CN101831178A - Quartz fiber reinforced composite material and preparation method thereof - Google Patents
Quartz fiber reinforced composite material and preparation method thereof Download PDFInfo
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- CN101831178A CN101831178A CN 201010161757 CN201010161757A CN101831178A CN 101831178 A CN101831178 A CN 101831178A CN 201010161757 CN201010161757 CN 201010161757 CN 201010161757 A CN201010161757 A CN 201010161757A CN 101831178 A CN101831178 A CN 101831178A
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Abstract
The invention belongs to the technical field of fiber reinforced composite materials and preparation methods thereof, and particularly discloses a quartz fiber reinforced composite material and a preparation method thereof. The composite material uses silicon dioxide and organic silicon resin in a mass ratio of (0.5-3): 1 as composite matrix and uses quartz fiber as a reinforcing phase, wherein the quartz fiber accounts for 30 to 55 percent of the volume of the composite material. The preparation method for the composite material comprises the following steps of: firstly, performing pretreatment operations such as soaking, drying, thermal treatment and the like on a quartz fiber fabricated part; secondly, placing the quartz fiber fabricated part into ion-free silicon sol to perform vacuum impregnation so as to introduce the silicon dioxide matrix; thirdly, machining and cleaning the quartz fiber fabricated part, and then placing the quartz fiber fabricated part into anhydrous ethanol solution of organic silicon resin to perform secondary vacuum impregnation and pressure impregnation; and finally, performing cross linking on the quartz fiber fabricated part to obtain the quartz fiber reinforced composite material. The quartz fiber reinforced composite material has the advantages of good dielectric property, high wave transmittance, strong capability of resisting long-time heating of ultrahigh power density microwave, good weather resistance, good rigidity and the like.
Description
Technical field
The present invention relates to a kind of matrix material and preparation method thereof, relate in particular to a kind of fibre-reinforced matrix material and preparation method thereof.
Background technology
In recent years, along with the appearance of new demand such as hyundai electronics development of science and technology and Radar Technology, electronic warfare, aerospace communication, the application of electromagnetic wave transparent material more and more widely, and is also more and more higher to its requirement.Oneself is difficult to satisfy saturating high frequency, superpower hertzian wave and the solar heat protection that development of new techniques brings/heat insulation, carrying, shock resistance, many-sided high performance requirements such as weather-proof, airtight conventional electromagnetic wave transparent material.Therefore, the high performance electromagnetic wave transparent material of development of new has become a focus.
At present; many devices need be worked under the situation of high transmit power, super high power density; this just requires to protect the long-time heating that the radome material of antenna can anti-super high power density microwave, requires it to have high saturating ripple rate, good weather and enough mechanical properties.At radome is under the situation of large size complex profile member, also needs radome material to have good moulding and processing characteristics.At this demand, what use at present is fiber reinforced polymer composites.The moulding process comparative maturity of this class material, intensity is also higher.Yet the dielectric properties and the resistance toheat of this class material are unsatisfactory, and saturating ripple rate is not high, and when the microwave heating of super high power density, material can be out of shape because of temperature rise is too high at short notice, variable color, even burns.In order to reach the requirement of high saturating ripple rate, this class material is often made honeycomb sandwich structure.Honeycomb sandwich structure brings big difficulty, the preparation of especially large complicated profile radome for the design of radome and manufacturing.In addition, fiber reinforced polymer composites is under environment such as sunlight irradiation, salt fog, wind sand, high low temperature alternation, mould, damp and hot, weathering during long-time the use, situation such as aging, decomposition, distortion can occur and cause degradation, its weathering resistance is necessary further improvement.
Than polymer composites, with quartz-ceramics and matrix material (silica fiber/SiO thereof
2) be advantages such as the inorganic electromagnetic wave transparent material of representative has that high temperature resistant, dielectric properties are stable, good weatherability, hardness and rigidity are big, corrosion-resistant, when the large complicated profile member of preparation, need not to be designed to complicated honeycomb structure.But inorganic electromagnetic wave transparent material exists also that intensity is lower, machine-shaping relatively difficulty, porosity is high and deficiencies such as the easy moisture absorption.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide the ability of good, the saturating ripple rate of a kind of dielectric properties height, anti-super high power density microwave long-time heating strong, the quartz fiber reinforced composite material of good weatherability, good rigidly, the preparation method of the quartz fiber reinforced composite material that a kind of technology is simple, equipment requirements is low also is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of quartz fiber reinforced composite material, this matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is (0.5～3) in the described complex matrix: 1, and the described volume fraction of silica fiber in matrix material as wild phase is 30%～55%.
In the above-mentioned quartz fiber reinforced composite material, the prefabricated component that is used for the described wild phase of moulding be preferably the three-dimensional preformed member of silica fibrage (for example three-dimensional four-way, three-dimensional five to, three-dimensional six to or three-dimensional seven to all can) or silica fiber cloth puncture preformed member, also can be the preformed member of 2.5D weaving manner braiding.Described silica fiber can be home-made A type or Type B silica fiber.
As a total technical conceive, the present invention also provides a kind of preparation method of quartz fiber reinforced composite material, may further comprise the steps:
(1) pre-treatment of silica fiber prefabricated component: at first make the silica fiber prefabricated component through braiding, place acetone to soak this silica fiber prefabricated component (being preferably the three-dimensional preformed member or the silica fiber cloth puncture preformed member of silica fibrage), soaking back taking-up oven dry (preferably places baking oven in 60 ℃ of following forced air dryings 4～10h), heat-treat omnidistance logical oxygen during thermal treatment then;
(2) introduce silica substrate: will place no ion silicon sol to carry out vacuum impregnation through pretreated silica fiber prefabricated component, vacuum impregnation can be carried out in vacuum tank, carry out vacuum-drying successively after dipping is finished, burn till, finish a processing cycle, repeat twice of this processing cycle above (preferred 2～5 times) and finish the introducing of silica substrate;
(3) mechanical workout and cleaning: the work in-process that will introduce behind the silica substrate carry out mechanical workout, obtain desired size and shape, then the work in-process after the mechanical workout are soaked with acetone, take out dry again;
(4) introduce the silicone resin matrix: will place the ethanol solution of silicone resin to carry out the vacuum impregnation second time and pressure impregnation through the work in-process after mechanical workout and the cleaning, dry (generally drying 6～24h in stink cupboard naturally gets final product) and carry out crosslinked after dipping is finished, finish a processing cycle, repeat this processing cycle twice above (preferred 2～6 times), finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
In the pre-treatment step of above-mentioned preparation method's silica fiber prefabricated component: the time that described silica fiber prefabricated component soaks in acetone (analytical pure) is preferably 24～48h; Described thermal treatment is meant the condition of surface of improving silica fiber by heating, the heat-up rate that concrete working method is preferably earlier with 5 ℃/min～20 ℃/min is warmed up to 400 ℃～800 ℃, be incubated 0.5～4h then, naturally cooling again (referring under the situation of logical oxygen, close heating power supply) with the stove cooling.Thermal treatment can be to carry out in retort furnace.Answer omnidistance logical oxygen in this heat treatment process, the method for omnidistance logical oxygen is preferably: the oxygen flow when intensification and insulation is controlled at 2～10L/min, and the oxygen flow during cooling is controlled at 5～20L/min.
In the step of above-mentioned preparation method's introducing silica substrate: preferably be evacuated to below the 10Pa during described vacuum impregnation, and then sucking described no ion silicon sol, the described vacuum-impregnated time (referring to suck the time of soaking behind the no ion silicon sol) is preferably 4～24h; Drying temperature during described vacuum-drying preferably is controlled at 100 ℃～200 ℃, is preferably 4～16h time of drying.
In the step of above-mentioned preparation method's introducing silica substrate: described concrete operations of burning till are meant that earlier the heat-up rate with 10 ℃/min～20 ℃/min is warmed up to 700 ℃～1000 ℃, lower the temperature naturally behind insulation 30～120min (implication is the same); In the described whole process of burning till in firing furnace logical oxygen, wherein heat up, oxygen flow preferably is controlled at 2～10L/min when being incubated, the oxygen flow during cooling preferably is controlled at 5～20L/min.
In the step of above-mentioned preparation method's introducing silicone resin matrix: the described vacuum impregnation second time preferably is meant and is evacuated to the following dipping of 10Pa 4～24h (sucking the time of soaking behind silicone resin/ethanolic soln); Described pressure impregnation preferably is meant the laggard horizontal high voltage dipping of inflated with nitrogen to 1～8MPa 4～24h, and pressure impregnation can carry out in autoclave.
In the step of above-mentioned preparation method's introducing silicone resin matrix: describedly crosslinkedly be meant that preferably being incubated 2～8h under 200 ℃～300 ℃ air atmosphere carries out crosslinked.
Among the above-mentioned preparation method, the mass ratio of silicone resin and dehydrated alcohol (analytical pure) is preferably (0.5～3) in the ethanol solution of described silicone resin: 1; Described silica fiber prefabricated component is preferably the three-dimensional preformed member or the silica fiber cloth puncture preformed member of silica fibrage.
Compared with prior art, the invention has the advantages that: than used fiber reinforced polymer composites, good (specific inductivity≤3.2 of the dielectric properties of quartz fiber reinforced composite material of the present invention, dielectric loss tangent value≤0.01), saturating ripple rate height is (in 11～13GHz wave band, saturating ripple rate 〉=90%), the ability of anti-super high power density microwave long-time heating is strong (at transmitted power 200～300W, power density 26～41W/cm
2, in the frequency 12.3GHz microwave behind the heating 30min, surface temperature rise is no more than 80 ℃, and does not have phenomenons such as distortion, ablation, variable color), weathering resistance is also relatively good.In addition, owing to contain high-modulus SiO in the matrix of matrix material of the present invention
2, so the rigidity of matrix material of the present invention is also better, matrix material of the present invention can directly be made lamellar, need not complicated honeycomb sandwich structure, thereby can alleviate the pressure of structure design and processing.Than quartz/SiO
2Matrix material (porosity is more than 25%), the porosity of quartz fiber reinforced composite material of the present invention low (＜15%), intensity is higher, and need not to do moistureproof the processing again.
In addition, the preparation technology of quartz fiber reinforced composite material of the present invention is simple, low for equipment requirements, the forming technique of portable polymer composites, workability is good, and the member ratio for preparing large complicated profile is easier to, at the Working environment towards high transmit power, super high power density microwave, can satisfy such as the active demand to performance index such as the saturating ripple rate of height, anti-super high power density microwave long-time heating such as radome material product, have good application prospects.
Description of drawings
The photo of the quartz fiber reinforced composite material that Fig. 1 prepares for the embodiment of the invention 1.
The photo of the quartz fiber reinforced composite material that Fig. 2 prepares for the embodiment of the invention 2.
The photo of the quartz fiber reinforced composite material that Fig. 3 prepares for the embodiment of the invention 3.
The photo of the quartz fiber reinforced composite material that Fig. 4 prepares for the embodiment of the invention 4.
Embodiment
Embodiment 1:
A kind of quartz fiber reinforced composite material as shown in Figure 1, this matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is 1.8: 1 in the complex matrix, and the volume fraction of silica fiber wild phase in matrix material is 45%.The prefabricated component that is used for this wild phase of moulding is the preformed member of homemade A type silica fiber by the braiding of 2.5D weaving manner.
The quartz fiber reinforced composite material of present embodiment is to prepare by following steps:
1, the pre-treatment of silica fiber prefabricated component
1.1 making prefabricated component: be raw material at first, make the silica fiber prefabricated component by the 2.5D weaving manner with homemade A type silica fiber;
1.2 pre-treatment: then this silica fiber prefabricated component is soaked 24h in analytically pure acetone, take out and to be placed in the baking oven, in retort furnace, heat-treat again in 60 ℃ of following forced air drying 8h; Heat treated program is: the heat-up rate with 10 ℃/min is warmed up to 600 ℃ earlier, and insulation 2h opens the fire door cooling then, and the thermal treatment whole process is logical oxygen in stove, and oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling.
2, introduce silica substrate
2.1 vacuum impregnation: will be positioned in the vacuum tank through pretreated silica fiber prefabricated component, and be evacuated down to below the 10Pa, and suck no ion silicon sol then, with the submergence of whole silica fiber prefabricated component, vacuum impregnation 4h; Used no ion silicon sol is colourless transparent liquid, wherein SiO
2The particle solid content is 30wt%, and particle diameter is 10～20nm, pH=7～8, various metal ion contents 1,000,000/below;
2.2 vacuum-drying: the silica fiber prefabricated component that will finish after the vacuum impregnation takes out, and carries out vacuum-drying, 120 ℃ of drying temperatures, time of drying 4h;
2.3 burn till: place retort furnace to burn till the silica fiber prefabricated component after the vacuum-drying, the program of burning till is: the heat-up rate with 10 ℃/min is warmed up to 800 ℃ earlier, and insulation 30min opens the fire door cooling; Lead to oxygen in the whole process of burning till in stove, oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling;
Above-mentioned 2.1～2.3 step 5 that repeat present embodiment are inferior, finish SiO
2The introducing of matrix.
3, mechanical workout and cleaning
To introducing SiO
2Work in-process behind the matrix carry out mechanical workout, obtain desired size and shape, add to guarantee that these work in-process are not subjected to the pollution of water, oil, metallic particles etc., avoid introducing impurity man-hour; After machining, work in-process are soaked 24h in analytical pure acetone, then at 60 ℃ of following forced air drying 6h.
4, introduce the silicone resin matrix
4.1 vacuum impregnation for the second time: will place vacuum tank through the work in-process after mechanical workout and the cleaning, and be evacuated down to below the 10Pa, and suck the ethanol solution of silicone resin then, with the complete submergence of whole work in-process, vacuum impregnation 4h; The main chain of used silicone resin is-Si-O-Si-, and the Si-OH group is contained in the termination, and side chain is methyl and phenyl, and its mass ratio by 1.5: 1 is dissolved in the ethanol solution that obtains aforesaid silicone resin in the analytically pure dehydrated alcohol;
4.2 pressure impregnation: will be positioned in the autoclave through the work in-process after the vacuum impregnation for the second time, inflated with nitrogen carries out high-pressure impregnation to 2MPa, dipping 6h;
4.3 dry: the work in-process that will finish behind the pressure impregnation take out, and place stink cupboard to dry 10h naturally;
4.4 crosslinked: the work in-process after will drying carry out crosslinked under 260 ℃ air atmosphere, crosslinked soaking time is 6h, after the cooling this surface of semi-finished is carried out manual grinding with diamond sand paper, will prevent also during polishing that it is not subjected to the pollution of water, oil, metallic particles etc., avoids introducing impurity;
Repeat above-mentioned 4.1～4.4 steps twice of present embodiment, finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
The density of the quartz fiber reinforced composite material that present embodiment prepares is 1.643g/cm
3, porosity is 13.1%, and specific inductivity is 2.95, and the dielectric loss tangent value is 0.004, and the saturating ripple rate in 11～13GHz wave band is 90%～94%, at power density 26.3W/cm
2, among the transmitted power 300W, frequency 12.3GHz microwave behind the heating 30min (reaching thermal equilibrium), 30 ℃ of surface temperature rises, phenomenons such as no distortion, variable color, ablation.
Embodiment 2:
A kind of quartz fiber reinforced composite material as shown in Figure 2, this matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is 1.5: 1 in the complex matrix, and the volume fraction of silica fiber wild phase in matrix material is 36%.The prefabricated component that is used for this wild phase of moulding is homemade A type silica fiber cloth puncture preformed member.
The quartz fiber reinforced composite material of present embodiment is to prepare by following steps:
1, the pre-treatment of silica fiber prefabricated component
1.1 making prefabricated component: be raw material at first, make the silica fiber prefabricated component by silica fiber cloth puncture mode with homemade A type silica fiber;
1.2 pre-treatment: then this silica fiber prefabricated component is soaked 24h in analytically pure acetone, take out and to be placed in the baking oven, in retort furnace, heat-treat again in 60 ℃ of following forced air drying 8h; Heat treated program is: the heat-up rate with 10 ℃/min is warmed up to 600 ℃ earlier, and insulation 2h opens the fire door cooling then, and the thermal treatment whole process is logical oxygen in stove, and oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling.
2, introduce silica substrate
2.1 vacuum impregnation: will be positioned in the vacuum tank through pretreated silica fiber prefabricated component, and be evacuated down to below the 10Pa, and suck no ion silicon sol then, with the submergence of whole silica fiber prefabricated component, vacuum impregnation 4h; Used no ion silicon sol is colourless transparent liquid, wherein SiO
2The particle solid content is 30wt%, and particle diameter is 10～20nm, pH=7～8, various metal ion contents 1,000,000/below;
2.2 vacuum-drying: the silica fiber prefabricated component that will finish after the vacuum impregnation takes out, and carries out vacuum-drying, 120 ℃ of drying temperatures, time of drying 4h;
2.3 burn till: place retort furnace to burn till the silica fiber prefabricated component after the vacuum-drying, the program of burning till is: the heat-up rate with 10 ℃/min is warmed up to 800 ℃ earlier, and insulation 30min opens the fire door cooling; Lead to oxygen in the whole process of burning till in stove, oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling;
Above-mentioned 2.1～2.3 step 5 that repeat present embodiment are inferior, finish SiO
2The introducing of matrix.
3, mechanical workout and cleaning
To introducing SiO
2Work in-process behind the matrix carry out mechanical workout, obtain desired size and shape, add to guarantee that these work in-process are not subjected to the pollution of water, oil, metallic particles etc., avoid introducing impurity man-hour; After machining, work in-process are soaked 24h in analytical pure acetone, then at 60 ℃ of following forced air drying 6h.
4, introduce the silicone resin matrix
4.1 vacuum impregnation for the second time: will place vacuum tank through the work in-process after mechanical workout and the cleaning, and be evacuated down to below the 10Pa, and suck the ethanol solution of silicone resin then, with the complete submergence of whole work in-process, vacuum impregnation 6h; The main chain of used silicone resin is-Si-O-Si-, and the Si-OH group is contained in the termination, and side chain is methyl and phenyl, and its mass ratio by 1.5: 1 is dissolved in the ethanol solution that obtains aforesaid silicone resin in the analytically pure dehydrated alcohol;
4.2 pressure impregnation: will be positioned in the autoclave through the work in-process after the vacuum impregnation for the second time, inflated with nitrogen carries out high-pressure impregnation to 2MPa, dipping 6h;
4.3 dry: the work in-process that will finish behind the pressure impregnation take out, and place stink cupboard to dry 10h naturally;
4.4 crosslinked: the work in-process after will drying carry out crosslinked under 260 ℃ air atmosphere, crosslinked soaking time is 6h, after the cooling this surface of semi-finished is carried out manual grinding with diamond sand paper, will prevent also during polishing that it is not subjected to the pollution of water, oil, metallic particles etc., avoids introducing impurity;
Repeat above-mentioned 4.1～4.4 steps twice of present embodiment, finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
The density of the quartz fiber reinforced composite material that present embodiment prepares is 1.668g/cm
3, porosity is 10.8%, and specific inductivity is 3.10, and the dielectric loss tangent value is 0.007, and the saturating ripple rate in 11～13GHz wave band is 90%～94%, at power density 26.3W/cm
2, among the transmitted power 300W, frequency 12.3GHz microwave behind the heating 30min (reaching thermal equilibrium), 45 ℃ of surface temperature rises, phenomenons such as no distortion, variable color, ablation.
Embodiment 3:
A kind of quartz fiber reinforced composite material as shown in Figure 3, this matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is 0.5: 1 in the complex matrix, and the volume fraction of silica fiber wild phase in matrix material is 38%.The prefabricated component that is used for this wild phase of moulding is homemade A type silica fiber cloth puncture preformed member.
The quartz fiber reinforced composite material of present embodiment is to prepare by following steps:
1, the pre-treatment of silica fiber prefabricated component
1.1 making prefabricated component: be raw material at first, make the silica fiber prefabricated component by silica fiber cloth puncture mode with homemade A type silica fiber;
1.2 pre-treatment: then this silica fiber prefabricated component is soaked 24h in analytically pure acetone, take out and to be placed in the baking oven, in retort furnace, heat-treat again in 60 ℃ of following forced air drying 8h; Heat treated program is: the heat-up rate with 10 ℃/min is warmed up to 600 ℃ earlier, and insulation 2h opens the fire door cooling then, and the thermal treatment whole process is logical oxygen in stove, and oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling.
2, introduce silica substrate
2.1 vacuum impregnation: will be positioned in the vacuum tank through pretreated silica fiber prefabricated component, and be evacuated down to below the 10Pa, and suck no ion silicon sol then, with the submergence of whole silica fiber prefabricated component, vacuum impregnation 4h; Used no ion silicon sol is colourless transparent liquid, wherein SiO
2The particle solid content is 30wt%, and particle diameter is 10～20nm, pH=7～8, various metal ion contents 1,000,000/below;
2.2 vacuum-drying: the silica fiber prefabricated component that will finish after the vacuum impregnation takes out, and carries out vacuum-drying, 120 ℃ of drying temperatures, time of drying 4h;
2.3 burn till: place retort furnace to burn till the silica fiber prefabricated component after the vacuum-drying, the program of burning till is: the heat-up rate with 10 ℃/min is warmed up to 800 ℃ earlier, and insulation 30min opens the fire door cooling; Lead to oxygen in the whole process of burning till in stove, oxygen flow is 3L/min when intensification and insulation, and oxygen flow is 5L/min during cooling;
Repeat above-mentioned 2.1～2.3 steps twice of present embodiment, finish SiO
2The introducing of matrix.
3, mechanical workout and cleaning
To introducing SiO
2Work in-process behind the matrix carry out mechanical workout, obtain desired size and shape, add to guarantee that these work in-process are not subjected to the pollution of water, oil, metallic particles etc., avoid introducing impurity man-hour; After machining, work in-process are soaked 24h in analytical pure acetone, then at 60 ℃ of following forced air drying 6h.
4, introduce the silicone resin matrix
4.1 vacuum impregnation for the second time: will place vacuum tank through the work in-process after mechanical workout and the cleaning, and be evacuated down to below the 10Pa, and suck the ethanol solution of silicone resin then, with the complete submergence of whole work in-process, vacuum impregnation 8h; The main chain of used silicone resin is-Si-O-Si-, and the Si-OH group is contained in the termination, and side chain is methyl and phenyl, and its mass ratio by 1.5: 1 is dissolved in the ethanol solution that obtains aforesaid silicone resin in the analytically pure dehydrated alcohol;
4.2 pressure impregnation: will be positioned in the autoclave through the work in-process after the vacuum impregnation for the second time, inflated with nitrogen carries out high-pressure impregnation to 4MPa, dipping 6h;
4.3 dry: the work in-process that will finish behind the pressure impregnation take out, and place stink cupboard to dry 10h naturally;
4.4 crosslinked: the work in-process after will drying carry out crosslinked under 260 ℃ air atmosphere, crosslinked soaking time is 6h, after the cooling this surface of semi-finished is carried out manual grinding with diamond sand paper, will prevent also during polishing that it is not subjected to the pollution of water, oil, metallic particles etc., avoids introducing impurity;
Above-mentioned 4.1～4.4 step 5 that repeat present embodiment are inferior, finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
The density of the quartz fiber reinforced composite material that present embodiment prepares is 1.560g/cm
3, porosity is 6.3%, and specific inductivity is 3.00, and the dielectric loss tangent value is 0.01, and the saturating ripple rate in 11～13GHz wave band is 90%～94%, at power density 26.3W/cm
2, among the transmitted power 300W, frequency 12.3GHz microwave behind the heating 30min (reaching thermal equilibrium), 35 ℃ of surface temperature rises, phenomenons such as no distortion, variable color, ablation.At power density 40.47W/cm
2, among the transmitted power 300W, frequency 12.3GHz microwave behind the heating 30min (reaching thermal equilibrium), 76 ℃ of surface temperature rises, phenomenons such as no distortion, variable color, ablation.
Embodiment 4:
A kind of quartz fiber reinforced composite material as shown in Figure 4, this matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is 3: 1 in the complex matrix, and the volume fraction of silica fiber wild phase in matrix material is 50%.The prefabricated component that is used for this wild phase of moulding is that the three-dimensional five of homemade A type silica fiber is to braided preforms.
The quartz fiber reinforced composite material of present embodiment is to prepare by following steps:
1, the pre-treatment of silica fiber prefabricated component
1.1 making prefabricated component: be raw material at first, make the silica fiber prefabricated component to weaving manner by silica fiber three-dimensional five with homemade A type silica fiber;
1.2 pre-treatment: then this silica fiber prefabricated component is soaked 48h in analytically pure acetone, take out and to be placed in the baking oven, in retort furnace, heat-treat again in 60 ℃ of following forced air drying 8h; Heat treated program is: the heat-up rate with 15 ℃/min is warmed up to 600 ℃ earlier, and insulation 2h opens the fire door cooling then, and the thermal treatment whole process is logical oxygen in stove, and oxygen flow is 5L/min when intensification and insulation, and oxygen flow is 10L/min during cooling.
2, introduce silica substrate
2.1 vacuum impregnation: will be positioned in the vacuum tank through pretreated silica fiber prefabricated component, and be evacuated down to below the 10Pa, and suck no ion silicon sol then, with the submergence of whole silica fiber prefabricated component, vacuum impregnation 12h; Used no ion silicon sol is colourless transparent liquid, wherein SiO
2The particle solid content is 30wt%, and particle diameter is 10～20nm, pH=7～8, various metal ion contents 1,000,000/below;
2.2 vacuum-drying: the silica fiber prefabricated component that will finish after the vacuum impregnation takes out, and carries out vacuum-drying, 120 ℃ of drying temperatures, time of drying 12h;
2.3 burn till: place retort furnace to burn till the silica fiber prefabricated component after the vacuum-drying, the program of burning till is: the heat-up rate with 15 ℃/min is warmed up to 800 ℃ earlier, and insulation 30min opens the fire door cooling; Lead to oxygen in the whole process of burning till in stove, oxygen flow is 5L/min when intensification and insulation, and oxygen flow is 10L/min during cooling;
Above-mentioned 2.1～2.3 step 7 that repeat present embodiment are inferior, finish SiO
2The introducing of matrix.
3, mechanical workout and cleaning
To introducing SiO
2Work in-process behind the matrix carry out mechanical workout, obtain desired size and shape, add to guarantee that these work in-process are not subjected to the pollution of water, oil, metallic particles etc., avoid introducing impurity man-hour; After machining, work in-process are soaked 24h in analytical pure acetone, then at 60 ℃ of following forced air drying 6h.
4, introduce the silicone resin matrix
4.1 vacuum impregnation for the second time: will place vacuum tank through the work in-process after mechanical workout and the cleaning, and be evacuated down to below the 10Pa, and suck the ethanol solution of silicone resin then, with the complete submergence of whole work in-process, vacuum impregnation 6h; The main chain of used silicone resin is-Si-O-Si-, and the Si-OH group is contained in the termination, and side chain is methyl and phenyl, and its mass ratio by 3: 1 is dissolved in the ethanol solution that obtains aforesaid silicone resin in the analytically pure dehydrated alcohol;
4.2 pressure impregnation: will be positioned in the autoclave through the work in-process after the vacuum impregnation for the second time, inflated with nitrogen carries out high-pressure impregnation to 1MPa, dipping 4h;
4.3 dry: the work in-process that will finish behind the pressure impregnation take out, and place stink cupboard to dry 10h naturally;
4.4 crosslinked: the work in-process after will drying carry out crosslinked under 260 ℃ air atmosphere, crosslinked soaking time is 6h, after the cooling this surface of semi-finished is carried out manual grinding with diamond sand paper, will prevent also during polishing that it is not subjected to the pollution of water, oil, metallic particles etc., avoids introducing impurity;
Repeat above-mentioned 4.1～4.4 steps twice of present embodiment, finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
The density of the quartz fiber reinforced composite material that present embodiment prepares is 1.453g/cm
3, porosity is 23%, and specific inductivity is 2.64, and the dielectric loss tangent value is 0.001, and the saturating ripple rate in 11～13GHz wave band is 94%～97%, at power density 26.3W/cm
2, among the transmitted power 300W, frequency 12.3GHz microwave behind the heating 30min (reaching thermal equilibrium), 32 ℃ of surface temperature rises, phenomenons such as no distortion, variable color, ablation.
Claims (10)
1. quartz fiber reinforced composite material, it is characterized in that: described matrix material is as complex matrix with silicon-dioxide and silicone resin, with the silica fiber is wild phase, the mass ratio of silicon-dioxide and silicone resin is (0.5～3) in the described complex matrix: 1, and the described volume fraction of silica fiber in matrix material as wild phase is 30%～55%.
2. quartz fiber reinforced composite material according to claim 1 is characterized in that: the prefabricated component that is used for the described wild phase of moulding is the three-dimensional preformed member or the silica fiber cloth puncture preformed member of silica fibrage.
3. the preparation method of a quartz fiber reinforced composite material may further comprise the steps:
(1) pre-treatment of silica fiber prefabricated component: at first make the silica fiber prefabricated component, place acetone to soak this silica fiber prefabricated component, soak the back and take out oven dry, heat-treat then, omnidistance logical oxygen during thermal treatment through braiding;
(2) introduce silica substrate: will place no ion silicon sol to carry out vacuum impregnation through pretreated silica fiber prefabricated component, carry out vacuum-drying successively after dipping is finished, burn till, finish a processing cycle, repeat this processing cycle and finish the introducing of silica substrate more than twice;
(3) mechanical workout and cleaning: the work in-process that will introduce behind the silica substrate carry out mechanical workout, obtain desired size and shape, then the work in-process after the mechanical workout are soaked with acetone, take out dry again;
(4) introduce the silicone resin matrix: will place the ethanol solution of silicone resin to carry out the vacuum impregnation second time and pressure impregnation through the work in-process after mechanical workout and the cleaning, dipping dries after finishing and carries out crosslinked, finish a processing cycle, repeat this processing cycle more than twice, finish the introducing of silicone resin matrix, obtain quartz fiber reinforced composite material.
4. the preparation method of quartz fiber reinforced composite material according to claim 3 is characterized in that, in the pre-treatment step of described silica fiber prefabricated component: the time of soaking in the described acetone is 24～48h; Described heat treated concrete operation method is warmed up to 400 ℃～800 ℃ for the first heat-up rate with 5 ℃/min～20 ℃/min, is incubated 0.5～4h then, lowers the temperature naturally again.
5. the preparation method of quartz fiber reinforced composite material according to claim 4, it is characterized in that, in the pre-treatment step of described silica fiber prefabricated component: the logical oxygen of described whole process is meant that specifically the oxygen flow when heating up and be incubated is controlled at 2～10L/min, and the oxygen flow during cooling is controlled at 5～20L/min.
6. according to the preparation method of claim 3 or 4 or 5 described quartz fiber reinforced composite materials, it is characterized in that, in the step of described introducing silica substrate: be evacuated to during described vacuum impregnation below the 10Pa, the described vacuum-impregnated time is 4～24h; Drying temperature during described vacuum-drying is controlled at 100 ℃～200 ℃, and be 4～16h time of drying.
7. according to the preparation method of claim 3 or 4 or 5 described quartz fiber reinforced composite materials, it is characterized in that, in the step of described introducing silica substrate: described concrete operations of burning till are meant that earlier the heat-up rate with 10 ℃/min～20 ℃/min is warmed up to 700 ℃～1000 ℃, lowers the temperature behind insulation 30～120min naturally; Logical oxygen in the described whole process of burning till wherein heats up, oxygen flow is controlled at 2～10L/min when being incubated, and the oxygen flow during cooling is controlled at 5～20L/min.
8. according to the preparation method of claim 3 or 4 or 5 described quartz fiber reinforced composite materials, it is characterized in that in the step of described introducing silicone resin matrix: the described vacuum impregnation second time is meant and is evacuated to the 4～24h of dipping below the 10Pa; Described pressure impregnation is meant the laggard horizontal high voltage dipping of inflated with nitrogen to 1～8MPa 4～24h.
9. according to the preparation method of claim 3 or 4 or 5 described quartz fiber reinforced composite materials, it is characterized in that, in the step of described introducing silicone resin matrix: describedly crosslinkedly be meant that being incubated 2～8h under 200 ℃～300 ℃ air atmosphere carries out crosslinked.
10. according to the preparation method of claim 3 or 4 or 5 described quartz fiber reinforced composite materials, it is characterized in that the mass ratio of silicone resin and dehydrated alcohol is (0.5～3) in the ethanol solution of described silicone resin: 1; Described silica fiber prefabricated component is the three-dimensional preformed member or the silica fiber cloth puncture preformed member of silica fibrage.
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