CN115195254B - Heat insulation/ablation resistance heat protection structure and preparation method thereof - Google Patents

Heat insulation/ablation resistance heat protection structure and preparation method thereof Download PDF

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CN115195254B
CN115195254B CN202210602383.4A CN202210602383A CN115195254B CN 115195254 B CN115195254 B CN 115195254B CN 202210602383 A CN202210602383 A CN 202210602383A CN 115195254 B CN115195254 B CN 115195254B
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ablation
heat
parts
resistant
phenolic resin
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CN115195254A (en
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谢永旺
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Aerospace Research Institute of Materials and Processing Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass

Abstract

The invention relates to a heat insulation/ablation resistance heat protection structure and a preparation method thereof. The heat insulation/ablation resistance heat protection structure comprises a heat insulation layer and an ablation resistance layer, and the preparation method comprises the following steps: preparing a lightweight insulating layer sheet comprising: phenolic resin, hollow glass microspheres, reinforcing phase chopped fibers, additives; preparing an ablation resistant prepreg comprising: phenolic resin, nano titanium dioxide, siC powder, zirconium diboride, additives and reinforced continuous woven cloth; and combining the light heat-insulating layer sheets with the corresponding layers and the ablation-resistant prepreg according to the designed thickness, pressurizing and curing to obtain the heat-insulating/ablation-resistant heat-protecting structure. The heat protection structure prepared by the invention has the advantages of light heat insulation and ablation resistance, adjustable thickness ratio of the heat insulation layer to the ablation resistance layer, capability of meeting the requirements of high heat flow/short-time or medium, low heat flow/medium and long-time flight heat environment, simple process flow, short production period and capability of meeting the development requirements of low cost.

Description

Heat insulation/ablation resistance heat protection structure and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, relates to a heat protection structure and a preparation method thereof, and particularly relates to a light heat protection structure with heat insulation and ablation resistance functions and a preparation method thereof.
Background
The condensation products of phenols and aldehydes are known as phenolic resins. Phenolic resins are the earliest synthetic resins in the world for industrial production and have been known for over a hundred years so far. The resin is still used as a main matrix resin of resin-based ablation-resistant materials so far due to the advantages of excellent mechanical property, heat resistance, cold resistance, dimensional stability, molding processability, flame retardance, low smoke property, low production cost and the like. The high-temperature-resistant heat-resistant ablation-resistant material manufactured by using phenolic resin as matrix resin is widely applied to the technical field of national defense tips such as aerospace and the like.
The thermal protection system (Thermal Protection System, TPS) is a critical structure that protects the spacecraft from returning smoothly to earth, with ablative heat protection being the most reliable heat protection scheme. The charring type ablation material is suitable for the service environment with high enthalpy value and high heat flux density, is an ablation heat-resistant material widely applied at present, and is typically represented by a carbon/phenolic aldehyde (C-Ph) composite material. The traditional C-Ph resin matrix composite material has higher density and higher heat conductivity coefficient, and is difficult to meet the field of high-performance aerospace, and weight reduction is a permanent pursuit of aerospace, so that the high-temperature-resistant light-weight ablative heat insulation material is a hot spot of research in recent years.
Patent CN201910261601.0 discloses a micro-ablative light phenolic resin and a preparation method thereof, hollow glass beads, titanium dioxide, zirconium diboride and the like are added into a resin matrix to cooperatively reduce the material density and improve the ablation resistance of the material. However, the weight reduction effect of the thermal protection material prepared by the method is still limited. Patent CN103449825a discloses a micro-ablative insulation material, which can adjust the ratio of rigid insulation material to ablative material and the composition and structure of rigid insulation material in the thickness direction, and can be made into various profiles and sizes as required. However, the porosity of the rigid insulating material contained in the material is variable; in addition, the ablative material is compounded with the rigid heat insulation material in a dipping, spraying or penetrating way, and the proportion of the rigid heat insulation material to the ablative resin material in the thickness direction cannot be accurately adjusted in the way; in addition, the material preform is high in cost, and the production period of the product is long.
Disclosure of Invention
The invention mainly aims to provide a heat insulation/ablation-resistant heat protection structure and a preparation method thereof, the heat protection structure prepared by the method has light heat insulation and ablation-resistant performance, the thickness ratio of a heat insulation layer to an ablation-resistant layer is adjustable, the requirements of high heat flow/short-time or medium, low heat flow/medium and long-time flying heat environment can be met, the process flow is simple, the production period is short, and the development requirement of low cost is met.
In a first aspect, the present invention provides a method for preparing a thermal insulation/ablation-resistant thermal protection structure, the thermal insulation/ablation-resistant thermal protection structure comprising a thermal insulation layer and an ablation-resistant layer, the method comprising the steps of:
preparing a lightweight insulating layer sheet comprising: phenolic resin, hollow glass microspheres, reinforcing phase chopped fibers, additives;
preparing an ablation resistant prepreg comprising: phenolic resin, nano titanium dioxide, siC powder, zirconium diboride, additives and reinforced continuous woven cloth;
and combining the light heat-insulating layer sheets with the corresponding layers and the ablation-resistant prepreg according to the designed thickness, pressurizing and curing to obtain the heat-insulating/ablation-resistant heat-protecting structure.
Further, the light heat-insulating layer sheet comprises the following components in parts by mass: 100 parts of phenolic resin, 40-60 parts of hollow glass microspheres, 25 parts of reinforcing phase chopped fibers and 0.5 part of additive.
Further, the ablation-resistant prepreg comprises the following components in parts by mass: 100 parts of phenolic resin, 10 parts of nano titanium dioxide, 10 parts of SiC powder, 20-40 parts of zirconium diboride and 0.5 part of additive.
Further, the preparation of the lightweight insulating layer sheet material comprises:
heating the kneader to 70 ℃, and taking 100 parts of phenolic resin in the kneader to be heated and melted;
weighing 0.5 part of additive, pouring into a kneader, and fully mixing;
weighing chopped fibers in corresponding proportion, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers;
weighing hollow glass microspheres in corresponding proportion, equally dividing into 3 parts, and sequentially pouring into a kneader;
and placing the uniformly mixed substances on a film coating machine, and starting to coat films to prepare the single-layer light heat-insulating layer sheet.
Further, the hollow glass microspheres are closed-cell hollow microspheres with the particle size of 100um and the ball breaking rate of less than 5% under the pressure of 1 MPa; the chopped fiber is spiral and is formed by mixing quartz fiber and Kevlar fiber in a ratio of 1:1 (number ratio), and the fiber length is 15-25 mm.
Further, the additive is a mixture of a dispersant and a toughening agent.
Further, the preparing of the ablation resistant prepreg includes:
heating the reaction kettle to 70 ℃, taking 100 parts of phenolic resin in equipment, and heating and melting;
weighing 0.5 part of additive, pouring into a reaction kettle, and fully mixing;
weighing nano titanium dioxide, siC powder and zirconium diboride in corresponding proportions, mixing uniformly, dividing into 2 parts, and sequentially pouring into a reaction kettle to obtain high-carbon residue modified phenolic resin;
and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the single-layer anti-ablation prepreg.
Further, the long continuous woven cloth is formed by weaving quartz fibers and Kevlar fibers according to a 1:1 (number ratio).
Further, the light heat-insulating layer sheet and the ablation-resistant prepreg are combined according to the designed thickness, and vacuum bag pressing-autoclave curing is carried out, wherein the curing procedure is as follows: 60 ℃ to 2 hours, 90 ℃ to 2 hours, 1MPa of pressurization, 120 ℃ to 4 hours, 160 ℃ to 4 hours, and curing and demolding to obtain the heat-insulating/ablation-resistant heat protection structure.
In a second aspect, the present invention also provides a thermally insulating/ablative thermal protective structure prepared according to the method of the invention described above.
The heat insulation/ablation resistance heat protection structure provided by the invention has the following main advantages:
1. the proportion of the ablation-resistant layer to the heat-insulating layer can be adjusted in the thickness direction according to the requirements of high heat flow/short-time or medium-low heat flow/medium-long-time flight heat environment;
2. the closed-cell hollow glass microspheres realize the functions of weight reduction and heat insulation, and simultaneously avoid the process fluctuation that the phenolic foaming is not easy to control;
3. nano titanium dioxide, siC powder, zirconium diboride modified phenolic resin and TiO 2 SiC improves the high temperature oxidation resistance of the material; siC, zrB 2 Ceramic reaction occurs in the ablation process, so that the ablation resistance of the material is improved;
the hollow microsphere with the ball breaking rate less than 5% under the pressure of 4.1MPa can realize the integral curing and forming of the ablation resistant layer and the heat insulation layer under the condition of high pressure, and the process flow is reduced;
5. the heat insulating layer and the ablation-resistant layer are the same in resin matrix and reinforcing phase material types (proportion), the linear expansion coefficients of the materials are similar, and the problem of an interlayer interface is avoided to the greatest extent.
6. The heat insulation layer, the spiral chopped fiber is provided with a net in the thickness direction, so that the integrity is better; the anti-ablation layer has better anti-ablation performance for long continuous woven cloth.
Detailed Description
The present invention will be described in further detail with reference to the following examples.
The invention provides a heat insulation/ablation-resistant heat protection structure, which mainly comprises a light heat insulation layer and a high-density ablation-resistant layer, and the preparation method comprises the following steps:
1. preparing a light heat insulation layer:
the light heat-insulating layer sheet mainly comprises 100 parts of phenolic resin, 40-60 parts of hollow glass microspheres, 25 parts of reinforcing phase chopped fibers and 0.5 part of additive in mass ratio.
The preparation method of the light heat-insulating layer sheet comprises the following steps:
1. heating the kneader to 70 ℃, taking 100 parts of phenolic resin in equipment, and heating and melting;
2. weighing 0.5 part of additive, pouring into a kneader, and fully mixing for 5min;
3. weighing chopped fibers in corresponding proportion, pouring the chopped fibers into a kneader, and fully mixing for 10min;
4. weighing hollow glass microspheres in corresponding proportion, equally dividing into 3 parts, sequentially pouring into a kneader, and separating for 10min each time;
5. and placing the uniformly mixed substances on a film coating machine, adjusting the gap between film coating rollers to be 1mm, starting film coating, and finally preparing the light heat-insulating layer sheet with the thickness of 1 mm.
Preferably, the hollow glass microspheres are closed-cell hollow microspheres, the particle size is 100um, and the ball breaking rate is less than 5% under the pressure of 1MPa.
Preferably, the chopped fibers are spiral and are formed by mixing quartz fibers and Kevlar fibers in a ratio of 1:1 (number ratio), and the fiber length is 15-25 mm.
Preferably, the additive is a mixture of a dispersant and a toughening agent. Wherein the dispersing agent can be polyvinyl alcohol, polyethylene glycol and the like, and the toughening agent can be carboxylated nitrile rubber, polyvinyl butyral and the like.
2. Preparing an ablation resistant layer:
the ablation-resistant prepreg mainly comprises 100 parts of phenolic resin, 10 parts of nano titanium dioxide, 10 parts of SiC powder, 20-40 parts of zirconium diboride, 0.5 part of additive (mass ratio) and reinforcing constructive continuous woven cloth.
The preparation method of the ablation-resistant layer comprises the following steps:
1. heating the reaction kettle to 70 ℃, taking 100 parts of phenolic resin in equipment, and heating and melting;
2. weighing 0.5 part of additive, pouring into a reaction kettle, and fully mixing for 5min;
3. weighing nano titanium dioxide, siC powder and zirconium diboride in corresponding proportions, mixing uniformly, dividing into 2 parts, sequentially pouring into a reaction kettle, and separating for 10min each time to obtain high carbon residue modified phenolic resin;
4. and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the ablation-resistant prepreg with the thickness of 0.25 mm.
Preferably, the long continuous woven cloth is formed by weaving quartz fibers and Kevlar fibers according to the number ratio of 1:1.
3. Preparation of a heat insulation/ablation resistant heat protection structure:
and (3) combining light heat-insulating layer sheets with corresponding layers and ablation-resistant prepreg layers according to the designed thickness, and curing by a vacuum bag press-autoclave, wherein the curing procedure is as follows: 60 ℃ to 2 hours, 90 ℃ to 2 hours, 1MPa of pressurization, 120 ℃ to 4 hours, 160 ℃ to 4 hours, and curing and demolding to obtain the heat-insulating/ablation-resistant heat protection structure.
Aiming at the use requirement and technical index of heat protection, the thought and key points of the heat insulation/ablation resistance heat protection structure are as follows:
1. adopts the structural design concept of ablation resistance and heat insulation;
2. independently designing the linear ablation rate and interlayer shearing key performance of the ablation-resistant layer, and the heat conductivity coefficient and compression strength key performance of the heat insulation layer;
3. attention is paid to the interface problem between the ablation resistant layer and the thermal insulation layer during the operation of the thermal insulation/ablation resistant thermal protection structure.
Example 1: preparation of light heat-insulating layer
1. Heating the kneader to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a kneader, and fully mixing for 5min;
3. weighing 250g of chopped fibers, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers for 10 minutes;
4. weighing 400g of hollow glass microspheres, equally dividing into 3 parts, sequentially pouring into a kneader, and separating for 10min each time;
5. placing the uniformly mixed substances on a film coating machine, adjusting the gap of a film coating roller to be 1mm, starting film coating, and finally preparing a single-layer 1mm thick light heat insulation layer sheet;
6.10 layers of sheet materials are paved and combined, vacuum bag pressing and autoclave curing are carried out, the temperature is 60 ℃ to 2 hours, the temperature is 90 ℃ to 2 hours, the pressure is 1MPa, the temperature is 120 ℃ to 4 hours, the temperature is 160 ℃ to 4 hours, and the light heat insulation layer is obtained after curing and demoulding.
Example 2: preparation of light heat-insulating layer
1. Heating the kneader to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a kneader, and fully mixing for 5min;
3. weighing 250g of chopped fibers, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers for 10 minutes;
4. weighing 500g of hollow glass microspheres, equally dividing into 3 parts, sequentially pouring into a kneader, and separating for 10min each time;
5. placing the uniformly mixed substances on a film coating machine, adjusting the gap of a film coating roller to be 1mm, starting film coating, and finally preparing a single-layer 1mm thick light heat insulation layer sheet;
6.10 layers of sheet materials are paved and combined, vacuum bag pressing and autoclave curing are carried out, the temperature is 60 ℃ to 2 hours, the temperature is 90 ℃ to 2 hours, the pressure is 1MPa, the temperature is 120 ℃ to 4 hours, the temperature is 160 ℃ to 4 hours, and the light heat insulation layer is obtained after curing and demoulding.
Example 3: preparation of light heat-insulating layer
1. Heating the kneader to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a kneader, and fully mixing for 5min;
3. weighing 250g of chopped fibers, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers for 10 minutes;
4. weighing 600g of hollow glass microspheres, equally dividing into 3 parts, sequentially pouring into a kneader, and separating for 10min each time;
5. placing the uniformly mixed substances on a film coating machine, adjusting the gap of a film coating roller to be 1mm, starting film coating, and finally preparing a single-layer 1mm thick light heat insulation layer sheet;
6.10 layers of sheet materials are paved and combined, vacuum bag pressing and autoclave curing are carried out, the temperature is 60 ℃ to 2 hours, the temperature is 90 ℃ to 2 hours, the pressure is 1MPa, the temperature is 120 ℃ to 4 hours, the temperature is 160 ℃ to 4 hours, and the light heat insulation layer is obtained after curing and demoulding.
The properties of the light insulating layers prepared in examples 1-3 are shown in Table 1.
TABLE 1
Density (g/cm) 3 ) Room temperature heat conductivity W/(m.K) Room temperature compressive strength (MPa)
Example 1 0.45 0.28 18.4
Example 2 0.4 0.22 13.2
Example 3 0.38 0.14 8.6
Example 4: preparation of ablation resistant layer
1. Heating the reaction kettle to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a reaction kettle, and fully mixing for 5min;
3. weighing 100g of nano titanium dioxide, 100g of SiC powder and 200g of zirconium diboride, mixing uniformly, dividing into 2 parts, sequentially pouring into a reaction kettle, and separating for 10min each time to obtain high carbon residue modified phenolic resin;
4. and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the ablation-resistant prepreg with the thickness of 0.25 mm.
5.40 layers of anti-ablation prepreg are paved and combined, vacuum bag pressing-autoclave curing is carried out, the temperature is 60 ℃ to 2h, the temperature is 90 ℃ to 2h, the pressure is 1MPa, the temperature is 120 ℃ to 4h, the temperature is 160 ℃ to 4h, and the anti-ablation layer is obtained after curing and demoulding.
Example 5: preparation of ablation resistant layer
1. Heating the reaction kettle to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a reaction kettle, and fully mixing for 5min;
3. weighing 100g of nano titanium dioxide, 100g of SiC powder and 300g of zirconium diboride, mixing uniformly, dividing into 2 parts, sequentially pouring into a reaction kettle, and separating for 10min each time to obtain high carbon residue modified phenolic resin;
4. and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the ablation-resistant prepreg with the thickness of 0.25 mm.
5.40 layers of anti-ablation prepreg are paved and combined, vacuum bag pressing-autoclave curing is carried out, the temperature is 60 ℃ to 2h, the temperature is 90 ℃ to 2h, the pressure is 1MPa, the temperature is 120 ℃ to 4h, the temperature is 160 ℃ to 4h, and the anti-ablation layer is obtained after curing and demoulding.
Example 6: preparation of ablation resistant layer
1. Heating the reaction kettle to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a reaction kettle, and fully mixing for 5min;
3. weighing 100g of nano titanium dioxide, 100g of SiC powder and 400g of zirconium diboride, mixing uniformly, dividing into 2 parts, sequentially pouring into a reaction kettle, and separating for 10min each time to obtain high carbon residue modified phenolic resin;
4. and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the ablation-resistant prepreg with the thickness of 0.25 mm.
5.40 layers of anti-ablation prepreg are paved and combined, vacuum bag pressing-autoclave curing is carried out, the temperature is 60 ℃ to 2h, the temperature is 90 ℃ to 2h, the pressure is 1MPa, the temperature is 120 ℃ to 4h, the temperature is 160 ℃ to 4h, and the anti-ablation layer is obtained after curing and demoulding.
The properties of the ablation resistant layers prepared in examples 4-6 are shown in Table 2.
TABLE 2
Density (g/cm) 3 ) Oxyacetylene line ablation rate (mm/s) Shear Strength at room temperature (MPa)
Example 4 1.96 0.128 59.2
Example 5 2.06 0.085 60.5
Example 6 2.15 0.048 62.3
Example 7: preparation of heat insulation/ablation-resistant heat protection structure
1. Heating the kneader to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
2. weighing 5g of additive, pouring into a kneader, and fully mixing for 5min;
3. weighing 250g of chopped fibers, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers for 10 minutes;
4. weighing 600g of hollow glass microspheres, equally dividing into 3 parts, sequentially pouring into a kneader, and separating for 10min each time;
5. placing the uniformly mixed substances on a film coating machine, adjusting the gap of a film coating roller to be 1mm, starting film coating, and finally preparing a single-layer 1mm thick light heat insulation layer sheet;
6. heating the reaction kettle to 70 ℃, taking 1kg of phenolic resin in the equipment, and heating and melting;
7. weighing 5g of additive, pouring into a reaction kettle, and fully mixing for 5min;
8. weighing 100g of nano titanium dioxide, 100g of SiC powder and 400g of zirconium diboride, mixing uniformly, dividing into 2 parts, sequentially pouring into a reaction kettle, and separating for 10min each time to obtain high carbon residue modified phenolic resin;
9. and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the ablation-resistant prepreg with the thickness of 0.25 mm.
10. And (3) combining 6 layers of light heat-insulating layer sheets and 16 layers of ablation-resistant prepreg layers, curing by vacuum bagging and autoclave, and obtaining the heat-insulating/ablation-resistant heat protection structure after curing and demoulding, wherein the curing procedures are 60 ℃ to 2 hours, 90 ℃ to 2 hours, pressurizing 1MPa,120 ℃ to 4 hours and 160 ℃ to 4 hours.
Carrying out an arc wind tunnel test on the obtained heat insulation/ablation resistance heat protection structure, wherein test parameters are as follows: 3-4MW/m 2 ，15s。
The test results of the arc wind tunnel test are as follows: the surface ablation backing amount is 2.1mm, the mass weight loss rate is 22.6%, and the back temperature of the flat plate is 56 ℃.
The above-disclosed embodiments of the present invention are intended to aid in understanding the contents of the present invention and to enable the same to be carried into practice, and it will be understood by those of ordinary skill in the art that various alternatives, variations and modifications are possible without departing from the spirit and scope of the invention. The invention should not be limited to what has been disclosed in the examples of the specification, but rather by the scope of the invention as defined in the claims.

Claims (8)

1. A method of making a thermal insulation/ablation-resistant thermal protective structure comprising a lightweight thermal insulation layer and an ablation-resistant layer, the method comprising the steps of:
preparing a lightweight insulating layer sheet comprising: phenolic resin, hollow glass microspheres, reinforcing phase chopped fibers, additives; the chopped fibers are formed by mixing quartz fibers and Kevlar fibers;
preparing an ablation resistant prepreg comprising: phenolic resin, nano titanium dioxide, siC powder, zirconium diboride, additives and reinforced continuous woven cloth; the long continuous woven cloth is formed by weaving quartz fibers and Kevlar fibers;
combining the light heat-insulating layer sheets with the corresponding layers and the ablation-resistant prepreg according to the designed thickness, pressurizing and curing to obtain a heat-insulating/ablation-resistant heat protection structure;
the light heat-insulating layer sheet comprises the following components in parts by mass: 100 parts of phenolic resin, 40-60 parts of hollow glass microspheres, 25 parts of reinforcing phase chopped fibers and 0.5 part of additive;
the ablation-resistant prepreg comprises the following components in parts by mass: 100 parts of phenolic resin, 10 parts of nano titanium dioxide, 10 parts of SiC powder, 20-40 parts of zirconium diboride and 0.5 part of additive;
the hollow glass microsphere has a ball breaking rate less than 5% under the pressure of 1 MPa;
the pressurizing and curing is vacuum bag pressure-autoclave curing, and the pressurizing pressure in the vacuum bag pressure-autoclave curing process is 1MPa.
2. The method of making according to claim 1, wherein the making of the lightweight insulating layer sheet comprises:
heating the kneader to 70 ℃, and taking 100 parts of phenolic resin in the kneader to be heated and melted;
weighing 0.5 part of additive, pouring into a kneader, and fully mixing;
weighing chopped fibers in corresponding proportion, pouring the chopped fibers into a kneader, and fully mixing the chopped fibers;
weighing hollow glass microspheres in corresponding proportion, equally dividing into 3 parts, and sequentially pouring into a kneader;
and placing the uniformly mixed substances on a film coating machine, and starting to coat films to prepare the single-layer light heat-insulating layer sheet.
3. The method of claim 1, wherein the hollow glass microspheres are closed-cell hollow microspheres having a particle size of 100um; the chopped fiber is spiral and is formed by mixing quartz fiber and Kevlar fiber in a ratio of 1:1, and the fiber length is 15-25 mm.
4. The method of claim 1, wherein the additive is a mixture of a dispersant and a toughening agent.
5. The method of preparing according to claim 1, wherein the preparing the ablation resistant prepreg comprises:
heating the reaction kettle to 70 ℃, taking 100 parts of phenolic resin in equipment, and heating and melting;
weighing 0.5 part of additive, pouring into a reaction kettle, and fully mixing;
weighing nano titanium dioxide, siC powder and zirconium diboride in corresponding proportions, mixing uniformly, dividing into 2 parts, and sequentially pouring into a reaction kettle to obtain high-carbon residue modified phenolic resin;
and compounding the high-carbon-residue modified phenolic resin with the reinforced constructive continuous woven cloth by using a hot-melting prepreg preparation process to prepare the single-layer anti-ablation prepreg.
6. The method according to claim 5, wherein the long continuous woven fabric is a long continuous woven fabric formed by weaving quartz fibers and kevlar fibers in a ratio of 1:1.
7. The method of claim 1, wherein the vacuum bagging autoclave curing is performed by: 60 ℃ to 2 hours, 90 ℃ to 2 hours, 1MPa of pressurization, 120 ℃ to 4 hours, 160 ℃ to 4 hours, and curing and demolding to obtain the heat-insulating/ablation-resistant heat protection structure.
8. A thermal insulation/ablation-resistant thermal protective structure prepared according to the method of any one of claims 1-7.
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CN115636967B (en) * 2022-12-05 2023-03-28 北京玻钢院复合材料有限公司 Environment-friendly ablation-resistant phenolic resin prepreg, composite material and preparation method
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145454A (en) * 2013-03-25 2013-06-12 西北工业大学 Method for preparing ZrB2-SiC anti-ablation coating from in-situ reaction
CN105906360A (en) * 2016-04-20 2016-08-31 大连理工大学 Zirconium diboride-based composite material toughened by colloid-dispersed chopped carbon fibers and preparation method thereof
CN108410125A (en) * 2018-04-24 2018-08-17 航天特种材料及工艺技术研究所 A kind of anti-heat-insulation integrative resin combination, anti-heat-insulation integrative resin base ablator and preparation method thereof
CN109749351A (en) * 2017-11-03 2019-05-14 航天特种材料及工艺技术研究所 A kind of phenol-formaldehyde resin modified, composite material and preparation method
CN109852122A (en) * 2019-01-11 2019-06-07 上海交通大学 The resistance to ablative coatings of ceramic screw fiber reinforcement ba phenolic resin and its application
CN109968757A (en) * 2019-04-22 2019-07-05 中国人民解放军国防科技大学 Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof
CN110028754A (en) * 2019-04-02 2019-07-19 航天特种材料及工艺技术研究所 A kind of micro-ablation lightweight phenolic resin and preparation method thereof
CN114013122A (en) * 2021-11-24 2022-02-08 航天特种材料及工艺技术研究所 High-temperature-resistant antioxidant resin-based composite material and preparation method thereof
CN114437464A (en) * 2021-12-20 2022-05-06 西安近代化学研究所 Preparation method of ablation-resistant low-thermal-conductivity composite material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070270302A1 (en) * 2006-05-22 2007-11-22 Zhang Shi C Pressurelessly sintered zirconium diboride/silicon carbide composite bodies and a method for producing the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145454A (en) * 2013-03-25 2013-06-12 西北工业大学 Method for preparing ZrB2-SiC anti-ablation coating from in-situ reaction
CN105906360A (en) * 2016-04-20 2016-08-31 大连理工大学 Zirconium diboride-based composite material toughened by colloid-dispersed chopped carbon fibers and preparation method thereof
CN109749351A (en) * 2017-11-03 2019-05-14 航天特种材料及工艺技术研究所 A kind of phenol-formaldehyde resin modified, composite material and preparation method
CN108410125A (en) * 2018-04-24 2018-08-17 航天特种材料及工艺技术研究所 A kind of anti-heat-insulation integrative resin combination, anti-heat-insulation integrative resin base ablator and preparation method thereof
CN109852122A (en) * 2019-01-11 2019-06-07 上海交通大学 The resistance to ablative coatings of ceramic screw fiber reinforcement ba phenolic resin and its application
CN110028754A (en) * 2019-04-02 2019-07-19 航天特种材料及工艺技术研究所 A kind of micro-ablation lightweight phenolic resin and preparation method thereof
CN109968757A (en) * 2019-04-22 2019-07-05 中国人民解放军国防科技大学 Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof
CN114013122A (en) * 2021-11-24 2022-02-08 航天特种材料及工艺技术研究所 High-temperature-resistant antioxidant resin-based composite material and preparation method thereof
CN114437464A (en) * 2021-12-20 2022-05-06 西安近代化学研究所 Preparation method of ablation-resistant low-thermal-conductivity composite material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
徐修成.高分子工程材料.北京航空航天大学出版社,1990,128-129. *
李然 ; 郭安儒 ; 吴文敬 ; 李杰 ; .纳米无机填料改性酚醛树脂基防热复合材料烧蚀性能研究现状.复合材料科学与工程.2020,(第06期),114-120. *
陈祥宝等.树脂基复合材料制造技术.冶金工业出版社,2000,134-135. *

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