Effect of Side Chains and Sulfonic Groups on the Performance of Polycarboxylate-Type Superplasticizers in Concentrated Cement Suspensions

Polycarboxylate-type superplasticizers (PCs) containing different side chains and sulfonic groups have been synthesized, and the effect of side chains and sulfonic groups on their performance in cementitious systems has been intensively investigated by measuring zeta potential, thickness of absorption layer, paste fluidity, rheological properties as well as the setting time in this paper. Results show that the PC containing both short poly(ethylene oxide) (PEO) side chains and long PEO side chains with the molar ratio of 1:1 has a better dispersibility than the PC containing only short PEO side chains or only long PEO side chains in cement suspensions. The shorter the side chain of the PC, the longer the setting time of cement paste incorporating it. An appropriate increase of sulfonic group content is beneficial for the improvement of dispersibility for the PC and leads to no obvious change for the setting time. It also suggests that there is a geometrical balance between the PEO side chains and sulfonic groups for the performance of PC. This work is not only helpful for understanding the relationship of molecular structure of PCs and their performance, but also further designing optimum molecular structure of PC to meet the requirement in different concrete system.     

Preparation,application and water reducing mechanism of a novel fluorescent superplasticizer with improved flow retaining ability and clay tolerance

Abstract

Novel fluorescent polycarboxylate superplasticizer modified by anhydride naphthalene groups was prepared, and characterized by ^1?H NMR and FTIR. Fluidity behaviors of cement suspensions mixed with the polycarboxylate indicated that the superplasticizer not only exhibited good fluidity maintaining properties but also demonstrated stable performance in the coexistence of clay. The addition of quaternary ammonium salt polymer can inhibit the water absorption and expansion of clay. Adsorption amounts, adsorption layer thickness and zeta potential were determined to elucidate the water reducing mechanism. The adsorbed layer thickness was linked to the steric hindrance, deciding the dispersing ability and dispersing retention ability.     

中分子毒素在碳纳米管上的吸附

研究了两种不同形态的碳纳米管(随机生长多壁碳纳米管(MWCNTs)及定向生长多壁碳纳米管(ACNTs))对典型中分子毒素的吸附性能. 并与两种现有商用血液灌流吸附材料(活性炭(AC)及大孔吸附树脂(MR))进行了对比. 结果显示, 碳纳米管(CNTs)具有优异的中分子吸附能力, 其中MWCNTs对典型中分子毒素的吸附量可达47.18 mg·g-1, 为活性炭的10.8倍, 为大孔吸附树脂的5.5倍. 此外, 碳纳米管的吸附非常迅速, 中分子毒素在MWCNTs及ACNTs达到吸附平衡的时间仅为10 min和15 min, 而活性炭及大孔吸附树脂则分别需要60 min及120 min. 碳纳米管优异的吸附性能得益于其独特的微观结构所形成的发达的中孔. 因此, 碳纳米管可望成为高效的吸附材料, 应用于血液灌流中.     

Characterization and Antioxidant Activity of Mannans from Saccharomyces cerevisiae with Different Molecular Weight

Polysaccharides were extracted from natural sources with various biological activities, which are strongly influenced by their chemical structure and molecular weight. In this research, mannans polysaccharides were obtained from Saccharomyces cerevisiae by ethanol precipitation. The molecular weight of YM50, YM70, and YM90 mannans was 172.90 kDa, 87.09 kDa, and 54.05 kDa, respectively. Scanning electron microscopy of YM 90 mannans showed a rough surface with numerous cavities, while the surfaces of YM50 and YM70 were relatively smooth. Sepharose CL-6B and FTIR indicated that mannans had the characteristic bands of polysaccharides. The antioxidant activities of polysaccharides were evaluated in vitro using various assays. Mannans showed a good scavenging activity of DPPH radicals which depend on the molecular weight and concentration, and a higher scavenging activity of hydroxyl radical than ferric-reducing power activities. For the three types of mannans, cytotoxicity and hemolytic activity were rarely detected in mice erythrocytes and Caco-2 cells. Those results could contribute to the further application of mannans from Saccharomyces cerevisiae in the food and medicine industry.     

聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究

针对被称为"第一代聚羧酸高性能减水剂"(以下简称为MPEG-type PCE)的甲基丙烯酸(MAA)/烯酸甲酯(MAA-MPEG)梳状共聚物分子,从高分子物理基础理论出发,构建等效自由连接链模型,结合前人的理论结果和实验数据,得到了MPEG-type PCE分子的回转半径、流体力学半径及其相应的支化参数的数学表达式.在此基础上,报道了以下三方面的工作:首先,将计算结果与文献中的实验结果进行比较,检验模型的合理性;其次,利用所建立的数学模型考察主链分子量、侧链分子量和侧链接枝密度对PCE分子的回转半径和流体力学半径的影响;最后,结合近年来发展的体积排除色谱分离理论,对PCE分子的真实分子量与其常规体积排除色谱"表观分子量"(又被称为GPC分子量)两者之间的差异进行了分析.本文所提出的计算模型和数学表达式没有不确定的指前因子,可用来估算MPEG-type PCE分子在稀水溶液中的尺寸以及根据其GPC分子量估算真实分子量.     

医用超高分子量聚乙烯摩擦磨损性能的研究进展

综述了影响医用超高分子量聚乙烯(UHMWPE)摩擦学性能的因素,以及改进的方法。总的来说,影响因素有填料的种类、润滑剂、接触面、运动轨迹、操作参数等多种因素。通过物理和化学的方法可以改进其摩擦学性能。     

Broadening the Polyethylene Molecular Weight Distribution by Periodic Variation of the Hydrogen Feed Rate

The ability to control the molecular weight distribution of the created polyethylene in gas‐phase fluidized‐bed reactors is discussed. This objective is achieved via nonlinear model predictive controller utilizing the hydrogen feed rate as the only manipulated variable. The idea for limited usage of manipulated variables is to avoid economically unfavorable operations such as excessive purge and/or reduced production rate. The simulation results indicated successful implementation of the control algorithm to attain the desired molecular weight distribution. The success depends on the improved hydrogen activities inside the reactor by employing a modified catalyst that is responsive to hydrogen variation and allowing a wider range for hydrogen feed rates.

     

Adsorbing behavior of polycarboxylate superplasticizer in the presence of the ester group in side chain

The effect of the ester group in side chain on adsorbing behavior and dispersion of polycarboxylate superplasticizer (PC) was studied by comparing the performance of two types of PC. The fluidity of cement paste was tested to discuss the dispersing ability and dispersing retention ability of PC. The total organic carbon analyzer was used to measure the adsorption amount, and the adsorption layer was obtained by x-ray photoelectron spectroscopy. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and pH value were used to verify the stability of the ester group, and the electrokinetic properties of cement particle were confirmed using the zeta potential measurement. The results show that the ester group in side chain reduces the initial dispersing ability while it increases the dispersing retention ability. The dispersing retention ability depends on the increase of adsorption amount and adsorption layer in 5–60 minutes, and the greater increase leads to the better dispersing retention ability. The ester group can be decomposed to release carboxyl group to enhance the adsorbing ability of PC under the condition of cement hydration, which is the main reason for the greater increase of adsorption amount and adsorption layer and the improvement in dispersing retention ability. It suggests that grafting the ester group is a good way to enhance the dispersing retention ability.     

松香改性苯乙烯聚合物分子量及分子量分布的GPC测定

本文利用凝胶渗透色谱测定新型高分子材料（苯乙烯-歧化松香树脂乙烯酯）的分子量及分子量分布，实验数据重视性较好。标准偏差为0．074，变异系数为3．360％。     

高平均分子量聚丙烯腈的制备、性能和应用

介绍了高平均分子量聚丙烯腈的主要制备方法，如混合溶剂自由基聚合、水相悬浮聚合、反相浮液聚合、离子聚合、紫外光辐射聚合等。还根据高平均分子量聚丙烯腈的性能探讨了其在高性能碳纤维前驱体聚丙烯腈原丝和高强高模中空纤维过滤膜方面的应用。     

Investigation of the Interactions in Complexes of Low Molecular Weight Chitosan with Ibuprofen

Complexation between ibuprofen and low molecular weight chitosan (LMWC) was studied. LMWC was prepared from high molecular weight chitosan using the acid hydrolysis method. The complexes were investigated by using DSC, FT-IR and liquid-state ¹H-NMR. Molecular mechanics (MM) calculations were used to give insight into the stoichiometry of the interaction of chitosan with ibuprofen. The results showed that complexation of ibuprofen with LMWC involves ionic interaction between the ammonium group of LMWC and the carboxylate anion of ibuprofen. It was also shown that it is more efficient to prepare the complexes using lower concentration solutions of the polymer. These results were supported by molecular mechanics calculations. The experimental results may explain the discrepancies in the literature where, in many studies, the concentration of chitosan and its low average molecular weight were not considered to be important factors in the complexation process.     

悬浮聚合法合成超高分子量的聚乙烯醇

用悬浮聚合法合成了超高分子量的聚乙烯醇,分子量260,000-350,000,聚合度6,000～8,000。     

高分子量聚苯硫醚树脂的合成

用H_2S、NaOH、p-C_6H_4Cl_2为原料,以Na_3PO_4作助剂,在六甲基磷酰三胺中进行常压缩聚反应4～5 h,得到线型、结晶性的高分子量聚苯硫醚。熔点>290℃,热分解温度>500℃,熔融低切变粘度为0.30～68.0×10~3Pa(303℃测定)。产品直接作抽丝试验,得到高分子量聚苯硫醚纤维。本法设备简单、操作容易、反应体系活性高、溶剂稳定。     

Effect of Molecular Weight on the Interfacial Dilational Viscoelasticity of Anionic Polyelectrolyte/Surfactant Systems

In this article, the effect of molecular weight on the interfacial tension and interfacial dilational viscoelasticity of polystyrene sulfonate/surfactant adsorption films at the water-octane interface have been studied by spinning drop method and oscillating barriers method respectively. The experimental results show that different interfacial behaviors can be observed in different type of polyelectrolyte/surfactant systems. PSS/cationic surfactant CTAB systems show the classical behavior of oppositely charged polyelectrolyte/surfactant systems and can be well explained by electrostatic interaction. Molecular weight of PSS plays a crucial role in the nature of adsorption film. The complex formed by CTAB and higher molecular weight PSS, which has larger dimension and stronger interaction, results in higher dilational modulus at lower surfactant bulk concentration. In the case of PSS/anionic surfactant SDS systems, the co-adsorption of PSS at interface through hydrophobic interaction with alkyl chain of SDS leads to the increase of interfacial tension and the decrease of dilational modulus at lower surfactant bulk concentration. For PSS/nonionic surfactant T × 100 systems, PSS may form a sublayer contiguous to the aqueous phase, which has little effect on interfacial tension but slightly decreases dilational modulus.     

Effect of Molecular Weight on Enthalpy Relaxation in Syndiotactic Poly(Methyl-Methacrylate)

The structural relaxation behaviour of narrow fractions (M_w/M_n < 1.1) of syndiotactic poly(methyl methacrylate) with molecular masses ranging from 2,000 to 200,000 Daltons have been studied by DSC with two classical procedures, namely: the rate of cooling and the isothermal approaches. The apparent activation energy (Δh*) of enthalpy relaxation was evaluated from the dependence of the glass transition temperature on the cooling rate while a comparison of the apparent relaxation rates was appraised from the enthalpy loss by annealing the different samples at the same level of undercooling (T_a = T_g − 10 °C). As expected, the increase of molecular weights gives rise to both a continuous increase of Δh* and a decrease of the apparent isothermal relaxation rate. More interestingly, both Δh* and the apparent isothermal relaxation rate showed abrupt changes around the syndiotactic PMMA entanglement mass (M_e ).     

Evaluation of the adsorption trends of a low molecular-weight polyelectrolyte with a site-binding model

The site-binding model is very useful for describing the adsorption of ions and small ionized molecules. It has been slightly modified to include multi-site adsorption of larger molecules such as oligomers and low molecular weight polyelectrolytes. We describe alterations of the classical model and the results of calculations for adsorption of polyacrylic acid onto titanium dioxide as an example. The triple layer model is used to relate charge densities to interfacial potential profiles. Comparison between adsorption trends and the surface layer composition as a function of pH and ionic strength demonstrates the prominent influence of ions binding in the adsorption process. The site-binding model makes it easy to simulate the ions displacement associated with polyelectrolyte adsorption. Strongly bound electrolyte anions prevent polyacrylic acid from adsorbing, and, in contrast, electrostatic screening due to cation condensation makes it easier. Calculations of the pH change in the solution, due to adsorption, are also made by comparing ionization ratios of both the surface and polymer units in the adsorbed layer and before adsorption. Trends in electrokinetic potentials as a function of the solution's parameters are evaluated assuming the identity of the shearing surface and the inner boundary of the diffuse layer. All data compare well with experimental values. The very good agreement betwen the experiment and model calculations supports the fact that (small) polyelectrolyte molecules adsorb essentially flat on the surface.     

Characteristics of the Molecular Weight of Polyhexamethylene Guanidine (PHMG) Used as a Household Humidifier Disinfectant

(1) Background: Household humidifier disinfectant (HD) brands containing polyhexamethylene guanidine (PHMG) have been found to cause the most HD-associated lung injuries (HDLIs) in the Republic of Korea. Nevertheless, no study has attempted to characterize the potential association of the health effects, including HDLI, with the physicochemical properties of PHMG dissolved in different HD brands. This study aimed to characterize the molecular weight (MW) distribution, the number-average molecular weight (M_n), the weight-average molecular weight (M_w), and the structural types of PHMG used in HD products. (2) Methods: Quantitative measurements were made using matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF MS). The M_n, M_w, and MW distributions were compared among various HD products. (3) Results: The mean M_n and M_w were 542.4 g/mol (range: 403.0–692.2 g/mol) and 560.7 g/mol (range: 424.0–714.70 g/mol), respectively. The degree of PHMG oligomerization ranged from 3 to 7. The MW distribution of PHMG indicated oligomeric compounds regardless of the HD brands. (4) Conclusions: Based on the molecular weight distribution, the average molecular weight of PHMG, and the degree of polymerization, the PHMG collected from HDLI victims could be regarded as an oligomer. PHMG, as used in household humidifiers, should not be exempted from toxic chemical registration as a polymer. Further study is necessary to examine the association of PHMG oligomeric compounds and respiratory health effects, including HDLI.     

高分子量聚合物对溶剂诱导低分子量聚合物薄膜去润湿动力学的影响

采用偏光显微镜及椭偏仪等研究了单分散低分子量聚苯乙烯(PS)薄膜、 单分散高分子量PS薄膜以及将二者按不同质量比共混制备的PS薄膜, 在室温下用丙酮溶剂诱导其去润湿的过程. 实验发现, 按不同质量比共混的PS薄膜的去润湿动力学与单分散的PS薄膜去润湿动力学有较大区别. 按不同质量比共混的PS薄膜, 低分子量的PS更易于富集在薄膜的表面, 其去润湿的速度介于单分散低分子量PS薄膜与单分散高分子量PS薄膜的去润湿速度之间. 但共混薄膜的去润湿速率并非随着高分子量PS的加入呈现单调的变化, 这是由大量接触分子的形成抑制了去润湿所致.     

不同聚合度聚乙二醇对A30碳钢的缓蚀性能

通过开路电位测量法、动电位极化曲线法和电化学阻抗谱法研究了表面活性剂聚乙二醇对A30碳钢的缓蚀作用,初步推测了其缓蚀机理．分别选取聚合度为600、2000、4000、6000的四种聚乙二醇进行实验,结果表明,聚乙二醇对碳钢的最高缓蚀率接近90％．聚乙二醇分子量对缓蚀作用有明显影响,相同浓度时聚合度越大,缓蚀性能越强．三种方法得到的结果具有同一性．     

超高分子量聚乙烯基导电复合材料的电性能和自发热性能的研究

超高分子量聚乙烯(UHMWPE)具有优异的综合性能,本文采用凝胶结晶溶液方法制备了分别以碳纤维(CF)和镀镍碳纤维(NiCF)为导电填料,UHMWPE为基体的3个系列导电聚合物复合材料—UHMWPE/CF、UHMWPE/NiCF和UHMWPE/EMMA/CF复合体系,并分别对它们进行了室温伽马射线辐射处理,重点研究了这些材料的电性能和自发热性能,利用DSC、SEM、WAXS、DMA和体积膨胀等仪器进行了一系列测试表征。结果表明,NiCF作为导电填料时体系的逾渗阈值最低,为3vol%。伽马射线辐射处理不仅能有效提高材料的PTC效应,而且在合适的辐射剂量时也能有效提高材料的自发热性能。对材料介电性能的研究揭示了材料的交流电阻率与温度、频率的依赖关系。