CN111662678B - High-temperature antioxidant flexible graphite filler, preparation method and high-temperature antioxidant flexible graphite packing - Google Patents
High-temperature antioxidant flexible graphite filler, preparation method and high-temperature antioxidant flexible graphite packing Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/12—Materials for stopping leaks, e.g. in radiators, in tanks
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention relates to the technical field of sealing fillers, in particular to a preparation method of a high-temperature oxidation-resistant flexible graphite filler, which comprises the following steps: soaking natural crystalline flake graphite in intercalation agent solution, washing with water, and expanding at 850-950 deg.c for 10-15 s to obtain expanded graphite worms; uniformly covering the surface of the reinforced material with the adhesive with the step-expanded graphite worms, and mechanically pressing to obtain a flexible graphite sheet; and (3) immersing the flexible graphite sheet in an antioxidant solution, drying, and heating in a gradient way to obtain the high-temperature antioxidant flexible graphite filler. The invention solves the problem of poor high-temperature oxidation resistance of flexible graphite in the prior art. The antioxidant is soaked on the surface of the flexible graphite sheet or inside the flexible graphite sheet, and the temperature is raised in a gradient way, so that the antioxidant permeates into the graphite material to be converted into a high-temperature antioxidant substance, and the high-temperature antioxidant substance is filled into the graphite material and covers the surface of the graphite. The antioxidant does not need to crush and impregnate the flexible graphite sheet material, and the operation is simpler and more convenient.
Description
Technical Field
The invention relates to the technical field of sealing fillers, in particular to a high-temperature oxidation-resistant flexible graphite filler, a preparation method and a high-temperature oxidation-resistant flexible graphite packing.
Background
Carbon materials are indispensable raw materials and products in modern industrial production. Carbon materials can be generally classified into conventional carbon materials and new carbon materials. Traditional carbon materials mainly include charcoal, activated carbon, natural graphite, graphite electrodes, and the like. With the development of industry and agriculture, the novel carbon material is a direction of important research and development in the field of carbon materials, and is of various kinds, mainly comprising diamond, flexible graphite, porous carbon, nuclear graphite, graphite interlayer compounds and the like. Among the novel carbon materials, flexible graphite is widely used due to its excellent properties: because of the special molding process, a large number of micro air holes are stored in the molded body in the preparation process, so that the flexible graphite has excellent compressibility, rebound resilience and lower stress relaxation (creep) rate, is widely applied to the sealing field, has wider use temperature range compared with the traditional sealing materials such as asbestos, rubber, cellulose and composite materials thereof, can be used in air within the range of-200 to 450 ℃, can reach 3000 ℃ in vacuum or reducing atmosphere, has small thermal expansion coefficient, and can solve the sealing problems such as running, overflowing, leaking and the like at high, normal and low temperatures. The deeply processed flexible graphite is a good sealing material, is called as a 'modern sealing king', is widely applied to the sealing fields of petrochemical industry, nuclear power and the like, and simultaneously maintains some excellent properties of natural graphite materials, such as high temperature resistance, corrosion resistance and excellent self-lubricating property, so that the flexible graphite is an excellent base material in the modern industrial field, and is widely applied to the high-tech fields of petrochemical industry, aerospace, ships, military and the like.
As the science and technology further develop, other excellent properties of flexible graphite will be further developed. However, the flexible graphite has the defect that the flexible graphite is easy to oxidize and corrode under the high-temperature oxygen-enriched condition as other carbon materials, and meanwhile, the special manufacturing process of the flexible graphite has the characteristics of large specific surface area, high porosity and the like, so that the high-temperature oxidation resistance is poorer than that of the common graphite materials.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a method for preparing a high-temperature oxidation-resistant flexible graphite filler, which is used for solving the problem of poor high-temperature oxidation resistance of flexible graphite in the prior art, and at the same time, the present invention also provides a high-temperature oxidation-resistant flexible graphite filler; in addition, the invention also provides a high-temperature oxidation-resistant flexible graphite packing. The antioxidant is soaked on the surface of the flexible graphite sheet or inside the flexible graphite sheet, and the temperature is raised in a gradient way, so that the antioxidant permeates into the graphite material to be converted into high-temperature antioxidant substances which are filled into the graphite material and cover the surface of the graphite material, thereby isolating oxidizing gas and blocking the gas from entering the graphite material from the pores, delaying the occurrence of oxidation reaction and improving the high-temperature oxidation resistance of the graphite material. The antioxidant does not need to crush and impregnate the flexible graphite sheet material, and the operation is simpler and more convenient.
To achieve the above-mentioned objects and other related objects,
in a first aspect of the invention, a method for preparing a high-temperature oxidation-resistant flexible graphite filler is provided, comprising the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution, washing with water, and expanding at a high temperature of 850-950 ℃ for 10-15 s to obtain expanded graphite worms;
step two, uniformly covering the expanded graphite worms in the step one on the surface of the reinforcing material with the adhesive, and mechanically pressing to obtain a flexible graphite sheet;
soaking the flexible graphite sheet material in the second step in an antioxidant solution, drying, heating to 110-130 ℃ and preserving heat for 8-12 min, continuously heating to 200-220 ℃ and preserving heat for 8-12 min, continuously heating to 320-340 ℃ and preserving heat for 25-35 min, and finally heating to 400-420 ℃ and preserving heat for 8-12 min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 10-20 parts of aluminum isopropoxide, 8-14 parts of sodium tetraborate, 5-10 parts of phosphoric acid, 5-10 parts of oxalic acid and 20-60 parts of water.
The natural crystalline flake graphite is put into an intercalation agent, the intercalation agent is inserted into sheets of graphite, and the intercalation agent is prepared into a graphite interlayer compound. The intercalating agent that has not intercalated into the interior of the graphite is removed by water washing. And then the interlayer intercalation agent is gasified to form high pressure by high-temperature expansion, so that the graphite particles are expanded along the direction of the C axis, and expanded graphite worms are formed.
The expanded graphite worms and the reinforcing material are pressed into a whole in advance, and the reinforcing material has good toughness and mechanical property and can complement the problem of poor mechanical property of flexible graphite. The flexible graphite sheet material formed by compression molding still keeps flexibility and can be freely bent, so that the application universality of the flexible graphite sheet material is improved.
The antioxidant is soaked on the surface of the flexible graphite sheet or inside the flexible graphite sheet, and the temperature is raised in a gradient way, so that the antioxidant permeates into the graphite material to be converted into high-temperature antioxidant substances which are filled into the graphite material and cover the surface of the graphite material, thereby isolating oxidizing gas and blocking the gas from entering the graphite material from the pores, delaying the occurrence of oxidation reaction and improving the high-temperature oxidation resistance of the graphite material. The antioxidant does not need to crush and impregnate the flexible graphite sheet material, and the operation is simpler and more convenient.
Aluminum isopropoxide can be hydrolyzed to generate aluminum oxide, and the aluminum oxide has good high-temperature oxidation resistance, so that the high-temperature oxidation resistance of the graphite plate is improved; and aluminum isopropoxide has a dehydration function, and is convenient for removing moisture in the drying process, so that the influence of the aluminum isopropoxide on high-temperature oxidation resistance is avoided. Phosphoric acid and oxalic acid can promote the ingress of antioxidants into the graphite sheet material, thereby allowing the antioxidants to fill the interior of the graphite material and cover the graphite surface.
In an embodiment of the present invention, the intercalating agent solution in the first step includes the following components in parts by weight: 10-15 parts of nitric acid, 1-3 parts of potassium permanganate and 5-8 parts of phosphoric acid.
The nitric acid, potassium permanganate and phosphoric acid do not introduce sulfur-containing substances, so that the high-temperature oxidation-resistant flexible graphite filler does not cause corrosion of metals when used for sealing. The volume of the expanded graphite treated by nitric acid, potassium permanganate and phosphoric acid is 450-550 times of the original volume, and the prepared expanded graphite has no sulfur, full expansion, low cost and simple operation.
In an embodiment of the present invention, the mass ratio of the natural crystalline flake graphite to the intercalation solution is 1: (1.0-2.5).
In an embodiment of the present invention, in the second step, the reinforcing material is carbon fiber, and the adhesive is vinyl acetate; the pressure of the mechanical pressing in the second step is 120-180 kg/cm 2 . The expanded graphite worms and the reinforcing material are pressed into a whole in advance, and the reinforcing material has good toughness and mechanical property and can complement the problem of poor mechanical property of flexible graphite. The flexible graphite sheet material formed by compression molding still keeps flexibility and can be freely bent, thereby improving the application range thereofGeneral character.
In one embodiment of the present invention, the mass ratio of the expanded graphite worms to the carbon fibers is 1: (0.4-0.6).
In an embodiment of the present invention, the antioxidant solution in the third step includes the following components in parts by weight: 10-15 parts of aluminum isopropoxide, 10-12 parts of sodium tetraborate, 7-8 parts of phosphoric acid, 7-8 parts of oxalic acid and 35-45 parts of water.
Aluminum isopropoxide can be hydrolyzed to generate aluminum oxide, and the aluminum oxide has good high-temperature oxidation resistance, so that the high-temperature oxidation resistance of the graphite plate is improved; and aluminum isopropoxide has a dehydration function, and is convenient for removing moisture in the drying process, so that the influence of the aluminum isopropoxide on high-temperature oxidation resistance is avoided. Phosphoric acid and oxalic acid can promote the ingress of antioxidants into the graphite sheet material, thereby allowing the antioxidants to fill the interior of the graphite material and cover the graphite surface.
In an embodiment of the present invention, the gradient heating in the third step is specifically: heating to 120deg.C, keeping the temperature for 10min, continuously heating to 210deg.C, keeping the temperature for 10min, continuously heating to 330 deg.C, keeping the temperature for 30min, and finally heating to 410 deg.C, keeping the temperature for 10min. The gradient heating avoids the excessively rapid conversion of the antioxidant into high-temperature antioxidant substances so as to disperse unevenly, and finally the high-temperature antioxidant substances are uniformly distributed in the graphite and cover the surface of the graphite, so that the high-temperature antioxidant performance of the high-temperature antioxidant flexible graphite filler is better.
In an embodiment of the present invention, the soaking temperature in the first step is 20-40 ℃ and the soaking time is 60-90 min; the dipping temperature in the third step is 60-80 ℃ and the dipping time is 60-90 min.
In a second aspect of the invention, a high-temperature oxidation-resistant flexible graphite filler is provided, and the high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
In a third aspect of the invention, a high-temperature oxidation-resistant flexible graphite packing is provided, and the high-temperature oxidation-resistant flexible graphite packing is formed by rolling, twisting or braiding the high-temperature oxidation-resistant flexible graphite packing. The high-temperature oxidation-resistant flexible graphite packing is prepared by adopting the conventional mode no matter the high-temperature oxidation-resistant flexible graphite packing is coiled, twisted or woven.
As described above, the high-temperature oxidation-resistant flexible graphite filler and the preparation method thereof and the high-temperature oxidation-resistant flexible graphite packing have the following beneficial effects:
the natural crystalline flake graphite is put into an intercalation agent, the intercalation agent is inserted into sheets of graphite, and the intercalation agent is prepared into a graphite interlayer compound. The intercalating agent that has not intercalated into the interior of the graphite is removed by water washing. And then the interlayer intercalation agent is gasified to form high pressure by high-temperature expansion, so that the graphite particles are expanded along the direction of the C axis, and expanded graphite worms are formed.
The expanded graphite worms and the reinforcing material are pressed into a whole in advance, and the reinforcing material has good toughness and mechanical property and can complement the problem of poor mechanical property of flexible graphite. The flexible graphite sheet material formed by compression molding still keeps flexibility and can be freely bent, so that the application universality of the flexible graphite sheet material is improved.
The antioxidant is soaked on the surface of the flexible graphite sheet or inside the flexible graphite sheet, and the temperature is raised in a gradient way, so that the antioxidant permeates into the graphite material to be converted into high-temperature antioxidant substances which are filled into the graphite material and cover the surface of the graphite material, thereby isolating oxidizing gas and blocking the gas from entering the graphite material from the pores, delaying the occurrence of oxidation reaction and improving the high-temperature oxidation resistance of the graphite material. The antioxidant does not need to crush and impregnate the flexible graphite sheet material, and the operation is simpler and more convenient.
Aluminum isopropoxide can be hydrolyzed to generate aluminum oxide, and the aluminum oxide has good high-temperature oxidation resistance, so that the high-temperature oxidation resistance of the graphite plate is improved; and aluminum isopropoxide has a dehydration function, and is convenient for removing moisture in the drying process, so that the influence of the aluminum isopropoxide on high-temperature oxidation resistance is avoided. Phosphoric acid and oxalic acid can promote the ingress of antioxidants into the graphite sheet material, thereby allowing the antioxidants to fill the interior of the graphite material and cover the graphite surface.
Drawings
FIG. 1 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 1 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 ℃ on the right).
FIG. 2 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 2 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 ℃ at different times on the right).
FIG. 3 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 3 (oxidation weight loss ratio of 1h at different temperatures on the left and of 600 ℃ at different times on the right).
FIG. 4 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 4 (oxidation weight loss ratio of 1h at different temperatures on the left and of 600 ℃ at different times on the right).
Fig. 5 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 5 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 c at different times on the right).
Fig. 6 is a flow chart of the preparation of the high temperature oxidation resistant flexible graphite filler of the example.
Fig. 7 is a flow chart of the preparation of the high temperature oxidation resistant flexible graphite packing according to the embodiment.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Example 1
A preparation method of high-temperature oxidation-resistant flexible graphite filler comprises the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution (soaking for 90min at 20 ℃), washing to be neutral, and expanding for 15s at a high temperature of 850 ℃ to obtain expanded graphite worms; the intercalation agent solution comprises the following components in parts by weight: 10 parts of nitric acid, 1 part of potassium permanganate and 5 parts of phosphoric acid; the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1:1.2;
step two, uniformly covering the expanded graphite worms in the step one on the reinforcement with the adhesiveThe surface of the material (carbon fiber) was mechanically pressed (120 kg/cm 2 ) Obtaining a flexible graphite plate; wherein, the mass ratio of the expanded graphite worms to the carbon fibers is 1:0.4;
soaking the flexible graphite sheet material in the step II in an antioxidant solution (soaking for 90min at 60 ℃), drying to remove water, heating to 110 ℃, preserving heat for 12min, continuously heating to 200 ℃ and preserving heat for 12min, continuously heating to 320 ℃ and preserving heat for 35min, and finally heating to 400 ℃ and preserving heat for 12min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 10 parts of aluminum isopropoxide, 8 parts of sodium tetraborate, 5 parts of phosphoric acid, 5 parts of oxalic acid and 30 parts of water.
The high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
The high-temperature oxidation-resistant flexible graphite packing is formed by rolling the high-temperature oxidation-resistant flexible graphite packing.
Example 2
A preparation method of high-temperature oxidation-resistant flexible graphite filler comprises the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution (soaking for 60min at 40 ℃), washing to be neutral, and expanding for 10s at a high temperature of 950 ℃ to obtain expanded graphite worms; the intercalation agent solution comprises the following components in parts by weight: 15 parts of nitric acid, 3 parts of potassium permanganate and 8 parts of phosphoric acid; the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1:2.0;
step two, uniformly covering the expanded graphite worms in the step one on the surface of a reinforcing material (carbon fiber) with an adhesive, and mechanically pressing (180 kg/cm 2 ) Obtaining a flexible graphite plate; wherein, the mass ratio of the expanded graphite worms to the carbon fibers is 1:0.6;
soaking the flexible graphite sheet material in the step II in an antioxidant solution (soaking for 60min at 80 ℃), drying to remove water, heating to 130 ℃, preserving heat for 8min, continuously heating to 220 ℃ and preserving heat for 8min, continuously heating to 340 ℃ and preserving heat for 25min, and finally heating to 420 ℃ and preserving heat for 8min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 20 parts of aluminum isopropoxide, 14 parts of sodium tetraborate, 10 parts of phosphoric acid, 10 parts of oxalic acid and 50 parts of water.
The high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
The high-temperature oxidation-resistant flexible graphite packing is twisted by the high-temperature oxidation-resistant flexible graphite packing.
Example 3
A preparation method of high-temperature oxidation-resistant flexible graphite filler comprises the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution (soaking for 75min at 30 ℃), washing to be neutral, and expanding for 12s at a high temperature of 900 ℃ to obtain expanded graphite worms; the intercalation agent solution comprises the following components in parts by weight: 12 parts of nitric acid, 2 parts of potassium permanganate and 7 parts of phosphoric acid; the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1:1.8;
step two, uniformly covering the expanded graphite worms in the step one on the surface of the reinforcing material (carbon fiber) with the adhesive, and mechanically pressing (150 kg/cm 2 ) Obtaining a flexible graphite plate; wherein, the mass ratio of the expanded graphite worms to the carbon fibers is 1:0.5;
soaking the flexible graphite sheet material in the step II in an antioxidant solution (soaking for 75min at 70 ℃), drying to remove water, heating to 120 ℃, preserving heat for 10min, continuously heating to 210 ℃ and preserving heat for 10min, continuously heating to 330 ℃ and preserving heat for 30min, and finally heating to 410 ℃ and preserving heat for 10min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 15 parts of aluminum isopropoxide, 12 parts of sodium tetraborate, 8 parts of phosphoric acid, 8 parts of oxalic acid and 45 parts of water.
The high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
The high-temperature oxidation-resistant flexible graphite packing is formed by weaving the high-temperature oxidation-resistant flexible graphite packing.
Example 4
A preparation method of high-temperature oxidation-resistant flexible graphite filler comprises the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution (soaking for 75min at 30 ℃), washing to be neutral, and expanding for 12s at a high temperature of 900 ℃ to obtain expanded graphite worms; the intercalation agent solution comprises the following components in parts by weight: 13 parts of nitric acid, 3 parts of potassium permanganate and 8 parts of phosphoric acid; the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1:1.8;
step two, uniformly covering the expanded graphite worms in the step one on the surface of the reinforcing material (carbon fiber) with the adhesive, and mechanically pressing (150 kg/cm 2 ) Obtaining a flexible graphite plate; wherein, the mass ratio of the expanded graphite worms to the carbon fibers is 1:0.5;
soaking the flexible graphite sheet material in the step II in an antioxidant solution (soaking for 75min at 70 ℃), drying to remove water, heating to 120 ℃, preserving heat for 10min, continuously heating to 210 ℃ and preserving heat for 10min, continuously heating to 330 ℃ and preserving heat for 30min, and finally heating to 410 ℃ and preserving heat for 10min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 13 parts of aluminum isopropoxide, 11 parts of sodium tetraborate, 8 parts of phosphoric acid, 7 parts of oxalic acid and 35 parts of water.
The high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
The high-temperature oxidation-resistant flexible graphite packing is formed by rolling the high-temperature oxidation-resistant flexible graphite packing.
Example 5
A preparation method of high-temperature oxidation-resistant flexible graphite filler comprises the following steps:
soaking natural crystalline flake graphite in an intercalation agent solution (soaking for 75min at 30 ℃), washing to be neutral, and expanding for 12s at a high temperature of 900 ℃ to obtain expanded graphite worms; the intercalation agent solution comprises the following components in parts by weight: 13 parts of nitric acid, 3 parts of potassium permanganate and 8 parts of phosphoric acid; the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1:1.8;
step two, uniformly covering the expanded graphite worms in the step one on the surface of the reinforcing material (carbon fiber) with the adhesive, and mechanically pressing (150 kg/cm 2 ) Obtaining a flexible graphite plate; wherein, the mass ratio of the expanded graphite worms to the carbon fibers is 1:0.5;
soaking the flexible graphite sheet material in the step II in an antioxidant solution (soaking for 75min at 70 ℃), drying to remove water, heating to 120 ℃, preserving heat for 10min, continuously heating to 210 ℃ and preserving heat for 10min, continuously heating to 330 ℃ and preserving heat for 30min, and finally heating to 410 ℃ and preserving heat for 10min to obtain the high-temperature antioxidant flexible graphite filler; wherein the antioxidant solution comprises the following components in parts by weight: 13 parts of aluminum isopropoxide, 11 parts of sodium tetraborate, 8 parts of phosphoric acid, 7 parts of oxalic acid and 40 parts of water.
The high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method.
The high-temperature oxidation-resistant flexible graphite packing is formed by weaving the high-temperature oxidation-resistant flexible graphite packing.
The high-temperature oxidation-resistant flexible graphite fillers of examples 1 to 5 were put into a muffle furnace for high-temperature firing, and the oxidation weight loss rates at different oxidation temperatures were measured and oxidation aging was performed for 1 hour at 500 ℃, 600 ℃, 700 ℃, 800 ℃, and 900 ℃ respectively. The test results are shown in table 1:
table 1
As can be seen from the data in table 1, the high temperature oxidation resistant flexible graphite filler of examples 1 to 5 was put into a muffle furnace for high temperature firing, and the oxidation weight loss rate was very low between 500 and 700 ℃. From this, it can be seen that the high temperature oxidation resistant flexible graphite packing materials of examples 1 to 5 have very strong high temperature oxidation resistance under high temperature conditions, and the graphite packing materials of examples 1 to 5 can be used in sealing environments at higher temperatures.
The high-temperature oxidation-resistant flexible graphite filler of examples 1 to 5 was put into a muffle furnace for high-temperature firing, and the oxidation weight loss rate was measured when firing in static air at 600 ℃ for different times. The test results are shown in table 2:
table 2
As can be seen from the data of table 2, the high temperature oxidation-resistant flexible graphite filler of examples 1 to 5 was put into a muffle furnace to burn at high temperature, the oxidation weight loss rate was low in 1 to 7 hours, and the oxidation weight loss rate was gradually increased without a sharp increase. From this, it is seen that the high temperature oxidation resistant flexible graphite filler of examples 1 to 5 does not form a high temperature oxidation resistant substance only on the surface thereof (if only the surface has a high temperature oxidation resistant substance, the oxidation weight loss rate increases sharply after 2 to 3 hours), but forms a high temperature oxidation resistant substance both inside and on the surface.
FIG. 1 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 1 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 ℃ on the right). FIG. 2 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 2 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 ℃ at different times on the right). FIG. 3 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 3 (oxidation weight loss ratio of 1h at different temperatures on the left and of 600 ℃ at different times on the right). FIG. 4 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 4 (oxidation weight loss ratio of 1h at different temperatures on the left and of 600 ℃ at different times on the right). Fig. 5 is a graph of the oxidation weight loss ratio of the high temperature oxidation resistant flexible graphite filler of example 5 (oxidation weight loss ratio of 1h at different temperatures on the left and oxidation weight loss ratio of 600 c at different times on the right).
From fig. 1 to fig. 5, it can be seen that the oxidation weight loss rate graphs of the high-temperature oxidation-resistant flexible graphite fillers in examples 1 to 5 are relatively similar, so that the preparation method has good stability, and the prepared high-temperature oxidation-resistant flexible graphite fillers in the preset range have small performance differences and good high-temperature oxidation resistance.
In summary, according to the invention, the antioxidant is impregnated on the surface of the flexible graphite sheet material or in the flexible graphite sheet material, and the inside of the graphite sheet material is changed into the high-temperature antioxidant substance through gradient heating, and the high-temperature antioxidant substance is filled in the graphite sheet material and covers the surface of the graphite sheet material, so that the oxidizing gas is isolated, the gas is prevented from entering the graphite sheet material from the pores, the oxidation reaction is delayed, and the high-temperature antioxidant property of the graphite sheet material is improved. The antioxidant does not need to crush and impregnate the flexible graphite sheet material, and the operation is simpler and more convenient. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The preparation method of the high-temperature oxidation-resistant flexible graphite filler is characterized by comprising the following steps of:
soaking natural crystalline flake graphite in an intercalation agent solution, washing with water, and expanding at a high temperature of 850-950 ℃ for 10-15 s to obtain expanded graphite worms; wherein, the mass ratio of the natural crystalline flake graphite to the intercalation agent solution is 1: (1.0-2.5), wherein the intercalation agent solution comprises the following components in parts by weight: 10-15 parts of nitric acid, 1-3 parts of potassium permanganate and 5-8 parts of phosphoric acid;
step two, uniformly covering the expanded graphite worms in the step one on the surface of the reinforcing material with the adhesive, and mechanically pressing to obtain a flexible graphite sheet;
soaking the flexible graphite sheet material in the second step in an antioxidant solution, drying, heating to 110-130 ℃ and preserving heat for 8-12 min, continuously heating to 200-220 ℃ and preserving heat for 8-12 min, continuously heating to 320-340 ℃ and preserving heat for 25-35 min, and finally heating to 400-420 ℃ and preserving heat for 8-12 min to obtain the high-temperature antioxidant flexible graphite filler;
wherein the antioxidant solution comprises the following components in parts by weight: 10-20 parts of aluminum isopropoxide, 8-14 parts of sodium tetraborate, 5-10 parts of phosphoric acid, 5-10 parts of oxalic acid and 20-60 parts of water.
2. The method for preparing the high-temperature oxidation-resistant flexible graphite filler according to claim 1, which is characterized in that: in the second step, the reinforcing material is carbon fiber, and the adhesive is vinyl acetate; the pressure of mechanical pressing in the second step is 120-180 kg/cm < 2 >.
3. The method for preparing the high-temperature oxidation-resistant flexible graphite filler according to claim 2, which is characterized in that: the mass ratio of the expanded graphite worms to the carbon fibers is 1: (0.4-0.6).
4. The method for preparing the high-temperature oxidation-resistant flexible graphite filler according to claim 1, which is characterized in that: the antioxidant solution in the third step comprises the following components in parts by weight: 10-15 parts of aluminum isopropoxide, 10-12 parts of sodium tetraborate, 7-8 parts of phosphoric acid, 7-8 parts of oxalic acid and 35-45 parts of water.
5. The method for preparing the high-temperature oxidation-resistant flexible graphite filler according to claim 1 or 4, which is characterized in that: the gradient heating in the third step is specifically as follows: heating to 120 ℃ for 10min, continuously heating to 210 ℃ for 10min, continuously heating to 330 ℃ for 30min, and finally heating to 410 ℃ for 10min.
6. The method for preparing the high-temperature oxidation-resistant flexible graphite filler according to any one of claims 1 to 4, which is characterized in that: the dipping temperature in the first step is 20-40 ℃ and the dipping time is 60-90 min; the dipping temperature in the third step is 60-80 ℃ and the dipping time is 60-90 min.
7. A high-temperature oxidation-resistant flexible graphite filler is characterized in that: the high-temperature oxidation-resistant flexible graphite filler is prepared by the preparation method of any one of claims 1 to 6.
8. The utility model provides a high temperature oxidation resistant flexible graphite packing which characterized in that: the high-temperature oxidation-resistant flexible graphite packing is formed by rolling, twisting or braiding the high-temperature oxidation-resistant flexible graphite packing according to claim 7.
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| CN114790000B (en) * | 2022-04-19 | 2024-04-02 | 宁波信远炭材料有限公司 | High-temperature-resistant sealing material based on expanded graphite and preparation method thereof |
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