CN101293755A - Surface modification method for hollow glass tiny bead and uses thereof - Google Patents
Surface modification method for hollow glass tiny bead and uses thereof Download PDFInfo
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- CN101293755A CN101293755A CNA2008101270943A CN200810127094A CN101293755A CN 101293755 A CN101293755 A CN 101293755A CN A2008101270943 A CNA2008101270943 A CN A2008101270943A CN 200810127094 A CN200810127094 A CN 200810127094A CN 101293755 A CN101293755 A CN 101293755A
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- glass micropearl
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- titanium
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- 239000011521 glass Substances 0.000 title claims abstract description 109
- 238000002715 modification method Methods 0.000 title abstract 2
- 239000011324 bead Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims description 44
- 230000004048 modification Effects 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
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- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229940045511 barium chloride Drugs 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001864 baryta Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 61
- 239000004408 titanium dioxide Substances 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 4
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- 238000007146 photocatalysis Methods 0.000 abstract description 2
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- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a modification method of a hollow glass microballoon surface. Titanium dioxide coating layers are uniformly clad on the hollow glass microballoon surface by adopting a titanium salt back dripping method, so that the heat insulating property of the hollow glass microballoon can be improved obviously, and the production process is simplified. The method can fully bring into play the characteristics of the hollow glass microballoon and titanium dioxide in performance, make the best of the two and lead to synergistic effect. Therefore, the filling material of the hollow glass microballoon, after being modified, has diverse filling functions and the advantages of heat resistance, heat reflection, photocatalysis etc., so as to meet different needs. The invention also provides the application of the method in the manufacture of head insulating coatings.
Description
Technical field
The present invention relates to a kind of surface modifying method of thermal insulating filling, particularly a kind of surface modifying method of hollow glass micropearl, and this method is in the application in preparation thermal insulating coating field.
Background technology
Hollow glass micropearl is a kind of thin-walled, sealed glass global shell, because its inside is vacuum or N
2, CO
2Gas, so cenosphere has characteristics such as lightweight, high-strength, sound insulation, heat insulation, insulation, day by day becomes the important filler in the fields such as building materials, aerospace, electronics, coal, metallurgy.In the U.S., many manufacturerss are using hollow glass micropearl to prepare artificial marble, and this kind artificial marble is in light weight, and impact resistance is good, and cost is low; In functional plastics and functional paint preparation field, hollow glass micropearl joined to can be made in the thermosetting resin have density is low, intensity the is high and remarkable heat-proof quality and the hollow glass micropearl syntactic foam of electrical property; The use of hollow glass micropearl in insulating mold coating except accessing the reflected light and thermal-radiating effect as the metallic aluminium powder, can also intercept adiabatic principle and improve the heat-insulating property of filming; Hollow glass micropearl is to produce the main raw with floating ability product, compares with the submarine armour that chloroprene rubber is made with the submarine armour that hollow glass micropearl is made, and not only ageing-resistant performance increases substantially, and heat insulation effect also improves 40～50%; In fields such as aerospace, medical skill, most advanced and sophisticated scientific researches, hollow glass micropearl is packed in the container outer wall abdominal cavity, after being evacuated, insulation effect is excellent, and it can make such as very low temperature liquid hydrogen (173 ℃), liquid nitrogen (269 ℃) adiabatic and do not gasify in accumulating and use; In addition, hollow glass micropearl also be at present known to the best a kind of emulsion explosive of performance adjust agent, its intensity height, closure are good, good fluidity, simple, the steady quality of adding technology, are used for emulsion explosive and can bear quite high ambient pressure and unlikely insensitiveness.
Current, overwhelming majority research for hollow glass micropearl (can be consulted Chinese patent CN97111059.X, CN98100584.5, CN98100583.7, CN200510121422.5 CN99119422.5) still concentrates on hollow glass micropearl production technique and hollow glass micropearl and directly prepares the incubation and thermal insulation function material as filler; Though (CN200610123961.7 CN200510057369.7), also only is confined to use as electromagnetic shielding material at the hollow glass micropearl electroplate to have a spot of research to relate to the research of hollow glass micropearl surface modification.
The present invention proposes a kind of new hollow glass micropearl surface modifying method under above-mentioned technical background, to promote the using value of hollow glass micropearl as thermal insulating filling.
Summary of the invention
The objective of the invention is to: a kind of new hollow glass micropearl surface modifying method is provided, makes hollow glass micropearl have higher heat insulating effect.
Another object of the present invention is to: the application of described hollow glass micropearl surface modifying method in the preparation heat preserving and insulating material is provided.
In view of the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of method of hollow glass micropearl surface modification is provided, may further comprise the steps:
(1) with 0.2～0.4mol.L
-1The aqueous solution of oxyhydroxide mix according to weight ratio 10.25: 1～307.5 with hollow glass micropearl, in this mixed solution, be to drip sodium dodecyl benzene sulfonate aqueous solution at 0.002～0.006: 1, obtain hollow glass micropearl suspension through stirring according to tensio-active agent Sodium dodecylbenzene sulfonate and hollow glass micropearl weight ratio;
(2) stir down, the temperature of keeping reaction system is 20～70 ℃, in 1～8 hour reaction times, in the hollow glass micropearl suspension that step (1) obtains, dripped with (1) in the aqueous solution volume ratio of oxyhydroxide be 0.5: 1～2, concentration is 0.05～0.1mol.L
-1The aqueous solution of tetravalent salt of titanium, left standstill after dropwising 1～4 hour, filter also washing, adding weight percent concentration and be 5～15% salts solution that contains the divalence barium ion or silver nitrate solution in filtrate does not have till the white precipitate, suction filtration obtains wet mash;
(3) the wet mash drying that step (2) is obtained is calcined then, obtains the hollow glass micropearl through modification.
In the aforesaid method,
The particle diameter of the described hollow glass micropearl of step (1) is 10～100 μ m, and specific surface area is 0.1～0.7m
2/ g; Described oxyhydroxide is selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide; The churning time of described stirring is 5～10 minutes.
The described tetravalent salt of titanium of step (2) is selected from titanium sulfate, titanyl sulfate or titanium tetrachloride; The described salts solution that contains the divalence barium ion is bariumchloride or nitrate of baryta.
The described drying of step (3) is following dry 2～4 hours at 100～110 ℃; Described method for calcinating is to be warming up to 400 ℃～700 ℃ and kept 2～4 hours with 100 ℃ of/hour heat-up rates.
All preferred distilled water of water in the various aqueous solution of using in the aforesaid method or deionized water.
Surface modification through method of modifying of the present invention, the thickness of the coating of titanium dioxide on hollow glass micropearl surface is generally 0.1～3.0 μ m, preferred 0.3～1.5 μ m, and the coating of titanium dioxide of this thickness is nano-pore structure, the aperture is generally 60～100nm, preferred 85～95nm.
The present invention also provides the application of method in the preparation thermal insulating coating of described hollow glass micropearl surface modification, after soon hollow glass micropearl will adopt described method to carry out surface modification, prepares thermal insulating coating as filler.
Titanium dioxide, nontoxic, under the normal temperature hardly with other substance reaction, water insoluble, fatty, also be insoluble to acid, alkali, only be dissolved in hydrofluoric acid.Titanium dioxide has peculiar photochemical activity, and under light action, the successive redox reaction can take place titanium dioxide, and organic pollutant degradation is carbonic acid gas and water the most at last, utilizes this characteristic can carry out the purification and the wastewater treatment of obnoxious flavour.Common titanium dioxide crystal form has two kinds of Detitanium-ore-type and rutile-types, and in actual applications, the titanium dioxide of two kinds of crystal formations has characteristics separately respectively.Mass density (the 3.894gcm of Detitanium-ore-type
-3) be slightly less than rutile-type (4.250gcm
-3), band gap (3.3eV) is slightly larger than rutile-type (3.1eV), thereby rutile titanium dioxide is to O
2Adsorptive power relatively poor, specific surface area is less, light induced electron and hole are compound easily, catalytic activity is under some influence; But rutile titanium dioxide specific refractory power (2.73) is higher than anatase titanium dioxide (2.55), and structure is tight, and irradiation that can ultraviolet resistance is difficult for efflorescence outdoor, and weathering resistance and glossiness are good.
The present invention is based on the mentality of designing of matrix material, utilize the surperficial uniform deposition cladding titanium dioxide film of the precipitator method at hollow glass micropearl, hollow glass micropearl is carried out surface modification, can give full play to hollow glass micropearl and the titanium dioxide advantage on performance, make up for each other's deficiencies and learn from each other, produce synergistic effect, thereby make hollow glass micropearl filler function diversification, can satisfy various demand through modification.
To be used to prepare all kinds of heat preserving and insulating materials as filler through the hollow glass micropearl of method modification of the present invention, the sound insulation of hollow glass micropearl, the advantage of heat insulation, good fluidity had both been acted on, make full use of the high characteristics of titanium deoxid film specific refractory power of the nanoscale of its surface deposition again, improved the heat reflection effect of hollow glass micropearl surface, further strengthened the heat insulating effect of filler solar radiation.And, by the photocatalysis characteristic of titanium dioxide, utilize all kinds of heat preserving and insulating materials of this filler preparation can effectively reduce VOC content in the heat preserving and insulating material, guarantee healthy human settlement.Therefore, the coated by titanium dioxide hollow glass micropearl filler that obtains through the inventive method modification is the novel material of the huge ecology of a kind of development potentiality, energy-saving and environmental protection.
Compared with prior art, the beneficial effect that had of hollow glass micropearl surface modifying method of the present invention is embodied in:
1. improved the heat reflection effect of hollow glass micropearl surface, strengthened the heat insulating effect of filler, optimized the speed and the ability of photocatalytic degradation formaldehyde solar radiation.
Because the sunlight reflectivity height of titanium dioxide so the present invention can strengthen hollow glass micropearl reflected solar radiation and the heat conducting ability of prevention in hollow glass micropearl surface cladding titanium dioxide coating, and then has improved its heat insulation effect.
Moreover, in the method for the present invention, because what the dispersion medium of initial hollow glass micropearl adopted is certain density basic solution, hollow glass micropearl is higher at the basic solution zeta-potential, have good dispersion and suspension property, thereby can reduce because the uneven problem of coated by titanium dioxide that hollow glass micropearl is reunited and caused; And basic solution can also fall to remove the impurity on hollow glass micropearl surface, more helps the precipitation of titanium dioxide on the hollow glass micropearl surface.So do not compare as the similar approach of dispersion medium with using basic solution, method of the present invention can further significantly improve the quality and the performance of coated by titanium dioxide hollow glass micropearl product, sees the and the following test for details:
A. scanning electron microscope analysis
Adopting U.S. FEI QUANTA 200 type scanning electron microscopes to observe method of the present invention and coating process does not adopt basic solution to make the pattern of hollow glass micropearl of the method institute modification of dispersion medium.The results are shown in Figure 1.Wherein Fig. 1 a is to use the distillation water compositing dispersion medium, drips titanium liquid and ammoniacal liquor under 60 ℃ simultaneously, keeps reaction system pH=7, and preparation coated by titanium dioxide layer thickness is the SEM figure of the modification hollow glass micropearl of 1 μ m; Fig. 1 b is under 60 ℃, adopts the method for modifying of the embodiment of the invention 2 to prepare the SEM figure that coated by titanium dioxide layer coating thickness is the modification hollow glass micropearl of 1 μ m.Relatively find, under the condition of same thickness coated by titanium dioxide layer, owing to adopted basic solution as dispersion medium in the inventive method, make the coated by titanium dioxide layer on hollow glass micropearl surface of institute's modification be more evenly distributed.
B. the heat reflectivity of reflectance coating test
The hollow glass micropearl product of two kinds of different methods modifications shown in Fig. 1 is disperseed to make two kinds of thermal insulating coatings respectively by same recipe (seeing Table 1) on the sand mill in the experiment of SDF400 type, divide three roads evenly to be painted on thin aluminum sheet (thickness 0.5mm) surface of 10cm * 10cm, coating thickness is 0.18mm, and the apparatus and method that adopt CN 1927954A to be introduced after the seasoning are carried out the heat reflectivity test to the thermal insulating coating that contains coated by titanium dioxide hollow glass micropearl product.Test result shows: using of the present invention is that hollow glass micropearl after the method modification of dispersion medium reaches 99.8% as the heat reflectivity of the prepared thermal insulating coating of filler with the basic solution, only is 96.2% and do not adopt the heat reflectivity of the prepared thermal insulating coating of hollow glass micropearl of the prior art modification of basic solution (for example adopting distilled water is dispersion medium).
Table 1 modification hollow glass micropearl prepares the prescription of thermal insulating coating
By above every test as can be seen, compared with prior art, utilize the inventive method that hollow glass micropearl is carried out the heat-proof quality that surface modification can significantly improve hollow glass micropearl.
2. method of the present invention is simple, more is applicable to suitability for industrialized production.
Method of the present invention can quantitatively go out the amount of required dropping titanium salt solution according to the amount of the basic solution of initial adding, need not the hierarchy of control in reaction process the pH value and judge the terminal point of reaction, and be reflected in the basic solution and carry out, can guarantee the titanium salt sufficient reacting that drips, so method has been simplified operation sequence when promoting product performance, for suitability for industrialized production is had laid a good foundation.
3. the hollow glass micropearl through surface modification of the present invention can effectively reduce airborne VOC content.
Get two kinds of coating that prepare among the above-mentioned experiment b, be painted on the model of gas catalysis reactor (manufacturing of Beijing company), use the 300W medium pressure mercury lamp to be light source, feeding a certain amount of concentration in reactor is C
0Formaldehyde gas, with Agilent 6890 gas chromatograph analyses concentration of formaldehyde C in the record reactor also, concentration of formaldehyde is represented with ppm at set intervals.Relatively find, be better than prior art through the effect of the hollow glass micropearl photocatalytic degradation formaldehyde of surface modification of the present invention.Therefore, the hollow glass micropearl through modification of the present invention can effectively reduce VOC content in the air.
Test result such as Fig. 3, among the figure:
1---employing distilled water is dispersion medium, drips titanium liquid and ammoniacal liquor under 60 ℃ simultaneously, and keeping the prepared coated by titanium dioxide layer thickness of reaction system pH=7 is the modification hollow glass micropearl of 1 μ m;
2---adopting the coated by titanium dioxide layer coating thickness of the present invention 2 method preparation is the modification hollow glass micropearl of 1 μ m.
Description of drawings
Fig. 1 a is that employing distilled water is the hollow glass micropearl Electronic Speculum figure of dispersion medium modification.
Fig. 1 b is the hollow glass micropearl Electronic Speculum figure that the method for the employing embodiment of the invention 2 is carried out surface modification.
Fig. 2 is the kinetic curve through the hollow glass micropearl photocatalytic degradation formaldehyde of different methods surface modification.
Embodiment
The mode of employing embodiment is described further the method for hollow glass micropearl surface modification of the present invention below, but the present invention is not limited to these embodiment.
With the concentration of 256.25ml is 0.4mol.L
-1Aqueous sodium hydroxide solution and particle diameter are 10～100 μ m, and specific surface area is 0.1～0.7m
2The hollow glass micropearl 5g of/g adds in the 1000ml flask, and the concentration that drips 0.3ml in this flask is the tensio-active agent sodium dodecyl benzene sulfonate aqueous solution of 0.1g/ml, and fully hollow glass micropearl suspension is made in stirring; With 60 rev/mins at the uniform velocity under the whipped state, the temperature of keeping reaction system is 60 ℃ at electric mixer, and the concentration that dripped 256.25ml in 6 hour reaction times in this hollow glass micropearl suspension is 0.1mol.L
-1Titanium sulfate aqueous solution, left standstill after dropwising 2 hours, filter, wash and add 10% barium chloride solution to the filtrate and do not have till the white precipitate, suction filtration obtains wet mash.This wet mash was descended dry 3 hours at 100～110 ℃, be warming up to 600 ℃ of calcinings 2 hours with 100 ℃ of/hour temperature rise rates then, obtain the hollow glass micropearl filler through surface modification, its surface titanium dioxide coating thickness is 0.5 μ m.
With the concentration of 512.5ml is 0.2mol.L
-1Potassium hydroxide aqueous solution and particle diameter are 10～100 μ m, and specific surface area is 0.1～0.7m
2The hollow glass micropearl 5g of/g adds in the 2000ml flask, and the concentration that drips 0.3ml in this flask is the tensio-active agent sodium dodecyl benzene sulfonate aqueous solution of 0.1g/ml, and fully hollow glass micropearl suspension is made in stirring; With 60 rev/mins at the uniform velocity under the whipped state, the temperature of keeping reaction system is 40 ℃ at electric mixer, and the concentration that dripped 1025ml in 8 hour reaction times in this hollow glass micropearl suspension is 0.05mol.L
-1Aqueous solution of titanyle sulfate, left standstill after dropwising 2 hours, filter, wash and add 15% barium nitrate aqueous solution to the filtrate and do not have till the white precipitate, suction filtration obtains wet mash.This wet mash was descended dry 3 hours at 100～110 ℃, be warming up to 600 ℃ of calcinings 2 hours with 100 ℃ of/hour temperature rise rates then, obtain the hollow glass micropearl filler through surface modification, its surperficial coating of titanium dioxide thickness is 1 μ m.
Embodiment 3
With the concentration of 768.75ml is 0.2mol.L
-1Aqueous sodium hydroxide solution and particle diameter are 10～100 μ m, and specific surface area is 0.1～0.7m
2The hollow glass micropearl 2.5g of/g adds in the 2000ml flask, and the concentration that drips 0.1ml in this flask is the tensio-active agent sodium dodecyl benzene sulfonate aqueous solution of 0.1g/ml, and fully hollow glass micropearl suspension is made in stirring; With 60 rev/mins at the uniform velocity under the whipped state, the temperature of keeping reaction system is 40 ℃ at electric mixer, and the concentration that dripped 384.38ml in 8 hour reaction times in this hollow glass micropearl suspension is 0.1mol.L
-1Titanium sulfate aqueous solution, left standstill after dropwising 2 hours, filter, wash and add 15% barium nitrate aqueous solution to the filtrate and do not have till the white precipitate, suction filtration obtains wet mash.This wet mash was descended dry 3 hours at 100～110 ℃, be warming up to 600 ℃ of calcinings 2 hours with 100 ℃ of/hour temperature rise rates then, obtain the hollow glass micropearl filler through surface modification, its surperficial coating of titanium dioxide thickness is 1.5 μ m.
Embodiment 4
With the concentration of 512.5ml is 0.2mol.L
-1Ammonium hydroxide (ammoniacal liquor) solution and particle diameter are 10～100 μ m, and specific surface area is 0.1～0.7m
2The hollow glass micropearl 10g of/g adds in the 2000ml flask, and the concentration that drips 0.6ml in this flask is the tensio-active agent sodium dodecyl benzene sulfonate aqueous solution of 0.1g/ml, and fully hollow glass micropearl suspension is made in stirring; With 60 rev/mins at the uniform velocity under the whipped state, the temperature of keeping reaction system is 40 ℃ at electric mixer, and the concentration that dripped 1025ml in 8 hour reaction times in this hollow glass micropearl suspension is 0.05mol.L
-1Titanium tetrachloride aqueous solution, left standstill after dropwising 2 hours, filter, wash and add 15% silver nitrate aqueous solution to the filtrate and do not have till the white precipitate, suction filtration obtains wet mash.This wet mash was descended dry 3 hours at 100～110 ℃, be warming up to 600 ℃ of calcinings 2 hours with 100 ℃ of/hour temperature rise rates then, obtain the hollow glass micropearl filler through surface modification, its surperficial coating of titanium dioxide thickness is 0.5 μ m.
Claims (10)
1. the method for a hollow glass micropearl surface modification may further comprise the steps:
(1) with 0.2～0.4mol.L
-1The aqueous solution of oxyhydroxide mix according to weight ratio 10.25: 1～307.5 with hollow glass micropearl, in this mixed solution, be to drip sodium dodecyl benzene sulfonate aqueous solution at 0.002～0.006: 1, obtain hollow glass micropearl suspension through stirring according to tensio-active agent Sodium dodecylbenzene sulfonate and hollow glass micropearl weight ratio;
(2) stir down, the temperature of keeping reaction system is 20～70 ℃, in 1～8 hour reaction times, in the hollow glass micropearl suspension that step (1) obtains, dripped with (1) in the aqueous solution volume ratio of oxyhydroxide be 0.5: 1～2, concentration is 0.05～0.1mol.L
-1The aqueous solution of tetravalent salt of titanium, left standstill after dropwising 1～4 hour, filter also washing, adding weight percent concentration and be 5～15% salts solution that contains the divalence barium ion or silver nitrate solution in filtrate does not have till the white precipitate, suction filtration obtains wet mash;
(3) the wet mash drying that step (2) is obtained is calcined then, obtains the hollow glass micropearl through modification.
2. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the particle diameter of the described hollow glass micropearl of step (1) is 10～100 μ m, and specific surface area is 0.1～0.7m
2/ g.
3. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the described oxyhydroxide of step (1) is selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide.
4. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the churning time of the described stirring of step (1) is 5～10 minutes.
5. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the described tetravalent salt of titanium of step (2) is selected from titanium sulfate, titanyl sulfate or titanium tetrachloride.
6. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the described salts solution that contains the divalence barium ion of step (2) is bariumchloride or nitrate of baryta.
7. the method for the described hollow glass micropearl surface modification of claim 1 is characterized in that: the described drying of step (3) be 100～110 ℃ dry 2～4 hours down.
8. the method for the described hollow glass micropearl surface modification of claim 1 is characterized in that: the described method for calcinating of step (3) is to be warming up to 400 ℃～700 ℃ and kept 2～4 hours with 100 ℃ of/hour heat-up rates.
9. the method for the described hollow glass micropearl surface modification of claim 1, it is characterized in that: the water in the described various aqueous solution is distilled water or deionized water.
10. the application of the method for the described hollow glass micropearl surface modification of claim 1 in the preparation thermal insulating coating is characterized in that: after adopting described method to carry out surface modification hollow glass micropearl, prepare thermal insulating coating as filler.
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