CN110357424A - A kind of complex phase fluorescent glass and its cryogenic high pressure sintering preparation method - Google Patents
A kind of complex phase fluorescent glass and its cryogenic high pressure sintering preparation method Download PDFInfo
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- CN110357424A CN110357424A CN201910558641.1A CN201910558641A CN110357424A CN 110357424 A CN110357424 A CN 110357424A CN 201910558641 A CN201910558641 A CN 201910558641A CN 110357424 A CN110357424 A CN 110357424A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
Abstract
The invention discloses a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass, preparation process is the following steps are included: raw material mixing, compression molding, cryogenic high pressure sintering and cutting sanding and polishing.It is high that the complex phase fluorescent glass that the technical solution provided according to the present invention obtains has many advantages, such as that sintering temperature is low, fluorescent powder lattice corrodes small, host glass transmitance height, the luminous efficiency of fluorescent glass.
Description
Technical field
The invention belongs to technical field of semiconductor illumination, more particularly to a kind of preparation method of fluorescence transition material, tool
Body is a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass.
Background technique
In recent years, the fluorescence that the blue light laser diode (Laser diode, abbreviation LD) with high optical power density excites
Conversion hysteria white-light illuminating technology becomes the research hotspot of technical field of semiconductor illumination, and Shuji Nakamura is pointed out blue in the near future
Light LED technology will be limited by the physics limit of its luminous efficiency, finally replaced blue light laser diode technology, and openly
Indicate " 10 years following, laser lighting will replace LED illumination ".2014, BMW brought in Beijing Auto Show and is loaded in i8 vehicle
On the first volume production laser headlight in the whole world, and declare the replacer that " laser headlight " is appointed as to " LED headlight ".The same year, Audi
It also announces to be equipped with laser headlight on volume production vehicle R8 LMX for the first time in the car exhibition of Paris.On this basis, Audi and Bosch,
Cross-cutting cooperation is unfolded in Ou Silang and lighting engineering research institute, the Karlsruhe Institute of Technology, has developed completely new " high definition
Matrix form laser headlight ", wherein then blue light laser diode reflects again first by the laser emission to reflecting mirror of 450nm
To photoconverter, so that converting white light for blue laser projects road surface." the yellow phosphorus filter used in above two laser headlight
Mirror " or " photoconverter " are a kind of special fluorescence transition material, the high-energy blue that laser diode issues can be swashed
Light is converted to white light, plays the role of fluorescence conversion.
Blue light LD is different from the physical structure of blue-ray LED, and joined one layer between PN junction has photoactive semiconductor, and
And make two end faces that there is part reflection function after polishing, form an optical cavity.In the case where forward bias, electricity
Son is spontaneous compound with hole and generates spontaneous radioluminescence, and photon caused by spontaneous radiation can lure the current-carrying excited into
Son is compound and issues new photon, i.e. generation stimulated radiation.Blue-ray LED its luminous efficiency in large driven current density rises with electric current
And obviously weaken (i.e. Efficiency droop), while the problem of there is also " blue light harms ", and blue light LD can effectively be kept away
Exempt from the problem.Compared with blue-ray LED luminescence technology, the white light spectrum output of LD is abundant, and spectrum coverage rate is big, and colour rendering index is high
In typical white light LEDs, and the monochromaticjty of laser lighting is good, high directivity, luminous zone density are 1000 times of LED or more, no
It only can increase projection distance, improve safety, while volume is smaller, more compact structure.
The excitation light source of laser lighting belongs to point light source, and hot spot very little (~100 μm), optical power density is very high (to be greater than
380W/mm2), and the halfwidth of excitation spectrum is very narrow, and exciting light energy is highly concentrated in bandwidth extremely narrow near peak position
(~3nm), there is very high energy density.Therefore, traditional fluorescence transition material is unable to satisfy high optical power density excitation and shines
Bright growth requirement.The encapsulating material being widely used in current white light LED part is epoxy resin and silica type material, material
Thermal resistance is high, and anti-aging property is poor, temperature quenching effect easily occurs, is remarkably decreased launching efficiency, therefore, utilizes fluorescent powder and ring
Oxygen resin or the technology path of organic silica gel assembled package gross incompetence the lighting engineering of high optical power density excitation.Laser
Lighting system is for the excitation of fluorescence transition material and emission characteristics, heating conduction, thermal shock resistance, anti-high and low-temp thermal cycle
The performance indicators such as ability, high-temperature thermal stability performance and high temperature fluorescence conversion efficiency have more harsh composite request.Therefore,
Have to abandon epoxy resin or organic silica gel encapsulation technology route, it would be highly desirable to research be suitable for bloom power density laser excitation and
The stable novel high-performance fluorescence transition material of physical and chemical performance.
Glass is a kind of inorganic non-metallic material with high optical transparency matter, heating conduction, thermal-shock resistance
Energy, corrosion resistance and high temperature resistance are significantly larger than epoxy resin and organic silica gel material, can be with the controllable complex of fluorescent powder
At a kind of novel high-performance fluorescence transition material, i.e. fluorescent glass.Fluorescent powder grain is uniformly coated on residuite glass
In, the light conversion efficiency and thermal stability of fluorescent powder can be greatly improved, both can be used for laser lighting, be also very applicable for
The encapsulation of large power white light LED.For existing epoxy resin or organic silica gel packing forms, fluorescent glass has as follows
Advantage: (1) physicochemical properties are more stable, and have more high thermal stability；(2) it avoids conventional fluorescent powder and is distributed in asphalt mixtures modified by epoxy resin
Fluorescent glass and blue light LD or high-power LED chip, are directly carried out spiral-lock by the process that dispensing coating is carried out in rouge or silica gel,
Simplify packaging technology；(3) fluorescent powder is uniformly dispersed in host glass, and photochromic consistency is strong, and quality white light is more preferable；(4) glimmering
Light glass preparation process is simple, at low cost, can be fabricated to various shape, and uniformity and transparency are good.Just because of fluorescence glass
Glass has the advantages that above-mentioned a series of, becomes a kind of ideal novel fluorescence transition material, in laser lighting and high-power
More and more advantages are shown in white-light LED encapsulation field.
For fluorescent glass and preparation method thereof, researchers at home and abroad have carried out a large amount of research.Specially such as China
Sharp (CN 201811320403.9) discloses a kind of fluorescent glass and preparation method thereof and light emitting device, it is characterised in that preparation
Process is heated to each of the glass matrix the following steps are included: take each component and fluorescent powder of glass matrix after mixing
Component fusing, then cooling makes its solidification.The shortcomings that technical solution is the glass metal of fusing since the fusion temperature of glass is high
It is easy to cause lattice corrosion function to fluorescent powder, and then the luminous efficiency of fluorescent glass is caused to decline.Chinese patent (CN
201810283374.7) a kind of fluorescent glass and preparation method thereof of composite phosphor is disclosed, it is characterized in that preparation process packet
Include following steps: (1) frit mixed melting；(2) composite phosphor mixes；(3) mixed powder co-sintering is handled.The technical solution
The shortcomings that be since the sintering temperature of step (3) is low so that the transmitance of host glass is low, and then lead to fluorescent glass goes out light
Low efficiency.Therefore, when facing the specific preparation method of fluorescent glass, there are still many key technical problems to need in the prior art
It solves, such as: (1) host glass corrodes seriously the lattice of fluorescent powder when high-temperature fusion: good to obtain fluorescent glass
Light extraction efficiency, it is necessary to so that host glass is kept good optical transmittance, and in the prior art, it is desirable to obtain host glass
Good transmitance, the method being readily apparent that is that high-temperature fusion is re-started to host glass, but under high temperature fused state,
Glass metal will cause serious lattice corrosion function to fluorescent powder, or even fluorescent powder is fused into glass phase completely, and then causes
The luminous efficiency of fluorescent glass drastically reduces；(2) the host glass transmitance that low temperature co-fired knot obtains is low: in order to protect fluorescent powder
It is not corroded by host glass, the method being readily apparent that in the prior art is to reduce the sintering temperature of fluorescent glass, but pass through
It can be found that when the sintering temperature of fluorescent glass is lower than glass melting temperature, the sample interior of acquisition exists a large amount of for research
Bubble and boundary defect cause the transmitance of host glass extremely low, and then the light extraction efficiency of fluorescent glass is caused to drastically reduce.
Summary of the invention
Host glass is to fluorescence when in order to overcome high-temperature fusion existing for the above-mentioned preparation process of fluorescent glass in the prior art
The technical problems such as host glass transmitance is low that the lattice of powder corrodes that serious, low temperature co-fired knot obtains, the present invention provides one kind
, fluorescent powder lattice low with sintering temperature corrodes the complex phase that small, host glass transmitance is high, fluorescent glass luminous efficiency is high
The cryogenic high pressure sintering preparation method of fluorescent glass.
A kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass, comprising the following steps:
(1) raw material mixes: weighing fluorescent powder and glass dust raw material according to mass percent, and puts it into agate mortar and grind
Mixing 10 ~ 30 minutes obtains fluorescent powder and is dispersed in the mixed raw material in glass powder；
(2) compression molding: the mixed raw material of step (1) acquisition is weighed, puts it into stainless steel mould, utilizes type mechanical tableting machine
Die cast obtains sheet raw embryo after demoulding, wherein the pressure of compression molding is 50 ~ 100MPa；
(3) cryogenic high pressure is sintered: the sheet raw embryo that step (2) obtain being put into graphite jig, then by sample and graphite jig
It is put into togerther hot-pressed sintering furnace, cryogenic high pressure is carried out and is sintered 20 ~ 60 minutes, sample is cooled to room temperature with furnace after the completion of sintering, i.e.,
It can get complex phase fluorescent glass semi-finished product；
(4) it cuts sanding and polishing: the complex phase fluorescent glass semi-finished product that step (3) obtain being cut, are polished, polishing treatment,
It can be obtained a kind of for great power LED or the complex phase fluorescent glass finished product of laser lighting.
Preferably, further include step (2.1) isostatic cool pressing step between step (2) and step (3), step (2) are obtained
Sheet raw embryo carry out isostatic cool pressing processing, obtain sheet raw embryo Jing Guo isostatic cool pressing, the pressure of isostatic cool pressing for 150 ~
200MPa；The sheet raw embryo of step (3) is the sheet raw embryo that step (2.1) obtain.
It preferably, further include that step (2.2) are pre-sintered between step (2) and step (3), by the sheet raw embryo of acquisition normal
Pressure is pre-sintered, and obtains the sheet raw embryo by being pre-sintered, sintering temperature be glass softening point temperature and melting temperature it
Between, sintering time is 30 ~ 60 minutes；The sheet raw embryo of step (3) is the sheet raw embryo that step (2.2) obtain.
It preferably, further include that step (2.2) are pre-sintered between step (2.1) and step (3)；By the sheet raw embryo of acquisition
It is pre-sintered under normal pressure, obtains the sheet raw embryo by being pre-sintered, sintering temperature is glass softening point temperature and melting temperature
Between degree, sintering time is 30 ~ 60 minutes；The sheet raw embryo of step (3) is the sheet raw embryo that step (2.2) obtain.
Preferably, the fluorescent powder used is SrSi2O2N2: Eu2+Green emitting phosphor, Y3Al5O12: Ce3+Yellow fluorescence
Powder, Sr2Si5N8: Eu2+Red fluorescence powder and CaAlSiN3: Eu2+One of red fluorescence powder or several combinations.
Preferably, the glass powder used is silicate glass powder, phosphate glass powder, tellurate glass powder, bismuthic acid
One of salt glass powder.
Preferably, the mass percent value range of the fluorescent powder and glass powder is 0.1 ~ 50%.
Preferably, the sintering temperature is between glass softening point temperature and melting temperature, sintering pressure be 50 ~
100MPa, sintering atmosphere are one of vacuum atmosphere, inert atmosphere and reducing atmosphere.
Compared with prior art, the beneficial effects of the present invention are:
(1) luminous efficiency is high: since sample is to be sintered at a lower temperature, i.e. host glass and not up to molten
State, therefore the viscosity of sintering process mesostroma glass is larger, so that host glass is very micro- to the lattice corrosion function of fluorescent powder
It is small, the luminescent properties of fluorescent powder are effectively protected, overcome leads to fluorescent powder quilt since sintering temperature is excessively high in the prior art
The technical issues of erosion is serious, and luminous efficiency sharply declines；
(2) light scattering loss is low: since sample is during the sintering process by great ambient pressure, during the sintering process
Existing gap between feed particles can be effectively excluded, and then substantially reduces stomata in host glass and the scattering of light is damaged
Consumption, improves the optical transmittance of fluorescent glass, effectively overcomes and lead in the prior art since sintering temperature is too low under condition of normal pressure
The technical problem for causing the optical transmittance of fluorescent glass too low；
(3) optical transmittance is high: since sample is during the sintering process by great ambient pressure, glass powder particles are soft
It can be preferably pressed together under change state, overcome the surface tension effects of glass powder particles, greatly improve glass powder
Contact interface between particle can be such that glass powder is preferably fused together with glass powder, under the effect of certain outside energy,
So that glass powder particles is bonded and be formed Glassy Space network structure again in interface, eliminate the boundary defect of glass powder particles,
Improve fluorescent glass spatially uniform, further increase the optical transmittance of glass, effectively overcome in the prior art due to
The not high technical problem of the too low optical transmittance for leading to fluorescent glass of sintering temperature under condition of normal pressure；
(4) compared with the crystalline ceramics that high temperature and pressure prepares, complex phase fluorescent glass provided by the invention is in material composition, knot
There is significant difference in structure, performance and preparation method, the beneficial effects of the present invention are: 1. the sintering of normally transparent ceramics needs to surpass
1500 DEG C are crossed, and the present invention provides not more than 1000 DEG C of sintering temperature of complex phase fluorescent glass preparation method, therefore, this hair
Bright sintering temperature is low, can save mass energy consumption；2. crystalline ceramics is able to maintain good rigidity in sintering process, hold
Higher ambient pressure is easily born, and glass sample is heated on softening point temperature and can soften, and is not easy to bear higher
Ambient pressure, therefore, technical solution provided by the invention needs the relationship between preferable control sintering temperature and pressure, is
Improvements over the prior art and innovation, are not obvious results；3. crystalline ceramics is polycrystalline material, when light is through saturating
Birefringent loss is easily caused in grain boundaries when bright ceramics, and complex phase fluorescent glass main component provided by the invention is unformed
The glass material of state, there is no the birefringent losses of crystal boundary, therefore light extraction efficiency is higher；4. crystalline ceramics hardness is too high, it is not easy
It is machined, and complex phase fluorescent glass hardness provided by the invention is relatively low, it is easy to process at various sizes and shape
Sample.
Detailed description of the invention
Fig. 1 is the sample and mold schematic diagram when cryogenic high pressure is sintered；
Fig. 2 is the shooting photo in kind of embodiment 1；
Fig. 3 is 1 microscopically observation photo of embodiment；
Fig. 4 is the fluorescent emission figure of embodiment 1；
Fig. 5 is the shooting photo in kind of comparative example 1；
Fig. 6 is 1 microscopically observation photo of comparative example；
Fig. 7 is the shooting photo in kind of comparative example 2；
Fig. 8 is 2 microscopically observation photo of comparative example；
Fig. 9 is the full transmitance curve graph of comparative example 1 and 2.
Specific embodiment
Invention is further described in detail with specific embodiment with reference to the accompanying drawings of the specification, it should be noted that
Figure of description and following embodiments are merely to illustrate the present invention, are not used to limit practical range of the invention.
Embodiment 1
Y is weighed respectively3Al5O12: Ce3+Yellow fluorescent powder 0.5g, silicate glass powder 10g, then put it into agate mortar
Ground and mixed 30 minutes；Weighing uniformly mixed mixture 1g and putting it into diameter is to utilize machine in 15mm stainless steel mould
Tool tablet press machine die cast, molding pressure are 70MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；By piece
Shape raw embryo carries out isostatic cool pressing processing, and the pressure of isostatic cool pressing is 200MPa；By the sheet raw embryo Jing Guo isostatic cool pressing in normal pressure
Under be pre-sintered, sintering temperature be 800 DEG C, sintering time be 30 minutes, obtain through pre-sintering sheet raw embryo；It will obtain
Sheet raw embryo be put into graphite jig, then by sample and graphite jig be put into togerther hot-pressed sintering furnace carry out cryogenic high pressure burning
Knot, sintering temperature are 750 DEG C, and sintering time is 30 minutes, and sintering pressure 100MPa, sintering atmosphere is vacuum atmosphere, sintering
Sample is cooled to room temperature with furnace after the completion, and cooling sample is finally carried out cutting sanding and polishing, and it is yellow to can be obtained a kind of transmitting
The complex phase fluorescent glass finished product of light.
Embodiment 2
SrSi is weighed respectively2O2N2: Eu2+Green emitting phosphor 0.5g, phosphate glass powder 10g, then put it into agate mortar
Middle ground and mixed 10 minutes；Weighing uniformly mixed mixture 1g and putting it into diameter is to utilize in 15mm stainless steel mould
Type mechanical tableting machine die cast, molding pressure are 100MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；It will
Sheet raw embryo carries out isostatic cool pressing processing, and the pressure of isostatic cool pressing is 150MPa；Sheet raw embryo Jing Guo isostatic cool pressing is put into
Then sample and graphite jig are put into togerther hot-pressed sintering furnace and carry out cryogenic high pressure sintering, sintering temperature 500 by graphite jig
DEG C, sintering time is 40 minutes, sintering pressure 50MPa, and sintering atmosphere is inert atmosphere, and sample cools down with furnace after the completion of sintering
To room temperature, cooling sample is finally subjected to cutting sanding and polishing, can be obtained it is a kind of emit green light complex phase fluorescent glass at
Product.
Embodiment 3
Sr is weighed respectively2Si5N8: Eu2+Red fluorescence powder 0.2g, tellurate glass powder 10g, then put it into agate mortar
Middle ground and mixed 15 minutes；Weighing uniformly mixed mixture 1g and putting it into diameter is to utilize in 15mm stainless steel mould
Type mechanical tableting machine die cast, molding pressure are 50MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；It will
The sheet raw embryo of acquisition is pre-sintered under normal pressure, and sintering temperature is 450 DEG C, and sintering time is 30 minutes, is obtained by pre-
The sheet raw embryo of sintering；The sheet raw embryo of acquisition is put into graphite jig, sample and graphite jig are then put into togerther hot pressing
Sintering furnace carries out cryogenic high pressure sintering, and sintering temperature is 400 DEG C, and sintering time is 30 minutes, sintering pressure 80MPa, sintering
Atmosphere is reducing atmosphere, and sample is cooled to room temperature with furnace after the completion of sintering, and cooling sample is finally carried out cutting sanding and polishing,
It can be obtained a kind of complex phase fluorescent glass finished product for emitting feux rouges.
Embodiment 4
CaAlSiN is weighed respectively3: Eu2+Red fluorescence powder 0.01g, bismuthate glass powder 10g, then puts it into agate mortar
Middle ground and mixed 20 minutes；Weighing uniformly mixed mixture 1g and putting it into diameter is to utilize in 15mm stainless steel mould
Type mechanical tableting machine die cast, molding pressure are 60MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；It will
The sheet raw embryo of acquisition is put into graphite jig, and sample and graphite jig are then put into togerther hot-pressed sintering furnace and carry out cryogenic high pressure
Sintering, sintering temperature are 430 DEG C, and sintering time is 40 minutes, and sintering pressure 60MPa, sintering atmosphere is reducing atmosphere, sintering
Sample is cooled to room temperature with furnace after the completion, and cooling sample is finally carried out cutting sanding and polishing, and it is red to can be obtained a kind of transmitting
The complex phase fluorescent glass finished product of light.
Embodiment 5
SrSi is weighed respectively2O2N2: Eu2+Green emitting phosphor 0.2g, Y3Al5O12: Ce3+Yellow fluorescent powder 0.5g, Sr2Si5N8:
Eu2+Then red fluorescence powder 0.1g, silicate glass powder 10g put it into ground and mixed 25 minutes in agate mortar；It weighs mixed
Closing uniform mixture 1g and putting it into diameter is to utilize type mechanical tableting machine die cast, molding in 15mm stainless steel mould
Pressure be 75MPa, after demoulding obtain have certain mechanical strength sheet raw embryo；Sheet raw embryo progress isostatic cool pressing is added
Work, the pressure of isostatic cool pressing are 180MPa；Sheet raw embryo Jing Guo isostatic cool pressing is pre-sintered under normal pressure, sintering temperature
It is 780 DEG C, sintering time is 40 minutes, obtains the sheet raw embryo by being pre-sintered；The sheet raw embryo of acquisition is put into graphite mo(u)ld
Then sample and graphite jig are put into togerther hot-pressed sintering furnace and carry out cryogenic high pressure sintering by tool, sintering temperature is 730 DEG C, is burnt
Tying the time is 35 minutes, sintering pressure 80MPa, and sintering atmosphere is vacuum atmosphere, and sample is cooled to room with furnace after the completion of sintering
Cooling sample is finally carried out cutting sanding and polishing by temperature, can be obtained it is a kind of emit broadband spectral complex phase fluorescent glass at
Product.
Embodiment 6
Y is weighed respectively3Al5O12: Ce3+Yellow fluorescent powder 5.0g, phosphate glass powder 10g, then put it into agate mortar
Ground and mixed 15 minutes；Weighing uniformly mixed mixture 1g and putting it into diameter is to utilize machine in 15mm stainless steel mould
Tool tablet press machine die cast, molding pressure are 80MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；It will obtain
The sheet raw embryo obtained is put into graphite jig, and sample and graphite jig are then put into togerther hot-pressed sintering furnace and carry out cryogenic high pressure burning
Knot, sintering temperature are 520 DEG C, and sintering time is 20 minutes, and sintering pressure 90MPa, sintering atmosphere is inert atmosphere, has been sintered
It is cooled to room temperature with furnace at rear sample, cooling sample is finally subjected to cutting sanding and polishing, can be obtained a kind of transmitting yellow light
Complex phase fluorescent glass finished product.
For substantive distinguishing features and the marked improvement for further illustrating technical solution of the present invention, specifically compared below with reference to two
Example is described in detail, and has same similar technical effect using other samples of technical solution of the present invention preparation:
Comparative example 1
Weighing 1g silicate glass powder and putting it into diameter is to be cast into 15mm stainless steel mould using type mechanical tableting machine
Type, molding pressure are 70MPa, and the sheet raw embryo with certain mechanical strength is obtained after demoulding；Sheet raw embryo is carried out cold etc.
Static pressure processing, the pressure of isostatic cool pressing are 200MPa；Sheet raw embryo Jing Guo isostatic cool pressing is sintered under normal pressure, is sintered
Temperature be 750 DEG C, sintering time be 30 minutes, sample is cooled to room temperature with furnace after the completion of sintering, finally by cooling sample into
Row cutting sanding and polishing, can be obtained a kind of host glass piece being sintered by low-temperature atmosphere-pressure.
Comparative example 2
Preparation process and parameter of the comparative example 2 with comparative example 1 in early period keep identical, and difference place, which is only that, finally adopts
It is prepared with the method that cryogenic high pressure is sintered, detailed process is as follows: weighing 1g silicate glass powder and put it into diameter and be
In 15mm stainless steel mould, using type mechanical tableting machine die cast, molding pressure is 70MPa, and obtaining after demoulding has centainly
The sheet raw embryo of mechanical strength；Sheet raw embryo is subjected to isostatic cool pressing processing, the pressure of isostatic cool pressing is 200MPa；By acquisition
Sheet raw embryo is put into graphite jig, and sample and graphite jig are then put into togerther hot-pressed sintering furnace and carry out cryogenic high pressure sintering,
Sintering temperature is 750 DEG C, and sintering time is 30 minutes, and sintering pressure 80MPa, sintering atmosphere is vacuum atmosphere, and sintering is completed
Sample is cooled to room temperature with furnace afterwards, and cooling sample is finally carried out cutting sanding and polishing, can be obtained a kind of high by low temperature
Press the host glass piece of sintering.
Fig. 1 is that the sample and mold schematic diagram, middle section when cryogenic high pressure is sintered represent sheet raw embryo, periphery black part
Divide and represent graphite jig, sample is placed in the most intermediate of mold, and ambient pressure first acts on graphite jig during the sintering process, so
Being transmitted to again on sample afterwards acts on it by high pressure.Fig. 2 is the shooting photo in kind of 1 fluorescent glass of embodiment, and the sample is thick
Spending is 2mm, and the mass percent of fluorescent powder and glass powder is 5%, and actual color is bright yellow, it can be seen from the figure that should
The straight line transmittance of sample is lower, the reason is that a large amount of fluorescent powder is doped in host glass, when light is incident on sample
When internal, fluorescent powder grain can cause complicated scattering effect, this process can promote the exciting light of portions incident abundant
It absorbs, is then converted into the light of other wavelength, improve fluorescent powder to the absorption efficiency of exciting light, and then improve fluorescent glass
Fluorescence conversion efficiency；Meanwhile it even if examining it is also found that a large amount of fluorescent powder grain is doped in sample, in sample
It still is able to observe " fluorescence " printed words on paper in the case where thickness thicker (2mm), shows that the host glass of the sample has
Higher transmitance, to make other wavelength lights after part exciting light and conversion that can preferably launch from sample
Come, and then synthesize white light, improves the light extraction efficiency of fluorescent glass.Fig. 3 is 1 microscopically observation photo of embodiment, it can be seen that
Fluorescent powder grain is evenly dispersed in glass phase, and interface is clear, shows fluorescent powder almost without the erosion by glass phase
Effect.Fig. 4 is the fluorescent emission figure of embodiment 1, and the spectrum launched is consistent with YAG yellow fluorescent powder, shows that fluorescent powder does not have
It is destroyed and luminous efficiency is high.
Fig. 5 is the shooting photo in kind of comparative example 1, it can be seen that the matrix glass prepared using existing low-temperature atmosphere-pressure method
Glass piece transparency is very low.Fig. 6 is the photo of 1 microscopically observation of comparative example, it can be seen that there are a large amount of gas for sample interior
Bubble, the presence just because of these a large amount of bubbles cause its transparency very low, cause the light extraction efficiency of fluorescent glass low.
Fig. 7 is the shooting photo in kind of comparative example 2, it can be seen that is prepared using cryogenic high pressure method provided by the invention
Host glass piece transparency it is very high.Fig. 8 is the photo of 2 microscopically observation of comparative example, it can be seen that sample interior is almost
There is no bubbles, and inside glass is highly uniform, without apparent boundary defect, therefore can obtain very high optical clear
Degree.It is mixed when host glass powder and fluorescent powder, when carrying out cryogenic high pressure sintering using same technical solution, matrix
Glass can equally obtain very high transmitance, and then improve the light extraction efficiency of fluorescent glass.
Fig. 9 is the full transmitance curve graph of comparative example 1 and 2, it can be seen that in visible-range, the full impregnated of comparative example 1
Rate is crossed no more than 30%, and the full transmitance of comparative example 2 for using technical solution of the present invention to obtain has been more than 90%, shows skill of the present invention
Art scheme has substantive distinguishing features and marked improvement.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention, and there is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (9)
1. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass, which comprises the following steps:
(1) raw material mixes: weighing fluorescent powder and glass dust raw material according to mass percent, and puts it into agate mortar and grind
Mixing 10 ~ 30 minutes obtains fluorescent powder and is dispersed in the mixed raw material in glass powder；
(2) compression molding: the mixed raw material of step (1) acquisition is weighed, puts it into stainless steel mould, utilizes type mechanical tableting machine
Die cast obtains sheet raw embryo after demoulding, wherein the pressure of compression molding is 50 ~ 100MPa；
(3) cryogenic high pressure is sintered: the sheet raw embryo that step (2) obtain being put into graphite jig, then by sample and graphite jig
It is put into togerther hot-pressed sintering furnace, cryogenic high pressure is carried out and is sintered 20 ~ 60 minutes, sample is cooled to room temperature with furnace after the completion of sintering, i.e.,
It can get complex phase fluorescent glass semi-finished product；
(4) it cuts sanding and polishing: the complex phase fluorescent glass semi-finished product that step (3) obtain being cut, are polished, polishing treatment,
It can be obtained a kind of for great power LED or the complex phase fluorescent glass finished product of laser lighting.
2. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that step
It (2) further include step (2.1) isostatic cool pressing step between step (3), the sheet raw embryo that step (2) are obtained carries out cold etc. quiet
Pressure processing, obtains the sheet raw embryo Jing Guo isostatic cool pressing, and the pressure of isostatic cool pressing is 150 ~ 200MPa；The sheet of step (3) is raw
Embryo is the sheet raw embryo that step (2.1) obtain.
3. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that step
(2) further include that step (2.2) are pre-sintered between step (3), the sheet raw embryo of acquisition is pre-sintered under normal pressure, is obtained
Sheet raw embryo by pre-sintering, for sintering temperature between glass softening point temperature and melting temperature, sintering time is 30 ~ 60 points
Clock；The sheet raw embryo of step (3) is the sheet raw embryo that step (2.2) obtain.
4. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 2, which is characterized in that in step
It suddenly further include that step (2.2) are pre-sintered between (2.1) and step (3)；The sheet raw embryo of acquisition is pre-sintered under normal pressure,
Obtain the sheet raw embryo by being pre-sintered, sintering temperature for glass softening point temperature and melting temperature between, sintering time for 30 ~
60 minutes；The sheet raw embryo of step (3) is the sheet raw embryo that step (2.2) obtain.
5. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that described
Fluorescent powder be SrSi2O2N2: Eu2+Green emitting phosphor, Y3Al5O12: Ce3+Yellow fluorescent powder, Sr2Si5N8: Eu2+It is red glimmering
Light powder and CaAlSiN3: Eu2+One of red fluorescence powder or several combinations.
6. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that described
Glass powder be one of silicate glass powder, phosphate glass powder, tellurate glass powder, bismuthate glass powder.
7. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that described
The mass percent value range of fluorescent powder and glass powder is 0.1 ~ 50%.
8. a kind of cryogenic high pressure sintering preparation method of complex phase fluorescent glass according to claim 1, which is characterized in that described
Sintering temperature is between glass softening point temperature and melting temperature, and sintering pressure is 50 ~ 100MPa, and sintering atmosphere is vacuum gas
One of atmosphere, inert atmosphere and reducing atmosphere.
9. a kind of complex phase fluorescent glass, which is characterized in that high using low temperature described in claim 1 ~ 8 any one claim
Pressure sintering preparation method obtains.
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Application publication date: 20191022 |