CN116161963B - Silicon carbide ultrafine powder surface modification method - Google Patents
Silicon carbide ultrafine powder surface modification method Download PDFInfo
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- CN116161963B CN116161963B CN202310192585.0A CN202310192585A CN116161963B CN 116161963 B CN116161963 B CN 116161963B CN 202310192585 A CN202310192585 A CN 202310192585A CN 116161963 B CN116161963 B CN 116161963B
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000843 powder Substances 0.000 title claims abstract description 103
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 73
- 238000002715 modification method Methods 0.000 title abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 66
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 29
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 26
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 17
- 239000007787 solid Substances 0.000 abstract description 17
- 238000005054 agglomeration Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 239000007822 coupling agent Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
Abstract
The application relates to the technical field of silicon carbide ultrafine powder, and in particular discloses a surface modification method of silicon carbide ultrafine powder, which comprises the following steps: firstly, at least one of an ammonium carbonate aqueous solution and an ammonium bicarbonate aqueous solution is used as a impurity removing agent to remove impurities on the surface of a silicon carbide ultrafine powder raw material, then a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent are used for further modifying the silicon carbide ultrafine powder after impurity removal, and finally sodium acrylate, acrylamide and a cross-linking agent are used for copolymerization and further modification to obtain modified silicon carbide ultrafine powder. The modification method provided by the application is simple to operate, and the obtained modified silicon carbide ultrafine powder is not easy to generate agglomeration phenomenon in the process of preparing slurry; meanwhile, the volume solid content of the obtained slurry can reach more than 60%, the apparent viscosity is in the range of 1-1.5Pa.s, and the comprehensive performance is good.
Description
Technical Field
The application relates to the technical field of silicon carbide ultrafine powder, in particular to a surface modification method of silicon carbide ultrafine powder.
Background
Silicon carbide ceramics not only have excellent normal temperature mechanical properties such as high flexural strength, excellent oxidation resistance, good corrosion resistance, high abrasion resistance and low coefficient of friction, but also high temperature mechanical properties are the best of the known ceramic materials. Silicon carbide ceramics are widely used in the fields of manufacturing high temperature resistant materials, wear resistant materials, semiconductors and the like.
In recent years, new colloidal molding such as press molding, gel casting, direct solidification casting, etc. is an effective method for producing highly reliable, complex-shaped ceramic parts, and the production of a high-solids, low-viscosity, uniform and stable ceramic slurry is a precondition and key for molding by using these techniques. Because the silicon carbide powder has small particle size and high surface energy, agglomeration phenomenon easily occurs when preparing silicon carbide slurry.
Therefore, it is necessary to design a surface modification method for silicon carbide powder, so as to overcome the defect that agglomeration phenomenon is easy to occur when preparing silicon carbide slurry, and promote the obtained silicon carbide slurry to have the characteristics of high solid content and low viscosity.
Disclosure of Invention
In order to overcome the defect that agglomeration of silicon carbide slurry is easy to occur, and simultaneously obtain the silicon carbide slurry with high solid content and low viscosity, the application provides a surface modification method of silicon carbide ultrafine powder, which adopts the following technical scheme:
a method for modifying the surface of a silicon carbide ultrafine powder, the method comprising the steps of:
(1) Removing impurities on the surface of the silicon carbide ultrafine powder raw material by using a impurity removing agent, wherein the impurity removing agent comprises at least one of an ammonium carbonate aqueous solution and an ammonium bicarbonate aqueous solution, so as to obtain the impurity-removed silicon carbide ultrafine powder;
(2) Dissolving a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent in a solvent, adding the silicon carbide ultrafine powder subjected to impurity removal under the condition of heating and stirring, reacting under the condition of inert gas atmosphere and heating, and after the reaction is finished, sequentially centrifuging and drying to obtain the preliminarily modified silicon carbide ultrafine powder;
(3) Adding the preliminarily modified silicon carbide ultrafine powder into deionized water, adding sodium acrylate, acrylamide and a cross-linking agent, heating and stirring to react, and centrifuging and drying in sequence after the reaction is finished to obtain the modified silicon carbide ultrafine powder.
When the modified silicon carbide ultrafine powder obtained by the modification method is used for preparing slurry, the agglomeration phenomenon is not easy to occur, the volume solid content can reach more than 60%, the apparent viscosity is kept at 1-1.5Pa.s, and the comprehensive performance is good. Meanwhile, the whole modification method is simpler, can realize industrial production, and has better practicability.
More specifically, in the modification method, firstly, impurity on the surface of the silicon carbide ultrafine powder raw material is removed by adopting an impurity removing agent, and the impurity removing agent adopts at least one of an ammonium carbonate aqueous solution and an ammonium bicarbonate aqueous solution. On the basis of better removing impurities on the surface of the silicon carbide ultrafine powder, the corrosion problem generated when impurity ions are removed by common acid and alkali can be effectively solved; and the problem that the hydroxyl groups on the surface of silicon carbide are easy to completely remove and no active contact of the coupling agent exists in the acid-base treatment process is avoided, and the method is suitable for the subsequent process of further modifying by adopting the silane coupling agent.
Meanwhile, the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent are adopted to further modify the silicon carbide ultrafine powder after impurity removal, compared with the common aminosilane coupling agent, the modified effect is better, and the problem that the silicon carbide ultrafine powder is agglomerated again due to the fact that amino groups are easy to form hydrogen bonds after the common aminosilane coupling agent is modified can be effectively solved.
In addition, the application further utilizes copolymerization of sodium acrylate, acrylamide and a cross-linking agent to modify the preliminarily modified silicon carbide ultrafine powder, and the surface of the obtained modified silicon carbide ultrafine powder has electrostatic-steric hindrance effect, and can effectively prevent the particles from being close together, thereby laying a foundation for preparing high-volume solid-content slurry.
In conclusion, the modification method modifies the silicon carbide ultrafine powder through multiple dimensions, objective defects existing in the traditional modification method can be effectively overcome, the modified silicon carbide ultrafine powder which is not easy to cause agglomeration is finally obtained, the modified silicon carbide ultrafine powder can be used for preparing slurry with high volume solid content and low viscosity, and the practicability is high.
In a specific embodiment, in the step (1), the mass concentration of the impurity removing agent is 0.8 to 1.3%.
In a specific embodiment, in step (1), the volume of the silicon carbide ultra-fine powder raw material is 19-24% of the total volume of the silicon carbide ultra-fine powder raw material and the impurity removing agent.
In a specific embodiment, in the step (1), the impurity removing agent removes impurities on the surface of the raw material of the ultrafine silicon carbide powder as follows: adding the silicon carbide ultrafine powder raw material into a impurity removing agent, reacting for 3-5 hours, and sequentially centrifuging and drying to obtain the silicon carbide ultrafine powder after impurity removal.
In a specific embodiment, in the step (2), the mass ratio of the gamma-mercaptopropyl trimethoxysilane coupling agent to the vinyl tris (2-methoxyethoxy) silane coupling agent is 3: (1.5-2.5).
By adopting the technical scheme, the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent are compounded according to the proportion, so that the modification effect is better.
In a specific embodiment, in the step (2), the total mass of the gamma-mercaptopropyl trimethoxysilane coupling agent and the vinyl tris (2-methoxyethoxy) silane coupling agent accounts for 2-3.5% of the mass of the ultra fine silicon carbide powder after the impurity removal.
In a specific embodiment, in the step (3), the mass of the sodium acrylate accounts for 2-5% of the mass of the silicon carbide ultrafine powder after the preliminary modification.
In a specific embodiment, in the step (3), the mass of the acrylamide accounts for 1-3% of the mass of the silicon carbide ultrafine powder after the preliminary modification.
In a specific embodiment, in the step (3), the cross-linking agent accounts for 0.02 to 0.08% of the total mass of the sodium acrylate and the acrylamide.
In a specific embodiment, in the step (3), the reaction is performed by heating and stirring to 60-70 ℃ for 3-4 hours.
In summary, the application has the following beneficial effects:
1. according to the application, the ammonium carbonate aqueous solution or the ammonium bicarbonate aqueous solution is used as a impurity removing agent to remove impurities on the surface of silicon carbide, so that the problem of corrosiveness generated when impurity ions are removed by common acid and alkali is solved; meanwhile, the problem that the hydroxyl groups on the surface of silicon carbide can be completely removed by acid-base treatment without active joints of a coupling agent is solved.
2. The application adopts gamma-mercaptopropyl trimethoxy silane and vinyl tri (2-methoxyethoxy) silane coupling agent to replace common aminosilane coupling agent to modify silicon carbide ultrafine powder, thus solving the problem that the silicon carbide ultrafine powder is agglomerated again due to easy formation of hydrogen bond of amino after the common aminosilane coupling agent is modified.
3. The application further modifies the silicon carbide ultrafine powder by copolymerization of sodium acrylate, acrylamide and a cross-linking agent, and the modified powder surface has electrostatic-steric hindrance effect, can prevent the particles from being close together, and lays a foundation for preparing high-solid-content slurry.
Detailed Description
The application is described in further detail below with reference to examples and comparative examples, all of which are commercially available, wherein the gamma-mercaptopropyl trimethoxysilane coupling agent is KH-590, and the vinyl tris (2-methoxyethoxy) silane coupling agent is GR-SI172.
Example 1
A surface modification method of silicon carbide ultrafine powder comprises the following steps:
(1) 600ml of ammonium carbonate aqueous solution with the mass concentration of 1% is prepared as a impurity removing agent, and the silicon carbide superfine powder raw material with the particle diameter of 0.5-1 mu m is added into the impurity removing agent while stirring, wherein the volume of the silicon carbide superfine powder raw material accounts for 20% of the total volume of the silicon carbide superfine powder raw material and the impurity removing agent; after the addition of 20min, sequentially carrying out centrifugal and drying treatment after 4h, wherein the centrifugal speed is 5000rpm, and the centrifugal time is 10min; the drying temperature is 80 ℃ and the drying time is 8 hours, and the silicon carbide ultrafine powder after impurity removal is obtained;
(2) Firstly, dissolving a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent in dimethylbenzene, wherein the mass ratio of the gamma-mercaptopropyl trimethoxy silane coupling agent to the vinyl tri (2-methoxyethoxy) silane coupling agent is 3:2, and stirring for 15min while heating; adding the silicon carbide ultrafine powder after impurity removal in a stirring state for 30min, wherein the total mass of the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent is 2.5% of the mass of the silicon carbide ultrafine powder after impurity removal; carrying out reaction in an inert gas atmosphere at 85 ℃ for 5 hours, and sequentially centrifuging and drying at 5000rpm for 10 minutes; the drying temperature is 70 ℃ and the drying time is 10 hours, so as to obtain the preliminarily modified silicon carbide ultrafine powder;
(3) 250g of preliminarily modified silicon carbide ultrafine powder is weighed and added into 300ml of deionized water, then sodium acrylate, acrylamide and a cross-linking agent are added, wherein the cross-linking agent is N, N-methylene bisacrylamide, the mass of sodium acrylate accounts for 3.5% of the mass of the preliminarily modified silicon carbide ultrafine powder, the mass of acrylamide accounts for 2.5% of the mass of the preliminarily modified silicon carbide ultrafine powder, and the mass of the cross-linking agent accounts for 0.05% of the total mass of sodium acrylate and acrylamide; controlling the stirring speed to 250rpm, heating to 70 ℃, reacting for 3.5h, and sequentially centrifuging and drying, wherein the centrifuging speed is 5000rpm, and the centrifuging time is 20min; the drying temperature is 105 ℃ and the drying time is 10 hours, and the modified silicon carbide ultrafine powder is obtained.
Example 2
A surface modification method of silicon carbide ultrafine powder comprises the following steps:
(1) 600ml of ammonium carbonate aqueous solution with the mass concentration of 0.8% is prepared as a impurity removing agent, and the silicon carbide superfine powder raw material with the particle diameter of 0.5-1 mu m is added into the impurity removing agent while stirring, wherein the volume of the silicon carbide superfine powder raw material accounts for 19% of the total volume of the silicon carbide superfine powder raw material and the impurity removing agent; after the addition of 20min, sequentially carrying out centrifugal and drying treatment after 3h, wherein the centrifugal speed is 5000rpm, and the centrifugal time is 10min; the drying temperature is 80 ℃ and the drying time is 8 hours, and the silicon carbide ultrafine powder after impurity removal is obtained;
(2) Firstly, dissolving a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent in dimethylbenzene, wherein the mass ratio of the gamma-mercaptopropyl trimethoxy silane coupling agent to the vinyl tri (2-methoxyethoxy) silane coupling agent is 3:1.5, and stirring for 15min while heating; adding the silicon carbide ultrafine powder after impurity removal in a stirring state for 30min, wherein the total mass of the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent is 2% of the mass of the silicon carbide ultrafine powder after impurity removal; carrying out reaction in an inert gas atmosphere at 80 ℃ for 5 hours, and sequentially centrifuging and drying at 5000rpm for 10 minutes; the drying temperature is 70 ℃ and the drying time is 10 hours, so as to obtain the preliminarily modified silicon carbide ultrafine powder;
(3) 250g of preliminarily modified silicon carbide ultrafine powder is weighed and added into 300ml of deionized water, then sodium acrylate, acrylamide and a cross-linking agent are added, wherein the cross-linking agent is N, N-methylene bisacrylamide, the mass of the sodium acrylate accounts for 2% of the mass of the preliminarily modified silicon carbide ultrafine powder, the mass of the acrylamide accounts for 1% of the mass of the preliminarily modified silicon carbide ultrafine powder, and the mass of the cross-linking agent accounts for 0.02% of the total mass of the sodium acrylate and the acrylamide; controlling the stirring speed to 250rpm, heating to 60 ℃, reacting for 3 hours, and sequentially centrifuging and drying, wherein the centrifuging speed is 5000rpm, and the centrifuging time is 20 minutes; the drying temperature is 105 ℃ and the drying time is 10 hours, and the modified silicon carbide ultrafine powder is obtained.
Example 3
A surface modification method of silicon carbide ultrafine powder comprises the following steps:
(1) 600ml of ammonium carbonate aqueous solution with the mass concentration of 1.3% is prepared as a impurity removing agent, and the silicon carbide superfine powder raw material with the particle diameter of 0.5-1 mu m is added into the impurity removing agent while stirring, wherein the volume of the silicon carbide superfine powder raw material accounts for 24% of the total volume of the silicon carbide superfine powder raw material and the impurity removing agent; after the addition of 20min, sequentially carrying out centrifugal and drying treatment after 5h, wherein the centrifugal speed is 5000rpm, and the centrifugal time is 10min; the drying temperature is 80 ℃ and the drying time is 8 hours, and the silicon carbide ultrafine powder after impurity removal is obtained;
(2) Firstly, dissolving a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent in dimethylbenzene, wherein the mass ratio of the gamma-mercaptopropyl trimethoxy silane coupling agent to the vinyl tri (2-methoxyethoxy) silane coupling agent is 3:2.5, and stirring for 15min while heating; adding the silicon carbide ultrafine powder after impurity removal in a stirring state for 30min, wherein the total mass of the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent is 3.5% of the mass of the silicon carbide ultrafine powder after impurity removal; carrying out reaction in an inert gas atmosphere at 90 ℃ for 5 hours, and sequentially centrifuging and drying at 5000rpm for 10 minutes; the drying temperature is 70 ℃ and the drying time is 10 hours, so as to obtain the preliminarily modified silicon carbide ultrafine powder;
(3) 250g of preliminarily modified silicon carbide ultrafine powder is weighed and added into 300ml of deionized water, then sodium acrylate, acrylamide and a cross-linking agent are added, wherein the cross-linking agent is N, N-methylene bisacrylamide, the mass of the sodium acrylate accounts for 5% of the mass of the preliminarily modified silicon carbide ultrafine powder, the mass of the acrylamide accounts for 3% of the mass of the preliminarily modified silicon carbide ultrafine powder, and the mass of the cross-linking agent accounts for 0.08% of the total mass of the sodium acrylate and the acrylamide; controlling the stirring speed to 250rpm, heating to 70 ℃, reacting for 4 hours, and sequentially centrifuging and drying, wherein the centrifuging speed is 5000rpm, and the centrifuging time is 20 minutes; the drying temperature is 105 ℃ and the drying time is 10 hours, and the modified silicon carbide ultrafine powder is obtained.
Example 4
This example differs from example 1 in that in step (1), the mass concentration of the impurity removing agent is 0.8%.
Example 5
This example differs from example 1 in that in step (1), the mass concentration of the impurity removing agent is 1.3%.
Example 6
The difference between this example and example 1 is that in step (1), the impurity removing agent is an aqueous ammonium bicarbonate solution with a mass concentration of 1%.
Example 7
This example differs from example 1 in that in step (1), the impurity removing agent consists of 300ml of an aqueous solution of ammonium carbonate having a mass concentration of 1% and 300ml of an aqueous solution of ammonium bicarbonate having a mass concentration of 1%.
Example 8
This example differs from example 1 in that in step (1), the volume of the silicon carbide ultra-fine powder raw material is 19% of the total volume of the silicon carbide ultra-fine powder raw material and the impurity removing agent.
Example 9
This example differs from example 1 in that in step (1), the volume of the silicon carbide ultra-fine powder raw material is 24% of the total volume of the silicon carbide ultra-fine powder raw material and the impurity removing agent.
Example 10
This example differs from example 1 in that in step (2), the mass ratio of the gamma-mercaptopropyl trimethoxysilane coupling agent to the vinyl tris (2-methoxyethoxy) silane coupling agent is 3:1.5.
example 11
This example differs from example 1 in that in step (2), the mass ratio of the gamma-mercaptopropyl trimethoxysilane coupling agent to the vinyl tris (2-methoxyethoxy) silane coupling agent is 3:2.5.
example 12
This example differs from example 1 in that in step (2), the total mass of the gamma-mercaptopropyl trimethoxysilane coupling agent and the vinyl tris (2-methoxyethoxy) silane coupling agent is 2% of the mass of the ultra fine silicon carbide powder after the removal of impurities.
Example 13
This example differs from example 1 in that in step (2), the total mass of the gamma-mercaptopropyl trimethoxysilane coupling agent and the vinyl tris (2-methoxyethoxy) silane coupling agent is 3.5% of the mass of the ultra fine silicon carbide powder after the removal of impurities.
Example 14
This example differs from example 1 in that in step (3), the mass of sodium acrylate is 2% of the mass of the preliminarily modified silicon carbide ultrafine powder.
Example 15
This example differs from example 1 in that in step (3), the mass of sodium acrylate is 5% of the mass of the preliminarily modified silicon carbide ultrafine powder.
Example 16
This example differs from example 1 in that in step (3), the mass of acrylamide is 1% of the mass of the preliminarily modified silicon carbide ultrafine powder.
Example 17
This example differs from example 1 in that in step (3), the mass of acrylamide is 3% of the mass of the preliminarily modified silicon carbide ultrafine powder.
Comparative example 1
This comparative example differs from example 1 in that step (1) was not performed and the silicon carbide ultrafine powder after the impurity removal in step (2) was replaced with an equal amount of the silicon carbide ultrafine powder raw material.
Comparative example 2
This comparative example differs from example 1 in that in step (1), the impurity removing agent was replaced with an equivalent amount of 10wt% sulfuric acid solution.
Comparative example 3
This comparative example is different from example 1 in that in step (2), the gamma-mercaptopropyl trimethoxysilane coupling agent is not added and the balance is made up with the vinyltris (2-methoxyethoxy) silane coupling agent.
Comparative example 4
This comparative example is different from example 1 in that in step (2), a vinyltris (2-methoxyethoxy) silane coupling agent is not added, and the balance is made up with a gamma-mercaptopropyl trimethoxysilane coupling agent.
Comparative example 5
This comparative example differs from example 1 in that the vinyl tris (2-methoxyethoxy) silane coupling agent and the gamma-mercaptopropyl trimethoxy silane coupling agent were replaced with equal amounts of KH-550.
Comparative example 6
The present comparative example is different from example 1 in that step (2) is not performed, i.e., the preliminarily modified silicon carbide ultrafine powder in step (3) is the purified silicon carbide ultrafine powder obtained in step (1).
Comparative example 7
The difference between this comparative example and example 1 is that step (3) is not performed, i.e., the preliminary modified silicon carbide ultrafine powder obtained in step (2) is the finished modified silicon carbide ultrafine powder.
Performance detection test method
The modified silicon carbide ultrafine powders in examples 1 to 17 and comparative examples 1 to 7 were dispersed in water to prepare slurries having a volume solids content of 50%, respectively, and apparent viscosities and maximum volume solids contents were measured, respectively.
Table 1 test data table
Through the detection data about the maximum volume solid content and apparent viscosity in table 1, the maximum volume solid content of the slurry prepared by the modified silicon carbide ultrafine powder in examples 1-17 is kept above 61%, the apparent viscosity is about 1.3Pa.s, the performance is better, and the modified silicon carbide fine powder is not easy to generate agglomeration phenomenon after being modified by the modification method provided by the application, and can reach higher volume solid content.
In particular, as shown by combining the detection results of the embodiment 1 and the comparative examples 1-2, the maximum volume solid content of the slurry prepared from the modified silicon carbide in the comparative example 1 is only 54.3 without performing the step (1), that is, without performing the impurity removal treatment, which is obviously lower than that of the embodiment 1, and the analysis shows that the performance of reducing the agglomeration phenomenon of the modified silicon carbide ultrafine powder after the impurity removal is better, and the subsequent further modification is more favorable after the impurity removal. In comparative example 2, the maximum volume solids content was improved but still lower than in example 1, and analysis revealed that the sulfuric acid solution, although capable of removing impurities, could cause the problem of elimination of the active sites of the silicon carbide surface coupling agent, and thus also affected the subsequent further modification.
From the specific combination of the detection results of the example 1 and the comparative examples 3-6, the maximum volume solid content of the comparative examples 3-4 is obviously lower than that of the example 1, which indicates that the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent have a certain synergistic interaction in the modification effect, and the combination effect of the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent is better.
In contrast, in comparative example 5, the modification with the conventional aminosilane coupling agent was performed, and the maximum volume solids content was significantly lower than in example 1, and the analysis was probably due to the fact that the conventional aminosilane coupling agent was modified to cause the agglomeration of the ultrafine silicon carbide powder due to the formation of hydrogen bonds by amino groups. And in the scheme of comparative example 6 in which step (2) was not performed, the maximum volume solids content was also significantly lower than in example 1, indicating that the modification effect of step (2) was significant.
From a specific combination of the results of the test of example 1 and the test of comparative example 7, the comparative example 7 was not conducted in the step (3), and the maximum volume solids content of the slurry prepared from the obtained modified silicon carbide ultrafine powder was significantly lower than that of the slurry prepared in the example 1, indicating that the further modification effect of the step (3) was also significant.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (4)
1. A method for modifying the surface of ultrafine silicon carbide powder, which is characterized by comprising the following steps:
(1) Removing impurities on the surface of the silicon carbide ultrafine powder raw material by using a impurity removing agent, wherein the impurity removing agent comprises at least one of an ammonium carbonate aqueous solution and an ammonium bicarbonate aqueous solution, so as to obtain the impurity-removed silicon carbide ultrafine powder;
(2) Dissolving a gamma-mercaptopropyl trimethoxy silane coupling agent and a vinyl tri (2-methoxyethoxy) silane coupling agent in a solvent, adding the silicon carbide ultrafine powder after impurity removal under the condition of heating and stirring, reacting at 80 ℃ or 85 ℃ or 90 ℃ in an inert gas atmosphere for 5 hours, and sequentially centrifuging and drying to obtain the silicon carbide ultrafine powder after preliminary modification;
(3) Adding the preliminarily modified silicon carbide ultrafine powder into deionized water, adding sodium acrylate, acrylamide and a cross-linking agent, heating and stirring to react, and centrifuging and drying in sequence after the reaction is finished to obtain modified silicon carbide ultrafine powder;
in the step (3), the mass of sodium acrylate accounts for 2-5% of the mass of the preliminarily modified silicon carbide ultrafine powder;
in the step (3), the mass of the acrylamide accounts for 1-3% of the mass of the preliminarily modified silicon carbide ultrafine powder;
the weight of the cross-linking agent accounts for 0.02-0.08% of the total weight of the sodium acrylate and the acrylamide;
in the step (2), the mass ratio of the gamma-mercaptopropyl trimethoxy silane coupling agent to the vinyl tri (2-methoxyethoxy) silane coupling agent is 3: (1.5-2.5);
in the step (2), the total mass of the gamma-mercaptopropyl trimethoxy silane coupling agent and the vinyl tri (2-methoxyethoxy) silane coupling agent accounts for 2-3.5% of the mass of the silicon carbide ultrafine powder after impurity removal;
in the step (3), heating and stirring to perform reaction means heating to 60-70 ℃ and reacting for 3-4h.
2. The method for modifying the surface of ultrafine silicon carbide powder according to claim 1, wherein the mass concentration of the impurity removing agent in the step (1) is 0.8-1.3%.
3. The method for surface modification of ultrafine silicon carbide powder according to claim 1, wherein in the step (1), the volume of the ultrafine silicon carbide powder raw material is 19-24% of the total volume of the ultrafine silicon carbide powder raw material and the impurity removing agent.
4. The method for modifying the surface of ultrafine silicon carbide powder according to claim 1, wherein in the step (1), the specific operation of removing impurities on the surface of the raw material of the ultrafine silicon carbide powder by the impurity removing agent is as follows: adding the silicon carbide ultrafine powder raw material into a impurity removing agent, reacting for 3-5 hours, and sequentially centrifuging and drying to obtain the silicon carbide ultrafine powder after impurity removal.
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