An investigation of graphite PEEK composite under compression with a centrally located circular discontinuity

The failure characteristic of graphite polyetheretherketone (Gr/PEEK) under compression with a centrally located circular discontinuity was investigated through experimentation and a nonlinear ply-by-ply finite element technique. The stacking sequence of the laminates investigated were: [0 °₁₆], [90 °₁₆], [±45 °]_4S [0 °/90 °]_4S, and [0 °/ ± 45 0°/90 °]_2S. In the experimentation, [90 °]₁₆, [0 °/90 °]_4S, and [0 °/ ±45 °/90 °]_2S laminates, as well as three of the [0 °]₁₆, failed due to a crack that was normal to the loading direction and initiated from the edge of the hole progressing to the outer edges of the specimen. The [±45 °]_4S specimens failed to support the load due to an internal crack that originated from the hole's edge and then traveled at an angle of about 42% to the direction of loading. The finite element method used to analytically model the failure of Gr/PEEK accurately modeled the response of the specimens tested experimentally.     

Damage detection of surface cracks in composite laminates using modal analysis and strain energy method

This paper presents an approach to detect surface cracks in various composite laminates. Carbon/epoxy composite AS4/PEEK was used to fabricate laminated plates, [0]₁₆, [90]₁₆, [(0/90)₄]_S and [±45/0/90]_2S. Surface crack damage was created on one side of the plate using a laser cutting machine. Modal analysis was performed to obtain the mode shapes from both experimental and finite element analysis results. The mode shapes were then used to calculate strain energy using the differential quadrature method (DQM). Consequently, the strain energies of laminated plates before and after damaged were used to define a damage index which successfully identified the surface crack location.     

Beam analysis of angle-ply laminate end-notched flexure specimens

Analysis and experiments on quasi-unidirectional and angle-ply laminate end-notched flexure specimens are presented. The analysis is based on laminated beam theory incorporating first-order shear deformation theory. Compliance and strain-energy release rate determined for relatively thin unidirectional and angle-ply laminate ENF specimens were in good agreement with a previous classical plate theory formulation. For thicker laminates, however, effects of shear deformation on the compliance of the ENF specimen become significant. An experimental study on glass/polyester quasi-unidirectional and angle-ply laminate ENF specimens was conducted. Specifically, [0]₆, [±30]₅ and [±45]₅ laminates with mid-plane delaminations were considered. Experimental compliance data agreed well with analytical predictions. The fracture toughness increased with increased angle θ at the ±θ interface. This is attributed to the fracture work associated with the debonding of transversely oriented fiber bundles in the quasi-unidirectional plies. The angle-ply laminates displayed more yarn debonding than the quasi-unidirectional laminate. For all laminates it was observed that the crack propagated in a non-uniform manner which is correlated with elastic coupling effects with cracked regions of the laminate beams.     

Physical aging behavior of high-performance composites

The effect of physical aging on the viscoelastic creep properties of a thermoplastic-toughened cyanate ester resin (Fiberite 954-2) and its IM8/954-2 composites, and a semi-crystalline thermoplastic (Fiberite ITX) and its IM8/ITX composites was investigated. The study was carried out by using dynamic mechanical analysis (DMA) and tensile creep tests. Tests were performed on plain resin, [90 °]_4s, and [± 45 °]_2s composite specimens. Creep tests were conducted up to an aging time of 54 h with the logarithmic aging shift rate, μ, and its dependence on sub-glass transition aging temperature, being determined. The results showed significant physical aging in both material systems. To study the effect of long-term aging on creep behavior, momentary creep tests were conducted on the [± 45 °]_2s composites of both material systems at temperatures between 140 and 200 °C. Master curve plots were drawn from these momentary creep tests using the time/temperature superposition principle (TTSP). Effective time theory (ETT) was then used to modify TTSP and incorporate physical aging effects.     

Chemical vapor deposition of copper–cobalt binary films

Chemical vapor co-deposition of Cu–Co films has been demonstrated using (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)Cu(II) [Cu(hfac)₂] [hfac=hexafluoroacetylacetonate] and (acetylacetonate)Co(II) [Co(acac)₂] [acac=acetylacetonate] as precursors. The deposition was performed at the substrate temperature of 270°C in a warm-wall impinging jet type reactor. The precursor Co(acac)₂ was sublimed at 140°C to achieve reasonable precursor delivery rates and avoid decomposition of precursor in the sublimator. Films with varying Cu content from 17 wt.% to 98 wt.% were deposited by subliming Cu(hfac)₂ in the temperature range of 40–100°C with a fixed Co(acac)₂ delivery rate. The morphologies and crystallinities of the binary films were strongly dependent on the film stoichiometry. Overall, this study provides insights into the mechanism of Cu–Co binary film formation by CVD.     

Growth of delamination cracks due to bending in a [905/05/905] laminate

A study of the growth of delamination due to bending in a [90₅/0₅/90₅] graphite/epoxy laminate is presented. A plane strain finite element analysis is used to determine the strain energy release rate during delamination in a three-point-bend specimen. A closed form expression for energy release rate is obtained from classical lamination theory and Timoshenko beam theory and is compared with the finite element analysis result. These results combined with the experimentally determined critical load, P_crit, are used to calculate the critical strain energy release rate, G_C. The critical energy release rate is also determined experimentally by the compliance method.     

Pyrolytic Trifluoromethylation of [76]-, [78]-, [84]-, and Aza[60]Fullerenes with Silver Trifluoroacetate; Evidence for Coordination of Fullerenes to Silver

Pyrolytic trifluoromethylation of [76], [78], [84], and aza[60]fullerenes with silver trifluoroacetate at 300°C results in extensive polyaddition of up to 18, 18, 20 and 20 CF₃ groups, respectively. In contrast to trifluoromethylation of [60]- and [70]fullerenes that give a full range of derivatives ranging upwards from C_n(CF₃)₂, [76]-, [78]-, and [84]-fullerenes only give C_n(CF₃)_6-18 derivatives, largely in the 10-12 CF₃ range; reaction with [76]fullerene is accompanied by formation of C₆₀(CF₃)₆ attributed to cage fragmentation. For aza[60]fullerene the hexa-addition level dominates, in contrast to its other reactions which give predominantly penta-addition products. All the compounds showed peaks at 1256±2 and 1180-1190 cm^-1, due to the CF₃ group, and peaks in this region are shown also by the soluble extract obtained on trifluoromethylation of nanotubes. As in trifluoromethylation of [60]- and [70]-fullerenes, the products obtained initially are involatile, attributed to formation os silver complexes; these are decomposed on subsequent solution in toluene. Mixed isomeric trifluoromethylated C₆₀F₈ derivatives viz. C₆₀F₇CF₃, C₆₀F₆(FG₃)₂, C₆₀F₅(CF₃)₃ and C₆₀F₄(CF₃)₄, and C₆₀F₄CF₃CF₂CF₃ (a C₆₀F₆ derivative) have been isolated from fluorination of [60]fullerene with MnF₃/K₂NilF₆ at 510°C.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

ISOLATION AND CHARACTERISATION OF C60(CF3)2

From the products of reactions of [60]fullerene with either K₂PtF₆ at 470 °C or AgF at 520 °C, we have isolated C₆₀(CF₃)₂, the simplest trifluoromethylfullerene, which gives a single ¹⁹F NMR line at -69.5 ppm. The HPLC retention time is less than that of C₆₀F₂ confirming the trend observed for other fluoro- vs. trifluoromethylfullerenes namely that the latter elute more rapidly. Other trifluoromethyl- containing species, C₆₀(CF₃)₄O, C₆₀F₅CF₃, C₆₀(CF₃)₄H₂, C₆₀(CF₃)₆H₂, and C₆₀(CF₃H)₃ were detected in the product mixture.     

High strain rate compressional behavior of stitched and unstitched composite laminates with radial constraint

This paper is concerned with the high strain rate compressional behaviour of glass/epoxy (Hy-E 9134B, Fiberite, USA) composite laminates with or without stitching reinforcement by untwisted Kevlar-49 threads (1140 denier). The split Hopkinson pressure bar (SHPB) apparatus is used in performing the high strain rate tests. Test data are analyzed in a manner similar to that reported by Hauser Exp. Mech., 6 (1966) 395. Specimens are tested at strain rates up to 10⁴ s⁻¹. Unidirectional laminated parallelepiped samples are impacted along their fiber direction. Their high velocity compressive ductility is observed. Both [0°]₂₄ and [(0°/90°)₆]_S glass/epoxy circular specimens with disc diameters of 10 and 50·8 mm are transversely impacted by an input bar in order to study their high strain rate behavior. Moreover, two sets of stitched circular specimens with disc diameters of 10 and 50·8 mm are also examined. The effect of strain rate and radial constraint on the dynamic properties of stitched and unstitched GFRP laminated specimens and their associated damage patterns are described.     

Analysis of stiffness reduction of cracked cross-ply laminates

Stiffness reduction of cracked [0°_m/90°_n]_s laminates is analyzed by variational methods on the basis of the principle of minimum complementary energy. For this purpose admissible stress systems are constructed which satisfy equilibrium and all boundary and interface conditions. The optimal stress field is then determined by minimization of complementary energy. The analysis allows for crack interaction and random crack distribution. Results are given for Young's modulus, shear modulus and Poisson's ratio. Young's modulus results are in excellent agreement with experimental data for [[0°/90°₃]]_s glass/epoxy laminate.     

Synthesis, structure and luminescent properties of Lu(PO3)3

A new structural type of rare earth metaphosphate, Lu(PO₃)₃, was prepared from high-temperature solution, of which the crystal structure was solved in S.G. of Cc (No.9) and Z = 4 with unit cell dimensions of a = 13.972(3) Å, b = 6.6710(13) Å, c = 9.958(2) Å and β = 127.36(3)°. In Lu(PO₃)₃, [LuO₆] octahedra connect with the non-bridging oxygens on (PO₃)_n infinite zigzag chains that extended along c-axis. The VUV and X-ray excited luminescent properties of undoped and Ln³⁺ (Ln = Ce, Eu, Tb) doped samples were examined, from which the optical band gap was estimated to be 8.3 eV. Besides, in the undoped sample a STE emission within 320–480 nm was observed, which probably be related to oxygen defects. However, in the Lu(PO₃)₃:Ce sample the Ce³⁺ emission was weak and STE emission was totally quenched under hard X-ray excitation.     

Ionic Conductivity and Mechanical Properties of Post-HIPed Cubic Zirconia/Alumina Composites

8 mol.% yttria-doped cubic zirconia (8Y-CSZ)/AI₂O₃ composites containing 0-30 vol.% Al₂O₃ particles were fabricated by sintering, followed by hot isostatic pressing (post-HIPing). All composites were densified to at least 99·5% of the theoretical density by post-HIPing. The bending strength of composites sintered at 1500°C in air was independent of A1₂O₃ content, but a significant improvement in the bending strength was achieved by the post-HIPing technique. The bending strength and the fracture toughness of the HIPed composites increased with increasing A1₂O₃ content. Ionic conductivity of the composites was evaluated and the total, lattice, and grain boundary conductivities slightly decreased with increasing A1₂O₃ content. The HIPed composites containing up to 20 vol.% A1₂0₃ appear to be suitable candidate materials as electrolyte for solid oxygen fuel cell.     

Growth of calcium carbonate by the atomic layer chemical vapour deposition technique

Thin films of CaCO₃ (calcite) have been grown with the atomic layer chemical vapour deposition (ALCVD) technique, using Ca(thd)₂ (Hthd=2,2,6,6-tetramethylheptan-3,5-dione), CO₂, and ozone as precursors. Pulse parameters for the ALCVD-type growth are found and self-limiting reaction conditions are established between 200 and 400 °C. Calcium carbonate films have been deposited on soda-lime glass, Si(100), -Al₂O₃(001), -Al₂O₃(012), -SiO₂(001), and MgO(100) substrates. The observed textures were: in-plane oriented films with [100](001)CaCO₃ [100](001)Al₂O₃ and [100](001)CaCO₃[110](001)Al₂O₃ on -Al₂O₃(001), amorphous films on -Al₂O₃(012) when grown at 250 °C, and columnar oriented films on soda-lime glass, Si(001), -SiO₂(001), and MgO(100) substrates with (00l) and (104) parallel to the substrate plane at 250 and 350 °C, respectively. The film topography was studied by atomic force microscopy and AC impedance characteristics were measured on as-deposited films at room temperature. The films were found to be insulating with a dielectric constant (_r) typically approximately 8. Thin films of CaO were obtained by heat treatment of the carbonate films at 670 °C in a CO₂-free atmosphere, but the thermal decomposition led to a significant increase in surface roughness.     

Thermolysis and Photolysis of C60 Diozonides

Ozonation of C₆₀ in o-xylene produced three C₆₀(O₃)₂ diozonides that were separated from one another and from two C₆₀(O₃)₃ triozonides by High Performance Liquid Chromatography (HPLC). Upon thermolysis at 10, 15, and 16.6°C, each of the diozonides dissociated sequentially, first to a C₆₀O(O₃) oxyozonide, then to a C₆₀O₂ diepoxide. The three diepoxides were stable in solution for at least 3 weeks. The mean lifetimes of the three diozonides were 52 ± 5, 62 ± 6, and 17.3 ± 1.8 min, respectively (all at 15°C). The mean lifetimes of the three oxyozonides were 69.7 ± 0.7 and 58 ± 6 min at 16.6°C, respectively and about 240 min at 10°C. Photolysis of the diozonides yielded two dioxidoannulenes with UV-Vis adsorption maxima at 333 and 332 nm, and what appeared to be an epoxide-oxidoannulene with UV-Vis adsorption maximum at 327 nm. These annulenes were observed to form dimers. We have synthesized and characterized six C₆₀O₂ dioxides, at least three and possibly four of which were hitherto unknown. We report the discovery of oxyozonides that form during the dissociation of diozonides.     

Langmuir–Blodgett films of substituted bis(naphthalocyaninato) rare earth complexes: structure and interaction with nitrogen dioxide

Ordered molecular assemblies of novel alkylthio-substituted bis(naphthalocyaninato) rare earth complexes M[2,3-Nc(SC₁₂H₂₅)₈]₂ (M=Gd, Er) have been fabricated by Langmuir–Blodgett (LB) technique and characterized by surface pressure-area isotherm measurements, electronic absorption and polarized electronic absorption spectroscopy and low-angle X-ray diffractometry. The interaction between the thin films and NO₂ gas was investigated. The experimental results indicate that the bis(naphthalocyaninato) rare earth molecules form well-ordered stable monolayers with face-to-face orientation for the macrocycles and edge-on configuration for the molecules at the air–water interface and lamellar multilayers on solid substrates. The orientation angles of naphthalocyanine rings with respect to the quartz plate surface in the LB films for M[2,3-Nc(SC₁₂H₂₅)₈]₂ with M of Gd and Er have been determined based on the polarized absorbance and found to be 50° and 54°, respectively. The adsorption–desorption process of NO₂ on LB films of M[2,3-Nc(SC₁₂H₂₅)₈]₂ has been monitored by electronic absorption spectroscopy. A process of gas desorption was found to obey the Elovich equation.     

Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Sintering of Fused Mullite Based Particulate Composites Containing Zirconia

2r0₂ and its modified versions containing MgO and Y₂0₃ were selected as particulate reinforcement in order to achieve better mechanical properties in fused mullite. Particulate composites containing up to 25 vol% Zr0₂ and its modifications were pressed to 65% relative density at 350 MPa followed by sintering at 1650°C and 1700°C for one hour. Studies were conducted on fracture toughness, transverse rupture strength, dielectric constant, microstructure, fractography and thermal shock resistance. Composites sintered at 1700°C were found superior in properties than those sintered at 1650°C.