TW460410B - Rare earth borate of the formula LnBO3 and its precursor composition, preparation process and use in visualization process and system - Google Patents

Abstract

The invention relates to a borate of lanthanum, lutetium, yttrium or gadolinium comprising two doping agents, the precursor of this borate and the use of the borate in plasma or X-ray systems. The rare earth borate of the invention corresponds to the formula LnBO3, where Ln represents one or more rare earths chosen from lanthanum, lutetium, yttrium and gadolinium, and it also comprises at least one first element chosen from the trivalent elements which are capable of collecting electrons, such as europium, samarium, thulium and ytterbium, and at least one second element chosen from europium II and the trivalent elements which are capable of collecting holes, such as cerium, terbium, praseodymium, bismuth, lead, antimony, chromium and iron.

Description

The present invention is directed to the inclusion of two dopants, their precursors, and their use in plasma or X-ray plasma systems (barriers and lamps). A specific example is a lighter front TV screen, one that is used in a plasma system and is channelized. High energy luminescent materials are emitted during this procedure. Furthermore, it is effective in the use of X-ray systems. This material must be absorbing in the range of linear radiation and the borates of known rare earth metals with light s. It is still necessary to look for better luminous yield. So the present invention The purpose is to obtain "LnB03" of the present invention, which is characterized in that Ln represents a rare earth metal + 'and it also contains a second-type element, which is the third-valent element and the second-type element system.素 和 铕 II. The present invention also relates to such a rare earth metal carbonate or carbon 11H reaction environment is in the form of an aqueous solution, the use of lanthanum 'rhenium, yttrium or thorium borate, the use of the wire system D-some new developments in visualization and lighting Technology and smaller size flat screen to replace the plasma plasma panel to resolve the particle replacement. The electromagnetic radiation of the ion volume of the gas in the chamber during the discharge. The photon is directed towards the system. The photon can excite the luminescent material. A luminescent substance that is excellent in plasma or X-ray yield in the visible range-suitable for such materials. But obvious product. The rare earth metal salt of material with better luminous yield is equivalent to one or more selected from the group consisting of lanthanum, aluminum, aluminum, and at least one element of the first type and at least one element selected from the ability to collect electrons. A method for preparing a trivalent binary earth metal borate capable of collecting holes, which is characterized in that the acid hydrogen salt and the element react with He Jun, and the reaction product is calcined.

4 604 10 V. Description of the invention (2)-By reading the following description and many specific but non-limiting examples to be explained, other features, details and advantages of the present invention can be fully presented. Only the borate of the present invention is based on one or more rare earth metals Ln, which can be opened; and j forms a substrate containing boron products. Ln represents at least one rare earth metal selected from the group consisting of lanthanum, chrysozoene, and chalcogenide of at least two of these rare earth metals. In the example of the composition, the representative components of the various plutonium metals may be as desired. According to a specific embodiment of the present invention, yttrium and chaos are included in the composition. The borate of the present invention also contains first and second types of additional elements, which can be said to function as dopants. As mentioned above, the first type of element is selected from trivalent elements capable of collecting electrons. This is a kind of pin that can effectively collect electrons is larger than the effective receipt. The pins, shovel, and thorium may be specifically mentioned as the "type element. Some elements may exist by themselves or in a composition." : The content of Peng is at most between 2% and 25%. 'Preferably between ». This content is based on the mole number of rhenium and / or rhenium relative to all rare earth metals and additional elements or The molar number of the borate dopant is shown in the following table: No .: Predicate: Ratio [Dl] / [S (Ln + M1) 2)], Di refers to the sum of the first element and prime i (in the current Examples are samarium and / or samarium), and the total samarium of samarium or other elements of the second type is samarium II. It is used as a dopant in the surface and is between 0.1% and 5%. And the content recorded is preferably between 1% and 2 expressed in the way of> Μ ^. ~ ~. The content of 铥 and 镱 is the same as the 铕 and 钐 listed above.

5. Description of the invention (3) The borate species of the present invention, which is combined with the first type of element or the push-mixing agent, is the first type of element, which is selected from the group consisting of rhenium II and capable of collecting electricity. This is an element that can effectively collect holes. j In particular, this second group of elements may be selected from the group consisting of rhenium, osmium, osmium, antimony, chromium, and iron, and these elements may be present by themselves or in combination. According to a specific embodiment of the present invention, the first-type element and the second-type element may be rhenium. Special mention is made of yttrium and thorium borate including thallium and thorium. According to another specific specific example, it is possible that the acid salt contains an element-type chain and an element-type element. In the specific embodiment of the present invention, the first type of element may be zirconium and thorium, especially the borate which may be thorium in this example. The total content of the second type of element is preferably the ppm and Between 1,000 ppm, this content can also be expressed relative to the mole number of the element in the borate. Example [D2] / [Σ (L n + D〗 + D2)] ^ More specifically, this content can be between 500 ppm and 'preferably introduced ppm *, which is called ^ in the second example of this specific example In other words, the content of the acid salt is preferably between 0.1% and 15%: between 0.5% and 10%, and more particularly between 5 and 10%. Can be committed between 5 ppm * 5,000 ppm, compared to 50 and 5,000 ppm ° This borate may be in the form of particles whose size ratio can be used to collect electrons in a tri-compensator containing at least one hole, The method of ship and material can be tritium and combination, which also mentions that boron of steel can be acidified according to the third type II element. The number of ears is between 5 and rare earth metals. In other words, the ratio is between 10 ppm. The shed of the chain and the sieve is changed in particular, especially in a wide range. -〆 丨 0 V. Description of the invention (4). However, the volume intermediate diameter of the particles is generally at most 10 micrometers, more specifically at most 5 micrometers, and more particularly, it can be between 0.5 and 5 micrometers _ all the entire description of the value of the median diameter and one that will be mentioned later The index of dispersion, i.e., the dispersion index, is a value obtained using a laser diffraction technique using a Cou 11 er LS 2 3 0 particle sizer. According to a specific specific example of the present invention, 'the borate of the present invention has a specific morphology'. In other words, it can be a cube, a parallelepiped (disc), or a spherical particle. The shape of the particles depends on the rare earth metal forming the borate. It depends. In the example of the Ganghe mine, the 'lateral acid salt is preferably in the form of a parallelepiped or a disk, and in the example of the period, it is spherical.' For the rare earth period and the composition of this type, it is in the form of a cube. Furthermore, the dispersion index of borate does not exceed 0.8. More specifically, this index does not exceed 0.7 and more particularly does not exceed 0.6. It is possible to obtain a product with a dispersion index of 0.4 or 0.5 in the article of the present invention. The dispersion index can be understood in a proportional sense: (7 / m = (d90- d, 〇) / 2d50 where: -d9 () is the equivalent diameter when the passing material is equal to 90%; -d1Q is when the passing material is equal to 10 % -Equivalent diameter; r-d5 () is the median diameter of the particles. The shed salt of the present invention can be obtained by any known method. It may be mentioned to utilize a precursor of an element contained in a borate composition such as an oxide Or the method of mixing / melting carbonate to perform solid / solid reaction.

No. 8 Yin 5. Description of the invention (5) ^ a " — ^ The more specific method is described below. More specifically, this method is applied to the preparation of borate with the above morphology (parallel hexahedron or disc, spheroid, cube) and the $ index does not exceed 0-8. This method uses carbonates or hydroxycarbonates of one or more rare earth metals or one or more doping elements contained in the carbonate composition to inflame the precursors of these rare earth metals or dopants. It can start with a carbonate or hydroxycarbon mixture of a rare earth metal and various dopants or a mixed carbonate or hydroxycarbon dicarbonate of a rare earth metal and a dopant. The carbohydrate or hydroxycarbonate of the rare earth metal is of the prior art and is known and it can be obtained, for example, by the effect of one or more earth metals with the Shen Dian of ammonium carbonate or a broken nitrogen salt. These carbonates or hydroxycarbonates can be used directly or after appropriate washing and / or drying. The starting carbonate or hydroxycarbonate is reacted with boric acid. This reaction is carried out under the most treacherous effect, for example between 40%. At a temperature between 〇 and 9 〇c, it is advanced. According to another feature of this method, the reaction environment is in the form of an aqueous solution. This means that the amount of water present in the reaction environment is such that the weight ratio of water / butterfic acid + carbonate is at least 300% ', more particularly at least 600%, and more particularly, this ratio is at least 1,000%. The procedure may be performed with an excess of boric acid. This excess may, for example, be between 1 mole% and 250 mole% (in other words, [Β] / [Σ (Ln + h + Ddhl. 〇1 to 5). I is preferably formed by removing the reaction process. The reaction of C02 is carried out in 1. The removal can be, for example, flushing the reaction environment with a neutral gas such as nitrogen to reach 4604 10.5. Description of the invention (6) ~ ° This modification method can obtain a product with a fine particle size. A precipitate can be obtained at the end of the reaction. _ According to a modification method of the present invention, it is preferred that the precipitate can be formed in the reaction environment by keeping the reaction environment at the same temperature as the reaction occurrence temperature. Here During the formation process, 'the pH of the forming environment may also be fixed. This pH may be fixed at a predetermined value', which may be, for example, the pjj of the reaction mixture at the end of the reaction, that is, when boric acid is introduced into the east. The addition of a base is maintained, for example, by adding an ammonia solution. The formation process may last between 1 and 3 hours. The precipitate is then separated from the reaction environment by any known method, such as by filtration. Appropriate Cleaning out Precipitate and then dry it. One of the advantages of the described method is that it obtains a precipitate that is easy to filter and clean. After drying, it can also be diluted with an acid such as nitric acid to remove any traces of incomplete reaction that may be present The carbonate is then calcined. The calcination can obtain the borate. It is generally between 500 and 1,400 ° C ', more particularly between 500 and 1, 100 ° C. It is possible to perform the calcination completely under air. Of course, this calcination can also use a reducing environment (such as hydrogen) or a neutral environment (argon) or a mixture thereof. This calcination can also develop the luminescence of the product. Properties. If higher " luminous properties are required, this calcination can be performed at higher temperatures. A modification method of the calcination step may be mentioned. This modification method includes mixing the dried sink and the butterfly acid, Wherein the amount of the acid to be used may be, for example, 5% to 15%. Then it may be between, for example, 900. (: and 1,10CTC

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I. Fifth, invention description (7) The sintering effect is performed at a temperature of (7). This modification method provides a borate with good luminous properties at a relatively small increase in calcination temperature. -The present invention also relates to a borate precursor composition which will be described below. This composition is characterized in that it consists of boron, one or more rare earth metals selected from the group consisting of lanthanum, scandium, yttrium, and ytterbium, at least one element selected from the group consisting of trivalent elements capable of collecting electrons, and at least one element selected from europium II. And the second type of element capable of collecting the trivalent element of the hole is the matrix. After calcination, it is possible to obtain a rare earth metal borate of the formula LnB03, where Ln represents the rare earth metal or a plurality of rare earth metals. It also contains at least one element of the first type and at least one element of the second type. The first type of element may be selected from the group consisting of 铕 '锸, 锸, and 镱, and the second type of element may be selected from the group consisting of 钸, 铽, 鐯, bismuth,, 、, 铬, chromium, and iron. This composition can be prepared by mixing a boron compound, a rare-earth metal compound, and other compounds of the elements. These compounds are selected from the compounds which can obtain the desired borate after calcination. These rare earth metal compounds and other element compounds may be, for example, oxides or carbonates. The composition can also be prepared by a more specific method of the type of borate described above. This method is characterized in that at least one of the rare earth metal, at least one of the first type of element and at least one of the second type of element is reacted with a carbonate or via a carbonate, and the reaction environment is in the form of an aqueous solution and appropriately cleaned- and And / or drying the reaction product. All statements made on this method are also applied here until sinking; the housework, separation and proper washing and / or drying. The obtained Shen Dianwu is one of the rare earth metals represented by the formula 1 ^ 6 (011) 4 (; 03;

Page 11 I. V. Description of the invention (8) — " ————————— Based on carbohydrate and at least one iridium-main substance. The composition of the first type of hydroxycarbonate-based = base-based carbonate can have the same morphological characteristics as the above-mentioned salts (cube, stilbium; and particle size characteristics) And especially dispersed; the purpose is not more than :) 8? Spherical particles) is used to order 'for example' as described above, at least 500, furthermore, the present invention relates to the above The meaning of borate in any chemical system and lighting program is used as a luminescent substance to understand the conditions of the pulp system, in other words, using one of the following: two out = length at least equivalent to located at about 100 nanometers and about 2000 nanometers 2: The more specific radiation gas is also between 140 nanometers and 200 nanometers. The invention also relates to such a visualization and lighting system, which comprises-the borate of the invention as a luminescent substance. It is very reasonable that such visualization and lighting systems may be mentioned as poly-electric barriers and lights. The rotten salt of the present invention can also be used in any system using X-rays. Radiation can be considered as the meaning of these rays that are earlier by light with an energy between about 1Q and about QoV. The present invention also relates to X-ray visualization systems and may be mentioned especially medical imaging. The borate is used for plasma production or X-rays according to well-known techniques, such as silk screen, thunder, ice and ice precipitation. Niuzhutong Page 12 460410 ---------------- V. Description of Invention (9) Examples will now be provided. Examples 1 to 4 _ Prepare products with the final composition as follows, and the content of doping elements is expressed by the above formula: Example U Control): YQ.mGdfl.318EU. .Ca B03 Example 2: A product with the same composition as Example 1 but with 70 ppm rhenium. Example 3 (control): Yfl 79GdQ.15EUu6B〇3 Example 4: A product with the same composition as Example 3 but with 50 ppm rhenium. Preparation method: 1. 1 under the action of heat (80) for 1 hour Add 1.3 M / 1 ammonium bicarbonate solution to 1.5 liters of dilute soil nitrate mixture solution with a concentration of 0.7 M / 1 to make the molar ratio of C03 / Ln equal to 1.6, appropriate Stir to prepare a carbonate suspension of the rare earth metal (Ln) contained in all product compositions. 5。 Then under 30 minutes under the action of heat (80 it) continued stirring and 0.8 M / 1 boric acid solution was added to the same medium, so that the molar ratio of B / Ln equal to 1.5. The temperature was then maintained at 60 ° and a 6 N ammonia solution was added to bring the pH to a minimum of 4,6 to allow the obtained suspension to mature. After this phase has matured for 3 hours, a white precipitate can be obtained, which can be separated by filtration, and then washed with deionized water. The wet product was then dried overnight at 60 ° C, followed by calcination (in air) in a flame furnace in the presence of 丨, 00 ° C, and 1 SSHgBO3 for 2 hours to obtain a rare earth metal borate. The Cou 11 er technique was used to determine the particle size of the product of Example 2. The test was also mentioned

Page 13 V. Description of the invention (10) The amount is carried out in a dispersion formed by the calcined product in a 0.1% by weight aqueous solution of sodium hexametascalate. The dispersion is detected by an ultrasonic wave in advance. (The diameter of the probe tip is 12 cm, 450 watts) for 3 minutes. The product of Example 2 had a median diameter of 2.3 microns and a dispersion index of 0.48. Properties: Special) Boronate in powder form prepared by X-ray excitation (XR: 30 彳 dryness). The intensity of the radiation peak at 597 nm is measured according to the content of tritium (money or thorium). The results are shown in Table 1 below. Table 1 Example of the content of the second type of element (Ppm) Radiation intensity (arbitrary unit) at 597 nm 1 0 100 2 70 130 3 0 100 4 50 125 νυν The photometer measures the peak emission intensity of Example i in the form of plasma excited powder and the product at 150 nanometers. The results are shown in Table 2 below.

I

Example ------ Content of the second type of element (Ppm) Radiation intensity (arbitrary unit) at 150 nm 1 0 4,200 _ 2 70-5,100 Page U ·, 4 604 1 〇 V. Description of the invention ( 11) Examples 5 and 6 The products of the following two compositions were prepared in the manner shown in the previous examples:-Example 5 (control): GAjCeuJOa Example 6 · Gdo.ggCeo.oUsTlIlo.DogBOg in powder form prepared by X-ray excitation The intensity of the radiation peak at 597 nm was measured under the condition of borate (XR: 30 仟 V). The results are shown in Table 3 below. Table 3 Examples Intensity 5 0.186 6 0.196 It was found that compounds with 0.5% erbium and 0.5% erbium doped with a higher radio intensity than those with 2% erbium doped.

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Claims (1)

Month 6, ¥ Zhuzhenli Fanyuan 1. One or more elements containing at least one type of element are selected from thorium 2. Based on the system selected from Pinxue, Cuo, 3 · based on thorium and 4. based on the content of rare earth Jinpeng 5. based on the rare earth metal Mor % And 5 6. According to the rare earth metal ear% and 2. 5 7. According to the content of elemental ppm and the second class of 5 0 8. The rare earth metal borate according to the formula LnB03, characterized in that Ln represents a species selected from steel, And rare earth metals, and it also contains a first type of element and at least one second type of element, wherein the first is selected from the trivalent element capable of collecting electrons and the second element II and capable of collecting electricity The trivalent element of the hole. Borate No. 1 in the scope of the patent application, wherein the first group of elements, rhenium, osmium, and rhenium, and the second group of elements are selected from the group consisting of rhenium, osmium, osmium, antimony, chromium, and iron. Borate No. 2 in the scope of patent application, in which the first element and the second element are thallium. For the borate in the first or second scope of the patent application, with respect to the mol number of the element that belongs to the borate, the rhenium in the first type of element is rhenium or between 2 mol% and 25 mol%.钐 Mol number. The borate of item 2 of the scope of the patent application, wherein the content of scandium is 0.1 mol% relative to the mole number of all and the borate element. The borate of item 2 of the scope of the patent application, wherein the content of scandium is relative to the mole number of all and the borate element, the scandium content is between 1 mole%. Borate No. 1 in the scope of the patent application, wherein the second element is between 5 ppm and 1,000 ppm and especially between 10 ppm with respect to all rare earth metals and the Mohr number element of the element Morse number. Borate No. 1 or 2 of the patent application, where Ln represents yttrium II O: \ 60 \ 6O243.ptc Page 1 2001.03.09.017 460410 Β Reaction Product A_M Case No. 88115212 6. Scope of Patent Application The reaction of basic carbonate with boric acid is carried out in a water-soluble and calcined environment. He 3. ~ 9 16. The method according to item 15 of the scope of patent application, wherein the reaction environment is the use of water at least 300% by weight, especially at least 600% by weight of water / boric acid + carbonate or hydroxycarbonate Formed. 1 7. The method according to item 15 of the scope of patent application, wherein the reaction is completed by removing the (: 02) formed in the process. 18. — Manufacturing a precursor composition according to item 12 or 13 of the scope of patent application Method, wherein at least one of the rare earth metal, at least one of the first type of element, and at least one of the second type of element carbonate or hydroxycarbonate are reacted with boric acid, and the reaction environment is in the form of an aqueous solution and the reaction product is washed as appropriate and / or It is used as a luminescent substance in the visible light method using plasma excitation or X-ray according to the borate of item 1, 2, or 3 according to the scope of the patent application < Borate in items 2, 2 or 3 using plasma excitation or X-ray visible light system < O: \ 60 \ 60243.ptc Page 3 2001.03. 09.019 Announcement zv- (The above blocks are filled by this bureau) —year and month Case No. 8811 Silicon 19 __Invention Patent Specification 46 ″ 4i〇 Chinese Rare Earth Boric Acid Drum Preparation Method and the Invention Name English Name (Chinese) 1. Villaria Cicada Bert 2. Denis Xu Juni Inventor Applicant Name (English) Nationality Residence and Residence Name (Name) (Chinese 5 Name ((IS National Residence, Residence (Office) Representative Name (Chinese) Representative Name (English) 1. VALERIE ARCHAMBAULT 2. DENIS HUGUENIN 1. France 2. France Λ. No. 186, Wesel Road, Paris, France2., No. 12, Ascherie-Sor-Lisse, France, France. L. Rhodia Chimie, France. 1. Paul, Cobivo, France 25 Dumer Road Philip Dubruck 1. PHILIPPE DUBRUC O: \ 60 \ 60243.ptc Page 1 2001.03. 09. 001 460410 Case No. 88115212 Λ_η Revision IV. Abstract of Chinese Invention (Name of the invention: Rare earth collar acid of chemical formula LnB03 _ Visualization method and system use) The method and method of the present invention are related to precursors and pathways containing two salts of this salt. The rare earth metal of the present invention is one or more selected from steel and contains at least one element of the first type. And the second type of elemental elements such as bromide, bromide, ytterbium, gold dopant lanthanum, yttrium or thorium borate, the borate used in plasma or X-ray system is equivalent to the formula LnB03, where Ln represents the rare earth metal of ore, period and iL, and it also contains element and at least one element of the second type, in which the first trivalent element for collecting electrons such as thorium, thorium, thorium and selected from thorium II and capable of collecting holes The trivalent element, ship, record, chromium and iron. Abstract of English Invention (RARE EARTH BORATE OF THE FORMULA LnB03 AND ITS PRECURSOR COMPOSITION, PREPARATION PROCESS AND USE IN VISUALIZATION PROCESS AND SYSTEM) lanthanum, lutetium, yttrium or gadolinium includes two doping agents, the precursor of this borate and the use of the borate in plasma or X-ray systems. The rare earth borate of the invention corresponds to the formula LnB03, where Ln represents one or more rare earths chosen from lanthanum, lutetium, yttrium and gadolinium, and it also includes at least one first element chosen from the trivalent elements which are O: \ 60 \ 60243.ptc Page 2 2001.03. 09.002 June 6. ¥ Zhuzhenli Fanyuan 1. One or more elements containing at least one type of element are selected from thorium 2. Based on the system selected from Pinxue, Cuo, 3 · based on thorium and 4. based on the content of rare earth Jinpeng 5. based on the rare earth metal Mor % And 5 6. According to the rare earth metal ear% and 2. 5 7. According to the content of elemental ppm and the second class of 5 0 8. The rare earth metal borate according to the formula LnB03, characterized in that Ln represents a species selected from steel, And rare earth metals, and it also contains a first type of element and at least one second type of element, wherein the first is selected from the trivalent element capable of collecting electrons and the second element II and capable of collecting electricity The trivalent element of the hole. Borate No. 1 in the scope of the patent application, wherein the first group of elements, rhenium, osmium, and rhenium, and the second group of elements are selected from the group consisting of rhenium, osmium, osmium, antimony, chromium, and iron. Borate No. 2 in the scope of patent application, in which the first element and the second element are thallium. For the borate in the first or second scope of the patent application, with respect to the mol number of the element that belongs to the borate, the rhenium in the first type of element is rhenium or between 2 mol% and 25 mol%.钐 Mol number. The borate of item 2 of the scope of the patent application, wherein the content of scandium is 0.1 mol% relative to the mole number of all and the borate element. The borate of item 2 of the scope of the patent application, wherein the content of scandium is relative to the mole number of all and the borate element, the scandium content is between 1 mole%. Borate No. 1 in the scope of the patent application, wherein the second element is between 5 ppm and 1,000 ppm and especially between 10 ppm with respect to all rare earth metals and the Mohr number element of the element Morse number. Borate No. 1 or 2 of the patent application, where Ln represents yttrium II O: \ 60 \ 6O243.ptc Page 1 2001.03.09.017 460410 Β Reaction Product A_M Case No. 88115212 6. Scope of Patent Application The reaction of basic carbonate with boric acid is carried out in a water-soluble and calcined environment. He 3. ~ 9 16. The method according to item 15 of the scope of patent application, wherein the reaction environment is the use of water at least 300% by weight, especially at least 600% by weight of water / boric acid + carbonate or hydroxycarbonate Formed. 1 7. The method according to item 15 of the scope of patent application, wherein the reaction is completed by removing the (: 02) formed in the process. 18. — Manufacturing a precursor composition according to item 12 or 13 of the scope of patent application Method, wherein at least one of the rare earth metal, at least one of the first type of element, and at least one of the second type of element carbonate or hydroxycarbonate are reacted with boric acid, and the reaction environment is in the form of an aqueous solution and the reaction product is washed as appropriate and / or It is used as a luminescent substance in the visible light method using plasma excitation or X-ray according to the borate of item 1, 2, or 3 according to the scope of the patent application < Borate in items 2, 2 or 3 using plasma excitation or X-ray visible light system < O: \ 60 \ 60243.ptc Page 3 2001.03. 09.019