Igors Sics

Molecular orientation and structural development in vulcanized polyisoprene rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction

Abstract Molecular orientation and strain-induced crystallization of vulcanized natural rubbers (by sulfur and peroxide) and synthetic polyisoprene rubber (by sulfur) during uniaxial deformation at 0 °C were studied by in situ synchrotron wide-angle X-ray diffraction. The high intensity of synchrotron X-rays and new image analysis methods made it possible to estimate the mass fractions of strain-induced crystals and amorphous chains in both oriented and unoriented states. Most of the polymer chains (∼75%) were found to be in the random coil state even at large strains (>5.0). Only about 5% the amorphous chains were oriented, whereas the rest of the chains (∼20%) were in the crystalline phase. Sulfur vulcanized and peroxide vulcanized natural rubbers did not exhibit notable differences in structure and property relationships. In contrast, synthetic polyisoprene rubber showed a different behavior of deformation-induced structural changes, which can be attributed to the difference in cross-link topology. Our results indicated that strain induces a network of microfibrillar crystals in both natural and synthetic polyisoprene rubbers due to the inhomogeneity of cross-link distribution that is responsible for their elastic properties.

Mechanism of strain-induced crystallization in filled and unfilled natural rubber vulcanizates

Structure evolution during deformation of unfilled natural rubber (NR) vulcanizate and filled ones with carbon black or calcium carbonate was investigated by the synchrotron x-ray diffraction. The crystallization onset strain, α0, was found to decrease by the inclusion of the filler. However, corrected α0 values into the effective strain ratio of deformable rubber portion were almost constant between filled and unfilled samples. Accordingly, our model of strain-induced crystallization of unfilled NR vulcanizates, assuming that melting temperature is independent of network-chain length (n), was applied to the filled samples. The discrepancy between classical theories and experimental results was thought to come from the distribution of n. By the inclusion of filler, the lateral crystallite size was decreased but the orientational fluctuation increased. The lattice of the strain-induced crystallites changed almost linearly with the nominal stress. In addition, the degree of lattice deformation decreased wit...

Orientation‐induced crystallization in isotactic polypropylene melt by shear deformation

Development of orientation-induced precursor structures (nuclei) prior to crystallization in isotactic polypropylene melt under shear flow was studied by in-situ synchrotron small-angle X-ray scattering (SAXS) and rheo-optical techniques. SAXS patterns at 165 °C immediately after shear (rate = 60 s -1 , t s = 5 s) showed emergence of equatorial streaks due to oriented structures (microfibrils or shish) parallel to the flow direction and of meridional maxima due to growth of the oriented layer-like structures (kebabs) perpendicular to the flow. SAXS patterns at later times (t = 60 min after shear) indicated that the induced oriented structures were stable above the nominal melting point of iPP. DSC thermograms of sheared iPP samples confirmed the presence of two populations of crystalline fractions; one at 164 °C (corresponding to the normal melting point) and the other at 179 °C (corresponding to melting of oriented crystalline structures). Time-resolved optical micrography of sheared iPP melt (rate = 10 s -1 , t s = 60 s, T = 148 °C) provided further information on orientation-induced morphology at the microscopic scale. The optical micrographs showed growth of highly elongated micron size fibril structures (threads) immediately after shear and additional spherulities nucleated on the fibrils at the later stages. Results from SAXS and rheo-optical studies suggest that a stable scaffold (network) of nuclei, consisting of shear-induced microfibrillar structures along the flow direction superimposed by layered structures perpendicular to the flow direction, form in polymer melt prior to the occurance of primary crystallization. The scaffold dictates the final morphological features in polymer.

Effect of network-chain length on strain-induced crystallization of NR and IR vulcanizates

Abstract Strain-induced crystallization of natural rubber (NR) and synthetic isoprene rubber (IR) with various crosslinking densities was investigated by wide angle X-ray diffraction using a synchrotron radiation and simultaneous tensile measurements. The elongation ratio at the onset of crystallization (αc) was almost independent of crosslinking density. IR samples showed larger αc values than NR because of the lower stereoregularity of IR. These results suggest that the onset of crystallization is determined by increased melting temperature by strain due to an entropic reason. The amount of oriented amorphous component changed approximately linearly with strain, and was a little larger in IR than in NR when compared at the same elongation ratio. At small strain (and stress), crystallinity in IR was lower than in NR. These results indicate that, at small strain region, the more stress is assigned to oriented amorphous in IR than in NR.

Strain-induced molecular orientation and crystallization in natural and synthetic rubbers under uniaxial deformation by in-situ synchrotron X-ray study

Abstract In-situ synchrotron wide-angle X-ray diffraction (WAXD) studies and simultaneous measurements of stress and strain during uniaxial stretching of various vulcanized rubbers were carried out (at room temperature and 0°C) to reveal the strain-induced molecular orientation and crystallization relationships. Rubbers evaluated included natural rubber (NR), synthetic poly-isoprene rubber (IR), poly-cis-1,4-butadiene rubber (BR) and butyl rubber (IIR). Some universal features were observed in these systems: (i) At high strains (> 5.0), the majority of the chains (up to 50 ≈ 75%) in natural and synthetic rubbers remained in the un-oriented amorphous state with only a small amount of crystalline fraction formed (10–20%). The rest of the chains were in the oriented amorphous state. (ii) During deformation, the oriented amorphous chains acted as precursors to strain-induced crystallization. A network of micro-fibrillar crystallites is formed within the closely populated vulcanization points, leading to the e...

Lateral Packing of Mineral Crystals in Bone Collagen Fibrils

Combined small-angle x-ray scattering and transmission electron microscopy studies of intramuscular fish bone (shad and herring) indicate that the lateral packing of nanoscale calcium-phosphate crystals in collagen fibrils can be represented by irregular stacks of platelet-shaped crystals, intercalated with organic layers of collagen molecules. The scattering intensity distribution in this system can be described by a modified Zernike-Prins model, taking preferred orientation effects into account. Using the model, the diffuse fan-shaped small-angle x-ray scattering intensity profile, dominating the equatorial region of the scattering pattern, could be quantitatively analyzed as a function of the degree of mineralization. The mineral platelets were found to be very thin (1.5 nm approximately 2.0 nm), having a narrow thickness distribution. The thickness of the organic layers between adjacent mineral platelets within a stack is more broadly distributed with the average value varying from 6 nm to 10 nm, depending on the extent of mineralization. The two-dimensional analytical scheme also leads to quantitative information about the preferred orientation of mineral stacks and the average height of crystals along the crystallographic c axis.

Shear‐Induced Orientation and Structure Development in Isotactic Polypropylene Melt Containing Modified Carbon Nanofibers

The shear‐induced crystallization behavior of isotactic polypropylene (iPP) nanocomposite melt containing modified carbon nanofibers (MCNFs) was investigated by rheo‐SAXS (small‐angle X‐ray scattering) and rheo‐WAXD (wide‐angle X‐ray diffraction) techniques using synchrotron radiation. Under quiescent conditions, the nucleating effect of MCNFs on crystallization of iPP was pronounced and the system exhibited a remarkably low saturation point (ca. 0.05 wt% of MCNF). In‐situ SAXS and WAXD results showed the development of shear‐induced crystalline structures and lamellar morphology in nanocomposite melts. Under the same shear conditions, the filled system exhibited notably faster kinetics compared with the unfilled system. The oriented crystalline fraction was found to decrease with the MCNF loading, indicating the competition between oriented crystals (induced by shear) and unoriented crystals (due to the nucleating effect of MCNF). At the early stages of crystallization, the amount of the oriented crystals increased with the MCNF concentration, suggesting that the nanofiller hindered the motion of polymer chains after the cessation of flow resulting in the delayed relaxation of stretched polymer segments. Dedicated to Prof. Phillip H. Geils seventy‐fifth birthday.

Cold crystallization of poly(ethylene naphthalene-2,6-dicarboxylate) by simultaneous measurements of X-ray scattering and dielectric spectroscopy

The isothermal cold crystallization of poly(ethylene naphthalene-2,6-dicarboxylate) was investigated by simultaneous small and wide angle X-ray scattering and dielectric spectroscopy (DS). By this experimental approach, simultaneously collected information was obtained about the specific changes occurring in both crystalline and amorphous phases during crystallization, namely about the chain ordering through wide angle X-ray scattering, about the lamellar crystals arrangement by means of small angle X-ray scattering, and about the amorphous phase evolution by means of DS. The results indicate that average mobility of the amorphous phase suffers a discontinuous decrease upon passing from the primary to the secondary crystallization regime. We interpret these results assuming that the restriction to the mobility of the amorphous phase occurs mainly in the amorphous regions between the lamellar stacks and not in the amorphous regions within the lamellar stacks.

Combined techniques of Raman spectroscopy and synchrotron two-dimensional x-ray diffraction for in situ study of anisotropic system: Example of polymer fibers under deformation

Simultaneous measurements of Raman spectroscopy and synchrotron two-dimensional (2D) wide-angle x-ray diffraction (WAXD) have been successfully demonstrated for in situ study of an anisotropic system: isotactic polypropylene (iPP) fiber under tensile deformation. A fiber-optic probe was used to remotely deliver the incident laser beam on the sample as well as to collect the Raman signal based on the confocal arrangement, whereas high resolution 2D WAXD patterns were obtained simultaneously at the same position during deformation of polymers. The combined techniques yielded complementary information on the molecular structural evolution in both crystalline and amorphous phases. 2D WAXD results showed that the α-form iPP crystals were converted into the mesophase upon stretching at room temperature. Corresponding Raman spectra showed that characteristic bands from the crystal phase became weaker or disappeared during the transition from the crystal phase to the mesophase. However, the bands associated with ...

Small-angle X-ray study of the three-dimensional collagen/mineral superstructure in intramuscular fish bone

Synchrotron small-angle X-ray scattering (SAXS) was conducted on native intramuscular shad/herring bone samples. Two-dimensional SAXS patterns were quantitatively analyzed with special consideration for preferred orientation effects, leading to new insights into the three-dimensional superstructure of mineralized collagen fibrils in shad/herring bone.