The effect of molecular weight on the structure and thermal properties of polyethylene

The morphology of polyethylene single crystals prepared isothermally in solution was found to be independent of molecular weight. The enthalpy of fusion, lamellar fold period, and optical appearance were invariant for samples grown from fractions ranging from 20,000 to 2,000,000 in molecular weight. The mass fraction of lamellae which thicken during heating decreased linearly with increasing log molecular weight. The melting temperature of the crystals was also nearly independent of molecular weight.

The superheating of polyethylene crystals was observed to be a function of molecular weight and morphology. At a comparatively high molecular weight the heating rate of the calorimeter exceeded the crystal melting rate, which shifted the observed melting temperature to an anomalously high value. The incorporation of defects within the crystals by irradiation-induced cross-links or chain entanglements increased the melting rate of the high molecular weight samples and thereby minimized the effects of superheating.

The apparent heat of fusion of melt crystallized polyethylene decreased linearly with increasing log molecular weight. In contrast to this behavior the crystallinity of single crystals from dilute solution was independent of molecular weight.

In previous papers we have shown that reorganization of polymer single crystals is suppressed by cross-linking [1—3]. With the appropriate selection of heating rate and irradiation dose, the melting temperatures of solution grown crystals of various morphologies were determined in the absence of lamellar thickening. The observed melting temperatures of polyethylene single crystals with different X-ray fold periods were found to fit the following expression:

T_m = T_m0[1—2σ_e/H_f?] with an equilibrium melting temperature (T_m0) of 145.8 ± 1.0°C and a surface free energy (σ_e) of 89 ± 5 ergs cm^?2 for a polyethylene crystal of infinite dimensions. In addition, at a constant heating rate it was observed that the fraction of crystals which thickened prior to melting decreased with increasing fold period.

Since cross-linking polyethylene increases the molecular weight of the material, it is instructive to investigate the reorganization characteristics of single crystals prepared from polyethylene fractions. Single crystals were prepared in xylene from molecular weight fractions of polyethylene and the effect of molecular weight upon the structure and thermal properties of the crystals was determined.     

Structure and mechanical properties of nylon 6.12 prepared by temperature slope crystallization. II. Rolling deformation and microhardness of the oriented negative spherulite

Oriented negative spherulites of nylon 6.12 were crystallized by the temperature slope method. Rolling deformation of the negative texture was performed in three directions. The deformation mechanism of the negative spherulites was investigated by x-ray diffraction and microhardness measurements. Slip deformation between crystalline lamellae (interlamellar slip) was observed in the first stage of deformation. The results are compared with the rolling deformation of other polymer textures such as the positive spherulites of nylon 6.12 and β-phase isotactic polypropylene. In the rolling deformation of nylon 6.12, hydrogen-bonded (010) planes play an important role. For large deformations (λ > 1.5), preferential slip between (010) planes appears, resulting in a lamellar inclination of 60° and a decrease of the lamellar thickness. Microhardness measurements after rolling deformation of the oriented negative texture show good agreement with the structural analysis. The rapid decrease in the microhardness with increasing deformation can be explained by the lamellar thickness decrease brought about by the preferential slip between the (010) planes.     

Crystallization in Microdomains of a Block Copolymer Comprising Semicrystalline Block Observed by Simultaneous Measurement of SAXS and WAXS with H v‐SALS or DSC

Abstract

Semicrystalline block copolymers provide us with a fascinating model for studying the kinetics of crystallization. We performed the simultaneous measurement of small‐ (SAXS) and wide‐angle (WAXS) x‐ray scattering (SWAXS) with differential scanning calorimetry (DSC), or SWAXS with small‐angle light scattering (H _v‐SALS). The specimen used was polyethylene‐b‐poly(ethylene propylene) (PE‐b‐PEP) with the molecular weight of 44,200. The PE block has the melting point (T _m) at 108°C. We observed the time evolution of crystallization in the lamellar microdomains of PE‐b‐PEP after a temperature drop from 180°C (?T _m) to a variety of temperatures slightly below T _m. The exothermic signal was observed by DSC right after the temperature drop, while the four‐leaf‐clover pattern of H _v‐SALS and the SAXS peaks due to the lamellar microdomains were observed several minutes after the temperature equilibration. The WAXS peaks of (110) and (200) reflection were almost simultaneously detected with the H _v‐SALS and the SAXS peaks at crystallization temperature of 100°C. With the crystallization temperature closer to T _m, the WAXS crystalline signals showed up with longer time lag after the H _v‐SALS and the SAXS peaks began to appear. Interestingly, these phenomena are interpreted as that long‐range order of density fluctuation up to the order of micrometers was generated prior to the formation of crystals with partially ordered phase rather than the instantaneous crystalline nucleation.     

ELECTROCHEMICAL OXIDATION OF La2CuO4 SINGLE CRYSTALS

Bulk superconducting La₂CuO_4+δ single crystals are obtained by using electrochemical intercalation technique from the as-grown insulating samples. Oxidation is carried out by constant current I=10μA at temperature T=70℃ and room temperature, respectively. Structure and magnetic properties are studied by low-temperature X-ray diffraction and susceptibility measurements. A superconducting phase with T_c of 19K and δ-0.12 can be attributed to the formation of oxygen clusters. Room temperature oxidation is inhomogeneous: two superconducting phases with T_c1 of 24K and T_c2 of 8K and an antiferromagnetic phase are coexisting in the crystal. It is found that the appearance of T_c in this system has the "step" tendency.     

Effect of annealing on the structure and morphology of nylon 6 fibers

Changes in the structure of nylon 6 fibers annealed in dry and wet atmospheres were studied by small-and wide-angle x-ray diffraction. In the presence of water or saturated steam, fibers can be annealed to the same strucutral state at temperatures 70°C lower than in dry atmosphere. This is due to the enhanced mobility of the molecular segments in the amorphous region, a mechanism which is also known to lower the T_g by the same amount. Upon annealing under unconstrained conditions, lamellar spacing, crystallite size in the equatorial plane, crystalline as well as fiber density, and the chain-axis repeat increase with annealing-temperature; whereas crystalline orientation and the Van der Waals separation of the hydrogen-bonded sheets decrease. The monoclinic angle 8 remains constant at 66.7° (σ = 0.3°) and might depend on the starting fiber rather than on the treatment of the fiber. Most of these changes occur above a critical temperature of 170°C if dry, or 100°C if wet; rate of crystallization is also the highest under these conditions in nylon. The effect of these changes on such fiber properties as dyeing and the role of micro voids in dye diffusion and in dye uptake are discussed. Surface premelting and the accompanying changes in the surface structure of the lamellae, selective melting, and more importantly, the longitudinal motion of the nylon 6 chains and the resulting folding of interfibrillar extended amorphous chains are invoked to explain the shrinkage of the fiber, disorientation of the crystallites, increase in crystalline perfection, and the increase in lamellar spacing.     

Thermal conductivity of high-porosity biocarbon precursors of white pine wood

This paper reports on measurements of the thermal conductivity κ and the electrical conductivity σ of high-porosity (cellular pores) biocarbon precursors of white pine tree wood in the temperature range 5–300 K, which were prepared by pyrolysis of the wood at carbonization temperatures (T _carb) of 1000 and 2400°C. The x-ray structural analysis has permitted the determination of the sizes of the nanocrystallites contained in the carbon framework of the biocarbon precursors. The sizes of the nanocrystallites revealed in the samples prepared at T _carb = 1000 and 2400°C are within the ranges 12–35 and 25–70 Å, respectively. The dependences κ(T) and σ(T) are obtained for samples cut along the tree growth direction. As follows from σ(T) measurements, the biocarbon precursors studied are semiconducting. The values of κ and σ increase with increasing carbonization temperature of the samples. Thermal conductivity measurements have revealed that samples of both types exhibit a temperature dependence of the phonon thermal conductivity κ_ph, which is not typical of amorphous (and amorphous to x-rays) materials. As the temperature increases, κ_ph first varies proportional to T, to scale subsequently as ～T ^1.7. The results obtained are analyzed.     

Theoretical analysis of the effect of crystallization temperature on structure formation in flexible-chain polymers

Theoretical analysis of flexible-chain polymer crystallization was carried out over a wide temperature range from glass transition temperature T_g to melting temperature T_m. Temperature dependence of dynamic behavior manifesting in the decrease of crystallizing length with decreasing temperature was taken into account. The dependence of crystallizing length on temperature was obtained using chosen values of it at T_g and T_m. The crystallization with the formation of folded-chain crystals (type I) and uncoiled-chain crystals (type II) was considered. The analysis of thermodynamical favorability of both types of crystals with respect to temperature made it possible to obtain a flexible-chain crystallizing polymer phase diagram. This diagram shows the existence of two ranges where type II crystal formation is more favorable: a narrow range near T_m and the wider one near T_g, separated by the temperature range of crystallization with chain folding. Temperature dependences of type II crystals fraction in the system and their size were calculated. It is shown that the crystallization at considerable supercooling leads to the appearance of a great number of type II small crystals connected by tie chains. The system formed is characterized by a high degree of crystallite interconnection.     

Structure and crystallization of molecular complexes between poly(ethylene oxide) and hydroxybenzenes

The phase diagrams of the binary systems poly(ethylene oxide) (PEO)-resorcinol and poly(ethylene oxide)-p-nitrophenol show the presence of molecular complexes with well-defined stoichiometries. The crystal structure of these two molecular complexes has been determined from wide-angle x-ray diffraction patterns of stretched films and spherulites. The morphology of the two complexes crystallized from the melt is investigated by differential scanning calorimetry and small-angle x-ray scattering. The crystallization of the PEO-resorcinol complex from the melt gives integral-folded crystals with either extended chains (EC) or n-folded chains (n-FC). As observed for PEO oligomers, the fraction of EC crystals of the PEO-resorcinol complex increases with the crystallization temperature to give finally only EC crystals but in a larger range of crystallization temperatures than for pure PEO. On the other hand, the PEO-p-nitrophenol complex crystallizes over all the studied crystallization range as stable nonintegral-folded (NIF) crystals. Two proposals related to the crystal structure of these complexes and their mode of growth are invoked to explain these two greatly different morphologies at the lamellar level.     

Electrochemical determinations of the chemical diffusion coefficient and non-stoichiometry in AgCl

Measurements were made of the electronic conductivities, σ_e and σ_h, of AgCl as a function of P_Cl2 and of the chemical diffusion coefficient of n-type and p-type AgCl, respectively, in the temperature range of 360–440°C by means of the improved dc polarization technique. The deviation from stoichiometry, δ, in the formula Ag_1+δCl was calculated from the measured electronic conductivities and chemical diffusion coefficients. It was found that δ ranges from -10^?4 to 10^?6 according to P_Cl2. Based on the determined δ values, the imperfection equilibrium in AgCl are discussed.     

Effect of zinc salt on transport,structural, and thermal properties of PEG-based polymer electrolytes for battery application

Solid polymer polyethylene glycol (PEG)-based electrolytes composed with zinc acetate Zn(CH₃COO)₂ have been prepared by using solution blending. We proposed a scheme of PEG–zinc acetate for battery application. The structure confirmation was done by using X-ray diffraction studies detecting the phase variation. The thermal properties demonstrate the optimization of melting point (T _m) as a function of loading zinc acetate. The impedance analysis reveals that the role of ionic conductivity depends on the controlled concentration of Zn(CH₃COO)₂. Optimum ionic conductivity σ?~?1.55?×?10^?6 S?cm^?1 at room temperature (303 K) was observed for 70:30 composition. The linear variation in log σ vs 1000/T plot is based on the Arrhenius-type thermally activated process. The simultaneous discharge profile was confirmed by the solid-state electrochemical cell. Hence, the PEG–zinc acetate composition was suggested for polymer electrolyte battery application.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

Thermal desorption of Ag from oxidized W

Thermal desorption spectra (TDS) of Ag condensates deposited at two substrate temperatures T_s = 300 K and T_s = 779 K have been obtained. A shift of the temperature T_m of the maximum of the desorption flux R_e was observed. It was established that the shift of the maximum depends on the value of the initial coverage σ₀. A significant difference was found to exist between TDS of silver condensates deposited on oxidized and clean W substrates due to differences in the mechanism of condensation. Silver condensates were deposited on oxidized W at different initial conditions (T_s, impingement rates R_i, etc.) but equal σ₀. The corresponding TDS were compared and a conclusion has been drawn that the shift of T_m is due to the different structure of Ag condensates. TDS of Ag condensates deposited at room temperature (T_s = 300 K) were interpreted using the method of Bauer et al. [J. Appl. Phys. 45 (1974) 5164: Surface Sci. 53 (1975) 87]. The dependence of the desorption flux R_e on the substrate temperature T_s and coverage σ was treated on the basis of the Polanyi-Wigner equation and some parameters of the condensation process were evaluated.     

Microstructure,elastic, and inelastic properties of biomorphic carbons carbonized using a Fe-containing catalyst

The microstructure and amplitude dependences of the Young’s modulus E and internal friction (logarithmic decrement δ), and microplastic properties of biocarbon matrices BE-C(Fe) obtained by beech tree carbonization at temperatures T _carb = 850–1600°C in the presence of an iron-containing catalyst are studied. By X-ray diffraction analysis and transmission electron microscopy, it is shown that the use of Fe-catalyst during carbonization with T _carb ≥ 1000°C leads to the appearance of a bulk graphite phase in the form of nanoscale bulk graphite inclusions in a quasi-amorphous matrix, whose volume fraction and size increase with T _carb. The correlation of the obtained dependences E(Т _carb) and δ(T _carb) with microstructure evolution with increasing Т _carb is revealed. It is found that E is mainly defined by a crystalline phase fraction in the amorphous matrix, i.e., a nanocrystalline phase at Т _carb < 1150°C and a bulk graphite phase at T _carb > 1300°C. Maximum values E = 10–12 GPa are achieved for samples with Т _carb ≈ 1150 and 1600°C. It is shown that the microplasticity manifest itself only in biocarbons with T _carb ≥ 1300°C (upon reaching a significant volume of the graphite phase); in this case, the conditional microyield stress decreases with increasing total volume of introduced mesoporosity (free surface area).     

Structure and properties of polybutylene crystallized from the glassy state. I. X-ray scattering,DSC, and torsion pendulum

Isotactic polybutene (PB) can be quenched into a completely glassy state by quenching molten films into a solid-liquid mixture of isopentane, Freon, or ethanol. The crystallization of PB from the glass form was studied by x-ray scattering, differential scanning calorimetry (DSC), and dynamic mechanical spectroscopy (torsion pendulum). As for crystallization from the melt, PB crystallizes from the glass into a tetragonal crystal structure (Form II) at ca. 0°C, depending on sample thickness, and then transforms to the twinned hexagonal structure (Form I) upon aging at room temperature. In the presence of isopentane, PB crystallizes partially from the glass into the untwinned hexagonal (Form 1′) structure at ca. -70°C; the rest of the sample starts to transform to tetragonal structure at ca. -30°C and nearly completes crystallization at ca. 0°C. The exact temperatures of both transformations depend on the amount of isopentane present and sample thickness. Upon aging at room temperature the tetragonal structure converts to the twinned hexagonal structure even faster than in the absence of isopentane. Dynamic mechanical experiments show the presence of two relaxation-like peaks for the ultraquenched samples: T_r (L) = -27°C and T_r (U) = -15°C. X-ray diffraction, DSC, and torsion pendulum experiments show that PB crystallizes from the glass at T_r (U).     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.     

The magnetic field dependence of the structural transition temperature in La3S4 and La3Se4

The magnetic field dependence of the structural transition temperature T_m from the cubic to the tetragonal phase has been determined for single crystals of La₃S₄ and La₃Se₄. The observed field dependence of T_m can be accounted for by the band Jahn-Teller model of the coupling of an e_g-band to the shear mode of the cubic lattice without invoking any coupling to acoustic or optical phonons.     

Magnetic susceptibility and superconductivity of cubic vanadium nitrides

The superconducting transition temperature T_C and the magnetic susceptibility from 77 to 300°K have been measured on five cubic vanadium nitrides: VN, VN_0.91, VN_0.82, VN_0.84 and VN_0.75. The materials were carefully prepared to exclude oxygen and ferromagnetic impurities.The value of T_C, falls from 8.1°K for VN to 2.3°K for VN_0.75. The mass-susceptibility decreases from +3.94 × 10^?6e.m.u./g for VN to 1.88 × 10^?6e.m.u./g for VN_0.75 at 300°K. All samples showed a small positive slope for the susceptibility temperature curve.The results are discussed in terms of the rigid band model. The main features are a high density of states of d electrons, 2.4 states/atom eV for VN that drops off as the nitrogen content decreases, to 0.8 states/atom eV.Preliminary considerations indicate that many-body effects could reduce this density of states by as much as a factor of 2. Lack of experimental results on Knight shifts and low-temperature specific heats prevent a more quantitative estimate being made.     

Magnetic, electrical, and optical properties of electron-doped Ca1 − x LaxMnO3 − δ(x ≤ 0.12) single crystals

The magnetic, electrical, and optical properties of Ca_{1 ? x} La_xMnO_{3 ? δ}(x ≤ 0.12) manganite single crystals have been studied. The state with a spatially inhomogeneous electron distribution has been found. Interrelations between the electric and magnetic subsystems are analyzed. The obtained magnetic data show evidence for the formation of a G-type antiferromagnetic (G-AFM) phase with a spin-canted structure in the crystal with x = 0.05, for which the Curie and Néel temperatures are T _C = T _N(G) = 115 K. On cooling from the paramagnetic state, the crystals with x = 0.10 and 0.12 exhibit transitions from the paramagnetic to a C-type antiferromagnetic (C-AFM) phase in a part of the volume at T _N(C) = 150 and 200 K, and from the paramagnetic to the G-type antiferromagnetic (G-AFM) phase in the remaining volume at T _N(G) = 110 and 108 K, respectively. The onset of the C-type magnetic phase nucleation in crystals is observed at lower dopant (La) concentrations than in polycrystalline samples, which is explained by the deviation of single crystals from the stoichiometry with respect to oxygen. The magnetic phase transitions are manifested by anomalies in the electric resistance and magnetoresistance of doped crystals. An analysis of the electrical and optical properties of the samples shows evidence of (i) the formation of a charge energy gap in the C-AFM phase with retained paramagnetic metallic regions and (ii) the presence of ferromagnetic “metallic” droplets in the insulating G-AFM phase. The multiphase state of Ca_{1 ? x} La_xMnO_{3 ? δ} manganite single crystals featuring the coexistence of two magnetic phases, the regions with orbital/charge ordering, and the FM “metallic” droplets is related to a competition of exchange interactions by the superexchange and double exchange mechanisms.     

Elimination of the mott interband s-d enhancement of the electrical resistance of nickel and platinum owing to the excitation of electrons by femtosecond laser pulses

The dependence of electrical, σ, and thermal, κ, conductivities of metals on the electron temperature T _e at high (～1 eV) T _e values has been calculated. The two-temperature states for which the temperature T _e of heated electrons exceeds the temperature T _i of ions in the crystal lattice result from the excitation of electrons by femtosecond laser pulses. It is well known that the existence of empty d levels with a high density of states near the Fermi surface (as, e.g., in nickel, platinum, and iron) leads to a pronounced enhancement of the electrical resistance (Mott, 1936). This is due to an increase in the statistical factor related to the electron transitions to the empty states induced by collisions with phonons. It is found that the excitation of the electron subsystem significantly reduces the electron-phonon scattering to unoccupied d states since the chemical potential μ(T _e ) rises above the upper edge of the d band. The decrease in the scattering probability leads to the anomalous behavior of the conductivity σ_el-ph, which increases with the temperature T _e . Such a behavior turns out to be inverse with respect to the usual situation in condensed matter.     

Superconductivity of niobium nitride single crystals after implantation of carbon and nitrogen

Single crystals of δ-NbN_0.85 with a superconducting transition temperature T_c of 14.3 K were implanted with nitrogen and carbon ions at room temperature and subsequently annealed at high temperatures. Implantation was also performed at high substrate temperatures. After implantation at about 920°C maximum T_c-values of 16.5 and 17.8 K were obtained with N- and C-ions respectively. Disorder observed after room temperature implantation consisted of displaced Nb-atoms which could not be completely annealed in an isochromous annealing process up to 1000°C. For annealing temperatures above 1100°C nitrogen diffusion out of the implanted layers resulted in a reduction of T_c.