CN103449825A - Micro-ablation insulating material and preparation method thereof - Google Patents
Micro-ablation insulating material and preparation method thereof Download PDFInfo
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- CN103449825A CN103449825A CN2013103608921A CN201310360892A CN103449825A CN 103449825 A CN103449825 A CN 103449825A CN 2013103608921 A CN2013103608921 A CN 2013103608921A CN 201310360892 A CN201310360892 A CN 201310360892A CN 103449825 A CN103449825 A CN 103449825A
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Abstract
The invention discloses a micro-ablation insulating material. The micro-ablation insulating material comprises an ablation resin material and a rigid thermal-insulation material, wherein the rigid thermal-insulation material comprises a ceramic base body and an aerogel material. The invention also provides a preparation method of the micro-ablation insulating material. The method comprises the steps of compounding the aerogel material and the ceramic base body to manufacture the rigid thermal-insulation material, compounding the rigid thermal-insulation material and the ablation resin material, and gelling, drying and curing the ablation resin material. The proportions of the rigid thermal-insulation material and the ablation resin material, and the composition and the structure of the composition of the rigid thermal-insulation material and the ablation resin material in the thickness direction can be adjusted according to different using requirements. The micro-ablation insulating material has high designability, excellent superhigh-temperature heat-insulating property, strong variable-dimension ability and good processing performance, can be manufactured into various profiles and sizes, and has good application prospect in the fields of external protection of reentry type aircrafts and thermal protection of superhigh-temperature engines.
Description
Technical field
The present invention relates to a kind of ablative composite material and preparation method thereof, particularly relate to a kind of ablative composite material that possesses dimension shape and functionally gradient and preparation method thereof.
Background technology
When reentering the formula aerospacecraft and flying in endoatmosphere, the aircraft outside surface has born the high gas flow punching just, and temperature, up to 2000-10000 ℃, must adopt efficient ablation heat absorption/heat-insulation integrative system to carry out thermal protection to aircraft.
It is the ablation matrix that the tradition ablator (comprising low density and high-density) be take resol, epoxy resin, silicone resin, tetrafluoroethylene etc., usings fiber, phenolic aldehyde microballoon, glass microsphere and frp honeycomb etc. to be composited as weighting agent or strongthener.Under high aerodynamic heating, absorb heat by ablated surface, thereby maintain the lower surface material below certain temperature, guarantee the structural stability of lower surface material.Yet after the type material ablation, thermal conductivity is larger, can't further stops the hot-fluid transmission, thereby can't bring into play the long-term ablation/heat-proof quality of material.And, owing to the phenomenon such as easily occurring coming off, peel off after the strongtheners such as glass fibre, carbon fiber, basalt cotton, glass microsphere or filler ablation, be difficult to maintain the aerodynamic configuration of ablation/lagging material.
Be difficult to maintain aerodynamic configuration and ablation and the shortcoming such as heat insulation can't grow the time for traditional ablator, the application provides a kind of micro-ablation heat-insulation composite material, this material is prepared from by Ablative resin Material cladding rigidity lagging material, the Ablative resin material possesses ablation and heat insulating function, and the rigidity lagging material possesses dimension shape and heat insulating function.The advantage of giving this material maximum is: safe and reliable, adapt to that the ability that indirect heating changes is strong, longevity of service, and can bear high aerodynamic heating, dimension shape and heat-insulating capability are strong.Therefore, the type material likely is applied all kinds of reentering on the formula aircraft as ablation, dimension shape and lagging material, and its special performance also will make it become the candidate materials of ultrahigh-temperature engine.
Summary of the invention
The purpose of this invention is to provide a kind of efficient micro-ablation heat-insulation composite material and preparation method thereof, the material prepared by the method can effectively be brought into play ablation, heat insulation and dimension shape function, be expected to be applied on all kinds of hypersonic aerospacecrafts as outer heat insulation material, more likely be used widely reentering on the formula aerospacecraft.
The objective of the invention is to realize by following technical solution:
1, a kind of micro-ablation heat-insulation composite material, wherein, described micro-ablation heat-insulation composite material comprises Ablative resin material and rigidity lagging material, and described rigidity lagging material comprises ceramic matrix and aerogel material.
2, micro-ablation heat-insulation composite material as described as technical scheme 1, wherein, described micro-ablation heat-insulation composite material is made by the described rigid material of described Ablative resin Material cladding, and described rigidity lagging material is made by described ceramic matrix composite aerogel material.
3, micro-ablation heat-insulation composite material as described as technical scheme 1 or 2, described ceramic matrix is made by ceramic matrix material, and described ceramic matrix material comprises ceramic fiber matrix or ceramic foam.
4, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 3, wherein, the density of described ceramic matrix is 0.05g/cm
3-1.5g/cm
3.
5, micro-ablation heat-insulation composite material as described as technical scheme 3, wherein, described ceramic foam comprises one or more in the group be comprised of zirconium white, aluminum oxide, silicon oxide.
6, micro-ablation heat-insulation composite material as described as technical scheme 5, wherein, the porosity of described ceramic foam is 30%～95%.
7. micro-ablation heat-insulation composite material as described as technical scheme 3, wherein, high-temperature fibre and high-temperature fibre additive that described ceramic fiber matrix is 100: 1～20 by weight ratio form.
8. micro-ablation heat-insulation composite material as described as technical scheme 7, wherein, described high-temperature fibre comprises one or more in the group be comprised of Zirconium oxide fibre, silica fiber, sapphire whisker, mullite fiber, aluminum silicate fiber, high silica fiber and basalt fibre.
9. micro-ablation heat-insulation composite material as described as technical scheme 7 or 8, wherein, the diameter of described high-temperature fibre is 1 μ m～20 μ m.
10. micro-ablation heat-insulation composite material as described as technical scheme 9, wherein, the diameter of described high-temperature fibre is 1 μ m～3 μ m.
11, micro-ablation heat-insulation composite material as described as any one in technical scheme 7 to 10, wherein, the staple length of described high-temperature fibre is 1mm～100mm.
12, micro-ablation heat-insulation composite material as described as technical scheme 11, wherein, the staple length of described high-temperature fibre is 2mm～5mm.
13, micro-ablation heat-insulation composite material as described as any one in technical scheme 7 to 12, wherein, the temperature tolerance of described high-temperature fibre is not less than 1000 ℃.
14, micro-ablation heat-insulation composite material as described as any one in technical scheme 7 to 13, wherein, the temperature tolerance of described high-temperature fibre is greater than 1200 ℃.
15, micro-ablation heat-insulation composite material as described as any one in technical scheme 7 to 14, wherein, described high-temperature fibre additive comprises antiradiation agent and/or high-temperature agglomerant.
16, micro-ablation heat-insulation composite material as described as any one in technical scheme 7 to 15, wherein, the mass ratio of described Ablative resin material and rigidity lagging material is 1: 0.2～30.
17, micro-ablation heat-insulation composite material as described as technical scheme 16, wherein, described antiradiation agent selects free SiC, Cr
2o
3, CoO
2, TiO
2and Al
2o
3one or more in the group formed.
18, micro-ablation heat-insulation composite material as described as technical scheme 16 or 17, wherein, and the weight ratio of described antiradiation agent and described high-temperature fibre is 1～30: 100.
19, micro-ablation heat-insulation composite material as described as any one in technical scheme 16 to 18, wherein, described high-temperature agglomerant selects free borosilicate, B
4c, B
4n, B
2o
3one or more in the group formed.
20, micro-ablation heat-insulation composite material as described as any one in technical scheme 16 to 19, wherein, the weight ratio 1～10: 100 of described high-temperature agglomerant and described high-temperature fibre.
21, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 20, wherein, described aerogel selects free SiO
2aerogel, Al
2o
3aerogel, ZrO
2one or more in the group that aerogel, charcoal-aero gel and ceramic aerogel form.
22, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 21, wherein, the weight ratio of described aerogel and described ceramic matrix is 0.1～90: 0.2～30.
23, the micro-ablation heat-insulation composite material described in technical scheme 21 or 22, wherein, the group that described ceramic aerogel selects free silicon carbide aerogel and Si-B-C-N aerogel to form.
24, the micro-ablation heat-insulation composite material described in technical scheme 1 to 23, wherein, described micro-ablation heat-insulation composite material also comprises Ablative resin solidifying agent and/or Ablative resin additive.
25, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 24, wherein, described Ablative resin comprises one or more in the group be comprised of boron bakelite resin, ba phenolic resin, high char yield phenolic resin, silicone resin.
26, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 24, wherein, 1 % by weight-100 % by weight that described Ablative resin is described micro-ablation heat-insulation composite material.
27. micro-ablation heat-insulation composite material as described as any one in technical scheme 24 to 26, wherein, one or more in the group that described Ablative resin solidifying agent comprises hexamethylenetetramine, aniline, trimeric cyanamide, tosic acid, Tosyl chloride and mahogany acid composition.
28, micro-ablation heat-insulation composite material as described as any one in technical scheme 24 to 27, wherein, the weight ratio that described Ablative resin materials curing agent accounts for described Ablative resin material is 0.1-10%.
29, micro-ablation heat-insulation composite material as described as any one in technical scheme 24 to 27, wherein, described Ablative resin additive is polyhedral oligomeric silsesquioxane hybrid and/or paracril.
30, micro-ablation heat-insulation composite material as described as any one in technical scheme 24 to 29, wherein, the weight ratio that described Ablative resin additive accounts for described Ablative resin material is 0-80%.
31, micro-ablation heat-insulation composite material as described as any one in technical scheme 1 to 30, wherein, the Compound Degree of described Ablative resin material and rigidity lagging material along rigidity lagging material thickness direction in 15% to 100% range.
31, a kind of method of the described micro-ablation heat-insulation composite material of any one in technology of preparing scheme 1 to 31, described method comprises the steps:
(1) prepare the rigidity lagging material;
(2) preparation Ablative resin material mixing liquid;
(3) Ablative resin Material cladding rigidity lagging material;
(4) Ablative resin material gel; With
(5) Ablative resin material cured.
32, method as described as technical scheme 31, wherein, in (1) step, by high-temperature fibre and water in 100g: 5～10L ratio is mixed, and makes the formation fibre stuff.
33, method as described as technical scheme 31 or 32, wherein, to the additive that adds 1 % by weight that accounts for described high-temperature fibre～30 % by weight in described fibre stuff.
34, method as described as any one in technical scheme 31 to 33, wherein, to the high-temperature agglomerant that adds 1 % by weight that accounts for described high-temperature fibre～10 % by weight in described fibre stuff.
35, method as described as any one in technical scheme 31 to 34, wherein, in step (1), thereby also comprise and fibre stuff being transferred in the former mould with suction filtration function and suction filtration is discharged the step (1a) that most moisture forms wet first base.
36,, as gone the described method of any one in 31 to 35, wherein, in step (1), also comprise described just base is placed in to the dry step of baking oven.
37,, as gone the described method of any one in 31 to 36, wherein, in step (1), also comprise the step that calcining furnace that the described just base through super-dry is placed in to 150 ℃ of initial temperature is calcined.
38, method as described as technical scheme 37, wherein, the temperature rise rate of described calcining furnace is: 1～8 ℃/min is warming up to 1000 ℃～1700 ℃ from 150 ℃, insulation 0.5～5h, then be down to room temperature with 1～10 ℃/min, the ripe base burnt till is come out of the stove, obtain rigid matrix.
39, as gone the described method of any one in 31 to 38, wherein, in step (1), also comprise preparation aerogel precursor liquid solution, and by vacuum mode flood rigid matrix, by compound, the solvent exchange of collosol and gel mode, supercritical drying, obtain thus the rigidity lagging material.
40, as gone the described method of any one in 31 to 39, wherein, in step (1), the weight ratio of described rigid matrix and aerogel is 100: 10～200.
41, method as described as any one in technical scheme 31 to 40, wherein, described ceramic matrix is ceramic foam.
42, method as described as technical scheme 41, wherein, the weight ratio of described ceramic foam and aerogel is 100: 10～300.
43, method as described as technical scheme 41, wherein, step (2) is carried out in the following way: Ablative resin material, solvent are mixed with 1: 0.5～100 weight ratio, obtain Ablative resin material mixing solution.
44, method as described as technical scheme 43, wherein, described Ablative resin mixing solutions also adds solidifying agent or additive.
45, method as described as technical scheme 44, wherein, described solidifying agent accounts for 0.1 % by weight-10 % by weight of described Ablative resin material, the 0-80 % by weight that described additive is described Ablative resin material.
46, method as described as any one in technical scheme 31 to 45, wherein, in step (3), choosing density is 0.05-1.5g/cm
3the rigidity lagging material, be placed in container, adopt dipping, spraying or penetration mode with the solution combined described rigidity lagging material of described Ablative resin material mixing.
47, method as described as any one in technical scheme 31 to 46, wherein, in step (4), adopt the mode of oven dry or original flavor gel to carry out gelation.
48, method as described as technical scheme 47, wherein, described situ-gel be temperature in room temperature-120 ℃ ,-pressure of 0.1MPa-3MPa and carrying out within the time of 0-72 hour, thereby make the reaction of Ablative resin material generation situ-gel.
49, method as described as any one in technical scheme 31 to 48, wherein, repeating said steps (2) is to (5), to make the multiple Ablative resin material of described Ablative resin material along described rigidity lagging material thickness direction distribution gradient.
50, a kind of micro-ablation heat-insulation composite material that the described method of any one makes in technical scheme 31 to 49.
Micro-ablation heat-insulation composite material of the present invention is prepared from by the compound Ablative resin material of rigidity lagging material, possesses carrying and dimension shape ability, and has super micro-nano porous structure concurrently, effectively brings into play the heat-proof quality of self.
With other published traditional ablator, compare, the present invention has the following advantages:
(1) the prepared micro-ablative-insulative material of the present invention is except having good ablation thermal insulation ability, and in ablation process, the reaction of material surface generation ceramic, possess dimension type ability;
(2) the prepared micro-ablative-insulative material of the present invention has good ablation property, and Ablative resin material layer thickness is controlled along rigidity lagging material thickness direction, and structure composition and the content of Ablative resin material are adjustable, can effectively control the matrix material ablation property;
(3) the prepared micro-ablative-insulative material of the present invention has good ablation property, can realize that multicomponent Ablative resin material is compound along rigidity lagging material thickness direction functionally gradient, is beneficial to the various Ablative resin material ablation characteristics of performance.
(4) the prepared micro-ablative-insulative material of the present invention has good heat-proof quality, and the rigidity lagging material of not compound Ablative resin material is aerogel heat-insulating material, continues the excellent heat-proof quality of performance;
(5) the prepared micro-ablative-insulative material of the present invention has good heat-proof quality, in high hot-fluid Airflow Environment, rigidity lagging material porous surface structure generation melting transition, form fine and close viscosity flow layer, to a certain degree hinder oxygen and enter ablation layer, protect the carbon residue structure of Ablative resin material, be beneficial to high temperature insulating;
(6) the prepared micro-ablative-insulative material of the present invention has good dimension shape ability, and the rigidity lagging material has higher mechanical strength and resistance of oxidation, and surfacing, under hot conditions, melting transition occurs, and forms the viscosity flow layer, the protection inner structural strength.
(7) the prepared micro-ablative-insulative material of the present invention has good dimension shape ability, and rigidity lagging material and Ablative resin material realize that under hot environment ceramic changes, and has increased rigidity lagging material mechanical strength.
(8) can make according to use occasion and position micro-ablative-insulative material of various Special-Shaped Surface and size.
The prepared micro-ablative-insulative material of the present invention has important using value in reentering the big area thermal protection field of formula aerospacecraft, also is hopeful to be applied to ultrahigh-temperature engine thermal protection field.
Embodiment
As mentioned above, the invention provides a kind of micro-ablative-insulative material and preparation method thereof, and the material made by described method.
First aspect, the invention provides a kind of micro-ablative-insulative material, and described micro-ablation heat-insulation composite material comprises Ablative resin material and rigidity lagging material, and described rigidity lagging material comprises ceramic matrix and aerogel material.
In some embodiments, described micro-ablation heat-insulation composite material is made by the described rigid material of described Ablative resin Material cladding, and described rigidity lagging material is made by described ceramic matrix composite aerogel material.
In some embodiments, the mass ratio of described Ablative resin material and rigidity lagging material is 1: 0.2～30.Described mass ratio can be for example 1: (0.2,1,5,10,20 or 30).The Ablative resin material content is depending on reentering formula aircraft reentry environment, and as in reentry environment, the high state temperature is higher, the time is longer, the Ablative resin material content can improve by design; As lower as high state temperature in reentry environment, the time is shorter can reduce the Ablative resin material content in right amount, improves lagging material content, thereby realizes the optimization of ablation and effect of heat insulation.
In some embodiments, described ceramic matrix is made by ceramic matrix material, and described ceramic matrix material comprises ceramic fiber matrix or ceramic foam.
In some embodiments, the density of described ceramic matrix is 0.05g/cm
3-1.5g/cm
3, for example described density can be 0.05g/cm
3, 0.10g/cm
3, 0.20g/cm
3, 0.30g/cm
3, 0.40g/cm
3, 0.50g/cm
3, 0.60g/cm
3, 0.70g/cm
3, 0.80g/cm
3, 0.90g/cm
3, 1.00g/cm
3, 1.10g/cm
3, 1.20g/cm
3, 1.30g/cm
3, 1.40g/cm
3or 1.50g/cm
3.If described volume density is lower than 0.05g/cm
3, may cause material mechanical performance poor, can't maintain stable mechanical strength; If described volume density higher than 1.5g/cm3, may cause heat-proof quality significantly to reduce.
In some embodiments, described ceramic foam comprises one or more in the group be comprised of zirconium white, aluminum oxide, silicon oxide.
In some embodiments, the porosity of described ceramic foam is 30%～95%, is for example 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%.
In some embodiments, described ceramic fiber matrix is 100: 1～20 by weight ratio high-temperature fibre and high-temperature fibre additive form.This part by weight is as can be 100: 1,100: 5,100: 10,100: 15 or 100: 20.
Some preferred embodiment in, described high-temperature fibre comprises one or more in the group be comprised of Zirconium oxide fibre, silica fiber, sapphire whisker, mullite fiber, aluminum silicate fiber, high silica fiber and basalt fibre.More preferably, the diameter of described high-temperature fibre is 1 μ m～20 μ m, is for example 1 μ m, 5 μ m, 10 μ m, 15 μ m or 20 μ m.Further preferably, the diameter of described high-temperature fibre is 1 μ m～3 μ m, is for example 1 μ m, 2 μ m or 3 μ m.In addition preferably, the staple length of described high-temperature fibre is 1mm～100mm, can be for example 1mm, 5mm, 10mm, 20mm, 30mm, 40mm, 50mm, 60mm, 70mm, 80mm, 90mm or 100mm.Further preferably, the staple length of described high-temperature fibre is 2mm～5mm, can be for example 2mm, 3mm, 4mm or 5mm.
In some embodiments, the temperature tolerance of described high-temperature fibre is not less than 1000 ℃.In some embodiments, the temperature tolerance of described high-temperature fibre is greater than 1200 ℃.
In some embodiments, described high-temperature fibre additive comprises antiradiation agent and/or high-temperature agglomerant.In some embodiments, described antiradiation agent selects free SiC, Cr
2o
3, CoO
2, TiO
2and Al
2o
3one or more in the group formed.
In some embodiments, and the weight ratio of described antiradiation agent and described high-temperature fibre is 1～30: 100, is for example 1: 100,5: 100,10: 100,15: 100,20: 100,25: 100 or 30: 100.
In some embodiments, described high-temperature agglomerant selects free borosilicate, B
4c, B
4n, B
2o
3one or more in the group formed.
In some embodiments, the weight ratio 1～10: 100 of described high-temperature agglomerant and described high-temperature fibre, be for example 1: 100,2: 100,3: 100,4: 100,5: 100,6: 100,7: 100,8: 100,9: 100 or 10: 100.
In some embodiments, described aerogel selects free SiO
2aerogel, Al
2o
3aerogel, ZrO
2one or more in the group that aerogel, charcoal-aero gel and ceramic aerogel form.In some embodiments, described ceramic aerogel comprises silicon carbide aerogel and Si-B-C-N.
In some embodiments, the weight ratio of described aerogel and described ceramic matrix is 0.1～90: 0.2～30, for example, the ratio value of aerogel can be 0.1,0.5,1.0,10,20,30,40,50,60,70,80 or 90, and the ratio value of ceramic matrix is 0.2,0.5,1.0,5.0,10,15,20,25 or 30.
In some embodiments, described ceramic aerogel is selected the group that free silicon carbide aerogel and Si-B-C-N aerogel form.
In some embodiments, described micro-ablation heat-insulation composite material also comprises Ablative resin solidifying agent and/or Ablative resin additive.
In some embodiments, described Ablative resin comprises one or more in the group be comprised of boron bakelite resin, ba phenolic resin, high char yield phenolic resin, silicone resin.In some embodiments, described Ablative resin is that high char yield phenolic resin and aerogel are aerosil.
In some embodiments, 1 % by weight-100 % by weight that described Ablative resin is described micro-ablation heat-insulation composite material, be for example 1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.
In some embodiments, one or more in the group that described Ablative resin solidifying agent comprises hexamethylenetetramine, aniline, trimeric cyanamide, tosic acid, Tosyl chloride and mahogany acid composition.
In some embodiments, the weight ratio that described Ablative resin materials curing agent accounts for described Ablative resin material is 0.1-10%, is for example 0.1%, 0.5%, 1%, 5% or 10%.
In some embodiments, described Ablative resin additive is polyhedral oligomeric silsesquioxane hybrid and/or paracril.
In some embodiments, the weight ratio that described Ablative resin additive accounts for described Ablative resin material is 0-80%, is for example 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%.
In some embodiments, the Compound Degree of described Ablative resin material and rigidity lagging material along rigidity lagging material thickness direction in 15% to 100% range, for example, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.
In second aspect, the invention provides a kind of method for preparing above-mentioned micro-ablation heat-insulation composite material, described method comprises the steps:
(1) prepare the rigidity lagging material;
(2) preparation Ablative resin material mixing liquid;
(3) Ablative resin Material cladding rigidity lagging material;
(4) Ablative resin material gel; With
(5) Ablative resin material cured.
The technical superiority of described method of the present invention is:
(1) at first prepare the rigidity lagging material, aerogel material and ceramic matrix compound, realized the effectively insulating of micro-ablative-insulative material.
(2) then compound different content, different thickness Ablative resin material, realized the heat insulation purpose of efficient ablation of material.
(3) the nano level blend of last Ablative resin material and aerogel material, contribute to ablator to react with aerogel material generation ceramic.
In some embodiments, in (1) step, by high-temperature fibre and water in 100g: 5～10L ratio is mixed, and makes the formation fibre stuff, and this ratio can be for example 100g: 5L, 100g: 6L, 100g: 7L, 100g: 8L, 100g: 9L or 100g: 10L.
In some embodiments, the additive to adding 1 % by weight that accounts for described high-temperature fibre～30 % by weight in described fibre stuff, for example add the additive of 1 % by weight, 5 % by weight, 10 % by weight, 20 % by weight or 30 % by weight.
In some embodiments, to the high-temperature agglomerant that adds 1 % by weight that accounts for described high-temperature fibre～10 % by weight in described fibre stuff, for example account for the high-temperature agglomerant of 1 % by weight, 2 % by weight, 3 % by weight, 4 % by weight, 5 % by weight, 6 % by weight, 7 % by weight, 8 % by weight, 9 % by weight or 10 % by weight of described high-temperature fibre
In some embodiments, in step (1), thereby also comprise and fibre stuff being transferred in the former mould with suction filtration function and suction filtration is discharged the step (1a) that most moisture forms wet first base.
In some embodiments, in step (1), also comprise described just base is placed in to the dry step of baking oven.
In some embodiments, in step (1), also comprise the step that calcining furnace that the described just base through super-dry is placed in to 150 ℃ of initial temperature is calcined.
In some embodiments, the temperature rise rate of described calcining furnace is: 1～8 ℃/min (for example 1,2,3,4,5,6,7 or 8 ℃/min) is warming up to 1000 ℃～1700 ℃ (for example being warming up to 1000,1100,1200,1300,1400,1500,1600 or 1700 ℃) from 150 ℃, insulation 0.5～5h (for example 0.5,1,2,3,4 or 5 hour, then for example, be down to room temperature with 1～10 ℃/min (1～8 ℃/min (1,2,3,4,5,6,7,8,9 or 10 ℃/min)), the ripe base burnt till is come out of the stove, obtain rigid matrix.
In some embodiments, in step (1), also comprise preparation aerogel precursor liquid solution, and by vacuum mode flood rigid matrix, pass through that the collosol and gel mode is compound, solvent exchange, supercritical drying, obtain thus the rigidity lagging material.
In some embodiments, in step (1), the weight ratio of described rigid matrix and aerogel is 100: 10～200, is for example 100: 10,100: 20,100: 30,100: 40,100: 50,100: 60,100: 70,100: 80,100: 90,100: 100,100: 110,100: 120,100: 130,100: 140,100: 150,100: 160,100: 170,100: 180,100: 190 or 100: 200.
In some embodiments, described ceramic matrix is ceramic foam.
In some embodiments, the weight ratio of described ceramic foam and aerogel is 100: 10～300, is for example 100; 10,100: 20,100: 30,100: 40,100: 50,100: 60,100: 70,100: 80,100: 90,100: 100,100: 150,100: 200,100: 250 or 100: 300.
In some embodiments, step (2) is carried out in the following way: Ablative resin material, solvent be take to the weight ratio of 1: 0.5～100 (being for example 1: 0.5,1,5,10,20,40,60,80 or 100) and mix, obtain Ablative resin material mixing solution.
In some embodiments, described Ablative resin mixing solutions also adds solidifying agent or additive.More preferably, described solidifying agent accounts for 0.1 % by weight-10 % by weight (being for example 0.1,0.5,1.0,5 or 10 % by weight) of described Ablative resin material, the 0-80 % by weight that described additive is described Ablative resin material (being for example 10,20,30,40,50,60,70 or 80 % by weight).
In some embodiments, in step (3), choosing density is 0.05-1.5g/cm
3(be for example 0.05,0.10,0.20,0.40,0.80,1.0,1.2,1.4 or 1.5g/cm
3) the rigidity lagging material, be placed in container, adopt dipping, spraying or penetration mode with the solution combined described rigidity lagging material of described Ablative resin material mixing.
In some embodiments, in step (4), adopt the mode of oven dry or original flavor gel to carry out gelation.
In some embodiments, described situ-gel be temperature (for example 25,30,40,50,60,70,80,90,100,110 or 120 ℃) in room temperature-120 ℃ ,-pressure of 0.1MPa-3MPa (for example-0.1,1,2 or 3MPa) and carrying out within the time of 0-72 hour (1,2,3,6,9,12,15,18,21,24,36,48,60 or 72 hour), thereby make the reaction of Ablative resin material generation situ-gel.
In some embodiments, repeating said steps (2) is to (5), to make the multiple Ablative resin material of described Ablative resin material along described rigidity lagging material thickness direction distribution gradient.
For example, the technology of preparation method of micro-ablative-insulative material of the present invention, can carry out: Ablative resin material and solvent are configured to mixed solution by certain weight ratio, flood or permeate compound rigidity lagging material in the following way, gel drying, curing molding, obtain micro-ablative-insulative material.The concrete steps of described method can for example comprise:
(1) prepare the rigidity lagging material: by high-temperature fibre and water in 100g: 5～10L ratio is mixed, and adopts high speed dispersor to be uniformly dispersed, and forms fibre stuff; Add the additive of fiber quality 1%～30% and be uniformly dispersed in this fibre stuff; If the interpolation high temperature adhesive, caking agent accounts for 1%～10% of fiber quality, and is uniformly dispersed;
Slurry being transferred to rapidly in the former mould with suction filtration function to suction filtration discharges most moisture and forms wet first base;
First base is placed in to baking oven dry.The calcining furnace that dried first base is placed in to 150 ℃ of initial temperature is calcined, and the calcining furnace temperature rise rate is: 1～8 ℃/min is warming up to 1000 ℃～1700 ℃ from 150 ℃, is incubated 0.5～5h.Then be down to room temperature with 1～10 ℃/min, the ripe base now burnt till is come out of the stove, and obtains rigid matrix.
Configuration SiO
2aerogel, A1
2o
3aerogel, ZrO
2aerogel, organic aerogel, ceramic aerogel precursor solution or arbitrary combination wherein, then vacuum impregnation rigid matrix, obtain the rigidity lagging material after, solvent exchange compound by the collosol and gel mode, supercritical drying, the weight ratio of described rigid matrix and aerogel is 100: 10～200.As to adopt ceramic foam, the weight ratio of ceramic foam and aerogel be 100: 10～300.
(2) Ablative resin material mixing liquid configuration: mix with 1: 0.5～100 weight ratio with Ablative resin material, solvent, obtain one or more Ablative resin material mixing solution, if need add solidifying agent or additive, solidifying agent should be the 0.1-10% of Ablative resin material, and additive should be the 0-80% of Ablative resin material;
(3) Ablative resin Material cladding rigidity lagging material: choosing density is 0.05-1.5g/cm
3the rigidity lagging material, be placed in container, the volume of required Ablative resin material solution while calculating compound 0-100% thickness rigidity lagging material, adopt dipping, spraying or the compound Ablative resin material mixing of penetration mode solution.
(4) Ablative resin material gel: the gel mode of Ablative resin material can be divided into two kinds, 1. dries, and takes out compound good rigidity lagging material, at the baking oven inner drying, after solvent volatilizees fully, realizes the Ablative resin material gel; 2. situ-gel, do not take out the rigidity lagging material, in specified temp (room temperature-120 ℃), specified pressure (0.1MPa-3MPa) and specified time scope (0-72h), the situ-gel reaction occurs in the Ablative resin material under the effects such as solidifying agent;
(5) Ablative resin material cured: after the system gel, be placed in baking oven, solidify by specific.
If prepare the functionally gradient ablator, repeating step (2)-(5), make the ablator of different Ablative resin materials along rigidity lagging material thickness direction distribution gradient;
Described Ablative resin material of the present invention possesses the ablation heat insulating function, and has the ablation bearing structure concurrently, has certain dimension shape ability.
In some embodiments, the density of described micro-ablation heat-insulation composite material can be 0.1-2.2g/cm
3, be for example 0.1g/cm
3, 0.2g/cm
3, 0.5g/cm
3, 1.0g/cm
3, 1.5g/cm
3, 2.0g/cm
3or 2.2g/cm
3.In some embodiments, the room temperature thermal conductivity of described micro-ablation heat-insulation composite material is 0.03-0.15W/mK, is for example 0.03W/mK, 0.06W/mK, 0.09W/mK, 0.12W/mK or 0.15W/mK.
The third aspect, the invention provides the micro-ablation heat-insulation composite material made by the above method.
In this article, except as otherwise noted, otherwise term " wherein arbitrary combination " refers to and is selected from any two kinds or above arbitrary combination in described group.
Except as otherwise noted, otherwise described herein and numerical range comprise the arbitrary value between end value and endpoints thereof (being upper and lower bound).
In addition, in the present invention, term " micro-ablation " has art-recognized implication, but means that material ablation material surface is not reversed.
Embodiment
The invention will be further described by the following examples, and for explaining main innovate point of the present invention, but these embodiment must not be for explaining limiting the scope of the invention.
Embodiment 1: the preparation of the compound rigidity lagging material of ba phenolic resin
(1) adopt 3-5 μ m silica fiber, borosilicate binding agent and titanium dioxide antiradiation agent, by the quality of 100: 3: 10, than blend, make the rigid fiber matrix, density is 0.2g/cm
3.
(2) the rigid fiber matrix made by step (1) that will be of a size of 100mm * 100mm * 20mm is placed in container, vacuumize, get rid of the gas in the material hole, the compound 20% aerosil precursor water solution of vacuum impregnation then, acquisition density is 0.40g/cm
3the rigidity lagging material.
(3) get the 200g ba phenolic resin and join in 800g ethanol, add the 10g hexamethylenetetramine, use the mechanical stirrer stirring and dissolving, be made into 20% ba phenolic resin ethanolic soln;
(4) open the container vacuum valve, the phenol resin solution for preparing, under inside and outside pressure difference effect, is injected in frock to thorough impregnation rigidity lagging material automatically;
(5) the rigidity lagging material of abundant impregnated phenolic resin is taken out fast, be placed in baking oven, solidify, obtain micro-ablation heat-insulation composite material.
Embodiment 2 to 12, and except the rear note content of content and table 1 shown in table 1, other all carry out according to the mode identical with embodiment 1.
The raw material that table 1 embodiment adopts and ratio thereof and other parameters
Embodiment 13: the compound rigidity lagging material of boron bakelite resin upper layer
(1) adopt 3-5 μ m silica fiber, sapphire whisker, borosilicate binding agent and potassium titanate crystal whisker antiradiation agent, by 78: 22: 3:: 10 quality, than blend, makes the rigid fiber matrix, and density is 0.25g/cm
3.
(2) will be of a size of the rigid fiber matrix that 100mm * 100mm * 20mm makes by step (1) and be placed in container, vacuumize, get rid of the gas in the material hole, the compound 25% aerosil presoma of vacuum impregnation then, acquisition density is 0.50g/cm
3the rigidity lagging material.
(3) get the 300g ba phenolic resin and join in 700g ethanol, add the hexamethylenetetramine of 10g, use the mechanical stirrer stirring and dissolving, be made into 30% ba phenolic resin ethanolic soln;
(4) open the container vacuum valve, the boron bakelite resin solution prepared is slowly injected to container under inside and outside pressure difference effect, by the by-pass valve control size adjustment, advance glue speed;
(5) will flood complete rigidity lagging material and take out fast, and be placed in baking oven, and solidify, obtaining ablation layer thickness is micro-ablation heat-insulation composite material of 20mm.As ablation layer does not meet density requirements, can repeated impregnations, curing process, until meet design requirement.
Embodiment 14 to 18, and except content shown in table 2, other all carry out according to the mode identical with embodiment 13.
The raw material that table 2 embodiment adopts and ablation layer thickness
Embodiment 19: the two compound rigidity lagging materials of upper layer of boron bakelite resin-PMMA
(1) will be of a size of 150mm * 150mm * 25mm, density is 0.3g/cm
3quartz substrate, put into 210mm * 210mm * 40mm container, vacuumize, get rid of the gas in the material hole, the compound 20% aerosil presoma of vacuum impregnation then, the rigidity lagging material that to obtain density be 0.50g/cm3;
(2) get the 200g boron bakelite resin and add in the 800g alcohol solvent, use the mechanical stirrer stirring and dissolving, until completely dissolved, add 10g tosic acid solidifying agent, be made into 20% boron phenolic aldehyde ethanolic soln, measure 120ml solution;
(3) open the container vacuum valve, the boron bakelite resin solution prepared is slowly injected to container under inside and outside pressure difference effect, by the by-pass valve control size adjustment, advance glue speed;
(4) will flood complete rigidity lagging material and take out fast, and be placed in baking oven, the impregnate layer level down, is solidified, and obtains the ablative-insulative material of ablation layer thickness 5mm;
(5) will solidify complete rigidity heat-insulation composite material and again be placed in the container cleaned, the phenolic aldehyde ablation layer upward, to be impregnated facing down, horizontal positioned, vacuumize, and gets rid of the gas in the material hole, calculates the volume of the required PMMA resin solution of dipping thickness;
(6) get 200g PMMA resin and add in the 400g acetone solvent, use the mechanical stirrer stirring and dissolving, be made into 33.3% PMMA acetone soln, measure 120ml solution;
(7) open the container vacuum valve, the PMMA resin solution slow (5-50ml/min) under inside and outside pressure difference effect prepared is injected to container, by the by-pass valve control size adjustment, advance glue speed;
(8) will flood complete rigidity lagging material and take out fast, and be placed in baking oven, the impregnate layer level down, is solidified, and obtains micro-ablation heat-insulation composite material of phenolic aldehyde layer 5mm, aerogel layer 15mm, PMMA layer 5mm.
This patent has been tested mechanical strength and surface ceramic deposition degree after the ablator cracking, as shown in table 3, can find out, select suitable combination of raw materials, can realize the surface ceramic deposition in the ablator ablation process, the ablator of ceramic still can keep higher mechanical property.
Embodiment material ceramic degree and mechanical strength after table 31600 ℃ heat 60s
The ablation heat-proof quality that this patent adopts oxygen/acetylene heating unit to test different thickness hierarchical composite ablator, as shown in table 4, can find out, under the particular thermal envrionment conditions, can select suitable layered structure ablator.
The basic physical properties parameter of table 4 embodiment material and heat-proof quality are relatively
In the present invention, density is measured according to the GB/T6343-2009 method; Thermal conductivity is measured according to GB/T10295-2008; Compressive strength is measured according to GB8489-87; The ceramic degree is used transmission electron microscope (TEM model JEM-2100F) to be observed.The ablated surface situation adopts naked eyes to observe.
Claims (10)
1. a micro-ablation heat-insulation composite material, wherein, described micro-ablation heat-insulation composite material comprises Ablative resin material and rigidity lagging material, and described rigidity lagging material comprises ceramic matrix and aerogel material.
2. micro-ablation heat-insulation composite material as claimed in claim 1, wherein, described ceramic matrix is made by ceramic matrix material, and described ceramic matrix material comprises ceramic fiber matrix or ceramic foam, and density is 0.05g/cm
3-1.5g/cm
3.
3. micro-ablation heat-insulation composite material as claimed in claim 2, wherein, described ceramic foam comprises one or more in the group be comprised of zirconium white, aluminum oxide, silicon oxide, and porosity is 30%～95%.
4. micro-ablation heat-insulation composite material as claimed any one in claims 1 to 3, wherein, high-temperature fibre and high-temperature fibre additive that described ceramic fiber matrix is 100: 1～20 by weight ratio form.
5. micro-ablation heat-insulation composite material as claimed in claim 4, wherein, described high-temperature fibre comprises one or more in the group be comprised of Zirconium oxide fibre, silica fiber, sapphire whisker, mullite fiber, aluminum silicate fiber, high silica fiber and basalt fibre, preferably, the diameter of described high-temperature fibre is 1 μ m～20 μ m, more preferably 1 μ m～3 μ m; Further preferably, the staple length of described high-temperature fibre is 1mm～100mm, more preferably 2mm～5mm; The temperature tolerance of described high-temperature fibre is not less than 1000 ℃, more preferably greater than 1200 ℃.
6. micro-ablation heat-insulation composite material as claimed in claim 5, wherein, described high-temperature fibre additive comprises antiradiation agent and high-temperature agglomerant; Preferably, described antiradiation agent selects free SiC, Cr
2o
3, CoO
2, TiO
2and Al
2o
3one or more in the group formed, and the weight ratio of described antiradiation agent and described high-temperature fibre is 1～30: 100; Preferably, described high-temperature agglomerant selects free borosilicate, B
4c, B
4n, B
2o
3one or more in the group formed, and the weight ratio 1～10: 100 of described high-temperature agglomerant and described high-temperature fibre.
7. micro-ablation heat-insulation composite material as described as any one in claim 1 to 6, wherein, described aerogel selects free SiO
2aerogel, Al
2o
3aerogel, ZrO
2one or more in the group that aerogel, charcoal-aero gel and ceramic aerogel form; Preferably, the weight ratio of described aerogel and described ceramic matrix is 0.1～90: 0.2～30; Further preferably, described ceramic aerogel is selected the group that free silicon carbide aerogel and Si-B-C-N aerogel form.
8. micro-ablation heat-insulation composite material as described as any one in claim 1 to 7, wherein, described micro-ablation heat-insulation composite material also comprises Ablative resin solidifying agent and/or Ablative resin additive; Preferably, one or more in the group that described Ablative resin solidifying agent comprises hexamethylenetetramine, aniline, trimeric cyanamide, tosic acid, Tosyl chloride and mahogany acid composition, described Ablative resin additive is polyhedral oligomeric silsesquioxane hybrid and/or paracril, the weight ratio that wherein said Ablative resin materials curing agent accounts for described Ablative resin material is 0.1-10%, and the weight ratio that described Ablative resin additive accounts for described Ablative resin material is 0-80%.
9. micro-ablation heat-insulation composite material as described as any one in claim 1 to 8, wherein, described Ablative resin comprises one or more in the group be comprised of boron bakelite resin, ba phenolic resin, high char yield phenolic resin, silicone resin, and described Ablative resin 1 % by weight-100 % by weight that is described micro-ablation heat-insulation composite material.
10. micro-ablation heat-insulation composite material as claimed in any one of claims 1-9 wherein, wherein, the Compound Degree of described Ablative resin material and rigidity lagging material along rigidity lagging material thickness direction in 15% to 100% range.
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