CN108299825B - Long-time high-temperature-resistant resin-based composite wave-transmitting material and preparation method thereof - Google Patents
Long-time high-temperature-resistant resin-based composite wave-transmitting material and preparation method thereof Download PDFInfo
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- CN108299825B CN108299825B CN201810244205.2A CN201810244205A CN108299825B CN 108299825 B CN108299825 B CN 108299825B CN 201810244205 A CN201810244205 A CN 201810244205A CN 108299825 B CN108299825 B CN 108299825B
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Abstract
The invention relates to a long-time high-temperature-resistant resin-based composite wave-transmitting material and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a polyimide resin solution; (2) compounding resin and quartz fiber; (3) heat treatment under vacuum condition; (4) laying or winding; (5) curing and post-curing. The composite material prepared by the invention does not release small molecules in the curing process, and the obtained composite material has low porosity; meanwhile, the composite material has better heat-resistant grade, still has better mechanical property and dielectric property when used under the conditions of high temperature and long time, has simple preparation process and high production efficiency, and has important engineering application value.
Description
Technical Field
The invention relates to the technical field of wave-transmitting materials, in particular to a long-time high-temperature-resistant resin-based composite wave-transmitting material and a preparation method thereof.
Background
The traditional fiber reinforced resin matrix composite (such as epoxy resin matrix composite wave-transmitting material) has excellent mechanical properties such as high specific strength, high specific stiffness, good fatigue fracture resistance and the like, but is often poor in heat resistance, and is greatly limited in application in the fields of national defense, aerospace and the like.
Polyimide resin (PI) is a heat-resistant polymer material with very excellent performance, and has high heat resistance (T)g>350 ℃), good dielectric properties (below 50MHz, the dielectric constant of 3.1-3.3 and the dielectric loss of 0.006-0.007), excellent mechanical properties, chemical resistance and dimensional stability, is a resin matrix for wave-transmitting materials with development potential, and has irreplaceable effects in the field of high-temperature-resistant wave-transmitting materials.
The conventional preparation method of the fiber reinforced resin matrix composite material generally comprises three steps of glue solution preparation, prepreg preparation and curing molding. During the curing and forming process, carbon deposition is generated by high-temperature thermal decomposition, which easily causes the dielectric property of the composite material to be greatly reduced. In addition, the quartz fiber reinforced polyimide resin composite material prepared at the present stage generally has a long-time use temperature of 300-350 ℃, and can not meet the performance requirement of long-time use at a higher temperature. Meanwhile, the dielectric property of the carbon deposit is greatly reduced due to the carbon deposit generated by thermal decomposition. At present, along with the continuous development of the aerospace field, the performance requirement of the wave-transparent composite material is higher and higher, and the common composite material cannot meet the requirement, so that the preparation of the composite material with high strength and high heat-resistant grade is very critical.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a high-strength and heat-resistant quartz fiber reinforced polyimide resin composite material. The composite material still has mechanical property and dielectric property when used at 450-500 ℃ for a long time (30min), no small molecules are released in the mould pressing process, and the obtained composite material has low porosity.
(II) technical scheme
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a long-time high-temperature-resistant resin-based composite wave-transmitting material comprises the following steps:
(1) preparing a polyimide resin solution: dissolving polyimide resin in an organic solvent to prepare a polyimide resin solution;
(2) compounding of resin and quartz fiber: compounding the polyimide resin solution and the quartz fiber fabric to prepare a resin/quartz fiber composite material;
(3) heat treatment under vacuum: airing the composite material, and then carrying out heat treatment under a vacuum condition;
(4) laying or winding: cutting the composite material processed in the step (3) into a proper size, and layering or winding according to a set mode;
(5) curing and post-curing: and heating and pressurizing the layered or wound composite material for curing and post-curing to obtain the resin-based composite wave-transmitting material.
Preferably: in the step (3), the composite material is aired in an environment with the temperature of 0-40 ℃ and the humidity of below 40%.
Preferably, the airing time is controlled to be 5-24 hours.
Preferably: in the step (3), a vacuum oven is adopted for heat treatment, the vacuum degree is-0.09 to-0.1 MPa, the temperature is 150 to 250 ℃, and the time is 1.5 to 3 hours.
Preferably: the solidification and post-solidification are carried out by stages by adopting a vacuum hot press, and the process conditions of each stage are as follows:
a first curing stage: heating the vacuum hot press to 250-300 ℃ and preserving heat for 1-1.5 h;
and (3) a second curing stage: heating the vacuum hot press to 320-350 ℃, preserving heat for 5-15 min, applying pressure of 5-20 MPa, preserving heat and maintaining pressure for 0.5-1 h;
and a third curing stage: heating the vacuum hot press to 370-380 ℃, and maintaining the temperature and the pressure for 2-4 h;
a fourth post-curing stage: and heating the vacuum hot press to 390-400 ℃, and keeping the temperature and pressure for 2-4 h.
Preferably: the polyimide resin solution is coated on the quartz fiber fabric by a coating method to be compounded.
Preferably: the mass of the resin is 50-100% of that of the quartz fiber fabric.
Preferably: the organic solvent is a high boiling point organic solvent with a boiling point of more than 100 ℃, and is preferably any one or more of dioxane, dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
Preferably: in the polyimide resin solution, the mass concentration of the polyimide is 15-50%.
The invention provides a long-time high-temperature-resistant resin-based composite wave-transmitting material which is prepared by adopting the preparation method.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
when the composite material consisting of the resin and the quartz fiber is treated in a vacuum oven, the organic solvent can be removed, the imidization process is completed, and micromolecular substances are released. Therefore, no small molecules are released in the heating and pressurizing curing process, the porosity of the composite material is effectively reduced, and the heat-resistant grade and the heat-resistant time are improved. The process has the advantages that the process is simplified, the efficiency is improved, the internal stress of a workpiece can be effectively eliminated, and better mechanical property and dielectric property can be still kept when the vacuum hot press is used at high temperature for a long time.
The quartz fiber reinforced modified polyimide resin composite material prepared by the invention does not release small molecules in the curing process, and the obtained composite material has low porosity; meanwhile, the composite material has better heat-resistant grade, still has better mechanical property and dielectric property when used under the conditions of high temperature and long time, has simple preparation process and high production efficiency, and has important engineering application value.
Drawings
FIG. 1 is a schematic flow diagram of a preparation method provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a long-time high-temperature-resistant resin-based composite wave-transmitting material, which comprises the following steps of:
(1) preparation of polyimide resin solution
The resin glue solution used by the invention is polyimide resin solution prepared from polyimide resin, and the solvent is organic solvent. When in preparation, the polyimide resin is mixed with an organic solvent. Of course, the polyimide resin may be stirred at a speed of not more than 400 rpm, preferably 200 to 300 rpm, to sufficiently dissolve the polyimide resin, thereby preventing the generation of a large amount of bubbles in the solution.
In this step, the type of polyimide resin used is not particularly limited, and any conventional polyimide resin may be used, and T is preferablegPoly (greater than 400℃)Imide resins, for example, PMR type, ethynyl terminated type, soluble type. The type of the organic solvent used is not particularly limited, and any organic solvent having a high boiling point (boiling point of 100 ℃ or higher) capable of dissolving the polyimide resin may be used, but it is preferable to use any one or more selected from dioxane, dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone. The organic solvent not only meets the requirement that the boiling point is above 100 ℃, but also has stronger polarity, and is very suitable for preparing polyimide resin solution.
The concentration of the polyimide resin solution to be used is not particularly limited, but the mass concentration of the polyimide resin solution to be prepared is preferably 15% to 50%, and may be specifically 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, for example.
(2) Composition of resin and quartz fiber
And (3) coating the polyimide resin solution and compounding with quartz fiber fabric to obtain the resin/quartz fiber composite material. The compounding method may be impregnation, coating, or the like, and is preferably a coating method. The coating process may be operated as follows: a brush or other coating tool is used to dip the polyimide resin solution and uniformly coat at least one surface of the quartz fiber fabric. In this step, the mass of the resin coated is 50% to 100% of the mass of the quartz fiber fabric, for example, may be specifically 50%, 60%, 70%, 80%, 90%, 100%.
When the impregnation method is adopted for compounding, the resin can be impregnated by a dipping tank or other tools, and the temperature of the constant-temperature dipping tank is kept within the range of 150-180 ℃, so that the resin solution is kept in a molten state for impregnation. In this case, the mass concentration of the resin solution in the dip tank is preferably 30% to 40%. The impregnation method is the same as the conventional technique and will not be described in detail.
(3) Heat treatment under vacuum
The composite material is air-cured and then heat-treated under vacuum conditions. In the step, when the composite material is aired, the temperature of the airing environment is preferably 0-40 ℃, the humidity is below 40%, and the time can be controlled to be 5-24 hours. The heat treatment can be carried out by adopting a vacuum oven, the vacuum degree is-0.09 to-0.1 MPa, the temperature is 150 to 250 ℃, and the time is 1.5 to 3 hours.
When the composite material is treated in a vacuum oven, the organic solvent can be removed, the imidization process is completed, and small molecular substances are released. Therefore, no small molecules are released in the heating and pressurizing curing process, the void ratio of the composite material is effectively reduced, and the heat-resistant grade and the heat-resistant time are improved.
(4) Laying or winding
Cutting the composite material processed in the step (3) into a proper size, and layering or winding according to a set mode.
(5) Curing and post-curing
And heating and pressurizing the composite material subjected to layering or winding treatment for curing and post-curing to obtain the resin-based composite wave-transmitting material.
The solidification and post-solidification are carried out by stages by adopting a vacuum hot press, and the process conditions of each stage are as follows:
a first curing stage: heating the vacuum hot press to 250-300 ℃ and preserving heat for 1-1.5 h;
and (3) a second curing stage: heating the vacuum hot press to 320-350 ℃, preserving heat for 5-15 min, applying pressure of 5-20 MPa, preserving heat and maintaining pressure for 0.5-1 h;
and a third curing stage: heating the vacuum hot press to 370-380 ℃, and maintaining the temperature and the pressure for 2-4 h;
a fourth post-curing stage: and heating the vacuum hot press to 390-400 ℃, and keeping the temperature and pressure for 2-4 h.
The traditional mould pressing solidification is carried out by adopting a common hot press or an autoclave, and then the postsolidification is carried out by adopting a vacuum oven or a vacuumizing mode, which wastes a large amount of time. The invention adopts the vacuum hot press for curing and post-curing, not only can simplify the process and improve the efficiency, but also can effectively eliminate the internal stress of the parts and ensure that better mechanical property and dielectric property can be kept when the vacuum hot press is used at high temperature for a long time.
The invention also provides a long-time high-temperature-resistant resin-based composite wave-transmitting material prepared by the preparation method.
The following are examples of the present invention.
Example 1
The first step is as follows: preparing a polyimide resin solution, wherein a solvent is dioxane mixed with Dimethylacetamide (DMAC), the proportion of dioxane in the solvent is 70%, and the mass percentage content of the polyimide resin in the solution is 45%.
The second step is that: dipping the polyimide resin solution by a brush, and uniformly coating the polyimide resin solution on quartz fiber fabrics, wherein the mass of the resin is 66% of that of the quartz fiber fabrics, so as to prepare the polyimide resin/quartz fiber composite material.
The third step: the composite material is aired for 12 hours in an environment with the temperature of 25 ℃ and the humidity of 20 percent, and then is put into a vacuum oven with the vacuum degree of-0.096 MPa for treatment at the temperature of 200 ℃/2 hours.
And fourthly, cutting the composite material processed in the third step into a rectangle of 250mm × 130mm, cutting 20 layers, and then spreading the rectangle in a mould.
The fifth step: and putting the paved composite material into a vacuum hot press for staged curing and post-curing, and naturally cooling to 80 ℃ under pressure after the post-curing is finished, and demolding to obtain the quartz fiber reinforced polyimide resin composite material. The concrete curing process at each stage comprises the following steps:
a first curing stage: heating to 300 ℃ and preserving heat for 1 h;
and (3) a second curing stage: heating to 350 deg.C, maintaining for 7min, pressurizing to 10MPa, and maintaining for 0.8 h;
and a third curing stage: heating to 370 deg.C, maintaining the temperature and pressure for 2.5 h;
a fourth post-curing stage: heating to 400 ℃, and keeping the temperature and pressure for 3 h.
Example 2
The first step is as follows: preparing a polyimide resin solution, wherein the solvent is N, N-dimethylformamide, and the mass percentage content of the polyimide resin in the solution is 50%.
The second step is that: and (2) placing the resin solution into a glue dipping tank, keeping the glue dipping tank at a constant temperature of 150 ℃, and compounding the polyimide resin and the quartz fiber fabric through a dipping process to obtain the polyimide resin/quartz fiber composite material, wherein the mass of the resin solution accounts for 50% of the mass of the quartz fiber fabric.
The third step: the composite material is aired for 24 hours in an environment with the temperature of 30 ℃ and the humidity of 20 percent, and then is put into a vacuum oven with the vacuum degree of-0.093 MPa for 150 ℃/3 hours for treatment.
And fourthly, cutting the composite material processed in the third step into a rectangle of 250mm × 130mm, cutting 20 layers and spreading the cut composite material in a mould.
The fifth step: and putting the paved composite material into a vacuum hot press for staged curing and post-curing, and naturally cooling to 80 ℃ under pressure after the post-curing is finished, and demolding to obtain the quartz fiber reinforced polyimide resin composite material. The concrete curing process at each stage comprises the following steps:
a first curing stage: heating to 290 ℃ and preserving heat for 1 h;
and (3) a second curing stage: heating to 340 deg.C, maintaining for 5min, pressurizing at 20MPa, and maintaining for 0.5 h;
and a third curing stage: heating to 375 ℃, and keeping the temperature and pressure for 3 hours;
a fourth post-curing stage: heating to 390 ℃, and preserving heat and pressure for 4 h.
Examples 3 to 5
The preparation method is basically the same as that of example 1 except for the differences shown in Table 1.
Comparative example 1
The preparation method of comparative example 1 is substantially the same as that of example 1 except that:
in the third step, the prepreg is dried at normal temperature without the above-mentioned heat treatment.
Comparative example 2
The comparative example 2 was prepared substantially the same as example 1, except that:
and in the third step, the aired prepreg is subjected to heat treatment in a common drying oven, wherein the heat treatment temperature is 200 ℃ and the time is 2 hours.
Comparative example 3
The comparative example 3 was prepared substantially the same as example 1, except that:
in the fourth step, an autoclave is used for curing, and the method specifically comprises the following steps: placing the paved quartz fiber reinforced modified polyimide resin prepreg into an autoclave for curing, wherein the specific curing process comprises the following steps: the incubation was carried out at 240 ℃ for 2h and then at 370 ℃ for 2 h.
After the resin composite materials prepared by the above embodiments and comparative examples are insulated at 450 ℃ for 10min, the mechanical properties of the materials are tested, and the specific performance test results are shown in table 2.
TABLE 2
As can be seen from the detection results in Table 2, the prepreg in the preparation method provided by the invention can remove the organic solvent and complete the imidization process when being treated in a vacuum oven, and release small molecular substances, so that no small molecules are released in the heating and pressurizing curing process, the porosity of the composite material is effectively reduced, and the heat-resistant grade and the heat-resistant time are improved; the curing and post-curing procedures are carried out in the vacuum hot press, so that the internal stress of the workpiece can be effectively eliminated, and the good mechanical property and dielectric property can be ensured to be still kept when the vacuum hot press is used at high temperature for a long time. The composite material prepared by the method has better mechanical property and electrical property even if the composite material is used at the high temperature of 450 ℃ for 10 min. After verification, the composite material prepared by the invention still has good mechanical property and electrical property after being used for 30min at 500 ℃, and has important engineering application value.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A preparation method of a long-time high-temperature-resistant resin-based composite wave-transmitting material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a polyimide resin solution: dissolving polyimide resin in an organic solvent to prepare a polyimide resin solution; the organic solvent is any one or more of dioxane, dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone;
(2) compounding of resin and quartz fiber: compounding the polyimide resin solution and the quartz fiber fabric to prepare a resin/quartz fiber composite material;
(3) heat treatment under vacuum: airing the composite material, and then carrying out heat treatment under a vacuum condition; airing the composite material at 0-40 ℃ in an environment with the humidity of below 40%; carrying out heat treatment by adopting a vacuum oven, wherein the vacuum degree is-0.09 to-0.1 MPa, the temperature is 150 to 250 ℃, and the time is 1.5 to 3 hours;
(4) laying or winding: cutting the composite material processed in the step (3) into a proper size, and layering or winding according to a set mode;
(5) curing and post-curing: heating and pressurizing the layered or wound composite material for curing and post-curing to obtain the resin-based composite wave-transmitting material; the solidification and post-solidification are carried out by stages by adopting a vacuum hot press, and the process conditions of each stage are as follows:
a first curing stage: heating the vacuum hot press to 250-300 ℃ and preserving heat for 1-1.5 h;
and (3) a second curing stage: heating the vacuum hot press to 320-350 ℃, preserving heat for 5-15 min, applying pressure of 5-20 MPa, preserving heat and maintaining pressure for 0.5-1 h;
and a third curing stage: heating the vacuum hot press to 370-380 ℃, and maintaining the temperature and the pressure for 2-4 h;
a fourth post-curing stage: and heating the vacuum hot press to 390-400 ℃, and keeping the temperature and pressure for 2-4 h.
2. The method of claim 1, wherein: the airing time is controlled to be 5-24 hours.
3. The production method according to any one of claims 1 to 2, characterized in that: the polyimide resin solution is coated on the quartz fiber fabric by a coating method to be compounded.
4. The production method according to claim 3, characterized in that: the mass of the resin is 50-100% of that of the quartz fiber fabric.
5. The method of claim 1, wherein: in the polyimide resin solution, the mass concentration of the polyimide is 15-50%.
6. The long-time high-temperature-resistant resin-based composite wave-transmitting material is characterized in that: prepared by the preparation method of any one of claims 1 to 5.
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| CN109483908A (en) * | 2018-11-26 | 2019-03-19 | 航天特种材料及工艺技术研究所 | A kind of compound material insulation end hoop and preparation method thereof |
| CN112391052B (en) * | 2020-11-13 | 2022-09-02 | 航天特种材料及工艺技术研究所 | Foam material and preparation method thereof |
| CN114315690B (en) * | 2022-03-04 | 2022-06-21 | 北京玻钢院复合材料有限公司 | Imide ring-containing bisphthalonitrile compound, high-heat-resistance wave-transmitting composite material and preparation method thereof |
| CN115449219B (en) * | 2022-09-01 | 2024-02-02 | 中国建筑材料科学研究总院有限公司 | Silica aerogel quartz fiber polyimide ternary composite material and preparation method and application thereof |
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| US8708651B2 (en) * | 2007-10-26 | 2014-04-29 | David Greenblatt | Aerodynamic performance enhancements using discharge plasma actuators |
| CN101412849B (en) * | 2008-11-27 | 2010-12-01 | 东华大学 | Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material |
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