CN105038109A - Preparation method of high temperature heat-proof resin composite material - Google Patents
Preparation method of high temperature heat-proof resin composite material Download PDFInfo
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- CN105038109A CN105038109A CN201510337694.2A CN201510337694A CN105038109A CN 105038109 A CN105038109 A CN 105038109A CN 201510337694 A CN201510337694 A CN 201510337694A CN 105038109 A CN105038109 A CN 105038109A
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Abstract
The invention discloses a preparation method of a high temperature heat-proof resin composite material, and relates to the technical field of composite material production. The preparation method comprises the following steps: adding a glue solution into a glue soaking tank; starting a glue soaking machine; soaking dehumidified non-alkali glass fiber cloths into the glue soaking tank; after glue soaking, rolling and cutting to obtain prepreg cloths; heating a 100 T four-column oil press; smearing an external releasing agent on a mould; after the mould temperature rises to 120 DEG C and remains stable, laying up the prepreg cloths according to the designed layer number, and putting into the mould for pressing; when the mould temperature naturally drops to 60 DEG C or below, demoulding, so as to obtain the high temperature heat-proof resin composite material. The composite material prepared through the preparation method is applicable to thermal protection materials, ablative materials, function materials, and the like, of weaponry, and is also applicable to the fields with special demands like high temperature, thermal insulation, flame retardance and abrasion resistance of the civilian industry.
Description
Technical field:
The present invention relates to matrix material production technical field, be specifically related to a kind of preparation method of high temperature solar heat protection resin composite materials.
Background technology:
In sophisticated technology fields such as space flight and bullet arrow weapons, need the structure heat insulation material having solar heat protection and structure-bearing function concurrently, structure heat insulation material is except needing to possess except as far as possible little thermal conductivity, also require the high specific strength of general high temperature structural composite material, high ratio modulus, high second-order transition temperature or fusing point, good antioxidant property.In addition, residing for thermal protection struc ture matrix material, variation of ambient temperature possibility amplitude is large, and frequency is high, therefore requires that its thermal shock resistance is good.Solar heat protection ablative composite material mainly contains several large classes such as resin base ablator, carbon back ablator, ceramic base ablator.The manufacture tool of high temperature resistant solar heat protection polymer matrix composites to space flight and aviation aircraft is of great significance, because ablative heat prevention has numerous superior cooling mechanism, effectively can guarantee that inside configuration is in lower temperature, be widely used in the thermal protection of various aerospacecraft height hot-fluid parts.At present, in thermal-protect ablation material, mainly phenolic aldehyde sill and C/C material competitively develop, compared with C/C material, alkyd resin based thermal-protect ablation material has that cost is low, thermal conductivity is low and the advantage such as good heat-insulation effect, in common ablation environment, have good application, be comparatively widely used ablation resistant material.
There is the shortcomings such as fragility is large, carbon yield is low in tradition resol, in order to improve resistance toheat and ablation resistance further, our company has carried out the study on the modification work to resol, and wherein boron modified phenolic resin is the one that in modified phenolic resins kind, performance is comparatively given prominence to.Boron bakelite resin introduces inorganic boron in the molecular structure of resol, generate the B-O key that bond energy is higher, simultaneously due to the three-dimensional crosslinking structure of boron, easily six-ring is formed in solidification process, make the thermotolerance of boron modified phenolic resin, ablation resistance and much better than phenolic resin of mechanical property, the mechanical property of made heat-resistant composite material particularly high-temperature behavior and ablation resistance excellent, do not need interpolation organic, inorganic combustion inhibitor, possesses few cigarette simultaneously, low toxicity, flame retardant properties, the linear ablative rate of boron bakelite resin is-0.079mm/s, mass ablative rate is 0.0333g/s, the high performance requirements of leading-edge field to heat-resistant composite material can be met.
Most polymers is all combustible, need change flame retardant properties by adding fire retardant, but boron bakelite resin and the existing flame retardant properties of matrix material thereof, there is again low heat release value and hypotoxicity, do not need to add any fire retardant and just can reach UL94V-0 level.The novel solar heat protection polymer matrix composites of this project have do not burn, rate of being fuming is low, less or nontoxic gas release, not halogen-containing, high containing the flame retardant resistance solid packing insoluble with matrix, intensity, good toughness is a kind of novel solar heat protection based composites of resistance to Ablative resin of high comprehensive performance.This matrix material, for the thermally protective materials, ablator, functional materials etc. of weaponry, also can be used for the high temperature of civilian industry, the particular requirement field such as heat insulation, fire-retardant, wear-resisting.
Summary of the invention:
Technical problem to be solved by this invention is to provide that a kind of input cost is low, the preparation method of the high temperature solar heat protection resin composite materials of excellent performance.
Technical problem to be solved by this invention adopts following technical scheme to realize:
A preparation method for high temperature solar heat protection resin composite materials, comprises the following steps:
(1) glue is added in steeping vat, then start cement dipping machine, the alkali-free glass fiber cloth after dehumidifying is immersed in steeping vat, the cement dipping machine speed of a motor vehicle is 0.5-1.5m/min, bake out temperature is leading portion 80 DEG C, 100 DEG C, stage casing, latter end 120 DEG C, and impregnation terminates rear rolling, cutting, obtained prepreg cloth;
(2) 100T tetra-post oil press is heated, mould is coated with external release agent, after die temperature is raised to 120 DEG C and is stable, by prepreg cloth by designing number of plies laying and putting into mould, precompressed 30min, then die temperature is risen to 150 DEG C, insulation 2-3h, then mould is warmed up to 180 DEG C, 8-12h is incubated under pressure 3-7MPa, stop heating subsequently, mould unloading time below mould Temperature fall to 60 DEG C, obtains high temperature solar heat protection resin composite materials;
Described glue is made up of the component of following massfraction: boron bakelite resin 35-45%, dehydrated alcohol 55-65%, coupling agent KH5500.1-0.2%, oleic acid 0.1-1%, nano silicon 1.0-2.0%, its compound method is for first will adopt ultrasonic wave to be dissolved in dehydrated alcohol after boron bakelite resin fragmentation, then nano silicon is added, make it be uniformly dispersed, add coupling agent KH550 and oleic acid after 30min, mix under high-speed stirring.
It is 140g/m that described alkali-free glass fiber cloth is selected from area density
2, 200g/m
2alkali-free plain weave glass-fiber-fabric and alkali-free plain weave glass-fiber-fabric through pyroprocessing.
The decomposition temperature of described boron bakelite resin is more than 500 DEG C, and at 900 DEG C, carbon yield reaches 70%.
Described external release agent is happy auspicious solid 1165C.
The invention has the beneficial effects as follows:
(1) use temperature of made matrix material is-55 DEG C ~ 450 DEG C, and have excellent mechanical property and high-temperature behavior, thermal conductivity is low;
(2) do not add fire retardant, made matrix material does not burn, rate of being fuming is low, less or nontoxic gas release;
(3) not halogen-containing, not containing the flame retardant resistance solid packing insoluble with matrix;
(4) can be used for the thermally protective materials of weaponry, ablator, functional materials etc., also can be used for the high temperature of civilian industry, the particular requirement field such as heat insulation, fire-retardant, wear-resisting.
Embodiment:
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
1, the preparation of glue
Glue is made up of the raw material of following massfraction:
Boron bakelite resin 35-45%, dehydrated alcohol 55-65%, coupling agent KH5500.1-0.2%, oleic acid 0.1-1%, nano silicon 1.0-2.0%.
Compound method is as follows:
First by adopting ultrasonic wave to be dissolved in dehydrated alcohol after boron bakelite resin fragmentation, then adding nano silicon, making it be uniformly dispersed, after 30min, add coupling agent KH550 and oleic acid, mix under high-speed stirring.
2, the preparation of high temperature solar heat protection resin composite materials
(1) first glue is added in steeping vat, then cement dipping machine is started, by after dehumidifying alkali-free plain weave glass-fiber-fabric immerse in steeping vat, the cement dipping machine speed of a motor vehicle is 0.5-1.5m/min, bake out temperature is leading portion 80 DEG C, 100 DEG C, stage casing, latter end 120 DEG C, impregnation terminates rear rolling, cutting, and obtained prepreg cloth, wherein alkali-free plain weave glass-fiber-fabric selects area density to be 200g/m
2, 140g/m
2alkali-free plain weave glass-fiber-fabric and alkali-free plain weave glass-fiber-fabric through pyroprocessing;
(2) 100T tetra-post oil press is heated, the happy auspicious solid 1165C of mould painting external release agent, after die temperature is raised to 120 DEG C and is stable, by prepreg cloth by designing number of plies laying and putting into mould, precompressed 30min, then die temperature is risen to 150 DEG C, insulation 2-3h, then mould is warmed up to 180 DEG C, 8-12h is incubated under pressure 3-7MPa, stop heating subsequently, mould unloading time below mould Temperature fall to 60 DEG C, obtains EWF, EWF-1 and EWF-2 high temperature solar heat protection resin composite materials.
The technical indicator of table 1 prepreg cloth
The mechanical property of table 2EWF, EWF-1 and EWF-2
As can be seen from table 1,2, on obtained prepreg cloth, resin content is higher, fugitive constituent is low, and soluble resin content reaches more than 90%, and repressed rear obtained EWF, EWF-1 and EWF-2 high temperature solar heat protection resin composite materials of prepreg cloth has good mechanical property.
In the ablation process of solar heat protection ablative composite material, material passes through loss part mass and forms fine and close charring layer in thermal environment, to reach thermo-lag object, therefore the residual qualities after material decomposes is the most important condition investigating its ablation property, thermogravimetric analysis can be used to measure decomposition, oxidation, reduction, evaporation, distillation and other quality change, residual qualities mark after material decomposes completely is generally carbon forming rate, and the massfraction lost is rate of weight loss.Therefore, thermogravimetric analysis is the important means investigating polymer heat-resistant, and general weight retention is higher, and namely carbon yield is higher, and rate of weight loss is low, and the thermotolerance of high score material is better.
The boron bakelite resin decomposition temperature that this project adopts is more than 500 DEG C, and the carbon yield at 900 DEG C reaches about 70%, at high temperature generates the three-dimensional crosslinking structure of boron, therefore the fine heat-resisting performance of resin.Under nitrogen protection, heat up by per minute 10 DEG C/min, measure the thermogravimetric retention rate of high temperature heat-resistant composite material, structure is in table 3.
Table 3EWF, EWF-1 and EWF-2 thermogravimetric retention rate (%) at different temperatures
| Project | 200℃ | 300℃ | 400℃ | 500℃ | 600℃ | 700℃ | 800℃ |
| EWF | 95.9 | 94.3 | 93 | 90.2 | 85.4 | 78.9 | 74.6 |
| EWF-1 | 97.7 | 96.8 | 95.5 | 93.7 | 90.2 | 86.1 | 84.4 |
| EWF-2 | 97.2 | 96.0 | 94.5 | 92.2 | 88.2 | 84.5 | 83.4 |
EFW-1 and the rate of weight loss of-2 two kinds of high temperature solar heat protection resin composite materials at 800 DEG C are only about 16%, in solid propellant rocket, when after propelling agent Thorough combustion, ablation layer near high-temperature fuel gas stream is in oxygen deprivation state substantially, thus, EWF series of high temperature solar heat protection resin composite materials is the desirable ablator of Solid rocket nozzle thermal insulating liner, and the static line ablation rate of high silica/boron phenolic composite is 0.081mm/s, and mass ablative rate is 0.0527g/s.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (4)
1. a preparation method for high temperature solar heat protection resin composite materials, is characterized in that, comprises the following steps:
(1) glue is added in steeping vat, then start cement dipping machine, the alkali-free glass fiber cloth after dehumidifying is immersed in steeping vat, the cement dipping machine speed of a motor vehicle is 0.5-1.5m/min, bake out temperature is leading portion 80 DEG C, 100 DEG C, stage casing, latter end 120 DEG C, and impregnation terminates rear rolling, cutting, obtained prepreg cloth;
(2) 100T tetra-post oil press is heated, mould is coated with external release agent, after die temperature is raised to 120 DEG C and is stable, by prepreg cloth by designing number of plies laying and putting into mould, precompressed 30min, then die temperature is risen to 150 DEG C, insulation 2-3h, then mould is warmed up to 180 DEG C, 8-12h is incubated under pressure 3-7MPa, stop heating subsequently, mould unloading time below mould Temperature fall to 60 DEG C, obtains high temperature solar heat protection resin composite materials;
Described glue is made up of the component of following massfraction: boron bakelite resin 35-45%, dehydrated alcohol 55-65%, coupling agent KH5500.1-0.2%, oleic acid 0.1-1%, nano silicon 1.0-2.0%, its compound method is for first will adopt ultrasonic wave to be dissolved in dehydrated alcohol after boron bakelite resin fragmentation, then nano silicon is added, make it be uniformly dispersed, add coupling agent KH550 and oleic acid after 30min, mix under high-speed stirring.
2. the preparation method of high temperature solar heat protection resin composite materials according to claim 1, is characterized in that: it is 140g/m that described alkali-free glass fiber cloth is selected from area density
2, 200g/m
2alkali-free plain weave glass-fiber-fabric and alkali-free plain weave glass-fiber-fabric through pyroprocessing.
3. the preparation method of high temperature solar heat protection resin composite materials according to claim 1, is characterized in that: the decomposition temperature of described boron bakelite resin is more than 500 DEG C, and at 900 DEG C, carbon yield reaches 70%.
4. the preparation method of high temperature solar heat protection resin composite materials according to claim 1, is characterized in that: described external release agent is happy auspicious solid 1165C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949415A (en) * | 2016-07-12 | 2016-09-21 | 湖南金化科技集团有限公司 | {0><}0{>Nitrile-alkenyl phenolic resin and thermal-protection ablation molding compound and preparation method thereof |
| CN108215427A (en) * | 2017-12-28 | 2018-06-29 | 江阴市沪澄绝缘材料有限公司 | A kind of production line of the highly dense corrosion resistant phenol aldehyde glass cloth laminated board of high-end equipment |
| CN113306173A (en) * | 2021-05-25 | 2021-08-27 | 蚌埠市天宇高温树脂材料有限公司 | Ablation-resistant heat-proof high-silica cloth/boron phenolic resin matrix composite material and preparation method thereof |
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| CN1834151A (en) * | 2006-03-09 | 2006-09-20 | 同济大学 | Prepn. process of nano SiO2/boron bakelite resin nano composite material |
| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN103183907A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | High-temperature-resistant phenolic glass fibre reinforced plastic material |
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| CN1834151A (en) * | 2006-03-09 | 2006-09-20 | 同济大学 | Prepn. process of nano SiO2/boron bakelite resin nano composite material |
| CN103183907A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | High-temperature-resistant phenolic glass fibre reinforced plastic material |
| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949415A (en) * | 2016-07-12 | 2016-09-21 | 湖南金化科技集团有限公司 | {0><}0{>Nitrile-alkenyl phenolic resin and thermal-protection ablation molding compound and preparation method thereof |
| CN105949415B (en) * | 2016-07-12 | 2018-01-12 | 湖南金化科技集团有限公司 | Nitrile alkenyl phenolic resin and thermal protection ablation moulding compound and preparation method thereof |
| CN108215427A (en) * | 2017-12-28 | 2018-06-29 | 江阴市沪澄绝缘材料有限公司 | A kind of production line of the highly dense corrosion resistant phenol aldehyde glass cloth laminated board of high-end equipment |
| CN108215427B (en) * | 2017-12-28 | 2023-10-27 | 江阴市沪澄绝缘材料有限公司 | Production line of high-end equipment high-density corrosion-resistant phenolic glass cloth laminated board |
| CN113306173A (en) * | 2021-05-25 | 2021-08-27 | 蚌埠市天宇高温树脂材料有限公司 | Ablation-resistant heat-proof high-silica cloth/boron phenolic resin matrix composite material and preparation method thereof |
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