CN109650941B - Ceramic sheet synthesized by ceramic polishing waste at low temperature and having humidity regulating function - Google Patents

Ceramic sheet synthesized by ceramic polishing waste at low temperature and having humidity regulating function Download PDF

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CN109650941B
CN109650941B CN201811618879.0A CN201811618879A CN109650941B CN 109650941 B CN109650941 B CN 109650941B CN 201811618879 A CN201811618879 A CN 201811618879A CN 109650941 B CN109650941 B CN 109650941B
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ceramic
ceramic sheet
waste
humidity
polishing waste
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CN109650941A (en
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萧礼标
景镇子
成铭钊
兰浩然
黄玲艳
郦怡
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Shanghai Haigu New Material Technology Co ltd
Monalisa Group Co Ltd
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Shanghai Haigu New Material Technology Co ltd
Monalisa Group Co Ltd
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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
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • 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
    • C04B33/132—Waste materials; Refuse; Residues
    • 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
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/1328—Waste materials; Refuse; Residues without additional clay
    • 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
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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

Abstract

The invention relates to a ceramic sheet synthesized by ceramic polishing waste at low temperature and having a humidity regulating function, which comprises the following raw materials in formula: 30-80% of ceramic polishing waste, 5-25% of calcium oxide source, less than 40% of diatomite, less than 5% of curing agent and 5-15% of water by mass.

Description

Ceramic sheet synthesized by ceramic polishing waste at low temperature and having humidity regulating function
Technical Field
The invention relates to a ceramic sheet synthesized by ceramic waste at low temperature and having a humidity regulating function, belonging to the field of solid waste recycling.
Background
The indoor humidity-regulating material is a novel functional material which can sense the humidity change of indoor air by means of self respiration without any artificial energy and mechanical equipment, thereby automatically regulating the relative humidity of the air. The action mechanism of humidity control materials varies depending on the type, but the moisture vapor is absorbed and released by the capillary condensation of mesopores, which is basically achieved by utilizing the porosity of the materials. In recent decades, attention has been paid to the humidity conditioning function of conventional materials, and some of the conventional materials have been modified to prepare humidity conditioning materials. FIG. 1 is a schematic diagram showing the mechanism of a humidity controlling material. When the indoor environment humidity is too high, the humidity control material can spontaneously absorb water vapor in the indoor air by virtue of a large number of microscopic pores in the humidity control material, so that the indoor humidity is reduced; on the contrary, when the indoor humidity is lower, the humidity control material can spontaneously release water vapor into the air, so as to improve the indoor humidity. Finally, the humidity control material depends on the autonomous 'breathing function', and the humidity in the control room is constant in the optimal range under the condition of not consuming external energy. However, the conventional humidity control materials have limited humidity control ability, i.e., low maximum moisture absorption and poor moisture release ability. Meanwhile, the problems of low moisture absorption and desorption speed and poor durability and corrosion resistance exist.
The ceramic waste mainly refers to waste generated in each process link in the production process of ceramic products, and can be mainly divided into ceramic polishing waste, ceramic non-polishing waste (blank waste, waste glaze, firing waste) and the like. At present, the annual output of Chinese ceramic waste reaches 1800 ten thousand tons, wherein the ceramic polishing waste accounts for more than half of the total amount. The common treatment mode at present is sanitary landfill, but the treatment mode occupies a large amount of land, and the ceramic waste is difficult to naturally degrade. In terms of chemical properties, the organic matter content of the ceramic waste is very low, and more than 95 percent of the ceramic waste is inorganic matter. The main component of the ceramic is silicon dioxide, namely quartz obtained after sintering, and other components have larger difference, some have higher aluminum content and some have higher potassium content, namely the ceramic corresponds to different oxide types. Because of the rich silicon dioxide, the silicon dioxide can be used as a silicon source for synthesizing porous minerals.
At present, there are many patents on the preparation of humidity-controlling materials, and the preparation methods are different, for example, Chinese patent "preparation method of a silica humidity-controlling material" (publication number: CN104402005A) provides a method for synthesizing a functional humidity-controlling material by compounding raw materials such as sodium silicate, polyacrylic acid, dilute nitric acid, deionized water and the like; chinese patent "a preparation method of composite humidity-controlling material" (publication number: CN102964758A) provides a method for synthesizing humidity-controlling material by utilizing polypropylene resin, potassium carbonate, sodium chloride, polyvinyl alcohol, urea, sepiolite and the like. The two methods can effectively prepare materials with certain humidity regulating function, but the raw materials have high cost and very complex preparation process, and a series of organic chemical reactions are required; meanwhile, the prepared material is gel-like and cannot be directly used in the building material industry. For example, Chinese patent ZL200810017527.X discloses a humidity-controlling building material prepared from beta hemihydrate gypsum, plant fiber, super absorbent resin gel, portland cement clinker and the like, which has poor humidity-controlling performance and only barely meets the requirements of industrial standards, and a large amount of resin gel with humidity-controlling function is added into the material, so that the cost is far higher than that of similar building wall materials sold in the market.
Disclosure of Invention
The invention aims to solve the problems in the prior art and synthesize a ceramic thin plate with excellent humidity-regulating performance and certain mechanical strength by using ceramic waste. The invention is synthesized under the condition of low temperature, the reaction energy consumption is low, and no secondary pollution is generated; meanwhile, the invention fully utilizes the raw material characteristics of the ceramic waste, has higher utilization rate of the ceramic waste, effectively carries out resource treatment on the ceramic waste, and prepares the ceramic waste into a ceramic thin plate for building use, thereby realizing element circulation.
In one aspect, the invention provides a ceramic sheet with a humidity conditioning function, and the raw material formula of the ceramic sheet comprises: 30-80% of ceramic waste, 5-25% of calcium oxide source, less than 40% of diatomite, less than 5% of curing agent and 5-15% of water by mass.
The ceramic sheet of the present invention has excellent porosity, especially, a high mesoporous content. Spontaneous humidity regulation can be realized through the capillary condensation of mesopores. The raw materials of the ceramic sheet comprise porous diatomite on one hand, and a proper amount of calcium oxide and a curing agent are added by utilizing silicon dioxide in ceramic waste on the other hand. Therefore, the obtained ceramic sheet not only retains the porosity of the diatomite minerals, but also has acicular tobermorite crystals, further improves the richness of the microporous structure, and simultaneously provides enough strength for the sheet.
In the invention, the maximum moisture absorption capacity of the ceramic sheet in 24 hours can be 80-220 g/m2The 24 hour maximum moisture release may be 70% to 90% of the 24 hour maximum moisture absorption.
In the invention, the flexural strength of the ceramic sheet can be 15-22 MPa.
Preferably, the calcium oxide source is at least one selected from the group consisting of slaked lime, limestone, quicklime and dolomite.
Preferably, the content of the diatomite is 5-40%.
Preferably, the curing agent is commercially available nano silicon, and is preferably at least one selected from alkaline nano silica sol, nano silica solution and nano silicon powder.
Preferably, the ceramic thin plate is a ceramic plate with the thickness less than or equal to 6 mm.
In another aspect, the present invention provides a method for preparing the ceramic sheet, including the steps of:
uniformly mixing the raw materials in proportion to obtain a mixture;
pressing and forming the mixture to obtain a green body;
and (3) treating the green body for 12-24 hours at the temperature of 160-220 ℃ and under the steam pressure of 0.6-2.3 MPa, and drying for 4-12 hours to obtain the ceramic sheet.
The invention is synthesized at low temperature, has low reaction energy consumption and does not produce secondary pollution. Under the low temperature condition, the underground diagenesis process is simulated through gas pressure, the porosity of diatomite minerals is reserved in the reaction process, the growth of acicular tobermorite crystals is promoted, the richness of a micro-pore structure is further improved, and meanwhile, enough strength is provided for the thin plate.
Preferably, the ceramic waste is taken as a 100-mesh screen residue.
Preferably, the pressing pressure is 20 to 40 MPa.
Drawings
FIG. 1: humidity control mechanism diagram of humidity control material.
FIG. 2: indoor building material damping performance test equipment.
FIG. 3: the different amounts of diatomite affect the humidity-regulating performance of the ceramic sheet.
FIG. 4: and (3) a temperature and humidity simulation curve of the ceramic sheet prepared by the diatomite with different doping amounts.
FIG. 5: scanning electron micrographs of ceramic sheets were prepared from ceramic polishing waste.
FIG. 6: scanning electron micrographs of ceramic sheets were prepared from ceramic non-polishing waste.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Disclosed herein is a ceramic sheet having a humidity control function. The humidity adjusting function means that the material achieves the purpose of spontaneously adjusting the indoor air humidity through the automatic absorption and release effect on water vapor. Fig. 1 is a schematic view showing a humidity control mechanism of the ceramic sheet having a humidity control function. As shown in fig. 1, when the humidity of the indoor environment is too high, the ceramic thin plate with humidity control function can spontaneously absorb water vapor in the indoor air by virtue of a large amount of microscopic pores therein, so as to reduce the indoor humidity; on the contrary, when the indoor humidity is lower, the ceramic thin plate with the humidity adjusting function can spontaneously release water vapor into the air, so that the indoor humidity is improved. Finally, the ceramic sheet with the humidity adjusting function depends on the autonomous 'breathing function', and the humidity in the adjusting and controlling room is constantly in the optimal range under the condition of not consuming external energy.
In the present disclosure, the ceramic sheet refers to a ceramic plate with a thickness of 6mm or less.
In the present disclosure, the ceramic sheet may be used as a wall tile, a ceiling tile, a floor tile, or the like.
In one embodiment, the raw material formulation of the ceramic sheet comprises: 30-80% of ceramic waste, 5-25% of calcium oxide source, less than 40% of diatomite, less than 5% of curing agent and 5-15% of water by mass.
The ceramic waste refers to waste generated in each process link in the production process of ceramic products, and comprises two main types. One kind of waste ceramic polishing material, named as waste polished tile material and waste polished tile slag, is produced mainly in the grinding and polishing process of ceramic sheet, and consists of mainly silicon carbide, magnesium oxide, magnesium chloride, brick scraps, etc. the waste ceramic polishing material accounts for over half of the total output of waste ceramic material. Another class is ceramic non-polishing waste, i.e., ceramic waste other than ceramic polishing waste, including green body waste, waste glaze, firing waste, and the like. The green body waste refers to waste green body materials. The waste glaze refers to waste glaze. The fired waste refers to a defective product or a scrap after firing. The components of the waste are similar to those of ceramic polishing waste, and the waste is mainly characterized by being massive, large in granularity, relatively high in activity and relatively easy to recycle. The main difference between the ceramic polishing waste and the ceramic non-polishing waste is that the polishing waste has low activity and is not easy to participate in the reaction, so the reaction condition in the production process is more rigorous, and the requirement on the addition content of the curing agent and the diatomite is higher. In one embodiment, the ceramic waste may be entirely ceramic polishing waste. In this embodiment, preferably, the raw material formulation of the ceramic sheet includes: by mass, 30-55% of ceramic polishing waste, 10-15% of a calcium oxide source, 20-40% of diatomite, 4-5% of a curing agent and 5-15% of water. In another embodiment, the ceramic waste may use ceramic non-polishing waste, for example, at least one selected from green body waste, waste glaze, firing waste. In this embodiment, preferably, the raw material formulation of the ceramic sheet includes: by mass, 50-80% of ceramic non-polishing waste, 5-15% of calcium oxide source, 5-20% of diatomite, 1-3% of curing agent and 5-10% of water.
The calcium oxide source can be selected from one or more of slaked lime, limestone, quicklime and dolomite which are mixed according to any proportion to obtain a commercial industrial grade calcium oxide source.
The content of diatomite is below 40%. If the content of the diatomite is too high, the product structure is too loose, so that the product is easy to expand and crack and difficult to form, the yield of the product is greatly reduced, and the addition amount of the diatomite is not more than 40%. More preferably, the content of the diatomaceous earth is 5 to 40%, still more preferably 10 to 40%, and still more preferably more than 30% and 40% or less. In the range of 40% or less, the ceramic sheet has more excellent humidity control performance and mechanical strength when the content of the diatomite is higher. The diatomite is one of porous minerals, has large specific surface area, has a micro pore structure which is independently dispersed small pores and is completely different from other pore structures (such as layered pores of sepiolite), can not be blocked in the reaction process, and is beneficial to the synthesis of the humidity-regulating ceramic sheet.
The curing agent can promote the growth of acicular tobermorite crystals, and further improve the richness of a micro-pore structure, thereby providing enough strength for the thin plate. If the curing agent is not contained, the amount of crystal growth is small, the crystal growth is slow, the reaction rate is greatly reduced, and if the curing agent has sufficient strength, a long reaction time is required.
The content of the curing agent may be 5% or less. If the content of the curing agent is continuously increased, the reaction process is not obviously improved.
The curing agent can be selected from at least one of alkaline nano silica sol, nano silica solution and nano silica powder, wherein the alkaline nano silica sol is more preferable because the reaction is facilitated to be carried out in the forward direction under alkaline conditions, and the nano silica sol has stronger dispersibility and higher reactivity.
The ceramic sheet of the present disclosure may have a 24h maximum moisture absorption of 220g/m2The maximum moisture absorption capacity of superior products far exceeding the maximum moisture absorption capacity of superior products specified in the industry standard JC-T2082-one 2011 humidity-adjusting function indoor building decoration material is not less than 60g/m2An index of (1); the maximum moisture release capacity can reach more than 70% of the maximum moisture absorption capacity in 24 hours, the requirement of the specification is met, the moisture absorption and release rate of the product is high, and the humidity adjusting capacity is strong. Meanwhile, the flexural strength of the material can reach 15-22 MPa, the mechanical property of the material also meets the national building material strength standard for non-bearing block walls, and the material can be applied to wall and floor tiles for interior decoration and the like.
The ceramic thin plate disclosed by the invention is of a porous structure, and the specific surface area of the ceramic thin plate is 20-60 m2·g-1The average pore diameter is 10 to 20nm, and the pore volume is 0.08 to 0.28cc g-1. The ceramic sheet of the present disclosure contains acicular tobermorite crystals. The width of the tobermorite crystal is 0.1-2 μm, and the length is 1-20 μm。
Next, an embodiment of the method for producing a ceramic thin plate of the present disclosure will be described.
Firstly, taking ceramic waste powder according to mass percent: a calcium oxide source: diatomite: curing agent: 30-80% of water: 5-25%: 0-40%: 0-5%: 5-15%, and uniformly stirring to obtain a mixture. The stirring means may be grinding or the like.
Wherein the ceramic waste powder can be obtained by drying, crushing, sieving and grading the ceramic waste and taking the residue of 100 meshes. The ceramic waste with the fineness can ensure that the particles are contacted more closely in the reaction process and the reaction is more sufficient.
And pressing and forming the mixture to obtain a green body. The pressing pressure can be 20-40 MPa. In one example, a 5.5mm thick sheet is pressed.
And (3) treating the green body at a low temperature for 12-24 hours in a wet environment with the temperature of 160-220 ℃ and the steam pressure of 0.6-2.3 MPa. According to the treatment, the underground diagenesis process is simulated through gas pressure under the low-temperature condition, the porosity of the diatomite mineral is reserved in the reaction process, the growth of the acicular tobermorite crystal is promoted, the richness of the microporous structure is further improved, and meanwhile, enough strength is provided for the thin plate. In one example, the green body is placed in a reaction kettle, water is added into the reaction kettle, the addition amount of the water can be 8-10% of the volume of the reaction kettle, and then heating treatment is carried out.
After the low-temperature treatment, the ceramic sheet is dried to obtain a ceramic sheet having a humidity control function. The drying method can be natural drying or drying at 50-80 ℃ for 4-12 hours. The water content can be dried to 0-1%.
Through detection, the moisture adjusting performance of the thin plate is far higher than the maximum moisture absorption capacity of superior products specified in the industry standard JC-T2082-plus 2011 moisture adjusting function indoor building decoration material and is not lower than 60g/m2The maximum moisture release amount is not less than 70% of the maximum moisture absorption amount, the mechanical property also meets the national building material strength standard for non-bearing block walls, and the building material can be applied to wall and floor tiles for indoor decoration and the like.
The embodiments of the present invention have the following advantages.
1. The components are simple, particularly, the ceramic waste which is difficult to utilize is used as a main raw material (the addition amount is 30-80%), the reutilization rate is high, and the resource reutilization of the ceramic waste is effectively realized.
2. Compared with other conventional humidity control materials, the humidity control ceramic sheet of the embodiment of the invention has excellent performance and far exceeds the high-grade product requirement of the industrial standard.
3. The embodiment of the invention utilizes a low-temperature synthesis method to prepare the humidity-regulating ceramic sheet, and has the advantages of simple production process, low energy consumption in the preparation process, low production cost and high process feasibility.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Weighing 80% of ceramic non-polishing waste, 5% of calcium oxide, 8% of diatomite, 2% of curing agent (nano silicon powder, obtained from Shanghai Xinding metallurgy materials Co., Ltd., type Si-4) and 5% of water in mass ratio, fully grinding and stirring the raw materials, and then pressing and molding to obtain a green body, wherein the sample is a square thin plate with the side length of 100mm and the thickness of about 5.5mm, and the molding pressure is 20 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 180 ℃, the steam pressure is 0.98MPa, and the time is 12 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 8 hours to obtain the humidity-regulating ceramic sheet.
FIG. 2 is a schematic diagram of humidity control performance testing equipment built according to the industry standard JC-T2082-2011 humidity control function indoor building decoration material, and the constant temperature and humidity in the equipment are controlledAnd monitoring the amount of water vapor adsorbed or released by the product in real time, thereby representing the maximum amount and the rate of moisture adsorption and release of the material so as to judge the quality of the moisture regulation performance of the material. The maximum moisture absorption capacity of 24 hours is 90g/m2And the maximum 24h moisture release capacity is 70% of the maximum moisture absorption capacity, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 16MPa, and the requirement on the strength of the building material is also met.
Example 2
Weighing 60% of ceramic non-polishing waste, 10% of calcium oxide, 20% of diatomite, 2% of curing agent (nano silicon dioxide solution, obtained from Hangzhou intelligent titanium purification technology Co., Ltd., type VK-S01N) and 8% of water in mass ratio, fully grinding and stirring the raw materials, and then pressing and forming to obtain a green body, wherein the sample is a square thin plate with the side length of 100mm and the thickness of about 5.5mm, and the forming pressure is 25 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 160 ℃, the steam pressure is 0.6MPa, and the time is 16 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 8 hours to obtain the humidity-regulating ceramic sheet. The maximum moisture absorption capacity of 24 hours is 130g/m2And the maximum 24h moisture release amount is 76% of the maximum moisture absorption amount, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 18MPa, and the requirement on the strength of the building material is also met.
Example 3
Weighing 30% by mass of ceramic non-polishing waste, 25% by mass of calcium oxide, 33% by mass of diatomite, 2% by mass of curing agent (nano silicon powder, available from Shanghai Xinding metallurgy materials Co., Ltd., type Si-4) and 10% by mass of water, fully grinding and stirring the raw materials, pressing and molding the raw materials to obtain a green body, wherein the sample is a square thin plate with the side length of 100mm and the thickness of about 5.5mm, and the molding pressure is 20 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 200 ℃, the steam pressure is 1.56MPa, and the time is 12 h; sample removal after completion of treatmentAnd then drying the ceramic sheet in an oven at 80 ℃ for 8 hours to obtain the humidity-regulating ceramic sheet. The maximum moisture absorption capacity of 24 hours is 180g/m2And the maximum 24h moisture release amount is 78% of the maximum moisture absorption amount, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 21MPa, and the requirement on the strength of the building material is also met.
Example 4
Weighing 80% of ceramic polishing waste, 5% of calcium oxide, 5% of diatomite, 5% of curing agent (nano silicon dioxide solution, obtained from Hangzhou intelligent titanium purification science and technology limited company, with the model of VK-S01N) and 5% of water in mass ratio, fully grinding and stirring the raw materials, and then pressing and molding the raw materials to obtain a green body, wherein the sample is a rectangular thin plate with the length of 100mm, the width of 50mm and the thickness of 5.5mm, and the molding pressure is 30 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 200 ℃, the steam pressure is 1.56MPa, and the time is 24 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 4 hours to obtain the humidity-regulating ceramic sheet. The maximum moisture absorption capacity of 24h is 82g/m2And the maximum 24h moisture release amount is 72% of the maximum moisture absorption amount, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 15MPa, and the requirement on the strength of the building material is also met.
Example 5
Weighing 50% of ceramic polishing waste, 15% of calcium oxide, 20% of diatomite, 4% of curing agent (alkaline nano-silica sol, purchased from Shandong Yousio chemical engineering Co., Ltd., model ZS-30) and 11% of water in mass ratio, fully grinding and stirring the raw materials, and then pressing and molding to obtain a green body, wherein the sample is a square thin plate with the side length of 100mm and the thickness of about 5.5mm, and the molding pressure is 35 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 220 ℃, the steam pressure is 2.30MPa, and the time is 18 h; taking out the treated sample, and drying in an oven at 80 ℃ for 4h to obtain the humidity-regulating ceramicA thin plate. The maximum moisture absorption capacity of 24 hours is 140g/m2And the maximum 24h moisture release capacity is 85% of the maximum moisture absorption capacity, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 22MPa, and the requirement on the strength of the building material is also met.
Example 6
Weighing 30% of ceramic polishing waste, 15% of calcium oxide, 40% of diatomite, 5% of curing agent (nano silicon dioxide solution, obtained from Hangzhou intelligent titanium purification science and technology limited company, with the model of VK-S01N) and 10% of water in mass ratio, fully grinding and stirring the raw materials, and then pressing and molding the raw materials to obtain a green body, wherein the sample is a rectangular thin plate with the length of 100mm, the width of 50mm and the thickness of 5.5mm, and the molding pressure is 30 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 200 ℃, the steam pressure is 1.56MPa, and the time is 24 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 4 hours to obtain the humidity-regulating ceramic sheet. The maximum moisture absorption capacity of 24 hours is 210g/m2And the maximum 24h moisture release capacity is 81 percent of the maximum moisture absorption capacity, which is superior to the related industry standard. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample can reach 19MPa, and the requirement on the strength of the building material is also met.
Comparative example 1
Weighing 70% of ceramic polishing waste, 15% of calcium oxide, 4% of curing agent (nano silicon dioxide solution) and 11% of water (comparative example 5) in mass ratio, fully grinding and stirring the raw materials, and then pressing and molding to obtain a green body, wherein the sample is a rectangular thin plate with the length of 100mm, the width of 50mm and the thickness of 5.5mm, and the molding pressure is 35 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 220 ℃, the steam pressure is 2.30MPa, and the time is 18 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 4 hours to obtain the humidity-regulating ceramic sheet.
FIG. 3 shows the ceramics obtained under different diatomite mixing amountsMoisture absorption and desorption curves of the sheet. The ceramic tailings (ceramic waste) in fig. 3 refer to the unreacted ceramic polishing waste used in example 5, and the "diatomaceous earth 0%" curve refers to the sample obtained in comparative example 1 without added diatomaceous earth; the "diatomaceous earth 20%" curve corresponds to the sample of example 5; the "diatomaceous earth 40%" curve corresponds to the sample in example 6. As can be seen from the curves, the incorporation of diatomaceous earth as an additive has a large influence on the wettability of the ceramic sheet. When the ambient humidity is as high as 75%, the unreacted ceramic polishing waste can hardly absorb water vapor and has no humidity control performance. Sheet without any additive (FIG. 3, "diatomaceous earth 0%"), and 24-hour maximum moisture absorption of 50g/m2Still below 60g/m as required in the row standard2When the content of the diatomite is 40 percent, the maximum moisture absorption amount is improved to 200g/m2The above. Meanwhile, in any formula, the maximum moisture release capacity of the product meets the requirement, and the moisture absorption and release rate of the product is high.
The ceramic polishing waste material in comparative example 1 was replaced with a ceramic non-polishing waste material, and the obtained ceramic sheet was also tested to have a wettability not meeting the specification.
FIG. 4 shows the performance of the ceramic sheet material in temperature and humidity simulation experiments under different diatomite doping amounts. The temperature is controlled to change in a sine rule in 24h in the simulation experiment, and because the indoor temperature is closely related to the humidity, the relative humidity in the space should change in a cosine rule synchronously. When the sample does not have the humidity regulation performance, the fluctuation range of the humidity is large; when the sample has strong humidity regulation performance, the fluctuation range of the humidity is small, which indicates that the sample can well control the indoor humidity to be in the optimum range. The results in the figure show that the products with different diatomite mixing amounts have good and bad performance, but all have better humidity regulating performance. In the range of 40% or less, the higher the content of diatomaceous earth, the better the humidity control performance.
FIG. 5 shows a scanning electron micrograph of a ceramic sheet prepared from the ceramic polishing waste in example 6, and FIG. 6 shows a scanning electron micrograph of a ceramic sheet prepared from the ceramic non-polishing waste in example 3. As is evident from both figures, a large number of acicular tobermorite crystals are generated in the sample, the pore volume is increased, and the contribution to the moisture-adjusting performance of the sheet material is huge.
Comparative example 2
Weighing 60% by mass of ceramic non-polishing waste, 10% by mass of calcium oxide, 20% by mass of diatomite and 10% by mass of water (comparative example 2), fully grinding and stirring the raw materials, and then performing compression molding to obtain a green body, wherein the sample is a square thin plate with the side length of 100mm and the thickness of about 5.5mm, and the molding pressure is 25 MPa; transferring the formed green body into a closed reaction kettle, adding a certain volume of water into the reaction kettle, wherein the specific addition amount is 10% of the volume of the reaction kettle, and then carrying out heating treatment, wherein the heating temperature is 160 ℃, the steam pressure is 0.6MPa, and the time is 16 h; and taking out the treated sample, and drying the sample in an oven at 80 ℃ for 8 hours to obtain the humidity-regulating ceramic sheet. The maximum moisture absorption capacity of 24 hours is 85g/m2And the moisture content is better than the related industry standard, but the maximum moisture content of 24h is 62 percent of the maximum moisture absorption amount, and the requirement of 70 percent of the industry standard is not met. Meanwhile, the three-point method is used for testing the flexural strength, and the result shows that the flexural strength of the sample is only 8MPa and does not meet the strength requirement of the building material.
The ceramic non-polishing waste material in the comparative example 2 is replaced by the ceramic polishing waste material, and the obtained ceramic sheet does not meet the strength requirement of the building material through testing.
The specific surface area, pore volume, and average pore diameter were measured by the BET nitrogen adsorption method. The specific surface area of the ceramic sheet obtained in example 1 was 21.0m2·g-1Pore volume of 0.087cc g-1The average pore diameter is 14.8 nm; the specific surface area of the ceramic sheet obtained in example 2 was 36.5m2·g-1Pore volume of 0.197cc g-1The average pore diameter is 13.1 nm; the ceramic sheet obtained in example 3 had a specific surface area of 57.2m2·g-1Pore volume of 0.254cc g-1The average pore diameter is 12.8 nm; the ceramic sheet obtained in example 4 had a specific surface area of 20.7m2·g-1Pore volume of 0.089cc g-1The average pore diameter is 16.9 nm; the ceramic sheet obtained in example 5 had a specific surface area of 38.6m2·g-1The pore volume was 0.211cc g-1The average pore diameter is 16.2 nm;the specific surface area of the ceramic sheet obtained in example 6 was 59.2m2·g-1Pore volume of 0.278cc g-1The average pore diameter is 13.4 nm; the ceramic sheet obtained in comparative example 1 had a specific surface area of 4.5m2·g-1The pore volume is 0.017cc g-1The average pore diameter is 14.4 nm; the ceramic sheet obtained in comparative example 2 had a specific surface area of 18.3m2·g-1Pore volume of 0.087cc g-1The average pore diameter was 19.1 nm.

Claims (6)

1. A ceramic sheet synthesized by ceramic polishing waste at low temperature and having a humidity regulating function is characterized in that the raw material formula of the ceramic sheet comprises: by mass, 30-55% of ceramic polishing waste, 10-15% of a calcium oxide source, 20-40% of diatomite, 4-5% of a curing agent and 5-15% of water; the curing agent is at least one selected from alkaline nano silica sol, nano silica solution and nano silica powder;
the ceramic thin plate is of a porous structure, and the specific surface area of the ceramic thin plate is 20-60 m2•g-1An average pore diameter of 10 to 20nm and a pore volume of 0.08 to 0.28cc-1(ii) a The ceramic thin plate contains acicular tobermorite crystals;
the ceramic sheet has a maximum moisture absorption of 80-220 g/m in 24 hours2The maximum 24-hour moisture release amount is 70-90% of the maximum 24-hour moisture absorption amount;
the flexural strength of the ceramic sheet is 15-22 MPa.
2. The ceramic sheet of claim 1, wherein the source of calcium oxide is selected from at least one of slaked lime, limestone, quicklime, dolomite.
3. The ceramic sheet according to claim 1, wherein the ceramic sheet has a thickness of 6mm or less.
4. A method for producing a ceramic sheet according to any one of claims 1 to 3, comprising the steps of:
uniformly mixing the raw materials in proportion to obtain a mixture;
pressing and forming the mixture to obtain a green body;
and (3) treating the green body for 12-24 hours at the temperature of 160-220 ℃ and under the steam pressure of 0.6-2.3 MPa, and drying to obtain the ceramic sheet.
5. The production method according to claim 4, wherein the ceramic polishing waste takes a 100-mesh-size fraction.
6. The method according to claim 4, wherein the pressing pressure is 20 to 40 MPa.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102086116A (en) * 2009-12-08 2011-06-08 沈阳临德陶瓷研发有限公司 Method for preparing calcium silicate board from ceramic polishing waste
CN103172333A (en) * 2011-12-22 2013-06-26 浙江阿斯克新型保温材料有限公司 Technology method for preparing ultra-light torbay mullite calcium silicate heat preservation material
CN104402010A (en) * 2014-11-06 2015-03-11 西南科技大学 Preparation method of xonotlite-type calcium silicate material
CN105439548A (en) * 2014-08-07 2016-03-30 辽宁利永盛新材料有限公司 Ceramic-polishing-waste-containing breathing brick and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102086116A (en) * 2009-12-08 2011-06-08 沈阳临德陶瓷研发有限公司 Method for preparing calcium silicate board from ceramic polishing waste
CN103172333A (en) * 2011-12-22 2013-06-26 浙江阿斯克新型保温材料有限公司 Technology method for preparing ultra-light torbay mullite calcium silicate heat preservation material
CN105439548A (en) * 2014-08-07 2016-03-30 辽宁利永盛新材料有限公司 Ceramic-polishing-waste-containing breathing brick and preparation method thereof
CN104402010A (en) * 2014-11-06 2015-03-11 西南科技大学 Preparation method of xonotlite-type calcium silicate material

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