Crack growth in a pipe grade PVC material under static and cyclic loading conditions

The creep crack growth (CCG) and the fatigue crack growth (FCG) behavior of a commercial pipe grade PVC material was studied based on a linear elastic fracture mechanics (LEFM) methodology. The FCG tests were performed under sinusoidal load control at a frequency of 5 Hz and at R-ratios (F_min/F_max) of 0.1, 0.3 and 0.5; the test temperatures were 23°C and 60°C. The creep crack growth behavior (corresponding to R = 1) was studied at a test temperature of 60°C. The results of the FCG tests revealed that fatigue crack propagation is primarily controlled by the cyclic component of the crack tip stress field rather than by the mean stress level. Comparing FCG and CCG data in terms of K_Imax and K_I, respectively, also confirmed the deteriorating effect of the fatigue loading on the crack growth resistance. Fracture surface investigations for both fatigue and static loading were performed to gain insight into the micromechanisms of crack advance.     

Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 - Dihydrogen bonding and H2 formation with protic donors

The hydridic reactivity of the complex W(CO)(H)(NO)(PMe₃)₃ (1) was investigated applying a variety of protic donors. Formation of organyloxide complexes W(CO)(NO)(PMe₃)₃(OR) (R = C₆H₅ (2), 3,4,5-Me₃C₆H₂ (3), CF₃CH₂ (4), C₆H₅CH₂ (5), Me (6) and iPr (7)) and H₂ evolution was observed. The reactions of 1 accelerated with increasing acidity of the protic donor: Me₂CHOH (pK_a = 17) < MeOH (pK_a = 15.5) < C₆H₅CH₂OH (pK_a = 15) < CF₃CH₂OH (pK_a = 12.4) < C₆H₂Me₃OH (pK_a = 10.6) < C₆H₅OH (pK_a = 10).Regioselective hydrogen bonding of 1 was probed with two of the protic donors furnishing equilibrium formation of the dihydrogen bonded complexes ROH···HW(CO)(NO)(PMe₃)₃ (R = 3,4,5-Me₃C₆H_2,3a and iPr, 7a) and the O_NO hydrogen bonded species ROH···ONW(CO)(H)(PMe₃)₃ (R = C₆H₂Me_3,3b and iPr, 7b) which were studied in hexane and d₈-toluene solutions using variable temperature IR and NMR spectroscopy. Quantitative IR experiments at low temperatures using 3,4,5-trimethylphenol (TMP) confirmed the two types of competitive equilibria: dihydrogen bonding to give 3a (ΔH₁ = −5.8 ± 0.4 kcal/mol and ΔS₁ = −15.3 ± 1.4 e.u.) and hydrogen bonding to give 3b (ΔH₂ = −2.8 ± 0.1 kcal/mol and ΔS₂ = −5.8 ± 0.3 e.u.). Additional data for the hydrogen bonded complexes 3a,b and 7a,b were determined via NMR titrations in d₈-toluene from the equilibrium constants K_(Δδ) and K_(ΔR1) measuring either changes in the chemical shifts of H_W(_Δδ) or the excess relaxation rates of H_W (ΔR₁) (3a,b: ΔH_(Δδ) = −0.8 ± 0.1 kcal/mol; ΔS_(Δδ) = −1.4 ± 0.3 e.u. and ΔH_(ΔR1) = −5.8 ± 0.4 kcal/mol; ΔS_(ΔR1) = −22.9 ± 1.9 e.u) (7a,b: ΔH_(Δδ) = −2.3 ± 0.2 kcal/mol; ΔS_(Δδ) = −11.7 ± 0.9 e.u. and ΔH_(ΔR1) = −2.9 ± 0.2 kcal/mol; ΔS_(ΔR1) = −14.6 ± 1.0 e.u). Dihydrogen bonding distances of 1.9 Å and 2.1 Å were derived for 3a and 7a from the NMR excess relaxation rate measurements of H_W in d₈-toluene. An X-ray diffraction study was carried out on compound 2.     

The relation between relaxed enthalpy and volume during physical aging of amorphous polymers and selenium

This paper reports physical aging results for PMMA, PMMA/PEO blends, PS, PC, PVC and PET (semicrystalline). Also included in this study is amorphous selenium. Temperature down-jumps from equilibrium above T_g to a temperature below T_g were carried out. Relaxed enthalpy, Δh and volume contraction, Δv, were measured. From the aging records, the constant ratio Δh/Δv = K_a was evaluated. For the polymeric samples K_a values of about 2 GPa were observed, thus similar to the inverse value of the isothermal compressibility close to T_g. Similarly for Se the K_a value obtained from Δh and Δv was in fair agreement with its isothermal compressibility.     

Sterically hindered and completely arrested nitrogen inversion in pyrazolidines

Syntheses of trans-1,2-di-tert-butylpyrazolidine 1, d,l- and semi-meso-1,2-diisopropyl-3,5-dimethylpyrazolidines, 2a and 2b, respectively, have been developed. Activation parameters of the nitrogen inversion in 1 (ΔG^≠ = 123 kJ mol⁻¹ at 110 °C, ΔH^≠ = 114 kJ mol⁻¹, ΔS^≠ = −15 J K⁻¹ mol⁻¹) have been determined. The steric veto of the nitrogen inversion in 2a has been confirmed. Chemical transformations of 1 have been studied, and the crystal structures of 2a·picrate and 2b·HCl determined.     

The direct l-type resonance spectrum of CF3CCH in the vibrational state v10=3: Extension of the theory of reduction to H6n terms

The direct l-type resonance spectrum of CF₃CCH has been measured in the v₁₀=3 vibrational state by means of waveguide microwave Fourier transform spectroscopy in the range 8–26 GHz. Three types of direct l-type resonance transitions induced by the (Δk=Δl=±2) interaction could be observed: 140 transitions following the ΔJ=0, Δk=Δl=±2, Δ|l|=0, selection rule covering values of J=17–61 and G=|k−l| from 1 to 7, 94 transitions following the ΔJ=0, Δk=Δl=±2, Δ|l|=±2, selection rule covering values of J=26–57 and G from 15 to 24, 90 transitions following the ΔJ=0, Δk=Δl=±4 selection rule covering values of J=34–80 and G from 3 to 12 and 13 transitions following the ΔJ=0, Δk=Δl=±6, k=∓1, l=∓1⇔k=±5, l=±3 selection rule for J=71-83. 14 A₁–A₂ splitting transitions with kl=+1 were measured from J=33 to 49. Strong perturbations due to Δ(k−l)=±3 interactions made possible the observation of perturbation-allowed transitions with selection rule k=±4, l=±3⇔k=±3, l=∓1. Furthermore, the rotational transitions J=2–1, 3–2 and 4–3 have been measured. To make use of the multiple fitting concept, the theory of reduction developed for the v_t=2 vibrational state by Sarka and Harder [K. Sarka, H. Harder, J. Mol. Spectrosc. 197 (1999) 254] has been extended to the v_t=3 vibrational state including terms up to H₆₂. Owing to problems in the reproduction of data with low K and A₁–A₂ symmetry, two types of fits have been performed using five reduced forms of the effective Hamiltonian. The first type of fit used a reduced data set for which part of the transitions has been omitted. The unitary equivalence of the determined parameter sets has been demonstrated including newly derived relations for parameters in v₁₀=3. In the second type of fit, the complete data set has been included, yielding satisfactory results only in one reduction. In both type of fits, parameters up to sixth order have been determined including the axial rotational constant A and the Coriolis constant Aζ for both values of l. General features of the direct l-type resonance spectrum in a v_t=3 level are discussed.     

Fracture resistance measurement of fused deposition modeling 3D printed polymers

A method is presented to characterize the fracture resistance and interlayer adhesion of fused deposition modeling (FDM) 3D printed materials. Double cantilever beam (DCB) specimens of acrylonitrile butadiene styrene (ABS) were designed and printed with a precrack at the layers' interface. The DCBs were loaded in an opening mode and the load-displacement curves were synchronized with the optical visualization of the crack tip to detect the critical load at the crack initiation. A finite element model, coupled with J-integral method and fracture surface analysis was then developed to obtain the apparent fracture resistance (J_cr,a) and the interlayer fracture resistance (J_cr,i), as a measure of the interlayer adhesion. The maximum J_cr,i was measured to be 4017 J/m², a value close to the fracture resistance of bulk ABS. Both J_cr,a and J_cr,i increased with the printing temperature. This method can find a great importance in the structural applications of printed materials.     

Influence of multidentate N-donor ligands on highly electrophilic zinc initiator for the ring-opening polymerization of epoxides

A set of multidentate ligands have been synthesized and used to stabilize the putative highly electrophilic zinc species initiating ring-opening polymerization (ROP) of cyclohexene oxide (CHO) and propylene oxide (PO). Reaction of the bidentate C₂-chiral bis(oxazoline) ligand (^R2,R3BOX: R₂ = (4S)-tBu, R₃ = H (a); R₂ = (4S)-Ph, R₃ = H (b); R₂ = (4R)-Ph, R₃ = (5S)-Ph (c)) with Zn(R₁)₂ (R₁ = Et (1), Me (2)) led to the heteroleptic three-coordinate complexes (^R2,R3BOX)ZnR₁, 1a-c and 2a, which were isolated in 92-96% yield. Next, two pyridinyl-functionalized N-heterocyclic carbene (NHC) ligands have been designed and synthesized: the 1,3-bis(2-pyridylmethyl)imidazolinium salt (d) and the protected NHC adduct 2-(2,3,4,5,6-pentafluorophenyl)-1,3-bis(2-pyridylmethyl)imidazolidine (e). The reaction of ligands d and e with ZnEt₂ led directly to the formation of (NHC)ZnEt(Cl) 3d complex with ethane elimination and the adduct (NHC-C₆F₅(H))ZnEt₂4e, respectively, in high yield. In situ combinations of selected complexes 1a-c, 3d and 4e with B(C₆F₅)₃ (1 or 2 equivalents) give active systems for ROP, with high productivity (3.3-5.9 10⁶ g_polym. mol_Zn⁻¹ h⁻¹) and high molecular weight (M_n up to 132 10³ g mol⁻¹) for CHO polymerization. Although the in situ B(C₆F₅)₃-activated zinc species were not isolated, the sterically demanding BOX ligands (1c > 1b > 1a) and functionalized NHC ligands seem to enhance the stability of highly electrophilic zinc complexes over ligand redistribution, allowing a better control of the cationic ROP as reflected particularly for 3d and 4e complexes by their respective efficiency (42-88%).     

Thiazolylhydrazone dervatives as inhibitors for insect N-acetyl-β-d-hexosaminidase and chitinase

Insect chitinase and N-acetyl-β-d-hexosaminidases (Hex) are potential targets for developing new pesticides. Here, a series of thiazolylhydrazones I (with substituted group R₁ at N3) and II (with substituted group R₁ at N2) were designed, synthesised and evaluated as competitive inhibitors of OfHex1 and OfChi-h, from the agricultural pest Ostrinia furnacalis. Derivatives I-3d and II-3d, with phenoxyethyl group at R₁, demonstrated the best inhibitory activities against OfHex1 and OfChi-h. Molecular docking analysis indicated that the branched conformation compound II-3d (K_i = 1.5 μmol/L) formed more hydrogen bonds with OfHex1 than the stretched conformation compound I-3d (K_i = 5.9 μmol/L). The differences in compounds’ binding conformations with OfChi-h explained differences in inhibitory activity of compounds I-3d (K_i = 1.9 μmol/L) and II-3d (K_i = 4.1 μmol/L). This work suggests a novel scaffold for developing specific Hex and Chi-h inhibitors.     

Stereoselective synthesis of novel tetrahydroxypyrrolizidines

N-Benzyloxycarbonyl-2,5-dideoxy-2,5-imino-3,4-O-isopropylidene-l-ribose 12a has been converted into (1R,2S,6R,7S,7aS)-5 and (1R,2S,6S,7R,7aR)-1,2,6,7-tetrahydroxypyrrolidin-5-ones 6 and (1R,2S,6S,7S,7aS)-7 and (1R,2S,6R,7R,7aS)-1,2,6,7-tetrahydroxypyrrolizidines 8 following stereoselective paths. These new compounds have been assayed for their inhibitory activities towards 25 glycosidases. Pyrrolizidines 7 and 8 are moderate but selective inhibitors of amyloglucosidase from Rhizopus mold (7: IC₅₀=130 μM, K_i=120 μM; 8: IC₅₀=200 μM, K_i=180 μM, mixed type of inhibition).     

Intramolecularly donor-stabilized silenes: Part 6. The synthesis of 1-[2,6-bis(dimethylaminomethyl)phenyl]silenes and their reaction with aromatic aldehydes

The intramolecularly donor-stabilized silenes ArR¹SiC(SiMe₃)₂ (3a–d) (3a: R¹ = Me; 3b: R¹ = t-Bu; 3c: R¹ = Ph; 3d: R¹ = SiMe₃; Ar = 2,6-(Me₂NCH₂)₂C₆H₃) were prepared by treatment of the (dichloromethyl)oligosilanes (Me₃Si)₂R¹Si–CHCl₂ (1a–d), with 2,6-bis(dimethylaminomethyl)phenyllithium (molar ratio 1:2). For 3c and 3d, X-ray structural analyses were performed indicating that only one dimethylamino group of the tridentate ligand is coordinated to the electrophilic silene silicon atoms, i.e., the central silicon atoms are tetracoordinated. The N → Si donation leads to pyramidalization at the silene silicon atoms; the configuration at the silene carbon atoms is planar. For a chemical characterization 3a and 3c were treated with water to give the silanols ArR¹Si(OH)–CH(SiMe₃)₂ (5a,c). Studies of the reactions of 3a and 3c with benzaldehyde, 4-chlorobenzaldehyde or 4-methoxybenzaldehyde, respectively, revealed an unexpected reaction path leading to the substituted 2-oxa-1-sila-1,2,3,4-tetrahydronaphthalenes 12a, 12c, 13 and 14. Both 12a and 12c were structurally characterized by X-ray analyses. The formation of these six-membered cyclic compounds, which is discussed in detail, gives support to a dipolar mechanism for the general reaction of silenes with carbonyl derivatives.     

Epoxy/CNT@X nanocomposite: Improved quasi-static,dynamic fracture toughness,and conductive functionalities by non-ionic surfactant treatment

The present work investigated the effects of non-ionic surfactant treatment on the dispersibility, surface chemistry and structure of carbon nanotube (CNT) particles. Subsequently, the fracture experiments of as-prepared epoxy/CNT@X nanocomposites were carried out under quasi-static and dynamic loading conditions. By simply introducing the steric repulsive force between CNT@X filler and epoxy matrix, improved mode-I critical-stress-intensity factor (K_Ic) and dynamic crack initiation toughness (K_Ii^d) of the epoxy/CNT@X nanocomposite were simultaneously obtained without compromising other desired physical properties, such as electrical properties and electro-thermal behavior. In the case of SHPB impact loading, high-speed imaging along with digital-image-correlation (DIC) technology was utilized to determine dynamic fracture parameters. The results showed a notable reinforcement for the epoxy/CNT@X nanocomposite category, producing maximum increase of ~79% and ~153% in K_Ic and K_Ii^d values relative to epoxy/CNT nanocomposite at such maximum content of 1.0 wt%, respectively. The most delayed crack initiation time (59.9–68.4 μs) and slowest crack-tip velocity (229 ± 28 m/s) were also observed in the epoxy/CNT@X_1.0 case. These results may be explained by improved dispersibility and interfacial adhesion after surfactant treatment.     

The enantiomeric recognition of chiral organic ammonium salts by chiral pyridino-macrocycles bearing aminoalcohol subunits

Pyridine-based macrocycles were prepared by treating 2,6-bis[[2′6′-bis(bromomethyl)-4′-methylphenoxy]methyl]pyridine 3 with the appropriate chiral aminoalcohols. The enantiomeric recognition of these macrocycles bearing aminoalcohol subunits of the pyridinocrown type ligand was evaluated for chiral organic ammonium salts by UV titration. The important differences were observed in the K_a values of (R)-Am2 and (S)-Am2 for (S,S,S)-1, (S,S,S)-2 and (S,S,S)-3 hosts, K_S/K_R = 5.0, K_S/K_R = 2.4 and K_S/K_R = 5.0, respectively. There seems to be a general tendency for hosts to recognise (S)-enantiomers for both Am1 and Am2.     

Iridium aminyl radical complexes as catalysts for the catalytic dehydrogenation of primary hydroxyl functions in natural products

The cationic tetra-coordinated 16 electron complex [Ir(trop₂dach)]⁺OTf⁻ (1) where (OTf⁻ = CF₃SO₃⁻) and the neutral amine amido complex [Ir(trop₂dach-1H)] (2) were isolated and structurally characterized. The NH function in 1 is easily deprotonated (pK_a^DMSO = 10.5) to yield the amino amido complex [Ir(trop₂dach-1H)] (2), which is deprotonated at pK_a^DMSO = 19.6 to the anionic di(amido) iridate [Ir(trop₂dach-2H)]⁻ (3); [(R,R)-top₂dach stands for the tetrachelating diamino diolefin ligand (R,R)-N,N′-bis(5H-dibenzo[a,d]cyclohepten-5-yl)-1,2-diaminocyclohexane; (R,R)-top₂dach-1H and (R,R)-top₂dach-2H indicate the mono and double deprotonated form]. Complex 3 is easily oxidized by 1,4-benzoquinone (BQ) to the neutral iridium aminyl radical complex [Ir(trop₂dach-2H)] (4). In combination with BQ as hydrogen acceptor and catalytic amounts of base, 4 serves as catalyst in the highly efficient dehydrogenation of functionalized primary alcohols to the corresponding aldehydes, RCH₂OH + BQ → RCHO + H₂BQ (H₂BQ = catechol). Alcohols like geraniol and retinol are rapidly converted to geranial and retinal, while the conversion of sterically hindered alcohols like lavandulol is slower and the primary product, lavandulal, isomerizes to isolavandulal in a classical base-catalyzed reaction.     

Single crystal growth and structural characterization of four complex uranium oxides: CaUO4, β-Ca3UO6, K4CaU3O12, and K4SrU3O12

Single crystals of complex uranium oxides, CaUO₄, β-Ca₃UO₆, K₄CaU₃O₁₂ and K₄SrU₃O₁₂ were grown from carbonate melts. The crystal structures of the four uranates were determined by single crystal X-ray diffraction. CaUO₄ crystallizes in the hexagonal space group R-3m, with lattice parameters a = 6.2570(7) Å and α = 36.04(2)°. The U⁶⁺ atom in CaUO₄ is 8-coordinate and exhibits hexagonal bipyramidal geometry with six long and two short U–O bonds, typical of a uranyl species. β-Ca₃UO₆ forms in the monoclinic space group P2₁/n, with lattice parameters a = 5.728(1) Å, b = 5.956(1) Å, c = 8.298(2) Å, and β = 90.55(3)°, and adopts a distorted double perovskite structure. K₄CaU₃O₁₂ and K₄SrU₃O₁₂ crystallize in the cubic space group Im-3m with lattice parameters a = 8.483(1) Å and a = 8.582(1) Å, respectively. In all three perovskite-type oxides, the U(VI) cation is located in an octahedral coordination environment and exhibits typical uranyl geometry with four long and two short U–O bonds.     

Synthesis of rigid and C2-symmetric 18-crown-6 type macrocycles bearing diamide–diester groups: enantiomeric recognition for α-(1-naphthyl)ethylammonium perchlorate salts

A series of rigid and chiral C₂-symmetric 18-crown-6 type macrocycles (S,S)-4, (S,S)-5, (S,S)-6 and (R,R)-2 bearing diamide–ester groups were synthesized. The binding properties of these macrocycles were examined for α-(1-naphthyl)ethylammonium perchlorates salts by an ¹H NMR titration method. Taking into account the host employed, important differences were observed in the K_a values of (R)- and (S)-enantiomers of guests for macrocycles (S,S)-4 and (S,S)-6, K_S/K_R = 3.6, and K_S/K_R = 0.1 (K_R/K_S = 10.3) ΔΔG = 3.19 and ΔΔG = ?5.77 kJ mol^?1, respectively. The results indicated excellent enantioselectivity of macrocyclic (S,S)-6 towards the enantiomers of α-(1-naphthyl)ethylammonium perchlorate salts.     

J and term dependences in the isotope shift of Eu I

High-resolution laser atomic beam spectroscopy has been applied to studyJ and term dependences in the isotope shift of the levels 4f ⁷5d6s a ¹⁰ D _J ,a ⁸ D _J of Eu I. A parametric analysis of the isotope shift has been performed. TheJ dependence is interpreted through two term-dependent parametersz _5d , and the term dependence through one parameterΔT:z _5d (a ¹⁰ D)=44.1 (2.6) MHz,z _5d (a ⁸ D)=55.9 (2.3) MHz,ΔT=408.5 (3.2) MHz. Ab initio Hartree-Fock and Dirac-Fock calculations have been made to interpret these parameters. Within the accuracy of the calculations the parameters can be attributed to field shift effects.     

About the OH yield in the radiolysis of an aqueous/H2O2 system. Its optimisation for water treatment

Unless the radiolytic reducing species are neutralised or converted into oxidising species, an EB remediation system cannot be considered a true Advanced Oxidation Processes (AOP). A water/H₂O₂ system irradiated by UVC mercury lamps constitutes a widely used OH production method. Employing H₂O₂ in radiolysis as well, an enhancement of the oxidative efficiency of an EB treatment can be obtained. Pulse radiolysis measurements of an aerated aqueous/H₂O₂/KSCN system have been systematically undertaken to assess the optimal H₂O₂ concentration. By linearly fitting a competition kinetics relationship, it is found that the scavengeable extra-yield of OH is ΔG(OH)=0.24 μmol J^?1 (R=0,9958), while the maximum experimental yield is measured G(OH)_max=(0.52±0.02) μmol J^?1 when [H₂O₂]=5–10 mM. Exceeding these concentrations the OH yield drops off.     

Laser fluorescence studies of HF rotational relaxation

Rotation relaxation of HF in HF-Ar mixtures was observed using a laser infrared fluorescence technique. A specific vibrational-rotational state of HF was excited, and the fluorescence from HF was monitored. Total rotational energy-transfer rates, and individual state-to-state transition probabilities were obtained for υ = 1, J = 3 (ΔJ = ± 1, ±2) and υ = 1, J = 5; (ΔJ= ±1, ?2, ?3). The transition probabilities decreased with increasing ΔE_J,J, the energy transferred from R → T (rotation to translation). The data were fitted to a simple exponential model k_JJ, α exp(-ClΔE_J,J'l). C was estimated to be 1.55 ± 0.25 kcal^?1 mole.     

Synthesis and structure of {{amino(triorganosilyl)carbene}pentacarbonyltungsten(0)} complexes and attempted synthesis of {[2-bis(trimethylsilyl)methyl-3-triorganosilyl-2H-azaphosphirene-κP]pentacarbonyltungsten(0)}

First examples of tungsten aminocarbene complexes [(OC₅)W{C(SiR¹_nR²_3-n)NH₂}] 2a-d (R¹ = Ph, R² = Me) were synthesized via ammonolysis of the corresponding methoxycarbene complexes 1a-d. They were characterized by NMR spectroscopy, MS, IR, UV/Vis and elemental analysis, and in the case of the C-triphenylsilyl derivative 2a by single-crystal X-ray structure analysis. The reaction of P-chloro alkylidenephosphane 3 with complexes 2a-d, meant to give 2H-azaphosphirene complexes, was monitored by ³¹P NMR spectroscopy to reveal the formation of the products 4-7, which were presumably formed via decomposition of the transient complexes 10a-d.     

Influence of Water Content on Basicities in Acetonitrile

The influence of water content at impurity level (5–10,000 ppm) in acetonitrile, on the changes in relative basicity differences (ΔpK _a values) of 13 pairs of bases, was studied both experimentally and computationally (COSMO-RS). The ΔpK _a values involving smaller bases with localized charge in the cationic form were found to be more affected. A computational parameter, weighted average negative sigma (WANS), was proposed to quantify the charge delocalization in cations and succeeded in describing the observed changes of ΔpK _a. The results validate the previously published basicity scale in acetonitrile with respect to solvent dryness and give guidelines for better experimental planning.