CN109370148A - A kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film and preparation method thereof - Google Patents
A kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film and preparation method thereof Download PDFInfo
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- CN109370148A CN109370148A CN201811151650.0A CN201811151650A CN109370148A CN 109370148 A CN109370148 A CN 109370148A CN 201811151650 A CN201811151650 A CN 201811151650A CN 109370148 A CN109370148 A CN 109370148A
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- 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
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- 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
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- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
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- 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
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- 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
Abstract
It can porcelain phenolic resin infiltration film and preparation method thereof the invention discloses a kind of high-densit high temperature suitable for RFI moulding process, by 100 parts of RTM phenolic resin system, 150~200 parts of magnesium aluminate spinel particle, 120~150 parts of forsterite particle, 80~100 parts of silicon carbide whisker heating 3, mixing, stirring post-calendering film forming；It then takes out, is cooled to room temperature the film for being prepared into 0.6~0.8mm.At 70 DEG C~80 DEG C, viscosity is decreased obviously film prepared by the present invention, is had good infiltration, can be prepared composite material by RFI technique wetting fibre braided fabric；At 150 DEG C~180 DEG C, heat cure molding；1000 DEG C or more, can while phenolic aldehyde matrix is by thermal cracking in porcelain phenolic resin film, with silicon carbide whisker, high-temperature phase-change inorganic particle together be changed into high-densit antiscour ceramic layer.Applied to advanced aerospace craft component, high hot-fluid, the high thermal environment washed away are resisted.
Description
Technical field
The present invention relates to High temperature polymer composites fields, relate particularly to a kind of suitable for RFI molding work
The high-densit high temperature of skill can porcelain phenolic resin infiltration film and preparation method thereof.
Background technique
Resin Film Infusion (Resin Film Infusion, RFI) technique is a kind of resin infiltration and fiber preform phase
In conjunction with a kind of Resin impregnation techniques, have that easy to operate, product fiber content is low, have excellent performance, is at low cost, is suitble to preparation
The advantages that large-sized structural parts.
RFI moulding process is more demanding to resin film matrix craftsmanship, it requires resin matrix at room temperature can be at
Film, and the resin film being prepared has good toughness, and tack-free；Under melting temperature, when resin is able to maintain one section
Between low viscosity, fiber preform can be thoroughly impregnated；Then with the raising of temperature, viscosity comparatively fast increases；The solidification temperature of resin
Degree should be higher than that its melting temperature.The resin matrix for being widely used in RFI technique at present has: epoxy resin, unsaturated polyester (UP), second
Alkenyl esters resin, dimaleoyl imino resin etc..A kind of nano silica as disclosed in publication number CN106928656 changes
The preparation method of property RFI epoxy resin film, it is pre- by nano-silicon dioxide modified epoxy resin and boron trifluoride ethylamine complex compound
Aggressiveness is made.A kind of preparation method of modified epoxy resin film as disclosed in publication number CN101735573, by diamine and double
Maleimide performed polymer modified epoxy resin is made.But due to epoxy resin, unsaturated polyester (UP), vinyl ester resin, span
Carry out the matrixes such as acid imide, flame retardant property, high temperature resistance, ablation resistance are poor, limit RFI moulding process advanced
The application of aerospace craft heat shield member.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to resist advanced aerospace craft
The high hot-fluid of the components such as air intake duct, the jet pipe of engine, the high thermal environment washed away, preparation are suitable for the high-densit of RFI moulding process
High temperature can porcelain phenolic resin infiltration film, meet advanced space flight and aviation aircraft component and resist high hot-fluid, high wash away thermal environment
Thermal protection demand improves the reliability of advanced space flight and aviation aircraft component thermal protection.
In order to solve the above technical problem, the present invention provides a kind of high-densit high temperature suitable for RFI moulding process can porcelain
The preparation method for changing phenolic resin infiltration film, comprises the following steps:
(1) by RTM phenolic resin system, magnesium aluminate spinel particle, forsterite particle, silicon carbide whisker at 65-75 DEG C
Lower heating 20-40 minutes；RTM phenolic resin system viscosity is decreased obviously at this time；
(2) each component after step (1) heating is quickly mixed with mechanical stirring equipment, stirring 5~after ten minutes, it mixes
Object is closed into homogeneous system；
(3) the resulting uniformly mixed material of step (2) is poured into bolster to be covered in the mold of release cloth, mold
80 DEG C of temperature, calendering film forming；
(4) after rolling, the film up and down with release cloth is taken out, is cooled to room temperature, release cloth can freely be taken off
It opens, after rolling, the thickness control of film is in 0.6~0.8mm.
As a preferred embodiment of the above technical solution, the high-densit high temperature provided by the invention suitable for RFI moulding process can porcelain
Changing phenolic resin infiltration film and preparation method thereof further comprises some or all of following technical characteristic:
As an improvement of the above technical solution, in the step (1), by weight: RTM phenolic resin system 100
Part, 150~200 parts of magnesium aluminate spinel particle, 120~150 parts of forsterite particle, 80~100 parts of silicon carbide whisker.
As an improvement of the above technical solution, in the step (2), the revolving speed of stirring is 300~500 revs/min.
As a preferred embodiment of the above technical solution, the RTM phenolic resin system is B80 phenolic resin, solvent-free liquid
Phenolic resin, Phenolic Resin Modified By Bismaleimide and any two or a variety of mixtures in phenylpropyl alcohol oxazines resin.
As a preferred embodiment of the above technical solution, the median of the magnesium aluminate spinel particle is 1~3um, and purity is greater than
99%.
As a preferred embodiment of the above technical solution, the median of the forsterite particle is 1~3um, and purity is greater than
99%.
As a preferred embodiment of the above technical solution, the silicon carbide whisker draw ratio is about 10~20, and whisker average length exists
10-20um, purity are greater than 99%.
A kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film, the permeable membrane is by upper
Any means preparation gained stated.
As a preferred embodiment of the above technical solution, the high-densit high temperature provided by the invention suitable for RFI moulding process can porcelain
Changing phenolic resin infiltration film further comprises some or all of following technical characteristic:
As an improvement of the above technical solution, it is described it is high-densit can porcelain phenolic resin film have at room temperature it is good
Good film forming, viscosity is 15000~17000mPas at room temperature；It is minimum in 70 DEG C~80 DEG C viscosity, be 2000~
2200mPas, and hold time at 30 minutes or more, there is good infiltration.At 150 DEG C~180 DEG C, viscosity liter
Height is 7400~7600mPas.
As a preferred embodiment of the above technical solution, it is described it is high-densit can porcelain phenolic resin film, under air atmosphere, 1450
DEG C weight retention >=100%, oxy-acetylene linear ablative rate≤0.015mm/s.Formed high-densit antiscour ceramic layer with
Mullite, sillimanite and magnesia are principal crystalline phase.
The present invention is high temperature resistant, the high RTM phenolic resin system of carbon yield, the resin matrix using resin matrix
The resin film that can be formed a film, and be prepared at room temperature has good toughness, and tack-free；Under melting temperature,
Resin is able to maintain the low viscosity of a period of time, can be thoroughly impregnated fiber preform；Then with the raising of temperature, viscosity comparatively fast increases
It is long；The solidification temperature of resin should be higher than that its melting temperature.
Using phenolic resin high temperature resistant, carbon yield is high the features such as, as being suitable for RFI moulding process resin film
Matrix, a kind of patent of invention of this type Resin film infusion as disclosed in 104774424 A of publication number CN is with resistance to ablation tree
Rouge and preparation method thereof exactly prepares resin film using the resistance to ablation characteristics of phenolic resin as matrix resin itself.The invention patent with
Foregoing invention patent is compared to there is following differences: (1) matrix that the present invention uses is the RTM phenolic resin system compounded,
It is not certain single phenolic resin, viscosity is lower under melting temperature, infiltration ability is stronger；(2) present invention also added
A large amount of inorganic particle and whisker are modified and adulterate to RTM phenolic resin system, such as magnesium aluminate spinel particle, magnesium olive
Stone particle, silicon carbide whisker etc. greatly improve the thermal stability and weight retention of resin film under air.The present invention obtains
The high-densit high temperature arrived can porcelain phenolic resin infiltration film, at room temperature have good film forming, have at 70 DEG C~80 DEG C good
Good infiltration, can prepare composite material by RFI technique wetting fibre braided fabric；At 150 DEG C~180 DEG C, thermosetting chemical conversion
Type；At 1000 DEG C or more, it is high-densit can ceramic phenolic resin film be changed into high-densit antiscour ceramic layer.
Polymer matrix composite can ceramic technology, be to improve polymer matrix composite high temperature resistant, resistance to ablation, anti-
The brand-new route washed away.One kind as disclosed in publication number CN 102675822 can ceramic carbon-based polymer composite wood
Material and preparation method thereof, by carbon-based resin, high temperature resistant coupling agent, fibre reinforced materials, aluminium silicate mineral matter powder and non-oxygen
The property changed ceramic powders are suppressed through mixing.One kind as disclosed in publication number CN103058632 can the high carbon polymer of ceramic
Based composites and preparation method thereof, by the high carbon-based resin of thermosetting property, eutectic mixture, clay class layer structure mineral powder
Material and shaping assistant hot melt mixing, pour and cast from mold, heat cure molding.The present invention can porcelain in carbon-based polymer high temperature
Under theoretical guide, have following difference with the above invention: (1) above two invention preparation is that fiber-reinforced polymer-matrix is multiple
Condensation material, and it is prepared by the present invention be suitable for RFI moulding process can porcelain phenolic resin infiltration film；(2) present invention addition
High-purity magnesium-aluminum spinel particle, forsterite particle, silicon carbide whisker lead to from different in when preparation method
Cross RFI technique wetting fibre fabric curing molding, at high temperature heating surface by can porcelainization reaction can form high-densit, resistance to punching
The ceramic heat insulation layer of brush.
Compared with prior art, technical solution of the present invention has the following beneficial effects: at room temperature, can porcelain phenolic aldehyde tree
Adipose membrane by modified and doping, viscosity is high, it is tack-free, with good film forming；At 70 DEG C~80 DEG C, viscosity is decreased obviously,
With good infiltration, composite material can be prepared by RFI technique wetting fibre braided fabric；At 150 DEG C~180 DEG C, heat
Curing molding；It 1000 DEG C or more, can be while phenolic aldehyde matrix be by thermal cracking in porcelain phenolic resin film, with silicon carbide whisker, height
The inorganic particle of warm phase transformation is changed into high-densit antiscour ceramic layer together.Applied to advanced aerospace craft component, resist
High hot-fluid, the high thermal environment washed away.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will make simply to the attached drawing of embodiment below
It introduces.
The high-densit high temperature of Fig. 1 (a) can porcelain phenolic resin film temperature-viscosity curve figure；
The high-densit high temperature of Fig. 1 (b) can porcelain phenolic resin film viscosity profile over time figure；
The high-densit high temperature of Fig. 2 (a) can 40 carbon fibre fabric thickness direction scanning electron microscope of porcelain phenolic resin film infiltration
Figure；
The high-densit high temperature of Fig. 2 (b) can 40 carbon fibre fabric thickness direction Al member vegetarian noodles of porcelain phenolic resin film infiltration sweep
Figure；
The high-densit high temperature of Fig. 3 can porcelain phenolic resin film room temperature~1450 DEG C in air atmosphere thermogravimetric analysis figure；
The high-densit high temperature of Fig. 4 can form the micro-structure diagram of high-densit ceramic layer after porcelain phenolic resin film ablation；
The high-densit high temperature of Fig. 5 can XRD object phasor under porcelain phenolic resin film different temperatures.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become a mesh by the detailed description
So.
Embodiment 1:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide
10 parts of phenol-formaldehyde resin modified, 10 parts of phenylpropyl alcohol oxazines resin constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 200
Part, 150 parts of forsterite particle, 100 parts of silicon carbide whisker.
Step 1: each component by weight after weighing respectively, is put into 70 DEG C of baking oven and heats 30 minutes.Use machine
Tool mixing plant quickly mixes each component after heating, and stir about 5~after ten minutes, mixture is at homogeneous system.It will mixing
Uniform material pours into bolster and is covered in the mold of release cloth, and 80 DEG C of mold temperature, calendering film forming.After calendering,
Film up and down with release cloth is taken out together.It is cooled to room temperature, release cloth can be opened freely.After rolling, the thickness of film
Control is in 0.6~0.8mm.
Complete step 1, can be obtained a kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin seep
Permeable membrane.
Embodiment 2:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide change
Property 10 parts of phenolic resin, 10 parts of phenylpropyl alcohol oxazines resin, constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 150
Part, 120 parts of forsterite particle, 80 parts of silicon carbide whisker.
Step 1: with the step one in embodiment 1；
Step 2: taking a certain amount of permeable membrane, and the viscosity-temperature curve and viscosity-of the film are measured using plate rheometer
Time graph, i.e. Fig. 1.Fig. 1 (a) is the temperature-viscosity curve figure of film.By Fig. 1 (a) it is found that as the temperature increases, film
Viscosity presentation first reduces the phenomenon that increasing afterwards, and minimum in 70 DEG C~80 DEG C viscosity, temperature-viscosity curve is in U-shape.U shape is viscous
Degree-temperature curve makes film at room temperature with good film forming, 70 DEG C~80 DEG C good infiltrations, 150 DEG C~180
The features such as DEG C heat cure molding.Fig. 1 (b) is the viscosity profile over time figure of film.By Fig. 1 (b) it is found that at 70 DEG C~110 DEG C
Each temperature section, the increase at any time of the viscosity of film and increase.But within the scope of 70 DEG C~80 DEG C, viscosity speed increase with time
More slowly.Within the scope of 70 DEG C~80 DEG C, viscosity value added is respectively less than 50mPas in 50 minutes, and film has the sufficient time
Infiltration and wetting fibre fabric guarantee smoothly completing for RFI technique.
Embodiment 3:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide
10 parts of phenol-formaldehyde resin modified, 10 parts of phenylpropyl alcohol oxazines resin constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 200
Part, 120 parts of forsterite particle, 80 parts of silicon carbide whisker.
Step 1: with the step one in embodiment 1；
Step 2: it is that 100 × 100 × 0.28mm carbon fiber plain cloth presses 0 °/90 ° direction layings by 40 chip sizes, takes two
Permeable membrane is covered on a side surface of carbon fiber laying fabric, with refractory seals glue, had by the permeable membrane that piece prepares
The vacuum bag of vacuumizing joint seals, and is put into autoclave, using RFI process heat curing molding.Vacuum degree in vacuum bag
0.1MPa, autoclave normal pressure 0.2MPa, 2 DEG C/minute of heating rate, autoclave normal pressure rate of pressure rise 50KPa/ points.Temperature is bent
Line are as follows: 100 DEG C, 1 hour；120 DEG C, 0.5 hour；150 DEG C, 0.5 hour；180 DEG C, 1 hour；60 DEG C of natural cooling is by sample
It takes out.
Step 3: being scanned Electronic Speculum member vegetarian noodles in thickness direction for the sample of curing molding and sweep, i.e. Fig. 3.
Fig. 2 (a) is 40 carbon fibre fabric thickness direction scanning electron microscope (SEM) photographs of film infiltration, and Fig. 2 (b) is 40 carbon of film infiltration
Fabric thickness direction Al member vegetarian noodles sweeps figure, and Al rubidium marking point is blue dot in figure.Due to being added to magnalium in permeable membrane
Spinel particle (MgAl2O4), so the Al member in selection magnesium aluminate spinel particle usually knit by 40 carbon fibers of evaluated for film infiltration
The infiltration of object.By Fig. 2 (a) and 2 (b) comparison, without any reunion point in Fig. 2 (b), expression Al element exists blue dot
40 layers of carbon fibre composite thickness direction distributes very evenly, and without any agglomeration, illustrates that high-densit high temperature can porcelain
The infiltration for changing phenolic resin film is good.
Embodiment 4:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide
10 parts of phenol-formaldehyde resin modified, 10 parts of phenylpropyl alcohol oxazines resin constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 150
Part, 120 parts of forsterite particle, 100 parts of silicon carbide whisker.
Step 1: with the step one in embodiment 1；
Step 2: permeable membrane is subjected to heat cure in baking oven.Temperature curve are as follows: 100 DEG C, 1 hour；120 DEG C, 0.5 is small
When；150 DEG C, 0.5 hour；180 DEG C, 1 hour；60 DEG C of natural cooling are taken out sample.
Step 3: thermogravimetric analyzer is utilized, in air atmosphere, with the heating rate of 10 DEG C/min, 30 DEG C~1450
DEG C to permeable membrane carry out thermal weight loss test.Fig. 3 is the thermogravimetric analysis figure of film room temperature~1450 DEG C in air atmosphere.It can by Fig. 3
Know, high-densit high temperature can porcelain phenolic resin film high high-temp stability it is excellent, 1450 DEG C of weight retention reaches
110%.
Embodiment 5:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide
10 parts of phenol-formaldehyde resin modified, 10 parts of phenylpropyl alcohol oxazines resin constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 200
Part, 150 parts of forsterite particle, 100 parts of silicon carbide whisker.
Step 1: with the step one in embodiment 1；
Step 2: permeable membrane cutting, lamination are put into mold, then carry out heat cure in vulcanizing press.Temperature curve
Are as follows: 100 DEG C, 1 hour；120 DEG C, 0.5 hour；150 DEG C, 0.5 hour；180 DEG C, 1 hour；60 DEG C of natural cooling take sample
Out.120 DEG C start to pressurize, pressure 5MPa.
Step 3: sample is machined, and is processed into the ablation sample of 30 × 10mm of Φ.Utilize oxyacetylene ablation machine
Ablation test is carried out to sample, 5 samples are one group, and linear ablative rate is averaged.It is tested through oxyacetylene ablation, the line of sample
Ablating rate is 0.012mm/s.Fig. 4 is the microstructure of the film surface after ablation.As seen from Figure 4, film surface is in after ablation
Show fine and close ceramic structure, the crystal boundary between crystal grain is high-visible, and average grain size is 300~400nm."
Embodiment 7:
Component: by weight: 50 parts of B80 phenolic resin, 30 parts of solvent-free liquid phenolic resin, bismaleimide
10 parts of phenol-formaldehyde resin modified, 10 parts of phenylpropyl alcohol oxazines resin constitute 100 parts of RTM phenolic resin system.Magnesium aluminate spinel particle 200
Part, 120 parts of forsterite particle, 80 parts of silicon carbide whisker.
Step 1: with the step one in embodiment 1；
Step 2: permeable membrane is subjected to heat cure in baking oven.Temperature curve are as follows: 100 DEG C, 1 hour；120 DEG C, 0.5 is small
When；150 DEG C, 0.5 hour；180 DEG C, 1 hour；60 DEG C of natural cooling are taken out sample.
Step 3: the permeable membrane after solidification is heat-treated in Muffle furnace.Heat treatment temperature be respectively as follows: 1000 DEG C,
1200 DEG C, 1450 DEG C, heat treatment time 30 minutes.
Step 4: utilizing X-ray diffractometer, by nonheat-treated permeable membrane, 1000 DEG C, 1200 DEG C, 1450 DEG C of heat treatments
Permeable membrane afterwards carries out material phase analysis.Fig. 5 is the XRD object phasor under film different temperatures, as shown in Figure 5, nonheat-treated infiltration
The object of film at room temperature is mutually magnesium aluminate spinel crystal phase (MgAl2O4), forsterite crystal phase (MgSiO4), silicon carbide crystal phase
(SiC).At 1000 DEG C~1200 DEG C, along with magnesium aluminate spinel crystal phase (MgAl2O4) and forsterite crystal phase (MgSiO4)
It decomposes:
MgAl2O4(s)=MgO (s)+Al2O3(s) (1)
Mg2SiO4(s)=2MgO (s)+SiO2(s) (2)
Mullite crystalline phase (Al6Si2O13) and sillimanite crystal phase (Al2SiO5) start to gradually form:
3Al2O3(s)+2SiO2(s)=Al6Si2O13(s) (3)
Al2O3(s)+SiO2(s)=Al2SiO5(s) (4)
At 1200 DEG C~1450 DEG C, along with the oxidation of silicon carbide crystal phase (SiC), while absorbing oxygen in air, generate
Silica continue to participate in solid phase reaction (3) and (4):
SiC(s)+2O2(g)=SiO2(s)+CO2(g) (5)
At 1450 DEG C, permeable membrane by high temperature can porcelainization transformation, final object is mutually mullite crystalline phase (Al6Si2O13)、
Sillimanite crystal phase (Al2SiO5) and magnesia crystal phase (MgO).
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film preparation method, feature
It is:
It comprises the following steps:
(1) RTM phenolic resin system, magnesium aluminate spinel particle, forsterite particle, silicon carbide whisker are added at 65-75 DEG C
It is 20-40 minutes hot；
(2) each component after step (1) heating is quickly mixed with mechanical stirring equipment, is stirred 5~10 minutes；
(3) the resulting uniformly mixed material of step (2) is poured into bolster to be covered in the mold of release cloth, mold temperature 80
DEG C, calendering film forming；
(4) after rolling, the film up and down with release cloth is taken out, is cooled to room temperature, release cloth can be opened freely, through pressing
It delays, the thickness control of film is in 0.6~0.8mm.
2. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that:
In the step (1), by weight: 100 parts of RTM phenolic resin system, 150~200 parts of magnesium aluminate spinel particle, magnesium
120~150 parts of olivine particles, 80~100 parts of silicon carbide whisker.
3. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that: in the step (2), the revolving speed of stirring is 300~500 revs/min.
4. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that: the RTM phenolic resin system is B80 phenolic resin, solvent-free liquid phenolic resin, span
Come imide-modified phenolic resin and any two or a variety of mixtures in phenylpropyl alcohol oxazines resin.
5. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that: the median of the magnesium aluminate spinel particle is 1~3um, and purity is greater than 99%.
6. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that: the median of the forsterite particle is 1~3um, and purity is greater than 99%.
7. as described in claim 1 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film system
Preparation Method, it is characterised in that: the silicon carbide whisker draw ratio is about 10~20, and for whisker average length in 10-20um, purity is big
In 99%.
8. a kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film, it is characterised in that: the infiltration
Permeable membrane any means as described in claim 1-7 preparation gained.
9. as claimed in claim 8 suitable for the high-densit high temperature of RFI moulding process can porcelain phenolic resin infiltration film, it is special
Sign is: it is described it is high-densit can porcelain phenolic resin film viscosity is 15000~17000mPas at room temperature；70 DEG C~
80 DEG C of viscosity are minimum, are 2000~2200mPas, and hold time at 30 minutes or more, at 150 DEG C~180 DEG C, viscosity
For 7400~7600mPas.
10. as claimed in claim 8 suitable for RFI moulding process high-densit high temperature can porcelain phenolic resin infiltration film,
Be characterized in that: it is described it is high-densit can porcelain phenolic resin film, under air atmosphere, 1450 DEG C of weight retention >=100%, oxygen
Acetylene linear ablative rate≤0.015mm/s.
Priority Applications (1)
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Cited By (2)
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| CN110194609A (en) * | 2019-04-22 | 2019-09-03 | 湖南远辉新材料研究院有限公司 | A kind of high temperature resistant, it is anti-oxidant can ceramic resin composite materials and preparation method thereof |
| CN115447218A (en) * | 2022-09-23 | 2022-12-09 | 湖北航天技术研究院总体设计所 | Light heat-proof and heat-insulating integrated structure with surface layer porcelainized and enhanced and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194609A (en) * | 2019-04-22 | 2019-09-03 | 湖南远辉新材料研究院有限公司 | A kind of high temperature resistant, it is anti-oxidant can ceramic resin composite materials and preparation method thereof |
| CN110194609B (en) * | 2019-04-22 | 2021-07-16 | 湖南远辉新材料研究院有限公司 | High-temperature-resistant and oxidation-resistant ceramizable resin composite material and preparation method thereof |
| CN115447218A (en) * | 2022-09-23 | 2022-12-09 | 湖北航天技术研究院总体设计所 | Light heat-proof and heat-insulating integrated structure with surface layer porcelainized and enhanced and preparation method thereof |
| CN115447218B (en) * | 2022-09-23 | 2023-11-17 | 湖北航天技术研究院总体设计所 | Surface porcelain reinforced light heat-proof and heat-insulating integrated structure and preparation method thereof |
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Application publication date: 20190222 |