CN114350350B - Pigment with photoluminescence, mechanoluminescence and light-dependent heterochromatic effect as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a coloring material having both photoluminescence, mechanoluminescence and photochromic effects, a preparation method and an application thereof. The coloring material with photoluminescence, mechanoluminescence and photochromic effects of the present invention comprises the following components in mass percent: europium-dysprosium-zirconium co-doped strontium aluminate fluorescent powder: 10% to 90%; Pigment with light-variable color effect: 10% to 90%. The preparation method of the coloring material with photoluminescence, mechanoluminescence and photochromic effect of the present invention comprises the following steps: co-doping europium-dysprosium-zirconium aluminate phosphor with photochromic effect The colorants are physically mixed and obtained. The colorant of the present invention has both photoluminescence, mechanoluminescence and photochromic effects, and the color changing effect is obvious under different light source conditions, and its preparation process is simple, the cost is low, and it is easy to carry out industrial production. It has broad application in the field of anti-counterfeiting technology application prospects.

Description

A kind of colorant with photoluminescence, mechanoluminescence and photochromic effect and its preparation preparation methods and applications

technical field

The invention relates to the field of anti-counterfeiting technology, in particular to a coloring material with photoluminescence, mechanoluminescence and photochromic effects, and a preparation method and application thereof.

Background technique

Anti-counterfeiting technology refers to the measures taken to facilitate users to distinguish the authenticity for the purpose of anti-counterfeiting, which has practical application value for social stability and economic development. Traditional anti-counterfeiting technologies such as scratch-off, barcode, and watermark all have problems such as single mode and easy to be counterfeited, and the security is not high, while advanced anti-counterfeiting technologies such as radio frequency identification and laser holography have the problem of high cost, and their application is greatly restricted . In recent years, fluorescent anti-counterfeiting technology has become the frontier and hot spot of research, and optical materials are the key to fluorescent anti-counterfeiting technology. Existing fluorescent anti-counterfeiting technologies generally use optical materials such as organic dyes, semiconductor quantum dots, and rare earth-doped luminescent powders. These optical materials do not have anti-counterfeiting capabilities under normal circumstances, but can only be displayed under the excitation of specific wavelength light. Luminescence characteristics, a single anti-counterfeiting mode, and high imitability are still difficult to fully meet the needs of practical applications.

Therefore, it is particularly important to develop a multifunctional powder that is non-toxic, stable in chemical properties, and can exhibit different colors and luminescent properties under different environmental conditions, which will help broaden the application mode of fluorescent anti-counterfeiting technology and significantly improve anti-counterfeiting safety.

Contents of the invention

The object of the present invention is to provide a coloring material with photoluminescence, mechanoluminescence and photochromic effects, its preparation method and application.

The technical scheme that the present invention takes is:

A coloring material having both photoluminescence, mechanoluminescence and photochromic effects, which comprises the following components in mass percentage:

Europium-dysprosium-zirconium co-doped strontium aluminate phosphor: 10% to 90%;

Pigment with light-variable color effect: 10% to 90%.

Preferably, the general chemical formula of the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is: SrAl ₂ O ₄ :Eu ²⁺ _0.02 ,Dy ^{3 +} _0.03 ,Zr ⁴⁺ _x , where 0<x ≤0.2.

Preferably, the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is prepared by the following method: referring to the general chemical formula SrAl ₂ O ₄ :Eu ²⁺ _0.02 ,Dy ³⁺ _0.03 ,Zr ⁴⁺ each element in _x The stoichiometric ratio is mixed with SrCO ₃ , Al ₂ O ₃ , Eu ₂ O ₃ , Dy ₂ O ₃ , ZrO ₂ and flux, then placed in a reducing atmosphere for calcination, and then ground and sieved after cooling to obtain Europium-dysprosium-zirconium co-doped strontium aluminate phosphor.

Preferably, the flux is selected from at least one of boric acid, chloride salts, fluoride salts, and ammonium salts.

Preferably, the amount of flux added is 0-12% of the total mass of SrCO ₃ , Al ₂ O ₃ , Eu ₂ O ₃ , Dy ₂ O ₃ and ZrO ₂ .

Preferably, the reducing atmosphere is a N ₂ -H ₂ mixed atmosphere.

Preferably, the calcination is carried out at 1100° C. to 1400° C., and the holding time is 1 h to 6 h.

Preferably, the mesh size selected for the sieving is 100 mesh to 325 mesh.

Preferably, the particle size of the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is ≤150 μm.

Preferably, the colorant with light-dependent color effect is selected from at least one of holmium molybdate, neodymium molybdate, neodymium disilicate, and neodymium aluminate.

Preferably, the colorant with photochromic effect is prepared by the following method: refer to the stoichiometry of each element in the general chemical formula Ho ₂ MoO ₆ , Nd ₂ MoO ₆ , NdAlO ₃ and Nd ₂ Si ₂ O ₇ Weigh Ho ₂ O ₃ , Nd ₂ O ₃ , MoO ₃ , Al ₂ O ₃ , SiO ₂ and flux, mix them, place them in air atmosphere for calcination, and then grind and sieve after cooling to obtain Pigment with light-dependent effect.

Preferably, the flux is selected from at least one of boric acid, chloride salts, fluoride salts, and ammonium salts.

Preferably, the added amount of the fluxing agent is 0-6% of the total mass of other raw materials.

Preferably, the calcination is carried out at 1000° C. to 1300° C., and the holding time is 1 h to 6 h.

Preferably, the mesh size selected for the sieving is 100 mesh to 325 mesh.

Preferably, the particle size of the colorant with light-shifting effect is ≤150 μm.

The preparation method of the above-mentioned colorant with photoluminescence, mechanoluminescence and light-dependent color effect comprises the following steps: co-doping europium-dysprosium-zirconium strontium aluminate phosphor and the light-dependent color material By physical mixing, a color material with both photoluminescence, mechanoluminescence and photochromic effects can be obtained.

The beneficial effects of the present invention are: the colorant of the present invention has both photoluminescence, mechanoluminescence and photochromic effects, and the color changing effect is obvious under different light source conditions, and its preparation process is simple, low in cost, and easy to carry out industrial production , has broad application prospects in the field of anti-counterfeiting technology.

Specifically:

1) The color material of the present invention has obvious discoloration effects under different light source conditions (for example: D65, A, F2, F11 and ultraviolet light), and can be effectively excited by ultraviolet light, sunlight and fluorescence to emit yellow-green light;

2) The pigment of the present invention can also emit light under mechanical excitation;

3) The preparation process of the pigment of the present invention is simple, low in cost, easy to carry out industrialized production, and can be applied to the field of anti-counterfeiting security technology.

Description of drawings

Fig. 1 is the XRD pattern of the color material having both photoluminescence, mechanoluminescence and photochromic effects of Example 1.

Fig. 2 is the PL diagram of the coloring material having both photoluminescence, mechanoluminescence and photochromic effects in Example 1.

Fig. 3 is the ML diagram of the colorant of Example 1 having both photoluminescence, mechanoluminescence and photochromic effects.

Detailed ways

The present invention will be further explained and illustrated below in conjunction with specific embodiments.

Example 1:

A coloring material having both photoluminescence, mechanoluminescence and photochromic effects, the preparation method of which comprises the following steps:

1) Referring to the general chemical formula SrAl ₂ O ₄ : 0.02Eu ²⁺ , 0.03Dy ³⁺ , 0.05Zr ⁴⁺ , weigh 2.9526g of SrCO ₃ , 2.0392g of Al ₂ O ₃ , and 0.0704g of Eu according to the stoichiometric ratio ₂ O ₃ , 0.01119g of Dy ₂ O ₃ , 0.1232g of ZrO ₂ and 0.1059g of H ₃ BO ₃ were mechanically mixed, and then the obtained mixed powder was added to an alumina crucible and placed in a tube furnace, filled with In a reducing atmosphere composed of _N2 and _H2 at a volume ratio of 19:1, heat at 1300°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain europium-dysprosium-zirconium co-doped strontium aluminate phosphor;

2) Referring to the general chemical formula Ho ₂ MoO ₆ , weigh 7.5572g of Ho ₂ O ₃ and 2.8788g of MoO ₃ according to the stoichiometric ratio for mechanical mixing, then add the obtained mixed powder into an alumina crucible and place it in a tubular In the furnace, fill with air, keep warm at 1000°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain holmium molybdate pigment;

3) Mix europium-dysprosium-zirconium co-doped strontium aluminate phosphor and holmium molybdate coloring material according to the mass ratio of 1:1, and grind them to obtain photoluminescence, mechanoluminescence and photochromic effects colorant.

Performance Testing:

1) The X-ray diffractometer whose model is X'Pert Pro of PANalytical Company of the Netherlands is used to test the crystal structure of the colorant having both photoluminescence, mechanoluminescence and photochromic effects in this embodiment, and the obtained X-ray The diffraction (XRD) pattern is shown in FIG. 1 .

It can be seen from Fig. 1 that the diffraction peaks of the coloring material of this embodiment with both photoluminescence, mechanoluminescence and light-dependent heterochromatic effects are sharp, and the crystallinity is good, and its crystal phase includes SrAl ₂ O ₄ crystal phase and Ho ₂ MoO ₆ crystal phases, all of which are monoclinic crystals.

2) The fluorescence emission performance of the coloring material having both photoluminescence, mechanoluminescence and photochromic effect of this embodiment is tested by using a fluorescence spectrometer of the model TRIA-320 from Edinburgh, UK, and the obtained photoluminescence ( PL) spectrogram shown in Figure 2.

It can be seen from FIG. 2 that the color material with photoluminescence, mechanoluminescence and phototropic effects of this embodiment has a broad emission spectrum at 450nm-600nm (yellow-green light) under excitation of light with a wavelength of 365nm.

3) The mechanoluminescence performance of the coloring material having both photoluminescence, mechanoluminescence and photochromic effect of this embodiment is tested by using a mechanoluminescence instrument, and the obtained mechanoluminescence (ML) spectrum is shown in Figure 3 shown.

It can be seen from Fig. 3 that the colorant of this embodiment with both photoluminescence, mechanoluminescence and photochromic effects has obvious mechanoluminescence performance, and the test sample will have a clear mechanoluminescence peak under the excitation of impact force , the luminous intensity increases sharply at first, and then gradually decreases.

According to the comprehensive test, the color material in this embodiment with both photoluminescence, mechanoluminescence and photochromic effects can be effectively excited by ultraviolet light, sunlight and fluorescence, and emit yellow-green light visible to the naked eye. Under the action of mechanical force such as extrusion force, it emits yellow-green light, and it can also have a different color effect under different light sources (such as: sunlight D65, incandescent lamp A, cool white fluorescent lamp F2 and triple-frequency fluorescent lamp F11), L*a*b* The value test results show that the color difference between the standard light source D65 (light yellow-green) and F11 (red tone) is 12.48.

Example 2:

A coloring material having both photoluminescence, mechanoluminescence and photochromic effects, the preparation method of which comprises the following steps:

1) Referring to the general chemical formula SrAl ₂ O ₄ : 0.02Eu ²⁺ , 0.03Dy ³⁺ , 0.05Zr ⁴⁺ , weigh 2.9526g of SrCO ₃ , 2.0392g of Al ₂ O ₃ , and 0.0704g of Eu according to the stoichiometric ratio ₂ O ₃ , 0.01119g of Dy ₂ O ₃ , 0.1232g of ZrO ₂ and 0.1059g of H ₃ BO ₃ were mechanically mixed, and then the obtained mixed powder was added to an alumina crucible and placed in a tube furnace, filled with In a reducing atmosphere composed of _N2 and _H2 at a volume ratio of 19:1, heat at 1300°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain europium-dysprosium-zirconium co-doped strontium aluminate phosphor;

2) Referring to the general chemical formula Nd ₂ MoO ₆ , weigh 6.7296g of Nd ₂ O ₃ and 2.8788g of MoO ₃ according to the stoichiometric ratio for mechanical mixing, then add the obtained mixed powder into an alumina crucible and place it in a tubular In the furnace, fill with air, keep warm at 1200°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain holmium molybdate pigment;

3) Mix europium-dysprosium-zirconium co-doped strontium aluminate phosphor and holmium molybdate coloring material according to the mass ratio of 1:1, and grind them to obtain photoluminescence, mechanoluminescence and photochromic effects colorant.

According to the comprehensive test, the color material of this embodiment with both photoluminescence, mechanoluminescence and photochromic effects can be effectively excited by ultraviolet light, sunlight and fluorescence, and emit yellow-green light visible to the naked eye. Under the action of mechanical force such as extrusion force, it emits yellow-green light, and it can also have a different color effect under different light sources (such as: sunlight D65, incandescent lamp A, cool white fluorescent lamp F2 and triple-frequency fluorescent lamp F11), L*a*b* The value test results show that: the color difference between the standard light source A (purple) and F11 (cyan) is 8.09.

Example 3:

A coloring material having both photoluminescence, mechanoluminescence and photochromic effects, the preparation method of which comprises the following steps:

1) Referring to the general chemical formula SrAl ₂ O ₄ : 0.02Eu ²⁺ , 0.03Dy ³⁺ , 0.05Zr ⁴⁺ , weigh 2.9526g of SrCO ₃ , 2.0392g of Al ₂ O ₃ , and 0.0704g of Eu according to the stoichiometric ratio ₂ O ₃ , 0.01119g of Dy ₂ O ₃ , 0.1232g of ZrO ₂ and 0.1059g of H ₃ BO ₃ were mechanically mixed, and then the obtained mixed powder was added to an alumina crucible and placed in a tube furnace, filled with In a reducing atmosphere composed of _N2 and _H2 at a volume ratio of 19:1, heat at 1300°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain europium-dysprosium-zirconium co-doped strontium aluminate phosphor;

2) Referring to the general chemical formula Nd ₂ Si ₂ O ₇ , according to the stoichiometric ratio, weigh 6.7296g of Nd ₂ O ₃ , 2.4032g of SiO ₂ and 0.1827g of H ₃ BO ₃ for mechanical mixing, and then mix the obtained mixed powder Put the body into an alumina crucible and place it in a tube furnace, fill it with air, keep it warm at 1200°C for 3 hours, then cool, grind, and pass through a 150-mesh sieve to obtain holmium molybdate pigment;

3) Mix europium-dysprosium-zirconium co-doped strontium aluminate phosphor and holmium molybdate coloring material according to the mass ratio of 1:1, and grind them to obtain photoluminescence, mechanoluminescence and photochromic effects colorant.

According to the comprehensive test, the color material in this embodiment with both photoluminescence, mechanoluminescence and photochromic effects can be effectively excited by ultraviolet light, sunlight and fluorescence, and emit yellow-green light visible to the naked eye. Under the action of mechanical force such as extrusion force, it emits yellow-green light, and it can also have a different color effect under different light sources (such as: sunlight D65, incandescent lamp A, cool white fluorescent lamp F2 and triple-frequency fluorescent lamp F11), L*a*b* The value test results show that the color difference between the standard light source A (light pink) and F11 (light yellow) is 6.61.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (7)

1. A coloring material having both photoluminescence, mechanoluminescence and photochromic effects, characterized in that it comprises the following components in mass percent: Europium-dysprosium-zirconium co-doped strontium aluminate phosphor: 10% to 90%; Pigment with light-variable color effect: 10% to 90%; The general chemical formula of the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is: SrAl ₂ O ₄ :Eu ²⁺ _0.02 ,Dy ³⁺ _0.03 ,Zr ⁴⁺ _x , where 0<x≤0.2; The colorant having the effect of varying color with light is selected from at least one of holmium molybdate, neodymium molybdate, neodymium disilicate, and neodymium aluminate; The particle size of the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is ≤150 μm; The particle diameter of the colorant with light-dependent color effect is ≤150 μm. 2. The coloring material having photoluminescence, mechanoluminescence and photochromic effect according to claim 1, characterized in that: the europium-dysprosium-zirconium co-doped strontium aluminate phosphor is obtained by the following method Prepared: _refer to the stoichiometric ratio _{of each element} in the general chemical _formula SrAl ₂ O ₄ :Eu ^{2 +} _0.02 , Dy ³⁺ _{0.03 ,} Zr ⁴⁺ _{x 3.} ZrO ₂ is mixed with a flux, then placed in a reducing atmosphere for calcination, and then ground and sieved after cooling to obtain europium-dysprosium-zirconium co-doped strontium aluminate phosphor. 3. The coloring material with photoluminescence, mechanoluminescence and light-following effect according to claim 2, characterized in that: the flux is selected from boric acid, chloride salt, fluoride salt, ammonium salt at least one of the 4. The coloring material with photoluminescence, mechanoluminescence and photochromic effects according to claim 2, characterized in that: the amount of flux added is SrCO ₃ , Al ₂ O ₃ , Eu ₂ 0-12% of the total mass of O ₃ , Dy ₂ O ₃ and ZrO ₂ . 5. The colorant with photoluminescence, mechanoluminescence and photochromic effects according to claim 2, characterized in that: the calcination is carried out at 1100°C-1400°C, and the holding time is 1h-6h . 6. The preparation method of the colorant having photoluminescence, mechanoluminescence and photochromic effect according to any one of claims 1 to 5, characterized in that it comprises the following steps: mixing europium-dysprosium-zirconium The co-doped strontium aluminate phosphor is physically mixed with the color material with light-dependent color effect, and the color material with photoluminescence, mechanoluminescence and light-dependent color effect is obtained. 7. The application of the coloring material having photoluminescence, mechanoluminescence and photochromic effects described in any one of claims 1 to 5 in the field of anti-counterfeiting.

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