Viscoelastic relaxation in poly-1-butenes of low molecular weight

1967 ◽  
Vol 300 (1462) ◽  
pp. 356-372 ◽  
Keyword(s):  
Molecular Weight ◽  
Steady Flow ◽  
Simple Liquid ◽  
Viscoelastic Relaxation ◽  
Low Frequencies ◽  
Chain Polymer ◽  
Molecular Weights ◽  
Wide Range ◽  
Volume Equation ◽  
Rouse Theory

Measurements have been made of the viscoelastic properties of a range of poly-1-butene liquids of different molecular weights under cyclic shearing stress. The five liquids studied range in steady-flow viscosity at 20 °C from 5.5 to 9330 P corresponding to number average molecular weights from 448 to 2700. Measurements over the temperature range – 60 to +90 °C were made at frequencies of alternating shear of 64 kc/s, 6, 18 and 30 Mc/s. The liquid of lowest molecular weight (448) was nominally pure, having eight repeat units, while the remaining four each had a distribution of molecular weights. In all cases, the dependence of steady flow viscosity upon temperature follows the equation In η = A + B /(T - T 0 ), (1) which is derived from the free-volume equation with a linear dependence of density upon temperature. Recent measurements on a wide range of pure liquids which have viscosities described by equation (1) have been interpreted in terms of a simple phenomenological model for viscoelastic relaxation which allows the behaviour to be predicted (Barlow, Erginsav & Lamb 1967 b ). Analysis of the present results on the liquid of lowest molecular weight shows that the measured behaviour can also be described by this model. For the four liquids of higher molecular weight a second relaxation process is found at lower frequencies. This is attributed to the increased chain length of the molecules giving rise to 'quasi-Rouse’ modes of motion. At low frequencies the results for these four liquids show a behaviour intermediate between that of a simple liquid and that exhibited by a long chain polymer which conforms to the extended form of the Rouse theory.

Viscoelastic Relaxation of Rubber Vulcanizates Between the Glass Transition and Equilibrium

1966 ◽  
Vol 39 (4) ◽  
pp. 870-880 ◽  
Author(s):  
R. Chasset ◽  
P. Thirion
Keyword(s):  
Molecular Weight ◽  
Dynamic Properties ◽  
Average Length ◽  
Linear Part ◽  
Polymer Networks ◽  
Relaxation Times ◽  
Distribution Functions ◽  
Viscoelastic Relaxation ◽  
Theoretical Understanding ◽  
Rouse Theory

Abstract In agreement with the results of dynamic experiments of Stratton and Ferry, this study of relaxation of rubber vulcanizates entirely confirms the existence of peculiar, slow, viscoelastic processes in high polymer networks. Characteristic differences with the rheological behavior of unvulcanized polymers are best reflected by the shape of the end of the distribution functions of relaxation times. The box distribution found for free chains is replaced, for crosslinked polymers, by a long incline extending during several decades of time. The slope of this linear part of the spectrum is only slightly dependent on nature of the polymer and type of vulcanizate. On the other hand, the position of the incline along the time scale is very sensitive to the mean molecular weight Mc of the vulcanizates, by far the most important factor controlling the phenomenon. The downward deviations observed at the end of the incline also occur later for larger values of Mc. A useful step towards theoretical understanding of this behavior should be a quantitative knowledge of the effect of molecular weight in a broader range of Mc than studied here. If the chain entanglements are of primary importance, as considered probable by Ferry it seems that some singularity should occur for a critical molecular weight fitting the corresponding value for the viscosity of free chains. The role of crosslink mobility might be tested by comparing the relaxation of ordinary random vulcanizates with that of eventually more regular polybutadiene networks prepared by end group crosslinking of carboxy-terminated and mono-disperse chains. In fact, the displacement of a crosslink away from its affine position requires, apart from the Brownian fluctuations, an unbalance between the forces exerted by the four radiating chains. This implies that the lengths of the strands present large differences and that the shortest chains are approaching their limit of extensibility. As the latter condition can hardly be fullfilled at small deformations, it seems doubtful that this mechanism may be predominant either for dynamic properties or the relaxation experiments reported here. Another cause sometimes invoked is the presence of free chains attached to the networks and we are presently studying their effect on viscoelastic relaxation. At this stage, it is already apparent that they do not have a large effect, as might be expected on theoretical grounds. In our opinion, special attention should be paid to the reason why the experimentally found relaxation times are so large, in spite of the relatively short average length of the network strands. If the usual notion of entanglements developed for free chains, as an extension of the Rouse theory, should fail in this respect, it would be necessary to reconsider the non-equilibrium statistics of single chains with fixed ends, taking into account the proper inter- and intramolecular forces hindering their motion. This more direct approach to the problem, already outlined by Kirkwood, ought to express mathematically the fact that the presence of crosslinks tends to prevent longitudinal slippage of large parts of the chains. The slow changes of configuration should occur therefore rather through lateral motions to which the neighboring medium opposes a much greater resistance.

Equation for osmotic pressure of serum protein (fractions)

2004 ◽  
Vol 96 (2) ◽  
pp. 762-764 ◽  
Author(s):  
Johan Ahlqvist
Keyword(s):  
Molecular Weight ◽  
Regression Analysis ◽  
Osmotic Pressure ◽  
Serum Protein ◽  
Protein Fractions ◽  
Fibrinogen Concentration ◽  
Nonlinear Regression Analysis ◽  
Molecular Weights ◽  
Wide Range ◽  
Better Than

The colloid or protein osmotic pressure (Π) is a function of protein molarity (linear) and of Donnan and other effects. Albumin is the major osmotic protein, but also globulins influence Π. Equations based on concentrations of albumin and nonalbumin (globulin concentration + fibrinogen concentration) protein approximate Π better than albumin alone. Globulins have a wide range of molecular weights, and a 1956 diagram indicated that Π of globulin fractions decreased in the order α1-, α2-, β-, and γ-globulin. The molecular weight of the serum protein fractions had been extrapolated, so van't Hoff's law and nonlinear regression analysis of the curves permitted expression of the diagram as an equation: [Formula: see text], where Πs,Ott,2°C,cmH2O is Π of serum at 2°C (in cmH2O) computed from the 1956 diagram, Ctot is the concentration (g/l) of total protein in serum, and xalb, xα1, xα2, xβ, and xγ are the fractions of albumin, α1-, α2-, β-, and γ-globulin, respectively. At one and the same concentration of fractions, Π“Ott” decreases in the order α1-globulin, albumin, α2-globulin, β-globulin, and γ-globulin.

Dynamic Mechanical Properties of Cross-Linked Rubbers. II. Effects of Crosslink Spacing and Initial Molecular Weight in Polybutadiene

1966 ◽  
Vol 39 (4) ◽  
pp. 905-914
Author(s):  
Etsuji Maekawa ◽  
Ralph G. Mancke ◽  
John D. Ferry
Keyword(s):  
Molecular Weight ◽  
Crosslink Density ◽  
Low Frequency ◽  
Dynamic Mechanical Properties ◽  
Cross Linking ◽  
Loss Mechanism ◽  
Low Frequencies ◽  
Molecular Weights ◽  
Monomeric Friction Coefficient ◽  
Lower Frequencies

Abstract The complex shear compliances of eight samples of polybutadiene crosslinked by cumyl peroxide and four samples crosslinked by sulfur have been measured over a frequency range from 0.2 to 2 cps at temperatures from − 6 to 45° C by a torsion pendulum. On four of the samples, measurements were extended by the Fitzgerald transducer from 45 to 600 cps at temperatures from − 71 to 55°. The vulcanizates had been prepared from polymers of two different molecular weights (180,000 and 510,000) with sharp molecular weight distribution; the physical crosslink density ranged from 0.57 to 2.68×10−4 mole/cm3, and the chemical crosslink density calculated following Kraus ranged from 0.22 to 1.49×10−4 mole/cm3. The mechanical data were all reduced to T0=298° K by shift factors calculated from the equation log aT=−3.64(T−T0)/(186.5+T−T0). In the transition zone of frequencies, the viscoelastic functions of the cumyl peroxide vulcanizates were closely similar, except for a shift toward lower frequencies with increasing crosslinking, corresponding to a small but unexpected increase in the monomeric friction coefficient. Cross-linking by sulfur caused a somewhat larger shift toward lower frequencies at a comparable crosslink density. In the rubbery zone, the sample with least cross-linking exhibited a substantial secondary loss mechanism at very low frequencies. The low-frequency losses are evident in all the samples, but their magnitude falls rapidly with increasing crosslink density as previously found for natural rubber. It also falls somewhat with increasing initial molecular weight, indicating a contribution from network strands with loose ends. The possible relation of the low-frequency losses to trapped entanglements is discussed.

The viscoelastic properties of polystyrene solutions

1964 ◽  
Vol 281 (1385) ◽  
pp. 207-222 ◽  
Keyword(s):  
Molecular Weight ◽  
Viscoelastic Properties ◽  
Polymer Molecule ◽  
Viscoelastic Behaviour ◽  
Torsional Mode ◽  
Quartz Crystals ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Polystyrene Sample ◽  
Rouse Theory

Quartz crystals resonant in the fundamental torsional mode at frequencies of 40 and 73 kc/s have been used to measure the viscoelastic properties of solutions of polystyrene in toluene, methylethyl ketone and cyclohexane. A monodisperse polystyrene sample of molecular weight 2.39 x 10 5 was employed. The results have been compared with those of Harrison, Lamb & Matheson (1964) for dilute solutions in toluene of a number of polystyrene samples of different molecular weights. In toluene it is found that 25 % of the contribution of the polymer to the viscosity of the solution is not able to take part in viscoelastic relaxation, and that the dynamic viscosity at high frequencies (the ‘Einstein viscosity’) is greater than the solvent viscosity. Under these conditions the viscoelastic behaviour of all the solutions in toluene of polystyrene samples of different molecular weights agrees with the predictions of the Rouse theory. From the value obtained for the Einstein viscosity of the solutions, it is shown that the radius of the equivalent hydrodynamic sphere is approximately proportional to the square root of the molecular weight of the polymer molecule. If one assumes that the radius of the equivalent hydrodynamic sphere of a given polymer molecule is the same in all solvents, then the viscoelastic behaviour of the solution in methylethyl ketone is intermediate between the predictions of the Zimm and Rouse theories. The solution in cyclohexane seems to show behaviour close to that predicted by the Zimm theory. The possibility of using such measurements to determine molecular weight distributions is discussed.

Vaginal Absorption of Polyvinyl Alcohol in Fischer 344 Rats

1990 ◽  
Vol 9 (2) ◽  
pp. 71-77 ◽  
Author(s):  
J.M. Sanders ◽  
H.B. Matthews
Keyword(s):  
Molecular Weight ◽  
Polyvinyl Alcohol ◽  
Low Molecular Weight ◽  
Fischer 344 Rats ◽  
Gi Tract ◽  
Molecular Weights ◽  
Fischer 344 ◽  
Human Dose ◽  
Wide Range ◽  
Intravaginal Administration

Polyvinyl alcohol (PVA) is a polymer with a wide range of molecular weights and uses. Recently, low molecular weight formulations of PVA have been used as components of contraceptive products designed for intravaginal administration in human females. Previous studies in animals have determined that little or no absorption of PVA occurs from the gastrointestinal (GI) tract. However, there is some concern that PVA of lower molecular weights might be absorbed across membranes of the reproductive tract. Consequently, this work has investigated the absorption of low molecular weight PVA across biological membranes of the reproductive and GI tracts of Fischer 344 rats. Oral administration of ten consecutive daily doses of 14C PVA resulted in little apparent absorption of the dose from the GI tract. In contrast, intravaginal administration of 14C PVA resulted in increasing concentrations of PVA-derived radioactivity in major tissues following one, three or ten daily doses of the estimated human dose of 3 mg/kg. PVA-derived radioactivity was concentrated mainly in the liver, reaching a peak greater than 1750 ng equivalents/g tissue 24 hours following ten daily doses. Over 300 ng equivalents/g tissue were still present in the liver 30 days following the last dose.

Molecular-weight changes in the degradation of long-chain polymers

1954 ◽  
Vol 224 (1156) ◽  
pp. 120-128 ◽  
Keyword(s):  
Molecular Weight ◽  
Main Chain ◽  
High Energy ◽  
Initial Distribution ◽  
Weight Changes ◽  
Chain Polymer ◽  
High Energy Radiation ◽  
Molecular Weights ◽  
Random Fracture ◽  
Long Chain

The changes in molecular weight of a long-chain polymer (initially of arbitrary molecular-weight distribution) are studied when the main chain is subjected to random fracture, such as occurs when certain polymers are exposed to high-energy radiation. For several distributions studied, all trace of the initial distribution curve is lost after an average of some 3 to 8 main-chain fractures per molecule. For lower degrees of degradation the shape of the curve of weight average against degradation can provide information as to the initial weight average, z average, z + 1 average molecular weights. The initial number-average can be obtained by a method of extrapolation.

scholarly journals The Influence of the Different Disposition Characteristics of Snake Toxins on the Pharmacokinetics of Snake Venom

Toxins ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 188 ◽  
Author(s):  
Suchaya Sanhajariya ◽  
Geoffrey K. Isbister ◽  
Stephen B. Duffull
Keyword(s):  
Molecular Weight ◽  
Snake Venom ◽  
Time Course ◽  
Total Concentration ◽  
Weight Fraction ◽  
Pharmacokinetic Parameters ◽  
Time Data ◽  
Molecular Weights ◽  
Concentration Time ◽  
Wide Range

Snake venom is comprised of a combination of different proteins and peptides with a wide range of molecular weights and different disposition processes inherent to each compound. This causes venom to have a complex exposure profile. Our study investigates 1) how each molecular weight fraction (toxin) of venom contributes to the overall time course of the snake venom, and 2) the ability to determine toxin profiles based on the profile of the overall venom only. We undertook an in silico simulation and modelling study. Sixteen variations of venom, comprising of two to nine toxins with different molecular weights were investigated. The pharmacokinetic parameters (i.e., clearance,  C L , and volume of distribution,  V ) of each toxin were generated based on a log-linear relationship with molecular weight. The concentration–time data of each toxin were simulated for 100 virtual patients using MATLAB and the total concentration–time data of each toxin were modelled using NONMEM. We found that the data of sixteen mixtures were best described by either two- or three-compartment models, despite the venom being made up of more than three different toxins. This suggests that it is generally not possible to determine individual toxin profiles based on measurements of total venom concentrations only.

Thermomechanical Characterization of the Molecular Weight of Linear Polymers Exemplified by Natural Rubber

1964 ◽  
Vol 37 (1) ◽  
pp. 99-102
Author(s):  
B. Ya Teitelbaum ◽  
K. F. Gubanov
Keyword(s):  
Molecular Weight ◽  
Experimental Studies ◽  
Thermomechanical Properties ◽  
Linear Polymers ◽  
Molecular Weights ◽  
Calculated Molecular Weight ◽  
Low Degree ◽  
Wide Range ◽  
High Elasticity

Abstract In the previous work of Kargin and Slonimskii and that of Kargin and Sogolov who studied the behavior of polymers over a wide range of temperature, it was shown that the shape of thermomechanical curves depends on magnitude of molecular weight of the polymers. As a result of investigation of theory and actual experimental studies in which polyisobutylene was employed, it was demonstrated that molecular weight could be estimated on the basis of thermomechanical properties. This suggested a relationship between the magnitude of molecular weight M found from the thermomechanical curves and that which was determined from glass temperatures Tg and fluid temperatures Tf. For practical use of this relationship, it is necessary to know the magnitude of the segments and two empirical constants. These values can be found by calculation of molecular weights of three different fractions of the polymer. This can be accomplished experimentally by any independent method. Once these magnitudes are determined, it is necessary to find, by means of the thermomechanical curve, the values Tg and Tf, in order to calculate the molecular weight of any sample of the same polymer. Because of the low degree of accuracy of determination of these values, and because of the peculiar differences, the reliability of the calculated molecular weight cannot be great, especially since the equation utilizes the logarithm of the molecular weight figure and not the molecular weight itself. Apparently the graphic solution is simpler than analytical methods: by means of the data of thermomechanical studies for various fractions of known molecular weights it is possible to graph the dependence of M or log Mon Tf−Tg. From what has been said, it is evident that we may use the demonstrated method only for polymers of high elasticity, and furthermore, only for those fractions in which Tf−Tg is greater than zero.

A variety of morphologies in diblock copolymer/homopolymer blends

1989 ◽  
Vol 47 ◽  
pp. 346-347
Author(s):  
Edwin L. Thomas ◽  
Karen I. Winey
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Diblock Copolymer ◽  
Copolymer Composition ◽  
Molecular Weights ◽  
Copolymer Concentration ◽  
Wide Range ◽  
Homopolymer Blends ◽  
Long Range Ordering ◽  
Double Diamond

A wide range of morphologies and thereby physical properties can be achieved in block copolymer/homopolymer blends by varying the copolymer composition, copolymer concentration and molecular weights. Recently we investigated micelle shape transitions in diblock copolymer with homopolymer blends at low copolymer concentration. In this paper we study the microstructure over a wider concentration range for a polystyrene-polybutadiene (PS/PB) diblock copolymer of molecular weight 20.5 × 103/20.5 × 103 blended with 17.2 × 103 molecular weight homopolystyrene (hPS).Figure 1 shows schematically a possible spectrum of microdomain structures dependent on the copolymer concentration of a lamellar PS/PB and hPS. Below the critical micelle concentration (CMC) the block copolymer is molecularly dispersed in the homopolymer exhibiting a homogeneous phase. As diblock concentration increases the minority (i.e. PB) forms spherical and/or cylindrical micelles randomly dispersed in the hPS. Further increases in diblock concentration induces long range ordering of various microdomains. In addition three biphasic regions are proposed in which two phases coexist: isotropic cylinders with ordered cylinders, ordered cylinders with ordered bicontinuous double diamond (OBDD), and OBDD with swollen lamellae.

scholarly journals UHPLC Q-Exactive MS-Based Serum Metabolomics to Explore the Effect Mechanisms of Immunological Activity of Astragalus Polysaccharides With Different Molecular Weights

2020 ◽  
Vol 11 ◽  
Author(s):  
Ke Li ◽  
Lian-Jie Cui ◽  
Yu-Xin Cao ◽  
Shu-Ying Li ◽  
Li-Xia Shi ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Biological Activities ◽  
Tricarboxylic Acid Cycle ◽  
Mouse Serum ◽  
Immunomodulatory Activity ◽  
Molecular Weights ◽  
Wide Range ◽  
Q Exactive ◽  
Relative Molecular Weight ◽  
Metabolomics Analysis

Astragalus polysaccharides (APS) have a wide range of biological activities. Most researchers discuss total APS as the main research object. However, because the relative molecular weight of APS has a wide distribution, in-depth studies on the mechanisms of the biological activity of notable molecules are limited. For example, the relationship between the immunomodulatory effect of APS and its relative molecular weight has not been clearly defined. Therefore, in this paper, we separated and obtained APS of different molecular weights by ultrafiltration technology and then constructed a mouse cyclophosphamide-induced immunosuppression model to investigate the immune activity of APS of different molecular weights. The immune enhancement mechanism of APS was explored by examining changes in routine blood indicators, body weight, immune organs, and differential metabolites in mouse serum. Results showed that APS-I (molecular weight, >2,000 kDa), APS-II (molecular weight, 1.02 × 104 Da) and APS-III (molecular weight, 286 Da) could increase the number of immune cells in mouse serum and improve immune organ damage to varying degrees. Among the samples obtained, APS-II showed the best effects. Compared with those in the blank group, 29 metabolites determined by UHPLC Q-Exactive MS in the serum of the model group changed remarkably, and APS-I, APS-II, and APS-III respectively restored 13, 25, and 19 of these metabolites to normal levels. Metabolomics analysis revealed that APS-II is mainly responsible for the immunomodulatory activity of APS. Metabolomics analysis revealed that the mechanisms of this specific molecule may involve the regulation of phenylalanine metabolism, cysteine and methionine metabolism, tricarboxylic acid cycle (TCA cycle) and arginine and proline metabolism.

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