CN107082561B - A kind of calcium tantalum aluminate glass and its preparation method and application - Google Patents
A kind of calcium tantalum aluminate glass and its preparation method and application Download PDFInfo
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- CN107082561B CN107082561B CN201710211672.0A CN201710211672A CN107082561B CN 107082561 B CN107082561 B CN 107082561B CN 201710211672 A CN201710211672 A CN 201710211672A CN 107082561 B CN107082561 B CN 107082561B
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
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- 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
- C03B5/23—Cooling the molten glass
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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Abstract
The present invention relates to a kind of calcium tantalum aluminate glass and preparation method thereof, the raw material of the calcium tantalum aluminate glass is made of calcium source, silicon source, tantalum source, and calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5Meter, each component Mole percent composition are as follows: 10≤CaO≤35,32.5≤Al2O3≤ 54,26≤Ta2O5≤45；The calcium tantalum aluminate glass visible region transmitance is 79-82%, refractive index ndFor 1.93-2.03, Vickers hardness 8.59-9.06GPa, glass transition temperature is 822.3-855.3 DEG C.Preparation method includes that glass raw material mixing, frit tabletting, frit pre-burning, pneumatic suspension prepare glass without container method and make annealing treatment five steps.Calcium tantalum aluminate glass manufactured in the present embodiment has the excellent physical properties such as the excellent optical property such as high refractive index, high transmittance and high temperature resistant, high rigidity.
Description
Technical field
The present invention relates to technical field of inorganic material, and in particular to a kind of calcium tantalum aluminate glass and preparation method thereof and uses
On the way.
Background technique
Optical glass may be defined as under the action of extraneous physical condition changes, and the optical property of glass changes, and
The glass material that there is detection and convert such performance derived in conjunction with these variations.Optical glass material can manufacture various light
Learn instrument, component.In recent years, with optoelectronic areas, atomic energy field, aerospace field, optical communication field, infrared neck
The rapid development in domain and laser field, it is important in each field that various novel optical functional glass have gradually embodied them
Property.Optical glass is needed toward thinner and lighter, but the performances such as intensity, hardness, refractive index more preferably develop in direction, to adapt to people
The requirements at the higher level of life and work.
Existing commercialization glass of high refractive index depends on heavy metallic oxide component, the glass pollution environment containing PbO,
Endanger the health of people.And contain Bi2O3、TeO2Glass of high refractive index due to limiting it there are heavy metal ion coloring
Visible region and near-infrared region application.Although higher refractive index may be implemented in titan silicate glass, but due to it
Middle silicon oxygen bond phonon energy is high, it is difficult to be applied to middle infrared band.Therefore, at present still without a kind of ideal high refractive index glass
Glass can be applied to the entire red wave band in visible light-China and foreign countries.
The ranges of indices of refraction of general glass is between 1.45-1.75, and glass of high refractive index of the refractive index greater than 1.75 is often
Biggish tendency towards devitrification and higher fusion temperature are shown, is prepared relatively difficult.The most common optical glass prepares work at present
There are two types of skills, and one is crucible manufacturing process, and one is sol-gal process preparation processes.When using crucible manufacturing process, optics
Glass is more demanding to crucible, need to there is that iron-content is low, it is good to resist glass metal erosion performance, loading softening deformation temperature is high, heat
It has good stability, the problem of product parameters are easy fluctuation even can be also encountered using platinum crucible method.Collosol and gel legal system
Then there are the technical problems such as hair check when how to prevent gelation and vitrifying in standby optical glass.
Tokyo University and the research group of Japanese Synchrotron Radiation Study mechanism JASRI report a kind of novel 54Al2O3-
46Ta2O5Binary system glass is prepared using gas suspension without container technique, with up to 1.94 refractive index ndBe more than general
The properties such as the hardness of metal material.However the formation area of this glass is very limited, high temperature viscosity is big, in disturbing for air-flow
Minute bubbles are easily generated under dynamic and are not easy to be discharged.
Summary of the invention
It is a kind of with excellent the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
Calcium tantalum aluminate glass of good optical property and physical property and preparation method thereof is able to solve existing preparation process and easily analyses
Crystalline substance is also easy to produce the problems such as bubble.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of calcium tantalum aluminate glass is provided, the raw material of the calcium tantalum aluminate glass is made of calcium source, silicon source, tantalum source,
Calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5Meter, each component Mole percent composition are as follows: 10≤CaO≤35,32.5
≤Al2O3≤ 54,26≤Ta2O5≤ 45, the sum of three component molar percentages are 100%；
The calcium tantalum aluminate glass visible region transmitance is 79-82%, refractive index ndFor 1.93-2.03, Vickers is hard
Degree is 8.59-9.06GPa, and glass transition temperature is 822.3-855.3 DEG C.
According to the above scheme, the calcium source is CaSO4Powder, Ca (OH)2Powder, CaCO3Powder, Ca (HCO3)2In powder
It is a kind of；Source of aluminium is Al (OH)3Powder, Al2(SO4)3Powder, α-Al2O3One of powder；The tantalum source is Ta2O5Powder
End；The calcium source is that 99.99% analysis is pure, and silicon source is that 99.99% analysis is pure, and tantalum source is that 99.5% analysis is pure.
The present invention also provides the preparation methods of above-mentioned calcium tantalum aluminate glass comprising glass raw material mixing, frit pressure
Piece, frit pre-burning, pneumatic suspension prepare five steps of glass and annealing without container method, the specific steps are as follows:
1) glass raw material mixes: calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5It counts, in molar ratio 10≤CaO
≤ 35,32.5≤Al2O3≤ 54,26≤Ta2O5≤ 45 weigh raw material, and raw material is placed in mortar or ball grinder and is fully ground
Mixing, obtains uniform glass mixture；
2) frit tabletting: glass mixture obtained by step 1) is placed in tabletting in mold, pressure 5-30Mpa is set, is obtained
To foliated glass mixture；
3) frit pre-burning: sheet glass mixture obtained by step 2) is fitted into crucible, crucible is then placed in Muffle
Pre-burning in furnace obtains block shape glass mixture；
4) pneumatic suspension prepares glass without container method: block shape glass mixture obtained by step 3) is broken into small blocks sample
Product, taking quality is that the block sample of 20-25mg is placed on the nozzle of pneumatic suspension furnace, is suspended in block sample with high-purity gas
In the air, after suspending stabilized, carrying out heating to block sample with laser makes its fusing, is uniformly mixed to gained liquid glass material
Afterwards, laser is closed, stopping heats it, then cools down liquid glass material rapidly, obtains glass marble；
5) it makes annealing treatment: glass marble obtained by step 4) being placed in Muffle furnace and is made annealing treatment, with furnace after annealing
It is cooled to room temperature, obtains calcium tantalum aluminate glass.
According to the above scheme, step 3) the pre-sinter process condition are as follows: calcined temperature is 1000-1200 DEG C, and burn-in time is
6-12 hours.
According to the above scheme, the step 4) high-purity gas is Ar, O2、N2One of, purity >=99.99%.
According to the above scheme, the step 4) method for cooling down liquid glass material rapidly is rapidly cold using wind cooling method
But, cooling rate 300-400K/s.
According to the above scheme, step 5) the annealing treating process condition are as follows: annealing temperature is 800-850 DEG C, annealing time
For 1-4h.
The invention also includes application of the above-mentioned calcium tantalum aluminate glass in optical element and optical window resistant to high temperature.
And application of the above-mentioned calcium tantalum aluminate glass in high hardness wear-resisting coating material.
Calcium tantalum aluminate glass has very high melting temperature, and glass forming ability is lower, and this glass is made
It is often extremely difficult, very high high-temperature fusion liquid cooling rate is needed, such component is using conventional melt cooling can not
Form glass.The present invention by using pneumatic suspension without container freezing method so that can not be at the calcium tantalum of glass using conventional method
Aluminate component is capable of forming glass, then eliminates internal stress by subsequent annealing and obtain calcium tantalum aluminate glass, studies
The corresponding each component molar content of calcium tantalum aluminate glass is formed under the experiment condition, obtains optical property and physical property
All more superior calcium tantalum aluminate glass.
No container technique is exactly a kind of effective means for preparing novel glass of high refractive index material, it can by control from
The high-speed flow ejected in the nozzle of certain structure realizes the suspension of sample, and by laser heating, using its without crucible,
The effect of contraction of contactless feature and surface tension of high-temperature melt prepares excellent optical performance, normal condition is difficult to make
Standby novel glass of high refractive index material.No container technique can be divided into electromagnetic suspension, electrostatic suspension, gas film suspending and acoustic levitation with
And pneumatic suspension, so-called no container technique are exactly to make object using power the effects of magnetic field, electric field and gas to offset gravity
It suspends, laser heating fusing is recycled to carry out the process of nonequilibrium state solidification.Currently, measurement thermophysics performance is surveyed without container
There are mainly five types of amount methods.Electromagnetic suspension technology, principle are the vortex that are generated using electromagnetic field of high frequency in metal surface to realize
Suspension to metal ball, but need to be manipulated in micro-gravity conditions.Electrostatic suspension technology, advantage are that heating metal can be single
It solely carries out, and can be studied at a lower temperature, but surface tension and viscosity may be influenced, and can be in height respectively
It is carried out under vacuum condition.Gas film suspending technology, the disadvantage is that drop can be made from spherical shape to serious distortion, lead to surface tension and glued
The measurement of degree is not so ideal.Acoustic levitation technique is the key that realization material solvent-catalyst free skill under ground and steric requirements
One of art is compared with electromagnetic suspension technology, is limited whether it is not by materials conductive, and is suspended and heated and control respectively, thus
It can be used for studying solidifying without container for nonmetallic materials and low-melting alloy.Conical nozzle pneumatic suspension technology, mainly from
Bottom, which sprays gas, makes sample suspend, and recycles laser heating melting sample.
Al in simple glass2O3Content it is often very low, although pure alumina cannot form glass, calcium oxide, oxygen is added
Aluminate glass can be formed after changing the oxides such as strontium, barium monoxide, magnesia, beryllium oxide.Wherein, with " CaO-Al2O3" (oxidation
Aluminium mass percent is 38%~65%) system is most widely used.In this kind of glass, aluminium ion is mainly with [AlO4] co-ordination state
In the presence of.Aluminate glass has good mechanics, calorifics, optical property, is infrared (wavelength is more than 3 microns) oxide glass
In it is preferable a kind of.The introducing of tantalum pentoxide is the key factor that calcium tantalum aluminate glass has high hardness value, five oxygen
Change the bulk density that two tantalums increase system, while tantalum pentoxide has high dissociation energy, so that alumina hight coordinate.
The biggish bivalent metal ion of ionic radius, such as Ca2+、Sr2+、Ba2+, mostly there is higher ligancy (being greater than 6),
Generally it is filled in oxygen-octahedron or aluminum-oxygen tetrahedron.Al2O3-Ta2O5System glass in a certain range, CaO (both Ca2+)
The increase of content, Ca2+It is filled in aluminum-oxygen tetrahedron, plays the role of accumulation in aluminate glass, make the refractive index, close of network
The performances such as degree and hardness improve, and facilitate the formation of glass.CaO is network modifying oxide, Ca2+It is network-modifying ion, by
In Ca2+Radius itself is big, and electricity price is small, they do not polarize vulnerable to the effect of extra electric field.Moreover, Ca2+To the O of surrounding2-
The electron cloud constraint of ion is small, makes O2-Ion does not polarize vulnerable to the effect of external electric field, is added one in system in view of the foregoing
Quantitative Ca2+To Al2O3-Ta2O5The refractive index of system glass is little.
Process aspect, it is contemplated that Al2O3-Ta2O5During the experiment, molten state drop is inevitably by air-flow for system
Disturbance and be readily incorporated bubble, appropriate CaO is then added in former binary system to reach reduce glass metal high temperature it is glutinous
Degree, the fusing and clarification for promoting glass metal, to achieve the purpose that fundamentally to reduce or eliminate minute bubbles.
In short, being temporarily directed to CaO-Al without open both at home and abroad so far2O3-Ta2O5The invention of ternary system glass is special
Benefit, the present invention is by pneumatic suspension without container solidification technology, and preparing oxide raw material, proportion is different out but size is more uniform
CaO-Al2O3-Ta2O5System glass pellet can be applied to optical element and optical window resistant to high temperature, in micro mist shape
State can apply to high hardness wear-resisting coating material.
Calcium aluminium tantalates glass have very high melting temperature, and glass forming ability (crystallization temperature of glass with
The difference of glass transformation temperature) very low (60K or so), it is often extremely difficult to be made this glass, needs very high high temperature melting
Melt liquid cooling rate.The present invention has prepared calcium tantalum aluminate glass without container solidification technology by pneumatic suspension, the calcium tantalum
Aluminates system glass has good optical property and physical property.
The beneficial effects of the present invention are: 1, in of the present invention constitutive material there was only Al2O3A kind of intermediate oxide serves as
Network in calcium tantalum aluminate glass glass system generates oxide body, CaO and Ta2O5In calcium tantalum aluminate glass system
It serves as network modifying oxide and does not participate in grid.Traditional glass is that the aluminium oxide of 6% or more the addition in silicate glass comes
Increase refractive index, still with [SiO4] it is used as Network ontology structure, since the improvement of refractive index is largely related with aluminium, folding
The rate of penetrating is difficult to more than 1.75, and aluminium content is also extremely limited to general so-called high alumina in fact.And this system raw material is single, system
Completely with [AlO4] structure is served as, aluminium oxide is directly largely introduced, high aluminium content has been really achieved；2, of the invention by CaSO4
(or Ca (OH)2、CaCO3、Ca(HCO3)2) powder, Al (OH)3(or Al2(SO4)3、α-Al2O3) powder, Ta2O5Powder is according to the ratio
Mixing, and transparent glass is made without container method by pneumatic suspension；Transparent glass is eliminated in Tg temperature heat treated below
Thermal stress makes it have an excellent optical property such as high refractive index, high transmittance, excellent physical such as high temperature resistant, high rigidity
(after tested, gained calcium tantalum aluminate glass glass transition temperature Tg reaches 822.3-855.3 DEG C to energy, a crystallization temperature Tp1It reaches
877.4-912.6 DEG C, Δ T reaches 48.1-57.3 DEG C, and vickers microhardness Hv reaches 8.591-9.061GPa, refractive index ndIt reaches
1.936-2.032), optical element and optical window resistant to high temperature be can be used as, or applied with micronised state applied to high hardness wear-resisting
Layer material.
Detailed description of the invention
Fig. 1 is the photo of calcium tantalum aluminate glass prepared by the embodiment of the present invention 2；
Fig. 2 is the DSC figure of calcium tantalum aluminate glass prepared by embodiment 1；
Fig. 3 is the microhardness figure of calcium tantalum aluminate glass prepared by embodiment 1；
Fig. 4 is the refractive index curve chart of calcium tantalum aluminate glass prepared by embodiment 1.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
The laser of AALF-1 type shower furnace used in the embodiment of the present invention heats and control system contains three CO2Laser,
In the power of two bottom lasers be 40W, the power of another top lasers device is 80W.
Calcium source (CaSO used in the present embodiment4Powder, Ca (OH)2Powder, CaCO3Powder, Ca (HCO3)2Powder) be
99.99% analyzes pure, silicon source (Al (OH)3Powder, Al2(SO4)3Powder, α-Al2O3Powder) it is 99.99% pure, the tantalum source of analysis
(Ta2O5Powder) it is that 99.5% analysis is pure.
Embodiment 1
Prepare 10CaO-45Al2O3-45Ta2O5Calcium tantalum aluminate glass, steps are as follows:
(1) frit mixes
By analytically pure CaCO3Powder, α-Al2O3Powder, Ta2O5Powder is according to 10CaO:45Al2O3: 45Ta2O5(mole
Percentage) proportion accurate weighing be placed in mortar, be fully ground mixing in the agate mortar, obtain uniform glass mixing
Material.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 15MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1100 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 20.25mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, cooling rate 300-400K/s, calcium tantalum aluminate is made
Glass.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 835 DEG C, soaking time 2h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=855.3 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=912.6 DEG C, T=57.3 DEG C of Δ.Its vickers microhardness Hv=924 (1Hv=9.80665MPa)=
9.061GPa refractive index nd(wavelength X=587.6nm)=2.032.
Fig. 2 show the DSC figure of calcium tantalum aluminate glass manufactured in the present embodiment, it is known that the high Tg=of its glass transformation temperature
855.3 DEG C (transition temperature of normal silicate glass is usually no more than 600 DEG C).Fig. 3 is calcium tantalum aluminic acid manufactured in the present embodiment
The microhardness figure of salt glass, lateral diagonal line value and longitudinal cornerwise difference range show the table of test less than 0.5 micron
Flatness needed for face meets；With, without obvious scratch and concave point, test surfaces polishing preferably, is shown in 40 times of amplified figures of focal length
Microhardness value is 924Hv (9.06GPa), has wear-resisting, scratch resistance glass characteristic.Fig. 4 is calcium tantalum aluminic acid manufactured in the present embodiment
The refractive index curve chart of salt glass, refractive index value reduces, refractive index n with the increase of wavelength in 375-900nm wave-length coveraged
(wavelength X=587.6nm)=2.032, it is known that its refractive index in visible wavelength region is high, spy with a high refractive index
Property.
Embodiment 2
Prepare calcium tantalum aluminate glass 10CaO-48.6Al2O3-41.4Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure CaSO4Powder, Al (OH)3Powder, Ta2O5Powder is according to 10CaO:48.6Al2O3: 41.4Ta2O5
The proportion accurate weighing of (molar percentage) is placed in mortar, is fully ground mixing in the agate mortar, obtains uniform glass
Glass mixture.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 15MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1100 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 21.37mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 810 DEG C, soaking time 2h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=832.1 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=886.6 DEG C, T=54.5 DEG C of Δ.Its vickers microhardness Hv=902 (1Hv=9.80665MPa)=
8.846GPa refractive index nd(wavelength X=587.6nm)=1.973.
Embodiment 3
Prepare calcium tantalum aluminate glass 20CaO-40Al2O3-40Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure Ca (OH)2Powder, Al2(SO4)3Powder, Ta2O5Powder is according to 20CaO:40Al2O3: 40Ta2O5
The proportion accurate weighing of (molar percentage) is placed in mortar, is fully ground mixing in the agate mortar, obtains uniform glass
Glass mixture.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 15MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1100 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 21.95mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 810 DEG C, soaking time 2h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=850.6 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=903.1 DEG C, T=52.5 DEG C of Δ.Its vickers microhardness Hv=897 (1Hv=9.80665MPa)=
8.797GPa refractive index nd(wavelength X=587.6nm)=1.971.
Embodiment 4
Prepare calcium tantalum aluminate glass 20CaO-43.2Al2O3-36.8Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure Ca (HCO3)2Powder, α-Al2O3Powder, Ta2O5Powder is according to 20CaO:43.2Al2O3:
36.8Ta2O5The proportion accurate weighing of (molar percentage) is placed in mortar, is fully ground mixing in the agate mortar, is obtained
Uniform glass mixture.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 15MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1100 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 22.03mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 810 DEG C, soaking time 2h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=840.0 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=888.1 DEG C, T=48.1 DEG C of Δ.Its vickers microhardness Hv=889 (1Hv=9.80665MPa)=
8.718GPa refractive index nd(wavelength X=587.6nm)=1.969.
The transmission cutoff wavelength of calcium tantalum aluminate glass, light transmittance prepared by embodiment 1-4, optical band gap energy test result
It is shown in Table 1.
Table 1
As shown in Table 1, the calcium tantalum aluminate glass light transmittance (79.865- with higher of preparation of the embodiment of the present invention
81.967%) and lesser through cutoff wavelength (284-290nm), optical band gap can be 4.28-4.37, eV, show negative in glass
The degree of polarization of ion is stronger, illustrates that influence of the increase of calcium oxide content to light transmittance is little, still can meet compact optical
Parameter request of the instrument window glass to light transmittance (being greater than 75%).
Embodiment 5
Prepare calcium tantalum aluminate glass 10CaO-54Al2O3-36Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure CaSO4Powder, α-Al2O3Powder, Ta2O5Powder is according to 10CaO:54Al2O3: 36Ta2O5(mole
Percentage) proportion accurate weighing be placed in mortar, be fully ground mixing in the agate mortar, obtain uniform glass mixing
Material.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 5MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1000 DEG C,
Soaking time is 6 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 22.63mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 800 DEG C, soaking time 1h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=822.3 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=877.4 DEG C, T=55.1 DEG C of Δ.Its vickers microhardness Hv=885 (1Hv=9.80665MPa)=
8.679GPa refractive index nd(wavelength X=587.6nm)=1.956.
Embodiment 6
Prepare calcium tantalum aluminate glass 35CaO-32.5Al2O3-32.5Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure Ca (OH)2Powder, α-Al2O3Powder, Ta2O5Powder is according to 35CaO:32.5Al2O3: 32.5Ta2O5
The proportion accurate weighing of (molar percentage) is placed in mortar, is fully ground mixing in the agate mortar, obtains uniform glass
Glass mixture.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 30MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1200 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 23.93mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 850 DEG C, soaking time 4h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=839.7 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=893.1 DEG C, T=53.4 DEG C of Δ.Its vickers microhardness Hv=881 (1Hv=9.80665MPa)=
8.639GPa refractive index nd(wavelength X=587.6nm)=1.948.
Embodiment 7
Prepare calcium tantalum aluminate glass 20CaO-43.2Al2O3-36.8Ta2O5, steps are as follows:
(1) frit mixes
By analytically pure Ca (HCO3)2Powder, α-Al2O3Powder, Ta2O5Powder is according to 20CaO:43.2Al2O3:
36.8Ta2O5The proportion accurate weighing of (molar percentage) is placed in mortar, is fully ground mixing in the agate mortar, is obtained
Uniform glass mixture.
(2) frit tabletting
Frit is placed in tabletting in grinding tool, setting pressure is 30MPa.
(3) frit pre-burning
Crucible equipped with foliated glass mixture is placed in pre-burning in Muffle furnace, the temperature that Muffle furnace is arranged is 1200 DEG C,
Soaking time is 12 hours.
(4) pneumatic suspension prepares glass without container method
Block shape glass mixture is broken into small blocks sample, taking quality is that the block sample of 24.88mg is placed in pneumatically
On the nozzle of shower furnace, sample is suspended in the air with high-purity argon gas, is not in contact with any utensil；After suspending stabilized,
Use CO2Laser heats sample and closes its fusing after mixing to liquid glass material by laser, stops
It is heated；Liquid glass material is cooled down rapidly using wind cooling method, calcium tantalum aluminate glass is made.
(5) it makes annealing treatment
Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 850 DEG C, soaking time 4h, is protected
It is down to room temperature naturally with furnace temperature after temperature.
After tested, glass transition temperature Tg=831.3 DEG C of calcium tantalum aluminate glass prepared by the present embodiment, once
Crystallization temperature Tp1=883 DEG C, T=51.7 DEG C of Δ.Its vickers microhardness Hv=876 (1Hv=9.80665MPa)=
8.591GPa refractive index nd(wavelength X=587.6nm)=1.936.
Claims (9)
1. a kind of calcium tantalum aluminate glass, which is characterized in that the raw material of the calcium tantalum aluminate glass is by calcium source, silicon source, tantalum source
Composition, calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5Meter, each component Mole percent composition are as follows: 10≤CaO≤35,
32.5≤Al2O3≤ 54,26≤Ta2O5≤ 45, the sum of three component molar percentages are 100%；
The calcium tantalum aluminate glass visible region transmitance is 79-82%, refractive index ndFor 1.93-2.03, Vickers hardness is
8.59-9.06GPa, glass transition temperature are 822.3-855.3 DEG C；
Preparation method includes that glass raw material mixing, frit tabletting, frit pre-burning, pneumatic suspension without container method prepare glass
With five steps of annealing, the specific steps are as follows:
1) glass raw material mixes: calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5It counts, in molar ratio 10≤CaO≤35,
32.5≤Al2O3≤ 54,26≤Ta2O5≤ 45 weigh raw material, and raw material is placed in mortar or ball grinder and is fully ground mixing,
Obtain uniform glass mixture；
2) frit tabletting: glass mixture obtained by step 1) is placed in tabletting in mold, pressure 5-30Mpa is set, piece is obtained
Shape glass mixture；
3) frit pre-burning: sheet glass mixture obtained by step 2 is fitted into crucible, then crucible is placed in Muffle furnace
Pre-burning obtains block shape glass mixture；
4) pneumatic suspension prepares glass without container method: block shape glass mixture obtained by step 3) is broken into small blocks sample,
Taking quality is that the block sample of 20-25mg is placed on the nozzle of pneumatic suspension furnace, and block sample is suspended in sky with high-purity gas
In, after suspending stabilized, carrying out heating to block sample with laser makes its fusing, is uniformly mixed to gained liquid glass material
Afterwards, laser is closed, stopping heats it, then cools down liquid glass material rapidly, obtains glass marble；
5) it makes annealing treatment: glass marble obtained by step 4) being placed in Muffle furnace and is made annealing treatment, furnace cooling after annealing
To room temperature, calcium tantalum aluminate glass is obtained.
2. calcium tantalum aluminate glass according to claim 1, it is characterised in that the calcium source is CaSO4Powder, Ca (OH)2
Powder, CaCO3Powder, Ca (HCO3)2One of powder；Source of aluminium is Al (OH)3Powder, Al2(SO4)3Powder, α-Al2O3
One of powder；The tantalum source is Ta2O5Powder；The calcium source is that 99.99% analysis is pure, and silicon source is 99.99% pure, the tantalum of analysis
Source is that 99.5% analysis is pure.
3. a kind of preparation method of calcium tantalum aluminate glass of any of claims 1 or 2, it is characterised in that mixed including glass raw material
Conjunction, frit tabletting, frit pre-burning, pneumatic suspension prepare five steps of glass and annealing, specific steps without container method
It is as follows:
1) glass raw material mixes: calcium source is in terms of CaO, and silicon source is with Al2O3Meter, tantalum source is with Ta2O5It counts, in molar ratio 10≤CaO≤35,
32.5≤Al2O3≤ 54,26≤Ta2O5≤ 45 weigh raw material, and raw material is placed in mortar or ball grinder and is fully ground mixing,
Obtain uniform glass mixture；
2) frit tabletting: glass mixture obtained by step 1) is placed in tabletting in mold, pressure 5-30Mpa is set, piece is obtained
Shape glass mixture；
3) frit pre-burning: sheet glass mixture obtained by step 2 is fitted into crucible, then crucible is placed in Muffle furnace
Pre-burning obtains block shape glass mixture；
4) pneumatic suspension prepares glass without container method: block shape glass mixture obtained by step 3) is broken into small blocks sample,
Taking quality is that the block sample of 20-25mg is placed on the nozzle of pneumatic suspension furnace, and block sample is suspended in sky with high-purity gas
In, after suspending stabilized, carrying out heating to block sample with laser makes its fusing, is uniformly mixed to gained liquid glass material
Afterwards, laser is closed, stopping heats it, then cools down liquid glass material rapidly, obtains glass marble；
5) it makes annealing treatment: glass marble obtained by step 4) being placed in Muffle furnace and is made annealing treatment, furnace cooling after annealing
To room temperature, calcium tantalum aluminate glass is obtained.
4. preparation method according to claim 3, it is characterised in that pre-sinter process condition described in step 3) are as follows: calcined temperature
It is 1000-1200 DEG C, burn-in time is 6-12 hours.
5. preparation method according to claim 3, it is characterised in that high-purity gas described in step 4) is Ar, O2、N2In one
Kind, purity >=99.99%.
6. preparation method according to claim 3, it is characterised in that cool down liquid glass material rapidly described in step 4)
Method is using wind cooling method rapid cooling, cooling rate 300-400K/s.
7. preparation method according to claim 3, it is characterised in that annealing treating process condition described in step 5) are as follows: annealing
Temperature is 800-850 DEG C, annealing time 1-4h.
8. application of the calcium tantalum aluminate glass in optical element and optical window resistant to high temperature as claimed in claim 1 or 2.
9. application of the calcium tantalum aluminate glass as claimed in claim 1 or 2 in high hardness wear-resisting coating material.
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