CN104066692A - Preparation method of foam glass using waste glass, and prediction method of foaming range of glass using dilatometer - Google Patents

Preparation method of foam glass using waste glass, and prediction method of foaming range of glass using dilatometer Download PDF

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Publication number
CN104066692A
CN104066692A CN201180076280.9A CN201180076280A CN104066692A CN 104066692 A CN104066692 A CN 104066692A CN 201180076280 A CN201180076280 A CN 201180076280A CN 104066692 A CN104066692 A CN 104066692A
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glass
foaming
temperature
foam
cullet
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CN104066692B (en
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朴商晔
郑俊基
方喜坤
金成振
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KANGNUNG WONJU NAT UNIVERSITY
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KANGNUNG WONJU NAT UNIVERSITY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

According to one aspect of the present invention, provided is a preparation method of foam glass using waste glass comprising the steps of: pressurizing a waste glass powder comprising sodium silicate or boroaluminosilicate without adding a foaming agent in a mold to prepare a molded product; and firing and foaming the molded product at 600-1000 DEG C, wherein a preparation method of the waste glass powder comprises the step of pulverizing waste glass comprising sodium silicate or boroaluminosilicate by wet pulverization.

Description

Use cullet to manufacture the method for multicellular glass and use the method for the foaming scope of dilatometer prediction glass
Technical field
The present invention relates to manufacture the method for multicellular glass and the method for prediction foaming scope, relate more particularly to wherein use cullet in the situation that not adding whipping agent (or bubble formation agent (bubble-formingagent)), to manufacture the method for the multicellular glass manufacture method of multicellular glass and the foaming scope of use dilatometer prediction glass by grinding and heat treating method as raw material.
Background technology
Multicellular glass is for needing the application of industrial water-repellancy, thermotolerance and weather resistance, and this is because it is in lightweight excellent fire prevention, insulation, the heat-resisting and sound absorption qualities of demonstrating simultaneously.Particularly, multicellular glass is used as excellent lagging material and sound absorbent material in structure or building.
The manufacture principle of multicellular glass was proposed in late 1930s.For example, the whipping agent of reductive agent (as carbon) and the oxidation component that contains oxide compound, vitriol or other type is mixed with the glass with specific composition, and pulverize the mixture so obtaining.Then, the mixture after pulverizing is placed in predetermined container or mould, thereby calcined before softening or melting.
In heat treatment process, between carbon and oxysulfide (or the oxide compound of glass or oxygenant), there is oxidation-reduction reaction.As a result, the glass of melting can contain SO 2, CO 2, N 2, H 2s or other gas.This can produce and form the material that has low density and thermal conduction and thermal radiation are had to the structure of tolerance, and this can form free gas.As a result, in the time obtaining optimum, the structure of glass can have blind hole, and water, water vapor or other liquid or gas can not infiltrate in this hole.
Numerous results of study and the Patents of the manufacture method of the foam-glass block that the above manufacture principle of having given chapter and verse is manufactured.In order to manufacture the business-like multicellular glass by Pittsburg Corning of the United States of America, must first prepare the frit for the manufacture of multicellular glass with specific composition.For this reason, for the preparation of the frit of manufacturing multicellular glass, described frit can pass through various components (as Na 2sO 4, CaCO 3, MgCO 3, Na 2o and As 2o 3) add to for the manufacture of in the typical feedstock composition of glass and implement melting method and manufacture multicellular glass in the temperature range of 1300 DEG C to 1600 DEG C.Pulverize so glass of preparation, carbon is added to wherein and fully and mixed as forming auxiliary agent (described formation auxiliary agent has produced by serving as the gas of direct whipping agent with other component reaction).Then, mixed frit powder for the manufacture of multicellular glass is placed in predetermined container, in the temperature range of 400 DEG C to 650 DEG C, carry out preheating, make it in the temperature range of 800 DEG C to 900 DEG C, stand foaming process, then stand heat treating method (as the cooling and Slow cooling for stable).The product so obtaining is cut into predetermined size and packs with for sale.
But, in the method, because the thermal treatment temps of 1300 DEG C to 1600 DEG C as above are necessary in the method for the frit for the preparation of manufacture multicellular glass, so need a large amount of energy.Therefore, the investment of equipment and overhead charges are necessary, thereby, may account for the half that exceedes of multicellular glass production cost for the manufacture of the production cost of the frit of multicellular glass.
In the manufacture of multicellular glass, the foaming scope of the glass that calculates to a nicety is as far as possible very important.Numerous results of study and the Patents of the manufacture method of the foam-glass block that the above manufacture principle of having given chapter and verse is manufactured.But, unimportant for the research of the generation scope of multicellular glass.
Conventionally, used hot-stage microscope in macroscopic view, to carry out the accurately predicting experiment of the generation scope of multicellular glass by realtime graphic.But, the foaming scope of this glass that cannot calculate to a nicety, unit of measure also may be limited to only millimeter (mm) unit.
Summary of the invention
technical problem
The invention provides in the situation that not using whipping agent, by with cullet simultaneously without glass melting, hydrolysis or there is the method for colourless or coloured multicellular glass of even pore distribution and effective efficiency for the preparation of any other pre-treatment manufacture of specific group compound.
The present invention also provides use dilatometer according to the method for the foaming scope of various measurands (as temperature range, temperature rise rate, hold-time and rate of cooling) accurately predicting glass.
technical scheme
According to an aspect of the present invention, provide and used cullet to manufacture the method for multicellular glass, having comprised: the cullet powder by suppressing in shaping dies in the situation that not adding whipping agent with water glass or boroaluminosilicate component has been prepared moulded parts; With the temperature range at 600 DEG C to 1,000 DEG C, moulded parts is calcined and made its foaming, wherein, by adopting wet milling process to grind the cullet with water glass or boroaluminosilicate component, prepare cullet powder.
In this case, can be by least one or the multiple solvent as described wet milling process that are selected from water, ethanol, methyl alcohol and acetone.
In addition, described method is dry grinded to the described cullet with water glass or boroaluminosilicate component before can also being included in and grinding by wet milling process.
The size of cullet powder can be 1 μ m to 10 μ m.
Can add to metal oxide as tinting material in described cullet powder, described metal oxide can be cobalt/cobalt oxide (Co 3o 4) or Mn oxide (MnO 3) in any one or multiple.
Can or before grinding by wet milling process, metal oxide be added in cullet powder before calcining and foaming.
According to a further aspect in the invention, the method of the foaming scope of prediction glass is provided, comprise use do not foam precursor according to the change of shape curve of temperature with the do not foam foaming scope of precursor of prediction, the described change of shape curve according to temperature adopts dilatometer to measure.
Can obtain by following steps described according to the change of shape curve of temperature: the precursor that will not foam is introduced in dilatometer; With when the foaming starting temperature of the precursor that do not foam described in the described precursor that do not foam is heated above, length or the volume change of the precursor that do not foam described in measurement.
Can be under 200cN or condition still less, to obtain described change of shape curve in vertical load or impellent.
Can by change measure in temperature range, temperature rise rate, rate of cooling or temperature hold-time any one or multiple, obtain described change of shape curve.For example, described measurement temperature range can change in the scope of room temperature to 1400 DEG C, described temperature rise rate can change in the scope of 0.1 DEG C/min to 50 DEG C/min, described rate of cooling can change in the scope of 0.1 DEG C/min to 50 DEG C/min, and the described hold-time can change in 24 hours or scope still less.
The precursor that do not foam can be powder type or the piece material form with predetermined shape.
beneficial effect
In the present invention, owing to using discarded cullet to manufacture multicellular glass in the situation that not adding whipping agent under process control, so can simplify this process.Therefore, not only can contribute to process control, but also can manufacture the multicellular glass with even pore structure and good aesthetic.Therefore the multicellular glass of, so manufacturing can be in the relevant product of various Architecture and Environments.
In addition, in the present invention, owing to becoming possibility by the glass foaming scope that adopts dilatometer to analyze to make accurately predicting there are various variablees, so it can contribute to the optimization of process control and production method.Therefore the multicellular glass that, it can be suitable for that accurate blowing temperature is set and manufacture the density with optimization.
Effect of the present invention is not limited to aforementioned content, but those skilled in the art according to following explanation by other effect that is expressly understood that the application does not address.
Brief description of the drawings
Fig. 1 is the schema of illustrating the method for cullet manufacture multicellular glass used according to the invention;
Fig. 2 is the result of illustrating the microstructure of the multicellular glass of manufacturing according to embodiments of the invention 1 and 4;
Fig. 3 is the result of observing the outward appearance of the multicellular glass of manufacturing according to embodiment 1;
Fig. 4 observes according to the result of the outward appearance of the multicellular glass of embodiment 5 to 8 manufactures;
Fig. 5 has illustrated according to the embodiment of the present invention by the change of shape curve that uses dilatometer to obtain;
Fig. 6 has illustrated according to embodiments of the invention 9 to 12 by the change of shape curve that uses dilatometer to obtain;
Fig. 7 has illustrated separately the change of shape curve obtaining according to embodiments of the invention 10;
Fig. 8 is the blow point of illustrating in Fig. 7 and the result lower than the electron microscope observation of the microstructure of multicellular glass when higher than described blow point; With
Fig. 9 a and 9b are illustrated in the horizontal type dilatometer that uses in the method for predicting according to the embodiment of the present invention glass foaming scope and the cross sectional view of vertical-type dilatometer.
Embodiment
Hereinafter, now describe more all sidedly with reference to the accompanying drawings the present invention, wherein show illustrative embodiments of the present invention.But the present invention can implement with multiple different form, and should be interpreted as being limited to the embodiment that the application proposes; And should be interpreted as, it is fully completely to make the disclosure that these embodiments are provided, and has passed on all sidedly thought of the present invention to those skilled in the art.In addition,, for the ease of explaining, key element size in the accompanying drawings may be exaggerated.
The invention is characterized in that with cullet, by directly making cullet foaming and not manufacturing multicellular glass by any special pre-treatment method for the manufacture of multicellular glass, described cullet results from daily life or industry.Fig. 1 illustrates the schema of progressively manufacturing according to the embodiment of the present invention the method for multicellular glass.Hereinafter, with reference to Fig. 1, the method for manufacturing according to the embodiment of the present invention multicellular glass has been described.
With reference to Fig. 1, preparation has the cullet of water glass or boroaluminosilicate component as the raw material (S1) of multicellular glass.This reason is, when the cullet with water glass or boroaluminosilicate component is during as the raw material of multicellular glass, can manufacture multicellular glass in the case of not adding independent whipping agent.
Then, grind prepared cullet with the raw material powder (S2) for the preparation of foaming.In this case, use grinding instrument (as disc refiner or ball mill) to grind prepared cullet by wet milling process.In this case, at least one solvent being selected from water, ethanol, methyl alcohol and acetone can be used as solvent.
Can be by carrying out the grinding of cullet for multiple steps of effectively grinding.For example, can implement by dry method the first corase grind of cullet, then can implement secondary fine grinding with the comparatively meticulous powder of preparation by wet milling process.
The granularity of expecting the powder after the final grinding of preparation is meticulous as far as possible.But, for the consideration of the Financial cost of powder preparation, the granularity of powder can be controlled in the scope of 1 μ m to 10 μ m.
Afterwards, in the situation that not adding whipping agent, cullet powder is placed in shaping dies, suppresses with balanced compacting described cullet powder preparation is become to moulded parts (S3) by single shaft.By calcining in the temperature range at 600 DEG C to 1,000 DEG C and foaming, moulded parts is prepared as to multicellular glass (S5).
In the present invention, with reference to the formation mechanism of having described multicellular glass with following formula 1.
(formula 1)
As shown in fig. 1, for the frit with specific composition, for example, and when the M in formula 1 is during as the sodium in water glass (Na), the H in the time adding water in water +ion and the Na+ ion in glass exchange by hydrolysis, and form NaOH alkaline solution (the 1st step).Then, the OH-iontophoretic injection in NaOH alkaline solution enters in glass, to destroy SiO 2network structure (the 2nd step).Afterwards, in the time standing calcining and foaming process, be included in the OH that is free state in glass as the result of hydrolysis -component or moisture are decomposed to form the bubble in the glass particle of softening or melting.Due to the bubble being trapped in glass particle, thereby can in glass, form bubble, to become multicellular glass.
Multicellular glass by manufacture method manufacture according to the embodiment of the present invention can have uniform pore structure, and can have good aesthetic feeling and excellent mechanical property.For example, when, the physicals of the multicellular glass by above manufacture method manufacture can be included in 25 DEG C thermal conductivity, the 287kg/m of 0.070kcal/mh DEG C 3density, 88% porosity and the compressive strength of 1.4MPa.
As another example of the present invention, can provide the method for manufacturing coloured multicellular glass with multiple color.Can in cullet powder, realize coloured multicellular glass by adding to metal oxide as tinting material.In this case, for example, can be cobalt/cobalt oxide (Co as the metal oxide of tinting material 3o 4) or Mn oxide (MnO 3).In the time that the cullet powder to comprising metal oxide is calcined and make its foaming, can manufacture the coloured multicellular glass painted with particular color.
Can in the process of grinding cullet, add the metal onidiges as tinting material.For example, metal oxide is added in cullet powder, this powder, by adopting the prepared cullet of the first corase grind of wet milling process, is then implemented secondary fine grinding by wet milling process and is prepared to prepare cullet powder.Alternatively, metal oxide is added in the completed powder of secondary fine grinding, then can carry out processing subsequently.In addition, as long as added metal oxide before calcining and foaming process, can use any method, for example, before grinding prepared cullet, add metal oxide, then implement milled processed, or grind cullet and prepare final cullet powder, then before molding, add metal oxide.
Substantially can be included in heating according to the manufacture of the multicellular glass of embodiment of the present invention does not foam in the process of precursor and foams.In this application, statement " precursor does not foam " refers to the glass in state as described below: wherein foaming not yet occurs, but can foam in the time of heating glass.In this case, the precursor that do not foam can be glass particle or the piece material form (comprising the moulded parts forming by pressed glass powder) with predetermined shape.The foaming scope of precursor of can not foaming by calculating to a nicety to control comparatively exactly the manufacturing processed of multicellular glass.
Conventionally,, in order to predict the foaming scope of multicellular glass, in macroscopic view, use hot-stage microscope.But, according to the method for prediction glass foaming scope of the present invention, can not use in the situation of hot-stage microscope and measure length or the volume change that moulded parts occurs during foaming under various conditions by using dilatometer, predict that meeting the two the foam of glass of macroscopic perspective and microcosmic angle produces scope and behavior.Therefore, because the method for prediction glass foaming scope of the present invention can have the technical characterictic of the thermal behavior by using contraction or expansion curve (described curve negotiating dilatometer obtains) sight glass, so comparatively accurate blowing temperature scope can be set in the manufacture of multicellular glass.
Can, by calculate the pucker & bloat behavior of glass with following formula 2 and 3, can release according to the length of the glass of temperature variation or volume change based on formula 2 and 3.
(formula 2)
α＝[(L 2-L 1)/L 0(T 2-T 1)]
＝(XL/L 0)/XT
L 0=at the sample length of initial temperature
L 1=at lesser temps T 1sample length
L 2=at comparatively high temps T 2sample length
Wherein α represents the coefficient of linear expansion, and it refers to the ratio of length variations and temperature variation.
(formula 3)
V＝L 1L 2L 3
dV dT = L 1 L 2 dL 3 dT + L 1 L 3 dL 2 dT + L 2 L 3 dL 1 dT
β = 1 V dV dT = 1 L 3 dL 3 dT + 1 L 2 dL 2 dT + 1 L 1 dL 1 dT
β＝3α
Volume expansivity β is defined as minute changing and the ratio of temperature variation under constant pressure volume.
As measuring the required length of above equation or the technology of volume change, can classify as dilatometry and thermomechanical analysis (TMA) method of the degree that depends on applied load for measuring at the state using constant load applying in sample as the thermoanalysis technology of the length variations (Δ L) of the function of temperature and time.
TMA method has been measured in the state that applies permanent load the length variations as the function of temperature and time, and dilatometry refers to measure the method as the length variations of the function of temperature and time in the state of applied load hardly.But, in ASTM standard and actual measurement, because the test that adopts TMA method to carry out is implemented conventionally in the time applying the power of tens of cN, and in dilatometry, also apply the power of tens of cN, so be nonsensical by these two kinds of measuring method classification.
Conventionally, dilatometer uses the displacement measurement sensor that is called linear variable difference transformer (LVDT) to measure length variations, and described dilatometer comprises and regulates the process furnace of temperature and the support of fixed sample (holder) to install.
Dilatometer can be divided into as the horizontal type in Fig. 9 a with as the vertical-type in Fig. 9 b.In horizontal type, the sample holder 90a that comprises sample 91a flatly can be introduced in process furnace 92a.On the contrary, for vertical-type, the sample holder 90b that comprises sample 91b vertically can be introduced in process furnace 92b.The two all can comprise respectively that thermopair 94a and 94b carry out the temperature of measure sample 91a and 91b horizontal type and vertical-type.Can be by push rod 93a and 93b by predetermined load applying in sample 91a and 91b.For example, for horizontal type dilatometer, can be to measure under 200cN or condition still less in the power that promotes push rod 93a, for vertical-type dilatometer, can be to measure under 200cN or condition still less in the vertical load that promotes push rod 93b.For vertical-type dilatometer, the vertical load that can equal to promote by only applying himself weight of load 93b is measured.
Due to can be by usage level type dilatometer the measurement under the condition of impellent and with vertical-type dilatometer the measurement under the condition of vertical load carry out complementary measurement, so the optimal temperature conditions that forms foam ratio can be set.
In the time using this dilatometer, can identify the pucker & bloat behavior of the precursor that do not foam, to understand in real time the conversion process to multicellular glass.In addition, can depend on the variation of temperature rise rate, produce behavior at the foam of the hold-time of steady temperature scope and the variation of rate of cooling at the angle observation and analysis of both macro and micro.
For example, can observe in real time the foam behavior being caused by the pucker & bloat of glass, simultaneously in the scope of room temperature to 1400 DEG C transformation temperature, in the scope of 0.1 DEG C/min to 50 DEG C/min, change temperature rise rate, transformation temperature hold-time and change rate of cooling in the scope of 0.1 DEG C/min to 20 DEG C/min in the scope of 0 hour to 24 hours.
The method of the foaming scope of prediction glass is described hereinafter, with reference to the accompanying drawings particularly.
The curve (this is called " change of shape curve ") that Fig. 5 illustrates has shown the example of the pucker & bloat behavior of the water soda glass obtaining by usage level type dilatometer.Specifically, change of shape curve is measured the result that the shape (as the length of glass or volume) that produces during as described below changes: as described in during the moulded parts of water soda glass powder is introduced in dilatometer, moulded parts is heated to 700 DEG C in the load of 25cN from room temperature with the temperature rise rate of 5 DEG C/min, keep 120 minutes 700 DEG C of temperature, then moulded parts is cooled to room temperature with the rate of cooling of 5 DEG C/min.
In Fig. 5, x axle represents the time, and the y axle on the left side represents linear shrinkage (Δ L/L, %), and the y axle on the right represents temperature.Fig. 5 (a) has illustrated temperature according to the variation of time, and Fig. 5 (b) has illustrated change of shape curve, and it has shown the pucker & bloat behavior of the water soda glass producing in response to temperature variation.
With reference to change of shape curve illustrated in Fig. 5, in the time that temperature increases, the contraction of glass occurs linearly, until blow point.But the foaming of the precursor that do not foam in the time that the hold-time increases occurs in the blow point of approximately 600 DEG C.Therefore, a part can occur, volume is to increase linearly with mode identical in part 2 therein.Part 3 represents the variation of volume with the reduction of temperature, and can observe in real time according to the appearance in the shrinking percentage of the multicellular glass of the reduction of temperature and the crack that during cooling produced.
According to the method for the measurement foaming scope according to embodiment of the present invention, can, by measure the variation (as the variation of length or volume) of shape during the foaming process of glass, measure in real time the foaming scope of glass.Therefore,, in the time using the method for measuring foaming scope, can for example, know foaming character according to various foaming conditions (, temperature, heating and hold-time condition).Therefore the optimization of various conditions that, can be based on implement to be applicable to the multicellular glass of manufacturing the physicals with expectation about the data of foaming character.
Hereinafter, will describe the present invention in detail according to specific embodiment.But, the invention is not restricted to this.
embodiment 1 to 4: use cullet to manufacture multicellular glass
Use the first cullet with water glass component that grinds of disc refiner.Using method for recycling to proceed to many three times grinds.In the distilled water as solvent, use planetary-type grinding machine first grinding to acquisition like this taking the speed of 100rpm to 400rpm powder (mean particle size as 120 μ m) carry out 1 hour to 72 hours secondary wet-milling (mean particle size as 2 μ m).
In baking oven in 60 DEG C by the powder for drying of regrind 24 hours.Use the 200 order mesh screens dry powder that sieves.The powder sieving so obtaining is placed in shaping dies as the precursor that do not foam, by suppressing by its molding, to prepare the precursor that do not foam.Use electric furnace to be heated to 700 DEG C with the various temperature rise rates of 1 DEG C/min, 5 DEG C/min, 10 DEG C/min and the 20 DEG C/min precursor that will not foam from room temperature, and make it stand calcining and foaming process 2 hours, thus manufacture multicellular glass (embodiment 1 to 4).Table 1 has been introduced the actual conditions of embodiment 1 to 4.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Temperature rise rate (DEG C/min) 1 5 10 20
Calcining temperature (DEG C) 700 700 700 700
Calcination time (hour) 2 2 2 2
Fig. 2 a to 2d has illustrated respectively according to the result of the electron microscope observation of the microstructure of the multicellular glass of the embodiment of the present invention 1 to 4 manufacture.With reference to Fig. 2 a to 2d, can understand in the multicellular glass that hole is evenly dispersed in manufacturing, the mean sizes that can be observed hole increases with the increase of temperature rise rate.In addition,, as the result of observing its outward appearance, good aesthetic feeling is accomplished.In Fig. 3, exemplarily illustrate the result of observing the outward appearance of the multicellular glass of embodiment 2.
embodiment 5 to 8: use cullet to manufacture the artistic multicellular glass of tool
Embodiment 5 to 8 relates to coloured multicellular glass of the painted acquisition of multicellular glass to embodiment 1 to 4 by the color to be scheduled to.Particularly, use disc refiner with the first cullet with water glass component that grinds of the mode identical with embodiment 1 to 4.Using as the 1wt% of tinting material or the cobalt/cobalt oxide (Co of 2wt% 3o 4) or Mn oxide (MnO 3) add to the first grinding of acquisition like this powder (mean particle size be 120 μ m) in, then in the distilled water as solvent, use the mixture 8 hours that planetary-type grinding machine so obtains taking the speed secondary wet-milling of 200rpm (mean particle size as 2 μ m).
In baking oven in 60 DEG C by the powder for drying of regrind 24 hours.Use the 200 order mesh screens dry powder that sieves.The powder sieving so obtaining is placed in shaping dies as the precursor that do not foam, by suppressing by its molding, to prepare the precursor that do not foam.Stand calcining and foaming process by using electric furnace to heat at 700 DEG C the precursor that makes not foam for 2 hours with the temperature rise rate of 5 DEG C/min, thereby manufacture the multicellular glass with multiple color.Table 2 has been introduced the actual conditions of embodiment 5 to 8 and the color of multicellular glass.
Table 2
Fig. 4 has illustrated according to the observations of the color of the multicellular glass of embodiment 5 to 8 manufactures with upper left side, upper right side, lower left and bottom-right order.
With reference to upper left side and the upper right side of Fig. 4, when the amount with 1wt% is added cobalt/cobalt oxide (Co 3o 4) time, obtain grey and 297kg/m 3density.But in the time that the addition of cobalt/cobalt oxide is increased to 2wt%, the color of multicellular glass becomes and has the light blue of fabulous aesthetic feeling, and density is increased to 476kg/m 3.This reason is that the foaming character of glass changes according to the addition of cobalt/cobalt oxide.
With reference to lower left and the lower right of Fig. 4, when the amount with 1wt% is added Mn oxide (MnO 3) time, obtain military blueness and 202kg/m 3density.But, in the time that the addition of Mn oxide is increased to 2wt%, obtained lilac, and density is increased to 306kg/m 3.
Therefore, will be understood that, consider the color of multicellular glass and density the two, can be by suitably regulating the addition manufacture of tinting material to there is the multicellular glass of color and the density of expectation.
embodiment 9 to 12: the foaming scope that uses dilatometer prediction glass
In order to use the foaming scope of the glass prediction multicellular glass with water glass component, by sieving powder and prepare the precursor that do not foam with this powder of shaping dies molding.Prepared not foaming precursor is introduced in dilatometer, with the various temperature rise rates (embodiment 9 to 12) of the 1 DEG C/min as illustrated in table 3,5 DEG C/min, 10 DEG C/min and 20 DEG C/min, in the time applying the load of 25cN, observe in real time the behavior of multicellular glass.
Table 3
Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Temperature rise rate (DEG C/min) 1 5 10 20
Load change (cN) 25 25 25 25
Rate of cooling (DEG C/min) - - - -
Hold-time (min) - - - -
Fig. 6 has illustrated change of shape curve, described curve display the pucker & bloat behavior of the precursor that do not foam under the various temperature rise rates of 1 DEG C/min, 5 DEG C/min, 10 DEG C/min and 20 DEG C/min.With reference to Fig. 6, in the time that temperature increases, the precursor linear shrinkage of not foaming.But, will be understood that, due to by the foaming starting temperature hole forming of foaming, volume is linear expansion again.In this case, verifiable is that the do not foam foaming starting temperature of precursor trends towards increasing with the increase of temperature rise rate.
Fig. 7 has illustrated the change of shape curve according to temperature in the time that temperature rise rate is 5 DEG C/min individually, and the starting temperature that wherein foams is 693 DEG C.
Fig. 8 a, 8b and 8c have illustrated the microstructure of multicellular glass in the time of the temperature of 673 DEG C shown in Fig. 7,693 DEG C and 713 DEG C.
Will be understood that, not observing hole lower than the temperature of foaming starting temperature, (Fig. 8 a), (Fig. 8 b), and due to violent foamed phenomenon observing relatively coarse hole higher than the temperature of foaming starting temperature, (Fig. 8 c) to observe hole in foaming starting temperature.
Therefore, verifiable is can be by by foaming behavior curve controlled with foaming condition manufacture is set has the multicellular glass of optimum physical properties.
Although shown particularly with reference to illustrative embodiments of the present invention and described the present invention, but those those skilled in the art will appreciate that the spirit and scope of the invention in the case of not departing from claims restriction, can carry out therein the many variations in form and in details.

Claims (14)

1. use cullet to manufacture the method for multicellular glass, described method comprises:
The cullet powder by suppressing in shaping dies in the situation that not adding whipping agent with water glass or boroaluminosilicate component is prepared moulded parts; With
The temperature ranges of 600 DEG C to 1,000 DEG C, described moulded parts is calcined and is made its foaming,
The preparation method of wherein said cullet powder comprises by wet milling process and grinds the cullet with water glass or boroaluminosilicate component.
2. the process of claim 1 wherein at least one or the multiple solvent as described wet milling process that are selected from water, ethanol, methyl alcohol and acetone.
3. the method for claim 1, it is dry grinded to the described cullet with water glass or boroaluminosilicate component before being included in further and grinding by described wet milling process.
4. the process of claim 1 wherein that described cullet powder is of a size of 1 μ m to 10 μ m.
5. the process of claim 1 wherein and add to metal oxide as tinting material in described cullet powder.
6. the method for claim 5, wherein said metal oxide is cobalt/cobalt oxide (Co 3o 4) or Mn oxide (MnO 3) in any one or multiple.
7. the method for claim 6, wherein, before calcining and foaming, adds described metal oxide in described cullet powder to.
8. the method for claim 7 was wherein added described metal oxide before grinding by described wet milling process.
9. the method for foaming scope of prediction glass, described method comprises the foaming scope of the precursor that do not foam described in predicting according to the change of shape curve of temperature with the precursor that do not foam, described change of shape curve adopts dilatometer to measure.
10. the method for claim 9, wherein obtains described according to the change of shape curve of temperature by following steps:
The precursor that will not foam is introduced in dilatometer; With
In the time of the foaming starting temperature of the precursor that do not foam described in the described precursor that do not foam is heated above, length or the volume change of the precursor that do not foam described in measurement.
The method of 11. claims 9 is wherein under 200cN or condition still less, to obtain described change of shape curve in vertical load or impellent.
The method of 12. claims 9, wherein by change measure in temperature range, temperature rise rate, rate of cooling or temperature hold-time any one or multiple, obtain described change of shape curve.
The method of 13. claims 11, wherein said measurement temperature range changes in the scope of room temperature to 1400 DEG C, described temperature rise rate changes in the scope of 0.1 DEG C/min to 50 DEG C/min, described rate of cooling changes in the scope of 0.1 DEG C/min to 50 DEG C/min, and the described hold-time changes in 24 hours or scope still less.
The method of 14. claims 9, the wherein said precursor that do not foam is powder type or the piece material form with predetermined shape.
CN201180076280.9A 2011-11-22 2011-11-22 Use the method for cullet manufacture foam glass and the method for the foaming scope using dilatometer prediction glass Expired - Fee Related CN104066692B (en)

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