A siliceous torpedo can mouth material and a preparation process thereof

Abstract

The application provides a siliceous torpedo tank mouth material and a preparation process thereof, and belongs to the technical field of refractory materials. The method comprises the following steps: oxidizing carbon fiber balls prepared by electrolysis-ultrasonic treatment of polyacrylonitrile, N,N-dimethylformamide and a sodium sulfate solution; taking tetraethyl orthosilicate as a precursor, obtaining composite silicon powder through an acid sol-gel and sintering process; obtaining modified zirconia fibers by sequentially performing plasma activation, poly(3,4-ethylenedioxythiophene) conductive coating and 3-aminopropyl triethoxysilane interface bonding treatment on zirconia fibers; and mixing mullite, brown corundum, leaf wax stone powder, the composite silicon powder, the modified zirconia fibers, water and a polycarboxylic acid water reducing agent, uniformly dispersing the mixture into a slurry under a pulse current, and preparing the torpedo tank mouth material through forming, demolding, curing and heating. The application is helpful to improve the mechanical strength and thermal shock stability of the siliceous torpedo tank mouth material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of refractory materials, in particular to a silicon torpedo ladle mouth material and a preparation process thereof. BACKGROUND

[0002] As an important part of molten iron transportation equipment, the torpedo ladle is subjected to long-term high-temperature molten iron scouring and thermal shock cycles in the ladle mouth area, which is prone to cracking and reduction of material strength. Therefore, improving the mechanical strength and thermal shock stability of the torpedo ladle mouth material is one of the key technologies to ensure the safe, stable and long-term operation of the torpedo ladle.

[0003] The torpedo ladle mouth material is usually composed of mullite, corundum, silicon powder, binder and inorganic reinforcing fibers. However, the current torpedo ladle mouth material still has some defects: in the process of high-low temperature rapid cycle, the internal volume of the material is prone to expansion and contraction due to sudden temperature changes, which induces micro-cracks and leads to a decrease in thermal shock stability; inorganic reinforcing fibers are prone to agglomeration and sedimentation in the castable system, resulting in unstable reinforcing effect, and the interface bonding force between inorganic reinforcing fibers and inorganic aggregates (such as mullite and corundum) is also insufficient, which is an important factor leading to performance degradation.

[0004] For example, the patent application file with publication number CN114163220A discloses a composite torpedo ladle mouth cast body and its construction method. The torpedo ladle mouth cast body is composed of two parts: the iron tapping surface and the non-iron tapping surface. The raw materials of the refractory castable layer of the iron tapping surface consist of 35%~50% sintered mullite, 20%~35% titanium corundum, 5%~15% brown corundum powder, 2%~5% pyrophyllite powder, 2%~6% silicon powder, 5%~10% silicon carbide powder, 1%~3% steel fiber, 2%~4% aluminate cement and 0.1%~0.3% water reducing agent, by weight percentage. The expansion and contraction of silicon powder in high-low temperature environment in this scheme leads to micro-cracks in the material, which also reduces the thermal shock stability of the material; the dispersion of steel fiber is poor, which is prone to agglomeration and segregation, resulting in uneven material during casting, and further affecting the mechanical properties of the material.

[0005] In summary, it is necessary to provide a silicon torpedo ladle mouth material and a preparation process thereof to solve the problems existing in the prior art. SUMMARY

[0006] In view of the problems of silicon powder expansion and contraction and uneven dispersion of inorganic fiber material in the prior art, which lead to a decrease in the thermal shock stability and mechanical strength of the silicon torpedo ladle mouth material, the present application provides a silicon torpedo ladle mouth material and a preparation process thereof.

[0007] To achieve the above object, a preparation process of a siliceous torpedo can mouth material comprises the following preparation steps:

[0008] S1, polyacrylonitrile, N, N-dimethylformamide and sodium sulfate solution is mixed, electrolysis and ultrasonic treatment is carried out simultaneously, filtration, washing, oxidation, carbonization, carbon fiber ball is obtained;Tetraethyl orthosilicate and ethanol solution is mixed, adjust pH to acid, add carbon fiber ball, stir, aging, filtration, washing, drying, sintering, obtain composite silicon powder;

[0009] S2, after zirconia fiber is treated by plasma activation, poly (3,4-ethylenedioxythiophene) and deionized water are mixed, stirring, filtration and drying, pour into 3-aminopropyl triethoxysilane solution, stirring, filtration and drying, obtain modified zirconia fiber;

[0010] S3, mullite, brown corundum, pyrophyllite powder, composite silicon powder, deionized water, modified zirconia fiber and polycarboxylic acid water reducing agent are mixed, pulse current is applied, stirring, slurry is moulded, static demoulding, curing, heating, and torpedo can mouth material is prepared.

[0011] The amorphous silicon dioxide in conventional silicon powder expands when the temperature rises, and shrinks when the temperature drops, which not only causes microcracks in the material to reduce the thermal shock stability of the material, but also causes the silicon powder to fall off to further reduce the mechanical strength of the material. In view of these problems, the present application introduces composite silicon powder combined with carbon fiber ball, which utilizes the porous structure and elastic properties of the carbon fiber ball to reduce the volume change of the composite silicon powder, thereby improving the mechanical strength and thermal shock stability of the material.

[0012] The present application uses polyacrylonitrile, N, N-dimethylformamide and tetraethyl orthosilicate as raw materials, and uses electrolysis to prepare oxygen and sol-gel method to prepare composite silicon powder, so as to improve the volume stability of the composite silicon powder. Oxygen bubbles are continuously generated by electrolysis of water and distributed in the solution, so that the carbon fiber ball can form a three-dimensional network structure based on the oxygen bubbles, and the ultrasonic auxiliary is used to improve the dispersion uniformity of the oxygen bubbles in the solution, thereby increasing the uniformity of the pore structure on the carbon fiber ball. Then, tetraethyl orthosilicate and carbon fiber ball are mixed, so that tetraethyl orthosilicate enters the pore structure of carbon fiber ball by liquid phase penetration, and the composite silicon powder prepared by sol-gel method combined with sintering treatment makes silicon dioxide and carbon fiber ball fully combined. During the high and low temperature cycle change process, the volume of silicon dioxide expands or shrinks, and the carbon fiber ball can relieve the volume change of silicon dioxide due to its good elastic properties, thereby reducing the volume change of the composite silicon powder, avoiding the surrounding material of the composite silicon powder from being extruded to produce cracks, and further improving the thermal shock stability of the material.

[0013] Meanwhile, the carbon fiber ball itself has good high-temperature stability, can maintain the original network structure in a high-low temperature cyclic change environment, binds the silicon dioxide in the composite silicon powder, prevents the silicon dioxide from falling off, and thus avoids the problem of mechanical strength reduction caused by the falling off of the silicon dioxide.

[0014] The modified zirconia fiber with electrical response stability and interface enhancement capability is prepared by the synergistic method of plasma activation, conductive coating of poly(3,4-ethylenedioxythiophene) and interfacial chemical grafting of amino silane based on zirconia fiber. First, the surface of the zirconia fiber is treated by plasma, a large number of active hydroxyl sites are formed on the surface, and reaction sites are provided for the subsequent coupling reaction of conductive polymer and interface; then the zirconia fiber is coated with poly(3,4-ethylenedioxythiophene), a continuous conductive network is constructed on the surface of the zirconia fiber, the zirconia fiber can produce stable electrophoretic suspension behavior in an external pulse current field, so as to effectively inhibit the sedimentation and agglomeration of the modified zirconia fiber in the subsequent slurry stirring, and improve the three-dimensional uniform distribution of the modified zirconia fiber in the slurry; then the hydrolysis-condensation reaction of 3-aminopropyl triethoxysilane is carried out, the silicon-oxygen structure of the amino silane forms a Zr-O-Si bond with the surface of the zirconia fiber, and the amino end produces a hydrogen bond or chemical action with the inorganic aggregate such as mullite and brown corundum, so as to construct a stable interface bridge structure between the fiber and the inorganic matrix, and enhance the interface anchoring effect of the modified zirconia fiber. Through the above action mechanism, not only the dispersion uniformity of the modified zirconia fiber in the material is improved, but also the combination performance of the modified zirconia fiber and the inorganic aggregate is improved, and the mechanical strength of the material is further increased.

[0015] Optionally, the brown corundum is modified brown corundum, the modified brown corundum is prepared by mixing brown corundum, sulfobetaine methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N,N'-methylenebisacrylamide and deionized water, stirring at a speed of 500-800 rpm for 30-60 min, slowly adding ammonium persulfate, stirring at a speed of 300-400 rpm for 15-30 min, introducing nitrogen to remove oxygen, heating to 60-70 DEG C constant temperature treatment for 2-3 h, filtering, washing 3-5 times with deionized water, and blowing dry at 45-55 DEG C for 4-6 h.

[0016] The present application introduces a hydrogel film formed by in-situ polymerization of sulfobetaine methacrylate, 2-acrylamido-2-methylpropanesulfonic acid and N,N'-methylenebisacrylamide on the surface of brown corundum, so that the brown corundum aggregate has significantly improved fluidity and interfacial wettability. The sulfobetaine group and the sulfonic acid group have strong hydrophilicity, which can construct a stable charged hydration film on the surface of brown corundum, so that a continuous low-friction sliding interface is formed between the aggregate particles, thereby effectively reducing the inter-particle frictional resistance generated during the mixing of the slurry; the three-dimensional cross-linked network provided by N,N'-methylenebisacrylamide enables the hydrogel film to remain intact without falling off under the shear stress during stirring and vibration, further enhancing the dispersibility of brown corundum. By improving the fluidity and interfacial compatibility of the modified brown corundum, the modified brown corundum can be more uniformly arranged and has higher filling efficiency during the forming process, thereby improving the overall density of the material and further enhancing the mechanical strength of the torpedo tank mouth material.

[0017] Optionally, in step S1, polyacrylonitrile and N,N-dimethylformamide are mixed, a sodium sulfate solution is added, poured into an electrolytic cell, an electric current of 0.5-1A is set for electrolysis, and ultrasonic treatment is simultaneously performed at a frequency of 20-30 kHz for 2-4 hours, then filtration is performed to obtain a solid, the solid is washed with deionized water for 3-5 times, heated to 200-300 DEG C for oxidation treatment for 2-4 hours, and then heated to 1000-1500 DEG C for carbonization for 2-4 hours to obtain carbon fiber spheres.

[0018] In the present application, under the electrolytic condition, the polyacrylonitrile in the solution forms a large number of uniformly distributed oxygen bubble structures through the synergistic effect of ultrasonic treatment, and then through the oxidation and high-temperature carbonization process, these bubble sites are converted into stable pores, and finally the carbon fiber spheres with a porous structure are obtained. The porous structure improves the adsorption capacity of the carbon fiber spheres, so that they can more fully absorb tetraethyl orthosilicate in the subsequent sol-gel coating process, which is beneficial to the formation of a uniform intercalation structure of silica and carbon fiber spheres, thereby improving the volume stability of the composite silicon powder.

[0019] Optionally, in step S1, tetraethyl orthosilicate is mixed with an ethanol solution, hydrochloric acid is added to adjust the pH of the solution to 4-5, carbon fiber spheres are added, stirring is performed at a speed of 200-300 rpm for 2-3 hours, aging is performed at room temperature for 24-30 hours, filtration is performed, the obtained product is washed with deionized water for 2-3 times, drying is performed at 60-80 DEG C for 12-15 hours, and then heating is performed to 950-1000 DEG C for sintering for 4-5 hours to obtain the composite silicon powder.

[0020] Optionally, in step S2, the zirconia fibers are laid in the plasma generator cavity, vacuumed to 40-50 Pa, oxygen is introduced, plasma treatment is carried out at a power of 100-200 W for 5-15 min, then mixed with poly(3,4-ethylenedioxythiophene) and deionized water, stirred at a speed of 300-500 rpm for 2-3 h, filtered, dried at 80-90 DEG C for 1-2 h, poured into a 3-aminopropyl triethoxysilane solution, stirred at 20-25 DEG C for 2-3 h, filtered, dried at 70-80 DEG C for 2-3 h, to obtain modified zirconia fibers.

[0021] In the application, the surface of the zirconia fibers is activated by plasma to form high-activity hydroxyl sites, and then the surface is coated with conductive poly(3,4-ethylenedioxythiophene) and interface grafted with 3-aminopropyl triethoxysilane, so that the surface of the fibers has good conductivity and interface reactivity; the synergistic modification significantly improves the dispersibility and interface bonding force of the zirconia fibers in the slurry, and the fibers can more effectively play a bridging and toughening role in use, thereby improving the thermal shock stability and mechanical strength of the material.

[0022] Optionally, in step S3, the mullite, brown corundum, leaf wax stone powder, composite silicon micro powder, deionized water, modified zirconia fibers and polycarboxylic acid water reducing agent are mixed, a pulse current is applied in the vertical direction, and stirring is carried out for 10-15 min, then the slurry is slowly injected into a mold cavity, demolding is carried out after standing for 24-36 h, curing treatment is carried out, and heating is carried out, to obtain a torpedo tank spout material.

[0023] In the application, by applying a pulse current in the vertical direction during the mixing stage, the electrophoretic suspension effect of the modified zirconia fibers can be enhanced, so that the fibers are uniformly distributed in the slurry and sedimentation and agglomeration are avoided; meanwhile, the interface wetting between the composite silicon micro powder, brown corundum and mullite is promoted, and the uniformity and forming density of the slurry are improved.

[0024] Optionally, the current density of the pulse current is 5-8 mA / cm 2 , and the frequency is 30-50 Hz.

[0025] Optionally, the relative humidity of the curing treatment is 60%-80%, and the curing time is 3-5 d; the temperature of the heating treatment is 110-150 DEG C, and the heating time is 5-10 h.

[0026] In the application, the curing humidity of the torpedo tank spout material is controlled to be 60%-80% and curing is carried out for 3-5 d, which can promote the internal hydration reaction and structure of the slurry to gradually stabilize, and heating to 110-150 DEG C for 5-10 h can further remove the combined water and improve the density and structural stability of the material.

[0027] The siliceous torpedo can mouth material comprises the following raw materials in parts by weight: 90-100 parts of mullite, 110-125 parts of brown corundum, 8-12 parts of pyrophyllite powder, 20-24 parts of composite silicon powder, 7-11 parts of modified zirconia fiber, 15-22 parts of deionized water and 0.5-1.2 parts of polycarboxylic acid water reducing agent; the composite silicon powder comprises the following raw materials in parts by weight: 40-48 parts of tetraethyl orthosilicate, 280-340 parts of 75wt% ethanol solution and 8-10 parts of carbon fiber spheres; the modified zirconia fiber comprises the following raw materials in parts by weight: 7-11 parts of zirconia fiber, 2-5 parts of poly(3,4-ethylenedioxythiophene), 60-80 parts of deionized water and 20-25 parts of 2wt% 3-aminopropyl triethoxysilane solution.

[0028] Optionally, the carbon fiber spheres comprise the following raw materials in parts by weight: 10-20 parts of polyacrylonitrile, 50-100 parts of N,N-dimethylformamide and 10-15 parts of 10wt% sodium sulfate solution.

[0029] The brown corundum is modified brown corundum comprising the following raw materials in parts by weight: 110-125 parts of brown corundum, 1-2 parts of sulfobetaine methacrylate, 3-5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.1-0.3 parts of N,N'-methylenebisacrylamide, 80-100 parts of deionized water and 0.1-0.3 parts of ammonium persulfate.

[0030] The above technical solution of the present application at least has the following beneficial effects:

[0031] The present application uses polyacrylonitrile, N,N-dimethylformamide and tetraethyl orthosilicate as raw materials, and prepares the composite silicon powder by electrolytic oxygen and sol-gel method, thereby improving the volume stability of the composite silicon powder. The oxygen bubbles continuously generated in the electrolysis process are uniformly dispersed under the action of ultrasonic waves, so that the carbon fiber spheres form a three-dimensional network with uniform pore structure. Then, the tetraethyl orthosilicate is liquid phase infiltrated with the carbon fiber spheres, and is subjected to sol-gel and sintering treatment, so that the silicon dioxide and the carbon fiber spheres construct an interpenetrating structure. This structure can absorb stress by the elastic deformation of the carbon fiber spheres when the silicon dioxide undergoes high and low temperature volume changes, thereby reducing the volume change of the composite silicon powder particles, avoiding the generation of cracks caused by extrusion, and improving the thermal shock stability and mechanical strength of the material.

[0032] The application takes zirconia fiber as a base material, and is modified by plasma activation, poly(3,4-ethylenedioxythiophene) conductive coating, and 3-aminopropyl triethoxysilane interfacial grafting. Plasma treatment introduces active hydroxyl sites on the surface of the zirconia fiber, and poly(3,4-ethylenedioxythiophene) forms a continuous conductive network on the surface of the fiber, so that the fiber produces stable electrophoretic suspension behavior in the pulsed current field, thereby inhibiting its settlement and agglomeration in the subsequent slurry stirring; 3-aminopropyl triethoxysilane forms a stable interfacial bridging structure between the fiber and mullite and brown corundum through Zr-O-Si bonds and the action of the amino group on the inorganic aggregate. Through the above action mechanism, the zirconia fiber obtains more uniform three-dimensional distribution and stronger interfacial anchoring capacity in the material, further enhancing the mechanical strength of the torpedo tank mouth material. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. The described embodiments are part of the embodiments of the present application, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present application belong to the scope of protection of the present application.

[0034] Embodiment 1

[0035] 10 parts of polyacrylonitrile and 50 parts of N,N-dimethylformamide were mixed, 10 parts of a 10wt% sodium sulfate solution was added, poured into an electrolytic cell, and electrolysis was performed with a current of 0.5A, while ultrasonic treatment was performed at a frequency of 20kHz for 2h, and a solid was obtained by filtration, washed with deionized water 3 times, placed in an oxidation furnace, heated to 200℃ for oxidation treatment for 2h, and then heated to 1000℃ for carbonization for 2h, to obtain carbon fiber balls; 40 parts of tetraethyl orthosilicate was mixed with 280 parts of a 75wt% ethanol solution, and 37wt% hydrochloric acid was added to adjust the pH of the solution to 4, 8 parts of the carbon fiber balls were added, stirred at a speed of 200rpm for 2h, aged at room temperature for 24h, impurities were removed by filtration, washed with deionized water 2 times, dried at 60℃ for 12h, and sintered at 950℃ for 4h to obtain composite silicon powder.

[0036] 7 parts of zirconia fiber was laid flat in the cavity of a plasma generator, vacuumed to 40Pa, oxygen was introduced into the cavity, and plasma treatment was performed at a power of 100W for 5min, then mixed with 2 parts of poly(3,4-ethylenedioxythiophene) and 60 parts of deionized water, mechanically stirred at a speed of 300rpm for 2h, filtered, dried at 80℃ for 1h, poured into 20 parts of a 2wt% 3-aminopropyl triethoxysilane solution, treated at 20℃ for 2-3h, filtered, and dried at 70℃ for 2h to obtain modified zirconia fiber.

[0037] Mix 110 parts of brown corundum, 1 part of sulfobetaine methacrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.1 part of N,N'-methylenebisacrylamide and 80 parts of deionized water, stir at a speed of 500 rpm for 30 min, slowly add 0.1 part of ammonium persulfate, stir at a speed of 300 rpm for 15 min, blow nitrogen to remove oxygen, heat to 60℃ constant temperature treatment for 2h, filter, wash with deionized water for 3 times, blow dry at 45℃ for 4h, get modified brown corundum.

[0038] Mix 90 parts of mullite, 110 parts of modified brown corundum, 8 parts of lepidolite powder, 20 parts of composite silicon micro powder, 15 parts of deionized water, 7 parts of modified zirconia fiber and 0.5 parts of polycarboxylic acid superplasticizer, apply pulse current along the vertical direction (current density is 5mA / cm 2 , frequency is 30Hz), stir at a speed of 100 rpm for 10 min, slowly inject the slurry into the mold cavity, demold after standing for 24h, maintain in an environment with a relative humidity of 60% for 3d, heat at 110℃ for 5h, and prepare the torpedo tank mouth material.

[0039] Example 2

[0040] Mix 15 parts of polyacrylonitrile and 80 parts of N,N-dimethylformamide, add 13 parts of 10wt% sodium sulfate solution, pour into the electrolytic cell, set the current to 0.8A for electrolysis, and ultrasonic treatment at a frequency of 25kHz for 3h at the same time, filter to obtain a solid, wash with deionized water for 4 times, put into the oxidation furnace, heat to 250℃ for oxidation treatment for 3h, and then heat to 1250℃ for carbonization for 3h, to obtain carbon fiber balls; mix 45 parts of tetraethyl orthosilicate with 300 parts of 75wt% ethanol solution, and add 37wt% hydrochloric acid to adjust the pH of the solution to 4.5, add 9 parts of carbon fiber balls, stir at a speed of 250 rpm for 2.5h, age at room temperature for 28h, remove impurities by filtration, wash with deionized water for 2 times, dry at 70℃ for 14h, and sinter at 980℃ for 4.5h to obtain composite silicon micro powder.

[0041] Lay 9.5 parts of zirconia fiber in the plasma generator cavity, vacuumize to 45Pa, introduce oxygen into the cavity, after plasma treatment at a power of 150W for 10min, mix with 3.5 parts of poly(3,4-ethylenedioxythiophene) and 70 parts of deionized water, mechanically stir at a speed of 400 rpm for 2.5h, filter, dry at 85℃ for 1.5h, pour into 22 parts of 2wt% 3-aminopropyltriethoxysilane solution, treat at 22℃ for 2.5h, filter, dry at 75℃ for 2.5h to obtain modified zirconia fiber.

[0042] Mix 115 parts of brown corundum, 1.5 parts of sulfobetaine methacrylate, 4 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.2 parts of N,N'-methylenebisacrylamide and 90 parts of deionized water, stir at a speed of 650 rpm for 45 min, slowly add 0.2 parts of ammonium persulfate, stir at a speed of 350 rpm for 22 min, blow in nitrogen to remove oxygen, heat to 65℃ and keep constant for 2.5 h, filter, wash with deionized water for 4 times, blow dry at 50℃ for 5 h, to obtain modified brown corundum.

[0043] Mix 95 parts of mullite, 115 parts of modified brown corundum, 10 parts of lepidolite powder, 22 parts of composite silicon micro powder, 18 parts of deionized water, 8.5 parts of modified zirconia fiber and 0.7 parts of polycarboxylic acid superplasticizer, apply pulse current along the vertical direction (current density is 6.5 mA / cm 2 , frequency is 40 Hz), stir at a speed of 150 rpm for 12 min, slowly inject the slurry into the mold cavity, demold after standing for 30 h, maintain in an environment with a relative humidity of 70% for 4 d, heat at 125℃ for 7 h, to obtain a torpedo tank spout material.

[0044] Example 3

[0045] Mix 20 parts of polyacrylonitrile and 100 parts of N,N-dimethylformamide, add 15 parts of 10wt% sodium sulfate solution, pour into an electrolytic cell, set the current to 1A for electrolysis, and ultrasonic treatment at a frequency of 30 kHz for 4 h, filter to obtain a solid, wash with deionized water for 5 times, put into an oxidation furnace, heat to 300℃ for oxidation treatment for 4 h, and then heat to 1500℃ for carbonization for 4 h, to obtain carbon fiber balls; mix 48 parts of tetraethyl orthosilicate with 340 parts of 75wt% ethanol solution, and add 37wt% hydrochloric acid to adjust the pH of the solution to 5, add 10 parts of carbon fiber balls, stir at a speed of 300 rpm for 3 h, age at room temperature for 30 h, filter to remove impurities, wash with deionized water for 3 times, dry at 80℃ for 15 h, and sinter at 1000℃ for 5 h, to obtain composite silicon micro powder.

[0046] Lay 11 parts of zirconia fiber in the cavity of the plasma generator, vacuumize to 50 Pa, blow in oxygen into the cavity, after plasma treatment at a power of 200 W for 15 min, mix with 5 parts of poly(3,4-ethylenedioxythiophene) and 80 parts of deionized water, mechanically stir at a speed of 500 rpm for 3 h, filter, dry at 90℃ for 2 h, pour into 25 parts of 2wt% 3-aminopropyltriethoxysilane solution, treat at 25℃ for 3 h, filter, dry at 80℃ for 3 h, to obtain modified zirconia fiber.

[0047] Mix 125 parts of brown corundum, 2 parts of sulfobetaine methacrylate, 5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.3 parts of N,N'-methylenebisacrylamide and 100 parts of deionized water, stir at a speed of 800 rpm for 60 min, slowly add 0.3 parts of ammonium persulfate, stir at a speed of 400 rpm for 30 min, blow in nitrogen to remove oxygen, heat to 70℃ and keep constant for 3h, filter, wash with deionized water for 5 times, blow dry at 55℃ for 6h, to obtain modified brown corundum.

[0048] Mix 100 parts of mullite, 125 parts of modified brown corundum, 12 parts of pyrophyllite powder, 24 parts of composite silicon micro powder, 22 parts of deionized water, 11 parts of modified zirconia fiber and 1.2 parts of polycarboxylic acid superplasticizer, apply pulse current along the vertical direction (current density is 8mA / cm 2 , frequency is 50Hz), stir at a speed of 200 rpm for 15 min, slowly inject the slurry into the mold cavity, demold after standing for 36h, maintain in an environment with a relative humidity of 80% for 5d, heat at 150℃ for 10h, to obtain a torpedo tank spout material.

[0049] Example 4

[0050] Mix 10 parts of polyacrylonitrile and 50 parts of N,N-dimethylformamide, add 10 parts of 10wt% sodium sulfate solution, pour into an electrolytic cell, set the current to 0.5A for electrolysis, and ultrasonic treatment at a frequency of 20kHz for 2h, filter to obtain a solid, wash with deionized water for 3 times, put into an oxidation furnace, heat to 200℃ for oxidation treatment for 2h, and then heat to 1000℃ for carbonization for 2h, to obtain carbon fiber balls; mix 40 parts of tetraethyl orthosilicate with 280 parts of 75wt% ethanol solution, and add 37wt% hydrochloric acid to adjust the pH of the solution to 4, add 8 parts of carbon fiber balls, stir at a speed of 200 rpm for 2h, age at room temperature for 24h, filter to remove impurities, wash with deionized water for 2 times, dry at 60℃ for 12h, and sinter at 950℃ for 4h, to obtain composite silicon micro powder.

[0051] Lay 7 parts of zirconia fiber in the cavity of the plasma generator, vacuumize to 40Pa, introduce oxygen into the cavity, plasma treat at a power of 100W for 5min, mix with 2 parts of poly(3,4-ethylenedioxythiophene) and 60 parts of deionized water, mechanically stir at a speed of 300 rpm for 2h, filter, dry at 80℃ for 1h, pour into 20 parts of 2wt% 3-aminopropyltriethoxysilane solution, treat at 20℃ for 2~3h, filter, dry at 70℃ for 2h, to obtain modified zirconia fiber.

[0052] Mix 90 parts of mullite, 110 parts of brown corundum, 8 parts of pyrophyllite powder, 20 parts of composite silicon micro powder, 15 parts of deionized water, 7 parts of modified zirconia fiber and 0.5 parts of polycarboxylic acid water reducing agent, apply pulse current (current density is 5 mA / cm 2 , frequency is 30 Hz) along the vertical direction, stir at a speed of 100 rpm for 10 min, slowly inject the slurry into the mold cavity, demold after standing for 24 h, maintain in an environment with a relative humidity of 60% for 3 d, heat at 110℃ for 5 h, and prepare a torpedo tank spout material.

[0053] Example 5

[0054] Mix 15 parts of polyacrylonitrile and 80 parts of N,N-dimethylformamide, add 13 parts of 10 wt% sodium sulfate solution, pour into an electrolytic cell, set the current to 0.8 A for electrolysis, and simultaneously ultrasonic treatment at a frequency of 25 kHz for 3 h, filter to obtain a solid, wash with deionized water for 4 times, put into an oxidation furnace, heat to 250℃ for oxidation treatment for 3 h, and then heat to 1250℃ for carbonization for 3 h to obtain carbon fiber balls; mix 45 parts of tetraethyl orthosilicate with 300 parts of 75 wt% ethanol solution, and add 37 wt% hydrochloric acid to adjust the solution pH to 4.5, add 9 parts of carbon fiber balls, stir at a speed of 250 rpm for 2.5 h, age at room temperature for 28 h, filter to remove impurities, wash with deionized water for 2 times, dry at 70℃ for 14 h, and sinter at 980℃ for 4.5 h to obtain composite silicon micro powder.

[0055] Lay 9.5 parts of zirconia fiber in the cavity of a plasma generator, vacuumize to 45 Pa, introduce oxygen into the cavity, and after plasma treatment at a power of 150 W for 10 min, mix with 3.5 parts of poly(3,4-ethylenedioxythiophene) and 70 parts of deionized water, mechanically stir at a speed of 400 rpm for 2.5 h, filter, dry at 85℃ for 1.5 h, pour into 22 parts of 2 wt% 3-aminopropyltriethoxysilane solution, treat at 22℃ for 2.5 h, filter, and dry at 75℃ for 2.5 h to obtain modified zirconia fiber.

[0056] Mix 95 parts of mullite, 115 parts of brown corundum, 10 parts of pyrophyllite powder, 22 parts of composite silicon micro powder, 18 parts of deionized water, 8.5 parts of modified zirconia fiber and 0.7 parts of polycarboxylic acid water reducing agent, apply pulse current (current density is 6.5 mA / cm 2 , frequency is 40 Hz) along the vertical direction, stir at a speed of 150 rpm for 12 min, slowly inject the slurry into the mold cavity, demold after standing for 30 h, maintain in an environment with a relative humidity of 70% for 4 d, heat at 125℃ for 7 h, and prepare a torpedo tank spout material.

[0057] Example 6

[0058] Mix 20 parts of polyacrylonitrile and 100 parts of N,N-dimethylformamide, add 15 parts of 10wt% sodium sulfate solution, pour into an electrolytic cell, set the current to 1A for electrolysis, and ultrasonic treatment at a frequency of 30kHz for 4h, filter to obtain a solid, wash with deionized water for 5 times, put into an oxidation furnace, heat to 300℃ for oxidation treatment for 4h, and then heat to 1500℃ for carbonization for 4h to obtain carbon fiber balls; mix 48 parts of tetraethyl orthosilicate with 340 parts of 75wt% ethanol solution, and add 37wt% hydrochloric acid to adjust the pH of the solution to 5, add 10 parts of carbon fiber balls, stir at a speed of 300rpm for 3h, age at room temperature for 30h, remove impurities by filtration, wash with deionized water for 3 times, dry at 80℃ for 15h, and sinter at 1000℃ for 5h to obtain composite silicon micro powder.

[0059] Lay 11 parts of zirconia fiber in the cavity of a plasma generator, vacuumize to 50Pa, introduce oxygen into the cavity, and perform plasma treatment at a power of 200W for 15min, then mix with 5 parts of poly(3,4-ethylenedioxythiophene) and 80 parts of deionized water, mechanically stir at a speed of 500rpm for 3h, filter, dry at 90℃ for 2h, pour into 25 parts of 2wt% 3-aminopropyltriethoxysilane solution, treat at 25℃ for 3h, filter, and dry at 80℃ for 3h to obtain modified zirconia fiber.

[0060] Mix 100 parts of mullite, 125 parts of brown corundum, 12 parts of pyrophyllite powder, 24 parts of composite silicon micro powder, 22 parts of deionized water, 11 parts of modified zirconia fiber and 1.2 parts of polycarboxylic acid water reducer, apply a pulse current (current density is 8mA / cm 2 , frequency is 50Hz) in the vertical direction, stir at a speed of 200rpm for 15min, slowly inject the slurry into the mold cavity, demold after standing for 36h, maintain in an environment with a relative humidity of 80% for 5d, and heat at 150℃ for 10h to prepare a torpedo tank spout material.

[0061] The present application also carries out comparative examples and related tests.

[0062] Comparative Example 1

[0063] The difference compared with Example 1 is only that ordinary silicon micro powder is used instead of composite silicon micro powder, and other components and preparation steps are completely consistent, to prepare a torpedo tank spout material.

[0064] Comparative Example 2

[0065] The difference compared with Example 1 is only that electrolysis and ultrasonic treatment operations are not performed, and other components and preparation steps are completely consistent, to prepare a torpedo tank spout material.

[0066] Comparative Example 3

[0067] The difference between Example 1 and Comparative Example 1 is that no poly(3,4-ethylenedioxythiophene) is added, and the other components and preparation steps are completely consistent, and a torpedo tank mouth material is prepared.

[0068] Comparative Example 4

[0069] The difference between Example 1 and Comparative Example 1 is that no poly(3,4-ethylenedioxythiophene) is added, and the other components and preparation steps are completely consistent, and a torpedo tank mouth material is prepared.

[0070] Performance test:

[0071] The torpedo tank mouth materials prepared in Examples 1-6 and Comparative Examples 1-4 are respectively subjected to performance tests:

[0072] The mechanical strength of the torpedo tank mouth material is tested for normal temperature pressure resistance and normal temperature bending resistance according to the national standards GB / T 5072-2023 “Fire-resistant materials Test method for normal temperature compressive strength” and GB / T 3001-2017 “Fire-resistant materials Test method for normal temperature bending strength”; the high temperature performance of the torpedo tank mouth material is tested for high temperature bending resistance according to the national standard GB / T 13243-1991 “Fire-resistant materials Test method for high temperature bending strength”; the thermal shock stability of the torpedo tank mouth material is tested for thermal shock resistance according to the industry standard YB / T 376.3-2004 “Fire-resistant products Test method for thermal shock resistance (water quenching-crack determination method) ”, the torpedo tank mouth material is subjected to heating / rapid cooling treatment until the torpedo tank mouth material cracks, wherein each time of cold and hot alternation is counted as once, and the time of cold and hot alternation when the crack appears is not counted, the number of cold and hot alternation is recorded, and the test results are shown in Table 1.

[0073] Table 1

[0074]

[0075] Compared with Examples 1-3, the torpedo tank mouth materials in Examples 4-6 do not use modified brown corundum. According to the test results in Table 1, the normal temperature pressure resistance and normal temperature bending resistance of the torpedo tank mouth materials in Examples 4-6 are significantly decreased, which shows that the modified brown corundum helps to improve the mechanical strength of the torpedo tank mouth material.

[0076] Compared with Example 1, the high-temperature bending strength and the cold and hot alternating times of the torpedo tank mouth material in Comparative Example 1 are decreased, which indicates that the composite silicon powder helps to improve the thermal shock stability of the torpedo tank mouth material; compared with Example 1, the high-temperature bending strength and the cold and hot alternating times of the torpedo tank mouth material in Comparative Example 2 are also decreased, which indicates that the operation of electrolysis and ultrasonic treatment at the same time helps to improve the thermal shock stability of the torpedo tank mouth material; compared with Example 1, the normal temperature pressure resistance strength and the normal temperature bending strength of the torpedo tank mouth material in Comparative Example 3 are obviously decreased, which indicates that poly (3, 4-ethylenedioxythiophene) helps to improve the mechanical strength of the torpedo tank mouth material; compared with Example 1, the normal temperature pressure resistance strength and the normal temperature bending strength of the torpedo tank mouth material in Comparative Example 4 are also decreased, which indicates that the application of pulse current helps to improve the mechanical strength of the torpedo tank mouth material.

[0077] The above is the preferred embodiment of the present application, and those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A process for the preparation of a siliceous fish can end material, characterized in that, The preparation steps include the following steps: S1, polyacrylonitrile, N, N-dimethylformamide and sodium sulfate solution are mixed, electrolysis and ultrasonic treatment are carried out at the same time, filtration, washing, oxidation, carbonization are carried out, carbon fiber balls are obtained; tetraethyl orthosilicate and ethanol solution are mixed, the pH is adjusted to be acidic, the carbon fiber balls are added, stirring, aging, filtration, washing, drying, sintering, composite silicon powder is obtained; S2, after the zirconia fiber is treated by plasma activation, the zirconia fiber is mixed with poly (3, 4-ethylenedioxythiophene) and deionized water, stirring, drying, pouring into 3-aminopropyl triethoxysilane solution, stirring, drying, obtaining modified zirconia fiber; S3, mixing mullite, brown corundum, lepidolite powder, composite silicon powder, deionized water, modified zirconia fiber and polycarboxylic acid water reducing agent, applying pulse current, stirring, slurry molding, standing demolding, curing, heating, preparing torpedo tank mouth material.

2. A process for the preparation of a siliceous torpedo can end material according to claim 1, characterized in that, The brown corundum is modified brown corundum, the modified brown corundum is prepared by mixing brown corundum, sulfobetaine methacrylate, 2-acrylamide-2-methylpropane sulfonic acid, N, N'-methylene bisacrylamide and deionized water, stirring at a speed of 500-800 rpm for 30-60 min, slowly adding ammonium persulfate, stirring at a speed of 300-400 rpm for 15-30 min, purging nitrogen to remove oxygen, heating to 60-70 DEG C constant temperature treatment for 2-3 h, filtering, washing with deionized water for 3-5 times, blowing drying at 45-55 DEG C for 4-6 h.

3. The process for preparing a siliceous torpedo can mouth material according to claim 1, characterized in that, In step S1, polyacrylonitrile and N, N-dimethylformamide are mixed, sodium sulfate solution is added, poured into an electrolytic cell, the current is set to 0.5-1 A for electrolysis, and ultrasonic treatment is carried out at a frequency of 20-30 kHz at the same time for 2-4 h, the solid is filtered, washed with deionized water for 3-5 times, oxidized at 200-300 DEG C for 2-4 h, and carbonized at 1000-1500 DEG C for 2-4 h to obtain carbon fiber balls.

4. The process for preparing a siliceous torpedo can mouth material according to claim 1, characterized in that, In step S1, tetraethyl orthosilicate and ethanol solution are mixed, hydrochloric acid is added to adjust the pH of the solution to 4-5, carbon fiber balls are added, stirring at a speed of 200-300 rpm for 2-3 h, aging at room temperature for 24-30 h, filtering, washing with deionized water for 2-3 times, drying at 60-80 DEG C for 12-15 h, and sintering at 950-1000 DEG C for 4-5 h to obtain composite silicon powder.

5. The process for preparing a siliceous torpedo can mouth material according to claim 1, characterized in that, In step S2, the zirconia fiber is laid in the plasma generator cavity, vacuumed to 40-50 Pa, oxygen is introduced, plasma treatment is carried out at a power of 100-200 W for 5-15 min, then poly (3, 4-ethylenedioxythiophene) and deionized water are mixed, stirring at a speed of 300-500 rpm for 2-3 h, filtering, drying at 80-90 DEG C for 1-2 h, pouring into 3-aminopropyl triethoxysilane solution, stirring at 20-25 DEG C for 2-3 h, filtering, drying at 70-80 DEG C for 2-3 h, obtaining modified zirconia fiber.

6. The process for preparing a siliceous torpedo can mouth material according to claim 1, characterized in that, In step S3, the mullite, brown corundum, phlogopite powder, composite silicon micro powder, deionized water, modified zirconia fiber and polycarboxylic acid water reducing agent are mixed, a pulse current is applied in the vertical direction, stirring for 10-15 min, the slurry is slowly injected into the mold cavity, and after standing for 24-36 h, the mold is removed, cured and treated, heated, and the torpedo tank mouth material is prepared.

7. A process for the preparation of a siliceous torpedo can end material according to claim 6, characterized in that, The pulse current has a current density of 5-8 mA / cm 2 and a frequency of 30-50 Hz.

8. The process for preparing a siliceous torpedo can mouth material according to claim 6, characterized in that, The relative humidity of the curing treatment is 60%-80%, and the curing time is 3-5 d; the temperature of the heating treatment is 110-150 DEG C, and the heating time is 5-10 h.

9. A siliceous can end material for a fish can, which is produced by the production process of any one of claims 1 to 8, characterized in that, The composite silicon micro powder comprises the following raw materials in parts by weight: tetraethyl orthosilicate 40-48 parts, 75wt% ethanol solution 280-340 parts, and carbon fiber ball 8-10 parts; the modified zirconia fiber comprises the following raw materials in parts by weight: zirconia fiber 7-11 parts, poly (3, 4-ethylene dioxythiophene) 2-5 parts, deionized water 60-80 parts, and 2wt% 3-aminopropyl triethoxysilane solution 20-25 parts.

10. A siliceous torpedo can end material according to claim 9, wherein, The carbon fiber ball comprises the following raw materials in parts by weight: polyacrylonitrile 10-20 parts, N, N-dimethylformamide 50-100 parts, and 10wt% sodium sulfate solution 10-15 parts; The brown corundum is modified brown corundum comprising the following raw materials in parts by weight: brown corundum 110-125 parts, sulfobetaine methacrylate 1-2 parts, 2-acrylamide-2-methylpropane sulfonic acid 3-5 parts, N, N'-methylene bisacrylamide 0.1-0.3 parts, deionized water 80-100 parts, and ammonium persulfate 0.1-0.3 parts.

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