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All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Physical and Biological Properties of Cobalt- and Copper-Doped Calcium Phosphates as Bone Substitute Materials

Arthritis, osteoporosis, and other bone diseases and defects are common medical issues worldwide. By utilizing ceramic biomaterials as bone substitutes to treat these diseases, bone regeneration can be promoted and toxicity from the substitute material can be limited. Calcium phosphate (CaP) ceramics have become popular as bone substitutes due to their biocompatibility and similarity in composition to natural bone. The purpose of this research was to investigate the physical properties and biological responses of CaP-based bone substitutes, doped with metal ions. Some metal ions are present in natural bone in small amounts, and recent studies show they affect the biological responses of CaPs significantly. Dopants such as magnesium (Mg), strontium (Sr), silicon (Si) and iron (Fe) alter the phase composition, mechanical properties, osteogenesis and angiogenesis properties of CaPs, depending on their concentration and method of addition. In the present study, the effects of cobalt (Co) and copper (Cu) on the physical and biological properties of two main CaP materials, brushite cement (BrC) and tricalcium phosphate (TCP), have been investigated. Different concentrations of dopants in forms of oxide and/or chloride were selected and their effect on phase composition, sintering behavior, density, setting time, compressive strength and in vitro interaction with osteosarcoma and osteoblast cells were studied. Different techniques of sample preparation, challenges during cement preparation and compact sample pressing, sintering, and methods of dopant addition are discussed. The presence of Cu in tricalcium phosphate was found to increase thermal stability of the material and decrease the impact of sintering temperature on porosity. In addition, Cu caused a reduction in expression of inflammatory gene markers by human osteoblast cells and an increased expression at early time points due of osteoinductive markers.The addition of Cu and Co to brushite cement caused an increase in thermal stability of the material, and the addition of Cu caused significant increase in setting time. Small dopant amounts of Co caused decrease in setting time, but higher amounts caused an increase. In addition, Cu dopant in small amounts resulted in an increase of compressive strength. Both Cu and Co led to a decrease in expression of inflammatory gene markers by osteoblast and osteosarcoma cells respectively, and Cu also caused an increase in osteoinductive marker expression. Thus, these results indicate that Cu and Co have a positive impact on the physical, mechanical and biological properties of calcium phosphate biomaterials.

Cummings, Haley V.↗
NASA NTRS1995

Structural, dynamical and electronic properties of CaCuO2

The scalar relativistic version of an accurate first principles full potential self-consistent linearized muffin tin orbital (LMTO) method has been employed for describing the physical properties of the parent system of the high-T(sub c) oxide superconductors, i.e., CaCuO2. The presently employed modified version of the LMTO method is quite fast and goes beyond the usual LMTO ASA method in the sense that it permits a completely general shape of the potential and the charge density. Also, in contrast to LMTO ASA, the present method is also capable of treating distorted lattice structures accurately. The calculated values of the lattice parameters of pure CaCuO2 lie within 3% of the experimentally measured values for the Sr-doped system Ca(0.86)Sr(0.14)CuO(2). The computed electronic structures and the density of states is quite similar to those of the other oxide superconductors, except of their three- dimensional character because of the presence of strong coupling between the closely spaced CuO2 layers. The van Hove singularity peak appears slightly below the Fermi level and a small concentration of oxygenation /or/ substitutional doping may pin it at the Fermi level. The calculated frequencies for some symmetric frozen phonons for undoped CaCuO2 are quite near to the measured data for the Sr-doped CaCuO2.

Agrawal, Bal K.↗
NASA NTRS1990

Growth and properties of Hg-based quantum well structures and superlattices

An overview of the properties of HgTe-CdTe quantum well structures and superlattices (SL) is presented. These new quantum structures are candidates for use as new long wavelength infrared (LWIR) and very long wavelength infrared (VLWIR) detectors, as well as for other optoelectronic applications. Much has been learned within the past two years about the physics of such structures. The valence band offset has been determined to be approx. 350 meV, independent of temperature. The occurrence of electron and hole mobilities in excess of 10(exp 5)cm(exp 2)/V center dot s is now understood on the basis of SL band structure calculations. The in-plane and out-of-plane electron and hole effective masses have been measured and interpreted theoretically for HgTe-CdTe superlattices. Controlled substitutional doping of superlattices has recently been achieved at North Carolina State University (NCSU), and modulation-doped SLs have now been successfully grown and studied. Most recently, a dramatic lowering of the growth temperature of Hg-based quantum well structure and SLs (to approx. 100 C) has been achieved by means of photoassisted molecular beam epitaxy (MBE) at NCSU. A number of new devices have been fabricated from these doped multilayers.

Schetzina, J. F.↗
NASA NTRS1999

Optical Fiber Spectroscopy

This is the final report of work done on NASA Grant NAG-1-443. The work covers the period from July 1, 1992 to December 1, 1998. During this period several distinct but related research studies and work tasks were undertaken. These different subjects are enumerated below with a description of the work done on each of them. The focus of the research was the development of optical fibers for use as distributed temperature and stress sensors. The initial concept was to utilize the utilize the temperature and stress dependence of emission from rare earth and transition metal ions substitutionally doped into crystalline or glass fibers. During the course of investigating this it became clear that fiber Bragg gratings provided a alternative for making the desired measurements and there was a shift of research focus on to include the photo-refractive properties of germano-silicate glasses used for most gratings and to the possibility of developing fiber laser sources for an integrated optical sensor in the research effort. During the course of this work several students from Christopher Newport University and other universities participated in this effort. Their names are listed below. Their participation was an important part of their education.

Buoncristiani, A. M.↗
NASA NTRS1990

Preparation and characteristics of superconducting cuprate thin films: Nd(2-x)Ce(x)CuO4 and substituted Bi-system

Characteristics of the electron-doped-type Nd(2-x)Ce(x)CuO4 systems and substituted Bi2(Sr,Ln)3Cu2Oy system were systematically studied using the high quality thin-film samples. The Nd(2-x)Ce(x)CuO4 thin films with various Ce concentrations, x, were prepared by RF magnetron sputtering on SrTiO3 heated at around 500 C. After subsequent annealing at 1100 C in air, the films showed the c-axis orientation normal to the substrates. By means of the reducing treatment (annealing in a vacuum), superconductivity was induced for the films with 0.14 is less than or equal to x is less than or equal to 0.18. The superconductivity and transport properties of the films were strongly affected by the reducing treatment. The x = 0.15 film exhibited a sharp superconducting transition with zero resistivity at 22 K, in consistent with the diamagnetic properties. The resistivity of the films was fairly low with metallic characteristics, and the sight of the Hall coefficient was negative in the normal state. On the other hand, the normal-state optical measurements showed that the undoped Nd2CuO4 is a semiconductor with a charge transfer gap of 1.3 eV, and that, when Ce ions were doped, a plasma reflection due to the free-carriers came to be seen with the plasma frequency of 1.07 eV for 0.14 is less than or equal to x is less than or equal to 0.18. Moreover, x ray photoemission study revealed that the Cu valence of the film decreased for 2(+) for x = 0 to 1(+) for x = 0.15. These physical properties are in contrast with those of hole-doped-type cuprate superconductors. Bi2(Sr,Ln)3Cu2Oy thin films were also prepared on MgO substrates heated at 600 to 700 C by similar methods. It was found that the growth conditions for Bi-systems with two CuO2 planes were different for each composition and species of lanthanoid in the films. Moreover, preparation of Bi-system with three CuO2 planes was very difficult when lanthanoid atoms were doped in the system. Their electric transport properties and x ray photoemission spectroscopy were investigated. Carrier concentration and Cu valence were discussed with regard to the superconductivity.

Adachi, H.↗
NASA NTRS1992

Novel Cr(4+)-based tunable solid-state lasers

Spectroscopic and laser properties of chromium-doped forsterite (Cr:Mg2SiO4) are reviewed and future directions in development of other Cr(4+)-doped tunable solid-state lasers are discussed. The unique property of chromium-doped forsterite is that the lasing center was identified as tetravalent chromium (Cr(4+)) substituting for tetrahedrally coordinated Si(4+). Development of chromium-doped forsterite laser may stimulate the generation of a new class of tunable solid state lasers based on tetravalent chromium as a laser active ion for the near-IR eyesafe spectral range. The criteria for the development of new Cr(4+)-based tunable solid-state laser crystals are discussed. We also present current research efforts to identify potential low field host crystals, such as silicates, titanites, and germanates, that may be doped with Cr(4+) as an active ion. These new laser materials are expected to cover the wavelength region from 1 - 2 microns, which may be of great technological importance.

Petricevic, V.↗
NASA NTRS1994

Rare Earth Garnet Selective Emitter

Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approx. = 0.75, sup 4)|(sub 15/2) - (sup 4)|(sub 13/2),for Er-YAG and epsilon(sub lambda) approx. = 0.65, (sup 5)|(sub 7) - (sup 5)|(sub 8) for Ho-YAG) at 1500 K. In addition, low out-of-band spectral emittance, epsilon(sub lambda) less than 0.2, suggest these materials would be excellent candidates for high efficiency selective emitters in thermophotovoltaic (TPV) systems operating at moderate temperatures (1200-1500 K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. Selective emitters in the near IR are of special interest for thermophotovoltaic (TPV) energy conversion. The most promising solid selective emitters for use in a TPV system are rare earth oxides. Early spectral emittance work on rare earth oxides showed strong emission bands in the infrared (0.9 - 3 microns). However, the emittance outside the emission band was also significant and the efficiency of these emitters was low. Recent improvements in efficiency have been made with emitters fabricated from fine (5 - 10 microns) rare earth oxide fibers similar to the Welsbach mantle used in gas lanterns. However, the rare earth garnet emitters are more rugged than the mantle type emitters. A thin film selective emitter on a low emissivity substrate such as gold, platinum etc., is rugged and easily adapted to a wide variety of thermal sources. The garnet structure and its many subgroups have been successfully used as hosts for rare earth ions, introduced as substitutional impurities, in the development of solid state laser crystals. Doping, dependent on the particular ion and crystal structure, may be as high as 100 at. % (complete substitution of yttrium ion with the rare earth ion). These materials have high melting points, 1940 C for YAG (Yttrium Aluminum Garnet), and low emissivity in the near infrared making them excellent candidates for a thin film selective emitter. As previously stated, the spectral emittance of a rare earth emitter is characterized by one or more well defined emission bands. Outside the emission band the emittance(absorptance) is much lower. Therefore, it is expected that emission outside the band for a thin film selective emitter will be dominated by the emitter substrate. For an efficient emitter (power in the emission band/total emitted power) the substrate must have low emittance, epsilon(sub S). This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium(Ho) and erbium (Er) doped YAG thin film selective emitters at (1500 K), and compares those results with the theoretical spectral emittance.

Lowe, Roland A.↗
NASA NTRS1984

Magnesium doping of efficient GaAs and Ga(0.75)In(0.25)As solar cells grown by metalorganic chemical vapor deposition

Magnesium has been substituted for zinc in GaAs and Ga(0.75)In(0.25)As solar cells grown by metalorganic chemical vapor deposition (MOCVD). Bis(cyclopentadienyl)magnesium (Cp2Mg) is used as the MOCVD transport agent for Mg. Full retention of excellent material quality and efficient cell performance results. The substitution of Mg for Zn would enhance the abruptness and reproducibility of doping profiles, and facilitate high temperature processing and operation, due to the much lower diffusion coefficient of Mg, relative to Zn, in these materials.

Lewis, C. R.↗
NASA NTRS1995

High pressure synthesis and magnetic studies of quasi one dimensional systems Sr(n-1)Cu(n+1)O(2n) (n=3,5)

SrCu2O3 and Sr2Cu3O5 containing two-leg and three-leg S = 1/2 ladders made of antiferromagnetic Cu-O-Cu linear bonds, respectively, were synthesized at high pressure, and their crystallographic and magnetic properties were investigated. Both susceptibility and T(1) data of NMR (nuclear magnetic resonance) revealed the existence of a large spin gap only for SrCu2O3. Superconductivity, which had been predicted theoretically for carrier-doped SrCu2O3 could not be realized although partial substitution of La(3+) for Sr(2+) seemed to be carried out successfully. Electron carriers injected seems to remain localized.

Azuma, M.↗
NASA NTRS1988

Carbon doping in molecular beam epitaxy of GaAs from a heated graphite filament

Carbon doping of GaAs grown by molecular beam epitaxy has been obtained for the first time by use of a heated graphite filament. Controlled carbon acceptor concentrations over the range of 10 to the 17th-10 to the 20th/cu cm were achieved by resistively heating a graphite filament with a direct current power supply. Capacitance-voltage, p/n junction and secondary-ion mass spectrometry measurements indicate that there is negligible diffusion of carbon during growth and with postgrowth rapid thermal annealing. Carbon was used for p-type doping in the base of Npn AlGaAs/GaAs heterojunction bipolar transistors. Current gains greater than 100 and near-ideal emitter heterojunctions were obtained in transistors with a carbon base doping of 1 x 10 to the 19th/cu cm. These preliminary results indicate that carbon doping from a solid graphite source may be an attractive substitute for beryllium, which is known to have a relatively high diffusion coefficient in GaAs.

Malik, R. J.↗
NASA NTRS1991

Preparation and characteristics of superconducting cuprate thin films: Nd(2-x)Ce(x)CuO4 and substrated Bi-system

Characteristics of the electron-doped-type Nd(sub 2-x)Ce(sub x)CuO4 system and substituted Bi-system were studied using the high quality thin film samples grown by rf magnetron sputtering and/or subsequent heat treatment. The Nd(sub 2-x)Ce(sub x)CuO4 samples with excellent superconducting properties were obtained in thin films and their optical and X-ray photoelectron spectroscopy (XPS) studies were performed with regard to the Ce content and reducing treatment. Substituted BiSr-Ln-Cu-O thin films were prepared and growth conditions for Bi-system with 2-2-1-2 and 2-2-2-2 phases were found. Moreover, a new 2-2-1-2 phase in the simple Bi-Sr-Cu-O system was fabricated by thin film processing and 80 K superconductivity was obtained.

Adachi, H.↗
NASA NTRS2001

Optical Sensors Based on Single Arm Thin Film Waveguide Interferometer

Single-arm double-mode double-order optical waveguide interferometer utilizes interference between two propagating modes of different orders. Sensing effect results from the change in propagation conditions of the modes caused by the environment. The waveguide is made as an open asymmetric slab structure containing a dye-doped polymer film onto a fused quartz substrate. It is more sensitive to the change of environment than its conventional polarimetric analog using orthogonal modes (TE and TM) of the same order. The sensor still preserves the option of operating in polarimetric regime using a variety of mode combinations such as TE(sub 0)/TM(sub 0) (conventional), TE(sub 0)/TM(sub 1), TE(sub 1)/TM(sub 0), or TE(sub 1)/TM(sub 1) but can also work in nonpolarimetric regime using combinations TE(sub 0)/TM(sub 1) or TE(sub 0)/TM(sub 1). Utilization of different mode combinations simultaneously makes the device more versatile. Application of the sensor to gas sensing is based on doping polymer film with an organic indicator dye sensitive to a particular gas. Change of optical absorption spectrum of the dye caused by the gaseous pollutant results change of the reactive index of the dye-doped polymer film that can be detected by the sensor. As an indicator dyes, we utilize Bromocresol Purple doped into polymer poly(methyl) methacrylate, which shows a reversible growth of the absorption peak neat 600 nm after exposure to wet ammonia. We have built a breadboard prototype of the sensor with He-Ne laser as a light source and with a single mode fiber input and a multimode fiber output. The prototype showed sensitivity to temperature change of the order of 2 C per one full oscillation of the signal. The sensitivity of the sensor to the presence of wet ammonia is 200 ppm per one full oscillation of the signal. The further improvements include switching to a longer wavelength laser source (750-nm semiconductor laser), substitution of poly(methyl) methacrylate with hydrophilic high-temperature polyimide, and increase the doping rate of indicator dye. All these improvements are expected to bring sensitivity to 10 ppm of ammonia per one full oscillation of signal independent on the humidity of ambient air. The proposed sensor can be used as a robust and inexpensive stand-alone instrument for continuous environment pollution monitoring.

Sarkisov, S. S.↗
NASA NTRS1997

Space Environment Stability and Physical Properties of New Materials for Space Power and Commercial Applications

Useful and informative results were obtained on virtually all materials investigated. For example, the stability of ITO-based arc-proof transparent coatings was greatly improved by substitution of silicon oxide for magnesium fluoride as a dopant. Research on 'air-doped' ITO films has yielded new insight into their conduction mechanism which will help in further development of these coatings. Some air-doped films were found to be extremely pressure sensitive. This work may lead to improved, low-cost gas sensors and vacuum gauges. Work on another promising transparent arc-proof coating (titanium oxide) was initiated in collaboration with industry. Graphite oxide-like materials were synthesized and tested for possible use in high energy-density batteries and other applications. We also started a high-priority project to find the cause of unexpected environmental damage to the exterior of the Hubble Space Telescope (HST) discovered on a recent Shuttle mission. Materials were characterized before and after exposure to soft x-rays and other threats in ground-based simulators.

Hambourger, Paul D.↗
NASA NTRS1981

Reduced annealing temperatures in silicon solar cells

Cells irradiated to a fluence of 5x10,000,000,000,000/square cm showed short circuit current on annealing at 200 C, with complete annealing occurring at 275 C. Cells irradiated to 100,000,000,000,000/square cm showed a reduction in annealing temperature from the usual 500 to 300 C. Annealing kinetic studies yield an activation energy of (1.5 + or - 2) eV for the low fluence, low temperature anneal. Comparison with activation energies previously obtained indicate that the presently obtained activation energy is consistent with the presence of either the divacancy or the carbon interstitial carbon substitutional pair, a result which agrees with the conclusion based on defect behavior in boron-doped silicon.

Weinberg, I.↗
NASA NTRS1993

Synthesis of novel electrically conducting polymers: Potential conducting Langmuir-Blodgett films and conducting polymers on defined surfaces

Based on previous results involving thiophene derived electrically conducting polymers in which it was shown that thiophene, 3-substituted thiophenes, furans, and certain oligomers of these compounds showed electrical conductivity after polymerization. The conductivity was in the order of up to 500 S/cm. In addition, these polymers showed conductivity without being doped and most of all they were practically inert toward ambient conditions. They even could be used in aqueous media. With these findings as a guide, a number of 3-long-chain-substituted thiophenes and 1-substituted-3-long-chain substituted pyrrols were synthesized as monomers for potential polymeric electrically conducting Langmuir-Blodgett films.

Zimmer, Hans↗
NASA NTRS1994

High Efficiency InP Solar Cells from Low Toxicity Tertiarybutylphosphine

Large scale manufacture of phosphide based semiconductor devices by organo-metallic vapor phase epitaxy (OMVPE) typically requires the use of highly toxic phosphine. Advancements in phosphine substitutes have identified tertiarybutylphosphine (TBP) as an excellent precursor for OMVPE of InP. High quality undoped and doped InP films were grown using TBP and trimethylindium. Impurity doped InP films were achieved utilizing diethylzinc and silane for p and n type respectively. 16 percent efficient solar cells under air mass zero, one sun intensity were demonstrated with Voc of 871 mV and fill factor of 82.6 percent. It was shown that TBP could replace phosphine, without adversely affecting device quality, in OMVPE deposition of InP thus significantly reducing toxic gas exposure risk.

Hoffman, Richard W., Jr.↗
NASA NTRS1994

Rare earth garnet selective emitter

Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approximately equal to 0.74, ((4)l(sub 15/2)) - ( (4)l(sub13/2)), for Er-YAG and epsilon(sub lambda) approximately equal to 0.65, ((5)l(sub 7))-((5)l(sub 8)) for Ho-YAG) at excellent candidates for high efficiency selective emitters in the thermophotovoltaics (TPV) systems operating at moderate temperatures (1200-1500K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium (Ho), and erbium (Er) doped YAG thin film selective emitters at 1500 K, and compares those results with the theoretical spectral emittance.

Lowe, Roland A.↗
NASA NTRS2006

Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (~1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

Jones, John↗