CN114773089A - Nitrogen-doped tungsten-based ferrous crystal glaze ceramic product capable of promoting photocatalytic activity and preparation method thereof - Google Patents

Nitrogen-doped tungsten-based ferrous crystal glaze ceramic product capable of promoting photocatalytic activity and preparation method thereof Download PDF

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CN114773089A
CN114773089A CN202210402669.8A CN202210402669A CN114773089A CN 114773089 A CN114773089 A CN 114773089A CN 202210402669 A CN202210402669 A CN 202210402669A CN 114773089 A CN114773089 A CN 114773089A
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glaze
temperature
ceramic
nitrogen
ferrous
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CN114773089B (en
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刘一军
李嘉胤
曹丽云
黄剑锋
黄玲艳
张金津
潘利敏
汪庆刚
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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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials

Abstract

The invention discloses a nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting photocatalytic activity and a preparation method thereof. The preparation method comprises the following steps: applying tungsten-based ferrous ceramic crystal glaze with optical function activity on the surface of a ceramic body; firing the ceramic body after applying the tungsten-based ferrous ceramic crystal glaze; and calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.

Description

Nitrogen-doped tungsten-based ferrous crystal glaze ceramic product capable of promoting photocatalytic activity and preparation method thereof
Technical Field
The invention belongs to the field of ceramic glaze materials, and particularly relates to a nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting photocatalytic activity and a preparation method thereof.
Background
The building sanitary ceramic industry at home and abroad has been developed greatly in recent years. In addition to the improvement of the yield, the upscaling of products and the diversification of varieties have remarkable progress, and the progress is connected with the progress of decoration technology and devices. The intense competition in the ceramic market has led to the development of many new products, and the crystalline glaze is a decorative material produced under the circumstances. The crystal glaze as a glaze with special effect has unique artistic charm due to the thousand-pose and hundreds-state crystal flowers and the changeable and magnificent and colorful patterns, and is popular and praised by people. At present, the crystal glaze is mainly applied to technical ceramics and daily ceramics, and is relatively rarely applied to building ceramics mainly because of high sintering temperature, long sintering period (more than ten hours) and complex technical conditions of the crystal glaze, and the defects seriously influence the popularization and application of the crystal glaze in the field of building ceramics.
Disclosure of Invention
Aiming at the problems, the invention provides a nitrogen-doped tungsten-based ferrous iron crystal glaze ceramic product for promoting photocatalytic activity and a preparation method thereof.
In a first aspect, the invention provides a preparation method of a nitrogen-doped tungsten-based ferrous crystalline glaze ceramic product for promoting photocatalytic activity. The preparation method comprises the following steps:
will have optical functional activityApplying the tungsten-based ferrous ceramic crystal glaze on the surface of the ceramic body; the tungsten-based ferrous ceramic crystalline glaze comprises the following raw materials: the powder material A comprises 80-90% of powder material A, 5-10% of ferrous tungstate and 5-10% of kaolin in percentage by mass; the powder A comprises the following raw materials: in terms of mass percent, SiO2 15～20％、K3PO4 6～10％、FeCl2 6～10％、Na3AlF6 15～25％、AlPO4 8～15％、Li3PO4 20～30％、Na3PO4 10～20％；
Firing the ceramic body after applying the tungsten-based ferrous ceramic crystal glaze;
and calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.
In the glaze composition composed of conventional oxides such as silicon oxide, aluminum oxide, calcium oxide, sodium oxide, etc., the crystalline component is not easily exposed sufficiently on the surface of the glaze layer, and the active ingredient of the glaze does not easily exhibit good photocatalytic activity. The ground glaze component of the phosphate system has a different melt liquid viscosity and metal ion diffusion rate at high temperature compared to the glaze composition of the oxide system, under which conditions the rate of oriented growth of the crystalline glaze component and the normal distribution within the bulk crystalline glaze layer exhibit significant variation. Specifically, under a phosphate-based ground glaze system, the oriented growth of the ferrocenyl tungstate crystal glaze can be preferentially distributed on the surface of the glaze layer, and one-dimensional orientation is formed, so that conditions can be provided for the sufficient exposure and growth of a high-activity crystal glaze system. In particular, cryolite (Na)3AlF6) The addition of (A) significantly promotes the solubility of the crystalline component in the ground glaze glass phase, ferrous chloride (FeCl)2) The addition of the element (A) can promote the nucleation and crystallization rate of the ferrous tungstate under the high-temperature liquid environment of the glaze, and further obtain a ferrous tungstate crystal with obvious oriented growth. If the above-mentioned crystalline glaze does not contain cryolite and ferrous chloride, the nucleation rate and crystallization growth rate of the ferrous tungstate crystalline glaze are severely limited, and it is difficult to obtain a significant crystal pattern effect even under the same firing conditions. In addition, the invention makes nitrogen element after sinteringThe crystal glaze is introduced with the elements, nitrogen elements can be embedded into the surface of the glass phase of the glaze in the form of solid solution, the surface cation migration can be stabilized by means of nitrogen doping in repeated catalytic circulation, the structural activity is maintained, and the cycle life is further prolonged.
Preferably, the powder A is powder in the form of frit; preferably, the frit is prepared by the following steps: weighing the raw materials according to the content of each component of the powder A, mixing, grinding and sieving the raw materials, keeping the temperature at the first temperature for 10-20 minutes, keeping the temperature at the second temperature for 10-20 minutes, keeping the temperature at the third temperature for 10-20 minutes, taking out the mixture, pouring the mixture into water, and quenching the mixture to prepare a frit; wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1100-1400 ℃; more preferably, the second temperature is 50 to 150 ℃ higher than the first temperature.
Preferably, the mesh number of the screen is 30 to 100 meshes.
Preferably, the particle size of the powder A is 100-300 meshes.
Preferably, the tungsten-based ferrous ceramic crystal glaze generates a ferrous tungstate crystal growing in a one-dimensional orientation under a high-temperature sintering environment.
Preferably, the maximum firing temperature is 800-1300 ℃, and the firing period is 90-170 minutes.
Preferably, the inert atmosphere for calcination is argon.
Preferably, the calcination temperature is 400-800 ℃ and the calcination time is 30-90 minutes.
Preferably, the enamel composition is applied to the surface of the ceramic body in the form of a glaze slip; the glaze slip comprises a dispersant and water in addition to the glaze composition; preferably, the water accounts for 40-60% of the mass of the glaze slip, and the dispersant accounts for 0.1-0.5% of the mass of the glaze slip.
Preferably, the glaze slip forms a crystalline glaze layer with a thickness of 0.05-0.3 mm on the surface of the ceramic body.
In a second aspect, the invention provides a nitrogen-doped tungsten-based ferrous crystalline glaze ceramic product with promoted photocatalytic activity, which is obtained by the preparation method described in any one of the above.
Drawings
FIG. 1 is an XRD pattern of the glaze layer of example 1;
FIG. 2 is a graph of the performance of comparative example 1 and examples 1-3 for photocatalytic degradation of oleylamine;
FIG. 3 is a graph showing the photocatalytic degradation of oleic acid in comparative example 1 and examples 1 to 3.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention. Unless otherwise specified, each percentage refers to a mass percentage. The preparation method of the nitrogen-doped tungsten-based ferrous crystalline glaze ceramic product for promoting photocatalytic activity is exemplified below.
Applying the tungsten-based ferrous ceramic crystal glaze with the optical function activity on the surface of the ceramic body. The composition and specification of the ceramic body are not particularly limited, and a construction ceramic body commonly used in the art may be used.
The tungsten-based ferrous ceramic crystalline glaze comprises the following raw materials: the powder material A comprises 80-90% by mass, 5-10% by mass of ferrous tungstate and 5-10% by mass of kaolin.
The powder A is the main component of the crystal glaze. The powder A comprises the following raw materials: in terms of mass percent, SiO2 15～20％、K3PO4 6～10％、FeCl2 6～10％、Na3AlF6 15～25％、AlPO4 8～15％、Li3PO4 20～30％、Na3PO410 to 20 percent. The powder A is used as the ground coat of the crystal glaze, and provides a liquid environment for nucleation and growth of active ferrous tungstate crystals in a high-temperature environment, so that the active ferrous tungstate crystals can grow at a higher rate.
The composition of the powder A has an important influence on the appearance of the crystalline glaze. As described above, powder A provides a growth environment for nucleation of crystals, promoting rapid nucleation. If the powder A is replaced by the traditional feldspar and clay, the grain size in the crystallized glaze is very small and even the crystal glaze cannot grow normally, and the more crystal orientation growth structure is difficult to obtain. This is because the nucleation rate of the nuclei of ferrous tungstate is low when the above ferrous tungstate crystal glaze is formed using the conventional feldspar clay, and it is difficult to directly nucleate and grow in a short time. And the traditional feldspar and/or clay are used as the ground glaze of the crystalline glaze, so that the crystalline glaze can have a little crystallization effect when the sintering period is more than 15 hours and the heat preservation time of the highest temperature reaches 4-10 hours. The powder A with the composition can form crystal flowers with easily controlled morphology under the conditions that the firing period is 1.5-5 hours (preferably 90-170 minutes), and the heat preservation time of the highest firing temperature is 5-20 minutes, so that the energy consumption can be obviously saved.
The mass percentage of the powder A in the crystallized glaze is controlled to be 80-90% so as to provide a sufficient liquid phase environment in a high-temperature melting state. If the mass percentage of the powder A in the crystal glaze is lower than 80%, the crystal components can not effectively migrate in a high-temperature melting state to promote crystal growth, the crystal glaze is difficult to nucleate, the growth size distribution of crystal nuclei is uneven, and the decorative effect of the crystal glaze is poor. If the mass ratio of the powder A in the crystallized glaze is higher than 90%, the crystal grains are easily melted, the number of the crystallized grains becomes small, and the decorative effect is also deteriorated.
Preferably, said powder a is a powder in the form of a frit. Although the preparation of powder A into a raw material can also promote crystallization, the crystal growth of the crystallized glaze is difficult to control, the repeatability is extremely poor, the crystal size is limited, and the catalytic effect is also limited. In the process of preparing the frit, the raw materials are heated firstly to ensure that the ground glaze is vitrified in advance, so the powder A in the form of the frit has better mixing uniformity than the raw materials, and the size and the components of the crystal flowers generated by nucleation are more uniform.
Weighing the raw materials according to the raw material composition of the powder A, mixing, grinding and sieving to obtain a mixture. The mixing means may be dry mixing. The mesh number of the sieve is preferably 30-100 meshes. And putting the mixture into a crucible, putting the crucible into an electric furnace, keeping the temperature at the first temperature for 10-20 minutes, keeping the temperature at the second temperature for 10-20 minutes, keeping the temperature at the third temperature for 10-20 minutes, taking out the mixture, pouring the mixture into water, and quenching the mixture to obtain the fusion cake. Wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1100-1400 ℃; preferably, the second temperature is 50 to 150 ℃ higher than the first temperature. In some embodiments, the frit is removed from the water, dried, and placed in a ball mill jar for ball milling. For example, the particle size of the grinding ball is 5-20 mm, the ball milling speed is 100-400 r/min, and the material: the mass ratio of the grinding balls is 1: 2-1: 4, grinding is carried out for 4-10 hours, then the ground materials are sieved by a sieve of 100-300 meshes, and drying is carried out for standby. The powder A is prepared into the frit with fine particle size, so that the components of the powder A are fully and uniformly distributed under the high-temperature condition.
Ferrous tungstate is used as an active material in the crystallized glaze to play a role in photocatalysis. The mass percentage of the ferrous tungstate in the crystalline glaze is controlled to be 5-10%. The photocatalytic effect is obviously weakened when the content of the ferrous tungstate is too much or too little. The reason is that the amount of crystal flowers is small due to the low content of the ferrous tungstate, the content of photocatalytic degradation components is reduced, and the catalytic effect is weakened; the high content of ferrous tungstate can also lead to non-uniform nucleation crystal patterns, limited decorative effect and weakened photocatalysis effect.
It should be noted that it is not possible to design ferrous tungstate in the composition of the powder material A, because the addition of ferrous tungstate into the powder material A will cause the growth of the ferrous tungstate in advance during the preparation of the frit, resulting in the failure of the crystal glaze to grow an oriented crystal structure during high temperature firing.
The kaolin contains Al2O3·2SiO2·2H2And (O). The kaolin can increase the melting temperature of the glaze and improve the suspension property so that the glaze is not easy to settle. If the content of the kaolin is too small, the dispersion uniformity and stability of the glaze cannot be effectively ensured; if the content of kaolin is too high, the active ingredients of the glaze are easily wrapped by the kaolin and cannot be exposed, so that the catalytic degradation performance of the crystallized glaze is limited.
Preparing the tungsten-based ferrous ceramic crystalline glaze with the optical function activity. Mixing the powder A, the ferrous tungstate and the kaolin, grinding, sieving and drying to obtain the tungsten-based ferrous ceramic crystal glaze with the optical function activity. Milling may be carried out by ball milling, for example, by controlling the mass: the mass ratio of the grinding balls is 1: 1, grinding for 1-10 hours, sieving by a 300-mesh sieve, and drying for later use.
And sintering the ceramic body after applying the tungsten-based ferrous ceramic crystal glaze with the optical function activity. And (3) sintering by oxidizing flame in a roller kiln, preferably quick sintering. The maximum firing temperature is 800-1300 ℃, and the firing period is 90-170 minutes. The heat preservation time of the highest firing temperature can be 5-20 minutes.
The tungsten-based ferrous ceramic crystal glaze with the optical function activity can be prepared into a glaze slip form and applied to the surface of the ceramic body. The glaze slip contains water and a dispersant in addition to the glaze composition. The mass percentage of water in the glaze slip is 40-60%, and the mass percentage of the dispersing agent is 0.1-0.5%. The dispersant includes, but is not limited to, polyacrylic acid ammonium salts and the like. The components in the glaze slip are uniformly dispersed by stirring. The glaze slip forms a crystal glaze layer with the thickness of 0.05-0.3 mm on the surface of the ceramic body. In this case, the ceramic body may be dried before firing. For example, drying at 50-100 deg.C.
And calcining the sintered ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity. The nitrogen-containing powder can be spread on the surface of the sintered ceramic body. The mass percentage of nitrogen element in the nitrogen-containing powder can be 20-70%. For example, urea powder is spread on the surface of the ceramic body after firing. The dosage of urea powder can be 100cm20.5-2.0 g of urea powder is used on the surface of the ceramic body. The urea powder can also be replaced by melamine and the like. The temperature can be kept at 400-800 ℃ for 30-90 min under the argon atmosphere, so that the decomposition of the nitrogen-containing powder and the doping of nitrogen elements can be controlled. The nitrogen-containing powder cannot be laid on the surface of the ceramic body applied with the tungsten-based ferrous ceramic crystalline glaze and then sintered, because the growth of crystals in a crystalline glaze layer and the formation of a glass phase structure are influenced, and the nitrogen-containing powder is quickly oxidized into a gaseous substance under the high-temperature environment of sintering to lose the expected doping effect. Similarly, it is not possible to introduce nitrogen-containing powder directly into the tungsten-based ferrous ceramic crystal glaze, because this would also affect the crystal growth and glass phase structure formation in the crystal glaze layer, and the nitrogen-containing powder would also be rapidly oxidized into gaseous substances under the high temperature environment of firing and lose the expected doping effect. In addition, the fired ceramic body is directly fired in a nitrogen atmosphere since nitrogen is an inert gasBulk, the desired nitrogen doping cannot be achieved.
The ceramic glaze surface of the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity can decompose or degrade organic matters such as oleic acid, oleylamine and the like under the illumination condition, the degradation rate can even reach over 90 percent, the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product has an obvious promotion effect on the purification of a home environment, and can improve the living environment and the living standard.
Moreover, the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity also has excellent surface decoration effect. The glaze is brown, has beautiful color, strong covering capability, flat and smooth glaze, no pinhole and other defects.
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 insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. 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
The preparation method of the nitrogen-doped tungsten-based ferrous iron crystal glaze ceramic product for promoting the photocatalytic activity comprises the following steps:
1) and preparing a material A. The materials are prepared according to the following mass and chemical component proportion: SiO 22 18％：K3PO4 8％：FeCl 28％：Na3AlF6 22％：AlPO4 13％：Li3PO4 20％：Na3PO4And 11 percent. The powder materials are dry-mixed and ground, the mixture is sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible and put into an electric furnace to be kept warm for 20min at 900 ℃, kept warm for 20min at 1000 ℃, kept warm for 20min at 1400 ℃, taken out and poured into water to be quenched to obtain the fusion cake. Taking out the frits from the water, drying and putting the frits into a ball milling tank, wherein 1/3 are respectively selected from the pebbles with the particle sizes of 5mm, 10mm and 15mm, and the rotating speed is 200 r/minThe clock, control material: the mass ratio of the grinding balls is 1: and 4, grinding for 10 hours, sieving by using a 300-mesh sieve, and drying for later use to obtain powder marked as material A.
2) And preparing a material B. Taking the material A, the ferrous tungstate and the kaolin as the material A according to the mass ratio: ferrous tungstate: 84% of kaolin: 8%: 8 percent of the mixture ratio is proportioned, evenly mixed and put in a ball milling tank, the ball stone is 1/3 with the grain size of 5mm, 10mm and 15mm respectively, the rotating speed is 300 r/min, and the materials are controlled: the mass ratio of the grinding balls is 1:4, grinding for 10 hours, and then sieving by a 200-mesh sieve, wherein the powder is marked as a material B.
3) And adding water into the material B, stirring and uniformly mixing to prepare glaze slurry, and adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of the water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slip on the surface of the ceramic, controlling the glazing thickness to be 0.2mm, drying at 80 ℃, firing by oxidizing flame of a roller kiln, keeping the temperature at 400 ℃ for 15min, heating to 900 ℃ and keeping the temperature for 15min, and controlling the total time of the firing period to be 120 min.
5) Spreading urea powder on the surface of the sintered ceramic body every 100cm2The surface of the ceramic body is calcined for 90 minutes at 400 ℃ in an inert atmosphere by using 0.5g of urea powder, so as to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.
XRD analysis was performed on the glaze layer of the ceramic product of example 1, and the results are shown in fig. 1. Compared with PDF card, known as FeWO4。
SEM analysis and elemental analysis of the glaze layer of the ceramic product of example 1 show that FeWO is present4The crystal is needle-shaped grown in one-dimensional orientation, the surface of the prepared glaze layer has obvious prismatic protrusions, the width can reach 300 mu m, the length exceeds 800 mu m, and the glaze layer is crossed at a certain geometric angle. As can be seen from the element distribution, the proportion of Fe, W and O in the convex element components on the surface of the glaze layer is more, which is similar to the crystal structure FeWO of the crystal glaze in the XRD pattern4The results of (1) correspond to (b); the main element components of the dark part on the surface of the glaze layer are Na, Al, Si and O, the components are from powder A, and the powder A form tungstenic acid under a high temperature stateThe glassy liquid phase environment required for iron crystallization nucleation corresponds. Since the urea powder has a low surface doping amount, nitrogen cannot be detected in the detection limit of the element distribution.
Example 2
The preparation method of the nitrogen-doped tungsten-based ferrous iron crystal glaze ceramic product for promoting the photocatalytic activity comprises the following steps:
1) and (4) preparing a material A. The materials are prepared according to the following mass and chemical component proportion: SiO 22 18％：K3PO4 8％：FeCl 28％：Na3AlF6 22％：AlPO413％：Li3PO4 20％：Na3PO411 percent. The powder materials are dry-mixed and ground, the mixture is obtained by sieving the powder materials with a 100-mesh sieve, the mixture is put into a crucible, the crucible is put into an electric furnace and is insulated for 20min at 900 ℃, is insulated for 20min at 1000 ℃, is insulated for 20min at 1400 ℃, is taken out and is poured into water for quenching to obtain the fusion cake. Taking out the clinker from water, drying and putting into a ball milling tank, wherein 1/3 are respectively selected from the pebbles with the particle size of 5mm, 10mm and 15mm, the rotating speed is 200 r/min, and the materials are controlled as follows: the mass ratio of the grinding balls is 1: and 4, grinding for 10 hours, sieving by using a 300-mesh sieve, and drying for later use to obtain powder material marked as material A.
2) And preparing a material B. Taking the material A, the ferrous tungstate and the kaolin as the material A according to the mass ratio: ferrous tungstate: kaolin 84%: 8%: 8 percent of the mixture ratio is proportioned, evenly mixed and put in a ball milling tank, the ball stone is 1/3 with the grain size of 5mm, 10mm and 15mm respectively, the rotating speed is 300 r/min, and the materials are controlled: the mass ratio of the grinding balls is 1:4, grinding for 10 hours, and then sieving by a 200-mesh sieve, wherein the powder is marked as a material B.
3) And adding water into the material B, stirring and uniformly mixing to prepare glaze slurry, and adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of the water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slip on the surface of the ceramic, controlling the glazing thickness to be 0.2mm, drying at 80 ℃, firing by oxidizing flame in a roller kiln, keeping the temperature at 400 ℃ for 15min, heating to 900 ℃ and keeping the temperature for 15min, and controlling the total time of the firing period to be 120 min.
5) Spreading urea powder on the sintered ceramicSurface of the body, per 100cm2The surface of the ceramic body is calcined for 60 minutes at 600 ℃ in an inert atmosphere by using 1.5g of urea powder, so as to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.
Example 3
The preparation method of the nitrogen-doped tungsten-based ferrous crystalline glaze ceramic product for promoting the photocatalytic activity comprises the following steps:
1) and preparing a material A. The materials are prepared according to the following mass and chemical component proportion: SiO 22 18％：K3PO4 8％：FeCl 28％：Na3AlF6 22％：AlPO4 13％：Li3PO4 20％：Na3PO4And 11 percent. The powder materials are dry-mixed and ground, the mixture is sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible and put into an electric furnace to be kept warm for 20min at 900 ℃, kept warm for 20min at 1000 ℃, kept warm for 20min at 1400 ℃, taken out and poured into water to be quenched to obtain the fusion cake. Taking out the frits from water, drying and putting into a ball milling tank, wherein 1/3 are respectively taken from the pebbles with the particle sizes of 5mm, 10mm and 15mm, the rotating speed is 200 r/min, and the materials are controlled: the mass ratio of the grinding balls is 1: and 4, grinding for 10 hours, sieving by using a 300-mesh sieve, and drying for later use to obtain powder material marked as material A.
2) And preparing a material B. Taking the material A, the ferrous tungstate and the kaolin as the material A according to the mass ratio: ferrous tungstate: 84% of kaolin: 8%: 8% ratio is batched, and the misce bene is and in the ball-milling jar, and the ball stone is got and is respectively 1/3 of footpath grain size 5mm, 10mm, 15mm, and the rotational speed 300 changes/minute, control material: the mass ratio of the grinding balls is 1:4, after grinding for 10 hours, sieving by a 200-mesh sieve, and marking the powder as material B.
3) And adding water into the material B, stirring and uniformly mixing to prepare a glaze slip, and adding ammonium polyacrylate serving as a dispersing agent, wherein the mass percentage of the water in the glaze slip is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slip on the surface of the ceramic, controlling the glazing thickness to be 0.2mm, drying at 80 ℃, firing by oxidizing flame in a roller kiln, keeping the temperature at 400 ℃ for 15min, heating to 900 ℃ and keeping the temperature for 15min, and controlling the total time of the firing period to be 120 min.
5) Spreading urea powder on the surface of the sintered ceramic body every 100cm2The surface of the ceramic body is calcined for 30 minutes at 800 ℃ in an inert atmosphere by using 2.0g of urea powder, so as to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.
Comparative example 1
Preparing a ceramic product:
1) and preparing a material A. The materials are prepared according to the following mass and chemical component proportion: SiO 22 18％：K3PO4 8％：FeCl 28％：Na3AlF6 22％：AlPO4 13％：Li3PO4 20％：Na3PO411 percent. The powder materials are dry-mixed and ground, the mixture is sieved by a 100-mesh sieve to obtain a mixture, the mixture is put into a crucible and put into an electric furnace to be kept warm for 20min at 900 ℃, kept warm for 20min at 1000 ℃, kept warm for 20min at 1400 ℃, taken out and poured into water to be quenched to obtain the fusion cake. Taking out the frits from water, drying and putting into a ball milling tank, wherein 1/3 are respectively taken from the pebbles with the particle sizes of 5mm, 10mm and 15mm, the rotating speed is 200 r/min, and the materials are controlled: the mass ratio of the grinding balls is 1: and 4, grinding for 10 hours, sieving by using a 300-mesh sieve, and drying for later use to obtain powder marked as material A.
2) And preparing a material B. Taking the material A, the ferrous tungstate and the kaolin as the material A according to the mass ratio: ferrous tungstate: kaolin 84%: 8%: 8% ratio is batched, and the misce bene is and in the ball-milling jar, and the ball stone is got and is respectively 1/3 of footpath grain size 5mm, 10mm, 15mm, and the rotational speed 300 changes/minute, control material: the mass ratio of the grinding balls is 1:4, after grinding for 10 hours, sieving by a 200-mesh sieve, and marking the powder as material B.
3) And adding water into the material B, stirring and uniformly mixing to prepare a glaze slip, and adding ammonium polyacrylate serving as a dispersing agent, wherein the mass percentage of the water in the glaze slip is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slip on the surface of the ceramic, controlling the glazing thickness to be 0.2mm, drying at 80 ℃, firing by oxidizing flame in a roller kiln, keeping the temperature at 400 ℃ for 15min, heating to 900 ℃ for 15min, and controlling the total firing period time to be 120 min to obtain the ceramic product.
The ceramic products containing the crystalline glaze obtained in comparative example 1, example 2 and example 3 were subjected to a photocatalytic test. The photocatalytic performance of the samples was tested using a model BL-GHX-V photocatalyst (BILANS Biotech Co., Ltd.).
Cleaning and drying the surface of the ceramic product, uniformly coating a certain amount of oleic acid or oleylamine on the surface of the ceramic product with the length of 6cm multiplied by 1cm, and drying at low temperature to constant weight. The ultraviolet lamp is fixed above the ceramic product. Samples were taken at regular intervals and weighed. The ratio of the remaining content of oleic acid or oleylamine divided by the initial content of oleic acid or oleylamine at different time points was calculated to obtain the remaining content (ratio) of oleic acid or oleylamine, and a curve was drawn. The test conditions were: irradiation intensity of 3.0mW/cm2The dominant wavelength is 253.7nm, the temperature fluctuation is +/-0.1 ℃, and the humidity fluctuation is +/-1%.
Under the same degradation conditions, the residual oleic acid amounts had the following ranking trend: per 100cm2The surface of the ceramic body of (1) is coated with 0g of urea powder (comparative example 1) > per 100cm2The surface of the ceramic body of (1) was coated with 0.5g of urea powder (example 1) > per 100cm2The surface of the ceramic body of (1) was coated with 2.0g of urea powder (example 3) > per 100cm21.5g of urea powder was used for the surface of the ceramic body (example 2). Likewise, the ranking trend of the residual oleylamine amount was: per 100cm2The surface of the ceramic body of (1) is coated with 0g of urea powder (comparative example 1) > per 100cm2The surface of the ceramic body of (1) was coated with 0.5g of urea powder (example 1) > per 100cm2The surface of the ceramic body of (1) was coated with 2.0g of urea powder (example 3) > per 100cm21.5g of urea powder was used for the surface of the ceramic body (example 2). As an example, 8% FeWO is contained4After the tungsten-based ferrous crystalline glaze ceramic product doped with the nitrogen element is degraded for 4 hours, the residual amount of oleic acid and the residual amount of oleylamine can reach below 10% and even below 5%, and are obviously reduced compared with the tungsten-based ferrous crystalline glaze ceramic product not doped with the nitrogen element, which shows that the degradation performance of the ferrous tungstate crystalline glaze ceramic product can be improved by doping the nitrogen element.

Claims (9)

1. A preparation method of a nitrogen-doped tungsten-based ferrous crystalline glaze ceramic product for promoting photocatalytic activity is characterized by comprising the following steps:
applying the tungsten-based ferrous ceramic crystal glaze with optical function activity on the surface of the ceramic body; the tungsten-based ferrous ceramic crystalline glaze comprises the following raw materials: by mass percentage, 80-90% of powder A, 5-10% of ferrous tungstate and 5-10% of kaolin; the powder A comprises the following raw materials: by mass percent, SiO2 15～20%、K3PO4 6～10%、FeCl2 6～10%、Na3AlF6 15～25%、AlPO4 8～15%、Li3PO4 20～30%、Na3PO4 10～20%；
Firing the ceramic body after applying the tungsten-based ferrous ceramic crystal glaze;
and calcining the fired ceramic body and the nitrogen-containing powder in an inert atmosphere to obtain the nitrogen-doped tungsten-based ferrous crystal glaze ceramic product for promoting the photocatalytic activity.
2. The method according to claim 1, wherein the frit A is a frit in the form of a frit; preferably, the preparation process of the frit comprises the following steps: weighing raw materials according to the content of each component of the powder A, mixing, grinding and sieving, keeping the temperature for 10-20 minutes at a first temperature, keeping the temperature for 10-20 minutes at a second temperature, keeping the temperature for 10-20 minutes at a third temperature, taking out, pouring into water, and quenching to prepare a frit; wherein the first temperature is 600-900 ℃, the second temperature is 700-1000 ℃, and the third temperature is 1100-1400 ℃; more preferably, the second temperature is 50 to 150 ℃ higher than the first temperature.
3. The preparation method according to claim 1, wherein the tungsten-based ferrous ceramic crystalline glaze generates a ferrous tungstate crystal growing in a one-dimensional orientation in a high-temperature firing environment.
4. The method according to claim 3, wherein the maximum firing temperature is 800 to 1300 ℃ and the firing period is 90 to 170 minutes.
5. The method of claim 1, wherein the inert atmosphere for calcination is argon.
6. The method according to claim 1, wherein the calcination temperature is 400 to 800 ℃ and the calcination time is 30 to 90 minutes.
7. The method for preparing according to claim 1, wherein the glaze composition is applied to the surface of the ceramic body in the form of a glaze slip; the glaze slip comprises a dispersant and water in addition to the glaze composition; preferably, the water accounts for 40-60% of the glaze slip by mass, and the dispersant accounts for 0.1-0.5% of the glaze slip by mass.
8. The method according to claim 7, wherein the glaze slurry forms a crystalline glaze layer having a thickness of 0.05 to 0.3mm on the surface of the ceramic body.
9. Nitrogen-doped tungsten-based ferrous crystalline enamel ceramic product promoting photocatalytic activity obtained by the production method according to any one of claims 1 to 8.
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