Interferometric study of creep deformation and some structural properties of polypropylene fiber at three different temperatures

Influence of temperature on creep deformation for polypropylene PP fiber under a constant load was studied interferometrically. The automated multiple‐beam Fizeau system in transmission was equipped with a mechanical creep device attached to a wedge interferometer. This system was used to determine the optical properties (n^∥, n^?, and Δn) of PP fiber during the creep process at constant loading with varying temperature. The creep compliance was drawn as a function of both time and temperature. An empirical formula was suggested to describe the creep compliance curves for PP fibers and the constants of this formula were determined. Two Kelvin elements combined in series were used to provide an accurate fit to the experimental compliance curves. The stress–strain curve via creep was studied to determine some mechanical parameter of PP fibers, Young's modulus E, yield stress σ_y, and yield strain ε_y. The optical orientation function f(θ), the dielectric constant d, the dielectric susceptibility χ, the surface reflectivity , and the average work per chain W′ were also calculated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Some Aspects of Thermal Stability and the Characteristics of Poly(ethylene terephthalate) (PET) under Stress

In this work we use thermal shrinkage for estimating the internal stresses accumulated in a sample during a technological process. This can be a precious instrument available for every manufacturer interested in the thermal treatment efficiency. Based on the Kelvin‐Voight rheological model, we have established a correlation between the internal stresses appearing during the technological formation processes of yarns and their shrinkage at different temperatures. In this work (PET) fibers were used for study, with different birefringences ranging between 4.2×10^–3–2.2×10^–3. Thermal treatment was performed with warm air at temperatures between 333–453 K. The applied unitary stress changed within the range 5.09×10¹⁰–18.84×10¹³ N·m^–2. From the examination of the curves obtained for free contraction Δε = f (T) for different birefringences Δn for the preoriented PET fibers, contraction increases with increasing temperature up to a maximum situated at ≈ 353 K and then decreases to a constant value. From the examination of the curves, the dimensional change vs. contraction σ = f (Δε), to a thermal treatment under stress for different birefringences Δn, when an external stress σ is applied the thermal stability of the fibers already having on orientation, made evident by the birefringence magnitude, that in the case of a slight orientation, the retraction decreases with increasing temperature. Singular points registered for fibers with Δn = 22×10^–3 for a temperature exceeding 393 K indicate that for the partially orientated fibers the sample is subjected to a stretching process during the thermal stability under stress. We established experimentally a correlation between the strain σ and Δn, Δn = ct. σ/T, i. e., a decrease of the birefringence with increasing temperature.     

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     

Compressional behavior of inked open-cell foams

The mechanical behavior of various classes of inked and non-inked (dry) open-cell foam rollers has been investigated from stress/strain measurements in compression. Hysteresis, creep, and recovery in dynamic loading were used to differentiate the rollers as to their utility in printing applications. Creep, ?_c(t), and recovery, ?_r(t), were determined in a compression mode from force measurements and strain decay, ?(t), i.e., Δ?_c(t) = ?₀ – ?(t) [?₀ = ?(t = 0)] or ?_c(t) = 2?₀ – ?(t). The creep function, Δ?_c(t), represents the plastic strain, ?_pl(t = t_h), and is uniquely defined from the recovery function, Δ?_c(t) = ?_r(t = t_h), where t_h is the hold or contact time. The recovery results for a polyurethane ester (PUE) and acrylonitrile/butadiene (AB) rollers (dry/ink), poly(vinylidene fluoride) film (PVF₂) (air/vapor) and low-density polyethylene film (LDPE) (air/vapor) were found to fit a master curve of the form F_r(θ) = EXP[-K_r(t_h)θ] = [?_r(t) – ?_∞(t_h)]/[?₀(t = O) – ?_∞(t_h)] at a reduced time of K_r(t_h)θ {θ = t/t_h and K_r(t_h) = k′_r(t_h)t_h = C₀/(t_h)^α?1 (where C₀ depends on the material's “dry” or “wet” state, α is a function of the type of material, and ?_∞ is the permanent set). These empirical results are consistent with the observed decreases in print intensity during transfer to a paper substrate and weight changes of the roller, i.e., creep and recovery are important in the printing characteristics of a given roller material. Other factors of importance in the overall transfer and print quality, but of longer-term considerations, are diffusion processes within the polymer and the nature of the polymer (e.g., porosity, chemical constitution, surface and interfacial tensions).     

Study of stability and thermodynamic properties for polychlorinated dihydrophezines by density functional theory

The thermodynamic properties of 76 polychlorinated dihydrophezines (PCDPs) in the gaseous state at 298.15 K and 101.325 kPa, have been calculated using the density functional theory (the BHANDHLYP/6‐31G*) with Gaussian 03 program. Based on these data, the isodesmic reactions were designed to calculate the standard formation heat (Δ_fH^θ), standard Gibbs free energy of formation (Δ_fG^θ) of PCDPs in the gaseous state. The relations of these thermodynamic parameters with the number and position of chlorine substituents (N_PCS) were discussed, and it was found that there exist good correlation between thermodynamic parameters, including heat capacity at constant volume , entropy (S^θ), enthalpy (H^θ), free energy (G^θ), Δ_fH^θ, Δ_fG^θ, and N_PCS. The relative stability order of PCDP congeners was theoretically proposed based on the relative magnitude of their Δ_fG^θ. In addition, the values of molar heat capacity at constant pressure (C_p,m) for PCDP congeners have been calculated.     

On the relationship between K and a and between Kθ and the molecular weight per chain atom

It is shown that in [η] = KM^a there exists a relationship between K and a of the form log K = C ? Ba. The parameters C and B are typical of each polymer and, under θ conditions, define a characteristic K_θ for the polymer. When plotted against m₀/z, the molecular weight per backbone atom, the values of log K_θ cluster along three distinct lines. In a fashion similar to the observed dependence of number of atoms between chain entanglements on m₀/z, the lines are associated with highly flexible polymers, intermediate flexibility polymers, and stiff chain polymers. Deviations from the intermediate flexibility line are explained on the basis of changes in the distribution of mass in the plane perpendicular to the overall direction of the backbone chain.     

Long-chain branching in low-density polyethylene

A sample of a commercial low-density polyethylene was fractionated and values of number ? M_n and weight-average M_w, molecular weights obtained together with intrinsic viscosities [η], measured in decalin at 135° and in a theta-solvent, diphenyl at 118°. Results are compared with those obtained using samples of high-density polyethylene, of narrow molecular weight distribution, in decalin at 135° and in diphenyl at 125°. Values of the z-average mean square radius of gyration (S^?2)_z, are converted to the weight-average unperturbed state. The branching parameters g and g¹ thus obtained, indicate that long-chain branching increases with increasing molecular weight. Intrinsic ivscosities under theta-conditions for the low-density polyethylene fractions lead to a relationship [η]_θ = K _w^0·20, agreeing with the treatment of Zimm and Kilb. Some of the approximations involved in the estimation of long-chain branching are discussed.     

On‐line opto‐viscoelastic analysis of polypropylene fibres using multiple‐beam Fizeau fringes in transmission and a modified creep device

A creep device attached to an automated multiple‐beam Fizeau system in transmission was modified with a designed digital ruler. This device allows on‐line measurements of fibre length during creep experiments in terms of an analogue voltage value. The influence of sustained stress values on creep deformation and optical properties (n^||, n^? and Δn) for polypropylene (PP) fibres was studied interferometrically. The opto‐viscoelastic properties of PP fibres were determined for three different values of constant applied stress of 11.536, 18.717 and 25.905 MPa, at room temperature. Also, the variations of the cross‐sectional area and Poisson's ratio were studied during creep extensions. The compliance curves were obtained as a function of both time and applied stresses. Empirical formulae are suggested to describe the creep compliance curves for PP fibres, and the constants of these formulae were determined and described at each applied stress. A Kelvin chain was used to model the mechanical behaviour of the PP fibres under study. The effect of strain on the mean refractive indices, orientation function density and crystallinity was investigated as a result of the recorded data. Microinterferograms are given for illustration. The modified creep device with the designed digital ruler enables one to obtain instantaneous automatic accurate recording of fibre length values during creep experiments. Calculation of refractive indices, orientation function and crystallinity shows a difference in material behaviour at small stresses from that at higher stresses which may be attributed to different strain rates caused by different stresses. Copyright © 2010 Society of Chemical Industry     

Programmed polymer light-scattering data

An ALGOL computer program has been devised to manipulate light-scattering data from the Brice-Phoenix photometer. The input consist of experimental values of the galvanometer deflections and filter factors used for each concentration c and angle of measurement θ. These are transformed to the appropriate variables in the fundamental equation including the particle scattering factor, viz: c/Qθ = (W/K^*)M?_w^?1[1 + (16/3) × π²n₁²λ〈S²〉 sin² (θ/2)] + (W/K^*)2A₂c + (W/K^*)3A₃c² in which Qθ is a corrected from of the Rayleigh ratio and (W/K^*) is a composite constant term for the instrument and polymer–solvent system. By writing X?_ij for the variable c/Q_θ at θ_i and c_j, a function X is found by least squares to fit X?_ij, thus X = l + m sin (θ/2) + nc_j + bc_j². The equations arising from minimizing Σ_i^K=1 Σ_j^L=1 (X_ij ? X?_ij)² are solved by the computer to yield the best-fitting coefficients l, m, n, and b. These can then be related simply to the molecular weight, root-mean-square radius of gyration, second and third virial coefficients, respectively. The final portion of the program is designed to check the fit of these coefficients. It yields a table of the differences between all experimental c/Qθ values and the coressponding ones obtained by inserting the derived l, m, n, and b into the fundamental equation. The procedure has been tested satisfactorily by using a well-standardized sample of polystyrene in toluene at 30°C. and a wavelength of 436 mμ.     

The Softness Parameters of Ions. Prediction of the Occurrence of Miscibility Gaps in Molten Salt Mixtures

Softness parameters σ_M for cations and σ_X for anions, have been calculated as dimensionless quantities for approx. 90 cations and 18 anions. They are given by σ_M = [σ_A (M^m+) - σ_A(H⁺)]/σ_A(H⁺) and σ_X = [σ_B(X^a?) - σ_B(OH^?)]/σ_A(H⁺) where σ_A = [σI_i(M) + ΔH⁰_h(M^m+)]/m and σ_B = [-E_a(X) + ΔH⁰_h(X^a?)]/a are Ahrland's parameters. The new normalized and comparative (to the test ions H⁺ and OH^?) softness parameters are positive for soft ions and negative for hard ones. These parameters, obtained independently, are used with a four-coefficient equation to calculate coordinate bond energies for metal halides with acceptable accuracy. Considerations of the average coordination in reciprocal molten salt mixture lead to an expression for the metathesis energy change as proportional to the product of the differences in softness parameters of the two cations and the two anions. An empirical one-coefficient equation involving the softness parameters is proposed to deal with next-nearest-neighbor interactions in binary common-ion molten salt mixtures. These relationships are then used with Blander and Topol's equation to predict the occurrence of irascibility gaps in uni-univalent reciprocal salt mixtures. The gaps found in other systems are also discussed in terms of the softness of the constituent ions.     

Generalized warpage parameter

A warpage index (Δψ_m) was introduced for studying warpage characteristics of a plastic part injection molded from PA66 compounded with 30 wt% glass fiber. Δψ_m is defined as Δψ_m = (Δψ_m)_max – (Δψ_m)_min, where ψ_m = ψ(θ)_max, where ψ(θ) = (ε(θ) – α(θ)ΔT)/| α(θ)ΔT|, where ε is the total strain, α is the linear thermal expansion coefficient, ΔT is temperature difference, and θ is the angle along which ε and α are calculated. Finite element analysis was used for calculating flow field in injection, fiber orientation, material anisotropy and warpage. ψ_m is calculated in each finite element, and Δψ_m is calculated in a whole finite element model. Δψ_m is a measure of the ratio of actual shrinkage to the amount of shrinkage that would occur if an element freely shrank. The characteristics of Δψ_m were studied. It has been found that warpage is null if Δψ_m = 0, but that null warpage generally does not indicate Δψ_m = 0. It is shown that Δψ_m quantitatively represents the warped and unwarped state. Δψ_m distinguishes the null warpage state with possible buckling from the null warpage state without possible buckling. It has been shown that material anisotropy is possibly described with Δψ_m, and that the cause of warpage is self-restrictive deformation in an injection molded part. It has been deduced that it is generally not possible to eliminate warpage only by controlling material properties. Δψ_m is obtainable for a plastic part with complex geometry and complex fiber orientation state, and for arbitrary materials. Applications of Δψ_m are left for future study.     

26-Year creep and recovery of poly(vinyl chloride) and polyethylene

Creep experiments on two thermoplastics at constant values of tensile stress, temperature, and relative humidity previously reported for 132,000 h were continued to about 230,000 h. An equation of the form ? = ?^o + ?⁺tⁿ was used to predict the creep, where t is time and ?^o, ?⁺, and n are constants for a given stress. ?^o, ?⁺, and n were determined from the first 1900 h of data and were used to predict the creep to 230,000 h. The subsequent recovery on unloading was predicted using the same equation together with the superposition principle. Also reported are creep and recovery of companion specimens aged for about 98,000 h.     

A physical model of the pressure dependence and biaxial mechanical properties of solid polymers

We give here a model for the pressure dependent, biaxial mechanical behavior of glassy polymers based on the thermally activated growth of deformation zones (Somigliana dislocation loops). The Coulomb criterion of plasticity, σ_c = S ? mσ_n, is found as the critical threshold needed to propagate Somigliana loops, in the same way as yield in crystals is found as the stress to move Volterra dislocation loops. While S is the shear strength, it is proposed that m follows basically from chain spacing fluctuations in the polymer glass; the temperature dependences of both parameters are derived. Application to tensile and compressive tests under a confinement pressure P is developed, with the aim to derive the pressure dependent (biaxial) strain-rate law. In particular, the pressure effect on dislocation density, that is, on plasticity defect nucleation, is shown to have a definite role in the plasticity of these solids. It introduces in the strain-rate law a normal stress dependent term (exp Dσ_n), which may have a decisive importance in a number of situations like multiaxial solicitations, solid state polymer shaping, second phase effects in polymer blends, and so on. Finally, a set of constant strain rate experiments is presented on an unsaturated polyester resin crosslinked with styrene. Measurements fit reasonably well with the predictions of the above model up to ～50 K below the glass transition, at which collective molecular motions invalidate its basic assumptions. The fit includes: (i) the Coulomb Criterion and its temperature dependence; and (ii) the dilative and shear apparent activation volumes at yield at all pressures.     

The extensional flow of poly(methyl methacrylate) and high-impact polystyrene at thermoforming temperatures

The work described in the present paper was performed to establish stress–strain–time relationships at plastic sheet thermoforming temperatures. The relationships are correlated with sheet-forming “formability”. Specimens of poly(methyl methacrylate) at 165°C and high-impact polystyrene at 122°C were extended to large strains at constant cross-head velocities. Initial strain rates were between 4.2 × 10^?3/sec and 1.6 × 10^?1/sec. It was found that the flow stress σ was related to the true strain ε and the elapsed time t by a relation σ = Kt^m′εⁿ, where K is a constant and n and m′ are indices. The value of n for both materials was approximately one. The value of m′ was ?0.052 and ?0.33 for poly(methyl methacrylate) and high-impact polystyrene, respectively. Tests were also performed in which the cross-head velocity was increased in steps. It was found that the flow stress in these tests followed the same relationship as in the constant cross-head velocity tests.     

A constitutive equation for creep in polymer concretes and their resin binders

We present here a method for superposing creep measurements on polymer concrete (PC), taken at different temperatures, imposed stresses, and resin contents, onto master curves, which describe the respective responses of various PC systems and their resin binders, to compressive, tensile, and flexural loads. This treatment is extended to systems reinforced with chopped glass fiber and montmorillonite (MMT). The general applicability of this superposition is tested with creep measurements by other investigators under tensile, compressive, and flexural loads. The results make it possible to predict the long-term creep behavior of unfilled as well as reinforced glassy polymer systems at different temperatures and load conditions from limited, short-term data. Success of the multiple superposition suggests a generalized constitutive equation, which describes the creep compliance of these systems as a product of separable functions of each parameter in the form of shift factors for temperature (α_T), stress (α_σ), resin content (α_υ), fiber reinforcement (α_F), and MMT reinforcement (α_M): J(PC) = J_rα_Tα_σα_υα_Fα_Mt^m, where J_r is an appropriately chosen reference creep compliance. The time exponent m does not depend on the chemical nature of the polymer matrix.     

Bacillus cereus adhesion: an investigation of the physicochemical characteristics of surface and effect of bio adhesion on the properties of silicone

The initial microorganism adhesion on substrate is an important step for biofilm formation. The surface properties of the silicone and Bacillus cereus were characterized by the sessile drop technique. Moreover, the physicochemical properties (hydrophobicity; electron donor/electron acceptor) of surface adhesion and the impact of bio adhesion on the silicone were determined at different time of contact (3, 7, and 24?h). The results showed that the strain was hydrophilic (Giwi?=?3.37?mJ/m²), whereas the silicone has hydrophobic character (Giwi?=??68.28?mJ/m²). Silicone surface presents a weak electron-donor character (γ ^??=?2.2?mJ/m²) conversely to B. cereus that presents an important electron donor-parameter (γ ^??=?31.6?mJ/m²). The adhesion of B. cereus to silicone was investigated using environmental scanning electron microscope and image analysis was assessed with the Matlab^® program. After 3?h of contact, the data analysis, confirmed the bio adhesion with an amount of 9.610⁵?cfu/cm² adhered cells. After 24?h, the percentage of silicone covered reached 93%. Furthermore, despite the difference in hydrophohbicity, the interaction between B. cereus and substrata was favoured by the thermodynamic model of adhesion (ΔG _adhesion ?<?0). The real time investigation of the effect of B. cereus adhesion on the physicochemical properties of silicone has revealed that the substrata becomes hydrophilic (θ°?=?47.3, ΔGiwi?=?23.7?mJ/m²), after 7?h of contact. This bio adhesion had also favoured the increase of electron donor/acceptor character of silicone (γ ^??=?53.1?mJ/m² and γ ⁺?=?5.3?mJ/m²).     

Mechanical Behavior of Polyacetal and Thermoplastic Polyurethane Elastomer Toughened Polyacetal

In view of the high potential of polyacetal (polyoxymethylene, POM)/thermoplastic polyurethane (TPU) elastomer blends in engineering applications, greater emphasis is placed on long-term properties of these blends. Though the creep behavior of pure viscoelastic polymers has been extensively studied and the temperature effect within the linear viscoelastic range has been explained on the basis of time–temperature superposition principle, only a little information is available about these blends. This work was carried out in pursuit of workable theories for actual engineering applications with their applicability defined, and secondly, to seek comprehension of the physical mechanisms which control the manifestation of nonlinear viscoelastic behavior in these blends. Validity of an equation of the type ? = ?° + ?⁺ tⁿ has been analyzed. The blends creep more than POM and the tendency to creep increases as the TPU content increases. It is found that n is a constant for a given blend and is independent of stress over the stress range considered. For all the blends, ?° is approximately a linear function of stress, whereas ?⁺ is a nonlinear function of stress irrespective of the composition of the blend. Monotonic tension tests have been carried out at three different strain rates and both POM and blends are found to be rate sensitive. Activation volume of POM and its blends with TPU has been evaluated and is found to increase as stress increases, in both cases.     

Comparison of the viscous and elastic components of two ABS materials with creep,stress relaxation and constant strain rate measurements using the universal viscoelastic model

In general, the universal viscoelastic model evaluated in this study was found to adequately predict constant strain rate, creep, and/or stress relaxation measurements from the constants determined from constant strain rate measurements. The elastic and viscous components for two acrylonitrile–butadiene–styrene (ABS) viscoelastic materials were also easily isolated using this new universal viscoelastic model. The creep measurements for ABS‐A (25383‐A) and ABS‐N (LL‐4102‐N) at three different stresses allowed elucidation of the common creep intercept strain of the calculated creep slopes that was designated as the “projected elastic limit.” Once the values for n and β were evaluated from creep measurements, then the creep variation of the universal viscoelastic model yielded a reasonably good fit of the measured creep data for both ABS‐A and ABS‐N. The extensional viscosity constant λ_E was found to be 7.2% greater for ABS‐A than for ABS‐N. Consequently, ABS‐N was found to have a lower extensional viscosity in secondary creep than that of ABS‐A at any specific strain rate. The value of the efficiency of yield energy dissipation n for ABS‐N as determined from creep measurements was also 37.6% larger than the value of n for ABS‐A. In addition, the projected elastic limit ?_I for ABS‐A was 2% greater than the projected elastic limit for ABS‐N. These observations indicated that ABS‐A should be slightly more solidlike than ABS‐N. However, both ABS‐A and ABS‐N were significantly more solidlike than liquidlike because both of their values for the efficiency of yield energy dissipation n were very close to zero. In general, values of n range from 0 < n < 1 with a material characterized as being essentially pure elastic having a value of n = 0. Using the yield strain as the failure condition for constant strain rate and stress relaxation measurements and the strain at critical creep, the failure condition for creep, it was found that the universal viscoelastic model allowed these failure criteria to yield remarkably good agreement on a projected time scale. This agreement resulted even though separate and independent data were used to evaluate these three different techniques for both ABS‐A and ABS‐N. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1298–1318, 2003     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

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.