CN116143537B - Composite carbon-carbon crucible containing antioxidant coating and preparation method thereof - Google Patents
Composite carbon-carbon crucible containing antioxidant coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite carbon-carbon crucible containing an antioxidant coating and a preparation method thereof, and relates to the technical field of carbon fiber material forming processes. The carbon/carbon composite crucible comprises: the high-density carbon fiber preform is prepared by laying a weft-free cloth layer and a net tire layer according to a layer-by-layer alternate laying method, spreading graphite powder layer by layer and carrying out composite needling; and a carbonized matrix formed by carbonizing a resin liquid distributed on the surface of the high-density carbon fiber preform and in the structure thereof; the resin liquid at least comprises resin and N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid. The density of the carbon-carbon thermal field crucible prepared by the invention is effectively improved, and the mechanical property is obviously enhanced; meanwhile, after the surface is coated with the antioxidation coating, the anti-oxidation coating has excellent antioxidation capability and thermal shock resistance, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of carbon fiber material forming processes, and particularly relates to a composite carbon-carbon crucible containing an antioxidant coating and a preparation method thereof.
Background
In recent years, the photovoltaic power generation industry has a great demand for single crystal silicon. As an important thermal field material for producing single crystal silicon (rod), carbon-carbon composite crucibles have also been rapidly developed. Currently, when a single crystal silicon furnace pulls a single crystal silicon rod, a quartz crucible containing polycrystalline silicon is placed in a crucible made of carbon-carbon composite materials. In the process of drawing the monocrystalline silicon rod, the temperature in the furnace is about 1500 ℃, the quartz crucible is softened, and the crucible is supported by the carbon-carbon composite material. Under the working condition, the softened quartz crucible extrudes and reacts on the carbon-carbon composite material crucible, and simultaneously silicon vapor, silicon-containing gas and splashed silicon liquid can react with the carbon-carbon composite material crucible at high temperature, so that the carbon-carbon composite material crucible is corroded, even fails, and the service life of the carbon-carbon composite material crucible is seriously influenced. How to effectively solve the problem that the carbon-carbon composite material is corroded under the working condition of drawing a monocrystalline silicon rod so as to prolong the service life of a carbon-carbon composite material crucible is a problem which needs to be solved for further reducing the cost of the monocrystalline silicon solar cell. The silicon dioxide/silicon coating is prepared on the carbon-carbon composite material crucible body, so that the corrosion resistance of the carbon-carbon composite material crucible can be improved, and the service life of the carbon-carbon composite material crucible can be effectively prolonged.
A uniform and compact silicon carbide coating is coated on the inner surface of the carbon-carbon composite material crucible by utilizing a brushing process, so that corrosion resistance of silicon vapor, silicon-containing gas, splashed silicon liquid and the like to the crucible can be effectively prevented, and the service life of the carbon-carbon composite material crucible can be effectively prolonged. Patent CN103553711a discloses a composite coating carbon/carbon composite material crucible and a preparation method thereof, and the silicon carbide coating and the silicon nitride coating are generated by in-situ reaction on the inner surface of the carbon/carbon composite material crucible by adopting a chemical vapor deposition process, so that the corrosion of silicon-containing steam on the inner surface of the carbon/carbon crucible can be effectively inhibited. Patent CN103553711a proposes to prepare a composite coating layer of silicon carbide coating layer/silicon nitride coating layer on the surface of a carbon/carbon composite material thermal insulation cylinder, so as to effectively inhibit corrosion of silicon vapor generated after melting of silicon material on the surface of the carbon/carbon thermal insulation cylinder; in addition, patent CN111848201a also proposes to form a silicon carbide coating/silicon coated carbon/carbon crucible on the surface of the carbon/carbon crucible by a plasma spraying method, so as to improve the anti-siliconizing corrosion capability of the carbon/carbon crucible, thereby prolonging the service life of the crucible. Therefore, the development of a new route for preparing the carbon/carbon composite material is important for expanding the application field of the carbon/carbon composite material.
Disclosure of Invention
The invention aims to provide a composite carbon-carbon crucible containing an antioxidant coating and a preparation method thereof, wherein the density of the carbon-carbon thermal field crucible is effectively improved, and the mechanical property is obviously enhanced; meanwhile, after the surface is coated with the antioxidation coating, the anti-oxidation coating has excellent antioxidation capability and thermal shock resistance, and has wide application prospect.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a method for preparing a carbon/carbon composite crucible, comprising: preparing a high-density carbon fiber preform, paving a non-woven cloth layer and a net tire layer according to a layer-by-layer alternate paving method, spreading graphite powder layer by layer, and performing composite needling to obtain the high-density carbon fiber preform;
and carbonizing the resin liquid to form carbonized matrix, wherein the resin liquid is distributed on the surface and the structure of the high-density carbon fiber preform;
the resin liquid at least comprises resin and N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid. According to the invention, graphite powder is added into the carbon fiber preform structure, and the carbon/carbon composite material crucible is prepared after series of operations such as brushing, resin dipping and the like, and has higher density and excellent mechanical properties. The reason is probably that the existence of graphite powder can effectively adsorb molecular chains of the resin matrix to play a role of physical crosslinking points, so that the binding force inside the resin is enhanced; and the carbon fiber-resin composite material can act on the interface of the carbon fiber and the resin, so that the bonding performance of the interface is improved, and the carbon residue rate of the composite material after high-temperature carbonization is improved. Meanwhile, the N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is added into the resin liquid, is compounded with the resin in a synergistic way, acts on the high-density carbon fiber preform, and the prepared carbon/carbon composite material crucible has higher density and better mechanical property, and obviously improves the tensile strength, the compressive strength and the bending strength. The reason for this may be that the presence of N-hydroxyethyl ethylenediamine-N, N' -triacetic acid may promote retention of more resin in the matrix of the composite material during the impregnation operation by means of partial physical/chemical actions, thereby improving the impregnation effect, shortening the densification cycle, promoting rapid densification of the C/C material, improving the density of the composite material, and improving the mechanical properties of the carbon fiber composite material.
Preferably, there are n layers of laid fabric layer, n-1 layers of net tire layer, where n is greater than or equal to 2.
Preferably, the interweaving angle of the laid layer and the carcass layer is 90 °.
Preferably, the granularity of the graphite powder is 100-300 meshes.
Preferably, the resin liquid further comprises sodium cyclohexylsulfamate and p-toluenesulfonic acid. According to the invention, sodium cyclohexylsulfamate and p-toluenesulfonic acid are also added into the resin liquid to be compounded in a synergistic way with other components, and the resin liquid acts on the high-density carbon fiber preform, so that the density of the carbon/carbon composite material crucible is further increased, the mechanical property, tensile property, compression property and bending property of the carbon/carbon composite material crucible are enhanced, and the mechanical property, compression property and bending property of the carbon/carbon composite material crucible are effectively improved. The reason for this may be that the presence of N-hydroxyethyl ethylenediamine-N, N' -triacetic acid, sodium cyclohexylsulfamate and p-toluenesulfonic acid, possibly through partial physical/chemical action, may on the one hand be able to enter into the grooves or pores of the carbon fiber surface as small molecular substances, playing a certain role in modifying the carbon fiber surface, improving the interface problem with the resin; the other side possibly forms a stable network structure with the resin, so that the resin and the like can stay in the pore structure of the preform matrix better, the impregnation effect is improved, the densification process of the C/C material is improved, the density of the composite material is further increased, and the mechanical property of the composite material is enhanced.
The weight ratio of the sodium cyclohexylsulfamate to the resin is 3-5:1, and the weight ratio of the sodium cyclohexylsulfamate to the N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is 1:0.4-0.6; the weight ratio of the p-toluenesulfonic acid to the resin is 0.2-0.5:1.
The invention discloses a specific preparation method of the carbon/carbon composite material crucible, which comprises the following steps:
s1: alternately laminating the non-woven cloth and the net tyre at 0 degrees and 90 degrees, uniformly spreading graphite powder on each layer of net tyre, performing needling, spreading on a core mould to prepare a crucible shape, and preparing a high-density carbon fiber preform with the designed thickness;
s2: brushing resin liquid on the high-density carbon fiber preform prepared in the step S1, and then dehydrating and curing in a vacuum drying oven at 130-170 ℃ for 1-3 min; carbonizing in a carbonization furnace; then placing the mixture in a pressure impregnation tank for densification treatment, specifically: and (3) carbonizing the impregnated resin liquid in a carbonizing furnace for repeated operation, and finally obtaining the carbon/carbon composite material crucible with the required density.
Preferably, the density of the high-density carbon fiber preform is 0.7-0.9 g/cm 3 。
Preferably, the resin liquid used in the process of brushing the resin liquid and dipping the resin liquid comprises resin and ethanol.
The resin includes a phenol resin or a furan resin; the concentration of the ethanol is 70-80%.
Preferably, the mass ratio of the resin to the ethanol is 1:3-4.
Preferably, the resin liquid impregnation process specifically comprises: adding 5-10wt% of phosphoric acid serving as a curing agent into the resin liquid, uniformly stirring, then impregnating the high-density carbon fiber preform, and filling nitrogen in the impregnation process, wherein the pressure is 1.5-2 mpa, the impregnation temperature is 60-80 ℃, and the time is 1-3 h; and then heating and solidifying, wherein the nitrogen pressure is 1.5-2 Mpa, the temperature is 160-200 ℃ and the time is 1-3 h.
Preferably, the carbonization process specifically includes: firstly, the temperature is increased to 90-100 ℃ from 20-30 ℃ at a temperature increasing rate of 35-40 ℃, then the temperature is increased to 800-900 ℃ at a temperature increasing rate of 95-100 ℃/h, then the temperature is increased to 1800-1900 ℃ at a temperature increasing rate of 30-35 ℃/h, then the temperature is reduced to 800-900 ℃ at a temperature reducing rate of 40-45 ℃/h, then the temperature is reduced to 100-110 ℃ at a temperature reducing rate of 50-55 ℃/h, and finally the temperature is naturally cooled to 20-30 ℃.
The invention also discloses a preparation method of the antioxidant coating on the surface of the carbon/carbon composite material crucible, which comprises the following steps:
preparing slurry, namely mixing and stirring Si powder, mo powder and silica sol to prepare the slurry;
and (3) preparing a coating, namely uniformly brushing the slurry on the surface of the carbon/carbon composite material crucible, and performing high-temperature treatment in a vacuum siliconizing furnace to obtain the antioxidation coating.
Further specifically, the preparation method of the antioxidant coating on the surface of the carbon/carbon composite crucible comprises the following steps:
preparing slurry, mixing Si powder, mo powder and silica sol according to a mass ratio, and stirring for at least 30min to obtain the slurry;
the preparation of the coating, namely uniformly brushing the slurry on the surface of a carbon/carbon composite material crucible, drying at 45-55 ℃, then placing the crucible in a graphite mold, placing the graphite mold in a vacuum siliconizing furnace, vacuumizing, filling Ar to normal pressure, heating the furnace temperature to 1430-1530 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 5-30 min, then cooling to 950-1000 ℃ at a cooling rate of 8-12 ℃/min, taking out a sample after power supply is naturally cooled to the room temperature, and obtaining the Mo-Si coating, wherein the furnace pressure is kept to normal pressure in the whole process.
Preferably, the mass ratio of the Si powder to the Mo powder to the silica sol is 3-4:1-2:5-6.
Preferably, the thickness of the antioxidation coating is 0.05-0.35 mm.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, graphite powder is added into the carbon fiber preform, so that the density of the preform is improved, and the CVI densification or impregnation carbonization time period is reduced; and the resin is brushed on the surface of the carbon fiber preform, and then the carbon fiber preform is solidified and carbonized, so that the density of the preform is quickly improved, the strength of the preform is increased, the CVI densification process step is reduced, the resin impregnation efficiency is improved, the deformation of the carbon fiber preform in the pressure impregnation process is avoided, and the process period is greatly shortened; meanwhile, the surface of the prepared carbon/carbon composite material crucible is coated with a coating, so that the crucible has excellent oxidation resistance and thermal shock resistance, and can meet the requirement of long-term use in an oxidation environment at 1400 ℃. In addition, sodium cyclohexylsulfamate and p-toluenesulfonic acid are added into the resin liquid to be compounded in a synergistic way with other components, and the resin liquid acts on the high-density carbon fiber preform, so that the density of the carbon/carbon composite material crucible is further increased, the mechanical property, the tensile property, the compression property and the bending property of the carbon/carbon composite material crucible are effectively improved.
Therefore, the invention provides the composite carbon-carbon crucible containing the antioxidation coating and the preparation method thereof, the density of the carbon-carbon thermal field crucible is effectively improved, and the mechanical property is obviously enhanced; meanwhile, after the surface is coated with the antioxidation coating, the anti-oxidation coating has excellent antioxidation capability and thermal shock resistance, and has wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of a modified furan resin in examples 6 and 8 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
the net tire used in the embodiment of the invention is prepared by scattering, carding, net laying and needling chopped carbon fibers, and the gram weight is 80g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The non-woven cloth is carbon fiber non-woven cloth.
The graphite powder used in the examples of the present invention had an average particle size of 150 mesh.
Si powder and Mo powder are all commercially available, and the particle size is 100-200 meshes; silica sol was purchased from tabacco Hengxin chemical technology limited.
Example 1:
preparation of a carbon/carbon composite crucible:
s1: alternately laminating the non-woven layer and the mesh tire layer at 0 degree and 90 degrees, uniformly spreading graphite powder with certain granularity on each layer of mesh tire, performing needling, spreading on a core mold to prepare crucible shape, and preparing into high-density carbon fiber preform with a bulk density of 0.84g/cm 3 ；
S2: brushing resin liquid (furan resin: 75% ethanol=1:4) on the high-density carbon fiber preform prepared in the step S1, and then dehydrating and curing in a vacuum drying oven at 160 ℃ for 2min; carbonizing in a carbonization furnace; then placing the mixture in a pressure impregnation tank for densification treatment, specifically: and (3) carbonizing the impregnated resin liquid in a carbonizing furnace for repeated operation, and finally obtaining the carbon/carbon composite material crucible with the required density.
It should be noted that:
the resin liquid impregnating process specifically comprises the following steps: adding 8wt% of phosphoric acid serving as a curing agent into the resin solution, uniformly stirring, then impregnating the high-density carbon fiber preform, and filling nitrogen in the impregnation process, wherein the pressure is 2Mpa, the impregnation temperature is 70 ℃, and the time is 2h; then heating and solidifying, wherein the nitrogen pressure is 2Mpa, the temperature is 180 ℃ and the time is 2h;
the carbonization process specifically comprises the following steps: firstly, the temperature is increased to 100 ℃ from 25 ℃ at a temperature increasing rate of 36 ℃, then the temperature is increased to 900 ℃ at a temperature increasing rate of 100 ℃/h, then the temperature is increased to 1850 ℃ at a temperature increasing rate of 35 ℃/h, then the temperature is reduced to 900 ℃ at a temperature reducing rate of 40 ℃/h, then the temperature is reduced to 100 ℃ at a temperature reducing rate of 55 ℃/h, and finally the temperature is naturally cooled to 25 ℃.
Preparing an antioxidation coating on the surface of the carbon/carbon composite material crucible:
preparing slurry, mixing Si powder, mo powder and silica sol according to the mass ratio of 3.6:1.4:5.5, and stirring for at least 30min to obtain slurry;
the preparation of the coating, the slurry is evenly brushed on the surface of a carbon/carbon composite material crucible, the crucible is dried at 50 ℃, then the crucible is put into a graphite mold, the graphite mold is put into a vacuum siliconizing furnace, ar is filled to normal pressure after vacuumizing, the furnace temperature is increased to 1480 ℃ from room temperature at a heating rate of 8 ℃/min, the temperature is kept for 20min, then the temperature is reduced to 1000 ℃ at a cooling rate of 10 ℃/min, a sample is taken out after the power source is cooled to room temperature, the antioxidation coating (thickness is 0.185 mm) is obtained, and the furnace pressure is kept to normal pressure in the whole process.
Example 2:
the preparation of a carbon/carbon composite crucible was different from that of example 1:
sodium cyclohexylsulfamate, N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid and p-toluenesulfonic acid are also added into the resin solution; wherein, the weight ratio of the sodium cyclohexylsulfamate to the resin is 4:1, and the weight ratio of the sodium cyclohexylsulfamate to the N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is 1:0.5; the weight ratio of the p-toluenesulfonic acid to the resin is 0.35:1.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 1: the preparation of the carbon/carbon composite crucible was that of this example.
Example 3:
the preparation of a carbon/carbon composite crucible was different from that of example 2:
the density of the high-density carbon fiber preform is 0.76g/cm 3 ；
In the resin liquid, the mass ratio of the resin to the ethanol is 1:3; the weight ratio of the sodium cyclohexylsulfamate to the resin is 3:1, and the weight ratio of the sodium cyclohexylsulfamate to the N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is 1:0.4; the weight ratio of the p-toluenesulfonic acid to the resin is 0.25:1;
the carbonization process specifically comprises the following steps: firstly, the temperature is increased to 95 ℃ from 20 ℃ at a temperature increasing rate of 40 ℃, then the temperature is increased to 850 ℃ at a temperature increasing rate of 95 ℃/h, then the temperature is increased to 1800 ℃ at a temperature increasing rate of 30 ℃/h, then the temperature is reduced to 900 ℃ at a temperature reducing rate of 40 ℃/h, then the temperature is reduced to 100 ℃ at a temperature reducing rate of 50 ℃/h, and finally the temperature is naturally cooled to 20 ℃.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 2: the preparation of the carbon/carbon composite crucible was that prepared in this example;
si powder, mo powder and silica sol in a mass ratio of 3:1:5; the thickness of the oxidation-resistant coating is 0.124mm.
Example 4:
the preparation of a carbon/carbon composite crucible was different from that of example 2:
sodium cyclohexylsulfamate is not added into the resin liquid.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 2: the preparation of the carbon/carbon composite crucible was that of this example.
Example 5:
the preparation of a carbon/carbon composite crucible was different from that of example 2:
n-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is not added to the resin liquid.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 2: the preparation of the carbon/carbon composite crucible was that of this example.
Example 6:
the preparation of a carbon/carbon composite crucible was different from that of example 2:
the modified furan resin prepared in this example was used instead of furan resin.
The preparation method of the modified furan resin comprises the following steps:
mixing formaldehyde solution and phenol according to the molar ratio of formaldehyde to phenol of 1.5-1.7:1, adding sodium hydroxide to adjust the pH to 8.5-9.5, reacting with the mixture for 0.5-1 h at 94-97 ℃, then adding 5-methoxy-2-nitrophenol (the molar ratio of the mixture to phenol of 1:3-5), and reacting for 0.5-1 h at constant temperature; dehydrating, adding furfuryl alcohol (the addition amount is 45-60wt% of the total amount of the reaction system), regulating the pH to 5-6 by oxalic acid, heating to 85-95 ℃, reacting at constant temperature for 1-2 h, cooling, and discharging to obtain the modified furan resin (the viscosity is 10-12 mPa.s). In the preparation process of the furan resin, the 5-methoxy-2-nitrophenol is added as one of the polymerization monomers to prepare the modified furan resin, so that the modified furan resin has more excellent bonding performance, can further enhance the density of the carbon fiber plate and improve the comprehensive performance of the carbon fiber plate when being applied to the preparation process of the carbon fiber plate; and the mechanical property of the composite is obviously improved, and the tensile property, the compression property and the bending property of the composite are further enhanced.
In this example, the modified furan resin was prepared specifically as follows:
mixing formaldehyde solution and phenol according to the molar ratio of formaldehyde to phenol of 1.6:1, adding sodium hydroxide to adjust the pH value to 9.0, reacting with the mixture for 0.5h at 95 ℃, then adding 5-methoxy-2-nitrophenol (the molar ratio of the mixture to phenol of 1:4), and reacting for 1h at constant temperature; dehydrating, adding furfuryl alcohol (the addition amount is 52wt% of the total amount of the reaction system), regulating the pH to 5.5 by oxalic acid, heating to 90 ℃, reacting at constant temperature for 1.5 hours, cooling, and discharging to obtain the modified furan resin (the viscosity is 11.2 mPa.s).
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 2: the preparation of the carbon/carbon composite crucible was that of this example.
Example 7:
the preparation of a carbon/carbon composite crucible was different from that of example 1:
the modified furan resin prepared in this example was used instead of furan resin.
The modified furan resin was prepared as in example 6.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 1: the preparation of the carbon/carbon composite crucible was that of this example.
Example 8:
the preparation of a carbon/carbon composite crucible was different from example 6:
the modified furan resin was prepared in this example.
The preparation of the modified furan resin was different from example 6:
the 5-methoxy-2-nitrophenol was replaced with an equivalent molar amount of phenol.
The preparation of the above-mentioned carbon/carbon composite crucible surface oxidation-resistant coating is different from that of example 6: the preparation of the carbon/carbon composite crucible was that of this example.
Test example 1:
infrared test
The test is carried out by a Fourier infrared spectrometer, and the sample structure is characterized by a potassium bromide tabletting method. Wherein the wave number range is 4000-500 cm -1 。
The modified furan resins prepared in example 6 and example 8 were subjected to the above test, and the results are shown in fig. 1. As can be seen from the analysis in the figure, in the infrared spectrum of the modified furan resin prepared in example 6, 1518cm compared with that in the infrared spectrum of the modified furan resin prepared in example 8 -1 、1340cm -1 、868cm -1 Characteristic absorption peaks of the nitro groups appear nearby, and the above results indicate that the modified furan resin in example 5 was successfully produced.
Density determination
Density determination was performed using the Archimedes method.
The above test was performed on the carbon/carbon composite crucibles prepared in examples 1 to 8, and the results are shown in table 1:
TABLE 1 Density test results
As can be seen from the analysis in Table 1, the density of the carbon/carbon composite crucible prepared in example 2 was significantly higher than that of example 1, and the effect of example 2 was better than that of examples 4-5, and the effect of examples 4-5 was better than that of example 1, indicating that the addition of sodium cyclohexylsulfamate and/or N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid to the resin solution was able to improve the overall density of the carbon/carbon composite crucible; and under the condition that the two materials exist at the same time, the compound enhancement effect is achieved, and the density enhancement effect of the carbon/carbon composite material crucible is better. Example 6 is better than example 2 and example 8, and example 7 is better than example 1, indicating that the modified furan resin is prepared by adding 5-methoxy-2-nitrophenol during the preparation of the modified resin, and the density of the carbon/carbon composite crucible can be further enhanced when the modified furan resin is applied to the preparation of the carbon/carbon composite crucible.
Test example 2:
mechanical property test
Tensile property measurement: the axial tensile property of the sample is tested, the sample size is 100X 10X 3mm, and the test instrument is a three-SiGMT-5205 universal tester. The tensile strength was calculated according to the following equation:
tensile strength=p b /F
Wherein P is b Represents the maximum tensile load, N; f represents the cross-sectional area of the sample in cm 2 。
Compression performance measurement: the size of the test sample is 10 multiplied by 10mm, the test instrument is a three-Sitting GMT-5205 universal tester, and the parallel direction is measured. Compressive strength was calculated according to the following formula:
compressive strength=p m /A
Wherein P is m Represents the maximum compression load, N; a represents the pressure area of the test sample, mm 2 。
Flexural performance measurement: the sample size was 55X 10X 4mm and the span was 40mm using the three-point bending method test. The flexural strength was calculated according to the following equation:
flexural strength=3p n L/(2bd 2 )
Wherein P is n Represents the maximum bending load, N; l represents span, mm; b represents the width of the test sample, mm; d represents the thickness of the test specimen, mm.
The above test was performed on the carbon/carbon composite crucibles prepared in examples 1 to 8, and the results are shown in table 2:
TABLE 2 mechanical test results
As can be seen from the analysis in Table 2, the tensile strength, compressive strength and bending strength of the carbon/carbon composite crucible prepared in example 2 are significantly higher than those of example 1, and the effect of example 2 is better than that of examples 4-5, and the effect of examples 4-5 is better than that of example 1, which indicates that the mechanical properties, tensile strength, compressive strength and bending strength of the carbon/carbon composite crucible can be improved by adding sodium cyclohexylsulfamate and/or N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid into the resin solution; and under the condition that the two materials exist at the same time, the composite reinforcing effect is achieved, and the mechanical property improvement effect of the carbon/carbon composite material crucible is better. Example 6 is better than example 2 and example 8, and example 7 is better than example 1, indicating that the mechanical properties of the carbon/carbon composite crucible can be further enhanced by adding 5-methoxy-2-nitrophenol during the preparation of the modified resin to prepare the modified furan resin, and applying the modified furan resin to the preparation of the carbon/carbon composite crucible.
Test example 3:
antioxidant and thermal shock resistance test
The surface condition of the material was observed after 10 hours of oxidation in air at 1500 ℃ and 10 times of thermal shock tests, and the mass change before and after the treatment was calculated.
The weight gain rate was 0.73%.
The carbon/carbon composite material crucible with the surface coating treated prepared in examples 1 to 8 was subjected to the above test, and the surface coating was observed to remain intact without falling off and chipping, and the weight change results are shown in table 3:
TABLE 3 antioxidant and thermal shock resistance test results
As can be seen from the analysis in Table 3, the carbon/carbon composite material crucible with the surface coating layer prepared in examples 1-8 has the weight gain rate less than 2.1% after the oxidation resistance and thermal shock resistance test, and has excellent oxidation resistance and thermal shock resistance.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for preparing a carbon/carbon composite crucible, comprising: preparing a high-density carbon fiber preform, paving a non-woven cloth layer and a net tire layer according to a layer-by-layer alternate paving method, spreading graphite powder layer by layer, and performing composite needling to obtain the high-density carbon fiber preform;
and a carbonization process, the carbonization process comprising:
brushing resin liquid on the high-density carbon fiber preform, and then dehydrating and curing in a vacuum drying oven at 130-170 ℃ for 1-3 min; carbonizing in a carbonization furnace; then placing the mixture in a pressure impregnation tank for densification treatment, specifically: carbonizing the impregnated resin liquid in a carbonizing furnace for repeated operation to obtain the carbon/carbon composite material crucible with the required density;
the method is characterized in that: the resin liquid at least comprises resin, N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid and sodium cyclohexylsulfamate; the weight ratio of the sodium cyclohexylsulfamate to the resin is 3-5:1, and the weight ratio of the sodium cyclohexylsulfamate to the N-hydroxyethyl ethylenediamine-N, N ', N' -triacetic acid is 1:0.4-0.6.
2. The method for preparing a carbon/carbon composite crucible according to claim 1, wherein: and n layers of the weft-free fabric layer and n-1 layers of the net tire layer, wherein n is more than or equal to 2.
3. The method for preparing a carbon/carbon composite crucible according to claim 1, wherein: the interweaving angle of the non-woven fabric layer and the net tire layer is 90 degrees.
4. The method for preparing a carbon/carbon composite crucible according to claim 1, wherein: the granularity of the graphite powder is 100-300 meshes.
5. The method for preparing a carbon/carbon composite crucible according to claim 1, wherein: the resin liquid also comprises p-toluenesulfonic acid.
6. The method for preparing a carbon/carbon composite crucible according to claim 1, wherein: the resin is selected from phenolic resin or furan resin.
7. A preparation method of an antioxidant coating on the surface of a carbon/carbon composite crucible comprises the following steps:
preparing slurry, namely mixing and stirring Si powder, mo powder and silica sol to prepare the slurry;
and (3) preparing a coating, namely uniformly brushing the slurry on the surface of the carbon/carbon composite material crucible prepared by the preparation method of claim 1, and performing high-temperature treatment in a vacuum siliconizing furnace to obtain the antioxidation coating.
8. The method for preparing the carbon/carbon composite crucible surface oxidation-resistant coating according to claim 7, wherein: the mass ratio of the Si powder to the Mo powder to the silica sol is 3-4:1-2:5-6.
9. The method for preparing the carbon/carbon composite crucible surface oxidation-resistant coating according to claim 7, wherein: the thickness of the antioxidation coating is 0.05-0.35 mm.
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