CN108191433A - A kind of modified silicon nitride and powder preparation method and purposes containing modified silicon nitride - Google Patents
A kind of modified silicon nitride and powder preparation method and purposes containing modified silicon nitride Download PDFInfo
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- CN108191433A CN108191433A CN201711395824.3A CN201711395824A CN108191433A CN 108191433 A CN108191433 A CN 108191433A CN 201711395824 A CN201711395824 A CN 201711395824A CN 108191433 A CN108191433 A CN 108191433A
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Abstract
Powder preparation method and purposes the invention discloses a kind of modified silicon nitride and containing modified silicon nitride.Carry out surface graft modification is reacted successively with halogenated silanes and hydroxyl organic molecule using beta-silicon nitride powder surface hydroxyl, so as to obtain the beta-silicon nitride powder of organic molecule surface graft modification.The purpose is to improve the dispersibility of beta-silicon nitride powder water-based slurry and rheological characteristic, for Direct Coagulation Casting technique.Compared to beta-silicon nitride powder water-based slurry before modified（Solid concentration 30 37vol%, 1 Pa.s）, the modification beta-silicon nitride powder water-based slurry solid content that the present invention obtains is up to 57 62vol%（1 Pa.s）.
Description
Technical field
The present invention relates to a kind of with method of organic molecule surface graft modification beta-silicon nitride powder and application thereof, specifically
It is a kind of method of halogenated silanes and hydroxyl organic molecule graft modification beta-silicon nitride powder and application thereof.
Background technology
The preparation of high-performance fine ceramics needs the powder of high quality and the moulding process of maturation to ensure.Ceramic colloidal
Forming technique can the variously-shaped complexity of near-net-shape ceramic component, be a kind of important shaping method of ceramics, the technology
Key be prepare low viscosity, high solid loading ceramic concentrate suspension, as gel casting forming (GC) requires ceramic slurry
Minimum solid concentration is 50% (volume fraction, similarly hereinafter), and Direct Coagulation Casting (DCC) generally requires the solid concentration of slurry
More than 55%, and the viscosity of slurry is required to be less than 1Pa.s.
Silicon nitride ceramics becomes height due to its intensity height, thermal shock resistance and good in oxidation resistance are when excellent physical and mechanical property
One of warm structural ceramics preferred material.But the silicon nitride ceramics manufactured with common process, because grade low with reliability of high cost is former
Because limiting its scope of application.The in-situ colloidal forming process proposed in recent years such as DCC and Gel casting are to solve
A kind of effective way of these problems.
Silicon nitride is a kind of non-oxide powder, due to the irregular configuration of surface of its powder, complicated surface chemistry base
The different size mixed in group's (such as amino, hydroxyl and silylation etc.) and preparation process and the oxidation and sinter agent of content,
So that it is difficult to disperse in a solvent, and the dispersing characteristic of different size business beta-silicon nitride powder in water is often because different
Preparation process and be not quite similar, be accordingly difficult to directly prepare high solid loading low viscosity concentrate suspension.Therefore, to silicon nitride
Etc. for non-oxide ceramic powders, it is to prepare height to improve its dispersibility and rheological characteristic in water using the method that surface is modified
Solid volume fraction, low viscosity water-base silicon nitride dense suspension only way and be widely noticed in recent years research neck
Domain.Therefore research beta-silicon nitride powder process for modifying surface has extremely important science and application value, has also obtained at present more next
More concerns.
The shortcomings that being difficult to disperse in water for beta-silicon nitride powder, although current research has made great progress,
It is difficult to prepare Silicon Nitride of the solid concentration higher than 55% suitable for directly solidification molding process, effect is also difficult to make not
Same type beta-silicon nitride powder reaches application request.
Invention content
To solve problems of the prior art, the present invention is directed to prepare one by the method for organic molecule surface grafting
The powder of the modified silicon nitride of kind, so as to improve its rheological characteristic and dispersibility in water, obtains the nitrogen of high solid loading low viscosity
SiClx powder water-based slurry, to prepare high-performance silicon nitride ceramics by Direct Coagulation Casting technique.
One of goal of the invention to realize the present invention, the technical solution of use is as follows, provides a kind of new silicon nitride chemical combination
Object.
A kind of modification silicon nitride compound as led to shown in formula (I)：
Wherein, R is selected from-H ,-Cl ,-Br ,-I ,-CH3、-CH2CH3、-C6H5；
R' is selected from-(CH2)nCH3、-CH(CH3)(CH2)nCH3、-CH2C6H5、-(CH2)nOH、 N is 0 or arbitrary positive integer in above formula.
The two of goal of the invention to realize the present invention, adopt the following technical scheme that, provide containing above-mentioned modified silicon nitride
Powder preparation method.
Beta-silicon nitride powder of the present invention is domestic commercially available business powder, and α-phase content is more than 90%, the moment of volume of particle
For average diameter at 0.7-8 μm, grain shape is irregular.
Technical principle is as follows：The organic molecule surface graft modification is by beta-silicon nitride powder surface silanol group and halogen
It is different organic so as to be grafted in the form of covalent bond in silicon nitride surface for being grafted again from hydroxyl small molecule after silane reaction
Molecule.
Powder preparation method containing above-mentioned modified silicon nitride, includes the following steps：
(1) salt acid elution：The purpose of this step is to wash away the impurity metal ion being complexed with silicon nitride surface silicone hydroxyl, is carried
High surface silanol group concentration, so as to improve the efficiency of graft modification.
Beta-silicon nitride powder is made into the suspended substance of 20-35vol% with 2M hydrochloric acid, is transferred in ball grinder, is 1 in material ball ratio:1
~2.5, rotating speed is ball milling under conditions of 200-500 revs/min or mechanical agitation 2-8 hour, is centrifuged after ball milling, removal supernatant
Liquid.
(2) deionized water is washed：The purpose of this step is the solable matter that generates and extra after demineralizing acid washing
Hydrochloric acid.
Step (1) is washed with deionized treated beta-silicon nitride powder, then carry out CENTRIFUGAL ACCELERATING powder precipitation, and go
Except supernatant, repeat above-mentioned washing step until supernatant conductivity value close to deionized water conductivity value.
(3) graft modification：The purpose of this step is by halogenated silanes and hydroxyl organic molecule substep graft modification
Method is covalently attached organic molecule on beta-silicon nitride powder surface, improves the dispersibility and rheological characteristic of powder.
Anhydrous methylene chloride, which is suspended in, after beta-silicon nitride powder drying after step (2) is washed is made into 20-40vol% suspensions
Then body adds in the halogenated silanes of 0.01-0.2wt% (this content is the percentage of silicon nitride powder weight), is in material ball ratio
1:1~2.5, rotating speed is carries out ball milling or mechanical agitation 8-24 hours under conditions of 200-500 revs/min；
Then, excessive hydroxyl organic molecule is added in, is 1 in material ball ratio:1~2.5, rotating speed is 200-500 revs/min
Under the conditions of ball milling or mechanical agitation 8-24 hours, the anhydrous methylene chloride solvent is then removed under reduced pressure, is washed with water after washing and dries
It can be obtained containing modified silicon nitride compound powder after dry.
It is preferred that the halogenated silanes be selected from dichlorosilane, trichlorosilane, dichloromethylsilane, ethyl dichloro hydrogen silane,
Any one of methyl dibromo hydrogen silane, methyl diiodo- hydrogen silane, ethyl dibromo hydrogen silane, phenyl dichloro hydrogen silane.
It is preferred that the hydroxyl organic molecule is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, Zhong Ding
Alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, benzylalcohol, ethylene glycol, 1,3- propylene glycol, 1,4- butanediols, poly- second
Any one of glycol and poly glycol monomethyl ether.
The three of goal of the invention to realize the present invention are provided and are prepared using the above-mentioned powder containing modified silicon nitride compound
The method of modified water-base silicon nitride slurry.
The preparation method of modified water-base silicon nitride slurry is as follows：
Modified beta-silicon nitride powder is added in deionized water, wherein the volume ratio of the modified beta-silicon nitride powder and water is 1:
(0.5~1.5) is 1 in material ball ratio loaded in mixing tank:1~2.5, rotating speed carries out ball milling under conditions of being 200-500 revs/min
Or mechanical agitation until slurry viscosity is relatively reduced and reaches stable, that is, prepares solid concentration as 57- after 8-24 hours
62vol%, viscosity are not higher than the water-base silicon nitride slurry of 1Pa.s, which is used to prepare high-performance silicon nitride
Ceramics.
The four of goal of the invention to realize the present invention provide the above-mentioned purposes containing modified silicon nitride compound powder.
The above-mentioned purposes containing modified silicon nitride compound powder, is used to prepare high-performance silicon nitride ceramics purposes；It is excellent
Choosing is used to prepare the purposes of the beta-silicon nitride powder water-based slurry of high solid loading low viscosity.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 halogenated silanes and hydroxyl organic molecule graft modification beta-silicon nitride powder schematic diagram.
Specific embodiment
In order to be best understood from and implement, with reference to embodiment, the present invention will be described in detail, but protection scope of the present invention
It is not limited to these embodiments, every protection model that the present invention is included in without departing substantially from the change of present inventive concept or equivalent substitute
Within enclosing.
In addition, it is necessary to which explanation is in embodiment 1-9, the excessive hydroxyl organic molecule of the addition each means addition matter
Amount is more than the hydroxyl organic molecule of silicon nitride powder weight 1% described in this；Modified water-base silicon nitride slurry in embodiment 1-9
The preparation method of material is consistent with the preparation method of Summary, i.e., modified beta-silicon nitride powder is added in deionized water first
In, wherein the volume ratio of the modified beta-silicon nitride powder and water is 1:(0.5~1.5) is 1 in material ball ratio loaded in mixing tank:
1~2.5, rotating speed carried out ball milling or mechanical agitation after 8-24 hours under conditions of being 200-500 revs/min, until slurry viscosity phase
Stablize acquisition to reducing and reaching.
Embodiment 1：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 0.7 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 36vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 30vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 8 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 30vol% suspended substances, then adds in the methyl two of 0.1wt% (this content is the percentage of silicon nitride powder weight)
Chlorine hydrogen silane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling in the range of being 200-500 revs/min or mechanical agitation 24 is small
When, it adds in after excessive n-hexyl alcohol with same method ball milling or mechanical agitation 24 hours, solvent is then removed, after being washed with water
Drying.The water-based slurry that the beta-silicon nitride powder prepared in aforementioned manners is prepared is after 18 hours ball millings or mechanical agitation dispersion in table
When seeing viscosity as 1Pa.s, solid concentration 62vol%.
Embodiment 2：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 0.7 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 36vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 30vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 8 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 30vol% suspended substances, then adds in the trichlorine of 0.05wt% (this content is the percentage of silicon nitride powder weight)
Silane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 12 hours in the range of being 200-500 revs/min, removes
It is dried in vacuo after removing solvent, is resuspended in anhydrous methylene chloride and is made into 30vol% suspended substances, added in after excessive n-amyl alcohol with together
The method ball milling of sample or mechanical agitation 8 hours, then remove solvent, are dried after being washed with water.The nitridation prepared in aforementioned manners
After 24 hours ball millings or mechanical agitation dispersion when apparent viscosity is 1Pa.s, solid phase contains the water-based slurry that silicon powder is prepared
It measures as 60vol%.
Embodiment 3：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 0.7 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 36vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 30vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 8 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 25vol% suspended substances, then adds in the dichloro silicon of 0.2wt% (this content is the percentage of silicon nitride powder weight)
Alkane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 hours in the range of being 200-500 revs/min, removes
It is dried in vacuo after solvent, is resuspended in anhydrous methylene chloride and is made into 30vol% suspended substances, added in after excessive n-hexyl alcohol with equally
Method ball milling or mechanical agitation 24 hours, then remove solvent, dried after being washed with water.The silicon nitride prepared in aforementioned manners
Powder prepare water-based slurry through 18 hours ball millings or mechanical agitation dispersion after apparent viscosity be 1Pa.s when, solid concentration
For 59vol%.
Embodiment 4：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 2.3 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 33vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 25vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 2 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 25vol% suspended substances, then adds in the methyl two of 0.1wt% (this content is the percentage of silicon nitride powder weight)
Chlorine hydrogen silane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling in the range of being 200-500 revs/min or mechanical agitation 24 is small
When, it is dried in vacuo after removing solvent, is resuspended in anhydrous methylene chloride and is made into 25vol% suspended substances, add in excessive n-hexyl alcohol
Afterwards with same method ball milling or mechanical agitation 24 hours, solvent is then removed, is dried after being washed with water.It prepares in aforementioned manners
Beta-silicon nitride powder prepare water-based slurry through 24 hours ball millings or mechanical agitation dispersion after apparent viscosity be 1Pa.s when,
Solid concentration is 59vol%.
Embodiment 5：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 2.3 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 33vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 25vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 2 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 25vol% suspended substances, then adds in the trichlorine of 0.01wt% (this content is the percentage of silicon nitride powder weight)
Silane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 hours in the range of being 200-500 revs/min, removes
It is dried in vacuo after removing solvent, is resuspended in anhydrous methylene chloride and is made into 25vol% suspended substances, added in after excessive n-amyl alcohol with together
The method ball milling of sample or mechanical agitation 24 hours, then remove solvent, are dried after being washed with water.The nitridation prepared in aforementioned manners
After 24 hours ball millings or mechanical agitation dispersion when apparent viscosity is 1Pa.s, solid phase contains the water-based slurry that silicon powder is prepared
It measures as 61vol%.
Embodiment 6：
Commercially available business silicon nitride powder, α-phase content are more than 90%, and the volume moment mean diameter of particle is at 2.3 μm, purity
More than 99%, grain shape is irregular, and water-based slurry original solids content is 33vol% (1Pa.s).Powder-modified treatment process
It is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 25vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:1~
2.5, ball milling or mechanical agitation 2 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant.
(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned step
Suddenly, until supernatant conductivity value close to deionized water conductivity value.(3) it is suspended in anhydrous dichloro after beta-silicon nitride powder drying
Methane is made into 25vol% suspended substances, then adds in the dichloro silicon of 0.1wt% (this content is the percentage of silicon nitride powder weight)
Alkane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 hours in the range of being 200-500 revs/min, removes
It is dried in vacuo after solvent, is resuspended in anhydrous methylene chloride and is made into 25vol% suspended substances, added in after excessive n-hexyl alcohol with equally
Method ball milling or mechanical agitation 24 hours, then remove solvent, dried after being washed with water.The silicon nitride prepared in aforementioned manners
Powder prepare water-based slurry through 24 hours ball millings or mechanical agitation dispersion after apparent viscosity be 1Pa.s when, solid concentration
For 57vol%.
Embodiment 7：
Commercially available business nano-grade silicon nitride powder, α-phase content are more than 90%, the volume moment mean diameter of particle in 40nm,
Purity is more than 99%, and grain shape is irregular, and water-based slurry original solids content is 30vol% (1Pa.s).Powder-modified processing
Technique is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 20vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:
1~2.5, ball milling or mechanical agitation 6 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant
Liquid.(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned
Step, until conductivity value of the supernatant conductivity value close to deionized water.(3) anhydrous two are suspended in after beta-silicon nitride powder drying
Chloromethanes is made into 25vol% suspended substances, then adds in the methyl of 0.1wt% (this content is the percentage of silicon nitride powder weight)
Dichloro hydrogen silane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 in the range of being 200-500 revs/min
Hour, be dried in vacuo after removing solvent, be resuspended in anhydrous methylene chloride and be made into 25vol% suspended substances, add in it is excessive just oneself
With same method ball milling or mechanical agitation 24 hours after alcohol, solvent is then removed, is dried after being washed with water.It makes in aforementioned manners
The water-based slurry that standby beta-silicon nitride powder is prepared after 24 hours ball millings or mechanical agitation dispersion when apparent viscosity is 1Pa.s,
Its solid concentration is 57vol%.
Embodiment 8：
Commercially available business nano-grade silicon nitride powder, α-phase content are more than 90%, the volume moment mean diameter of particle in 40nm,
Purity is more than 99%, and grain shape is irregular, and water-based slurry original solids content is 30vol% (1Pa.s).Powder-modified processing
Technique is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 20vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:
1~2.5, ball milling or mechanical agitation 2 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant
Liquid.(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned
Step, until conductivity value of the supernatant conductivity value close to deionized water.(3) anhydrous two are suspended in after beta-silicon nitride powder drying
Chloromethanes is made into 25vol% suspended substances, then adds in the three of 0.05wt% (this content is the percentage of silicon nitride powder weight)
Chlorosilane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 hours in the range of being 200-500 revs/min,
It is dried in vacuo after removing solvent, is resuspended in anhydrous methylene chloride and is made into 25vol% suspended substances, used after adding in excessive n-amyl alcohol
Same method ball milling or mechanical agitation 24 hours, then remove solvent, are dried after being washed with water.The nitrogen prepared in aforementioned manners
SiClx powder prepare water-based slurry through 24 hours ball millings or mechanical agitation dispersion after apparent viscosity be 1Pa.s when, solid phase
Content is 58vol%.
Embodiment 9：
Commercially available business nano-grade silicon nitride powder, α-phase content are more than 90%, the volume moment mean diameter of particle in 40nm,
Purity is more than 99%, and grain shape is irregular, and water-based slurry original solids content is 30vol% (1Pa.s).Powder-modified processing
Technique is as follows：(1) beta-silicon nitride powder is made into the suspended substance of 20vol% with 2M hydrochloric acid, is transferred in ball grinder, using material ball ratio as 1:
1~2.5, ball milling or mechanical agitation 2 hours in the range of rotating speed is 200-500 revs/min are centrifuged after ball milling, remove supernatant
Liquid.(2) beta-silicon nitride powder that is washed with deionized that treated, CENTRIFUGAL ACCELERATING powder precipitation remove supernatant, repeat above-mentioned
Step, until conductivity value of the supernatant conductivity value close to deionized water.(3) anhydrous two are suspended in after beta-silicon nitride powder drying
Chloromethanes is made into 25vol% suspended substances, then adds in the two of 0.05wt% (this content is the percentage of silicon nitride powder weight)
Chlorosilane is 1 in material ball ratio:1~2.5, rotating speed carries out ball milling or mechanical agitation 24 hours in the range of being 200-500 revs/min,
It is dried in vacuo after removing solvent, is resuspended in anhydrous methylene chloride and is made into 25vol% suspended substances, used after adding in excessive n-hexyl alcohol
Same method ball milling or mechanical agitation 24 hours, then remove solvent, are dried after being washed with water.The nitrogen prepared in aforementioned manners
SiClx powder prepare water-based slurry through 24 hours ball millings or mechanical agitation dispersion after apparent viscosity be 1Pa.s when, solid phase
Content is 57vol%.
Claims (7)
1. a kind of modification silicon nitride compound as led to shown in formula (I), which is characterized in that
Wherein, R is selected from-H ,-Cl ,-Br ,-I ,-CH3、-CH2CH3、-C6H5；
R' is selected from-(CH2)nCH3、-CH(CH3)(CH2)nCH3、-CH2C6H5、-(CH2)nOH、 n
For 0 or arbitrary positive integer.
2. a kind of powder preparation method containing silicon nitride modified described in claim 1, it is characterised in that include the following steps,
In, beta-silicon nitride powder used is that the volume moment mean diameter that α-phase content is more than 90%, particle is that 0.7 μm of -40nm, purity are more than
99% beta-silicon nitride powder,
(1) salt acid elution：
The beta-silicon nitride powder is made into the suspended substance of a concentration of 20-35vol% of beta-silicon nitride powder with 2M hydrochloric acid, is then transferred to ball
It is 1 in material ball ratio in grinding jar:Ball milling or mechanical agitation 2-8 hours under conditions of (1~2.5), rotating speed are 200-500 revs/min,
Centrifugation removal supernatant is carried out after ball milling；
(2) deionized water is washed：
Step (1) is washed with deionized treated the beta-silicon nitride powder, then carry out silicon nitride powder described in CENTRIFUGAL ACCELERATING
Body precipitates and removes supernatant, repeat above-mentioned washing step until supernatant conductivity value close to deionized water conductivity value；
(3) graft modification：
Anhydrous methylene chloride, which is suspended in, after beta-silicon nitride powder drying after step (2) is washed is made into silicon nitride powder bulk concentration
For 20-40vol% suspended substances, the halogenated silanes that quality is the silicon nitride powder weight 0.01-0.2wt% is then added in,
Material ball ratio is 1:(1~2.5), rotating speed carry out ball milling or mechanical agitation 8-24 hours under conditions of being 200-500 revs/min；
Then the hydroxyl organic molecule that quality is more than the silicon nitride powder weight 1% is added, is 1 in material ball ratio:(1~
2.5), rotating speed is ball milling under conditions of 200-500 revs/min or mechanical agitation 8-24 hours, then removes the anhydrous dichloromethane
Alkane solvents are washed with water and the powder containing silicon nitride modified described in claim 1 are obtained after being dried after washing.
3. preparation method according to claim 2, it is characterised in that the halogenated silanes is selected from dichlorosilane, trichlorine silicon
Alkane, dichloromethylsilane, ethyl dichloro hydrogen silane, methyl dibromo hydrogen silane, methyl diiodo- hydrogen silane, ethyl dibromo hydrogen silicon
Any one of alkane, phenyl dichloro hydrogen silane.
4. preparation method according to claim 2, it is characterised in that the hydroxyl organic molecule be selected from methanol, ethyl alcohol,
Normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, benzylalcohol, second
Any one of glycol, propylene glycol, butanediol, polyethylene glycol and poly glycol monomethyl ether.
5. the powder containing the modified silicon nitride that a kind of preparation method using claim 2 obtains prepares modified silicon nitride
The method of water-based slurry, it is characterised in that deionized water will be added in and loaded on mixing tank containing the powder of the modified silicon nitride
It is interior, wherein, the volume ratio of powder and water containing the modified silicon nitride is 1:(0.5~1.5) is 1 in material ball ratio:(1~
2.5), rotating speed is carries out ball milling or mechanical agitation 8-24 hour under conditions of 200-500 revs/min up to slurry viscosity is relatively reduced
And reach stable, that is, prepare the modification water-base silicon nitride slurry that solid concentration is not higher than 1Pa.s for 57-62vol%, viscosity.
6. the purposes of the powder containing modified silicon nitride prepared by Claims 2 or 3 or 4 preparation methods, it is characterised in that
The powder containing modified silicon nitride is used to prepare high-performance silicon nitride ceramics purposes.
7. purposes according to claim 6, it is characterised in that the powder containing modified silicon nitride is used to prepare Gao Gu
Phase content, low viscosity beta-silicon nitride powder water-based slurry purposes.
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Cited By (6)
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| CN109896818A (en) * | 2018-06-27 | 2019-06-18 | 湖北工业大学 | A kind of preparation method of the modified adhering and sealing grouting material of silicon nitride nano particles |
| CN109721370A (en) * | 2019-03-05 | 2019-05-07 | 青岛瓷兴新材料有限公司 | Silicon nitride, ceramic slurry and preparation method |
| WO2020177465A1 (en) * | 2019-03-05 | 2020-09-10 | 青岛瓷兴新材料有限公司 | Silicon nitride, ceramic slurry and preparation method |
| CN110297020A (en) * | 2019-06-28 | 2019-10-01 | 济南大学 | A kind of preparation method of calcium analysis silicon nitride graphene paste electrode sensor |
| CN110965340A (en) * | 2019-11-28 | 2020-04-07 | 浙江圣山科纺有限公司 | Application of high-gloss and super-bright silver-aluminum paste to umbrella surface cloth |
| CN113800917A (en) * | 2021-08-17 | 2021-12-17 | 航天特种材料及工艺技术研究所 | Preparation method of homogenized large-size silicon nitride ceramic flat plate |
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