CN112430112A - Preparation method of toughened boron nitride nanosheet silicon nitride ceramic composite material - Google Patents
Preparation method of toughened boron nitride nanosheet silicon nitride ceramic composite material Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000002135 nanosheet Substances 0.000 title claims abstract description 117
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 111
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 110
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000000919 ceramic Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 72
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229920001709 polysilazane Polymers 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 12
- NXCOSEIUCIOFNB-UHFFFAOYSA-N 2-aminobenzenediazonium Chemical class NC1=CC=CC=C1[N+]#N NXCOSEIUCIOFNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 238000006557 surface reaction Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 27
- -1 aminophenyl Chemical group 0.000 claims description 24
- 230000001681 protective effect Effects 0.000 claims description 21
- JJMDCOVWQOJGCB-UHFFFAOYSA-N 5-aminopentanoic acid Chemical compound [NH3+]CCCCC([O-])=O JJMDCOVWQOJGCB-UHFFFAOYSA-N 0.000 claims description 20
- 150000001263 acyl chlorides Chemical class 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000011085 pressure filtration Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 2
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- 238000002604 ultrasonography Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material, which comprises the following steps: s1, performing surface functionalization treatment on the hexagonal boron nitride to obtain a functionalized boron nitride nanosheet, and then reacting the functionalized boron nitride nanosheet with aminophenyl diazonium salt to obtain a modified boron nitride nanosheet; s2, grafting modification is carried out on the nano silicon nitride fiber by adopting polyacrylic chloride to obtain the nano silicon nitride fiber grafted with the polyacrylic chloride; s3, reacting the nanometer silicon nitride fiber grafted with polyacrylic chloride with a modified boron nitride nanosheet to obtain a mixture A; and S4, dipping the mixture A in a polysilazane precursor, and curing and sintering at high temperature to obtain the boron nitride nanosheet/silicon nitride ceramic composite material. According to the invention, the hexagonal boron nitride and the nano silicon nitride fibers are respectively modified and then grafted, so that the dispersibility of the hexagonal boron nitride and the nano silicon nitride fibers in the matrix is improved, and the obtained boron nitride nanosheet/silicon nitride ceramic composite material has excellent breaking and toughening properties and bending strength.
Description
Technical Field
The invention relates to the technical field of material modification treatment, in particular to a preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material.
Background
The silicon nitride ceramic as a high-temperature structural ceramic has the characteristics of high strength, good thermal shock resistance, small high-temperature creep, wear resistance, excellent oxidation resistance, high chemical stability and the like, and is one of excellent engineering ceramics. Therefore, the silicon nitride ceramic has wide application range and development prospect, and has great market and application potential in the aspects of high-temperature structural materials, tool ceramic materials, wear-resistant ceramic materials and corrosion-resistant ceramic materials.
Although silicon nitride has good properties, it also has the common property of ceramics, namely brittleness. Silicon nitride ceramics are polycrystalline sintered bodies composed of crystal grains that are ionically or covalently bonded. The extremely strong chemical bonding of the directionality determines that the grain dislocation density in the ceramic is low, the slip system is few, and the energy for crack growth is small. In the fracture process, besides the addition of new fracture surface energy, there is almost no other mechanism for dissipating energy, thereby resulting in the disadvantages of low strength, insufficient toughness, etc. And the brittleness is consistent with a weak point, so that the reliability of the application of the material is not guaranteed. Therefore, improving the toughness and improving the reliability of the silicon nitride ceramic are always important directions for the research of the silicon nitride ceramic.
The two-dimensional material boron nitride nanosheet is a material with a structure similar to that of graphene. Melting point of 300 deg.C in high pressure nitrogen, sublimation and partial decomposition will not occur until heating to 2500 deg.C under normal pressure, and theoretical density is 2.37g/cm3BN is a good thermal conductor and an electrical insulator, and BNNSs has good mechanical property, thermal property and chemical stability, and is widely applied to the fields of super-hydrophobic coatings, transparent composite materials, ultraviolet emitters and the like. However, due to the strong van der waals acting force existing between the boron nitride nanosheets, a large number of secondary agglomerated large particles are easily formed in various dispersion systems, and further the actual application effect of the boron nitride nanosheets is greatly influenced.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material.
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material is characterized by comprising the following steps:
s1, performing surface functionalization treatment on the hexagonal boron nitride to obtain a functionalized boron nitride nanosheet, and then reacting the functionalized boron nitride nanosheet with aminophenyl diazonium salt to obtain a modified boron nitride nanosheet;
s2, grafting modification treatment is carried out on the nano silicon nitride fiber by adopting polyacrylic chloride to obtain the nano silicon nitride fiber grafted with the polyacrylic chloride;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acid chloride into the modified boron nitride nanosheet, stirring for reaction, and neutralizing after the reaction is finished to obtain a mixture A;
and S4, dipping the mixture A in a polysilazane precursor solution, and curing and sintering at high temperature to obtain the boron nitride nanosheet/silicon nitride ceramic composite material.
Preferably, in step S1, performing surface functionalization treatment on hexagonal boron nitride to obtain functionalized boron nitride nanosheets, and then reacting the functionalized boron nitride nanosheets with aminophenyl diazonium salt to obtain modified boron nitride nanosheets, including the following steps: adding hexagonal boron nitride and 5-aminopentanoic acid into a ball milling tank, adding deionized water for mechanical ball milling treatment, after ball milling is finished, carrying out suction filtration, washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution, and then adding aminophenyl diazonium salt for coupling reaction to obtain the modified boron nitride nanosheet.
Preferably, in the mechanical ball milling treatment, the mass ratio of the hexagonal boron nitride to the deionized water to the 5-aminopentanoic acid is 50-70: 15-25: 1, the ball milling speed is 900-1200 rpm, and the ball milling time is 12-18 h.
Preferably, in the coupling reaction, the reaction temperature is 100-200 ℃, the mass concentration of the concentrated sulfuric acid solution is 40-65%, and the mass ratio of the aminophenyl diazonium salt to the functionalized boron nitride nanosheet is 6-12: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 12-35%.
Preferably, the aminophenyl diazonium salt is 4-aminodiphenyldiazohydrogensulfate.
Preferably, in step S2, the step of performing graft modification on the nano silicon nitride fiber by using polyacrylic acid chloride to obtain the polyacrylic acid chloride-grafted nano silicon nitride fiber includes the following steps: carrying out high-temperature liquid phase reaction on nano silicon nitride fibers in a strong base mixture solution to obtain hydroxylated nano silicon nitride fibers, adding the obtained hydroxylated nano silicon nitride fibers into an anhydrous organic solvent, fully dispersing the fibers by ultrasonic to obtain a dispersion liquid, then adding polyacrylic acyl chloride into the dispersion liquid, carrying out heat preservation reaction under a protective gas atmosphere, adding triethylamine to neutralize the solution after the reaction is finished until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fibers grafted with the polyacrylic acyl chloride.
Preferably, in the high-temperature liquid phase reaction, the reaction temperature is 180-250 ℃, the reaction time is 1.0-3.0 h, the strong base mixture solution is an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and the mass ratio of the sodium hydroxide to the potassium hydroxide in the strong base mixture is 1-3.5: 1, the mass ratio of the strong base mixture to the nano silicon nitride fiber is 1.5-4: 1, the anhydrous organic solvent is anhydrous DMF, DMSO, THF or 1, 4-dioxane, and the mass concentration of the anhydrous organic solvent is 0.6-0.9 mg/mL; the mass ratio of the polyacrylic acyl chloride to the nano silicon nitride fiber is 35-50: 1-1.5, wherein in the heat preservation reaction, the reaction temperature is 60-85 ℃, and the reaction time is 10-15 h.
Preferably, in step S3, the reaction temperature is 60 to 100 ℃, the reaction time is 3 to 8 hours, and the neutralizing reagent is triethylamine.
Preferably, in step S4, the step of immersing the mixture a in a polysilazane precursor solution, curing, and sintering at high temperature to obtain the boron nitride nanosheet/silicon nitride ceramic composite material includes the following steps: placing the polysilazane precursor solution and the mixture A in a closed container, heating to 80-300 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at a high temperature of 1650-1850 ℃ in a protective gas atmosphere or vacuum to form the boron nitride nanosheet/silicon nitride ceramic composite material.
Preferably, the polysilazane precursor solution is a polysilazane-xylene solution or a polysilazane-toluene solution, and the mass concentration of polysilazane in the polysilazane precursor solution is 25-45%.
The invention also aims to provide the toughened boron nitride nanosheet/silicon nitride ceramic composite material obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the invention, the hexagonal boron nitride and the 5-aminovaleric acid are ball-milled by a wet method, so that not only is a single-layer boron nitride nanosheet obtained, but also hydroxyl and amino are simultaneously connected to the surface of the boron nitride nanosheet, namely, obtaining a functionalized boron nitride nanosheet, then reacting the functionalized boron nitride nanosheet with amino-substituted phenyl diazonium salt in a hot concentrated acid solution, decomposing the amino-substituted phenyl diazonium salt in the reaction to lose nitrogen and generate an extremely active amino-substituted phenyl carbonium ion, reacting the amino-substituted phenyl carbonium ion with boron hydroxyl and boron amino on the surface of the modified boron nitride nanosheet to release hydrogen, and simultaneously introducing aminophenyl in the amino-substituted phenyl diazonium salt into the boron nitride nanosheet, thereby not only preparing for nucleophilic substitution reaction with acyl chloride in the next step, but also improving the dispersibility of the boron nitride nanosheet.
(2) According to the preparation method, a small amount of hydroxyl functional groups are introduced into the nano silicon nitride fibers through strong alkali treatment, and the linear polyacrylic acyl chloride with high reaction activity is grafted to the surfaces of the nano silicon nitride fibers through acylation reaction, wherein a small amount of hydroxyl only consumes a small amount of acyl chloride groups, and most of acyl chloride side groups are remained on a grafted polymer, so that a small amount of hydroxyl reaction points on the surfaces of the nano silicon nitride fibers are converted into high-activity acyl chloride of a plurality of polymers, and an active platform is provided for the next grafting reaction.
(3) According to the invention, nucleophilic substitution reaction is carried out on the boron nitride nanosheet introduced with the aminophenyl and acyl chloride which is not grafted in the branched chain of the hydroxylated nano silicon nitride fiber grafted with polyacrylic acid chloride, and the boron nitride nanosheet and the nano silicon nitride fiber can further improve the dispersing performance of the boron nitride nanosheet and the nano silicon nitride fiber in a subsequent polysilazane precursor through grafting, so that the boron nitride nanosheet/silicon nitride ceramic composite material obtained through curing and high-temperature sintering has excellent breaking toughness performance, hardness and bending strength.
(4) The preparation method is simple, easy to operate, easy to control the reaction temperature and easy to realize large-scale production.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material comprises the following steps:
s1, weighing 100mg of hexagonal boron nitride, placing the hexagonal boron nitride into an 80ml ball milling tank, sealing the ball milling tank by 2g of 5-aminopentanoic acid and 35ml of deionized water, mechanically milling for 16h at the ball milling speed of 1000rpm, then performing suction filtration, water washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution with the mass concentration of 55%, then adding 4-aminodiphenyl diazo ammonium bisulfate to perform a coupling reaction at 120 ℃ to obtain a modified boron nitride nanosheet, wherein the mass ratio of the 4-aminodiphenyl diazo ammonium bisulfate to the functionalized boron nitride nanosheet is 10: 1, in the obtained modified boron nitride nanosheet, the mass ratio of the aminophenyl group bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 30: 100, respectively;
s2, adding the nano silicon nitride fiber into an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and carrying out high-temperature liquid phase reaction for 2h at 200 ℃ to obtain the hydroxylated nano silicon nitride fiber, wherein the mass ratio of the sodium hydroxide to the potassium hydroxide is 2: adding the obtained hydroxylated nano silicon nitride fiber into anhydrous 1, 4-dioxane, fully dispersing the fiber through ultrasound to obtain a dispersion liquid, ensuring that the mass concentration of the system is 0.8mg/mL at the moment, then dripping polyacrylic chloride into the dispersion liquid, carrying out heat preservation reaction for 12 hours at 80 ℃ in a protective gas atmosphere, adding triethylamine to neutralize the reaction product until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fiber grafted with the polyacrylic chloride, wherein the mass ratio of the polyacrylic chloride to the nano silicon nitride fiber is 40: 1;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acyl chloride into the modified boron nitride nanosheet, stirring and reacting for 6 hours at 80 ℃, and neutralizing with triethylamine after the reaction is finished to obtain a mixture A;
s4, placing the polysilazane precursor solution and the mixture A in a closed container, heating to 80-300 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at 1800 ℃ in the protective gas atmosphere or vacuum to convert the polysilazane precursor into ceramic through pyrolysis, thus obtaining the boron nitride nanosheet/silicon nitride ceramic composite material.
Example 2
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material comprises the following steps:
s1, weighing 100mg of hexagonal boron nitride, placing the hexagonal boron nitride into an 80ml ball milling tank, sealing the ball milling tank by 2g of 5-aminopentanoic acid and 45ml of deionized water, mechanically milling for 12 hours at the ball milling speed of 1200rpm, then carrying out suction filtration, water washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution with the mass concentration of 55%, then adding 4-aminodiphenyl diazo ammonium bisulfate to carry out a coupling reaction at 110 ℃ to obtain a modified boron nitride nanosheet, wherein the mass ratio of the 4-aminodiphenyl ammonium bisulfate to the functionalized boron nitride nanosheet is 6: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 30: 100, respectively;
s2, adding the nano silicon nitride fiber into an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and carrying out high-temperature liquid phase reaction for 3 hours at 180 ℃ to obtain the hydroxylated nano silicon nitride fiber, wherein the mass ratio of the sodium hydroxide to the potassium hydroxide is 3: adding the obtained hydroxylated nano silicon nitride fiber into anhydrous DMF (dimethyl formamide), fully dispersing the hydroxylated nano silicon nitride fiber by ultrasound to obtain a dispersion liquid, ensuring that the mass concentration of the system is 0.8mg/mL, then dripping polyacrylic acid chloride into the dispersion liquid, carrying out heat preservation reaction for 12 hours at 70 ℃ in a protective gas atmosphere, adding triethylamine to neutralize the solution after the reaction is finished until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fiber grafted with the polyacrylic acid chloride, wherein the mass ratio of the polyacrylic acid chloride to the nano silicon nitride fiber is 50: 1;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acyl chloride into the modified boron nitride nanosheet, stirring and reacting for 4 hours at 80 ℃, and neutralizing with triethylamine after the reaction is finished to obtain a mixture A;
s4, placing the polysilazane precursor solution and the mixture A in a closed container, heating to 200 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at a high temperature of 1700 ℃ in a protective gas atmosphere or vacuum to ensure that the polysilazane precursor is cracked at a high temperature and converted into ceramic, thus obtaining the boron nitride nanosheet/silicon nitride ceramic composite material.
Example 3
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material comprises the following steps:
s1, weighing 120mg of hexagonal boron nitride, placing the hexagonal boron nitride into an 80ml ball milling tank, sealing the ball milling tank by 2g of 5-aminopentanoic acid and 35ml of deionized water, mechanically milling for 16h at the ball milling speed of 1200rpm, then carrying out suction filtration, water washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution with the mass concentration of 55%, then adding 4-aminodiphenyl diazo ammonium bisulfate to carry out a coupling reaction at 100 ℃ to obtain a modified boron nitride nanosheet, wherein the mass ratio of the 4-aminodiphenyl ammonium bisulfate to the functionalized boron nitride nanosheet is 12: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 35: 100, respectively;
s2, adding the nano silicon nitride fiber into an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and carrying out high-temperature liquid phase reaction for 2h at 180 ℃ to obtain the hydroxylated nano silicon nitride fiber, wherein the mass ratio of the sodium hydroxide to the potassium hydroxide is 1.5: adding the obtained hydroxylated nano silicon nitride fiber into anhydrous 1, 4-dioxane, fully dispersing the fiber through ultrasound to obtain a dispersion liquid, wherein the mass concentration of the system is 0.8mg/mL, then dripping polyacrylic chloride into the dispersion liquid, carrying out heat preservation reaction for 12 hours at 80 ℃ in a protective gas atmosphere, adding triethylamine to neutralize the reaction product until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fiber grafted with the polyacrylic chloride, wherein the mass ratio of the polyacrylic chloride to the nano silicon nitride fiber is 40: 1;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acyl chloride into the modified boron nitride nanosheet, stirring and reacting for 3 hours at 100 ℃, and neutralizing with triethylamine after the reaction is finished to obtain a mixture A;
s4, placing the polysilazane precursor solution and the mixture A in a closed container, heating to 300 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at 1800 ℃ in the protective gas atmosphere or vacuum to convert the polysilazane precursor into ceramic through pyrolysis, thus obtaining the boron nitride nanosheet/silicon nitride ceramic composite material.
Example 4
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material comprises the following steps:
s1, weighing 140mg of hexagonal boron nitride, placing the hexagonal boron nitride into an 80ml ball milling tank, sealing the ball milling tank by 2g of 5-aminopentanoic acid and 50ml of deionized water, mechanically milling for 12 hours at the ball milling speed of 900rpm, then carrying out suction filtration, water washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution with the mass concentration of 65%, then adding 4-aminodiphenyl diazo ammonium bisulfate to carry out a coupling reaction at 200 ℃ to obtain a modified boron nitride nanosheet, wherein the mass ratio of the 4-aminodiphenyl ammonium bisulfate to the functionalized boron nitride nanosheet is 8: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 15: 100, respectively;
s2, adding the nano silicon nitride fiber into an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and carrying out high-temperature liquid phase reaction for 1h at 220 ℃ to obtain the hydroxylated nano silicon nitride fiber, wherein the mass ratio of the sodium hydroxide to the potassium hydroxide is 2: adding the obtained hydroxylated nano silicon nitride fiber into anhydrous 1, 4-dioxane, fully dispersing the fiber through ultrasound to obtain a dispersion liquid, wherein the mass concentration of the system is 0.8mg/mL, then dripping polyacrylic chloride into the dispersion liquid, carrying out heat preservation reaction for 10 hours at 85 ℃ in a protective gas atmosphere, adding triethylamine to neutralize the reaction liquid until the pH value is neutral after the reaction is finished, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fiber grafted with the polyacrylic chloride, wherein the mass ratio of the polyacrylic chloride to the nano silicon nitride fiber is 45: 1;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acyl chloride into the modified boron nitride nanosheet, stirring and reacting for 6 hours at 80 ℃, and neutralizing with triethylamine after the reaction is finished to obtain a mixture A;
s4, placing the polysilazane precursor solution and the mixture A in a closed container, heating to 100 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at 1650 ℃ in the protective gas atmosphere or vacuum to convert the polysilazane precursor into ceramic through pyrolysis, thereby obtaining the boron nitride nanosheet/silicon nitride ceramic composite material.
Example 5
A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material comprises the following steps:
s1, weighing 100mg of hexagonal boron nitride, placing the hexagonal boron nitride into an 80ml ball milling tank, sealing the ball milling tank by 2g of 5-aminopentanoic acid and 35ml of deionized water, mechanically milling for 16h at the ball milling speed of 1200rpm, then performing suction filtration, water washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution with the mass concentration of 55%, then adding 4-aminodiphenyl diazo ammonium bisulfate to perform a coupling reaction at 110 ℃ to obtain a modified boron nitride nanosheet, wherein the mass ratio of the 4-aminodiphenyl diazo ammonium bisulfate to the functionalized boron nitride nanosheet is 10: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 12: 100, respectively;
s2, adding the nano silicon nitride fiber into an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and carrying out high-temperature liquid phase reaction for 2h at 180 ℃ to obtain the hydroxylated nano silicon nitride fiber, wherein the mass ratio of the sodium hydroxide to the potassium hydroxide is 2: adding the obtained hydroxylated nano silicon nitride fiber into anhydrous DMSO (dimethylsulfoxide), fully dispersing the hydroxylated nano silicon nitride fiber through ultrasound to obtain a dispersion liquid, wherein the mass concentration of a system is 0.8mg/mL, then dripping polyacrylic chloride into the dispersion liquid, carrying out heat preservation reaction at 60 ℃ for 15 hours in a protective gas atmosphere, adding triethylamine to neutralize the reaction solution after the reaction is finished until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fiber grafted with the polyacrylic chloride, wherein the mass ratio of the polyacrylic chloride to the nano silicon nitride fiber is 35: 1.5;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acyl chloride into the modified boron nitride nanosheet, stirring and reacting for 3 hours at 90 ℃, and neutralizing with triethylamine after the reaction is finished to obtain a mixture A;
s4, placing the polysilazane precursor solution and the mixture A in a closed container, heating to 80 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at a high temperature of 1700 ℃ in the protective gas atmosphere or vacuum to ensure that the polysilazane precursor is cracked at a high temperature and converted into ceramic, thus obtaining the boron nitride nanosheet/silicon nitride ceramic composite material.
Comparative example 1
The procedure was the same as in example 1 except that boron nitride nanosheet was added unmodified.
Comparative example 2
The procedure was as in example 1 except that the nano silicon nitride fibers were added unmodified.
Comparative example 3
The procedure was as in example 1 except that the addition of the nano silicon nitride fibers and the addition of boron nitride were both unmodified.
The boron nitride nanosheet/silicon nitride ceramic composite materials obtained in the embodiments 1-5 and the comparative examples 1-3 are subjected to performance tests, and the detection results are detailed in table 1.
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a toughened boron nitride nanosheet silicon nitride ceramic composite material is characterized by comprising the following steps:
s1, performing surface functionalization treatment on the hexagonal boron nitride to obtain a functionalized boron nitride nanosheet, and then reacting the functionalized boron nitride nanosheet with aminophenyl diazonium salt to obtain a modified boron nitride nanosheet;
s2, grafting modification treatment is carried out on the nano silicon nitride fiber by adopting polyacrylic chloride to obtain the nano silicon nitride fiber grafted with the polyacrylic chloride;
s3, adding the nanometer silicon nitride fiber grafted with polyacrylic acid chloride into the modified boron nitride nanosheet, stirring for reaction, and neutralizing after the reaction is finished to obtain a mixture A;
and S4, dipping the mixture A in a polysilazane precursor solution, and curing and sintering at high temperature to obtain the boron nitride nanosheet/silicon nitride ceramic composite material.
2. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 1, wherein in step S1, the surface functionalization treatment is performed on hexagonal boron nitride to obtain functionalized boron nitride nanosheets, and then the functionalized boron nitride nanosheets are reacted with aminophenyl diazonium salt to obtain modified boron nitride nanosheets, comprising the steps of: adding hexagonal boron nitride and 5-aminopentanoic acid into a ball milling tank, adding deionized water for mechanical ball milling treatment, after ball milling is finished, carrying out suction filtration, washing and drying to obtain a functionalized boron nitride nanosheet, adding the obtained functionalized boron nitride nanosheet into a concentrated sulfuric acid solution, and then adding aminophenyl diazonium salt for coupling reaction to obtain the modified boron nitride nanosheet.
3. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 2, wherein in the mechanical ball milling treatment, the mass ratio of hexagonal boron nitride to deionized water to 5-aminovaleric acid is 50-70: 15-25: 1, the ball milling speed is 900-1200 rpm, and the ball milling time is 12-18 h.
4. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 2, wherein in the coupling reaction, the reaction temperature is 100-200 ℃, the mass concentration of the concentrated sulfuric acid solution is 40-65%, and the mass ratio of the aminophenyl diazonium salt to the functionalized boron nitride nanosheet is 6-12: 1, the mass ratio of the aminophenyl bonded to the boron nitride nanosheet to the modified boron nitride nanosheet is 12-35%.
5. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 1, wherein in step S2, the nanometer silicon nitride fiber is subjected to graft modification treatment with polyacrylic acid chloride to obtain the polyacrylic acid chloride-grafted nanometer silicon nitride fiber, and the preparation method comprises the following steps: carrying out high-temperature liquid phase reaction on nano silicon nitride fibers in a strong base mixture solution to obtain hydroxylated nano silicon nitride fibers, adding the obtained hydroxylated nano silicon nitride fibers into an anhydrous organic solvent, fully dispersing the fibers by ultrasonic to obtain a dispersion liquid, then adding polyacrylic acyl chloride into the dispersion liquid, carrying out heat preservation reaction under a protective gas atmosphere, adding triethylamine to neutralize the solution after the reaction is finished until the pH value is neutral, then carrying out reduced pressure filtration, washing and drying to obtain the hydroxylated nano silicon nitride fibers grafted with the polyacrylic acyl chloride.
6. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material as claimed in claim 5, wherein in the high temperature liquid phase reaction, the reaction temperature is 180-250 ℃, the reaction time is 1.0-3.0 h, the strong base mixture solution is an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide, and the mass ratio of sodium hydroxide to potassium hydroxide in the strong base mixture is 1-3.5: 1, the mass ratio of the strong base mixture to the nano silicon nitride fiber is 1.5-4: 1, the anhydrous organic solvent is anhydrous DMF, DMSO, THF or 1, 4-dioxane, and the mass concentration of the anhydrous organic solvent is 0.6-0.9 mg/mL; the mass ratio of the polyacrylic acyl chloride to the nano silicon nitride fiber is 35-50: 1-1.5, wherein in the heat preservation reaction, the reaction temperature is 60-85 ℃, and the reaction time is 10-15 h.
7. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 1, wherein in step S3, the reaction temperature is 60-100 ℃, the reaction time is 3-8 h, and the neutralizing reagent is triethylamine.
8. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 1, wherein in step S4, the mixture a is immersed in a polysilazane precursor solution, cured and sintered at a high temperature to obtain the boron nitride nanosheet/silicon nitride ceramic composite material, and the method comprises the following steps: placing the polysilazane precursor solution and the mixture A in a closed container, heating to 80-300 ℃, preserving heat in a protective gas atmosphere until solidification, and then sintering the obtained condensate at a high temperature of 1650-1850 ℃ in a protective gas atmosphere or vacuum to form the boron nitride nanosheet/silicon nitride ceramic composite material.
9. The preparation method of the toughened boron nitride nanosheet silicon nitride ceramic composite material according to claim 1 or 8, wherein the polysilazane precursor solution is a polysilazane-xylene solution or a polysilazane-toluene solution, and the mass concentration of polysilazane in the polysilazane precursor solution is 25-45%.
10. The toughened boron nitride nanosheet/silicon nitride ceramic composite material is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN115197490A (en) * | 2022-07-25 | 2022-10-18 | 泛海海工(山东)智能装备有限公司 | Marine reinforced polyethylene material, preparation method and application |
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