CN111792923A - 一种耐火材料砖及其制备方法 - Google Patents
一种耐火材料砖及其制备方法 Download PDFInfo
- Publication number
- CN111792923A CN111792923A CN202010701638.3A CN202010701638A CN111792923A CN 111792923 A CN111792923 A CN 111792923A CN 202010701638 A CN202010701638 A CN 202010701638A CN 111792923 A CN111792923 A CN 111792923A
- Authority
- CN
- China
- Prior art keywords
- particle
- parts
- nano
- refractory brick
- grinding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011449 brick Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims description 32
- 239000002245 particle Substances 0.000 claims abstract description 198
- 239000000463 material Substances 0.000 claims abstract description 159
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000005350 fused silica glass Substances 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052849 andalusite Inorganic materials 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 28
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 239000007767 bonding agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims description 73
- 238000001035 drying Methods 0.000 claims description 48
- 230000035939 shock Effects 0.000 claims description 32
- 238000003892 spreading Methods 0.000 claims description 31
- 230000007480 spreading Effects 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000004375 Dextrin Substances 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 238000006703 hydration reaction Methods 0.000 abstract description 15
- 230000036571 hydration Effects 0.000 abstract description 13
- 239000002893 slag Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 67
- 229910010271 silicon carbide Inorganic materials 0.000 description 51
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011819 refractory material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 10
- 229910052863 mullite Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000001976 improved effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62857—Coating fibres with non-oxide ceramics
- C04B35/62873—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
- C04B35/6316—Binders based on silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9684—Oxidation resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开了一种耐火材料砖，由以下重量份的原料制成：大颗粒红柱石、小颗粒红柱石、大颗粒熔融石英、中颗粒熔融石英、小颗粒熔融石英、石墨烯片改性纳米氧化铝、C@SiC晶须粉末、纳米氧化铝、纳米氧化钛、纳米氧化钒、结合剂。本发明通过分级混料，使得物料颗粒充分活化，同时采用分层铺料，使物料层之间形成了有序的功能结构，使得耐火材料砖具有良好的抗腐蚀性能、抗渣性能和抗水化性能，由外层向内层颗粒粒度逐层增大，经压制及烧结后形成抗裂纹能力逐步增强的骨架结构，使得耐火材料砖具有高的耐压强度和韧性。
Description
技术领域
本发明涉及耐火材料技术领域，具体涉及一种耐火材料砖及其制备方法。
背景技术
耐火材料一般是指耐火度不低于1580℃的无机非金属材料或者制品，主要用于炼铁工业的高炉、转炉、焦炉，炼钢行业的转炉、二次精炼炉、连铸等，还用于水泥窑以及玻璃、有色金属的窑炉等。
随着行业技术的不断革新，各行各业对于使用的耐火材料的综合性能要求也随之提高。选用中小粒度的物料能够降低显气孔率，提高耐火材料的抗腐蚀性及抗水性，但由于中小颗粒对裂纹的阻挡能力较弱，会造成耐压强度及韧性的明显下降，导致耐火材料使用寿命缩短。因此，研发低显气孔率同时又具有良好的韧性、抗水化性和抗腐蚀性，且使用周期长的耐火材料产品具有重要意义。
发明内容
针对现有耐火材料的不足，本发明提供了一种韧性好、抗腐蚀性强、使用周期长的耐火材料砖。本发明还提供了该耐火材料砖的制备方法。
本发明的目的通过如下技术方案实现：
一种耐火材料砖，由以下重量份的原料制成：大颗粒红柱石6～12份、小颗粒红柱石9～18份、大颗粒熔融石英15～30份、中颗粒熔融石英5～10份、小颗粒熔融石英10～20份、石墨烯片改性纳米氧化铝5～9份、C@SiC晶须粉末7～12份、纳米氧化铝8～16份、纳米氧化钛3～5份、纳米氧化钒2～3份、结合剂4～8份。
进一步地，所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
进一步地，所述结合剂包括结合剂A和结合剂B；结合剂A为聚合氯化铝、糊精、聚乙二醇中的一种或几种；结合剂B为碱性纳米硅溶胶。
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：将大颗粒红柱石、大颗粒熔融石英混合均匀，采用震击式球磨仪研磨后烘干，然后将3～5份结合剂A加入烘干的物料中，搅拌使物料表面湿润，得物料1；
将小颗粒红柱石、中颗粒熔融石英混合均匀，采用震击式球磨仪研磨后烘干，得物料2；
将小颗粒熔融石英、石墨烯片改性纳米氧化铝、C@SiC晶须粉末混合均匀，采用震击式球磨仪研磨后烘干，得物料3；
将纳米氧化铝、纳米氧化钛、纳米氧化钒混合均匀，采用纳米研磨机研磨后烘干，然后将1～3份结合剂B加入烘干的物料中，搅拌使物料表面湿润，得物料4；
(2)铺料：将物料4在模具底部平铺一层，之后再平铺一层物料3，再平铺一层物料2，最后平铺一层物料1，接着平铺一层物料2，再平铺一层物料3，最上层平铺一层物料4；
(3)制坯：压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在110～130℃烘烤4～12h，再转入高温炉1200～1500℃下烧结3～5h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，步骤(1)中采用震击式球磨仪研磨的具体操作为：加入物料重量2倍的助磨剂，物料重量一半的研磨球，采用震击式球磨仪研磨，将研磨后的物料在60～80℃下烘干。
进一步地，步骤(1)中采用震击式球磨仪研磨所用的助磨剂为无水乙醇，研磨时间0.5～2h。
进一步地，步骤(1)中采用纳米研磨机研磨所用的助磨剂为质量分数为40％～60％的油酸溶液，研磨时间2～4h。
进一步地，步骤(1)中研磨后物料的烘干温度为60～80℃。
进一步地，步骤(3)中压制的强度为60～130MPa。
本发明采用分级混合、研磨的方法，将粒径接近的组分混合均匀后研磨，物料颗粒能够充分与研磨球接触，不会发生沉底、成团现象，随着研磨时间的增加，物料颗粒表面会存在一些机械性损伤的磨蚀创伤面，进而产生新的活化点，同时颗粒内部产生缺陷和裂纹，有利于烧结过程中晶格活化，形成莫来石。
本发明采用分层铺料的方法，打破常规碾混使各物料的粒径及分布尽可能均匀的方法，由于分层采用纳米颗粒层--小颗粒层--中颗粒层--大颗粒层--中颗粒--小颗粒层—纳米颗粒层的顺序自下而上铺料，物料1即表面浸润有结合剂的大颗粒层和物料2即中颗粒层位于耐火材料砖的中间，中颗粒通过结合剂的作用与大颗粒结合成为一体，作为耐火材料的骨架，保证耐火材料砖的机械强度，物料3小颗粒层含有石墨烯片改性纳米氧化铝和C@SiC晶须粉末在煅烧过程中能够将大颗粒层与中颗粒层结合在一起，通过起到增韧功效，物料4纳米颗粒层经油酸改性的氧化钛能提升耐火材料的抗水化性能，同时经硅溶胶润湿后的纳米颗粒层经压制和烧结后结构致密，还能减少杂质的引入，使得耐火材料砖具有良好的抗水化和抗腐蚀性能。
本发明所用红柱石在耐火材料砖坯体烧结过程中会发生不可逆的晶体转化，从而形成具有莫来石网络的莫来石，本发明分层铺料的过程中大颗粒层和中颗粒层分别含有粒径为1～3mm的红柱石大颗粒和粒径为0.1～1mm红柱石小颗粒，烧结过程中红柱石转化成的莫来石网络贯穿大颗粒层与两侧的中颗粒层使其成为一体整体，制备得到的耐火材料砖具有1800℃以上的耐火性能，且机械强度大、抗热冲击力和抗渣性强、耐骤冷骤热、荷重转化点高，还具有优异的化学稳定性和抗化学腐蚀性。
本发明所用熔融石英按粒径分为三级，大颗粒熔融石英与大颗粒红柱石混合研磨后用结合剂润湿作为物料1，其能够大大降低耐火材料砖骨架的热膨胀率和化学稳定性，提高耐火材料砖的综合性能；熔融石英在高温时液相的粘度很大，因此高温时耐侵蚀冲刷性能很好，中颗粒熔融石英和小颗粒熔融石英分层分布，且小颗粒熔融石英分布在靠外侧，与纳米颗粒层烧结后，能够大大提高耐火材料砖的抗腐蚀性和高温耐侵蚀性能。
本发明所用石墨烯片改性纳米氧化铝，通过高倍透射电子显微镜观察发现石墨烯的增强增韧方式主要有颗粒钉扎、石墨烯拔出和裂纹桥接，此外石墨烯引入还能抑制纳米氧化铝晶粒生长。C@SiC晶须粉末作为小颗粒层的物料，与表层紧密结合，C@SiC晶须粉末为石墨包裹碳化硅的核壳结构，碳化硅在高温下仍能保持高的键合强度，硬度高，弹性膜量大，能够防止耐火材料被酸碱溶液所侵蚀，高温下石墨层能够阻止碳化硅发生氧化，从而避免材料内部产生厚的氧化层导致结构疏松，使得C@SiC晶须粉末的增韧功效能够长效保持，延长耐火材料砖的使用寿命。
硅溶胶的结合机理是溶胶中SiO2粒子通过表面的极性硅氧基(-Si-O-)发生脱水缩合反应，将硅溶胶中SiO2粒子连接在一起形成稳定的三维网络结构，进而将小颗粒层和纳米颗粒层粘结成整体，提供耐火材料砖的初期强度。碱性纳米硅溶胶作为结合剂能克服其他结合剂对温度过于敏感的缺点，改善材料的中温强度；另外碱性纳米硅溶胶作为结合剂，能减少杂质的引入，提高材料的高温性能和抗腐蚀性能。
氧化钒(V2O5)对莫来石晶须的生长有促进作用，主要体现在两个方面：一是氧化钒在高温下挥发，促进莫来石气-固生长机制；二是氧化钒具有活化作用，能增加氧化铝的晶格缺陷，活化晶格，促进莫来石的形成。研究表明，适量的氧化钒加入有利于莫来石的形成，过量则会促使鳞片状(块状)莫来石含量增加，而导致材料的强度降低。
本发明与现有技术相比具有以下有益效果：
(1)本发明提供的耐火材料砖制备方法通过分级混料，使得物料颗粒充分活化，同时采用分层铺料，使物料层之间形成了有序的功能结构，大颗粒及中颗粒层作为耐火材料砖的骨架，保证耐火材料砖的机械强度；小颗粒层含有增韧材料石墨烯片改性纳米氧化铝提升耐火材料砖的韧性，C@SiC晶须粉末提高材料的抗氧化和抗腐蚀性能，此外，C@SiC晶须粉末具有良好的吸波性能，还能够大大提高材料的保温性能；纳米颗粒层物料粒径小，且经油酸改性，经压制和烧结后结构致密、性质稳定，具有良好的抗渣、抗腐蚀及抗水性能。
(2)本发明提供的耐火材料砖由于特殊的分层铺料工艺，熔融石英高温烧结时包覆在红柱石晶化生成的莫来石颗粒表面，高温条件下内部晶粒发育良好，存在大量闭口气孔，降低了耐火材料的体积密度，制得的耐火材料砖质轻，保温隔热性能好，表层纳米颗粒层致密，在碱性纳米硅溶胶的作用下压制和烧结过程中形成致密的陶瓷结构，因而具有良好的抗腐蚀性能、抗渣性能和抗水化性能，由外层向内层颗粒粒度逐层增大，经压制及烧结后形成抗裂纹能力逐步增强的骨架结构，使得耐火材料砖具有高的耐压强度和韧性。
附图说明
图1为本发明分层铺料示意图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合附图及具体实施例进行详细描述。
实施例1
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：以下份数均为重量份数，将大颗粒红柱石6份、大颗粒熔融石英15份混合均匀，加入42份的无水乙醇，10.5份的研磨球，采用震击式球磨仪研磨，研磨时间0.5h，将研磨后的物料在60℃下烘干，然后将3份聚合氯化铝加入烘干的物料中，搅拌使物料表面湿润，得物料1；
将小颗粒红柱石9份、中颗粒熔融石英5份混合均匀，加入28份的无水乙醇，7份的研磨球，采用震击式球磨仪研磨，研磨时间0.5h，将研磨后的物料在60℃下烘干，得物料2；
将小颗粒熔融石英10份、石墨烯片改性纳米氧化铝5份、C@SiC晶须粉末7份混合均匀，加入44份的无水乙醇，11份的研磨球，采用震击式球磨仪研磨，研磨时间0.5h，将研磨后的物料在60℃下烘干，得物料3；
将纳米氧化铝8份、纳米氧化钛3份、纳米氧化钒2份混合均匀后，加入26份的质量分数为40％的油酸溶液，采用纳米研磨机研磨2h，将研磨后的物料在60℃下烘干，然后将1份碱性纳米硅溶胶加入烘干的物料中，搅拌使物料表面湿润，得物料4；
(2)铺料：将物料4在模具底部平铺一层，之后再平铺一层物料3，再平铺一层物料2，最后平铺一层物料1，接着平铺一层物料2，再平铺一层物料3，最上层平铺一层物料4(如图1所示)；
(3)制坯：60MPa下压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在110℃烘烤4h，再转入高温炉1200℃下烧结3h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
实施例2
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：以下份数均为重量份数，将大颗粒红柱石9份、大颗粒熔融石英21份混合均匀，加入60份的无水乙醇，15份的研磨球，采用震击式球磨仪研磨，研磨时间1h，将研磨后的物料在70℃下烘干，然后将4份糊精加入烘干的物料中，搅拌使物料表面湿润，得物料1；
将小颗粒红柱石12份、中颗粒熔融石英8份混合均匀，加入40份的无水乙醇，10份的研磨球，采用震击式球磨仪研磨，研磨时间1h，将研磨后的物料在70℃下烘干，得物料2；
将小颗粒熔融石英15份、石墨烯片改性纳米氧化铝7份、C@SiC晶须粉末10份混合均匀，加入64份的无水乙醇，其16份的研磨球，采用震击式球磨仪研磨，研磨时间1h，将研磨后的物料在70℃下烘干，得物料3；
将纳米氧化铝14份、纳米氧化钛4份、纳米氧化钒2份混合均匀后，加入二者重量2倍的质量分数为50％的油酸溶液，采用纳米研磨机研磨3h，将研磨后的物料在70℃下烘干，然后将2份碱性纳米硅溶胶加入烘干的物料中，搅拌使物料表面湿润，得物料4；
(2)铺料：将物料4在模具底部平铺一层，之后再平铺一层物料3，再平铺一层物料2，最后平铺一层物料1，接着平铺一层物料2，再平铺一层物料3，最上层平铺一层物料4(如图1所示)；
(3)制坯：100MPa下压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在120℃烘烤8h，再转入高温炉1400℃下烧结4h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
实施例3
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：以下份数均为重量份数，将大颗粒红柱石12份、大颗粒熔融石英30份混合均匀，加入64份的无水乙醇，16份的研磨球，采用震击式球磨仪研磨，研磨时间2h，将研磨后的物料在80℃下烘干，然后将5份聚乙二醇加入烘干的物料中，搅拌使物料表面湿润，得物料1；
将小颗粒红柱石18份、中颗粒熔融石英10份混合均匀，加入56份的无水乙醇，14份的研磨球，采用震击式球磨仪研磨，研磨时间2h，将研磨后的物料在80℃下烘干，得物料2；
将小颗粒熔融石英20份、石墨烯片改性纳米氧化铝9份、C@SiC晶须粉末12份混合均匀，加入82份的无水乙醇，20.5份的研磨球，采用震击式球磨仪研磨，研磨时间2h，将研磨后的物料在80℃下烘干，得物料3；
将纳米氧化铝16份、纳米氧化钛5份、纳米氧化钒3份混合均匀后，加入48份的质量分数为60％的油酸溶液，采用纳米研磨机研磨4h，将研磨后的物料在80℃下烘干，然后将3份碱性纳米硅溶胶加入烘干的物料中，搅拌使物料表面湿润，得物料4；
(2)铺料：将物料4在模具底部平铺一层，之后再平铺一层物料3，再平铺一层物料2，最后平铺一层物料1，接着平铺一层物料2，再平铺一层物料3，最上层平铺一层物料4(如图1所示)；
(3)制坯：130MPa下压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在130℃烘烤12h，再转入高温炉1500℃下烧结3～5h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，步骤(1)所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，步骤(1)所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，步骤(1)所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，步骤(1)所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，步骤(1)所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
性能测试
①荷软温度
根据GB/T 5989-2008示差升温法测试耐火材料的荷重软化温度。将试样制作成中心带通孔的圆柱体，直径Φ50mm，高度50mm，中心通孔直径Φ12～Φ12mm，并与圆柱体同轴。对试样施加0.2MPa的压力，升温程序：≤1000℃时，升温速率为10℃/min；＞1000℃时，升温速率为5℃/min，直至试验结束。试样变形量为0.6％时，记录结果。
②显气孔率
根据GB/T 2997-2000)和ISO 5017测试气孔率。使用50mm3的立方体试样，先称量干燥试样的质量m1，然后让试样在容器中抽真空，在加入水充分饱和试样，称量水饱和试样的质量在水中的悬浮重量m2以及水饱和试样在空气中的质量m3。显气孔率的计算公式为：
体积密度的计算公式为：
式中πa——耐火材料砖的显气孔率，％；ρb——耐火材料砖的体积密度，g/cm3；m1——干燥试样的质量，g；；m2——水饱和试样的悬浮质量，g；；m3——饱和试样在空气中的质量，g。
③常温耐压强度
耐火材料的常温耐压强度按GB/T 5072，GB/T 3001规定的方法测定。在机械或液压试验机上以规定的加压速率对圆形或者方形的试样加荷，直到试样破碎。根据记录的最大载荷和试样受载荷的面积，用公式(3)计算试样的耐压强度：
式中S——试样的耐压强度，MPa；P——试样破碎时的最大载荷，N；A1，A2——分别为试样上下受压面的面积，mm2。
④高温抗折强度
高温抗折强度根据GB/T 3002～2004进行测试。将经过高温烧成并冷却的条形试样按规定间隔置于可移动间距为125mm的两个下刀口的滑板上装进试验炉内，调节试样与上刀口的间距不小于5mm。加热到1350℃时保温30min后，将试样对称地置于下刀口上，使上刀口在试样的压力面中部垂直均匀加荷直至断裂，记录断裂时的最大载荷。按照公式(4)计算抗折强度：
式中，Re——抗折强度，MPa；Fmax——试样断裂时的最大载荷，N；Ls——支承刀口之间的距离，mm；b——试样的宽度，mm；h——试样的高度，mm。
⑤抗热震性能
试样干燥：试样于110±5℃，或允许的较高的温度下干燥至恒重。干燥后式样不能受潮。
试样急热过程：将干燥后的试样，放入预加热至200～300℃的干燥箱内至少保持2h。加热炉预加热至950±10℃保温15min后，迅速将试样移入炉膛内。立即关闭炉门，炉温下降不应大于0℃。5min内将炉温升至950±10℃。试样在此温度下保持30min。
试样的急冷过程：将试样迅速从炉膛内取出，用冷空气吹5min。
重复以上冷热交替实验5次，试样在热冷交替的过程中，严禁发生碰撞、摔裂等外力损伤。
试样的常温耐压强度的保持率来表示抗热震性的好坏。计算公式如下：
式中，σFR——常温抗压强度保持率，％；σFa——热震后试样的常温抗压强度，MPa；σFb——热震前试样的常温抗压强度，MPa。
⑥抗水化性能
将20ml的小烧杯洗干净放干燥箱内烘干至恒重，试样破碎过40目筛，要筛上样，称取10g～50g(m1)，放入烧杯中，再将烧杯放置20℃、90％湿度的恒温恒湿箱中72h，水化完成后将试样放入干燥箱内，烘干至恒重(m2)。试样的水化增重率为：
式中，ψ(％)——试样的水化增重率，％；m1——试样水化前的质量，g；m2——试样水化后的质量，g。
⑦抗腐蚀性能
根据国标GB/T14983-2008中的熔碱坩埚法对样品进行抗碱腐蚀性测试。试样的抗熔碱性以试样的质量变化率mr表示，数值以％计，按式(7)计算：
式中，mr——试样的质量变化率；m——抗碱试验前试验的质量，g；m1——抗碱试验后试样的质量，g。
对实施例1～3制得的耐火材料砖样品进行上述性能测试，测试结果如下表1所示：
表1
| 检测项 | 实施例1 | 实施例2 | 实施例3 |
| 荷软温度(℃) | 1745 | 1746 | 1742 |
| 显气孔率π<sub>a</sub>(％) | 6.52 | 6.19 | 6.65 |
| 体积密度ρ<sub>b</sub>(g/cm<sup>3</sup>) | 2.38 | 2.27 | 2.34 |
| 常温耐压强度S(MPa) | 145.69 | 148.21 | 148.03 |
| 高温抗折强度Re(MPa) | 15.5 | 15.8 | 15.9 |
| 抗热震性能σ<sub>FR</sub>(％) | 82.37 | 84.55 | 84.06 |
| 抗水化性能ψ(％) | 10.6 | 11.4 | 11.3 |
| 抗腐蚀性能m<sub>r</sub> | 4.2 | 4.5 | 4.4 |
从表1可以看出，本发明实施例1～3制得耐火材料砖荷软温度大于1700℃，显气孔率低于7％，体积密度在2.2～2.4g/cm3之间，常温耐压强度大于145MPa，高温抗折强度大于15MPa，抗热震和抗水化性能优异。
对比例1
除步骤(1)红柱石粒径均为1～3mm，即用大颗粒红柱石替换小颗粒红柱石外，其余同实施例2。
对比例2
除步骤(1)红柱石粒径均为0.1～1mm，即用小颗粒红柱石替换大颗粒红柱石外，其余同实施例2。
对比例3
除步骤(1)熔融石英粒径均为1～3mm，即用大颗粒熔融石英替换中颗粒和小颗粒熔融石英外，其余同实施例2。
对比例4
除步骤(1)熔融石英粒径均为0.1～1mm，即用中颗粒熔融石英替换大颗粒和小颗粒熔融石英外，其余同实施例2。
对比例5
除步骤(1)熔融石英粒径均为400目，即用小颗粒熔融石英替换大颗粒和中颗粒熔融石英外，其余同实施例2。
对比例6
除步骤(1)用微米级氧化铝、氧化钛、氧化钒替换粒径为200～500nm的纳米氧化铝、纳米氧化钛、纳米氧化钒外，其余同实施例2。
对对比例1～6制得的耐火材料砖样品进行上述性能测试，测试结果如下表2所示：
表2
从表2可以看出，本发明对比例1～6制得耐火材料砖的体积密度随中颗粒和小颗粒用量的增加而增大，显气孔率随中颗粒和小颗粒颗粒用量的增加而减小，但是中颗粒和小颗粒用量增加后，耐火材料砖的常温耐压强度和高温抗折强度急剧下降，抗热震性能也大大减弱，这可能是由于不含大颗粒时，材料在受压时微裂纹容易穿过中细颗粒，导致材料开裂崩溃，因此合理配比各粒度原料对耐火材料砖的性能具有重要影响。对比例6纳米颗粒替换为微米颗粒，表层致密度下降，抗水化性能大大减弱，体积密度减小，显气孔率增大，耐压强度、高温抗折强度和抗热震性能均有大幅下降，说明材料表层的致密度对材料的整体性能有较大影响。
对比例7
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：以下份数均为重量份数，将大颗粒红柱石9份、大颗粒熔融石英21份、小颗粒红柱石12份、中颗粒熔融石英8份、小颗粒熔融石英15份、石墨烯片改性纳米氧化铝7份、C@SiC晶须粉末10份混合均匀，加入164份的无水乙醇，41份的研磨球，采用震击式球磨仪研磨，研磨时间1h，将研磨后的物料在70℃下烘干，然后将4份糊精加入烘干的物料中，搅拌使物料表面湿润，得物料A；
将纳米氧化铝14份、纳米氧化钛4份、纳米氧化钒2份混合均匀后，加入二者重量2倍的质量分数为50％的油酸溶液，采用纳米研磨机研磨3h，将研磨后的物料在70℃下烘干，然后将2份碱性纳米硅溶胶加入烘干的物料中，搅拌使物料表面湿润，得物料B；
(2)铺料：将物料B在模具底部平铺一层，之后再平铺一层物料A，最上层平铺一层物料B；
(3)制坯：100MPa下压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在120℃烘烤8h，再转入高温炉1300℃下烧结4h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
对比例8
一种耐火材料砖的制备方法，包括以下步骤：
(1)配料：以下份数均为重量份数，将大颗粒红柱石9份、大颗粒熔融石英21份、小颗粒红柱石12份、中颗粒熔融石英8份、小颗粒熔融石英15份、石墨烯片改性纳米氧化铝7份、C@SiC晶须粉末10份混合均匀，加入164份的无水乙醇，41份的研磨球，采用震击式球磨仪研磨，研磨时间1h，将研磨后的物料在70℃下烘干，然后将4份糊精加入烘干的物料中，搅拌使物料表面湿润，得物料A；
将纳米氧化铝14份、纳米氧化钛4份、纳米氧化钒2份混合均匀后，加入二者重量2倍的质量分数为50％的油酸溶液，采用纳米研磨机研磨3h，将研磨后的物料在70℃下烘干，然后将2份碱性纳米硅溶胶加入烘干的物料中，搅拌使物料表面湿润，得物料B；
(2)铺料：将物料A与物料B混合均匀后，平铺到模具中；
(3)制坯：100MPa下压制成型，制得耐火材料砖坯体；
(4)烧结：将耐火材料砖坯体在120℃烘烤8h，再转入高温炉1300℃下烧结4h，烧结完成后自然冷却、切割，即得耐火材料砖。
进一步地，所述大颗粒红柱石粒径为1～3mm，小颗粒红柱石粒径为0.1～1mm。
进一步地，所述大颗粒熔融石英粒径为1～3mm，中颗粒熔融石英粒径为0.1～1mm，小颗粒熔融石英粒径为400目。
进一步地，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0wt％的石墨烯片，放入高频感应加热机中，1500℃下热处理1～2h。
进一步地，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2·6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
进一步地，所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200～500nm。
对比例9
除步骤(4)烧结高温炉温度为1100℃外，其余同实施例2。
对比例10
除步骤(4)烧结高温炉温度为1600℃外，其余同实施例2。
对对比例7～10制得的耐火材料砖样品进行上述性能测试，测试结果如下表3所示：
表3
| 检测项 | 实施例2 | 对比例7 | 对比例8 | 对比例9 | 对比例10 |
| 荷软温度(℃) | 1746 | 1654 | 1627 | 1426 | 1743 |
| 显气孔率π<sub>a</sub>(％) | 6.19 | 15.38 | 15.74 | 10.19 | 6.08 |
| 体积密度ρ<sub>b</sub>(g/cm<sup>3</sup>) | 2.27 | 2.45 | 2.42 | 2.11 | 2.56 |
| 常温耐压强度S(MPa) | 148.21 | 81.04 | 66.43 | 123.25 | 148.20 |
| 高温抗折强度Re(MPa) | 15.8 | 10.5 | 8.1 | 13.8 | 15.9 |
| 抗热震性能σ<sub>FR</sub>(％) | 84.55 | 72.46 | 69.28 | 68.64 | 84.52 |
| 抗水化性能ψ(％) | 11.4 | 15.3 | 15.8 | 16.7 | 11.3 |
| 抗腐蚀性能m<sub>r</sub> | 4.5 | 12.5 | 13.7 | 9.4 | 4.3 |
从表3可以看出，对比例7和对比例8制得的耐火材料砖各项性能均不及实施例2，表明本发明分级混料及分层铺料对提升耐火材料砖的性能起到关键作用；对比例9烧结温度较低，耐火材料砖的显气孔率较高，抗水化性能较差，耐压强度和高温抗折强度也明显降低，这可能是由于材料结构不够致密，导致各项性能变差；对比例10烧结温度较高，除显气孔率略有下降外，其余各项性能与实施例2相比没有明显提升，从能源节约的角度选定烧结温度为1200～1500℃。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，本领域普通技术人员对本发明的技术方案所做的其他修改或者等同替换，只要不脱离本发明技术方案的精神和范围，均应涵盖在本发明的权利要求范围当中。
Claims (9)
1.一种耐火材料砖，其特征在于，由以下重量份的原料制成：大颗粒红柱石6~12份、小颗粒红柱石9~18份、大颗粒熔融石英15~30份、中颗粒熔融石英5~10份、小颗粒熔融石英10~20份、石墨烯片改性纳米氧化铝5~9份、C@SiC晶须粉末7~12份、纳米氧化铝8~16份、纳米氧化钛3~5份、纳米氧化钒2~3份、结合剂4~8份。
2.根据权利要求1所述的耐火材料砖，其特征在于，所述大颗粒红柱石粒径为1~3 mm，小颗粒红柱石粒径为0.1~1 mm；所述大颗粒熔融石英粒径为1~3 mm，中颗粒熔融石英粒径为0.1~1 mm，小颗粒熔融石英粒径为400目；所述纳米氧化铝、纳米氧化钛、纳米氧化钒的粒径均为200~500 nm。
3.根据权利要求1所述的耐火材料砖，其特征在于，所述石墨烯片改性纳米氧化铝的制备方法为：在纳米氧化铝粉中加入0.25-3.0 wt%的石墨烯片，放入高频感应加热机中，1500℃下热处理1~2 h。
4.根据权利要求1所述的耐火材料砖，其特征在于，所述C@SiC晶须粉末的制备方法为：S1、将SiC晶须粉末在空气气氛中烘烧，再用HF溶液浸泡；S2、用NiCl2 ▪6H2O颗粒和去离子水配置NiCl2溶液；S3、向步骤二配置的NiCl2溶液中加入经步骤一处理的SiC晶须，水浴搅拌，然后烘干，研磨均匀，得到NiCl2包覆SiC晶须粉末；S4、然后在惰性气体保护下高温处理，除去杂质，烘干，研磨，得到C@SiC晶须粉末。
5.根据权利要求1所述的耐火材料砖，其特征在于，所述结合剂包括结合剂A和结合剂B；结合剂A为聚合氯化铝、糊精、聚乙二醇中的一种或几种；结合剂B为碱性纳米硅溶胶。
6.一种权利要求1~5任一项所述的耐火材料砖的制备方法，其特征在于，包括以下步骤：
（1）配料：将大颗粒红柱石、大颗粒熔融石英混合均匀，采用震击式球磨仪研磨后烘干，然后将结合剂A加入烘干的物料中，搅拌使物料表面湿润，得物料1；
将小颗粒红柱石、中颗粒熔融石英混合均匀，采用震击式球磨仪研磨后烘干，得物料2；
将小颗粒熔融石英、石墨烯片改性纳米氧化铝、C@SiC晶须粉末混合均匀，采用震击式球磨仪研磨后烘干，得物料3；
将纳米氧化铝、纳米氧化钛、纳米氧化钒混合均匀，采用纳米研磨机研磨后烘干，然后将结合剂B加入烘干的物料中，搅拌使物料表面湿润，得物料4；
（2）铺料：将物料4在模具底部平铺一层，之后再平铺一层物料3，再平铺一层物料2，最后平铺一层物料1，接着平铺一层物料2，再平铺一层物料3，最上层平铺一层物料4；
（3）制坯：压制成型，制得耐火材料砖坯体；
（4）烧结：将耐火材料砖坯体在110~130 ℃烘烤4~12 h，再转入高温炉1200~1500 ℃下烧结3~5 h，烧结完成后自然冷却、切割，即得耐火材料砖。
7.根据权利要求6所述耐火材料砖的制备方法，其特征在于，步骤（1）中采用震击式球磨仪研磨的具体操作为：加入物料重量2倍的助磨剂，物料重量一半的研磨球，采用震击式球磨仪研磨，将研磨后的物料在60~80 ℃下烘干。
8.根据权利要求6所述耐火材料砖的制备方法，其特征在于，步骤（1）中采用震击式球磨仪研磨所用的助磨剂为无水乙醇，研磨时间0.5~2 h；采用纳米研磨机研磨所用的助磨剂为质量分数为40%~60%的油酸溶液，研磨时间2~4 h。
9.根据权利要求6所述耐火材料砖的制备方法，其特征在于，步骤（3）中压制的强度为60~130 MPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010701638.3A CN111792923B (zh) | 2020-07-20 | 2020-07-20 | 一种耐火材料砖及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010701638.3A CN111792923B (zh) | 2020-07-20 | 2020-07-20 | 一种耐火材料砖及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111792923A true CN111792923A (zh) | 2020-10-20 |
| CN111792923B CN111792923B (zh) | 2022-05-13 |
Family
ID=72807966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010701638.3A Active CN111792923B (zh) | 2020-07-20 | 2020-07-20 | 一种耐火材料砖及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111792923B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754451A (zh) * | 2021-10-22 | 2021-12-07 | 辽宁工业大学 | 利用工业固体废弃物制备的耐火砖及其制备方法 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5843859A (en) * | 1990-05-29 | 1998-12-01 | Claussen; Nils | Reaction-formed moulded ceramic body containing mullite, its production and its use |
| CN1861549A (zh) * | 2006-04-29 | 2006-11-15 | 巩义市华西炉料有限公司 | 硅线石、红柱石微粉结合的耐火球 |
| WO2011055642A1 (ja) * | 2009-11-06 | 2011-05-12 | 三井金属鉱業株式会社 | ムライトセラミックス及びその製造方法 |
| CN103319186A (zh) * | 2013-05-24 | 2013-09-25 | 霍山县新裕炉窑模具有限公司 | 熔铝炉浇注耐火材料及其制备方法 |
| CN105439580A (zh) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | 一种高性能耐火材料 |
| CN106278299A (zh) * | 2016-07-21 | 2017-01-04 | 济源市金峰耐火材料有限公司 | 红柱石复合耐火砖及其制备方法和应用 |
| CN107628808A (zh) * | 2017-10-20 | 2018-01-26 | 广西银英生物质能源科技开发股份有限公司 | 一种陶瓷耐火材料 |
| CN108425008A (zh) * | 2018-06-21 | 2018-08-21 | 攀钢集团攀枝花钢铁研究院有限公司 | 一种菱铁矿的分级布料烧结方法 |
| CN108840670A (zh) * | 2018-08-23 | 2018-11-20 | 江苏江能新材料科技有限公司 | 一种保存时间长的可塑料及其制备方法 |
| CN109053153A (zh) * | 2018-09-11 | 2018-12-21 | 郑州荣盛窑炉耐火材料有限公司 | 一种抗温度急变耐剥落低气孔粘土砖及其制备方法 |
| CN110564366A (zh) * | 2019-09-30 | 2019-12-13 | 哈尔滨工业大学 | 一种使用NiCl2制备耐高温介电性吸波剂C@SiC晶须粉末的制备方法 |
-
2020
- 2020-07-20 CN CN202010701638.3A patent/CN111792923B/zh active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5843859A (en) * | 1990-05-29 | 1998-12-01 | Claussen; Nils | Reaction-formed moulded ceramic body containing mullite, its production and its use |
| CN1861549A (zh) * | 2006-04-29 | 2006-11-15 | 巩义市华西炉料有限公司 | 硅线石、红柱石微粉结合的耐火球 |
| WO2011055642A1 (ja) * | 2009-11-06 | 2011-05-12 | 三井金属鉱業株式会社 | ムライトセラミックス及びその製造方法 |
| CN103319186A (zh) * | 2013-05-24 | 2013-09-25 | 霍山县新裕炉窑模具有限公司 | 熔铝炉浇注耐火材料及其制备方法 |
| CN105439580A (zh) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | 一种高性能耐火材料 |
| CN106278299A (zh) * | 2016-07-21 | 2017-01-04 | 济源市金峰耐火材料有限公司 | 红柱石复合耐火砖及其制备方法和应用 |
| CN107628808A (zh) * | 2017-10-20 | 2018-01-26 | 广西银英生物质能源科技开发股份有限公司 | 一种陶瓷耐火材料 |
| CN108425008A (zh) * | 2018-06-21 | 2018-08-21 | 攀钢集团攀枝花钢铁研究院有限公司 | 一种菱铁矿的分级布料烧结方法 |
| CN108840670A (zh) * | 2018-08-23 | 2018-11-20 | 江苏江能新材料科技有限公司 | 一种保存时间长的可塑料及其制备方法 |
| CN109053153A (zh) * | 2018-09-11 | 2018-12-21 | 郑州荣盛窑炉耐火材料有限公司 | 一种抗温度急变耐剥落低气孔粘土砖及其制备方法 |
| CN110564366A (zh) * | 2019-09-30 | 2019-12-13 | 哈尔滨工业大学 | 一种使用NiCl2制备耐高温介电性吸波剂C@SiC晶须粉末的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 张电: "高强陶瓷薄板的研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754451A (zh) * | 2021-10-22 | 2021-12-07 | 辽宁工业大学 | 利用工业固体废弃物制备的耐火砖及其制备方法 |
| CN113754451B (zh) * | 2021-10-22 | 2022-09-27 | 辽宁工业大学 | 利用工业固体废弃物制备的耐火砖及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111792923B (zh) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Fabrication of SiC reticulated porous ceramics with multi-layered struts for porous media combustion | |
| Bag et al. | Study on low carbon containing MgO-C refractory: Use of nano carbon | |
| US20070203013A1 (en) | Ceramic Batch And Associated Product For Fireproof Applications | |
| CN111704448B (zh) | 一种高强度耐火材料砖及其制备方法 | |
| CN106800420B (zh) | 一种碳化硅晶须原位复合刚玉高温陶瓷材料及其制备方法 | |
| WO2021147592A1 (zh) | 间歇式操作高温窑炉近零热损耐火材料衬体及其制备方法 | |
| CN110028316B (zh) | 一种堇青石窑具匣钵及其制备方法 | |
| Akpinar et al. | Microwave assisted sintering of in-situ cordierite foam | |
| CN110746180A (zh) | 炼铜阳极炉用烧成铝铬锆滑板砖及其制备方法 | |
| CN111792923B (zh) | 一种耐火材料砖及其制备方法 | |
| CN102161590B (zh) | 干熄焦装置关键部位用莫来石-红柱石制品及其制法 | |
| CN111548182A (zh) | 一种多孔陶瓷及其制备方法 | |
| CN113213887A (zh) | 一种高抗热震性陶瓷器皿及其制备方法 | |
| CN114163228B (zh) | 一种铝钙碳质转炉挡渣滑板及其制备方法 | |
| CN111423241A (zh) | 一种具有纤维增韧的莫来石砖及其制备方法 | |
| Amkpa et al. | Influence of sintering temperatures on physico-mechanical properties and microstructure of refractory fireclay bricks | |
| RU2380138C2 (ru) | Усовершенствованный пенокерамический фильтр для улучшения фильтрования расплавленного чугуна | |
| CN106830955B (zh) | 一种微波干燥制备不烧改性高纯镁铝尖晶石复合砖的方法 | |
| Chen et al. | Improved thermal shock resistance of MgO–C refractories with addition of calcium magnesium aluminate (CMA) aggregates | |
| CN109293379B (zh) | 氧化铬砖及其制备方法 | |
| Chen et al. | Improved comprehensive properties of Al2O3-MgO-C refractories containing lightweight tabular alumina aggregates | |
| CN114644525A (zh) | 添加废弃料的复合匣钵及其制备方法 | |
| CN114031381B (zh) | 一种添加氮化硅铁硅砖及其制备方法 | |
| CN112279657B (zh) | 一种轻量矾土基耐火砖及其制备方法 | |
| Wang et al. | Damage mechanism and corrosion resistance improvement of corundum-mullite kiln furniture during calcining of Li-ion cathode materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A refractory brick and its preparation method Effective date of registration: 20221009 Granted publication date: 20220513 Pledgee: Bank of China Limited by Share Ltd. Jiyuan branch Pledgor: JIYUAN JINFENG REFRACTORY MATERIAL Co.,Ltd. Registration number: Y2022980017736 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231024 Granted publication date: 20220513 Pledgee: Bank of China Limited by Share Ltd. Jiyuan branch Pledgor: JIYUAN JINFENG REFRACTORY MATERIAL Co.,Ltd. Registration number: Y2022980017736 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |