CN110183104A - A kind of deep ultraviolet glass and preparation method thereof, application - Google Patents
A kind of deep ultraviolet glass and preparation method thereof, application Download PDFInfo
- Publication number
- CN110183104A CN110183104A CN201910577996.5A CN201910577996A CN110183104A CN 110183104 A CN110183104 A CN 110183104A CN 201910577996 A CN201910577996 A CN 201910577996A CN 110183104 A CN110183104 A CN 110183104A
- Authority
- CN
- China
- Prior art keywords
- glass
- deep ultraviolet
- ultraviolet
- melting
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
Abstract
The invention discloses a kind of deep ultraviolet glass materials and preparation method thereof, application, which includes the component of following weight percentage: 54.0-67.0%P2O5, 3.0-10.0%SiO2, 6.0-13.0%Al2O3, 10.0-25.0%B2O3, 4.0-7.0%ZnO, 0-2.0%Li2O, 0-2.0%Na2O, 0-2.0%K2Its transmitance at 185nm is (60 ± 3) × 10 in 30-300 DEG C of range thermal expansion coefficient 50% or more when O, holvi glass thickness 1.0mm‑7/ DEG C, have low softening temperature, softening temperature less than 500 DEG C, have good chemical stability, II grade of endurance；The preparation method of the saturating deep ultraviolet glass is simple, environment friendly and pollution-free, does not introduce environmentally harmful heavy metal ion, and glass melting temperature is lower.
Description
Technical field
The present invention relates to special glass material and its preparation technical field, in particular to a kind of deep ultraviolet glass and its system
Preparation Method, application.
Background technique
Ultraviolet light is a kind of electromagnetic wave generally existing in nature, and light of the solar spectrum medium wavelength less than 380nm claims
For ultraviolet light (Ultraviolet Radiation), ultraviolet-sterilization, it is ultraviolet test it is pseudo-, in terms of have it is important
Effect, while intensive ultraviolet can also generate certain harm to human skin, eyes etc..Ultraviolet light divides again according to its wave-length coverage
For UV-A (315-380nm), UV-B (280-315nm), three kinds of UV-C (100-280nm), the warp of ultraviolet light contained in sunlight
After atmosphere, the UV-C less than 290nm is absorbed by the ozone layer in atmosphere mostly, this some ultra violet rays SPECTRAL REGION is claimed
For " day-old chick ", if having detected " day-old chick " UV signal in endoatmosphere, can be concluded that substantially be by artificial aircraft such as
What the transmittings such as guided missile, rocket generated.Because the light that the propeller plumage flame of these aircraft is issued contains strong 220-280nm
Wave band deep ultraviolet light, so that 220-280nm ultraviolet light becomes the characteristic light that aircraft issues.Ultraviolet detector is exactly to pass through
The feature ultraviolet light of the propeller plumage flame of explorer vehicle threatens direction and degree with judgement, send a warning in real time so as to
Proper moment is selected, implements effectively interference, takes evade Deng measures, fight the attack of enemy.And ultraviolet detection field is current
The wave-length coverage of the research hotspot of ultraviolet regime in the world, detection is 185-280nm, is not generated to the wavelength of 280nm or more
Day blind ultraviolet characteristic is really realized in response.Therefore, to the dark purple outskirt signal of deep UV especially 185nm~280nm range
Detection be of great significance.But due to the distal end that 185-280nm is in deep UV, partially already belong to vacuum ultraviolet
The ability in domain, ray is especially high, and according to the theory of electromagnetic wave slippages in the medium, wavelength is shorter, is lost bigger, therefore works as
The saturating UV materials kind that can be commercialized in modern world wide is seldom, and transmitance is all very low at 185nm.
Have more research to saturating UV materials both at home and abroad, these saturating UV materials be concentrated mainly on fluoride single crystal,
In terms of halide glass and silica glass material.Wherein crystal of fluoride (such as CaF2、MgF2Crystal) because crystal growth is difficult,
Processing preparation is difficult, expensive, and crystal, because of anisotropic, there are inherent shortcoming, poor chemical stability, geometry is several very little
It is small, so using limited；And halide glass because contain fluoride or chloride, during the high temperature melting of glass, this
A little halide cause a degree of corrosion function to platinum crucible, cost and production safety hidden danger are increased, so that preparing item
Part requires harshness, expensive；Although pure quartz glass in 254nm transmitance up to 91%, quartz glass glass melting temperature
High, preparation condition requires harshness, and expensive, thermal expansion coefficient differs larger with the thermal expansion coefficient of kovar alloy, Bu Nengyu
The direct sealing-in of kovar alloy, limits use scope, so that its application is affected by limitation.
Holvi glass material is since uniformity is good, and transmitance is high, and geometry is controllable, and price is low, is for national defence section
The preferred material in the fields such as skill, high-tech.China just has been developed that holvi glass material early in 1970s, and
Be widely used in power grid security monitoring, forest fire alarm, large scale integrated circuit photoetching, crop pests prevention and treatment, it is ultraviolet
Special opticals instrument such as optical lens, ultraviolet spectrometer etc. lacks the saturating deep ultraviolet for being used for deep ultraviolet field of detecting at present
Glass material.External holvi glass material product mainly has 9471 holvi glass of 8337B and U.S. CORNING of German Xiao Te
Material, the two are 40% and 35% (thickness 1mm) respectively in the transmitance of 200nm, and the transmitance at 185nm is lower, far not
It is able to satisfy the detection requirement of deep ultraviolet.
Summary of the invention
It is an object of the invention to overcome the shortcomings of currently available technology, provide that a kind of deep ultraviolet transmitance is high, thermal expansion
Coefficient can be with kovar alloy sealing-in matching, the saturating deep ultraviolet glass of low softening temperature that softening temperature is low, chemical stability is excellent.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of deep ultraviolet glass, the component including following weight percentage:
The alkali metal oxide is selected from Li2O、Na2O and K2At least one of O.
The Li2O、Na2O and K2The weight percentage of O is as follows:
Li2O 0-2.0%
Na2O 0-2.0%
K2O 0-2.0%.
The holvi glass with a thickness of 1.0mm when, the transmitance at 185nm is 50% or more, in 30-300
DEG C range thermal expansion coefficient is (60 ± 3) × 10-7/ DEG C, softening temperature is less than 500 DEG C.
The transition metal oxide Fe contained in the deep ultraviolet glass2O3And TiO2Total amount be less than 1PPm.
The present invention also provides a kind of preparation methods of deep ultraviolet glass, comprising the following steps:
(1) iron and conversion are removed: raw material handle except iron, then matches high pure raw material by the component of design,
According to the weight percent of each component, conversion obtains corresponding raw material weight；
(2) fritting and high temperature melt: uniformly mixed mixed powder is added at one time in platinum crucible, 700- is put into
It is melted in advance in 850 DEG C of glass furnace 50-80 minutes；Then it heats up again and carries out high temperature melting operation, with 5-10 DEG C/min
Heating rate is continuously heating to 1200-1350 DEG C, melts 4-8 hours, and carries out 2-3 times in fusion process to mixed powder
Stirring, obtains glass melting liquid；It is melted when the mixed powder melts using protection of reducing atmosphere；
(3) moulding by casting: after powder melting uniformly to be mixed, then by obtained glass melting liquid from glass furnace
It takes out, pours into the heat-resisting steel mold for have been preheated with 450-550 DEG C and pour into defined specification, obtain predetermined formed glass；
(4) it makes annealing treatment: predetermined formed glass being put into annealing furnace and is made annealing treatment, cooling obtains colourless, transparent, equal
Even, bubble-free, estriate blocky holvi glass material.
Gas in the reducing atmosphere is carbon monoxide, the acquisition process of the CO gas reducing atmosphere be by
Small crucible equipped with carbon dust or graphite powder is placed in melting furnace and keeps the temperature 1.5-2.5 hours.
The present invention provides a kind of above-mentioned saturating deep ultraviolet glass again, purple in sealing-in, the manufacture of deep ultraviolet detection window material
Outer lamp, optical window, ultraviolet spectrometer and require all very high optical instrument of ultraviolet-visible light transmission rate, on pick-up lens
Application.
Compared with prior art, the phosphate glass of saturating deep ultraviolet of the invention has characteristics that
(1) there is excellent saturating deep ultraviolet performance, 1mm heavy sheet glass transmitance at 185nm is greater than 50%；
(2) there is suitable thermal expansion coefficient, thermal expansion coefficient is (60 ± 3) × 10-7/℃；
(3) there is low softening temperature, softening temperature is less than 500 DEG C；
(4) and have good chemical stability, II grade of endurance.
In the present invention, P2O5It is the main body that glass forms skeleton structure, is the ingredient to play a major role in glass skeleton,
It is the main component for improving ultraviolet permeability.Phosphate glass system UV cut-off wavelength is short, has and develops high transmission purple
The basic system of outer glass, generally with the [PO of double bond in the network structure of glass4] tetrahedron be unit, mutual apex angle phase
Even, P2O5Weight percent be 54.0-67.0%, P2O5When content is lower than 54%, it is not easy to obtain the ultraviolet glass of high transmittance
Glass, P2O5When content is higher than 67%, the refractive index of glass can be reduced, and the coefficient of expansion increases, while the chemically-resistant that can reduce glass is steady
It is qualitative.
SiO2It is also the main body that glass forms skeleton structure, is the ingredient to play a major role in glass skeleton.SiO2A small amount of
When introducing, [SiO4] tetrahedron and [PO4] tetrahedron apex angle be connected, enhance network structure, the UV absorption limit to shortwave direction move
It is dynamic；When introduction volume is more, [PO4] tetrahedron substantially exists with reticular structure, [SiO4] tetrahedron is superfluous mutually self is connected,
SiO2Ultraviolet cut-on wavelength be 160nm, B2O3Ultraviolet cut-on wavelength be 170nm, P2O5Ultraviolet cut-on wavelength be 145nm,
Due to P2O5Compare SiO2Saturating ultraviolet performance it is good, so generating the UV absorption limit phenomenon mobile to long wave direction.SiO2Weight
Amount percentage is 3.0-10.0%, SiO2Content is lower than 3.0%, is not easy to obtain the uviol of high transmitance thoroughly, while can drop
The chemical-resistant stability of low glass；SiO2When content is higher than 10.0%, the high-temperature viscosity of glass be will increase, and cause glass ultraviolet
Cross rate reduction.
B2O3For network former, and the ingredient of composition glass skeleton.Boron oxygen triangle body [BO3] and boron oxygen four sides
Body [BO4] it is structural component, boron may be with triangle body [BO at different conditions3] or boron oxygen tetrahedron [BO4] exist, in high temperature
It when melting conditions, is generally more difficult to form boron oxygen tetrahedron, and can only be deposited in a manner of trihedral, but in low temperature, in certain item
B under part3+Have and capture free oxygen and form tetrahedral trend, makes close structure and improve the low temperature viscosity of glass, but due to B2O3
There is the characteristic that high temperature reduces glass viscosity and low temperature improves glass viscosity, and reduce the main component of glass refraction, thus
Determine B2O3Content range it is smaller.P2O5Since double bond exists, tetrahedron connection fracture in double bond one end can not form three-dimensional
Network, but layer structure is formed, this will result in phosphate glass poor chemical stability, and the coefficient of expansion is high, and in glass
Introduce the B that can enter glass network2O3Afterwards, internal suspension structure can be repaired, glass has just turned to three from two-dimensional layer structure
The skeleton structure of dimension improves cycle chemistry stability, is conducive to UV absorption and ends to short wave mobile.B2O3Weight percent
For 10.0-25.0%, B2O3Content be lower than 10.0%, the chemical stability of glass can be reduced；B2O3Content be greater than
25.0%, it will increase the thermal expansion coefficient of glass, be inclined to the split-phase of glass and increase.
Al2O3For glass intermediate oxide, Al is added in phosphate glass2O3Afterwards, Al3+It draws in phosphorus oxygen tetrahedron
Double bond oxygen, with [PO4] tetrahedron forms new [AlPO4] structure, the structure and [SiO4] tetrahedral structure is closely similar,
Therefore, [AlPO4] it is to be connected between tetrahedron with bridging oxygen, and by [PO4]、[AlO4] it is folded composition, add network structure
By force, not only chemical stability increases substantially, and can also reduce the coefficient of expansion, and more valuable is that this structure does not reduce bridging oxygen
Quantity, the UV absorption limit and the available guarantee of ultraviolet permeability.Al2O3Weight percent be 6.0-13.0%, Al2O3
Content be lower than 6.0%, glass endurance reduce, transition temperature reduce, Al2O3Content be greater than 13.0%, ultraviolet permeability meeting
It reduces.
Chemical stability can be improved in a small amount of introducing of ZnO, can introduce the chemical property for improving glass, but introduction volume on a small quantity
Glass ultraviolet permeability can be excessively reduced, keeps ultraviolet cut-on wavelength mobile to long wave direction, the weight percent of ZnO is 4.0-
When the content of 7.0%, ZnO are lower than 4.0%, the endurance of glass can be reduced, when the content of ZnO is greater than 7.0%, glass it is ultraviolet
Transmitance can decline.
Li2O、Na2O、K2O is alkali metal oxide, is glass network modifier oxides, main in phosphate glass system
Network breakpoint effect is played, generates non-bridging oxygen, the saturating ultraviolet performance of glass is related with bridging oxygen quantity in glass, and bridging oxygen quantity is more
Then the UV transmission limit is mobile to shortwave direction, and transmitance increases, conversely, transmitance reduces.But because in phosphate system
Because joined SiO2And B2O3, the Li of addition2O、Na2O、K2O has but repaired [PO first4]、[SiO4] and [BO3] between it is disconnected
Knick point, by [BO3] triangle layer structure is transformed into [BO4] tetrahedron make network connection reinforce, bridging oxygen quantity increase, non-bridge
Oxygen content is reduced, so that ultraviolet Intrinsic Gettering is mobile to shortwave direction.The content of alkali metal oxide is 1-5%, the alkali
Metal oxide is selected from Li2O、Na2O and K2At least one of O, wherein Li2The weight percent content of O is 0-2.0%, Na2O
Weight percent content be 0-2.0%, K2The weight percent content of O is 0-2.0%.Because of Li+Atomic radius is small, field strength
Greatly, polarizability is high, but glass metal corrodes crucible serious when weight percent content is greater than 2%, causes glass cord serious,
Influence glass quality；Na2Glass can be improved into glass range in the introducing of O, reduce glass phase-separating and tendency towards devitrification, but weight percent
Ultraviolet permeability can be greatly reduced when being greater than 2% than content.
Of the existing technology in order to solve the problems, such as, the present invention successfully develops 1mm thickness by glass ingredient design optimization
The glass of the glass saturating deep ultraviolet of transmitance greater than 50% at 185nm wavelength is spent, the method for glass preparation is simple, and environmental protection is without dirt
Dye, does not introduce heavy metal ion, and glass melting temperature is lower, and the dark purple outskirt within the scope of 185nm~280nm has ultraviolet permeability
High, the features such as thermal expansion coefficient is suitable, softening temperature is low, chemical stability is excellent, it is suitble to carry out sealing-in with kovar alloy, can uses
In the sealing-in of deep ultraviolet detection window material, it can also be used to manufacture ultraviolet lamp, ultraviolet optics window, ultraviolet spectrometer and requirement
In terms of the first-class deep ultraviolet of all very high optical instrument of ultraviolet-visible light transmission rate, camera lens.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made below further
Ground detailed description.
The present invention provides a kind of deep ultraviolet glass, the component including following weight percentage:
Saturating deep ultraviolet glass of the invention, contains substantially no Cl-、SO3 2-, clarifying agent is not introduced in glass melting process；
The melting of traditional glass needs to be added clarifying agent to achieve the purpose that eliminate Bubbles in Glass, but either uses As2O3、
Sb2O3Equal valence variation elements, can serious absorption far ultraviolet or reduction glass still using F, Cl element for reducing viscosity of glass metal
Chemical stability, do not introduce clarifying agent in glass melting process, it is therefore desirable to could be used without the glass melting of clarifying agent
To prepare saturating deep ultraviolet phosphate glass of the invention.
Saturating deep ultraviolet glass of the invention belongs to phosphate glass system, does not also contain the oxidation of valence variation element substantially
Object, environmentally harmful metal oxide and the oxide with glass coloration function, such as As2O3、Sb2O5、PbO、CdO、
Cr2O3、CuO、CoO、NiO、BeO、CeO2、V2O5、WO3、MoO3、MnO2、SnO2、Ag2O、Nd2O3Any one of Deng, they
Electronic transition energy is lower, and transition occurs for Electron absorption energy under high-energy ray irradiation, therefore in ultraviolet region, especially remote
Ultraviolet region has obvious absorption to ultraviolet light, and therefore, the total amount of objectionable impurities determines that the ultraviolet light of window glass material penetrates
Rate and cutoff wavelength.For there is the glass of requirement in the far-ultraviolet region of 185-200nm, internal impurity Cr, Mn's etc. contains
Amount is less than 1ppm.
Preferably, the alkali metal oxide is selected from Li2O、Na2O and K2At least one of O.
Preferably, the Li2O、Na2O and K2The weight percentage of O is as follows:
Li2O 0-2.0%
Na2O 0-2.0%
K2O 0-2.0%.
Preferably, the holvi glass with a thickness of 1.0mm when, transmitance at 185nm 50% or more,
30-300 DEG C of range thermal expansion coefficient is (60 ± 3) × 10-7/ DEG C, have low softening temperature, softening temperature less than 500 DEG C,
With good chemical stability, II grade of endurance.
Preferably, the transition metal oxide Fe contained in the deep ultraviolet glass2O3And TiO2Total amount be less than
1PPm。
Saturating deep ultraviolet glass of the invention contains substantially no transition metal oxide Fe2O3And TiO2Even if containing being also
Since impurity is brought into raw material, total amount is less than 1PPm；The many because being known as of deep ultraviolet glass ultraviolet permeability are influenced, in addition to
Outside the ingredient of glass, such as Fe containing objectionable impurities, Ti etc. are a key factors, seriously affect glass denier impurity
UV transmission, therefore to prevent in the entire production process of glass the pollution of objectionable impurities.
The specific ingredient that contains substantially no in the present invention refers to the meaning that do not add intentionally, it is not excluded that from raw material
Impurity etc. is inevitably mixed into extremely micro impurity, and the degree that will not be impacted to desired characteristic contains, i.e.,
Make the amount containing extremely pettiness be also due to other glass raw materials to be brought into, but these appraise at the current rate when to the introducing of glass raw material
The content of element will be strict controlled in 1ppm or less.
The present invention also provides a kind of preparation methods of deep ultraviolet glass, comprising the following steps:
(1) iron and conversion are removed: raw material handle except iron, then matches high pure raw material by the component of design,
According to the weight percent of each component, conversion obtains corresponding raw material weight；
Primary raw material handled except iron to improve the purity of glass raw material, P in the present invention by the present invention2O5With high purity phosphorus
Acid introduce, first other raw materials are prepared in blending process it is uniformly mixed, then by load weighted P2O5It is slowly added into and matches in batches
It closes in material, is gently mixed uniformly；
(2) fritting and high temperature melt: uniformly mixed mixed powder is added at one time in platinum crucible, 700- is put into
It is melted in advance in 850 DEG C of glass furnace 50-80 minutes；Then it heats up again and carries out high temperature melting operation, with 5-10 DEG C/min
Heating rate is continuously heating to 1200-1350 DEG C, melts 4-8 hours, and carries out 2-3 times in fusion process to mixed powder
Stirring, obtains glass melting liquid；It is melted when the mixed powder melts using protection of reducing atmosphere；
Due to P2O5Heat volatile quantity it is big, cause glass ingredient not easy to control, therefore the present invention is using disposable charging,
Low temperature fritting technology.
It is melted when glass mixture melts using protection of reducing atmosphere, is more advantageous to using reducing atmosphere than oxidizing atmosphere
To the stable saturating far ultraviolet glass of high transmittance；And be stirred with basket formula blender, so that high-temperature glass liquid clarification is eliminated bubble,
The homogenizing that futher stirs after taking bubble-free eliminates striped.
(3) moulding by casting: after powder melting uniformly to be mixed, then by obtained glass melting liquid from glass furnace
It takes out, pours into rapidly in the heat-resisting steel mold for have been preheated with 450-550 DEG C and pour into defined specification, obtain predetermined molding glass
Glass；
(4) it makes annealing treatment: predetermined formed glass being put into annealing furnace and is made annealing treatment, cooling obtains colourless, transparent, equal
Even, bubble-free, estriate blocky holvi glass material.
Preferably, the gas in the reducing atmosphere is carbon monoxide, the acquisition of the CO gas reducing atmosphere
Process is that the small crucible equipped with carbon dust or graphite powder is placed in melting furnace to keep the temperature 1.5-2.5 hours.
Preparation method of the present invention is simple, and glass melting temperature is lower, prepared saturating deep ultraviolet light glass material function admirable, fits
It closes and carries out sealing-in with kovar alloy, can be used for the sealing-in of deep ultraviolet detection window material, it can also be used to manufacture ultraviolet lamp, optical window
Mouthful, ultraviolet spectrometer and require all very high optical instrument of ultraviolet-visible light transmission rate, pick-up lens etc., have wide
Wealthy market application prospect.
Below by specific embodiment, the present invention is further illustrated:
List the glass chemistry composition (wt.%) and glass properties of embodiment in detail in table 1.
(1) uv transmittance T [transmitance of glass when λ=185nm]；
(2) thermalexpansioncoefficientα30/300For 30-300 DEG C of mean thermal expansion coefficients α30/300[10-7/℃]。
Wherein, sample carries out various physical and chemical performance tests according to test request after surface grinding, polishing treatment；Glass
Uv transmittance T at 185nm is tested using spectrophotometer；30-300 DEG C of linear expansion coefficient uses horizontal expander
Instrument measurement, is indicated with average linear expansion coefficient, is measured using method as defined in ISO 7991.
The chemical composition (wt.%) and glass properties of 1 embodiment of table
Embodiment 1
Firstly, selecting glass raw material by 1 embodiment of table, 1 glass composition, and primary raw material in glass raw material is removed
Iron is handled to improve the purity of glass raw material, to the oxide such as Fe of valence variation element2O3Deng progress strict control, finished glass
Fe2O3Content is less than 1PPm, by glass sand (Fe2O3Content is less than 1PPm), boric anhydride (400 μm of oversizes are 10% or less,
63 μm of screenings are 10% or less), high-purity phosphoric acid, aluminum acetate (analysis is pure) after mixing, add alkali metal and introduce raw material
Lithium carbonate (analysis is pure), sodium carbonate (analysis is pure), potassium carbonate (analysis is pure) mixing, chemically react when to avoid mixing, make
The batch got ready not placed for a long time, carry out feeding operation as early as possible, react generation group to avoid phosphoric acid and raw material
It is poly-.The volatilization of phosphoric acid is very big, in order to ensure the glass prepared and design ingredient are almost the same, using low temperature fritting means by phosphorus
The volatile batch such as hydrochlorate is melting into glass clinker, and when fritting uses covered pot, to reduce glass component volatilization, fritting
It is heated in the glass furnace that temperature is 800 DEG C 1 hour, is then continuously heating to 1300 DEG C with 8 DEG C/min of heating rate and melts
Change 6 hours, be melted when glass mixture melts using protection of reducing atmosphere, the gas in reducing atmosphere is carbon monoxide, described
The acquisition process of CO gas reducing atmosphere is that the small crucible equipped with carbon dust or graphite powder is placed in heat preservation 2 in melting furnace is small
When.Since the density difference of various raw materials is larger, it is easy to produce uneven concentration phenomenon and makes the reduction of glass transmitance, therefore
It needs to be stirred glass melting liquid 2-3 times in fusion process, keeps glass smelting uniform, after glass melting, then by glass
Glass molten liquid from furnace take out rapidly pour into the heat-resisting steel mold for having been preheated with 500 DEG C pour into as defined in test article want
It asks, is then placed in annealing furnace and makes annealing treatment, it is cooling to obtain colourless, transparent, uniform, bubble-free, estriate bulk thoroughly deeply
Uviol material.Its test performance is as shown in table 1, and uv transmittance reaches 52.1% when (1) wavelength 185nm；(2)30-
300 DEG C of average linear expansion coefficient 63 × 10-7/℃。
Embodiment 2
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 2 of table
It heats 80 minutes in the glass furnace that prefusing temperature is 700 DEG C, is then continuously heating to 5 DEG C/min of heating rate
1350 DEG C, the melting process system of melting 4 hours, and select to be preheating in 550 DEG C of heat-resisting steel mold and pour into defined survey
Preproduction and test condition same as Example 1 show the basic performance of sample in table 1.(1) ultraviolet when wavelength 185nm
Light transmission rate reaches 51.2%；(2) 30-300 DEG C of average linear expansion coefficient 58 × 10-7/℃。
Embodiment 3
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 3 of table
It heats 50 minutes in the glass furnace that prefusing temperature is 850 DEG C, is then continuously heating to 10 DEG C/min of heating rate
8 hours melting process systems are melted at 1200 DEG C, and are selected to be preheating in 450 DEG C of heat-resisting steel mold and poured into defined survey
Preproduction and test condition same as Example 1 show the basic performance of sample in table 1.(1) ultraviolet when wavelength 185nm
Light transmission rate reaches 51.4%；(2) 30-300 DEG C of average linear expansion coefficient 59 × 10-7/℃。
Embodiment 4
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 4 of table
Identical melting process system and test condition show the basic performance of sample in table 1.(1) UV light permeability when wavelength 185nm
Rate reaches 52.2%；(2) 30-300 DEG C of average linear expansion coefficient 61 × 10-7/℃。
Embodiment 5
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 5 of table
Identical melting process system and test condition show the basic performance of sample in table 1.(1) UV light permeability when wavelength 185nm
Rate reaches 51.2%；(2) 30-300 DEG C of average linear expansion coefficient 58 × 10-7/℃。
Embodiment 6
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 5 of table
Identical melting process system and test condition show the basic performance of sample in table 1.(1) UV light permeability when wavelength 185nm
Rate reaches 52.3%；(2) 30-300 DEG C of average linear expansion coefficient 59 × 10-7/℃。
The present invention also provides a kind of deep ultraviolet glass in the application for carrying out sealing-in with kovar alloy, can be used for deep ultraviolet spy
Survey the sealing-in of window material, it can also be used to manufacture ultraviolet lamp, optical window, ultraviolet spectrometer and require ultraviolet-visible light saturating
Cross all very high optical instrument of rate, pick-up lens etc..
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of deep ultraviolet glass, which is characterized in that the component including following weight percentage:
2. a kind of deep ultraviolet glass according to claim 1, which is characterized in that the alkali metal oxide is selected from
Li2O、Na2O and K2At least one of O.
3. a kind of deep ultraviolet glass according to claim 2, which is characterized in that the alkali metal oxide Li2O、Na2O
And K2The weight percentage of O is as follows:
Li2O 0-2.0%
Na2O 0-2.0%
K2O 0-2.0%.
4. a kind of deep ultraviolet glass according to claim 1-3, which is characterized in that the holvi glass
When with a thickness of 1.0mm, transmitance at 185nm be 50% or more, in 30-300 DEG C of range thermal expansion coefficient (60 ±
3)×10-7/ DEG C, softening temperature is less than 500 DEG C.
5. a kind of deep ultraviolet glass according to claim 4, which is characterized in that contain in the deep ultraviolet glass
Transition metal oxide Fe2O3And TiO2Total amount be less than 1PPm.
6. a kind of preparation method of deep ultraviolet glass according to claim 1-5, which is characterized in that including with
Lower step:
(1) iron and conversion are removed: raw material handle except iron, then matches high pure raw material by the component of design, according to
The weight percent of each component, conversion obtain corresponding raw material weight；
(2) fritting and high temperature melt: uniformly mixed mixed powder is added at one time in platinum crucible, 700-850 is put into
DEG C glass furnace in melt in advance 50-80 minutes；Then it heats up again and carries out high temperature melting operation, with 5-10 DEG C/min of liter
Warm rate is continuously heating to 1200-1350 DEG C, melts 4-8 hours, and stir for 2-3 times to mixed powder in fusion process
It mixes, obtains glass melting liquid；It is melted when the mixed powder melts using protection of reducing atmosphere；
(3) moulding by casting: after powder melting uniformly to be mixed, then obtained glass melting liquid is taken from glass furnace
Out, it pours into the heat-resisting steel mold for have been preheated with 450-550 DEG C and pours into defined specification, obtain predetermined formed glass；
(4) make annealing treatment: predetermined formed glass being put into annealing furnace and is made annealing treatment, it is cooling obtain it is colourless, transparent, uniform,
Bubble-free, estriate blocky holvi glass material.
7. preparation method according to claim 6, which is characterized in that the gas in the reducing atmosphere is carbon monoxide,
The acquisition process of the CO gas reducing atmosphere is that the small crucible equipped with carbon dust or graphite powder is placed in melting furnace to protect
It is 1.5-2.5 hours warm.
8. a kind of a kind of described in any item deep ultraviolet glass of claim 1-5, deep ultraviolet detection window material sealing-in,
It manufactures ultraviolet lamp, optical window, ultraviolet spectrometer and requires all very high optical instrument of ultraviolet-visible light transmission rate, camera shooting
Application on camera lens.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910577996.5A CN110183104B (en) | 2019-06-28 | 2019-06-28 | Deep ultraviolet transparent glass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910577996.5A CN110183104B (en) | 2019-06-28 | 2019-06-28 | Deep ultraviolet transparent glass and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110183104A true CN110183104A (en) | 2019-08-30 |
| CN110183104B CN110183104B (en) | 2021-09-28 |
Family
ID=67724223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910577996.5A Active CN110183104B (en) | 2019-06-28 | 2019-06-28 | Deep ultraviolet transparent glass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183104B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114430731A (en) * | 2019-11-05 | 2022-05-03 | 日本电气硝子株式会社 | Ultraviolet ray transmitting glass |
| CN115975407A (en) * | 2022-12-23 | 2023-04-18 | 西安交通大学 | Nickel-based alloy surface photoelastic glass coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173456A (en) * | 1990-12-20 | 1992-12-22 | Schott Glass Technologies, Inc. | Phosphate glass useful in high energy lasers |
| CN102545029A (en) * | 2010-09-13 | 2012-07-04 | 肖特公司 | Aluminophosphate glass composition |
| CN106966590A (en) * | 2017-05-18 | 2017-07-21 | 南通市国光光学玻璃有限公司 | The preparation method of the optical glass of ultraviolet band high transmission and resistance to ultraviolet irradiation |
| JP2018151367A (en) * | 2017-03-14 | 2018-09-27 | 日本電気硝子株式会社 | Regenerating method of radiation detection glass |
| JP2018150190A (en) * | 2017-03-13 | 2018-09-27 | 日本電気硝子株式会社 | Glass for radiation detection |
-
2019
- 2019-06-28 CN CN201910577996.5A patent/CN110183104B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173456A (en) * | 1990-12-20 | 1992-12-22 | Schott Glass Technologies, Inc. | Phosphate glass useful in high energy lasers |
| JPH0640743A (en) * | 1990-12-20 | 1994-02-15 | Schott Glass Technol Inc | Phosphate glass being useful for high energy laser |
| CN102545029A (en) * | 2010-09-13 | 2012-07-04 | 肖特公司 | Aluminophosphate glass composition |
| JP2018150190A (en) * | 2017-03-13 | 2018-09-27 | 日本電気硝子株式会社 | Glass for radiation detection |
| JP2018151367A (en) * | 2017-03-14 | 2018-09-27 | 日本電気硝子株式会社 | Regenerating method of radiation detection glass |
| CN106966590A (en) * | 2017-05-18 | 2017-07-21 | 南通市国光光学玻璃有限公司 | The preparation method of the optical glass of ultraviolet band high transmission and resistance to ultraviolet irradiation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114430731A (en) * | 2019-11-05 | 2022-05-03 | 日本电气硝子株式会社 | Ultraviolet ray transmitting glass |
| CN115975407A (en) * | 2022-12-23 | 2023-04-18 | 西安交通大学 | Nickel-based alloy surface photoelastic glass coating and preparation method thereof |
| CN115975407B (en) * | 2022-12-23 | 2023-12-19 | 西安交通大学 | Nickel-based alloy surface photoelastic glass coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110183104B (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0640571B1 (en) | A wavelength up-conversion glass ceramic and a process for the production thereof | |
| CN101190827B (en) | Glass article and method for making thereof | |
| CN110240402B (en) | Environment-friendly deep ultraviolet-transmitting borosilicate glass and preparation method and application thereof | |
| Boulos et al. | Structure and properties of silver borate glasses | |
| CA1230893A (en) | Lithium alumino-silicate glass-ceramics | |
| CN110040941B (en) | Visible light absorption glass and preparation method and application thereof | |
| CN106477877B (en) | Extra-high refraction high density environment-friendly type cameo glass of one kind and preparation method thereof | |
| CN110204192B (en) | Deep ultraviolet transparent phosphate glass and preparation method and application thereof | |
| CN105102389A (en) | Nanostructured lenses and vitroceramics that are transparent in visible and infrared ranges | |
| CN107082562A (en) | Optical glass, optical element and preformed articles for precise pressurization shaping | |
| CN110183104A (en) | A kind of deep ultraviolet glass and preparation method thereof, application | |
| CN105481245B (en) | Composition of scintillation glass for preparing flash fiber panel and preparation method thereof | |
| CN110156317B (en) | Ultraviolet, visible and near-infrared light absorbing glass and preparation method and application thereof | |
| CN110240404B (en) | Tellurate infrared-transmitting glass and preparation method thereof | |
| ElBatal et al. | γ-ray interaction with bioglasses containing transition metal ions | |
| CN103848570B (en) | A kind of high refractive index mid-infrared light glass and preparation method thereof | |
| CN110255898B (en) | Deep ultraviolet transparent glass, preparation method, application and melting device thereof | |
| HARRISON et al. | Reactions in the System TiO2‐P2O5 | |
| CN105923991B (en) | Optical glass, its preparation method and application | |
| CN110128006B (en) | Environment-friendly high-refractive-index ultraviolet-transmitting glass and preparation method thereof | |
| CN110117158A (en) | It is a kind of with low-refraction, the optical glass of high transmittance and its preparation method and application | |
| CN109734310B (en) | High-transmittance optical glass with visible light deep cutoff | |
| Gliemeroth | Optical properties of optical glass | |
| CN110156335A (en) | A kind of middle numerical aperture fiber optical glass and its preparation method and application | |
| Siligardi et al. | Vanadium doping in CaO-ZrO2-SiO2 glasses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |