CN104703931A - Method for manufacturing foamed glass by using waste glass and foamed glass manufactured thereby - Google Patents
Method for manufacturing foamed glass by using waste glass and foamed glass manufactured thereby Download PDFInfo
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- CN104703931A CN104703931A CN201380052346.XA CN201380052346A CN104703931A CN 104703931 A CN104703931 A CN 104703931A CN 201380052346 A CN201380052346 A CN 201380052346A CN 104703931 A CN104703931 A CN 104703931A
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- glass
- foamed
- foamed glass
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- 239000011521 glass Substances 0.000 title claims abstract description 243
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title abstract 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 83
- 230000015572 biosynthetic process Effects 0.000 claims description 57
- 239000006063 cullet Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008447 perception Effects 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229940032158 sodium silicate Drugs 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019794 sodium silicate Nutrition 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- -1 such as Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/08—Other methods of shaping glass by foaming
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The present invention provides a method for manufacturing foamed glass having a low density and uniform pore distribution by using waste glass through a simple process, which does not require prior processes such as melting or hydrolyzing glass. The method for manufacturing the foamed glass according to one embodiment of the present invention, comprises the steps of: preparing the waste glass; adding a pore-forming agent and an oxygen supply agent for forming pores through a chemical reaction with the waste glass, and crushing the waste glass to form crushed glass; forming a glass molded product by molding the crushed glass; and forming the foamed glass comprising pores by heat-treating the glass molded product.
Description
Technical field
Technical conceive of the present invention relates to foamed glass, in detail, relates to the manufacture method of the foamed glass utilizing cullet.
Background technology
Foamed glass is lightweight, and remarkable performance can be played in fire-retardant, adiabatic, heat-resisting, sound-absorbing etc., industrially be used in the aspect being required there is water-repellancy, thermotolerance, weather resistance, particularly in works, buildings, be used in excellent heat-insulation material and sound absorbent material.
The manufacturing theory of foamed glass was disclosed for the later stage as far back as nineteen thirty.As one example, on the glass of specific composition together mixing as the reductive agent of carbon etc. and oxide compound, sulfonated bodies (sulfate) or the bubble formation agent of oxydised component containing other form, and it is pulverized, then, this pulverized mixture is put on certain container or framework, be softened or melting temperature under it burnt till and formed.
In such heat treatment process, redox reaction occurs, its result between carbon and azochlorosulfonate acid compound (or oxygenant, or the oxide compound of glass), melten glass can contain SO
2, CO
2, N
2, H
2s or other gas, by containing this gas, form the material of following a kind of structure, this structure is the structure having low density, heat trnasfer and radiation are become to obstruction, forms glass gas thus.Its result, when obtaining optimal result, above-mentioned glass structure is lockedin air space by what comprise that water, water vapour or other liquids and gases etc. can not infiltrate.
About by this manufacturing theory manufactured go out the manufacturing process of foamed glass, disclosed a lot of result of study and Patents.Such as, carrying out business-like foamed glass to manufacture pittsburgh,U.S.A healthy and free from worry (PittsburgCorning) company, the foamed glass production of raw material for use glass of specific composition should be manufactured once.For this reason, in common glass manufacture material composition, in order to foamed glass can be formed, add Na
2sO
4, CaCO
3, MgCO
3, Na
2o, As
2o
3deng composition, and pass through the melting process at 1300 DEG C to 1600 DEG C, form the foamed glass production of raw material for use glass that can manufacture foamed glass.In addition, the glass manufactured like this is pulverized, and interpolation fully mixes as after the carbon of frothing aid, wherein, carry out reacting as the carbon of frothing aid and other compositions and produce the gas directly playing whipping agent effect, then, the foamed glass production of raw material for use glass powder this being carried out mix is put into certain container and carry out preheating to it at 400 DEG C to 650 DEG C, and through foaming at 800 DEG C to 900 DEG C, then through the cooling for stabilization, the heat treatment processes such as annealing, the material of such acquisition is cut off with a certain size and packs laggard marketing and sells.
But, this operation in manufacture foamed glass production of raw material for use glass process as described above its thermal treatment temp reach 1300 DEG C to 1600 DEG C, therefore by lot of energy, and need facility investment thereupon and overhead charges, thus, the productive expense of foamed glass production of raw material for use glass can occupy the over half of foamed glass production cost.
In addition, when the foamed glass manufactured by cutting off with a certain size, the generation (even reaching 20wt% time many) of the residual foamed glass of incidental a lot of amount can become another major reason that cannot reduce glass block production cost.
Because of above-mentioned reason, after manufacturing works' startup of the foamed glass of this pittsburgh,U.S.A Corning Incorporated so far, existing many patents of being suggested about the improvement of foamed glass manufacturing process and result of study, the focus major part of its object is all the operation without high energy before foaming step.Therefore, before foaming step, the operation reducing high energy is necessary.
Summary of the invention
Technical task
The technical task that technical conceive of the present invention will realize is, utilize cullet, do not need the melting of glass, hydrolyzable or prior operation in addition, utilize simple operation, the manufacture method of the foamed glass with low density and uniform bubble distribution is provided.
The technical task that technical conceive of the present invention will realize is, provides a kind of and utilizes the manufacture method of above-mentioned foamed glass and the foamed glass formed.
But this technical task is illustrative, technical conceive of the present invention is not limited to this.
The means of technical solution problem
For realizing the manufacture method of the foamed glass according to the technology of the present invention design of above-mentioned technical task, comprise the following steps: prepare cullet; Add in described cullet and mutually carry out chemical reaction and the bubble formation agent and the oxygenate that form bubble, and described cullet is pulverized and forms glass powder and mince; Described glass powder is minced and carries out shaping and form glass ware forming thing; Described glass ware forming thing is heat-treated and forms the foamed glass comprising bubble.
In one embodiment of the invention, form the step that described glass powder minces and may further include following steps: first time is carried out to described cullet and pulverizes and form first time glass powder and mince; Described first time glass powder add described bubble formation agent and described oxygenate in mincing; The described first time glass powder being added described bubble formation agent and described oxygenate is minced and carries out second time and pulverize and form second time glass powder and mince.
In one embodiment of the invention, form described first time step of mincing of glass powder can utilize dry method to carry out.
In one embodiment of the invention, form the step that described second time glass powder minces and can utilize wet method to carry out, wherein use at least one in distilled water, ethanol, methyl alcohol and acetone as solvent.
In one embodiment of the invention, after carrying out being formed the step that described second time glass powder minces, may further include minces to described second time glass powder carries out dry step.
In one embodiment of the invention, after forming the step that minces of described glass powder, may further include and described glass powder is minced the step of screening.
In one embodiment of the invention, described glass ware forming thing to be heat-treated and the step forming the foamed glass comprising bubble can comprise the following steps: described glass ware forming thing is formed glass basis by burning till; The described bubble formation agent and the described oxygenate that are included in described glass ware forming thing mutually carry out chemical reaction and form described bubble in described glass basiss.
In one embodiment of the invention, described glass ware forming thing to be heat-treated and the step forming the foamed glass comprising bubble can be carried out in the temperature range of 900 DEG C to 1100 DEG C.
In one embodiment of the invention, described cullet can comprise boroaluminosilicate (boroalumino-silicate).
In one embodiment of the invention, described bubble formation agent can comprise the material forming the gas of filling described bubble.
In one embodiment of the invention, described bubble formation agent can comprise aln precipitation (AlN), silicon nitride (Si
3n
4), at least one in boron nitride (BN), titanium nitride (TiN) and silicon carbide (SiC).
In one embodiment of the invention, described oxygenate can comprise for carrying out the oxygen of chemical reaction with described bubble formation agent.
In one embodiment of the invention, described oxygenate can comprise cobalt/cobalt oxide (Co
3o
4), calcium carbonated (CaCO
3), barium oxide (V
2o
5), arsenic oxide (As
2o
5), sb oxide (Sb
2o
5), ferriferous oxide (Fe
2o
3) and sodium azochlorosulfonate acid compound (Na
2sO
4) at least one.
In one embodiment of the invention, in the step that the described glass powder of formation minces, the described glass powder with 1 μm of powder shape to 10 μm of diameters can be formed and mince.
In one embodiment of the invention, included in described foamed glass described bubble can comprise the mixed gas of nitrogen, carbon dioxide or these gases.
For realizing the foamed glass according to the technology of the present invention design of above-mentioned technical task, the manufacture method of above-mentioned foamed glass can be utilized and manufacture.
In one embodiment of the invention, described foamed glass can have density is 180kg/m
3to 200kg/m
3, void content is 85% to 95%, and ultimate compression strength is 1.0MPa to 2.5MPa, at 25 DEG C, have 0.04Wm
-1k
-1to 0.125Wm
-1k
-1the characteristic of thermal conductivity.
The effect of invention
According to the foamed glass manufacture method of the technology of the present invention design, owing to adding bubble formation agent and oxygenate and by based on the heat treated formation foamed glass that burns till and foam in pulverized cullet, therefore can produce the simple and Working Procedure Controlling of operation easily, there is uniform air hole structure, foamed glass that aesthetical perception is excellent.
In addition, do not utilize mould profile according to the manufacture method of the foamed glass of the technology of the present invention design and utilize common fashion of extrusion to form glass ware forming thing and foamed glass, therefore operation is simple, and Working Procedure Controlling becomes easy.
The foamed glass formed by the manufacture method of foamed glass conceived according to the technology of the present invention has following characteristic: its lightweight, easy process, can not be burnt, do not produce toxic gas by fire, therefore can be used on the product of multiple building, civil engineering work, relevant contexts.
Effect of the present invention as above records in the mode of illustrative, and scope of the present invention is not limited to these effects.
Accompanying drawing explanation
Fig. 1 represents the schema according to the manufacture method S1 of the foamed glass of one embodiment of the invention;
Fig. 2 is the photo of the outward appearance of the foamed glass representing the experimental example 1 to 4 formed by the manufacture method of the foamed glass according to one embodiment of the invention;
Fig. 3 is the electron scanning micrograph of the microtexture of the foamed glass representing the experimental example 1 to 4 formed by the manufacture method of the foamed glass according to one embodiment of the invention.
For the preferred implementation carried out an invention
Below, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.Embodiments of the invention provide to absolutely prove the present invention to those skilled in the art, and following examples can be deformed into other form various, and technical conceive of the present invention is not limited to following examples.On the contrary, following examples are in order to enrich further and improve the present invention, fully transmit technical conceive of the present invention and provide to those skilled in the art.As used in this specification, term "and/or" to be included in enumerated project any one or more than one all combinations.Same-sign refers to identical element all the time, and various key element in the accompanying drawings and region are that outline represents.Therefore, technical conceive of the present invention is not limited to relative size described in accompanying drawing or spacing.
Fig. 1 represents the schema according to the manufacture method S1 of the foamed glass of one embodiment of the invention.
With reference to Fig. 1, foamed glass manufacture method comprises: the step S10 preparing cullet; The step S20 that first time pulverizes and formation first time glass powder minces is carried out to described cullet; Described first time glass powder add in mincing and mutually carry out chemical reaction and form the bubble formation agent of bubble and the step S30 of oxygenate; The described first time glass powder being added with described bubble formation agent and described oxygenate is minced and carries out second time and pulverize and form the step S40 that second time glass powder minces; Described second time glass powder is minced and carries out dry step S50; Dried described second time glass powder is minced and screens the step S60 of (sieving); Described second time glass powder is minced and carries out shaping and form the step S70 of glass ware forming thing; Described glass ware forming thing is heat-treated and forms the step S80 of the foamed glass comprising bubble.
In the step S10 preparing cullet, prepare the cullet as foamed glass raw material.Described cullet such as can comprise boroaluminosilicate (boroalumino-silicate), or comprises sodium silicate (sodium-silicate), or comprises these mixture.Described cullet can comprise LCD (liquid crystal dusplay) glass, PDP (Plasma display panel) glass, OLED (organic light emitting device) glass or picture tube glass etc.Table 1 represents the composition that can be used as the LCD glass of cullet.But the kind of such cullet and composition are illustrative, and technical conceive of the present invention is not limited to this.
Table 1
| Material | B 2O 3 | Al 2O 3 | SiO 2 | CaO | SrO | MgO | Cr 2O 3 | Fe 2O 3 |
| ％ | 10.6 | 17.8 | 58 | 8.76 | 1.05 | 1.75 | 0.54 | 0.898 |
Being formed carrying out described cullet first time to pulverize in the step S20 that glass powder minces for the first time, utilizing disc flour mill (disk mill) or ball mill (ball mill) etc. to carry out first time to prepared described cullet and pulverizing.Described first time pulverizes and dry method can be utilized to carry out.Described first time, the size of powder particles that minces of glass powder can be 10 μm to 1000 μm.Described first time pulverizes and method for recycling can be utilized repeatedly to carry out.Described first pulverising step is optionally, can omit.
Add in the step S30 of bubble formation agent and oxygenate in described first time crushed material, add and mix the described bubble formation agent that can form bubble and the oxygenate that can be provided for carrying out with described bubble formation agent chemical reaction for forming described bubble.Described bubble formation agent and described oxygenate can have the almost identical size of powder particles that to mince with described first time glass powder, or, size of powder particles less compared with mincing with described first time glass powder can be had.Described first time crushed material, described bubble formation agent, the preferred Homogeneous phase mixing of described oxygenate.
Described bubble formation agent can be added to 5.0wt% scope with about 1.0wt% (weight ratio) relative to described mixture.In addition, described oxygenate can add to 5.0wt% scope with about 1.0wt% (weight ratio) relative to described mixture.
Described bubble formation agent can comprise the material forming the gas of filling described bubble, such as, can comprise nitride or carbide, such as, can comprise aln precipitation (AlN), silicon nitride (Si
3n
4), at least one in boron nitride (BN), titanium nitride (TiN) and silicon carbide (SiC).But this is illustrative, design of the present invention is not limited to the kind of this bubble formation agent.
Described oxygenate can comprise for carrying out the oxygen of chemical reaction with described bubble formation agent, such as, and cobalt/cobalt oxide (Co
3o
4), calcium carbonated (CaCO
3), barium oxide (V
2o
5), arsenic oxide (As
2o
5), sb oxide (Sb
2o
5), ferriferous oxide (Fe
2o
3) and sodium azochlorosulfonate acid compound (Na
2sO
4) at least one.But this is illustrative, design of the present invention is not limited to the kind of this oxygenate.
Described bubble formation agent and described oxygenate can form bubble by the reaction as following chemical formula 1.In chemical formula 1, citing represents as described bubble formation agent use AlN, uses Fe as oxygenate
2o
3.
Chemical formula 1
2AlN+Fe
2O
3→Al
2O
3+2Fe+N
2↑
As shown in above-mentioned chemical formula 1, described bubble formation agent and described oxygenate is added, when heating in follow-up heat treatment step in described cullet, described bubble formation agent and described oxygenate react, form nitrogen, described nitrogen is caught in glass and forms bubble, can form foamed glass thus.
When described bubble formation agent comprises nitride, the nitrogen be included in described nitride can be used as nitrogen and forms bubble.When described bubble formation agent comprises carbide, the carbon be included in described carbide can be used as carbon dioxide and forms bubble.
Carry out second time and pulverize and formed in the step S40 that second time glass powder minces mincing to the described first time glass powder being added with described bubble formation agent and described oxygenate, utilize disc flour mill (disk mill) or ball mill (ball mill) etc. to carry out second time pulverizing.Described second time is pulverized and the wet method using at least one in such as distilled water, ethanol, methyl alcohol and acetone uses as solvent can be utilized to carry out.Described solvent is illustrative, and design of the present invention is not limited to the kind of this solvent.
The size of powder particles that described second time glass powder minces is more fine more preferred.Such as, consider to devote the expense economically manufacturing the powder that described second time glass powder minces, the size of powder particles (diameter) that described second time glass powder minces can be 1 μm to 10 μm.In addition, during mincing to described first time glass powder and pulverizing, together can pulverize described bubble formation agent and described oxygenate, therefore, described second time glass powder minces and may further include described bubble formation agent and described oxygenate.The size of powder particles that described second time glass powder minces is preferably almost identical with described oxygenate size with described bubble formation agent.In order to ensure the homogeneity of the size of powder particles that described second time glass powder minces, be necessary to pulverize within the sufficient time, such as, can abrasive dust two hours degree further after pulverizing.
Carry out in dry step S50 mincing to described second time glass powder, described second time glass powder is minced and carries out drying and remove described solvent.Described drying can be carried out in normal temperature to the temperature range of about 200 DEG C, and can carry out 1 little of 24 hours.
In the step S60 screened being minced by the described second time glass powder of described drying, utilizing sieve (sieve) to be minced by described dried described second time glass powder and being divided into large powder and fines.Described sieve can be selected according to required fines size, such as, can utilize the sieve of 200 orders (mesh).Screened large powder can be put to first time pulverising step or second time pulverising step in, described fines can be put to the step of follow-up formation forming composition.Described screening step S60 is optionally, can be omitted.
Carry out shaping and formed in the step S70 of glass ware forming thing mincing to described second time glass powder, described second time glass powder is minced and loads forming mould and carry out pressurizeing and be shaped to desired shape.The step S70 of described formation glass ware forming thing can utilize extrusion process etc., such as can utilize single shaft extrusion process or etc. direction extruding (three axles extruding) method.The step S70 of described formation glass ware forming thing can carry out in the temperature range of normal temperature to about 300 DEG C.
Being formed in the step S80 of foamed glass heat-treating described glass ware forming thing, described glass ware forming thing being heated and burns till (firing) and foaming, to form foamed glass.The step S80 of described formation foamed glass such as can carry out in the temperature range of 900 DEG C to 1100 DEG C, such as, can carry out to the temperature range of 1050 DEG C at about 950 DEG C.
In the step S80 forming foamed glass, be included in glass ingredient in described glass ware forming thing to be combined with each other formation glass basis by (firing) process of burning till, and the described bubble formation agent be included in described glass ware forming thing and described oxygenate carry out chemical reaction as shown in above-mentioned chemical formula 1 and as described in formed in glass basis as described in bubble.Thereby, it is possible to be formed in the foamed glass being distributed with described bubble in described glass basis.Described bubble can comprise multiple gases according to described bubble formation agent, such as, can comprise nitrogen, carbon dioxide or these mixed gas.
As a kind of scheme, tinting material can be added in described second time glass powder minces, and carry out described step S40 to step S80 formation colored hair bulb glass.Described tinting material can use many kinds of substance according to required color, such as, can use cobalt/cobalt oxide (Co
3o
4) or Mn oxide (MnO
3) etc.
According to the manufacture method of the foamed glass of technical conceive of the present invention, easily can be formed and there is uniform fine pores structure, foamed glass that aesthetical perception is excellent.Such as, the foamed glass formed by the manufacture method of the foamed glass of technical conceive according to the present invention such as can present following characteristic: density is about 180kg/m
3to about 200kg/m
3, void content is about 85% to 95%, and ultimate compression strength is about 1.0MPa to 2.5MPa, and breaking tenacity is about 1.5MPa to 4.0MPa, has and be about 0.04Wm at about 25 DEG C
-1k
-1to 0.125Wm
-1k
-1thermal conductivity.Described foamed glass such as can present following characteristic: density is about 194kg/m
3, void content is about 92%, and ultimate compression strength is about 1.845MPa, and breaking tenacity is about 2.142MPa, has and be about 0.047Wm at about 25 DEG C
-1k
-1thermal conductivity.
experimental example: the manufacture utilizing the foamed glass of cullet
Prepared to have the cullet that borosilicate (borosilicate) forms, the composition of described cullet has the composition of above-mentioned table 1.
Then, utilize disc flour mill to carry out first time to described cullet and pulverize, form glass powder for the first time thus and mince.Described first time pulverizes and utilizes method for recycling to carry out, and its recirculation proceeds to three times.Described first time, glass powder minced the average powder size having and be about 120 μm.
Then, described first time glass powder with the addition of bubble formation agent and oxygenate in mincing.The described bubble formation agent added and described oxygenate as shown in table 2.
Table 2
| Experimental example 1 | Experimental example 2 | Experimental example 3 | Experimental example 4 | |
| Bubble formation agent | AlN | AlN | AlN | AlN |
| Oxygenate | V 2O 5 | Co 3O 4 | CaCO 3 | Fe 2O 3 |
Then, utilize wet method to mince to the described first time glass powder being added with described bubble formation agent and described oxygenate and carry out second time and pulverize, form second time glass powder thus and mince.Described second time is pulverized and is utilized as solvent by the mixing solutions of distilled water and ethanol, and make use of the planetary pulverizing mill (planetary mill) rotated with 300rpm speed and carried out two hours.Described second time glass powder minces the average powder size having and be about 120 μm.
Then, utilize baking box to mince to described second time glass powder at about 60 DEG C and carry out drying in 24 hours.
Then, utilize 200 mesh sieve to mince to described dry second time glass powder to screen.By described screening, described second time glass powder is minced and is separated into large powder and fines.
Then, the second time glass powder of described fines is minced and loads in forming mould, utilize pressing method to carry out pressurizeing and manufacturing glass ware forming thing.
Then, electric furnace is utilized to burn till described glass ware forming thing and produced foamed glass through foamed process.In this step, heat-up rate is about 3 DEG C/min, and temperature is about adjusted to 950 DEG C, and the time has carried out two hours.
Fig. 2 is the photo of the outward appearance of the foamed glass representing the experimental example 1 to 4 formed by the manufacture method of the foamed glass according to one embodiment of the invention.
With reference to Fig. 2, the foamed glass confirming experimental example 1 to 4 has the outward appearance with aesthetical perception characteristic.The color of described foamed glass presents different colors according to the kind of added oxygenate.Described foamed glass presents characteristic as shown in table 3.
Table 3
Simple glass density is about 2520kg/m
3, therefore, the foamed glass according to the technology of the present invention design has low-down low density characteristic compared with simple glass.In addition, the ultimate compression strength of simple glass is about 170MPa, therefore, has the high compressive strength characteristic of more than about 10 times according to the foamed glass of the technology of the present invention design compared with simple glass.In addition, the thermal conductivity of simple glass is about 0.893Wm
-1k
-1, therefore, the foamed glass according to the technology of the present invention design has low-down thermal conductivity characteristics compared with simple glass.
Fig. 3 is the electron scanning micrograph of the microtexture of the foamed glass representing the experimental example 1 to 4 formed by the manufacture method of the foamed glass according to one embodiment of the invention.
Known with reference to Fig. 3, in foamed glass, be distributed with bubble.Described bubble has uniform size and uniform distribution, and is distributed in described foamed glass.V is used as oxygenate
2o
5the Air Bubble Size of experimental example 1 relatively large, use CaCO as oxygenate
3the Air Bubble Size of experimental example 3 relatively little.In addition, Fe is used as oxygenate
2o
3the size distribution of bubble of experimental example 4 the most even.Above-mentioned experimental example, because employ AlN as bubble formation agent, therefore can capture nitrogen in measurable bubble.
According to the foamed glass manufacture method of the technology of the present invention design, owing to adding bubble formation agent and oxygenate and by based on the heat treated formation foamed glass that burns till and foam in pulverized cullet, therefore can produce the simple and Working Procedure Controlling of operation easily, there is uniform air hole structure, foamed glass that aesthetical perception is excellent.
In addition, do not utilize mould profile according to the manufacture method of the foamed glass of the technology of the present invention design and utilize common fashion of extrusion to form glass ware forming thing and foamed glass, therefore operation is simple, and Working Procedure Controlling becomes easy.
The foamed glass formed by the manufacture method of foamed glass conceived according to the technology of the present invention has following characteristic: its lightweight, easy process, can not be burnt, do not produce toxic gas by fire, therefore can be used on the product of multiple building, civil engineering work, relevant contexts.
Technical conceive of the present invention as above is not limited to the above embodiments and accompanying drawing, concerning technical conceive those of ordinary skill in the field of the present invention, it is apparent for can carrying out multiple replacement, distortion and change in the scope not exceeding the present invention's design.
Claims (17)
1. a manufacture method for foamed glass, comprises the following steps:
Prepare cullet;
Add in described cullet and mutually carry out chemical reaction and the bubble formation agent and the oxygenate that form bubble, and described cullet is pulverized and forms glass powder and mince;
Described glass powder is minced and carries out shaping and form glass ware forming thing;
Described glass ware forming thing is heat-treated and forms the foamed glass comprising bubble.
2. the manufacture method of foamed glass according to claim 1, is characterized in that, forms the step that described glass powder minces further comprising the steps:
First time pulverizing is carried out to described cullet and formation first time glass powder minces;
Described first time glass powder add described bubble formation agent and described oxygenate in mincing;
The described first time glass powder being added with described bubble formation agent and described oxygenate is minced and carries out second time and pulverize and form second time glass powder and mince.
3. the manufacture method of foamed glass according to claim 2, is characterized in that, forming described first time step of mincing of glass powder is utilize dry method to carry out.
4. the manufacture method of foamed glass according to claim 2, is characterized in that, forming the step that described second time glass powder minces is utilize wet method to carry out, and wherein uses at least one in distilled water, ethanol, methyl alcohol and acetone as solvent.
5. the manufacture method of foamed glass according to claim 2, is characterized in that, after carrying out being formed the step that described second time glass powder minces, comprising further minces to described second time glass powder carries out dry step.
6. the manufacture method of foamed glass according to claim 1, is characterized in that, after forming the step that minces of described glass powder, comprising further minces to described glass powder screens the step of (sieving).
7. the manufacture method of foamed glass according to claim 1, is characterized in that, heat-treats and the step forming the foamed glass comprising bubble comprises the following steps to described glass ware forming thing:
Described glass ware forming thing is burnt till (firing) and is formed glass basis;
The described bubble formation agent and the described oxygenate that are included in described glass ware forming thing mutually carry out chemical reaction and form described bubble in described glass basiss.
8. the manufacture method of foamed glass according to claim 1, is characterized in that, heat-treats and the step forming the foamed glass comprising bubble is carried out in the temperature range of 900 DEG C to 1100 DEG C to described glass ware forming thing.
9. the manufacture method of foamed glass according to claim 1, is characterized in that, described cullet comprises boroaluminosilicate (boroalumino-silicate).
10. the manufacture method of foamed glass according to claim 1, is characterized in that, described bubble formation agent comprises the material forming the gas of filling described bubble.
The manufacture method of 11. foamed glass according to claim 1, is characterized in that, described bubble formation agent comprises aln precipitation (AlN), silicon nitride (Si
3n
4), at least one in boron nitride (BN), titanium nitride (TiN) and silicon carbide (SiC).
The manufacture method of 12. foamed glass according to claim 1, is characterized in that, described oxygenate comprises for carrying out the oxygen of chemical reaction with described bubble formation agent.
The manufacture method of 13. foamed glass according to claim 1, is characterized in that, described oxygenate comprises cobalt/cobalt oxide (Co
3o
4), calcium carbonated (CaCO
3), barium oxide (V
2o
5), arsenic oxide (As
2o
5), sb oxide (Sb
2o
5), ferriferous oxide (Fe
2o
3) and sodium azochlorosulfonate acid compound (Na
2sO
4) at least one.
The manufacture method of 14. foamed glass according to claim 1, is characterized in that, in the step that the described glass powder of formation minces, forms the described glass powder with 1 μm of powder shape to 10 μm of diameters and minces.
The manufacture method of 15. foamed glass according to claim 1, is characterized in that, described bubble included in described foamed glass comprises the mixed gas of nitrogen, carbon dioxide or these gases.
16. 1 kinds of foamed glass, utilize the manufacture method of the foamed glass according to any one of claim 1 to 15 and are formed.
17. foamed glass according to claim 16, is characterized in that, its density of described foamed glass is 180kg/m
3to 200kg/m
3, void content is 85% to 95%, and ultimate compression strength is 1.0MPa to 2.5MPa, at 25 DEG C, have 0.04Wm
-1k
-1to 0.125Wm
-1k
-1thermal conductivity.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0111301 | 2012-10-08 | ||
| KR1020120111301A KR101437826B1 (en) | 2012-10-08 | 2012-10-08 | Method for manufacturing foam glass using waste glass and foam glass formed by the same |
| PCT/KR2013/008975 WO2014058204A1 (en) | 2012-10-08 | 2013-10-08 | Method for manufacturing foamed glass by using waste glass and foamed glass manufactured thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104703931A true CN104703931A (en) | 2015-06-10 |
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|---|---|---|---|
| CN201380052346.XA Pending CN104703931A (en) | 2012-10-08 | 2013-10-08 | Method for manufacturing foamed glass by using waste glass and foamed glass manufactured thereby |
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| Country | Link |
|---|---|
| KR (1) | KR101437826B1 (en) |
| CN (1) | CN104703931A (en) |
| WO (1) | WO2014058204A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106630649A (en) * | 2016-12-29 | 2017-05-10 | 扬州大学 | Method for preparing foam glass with high foaming rate by utilizing lead-free high-barium abandoned lamp tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2966044T3 (en) * | 2014-07-07 | 2019-01-02 | As Graasten Teglværk | METHOD FOR MAKING FOAM GLASS |
| WO2019065489A1 (en) | 2017-09-27 | 2019-04-04 | 株式会社鳥取再資源化研究所 | Method for recycling solar cell module glass |
| HUP2200391A1 (en) * | 2022-09-30 | 2024-04-28 | Daniella Ipari Park Kft | Process for red mud oxidising agent application in foam glass formulation to improve the foaming of foam glass |
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| JPH11343128A (en) * | 1998-05-29 | 1999-12-14 | Hitachi Zosen Corp | Glass expanded body and its production |
| CN101113077A (en) * | 2007-07-20 | 2008-01-30 | 内蒙古自治区建筑材料工业科学研究设计院 | Preparation method of foam glass |
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| JP4203946B2 (en) | 2003-01-10 | 2009-01-07 | 積水ハウス株式会社 | Waste glass material recycling method and glass cullet produced by the method |
| JP4494311B2 (en) | 2004-08-13 | 2010-06-30 | 改造 古川 | Glass foam |
-
2012
- 2012-10-08 KR KR1020120111301A patent/KR101437826B1/en active IP Right Grant
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| JPH11343128A (en) * | 1998-05-29 | 1999-12-14 | Hitachi Zosen Corp | Glass expanded body and its production |
| CN101113077A (en) * | 2007-07-20 | 2008-01-30 | 内蒙古自治区建筑材料工业科学研究设计院 | Preparation method of foam glass |
| KR20110128541A (en) * | 2010-05-24 | 2011-11-30 | 강릉원주대학교산학협력단 | Method for manufacturing foamed glass from waste glass |
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| CN106630649A (en) * | 2016-12-29 | 2017-05-10 | 扬州大学 | Method for preparing foam glass with high foaming rate by utilizing lead-free high-barium abandoned lamp tube |
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|---|---|
| KR20140048361A (en) | 2014-04-24 |
| KR101437826B1 (en) | 2014-09-15 |
| WO2014058204A1 (en) | 2014-04-17 |
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