CN102432183A - 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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- CN102432183A CN102432183A CN2011102652152A CN201110265215A CN102432183A CN 102432183 A CN102432183 A CN 102432183A CN 2011102652152 A CN2011102652152 A CN 2011102652152A CN 201110265215 A CN201110265215 A CN 201110265215A CN 102432183 A CN102432183 A CN 102432183A
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000075 oxide glass Substances 0.000 title claims abstract description 22
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 title abstract 7
- 239000000843 powder Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 81
- 239000010936 titanium Substances 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000004615 ingredient Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 5
- 239000004038 photonic crystal Substances 0.000 abstract description 4
- 238000012634 optical imaging Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000005304 optical glass Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 6
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 22
- 238000003746 solid phase reaction Methods 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
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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 the optical glass material technical field, particularly a kind of nano-micro level titanium oxide glass sphere and preparation method thereof.
Background technology
Glass material is the non-crystalline solids of atom in atom short range order arrangement in the space, is made up of the polyhedral structure unit that glass-formers such as Si-O or B-O constitute usually.In the last few years, the novel glass material that did not contain conventional glass-former has caused lot of domestic and foreign scholar's great interest.Because at the unique texture of atomic scale, such glass has excellent optics, dielectric and mechanical property.Simultaneously, owing to lack glass-former, such novel glass material can not use the preparation means of conventional glass such as float glass process, founding, and the method that can only adopt chilling or suspension is to avoid the crystalline polamer in the melt cools.Recently, people such as Japanese J.D.Yu utilize the pneumatic suspension method, prepare the BaTi that diameter is 0.1～10mm
2O
5And La
4Ti
9O
24The spherical glass block materials.Performance test shows, said material specific refractory power in visible-range and also finds to have huge dielectric effect [Yu Yejian is fixed, titanium-containing oxide glass and method of manufacture thereof, CN101516795] up to 2.4 near glass transition temperature.Therefore, can predict, the novel glass material that does not contain conventional glass-former has 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 crucial that the spherical glass material of micro-meter scale is received in preparation.For example, NFM solid immersion camera lens, solar cell light trapping structure and photonic crystal component units etc. as the ultrahigh resolution imaging all need use nanometer or micron-sized single particle spheroid.But; Adopt the existing preparation means; Can't obtain the glass sphere of this yardstick, the titanium oxide glass sphere that the pneumatic suspension technology obtains also can only obtain the strip sample with quick cooling method between 0.1～10mm; Even grind strip and receive micro-meter scale, particle also is irregularly shaped but not complete sphere.Therefore, press for the new technique means of exploitation, prepare nano-micro level titanium oxide glass sphere, satisfy the demand of many optical fields.
Summary of the invention
Order of the present invention is to provide a kind of nano-micro level titanium oxide glass sphere and preparation method thereof, and it is limited to help to solve present titanium oxide glass geometrical dimension, is difficult to obtain the problem of practical application.
Glass sphere chemical ingredients of the present invention, constitutional features are following:
The glass sphere chemical ingredients is (M1)
1-x(M2)
x(Ti
1-y1(M3)
Y1)
Y2O
zWherein, M1 is a kind of element that is selected among La, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Na and the Ca.M2 is at least a 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 a 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.Relation below x, y1, y2 and z satisfy:
0≤x≤0.5
0≤y1＜0.31
1.4＜y2＜3.3
3.9＜z＜8.0
The glass sphere diameter is between 5nm～2000 μ m, and outward appearance is the sphere 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 prepares 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.Express formula according to the titanium oxide chemical ingredients; 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 and insulation, obtain single-phase crystalline state titanium oxide powder.
Single-phase crystalline state titanium oxide powder after synthetic directly is used for preparing the titanium oxide glass sphere, or preparation titanium oxide glass sphere behind the ball milling, or behind the ball milling through granulation, sieve, obtain preparation titanium oxide glass sphere behind the pelletizing of different-grain diameter scope.
Different with raw material according to the titanium oxide composition, temperature of reaction is between 1000～1750 ℃, and soaking time is between 0.5～48 hour.With the thing phase composite of X-ray diffractometer analytical reaction product, be standard to obtain single-phase titanium oxide, confirm temperature of reaction and soaking time.
(2) preparation nano-micro level titanium oxide glass sphere
Single-phase crystalline state titanium oxide powder, evenly infeed more than 2000 ℃ in the high temperature line, titanium oxide powder is heated to fusing by the high temperature line and forms drop, or evaporates into steam; Drop is shrunk to sphere earlier in the terminal whereabouts of high temperature line, then cools off, solidifies the formation glass sphere; Steam is condensed into the nano level spherical drop earlier, falls, cools off, solidifies to form the nanometer glass ball then, and drop does not come in contact in order to avoid trigger crystallization with wall or impurity in cooling or process of setting.
For single-phase crystalline state titanium oxide powder, when in the high temperature line, all evaporating into steam, final product is the nanometer glass ball of uniform particle diameter; The not volatilization when in the high temperature line, only being fused into drop, final product is the micron order glass sphere; When part volatilization in the 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 during to mixture separation, in alcohol or pure water, carry out mixture to leave standstill after the supersound process, the micron order glass sphere can be deposited to bottom, and the nanometer glass ball is kept in the suspension-s of upper strata.
During preparation nanometer glass ball, need container with the constraint steam; For the micron order glass sphere, can in the atmosphere open environment, prepare, also can in container, prepare.
The 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 the high temperature line is plasma beam, need carrier gas to come 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 the argon gas mixed gas, and gas velocity is 1～500m
3/ h; For the radio-frequency plasma bundle, the gas that produces plasma body is from radially infeed with the tangential simultaneously, and titanium oxide powder infeeds from the axial centre of radio-frequency plasma bundle; For direct current and radio frequency-direct current hybrid plasma bundle, titanium oxide powder infeeds from the outside of plasma beam, or infeeds from the axial centre of direct-current plasma bundle.
Advantage of the present invention is following:
What (1) the present invention relates to receives micro-meter scale titanium oxide glass sphere, has 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.
(2) the nano-micro level titanium oxide glass sphere that the present invention relates to; Except can be directly as the devices such as high-resolution optics camera lens; Can also go out the bulk glass of any size and dimension as the powder stock sintering; Prior art means such as breakthrough suspension method prepare the limit (10mm) of material, thereby have more wide application prospect.
(3) preparation method who the present invention relates to is suitable on the principle that all do not contain conventional glass-former, needs are contactless or does not have the material of container preparation condition, comprises titanium oxide glass, bulk amorphous alloy etc.
(4) preparation method who the present invention relates to comprises plasma body and flame etc., all based on the suitability for industrialized production technology of comparative maturity, not only realize extensive and serialization production easily, and product cut size is controlled.
Description of drawings
Fig. 1 is La
4(Zr, Ti)
9O
24The spherical looks (transmission electron microscope photo) of nanometer glass, particle diameter is 5～50nm.
Fig. 2 is the SEAD style of nanometer glass ball among Fig. 1.
Fig. 3 is a nano grade titanium oxide glass ball X ray diffracting spectrum.
Fig. 4 is a high temperature solid state reaction synthetic titanium oxide powder pattern (electron scanning micrograph), 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 a glass sphere mixture X XRD X 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
5The glass sphere X ray diffracting spectrum.
Embodiment
(1) nano level La
4Ti
9O
24The glass sphere preparation
Adopt the synthetic La of high-temperature solid phase reaction method
4Ti
9O
24Powder.Use La
2O
3And TiO
2Powder is expressed formula according to chemical ingredients various raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1250 ℃ of reactions and is incubated 4 hours, obtains single-phase crystalline state La
4Ti
9O
24Powder.Synthetic back powder ball milling to 1～2 μ m.
The La behind the ball milling
4Ti
9O
24Powder, it is intrafascicular evenly to infeed radio-frequency plasma with oxygen as carrier gas, and carrier gas flux is 0.1m
3/ h, supplying powder speed is 0.1g/min.The power of RF plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 0.2m
3/ h and 0.8m
3/ h.
It is following that the nano-glass ball forms process: La
4Ti
9O
24Synthetic powder is rapidly heated to more than the boiling point in the plasma body line, and volatilization forms steam fully.Steam is terminal at plasma beam, is condensed into the nano level spherical drop earlier, and the contactless formation glass sphere that solidifies takes place for free-falling then, cooling.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Whole process is carried out in reaction chamber, the logical recirculated water cooling of reaction chamber wall.
(2) nano level La
4Zr
1.35Ti
7.65O
24The glass 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 is expressed formula according to chemical ingredients various raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1300 ℃ of reactions and is incubated 48 hours, obtains single-phase crystalline state La
4Zr
1.35Ti
7.65O
24Powder.Synthetic back powder ball milling to 1～2 μ m.
The La behind the ball milling
4(Zr
xTi
1-x)
9O
24Powder, it is intrafascicular evenly to infeed radio-frequency plasma with oxygen as carrier gas, and carrier gas flux is 0.4m
3/ h, supplying powder speed is 0.1g/min.The power of RF plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 0.4m
3/ h and 4m
3/ h.
It is following that the nano-glass ball forms process: La
4Zr
1.35Ti
7.65O
24Synthetic powder is rapidly heated to more than the boiling point in the plasma body line, and volatilization forms steam fully.Steam is terminal at plasma beam, is condensed into the nano level spherical drop earlier, and the contactless formation glass sphere that solidifies takes place for free-falling then, cooling.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Whole process is carried out in reaction chamber, the logical recirculated water cooling of reaction chamber wall.
Nano level La
4Zr
1.35Ti
7.65O
24The glass sphere pattern is as shown in Figure 1, and median size is between the 30nm.Amorphous structure is proved by Fig. 2 (transmission electron microscope SEAD collection of illustrative plates) and Fig. 3 (the x-ray diffractogram of powder spectrum of product).The single-phase crystalline state titanium oxide powder of synthetic pattern is as shown in Figure 4.
(3) nano level La
4Zr
1.35Ti
7.65O
24The glass 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 is expressed formula according to chemical ingredients various raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1300 ℃ of reactions and is incubated 48 hours, obtains single-phase crystalline state La
4Zr
1.35Ti
7.65O
24Powder.Use the PVA aqueous solution as sticker powder to be carried out granulation, 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 the radio frequency plasma bundle is positioned at direct current plasma bundle below, and two beam-plasmas are coaxial.Infeed pelletizing from the intrafascicular heart of direct-current plasma equably as carrier with oxygen, the direct current plasma generator power is 15KW, and carrier gas flux is 50m
3/ h, supplying powder speed is 500g/min, and the gas that produces plasma body is argon gas, and flow is 50m
3/ h.The power of RF plasma reactor is 35KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 50m
3/ h and 400m
3/ h.
It is following that the nano-glass ball forms process: La
4Zr
1.35Ti
7.65O
24Synthetic powder is rapidly heated to more than the boiling point in the plasma body line, and volatilization forms steam fully.Steam is terminal at plasma beam, is condensed into the nano level spherical drop earlier, and the contactless formation glass sphere that solidifies takes place for free-falling then, cooling.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Whole process is carried out in reaction chamber, the logical recirculated water cooling of reaction chamber wall.
(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 is expressed formula according to chemical ingredients various raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1300 ℃ of reactions and is incubated 48 hours, obtains single-phase crystalline state La
4Zr
1.35Ti
7.65O
24Powder.Synthetic back powder ball milling to 1～2 μ m uses the PVA aqueous solution to carry out granulation as sticker again.Pelletizing 140～200 orders that granulation forms sieve, and particle diameter is at 75～100 μ m.
As carrier gas, it is intrafascicular evenly to infeed radio-frequency plasma to pelletizing with oxygen, and carrier gas flux is 0.4m
3/ h, supplying powder speed is 50g/min.The power of RF plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 4m
3/ h and 0.4m
3/ h.
Glass sphere mixture forming process is following: La
4Zr
1.35Ti
7.65O
24Pelletizing in the plasma body line in the moving process by rapid heating, temperature rises to the above drop that forms of fusing point earlier, rises to more than the boiling point again, the volatilization of drop external portion forms steam.Residual droplets is shrunk to sphere earlier in the terminal whereabouts of high temperature line, then constantly is cooled to contactless solidifying taken place below the fusing point, forms the micron order glass sphere.Steam is condensed into the nano level spherical drop earlier, cools off, solidifies formation nanometer glass ball then.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Final product is the mixture of nanometer and micron order glass sphere.Whole process is carried out in reaction chamber, the logical recirculated water cooling of reaction chamber wall.Mixture leaves standstill through after the supersound process in alcohol or pure water, and the micron order glass sphere can be deposited to bottom, and the nanometer glass ball is retained in the suspension-s of upper strata.
La
4Zr
1.35Ti
7.65O
24Glass sphere mixture pattern is as shown in Figure 5, and the nanometer glass ball is attached to micron order glass sphere surface.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 is expressed formula according to chemical ingredients various raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1300 ℃ of reactions and is incubated 48 hours, obtains single-phase crystalline state La
4Zr
1.35Ti
7.65O
24Powder.Synthetic back powder ball milling to 1～2 μ m uses the PVA aqueous solution to carry out granulation as sticker again.Pelletizing 140～200 orders that granulation forms sieve, and particle diameter is at 75～100 μ m.
The La behind the ball milling
4(Zr
xTi
1-x)
9O
24Powder, it is intrafascicular evenly to infeed radio-frequency plasma with oxygen as carrier gas, and carrier gas flux is 0.4m
3/ h, supplying powder speed is 1g/min.The power of RF plasma reactor is 10KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 0.4m
3/ h and 4m
3/ h.
Micron order glass sphere forming process is following: La
4Zr
1.35Ti
7.65O
24Pelletizing is rapidly heated in the intrafascicular moving process of plasma body and forms drop more than the fusing point, and drop is shrunk to sphere earlier in the terminal whereabouts of beam-plasma, then constantly is cooled to contactless solidifying taken place below the fusing point, forms the micron order glass sphere.Whole process is carried out in atmospheric environment.Micron order glass sphere pattern is as shown in Figure 7, and median size is 4 μ m.
(6) nano level BaTi
2O
5The glass sphere preparation
Adopt the synthetic BaTi of high-temperature solid phase reaction method
2O
5Powder.Use BaTiO
3And TiO
2Powder is expressed formula according to chemical ingredients two kinds of raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1200 ℃ of reactions and insulation 15h, furnace cooling.
The powder after synthetic, it is intrafascicular evenly to infeed radio-frequency plasma with oxygen as carrier gas, and carrier gas flux is 0.4m
3/ h, supplying powder speed is 0.1g/min.The power of RF plasma reactor is 15KW, and frequency is 4MHz, and the gas that produces plasma body is argon gas, and from radially infeeding simultaneously with the tangential both direction of plasma generator, flow is respectively 4m
3/ h and 0.4m
3/ h.
It is following that the nanometer glass ball forms process: BaTi
2O
5Synthetic powder in the plasma body line in the moving process by rapid heating, temperature rises to the above drop that forms of fusing point earlier, rises to more than the boiling point again, volatilization forms steam fully.Steam is terminal at plasma beam, is condensed into the nano level spherical drop earlier, and the contactless formation glass sphere that solidifies takes place for free-falling then, cooling.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Whole process reaction chamber in carry out the logical recirculated water cooling of reaction chamber wall.
Nano level BaTi
2O
5The glass sphere pattern is as shown in Figure 8, and median size is between the 80nm.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
5The glass 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 is expressed formula according to chemical ingredients two kinds of raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1200 ℃ of reactions and insulation 15h, obtains single-phase crystalline state Ba
0.15Sr
0.85Ti
2O
5Powder.
Ba
0.15Sr
0.85Ti
2O
5Powder evenly infeeds in hydrogen-oxygen flame, and supplying powder speed is 0.1g/min, and whole process is carried out in atmospheric environment.
It is following that the nanometer glass ball forms process: Ba
0.15Sr
0.85Ti
2O
5By rapid heating, temperature rises to the above drop that forms of fusing point earlier to synthetic powder, rises to more than the boiling point again in flame, and volatilization forms steam fully.Steam is terminal at flame, is condensed into the nano level spherical drop earlier, and the contactless formation glass sphere that solidifies takes place for free-falling then, cooling.The free-falling distance is wanted to guarantee that drop and steam have the sufficient time to undergo phase transition the formation glass sphere.Whole process reaction chamber in carry out.
(8) micron order Ba
0.15Sr
0.85Ti
2O
5The glass 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 is expressed formula according to chemical ingredients two kinds of raw materials is weighed as raw material, behind the thorough mixing, in air, is heated to 1200 ℃ of reactions and insulation 15h, obtains single-phase crystalline state Ba
0.15Sr
0.85Ti
2O
5Powder.
Ba
0.15Sr
0.85Ti
2O
5Powder evenly infeeds in hydrogen-oxygen flame, and supplying powder speed is 50g/min, and whole process is carried out in atmospheric environment.
Micron order glass sphere forming process is following: Ba
0.15Sr
0.85Ti
2O
5By rapid heating, temperature rises to the above drop that forms of fusing point earlier to synthetic powder in flame, and drop is shrunk to sphere earlier in the terminal whereabouts of thermal-flame, then constantly is cooled to contactless solidifying taken place below the fusing point, forms the micron order glass sphere.
Claims (9)
1. a nano-micro level titanium oxide glass sphere is characterized in that, chemical ingredients expression formula is: (M1)
1-x(M2)
x(Ti
1-y1(M3)
Y1)
Y2O
zWherein, M1 is any one element that is selected among La, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Na and the Ca; M2 is at least a 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 a 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, relation below x, y1, y2 and z satisfy:
0≤x≤0.5，0≤y1＜0.31，1.4＜y2＜3.3，3.9＜z＜8.0
Glass sphere is the sphere of rule, and diameter is between 5nm～2000 μ m.
2. the preparation method of the described nano-micro level titanium oxide of claim 1 glass sphere is characterized in that, may further comprise the steps:
The first step is expressed formula according to the titanium oxide chemical ingredients, 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 and insulation; Obtain single-phase crystalline state titanium oxide powder
Second step single-phase crystalline state titanium oxide powder, evenly infeeded more than 2000 ℃ in the high temperature line, and titanium oxide powder is heated to fusing formation drop by the high temperature line, or evaporates into steam; Drop is shrunk to sphere earlier in the terminal whereabouts of high temperature line, then cools off, solidifies the formation glass sphere; Steam is condensed into the nano level spherical drop earlier, falls, cools off, solidifies to form the nanometer glass ball then, and drop does not come in contact in order to avoid trigger crystallization with wall or impurity in cooling or process of setting.
3. preparation method according to claim 2 is characterized in that, described temperature of reaction is between 1000～1750 ℃, and soaking time is between 0.5～48 hour.
4. preparation method according to claim 2; It is characterized in that; Described single-phase crystalline state titanium oxide powder directly is used for preparing the titanium oxide glass sphere, or preparation titanium oxide glass sphere after the granulation, or preparation titanium oxide glass sphere behind the ball milling; Or behind the ball milling through granulation, sieve, obtain preparation titanium oxide glass sphere behind the pelletizing of different-grain diameter scope.
5. preparation method according to claim 1 is characterized in that, described single-phase crystalline state titanium oxide powder,
When in the high temperature line, all evaporating into steam, final product is the nanometer glass ball of uniform particle diameter;
The not volatilization when in the high temperature line, only being fused into drop, final product is the micron order glass sphere;
When part volatilization in the 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.
6. 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.
7. preparation method according to claim 6 is characterized in that, when the high temperature line is plasma beam, needs carrier gas to come 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 the argon gas mixed gas, and gas velocity is 1～500m
3/ h; For the radio-frequency plasma bundle, the gas that produces plasma body is from radially infeed with the tangential simultaneously, and titanium oxide powder infeeds from the axial centre of radio-frequency plasma bundle; For direct current and radio frequency-direct current hybrid plasma bundle, titanium oxide powder infeeds from the outside of plasma beam, or infeeds from the axial centre of direct-current plasma bundle.
8. preparation method according to claim 2 is characterized in that, when preparation nanometer glass ball, needs container with the constraint steam; Prepare in the atmosphere open environment for the micron order glass sphere, or in container, prepare.
9. preparation method according to claim 5; It is characterized in that,, in alcohol or pure water, carry out mixture to leave standstill after the supersound process when needs during to mixture separation; The micron order glass sphere can be deposited to bottom, and the nanometer glass ball is kept in the suspension-s of upper strata.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121105A (en) * | 2013-03-19 | 2013-05-29 | 北京科技大学 | Method for preparing micro spherical niobium (Nb)-wolfram (W)-molybdenum (Mo)-zirconium (Zr) alloy powder |
| CN104030573A (en) * | 2014-06-12 | 2014-09-10 | 中国科学院过程工程研究所 | Colorless niobium oxide glass and preparation method and application thereof |
| CN110983270A (en) * | 2019-12-03 | 2020-04-10 | 天津大学 | Oxide-metal composite nano glass material |
| CN116041057A (en) * | 2022-12-26 | 2023-05-02 | 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 single-phase polycrystalline powder of fluoroboroberberic acid salt |
| 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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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 single-phase polycrystalline powder of fluoroboroberberic acid salt |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121105A (en) * | 2013-03-19 | 2013-05-29 | 北京科技大学 | Method for preparing micro spherical niobium (Nb)-wolfram (W)-molybdenum (Mo)-zirconium (Zr) alloy powder |
| 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 |
| CN104030573A (en) * | 2014-06-12 | 2014-09-10 | 中国科学院过程工程研究所 | Colorless niobium oxide glass and preparation method and application thereof |
| CN110983270A (en) * | 2019-12-03 | 2020-04-10 | 天津大学 | Oxide-metal composite nano glass material |
| CN116041057A (en) * | 2022-12-26 | 2023-05-02 | 广东微容电子科技有限公司 | Barium titanate powder, preparation method and chip type multilayer ceramic capacitor |
| 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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