The effects of adsorption of superplasticizers on the surface of cement

The effects of different types of superplasticizers in cement-water systems were investigated by microelectrophoresis and UV-absorption techniques. The purpose of the experiments was to investigate any differences in the magnitude of the Zeta Potential (ZP) and in the amount of superplasticizer adsorbed by using sulfonated polymers of different type, naphthalene, melamine, and polystyrene, with the respective molecular weights, MW=15,000 g/mole, MW=19,500 g/mole and MW=70,000 g/mole. The results show that the superplasticizer with the largest molecular weight gives the largest negative ZP, and is therefore concluded to have a higher dispersing capability. UV-absorption results have shown that the superplasticizer with the smallest molecular weight is the most adsorbed. That the polymer which is the least adsorbed gives the highest negative ZP can be expleined by the diffuse double-layer theory and a model is presented.     

The effect of superplasticizers and air-entraining agents on the Zeta potential of cement particles

The effect of superplasticizers and air-entraining agents on the Zeta Potential (ZP) of a Portland cement was studied by microelectrophoresis. The purpose of the experiments was to investigate the adsorption mechanism of electronegative polymers and surface-active agents, and the interaction between these when added in combination. As a preliminary experiment the microelectrophoresis technique was investigated in order to obtain the most precise and reproducible method of measuring Zeta Potentials. The results show that the superplasticizer type with the longer polymer chain and thereby the largest amount of electronegative charges per chain gives the highest negative Zeta Potential. This is interpreted as indicating that this type of superplasticizer has a higher dispersing capability. Data from dosage of air-entraining agents show that a part of the air-entraining effect is due to the fact that the molecules are adsorbed on the cement surface, thereby making it hydrophobic. The results of combined use of superplasticizers and air-entraining agents show that only a slightly smaller ZP is obtained than when a superplasticizer is dosed alone, which however still indicates an interaction. Finally the ZP has been determined of cement alone.     

Molecular characteristics of room‐temperature soluble fractions of low‐density polyethylene film resins

The molecular characteristics of the room‐temperature soluble fractions (RT solubles) of three low‐density polyethylene film resins were characterized by size‐exclusion chromatography (SEC), SEC combined with FTIR (SEC–FTIR), and nuclear magnetic resonance spectroscopy (NMR). The high‐molecular‐weight components of the RT solubles were found to be highly branched components with uniform short‐chain branching (SCB) profiles. For the low‐molecular‐weight components, however, SCB content was a function of molecular weight (MW), increasing with an increase in MW. When the chain ends were considered as SCB equivalents, the distribution of the sum of SCB and chain ends across the molecular weight distribution was practically flat, suggesting that the driving force for polymer chains remaining in solution at RT was the length of the undisrupted methylene sequence in the backbone, or methylene run length, which was too short to form crystal lamellae with a melting temperature above RT, regardless of the molecular weight of the polymer. Moreover, the NMR results revealed that the polymer components of the RT solubles had “superrandom” SCB distributions, that is, the fraction of comonomer clusters in the polymer chains of the RT solubles was lower than that predicted by Bernoullian statistical analysis, indicating that the probability of adding a comonomer to a comonomer‐ended propagating chain was lower than that of adding a comonomer to an ethylene‐ended one, presumably because of an unfavorable steric effect. Furthermore, contrary to the common belief that RT solubles are mainly low‐molecular‐weight polymers, high‐molecular‐weight components were found in high concentrations in the RT solubles, with a cutoff MW as high as 1,000,000 g/mol. The proportion of RT solubles in the film resins was found to depend on the type of resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4992–5006, 2006     

Development of internal structure of polymer-modified asphalts via transformations of the reduced frequency

The independent variable of dynamic material functions and corresponding master curves, the reduced angular frequency , was transformed into the apparent molecular weight MW*. As a function of MW*, the normalized master phase angle represented an apparent cumulative molecular weight. This function's numerical differentiation yielded the probability density function of the apparent molecular weight, f(MW*). While this procedure is unproblematic in conventional (straight run) asphalts, it is yielding peaks of negative MW* in polymer modified asphalts. Thus reduced frequency was also transformed to the temperature, which allowed us to determine that the apparent glass transition temperature as the maximum on the master curve of loss modulus G"(T). The master curve of the normalized phase angle as a function of temperature helped to explain the phenomenon associated with the probability density function in modified asphalts. The results presented in this article were obtained numerically, without the use of rheological models.     

聚丙烯酸钠陶瓷减水剂的制备及分散性能研究

以丙烯酸为单体,过硫酸铵-亚硫酸氢钠为氧化还原引发体系,制得可用于分散陶瓷浆料的中等相对分子质量(简称分子量,下同)聚丙烯酸钠。探讨了过硫酸铵用量、亚硫酸氢钠加入量、单体含量及反应温度对聚合物分子量的影响,并对不同分子量的产物在陶瓷料浆中的流动性进行了考察。聚丙烯酸钠的最佳合成条件为:过硫酸铵用量为单体总质量的0.8%,亚硫酸氢钠用量为单体总质量的10%～12%,单体占溶液总质量的24%～26%,反应温度为70～80℃。采用FTIR、GPC对聚合物进行表征,并对添加不同量聚合物的料浆Zeta电位、黏度及其复合后制得粗坯的弯曲强度进行了研究。结果表明,聚合物质量浓度为1 g/L时,Zeta电位绝对值由16.7 mV升高到54.6 mV。聚合物质量分数为0.25%,料浆体系的黏度从996 mPa.s降低到179 mPa.s。与添加无机陶瓷分散剂及聚合物的陶瓷粗坯样条相比,聚合物与无机电解质三聚磷酸钠以质量比1∶1复合后制得的粗坯弯曲强度可提高33.33%。     

Analysis of the action mechanism of polymer dispersant on dense ethanol alumina suspension using colloidal probe AFM

The action mechanism of a polymer dispersant on dense Al₂O₃ ethanol suspension was investigated using a colloidal probe AFM and branched and linear polyethyleneimines (PEIs). To obtain the minimum viscosity and Newtonian flow property of the dense ethanol suspension, the optimum molecular weights of the branched PEIs were determined over the range from 10,000 to 70,000. The linear PEI with Mw 1400 did not reduce the suspension viscosity compared to the branched PEI with the same molecular weight. The amount of adsorbed PEI did not significantly change regardless of the molecular structure and weight of the PEIs. However, the surface interaction between α-Al₂O₃ solids depended on the molecular structure and weight of the PEIs. The branched chain of the PEI adsorbed on the Al₂O₃ surface facilitated the short-range steric repulsion between particles. Based on the results, the increase in steric repulsive force and the disappearance of the adhesion force by the adsorption of the polymer prompted the dispersion of aggregates in suspension and reduced the viscosity of ethanol dense suspension.     

Molecular Weight Distribution Study of Delignification of Spruce Wood Meal With Chloroacetic Acids

The amount of lignin removed from spruce wood meal at 50°C to 110°C with mono-, di-, and trichloroacetic acid, as well as its molecular weight (MW) distribution was studied. Trichloroacetic acid gives rise to the lowest M_n (2,000–4,000), the lowest M_w (4,500–8,000), the lowest upper MW limit (～40,000), and the lowest polydispersity (1.5–3.0) of lignin. The removed lignin is split by the tested acids to different extents.     

Effect of multiple feeds on a termination-free polymerization in continuous stirred tank reactors

The effect of monomer and initiator feeds to each of a series of continuous stirred tank reactors (CSTR) on the molecular weight distributions, average molecular weight, polymer production rate, and initiator and monomer conversions is studied for the termination-free polymerization system. For initiator feed concentrations less than 0.001 mole/liter, the distribution becomes narrower as the polymer progresses from reactor 1 to reactor 3. But for concentrations of initiator of 0.01 mole/liter, the distribution may be broadened from reactor 1 to reactor 3. The broadening of the distribution results in the production of a lower molecular weight polymer.     

Swelling of poly(methyl methacrylate) thin films in low molecular weight alcohols

The effects of solvent size, temperature, and polymer molecular weight on the swelling of poly(methyl methacrylate) (PMMA) thin films in low molecular weight alcohols were investigated using an in situ ellipsometer. Apparent activation energies were indicative of non-Fickian diffusion, although optical data showed substantial Fickian character for swelling in methanol and moderate Fickian character in ethanol. Penetration rates were strongly dependent on the solvent molar volume for methanol, ethanol, and isopropanol, but 1-butanol and 2-pentanol had rates similar to isopropanol. The effective cross sections of these longer molecules are similar to isopropanol, and this apparently explains the similar penetration rates. The effect of polymer molecular weight (MW) on methanol penetration rates (21–27°C) was investigated with monodisperse PMMA (M_n = 6.4–40.0 × 10⁴ g/mol). A minimum at intermediate MW was observed. Isopropanol swelling rates (45–52°C) were insensitive to MW. The swelling data were also used to determine parameters for transport models that describe the swelling of thin polymer films.     

Influence of Resin Molecular Weight on Curing and Thermal Degradation of Plywood Made From Phenolic Prepreg Palm Veneers

The present work evaluates curing and the thermal behavior of different molecular weight phenol formaldehyde (PF) resins used to prepare PF prepreg oil palm stem veneers. The physical properties (solid contents, gelation time, pH, and viscosity) of PF resins were determined. The molecular weight of resins was characterized by gel permeation chromatography, whilst thermal properties were determined by differential scanning calorimetry and thermogravimetric analyses. The average molecular weight of PF resins were 526 g/mole (low), 1889 g/mole (medium), and 5178 g/mole (control - commercial). Among the resins, medium (MMwPF) gives better thermal stability with a retained weight of 48.9% at 300°C. High (Commercial PF) had a low decomposition temperature (109.3°C) which occurred within 11 min. Both low (LMwPF) and MMwPF started to melt at ≥120°C. Based on strength and shear values, phenolic prepreg palm veneers can be prepared using either low or medium molecular weight PF but with varying results. In all cases, the mechanical properties of palm plywood made from PF prepreg veneers were superior to those made from PF-bonded plywood using the commercial process.     

聚羧酸减水剂的合成及其分散性能

以甲氧基聚乙二醇甲基丙烯酸酯(PMA45)、甲基丙烯酸(MAA)、甲基丙烯磺酸钠(MAS)为单体,以过硫酸铵(APS)为引发剂,采用水溶液自由基聚合法合成了聚羧酸高效减水剂(PC),分析了合成过程中不同单体摩尔比、相对分子质量(简称分子量,以下同)大小对其分散性能的影响。结果表明,单体和引发剂的用量同时影响聚羧酸减水剂分子量和分散性能;当n(MAS)∶n(MAA)∶n(PMA45)=0.5∶3.75∶1,APS用量为单体总质量的0.4%时,产品聚羧酸特性黏度为45.09 mL/g;当水灰质量比为0.25,聚羧酸减水剂掺量为水泥质量的0.2%时,净浆初始流动度达到最大269 mm,30 m in经时流动度为281 mm。     

Synthesis,spinning, and properties of very high molecular weight poly(acrylonitrile-co-methyl acrylate) for high performance precursors for carbon fiber

In this paper, synthesis of very high molecular weight (VHMW) polyacrylonitrile-co-methyl acrylate (PAN-co-MA) polymers with weight average molecular weights of at least 1.7 million g/mole were repeatedly achieved on a laboratory scale using emulsion polymerization. The development of a hybrid dry-jet gel solution spinning technique for the VHMW PAN-co-MA enabled continuous spinning of 100 filament count tows, 100s of meters in length. Single filaments were analyzed and tested for tensile performance. Experimentally, the hybrid spinning method coupled with VHMW polymers produced precursor fibers with excellent tensile properties, averaging 954 MPa in strength and 15.9 GPa in elastic modulus (N = 296), with small filament diameters (5 μm). Results indicate a strong correlation between decreasing filament diameter, facilitated by high molecular weight polymer, and exponentially increasing tensile properties, using a hybrid dry-jet gel spinning process.     

Synthesis and the effects of water-soluble sulfonated acetone-formaldehyde resin on the properties of concrete

Water-soluble sulfonated acetone-formaldehyde (SAF) resins were synthesized by the reaction among acetone, formaldehyde, and sodium bisulfite. The surface activity of SAF resins and their performance in concrete were evaluated. The effect of molecular weight (MW) of synthesized SAF resins on the performance of the superplasticized concrete was determined. The results showed that the SAF resin has the potential to be developed as a superplasticizer used in concrete.     

Molecular weight and polydispersity measurements of polystyrene by quasielastic light scattering

The molecular weight and polydispersity of a polydisperse polystyrene sample was measured by quasielastic light scattering. The molecular weight distribution of the polymer was represented by the Schultz distribution. The weight average molecular weight and polydispersity of distribution was adjusted until the quasielastic light scattering spectra calculated for the distribution agreed with the measured spectra. The calculation was repeated using the logarithmic normal distribution for the polymer. The calculated value of the weight average molecular weight is accurate and insensitive to the assumed molecular distribution function. However, the calculated values of the polydispersity are only of fair accuracy. Thus quasielastic light scattering gives values of the weight average molecular weight at least as accurate as elastic light scattering and gives a crude estimate of the polydispersity of the polymer.     

纳米SiO2对聚羧酸减水剂的吸附作用研究

采用红外光谱、紫外-可见分光光度计研究了纳米SiO2对聚羧酸减水剂的吸附作用,并利用纳米粒度zeta电位仪、旋转粘度计研究了纳米SiO2吸附减水剂后对其分散性以及新拌水泥浆体流动性的影响.研究结果表明,纳米SiO2对聚羧酸减水剂存在吸附作用,吸附量随减水剂浓度的增大而增加,当减水剂浓度增加到5g/L时,吸附量趋近饱和.纳米SiO2对聚羧酸减水剂的吸附作用,使其团聚粒径增大,粒径分布曲线整体向大颗粒方向偏移,分散性大大降低.将纳米SiO2溶于拌和水中,先加入水泥搅拌,然后再加入减水剂搅拌,可减小纳米SiO2对减水剂的吸附,增大减水剂的利用效率,提高水泥浆体的流动性.     

Free radical copolymerization of methyl methacrylate and allyl acetate Part 2 structure and properties

The structure of the product from the free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) was investigated. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. Molecular weight (MW) and molecular weight distribution (MWD) are completely altered when the feed composition is dominantly AAc. NMR spectroscopy confirmed the incorporation of AAc into the polymer. However, no allyl–allyl linkages were observed at low conversions. T_g was found to be affected by the incorporation of AAc into the polymer. © 2001 Society of Chemical Industry     

Small-angle neutron scattering from polystyrene—DVB networks containing a delta fraction of deuterated polystyrene: Evidence for aggregation during polymerization

Homopolymer polystyrene-divinylbenzene, PS-DVB, networks were made by free radical chemistry u.v. photopolymerization techniques, and characterized by small-angle neutron scattering (SANS). The networks contained a delta fraction of chains labelled with deuterium. Two different series of samples were made: Method A in which the insertion was made centrally or at the end of the polymerization; Method B in which the delta fraction of deuterated primary chains was inserted at the beginning of the polymerization. Method B samples yielded a molecular weight of about 70,000 g/mole and a radius of gyration of about 120 Å, values in the range expected for single primary chains. Method A samples, however, gave molecular weights of 1–2 million and radii of gyration ranging from 350 to 400 Å. Intrinsic viscosity and gel permeation chromatography (g.p.c.) studies on parallel fractions yielded weight-average molecular weights near 72,000 g/mole for most of the polymerization. These results strongly suggest the existence of aggregation of primary chains synthesized in the same conversion period within the network. A new method of characterizing crosslinking between network chains is proposed, since these experiments count the probability of a chain crosslinking with a chain polymerized immediately before in time.     

Effect of deformation on the surface composition of multicomponent polymers: Blends of poly(dimethyl siloxane) in polychloroprene

X-ray photoelectron spectroscopy and scanning electron microscopy are used to follow the effect of uniaxial stretching on the surface composition and morphology of poly(dimethyl siloxane)/poly(chloroprene) blends. Before stretching, the blends exhibit a high surface segregation of siloxane due to an extremely low surface energy of the latter. The stretching gives rise to a substantial drop in the siloxane surface enrichment, whereas the subsequent unloading has the reverse effect. The surface behavior of the blends upon deformation strongly depends on the molecular weight of the siloxane component. Oligomeric siloxane (MW = 2500) shows a much stronger surface depletion with stretching, compared to that observed with a siloxane polymer (MW = 625,000). Furthermore, the surface behavior of the blends of the polymeric siloxane is completely reversible in sample length, whereas the blends of the oligomeric siloxane have different surface compositions on stretching and contraction. © 1996 John Wiley & Sons, Inc.     

线状聚羧酸高效减水剂在陶瓷坯料颗粒表面的吸附行为

采用静态吸附实验,研究了陶瓷坯料吸附两种自制聚羧酸高效减水剂的动力学规律,用准二级动力学模型对其吸附过程进行拟合,并通过测定添加了两种自制不同分子结构聚羧酸高效减水剂的陶瓷坯体料浆黏度以评价其分散性能,结果显示,在陶瓷坯体料浆中,线状MA/AA/AMPS聚羧酸高效减水剂的平衡吸附量是梳状AMPS改性聚丙烯酸高效减水剂的2倍以上,陶瓷坯料颗粒表面对两种聚羧酸高效减水剂的吸附均符合准二级反应动力学模型;线状MA/AA/AMPS聚羧酸高效减水剂的分散效能明显好于梳状AMPS改性聚丙烯酸高效减水剂。     

Synthesis of poly(ester‐anhydride)s based on poly(ϵ‐caprolactone) prepolymer

The objective of this study was to prepare high molecular weight poly(ester‐anhydride)s by melt polycondensation. The polymerization procedure consisted of the preparation of carboxylic acid terminated poly(?‐caprolactone) prepolymers that were melt polymerized to poly(?‐caprolactone)s containing anhydride functions along the polymer backbone. Poly(?‐caprolactone) prepolymers were prepared using either 1,4‐butanediol or 4‐(hydroxymethyl)benzoic acid as initiators, yielding hydroxyl‐terminated intermediates that were then converted to carboxylic acid‐terminated prepolymers by reaction with succinic anhydride. Prepolymers were then allowed to react with an excess of acetic anhydride, followed by subsequent polycondensation to resulting high molecular weight poly(ester‐anhydride)s. Upon coupling of prepolymers, size exclusion chromatography analyses showed an increase from 3600 to 70,000 g/mol in number‐average molecular weight (M_n) for the 1,4‐butanediol initiated polymer, and an increase from 7200 to 68,000 g/mol for the 4‐(hydroxymethyl)benzoic acid‐initiated polymer. 4‐Hydroxybenzoic acid and adipic acid were also used as initiators in the preparation of poly(?‐caprolactone) prepolymers. However, with these initiators, the results were not satisfactory. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 176–185, 2001