Viscosity characteristics of aqueous solutions of block copolymers of propylene and ethylene oxides

Brookfield viscosity measurements were made on aqueous solutions of surface-active agents composed of block copolymers of propylene and ethylene oxides in which the molecular weights of the polymers varied from 1100 to over 15,000. The hydrophobia bases were polyoxypropylene glycols varying in molecular weight from 940 to 4000. To these were added varying amounts of ethylene oxide so that the polyoxyethylene hydrophil comprised from 15 to 80% of the surfactant total weight. This work has materially expanded previous viscosity studies of aqueous solutions of nonionic surfactants by using a unique type of hydrophobe, two ethylene oxide chains, and far higher molecular weights of hydrophobe and of hydrophil, up to 280 moles of ethylene oxide. The surface-active agents with hydrophobe base molecular weights from 940 to 1100, and in which the polyoxyethylene sections comprised from 15 to 80% of the total weight, did not form gels in aqueous solution. Some surfactants with a hydrophobe base molecular weight of 1750 to 2750, to which varying amounts of polyoxyethylene were added, formed gels in water at a surfactant concentration range of 40% to 80%. With a hydrophobe molecular weight of 3250, gels formed at from 30% to 90% surfactant concentration, while with one nonionic derived from a 4000 molecular weight hydrophobe, a gel formed at only 20% polyol concentration. Two viscosity maxima were found in some cases, as reported occasionally for other systems. An increase in temperature from 0C to 50C generally reduced the viscosity of systems based on hydrophobes of 1175 and lower molecular weights, and increased it in systems based on hydrophobes of 1750 and higher molecular weights. The behavior of these surfactants in forminggels is explained on the basis of hydrogen bonding, micellar aggregation and water entrapment. The moles of water per ethylene oxide group in the adduct varied with the hydrophobe base weight and with the polyoxyethylene hydrophil, and within systems showing maximum viscosities, ranged from 0.3 to 17.1, at 25C, which is much higher than observed in other nonionics.     

Factors effecting a loss of flocculation activity of polyacrylamide solutions: Shear degradation,cation complexation,and solution aging

Polyacrylamide and poly(acrylamide-co-acrylic acid) flocculant solutions were subjected to shear degradation in a rotating cone instrument. At constant shear rate, shear degradation was minimized (highest limiting intrinsic viscosity) by the use of a lower solution concentration and high ionic strength of the polymer solution. Resistance to shear degradation also increased with increasing anionic character of the polyacrylamide. Sheared polymers showed reduced performance as flocculants of coal preparation plant tailings, their major commerical application in the U.K. Partially anionic polyacrylamide solutions were completely inactivated in the presence of certain multivalent cations. Aluminium, iron_III, lead, copper, and zinc ions formed complexes with the carboxyl groups on the polymer, resulting in zero flocculation activity. Nonionic polyacrylamides were unaffected. Viscosity–aging of polyacrylamide solutions was observed over a period of several months, but was insufficient to affect the flocculation activity. In the presence of 3% ethanol or methanol, no aging was observed in solutions stored for over a year.     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

The effect of shear rate on the molecular weight determination of acrylamide polymers from intrinsic viscosity measurements

The rheological response of dilute solutions of high molecular weight polyacrylamides at low shear rates has been measured using a capillary viscometer that provided for a fivefold variation in shear rate at each concentration. The non-Newtonian effects were found to be significant for polyacrylamides with number-average molecular weights exceeding 10⁶. The molecular weight average–intrinsic viscosity relationship most widely used in the literature, [η] = 6.80 × 10^?4M , was found to be valid when [η] was measured at high shear rates where the polymer solutions approached Newtonian behavior. A new relationship was developed relating M _n to the intrinsic viscosity extrapolated to zero shear rate.     

Compatibility analysis of pectin at different esterification degree from intrinsic viscosity data of diluted ternary solutions

This paper aims to set-up a compatibility criterion for couple of pectins at different degree of methoxylation (DM) based on specific viscosity data, slightly modifying a criterion already proposed in the field of synthetic polymers. Four different commercial pectins were preliminarily characterised by using dilute solution viscosity measurements and molecular weight was calculated from intrinsic viscosity data. Four ternary dilute solutions of pectin at different DM, were also investigated and two compatibility criteria, based on viscosity data, were applied. Data revealed that positive molecular interactions take place when pectins in solution have a different DM (i.e. HM/LM mixtures), whilst an incompatible behaviour was found for similar pectin in solution (i.e. both HM or LM). In addition, in the case of incompatible pairs of pectin, also the apparent average molecular weight of mixed pectin, obtained by measurements carried out on ternary solutions, showed an increase with respect to the additive mixing rule, owing to repulsive forces. On the contrary, owing to attractive forces in case of compatible pectin pairs, the apparent molecular weight is lower than the calculated average.     

不同絮凝剂对高泥氧化铜浸出液沉降的影响

为解决云南某氧化铜现场生产中酸浸矿浆含泥量高、沉降速度慢、固液分离困难的问题,对其浸出矿浆进行絮凝沉降实验研究. 实验用浸出矿浆浓度为28.73%,考察了絮凝剂种类、用量、浓度对矿浆沉降的影响. 结果表明,明矾、十二烷基丙磺酸钠、聚丙烯酰胺、明胶、改性阴离子型聚丙烯酰胺、改性阳离子型聚丙烯酰胺均不能有效改善沉降速度,而改性非离子型聚丙烯酰胺(GH-6C)可使矿浆沉降速度大大加快. 这是由于GH-6C分子链上的官能团与浸出液中的胶体粒子发生吸附架桥作用,使颗粒逐渐变大而絮凝沉降. GH-6C分子量较大,在水相中流体力学尺寸或体积也较大,絮凝网捕能力也大,可有效降低絮凝剂的使用浓度、提高絮凝效率. GH-6C浓度为0.1%、用量为0.067 g/L时,沉降指标较好.     

Interaction mechanism of flocculants with coal waste slurry

Coal tailings are the inevitable by-product of coal mining and preparation plants, and often are problematic in terms of dewatering and solid-liquid separation. The interaction of multi-component fine coal tailings with various coagulants and flocculants are important in dewatering processes. Tunçbilek coal preparation plant wastes are composed of 81% inorganic solids with negative surface charges dominating at all pHs. The highest settling rate and turbidity values without flocculant are obtained at natural pH of 8.3 due to the presence of inorganic ions in the suspension particularly Mg²⁺and Ca²⁺that act as natural coagulants. Additon of medium and low charge density anionic flocculants with high molecular weight at natural pH produced higher settling rates at lower dosages than nonionic and cationic flocculants. It shown that the charge density of anionic flocculants has a significant effect on both settling rate and supernatant turbidity, also the settling rate increases with increasing the degree of anionicity. Anionic flocculants having high molecular weight and high anione charge density produced flocs at sufficient size necessary for settling conditions, yet anionic flocculants having low charge density were more effective in the clarification of suspensions containing clay minerals of high stability. The multivalent ions act as a bridge between negatively charged coal, quartz and clay minerals with anionic groups (-CH₂-(CH-CO)-COO groups) of the polymer. Non-ionic flocculants required higher dosages than other flocculants to achieve equivalent settling rates; though excellent turbidity values were obtained in most common pH values. Cationic flocculants of higher charge densities (%70) achieved good settling rates and low supernatant turbidities (9.9 NTU) at natural pH for a dosage of 119.7 g/t-solids flocculant. An interaction mechanism of each polymer type with different components of the tailings is proposed.     

An empirical model relating the molecular weight distribution of high-density polyethylene to the shear dependence of the steady shear melt viscosity

An empirical model has been developed to relate molecular weight distribution to the shear dependence of the steady shear viscosity in high-density polyethylene melts. It uses a molecular weight, M_c, which partitions molecular weights into two classes; those below M_c contribute to the viscosity as they do at zero shear, and those above M_c contribute to the viscosity as though they were of molecular weight M_c at zero shear. Each individual molecular weight species contributes on the basis of its weight fraction. M_c is proposed to be a unique function of the shear rate. Using this method of treating the molecular weight distribution, and the zero shear relation for relating η0 to molecular weight, the calculated steady shear viscosities at various shear rates for polyethylene samples of widely varying polydispersities agree well with experimental results. The model makes no judgment on the existence or importance of entanglements in non-Newtonian behavior since it has no specific parameters involving an entanglement concept. Use of the model suggests that for the samples studied, only the upper portion of the molecular weight distribution contributes toward the experimentally observed decrease of steady shear viscosity with shear rate for shear rates of up to 10,000 sec^?1. The lower molecular weight species are assumed to behave in a Newtonian manner.     

Hydroxypropylmethylcellulose–anionic surfactant interactions in aqueous systems

The increase in the viscosity of an aqueous solution or gel of hydroxypropylmethylcellulose (HPMC) in the presence of an anionic surfactant is attributed to a two-step process: (a) the surfactant undergoes ion–dipole interaction with the ethereal oxygen in HPMC, in the absence or presence of water, and (b) hydrocarbon moieties in the now pendant surfactant molecules undergo hydrophobic bonding, in the presence of water, resulting in an apparent increase in the molecular weight of the HPMC. DSC of dry blends and dried gels or films confirmed HPMC–sodium lauryl sulfate interaction. Work-to-break measurements on films cast from aqueous solutions of HPMC, in the absence or presence of anionic surfactants, indicated an apparent increase in the molecular weight of HPMC in the presence of surfactants.     

Shear flow behaviors of poly(p‐phenylene benzobisoxazole) spinning dope

In this study, the shear flow properties of Poly(p‐phenylene benzobisoxazole) (PBO)/poly(phosphoric acid) (PPA) spinning dope were studied by means of capillary rheometer. The effect of shear stress, temperature, PBO concentration, and PBO molecular weight on the apparent viscosity of PBO/PPA dope was discussed. The results showed that the apparent viscosity of the dope decreased with the increase of the shear stress and the temperature. The flow behavior index increased with the increase of temperature, which indicated that the non‐Newtonian behavior of the dope became weaker at high temperature. Moreover, it was also found that at high shear stress, the apparent viscosity of the dope was insensitive to the temperature, PBO molecular weight, and PBO concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

The degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate), a member of the Nodax family of polymers, were investigated using transient constant shear rate and dynamic time sweep rheological tests. The rate of chain scission at several times and temperatures was correlated with viscosity data and verified using molecular weight determination of the degraded samples. The experimental results show that the molecular weight and the viscosity of Nodax decrease with time over the range of temperatures that were studied (155–175°C). The degradation kinetics, which exhibited first‐order behavior, were determined as a function of the flow history and thermal history. An apparent activation energy of 189 ± 5 kJ/mol for thermal degradation was found by modeling variations in the rate with temperature using an Arrhenius law model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 66–74, 2005     

Viscosity and molecular weight distribution of ultrahigh molecular weight polyethylene using a high temperature low shear rate rotational viscometer

To obtain accurate measurements of the limiting viscosity number (LVN) or the intrinsic viscosity [η] of solutions of ultrahigh molecular weight polyethylene (UHMWPE), a low shear floating-rotor viscometer of the Zimm-Crothers type was constructed to measure viscosities at elevated temperatures (135°C) and near zero shear rate. The zero shear rate measurements for UHMWPE whole polymer and UHMWPE fractionated by hydrodynamic crystallization were compared with viscosity measurements at moderate and high shear rates (up to 2000 _s^?1) carried out in a capillary viscometer. The limiting viscosity number of UHMWPE decreases, as expected, with shear rate. The higher shear rate data could not be extrapolated to yield the correct zero-shear rate viscosities. Fractionation of UHMWPE gave 10 fractions ranging in LVN from 9 to 50 dL/g. A tentative integral molecular weight distribution for the whole polymer was calculated on the basis of the Mark-Houwink equation, but because it had been previously established only for lower molecular weight polyethylenes, it may not be accurate. A correlation was found between the LVNs for the fractions in the two types of viscometers.     

Rheological Behaviors of Polyacrylonitrile/1-Butyl-3-Methylimidazolium Chloride Concentrated Solutions

One of the room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was chosen to prepare the concentrated solutions of Polyacrylonitrile (PAN). The rheological behaviors of the solutions were measured with rotational rheometry under different conditions, including temperatures, concentration, and molecular weight of PAN. The solutions exhibited shear-thinning behaviors, similar to that of PAN/DMF solutions. The viscosities decreased with the increasing of shear rates. However, the viscosity decreased sharply at high shear rates when the concentration was up to 16wt%. The dependence of the viscosity on temperature was analyzed through the determination of the apparent activation energy. Unusually, the viscosity of solutions of higher concentration is lower than that of lower concentration. Similarly, the viscosity of low molecular weight PAN was higher than high molecular weight PAN at high shear rates. The dynamic rheological measurement indicates the loss modulus is much higher than storage modulus. The trend of complex viscosity is similar with the result of static rheological measurement. The interaction between PAN and ionic liquid [BMIM]Cl was discussed.     

N -琥珀酰壳聚糖的吸湿保湿性评价

以不同黏均分子质量(M0)和不同脱乙酰度(DD)的壳聚糖制备出一系列N-琥珀酰壳聚糖(NSC),研究了NSC的吸湿保湿性、稳定性和与表面活性剂的配伍性,并以透明质酸为对照,测定了NSC在化妆品配方中的保湿性.结果表明在相对湿度81%和32%时,NSC的吸湿保湿性随M0(1.04×106～1.00×105)的降低和DD(44%～100%)的增加而增强;在硅胶中,其吸湿保湿性能随M0的降低和DD的增加而减弱;在不同pH溶液中的特性黏度变化率小于6.5%,能与阴离子和非离子表面活性剂配伍,在化妆品配方中,其保湿性能好于透明质酸.     

聚烯烃弹性体的结构与熔体黏度关系的研究

采用凝胶渗透色谱仪和核磁共振仪表征了一系列聚烯烃弹性体（POE）样品的结构,并用毛细管流变仪考察了其挤出稳定性、剪切依赖性和黏温依赖性,分析了熔体黏度与聚合物结构的关系。结果表明,随着剪切速率的提高,高相对分子质量的POE熔体易出现不稳定流动,挤出物表面发生畸变;相对分子质量越大、温度越低、共聚单体含越高,发生不稳定流动的临界剪切速率c越低;POE的剪切黏度很大程度上受相对分子质量的影响,与共聚单体的含量关系不大;不同相对分子质量及组成的POE熔体的黏流活化能相近,约为2.8×10^4 J/mol。基于Carreau、Cross和Arrhenius等方程,分别建立了关联熔体零切黏度与聚合物重均相对分子质量和温度关系的半经验式、关联熔体表观黏度与零切黏度和剪切速率关系的半经验式;两式可用于预测POE熔体的黏度,其适用范围为温度为130~190 ℃,剪切速率为10~2 000 s-1,重均相对分子质量（Mw）为4.2×10^4~1.24×10^5 g/mol。     

Influences of polymer matrix melt viscosity and molecular weight on MWCNT agglomerate dispersion

In order to study the influence of melt viscosity and molecular weight on nanotube dispersion and electrical volume resistivity, three different polycarbonates (PCs) varying in molecular weight were melt compounded with 1 wt% multiwalled carbon nanotubes (MWCNTs, Baytubes^® 150 HP) using a small-scale compounder. The experiments were performed at constant melt temperature but at varying mixing speeds, thereby applying different magnitudes of shear stress. Light transmission microscopy was used to access the state of agglomerate dispersion, and electrical resistivities of the composites were measured on pressed plates. The results indicate that with increasing matrix viscosity the agglomerate dispersion gets better when using constant mixing conditions but worse considering comparable shear stress values. To study the effect of molecular weight, in a second set of experiments melt temperatures were adjusted so that all PCs had similar viscosity and mixing was performed at constant mixing speed. As investigated on two viscosity levels, the composites based on the low molecular weight matrix showed smaller sized un-dispersed primary agglomerates as compared to composites with higher molecular weight matrices, highlighting the role of matrix infiltration into primary nanotube agglomerates as the first step of dispersion. The resistivity values of composites prepared using low viscosity matrices were lower than those of composites from high viscosity matrix.     

Microelectrophoresis and electron-microscope studies with polymeric flocculants

Mechanisms for the stabilization and flocculation of colloids have been indicated by microelectrophoresis measurements and electron-microscope observations with model colloids and polymeric flocculants. Zeta-potential (ζ) changes and details of floc structure were observed with silica and polystyrene latex colloids. Bridging fibers of polyamine-type flocculants appear to extend radially from the colloidal particles and vary in thickness from 20 to 300 Å. Charge neutralization and bridging may function simultaneously. Incremental additions of cationic flocculants produce gradual reduction in the negative ζ, and maximum flocculation is observed near zero ζ. Subsequent addition of flocculant reverses the potential and finally effects redispersion of the colloid. If incipient charge reversal is produced with a relatively low molecular weight cationic polymer, large flocs may then be formed on the addition of a high molecular weight anionic flocculant. Direct addition of an anionic polymeric flocculant to a negatively charged colloid may raise the negative ζ to a surprisingly high value and may thus effect stabilization instead of flocculation of the colloid.     

Light scattering studies on the ripening of viscose solution

Investigations were made on cellulose xanthate molecular weights by light scattering during the ripening of the solutions of (a) viscose-containing colored thio salts and (b) pure cellulose xanthate separated from viscose. Though an apparent reduction in molecular weight was recorded with time of ripening for the viscose solution, no such fall was observed with pure cellulose xanthate. The apparent fall of molecular weight in the case of viscose has been shown to be due to the increasing absorption of the incident beam and to the change in the value of dn/dc with progressive color formation. Reproducible results can be obtained for cellulose xanthate solutions freed from color. Intrinsic viscosity of the viscoses and the degree of polymerization (D.P.) of the regenerated cellulose from viscoses during ripening were also measured and found to be constant. The results indicate that no degradation of alkali cellulose molecule takes place during the ripening process, irrespective of the state of degradation of alkali cellulose from which the viscose is made.     

Thermal response of low molecular weight poly-(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) polymers in aqueous solution

Temperature-induced phase transition of three low-molecular-weight samples (M _w  < 1.2 × 10⁴) of poly(N-isopropylacrylamide) was studied with the aid of turbidimetry, dynamic light scattering, and rheology. We have demonstrated that the lower critical solution temperature depends on the length of the chain and the concentration of the polymer in the low molecular weight range. The turbidity results show a transition peak in the turbidity curve at intermediate temperatures. This peak, as well as the cloud point, is shifted toward lower temperatures when the molecular weight and the concentration of the polymer increase. The DLS measurements disclose a fast and a slow relaxation mode, which in both cases are found to be diffusive. The fast mode is linked to the diffusion of small species in the solution, and the slow mode is associated with the formation of large aggregates. The formation of these aggregates is less pronounced in solutions of polymers with low molecular weight and the incipient aggregation is shifted to higher temperatures. The shear viscosity measurements show the formation of weak aggregates, which are easily broken in solutions of short polymers. This effect is less pronounced when the molecular weight of the sample is increased. At certain shear rates, temperature-induced transition peaks of the viscosity are observed.     

Apparent elongational viscosity of dilute polymer solutions

Apparent elongational viscosity studies were made on dilute solutions of high molecular weight polymers using a fiber spinning apparatus designed for low shear viscosity liquids with substantial elongational effects. The experimental method involved the flow of solutions of polyacrylamide and poly(ethylene oxide) from a tube into an evacuated vessel. Experimental results showed that the apparent elongational viscosity obtained from the jet shape increased linearly with the stretch rate.