CN117247269A - Preparation method of high-temperature-resistant composite bone ash crystal material - Google Patents
Preparation method of high-temperature-resistant composite bone ash crystal material Download PDFInfo
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- CN117247269A CN117247269A CN202311508504.XA CN202311508504A CN117247269A CN 117247269 A CN117247269 A CN 117247269A CN 202311508504 A CN202311508504 A CN 202311508504A CN 117247269 A CN117247269 A CN 117247269A
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000012467 final product Substances 0.000 claims abstract description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 9
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical group [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- SKEUORFFKHNEGA-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(CC)OC(=O)C(C)=C SKEUORFFKHNEGA-UHFFFAOYSA-N 0.000 claims description 4
- -1 2-acryloxyisopentenyl sulfonic acid Chemical compound 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- CXIIVBDEBISQRW-UHFFFAOYSA-N 2-prop-2-enoyloxybutane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(CC)OC(=O)C=C CXIIVBDEBISQRW-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004575 stone Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C04B32/00—Artificial stone not provided for in other groups of this subclass
- C04B32/005—Artificial stone obtained by melting at least part of the composition, e.g. metal
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/10—Burned or pyrolised refuse
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a preparation method of a high-temperature-resistant composite bone ash crystal material, which comprises the following steps: mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof, reacting, and filtering a product after the reaction is finished to obtain a product I; mixing sulfonic acid monomer, methacrylamide and vinyl pyrrolidone, dissolving in enough water, adding a pH regulator to control the pH value of the system, adding an initiator to stir and react, and then adding a stabilizer and a cross-linking agent to react to obtain a product II; and ultrasonically dispersing bone ash in a dilute acid solution to obtain a product III, mixing the products I, II and III, fully and uniformly stirring, and then calcining, crushing and melting the mixture in sequence, and then cooling and molding the mixture in a mold to obtain a final product. The product obtained by the invention has excellent physicochemical properties.
Description
Technical Field
The invention belongs to the technical field of preparation of bone ash stone materials, and particularly relates to a preparation method of a high-temperature-resistant composite bone ash stone material.
Background
The bone ash stone is prepared by taking bone ash as a main raw material and crystalline powder as an auxiliary material. Wherein the crystal powder is formed by mixing sodium oxide, boric acid, quartz sand and inorganic salt. Because the main components of the bone ash are calcium phosphate and other small amount of salts and oxides, when the external temperature reaches 1400-1500 ℃, the bone ash is in a molten state, and the bone ash stone is obtained after the molten bone ash is cooled and molded. Based on this principle, in the manufacturing process, ashes are mixed with crystalline powder to form a powder mixture, which is then placed in a sigma ashes crystal furnace. The powder is mixed and melted when the temperature in the furnace is heated to a very high temperature of about 1400-1500 c. The furnace body then creates a negative pressure or build-up that causes the melt to enter a cooling chamber. During cooling, the melt begins to crystallize and form crystalline stones. This process takes about days or even weeks to ensure that the bone ash crystals have sufficient quality and strength. This causes an increase in cost.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a high-temperature-resistant composite bone ash crystal material. The composite bone ash stone has the advantages of short preparation time, stable structure, high temperature resistance, high hardness, low porosity and high compressive strength.
The aim and the technical problems of the invention are realized by adopting the following technical proposal.
An embodiment of the invention provides a preparation method of a high-temperature-resistant composite bone ash crystal material, which comprises the following steps:
mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the suspension with alkaline solution of metal or metal compound according to the volume ratio of 1:0.08-0.1, reacting for 4-8h at 100-150 ℃, cooling to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder to the silicon nitride powder to the water is 1g:3-6g: mixing in an amount of 20-40 mL;
according to mass percent, 30-50% of sulfonic acid monomer, 20-40% of methyl acrylamide and 30-50% of vinyl pyrrolidone are mixed and dissolved in enough water, meanwhile, a pH regulator is added to control the pH value of the system to be 8.0-10.0, the solution is heated to 30-50 ℃, then an initiator is added to stir and react for 6-10 hours, a stabilizer and a cross-linking agent are added into the obtained solution to react for 4-6 hours at 60-80 ℃, and after the reaction is finished, the solution is cooled to room temperature, thus obtaining a product II; the initiator, the stabilizer and the cross-linking agent are added according to the mass ratio of 1:0.1-0.7:1;
according to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 30-40% diluted acid solution in an amount of 10-20mL to obtain a product III, mixing the products I, II and III according to a volume ratio of 0.5-0.8:0.03-0.1:1, fully and uniformly stirring, calcining the mixture at 600-800 ℃ for 35-45min, crushing, melting at 1400-1500 ℃ for 20-40min under 0.15-0.25MPa, and cooling and molding in a mold to obtain the final product.
Further, the alkaline solution of the metal or the compound thereof is prepared from the metal or the compound thereof and ammonia water according to the mass volume ratio of 1-3g:10-15mL of the mixed solution is evenly stirred at normal temperature.
Further, the metal or the compound thereof is selected from one or a mixture of at least two of the following metal simple substances or oxides or hydroxides thereof, and the group consists of: magnesium, calcium, aluminum, iron, titanium, manganese, copper, zinc.
Further, the sulfonic acid monomer is selected from any one of 2-methacryloxybutyl sulfonic acid, 2-acryloxybutyl sulfonic acid and 2-acryloxyisopentenyl sulfonic acid.
Further, the initiator is an oxidation-reduction initiation system, the oxidant is one of potassium persulfate, ammonium persulfate and hydrogen peroxide, and the reducing agent is one of sodium bisulphite, sodium sulfite, sodium thiosulfate, tetramethyl ethylenediamine, ferrous chloride and cuprous chloride.
Further, the stabilizer is thiourea or cobalt chloride.
Further, the cross-linking agent is chromium acetate or zirconium acetate.
Further, the pH regulator is sodium hydroxide or potassium hydroxide.
Further, the dilute acid solution comprises hydrochloric acid, nitric acid, acetic acid, oxalic acid or citric acid.
The invention has the following expected effects and advantages: the invention takes silicon powder and silicon nitride powder as raw materials, and the silicon powder and the silicon nitride powder are mixed with alkaline solution of metal or a compound thereof and then react at a set temperature to obtain metal ion modified silica sol solution, and the silicon powder and the silicon nitride powder are used as raw materials of silica sol, have rich sources and are dissolved in water to form suspension. The alkaline solution of the metal or the compound thereof can provide a metal cation and an alkaline reaction system for the reaction process, the metal cation has positive charge activity, and suspension formed by silicon and silicon nitride in the system can be modified, so that the obtained silica sol solution has excellent high temperature resistance, enhanced ageing resistance, fireproof performance and the like. The method comprises the steps of initiating free radical polymerization reaction by using three substances of sulfonic acid monomers, methyl acrylamide and vinyl pyrrolidone as monomers under the action of an initiator to obtain a triplet copolymer, and then carrying out cross-linking reaction between the copolymers under the action of a stabilizer and a cross-linking agent to obtain a copolymer solution. Mixing the above two materials with acid solution of bone ash, calcining, pulverizing, melting, cooling, and shaping to obtain bone ash spar. The bone ash spar has excellent high temperature resistance, and simultaneously, the metal ion modified silica sol solution and the polymer solution are used as auxiliary materials, so that the adhesiveness between bone ash particles can be improved, and the obtained spar has high stability. Compared with the traditional method, the method of the invention greatly shortens the preparation time and saves the cost.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purposes and the effects of the present invention easy to understand, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof (mixed solution of magnesium, calcium oxide and titanium which are uniformly stirred with ammonia water at normal temperature according to the mass volume ratio of 2g to 13mL, wherein the mass ratio of the mixed solution is 1 to 1.5), reacting the mixed solution at 125 ℃ for 6 hours, cooling the mixed solution to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder, the silicon nitride powder and the water is 1g:4.5g: an amount of 30mL was mixed.
According to mass percent, 2-methacryloxybutyl sulfonic acid 40%, methacrylamide 30% and vinyl pyrrolidone 30% are mixed and dissolved in enough water, sodium hydroxide is added at the same time to control the pH value of the system to be 8.0-10.0, an initiator (a system consisting of 50% potassium persulfate and 50% sodium bisulfite) is added after the temperature of the solution is raised to 40 ℃ for stirring reaction for 8 hours, thiourea and zirconium acetate are added into the obtained solution for reaction for 5 hours at 70 ℃, and the product II is obtained after the reaction is finished and cooled to room temperature; the initiator, thiourea and zirconium acetate are added in the mass ratio of 1:0.4:1.
According to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 35% hydrochloric acid solution in 15mL to obtain a product III, mixing the products I, II and III according to the volume ratio of 0.6:0.07:1, fully and uniformly stirring, calcining the mixture at 700 ℃ for 40min, crushing, melting at 1450 ℃ under 0.20MPa for 30min, and then cooling and molding in a mold to obtain the final product.
Example 2: mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof (mixed solution of magnesium oxide, calcium and aluminum oxide which are uniformly stirred with ammonia water at normal temperature according to the mass volume ratio of 3g to 15mL, wherein the mass ratio of the mixed solution is 1:1:1), reacting for 8 hours at 100 ℃, cooling to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder, the silicon nitride powder and the water is 1g:3g: an amount of 20mL was mixed.
According to mass percent, mixing 30% of 2-acryloxybutyl sulfonic acid, 40% of methacrylamide and 30% of vinylpyrrolidone, dissolving in enough water, simultaneously adding sodium hydroxide to control the pH value of a system to be 8.0-10.0, heating the solution to 50 ℃, adding an initiator (a system consisting of 50% of potassium persulfate and 50% of sodium bisulfite), stirring and reacting for 6 hours, adding thiourea and zirconium acetate into the obtained solution, reacting for 6 hours at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a product II; the initiator, thiourea and zirconium acetate are added in the mass ratio of 1:0.1:1.
According to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 40% hydrochloric acid solution in an amount of 10mL to obtain a product III, mixing the products I, II and III according to a volume ratio of 0.5:0.1:1, fully and uniformly stirring, calcining the mixture at 600 ℃ for 45min, crushing, melting at 1500 ℃ under 0.15MPa for 40min, and then cooling and molding in a mold to obtain a final product.
Example 3: mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof (mixed solution of titanium, iron, calcium oxide and aluminum oxide which are uniformly stirred at normal temperature with ammonia water according to the mass volume ratio of 1g to 10mL and the mass volume ratio of 1:1:1), reacting for 4 hours at 100 ℃, cooling to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder, the silicon nitride powder and the water is 1g:6g: an amount of 40mL was mixed.
According to the mass percentage, 50% of 2-acryloyloxyisopentenyl sulfonic acid, 20% of methacrylamide and 30% of vinylpyrrolidone are mixed and dissolved in enough water, sodium hydroxide is added at the same time to control the pH value of the system to be 8.0-10.0, the solution is heated to 30 ℃, an initiator (a system consisting of 50% potassium persulfate and 50% sodium bisulfite) is added to react for 10 hours under stirring, cobalt chloride and chromium acetate are added to the obtained solution to react for 4 hours at 60 ℃, and the product II is obtained after the reaction is finished and cooled to room temperature; the initiator, cobalt chloride and chromium acetate are added according to the mass ratio of 1:0.7:1.
According to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 30% acetic acid solution in the amount of 20mL to obtain a product III, mixing the products I, II and III according to the volume ratio of 0.8:0.03:1, fully and uniformly stirring, calcining the mixture at 800 ℃ for 35min, crushing, melting at 1500 ℃ under 0.25MPa for 20min, and then cooling and molding in a mold to obtain the final product.
Example 4: mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof (mixed solution of magnesium, calcium, aluminum and copper according to the mass ratio of 1:1:1, wherein the obtained mixture ammonia water is uniformly stirred at normal temperature according to the mass volume ratio of 2g:12 mL), reacting for 6 hours at 125 ℃, cooling to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder, the silicon nitride powder and the water is 1g:5g: an amount of 40mL was mixed.
According to mass percent, 30 percent of 2-acryloyloxyisopentenyl sulfonic acid, 20 percent of methacrylamide and 50 percent of vinylpyrrolidone are mixed and dissolved in enough water, sodium hydroxide is added at the same time to control the pH value of the system to be 8.0-10.0, the solution is heated to 50 ℃, an initiator (a system consisting of 50 percent of potassium persulfate and 50 percent of sodium bisulfite) is added to react for 8 hours, cobalt chloride and chromium acetate are added into the obtained solution to react for 5 hours at 60 ℃, and the product II is obtained after the reaction is finished and cooled to room temperature; the initiator, cobalt chloride and chromium acetate are added according to the mass ratio of 1:0.4:1.
According to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 35% acetic acid solution in 15mL to obtain a product III, mixing the products I, II and III according to the volume ratio of 0.7:0.06:1, fully and uniformly stirring, calcining the mixture at 700 ℃ for 40min, crushing, melting at 1400 ℃ under 0.20MPa for 30min, and then cooling and molding in a mold to obtain the final product.
Comparative example 1:
according to mass percent, 2-methacryloxybutyl sulfonic acid 40%, methacrylamide 30% and vinyl pyrrolidone 30% are mixed and dissolved in enough water, sodium hydroxide is added at the same time to control the pH value of the system to be 8.0-10.0, an initiator (a system consisting of 50% potassium persulfate and 50% sodium bisulfite) is added after the temperature of the solution is raised to 40 ℃ for stirring reaction for 8 hours, thiourea and zirconium acetate are added into the obtained solution for reaction for 5 hours at 70 ℃, and the product II is obtained after the reaction is finished and cooled to room temperature; the initiator, thiourea and zirconium acetate are added in the mass ratio of 1:0.4:1.
According to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 35% hydrochloric acid solution in 15mL to obtain a product III, mixing the products II and III according to the volume ratio of 0.07:1, fully and uniformly stirring, calcining the mixture at 700 ℃ for 40min, crushing, melting at 1450 ℃ under 0.20MPa for 30min, and then cooling and molding in a mold to obtain the final product.
Comparative example 2:
mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the obtained suspension with alkaline solution of metal or a compound thereof (mixed solution of magnesium, calcium oxide and titanium which are uniformly stirred with ammonia water at normal temperature according to the mass volume ratio of 2g to 13mL, wherein the mass ratio of the mixed solution is 1 to 1.5), reacting the mixed solution at 125 ℃ for 6 hours, cooling the mixed solution to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder, the silicon nitride powder and the water is 1g:4.5g: an amount of 30mL was mixed.
According to the mass volume ratio of 1g: the bone ash is ultrasonically dispersed in 35 percent hydrochloric acid solution in the amount of 15mL to obtain a product III, and the product I, III is prepared according to the volume ratio of 0.6:1, then calcining the mixture at 700 ℃ for 40min, crushing, melting at 1450 ℃ under 0.20MPa for 30min, and then placing the mixture in a mould for cooling and forming to obtain the final product.
Comparative example 3:
according to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 35% hydrochloric acid solution to obtain a product III, calcining the product III at 700 ℃ for 40min, crushing, melting at 1450 ℃ under 0.20MPa for 30min, and then placing the product III in a mould for cooling and forming to obtain a final product.
Test example 1 comparison of physicochemical Properties of different products
The products of examples 1-4 and comparative examples 1-3 were tested for density, mohs hardness with reference to the GB/T16553-2010 "jewellery jade-appraisal" standard; the products of examples 1 to 4 and comparative examples 1 to 3 were tested for compressive strength and porosity at room temperature with reference to GB/T10325-2012 Standard of sampling test for the acceptance of shaped refractory products, and the results are shown in Table 1.
TABLE 1 comparison of physicochemical Properties of different products
| Group of | Compressive strength MPa | Porosity% | Average pore diameter μm | Density g/cm 3 | Hardness of Mohs |
| Example 1 | 93 | 5 | 5 μm or less | 9.73 | 9 |
| Example 2 | 87 | 9 | Less than 6 mu m | 9.65 | 8.5 |
| Example 3 | 90 | 7 | Less than 6 mu m | 9.70 | 8.5 |
| Example 4 | 92 | 7 | 5 μm or less | 9.77 | 8.5 |
| Comparative example 1 | 76 | 11 | Less than 6 mu m | 9.51 | 6 |
| Comparative example 2 | 73 | 14 | Less than 6 mu m | 9.49 | 6.5 |
| Comparative example 3 | 42 | 19 | Below 8 μm | 9.12 | 5 |
As can be seen from the results of Table 1, the bone ash material obtained in examples 1 to 4 of the present invention is excellent in physicochemical properties as compared with comparative examples 1 to 3.
While the invention has been described with respect to preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and that any such changes and modifications as described in the above embodiments are intended to be within the scope of the invention.
Claims (9)
1. The preparation method of the high-temperature-resistant composite bone ash crystal material is characterized by comprising the following steps of:
mixing silicon powder and silicon nitride powder, re-suspending the mixture in water to obtain suspension, mixing the suspension with alkaline solution of metal or metal compound according to the volume ratio of 1:0.08-0.1, reacting for 4-8h at 100-150 ℃, cooling to room temperature after the reaction is finished, and filtering the product to obtain a product I; the mass volume ratio of the silicon powder to the silicon nitride powder to the water is 1g:3-6g: mixing in an amount of 20-40 mL;
according to mass percent, 30-50% of sulfonic acid monomer, 20-40% of methyl acrylamide and 30-50% of vinyl pyrrolidone are mixed and dissolved in enough water, meanwhile, a pH regulator is added to control the pH value of the system to be 8.0-10.0, the solution is heated to 30-50 ℃, then an initiator is added to stir and react for 6-10 hours, a stabilizer and a cross-linking agent are added into the obtained solution to react for 4-6 hours at 60-80 ℃, and after the reaction is finished, the solution is cooled to room temperature, thus obtaining a product II; the initiator, the stabilizer and the cross-linking agent are added according to the mass ratio of 1:0.1-0.7:1;
according to the mass volume ratio of 1g: ultrasonically dispersing bone ash in 30-40% diluted acid solution in an amount of 10-20mL to obtain a product III, mixing the products I, II and III according to a volume ratio of 0.5-0.8:0.03-0.1:1, fully and uniformly stirring, calcining the mixture at 600-800 ℃ for 35-45min, crushing, melting at 1400-1500 ℃ for 20-40min under 0.15-0.25MPa, and cooling and molding in a mold to obtain the final product.
2. The preparation method according to claim 1, wherein the alkaline solution of the metal or the compound thereof is prepared from the metal or the compound thereof and ammonia water according to the mass volume ratio of 1-3g:10-15mL of the mixed solution is evenly stirred at normal temperature.
3. The method according to claim 2, wherein the metal or the compound thereof is selected from the group consisting of a simple metal or an oxide thereof or a hydroxide thereof, or a mixture of at least two of the following: magnesium, calcium, aluminum, iron, titanium, manganese, copper, zinc.
4. The method according to claim 1, wherein the sulfonic acid monomer is selected from any one of 2-methacryloxybutyl sulfonic acid, 2-acryloxybutyl sulfonic acid, and 2-acryloxyisopentenyl sulfonic acid.
5. The method according to claim 1, wherein the initiator is an oxidation-reduction initiation system, the oxidant is one of potassium persulfate, ammonium persulfate, and hydrogen peroxide, and the reducing agent is one of sodium bisulfite, sodium sulfite, sodium thiosulfate, tetramethyl ethylenediamine, ferrous chloride, and cuprous chloride.
6. The method of claim 1, wherein the stabilizer is thiourea or cobalt chloride.
7. The method of claim 1, wherein the cross-linking agent is chromium acetate or zirconium acetate.
8. The method of claim 1, wherein the pH adjuster is sodium hydroxide or potassium hydroxide.
9. The method of claim 1, wherein the dilute acid solution comprises hydrochloric acid, nitric acid, acetic acid, oxalic acid, or citric acid.
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