CN115028445A - Low-energy-consumption corrosion-resistant tin oxide electrode for glass kiln and preparation method thereof - Google Patents
Low-energy-consumption corrosion-resistant tin oxide electrode for glass kiln and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-energy-consumption corrosion-resistant tin oxide electrode for a glass kiln and a preparation method thereof, aiming at the enrichment phenomenon of copper in the use process of the tin oxide electrode, and belongs to the technical field of tin oxide electrodes. The technical scheme is as follows: comprises tin dioxide, sintering promoting agent, conductive additive, dispersant and binder; the sintering promoter is zinc oxide and copper oxide, and the mass ratio of the zinc oxide to the copper oxide is 0.3-0.5: 100, and the addition amount of zinc oxide is greater than that of copper oxide; the conductive additive is antimony trioxide, and the mass ratio of the antimony trioxide to the tin dioxide is 0.8-1.5: 100, respectively; the mass ratio of the total weight of the dispersing agent and the binder to the tin dioxide is 0.5-1.5: 100. the tin oxide electrode prepared by the invention has the advantages of high density, low room temperature resistivity, no pollution to glass, strong glass liquid erosion resistance and the like.
Description
Technical Field
The invention relates to the technical field of tin oxide electrodes, in particular to a low-energy-consumption corrosion-resistant tin oxide electrode for a glass kiln and a preparation method thereof.
Background
The tin dioxide electrode is a ceramic material and has good glass erosion resistance. Tin dioxide ceramic is used as an electrode material in a glass electric melting furnace, and the purposes of resisting glass erosion and reducing the energy consumption of the glass furnace can be achieved only by solving the problems of sintering density of the material and improving the conductivity. SnO 2 -Sb 2 O 3 The tin oxide electrode of the CuO system is successfully developed since 1960 s, and is still a mainstream product at home and abroad at present, and the only defect of the system is that copper can be enriched in the use process of the tin oxide electrode, enters glass at a certain concentration, reduces the transmission of a visible region and an infrared region, causes pollution to the glass, and influences the coloring and optical loss of finished glass.
The composition formula of U.S. Pat. No. 3287284 is 0.1-0.5% of CuO, 0.5-1% of ZnO, and 0.7-1.2% of Sb 2 O 3 The other main component is SnO 2 The resistivity of the prepared tin oxide electrode product is less than 1 omega-cm, but the compactness is not high, and the volume density of the product prepared under the contents of 0.05 percent of CuO and 0.95 percent of ZnO is less than 6g/cm 3 The effect of corrosion resistance cannot be achieved.
Chinese patent publication No. CN101001815A discloses the addition of a% CuO (0.025-0.35%), b% ZnO (about 0.5%), c% Sb 2 O 3 (0.5-1.5%) the open porosity of tin dioxide ceramic electrode made of said material is less than 0.7%, and its resistivity is less than or equal to 1.0ohm cm, but said product is too compact, its blank body is brittle, and is easy to produce crack phenomenon, so that it is difficult to ensure its long-term use stability.
Chinese patent publication No. CN101182096 discloses a pharmaceutical composition in accordance with Sb 2 O 3 CuO, ZnO and SnO 2 The mass ratio is 1: 0.5: 0.5: 98, the product has large comprehensive addition amount of copper oxide and zinc oxide, and can cause pollution to glass to a certain extent.
Chinese patent with publication number CN101948304B discloses adding SnO 2 、CuO、Sb 2 O 3 The mass ratio is 100: (0.15-1): (0.1-2.4), the obtained stannic oxide electrode has high density (more than 94%) and low room-temperature resistivity (less than 25 omega cm). However, the added copper oxide has too high content, which causes the phenomenon of copper oxide enrichment and causes pollution of glass, and the room temperature resistivity does not reach the index of advanced products (less than 1 omega cm) in the market.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prepared tin oxide electrode has the advantages of high density, low room temperature resistivity, no pollution to glass, strong glass liquid erosion resistance and the like.
The technical scheme of the invention is as follows:
on one hand, the invention provides a low-energy consumption corrosion-resistant tin oxide electrode for a glass kiln, which comprises tin dioxide, a sintering promoter, a conductive additive, a dispersing agent and a binder; the sintering promoter is zinc oxide and copper oxide, and the mass ratio of the zinc oxide to the copper oxide is 0.3-0.5: 100, and the addition amount of zinc oxide is greater than that of copper oxide; the conductive additive is antimony trioxide, and the mass ratio of the antimony trioxide to the tin dioxide is 0.8-1.5: 100; the mass ratio of the total weight of the dispersing agent and the binder to the tin dioxide is 0.5-1.5: 100.
preferably, the zinc oxide and the copper oxide are submicron or nanometer powder, and the particle size is less than 1 μm.
The powder can greatly improve the surface area and activity of the powder when reaching the granularity below the submicron level, so that the additive can be fully and uniformly dispersed among tin dioxide particles, the phenomenon that large particles are locally enriched is prevented, and meanwhile, the uniformity of overall shrinkage in the material sintering process is ensured, and the problem of cracking caused by inconsistent blank body shrinkage is avoided.
Preferably, the antimony trioxide has the particle size of less than 45 mu m and the average particle size of less than 325 meshes, and is suitable for the electric conduction of a tin oxide blank.
On the other hand, the invention also provides a preparation method of the low-energy-consumption corrosion-resistant tin oxide electrode for the glass kiln, which comprises the following steps:
s1, wet ball milling and mixing: firstly, adding a dispersing agent and a binder into a stirring mill, stirring, adding zinc oxide, copper oxide and antimony trioxide, stirring, uniformly dispersing, adding tin dioxide, stirring, and fully and uniformly mixing to obtain pug;
s2 granulation: putting the pug prepared in the step S1 into a mud storage container, drying for 6-12h at the temperature of not less than 110 ℃, crushing after drying, and sieving by a 40-80 mesh sieve to obtain granulation powder;
s3 cold isostatic pressing: adding the granulation powder prepared in the step S2 into a rubber blank in a steel mold, sealing, vacuumizing, and performing isostatic pressing, wherein the molding pressure is controlled at 100-200 MPa;
s4 destressing: standing the blank formed in the step S3 for 3-5 days, and performing stress relief treatment;
s5, sintering under normal pressure: loading the blank obtained in the step S4 into a sintering furnace, and sintering at 1350-;
s6 post-processing: and (4) cutting and grinding the tin dioxide electrode material obtained in the step (S5) to obtain a tin oxide electrode product.
Preferably, in step S2, the granulated powder has a water content of less than 0.5%, and the molded green body can be directly sintered without drying.
Preferably, in step S5, the normal pressure sintering process includes a low temperature direct degumming in a furnace to remove organic substances and a high temperature sintering stage, wherein air is introduced below 800 ℃ to perform semi-closed sintering, and the whole-closed sintering is performed from 800 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the tin oxide electrode prepared by the invention has the advantages of high density, low room temperature resistivity, no pollution to glass, strong glass liquid erosion resistance and the like. The preparation method has the advantages of simple process, easy operation, short production period, low production cost, stable and reliable product quality and suitability for industrial production.
2. The equipment and the production operation flow adopted by the invention are simple, the production efficiency is high, a small amount of the submicron and nanoscale zinc oxide and copper oxide combined composite sintering agent with better activity and more favorable dispersity is adopted, the prepared powder has good uniformity, the uniformity of the material can be improved by the powder, the uniformity of the overall performance of the material is better facilitated, the enrichment phenomenon of copper oxide is limited, and the prepared product has high purity (SnO) 2 The content reaches more than 98 percent), realizes the densification and high conductivity of the tin oxide electrode ceramic, and achieves the effects of energy conservation and erosion resistance.
3. In the isostatic pressing process, the blank is compressed, and the internal stress is released along with the compression process, but the blank has high strength and inevitably has incomplete stress release. The invention adopts a standing stress-removing measure, can fully stabilize the green body, prevent the cracking phenomenon caused by the instant expansion of the green body in firing and improve the qualification rate of products.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the bulk density and porosity were measured by the GB/T2997-2000 bulk density, apparent porosity and true porosity test methods for densely shaped refractory articles.
Example 1
Tin dioxide powder (granularity 10 mu m, purity more than or equal to 99.5 percent), zinc oxide powder (granularity 0.5 mu m, purity more than or equal to 99 percent), copper oxide powder (granularity 0.5 mu m, purity more than or equal to 99 percent) and antimony trioxide powder according to the mass ratio of tin dioxide, zinc oxide, copper oxide and antimony trioxide of 100: 0.4: 0.1: 1, adding a dispersant sodium polyacrylate and a binder polyvinyl alcohol respectively according to 0.3 percent and 0.2 percent of the mass of the tin dioxide.
The preparation method of the tin oxide electrode material of the embodiment comprises the following steps:
s1 wet ball milling and mixing: firstly, adding a dispersing agent and a binder into a stirring mill at a speed of 100r/min, stirring for 5min, then adding zinc oxide, copper oxide and antimony trioxide at a speed of 50r/min, stirring for 10min, after uniform dispersion, adding tin dioxide powder at a speed of 100r/min, stirring for 10min, and fully and uniformly mixing to obtain pug;
s2 granulation: putting the pug prepared in the step S1 into a mud storage container, drying for 12h at 110 ℃, crushing after drying, and sieving with a 50-mesh sieve to obtain granulation powder;
s3 cold isostatic pressing: adding the granulation powder prepared in the step S2 into a rubber blank in a steel die, sealing, vacuumizing, and carrying out isostatic pressing, wherein the molding pressure is controlled at 150 MPa;
s4 destressing: standing the blank formed in the step S3 for 3 days, and performing stress relief treatment;
s5, sintering under normal pressure: and (4) loading the blank obtained in the step (S4) into a sintering furnace, and carrying out semi-closed normal-pressure sintering at the temperature of below 800 ℃ by introducing air, and carrying out totally closed normal-pressure sintering at the temperature of above 800 ℃ by 1350 ℃.
And S6 post-processing: and (4) cutting and grinding the tin dioxide electrode material obtained in the step (S5) to obtain a tin oxide electrode product, wherein the porosity of the finally obtained product is 5.7%, the room-temperature resistivity is 1.5 omega-cm, and the thickness of the completely non-conductive skin of the fired material is 3 mm.
Example 2
Tin dioxide powder (granularity 20 mu m, purity more than or equal to 99.5 percent), zinc oxide powder (granularity 0.2 mu m, purity more than or equal to 99 percent), copper oxide powder (granularity 0.5 mu m, purity more than or equal to 99 percent) and antimony trioxide powder according to the mass ratio of tin dioxide, zinc oxide, copper oxide and antimony trioxide of 100: 0.3: 0.1: 0.8, and respectively adding a dispersant sodium polyacrylate and a binder polyvinyl alcohol according to 0.5 percent of the mass of the tin dioxide.
The preparation method of the tin oxide electrode material of the embodiment comprises the following steps:
s1, wet ball milling and mixing: firstly, adding a dispersing agent and a binder into a stirring mill for 100r/min, stirring for 5min, then adding zinc oxide, copper oxide and antimony trioxide for 50r/min, stirring for 5min, after uniform dispersion, adding tin dioxide powder for 100r/min, stirring for 10min, and fully and uniformly mixing to obtain pug;
s2 granulation: putting the pug prepared in the step S1 into a mud storage container, drying for 10h at 110 ℃, crushing after drying, and sieving by a 40-mesh sieve to obtain granulation powder;
s3 cold isostatic pressing: adding the granulation powder prepared in the step S2 into a rubber blank in a steel die, sealing, vacuumizing, and carrying out isostatic pressing, wherein the molding pressure is controlled at 100 MPa;
s4 destressing: standing the blank formed in the step S3 for 4 days, and performing stress relief treatment;
s5, sintering under normal pressure: and (4) loading the blank obtained in the step (S4) into a sintering furnace, and carrying out semi-closed normal-pressure sintering at the temperature of below 800 ℃ by introducing air, and carrying out 1390 ℃ normal-pressure sintering at the temperature of above 800 ℃ by totally closing.
And S6 post-processing: and (4) cutting and grinding the tin dioxide electrode material obtained in the step (S5) to obtain a tin oxide electrode product, wherein the porosity of the finally obtained product is 2.5%, and the room-temperature resistivity is 0.9 omega-cm.
Example 3
Tin dioxide powder (granularity 20 mu m, purity more than or equal to 99.5 percent), zinc oxide powder (granularity 0.2 mu m, purity more than or equal to 99 percent), copper oxide powder (granularity 0.2 mu m, purity more than or equal to 99 percent) and antimony trioxide powder according to the mass ratio of tin dioxide, zinc oxide, copper oxide and antimony trioxide of 100: 0.2: 0.1: 1.5, and respectively adding a dispersant sodium polyacrylate and a binder polyvinyl alcohol according to 0.75 percent of the mass of the tin dioxide.
The preparation method of the tin oxide electrode material of the embodiment comprises the following steps:
s1 wet ball milling and mixing: firstly, adding a dispersing agent and a binder into a stirring mill for 100r/min, stirring for 10min, then adding zinc oxide, copper oxide and antimony trioxide for 100r/min, stirring for 5min, after uniform dispersion, adding tin dioxide powder for 100r/min, stirring for 10min, and fully and uniformly mixing to obtain pug;
s2 granulation: putting the pug prepared in the step S1 into a mud storage container, drying for 6h at 110 ℃, crushing after drying, and sieving with a 80-mesh sieve to obtain granulation powder;
s3 cold isostatic pressing: adding the granulation powder prepared in the step S2 into a rubber blank in a steel die, sealing, vacuumizing, and carrying out isostatic pressing, wherein the molding pressure is controlled at 200 MPa;
s4 destressing: standing the blank formed in the step S3 for 5 days, and performing stress relief treatment;
s5, sintering under normal pressure: and (4) loading the blank obtained in the step (S4) into a sintering furnace, carrying out semi-closed atmospheric sintering at the temperature of below 800 ℃ with air, and carrying out totally closed atmospheric sintering at the temperature of above 800 ℃ at the temperature of 1500 ℃.
And S6 post-processing: and (4) cutting and grinding the tin dioxide electrode material obtained in the step (S5) to obtain a tin oxide electrode product, wherein the porosity of the finally obtained product is 2.0%, and the room-temperature resistivity is 0.3 omega-cm.
Comparative example 1
The difference from example 2 is that: tin dioxide (granularity 20 μm, purity more than or equal to 99.5%), zinc oxide (granularity 0.2 μm, purity more than or equal to 99%), copper oxide (granularity 0.5 μm, purity more than or equal to 99%) and antimony trioxide powder according to the mass ratio of tin dioxide, zinc oxide, copper oxide and antimony trioxide being 100: 0.3: 0.3: 0.8 weight percent.
The final product of comparative example 1 had a porosity of 11% and a room temperature resistivity of 50.5. omega. cm.
Comparative example 2
The difference from example 1 is that: tin dioxide (with the particle size of 10 mu m and the purity of more than or equal to 99.5 percent), zinc oxide powder (with the particle size of 0.5 mu m and the purity of more than or equal to 99 percent) and antimony trioxide powder are weighed according to the mass ratio of 100:0.5:1.1 of the tin dioxide, the zinc oxide and the antimony trioxide.
Comparative example 2 the final product had a porosity of 15.0% and a room temperature resistivity of 495. omega. cm.
Comparative example 3
The difference from example 1 is that: in comparative example 3, zinc oxide powder (particle size 48 μm, purity not less than 99%) and copper oxide powder (particle size 48 μm, purity not less than 99%) were used.
Comparative example 3 the final product had a porosity of 9.8%, a room temperature resistivity of 45.2 Ω. cm and a skin thickness of 20mm after firing, which was completely non-conductive.
Comparative example 4
The difference from example 2 is that: in the step S5 normal pressure sintering, after the blank is loaded into a sintering furnace, the 1390 ℃ normal pressure sintering is carried out in a totally closed way from the beginning to the high temperature sintering process without degumming treatment.
Comparative example 4 the final product had a porosity of 7.5% and a room temperature resistivity of 390 Ω. cm.
Comparative example 5
The difference from example 1 is that: in comparative example 5, the zinc oxide powder (with the granularity of 0.5 mu m and the purity of more than or equal to 99 percent) and the copper oxide powder (with the granularity of 0.5 mu m and the purity of more than or equal to 99 percent) are prepared according to the mass ratio of zinc oxide to copper oxide of 0.1: 0.4 weight percent.
Comparative example 5 the final product had a porosity of 4.5% and a room temperature resistivity of 1.1. omega. cm.
As can be seen from the product performance data of examples 1 to 3 and comparative examples 1 to 2, when zinc oxide was used as a sintering aid in the formulation in total and the mass percentage reached 0.5% (comparative example 2), or when the combined amount of both zinc oxide and copper oxide was more than 0.5% (comparative example 1), the porosity and room temperature resistivity of the tin oxide electrode increased significantly; when zinc oxide and copper oxide in the ingredients are used as composite sintering promoting agents, the total amount is less than 0.5 percent by mass, and the content of the zinc oxide is more than that of the copper oxide, Sb in the ingredients is controlled 2 O 3 The mass percentage of the tin dioxide is 0.8-1.5%, and the tin dioxide electrode material with low room temperature resistivity, high density, low energy consumption and erosion resistance can be obtained. Meanwhile, the invention can prevent the pollution to the glass by reducing the content of the copper oxide.
It can be seen from example 1 and comparative example 3 that, in comparative example 3, zinc oxide and copper oxide with general particle sizes are adopted, and after firing, compared with the properties of thin skin, good homogeneity, high density and the like of the product in example 1, the thickness of the skin around the product in comparative example 3 is very large, so that the additive has a serious enrichment phenomenon on the skin, high porosity and difficulty in densification, the purpose of consistency of material components cannot be met, and the use process has a safety risk.
It is understood from example 2 and comparative example 4 that in comparative example 4, the whole process is completely fired, and the organic matter in the green body is oxidized and hardly discharged into the furnace, and the oxygen partial pressure in the furnace is lowered. In the embodiment 2, air is introduced into the furnace below 800 ℃, the organic matters are oxidized and then are discharged out of the furnace along with the air, and a certain oxygen partial pressure can be maintained in the furnace. After sintering, the density and the conductivity of the product in example 2 are high, while the density and the conductivity of the product in comparative example 4 are obviously reduced, and the conductivity is reduced, presumably because oxygen molecules enter a solid phase lattice when the oxygen partial pressure of the tin oxide ceramic electrode is higher under an oxidizing atmosphere, and p-type electrons are generated to achieve the purpose of conductivity; when the oxygen partial pressure is lower, the lattice in the crystal is lack of oxygen, and n-type electrons are generated to reduce the conductivity of the sample.
Elemental analysis was performed on the products of example 1 and comparative example 5 using a scanning electron microscope-energy spectrometer, and it was found that in comparative example 5, when the copper oxide content was greater than the zinc oxide content, many copper-rich regions, i.e., a problem of glass coloration existed in the products, whereas in example 1, when the copper oxide content was less than the zinc oxide content, no copper-rich regions existed in the products.
Claims (6)
1. The low-energy consumption corrosion-resistant tin oxide electrode for the glass kiln is characterized by comprising tin dioxide, a sintering promoting agent, a conductive additive, a dispersing agent and a binder; the sintering promoter is zinc oxide and copper oxide, and the mass ratio of the zinc oxide to the copper oxide is 0.3-0.5: 100, and the addition amount of zinc oxide is greater than that of copper oxide; the conductive additive is antimony trioxide, and the mass ratio of the antimony trioxide to the tin dioxide is 0.8-1.5: 100, respectively; the mass ratio of the total weight of the dispersing agent and the binder to the tin dioxide is 0.5-1.5: 100.
2. the low energy consumption erosion resistant tin oxide electrode for glass kilns as in claim 1, wherein the tin dioxide has a particle size of less than 45 μm.
3. The low energy consumption corrosion resistant tin oxide electrode for glass kilns as claimed in claim 1, wherein said zinc oxide and copper oxide are submicron or nanoscale powders with a particle size of less than 1 μm.
4. The method for preparing the low-energy consumption corrosion-resistant tin oxide electrode for the glass kiln as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1 wet ball milling and mixing: firstly, adding a dispersing agent and a binder into a stirring mill, stirring, adding zinc oxide, copper oxide and antimony trioxide, stirring, uniformly dispersing, adding tin dioxide, stirring, and fully and uniformly mixing to obtain pug;
s2 granulation: putting the pug prepared in the step S1 into a mud storage container, drying, crushing after drying, and sieving by a 40-80 mesh sieve to obtain granulation powder;
s3 cold isostatic pressing: adding the granulation powder prepared in the step S2 into a rubber blank in a steel mold, sealing, vacuumizing, and carrying out isostatic pressing, wherein the molding pressure is controlled at 100-200 MPa;
s4 destressing: standing the blank formed in the step S3 for 3-5 days, and performing stress relief treatment;
s5, sintering under normal pressure: loading the blank obtained in the step S4 into a sintering furnace, and sintering at 1350-;
s6 post-processing: and (4) cutting and grinding the tin dioxide electrode material obtained in the step (S5) to obtain a tin oxide electrode product.
5. The method for preparing the low-energy-consumption corrosion-resistant tin oxide electrode for the glass kiln as claimed in claim 4, wherein in the step S2, the water content of the granulated powder is less than 0.5%.
6. The method for preparing the low-energy-consumption corrosion-resistant tin oxide electrode for the glass kiln as claimed in claim 4, wherein in the step S5, air is introduced below 800 ℃ in the normal-pressure sintering process for semi-closed sintering, and the full-closed sintering is started from 800 ℃.
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