Influence of in-plane fibre orientation on mode I interlaminar fracture toughness of stitched glass/polyester composites

The influence of in-plane fibre orientation on the mode I interlaminar fracture toughness, G_Ic of unstitched and stitched glass/polyester composites is investigated in this paper. The G_Ic of planar specimens depends on the fibre orientation, θ in the layers adjacent to the fracture plane, in addition to the property of matrix material. The mode I fracture toughness and fracture behavior of unstitched and stitched 0/0, 30/−30, 45/−45, 60/−60, 90/90 and 0/90 interfaces of unidirectional fibre mats (UD) and 30/−30, 45/−45 and 90/90 interfaces of woven roving mats (WRM) are studied. WRM layer orientation is represented by the direction of warp fibres. Stitching is done by untwisted Kevlar fibre roving of Tex 175 g/km at the stitch densities (number of stitches per unit area) of 10.24 and 20.48 stitches/inch². The specimens having same stitch density, but different stitch distributions are prepared, and the influence of stitch distribution on G_Ic is studied. Double cantilever beam (DCB) tests are carried out and the G_Ic is determined using modified beam theory. The G_Ic of both unstitched and stitched specimens increases with increase in orientation angle, θ upto 45° above which it decreases. The G_Ic values of unstitched 45/−45 delamination interface is around 2.4 times that of the unstitched 0/0 interfaces. The influence of fibre orientation on G_Ic is clearly observed in unstitched specimens, whereas in the stitched specimens, stitching plays an important role in improving the G_Ic and suppresses the influence of fibre orientation; degree of suppression increases with increasing stitch density. When the value of θ is above 45°, transverse cracks are observed in the delamination interface surrounded by UD layers; while in the delamination interface surrounded by WRM layers, transverse cracks are not initiated irrespective of the fibre orientation angle.     

D.c. properties of ZnO thin films prepared by r.f. magnetron sputtering

In the development of ZnO-based varistors the electrical properties of ZnO/Bi₂O₃ junctions and of the two individual oxides are being investigated. Following our recent work on a.c. conductivity in Al---ZnO---Al sandwich structures we currently report d.c. measurements. The structures were prepared by r.f. magnetron sputtering in an argon/oxygen mixture in the ratio 4:1. Capacitance-voltage data confirm that the Al/ZnO interface does not form a Schottky barrier and measurements of the dependence of capacitance on film thickness indicate that the relative permittivity of the films is approximately 9.7. With increasing voltage the current density changed from an ohmic to a power-law dependence with exponent n≈3. Furthermore measurements of current density as a function of reciprocal temperature showed a linear dependence above about 240 K, with a very low activation energy below this temperature consistent with a hopping process. The higher temperature results may be explained assuming a room-temperature electron concentration n₀ and space-charge-limited conductivity, dominated by traps exponentially distributed with energy E below the conduction band edge according to N = N₀exp(−E/kT_t), where k is Boltzmann's constant. Typical derived values of these parameters are: n₀ = 7.2 × 10¹⁶ m⁻³, N₀ = 1.31 × 10⁴⁵ J⁻¹ m⁻³ and T_t = 623 K. The total trap concentration and the electron mobility were estimated to be 1.13 × 10²⁵ m⁻³ and (5.7−13.1) ×10⁻³m²V⁻¹s⁻¹ respectively.     

Parameter of local cyclic strain distribution

The local cyclic strain distribution near the crack tip was investigated by the Computer Aided Fine Grid Method. This method makes it possible to measure continuously every in-plane component of local cyclic strain distribution. It was found that the magnitude of the local cyclic strain distribution near the crack tip was varied by the applied cyclic load level and the material, but the shape of the local cyclic strain distribution near the crack tip was experimentally scarcely altered.

The local cyclic strain field near the crack tip could be written as the following equation. Δε_eq(r, θ) = ΔA · f(θ) · r⁻¹ A single parameter ΔA, which characterizes the local cyclic strain field near the crack tip, was newly proposed by authors.     

Investigation of the nucleation mechanism in bias-enhanced diamond deposition on silicon and molybdenum

Polycrystalline diamond films were deposited on Si and Mo substrates in a microwave plasma-enhanced chemical vapour deposition reactor employing bias-enhanced nucleation. The deposition process was subdivided into two consecutive steps: the pretreatment (bias-enhanced nucleation) and the diamond growth step. To investigate the nucleation process we kept the deposition parameters during the diamond growth step constant and only changed the parameters during the pretreatment. The methods employed to analyze the deposited films after the pretreatment step were electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy.

The nucleation density (N_D) on Si following the complete deposition cycle (pretreatment and diamond growth step) increases considerably from 5 × 10⁸ cm⁻² to 5 × 10¹⁰ cm⁻² with an increase in the substrate temperature during the pretreatment (T_p) in the temperature range from 680 to 750 °C. For T_p ≥ 770 °C continuous films are formed. The structure of the pretreatment deposit undergoes likewise considerable changes: if T_p exceeds 770 °C the appearance of an intense diamond plasmon at 34 eV is observed, indicative of an increase in the concentration of diamond crystallites embedded in an otherwise amorphous carbon matrix. Our experiments suggest that diamond crystallites formed during the pretreatment serve as nucleation centres for the subsequent diamond growth.

The same deposition parameters which result in the formation of a continuous diamond film on Si, yield only low nucleation densities on Mo. An increase in N_D from 6 × 10⁶ cm⁻² to 2 × 10⁸ cm⁻² can be achieved by raising the methane concentration [CH₄] in the gas phase during the pretreatment from 5 to 50% (T_p = 820 °C). The carbon concentration at the surface for the pretreatment deposit, determined by XPS analysis, increases likewise with [CH₄]. According to the EELS analysis the structure of the pretreatment deposit is comparable with disordered graphite or a-C and no diamond plasmon is observed. The high [CH₄] is required to form the Mo-carbide interface and balance the diffusion of carbon into the metal before the a-C layer can be formed.

The formation of nucleation centres during the bias-enhanced nucleation seems under these deposition conditions to proceed via different pathways on Si and Mo. While the nucleation on Si appears to be linked to the formation of diamond nanocrystals during the pretreatment, this is not the case for Mo.     

Highly homogeneous silica coatings for optical and protective applications deposited by PECVD at room temperature in a planar uniform distributed electron cyclotron resonance plasma reactor.

Thin near-stoichiometric silica films were deposited by plasma-enhanced chemical vapour deposition (PECVD) using pure SiH₄ and O₂ in a planar plasma reactor based on the proprietary uniform distributed electron cyclotron resonance (UDECR) technology. Samples were kept approximately at room temperature during the process. In the pressure range 0.1–0.4 Pa, dense ( > 5 × 10¹⁰ cm⁻³) diffusion plasmas could be sustained very homogeneously over areas larger than 200 mm× 200 mm. In conjunction with appropriate distributed gas injection set-up, extremely good layer uniformities were obtained, with no visible irisations for thicknesses of 0.1–6 μm. The reactor concept intrinsically lends itself to process scale-up which is even trivial along one dimension. The effects of gas flow rates and substrate r.f. bias were investigated, mainly by Fourier transform infrared absorption spectroscopy and spectroscopic ellipsometry (1.4–5.0 eV). The Si-H and O-H bond contents were found to be very low for all samples. For films deposited under sufficient ion bombardment energy, typical values for the refractive index at 2.0 eV (1.458) and the Si-O-Si stretching frequency (1075 cm⁻¹) were very close to those obtained in the case of thermally grown silica, indicating an unusually dense microstructure for the as-deposited PECVD films grown at quasi-ambient temperature.

Transparent protective coatings 3–5 μm thick showing excellent abrasion resistance and weatherability could thus be deposited on metals and optical polymers.     

Crystallinity properties of parylene-n affecting its use as an ILD in submicron integrated circuit technology

Parylene-n (Poly-p-xylylene) (PA-n) [1–3] has a long history of use as a moisture barrier for printed circuit boards and hybrids. This paper evaluates this compound as a candidate vapor-depositable polymer interlayer dielectric for submicron integrated circuit technology due to its low dielectric constant, good step coverage, and high etch selectivity. To apply PA-n on high-density very large scale integrated circuits, its properties, such as deposition rate, deposition yield, and Crystallinity, are investigated as a function of deposition pressure and annealing temperature. The deposition rate was found in the range of 2.66 Pa to 13.3 Pa to be a linearly increasing function of pressure. Good-quality films were obtained when pressure was controlled below 10.64 Pa. Cloudy films, however, were found at 13.3 Pa. The deposition rate could be as high as 3.33 × 10⁻¹⁰ m s⁻¹ when deposited at 10.64 Pa. The plot of PA-n yield vs. pressure showed a constant plateau of 1 × 10⁻⁴ m kg⁻¹ from 2.66 Pa to 10.64 Pa. The optimum deposition rate was hence obtained at 10.64 Pa without compromising the deposition yield. The crystallinity-associated properties examined were hardness, dielectric constant, and water permeability. A lower deposition pressure was observed to produce higher Crystallinity that could be further enhanced by thermal annealing. A 5 × 10⁻⁸ m hard surface layer was detected with hardness 3.5 GPa, that was 3˜7 times larger than that of bulk hardness which was 0.4˜0.7 GPa. The bulk hardness was found to increase as Crystallinity increased. The dielectric constant tended to increase when the deposition pressure decreased. Furthermore, the dielectric constant was nearly constant when the polymer was heated up to temperatures as high as 698 K. This behavior, together with the formation of the hard layer and a higher Crystallinity, was believed to result from the improved film organization of the deposited films. The competition between the film build-up in the surface region and the monomer diffusion into the bulk region (penetration) was theorized to be responsible for the film organization. The water permeability, which was measured to be as low as 1.2 × 10⁻¹⁵ kg m⁻¹ s⁻¹ Pa⁻¹ and was found to increase as the deposition pressure was increased, further strengthened the film organization claim.     

Effect of strain rate on interlaminar shear properties of carbon/epoxy composites

In this paper, the effect of strain rate on interlaminar shear properties of laminates is studied. The material tested was a T300/5208 carbon/epoxy composite, and the range of strain rates explored was about 10⁻³ − 10³ s⁻¹. The specimens used were designed and optimized by finite element analysis, and the calculations are presented here. One of the specimens permitted the determination of the interlaminar shear modulus, G₁₃, and the other permitted the determination of the interlaminar shear strength, S₁₃. No influence of testing speed on interlaminar properties was observed at low, intermediate and high strain rates. Fracture surfaces were studied by scanning electron microscopy: a slight difference was observed between specimens tested at low and high strain rates.     

Space-charge-limited conductivity in evaporated cadmium selenide thin films

We have studied the basic d.c. electrical properties of evaporated CdSe films in the context of the development of inexpensive solar cells. Earlier measurements have shown significant variations, which depend on the preparation and previous treatment of the films. In the present work Al---CdSe---Al sandwich structures were studied, with the CdSe thickness in the range 0.1–1.0 (μm. D.c. capacitance varied inversely with film thickness, yielding a permittivity of 7.82 × 10⁻¹¹ F m⁻¹ (relative permittivity 8.83). Current density was proportional to applied voltage at low voltage levels, but followed a power law at higher voltages with exponent typically 2.5; the transitional voltage was directly proportional to the square of the film thickness. The results were interpreted as ohmic conduction at low voltages and space-charge-limited conductivity (SCLC) dominated by an exponential trap distribution, at higher voltage levels. Measurements of current density as a function of inverse temperature for different applied voltages in the SCLC region enabled the derivation of typical mobilities in the range of ( 7.65–10.15) × 10⁻⁵ m² V⁻¹ s⁻¹ using the results of our existing theory. This value of mobility and the derived trapping parameters were in general agreement with some earlier measurements.     

Growth mechanism of stress corrosion cracking in high strength steel

Stress corrosion crack growth rates are measured at sveral stress intensity levels for low-tempered 4340 steel in 0.1N H₂SO₄ solution. The characteristics of the growth rates are divided into three regions of stress intensity factors: Region I near K_1SCC; Region III near unstable fracture toughness, K_1SC; and Region II, which lies between the two. K_1SCC is the value of K at which no crack growth can be detected after 240 hr.

In order to explain these experimental results, the crack initiation analysis reported in a previous paper is extended to the growth rates. A detached crack initiates and grows at the tip of an already existing crack. When the detached crack reaches the tip of the main crack, the process repeats as a new existing crack.

A relationship between crack growth rate, v, and stress intensity factor, K, is obtained as a function of b/a and a = b + d, where b is the distance from the tip of the main crack to the detached crack, and d is the ydrogen atom saturated domain.

The experimental data are in good agreement with the theoretical values in Region II when a = 0.02 mm, b/a = 0.8, c₁/c₀ = 2.8 for 200°C tempered specimens and a = 0.015 mm, b/a = 0.7, c₁/c₀ = 3.0, ρ_b = 0.055 mm for 400°C tempered specimens, where ρ_b is a fictitious notch radius. The plateau part in Region II for 400°C tempered specimens is also successfully explained by the present theory. For Region III, the value of b/a will be almost equal to 1 because v → ∞ for b/a → 1. On the other hand, for Region I, b/a will be zero, since the value of v becomes negligibly small and no crack growth is observable.     

Characteristics of brittle fracture under general combined modes including those under bi-axial tensile loads

In this paper, the brittle fracture initiation characteristics under general combination of the opening mode (Mode I), sliding mode (Mode II) and tearing mode (Mode III) were investigated both theoretically and experimentally.

First, the perfectly brittle fracture tests were conducted on specimens of PMMA (Polymethylmethacrylate) for all possible combinations of the fracture modes including respective pure modes. The experimental fracture strengths were compared with those predicted by the fracture criteria which are represented in terms of: (1) maximum tangential stress, [σ_gq]_max, extended to general combined modes, (2) maximum energy release rate at the propagation of a small kinked crack, [G^k(γ)]_max, and (3) newly derived maximum energy release rate at the initiation of a small kinked crack, [G(γ)]_max. It was found that the [G^k(γ)]_max or [G(γ)]_max criterion was very effective to predict both the direction of initial crack propagation and the fracture strength. These energy release rates are expressed in closed forms, and the interaction curves of the brittle fracture strength under arbitrary combinations of Modes I, II and III were derived.

Next, for fracture accompanied by plastic deformation, tests were carried out on specimens of mild steel (SM 41) imposing bi-axial tensile loads at various low temperatures. Then, brittle fracture with plastic deformation occurs under a combination of Modes I and II. In the case of brittle fracture with small scale yielding, the [G(γ)]_max criterion predicts well the direction of initial crack propagation but estimates only lower fracture strength than the experimental one. In the cases of brittle fracture with large scale yielding and under general yielding, it was found from the fracture tests that the direction of initial crack propagation was nearly normal to the resultant vector of the crack opening displacements in the opening and sliding modes at the notch tip. To this type of fracture, the modified COD criterion predicts well the direction of initial crack propagation, but lower fracture strength.

When brittle fracture occurs under the influence of plastic deformation, in such cases as the last three mentioned above, the actual fracture strength is higher than what the most reliable criterion predicts and it increases as deformation in Mode II becomes larger.     

Semiconducting and structural properties of CrSi2 A-type epitaxial films on Si(111)

Chromium disilicide (CrSi₂) films 1 000 Å thick have been prepared by molecular beam epitaxy on CrSi₂ templates grown on Si(111) substrate. The effect of the substrate temperature on the structural, electrical and optical properties of CrSi₂ films has been studied by transmission and scanning electron microscopies, optical microscopy, electrical resistivity and Hall effect measurements and infrared optical spectrometry. The optimal temperature for the formation of the epitaxial A-type CrSi₂ film have been found to be about 750°C. The electrical measurement have shown that the epitaxial A-type CrSi₂ film is p-type semiconductor having a hole concentration of 1 × 10¹⁷cm⁻³ and Hall mobility of 2 980 cm² V⁻¹ s⁻¹ at room temperature. Optical absorption coefficient data have indicated a minimum, direct energy gap of 0.34 eV. The temperature dependence of the Hall mobility (μ) in the temperature range of T = 180–500 K can be expressed as μ = 7.8 × 10¹⁰T⁻³cm²V⁻¹s⁻¹.     

Thermal evolution of TiO2---ZrO2 composites prepared by chemical coating processing

A xZrO₂ (100−x)TiO₂ composite gel powder (x = 50 mol%) has been prepared by chemical processing of anatase as inner core coated with in situ precipitated amorphous zirconia as outer core, which was obtained from controlled hydrolysis of zirconyl chloride using ammonia at pH=9–10. The thermal evolution of this composite is reported, showing the crystallization of metastable cubic/tetragonal zirconia at 437°C, as detected by DTA at 10°C min⁻¹ and XRD, with activation energy of 407 ± 10 kJ mol⁻¹, and the feasibility of preparing zirconium titanate powders by reaction of TiO₂ and ZrO₂ by heating at higher temperatures is discussed.     

Highly conducting indium tin oxide (ITO) thin films deposited by pulsed laser ablation

Highly conducting and transparent indium tin oxide (ITO) thin films were prepared on SiO₂ glass and silicon substrates by pulsed laser ablation (PLA) from a 90 wt.% In₂O₃-10 wt.% SnO₂ sintered ceramic target. The growths of ITO films under different oxygen pressures (P_O2) ranging from 1×10⁻⁴–5×10⁻² Torr at low substrate temperatures (T_s) between room temperature (RT) and 200°C were investigated. The opto-electrical properties of the films were found to be strongly dependent on the P_O2 during the film deposition. Under a P_O2 of 1×10⁻² Torr, ITO films with low resistivity of 5.35×10⁻⁴ and 1.75×10⁻⁴ Ω cm were obtained at RT (25°C) and 200°C, respectively. The films exhibited high carrier density and reasonably high Hall mobility at the optimal P_O2 region of 1×10⁻² to 1.5×10⁻² Torr. Optical transmittance in excess of 87% in the visible region of the solar spectrum was displayed by the films deposited at Po₂≥1×10⁻² Torr and it was significantly reduced as the P_O2 decreases.     

The growth of fatigue cracks through particulate sic reinforced aluminum alloys

Crack growth rates for large fatigue cracks in 12 variations of particulate silicon carbide reinforced aluminum alloy composites have been measured. Composites with seven different matrix alloys were tested, four of which were of precipitation hardening compositions, and those were tested in both as-extruded and peak aged conditions. Five of the materials were made by casting, ingot metallurgical methods and two of the alloys by mechanical alloying, powder metallurgical methods. For both manufacturing methods, primary fabrication was followed by hot extrusion. The fatigue crack growth curves exhibited an approximately linear, or Paris law, region, fitting the function da/dN = BΔK^s, and a threshold stress intensity factor, ΔK_th. As has been found for other materials, the coefficients B and s are correlated; for these composites In B= −16.4−2.1s. A correlation was also found between ΔK_th and s, and it was found possible to compute the magnitude of ΔK_th using a simple model for the threshold together with yield stress and SiC size and volume fraction. These results were explained using a relationship between ΔK_th and crack closure determined previously for unreinforced aluminum alloys. The path of fatigue crack growth is through the matrix for these composites, and SiC has the effect of altering the slip distance, therefore, the plasticity accompanying fatigue cracks. It was shown that all the crack growth rate curves were reduced to one equation having the form da/dN = B'ΔK_eff^s' where B' = 6.5 × 10^-9m/cy and s' = 1.7. A partly theoretical method for predicting fatigue crack growth rates for untested composites is given. Fatigue crack surface roughness was measured and found to be described by a fractal dimension, but no correlation could be obtained between surface roughness parameters and ΔK_th.     

On the question of flow stress at high strain rates controlled by dislocation viscous flow

Moving dislocation experience a damping force because of their interactions with lattice phonons and electrons. Except at velocities close to the transverse sound velocity this force is proportional to the dislocation velocity. A high plastic strain rates dislocations may be required to move so quickly that dislocation damping forces determine the flow stress. In this note an estimate is made of strain rate at which dislocation damping becomes important. In the plastic flow stress range of 10 MPa to 100 MPa (for aluminum) the critical strain rate is of the order of 4 × 10⁵ s⁻¹to 10⁶ s⁻¹ if almost all the dislocation within a piece of metal are mobile during plastic straining. If only a small fraction of the dislocations during plastic straining is mobile, the critical strain rate is reduced by an amount equal to this fraction.     

Weight function calculations for mixedmode fracture problems with the virtual crack extension technique

An efficient finite element method is presented for calculating the stress intensity factors (K_I and K_II) and the weight functions for mixed-mode cracks with one virtual crack extension. The computational efficiency is enhanced through the use of singular elements and the application of colinear virtual crack extension (VCE) technique to symmetric mesh in cracktip neighborhood. This symmetric mesh in crack-tip vicinity permits the analytical separation of strain energy release rate into G_I for Mode I and G_II for Mode II for the mixed fracture problems with the colinear virtual crack extension.

Rice's displacement derivative representation of weight function vector for symmetric crack has been extended to the mixed fracture mode at nodal location (x_i,y_i) with crack length (a) and inclination angle (β) as h_I(II)(x_i, y_i, a, β) = (H/2K_I(II)(∂U_I(II)(x_i, y_i, a, β/∂a).

This equation permits explicit determination of weight functions for the entire structure of a given asymmetric crack geometry with colinear VCE technique. The explicit weight functions for mixed fracture mode depend strongly on the constraint conditions. The method of obtaining the required stress intensity factors of a given asymmetric crack geometry, from the weight function concept under the selected constraint conditions, which are different from constraint conditions used in the available weight functions for the same crack geometry, is also presented in this paper. This is accomplished by combining the predetermined explicit weight functions with the self-equilibrium forces at their application locations. These self-equilibrium forces include both the applied surface tractions and the reaction forces induced from the constraint conditions.     

Thermal optical properties of TiO2 films

A fibre optic experimental arrangement was used to determine the thermo-optic coefficient (dn/dT) of electron beam deposited titanium dioxide coatings on the cleaved end faces of multimode optical fibres for a wavelength range between 600 and 1050 nm. The temperature-induced change in the index of refraction (n) and extinction coefficient (k) were successfully determined from reflection spectra. Measurements of n and k at various wavelengths for different temperatures enabled the determination of dn/dT and dk/dT. It was found that dn/dT takes different values at different temperature ranges. For example, at 800 nm, dn/dT was (−1.77±0.7)×10⁻⁴ K⁻¹, between 18°C and 120°C, and took a value of (−3.04±0.7)×10⁻⁴ K⁻¹ between 220°C and 325°C.     

Corrosion of tin in citric acid solution and the effect of some inorganic anions

The corrosion behaviour of tin in different concentrations of citric acid solutions (0.3–1.0 M, pH=1.8) was studied at 30 °C by potentiodynamic technique. The E/I profiles exhibit an active passive behaviour. The active dissolution involves one anodic peak A associated with a dissolution of the metals as Sn(II) species. The passivity is due to the formation of thin film of SnO₂ and or Sn(OH)₄ on the anode surface. The cathodic sweep shows a small peak C related to the reduction of the passive film. The peak current density I_p of peak A increases with increasing both acid concentration and sweep rate.

The effects of adding increasing concentrations of Na₂CrO₄, NaMoO₄, NaNO₃ and NaNO₂ on the corrosion of tin in 0.5 M citric acid at 30 °C were investigated. Both CrO₄²⁻ and MoO₄²⁻ ions inhibit the corrosion of tin and the extent of inhibition enhances with their concentrations. Addition of either NO₃⁻ or NO₂⁻ accelerates the corrosion of tin. NO₃⁻ ions are more aggressive than NO₂⁻ ions.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.