Intrinsic viscosity–number average molecular weight relationship for poly(1,4‐butylene adipate) diol

The relationship between number average molecular weight (M_n) and intrinsic viscosity ([η]) was studied for poly(1,4‐butylene adipate) diol (PBAD) in tetrahydrofuran, toluene, and ethyl acetate at 25°C. Thus, a series of PBAD samples were prepared by polymerization between 1,6‐adipic acid and 1,4‐butanediol. The values of M_n for the samples were determined by end‐group analysis as well as by ebulliometry, and the average difference of M_n between the two analysis ways was about 2.69%. The Mark–Houwink–Sakurada equations for PBAD were obtained to relate [η] with M_n in the range of 1900–10,000. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological aspects of fiber spinning from cellulose solutions in N‐methylmorpholine‐N‐oxide

Based on rheological experiments with a cellulose solution in N‐methylmorpholine‐N‐oxide (NMMO), it was found that the shearing stress generated in the flowing viscoelastic fluid decreases with an l/d ratio in a rheometer capillary. This reduces the elastic response and the outflow of the fluid becomes more uniform. At constant temperature, the elongational viscosity of the solidified stream of the cellulose solution in NMMO is reduced with increase of the deformation rate, which makes it possible to increase the fiber‐formation velocity within the air zone. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1860–1868, 2001     

Viscosity–molecular weight relationship for aminopropyl‐terminated poly(dimethylsiloxane)

Aminopropyl‐terminated poly(dimethylsiloxane) (ATPS) with different molecular weights was prepared by base‐catalyzed equilibration of octamethylcyclotetrasiloxane and 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetramethyldisiloxane with different ratios. Their number‐average molecular weights (M_n) were determined by end–group analysis, and intrinsic viscosity ([η]) in toluene was measured with a Ubbelohde viscometer. A relationship between M_n and [η] was obtained for ATPS. For 1.0 × 10⁴ < M_n < 6.0 × 10⁴, it was in accord with [η]_{toluene,25°C} = 5.26 × 10^?2 M_n^0.587. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 975–978, 2001     

Molecular weight determination of 83% degree of decetylation chitosan with non‐Gaussian and wide range distribution by high‐performance size exclusion chromatography and capillary viscometry

Molecular weight determination of 83% degree of deacetylation (DD) chitosan with non‐Gaussian and broad molecular weight distribution by high‐performance size exclusion chromatography (HPSEC) and by capillary viscometry were proposed. The relationships between weight average retention volumes (RVw) of HPSEC and intrinsic viscosities ([η]) measured by capillary viscometer and the weight average molecular weight (Mw) measured by static light scattering were established for routine molecular weight determination of chitosans either by HPSEC or by the capillary viscometry method, respectively. These results showed: relationships of RVw and Mw for different Mw of 83.0% DD chitosans can be expressed by the equation Log Mw = −0.433 RVw + 11.66. The RVw of other DD chitosans do not correlate well with this equation. It indicated that DD of chitosan affected the relationship of RVw and Mw of chitosans studied. The Mark–Houwink constant a decreased from 0.715 to 0.521, as the solution ionic strength increased from 0.01M to 0.30M, whereas constant k increased from 5.48 × 10⁻⁴ to 2.04 × 10⁻³ over the same range of ionic strength solutions. The established RVw and Mw equation and [η] and Mw equation (Mark–Houwink equation) can be routinely used to determine the molecular weight from RVw or [η] of chitosan by HPSEC or by capillary viscometer, respectively, without the need of expensive instrumentation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1905–1913, 1999     

Determination of Mark–Houwink parameters of ethylene–norbornene copolymers and molecular characteristics estimation

Ethylene–norbornene copolymers (ENC) with ～ 50%, ～ 25% and ～ 15% norbornene (NB) fraction in a wide range of molecular weight were produced by metallocene catalysts. By coupling the gel permeation chromatography (GPC) with the intrinsic viscosity data in 1,2,4‐trichlorobenzene (TCB)at 150°C, the Mark–Houwink parameters of ENC were determined and compared with previous classical analysis using polyethylene's relative parameters. The results indicated that parameter K was considerably increased with decreasing NB fraction in ENC but parameter α was only increased slightly. Furthermore, the structure characteristics and correlative rheological parameters of resultant ENC were also calculated and discussed by the Stockmayer–Fixman analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Urea‐induced conformational changes of chitosan molecules and the shift of break point of Mark–Houwink equation by increasing urea concentration

Chitosan solutions of the same 83% degree of deacetylation (DD) but different weight average molecular weights (M_ws) (78–914 kDa) in 0.01M HCl containing different concentrations of urea (0–6M) were prepared. Intrinsic viscosity ([η]) and weight average molecular weight (M_w) of chitosan were measured with a capillary viscometer and light scattering, respectively. Mark–Houwink exponent a was used as the parameter of conformational index. The Mark–Houwink exponent a increased with increasing concentrations of urea. When solutions contained 0, 2, 3, 4, and 6M urea, the value of a increased from 0.715 to 0.839, 0.894, 1.000, and 1.060, respectively. This indicates the occurrence of urea‐induced conformational transitions of chitosans. The break point shifted from 223 kDa in solutions containing no urea to 280 kDa in 2M urea solutions, to 362 kDa in 4M urea solutions and further to 481 kDa in 6M urea solutions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 452–457, 2000     

Intrinsic viscosity–molecular weight relationship and hydrodynamic volume for pullulan

A numerical method for determination of Mark–Houwink–Sakurada (MHS) equation constants, a and K, was tested with success for two series of pullulan standard samples having narrow and broad molecular weight distributions (MWD) and taken into account their polydispersity. Different solvents, which were used to determine the intrinsic viscosities and the viscometric constants, a and K (published in the literature for pullulan), were compared. The various parameters affecting the constants are discussed. The procedure to determine the correct value of the hydrodynamic volume for pullulan was also described. This study resulted in the following MHS equations for narrow and broad MWD series of pullulan samples with M_w in the range of 5–1000 kDa: where q_MHS is the polydispersity correction factor and [η] is the intrinsic viscosity in dL g^?1. The plot of log K versus exponent a was linear and inversely related. This curve was used to estimate the constant K for pullulan with a known exponent a. Among various reported solvents, the diluted aqueous salt solutions have more advantages than other solvents. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4325–4332, 2006     

Physical properties of lyocell fibers spun from different solution‐dope phases

The hydration number (n) of NMMO hydrates has a significant effect on the rheological properties and phase of the cellulose solutions in the hydrates. The physical properties of the lyocell fibers spun from the cellulose solutions in NMMO hydrates with different values of n were investigated relative to the phase of the solution dope. NMMO hydrate with n = 1.1 could not fully dissolve cellulose, resulting in a heterogeneous solution. NMMO hydrate with n = 0.72 produced a mesophase solution that exhibited a good spinnability. When NMMO hydrates with n = 0.72 and 1.0 were used, the lyocell fiber spun from 15 wt % solution dope gave higher tensile strength than that spun from 12 wt % solution dope. NMMO hydrate with n = 1.0 produced a lyocell fiber whose tensile strength was slightly affected by spin–draw ratio but the tensile strength of the lyocell fiber prepared from NMMO hydrate with n = 0.72 was monotonically increased with increasing spin–draw ratio. Further, the latter gave higher birefringence. The lyocell fiber spun from 15 wt % solution in NMMO hydrate with n = 0.72 produced finely fibrillated structures. When treated with sonic wave the lyocell fiber prepared from 15 wt % cellulose (DP_w 940) solution in NMMO hydrate with n = 0.72 yielded the most serious fibrillation on the fiber surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 981–989, 2002     

Polybenzimidazole (PBI) molecular weight and Mark‐Houwink equation

The molecular weight, and intrinsic viscosity of polybenzimidazole (PBI) and its phosphonylated derivatives are reported. The relationship between intrinsic viscosity [η] and weight average molecular weight (M_w) for PBI has been established in H₂SO₄ and DMF‐LiCl. The Mark Houwink constants K_w of 5.2 × 10^?3 mL/g, α of 0.92 for H₂SO₄ solvent systems and, K_w of 3.2 × 10^?2 mL/g, α of 0.754 for DMF‐LiCl solvent system have been determined at M_w < 65,000. The intrinsic viscosity of PBI determined by the Huggins–Kraemer method was compared with a single point method, and found that both methods fit well for PBI in relatively low concentration solvent system, giving ～ 99% accuracy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheology of cellulosic N‐methylmorpholine oxide monohydrate solutions of different degrees of polymerization

Preparation and shear and elongational rheology of cellulose solutions of different degrees of polymerization (DP) in N‐methylmorpholine oxide monohydrate (lyocell) were investigated. The dissolution process takes place in two stages, depending on the content of low and high DP fractions from the dissolving pulp blends. The influence of the DP of cellulosic chains on elongational and shear viscosity is greater at low deformation rates. Low DP solutions behave more like viscous fluids and the increase of the chain length brings about an increase of the elastic component. Orientation induced by the convergence flow is enhanced by the higher DP cellulosic chains. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 396–405, 2001     

Rheological characterization of concentrated cellulose solutions in 1‐allyl‐3‐methylimidazolium chloride

The rheological properties of high concentrated wood pulp cellulose 1‐allyl‐3‐methy‐limidazolium Chloride ([Amim]Cl) solutions were investigated by using steady shear and dynamic viscoelastic measurement in a large range of concentrations (10–25 wt %). The measurement reveals that cellulose may slightly degrade at 110°C in [Amim]Cl and the Cox–Merz rule is valid for 10 wt % cellulose solution. All of the cellulose solutions showed a shear thinning behavior over the shear rate at temperature from 80 to 120°C. The zero shear viscosity (η_o) was obtained by using the simplified Cross model to fit experimental data. The η_o values were used for detailed viscosity‐concentration and activation energy analysis. The exponent in the viscosity‐concentration power law was found to be 3.63 at 80°C, which is comparable with cellulose dissolved in other solvents, and to be 5.14 at 120°C. The activation energy of the cellulose solution dropped from 70.41 to 30.54 kJ/mol with an increase of concentration from 10 to 25 wt %. The effects of temperature and concentration on the storage modulus (G′), the loss modulus (G″) and the first normal stress difference (N₁) were also analyzed in this study. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. II. Solution character and preparation

The focus of this article of a three part series is the effects of preparation and composition on the shear rheology of cellulose in the ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl). Included are the effects of three different degrees of polymerization, (i.e., average molecular weight), manual versus high shear mixing, a range of cellulose concentrations, and the effects of controlled amounts of lignin and a hemicellulose. The rheology implies that a gel phase develops at higher degrees of polymerization, higher concentration, and at lower temperatures. The first article focused primarily on shear rheology of cellulose in [Bmim]Cl with a high shear preparation technique, one degree of polymerization, a narrow range of cellulose concentrations, and temperature. The third article focuses on elongational rheology of cellulose in [Bmim]Cl. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of the degree of acetylation of o-cresol resin on its molecular conformation in solution

o-Cresol-formaldehyde resin (OC) and five kinds of acetylated OC (AC-X-OC; X is the degree of acetylation) were prepared. The Θ-temperature for each resin was determined by means of the Shultz-Flory method, and their molecular conformations in both tetrahydrofuran (THF) and Θ-solvent were estimated from the values of the exponents in the Mark–Houwink–Sakurada equations. The effect of the degree of acetylation on the exponent was negligible in THF, but was remarkable in Θ-solvent. In THF, the molecular chains of these resins are relatively extended, because the hydrogen bond between phenolic hydroxyl groups is loosely formed. In Θ-solvent, however, the molecular conformation is compact and the resins are considered to form a pseudo cross-linked network structure through inter- and/or intra-molecular hydrogen bonds. The Mark–Houwink–Sakurada equation for AC-100-OC in 2-ethoxyethanol at 92.0°C was found to be [η]_θ = 0.0773 M?^0.50_n, where [η]₀ is the limiting viscosity number under the Θ-condition, and M?_n is the number-average molecular weight. The unperturbed dimension, (〈r²₀〉/M?_n)^1/2, 〈r²₀〉 being the unperturbed mean square end-to-end distance, for AC-100-OC was found to be 0.659×10^?8 cm g^?1/2 mol^1/2.     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. III. Elongational rheology

The elongational rheology of solutions of cellulose in the ionic liquid solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was measured at 80, 90, and 100°C; 8, 10, and 12 wt% cellulose; Hencky strains 5, 6, 7; and strain rates from 1 to 100 s^?1. Master curves were generated by shifting the elongational viscosity curves with respect to temperature and Hencky strain. Also, general master curves were generated by simultaneously shifting with respect to both temperatures and Hencky strain. From the Arrhenius plots of the temperature shift factors, the activation energy for elongational flow was determined. The elongational rheology of these solutions was elongational strain rate thinning similar to that of their shear behavior and polymer melts and they were also strain hardening. Both effects and the viscosity increased with cellulose concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The morphology and photoelectronic properties of poly(9,9′‐dioctylfluorene)/ethyl‐cyanoethyl cellulose blends

The morphology and photoelectronic properties of blend films of poly(9,9′‐dioctylfluorine) (PF) and ethyl–cyanoethyl cellulose [(E‐CE)C] were investigated. It was found that the morphology of the blends was changed with the blend composition. The lateral phase separation was observed in submicron scale, and a nanoscale vertical phase separation occurred with enrichment of the (E‐CE)C at the surface of the blend films. The photoluminescent spectra of the blend films are blue‐shifted with the increase of the (E‐CE)C. The photoelectronic properties of the blends varied with the morphology of the blends. In the electroluminescent device, the turn‐on voltage was almost identical for the device with 50% or above 50 wt % PF in blend films and markedly improved for the device with only 25 wt % PF. The external quantum efficiency of the device fabricated with 75% PF is the highest among the device fabricated with the PF/(E‐CE)C blend films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheological characterization of cellulose solutions in N‐methyl morpholine N‐oxide monohydrate

Three different modes of rheological properties were measured on 11 and 13 wt % solutions of cellulose in N‐methyl morpholine N‐oxide (NMMO) monohydrate, in which concentration range lyocell fibers of much reduced fibrillation are preferably produced. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions. Both cellulose solutions showed a shear thinning behavior over the shear rate measured at 85, 95, 105, and 115°C. However, 13 wt % solution gave rise to yield behavior at 85ºC. The power law index ranged from 0.36 to 0.58. First normal stress difference (N₁) was increased with lowering temperature and with increasing concentration as expected. Plotting N₁ vs shear stress (τ_ω) gave almost a master curve independent of temperature and concentration, whose slope was about 0.93 for both cellulose solutions over the shear rate range observed (τ_ω > 500 Pa). In addition, the cellulose solutions gave high values of recoverable shear strain (S_R), ranging from 60 to 100. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 216–222, 2002     

Scaling functions of polymer‐induced turbulent drag reduction focusing on the polymer–solvent interaction

Based on turbulent drag reduction characteristics of polystyrene and polyisobutylene in a pipe flow and a rotating‐disk flow, respectively, a relationship between polymer concentration and drag reduction at a given Reynolds number was considered. The universal drag reduction equation of a three‐parameter relationship between drag reduction and polymer concentration was modified using intrinsic concentration and intrinsic viscosity, and it was then found to be the most useful formula for correlating DR data, especially for polymer–solvent interactions in a turbulent flow. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1836–1839, 2003     

A study on the solution behavior of IPBC‐hydrophobically‐modified hydroxyethyl cellulose

Through the macromolecule reaction method, a series of 4‐isopropylbenzyl chloride (IPBC) hydrophobically‐modified hydroxyethyl cellulose (HAHEC) were synthesized. The use of suitable amount of hydrophobic monomer can ensure both the strong intermolecular association and good water‐solubility of HAHEC. Effects of polymer concentration, shear rates, temperature, and electrolytes on the solution behavior of HAHEC were comprehensively studied, which indicated that the polymers show high viscosification property, excellent viscosity retention in brine water, and surface activity. FTIR, DSC, and UV measurements were applied to characterize the molecular structure and composition of HAHEC to confirm the incorporation of hydrophobic group into the polymer chain. Atomic force microscope (AFM) and fluorescence spectrum measurements were applied to study the formation of the molecule aggregation and hydrophobic microdomain of HAHEC, and revealed the close relationship between the rheological behaviors and the hydrophobic viscosification effect. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2824–2831, 2006     

Effect of the dissolution time on the structure and properties of lyocell‐fabric‐based all‐cellulose composite laminates

In this study, all‐cellulose composite laminates were prepared from lyocell fabric with ionic liquid (1‐butyl‐3‐methyl imidazolium chloride), a conventional hand layup method, and compression molding. Eight layers of lyocell fabric, which were impregnated with ionic liquid, were stacked symmetrically and hot‐pressed under compression molding for various times; this resulted in the partial dissolution of the surface of the lyocell fibers. The dissolved cellulose held the laminas together and resulted in a consolidated laminate. Finally, the prepared laminate was impregnated in water to remove the ionic liquid and to regenerate a matrix phase in situ; this was followed by hot‐press drying. Optical microscopy and scanning electron microscopy studies were used to analyze composite structures. With increasing dissolution time, the void content in the composites decreased, and the interlaminar adhesion improved. For LC‐2h and LC‐3h, the highest tensile strength and modulus values obtained were 48.2 MPa and 1.78 GPa, respectively. For LC‐4h, the highest flexural strength and modulus values obtained were 53.96 MPa and 1.2 GPa, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43398.     

Preparation and characteristics of a water‐soluble chitosan–heparin complex

To improve the wound‐healing ability of chitosan, heparin, known to be effective in wound healing, was complexed with water‐soluble chitosan (WSC) by chemical reaction. The chemical structure of the water‐soluble chitosan–heparin (CH) complex was analyzed, and CH complex formation was confirmed with an FTIR spectrometer. The mechanical and thermal properties of the CH complex were measured by a tensile tester and thermal analyzers (DSC and TGA). Within the heparin content up to ≈470 IU/g in the aqueous CH complex solution, the intrinsic viscosity and tensile strength of the water‐soluble CH complex gradually increased, but thermal stability slightly decreased by introducing the heparin into the WSC. When the heparin content was greater than these values (470 IU/g), the water‐insoluble CH complex, which is supposed to have a multisubstituted or crosslinked structure, precipitated in the aqueous water‐soluble CH complex solution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1784–1789, 2003