Experimentally- and theoretically-evaluated ultimate 3-dimensional elastic constants of trans-1,4-polyisoprene α and β crystalline forms on the basis of the newly-refined crystal structure information

The ultimate 3-dimensional elastic constants and compliance tensors have been evaluated for trans-1,4-polyisoprene (Gutta percha) α and β crystalline forms experimentally and theoretically. The theoretical estimation was performed by the molecular mechanics method on the basis of the newly-refined atomic coordinates obtained by quantitative analysis of the crystal structures using many numbers of X-ray reflections from the highly-oriented and highly-pure α and β crystalline samples. The calculated Young's modulus along the chain axis was 85.8 GPa for the α form and 72.3 GPa for the β form, in good agreement with the experimentally-obtained X-ray crystallite moduli, 72.4 GPa and 61.4 GPa, respectively.     

Molecular dynamics simulation of the structural and mechanical property changes in the Brill transition of nylon 10/10 crystal

In order to confirm the structural features in the Brill transition of aliphatic nylons, molecular dynamics calculation has been performed at the various temperatures for nylon 10/10 crystal as a model. With an increase in temperature, the torsional motions around the methylene-amide and methylene-methylene bonds were activated. These motions became more remarkable above 420 K and the interconversion between trans and gauche forms occurred frequently, resulting in the disordered conformation of the methylene sequences and the pseudo-hexagonal packing of these parts. During such a drastic structural disordering, however, the hydrogen bonds were kept alive although the bond strength became weaker. These calculations were found to be consistent with the experimental results by the temperature-dependent X-ray diffraction and infrared spectral measurements. The Young's modulus along the chain axis was also calculated as a function of temperature: it decreased remarkably from 250 GPa at 0 K to 180 GPa at 300 K due to a small contraction of the skeletal chain by only about 0.2-0.5% through the torsional motion of the skeletal chains, and the modulus decreased furthermore to 80 GPa at 550 K because of the larger conformational disordering of the skeletal chains. The Young's modulus in the direction perpendicular to the chain axis was also found to decrease remarkably in parallel to the change of the chain packing mode.     

黑梯炸药力学性能与感度的分子动力学研究

为了研究黑梯炸药配方对其力学性能与感度的影响,用Materials Studio软件建立了黑梯炸药的晶胞模型。采用分子动力学方法,计算了不同配方的黑梯炸药的力学性能、引发键键长分布、键连双原子作用能与内聚能密度,并对其变化情况并进行了比较。结果表明,在黑梯炸药中,随着RDX的质量分数从30%增加到80%,黑梯炸药的力学性能参数在一定范围内波动,其中拉伸模量变化范围为1.772 3~2.825 1GPa,剪切模量变化范围为0.636 6~1.042 8GPa,体积模量变化范围为2.734 1~3.747 9GPa,柯西压变化范围为1.203 2~2.181 6GPa,泊松比变化范围为0.354 6~0.397 0,而最大键长从0.155 4nm增至0.162 6nm,键连双原子作用能从167.6kJ/mol减至152.3kJ/mol,内聚能密度从0.899kJ/cm~3减至0.678kJ/cm~3,表明炸药的感度增大。     

Theoretical conformational study of 1,1,1-trifluoro-4-mercapto-but-3-ene-2-thione and the importance of intramolecular hydrogen bonding in ground and first electronic excited state

Quantum chemical calculations of energies, geometrical structure, intramolecular hydrogen bonding (HB) and vibrational frequencies of 1,1,1-trifluoro-4-mercapto-but-3-ene-2-thione were carried out by the ab initio Hartree–Fock, Moller–Plesset second-order perturbation (MP2) and density functional theory (DFT) methods with 6-311++G** basis set in gas phase and water solution. The nature of the intramolecular hydrogen bond in the most stable chelated conformers has been studied by using the atoms in molecules theory of Bader, which is based on topological properties of the electron density. Natural bond orbital (NBO) analysis was also performed for better understanding of the nature of intramolecular interactions. The influence of the solvent on the stability order of conformers and the strength of intramolecular HB was considered using Tomasi's polarized continuum model. The HOMA, NICS, PDI, ATI, FLU and FLU _π indices as well-established aromaticity indicators are examined. The excited-state properties of intramolecular HB in hydrogen-bonded systems have been investigated theoretically using the time-dependent DFT method. The calculated highest occupied molecular orbital (MO) and lowest unoccupied MO with frontier orbital gap are presented. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis.     

Effect of molecular rigidity and hydrogen bond interaction on mechanical properties of polyimide fibers

Six kinds of polyimide (PI) fibers with different molecular rigidity and hydrogen bond interactions were designed and prepared in order to investigate the relationship between structure and mechanical properties. The rigidity, aggregation structure, fracture morphology, hydrogen bond, and charge transfer (CT) interactions were investigated in detail. Conformational rigidity of six PI fibers were simulated and measured by D‐values of energy barrier and bottom in potential energy curves of PI units. Rigid rod‐like PI macromolecules tend to pack in order and show better mechanical properties. However, with the increase of D‐values, fracture mechanisms change from ductile fracture to brittle fracture. Brittle fracture resulting from high conformational rigidity is adverse to improvement of mechanical properties of PI fibers. Besides, strength of hydrogen bond and CT interactions are characterized by infrared spectroscopy and ultraviolet absorption spectra, respectively. The results indicate that higher interactions lead to higher tensile strength and initial modulus. Finally, PI fibers, which possess moderate conformational rigidity and strong hydrogen bond interactions, exhibit highest tensile strength (1.82 GPa) and initial modulus (85.7 GPa) in six kinds of PI fibers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43677.     

Effect of water on the mechanism of deformation of nylon 6

Lattice spacings perpendicular to the molecular chain axes and crystallite orientation of dried and moist (boiled in water) bulk nylon 6 were determined by x-ray diffraction under tension of 30–300 kg./cm.². The deformation of the specimen was also measured. The lattice spacings are changed reversibly by the presence of water in nylon 6, but the elastic moduli of the lattice are not affected. The lattice elastic modulus in the direction of the hydrogen bonds is approximately double its value in the direction normal to the hydrogen bonds. The elastic modulus of the dried nylon 6 approaches the value of the lattice elastic modulus in the direction normal to the molecular axes, while the modulus of the moist nylon 6 is several times lower. From these facts, and especially from the relations between the lattice deformation, crystallite orientation, and specimen deformation, the principal differences in the deformation mechanism of dried and moist nylon 6 were deduced. The results obtained have also made possible some general conclusions about the crystalline structure of nylon 6 and the deformation mechanism of linear polymers.     

Theoretical estimation of the effect of solvent on unperturbed dimensions: 1. Isotactic poly(vinyl alcohol)

The effect of the quality of solvent on the unperturbed chain dimensions $\text{r}{}_0{}^2$ of perfectly isotactic poly(vinyl alcohol) (iso-PVA) was studied by means of some model calculations according to the matrix method of Flory et al. These investigations were based on the assumption that the quality of solvent affected mainly the energy of the intramolecular hydrogen bond, while the magnitude of the interactions between other groups, hardly varied with the change of solvent. The individual conformation energies in a chain of iso-PVA were estimated from the analysis of structurally similar polymers, as well as the results obtained with 2,4-pentanediol. It was found that the characteristic ratio $\text{C =}\text{r}{}_0{}^2\text{nl}{}^2$ increased in non-polar solvents, with energy of the intramolecular hydrogen bond stabilizing the stretched zig-zag conformation of chain. Conversely, the characteristic ratio, monotonously decreased with increasing polarity of solvent to the value of about 6, typical of a flexible random coil. The existence of an analogous relationship, valid for other polymers, able to form an intramolecular hydrogen bond in the chain, was also discussed.     

The effect of nanostructure upon the deformation micromechanics of carbon fibres

We have used the Mori–Tanaka theory to develop a new micromechanical model to predict the Young’s modulus for carbon fibres, taking into account both the crystallites and amorphous components of the fibre structure. In order to follow the dependence of the mechanical properties of the fibres upon nanostructure, we prepared five different types of PAN-based fibres, with Young’s moduli in the range 200–500 GPa. The axial elastic constants of the bulk carbon fibres were measured directly by X-ray diffraction and an axial shear modulus of about 20 GPa was calculated. The elastic constants of the amorphous carbon in the fibres and the volume fractions of crystallites were estimated. It was found that the amorphous modulus was approximately 200 GPa and the volume fractions of crystallites were 0.4–0.8, depending upon the nanostructure of the carbon fibres. Also, as it is known that the Raman G band shift rate per unit strain is related to the crystallite modulus, the data indicated a nearly constant value of 1.1 TPa. The results show clearly that the behavior of carbon fibres can be expressed through a composite mechanical model that assumes they consist of both crystalline and amorphous carbon components.     

Synthesis and characterization of polymers containing naphthyl-2H-benzotriazoles, 3. Hydrogen bonding in monomers and polymers containing naphthyl-2H-benzotriazole

The UV absorption characteristics of a number of dihydroxynaphthyl-2H-benzotriazoles, their (meth)acryloyloxy derivatives and the corresponding polymers have been studied in a range of solvents of different polarity. It was shown that the formation of hydrogen bonds in these compounds strongly depends on the polarity of the solvent and an equilibrium exists between intramolecular and intermolecular hydrogenbonded states. The stability of the intramolecular hydrogen bond was determined quantitatively. The equilibrium between the intramolecular and the intermolecular hydrogen-bonded state of the molecule was strongly affected by the chemical structure of the naphthyl-2H-benzotriazole. The stability of the intramolecular hydrogen bond increased when electron-donating substituents were introduced into the benzotriazole or when the naphthyl-2-benzotriazole was fixed to a polymer backbone.     

Influence of high pressure on the structure,hardness and brittle-to-ductile transition of NbSi2 ceramics

We apply first-principles calculations to study the influence of pressure on the structure, elastic modulus, hardness, brittle-or-ductile behavior and melting point of NbSi₂. Four NbSi₂ phases: C40, C11_b, C54 and C49 are considered based on the structural feature. The results show that the calculated formation enthalpy of the four NbSi₂ phases is negative within the pressure range of 0–60 GPa, indicating that they are thermodynamically stable in whole pressure. In particular, the calculated formation enthalpy of the C54 NbSi₂ is smaller than the other NbSi₂ phases, indicating that the C54 NbSi₂ is more thermodynamically stable than the other NbSi₂ phases. The calculated elastic modulus and Vickers hardness of NbSi₂ increase with increasing pressure. Note that the pressure results in brittle-to-ductile transition of the C40 NbSi₂, C11_b NbSi₂ and C54 NbSi₂ between 30 GPa and 60 GPa. Naturally, the increasing of mechanical properties is that the pressure enhances the electronic hybridization between Nb and Si, which is demonstrated by the chemical bonding such as Nb–Si bond and Si–Si bond.     

热处理对木质纤维素Iβ结构及其力学性能影响的分子动力学模拟

采用分子动力学模拟方法对木材主要成分纤维素I_β在热处理环境下的结构和力学性能进行研究,建立了用于模拟的3×3×3纤维素超胞模型,得到350~550 K的体积、密度及氢键变化图,分析了纤维素微观结构的变化并计算了其力学性能。结果表明：升温过程中晶胞体积逐渐增大,由350 K的11.99 nm³增加至550 K的12.26 nm³,模型密度为1.581~1.617 g/cm³,与实验结果一致。氢键数量总数减小了24%,分子链内氢键部分断裂而形成了新的链间氢键,链内氢键与链间氢键的比值由2.1：1变成1：1.5,进而影响了其力学性能。随着温度的升高,杨氏模量逐渐降低,变化率约为13%。相比于杨氏模量,剪切模量和体积模量受温度影响较小,没有明显的变化趋势。     

Solid state extrusion of ultra high molecular weight polyethylene. Processing and properties

The techniques of solid state coextrusion and powder extrusion have been employed for the deformation of ultra high molecular weight polyethylene. Chain folded and chain extended morphologies obtained under different crystallization conditions were coextruded within a nylon 11 casing acting as a processing aid at an extrusion draw ratio (EDR) of 5 at ≤ 120°C and 0.20 GPa. The powder was compacted and extruded at ≤ 128°C and 0.23 GPa up to an EDR of 24. The physical and mechanical properties of the extrudates were evaluated and found to be dependent on intial morphology. An extrudate from the chain-folded morphology gave a low modulus of 0.71 GPa, the chain-extended morphology a modulus of 6.7 GPa, and the compacted powder a modulus of 15 GPa.     

Structure and mechanical properties of PGA crystals and fibres

The elastic constants of poly(glycolic acid) (PGA) crystals are reported on the basis of a commercial software package and the published crystal structure of the polymer. Due to the planar zigzag conformation of the molecular chains, very high elastic anisotropy is found with a tensile chain modulus of 294 GPa and a longitudinal shear modulus for a fibre of 6 GPa. A combination of small and wide angle X-ray scattering and differential scanning calorimetry are used to characterise the structure of highly oriented PGA fibres. The combination of long period data, crystal size and crystallinity measurements suggests a structure similar to the Prevorsek model, with alternating crystalline and amorphous regions along the fibre axis, and layers of amorphous material in parallel. A parallel-series Takayanagi model, using the theoretically calculated chain modulus, is shown to give good agreement with the experimental data in a wide temperature range.     

New model for the high modulus and strength performance of ultradrawn polyethylenes

A new morphological model is discussed which is based on the relation of tensile modulus and strength to the macrofibrillar dimensions (aspect ratio) and the shear modulus of ultrahigh molecular weight polyethylene fibrillar structures of draw ratio DR ≤ 200–300. Such structures were obtained by solid state deformation of the as-received powder and solution grown crystals using an extrusion-drawing process. According to this model, the highest tensile modulus and tensile strength values that can be obtained are 212 GPa and 13.3 GPa, i.e., significantly close to the theoretically calculated values.     

Microscopically-viewed relationship between the chain conformation and ultimate Young's modulus of a series of arylate polyesters with long methylene segments

Relationship between the chain conformation in the crystal lattice and the ultimate Young's modulus has been discussed on the basis of the crystal structural information revealed by the X-ray diffraction analysis for a series of arylate polyesters with long methylene segments (–[–COC₆H₄CO–O(CH₂)_mO–]_n–). The X-ray structural analysis revealed that the molecular chains take the all-trans-zigzag conformations for all of the even-numbered polyesters and their model compounds as well as the odd-numbered polyesters with the methylene segmental length longer than (CH₂)₁₄. These chain conformations have been correlated well to the ultimate Young's modulus along the chain axis or the crystallite modulus E_c, which has been estimated experimentally by the X-ray diffraction method under a constant stress and also predicted theoretically using the X-ray-analyzed crystal structures on the basis of the molecular mechanics method. The E_c was found to show the minimum at around m = 4–6 and increased gradually with an increment of m and approached the crystallite modulus of polyethylene, 235 GPa (X-ray value) ∼ 316 GPa (calculate) at an infinite m value. This behavior of E_c as a function of the number of methylene segmental units m was reasonably interpreted by developing the theoretical equation of E_c for a simplified zigzag chain model composed of a repetition of two linear rods representing the benzene–ester and methylene segmental parts respectively. These findings may promise that the mechanical property of arylate polyester can be controlled by adjusting the methylene segmental length m.     

Comparison of experimental and theoretical transverse elastic modulus of carbon fibers

The transverse elastic modulus of PAN-based carbon fibers as measured by experimental methods, calculated from theoretical equations and analyzed by the finite element method (FEM) is discussed. Raman spectroscopy was the primary method utilized to measure the transverse elastic modulus of carbon fibers in carbon-fiber reinforced plastics (CFRP). A lead oxide (PbO) thin film was deposited on the surface of a CFRP specimen using physical vapor deposition as the pretreatment in order to measure the strains of the carbon fibers and epoxy matrix phases by Raman spectroscopy. Since the relation between the Raman peak wave number of PbO thin films and tensile strain has already been developed, the transverse strain of the carbon fibers could be measured. The transverse strain of the carbon fibers was analyzed using a 2-D FEM model. The transverse modulus of the carbon fibers was determined by fitting the experimental result from Raman spectroscopy to the FEM model. The determined transverse modulus (10.4 GPa) is compared with those experimentally measured by nanoindentation (13.4 GPa), numerically analyzed using 2-D and 3-D FEM models (5.25 GPa and 28.7 GPa, respectively), and theoretically calculated from the Mori-Tanaka, Halpin-Tsai, and Uemura equations (24.8 GPa, 17.4 GPa, and 28.4 GPa, respectively).     

Cross-linking of ultra-high strength polyethylene fibres by means of electron beam irradiation

Summary Ultra-high strength polyethylene fibres, with a tensile strength at break of 3.0 and 3.4 GPa, were irradiated, at various temperatures in a hydrogen atmosphere, by means of high energy electrons.When the fibres were not annealed, the tensile strength at break was found to decrease upon irradiation, while the Young's modulus remained unchanged. A maximal obtainable tensile strength of 22 GPa was calculated from the decrease in tensile strength and the gel-sol measurements. Gel contents upto 100% were obtained for fibres irradiated in the hexagonal phase.     

Intermolecular interactions and crystallization behaviors of biodegradable polymer blends between poly (3-hydroxybutyrate) and cellulose acetate butyrate studied by DSC, FT-IR, and WAXD

Relationships between composition- and temperature-dependent intermolecular interactions and cold crystallization behaviors of poly(3-hydroxybutyrate) (PHB)/ cellulose acetate butyrate (CAB) blends have been investigated mainly by infrared (IR) spectroscopy, together with differential scanning calorimetry, and wide-angle X-ray diffraction (WAXD). Weak intermolecular hydrogen bondings between OH groups in CAB and CO groups in amorphous part of PHB define as inter were detected in OH stretching bands of the blends. These interactions occur in the blends with high CAB content (w_CAB) and highly depend on temperature. For all the blends having 0.2 ≤ w_CAB ≤ 0.7, when temperature is raised (e.g., above 90 °C for the blend with w_CAB = 0.5) the cold crystallization of PHB was discerned, as evidenced by an increase of the absorbance of the band due to CO stretching in the crystal field. The crystallization was found to involve the dissociation of inter and transformation of inter into intramolecular hydrogen bondings within PHB and within CAB as summarized in Table 2 in this text, which promotes the crystallization and enhances stabilization of the crystals. Consequently, the crystallization of the PHB is influenced by exchanges of the hydrogen bondings as described above with raising temperatures. X-ray diffraction from PHB crystals in the blends show a remarkable decrease of crystallinity with w_CAB and eventually disappear when w_CAB ≥ 0.8.     

Quantum chemical studies on molecular conformations,energetic and intramolecular hydrogen bonding in ground and electronic excited state of (thioxosilyl) ethyleneselenol

In this work, a conformational analysis of (thioxosilyl) ethyleneselenol was performed using several computational methods, including density-functional theory (DFT) (B3LYP), MP2 and G2MP2. Harmonic vibrational frequencies were estimated at the same levels to confirm the nature of the stationary points found and also to account for the zero point vibrational energy correction. MES-1 and TES-1 conformers exhibit hydrogen bonding. This feature, although is not the dominant factor in the stability of conformers, appears to be of foremost importance to define the geometry of the molecule. Two intramolecular hydrogen bonds established between the polar groups were identified by the structural geometric parameters. These involved the thiol and selenol functional groups and were identified and characterized by the frequency shift in their stretching vibration modes. Furthermore, the excited-state properties of intramolecular hydrogen bonding have been investigated theoretically using the time-dependent DFT method. The influence of the solvent on the stability order of conformers and the strength of intramolecular hydrogen bonding was considered using the PCM (polarizable continuum model), SCI-PCM (self consistent isodensity-polarizable continuum model) and IEF-PCM (integral equation formalism-polarizable continuum model) methods. The “atoms in molecules” theory of Bader was used to analyze critical points and to study the nature of hydrogen bond in these systems. Natural bond orbital (NBO) analysis was also performed for better understanding the nature of intramolecular interactions. The calculated highest occupiedmolecular orbital and lowest unoccupied molecular orbital energies show that charge transfer occur within the molecule. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis. Calculations of the ¹H NMR chemical shift at the GIAO/B3LYP/6–311++G** level of theory are also presented.     

Elastic moduli of liquid crystalline copolymers

Dynamic tensile and shear moduli measurements have been carried out on highly oriented thermotropic liquid crystalline copolymers formed by random copolymerization of 2-hydroxy-6-naphthoic acid, terephthalic acid and p-aminophenol. This liquid crystalline copolymer is known as HNATA. Application of the aggregate model of units of structure gives rise to an estimation of the orientation angle θ = 5° and a chain modulus E_c = 230 GPa. The fall in tensile modulus with increasing temperature is related to two factors: a decrease in the intrinsic chain modulus and a reduction in the shear modulus.