SA07280012B1 - Titanium Dioxide Pigment Particles with Doped,Dense SiO2 Skin and Methods for their Manufacture - Google Patents

Abstract

The invention relates to titanium dioxide pigment particles which have improved photo stability, their surface being coated with a dense SiO2 skin that is doped with at least one doping element. The SiO2 skin is characterized in that the doping with the at least one doping element reduces the energy level densities in the valence band and/or in the conduction band in the vicinity of the band gap or that additional energy levels in the band gap are produced. The doped dense SiO2 skin is applied using known wet-chemical methods or is applied in the gas phase to the surface of the titanium dioxide particles. Particularly suitable doping elements are Sn, Sb, In, Ge, Y, Nb, F, Mn, Cu, Mo, Cd, Ce, W and Bi. The following known doping elements AI, B, Ge, Mg, Nb, P, Zr for the gas phase method and Ag, AI, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Mg, Mn, Ni, Nb, Sn, Sr, Ti, Zn, Zr for the wet-chemical method are excluded from the invention.

Description

- y = pigment particles of titanium dioxide with a dense layer similar to silicon dioxide, and methods for its manufacture

Titanium dioxide pigment particles with doped, dense sio; skin and methods for their manufacture FULL DESCRIPTION BACKGROUND TiO, titanium dioxide for pigment particles The present invention relates to particles of dense pigment containing like elements; and methods of manufacturing. showing SiO particles; Provides its surface with a © . Greater photostability to light Leslie titanium dioxide J is a pigment It is used ¢ titanium dioxide J high refractive index Due to the high refractive index of plastic Jue sectors; in many sectors high-quality pigment as a high pigment Quality, however; Fibers and fibers are paper; And paper coatings and coating materials ¢ plastics, that is, photocatalytic reactions » photoactive to light Sle lie titanium dioxide 0 to absorb unwanted ultraviolet radiation dam photocatalytic reactions occur

The Chemical Nature of Chalking) » UV absorption in the Presence of Titanium Dioxide Pigments, H. G. Volz, G. Kaempf, H. 6. Fitzky, A.

Klaeren, ACS Symp. Ser. 1981, 151, Photodegradation and Photostabilization of

Coatings). 0

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- DS i; What is UV light in the ultraviolet range? Titanium dioxide in this context; absorb It leads to the formation of highly effective electron-hole cracks resulting in pairs of electron holes. titanium dioxide surface highly reactive organic radicals on the surface of titanium dioxide on the cracks that are produced in this way the dissolution of the adhesive in an organic medium plays a major role in the catalytic process hydroxyl ions proves through practical studies that media©

Photocatalytic Degradation of Organic Water ) photocatalytic process CONTAMINANTS: Mechanism Involving Hyroxyl Radical Attack, C. 5. Turchi, D. F. Ollis,

Journal of Catalysis 122, 1990, 178-192).

TiO, by means of dyeing TiO particles; J photoactivity It is known that photocatalysis can be reduced by means of inorganic surface treatment or by means of an organic surface treatment (Se titanium (b | 0) and / or aluminum and / ar oxides of silicon (for example By coating with compounds

Industrial Inorganic Pigments, ed. by 6. Buxbaum, VCH, New York 1993, ( (zirconium).

Seite 58 — 60). The most amorphousigysily In particular, many patents have shown the placement of a 5:2 dense skin layer. The purpose of this layer is to prevent the formation of free cracks

ALO; Coating Lads (SiO; thick layer of #l53Y wet-chemical Wet chemical methods are indicated in two patents (TiO; in particular inorganic particles available in organic particulate matter 17405446 EP No. USRE 7778148 numeric, 1040877175, 4176417, and 0 indicate a method that can be performed at relatively low temperatures from 36 to 500°C; YYY¢

B _ _

As a result of the immediate addition of a solution of it and 510d112 and a solution of it and 820. Dense-skin treatments of 58:02 are also used to increase the abrasion resistance of the glass fibers covered in this way and to reduce the sliding properties of the fibers in the products that are manufactured. In this regard; US Application No. 7,517,419 indicates a method

© wet-chemical silicic acid cui Led is applied to the particle surface with polyvalent metal ions “Cu Jie ¢ polyvalent metal jons” Rev Radgle “Sr” Ca “Bes Mg and 70 Ni «Co «Mn «Cr «Pb «Sng Zr «Tig ¢Al 5 »Cds per German Patent No. Ya 0 £0TYYVY 0 ) = 1a; The method increases the light resistance of Dense Layer 110 pigments. It is based on Merge 58; or 21 or Zr in a layer of SiO;

. wet-chemical used by a wet-chemical process 0 There are also (TiO) methods, in addition to the well-known wet-chemical methods for surface coating of particles in this case; during the . gas phase at the gas phase SiO; Through which a dense layer of silicon is deposited, a chloride compound is added by means of a titanium dioxide production process of 0 °C, so that a layer of 0001 is formed to the particle stream at a temperature higher than 4 °C. particle surface on the surface of SiO particles; Or “Mg” or “P titanium dioxide” for pigment particles. This matter is solved by using pigment particles and its like gas phase deposited on the SiO gas phase; its surface is coated with a thick layer of

M Q — with one doping element on JY) with which the doping element is determined from the group including «Ce »Cds «Mo 3 »Cus «Mn Fs «Zn »Zr 3 Ys Ins «Sb s «Sn, 177 and Bi, as well as mixtures thereof. The matter is also solved by using pigment particles of titanium dioxide whose surface is dha © covered with a dense layer of SiO; produced in a wet-chemical process and doped with a single doping element at least ; Through which the similarity element is determined from the group that includes “Sb” “Ges” and “F” “Nb” and “W” Ce and 31, as well as mixtures thereof. The material is also dissolved using a method to fabricate Pigment particles of Dioxide Vo whose surface is coated with a dense layer of SiO, doped with at least one doping element; It includes the steps: 1 reaction of titanium tetrachloride in gas phase with aluminum halide and oxygen-containing gas in a reactor at temperature above 1000°C; In order to create a particle stream containing TiO particles; (VO contacting of the particle stream with at least two compounds; Cua the first compound is a silicon oxide-producing compound and the second compound is selected from the included group On “Sn” and “Ing energy” and “Cdg Mos” “Cus Mn” “Zn” and “©”; “Wg and Bi” and compounds produced for 7 as well as mixtures thereof. (z particle stream cooling Cooling of the particle stream; in order to create the YVY§ doping pigment particles, they are doped with a SiO-like element, which are coated with a dense layer of pigment particles, 70 and one “Zr s” Ys “Ins” Shy “Sn at least from the collection containing element

Ces, Cds, Mos, Cus < Mn 3, W, Bi, and mixtures thereof. opal There is another solution to this matter, which is a method for manufacturing pigment particles 8 of titanium dioxide, the surface of which is coated with a thick layer of 5:02 that is doped with an element similar to

doping element at least one; It includes the steps:

{Providing an aqueous solution for particles: 110 that increases its pH value

Ne about

b) Adding an aqueous solution of the alkali silicon component and at least one 0 aqueous solution of a doping element “

Where al is the likeness element of the included set = Sb, l, 6, l, tla, and

Mo, CeW, and Bi, as well as mixtures thereof.

6 Deposition of a dense layer of SiO; doped with at least one doping element

on the particle surface by reducing the pH value of the suspension to 01 a value less than 4” and preferably less than (A) where the doping elements are determined from the group

,. As well as mixtures including Bi, Ce Ww and “Mos Fg” Nb Ys “Ge” In ¢ Sb that contain

Other distinct embodiments of the invention are referred to in the subsidiary claims.

The material of the invention is coated with titanium dioxide pigments

improved in terms of its light resistance.

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General description of the invention titanium of the present invention; The pigments contained in the form of a dense layer with a particle surface as,

106 on “Hazazu” ranged from 1.1 to 716.0 wt. and preferably from 1.7 to 0 lb wt.; And done

Calculated as SIO; and alloy elements ranging from 00 to Tor by weight; preferably from ene to Fro 5 by weight; calculated as oxide or in Ala using © as element relative to total hemoglobin total

. pigment

in preferred form; Particles are coated with an additional layer ranging from 00 to 6.0 by weight; Preferably

from 001 to 4.0 by weight; Aluminum oxides or hydrous aluminum oxide

oxide + and is calculated as Bes ALO; to the total hemoglobin.

,. rutile titanium dioxide particles. It is preferable that the titanium dioxide particles be 0, the special element as an atom or 8, or a special compound, “doping element.” Here, the word “doping element” means the coatings that are produced; Where appropriate. In the context of describing oxide coating materials such as “oxide” compounds; Wet-chemical is also meant here using the corresponding wet chemical process. It should be stated that all data disclosed here are the corresponding hydrates or compounds

0 with respect to the pH value of 11°C, the temperature, and the concentration of 7 by weight or volume; etc. includes all values within the respective range of measurement accuracy known to those skilled in the art. The invention is based on the fact that to increase the photoresistance » the photocatalytic process 95 must be demonstrated in an appropriate manner; That is, the production of highly effective cracks must be made using pairs

A — } _ excited electron-holes are more difficult. This can be achieved using allll kits eg by increasing the speed of re-fusion of electron-hole pairs or by forming an active barrier on the surface of the pigment. A dense layer of Si0, applied in a system, does indeed form an active barrier on the “TiO,©” surface as can be revealed by the diluted energy state density in the valence band and in the transmission band of the TiO surface. , coated compared to the untreated TiO surface. Surprisingly, doping a 0:5 layer with specific elements leads to an even greater reduction in state energy; This raises the active barrier and thus improves the light resistance of the TIO, liad coated in this way. Additional states of energy within the band gap between the value band Sal 0 and the transport band promote the recombination of the electron-hole pairs. Doping the SiO layer with bound elements induces these energy states and thus also influences the photoresistance improvement compared to the non-doping SiO layer. It has been proven that the metals “Sn Ray” Ges “Ins Rat Rala Nb Dicky Ramtel “Mo 5” Cu “Mn” Wy “Ce” Cd and Bi are suitable doping components. A SiO layer containing YO elements can be placed similarly to the wet-chemical method and the gas phase method. though »; It is known that the gas phase method is generally able to lay a more uniform layer than the wet chemical method. An example of the present invention is described below using Figures 1 through AA

Brief explanation of the drawings Figure 1: It shows the energy states in the transition from the atom to the solid body 0 shown in: P.A.

Cox, "The Electronic Structure and Chemistry of Solids", Oxford Science Publications 1987, p. 13 © 7 Figure : Y showing the Als energy density of “May TIO2 energy state density 98:02 or without surface. the shape ? : shows the energy state density of the TIO surface with SiO coating and with SiO coating containing the Sn dopant element. Figure 2: Shows the energy state density of the TIO surface; with a coating: 510 and with a SiO coating, containing 01 Sb doping elements. on the Jn dopant. Figure 1: shows the Alls energy density of the surface of TiO, with a SiO coating; and with a SiO coating, containing the dopant element 06. Vo Figure vo: Between the density of the state The energy of a TiO surface with SiO coating and SiO coating containing Nb: shows the energy state density of the TIO surface with SiO coating and SiO coating containing the dopant element Nb in

11. E - Figure 9: Between the energy state density of a TiO surface, with a SiO coating; and a SiO coating containing the F-like element. Figure 01: Shows the energy state density of a TIO surface, with a coating SiO and SiO coatings containing Mn dopant © Figure 11: shows the energy state density of the TiO surface with SiO coatings and SiO coatings containing Cu dopant. Figure 11: Shows the energy state density of the TiO surface; with a SiO coating; and with a SiO coating; containing the Mo doyle element. Figure 11: Shows the Alls energy density of the TIO surface, with a SiO coating Figure 4: Shows the energy state density of the surface of TiO, with SiO coating, and with SiO coating containing Ce douber element. Figure Yo: shows the Als energy density of a TiO surface with a SiO coating and a 5:0 coating containing the None dopamine element. Vo Figure 11: Shows the Alla energy density of a TiO surface with a SiO coating and a SiO coating containing the Bi dopant element | Shika 1 VY shows the energy state density of a TiO surface with a SiO coating, and with a SiO coating containing the -Mg dopant.

Figure YA : shows the energy state density of a TiO surface, with a SiO coating; and with a SiO coating, containing the Al dopant element. The energy state density values were quantitatively calculated using the CASTEP software package (version 1 1 Jun (Yoo) of Cave Inc., San Diego These calculations were performed using Sid© clean for CASTEP density at a local density approximation of 681 m1. Detailed information was published by: V.

Milman et al. in: International Journal of Quant.

Chemistry 77 (2000), p. 895 to 910 The following equivalences were used; including semi-subterranean; 4s 53d «3p» 3s 'titanium and m4. The states of 2s LEH and m2 for oxygen were used; and the valence states of 53s m3 for silicon 0 with respect to the analogues; 54s of 4d m 4 sf m 2 semi-subterranean states for indium ¢ magnesium y yttrium are included. The base group used for the dopants is as follows: Sn: Ss, Sp, 6s, 6p, 5 Sb: 5s, 5p, 6s, 6p, 7s In: 4d, 5s, 5p, 6s, 6p, 7s Ge: © 4s, 4p, 4d Y: 4s, 4p, 4d, 5s, 5p Nb: 4s, 4p, 4d, 5s, Sp YYY¢

1 Y -— - — F: 2s,2p Mn: 3d, 4s, 4p Cu: 30 45 4p Mo: 4s, 4p, 4d, Ss, 5p h Cd: 4d, 5s, Sp, 6s, 6p Ce: 4f, Ss, 5p, 6s, 6p, 7s, 70 5 W: 5d, 6s, 6p Bi: 6s, 6p, 7s, 7p, 8s Mg : 2p, 3s, 3p Al: V+ 3s, 3p The kinetic energy of the YAY plane waves is one electronvolt. Structural engineering optimization was not achieved; As it was possible to evaluate the mathematical model and confirm it based on the known experimental results (coating with «Sn Uh; Zr and 20]. And therefore; The model calculations provide sufficient accuracy to calculate the photoresistance. Vo state density calculations were based on a lattice according to the Monkhorst-Pack scheme. Surface calculations were performed according to the “slice model method” with a blank thickness of 01 angstroms.

1” -: - Examples The invention was demonstrated based on ARNT from 1 to VE (doping the Si0 layer; with an element of the Gey “Ins” Sb “Sn” doping element “Bi” Comparison example 1 (pure layer of SiO); (Al) Calculation of reference example 1 is based on covering the surface of TiO, (1114) with the entire 5:0 monolayer. In this context, the unit cell contains an OY atom (Ti8Si8036) when coating is applied. Monomolecular: Calculated as 5:07 dels has a layer of approximately 0.7 nm on the pigment; it results in approximately 77% by weight of “SiO; relative to TiO; 0 The percentage by weight was calculated Based on the following values: Typical value of the specific surface (relative to BET) of the TIO particles, which are manufactured using the alu tz process: 6.7 chloride monolayer: 17 nm; layer density ; 1510 7,7 c.” Examples 1 to VE and comparative examples ¥ and 3” show a surface coverage of TIO, with a monomolecular S10; containing a duly doping element atomic ranging from 1 Cognate element 1: (X (TiO; In other words, the unit cell contains 1185:7701036. When placed on o(Si) 0:1102 pigment attributed to oxide, this leads to the following weight ratios of the alloy elements; calculated as

sn0; wt approx 1 : 70.00 Ex “Sby03 Ex 7: 76028 wt approx YVY¢

1 - z - Ex 07 70.09 approximately by weight from and 1070; Example 4: approximately 0.097 wt. wt Foye Ex. 8: Approximately 70.1 wt of MnO; | Example 9: Approximately 20.056 by weight of CuO Example 70.01: Approximately 01 by weight of MoOs Example 11: Approximately 70.08 by weight of CAO Ve Example VY VY , + approx wt. of CeO Example 1: approx. 70.16 wt. of 170; approx. 118 70.04 wt. 3:20 reference Example 1: 0.07 7 approx. wt. of MgO ref. 27 4 0.0 7 wt. of ALO; in

- 1 and

The results are the result of ©8517 quantum mechanical calculations. This is an electronic structure. This can be analyzed as band structures (energy bands (spatially resolved or Ala density values) (energy states). 2:60p. 1016).

© Detailed description Figure 1 shows a simplified schematic diagram (d) of the electronic structure The schematic diagram shows only the energy bandwidth and position. The state density (e) is used to distribute the energy state in the .energy band

the shape ? Shows the effect of the pure SIO coating; Not containing a doping element:

0 (for reference example 1) on THO, photosensitivity: calculated state density for the pure, (1011) TIO surface, is shown as a broken line; and for the surface coated with B,510, as a solid line. The positive effect of coating is based on SiO photostability is partly reduced state density in the (08) transmission band compared to the uncoated TiO surface resulting in less electron-hole pairs transfer to the adjacent matrix. Meanwhile, the effect is intensified

,. positive valence band due to the additional decrease in state density in the 0 5:0 valence band, in state density values; Compared to (1) coating the example Sn with SiO; Fig. © shows the doping effect of the pure layer. In this case, the valence band state density will be further reduced, resulting in improved photostability. form ;); in oY (Example 55 SiO; Figures 8–8 show the effect of layer analogy

1 - 0 - (example oF figure *); and 68 (example of Fig. 6); and 7 (Example co Fig. 7) and Nb (Example 6; Fig. L(A) It is surprising that the decrease in Alla density can be seen in the valence band in all lla i.e. these coatings Increases the coating resistance Doping the SiO2 layer with Zr or 20 leads to greater stability compared to the uncoated 5:02 © Figures 9-01 show the effect of SiO doping Aids b F (Example 7; Fig. 3), Mn (Example A Fig. 01 1), Cu (Example Mo ) 11 Jal a (Example 0 Fig. Cd o 11 VY Jal) Fig. oF and Ce (Example 10; Fig. 1); 17 (Example VY; Fig. 11) and Bi JU; 0; Fig. (VT Surprisingly, the analogy of the 58:0 layer with Mn fF, Cu, Mo, Cd, Ce, W, or 31 to additional energy states in the band gap that works 0 as the centers of coalescence of the electron-hole pairs, and thus to a greater resistance to light. In this case, the state density of the valence band all ¢ will increase, that is, doping the SiO2 layer with Mg will lead to photoresistance. Figure 18 shows the effect of doping the SiO2 layer with Al (comparative example?) on the energy state density values. In 0 in this case; The valence band state density will increase; That is, doping the 5:0 layer with Al will lead to no photoresistance. Process control Methods for coating titanium dioxide particles with a thick layer of 507 are demonstrated. Conventional processes operate through the aqueous phase. To this end; A particulate suspension is produced

- 11”

(TIO), and mixed with a dispersant material where appropriate and grinded while wet where appropriate. A thick layer of .510 is usually deposited by adding alkali metal- silicate solutions and an appropriate control in dad number pH [] M. The doping element is added in the form of a salt solution, combined with silicate solutions.

© or separated before or after adding a silicate solution. A person skilled in the art understands the appropriate compounds and quantities needed to control the pH value of 11M to produce a thick film. According to this invention; A thickening of 0,5:0 can be made by adding the following salts to the suspension; Provided that it is not understood from this combination that the invention is limited to it. Similarity to: Sb

antimony chloride, antimony chloride oxide, antimony fluoride, antimony sulphate Ye Z Cognate B Indium chloride, indium sulphate Cognate B Germanium chloride, germanates Cognate B: yttrium chloride, yttrium fluoride Cognate: Y Cognate B niobium chloride, niobates :Nb 0, similar to florine hydrogen, fluorides: F, similar to manganese chloride, manganese sulphate: Mn, similar to copper chloride, copper sulphate: Cu, similar to molybdenum chloride, molybdates :Mo YVY§

M1 - Similarity to cadmium chloride, cadmium sulphate:Cd Similarity to cerium nitrate, cerium sulphate:Ce Similarity to B 177: wolframates Similarity to bismuth nitrate, bismuth sulphate:Bi In a preferred model in the form of pala Traditionally, an outer layer of aqueous aluminum oxide is applied to the particles by the known methods. In another embodiment of the invention; A dense layer of 0:5 is deposited on the surface of the gas phase. There are many known methods for this. For example; Fluidized bed coating is possible at temperatures below approximately 1,000°C. These methods are described in US Patent 087445? or UK Patent No. 13701697 or US Patent No. 701 INTK and alternatively; The plating takes place in a tubular reactor directly following particle formation (TIO; chloride process) These methods are described, for example, in patents or patent applications TEEN 8/0 - 1a; and the European Patent VAVYOR No. 1b” and EP Yo No. 474:08 10-01b and PI 081411/11 - ?a. for coating in tubular Jolie; ale What is the producing compound of SiO; is halide 111608 in particular O8:0, which is generally inserted after the point at which reactants 11014 and AIC are combined with the gas containing 0. For example, the International Order IY - 11/081418 indicates that a silicon 56 at the point at which the TIO formation reaction is complete, by at least 797. In any Ala

The temperatures at the entry point must be greater than 1,000°C; Preferably 0101 degrees Celsius. The resulting compound is oxidized to 0:5 and deposited on the surface of the TIO particles in the form of a dense layer of silicon dioxide. In contrast to the wet chemical method 761-0101081 free oxide layers are formed from water and hydrates during treatment in the gas-phase treatment Lise ¢ gas-phase treatment to absorb hydroxyl ions and water molecules Jad molecules are on the roof. The particle stream is also added as a bie compound either in parallel with the compound producing Jf (Si02 |!! before or after it. The temperature of the particle stream at the point of entry must be greater than 0 °C; preferably 00 degrees hydrogen The following compounds are a suitable product compound 0 for metal oxides compounds, provided that this combination is not understood as a spall on this invention. antimony chloride (fis » antimony halide :Sb analogue to indium halide :In ¢ similar to indium chloride analogous to yttrium halide :Y ¢ analogous to yttrium chloride 0 analogous to zirconium chloride (fis ¢ zirconium Halide: Zr Similar to zinc halide: Zn ¢ Same as zinc chloride Similar to niobium halide: Nb ¢ Similar to niobium chloride Similar to fluorine, fluorine hydrogen, fluorides: F

- 1 manganese chloride:Mn Cognate with copper chloride:Cu Cocoon molybdenum chloride:Mo Cognate with cadmium chloride:Cd Cocoon with cerium chloride:Ce 2 Cocoon ©

The doppelganger tungsten chloride:W the doppelganger to bismuth chloride:Bi in a particularly favored embodiment; Traditionally, an outer layer of aluminum oxide is placed on the particles by the methods known by the introduction of a suitable product compound for aluminum oxide » such as

AIC 0 beyond the particle stream. cya can also be treated with Le titanium dioxide pigments if they have been coated in suspension or in the gas phase. For example"; Inorganic layers of one or more metal oxides can also be applied

0 . Furthermore it; Other surface treatment can be done with nitrate and/or organic surface treatment Compounds known to the skilled in the art for organic surface treatment of titanium dioxide pigment particles are also suitable for particle surface treatment according to of the present invention; For example; vehicles

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_ \ a — organosilanes ¢ and organosiloxanes ; organophosphonates; etc; or polyalcohols; Such as trimethylethane (TME), i.e. (TMP), asma: mabbatastan, etc. Lai, of the present invention “pigment particles of dalla titanium dioxide© for use in paints; And paint and paper. May also be used as a starter in suspensions for production; For example; Paper or coatings.

Claims (1)

Claims 1-1 A method for manufacturing pigment particles from titanium dioxide, TiO, the surface of which is coated with a thick layer of 0:5 that is doped with a doping element one on one. 0 at least; and it includes the steps: a) providing an aqueous suspension of TIO particles, core, where the aqueous suspension has a pH greater than 10°; 0) adding an aqueous solution of an alkali silicon component and an aqueous solution At least one of the VY components contains at least one doping element, whereby at least one doping element A is chosen from the set of Ge, Wala, Tla and Mos: 4 and for Bi, as well as LDA thereof. TIO; core 1 particles ?- method according to claim 0 where tla 2) involves adding an aqueous solution of an aluminum-containing component to the suspension to obtain another ¥ layer of oxide 1 for aluminum oxide or hydrous aluminum oxide; aluminum oxide on a dense, SiO shell. 1 *- method in accordance with claim 7; It also includes: Y e) Adding an aqueous solution of an organic component to obtain another layer of organic material on the ov layer of aluminum oxide or hydrous aluminum oxide .oxide ¢ YVY§ Y Y -_ _ 1 +- method according to the oF claim which also includes: (s Y addition of TiO pigment particles, produced in step —) to a process for manufacturing dasa Y paints; coatings or paper. paints; coatings; or paper. 1 +- Claim 1 method wherein the silicon content of the dense crust ranges from 1" to 726.0 by weight; it is calculated as 5:0 and is referred to as the total hemoglobin. 1 7 - Claim 1 method Protection 1 where the silicon content in the dense crust ranges from 7 to 75.0 by weight; it is calculated as SIO; it is referred to as the total hemoglobin. Y in dense crust is from 00 to 77.0 by weight; calculated as oxide or in Ula' using SF as elemental form. 1 4- The method according to protection (A) where the content of doping elements in the dense crust ranges from 0.05 to 727.0 by weight; it is calculated in the form of oxide or in Ula using F in Object image -01 1 The method according to the claim Cun) also includes: d) the addition of TIO hemoglobin particles, produced in step c) to a process to manufacture the material YVY¢ Y ¢ — — plastic; or paints; or coatings; or paper.