CN102815856A - Method for preparing multihole glass material by using glass powder - Google Patents
Method for preparing multihole glass material by using glass powder Download PDFInfo
- Publication number
- CN102815856A CN102815856A CN2012103187627A CN201210318762A CN102815856A CN 102815856 A CN102815856 A CN 102815856A CN 2012103187627 A CN2012103187627 A CN 2012103187627A CN 201210318762 A CN201210318762 A CN 201210318762A CN 102815856 A CN102815856 A CN 102815856A
- Authority
- CN
- China
- Prior art keywords
- glass
- powder
- preparation
- acid
- solution
- 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.)
- Granted
Links
Images
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a method for preparing a multihole glass material by using glass powder, relates to a method for preparing a multihole material, and aims to solve the problems that the conventional prepared multihole glass material cannot meet the requirements on micron aperture, uniform size and high porosity. The method comprises the following steps of: 1, performing ultrasonic cleaning and drying on metal to obtain clean metal powder; 2, preparing glass gel; 3, preparing the glass powder; 4, preparing a mixture of the metal powder and the glass powder; 5, transferring the metal powder and glass gel mixture into a die, performing high-temperature hot-press and sintering, cooling to the room temperature along with a furnace, and demolding, so as to obtain a sintered material; and 6 putting the sintered material into acid for acidic corrosion, and removing the metal powder from the sintered material, and thus obtaining the multihole glass material. The method has the advantages that 1, the requirements on micron aperture, uniform aperture size and uniform distribution are met, and the porosity can be up to over 70 percent; and 2, the multihole glass is high in intensity. The method is mainly used for preparing the multihole glass material.
Description
Technical field
The present invention relates to a kind of preparation method of porous material.
Background technology
Since the research staff of Corning Incorporated after 20th century, prepared sintered glass the thirties, sintered glass just develops into a kind of new function material gradually, because its unique advantage and individual character, makes that the position in porous material becomes even more important.
Sintered glass is as a kind of novel porous material, have the thermostability height, corrosion-resistant, intensity is high, low price, strong, the advantages of environment protection of regenerative power, be suitable for as sorbent material, finishing agent, medicinal slow release agent and support of the catalyst.Along with the continuous development of modern chemical industry, biochemistry, environmental protection, medicine and other fields, the research and the application of sintered glass deepen continuously.
The preparation method of sintered glass has a variety of; Mainly comprise foaming sintering process, fusion split-phase method, foam impregnation method, add pore-forming material method, sol-gel method etc.; The sintered glass of diverse ways preparation has very big difference, and this several method introduction is following:
1, foaming sintering process: invent by U.S. Bi Zibao Corning Incorporated the earliest; Raw material is glass cullet, whipping agent, foamed promoter and property-modifying additive etc., through pulverization process, behind the uniform mixing; Pass through high temperature melting again, the porous glass material that operations such as foaming, annealing are processed.The sintered glass that this method prepares is main with oversized hole, and the aperture is micron order (being generally more than the 100 μ m), even several millimeter.Major function is heat insulation and absorbs sound wave, therefore is widely used in heat insulation, the sound insulation of construction wall, the lagging material of industrial equipments wall.In addition; This sintered glass density is very for a short time to be about 1/4th of water; And regulation and control easily, its physical strength is directly proportional with global density, therefore can control the sintered glass that working condition is prepared various compressive properties; Because therefore the porous glass material mean pore size of this method preparation can not be used for as fixed cell carrier greater than more than the 200 μ m.
2, fusion split-phase method: raw material is inorganic materials such as silicon oxide, sodium oxide, boron oxide; Pulverization process and mix the back prepare the sodium borosilicate glass body 1400 ℃ ~ 1500 ℃ left and right sides fusions; Phase-splitting is handled under 550 ℃ ~ 700 ℃ high temperature then, analyses through acidleach and can obtain sintered glass.This preparation method is because raw material all is an inorganic materials, so raw materials cost is lower, but melt temperature is up to 1500 ℃, and its energy consumption cost is too high, and equipment is also had very harsh requirement.Boron oxide volatilizees easily under so high temperature, therefore glass ingredient is had very big influence, is difficult for accurate control borosilicic acid and receives the component proportions of glass, the sintered glass aperture that obtains.
3, foam impregnation method: put forward by people such as Schwartzwalden as far back as 1963.Raw material is that tetraethyl silicate, triethyl phosphate, four water-calcium nitrate etc. are through Prepared by Sol Gel Method bioactivity glass 58S; Its composition is silicon oxide, phosphorus oxide and quicklime; Be that template is put into 58S bioactive glass powder sauce and flooded then with the polyurethane foam; Thermal treatment goes can obtain sintered glass after the template, mainly as the bio-vitric porous support materials.The multiporous biological glass voidage of this method preparation is high, and good connectivity is arranged, and the aperture of easy feed glass.Because have perforate three-dimensional space mesh skeleton structure, can become ideal bone tissue restoration timbering material.
4, add the pore-forming material method: with metallic zinc and ydrogen peroxide 50 prepared in reaction Zn (OH)
2, use tetraethyl silicate, second alcohol and water prepared in reaction silicon sol is prepared after then both being mixed and is embedded with Zn (OH)
2The glass precursor, through for a long time aging, thermal treatment, make Zn (OH) then
2Dehydration forms nano granular of zinc oxide and embeds in the silica glass, removes zinc oxide with acid at last and can obtain mesoporous glass.This method is to be pore-forming material with the nano zine oxide, because the size of nano granular of zinc oxide is more even, is that the mesoporous glass pore size distribution prepared of template is very narrow with it therefore.But shortcoming is this mesoporous glass is not the glass on the essential meaning in fact, because its treatment temp is lower, this should be mesoporous silica gel for strictness.Moreover be template with the nano zine oxide, also be difficult to realize continuity even pore-forming material is evenly distributed, so acidleach to analyse that the zinc oxide of material internal is difficult to separate out when removing pore-forming material, this so-called mesoporous glass resistance to elevated temperatures is poor.
5, sol-gel method: traditional sol-gel method utilizes organic alkoxide such as ethyl orthosilicate, ethyl-borate and sodium ethylate to synthesize to come through hydrolysis; In order to practice thrift cost; Alkoxide except that tetraethyl silicate is used boric acid; Sodium hydroxide and SODIUMNITRATE replace, and have also reduced the toxicity that organic composition brings when so having reduced cost.After going out the active precursor of glass through Prepared by Sol Gel Method, be that melting obtains sodium borosilicate glass about 1170 ℃, analyse through acidleach again after 600 ℃ of following phase-splittings and remove boron sodium and can obtain sintered glass mutually.The sintered glass of this method preparation can be controlled pore size distribution and pore volume easily, therefore can prepare micropore glass, mesoporous glass and macropore glass, and so the variety of sintered glass can satisfy a lot of Application for Field.The sintered glass maximum diameter of hole hundreds of nanometer of but this method preparation can not prepare more wide-aperture sintered glass.
The sintered glass hole of fusion split-phase method, foam impregnation method, interpolation pore-forming material method and sol-gel method preparation is all between 10nm ~ 500nm in aforesaid method.Yet in the practical application, the sintered glass of nano level hole can not satisfy widespread demand.Particularly as some fixed cell carrier, the micrometer grade hole gap structure helps reducing that reactant molecule gets into and the resistance of product molecule when leaving, and avoids hole path to stop up.Though the foaming sintering process can prepare the sintered glass of micron order aperture size, but have the uneven phenomenon of pore size distribution, and porosity is lower.Therefore the porous glass material of existing preparation can not satisfy simultaneously and has micron pore size, and size is even, and the problem of high porosity.
Summary of the invention
The porous glass material that the present invention seeks to solve existing preparation can not satisfy simultaneously and has micron pore size, and size is even, and the problem of high porosity, and a kind of preparation method who uses the porous glass material of glass powder is provided.
A kind of preparation method who uses the porous glass material of glass powder; Specifically accomplish according to the following steps: one, clean: be in the metal powder adding absolute ethyl alcohol of 1 μ m ~ 150 μ m at first particle diameter; And be to carry out ultrasonic cleaning under 24KHz ~ 35KHz 1 ~ 3 time in frequency; The single ultrasonic cleaning time is 10min ~ 30min, is 20 ℃ ~ 40 ℃ dry 20min ~ 40min down in temperature then, promptly obtains clean metal powder; Two, preparation glass colloidal sol: 1., preparation glass-former solution: the glass-former alkoxide is dissolved in the organic solvent, adds the deionized water mixing again, be i.e. glass-former solution; 2., preparation glass solution of additive: the glass additive is dissolved in the solvent, is the glass solution of additive behind the mixing; 3., mix: glass-former solution is added in the glass solution of additive; Being 15 ℃ ~ 65 ℃ in temperature then is that 180r/min ~ 600r/min speed mixes 10min ~ 120min with stirring velocity; Obtain glass-former/glass additives mixed thing; Be that 0.5mL/min ~ 1.5mL/min adds acidic aqueous solution or is that 0.5mL/min ~ 1.5mL/min adds alkaline aqueous solution with the rate of addition then with the rate of addition, if the adding acidic aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 2 ~ 6; Promptly obtain acid glass colloidal sol; If add alkaline aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 8 ~ 12, promptly obtains alkali glass colloidal sol; Three, preparation glass powder: the acid glass colloidal sol of step 2 preparation or the alkali glass colloidal sol of step 2 preparation are placed in the drying baker; And, temperature is incubated 5h ~ 30h under being 100 ℃ ~ 500 ℃; Put into planetary ball mill after the taking-up; With grinding element and material ratio (5 ~ 6): 1 with rotating speed be ball milling 30min ~ 120min under 300r/min ~ 500r/min condition, cross 1500 mesh sieves then, promptly obtain the glass powder of particle diameter≤10 μ m; Four, preparation metal powder/glass powder mixture: at first in clean metal powder, add USP Kosher; Low whipping speed is that 15r/min ~ 60r/min mixes 20min ~ 50min down then; The glass powder that adds particle diameter≤10 μ m again; And continue 15r/min ~ 60r/min and mix 20min ~ 90min down, promptly obtain metal powder/glass powder mixture; Five, sintering: at first metal powder/glass powder mixture is transferred in the mould, being 600 ℃ ~ 1200 ℃ in temperature then is sintering 1h ~ 4h under the vacuum condition of 20MPa ~ 40MPa with mechanical compression power, cools to room temperature then with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: agglomerated material is put into acid carry out acid corrosion, till the metal powder in acid corrosion to the agglomerated material is all removed, promptly obtain porous glass material; The glass-former of step 2 described in 1. and volume of organic solvent are than being (0.5 ~ 2): 1; The glass-former of step 2 described in 1. and the volume ratio of deionized water are (2 ~ 5): 1; The quality of the glass additive of step 2 described in 2. and the volume ratio of solvent are (10g ~ 1000g): 1L; The glass-former solution of step 2 described in 3. and the volume ratio of glass solution of additive are (0.5 ~ 10): 1; USP Kosher that adds described in the step 4 and clean metal powder mass ratio are (0.01 ~ 0.05): 1; Add the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio described in the step 4 and be (0.05 ~ 0.25): 1.
Advantage of the present invention: one, the present invention is through the size and the distribution of control metal-powder; Reach the pore size of control porous glass material and the purpose of distribution; The porous glass material aperture of preparation is 1 μ m ~ 150 μ m; Compare as the porous glass material of 10nm ~ 500nm with the aperture when using and help reducing that reactant molecule gets into and the resistance of product molecule when leaving as fixed cell carrier; Avoid hole path to stop up, and the porous glass material porosity of the present invention's preparation can reach more than 70%; Two, the present invention adopts Prepared by Sol Gel Method glass colloidal sol, so the control of its chemical ingredients and proportioning accurately, again glass colloidal sol is prepared into glass powder, mixes with metal-powder then, passes through the pyritous hot pressed sintering, strengthened porous glass material intensity.
The porous glass material of the present invention's preparation can be used for fixed cell carrier or sound absorption etc.
Description of drawings
Fig. 1 is the SEM figure of 1000 times of the porous glass materials of test one preparation; Fig. 2 is the SEM figure of 200 times of the porous glass materials of this test preparation.
Embodiment
Embodiment one: this embodiment is a kind of preparation method who uses the porous glass material of glass powder, specifically accomplishes according to the following steps:
One, cleans: be in the metal powder adding absolute ethyl alcohol of 1 μ m ~ 150 μ m at first particle diameter; And be to carry out ultrasonic cleaning under 24KHz ~ 35KHz 1 ~ 3 time in frequency; The single ultrasonic cleaning time is 10min ~ 30min; Be 20 ℃ ~ 40 ℃ dry 20min ~ 40min down in temperature then, promptly obtain clean metal powder; Two, preparation glass colloidal sol: 1., preparation glass-former solution: the glass-former alkoxide is dissolved in the organic solvent, adds the deionized water mixing again, be i.e. glass-former solution; 2., preparation glass solution of additive: the glass additive is dissolved in the solvent, is the glass solution of additive behind the mixing; 3., mix: glass-former solution is added in the glass solution of additive; Being 15 ℃ ~ 65 ℃ in temperature then is that 180r/min ~ 600r/min speed mixes 10min ~ 120min with stirring velocity; Obtain glass-former/glass additives mixed thing; Be that 0.5mL/min ~ 1.5mL/min adds acidic aqueous solution or is that 0.5mL/min ~ 1.5mL/min adds alkaline aqueous solution with the rate of addition then with the rate of addition, if the adding acidic aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 2 ~ 6; Promptly obtain acid glass colloidal sol; If add alkaline aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 8 ~ 12, promptly obtains alkali glass colloidal sol; Three, preparation glass powder: the acid glass colloidal sol of step 2 preparation or the alkali glass colloidal sol of step 2 preparation are placed in the drying baker; And, temperature is incubated 5h ~ 30h under being 100 ℃ ~ 500 ℃; Put into planetary ball mill after the taking-up; With grinding element and material ratio (5 ~ 6): 1 with rotating speed be ball milling 30min ~ 120min under 300r/min ~ 500r/min condition, cross 1500 mesh sieves then, promptly obtain the glass powder of particle diameter≤10 μ m; Four, preparation metal powder/glass powder mixture: at first in clean metal powder, add USP Kosher; Low whipping speed is that 15r/min ~ 60r/min mixes 20min ~ 50min down then; The glass powder that adds particle diameter≤10 μ m again; And continue 15r/min ~ 60r/min and mix 20min ~ 90min down, promptly obtain metal powder/glass powder mixture; Five, sintering: at first metal powder/glass powder mixture is transferred in the mould, being 600 ℃ ~ 1200 ℃ in temperature then is sintering 1h ~ 4h under the vacuum condition of 20MPa ~ 40MPa with mechanical compression power, cools to room temperature then with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: agglomerated material is put into acid carry out acid corrosion, till the metal powder in acid corrosion to the agglomerated material is all removed, promptly obtain porous glass material.
The glass-former of this embodiment step 2 described in 1. and volume of organic solvent are than being (0.5 ~ 2): 1; The glass-former of this embodiment step 2 described in 1. and the volume ratio of deionized water are (2 ~ 5): 1; The quality of the glass additive of this embodiment step 2 described in 2. and the volume ratio of solvent are (10g ~ 1000g): 1L; The glass-former solution of this embodiment step 2 described in 3. and the volume ratio of glass solution of additive are (0.5 ~ 10): 1.
USP Kosher that adds described in this embodiment step 4 and clean metal powder mass ratio are (0.01 ~ 0.05): 1; Add the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio described in this embodiment step 4 and be (0.05 ~ 0.25): 1.
The thermal expansivity of two kinds of materials in a kind of material does not match, and when the high temperature hot pressed sintering, be easy to produce internal stress at material internal, and this stress is deleterious to finally obtaining complete porous glass material.If stress is excessive, remove in the process of metal-powder in chemical corrosion probably, the fracture even the disintegration of glass take place.So in the selection of glass, will make its thermal expansivity as far as possible and the matched coefficients of thermal expansion of metal-powder.Here be that metal-powder is an example with the straight iron powder.The thermal expansivity of pure iron is 12 * 10
-6About/K, as select for use and contain SiO
2Gel make coating layer, glass forming substances SiO wherein
2Thermal expansivity 5.5 * 10
-7/ K, the thermal expansivity of this and pure iron differs very big, should select those oxide compounds that can significantly improve thermal expansion coefficient of glass when therefore selecting the glass additive, can carry out the thermal expansion coefficient of glass design with reference to Jie Mujinnafa or high bridge Itou Kentaro method.With high bridge Itou Kentaro method is example; Its thermal expansion additivity coefficient that has provided common oxide compound (can be interpreted as simply that here thermal expansion additivity coefficient is big more; It can make the thermal expansivity increase of glass big more); Here the oxide compound that thermal expansion additivity coefficient is bigger has: IA family, IIA family oxide compound and PbO, and the additivity coefficient of IA family oxide compound is maximum, PbO takes second place.According to high bridge Itou Kentaro method we to estimate massfraction be 66% SiO
2, massfraction is that 4% CaO and massfraction are 30% Na
2The thermal expansion coefficient of glass that O forms is 12 * 10
-6Thermal expansivity with pure iron about/K matees basically.The thermal expansivity of common glass-former is all quite low, and to add IA family, IIA family oxide compound or PbO be effective means as improving its thermal expansivity.
This embodiment is through the size and the distribution of control metal-powder; Reach the pore size of control porous glass material and the purpose of distribution; The porous glass material aperture of preparation is 1 μ m ~ 150 μ m; Compare as the porous glass material of 10nm ~ 500nm with the aperture when using and help reducing that reactant molecule gets into and the resistance of product molecule when leaving, avoid hole path to stop up, and the porous glass material porosity of the present invention's preparation can reach more than 70% as fixed cell carrier.
This embodiment adopts Prepared by Sol Gel Method glass colloidal sol, so its chemical ingredients and proportioning control are accurately, again glass colloidal sol are prepared into glass powder, mix with metal-powder then, pass through the pyritous hot pressed sintering, strengthened porous glass material intensity.
The porous glass material of this embodiment preparation can be used for fixed cell carrier or sound absorption etc.
Embodiment two: this embodiment with the difference of embodiment one is: the metal powder described in the step 1 is acid-soluble metal-powder or acid-soluble metal oxide powder; Wherein said acid is that massfraction is 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid or 4mol/L ~ 10mol/L acetic acid aqueous solution.Other are identical with embodiment one.
The described metal powder of this embodiment is pure Fe powder, iron alloy powder, Al Al alloy powder, Mg magnesiumalloy powder, steel copper alloy powder, pure copper powder or Fe
3O
4Powder.
Embodiment three: this embodiment and embodiment one or one of two difference are: the organic solvent of step 2 described in 1. is one or more the mixture in methyl alcohol, ethanol, terepthaloyl moietie and the propyl alcohol; The glass-former alkoxide of step 2 described in 1. is Si (OC
2H
5)
4Or Si (OCH
3)
4Other are identical with embodiment one or two.
When the described organic solvent of this embodiment is mixture, press between each component arbitrarily than mixing.
Embodiment four: the difference of one of this embodiment and embodiment one to three is: the solvent of step 2 described in 2. is one or more the mixture in methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol and the deionized water; The glass additive of step 2 described in 2. is the one or more combination in glass additive alkoxide and the inorganic salt; Wherein said glass additive alkoxide is M for meeting chemical formula
X+[(OR)
-]
xCompound in a kind of or wherein several kinds of combinations, chemical formula M
X+[(OR)
-]
xDescribed in M be Be, A1, Ga, Ti, Na, K, Ca, Mg, Ba, La or Th, chemical formula M
X+[(OR)
-]
xDescribed in R be C
nH
2n+1, and n is 1,2,3 or 4, chemical formula M
X+[(OR)
-]
xDescribed in x be: 1≤x≤5; Wherein said inorganic salt are nitrate salt.Other are identical with embodiment one to three.
When the described organic solvent of this embodiment is mixture, press between each component arbitrarily than mixing.
When the described glass additive of present embodiment is several material, between several materials by arbitrarily than making up, and every kind of material is dissolved in earlier respectively in the organic solvent, mixing, and is the glass solution of additive behind the mixing.
When the described glass additive of this embodiment alkoxide is M for meeting chemical formula
X+[(OR)
-]
xCompound in several kinds of whens combination wherein, several kinds meet chemical formula is M
X+[(OR)
-]
xCompound by arbitrarily than making up.
The described glass additive of this embodiment alkoxide is NaOC
2H
5, KOC
2H
5, Ca (OC
2H
5)
2, Ge (OC
3H
7)
4, Ti (OC
2H
5)
4, In (OC
3H
7)
3, Al (OC
4H
9)
3, Zr (OC
5H
11)
4And Ta (OC
3H
7)
5In one or more combination, when described glass additive alkoxide is mixture, between each component by arbitrarily than mixing.
The described nitrate salt of this embodiment is NaNO
3And Ca (NO
3)
24H
2Among the O one or both are arbitrarily than combination.
Embodiment five: the difference of one of this embodiment and embodiment one to four is: the acidic aqueous solution of step 2 described in 3. is that massfraction is that 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid, 4mol/L ~ 10mol/L acetic acid aqueous solution or massfraction are 0.1% ~ 5% aqueous citric acid solution; The alkaline aqueous solution of step 2 described in 3. is that massfraction is 5% ~ 25% ammoniacal liquor.Other are identical with embodiment one to four.
Embodiment six: this embodiment with the difference of one of embodiment one to five is: the acid described in the step 6 is that massfraction is 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid or 4mol/L ~ 10mol/L acetic acid aqueous solution.Other are identical with embodiment one to five.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method who uses the porous glass material of glass powder; Specifically accomplish according to the following steps: one, clean: be in the pure Fe powder adding absolute ethyl alcohol of 3 μ m ~ 7 μ m at first the 50g particle diameter; And be to carry out ultrasonic cleaning under the 30KHz 2 times in frequency; The single ultrasonic cleaning time is 20min, is 30 ℃ of dry 30min down in temperature then, promptly obtains clean metal powder; Two, preparation glass colloidal sol: 1., preparation glass-former solution: the methyl silicate of 25mL is dissolved in the ethanol of 25mL, adds the deionized water of 5mL again, and then stirring velocity is that 300r/min stirs 30min, i.e. glass-former solution down; 2., preparation glass solution of additive: at first sodium ethylate is dissolved in the ethanol, configuration 30mL mass concentration is 10% alcohol sodium alcohol solution, then with the Ca (NO of 2.5g
3)
24H
2O is dissolved in the ethanol of 30mL, obtains Ca (NO
3)
24H
2The O/ ethanolic soln is again with Ca (NO
3)
24H
2It is in 10% the alcohol sodium alcohol solution that the O/ ethanolic soln adds the 30mL mass concentration, and low whipping speed 300r/min stirs 30min down, promptly obtains the glass solution of additive; 3., mix: in the glass solution of additive that 2. the glass-former solution adding step 2 that 1. step 2 is obtained obtains; Then temperature be 40 ℃ with stirring velocity mix 60min for 300r/min speed; Obtain glass-former/glass additives mixed thing; With the rate of addition be then 1mL/min to add mass concentration be 25% ammoniacal liquor, the pH value of glass organizer/glass additives mixed thing is adjusted to 9, promptly obtain alkali glass colloidal sol; Three, preparation glass powder: the acid glass colloidal sol of step 2 preparation or the alkali glass colloidal sol of step 2 preparation are placed in the drying baker; And, temperature is incubated 18h under being 200 ℃; Put into planetary ball mill after the taking-up; With grinding element and material ratio 5:1 and rotating speed is ball milling 60min under the 300r/min condition, crosses 1500 mesh sieves then, promptly obtains the glass powder of particle diameter≤10 μ m; Four, preparation metal powder/glass powder mixture: at first prepare and add the 1.5g USP Kosher in the clean metal powder to step 1; Low whipping speed is that 30r/min mixes 30min down then; The glass powder that adds 8g particle diameter≤10 μ m again; And continue 30r/min and mix 30min down, promptly obtain metal powder/glass powder mixture; Five, sintering: at first metal powder/glass powder the mixture with step 4 preparation is transferred in the mould, and being 700 ℃ in temperature then is sintering 1.5h under the vacuum condition of 40MPa with mechanical compression power, cools to room temperature then with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: it is that 10% Hydrogen chloride carries out acid corrosion that agglomerated material is put into massfraction, and (the acid corrosion time is 120h) promptly obtained porous glass material till the metal powder in acid corrosion to the agglomerated material was all removed.
Adopt the porous glass material of this test of sem observation preparation; As shown in Figure 1; Fig. 1 is the SEM figure of 1000 times of the porous glass materials of this test preparation, but the about 5 μ m in porous glass material aperture through Fig. 1 knowledge capital test preparation, and porosity is about 70%.
Adopt universal electrical mechanical test machine that the porous glass material of this test preparation is carried out compressive strength and detect, but be 1.9MPa through the compressive strength that detects the porous glass material that the knowledge capital test prepares.
Test two: a kind of preparation method who uses the porous glass material of glass powder; Specifically accomplish according to the following steps: one, clean: be in the pure copper powder adding absolute ethyl alcohol of 1 μ m ~ 5 μ m at first the 35g particle diameter; And be to carry out ultrasonic cleaning under the 30KHz 2 times in frequency; The single ultrasonic cleaning time is 20min, is 30 ℃ of dry 30min down in temperature then, promptly obtains clean metal powder; Two, preparation glass colloidal sol: 1., preparation glass-former solution: the methyl silicate of 25mL is dissolved in the ethanol of 25mL, adds the deionized water of 5mL again, and then stirring velocity is that 300r/min stirs 30min, i.e. glass-former solution down; 2., preparation glass solution of additive: at first sodium ethylate is dissolved in the ethanol; Configuration 30mL mass concentration is 10% alcohol sodium alcohol solution; Then calcium methylate is dissolved in the methyl alcohol, configuration 10mL mass concentration is 5% calcium methylate methanol solution, again with ASBD (Al (C
4H
9)
3) be dissolved in the ethanol; Configuration 10mL mass concentration is 5% ASBD ethanolic soln; Be that 10% alcohol sodium alcohol solution, 10mL mass concentration are that 5% calcium methylate methanol solution and 10mL mass concentration are that 5% ASBD ethanolic soln is admixed together with the 30mL mass concentration then; And stir 30min under the low whipping speed 400r/min, promptly obtain the glass solution of additive; 3., mix: in the glass solution of additive that 2. the glass-former solution adding step 2 that 1. step 2 is obtained obtains; Then temperature be 40 ℃ with stirring velocity mix 60min for 300r/min speed; Obtain glass-former/glass additives mixed thing; With the rate of addition be then 1mL/min to add mass concentration be 25% ammoniacal liquor, the pH value of glass organizer/glass additives mixed thing is adjusted to 9, promptly obtain alkali glass colloidal sol; Three, preparation glass powder: the acid glass colloidal sol of step 2 preparation or the alkali glass colloidal sol of step 2 preparation are placed in the drying baker; And, temperature is incubated 18h under being 200 ℃; Put into planetary ball mill after the taking-up; With grinding element and material ratio 5:1 and rotating speed is ball milling 60min under the 300r/min condition, crosses 1500 mesh sieves then, promptly obtains the glass powder of particle diameter≤10 μ m; Four, preparation metal powder/glass powder mixture: at first prepare and add the 1.5g USP Kosher in the clean metal powder to step 1; Low whipping speed is that 30r/min mixes 30min down then; The glass powder that adds 8g particle diameter≤10 μ m again; And continue 30r/min and mix 30min down, promptly obtain metal powder/glass powder mixture; Five, sintering: at first metal powder/glass powder the mixture with step 4 preparation is transferred in the mould, and being 700 ℃ in temperature then is sintering 1.5h under the vacuum condition of 40MPa with mechanical compression power, cools to room temperature then with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: it is that 10% Hydrogen chloride carries out acid corrosion that agglomerated material is put into massfraction, and (the acid corrosion time is 120h) promptly obtained porous glass material till the metal powder in acid corrosion to the agglomerated material was all removed.
Adopt the porous glass material of this test of sem observation preparation; As shown in Figure 2; Fig. 2 is the SEM figure of 200 times of the porous glass materials of this test preparation, but the about 5 μ m in porous glass material aperture through Fig. 2 knowledge capital test preparation, and porosity is about 72%.
Adopt universal electrical mechanical test machine that the porous glass material of this test preparation is carried out compressive strength and detect, but be 1.8MPa through the compressive strength that detects the porous glass material that the knowledge capital test prepares.
Claims (6)
1. preparation method who uses the porous glass material of glass powder; Porous glass material that it is characterized in that using glass powder and preparation method thereof is accomplished according to the following steps: one, clean: be that the metal powder of 1 μ m ~ 150 μ m adds in the absolute ethyl alcohol with particle diameter at first; And be to carry out ultrasonic cleaning under 24KHz ~ 35KHz 1 ~ 3 time in frequency; The single ultrasonic cleaning time is 10min ~ 30min, is 20 ℃ ~ 40 ℃ dry 20min ~ 40min down in temperature then, promptly obtains clean metal powder; Two, preparation glass colloidal sol: 1., preparation glass-former solution: the glass-former alkoxide is dissolved in the organic solvent, adds the deionized water mixing again, be i.e. glass-former solution; 2., preparation glass solution of additive: the glass additive is dissolved in the solvent, is the glass solution of additive behind the mixing; 3., mix: glass-former solution is added in the glass solution of additive; Being 15 ℃ ~ 65 ℃ in temperature then is that 180r/min ~ 600r/min speed mixes 10min ~ 120min with stirring velocity; Obtain glass-former/glass additives mixed thing; Be that 0.5mL/min ~ 1.5mL/min adds acidic aqueous solution or is that 0.5mL/min ~ 1.5mL/min adds alkaline aqueous solution with the rate of addition then with the rate of addition, if the adding acidic aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 2 ~ 6; Promptly obtain acid glass colloidal sol; If add alkaline aqueous solution, then the pH value with glass organizer/glass additives mixed thing is adjusted to 8 ~ 12, promptly obtains alkali glass colloidal sol; Three, preparation glass powder: the acid glass colloidal sol of step 2 preparation or the alkali glass colloidal sol of step 2 preparation are placed in the drying baker; And, temperature is incubated 5h ~ 30h under being 100 ℃ ~ 500 ℃; Put into planetary ball mill after the taking-up; With grinding element and material ratio (5 ~ 6): 1 with rotating speed be ball milling 30min ~ 120min under 300r/min ~ 500r/min condition, cross 1500 mesh sieves then, promptly obtain the glass powder of particle diameter≤10 μ m; Four, preparation metal powder/glass powder mixture: at first in clean metal powder, add USP Kosher; Low whipping speed is that 15r/min ~ 60r/min mixes 20min ~ 50min down then; The glass powder that adds particle diameter≤10 μ m again; And continue 15r/min ~ 60r/min and mix 20min ~ 90min down, promptly obtain metal powder/glass powder mixture; Five, sintering: at first metal powder/glass powder mixture is transferred in the mould, being 600 ℃ ~ 1200 ℃ in temperature then is sintering 1h ~ 4h under the vacuum condition of 20MPa ~ 40MPa with mechanical compression power, cools to room temperature then with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: agglomerated material is put into acid carry out acid corrosion, till the metal powder in acid corrosion to the agglomerated material is all removed, promptly obtain porous glass material; The glass-former of step 2 described in 1. and volume of organic solvent are than being (0.5 ~ 2): 1; The glass-former of step 2 described in 1. and the volume ratio of deionized water are (2 ~ 5): 1; The quality of the glass additive of step 2 described in 2. and the volume ratio of solvent are (10g ~ 1000g): 1L; The glass-former solution of step 2 described in 3. and the volume ratio of glass solution of additive are (0.5 ~ 10): 1; USP Kosher that adds described in the step 4 and clean metal powder mass ratio are (0.01 ~ 0.05): 1; Add the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio described in the step 4 and be (0.05 ~ 0.25): 1.
2. a kind of preparation method who uses the porous glass material of glass powder according to claim 1 is characterized in that the metal powder of stating in the step 1 is acid-soluble metal-powder or acid-soluble metal oxide powder; Wherein said acid is that massfraction is 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid or 4mol/L ~ 10mol/L acetic acid aqueous solution.
3. a kind of preparation method who uses the porous glass material of glass powder according to claim 2 is characterized in that the organic solvent described in step 2 1. is one or more the mixture in methyl alcohol, ethanol, terepthaloyl moietie and the propyl alcohol; The glass-former alkoxide of step 2 described in 1. is Si (OC
2H
5)
4Or Si (OCH
3)
4
4. a kind of preparation method who uses the porous glass material of glass powder according to claim 3 is characterized in that the solvent described in step 2 2. is one or more the mixture in methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol and the deionized water; The glass additive of step 2 described in 2. is the one or more combination in glass additive alkoxide and the inorganic salt; Wherein said glass additive alkoxide is M for meeting chemical formula
X+[(OR)
-]
xCompound in a kind of or wherein several kinds of combinations, chemical formula M
X+[(OR)
-]
xDescribed in M be Be, A1, Ga, Ti, Na, K, Ca, Mg, Ba, La or Th, chemical formula M
X+[(OR)
-]
xDescribed in R be C
nH
2n+1, and n is 1,2,3 or 4, chemical formula M
X+[(OR)
-]
xDescribed in x be: 1≤x≤5; Wherein said inorganic salt are nitrate salt.
5. according to claim 1,2,3 or 4 described a kind of preparing methods that use the porous glass material of glass powder, it is characterized in that the acidic aqueous solution described in step 2 3. is that massfraction is that 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid, 4mol/L ~ 10mol/L acetic acid aqueous solution or massfraction are 0.1% ~ 5% aqueous citric acid solution; The alkaline aqueous solution of step 2 described in 3. is that massfraction is 5% ~ 25% ammoniacal liquor.
6. a kind of preparation method who uses the porous glass material of glass powder according to claim 5 is characterized in that the acid described in the step 6 is that massfraction is 5% ~ 30% aqueous hydrochloric acid, 5mol/L ~ 12mol/L aqueous sulfuric acid or 4mol/L ~ 10mol/L acetic acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210318762.7A CN102815856B (en) | 2012-08-31 | 2012-08-31 | Method for preparing multihole glass material by using glass powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210318762.7A CN102815856B (en) | 2012-08-31 | 2012-08-31 | Method for preparing multihole glass material by using glass powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102815856A true CN102815856A (en) | 2012-12-12 |
| CN102815856B CN102815856B (en) | 2014-08-20 |
Family
ID=47300363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210318762.7A Active CN102815856B (en) | 2012-08-31 | 2012-08-31 | Method for preparing multihole glass material by using glass powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102815856B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880285A (en) * | 2013-03-14 | 2014-06-25 | 美国诺邦生物制品有限公司 | Sol-gel Bioactive Glass Initial Solution And A Preparation Method Of The Sol-gel Bioactive Glass And The Prepared Sol-gel Bioactive Glass Initial Solution |
| CN104692667A (en) * | 2015-02-11 | 2015-06-10 | 陕西科技大学 | Method for preparing porous glass filter element for water purifier |
| CN107117822A (en) * | 2017-06-30 | 2017-09-01 | 合肥利裕泰玻璃制品有限公司 | A kind of preparation method of the cellular glass containing various metals |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03257029A (en) * | 1990-03-08 | 1991-11-15 | Mitsubishi Gas Chem Co Inc | Production of quartz glass |
| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
-
2012
- 2012-08-31 CN CN201210318762.7A patent/CN102815856B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03257029A (en) * | 1990-03-08 | 1991-11-15 | Mitsubishi Gas Chem Co Inc | Production of quartz glass |
| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| SHICHAO ZHAO ET AL.: "Synthesis of mesoporous Si02 glass by a novel chemical method", 《MATERIALS LETTERS》, vol. 61, no. 3, 28 February 2007 (2007-02-28) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880285A (en) * | 2013-03-14 | 2014-06-25 | 美国诺邦生物制品有限公司 | Sol-gel Bioactive Glass Initial Solution And A Preparation Method Of The Sol-gel Bioactive Glass And The Prepared Sol-gel Bioactive Glass Initial Solution |
| CN104692667A (en) * | 2015-02-11 | 2015-06-10 | 陕西科技大学 | Method for preparing porous glass filter element for water purifier |
| CN107117822A (en) * | 2017-06-30 | 2017-09-01 | 合肥利裕泰玻璃制品有限公司 | A kind of preparation method of the cellular glass containing various metals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102815856B (en) | 2014-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107399989B (en) | Preparation method of reinforced silicon carbide-alumina composite foamed ceramic | |
| CN102795783A (en) | Preparation method of porous glass material | |
| CN104177099B (en) | A kind of micro-closed pore light-weight corundum fireproof aggregate and preparation method thereof | |
| CN105271784A (en) | Hollow glass microsphere | |
| CN106220218A (en) | A kind of ceramic foam filter and manufacture method thereof | |
| CN104177071B (en) | White olivine saggar and preparation method thereof | |
| KR20130040083A (en) | Manufacture method of inorganic foam using magnesia and its hardner at room temperature | |
| CN103553686A (en) | Magnesium aluminate spinel foamed ceramic filter as well as preparation method thereof | |
| CN108530041A (en) | A kind of high-purity high-strength aluminium oxide ceramics and its low temperature preparation method | |
| CN102815856B (en) | Method for preparing multihole glass material by using glass powder | |
| CN109052970B (en) | Method for preparing functional glass ceramics by directly sintering asbestos tailings | |
| CN103771426B (en) | A kind of take diatomite as the method for raw material low-firing porous cristobalite | |
| CN102731118A (en) | Corundum micro-pore heat-insulating and fireproof material and preparation method thereof | |
| CN104046826A (en) | Foamed magnesium-based material and preparation method thereof | |
| CN110540414A (en) | Preparation method of nano microporous corundum | |
| CN106045322A (en) | High-strength whitening glaze slurry for ceramic and preparation method of high-strength whitening glaze slurry | |
| CN105254327A (en) | Environment-friendly autoclaved aerated concrete block and preparation method thereof | |
| CN1425606A (en) | Ordered nano mesoporous carbon material of two-way connection and 3-D cubic structure and its preparing method | |
| CN105036748A (en) | Silicon carbide brick and preparation method thereof | |
| CN110294636A (en) | A kind of lightweight heat-proof metallurgy of nickel waste residue foamed ceramics and preparation method thereof | |
| CN102602982A (en) | Method for preparing porous ZnO by means of combining dealloying method with ceramic coating | |
| KR101300772B1 (en) | Manufacture method for inorganic form of light weight using magnesia and its hardner without foaming step at room temperature | |
| CN104073673A (en) | Preparation method of ceramic reinforced metal-based composite material | |
| CN104371703A (en) | Method for preparing oil fracturing proppant from high-aluminum fly ash | |
| CN103936400B (en) | Alumina based porous ceramic thermal insulation material and preparation method |
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 |