CN102432183B - Nanomicro-grade titanium oxide glass spheres and preparation method thereof - Google Patents
Nanomicro-grade titanium oxide glass spheres and preparation method thereof Download PDFInfo
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- CN102432183B CN102432183B CN201110265215.2A CN201110265215A CN102432183B CN 102432183 B CN102432183 B CN 102432183B CN 201110265215 A CN201110265215 A CN 201110265215A CN 102432183 B CN102432183 B CN 102432183B
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Abstract
The invention relates to nanomicro-titanium oxide glass spheres and a preparation method thereof. The invention belongs to the technical field of optical glass materials. The diameters of the glass spheres are 5nm-2000mum, and the glass spheres are shaped as regular balls. The preparation method comprises steps that: single-phase crystalline-state titanium oxide powder is uniformly fed into a high-temperature beam current; the powder is heated and melted into liquid drops, or even completely or partially volatilized into vapor; the liquid drops fall at the end of the high-temperature beam current; first, the liquid drops are contracted into balls, and then the balls are cooled and solidified into glass spheres; the vapor is first condensed into nano-grade ball-shaped liquid drops, and then the drops are cooled and solidified into nano-grade glass spheres. During the cooling and solidifying processes, the liquid drops are required not to be contacted. The liquid drops do not contact a vessel wall or impurities, such that the triggering of crystallization is avoided. The glass spheres have a wide application prospect in various optical fields such as high-resolution optical imaging, high-density storage, solar cells, LEDs and photonic crystals. With the method, large-scale and continuous productions can easily be realized.
Description
Technical field
The invention belongs to optical glass material technical field, particularly a kind of Nanomicro-grade titanium oxide glass spheres and preparation method thereof.
Background technology
Glass material be atom at atom the non-crystalline solids at space short distance order, the polyhedral structure unit conventionally consisting of glass-formers such as Si-O or B-O forms.In the last few years, containing the New Glasses Materials of conventional glass-former, do not caused lot of domestic and foreign scholar's great interest.Due to the unique texture at atomic scale, such glass has excellent optics, dielectric and mechanical property.Meanwhile, owing to lacking glass-former, such New Glasses Materials can not be used the preparation means of the conventional glass such as float glass process, founding, and can only adopt the method for chilling or suspension to avoid the crystalline polamer in melt cools.Recently, the people such as Japanese J.D.Yu utilize pneumatic suspension method, prepare the BaTi that diameter is 0.1～10mm
2o
5and La
4ti
9o
24spherical glass block materials.Performance test shows, such material specific refractory power in visible-range, up to 2.4, and also finds to have huge dielectric effect [Yu Yejian is fixed, titanium-containing oxide glass and manufacture method thereof, CN101516795] near glass transition temperature.Therefore, can predict, the New Glasses Materials containing conventional glass-former does not have boundless application prospect at many optical fields such as high resolution optical imaging, high-density photoetching storage (solid immersion lens), solar cell, LED and photonic crystals.
At above-mentioned optical field, it is very important that the spherical glass material of micro-meter scale is received in preparation.For example, Near-field Optical Microscope solid immersion camera lens, solar cell light trapping structure and photonic crystal component units etc. as ultrahigh resolution imaging, all need to use nanometer or micron-sized single particle spheroid.But, adopt existing preparation means, cannot obtain the glass sphere of this yardstick, the titanium oxide glass sphere that pneumatic suspension technology obtains is between 0.1～10mm, with quick cooling method, also can only obtain strip sample, even strip is ground and receives micro-meter scale, particle is also irregularly shaped and incomplete spherical.Therefore, in the urgent need to developing new technique means, prepare Nanomicro-grade titanium oxide glass spheres, meet the demand of many optical fields.
Summary of the invention
Order of the present invention is to provide a kind of Nanomicro-grade titanium oxide glass spheres and preparation method thereof, contributes to solve current titanium oxide glass geometrical dimension limited, is difficult to obtain the problem of practical application.
Glass sphere chemical composition of the present invention, following structural features:
Glass sphere chemical composition is (M1)
1-x(M2)
x(Ti
1-y1(M3)
y1)
y2o
z.Wherein, M1 is a kind of element being selected from La, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Na and Ca.M2 is at least one element that is selected from Mg, Ba, Ca, Sr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na, Sc, Y, Hf, Bi and Ag.M3 is at least one element that is selected from V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Al, Si, P, Ga, In, Sn, Sb and Te.X, y1, y2 and z meet following relation:
0≤x≤0.5
0≤y1＜0.31
1.4＜y2＜3.3
3.9＜z＜8.0
Glass sphere diameter is between the μ m of 5nm～2000, and outward appearance is the spherical of rule, and microtexture is the non-crystalline state of atom long-range lack of alignment.
Nano-micro level glass sphere of the present invention is prepared according to the following steps:
(1) synthetic single-phase crystalline state titanium oxide powder
Adopt the synthetic single-phase crystalline state titanium oxide powder of high-temperature solid phase reaction method.According to titanium oxide chemical composition, express formula, use single element oxide powder or certain two kinds of elements compounding oxide powder as raw material, weigh in proportion, after mixing, under air or oxygen atmosphere, be heated to temperature of reaction insulation, obtain single-phase crystalline state titanium oxide powder.
Single-phase crystalline state titanium oxide powder after synthetic is directly used for preparing titanium oxide glass sphere, or after ball milling, prepares titanium oxide glass sphere, or after ball milling through granulation, sieve, prepare titanium oxide glass sphere after obtaining the pelletizing of different-grain diameter scope.
Different with raw material according to titanium oxide composition, temperature of reaction is between 1000～1750 ℃, and soaking time is between 0.5～48 hour.By the phase of X-ray diffractometer analytical reaction product, form, take and obtain single-phase titanium oxide as standard, determine temperature of reaction and soaking time.
(2) prepare Nanomicro-grade titanium oxide glass spheres
Single-phase crystalline state titanium oxide powder, evenly feed in 2000 ℃ of above high temperature lines, titanium oxide powder is heated to fusing by high temperature line and forms drop, or evaporates into steam; Drop falls at high temperature line end, be first shrunk to spherical, then cooling, solidify formation glass sphere; Steam is first condensed into nano level spherical drop, then fall, cooling, solidify and form nanometer glass ball, drop does not come in contact in order to avoid triggers crystallization with wall or impurity in cooling or process of setting.
For single-phase crystalline state titanium oxide powder, when all evaporating into steam in high temperature line, the nanometer glass ball that final product is uniform particle diameter; The not volatilization when be only fused into drop in high temperature line, final product is micron order glass sphere; When part volatilization in high temperature line, form the mixture of steam and residual droplets, final product is the mixture of nanometer and two kinds of dimension glass balls of micron.When needs are during to mixture separation, mixture is carried out in alcohol or pure water after supersound process standingly, micron order glass sphere can be deposited to bottom, and nanometer glass ball is kept in the suspension of upper strata.
While preparing nanometer glass ball, need container with constraint steam; For micron order glass sphere, can in atmosphere open environment, prepare, also can in container, prepare.
High temperature line is flame, electron beam or the laser beam that plasma beam, fuel combustion form; Plasma beam comprises radio-frequency plasma bundle, direct-current plasma bundle or radio frequency-direct current hybrid plasma bundle; Fuel comprises acetylene, hydrogen, carbon monoxide, methane and mixed fuel, also comprises alcohol, gasoline and diesel oil.
When high temperature line is plasma beam, need carrier gas to carry out even feed titanium oxide powder.Carrier gas is a kind of in oxygen, argon gas and the two mixed gas, and gas velocity is 0.1～50m
3/ h, supplies powder speed between 0.1～500g/min.The gas that produces plasma body is a kind of in argon gas, oxygen, hydrogen and argon gas mixed gas, and gas velocity is 1～500m
3/ h; For radio-frequency plasma bundle, produce the gas of plasma body from radially and tangentially feed simultaneously, titanium oxide powder feeds from the axial centre of radio-frequency plasma bundle; For direct current and radio frequency-direct current hybrid plasma bundle, titanium oxide powder feeds from the outside of plasma beam, or feeds from the axial centre of direct-current plasma bundle.
Advantage of the present invention is as follows:
(1) what the present invention relates to receives micro-meter scale titanium oxide glass sphere, at many optical fields such as high resolution optical imaging, high-density photoetching storage (solid immersion lens), solar cell, LED and photonic crystals, has boundless application prospect.
(2) Nanomicro-grade titanium oxide glass spheres the present invention relates to, except can being directly used as the devices such as high-resolution optics camera lens, can also go out as powder stock sintering the bulk glass of any size and dimension, break through the prior art means such as suspension method and prepare the limit (10mm) of material, thereby there is more wide application prospect.
(3) preparation method who the present invention relates to, in principle, be suitable for all containing conventional glass-former, needs are contactless or without the material of container preparation condition, comprise titanium oxide glass, bulk amorphous alloy etc.
(4) preparation method who the present invention relates to, comprises plasma body and flame etc., and all ripe Industrialized processing technique based on the comparison, not only easily realize extensive and serialization production, and product cut size is controlled.
Accompanying drawing explanation
Fig. 1 is La
4(Zr, Ti)
9o
24the spherical looks of nanometer glass (transmission electron microscope photo), particle diameter is 5～50nm.
Fig. 2 is the selected area electron diffraction style of nanometer glass ball in Fig. 1.
Fig. 3 is nano grade titanium oxide glass ball X ray diffracting spectrum.
Fig. 4 is the synthetic titanium oxide powder pattern (electron scanning micrograph) of high temperature solid state reaction, does not pass through granulation.
Fig. 5 nano level and micron order La
4zr
1.35ti
7.65o
24glass sphere mixture pattern (electron scanning micrograph).
Fig. 6 is glass sphere mixture X ray diffraction collection of illustrative plates.
Fig. 7 is micron order La
4zr
1.35ti
7.65o
24glass sphere pattern (electron scanning micrograph).
Fig. 8 is BaTi
2o
5micron order glass sphere pattern (electron scanning micrograph).
Fig. 9 is micron order BaTi
2o
5glass sphere X ray diffracting spectrum.
Embodiment
(1) nano level La
4ti
9o
24glass sphere preparation
Adopt the synthetic La of high-temperature solid phase reaction method
4ti
9o
24powder.Use La
2o
3and TiO
2powder, as raw material, is expressed formula according to chemical composition various raw materials is weighed, and after fully mixing, is heated to 1250 ℃ and reacts and be incubated 4 hours in air, obtains single-phase crystalline state La
4ti
9o
24powder.After synthetic, powder is milled to 1～2 μ m.
The La after ball milling
4ti
9o
24powder, evenly feeds radio-frequency plasma with oxygen as carrier gas intrafascicular, and carrier gas flux is 0.1m
3/ h is 0.1g/min for powder speed.The power of radio-frequency (RF) plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 0.2m
3/ h and 0.8m
3/ h.
Nano-glass ball forming process is as follows: La
4ti
9o
24more than synthetic powder is rapidly heated to boiling point in plasma body line, volatilization forms steam completely.Steam, at plasma beam end, is first condensed into nano level spherical drop, then free-falling, the contactless formation glass sphere that solidifies of cooling generation.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Whole process is carried out in reaction chamber, and reaction chamber wall is led to circulating water.
(2) nano level La
4zr
1.35ti
7.65o
24glass sphere preparation
Adopt the synthetic La of high-temperature solid phase reaction method
4zr
1.35ti
7.65o
24powder.Use La
2o
3, TiO
2, ZrO
2oxide powder, as raw material, is expressed formula according to chemical composition various raw materials is weighed, and after fully mixing, is heated to 1300 ℃ and reacts and be incubated 48 hours in air, obtains single-phase crystalline state La
4zr
1.35ti
7.65o
24powder.After synthetic, powder is milled to 1～2 μ m.
The La after ball milling
4(Zr
xti
1-x)
9o
24powder, evenly feeds radio-frequency plasma with oxygen as carrier gas intrafascicular, and carrier gas flux is 0.4m
3/ h is 0.1g/min for powder speed.The power of radio-frequency (RF) plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 0.4m
3/ h and 4m
3/ h.
Nano-glass ball forming process is as follows: La
4zr
1.35ti
7.65o
24more than synthetic powder is rapidly heated to boiling point in plasma body line, volatilization forms steam completely.Steam, at plasma beam end, is first condensed into nano level spherical drop, then free-falling, the contactless formation glass sphere that solidifies of cooling generation.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Whole process is carried out in reaction chamber, and reaction chamber wall is led to circulating water.
Nano level La
4zr
1.35ti
7.65o
24as shown in Figure 1, median size is between 30nm to glass sphere pattern.Amorphous structure is proved by Fig. 2 (transmission electron microscope selected area electron diffraction collection of illustrative plates) and Fig. 3 (the x-ray diffractogram of powder spectrum of product).Synthetic single-phase crystalline state titanium oxide powder pattern as shown in Figure 4.
(3) nano level La
4zr
1.35ti
7.65o
24glass sphere preparation
Adopt the synthetic La of high-temperature solid phase reaction method
4zr
1.35ti
7.65o
24powder.Use La
2o
3, TiO
2, ZrO
2oxide powder, as raw material, is expressed formula according to chemical composition various raw materials is weighed, and after fully mixing, is heated to 1300 ℃ and reacts and be incubated 48 hours in air, obtains single-phase crystalline state La
4zr
1.35ti
7.65o
24powder.With the PVA aqueous solution, be that binding agent carries out granulation to powder, the pelletizing of formation sieves at 140～200 orders, and particle diameter is at 75～100 μ m.
Use direct current-radio frequency hybrid plasma bundle, wherein radio frequency plasma bundle is positioned at direct current plasma bundle below, and two beam-plasmas are coaxial.Pelletizing is fed from the intrafascicular heart of direct-current plasma as carrier equably with oxygen, and direct current plasma generator power is 15KW, and carrier gas flux is 50m
3/ h, is 500g/min for powder speed, and the gas that produces plasma body is argon gas, and flow is 50m
3/ h.The power of radio-frequency (RF) plasma reactor is 35KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 50m
3/ h and 400m
3/ h.
Nano-glass ball forming process is as follows: La
4zr
1.35ti
7.65o
24more than synthetic powder is rapidly heated to boiling point in plasma body line, volatilization forms steam completely.Steam, at plasma beam end, is first condensed into nano level spherical drop, then free-falling, the contactless formation glass sphere that solidifies of cooling generation.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Whole process is carried out in reaction chamber, and reaction chamber wall is led to circulating water.
(4) nanometer and micron order La
4zr
1.35ti
7.65o
24the preparation of glass sphere mixture
Adopt the synthetic La of high-temperature solid phase reaction method
4zr
1.35ti
7.65o
24powder.Use La
2o
3, TiO
2, ZrO
2oxide powder, as raw material, is expressed formula according to chemical composition various raw materials is weighed, and after fully mixing, is heated to 1300 ℃ and reacts and be incubated 48 hours in air, obtains single-phase crystalline state La
4zr
1.35ti
7.65o
24powder.After synthetic, powder is milled to 1～2 μ m, then is that binding agent carries out granulation with the PVA aqueous solution.Pelletizing 140～200 orders that granulation forms sieve, and particle diameter is at 75～100 μ m.
With oxygen, as carrier gas, pelletizing is evenly fed to radio-frequency plasma intrafascicular, carrier gas flux is 0.4m
3/ h is 50g/min for powder speed.The power of radio-frequency (RF) plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 4m
3/ h and 0.4m
3/ h.
Glass sphere mixture forming process is as follows: La
4zr
1.35ti
7.65o
24pelletizing in plasma body line in moving process by rapid heating, temperature first rises to fusing point and forms above drop, then more than rising to boiling point, the volatilization of drop external portion forms steam.Residual droplets falls at high temperature line end, is first shrunk to spherically, is then constantly cooled to following contactless solidifying, the formation micron order glass sphere of occurring of fusing point.Steam is first condensed into nano level spherical drop, then cooling, solidify and form nanometer glass ball.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Final product is the mixture of nanometer and micron order glass sphere.Whole process is carried out in reaction chamber, and reaction chamber wall is led to circulating water.Mixture is standing after supersound process in alcohol or pure water, and micron order glass sphere can be deposited to bottom, and nanometer glass ball is retained in the suspension of upper strata.
La
4zr
1.35ti
7.65o
24as shown in Figure 5, nanometer glass ball is attached to micron order glass sphere surface to glass sphere mixture pattern.Micron order glass sphere median size is 4 μ m.Amorphous structure is proved by Fig. 6 (the x-ray diffractogram of powder spectrum of product).
(5) micron order La
4zr
1.35ti
7.65o
24the preparation of glass sphere
Adopt the synthetic La of high-temperature solid phase reaction method
4zr
1.35ti
7.65o
24powder.Use La
2o
3, TiO
2, ZrO
2oxide powder, as raw material, is expressed formula according to chemical composition various raw materials is weighed, and after fully mixing, is heated to 1300 ℃ and reacts and be incubated 48 hours in air, obtains single-phase crystalline state La
4zr
1.35ti
7.65o
24powder.After synthetic, powder is milled to 1～2 μ m, then is that binding agent carries out granulation with the PVA aqueous solution.Pelletizing 140～200 orders that granulation forms sieve, and particle diameter is at 75～100 μ m.
The La after ball milling
4(Zr
xti
1-x)
9o
24powder, evenly feeds radio-frequency plasma with oxygen as carrier gas intrafascicular, and carrier gas flux is 0.4m
3/ h is 1g/min for powder speed.The power of radio-frequency (RF) plasma reactor is 10KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 0.4m
3/ h and 4m
3/ h.
It is as follows that micron order glass sphere forms process: La
4zr
1.35ti
7.65o
24pelletizing is rapidly heated to and more than fusing point forms drop in the intrafascicular moving process of plasma body, and drop falls at beam-plasma end, is first shrunk to spherically, is then constantly cooled to following contactless solidifying, the formation micron order glass sphere of occurring of fusing point.Whole process is carried out in atmospheric environment.As shown in Figure 7, median size is 4 μ m to micron order glass sphere pattern.
(6) nano level BaTi
2o
5glass sphere preparation
Adopt the synthetic BaTi of high-temperature solid phase reaction method
2o
5powder.Use BaTiO
3and TiO
2powder, as raw material, is expressed formula according to chemical composition two kinds of raw materials is weighed, and after fully mixing, is heated to 1200 ℃ and reacts and be incubated 15h, furnace cooling in air.
Powder after synthetic, evenly feeds radio-frequency plasma with oxygen as carrier gas intrafascicular, and carrier gas flux is 0.4m
3/ h is 0.1g/min for powder speed.The power of radio-frequency (RF) plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially feeding with tangential both direction of plasma generator simultaneously, flow is respectively 4m
3/ h and 0.4m
3/ h.
Nanometer glass ball forming process is as follows: BaTi
2o
5synthetic powder in plasma body line in moving process by rapid heating, temperature first rises to fusing point and forms above drop, then more than rising to boiling point, volatilization forms steam completely.Steam, at plasma beam end, is first condensed into nano level spherical drop, then free-falling, the contactless formation glass sphere that solidifies of cooling generation.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Whole process reaction chamber in carry out, reaction chamber wall is led to circulating water.
Nano level BaTi
2o
5as shown in Figure 8, median size is between 80nm to glass sphere pattern.Amorphous structure is proved by Fig. 9 (the x-ray diffractogram of powder spectrum of product).
(7) nano level Ba
0.15sr
0.85ti
2o
5glass sphere preparation
Adopt the synthetic Ba of high-temperature solid phase reaction method
0.15sr
0.85ti
2o
5powder.Use BaTiO
3, SrTiO
3and TiO
2powder, as raw material, is expressed formula according to chemical composition two kinds of raw materials is weighed, and after fully mixing, is heated to 1200 ℃ and reacts and be incubated 15h in air, obtains single-phase crystalline state Ba
0.15sr
0.85ti
2o
5powder.
Ba
0.15sr
0.85ti
2o
5powder evenly feeds in hydrogen-oxygen flame, for powder speed, is 0.1g/min, and whole process is carried out in atmospheric environment.
Nanometer glass ball forming process is as follows: Ba
0.15sr
0.85ti
2o
5synthetic powder is by rapid heating in flame, and temperature first rises to fusing point and forms above drop, then more than rising to boiling point, volatilization forms steam completely.Steam, at flame end, is first condensed into nano level spherical drop, then free-falling, the contactless formation glass sphere that solidifies of cooling generation.Free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition formation glass sphere.Whole process reaction chamber in carry out.
(8) micron order Ba
0.15sr
0.85ti
2o
5glass sphere preparation
Adopt the synthetic Ba of high-temperature solid phase reaction method
0.15sr
0.85ti
2o
5powder.Use BaTiO
3, SrTiO
3and TiO
2powder, as raw material, is expressed formula according to chemical composition two kinds of raw materials is weighed, and after fully mixing, is heated to 1200 ℃ and reacts and be incubated 15h in air, obtains single-phase crystalline state Ba
0.15sr
0.85ti
2o
5powder.
Ba
0.15sr
0.85ti
2o
5powder evenly feeds in hydrogen-oxygen flame, for powder speed, is 50g/min, and whole process is carried out in atmospheric environment.
It is as follows that micron order glass sphere forms process: Ba
0.15sr
0.85ti
2o
5synthetic powder is by rapid heating in flame, and temperature first rises to fusing point and forms above drop, and drop falls at thermal-flame end, is first shrunk to spherically, is then constantly cooled to following contactless solidifying, the formation micron order glass sphere of occurring of fusing point.
Claims (7)
1. a Nanomicro-grade titanium oxide glass spheres, is characterized in that, chemical composition expression formula is:
(M1)
1-x(M2)
x(Ti
1-y1(M3)
y1)
y2o
z, wherein, M1 is for being selected from La, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, any one element in Na and Ca, M2 is for being selected from Mg, Ba, Ca, Sr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Na, Sc, Y, Hf, at least one element of Bi and Ag, M3 is for being selected from V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Al, Si, P, Ga, In, Sn, at least one element of Sb and Te, x, y1, y2 and z meet following relation:
0≤x≤0.5，0≤y1<0.31，1.4<y2<3.3，3.9<z<8.0
Glass sphere is the spherical of rule, and diameter is between the μ m of 5nm～4.
2. a preparation method for Nanomicro-grade titanium oxide glass spheres claimed in claim 1, is characterized in that, comprises the following steps:
The first step, expresses formula according to titanium oxide chemical composition, uses single element oxide powder or binary oxide powder as raw material, raw material is weighed in proportion, after mixing, under air or oxygen atmosphere, be heated to temperature of reaction insulation, obtain single-phase crystalline state titanium oxide powder
Second step, single-phase crystalline state titanium oxide powder, evenly feeds in 2000 ℃ of above high temperature lines, and titanium oxide powder is heated to fusing by high temperature line and forms drop, or evaporates into steam; Drop falls at high temperature line end, be first shrunk to spherical, then cooling, solidify formation glass sphere; Steam is first condensed into nano level spherical drop, then fall, cooling, solidify and form nanometer glass ball, drop does not come in contact in order to avoid triggers crystallization with wall or impurity in cooling or process of setting;
Described temperature of reaction is between 1000～1750 ℃, and soaking time is between 0.5～48 hour;
Described single-phase crystalline state titanium oxide powder is directly used for preparing titanium oxide glass sphere, or after granulation, prepare titanium oxide glass sphere, or after ball milling, prepare titanium oxide glass sphere, or after ball milling through granulation, sieve, prepare titanium oxide glass sphere after obtaining the pelletizing of different-grain diameter scope.
3. preparation method according to claim 2, is characterized in that, described single-phase crystalline state titanium oxide powder,
When all evaporating into steam in high temperature line, the nanometer glass ball that final product is uniform particle diameter;
The not volatilization when be only fused into drop in high temperature line, final product is micron order glass sphere;
When part volatilization in high temperature line, form the mixture of steam and residual droplets, final product is the mixture of nanometer and two kinds of dimension glass balls of micron.
4. preparation method according to claim 2, is characterized in that, described high temperature line is flame, electron beam or the laser beam that plasma beam, fuel combustion form;
Plasma beam comprises radio-frequency plasma bundle, direct-current plasma bundle or radio frequency-direct current hybrid plasma bundle;
Fuel comprises acetylene, hydrogen, carbon monoxide, methane and mixed fuel, also comprises alcohol, gasoline and diesel oil.
5. preparation method according to claim 4, is characterized in that, when high temperature line is plasma beam, needs carrier gas to carry out even feed titanium oxide powder; Carrier gas is a kind of in oxygen, argon gas and the two mixed gas, and gas velocity is 0.1～50m
3/ h, supplies powder speed between 0.1～500g/min; The gas that produces plasma body is a kind of in argon gas, oxygen, hydrogen and argon gas mixed gas, and gas velocity is 1～500m
3/ h; For radio-frequency plasma bundle, produce the gas of plasma body from radially and tangentially feed simultaneously, titanium oxide powder feeds from the axial centre of radio-frequency plasma bundle; For direct current and radio frequency-direct current hybrid plasma bundle, titanium oxide powder feeds from the outside of plasma beam, or feeds from the axial centre of direct-current plasma bundle.
6. preparation method according to claim 2, is characterized in that, when preparing nanometer glass ball, needs container with constraint steam; For micron order glass sphere, in atmosphere open environment, prepare, or prepare in container.
7. preparation method according to claim 3, it is characterized in that, when needs are during to mixture separation, mixture is carried out in alcohol or pure water after supersound process standing, micron order glass sphere can be deposited to bottom, and nanometer glass ball is kept in the suspension of upper strata.
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| CN103121105B (en) * | 2013-03-19 | 2015-04-01 | 北京科技大学 | Method for preparing micro spherical niobium (Nb)-wolfram (W)-molybdenum (Mo)-zirconium (Zr) alloy powder |
| CN104030573B (en) * | 2014-06-12 | 2017-02-15 | 中国科学院过程工程研究所 | Colorless niobium oxide glass and preparation method and application thereof |
| CN110983270B (en) * | 2019-12-03 | 2021-12-03 | 天津大学 | Oxide-metal composite nano glass material |
| CN116041057B (en) * | 2022-12-26 | 2023-11-24 | 广东微容电子科技有限公司 | Barium titanate powder, preparation method and chip type multilayer ceramic capacitor |
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| CN1394680A (en) * | 2002-02-01 | 2003-02-05 | 重庆大学 | Nano-grade lanthanum titanium compound oxide, its preparation method and application |
| CN101200809A (en) * | 2006-12-12 | 2008-06-18 | 中国科学院理化技术研究所 | Method for synthesizing beryllium fluoroborate single-phase polycrystalline powder |
| CN101516795A (en) * | 2006-09-14 | 2009-08-26 | 独立行政法人宇宙航空研究开发机构 | Titanium-containing oxide glass and method for production thereof |
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| CN1394680A (en) * | 2002-02-01 | 2003-02-05 | 重庆大学 | Nano-grade lanthanum titanium compound oxide, its preparation method and application |
| CN101516795A (en) * | 2006-09-14 | 2009-08-26 | 独立行政法人宇宙航空研究开发机构 | Titanium-containing oxide glass and method for production thereof |
| CN101200809A (en) * | 2006-12-12 | 2008-06-18 | 中国科学院理化技术研究所 | Method for synthesizing beryllium fluoroborate single-phase polycrystalline powder |
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