ES2369616T3 - LUMINISCENT MATERIAL OF PROLONGED LIGHTING PERSISTENCE, AND ITS PREPARATION METHOD. - Google Patents

Abstract

A material of prolonged light persistence, characterized in that it is a luminescent material composed of aluminate, comprising sulfur and / or selenium, or comprising sulfur and / or selenium and phosphorus as well as activating ions, and its main chemical composition is expressed by the following formula: where: a MO · b M '(SßSe1-ß) · c Al2O3 · d B2O3 · e P2O5: x Eu · and Ln M is selected between Sr, Ca, Ba and Mg, and any combination thereof; M 'is selected (n) from Sr, Ca, and Ba, and any combination thereof; Ln (n) is selected from Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi and Sm and any combination thereof; a, b, c, d, e, x and y, are molar ratios and satisfy the conditions: 0.5 <a <6.0, 0.0001 <= b <= 2.0, 0.5 <= c <= 9.0, 0 <= d <= 1.0 0 <= e <= 1.0, 0.00001 <= x <= 0.25, 0.00001 <= y <= 0.3, 0 <= ß <= 1.0, 0.5 <(a + b) <= 6.0, 0 <(d + e) <= 1.0.

Description

Luminescent material of prolonged light persistence, and its method of preparation

FIELD OF THE INVENTION

The present invention relates to a luminescent material of prolonged light persistence, particularly to a luminous compound compound based on aluminate, which comprises sulfur and / or selenium, or a luminescent composite material based on aluminate, which comprises sulfur and / or selenium and elemental phosphorus, as well as one or more activating ions, and the method of manufacturing it.

BACKGROUND OF THE INVENTION

Since its invention in the nineteenth century, the traditional luminescent material of prolonged light persistence, of the ZnS series has undergone continuous improvements, which have developed several typical products such as ZnS: Cu (which emits a green light ), the (CaSr) S: Bi (which emits a blue light), and the (ZnCd) S: Cu (which emits an orange yellow light), and have been applied in some commercial fields, but nevertheless, these materials they have some defects, such as very poor stability, a tendency to decompose in the air, a tendency to turn gray and even dark in the sun's rays, a short period of luminescence persistence, usually since about 0.5 to about 2 hours and a low luminescent brightness, etc., and cannot meet the requirement of practical use. In order to improve the brightness and light persistence time of these materials, radioactive elements such as Co, Ra, H3 have been added to these materials to produce luminescent materials of prolonged light persistence with radioactivity. These materials give light continuously and have always been used in the fields of aeronautical instruments, watches, etc., however their applications have been largely limited due to radioactive contamination and high cost.

The luminescent materials of prolonged light persistence of the aluminate system were invented in the early 1990s, as described in Chinese patents ZL 92110744, ZL 98109570.4, ZL 95118116.5, US patents No. 5. 376.303, and No. 5. 424 006, its luminescent brightness, its property of prolonged light persistence and stability, were markedly superior to the products of the sulfide series, described above, and the materials have been used in daily consumer items, safety signs, watches, etc. However, the luminescent materials of prolonged light persistence of the aluminate system described above still suffer from some disadvantages in practical applications, such as:

one.

Short time of light persistence: the luminescent materials of prolonged persistent luminescence of the aluminate system have a nominal time of light persistence above 24 hours, which however is determined based on the intensity of the final luminescence equivalent to the brightness of 0.3 mcd / m2. In fact, the ability to identify with the naked eye is very weak under such luminosity, and the application of materials with a prolonged light persistence is greatly limited.

2.

Poor applicability: a luminescent material with a high brightness does not necessarily mean that products made of the luminescent material have a high brightness. The brightness of a luminescent product depends to a large extent on the correspondence of the luminescent material with the medium for the manufacture of the luminescent product. Many luminescent products cannot meet the requirements required in certain applications, and in practical applications, so most luminescent materials are used after being converted into products.

3.

A fast charge is impossible: the light absorption rate of the luminescent material of prolonged persistence, prepared according to the old technique, is slow, and very difficult to reach saturation, which results in the luminescent intensity and the Light persistence time of luminescent materials and luminescent products cannot meet the requirements of practical use well.

Four.

Lack of variety in the color of the luminescence: the color of the luminescence suffers from lack of variety, and if it is desired to obtain multiple colors (wavelength of the emission spectrum peak: 440-620 nm), it is necessary to use a number of luminescent materials of different systems. It is still unattainable for luminescent materials of the same system, to obtain a multi colored luminescence.

SUMMARY OF THE INVENTION

In view of the previous defects of the ancient technique, the present inventors have made a large number of studies on the luminescent materials of prolonged light persistence, these studies were mainly oriented to improve the time of light persistence, luminescent intensity, rapid absorption performance of light with a dim light and a multiple luminescent color of the luminescent materials of prolonged light persistence and the products thereof. After long periods of testing and a large number of fundamental experiments, the inventors discovered that a new composite aluminate structure could be produced by partially replacing the oxygen element in the aluminate activated by divalent europium with S and / or Se and also by doping optionally with element P, to obtain large

5 improvements in the luminescent brightness and the light persistence time as well as in the application in products of luminescent materials in terms of luminescent brightness and light persistence time of the products. These current luminescent materials of prolonged light persistence are superior to the materials of the ancient technique, particularly with respect to the light absorption range and the light persistence time under conditions of a dim light. In addition, the invention has developed new luminescent materials of prolonged light persistence with luminescence colors that cannot be achieved with the luminescent materials of prolonged light persistence of the ancient technique, such as the simple aluminate system or the sulphide system.

The present invention provides a luminescent material of prolonged light persistence of a new

15 system other than the luminescent materials of prolonged light persistence of the aluminate system and the silicate system. The present luminous compound aluminate material comprises sulfur and / or selenium, or comprises sulfur and / or selenium and elemental phosphorus as well as activating ions.

The present invention provides a luminescent material of prolonged light persistence and the manufacturing process thereof, which material has a wide variety of luminescent colors, a wide spectral range, good stability, a high intensity of light persistence and an extra time of a prolonged light persistence, capacity for a fast load working with a dim light, and an outstanding luminescent performance of the products that contain the present material.

The main chemical composition of the luminescent material of long light persistence of the present invention can be expressed by the formula (1):

a MO · b M '(SβSe1-β) · c Al2O3 · d B2O3 · e P2O5: x Eu · and Ln (1)

where:

M is selected (n) from Sr, Ca, Ba and Mg and any combinations thereof; M 'is selected between Sr, Ca and Ba and any combinations thereof; Ln (n) is selected from Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi and Sm and any combinations of the themselves; a, b, c, d, e, x and y, are molar ratios and satisfy the conditions: 0.5 <a <6.0, 0.0001≤ b ≤ 2.0, 0.5 ≤ c ≤

35 9.0, 0 ≤ d ≤ 1.0, 0 ≤ e ≤ 1.0, 0.00001 ≤ x ≤ 0.25, 0.00001 ≤y ≤ 0.3, 0 ≤ β ≤ 1.0, 0 , 5 <(a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0.

In accordance with a preferred version of the present invention, a luminescent material of long light persistence is provided, wherein M in formula (1) is selected from Sr, Ca and Mg, and any combinations thereof; M 'is selected (n) between Sr and Ca and any combinations thereof; Ln (n) is selected from Nd, Dy, Tm, La, Pr, Sm and Ce and any combinations thereof, where after being excited by a light of short wavelength, with a wavelength of 500 nm or less, the material exhibits an emission spectrum between 420 and 650 nm with a peak at 440-620 nm and has a luminescence color of purple blue, green blue, green yellow, white, red, etc., and said material can have the

45 characteristic of a fast charge.

In accordance with another preferred version of the present invention, a luminescent material of long light persistence is provided, wherein e = 0 in formula (1), introducing sulfur and / or selenium in said luminescent material of long light persistence, to replace partially oxygen in the reticle.

In accordance with another preferred version of the present invention, a luminescent material of long light persistence is provided, wherein e in formula (1), introducing sulfur and / or selenium into

Dicho 0 said material

luminescent of long light persistence to partially replace the oxygen in the lattice, and at the same time optionally introducing phosphorus as a constituent component, as well as a dopant.

In accordance with another preferred version of the present invention, a luminescent material of long light persistence is provided, wherein the ratios of the moles in the formula (1) satisfy the following ranges: 0.5 <to <6.0, 0.0001 ≤b≤0.1, 0.5≤c ≤6.6, 0≤d≤1.0, 0≤e≤1.0, 0.001≤x≤0.1, 0.001≤y≤0, 2, 0≤β≤1.0, where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0, (a + b) / c = 0.8 - 1.2; the amount (expressed in moles) of Sr is not less than 3.5 times the sum of Ca and Mg; or the amount (expressed in moles) of Sr is not less than 3.5 times the sum of Ca or Mg; The material presents a yellow-green emission after excitation. According to another preferred version of the present invention, a luminescent material of long light persistence is provided, wherein the moles ratios in the formula (1) satisfy: 0.5 <a <6.0, 0.0001 ≤ b ≤ 0,1, 0,75 ≤c ≤9,0, 0 ≤d ≤1,0, 0≤e≤1,0,0,001 ≤x≤0,1, 0,001 ≤y≤0,2, 0 ≤β ≤1.0, where 0.5 <(a + b) ≤6.0.0 <(d + e) ≤ 1.0, c / (a + b) = 1.5 - 1.9; and the luminescence color of prolonged light persistence of the material, is a blue-green color after excitation.

In accordance with another preferred version of the present invention, a luminescent material of prolonged light persistence is provided, wherein the ratios of the moles in the formula (1) satisfy: 0.5 <to <6.0, 0.0001 ≤ b≤ 0.1, 0.5 ≤ c ≤6.6, 0 ≤ d ≤1.0, 0 ≤ e ≤1.0, 0.001≤x ≤0.1, 0.001≤y≤ 0.2, 0 ≤ β ≤ 1.0, where (a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0, (a + b) / c = 0.8 - 1.2; the amount (expressed in moles) of Ca is not less than 3.5 times the sum of Sr and Mg; or the amount (expressed in moles) of Ca is not less than 3.5 times the sum of Sr or Mg; The material has a purple-blue luminescence after excitation.

In accordance with another preferred version of the present invention, a luminescent material of prolonged light persistence is provided, wherein the ratios of the moles in the formula (1) satisfy: 0.5 <a <6.0, 0.0001 ≤ b ≤0.1, 0.5 ≤ c ≤ 6.6, 0 ≤ d ≤1.0, 0 ≤ e ≤1.0, 0.001 ≤x ≤ 0.1, 0.001 ≤y≤0.2, 0 ≤ β ≤1.0, where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0, (a + b) / c = 0.9 - 1.1; the ratio of the amount (expressed in moles) between Ca and Sr is between 0.6 and 1.5; The color of the luminescence of prolonged light persistence of the material is white after excitation.

In accordance with another preferred version of the present invention, a luminescent material of prolonged light persistence is provided, wherein the ratios of the moles in the formula (1) satisfy: 0.5 <to <6.0, 0.0001 ≤ b ≤0.1, 0.5 ≤c ≤3.5, 0 ≤d ≤1.0, 0 ≤e ≤1.0, 0.001 ≤x≤0.2, 0.00001 ≤y≤0.2, 0 ≤β≤1.0, where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0, (a + b) / c = 2.0 - 3.3 ; and the luminescence of the material is red after excitation.

In accordance with another preferred version of the present invention, a luminescent material of prolonged light persistence is provided, wherein the ratios of the moles in the formula (1) satisfy: 0.01 ≤ x ≤ 0.25, 0.01 ≤ and ≤ 0.3, the material is also characterized by rapid loading.

In the chemical composition of the luminescent material of prolonged light persistence of the present invention, the oxygen sites in the lattice are partially replaced by sulfur and / or selenium, forming sulfur and / or selenium defects in the crystal, whereby the Luminescence properties of the luminescent material and the yields of the products thereof can be greatly improved; phosphorus can partially replace aluminum and if phosphorus is used in combination with sulfur and / or selenium, the material of prolonged light persistence can be greatly improved in terms of luminescence properties, and the powders of the luminescent material will be looser and easy to be crushed so that the loss of luminescence is reduced during the grinding process.

In the preparation of the luminescent material of prolonged light persistence of the present invention, the compounds of the elements in the formula (1) are used as raw materials, such as sulfur and / or selenium, the sulfur element and / or the Selenium element can also be used as raw materials being the molar ratios of the elements of the first materials:

M:

 0.5-6;

M:

0.0001-2.0;

S: 0.0001-2.0; Se: 0.0001-2.0; Al: 1.0-18;

B: 0-2.0;

P: 0-2.0; Eu: 0.00001-0.25; Ln: 0.00001-0.3.

A solid state high temperature reaction procedure was employed in the preparation method of this invention. The raw materials of the compounds of each element were weighed in molar ratios, ground and mixed homogeneously to produce a mixture, then the mixture was placed in a crucible, then sintered at a temperature between 700 and 1100 ° C for 2 -20 hours in an oxidizing atmosphere. After this, it is sintered at a temperature between 1100 and 1550 ° C for 2-30 hours in a reducing atmosphere (the reducing atmosphere is an atmosphere comprising hydrogen, ammonia, a mixture of hydrogen and nitrogen, or in the presence of carbon particles , and the atmosphere may further comprise less than 10% hydrogen sulfide) depending on the capacity of the furnace, the weight, the type, and the formulation of the fillers.

The method of preparation of this invention is a two-stage process comprising an oxidizing reaction stage and a reducing reaction stage. In this method, the diffusion of the rare earth activating ions in the luminescent material of prolonged light persistence, and the growth of the crystalline grain of the luminescent material of prolonged light persistence, are advantageously promoted. Additionally, a reducing atmosphere comprising less than 10% hydrogen sulfide (H2S) eased the volatilization of sulfur and / or selenium in the raw materials during the high temperature reaction, thereby facilitating the preparation of the new luminescent material of prolonged luminous persistence of aluminate comprising sulfur and / or selenium, of the present invention.

In order to improve the quality of the materials, a small amount (not more than 30% by weight of the mixed materials) of other compounds such as NH4Cl, NH4F, (NH4) 2HPO4, glucose can be added to the raw materials , urea, Li2CO3, SrF2, CaF2, CaSO4, SrS, CaS, SrSO4, SrHPO4 or CaHPO4, to participate in the solid phase reaction. After sintering, the sintered mixture is cooled, pulverized, and screened in batches of several particles depending on the requirements of the application.

In the invention, the brightness of the persistent luminescence and the persistence time of the samples can be measured by two types of methods: one is the direct test of the pulverized samples, wherein the powder samples are tested to determine the yield of the luminescence; and the other method is to previously make a luminescent film with the powder samples, and the luminescent film samples are tested to determine the luminescence performance.

In the method for testing the powder sample, the sample is placed in a round container 50 mm in diameter, 5 mm deep, and kept in the dark for more than 24 hours for excitation, then removed and exposed to a standard D65 light source under 1000 lux illumination for a 5-minute excitation, the luminescence intensity is measured as a function of time with a device for measuring the brightness of the luminescence equipped with a photomultiplier-marked tube as "routine test of dust sample" (As for a quick sample of luminescent powder with a fast charge working with a dim light), the sample is placed in a round container 50 mm in diameter and 5 mm deep, and the container is kept in the dark for no less 24 hours during extinction, then removed and exposed to a standard D65 light source under 25 lux illumination for 15 minutes excitation, the brightness of the persistent luminescence is measured as a function of time with a device measure the brightness of the luminescence equipped with a photomultiplier tube, and it is marked as "dim light test of the dust sample". While the test is being carried out, a comparative sample of the ancient technique is excited under the same conditions, and the persistent light brightness of the comparative sample is adjusted to 100, and in this way the relative brightness of the samples can be calculated.

The powder sample is prepared in luminescent films, and is subjected to the following test: the powder sample is uniformly mixed with a transparent resin in a ratio of 1: 1 by weight to form a mixture, and the mixture is used to coat uniformly a plastic sheet with a coating device to form a coating with a thickness of approximately 0.3 ± 0.002 mm, and then the coating is dried and cut into discs with a diameter of 54 mm, the standard coating is adjusted to 200 ± 2 grams of luminescent powder per square meter. (In the examples below, all sample films are prepared in the same process and conform to the same standard). The sample films are placed in the dark for no less than 24 hours for extinction, then removed and exposed to a standard D65 light source under 1000 lux of illumination for excitation for 5 minutes, the brightness of the luminescence Persistent as a function of time, it is measured with a device to measure the brightness of the luminescence equipped with a photomultiplier tube - and is signaled as a "routine film test". (films made of fast luminescent powders with fast charge under a dim light), the films are kept in the dark for no less than 24 hours for extinction, then removed and exposed to a standard D65 light source under lighting 25 lux for excitation for 15 minutes, the brightness of the persistent luminescence of the films is measured as a function of time, with a device for measuring the brightness of the luminescence equipped with a photomultiplier tube - and is signaled as &quot; test with dim light of the movie &quot;). While the test is being carried out, a comparative sample film of the prior art is excited under the same conditions, and the persistent brightness of the comparative sample film is set to 100, on which basis, the relative brightness of the Sample movies.

Samples of the examples of this invention and comparative samples were prepared with powders made in accordance with the present invention and the ancient technique respectively, the corresponding luminescent films were manufactured according to the method of making luminescent films as described above. under the same conditions. The powders and luminescent films of each sample were tested and measured with the methods for testing and measuring the corresponding luminescent powders and films as described above, the relative brightness values for all samples were measured every tenth. minute after the excitation was canceled.

The excitation spectrum and the emission spectrum of the materials were measured using an F-4500 fluorescence spectrometer.

This invention provides a new system of luminescent material with a new composite aluminate structure that combines the property of a fast loading of the simple sulphide or the oxisulfide system of luminescent materials and the longer persistence time of the luminescent materials of the simple aluminate system .

Compared to the various luminescent materials of the ancient technique, the luminescent material of the new system according to this invention has the following important advantages:

one.

The brightness of the luminescence and the light persistence time of the luminescent material powder has greatly improved, the luminescence of the luminescent material of this invention lasts no less than 90 hours before the brightness decreases to 0.3 mcd / m2, measured in accordance with the German standard test of luminescent materials DIN 67510;

2.

The luminescent material according to this invention is very well coupled with organic materials, the luminescent products thereof show great improvements in the intensity of the luminescence as well as in the time of light persistence;

3.

The luminescent material according to this invention appears in various luminescence colors, including purple-blue, blue-green, yellow-green, red and white, etc .;

Four.

The luminescent material according to this invention has the property of rapidly charging, of being able to absorb energy quickly and maintaining luminescence with low attenuation, even under lighting 40 times less than a normal light source;

5.

The luminescent material according to this invention has a broad excitation spectrum and a broad emission spectrum, and can be used in wide fields of application.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1. Powder sample emission spectrum of examples 1, 5, 7 and comparative example A.

(to)

SrO · Al2O3 · 0.02 B2O3: 0.004 Eu

(b)

SrO · 0.003 SrS · 0.001 SrSe · Al2O3 · 0.02 B2O3: 0.004 Eu

(C)

SrO · 0.005 SrSe · Al2O3 · 0.02 B2O3: 0.004 Eu

(d)

SrO · 0.002 SrS · Al2O3 · 0.02 B2O3 · 0.01 P2O5: 0.004 Eu

Figure 2. Luminescence brightness after excitation as a function of the light persistence time of the luminescent powder samples of Example 10 and their corresponding comparative sample

(to)

SrO · 0,01SrS · Al2O3 · 0,05B2O3 ·· 0,1P2O5: 0.005Eu · 0,01Dy

(b)

SrO · Al2O3 · 0.05B2O3: 0.005Eu · 0.01Dy

Figure 3. Emission spectrum of the luminescent powder samples of Example 27 and their corresponding comparative example.

(to)

4 SrO · 7Al2O3 · 0,3B2O3: 0,00001Eu · 0,00001Dy

(b)

4SrO · 0.005SrS · 7Al2O3 · 0.3B2O3 · 0.02P2O5: 0.00001Eu · 0.00001Dy

Figure 4. Emission spectra of the luminescent film products of Example 44 and their corresponding comparative example.

(to)

CaO · Al2O3 · 0.05B2O3: 0.001Eu · 0.0015Nd

(b)

   CaO · 0.01CaS · Al2O3 · 0.05B2O3 · 0.02P2O5: 0.001 Eu · 0.0015Nd

Figure 5. Excitation spectrum of the sample of example 58. Figure 6. Emission spectrum of the sample of example 58. Figure 7. Excitation spectrum of the luminescent powder sample of example 63. Figure 8. Emission spectrum of the luminescent powder sample of example 63. Figure 9. Luminescence brightness after excitation as a function of light persistence time of the luminescent films of example 63 and their corresponding comparative example.

DETAILED DESCRIPTION OF THE PREFERRED VERSIONS

The examples of the present invention will now be described in more detail below, the present invention not being limited by these examples. Sulfur (S) and selenium (Se) belong to the same group of the periodic table and, both elements, either in their elemental form or as a compound, play a similar role on luminescent materials of prolonged light persistence. Therefore only particular examples will be described, which in no way limit the application of sulfur (S) and selenium (Se) to the examples of the invention.

The present invention includes a luminescent material of prolonged light persistence, which has a yellow-green luminescence, and the method of preparation thereof. The present invention will be further explained with reference to examples 1-19.

Example 1

Raw material

Weight (g)

SrCO3

147.63

Al2O3

101.96

H3BO3

2.47

Mr

0.24

(NH4) 2HPO4

2.64

Eu2O3

0.7

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, then placed in a crucible and placed in an electric oven, and then sintered in an oxidizing atmosphere at 900 ° C for 10 hours, the crucible was removed after cooling. After the sintered product in the crucible had cooled itself to room temperature, it was sintered in a furnace through which a gaseous stream of a gas mixture that included 95% hydrogen, 3% of nitrogen and 2% hydrogen sulfide, the oven temperature was increased from 400 ° C to 1400 ° C for 10 hours, and maintained at 1400 ° C for 5 hours to sinter. Then the oven temperature was lowered to 200 ° C

15 for 6 hours, and the crucible was removed. After the sintered product in the crucible had cooled itself to room temperature, it was pulverized and ground in a ball mill, and then the luminescent particles were collected by sieving with a 325 mesh screen, to obtain a luminescent material according to the present invention SrO · 0.002 SrS · Al2O3 · 0.02 B2O3 · 0.01 P2O5: 0.004 Eu. The material was indicated as example 1.

20 Examples 1-7

The luminescent materials of prolonged light persistence, with a yellow-green color of the luminescence, of examples 2-7, were prepared by the same method of example 1, and compared with the luminescent material 25 of prolonged light persistence of the comparative example A of the ancient technique (SrO · Al2O3 · 0.02 B2O3: 0.004 Eu). The compositions of Examples 1-7 are listed in Table 1. In Table 1 and in the tables in the following examples, the term "comparative example (s)" means (n) the corresponding luminescent materials of long light persistence, prepared according to the ancient technique, and abbreviated with the term "comparative sample". Table 1 shows the compositions of luminescent materials, and the

30 values of the relative brightness of the powders and luminescent films corresponding to minute 10 after excitation, determined with respect to the value of the luminescent brightness of the powder and that of the comparative sample A film, to which the value was assigned 100

Figure 1 shows the emission spectra of the luminescent powders of Examples 1, 5, 7 and the sample

35 comparative A, the axis of the &quot; and &quot; Represents the relative brightness. It can be seen from Table 1 and Figure 1, that the new composite aluminate material according to the present invention has a slightly displaced red peak of the emission spectrum, and a luminescence brightness greatly enhanced, especially the property of adaptation with organic materials substantially improved, compared with the luminescent material of long yellow-green light persistence of the prior art.

40 Table 1

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

one

SrO · 0.002SrS · Al2O3 · 0.02 B2O3 · 0.01P2O5 · 0.004Eu 128 130

2

SrO · 0.01SrS · Al2O3 · 0.02 B2O3 · 0.1P2O5 · 0.004Eu 136 138

3

SrO · 0.0001SrSe · Al2O3 · 0.02 B2O3 · 0.005P2O5 · 0.004Eu 108 114

4

SrO · 0.001SrS · 0.000SrSe · Al2O3 · 0.02 B2O3 · 0.5P2O5 · 0.004Eu 122 128

5

SrO · 0.005SrSe · Al2O3 · 0.02 B2O3: 0.004Eu 121 128

6

SrO · 0.2SrS · Al2O3 · 0.02 B2O3: 0.004Eu 103 113

7

SrO · 0.003SrS · 0.001SrSe · Al2O3 · 0.02B2O3: 0.004Eu 112 118

Comparative Example A

SrO · Al2O3 · 0.02B2O3: 0.004Eu 100 100

Examples 8-12

The luminescent materials with long light persistence with different amounts (expressed in mmoles) of europium and dysprosium of examples 8-12, were prepared by the same procedure of example 1, the corresponding 5 comparative samples were prepared according to the ancient technique, and the luminescence brightness determination of these luminescent powders and films in minute 10 after excitation was suppressed and measured with the same methods of the routine dust test and the routine film test. Each of the examples and the comparative samples as well as the results of their relative brightness are listed in Table 2. The effect of adding different amounts of europium and dysprosium on the luminescent materials of long light persistence was well known in the technique, which provided luminescent powders and films of the luminescent materials of long light persistence, with different brightness. In the present invention a new composite aluminate structure was formed by the addition of sulfur and / or selenium

or addition of sulfur and / or selenium together with phosphorus, obtaining a relative brightness greater than that of comparative samples prepared according to the prior art.

Fig. 2 shows the luminescence brightness after excitation as a function of the light persistence time of the luminescent powder of Example 10 compared to its corresponding comparative sample. From Figure 2, it can be seen that the luminescence performance over the prolonged time of the luminescent materials of Example 10 was much better than that of its comparative sample. In addition, the slowest

20 luminescence attenuation was more important over time. The light persistence time of the material of example 10 was up to 70 hours before the luminescence was reduced to a brightness of 0.3 mcd / m2.

Table 2

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

8

SrO · 0.005SrS · Al2O3 · 0.05B2O3: 0.00001Eu · 0.00001Dy 119 122

Comparative Sample No. 8

SrO · Al2O3 · 0.05B2O3 · 0.00001Eu · 0.00001Dy 100 100

9

SrO · 0.005CaS · 0.005SrSe · Al2O3 · 0.05B2O3: 0.0001Eu · 0.0015 Dy 125 131

Comparative Sample No. 9

 SrO · Al2O3 · 0.05B2O3: 0.0001Eu · 0.0015Dy 100 100

10

SrO · 0.01SrS · Al2O3 · 0.05B2O3 · 0.1 P2O5: 0.005EU · 0.01 Dy 131 138

Comparative Sample No. 10

SrO · Al2O3 · 0.05 B2O3: 0.005Eu · 0.01Dy 100 100

eleven

SrO · 0.001CaSe · Al2O3 · 0.05 B2O3: 0.01Eu · 0.005Dy 111 116

Comparative Sample No. 11

SrO · Al2O3 · 0.05B2O3: 0.01Eu · 0.005Dy 100 100

12

 SrO · 0.1 SrS · 0.001SrSe · Al2O3 · 0.05B2O3 · 0.01P2O5: 0.15 Eu · 0.2Dy 103 105

Comparative Sample No. 12

SrO · Al2O3 · 0.05B2O3: 0.15 Eu · 0.2Dy 100 100

25 Examples 13-19

The luminescent materials of prolonged light persistence of examples 13-19 with Europium as activator and different amounts (expressed in moles) of other elements such as Nd, Dy, Ho, Tm, La, Ce, Er,

30 Pr, Bi, Sm, as coactivators, were prepared by the same method of example 1, the corresponding comparative samples were prepared according to the prior art. The luminescence brightness of these luminescent powders and films was measured in minute 10 after suppressing excitation. Each sample sample and the comparative sample, as well as the results of their corresponding brightness, are listed in Table 3. (In the following examples it should be noted that the combination of activators and coactivators is not limited to those above).

Table 3

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

13

0.6BaO · 0.02 SrS · 0.5Al2O3 · 0.02 B2O3 · 0.01P205: 0.005Eu · 0.004Dy · 0.0005Nd 121 121

Comparative Sample No. 13

0.6BaO · 0.5Al2O3 · 0.02B2O3: 0.005Eu · 0.004Dy · 0.0005Nd 100 100

14

(Sr0.8Ca0.2) O · 0.0002CaS · 0.0002 SrSe · Al203 · 0.05 B2O3: 0.005Eu · 0.0005Ho 110 113

Comparative Sample No. 14

(Sr0.8Ca0.2) O · Al2O3 · 0.05B2O3: 0.005Eu · 0.0005Ho 100 100

fifteen

(Sr0.9Mg0.1) O · 0.05SrS · Al2O3 · 0.05B2O3: 0.005 Eu 0.0005Tm 120 125

Comparative Sample No. 15

(0.95SrO · 0.1MgO) · Al2O3 · 0.05 B2O3: 0.005Eu · 0.0005 Tm 100 100

16

1.8 SrO · 0.1 SrS · 2.0 Al2O3 · 0.08 B2O3: 0.005 Eu · 0.0005 La 120 122

Comparative Sample No. 16

1.9 SrO · 2.0Al2O3 · 0.08 B2O3: 0.005 Eu · 0.0005 La 100 100

17

2,8SrO0,01CaS 3,0Al2O3 0,3B2O3 0,2P2O5 0,005Eu 0,0005 Er 127 131

Comparative Sample No. 17

(2.8SrO0.01CaO) 3.0Al2O3 0.3 0.3O3: 0.005Eu 0.0005Er 100 100

18

(Sr0.8Ca0.1 Mg0.1) O · 0.0015SrS · 0.0015SrSe · Al2O3: 0.005Eu · 0.004 La · 0.0005 Sm 127 133

Comparative Sample No. 18

(Sr0.8Ca0.1 Mg0.1) O · Al2O3 · 0.04B2O3: 0.005 Eu · 0.004 La · 0.0005Sm 100 100

19

2SrO · 0.0002CaSe · 2Al2O3 · 1.0P2O5: 0.015Eu · 0.004 Dy · 0.0005Ce 106 108

Comparative Sample No. 19

2SrO · 2AI2O3 · 0,1B2O3: 0,015Eu · 0,004 Dy · 0,0005 Ce 100 100

The present invention also comprises a luminescent material of prolonged light persistence with a blue-green luminescence, and method of preparation thereof. Next, the invention will be described with reference to examples 20-40.

Example 20

Raw material

Weight (g)

SrCO3

590.52

Al203

713.72

H3BO3

12.37

Mr

0.6

(NH4) 2HP04

1.32

Eu203

1.41

The raw materials of the previous composition were ground in a wedding mill and mixed thoroughly, then loaded into a crucible and placed in an electric oven, and sintered in an oxidizing atmosphere

10 to 1000 ° C for 20 hours. The crucible was removed after cooling, and the sintered product in the crucible was cooled by itself to room temperature, and then the product was sintered in an oven through which a gas mixture consisting of 54% hydrogen was passed. , 41% nitrogen and 5% hydrogen sulfide, the oven temperature was increased from 400 ° C to 1550 ° C for 18 hours, and maintained at 1550 ° C for 8 hours for sintering. The oven temperature was then decreased to 200 ° C for 6 hours, and the

15 crucible was removed from it. The sintered product in the crucible was cooled by itself to room temperature, then pulverized and ground in a ball mill, and screened with a 325 mesh screen, obtaining a luminescent material of the present invention, 4SrO · 0.005 SrS · 7Al2O3 · 0,1B2O3 · 0,01P2O5: 0,008Eu. The material was indicated as example 20.

20 Examples 20-26

The luminescent materials of prolonged light persistence with blue-green luminescence of Examples 21-26, were prepared by the same method of Example 20, and compared with the luminescent material of prolonged light persistence of the comparative sample B of the technique old (4SrO · 7Al2O3 ·

25 0,1B2O3: 0,008Eu). The compositions of Examples 20-26 are listed in Table 4. The brightness of the luminescence at 10 minutes after excitation of the luminescent powders and films was measured using the same test method described above. Each of the examples and comparative samples as well as the results of the relative brightness are listed in Table 4.

From table 4 it is clear that according to that invention a luminescent material with a long luminous persistence with blue-green luminescence can be prepared, and obtaining a luminescent material of prolonged light persistence with a higher brightness than the prepared material according to the ancient technique,

35 Table 4 Example 27-35

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

twenty

4SrO0.005SrS7Al2O30.1B2O30.01P2O5: 0.008Eu 126 131

twenty-one

4SrO · 0.2SrS · 7Al2O3 · 0,1B2O3 · 0,02P2O5: 0,008Eu 102 105

22

4SrO0.005SrS7Al2O30.1B2O3 0.005P2O5: 0.008Eu 139 144

2. 3

4SrO · 0.0001CaSe · 7Al2O3 · 0.9P2O5: 0.008Eu 103 105

24

4SrO · 0.005SrSe · 7Al203 · 0.1 B203: 0.008Eu 122 123

25

4SrO · 0.007SrS · 0.003SrSe · 7Al2O3 · 0,1B2O3: 0.008Eu 113 116

26

4SrO · 0.007CaS · 0.003CaSe · 7Al2O3 · 0.1B2O3 · 0.5P2O5: 0.008Eu 119 119

Comparative Sample B

4SrO7Al2O30.1B2O3: 0.008Eu 100 100

Luminescent materials of prolonged light persistence, with different quantities (expressed in moles)

5 of europium and dysprosium of examples 27-35, were prepared by the same method of example 20, the corresponding comparative samples were prepared according to the prior art, and the luminescence brightness of these powders and luminescent films were measured. minutes after the excitation was canceled. Each of these examples and comparative samples as well as the results of their relative brightness are listed in Table 5.

10 Figure 3 shows the emission spectra of the luminescence powder of Example 27 and its corresponding comparative sample. From the emission spectra, it can be seen that only by the addition of sulfide, the emission wavelength of the emission spectrum of the blue-green luminescent material of Example 27 was slightly offset to red compared to the comparative sample , in which there was no

15 substantial change in the color of the luminescence. Meanwhile it can be clearly seen that the luminescence intensity increased greatly when comparing the relative brightness of the emission spectra and the relative brightness of the powders and films. Table 5

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

27

4SrO · 0.005SrS · 7Al2O3 · · 0.3B2O3 · 0.02P2O5: 0.00001Eu · 0.00001Dy 120 123

Comparative Sample No. 27

4SrO · 7Al2O3 · 0.3B2O3: 0.00001Eu · 0.00001Dy 100 100

28

5.8SrO · 0.01SrS · 9Al2O3 · 0.5B2O3: 0.0001Eu · 0.0015Dy 116 121

Comparative Sample No. 28

5.8SrO · 9Al2O3 · 0.5B2O3: 0.000lEu · 0.0015Dy 100 100

29

4SrO · 0.0005SrSe · 7Al2O3 · 0.4B2O3 · 0.1P2O5: 0.001Eu · 0.001Dy 123 125

Comparative Sample No. 29

4SrO7AI2O3 0.4B2O3: 0.001Eu 0.001Dy 100 100

30

3.5SrO · 0.02SrS · 0.002SrSe · 5.6Al2O3 · 0.35B2O3 · 0.005P2O5: 0.01Eu · 0.01Dy 117 119

Comparative Sample No. 30

3.5SrO5.6Al2O30.35B2O3: 0.01Eu0.01Dy 100 100

31

4SrO · 0.002SrSe · 7Al2O3 · 0.15B2O3: 0.15 Eu · 0.2Dy 107 110

Comparative Sample No. 31

4SrO · 7Al2O3 · 0.15B2O3 · 0.15Eu · 0.2Dy 100 100

Examples 32-40

5 The luminescent materials of prolonged light persistence of Examples 32-40, which comprise Europium as an activator and different amounts (expressed in moles) of other elements such as Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm as coactivators, were prepared by the same method as in Example 20, the corresponding comparative samples were prepared according to the ancient technique, and the brightness of the luminescence was suppressed 10 minutes after the excitation of these powders and films. luminescent, and it was measured

10 with the same method as described above. The compositions of each example and comparative sample as well as the results of their relative brightness are related in Table 6. From these results it can be seen that the addition of different amounts of coactivators in the composite aluminates that were doped with sulfur and / or selenium or with sulfur and / or selenium in combination with phosphorus, resulted in improvements of various degrees in the luminescence brightness of the luminescent powders and the corresponding films of the

The same, so that the relative brightness of the luminescent powders and the films of each example were substantially enhanced (in the following examples, it will be appreciated that the combination of activators and coactivators is not limited to the above).

Table 6 20

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

32

0.6SrO0.015SrS0.92Al2O30.01 B203: 0.005Eu0,0005Nd 106 107

Comparative Sample No. 32

0.6SrO0.92Al2O30.01 B203: 0.005Eu0,0005Nd 100 100

33

4,2SrO0,05SrS7Al2O30,5B2O3 0,05P2O5 0,005Eu 0,004Dy0,0005 Nd 115 118

Comparative Sample No. 33

4.2SrO · 7Al2O3 · 0.5B2O3: 0.005Eu · 0.004Dy · 0.0005Nd 100 100

3. 4

(2,6SrO · 0,3CaO) · 0,001 SrSe · 0.001 SrS · 5Al2O3 · 0,4B2O3 · 0,1P2O5: 0,005Eu · 0,004Dy · 0,0005Ho 125 128

Comparative Sample No. 34

(2.6SrO · 0.3CaO) · 5Al2O3 · 0.4B2O3: 0.005Eu · 0.004Dy · 0.0005Ho 100 100

35

(3,4SrO · 0,1MgO) · 0,04SrS · 0,02CaS · 6Al2O3 · 0,2B2O3: 0,005Eu · 0,004Dy · 0,0005Tm 110 109

Comparative Sample No. 35

(3.44SrO · 0.1MgO · 0.02CaO) · 6Al2O3 · 0.2B2O3: 0.005Eu · 0.004Dy · 0.0005Tm 100 100

36

3,7SrO · 0,1SrS · 5,8Al2O3 · 0,4B2O3 · 0,1P2O5: 0,005Eu · 0,004Dy · 0,0005La 98 103

Comparative Sample No. 36

3.7SrO · 5.8 Al2O3 · 0.4B2O3: 0.005Eu · 0.004Dy · 0.0005La 100 100

37

4.36SrO · 0.2SrS · 8.0AI2O3 · 0.8B2O3 · 0.02P2O5: 0.005Eu · 0.004Dy · 0.0005Er 100 103

Comparative Sample No. 37

4.56SrO8.0AI2O30.8B2O3: 0.005Eu0.004Dy0,0005Er 100 100

38

(3.8SrO · 0.1CaO · 0.1 MgO) 0.001SrSe · 0.02CaS · 7Al2O3 · 0.4B2O3: 0.005Eu · 0.004Dy · 0.0005Sm 115 120

Comparative Sample No. 38

(3.8SrO · 0.1 CaO · 0.1MgO) · 7Al203 · 0.4B2O3: 0.005Eu · 0.004Dy · 0.0005Sm 100 100

39

3.7SrO · 0.07CaSe · 7Al2O3 · 0.5B2O3 · 0.5P2O5: 0.005Eu · 0.004Dy · 0.0005Ce 108 109

Comparative Sample No. 39

(3.7SrO · 0.07CaO) · 7Al2O3 · 0.5B2O3: 0.005Eu · 0.004Dy · 0.0005Ce 100 100

40

4SrO · 0.02SrS · 7.05Al2O3 · 0.45B2O3 · 0.05P2O5: 0.005Eu · 0.005Nd · 0.004Pr 130 133

Comparative Sample No. 40

4SrO7.05Al2O30.45B2O3: 0.005Eu0.005Nd0.004Pr 100 100

The present invention also comprises a luminescent material of prolonged light persistence with purple-blue luminescence, and the method of preparation thereof. The same is described below with reference to examples 41-54.

Example 41

Raw material

Weight (g)

CaC03

100

Al203

101.96

H3B03

2.47

CaS

0.36

(NH4) 2HP04

1.32

Eu2O3

0.88

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, to

Then they were loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 700 ° C for 10 hours, the crucible was removed after cooling. The sintered product in the crucible cooled itself to room temperature, and then sintered in an oven through which a gas mixture containing 95% hydrogen, 3% nitrogen and 2% sulfide was passed. hydrogen, the oven temperature was increased from 400 ° C to 1300 ° C for 10 hours and maintained at 1300 ° C for 5 hours

15 for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, and the crucible was removed, the product was sintered in the crucible, cooled itself to room temperature, and then pulverized and ground in a mill of balls, it was screened in a 250 mesh screen to obtain a luminescent material according to the present invention CaO · 0.005CaS · Al2O3 · 0.02B2O3 · 0.005P2O5: 0.005. The material was labeled as example # 41.

20 Examples 41-43

The luminescent material of prolonged light persistence with purple-blue luminescence of Examples 42-43, was prepared by the same method of Example 41 and the luminescent material of prolonged

The light persistence of the comparative sample C was prepared according to the old technique (CaO · Al2O3 · 0.02 B2O3: 0.005Eu). The luminescent powders and films of the examples and comparative samples were measured with the methods for the routine testing of the powders and the routine methods of the films respectively. The compositions and test results of the examples and comparative samples are listed in Table 7.

From table 7 it can be seen that according to this invention a luminescent material of prolonged light persistence with purple-blue luminescence can be prepared. Due to the new composite aluminate structure, the brightness of the luminescence of the luminescent material of prolonged light persistence with purple-blue luminescence prepared in accordance with this invention, was substantially enhanced, and

35 the products thereof were presented for their greater brightness, compared to the material prepared according to the ancient technique.

Table 7

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

41

CaO · 0.005CaS · Al2O3 · 0.02B2O3 · 0.005P2O5: 0.005Eu 139 143

42

CaO · 0.005CaS · 0.002CaSe · Al2O3 · 0.02B2O3: 0.005Eu 120 122

43

CaO · 0.002CaSe · Al2O3 · 0.02B2O3 · 0.01P2O5: 0.005Eu 120 123

Comparative Sample C

CaO · Al2O3 · 0.02B2O3: 0.005Eu 100 100

Examples 44-46

5 The luminescent materials of prolonged light persistence with different amounts (expressed in moles) of europium and dysprosium of Examples 44-46, were prepared by the same method of Example 41, the corresponding comparative samples were prepared according to the prior art, and the brightness of the luminescence was suppressed at 10 minutes after the excitation of these luminescent powders and films, and was measured by the same method as described above. The compositions of each example and samples

10 comparatives as well as the results of their relative brightness are listed in table 8.

Figure 4 shows the comparison of the emission spectrum of a luminescent film product of Example 44 with the corresponding comparative example.

15 By observation, it can be deduced from Figure 4, that the luminescent material of prolonged light persistence of the new system according to this invention could be manufactured in products with greater luminescence intensity when compared with the luminescent material of prolonged light persistence with a purple luminescence color, prepared according to the ancient technique.

Table 8 20

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

44

CaO · 0.01CaS · Al2O3 · 0.05B2O3 · 0.02P2O5: 0.001Eu · 0.0015Nd 127 130

Comparative Sample No. 44

CaO · Al2O3 · 0.05B2O3: 0.001Eu · 0.0015Nd 100 100

Four. Five

CaO · 0.005CaS · 0.002SrSe · Al2O3 · 0.001B2O3 · 0.01P2O5: 0.001Eu · 0.0015Nd 134 135

Comparative Sample No. 45

CaO · Al2O3 · 0.01B2O3: 0.001Eu · 0.0015Nd 100 100

46

CaO · 0.001CaS · Al2O3 · 0.01B2O3: 0.01Eu · 0.01Nd 118 121

Comparative Sample No. 46

CaO · Al2O3 · 0.01B2O3: 0.01Eu · 0.02Nd 100 100

Examples 47-54

The luminescent materials of prolonged light persistence of Examples 47-54 were prepared, including the europium as activator and different amounts (expressed in moles) of other elements such as Nd,

5 Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm as coactivators, by the same method as example 41, the corresponding comparative samples were prepared according to the old technique, the brightness of the luminescence was suppressed At 10 minutes after the excitation of these luminescent powders and the films, they were measured with the same method as described above. The compositions of each example and the comparative sample as well as the results of their relative brightness are listed in Table 9.

10 Table 9 The present invention also provides a luminescent material of prolonged light persistence with a white luminescence compound. Compositions, properties and method of preparation of the material will be described with reference to examples 55-57.

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

47

0.7CaO · 0.003CaS · 0.8Al2O3 · 0.015B2O3 · 0.000lEu · 0.0015Nd · 0.004Pr 119 121

Comparative Sample No. 47

0.7 CaO · 0.8Al2O3 · 0.015B2O3 · 0.0001Eu · 0.0015Nd · 0.004Pr 100 100

48

 (Ca0.9Sr0.1) O · 0.002CaSe · Al2O3 · 0.03B2O3 · 0.1P2O5 · 0.001Eu · 0.001Nd · 0.0005Ho 116 117

Comparative Sample No. 48

(Ca0.9Sr0.1) O · Al2O3. 0.03B2O3 0.00l Eu · 0.001Nd · 0.0005Ho 100 100

49

(Ca0.8Mg0.2) O · 0.006CaS · 0.001CaSe · Al2O3 · 0.05B2O3 · 0.005Eu · 0.004Nd · 0.0005Tm 116 115

Comparative Sample No. 49

(Ca0.8Mg0.2) O · Al2O3 · 0.05B2O3 · 0.005Eu · 0.004Nd · 0.0005Tm 100 100

fifty

 2.85CaO · 0.02CaS · 3.0Al2O3 · 0.05B2O3 · 0.02P2O5 · 0.15Eu · 0.2Nd · 0.0001Er 117 113

Comparative Sample No. 50

2.87CaO · 3.0Al2O3 · 0.05B2O3 · 0.15Eu · 0.2Nd · 0.0001Er 100 100

51

(Ca0.8Sr0.1Mg0.1) O · 0.01CaS · Al2O3 · 0.02B2O3 · 0.02P2O5: 0.005Eu · 0.004Nd · 0.0005Sm 129 132

Comparative Sample No. 51

(Ca0.8Sr0.1Mg0.1) O · Al2O3 · 0.02B2O3: 0.005Eu · 0.004Nd · 0.0005Sm 100 100

52

 0.95CaO · 0.003CaS · 0.003SrSe · Al2O3 · 0.01B2O3 · 0.07P2O5 · 0.005Eu · 0.004 Nd · 0.0005Ce 126 124

Comparative Sample No. 52

0.95CaO · Al2O3 · 0.01B2O3: 0.005Eu · 0.004Nd · 0.0005Ce 100 100

53

0.98CaO · 0.01SrS · 1.05Al2O3 · 0.3P2O5: 0.005Eu · 0.005Nd · 0.004Pr · 0.001La 108 111

Comparative Sample No. 53

0.98 CaO · 1.05 Al2O3 · 0.0015B2O3: 0.005Eu · 0.005Nd · 0.004 Pr · 0.001La 100 100

54

 2.0CaO · 0.15CaS · 1.8Al2O3 · 0.03B2O3: 0.15Eu · 0.1Nd · 0.004Sm · 0.05La 108 113

Comparative Sample No. 54

 2.0CaO · 1.8Al2O3 · 0.03B2O 3: 0.15Eu · 0.1 Nd · 0.004Sm · 0.05La 100 100

Example 55

Raw material

Weight (g)

CaC03

fifty

SrC03

73.82

Al203

101.98

H3BO3

2.47

CaS

0.007

(NH4) 2HP04

5.28

Eu203

0.88

Nd203

5.06

10 The raw materials of the above composition were ground in a ball mill and thoroughly mixed, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 800 ° C for 10 hours, the crucible was removed after cooling. The sintered product in the crucible cooled itself to room temperature, and then sintered in an oven through which a gas stream consisting of 100% hydrogen was passed, the oven temperature was increased from 400 ° C

15 to 1450 ° C for 6 hours, and kept at 1450 ° C for 2 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, and the crucible was removed, and the sintered product in the crucible cooled itself to room temperature, and was pulverized, and ground in a mill of balls, and it was screened with a 325 mesh sieve obtaining the luminescent material according to the present invention (Sr0.5Ca 0.5) O · 0.0001CaS · Al2O3 · 0.02B2O3 · 0.02P2O5: 0.005Eu · 0 , 03Nd. The material was indicated as example 55.

20 Example 55-57

The luminescent materials of prolonged light persistence of Example 56-57, with a white luminescence, were prepared by the same method of Example 55. The compositions are referenced in

25 table 10. Since in the ancient technique there was no luminescent material of prolonged light persistence with a white luminescence, the comparative sample was not available.

Table 10

Example No.

Composition of the examples

55

(Sr0.5Cao.5) O · 0.0001CaS · H203 · 0.02B203 · 0.02P205: 0.005Eu · 0.03Nd

56

3.54SrO · 2.36CaO · 0.01CaS · 6.0Al2O3 · 0.02B2O3: 0.01Eu · 0.02Nd · 0.005Dy

57

(Sr0.4Ca0.6) O · 0.0001SrSe · AI2O3 · 0.02B2O3 · 0.002P2O5: 0.01Eu · 0.03Dy

5 Another new discovery of this invention was described as follows. In the case of introducing respectively sulfur and / or selenium, or sulfur and / or selenium in combination with phosphorus into the composite aluminate structure, a material of prolonged light persistence could be obtained with a luminescence of red color with an intense emission peak at 590-620 nm, loading the matrix composition, that is, adjusting within certain margins

10 the molar ratio between Sr and Al, as well as the amounts (expressed in moles) of the activator ions.

Next, the present invention is described with reference to examples 58-62.

Example 58 15

Raw material

Weight (g)

SrC03

664.34

Al203

203.92

H3BO3

2.47

Mr

35.9

(NH4) 2HP04

52.82

Eu2O3

28.16

Tm203

0.06

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 1100 ° C for 2 hours, the crucible He retired after cooling. The sintered product in the crucible was cooled by itself to room temperature, and then sintered in an oven through which a mixture of gases consisting of 88% hydrogen, 2% nitrogen and 10% hydrogen sulfide was passed. , the oven temperature was increased from 400 ° C to 1100 ° C for 8 hours, and maintained at 1100 ° C for 3 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, the crucible was removed, and the

The sintered product in the crucible was cooled by itself to room temperature, pulverized, and ground in a ball mill, then screened with a 325 mesh screen to obtain a luminescent material in accordance with the present invention (4 , 5SrO · 0.3SrS · 2Al2O3 · 0.02B2O3 · 0.2P2O5: 0.16Eu · 0.0003Tm). The material was indicated as example 58.

Examples 58-62

The luminescent materials of prolonged light persistence of Examples 59-62 were prepared with a red luminescence, by the same method as Example 58. The compositions are listed in Table 11.

Figure 6 clearly shows the emission peak of example 58 which is located at approximately 615 nm, and its luminous persistent luminescence was red. Comparing the conventional long-lasting luminescent material SrS · CaS · 0.02B2O3: 0.004Eu with a red luminescence, with the

With luminescent material of prolonged light persistence with a red luminescence of the invention, the latter had better chemical stability and greater temperature resistance.

Table 11 15

Example No.

Composition of the examples

58

4,5SrO · 0,3SrS · 2Al2O3 · 0,02B2O3 · 0,2P2O5: 0,16Eu · 0,0003Tm

59

0.6SrO · 0.7SrS · 0.5Al2O3 · 0.02B2O3 · 0.02P2O5: 0.008Eu · 0.0001Dy

60

6.0SrO · 1.5SrS · 3.0Al2O3 · 1.0P2O5: 0.25Eu · 0.05Tm · 0.001 Pr

61

3.0SrO · 2.0SrS · 2.5Al2O3 · 0.02B2O3: 0.015Eu · 0.0001Ce

62

2.5SrO · 0.4SrS · 0.1SrSe · 1.0Al2O3 · 0.02B2O3 · 0.02P2O5: 0.04Eu · 0.005Nd

Another new discovery of this invention is described as follows. In the case of introducing sulfur and / or selenium, or

sulfur and / or selenium in combination with phosphorus within the composite aluminate structure, the materials of long light persistence with various luminescent colors of the invention exhibit a rapid loading by means of the

adjustment of the molar ratio between alkaline earth metals and aluminum, as well as the contents of ions

rare earth activators. It is well known in the art that a luminescent material having a

Fast charging performance is inevitably accompanied by very fast attenuation. Therefore said

Materials are greatly limited in practical applications. However, the present invention solves this problem very well, providing luminescent materials of prolonged light persistence

With both features, fast charging and slow dimming.

Next, the present invention will be described with reference to examples 63-65.

30 Example 63

Raw material

Weight (g)

SrCOs

147.63

Al2O3

96.86

H3BO3

2.47

Mr

0.72

(NH4) 2HP04

5.28

Eu203

8.8

Dy203

5.6

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 800 ° C for 8 hours. The crucible was removed after cooling. The sintered product in the crucible cooled itself to room temperature, and then sintered in an oven through which a mixture of gases consisting of 90% hydrogen, 5% nitrogen and 5% hydrogen sulfide was passed. , the oven temperature was increased from 400 ° C to 1450 ° C for 4 hours, and maintained at 1450 ° C for 3 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, and the

10 crucible withdrew. The sintered product in the crucible was cooled by itself to room temperature, pulverized, and ground in a ball mill, then screened with a 325 mesh screen to obtain a luminescent material in accordance with the present invention (SrO · 0.006SrS · 0.95Al2O3 · 0.02B2O3 · 0.02P2O5: 0.05Eu · 0.03Dy). The material was indicated as example 63.

15 Example 64

Raw material

Weight (g)

Sr (N03) 2

952.34

Al (OH) 3

1076.4

H3BO3

61.83

Mr

0.36

(NH4) 2HP04

2.39

Eu203

26.4

Dy203

37.3

The raw materials of the previous composition were ground in a ball mill and mixed

20 completely, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 1000 ° C for 20 hours and the crucible was removed after cooling. The sintered product in the crucible was cooled by itself to room temperature and then sintered in an oven through which a gas mixture consisting of 62% nitrogen, 33% nitrogen and 5% hydrogen sulfide was passed, the oven temperature was increased from 400 ° C to 1550 ° C for 18 hours

25 and was maintained at 1550 for 8 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, and the crucible was removed. The sintered product in the crucible was cooled by itself to room temperature, pulverized, ground in a ball mill, and screened with a 325 mesh screen, giving a luminescent material in accordance with the present invention: 5SrO · 0.003SrS · 6.9Al2O3 · 0.5B2O3 · 0.01P2O5: 0.15Eu · 0.20Dy. The material was indicated as example 64.

30 Example 65

Raw material

Weight (g)

CaCO3

100

Al2O3

99.92

H3BO3

1.7

CaS

0.36

(NH4) 2HP04

1.32

Eu203

8.8

Nd203

3.36

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 700 ° C for 10 hours and the crucible was removed after cooling. The sintered product in the crucible was cooled by itself to room temperature and then sintered in an oven through which a gas mixture consisting of 95% hydrogen, 3% nitrogen and the gas was passed. 2% hydrogen sulfide, the oven temperature was increased from 400 ° C to 1300 ° C for 10 hours, and maintained at 1300 ° C for 5 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 6 hours, and the crucible was removed, the sintered product in the crucible cooled itself to the temperature

10, and it was pulverized and ground in a ball mill, then screened with a 250 mesh screen, obtaining a luminescent material according to the present invention: CaO · 0.005CaS · 0.98 Al2O3 · 0.01B2O3 0.005P2O5: 0.05Eu0.02Nd2O3. The material was indicated as example 65.

Table 12 shows the compositions and measurements of the brightness of the powder and film products of the

15 examples 63-65 in comparison with the corresponding comparative samples of the ancient technique. The powders and films of all the samples were tested for brightness, with the methods of testing with dim light, of the powders and of the films respectively.

Table 12 20

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

63

SrO · 0.006SrS · 0.95Al2O3 · 0.02B2O3 · 0.02 P2O5: 0.05Eu · 0.03Dy 121 127

Comparative Sample 63

0.94SrO · Al2O3 · 0.02B2O3: 0.005Eu · 0.025Dy 100 100

64

4,5SrO · 0,003SrS · 6,9Al2O3. 0,5B2O3 0,01P2O5: 0,15Eu 0,2Dy 121 124

Comparative Sample 64

4.5SrO · 6.9Al2O3 · 0.5B2O3: 0.15Eu · 0.2Dy 100 100

65

CaO · 0.005CaS · 0.98Al2O3 · 0.01B2O3 · 0.005P2O5: 0.05Eu0 · 0.02Nd2O3 114 112

Comparative Sample 65

CaO0.98Al2O30.01B2O3: 0.05Eu0.02Nd 100 100

Figure 7 and Figure 8 show the excitation spectrum and the emission spectrum of the luminescent powder of example 63. From the two figures, it can be seen that the luminescent powder of the example had a very wide excitation spectrum, and that Its emission spectrum was within the range of yellow-green light, the powder is very suitable to be used for indication under conditions of a dim light.

Figure 9 shows the brightness attenuation curves of the luminescence as a function of the luminescence time of the luminescent film of example 63 and the corresponding comparative example after being exposed to 25 lux of illumination for 15 minutes under a light source D65 standard. From the

5 comparing the curves, it can be clearly seen that, after the same excitation under a dim light source, the initial brightness after the 1st minute and the brightness at minute 60 of the products of example 63 were much greater than those of the comparative sample, and the light persistence time was 2 times or longer than that of the comparison sample. In addition, it was shown that the examples according to this invention had a strong fast chargeability in low light conditions, and their attenuation was low.

10 With reference to Table 12 and Figures 7-9, the present luminescent composite aluminate material, comprising sulfur and / or selenium, or sulfur and / or selenium in combination with phosphorus, has a faster loading and a slower attenuation , compared to the luminescent materials of prolonged light persistence of the ancient technique.

The inventors discovered that the brightness of the luminescence of the materials could be improved by several degrees by adding additives such as NH4CI, NH4F, (NH4) 2HP04, glucose, urea, Li2C03, SrF2, CaF2, CaS04, SrS, CaS, SrS04, SrHP04, CaHP04 and the like in an amount from 0 to 30% based on the total weight of the raw materials, which will be explained by the following examples.

20 Example 66

A mixture is prepared according to the chemical composition of SrO · 0.001SrS · Al2O3 · 0.02B2O3: 0.005Eu · 0.01Dy, with the addition of 30% (by weight) of urea. The detail of the content was as follows:

First subject

Weight (g)

SrCO3

147.63

Al203

101.96

H3BO3

2.47

Mr

0.12

Eu2O3

0.88

Dy2O3

1.87

Urea

76.48

The raw materials of the previous composition were ground in a ball mill and mixed thoroughly, then loaded into a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 1000 ° C for 2 hours, and the crucible was removed after cooling. The sintered product in the crucible was cooled by itself to room temperature and covered with a lid, the product was then buried in a crucible filled with carbon particles, and covered with a lid and placed in an oven, The oven temperature was increased from 400 ° C to 1200 ° C for 8 hours, and kept at 1200 ° C for 3 hours for sintering. Then, the oven temperature was lowered to 200 ° C for 4 hours, and the crucible was

35 withdrew. The sintered product in the crucible cooled itself to room temperature, and was pulverized, ground in a ball mill, and then screened with a 325 mesh screen to obtain the luminescent particles. The material was indicated as example 66.

After the X-ray analysis, no new crystalline phase was identified, but the material obtained showed a

40 improves both brightness of light persistence and a decrease in dimming speed. Table 13 showed the results of the comparison.

Table 13

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

66

SrO · 0.00l SrS · Al2O3 · 0.02 B2O3: 0.005Eu · 0.01Dy + 30% (weight) of urea 108 110

Comparative Sample No. 66

SrO · 0.001SrS · Al2O3 · 0.02B2O3: 0.005Eu · 0.01Dy 100 100

It was demonstrated by the corresponding experiments that NH4CI, NH4F, (NH4) 2HP04, glucose, 5 urea, SrHP04 or CaHPO4 had an effect similar to that of urea. Example 67

A mixture was prepared according to the chemical composition of 4SrO · 7Al2O3 · 0.04B2O3 · 0.02P2O5: 0.005Eu · 0.001Dy, with the addition of 1% (by weight) of CaS04. The content detail was as follows: 10

Raw material

Weight (g)

SrC03

147.63

Al2O3

178.43

H3BO3

4.94

(NH4) 2HP04

5.28

Eu203

0.88

Dy203

0.19

Ca04

3.37

The raw materials of the above composition were ground in a ball mill and mixed thoroughly, then loaded in a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 1000 ° C for 15 hours, the crucible was removed after cooling. The sintered product in the crucible was cooled by itself to room temperature, and then sintered in a furnace through which a gaseous mixture consisting of 100% ammonia was passed, the oven temperature was increased from 400 ° C up to 1450 ° C for 8 hours, and kept at 1450 ° C for 10 hours for sintering. The oven temperature was then lowered to 200 ° C for 8 hours, and the crucible was removed. The sintered product in the crucible cooled itself until room temperature was pulverized, ground in a ball mill and then

Then, it was screened with a 325 mesh screen to obtain luminescent particles. The material was indicated as example 67.

After the test, the material obtained showed certain improvements in the persistent brightness of the illumination, and the slowing down of the dimming speed. Table 14 shows the results of the comparison. 25

Table 14

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

67

4SrO · 7Al2O3 · 0.04B2O3 · 0.02P2O5 · 0.005Eu · 0.001Dy + 1% (weight) CaS04 105 107

Comparative Sample No. 67

4SrO · 7Al2O3 · 0.04B2O3 · 0.02P2O5: 0.005Eu · 0.001Dy 100 100

It was experimentally proven that SrS, CaS and SrSO4 all had similar effects. 5 Example 68

A mixture was prepared according to the chemical composition CaO · 0.001CaS · Al2O3 · 0.01B2O3 · 0.02P2O5: 0.002Eu · 0.005Nd, with the addition of 10% (by weight) of CaF2. The content detail was as follows: 10

First material

Weight (g)

CaC03

100

Al2O3

101 of 96

CaS

0.072

H3B03

1.74

(NH4) 2HP04

30

Eu203

0.35

Nd203

0.84

CaF2

23.49

The raw materials of the previous composition were ground in a ball mill and mixed thoroughly, then loaded in a crucible and placed in an electric oven, then sintered in an oxidizing atmosphere at 700 ° C for 10 hours and the crucible was removed after cooling. The sintered product in the crucible was cooled on its own to room temperature, and then sintered in an oven through which a gas mixture consisting of 100% hydrogen was passed, the oven temperature was increased from 400 ° C up to 1300 ° C for 10 hours, and kept at 1300 ° C for 5 hours for sintering. The oven temperature was then decreased to 200 ° C for 6 hours, and the crucible was

20 removed, the sintered product in the crucible was cooled on its own to room temperature, and pulverized, ground in a ball mill, and then screened with a 325 mesh screen to obtain luminescent particles. The material was indicated as example 68. After the test, the material obtained showed improvements in the persistent light brightness and the slowing down of the attenuation speed. Table 15 shows the results of the comparison.

Table 15

Example No.

Composition of the examples Relative powder brightness Relative brightness of the luminescent film

68

CaO · 0.001CaS · Al2O3 · 0.01B2O3 · 0.02P2O5: 0.002Eu · 0.005Nd + 10% (by weight) of CaF2 110 113

Comparative Sample 68

CaO · 0.001CaS · Al2O3 · 0.01B2O3 · 0.02P2O5: 0.002Eu · 0.005Nd 100 100

5 It was experimentally proven that both Li2CO3 and SrF2 had a similar effect.

Industrial application

The products of this invention can be widely used in all kinds of persistence products.

10 prolonged lighting as indicators or ornaments in dark environments, combined with paint; plastics; printing ink, rubber, etc., these luminescent materials find good applications in fields of architecture, traffic, decoration, wrist watches and foot watches, fishing tackle, toys and other items of daily use, and are especially suitable for the production of long light persistence safety products, such as warning signs, mandatory signs and route exit signals. These

15 materials can also be used for white LEDs.

Claims (14)

1. A material of prolonged light persistence, characterized in that it is a luminescent material composed of aluminate, comprising sulfur and / or selenium, or comprising sulfur and / or selenium and phosphorus as well as activating ions, and its main chemical composition comes expressed by the following formula: a MO · b M '(SβSe1-β) · c Al2O3 · d B2O3 · e P2O5: x Eu · and Ln where: M is selected (n) from Sr, Ca, Ba and Mg, and any combination thereof; M 'is selected (n) from Sr, Ca, and Ba, and any combination thereof; Ln (n) is selected from Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi and Sm and any combination thereof; a, b, c, d, e, x and y, are molar ratios and satisfy the conditions: 0.5 <a <6.0, 0.0001≤ b ≤2.0, 0.5 ≤ c ≤ 9.0, 0 ≤d ≤ 1.0 0≤ e ≤ 1.0, 0.00001≤ x ≤ 0.25, 0.00001 ≤y ≤0.3, 0 ≤ β ≤ 1.0, 0, 5 <(a + b) ≤ 6.0, 0 <(d + e) ≤ 1.0.

2.

The luminescent material of prolonged light persistence, according to claim 1, characterized in that, in the formula, M is selected from Sr, Ca and Mg and any combinations thereof; M 'is selected (n) between Sr and Ca and any combinations thereof; Ln (n) is selected from Nd, Dy, Tm, La, Pr, Sm and Ce and any combinations thereof, where after excited by light with a wavelength of 500 nm or less, the material emits a spectrum between 420-650 nm with a peak located within 440-620 nm, and has luminescence colors of prolonged light persistence selected from the colors purple-blue, blue-green, yellow-green, white and red, and in where the material has a fast charge.

3.

The luminescent material of prolonged light persistence, according to claim 1 or 2, characterized in that, in the formula, e = 0 and M 'is (n) selected between Sr and Ca, and any combinations thereof.

Four.

The luminescent material of prolonged light persistence, according to claim 1 or 2, characterized in that, in said chemical composition formula, e ≠ 0 and M 'is (s) selected between Sr, and Ca and any combinations of the same.

5.

The luminescent material of prolonged light persistence, according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.5 <a <6.0, 0.0001 ≤ b ≤ 0.1, 0.5 ≤ c ≤ 6.6, 0 ≤ d ≤ 1.0 0 ≤e≤1.0, 0.001≤x ≤0.1, 0.001≤y≤0.2, 0 ≤β≤1.0 where 0.5 <(a + b) ≤6.0, 0 <(d + e) ≤1.0, (a + b) / c = 0.8 - 1.2; the amount (expressed in moles) of Sr is not less than 3.5 times the sum of Ca and Mg; or the amount (expressed in moles) of Sr is not less than 3.5 times the amount of Ca or Mg; and the color of the luminescence is yellow-green after excitation.

6.

The luminescent material of prolonged light persistence according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.5 <a <6.0, 0.0001 ≤ b ≤0.1, 0.75≤ c ≤ 9.0, 0≤d ≤ 1.0 0 ≤ e ≤1.0, 0.001 ≤x ≤ 0.1, 0.001 ≤y ≤ 0.2, 0 ≤β ≤ 1.0 where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤1.0, c / (a + b) = 1.5 - 1.9: and the color of the luminescence is blue-green after excitation .

7.

The luminescent material of prolonged light persistence according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.5 <a <6.0, 0.0001 ≤b≤0.1, 0.5≤c ≤ 6.6, 0≤d≤1.0 0 ≤e≤1.0, 0.001≤x≤ 0.1, 0.001 ≤y ≤ 0.2, 0 ≤β ≤ 1.0 where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤1.0, (a + b) / c = 0.8 - 1.2: the amount (expressed in moles) of Ca is not less than 3 , 5 times the sum of Sr and Mg; or the amount (expressed in moles) of Ca is not less than 3.5 times the amount of Sr or Mg; and the color of the luminescence is purple-blue after excitation.

8.

The luminescent material of prolonged light persistence according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.5 <a <6.0, 0.0001 ≤b≤0.1, 0.5≤c ≤ 6.6, 0≤d≤1.0 0 ≤ e ≤1.0, 0.001 ≤x ≤ 0.1, 0.001 ≤y ≤ 0.2, 0 ≤β ≤ 1.0 where 0.5 <(a + b) ≤ 6.0, 0 <(d + e) ≤1.0, (a + b) / c = 0.9 - 1.1: the ratio of the quantity (expressed in moles) between Ca and Sr is 0.6 to 1.5; and the color of the luminescence is white after excitation.

9.

The luminescent material of prolonged light persistence according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.5 <a <6.0, 0.01 ≤ b ≤1.5, 0.5 ≤ c ≤ 3.5, 0≤ d ≤1.0 0 ≤e ≤1.0, 0.001≤x ≤0.2, 0.00001≤y≤0.2, 0 ≤β≤1.0 where 0.5 < (a + b) ≤6.0, 0 <(d + e) ≤1.0, (a + b) / c = 2.0 - 3.3: and the color of the luminescence is red after excitation .

10.

The luminescent material of prolonged light persistence according to claim 1 or 2, characterized in that said molar ratios satisfy: 0.01 ≤ x ≤ 0.25, 0.01 ≤ and ≤ 0.3, and the material has a load fast

eleven.

A method for the preparation of a luminescent material of prolonged light persistence, characterized in that, the raw materials used are composed of the following elements, or the sulfur and / or selenium is (are) used elementally, and the Elements are formulated with molar ratios satisfying the formula:

aMO-bM '(Sβ Se1-β · c Al2O3 · d B2O3 · e P2O5: x Eu · and Ln where: M is (n) selected from Sr, Ca, Ba and Mg, and any combinations thereof; M 'is (s) selected between Sr, Ca and Ba, and any combinations thereof; Ln (n) is selected from Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, and Sm and any combinations thereof; a, b, c, d, e, x and y, are molar ratios, where 0.5 <a <6.0, 0.0001 ≤ b≤ 2.0, 0.5≤ c ≤9.0, 0 ≤ d ≤ 1.0, 0 ≤ e ≤ 1.0, 0.00001 ≤x ≤ 0.25, 0.00001 ≤y ≤ 0.3, 0 ≤ β ≤ 1.0 0.5 <(a + b) ≤ 6.0 0 <(d + e) ≤ 1.0 The preparation process is a solid state high temperature reaction method, the raw materials of the elements are weighed and mixed homogeneously to form a mixture, said mixture is it is first sintered at a temperature between 700 and 1100 ° C for 2-20 hours in an oxidizing atmosphere, then sintered at a temperature between 1100 ° C and 1550 ° C for 2-30 hours in a reducing atmosphere, and then cooled , it is pulverized and screened.

12.

The method of preparing luminescent materials of prolonged light persistence, according to claim 11, characterized in that said reducing atmosphere is selected from hydrogen, ammonia, nitrogen and hydrogen or the presence of carbon particles.

13.

The method for the preparation of luminescent materials of prolonged light persistence according to claim 12, characterized in that said reducing atmosphere comprises no more than 10% H2S.

14.

The method for the preparation of luminescent materials of prolonged light persistence according to claim 11, characterized in that NH4Cl, NH4F, (NH4) 2HPO4, glucose, urea, Li2CO3, SrF2, CaF2, CaSO4, SrS, CaS, SrSO4 are added , SrHPO4 or CaHPO4, in an amount of 0-30% by weight based on the weight of the raw materials in the raw materials to participate in the solid phase reaction.