CN1303831A - Glowing Glaze - Google Patents

Abstract

A light-storage type luminescent glaze is composed of a variety of ion-activated long afterglow luminescent materials and a basic flux. The weight ratio of the long afterglow luminescent material to the basic flux is 45-2% to 55-98%. The luminescent glaze can be used to manufacture luminescent ceramics, luminescent enamels and luminescent glass products, which have high luminescent brightness, clear patterns, various colors, excellent glaze quality, strong mechanical properties and high chemical stability.

Description

Glowing Glaze

The invention relates to glazes, especially glazes with long afterglow luminous function.

Due to the emergence of luminous luminous materials, ceramics, enamel and other glazed silicate products with luminous function have been developed successively. Such as CN1197043A is a printing glaze composed of frit powder, fluorescent powder and printing oil, which is applied to glazed tiles and fired to form luminous glazed tiles, which have a luminous function after light irradiation. However, the afterglow time is not long (5+ hours). CN1198413A and CN1202472A provide luminescent enamel and ceramic glaze, which are composed of luminescent powder, basic glaze and additives, especially the composition formula of the luminescent powder used is MO·nAl ₂ O ₃ :Eu ⁺² where M=Sr, Mg, Ba, Ca, can be one or more, n=1-3; each part is composed of (parts by weight): luminescent powder 20-50, basic glaze 45-100, auxiliary material 5-20, the luminescent material is a single Aluminate long afterglow materials excited by europium ions have relatively low luminous brightness and single luminescent color; and the luminescent material has a single component, which is combined with a basic flux to make a luminescent glaze, which will cause defects such as uneven glaze surface and poor quality when used , its performance is unsatisfactory.

Aiming at the defects in the above-mentioned prior art, the present invention uses a variety of ion-activated long-lasting luminescent materials to produce a luminescent glaze with wide application range, high luminous brightness, long luminescent time and excellent glaze quality.

The luminescent glaze provided by the invention contains a basic flux (1) and multiple ion-activated high-efficiency light storage type long-lasting luminescent materials (2).

1. The glaze formula of the basic flux is:

Wherein R is the combination of one or more elements in Li, Na, K;

M is a combination of one or more elements of Ca, Mg, Sr, Ba, Zn, and Pb;

a, b, c, d, and e are all coefficients, and their values are: 0.1≤a≤0.9; 0.1≤b≤0.9; 0.05≤c≤2.5; 0.5≤d≤12.0; 0.5≤e≤11.0; and a+ b=1.0.

In the luminescent glaze, the ratio of the basic flux (1) to the long-lasting luminescent material (2) is 55%-98% to 45%-2%, preferably 82%-95% to 18%-5%. Due to the use of high-efficiency long-lasting luminous materials, and the appropriate ratio of basic flux and luminous materials, products made of this luminous glaze can achieve both excellent glaze quality and luminous brightness.

The luminescent material used in the present invention is a variety of ion-activated long-lasting luminescent materials (2), including four types of silicates, aluminates, mixtures of silicates and aluminates, and sulfides.

2-1． The composition expression of a variety of ion-activated silicate long-lasting luminescent materials is:

αMO·βM'O·γSiO ₂ ·δR:Eu _x Ln _y

Wherein M is a combination of one or more elements in Sr, Ca, Ba, Zn;

M' is a combination of one or more elements in Mg, Cd, Be;

R is one of B ₂ O ₃ , P ₂ O ₅ or a combination of two compounds;

Ln is a combination of one or more elements of Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Er, Mn, Bi, Sn, Sb;

α, β, γ, δ, x, y are molar coefficients,

0.6≤α≤6; 0≤β≤5; 1≤γ≤9;

0≤δ≤0.7; 0.00001≤x≤0.2; 0≤y≤0.3.

Further experiments have shown that among the above-mentioned silicate luminescent materials, the following two types of luminescent materials can be used to produce luminescent glazes with higher brightness, and the main chemical composition is:

2-1-1.(Sr _1-z Ca _z ) ₂ MgSi ₂ O ₇ :Eu _x Ln _y

2-1-2． (Sr _1-z Ca _z ) ₃ MgSi ₂ O ₈ :Eu _x Ln _y

Ln is a combination of one or more elements in La, Ce, Dy, Tm, Ho, Nd, Er, Sb, Bi;

z is a coefficient: 0≤z≤1;

x and y are molar coefficients: 0.0001≤x≤0.2; 0.0001≤y≤3.0.

The above two types of preferred silicate long-lasting luminescent materials can emit blue, blue-green, green, yellow-green, and yellow light respectively with different z values. For example, when z=0, they emit blue light; when z=0.5, they emit blue light. green light.

2-2． The composition expression of various ion-activated aluminate long-lasting luminescent materials is:

αMO·βAl ₂ O ₃ ·γB ₂ O ₃ :Eu _x Ln _y

Wherein M is a combination of one or more elements in Mg, Ca, Sr, Ba, Zn, Cd;

Ln is a combination of one or more elements of Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi;

α, β, γ, x, y are molar coefficients,

0.5≤α≤6; 0.5≤β≤9; 0.0001≤γ≤0.3;

0.00001≤x≤0.15; 0.00001≤y≤0.2.

Further experiments show that the above-mentioned aluminate luminescent materials are preferred, and the following two types of luminescent materials with main chemical compositions can produce higher brightness luminescent glazes:

2-2-1． MAl ₂ O ₄ :Eu _x Ln _y

Wherein Ln is a combination of one or more elements in La, Ce, Dy, Ho, Nd, Er;

M is one or a combination of two elements in Sr, Ca, Mg, Ba, Zn;

x and y are molar coefficients, 0.0001≤x≤0.15;

0.0001≤y≤0.2. Depending on the M, the luminous color is different. For example, when M=Sr, it is yellow-green luminous; when M=Ca, it is blue-purple luminous.

2-2-2． M ₄ Al ₁₄ O ₂₅ :Eu _x Ln _y

Wherein Ln is a combination of one or more elements in Pr, Ce, Dy, Ho, Nd, Er;

M is a combination of one or more elements in Sr, Ca, Mg, Ba, Zn;

x and y are molar coefficients, 0.0001≤x≤0.25; 0.0001≤y≤0.3.

2-3． The chemical composition expression of various ion-activated sulfide long-lasting luminescent materials is:

(Ca _1-z Sr _z )S:Eu _x Ln _y

Wherein Ln is a combination of one or more elements in Er, Dy, La, Tm, Y;

z is a coefficient, 0≤z≤1;

x, y are molar coefficients, 0.00001≤x≤0.2; 0.00001≤y≤

0.15.

The material can emit red and orange light depending on the z value.

2-4． In order to improve the quality of the luminous glaze surface and rich luminous colors, the above-mentioned silicate long afterglow luminescent materials and aluminate long afterglow materials can also be used in combination. Generally speaking, the glaze quality of the luminous glaze using the above-mentioned silicate long-lasting luminescent material is better, and the luminous color is also richer; while the luminous glaze using the above-mentioned aluminate long-lasting luminescent material has relatively high brightness, and the mixed use of two The luminous glaze of the latter can achieve better glaze quality and stronger luminous intensity.

Due to the different materials of the green bodies, their physical and chemical properties vary greatly. The basic flux can be adjusted accordingly for different green bodies to adapt to the properties of the green bodies and achieve the best effect.

Secondly, because the luminescent materials used are divided into four types: silicates, aluminates, mixtures of silicates and aluminates, and sulfides, some components in the basic flux for different types of luminescent materials should also be adjusted accordingly. Because at high temperature, liquid-liquid and liquid-solid reactions will occur between the luminescent material and the base glaze. If the base glaze cannot match the luminescent material, the afterglow intensity will decrease, and the smoothness and gloss of the glaze surface will be poor. Defects such as air bubbles, sinking glaze, rolling glaze, etc. Therefore, the content of each component in the basic glaze is adjusted according to the content of the components in the above four types of luminescent materials that will react with the glaze.

According to the various proportions of the basic flux, through a series of experiments, the following basic flux is preferred in the present invention: 1-1. As mentioned above (1) in the glaze formula of the basic flux, the coefficient value in the glaze formula of the better basic flux is:

0.1≤a≤0.5; 0.5≤b≤0.9; 0.05≤c≤1.0;

1.0≤d≤8.0; 0.5≤e≤8.0. 1-2. As mentioned above (1) in the glaze formula of the basic flux, the coefficient value in the glaze formula of the better basic flux is:

0.15≤a≤0.45; 0.55≤b≤0.85; 0.1≤c≤0.7;

1.0≤d≤6.0; 1.0≤e≤6.0. 1-3. As mentioned above (1) in the glaze formula of the basic flux, the coefficient value in the glaze formula of the better basic flux is:

1-5．如上所述(1)基础熔剂的釉式中，其较好的基础熔剂的1-5．如上所述(1)基础熔剂的釉式中，其较好的基础熔剂的釉式为：

a=0.43; b=0.57; c=0.41; d=1.36; e=1.29. 1-4. As mentioned above (1) in the glaze formula of the basic flux, the glaze formula of the better basic flux is:

1-5． As mentioned above (1) in the glaze formula of the basic flux, 1-5 of the preferred basic flux. As mentioned above (1) in the glaze formula of the basic flux, the glaze formula of the better basic flux is:

For example, in the glaze formula of the above-mentioned basic flux (1), some components that basically have no or little influence on the luminescent glaze are not listed, such as a small amount of Bi ₂ O ₃ , Sb ₂ O ₃ , ZrO ₂ or Some rare earth elements and Fe ₂ O ₃ brought in due to the purity of raw materials are not essential components of the glaze. However, a small amount of addition has no effect on the luminous glaze itself, as long as the main composition of the basic flux is in the listed basic flux (1), it is the scope of protection required by this patent.

The manufacturing method of the luminous glaze is that the basic flux is fired first, and then the glaze is made by using the basic flux and the long-lasting luminescent material. The steps are:

1) Preparation of basic flux: ingredients are prepared according to the formula of basic flux. The raw materials containing these elements can be oxides, hydroxides, carbonates, boric acid (salt), oxalate, feldspar, quartz, clay, etc. Mix it evenly, burn it at 1000-1300°C for 0.5-5 hours, keep it warm for 0.5-2 hours, then quench it in water, dry it, crush it and sieve it.

2) Preparation of long-lasting luminescent materials: adopt solid-state reaction method, carry out ingredients according to the chemical composition of the above-mentioned long-lasting luminescent materials, and select raw materials containing these elements, which can be their oxides, hydroxides, carbonates, sulfates, grasses, etc. salt, etc., grind it finely and mix it, then fire it at 1000-1550°C for 0.5-5 hours, use reducing atmosphere such as H ₂ , N ₂ +H ₂ , CO, C powder, etc., crush it after cooling, and sieve made.

3) Synthesis of luminescent glaze: mix the basic flux and long-lasting luminescent material according to the designed ratio. Made by ball milling.

The luminescent glaze can be made into a glaze suitable for ceramics, enamel and glass due to the difference in the formula of the basic flux, and the firing temperature of the glaze is 580-1200°C.

The test method for the luminous afterglow intensity of the luminous glaze is to apply the prepared luminous glaze on the ceramic body or enamel plate with a thickness of 0.2mm, and sinter it to make a luminous glaze, store it in the dark room for more than 10 hours, take it out and place it in the standard The D65 light source is irradiated for 10 minutes under the illumination of 1000Lx. The luminous intensity over time was measured with a luminance meter. Simultaneously with the test, the comparison sample of the prior art is stimulated to test and compare under the same conditions.

The product of the present invention uses a high-efficiency light storage type long afterglow luminescent material, which has high luminous brightness and long time, and can have multiple luminescent colors such as red, orange, yellow-green, green, blue-green, blue, purple, etc. Juan or special purpose has an excellent effect. Various luminescent ceramics, enamel and glass products can be manufactured. Such as luminous ceramic handicrafts, luminous ceramics, enamel signs, luminous ceramic waist strips, waistlines, decorative tiles, floor tiles. The luminescent product has the advantages of high luminous brightness, clear patterns, various colors, excellent glaze quality, strong mechanical properties and high chemical stability. It has good application value in the fields of architectural decoration, handicraft products, fire indication system and so on. In addition, due to the reasonable formula, it is more obvious than the existing technology in terms of glaze quality and light storage and luminescence performance.

The following examples are further compared and explained: Example 1: Luminescent glaze for ceramics (1) preparation of basic flux: basic flux glaze formula: Raw material ratio (grams):

SiO ₂ : 34.g Al ₂ O ₃ : 4.6g

H ₃ BO ₃ : 20.8 g CaCO ₃ : 10.2 g

MgO: 0.7g SrCO ₃ : 7.6g

Na ₂ CO ₃ : 9.3 g KNO ₃ : 12 g

Calculate the corresponding raw material composition formula according to the chemical composition of the basic flux, accurately weigh, mix, and keep warm at 1150°C for 0.5 hours to obtain a frit, which is passed through a 300-mesh sieve by dry ball milling to obtain the basic flux.

(2) Long afterglow luminescent material

Strontium aluminate blue green long-lasting luminescent material activated by europium, dysprosium and lanthanum, in the aluminate long-lasting luminescent material in specification 2-2, select M=Sr,Ln=Dy _0.09 La _0.02 ,x=0.06,a =4,b=7,c=0.05, namely

4SrO 7Al ₂ O ₃ 0.05B ₂ O ₃ :Eu _0.06 Dy _0.09 La _0.02

According to the element composition in the above formula, select the raw materials, mix them thoroughly, and sinter at 1320°C in a reducing atmosphere of H ₂ 5%+ _N 95% for 3 hours at high temperature, and cool through a 300-mesh sieve to obtain a blue-green long afterglow Luminescent material.

3) Preparation of luminescent glaze

Mix the above-mentioned blue-green strontium aluminate long-lasting luminescent material with the above-mentioned basic flux at a ratio of 20% to 80% to prepare a blue-green luminescent glaze suitable for ceramics, and the firing temperature is 850-900°C.

In order to compare the effects of luminescent glazes prepared from various ion-activated and single Eu ion-activated aluminate long-lasting materials, the present invention selects single-europium ion-activated aluminate long-lasting luminescent materials, and its main chemical composition is:

4SrO 7Al ₂ O ₃ 0.05B ₂ O ₃ :Eu _0.06

Using the same method as in Example 1 to make a single europium ion-activated luminescent glaze for ceramics, the above-mentioned single-ion-activated blue-green strontium aluminate long-lasting luminescent material 4SrO 7Al ₂ O ₃ 0.05B ₂ O ₃ :Eu0 .06 is mixed evenly with the above-mentioned base flux at a ratio of 40% to 60%, that is, comparative sample 1.

The luminescent glazes for ceramics prepared in Example 1 and Comparative Sample 1 were mixed with 1.5% CMC, respectively applied to the surface of ordinary ceramic bodies, dried and kept at 860°C for 1 hour, and the luminous afterglow brightness was tested respectively. The results are shown in the table 1. Table 1 sample Luminous afterglow intensity (mcd/m ² ) 5min 10min 30min 60min 120min Comparative Sample 1 Example 1 41 13 4 2 0.9272 142 43 22 12

原料配比It can be seen from the table that the brightness of Example 1 is much higher than that of Comparative Sample 1, and the afterglow time is also longer. Under the same conditions, the glazed surface of Example 1 is smooth and flat, basically without air bubbles, while Comparative Sample 1 has a small amount of air bubbles, and the glazed surface appears uneven. Embodiment 2: Preparation of luminescent glaze for ceramics (1) basic flux Basic flux glaze formula:

Raw material ratio

SiO ₂ : 32.7g Al ₂ O ₃ : 4.4g

H3BO ₃ : 2.2g CaCO ₃ : 10.7g

MgO: 0.8g SrCO ₃ : 8g

Na ₂ CO ₃ : 9.5 g KNO ₃ : 9.8 g

Feldspar: 2 grams

According to the chemical composition of the basic flux, the corresponding raw material composition formula is accurately weighed and mixed, and kept at 1180°C for 0.5 hours. After the frit is obtained, it is dry ball milled and passed through a 300-mesh sieve to obtain the basic flux.

(2) Long afterglow luminescent material

Strontium aluminate yellow-green long-lasting luminescent material activated by europium, dysprosium and praseodymium, its main chemical composition is: SrAl ₂ O ₄ :Eu _0.06 Dy _0.09 Pr _0.01

(3) Preparation of luminescent glaze

Mix the above-mentioned yellow-green strontium aluminate long-lasting luminescent material with the above-mentioned basic flux at a ratio of 13% to 87% to prepare a yellow-green luminescent glaze suitable for ceramics, and the firing temperature is 800-850°C.

In order to compare the effects of luminescent glazes prepared from various ion-activated and single Eu ion-activated aluminate long-lasting materials, the present invention selects single-europium ion-activated aluminate long-lasting luminescent materials, and its main chemical composition is: SrAl ₂ O ₄ :Eu _0.06

The luminous glaze for ceramics activated by single europium ions is prepared by the same method as in Example 2, and the above-mentioned single-ion-activated yellow-green strontium aluminate long-lasting luminescent material SrAl ₂ O ₄ :Eu _0.06 is mixed with the above-mentioned basic flux by 40% Mix evenly at a ratio of 60%, that is, comparative sample 2.

The luminescent glazes for ceramics prepared in Example 2 and Comparative Sample 2 were mixed with 1.5% CMC, respectively applied to the surface of ordinary ceramic bodies, dried and kept at 820°C for 1 hour, and the luminous afterglow brightness was tested respectively. The results are shown in the table 2. Table 2 sample Luminous afterglow intensity (mcd/m ² ) 5min 10min 30min 60min 120min Comparative Sample 2 Example 2 45 12 2.1 0.6 0.3278 125 29 9 4

It can be seen from the table that the brightness of Example 2 is much higher than that of Comparative Sample 2, and the afterglow time is also longer. Under the same conditions, the glazed surface of Example 2 is smooth and flat, basically without air bubbles, while comparative sample 2 has a small amount of air bubbles, and the glazed surface appears uneven.

原料配比(克)：Example 3: Preparation of Luminous Glaze for Ceramics (1) Basic Flux Basic Flux Glaze

Raw material ratio (grams):

SiO ₂ : 38.7 Al ₂ O ₃ : 4.8

H ₃ BO ₃ : 1.5 CaCO ₃ : 0.5

MgO: 0.8 SrCO ₃ : 7.8

Na ₂ CO ₃ : 16.3

Calculate the corresponding raw material composition formula according to the chemical composition of the basic flux, accurately weigh, mix and keep warm at 1200°C for 0.5 hours, after the frit is obtained, dry ball milling, and pass through a 300-mesh sieve to obtain the basic flux.

(2) Long afterglow luminescent material:

The blue-green luminescent material of calcium strontium silicate activated by Eu, Dy, and Bi and the blue-green luminescent material of strontium calcium aluminate activated by Eu, Dy, and La are mainly composed of:

(Ca _0.5 Sr _1.5 )MgSi ₂ O ₇ :Eu _0.06 Dy _0.15 Bi _0.01

(Ca _0.15 Sr _0.85 ) ₄ Al ₁₄ O ₂₅ :Eu _0.06 Dy _0.09 La _0.02

(3) Preparation of luminescent glaze

The above blue-green strontium silicate long-lasting luminescent material (Ca _0.5 Sr _1.5 )MgSi ₂ O ₇ :Eu _0.06 Dy _0.15 Bi _0.01 and the blue-green strontium aluminate long-lasting luminescent material (Ca _0.15 Sr _0.85 ) ₄ Al ₁₄ O ₂₅ : Eu _0.06 Dy _0.09 La _0.02 is uniformly mixed with the above-mentioned basic flux at a ratio of 8% to 7% to 85% to prepare a blue-green luminescent glaze suitable for ceramics, and the firing temperature is 900-950°C.

原料配比(克)：Example 4: Preparation of Luminous Glaze for Ceramics (1) Basic Flux Basic Flux Glaze

Raw material ratio (grams):

SiO ₂ : 46.3 Al ₂ O ₃ : 6.2

H ₃ BO ₃ : 16.2 CaCO ₃ : 7.9

MgO: 0.6 SrCO ₃ : 5.9

Na ₂ CO ₃ : 14.9 KNO ₃ : 2.0

Calculate the corresponding raw material composition formula according to the chemical composition of the basic flux, accurately weigh, mix, and keep warm at 1250°C for 0.5 hours to obtain a frit, which is passed through a 300-mesh sieve by dry ball milling to obtain the basic flux. (2) Preparation of long afterglow luminescent material:

Strontium calcium silicate blue luminescent material activated by Eu, Ho, Dy, its main chemical composition is: Sr _1.8 Ca _0.2 MgSi ₂ O ₇ :Eu _0.06 Ho _0.05 Dy _0.1

(3) Preparation of luminescent glaze

原料配比(克)：The blue luminescent material of strontium calcium silicate and the above basic flux are uniformly mixed at a ratio of 9% to 91%, and a blue luminescent glaze suitable for ceramics is prepared, and the firing temperature is 800-850°C. Example 5: Luminous glaze for enamel Example 5: Luminous glaze for enamel (1) Preparation of basic flux: Basic flux Glaze formula:

Raw material ratio (grams):

SiO ₂ 44.2 Al ₂ O ₃ 5.8

H ₃ BO ₃ 17.1 CaCO ₃ 8.3

MgO 0.6 SrCO ₃ 6.3

Na ₂ CO ₃ 13.7 KNO ₃ 4.0 (2) Long afterglow luminescent material:

Calcium strontium silicate blue luminescent material activated by Eu, Dy, Sb, its chemical composition is: Sr _1.9 Ca _0.1 MgSi ₂ O ₇ : Eu _0.06 Dy _0.08 Sb _0.02 (3) Preparation of luminescent glaze

Mix the above calcium strontium silicate blue luminescent material with the above basic flux at a ratio of 11% to 89% to prepare a blue luminescent glaze suitable for ceramic enamel, and the firing temperature is 700-800°C

Example 6. Luminous enamel products

Take 100 grams of luminous enamel glaze described in Example 5, add 3 grams of urea, 0.1 grams of barium chloride, and 0.1 grams of magnesium sulfate, and mix in proportion to prepare a glaze slurry. Apply the glaze slurry to the surface of the white enamel by dipping and enamelling, and then spin off the excess glaze slurry for one minute to obtain a smooth and shiny enamel product.

Embodiment 7: A kind of luminous glazed brick product

Ball mill or stir 100 grams of luminous glaze for ceramics in Example 1 and 67 grams of printing oil evenly, take a piece of white glazed tile, and print the luminous glaze on the glazed tile with a water-based or water-oil dual-purpose printing screen. Keep it for 10 minutes, and you can fire the luminous glazed tiles with luminous patterns.

Claims (14)

1. a luminescent glaze contains basic flux and luminescent material, it is characterized in that luminescent material is the long after glow luminous material of different kinds of ions activated silicate, aluminate, sulfide or silicate and aluminate mixture; The glaze formula of basis flux is: Wherein R is the combination of one or more elements among Li, Na, the K;

M is the combination of one or more elements among Ca, Mg, Sr, Ba, Zn, the Pb;

A, b, c, d, e are coefficient, 0.1≤a≤0.9; 0.1≤b≤0.9;

0.05≤c≤2.5; 0.5≤d≤12.0; 0.5≤e≤11.0; And

a+b=1.0；

Long after glow luminous material is the 45-2% ratio with the weight percent proportioning of basic flux

55-98％。

2. luminescent glaze according to claim 1 is characterized in that the long after glow luminous material and the weight percent proportioning of basic flux are that 18-5% compares 82-95%.

3. luminescent glaze according to claim 1 is characterized in that the composition expression of described different kinds of ions activated long persistence luminescent silicate material is:

αMO·βM’O·γSiO ₂·δR:Eu _xLn _y

Wherein M is the combination of one or more elements among Sr, Ca, Ba, the Zn;

M ' is the combination of one or more elements among Mg, Cd, the Be;

R is B ₂O ₃, P ₂O ₅In one or both combination;

Ln be Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Er, Mn, Bi, Sn,

The combination of one or both elements among the Sb;

α, β, γ, δ, x, y are mole coefficient,

0.6≤α≤6；0≤β≤5；1≤γ≤9；

0≤δ≤0.7；0.00001≤x≤0.2；0≤y≤0.3。

4. luminescent glaze according to claim 1 is characterized in that the composition expression of described different kinds of ions activated aluminate long after glow luminous material is:

α MO β Al ₂O ₃γ B ₂O ₃: Eu _xLn _yWherein M is the combination of one or more elements among Mg, Ca, Sr, Ba, Zn, the Cd; Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, the Bi; α, β, γ, x, y are mole coefficient, 0.5≤α≤5; 0.5≤β≤9; 0.0001≤γ≤0.3; 0.00001≤x≤0.15; 0.00001≤y≤0.2.

5. different kinds of ions activated long persistence luminescent silicate material as claimed in claim 3 is characterized in that the main chemical constitution expression of luminescent material is:

(Sr _1-zCa _z) ₂MgSi ₂O ₇: Eu _xLn _yWherein Ln is the combination of one or more elements among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;

Z is a coefficient, 0≤z≤1;

X, y are mole coefficient, 0.0001≤x≤0.2; 0.0001≤y≤0.3.

6. different kinds of ions activated long persistence luminescent silicate material as claimed in claim 3 is characterized in that the main chemical constitution expression of luminescent material is:

(Sr _1-zCa _z) ₃MgSi ₂O ₈: Eu _xLn _yWherein Ln is the combination of one or more elements among La, Ce, Dy, Tm, Ho, Nd, Er, Sb, the Bi;

Z is a coefficient, 0≤z≤1;

X, y are mole coefficient, 0.0001≤x≤0.2; 0.0001≤y≤0.3.

7. different kinds of ions activated aluminate long after glow luminous material as claimed in claim 4 is characterized in that the main chemical constitution expression of luminescent material is:

MAl ₂O ₄: Eu _xLn _yWherein Ln is the combination of one or more elements among La, Ce, Dy, Ho, Nd, the Er;

M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;

X, y are mole coefficient, 0.0001≤x≤0.15; 0.0001≤y≤0.2.

8. different kinds of ions activated aluminate long after glow luminous material as claimed in claim 4 is characterized in that the main chemical constitution expression of luminescent material is:

M ₄Al ₁₄O ₂₅: Eu _xLn _yWherein Ln is the combination of one or more elements among Pr, Ce, Dy, Ho, Nd, the Er;

M is the combination of one or more elements among Sr, Ca, Mg, Ba, the Zn;

X, y are mole coefficient, 0.0001≤x≤0.25; 0.0001≤y≤0.3.

9. luminescent glaze according to claim 1 is characterized in that the main chemical constitution expression of described different kinds of ions activated long persistence luminous sulfide material is:

(Ca _1-zSr _z) S:Eu _xLn _yWherein Ln is the combination of one or more elements among Er, Dy, La, Tm, the Y;

Z is a coefficient, 0≤z≤1;

X, y are mole coefficient, 0.00001≤x≤0.2; 0.00001≤y≤0.15.

10. luminescent glaze according to claim 1 is characterized in that the coefficient in the glaze formula of described basic flux, and its numerical value is:

0.1≤a≤0.5；0.5≤b≤0.9；0.05≤c≤1.0；

1.0≤d≤8.0；0.5≤e≤8.0。

11. luminescent glaze according to claim 1 is characterized in that the coefficient in the glaze formula of described basic flux, its numerical value is:

0.15≤a≤0.45；0.55≤b≤0.85；0.1≤c≤0.7；

1.0≤d≤6.0；1.0≤e≤6.0。

12. luminescent glaze according to claim 1 is characterized in that the coefficient in the glaze formula of described basic flux, its numerical value is:

a=0.43；b=0.57；c=0.41；d=1.36；e=1.29。

13. luminescent glaze according to claim 1 is characterized in that the glaze formula of described basic flux is:

14. luminescent glaze according to claim 1, the glaze formula of described basic flux is during its feature: