CN101838109B - Hollow glass microsphere prepared by soft template method and preparation method thereof - Google Patents
Hollow glass microsphere prepared by soft template method and preparation method thereof Download PDFInfo
- Publication number
- CN101838109B CN101838109B CN2009102289250A CN200910228925A CN101838109B CN 101838109 B CN101838109 B CN 101838109B CN 2009102289250 A CN2009102289250 A CN 2009102289250A CN 200910228925 A CN200910228925 A CN 200910228925A CN 101838109 B CN101838109 B CN 101838109B
- Authority
- CN
- China
- Prior art keywords
- hollow glass
- hollow
- microballon
- glass micropearl
- glass microsphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004005 microsphere Substances 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 17
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 12
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 9
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000001110 calcium chloride Substances 0.000 claims abstract description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 35
- 238000007670 refining Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- 239000000498 cooling water Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 8
- 238000005553 drilling Methods 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- -1 NSC 9824s Chemical class 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006196 drop Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
Images
Landscapes
- Glass Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a hollow glass microsphere prepared by a soft template method and a preparation method thereof. The hollow glass microsphere comprises the following raw materials in parts by weight: 93 parts of tetraethoxysilane, 11-35 parts of n-amine, 1.5-3.5 parts of inorganic ionic salt and 8-20 parts of borax, wherein, the n-amine is at least one of n-octylamine, n-nonyl amine or n-decylamine; and the inorganic ionic salt is at least one of sodium chloride, potassium chloride, calcium chloride, sodium sulfate, sodium carbonate and potassium carbonate. The balling rate of the hollow glass microsphere exceeds 99% and the hollow rate thereof exceeds 99%; the hollow glass microsphere has uniform structure, and the particle size thereof can be self-regulated and controlled into 10-400mum as needed; the corresponding stacking density is 0.60-0.15g/cm<3>; and the hollow glass microsphere can be widely applied to fields such as automobile, building materials, heat insulation, sound insulation, deep-sea drilling, aerospace and the like.
Description
Technical field
The present invention relates to the preparation of inorganic hollow material, be specifically related to hollow glass micropearl of a kind of soft template method preparation and preparation method thereof.
Background of invention
The hollow glass micropearl that is described as " Space Age material " is a kind of sphere, the fine vitreum of Multifunction hollow, that include gas; It has the incomparable physico-chemical property of many other fillers; Have that fusing point height, resistivity are high, electrical insulating property is good, density is low, good fluidity, a series of characteristics such as shrinking percentage is little, stability is strong, heat insulation, sound insulation, high temperature resistant, heat-conduction coefficient and Thermal Contraction Coefficient are little; Make it become a kind of good filling and material modified; When the cost that is filled product is reduced greatly; Therefore also give the multiple function that is filled product simultaneously, be widely used in fields such as aerospace, deep sea drilling, automobile, building, electrically insulating material, heat insulation, sound insulation and military special material
Hollow glass micropearl will definitely be divided into flyash hollow glass micro-bead and artificial hollow glass microballon according to different contingency table.The hollow glass micropearl low price that the flyash method is extracted, abundant raw material, its development is very fast, but impurity level is many, and color is dark, and added value is low, and Application Areas is narrow; The hollow glass micropearl of high added value mainly relies on artificial the manufacturing.The working method of present home and abroad artificial hollow glass microballon; Mainly contain sessile drop method, powder method, spray-drying process, sol-gel method, flame method, glass cullet high-temperature calcination etc.; These methods mainly are at high temperature to fire with the raw material powder that is mixed with whipping agent, drop or glass cullet to form, and its emphasis also is how difficult point is that in the high-temperature molding stove effective control cenosphere prepares the complicated technology of a series of mutual cross influences such as wall thickness of the transfer rate of the heat that transmits between the hot gas in atmosphere, powder and the body of heater in the process, the particle/time of microballon stop, the temperature of firing, material, microballon.The balling ratio of hollow glass micropearl product is low, productive rate is low, efficient is low, the aberration rate height is the major defect of these methods.
The development of China's high quality hollow glass micropearl still is in laboratory study and lab scale stage with production.The Dongguan, Guangdong was once helped and sodium metasilicate and boron-containing compound are made into mixed solution are adopted spray drying method for preparation to go out hollow glass micropearl; Shandong Province New Materials Inst., Zibo City Lee waterside nine grades adopt the secondary spray-on process also to prepare hollow glass micropearl after on this basis sodium metasilicate and ammonium borate being made into mixed solution; The graduate Qiu Long meeting of Chinese Academy of Sciences's gongwu, lacquer small echo, Zhang Zhanwen etc. utilize sessile drop method, spray drying process and sol-gel process successfully to make the hollow glass micropearl that should in driving, produce neutron, but the hollow glass micropearl size that these methods prepare is uncontrollable with distribution, balling ratio is low, hollow rate is low; Simultaneously reason such as block because of the core technology that the high added value hollow glass micropearl is prepared abroad again; China only has that the factory technics of several production glass microballoons falls behind, is simply equipped, cost is high, benefit is not good; Produce total capacity ten thousand tons of less thaies still at present per year; Industrial products are main with polishing pearl and abrasive media microballon mainly, and added value is low.The whole dependence on import of the hollow glass micropearl of required high added value, and import price up to 5～80,000/ton, this demand with the hollow glass micropearl that increases severely day by day forms sharp contrast.
With the tetraethoxy is the silicon source; Though hydrolysis under diluted acid property condition prepares the existing report of meso-porous hollow silicon dioxide microsphere as template with positive amines such as NSC 9824s, the microballon for preparing is calcined in 500～700 ℃ of retort furnaces, and it is mesoporous that the gas that template is decomposed during calcining is covered with bead surface; Seepage rate is very high after being scattered in the water; Product is without glass transition simultaneously, and compressive strength is very low, and the general normal pharmaceutical carrier of doing is used.Improve calcining temperature and make the microballoon vitrifying, then all silicon dioxide microspheres that are in molten state under static conditions, be melt into a bulk of, can't balling-up.
Summary of the invention
The object of the present invention is to provide hollow glass micropearl of a kind of soft template method preparation and preparation method thereof; Can overcome the defective of prior art; The present invention adds ionic compound earlier under acid-free condition; Elements such as interpolation boron are prepared the hollow borosilicate microballon that internal layer includes the template vesica fast; Make spherical shell generation glass transition when in the vertical glass microballon moulding of high temperature stove, burning template then, obtained that hollow rate is high, balling ratio is high, structure does not have the meso-porous hollow glass microballon very uniformly.The glass microballon balling ratio of the present invention preparation surpasses 99%, hollow rate surpasses 99%, and balling-up is very perfect, size can according to the demand difference voluntarily modulation process be 10～400 μ m, its corresponding tap density is 0.60～0.15g/cm
3The present invention is the preparation method of the hollow glass micropearl of a kind of succinct, efficient, particle diameter and controllable density.
The present invention provides the quality group of raw material of the hollow glass micropearl of a kind of soft template method preparation to become:
93 parts of tetraethoxys
11～35 parts of positive amine
1.5～3.5 parts of inorganic ion salts
8～20 parts of boraxs
Positive amine is at least a in NSC 9824, positive nonyl amine or the n-Decylamine.
Inorganic salt are at least a in sodium-chlor, Repone K, calcium chloride, sodium sulfate, yellow soda ash, the salt of wormwood.
The particle diameter of hollow glass micropearl of the present invention is 10～400 μ m, and corresponding tap density is 0.60～0.15g/cm
3
The present invention provides a kind of preparation method of hollow glass micropearl of soft template method preparation may further comprise the steps:
1) by metering tetraethoxy and positive aminated compounds are mixed; Stirred 3～8 minutes, and added the ion salt aqueous solution and borax solution, constant speed stirs; Stir speed (S.S.) is 100～800 rev/mins; Churning time is 5～20 minutes, filters, and promptly gets the hollow borosilicate microballon that size distribution evenly comprises template after the white precipitate drying.
2) join in the vertical glass microballon moulding of the high temperature stove this hollow borosilicate microballon refining uniformly; The furnace temperature temperature is controlled to be 1100 ℃～1500 ℃; The glass microballon that spherical shell is in molten state directly is imported into quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen.
The present invention can overcome the defective of prior art.At first adopt inorganic ion salt to replace dilute acid soln to prepare the hollow borosilicate microballon that internal layer includes the template vesica fast; In the high temperature vertical furnace, burn template then and make spherical shell generation glass transition simultaneously, obtained that hollow rate is high, balling ratio is high, structure does not have the meso-porous hollow glass microballon very uniformly.Adopt another advantage of High Temperature Furnaces Heating Apparatus method preparation to be: can not bump and pile up in the process that glass microballon falls in vertical furnace; But hot environment makes also coated die plate evaporable gas of bead surface Flashmelt in addition, and this is very beneficial for balling-up and improves hollow rate.Through the made hollow glass micropearl balling ratio of this present invention surpass 99%, hollow rate surpasses 99%, balling-up is very perfect, size can according to the demand difference voluntarily modulation process be 10～400 μ m, its corresponding tap density is 0.60～0.15g/cm
3Can be widely used in fields such as automobile, building materials, heat insulation, sound insulation, deep sea drilling, space flight and aviation.
Description of drawings
Fig. 1 is the preparation principle synoptic diagram of hollow glass micropearl.
Fig. 2 is the light micrograph that the NSC 9824 micro-capsule steeps in the tetraethoxy under the different stir speed (S.S.)s.
Fig. 3 comprises the light micrograph of positive amine template cenosphere and the corresponding Photomicrograph that differs for instance 2 internal layers.
Fig. 4 is the light micrograph and the corresponding Photomicrograph that differs of the hollow glass micropearl after instance 4 is made with extra care.
Fig. 5 is before instance 4 hollow glass micropearls are made with extra care and the little angle XRD comparison diagram after refining.
Embodiment
Fig. 1 is the principle schematic of preparation hollow glass micropearl of the present invention; From figure, can know; Elder generation formed fine vesica when positive amine such as NSC 9824 mixed with tetraethoxy, and after containing the adding wherein of ionic mixed solution, (early stage report is necessary for the diluted acid adding sol gel reaction just takes place; Find in this instance to replace diluted acid not only can make the generation that is swift in response with a spot of ionic compound; Also can other elements be added in the product) sol gel reaction takes place rapidly in tetraethoxy on vesica surface, form the uniform borosilicate compound of a layer thickness, and this microballon spherical shell is not through glass transition; Intensity is very low, so churning time can not be oversize in order to avoid broken.Then the top of this thick cenosphere from the vertical glass microballon moulding of high temperature stove at the uniform velocity added; Because of the thermal conductivity of microballon is high, the fusion of at high temperature absorbing heat rapidly of microballon top layer makes viscosity and surface tension decline, and the positive amine vesica that is included in internal layer simultaneously becomes gases such as carbonic acid gas because of pyrolytic decomposition; Along with air pressure increases; Microballon volumetric expansion, housing attenuation occur mesoporous simultaneously at weakness, portion gas is from mesoporous volatilization, but at the later stage of microballon moulding; Evaporable gas reduces; Mesoporously sealed again by melt that simultaneously portion gas is packed, after the molten state microballon that glass transition taken place is directed to tank, spherical shell shrink and sclerosis after promptly become required hollow glass micropearl product.
Shown in Figure 2 is to be the light micrograph of stir speed (S.S.) to NSC 9824 vesica influence in the tetraethoxy; From figure, can know; The particle diameter of the big or small remarkably influenced vesica of stir speed (S.S.); Less stir speed (S.S.) generates bigger vesica, and bigger stir speed (S.S.) generates less vesica, and we control particle diameter and then the particle diameter of control cenosphere finished product that internal layer is surrounded by the hollow borosilicate microballon of positive amine vesica through the adjustment stir speed (S.S.) just.a：100r/min，b：300r/min，c：500r/min
Instance 1: with 100ml tetraethoxy and positive nonyl amine of 15ml and the mixing of 10ml n-Decylamine; Stir subsequent use after 4 minutes; Pour above-mentioned mixed solution fast into after fully being dissolved in 1.0g sodium-chlor, 0.5g calcium chloride and 8g borax in 80 ℃ of water simultaneously, constant speed stirs, 100 rev/mins of stir speed (S.S.)s; Churning time 5 minutes; After stirring stops product being filtered, be drying to obtain the hollow borosilicate microballon that contains soft template, it is that (the inferior magnificent electric furnace in Wuhan ltd produces model to the 1100 ℃ of vertical glass microballon moulding of high temperature stoves: refining KY-30-6) that this cenosphere is joined temperature; The hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 400 μ m, corresponding tap density is 0.15g/cm
3.
Instance 2: 100ml tetraethoxy and 25ml NSC 9824 are mixed; Stir subsequent usely after 3 minutes, pour above-mentioned mixed solution fast into after fully being dissolved in 2.5g Repone K and 10.0g borax in 80 ℃ of water simultaneously, constant speed stirs; 800 rev/mins of stir speed (S.S.)s; The hollow borosilicate microballon that contains soft template is filtered, is drying to obtain to churning time 10 minutes with product after stirring stops, and it is refining in 1500 ℃ of refining stoves that this cenosphere is joined temperature; The hollow glass micropearl that spherical shell is in molten state directly is imported into quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 33 μ m, corresponding tap density is 0.54g/cm
3
Fig. 3 and 4 shown in respectively be for internal layer in the instance 2 comprise the cenosphere of positive amine template refining before with instance 4 hollow core microballons the light micrograph and the corresponding Photomicrograph that differs after refining; Can know from Fig. 3 (a) [instance 2]; Adopt hollow borosilicate microballon balling ratio that soft template method makes, circularity is very high, size is comparatively even; For having the heavy-walled hollow structure, there is not the cross frosting phenomenon from this microballon of Fig. 3 (b) susceptible of proof; And can know from Fig. 4 (a) [instance 4], after hollow borosilicate microballon is fired, the obvious attenuation of wall thickness; Slightly glossy; Can know that from Fig. 4 (b) of correspondence prepared hollow glass micropearl all presents chromatic cross frosting phenomenon, this proves absolutely: not only hollow rate height and concentricity (symmetry) that the glass transition product has taken place are very high; And spherical shell structure is even, and balling-up is perfect.
Instance 3: with 100ml tetraethoxy and 20ml NSC 9824 and the positive nonyl amine of 15ml mix stir after 8 minutes subsequent use; Pour above-mentioned mixed solution fast into after fully being dissolved in 0.5g sodium sulfate, 2.0g yellow soda ash and 10g borax in 80 ℃ of water simultaneously; Constant speed stirs, 600 rev/mins of stir speed (S.S.)s, churning time 15 minutes; After stirring stops product being filtered, is drying to obtain the hollow borosilicate microballon that contains soft template; It is refining in 1300 ℃ of refining stoves that this cenosphere is joined temperature, and the hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 57 μ m, corresponding tap density is 0.38g/cm
3.
Instance 4: with 100ml tetraethoxy and 15ml NSC 9824 and 15ml n-Decylamine mix stir after 5 minutes subsequent use; Pour above-mentioned mixed solution fast into after fully being dissolved in 1.5g sodium sulfate, 1.1g sodium-chlor and 15g borax in 80 ℃ of water simultaneously; Constant speed stirs, 500 rev/mins of stir speed (S.S.)s, churning time 20 minutes; After stirring stops product being filtered, is drying to obtain the hollow borosilicate microballon that contains soft template; It is refining in 1250 ℃ of refining stoves that this cenosphere is joined temperature, and the hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 63 μ m, corresponding tap density is 0.40g/cm
3
What Fig. 5 described is thick hollow borosilicate microballon refining preceding (a) and (b) little angle, refining back XRD comparison diagram in the instance 4; Among the figure (a) diffraction peak is arranged; This explains that hollow borosilicate microballon has tangible meso-hole structure before refining; Can know that from figure refining back diffraction peak disappears (b), before this explanation earlier because of the template gaseous volatilization bead surface form mesoporous by encapsulation again.
Instance 5: 100ml tetraethoxy and the positive nonyl amine mixing of 25ml stirring is subsequent use after 5 minutes; Pour above-mentioned mixed solution fast into after fully being dissolved in 0.5g salt of wormwood, 0.5g Repone K, 0.5g calcium chloride, 0.5g sodium sulfate and 15g borax in 80 ℃ of water simultaneously; Constant speed stirs, 800 rev/mins of stir speed (S.S.)s, churning time 10 minutes; After stirring stops product being filtered, is drying to obtain the hollow borosilicate microballon that contains soft template; It is refining in 1400 ℃ of refining stoves that this cenosphere is joined temperature, and the hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 15 μ m, corresponding tap density is 0.51g/cm
3.
Instance 6: 100ml tetraethoxy and 10ml NSC 9824, the positive nonyl amine of 10m and 10m n-Decylamine mixing stirring is subsequent use after 6 minutes; Pour above-mentioned mixed solution fast into after fully being dissolved in 0.2g salt of wormwood, 0.5g sodium sulfate, 2.1g Repone K and 8g borax in 80 ℃ of water simultaneously; Constant speed stirs, 800 rev/mins of stir speed (S.S.)s, churning time 15 minutes; After stirring stops product being filtered, is drying to obtain the hollow borosilicate microballon that contains soft template; It is refining in 1300 ℃ of refining stoves that this cenosphere is joined temperature, and the hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/em
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 10 μ m, corresponding tap density is 0.60g/cm
3.
Instance 7: 100ml tetraethoxy and 5.0ml NSC 9824, the positive nonyl amine of 12.0ml and 15.0ml n-Decylamine mixing stirring is subsequent use after 7 minutes; Pour above-mentioned mixed solution fast into after fully being dissolved in 0.3g sodium-chlor, 1.3g Repone K, 0.2g calcium chloride, 0.5g sodium sulfate, 0.5g yellow soda ash, 0.5g salt of wormwood and 20g borax in 80 ℃ of water simultaneously; Constant speed stirs; 200 rev/mins of stir speed (S.S.)s; The hollow borosilicate microballon that contains soft template is filtered, is drying to obtain to churning time 20 minutes with product after stirring stops, and it is refining in 1400 ℃ of refining stoves that this cenosphere is joined temperature; The hollow glass micropearl that spherical shell is in molten state directly is imported into quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 175 μ m, corresponding tap density is 0.27g/cm
3.
Instance 8: 100ml tetraethoxy and 35ml n-Decylamine mixing stirring is subsequent use after 3 minutes; Pour above-mentioned mixed solution fast into after fully being dissolved in 0.5g salt of wormwood, 1.5g sodium-chlor, 1.5g Repone K and 10.0g borax in 80 ℃ of water simultaneously; Constant speed stirs, 800 rev/mins of stir speed (S.S.)s, churning time 5 minutes; After stirring stops product being filtered, is drying to obtain the hollow borosilicate microballon that contains soft template; It is refining in 1100 ℃ of refining stoves that this cenosphere is joined temperature, and the hollow glass micropearl that spherical shell is in molten state is directly imported quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product after constant temperature (80 ℃) drying through filter screen, this product balling ratio surpasses 99%, hollow rate surpasses 99%, particle diameter is 13 μ m, corresponding tap density is 0.60g/cm
3.
Claims (4)
1. the hollow glass micropearl of soft template method preparation is characterized in that the quality group of its raw material becomes:
Described positive amine is at least a in NSC 9824, positive nonyl amine or the n-Decylamine;
Described inorganic ion salt is at least a in sodium-chlor, Repone K, calcium chloride, sodium sulfate, yellow soda ash, the salt of wormwood;
The preparation method may further comprise the steps:
1) by metering ethyl orthosilicate and positive aminated compounds are mixed; Stirred 3～8 minutes; Add inorganic ions saline solution and borax solution; Constant speed stirs; Stir speed (S.S.) is 100～800 rev/mins; Mixing time is 5～20 minutes, filters, and promptly gets particle diameter after the white precipitate drying and is evenly distributed and comprises the hollow borosilicate microballon of template;
2) this hollow borosilicate microballon is joined in the vertical glass microballon moulding of the high temperature stove uniformly refining, the glass microballon that spherical shell is in molten state directly is imported into quenching in the tank that is connected with recirculated cooling water, and density is less than 1g/cm
3Hollow glass micropearl float on waterbornely, this is floated pearl collects, gets product behind the freeze-day with constant temperature through filter screen.
2. hollow glass micropearl according to claim 1, the particle diameter that it is characterized in that described hollow glass micropearl are 10～400 μ m, and corresponding tap density is 0.6～0.15g/cm
3
3. hollow glass micropearl according to claim 1, the furnace temperature that it is characterized in that described moulding stove are 1100 ℃～1500 ℃.
4. hollow glass micropearl according to claim 1 is characterized in that described constant temperature is 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102289250A CN101838109B (en) | 2009-12-02 | 2009-12-02 | Hollow glass microsphere prepared by soft template method and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102289250A CN101838109B (en) | 2009-12-02 | 2009-12-02 | Hollow glass microsphere prepared by soft template method and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101838109A CN101838109A (en) | 2010-09-22 |
| CN101838109B true CN101838109B (en) | 2012-02-01 |
Family
ID=42741818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102289250A Expired - Fee Related CN101838109B (en) | 2009-12-02 | 2009-12-02 | Hollow glass microsphere prepared by soft template method and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101838109B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674662A (en) * | 2012-05-28 | 2012-09-19 | 中国海洋大学 | Process for preparing hollow glass-ceramics microballoon sphere |
| TWI680259B (en) * | 2018-05-11 | 2019-12-21 | 陳宣甫 | Volume reduction method of biological bone ash and permanent preservation method of the same |
| CN110252246A (en) * | 2019-07-01 | 2019-09-20 | 河南城建学院 | A kind of coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material and its preparation method and application |
| CN111734950A (en) * | 2020-07-01 | 2020-10-02 | 西安维国电子科技有限公司 | Method and device for filling and recovering electric insulating gas in closed space |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028247A (en) * | 1989-05-18 | 1991-07-02 | Chisso Corporation | Process for the preparation of silica glass powders |
| CN1575262A (en) * | 2001-10-24 | 2005-02-02 | 3M创新有限公司 | Glass beads and uses thereof |
-
2009
- 2009-12-02 CN CN2009102289250A patent/CN101838109B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028247A (en) * | 1989-05-18 | 1991-07-02 | Chisso Corporation | Process for the preparation of silica glass powders |
| CN1575262A (en) * | 2001-10-24 | 2005-02-02 | 3M创新有限公司 | Glass beads and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101838109A (en) | 2010-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704632B (en) | Preparation method of high-strength low-density hollow glass bead | |
| JP3633091B2 (en) | Method for producing minute inorganic spherical solid body | |
| CA1278688C (en) | Manufacturing vitreous beads | |
| CN103979796A (en) | High-strength hollow glass beads and preparation method thereof | |
| CN101596745B (en) | Vitrified bond for diamond grinding wheel and method for preparing diamond grinding wheel | |
| CN102320743B (en) | High strength aluminosilicate hollow glass microsphere and preparation method thereof | |
| CN101838109B (en) | Hollow glass microsphere prepared by soft template method and preparation method thereof | |
| CN102101754B (en) | Method for preparing boron-containing foam glass | |
| CN101792266B (en) | Particle-reinforced foam glass and preparation method thereof | |
| CN108585519A (en) | A method of preparing foam pyroceram using red mud | |
| CA2632760A1 (en) | Engineered low-density heterogeneous microparticles and methods and formulations for producing the microparticles | |
| TW200422276A (en) | Synthetic hollow microspheres | |
| CN107998996B (en) | Preparation method of silicon-aluminum composite aerogel powder | |
| CN103073176A (en) | Preparation method of hollow glass microbead | |
| CN103467018A (en) | Preparation method for preparing low-density oil well cementing cement briquettes by vermiculites | |
| CN108126651B (en) | Fly ash floating bead loaded lithium ion sieve sheet and preparation method thereof | |
| CN105948512A (en) | Micro-crystallographic foamed glass prepared from tailings of titanium separation and preparation method | |
| CN112079647B (en) | Preparation method of ceramic fiber board | |
| AU2014290627B2 (en) | Glass microbubbles, raw product, and methods of making the same | |
| CA2885643C (en) | Synthetic microparticles | |
| CN102515825B (en) | Chromium slag and chromium reducing furnace slag high-temperature melt foaming method and foaming device | |
| CN106630615B (en) | A method of hollow glass micropearl is manufactured using cullet | |
| CN102795783A (en) | Preparation method of porous glass material | |
| CN107162565A (en) | A kind of high intensity geopolymer tiny balloon and preparation method thereof | |
| CN110526586A (en) | A kind of preparation method of low-density hollow glass bead |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: NANJING LONGJU TECHNOLOGY INDUSTRY CO., LTD. Free format text: FORMER OWNER: TIANJIN UNIVERSITY Effective date: 20130514 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 300072 NANKAI, TIANJIN TO: 210007 NANJING, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130514 Address after: 210007, room 410, business building, great light road, 35 great light road, Jiangsu, Nanjing Patentee after: Nanjing Longju Technology Industrial Co. Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
|
| DD01 | Delivery of document by public notice |
Addressee: Huang Xiaoqing Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Nanjing Longju Technology Industrial Co. Ltd. Document name: Notification of Termination of Patent Right |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120201 Termination date: 20131202 |