Polymers adsorption measurements

Polymer adsorption measurements have been carreid out in dilute sclutior.s by traditional method as described elsewhere (ref. 9i 10). Adsorption excess values for polymers were calculated by the difference ( a 0) of the solution concentrations before and after adsorption measurements. 

A recent design of the maximum bubble pressure instrument for measurement of dynamic surface tension allows resolution in the millisecond time frame [119, 120]. This was accomplished by increasing the system volume relative to that of the bubble and by using electric and acoustic sensors to track the bubble formation frequency. Miller and co-workers also assessed the hydrodynamic effects arising at short bubble formation times with experiments on very viscous liquids [121]. They proposed a correction procedure to improve reliability at short times. This technique is applicable to the study of surfactant and polymer adsorption from solution [101, 120]. 

If only electrostatic effects are responsible for polymer adsorption and flocculation, our results can be explained according to the same scheme as that used by Furusawa et Al.(20) to interprete the destabilization of negatively charged latex by a cationic polymer. In a first step, the adsorption of the polymer leads to the neutralization of the particles which are no more stabilized by electrostatic repulsions and there is flocculation (we have not studied this step since in our experiments polymer was always in large excess with respect to Al(0H)3). In a second step the adsorption inverses the charge and (we have indeed measured by... 

Adsorption on Kaolinite. For kaolinite, the polymer adsorption density is strongly dependent on the solid/liquid ratio, S/L, of the clay suspension. As S/L increases, adsorption decreases. This S/L dependence cannot be due totally to autocoagulation of the clay particles since this dependence is observed even in the absence of Ca2+ at pH 7 and at low ionic strength where auto-coagulation as measured by the Bingham yield stress is relatively weak (21). Furthermore, complete dispersion of the particles in solvent by ultra-sonication before addition of... 

In this paper we present results for a series of PEO fractions physically adsorbed on per-deutero polystyrene latex (PSL) in the plateau region of the adsorption isotherm. Hydro-dynamic and adsorption measurements have also been made on this system. Using a porous layer theory developed recently by Cohen Stuart (10) we have calculated the hydrodynamic thickness of these adsorbed polymers directly from the experimental density profiles. The results are then compared with model calculations based on density profiles obtained from the Scheutjens and Fleer (SF) layer model of polymer adsorption (11). 

For adsorption measurements a known mass (usually 0.500g) of silica 186 was contacted with 20 cm of polymer solution and the system gently agitated at 25° for 20h., after which the supernatant was separated by centrifugation and the solute concentration determined gravimetrically. 

Flocculation is indeed dependent on polymer adsorption, and there are hypotheses correlating the two phenomena, but often these have been put forth without detailed measurement of the two phenomena simultaneously (10-13). In this paper, flocculation is investigated as a function of polymer and solution properties and hydrodynamic conditions by measuring different properties of the system, including adsorption, using well characterized kaolinite and polymer samples prepared specifically for this purpose. Also, the role of concentration and charge density of polyacrylamide and polyacrylamide-polyacrylic acid co-polymers in determining kaolinite flocculation is examined under controlled hydrodynamic conditions. 

Percent solid settled In tests where adsorption and flocculation were determined simultaneously, the 200 ml sample was allowed to settle for 30 seconds and then 100 ml of the supernatant was removed using a suction device and after centrifugation analyzed for residual polymer concentration. The minimum level of detection was at 0.5 to 1 ppm and the reproducibility of the adsorption measurements was 2-3%. The settled 100 ml portion was analyzed for solid content. Flocculation due to polymer addition is measured by noting % solid settled as a function of polymer concentration. 

Flocculation rate limitation. The adsorption step was rate limiting for the overall flocculation process in this system. Polymer adsorption rate measurements for dispersed systems reported in the literature (2,26) do not lend themselves to direct comparisons with the present work due to lack of information on shear rates, flocculation rates, and particle and polymer sizes. Gregory (12) proposed that the adsorption and coagulation halftimes, tA and t, respectively, should be good indications of whether or not the adsorption step is expected to be rate limiting. The halftimes, tA and t, are defined as the times required to halve the initial concentrations of polymer and particles, respectively. Adsorption should not limit the flocculation rate if... 

This paper contributes to the literature by quantifying anionic polymer adsorption onto the clay minerals kaolinite, feldspar, mica and quartz by X-ray photoelectron spectroscopy (XPS). XPS measures the sorbed amount directly rather than by a subtraction technique. This enables an insight into how effective selective flocculation is for obtaining kaolinite from a mineral mixture. Atomic force microscopy (AFM) is also used to image polymer adsorption onto mineral surfaces and the effectiveness of this technique applied to mineral surfaces is discussed here. 

The popular weak solvents, which promote polymer adsorption are cyclohexane, dichloro methane, dichloroethane and toluene. Unfortunately, any standardization of the eluent purity/content of admixtures does not exist. This might be one of reasons why it is sometimes difficult to maintain long-term repeatability and interlaboratory reproducibility of measurements in polymer HPLC. 

Concerning the experimental side of polymer adsorption studies the quantity A was only measurable at the early stage of the study, but in 19SS the thickness of the adsorbed layer became accessible to measurement by a hydrodynamic method and in 1961 the quantity p was first determined by infrared spectroscopy. Ellipsometry came up in 1963, which enabled both the adsorbance and the thickness of the adsorbed layer to be measured simultaneously. 

No quantitative comparison between theory and experiment on polymer adsorption was attempted until the end of the 1970 s. There were two reasons for this delay. First, no acceptable theory had been established. Second, some of the parameters used in most of the published theories could not be directly correlated to experimentally measurable quantities. 

Polymer adsorption has been reviewed by many authors28-37. An earlier volume of this journal presented an article which dealt with polymer adsorption studies made before 196429. This paper gives a review of subsequent advances in this field of study. In Chap. B, the principal theories are described, confining ourselves to those which are amenable to experimental teste. Chapter C gives a brief survey of typical measuring techniques. In Chap. D, important experimental data on the thickness of the adsorbed polymer layer and the fraction of adsorbed segments are summarized and discussed, along with their comparison with relevant theories. 

Polymer Adsorption. A review of the theory and measurement of polymer adsorption points out succinctly the distinquishing features of the behavior of macromolecules at solid - liquid interfaces (118). Polymer adsoiption and desorption kinetics are more complex than those of small molecules, mainly because of the lower diffusion rates of polymer chains in solution and the "rearrangement" of adsorbed chains on a solid surface, characterized by slowly formed, multi-point attachments. The latter point is one which is of special interest in protein adsoiption from aqueous solutions. In the case of proteins, initial adsoiption kinetics may be quite rapid. However, the slow rearrangement step may be much more important in terms of the function of the adsorbed layer in natural processes, such as thrombogenesis or biocorrosion / biofouling caused by cell adhesion. 

Up to date, besides the SFA, several non-interferometric techniques have been developed for direct measurements of surface forces between solid surfaces. The most popular and widespread is atomic force microscopy, AFM [14]. This technique has been refined for surface forces measurements by introducing the colloidal probe technique [15,16], The AFM colloidal probe method is, compared to the SFA, rapid and allows for considerable flexibility with respect to the used substrates, taken into account that there is no requirement for the surfaces to be neither transparent, nor atomically smooth over macroscopic areas. However, it suffers an inherent drawback as compared to the SFA It is not possible to determine the absolute distance between the surfaces, which is a serious limitation, especially in studies of soft interfaces, such as, e.g., polymer adsorption layers. Another interesting surface forces technique that deserves attention is measurement and analysis of surface and interaction forces (MASIF), developed by Parker [17]. This technique allows measurement of interaction between two macroscopic surfaces and uses a bimorph as a force sensor. In analogy to the AFM, this technique allows for rapid measurements and expands flexibility with respect to substrate choice however, it fails if the absolute distance resolution is required. 

Labelled polystyrene-14C (PS-14C) was the adsorbate. Two batches were prepared by an identical procedure with only one of them containing radioactive 14C. The labelled polymer was used for the adsorption measurements, whereas the unlabelled polymer was used for the determination of the solution properties. The polystyrene was prepared by emulsion polymerization of redistilled styrene. In order to remove unreacted monomer the polystyrene was freeze-dried from benzene solution. 

Brown RH. 1988b. Determination of benzene, toluene, and xylene in industrial air by porous polymer adsorption tube, thermal desorption and gas chromatography. In Fishbein L, O Neill JK, eds. Environmental carcinogens method of analysis and exposure measurement Vol. 10—benzene and alkylated benzene. New York, NY Oxford University Press, 235-242. 

The usual way of representing polymer adsorption onto clay surfaces is to plot an isotherm showing the amount of polymer adsorbed in grams per gram of clay as a function of the equilibrium concentration of polymer in units of g cm 3. We have to be careful in comparing our results with standard isotherms because we are measuring the total amount of PEO inside the clay. This absorbed mass is not necessarily adsorbed onto the clay surfaces, but may be located in the interlayer solution. To reflect this difference, we have used the unusual nomenclature absorption isotherm rather than the usual adsorption isotherm in the presentation of the data. 

Lassen and Malmsten have performed ellipsometrically determined in situ protein adsorption measurements on the above plasma polymer surfaces with human serum albumin (HSA). human immunoglobulin (IgG), and human fib-... 

Several papers compare the properties of sulfobetaine (meth)acrylic polymers. NMR spectra and solution properties of 23a and 23b [59,60] are correlated with data from the corresponding polycarbobetaines [26]. The photophysical and solution properties of pyrene-labeled 23c were studied in terms of fluorescence emission. Addition of surfactants induces the formation of mixed micelles in aqueous solution [61]. Excluded volume effects of the unlabeled polymer were measured by light scattering [62], its adsorption on silica was studied by adsorbance measurement and ellipsometry [62,63], and the electrostimulated shift of the precipitation temperature was followed at various electric held intensities [64]. Polysulfobetaines may accelerate interionic reactions, e.g., oxidation of ferrocyanide by persulfate [65]. The thermal and dielectric properties of polysulfobetaines 23d were investigated. The flexible lateral chain of the polymers decreased Tg, for which a linear relationship with the number of C atoms was shown [66,67]. 

The shapes of the d (r) curves in flg. 5.24 have a number of consequences that are important in the interpretation of experiments. If, for a given polymer, is measured as a function of the adsorbed amount F, there should (in dilute solutions) be no effect of the molar mass Af. However, in the steep part of the d (r) curve, which is In the (pseudo)plateau region of the adsorption isotherm. F... 

The adsorbed amount is one of the basic parameters in polymer adsorption. Yet its measurement Is not without pitfalls and examples of good experiments on well-defined systems over a wide range of parameters are scarce. As mentioned above, the adsorbed amount is meiinly determined the loops and the trains. 

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