USRE45382E1 - Substituted tin niobium pyrochlore and tin niobium oxide pigments - Google Patents
Substituted tin niobium pyrochlore and tin niobium oxide pigments Download PDFInfo
- Publication number
- USRE45382E1 USRE45382E1 US14/294,619 US201414294619A USRE45382E US RE45382 E1 USRE45382 E1 US RE45382E1 US 201414294619 A US201414294619 A US 201414294619A US RE45382 E USRE45382 E US RE45382E
- Authority
- US
- United States
- Prior art keywords
- pigment
- tin
- sulfur
- color
- selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000049 pigment Substances 0.000 title claims description 61
- KJSMVPYGGLPWOE-UHFFFAOYSA-N niobium tin Chemical class [Nb].[Sn] KJSMVPYGGLPWOE-UHFFFAOYSA-N 0.000 title description 3
- LZTOVUIDOJNVHA-UHFFFAOYSA-N niobium(5+) oxygen(2-) tin(4+) Chemical compound [O-2].[Nb+5].[Sn+4] LZTOVUIDOJNVHA-UHFFFAOYSA-N 0.000 title 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052718 tin Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000010955 niobium Substances 0.000 claims abstract description 15
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- ZIJTYIRGFVHPHZ-UHFFFAOYSA-N selenium oxide(seo) Chemical compound [Se]=O ZIJTYIRGFVHPHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011135 tin Substances 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011669 selenium Substances 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 49
- 229910052984 zinc sulfide Inorganic materials 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910000484 niobium oxide Inorganic materials 0.000 description 12
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 12
- 239000011872 intimate mixture Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000005083 Zinc sulfide Substances 0.000 description 10
- 239000011701 zinc Chemical group 0.000 description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical group [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical group C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PGWFQHBXMJMAPN-UHFFFAOYSA-N ctk4b5078 Chemical group [Cd].OS(=O)(=O)[Se]S(O)(=O)=O PGWFQHBXMJMAPN-UHFFFAOYSA-N 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical compound OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QXJLMKRKOWZCRC-UHFFFAOYSA-N niobium(5+) oxygen(2-) tin(4+) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[Nb+5].[Nb+5].[Sn+4] QXJLMKRKOWZCRC-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/36—Three-dimensional structures pyrochlore-type (A2B2O7)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
Definitions
- Pigments with high chromaticity and temperature stability possessing required color characteristics have traditionally been made from cadmium sulfide, cadmium sulfo-selenide or zinc substituted cadmium sulfo-selenides.
- Tin niobium pyrochlore is formally Sn 2 Nb 2 O 7 .
- the use of this general class of compound as a pigment or colorant to replace cadmium sulfide or sulfo-selenide pigments is proposed and disclosed in U.S. Pat. No. 7,594,961.
- the disclosure in the above referenced patent contemplates making the pure pyrochlore, Sn 2 Nb 2 O 7 . Additionally, the referenced application posits pigments in which tin sulfide is used in lieu of stannous oxide in the synthesis of the finished pigment. Finally, the referenced patent posits substitution of the pentavalent niobium atoms with other transition metals that can exhibit a high valence state, such as tungsten or molybdenum in the form of MoO 3 or WO 3 . These substitutions are intended to modify the color of the pigments produced.
- An inorganic pigment comprising tin; a divalent metal; niobium; and an oxysulfide, an oxyselenide, or oxysulfo-selenide
- FIG. 1 is a UV-visible spectrum for examples 1-6 when the pigments are printed on Leneta cards out of an acrylic paint vehicle.
- FIG. 2 is a Kubelka Remission plot for examples 1-6 when the pigments are printed on Leneta cards out of an acrylic paint vehicle.
- FIG. 3 is a powder x-ray diffraction pattern for example 2.
- FIG. 4 is a powder x-ray diffraction pattern for example 4.
- FIG. 5 is a powder x-ray diffraction pattern for example 11.
- Inorganic pigments based on tin niobium niobium oxide may be substituted at the location of the tin atom in the lattice to adjust color or improve ease of synthesis.
- stannous oxide on thermal decomposition will yield tin metal (along with an equimolar proportion of stannic oxide).
- the temperature at which such decomposition occurs under an inert atmosphere is known to be as low as 300° C. when stannous oxide is heated independent of other components.
- stannous oxide is calcined with other oxides with the aim of obtaining a new mixed-metal oxide, such as tin niobium pyrochlore, SnNb 2 O 7 , a competition is set up between the desired solid-state ionic diffusion to yield the pyrochlore lattice and undesirable decomposition of the stannous oxide—yielding tin metal and stannous oxide.
- Substitution at the divalent metal center in Sn 2 Nb 2 O 7 pyrochlore can improve color of the derived pigment, control onset of absorbance in a manner expected for a band-gap colorant, reduce the firing temperature demanded to complete synthesis, and eliminate the requirement to conduct acid washing of the calcined product to rid it of contaminants such as metallic tin.
- the inorganic pigment comprises tin; a divalent metal; niobium; and an oxysulfide, an oxyselenide, or oxysulfo-selenide.
- the pigments has the empirical formula: M 2 Nb 2 Z 7 .XMNb 2 Z 6 where M comprises tin and a divalent metal; Z comprises oxygen and either sulfur, selenium, or a mixture of sulfur and selenium; and X ranges from 0 to 100. In one embodiment, X may be from about 0 to about 0.15; about 0 to about 0.25; about 0.25 to about 0.5; about 0.5 to about 1.0; about 1.0 to about 10; about 10 to about 50; or about 50 to about 100.
- M 2 Nb 2 Z 7 .XMNb 2 Z 6 X is a coefficient. When X is 50 the empirical formula is M 2 Nb 2 Z 7 .50MNb 2 Z 6 . When X is 0.1 the empirical formula is M 2 Nb 2 Z 7 .0.1MNb 2 Z 6 , which is equivalent to 10M 2 Nb 2 Z 7 .MNb 2 Z 6 .
- Divalent metals are those where the common oxidation state or more stable oxidation state is +2, such as zinc, tin, cobalt, manganese, iron, calcium, and magnesium.
- Metals with common oxidation states or stable oxidation states that are not +2 are not divalent metals, such as tungsten and molybdenum.
- the divalent metal comprises zinc.
- the ratio of tin to zinc may range from about 10 to 1; to about 1 to 10. In one embodiment the ratio of tin to zinc is about 4 to 1; about 3 to 1; about 2 to 1; about 1 to 1; about 1 to 2; about 1 to 3; or about 1 to 4.
- divalent metals include alkali earth metals, or transition metals.
- tin oxide may be partially replaced with zinc sulfide or zinc selenide. This substitution may lower the synthesis temperature by at least 100° C. from around 1000° C. to about 850° C. This also frees the pigment from the requirement that it be cleaned of unreacted stannous oxide or metallic tin by acid extraction.
- the pigment may be substituted by metals other than zinc at the divalent “A” site in this A 2 B 2 O 7 pyrochlore, or AB 2 O 6 foordite structure. This may be accomplished with or without zinc sulfide to lower the onset of reaction.
- Pigments with higher ratios of selenium compared to sulfur tend to have colors that are shifted from a more yellow to a more orange tone.
- X has the structure of a pyrochlore compound. At higher values of X, greater than about 1, the dominant structure adopted may become that of foordite, SnNb 2 O 6 .
- X is 0, so the empirical formula for the pigment is M 2 Nb 2 Z 7 .
- M comprises tin and zinc, and Z comprises sulfur and oxygen so that the ZnS:SnO ratio is between 0.04:1.96 and 0.20:1.80.
- the pigment has the empirical formula: MNb 2 Z 6 , where M comprises tin and a divalent metal; and Z comprises oxygen and either sulfur, selenium, or a mixture of sulfur and selenium.
- the pigment has the empirical formula: MNb 2 Z 6 , where M comprises tin and zinc; and Z comprises oxygen and either sulfur, selenium, or a mixture of sulfur and selenium
- the inorganic pigments may be synthesized by creating a mixture of metal oxides and intensively blending them in a mixer. The mixture is heated under an inert gas from about 850° C. to about 1000° C.
- the color of the pigment may be measured as an acrylic masstone using the procedure described in Example 10.
- the color of the acrylic masstone of the pigment has an L* of about 73.7 to about 82.8, an a* of about 4.9 to about 21.1, and a b* of about 72 to about 84.7.
- the acrylic masstone of the pigment has an L* of about 77.1 to about 78.4, an a* of about 8.0 to about 16.5, and a b* of about 76.6 to about 79.5.
- the acrylic masstone of the pigment has an L* of about 77.1 to about 78, an a* of about 8.0 to about 16.5, and a b* of about 76.6 to about 78.8.
- the crystal structure of the inorganic pigment has an effect upon the color produced by the pigment.
- the inorganic pigment is characterized by an X-ray powder diffraction pattern comprising d-spacings of about 3.095 ⁇ , 3.056 ⁇ , 2.841 ⁇ , 2.645 ⁇ , 1.871 ⁇ , 1.677 ⁇ , and 1.596 ⁇ .
- the inorganic pigment is characterized by an X-ray powder diffraction pattern comprising d-spacings of about 3.584 ⁇ , 3.066 ⁇ , 2.836 ⁇ , 2.779 ⁇ , 2.434 ⁇ , and 1.910 ⁇ .
- the inorganic pigment is characterized by an X-ray powder diffraction pattern comprising d-spacings of about 3.056 ⁇ , 2.647 ⁇ , 1.872 ⁇ , and 1.596 ⁇ .
- the process of making the pigments does not require an acid wash to remove contaminants of stannous oxide decomposition.
- the inorganic pigments may be used in many applications such as coatings, or colored plastics such as vinyl siding.
- a desirable property in these applications is the high IR reflection exhibited by the pigments. This property allows the pigments to develop the desired color in the visible range, while reflecting a large amount of the IR radiation outside of this visible range. This means that the surface of objects colored with the present IR reflective pigments remain cooler under solar radiation than those not colored with IR reflective pigments.
- the reflectance properties of the inorganic pigments may be higher at IR wavelengths (greater than 700 nm) compared to visible wavelengths (400-700 nm). Infrared reflectance may be measured on the compressed dry powder inorganic pigment using an integrating sphere instrument in accordance with ASTM E903-96. In one embodiment the IR reflectance is greater than about 50%, 60%, 70%, or 80% on average throughout the region from 700 nm to 2500 nm.
- An intimate mixture of stannous oxide, niobium oxide and zinc sulfide is made using an intensive blending mixer in molar ratios 1.5, 1, 0.5.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a uniform yellow colored powder with an orange tone.
- An intimate mixture of stannous oxide, niobium oxide, and zinc sulfide is made using an intensive blending mixer in molar ratios 1.3, 1, 0.7.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a uniform yellow colored powder with a slight orange tone.
- An intimate mixture of stannous oxide, niobium oxide, and zinc sulfide is made using an intensive blending mixer in molar ratios 1.0, 1, 1.0.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a uniform yellow colored powder.
- An intimate mixture of stannous oxide, niobium oxide, zinc sulfide, and zinc selenide is made using an intensive blending mixer in molar ratios 0.375, 0.25, 0.0765, 0.0485.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a uniform yellow colored powder with an orange tone.
- An intimate mixture of stannous oxide, niobium oxide and zinc selenide is made using an intensive blending mixer in molar ratios 0.375, 0.25, 0.125.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a uniform yellow colored powder with a marked orange tone.
- An intimate mixture of stannous oxide and niobium oxide is made using an intensive blending mixer in molar ratios 0.5, 0.25.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 850° C., 1565° F.
- the resulting product is a very green-shade yellow colored powder indicative of incomplete reaction.
- An intimate mixture of stannous oxide and niobium oxide is made using an intensive blending mixer in molar ratios 0.5, 0.25.
- the raw batch so produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or around 1050° C., 1925° F.
- inert gas either nitrogen or argon
- Example 1 An intimate mixture of stannous oxide, niobium oxide, zinc sulfide, and cobalt carbonate is made in molar ratios of 0.465, 0.25, 0.015, 0.02.
- the raw batch is calcined as in Example 1 to yield a yellow powder more green in tone than Example 8.
- Example 7 The products from Examples 1 through 5 and Example 7 are finely ground and introduced into an acrylic paint vehicle. The resulting color in masstone, and in reduction (4:1) with TiO 2 is shown below.
- Masstone samples were produced by introducing 21.9 g of pigment into 39.6 grams of a clear modified acrylic resin solution (46.6 resin weight percent).
- Tint samples were created by cross-blending at appropriate ratios 1 part of the colored enamel, made as above, with 4 parts of a similarly created white acrylic paint wherein all the pigment was titanium dioxide.
- Color cards were prepared by drawing down the enamels using a 10-mil Bird gage, allowing them to air dry for 30 minutes, then finish drying at 125° F. for 45 minutes. Color data is reported below in the CIELAB color space, (D65 illuminant) using 2-degree observer, made on an integrating sphere MacBeth Color-Eye 7000 instrument with, specular reflectance included.
- An intimate mixture of stannous oxide, niobium oxide, and zinc sulfide is made using an intensive blending mixer in molar ratios 1.9, 1, 0.1.
- the raw batch produced is loaded into open top alumina boats and fired under flowing inert gas (either nitrogen or argon) at or between 850° C., 1565° F. and 1000° C., 1832° F.
- the resulting product is a uniform yellow colored powder with a strong orange tone.
- the products of this example exhibit a single pyrochlore phase in their x-ray powder diffraction pattern for ratios of ZnS:SnO between 0.04:1.96 and 0.20:1.80.
- the sub-set of such products exhibit uniform shifts in observed color coordinates commensurate with increasing ZnS doping into the pyrochlore lattice showing increased red hue and improvements in yellow masstone.
- At molar ratios of ZnS:SnO of 0.25:1.75 and above the red hue no longer improves, while yellow tone continues to develop strength.
- This sub-set of products exhibits traces of foordite along with pyrochlore (as the dominant phase) in their x-ray powder diffraction patterns.
Abstract
Description
Firing | |||||||
Sample | L* | a* | b* | C* | h° | Temperature | {ZnS + ZnSe} |
Example 6 | 78.29 | 0.69 | 75.21 | 75.22 | 89.48 | 850° C. | 0 |
Example 1 | 79.89 | 13.04 | 80.58 | 81.63 | 80.81 | 850° C. | 0.25 |
Example 2 | 81.6 | 8.44 | 82.44 | 82.87 | 84.15 | 850° C. | 0.33 |
Example 3 | 82.82 | 4.9 | 84.69 | 84.83 | 86.69 | 850° C. | 0.5 |
Example 4 | 76.67 | 18.11 | 75.93 | 78.06 | 76.58 | 850° C. | 0.25 |
Example 5 | 73.68 | 21.14 | 72 | 75.04 | 73.64 | 850° C. | 0.25 |
Example 7 | 79.34 | 9.52 | 81.85 | 82.4 | 83.37 | 1050° C. | 0 |
Firing | |||||||
Sample | L* | a* | b* | C* | h° | Temperature | {ZnS + ZnSe} |
Example 6 | 88.68 | −3.69 | 42.75 | 42.91 | 94.94 | 850° C. | 0 |
Example 1 | 89.68 | 1.97 | 44.62 | 44.67 | 87.48 | 850° C. | 0.25 |
Example 2 | 90.85 | −0.74 | 45.32 | 45.33 | 90.94 | 850° C. | 0.33 |
Example 3 | 92.7 | −1.97 | 36.68 | 36.73 | 93.08 | 850° C. | 0.5 |
Example 4 | 88.44 | 4.81 | 40.68 | 40.96 | 83.25 | 850° C. | 0.25 |
Example 5 | 86.88 | 6.82 | 37.18 | 37.8 | 79.6 | 850° C. | 0.25 |
Example 7 | 91.72 | 0.67 | 30.93 | 30.94 | 88.76 | 1050° C. | 0 |
Mole Ratio | ||||
Sample | L* | a* | b* | Zn:Sn |
a | 77.16 | 8.01 | 76.57 | 0.04:1.96 |
b | 77.11 | 11.4 | 77.13 | 0.06:1.94 |
c | 77.73 | 14.35 | 78.43 | 0.08:1.92 |
d | 77.63 | 15.89 | 78.56 | 0.1:1.90 |
e | 77.75 | 16.53 | 78.78 | 0.15:1.85 |
f | 77.95 | 16.41 | 78.68 | 0.20:1.80 |
g | 78.39 | 15.58 | 79.36 | 0.25:1.75 |
h | 78.42 | 15.4 | 79.45 | 0.30:1.70 |
Mole Ratio | ||||
Sample | L* | a* | b* | Zn:Sn |
a | 89.07 | −0.12 | 38.84 | 0.04:1.96 |
b | 89.06 | 1.55 | 38.99 | 0.06:1.94 |
c | 89.33 | 2.96 | 38.88 | 0.08:1.92 |
d | 89.31 | 3.63 | 38.43 | 0.1:1.90 |
e | 89.15 | 4.11 | 38.71 | 0.15:1.85 |
f | 89.06 | 4.23 | 39.29 | 0.20:1.80 |
g | 89.48 | 3.47 | 38.94 | 0.25:1.75 |
h | 89.58 | 3.2 | 39.1 | 0.30:1.70 |
Claims (17)
M2Nb2Z7.XMNb2Z6 or MNb2Z6
MNb2Z6
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/294,619 USRE45382E1 (en) | 2010-06-08 | 2014-06-03 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35249710P | 2010-06-08 | 2010-06-08 | |
US13/154,777 US8192541B2 (en) | 2010-06-08 | 2011-06-07 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
US14/294,619 USRE45382E1 (en) | 2010-06-08 | 2014-06-03 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/154,777 Reissue US8192541B2 (en) | 2010-06-08 | 2011-06-07 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE45382E1 true USRE45382E1 (en) | 2015-02-24 |
Family
ID=44317960
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/154,777 Ceased US8192541B2 (en) | 2010-06-08 | 2011-06-07 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
US14/294,619 Active USRE45382E1 (en) | 2010-06-08 | 2014-06-03 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/154,777 Ceased US8192541B2 (en) | 2010-06-08 | 2011-06-07 | Substituted tin niobium pyrochlore and tin niobium oxide pigments |
Country Status (11)
Country | Link |
---|---|
US (2) | US8192541B2 (en) |
EP (1) | EP2580163B1 (en) |
JP (1) | JP5778264B2 (en) |
KR (1) | KR101809028B1 (en) |
CN (1) | CN103097299B (en) |
AU (1) | AU2011264994B2 (en) |
BR (1) | BR112012031404A2 (en) |
CA (1) | CA2801260C (en) |
ES (1) | ES2522215T3 (en) |
PL (1) | PL2580163T3 (en) |
WO (1) | WO2011156362A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2969959B1 (en) | 2013-03-14 | 2019-05-08 | The Shepherd Color Company | Pigments of simultaneously substituted pyrochlore |
DE202017107156U1 (en) | 2017-11-24 | 2017-12-05 | Certoplast Technische Klebebänder Gmbh | Orange stain taking into account transition metal based pigments |
CN117715964A (en) | 2021-07-30 | 2024-03-15 | 罗姆化学有限责任公司 | Opaque light-colored thermoplastic molding compositions |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5143711A (en) * | 1989-12-05 | 1992-09-01 | Asea Brown Boveri Ltd. | Process for manufacturing a precursor powder for use in making a varistor and a powder manufactured in this process |
CN1324387A (en) | 1998-10-26 | 2001-11-28 | 格尔德·雨果 | Coating with spectral selectivity |
US20020170429A1 (en) * | 2001-03-19 | 2002-11-21 | Advanced Technology Materials Inc. | Oxygen enhanced CDA modification to a CDO integrated scrubber |
US6830822B2 (en) * | 1996-09-03 | 2004-12-14 | Nanoproducts Corporation | Inorganic colors and related nanotechnology |
CN1671816A (en) | 2001-05-15 | 2005-09-21 | 欧罗克拉公司 | Thermochromic material |
US20070026247A1 (en) * | 2005-07-29 | 2007-02-01 | Paranthaman Mariappan P | Doped LZO buffer layers for laminated conductors |
CN1954036A (en) | 2003-11-20 | 2007-04-25 | 约翰逊马西有限公司 | Inorganic pigments |
US7387673B2 (en) * | 1996-09-03 | 2008-06-17 | Ppg Industries Ohio, Inc. | Color pigment nanotechnology |
JP2009073675A (en) | 2007-09-18 | 2009-04-09 | Mitsui Mining & Smelting Co Ltd | Metal oxide powder and method for producing the same |
CN102307954A (en) | 2009-02-09 | 2012-01-04 | 威士伯采购公司 | In-store tintable non-infrared-absorptive paint and stain system |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02217309A (en) * | 1989-02-15 | 1990-08-30 | Agency Of Ind Science & Technol | Multimetal chalcogenide superconductor |
FR2712596B1 (en) * | 1993-11-18 | 1996-03-08 | Rhone Poulenc Chimie | Pigments based on zirconium oxide and cerium, praseodymium and / or terbium, process for their preparation and their use. |
DE4429532A1 (en) * | 1994-08-19 | 1996-02-22 | Cerdec Ag | Color pigments based on oxide nitrides, their production and use |
JP2009516589A (en) | 2005-11-22 | 2009-04-23 | アルテアナノ インコーポレイテッド | Method for producing high surface area nanoporous catalyst and catalyst support structure |
-
2011
- 2011-06-07 BR BR112012031404A patent/BR112012031404A2/en not_active Application Discontinuation
- 2011-06-07 KR KR1020137000411A patent/KR101809028B1/en active IP Right Grant
- 2011-06-07 JP JP2013514300A patent/JP5778264B2/en active Active
- 2011-06-07 US US13/154,777 patent/US8192541B2/en not_active Ceased
- 2011-06-07 EP EP20110727369 patent/EP2580163B1/en active Active
- 2011-06-07 WO PCT/US2011/039432 patent/WO2011156362A1/en active Application Filing
- 2011-06-07 PL PL11727369T patent/PL2580163T3/en unknown
- 2011-06-07 ES ES11727369.8T patent/ES2522215T3/en active Active
- 2011-06-07 AU AU2011264994A patent/AU2011264994B2/en active Active
- 2011-06-07 CA CA2801260A patent/CA2801260C/en not_active Expired - Fee Related
- 2011-06-07 CN CN201180028432.8A patent/CN103097299B/en active Active
-
2014
- 2014-06-03 US US14/294,619 patent/USRE45382E1/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5143711A (en) * | 1989-12-05 | 1992-09-01 | Asea Brown Boveri Ltd. | Process for manufacturing a precursor powder for use in making a varistor and a powder manufactured in this process |
US6830822B2 (en) * | 1996-09-03 | 2004-12-14 | Nanoproducts Corporation | Inorganic colors and related nanotechnology |
US7387673B2 (en) * | 1996-09-03 | 2008-06-17 | Ppg Industries Ohio, Inc. | Color pigment nanotechnology |
CN1324387A (en) | 1998-10-26 | 2001-11-28 | 格尔德·雨果 | Coating with spectral selectivity |
US20020170429A1 (en) * | 2001-03-19 | 2002-11-21 | Advanced Technology Materials Inc. | Oxygen enhanced CDA modification to a CDO integrated scrubber |
CN1671816A (en) | 2001-05-15 | 2005-09-21 | 欧罗克拉公司 | Thermochromic material |
CN1954036A (en) | 2003-11-20 | 2007-04-25 | 约翰逊马西有限公司 | Inorganic pigments |
US7594961B2 (en) | 2003-11-20 | 2009-09-29 | Loughborough University Enterprises Limited | Inorganic pigments |
US20070026247A1 (en) * | 2005-07-29 | 2007-02-01 | Paranthaman Mariappan P | Doped LZO buffer layers for laminated conductors |
JP2009073675A (en) | 2007-09-18 | 2009-04-09 | Mitsui Mining & Smelting Co Ltd | Metal oxide powder and method for producing the same |
CN102307954A (en) | 2009-02-09 | 2012-01-04 | 威士伯采购公司 | In-store tintable non-infrared-absorptive paint and stain system |
Non-Patent Citations (3)
Title |
---|
Chinese Office Action dated Jun. 4, 2014 for Aplication No. 201180028432.8. |
Cruz, L., et al., "Synthesis and Characterization of Tin Niobates," Journal of Solid State Chemistry, vol. 156(2) (Feb. 1, 2001) pp. 349-354. |
International Search Report and Written Opinion dated Aug. 19, 2011 for Application PCT/US2011/039432. |
Also Published As
Publication number | Publication date |
---|---|
AU2011264994A1 (en) | 2012-12-06 |
KR20130083431A (en) | 2013-07-22 |
JP2013528156A (en) | 2013-07-08 |
ES2522215T3 (en) | 2014-11-13 |
WO2011156362A1 (en) | 2011-12-15 |
US20110297045A1 (en) | 2011-12-08 |
AU2011264994B2 (en) | 2014-01-16 |
CN103097299A (en) | 2013-05-08 |
EP2580163B1 (en) | 2014-08-13 |
CA2801260C (en) | 2015-01-27 |
PL2580163T3 (en) | 2015-01-30 |
JP5778264B2 (en) | 2015-09-16 |
CA2801260A1 (en) | 2011-12-15 |
CN103097299B (en) | 2015-12-16 |
KR101809028B1 (en) | 2017-12-14 |
EP2580163A1 (en) | 2013-04-17 |
US8192541B2 (en) | 2012-06-05 |
BR112012031404A2 (en) | 2016-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103351023B (en) | Infrared reflective material and preparation method thereof and paint and resin combination containing the material | |
US9868860B2 (en) | Bismuth vanadate pigments | |
USRE45382E1 (en) | Substituted tin niobium pyrochlore and tin niobium oxide pigments | |
JP2019509959A (en) | Modified black spinel pigments for glass and ceramic enamel applications | |
ES2772301T3 (en) | Copper oxide infrared pigments, methods for their production and paints comprising pigments | |
Zou et al. | Yellow β-Bi2O3/BaCO3 complex pigments with impressive near infrared reflectance and excellent color performance | |
US10035914B2 (en) | Inorganic blue pigments from cobalt doped magnesium having transition element oxides and a process for the preparing the same | |
US9238735B2 (en) | Copper containing infrared reflective pigment compositions | |
US20230052771A1 (en) | Electromagnetic wave absorbing particles, electromagnetic wave absorbing particle dispersion liquid, and method for manufacturing electromagnetic wave absorbing particles | |
US10619025B2 (en) | Pink and violet pigments that display heat stability, resistance to acidic conditions, and good lightfastness | |
Sorlí et al. | Structure and color of NixA1− 3xB2xO2 (A= Ti, Sn; B= Sb, Nb) solid solutions | |
US4919723A (en) | Rutile mixed phase pigments with improved coloristic properties | |
White | Complex inorganic color pigments: an overview | |
CZ285333B6 (en) | Process of enhanced preparation of bismuth-vanadate compounds | |
Pfaff | 45 Mixed metal oxide pigments | |
KR20220160736A (en) | Thermochromic pigment and method for preparing thereof | |
KR20000048852A (en) | Method for preparing coloured pigments with titanium dioxide base |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Fee payment |
Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2552); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 8 |
|
AS | Assignment |
Owner name: BANK OF AMERICA, N.A., AS THE ADMINISTRATIVE AGENT, NORTH CAROLINA Free format text: NOTICE OF GRANT OF SECURITY INTEREST IN PATENTS;ASSIGNOR:THE SHEPHERD COLOR COMPANY;REEL/FRAME:060436/0054 Effective date: 20220622 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2553); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 12 |