CN102815856B - Method for preparing multihole glass material by using glass powder - Google Patents
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- CN102815856B CN102815856B CN201210318762.7A CN201210318762A CN102815856B CN 102815856 B CN102815856 B CN 102815856B CN 201210318762 A CN201210318762 A CN 201210318762A CN 102815856 B CN102815856 B CN 102815856B
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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 is after 20th century, prepared sintered glass the thirties, sintered glass just develops into a kind of new function material gradually, due to its unique advantage and individual character, makes the position in porous material become even more important.
Sintered glass is as the novel porous material of one, has that thermostability is high, corrosion-resistant, intensity is high, low price, regenerative power are strong, advantages of environment protection, are suitable for use as sorbent material, finishing agent, medicinal slow release agent and support of the catalyst.Along with the development of modern chemical industry, biochemistry, environmental protection, medicine and other fields, research and the application of sintered glass deepen continuously.
The preparation method of sintered glass has a variety of, mainly comprise foaming sintering process, melting split-phase method, foam impregnation method, add pore-forming material method, sol-gel method etc., sintered glass prepared by diverse ways has very large difference, and this several method is described below:
1, foaming sintering process: invented by Bi Zibao Corning Incorporated of the U.S. the earliest, raw material is glass cullet, whipping agent, foamed promoter and property-modifying additive etc., through pulverization process, after evenly mixing, pass through again high temperature melting, the porous glass material that the operations such as foaming, annealing are made.The sintered glass that this method prepares is taking oversized hole as main, and aperture is in micron order (more than being generally 100 μ m), even several millimeter.Major function is heat insulation and absorbs sound wave, is therefore 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 little is 1/4th left and right of water, and easily regulation and control, its physical strength is directly proportional with global density, therefore can production control condition prepare the sintered glass of various compressive properties, because therefore porous glass material mean pore size prepared by this method can not be used for as fixed cell carrier more than being greater than 200 μ m.
2, melting split-phase method: raw material is the inorganic materials such as silicon oxide, sodium oxide, boron oxide, pulverization process and mix after prepare sodium borosilicate glass body 1400 DEG C～1500 DEG C left and right meltings, then phase-splitting processing under 550 DEG C～700 DEG C high temperature, then can obtain sintered glass through Acid Leaching.This preparation method is because raw material is all inorganic materials, and therefore raw materials cost is lower, but melt temperature is up to 1500 DEG C, and its energy consumption cost is too high, and equipment is also had to very harsh requirement.At so high temperature, boron oxide easily volatilizees, and therefore glass ingredient is had a significant impact, and is difficult for accurately controlling borosilicic acid and receives the component proportions of glass, the sintered glass aperture obtaining.
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 prepared bioactivity glass 58S by sol-gel method, its composition is silicon oxide, phosphorus oxide and calcium oxide, then put into 58S bioactive glass powder sauce floods taking polyurethane foam as template, thermal treatment goes can obtain sintered glass after template, mainly as bio-vitric porous support materials.Porous bioglass voidage prepared by this method is high, has good connectivity, and easily controls the aperture of glass.Because there is perforate three-dimensional space mesh skeleton structure, can become desirable bone tissue restoration timbering material.
4, add pore-forming material method: with metallic zinc and hydrogen peroxide reaction preparation Zn (OH)
2, with tetraethyl silicate, silicon sol is prepared in the reaction of second alcohol and water, after then both being mixed, prepares and is embedded with Zn (OH)
2glass precursor, then pass through aging, thermal treatment for a long time, make Zn (OH)
2dehydration forms nano granular of zinc oxide and embeds in silica glass, finally removes zinc oxide with acid and can obtain mesoporous glass.This method is taking nano zine oxide as pore-forming material, and because the size of nano granular of zinc oxide is more even, the mesoporous glass pore size distribution of therefore preparing taking it as template is very narrow.But shortcoming is this mesoporous glass is not the glass on essential meaning in fact, because its treatment temp is lower, this should be mesoporous silica gel strictly.Moreover taking nano zine oxide as template, be also difficult to realize continuity even if pore-forming material is evenly distributed, and when therefore Acid Leaching removes pore-forming material, the zinc oxide of material internal is difficult to separate out, and this so-called mesoporous glass resistance to elevated temperatures is poor.
5, sol-gel method: traditional sol-gel method utilizes the organic alkoxides such as ethyl orthosilicate, ethyl-borate and sodium ethylate to come by hydrolysis, for cost-saving, alkoxide boric acid except tetraethyl silicate, sodium hydroxide and SODIUMNITRATE replace, and have also reduced the toxicity that organic composition brings when so having reduced cost.Preparing after the active precursor of glass by sol-gel method, is that melting obtains sodium borosilicate glass 1170 DEG C of left and right, removes boron sodium again at 600 DEG C can obtain mutually sintered glass after phase-splitting through Acid Leaching.Sintered glass prepared by this method can be controlled pore size distribution and pore volume easily, therefore can prepare micropore glass, mesoporous glass and macropore glass, and so the diversity of sintered glass can meet the application in a lot of fields.The sintered glass maximum diameter of hole hundreds of nanometer that but prepared by this method, can not prepare more wide-aperture sintered glass.
The sintered glass hole that in aforesaid method prepared by melting split-phase method, foam impregnation method, interpolation pore-forming material method and sol-gel method is all between 10nm～500nm.But in practical application, the sintered glass of nano level hole can not meet widespread demand.Particularly as some fixed cell carrier, micrometer grade hole gap structure is conducive to reduce resistance when reactant molecule enters and product molecule leaves, avoids hole path to stop up.Although foaming sintering process can be prepared the sintered glass of micron order aperture size, but have the inhomogeneous phenomenon of pore size distribution, and porosity is lower.Therefore the porous glass material of existing preparation can not meet and have micron pore size simultaneously, 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 meet and have micron pore size simultaneously, size evenly, and the problem of high porosity, and a kind of preparation method of the porous glass material that uses glass powder is provided.
A kind of preparation method of the porous glass material that uses glass powder, specifically complete according to the following steps: one, clean: the metal powder that by particle diameter is first 1 μ m～150 μ m adds in dehydrated alcohol, and be under 24KHz～35KHz, to carry out ultrasonic cleaning 1～3 time in frequency, the single ultrasonic cleaning time is 10min～30min, then be dry 20min～40min at 20 DEG C～40 DEG C in temperature, obtain clean metal powder, 1., prepare glass-former solution two, prepare glass colloidal sol:: glass-former alkoxide is dissolved in organic solvent, then adds deionized water to mix, be i.e. glass-former solution, 2., prepare glass solution of additive: glass additive is dissolved in solvent, is glass solution of additive after mixing, 3., mix: glass-former solution is added in glass solution of additive, then being 15 DEG C～65 DEG C in temperature is that 180r/min～600r/min speed is uniformly mixed 10min～120min with stirring velocity, obtain glass-former/glass additives mixed thing, then add acidic aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min or add alkaline aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min, if add acidic aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 2～6, obtain acid glass colloidal sol, if add alkaline aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 8～12, obtain alkali glass colloidal sol, three, prepare glass powder: alkali glass colloidal sol prepared by acid glass colloidal sol prepared by step 2 or step 2 is placed in drying baker, and be to be incubated 5h～30h at 100 DEG C～500 DEG C in temperature, after taking-up, put into planetary ball mill, taking grinding element and material ratio (5～6): 1 and rotating speed ball milling 30min～120min under 300r/min～500r/min condition, then cross 1500 mesh sieves, obtain the glass powder of particle diameter≤10 μ m, four, prepare metal powder/glass powder mixture: first in clean metal powder, add glycerol, then low whipping speed is to mix 20min～50min under 15r/min～60r/min, add again the glass powder of particle diameter≤10 μ m, and continue to mix 20min～90min under 15r/min～60r/min, obtain metal powder/glass powder mixture, five, sintering: first metal powder/glass powder mixture is transferred in mould, then be sintering 1h～4h under 600 DEG C～1200 DEG C and the mechanical compression power vacuum condition that is 20MPa～40MPa in temperature, then cool to room temperature with the furnace, obtain agglomerated material after moving back mould, six, acid corrosion: agglomerated material is put into acid and carry out acid corrosion, acid corrosion to the metal powder in agglomerated material obtains porous glass material till all removing, the glass-former alkoxide of step 2 described in 1. and the volume ratio of organic solvent are (0.5～2): 1, the glass-former alkoxide of step 2 described in 1. and the volume ratio of deionized water are (2～5): 1, the quality of glass additive and the volume ratio of solvent of step 2 described in is 2. (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, the glycerol adding described in step 4 and clean metal powder mass ratio are (0.01～0.05): 1, described in step 4, adding the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio is (0.05～0.25): 1.
Advantage of the present invention: one, the present invention is by controlling size and the distribution of metal-powder, reach and control the pore size of porous glass material and the object of distribution, the porous glass material aperture of preparation is 1 μ m～150 μ m, compared with the porous glass material that is 10nm～500nm with aperture while use as fixed cell carrier, be conducive to reduce resistance when reactant molecule enters and product molecule leaves, avoid hole path to stop up, and porous glass material porosity prepared by the present invention can reach more than 70%; Two, the present invention adopts sol-gel method to prepare glass colloidal sol, and therefore its chemical composition and proportioning control are accurate, then glass colloidal sol is prepared into glass powder, then mixes with metal-powder, through the hot pressed sintering of high temperature, has strengthened porous glass material intensity.
Porous glass material prepared by the present invention can be used for fixed cell carrier or sound absorption etc.
Brief description of the drawings
Fig. 1 is the SEM figure that tests 1000 times of porous glass materials of preparing; Fig. 2 is the SEM figure of 200 times of the porous glass materials of this test preparation.
Embodiment
Embodiment one: present embodiment is a kind of preparation method of the porous glass material that uses glass powder, specifically completes according to the following steps:
One, clean: the metal powder that by particle diameter is first 1 μ m～150 μ m adds in dehydrated alcohol, and be under 24KHz～35KHz, to carry out ultrasonic cleaning 1～3 time in frequency, the single ultrasonic cleaning time is 10min～30min, then be dry 20min～40min at 20 DEG C～40 DEG C in temperature, obtain clean metal powder, 1., prepare glass-former solution two, prepare glass colloidal sol:: glass-former alkoxide is dissolved in organic solvent, then adds deionized water to mix, be i.e. glass-former solution, 2., prepare glass solution of additive: glass additive is dissolved in solvent, is glass solution of additive after mixing, 3., mix: glass-former solution is added in glass solution of additive, then being 15 DEG C～65 DEG C in temperature is that 180r/min～600r/min speed is uniformly mixed 10min～120min with stirring velocity, obtain glass-former/glass additives mixed thing, then add acidic aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min or add alkaline aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min, if add acidic aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 2～6, obtain acid glass colloidal sol, if add alkaline aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 8～12, obtain alkali glass colloidal sol, three, prepare glass powder: alkali glass colloidal sol prepared by acid glass colloidal sol prepared by step 2 or step 2 is placed in drying baker, and be to be incubated 5h～30h at 100 DEG C～500 DEG C in temperature, after taking-up, put into planetary ball mill, taking grinding element and material ratio (5～6): 1 and rotating speed ball milling 30min～120min under 300r/min～500r/min condition, then cross 1500 mesh sieves, obtain the glass powder of particle diameter≤10 μ m, four, prepare metal powder/glass powder mixture: first in clean metal powder, add glycerol, then low whipping speed is to mix 20min～50min under 15r/min～60r/min, add again the glass powder of particle diameter≤10 μ m, and continue to mix 20min～90min under 15r/min～60r/min, obtain metal powder/glass powder mixture, five, sintering: first metal powder/glass powder mixture is transferred in mould, then be sintering 1h～4h under 600 DEG C～1200 DEG C and the mechanical compression power vacuum condition that is 20MPa～40MPa in temperature, then cool to room temperature with the furnace, obtain agglomerated material after moving back mould, six, acid corrosion: agglomerated material is put into acid and carry out acid corrosion, acid corrosion to the metal powder in agglomerated material obtains porous glass material till all removing.
The glass-former alkoxide of present embodiment step 2 described in 1. and the volume ratio of organic solvent are (0.5～2): 1; The glass-former alkoxide of present embodiment step 2 described in 1. and the volume ratio of deionized water are (2～5): 1; The quality of glass additive and the volume ratio of solvent of present embodiment step 2 described in is 2. (10g～1000g): 1L; The glass-former solution of present embodiment step 2 described in 3. and the volume ratio of glass solution of additive are (0.5～10): 1.
The glycerol adding described in present embodiment step 4 and clean metal powder mass ratio are (0.01～0.05): 1; Described in present embodiment step 4, adding the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio is (0.05～0.25): 1.
The thermal expansivity of two kinds of materials in a kind of material does not mate, and be easy to produce internal stress at material internal, and this stress is harmful to finally obtaining complete porous glass material in the time of high temperature hot pressing sintering.If stress is excessive, probably to remove in the process of metal-powder in chemical corrosion, the fracture that glass occurs is even disintegrated.So will make its thermal expansivity as far as possible and the matched coefficients of thermal expansion of metal-powder in the selection of glass.Here be example taking straight iron powder as metal-powder.The thermal expansivity of pure iron is 12 × 10
-6/ K left and right, as select containing 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 large, should select those oxide compounds that can significantly improve thermal expansion coefficient of glass while therefore selecting glass additive, can carry out thermal expansion coefficient of glass design with reference to Jie Mujinnafa or high bridge Itou Kentaro method.Taking high bridge Itou Kentaro method as example, its thermal expansion additivity coefficient that has provided common oxide compound (can simply be interpreted as that thermal expansion additivity coefficient is larger here, it can make the thermal expansivity increase of glass larger), here the oxide compound that thermal expansion additivity coefficient is larger has: IA family, IIA family oxide compound and PbO, and the additivity coefficient maximum of IA family oxide compound, PbO takes second place.According to high bridge Itou Kentaro method we to estimate massfraction be 66% SiO
2, the Na that the CaO that massfraction is 4% and massfraction are 30%
2the thermal expansion coefficient of glass of O composition is 12 × 10
-6the thermal expansivity of/K left and right and pure iron mates substantially.The thermal expansivity of common glass-former is all quite low, and as improved its thermal expansivity, to add IA family, IIA family oxide compound or PbO be effective means.
Present embodiment is by controlling size and the distribution of metal-powder, reach and control the pore size of porous glass material and the object of distribution, the porous glass material aperture of preparation is 1 μ m～150 μ m, compared with the porous glass material that is 10nm～500nm with aperture while use as fixed cell carrier, be conducive to reduce resistance when reactant molecule enters and product molecule leaves, avoid hole path to stop up, and porous glass material porosity prepared by the present invention can reach more than 70%.
Present embodiment adopts sol-gel method to prepare glass colloidal sol, and therefore its chemical composition and proportioning control are accurate, then glass colloidal sol is prepared into glass powder, then mixes with metal-powder, through the hot pressed sintering of high temperature, has strengthened porous glass material intensity.
Porous glass material prepared by present embodiment can be used for fixed cell carrier or sound absorption etc.
Embodiment two: the difference of present embodiment and embodiment one is: the metal powder described in 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.
Metal powder described in present embodiment is pure Fe powder, iron alloy powder, Al Al alloy powder, Mg magnesium alloy powder, steel copper alloy powder, pure copper powder or Fe
3o
4powder.
Embodiment three: the difference of one of present embodiment and embodiment one or two is: the organic solvent of step 2 described in is 1. one or more the mixture in methyl alcohol, ethanol, ethylene glycol and propyl alcohol; The glass-former alkoxide of step 2 described in is 1. Si (OC
2h
5)
4or Si (OCH
3)
4.Other are identical with embodiment one or two.
In the time that the organic solvent described in present embodiment is mixture, between each component, be mixed by any ratio.
Embodiment four: the difference of one of present embodiment and embodiment one to three is: the solvent of step 2 described in is 2. one or more the mixture in methyl alcohol, ethanol, ethylene glycol, propyl alcohol and deionized water; The glass additive of step 2 described in is 2. the one or more combination in glass additive alkoxide and inorganic salt; Wherein said glass additive alkoxide is M for meeting chemical formula
x+[(OR)
-]
xcompound in a kind of or wherein several 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.Other are identical with embodiment one to three.
In the time that the organic solvent described in present embodiment is mixture, between each component, be mixed by any ratio.
In the time that the glass additive described in present embodiment is several material, between several materials, by any combination, and every kind of material is first dissolved in respectively in organic solvent, mixing, and is glass solution of additive after mixing.
When the glass additive alkoxide described in present embodiment is M for meeting chemical formula
x+[(OR)
-]
xcompound in wherein when several combination, several chemical formulas that meet are M
x+[(OR)
-]
xcompound by any combination.
Glass additive alkoxide described in present embodiment 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, be mixed by any ratio.
Nitrate described in present embodiment is NaNO
3and Ca (NO
3)
24H
2one or both any combinations in O.
Embodiment five: the difference of one of present embodiment and embodiment one to four is: the acidic aqueous solution of step 2 described in is 3. that massfraction is the aqueous citric acid solution 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%; The alkaline aqueous solution of step 2 described in is 3. that massfraction is 5%～25% ammoniacal liquor.Other are identical with embodiment one to four.
Embodiment six: the difference of one of present embodiment and embodiment one to five is: the acid described in 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 of the porous glass material that uses glass powder, specifically complete according to the following steps: one, clean: the pure Fe powder that by 50g particle diameter is first 3 μ m～7 μ m adds in dehydrated alcohol, and be under 30KHz, to carry out ultrasonic cleaning 2 times in frequency, the single ultrasonic cleaning time is 20min, then be dry 30min at 30 DEG C in temperature, obtain clean metal powder; 1., prepare glass-former solution two, prepare glass colloidal sol:: the methyl silicate of 25mL is dissolved in the ethanol of 25mL, then adds the deionized water of 5mL, and then stirring velocity is to stir 30min under 300r/min, be i.e. glass-former solution; 2., prepare glass solution of additive: first sodium ethylate is dissolved in ethanol, the alcohol sodium alcohol solution that configuration 30mL mass concentration is 10%, then by the Ca (NO of 2.5g
3)
24H
2o is dissolved in the ethanol of 30mL, obtains Ca (NO
3)
24H
2o/ ethanolic soln, then by Ca (NO
3)
24H
2it is in 10% alcohol sodium alcohol solution that O/ ethanolic soln adds 30mL mass concentration, and stirs 30min under low whipping speed 300r/min, obtains glass solution of additive; 3., mix: the glass-former solution that 1. step 2 is obtained adds in the glass solution of additive that 2. step 2 obtain, then being 40 DEG C in temperature is that 300r/min speed is uniformly mixed 60min with stirring velocity, obtain glass-former/glass additives mixed thing, then add the ammoniacal liquor of mass concentration as 25% taking rate of addition as 1mL/min, the pH value of glass-former/glass additives mixed thing is adjusted to 9, obtains alkali glass colloidal sol; Three, prepare glass powder: alkali glass colloidal sol prepared by acid glass colloidal sol prepared by step 2 or step 2 is placed in drying baker, and be to be incubated 18h at 200 DEG C in temperature, after taking-up, put into planetary ball mill, taking grinding element and material ratio 5:1 and rotating speed ball milling 60min under 300r/min condition, then cross 1500 mesh sieves, obtain the glass powder of particle diameter≤10 μ m; Four, prepare metal powder/glass powder mixture: first prepare and in clean metal powder, add 1.5g glycerol to step 1, then low whipping speed is to mix 30min under 30r/min, add again the glass powder of 8g particle diameter≤10 μ m, and continue to mix 30min under 30r/min, obtain metal powder/glass powder mixture; Five, sintering: metal powder/glass powder mixture of first being prepared by step 4 is transferred in mould, is then sintering 1.5h under 700 DEG C and the mechanical compression power vacuum condition that is 40MPa in temperature, then cools to room temperature with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: it is that 10% dilute hydrochloric acid carries out acid corrosion that agglomerated material is put into massfraction, and till acid corrosion to the metal powder in agglomerated material is all removed, (the acid corrosion time is 120h), obtains porous glass material.
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, the porous glass material aperture approximately 5 μ m that as shown in Figure 1 prepared by this test, and porosity is about 70%.
Adopting universal electrical mechanical test machine to carry out compressive strength to the porous glass material of this test preparation and detect, is 1.9MPa by detecting known the compressive strength of testing the porous glass material of preparation.
Test two: a kind of preparation method of the porous glass material that uses glass powder, specifically complete according to the following steps: one, clean: the pure copper powder that by 35g particle diameter is first 1 μ m～5 μ m adds in dehydrated alcohol, and be under 30KHz, to carry out ultrasonic cleaning 2 times in frequency, the single ultrasonic cleaning time is 20min, then be dry 30min at 30 DEG C in temperature, obtain clean metal powder; 1., prepare glass-former solution two, prepare glass colloidal sol:: the methyl silicate of 25mL is dissolved in the ethanol of 25mL, then adds the deionized water of 5mL, and then stirring velocity is to stir 30min under 300r/min, be i.e. glass-former solution; 2., prepare glass solution of additive: first sodium ethylate is dissolved in ethanol, the alcohol sodium alcohol solution that configuration 30mL mass concentration is 10%, then calcium methylate is dissolved in methyl alcohol, the calcium methylate methanol solution that configuration 10mL mass concentration is 5%, then by aluminium secondary butylate (Al (C
4h
9)
3) be dissolved in ethanol, the aluminium secondary butylate ethanolic soln that configuration 10mL mass concentration is 5%, then the aluminium secondary butylate ethanolic soln that the calcium methylate methanol solution that the alcohol sodium alcohol solution that is 10% by 30mL mass concentration, 10mL mass concentration are 5% and 10mL mass concentration are 5% is admixed together, and stir 30min under low whipping speed 400r/min, obtain glass solution of additive; 3., mix: the glass-former solution that 1. step 2 is obtained adds in the glass solution of additive that 2. step 2 obtain, then being 40 DEG C in temperature is that 300r/min speed is uniformly mixed 60min with stirring velocity, obtain glass-former/glass additives mixed thing, then add the ammoniacal liquor of mass concentration as 25% taking rate of addition as 1mL/min, the pH value of glass-former/glass additives mixed thing is adjusted to 9, obtains alkali glass colloidal sol; Three, prepare glass powder: alkali glass colloidal sol prepared by acid glass colloidal sol prepared by step 2 or step 2 is placed in drying baker, and be to be incubated 18h at 200 DEG C in temperature, after taking-up, put into planetary ball mill, taking grinding element and material ratio 5:1 and rotating speed ball milling 60min under 300r/min condition, then cross 1500 mesh sieves, obtain the glass powder of particle diameter≤10 μ m; Four, prepare metal powder/glass powder mixture: first prepare and in clean metal powder, add 1.5g glycerol to step 1, then low whipping speed is to mix 30min under 30r/min, add again the glass powder of 8g particle diameter≤10 μ m, and continue to mix 30min under 30r/min, obtain metal powder/glass powder mixture; Five, sintering: metal powder/glass powder mixture of first being prepared by step 4 is transferred in mould, is then sintering 1.5h under 700 DEG C and the mechanical compression power vacuum condition that is 40MPa in temperature, then cools to room temperature with the furnace, obtains agglomerated material after moving back mould; Six, acid corrosion: it is that 10% dilute hydrochloric acid carries out acid corrosion that agglomerated material is put into massfraction, and till acid corrosion to the metal powder in agglomerated material is all removed, (the acid corrosion time is 120h), obtains porous glass material.
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, the porous glass material aperture approximately 5 μ m that as shown in Figure 2 prepared by this test, and porosity is about 72%.
Adopting universal electrical mechanical test machine to carry out compressive strength to the porous glass material of this test preparation and detect, is 1.8MPa by detecting known the compressive strength of testing the porous glass material of preparation.
Claims (6)
1. one kind uses the preparation method of the porous glass material of glass powder, it is characterized in that using porous glass material of glass powder and preparation method thereof to complete according to the following steps: one, clean: the metal powder that by particle diameter is first 1 μ m～150 μ m adds in dehydrated alcohol, and be under 24KHz～35KHz, to carry out ultrasonic cleaning 1～3 time in frequency, the single ultrasonic cleaning time is 10min～30min, then be dry 20min～40min at 20 DEG C～40 DEG C in temperature, obtain clean metal powder, 1., prepare glass-former solution two, prepare glass colloidal sol:: glass-former alkoxide is dissolved in organic solvent, then adds deionized water to mix, be i.e. glass-former solution, 2., prepare glass solution of additive: glass additive is dissolved in solvent, is glass solution of additive after mixing, 3., mix: glass-former solution is added in glass solution of additive, then being 15 DEG C～65 DEG C in temperature is that 180r/min～600r/min speed is uniformly mixed 10min～120min with stirring velocity, obtain glass-former/glass additives mixed thing, then add acidic aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min or add alkaline aqueous solution taking rate of addition as 0.5mL/min～1.5mL/min, if add acidic aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 2～6, obtain acid glass colloidal sol, if add alkaline aqueous solution, the pH value of glass-former/glass additives mixed thing is adjusted to 8～12, obtain alkali glass colloidal sol, three, prepare glass powder: alkali glass colloidal sol prepared by acid glass colloidal sol prepared by step 2 or step 2 is placed in drying baker, and be to be incubated 5h～30h at 100 DEG C～500 DEG C in temperature, after taking-up, put into planetary ball mill, taking grinding element and material ratio (5～6): 1 and rotating speed ball milling 30min～120min under 300r/min～500r/min condition, then cross 1500 mesh sieves, obtain the glass powder of particle diameter≤10 μ m, four, prepare metal powder/glass powder mixture: first in clean metal powder, add glycerol, then low whipping speed is to mix 20min～50min under 15r/min～60r/min, add again the glass powder of particle diameter≤10 μ m, and continue to mix 20min～90min under 15r/min～60r/min, obtain metal powder/glass powder mixture, five, sintering: first metal powder/glass powder mixture is transferred in mould, then be sintering 1h～4h under 600 DEG C～1200 DEG C and the mechanical compression power vacuum condition that is 20MPa～40MPa in temperature, then cool to room temperature with the furnace, obtain agglomerated material after moving back mould, six, acid corrosion: agglomerated material is put into acid and carry out acid corrosion, acid corrosion to the metal powder in agglomerated material obtains porous glass material till all removing, the glass-former alkoxide of step 2 described in 1. and the volume ratio of organic solvent are (0.5～2): 1, the glass-former alkoxide of step 2 described in 1. and the volume ratio of deionized water are (2～5): 1, the quality of glass additive and the volume ratio of solvent of step 2 described in is 2. (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, the glycerol adding described in step 4 and clean metal powder mass ratio are (0.01～0.05): 1, described in step 4, adding the glass powder of particle diameter≤10 μ m and clean metal powder mass ratio is (0.05～0.25): 1.
2. the preparation method of a kind of porous glass material that uses glass powder according to claim 1, is characterized in that the metal powder described in 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. the preparation method of a kind of porous glass material that uses glass powder according to claim 2, is characterized in that the organic solvent described in step 2 is 1. one or more the mixture in methyl alcohol, ethanol, ethylene glycol and propyl alcohol; The glass-former alkoxide of step 2 described in is 1. Si (OC
2h
5)
4or Si (OCH
3)
4.
4. the preparation method of a kind of porous glass material that uses glass powder according to claim 3, is characterized in that the solvent described in step 2 is 2. one or more the mixture in methyl alcohol, ethanol, ethylene glycol, propyl alcohol and deionized water; The glass additive of step 2 described in is 2. the one or more combination in glass additive alkoxide and inorganic salt; Wherein said glass additive alkoxide is M for meeting chemical formula
x+[(OR)
-]
xcompound in a kind of or wherein several 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.
5. according to the preparation method of a kind of porous glass material that uses glass powder described in claim 1,2,3 or 4, it is characterized in that the acidic aqueous solution described in step 2 is 3. that massfraction is the aqueous citric acid solution 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%; The alkaline aqueous solution of step 2 described in is 3. that massfraction is 5%～25% ammoniacal liquor.
6. the preparation method of a kind of porous glass material that uses glass powder according to claim 5, is characterized in that the acid described in 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.
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| CN104692667B (en) * | 2015-02-11 | 2017-03-01 | 陕西科技大学 | A kind of water purifier preparation method of cellular glass filter element |
| 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 |
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| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
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Non-Patent Citations (3)
| Title |
|---|
| JP平3-257029A 1991.11.15 |
| Shichao Zhao et al..Synthesis of mesoporous Si02 glass by a novel chemical method.《Materials Letters》.2007,第61卷(第3期), |
| Synthesis of mesoporous Si02 glass by a novel chemical method;Shichao Zhao et al.;《Materials Letters》;20070228;第61卷(第3期);897-899 * |
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