EP2632874A1 - Particule en matiere ceramique fondue - Google Patents
Particule en matiere ceramique fondueInfo
- Publication number
- EP2632874A1 EP2632874A1 EP11781657.9A EP11781657A EP2632874A1 EP 2632874 A1 EP2632874 A1 EP 2632874A1 EP 11781657 A EP11781657 A EP 11781657A EP 2632874 A1 EP2632874 A1 EP 2632874A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particle
- oxides
- particle according
- less
- sio
- 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.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims abstract description 82
- 239000000919 ceramic Substances 0.000 title claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000000295 complement effect Effects 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000011324 bead Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000012768 molten material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 OTTAWA sand Chemical compound 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/481—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
-
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/484—Refractories by fusion casting
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
Definitions
- the present invention relates to new melted ceramic particles, in particular in the form of beads, to a process for producing these beads, and to the use of these particles as grinding agents, dispersants in a wet medium or for the treatment of surfaces.
- the mineral industry uses particles for the fine grinding of materials that may be dry-milled by conventional methods, in particular for calcium carbonate, titanium oxide, gypsum, kaolin and iron ore.
- the paints, inks, dyes, magnetic lakes and agrochemicals industries use particles for the dispersion and homogenization of the various liquid and solid constituents.
- the surface treatment industry finally uses particles, especially for cleaning metal molds (for making bottles for example), deburring parts, descaling, preparing a support for a coating, the treatment of pre-constraints ("shot peening"), the forming of parts (“peen forming”) ...
- the particles are conventionally substantially spherical and of a size of 0.005 to 4 mm in order to serve all the markets described above. For them to be used in these three types of applications, they must in particular have good resistance to wear.
- ⁇ Rounded sand such as OTTAWA sand
- OTTAWA sand is a natural, inexpensive product that is not suitable for modern, pressurized, high-volume mills. Indeed, the sand is not very resistant, of low density, variable in quality and abrasive for the material.
- Ceramic balls are also known. These beads have better strength than glass beads, higher density and excellent chemical inertness. We can distinguish :
- ⁇ sintered ceramic beads obtained by cold forming of a ceramic powder, then consolidation by baking at high temperature
- fused ceramic beads generally obtained by melting ceramic components, forming spherical drops from the melt, then solidifying said drops.
- the vast majority of the fused beads have a composition of the zirconia-silica type (Zr0 2 -SiO 2 ) in which the zirconia is crystallized in monoclinic form and / or partially stabilized in quadratic form (by suitable additions), and the silica as well as some of the optional additives form a glassy phase which binds the zirconia crystals.
- the fused ceramic beads provide optimum properties for grinding, ie good mechanical strength, high density, low chemical inertness and abrasiveness to the grinding material.
- Molten zirconia-based ceramic beads and their use for grinding and dispersing are for example described in FR 2,320,276 (US 4,106,947) and EP 0,662,461 (US 5,502,012). These documents describe the influence of SiO 2 , Al 2 O 3 , MgO, CaO, Y 2 O 3 , CeO 2 , and Na 2 0 on the main properties, in particular on the properties of crush resistance and resistance to abrasion.
- the invention aims to meet these needs by providing melted ceramic particles which have excellent resistance to breakage and wear, especially in basic medium. Summary of the invention
- the invention relates to a novel fused ceramic particle, preferably in the form of a ball, having the following chemical composition, in percentages by weight on the basis of the oxides and for a total of 100%:
- the inventors have unexpectedly found that the presence of lanthanum oxide (La 3 O 3 ) and yttrium oxide (Y 2 O 3 ) in the abovementioned proportions significantly improves the properties of the melted ceramic particles, in particular compared to the particles described in FR 2,320,276.
- La 3 O 3 lanthanum oxide
- Y 2 O 3 yttrium oxide
- the particles according to the invention are thus particularly well suited to wet dispersion, micro grinding and surface treatment applications.
- the particles according to the invention have improved breaking resistance during start-up and in use.
- the invention also relates to a particle powder comprising more than
- the invention also relates to a process for producing melted particles according to the invention, in particular melted balls, comprising the following successive steps:
- the raw materials are chosen in step a) so that the particles obtained in step c) are in accordance with the invention.
- oxides of lanthanum, yttrium and aluminum and / or one or more precursors of these oxides are added voluntarily and systematically into the feedstock, preferably in the oxide form, so as to ensure this conformity.
- the invention finally relates to the use of a powder of particles, in particular beads, according to the invention, in particular manufactured according to a process according to the invention, as grinding agents; dispersants in a humid environment; propping agents, in particular to prevent the closure of deep geological fractures created in the walls of an extraction well, in particular of oil; heat exchange agents for example for fluidized bed; or for the treatment of surfaces.
- particle is meant a solid product individualized in a powder.
- Ball means a particle having a sphericity, that is to say a ratio between its smallest diameter and its largest diameter, greater than 0.6, whatever the way in which this sphericity has been obtained.
- the balls according to the invention have a sphericity greater than 0.7.
- the "size" of a ball (or particle) is the average of its largest dimension dM and its smallest dimension dm: (dM + dm) / 2.
- fused ball or more broadly “melted particle” is meant a solid ball (or particle) obtained by solidification by cooling of a molten material.
- a “molten material” is a liquid mass that may contain some solid particles, but in an amount insufficient for them to structure said mass. To maintain its shape, a molten material must be contained in a container.
- impurities is meant the inevitable constituents, necessarily introduced with the raw materials.
- the compounds forming part of the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of sodium and other alkalis, iron, vanadium and chromium are impurities.
- impurities By way of examples, mention may be made of MgO, CaO, Fe 2 O 3 , TiO 2 or Na 2 O.
- the residual carbon is one of the impurities of the composition of the particles according to the invention.
- zirconia or Zr0 2 When reference is made to zirconia or Zr0 2 , it is necessary to understand (Zr0 2 + Hf0 2 ), that is to say Zr0 2 and traces of Hf0 2 . Indeed, a little Hf0 2 , chemically indissociable Zr0 2 in a fusion process and having similar properties, is still naturally present in zirconia sources at levels generally below 2%. Hafnium oxide is not considered an impurity.
- precursor of an oxide is meant a constituent capable of supplying said oxide during the manufacture of a particle according to the invention.
- FIG. 1 represents a snapshot of the reference product of the examples
- FIG. 2 represents a snapshot of the product of example 8.
- the feedstock is formed of the indicated oxides or precursors thereof.
- ZrSiO 4 natural zircon sand containing about 66% ZrO 2 and 33% SiO 2 , plus impurities is used.
- the addition of Zr0 2 and Si0 2 in the form of zircon is indeed much more economical than an addition in the form of free zirconia and silica.
- compositions may be adjusted by addition of pure oxides, mixtures of oxides or mixtures of precursors of these oxides, in particular by addition of Zr0 2 , Si0 2 , La 2 0 3 , Y 2 0 3 , and Al 2 0 3 .
- those skilled in the art adjust the composition of the feedstock so as to obtain, after step c), particles in accordance with the invention.
- the chemical analysis of the melted ceramic particles according to the invention is generally substantially identical to that of the feedstock.
- the skilled person knows how to adapt the composition of the feedstock accordingly.
- no raw materials other than those providing Zr0 2 + Hf0 2 , Si0 2 , La 2 0 3 , Al 2 0 3 , Y 2 0 3 and their precursors are deliberately introduced into the feedstock, the other oxides present being impurities.
- step b) the feedstock is melted, preferably in an electric arc furnace. Electrofusion makes it possible to manufacture large quantities of particles (preferably in the form of beads) with interesting yields. But all known furnaces are conceivable, such as an induction furnace or a plasma furnace, provided they allow to melt substantially completely the charge.
- step c) a stream of the molten liquid is dispersed in small liquid droplets which, as a result of the surface tension, take, for the majority of them, a substantially spherical shape.
- This dispersion can be performed by blowing, especially with air and / or steam and / or nitrogen, or by any other method of atomizing a molten material, known from the skilled in the art.
- a fused ceramic particle of a size of 0.005 to 4 mm can thus be produced.
- any conventional method for producing melted particles, especially molten beads, may be implemented, provided that the composition of the feedstock makes it possible to obtain particles having a composition in accordance with that of the particles according to the invention. For example, it is possible to manufacture a melted and cast block, then to grind it and, if necessary, to make a granulometric selection.
- a fused ceramic particle according to the invention has the following chemical composition, in percentages by weight on the basis of the oxides and for a total of 100%:
- a fused ceramic particle according to the invention preferably has a mass content of La 2 0 3 greater than 2.5%, greater than 3.0%, greater than 4.0%, or even greater than 5.0%.
- the mass content of La 2 0 3 is less than 14.0%, less than 12.0%, less than 10.0%, less than 9.5%, and even less than 9.0%.
- the mass content of yttrium oxide Y 2 O 3 is greater than 3.0%, greater than 3.5%, greater than 4.0%, or even greater than 4.5%, and / or less than 10.0%, less than 9.0%, less than 8.5%, or even less than 8.0%, less than 7.5%, less than 7.0%.
- a fused ceramic particle according to the invention preferably has a mass content of Al 2 O 3 greater than 0.8%, preferably greater than 1.0%, greater than 1.2%, greater than 1.5% by weight. %, greater than 1, 6% or even greater than 1, 8%.
- the Al 2 0 3 mass content is preferably less than 7.0%, less than 6.5%, less than 6.0%, less than 3.5%.
- the contents of zirconia and silica also influence the performance of a particle according to the invention.
- a fused ceramic particle according to the invention comprises a mass content of Zr0 2 greater than 50.0%, greater than 51.0%, greater than 52.0%, and even greater than 53.0%.
- this mass content is less than 70.0%, less than 65.0%, preferably less than 63.0%, or even less than 60.0% or less than 58.0%.
- a melted ceramic particle according to the invention comprises a mass content of SiO 2 greater than 16.0%, greater than 18.0%, preferably greater than 20.0%, more preferably greater than 22.0. %, preferably greater than 24.0%.
- this mass content is less than 31.0%, less than 30.0%, less than 29.0%, preferably less than 28.0%.
- a melted ceramic particle according to the invention has a ratio of the mass percentages Zr0 2 / SiO 2 greater than 1, 5, or even greater than 1, 8, or even greater than 2.0 or greater than 2.1, and / or less than 4.0, less than 3.0, preferably less than 2.5.
- a fused ceramic particle according to the invention has a ratio of Al 2 0 3 / SiO 2 mass percentages greater than 0.05, and / or less than 0.25, less than 0.20, preferably less than 0. 15.
- the “other oxides” are preferably present only in the form of impurities. It is considered that a total content of “other oxides” of less than 1.0% does not substantially modify the results obtained. However, preferably, the "other oxides" content, as a weight percentage based on the oxides, is less than 0.6%, preferably less than 0.5%, preferably less than 0.45%.
- the oxide content of a particle according to the invention represents more than 99.5%, preferably more than 99.9%, and more preferably substantially 100% of the total mass of said particle.
- a particle according to the preferred invention has the following chemical composition, in percentages by mass on the basis of the oxides and for a total of 100%:
- Zr0 2 + Hf0 2 complement to 100%, preferably 51.0% ⁇ Zr0 2 + Hf0 2 ⁇ 63.0%; 20.0% ⁇ SiO 2 ⁇ 30.0%;
- a particle according to the preferred invention has the following chemical composition, in percentages by mass on the basis of the oxides and for a total of 100%:
- Zr0 2 + Hf0 2 complement to 100%, preferably 52.0% ⁇ Zr0 2 + Hf0 2 ⁇ 63.0%; 22.0% ⁇ SiO 2 ⁇ 28.0%;
- a fused ceramic particle according to the invention may in particular have a size of less than 4 mm and / or greater than 0.005 mm.
- the melted ceramic particles according to the invention are particularly well suited as grinding agents or as dispersing agents in a wet medium, as well as for the treatment of surfaces.
- the invention therefore also relates to the use of a plurality of particles, in particular beads according to the invention, or beads made according to a process according to the invention, as grinding agents, or dispersion agents in a medium. wet.
- the properties of the beads in particular their strength, their density, as well as their ease of production, may make them suitable for other applications, especially as proppants or heat exchange agents or for the treatment of surfaces.
- the invention therefore also relates to a device selected from a suspension, a grinder, a surface treatment apparatus and a heat exchanger, said device comprising a particle powder according to the invention.
- the contents of the bowl are then washed on a sieve of 100 ⁇ so as to remove the residual silicon carbide and tearing material due to wear during grinding. After sieving through a sieve of 100 ⁇ , the particles are dried in an oven at 100 ° C. for 3 h and then weighed (mass m).
- the planetary wear is expressed as a percentage (%) and is equal to the mass loss of the balls reduced to the initial mass of the balls, ie: 100 (m 0 -m) / (m 0 ); the UP result is given in Table 1.
- the mill is started gradually until reaching a linear speed at the end of 10 m / s disks.
- the mill is kept in operation for a time t, between 16 and 24 hours, then stopped.
- the beads are rinsed with water, carefully removed from the mill and then washed and dried. They are then weighed (mass m ').
- the bead load is taken up and supplemented with (me-m ') grams of new beads so as to repeat the grinding operation as many times as necessary (n times) so that the cumulative grinding time is at least 100 hours and that the difference between the wear speed calculated in step n and in step n-1 is less than 15% in relative. Wear in a basic medium is the rate of wear measured in this stabilized situation (typically beyond 120 hours).
- the result UB is given in Table 1. It is considered that the results are particularly satisfactory if the products have an improvement in the base wear resistance (UB) of at least 20% compared with that of Example Ref. 1. Manufacturing protocol
- a zircon composition is used for the feedstock, and lanthanum oxide, yttrium oxide and aluminum oxide are added. This feedstock is melted in an electric Herault type arc furnace. The molten material is then dispersed into balls by blowing compressed air.
- the impurities represent, for each example, less than 1%.
- the reference beads of the example “Ref. 1 ", outside the invention, are beads commonly used in grinding applications.
- Example 4 shows that, surprisingly, the balls according to the invention tested have remarkable performances compared to the reference beads.
- Example 4 shows the synergistic effect from the addition of yttrium oxide and lanthanum oxide.
- a particle according to the invention thus has a microstructure comprising zirconia dendrites, preferably longer than 2 ⁇ , greater than 3 ⁇ , or greater than 5 ⁇ , embedded in a silicate phase comprising crystals of Zr0 2 , La 2 0 3 , Y 2 0 3 and Al 2 0 3 having a length of less than 0.3 ⁇ , less than 0.2 ⁇ , and even less than 0.1 ⁇ .
- the crystals of Zr0 2 , La 2 0 3 , Y 2 0 3 and Al 2 0 3 are distributed within the silicate phase so as to form a continuous network.
- more than 50%, more than 70%, or even more than 80% of these crystals are in contact with other crystals.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1058962A FR2966824B1 (fr) | 2010-10-29 | 2010-10-29 | Particule en matiere ceramique fondue. |
PCT/IB2011/054798 WO2012056420A1 (fr) | 2010-10-29 | 2011-10-28 | Particule en matiere ceramique fondue |
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EP2632874A1 true EP2632874A1 (fr) | 2013-09-04 |
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Application Number | Title | Priority Date | Filing Date |
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EP11781657.9A Withdrawn EP2632874A1 (fr) | 2010-10-29 | 2011-10-28 | Particule en matiere ceramique fondue |
Country Status (5)
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US (1) | US20130263523A1 (fr) |
EP (1) | EP2632874A1 (fr) |
CN (1) | CN103180265B (fr) |
FR (1) | FR2966824B1 (fr) |
WO (1) | WO2012056420A1 (fr) |
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FR3042792A1 (fr) * | 2015-10-21 | 2017-04-28 | Saint-Gobain Centre De Rech Et D'Etudes Europeen | Bille en un produit fondu |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2320276A1 (fr) | 1975-08-06 | 1977-03-04 | Prod Refractaires Europ | Billes ameliorees en matiere ceramique |
FR2714905B1 (fr) | 1994-01-11 | 1996-03-01 | Produits Refractaires | Billes en matière céramique fondue. |
US6749653B2 (en) * | 2002-02-21 | 2004-06-15 | 3M Innovative Properties Company | Abrasive particles containing sintered, polycrystalline zirconia |
FR2853898B1 (fr) * | 2003-04-17 | 2007-02-09 | Saint Gobain Ct Recherches | Grains ceramiques fondus a base d'alumine et de magnesie |
FR2872157B1 (fr) * | 2004-06-24 | 2006-10-13 | Saint Gobain Ct Recherches | Melange de grains d'alumine-zircone fondus |
FR2925485B1 (fr) * | 2007-12-20 | 2011-07-15 | Saint Gobain Ct Recherches | Produit en matiere ceramique fondue, procede de fabrication et utilisations. |
-
2010
- 2010-10-29 FR FR1058962A patent/FR2966824B1/fr not_active Expired - Fee Related
-
2011
- 2011-10-28 CN CN201180051329.5A patent/CN103180265B/zh active Active
- 2011-10-28 WO PCT/IB2011/054798 patent/WO2012056420A1/fr active Application Filing
- 2011-10-28 EP EP11781657.9A patent/EP2632874A1/fr not_active Withdrawn
- 2011-10-28 US US13/879,250 patent/US20130263523A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2012056420A1 * |
Also Published As
Publication number | Publication date |
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CN103180265B (zh) | 2015-05-13 |
WO2012056420A1 (fr) | 2012-05-03 |
FR2966824A1 (fr) | 2012-05-04 |
FR2966824B1 (fr) | 2013-04-05 |
CN103180265A (zh) | 2013-06-26 |
US20130263523A1 (en) | 2013-10-10 |
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