CN105237771B - A kind of polymethyl silicane containing metal and its application - Google Patents
A kind of polymethyl silicane containing metal and its application Download PDFInfo
- Publication number
- CN105237771B CN105237771B CN201510753062.4A CN201510753062A CN105237771B CN 105237771 B CN105237771 B CN 105237771B CN 201510753062 A CN201510753062 A CN 201510753062A CN 105237771 B CN105237771 B CN 105237771B
- Authority
- CN
- China
- Prior art keywords
- containing metal
- polymethyl silicane
- polymethyl
- stirring
- protective atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Ceramic Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of polymethyl silicane containing metal and its application, belong to ceramic composite preparing technical field.The molecular weight of the designed polymethyl silicane containing metal of the invention is that 1,300 1700 its room temperature viscosity are 0.04~0.1Pas；It is less than or equal to 0.03Pas in 60~120 DEG C of viscositys.The present invention is using the base substrate that porosity is 58.7~16% as prefabricated component, place the preform in polymethyl silicane containing metal, in the progress vacuum impregnations of 120 DEG C of room temperature, Pintsch process is carried out after obtaining after the prefabricated component of the polymethyl silicane containing metal after crosslinking curing repeated impregnations, crosslinking curing 34 times；By dipping, crosslinking curing 34 times, the process cycles once cracked can obtain consistency more than or equal to ceramic matric composite of the 92%, hardness more than or equal to 85HRC 3 times.The present invention is simple to operate, is easy to industrial applications.
Description
Technical field
The present invention relates to a kind of polymethyl silicane containing metal and its application, belongs to ceramic composite technology of preparing neck
Domain.
Background technology
Ceramic matric composite has high specific strength, high rigidity, wear-resistant, high temperature resistant and numerous excellent property such as anticorrosive
Can, thus there is wide application in the field such as chemical industry, coloured, metallurgical, space flight and aviation, national defence, the energy, and with the hair of science and technology
Exhibition, application field are widened, and more preferable requirement is proposed to its performance, and this requirement is mainly reflected in functional realization,
Such as：Conduction, heat conduction, magnetic, inhale ripple etc..And by the modification to ceramic base precursor, metallic element is introduced to precursor,
Then it is ceramic matrix by polymer pyrolysis by cracking infiltration pyrolysis (PIP) technique, metal will be disperseed in the form of atom level
In ceramic matric composite, the functionalization of composite can be effectively realized, while metal has the function that catalysis association, also
The ceramic yield of precursor can be improved.
Chinese patent CN104327275A and CN10430277A disclose a kind of synthetic method of polyaluminocarbosilane.But
Both approaches all have a disadvantage that：1) preparation of parent Polycarbosilane need to pass through the condensation of dimethyl monomer sodium, PDMS is refined, high
The processes such as warm solution, later stage modification needs solubilizer to dissolve parent, high temperature modified, the process such as filtering, vacuum distillation, when always preparing
Between it is long, cost is higher, also pollutes environment.2) the Si -- H bond activity of parent Polycarbosilane is relatively low, need to be at a temperature of 300-400 DEG C
It could be reacted with aluminum source compound.3) Polycarbosilane is rich carbon as ceramic matric composite prepared by maceration extract, and C/Si is about
1.8:1, serious rich carbon, this causes material at high temperature antioxygenic property poor, and in sintering process, there is the small molecule ease of many
Go out, ceramic yield is relatively low.CN101186704B discloses a kind of preparation method of metal chloride modified polymethyl silicane.The party
The metal modified polymethyl silicane that method is prepared is liquid ceramic precursor, but because ceramic precursor has viscosity high, is caused
It is greatly reduced in the density effect in density stage.In addition substantial amounts of HCl gases can be released during the technology use, are polluted
Environment and destruction equipment.Meanwhile remain in polymethyl silicane and have neither part nor lot in modified metal chloride during impregnation sintering,
The excellent properties of ceramic based material can be reduced；Moreover, metal chloride modified polymethyl silicane mistake used by the program
Cheng Zhong, purification need to be filtered, making metal modified polymethyl silicane, exposure in atmosphere, causes metal modified polymethyl silicane for a long time
Oxidation, influences maceration extract quality.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of polymethyl silicane containing metal and its application.
One kind polymethyl silicane containing metal of the invention；At least containing at least one of O-M, M-Si keys in its structure；Institute
State M and be selected from least one of Al, Cu, Zr, Fe, Ni, Mo, Ti.
One kind polymethyl silicane containing metal of the invention；Contain O-M keys and M-Si keys in its structure；The M be selected from Al,
At least one of Cu, Zr, Fe, Ni, Mo, Ti.
One kind polymethyl silicane containing metal of the invention, one kind in O-M keys, M-Si keys and M-C keys in its structure be present
It is or a variety of；The M is selected from least one of Al, Cu, Zr, Fe, Ni, Mo, Ti.
One kind polymethyl silicane containing metal of the invention；Its molecular weight is：1300-1700.
One kind polymethyl silicane containing metal of the invention；Its room temperature viscosity is 0.04~0.1Pas；In 60~120 DEG C stick
Degree is less than or equal to 0.03Pas.
One kind polymethyl silicane containing metal of the invention；Its preparation method is：
Step 1
Aluminium powder is added in sodium sand, under protective atmosphere, stirring, obtains standby sodium sand；
Step 2
By Na and Si mol ratio, Na：Si=2.5~1：2~1 with taking standby sodium sand and monomer；Under protective atmosphere, first
Sodium sand is fitted into reactor, then adds organic solvent；Stirring, after being warming up to 70-85 DEG C, divide at least 2 times by with the list taken
Body is instilled in reactor, stirring, carries out back flow reaction；Liquid after being reacted；The monomer is dichloro methyl silane；
Step 3
Under protective atmosphere, centrifugal treating is carried out to liquid after being reacted obtained by step 2, centrifugation gained liquid is in protective atmosphere
It is lower to be handled through distillation, obtain polymethyl silicane；
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：3.4~12, have with taking to be dissolved in after polymethyl silicane, crosslinking agent
In solvent, under protective atmosphere, 120~150 DEG C are warming up to after 40~50 DEG C of stirring reactions, continues stirring reaction, obtains
Polymethyl silicane containing metal；The crosslinking agent is acetyl acetone salt.
One kind polymethyl silicane containing metal of the invention, Al and Na mass ratio is 1 in standby sodium sand described in step 1:12
~1:15.
One kind polymethyl silicane containing metal of the invention, the granularity of aluminium powder described in step 1 are 30-50um, the granularity of sodium sand
For 0.5-10um.
One kind polymethyl silicane containing metal of the invention, in step 1, by aluminium powder addition sodium sand, under protective atmosphere, Yu Chang
Temperature is lower to be stirred, and obtains standby sodium sand；The speed of stirring is 100~130 revs/min.
One kind polymethyl silicane containing metal of the invention, sodium sand described in step 1 is prepared by following proposal：
Sodium block is immersed in the reactor equipped with toluene, in protective atmosphere, sodium block is heated to 97-98 DEG C, stirred,
Until sodium block is cooled to room temperature after crushing completely；Obtain the sodium sand that granularity is 0.5~10um.
One kind polymethyl silicane containing metal of the invention, in step 1, organic solvent described in step 2 is selected from alkane, fragrance
One kind in hydrocarbon.Preferably toluene
One kind polymethyl silicane containing metal of the invention, in step 2, organic solvent takes the ratio between volume of monomer to be with matching somebody with somebody
6:1~8:1；
One kind polymethyl silicane containing metal of the invention, in step 2, match somebody with somebody the monomer taken and divide in 3-6 addition reactor,
Add by the way of being added dropwise and add every time, the speed of dropwise addition is 20-30mL/min；After being added dropwise to complete every time, stirring 120~
Dropwise addition next time is carried out after 180min again.
One kind polymethyl silicane containing metal of the invention, in step 2, during progress back flow reaction, condensing agent used is low viscosity
Silicone oil；The viscosity of the silicone oil is 10cps-15cps；The speed of the stirring is 100-130 revs/min.
One kind polymethyl silicane containing metal of the invention, in step 3, resulting polymethyl silicane molecular weight for 800~
900, viscosity is 0.02~0.03Pas.
In order to further lift the quality of product, promote reaction thoroughly to carry out, during the course of the reaction, be continually fed into protection
Gas, by the flowing of protective gas, product is both protected, promote to react the direction progress toward generation product again, until reaction
Completely.In step 4 of the present invention, in mass ratio；Polymethyl silicane：Crosslinking agent=100：3.4~12, with take polymethyl silicane, hand over
It is dissolved in after connection agent in organic solvent, is continually fed into protective gas, in 40~50 DEG C of stirring reaction 3-6 hours, preferably 4-5 hour
After be warming up to 120~150 DEG C, continue stirring reaction, the reacting gas that protective gas is taken out of leads in sodium hydrate aqueous solution, when
Sodium hydrate aqueous solution pH value used does not change, and stops reaction, gained liquid is product.
In step 4 of the present invention, the acetyl acetone salt is selected from aluminium acetylacetonate, acetylacetone copper, acetylacetone,2,4-pentanedione
At least one of zirconium, ferric acetyl acetonade, nickel acetylacetonate, two (acetylacetone,2,4-pentanedione) molybdenum oxides, titanium acetylacetone.
In step 4 of the present invention, the volume ratio of organic solvent and polymethyl silicane is 5：1-1：1.Preferably 2.5：1~
0.8：1st, it is more preferably 1.25：1~0.6：1.Organic solvent uses too many, then unfavorable to reduce cost, uses general very little
Reaction is caused not to be properly completed.
In step 4 of the present invention, the organic solvent in toluene, dimethylbenzene, benzene, tetrahydrofuran, dimethyl sulfoxide extremely
Few one kind.Preferably toluene.
In step 4 of the present invention, the protective atmosphere is preferably nitrogen atmosphere.
In step 4 of the present invention, during stirring, rotating speed is controlled to turn/min for 400-600, rotating speed is too low, then cannot suitably divide
The product of son amount.Rotating speed is too high, then crosslinked, branched degree is excessive, and product is very glutinous, is unfavorable for the dipping in later stage.
A kind of application of the polymethyl silicane containing metal of the present invention, comprises the steps：
Step A
Using the base substrate that porosity is 58.7~16% as prefabricated component, by volume, prefabricated component：Polymethyl silicane containing metal=
1：2~1：3；Place the preform in polymethyl silicane containing metal, carry out vacuum impregnation in room temperature~120 DEG C, obtain containing containing
The prefabricated component of metal polymethyl silicane；
Step B
Under protective atmosphere, it is crosslinked in 180~250 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1
Solidification；
Step C
After repeat step A dipping, step B crosslinking curing 3-4 times, in 1000~1300 DEG C of progress under protective atmosphere
High temperature pyrolysis processing；
Step D
After repeat step C3-4 times, it is compound more than or equal to 85HRC ceramic base more than or equal to 92%, hardness to obtain consistency
Material.
A kind of application of the polymethyl silicane containing metal of the present invention, the prefabricated component are preferably C/C composite material prefabricated components, again
Crystalline silicon carbide base substrate and hot pressed sintering silicon carbide green body.
A kind of application of the polymethyl silicane containing metal of the present invention, step A middle dipping are vacuum impregnation, during vacuum impregnation,
Vacuum is controlled in below 2000Pa.
A kind of application of the polymethyl silicane containing metal of the present invention, by 3-4 dipping, crosslinking curing rear Pintsch process processing one
It is secondary, after cycle operates 3-4 times, you can obtain the ceramic base composite wood that consistency is more than or equal to 85HRC more than or equal to 92%, hardness
Material.This is with the prior art, at least needing 3-5 4 dippings, crosslinking curing rear-Pintsch process processing to compare, not exclusively
Production efficiency is improved, and the performance of products obtained therefrom is also advantageous over its products obtained therefrom.
Principle and advantage
The metal modified polymethyl silicane of the present invention is liquid at normal temperatures, and viscosity is reduced to 0.03Pa under heating condition
S or so, can be directly as high density, the maceration extract of low porosity ceramic matric composite.With traditional metal-modified poly- methyl
Silane is compared, and crosslinking curing temperature is lower, reduces the requirement to equipment, the viscosity of maceration extract is adjusted by temperature, significantly
The pickling efficiency that ceramic matric composite prepares the later stage is improved, dipping-solidification number can be reduced, it is compound effectively to reduce ceramic base
The manufacturing cost of material.Meanwhile compared with ceramic matric composite prepared by traditional maceration extract, under equal densities, the present invention
Ceramic matric composite mechanical property prepared by metal modified polymethyl silicane is more excellent, particularly hardness and intensity.
Brief description of the drawings
Accompanying drawing 1 is the embodiment of the present invention 1,2,3,4 and comparative example density time and the graph of a relation of density degree.
In Fig. 1, No. 1 curve is relation curve of the density time with density degree of comparative example 1；No. 2 curves are embodiments 1
Density time and density degree relation curve；No. 3 curves are relation song of the density time with density degree of embodiment 3
Line；No. 4 curves are relation curve of the density time with density degree of embodiment 4；No. 5 curves are the density time of embodiment 6
With the relation curve of density degree；As can be seen from Figure 1：Compared with polymethyl silicane, the dipping of metal modified polymethyl silicane
More efficient, composite consistency prepared by metal-modified polymethyl silicane is higher.
Embodiment
Embodiment 1
Step 1
Aluminium powder is added in sodium sand, under nitrogen atmosphere, stirring, obtains standby sodium sand；, Al and Na in the standby sodium sand
Mass ratio is 1:12；The granularity of the aluminium powder is 50um, and the granularity of sodium sand is 10um；
Step 2
By Na and Si mol ratio, Na:Si=2.5:1 with taking standby sodium sand and monomer (1750g)；In a nitrogen atmosphere,
First sodium sand is fitted into reactor, then adding organic solvent toluene, (organic solvent takes the ratio between volume of monomer as 6 with matching somebody with somebody:
1)；Stirring, after being warming up to 76-78 DEG C, 3.4L dichloromethyls are slowly added dropwise into the 10L there-necked flasks equipped with 3L sodium sand toluene solutions
Silane, dividing 3 times will instill in reactor with the monomer taken, add by the way of being added dropwise add every time, the speed of dropwise addition is
20mL/min；After being added dropwise to complete every time, dropwise addition next time is carried out after stirring 120min again, after dripping, is warming up to 80-85
DEG C, continue back flow reaction reaction 6h, cool down, filter, revolving, remove toluene solvant, liquid after being reacted；The monomer is
Dichloro methyl silane；When carrying out back flow reaction, condensing agent used is silicone oil with low viscosity；The viscosity of the silicone oil is 10cps-
15cps；The speed of the stirring is 100-130 revs/min；
Step 3
In a nitrogen atmosphere, centrifugal treating is carried out to liquid after being reacted obtained by step 2, centrifugation gained liquid is in protective atmosphere
It is lower to be handled through distillation, obtain polymethyl silicane 1050g；The mean molecule quantity of gained polymethyl silicane is 800, and viscosity is
0.02Pa·S。
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：6.5, it is molten after polymethyl silicane 1000g, crosslinking agent 65g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, in 40~50 DEG C of stirring reactions 4 hours
After be warming up to 120 DEG C, continue stir (speed of agitator be 500 turns/min) reaction 6 hours, obtain polymethyl silicane containing metal；Institute
It is ferric acetyl acetonade to state crosslinking agent.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 60：100.
The molecular weight of its gained finished product is 1470, and room temperature viscosity is 0.07Pas, and 100 DEG C of viscosity is 0.03Pas.
The application of finished product comprises the steps prepared by the embodiment：Prefabricated component is to be compiled using 3KPAN base fibers two-step method
8 knitted:1:1 three-dimensional carbon fiber preform, the volume fraction of fiber is 41.3%, and its porosity is 58.7% after conversion；
Initially density is 0.727g/cm3。
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5：15；Place the preform in polymethyl silicane containing metal
In, carry out vacuum impregnation at 80 DEG C；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, control vacuum exists
Below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 200 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 4 times, high temperature hot tearings are carried out in 1000 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C3 times, the ceramic base composite wood that consistency is more than or equal to 85HRC more than or equal to 92%, hardness is obtained
Material.
Gained end properties is：
Density is 1.98g/cm3
Porosity 8.5%
Bending strength 557MPa
Fracture toughness 27MPam1/2。
Comparative example 1
Other operations are completely consistent with embodiment 1, only without the operation for carrying out step 4, that is, obtain polymethyl silicane
Afterwards, i.e., operated according to step A, B, C, D；The performance of its resulting materials is：
Density is 1.73g/cm3
Porosity 21%
Bending strength 290MPa
Fracture toughness 14.5MPam1/2
Comparative example 2
The metal that patent CN101186704 (page 4~7) is modified in a manner of using metal chloride to polymethyl silicane
Modified polymethyl silicane is as precursor, after carrying out 4 dipping-solidification-cracking circular treatments, resulting Cf/ SiC composite woods
Material, its performance are as follows：
Density is 169~1.88g/cm3
Porosity 12.96~15.64%
311.15~386.32MPa of bending strength
15.74~18.95MPam of fracture toughness1/2
By embodiment 1, comparative example 1, comparative example 2 as can be seen that being used as using this patent metal modified polymethyl silicane
C prepared by precursorf/ SiC ceramic matrix composite material has the characteristics of consistency is high, voidage is small, excellent in mechanical performance.
Embodiment 2
Step 1
Aluminium powder is added in sodium sand, under nitrogen atmosphere, stirring, obtains standby sodium sand；, Al and Na in the standby sodium sand
Mass ratio is 1:15；The granularity of the aluminium powder is 30um, and the granularity of sodium sand is 5um；
Step 2
By Na and Si mol ratio, Na:Si=2:1 with taking standby sodium sand and monomer (1700g)；In a nitrogen atmosphere, first
Sodium sand is fitted into reactor, then adding organic solvent toluene, (organic solvent takes the ratio between volume of monomer as 8 with matching somebody with somebody:1；
Stirring, after being warming up to 80 DEG C, dividing 4 times will instill in reactor with the monomer taken, add by the way of being added dropwise add every time, drop
The speed added is 25mL/min；After being added dropwise to complete every time, dropwise addition next time is carried out after stirring 150min again, flow back instead
Should；Liquid after being reacted；The monomer is dichloro methyl silane；When carrying out back flow reaction, condensing agent used is silicone oil with low viscosity；
The viscosity of the silicone oil is 10cps-15cps；The speed of the stirring is 100-130 revs/min；
Step 3
In a nitrogen atmosphere, centrifugal treating is carried out to liquid after being reacted obtained by step 2, centrifugation gained liquid is in protective atmosphere
It is lower to be handled through distillation, obtain polymethyl silicane 1045g；The mean molecule quantity of gained polymethyl silicane is 880, and viscosity is
0.028Pa·S。
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：12, it is molten after polymethyl silicane 1000g, crosslinking agent 120g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, is risen in 50 DEG C of stirring reactions after 4 hours
Temperature continues to stir (speed of agitator is 600 turns/min) reaction 6 hours, obtains polymethyl silicane containing metal to 120 DEG C；The friendship
Connection agent is aluminium acetylacetonate.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 85：100.
The molecular weight of its gained finished product is 1800, and room temperature viscosity is 0.1Pas, and 120 degrees Celsius of viscosity is 0.03Pa
s。
The application of finished product comprises the steps prepared by the embodiment：
Using its porosity as 26%；Originally density is 2.0g/cm3Hot pressed sintering silicon carbide green body be prefabricated component.
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5:10；Place the preform in polymethyl silicane containing metal
In, carry out vacuum impregnation at 120 degrees Celsius；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, vacuum is controlled
In below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 180 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 3 times, high temperature hot tearings are carried out in 1000 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C4 times, the ceramic base composite wood that consistency is more than or equal to 88HRC more than or equal to 94%, hardness is obtained
Material.
Gained end properties is：
Density is 2.57g/cm3
Porosity 6.0%
Bending strength 330MPa
Fracture toughness 5MPam1/2。
Embodiment 3
Step 1
Aluminium powder is added in sodium sand, under nitrogen atmosphere, stirring, obtains standby sodium sand；, Al and Na in the standby sodium sand
Mass ratio is 1:13；The granularity of the aluminium powder is that the granularity of 40um sodium sands is 8um；
Step 2
By Na and Si mol ratio, Na:Si=2:1 with taking standby sodium sand and monomer (1700g)；In a nitrogen atmosphere, first
Sodium sand is fitted into reactor, then adding organic solvent toluene, (organic solvent takes the ratio between volume of monomer as 7 with matching somebody with somebody:1)；
Stirring, after being warming up to 78 DEG C, dividing 5 times will instill in reactor with the monomer taken, add by the way of being added dropwise add every time, drop
The speed added is 30mL/min；After being added dropwise to complete every time, dropwise addition next time is carried out after stirring 180min again, flow back instead
Should；Liquid after being reacted；The monomer is dichloro methyl silane；When carrying out back flow reaction, condensing agent used is silicone oil with low viscosity；
The viscosity of the silicone oil is 10cps-15cps；The speed of the stirring is 100-130 revs/min；
Step 3
In a nitrogen atmosphere, centrifugal treating is carried out to liquid after being reacted obtained by step 2, centrifugation gained liquid is in protective atmosphere
It is lower to be handled through distillation, obtain polymethyl silicane；The mean molecule quantity of gained polymethyl silicane is 850, viscosity 0.024PaS.
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：4.2, it is molten after polymethyl silicane 1000g, crosslinking agent 42g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, in 40~50 DEG C of stirring reactions 3 hours
After be warming up to 135 DEG C, continue stir (speed of agitator be 600 turns/min) reaction 5 hours, obtain polymethyl silicane containing metal；Institute
It is acetylacetone copper to state crosslinking agent.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 75：100.
The molecular weight of its gained finished product is 1300, and room temperature viscosity is 0.04Pas, and 60 degrees Celsius of viscosity is 0.03Pa
s。
The application of finished product comprises the steps prepared by the embodiment：
Using its porosity as 55.5%；Originally density is 0.8g/cm3C/C base substrates be prefabricated component
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5:15；Place the preform in polymethyl silicane containing metal
In, carry out vacuum impregnation at 60 degrees Celsius；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, vacuum is controlled
In below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 250 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 4 times, high temperature hot tearings are carried out in 1100 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C3 times, consistency is obtained more than or equal to the 86HRC ceramic base composite woods that 94%, hardness is more than or equal to
Material.
Gained end properties is：
Density is 1.98g/cm3
Porosity 5.8%
Bending strength 408MPa
Fracture toughness 15MPam1/2。
Embodiment 4
The operation of step 1 to step 3 is completely consistent with embodiment 1；
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：5.5, it is molten after polymethyl silicane 1000g, crosslinking agent 55g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, in 40~50 DEG C of stirring reactions 5 hours
After be warming up to 120 DEG C, continue stir (speed of agitator be 600 turns/min) reaction 6 hours, obtain polymethyl silicane containing metal；Institute
It is acetylacetone,2,4-pentanedione zirconium to state crosslinking agent.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 100：100.
The molecular weight of its gained finished product is 1300, and room temperature viscosity is 0.04Pas, and 60 degrees Celsius of viscosity is 0.03Pa
s。
The application of finished product comprises the steps prepared by the embodiment：
Using its porosity as 54%；Originally density is 0.85g/cm3C/C base substrates be prefabricated component
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5:15；Place the preform in polymethyl silicane containing metal
In, carry out vacuum impregnation at 60 degrees Celsius；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, vacuum is controlled
In below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 250 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 4 times, high temperature hot tearings are carried out in 1300 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C3 times, the ceramic base composite wood that consistency is more than or equal to 85HRC more than or equal to 93%, hardness is obtained
Material.
Gained end properties is：
Density is 1.95g/cm3
Porosity 6.2%
Bending strength 397MPa
Fracture toughness 14.7MPam1/2。
Embodiment 5
Step 1
The operation of step 1 to step 3 is completely consistent with embodiment 1；
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：4.4, it is molten after polymethyl silicane 1000g, crosslinking agent 44g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, in 40~50 DEG C of stirring reactions 5 hours
After be warming up to 120 DEG C, continue stir (speed of agitator be 600 turns/min) reaction 6 hours, obtain polymethyl silicane containing metal；Institute
It is nickel acetylacetonate to state crosslinking agent.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 100:100.
The molecular weight of its gained finished product is 1350, and room temperature viscosity is 0.04Pa.s, and 60 degrees Celsius of viscosity is 0.03Pa.s.
The application of finished product comprises the steps prepared by the embodiment：
Using its porosity as 50%；Originally density is 0.88g/cm3C/C base substrates be prefabricated component
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5:15；Place the preform in polymethyl silicane containing metal
In, carry out vacuum impregnation at 60 degrees Celsius；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, vacuum is controlled
In below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 250 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 4 times, high temperature hot tearings are carried out in 1300 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C3 times, the ceramic base composite wood that consistency is more than or equal to 86HRC more than or equal to 94%, hardness is obtained
Material.
Gained end properties is：
Density is 2.02g/cm3
Porosity 5.3%
Bending strength 472MPa
Fracture toughness 18MPam1/2。
Embodiment 6
The operation of step 1 to step 3 is completely consistent with embodiment 1；
Step 4
In mass ratio；Polymethyl silicane：Crosslinking agent=100：3.4, it is molten after polymethyl silicane 1000g, crosslinking agent 34g with taking
In toluene, protective gas nitrogen (flow velocity of nitrogen is 100ml/min) is continually fed into, in 40~50 DEG C of stirring reactions 5 hours
After be warming up to 150 DEG C, continue stir (speed of agitator be 600 turns/min) reaction 6 hours, obtain polymethyl silicane containing metal；Institute
It is two (acetylacetone,2,4-pentanedione) molybdenum oxides to state crosslinking agent.In the present embodiment, the volume ratio of toluene and polymethyl silicane is 125：100.
The molecular weight of its gained finished product is 1500, and room temperature viscosity is 0.07Pas.
The application of finished product comprises the steps prepared by the embodiment：
Using its porosity as 16%；Originally density is 2.6g/cm3Recrystallized silicon carbide base substrate be prefabricated component
Step A
By volume, prefabricated component：Polymethyl silicane containing metal=5:10；Place the preform in polymethyl silicane containing metal
In, vacuum impregnation is carried out at normal temperatures；Obtain the prefabricated component of the polymethyl silicane containing metal；During vacuum impregnation, control vacuum exists
Below 2000Pa；
Step B
Under protective atmosphere, crosslinking curing is carried out in 200 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；
Step C
After repeat step A dipping, step B crosslinking curing 3 times, high temperature hot tearings are carried out in 1300 DEG C under protective atmosphere
Solution processing；
Step D
After repeat step C4 times, the ceramic base composite wood that consistency is more than or equal to 90HRC more than or equal to 97%, hardness is obtained
Material.
Gained end properties is：Density is 2.97g/cm3
The bending strength 167MPa of porosity 3%
It is broken tenacity 3.5MPam1/2。
Claims (9)
- A kind of 1. polymethyl silicane containing metal；It is characterized in that：Contain O-M keys, M-Si keys in its structure；The M be selected from Al, At least one of Cu, Zr, Fe, Ni, Mo, Ti.
- 2. one kind polymethyl silicane containing metal according to claim 1；It is characterized in that：The polymethyl silicane containing metal Molecular weight be：1300-1700.
- 3. one kind polymethyl silicane containing metal according to claim 1；It is characterized in that：Its room temperature viscosity be 0.04 ~ 0.1Pa·s；It is less than or equal to 0.03 Pas in 60 ~ 120 DEG C of viscositys.
- 4. according to one kind polymethyl silicane containing metal described in claim 1-3 any one；Its preparation method is：Step 1Aluminium powder is added in sodium sand, under protective atmosphere, stirring, obtains standby sodium sand；Step 2By Na and Si mol ratio, Na：Si=2.5~1：2 ~ 1 with taking standby sodium sand and monomer；Under protective atmosphere, first by sodium sand It is fitted into reactor, then adds organic solvent；Stirring, after being warming up to 70-85 DEG C, dividing at least 2 times will instill with the monomer taken In reactor, stirring, back flow reaction is carried out；Liquid after being reacted；The monomer is dichloro methyl silane；Step 3Under protective atmosphere, centrifugal treating is carried out to liquid after being reacted obtained by step 2, centrifugation gained liquid passes through under protective atmosphere Distillation is handled, and obtains polymethyl silicane；Step 4In mass ratio；Polymethyl silicane：Crosslinking agent=100：3.4 ~ 12, with being dissolved in organic solvent after taking polymethyl silicane, crosslinking agent In, under protective atmosphere, 120 ~ 150 DEG C are warming up to after 40 ~ 50 DEG C of stirring reactions, continues stirring reaction, obtains gathering containing metal Methyl-monosilane；The crosslinking agent is acetyl acetone salt.
- 5. one kind polymethyl silicane containing metal according to claim 4；It is characterized in that：Standby sodium sand described in step 1 Middle Al and Na mass ratio are 1:12~1:15；The granularity of aluminium powder described in step 1 is 30-50um, and the granularity of sodium sand is 0.5-10um, and the sodium sand is by following sides Prepared by case：Sodium block is immersed in the reactor equipped with toluene, in protective atmosphere, sodium block is heated to 97-98 DEG C, stirred, until Sodium block is cooled to room temperature after crushing completely；Obtain the sodium sand that granularity is 0.5 ~ 10um；In step 1, aluminium powder is added in sodium sand, under protective atmosphere, is stirred under normal temperature, obtains standby sodium sand；The speed of stirring For 100 ~ 130 revs/min；The one kind of organic solvent in alkane, aromatic hydrocarbon described in step 2；In step 2, organic solvent takes the ratio between volume of monomer as 6 with matching somebody with somebody:1~8:1；In step 2, match somebody with somebody the monomer taken and divide in 3-6 addition reactor, add by the way of being added dropwise add every time, be added dropwise Speed be 20-30mL/min；After being added dropwise to complete every time, dropwise addition next time is carried out after 120 ~ 180min of stirring again；In step 2, when carrying out back flow reaction, condensing agent used is silicone oil with low viscosity；The viscosity of the silicone oil is 10cps- 15cps；The speed of the stirring is 100-130 revs/min；In step 3, resulting polymethyl silicane molecular weight is 800 ~ 900, and viscosity is 0.02 ~ 0.03 Pas；In step 4, the volume ratio of organic solvent and polymethyl silicane is 5：1-1：1；The organic solvent is selected from toluene, diformazan At least one of benzene, benzene, tetrahydrofuran, dimethyl sulfoxide；In step 4, the acetyl acetone salt is selected from aluminium acetylacetonate, acetylacetone copper, acetylacetone,2,4-pentanedione zirconium, acetylacetone,2,4-pentanedione Iron, nickel acetylacetonate, two（Acetylacetone,2,4-pentanedione）At least one of molybdenum oxide, titanium acetylacetone；In step 4, during stirring, rotating speed is controlled to turn/min for 400-600.
- 6. a kind of application of the polymethyl silicane containing metal as described in claim 1-3 any one, comprises the steps：Step AIt is 58.7 ~ 16% base substrate for prefabricated component using porosity, by volume, prefabricated component：Polymethyl silicane containing metal=1：2~1： 3；Place the preform in polymethyl silicane containing metal, carry out vacuum impregnation in room temperature ~ 120 DEG C, obtain the poly- methyl silicon containing metal The prefabricated component of alkane；Step BUnder protective atmosphere, crosslinking curing is carried out in 180 ~ 250 DEG C of prefabricated components to the polymethyl silicane containing metal obtained by step 1；Step CAfter repeat step A dipping, step B crosslinking curing 3-4 times, high temperature are carried out in 1000 ~ 1300 DEG C under protective atmosphere Thermal cracking processing；Step DAfter repeat step C3-4 times, the ceramic matric composite that consistency is more than or equal to 85HRC more than or equal to 92%, hardness is obtained.
- A kind of 7. application of polymethyl silicane containing metal according to claim 6, it is characterised in that：The prefabricated component is selected from At least one of C/C composite material prefabricated components, recrystallized silicon carbide base substrate and hot pressed sintering silicon carbide green body.
- A kind of 8. application of polymethyl silicane containing metal according to claim 6, it is characterised in that：Dipping is in step A Vacuum impregnation, during vacuum impregnation, control vacuum is in below 2000Pa.
- A kind of 9. application of polymethyl silicane containing metal according to claim 6, it is characterised in that：It is solid by dipping, crosslinking Pintsch process processing once, after cycle operates 3-4 times, obtains consistency and is more than or equal to more than or equal to 92%, hardness after changing 3-4 times 85HRC ceramic matric composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510753062.4A CN105237771B (en) | 2015-11-06 | 2015-11-06 | A kind of polymethyl silicane containing metal and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510753062.4A CN105237771B (en) | 2015-11-06 | 2015-11-06 | A kind of polymethyl silicane containing metal and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105237771A CN105237771A (en) | 2016-01-13 |
| CN105237771B true CN105237771B (en) | 2018-01-02 |
Family
ID=55035629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510753062.4A Active CN105237771B (en) | 2015-11-06 | 2015-11-06 | A kind of polymethyl silicane containing metal and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105237771B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114836044B (en) * | 2022-05-10 | 2023-03-14 | 中南大学 | Modification method of polymethylsilane and application thereof |
| CN116375501B (en) * | 2023-06-05 | 2023-07-28 | 烟台奥森制动材料有限公司 | Surface treatment process of carbon-ceramic composite material brake disc |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186704A (en) * | 2007-12-24 | 2008-05-28 | 中国人民解放军国防科学技术大学 | Metal modified polymethyl silicane, preparation method and application thereof |
| CN104194717A (en) * | 2014-09-24 | 2014-12-10 | 中国人民解放军国防科学技术大学 | Preparation method for high-temperature-resistant ceramic precursor adhesive |
| CN104327275A (en) * | 2014-11-24 | 2015-02-04 | 中国人民解放军国防科学技术大学 | Synthetic method of aluminum-containing polycarbosilane |
-
2015
- 2015-11-06 CN CN201510753062.4A patent/CN105237771B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186704A (en) * | 2007-12-24 | 2008-05-28 | 中国人民解放军国防科学技术大学 | Metal modified polymethyl silicane, preparation method and application thereof |
| CN104194717A (en) * | 2014-09-24 | 2014-12-10 | 中国人民解放军国防科学技术大学 | Preparation method for high-temperature-resistant ceramic precursor adhesive |
| CN104327275A (en) * | 2014-11-24 | 2015-02-04 | 中国人民解放军国防科学技术大学 | Synthetic method of aluminum-containing polycarbosilane |
Non-Patent Citations (1)
| Title |
|---|
| Macroporous SiC–MoSi2 ceramics from templated hybrid MoCl5–polymethylsilane;Hao Wang等;《APPLIED ORGANOMETALLIC CHEMISTRY》;20050322;第19卷;742-749 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105237771A (en) | 2016-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496508B (en) | Manufacture method based on the SiC ceramic base turbine blade that photocuring 3D prints | |
| JP4110244B2 (en) | Silicon carbide-based heat resistant porous structure and method for producing the same | |
| CN1876272A (en) | Preparation method of boron nitride ceramic shell for titanium and titanium alloy precision casting | |
| CN105237771B (en) | A kind of polymethyl silicane containing metal and its application | |
| CN104131363B (en) | A kind of porous mullite fibre | |
| CN113845367B (en) | Preparation method of high-temperature oxidation-resistant carbon fiber toughened zirconia ceramic material and high-temperature oxidation-resistant carbon fiber toughened zirconia ceramic material | |
| CN104926346B (en) | A kind of alumina fibre fabric containing interface phase strengthens silicon carbide ceramics and preparation method thereof | |
| CN101186704B (en) | Metal modified polymethyl silicane, preparation method and application thereof | |
| CN102838106A (en) | Method for preparing carbon film by using silicon carbide-enhanced polyimide composite film | |
| CN103435766B (en) | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof | |
| CN105421033B (en) | A kind of fiber, ceramics, the preparation method of metal three-dimensional network composite | |
| CN1317425C (en) | Production process of composite steel pipe with cermet lining | |
| CN108752037A (en) | A kind of porous silicon carbide silicon bulk and the preparation method and application thereof prepared based on Polycarbosilane | |
| CN106966744A (en) | A kind of fibre reinforced alumina ceramic composite material and preparation method thereof | |
| CN105503229A (en) | Preparation method of Al2O3f/SiOC radar wave-absorbing composite material | |
| EP2258811A1 (en) | Method for producing porous ceramics and multiphasic materials from cellulosic precursors | |
| CN105132897B (en) | A kind of preparation method of silicon carbide fibre alumina coating on surface | |
| CN109704775A (en) | A kind of continuous carbofrax fibre and preparation method thereof of beryllium gradient distribution | |
| CN105195738A (en) | Wrapped Al2O3/Al compound powder and preparing method thereof | |
| CN112300397B (en) | Polycarbosilane and preparation method thereof | |
| CN101870592B (en) | Preparation method of titanium-nitride silicon carbide fibers | |
| CN107523877A (en) | The method that graphite matrix surface prepares silicon carbide whisker coating | |
| CN109371505A (en) | A kind of biomass-based screw carbon fibre and preparation method thereof | |
| CN1057515C (en) | Method for deoxidisation and reinforcement of solid organic procursor of silicon nitride material | |
| CN107937839A (en) | A kind of high hardness wear-resisting steel alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191217 Address after: Room 901, building 10, lanjiangyuan, Xiangjiang Century City, No.199, Jintai Road, Kaifu District, Changsha City, Hunan Province Patentee after: Zhang Sihai Address before: 410200 No. 1 Tongxin Road, Wangcheng economic and Technological Development Zone, Changsha, Hunan Patentee before: HUNAN BOWANG CARBON CERAMIC CO., LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200107 Address after: Room 616, science and technology entrepreneurship service center, Hunan Green Chemical Industry Park, Yunxi District, Yueyang City, Hunan Province Patentee after: Hunan pioneer new material Co., Ltd Address before: Room 901, building 10, lanjiangyuan, Xiangjiang Century City, No.199, Jintai Road, Kaifu District, Changsha City, Hunan Province Patentee before: Zhang Sihai |
|
| TR01 | Transfer of patent right |