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1. Properties of Na2SiF6:Mn4+ and Na2GeF6:Mn4+ red phosphors synthesized by wet chemical etching
By Xu, Yan Kai; Adachi, Sadao
From Journal of Applied Physics (2009), 105(1), 013525/1-013525/6. Language: English, Database: CAPLUS,
DOI:10.1063/1.3056375
The authors report a simple method of synthesizing red phosphors, Na2SiF6:Mn4+ and Na2GeF6 :Mn4+, by wet chem.
etching of Si wafers and Ge shots in aq. HF soln. with the addn. of an oxidizing agent NaMnO4. The x-ray diffraction
anal. suggests that the red phosphors have the trigonal structure (space group = D2 3-P321). The optical properties of
these phosphors were studied using photoluminescence, photoluminescence excitation, optical absorption, and diffuse
reflectance spectroscopy. The spectral features show no clear difference between Na2SiF6:Mn4+ and Na2GeF6 :Mn4+
phosphors. They are well explained by the Tanabe-Sugano energy-level diagram with the crystal-field and Racah
parameters of Dq 1970 cm-1, B 775 cm-1, and C 3490 cm-1 with C/B 4.5. (c) 2009 American Institute of Physics.
~3 Citings
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2. Thermal behavior of ammonium-containing fluoro complexes of titanium and germanium (NH4)4Li2(AF6)3 and
NH4NaAF6 (A = Ge, Ti)
By Antokhina, T. F.; Flerov, I. N.; Savchenko, N. N.; Kaidalova, T. A.; Merkulov, E. B.; Ignat'eva, L. N.; Fokina, V. D.
From Zhurnal Neorganicheskoi Khimii (2008), 53(4), 639-643. Language: Russian, Database: CAPLUS
The title complexes were studied by thermogravimetric anal. and differential scanning calorimetry; the products of
thermal decompn. were identified by powder x-ray diffraction. The complex NH4NaTiF6 undergoes first-order
enantiotropic phase transitions at 126 and 111, the enthalpies of the transitions were detd. from the DSC curves. The
fluorogermanate NH4NaGeF6 decomps. at 760 to give Na2GeF6 and GeO2.
~0 Citings
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3. Syntheses and structures of Li3ScF6 and high pressure LiScF4 - luminescence properties of LiScF4, a new phase in
the system LiF-ScF3
By Tyagi, A. K.; Koehler, J.; Balog, P.; Weber, J.
From Journal of Solid State Chemistry (2005), 178(9), 2620-2625. Language: English, Database: CAPLUS,
DOI:10.1016/j.jssc.2005.04.038
Colorless single crystals of Li3ScF6 have been prepd. by reacting the binary components LiF and ScF3 at 820C for 16 h
in argon atm. This complex fluoride is the only stable phase in the system LiF-ScF3 under ambient pressure. According
to a structure refinement based on single crystal X-ray diffraction data it crystallizes in the centrosym. space group P3c1
with a = 8.783(1) and c = 9.518(1). The new structure of Li3ScF6 is a filled variant of the Na2GeF6 type structure and
can be described in terms of a hexagonal close packing of fluorine in which 2/3 of the octahedral holes are occupied by
Sc and Li. High pressure/high temp. studies of the system LiF-ScF3 show that the new phase LiScF4 is formed at around
5.5 GPa and 575C. According to Rietveld refinements of powder X-ray diffraction data LiScF4 adopts the Scheelite type
structure (space group I41/a) with a = 4.980(1) and c = 10.074(1) . A sample of LiScF4 doped with 1% Er exhibits an
intense luminescence in the far IR region.
~6 Citings
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4. Melt polycarbonate polymerization catalyst systems

By Lemmon, John Patrick; Mccloskey, Patrick Joseph; Siclovan, Oltea Puica
From U.S. (2001), US 6323304 B1 20011127, Language: English, Database: CAPLUS
This invention provides a method for prepg. polycarbonates, which utilizes polycondensation catalysts of the formula Ax
+MF -x, wherein A is an alkali metal or alk. earth cation; M is a transition metal of group IVA or VA, or M is a p-block
6
metal of group IIIB, IVB or VB; and x is 1, 2, or 3. We have found that this new class of catalysts provide excellent
polymn. rates for the prepn. of Bisphenol A polycarbonate from the melt polymn. of di-Ph carbonate and Bisphenol A.
Moreover, the catalysts of the invention were found to be very selective in substantially reducing the level of branching
side reaction, i.e., formation of Fries product, normally assocd. with the melt polycarbonate process.
~32 Citings
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5. On syntheses of single crystal complex fluorides of semimetal without solvents: lithium and sodium fluorogermanates
Li2[GeF6] and Na2[GeF6]
By Averdunk, F.; Hoppe, R.
From Zeitschrift fuer Anorganische und Allgemeine Chemie (1990), 582, 111-20. Language: German, Database:
CAPLUS
Colorless single crystals of Li2GeF6 and Na2GeF6 were prepd. in a sealed copper tube by reaction of CuF2 with Ge
powder in presence of LiF or NaF without solvent. The crystal structure is detd. with R = 3.5 and Rw = 3.5% for Li2GeF6
and R = 9.2 and Rw = 6.1% for Na2GeF6 . The compds. crystallize isotypic to Na2SiF6 in the space group P321, Z = 3.
The Madelung part of the lattice energy is calcd. and compared with values of the binary components and Cs3GeF7.
~5 Citings
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6. Acid-basic properties of fluorogermanates in melts of alkali metal nitrates

By Dratovsky, M.; Uchytilova, M.
From Elektrokhimiya (1987), 23(11), 1566-70. Language: Russian, Database: CAPLUS
The acid-base behavior of Na2GeO3, GeO2, K4Ge2F10O, Na2GeF6 , NaF, or K2Ge(IO3)6 in NaNO3-KNO3 melts was
studied potentiometrically by using on O-sensitive electrode. Three new fluorogermanate anions identified by titrn. of
these Lewis acids with Na2CO3 or NaGeO3 include GeF2O2 2-, Ge2F2O5 4-, and Ge4F6O9 8-.
~0 Citings
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7. Optical properties of some hexafluoro-complex compounds

By Levchishina, T. F.; Yamshchikov, E. F.
From Izvestiya Akademii Nauk SSSR, Neorganicheskie Materialy (1982), 18(4), 673-5. Language: Russian, Database:
CAPLUS
With the help of an improved immersion method the n was measured of microcrystals of Na2GeF6 , Rb2GeF6, Cs2GeF6,
Rb2SiF6, Cs2SiF6 in the interval of 436-656 nm with an accuracy of (2-4) 10-4. A relation of the type n = A + Bv2 was
found. Crystals of Na2GeF6 and Rb2GeF6 (hexagonal modification) were noted to have a weak birefringence.
~0 Citings
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8. Fusibility diagram of the sodium(1+), potassium(1+)hexafluorogermanate(2-), fluoride(1-) ternary reciprocal system

By Chernov, R. V.; Andriiko, A. A.
From Ukrainskii Khimicheskii Zhurnal (Russian Edition) (1979), 45(10), 928-31. Language: Russian, Database:
CAPLUS
The Na2GeF6 -K2GeF3 phase diagram and a planar projection of the Na+, K+ GeF3 2-, F- diagram were constructed from
visual-polythermal and DTA data. The stable diagonal is NaF-K2GeF6. Eutectics occur at 675, 670 and NaF 28, 26, KF
49, 2.5, and K2GeF6 23, 71.5 mol. %. Thermal stability of fluorogermanate melts is higher than that of fluorosilicate
melts.
~0 Citings
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9. Kinetics and mechanism of the thermal decomposition of sodium hexafluorogermanate

By Andriiko, A. A.; Chernov, R. V.
From Ukrainskii Khimicheskii Zhurnal (Russian Edition) (1979), 45(4), 298-303. Language: Russian, Database:
CAPLUS
The decompn. of Na2GeF6 was studied by thermogravimetric methods. No liq. phase is visible during the decompn. to
form GeF4 and the ultimate, incongruently melting Na3GeF7. The apparent m.p. depends on the rate of heating. Kinetic
data are interpreted in the light of stepwise loss of GeF4 from a polymeric (Na2GeF6 )15. The activation energy for the
loss of the 1st mol. of GeF4 is <65 kJ/mol. A table is given of rate consts. and of activation energies for the loss of the
first 3 mols.

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~0 Citings
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10. Fusibility diagrams of potassium hexafluorogermanate-potassium fluoride and sodium hexafluorogermanate-sodium

fluoride binary systems
By Andriiko, A. A.; Chernov, R. V.
From Ukrainskii Khimicheskii Zhurnal (Russian Edition) (1979), 45(3), 217-20. Language: Russian, Database: CAPLUS
The m.ps. of K2GeF6 and Na2GeF6 are 940-80. Exact detn. is hindered by their decompn. on heating to form GeF4.
The literature values for these m.ps. are close to those of eutectics. K3GeF7 m. congruently at 804. The eutectics, m.
773 and 735, contain 25 and 76% KF resp. The Na3GeF7 incongruently m. 650.
~0 Citings
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11. Rare earth metal oxysulfide phosphors

By Yamada, Hiromichi; Nakano, Masaki; Kano, Tsuyoshi; Yamamoto, Hajime
From Jpn. Kokai Tokkyo Koho (1977), JP 52024170 A 19770223, Language: Japanese, Database: CAPLUS
Fe compd(s). selected from Na2SiF6, K2SiF6, Li2SiF6, (NH4)2SiF6, Na2GeF6, (NH4)2GeF6, (NH4)2TiF6, and NH4PF6
are used as a flux during the prepn. of rare earth oxysulfide-type phosphors by heating a mixt. consisting of rare earth
metal oxides (or compds. that can be converted to the oxides by heating) required to form {M1-x-y-zEuxSmy(Tb1pPrp)z}2O3 (where M = Y, Gd, La, Lu; 0 z 1 10-4, 0 p 1; 0.024 x 0.04; 0.0005 y 0.009; but, the upper
limit for y decreases with increasing x; i.e. for x = 0.04 y 0.0025) and compds. required to form alkali metal sulfides
and/or polysulfides. Phosphor particles obtained by the method are relatively large and are planar, and hence, the
phosphor coatings prepd. with these phosphors have improved luminosity. Thus, Na2SiF6 1.62 g was added to a mixt.
consisting of Y2O3 18.86, Eu2O3 0.913, Sm2O3 0.136, Na2CO3 5.91, K3PO4 1.59, and S 5.91 g, the mixt. was then
heated 3 h at 1150, cooled, washed with H2O, 0.5% HCl, and with diionized water to give
(Y0.9655Eu0.03Sm0.0045)2O2S phosphors: the av. grain size was 11.6 , vs. 4.5 for a control prepd. without
Na2SiF6.
~0 Citings
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12. Rare earth oxysulfide type phosphors

By Yamada, Hiromichi; Nakano, Masaki; Kano, Tsuyoshi; Yamamoto, Hajime
From Jpn. Kokai Tokkyo Koho (1976), JP 51142486 A 19761208, Language: Japanese, Database: CAPLUS
In prepg. rare earth oxysulfide-type phosphors by firing a mixt. of (M11-x-yEuxM2y)2O3 [where 0.001 x 0.1, 0 y
10-4, M1 = Y, Gd, La, or Lu, and M2 = Tb and/or Pr] with alkali metal sulfide-forming constituents, 1 compd(s). selected
from Na2SiF6, Li2SiF6, K2SiF6, Na2GeF6, (NH4)2GeF6, (NH4)2SiF6, (NH4)2TiF6, and NH4PF6 are added as a flux to
increase the grain size of the phosphors and to increase the brightness. The phosphors are useful in color television
cathode-ray tubes. Thus, Na2SiF6 1.62 g was added to a mixt. of Y2O3 18.71, Eu2O3 1.28, Na2CO3 5.91, K3PO4 1.59,
and S 5.91 g, the mixt. was then fired 3 h at 1150, the sintered products were ball-milled in an appropriate amt. of water,
treated with dil. HCl soln., washed with distd. H2O, and dried at 120 to give (Y0.9577Eu0.0423)2O2S type phosphors
with av. particle size 11.6- vs. 4.5- for a control prepd. without adding Na2SiF6.
~0 Citings
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13. Nuclear magnetic resonance in hexafluorosilicates and hexafluorogermanates of alkali elements

By Gabuda, S. P.; Tychinskaya, I. P.; Lundin, A. G.
From Radiospektrosk. Tverd. Tela (1967), 118. Language: Russian, Database: CAPLUS

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From Ref. Zh., Fiz. D. 1967, Abstr. No. 9D503. At 20 and -196, the N.M.R. spectra of 19F in the compds. Na2SiF6 and
M2GeF6, where M = Li, Na, K, and Rb, was studied. Exptl. values for 2nd moments (S2) at -196 were (8.1 0.4) oe.2
for all the compds. studied and agreed with theoretical calcns. of other investigators. The width and shape of spectra of
the compds. studied (except the Na compd.) remained unchanged with increase in temp. The shape of the spectrum of
Na2SiF6 and Na2GeF6 changed from a wide unresolved singlet to an unresolved triplet with increase in temp. and S2
decreased to 5.5 0.2 oe.2 This was due to reorientation of 33% of the octahedral ions of [SiF6]-or [GeF6]-around their
axes. The S2 value for (NH4)2SiF6 at -196 was 11.5 0.5 oe.2 The increase in S2 of (NH4)2SiF6 as compared with
S2 values of other compds. is explained by the contribution of protons of NH4 groups to the N.M.R. spectrum of 19F.
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14. Fluorogermanates in systems of the M2GeF6-HF-H2O type

By Tychinskaya, I. I.; Nikolaev, N. S.
From Zhurnal Neorganicheskoi Khimii (1963), 8, 734-7. Language: Unavailable, Database: CAPLUS
The systems K2GeF6-HF-H2O and Na2GeF6HF-H2O (isotherm 0) were studied by the method of isothermal soly. within
the HF concn. range from 0 to 100%. The congruent character of dissoln. of the K and Na hexafluorogermanates in HF
of various concns. was shown. Salts of the type M2GeF6 (where M is K, Na, Cs, Li) dissolve in 100% HF without
decompn. The soly. of Li2GeF6 is 2.51 wt. %, Na2GeF6 31%, K2GeF6 43.8%, and Cs2GeF6 55%. The soly. of the
fluorogermanates in anhyd. HF increases with the ion radius of the cation. The possibility of the detn. of HF and the
hexafluorogermanates of the alkali metals in a single sample by direct alkalimetric titration with phenol red was shown.
~0 Citings
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15. Structure of sodium fluosilicate and fluogermanate

By Cipriani, Curzio
From Rendiconti della Societa Mineralogica Italiana (1955), 11, 58-77. Language: Unavailable, Database: CAPLUS
By the Patterson projection method the structure of the elementary lattice of Na2SiF6 and Na2-GeF6 (both prepd. by C.;
crystallographic consts. checked) was found to be the same for both and different from that of the K salts. The structure
is based on 3 octahedrons Si-F or Ge-F. Distances Na-F averaged 2.25 and 2.28 A., resp., for the 2 salts, distances Si-F
or Ge-F 1.88 and 1.91 A., resp. The elementary lattice is so represented as to have a layer structure with 4 layers, one
of Si (or Ge) and Na at z = 0, one of F at z = 0.25, one of Si (or Ge) at z = 0.5 and one of F at z = 0.75, approx.
~2 Citings
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16. Structure and crystallochemistry of Na2TiF6

By Cipriani, Curzio
From Periodico di Mineralogia (1956), 24, 361-76. Language: Unavailable, Database: CAPLUS
cf. Rend. soc. mineralog, ital. 11, 58(1955). Hexagonal prismatic crystals with {1010} {1120} {1011}, a:c = 0.557: 1;
optical consts.: = 1.412 0.001; = 1.419 0.001, for yellow light. Oscillation and Weissenberg diagrams give the
space group D3d 3, the same as in Na2SiF6 and Na2GeF6 . (loc. cit.); a0 = 9.20 0.01, c0 = 5.13 0.01, mol. vol. 376 2
cu. A., Z = 3 mols. Na2TiF6, d. 2.78. At. coordinates detd. were: Ti(I) in 1a 0, 0, 0; Ti(II) in 2d 1/3, 2/3, z(z = 1/2); Na in 6g
x, 0, 0 (x = 1/3); F(I) in 6i x1, x1, z1(x1 = 0.10; z1 = 0.23); F(II) in 6i x2, x2, z2(x2 = 0.24; z2 = 0.77); F(III) in 6i x3, x3, z3(x3 =
0.42; z = 0.23). Distances Ti(I)-F(I) 1.98 A.; Ti(II)-F(II) 2.04 A.; Ti(II)-F(III) 1.96 A.; Na-F (av.) 2.33 0.08 A. Expts. to
prep. cryst. solns. of Na2TiF6 and Na2SiF6 made evident that there is only a limited miscibility; it was esp. evident from xray precision measurements of a0 and c0. The miscibility gap extends from 18 to 97 mol. % Na2TiF6 (in dil. HF as
solvent, and temp. = 90). In the system Na2TiF6-Na2GeF6 the miscibility is probably complete, with a continuous series
of cryst. solns.
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17. Complex fluorides. III. Lattice constants of complex fluorides of lithium or sodium and quadrivalent elements
By Cox, B.
From Journal of the Chemical Society (1954), 3251-2. Language: Unavailable, Database: CAPLUS

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cf. C.A. 48, 9855b. By x-ray powder photography it is shown that an isomorphous series of complex Na salts exists.
These salts, with lattice consts. of the hexagonal cells are: Na2SiF6, a = 8.86, c = 5.02; Na2TiF6, a = 9.21, c = 5.15;
Na2GeF6 , a = 9.10, c = 5.13; Na2PtF6, a = 9.41, c = 5.16 A. In addn., Li2SiF6 is isomorphous with these, since a = 8.22,
c = 4.56 A. Li2GeF6 and Li2TiF6 cannot be indexed on this basis.
~4 Citings
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18. Geochemistry of germanium. Isomorphism between germanium and silicon

By Cipriani, Curzio
From Rendiconti della Societa Mineralogica Italiana (1954), 10, 253-68. Language: Unavailable, Database: CAPLUS
The possibility of existence and the properties of solid solns. of Na2SiF6-Na2GeF6 and K2SiF6-K2GeF6 were
investigated. From (crystg. at 50) solns. contg. Na2GeF6 30, 35, 45, 60, 70, 75, 80, 90, and 95% (molar ratios
throughout), solid solns. contg., resp., 8, 16, 18, 33, 35, 40, 52, 62, and 76% Na2GeF6 were obtained. From the soln. of
the K salts (1:1) a cubic phase contg. 5% K2GeF6, and then a hexagonal phase without K2GeF6 were obtained. The ns
for all mix crystals obtained are given: those of the Na salts increased regularly by increasing the percentage of Na2GeF6
(up to 75%). The crystn. habits and the lattice consts. of the pure salts and of a 40% Na2GeF6 -contg. crystal (I) are
given: a and c were 8.87 and 5.07, 8.99, and 5.12, 8.18 and -, 5.67 and 9.26, 5.77 and 9.38, and 8.92 and 5.09 A., resp.,
for Na2SiF6, Na2GeF6 , cubic K2SiF6, hexagonal K2SiF6, K2GeF6, and I. C. concludes that the presence of Ge in silicates
of pneumatolytic and hydrothermal origin should be ascribed to the isomorphous substitution of Ge for Si in alk.
fluosilicates.
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19. An interesting behavior of soluble metatungstates

By Smith, E. F.
From Proc. Am. Phil. Soc. (1926), 65(Supplement No. 5), 18-9. Language: Unavailable, Database: CAPLUS
The 5:12, 4:10 and 3:7 Na tungstates are combinations of the strongly basic 1:1 and acidic 1: 4 salts, into and from which
they can be resolved and synthesized. The action of Na2CrO4 and Na2MoO4 solns. on Na metatungstate is studied.
When Na or NH4 metatungstate and Na2CrO4 are gently heated together, crystals are obtained, after filtering off the
pptd. tungstic acid. on standing. Recrystn. gives a salt which analyzes as 4Na2O.10WO2.23H2O. Contrary to
expectation, Na2MoO4 also gives the 4:10 salt, no molybdic acid being found on heating to 250 with dry HCl. Thus no
such combination as xNa2O.MoO3yNa2O.4WO3 is formed.
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