Variation of crystallographic parameters in PEEKK with heat treatment temperature

Using the wide-angle X-ray diffraction method, the variation of crystallographic parameters of poly(aryl ether ether ketone ketone) (PEEKK) has been studied in different heat treatment temperatures. All the reflections and their intensities as well as their Miller indices are presented in detail according to an orthorhombic system. The investigation indicates that the unit cell parameters a, b, c and the unit cell volume V systematically decrease with increasing heat treatment temperature. This variation is interpreted by the change of conformation of polymer molecular chains during thermal treatment. The results calculated from the formula of degree of crystallinity (W-c,W-x) for PEEKK, which was derived based on X-ray scattering intensity theory and the graphic multipeak resolution method, are compatible with the density measurement (W-c,W-d) and calorimetry (W-c,W-h) values. (C) 1997 Elesevier Science Ltd.

Crystallization behavior of blends of high-density polyethylene with novel linear low-density polyethylene

Blends of high-density polyethylene (HDPE) with novel linear low-density polyethylene (LLDPE) samples in the whole range of compositions were investigated by means of differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). The LLDPEs are ethylene/octene-1 copolymers prepared with a single-site catalyst, with a narrower distribution of branches compared to Ziegler-Natta type polymers. It was found that cocrystallization or separate crystallization in the blends profoundly depends on the content of branches in the LLDPE, while the critical branch content of the novel LLDPE for separate crystallization is much lower than that of commercial LLDPE (prepared with Ziegler-Natta catalysts). This implies that the miscibility of linear and branched polyethylene is also affected by the distribution of branches. The marked expansion of the unit cell in cocrystals, which are formed by HDPE with the novel LLDPE, indicates that the branches are included in the crystal lattice during the cocrystallization process. The result is very helpful to understand the phenomenon that the unit cell dimensions of commercial branched polyethylene are larger than those of linear polyethylene.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .2. Poly(ether ether ketone ketone), PEEKK

The crystal structure, morphology and polymorphism induced by uniaxial drawing of poly(ether ether ketone ketone) [PEEKK] have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD). On the basis of WAXD and ED patterns,the crystal structure of unoriented PEEKK is determined to have two-chain orthorhombic packing with unit cell parameters of a 0.772 nm, b = 0.600 nm, c = 1.004 nm (form I), A stress-induced crystal modification (form II) is identified and found to possess a two-chain orthorhombic lattice with unit cell dimensions of a = 0.461 nm, b = 1.074 nm, c = 1.080 nm. The 7.5% increase in c-axis dimension for form II is attributed to an overextended chain conformation, arising from extensional deformation during uniaxial drawing and fixed ''in-situ'' through strain-induced crystallization. The average ether-ketone bridge bond angles in form II crystal are determined to be 148.9 degrees by using standard bond lengths. The crystal morphology of PEEKK bears a great similarity to that of PEEK. The crystals grow in the form of spherulites and have the b-axis of unit cell radial. The effects of draw rate on strain-induced crystallization and induction of form II structure are also discussed.

X-ray crystallographic structure of meta- and para-dimethyl ester of pyromellitic acid

The polycrystalline powder of para- and meta-dimethyl ester of pyromellitic acid (PMDE) have been prepared by fractional crystallization, and their crystal structures have been determined by Wide-Angle X-ray Diffraction (WAXD). Both p-PMDE and m-PMDE was found to be orthorhombic crystal system, and their unit cell parameters a = 0.840 nm, b = 0.707 nm, c = 1.136 nm and a = 1.032 nm; b = 0.835 nm, c = 0.714 nm, respectively. Space group all belongs to P-mmm. p-PMDE has two molecules per unit cell with crystal density 1.388 g . cm(-3), while m-PMDE has two molecules per unit cell with crystal density 1.522 g . cm(-3). Indices of crystal diffraction peaks are also detailed in the present work. The difference in crystal structures between p-PMDE and m-PMDE has thus been used to explain the curing behavior of isomerically pyromellitic dianhydride-based poly(amic ester)s.

Crystal structure and crystallinity of poly(aryl ether biphenyl ether ketone ketone)

The crystal structure of poly(aryl ether biphenyl ether ketone ketone) (PEDEKK) was determined to comprise a two-chain orthorhombic unit cell with dimensions a 0.778 nm, b = 0.606 nm and c = 2.375 nm by using wide-angle X-ray diffraction (WAXD). According to the orthorhombic system, the 12 reflections of this polymer were indexed. The crystallite size increases with increasing the crystallization temperature. The results of the degree of crystallinity (W-c,W-x) calculated from WAXD were compatible with those from density (W-c,W-d) and calorimetry (W-c,W-h) measurements.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .1. Poly(oxybiphenyl-4-4'-diyloxy-1,4-phenylenecarbonyl-1,3-phenylenecarbonyl-1,4-phenylene)

Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4'-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260 degrees C, far below the next melting temperature (306 degrees C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c-axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.

The crystal structure and supramolecular chain of [La(NO3)(3)(OH2)(2)(phen)]center dot 15-crown-5

[La(NO3)(3)(OH2)(2)(phen)]. 15-crown-5 is hexagonal, P6(5), with a = 10.955(2), c = 43.769(9) Angstrom, and D-calc = 1.668 g cm(-3) for Z = 6. In the complex, two nitrogen atoms (from phen) and eight oxygen atoms (six from three bidentate nitrate anions and two from water molecules) are coordinated to the central La(III) ion, forming a coordination polyhedron which is approximately a bicapped square antiprism. The coordinated water molecules donate hydrogen bonds to the oxygen atoms of the crown ether, forming polymeric hydrogen bonded chains which wrap helically along the unit cell direction c.

Crystallization behaviour of poly(ether ether ketone)/poly(ether sulfone) block copolymer

The crystallization and melting behaviours of a multiblock copolymer comprising poly(ether ether ketone) (PEEK) and poly(ether sulfone) (PES) blocks whose number average molecular weights <((M)over bar (n)'s)> were 10 000 and 2900, respectively, were studied. The effect of thermal history on crystallization was investigated by wide-angle X-ray diffraction measurement. A differential scanning calorimeter was used to detect the thermal transitions and to monitor the energy evolved during the isothermal crystallization process from the melt. The results suggest that the crystallization of the copolymer becomes more difficult as compared with that of pure PEEK. The equilibrium melting point of the copolymer was found to be 357 degrees C, about 30 degrees C lower than that of pure PEEK. During the isothermal crystallization, relative crystallinity increased with crystallization time, following an Avrami equation with exponent n approximate to 2. The fold surface free energy for the copolymer crystallized from the melt was calculated to be 73 erg cm(-2), about 24 erg cm(-2) higher than that of pure PEEK. Copyright (C) 1996 Elsevier Science Ltd.

Isolation and X-ray crystallographic structure of cyclic tetramer based on bisphenol A and o-phthaloyl dichloride

The polycrystalline powder of the cyclic tetramer based on bisphenol A and o-phthaloyldichloride has been prepared by recrystallization from nitrobenzene and its crystal structure has been determined by Wide-Angle X-ray Diffraction (WAXD). The unit cell is orthorhombic and its dimensions a = 0.967 6 nm, b = 0.869 9 nm, c = 2.085 9 nm, Space group belongs to Pmmm, With two tetramers per unit cell,the crystal density is 1.36 g . cm(-3), Indices of crystal diffraction peaks are also detailed in the present work.

Effect of heat treatment on the parameters of crystal structure and degree of crystallinity of poly(aryl-ether-ether-ketone)

The variations of unit cell parameters and crystallite size of nine PEEK samples treated at various temperatures have been studied by using Wide-Angle X-ray Diffraction (WAXD), The results indicate a decrease in unit cell parameter a,b and c but an increase in crystallite size L(hkl) With the increase beat treatment temperature. Based on X-ray scattering intensity theory and using the graphic multipeak resolution method, the formula of degree of crystallinity (W-c,W-X) for PEEK is derived. The results calculated are compatible with the density measurement and calorimetry.

X-ray crystallographic structure of cyclic tetramer ester based on bisphenol-A and o-phthaloyldichloride

The polycrystalline powder of the cyclic tetramer ester based on bisphenol-A and o-phthaloyldichloride has been prepared by recrystallization from nitrobenzene and its crystal structure determined by wide-angle X-ray diffraction. The unit cell is orthorhombic and has dimensions a=0.967 nm, b=0.8699 nm, c = 2.0859 nm. With two tetramers per unit cell, the crystal density is 1.36 g cm(-3). Indices of crystal diffraction peaks are also detailed in the present work. Copyright (C) 1996 Elsevier Science Ltd.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.

Ansa-metallocene derivatives .2. Syntheses and structures of tetramethyldisiloxandiyl bis(1-indenyl and tetrahydroindenyl) zirconium dichlorides

The ansa-zirconocene derivative tetramethyldisiloxandiyl bis(1-indenyl) zirconium dichloride (1) has been prepared by the reaction of the dilithium salt of 1,3-bis(l-indenyl) tetramethyldisiloxane with ZrCl4 . 2THF, After catalytic hydrogenation, the corresponding tetrahydroindenyl complex (2) has been formed. Both 1 and 2 have been shown by H-1 NMR spectra to be the mixture of the cis(meso) and trans(rac) isomers, The pure trans isomers 1(l), 2(l) and cis isomer 2(c) were obtained by recrystallization, The crystal structures of 1(l) and 2(c) were determined by X-ray diffraction. Both crystals of 1(l) and 2(c) are monoclinics, belonging to space groups P2(1)/n(1(l)) and P2(1)/c(2(c)). In the unit cell of 2(c), one of the six-membered rings of the tetrahydroindenyl Ligands has two different conformations which have the same probabilities.

Synthesis and structure of 1:1 complex of ethylphenyltin dichloride with N-4-methoxyphenyl-2-hydroxynaphthylideneimine

A novel organotin complex, EtPhSnCl(2) . 2HOC(10)H(6)CH = NC6H1OCH3 was synthesized, and its crystal structure was determined by X-ray diffraction method. The crystal is triclinic, belonging to space group, with unit cell parameters a = 1.150 8(5) nm, b = 1. 153 1(5) gm, c = 1. 004 6 (3) nm, alpha = 94. 15 (3)degrees, beta = 115.47 (3)degrees, r = 85. 94 (4)degrees, V = 1199 7(1) nm(3), Z=2, D-c=1.68 g/cm(3), mu=13. 20 cm(-1), F(000)=618 for 4 131 reflections tions. R=0. 047, R(w)=0. 047. The ligand coordinates to tin atom via phenolic oxygen atom. The complex has a distored trigonal bipyramidal structure, the phenolic oxygen atom of the ligand and one of two chlorine atoms occupy the axial position. The distance between noncoodinated nitrogen atom with phenolic oxygen atom is 0. 257 4 nm, which indicates that the intramolecular hydrogen bond of Schiff base ligand is retained in the complex.