Elongational flow studies on the molecular properties of collagen and its thermal denaturation

An elongational flow method established in polymer physics was applied to study dynamic structure and properties of biopolymers in solution. Type I collagen solutions in the dilute to semidilute region are studied in elongational flow fields, generated in a Taylor four-roll mill, for temperatures from 20°C through the melting temperature to 60°C. A nonlocalized birefringent signal, characteristic of stiff molecules, is observed at all temperatures. The conformational changes as a function of temperature can be divided into two separate temperature dependent stages. In stage I, at lower temperatures, the collagen molecule behaves as a rigid rod and the birefringent signal Δn rises as a function of increasing strain rate ε. Throughout this stage the type of molecular interaction in semidilute solution does not change but the rate of interaction is increased by thermal excitation. In stage II, a characteristic criticality in the Δn vs. ? plot is observed. For strain rates up to a characteristic value, ?₀, the birefringence remains zero and for ?>?₀ whole field bright birefringence is observed. The plateau values of birefringence, Δn_p, at high strain rates in the Δn vs. ? curve decreased with rising temperature in stage II. This criticality in behavior and the decreasing tendency in Δn_p with temperature are explained by the collagen molecule changing to a hinged-rod conformation. Thus the untwining of collagen as a function of temperature initiates at several places simultaneously, probably at specific amino acid sequences, within the collagen rodlike molecule.     

Effect of entrance geometry on the capillary flow of cellulose acetate–acetone solution

Capillary flow data were obtained for a 27.5% solution of cellulose acetate in acetone. The solution temperature was 50°C, and the range of apparent shear rates investigated was 1.7 × 10⁵ to 1.7 × 10⁶ sec^?1. Capillaries having tapered entrance angles of 37.88° to 120.63° were used. A power-law model was adequate to describe the shear stress at the wall (τ_w) and the corrected shear rate \documentclass{article}\pagestyle{empty}\begin{document}$(\dot \gamma )$\end{document} relationship. Entrance angle affected the entrance pressure drop corrected for kinetic energy, (ΔP_0,c); ΔP_0,c increased as the angle widened. Treating the entrance flow as an elongational flow situation facilitated superposition of the Delta;P_0,c data on a single curve. Estimated elongational viscosities decreased with increasing applied stress.     

Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers     

Elongational flow studies of hinged rodlike molecules

Poly(amino acid) in an intermediate state of its helix-coil transition is known to be in a hinged rodlike conformation. In this work, the responses of poly(amino acids) in the hinged rodlike conformation against an elongational flow field were investigated by monitoring their flow-induced birefringence. Poly(L-glutamic acids) (PGA) and poly(γ-benzyl-L-glutamate) (PBLG) were examined as polyelectrolyte and noncharged poly(amino acids), respectively, and the results were compared. In the plots of flow-induced birefringence, Δn, against strain rate, $ {\dot \varepsilon } $, for hinged rodlike PBLG, there was a critical strain rate, $ \dot \varepsilon_0 $, below which Δn was not observed. Over $ \dot \varepsilon_0 $, the birefringence pattern observed was identical with that of rodlike molecules. The Δn vs. $ {\dot \varepsilon } $ plot for hinged rodlike PGA had characteristics of a rigid rod at any strain rate and there was no $ \dot \varepsilon_0$ observed. The rotational diffusion coefficient, D_r, of PBLG in the hinged rodlike conformation was larger than that for its helical conformation, while D_r, for the hinged-rodlike PGA was smaller than that for its helical conformation. It is concluded that the hinged-rodlike PGA molecule is in an extended form and that the hinged-rodlike PBLG is hydrodynamically more compact and rigid than that in its quiescent state. It is deduced that at $\dot \varepsilon_0$ hinged rodlike PBLG molecules collapse to a conformation optically anisotropic and mechanically rigid. © 1996 John Wiley & Sons, Inc.     

Deformation of λ-phage DNA molecules in an elongational flow field

The response of λ-phage DNA molecules to a well-defined elongational flow field generated by a Taylor four-roller mill was investigated by observing the flow birefringence, Δn. Δn in the center of the four rollers, near the stagnation point, was localized at the mill exit symmetry plane. The intensity gradually increased from the off-symmetrical plane to the center of the mill, and at the exit symmetrical plane, the intensity was maximum. Δn also gradually increases with the strain rate, $\dot \varepsilon$. These observations indicate that DNA molecules in the solution would be free draining in nature. From the decay of λn at each point in the mill after a sudden stop of the mill operation at 24 s⁻¹, the rotational diffusion coefficient of molecules, D_r, at each point in the mill space was estimated, where the relaxation time of the decay of λn was considered to be related to the molecular disorienting process. It is concluded that at 24 s⁻¹ λ-phage DNA molecular coils near the stagnation point, which was assumed to be a prolate spheroid as a whole, was so deformed that the aspect ratio p (=b/a ≦ 1, where a and b are, respectively, the longer and shorter axes) would be ${\textstyle{1 \over {12}}}$ of that of the DNA molecule which has just entered the mill space. This result suggests that there is a possibility for the DNA molecule to be in a stretched conformation at a higher strain rate. © 1996 John Wiley & Sons, Inc.     

Influence of melt deformation history on orientation in vitrified polymers

An experimental study of the development of orientation in polystyrene melts during flow and its retention in vitrified parts is described. It is shown on the basis of elongational and shear flow experiments that orientation in vitrified polystyrenes may be predicted from a knowledge of the stress field at the time of vitrification and application of stress-optical laws. More generally a relationship between birefringence and principal stress difference is found which correlates (1) on-line isothermal shear flow, (2) on-line non-isothermal elongational flow (melt spinning), and (3) vitrified samples formed in both shear and elongational flow. It is further proposed that orientation in polymer chains in deforming melts is uniquely dependent on stress—specifically, that the ratio of the stress-optical constant C to the intrinsic birefringence Δ° is approximately a constant.     

Birefringence in gas‐assisted tubular injection moldings: Simulation and experiment

The influence of the processing variables on the birefringence and polymer/gas interface distribution is analyzed for polystyrene moldings obtained by gas‐assisted injection molding (GAIM) under various processing conditions. The processing variables studied were: melt and mold temperatures, shot size, gas pressure, injection speed, and gas‐delay time. Measurements and viscoelastic simulations of the radial distribution of birefringence components, Δn and n_rr ? n_θθ, the variation of the average birefringence, 〈n_zz ? n_θθ〉, along the molding and polymer/gas interface along the length of spiral‐shaped tubular moldings are presented. The polymer/gas interface distribution and flow stresses were simulated using a numerical scheme based on a hybrid finite element/finite difference/control volume method. The birefringence was calculated from the flow‐induced stresses using the stress‐optical rule. Simulations qualitatively agreed with measurements and correctly described theeffect of the processing variables on the birefringence andthe polymer/gas interface distribution in GAIM moldings. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Studies on the melt spinning of nylon 6. II. Effect of heating the threadline upon orientation and crystallization

The effect of heating nylon 6 threadline in a spinning tube upon its orientation and crystallization behavior was studied by measuring the filament birefringence Δn_H at the outlet of the spinning tube, the conditioned filament birefringence Δn_∞ after take-up, the filament densities and crystallinities of the γ-form, and by calculating the relative crystallinity of the threadline. Results were as follows: When the filament mean temperature \documentclass{article}\pagestyle{empty}\begin{document}$\overline{\theta _s \left(x \right)}$\end{document} in the spinning tube was about 80°C, the birefringence Δn_H showed a peculiar behavior in that, at this temperature, the Δn_H value decreased due to partial melting of the semistable molecular structure of the threadline that had been formed before the inlet of the spinning tube. And, when the temperature was over about 80°C, the Δn_H value increased due to the setting in of crystallization. The relative crystallinity χ of the threadline was calculated using the kinetic theory of nonisothermal crystallization neglecting the entropy effect of molecular orientation. Assuming that the crystal growth was spherulitic rather than fibroid, the calculated χ values approximately agreed with the experimental results.     

Birefringence in injection‐compression molding of amorphous polymers: Simulation and experiment

The influence of the processing variables on the residual birefringence was analyzed for polystyrene and polycarbonate disks obtained by injection‐compression molding under various processing conditions. The processing variables studied were melt and mold temperatures, compression stroke, and switchover time. The modeling of flow‐induced residual stresses and birefringence of amorphous polymers in injection‐compression molded center‐gated disks was carried out using a numerical scheme based on a hybrid finite element/finite difference/control volume method. A nonlinear viscoelastic constitutive equation and stress‐optical rule were used to model frozen‐in flow stresses in moldings. The filling, compression, packing, and cooling stages were considered. Thermally‐induced residual birefringence was calculated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the Young's relaxation modulus and strain‐optical coefficient functions. The residual birefringence in injection‐compression moldings was measured. The effects of various processing conditions on the measured and simulated birefringence distribution Δn and average transverse birefringence <n_rr?n_θθ> were elucidated. Comparison of the birefringence in disks manufactured by the injection molding and injection‐compression molding was made. The predicted and measured birefringence is found to be in fair agreement. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Assessment of the intrinsic birefringence of partially oriented poly(ethylene terephthalate) yarns

Partially oriented poly(ethylene terephthalate) yarns (PET POY) have been studied with respect to their birefringence, sonic modulus, and stress-optical properties in an effort to extract the values for the intrinsic birefringences of the crystalline (Δn_c°) and amorphous (Δn_a°) regions. The data have been analyzed within the framework of both the sonic modulus-birefringence treatment of Samuels and Dumbleton, and the Gaussian rubber elasticity theory using the usual shrinkage stress-birefringence relations. The following values have been determined: Δn_c° = 0.22 and Δn_a° = 0.19. The work was undertaken to resolve the discrepancy in the published literature values of these two parameters.     

Stress–optical behaviour of polyester networks

Thermoelastic networks were prepared by end‐linking hydroxyl terminated chains of poly(neopentylglycol hexafluoroglutarate) (PNGHFG) and poly(diethylene glycol terephthalate) (PDET) using, respectively, tri(p‐isocyanate‐phenyl)‐thiophosphate and 2,4‐bis(p‐isocyanate benzyl)‐p‐phenylisocyanate as crosslinking agents. The plots of birefringence versus stress for PNGHFG and PDET networks exhibit negative deviations from linearity at elongation ratios greater than 1.9 and 5, respectively. The values of the optical configuration parameter Δa for the former and latter networks are 2.98 ų at 5 °C and 20.80 ų at 30 °C, respectively. Theoretical calculations carried out using the conformational energies obtained from the critical analysis of the mean‐square dipole moments of diethyl hexafluoroglutarate and poly(neopentylglycol hexafluoroglutarate) give the value of 2.24 ų at 5 °C for this parameter, in fair agreement with the experimental result. Similar calculations carried out on PDET networks give Δa = 3.74 ų at 30 °C, a value significantly lower than the experimental result. The cause of the strong discrepancy between the theoretical and experimental results observed for the optical configuration parameter of PDET is discussed. © 2002 Society of Chemical Industry     

Thermal stresses and birefringence in quenched tubes and rods: Simulation and experiment

Measurements and simulations of the radial distribution of the thermal birefringence components, Δn and n_θθ ? n_rr, and the average birefringence, <n_zz ? n_θθ>, in free quenched tubes and rods of polystyrene (PS) and polycarbonate (PC) at different initial temperatures were carried out. The thermal stress and birefringence components were simulated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the Young's relaxation modulus and strain‐optical coefficient functions of polymers. The numerical procedures used to discretize the governing equations using finite difference method were described. The obtained numerical results provided the evolution of stress and birefringence components with time during and after quenching and an explanation of the measured residual birefringence distribution in quenched tubes and rods. It was also found that the thickness of the slices removed from the samples to measure the thermal birefringence components, Δn and n_θθ ? n_rr, was critical, in particular, when the initial temperatures were close to the glass transition temperature of polymers. With an increase of the initial temperature during quenching, a better agreement between the simulated and measured birefringence components was obtained. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Studies on synthetic polymer plates with high surface energy. III. Diethylene glycol bis(allyl carbonate)–unsaturated sulfonic acid system

Synthetic polymer plates (GPs) with high surface energy were prepared by the two-step copolymerization process previously reported, using diethylene glycol bis(allyl carbonate) (CR-39) as M₁ monomer and unsaturated sulfonates [sodium vinyl sulfonate (VS^?Na⁺), potassium styrene sulfonate (StS^?K⁺), and sodium 2-sulfoethyl methacrylate (SEM^?Na⁺)] as M₂ monomer. The contact angle (θ_H) of water for the acid-treated (immersed in an aqueous 0.1 N HCl solution for 2 h) GPs decreased in the order StS^?K⁺, VS^?Na⁺, and SEM^?Na⁺. In the case of M₂ = SEM^?Na⁺, the θ_H value was about 20°. By adding NaCl in the immersion solution and changing the pH of the immersion solution, the θ_H values for the CR-39–SEM^?Na⁺ GPs were lowered to 18.9 and 13.1°, respectively. The θ_H values for the above GPs were smaller than those for the CR-39–acrylic acid or the CR-39–methacrylic acid GPs in the previous report, whereas the contact angle (θ_Na) of water for the former after alkali treatment (immersed in an aqueous 0.1 N NaOH solution for 2h) was larger than those for the latter. The former had durability of water wettability superior to the latter because of the difference in dissociation characteristic of the respective functional group.     

Elongation flow studies of DNA as a function of temperature

The response of T4‐phage DNA molecules to an elongational flow field was monitored by flow‐induced birefringence as a function of temperature. The flow‐induced birefringence observed in this study was localized in the pure elongational flow area with a critical strain rate, indicating that the birefringence was attributed to a coil–stretch transition of DNA molecules. The slight decrease in the birefringence intensity with increases in temperature to 40°C was explained by a thermal‐activation process. At temperatures above 50°C, flow‐induced birefringence decreased remarkably, and no birefringence was observed at temperatures above 60°C. After the flow experiments, ambient temperature was reduced back to room temperature, and flow experiments at room temperature were performed again. Flow‐induced birefringence was recovered almost completely in samples for which the first flow measurements were made at temperatures below 53°C. Irreversible changes were observed for samples for which the first flow experiments were performed at temperatures above 55°C. The temperature dependence of UV‐absorption spectra revealed that the double‐strand DNA helix began to partially untwine at a temperature over 50°C, and duplexes became almost completely untwined at a temperature over 55°C. A comparison of electrophoresis patterns for untwined molecules showed that flow‐induced scission of DNA molecules occurred in a sample solution in flow experiments performed at 65°C, while no molecular weight reduction was observed in the sample solution at 55°C. In this article, this difference between the untwined DNA molecules is discussed on the basis of the thermally activated bond scission (TABS) model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1357–1365, 2002     

Pressure drop for single and two‐phase flow of non‐newtonian liquids in helical coils

New experimental results on pressure loss for the single and two‐phase gas‐liquid flow with non‐Newtonian liquids in helical coils are reported. For a constant value of the curvature ratio, the value of the helix angle of the coils is varied from 2.56° to 9.37°. For single phase flow, the effect of helix angle on pressure loss is found to be negligible in laminar flow regime but pressure loss increases with the increasing value of helix angle in turbulent flow conditions. On the other hand, for the two‐phase flow, the well‐known Lockhart‐Martinelli method correlates the present results for all values of helix angle (2.56‐9.37°) satisfactorily under turbulent/laminar and turbulent/turbulent conditions over the following ranges of variables as: 0.57 ≤ n′ ≤ 1; Re′ < 4000; Re_l < 4000; Re_g < 8000; 8 ≤ x ≤ 1000 and 0.2 ≤ De′ ≤ 1000.     

Opto-thermal properties of fibers. XI. The effect of thermal annealing of drawing behavior for Egyptian polyester fibers on the crystallinity and some optical parameters

The structure developed of annealed Egyptain poly(ethyleneterephthalate) (PET) fibers is studied interferometerically due to the drawing process. Using a two-beam Pluta polarizing interference microscope connected to a device to dynamically study the draw ratio with the birefringence changes, the relations of drawing changes with some optical parameters are given. The evaluation of density, the mean square density fluctuation η², crystallinity, amorphous orientation, crystalline orientation functions, number of chains per unit volume N_c, and number of random links between the network junction points N has been found. The results obtained clarify the effect of annealing time and temperature with different draw ratios on the structure of PET fibers. Empirical formula is suggested to correlate the changes in f_θ, θ, Δn_a, and A with the draw ratio. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1371–1386, 1998     

Glass transition and mechanical properties of PLLA and PDLLA‐PGA copolymer blends

The change of the glass transition temperatures (T_g) in the blend of poly(L ‐lactic acid) (PLLA) and the copolymers of poly(D,L ‐lactic acid) and poly(glycolic acid) (PDLLA‐PGA) with different D,L ‐lactic acid and glycolic acid composition ratio (50 : 50, 65 : 35, and 75 : 25) was studied by DSC. Dynamic mechanical measurement and tensile testing were performed at various temperatures around T_g of the blend. In the blend of PLLA and PDLLA‐PGA50 (composition ratio of PDLLA and PGA 50 : 50), T_g decreased from that of PLLA (about 58°C) to that of PDLLA‐PGA50 (about 30°C). A single step decrease was observed in the DSC curve around T_g between the weight fraction of PLLA (W(PLLA)) 1.0 and 0.7 (about 52°C) but two‐step changes in the curve are observed between W(PLLA) = 0.6 and 0.3. The T_g change between that of PLLA and that of PDLLA‐PGA and the appearance of two T_gs suggest the existence of PLLA rich amorphous region and PDLLA‐PGA copolymer rich amorphous region in the blend. A single step decrease of E′ occurs at around T_g of the pure PLLA but the two‐step decrease was observed at W(PLLA) = 0.6 and 0.4, supporting the existence of the PLLA rich region and PDLLA‐PGA rich region. Tensile testing for various blends at elevated temperature showed that the extension without yielding occurred above T_g of the blend. Partial miscibility is suggested for PLLA and PDLLA‐PGA copolymer blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2164–2173, 2004     

Study of kinematics and dynamics of film blowing of different polyethylenes

An extensive experimental study of the effects of material characteristics and processing parameters on the kinematics and dynamics of film blowing is presented. Three polyethylene resins, a high-density polyethylene (HDPE), a low-density polyethylene (LDPE), and a linear low-density polyethylene (LLDPE) were investigated. The convergent flow analysis of Cogswell was used to characterize the elongational flow behavior of the polymers. Strain rates and pressure inside the bubble (P_i) have been determined over a wide range of film blowing conditions. Moreover, on-line bubble temperature and birefringence measurements have been carried out along the length of the bubble. The experimental results reveal that the three polymers display different behaviors. The LLDPE requires the highest P_i value and the LDPE, the lowest. Consistent with this, the LLDPE shows the lowest in-plane birefringence and the LDPE, the highest. Interactions between various process parameters affecting the P_i value are characterized. Bubble instability is correlated to the apparent uniaxial elongational viscosity and P_i. The most stable polymer (LDPE) has the highest elongational viscosity and requires the lowest P_i. Stresses have been calculated with the help of the birefringence and P_i data. The stress and strain rate data were used to calculate an apparent nonuniform biaxial elongational viscosity of the melts, but could not be correlated through any simple constitutive equation.     

Melt rheology of nanometre‐calcium‐carbonate‐filled acrylonitrile–butadiene–styrene (ABS) copolymer composites during capillary extrusion

The melt flow properties during capillary extrusion of nanometre‐calcium‐carbonate‐filled acrylonitrile–butadiene–styrene (ABS) copolymer composites were measured by using a Rosand rheometer to identify the effects of the filler content and operation conditions on the rheological behaviour of the sample melts. The experiments were conducted under the following test conditions: temperature varied from 220 to 240 °C and shear rate ranged from 10 to 10⁴ s^?1. The filler volume fractions were 0, 10, 20, 30, 40 and 50%. The results showed that the shear flow did not strictly obey the power law under the test conditions, and that the entry pressure drop (ΔP_en) and the extension stress (σ_e) in entry flow increased nonlinearly, while the melt shear viscosity (η_s) and extension viscosity (η_e) decreased with increasing the wall shear stress (τ_w) at constant test temperature. The dependence of the melt shear viscosity on the test temperature was approximately consistent with the Arrhenius expression at fixed τ_w. When τ_w was constant, η_s and η_e increased while ΔP_en and σ_e decreased with the addition of the filler volume fraction. © 2002 Society of Chemical Industry     

Orientation development in the injection molding of amorphous polymers

Frozen-in orientation in the injection-molding of amorphous polymers has been considered in terms of flow- and cooling-induced birefringence. In particular, measurements of the frozen-in orientation distribution in polystyrene (PS) molded strips and circular runners have been performed. Three birefringence components, Δn, n₂₂ ? n₃₃, and n₁₁ ? n₃₃, have been measured for strips, and two components, Δn and n_rr ? n_θθ, for runners. The effects of various processing conditions, of strip thickness, and of runner diameter on orientation development have been analyzed and compared with those predicted by our previously developed viscoelastic theory. In addition to injection-molding experiments, free and constrained quenching experiments for PS and poly(methyl methacrylate) (PMMA) strips have been carried out and the gapwise distribution of cooling-induced (thermal) birefringence has been measured. Relaxation of thermal birefringence following quenching has been observed for PMMA. The effects of flow- and cooling-induced orientation on various components of birefringence in molded parts have been elucidated and limitations on the applicability of the stress-optical law to the injection-molding of amorphous polymers have been discussed.