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    • 专利摘要:
    Compound based on the crystalline structure of scheelite, composition that comprises it and its use. Compound based on the crystalline structure of scheelite of formula camand wz lc sd o4º ero2 .fdo2, where m is a cation of a metal chromophore selected from chromium, iron and manganese, l is a cation of an element selected from yttrium, lanthanum, cerium, praseodymium, neodymium and europium, s is a cation of a metal sensitizer selected from silicon, antimony, zirconium, titanium, aluminum, molybdenum, vanadium and nickel, r is a tetravalent cation of a selected element of between titanium, zirconium or tin, d is a tetravalent cation of silicon where the sum of y, z, c, and d is equal to 1. The invention also relates to compositions comprising said compound and its uses thereof as pigments and/or photocatalysts. Also, the compounds have a high solar reflection index sri for each color range. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2616347A1
    申请号:ES201730455
    申请日:2017-03-29
    公开日:2017-06-12
    发明作者:Guillermo MONRÓS TOMÁS；Carina GARGORI GARCÍA；Mario Ignacio LLUSAR VICENT；Vicente José ESTEVE CANO
    申请人:Universitat Jaume I de Castello；
    IPC主号:
    专利说明:

    The present invention relates to compounds based on the crystalline structure of Scheelite with high values of solar reflection index (hereinafter SRI, from the English Solar Reflectance Index) with high staining capacity, high durability and high opacity. Also, the present invention relates to compositions that
    10 comprise said compounds and the use thereof as pigments for, for example, paints, glasses and ceramics, as well as their use as photocatalysts. STATE OF THE TECHNIQUE
    Paints are normally formulated with a combination of pigments and fillers.
    15 to achieve coverage power, staining capacity, gloss, luster, color and resistance desired. The pigments used in paint can include organic and inorganic pigments, pigment flakes, insoluble dyes and other durable coloring matter. Titanium dioxide is widely used in paints and coatings to improve the
    20 luminosity and opacity, but it is an expensive primer pigment. Titanium dioxide stands out for its high refractive index (2.73 for rutile and 2.55 for anatase) and has a very pure white. Anatase was used as a bleach and opacifier after 1918, replacing the traditional toxic pigments based on Zn, Sb or Pb as the white albayalde (PbC03) 2Pb (OH) 2 or the lithopon white (a
    25 equimolecular coprecipitate of BaSO4 and ZnS). Anatase often has a potent photocatalytic capacity that disintegrates and discolors polymers. In 1940, rutile replaced anatase as an opacifier in paints due to its greater light scattering capacity, given its higher refractive index and, above all, because it did not cause the disintegration and discoloration of paint polymers due to its low
    30 photocatalytic capacity compared to anatase. In addition, ultraviolet radiation from the sun in the 300-350 nm range, in conjunction with other environmental factors such as oxygen, ozone and industrial pollutants, causes depolymerization of plastics by photochemical oxidation (photolysis). Both anatase and rutile absorb ultraviolet radiation from sunlight protecting the paints from their
    35 photolytic degradation (direct action of light on materials), However, anatase is usually a potent photocatalyst (degradation associated with an effect


    catalytic different from simple photolysis) and organic-based paints would not be protected with anatase, unless photocatalysis is controlled, allowing to act on the molecules we are interested in destroying (organic pollutants such as volatile organic compounds) and preserving those we are interested in maintaining
    5 molecules of the organic resin based on the paint, if applicable), in what is called selective photocatalysis. The development of new compounds that have high pigmentation capacity, as well as photocatalytic activity, as well as high SRI values, are of great interest in the field of dyes and pigments.
    10 Currently, there are no known compounds based on Scheelite structure that present these characteristics and that are susceptible of application as pigments. Scheelite, of formula CaWO4, is the structure of a tetragonal mineral, with a 4 / m point group and I41 / a spatial group being isostructural with fergusonite and
    15 powellite Its ABO4 structure can be considered derived from CaF2 fluorite by replacing Ca with cations A and B in a 1: 1 atomic ratio, A occupies a very deformed dodecahedral hole and B has tetrahedral coordination. This crystallography makes the structure suitable for solid solutions with YNbO4 fergusonite, CaMoO4 powellite, MnWO4 hubnerite, FeWO4 ferberite, PbWO4 stolzite.
    20 Scheelite meets the characteristics necessary to support pigments: a) high thermal and chemical stability against ceramic glazes, b) high refractive index, Scheelite is birefringent with values nω = 1.918 -
    1,921 nε = 1,935 - 1,938 similar to the zircon.c) low symmetry structure with distorted crystalline environments and capable of
    25 accommodating variable valence cations in solid solution. The present invention proposes new compounds based on the crystalline structure of Scheelite that have high pigmentation or staining capacity, as well as photocatalytic activity. In addition, they have high SRI values, high durability and high opacity, which makes them excellent candidates for application in the field of
    30 paints on metal (such as those applied on the car body), on wood of any type, cement, plaster and any other type of inorganic substrate. DESCRIPTION OF THE INVENTION
    In a first aspect, the present invention relates to a compound based on the crystalline structure of Scheelite of formula (I):


    CaMyWzLcSdO4 · eRO2.fDO2 (Formula I) where M is a cation of a chromophore metal selected from chromium, iron and manganese,
    5 L is a cation of an element selected from ytrium, lanthanum, cerium, praseodymium, neodymium and europium, S is a cation of a sensitizing metal selected from silicon, antimony, zirconium, titanium, aluminum, molybdenum, vanadium and nickel, R is a tetravalent cation of an element selected from titanium, zirconium and
    10 tin, D is a tetravalent silicon cation and has values between 0 and 0.2 z has values between 0.6 and 1.0 c has values between 0 and 0.3
    15 d has values between 0 and 0.3 and has values between 0 and 0.3 f has values between 0 and 0.3 where the sum of y, z, c, yd is equal to 1 and where at least one of y , c, and d is nonzero.
    The cation of the chromophore metal M, the cation L and the cation of the sensitizing metal S replace tungsten atoms (W) in the crystalline structure of Scheelita. In the present invention, chromophore cation is understood as the one that produces the color of the material. The compounds of formula (I) indicated above preferably have a
    25 yellowing in the case that y is nonzero and white in the case that y is zero. Preferably, the chromophore metal cations are selected from chromium (III), iron (III) and manganese (III). More preferably, the chromophore cation is a chromium (III) cation.
    30 The cations L selected from an element selected from ytrium, lanthanum, cerium, praseodymium, neodymium and europium are modifying agents that alter the crystal network, are integrated into the structure by modifying the crystalline field on the chromophore and, therefore, the color. Preferably, the L cations are trivalent cations of ytrium, lanthanum, cerium,
    35 praseodymium, neodymium or europium. More preferably, the cation L is a cerium (III) cation.


    Sensitizing metal cations (S) increase the reflectivity in the infrared. For example, silicon, antimony, zirconium are sensitizers in the entire wavelength range (4002500nm); in the low wavelength range (400-1300 nm) aluminum and tungsten. Molybdenum is sensitizing in the
    5 high wavelength range (1300-2500 nm). The sensitizing metal cations (S) are preferably silicon (IV), antimony (III), zirconium (IV), titanium (IV), aluminum (III), molybdenum (VI), vanadium (V) and nickel (II). More preferably the sensitizing metal cation (S) is a molybdenum cation (VI).
    10 RO2 and DO2 compounds modify the band gap or band jumps of the compound improving photocatalytic capacity, there are first-level or heavy-duty (R = tetravalent cation of Ti, Zr, Sn) and light second level or low load (D = tetravalent cation of Si). In one embodiment of the invention, e and f are zero.
    In another embodiment of the invention, e and f are zero and y is nonzero. Preferably y is 0.075 or 0.1 and c, d, e and f are zero, or y is 0.075, d is 0.1 and c, e and f are zero. In another embodiment of the invention, and it is zero. In a more preferred embodiment in which y is zero, d is 0.1 and c, e and f are zero. In another preferred embodiment in which y is
    20 zero, c is 0.1 and d, e and f are zero. In another preferred embodiment in which y is zero, d and c are zero and e and f are 0.1. The compounds of the present invention are preferably in the form of micrometer powders between 2m and 15m of average particle size. The size measurements were made by electron microscope and also with equipment
    25 measurement of particle size distribution by laser beam diffraction (device model: Coulter LS). They can also be in the form of concentrated emulsion. In this case, the compound powders would be emulsified in water and a surfactant. Preferably the emulsion in water contains between 30-45% by weight of the powder of the
    Compound and 0.2-0.7% by weight of surfactants such as alkylbenzylammonium (ABA), hexamethyltrimethylammonium (HTA) and sodium dodecyl sulfate (SDS). The compounds of the present invention can be obtained by the ceramic method (EC) starting from oxides or carbonates of the starting components, which are homeogenized in a dry or wet mill, preferably a ball mill.
    35 The MOD methodology can also be used (from English, Metal Organic Decomposition) ((1) T. Blaudeck, H. Lang, R-R Baumann, Concepts of metal-organic


    decomposition (MOD) silver inks for structured metallization by inkjet printing, MRS Online Proceeding Library Archive 1285: 772 · June 2011 DOI: 10.1557 / opl. 2011.772
    (2) C. Gargori, R. Galindo, S. Cerro, M.Llusar, A. GarcÃa, J. Badenes, G.Monrós,
    Ceramic pigments based on chromium and vanadium doped CaTiO3 perovskite
    5 obtained by Metal Organic Decomposition (MOD). Bowl. Soc. Esp. Ceram. Vidr. 51 (212) 313-320, doi: 10.3989 / cyv. 432012. (3) B. Pal, M. Sharon, Preparation of iron oxide thin film by metal organic deposition from Fe (III) -acetylacetonate: a study of photocatalytic properties, Thin Solid Films, 379, 1–2 (2000) 83–88 ) in which soluble salts, preferably nitrates, are dissolved in water and added to them
    10 a polycarboxylic acid as complexing. The general MOD methodology for the preparation of 100 g of compound is described below:
    -  Where appropriate, dissolution of CaCO3 and WO3 in 100 ml of 20% HNO3 by adding
    slowly said compounds in powder form on the acid to form the corresponding nitric solutions (nitrates),
    - water addition up to 500 ml,
    -  addition of the rest of the elements (chromophores (M), modifying elements (L) and sensitizers (S)) that will be part of the nitrate compound,
    -  addition of polycarboxylic acid (eg oxalic / citric) in molar ratio acid: sum of cations = 0.25, 1, 1.5 or 2,
    -  dropwise addition of 17.5% ammonia until gelation or pH 8,
    -  oven dried at 110 ° C,
    -  calcination at 500 ° C / 1h (carbonized),Chromophores are added to modulate the SRI value and color hue
    25 (M), modifying elements (L) and sensitizers (S). Sensitizers increase the NIR reflectivity of the formulation. The conventional method (EC) for preparing the compounds of the present invention is described below: tungsten oxides precursors (WO3), calcium carbonate (CaCO3) together with the precursor oxides or salts of chromophores cations (M),
    30 modifiers (L) and sensitizers (S) that are considered in the formulation are homogenized and mixed in a dry way in a mixer or in a wet way in a ball mill, adding 25-40% of water. The powder of the mixture is dried in an oven in the case of the wet track and in any case they are screened at 200 microns. As an example, as chrome precursors, Cr2O3 eskolaita can be used or
    35 any chromium salt preferably nitrate. As iron precursors, preferably Fe2O3 hematite or any iron salt, preferably nitrate or


    sulfate (Mohr salt). MnO2 pyrolusite can be used as a manganese precursor
    or any manganese salt, preferably nitrate.The oxide or any salt of ytrium, lanthanum, is used as precursors of the cations.cerium, praseodymium, neodymium and europium, preferably nitrates.
    As precursors of sensitizing cations S can be used: a) of the entire wavelength range, quartz, antimony oxide III (Sb2O3), monoclinic zirconium oxide (ZrO2), anatase TiO2), b) of low wavelength (400-1300 nm) Al2O3 corundum and tungsten oxide WO3, oc) high wavelength (1300-2500 nm) MoO3 molybdenum oxides or any salt thereof,
    10 preferably nitrate. Once the mixtures are obtained (either the carbonized mixture at 500 ° C by the MOD methodology or the EC dry mixture), these are calcined in an oven with heating rates of 5-10 ° C / min and maintained for 2-5 hours (time of retention t) at a temperature between 900 and 1200 ° C (cooking temperature T).
    15 Once the oven has cooled in free cooling, the powders are milled in a mill to an average particle size between 2m -15 m. and if necessary, wash with water until no positive visual reaction by adding a few drops of 1,5-diphenylcarbazide solution in acetone (5 g / L) to the wash waters (wash until Cr (VI) is absent by visual detection of violet coloration). Washing is necessary
    20 to eliminate soluble salts that can be generated in the calcined and that are not part of the compound. In the event that the compound includes RO2 and DO2 modifiers, these are added to the calcined obtained and mixed in the mill for homogenization-milling. Another aspect of the present invention relates to a composition comprising the
    Less a compound of formula (I) as described above. Preferably, the compound is in a proportion of 5% by weight in the composition. The composition comprising the compound of formula (I) may be a polymeric, vitreous or ceramic composition. Preferably, the composition is a
    30 polymeric base paint, for example, a vinyl or acrylic paint. Another aspect of the present invention relates to the use of the compound of formula (I)
    CaMyWzLcSdO4 · eRO2.fDO2 (Formula I) where 35 M is a cation of a chromophore metal selected from chromium, iron and manganese,


    L is a cation of an element selected from ytrium, lanthanum, cerium, praseodymium,neodymium and europium,S is a cation of a sensitizing metal selected from silicon, antimony,zirconium, titanium, aluminum, molybdenum, vanadium and nickel,
    5 R is a tetravalent cation of an element selected from titanium, zirconium and tin, D is a tetravalent silicon cation and has values between 0 and 0.2 z has values between 0.6 and 1.0
    10 c has values between 0 and 0.3 d has values between 0 and 0.3 and has values between 0 and 0.3 f has values between 0 and 0.3 where the sum of y, z, c, yd is equal to 1
    15 as a pigment and / or as a photocatalyst. Preferably, the compounds of formula (I) are used as cooling pigments. As previously mentioned, the chromophore metal cation (M), the cation (L) and the sensitization metal cation (S) replace tungsten atoms (W)
    20 in the crystal structure of Scheelita. Preferably, the chromophore metal cations are selected from chromium (III), iron (III) and manganese (III). More preferably, the chromophore cation is a chromium (III) cation. Preferably, the L cations are trivalent cations of ytrium, lanthanum, cerium,
    25 praseodymium, neodymium or europium. More preferably, the cation L is a cerium (III) cation. The sensitizing metal cations (S) are preferably silicon (IV), antimony (III), zirconium (IV), titanium (IV), aluminum (III), molybdenum (VI), vanadium (V) and nickel (II). More preferably the sensitizing metal cation (S) is a molybdenum cation.
    30 (VI). In a preferred embodiment in relation to the use of the compound of formula (I), e and f are zero. The compounds of formula (I) indicated above preferably have a yellow color in the case that y is nonzero and white in the case that
    35 and be zero.


    In a preferred embodiment of yellow pigments, and is 0.075 or 0.1 and c, d, e and f arezero. In another preferred embodiment of yellow pigments, and is 0.0075, d is 0.1 and c, eand f are zero.In a preferred embodiment of white pigments, d is 0.1 e and, c, e and f are zero.
    5 In a preferred embodiment of white pigments, c is 0.1 e and, d, e and f are zero. In another preferred embodiment of white pigments, y, c and d are zero and e and f are 0.1. The compounds of formula (I) used as pigments and / or photocatalysts are preferably in the form of micrometric powders between 2 and 15 micrometers of average particle size. They can also be in the form of
    10 concentrated emulsion. In this case, the compound powders would be emulsified in water and a surfactant. Compounds of formula (I) may be carried out through MOD (English, Metal Organic Decomposition) methodology or by conventional ceramic method (EC) using mechanical mixing such as a ball mill as described.
    15 above. The compounds of formula (I) are preferably used as pigments in polymeric substrates such as vinyl or acrylic paints, glass, enamel, or ceramics. These pigments provide color to the matrix or substrate that comprise them in addition to presenting a photocatalyst effect.
    The pigments are also preferably photocatalysts. Therefore, the compounds of formula (I) can also be used as photocatalysts. The described pigments, preferably yellow and white, based on the crystalline structure of Scheelita have high coloring capacity, high SRI values for each color range and photocatalytic capacity properly activated in
    25 glasses and ceramics, which gives them self-cleaning and pollutant removal capacity such as resistant organic compounds (azoderivatives, for example) and nitrogen oxides (NOx). In the case of paints, activated pigments have selective photocatalytic activity, preserving paint polymers but degrading air pollutants. In this sense they act degrading
    30 photocatalytically to simple organic compounds and protecting polymers from UV radiation (UV blocking effect). The pigments that are the object of the present invention are cooling or cold pigments ("cool pigments") that have high near-infrared reflectivity (NIR, 780-2500 nm), or equivalently, low absorptivity in the NIR,
    35 which allows a significant saving in the air conditioning of warm areas, protecting the building with a lining envelope with high light reflectivity


    infrared When the solar radiation affects the roof and walls of a building, part of the radiation is reflected and part is transferred to the interior of the building. The greater this transfer and the lower the reflected, the greater the energy cost to keep the building cool. In this sense, the white pigments of rutile base are
    5 has used as a cooling material in residential ceilings, presenting reflections of the order of 87%. However, many owners prefer non-white ceilings for aesthetic reasons. The pigments described in this invention can be obtained with white or yellow colorations, preferably with high NIR reflectivity and high SRI solar reflectivity index.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and
    15 are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES FIG. 1: X-ray diffraction diagram of compound (pigment) Yellow-1 (CaCr 0.075W0.925O4).
    20 FIG. 2: Standard solar spectrum of the American Society for Testing and Materials (ASTM G173-03, 2003). FIG. 3: Vis-NIR spectrum (300-2500nm) of compound Yellow -1 (the percentages indicated are in% by weight of the pigment in the material in question): A) in powder form; B) in 5% colorless base vinyl paint; C) in 5% sodoccalc glass; D) in
    Fried bicoction at 1050 ° C at 5%; E) in 5% mono-porous frit 1080 ° C (ripening temperature); F) in 1180 ° C 5% porcelain frit. FIG. 4: Scanning microscopic photomicrograph of the Yellow-1 compound in powder form performed with a LEYCA Leo-440i SEM (Scanning Electron Microscopy) electron microscope with X1000 magnification.
    30 FIG. 5: Comparison of the Vis-NIR total reflectivity spectra (350-2500 nm) of the Yellow-1 embodiment with those of a concentrated organic ink referred to in the figure as yellow 12 (organic) (Universal product reference dye: 16261714, obtained from Leroy Merlin España, SL). FIG. 6: Vis-NIR spectrum (300-2500nm) of the White-1 compound (CaWO4) (the
    35 percentages indicated are in% by weight of the pigment in the material in question): A)


    in monoporous frit (ceramic glaze that matures at 1080 ° C) at 5% B) in 5% porcelain stoneware. FIG. 7: Vis-NIR spectrum (300-2500nm) of the White -3 compound (CaWO4.0,1ZrO2.0,1SiO2) (the percentages indicated are in% by weight of the pigment
    5 in the material in question): A) in 5% Monoporose frit B) in 5% porcelain stoneware. FIG. 8: Scanning microscopic photomicrograph of White-1 in microporous enamel performed with a LEYCA Leo-440i SEM (Scanning Electron Microscopy) electron microscope with X5000 magnification. EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the compound of the invention. Example 1: Preparation of yellow and white pigments.
    15 By the conventional technique (EC) described above, the following pigments were made: yellow-1, yellow-2, yellow-3, yellow-4, yellow-5, white1, white-2 and white-3 shown in the Table 1. The yellow-6 compound was prepared by the MOD methodology explained above. Table 1 shows the composition of each of them, the compounds of
    20 heading for its preparation, as well as the reaction time and temperature. Table 1: Yellow and white pigments. Preparation parameters
    COMPOSITION STARTING COMPOUNDSt (h)T (ºC)
    YELLOW 1 CaCr 0.075W0.925O4 y = 0.075 z = 0.925 c, d, e, f = 0CaCO3 WO3 Cr2O331000
    YELLOW 2 CaCr0.075W0.825Mo0.1O4 y = 0.075 z = 0.825 c, e, f = 0 d = 0.1CaCO3 WO3 Cr2O3 MoO331000
    YELLOW 3 CaCr0.075W0.825Sb0.1O4 y = 0.075 z = 0.825 c, e, f = 0 d = 0.1CaCO3 WO3 Cr2O3 SbO331000
    YELLOW Cr0,1CaW0,9O4 y = 0.1 z = 0.9CaCO3 WO3 Cr2O331000


    4 c, d, e, f = 0
    YELLOW 5 Cr0.075Ce0.1CaW0.825O4 y = 0.075 z = 0.825 c = 0.1 d, e, f = 0CaCO3 WO3 Cr2O3 CeO231000
    YELLOW 6 CaCr 0.075W0.925O4 y = 0.075 z = 0.925 c, d, e, f = 0CaCO3 WO3 Cr (NO3) 3.9H2O31000
    WHITE-1 CaWO4 z = 1 y, c, d, e, f = 0CaCO3 WO331000
    WHITE-2 CaW0.9Mo0.1O4 z = 0.9 y, c, e, f = 0 d = 0.1CaCO3 WO3 MoO331000
    WHITE-3 CaWO4.0,1ZrO2.0,1SiO2 z = 1 y, c, d = 0 e, f = 0.1CaCO3 WO3 ZrO2 SiO231000
    WHITE-4 CaW0.9Ce0.1O4 z = 0.9 c = 0.1 y, d, e, f = 0CaCO3 WO3 CeO231000
    The pigments obtained were characterized by randomly oriented powder X-ray diffraction on a Siemens D5000 diffractometer with Cu K radiation in the range 10-70º2, scanning speed 0.05 º2 / s, time constant 10 s and
    5 conditions of 40 kV and 20 mA. X-ray diagrams demonstrated the presence of Scheelita's unique crystalline structure. Likewise, the CIEL * a * b * color parameters of powders (P) or glass enamels (V), bicoction ceramic frit at 1050ºC (B), ceramic fritters were measured
    10 monoporous at 1080ºC (M) and fried porcelain stoneware (PR) or applications in colorless vinyl paint (PI). The color of the painted or glazed platelets was measured using the color parameters L * a * b * following the CIE methodology (CIE Commission International de l'Eclairage, Recommendations on Uniform Color Spaces, Color Difference Equations,
    15 Psychometrics Color Terms. Supplement No. 2 of CIE Pub. No. 15 (E1-1.31) 1971, CIE Central Bureau, Paris (1978)) using the Jasco V670 spectrometer, with illuminant D65 and 10º observer. In this method, L * measures clarity (100 = white, 0 = black), a * and b * measure the color (Chroma) (- a * = green, + a * = red, -b * = blue, + b * = yellow)


    The SRI solar reflection index calculated according to the methodology described below was measured. The outer surfaces of buildings exposed to the sun absorb a part of the solar radiation (measured by the absorptivity coefficient ) and reflect the rest (measured
    5 for the reflectivity coefficient r = 1-). The radiation absorbed in the form of heat part is transmitted to the interior (measured by the conductivity of the material ) and the other part is re-transmitted to the outside through convection mechanisms and by radiation re-emission (proportional to the fourth power of the absolute temperature of the surface according to the Stefan-Boltzamann law and the characteristics of the
    10 material measured by the emittance coefficient ). In the thermal equilibrium of an insolated surface, equation 1 is fulfilled.
      (1-r) I =  (Ts4-Tsky4) + hc (Ts-Ta) +  (Ts-Tx) / x (equation 1)
    where:
    15 r = reflectance  = Stefan Boltzmann constant, 5.67 10-8 W / m2K4.  = emittance hc = convection coefficient (W / m2K) Ts = absolute temperature of the surface insolated in equilibrium.
    20 Tsky = reference temperature of the sky. Ta = air temperature. x = wall thickness Tx = temperature on the inside surface of the wall The normal or standard conditions of heat stroke, for the purpose of subsequent calculation, are
    25 consider: solar irradiation I = 1000 W / m2, normal air temperature Ta = 310K, convective coefficient hc = 12 W / m2K and apparent sky temperature Tsky = 300K.
    The SRI solar reflection coefficient is defined, for its acronym in English, to the value:
    (equation 2) 100 ೢೞ ି ் ି ் ್್ ்் ൌ ܵ ܵ 30
    Under the standard conditions defined above, considering the conduction heat transmission component negligible:
    Tb = ideal black body temperature, 355.61K (82.6 ° C)


    Tw = ideal white body temperature 317.76K (44.7 ° C).
    Under standard conditions it can be estimated as the value of the stationary surface temperature using equation 3.
    Ts (K) = 310.04 + 82.49  - 2.82 - 54.33  + 21.72 2 (equation 3)
    Where  is the surface absorptivity ( = 1-r).
    Equation 4 results when substituting data in equation 2, which relates the absolute temperature of the surface insolated in equilibrium (Ts) with the solar reflection coefficient SRI of the surface.
     SRI = 218 - 2.64 Ts (equation 4, with temperature in ° C)
    The measurement of the SRI solar reflection index can be done through the above methodology, based on the surface thermal equilibrium temperature under the standard solar irradiation conditions described above. Usually we choose the weighted averaging method based on the measurement of the total reflectivity of the surface, using the UV-Vis-NIR diffuse reflectance spectrometry technique (300-2500 nm) referred to that of the standard solar spectrum (total fraction of solar energy reflected in standard atmospheric conditions described above). The solar spectrum used is that of the American Society for Testing and Materials (ASTM G173-03, 2003), which is presented in Figure 2.
    Using this method, the total solar reflectivity of the surface R is calculated using equation 5.
    మఱబబ
    ୰ ሺሻ ୧ ሺሻ ୢ
    యబబ
    (equation 5) మఱబబ ׬ R ൌ
    ୧ ሺሻ ୢ
    యబబ
    ׬
    Where r () is the measure of the spectral reflectance at each wavelength of the surface studied and i () is the spectral irradiance at the wavelength considered, of the standard solar spectrum of the American Society for Testing and Materials (ASTM G173 -03, 2003) of Figure 2.


    With this value of R (r in equation 1) and that of the surface emittance, Ts is calculated using equation 1 under standard conditions, and with this value, that of SRI with equation 4. Usually the emissivity  of the surfaces are around 0.9 (eg water 0.96, ceramic 0.9. asphalt 0.88) except for non-anodized metals (eg Ag 0.02
    5 At 0.03 Cu 0.04), which when anodizing them take values of their oxides, also around 0.9. In short, the response of the envelope of a building to solar irradiation depends on a number of variables such as reflectivity, emittance, absorptivity, solar flow, sun-air temperature and the thermal resistance of the envelope.
    10 Approximately 50% of the solar flux is absorbed by the earth's surface, black surfaces absorb up to 90% of the radiation, the total solar reflectivity
    (R) would be 10% (SRI less than 6 with a minimum of -6 for R = 0% for ceramic samples), White absorbs only up to 25% with an R greater than 75% (SRI greater than 93 and a maximum of 129 for R = 100% for ceramic surfaces). The
    15 white surfaces remain cooler than black. Colored surfaces have intermediate values (R = 10-80%, SRI = 6-100). Likewise, the photocatalytic activity of the synthesized compounds was evaluated. This evaluation was carried out by measuring the degradation of Orange II in aqueous solution and removal of NOx from the air by oxidation to nitrates.
    20 Orange II is a persistent C16H11N2SO4Na monoazo sulfonate dye, which is widely used as a model dye in photocatalytic photodegradation studies. The degradation mechanism of this compound is well described in the literature (Konstantyinou I.K., Albanis T.A., 2004, TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations.
    25 review, App. Catalyst B: Environmental 49: 1-14.). To monitor the kinetics of photodegradation of the substrates, an assembly was carried out with a medium pressure mercury lamp of 125 W of power, with emission spectrum that has three characteristic lines at 254, 313 and 365 nm, used as a source of UV radiation on the solution contained in a quartz glass reactor (which
    30 minimizes the filtering of UV radiation from the source) cooled by a jacket with water flow. Orange II monoazo dye solutions of concentration 0.6 · 10-4 M buffered to pH 7.4 were used with a mixture of NaH2PO4 · 4H2O and Na2HPO4 · 7H2O (Panreac, SA) to which the photocatalyst powder was added in suspensions of 500 mg / l kept under continuous agitation. Degradation of
    Orange II was followed by colorimetry at 480 nm. Photodegradation curves are analyzed according to the Langmuir-Hinshelwood model (Galindo R., Gargori C., Badenes


    J., Llusar M., Tena MA, Monrós G., Photocatalytic degradation of orange II azo dye by low titania doped sol-gel glasses, XIVth International Sol-Gel Conference, Abstracts book, Montpellier (France) 2-7 September, 2007 ). With low initial concentrations (Co) and with low absorption by the photocatalyst this kinetic model follows equation 6:
    C
    ln  kKt  Kappt (equation 6)
    C
    where t = irradiation time, C = current dye concentration.
    When representing ln (C / Co) versus the irradiation time, the kinetics followed by the Langmuir-Hinshelwood model have a linear adjustment, the slope of the straight line being the apparent first order velocity constant Kapp. The half-life (t1 / 2) can be calculated considering the expressions:
    C
    ln 2
    ln02  Kt t1 / 2  (equation 7 and 8)
    app 1/2
    K
    c app
    The graphs of ln (C / Co) versus the irradiation time of the materials studied follow the Langmuir-Hinshelwood model. The photocatalytic capacity is evidenced by the kinetic parameters of the t1 / 2 photocatalytic reaction and the square of the linear correlation coefficient R2 of the line obtained calculated with the previous expressions.
    To follow the photocatalysis of the NOx nitrogen oxides of the air by oxidation to nitrates, a conventional colorless vinyl base paint mixed with the powder and water in proportion paint: powder: water = 7: 2: 5 is deposited by brush on a circular grid of 0.2 mm light aluminum and 2.5 cm radius and placed on a closed funnel with porous cotton and irradiated with a 75W UVA lamp with continuous circulation of 6 L / min of a known NOx air current (around 30 g / Nm3 of NOx measured as NO2) through the photocatalyst in the funnel for 48 h. of collection in these conditions. In the present study, environmental measurements with a manual NOx Gastec detector averaged every 12 hours were used as a reference (Galindo R., Gargori C., Badenes J., Llusar M., Tena MA, Monrós G., Photocatalytic degradation of orange II azo dye by low titania doped sol-gel glasses, XIVth International Sol-Gel Conference, Abstracts book, Montpellier (France) 2-7


    September, 2007). The 75W full-power UVA black lamp (3W effective UVA-ray power) is an incandescent filtered light with Wood glass, a special doped silica-sodium-barium glass with 9% nickel (RW Wood, "Secret communications concerning light rays." Journal of Physiology 1919, 5e 5 series: t IX). The intense blue-violet glass is opaque to radiation except for the longest red radiation and the shortest UV, so that it is practically transparent between 320 and 340 nm with an intensity peak at 365 nm as well as the lengths wavelengths longer than red and NIR from the lamp, so the system is kept refrigerated with a fan. After 48 hours of
    At irradiation, the funnel is washed with 10 ml of distilled water and nitrates are measured in the wash waters by colorimetry at 220 nm, calculating the collection efficiency E (%) under these conditions.
    Table 2 shows the results of the characterization of the compounds
    15 prepared Table 2 Achievements Yellow and white: characterization parameters. In particular, the following is shown: a) CIEL * a * b * color parameters of powders of pure compound (P) or of enamels in 5% glass (V), fried ceramic bicoction at 1050ºC at 5%
    20 (B), 5% 1080 ° monoporous ceramic frit (M) and 5% porcelain stoneware (PR) ceramic frit or applications in 5% vinyl colorless paint (PI) (percentages refer to the weight of the compound in the composition or matrix in question), b) crystalline phases detected by DRX, c) SRI solar reflection index calculated according to the methodology described above, d)
    25 half-life period t1 / 2 of the photodegradation of Orange II according to Langmuir-Hinshelwood model, e) Ex uptake efficiency (%) of NOx as nitrates according to the method described above.
    COMPOSITION L * a * b *SRIDRX phasest1 / 2 (min) Orange IIAND(%)
    YELLOW 1 CaCr 0.075W0.925O4 y = 0.075 z = 0.925 c, d, e, f = 0P: 82.1 / 4.9 / 57.6 V: 64.0 / -2.4 / 45.1 B: 72.8 / -5.5 / 37.1 M: 83.1 / -3.1 / 25.7 PR : 74.6 / -2.6 / 42.9 PI: 89.3 / -3.5 / 34.593 64 96 100 82 100Scheelita CaWO41877
    YELLOW 2 CaCr0.075W0.825Mo0.1O4 y = 0.075 z = 0.825 c, e, f = 0P: 73.4 / 0.8 / 48.6 B: 81.1 / -0.8 / 38.786 86Scheelita CaWO4


    d = 0.1
    YELLOW CaCr0.075W0.825Sb0.1O4P: 79.3 / 2.5 / 45.289Scheelita
    3 y = 0.075 z = 0.825 c, e, f = 0 d = 0.1B: 79.1 / -2.6 / 29.686CaWO42466
    YELLOW Cr0,1CaW0,9O4P: 71.8 / 7.6 / 49.880Scheelita
    4 y = 0.1 z = 0.9 c, d, e, f = 0PR: 75.2 / -0.5 / 49.072CaWO4
    YELLOW 5 Cr0.075Ce0.1CaW0.825O4 y = 0.075 z = 0.825 c = 0.1 d, e, f = 0P: 75.9 / -5.7 / 39.8 PR: 69.0 / -6.2 / 45.689 87Scheelita CaWO4; Ca3WO6 (very weak)160 9
    YELLOW 6 CaCr 0.075W0.925O4 y = 0.075 z = 0.925 c, d, e, f = 0P: 82.6 / 5.9 / 56.6 B: 72.8 / -5.5 / 37.1 M: 83.1 / -, 1 / 25.792 95 98Scheelita CaWO4187 8
    WHITE-1 CaWO4 z = 1 y, c, d, e, f = 0M: 91.66 / 0.16 / 1.02 PR: 92.6 / - 86 / 0.7499 93Scheelita CaWO41078
    WHITE-2 CaW0.9Mo0.1O4M: 90.76 / 0.36 / 1.1286Scheelita
    z = 0.9 and, c, e, f = 0 d = 0.1 PR: 91.3 / - 56 / 0.5486CaWO4
    WHITE-3 CaWO4.0,1ZrO2.0,1SiO2M: 94.5 / -0.32 / 1.52101Scheelita
    z = 1 y, c, d = 0 e, f = 0.1 PR: 94.3 / -1 / 1.393CaWO496 5
    WHITE-4 CaW0.9Ce0.1O4M: 93.7 / -0.2 / 1.1100Scheelita
    z = 0.9 c = 0.1 y, d, e, f = 0 PR: 92.3 / -0.8 / 1.491CaWO487 6
    Example 2: Comparison of the compound Yellow-1 with a conventional yellow based on the yellow pigment of praseodymium in zircon (DCMA 14-43-4). In order to compare the yellow Scheelita samples, a yellow one was optimized
    5 conventional, based on the yellow pigment of praseodymium in zircon (DCMA 14-434). For this, a calcine of (Pr0.05Zr0.85Mo0,1SiO4) was prepared. (7.5% NaF 6% NaCl) and addition to the mill of 0.1 mol of TiO2 by weight calcined formula. The following precursors were used to prepare said compound:
    10 Pr6O11, ammonium molybdate, quartz, anatase, NaF, NaCl. In MOD, the same precursors are used by dissolving Pr6O11 in the minimum amount of 35% nitric acid, and adding molybdate and subsequently TEOS (tetraethylorthosilicate), used as


    silicon precursor, followed by zirconyl chloride octahydrate, zirconium precursor,then the NaF and NaCl mineralizers.Ceramic mixing CE (performed in a conventional ball mill during theminus half an hour without exceeding the hour) or carbonized MOD powder,
    5 optionally pelletized by pressing tablets at 200 Kg / cm2 and calcined in an oven with heating rates of 5-10 ° C / min and kept for 2-5 hours (retention time t) at the temperature between 900 and 1200 ° C (cooking temperature T). Once the oven has cooled in free cooling, the powders are ground to an average particle size between 2-20 µm. and if necessary wash up
    10 conductivity less than 500 S. Thus was obtained the pigment that we will call Pr-Zircon. Table 3: Comparison of parameters / properties of yellow-1 with those obtained with optimized classical pigment (Pr-Zircon) including the values of the CMYK model (acronym for Cyan, Magenta, Yellow and Key: Cyan, Magenta, Yellow and Black)
    15 (proportions of the 4 pure CMYK components needed to produce the given color L * a * b *)
    Powder (P) In colorless vinyl paint (PI),In bicoction ceramic frit at 1050ºC (B)
    Pr-Zircon L * a * b *82.7 / 2.0 / 58.886.2 / -1.9 / 44.380.3 / 0.2 / 46.9
    CMYK 0/16/59/510/10/42/612/5/46/11
    SRI 838683
    YELLOW-1 L * a * b *82.1 / 4.9 / 57.689.3 / -3.5 / 34.572.8 / -5.5 / 37.1
    CMYK 0/18/60/46/6/33/60/4/32/25
    SRI 9310096
    In view of the examples presented, it can be concluded that yellow and white pigments, based on the crystalline structure of Scheelita, have high coloring capacity, high SRI values for each color range and high photocatalytic capacity properly activated in glass and ceramics , which gives them self-cleaning and pollutant removal capacity such as resistant organic compounds (azoderivatives, for example) and nitrogen oxides (NOx).

    权利要求:
    Claims (26)
    [1]
    1. Compound based on the crystalline structure of Scheelite of formula (I):
    5 CaMyWzLcSdO4 · eRO2.fDO2 (Formula I) where M is a cation of a chromophore metal selected from chromium, iron and manganese, L is a cation of an element selected from ytrium, lanthanum, cerium, praseodymium, neodymium and europium,
    10 S is a cation of a sensitizing metal selected from silicon, antimony, zirconium, titanium, aluminum, molybdenum, vanadium and nickel, R is a tetravalent cation of an element selected from titanium, zirconium and tin, D is a tetravalent cation of silicon,
    15 and has values between 0 and 0.2 z has values between 0.6 and 1.0 c has values between 0 and 0.3 d has values between 0 and 0.3 and has values between 0 and 0.3
    20 f has values between 0 and 0.3 where the sum of y, z, c, and d is equal to 1 and where at least one of y, c, and d is nonzero.
    [2]
    2. A compound according to claim 1, characterized in that the cation of the chromophore metal M is selected from chromium (III), iron (III) and manganese (III).
    3. A compound according to claim 2 characterized in that the cation of the chromophore metal M is chromium (III).
    [4]
    4. Compound according to any of the preceding claims characterized in that the cation L is a trivalent cation of ytrium, lanthanum, cerium, praseodymium, neodymium or europium.
    Compound according to claim 4 characterized in that the cation L is cerium (III).
    [6]
    6. Compound according to any of the preceding claims characterized in that the sensitizing metal cation S is selected from silicon (IV), antimony (III), zirconium (IV), titanium (IV), aluminum (III), molybdenum (VI), vanadium (V) and nickel (II).
    Compound according to claim 6 characterized in that the sensitizing metal cation S is molybdenum (VI).

    [8]
    8. Compound according to any of the preceding claims characterized in that e and f are zero.
    [9]
    9. Compound according to claim 8 characterized in that y is non-zero.
    A compound according to claim 9 characterized in that y is 0.075 or 0.1 and c and d are zero.
    [11]
    11. Compound according to claim 9 characterized in that y is 0.075, d is 0.1 and c is zero.
    [12]
    12. Compound according to any of claims 1 to 8 characterized in that y is zero.
    [13]
    13. Compound according to claim 12 characterized in that d is 0.1 and c, e and f are zero.
    [14]
    14. Compound according to claim 12 characterized in that c is 0.1 and d, e and f are zero.
    15. A compound according to any one of claims 1 to 7 characterized in that y, d and c are zero and e and f are 0.1.
    [16]
    16. Compound according to any of the preceding claims in powder form with an average particle size between 2 µm and 15 µm or in emulsion form.
    [17]
    17. Compound according to claim 1 selected from the following: CaCr 0.075W0.925O4; CaCr0.075W0.825Mo0.1O4; CaCr 0.075W0.825Sb0.1O4; Cr0,1CaW0,9O4;
    Cr0,1CaW0,9O4; Cr0,075Ce0,1CaW0,825O4; CaCr 0.075W0.925O4; CaW0.9Mo0.1O4; CaWO4.0,1ZrO2.0,1SiO2; CaW0.9Ce0.1O4.
    [18]
    18. Composition characterized in that it comprises the compound defined in any one of claims 1 to 17.
    Composition according to claim 18 characterized in that it comprises at least 5% by weight of the compound defined in any one of claims 1 to 17.
    [20]
    20. Composition according to claim 18 or 19 wherein the composition is polymeric, vitreous or ceramic.
    21. Composition according to claim 20 wherein the composition is polymeric and is a vinyl or acrylic paint.
    [22]
    22. Use of the compound of formula ICaMyWzLcSdO4ERO2.fDO2 (Formula I)
    where 35 M is a cation of a chromophore metal selected from chromium, iron and manganese,

    L is a cation of an element selected from ytrium, lanthanum, cerium, praseodymium,neodymium and europium,S is a cation of a sensitizing metal selected from silicon, antimony,zirconium, titanium, aluminum, molybdenum, vanadium and nickel,
    5 R is a tetravalent cation of an element selected from titanium, zirconium and tin, D is a tetravalent silicon cation and has values between 0 and 0.2 z has values between 0.6 and 1.0
    10 c has values between 0 and 0.3 d has values between 0 and 0.3 and has values between 0 and 0.3 f has values between 0 and 0.3 where the sum of y, z, c, yd is equal to 1 as pigment and / or photocatalyst.
    23. Use according to claim 22 as a cooling pigment.
    [24]
    24. Use according to claim 22 or 23, characterized in that the cation of the chromophore metal M is selected from chromium (III), iron (III) and manganese (III).
    [25]
    25. Use according to claim 24, characterized in that the cation of the chromophore metal M is chromium (III).
    Use according to claim 22 or 23, characterized in that the cation L is a trivalent cation of ytrium, lanthanum, cerium, praseodymium, neodymium or europium.
    [27]
    27.  Use according to claim 26, characterized in that the cation L is cerium (III).
    [28]
    28. Use according to claim 22 or 23, characterized by the metal cation
    Sensitizer S is selected from silicon (IV), antimony (III), zirconium (IV), titanium 25 (IV), aluminum (III), molybdenum (VI), vanadium (V) and nickel (II).
    [29]
    29. Use according to claim 28, characterized in that the sensitizing metal cation S is molybdenum (VI).
    [30]
    30 Use according to any of claims 22 to 29 characterized in that e and
    f are zero. 30. Use according to claim 30, characterized in that y is non-zero.
    [32]
    32 Use according to claim 31, characterized in that y is 0.075 or 0.1 and c and d are zero.
    [33]
    33. Use according to claim 31 characterized in that y is 0.075, d is 0.1 and c is zero.
    Use according to any of claims 22 to 30 characterized in that y is zero.

    [35]
    35 Use according to claim 34 characterized in that d is 0.1 and c, e and f are zero.
    [36]
    36. Use according to claim 34 characterized in that c is 0.1 and d, e and f are zero.
    5 37. Use according to any of claims 22 to 29 characterized in that y, d and c are zero and e and f are 0.1.
    [38]
    38. Use according to claim 22 to 37 characterized in that the compound of formula (I) is in powder form with an average particle size between 2 µm and 15 µm or in emulsion form.
    Use according to claim 22 or 23 wherein the compound is selected from
    CaCr 0.075W0.925O4; CaCr0.075W0.825Mo0.1O4; CaCr 0.075W0.825Sb0.1O4; Cr0,1CaW0,9O4; Cr0,1CaW0,9O4; Cr0,075Ce0,1CaW0,825O4; CaCr 0.075W0.925O4; CaW0.9Mo0.1O4; CaWO4.0,1ZrO2.0,1SiO2; CaW0.9Ce0.1O4; CaWO4.

    FIG. one
    FIG. 2

    % R
    100 90 80 70 60 50 40 30 20 10 0
    350 850 1350 1850 2350
      (nm)
    FIG. 3A
    FIG. 3B

    350 850 1350 1850 2350
      (nm)
    FIG. 3C
    350 850 1350 1850 2350
     (nm)
     FIG. 3D 

    350 850 1350 1850 2350
     (nm)
     FIG. 3E
    80 70 60 50 40 30 20 10 0
      (nm)
    % R
    FIG. 3F

    FIG. 4
    FIG. 5

    TO)
    10090807060fifty4030twenty10
    0 200 700 1200 1700 2200
    Long Wave (nm)
    B)
    % Diffuse reflectance
    FIG. 6

    TO)
    B)
    % Diffuse reflectance% Diffuse reflectance
    100 80 60 40 20 0
    200 700 1200 1700 2200
     Long. Wave (nm)
    100 90 80 70 60 50 40 30 20 10 0
    200 700 1200 1700 2200
    Long. Wave (nm)
     FIG. 7

    FIG. 8
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    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3338841A|1964-05-14|1967-08-29|Du Pont|Luminescent molybdate and tungstate compositions|
    CN102433117A|2011-09-05|2012-05-02|四川师范大学|Chemical solution preparation method for tungsten molybdate solid solution luminescent microcrystal|CN108906067A|2018-07-26|2018-11-30|遵义师范学院|A kind of ceria based composite catalyst and its preparation method and application|
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