CN109852374A - A kind of preparation method of three primary colours long-afterglow fluorescent PIG material - Google Patents
A kind of preparation method of three primary colours long-afterglow fluorescent PIG material Download PDFInfo
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- CN109852374A CN109852374A CN201910036170.8A CN201910036170A CN109852374A CN 109852374 A CN109852374 A CN 109852374A CN 201910036170 A CN201910036170 A CN 201910036170A CN 109852374 A CN109852374 A CN 109852374A
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Abstract
The invention discloses a kind of preparation methods of three primary colours long-afterglow fluorescent PIG material, belong to rare earth material illumination field.The present invention is by high-purity ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+It is mixed with borosilicate glass frit and carries out 30~60min of dry grinding mixing processing and obtain mixed powder；Mixed powder is placed in 5~30min of sintering processes under the conditions of temperature is 600~750 DEG C, then being placed in temperature is 10~15min of isothermal holding under the conditions of 150~200 DEG C, is cooled to room temperature, grinding obtains red blue green three primary colours long-afterglow fluorescent PIG material.The physical stability and chemical stability of long-afterglow fluorescent material can be substantially improved in three primary colours long-afterglow fluorescent PIG material of the invention, extend the application field of long-afterglow fluorescent material.
Description
Technical field
The present invention relates to a kind of preparation methods of three primary colours long-afterglow fluorescent PIG material, belong to rare earth luminescent material technology
Field.
Background technique
Traditional long-persistence luminous fluorescent powder is one kind last for several seconds after removing excitation light source, several minutes or even a few hours
Luminescent material.In general, the carrier that it depends on trap level to be captured, can occur, at room temperature because thermal energy is enough to swash
The carrier that trap living is captured, so that the carrier of defect center release is with the centre of luminescence to combine, to swash closing
Lasting shine is generated after rising.
Currently, long lad phosphor research causes the interest of many experts and scholars, have extensive use, includes emergency
Illumination, security display, electronic console and in-vivo imaging etc..Although now long-afterglow phosphor material achieve it is great at
Just, and for the research and development of the physics of long lad phosphor, chemical stability it is directed to the application of long afterglow powder stability
It is growing with the demand of the application of polychrome long afterglow toning.Height has been developed in aluminate, silicate and gallate at present
The long-afterglow material of effect, but the application of these fluorescent powders but only limits metastable environment, under extreme environmental condition often
It often undergoes phase transition, because acid, alkali, high humidity high pressure all make material phase structure change, luminescent properties is caused to weaken, or even lose
Effect.
In fact, in extreme environmental condition, such as acid, alkali, high humidity, it may make crystal to undergo phase transition.So that in defect
The heart, crystalline field environment locating for the centre of luminescence change, this can all reduce the long afterglow performance of fluorescent powder.There is presently no PIG
The research of the fluorescent material of long afterglow limits application of the long lad phosphor under unstable environment.
Summary of the invention
The technical issues of for long lad phosphor, the present invention provide a kind of system of three primary colours long-afterglow fluorescent PIG material
Preparation Method, the present invention use borosilicate glass frit that can soften in temperature for 580 DEG C~700 DEG C and are melt into transparent glass
Three bases of stability can be obtained by mixing and being sintered by long afterglow red-green-blue powder and borosilicate glass frit in body
Color long-afterglow fluorescent PIG material, wherein red PIG (ZnGa in three primary colours long-afterglow fluorescent PIG material2O4:Cr3+,Bi3+) hair
It penetrates as (λem=710nm), green PIG (SrAl2O4:Eu2+,Dy3+) be emitted as (λem=518nm), blue PIG (CaAl2O4:
Eu2+,Nd3+) be emitted as (λem=440nm), and red PIG (ZnGa2O4:Cr3+,Bi3+) excitation peak be (λex=
550nm, λex=413nm), blue and the green emitted wave band in three primary colours, blue are respectively corresponded, green emitting phosphor can activate
Red fluorescence powder can make up the insufficient defect of red afterglow intensity, and the stability of long afterglow powder can be improved using PIG technique, make it
Have the characteristics that antiacid, alkali, organic matter, expanded application in the acid such as chemical plant, seafood market, airport, highway, seashore, bathroom,
The extreme environments such as alkali, high humidity.
A kind of preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+With borosilicate system glass
Glass powder, which mixes and carries out 30~60min of dry grinding mixing processing, obtains mixed powder；
(2) mixed powder of step (1) is placed in 5~30min of sintering processes under the conditions of temperature is 600~780 DEG C, then set
10~15min of isothermal holding under the conditions of being 200~250 DEG C in temperature, is cooled to room temperature, and grinding obtains more than red blue green three primary colours length
Brightness fluorescence PIG material.
It is calculated in mass percent, B in the borosilicate glass frit2O3Account for 40~42%, SiO2Account for 42~43%, it
Remaining is ZnO.
Step (1) ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And borosilicate system
The mass ratio of glass powder is 1:1:1:(10~100).
Principle: the group of long afterglow powder becomes ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+,
Wherein Eu2+Easily it is oxidized at high temperature, under conditions of being higher than 800 DEG C of air calcinations, SrAl2O4:Eu2+,Dy3+Long afterglow powder
It will be oxidized inactivation, and under reducing atmosphere condition, process flow is again considerably complicated, and the condition higher than 800 DEG C will
The ZnGa made2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Long afterglow powder generates certain phase transformation, so that
The persistence of long afterglow powder shortens, and after-glow brightness can also weaken；Therefore selecting borosilicate system glass is because its is soft
Change point is lower than a phase transition temperature for long afterglow powder, can be before long afterglow powder inactivation, and softening completely wraps up it at the vitreum of melting,
Keep its not oxidized；It will lead to aggregation and redistribution of the long afterglow powder in glass melt if viscosity is too low, to influence PIG
The transparency, and viscosity is too low is also unfavorable for separating oxygen to the oxidation process of long afterglow powder；And viscosity is excessively high is unfavorable for
Melten glass is equally also unfavorable for preventing oxygen and long afterglow powder reaction process to the coating function of long afterglow glass；Finally originally
The borosilicate system glass of invention will not generate certain reaction with the substance in long-afterglow material, have when not shortening twilight sunset
Between, and improve the characteristic of the antiacid of long afterglow powder, alkali and organic matter.
The group of long afterglow powder of the present invention becomes ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+
It can be according to document " Influence of co-doping different rare earth ions on the
luminescence of CaAl2O4-based phosphors”、“A New Long Phosphorescent Phosphor
with High Brightness,SrAl2O4:Eu2+Dy3+" and " Storage of Visible Light for Long-
It is prepared by the preparation method of Lasting Phosphorescence in Chromium-Doped Zinc Gallate ".
Beneficial effects of the present invention:
The present invention is uniformly wrapped up three primary colours long afterglow powder using borosilicate system glass, so that fragile long afterglow powder tool
Standby firm transparency protected shell does not influence the afterglow intensity of long afterglow powder, persistence, the remaining meeting rate of decay, thermal stability
Etc. performances, and provide a stable space for long afterglow powder, resist extraneous extreme environment.
Detailed description of the invention
Fig. 1 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+XRD spectrum and
Former fluorescent material ZnGa2O4:Cr3+,Bi3+PDF card comparison；
Fig. 2 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material CaAl2O:Eu2+,Nd3+XRD spectrum and
Former fluorescent material CaAl2O:Eu2+,Nd3+PDF card comparison；
Fig. 3 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material SrAl2O4:Eu2+,Dy3+XRD spectrum and
Former fluorescent material SrAl2O4:Eu2+,Dy3+PDF card comparison；
Fig. 4 is the DTA curve of 4 borosilicate system glass of embodiment；
Fig. 5 is 4 three primary colours PIG fluorescent material of embodiment corresponding red PIG phosphor emission and exciting light at room temperature
Spectrum；
Fig. 6 is 4 three primary colours PIG fluorescent material of embodiment corresponding green PIG phosphor emission and exciting light at room temperature
Spectrum；
Fig. 7 is 4 three primary colours PIG fluorescent material of embodiment corresponding blue PIG phosphor emission and exciting light at room temperature
Spectrum；
Fig. 8 is the luminous intensity variations figure of 4 three primary colours PIG fluorescent material of embodiment at room temperature at any time；
Fig. 9 is the decay curve of 4 three primary colours PIG fluorescent material of embodiment at room temperature and former fluorescent material ZnGa2O4:Cr3 +,Bi3+Decay curve normalize comparison diagram；
Figure 10 is the decay curve of 4 three primary colours PIG fluorescent material of embodiment at room temperature and former fluorescent material CaAl2O:Eu2 +,Nd3+Decay curve normalize comparison diagram；
Figure 11 is the decay curve of 4 three primary colours PIG fluorescent material of embodiment at room temperature and former fluorescent material SrAl2O4:
Eu2+,Dy3+Decay curve normalize comparison diagram；
Figure 12 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material SrAl2O4:Eu2+,Dy3+Thermal stability pair
Than figure；
Figure 13 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+Thermal stability pair
Than figure；
Figure 14 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material CaAl2O:Eu2+,Nd3+Thermal stability pair
Than figure；
Figure 15 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+Thermoluminescence map
Comparison diagram (λem=413nm)；
Figure 16 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+Thermoluminescence map
Comparison diagram (λem=550nm)；
Figure 17 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material CaAl2O:Eu2+,Nd3+Thermoluminescence map
Comparison diagram (λem=550nm)；
Figure 18 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material SrAl2O4:Eu2+,Dy3+Thermoluminescence map
Comparison diagram (λem=419nm)；
Figure 19 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,
Nd3+、SrAl2O4:Eu2+,Dy3+It is respectively put into hydrochloric acid solution, sodium hydroxide solution, in water, green (SrAl2O4:Eu2+,Dy3+) and
Blue (CaAl2O4:Eu2+,Nd3+) it is using the color change for closing light source 5min after 254 and 365nm ultraviolet source irradiation 5min
Figure, red (SrAl2O4:Eu2+,Dy3+) it is the color change figure for closing light source 10s；Wherein a is former fluorescent material ZnGa2O4:Cr3 +,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Variation diagram in hydrochloric acid solution respectively, b are former fluorescent material
ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Variation diagram in sodium hydroxide solution respectively, c
For former fluorescent material ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Variation diagram in water respectively,
D is variation diagram of the three primary colours PIG fluorescent material in hydrochloric acid solution, and e is three primary colours PIG fluorescent material in sodium hydroxide solution
Variation diagram, f be the variation diagram of three primary colours PIG fluorescent material in water；
Figure 20 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,
Nd3+、SrAl2O4:Eu2+,Dy3+Chemical stability to the point nomogram(-raph) of specific luminance；
Figure 21 is 4 three primary colours PIG fluorescent material of embodiment and former fluorescent material ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,
Nd3+、SrAl2O4:Eu2+,Dy3+12 days XRD diagram are placed in hydrochloric acid solution, sodium hydroxide solution, water respectively.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
A kind of embodiment 1: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、SrAl2O4:Eu2+,Dy3+It is mixed with borosilicate glass frit
Merging carries out dry grinding mixing processing 45min and obtains mixed powder；It is calculated in mass percent, B in borosilicate glass frit2O3It accounts for
40%, SiO2Account for 43%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2 +,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:10；
(2) mixed powder of step (1) is placed in sintering processes 30min under the conditions of temperature is 600 DEG C, then is placed in temperature and is
Isothermal holding 15min under the conditions of 150 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 2: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 30min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 40.8%, SiO2Account for 43.5%, remaining is ZnO；ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、
SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:20；
(2) mixed powder of step (1) is placed in sintering processes 5min under the conditions of temperature is 750 DEG C, then is placed in temperature and is
Isothermal holding 10min under the conditions of 200 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 3: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 50min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 41.2%, SiO2Account for 44.5%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:
Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:30；
(2) mixed powder of step (1) is placed in sintering processes 25min under the conditions of temperature is 650 DEG C, then is placed in temperature and is
Isothermal holding 13min under the conditions of 160 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 4: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 50min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 40%, SiO2Account for 45%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,
Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:50；
(2) mixed powder of step (1) is placed in sintering processes 30min under the conditions of temperature is 600 DEG C, then is placed in temperature and is
Isothermal holding 15min under the conditions of 150 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+XRD spectrum and former glimmering
Luminescent material ZnGa2O4:Cr3,Bi3+PDF card comparison it is as shown in Figure 1；The present embodiment three primary colours PIG fluorescent material and original are glimmering
Luminescent material CaAl2O:Eu2+,Nd3+XRD spectrum and former fluorescent material CaAl2O:Eu2+,Nd3+PDF card comparison as scheme
Shown in 2；The present embodiment three primary colours PIG fluorescent material and former fluorescent material SrAl2O4:Eu2+,Dy3+XRD spectrum and former fluorescence
Material SrAl2O4:Eu2+,Dy3+PDF card comparison it is as shown in Figure 3；From Fig. 1~3 it is found that three primary colours PIG fluorescent material is
The superposition at crystal phase peak and amorphous peak has former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+And SrAl2O4:Eu2 +,Dy3+Characteristic peak, illustrate the fluorescent material ZnGa in three primary colours PIG fluorescent material2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+
And SrAl2O4:Eu2+,Dy3+Without structure change；
The DTA curve of the present embodiment borosilicate system glass is as shown in Figure 4；
Corresponding red PIG phosphor emission and excitation spectrum be such as at room temperature for the present embodiment three primary colours PIG fluorescent material
Shown in Fig. 5；Corresponding green PIG phosphor emission and excitation spectrum be such as at room temperature for the present embodiment three primary colours PIG fluorescent material
Shown in Fig. 6；Corresponding blue PIG phosphor emission and excitation spectrum be such as at room temperature for the present embodiment three primary colours PIG fluorescent material
Shown in Fig. 7；
The luminous intensity variations figure of the present embodiment three primary colours PIG fluorescent material at room temperature at any time is as shown in Figure 8；This reality
Apply the decay curve of three primary colours PIG fluorescent material at room temperature and former fluorescent material ZnGa2O4:Cr3,Bi3+Decay curve return
One change comparison diagram is as shown in Figure 9；The decay curve of the present embodiment three primary colours PIG fluorescent material at room temperature and former fluorescent material
CaAl2O:Eu2+,Nd3+Decay curve normalization comparison diagram it is as shown in Figure 10；The present embodiment three primary colours PIG fluorescent material is in room
Decay curve and former fluorescent material SrAl under temperature2O4:Eu2+,Dy3+Decay curve normalization comparison diagram it is as shown in figure 11；From
Fig. 8~11 are it is found that three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+With
SrAl2O4:Eu2+,Dy3+Decay of afterglow speed it is roughly the same, illustrate the fluorescent material in three primary colours PIG fluorescent material
ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+And SrAl2O4:Eu2+,Dy3+Afterglow property there is no weaken；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material SrAl2O4:Eu2+,Dy3+Thermal stability comparison diagram
As shown in figure 12；The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+Thermal stability comparison
Figure is as shown in figure 13；The present embodiment three primary colours PIG fluorescent material and former fluorescent material CaAl2O:Eu2+,Nd3+Thermal stability pair
It is more as shown in figure 14 than scheming；From Figure 12~14 it is found that blue PIG (CaAl2O4:Eu2+,Nd3+) and green PIG (SrAl2O4:Eu2+,
Dy3+) and former fluorescent material CaAl2O:Eu2+,Nd3+And SrAl2O4:Eu2+,Dy3+Thermal stability it is suitable, and red PIG
(ZnGa2O4:Cr3+,Bi3+) than former fluorescent material ZnGa2O4:Cr3+,Bi3+Thermal stability improve；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+Thermoluminescence map comparison diagram
(λem=413nm) as shown in figure 15；The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+'s
Thermoluminescence map comparison diagram (λem=550nm) as shown in figure 16；The present embodiment three primary colours PIG fluorescent material and former fluorescent material
CaAl2O:Eu2+,Nd3+Thermoluminescence map comparison diagram (λem=550nm) as shown in figure 17；The present embodiment three primary colours PIG fluorescence
Material and former fluorescent material SrAl2O4:Eu2+,Dy3+Thermoluminescence map comparison diagram (λem=419nm) as shown in figure 18；From Figure 15
~18 it is found that three primary colours PIG fluorescent material and former fluorescent material CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+With
ZnGa2O4:Cr3+,Bi3+Thermo-luminescence almost coincide, illustrate the method for the present embodiment to the trap depth of long-afterglow material and
Trap quantity has no adverse effect；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、
SrAl2O4:Eu2+,Dy3+It is respectively put into hydrochloric acid solution, sodium hydroxide solution, in water, green (SrAl2O4:Eu2+,Dy3+) and blue
(CaAl2O4:Eu2+,Nd3+) be using after 254 and 365nm ultraviolet source irradiation 5min close light source 5min color change figure,
Red (SrAl2O4:Eu2+,Dy3+) as shown in figure 19 to close the color change figure of light source 10s；Wherein a is former fluorescent material
ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Variation diagram in hydrochloric acid solution respectively, b are original
Fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Respectively in sodium hydroxide solution
Variation diagram, c are former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Respectively in water
Variation diagram, d be variation diagram of the three primary colours PIG fluorescent material in hydrochloric acid solution, e be three primary colours PIG fluorescent material in hydrogen-oxygen
Change the variation diagram in sodium solution, f is the variation diagram of three primary colours PIG fluorescent material in water；Do not handled by the present embodiment PIG
Long afterglow powder ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+More than only keeping in acid condition
Brightness performance about 12h, which is just corroded by hydrochloric acid solution, to be decomposed, and loses light-decay characteristic, there is no remaining with 254 and 365nm ultraviolet source irradiation
Brightness phenomenon generates；And the three primary colours PIG long-afterglow material Jing Guo the present embodiment PIG process, 12 are impregnated in hydrochloric acid solution
Its after-glow brightness, the rate of decay remain unchanged after it；Show that it has good repellence to acidic environment, may make long afterglow
It is used in acid extreme environment；Compare alkaline solution, the twilight sunset stability of water-soluble PIG long-afterglow material is also much superior to not
The long afterglow ZnGa handled through PIG2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、
SrAl2O4:Eu2+,Dy3+Chemical stability it is as shown in figure 20 to the point nomogram(-raph) of specific luminance；Green and blue long-afterglow material
It is in acid condition and unstable, it is red comparatively stable, but it can be improved in acid condition by PIG processing in the present embodiment
The stability of lower phase structure, to guarantee afterglow property, such as decay of afterglow speed, the stability of afterglow intensity；
The present embodiment three primary colours PIG fluorescent material and former fluorescent material ZnGa2O4:Cr3,Bi3+、CaAl2O:Eu2+,Nd3+、
SrAl2O4:Eu2+,Dy3+It is as shown in figure 21 that 12 days XRD diagram are placed in hydrochloric acid solution, sodium hydroxide solution, water respectively；Green
Placing response is complete in acid condition with blue colour fluorescent powder, and will do it hydrolysis in alkaline solution and aqueous solution makes mutually to tie
Structure generates variation, and twilight sunset stability and afterglow intensity is caused obviously to weaken；And the present embodiment handled using PIG method it is green
Color and blue long afterflow fluorescent material are but able to maintain the stabilization of phase structure；Green and blue long-afterglow material is compared, more than red is long
Brightness material is relatively stable, but still weakens crystallinity in acid solution, alkaline solution and aqueous solution, XRD peak value phase
Long-afterglow material to the present embodiment through PIG technical treatment, crystallinity reduce.
A kind of embodiment 5: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 60min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 41.8%, SiO2Account for 43.5%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:
Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:70；
(2) mixed powder of step (1) is placed in sintering processes 15min under the conditions of temperature is 680 DEG C, then is placed in temperature and is
Isothermal holding 12min under the conditions of 180 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 6: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 60min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 40.6%, SiO2Account for 44.2%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:
Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:100；
(2) mixed powder of step (1) is placed in sintering processes 8min under the conditions of temperature is 720 DEG C, then is placed in temperature and is
Isothermal holding 11min under the conditions of 190 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 7: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 60min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 41.8%, SiO2Account for 43.4%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:
Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:150；
(2) mixed powder of step (1) is placed in sintering processes 10min under the conditions of temperature is 700 DEG C, then is placed in temperature and is
Isothermal holding 12min under the conditions of 170 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
A kind of embodiment 8: preparation method of three primary colours long-afterglow fluorescent PIG material, the specific steps are as follows:
(1) by high-purity ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+And boron
Silicate Glass powder, which mixes and carries out dry grinding mixing processing 60min, obtains mixed powder；It is calculated in mass percent, borosilicate
B in glass frit2O3Account for 40.5%, SiO2Account for 44.8%, remaining is ZnO；ZnGa2O4:0.001Cr3,0.002Bi3+、CaAl2O:
Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is 1:1:1:200；
(2) mixed powder of step (1) is placed in sintering processes 20min under the conditions of temperature is 680 DEG C, then is placed in temperature and is
Isothermal holding 12min under the conditions of 180 DEG C is cooled to room temperature under air atmosphere, and grinding obtains red blue green three primary colours long-afterglow fluorescent
PIG material.
Claims (3)
1. a kind of preparation method of three primary colours long-afterglow fluorescent PIG material, which is characterized in that specific step is as follows:
(1) by high-purity ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+With borosilicate glass frit
It mixes and carries out 30~60min of dry grinding mixing processing and obtain mixed powder；
(2) mixed powder of step (1) is placed in 5~30min of sintering processes under the conditions of temperature is 600~780 DEG C, then is placed in temperature
Degree is 10~15min of isothermal holding under the conditions of 200~250 DEG C, is cooled to room temperature, and it is glimmering that grinding obtains red blue green three primary colours long afterglow
Light PIG material.
2. the preparation method of three primary colours long-afterglow fluorescent PIG material according to claim 1, it is characterised in that: with quality hundred
Score meter, B in borosilicate glass frit2O3Account for 40~42%, SiO2Account for 43~45%, remaining is ZnO.
3. the preparation method of three primary colours long-afterglow fluorescent PIG material according to claim 1 or claim 2, it is characterised in that: step
(1)ZnGa2O4:Cr3+,Bi3+、CaAl2O:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+Mass ratio with borosilicate glass frit is
1:1:1:(30~100).
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| CN113620599A (en) * | 2021-06-15 | 2021-11-09 | 福建江夏学院 | Novel long-afterglow luminescent glass-ceramic and preparation method thereof |
| CN115893847A (en) * | 2022-10-25 | 2023-04-04 | 福建江夏学院 | Multimode fluorescent microcrystalline glass and preparation and application thereof |
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| CN113620599A (en) * | 2021-06-15 | 2021-11-09 | 福建江夏学院 | Novel long-afterglow luminescent glass-ceramic and preparation method thereof |
| CN115893847A (en) * | 2022-10-25 | 2023-04-04 | 福建江夏学院 | Multimode fluorescent microcrystalline glass and preparation and application thereof |
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