Hydroxyapatite-coated metals: Interfacial reactions during sintering

Electrophoretic deposition (EPD) is a low cost flexible process for producing HA coatings on metal implants. Its main limitation is that it requires heating the coated implant in order to densify the HA. HA typically sinters at a temperature below 1150C, but metal implants are degraded above 1000C. Further, the metal induces the decomposition of the HA coating upon sintering. Recent developments have enabled EPD of metathesis-synthesised uncalcined HA which sinters at 1000C. The effects of temperature on HA-coated Ti, Ti6Al4V, and 316L stainless steel were investigated for dual coatings of metathesis HA sintered at 1000C. The use of dual HA coatings (coat, sinter, coat, sinter) enabled decomposition to be confined to the undercoat (HA layer 1), with the surface coating decomposition free. The tensile strength of the three metals was not significantly affected by the high sintering temperatures (925C < T < 1000C). XRD/SEM/EDS analyses of the interfacial zones revealed that 316L had a negligible HA:metal interfacial zone (1 m) while HA:Ti and HA:Ti6Al4V had large interfacial zones (>10 m) comprising a TiO₂ oxidation zone and a CaTiO₃ reaction zone.     

Mathematical modeling of a transient heat-conduction process

A numerical algorithm is proposed for solution of the transient heat-conduction equation by the Monte Carlo method. The calculated values of the temperature are compared with experimental data.Notation U temperature - t time - a thermal diffusivity - x, y, z coordinates - (x, y, z, t) temperature on the surface of the body - g(x, y, z) initial temperature - T finite time of investigation of the process - (x, y, z, t) = F (x, y, z, t)/c where F(x, y, z, t) is an internal heat source - c specific heat - density Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 39, No. 4, pp. 745–747, October, 1980.     

Dielectric and structural properties of A-cation-deficient perovskites, tetragonal tungsten bronzes and their composites in the K2Sr4(Mgx Nb10-x) Li3xO30 system

In the K2Sr4(MgxNb10-x) Li3xO30 system (0x1.33), two phases, one having a tetragonal tungsten bronze (TTB) structure and the other having a perovskite-type structure, are observed after calcination and sintering. The synthesis of single-phase samples, having either of these structure types, has allowed for the determination of their respective contribution to the system's dielectric properties, specifically r=f (T ) and tg=f (T) over the temperature range –60 to 150 °C. Using X-ray and electron diffraction techniques, scanning electron microscope observations and energy dispersive spectroscopy analysis, various A-cation-deficient perovskite phases were characterized, in particular Sr0.8(Mg0.2Nb0.8)O3. The compositional ability of the TTB structure in this system is also correlated to the r=f (T ) curves, which exhibit a broad maximum. © 1998 Kluwer Academic Publishers     

A calorimetric study of aluminium alloy AA-7075

The differential scanning calorimetry (DSC) technique has been used to examine the precipitation process in the commercial Al-Zn-Mg-Cu alloy AA-7075. In general the results are in good agreement with previous DSC data on a similar alloy and can be related to the precipitation process observed by electron microscopy. However, an additonal precipitation process has been detected at low temperatures, which is usually masked by coarsening and dissolution of Guinier-Preston (G-P) zones formed during room-temperature ageing. This precipitate, which is referred to as the precursor to after Lyman et al., does not redissolve on going to higher temperatures and is an important step in the ageing process in these alloys.     

Evidence for collective excitations in superconducting tin whiskers

Based on the assumption that a phase-slip center in a clean quasi-one-dimensional superconductor excites a collective oscillation, the time-averaged value of the electrochemical potential of quasiparticles is calculated. At larger distances from the phase-slip center, swings below (or above) the electrochemical potential _p of the Cooper pairs. This makes it possible to understand the unexpected results of previous measurements.     

On the re-inforcement of thermoplastics by imperfectly aligned discontinuous fibres

Studies of deformation behaviour of short fibre reinforced thermoplastics are complicated by the facts that usually a wide range of fibre lengths are present in moulded test pieces and that the fibres are not systematically oriented with respect to any test direction. An equation has been derived for the stress/strain curve of such a material. This has been used to determine fibre/matrix bond strengths in two glass/nylon 6.6 and two glass/polypropylene composites from measured stress/strain curves and fibre length distributions.It is concluded that major improvements in the properties of these materials will only be achieved by modifying processing to retain longer fibres.List of symbols E _c Modulus of composite - E _f Modulus of fibre - E _m Modulus of matrix - V _f Volume fraction of fibre - _c Stress in the composite - _f Peak stress in a fibre - Average stress in a fibre - _uf Ultimate strength of fibres - _m Stress in matrix at fibre failure strain - _uc Ultimate strength of the composite - _c Strain in composite - _uc Ultimate strain of the composite - Shear strength of the fibre matrix bond - L Fibre length - L Critical fibre length at a composite strain e - L _c Critical fibre length for fibre failure - r Fibre radius     

Subatmospheric Vapor Pressures for Fluoromethane (R41), 1,1-Difluoroethane (R152a), and 1,1,1-Trifluoroethane (R143a) Evaluated from Internal-Energy Measurements

Vapor pressures were evaluated from measured internal-energy changes U ⁽²⁾ in the vapor+liquid two-phase region. The method employed a thermodynamic relationship between the derivative quantity (U ⁽²⁾/V) _T , the vapor pressure p , and its temperature derivative (p/T). This method was applied at temperatures between the triple point and the normal boiling point of three substances: fluoromethane (R41), 1,1-difluoroethane (R152a), and 1,1,1-trifluoroethane (R143a). In the case of R41, vapor pressures up to 1 MPa were calculated to validate the technique at higher pressures. For R152a, the calculated vapor pressure at the triple-point temperature differed from a direct experimental measurement by less than the claimed uncertainty (5 Pa) of the measurement. The calculated vapor pressures for R41 helped to resolve discrepancies in several published vapor pressure sources. Agreement with experimentally measured vapor pressures for R152a and for R143a near the normal boiling point (101.325 kPa) was within the experimental uncertainty of approximately 0.04 kPa (0.04%) for the published measurements.     

Viscoelastic and rheological behavior of concentrated colloidal suspensions

Molecular approaches are discussed to the density (), viscoeleastic (), and rheological () behavior of the viscosity(,,) of concentrated colloidal suspensions with 0.3 < < 0.6, where, is the volume fraction, the applied frequency, and ; the shear rate. These theories are based on the calculation of the pair distribution functionP ₂(r,,), wherer is the relative position of a pair of colloidal particles. The linear viscoelastic behavior(,,=0) follows from an equation forP ₂(r,,) derived from the Smoluchowski equation for small, generalized to large by introducing the spatial ordering and (cage) diffusion typical for concentrated suspensions. The rheological behavior(,,=0) follows from an equation forP ₂(r,) of a dense hard-sphere fluid derived from the Liouville equation. This leads to a hard-sphere viscosity^hs(,) which yields the colloidal one(,) by the scaling relation(,) ₀=^hs(,) _B, where ₀ is the solvent viscosity. _B is the dilute hard-sphere (Boltzmann ) viscosity and the's are appropriately scaled,(,) and(,) agree well with experiment. A unified theore for(,,) is clearly needed and pursued.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994. Boulder, Colorado, U.S.A.     

Equation of state of3He near its liquid-vapor critical point

We report high-resolution measurements of the pressure coefficient (P/T) for³He in both the one-phase and two-phase regions close to the critical point. These include data on 40 isochores over the intervals–0.1t+0.1 and–0.2+0.2, wheret=(T–T _c )/T _c and =(– _c )/ _c . We have determined the discontinuity (P/T) of (P/T) between the one-phase and the two-phase regions along the coexistence curve as a function of . The asymptotic behavior of (1/) (P/T) versus near the critical point gives a power law with an exponent (+–1)^–1=1.39±0.02 for0.010.2 or–1×10 ^–2t–10 ^–6 , from which we deduce =1.14±0.01, using =0.361 determined from the shape of the coexistence curve. An analysis of the discontinuity (P/T) with a correction-to-scaling term gives =1.17±0.02. The quoted errors are fromstatistics alone. Furthermore, we combine our data with heat capacity results by Brown and Meyer to calculate (/T) _c as a function oft. In the two-phase region the slope (²/T ²)_c is different from that in the one-phase region. These findings are discussed in the light of the predictions from simple scaling and more refined theories and model calculations. For the isochores 0 we form a scaling plot to test whether the data follow simple scaling, which assumes antisymmetry of – ( _c ,t) as a function of on both sides of the critical isochore. We find that indeed this plot shows that the assumption of simple scaling holds reasonably well for our data over the ranget0.1. A fit of our data to the linear model approximation is obtained for0.10 andt0.02, giving a value of =1.16±0.02. Beyond this range, deviations between the fit and the data are greater than the experimental scatter. Finally we discuss the (P/T) data analysis for ⁴ He by Kierstead. A power law plot of (1/) P/T) versus belowT _c leads to =1.13±0.10. An analysis with a correction-to-scaling term gives =1.06±0.02. In contrast to ³ He, the slopes (²/T ²)_c above and belowT _c are only marginally different.Work supported by a grant from the National Science Foundation.     

A realistic microscopic theory for the high-Tc cuprates

The electronic structure of the high-T_c cuprates is worked out by decomposing the orbitals around the Fermi level into large-U and small-U components. The large-U orbitals are treated by the slave-fermion method, the small-U orbitals by a mean-field approach, and the hybridization between them is then worked out. It turns out that hopping energy binds the spin and the charge of the large-U orbitals. The state so obtained is either antiferromagnetic, or paramagnetic with antiferromagnetic fluctuations and with violation of parity. Two types of charge carriers are predicted: (i) spinless polarons with a very small bandwidth, explaining the anomalous thermoelectric power, the mid-infrared peak, lattice anomalies, etc.; (ii) anomalous carriers of both charge and spin, explaining marginal-Fermi-liquid behavior and deviations from it, anomalous relaxation time, the systematic behavior of the resistivity, the Hall constant, the Hall angle, etc.     

The role of silicon in the formation of the (Al5Cu6Mg2) σ phase in Al-Cu-Mg alloys

The role of silicon in the precipitation of the phase (Al₅Cu₆Mg₂) has been investigated through comparative studies on Al-3.63Cu-1.67Mg (wt%) and Al-3.63Cu-1.67Mg-0.5Si alloys. Both alloys were extensively examined after solution treating at 525°C for 2.5 h followed by ageing at 265°C for times up to 650 h. Limited studies were also undertaken on both alloys after ageing at 200 and 305°C. Precipitation of was observed in Al-3.62%Cu-1.66%Mg-0.5%Si for all ageing conditions studied but was absent in Si-free Al-3.62%Cu-1.66%Mg. In addition, S and phases were observed in both alloys. The volume fraction of phase in the Si containing alloy was substantially reduced by a pre-age stretch followed by ageing for 24 h at 265°C with S being the dominant precipitate type. The volume fraction of phase in the Si containing alloy was lower after ageing 24 h at 200°C than after 24 h at 265 and 305°C. Peak hardness was higher for the Si free alloy on ageing at 200 and 265°C, but the Si free alloy softened more rapidly, reflecting the more rapid coarsening kinetics of S compared with .     

The effective surface energy of brittle materials

The effective surface energy of four brittle materials, alumina, poly(methylmethacrylate), glass, and graphite, is calculated from load/deflection curves of notched bars deformed in three-point bending. Two of the methods, which are commonly used in fracture mechanics studies,viz the modified Griffith treatment and the compliance analysis method, are concerned with the effective surface energy at the initiation of fracture, _I . The third method, the work of fracture test, is concerned with the mean effective surface energy over the whole fracture process, _F . The two estimates of _I give consistent values, and there is no systematic variation of _I with notch depth. Values of _F decrease with increasing notch depth as the fracture process becomes more controlled. For alumina _{I F} . For PMMA and glass _I > _F because of a multiplicity of crack sources during fracture initiation. For graphite _I < _F because of subsidiary cracking as fracture proceeds.     

Universality and the scaling laws in the superfluid phase transition of3He-4He mixtures

From the second-sound velocityU ₂ near the superfluid transition point, the superfluid densities in³He-⁴He mixtures, _s (X) and _s (), were deduced along the paths of constant³He concentrationX and of constant chemical potential difference of³He and⁴He. The following critical exponents of _s are determined: (a) =XX for _s (X) in the(X, T) plane,(b) X for _s (X) in the(, T) plane, and(c) for _s () in the(, T) plane. It is found that and _X change by about 4–6% relative to with increasing³He concentration up toX=0.4 and by 8–10% up toX=0.53. It seems that, belowX=0.53, universality hold for . Values of have been found to be in good agreement with the critical exponent of _s in pure⁴He under constant pressure. The values of and _X forX0.53 are also found to be consistent with the scaling relations in the (,T) plane of³He-⁴He mixture.Work performed in part while at the Electrotechnical Laboratory.     

Morphological and crystallographic features of γ-γ′ Ni-Al and Ni-Al-Ti two-phase bicrystals

Several- Ni-Al and Ni-Al-Ti two-phase bicrystals were made by the solid-state diffusion couple method. Each couple consisted of a-phase single crystal and a pure-Ni polycrystal, and was annealed at 1473 K in an Ar gas atmosphere. Single crystal layers of-phase with uniform thickness always grow into the parent-phase single crystals. The resultant/ interface has no voids or facets regardless of the orientation of interface and the chemical composition of the-phase. Porosity formation due to the Kirkendall effect is observed in the diffused region. Concentration profiles exhibit nearly constant gradients in-phase. The orientation relationship between both phases is found to be 001//001, that is, the-phase grows epitaxially along the crystal orientation of-phase.     

Complexities in STEM analyses of polymer blend thin films

Polystyrene (PS)-polyether sulphone (PES) polymer blend thin films were prepared for examination in a scanning transmission electron microscope. The microstructures observed in 75 wt % PS-25 wt % PES films consisted of spherical inclusions, ranging from 0.2 to 1.2m in diameter. X-ray spectrometric analysis in the microscope revealed that the inclusions were PES-rich, while the matrix contained only PS. Attention in this paper is paid to the contrast in the annular dark-field detector (ADF) images from these thin films. This image contrast has a complicated dependence on both the angular range subtended by the dark-field detector and mass-thickness variations within the films. On microscopes with appropriate lens controls which permit the acceptance angle of the ADF detector to be varied, it becomes possible actually to reverse the contrast between the two phases.     

The Interplay of Electronic and Nuclear Magnetism in PtFe x at Milli-, Micro-, and Nanokelvin Temperatures

We have measured ac susceptibility, nuclear magnetic resonance, and nuclear heat capacity of two PtFe _x samples with concentrations of magnetic impurities x = 11 ppm and 41 ppm at magnetic fields (0 ± 0.05) mTB248 mT. The susceptibility data have been measured at temperatures of 0.3 KT100 mK, no hint for nuclear magnetic ordering could be detected to a temperature of 0.3 K. The nuclear heat capacity data taken at 1.4 KT10 mK show enhanced values which scale with x at low polarization. This effect is described by a model assuming an internal magnetic field caused by the impurities. No indication for nuclear magnetic ordering could be detected to 1.4 K. The nuclear magnetic resonance experiments have been performed on these samples at 0.8 KT0.5 mK and 2.5 mTB22.8 mT as well as on three other samples with x = 5, 10, 31 ppm in a different setup at 40 KT0.5 mK and at 5.4 mTB200 mT. Spin-lattice and effective spin-spin relaxation times ₁and ₂ ^* of ¹⁹⁵ Pt strongly depend on x and on the external magnetic field. No temperature dependence of ₁and ₂ ^* could be detected and the NMR data, too, give no hint for nuclear magnetic ordering to 0.8 K.     

Structure of martensite formed in Cu-Al-Fe single crystals duringin situ HVEM pseudoelastic tensile experiment

Single crystals of the CuAlFe alloy, containing 14.5 wt% Al and 2.2 wt% Fe were subjected toin situ tensile experiment using straining attachment in a 1 MV electron microscope. Loadelongation curves were obtained for three foil plane/tensile direction orientations: (001) [0 1 0], (0 0 1) [1 1 0] and (1 1 0) [¯1 1 2]. Each crystal was subjected to two cycles of pseudoelastic deformation up to maximum 2% strain, showing almost complete shape recovery. Structure observations and electron diffraction pattern indicated that during deformation of samples of (0 0 1) [1 1 0] and (1 1 0) [1 1 2] orientations, formation of ₁ martensite was observed and only at later stages narrow needles of ₁ nucleate in front of ₁. During pseudoelastic deformation in the (0 0 1) [1 0 0] direction, martensite forms as a mixture of narrow plates possessing either 2H or 18R structures. The following crystallographic relationship between the parent phase and both types of martensite was observed: [1 00] ₁ [101] ₁ and (0 0 1) ₁ (0 1 0)₁;(0 0 1) ₁ (0 1 0) ₁ and [1 1 0] ₁ [0 0 1] ₁. From the character of sidebands reflections presence of 1 0 1 1 0¯1 static displacement waves was inferred.     

Compressibility measurements of β- and β″ -alumina

The compressibilities of the a- and c-axes for sodium - and -aluminas were determined up to 10 GPa from the pressure dependence of powder X-ray diffraction measured at room temperature using synchrotron radiation as an X-ray source. Powders of sodium - and -aluminas which were prepared from grinding synthesized single crystals were used as the specimens for X-ray diffraction. The compressibilities of - and -aluminas are 1.5 ± 0.2 ×10^–12 and 1.7 ± 0.2 × 10^–12 Pa^–1 for the a-axis and 2.9 ± 0.2x10^–12 and 1.6 ± 0.2 ×10^–12 Pa^–1 for the c-axis, respectively. For the c-axis, the compressibility of -alumina is larger than that of -alumina. This experimental fact is explained by the different stacking of oxygen layers and the different content in sodium ion between - and -aluminas.     

Deformation of single crystals of gallium arsenide

Deformation of single crystals of gallium arsenide is reported in bend and tension up to 1000° C whilst maintaining stoichiometry in an arsenic atmosphere. Surface defects and impurity segregation are shown to be dislocation sources. The dislocation density is low enough, however, to show large yield drops which are analysed in detail. Strains of 39% are possible. The activation energy for dislocation movement is increased by heat-treatment owing to an increase in point defect population.Electron microscopy shows that the predominant slip systems are {111} 110 and the majority of dislocations have b=a/2 110, the axes lying along 110 and 112 directions. Sub-cell formation occurs with sub-boundaries lying along 110 directions.     

Nonlinear Response of a Continuous Wave NMR Spectrometer for Samples with a Large Magnetization

We present a new insight in the response of a CW NMR spectrometer for highly magnetized samples above 100 MHz. The spectrometer is a bridge made of a magic T. The output of the bridge is proportional to the reflection coefficient, , of a resonant circuit, which is built with a coil containing the sample. The sensitivity of the reflection coefficient to the complex susceptibility of the sample, () = () – j(), depends on the quality factor, Q, of the circuit and filling factor, . When the condition Q 1 is not fulfilled, we show indeed that the use of a simple crystal detector, which is only sensitive to || gives rise to a strong nonlinear response of the spectrometer. Measurements of the complex value of by means of phase sensitive detection allow to recover a linear behavior. We discuss and illustrate those issues with a few circuits we designed for our measurements on liquid ³ He with spin polarizations up to 15 %. A method is described to build in a reproducible and predictable way resonant circuits matched to 50 in the frequency range 100 – 400 MHz with a quality factor as high as 1000 at 4 K.