor pressure from 5 to 160 hPa by means of a thermogravimetric device. Two powders, exhibiting slight differences in their physical properties, were studied. However, for one of the powders and under some temperature and pressure conditions, the reaction is not complete. The difference of behavior between both CaO powders was interpreted by considering the effect of the morphological properties on the mechanism of growth of Ca(OH)₂.     

2-(2'-咪唑偶氮)萘酚-4-磺酸的合成及其分析性质的研究

合成了新显色剂咪唑偶氮－２－萘酚－４－磺酸（ＩＡＮ－４Ｓ）,研究了试剂的离解常数及其与金属离子的显色反应。     

Influence of bleed water reabsorption on cement paste autogenous deformation

The effects of bleed water reabsorption and subsequent early age expansion on observed autogenous deformation are investigated in this research. Bleeding was induced by varying superplasticizer and shrinkage-reducing admixture dosages and by increasing the water-to-cement ratio. This research revealed that significant early age expansion occurs with increasing chemical admixture dosages and higher water-to-cement ratios, as expected, due to increasing bleeding of those samples. When samples were rotated, negligible early age expansion was observed. Thus, bleed water reabsorption is shown to be the primary mechanism causing initial expansion in sealed autogenous deformation samples. Thermal dilation and ettringite growth appear to have a minimal influence on the observed expansion. Rotating the samples during setting eliminates the potential for bleed water reabsorption and is recommended for all autogenous deformation testing.     

Comparison between surface and bulk hydrophobic treatment against corrosion of galvanized reinforcing steel in concrete

The effectiveness of bulk hydrophobic treatment against corrosion of galvanized steel reinforcement in concrete specimens with w/c = 0.45 and w/c = 0.75 was compared with that of surface treatment, even in the presence of cracks 0.5 and 1 mm wide in the concrete cover. In this case surface hydrophobic treatments were applied both before and after cracking as a preventive and a restorative method against reinforced concrete deterioration, respectively. The obtained results in terms of water absorption, electrochemical measurements, chlorides penetration, and visual observations carried out on reinforced concrete specimens during the exposure to wet–dry cycles in 10% NaCl solution showed that bulk hydrophobization is the most effective treatment in improving the corrosion resistance of galvanized steel reinforcements in concrete also in the presence of cracks. Surface hydrophobization is very effective just in the first few exposure cycles to the aggressive environment and when used as a restorative method which is able to cancel the deleterious effect of cracks only 0.5 mm wide.     

Effect of plasma treatment of polymeric tape carriers on wetting behaviour of aqueous ceramic tape casting slurry

Due to environmental and health aspects, aqueous ceramic slurries are preferred to traditional organic solvent systems in tape casting. An important obstacle associated with the high surface energy of water is poor wetting of aqueous ceramic slurries on polymeric tape carriers. Therefore, we measured the contact angles of an aqueous epoxy-based ceramic slurry on polyethylene terephtalate (PET), polypropylene (PP), polymethyl methacrylate (PMMA), and aluminium-coated polyethylene terephtalate (PET-Al) films and investigated approaches to improving their wetting. We evaluated the effect of plasma treatment of the tape carrier surface on the wetting behaviour and compared it with the effect of adding non-ionic amphiphilic surfactants to the ceramic slurry. The treatment of the tape carrier surface by low-temperature plasma substantially improved the wetting behaviour of aqueous ceramic slurry. The lowest contact angle of 31° was obtained on the PET film. Although the addition of non-ionic surfactants improved both the wetting behaviour of the slurry and the detachment of the polymeric carrier from the ceramic tape even better than the plasma treatment of the carrier surface did, the plasma-treated carriers still present a useful alternative to the surfactants. In the case of the plasma-treated PET carrier the surfactants could be fully eliminated and potential drawbacks related to the use of surfactants could be prevented.