CN108455993B - Building refractory material and preparation method thereof - Google Patents
Building refractory material and preparation method thereof Download PDFInfo
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- CN108455993B CN108455993B CN201810334649.5A CN201810334649A CN108455993B CN 108455993 B CN108455993 B CN 108455993B CN 201810334649 A CN201810334649 A CN 201810334649A CN 108455993 B CN108455993 B CN 108455993B
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Abstract
The invention discloses a building refractory material and a preparation method thereof, belonging to the technical field of building material preparation. The building refractory material comprises the following raw materials: andalusite, nano-zirconia, crystalline flake graphite, silicon carbide, silicon nitride, silicon dioxide micropowder, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, wherein the building refractory material is prepared by the steps of micropowder preparation, premixing, mixing, press forming and the like. The building refractory material of the invention uses nano zirconia, crystalline flake graphite, silicon carbide and silicon nitride as a reinforcing system, and improves the fire resistance and the resistance of the material together.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of building material preparation, and particularly relates to a building refractory material and a preparation method thereof.
[ background of the invention ]
The refractory material is generally an inorganic non-metallic material having a refractoriness of 1580 ℃ or higher. It includes natural ore and various products made up by using a certain preparation process according to a certain requirements. The refractory material has certain high-temperature mechanical property and good volume stability, and is a necessary material for various high-temperature equipment. In recent years, along with the continuous upgrading of building regulations, the refractory materials are also increasingly applied to the building industry. Common building refractory materials comprise glass wool, aluminum silicate fibers, ceramic fibers and the like, but the traditional refractory materials generally have the defects of poor fire resistance, poor resistance and poor erosion resistance. Many drawbacks have limited the development of traditional refractory materials. Therefore, the development of a fire-resistant material for construction having good fire resistance and other characteristics has been a new direction.
The Chinese invention patent application document 'Sailong combined andalusite/SiC composite refractory material and a preparation method thereof (application number: 201410228821.0)' discloses a sialon combined andalusite/SiC composite refractory material and a preparation method thereof, belonging to the field of refractory materials. The raw materials of the invention are andalusite and alpha-Al2O3Powder, polysilicon waste, aluminum powder, and dextrin and phenolic resin as binding agents. During production, the raw materials are weighed according to the proportion, pug is obtained through mixing, and the pug is pressed and formed and is sintered in the nitrogen atmosphere with the temperature of 1200 and 1500 ℃. The refractory material has the advantages of high apparent porosity, small volume density, thermal shock resistance, creep deformation resistance, good erosion resistance and high compressive strength. However, they have problems of poor fire resistance, bending resistance and pressure resistance.
[ summary of the invention ]
The invention provides a building refractory material and a preparation method thereof, and aims to solve the technical problems that on the basis of a building refractory material disclosed in the Chinese invention patent application document 'Sailong combined andalusite/SiC composite refractory material and a preparation method thereof (application number: 201410228821.0)', the fire resistance, the bending resistance and the pressure resistance of the refractory material are enhanced by optimizing components, using amount and a preparation process and adding the synergistic effect of the components on the basis of using andalusite as a refractory material aggregate.
In order to solve the technical problems, the invention adopts the following technical scheme:
the building refractory material comprises the following raw materials: andalusite, nano-zirconia, crystalline flake graphite, silicon carbide, silicon nitride, distilled water, polyvinyl alcohol, dispersant sodium pyrophosphate and calcium aluminate cement aggregate;
the weight ratio of the nano zirconia to the crystalline flake graphite to the silicon carbide to the silicon nitride is (12-20): (33-45): (7-18): (4-12).
Preferably, in the building refractory material, the particle size of the nano zirconia is 40-60 nm.
Preferably, in the building refractory material, the scale graphite specification is less than or equal to 0.09 mm.
More preferably, in the building refractory material, the weight ratio of the nano zirconia to the crystalline flake graphite to the silicon carbide to the silicon nitride is 14: 40: 10: 8.
the invention also provides a preparation method of the building refractory material, which comprises the following steps:
s1: wet grinding andalusite, nano zirconia, crystalline flake graphite, silicon carbide, silicon nitride and silicon dioxide by using a planetary ball mill, wherein the rotating speed of a motor is 600-800 r/min, and the ball milling time is 35-45 min;
s2: sequentially adding the andalusite, the nano zirconia, the crystalline flake graphite, the silicon carbide, the silicon nitride and the silicon dioxide obtained in the step S1 into a stirring kettle, and premixing for 15-25 min at the rotating speed of 100-200 r/min;
s3: adding the mixed material obtained in the step S2 into a mixing roll, sequentially adding polyvinyl alcohol, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, and mixing for 25-30 min;
s4: placing the mixed material obtained in the step S3 in a pressure forming machine, and performing pre-pressing forming under the pressure of 100-150 MPa;
s5: putting the wet blank obtained in the step S4 into a vacuum drying oven, and heating and preserving heat for 24 hours at the temperature of 200 ℃;
s6: and (4) placing the sample obtained in the step S5 into a muffle furnace, and firing at 1200 ℃ for 18 h.
More preferably, in the preparation method of the building refractory material, the mass ratio of the raw materials to the abrasive grains in each ball milling tank in the step S1 is 1: 2;
more preferably, in the method for preparing the building refractory material, the specification of the material pre-pressed and formed in the step S4 is 150mm × 25mm × 6 mm.
Further, in the method for preparing the building refractory material, the muffle furnace temperature-raising program in the step S6 is: room temperature-1200 deg.c, 10 deg.c/min; 1000-1200 ℃ and 5 ℃/min.
The invention has the following beneficial effects:
(1) as can be seen from the data of examples 1-3 and comparative example 6, the building refractory prepared by the formulation and the steps of examples 1-3 has good breaking resistance and thermal shock resistance, and high initial oxidation temperature; meanwhile, as can be seen from the data of examples 1 to 3, example 2 is the most preferred example.
(2) As can be seen from the data of example 2 and comparative examples 1 to 5, the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride play a synergistic role in preparing the building refractory material, and the fire resistance, the thermal shock resistance and the toughness of the material are synergistically improved, namely:
1) andalusite has good high-temperature resistance, is irreversibly converted into mullite with small linear expansion and low impurity content at high temperature, has slow mullite process, ensures the volume stability of products, shows excellent performances of high mechanical strength, good thermal shock resistance and creep resistance, strong CO and alkali steam corrosion resistance and the like, and has good application prospect in the field of refractory materials. But due to [ SiO ] in the structure of the crystal formed after mullite4]And [ AlO ]4]The arrangement of the tetrahedron space can generate periodic oxygen vacancies with different degrees along with the change of the ratio of Al to Si, so that more gaps exist among crystal lattices, and further, the strength of the material is low, and the application of the material in industrial production is influenced.
2) The non-oxide has better thermal shock resistance because the non-oxide has lower thermal expansion coefficient, higher thermal conductivity and strength; the shape of the non-oxide crystals is mostly needle-like or longThe columnar shape can well induce the change of the thermal stress. When the non-oxide is embedded in the skeleton structure of the oxide, not only the high-temperature strength of the material can be improved, but also the spalling resistance of the material can be improved. For the composite material taking andalusite and zirconia as matrixes, the non-oxide silicon carbide and silicon nitride are embedded into the structure of the composite material, so that the original SiO4]And [ AlO ]4]The gaps among the tetrahedral crystal lattices enable the framework of the material to be a network structure of a mutual staggered network, so that the material has better toughness and strength compared with the material without adding non-oxides, and the material has low sensitivity to temperature change and good thermal shock resistance. By adding the non-oxide as the second phase, the performance of the oxide material can be obviously improved, and the silicon nitride and the silicon carbide are both high-quality high-temperature hard non-oxide materials and can be used as reinforcing phases to improve the comprehensive performance of the material.
3) The reduction of the zirconia grain size in a certain range is also beneficial to improving the resistance of the refractory material. This is because: larger ZrO2The particles are easily wrapped by glass phase containing Al and Si to form a similar crystal grain structure; smaller ZrO2The particles are easier to disperse on the grain boundary, thereby limiting SiO4And AlO4Growing crystal grains; for particularly small ZrO2The particles are easy to agglomerate in the process of mixing materials or flow along with the liquid phase and large-particle SiO in the process of sintering4And AlO4Are combined together. ZrO with the grade of 40-60 nm is selected2Ability to toughen SiO4And AlO4。
4) The flake graphite has good fire resistance. The research shows that in ZrO2-SiO4The graphite flake is added into the composite system, which is beneficial to inhibiting the growth of crystal grains; meanwhile, when the crystalline flake graphite is added into the refractory material, the carbon network formed by the crystalline flake graphite can absorb a part of thermal stress caused by thermal expansion, and the toughening mechanism of the refractory material is due to crack deflection, crack bridging, bifurcation and the stress absorption and release effects of cracks, so that the thermal shock resistance of the refractory material is improved.
(3) As can be seen from the data of comparative examples 6-8, the weight ratio of the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride is not (12-20): (33-45): (7-18): (4-12), the high temperature rupture strength, the initial oxidation temperature and the normal temperature compressive strength of the prepared refractory material are greatly different from those of the examples 1-3, are far smaller than those of the examples 1-3, and are equivalent to those of the prior art (comparative example 6). The invention relates to a reinforcing system of nano zirconia, crystalline flake graphite, silicon carbide and silicon nitride, which is prepared by controlling the weight ratio of the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride to be (12-20): (33-45): (7-18): (4-12), the nano zirconia is used as a main action raw material of the system in the reinforcing system, the crystalline flake graphite is used for inhibiting the formation and the absorption of thermal stress of large grains in the material, and the silicon carbide and the silicon nitride are embedded into the framework structure of oxide to increase the strength of the material and enhance the anti-stripping performance, so that the folding strength, the fire-resistant temperature and the compressive strength of the material can be effectively improved when the reinforcing system is applied to the refractory material.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In the embodiment, the building refractory material comprises the following raw materials in parts by weight: 45-76 parts of andalusite, 12-20 parts of nano zirconia, 33-45 parts of crystalline flake graphite, 7-18 parts of silicon carbide, 4-12 parts of silicon nitride, 20-38 parts of distilled water, 35-60 parts of polyvinyl alcohol, 7-16 parts of dispersant sodium pyrophosphate and 60-110 parts of calcium aluminate cement aggregate.
The particle size of the nano zirconia is 40-60 nm.
The scale graphite specification is less than or equal to 0.09 mm.
The preparation method of the building refractory material comprises the following steps:
s1: wet grinding andalusite, nano zirconia, crystalline flake graphite, silicon carbide, silicon nitride and silicon dioxide by using a planetary ball mill, wherein the rotating speed of a motor is 600-800 r/min, and the ball milling time is 35-45 min;
s2: sequentially adding the andalusite, the nano zirconia, the crystalline flake graphite, the silicon carbide, the silicon nitride and the silicon dioxide obtained in the step S1 into a stirring kettle, and premixing for 15-25 min at the rotating speed of 100-200 r/min;
s3: adding the mixed material obtained in the step S2 into a mixing roll, sequentially adding polyvinyl alcohol, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, and mixing for 25-30 min;
s4: placing the mixed material obtained in the step S3 in a pressure forming machine, and performing pre-pressing forming under the pressure of 100-150 MPa;
s5: putting the wet blank obtained in the step S4 into a vacuum drying oven, and heating and preserving heat for 24 hours at the temperature of 200 ℃;
s6: and (4) placing the sample obtained in the step S5 into a muffle furnace, and firing at 1200 ℃ for 18 h.
The present invention is illustrated by the following more specific examples.
Example 1
The building refractory material comprises the following raw materials in parts by weight: 45 parts of andalusite, 12 parts of nano zirconia with the particle size of 40nm, 33 parts of 0.06 mm-sized crystalline flake graphite, 7 parts of silicon carbide, 4 parts of silicon nitride, 20 parts of distilled water, 35 parts of polyvinyl alcohol, 7 parts of dispersant sodium pyrophosphate and 60 parts of calcium aluminate cement aggregate.
The preparation method of the building refractory material comprises the following steps:
s1: wet grinding andalusite, nano zirconia, crystalline flake graphite, silicon carbide, silicon nitride and silicon dioxide by using a planetary ball mill, wherein the mass ratio of the raw materials to the abrasive particles is 1:2, the rotating speed of a motor is 600r/min, and the ball milling time is 35 min;
s2: sequentially adding the andalusite, the nano zirconia, the crystalline flake graphite, the silicon carbide, the silicon nitride and the silicon dioxide obtained in the step S1 into a stirring kettle, and premixing for 25min at the rotating speed of 100 r/min;
s3: adding the mixed material obtained in the step S2 into a mixing roll, sequentially adding polyvinyl alcohol, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, and mixing for 25 min;
s4: placing the mixed material obtained in the step S3 into a pressure forming machine, and pre-pressing and forming under the pressure of 100MPa, wherein the forming specification is 150mm multiplied by 25mm multiplied by 6 mm;
s5: putting the wet blank obtained in the step S4 into a vacuum drying oven, and heating and preserving heat for 24 hours at the temperature of 200 ℃;
s6: the sample obtained in step S5 was placed in a muffle furnace using a temperature program of: room temperature-1200 deg.c, 10 deg.c/min; 1000-1200 ℃ and 5 ℃/min; firing at 1200 ℃ for 18 h.
Example 2
The building refractory material comprises the following raw materials in parts by weight: 76 parts of andalusite, 20 parts of nano zirconia with the particle size of 60nm, 45 parts of 0.09 mm-sized crystalline flake graphite, 18 parts of silicon carbide, 12 parts of silicon nitride, 38 parts of distilled water, 60 parts of polyvinyl alcohol, 16 parts of dispersant sodium pyrophosphate and 110 parts of calcium aluminate cement aggregate.
The preparation method of the building refractory material comprises the following steps:
s1: wet grinding andalusite, nano zirconia, crystalline flake graphite, silicon carbide, silicon nitride and silicon dioxide by using a planetary ball mill, wherein the mass ratio of the raw materials to the abrasive particles is 1:2, the rotating speed of a motor is 800r/min, and the ball milling time is 35 min;
s2: sequentially adding the andalusite, the nano zirconia, the crystalline flake graphite, the silicon carbide, the silicon nitride and the silicon dioxide obtained in the step S1 into a stirring kettle, and premixing for 15min at the rotating speed of 200 r/min;
s3: adding the mixed material obtained in the step S2 into a mixing roll, sequentially adding polyvinyl alcohol, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, and mixing for 30 min;
s4: placing the mixed material obtained in the step S3 into a pressure forming machine, and pre-pressing and forming under the pressure of 150MPa, wherein the specification of the formed material is 150mm multiplied by 25mm multiplied by 6 mm;
s5: putting the wet blank obtained in the step S4 into a vacuum drying oven, and heating and preserving heat for 24 hours at the temperature of 200 ℃;
s6: placing the sample obtained in the step S5 into a muffle furnace, wherein the temperature rising procedure is as follows: room temperature-1200 deg.c, 10 deg.c/min; 1000-1200 ℃ and 5 ℃/min; firing at 1200 ℃ for 18 h.
Example 3
The building refractory material comprises, by weight, 58 parts of andalusite, 16 parts of nano zirconia with the particle size of 50nm, 42 parts of flake graphite with the specification of 0.07mm, 12 parts of silicon carbide, 8 parts of silicon nitride, 32 parts of distilled water, 48 parts of polyvinyl alcohol, 12 parts of sodium pyrophosphate dispersant and 85 parts of calcium aluminate cement aggregate.
The preparation method of the building refractory material comprises the following steps:
s1: wet grinding andalusite, nano zirconia, crystalline flake graphite, silicon carbide, silicon nitride and silicon dioxide by using a planetary ball mill, wherein the mass ratio of the raw materials to the abrasive particles is 1:2, the rotating speed of a motor is 700r/min, and the ball milling time is 40 min;
s2: sequentially adding the andalusite, the nano zirconia, the crystalline flake graphite, the silicon carbide, the silicon nitride and the silicon dioxide obtained in the step S1 into a stirring kettle, and premixing for 20min at the rotating speed of 150 r/min;
s3: adding the mixed material obtained in the step S2 into a mixing roll, sequentially adding polyvinyl alcohol, sodium pyrophosphate dispersant and calcium aluminate cement aggregate, and mixing for 28 min;
s4: placing the mixed material obtained in the step S3 in a pressure forming machine, and pre-pressing and forming under the pressure of 130MPa, wherein the specification of the pre-pressed and formed material is 150mm multiplied by 25mm multiplied by 6 mm;
s5: putting the wet blank obtained in the step S4 into a vacuum drying oven, and heating and preserving heat for 24 hours at the temperature of 200 ℃;
s6: placing the sample obtained in the step S5 into a muffle furnace, wherein the temperature rising procedure is as follows: room temperature-1200 deg.c, 10 deg.c/min; 1000-1200 ℃ and 5 ℃/min; firing at 1200 ℃ for 18 h.
Comparative example 1
The preparation process is basically the same as that of example 2, except that the nano zirconia is absent from the raw materials for preparing the building refractory.
Comparative example 2
The procedure was essentially the same as in example 2, except that the raw materials used to make the construction refractory lacked exfoliated graphite.
Comparative example 3
The procedure was essentially the same as in example 2, except that the raw materials for the construction refractory were absent of silicon carbide.
Comparative example 4
The procedure was essentially the same as in example 2, except that the raw materials for the construction refractory were absent of silicon nitride.
Comparative example 5
The preparation process is basically the same as that of the example 2, except that the raw materials for preparing the building refractory material lack nano zirconia, crystalline flake graphite, silicon carbide and silicon nitride.
Comparative example 6
The building refractory material is prepared by adopting the formula and the process of the example 1-2 in the Chinese invention patent application document 'Sailong combined andalusite/SiC composite refractory material and the preparation method thereof (application number: 201410228821.0)'.
Comparative example 7
The preparation process is basically the same as that of the example 2, except that the raw materials for preparing the refractory material comprise 9 parts of nano zirconia, 28 parts of crystalline flake graphite, 25 parts of silicon carbide and 20 parts of silicon nitride.
Comparative example 8
The preparation process is basically the same as that of the example 2, except that the raw materials for preparing the refractory material comprise 25 parts of nano zirconia, 9 parts of crystalline flake graphite, 3 parts of silicon carbide and 15 parts of silicon nitride.
Comparative example 9
The preparation process is basically the same as that of the example 2, except that the raw materials for preparing the refractory material comprise 7 parts of nano zirconia, 12 parts of crystalline flake graphite, 26 parts of silicon carbide and 18 parts of silicon nitride.
The building refractory materials prepared by the embodiments 1-3 and the comparative examples 1-9 have the thickness of 6 cm. The materials were tested for high temperature rupture strength (1000 ℃), onset temperature of oxidation, and thermal shock resistance (room temperature compressive strength), and the test results are shown in the following table.
From the above table, it can be seen that: (1) as can be seen from the data of examples 1-3 and comparative example 6, the building refractory prepared by the formulation and the steps of examples 1-3 has good breaking resistance and thermal shock resistance, and high initial oxidation temperature; meanwhile, as can be seen from the data of examples 1 to 3, example 2 is the most preferred example.
(2) As can be seen from the data of example 2 and comparative examples 1 to 5, the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride play a synergistic role in preparing the building refractory material, and the fire resistance, the thermal shock resistance and the toughness of the material are improved synergistically, which may be that:
1) andalusite has good high-temperature resistance, is irreversibly converted into mullite with small linear expansion and low impurity content at high temperature, has slow mullite process, ensures the volume stability of products, shows excellent performances of high mechanical strength, good thermal shock resistance and creep resistance, strong CO and alkali steam corrosion resistance and the like, and has good application prospect in the field of refractory materials. But due to [ SiO ] in the structure of the crystal formed after mullite4]And [ AlO ]4]The arrangement of the tetrahedron space can generate periodic oxygen vacancies with different degrees along with the change of the ratio of Al to Si, so that more gaps exist among crystal lattices, and further, the strength of the material is low, and the application of the material in industrial production is influenced.
2) The non-oxide has better thermal shock resistance because the non-oxide has lower thermal expansion coefficient, higher thermal conductivity and strength; the shape of the non-oxide crystal is generally needle-like or long columnar, and the change of thermal stress can be well induced. When the non-oxide is embedded in the skeleton structure of the oxide, not only the high-temperature strength of the material can be improved, but also the spalling resistance of the material can be improved. For the composite material taking andalusite and zirconia as matrixes, the non-oxide silicon carbide and silicon nitride are embedded into the structure of the composite material, so that the original SiO4]And [ AlO ]4]The gaps between tetrahedral crystal lattices make the skeleton of the material be a network of mutually staggered networksThe structure of the material is improved, so that the material has better toughness and strength compared with the material without the non-oxide, and the material has low sensitivity to temperature change and good thermal shock resistance. By adding the non-oxide as the second phase, the performance of the oxide material can be obviously improved, and the silicon nitride and the silicon carbide are both high-quality high-temperature hard non-oxide materials and can be used as reinforcing phases to improve the comprehensive performance of the material.
3) The reduction of the zirconia grain size in a certain range is also beneficial to improving the resistance of the refractory material. This is because: larger ZrO2The particles are easily wrapped by glass phase containing Al and Si to form a similar crystal grain structure; smaller ZrO2The particles are easier to disperse on the grain boundary, thereby limiting SiO4And AlO4Growing crystal grains; for particularly small ZrO2The particles are easy to agglomerate in the process of mixing materials or flow along with the liquid phase and large-particle SiO in the process of sintering4And AlO4Are combined together. ZrO with the grade of 40-60 nm is selected2Ability to toughen SiO4And AlO4。
4) The flake graphite has good fire resistance. The research shows that in ZrO2-SiO4The graphite flake is added into the composite system, which is beneficial to inhibiting the growth of crystal grains; meanwhile, when the crystalline flake graphite is added into the refractory material, the carbon network formed by the crystalline flake graphite can absorb a part of thermal stress caused by thermal expansion, and the toughening mechanism of the refractory material is due to crack deflection, crack bridging, bifurcation and the stress absorption and release effects of cracks, so that the thermal shock resistance of the refractory material is improved.
(3) As can be seen from the data of comparative examples 6-8, the weight ratio of the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride is not (12-20): (33-45): (7-18): (4-12), the high temperature rupture strength, the initial oxidation temperature and the normal temperature compressive strength of the prepared refractory material are greatly different from those of the examples 1-3, are far smaller than those of the examples 1-3, and are equivalent to those of the prior art (comparative example 6). The invention relates to a reinforcing system of nano zirconia, crystalline flake graphite, silicon carbide and silicon nitride, which is prepared by controlling the weight ratio of the nano zirconia, the crystalline flake graphite, the silicon carbide and the silicon nitride to be (12-20): (33-45): (7-18): (4-12), the nano zirconia is used as a main action raw material of the system in the reinforcing system, the crystalline flake graphite is used for inhibiting the formation and the absorption of thermal stress of large grains in the material, and the silicon carbide and the silicon nitride are embedded into the framework structure of oxide to increase the strength of the material and enhance the anti-stripping performance, so that the folding strength, the fire-resistant temperature and the compressive strength of the material can be effectively improved when the reinforcing system is applied to the refractory material.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (2)
1. The building refractory material is characterized by comprising the following raw materials in parts by weight: 45-76 parts of andalusite, 12-20 parts of nano zirconia, 33-45 parts of crystalline flake graphite, 7-18 parts of silicon carbide, 4-12 parts of silicon nitride, 20-38 parts of distilled water, 35-60 parts of polyvinyl alcohol, 7-16 parts of dispersant sodium pyrophosphate and 60-110 parts of calcium aluminate cement aggregate;
the particle size of the nano zirconia is 40-60 nm.
2. The building refractory according to claim 1, wherein the scale graphite size is 0.09mm or less.
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