TWI583625B - Alumina, luminophores and mixed compounds, and associated preparation processes - Google Patents

Description

Alumina, luminophores and mixed compounds, and related preparation methods

The invention belongs to the following fields: aluminates and luminophores and their preparation and fluorescent coatings, in particular, for the manufacture of display screens, lighting equipment, projectors, especially for the manufacture of plasma screens or field emission screens, Backlight of LCD screen, LED, plasma excitation bulb and three primary color bulbs.

The fluorescent tube is made in its conventional form from a sealed glass tube filled with low pressure mercury vapor and a rare gas such as helium, argon or neon. In operation, the electrodes within the tube emit electrons that excite the gas mixture within the tube and cause illumination in the ultraviolet range (e.g., at about 300 nm).

This ultraviolet light is converted into visible light by means of a fluorescent coating deposited on the inside of the tube.

In the case of "single layer" coatings, the coating comprises, for example, luminophore particles known as BAM (yttrium-aluminum-magnesium), CAT (yttrium-aluminum-niobium) or YOx, and alumina particles acting as reflectors.

In general, 80% of this layer is composed of luminophore particles and 20% is alumina or gamma-type alumina particles.

The luminophore particles generally have a size d ₅₀ between 4 μm and 10 μm.

It is known today that the cost of a luminophore is a major part of the total cost of the coating.

In a paper that Serge Itjoko replied at the University of Paris 6 on October 17, 2008, a study was conducted to first model the properties of the phosphor layer, and secondly based on yield and cost. Identify ways to optimize. This paper is cited in the present patent application as a prior art.

In particular, this study of mixed layers or monolayers appears by "selecting a radius of the illuminating group that is much smaller than the existing illuminating group (ie, a radius between 0.4 μm and 1.2 μm) and much larger than the existing alumina particles. The alumina particle radius (i.e., a radius greater than 0.6 μm) can be optimized.

Since this study is a theoretical model study, it only gives theoretical results, and does not indicate how the luminophores and alumina particles can be obtained. In particular, page 173 of this paper states that "commercial luminophores have a radius in the range between 3 μm and 6 μm" and that luminophores having sizes smaller than this size have not yet been developed.

It is an object of the present invention to overcome the deficiencies of known coatings and to propose formulations and methods of preparation for achieving the theoretical objectives of the above studies.

In particular, one subject of the invention is an alpha alumina consisting essentially of particles having a dimension d ₅₀ between 0.3 μm and 2 μm and substantially spherical.

One of the objects of the present invention is also the use of alpha alumina consisting essentially of particles having a dimension d _{50 of} between 0.3 μm and 2 μm and substantially spherical, which serves as a matrix for the luminophore.

According to another aspect, the use of alpha alumina consisting essentially of particles having a dimension d _{50 of} between 0.3 μm and 2 μm and substantially spherical is used as a matrix for the luminophore in a fluorescent lamp coating. .

A subject of the present invention is also a process for preparing a substantially size d ₅₀ of α-type and a method of substantially spherical alumina particles constituted of, the method comprising the following operations between 0.3μm and 2μm: - alum obtained via the route The gamma alumina is mixed with the sintering agent and the alpha alumina seed crystal; - calcining the mixture in an oven at a temperature between 1150 ° C and 1400 ° C, especially 1350 ° C for between 1 hour and 6 hours, especially 2 hours - grinding the calcined mixture; - passing the milled mixture through a grid made of a non-contaminating material with a mesh size between 150 μm and 250 μm, in particular 200 μm.

The present invention may be alone or in combination, comprising one or more of the following features: According to one aspect of the present invention, the sintering agent is NH ₄ F.

According to another aspect of the present invention, the mixture weight ratio basis based γ-alumina obtained via the route of alum 85-95%, 2.5% to 13% α-alumina and 0.4% to 1.8% NH ₄ F configuration.

According to still another aspect of the present invention, the mixture is composed of about 93.5% by weight of gamma alumina obtained by the alum route, about 5.5% alpha alumina, and about 1% NH ₄ F.

According to another aspect of the invention, the calcined mixture is milled in a ball mill for at least 20 times the alumina abrasive beads of the calcined mixture for 16 hours.

According to a particular aspect, the alumina abrasive beads have a thickness of about 1 cm. Its diameter between 3cm and 5cm.

An object of the invention is also an aluminate luminophore in the form of aggregates having an average size of about 10 [mu]m, the aggregation systems being composed of particles having an average size between 0.25 [mu]m and 1.5 [mu]m.

According to another aspect of the invention, the luminophore is an aluminate in the form of a composition corresponding to the formula: a(M ¹ O).b(MgO).c(Al ₂ O ₃ ) (1)

Or a(M ² O _1.5 ).b(MgO).c(Al ₂ O ₃ ) (2)

Wherein M ¹ represents at least one alkaline earth metal, M ² represents oxime or lanthanum and cerium in combination, and a, b and c are integers or non-integers satisfying the following relationship: 0.25 a 4;0 b 2 and 0.5 c 9; wherein M ¹ and M ^{2 are} partially enthalpy and at least one other element belonging to the rare earth metal group, more specifically yttrium, lanthanum, cerium, lanthanum and cerium. Magnesium may be partially replaced by Zn, Mn or Co; and aluminum may be partially replaced by Ga, Sc, B, Ge and Si.

According to another aspect of the invention, the luminophore is selected from the group consisting of: (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ , (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ , Y ₃ Al ₅ O ₁₂ :Eu ^{2 +} , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₂ O ₃ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Mn ²⁺ , Zn ₂ SiO ₄ :Mn ²⁺ .

According to still another aspect of the present invention, the luminophore is of a BAM type, a CAT type, a YAG (yttrium-aluminum-garnet) type or a YOx type.

One of the subject matter of the present invention is also prepared via the alum route as defined above In bulk form, the aggregation system consists of particles having an average size between 0.25 μm and 1.5 μm, the method comprising the steps of: - mixing the ammonium cerium with at least one rare earth metal-based additive; - at 1100 ° C and 1200 ° C Calcining the mixture at a first temperature of 1150 ° C for a period of between 1 hour and 2 hours, in particular 1 hour 30 minutes; - passing the calcined mixture through a non-contaminating material with a mesh size of 150 μm and a grid of between 250 μm, in particular 200 μm; grinding the calcined mixture through the sieve; - passing the milled mixture through a non-contaminating material with a mesh size of between 150 μm and 250 μm, in particular 200 μm a grid; calcining the milled and sieved mixture between 1300 ° C and 1400 ° C, in particular at a temperature of 1350 ° C for between 3 hours and 5 hours, in particular 4 hours; - grinding the calcined a mixture; the milled mixture is passed through a grid made of a non-contaminating material and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to another aspect, magnesium sulfate heptahydrate is added to the mixture of ammonium cerium-based rare earth metal-based additives.

According to another aspect, the final step of reducing with a hydrogen-containing gas is added, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar are used at 1500 A stable phase of at least 1 hour at a temperature between °C and 1600 °C.

According to still another aspect, the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium. Rare earth metals of the group formed by 铒, 铒, 銩, 镱, 镏, 钇 and 钪.

According to another aspect of preparing BAM, anhydrous barium sulfate ground to d ₅₀ <1 μm is added to a mixture containing ammonium cerium, a rare earth metal-based additive, and magnesium sulfate heptahydrate.

A subject of the invention is also a process for the preparation of an aluminate luminophore as defined above via an alumina impregnation route in the form of aggregates having an average size of about 10 [mu]m, the aggregate system being averaged Having a size between 0.25 μm and 1.5 μm, the method comprises the following operations: - using at least one rare earth based gamma alumina heated with a first solution heated to between 80 ° C and 95 ° C, especially 90 ° C The metal additive is impregnated for the first time; - the impregnated gamma alumina is heated to a first temperature between 500 ° C and 700 ° C, in particular 600 ° C, for a period of between 2 hours and 4 hours, in particular 3 hours Subjected to the first denitration heat treatment; - passing the resulting material through a non-contaminating material and mesh size 500 μm grid; - grinding the impregnated, denitrated and sieved alumina; - passing the milled mixture through a grid made of non-contaminating material and having a mesh size of between 150 μm and 250 μm, in particular 200 μm - calcining the milled and sieved mixture between 1300 ° C and 1400 ° C, in particular at 1350 ° C for between 3 hours and 5 hours, in particular 4 hours; - grinding the resulting material; - passing the resulting material through A grid made of a non-contaminating material and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to another aspect, after the first impregnation and the first denitration treatment: - the impregnated and denitrated alumina is heated to a second solution between 80 ° C and 95 ° C, especially 90 ° C Impregnating the second time with at least one rare earth metal-based additive; - heating the impregnated gamma alumina to between 1 hour and 4 hours, preferably between 500 ° C and 700 ° C, especially 600 ° C. The second denitration heat treatment was carried out for 3 hours.

According to a further aspect, the final step of reduction with a hydrogen-containing gas is used, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar are used at 1500 A stable phase of at least 1 hour at a temperature between °C and 1600 °C.

According to another aspect, the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium. Rare earth metals of the group formed by lanthanum, cerium, lanthanum, cerium, lanthanum and cerium.

In the preparation of BAM, cerium nitrate is added to a mixture comprising ammonium cerium, a rare earth metal-based additive, and magnesium sulfate heptahydrate.

According to a further aspect, the alumina is preheated to a temperature between 80 ° C and 150 ° C, in particular at 120 ° C, for a period of between 10 minutes and 2 hours.

As a variant, an object of the invention is also a process for the preparation of an aluminate luminophore as defined above via an impregnation route, the aluminate luminophore being in the form of aggregates having an average size of about 10 [mu]m, such aggregation The system consists of particles having an average size between 0.25 μm and 1.5 μm, the process comprising the following operations: - alumina spinel heated with a first solution heated to between 80 ° C and 95 ° C, especially 90 ° C Impregnating with at least one rare earth metal-based additive; drying the impregnated alumina spinel between 100 ° C and 150 ° C, in particular at 120 ° C for between 3 hours and 5 hours, in particular 4 hours; Drying the resulting material through a non-contaminating material and mesh size a 500 μm grid; - subjecting the impregnated alumina spinel to a temperature of between 500 ° C and 700 ° C, in particular a first temperature of 600 ° C, for a period of between 2 hours and 4 hours, in particular 3 hours Denitration heat treatment; - grinding impregnated and denitrated alumina spinel; - passing the milled mixture through a grid made of non-contaminating material with a mesh size of between 150 μm and 250 μm, in particular 200 μm; Calcining the milled and sieved mixture between 1300 ° C and 1400 ° C, in particular at 1350 ° C, for a period of between 3 hours and 5 hours, in particular 4 hours; - grinding the resulting material; - passing the ground material obtained by grinding A grid made of a non-contaminating material and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to still another aspect, in the preparation of BAM, cerium nitrate is added to a mixture comprising an alumina spinel-rare earth metal-based additive.

According to a further aspect, the final step of reduction with a hydrogen-containing gas is used, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar are used at 1500 A stable phase of at least 1 hour at a temperature between °C and 1600 °C.

According to still another aspect, the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium. Rare earth metals of the group formed by 铒, 铒, 銩, 镱, 镏, 钇 and 钪.

According to yet another aspect, the alumina spinel is preheated to a temperature between 80 ° C and 150 ° C, especially 120 ° C, for a period of between 10 minutes and 2 hours.

An object of the invention is also the use of a luminophore as defined above for the manufacture of display screens, illumination devices, projectors, in particular for the manufacture of plasma or field emission screens, backlights for liquid crystal screens, illumination Diode, plasma excitation bulb and three primary color bulbs.

An object of the invention is also an alumina-luminescent group hybrid compound comprising between 50% and 95% substantially as defined above, consisting essentially of particles having a size d ₅₀ between 0.3 μm and 2 μm and being spherical. Alpha alumina, and between 5% and 50% luminophore.

According to one aspect of the mixed compound, the luminophore is a luminophore as defined above.

According to another aspect, the luminophore is an aluminate corresponding to the composition of the formula: a(M ¹ O).b(MgO).c(Al ₂ O ₃ ) (1)

Or a(M ² O _1.5 ).b(MgO).c(Al ₂ O ₃ ) (2)

Wherein M ¹ represents at least one alkaline earth metal, M ² represents oxime or lanthanum and cerium in combination, and a, b and c are integers or non-integers satisfying the following relationship: 0.25 a 4;0 b 2 and 0.5 c 9; wherein M ¹ and M ^{2 are} partially enthalpy and at least one other element belonging to the rare earth metal group, more specifically yttrium, lanthanum, cerium, lanthanum and cerium. Magnesium may be partially replaced by Zn, Mn or Co; and aluminum may be partially replaced by Ga, Sc, B, Ge and Si.

According to another aspect of the invention, the luminophore is selected from the group consisting of: (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ , (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ , Y ₃ Al ₅ O ₁₂ :Eu ^{2 +} , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₂ O ₃ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Mn ²⁺ , Zn ₂ SiO ₄ :Mn ²⁺ .

A subject of the invention is also a process for the preparation of a mixed compound as defined above, wherein: - between 50% and 95% consists essentially of particles having a size d ₅₀ between 0.3 μm and 2 μm and substantially spherical The constituent alpha alumina is mixed with a luminescent group between 5% and 50%; - the mixture is ground.

An object of the invention is also the use of a compound as defined above for the manufacture of display screens, illumination devices, projectors, in particular for the manufacture of plasma or field emission screens, backlights for liquid crystal screens, illuminations II Polar body, plasma excitation bulb and three primary color bulbs.

An object of the invention is also an aqueous suspension for the manufacture of a coating for a fluorescent lamp, in particular a fluorescent tube, comprising at least one mixed compound as defined above, polyethylene oxide, gamma alumina obtained from the alum route And demineralized water.

According to one aspect of the aqueous suspension, each weight ratio is: - 25% to 50% of at least one mixed compound as defined above; - 0.5% to 5% polyethylene oxide; - 0.3% to 1.5% by alum route The obtained gamma alumina; - and the rest is demineralized water.

According to another aspect of the aqueous suspension, it comprises three mixed compounds that form a combination of three primary colors.

According to another aspect of the aqueous suspension, the three mixed compounds are present in the following weight ratios: - 35% and 40%, preferably 38% of the mixed compound (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ - Alpha alumina consisting essentially of particles having a size d _{50 of} between 0.3 μm and 2 μm and having a spherical shape; - 10% and 15%, preferably 12% of a mixed compound (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ - α-alumina consisting essentially of particles having a size d _{50 of} between 0.3 μm and 2 μm and having a spherical shape; and the balance being a mixed compound Y ₂ O ₃ :Eu ³⁺ - consisting essentially of a size d ₅₀ of 0.3 μm And alpha alumina composed of spherical particles between 2 μm.

Other features and advantages of the present invention will be apparent from the following description, taken in conjunction with the accompanying drawings in the accompanying drawings, in which: FIG. 1 is substantially in the form of a size d ₅₀ between 0.3 μm and 2 μm and substantially spherical. Electron micrograph of alpha alumina composed of particles; - Figure 2 shows several diffraction spectra during the manufacture of BAM; - Figure 3 shows several diffraction spectra during the manufacture of CAT; and - Figure 4 shows during the manufacture of YAG Several diffraction spectra.

General notes:

For all grinding operations, the unit amount is treated with alumina abrasive beads in a ball mill such as a Sweco® brand DM1 batch ball mill. The amount of alumina beads is at least 10 times the unit amount. The amount of alumina abrasive beads generally used is 20 times the unit amount to be treated, so as to limit Grinding time and optimized sieving time.

For the sieving operation, a screen made of a non-contaminating material such as plastic, in particular polyamide, is selected to avoid any contamination of the sifter. For example, the term "200 μm screen or grid" means a screen in which a sieve aperture of 200 μm can be obtained.

For the calcination operation, a gas tunnel oven with a maximum temperature of 1200 ° C and a residence time which can vary between 1 hour and 3 hours and a gas batch oven with a maximum temperature of 1400 ° C and an adjustable residence time were used.

Spectral measurements were performed on an X-ray diffractometer: Rigaku®-D/Max 2200.

Photographs of alpha alumina were obtained by electron microscopy: Philips® XL Series XL30.

Particle size measurements were made using a Micromeritics® brand Sedigraph Particle Size 5100 Model 809 or a Horiba® Laser-Scatter Particle Size Analyzer Model LA920.

Alpha alumina

One subject of the invention is an alpha alumina having a size d ₅₀ between 0.3 μm and 2 μm and substantially spherical.

The diameter d ₅₀ is defined as the particle size as follows: 50% of the population volume is formed by particles having a diameter smaller than this value.

This alumina is shown in Figure 1 as an electron micrograph. It can be observed that these particles have a substantially spherical or elliptical shape, i.e., they have virtually no edges.

These alpha alumina particles are especially suitable as luminophores, in particular coatings, for example as matrices for the luminophores in the alumina-luminescence monolayer of fluorescent lamps.

In particular, it has been confirmed that in a fluorescent lamp, the alumina particles are used as The efficacy of the reflector of ultraviolet light generated by the excitation of the gas mixture by the electrode has been enhanced and allows this ultraviolet light to be more efficiently coupled to the luminophore particles.

For example, such novel aluminas having preferred properties in light reflection and coupling of luminophores are made according to the following preparation methods:

According to the first step, the gamma alumina, the sintering agent and the alpha alumina seed crystal obtained via the alum route are mixed together. The sintering agent is, for example, NH ₄ F.

With regard to this method, the term "gamma alumina obtained via the alum route" means that the crystal structure is mainly composed of gamma alumina, especially alumina composed of 80% or more or even 90% gamma alumina.

With respect to this method, the term "alpha alumina seed crystal" means a pure alpha alumina seed crystal or a seed crystal mainly composed of alpha alumina, especially composed of more than 80% or even 90% alpha alumina.

For example, the mixture is composed of 85% to 95% by weight of gamma alumina, 2.5% to 13% alpha alumina, and 0.4% to 1.8% NH ₄ F, more specifically, the mixture ratio by weight of γ-alumina obtained via a line basis of about 93.5% by the route of alum, about 5.5% α-alumina and about 1% NH ₄ F configuration.

Secondly, according to the second step, the mixture is calcined in an oven at a temperature between 1150 ° C and 1400 ° C, in particular 1350 ° C, for a period of between 1 hour and 6 hours, in particular 2 hours.

During the third step, the calcined mixture is milled, for example, in a ball mill at an amount of at least 10 times the alumina abrasive beads of the calcined mixture, for a period of between 8 hours and 30 hours, especially 16 hours.

More specifically, the calcined mixture can be milled in a ball mill for at least 20 times the alumina abrasive beads of the calcined mixture for 16 hours.

In a fourth step, the milled mixture is passed through a grid made of a non-contaminating material, such as a plastic, preferably polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

Example 1:

In order to obtain about 1 kg of alpha alumina consisting essentially of particles having a size d _{50 of} between 0.3 μm and 2 μm and substantially spherical, 1000 g of gamma alumina sold under the name Baikalex® B105, 60 g of Baikalox® BMA15 The alpha alumina sold under the name and 10g NH ₄ F are mixed together.

The alumina BMA15 in particular its crystal structure is 100% d ₅₀ is composed of α-alumina with a diameter of about 150nm.

In the second step, the mixture was then calcined at a temperature of 1350 ° C for 2 hours.

In a third step, the calcined mixture is milled with grinding beads in a ball mill. The alumina abrasive beads have a diameter of between about 1 cm, especially between 3 cm and 5 cm. The amount of abrasive beads was 20 times relative to the calcined mixture.

During the fourth and final steps, the resulting material was passed through a polyamine screen having a mesh size of 200 μm after grinding.

Figure 1 shows the obtained material obtained.

According to another test in which the calcination temperature was 1200 ° C during the second step and lasted for 4 hours, α alumina particles having a size d ₅₀ of 1 μm and substantially spherical were obtained with good uniformity. It has been found that lowering the calcination temperature and extending the residence time results in better dimensional uniformity of the spherical alumina particles.

2. Aluminate luminophore

An indicator of the invention is also an aluminate luminophore in the form of aggregates having an average size of about 10 [mu]m, which are composed of particles having an average size between 0.25 [mu]m and 1.5 [mu]m. The term "average size" generally means the diameter d ₅₀ as defined above.

These luminophores are aluminates in the form of a composition corresponding to the following formula: a(M ¹ O).b(MgO).c(Al ₂ O ₃ ) (1)

Or a(M ² O _1.5 ).b(MgO).c(Al ₂ O ₃ ) (2)

Wherein M ¹ represents at least one alkaline earth metal, M ² represents oxime or lanthanum and cerium in combination, and a, b and c are integers or non-integers satisfying the following relationship: 0.25 a 4;0 b 2 and 0.5 c 9; wherein M ¹ and M ^{2 are} partially enthalpy and at least one other element belonging to the rare earth metal group, more specifically yttrium, lanthanum, cerium, lanthanum and cerium.

Magnesium may be partially replaced by Zn, Mn or Co; and aluminum may be partially replaced by Ga, Sc, B, Ge and Si.

According to another aspect of the invention, the luminophore is selected from the group consisting of: (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ , (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ , Y ₃ Al ₅ O ₁₂ :Eu ^{2 +} , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₂ O ₃ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Mn ²⁺ , Zn ₂ SiO ₄ :Mn ²⁺ .

BAM, CAT and YOx are available in the blue, green and red areas respectively. See the light emission spectrum, which makes it possible to manufacture three primary color bulbs after mixing. As individual luminophores, it is possible, for example, to produce screen pixels or light-emitting diodes.

In order to prepare these novel specific luminophores, three alternative preparation methods are proposed.

2.1 Preparation of aluminate luminophores via alum pathway

Aluminate luminophores are prepared via the alum route as defined above (the aluminate luminophores are in the form of aggregates having an average size of about 10 μm, such aggregates having particles having an average size between 0.25 μm and 1.5 μm The method of constructing) performs the following operations.

In a first step, ammonium ruthenium is mixed with at least one rare earth metal-based additive.

The rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium , rare earth metals formed by groups of strontium, barium and strontium.

Depending on the luminophore, there may be a single rare earth metal nitrate [eg Eu(NO ₃ ) ₃ for the manufacture of BAM] or several rare earth metal nitrates [eg Tb(NO ₃ ) ₃ and Ce (NO for the manufacture of CAT) ₃ ) ₃ ].

According to a specific aspect of the preparation of BAM, anhydrous barium sulfate ground to d ₅₀ <1 μm was also added.

Especially in the manufacture of BAM and CAT, it may be reasonable to add a commercially available high chemical purity magnesium sulfate heptahydrate (MgsO ₄ .7H ₂ O) to this mixture. The sulfate is a salt that is compatible with the ammonium hydrazine in this process and is particularly compatible with the treatment of the oven outlet gas.

In a second step, the mixture is calcined at a first temperature between 1100 ° C and 1200 ° C, in particular at 1150 ° C, for a period of between 1 hour and 2 hours, in particular 1 hour 30 minutes.

In a third step, the calcined mixture is passed through a grid made of a non-contaminating material, such as a plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In a fourth step, the calcined mixture that has passed through the screen is milled between 8 hours and 30 hours, for example, in a ball mill with alumina abrasive beads in an amount of at least 10 times that of the calcined precursor.

Next, in a fifth step, the milled mixture is passed through a grid made of a non-contaminating material, such as a plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In a sixth step, the milled mixture is calcined at a second temperature between 1300 ° C and 1400 ° C, in particular 1350 ° C, for a period of between 3 hours and 5 hours, in particular 4 hours.

In a seventh step, the resulting material is ground, for example, in a ball mill at an amount of at least 10 times the alumina abrasive beads of the calcined precursor for between 8 hours and 30 hours.

In an eighth step, the resulting material is passed through a grid made of a non-contaminating material, such as a plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to the ninth step, depending on the type of luminophore, in particular for BAM and CAT, a final step of reduction with a hydrogen-containing gas is carried out, wherein a temperature rise of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, is used. Stage and at least one hour of stabilization at a temperature between 1500 ° C and 1600 ° C under a pressure of about 100 mbar.

Example 2: Method for preparing BAM via alum route

In order to obtain about 1 kg of BAM:EU(Ba _0.9 Eu _0.1 )MgAl ₁₀ O ₁₇ , the following were mixed together in the first step: - 5833 g of ammonium hydrazine; - 270 g of anhydrous barium sulfate ground to d ₅₀ < 1 μm ( BaSO ₄ ); - 308 g of magnesium sulfate heptahydrate (MgSO ₄ ‧7H ₂ O); and - 106.8 ml of cerium nitrate solution (Eu(NO ₃ ) ₃ ), 233 g of oxide per liter.

In the second step, the mixture was calcined at a first temperature of 1150 ° C for a period of 1 hour and 30 minutes.

In the third step, the calcined mixture was passed through a grid made of polyamidide plastic and having a mesh size of 200 μm.

In a fourth step, the calcined mixture having passed through the screen was ground in a ball mill for 8 hours with alumina abrasive beads in an amount of 20 times the calcined material.

In a fifth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the sixth step, the milled and sieved mixture was calcined at a second temperature of 1350 ° C for a period of 4 hours.

In the seventh step, the obtained material was ground in a ball mill in an amount of 20 times the amount of the calcined material obtained for 8 hours.

In an eighth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the ninth step, a final step of reduction with a hydrogen-containing gas (for example a mixture (95% N ₂ and 5% H ₂ )) is carried out, wherein a temperature rise phase of 14 ° C/min and a pressure of about 100 mbar are used. Stable phase at 1600 ° C for at least 1 hour.

Example 3: Method for preparing CAT via alum route

In order to obtain about 1 kg of CAT (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ , the following were mixed together in the first step: - 6400 g of ammonium ruthenium containing 11.25% of oxide; - 335.64 g of crystals containing 39.5% of oxide Ce(NO ₃ ) ₃ ;- 423.22g Tb(NO ₃ ) ₃ solution containing 22.68% oxide; - 315.55g crystals containing 16.4% oxide MgSO ₄ ‧7H ₂ O.

In the second step, the mixture was calcined at a first temperature of 1150 ° C for a period of 1 hour and 30 minutes (see the diffraction spectrum of Figure 3: CAT precursor 1150 ° C).

In the third step, the calcined mixture was passed through a grid made of polyamidide plastic and having a mesh size of 200 μm.

In the fourth step, the calcined mixture having passed through the screen was ground for 8 hours with alumina grinding beads in an amount of 20 times that of the calcined material.

In a fifth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the sixth step, the milled and sieved mixture was calcined at a second temperature of 1350 ° C for 4 hours (see diffraction spectrum of Figure 3: calcined CAT 1350 ° C).

In the seventh step, the obtained material was ground in a ball mill in an amount of 20 times the alumina-purified beads of the calcined material for 8 hours.

In an eighth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the ninth step, a final step of reduction with a hydrogen-containing gas (for example a mixture (95% N ₂ and 5% H ₂ )) is carried out, wherein a temperature rise phase of 14 ° C/min and a pressure of about 100 mbar are used. Stabilization phase at 1600 ° C for at least 1 hour (see diffraction spectrum of Figure 3: reduced CAT).

The diffraction spectrum of the reduced product did not show any crystalline material other than the CAT luminophore.

Example 4: Method for preparing YAG via alum route

In order to obtain about 1 kg of YAG:Ce, that is, Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , the following contents were mixed together in the first step: - 3833 g of ammonium hydrazine; - 570 g of cerium nitrate solution Y (NO ₃ ) ₃ , 359 g / l; - 4.4 g of cerium nitrate solution Ce (NO ₃ ) ₃ , 19.2%.

In the second step, the mixture was calcined at a first temperature of 1150 ° C for a period of 1 hour and 30 minutes (see the diffraction spectrum of Figure 4: YAG precursor 1150 ° C).

In the third step, the calcined mixture was passed through a polyamine plastic grid having a mesh size of 200 μm.

In a fourth step, the calcined mixture having passed through the screen was ground in a ball mill for 8 hours with alumina abrasive beads in an amount of 20 times the calcined material.

In a fifth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the sixth step, the milled and sieved mixture was calcined at a second temperature of 1350 ° C for 4 hours (see diffraction spectrum of Figure 3: calcined YAG 1350 ° C).

In the seventh step, the obtained material was ground in a ball mill in an amount of 20 times the alumina-purified beads of the calcined material for 8 hours.

In an eighth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

The diffraction spectrum does not show any crystalline material other than the YAG luminophore.

It should be noted that YAG doped with a mixture of Eu ³⁺ , Tb ⁴⁺ or Gd ³⁺ and the latter two dopants can be produced according to the same method. It should be noted that YAG doped with Ni ²⁺ , V ²⁺ , Co ²⁺ can be produced according to the same method, which requires a final reduction step according to the previously defined scheme.

More generally, YAG can be doped with transition element cations in an oxidized or reduced form between 0.1% and 5%. The alum pathway is particularly suitable for incorporating it into the cubic lattice of YAG.

2.2. Preparation of aluminate luminophore via gamma alumina impregnation pathway

As an alternative to the alum route, a process for the preparation of aluminate luminophores as defined above via an impregnation route is presented in the form of aggregates having an average size of about 10 [mu]m, the average size of such aggregate systems It is composed of particles between 0.25 μm and 1.5 μm.

In a first step of the process, the gamma alumina heated with a first solution of an alkaline earth metal salt of cerium and magnesium which has been heated to between 80 ° C and 95 ° C and especially 90 ° C is used with at least one rare earth metal-based additive. Dip the first time.

The rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium Separate rare earth metals or mixtures of groups formed by cerium, lanthanum, cerium and lanthanum.

In order to prepare BAM, in addition to the rare earth metal-based additive, the impregnation solution is also Contains magnesium sulfate and barium nitrate.

In order to prepare CAT, in addition to the rare earth metal-based additive, magnesium sulfate is also added to the mixture of the ammonium cerium-impregnation solution.

It has been found that this impregnation can be improved when the alumina is preheated to a temperature between 80 ° C and 150 ° C, especially 120 ° C, for a period of between 10 minutes and 2 hours.

In a second step, the impregnated gamma alumina is subjected to the first by heating to a first temperature between 500 ° C and 700 ° C, in particular 600 ° C, for a period of between 2 hours and 4 hours, in particular 3 hours. Secondary denitration heat treatment.

In the third step, the impregnated and denitrated alumina is passed through a grid made of a non-contaminating material such as a plastic, in particular polyamide, and having a mesh size of 500 μm. This step makes it possible to avoid any residual small pieces that are not desired to be entrained into the following grinding steps.

In a fourth step, the resulting material is ground, for example, in a ball mill at an amount of at least 10 times the alumina impregnated and denitrated alumina, for between 8 hours and 30 hours.

In a fifth step, the milled mixture is calcined at a temperature between 1300 ° C and 1400 ° C, in particular at 1350 ° C, for a period of between 3 hours and 5 hours, in particular 4 hours.

In the sixth step, the resulting material is ground, for example, in a ball mill at an amount of alumina abrasive beads at least 10 times the amount of the calcined precursor, for between 8 hours and 30 hours.

In a seventh step, the resulting material is passed through a grid made of a non-contaminating material, such as a plastic, in particular polyamine, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the eighth step, depending on the type of luminophore (for example, for BAM and CAT), a final reduction step with a hydrogen-containing gas, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar at 1500 ° C and 1600 ° C are used. A stable phase of at least 1 hour between temperatures.

Especially for BAM, it has been found to be more sensible to add a second impregnation step.

Therefore, after the first impregnation and the first denitration treatment, the following steps can be inserted, including: - the impregnated and denitrated alumina is heated to between 80 ° C and 95 ° C, especially 90 ° C Diluting the second solution with at least one rare earth metal-based additive; - subjecting the impregnated gamma alumina to a first temperature of between 500 ° C and 700 ° C, especially 600 ° C for 2 hours and 4 hours The second denitration heat treatment was carried out, especially for 3 hours.

Example 5: Method for preparing BAM via gamma alumina impregnation route

In order to obtain about 1 kg of BAM, in the first step of the process, 750 g of gamma alumina (sold as Baikalox® B105, having a 100% gamma crystal structure and an average size d _{50 of} about 6 μm) which has been heated to 120 ° C is used. 1825 ml of a solution which has been heated to 90 ° C and containing the following materials is impregnated for the first time: ‧ 205.3 g of cerium nitrate containing 59.3% of oxide; ‧ 254.16 g of magnesium nitrate hexahydrate containing 14% of oxide; and ‧ 39.42 g containing 39.4 % oxide of cerium nitrate.

Next, in the second step, the impregnated gamma alumina was subjected to a first denitration heat treatment by heating to a first temperature of 600 ° C for a period of 3 hours.

In the third step, the impregnated and denitrated alumina is heated with 1125 ml. A second solution was applied to a solution containing 90 ° C and the following: ‧136.9 g of cerium nitrate containing 59.3% of oxide; ‧169.44 g of magnesium nitrate hexahydrate containing 14% of oxide; and ‧26.28 g of 39.4% oxide Niobium nitrate.

In the fourth step, the impregnated gamma alumina is subjected to a second denitration heat treatment by heating at a first temperature of 600 ° C for 3 hours (see the diffraction spectrum of Figure 2, BAM precursor 600 ° C) ).

In the fifth step, the obtained material was ground in a ball mill in an amount of 20 times the amount of the calcined material to grind the obtained material for 16 hours.

In a sixth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In a seventh step, the milled mixture was calcined at a temperature of 1350 ° C for a period of 3 hours (see the diffraction spectrum of Figure 2, calcined BAM 1350 ° C).

In the eighth step, the obtained material was ground in a ball mill in an amount of 20 times the amount of the calcined material to grind the obtained material for 16 hours.

In a ninth step, the resulting material is passed through a grid made of plastic, in particular polyamine, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In a tenth step, the final reduction step is carried out with a hydrogen-containing gas, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar at 1500 ° C are used. Stabilization phase at a temperature of between 1600 ° C and at least 1 hour (see diffraction spectrum of Figure 2, reduced BAM).

Example 6: Method for preparing CAT via gamma alumina impregnation route

In order to obtain about 1 kg of CAT, in the first step of the process, 720 g of gamma alumina (sold as Baikalox® B105 and having a 100% gamma crystal structure and an average size d _{50 of} about 6 μm) is used with a solution containing the following: Impregnation: - 360 ml Ce(NO ₃ ) ₃ solution containing 368.3 g/l of oxide; - 258 ml of Tb(NO ₃ ) ₃ solution containing 372 g/l of oxide; - 576 ml of MgSO ₄ solution containing 89.8 g/l Oxide.

Next, in the second step, the impregnated gamma alumina is subjected to a first denitration heat treatment by heating at a first temperature of 600 ° C for a period of 3 hours.

In the third step, the obtained material was ground in a ball mill in an amount of 20 times the amount of the calcined material to grind the obtained material for 16 hours.

In a fourth step, the milled mixture is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In the fifth step, the milled mixture was calcined at a temperature of 1350 ° C for a period of 3 hours (see the diffraction spectrum of Figure 2, calcined BAM 1350 ° C).

In the sixth step, the obtained material was ground in a ball mill in an amount of 20 times the amount of the calcined material to grind the obtained material for 16 hours.

In a seventh step, the ground material obtained is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

In an eighth step, the final reduction step is carried out with a hydrogen-containing gas, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, in particular 14 ° C/min, and a pressure of about 100 mbar at 1500 ° C are used. Stabilization phase at a temperature of between 1600 ° C and at least 1 hour (see diffraction spectrum of Figure 2, reduced BAM).

2.3 Preparation of aluminate luminophores via alumina spinel impregnation route:

As a variant, a process for the preparation of an aluminate luminophore as defined above via an alumina spinel impregnation route, in the form of aggregates having an average size of about 10 μm, is also proposed. The system consists of particles having an average size between 0.25 μm and 1.5 μm. This method includes the following operations:

According to a first step, the alumina spinel heated with a first solution which has been heated to between 80 ° C and 95 ° C, in particular 90 ° C, is impregnated with at least one rare earth metal-based additive.

Such alumina spinels have been described in document US Pat. No. 6,251,150.

It has proven to be sensible to heat the alumina spinel for a period of between 10 minutes and 2 hours at a temperature between 80 ° C and 150 ° C, especially 120 ° C.

The rare earth metal-based additive is, for example, a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and M ³ is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, iridium, A separate rare earth metal or mixture of the group formed by ruthenium, osmium, iridium and osmium.

To prepare BAM, cerium nitrate is added to an impregnation solution of alumina spinel containing a rare earth metal-based additive.

According to a second step, the impregnated alumina spinel is dried between 100 ° C and 150 ° C, in particular at 120 ° C, for a period of between 3 hours and 5 hours, in particular 4 hours.

Then, according to the third step, the dried material is made through a non-contaminating material such as plastic, in particular polyamine, and the mesh size 500 μm grid.

According to a fourth step, the impregnated alumina spinel is subjected to a desorption by heating at a first temperature between 500 ° C and 700 ° C, in particular 600 ° C, for a period of between 2 hours and 4 hours, in particular 3 hours. Nitrogen heat treatment.

According to a fifth step, the impregnated and denitrated alumina spinel is milled, for example, in a ball mill at an amount of at least 10 times the alumina abrasive beads of the calcined precursor, for between 8 hours and 30 hours.

According to a sixth step, the ground material obtained is passed through a grid made of a non-contaminating material such as plastic, in particular polyamine, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to a seventh step, the milled and sieved mixture is calcined at a temperature between 1300 ° C and 1400 ° C, in particular at 1350 ° C, for a period of between 3 hours and 5 hours, in particular 4 hours.

According to the eighth step, the resulting material is ground, for example, in a ball mill in an amount of at least 10 times the alumina abrasive beads of the calcined precursor, for between 8 hours and 30 hours, especially 16 hours.

According to a ninth step, the ground material obtained is passed through a grid made of plastic, in particular polyamide, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to still another aspect, depending on the luminophore, the final tenth step of reduction with a hydrogen-containing gas is increased, wherein a temperature rise phase of between 10 ° C/min and 20 ° C/min, especially 14 ° C/min, and about A stable phase of at least 1 hour at a temperature between 1500 ° C and 1600 ° C under a pressure of 100 mbar.

Example 7: Method for preparing BAM via alumina spinel impregnation route

In order to obtain about 1 kg of BAM, according to the first step, 750 g of alumina spinel (5Al ₂ O ₃ .MgO) which has been preheated to a temperature of 120 ° C is impregnated with 1.66 liters of a solution which has been heated to 90 ° C and contains the following: : ‧320.75g cerium nitrate containing 59.3% oxide; and ‧98ml cerium nitrate solution containing 247.4 grams of oxide per liter.

Such alumina spinels have been described in document US Pat. No. 6,251,150, but may also be mixed by mixing 7000 g of ammonium cerium and 376.7 g of Mg(SO ₄ )‧7H ₂ O, and between 1100 ° C and 1200 ° C. This mixture is obtained, in particular, at a temperature of 1150 ° C for a period of between 1 hour and 2 hours, in particular 1 hour 30 minutes.

According to the second step, the impregnated alumina spinel is dried at a temperature of 120 ° C for a period of 4 hours.

Then, according to the third step, the dried substance is passed through a plastic, in particular polyamine, and the mesh size 500 μm grid.

According to the fourth step, the impregnated alumina spinel is subjected to a denitration heat treatment by heating at a first temperature of 600 ° C for a period of 3 hours.

According to the fifth step, the impregnated and denitrated alumina spinel was ground in a ball mill for 20 hours with an alumina abrasive bead of 20 times the amount of the obtained material.

According to a sixth step, the ground material obtained is passed through a grid made of plastic, in particular polyamine, and having a mesh size of 200 μm.

According to the seventh step, the milled and sieved mixture was calcined at a temperature of 1350 ° C for a period of 4 hours.

According to the eighth step, the obtained material was ground in a ball mill in an amount of 20 times the alumina abrasive beads of the obtained material for 16 hours.

According to the ninth step, the ground material obtained is passed through a grid made of plastic, in particular polyamine, and having a mesh size of 200 μm.

According to the final tenth step, the resulting material is reduced with a gas consisting of 95% N ₂ and 5% H ₂ , wherein a temperature rise phase of 14 ° C/min and a temperature of 1600 ° C at a pressure of about 100 mbar are used. The stable phase of the hour.

Luminous clusters as defined above can be used to manufacture display screens, lighting equipment (fluorescent lamps), projectors, especially for the manufacture of plasma screens or field emission screens, backlights for liquid crystal screens, light-emitting diodes, plasma excitation Light bulb and three primary color bulbs.

3. Alumina-luminescent group mixed compound

In particular for the production of a single-layer fluorescent lamp, an alumina-luminous hybrid compound comprising between 50% and 95% of alpha alumina having a size d ₅₀ as defined above and having a spherical shape between 0.3 μm and 2 μm is proposed. , and between 5% and 50% of the luminophore.

The luminophore is an aluminate corresponding to the composition of the following formula: a(M ¹ O).b(MgO).c(Al ₂ O ₃ ) (1)

Or a(M ² O _1.5 ).b(MgO).c(Al ₂ O ₃ ) (2)

Wherein M ¹ represents at least one alkaline earth metal, M ² represents oxime or lanthanum and cerium in combination, and a, b and c are integers or non-integers satisfying the following relationship: 0.25 a 4;0 b 2 and 0.5 c 9; wherein M ¹ and M ^{2 are} partially enthalpy and at least one other element belonging to the rare earth metal group, more specifically yttrium, lanthanum, cerium, lanthanum and cerium. Magnesium may be partially replaced by Zn, Mn or Co; and aluminum may be partially replaced by Ga, Sc, B, Ge and Si.

According to another aspect of the present invention, the luminophore is selected from the group consisting of: (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ , (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ , Y ₃ Al ₅ O ₁₂ :Eu ^{2 +} , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₂ O ₃ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Mn ²⁺ , Zn ₂ SiO ₄ :Mn ²⁺ .

It is possible to use a commercially available luminophore as a luminophore, and this mixed compound has a lower cost due to its composition at an equivalent performance quality. This is possible because the reflective properties of the alpha alumina particles are preferred.

The use of luminophores as defined above in items 2, 2.1, 2.2 and 2.3 is preferred.

This mixed compound can be prepared by the following preparation method, wherein: - between 50% and 95% of α-alumina consisting essentially of particles having a size d _{50 of} between 0.3 μm and 2 μm and substantially spherical and 5% and 50% of the luminophores are mixed together; - for example, grinding the mixture in an amount of at least 10 times the alumina grinding beads in a ball mill for between 8 hours and 30 hours; - the resulting material is ground By means of a grid made of a non-contaminating material such as plastic, in particular polyamine, and having a mesh size of between 150 μm and 250 μm, in particular 200 μm.

According to a variant, jet milling is conceivable, for example by means of an "Alpine" plate jet mill.

An object of the invention is also the use of a mixed compound as defined above for the manufacture of display screens, lighting devices, projectors, in particular for the manufacture of plasma or field emission screens, backlights for liquid crystal screens, illumination Diode, plasma excitation bulb and three primary color bulbs.

An object of the invention is also an aqueous suspension for the manufacture of a coating for a fluorescent lamp, in particular a fluorescent tube, comprising at least one mixed compound as defined above, polyoxidized Ethylene, gamma alumina obtained from the alum route and demineralized water.

In the aqueous solution, each weight ratio is: - 25% to 50% of at least one mixed compound as defined above; - 0.5% to 5% polyethylene oxide; - 0.3% to 1.5% gamma alumina obtained by the alum route ;- and the rest is demineralized water.

This aqueous solution may comprise three different mixed compounds that form a combination of three primary colors.

For example, three mixed compounds may be present in the following weight ratios: - 35% and 40%, preferably 38% of the mixed compound (Ce _0.6 Tb _0.4 ) MgAl ₁₁ O ₁₉ - substantially by size d ₅₀ of 0.3 μm and Α-alumina composed of spherical particles of between 2 μm; -10% and 15%, preferably 12% of mixed compound (Ba _0.9 Eu _0.1 ) MgAl ₁₀ O ₁₇ - substantially consisting of a size d ₅₀ of 0.3 Α-alumina composed of spherical particles between μm and 2 μm; and the remaining mixed compound Y ₂ O ₃ :Eu ³⁺ - consists essentially of spherical particles having a size d _{50 of} between 0.3 μm and 2 μm Alpha alumina.

Claims (15)

A method for preparing an aluminate luminophore by an alum route, wherein the aluminate luminophore is in the form of an aggregate having an average size of about 10 μm, and the aggregation system is composed of particles having an average size of between 0.25 μm and 1.5 μm. The method comprises the steps of: mixing ammonium cerium with at least one rare earth metal-based additive; calcining the mixture at a first temperature between 1100 ° C and 1200 ° C for a period of between 1 hour and 2 hours; making the calcined mixture By passing a grid of non-contaminating material and having a mesh size between 150 μm and 250 μm; grinding the calcined mixture through the sieve; passing the milled mixture through a non-contaminating material and mesh size a grid between 150 μm and 250 μm; calcining the milled and sieved mixture at a second temperature between 1300 ° C and 1400 ° C for a period of between 3 hours and 5 hours; grinding the resulting material; The mixture passed through a grid made of a non-contaminating material with a mesh size between 150 μm and 250 μm. A method of producing an aluminate luminophore via the alum route according to the first aspect of the patent application, wherein magnesium sulfate heptahydrate is added to the ammonium cerium-based rare earth metal-based additive mixture. A method for preparing an aluminate luminophore via the alum route according to the first aspect of the patent application, wherein the final step of reducing with a hydrogen-containing gas is added, wherein a temperature rise phase between 10 ° C/min and 20 ° C/min is used and At least 100 mbar at a temperature between 1500 ° C and 1600 ° C 1 hour stable phase. The method for preparing an aluminate luminophore by the alum route according to the first aspect of the patent application, wherein the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and the M ³ is selected from the group consisting of ruthenium, osmium and iridium. Separate rare earth metals or mixtures of the group formed by 钕, 鉕, 鉕, 钐, 铕, 釓, 鋱, 镝, 鈥, 铒, 銩, 镱, 镏, 钇 and 钪. A method for preparing an aluminate luminophore via the alum route of claim 2, which is used alone or in combination with any one of items 3 and 4 of the patent application for the preparation of BAM (钡-aluminum- Magnesium) to which anhydrous barium sulfate ground to d ₅₀ < 1 μm is added to the mixture containing the ammonium cerium, the rare earth metal-based additive, and the magnesium sulfate heptahydrate. A method for preparing an aluminate luminophore via the alum route according to the fourth aspect of the patent application, for preparing YAG (yttrium-aluminum-garnet), wherein the ammonium cerium and cerium nitrate and the second additive based on rare earth metal mixing. A method for preparing an aluminate luminophore via the alum route according to claim 6 of the patent application, for preparing YAG (yttrium-aluminum-garnet), wherein the second additive based on the rare earth metal is cerium nitrate. A method for preparing an aluminate luminophore via the alum route according to item 2 of the patent application, which is used alone or in combination with any one of items 3 and 4 of the patent application for the preparation of CAT (铯-aluminum-鋱), wherein the ammonium cerium is mixed with cerium nitrate and cerium nitrate. A method for producing an aluminate luminophore via the alum route according to the second aspect of the patent application, wherein the final step of reducing with a hydrogen-containing gas is added, wherein a temperature rise phase between 10 ° C/min and 20 ° C/min is used and A stable phase of at least one hour at a temperature between 1500 ° C and 1600 ° C under a pressure of about 100 mbar. The method for preparing an aluminate luminophore by the alum route according to the second aspect of the patent application, wherein the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and the M ³ is selected from the group consisting of ruthenium, osmium and iridium. Separate rare earth metals or mixtures of the group formed by 钕, 鉕, 鉕, 钐, 铕, 釓, 鋱, 镝, 鈥, 铒, 銩, 镱, 镏, 钇 and 钪. The method for preparing an aluminate luminophore by the alum route according to the third aspect of the patent application, wherein the rare earth metal-based additive is a rare earth metal nitrate M ³ (NO ₃ ) ₃ , and the M ³ is selected from the group consisting of ruthenium, osmium and iridium. Separate rare earth metals or mixtures of the group formed by 钕, 鉕, 鉕, 钐, 铕, 釓, 鋱, 镝, 鈥, 铒, 銩, 镱, 镏, 钇 and 钪. A method for preparing an aluminate luminophore via the alum route of claim 2, which is used alone or in combination with any one of claims 9 to 11 for the preparation of BAM (钡-aluminum- Magnesium) to which anhydrous barium sulfate ground to d ₅₀ < 1 μm is added to the mixture containing the ammonium cerium, the rare earth metal-based additive, and the magnesium sulfate heptahydrate. A method for preparing an aluminate luminophore via the alum route according to claim 10 or 11 of the patent application, for preparing YAG (yttrium-aluminum-garnet), wherein the ammonium cerium and cerium nitrate and the rare earth based metal The second additive is mixed. A method for preparing an aluminate luminophore via the alum route according to claim 13 of the patent application, for preparing YAG (yttrium-aluminum-garnet), wherein the second additive based on the rare earth metal is cerium nitrate. A method for preparing an aluminate luminophore via the alum route of claim 2, which is used alone or in combination with any one of claims 9 to 11 for the preparation of CAT (铯-aluminum-鋱), wherein the ammonium cerium is mixed with cerium nitrate and cerium nitrate.