CN116253568B - Construction of ZrBC organic precursor by coprecipitation method and synthesis of ZrB by synergistic carbothermal reduction 2 Method - Google Patents
Construction of ZrBC organic precursor by coprecipitation method and synthesis of ZrB by synergistic carbothermal reduction 2 Method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002243 precursor Substances 0.000 title claims abstract description 56
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 47
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 9
- 238000010276 construction Methods 0.000 title claims description 5
- 230000015572 biosynthetic process Effects 0.000 title claims description 4
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 81
- 238000006722 reduction reaction Methods 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229920000620 organic polymer Polymers 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000007865 diluting Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 57
- 238000001816 cooling Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 23
- 239000004327 boric acid Substances 0.000 claims description 22
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- -1 allyl phenolic resin Chemical compound 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910007746 Zr—O Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- YCRYSVKEWAWTGI-UHFFFAOYSA-N p,p'-Methoxychlor olefin Chemical compound C1=CC(OC)=CC=C1C(=C(Cl)Cl)C1=CC=C(OC)C=C1 YCRYSVKEWAWTGI-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- PEEKVIHQOHJITP-UHFFFAOYSA-N boric acid;propane-1,2,3-triol Chemical compound OB(O)O.OCC(O)CO PEEKVIHQOHJITP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QFSNCROGCLRZHC-UHFFFAOYSA-N 2,3-dihydroxypropoxyboronic acid Chemical compound OCC(O)COB(O)O QFSNCROGCLRZHC-UHFFFAOYSA-N 0.000 description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical group C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
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- C04B35/5805—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
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Abstract
The invention discloses a ZrBC organic precursor constructed by a coprecipitation method for synthesizing ZrB by synergetic carbothermal reduction 2 The method comprises the following steps: diluting the solution to be prepared, preparing a precipitate by coprecipitation, and preparing ZrB by curing treatment and carbothermal reduction at different temperatures 2 And (3) powder. The invention realizes that B, C element participates in constructing a polymer network of Zr by utilizing a coprecipitation method, and an organic polymer precursor with Zr, B, C, O, H is formed by coprecipitation. And the ZrB with high purity and uniform morphology and granularity is synthesized by the cooperation of carbothermic reduction reaction 2 And (3) powder. The method has the advantages of simple operation, short preparation period, high yield and easy industrial production.
Description
Technical Field
The invention relates to the preparation of ZrB 2 The method of powder, more particularly, refers to a method for synthesizing ZrB by adopting a coprecipitation method to construct ZrBC organic precursor and adopting a synergistic carbothermal reduction method 2 The method.
Background
ZrB 2 The ceramic has high melting point, high strength, high hardness, good electric and thermal conductivity, good flame retardance, heat resistance, corrosion resistance and trappingNeutrons and the like, so the ceramic material is widely developed and utilized in the fields of high-temperature structural ceramic materials, composite materials, refractory materials, nuclear control materials and the like, and is one of the most promising ultra-high-temperature ceramic materials.
ZrB 2 The uniformity of the purity, granularity and morphology of the ceramic powder directly influences ZrB 2 Based on the properties of the ultra-high temperature material and the composite material thereof. At present, the method has the industrial production of ZrB 2 The preparation method of the potential ceramic powder mainly comprises a solid phase method and a liquid phase method. Wherein ZrB prepared by adopting a solid phase method 2 The calcination temperature required by the ceramic powder is high, such as a carbon/boron carbide thermal reduction method; the raw materials are relatively expensive, such as a direct synthesis method, a borothermic reduction method and a silicothermic reduction method; impurities are easy to remain, so that the purity of the powder is not high, such as a mechanochemical method. The liquid phase method mainly comprises a hydrothermal method, a sol-gel method and a coprecipitation method. The hydrothermal method can possibly generate flammable and explosive gas in the reaction process, and has higher requirements on equipment and higher dangers. Although the sol-gel method has many advantages in synthesizing high-purity fine-size powder, it has the disadvantage of too long a gelation process time. The coprecipitation method has potential in synthesizing high-purity fine-size powder, has the advantages of simple operation, short preparation period and the like, and has good industrial application potential.
Disclosure of Invention
The invention aims to provide a method for constructing ZrBC organic precursor by a coprecipitation method and synthesizing ZrB by synergetic carbothermal reduction 2 Is a method of (2). The method utilizes the fact that the product obtained after the reaction between the raw materials is insoluble in the solvent diethylene glycol dimethyl ether, promotes the system to quickly and simultaneously produce the precipitation of the organic polymer network structure with Zr, B, C, O, H, and can synthesize pure ZrB with uniform morphology and particle size through the synergistic carbothermic reduction reaction at a lower temperature (1450 ℃) after full solidification 2 And (3) powder. The invention realizes that B, C element participates in constructing a polymer network of Zr by utilizing a coprecipitation method to form an organic polymer precursor with Zr, B, C, O, H at the same time, and synthesizes ZrB with high purity and uniform morphology and granularity by cooperating with carbothermal reduction reaction 2 And (3) powder. The method has the advantages of simple operation, shorter preparation period, high yield and easy preparationAnd (5) industrialized production.
The invention provides a method for constructing ZrBC organic precursor by co-carbothermic reduction to synthesize ZrB 2 The method is characterized by comprising the following steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
330g to 400g of poly-zirconium-oxygen, 200g to 270g of boric acid, 200g to 270g of glycerin, 29g to 40g of allyl phenolic resin, 480g to 580g of diethylene glycol dimethyl ether and 330g to 400g of ethanol;
step two, preparing a first solution;
diluting allyl phenolic resin in diethylene glycol dimethyl ether to obtain a first solution;
step three, preparing a second solution;
diluting the poly-zirconium-oxygen alkane in ethanol to obtain a second solution;
step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to be 200 r/min-400 r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 5-10 ℃ per minute under stirring, continuously stirring for 30-150 min at 200 ℃, and then cooling to 70-100 ℃ at a cooling rate of 5-10 ℃ per minute to obtain boric acid glyceride;
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 30-150 min, and cooling to 20-40 ℃ at a cooling rate of 1-5 ℃/min;
step 44, adding the first solution under stirring, and continuously stirring for 10-60 min;
step 45, adding the second solution under stirring, continuously stirring for 5-30 min, and standing until precipitation is complete to form a precipitation solution;
step 46, rotary evaporation is carried out to remove the solvent, the precipitation solution is poured into a rotary evaporator, and the yellowish powder precipitate is obtained after rotary evaporation for 30 to 60 minutes at the temperature of 50 to 100 ℃ and the rotating speed of 20 to 50 r/min;
step five, curing the precursor at different temperatures;
placing the precipitate in an oven, and curing to obtain a precursor according to a curing temperature curve;
the xerogel is obtained after the temperature is kept for 30min to 120min at the curing temperature of 120 ℃ and 160 ℃ and 200 ℃ and 250 ℃ respectively at the heating rate of 2 ℃/min to 10 ℃/min; sieving the xerogel through a 100-mesh sieve to obtain precursor powder;
the precursor powder is an organic polymer containing Zr, B, C, O, H;
step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible, placing the graphite crucible into an alumina tube furnace, and calcining ZrB according to a carbothermic reduction calcining temperature curve 2 Powder;
step B, heating to 1150 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1150 ℃ for 30-120 min;
step C, heating to 1450 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1450 ℃ for 10-60 min;
step D, cooling to 1000 ℃ at a speed of 1-10 ℃/min, cooling to 50-60 ℃ along with the furnace, and taking out to obtain the high-purity single-phase micron-sized rod-shaped ZrB 2 And (5) powder.
The invention adopts a coprecipitation method to construct ZrBC organic precursor and combines a carbothermic reduction method to prepare single-phase ZrB 2 The powder has the advantages that:
(1) the ZrBC organic polymer network structure sediment is synthesized by a coprecipitation method, the uniform mixing of the molecular/atomic level is realized among the raw materials, and the ZrB is generated by combining with carbothermal reduction reaction 2 。
(2) In the precipitation process of synthesizing the ZrBC polymer by the coprecipitation method, ammonia water is not needed to adjust the pH value, and the organic precursor can be promoted to be precipitated by only utilizing the poor solubility of reaction products among raw materials in a solvent.
(3) The method for synthesizing ZrBC polymer precipitation by adopting the coprecipitation method is simple in operation, and the preparation period of the precursor is short.
(4) Single phase ZrB by co-precipitation and carbothermic reduction 2 The powder has strong operability, high yield, easy industrialized production and low manufacturing cost.
(5) The sediment is solidified by adopting multistage temperature, and the gradient heating and the rapid cooling rate are matched during calcination, so that the precursor powder is preheated and calcined at different temperatures, and the full implementation of carbothermic reduction reaction is facilitated.
Drawings
FIG. 1 is a schematic diagram of the industrial production of ZrBC organic precursors by the coprecipitation method of the present invention.
FIG. 2 is an infrared spectrum of a ZrBC organic precursor generated by co-precipitation of the present invention prior to curing.
FIG. 3 is a graph of curing temperature for curing ZrBC organic precursors in accordance with the present invention.
FIG. 4 is a graph of calcination temperature for a carbothermally reduced ZrBC organic precursor in accordance with the present invention.
FIG. 5 is ZrB obtained by the method of example 1 of the present invention 2 XRD spectrum of ceramic powder.
FIG. 6 is ZrB obtained by the method of example 1 of the present invention 2 SEM spectrogram of ceramic powder.
FIG. 7 is ZrB obtained by the method of example 2 of the present invention 2 SEM spectrogram of ceramic powder.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples.
Referring to FIG. 1, the invention provides a method for synthesizing ZrB by adopting a coprecipitation method to construct a ZrBC organic precursor and adopting a carbon thermal reduction method 2 Comprising the following preparation steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
330g to 400g of poly-zirconyl-oxy-alkane (PNZ) and boric acid (H) 3 BO 3 ) 200 g-270 g, glycerin 200 g-270 g, allyl29 g-40 g of base phenolic resin (APF), 480 g-580 g of diethylene glycol dimethyl ether (DMDE) and 330 g-400 g of ethanol.
Step two, preparing a first solution;
and diluting the allyl phenolic resin in diethylene glycol dimethyl ether to obtain a first solution.
Step three, preparing a second solution;
the polyzirconyl amine is diluted in ethanol to obtain a second solution.
Step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to be 200 r/min-400 r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 5-10 ℃ per minute under stirring, continuously stirring for 30-150 min at 200 ℃, and then cooling to 70-100 ℃ at a cooling rate of 5-10 ℃ per minute to obtain boric acid glyceride;
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 30-150 min, and cooling to 20-40 ℃ at a cooling rate of 1-5 ℃/min;
step 44, adding the first solution under stirring, and continuously stirring for 10-60 min;
step 45, adding the second solution under stirring, continuously stirring for 5-30 min, and standing until precipitation is complete to form a precipitation solution;
and 46, rotary evaporating to remove the solvent, pouring the precipitation solution into a rotary evaporator, and rotary evaporating for 30-60 min at the temperature of 50-100 ℃ at the rotating speed of 20-50 r/min to obtain a milky yellow powdery precipitate.
In the fourth step of the invention, the raw materials are added in batches under the continuous stirring state with the stirring speed of 200 r/min-400 r/min, and the chemical reaction among the raw materials is utilized to lead the raw materials to be connected together by chemical bonds, so that the final sediment is ZrB simultaneously containing Zr, B, C, O, H 2 An organic polymer. Removing solvent from the precipitation solution by rotary evaporator, andcompared with oven drying, the rotary evaporation is favorable for removing the solvent, so that the components are uniform, and the rapid evaporation of the solvent can be realized.
Step five, curing the precursor at different temperatures;
the precipitate was placed in an oven and cured to produce a precursor according to the curing temperature profile shown in fig. 3.
The xerogel is obtained after the temperature is kept for 30min to 120min at the curing temperature of 120 ℃ and 160 ℃ and 200 ℃ and 250 ℃ respectively at the heating rate of 2 ℃/min to 10 ℃/min; sieving the xerogel through a 100-mesh sieve to obtain precursor powder;
the precursor powder is an organic polymer containing Zr, B, C, O, H.
Step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible and an alumina tube furnace, and calcining ZrB according to a carbothermic reduction calcining temperature curve shown in FIG. 4 2 Powder;
step B, heating to 1150 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1150 ℃ for 30-120 min;
step C, heating to 1450 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1450 ℃ for 10-60 min;
step D, cooling to 1000 ℃ at a speed of 1-10 ℃/min, cooling to 50-60 ℃ along with the furnace, and taking out to obtain the high-purity single-phase ZrB 2 And (5) powder.
ZrB prepared by the method 2 Analysis of Material Properties
The high-purity single-phase ZrB prepared by the method of the invention 2 The powder body is in a rod shape, and the carbon and oxygen content of the powder body is respectively 0.36 to 2.18 weight percent and 0.91 to 1.06 weight percent.
Example 1 preparation of ZrB with an average rod length of 1.5 μm 2 Powder
Referring to FIG. 1, a co-carbothermic reduction method is used to construct ZrBC organic precursor to synthesize ZrB 2 The method comprises the following preparation steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
polyzirconyl-oxy-alkane (PNZ) 376.5g, boric acid (H) 3 BO 3 ) 217.4g, 217.4g of glycerol, 34.3g of allylphenol formaldehyde resin (APF), 532g of diethylene glycol dimethyl ether (DMDE) and 376.5g of ethanol.
Step two, preparing a first solution;
the allylic phenol formaldehyde resin (APF) was diluted in diethylene glycol dimethyl ether (DMDE) to give a first solution. DMDE is used to reduce viscosity because APF is relatively viscous, thereby allowing APF to flow smoothly through the conduit into the coprecipitation vessel. And because DMDE is colorless neutral liquid with ether taste, the chemical property is stable, the chemical reaction is not easy to occur, various resins can be dissolved, and the DMDE can be mixed with ethanol in any proportion.
Step three, preparing a second solution;
the polyzirconyl amine is diluted in ethanol to obtain a second solution. Since PNZ is relatively viscous, ethanol is used to reduce viscosity, so that PNZ smoothly flows into the coprecipitation container through the pipeline.
Step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to 220r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 8 ℃/min under a stirring state, continuously stirring for 120min at the temperature, and then cooling to 100 ℃ at a cooling rate of 5 ℃/min to obtain glycerin borate;
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 90min, and cooling to 22 ℃ at a cooling rate of 3 ℃/min;
step 43 in the present invention is to completely dissolve the glyceryl borate in diethylene glycol dimethyl ether. Diethylene glycol dimethyl ether is a good solvent for glycerol borate, and does not react with glycerol borate. And the diethylene glycol dimethyl ether has a high boiling point, and can be rapidly dissolved and mixed with the boric acid glyceride under the condition of heating and stirring at 100 ℃.
Step 44, adding the first solution under stirring, and continuously stirring for 60min;
step 45, adding the second solution under stirring, continuously stirring for 10min, and standing until precipitation is complete to form a precipitation solution;
step 46, spin-evaporating to remove the solvent, pouring the precipitation solution into a rotary evaporator, and performing rotary evaporation for 60min at the temperature of 100 ℃ at the rotating speed of 20r/min to obtain a precipitate of cream yellow powder.
In the invention, the infrared spectrum of the precipitate obtained after the coprecipitation in the fourth step is shown in fig. 2, wherein the existence of Zr-O, zr-O-B, zr-O-C, B-O-C bonds indicates that the raw materials are connected together through chemical bonds in the precipitation process. Realizes the formation of ZrB simultaneously containing Zr, B, C, O, H by a coprecipitation method 2 An organic polymer precursor. The abscissa of fig. 2 is the wave number (wavenumbers), and the ordinate is the transmittance (transmissibility).
Step five, curing the precursor at different temperatures;
and (3) placing the precipitate in an oven, setting the curing temperature and the curing time, and curing to obtain precursor powder. See the curing temperature profile shown in fig. 3.
Keeping the temperature at the curing temperature of 120 ℃ and 160 ℃, 200 ℃ and 250 ℃ for 120min at a heating rate of 5 ℃/min to obtain xerogel; sieving the xerogel through a 100-mesh sieve to obtain precursor powder;
the precursor powder is an organic polymer containing Zr, B, C, O, H.
Step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible, placing the graphite crucible into an alumina tube furnace, and setting a staged calcining temperature and carbothermic reduction time for calcining; see figure 4 for carbothermic treatment time and calcination temperature.
Step B, heating to 1150 ℃ at a speed of 5 ℃/min, and preserving heat at 1150 ℃ for 120min;
step C, heating to 1450 ℃ at a speed of 5 ℃/min, and preserving heat at 1450 ℃ for 60min;
step D, cooling to 1000 ℃ at a speed of 2 ℃/min, and then cooling to 50 ℃ along with the furnace to obtain the high-purity single-phase ZrB 2 And (5) powder.
In example 1, the carbothermal reduction reaction was ZrO 2 (s)+5C(s)+B 2 O 3 (l,g)→ZrB 2 (s) +5CO (g). s represents a solid, l represents a liquid, and g represents a gas. In the invention, carbothermic reduction is one-step direct reduction, so that the energy utilization is reasonable, and the method is beneficial to mass industrialized continuous production. And step six, the required equipment has simple structure and mature process operation.
ZrB obtained by the method of example 1 2 Analysis of Material Properties
ZrB shown in FIG. 5 2 In XRD diffraction pattern of powder, diffraction peak and average in the pattern belong to ZrB 2 No impurity peak, illustrating that example 1 synthesizes single phase ZrB 2 And (3) powder.
ZrB shown in FIG. 6 2 In the SEM spectrum of the powder, a diagram showing ZrB synthesized in example 1 is shown 2 The powder is in a rod shape, the average rod length is 1.50 mu m, and the powder belongs to micron-sized powder.
Carbon element analysis by carbon-sulfur analyzer, oxygen element analysis by oxygen-nitrogen analyzer, micron ZrB synthesized in example 1 2 The carbon content of the powder was 0.36wt% and the oxygen content was 0.92wt%. ZrB synthesized by the method 2 The impurity element of the ceramic powder is carbon oxygen element, and ZrB is obtained when the impurity element content is lower 2 The purer the ceramic powder, the more advantageous the sintering. Because amorphous carbon and lattice oxygen content in the powder cannot be measured by XRD test, residual carbon content in the powder is measured by adopting a carbon-sulfur analyzer, and residual oxygen content in the system is measured by adopting an oxygen-nitrogen analyzer.
Example 2
Referring to FIG. 1, a co-carbothermic reduction method is used to construct ZrBC organic precursor to synthesize ZrB 2 The method comprises the following preparation steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
400g of poly-zirconyl-oxy-alkane (PNZ) and boric acid (H) 3 BO 3 ) 270g, 270g of glycerin, 29g of allylphenol formaldehyde resin (APF), 578g of diethylene glycol dimethyl ether (DMDE) and 400g of ethanol.
Step two, preparing a first solution;
and diluting the allyl phenolic resin in diethylene glycol dimethyl ether to obtain a first solution.
Step three, preparing a second solution;
the polyzirconyl amine is diluted in ethanol to obtain a second solution.
Step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to 300r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 10 ℃/min under a stirring state, continuously stirring for 90min at the temperature, then cooling to 80 ℃ at a cooling rate of 10 ℃/min to obtain glycerin borate,
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 60min, and cooling to 30 ℃ at a cooling rate of 5 ℃/min;
step 44, adding the first solution under stirring, and continuously stirring for 60min;
step 45, adding the second solution under stirring, continuously stirring for 25min, and standing for 30min until precipitation is complete to form a precipitation solution;
step 46, spin-evaporating to remove the solvent, pouring the precipitation solution into a rotary evaporator, and spin-evaporating for 30min at the rotation speed of 30r/min and the temperature of 80 ℃ to obtain a precipitate of cream yellow powder.
Step five, curing the precursor at different temperatures;
and (3) placing the precipitate in an oven, setting the curing temperature and the curing time, and curing to obtain precursor powder.
Keeping the temperature at 120deg.C, 160deg.C, 200deg.C and 250deg.C for 45min at a heating rate of 10deg.C/min to obtain xerogel; sieving with 100 mesh sieve to obtain precursor powder;
the precursor powder is an organic polymer containing Zr, B, C, O, H.
Step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible, and placing into an alumina tube furnace for carbothermic reduction calcination;
step B, heating to 1150 ℃ at a rate of 10 ℃/min, and preserving heat at 1150 ℃ for 30min;
step C, heating to 1450 ℃ at a speed of 5 ℃/min, and preserving heat at 1450 ℃ for 60min;
step D, cooling to 1000 ℃ at a speed of 5 ℃/min, and then cooling to 60 ℃ along with the furnace to obtain the high-purity ZrB 2 And (5) powder.
ZrB obtained by the method of example 2 2 Analysis of Material Properties
Single phase ZrB was synthesized in example 2 by XRD diffraction pattern analysis 2 And (3) powder.
ZrB shown in FIG. 7 2 In the SEM spectrum of the powder, a diagram showing ZrB synthesized in example 2 is shown 2 The powder is in a micron-sized short rod shape, the average rod length is 1.60 mu m, and the powder belongs to micron-sized.
Micron-sized ZrB synthesized in example 2 by elemental analysis 2 The carbon content of the powder was 2.18wt% and the oxygen content was 1.06wt%.
Example 3
Referring to FIG. 1, a co-carbothermic reduction method is used to construct ZrBC organic precursor to synthesize ZrB 2 The method comprises the following preparation steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
330g of poly-zirconyl-oxy-alkane (PNZ) and boric acid (H) 3 BO 3 ) 200g of glycerin, 200g of allyl phenolic resin (APF), 40g of diethylene glycol dimethyl ether (DMDE), 480g of ethanol and 330g of ethanol.
Step two, preparing a first solution;
and diluting the allyl phenolic resin in diethylene glycol dimethyl ether to obtain a first solution.
Step three, preparing a second solution;
the polyzirconyl amine is diluted in ethanol to obtain a second solution.
Step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to 400r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 5 ℃/min under a stirring state, continuously stirring for 150min at the temperature, and then cooling to 70 ℃ at a cooling rate of 5 ℃/min to obtain glycerin borate;
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 120min, and cooling to 40 ℃ at a cooling rate of 5 ℃/min;
step 44, adding the first solution under stirring, and continuously stirring for 30min;
step 45, adding the second solution under stirring, continuously stirring for 30min, and standing for 30min until precipitation is complete to form a precipitation solution;
step 46, spin-evaporating to remove the solvent, pouring the precipitation solution into a rotary evaporator, and spin-evaporating for 45min at the temperature of 60 ℃ at the rotation speed of 50r/min to obtain a precipitate of cream yellow powder.
Step five, curing the precursor at different temperatures;
and (3) placing the precipitate in an oven, setting the curing temperature and the curing time, and curing to obtain precursor powder.
Maintaining the temperature at 120deg.C, 160deg.C, 200deg.C and 250deg.C for 90min at heating rate of 2deg.C/min to obtain xerogel; sieving with 100 mesh sieve to obtain precursor powder;
the precursor powder contains Zr, B, C, O, H organic polymer.
Step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible, and placing into an alumina tube furnace for carbothermic reduction calcination;
step B, heating to 1150 ℃ at a speed of 8 ℃/min, and preserving heat at 1150 ℃ for 60min;
step C, heating to 1450 ℃ at a speed of 10 ℃/min, and preserving heat at 1450 ℃ for 10min;
step D, cooling to 1000 ℃ at a speed of 5 ℃/min, and then cooling to 55 ℃ along with a furnace to obtain the high-purity ZrB 2 And (5) powder.
ZrB obtained by the method of example 3 2 Analysis of Material Properties
Single phase ZrB was synthesized in example 3 by XRD diffraction pattern analysis 2 And (3) powder.
ZrB synthesized in example 3 by SEM spectrogram analysis 2 The powder is in a micron-sized short rod shape.
Micron-sized ZrB synthesized in example 3 by elemental analysis 2 The carbon content of the powder was 2.08wt% and the oxygen content was 0.91wt%.
Claims (4)
1. ZrBC organic precursor constructed by coprecipitation method and synthesized into ZrB by cooperative carbothermal reduction 2 The method is characterized by comprising the following steps:
step one, preparing raw materials;
100g of ZrB 2 The amounts of raw materials required for the powder are as follows:
330g to 400g of poly-zirconium-oxygen, 200g to 270g of boric acid, 200g to 270g of glycerin, 29g to 40g of allyl phenolic resin, 480g to 580g of diethylene glycol dimethyl ether and 330g to 400g of ethanol;
step two, preparing a first solution;
diluting allyl phenolic resin in diethylene glycol dimethyl ether to obtain a first solution;
step three, preparing a second solution;
diluting the poly-zirconium-oxygen alkane in ethanol to obtain a second solution;
step four, coprecipitation is carried out to prepare a precipitate;
step 41, setting the stirring speed of the coprecipitation container to be 200 r/min-400 r/min;
step 42, adding boric acid and glycerin into a coprecipitation container, heating to 200 ℃ at a heating rate of 5-10 ℃ per minute under stirring, continuously stirring for 30-150 min at 200 ℃, and then cooling to 70-100 ℃ at a cooling rate of 5-10 ℃ per minute to obtain boric acid glyceride;
step 43, adding diethylene glycol dimethyl ether into the boric acid glyceride under the stirring state, continuously stirring for 30-150 min, and cooling to 20-40 ℃ at a cooling rate of 1-5 ℃/min;
step 44, adding the first solution under stirring, and continuously stirring for 10-60 min;
step 45, adding the second solution under stirring, continuously stirring for 5-30 min, and standing until precipitation is complete to form a precipitation solution;
step 46, rotary evaporation is carried out to remove the solvent, the precipitation solution is poured into a rotary evaporator, and the yellowish powder precipitate is obtained after rotary evaporation for 30 to 60 minutes at the temperature of 50 to 100 ℃ and the rotating speed of 20 to 50 r/min;
step five, curing the precursor at different temperatures;
placing the precipitate in an oven, and curing to obtain a precursor according to a curing temperature curve;
the xerogel is obtained after the temperature is kept for 30min to 120min at the curing temperature of 120 ℃ and 160 ℃ and 200 ℃ and 250 ℃ respectively at the heating rate of 2 ℃/min to 10 ℃/min; sieving the xerogel through a 100-mesh sieve to obtain precursor powder;
the precursor powder is an organic polymer containing Zr, B, C, O, H;
step six, preparing ZrB by carbothermal reduction 2 A material;
step A, placing precursor powder into a graphite crucible, placing the graphite crucible into an alumina tube furnace, and calcining ZrB according to a carbothermic reduction calcining temperature curve 2 Powder;
step B, heating to 1150 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1150 ℃ for 30-120 min;
step C, heating to 1450 ℃ at a speed of 5-10 ℃/min, and preserving heat at 1450 ℃ for 10-60 min;
step D, cooling to 1000 ℃ at a speed of 1-10 ℃/min, cooling to 50-60 ℃ along with the furnace, and taking out to obtain the high-purity single-phase micron-sized rod-shaped ZrB 2 And (5) powder.
2. Construction of ZrBC organic precursor by the coprecipitation method according to claim 1 for synthesizing ZrB by synergistic carbothermal reduction 2 The method is characterized in that: in the precipitate obtained after the coprecipitation in the fourth step, the existence of Zr-O, zr-O-B, zr-O-C, B-O-C bonds indicates that all raw materials are connected together through chemical bonds in the precipitation process; realizes the formation of ZrB simultaneously containing Zr, B, C, O, H by a coprecipitation method 2 An organic polymer precursor.
3. Construction of ZrBC organic precursor by the coprecipitation method according to claim 1 for synthesizing ZrB by synergistic carbothermal reduction 2 The method is characterized in that: carbothermic reduction reaction is ZrO 2 (s)+5C(s)+B 2 O 3 (l,g)→ZrB 2 (s) +5CO (g); s represents a solid, l represents a liquid, and g represents a gas.
4. Construction of ZrBC organic precursor by the coprecipitation method according to claim 1 for synthesizing ZrB by synergistic carbothermal reduction 2 The method is characterized in that: the prepared high-purity single-phase ZrB 2 The carbon and oxygen content of the powder is 0.36 to 2.18 weight percent and 0.91 to 1.06 weight percent respectively.
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