Patent Application
20190203053
Pigments based on the LiSbO3 and LiNbO3 type structures have not been reported. Materials with these crystal structure types have been studied in relation to piezoelectric, linear, and nonlinear optical material applications. The following work discloses a wide range of new pigment types based on LiSbO3-type and LiNbO3-type structures. These materials possess unique coloristic qualities as well as unusually high chemical stability.
The pigments disclosed in this work are compounds that possess a crystal structure related to the LiSbO3-type or LiNbO3-type structures. These structures possess chemical formulas with the following variations:
M1M5Z3,
M1M2M4M5Z6,
M1M32M5Z6,
M1M2M3M6Z6,
M12M4M6Z6,
M1M5M6Z6,
or combination thereof,
where the cation M1 is an element with a valence of +1 or a mixture thereof;
where the cation M2 is an element with a valence of +2 or a mixture thereof;
where the cation M3 is an element with a valence of +3 or a mixture thereof;
where the cation M4 is an element with a valence of +4 or a mixture thereof;
where the cation M5 is an element with a valence of +5 or a mixture thereof;
where the cation M6 is an element with a valence of +6 or a mixture thereof;
with M selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, or Te; where the anion Z is selected from N, O, S, Se, Cl, F, hydroxide ion or a mixture thereof; and where vacancies may reside on the M or Z site such that the structural type is retained. The term dopant is used to refer to substitutions that result in a deficiency or excess of the anion Z away from the ideal stoichiometry without substantially changing the structure. As well as variants that include M dopant additions below 20 atomic %, where the dopant is selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, Bi, Te, or mixtures thereof.
A detailed explanation and illustrative examples of the above composition range follow below.
LiSbO3 and LiNbO3 both have unique structures. The LiSbO3-type structure has an orthorhombic crystal structure with space group Pncn or in the case of ordered LiSbO3-type structural variants with space group Pnn2. In the ideal LiSbO3-type structure consists of oxygen atoms form a distorted hexagonal close packed array (
The LiNbO3-type structure is a trigonal crystal structure with space group R3c (
Slight variances may occur in the space group for above structures where substitutions on the Sb/Nb site leads to additional ordering that increases structural symmetry from Pncn to Pnn2. In general the primary space group for the LiSbO3-type structure falls under No. 52 from the International Tables for Crystallography, but related structures have fallen under No. 56 and 34. Subgroups of space group No. 52 include No. 34, No. 33, No. 30, No. 017, No. 014, and No. 013 for k-index 1. The primary space group for the LiNbO3-type structure falls under No. 161 from the International Tables for Crystallography. A subgroup of space group No. 161 includes No. 146 for k-index 1.
The pigments of the present invention possess a crystal structure related to the LiSbO3-type or LiNbO3-type structures. These structures possess chemical formulas with the following variations:
M1M5Z3,
M1M2M4M5Z6,
M1M32M5Z6,
M1M2M3M6Z6,
M12M4M6Z6,
M1M5M6Z6,
or combination thereof,
where the cation M1 is an element with a valence of +1 or a mixture thereof;
where the cation M2 is an element with a valence of +2 or a mixture thereof;
where the cation M3 is an element with a valence of +3 or a mixture thereof;
where the cation M4 is an element with a valence of +4 or a mixture thereof;
where the cation M5 is an element with a valence of +5 or a mixture thereof;
where the cation M6 is an element with a valence of +6 or a mixture thereof;
with M selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, or Te, where the anion Z is selected from N, O, S, Se, Cl, F, hydroxide ion or a mixture thereof; and where vacancies may reside on the M or Z site such that the structural type is retained. The term dopant is used to refer to substitutions that result in a deficiency or excess of the anion Z away from the ideal stoichiometry without substantially changing the structure. As well as variants that include M dopant additions below 20 atomic %, where the dopant is selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, Bi, Te, or mixtures thereof. Also, in another example, for the formula M1M5Z6, M1 may at least be greater than 50 atomic % Li, and M5 may at least be greater than 50 atomic % Sb. Further, in another example, where the chemical formula is selected from: (M1M5)2-x(M2M4)xZ6, where 0<x<1; (M1M5)2-x(M3M3)xZ6, where 0<x<1; or combinations thereof, M1 may at least be greater than 50 atomic % lithium, and M2 may at least be greater than 50 atomic % cobalt.
Other pigments, derived from solid solutions, may include those between M1M5Z3 and M1M2M4M5Z6 of the form (M1M5)2-x(M2M4)xZ6 where 0<x<1 and between M1M5Z3 and M1M3M3M5Z6 of the form (M1M5)2-x(M3M3)xZ6 where 0<x<1. Pigments may also be solid solutions between (M1M5)2-x(M2M4)xZ6 and (M1M5)2-x(M3M3)xZ6 where 0<x<1. Specifically, such pigments may include (LiSb)2-x(CoTi)xO6, where 0<x<1, and where the pigment ranges from a pastel pink to a violet to a dull purple color; or where x=0.8, and the pigment is a violet color. Other pigments may include (LiSb)2-x(CoSn)xO6, where 0<x<1, and where the pigment ranges from a pastel pink to a red-shade violet to a dull red-shade violet color and when x=0.5, and the pigment is a red-shade violet color. Other pigments may also include (LiNb)2-x(CoTi)xO6, where 0<x<0.4 and where the pigment ranges from a off-white to a pastel purple to a dull purple shade black color, and when x=0.1, and the pigment is a pastel purple color. Other pigments may include (LiTa)2-x(CoTi)xO6 where 0<x<0.4, and where the pigment ranges from an off-white to a violet to a dull purple color, and when x=0.2, the pigment is a light violet color. Pigments of the form (M1M5)2-x(M3M3)xZ6 may include (LiSb)2-x(Fe2)xO6, where 0<x<1, and where the pigment ranges from an off-white to a yellow shade brown. Pigments with M dopant additions may be formed such as (Co,Al) doped LiSbO3 where the cobalt content is at 4 atomic % and the aluminum content is at 10 atomic % resulting a violet pigment.
Compounds in this technology may also include a LiSbO3-type or LiNbO3-type structure, with a chemical formula selected from the following formulae:
(M1M5)2-x(M2M4)xZ6, where 0<x<1,
(M1M5)2-x(M3M3)xZ6, where 0<x<1,
(M1M2M3)2-x(M6)xZ6, where 0<x<1,
(M1M1M4)2-x(M6)xZ6, where 0<x<1,
(M1M5)2-x(M6)xZ6, where 0<x<1,
or combination thereof,
where the cation M1 is an element with a valence of +1 or a mixture thereof,
where the cation M2 is an element with a valence of +2 or a mixture thereof,
where the cation M3 is an element with a valence of +3 or a mixture thereof,
where the cation M4 is an element with a valence of +4 or a mixture thereof,
where the cation M5 is an element with a valence of +5 or a mixture thereof,
where the cation M6 is an element with a valence of +6 or a mixture thereof,
where M selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, or Te, where the anion Z is selected from N, O, S, Se, Cl, F, hydroxide ion or a mixture thereof, where vacancies may reside on the M or Z site such that the structural type is retained. The term dopant is used to refer to substitutions that result in a deficiency or excess of the anion Z away from the ideal stoichiometry without substantially changing the structure. As well as variants that include M dopant additions below 20 atomic %, where the dopant is selected from H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Si, Ge, Sn, P, Sb, Bi, Te, or mixtures thereof.
Potential uses for these materials may be in sol-gel type coatings and coil coatings (PVDF, polyester) as well as in cement, roofing granules, paint, ink, glass, enamel, ceramic glaze, plastics, sol-gel coatings, or decorative cosmetic applications.
Synthesis Routes:
There are multiple synthetic methods that may be employed to synthesize these materials. These include solid state sintering, solution synthesis (hydrothermal, precipatation, flame spray pyrolosis, and combustion synthesis), and ion exchange (through solution or molten salt techniques).
One method involves the use of the solid state sintering technique. The approriate elemental precursors (including oxides, carbonates, hydroxides, etc.) at the desired stoichiometry are intimately mixed and fired at temperatures ranging from 900° F. to 2300° F. under various atmospheres depending on the selected precursors. The resulting material is then milled to the desired size scale and color. Various sintering aids/mineralizers may be employed as well to reduce the firing temperature and minimize the loss of volatile constituents.
A surface coating/treatment may be applied to the resulting pigment for stabilization or functionalization in a range of applications.
The pigment may be incorporated into, or synthesized as part of, a composite material to either impart a benefit or functionality to the composite or to improve or enhance a property of the pigment.
A mixture of 4.45 grams of cobalt oxide (Co3O4), 4.43 grams of titanium dioxide (TiO2), 18.43 grams of lithium carbonate (Li2CO3), and 72.70 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,150° F. for 4 hours in air. The resulting material is a red-shade violet which can be milled to a pigmentary particle size that is light red-shade violet in coloration. A reversible color shift from light red-shade violet at room temperature to gray at 660° F. occurs.
A mixture of 9.01 grams of cobalt oxide (Co3O4), 8.96 grams of titanium dioxide (TiO2), 16.59 grams of lithium carbonate (Li2CO3), and 65.44 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,150° F. for 4 hours in air. The resulting material is bright violet which can be milled to a pigmentary particle size that is light violet in coloration. A reversible color shift from light violet at room temperature to gray at 660° F. occurs.
A mixture of 13.69 grams of cobalt oxide (Co3O4), 13.62 grams of titanium dioxide (TiO2), 14.70 grams of lithium carbonate (Li2CO3), and 57.99 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,150° F. for 4 hours in air. The resulting material is bright violet which can be milled to a pigmentary particle size that is violet in coloration. A reversible color shift from violet at room temperature to gray at 660° F. occurs.
A mixture of 18.49 grams of cobalt oxide (Co3O4), 18.39 grams of titanium dioxide (TiO2), 12.76 grams of lithium carbonate (Li2CO3), and 50.35 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,150° F. for 4 hours in air. The resulting material is bright purple which can be milled to a pigmentary particle size that is light purple in coloration. A reversible color shift from light purple at room temperature to gray at 660° F. occurs. This substance is also stable in a glass frit and sol-gel based coatings.
A mixture of 23.42 grams of cobalt oxide (Co3O4), 23.29 grams of titanium dioxide (TiO2), 10.78 grams of lithium carbonate (Li2CO3), and 42.51 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,150° F. for 4 hours in air. The resulting material has a purple color which can be milled to a pigmentary particle size that is dull purple in coloration. A reversible color shift from dull purple at room temperature to gray at 660° F. occurs.
A mixture of 15.90 grams of cobalt oxide (Co3O4), 29.84 grams of stannic oxide (SnO2), 10.97 grams of lithium carbonate (Li2CO3), and 43.29 grams of antimony trioxide (Sb2O3) was homogenized using a Waring blender and calcined at 2,000° F. for 4 hours in air. The resulting material is a red-shade violet which can be milled to a pigmentary particle size that is light red-shade violet coloration.
A mixture of 2.37 grams of cobalt oxide (Co3O4), 2.36 grams of titanium dioxide (TiO2), 20.72 grams of lithium carbonate (Li2CO3), and 74.55 grams of niobium pentoxide (Nb2O5) was homogenized using a Waring blender and calcined at 1,800° F. for 4 hours in air. The resulting material is purple which can be milled to a pigmentary particle size that is pastel purple in coloration.
A mixture of 3.24 grams of cobalt oxide (Co3O4), 3.22 grams of titanium dioxide (TiO2), 13.40 grams of lithium carbonate (Li2CO3), and 80.14 grams of tantalum pentoxide (Ta2O5) was homogenized using a Waring blender and calcined at 1,920° F. for 4 hours in air. The resulting material has violet color which can be milled to a pigmentary particle size that is light violet in coloration.
A mixture of 6.47 grams of cobalt carbonate (CoCO3), 4 grams of titanium dioxide (TiO2), 16.65 grams of lithium carbonate (Li2CO3), and 72.89 grams of antimony pentoxide (Sb2O5) was homogenized using a Waring blender and calcined at 2,010° F. for 4 hours under flowing argon. The resulting material has a purple which can be milled to a pigmentary particle size that is light purple in coloration.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3), stannic oxide (SnO2) and cobalt phosphate octahydrate (Co3(PO4)2.8H2O) were weighed out in proportions according to the molar amounts listed in Table 1. The mixtures were homogenized by mortar and pestle and calcined in air at 1,093° C. for 4 hours. After firing, the color of the final product is listed in Table 1 and ranged from pale light violet to brown.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3), cupric oxide (CuO) and nickel oxide (NiO) were weighed out in proportions according to the molar amounts listed in Table 2. The mixtures were homogenized by mortar and pestle and calcined in air at temperatures ranging from 980° C. to 1,180° C. for 4 hours. After firing, the color of the final product is listed in Table 2 and ranged from bright violet to light yellow.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3), niobium pentoxide (Nb2O5) and tantalum pentoxide (NiO) were weighed out in proportions according to the molar amounts listed in Table 3. The mixtures were homogenized by mortar and pestle and calcined in air at temperatures ranging from 1,050° C. or 1,120° C. for 4 hours. After firing, the color of the final product is listed in Table 3 and the colors were shades of blue lilac.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3), cupric oxide (CuO), nickel oxide (NiO) and antimony pentoxide (Sb2O5) were weighed out in proportions according to the molar amounts listed in Table 4. The mixtures were homogenized by mortar and pestle and calcined in air at temperatures ranging from 900° C. or 1,180° C. for 4 hours. After firing, the color of the final product is listed in Table 4 and the colors were shades of blue lilac.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3), cobalt carbonate (CoCO3), cobalt hydroxide (Co(OH)2), lithium hydroxide monohydrate (LiOH.H2O), lithium antimonate (LiSbO3), lithium cobalt oxide (LiCoO2) and antimony pentoxide(Sb2O5) were weighed out in proportions according to the molar amounts listed in Table 5. The mixtures were homogenized by mortar and pestle and calcined in air at 1,150° C. for 4 hours. After firing, the color of the final product is listed in Table 5 and the colors ranged from pale dark purple to pale violet.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3) and zinc oxide (ZnO) were weighed out in proportions according to the molar amounts listed in Table 6. The mixtures were homogenized by mortar and pestle and calcined in air at 1,150° C. for 4 hours. After firing, the color of the final product is listed in Table 6 and the colors ranged from pale violet to mauve.
Mixtures of cobalt oxide (Co3O4), titanium dioxide (TiO2), lithium carbonate (Li2CO3), antimony trioxide (Sb2O3) and magnesium carbonate (MgCO3) were weighed out in proportions according to the molar amounts listed in Table 7. The mixtures were homogenized by mortar and pestle and calcined in air at 1,150° C. for 4 hours. After firing, the color of the final product is listed in Table 7 and the colors ranged from pale violet to light pastel violet.
Mixtures of cobalt oxide (Co3O4), stannic oxide (SnO2), lithium carbonate (Li2CO3) and antimony trioxide (Sb2O3) were weighed out in proportions according to the molar amounts listed in Table 8. The mixtures were homogenized by mortar and pestle and calcined in air at 1,180° C. for 4 hours. After firing, the color of the final product is listed in Table 8 and the colors ranged from dark mauve to orchid.
X-ray Powder Diffraction Data:
X-ray powder diffraction measurements were made at room temperature using a Rigaku X-ray diffractometer with Cu-Kα radiation at 40 kV and 40 mA. Powder diffraction measurements were made on Examples 1 to 8 along with single phase LiSbO3, LiNbO3, and LiTaO3. The single phase samples were synthesized for comparison at temperatures of 2,100° F. (LiSbO3), 1,800° F. (LiNbO3), and 1,800° F. (LiTaO3). The powder diffraction patterns for Examples 1 to 5 are displayed in
The X-ray diffraction pattern for Example 6 (Li1.2Co0.8Sn0.8Sb1.2O6) is displayed in
Single phase LiTaO3 and LiNbO3 are compared to Examples 7 (Li1.9Co0.1Ti0.1Nb1.9O6) and 8 (Li1.8Co0.2Ti0.2Ta1.8O6) in
Particle Size Distribution Data:
In order to run color measurements the compositions from Examples 1 to 8 were ground to the particle size distributions listed in Table 10 below. Particle size distribution measurements were made using a Microtrac S3500 system and ranged from a fifty percentile of 2.8 microns to 4.8 microns. It should be noted that as the compositions are ground to a pigmentary particle size close to 1 micron the color shifts lighter and less chromatic.
Reflectance Spectra/Color:
PVDF/Acrylic masstone coatings were prepared using pigments from Examples 1 to 8. The coatings were applied to primed alumina substrates with a final dry film thickness of 2.2 mil. The reflectance as a function of wavelength and CIE L*a*b* color values were measured on the PVDF/Acrylic masstone drawdowns using a Perkin Elmer Lambda 900 spectrophotometer. All CIE* color values are for a D65 illuminant and 10 degree observer. The reflectance spectra for Examples 1 to 5 are displayed in
In contrast to the LiCoTiSbO6—LiSbO3 solid solution the LiNbO3 and LiTaO3 analogs with the LiNbO3-type crystal structure display a narrow solid solution range where desirable color can be achieved. The most chromatic color for the Li2-xCoxTixSb2-xO6 and Li2-xSb2-xCoxSnxO6 solid solutions occur where x ranges from 0.4≤x≤0.8, while in the case of Li2-xCoxTixNb2-xO6 and Li2-xCoxTixTa2-xO6 the values are close to x=0.1 and 0.2, respectively. In general the CIE L*a*b* color values for the full composition range (LiNb)2-x(CoTi)1-xO6 where (0.05≤x≤0.4) displays values of L* from 70 to 80, a* from 4 to 8, and b* from −5 to −15. In general the CIE L*a*b* color values for the full composition range (LiTa)2-x(CoTi)1-xO6 where (0.05≤x≤0.4) displays values of L* from 65 to 75, a* from 5 to 10, and b* from −10 to −20.
Acid/Base Stability:
Modified Kesternich testing was performed in which primed aluminum panels coated with PVDF/acrylic underwent a series of 7-hour exposures to a sulfur dioxide atmosphere followed by measurements of color and gloss. The color measurements were performed on a Datacolor 600 reflection spectrophotometer and 60° gloss measurements were performed using a BYK Gardner Micro Tri-gloss meter. Along with drawdowns of Examples 1 through 8, C.I. Pigment Violet 14 (Shepherd Color Violet 92) and C.I. Pigment Blue 28 (Shepherd Color Blue 424) were included for comparison. The full Kesternich testing included a total of 8 cycles of 7-hour exposure to sulfur dioxide (SCTM 276). The color and gloss changes that occurred over these 8 cycles are displayed in
The insets to
Along with standard Kesternich testing two additional acid/base stability tests were performed on Example 4. In the first of these tests PVDF/acrylic panels of Example 4 and Shepherd Color Violet 92 were exposed to 5% solutions of HCl and NaOH. During the test 1 milliliter aliquots of 5% HCl and 5% NaOH solutions are placed on two separate spots on each panel and then covered with watch glasses. After 24 hours of exposure the solutions are removed and the panels are cleaned and evaluated for signs of failure or color change. Once evaluated the acid/base solutions are placed back on the same spots on the panels and this process continues for seven days. The results of this testing are displayed in
The second set of acid/base stability testing on Example 4 was performed on the pigment powder. During this test 1 gram of pigment based on Example 4 was placed in two separate 3 mL vials. The first of these vials was then filled with a 5% solution of HCl and the second filled with 5% NaOH. The samples were then monitored for color change to the powder or the solutions. In the case of Example 4 there was no observable change in color to the powder or solution following two months of exposure. As a reference Shepherd Color Violet 92 pigment powder was compared under the same conditions. Unlike Example 4, a color change was observed within hours for the vials containing Shepherd Color Violet 92.
Weathering:
Accelerated weathering measurements were performed with a QUV machine that included UV (WA-340 lamp) and moisture exposure. Test panels used for accelerated weathering are the same as the PVDF/acrylic drawdowns used for the modified Kesternich testing above. Color measurements were performed on a Datacolor 600 reflection spectrophotometer and 60° gloss measurements were performed using a BYK Gardner Micro Tri-gloss meter. Table 12 below shows the accelerated weather data at 500 and 1000 hours for Examples 1 to 8 and Shepherd Color Violet 92 and Blue 424. The weathering data in Table 12 show that overall change in color (ΔE*) is highest for Examples 1 and 2. As the composition increases in Co and Ti content in Examples 3 to 5, the ΔE* becomes lower than that for Blue 424 or Violet 92. The substitution of titanium by tin in Example 6 (Li1.2Co0.8Sn0.8Sb1.2O6) also results in improved weathering over Violet 92 and Blue 424. Examples 7 and 8 with the LiNbO3-type structure both display improved weathering over Violet 92 and Blue 424.
Pigments in the violet color space derived from the LiSbO3 and LiNbO3-type structures may have significant chemical and weathering stability over that of most violet pigments currently used in industry. In specific examples above the stability is such that these pigments are comparable in performance to the current industry standard complex inorganic pigments used for long term high durability applications.
This application claims priority to U.S. provisional application No. 62/074,317, entitled, “Pigments based on LiSbO3 and LiNbO3 related structures,” filed Nov. 3, 2014, which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62074317 | Nov 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14929949 | Nov 2015 | US |
| Child | 16225574 | US |
