CN111377751A - Foaming agent for producing foamed ceramics - Google Patents
Foaming agent for producing foamed ceramics Download PDFInfo
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- CN111377751A CN111377751A CN202010450691.0A CN202010450691A CN111377751A CN 111377751 A CN111377751 A CN 111377751A CN 202010450691 A CN202010450691 A CN 202010450691A CN 111377751 A CN111377751 A CN 111377751A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The invention belongs to the ceramic production technology, and particularly relates to a foaming agent for producing foamed ceramic. The foaming agent contains attapulgite, and the attapulgite can be used alone as the foaming agent or mixed with other foaming agents such as silicon carbide. Compared with the silicon carbide foaming agent in the prior art, the foaming agent containing the attapulgite is cheaper and has low foaming temperature, so that the sintering temperature of the foamed ceramic can be reduced, and the production energy consumption of the foamed ceramic is further reduced.
Description
Technical Field
The invention relates to a ceramic production technology, in particular to a foaming agent for producing foamed ceramic.
Background
The foamed ceramic is a light ceramic product containing closed pores, has the functions of light weight and heat insulation, and is a high-quality green environment-friendly building material. Foaming agent is needed to be used in the production of foamed ceramics, gas is discharged from the foaming agent in the high-temperature sintering process, the gas is sealed in a liquid phase generated after the ceramic raw material is melted, and after a blank body is cooled, the gas can form pores in the ceramic blank body, so that the ceramics have the characteristics of light weight, heat preservation and heat insulation.
At present, silicon carbide, iron oxide, carbon powder and the like are commonly used as foaming agents for industrially producing foamed ceramics, wherein the silicon carbide is the most common, because the foaming temperature of the silicon carbide is consistent with the sintering temperature of the conventional building ceramic wall and floor tiles, and a certain amount of silicon carbide can be contained in waste residues generated by polishing and grinding in the production process of the ceramic wall and floor tiles and can be used as a raw material for introducing the foaming agents. However, the foaming temperature of the silicon carbide foaming agent is relatively narrow, which limits the optimization of the production process of the foamed ceramic product, for example, the firing temperature is controlled between 1100 ℃ and 1200 ℃, the silicon carbide is difficult to decompose and foam at the firing temperature lower than 1100 ℃, and the generated bubbles are few; the firing temperature is higher than 1200 ℃ or the temperature rise rate is too high between 900 ℃ and 1200 ℃, so that the foaming gas can break through the pore walls, and the strength of the foamed ceramic product is influenced. The foaming agents such as iron oxide have similar problems, and other foaming agents known so far are often unstable as compared with silicon carbide, and therefore, they are rarely used for industrial production of foamed ceramics, and are often used in combination with silicon carbide even when added.
In addition, the silicon carbide content in the polishing slag is not stable and cannot be used as a stable foaming agent source. Therefore, a stable and cheap foaming agent with good matching performance to the production process is always searched in the field of foamed ceramic production.
Disclosure of Invention
Against the problems raised in the background art, the main object of the present invention is to provide a novel foaming agent for producing foamed ceramics.
A foaming agent for producing foamed ceramics contains attapulgite.
Preferably, the foaming agent further contains silicon carbide.
Preferably, the foaming agent further contains iron oxide and/or manganese oxide.
Preferably, the attapulgite is a rod-like nano-sized fiber powder.
Further preferably, the length of the fiber powder is less than or equal to 0.8-1.7 mu m, and the width is less than or equal to 12-27 nm.
Preferably, the iron oxide is ferric oxide and/or ferroferric oxide.
Preferably, the silicon carbide has a median particle diameter of 50 μm or less.
Preferably, the mass percentage of the attapulgite in the foaming agent is more than or equal to 50 percent.
Preferably, the mass ratio of the silicon carbide to the manganese oxide in the foaming agent is 1: 0.01-2.
Preferably, the mass ratio of the silicon carbide to the iron oxide in the foaming agent is 1: 0.01-2.
Compared with the silicon carbide foaming agent in the prior art, the foaming agent containing the attapulgite is cheaper and has low foaming temperature, so that the sintering temperature of the foamed ceramic can be reduced, and the production energy consumption of the foamed ceramic is further reduced.
Drawings
Fig. 1 is a schematic diagram of the crystal structure of attapulgite.
FIG. 2 is a graph showing the sintered morphology of attapulgite at 1180 ℃.
FIG. 3 is a differential thermal curve of attapulgite.
Detailed Description
The invention is described in detail below with reference to the figures and the detailed description.
Attapulgite, also known as Palygorskite (Palygorskite) or Palygorskite, is an aqueous magnesium-rich aluminosilicate clay mineral with a chain-layered structure. The structure of the compound belongs to 2: type 1 clay minerals. At each of 2: in the 1 unit structure layer, the tetrahedral wafer angle tops are reversed at a certain distance to form a layer chain. Channels are formed between the tetrahedral strips parallel to the chain. The channels are filled with zeolite water and crystal water, and can be seen in figure 1.
The attapulgite in China has the advantages of abundant mineral resources, good quality, easy mining, low price, and capacity of completely meeting the requirements of industrial production, and has obvious performance advantages compared with the resource attributes of other countries in the world. Therefore, the method has positive significance for fully utilizing the advantages of attapulgite mineral resources in China so as to improve the potential value and the utilization rate of the attapulgite.
The use of attapulgite as a blowing agent in the production of foamed ceramics has not been found. However, the experiments show that under the process condition that the firing temperature is 1100-1200 ℃, the use amount of the attapulgite reaches more than 30% of the total mass of the raw material formula, so that the fired green body has more visible air holes, the air holes are more open air holes, and when the use amount of the attapulgite reaches more than 50% of the total mass of the raw material formula, the air holes of the fired green body are more uniformly distributed. When a large amount of flux (for example, cullet) is used, the firing temperature can be further lowered. Therefore, the research of the attapulgite as the foaming agent of the foamed ceramics provides a new direction for reducing the sintering temperature of the foamed ceramics. FIG. 1 is a schematic representation of the crystal structure of attapulgite. FIG. 2 is a photograph of the sintered attapulgite at 1180 ℃.
Typical attapulgite minerals are constructed as shown in table 1 below.
TABLE 1
Differential thermal analysis was performed on the attapulgite, and the corresponding differential thermal curve is shown in fig. 3. Removing water adsorbed on the outer surface of the attapulgite from room temperature to 140 ℃ and water adsorbed on the empty islands; at 140-300 ℃, crystal water of the attapulgite is removed; when the temperature reaches 300-500 ℃, the structural water of other phases in the attapulgite is dehydrated; when the temperature reaches 650 ℃, the structural water in the attapulgite is basically removed, the quality of the dehydrated attapulgite tends to be stable, and the weight loss after 650 ℃ is the quality loss caused by the thermal decomposition of other impurity minerals such as montmorillonite. The attapulgite has violent dehydration reaction before 850 ℃, and a water vapor exhaust passage can be formed in the raw materials for producing the foamed ceramics by using the attapulgite as a foaming agent, so that gas generated by the exhaust decomposition of other raw materials can be smoothly discharged through the water vapor passage.
Therefore, the attapulgite used as the foaming agent has the characteristic of continuous foaming, the exhaust passage generated by violent dehydration in the preheating stage can enable the exhaust in the preheating stage to be smoother, the gas generated by continuous slow decomposition at 850 ℃ enables the exhaust passage generated by water vapor to be reserved in the liquid phase generated by melting, and further irregular flat air holes are formed after burning, and the air holes are mainly perforated. The foaming can still be realized under the condition that the sintering temperature of the raw material formula is lower.
When the attapulgite is used as a single-component foaming agent, the attapulgite accounts for 30-70% of the total mass of the raw materials. Here, 30 to 70% means any point between 30% and 70%, for example, 30%, 35%, 40%, 44%, 48%, 50%, 55%, 60%, 63%, 67%, 70%, etc.
Example 1
The raw materials are as follows according to the mass portion: 12 parts of pressed mud, 70 parts of attapulgite, 5 parts of talc and 13 parts of albite.
The pressed mud is obtained by recycling and treating waste mud generated in the ceramic production process, and the talc and the albite are common ceramic raw materials and mainly play a role in fluxing.
The specific production process comprises the following steps:
step 1: spray granulation: the raw materials are mixed and ball-milled to prepare slurry, and then spray granulation is carried out to prepare powder.
Step 2: and (3) sintering the cloth: and (2) scattering the powder obtained in the step (1) in a refractory kiln furniture, paving to form a powder layer with a certain thickness, then feeding the powder into a kiln together with the kiln furniture to be fired, keeping the maximum firing temperature at 1180 ℃ for 90 minutes, and cooling to obtain a foamed ceramic blank.
And step 3: polishing and cutting: and (3) polishing and grinding the obtained foamed ceramic blank to remove the skin, and then cutting to obtain the foamed ceramic product in the required shape.
The obtained foamed ceramic product was examined and the data was recorded as follows.
Appearance and appearance: the shape of the air holes is irregular, and the air holes are flat; the air holes are communicated open holes; the aperture is large and is mostly a large hole with the diameter of 1-5 mm.
Density: 695kg/m3(ii) a Closed porosity: 52 percent; breaking strength: 3.5MPa and 5.9MPa in compressive strength; thermal stability (200 ℃ C., times), 6 times no cracking.
Example 2
The raw materials are as follows according to the mass portion: 15 parts of pressed mud, 50 parts of attapulgite, 5 parts of talc, 20 parts of albite and 10 parts of waste brick powder.
The production process was the same as in example 1, and the obtained foamed ceramic product was examined and the data was recorded as follows.
Appearance and appearance: the shape of the air holes is irregular, and the air holes are flat; the air holes are provided with communicated open pores and a certain amount of closed pores which are not communicated; the aperture is large and is mostly a large hole with the diameter of 1-5 mm.
Density: 934kg/m3(ii) a Closed porosity: 65 percent; breaking strength: 3.8MPa and the compressive strength is 6.8 MPa; thermal stability (200 ℃ C., times), 6 times no cracking.
Example 3
The raw materials are as follows according to the mass portion: 15 parts of press mud, 30 parts of attapulgite, 5 parts of talc, 25 parts of albite, 10 parts of waste brick powder, 10 parts of bentonite and 5 parts of cullet.
The production process was substantially the same as in example 1, except that the firing temperature was 1100 ℃ and the holding time was 90 minutes, and the obtained foamed ceramic product was examined and the data was recorded as follows.
Appearance and appearance: the number of air holes is small, the shapes of the air holes are irregular, and the air holes are more flat; the pores are mostly closed pores which are not communicated, and the aperture is less than or equal to 1 mm.
Density: 1355kg/m3(ii) a Closed porosity: 78 percent; breaking strength: 4.8MPa and the compressive strength is 6.8 MPa; thermal stability (200 ℃ C., times), 6 times no cracking.
Through the embodiment, the attapulgite is used as a single foaming agent, the using amount is large, the shape of the air holes is mainly flat irregular air holes, and the produced foamed ceramic is high in density and compressive strength.
In addition, the firing temperature can be further lowered by adding a strong flux to the formulation of the foamed ceramic body, for example, when 30% or more of cullet is added to the formulation, the firing temperature can be lowered to about 1000 ℃, and the foamed ceramic pores are flat irregular pores as in examples 1 to 3, and the pore diameter of the pores is not more than 0.5 mm. The method shows that the attapulgite can widen the sintering temperature range of the foamed ceramics, and the foamed ceramics can still be obtained at lower sintering temperature, thereby providing possibility for reducing energy consumption in the production of the foamed ceramics.
The foaming agent with better performance can be obtained by adding silicon carbide into the attapulgite. In the background art, the characteristics of silicon carbide foaming agent have been introduced, which is a good foaming agent, and the generated bubbles are uniform, but the foaming temperature is too narrow, so that the firing system is more severe.
Of course, the silicon carbide can be introduced into the silicon carbide powder or the polishing slag containing the silicon carbide.
Generally, the amount of silicon carbide is 0.2-2% of the total mass of the raw materials. When silicon carbide is introduced, the amount of attapulgite used can be greatly reduced. And the iron oxide in the attapulgite can provide a large amount of oxygen elements for the decomposition of the silicon carbide in the sintering process, so that the decomposition of the silicon carbide is accelerated.
Because the dosage of the silicon carbide is less, the silicon carbide is mostly used as an additive, namely, the main raw materials are prepared according to the mass ratio of 100 parts, and then the silicon carbide is introduced in an additional form.
Example 4
The raw materials are as follows according to the mass portion: 15 parts of press mud, 30 parts of attapulgite, 5 parts of talc, 25 parts of albite, 10 parts of waste brick powder, 10 parts of bentonite, 5 parts of cullet and 0.35 part of silicon carbide powder.
The specific production process was the same as in example 3, and the obtained foamed ceramic product was tested and the data was recorded as follows.
Appearance and appearance: the shape of the air holes is mainly regular round or oval, and a small amount of irregular flat air holes exist; the pores are mainly closed pores, and the pore diameter is less than or equal to 1 mm.
Density: 643kg/m3(ii) a Closed porosity: 87 percent; breaking strength: 8.8MPa and 5.2MPa of compressive strength; thermal stability (200 ℃ C., times), 6 times no cracking.
Comparative example 4-1
The raw materials are as follows according to the mass portion: 15 parts of press mud, 30 parts of polishing slag, 5 parts of talcum, 25 parts of albite, 10 parts of waste brick powder, 10 parts of bentonite, 5 parts of cullet and 0.35 part of silicon carbide powder.
The specific production process was the same as in example 3, and the obtained foamed ceramic product was tested and the data was recorded as follows.
Appearance and appearance: the pores are fine and the aperture is less than 0.5mm, and the foaming of the foaming agent is not complete enough.
Density: 698kg/m3(ii) a Closed porosity: 88 percent; breaking strength: 8.6MPa and 3.5MPa of compressive strength; thermal stability (200 ℃ C., times), 6 times no cracking.
Comparing example 3, example 4 and example 4-1, we can find that the use of a combination of attapulgite and silicon carbide has better effects (density and compressive strength index) than the use of attapulgite and silicon carbide alone.
Of course, in the case of introducing silicon carbide, the amount of attapulgite may be reduced so that the pores in the foamed ceramic product are more regular, but at the same time, the minimum amount of attapulgite for forming the exhaust passage during the preheating process for firing the foamed ceramic is preferably not less than 2% by weight of the total mass of the raw materials, and the maximum amount of silicon carbide used as the foaming agent for the foamed ceramic is also 2% by weight of the total weight of the raw materials, so that when silicon carbide and attapulgite are compounded as the foaming agent, the total mass of the foaming agent is preferably not less than 50% by weight of attapulgite.
When the attapulgite and the silicon carbide are mixed and applied, the compressive strength of the foamed ceramic is greatly improved, and the using amount of the silicon carbide can be reduced, because the attapulgite has a layered structure, fine powder of the silicon carbide can enter the intercalation of the attapulgite in the process of mixing raw materials, so that the strength of a product, particularly the compressive strength, can be improved; in addition, the iron oxide in the attapulgite can provide more oxygen elements for the silicon carbide in the high-temperature sintering process to promote the decomposition of the silicon carbide. Under the condition that the basic formula proportion and the sintering process are consistent, the inflection point is formed when the median grain diameter of the silicon carbide is 50 microns, and silicon carbide particles with the median grain diameter of less than or equal to 50 microns can be better inserted into gaps of attapulgite in the ball milling process, so that the foamed ceramic has higher strength, and the using amount of silicon carbide powder can be properly reduced.
Example 5
In this example, we preprocessed attapulgite into rod-like nanoscale fiber powder. The attapulgite clay can be used as a foaming agent for producing the foamed ceramic product to improve the strength of the foamed ceramic product, and the attapulgite clay not only is used as the foaming agent, but also has the toughening effect to improve the strength of the foamed ceramic product. In example 5, the same mass ratio as in example 1 was used, except that the attapulgite used in example 1 was raw attapulgite. The flexural strength and the compressive strength of the tested product are respectively 6.7Mpa and 8.9Mpa, the lifting amplitude is obvious, and therefore, the effect of the pretreated attapulgite is better.
In practical industrial production and application, the addition amount of the nano-scale attapulgite fiber powder is small, otherwise, the production cost is high, and therefore, the nano-scale attapulgite fiber powder is often matched with silicon carbide for use.
When the attapulgite fiber powder is used with silicon carbide in a matching mode, the silicon carbide is used as a main foaming agent, one function of the attapulgite is favorable for exhaust in a preheating stage, but the exhaust channel has larger communicated holes formed by fusing air holes in a subsequent sintering process, so that the influence of the exhaust of water vapor on the subsequent foaming process is less by controlling the size of the attapulgite fiber powder to be improved, specifically when the length of the fiber powder is less than or equal to 0.8-1.7 mu m and the width of the fiber powder is less than or equal to 12-27 nanometers.
The attapulgite itself may be used as the blowing agent and therefore it may be used in combination with any of the known blowing agents which have been disclosed so far.
The large amount of free oxygen can promote the decomposition of the silicon carbide, so that manganese oxide and/or iron oxide which can decompose and release free oxygen elements are introduced into the foaming agent to have a positive effect, wherein the iron oxide is preferably ferric oxide and ferroferric oxide.
The amount of manganese oxide and iron oxide used is up to 2 times the mass of the silicon carbide.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. A foaming agent for producing foamed ceramics, characterized in that it contains attapulgite.
2. The foaming agent for producing foamed ceramics according to claim 1, wherein the foaming agent further contains silicon carbide.
3. The foaming agent for producing foamed ceramics according to claim 2, wherein the foaming agent further contains iron oxide and/or manganese oxide.
4. The foaming agent for producing foamed ceramics according to claim 1, wherein the attapulgite is a rod-like nano-scale fiber powder.
5. The foaming agent for producing foamed ceramics according to claim 4, wherein the fiber powder has a length of 0.8 to 1.7 μm and a width of 12 to 27 nm.
6. The foaming agent for producing foamed ceramics according to claim 3, wherein the iron oxide is ferric oxide and/or ferroferric oxide.
7. The foaming agent for producing foamed ceramics according to claim 2, wherein the silicon carbide has a median particle diameter of 50 μm or less.
8. The foaming agent for producing foamed ceramics according to claim 2, wherein the attapulgite is present in an amount of 50% by mass or more.
9. The foaming agent for producing foamed ceramics according to claim 3, wherein the mass ratio of the silicon carbide to the manganese oxide is 1:0.01 to 2.
10. The foaming agent for producing foamed ceramics according to claim 3, wherein the mass ratio of the silicon carbide to the iron oxide is 1:0.01 to 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110317067A (en) * | 2019-07-19 | 2019-10-11 | 广东金意陶陶瓷集团有限公司 | Foaming agent and its preparation method and application, foamed ceramic wallboard powder and preparation method thereof |
| CN117185831A (en) * | 2023-09-13 | 2023-12-08 | 信阳中毅高热材料有限公司 | Environment-friendly refractory ceramic plate and production process thereof |
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