Quantitative characterization of deformation in polypropylene fibers

A modus operandi is developed for characterizing, in quantitative morphological terms, the structural changes occurring during the preparation (spinning, drawing, and heat setting) and testing (tensile modulus) of isotactic polypropylene fiber. This involves the application of the following eight different physical techniques: wide-angle x-ray diffraction, birefringence, density, sonic modulus, small-angle x-ray diffraction, dark-field microscopy, small-angle light scattering, and tensile modulus. Structural changes on several organizational levels, the spherulitic, the interlamellar, and the molecular, are determined in this manner and related to the processes involved.     

Microstructural rearrangement during heat treatment of drawn nylon 66 fiber

Melt-spun nylon 66 fibers were drawn and subsequently heat treated isothermally and quenched. The heat-treated fibers were then examined by wide-and small-angle x-ray scattering (WAXS and SAXS), by differential scanning calorimetry (DSC), and by static mechanical testing. These measurements allow one to follow microstructural changes taking place during the course of the heat treatment. WAXS results show that as the treatment progresses, the crystallites become both more perfect and more disoriented with respect to the fiber axis. SAXS results show crystallite thickening. DSC results show that the melting point increases, goes through a maximum, and then decreases as the heat treatment progresses. The tensile modulus decreases with time to an asymptotic level. The changes in crystallite perfection and thickness occur more rapidly than do the changes in crystallite orientation, modulus, and melting point. A model is proposed whereby the two time frames are related to intracrystalline and intercrystalline processes, respectively.     

热处理对聚醚醚酮晶体结构参数及结晶度的影响

采用广角Ｘ射线衍射（ＷＡＸＤ）方法研究了不同热处理温度下聚醚醚酮（ＰＥＥＫ）的晶胞参数、微晶尺寸及结晶度的变化。根据Ｘ射线散射强度理论，运用图解多重峰方法导出了以ＷＡＸＤ方法计算ＰＥＥＫ结晶度的公式；用此公式对经不同热处理的ＰＥＥＫ样品进行计算，结果与由密度法及量热法测定的结果具有较好的可比性。     

Structural transformation of ultra-high modulus and molecular weight polyethylene fibers by high-temperature wide-angle X-ray diffraction

Wide-angle x-ray diffraction (WAXD) of the ultra-high modulus and molecular weight polyethylene (UHMWPE) fibers at room temperature shows a predominantly orthorhombic structure with trace amount of nonorthorhombic crystals and very low amorphous contents. The calculated unit cell dimensions a and b of the orthorhombic crystals are 7.36 (±0.04) Å, and 4.89 (±0.04) Å, respectively. The apparent crystallite sizes perpendicular to the orthorhombic 110 and 200 reflection planes are 169.8 and 143.4 Å, respectively. The crystallite size perpendicular to the nonorthorhombic 010 reflection is 149.4 Å. The crystal density is calculated to be 1.02 g/cc. With increasing temperature, the thermal expansion coefficient in the a direction is much higher than that in the b direction which explains the structural transformation from the orthorhombic crystals to a pseudohexagonal form. Tension along the fiber axis while being heated during the high-temperature x-ray diffraction (HTWAXD) scanning has shown enhanced structural transformation from the orthorhombic form to the monoclinic form. Structural transformation from the orthorhombic form to the pseudohexagonal phase is not observed on the UHMWPE fibers under axial tension or annealing conditions in HTWAXD. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 623–630, 1997     

热处理过程中聚酯长丝的形态变化

在自制的红外三因素处理机上~[1],用红外加热在定张力下对聚对苯二甲酸乙二酯(PET)成品长丝进行热处理(二次定型)。用X-光衍射(WAXS)、X-光小角散射(DAXS)、红外光谱(IR)和双折射方法,测定样品的热收缩、结晶度、晶粒尺寸和取向、非晶取向、长周期和链折叠带强度。所得形态参数的变化表明,处理温度在200℃以上时,张力不再阻碍链折叠。不同定张力样品的形态研究表明,存在阻碍链折叠的某个张力转折值。本文条件下,这个张力值为f_(critical)=0.066g/dtex 。张力大于此值,链折叠过程受阻。     

Deformation of lamellar structures: Simultaneous small- and wide-angle X-ray scattering studies of polyamide-6

Structural changes during tensile deformation in semicrystalline polymers are studied by the analysis of both small- and wide-angle X-ray scattering data from polyamide-6 fibers. The strain in the lamellar spacing is about the same as or higher than the fiber strain, suggesting that fiber elongation occurs by the deformation of the lamellar stack rather than slippage of the fibrils, especially during initial stages of elongation. The modulus of the lamellar structure is approximately 5 GN/m², and this is close to the fiber modulus, which is only 2–3% of the crystal modulus. Fiber modulus is, therefore, determined by the lamellar structure as much as by the interfibrillar oriented chain segments. The four-point small-angle X-ray scattering pattern in the relaxed fiber transforms reversibly into a two-point pattern under strain. The structures that correspond to these two patterns, the bistable states of the lamellae, coexist until fiber breakage. The structure that gives rise to the two-point pattern determines the ultimate strength of the fiber. Despite the small crystalline strain in the fiber direction, it is possible to follow the almost fully reversible changes in the orientation, size, and unit cell of the lamellar crystals. It is proposed that the appearance of the two-point pattern, the decrease in the lateral crystallite size, and the increase in the stack diameter are due to tilting of the lamellar surface caused by large-scale reversible strain in the interlamellar amorphous regions. This tilt is accomplished by slippage of the hydrogen-bonded sheets along the chain axis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 691–705, 2002     

乙烯-α-烯烃共聚物的结晶性能及其临界序列结晶长度的研究

本文用DSC、WAXD及偏光显微镜(PLM)方法,研究了化学反应法催化剂合成的乙烯-α-烯烃共聚物的结晶性能及其临界序列结晶长度。结果表明,随共聚物中α-烯烃含量增大,共聚物的微晶尺寸、结晶度及熔点均逐渐减小,而晶胞参数增大。变化的辐度戊烯>辛烯。共聚物的临界结晶序列长度(n)和k值均戊烯<辛烯。上述结果表明影响支链进入晶格的主要因素是α-烯烃支链长度和结构。     

Influence of film preparation procedures on the crystallinity, morphology and mechanical properties of LLDPE films

Influence of various film preparation procedures on the crystallinity, morphology and mechanical properties of pure linear low-density polyethylene and its calcite filled composite films has been studied using differential scanning calorimeter (DSC), wide-angle X-ray diffractometer (WAXRD), atomic force microscope (AFM) and ultimate tensile testing machine (UTM). The film preparation procedures include variation in cooling rates such as quenching, force (fan) and natural cooling and in techniques such as extrusion followed by melt squeezing and compression molding. The heat of fusion (from DSC), the degree of crystallinity (from WAXRD) and the crystallite size (from WAXRD and AFM) are found to be the highest for naturally cooled specimen, followed by fan cooled and quenched ones. The AFM images of surface topology exhibit stacked lamellar morphology for forcefully cooled (fan cooled and quenching) samples and spherulitic ‘lozenges’ for naturally cooled ones. The Young’s modulus and yield stress (from UTM) are the highest for naturally cooled samples, followed by fan cooled and quenched ones. Amongst the calcite filled composites, the ‘base film’, which is prepared by extrusion followed by melt squeezing and natural cooling, exhibits the lowest heat of fusion, degree of crystallinity and Young’s modulus, but the highest yield stress, elongation at break and tensile strength compared to the compression molded ones.     

Oriented crosslinked polyethylene pipes by a novel extrusion method

Crosslinking and stretching (2.5 times along the circumferential direction) of the molten polymer during extrusion produced pipes with dominantly circumferential orientation and a lower degree of axial chain orientation. Differential scanning calorimetry (crystallinity and crystal thickness), density measurements (crystallinity), X-ray diffraction (c-axis orientation), infrared dichroism measurements (crystalline and amorphous chain orientation) and contraction measurements (molecular draw ratio) assessed the microstructure of the pipe material. The mechanical properties of the oriented material were assessed by uniaxial tensile tests. The orientation was biaxial with the main orientation in the circumferential direction and a lesser orientation in the axial direction. The maximum degree of circumferential orientation was obtained at the inner wall of the pipe. The lower degree of crosslinking of the core material allowed slippage of chains during the stretching of the molten polymer and it is suggested that this is the cause of the lower degree of orientation of the core material. The oriented pipe material exhibited a 5-10% higher degree of crystallinity and higher crystal thickness than conventionally crosslinked material. The tensile modulus and the tensile strength of the oriented, cross-linked material was greater along the axial direction than along the circumferential direction. The circumferential and axial moduli for the oriented, crosslinked pipe were greater than the corresponding moduli of the non-oriented cross-linked pipe material. Another pipe based on crosslinked PE that were first circumferentially stretched 2.5 times and later axially stretched 10 times (in the molten state) showed, despite the fact that it exhibited pronounced axial orientation almost a balanced tensile modulus (4.3±0.2 GPa) in the axial-circumferential plane. Atomistic modelling showed that the orientational dependence of the density of the amorphous phase is small.     

Effect of gamma-irradiation on some structural characteristics of NiO

Pure NiO specimens were prepared by the thermal decomposition of pure basic nickel carbonate in air at 400 and 600°C. The obtained solids were exposed to different doses of γ-irradiation ranging between 10–80 Mrad. The change in residual microstrain, lattice parameter and crystallite size due to the irradiation process were investigated by X-ray diffraction analyses.The results revealed that γ-irradiation effected important changes in the structural characteristics of NiO lattice. No detectable change was observed for the crystalline size of NiO-400°C; however, the crystallite size of NiO-600°C decreased by increasing the dose up to 20 Mrad and increased at higher doses but still remaining smaller than that measured for the unirradiated specimen.The lattice parameters of NiO preheated at 400 or 600°C were found to increase as a function of the dose. These results were attributed to progressive removal of Ni³⁺ ions acting as lattice defects in NiO solid.The microstrains in NiO specimens precalcined either at 400 or 600°C were found to decrease progressively by increasing the dose falling to minimum values at doses of 40 and 80 Mrad for the solids preheated at 600 and 400°C, respectively. The augmentation of the exposure dose above 40 Mrad for NiO-600°C resulted in an increase in microstrain which, however, remained always smaller than those found for the unirradiated solid. The strain-relief in NiO-600°C due to γ-irradiation took place, mainly, via splitting of its crystallites. On the other hand, the progressive removal of lattice defects (Ni³⁺ ions) due to the irradiation process might account for the observed strain-relief in NiO-400°C.     

Effect of Calcination Temperature on the Structural,Thermodynamic, and Optical Properties of MoO3 Nanoparticles

Temperature dependence of the structural, thermodynamic, and optical properties of MoO₃ nanoparticles synthesized using sol–gel and sonication methods were studied. MoO₃ nanoparticles showed variation in crystallite shape from hexagonal to orthorhombic and crystallite size in the range 3.05–5.21 nm with bandgap in the range 4.11–4.36 eV with change in the calcination temperature and the method of synthesis. Rietveld refinement of the X‐ray diffraction (XRD) data confirmed the crystallite phase transition with space group PE and Pbnm with change in the lattice parameter ratio. Activation energy was calculated using XRD and TGA–DSC (thermogravimetry–differential thermal analysis) data and was found to be close to 4 kJ/mol. The bandgap fluctuation was due to the size dependence of the blue shift, which indicates strong quantum confinement due to the Bohr radius effect. Optical parameters such as the extinction coefficient, refractive index, optical conductivity, dielectric functions, and Urbach energy were calculated and found to depend on electron–phonon interactions.     

Properties and structure of solvent-spun and viscose-type fibres in the swollen state

The conditioned and wet tensile strength resp. modulus of solvent-spun and viscose-type cellulose fibres was correlated with their crystallite and amorphous orientation factor. It was found that the extrapolation of these tensile properties to the maximum degree of orientation results in identical values of the tensile strength resp. modulus in the conditioned and water swollen state. Proportional to a decreasing orientation factor the loss of strength and modulus by swelling increases. Additionally, a positive correlation was found between the wet tensile strength resp. modulus and the intensity of the interference of the equatorial small-angle x-ray scattering measured in the swollen state. This interference is caused by the elementary fibrils. The intensity of this interference is a measure for the fibrillar character of the swollen fibre structure. The fibrillability of the fibres suspended in water correlates positively with the crystallite orientation factor.Extracts presented at the Conference Cellulose '91 December 2–6, 1991 New Orleans, USA     

Structure and superstructure of carbon fibres

The structure of carbon fibres consists of stacks of carbon layers oriented parallel to the fibre axis. From X-ray wide-angle scattering studies (WAXS) one obtains various structural parameters characterizing the perfection of the stacking and the orientation of the layers. The latter is quantitatively related to the tensile modulus of the fibres. Small-angle scattering studies (SAXS) are used to determine size, shape and orientation of microvoids. For carbon fibres with high heat treatment temperatures (HTT), a correlation between microvoid content and elongation at break is observed which indicates an optimum value for the microvoid content. Electrochemical intercalation is used to obtain information on the accessibility of the carbon layer structure.     

Quantitative evaluation of stress distribution in bulk polymer samples through the comparison of mechanical behaviors between giant single‐crystal and semicrystalline samples of poly(trans‐1,4‐diethyl muconate)

The Raman shift and crystallite modulus were measured under the application of tensile force for a giant single crystal and a series of uniaxially oriented semicrystalline samples of poly(trans‐1,4‐diethyl muconate) (polyEMU). The apparent Raman shift factor α^app or a vibrational frequency shift per 1 GPa tensile stress was higher for the semicrystalline samples with lower crystallinity or lower bulk modulus. The apparent crystallite modulus E or Young's modulus along the chain axis in the crystalline region was not constant but varied remarkably between the giant single crystal and semicrystalline samples. A systematic change in α^app and E among the polyEMU samples with different preparation history could be interpreted quantitatively on the basis of a mechanical series parallel model consisting of crystalline and amorphous phases. The origin of different E and α^app was speculated to be a stress concentration on the taut‐tie chain contained as a parallel crystalline component in the mechanical model. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 444–453, 2003     

The effect of ‘crystallinity’ and structural disorder on the electrochemical performance of substituted nickel hydroxide electrodes

β_bc-Nickel hydroxide exhibit non-uniform broadening reflections in their PXRD pattern due to the presence of structural disorder. β_bc-Nickel hydroxide electrodes with smaller crystallite size and structural disorder reversibly exchanges 0.9e/Ni. Co/Zn/Ca/Cd-substituted β_bc-nickel hydroxide samples also display non-uniform broadening of reflections in their powder X-ray diffraction patterns with smaller crystallite size and exchanges 0.7–0.8e/Ni. Hydrothermal treatment of β_bc-nickel hydroxide slurry at 170 °C results in an ordering of reflections in their powder X-ray diffraction pattern with an increased crystallite size. Crystalline β-nickel hydroxide electrode reversibly exchanges 0.3–0.4e/Ni. Hydrothermal-treated Co/Zn/Ca/Cd-substituted β_bc-nickel hydroxide slurries at 170 °C display sharp reflections with similar crystallite size and electrochemical activities as that of crystalline β-nickel hydroxide. This clearly demonstrates that partial substitution of Co/Zn/Ca/Cd in the nickel hydroxide matrix does not show any dramatic improvement in their electrochemical activity at 25–30 °C. Structural disordered material with smaller crystallite size delivers electrochemical activity close to theoretical capacity.     

Polyurethane Ionomers from Cycloaliphatic Diisocyanate and Polytetramethylene Glycol

Abstract

Segmented polyurethane (PU) ionomers were prepared from cycloaliphatic diisocyanate [methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) and isophoron diisocyanate (IPDI)] and polytetramethylene glycol (PTMG) by using an anionic-type chain extender, viz., dimethylol propionic acid (DMPA). The effect of ionic content and butanediol (BD) on the state of dispersion and physical properties of emulsion-cast film was determined using Autosizer, transmission electron microscopy (TEM), Instron, and Rheovibron. With increased incorporations of DMPA in PU, particle size of emulsion decreased asymptotically, tensile modulus and strength increased, and the glass transition temperature (T _g) moved toward the higher temperature. On the other hand, with increased incorporation of BD in PU, particle size of emulsion, tensile modulus, and strength of the emulsion cast film increased, and the major transition of soft segment moved toward higher temperature. With regard to the structural effect of the isocyanate, H₁₂MDI gave finer dispersion and better mechanical properties over IPDI.     

Disorder in layered TiCl3. Symmetry of the coordination site

The structural layers of TiCl₃ consist of two monoatomic layers of chlorine atoms octahedrally coordinated to intercalating Ti atoms. Mechanical (grinding) and/or chemical treatment of the regular α- or γ-forms may produce the disordered δ-form, wherein shifts and rotations between neighboring layers give rise to the largest disorder compatible with close-packing of the chlorine layers, accompanied by reduction of crystallite size both along the layers and across them. A Bernoullian statistical model fully describes the statistical structure of the polycrystalline samples in terms of 4 parameters, two of them relating with the stacking disorder, the other two with crystallite size distribution. The catalytic sites for isospecific α-olefin polymerization lie on the side edges of the structural layers. It is shown that Ti atoms on these edges possess two isochiral free valencies, enabling them to exchange the roles of the (Ti-coordinated olefin) and of the (Ti-growing chain) bonds at each polymerization step with no change of the local chirality, in analogy with the metallocene-based isospecific catalysts.     

A New Molecular Theory of Non‐Linear Viscoelasticity for Vitrifiable (or Crystallizable) Thermoplastic Polyurethane Elastomers

The molecular theory of non‐linear viscoelasticity for vitrifiable thermoplastic polyurethane elastomers (VTPUE) is a refinement and extension of viscoelastic theory of thermoplastic elastomers and polyurethanes to glassy transition, a structural model and a mechanism of vitrification for glassy polymers were proposed. Five kinds of constituent chains with Nagai chain constraint consisting of soft‐domains, hard‐domains, and entanglements are used as the elementary structural and statistical ensemble units for the correlation of molecular and phase‐domain structures to the static and dynamic mechanical behaviors. So the influences of non‐Gaussian in character, the phase separation of domain, the network topology of structure, the affined deformation of constituent chains, and the thermal history are all taken into account in the constituent chains of the theory. Free energies of deformation for the VTPUE segment copolymer were calculated by the statistical mechanics with the probability distribution functions of the sizes for the five kinds of constituent chains. Then the static constitutive equations and modulus of four types of deformation and the dynamic shear viscosity, modulus and loss tangent of VTPUE are derived from the proposed theory. The theory is successful in relating the molecular chain parameters C₁₀₀, C₀₂₀, and C₂₀₀ to the constitutive equations and modulus under large deformations and the micro‐domain structure to the complex shear viscosity and modulus and the loss tangent. The dynamic shear modulus and loss tangent of VTPUE are related to the domain structures through the fraction of hard segments (W_h), the molecular weight of soft segment (M_ns), and the growth dimensional parameters of hard and soft domains (β). Two series of linear VTPUE copolymers (ES and ET) with different fractions(W_h) of hard segments and molecular weight (M_ns) of soft segments were prepared. Their static and dynamic mechanical properties were studied by uni‐axial extension and dynamic analysis tests. Then the constitutive equation at uni‐axial extension and the expressions of shear modulus and loss tangent are verified by these experimental data, and excellent agreement between the theory and experiments is achieved. It is shown, that the proposed theory can predict the viscoelastic behavior of vitrifiable thermoplastic polyurethanes.     

Weibull statistical analysis and experimental investigation of size effects on tensile behavior of dry unidirectional carbon fiber sheets

In this study, experimental tests and a statistical analysis are conducted to verify the size effects associated with length on the tensile behavior of dry unidirectional carbon fiber sheets (DUCFS). As a statistical method, the two-parameters Weibull theory is considered. To verify the validity of the Weibull theory, four sets of direct tensile test were made on DUCFS specimens having different lengths. The direct tensile tests consist to evaluate the size effects associated with length on the mechanical properties of DUCFS such as tensile strength and the Young's modulus. The experimental results show a size effect of length on the tensile strength of DUCFS. Indeed, the tensile strength decreases when increasing the specimen length. In addition, the experimental results demonstrate that there is no size effect on the failure mode and on the Young's modulus of DUCFS. Finally, Weibull weakest link theory is used to predict the tensile strength size effect on DUCFS specimens. A good agreement was shown between the test data and predicted results obtained using the Weibull weakest link theory.     

THE INFLUENCE OF HEAT TREATMENT ON STRUCTURES OF THE AGGREGATED STATE OF POLYAMIDE-1010

The structural parameters of the aggregated state of polyamide (PA)-1010 annealedat various temperatures were computed by means of the desmearing intensity from SmallAngle X-ray Scattering (SAXS) measurements and by using the concept of the distance dis-tribution function. The results indicated that the structural parameters of the aggregatedstate were strongly dependent upon heat treatment conditions and the maximum valuesof the structural parameters were obtained for the samples annealed at T = 175℃. Theparticle size Z annealed at different temperature was ranged between 8.1--12.8nm, and thevalues of the distance distribution function P_(max)(Z) were obtained when Z = 4.0--6.8nm.Using one dimension electron density correlation function (1D EDCF) method long period(L) and thickness of the lamellar (d_0) were estimated and were found to increase with theincrease of the degree of crystallinity.