Rheological behavior of waterborne polyurethane/starch aqueous dispersions during cure

Isothermal rheological behaviors of waterborne polyurethane (WPU)/starch aqueous dispersions during cure were investigated with a small-amplitude oscillatory shear flow experiment to evaluate their crosslinked structure and to predict their mechanical properties, for the first time. An abrupt increase in the elastic storage modulus (G′), the viscous loss modulus (G″), the complex dynamic viscosity (η^*) and the loss tangent (tan δ) was observed during the curing process of the dispersions, as a result of the formation of a fractal polymer gel. The gel point (t_gel) was determined from the intersection in tan δ vs curing time for different constant shear frequencies, where tan δ was frequency independent and all curves crossed over, indicating the validity of the Winter–Chambon criterion for the complex system. The values of the power law exponent (n) and the gel strength (S_g) at the gel point indicated that with an increase of starch content the crosslinked WPU/starch gels underwent a transition from weak fractal to strong elastic ones. Moreover, the WPU/starch composite sheets, obtained from the aqueous dispersions with relatively high S_g values, also exhibited the increased tensile strength (σ_b) and Young's modulus (E). Their structure–mechanical properties relationship and the phase transitions of dispersed starch–dual-phase continuity–starch matrix were revealed. This work confirmed that the rheological characters could be used to predict the mechanical properties of the WPU materials blended with natural polymer.     

Effect of dicarboxylic acids on the performance properties of polyurethane dispersions

A series of low molecular weight linear polyester polyols were synthesized by using various diacids, neopentyl glycol, as a diol, and a trimethylol propane, as a branching monomer. Polyurethane dispersions were prepared primarily from isophorone diisocyanate, polyester polyol, and dimethylol propionic acid, as potential ionic center for water dispersibility, and were subsequently chain extended with ethylene diamine. The effect of polyester polyols based on variable diacids, on the physico‐chemical and thermal properties of polyurethane dispersions were evaluated by hardness, flexibility, impact resistance, solvent resistance, thermogravimetric analysis, and differential scanning calorimetry. Particle size was evaluated by particle size analyzer. It was observed that the number of alkylene groups present in the polyester polyol soft segment in addition to its molecular weight had a pronounced effect on the particle size, physico‐chemical, and thermal properties. With a proper selection of the soft segment, it is possible to fine‐tune properties of aqueous polyurethane dispersion coatings with respect to the final application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological properties of concentrated solutions of agarose in ionic liquid

The rheological properties of agarose solutions were examined under the effect of entanglement coupling between agarose chains. Agarose solutions were prepared by using an ionic liquid 1‐butyl‐3‐methylimidazolium chloride as a solvent. The concentration of agarose was varied from 1.1 × 10¹–2.1 × 10² kg m^?3. The master curves of the angular frequency (ω) dependence of the storage modulus (G′) and the loss modulus (G″) showed a rubbery region in the middle ω region and a flow region at low ω region, respectively. The molecular weight between entanglements (M_e) for agarose was calculated from the plateau modulus. Moreover, M_e for agarose melt was determined to be 2.3 × 10³ from the concentration dependence curve of M_e. By using well‐known empirical relations in polymer rheology, information on molecular characteristics of sample agarose was derived. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

超浓乳液聚合稳定性的影响因素及研究进展

讨论了稳定剂体系、单体、连续相的黏度和pH值、电解质、温度、加工工艺等对超浓乳液聚合稳定性的影响,总结出了不同单体超浓乳液聚合的最佳稳定性条件。     

Optical characterization of concentrated dispersions: applications to laboratory analyses and on‐line process monitoring and control

Light scattering methods are often used to study the stability of suspensions or emulsions and to estimate the dispersed phase properties such as particle size and volume fraction. However, such optical methods often require a previous dilution of the dispersion because of a limited measurement range, and are then unable to give information about the real physical state of dense heterogeneous media. A new technology based on multiple light scattering analysis and called Turbiscan has been recently developed by a French company, Formulaction, to fill this gap and to characterize both diluted and concentrated dispersions. In the first part, we review the physical concepts of multiple light scattering by dispersions. In relation to the optical analyser Turbiscan, we present physical and statistical models for the radiative transfer in dense suspensions. In the second part, we investigate the influence of particle volume fraction and particle size (polystyrene latex bead suspensions) on the backscattered and transmitted light fluxes measured by Turbiscan. The experimental data are compared with results from the physical models. In the last section, we use the optical analyser Turbiscan Lab to detect and characterize various concentrated dispersions destabilization (coalescence, flocculation, creaming and sedimentation), and then the Turbiscan On Line to monitor and characterize an emulsification process under ultrasonic agitation. Copyright © 2004 Society of Chemical Industry     

Rheological properties and structure of step‐ and chain‐growth gels concentrated above the overlap concentration

Cross‐linked polymeric gels are widely used in applications ranging from biomaterial scaffolds to additives in enhanced oil recovery. Despite this, fundamental understanding of the effect of polymer concentration and reaction mechanism on the scaffold structure is lacking. We measure scaffold properties and structure during gelation using multiple particle tracking microrheology. To determine the effect of concentration, we measure gelation as polymer interactions are increased in the backbone precursor solution: below, at and above the overlap concentration, . To determine structural changes due to the gelation mechanism, we measure gelation between the same polymers undergoing both step‐ and chain‐growth reactions using self‐assembling maleimide:thiol and photo‐initiated acrylate:thiol chemistries, respectively. We determine the critical relaxation exponent, n, a measure of structure. n decreases with increasing concentration, indicating a change from a percolated ( ) to a tightly cross‐linked network ( ). The gelation mechanism does not have a measurable effect on the scaffold structure. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3168–3176, 2018     

Component interactions and the stability of some pigment/polymer dispersions

The sedimentation behavior of rutile and selected organic pigments dispersed in polymer solutions has been interpreted in terms of acid-base interactions at the polymer/pigment interface. The acid-base information was obtained from inverse gas chromatography. Moderate strengths of acid-base interaction were beneficial to the stability of dispersions, whereas both the absence of and excessive interaction resulted in the rapid deposition of solids. The effect is associated with the orientation of adsorbed polymer molecules, which must provide an adequate steric (entropic) barrier for the aggregation and deposition of solids. Implicated is the balance of interaction forces at pigment/polymer and polymer/solvent contacts. Rheological data for the dispersions have been used to obtain a parameter related to the thickness of the adsorbed polymer layer, by way of amplifying on the state of the pigment/polymer interface. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 245–253, 1998     

Effect of relative humidity on the oxidative and physical stability of encapsulated milk fat

Milk fat was used in this work as a model to study the effects of humidity and physical properties on lipid oxidation. Although milk fat is considered a relatively stable fat because of its low content of unsaturated FA, it can oxidize significantly under certain conditions, as observed, for example, in the case, of dairy-based powders. Humidity and physical properties have a profound influence on the oxidative stability of powders, containing fat, and these factors affect the surface and encapsulated fractions of the fat differently. To examine these effects, encapsulated milk fat powders were stored under conditions of controlled relative humidity. Oxidation of the encapsulated fat as assessed by measurements of PV, losses of FA, and hexanal production increased, with increasing relative humidity (RH). At higher RH, moisture penetrates into the hydrophilic wall, interacting with and plasticizing the components, thereby making them less effective as moisture and oxygen barriers. Total oxidation of the powders was strongly influenced by the extent of oxidation in the encapsulated fraction (>98% of total lipids) although the surface fat fraction was oxidized more rapidly. Better protection against oxidation was obtained when fats were encapsulated and stored at 14 and 44% RH than at 52% RH.     

Effect of fuel oil source on the preparation of coal-oil dispersions

BP has devised a preparative route to stable coal-oil dispersions (COD's) which involves the fine grinding of coal in oil. This paper investigates how COD preparation and properties are affected by oil composition. COD's were prepared using a range of fuel oils from different crude sources or refineries and containing straight run or cracked components. Wide variations in sedimentation stability-milling time profiles were measured and attempts have been made to correlate these data with fuel oil analytical parameters. The tendency of the asphaltenes in the oil to flocculate is thought to be an important parameter in determining stability for a given milling time. A preliminary explanation of the observed trends is proposed in this Paper.     

Curing reaction of amino‐terminated aqueous‐based polyurethane dispersions with triglycidyl‐containing compound

Amino‐terminated anionic aqueous‐based polyurethane (PU) dispersion was obtained from NCO‐terminated PU prepolymer, which was neutralized with an excess triethylamine (TEA) and chain extended by ethylenediamine (EDA) during water dispersion process. That PU prepolymer was obtained from a polyaddition reaction of isophorone diisocyanate (IPDI), polypropylene glycol‐2000 (PPG‐2000), and 2,2′‐dimethylol propanoic acid (DMPA). This aqueous‐based PU dispersion was treated with trimethylolpropane triglycidyl ether (TMPTGE) as a latent curing agent and resulted in a self‐cured PU resin on drying. A model ring‐opening curing reaction between oxirane group of TMPTGE with terminal amino group of PU was demonstrated by glycidol with n‐butyl amine. The physical and mechanical properties as well as thermogravimetric analyses of these self‐cured PU resins were evaluated in this article. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyaniline dispersions. 3. Influence of the polymerization conditions

Several series of polyaniline dispersions were prepared by oxidative polymerization of aniline in aqueous medium. Ammonium persulfate was used as an oxidizing agent and poly(vinyl alcohol) as a steric stabilizer of dispersions. The amount of dispersion particles their size and uniformity and the fraction of the steric stabilizer attached to the particles were determined in dependence on the concentration of the individual components and on temperature. The properties of resulting dispersions are controlled mainly by the concentration of the oxidizing agent and by the polyaniline/stabilizer ratio.     

Polyethylene dispersions in bitumen: The effects of the polymer structural parameters

Polymer‐modified bitumens are very important to the transportation sector. Polyethylene is one of the most used polymers in bitumen modification. The effects of the structural parameters of polyethylene on its dispersion in bitumen and the performance of the resulting polymer‐modified bitumens were studied. With the addition of different polyethylenes to bitumen, the performance of bitumen at high temperatures increased as the polymer melt‐flow index (MFI) decreased. At low temperatures, the performance of bitumen decreased as the polyethylene MFI decreased. Furthermore, a decrease in the polyethylene MFI intensified its dispersion instability. At very low MFIs, the dispersions were unstable, even under the very high shear forces applied by a double mixer. Moreover, changes in the polyethylene MFI did not improve the dispersion stability at an elevated temperature (165°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3183–3190, 2003     

部分相容聚合物共混体系相分离的流变学表征方法

针对具有不同动态非对称性的部分相容聚合物共混体系,阐述了用于表征和探测其相分离特征的流变学方法,包括小振幅振荡剪切考察时温叠加原理的有效性和温度扫描,以及稳态剪切温度扫描;并且分析了共混体系的复杂结构对温度依赖性形成差异的深层原因,总结比较了各方法应用时的优缺点及其针对不同强弱动态非对称体系的适用性。     

Factors affecting the decay of batch liquid-liquid dispersions

A model which predicts the shape of the time dependent sedimentation and coalescence profiles during batch decay, allowing for binary coalescence and increasing hold-up in the sedimentation zone, and the effect of the height of the dense-packed zone on the interfacial coalescence rate, is presented. The model is verified using the experimentally observed increase in drop size with time. Analysis of twenty five liquid-liquid systems covering a wide range of physical properties, operating conditions and settler geometry indicates that sigmoidal or exponential sedimentation profiles are obtained depending on whether the initial Reynolds number is less or greater than unity, respectively.     

PUAG-St超浓乳液共聚稳定性的研究

用甲苯二异氰酸酯(TDI)、聚丙二醇(N_(210))、丙烯酸-β-羟乙酯(β-HEA)、聚乙二醇-600(PEG-600)分三步制得含双键的非离子型聚氨酯PUAG,然后与苯乙烯单体,在MS-1、十六醇(CA)、聚乙烯醇(PVA- 1788)作乳化体系,以偶氮二异丁腈(AIBN)为引发剂,在55℃下引发聚合。研究了NCO/OH摩尔比、复合乳化剂质量浓度、引发剂质量浓度、内相比、聚合温度、PUAG的量等因素对聚合稳定性影响。用透射电子显微镜(TEM)观察聚合物乳胶粒子的形态,用红外光谱证明了PUAG的共聚物的生成。     

HDPE/纳米SiO2杂化材料的动态流变行为研究

通过熔融接枝反应将乙烯基三甲氧基硅烷(VTMS)接枝到高密度聚乙烯(HDPE)分子链上,以四乙氧基硅烷(TEOS)为前驱体,加入接枝的HDPE中,通过溶胶-凝胶法(Sol-Gel)制备了HDPE/SiO2杂化材料,使用平板流变仪研究了纳米SiO2对HDPE/纳米SiO2杂化材料的动态流变行为的影响.结果表明,当SiO2...     

Aqueous dispersions of DBSA‐doped polyaniline: One‐pot preparation,characterization, and properties study

Aniline was polymerized in the presence of dodecylbenzene sulfonic acid (DBSA) as a functionalized protonic acid, in an aqueous medium to directly synthesize polyaniline (PANI)‐DBSA particles. DBSA acted as a dopant and a surfactant with stabilizing PANI‐DBSA dispersions by formation of strong hydrogen bonds. The NH⁺…SO interactions between the PANI chains and the DBSA appeared at 1026 cm^?1 in Fourier transform infrared (FTIR) spectrum. Elemental analysis was used to determine the degree of sulfonation (S/N ratio) of PANI chains and resulted that the sulfur‐to‐nitrogen ratio is 0.35. Thermogravimetric analysis (TGA) technique was used to analyze thermal properties of the particles and resulted that the synthesized PANI‐DBSA particles have high thermal stability. The moisture, DBSA and PANI contents of the PANI‐DBSA were estimated from TGA curve, and then the number of aniline repeating units doped with one DBSA molecule was approximately calculated. X‐ray diffraction (XRD) analysis confirmed that a chemical crosslinking reaction occurs between the PANI chains during thermal treatment of PANI‐DBSA. The morphology of PANI‐DBSA powder was investigated by scanning electron microscopy technique and showed that the PANI particles develops from round particles to a smooth surface. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

农药水乳剂物理稳定性的研究进展

简要介绍了乳状液形成与稳定机理,重点综述了相关理论和方法在农药水乳剂物理稳定性中的研究与应用现状,分析了当前农药新剂型加工理论研究不足以及乳化剂环保性能有待提高等具体问题。     

含聚四氟乙烯涂膜的物理性能研究

以聚笨硫醚(PPS)和聚酰亚胺(PI)为复合粘结剂与聚四氟乙烯(PTFE)混合于合适的溶剂中,制成含PTFE的涂料。分别研究了复合粘结剂中PPS和PI的配比以及涂料中PTFE与复合粘结荆的配比对涂膜性能的影响。结果表明,当复合粘结剂中m(PPS):m(PI)=75:25,涂料中m(PIFE):m(复合粘结剂)=65:35时,所得涂膜性能优良:附着力1级,柔韧性1mm,冲击强度大于500 N／cm2。经过100℃,200℃和250℃的加热-淬冷以及十次加热-淬冷循环实验后,涂膜的物理性能不改变。     

超浓乳液聚合体系稳定性的研究

介绍了超浓乳液及其制备方法、讨论了超浓乳液形成的条件,指出了不同单体体系的超浓乳液聚合的最佳稳定性条件。