CN114349479B - Flaky alumina reinforced building thin ceramic plate and preparation method thereof - Google Patents
Flaky alumina reinforced building thin ceramic plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flaky alumina reinforced building thin ceramic plate and a preparation method thereof, belonging to the technical field of building ceramic preparation. The blank raw materials of the flaky alumina reinforced building thin ceramic plate comprise a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot-shaped structure on the surface; the mass ratio of the flaky alumina with the surface provided with the aluminum oxide with the convex dot-shaped structure to the ceramic matrix raw material is 3: 97-9: 91; the ceramic matrix raw material comprises: 29-66 parts by mass of a clay raw material, 7-15 parts by mass of a high-alumina raw material, 24-45 parts by mass of a feldspar dust removal powder-containing feldspar raw material and 8-20 parts by mass of a quartz raw material containing quartz dust removal powder; wherein, the mass percent of feldspar dust removal powder contained in the feldspar raw materials is not less than 50%, and the mass percent of quartz dust removal powder contained in the quartz raw materials is not less than 50%.
Description
Technical Field
The invention relates to a strengthening method of a building thin ceramic plate, belonging to the technical field of building ceramic preparation.
Background
The thinning of the building ceramic plate can not only reduce the consumption of mineral raw materials, reduce the waste discharge and shorten the firing period, but also reduce the related transportation and building load cost, and meet the development targets of energy conservation, consumption reduction, green and low carbon in the ceramic manufacturing industry. The thinning preparation of the building ceramic plate can reduce the usage amount of raw materials by about 60 percent and save energy by more than 40 percent. However, after the ceramic plate is thinned, the bearing capacity (breaking strength) of the ceramic plate is remarkably reduced, so that the service safety and reliability of the ceramic plate are reduced. Therefore, improving the mechanical properties of the architectural ceramic plate (developing a strengthening and toughening technology) is an effective means for realizing 'thinning without reducing the quality', and is one of the problems to be solved urgently in producing the architectural thin ceramic plate at present. Has important significance for promoting green and sustainable development of the building ceramic industry.
Two-dimensional reinforcement is an effective method for ceramic reinforcement, and is widely researched and applied in the field of ceramic reinforcement at present, and the application range of the two-dimensional reinforcement in the field of fine ceramics is far larger than that in the field of building ceramics. The mechanical property of the ceramic can be enhanced by utilizing the bridging, pinning and deflecting effects of the two-dimensional reinforcement on the cracks. The two-dimensional reinforcement is a reinforcing phase material with a two-dimensional shape, and the common two-dimensional reinforcement is mainly a fiber/whisker reinforcing phase and comprises alumina fibers, alumina silicate fibers, zirconia fibers, mullite fibers, silicon carbide whiskers and the like.
However, the dispersion characteristic of the whisker/fiber reinforcement is very important for the mechanical strengthening effect of the whisker/fiber reinforcement, and the uniform dispersion of the whisker/fiber in the building ceramic matrix is difficult to realize by the existing wet ball milling or dry mixing process, so that the application of the whisker/fiber is greatly limited. In contrast, the platelet material has the dual characteristics of the micron powder and the nano powder, is not easy to generate agglomeration, and has better dispersion performance and better reinforcing effect. Flaky Al 2 O 3 Is a functional ceramic powder material developed in recent years, not only has a typical two-dimensional platelet structure, but also has alpha-Al 2 O 3 Can be used as a reinforcement of materials such as ceramics, glass, metal and the like. At present, flaky Al 2 O 3 The research on reinforced and toughened ceramics mainly focuses on the field of fine ceramics (such as Al) 2 O 3 、ZrO 2 、TiO 2 WC, SiC, etc.), while relatively little research has been conducted in the field of architectural ceramic panels. CN 104355607A and CN 104355651B realize the reinforcement and toughening of the thin ceramic plate by simultaneously introducing inorganic crystal whiskers and flaky alumina powder into the building ceramic; however, this method uses only the tabular alumina having a small width/particle diameter (0.4 to 0.5 μm, 0.5 to 3 μm), and has little influence on densification of the building ceramics, but hardly exerts the composite strength of the tabular aluminaChemical/structural enhancement effects. Although the flaky alumina with larger width/grain diameter (more than 3 mu m) is beneficial to realizing the composite reinforcement of a flaky structure, the addition of the flaky alumina can obviously reduce the compactness of the building ceramic, and the interface bonding between the flaky alumina with large grain diameter and the building ceramic matrix is poorer, so that the strengthening and toughening effect of the flaky alumina is difficult to exert.
Disclosure of Invention
In view of the above, the invention provides a flaky alumina reinforced building thin ceramic plate and a preparation method thereof, wherein flaky alumina with convex dot-shaped alumina on the surface is introduced, and the inhibition effect of large-particle-size flaky alumina on the densification of building ceramics is weakened by enhancing the interface bonding of large-particle-size flaky alumina and the building ceramics, so that the technical problems that the compactness of the building ceramics is remarkably reduced by the large-particle-size flaky alumina, the interface bonding of the building ceramics is poor, and the mechanical strength and the toughness of the building ceramics are not favorably improved are solved.
In particular, in a first aspect, the present invention provides a sheet alumina reinforced architectural thin ceramic slab. The blank raw materials of the flaky alumina reinforced building thin ceramic plate comprise a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot-shaped structure on the surface; the mass ratio of the flaky alumina with the surface provided with the aluminum oxide with the convex dot-shaped structure to the ceramic matrix raw material is 3: 97-9: 91; the ceramic matrix raw material comprises: 29-66 parts by mass of a clay raw material, 7-15 parts by mass of a high-alumina raw material, 24-45 parts by mass of a feldspar dust removal powder-containing feldspar raw material and 8-20 parts by mass of a quartz raw material containing quartz dust removal powder; wherein, the mass percent of feldspar dust removal powder contained in the feldspar raw materials is not less than 50%, and the mass percent of quartz dust removal powder contained in the quartz raw materials is not less than 50%.
The surface of the flaky alumina powder is modified, and the surface of the flaky alumina powder is introduced with the aluminum oxide (alpha-Al) with the convex point structure based on a heterogeneous nucleation mechanism 2 O 3 Point-like particles), thereby increasing the surface roughness of the flake alumina, increasing the contact area of the flake alumina and the building ceramic matrix and enhancing the twoThe interface of (3) is bonded. The strong interface combination of the flaky alumina and the building ceramic matrix is beneficial to realizing the composite strengthening effect of the flaky alumina, and the mechanical strength of the thin ceramic plate can be greatly improved by combining the composite strengthening effect with the particle strengthening and matrix strengthening effects.
Moreover, the dust removal powder is generally used as solid waste for landfill treatment, and the feldspar dust removal powder and the quartz dust removal powder are innovatively used as blank raw materials of the ceramic plate, so that the forming temperature of a viscous phase in the building ceramic can be reduced, the sintering driving force of the building ceramic can be increased, the inhibition effect of the addition of the flaky alumina on the densification of the building ceramic can be weakened, and the preparation of the high-density building ceramic is facilitated; moreover, the introduction of quartz dust removal powder is beneficial to SiO 2 The glass phase is melted, so that the content of the network formers in the glass phase can be increased, the mechanical strength of the glass phase can be improved, and the thin ceramic plate can be effectively reinforced. In addition, the feldspar dust removal powder and the quartz dust removal powder can realize the reutilization of solid wastes, and have important significance for the green and low-carbon manufacture of the building thin ceramic plate.
Preferably, the mass of the aluminum oxide with the convex dot-shaped structure is 3-8% of that of the flaky aluminum oxide.
Preferably, the width of the flake alumina is more than 3 μm, preferably 3 to 10 μm; the width-thickness ratio of the flaky alumina is 3-8.
Preferably, the median particle size of the feldspar dust removal powder and the quartz dust removal powder is below 7 mu m.
Preferably, preparing the flaky alumina with the aluminum oxide with the convex dot structure on the surface: adding flaky alumina powder and a dispersing agent into an alumina precursor aqueous solution, and uniformly dispersing to form a suspension; dropwise adding an alkaline precipitator into the suspension under the stirring condition, so that the precipitated product aluminum hydroxide is distributed in a dotted manner and is coated on the surface of the flaky alumina; after filtering and cleaning, collecting solid matters, drying and calcining the solid matters, converting the punctate aluminum hydroxide on the surface of the flaky alumina into alpha-alumina, and obtaining the flaky alumina with the aluminum oxide with the convex punctate structure on the surface.
PreferablyControlling the introduction amount of the aluminum oxide with the convex point structure by adjusting the concentration of trivalent aluminum ions in the aluminum oxide precursor aqueous solution and the mass ratio of the flaky aluminum oxide powder to the precursor aqueous solution; preferably, the concentration of trivalent aluminum ions in the precursor water solution is 0.01-0.3 mol/L; further preferably, the alumina precursor is AlCl 3 、AlCl 3 ·6H 2 O、Al 2 (SO 4 ) 3 ·18H 2 At least one of O.
Preferably, the punctate distribution of the precipitated product aluminum hydroxide is realized by controlling the stirring speed and the dropping speed of the alkaline precipitator; preferably, the stirring speed is 100-500 rpm, and the dropping speed of the alkaline precipitator is 5-15 mL/min.
Preferably, the calcination temperature is 1100-1350 ℃, and the heat preservation time is 0.5-2 h.
In a second aspect, the present invention provides a method for preparing any one of the plate-shaped alumina reinforced architectural thin ceramic plates. The preparation method comprises the following steps:
uniformly mixing a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot-shaped structure on the surface to obtain ceramic blank powder;
and pressing and molding ceramic blank powder, and firing to obtain the flaky alumina reinforced building thin ceramic plate.
Preferably, the firing temperature is 1150-1220 ℃, and the heat preservation time of the highest firing temperature is 20-40 min.
Drawings
FIG. 1 is a schematic view of an exemplary preparation of a plate-shaped alumina reinforced architectural thin ceramic plate;
fig. 2 is a microscopic structural view of a cross section of the thin ceramic plate prepared in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. The content herein means a mass percentage content unless otherwise specified.
The blank raw material of the flaky alumina reinforced building thin ceramic plate comprises a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot structure on the surface. The prior art mentions the use of small particle size alumina to reinforce ceramic plates. However, the addition of the small-particle-size flaky alumina has little influence on the compactness of the building ceramic, but the composite strengthening effect of the flaky alumina structure is difficult to exert; although the flaky alumina with large particle size (more than 3 mu m) is beneficial to realizing the composite reinforcement of a flaky structure, the addition of the flaky alumina can obviously reduce the compactness of the architectural ceramic, and the interface bonding between the flaky alumina with large particle size and the architectural ceramic matrix is poor, so that the strengthening and toughening effects of the flaky alumina are difficult to exert. The technical problems to be solved by the invention are as follows: enhancing the interface combination of large-particle-size flaky alumina and building ceramic; secondly, the inhibition effect of the large-particle-size flaky alumina on the densification of the building ceramic is weakened.
Through sharp development, the invention introduces flaky alumina with aluminum oxide with convex dot-shaped structures on the surface into the ceramic plate. The flaky structure of the flaky alumina is beneficial to constructing a micro-area layered composite structure, thereby being beneficial to realizing the deflection and bridging of cracks and exerting the strengthening effect of the flaky structure. The invention selects large-size flaky alumina with larger width (more than or equal to 3 mu m), which is beneficial to exerting the composite strengthening effect of the flaky alumina. In addition, the flaky alumina powder is used as hard and brittle phase ceramic particles to be added into the building ceramic, so that the effect of particle reinforcement can be achieved; and the coefficient of thermal expansion of the tabular alumina (. apprxeq.8.5X 10) -6 K -1 ) Higher than the thermal expansion coefficient of the glass phase in the architectural ceramics (approximately equal to 5-8 multiplied by 10) -6 K -1 ) And residual compressive stress is introduced into the glass matrix phase due to thermal mismatch of the two phases, so that the generation and the expansion of cracks can be effectively inhibited, the weak phase (glass phase) in the architectural ceramic is strengthened, and the mechanical strength of the architectural ceramic is favorably improved.
More importantly, the surface roughness of the flaky alumina can be greatly increased by the flaky alumina with the convex point-shaped structure, so that the contact area of the flaky alumina and the building ceramic matrix is increased, and the interface combination of the flaky alumina and the building ceramic matrix is favorably enhanced; when the ceramic thin plate bears stress, the flaky alumina can effectively transfer and disperse load, and the function of reinforcing the building ceramic is achieved.
The flake alumina powder with the convex dot structure is modified flake alumina powder. Surface modification is carried out on the flaky alumina powder by utilizing a chemical precipitation technology, and alpha-Al is introduced on the surface of the flaky alumina powder based on a heterogeneous nucleation mechanism 2 O 3 And (4) point-shaped particles, thus preparing the flaky alumina with a convex point-shaped structure on the surface. The preparation of modified tabular alumina powder is illustrated. Based on a chemical precipitation process, placing flaky alumina powder with the width of 3-10 mu m and the width-thickness ratio of 3-8 and a dispersing agent into a precursor solution of alumina, performing ultrasonic dispersion treatment, and slowly dropwise adding the precipitating agent while stirring until the pH value of a suspension is 9.0-10.0; and (3) filtering to obtain a solid substance, re-dispersing the obtained solid substance in absolute ethyl alcohol for cleaning, then filtering, dispersing and cleaning again, and repeating the cleaning step for 1-3 times. And then drying and calcining to attach the point alumina to the surface of the flake alumina, thereby preparing the flake alumina powder with the surface provided with the convex point-structured alumina, namely the modified flake alumina powder.
In some embodiments, the precursor solution of alumina may be AlCl 3 、AlCl 3 ·6H 2 O、Al 2 (SO 4 ) 3 ·18H 2 Any one of O aqueous solution and Al in precursor solution 3+ The concentration can be controlled to be 0.01-0.30 mol/L. By adjusting Al in the alumina precursor solution 3+ The concentration and the mass ratio of the precursor solution to the flaky alumina powder can realize the regulation and control of the introduction amount of the convex point-shaped alumina. Preferably, the mass of the alumina introduced by the precursor (i.e. the mass of the convex punctate alumina) is between 3% and 8% of the mass of the plate-shaped alumina. The introduction amount is too low, so that the formed dot structure is not obvious, and the purpose of increasing the surface roughness of the flaky alumina is difficult to achieve. The introduction amount is too high, so that on one hand, a continuous coating layer structure rather than a point-shaped structure is easily formed; on the other hand, more alumina is introduced from the precursor solution, and chemical precipitation is carried outThe process is less operable and requires the consumption of large amounts of dispersion medium and precipitant.
The kind of the dispersant is not limited. In some embodiments, the dispersing agent may be any one of PEG 2000, PEG 6000, sodium carboxymethyl cellulose, polyvinyl pyrrolidone. The mixing amount of the dispersing agent can be 0.1-2% of the mass of the precursor solution of the alumina. The addition of a certain amount of dispersant can promote the obtainment of uniformly dispersed flaky alumina suspension, and lays a foundation condition for chemical precipitation.
In some embodiments, the precipitant may be industrial ammonia NH 3 ·H 2 O, wherein NH 3 The mass percentage of the component (A) is 25-28%. The dropping speed can be 5-15 mL/min. The stirring mode can be mechanical stirring by adopting a paddle stirrer or a magnetic stirrer, and the rotating speed is 100-500 rpm. The selection of slower stirring speed and faster precipitant dripping speed can conveniently obtain discontinuously distributed precipitation products (Al (OH) 3 ) And (3) a film coating layer, namely, the precipitated product is distributed on the surface of the flaky alumina in a dotted manner.
Before drying, absolute ethyl alcohol with low surface tension can be used for cleaning and removing high surface tension water on the surface of the flaky alumina, hard agglomeration of the flaky alumina powder in the drying process is avoided (the hard agglomeration can cause hardening/caking of the flaky alumina powder after subsequent calcining treatment), and then the modified flaky alumina powder with excellent dispersion property can be obtained after calcining.
In some embodiments, the parameters of the drying process may be: the drying temperature is 60-100 ℃, and the drying time is 2-6 h. The parameters of the calcination treatment process may be: the method is carried out in a muffle furnace, the calcining temperature is 1100-1350 ℃, and the heat preservation time is 0.5-2 h. The dotted Al (OH) on the surface of the flake alumina after calcination 3 Can be converted into alpha-Al 2 O 3 Thus, the sheet alumina with raised dot structure can be prepared. Therefore, the surface roughness of the flaky alumina can be greatly increased, the contact area of the flaky alumina and the building ceramic matrix can be further increased, and the interface bonding of the flaky alumina and the building ceramic matrix can be enhanced; then the thin ceramic plate is supportedWhen the load is stressed, the flaky alumina can effectively transmit and disperse the load, and plays a role in reinforcing the building ceramic.
The method is characterized in that the aluminum oxide particles distributed in a point shape are introduced into the surface of the flaky aluminum oxide by a chemical precipitation method to prepare the flaky aluminum oxide with a convex point-shaped structure so as to increase the surface roughness of the flaky aluminum oxide, thereby enhancing the interface combination of the flaky aluminum oxide and a building ceramic matrix and ensuring the realization of a composite strengthening effect.
It is noted that the acid etching method may be used to introduce etching pits on the surface of the tabular alumina, thereby increasing the surface roughness of the tabular alumina. The acid corrosion method comprises the following specific operation steps: preparing a sulfuric acid solution with the mass fraction of 30-50% and a hydrochloric acid solution with the mass fraction of 3-5%, and mixing the two solutions according to the mass ratio of 1:1 to prepare an acid solution; weighing a certain amount of flaky alumina powder, adding the flaky alumina powder into an acid solution to prepare a suspension, and controlling the mass concentration of the suspension to be 15-30%; thirdly, placing the suspension in a reaction kettle, and carrying out hydrothermal treatment for 1-3 h at the temperature of 80-120 ℃; and fourthly, after hydrothermal treatment, filtering and intercepting the solid matter, washing the solid matter for 1-3 times by using absolute ethyl alcohol, and drying the solid matter to obtain the modified flaky alumina. The method is characterized in that etching pits are introduced on the surface of the flaky alumina by an acid corrosion method, so that the surface roughness of the flaky alumina is increased. However, this method is difficult to operate, has a certain risk of strong acid, and is not an economical and reliable method because the strength of the flaky alumina itself is reduced by acid corrosion. The reinforcing effect of the modified flaky alumina obtained by the acid corrosion method on the ceramic plate is not as good as that of the flaky alumina modified by the dotted structure on the ceramic plate.
Preparing a ceramic matrix raw material. Weighing 29-66 parts by mass of clay raw material, 7-15 parts by mass of high-alumina raw material, 24-45 parts by mass of feldspar raw material (containing not less than 50 wt% of feldspar dust removal powder) and 8-20 parts by mass of quartz raw material (containing not less than 50 wt% of quartz dust removal powder). Ball clay, high-white bentonite, illite, talc mud and black mud belong to clay raw materials. Bauxite and calcined alumina belong to high-alumina raw materials. Albite, potassium feldspar and potassium alumina sand belong to feldspar raw materials. The silicon micropowder belongs to a quartzite raw material. In some embodiments, the ceramic matrix feedstock comprises: 3-16 parts of sodalite powder, 5-18 parts of potassium feldspar, 3-11 parts of potassium aluminum sand, 8-20 parts of illite, 2-4 parts of talc mud, 16-28 parts of ball clay, 3-6 parts of high-whiteness bentonite, 0-8 parts of black mud, 4-8 parts of bauxite, 3-6 parts of calcined alumina and 4-20 parts of silicon micropowder; wherein the mass of feldspar dust removal powder contained in the feldspar raw materials is not less than 50%, and the mass of quartz dust removal powder contained in the quartz raw materials is not less than 50%. Preferably, the quality of feldspar dust removal powder contained in the feldspar raw materials is not higher than 70%, and the quality of quartz dust removal powder contained in the quartz raw materials is not higher than 70%. More preferably, the quality of feldspar dust removal powder contained in the feldspar raw material is not higher than 60%, and the quality of quartz dust removal powder contained in the quartz raw material is not higher than 60%.
The feldspar dust removal powder and the quartz dust removal powder are processing byproducts formed in the processes of crushing, grinding, screening and the like of feldspar and quartz raw materials and are also called as dust removal ash. Preferably, the usage amount of the feldspar dust removal powder is not less than 50 wt% of the feldspar raw material, and the usage amount of the quartz dust removal powder is not less than 50 wt% of the quartzite raw material. More preferably, the median particle size of the feldspar dust removal powder and the quartz dust removal powder is less than or equal to 7 mu m. The smaller particle size of the feldspar dust removal powder is controlled, so that the specific surface energy of the feldspar material is increased, the liquid phase forming temperature is reduced, and the sintering driving force is increased; meanwhile, the aim of introducing the quartz dust removal powder is to promote the melting of small-particle quartz in a liquid phase and increase SiO in the liquid phase/glass phase 2 The content of the glass phase is increased, and the mechanical strength of the glass phase is improved.
The ceramic matrix raw material is prepared by adopting wet ball milling and spray drying, and the median particle size of the ceramic matrix raw material can be 12-18 microns.
And uniformly mixing the flaky alumina with the convex dot-shaped structure and the ceramic matrix raw material by using a dry powder mixer to obtain ceramic body powder. In some embodiments, the mass ratio of the platy alumina with the convex dot-shaped structures to the ceramic matrix raw material can be 3: 97-9: 91. The modified flaky alumina is too small in mixing amount, so that the enhancement effect is not obvious; and the excessive mixing amount of the modified flaky alumina can inhibit sintering, so that the density of the ceramic is low, and the reinforcing effect of the flaky alumina is not good for being exerted.
In some embodiments, the dry powder mixer may be any one of a horizontal twin-screw powder mixer, a V-type rotary mixer, and a drum-type high-speed mixer. By adopting a dry mixing mode, the self flaky structure and the surface dotted structure of the flaky alumina can be prevented from being damaged, and the better enhancement effect of the flaky alumina can be further ensured.
Increasing the compactness of architectural ceramics is crucial to improving the mechanical properties thereof. The invention innovatively introduces feldspar dust removal powder and quartz dust removal powder into the ceramic blank body: on one hand, the recycling of solid wastes can be realized, and the green low-carbon manufacturing of the thin ceramic plate is facilitated; on the other hand, by introducing the dust removal powder with a lower grain size, the temperature point for forming a viscous phase (glass phase) in the architectural ceramic can be reduced, so that the sintering driving force of the architectural ceramic can be increased, the inhibiting effect of the addition of the flaky alumina on the sintering densification of the architectural ceramic can be weakened, and the high-density sintering of the architectural ceramic can be ensured. In addition, the introduction of the quartz dust removal powder is beneficial to SiO 2 The glass phase is melted, so that the content of the network formers in the glass phase can be increased, the mechanical strength of the glass phase can be improved, and the thin ceramic plate can be effectively reinforced. The invention develops a new application of the dust removal powder, which is different from the application of the dust removal powder as a filler in a cement-based composite material, and the dust removal powder is applied to a ceramic material, so that the densification of ceramic sintering is promoted.
And (3) preparing a thin ceramic plate. Carrying out dry pressing molding on the ceramic body powder which is uniformly mixed to prepare a ceramic body; and then firing the ceramic blank to obtain the thin ceramic plate. The firing temperature of the thin ceramic plate can be 1150-1220 ℃, and the high-temperature heat preservation time can be 20-40 min. Of course, overglaze, decorative patterns and protective glaze may be applied to the surface of the green body before firing. The thin ceramic plate can have a length of 1200 to 3600mm, a width of 600 to 1800mm, and a thickness of 3 to 10.5 mm. The bending strength of the thin ceramic plate is more than 50 MPa.
Example 1
The preparation method of the flaky alumina reinforced building thin ceramic plate comprises the following specific steps.
1) Preparing modified flaky alumina powder. Weighing 7.8 parts by mass of AlCl 3 Adding proper amount of water to prepare Al 3+ Alumina precursor solution with the concentration of 0.01 mol/L; 97 parts by mass of flaky alumina (average width of 3 μm, width-to-thickness ratio = 3) and 0.1 part by mass of polyvinylpyrrolidone (average molecular weight of 8000) were weighed, added to the alumina precursor solution, sonicated for 30 min, and then mechanically stirred with a magnetic stirrer at a stirring speed of 100 rpm. Dropwise adding an ammonia water precipitator into the suspension by using a separating funnel, wherein the dropwise adding speed is controlled to be 15 mL/min; and simultaneously, monitoring the pH value of the suspension in real time by using a pH meter, and stopping titration of the precipitator when the pH value of the suspension reaches 9.0. Carrying out suction filtration on the suspension after titration, intercepting solid matters, washing with absolute ethyl alcohol once, and carrying out suction filtration again; then putting the solid matter after suction filtration into a blast drying oven for drying treatment (drying at 60 ℃ for 6 h); after drying, the powder is placed in a corundum crucible, and high-temperature calcination treatment is carried out in a muffle furnace (keeping the temperature at 1350 ℃ for 0.5 h) to prepare the modified flaky alumina powder. The modified flaky alumina powder is flaky alumina with aluminum oxide with a raised dot structure on the surface. Wherein, the mass of the aluminum oxide with the convex point structure introduced by the precursor is 3 percent of that of the flaky aluminum oxide.
2) And preparing ceramic body powder. Weighing 8 parts by mass of sodalite powder, 8 parts by mass of sodalite dust removal powder (the median particle size is 5.2 microns), 5 parts by mass of potassium feldspar dust removal powder (the median particle size is 6.8 microns), 5 parts by mass of potassium aluminum sand, 6 parts by mass of potassium aluminum sand dust removal powder (the median particle size is 3.9 microns), 11 parts by mass of illite, 2 parts by mass of talc mud, 28 parts by mass of ball clay, 3 parts by mass of high white bentonite, 8 parts by mass of bauxite, 3 parts by mass of calcined alumina, 4 parts by mass of silicon micropowder and 4 parts by mass of silicon micropowder dust removal powder (the median particle size is 1.8 microns), adding 0.2 part by mass of a blank reinforcing agent (modified starch) and 0.5 part by mass of a dispersing agent (water glass), carrying out ball milling for 12 hours, uniformly mixing, carrying out iron removal and ageing on the slurry, and measuring to obtain a ceramic blank with the median particle size of 12 microns; then spray drying is carried out to prepare the ceramic matrix raw material. Weighing 9 parts by mass of modified flaky alumina powder and 91 parts by mass of ceramic matrix raw material, and placing the raw materials in a horizontal double-helix powder mixer for dry mixing treatment to obtain ceramic body powder.
3) And (3) preparing a thin ceramic plate. Carrying out dry pressing molding on the uniformly mixed ceramic powder to obtain a ceramic blank; and then, firing the ceramic blank in a high-temperature roller kiln to obtain the thin ceramic plate. Wherein the sintering temperature is 1150 ℃, and the high-temperature fire-keeping time is 40 min.
Fig. 2 is a microscopic structural view of a cross section of the thin ceramic plate prepared in example 1. As can be seen from the figure, the flaky alumina is tightly combined with the interface of the building ceramic matrix, and the interface has no defects such as air holes, cracks and the like.
The thin ceramic slabs obtained in example 1 were cut according to GB/T3810.4-2016 ceramic tile test method part 4: measurement of modulus of rupture and breaking Strength the bending strength (modulus of rupture) of a sample of a thin ceramic plate was 75.6. + -. 6.7 MPa.
Example 2
The preparation method of the flaky alumina reinforced building thin ceramic plate comprises the following specific steps.
1) Preparing modified flaky alumina powder. Weighing 37.8 parts by mass of AlCl 3 ·6H 2 Adding O into proper amount of water to prepare Al 3+ Alumina precursor solution with the concentration of 0.3 mol/L; weighing 92 parts by mass of flaky alumina (average width of 10 μm, width-to-thickness ratio = 8) and 2 parts by mass of PEG 2000, adding into the alumina precursor solution, performing ultrasonic treatment for 50 min, and then performing mechanical stirring by using a magnetic stirrer, with the stirring speed set at 500 rpm. Dropwise adding an ammonia water precipitator into the suspension by using a separating funnel, wherein the dropwise adding speed is controlled to be 5 mL/min; and simultaneously, monitoring the pH value of the suspension in real time by using a pH meter, and stopping titration of the precipitator when the pH value of the suspension reaches 10.0. Filtering the suspension after titration, trapping solid matters, washing with absolute ethyl alcohol for three times,carrying out suction filtration again; then putting the solid matter after suction filtration into a blast drying oven for drying treatment (drying for 2 hours at 100 ℃); and after drying, placing the powder in a corundum crucible, and placing the corundum crucible in a muffle furnace for high-temperature calcination treatment (keeping the temperature at 1100 ℃ for 2 hours) to obtain the modified flaky alumina powder. The modified flaky alumina powder is flaky alumina with aluminum oxide with a raised dot structure on the surface. Wherein the mass of the aluminum oxide with the convex point structure introduced by the precursor is 8 percent of that of the flaky aluminum oxide.
2) And preparing ceramic body powder. Weighing 4 parts by mass of sodalite powder, 4 parts by mass of sodalite dust removal powder (the median particle size is 5.2 mu m), 9 parts by mass of potassium feldspar dust removal powder (the median particle size is 6.8 mu m), 3 parts by mass of potassium alumina sand dust removal powder (the median particle size is 3.9 mu m), 20 parts by mass of illite, 3 parts by mass of talc mud, 16 parts by mass of ball clay, 6 parts by mass of high-whiteness bentonite, 3 parts by mass of black mud, 4 parts by mass of bauxite, 6 parts by mass of calcined alumina, 5 parts by mass of silicon micropowder and 5 parts by mass of silicon micropowder dust removal powder (the median particle size is 1.8 mu m), adding 0.2 part by mass of a green body reinforcing agent (modified starch) and 0.5 part by mass of a dispersing agent (water glass), ball-milling for 10 hours, uniformly mixing, and carrying out iron removal and aging on the slurry, and measuring that the median particle size of the prepared ceramic blank is 15 mu m; then spray drying is carried out to prepare the ceramic matrix raw material. Weighing 3 parts by mass of modified flaky alumina powder and 97 parts by mass of ceramic matrix raw material, and placing the raw materials in a horizontal double-helix powder mixer for dry mixing treatment to obtain ceramic body powder.
3) And (3) preparing a thin ceramic plate. Carrying out dry pressing molding on the ceramic body powder which is uniformly mixed to prepare a ceramic body; and firing the ceramic blank in a high-temperature roller kiln to obtain the thin ceramic plate. Wherein the sintering temperature is 1190 ℃, and the high-temperature fire-keeping time is 30 min.
The thin ceramic slabs prepared in example 2 were cut according to GB/T3810.4-2016 ceramic tile test method part 4: measurement of modulus of rupture and breaking Strength the bending strength (modulus of rupture) of a sample of a thin ceramic plate was measured to be 82.5. + -. 8.1 MPa.
Example 3
The preparation method of the flaky alumina reinforced building thin ceramic plate comprises the following specific steps.
1) Preparing modified flaky alumina powder. Weighing 32.6 parts by mass of Al 2 (SO 4 ) 3 ·18H 2 O, adding proper amount of water to prepare Al 3+ Alumina precursor solution with the concentration of 0.1 mol/L; weighing 95 parts by mass of flaky alumina (average width of 5 μm, width-to-thickness ratio = 5) and 0.5 part by mass of sodium carboxymethylcellulose, adding into the alumina precursor solution, performing ultrasonic treatment for 20 min, and then performing mechanical stirring by using a magnetic stirrer, wherein the stirring speed is set to 300 rpm. Dropwise adding an ammonia water precipitator into the suspension by using a separating funnel, wherein the dropwise adding speed is controlled to be 10 mL/min; and simultaneously monitoring the pH value of the suspension in real time by using a pH meter, and stopping titration of the precipitator when the pH value of the suspension reaches 9.5. Carrying out suction filtration on the suspension after titration, intercepting solid matters, washing twice by using absolute ethyl alcohol, and carrying out suction filtration again; then putting the solid matter after suction filtration into a blast drying oven for drying treatment (drying for 4 hours at 80 ℃); and after drying, placing the powder in a corundum crucible, and placing the corundum crucible in a muffle furnace for high-temperature calcination treatment (keeping the temperature at 1200 ℃ for 1.5 h) to obtain the modified flaky alumina powder. The modified flaky alumina powder is flaky alumina with aluminum oxide with a raised dot structure on the surface. Wherein, the mass of the aluminum oxide with the convex point structure introduced by the precursor is 5 percent of that of the flaky aluminum oxide.
2) And preparing ceramic body powder. Weighing 3 parts by mass of sodalite powder, 6 parts by mass of sodalite dust removal powder (the median particle size is 5.2 mu m), 5 parts by mass of potassium feldspar, 6 parts by mass of potassium feldspar dust removal powder (the median particle size is 6.8 mu m), 3 parts by mass of potassium alumina sand, 4 parts by mass of potassium alumina sand dust removal powder (the median particle size is 3.9 mu m), 8 parts by mass of illite, 4 parts by mass of talc mud, 18 parts by mass of ball clay, 4 parts by mass of high-whiteness bentonite, 8 parts by mass of black mud, 6 parts by mass of bauxite, 5 parts by mass of calcined alumina, 8 parts by mass of silicon micropowder and 12 parts by mass of silicon micropowder dust removal powder (the median particle size is 1.8 mu m), adding 0.2 part by mass of a green body reinforcing agent (modified starch) and 0.5 part by mass of a dispersing agent (water glass), ball-milling for 6 hours, uniformly mixing, and carrying out iron removal and aging on the slurry, and measuring that the median particle size of the prepared ceramic blank is 18 mu m; then spray drying is carried out to prepare the ceramic matrix raw material. Weighing 5 parts by mass of modified flaky alumina powder and 95 parts by mass of ceramic matrix raw material, and placing the raw materials in a horizontal double-helix powder mixer for dry mixing treatment to obtain ceramic body powder.
3) And (3) preparing a thin ceramic plate. Carrying out dry pressing molding on the ceramic body powder which is uniformly mixed to prepare a ceramic body; and firing the ceramic blank in a high-temperature roller kiln to obtain the thin ceramic plate. Wherein the sintering temperature is 1220 ℃, and the high-temperature fire-keeping time is 20 min.
The thin ceramic slabs prepared in example 3 were cut according to GB/T3810.4-2016 ceramic tile test method part 4: measurement of modulus of rupture and breaking Strength the bending strength (modulus of rupture) of a sample of a thin ceramic plate was 96.3. + -. 8.7 MPa.
Comparative example 1
Basically the same as the scheme in the embodiment 1, the difference is mainly that: the comparative example used a flaky alumina powder which was not subjected to modification treatment.
The thin ceramic slabs prepared in comparative example 1 were cut according to GB/T3810.4-2016 ceramic tile test method part 4: measurement of modulus of rupture and breaking Strength the bending strength (modulus of rupture) of a sample of a thin ceramic plate was 56.8. + -. 5.9 MPa.
The bending strength of the thin ceramic plate obtained in comparative example 1 was 24.9% lower than that of the thin ceramic plate obtained in example 1. Therefore, the modification treatment of the flaky alumina (introducing a raised dot structure on the surface of the flaky alumina) is beneficial to improving the mechanical strength of the flaky alumina reinforced thin ceramic plate, namely the modification treatment of the flaky alumina is important for improving the mechanical strengthening effect of the flaky alumina.
Comparative example 2
Basically the same as the scheme in the embodiment 2, the difference is mainly that: the feldspar dust removal powder and the quartz dust removal powder are not used in the comparative example.
And preparing ceramic body powder. Weighing 8 parts by mass of sodalite powder, 18 parts by mass of potassium feldspar, 6 parts by mass of potassium aluminum sand, 20 parts by mass of illite, 3 parts by mass of talc mud, 16 parts by mass of ball clay, 6 parts by mass of high-whiteness bentonite, 3 parts by mass of black mud, 4 parts by mass of bauxite, 6 parts by mass of calcined alumina and 10 parts by mass of silicon micropowder, adding 0.2 part by mass of a blank reinforcing agent (modified starch) and 0.5 part by mass of a dispersing agent (water glass), performing ball milling for 10 hours, uniformly mixing, removing iron and aging slurry, and measuring that the median particle size of the prepared ceramic blank is 18 mu m; then spray drying is carried out to prepare a ceramic matrix raw material; weighing 3 parts by mass of modified flaky alumina powder and 97 parts by mass of ceramic matrix raw material, and placing the raw materials in a horizontal double-helix powder mixer for dry mixing treatment to obtain ceramic body powder.
The thin ceramic slabs prepared in comparative example 2 were cut according to GB/T3810.4-2016 ceramic tile test method part 4: measurement of modulus of rupture and breaking Strength the bending strength (modulus of rupture) of a sample of a thin ceramic plate was 52.7. + -. 4.5 MPa.
The bending strength of the thin ceramic plate obtained in comparative example 2 was 36.1% lower than that of the thin ceramic plate obtained in example 2, which shows that the introduction of feldspar and quartz-based raw material dust removal powder into the composition of the flaky alumina-reinforced thin ceramic plate is advantageous in improving the mechanical strength of the thin ceramic plate.
Claims (6)
1. The flaky alumina reinforced building thin ceramic plate is characterized in that a blank raw material of the flaky alumina reinforced building thin ceramic plate comprises a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot-shaped structure on the surface;
the mass ratio of the flaky alumina with the surface provided with the aluminum oxide with the convex dot-shaped structure to the ceramic matrix raw material is 3: 97-9: 91; the mass of the aluminum oxide with the convex point-shaped structure is 3 to 8 percent of that of the flaky aluminum oxide;
the width of the flaky alumina is 3-10 mu m, and the width-thickness ratio is 3-8;
the ceramic matrix raw material comprises: 29-66 parts by mass of a clay raw material, 7-15 parts by mass of a high-alumina raw material, 24-45 parts by mass of a feldspar dust removal powder-containing feldspar raw material and 8-20 parts by mass of a quartz raw material containing quartz dust removal powder; wherein, the mass percent of feldspar dust removal powder contained in the feldspar raw materials is not less than 50%, and the mass percent of quartz dust removal powder contained in the quartz raw materials is not less than 50%;
the high-alumina raw materials are bauxite and calcined alumina;
the feldspar dust removal powder is processing byproduct dust removal ash formed in the process of crushing, grinding and screening the feldspar material;
the quartz dust removal powder is processing byproduct dust removal ash formed in the crushing, grinding and screening processes of quartz raw materials.
2. The thin ceramic plate for building reinforced by tabular alumina as claimed in claim 1, wherein the median particle diameter of the feldspar dust powder and the quartz dust powder is 7 μm or less.
3. The plate-shaped alumina reinforced building thin ceramic plate as claimed in claim 1, wherein the preparation method of the plate-shaped alumina having the alumina with the convex dot-shaped structure on the surface comprises: adding flaky alumina powder and a dispersing agent into an alumina precursor aqueous solution, and uniformly dispersing to form a suspension; dropwise adding an alkaline precipitator into the suspension under the stirring condition, so that the precipitated product aluminum hydroxide is distributed in a dotted manner and is coated on the surface of the flaky alumina; after filtering and cleaning, collecting solid matters, drying and calcining the solid matters, converting the punctate aluminum hydroxide on the surface of the flaky alumina into alpha-alumina, and obtaining the flaky alumina with the aluminum oxide with the convex punctate structure on the surface.
4. The plate-shaped alumina reinforced building thin ceramic plate as claimed in claim 3, wherein the calcination temperature is 1100-1350 ℃ and the holding time is 0.5-2 h.
5. The method for manufacturing a plate-shaped alumina reinforced building thin ceramic plate according to any one of claims 1 to 4, comprising:
uniformly mixing a ceramic matrix raw material and flaky alumina with aluminum oxide with a raised dot-shaped structure on the surface to obtain ceramic blank powder;
and pressing and molding ceramic blank powder, and firing to obtain the flaky alumina reinforced building thin ceramic plate.
6. The production method according to claim 5, wherein the firing temperature is 1150 to 1220 ℃, and the holding time at the maximum firing temperature is 20 to 40 min.
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