CN101880174A - Carbon/carbon composite density gradient thermal-insulation material - Google Patents
Carbon/carbon composite density gradient thermal-insulation material Download PDFInfo
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Abstract
The invention relates to a carbon/carbon composite density gradient thermal-insulation material, which is comprised of five layers of materials in turn: a front compact carbon/carbon composite layer formed by combining modified linear phenolic resin varnish resin carbon and polyacrylonitrile-based carbon fiber heat insulation felt, a polyester carbon/carbon composite layer, an internal carbon/carbon composite core layer formed by combining soluble and thermosetting phenolic resin carbon and polyacrylonitrile-based carbon fiber heat insulation felt, a polyester carbon/carbon composite layer and a back compact carbon/carbon composite layer formed by combining modified linear phenolic resin varnish resin carbon and polyacrylonitrile-based carbon fiber heat insulation felt; and the polyacrylonitrile-based carbon fiber heat insulation felt is high temperature resistant carbon fiber thermal insulation felt in which the part ratio of an X-Y plane to fibers in a Z direction is 50:1 to 250:1.
Description
Technical field
The invention belongs to carbon/carbon composite heat-insulated material technical field; related in particular to the heat insulation formed material of a kind of carbon/carbon composite density gradient; be directly to be used in the High Temperature Furnaces Heating Apparatus of vacuum and protection of inert gas; can under 1300-2500 ℃ temperature, stablize the requisite lagging material of use, especially polycrystalline silicon ingot or purifying furnace and silicon single crystal vertical pulling stove thermal field.Also related to the expensive low a kind of making method of production efficiency.
Background technology
Characteristics such as that carbon/carbon composite heat-insulated material has is high temperature resistant, good rigidly, processibility are good, be widely used in aerospace, communication optical fiber, new forms of energy, high-performance ceramic manufacturing, field of crystal growth, and along with the lagging material of current polycrystalline ingot furnace of the development of new forms of energy photovoltaic industry and thermal field of single crystal furnace, extensively being subjected to again to pay close attention to becomes a focus.
Carbon current/carbon compound heat-insulation formed material is inner, top layer density homogeneous, and the top layer does not have densification, makes heat-proof quality, powder amount and work-ing life all undesirable.Its main performance index such as table 1
| Sequence number | Title | Volume density (g/cm 3) | Heat transfer coefficient (W/m/K) |
| ??1 | Isotropy carbon/carbon composite heat-insulated material | ?0.16 | ??0.5 |
| ??2 | Anisotropic carbon/carbon composite heat-insulated material | ?0.16 | ??0.22 |
Winding after the preparation method that said high temperature furnace used carbon/carbon compound material cylinder has been narrated a kind of cylinder among the Chinese patent publication number CN101445376A uses carbon cloth through the cement dipping machine impregnated phenolic resin, cure under pressure, carbonizing treatment are mended density again, pyroprocessing obtains the carbon/carbon compound material cylinder again, though this material technology high conformity tensile strength height, this density of material is 0.25-0.50g/cm
3, it is not good to do lagging material density heat insulation effect bigger than normal, only is fit to do the furnace construction material.
Chinese patent application 200610136811.X about silicon crystal growth oven with high purity cured carbon felt making method, its technology is: select the very low soft felt of metals content impurity to make blank of material, the high temperature pre-treatment becomes the graphite felt body, make even green body infiltration solidifying agent with the sticking system of graphite and be cured typing, the carbonizing treatment base substrate, again base substrate is carried out the chemical gas phase pre-deposition, to surperficial machining, pyroprocessing is removed metallic impurity top coat then again, make and solidify the carbon felt, metals content impurity is in 300ppm.This technology is numerous and diverse, and ability usefulness has increased cost after will at high temperature handling soft felt, and complicated operation costs an arm and a leg, and is difficult to promote.Production time, long productivity ratio was lower.And deposit thickness can't be controlled as required and causes density bigger than normal.
The Chinese invention patent that the name that the applicant applies on the same day is called " a kind of high-temperature resistant carbon fiber heat insulation felt " provides possibility for carbon/carbon composite density gradient thermal-insulation material of the present invention.
Summary of the invention
The object of the invention is to provide a kind of tensile strength height, the low heat-proof quality of thermal conductivity is good, powder amount is few and the heat insulation formed material of the carbon/carbon composite density gradient of long service life.
Another object of the present invention is to provide a kind of production efficiency height, simple to operate, the production method of the heat insulation formed material of carbon/carbon composite density gradient that cost is cheap relatively.
A kind of high-temperature resistant carbon fiber heat insulation felt that the present invention applies on the same day with the applicant is as blank of material, and its fiber orientation anisotropy X-Y plane and Z are 50～250: 1 to the fiber portion rate.Thickness is that 30 microns 20 micron pore size array unsaturated polyester templates are made the density gradient interfacial layer.The solubility heat-reactive phenolic resin is made low density blank of material soaker, the linear novolac resin of modification is made top layer base substrate soaker, carry out disposable press curing, behind the heavy carbon of 500 ℃ of liquid phases, form the top layer densification then, inner low-density density gradient, finally after 2400 ℃ of pyroprocessing, make metals content impurity at 200ppm with the heat insulation formed material of interior carbon/carbon composite density gradient.
The carbon/carbon composite density gradient structural representation as shown in Figure 1.
Referring to accompanying drawing 1 as can be known, be example according to the heat insulation formed material of 50 mm thick carbon/carbon composite density gradients, its different carbon/carbon compound material of density difference, thickness that is of five storeys constitutes.
The front densified carbon/carbon composite bed 1 of linear novolac resin of modification and the compound composition of PAN-based carbon fiber heat insulation felt, 30 microns polyester carbon/carbon composite layers 2, the compound heart layer 3 of the inside carbon/carbon of solubility heat-reactive phenolic resin and the compound composition of PAN-based carbon fiber heat insulation felt, 30 microns polyester carbon/carbon composite layers 4, the back side densified carbon/carbon composite bed 5 of linear novolac resin of modification and the compound composition of PAN-based carbon fiber heat insulation felt.
6 is 20 microns the holes of opening on the 30 micron thickness polyester planes among the figure, 10 holes, horizontal distribution hole/centimetre
2
Front tight zone 1:1 layer is formed, thickness 1-3 millimeter, density 0.45-0.78 gram per centimeter
3
Inner heart layer 3:1-30 layer is formed thickness 5-200 millimeter, density 0.16-0.20 gram per centimeter
3
Back side tight zone 5:1 layer is formed, thickness 1-3 millimeter, density 0.45-0.78 gram per centimeter
3
Total technological process figure as shown in Figure 2.
Concrete preparation method:
(1) cutting: with thickness is the 8-12 millimeter, and the door width of cloth is 1.5 meters, and grammes per square metre is a 350-700 gram/rice
2, tensile strength is 15-45N/2 centimetre, (X-Y plane and Z are 50～250 to the fiber portion rate: 1) the high-temperature resistant carbon fiber heat insulation felt rectangular parallelepiped that is cut into 3-32 sheet 1500X1420X12mm is made blank of material to a volume fiber orientation anisotropy of 20 meters of length.
(2) join glue: the PL-4246 of solid content 60% (group Rong Huagong) type solubility heat-reactive phenolic resin is made into the liquid impregnation agent of solid content 30～45% with 99% analytically pure alcohol, pours in the agitation vat after preparing and evenly stir, prepare against the usefulness of dipping.
(3) dipping: the blank of material that cuts in (1) is taken out 2 remaining blank of material flood with the soaker for preparing in (2), blank of material is 1: 1.15～1.40 with the ratio of soaker weight.The liquid impregnation agent that dipping calculates passing ratio at normal temperatures sprays in blank of material and gets final product, and spraying must be even.
(4) dress mould: post separate-type paper in mould, flooding in (3) in the neat mould of packing into of good blank of material, respectively lay 2 of 20 micron pore size array unsaturated polyester templates on upper and lower surface in the dress mold process again, its thickness is 30 microns.Respectively put 12 blank of material of taking out again 2 20 micron pore size array unsaturated polyester template above and below from (1), 2 blank of material to 20 micron pore size array unsaturated polyester template above and below spray the linear novolac resin of modification at normal temperatures then.The amount of spraying can be 1: 1.2～1.5 according to the ratio of the linear novolac resin weight of blank of material and modification.The linear novolac resin of described modification is a silicon modification F01-1 molded lines novolac resin, and solid content is 57-70%.The described immersion liquid that sprays the linear novolac resin of modification is the liquid impregnation agent that is made into solid content 45～50% with 99% analytically pure alcohol.
(5) press curing: the mould that installs blank of material in (4) is put into carries out disposal molding compacting in the 16T swaging machine.Pressure is 0.625Kg/cm
2Pressing solidly of band, solidification value room temperature to 175 ℃, 3～6 hours set times.Recommendation is raised to 175 ℃ per hour to heat up 50 ℃ from normal temperature, is cooled to then take out from press below 50 ℃.
(6) the heavy carbon of liquid phase: the product that step (5) the is cured high temperature sintering furnace of packing into, under 10-8000Pa pressure, per hour to heat up 75 ℃ to 400 ℃, per hour heat up 25 ℃ to 500 ℃, 500 ℃ of insulations 2 hours then.Linear novolac resin begins to form carbon in 400 ℃-500 ℃ scope, when the linear novolac resin of modification is forming fine and close high-density carbon/carbon compound material top layer with the carbonization under high temperature more of unsaturated polyester template behind the heavy carbon of 500 ℃ of liquid phases, and obtain global density gradient lagging material with the blank of material carbonization at high temperature formation low density carbon/carbon compound material internal layer of solubility heat-reactive phenolic resin dipping.
(7) high temperature sintering: under 10-8000Pa pressure, to the product behind the heavy carbon of 500 ℃ of liquid phases, per hour 25～100 ℃ temperature rise rate reaches 2400 ℃, at high temperature carries out purifying treatment, make metals content impurity at 200ppm with the heat insulation formed material of interior carbon/carbon composite density gradient; Described temperature rise rate suggestion: per hour heat up 25 ℃ to 600 ℃ from 500 ℃, per hour heat up 30 ℃ to 750 ℃, 750 ℃ of constant temperature 2 hours, per hour heat up 40 ℃ to 950 ℃ then, per hour heat up 50 ℃ to 1200 ℃, per hour heat up 55 ℃ to 1500 ℃, per hour heat up 60 ℃ to 1800 ℃, per hour heat up 70 ℃ to 2000 ℃, per hour heat up 75 ℃ to 2200 ℃, per hour heat up 80 ℃ to 2400 ℃, 2400 ℃ of insulations stop after 1 hour heating up, and come out of the stove after cooling to room temperature naturally.
The mask electron beam irradiating preparation process preparation of the CN101067027 patented technology microwell array polyester template that 20 micron pore size array unsaturated polyester templates in above-mentioned preparation method's step (4) have for the applicant.
Using 20 micron pore size array unsaturated polyester templates mainly is to intercept modification linear thermoplastic novolac resin to be infiltrated up in the blank of material under the unsaturated polyester template.
The unsaturated polyester template is opened 20 micron pore size arrays, and purpose is to allow in the blank of material carbon fiber of silk footpath 8-12 micron pass 20 micron pore size array unsaturated polyester templates make unsaturated polyester template and blank of material good binding.
The 16T press is the ordinary hot press in the above-mentioned steps (5).Pressing process be disposable be pressed into required thickness (as the thick carbon of 50mm/carbon composite heat-insulated material be behind the disposable 53mm of being pressed into sintering shrink form).
The heavy carbon of liquid phase in the above-mentioned steps (6) is to carry out in 400-500 ℃ liquid phase, and the carbon of liquid phase carbonization is by lamination, under deposition on the unsaturated polyester template.
The pyroprocessing of above-mentioned steps (7) is to modification linear thermoplastic novolac resin, unsaturated polyester template, the carbonization of solubility heat-reactive phenolic resin and greying.Along with the improving constantly them and be carbonized successively of temperature, finally make the heat insulation formed material of a kind of carbon/carbon composite density gradient 2400 ℃ of following greyings.
The heat insulation formed material characteristics of carbon/carbon composite density gradient of the present invention are:
One. the upper layer densification.
Positive fine and close high density material layer is because the big (0.56g/cm of density
3) space is little, purity height (ash content is less than 200PPm), therefore anti-ablation, resistance to oxidation.Remove acidproof, alkaline-resisting in addition.Especially it is fast to conduct heat in the planar all directions when there is one deck high density material on the surface as the thermal field material, makes plane temperature homogeneity everywhere good (＜± 5 ℃).And how heat passage very little owing to inner heart layer porous void on thickness direction, make the carbon/carbon composite density gradient material monolithic have anisotropic Heat transfer coefficient.The back surface layer density is less than the front, but is higher than inner heart layer, and (power thrusts is perpendicular to face direction: flexural strength 2.36MPa, and 5% o'clock flexural strength is 0.50MPa to make carbon/carbon composite density gradient thermal-insulation material intensity, good rigidity; Power thrusts is parallel to face direction: flexural strength 4.12MPa, and 5% o'clock flexural strength is 0.81MPa).The strength of materials, rigidity significantly improves, and helps operation and use.
Improve barrier properties for gases, helped suppressing convective heat transfer.Reduce specific surface area and improve the resistance to oxidation degree, improved work-ing life.Minimizing can effectively suppress the generation of carbon dust to the oxidation of hot-zone face, improves the furnace inner environment degree of cleaning, reduces that carbon content promotes crystal quality in the crystal.
Two. inner loose low-density material.
1. effectively control the volume density of carbon/carbon composite heat-insulated material, improve the effect that suppresses heat passage.
2. alleviate deadweight, be convenient to fitting operation.
3. reduce material self heat storage capacity, be beneficial to cooling, the CONTROL PROCESS time.
The effect of invention
The present invention has made the thick carbon/carbon composite density gradient thermal-insulation material of 50mm.Evenly heat transmission coefficient 1500 ℃ the time is 0.213W/M/K in the vacuum state stove after tested, and the evenly heat transmission coefficient of present commercially available stack pile anisotropic carbon/carbon composite heat-insulated material is 0.220W/M/K, and effect of heat insulation has improved 10%.Wherein, the unit of the W/M/K representative species capacity of heat transmission.
The evenly heat transmission coefficient of present commercially available stack pile isotropic carbon fiber lagging material has improved more than 1 times for the 0.5W/M/K effect of heat insulation.
Do silicon single-crystal thermal field base plate with the carbon/carbon composite heat-insulated material of density gradient of the present invention and replace energy efficient 30% behind traditional thermal field base plate.
Testing method: by heat flow method detect obtain under the various hot conditionss Heat transfer coefficient (500 ℃-2000 ℃).
The Heat transfer coefficient calculation formula is
Wherein λ represents heet transfer rate, and q represents heat flux, is recorded by heat flowmeter, and d is a sample thickness.T1 is the thermosphere temperature, is recorded by optical pyrometer; T2 is cold layer temperature, takes into account thermopair by hot-fluid and records.
Description of drawings
Fig. 1 is the carbon/carbon composite density gradient structural representation:
Fig. 2 is total technological process figure.
Nomenclature
In the accompanying drawing 2:
The front densified carbon/carbon composite bed of linear novolac resin carbon of 1-modification and the compound composition of PAN-based carbon fiber heat insulation felt.
2-30 micron polyester carbon/carbon composite layer.
The compound heart layer of the inside carbon/carbon of 3-solubility heat-reactive phenolic resin carbon and the compound composition of PAN-based carbon fiber heat insulation felt.
4-30 micron polyester carbon/carbon composite layer.
The back side densified carbon/carbon composite bed of linear novolac resin carbon of 5-modification and the compound composition of PAN-based carbon fiber heat insulation felt.
Embodiment
Below by embodiment, the present invention is described in further detail.But the present invention is not limited only to the following example.
(1) cutting: with thickness is 12 millimeters, and the door width of cloth is 1.5 meters, and grammes per square metre is 598 gram/rice
2, tensile strength is 20N/2 centimetre, (X-Y plane and Z are 50 to the fiber portion rate: 1-250: 1) the high-temperature resistant carbon fiber heat insulation felt rectangular parallelepiped that is cut into 11 1500X1420X12mm is made blank of material to a volume fiber orientation anisotropy of 20 meters of length.
(2) join glue: the PL-4246 of solid content 60% (group Rong Huagong) type solubility heat-reactive phenolic resin is made into the soaker of solid content 40% with 99% analytically pure alcohol, pours in the agitation vat after preparing and evenly stir, prepare against the usefulness of dipping.
(3) dipping: the blank of material that cuts in (1) is taken out 2 remaining blank of material flood with the soaker for preparing in (2), blank of material is 1: 1.3 with the ratio of soaker weight.And be uniformly impregnated within on 9 blank of material.
(4) dress mould: post separate-type paper in mould, flooding in (3) in the neat mould of packing into of 9 good blank of material, respectively lay 2 of 20 micron pore size array unsaturated polyester templates on upper and lower surface in the dress mold process again, its thickness is 30 microns.Respectively put 12 blank of material of from (1), taking out again 2 20 micron pore size array unsaturated polyester template above and below, then 2 blank of material of 20 micron pore size array unsaturated polyester template above and below are flooded the linear novolac resins of modification.Blank of material is 1: 1.35 with the ratio of soaker weight.The linear novolac resin of described modification is a silicon modification F01-1 molded lines novolac resin, and solid content is 57-70%.The described immersion liquid that sprays the linear novolac resin of modification is the liquid impregnation agent that is made into solid content 45～50% with 99% analytically pure alcohol.
(5) press curing: the mould that installs blank of material in (4) is put into carries out disposal molding compacting in the 16T swaging machine, pressure is 0.625Kg/cm
2, being pressed into thickness is 53mm.Heat up to solidify curing process simultaneously: be raised to 175 ℃ per hour to heat up 50 ℃ from normal temperature, be cooled to 50 ℃ then and from press, take out, obtain the curing work in-process of 1500X1420X53mm.
(6) the heavy carbon of liquid phase: the curing work in-process of 1500X1420X53mm are contained under 500 ℃, carry out the heavy carbon of liquid phase carbonization in the vacuum oven and handle.
Liquid phase is sunk carbon technology: under 10-8000Pa pressure, per hour to heat up 75 ℃ to 400 ℃, per hour heat up 25 ℃ to 500 ℃ then, 500 ℃ of insulations 2 hours.。
(7) high temperature sintering: the product behind the heavy carbon of 500 ℃ of liquid phases is then improved temperature at high temperature proceed high temperature graphitization and purifying treatment in same vacuum oven, final treatment temp is 2400 ℃, and making the compact surfaces layer thickness is the carbon/carbon composite density gradient thermal-insulation material of 1500X1420X50mm for the 2.5mm specification.
High-sintering process: per hour heat up 25 ℃ to 600 ℃ from 500 ℃, per hour heat up 30 ℃ to 750 ℃,, per hour heat up 40 ℃ to 950 ℃ then 750 ℃ of constant temperature 2 hours, per hour heat up 50 ℃ to 1200 ℃, per hour heat up 55 ℃ to 1500 ℃, per hour heat up 60 ℃ to 1800 ℃, per hour heat up 70 ℃ to 2000 ℃, per hour heat up 75 ℃ to 2200 ℃, per hour heat up 80 ℃ to 2400 ℃, 2400 ℃ of insulations stop after 1 hour heating up, and come out of the stove after cooling to room temperature naturally.
Make metals content impurity in 200ppm, surface layer thickness is the carbon/carbon composite density gradient thermal-insulation material of 1500X1420X50mm for the 2.5mm specification.Its surface layer body density is 0.56g/cm
3Inner thick-layer volume density is 0.16g/cm
3
Evenly heat transmission coefficient (50mm thickness) under the carbon/carbon composite density gradient thermal-insulation material decompression of the present invention is as table 1
Table 1
Carbon/carbon composite density gradient thermal-insulation material mechanical property of the present invention
1) power thrusts is perpendicular to face direction: flexural strength 1.86MPa, and 5% o'clock flexural strength is 0.40MPa
2) power thrusts is parallel to face direction: flexural strength 3.52MPa, and 5% o'clock flexural strength is 0.73MPa
(1) cutting: with thickness is 10 millimeters, and the door width of cloth is 1.5 meters, and grammes per square metre is 510 gram/rice
2, tensile strength is 18N/2 centimetre, (X-Y plane and Z are 50 to the fiber portion rate: 1-250: 1) the high-temperature resistant carbon fiber heat insulation felt rectangular parallelepiped that cuts out 13 1500X1420X12mm is again made blank of material to a volume fiber orientation anisotropy of 20 meters of length.
(2) join glue: the PL-4246 of solid content 60% (group Rong Huagong) type solubility heat-reactive phenolic resin is made into the soaker of solid content 40% with 99% analytically pure alcohol, pours in the agitation vat after preparing and evenly stir, prepare against the usefulness of dipping.
(3) dipping: the blank of material that cuts in (1) is taken out 2 remaining blank of material flood with the soaker for preparing in (2), blank of material is 1: 1.25 with the ratio of soaker weight.And be uniformly impregnated within on 11 blank of material.
(4) dress mould: post separate-type paper in mould, flooding in (3) in the neat mould of packing into of 11 good blank of material, respectively lay 2 of 20 micron pore size array unsaturated polyester templates on upper and lower surface in the dress mold process again, its thickness is 30 microns.Respectively put 12 blank of material of from (1), taking out again 2 20 micron pore size array unsaturated polyester template above and below, then 2 blank of material of 20 micron pore size array unsaturated polyester template above and below are flooded the linear novolac resins of modification.Blank of material is change in 1: 1.35 with the ratio of soaker weight.The linear novolac resin of described modification is a silicon modification F01-1 molded lines novolac resin, and solid content is 57-70%.The described immersion liquid that sprays the linear novolac resin of modification is the liquid impregnation agent that is made into solid content 45～50% with 99% analytically pure alcohol.
(5) press curing: the mould that installs blank of material in (4) is put into carries out disposal molding compacting in the 16T swaging machine, pressure is 0.625Kg/cm
2, being pressed into thickness is 53mm.Heat up to solidify curing process simultaneously: be raised to 175 ℃ per hour to heat up 50 ℃ from normal temperature, be cooled to 50 ℃ then and from press, take out, obtain the curing work in-process of 1500X1420X53mm.
(6) the heavy carbon of liquid phase: the curing work in-process of 1500X1420X53mm are contained under 500 ℃, carry out the heavy carbon of liquid phase carbonization in the vacuum oven and handle.
Liquid phase is sunk carbon technology: under 10-8000Pa pressure, per hour to heat up 75 ℃ to 400 ℃, per hour heat up 25 ℃ to 500 ℃ then, 500 ℃ of insulations 2 hours.
(7) high temperature sintering: the product behind the heavy carbon of 500 ℃ of liquid phases is at high temperature carried out purifying treatment, and final treatment temp is 2400 ℃, make metals content impurity at 200ppm with the heat insulation formed material of interior carbon/carbon composite density gradient.Surface layer thickness is 2.5mm.Specification is that its surface layer body density of 1500X1420X50mm is 0.56g/cm
3Inner thick-layer volume density is 0.16g/cm
3
High-sintering process: per hour heat up 25 ℃ to 600 ℃ from 500 ℃, per hour heat up 30 ℃ to 750 ℃,, per hour heat up 40 ℃ to 950 ℃ then 750 ℃ of constant temperature 2 hours, per hour heat up 50 ℃ to 1200 ℃, per hour heat up 55 ℃ to 1500 ℃, per hour heat up 60 ℃ to 1800 ℃, per hour heat up 70 ℃ to 2000 ℃, per hour heat up 75 ℃ to 2200 ℃, per hour heat up 80 ℃ to 2400 ℃, 2400 ℃ of insulations stop after 1 hour heating up, and come out of the stove after cooling to room temperature naturally.
Carbon/carbon composite density gradient thermal-insulation material mechanical property of the present invention
1) power thrusts is perpendicular to face direction: flexural strength 1.86MPa, and 5% o'clock flexural strength is 0.40MPa
2) power thrusts is parallel to face direction: flexural strength 3.52MPa, and 5% o'clock flexural strength is 0.73MPa
Embodiment 3
(1) cutting: with thickness is 12 millimeters, and the door width of cloth is 1.5 meters, and grammes per square metre is 598 gram/rice
2, tensile strength is 20N/2 centimetre, (X-Y plane and Z are 50 to the fiber portion rate: 1-250: 1) the high-temperature resistant carbon fiber heat insulation felt rectangular parallelepiped that is cut into 13 1500X1420X12mm is made blank of material to a volume fiber orientation anisotropy of 20 meters of length.
(2) join glue: the PL-4246 of solid content 60% (group Rong Huagong) type solubility heat-reactive phenolic resin is made into the soaker of solid content 40% with 99% analytically pure alcohol, pours in the agitation vat after preparing and evenly stir, prepare against the usefulness of dipping.
(3) dipping: the blank of material that cuts in (1) is taken out 2 remaining blank of material flood with the soaker for preparing in (2), blank of material is 1: 1.3 with the ratio of soaker weight.And be uniformly impregnated within on 11 blank of material.
(4) dress mould: post separate-type paper in mould, flooding in (3) in the neat mould of packing into of 11 good blank of material, respectively lay 2 of 20 micron pore size array unsaturated polyester templates on upper and lower surface in the dress mold process again, its thickness is 30 microns.Respectively put 12 blank of material of from (1), taking out again 2 20 micron pore size array unsaturated polyester template above and below, then 2 blank of material of 20 micron pore size array unsaturated polyester template above and below are flooded the linear novolac resins of modification.Blank of material is 1: 1.35 with the ratio of soaker weight.The linear novolac resin of described modification is a silicon modification F01-1 molded lines novolac resin, and solid content is 57-70%.The described immersion liquid that sprays the linear novolac resin of modification is the liquid impregnation agent that is made into solid content 45～50% with 99% analytically pure alcohol.
(5) press curing: the mould that installs blank of material in (4) is put into carries out disposal molding compacting in the 16T swaging machine, pressure is 0.625Kg/cm
2, being pressed into thickness is 53mm.Heat up to solidify curing process simultaneously: be raised to 175 ℃ per hour to heat up 50 ℃ from normal temperature, be cooled to then below 50 ℃,
From press, take out, obtain the curing work in-process of 1500X1420X53mm.
(6) the heavy carbon of liquid phase: the curing work in-process of 1500X1420X53mm are contained under 500 ℃, carry out the heavy carbon of liquid phase carbonization in the vacuum oven and handle.
Liquid phase is sunk carbon technology: under 10-8000Pa pressure, per hour to heat up 75 ℃ to 400 ℃, per hour heat up 25 ℃ to 500 ℃ then, 500 ℃ of insulations 2 hours.
(7) high temperature sintering: the product behind the heavy carbon of 500 ℃ of liquid phases is then improved temperature at high temperature proceed high temperature graphitization and purifying treatment in same vacuum oven, final treatment temp is 2400 ℃, making the compact surfaces layer thickness is the carbon/carbon composite density gradient thermal-insulation material of 1500X1420X50mm for the 2.5mm specification, and its surface layer body density is 0.55g/cm
3Inner thick-layer volume density is 0.18g/cm
3, metals content impurity is in 200ppm.
High-sintering process: per hour heat up 25 ℃ to 600 ℃ from 500 ℃, per hour heat up 30 ℃ to 750 ℃,, per hour heat up 40 ℃ to 950 ℃ then 750 ℃ of constant temperature 2 hours, per hour heat up 50 ℃ to 1200 ℃, per hour heat up 55 ℃ to 1500 ℃, per hour heat up 60 ℃ to 1800 ℃, per hour heat up 70 ℃ to 2000 ℃, per hour heat up 75 ℃ to 2200 ℃, per hour heat up 80 ℃ to 2400 ℃, 2400 ℃ of insulations stop after 1 hour heating up, and come out of the stove after cooling to room temperature naturally.
Carbon/carbon composite density gradient thermal-insulation material mechanical property of the present invention
1) power thrusts is perpendicular to face direction: flexural strength 2.36MPa, and 5% o'clock flexural strength is 0.50MPa
2) power thrusts is parallel to face direction: flexural strength 4.12MPa, and 5% o'clock flexural strength is 0.81MPa
Embodiment 4
(1) cutting: with thickness is 12 millimeters, and the door width of cloth is 1.5 meters, and grammes per square metre is 598 gram/rice
2, tensile strength is 20N/2 centimetre, (X-Y plane and Z are 50 to the fiber portion rate: 1-250: 1) the high-temperature resistant carbon fiber heat insulation felt rectangular parallelepiped that is cut into 11 1500X1420X12mm is made blank of material to a volume fiber orientation anisotropy of 20 meters of length.
(2) join glue: the PL-4246 of solid content 60% (group Rong Huagong) type solubility heat-reactive phenolic resin is made into the soaker of solid content 40% with 99% analytically pure alcohol, pours in the agitation vat after preparing and evenly stir, prepare against the usefulness of dipping.
(3) dipping: the blank of material that cuts in (1) is taken out 2 remaining blank of material flood with the soaker for preparing in (2), blank of material is 1: 1.1 with the ratio of soaker weight.And be uniformly impregnated within on 9 blank of material.
(4) dress mould: post separate-type paper in mould, flooding in (3) in the neat mould of packing into of 9 good blank of material, respectively lay 2 of 20 micron pore size array unsaturated polyester templates on upper and lower surface in the dress mold process again, its thickness is 30 microns.Respectively put 12 blank of material of from (1), taking out again 2 20 micron pore size array unsaturated polyester template above and below, then 2 blank of material of 20 micron pore size array unsaturated polyester template above and below are flooded the linear novolac resins of modification.Blank of material is 1: 1.35 with the ratio of soaker weight.
(5) press curing: the mould that installs blank of material in (4) is put into carries out disposal molding compacting in the 16T swaging machine, pressure is 0.625Kg/cm
2, being pressed into thickness is 53mm.Heat up to solidify curing process simultaneously: be raised to 175 ℃ per hour to heat up 50 ℃ from normal temperature, be cooled to then from press, take out below 50 ℃.Find layering to occur when solidifying product rigidity is serious inadequately, cause product rejection.
Claims (6)
1. the heat insulation formed material of carbon/carbon composite density gradient is characterized in that being made up of following five layers of material successively: linear novolac resin of modification and the compound heart layer of the PAN-based carbon fiber heat insulation felt compound inside carbon/carbon formed of compound front densified carbon/carbon composite bed, polyester carbon/carbon composite layer, solubility heat-reactive phenolic resin and the PAN-based carbon fiber heat insulation felt of forming, polyester carbon/carbon composite layer, the linear novolac resin of modification and the compound back side densified carbon/carbon composite bed of forming of PAN-based carbon fiber heat insulation felt; Described PAN-based carbon fiber heat insulation felt is that X-Y plane and Z are 50 to the fiber portion rate: 1-250: 1 high-temperature resistant carbon fiber heat insulation felt.
2. the heat insulation formed material of a kind of carbon/carbon composite density gradient as claimed in claim 1, the base material of the described high-temperature resistant carbon fiber heat insulation felt of its feature is that to become thickness with short PAN-based carbon fiber preparation of cutting length 50-150 millimeter be the 8-12 millimeter, grammes per square metre is a 500-700 gram/rice 2, the PAN-based carbon fiber heat insulation felt of tensile strength 12-50 ox/2 centimetre.
3. the heat insulation formed material of a kind of carbon/carbon composite density gradient as claimed in claim 1, the front densified carbon/carbon composite bed of linear novolac resin carbon of the described modification of its feature and the compound composition of PAN-based carbon fiber heat insulation felt, polyester carbon/carbon composite layer, the compound heart layer of the inside carbon/carbon of solubility heat-reactive phenolic resin carbon and the compound composition of PAN-based carbon fiber heat insulation felt, polyester carbon/carbon composite layer, the thickness of the back side densified carbon/carbon composite bed of linear novolac resin carbon of modification and the compound composition of PAN-based carbon fiber heat insulation felt is respectively the 1-3 millimeter, the 10-40 micron, the 5-200 millimeter, 10-40 micron and 1-3 millimeter.
4. the preparation method of the heat insulation formed material of a kind of carbon/carbon composite density gradient as claimed in claim 1, its feature be as follows:
(1) cutting of the described PAN-based carbon fiber heat insulation felt of claim 1 is become blank of material;
(2) flood or spray: at normal temperatures, the soaking in alcohol agent of solubility heat-reactive phenolic resin that will contain the solid content of 30-45% is flooded or is evenly sprayed blank of material in (1) step, and described blank of material is 1: 1.15～1.40 with the ratio of soaker weight;
(3) dress mould: 1～30 layer of blank of material plane that the dipping that step (2) is obtained is good superposes in the neat mould of packing into, lay 1 thickness on upper and lower surface respectively and be 30 microns 20 micron pore size array unsaturated polyester templates, respectively put 1 blank of material (1) again in 20 micron pore size array unsaturated polyester template above and below through spraying the blank of material of the linear novolac resin of modification, the amount of spraying is a blank of material (1) and the ratio of the linear novolac resin weight of liquid phase modification is 1: 1.2-1: 1.5.
(4) press curing: the mould that step (4) is installed blank of material carries out the disposal molding compacting in press: pressure 0.625Kg/cm
2With room temperature to 175 ℃ following curing 3～6 hours; The linear novolac resin of described modification is a silicon modification F01-1 molded lines novolac resin, and solid content is 57-70%.The described immersion liquid that sprays the linear novolac resin of modification is the liquid impregnation agent that is made into solid content 45～50% with 99% analytically pure alcohol.
(5) the heavy carbon of liquid phase: the product that step (4) is cured under 10-8000Pa pressure, per hour to heat up 75 ℃ to 400 ℃, per hour heats up 25 ℃ to 500 ℃ then in high temperature sintering furnace, 500 ℃ are incubated 2 hours.
(6) high temperature sintering: to the product behind the heavy carbon of the liquid phase of step (5), under 10-8000Pa pressure, per hour 25～100 ℃ temperature rise rate reaches 2400 ℃, and cooling obtains the heat insulation formed material of carbon/carbon composite density gradient.
5. the preparation method of the heat insulation formed material of a kind of carbon/carbon composite density gradient as claimed in claim 1, its feature wherein described press curing temperature of step 4) are per hour to heat up 50 ℃, to be raised to 175 ℃ from normal temperature, to be cooled to then take out below 50 ℃.
6. the preparation method of the heat insulation formed material of a kind of carbon/carbon composite density gradient as claimed in claim 4, its feature wherein temperature rise rate of the described high temperature sintering of step (6) is from per hour heating up 25 ℃ to 600 ℃ from 500 ℃, per hour heat up 30 ℃ to 750 ℃, 750 ℃ of constant temperature 2 hours, per hour heat up 40 ℃ to 950 ℃ then, per hour heat up 50 ℃ to 1200 ℃, per hour heat up 55 ℃ to 1500 ℃, per hour heat up 60 ℃ to 1800 ℃, per hour heat up 70 ℃ to 2000 ℃, per hour heat up 75 ℃ to 2200 ℃, per hour heat up 80 ℃ to 2400 ℃, 2400 ℃ of insulations stop after 1 hour heating up, and come out of the stove after cooling to room temperature naturally.
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