G. K. Marasinghe

Structural features of iron phosphate glasses

The structures and valence states of iron ions in several iron phosphate glasses with batch compositions similar to 40Fe2O3-60P2O5 (mol%) have been investigated using Mossbauer spectroscopy, X-ray absorption fine-structure spectroscopy (XAFS), X-ray photoelectron spectroscopy (XPS), differential thermal (DTA) and thermo-gravimetric (TGA) analysis and X-ray and neutron diffraction. Mossbauer spectra show that a redox equilibria corresponding to an Fe(II)/[Fe(II) + Fe(III)] ratio of 0.2–0.4 is reached under processing conditions described in this paper. Even though the valence state of iron ions in the glass appears to be insensitive to the oxygen content in the melting atmosphere, the Fe(II) content can be increased within the observed range of redox equilibria by increasing the partial pressure of a reducing gas in the melting atmosphere. Large amounts of Fe(II), Fe(II)/[Fe(II) + Fe(III)] ≥ 0.4, appear to be detrimental to the glass-forming ability of the iron phosphate melts. The local structure of the iron phosphate glasses appears to be related to the short range structure of crystalline Fe3(P2O7)2 which consists of a network of (Fe3O12)−16 clusters. These clusters consist of one iron(II) ion and two iron(III) ions in sixfold coordination with near-neighbor oxygen ions. The (Fe3O12)−16 clusters are interconnected via (P2O7)−4 groups. Compared to other phosphate glasses, the proposed structure for iron phosphate glasses contain a smaller number of POP bonds, a feature which is believed to be responsible for the unusually good chemical durability of iron phosphate glasses.

Effect of Melting Temperature and Time on Iron Valence and Crystallization of Iron Phosphate Glasses

The effect of melting temperature and time on iron valence, dissolution rate (DR) in deionized water, and crystallization of iron phosphate glasses was investigated using a 40Fe2O3–60P2O5, mol%, batch composition. The concentration of Fe2+ ions in these glasses increased from 17% to 57% as melting temperature increased from 1150°C to 1450°C, but remained nearly constant at about 20% for melting times longer than 1 h at 1200°C. Measurements by differential thermal analysis (DTA) combined with X-ray diffraction (XRD) and thermogravimetric analysis (TGA) showed that these glasses crystallized to Fe3(P2O7)2 and Fe4(P2O7)3 when heated in nitrogen between 600°C and 820°C, but with continued heating in air at 820°C the Fe3(P2O7)2 changed to Fe(PO4), which produced a weight gain in the sample associated with the oxidation of Fe2+ to Fe3+ ions. The DR (in deionized water) of these glasses was generally very low (∼10−9 g cm−2 min−1) and nearly independent of the relative concentration of Fe2+ or Fe3+ ions, but decreased with total iron content.

A neutron diffraction and Mössbauer effect study of the Nd2Fe17−xSix solid solutions

Abstract The substitution of silicon for iron in Nd 2 Fe 17 strongly raises the Curie temperature but leads to a reduction in the unit cell volume. Refinement of the neutron-diffraction pattern for Nd 2 Fe 12.91 Si 4.09 indicates that silicon preferentially occupies the 18h site in the Nd 2 Fe 17 structure, the site with the most neodymium near neighbors. This occupation is surprising because conventional arguments would suggest that replacement of iron on the 6c site, which has a very short iron to near-neighbor iron bond length, would yield an increase in the Curie temperature.

Mechanical and Structural Properties of Phosphate Glasses

Abstract Mechanical and structural properties of sodium (NAFP) and zinc (ZAFP) iron–aluminum–phosphate bulk glass and fibers have been investigated. Youngs modulus of the fibers was measured by a three-point bending method while the strength was measured by a two-point bending method. In general, the tensile strength of the ZAFP fibers (4.2–7.2 GPa) was higher than the tensile strength of the NAFP fibers (2.8–4.2 GPa). After exposing the fibers to air for 10 days, the strength decreased by 15–34%. The structure of bulk glass as well as fibers, studied by Mossbauer and IR spectroscopy, was very similar for all the compositions studied.

Properties of mixed Na2O and K2O iron phosphate glasses

Abstract Glass formation and properties of iron phosphate glasses containing Na 2 O and K 2 O have been investigated to determine the suitability of these glasses for disposing of certain types of nuclear wastes that contain one or more alkali oxides. Two series of glasses of the general composition x K 2 O–(20− x )Na 2 O–20Fe 2 O 3 –60P 2 O 5 and x K 2 O–(20− x )Na 2 O–32Fe 2 O 3 –48P 2 O 5 , mol%, with x =0, 5, 10, 15 and 20, were chosen for this investigation. The properties that have been measured include density, molar volume, chemical durability, electrical resistivity, dielectric constant and IR spectra. No typical mixed alkali effect, namely, a minimum or maximum in the properties as a function of the ratio of two alkali ions, was observed for these glasses. The present results show that iron phosphate glasses can be suitable for vitrifying nuclear wastes that contain amounts of one or more alkali oxides ⩽20 mol%. An Fe/P ratio of the compositions at about 0.67 and the O/P ratio between 3.5 and 3.7 are desirable to obtain the maximum chemical durability of the wasteforms.

Magnetic and crystallographic properties of SmMn/sub 6-x/Fe/sub x/Ge/sub 6/ intermetallics

The magnetic and crystallographic properties of induction-melted SmMn/sub 6-x/Fe/sub x/Ge/sub 6/ compounds, where x is 0, 0.5, 1.0, and 1.5, have been studied using X-ray diffraction and bulk magnetic measurements between 30 and 490 K. All of the samples crystallized in the YCo/sub 6/Ge/sub 6/-type structure with the space group P6/mmm. A small amount, less than 9 mol%, of Sm(MnFe)/sub 2/Ge/sub 2/ was present as an impurity in all samples. The unit cell volume decreases with increasing iron content at an average rate of 2.4% per substituted atom at room temperature. The a and c lattice parameters decrease at an average rate of 1.1 and 0.1% per substituted atom at room temperature, respectively. The magnetic properties deteriorate rapidly as the iron concentration increases beyond x=0.5. Magnetic behavior of SmMn/sub 5/Fe/sub 1/Ge/sub 6/ and SmMn/sub 4.5/Fe/sub 1.5/Ge/sub 6/ is indicative of antiferromagnetic or ferrimagnetic coupling. According to X-ray diffraction patterns of magnetically aligned powders, the easy direction of magnetization at room temperature for all of the samples lies close to the basal plane of the unit cell.

Site affinity of substituents in Nd2Fe17−xTx (T=Cu,Zr,Nb,Ti,V) alloys

In order to understand the magnetic properties of the substituted rare‐earth‐iron alloys, it is especially important to know the location of the substitutional atoms within the iron lattice. The site distributions of some nontransition‐metal substituents in the substituted Nd2Fe17−x T x alloys have previously been reported. Here we report the site distributions of some transition‐metal substituents (Cu,Zr,Nb,Ti,V) in the Nd2Fe17−x T x alloys and compare them with those of the nontransition‐metal substituted compounds.Rietveldanalysis of neutronpowderdiffraction data indicates that the nontransition‐metal substituents show very similar site affinity at low substituent content. For example Al, Ga, and Si all prefer the 18h sites. The transition‐metal substituents show a more complex site affinity. Ti and V atoms strongly prefer the 6c sites, Cu atoms prefer the 9d and 18f sites, Nb atoms prefer the 6c and 18h sites, and Zr atoms prefer 6c and 18f sites. It was also noted that the site affinity can change if carbon is included in the melting procedure of the sample preparation. The superconducting quantum interference device measurements show that all the substituted compounds have a Curie temperature higher than the unsubstituted parent compound. The relationship between the site distribution of substituents and the magnetic properties of the substituted Nd2Fe17−x T x alloys is discussed.

Magnetic and structural properties of Nd2Fe17−xMnx solid solutions

A series of Nd2Fe17−xMnx solid solutions with x values between 0 and 6 were prepared and analyzed using magnetic measurements, neutron diffraction, and Mossbauer spectroscopy. All of the Nd2Fe17−xMnx samples crystallized in the Th2Zn17−x-type rhombohedral structure. The lattice parameters and unit cell volumes decrease with increasing manganese content up to ∼x equal to 2, and then increase for higher manganese content. The magnetizations of Nd2Fe17−xMnx decrease with increasing manganese content and Nd2Fe17−xMnx is paramagnetic at room temperature for x greater than 3. The Curie temperature in Nd2Fe17−xMnx solid solutions is maximum for x equal to 0.5 and decreases at a rate of ∼10° per substituted manganese up to x equal to 3, after which it drops sharply. These results are discussed in terms of the manganese site occupancies in Nd2Fe17−xMnx.

Neutron‐diffraction and Mössbauer effect study of the Tb2Fe17−xAlx solid solutions

The magnetic properties of a series of Tb2Fe17−xAlx solid solutions, with nominal x compositions of 0, 2, 3, 4, 5, 6, 7, and 8, have been studied by neutron diffraction and Mossbauer spectroscopy. Neutron‐diffraction data indicate that the compounds all crystallize with the Th2Zn17 structure and that the aluminum atoms are excluded from the 9d site and show a distinct preference for the 6c site only for an aluminum content greater than 6. The unit‐cell volume increases by approximately 1% per aluminum atom substituted in the formula unit. The magnetic moment per formula unit, measured at 295 K, shows very little change for x less than or equal to 4, but decreases rapidly with increasing aluminum content for higher values of x. Mossbauer spectral results indicate that all the samples are ferromagnetically ordered at 85 K. However, at 295 K Tb2Fe9Al8 is paramagnetic and Tb2Fe10Al7 is either paramagnetic or has at most very small ferromagnetic moments. An analysis of the magnetic spectra with a basal magneti...

Neutron‐diffraction and Mössbauer effect study of the preferential silicon site occupation and magnetic structure of Nd2Fe14−xSixB

A neutron‐diffraction study of Nd2Fe14−xSixB has shown that silicon preferentially occupies the 4c site in the transition‐metal sublattice in Nd2Fe14B. Silicon also exhibits a moderate preference for the 8j1 site, is almost excluded from the 16k2 site, and avoids the 16k1, 8j2, and 4e sites. The silicon site occupancy is correlated with a preference for a silicon atom to have rare‐earth atoms in its coordination environment. The Mossbauer spectra of Nd2Fe14−xSixB have been fit with a model which takes into account the distribution of near‐neighbor environments of an iron atom due to the presence of silicon. These fits show that the substitution of silicon in the near‐neighbor environment of an iron atom primarily influences the long‐range contributions to the hyperfine field experienced by the iron. The mechanism for the increase in the Curie temperature when silicon is added to Nd2Fe14B‐type magnets is more subtle than previously believed, but can be explained by the relative decrease in the proportion o...