CN113234290A - Waste ceramic composite building material and preparation method and application thereof - Google Patents
Waste ceramic composite building material and preparation method and application thereof Download PDFInfo
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- CN113234290A CN113234290A CN202110500269.6A CN202110500269A CN113234290A CN 113234290 A CN113234290 A CN 113234290A CN 202110500269 A CN202110500269 A CN 202110500269A CN 113234290 A CN113234290 A CN 113234290A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to the technical field of building materials, in particular to a waste ceramic composite building material and a preparation method and application thereof, wherein the waste ceramic composite building material is prepared from the following raw materials in parts by weight: 100 portions and 150 portions of waste ceramic powder; 1-4 parts of a surface-modified coupling agent; 500 portions of refractory polymer material and 1000 portions of refractory polymer material; the surface modification is carried out on the waste ceramic powder, the compatibility of the waste ceramic powder and a fireproof high polymer material is improved, the waste ceramic powder and the high polymer material are blended, the waste ceramic powder is a flame-retardant or non-combustible material, the fireproof performance of the composite material is effectively improved under the action of mass blending of the waste ceramic powder, the secondary utilization of the waste ceramic powder is realized, the composite material with excellent fireproof performance is prepared, and the composite material is applied to building materials.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a waste ceramic composite building material and a preparation method and application thereof.
Background
Along with the development of the building industry, waste ceramics generated in the building industry is quite amazing, for example, the total daily production amount of industrial wastes of each production line of a ceramic city in the county of Fakuchi in Liaoning province reaches 4800 tons, the generation of the wastes is not effectively treated and recycled, the generation and elimination of the wastes affect and restrict the environmental quality and the development space of the northeast china ceramics, at present, the environmental protection is more and more concerned by people in the world, how to collect the ceramic wastes and then process and recycle the ceramic wastes is an important problem which needs to be considered at present, and the secondary utilization of the ceramic wastes not only can save natural resources and change waste into valuable, but also can reduce environmental pollution, improve ecological environment and promote the sustainable development of the ceramic industry and social economy.
With the increase of serious fire accidents related to wall heat-insulating materials, the construction field provides that the methods of fire prevention isolation, no cavity and the like are adopted in an external wall external heat-insulating system, so that the defects that flame is easy to spread and diffuse in the combustion characteristic of an organic heat-insulating material can be overcome, and the fire accidents caused by the spread and diffusion of flame due to flammable heat-insulating materials are avoided. However, the research on the fireproof structure cannot solve the problems of temperature resistance and flame resistance of the organic heat-insulating material on a wall structure, smoke gas release of the organic heat-insulating material in a fire disaster, melting and dripping of the thermoplastic organic heat-insulating materials such as EPS and XPS in the combustion process and the like. This means that the inherent disadvantages of low fire-proof rating, poor stability and durability of the organic thermal insulation material technology have not been able to meet the social requirements for building thermal insulation materials.
Disclosure of Invention
The invention aims to provide a waste ceramic composite building material and a preparation method and application thereof, aiming at overcoming the defects in the prior art, the invention firstly carries out surface modification on waste ceramic powder, improves the compatibility of the waste ceramic powder and a fireproof high polymer material, and then blends the waste ceramic powder and the high polymer material, wherein the waste ceramic powder is a flame-retardant or non-combustible material, and at the moment, under the action of mass blending of the waste ceramic powder, the fire resistance of the composite material is effectively improved, so that the secondary utilization of the waste ceramic powder is realized, and the composite material with excellent fire resistance is prepared and applied to the building material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a waste ceramic composite building material is prepared from the following raw materials in parts by weight: 100 portions and 150 portions of waste ceramic powder; 1-4 parts of a coupling agent; 500 portions of refractory polymer material.
Preferably, the porcelain also comprises 2-8 parts of porcelain powder; the ceramic powder comprises low-temperature ceramic powder, medium-temperature ceramic powder and high-temperature ceramic powder, wherein the low-temperature ceramic powder is aluminum hydroxide or magnesium hydroxide, the medium-temperature ceramic powder is one of montmorillonite, mica powder and diatomite, and the high-temperature ceramic powder is magnesium oxide or kaolin.
Preferably, the coupling agent is prepared from the following raw materials in parts by weight: 1-3 parts of an aluminate coupling agent; 5-9 parts of a silane coupling agent;
wherein, the aluminate coupling agent is DL-482, and the silane coupling agent is KH550 or KH 570.
Preferably, the fire-resistant polymer material is one or a mixture of any two of polystyrene resin, polyethylene resin and polypropylene resin.
Preferably, the particle size of the waste ceramic powder is 100-200 meshes.
The invention also provides a preparation method of the waste ceramic composite building material, which comprises the following steps:
(1) weighing: weighing the following raw materials in parts by weight: 100 portions and 150 portions of waste ceramic powder; 1-4 parts of a coupling agent; 500 portions of refractory polymer material and 1000 portions for standby;
(2) modifying the surface of the waste ceramic powder:
s1, adding the waste ceramic powder into ammonia water, and reacting for 8-12h under the boiling condition to obtain an intermediate;
wherein, the concentration of the ammonia water is 10-20%;
s2, dissolving a coupling agent in an ethanol aqueous solution to obtain a coupling agent mixed solution, adding the intermediate into the coupling agent mixed solution under the stirring condition, stirring at 60-80 ℃ for 360min, and drying to obtain modified waste ceramic powder;
(3) preparing a waste ceramic composite building material:
and (3) adding the modified waste ceramic powder obtained in the step (2) into the chopped and melted refractory polymer material, uniformly mixing, and airing at room temperature after a slush molding casting film is formed to obtain the waste ceramic composite building material.
Preferably, 2-8 parts of vitrified powder is weighed in the step (1), and is uniformly mixed with the chopped and melted refractory polymer material and the modified waste ceramic powder in the step (3), and the mixture is subjected to slush molding and tape casting to form a film.
Preferably, the solvent of step S2 is ethanol solution with 95% volume fraction.
The invention also protects the application of the waste ceramic composite building material in preparing a refractory building material.
Preferably, the composite building material is applied to an interior wall refractory material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention realizes the secondary utilization of the waste ceramic material, applies the waste ceramic material to the refractory high polymer material, and greatly mixes the waste ceramic material into the refractory high polymer material, thereby not only effectively lightening and blocking the combustion of the high polymer material, but also avoiding the problems of melting, dripping and the like generated by the high polymer material during the combustion, and further overcoming the technical defects of poor stability and durability in the prior art.
2. Ceramic raw materialComprises kaolin, clay, porcelain stone, porcelain clay, colorant, blue and white material, lime glaze and lime alkali glaze; the main raw materials of the ceramic material comprise alumina in kaolin and clay, and the crystal of the ceramic material is mainly single oxide (such as Al)2O3MgO) and composite oxides (e.g. spinel MgO. Al)2O3Lead zirconate titanate Pb (Zr, Ti) O3) In addition, the non-oxide ceramic material also contains crystals of corresponding components such as carbide, nitride, boride, silicide and the like, and the existence of the raw materials realizes the effective refractory performance of the waste ceramic powder;
because the waste ceramic powder has the technical defect of poor compatibility, the waste ceramic powder is difficult to be compatible with a refractory high polymer material, the waste ceramic powder can be subjected to surface modification, and the compatibility of the waste ceramic powder and the refractory high polymer material is improved through the surface modification, so that the refractory high polymer material and the waste ceramic powder can realize excellent blending and form a stable structure; the surface of the coupling agent selected by the invention has amphiphilic groups, namely hydrophilic groups and hydrophobic groups, and the hydrophilic groups on the surface of the coupling agent react with the hydroxyl groups on the surface of the modified ceramic powder, so that the coupling agent is stably coated on the surface of the waste ceramic material, and the coupling agent has excellent compatibility with the refractory high polymer material, thereby improving the blending with the refractory high polymer material and realizing the uniform distribution of the waste ceramic powder in the refractory high polymer material.
3. The invention also comprises inorganic ceramic powder which can be converted into an inorganic hollow ceramic material when the waste ceramic composite building material is subjected to flameless high temperature of more than 300 ℃ and flame ablation of more than 500 ℃, and the special material formed at high temperature can realize effective heat insulation and fire insulation effects and effectively protect the defects of melting, dripping and the like generated by the internal refractory high polymer material.
Drawings
FIG. 1 is a thermogravimetric analysis of samples of examples 2 and 4 of the present invention;
wherein line a is the thermogravimetric analysis plot of example 2; line b is the thermogravimetric analysis plot of example 4;
FIG. 2 is a graph showing the heat deformation properties of samples of examples 2 and 4 of the present invention;
where line a is the deformation-temperature curve of example 2 and line b is the deformation-temperature curve of example 4.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
The concentration of the ammonia water in the invention is prepared by diluting commercial 28% ammonia water.
Example 1
A preparation method of a waste ceramic composite building material comprises the following steps:
(1) weighing: weighing the following raw materials in parts by weight: 100 parts of waste ceramic powder; 2 parts of a coupling agent; 500 parts of polyethylene resin for later use;
the coupling agent comprises an aluminate coupling agent and a KH550 silane coupling agent, and the mass ratio of the aluminate coupling agent to the KH550 silane coupling agent is 1: 9;
(2) modifying the surface of the waste ceramic powder:
s1, adding the waste ceramic powder into ammonia water with the concentration of 20%, and reacting for 8 hours under the boiling condition to obtain an intermediate;
s2, dissolving a coupling agent in an ethanol aqueous solution to obtain a coupling agent mixed solution, adding the intermediate into the coupling agent mixed solution under the stirring condition, stirring at 60 ℃ for 360min, and drying to obtain modified waste ceramic powder;
(3) preparing a waste ceramic composite building material:
and (3) adding the modified waste ceramic powder obtained in the step (2) into the cut and melted polyethylene resin, uniformly mixing, and carrying out slush molding, tape casting and film forming, and then airing at room temperature to obtain the waste ceramic composite building material.
Example 2
A preparation method of a waste ceramic composite building material comprises the following steps:
(1) weighing: weighing the following raw materials in parts by weight: 130 parts of waste ceramic powder; 3 parts of a coupling agent; 750 parts of polystyrene resin for later use;
the coupling agent comprises an aluminate coupling agent and a KH570 silane coupling agent, and the mass ratio of the aluminate coupling agent to the KH570 silane coupling agent is 2: 6;
(2) modifying the surface of the waste ceramic powder:
s1, adding the waste ceramic powder into 15% ammonia water, and reacting for 10 hours under the boiling condition to obtain an intermediate;
s2, dissolving a coupling agent in an ethanol aqueous solution to obtain a coupling agent mixed solution, adding the intermediate into the coupling agent mixed solution under the stirring condition, stirring at 70 ℃ for 240min, and drying to obtain modified waste ceramic powder;
(3) preparing a waste ceramic composite building material:
and (3) adding the modified waste ceramic powder obtained in the step (2) into the cut and melted polystyrene resin, uniformly mixing, and carrying out slush molding, tape casting and film forming, and then airing at room temperature to obtain the waste ceramic composite building material.
Example 3
A preparation method of a waste ceramic composite building material comprises the following steps:
(1) weighing: weighing the following raw materials in parts by weight: 150 parts of waste ceramic powder; 4 parts of a coupling agent; 1000 parts of polypropylene resin for later use;
the coupling agent comprises an aluminate coupling agent and a KH550 silane coupling agent, and the mass ratio of the aluminate coupling agent to the KH550 silane coupling agent is 3: 5;
(2) modifying the surface of the waste ceramic powder:
s1, adding the waste ceramic powder into 10% ammonia water, and reacting for 12h under the boiling condition to obtain an intermediate;
s2, dissolving a coupling agent in an ethanol aqueous solution to obtain a coupling agent mixed solution, adding the intermediate into the coupling agent mixed solution under the stirring condition, stirring at 80 ℃ for 120min, and drying to obtain modified waste ceramic powder;
(3) preparing a waste ceramic composite building material:
and (3) adding the modified waste ceramic powder obtained in the step (2) into the chopped and melted polypropylene resin, uniformly mixing, carrying out slush molding, tape casting and film forming, and then airing at room temperature to obtain the waste ceramic composite building material.
Example 4
A preparation method of a waste ceramic composite building material comprises the following steps:
the preparation method is the same as the preparation method of the embodiment 2, except that 2-8 parts of the ceramic powder is weighed in the step (1), and is uniformly mixed with the chopped and melted refractory polymer material and the modified waste ceramic powder in the step (3), and then the mixture is subjected to slush molding and tape casting to form a film.
Examples 1-4 of the present invention all prepared materials with excellent fire resistance and similar properties, and comparative studies were performed on the samples of examples 1-4, and the study methods and results are shown below:
(1) research on oxygen index of waste ceramic composite building material
The oxygen index is the minimum oxygen concentration required to maintain smooth combustion of a sample in an oxygen-nitrogen mixture stream under specified conditions, expressed as a volume percent of oxygen, and is shown in Table 1 for examples 1-4:
TABLE 1 oxygen index comparison Table for examples 1-4
| Test items | Example 1 | Example 2 | Example 3 | Example 4 |
| Oxygen index/% | 33.7 | 37.6 | 35.2 | 38.3 |
As can be seen from Table 1, the oxygen index of example 4 is the largest, and the flame retardant property is the best, which shows that the flame retardant property of the composite building material is effectively improved by adding the inorganic ceramic powder; the oxygen indexes of the embodiments 1 to 4 reach 33 to 39 percent, which shows that the waste ceramic composite building materials prepared by the invention have excellent fire resistance and flame retardant property.
(2) Thermogravimetric analysis
The waste ceramic composite building materials prepared in example 2 and example 4 were respectively crushed, and the weight loss due to heat was measured by a thermogravimetric analyzer (usa. pe. co) under a nitrogen atmosphere, with a sample weight of 150mg, a temperature rise rate of 20 ℃/min, and a test temperature range of 60 to 550 ℃, and the results are shown in fig. 1:
wherein line a is the thermogravimetric analysis plot of example 2; line b is the thermogravimetric analysis plot of example 4; both the two are thermally decomposed at the temperature of 150 ℃ and 200 ℃, and the decomposed raw materials are small molecular substances such as adsorbed water molecules in the sample; the line b is a uniform decomposition curve, and two weight loss zones appear in the line a at the temperature of 150-200 ℃ and 200-250 ℃ respectively, which indicates that the thermal decomposition of the polystyrene occurs along with the increase of the temperature in the example 2, and no weight loss zone appears in the line b between 150-250 ℃ and indicates that the polystyrene is not decomposed; and with the increase of the temperature, the a line and the b line both have weight loss areas after 250 ℃, which shows that the polystyrene is decomposed at the moment, and the polystyrene is decomposed more along with the gradual increase of the temperature, and after the temperature reaches 500 ℃, the residual amount of example 2 is about 60 percent, and the residual amount of example 4 is about 70 percent, wherein the materials of example 2 are the residual waste ceramic and a small amount of polystyrene resin, example 4 is the residual waste ceramic, inorganic ceramic powder and a small amount of polystyrene resin, and the two materials of the waste ceramic and the inorganic ceramic powder are extremely difficult to burn. In conclusion, the composite material effectively overcomes the technical defect that the initial thermal decomposition temperature of polystyrene is low, the composite material in the embodiment 2 starts to be slowly oxidized at the temperature of 150 ℃, and the composite material in the embodiment 4 starts to be oxidized at the temperature of 250 ℃, so that the fire resistance is improved.
(3) Test of thermal deformation Property
The cured composite materials of example 2 and example 4 were processed into sample strips with a thickness of 3 + -0.5 mm, a width of 60 + -0.5 mm and a length of 30 + -0.5 mm, respectively, and the deformation-temperature curves were measured at a temperature rise rate of 12 ℃/min in a J-1 type high polymer deformation-temperature measuring instrument at a test temperature range of room temperature to 120 ℃, and the deformation temperature of the sample was determined, and the expansion coefficient was calculated, as shown in FIG. 2, wherein a line is the deformation-temperature curve of example 2, and b line is the deformation-temperature curve of example 4:
the thermal deformation of the material can reflect the heat resistance stability of the material to different degrees, and the thermal deformation performance of the material and the material is studied in the following, as can be seen from fig. 2, the thermal deformation temperature of example 2 is between about 90 ℃ and 110 ℃, and the thermal deformation temperature of example 4 is between about 110 ℃ and 120 ℃, which indicates that the thermal deformation performance of example 4 is better, and the initial thermal deformation of example 2 and example 4 is not obvious, indicating that the prepared composite material has excellent fire resistance.
The result shows that the composite material effectively improves the fire resistance of the fire-resistant material, effectively overcomes the technical defect of low initial thermal decomposition temperature of the fire-resistant high polymer material, is not easy to generate thermal deformation at the temperature of 100 ℃, and can be applied to fire-resistant building materials.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The waste ceramic composite building material is characterized by being prepared from the following raw materials in parts by weight: 100 portions and 150 portions of waste ceramic powder; 1-4 parts of a coupling agent; 500 portions of refractory polymer material.
2. The waste ceramic composite building material of claim 1, further comprising 2-8 parts of vitrified powder; the ceramic powder comprises low-temperature ceramic powder, medium-temperature ceramic powder and high-temperature ceramic powder, wherein the low-temperature ceramic powder is aluminum hydroxide or magnesium hydroxide, the medium-temperature ceramic powder is one of montmorillonite, mica powder and diatomite, and the high-temperature ceramic powder is magnesium oxide or kaolin.
3. The waste ceramic composite building material of claim 1, wherein the coupling agent is prepared from the following raw materials in parts by weight: 1-3 parts of an aluminate coupling agent; 5-9 parts of a silane coupling agent;
wherein, the aluminate coupling agent is DL-482, and the silane coupling agent is KH550 or KH 570.
4. The waste ceramic composite building material of claim 1, wherein the refractory polymer material is one or a mixture of any two of polystyrene resin, polyethylene resin and polypropylene resin.
5. The waste ceramic composite building material as claimed in claim 1, wherein the particle size of the waste ceramic powder is 100-200 mesh.
6. The method for preparing the waste ceramic composite building material as claimed in any one of claims 1 to 5, comprising the steps of:
(1) weighing: weighing the following raw materials in parts by weight: 100 portions and 150 portions of waste ceramic powder; 1-4 parts of a coupling agent; 500 portions of refractory polymer material and 1000 portions for standby;
(2) modifying the surface of the waste ceramic powder:
s1, adding the waste ceramic powder into ammonia water, and reacting for 8-12h under the boiling condition to obtain an intermediate;
wherein, the concentration of the ammonia water is 10-20%;
s2, dissolving a coupling agent in a solvent to obtain a coupling agent mixed solution, adding the intermediate into the coupling agent mixed solution under the stirring condition, stirring at 60-80 ℃ for 360min, and drying to obtain modified waste ceramic powder;
(3) preparing a waste ceramic composite building material:
and (3) adding the modified waste ceramic powder obtained in the step (2) into the chopped and melted refractory polymer material, uniformly mixing, and airing at room temperature after a slush molding casting film is formed to obtain the waste ceramic composite building material.
7. The method for preparing the waste ceramic composite building material according to claim 6, wherein 2-8 parts of the ceramic powder is weighed in the step (1), uniformly mixed with the chopped and melted refractory polymer material and the modified waste ceramic powder in the step (3), and subjected to slush molding and film casting to form the film.
8. The method for preparing a waste ceramic composite building material according to claim 6, wherein the solvent of the step S2 is an ethanol solution with a volume fraction of 95%.
9. Use of the waste ceramic composite building material according to claim 1 for preparing a refractory building material.
10. The use according to claim 9, wherein the composite building material is used for interior wall fire resistant materials.
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