CN111094213A - 烧结的锆石珠粒 - Google Patents
烧结的锆石珠粒 Download PDFInfo
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- CN111094213A CN111094213A CN201880060111.8A CN201880060111A CN111094213A CN 111094213 A CN111094213 A CN 111094213A CN 201880060111 A CN201880060111 A CN 201880060111A CN 111094213 A CN111094213 A CN 111094213A
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- 239000011324 bead Substances 0.000 title claims abstract description 165
- 229910052845 zircon Inorganic materials 0.000 title claims abstract description 29
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 50
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 46
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 29
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 29
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 28
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 28
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 28
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 241000588731 Hafnia Species 0.000 claims abstract description 17
- 239000010431 corundum Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 7
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 84
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
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- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000003082 abrasive agent Substances 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 150000001860 citric acid derivatives Chemical class 0.000 description 1
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- 125000001475 halogen functional group Chemical group 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
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- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-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
- 238000012795 verification Methods 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/10—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 aluminium oxide
- C04B35/107—Refractories by fusion casting
- C04B35/109—Refractories by fusion casting containing zirconium oxide or zircon (ZrSiO4)
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- 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
- C04B35/64—Burning or sintering processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
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- 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
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- 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
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- 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
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- C04B35/486—Fine ceramics
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- 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
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- Glass Compositions (AREA)
Abstract
本发明涉及一种烧结的珠粒,其具有:‑以下结晶相,以基于结晶相的质量百分比计且总计为100%:‑25%≤锆石,或“Z1”≤94%;‑4%≤稳定化的氧化锆+稳定化的二氧化铪,或“Z2”≤61%;‑单斜氧化锆+单斜二氧化铪,或“Z3”≤50%;‑刚玉≤57%;‑除Z1、Z2、Z3和刚玉之外的结晶相≤10%;‑以下化学组成,以基于氧化物的质量百分比计且总计为100%:33%≤ZrO2+HfO2,或“Z4”≤83.4%;HfO2≤2%;10.6%<Si2<34.7%;Al2O3≤50%;0%≤Y2O3,或“Z5”;0%<CeO2,或“Z6”;0.3%≤CeO2+Y2O3≤19%,条件是:(1)CeO2+3.76×Y2O3≥0.128×Z,并且(2)CeO2+1.3×Y2O3≤0.318×Z,其中,Z=Z4+Z5+Z6‑(0.67×Z1×(Z4+Z5+Z6)/(0.67×Z1+Z2+Z3));MgO≤5%;CaO≤2%;除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物≤5.0%。
Description
技术领域
本发明涉及烧结的锆石珠粒、用于制造这些珠粒的方法、以及这些珠粒用作研磨剂、湿分散剂或用于表面处理的用途。
背景技术
涂料、油墨、染料、磁性漆和农用化学品复合工业也使用珠粒将液体和固体成分分散和均化。
矿物工业使用珠粒对可以通过传统工艺进行干法预研磨的材料进行精细研磨,特别是对碳酸钙、钛氧化物、石膏、高岭土和铁矿石进行精细研磨。
微研磨领域使用圆形砂、玻璃珠粒、金属珠粒和陶瓷珠粒。
-圆形砂(例如OTTAWA砂)是一种天然的便宜的产品,但不适用于现代的增压的高流量磨机。事实上,砂的耐性不强、密度低、品质多变且对材料有磨损性。
-广泛使用的玻璃珠粒在更大的直径范围内具有更好的强度、更低的磨损性和可用性。
-金属珠粒、特别是钢珠粒,对经处理的产品具有低的惰性,尤其导致矿物填料的污染和涂料的灰化,并且密度过大,需要专门的破碎机。它们特别涉及设备的高能耗、高加热和高机械应力。
-陶瓷珠粒具有比玻璃珠粒更好的耐性、更高的密度和出色的化学惰性。
珠粒的尺寸通常为0.005mm至10mm。
可以区分:
-熔融的陶瓷珠粒,通常是通过熔化陶瓷成分、由熔融的材料形成球形液滴、然后固化所述液滴而获得的;以及
-烧结的陶瓷珠粒,通常是通过将陶瓷粉末冷成型,然后通过高温烧制使其固结而获得的。
与烧结的珠粒不同,熔融的珠粒通常具有非常丰富的晶间玻璃相,该相填充结晶晶粒的网络。因此,烧结的珠粒和熔融的珠粒在它们各自的应用中遇到的问题、以及为解决这些问题所采用的技术方案通常是不同的。此外,由于制造工艺之间的显著差异,开发用于生产熔融的珠粒的组成先验地不适合于生产烧结的珠粒,反之亦然。
为了服务于上述所有市场,珠粒必须同时具有良好的耐磨性和高的密度。
本发明的一个目的是提供满足这些限制的珠粒。
发明内容
本发明涉及一种烧结的珠粒,其具有:
-以下结晶相,以基于结晶相的质量百分比计且总计为100%:
-25%≤锆石,或“Z1”≤94%;
-4%≤稳定化的氧化锆+稳定化的二氧化铪,或“Z2”≤61%;
-单斜氧化锆+单斜二氧化铪,或“Z3”≤50%;
-刚玉≤57%;
-除Z1、Z2、Z3和刚玉之外的结晶相<10%;
-以下化学组成,以基于氧化物的质量百分比计且总计为100%:
33%≤ZrO2+HfO2,或“Z4”≤83.4%;
HfO2≤2%;
10.6%≤SiO2≤34.7%;
Al2O3≤50%;
0%≤Y2O3,或“Z5”;
0%≤CeO2,或“Z6”;
0.3%≤CeO2+Y2O3≤19%,条件是
(1)CeO2+3.76×Y2O3≥0.128×Z,并且
(2)CeO2+1.3×Y2O3≤0.318×Z,
其中,Z=Z4+Z5+Z6-(0.67×Z1×(Z4+Z5+Z6)/(0.67×Z1+Z2+Z3));
MgO≤5%;
CaO≤2%;
除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物<5.0%。
在实施方式中,烧结的珠粒具有:
-以下结晶相,以基于结晶相的质量百分比计且总计为100%:
-31%≤锆石,或“Z1”≤94%;
-4%≤稳定化的氧化锆+稳定化的二氧化铪,或“Z2”≤61%;
-单斜氧化锆+单斜二氧化铪,或“Z3”≤50%;
-刚玉≤40%;
-除Z1、Z2、Z3和刚玉之外的结晶相<10%;
-以下化学组成,以基于氧化物的质量百分比计且总计为100%:
37%≤ZrO2+HfO2,或“Z4”≤83.4%;
HfO2≤2%;
12.6%≤SiO2≤34.7%;
Al2O3≤35%;
0%≤Y2O3,或“Z5”;
0%≤CeO2,或“Z6”;
0.3%≤CeO2+Y2O3≤19%,条件是
(3)CeO2+3.76×Y2O3≥0.128×Z,并且
(4)CeO2+1.3×Y2O3≤0.318×Z,
其中,Z=Z4+Z5+Z6-(0.67×Z1×(Z4+Z5+Z6)/(0.67×Z1+Z2+Z3));
MgO≤5%;
CaO≤2%;
除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物<5.0%。
如将在下面的说明书中更详细地讨论的,发明人出人意料地发现,这些特征的组合显著改善了耐磨性质,同时提供了高的密度。
因此,根据本发明的烧结的珠粒特别很好地适合于湿分散、微研磨、热交换和表面处理应用。
根据本发明的烧结的珠粒还可以具有以下可选特征中的一个或多个:
-以基于氧化物的质量百分比计,ZrO2+HfO2的含量大于或等于31%、优选大于35%、优选大于40%、优选大于45%、优选大于50%,和/或小于80%、优选小于75%、优选小于70%;
-以基于氧化物的质量百分比计,SiO2含量大于或等于12.6%、优选大于14%、优选大于15%,和/或小于30%、优选小于25%;
-ZrO2+HfO2的含量与SiO2含量之比大于1.2、优选大于1.5、优选大于2、优选大于2.2、优选大于2.5和/或小于5、优选小于4.5、优选小于4、优选小于3.5;
-以基于氧化物的质量百分比计,Al2O3含量大于5%、优选大于10%,和/或小于40%、优选小于或等于35%、优选小于30%、优选小于25%、优选小于20%。有利地,珠粒的密度被提高;
-以基于氧化物的质量百分比计,MgO含量大于0.1%、优选大于0.15%、或甚至大于0.2%、或甚至大于0.3%,和/或小于4%、优选小于3%、优选小于2%、优选小于1.5%、优选小于1%;
-以基于氧化物的质量百分比计,CaO含量大于0.1%、优选大于0.2%、优选大于0.3%,和/或小于1.5%、优选小于1%;
-以基于氧化物的质量百分比计,CeO2+Y2O3的含量大于0.65%、优选大于0.95%、优选大于1.3%、优选大于1.6%、优选大于1.95%、优选大于2.2%、优选大于3%;
-化学组成使得CeO2+3.4×Y2O3≥0.16×Z、优选CeO2+2.89×Y2O3≥0.185×Z、优选CeO2+2.39×Y2O3≥0.212×Z、优选CeO2+1.84×Y2O3≥0.224×Z、优选CeO2+1.76×Y2O3≥0.229×Z;
-以基于氧化物的质量百分比计,CeO2+Y2O3的含量小于15.5%、优选小于14.3%、优选小于11.6%;
-化学组成使得CeO2+1.4×Y2O3≤0.259×Z;
-在优选的实施方式中,CeO2含量小于0.2%、优选小于0.1%、优选基本上为零;
-化学组成使得Y2O3≥1.82×Z、优选Y2O3≥3.44×Z、优选Y2O3≥5.38×Z;
-以基于氧化物的质量百分比计,除ZrO2、HfO2、SiO2、Al2O3、Y2O3、CeO2、CaO、MgO之外的氧化物的含量小于4%、优选小于3%、优选小于2、或甚至小于1.5%、或甚至小于1%。优选地,Na2O含量小于0.8%、优选小于0.5%、优选小于0.3%、优选小于0.2%,和/或K2O含量小于0.8%、优选小于0.5%、优选小于0.3%、优选小于0.2%;
-除ZrO2、HfO2、SiO2、Al2O3、Y2O3、CeO2、CaO、MgO之外的氧化物是杂质;
-优选地,根据本发明的珠粒的氧化物含量占所述珠粒的总质量的大于99%、优选大于99.5%、优选大于99.9%、并且优选基本上为100%;
-以基于结晶相的总量的质量百分比计,锆石(ZrSiO4相)含量大于或等于31%、优选大于35%、优选大于40%和/或小于90%、优选小于85%、优选小于80%、优选小于76%、优选小于72%、优选小于68%;
-以基于结晶相的总量的质量百分比计,稳定化的氧化锆(ZrO2相)+稳定化的二氧化铪(HfO2相)的含量大于5%、优选大于8%、优选大于10%、优选大于12%、优选大于15%、优选大于18%、优选大于20%、优选大于24%、优选大于27%和/或小于55%、优选小于50%、优选小于47%;
-以基于结晶相的总量的质量百分比计,单斜氧化锆(ZrO2相)+单斜二氧化铪(HfO2相)的含量小于45%、优选小于40%、优选小于35%、优选小于35%、优选小于30%、优选小于25%、优选小于20%、优选小于15%、优选小于10%、优选小于5%、优选基本上为零;
-以基于结晶相的总量的质量百分比计,刚玉(Al2O3相)含量大于5%、优选大于10%和/或小于50%、优选小于或等于40%、优选小于35%、优选小于30%、优选小于25%、优选小于20%;
-以基于结晶相的总量的质量百分比计,“其他结晶相”(即,除锆石、稳定化的氧化锆、稳定化的二氧化铪、单斜氧化锆、单斜二氧化铪和刚玉之外的结晶相)的含量小于8%、优选小于6%、或甚至小于5%、或甚至小于4%;
-“其他结晶相”的超过90质量%、超过95质量%、基本上100质量%是莫来石和/或方石英;
-在实施方式中,用示例所描述的测量方法无法检测出莫来石的含量;
-以基于珠粒质量的质量百分比计,非晶相、即玻璃相的质量小于25%、优选小于20%、优选小于17%;
-非晶相(以氧化物表示)包含MgO和SiO2,和/或Y2O3和/或Al2O3和/或CaO和/或Na2O和/或K2O和/或P2O5;
-非晶相(以氧化物表示)包含MgO和SiO2和Y2O3和Al2O3和Na2O和K2O和P2O5;
-总孔隙率小于6%、优选小于5.5%、优选小于5%、优选小于4.5%、或甚至小于4%、或甚至小于3%、或甚至小于2%;
-烧结的珠粒的尺寸小于10mm、优选小于2.5mm和/或大于0.005mm、优选大于0.5mm;
-烧结的珠粒的球形度大于0.7、优选大于0.8、优选大于0.85或甚至大于0.9;
-烧结的珠粒的密度大于4.2g/cm3、优选大于4.3g/cm3、或甚至大于4.4g/cm3和/或小于4.9g/cm3、优选小于4.8g/cm3。
在优选的实施方式中,根据本发明的烧结的珠粒最优选具有:
-以下结晶相,以基于结晶相的质量百分比计且总计为100%:
-31%≤锆石≤68%;
-25%≤稳定化的氧化锆+稳定化的二氧化铪≤47%;
-单斜氧化锆+单斜二氧化铪≤5%;
-4%≤刚玉≤25%;
-除锆石、稳定化的氧化锆、稳定化的二氧化铪、单斜氧化锆、单斜二氧化铪和刚玉之外的结晶相<5%;
-以下化学组成,以基于氧化物的质量百分比计且总计为100%:
50%≤ZrO2+HfO2≤70%;
HfO2≤2%;
15%≤SiO2≤25%;
5%≤Al2O3≤20%;
3%≤Y2O3≤8.3%;
CeO2≤0.1%;
0.1%≤MgO≤1%;
0.3%≤CaO≤1%;
除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物小于3%。
在该实施方式中,烧结的珠粒优选地具有:
-基于珠粒的质量,小于25%的非晶相,和
-小于或等于6%的总孔隙率。
优选地,CeO2含量基本上为零。
本发明还涉及一种珠粒粉末,以质量百分比计,该珠粒粉末包含大于90%、优选大于95%、优选基本上为100%的根据本发明的珠粒。
本发明还涉及用于制造根据本发明的烧结的珠粒的方法,该方法包括以下依次进行的步骤:
a)任选地,研磨一种或多种原料粉末,优选地通过共研磨来进行研磨,和
定量加入所述任选地研磨的原料粉末,
从而获得这样的颗粒状混合物:该颗粒状混合物具有小于0.6μm的中值粒度,并且该颗粒状混合物的组成适合于在步骤g)结束时获得具有与根据本发明的烧结的珠粒的组成一致的组成的烧结的珠粒,
该颗粒状混合物包含锆石颗粒、稳定化的氧化锆颗粒和包含MgO和/或SiO2的玻璃颗粒、和/或包含MgO的玻璃陶瓷颗粒、和/或包含MgO和SiO2的化合物颗粒、和/或这些氧化物的前体的粉末,
b)任选地,干燥所述颗粒状混合物,
c)由所述颗粒状混合物制备起始进料,所述颗粒状混合物任选地被干燥过,
d)将起始进料成型为原始珠粒的形式,
e)任选地,洗涤,
f)任选地,干燥,
g)在高于1330℃且低于1450℃的烧结温度下烧结以获得烧结的珠粒。
最后,本发明涉及根据本发明的珠粒粉末、特别是根据本发明的方法制造的珠粒粉末作为研磨剂;湿分散剂;支撑剂,特别是防止在开采井(特别是石油)的壁中形成的深部地质裂缝闭合的支撑剂;热交换剂,例如用于流化床的热交换剂;或用于表面处理的用途。
定义
-氧化物含量或结晶相的总和(即,这些含量由符号“+”连接的公式)并不意味着由该符号“+”连接的两种氧化物或结晶相必定同时存在。
-“颗粒状的”是指在粉末中个体化的固体产品。
-“烧结”是在超过1100℃下通过热处理使原始颗粒(颗粒状团聚物)固结,其某些(但不是全部)成分可以部分或全部熔化。
-“珠粒”是指球形度(即,其最小的费雷特(Feret)直径与其最大的费雷特直径之间的比率)大于0.6的颗粒,而与如何获得该球形度无关。优选地,根据本发明的珠粒具有大于0.7的球形度。
-珠粒的“尺寸”是其最小的费雷特直径。
-通常由D50表示的原料颗粒的粉末的“中值粒度”,是将该粉末的颗粒划分为质量相等的第一群体和第二群体的尺寸,这些第一群体和第二群体分别仅包含尺寸大于或小于中值粒度的颗粒。例如,可以使用激光粒度仪来估计中值粒度。
-“烧结的珠粒”是指通过烧结原始珠粒而获得的固体珠粒。
-“杂质”是指必然与原料一起引入的不可避免的成分。特别地,在实施方式中,属于钠和其他碱金属、铁、钒和铬的氧化物、氮化物、氮氧化物、碳化物、碳氧化物、碳氮化物的组的化合物是杂质。实例包括Fe2O3和TiO2。残留的碳是根据本发明的颗粒的组成中的杂质中的一者。
-当提及ZrO2或(ZrO2+HfO2)时,以基于ZrO2+HfO2的质量百分比计,这被理解为是指ZrO2和小于2%的HfO2。事实上,化学上与ZrO2不可分离且具有相似性质的一些HfO2总是以通常低于2%的水平(以基于ZrO2+HfO2的质量百分比计)天然地存在于ZrO2源中。氧化铪不被认为是杂质。
-氧化物的“前体”是能够在根据本发明的珠粒的制造过程中提供所述氧化物的成分。
-“稳定化的氧化锆”是指二次晶型和/或立方晶型的氧化锆。
为了清楚起见,术语“ZrO2”、“HfO2”、“SiO2”和“Al2O3”用于表示组成中这些氧化物的含量,“氧化锆”、“二氧化铪”和“刚玉”表示分别由ZrO2、HfO2、SiO2和Al2O3组成的这些氧化物的结晶相。但是,这些氧化物也可以以其他相存在。特别地,ZrO2和SiO2可以作为锆石(ZrSiO4)存在。
除非另有说明,否则本说明书中的所有百分比均为基于氧化物的质量百分比。
珠粒的所有特征都可以根据示例中描述的方案测量。
除非另有说明,否则术语“含有一”、“包含一”或“包括一”应被广义地解释,而没有限制。
具体实施方式
为了制造根据本发明的烧结的珠粒,可以进行上文描述并在下文详述的步骤a)至步骤g)。
在步骤a)中,如果以适合于制造根据本发明的珠粒的比例的原料粉末的混合物不形成中值粒度小于0.6μm的颗粒混合物,则可以单独地研磨原料粉末或优选地将原料粉末共研磨。该研磨可以是湿研磨。
优选地,将以所述颗粒状混合物的中值粒度小于0.5μm、优选小于0.4μm的方式进行研磨或共研磨。
优选地,所使用的粉末,特别是锆石ZrSiO4的粉末、稳定化的氧化锆ZrO2的粉末、任选地氧化铝Al2O3的粉末、包含MgO和/或SiO2的玻璃的粉末、和/或包含MgO的玻璃陶瓷的粉末、和/或包含MgO和SiO2的化合物的粉末,各自的中值粒度小于5μm、或甚至小于3μm、小于1μm、小于0.7μm、优选小于0.6μm、优选小于0.5μm、或甚至小于0.4μm。有利地,当这些粉末中的每一者的中值粒度小于0.6μm、优选小于0.5μm、或甚至小于0.4μm时,研磨是任选的。
在根据本发明的方法中,该颗粒状混合物包含锆石ZrSiO4的粉末、稳定化的氧化锆ZrO2的粉末、含有MgO和/或SiO2的玻璃的粉末、和/或含有MgO的玻璃陶瓷的粉末和/或含有MgO和SiO2的化合物的粉末、以及任选的氧化铝Al2O3粉末。
这些粉末也可以至少部分地被以等量引入的这些氧化物的前体的粉末代替。
优选地,所使用的锆石粉末的通过BET法计算的比表面积大于5m2/g、优选大于8m2/g、优选大于10m2/g,和/或小于30m2/g。有利地,步骤a)中的研磨通常在悬浮液中被促进。另外,可以降低步骤f)中的烧结温度。
优选地,所使用的稳定化的氧化锆粉末的通过BET法计算的比表面积大于0.5m2/g、优选大于1m2/g、优选大于1.5m2/g和/或小于20m2/g、优选小于18m2/g、优选小于15m2/g。有利地,步骤a)中的通常在悬浮液中的研磨是有促进作用的。另外,可以降低步骤f)中的烧结温度。
优选地,所使用的氧化铝粉末的中值粒度小于7μm、优选小于6μm、或甚至小于3μm、或甚至小于2μm、或甚至小于1.5μm。
在步骤(b)中,任选地,将研磨的原料粉末干燥,例如在烘箱中干燥或通过喷雾干燥,特别是如果研磨的原料粉末是通过湿研磨获得的。优选地,调节干燥步骤的温度和/或持续时间,使得原料粉末的残留水分小于2%或甚至小于1.5%。
在步骤c)中,制备起始进料,优选在室温下制备起始进料。
以基于起始进料的质量的质量计,起始进料以大于35%、优选大于40%和/或小于94%、优选小于90%、优选小于85%、优选小于80%、优选小于76%、优选小于72%、优选小于68%的量包含锆石粉末(即,ZrSiO4颗粒)。
以基于起始进料的质量的质量计,起始进料以大于5%、优选大于10%、优选大于15%、优选大于20%、优选大于25%和/或小于60%、优选小于55%、优选小于50%的量包含以能够稳定氧化锆的量同时包含ZrO2、HfO2、和Y2O3和CeO2的颗粒的粉末,优选在均匀混合物中以能够稳定氧化锆的量同时包含ZrO2、HfO2、和Y2O3和CeO2的颗粒的粉末,优选稳定化的氧化锆颗粒的粉末,即Y2O3和/或CeO2稳定化的ZrO2颗粒的粉末。
优选地,稳定化的氧化锆粉末是Y2O3稳定化的氧化锆粉末,并且基本上不包含CeO2。
优选地,稳定化的氧化锆粉末以立方晶型被稳定化。出人意料地,发明人发现珠粒的耐磨性大大提高。
在第一优选的实施方式中,稳定化的氧化锆粉末是使用Y2O3以立方晶型被稳定化的氧化锆粉末,并且基本上不包含CeO2。在所述实施方式中,基于ZrO2、Y2O3和CeO2的总含量,Y2O3的摩尔含量为7.5mol%至11mol%。
在第二优选实施方式中,以基于起始进料的质量的质量计,起始进料以大于5%、优选大于10%和/或小于45%、优选小于35%、优选小于30%、优选小于25%、优选小于20%的量包含氧化铝粉末(即,Al2O3颗粒)。优选地,所述氧化铝粉末是活性氧化铝粉末和/或煅烧的氧化铝粉末和/或过渡态氧化铝粉末。优选地,所述氧化铝粉末是活性氧化铝粉末。
在第三实施方式中,以基于起始进料的质量的质量百分比计,起始进料以优选大于0.5%、优选大于1%和/或小于6%、优选小于5%、优选小于4%、优选小于3%、优选小于2%的量包含二氧化硅粉末(即,SiO2颗粒)。
以质量计,含有MgO和/或SiO2的玻璃粉末和/或含有MgO的玻璃陶瓷粉末优选地含有大于40%、优选大于50%、或甚至大于60%、或甚至大于70%、或甚至大于80%的二氧化硅。
含有MgO和SiO2的化合物还优选含有Al2O3。优选地,所述化合物选自滑石、堇青石及其混合物。优选地,所述化合物是堇青石。
在第四实施方式中,以基于起始进料的质量的质量百分比计,起始进料以优选大于0.5%、优选大于1%、优选大于1.5%和/或小于15%、优选小于10%、优选小于8%、优选小于6%、优选小于5%、优选小于4%、优选小于3%的量包含堇青石。
在第五实施方式中,起始进料优选地以大于0.5%、优选大于1%、优选大于1.5%和/或小于5%、优选小于4%、优选小于3%的量包含黏土。
在实施方式中,上文刚刚描述的第一实施方式至第五实施方式被组合。
提供氧化物或前体的粉末优选地被选择,使得以基于氧化物的质量百分比计,除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物的总含量小于5%。
优选地,除锆石ZrSiO4的粉末、稳定化的氧化锆ZrO2的粉末、任选地氧化铝Al2O3的粉末、含有MgO和/或SiO2的玻璃的粉末、和/或含有MgO的玻璃陶瓷的粉末、和/或含有MgO和SiO2的化合物的粉末之外,没有其他原料被主动地引入到起始进料中,存在的其他氧化物是杂质。
起始进料还可以包含溶剂、优选为水,其量适合于步骤d)中的成型方法。
如本领域技术人员众所周知的,起始进料适合于步骤d)中的成型过程。
成型尤其可以由胶凝过程引起。出于该目的,将溶剂(优选水)添加至起始进料中以实现悬浮液。
悬浮液优选具有以质量计50%至70%的干物质含量。
该悬浮液还可以包含以下组分中的一者或多者:
-分散剂,以基于干物质的质量百分比计,比率为0至10%;
-表面张力改性剂,以基于干物质的质量百分比计,比率为0至3%;
-胶凝剂,以基于干物质的质量百分比计,比率为0至2%。
分散剂、表面张力改性剂和胶凝剂是技术人员众所周知的。
实例包括,
-作为分散剂,聚甲基丙烯酸钠或聚甲基丙烯酸铵家族、聚丙烯酸钠或聚丙烯酸铵家族、柠檬酸盐家族(例如柠檬酸铵)、磷酸钠家族、和碳酸酯家族;
-作为表面张力改性剂,有机溶剂(例如脂肪醇);
-作为胶凝剂,天然多糖。
优选地,氧化物粉末和/或前体粉末在球磨机中被添加到水和分散剂/抗絮凝剂的混合物中。在搅拌后,加入水,其中,预先已经溶解了胶凝剂,以获得悬浮液。
如果成型是挤出的结果,则可以将热塑性聚合物或热固性聚合物添加到起始进料中。
在步骤d)中,可以使用已知用于制造烧结的珠粒的任何常规成型工艺。
这些工艺的实例包括:
-造粒工艺,例如造粒机、流化床造粒机或造粒盘,
-凝胶工艺,
-注塑工艺或挤出成型工艺,以及
-压制工艺。
在凝胶工艺中,通过使悬浮液流过校准孔来获得上述悬浮液的液滴。从孔出来的液滴落入凝胶溶液(适于与胶凝剂反应的电解质)的浴中,在该浴中,液滴在恢复基本上球形的形状后硬化。
在步骤e)中,任选地,(例如用水)洗涤在前一步骤中获得的原始珠粒。
在步骤f)中,任选地,(例如在烘箱中)将可能经洗涤的原始珠粒干燥。
在步骤g)中,将可能经洗涤和/或经干燥的原始珠粒烧结。优选地,烧结在空气中、优选在电炉中、优选在大气压下进行。
步骤g)中的烧结在高于1330℃、优选高于1340℃、优选高于1350℃、优选高于1360℃、优选高于1370℃且低于1450℃、优选低于1430℃、优选低于1410℃、优选低于1400℃、优选低于1390℃的温度下进行。1375℃的烧结温度是非常合适的。低于1330℃的烧结温度不产生总孔隙率为6%或更小的颗粒。另一方面,高于1450℃的烧结温度导致锆石的离解过多,这不利于耐磨性。
优选地,烧结时间为2小时至5小时。4小时的烧结时间是非常合适的。
所获得的烧结的珠粒优选具有大于0.005mm、优选大于0.5mm且小于10mm、优选小于2.5mm的最小直径。
如果不遵守关系(1)和关系(2),则耐磨性不提高。这些关系使得可以对随大体上唯一地由稳定化的氧化锆提供的ZrO2的量的变化CeO2和Y2O3的总量限定条件。
因此,关系(1)表示Y2O3和CeO2以理论上适于稳定所有存在的氧化锆的量存在,关系(2)表示不存在不同于稳定化的氧化锆并且包含氧化物形式的锆和钇或包含氧化物形式的锆和铈的化合物。
根据本发明的烧结的珠粒特别很好地适合用作研磨剂或湿分散剂,以及用于表面处理。因此,本发明还涉及根据本发明的珠粒粉末或根据本发明的方法制造的珠粒作为研磨剂或在湿环境中作为分散剂的用途。
根据本发明的珠粒的性质、特别是其机械强度、密度和生产容易性,使其适合于其他应用,特别是作为支撑剂或热交换剂,或用于表面处理(特别是通过喷射根据本发明的珠粒进行表面处理)。
因此,本发明还涉及选自悬浮体、研磨机、表面处理设备和热交换器的物体,所述物体包括根据本发明的珠粒粉末。
实施例
出于说明本发明的目的,提供了以下非限制性实施例。
测量方案
使用以下方法测定不同的烧结的珠粒混合物的某些性能。这些方法为微研磨应用中的实际操作行为提供了优异的模拟。
为了测定珠粒的球形度,在由Horiba销售的Camsizer XT上测量最小的费雷特直径和最大的费雷特直径。
为了测定所谓的“行星式”耐磨性,对20ml(用量筒测量的体积)的待测珠粒(尺寸为1.6mm至2.0mm)进行称重(质量m0),并放入高速行星式研磨机(PM400,RETSCH)的4个涂覆有致密烧结氧化铝的转鼓(容量125ml)中的一者中。在已经含有珠粒的同一转鼓中,加入2.2g的Presi品牌的碳化硅(中值粒度D50为23μm)和40ml的水。关闭该转鼓并以400rpm旋转(行星式运动),每分钟反转旋转方向,持续1.5h。然后将转鼓中的内容物在100μm的筛网上洗涤,以去除残留的碳化硅和由于研磨过程中的磨损而引起的物料撕裂。在100μm的筛网上过筛后,将珠粒在100℃的烘箱中干燥3小时,然后称重(质量m1)。再次将所述珠粒(质量m1)引入具有SiC的悬浮液(与以前相同的浓度和量)的转鼓中的一者中,并进行与前一循环相同的新的研磨循环。然后将转鼓中的内容物在100μm的筛网上洗涤,以去除残留的碳化硅和由于研磨过程中的磨损而引起的物料撕裂。在100μm的筛网上过筛后,将珠粒在100℃的烘箱中干燥3小时,然后称重(质量m2)。再次将所述珠粒(质量m2)引入具有SiC的悬浮液(与以前相同的浓度和量)的转鼓中的一者中,并进行与前一循环相同的新的研磨循环。然后将转鼓中的内容物在100μm的筛网上洗涤,以去除残留的碳化硅和由于研磨过程中的磨损而引起的物料撕裂。在100μm的筛网上过筛后,将珠粒在100℃的烘箱中干燥3小时,然后称重(质量m3)。
行星式磨损(PW)以百分比(%)表示,并且等于相对于初始珠粒质量珠粒质量的损失,即100(m0-m3)/(m0);PW结果在表1中给出。
如果与实施例1(参考实施例)相比,产品的行星式耐磨性(PW)提高至少15%,则认为结果是特别令人满意的。
由根据以下方法制备的打磨的珠粒的样品进行根据本发明的烧结的珠粒中存在的结晶相的定量:对于每个实施例,基本上连续的单层的、尺寸为1.6mm至2mm的珠粒在等于180℃的温度下部分嵌入丙烯酸树脂中。
包含珠粒的树脂块的外径为25mm。
用粒度为65μm的砂纸打磨该块,直到观察到珠粒的中心为止。然后对该块进行更精细的打磨,倒数第二的打磨步骤是使用PRESI出售的Mecaprex LD32-E 1μm金刚石制品进行的,最后的打磨步骤是使用0.04μm的胶体二氧化硅溶液进行的。
存在于根据本发明的烧结的珠粒中的结晶相通过X射线衍射来测量,例如使用配备有铜DX管的Panalytical的X’Pert PRO衍射仪。由此设备在5°至80°的2θ角度范围内以0.017°的步长和150秒/步的计数时间进行衍射图的获取。前部光学器件具有固定的1/4°所使用的可编程发散槽,0.04rad的Soller槽,等于10mm的光罩和固定的1/2°防散射槽。样品自身旋转以限制优选方向。后部光学器件具有固定的1/4°所使用的可编程防散射槽,0.04rad的Soller槽和Ni滤光器。
然后使用EVA软件和ICDD2016数据库定性分析衍射图。
一旦确定了存在的相,就根据以下策略使用Rietveld精修的High Score Plus软件对衍射图定量分析:
-使用“处理”功能、“确定背景”并选择以下选项来进行背景信号的精修:“弯曲因子”等于0,并且“颗粒度”等于40。注意的是,如果观察到树脂引起的光晕,则可以逐点手动绘制基线。
-典型地,选择突出的和可量化的存在的相的ICDD表,并因此在精修时予以考虑;
-然后,通过选择先前确定的“使用可用背景”底部信号并选择“自动:选项:相拟合-默认Rietveld”模式来执行自动精修。
-然后,同时对所有选定的相的“B总”参数进行手动精修。
-最后,如果自动功能未执行,则同时手动精修二次氧化锆相和立方氧化锆相的Caglioti参数W。在这种情况下,为所述氧化锆相选择“W”,并再次进行精制。仅当第二精修的“拟合优度”参数低于第一精修的“拟合优度”参数时,才保留结果。
存在于根据本发明的烧结的珠粒中的非晶相的量通过X射线衍射来测量,例如使用配备有铜DX管的Panalytical的X’Pert PRO衍射仪。用与测定珠粒中存在的结晶相相同的方式,由该设备进行衍射图的获取,所分析的样品为粉末形式。所使用的方法包括添加已知量的完全结晶的标准品,在这种情况下,标准品为量等于20%(基于氧化锌和根据本发明的经研磨的烧结的珠粒的样品的质量)的氧化锌ZnO粉末。氧化锌粉末的最大尺寸为1μm,并且将根据本发明的珠粒被研磨以获得最大尺寸小于40μm的粉末。
将ZnO颗粒的最大尺寸输入到High Score Plus软件中以限制微吸收效应。
使用以下公式计算非晶相的比率(用百分比表示),QZnO是根据衍射图确定的ZnO的量:
非晶相的比率=100×(100/(100-20))×(1-(20/QZnO))
例如,如果QZnO等于22%,则非晶相的比率等于100×(100/(100-20))×(1-(20/22))=11.4%。
总孔隙率(用%表示)通过以下公式计算:
总孔隙率=100×(1-(d珠粒/d研磨的珠粒)),其中
-d研磨的珠粒是使用Aurec环型干磨机研磨珠粒40秒、然后过筛以仅保留通过160μm筛网的粉末用于测量而得到的粉末的密度。
制造方案
烧结的珠粒由以下制备:
-比表面积为约8m2/g、中值粒度为1.5μm、并且除ZrO2和SiO2之外的总氧化物含量为1.1%的锆石粉末,
-纯度大于95%且中值粒度小于63μm的堇青石粉末,
-中值粒度小于53μm、在1000℃下的烧失量为10%至15%、并且SiO2+Al2O3的总含量大于82%的黏土粉末,
-纯度大于98.5%且中值粒度为1.5μm的二氧化硅粉末,并且,根据所产生的实施例,
-纯度为99.5%且中值粒度小于5μm的氧化铝粉末,
-纯度大于99.5%且中值粒度为2.8μm的氧化铈粉末,
-由Saint-Gobain ZirPro销售的单斜晶型的不稳定化的氧化锆粉末CZ-5,
-由Saint-Gobain ZirPro销售的、Y2O3的摩尔含量等于3%、并且主要呈二次晶型的稳定化的氧化锆粉末CY3Z,
-由TOSOH销售的、Y2O3的摩尔含量等于10%、并且呈基本上完全立方晶型的稳定化的氧化锆粉末TZ-10Y。
表1汇总了实施例的起始进料。
将这些粉末混合,然后在湿环境中共研磨,直到获得中值粒度小于0.4μm的颗粒状混合物。然后将颗粒状混合物干燥。
然后从这种颗粒状混合物制备由水悬浮液组成的起始进料,以基于干物质的质量百分比计,该水悬浮液包含0.5%的羧酸分散剂、0.6%的磷酸钠分散剂和0.4%的胶凝剂(即,藻酸盐家族的多糖)。
为了获得良好的起始进料均匀度,将球磨机用于此制备过程:首先形成包含胶凝剂的溶液。随后,将颗粒状混合物和分散剂加入水中。然后加入含有胶凝剂的溶液。将所得混合物搅拌8小时。使用出售的Sedigraph5100沉降粒度分析仪(sedigraph)通过沉降来控制粒度(中值粒度<0.4μm),并加入确定量的水,以得到干物质为68%且粘度(使用Brookfield粘度计、使用LV3转子以20rpm的速度测量的)小于5000厘泊的水悬浮液。在用强碱调节后,悬浮液的pH于是约为9。
在本实施例的情况下,将悬浮液以在烧结后产生约1.6mm至2.0mm的珠粒的流速通过校准孔。悬浮液的液滴落入基于电解质(二价阳离子盐)的凝胶浴中,与胶凝剂反应。收集原始珠粒,洗涤并在80℃下干燥以除去水分。然后将珠粒转移到烧结炉中,在其中以100℃/h的速率将其加热至1375℃的温度。在此温度下4个小时结束时,通过自然冷却实现温度降低。
结果
所得结果汇总于表2中。
实施例中的珠粒粉末具有大于0.9的平均球形度。
实施例2至实施例9中的珠粒具有小于20质量%的非晶相量。
现有技术的实施例1中的参考珠粒是常用于研磨应用的烧结的锆石珠粒,其组成类似于US 2004/007789的实施例4的组成。
Z=Z4+Z5+Z6-(0.67×Z1×(Z4+Z5+Z6)/(0.67×Z1+Z2+Z3))
例如,对于实施例2,Z确定如下:
Z=0.667+0.06+0-(0.67×0.68×(0.667+0.06+0)/(0.67×0.68+0.32+0))=0.3,或30%。
条件(1)和条件(2)的验证如下确定:
0.128×Z等于0.128×30=3.84,0.318×Z等于0.318×30=9.54。
CeO2+3.76×Y2O3等于0+3.76×6=22.56,远高于3.84(0.128×Z):对于实施例2,条件(1)确实被验证。
CeO2+1.3×Y2O3等于0+1.3×6=7.8,远低于9.54(0.318×Z):对于实施例2,条件(2)确实被验证。
比较现有技术的实施例1和根据本发明的实施例2,显示出行星式磨损PW降低58%,这尤其归功于添加了用Y2O3稳定并且基本上完全是立方的氧化锆而获得。
比较现有技术的实施例1和根据本发明的实施例6,显示出行星式磨损PW降低38%,这主要是由于添加了主要是二次晶型的稳定化的氧化锆。
实施例1、实施例2和实施例6的比较表明,出人意料地,与等于4.5%的实施例1中的磨损相比,优选的是添加基本上完全是立方的稳定化的氧化锆而不是主要为二次晶型的稳定化的氧化锆:磨损分别等于1.9%和2.8%。
根据本发明的实施例2至实施例4的比较表明,随着氧化铝添加量的增加,磨损PW降低并且密度降低。
现有技术的实施例1和实施例5的比较表明,通过添加34%的非稳定化的氧化锆粉末,磨损PW劣化。
实施例1和实施例7、实施例8和实施例9的比较表明,对于根据本发明的分别具有30.5%的SiO2含量、36.3%的Al2O3含量、和Y2O3和CeO2稳定化的氧化锆的珠粒,磨损PW降低。
实施例出人意料地显示,与参考珠粒相比,所测试的根据本发明的珠粒具有优异的性能。
Claims (40)
1.一种烧结的珠粒,其具有:
-以下结晶相,以基于结晶相的质量百分比计且总计为100%:
-25%≤锆石,或“Z1”≤94%;
-4%≤稳定化的氧化锆+稳定化的二氧化铪,或“Z2”≤61%;
-单斜氧化锆+单斜二氧化铪,或“Z3”≤50%;
-刚玉≤57%;
-除Z1、Z2、Z3和刚玉之外的结晶相<10%;
-以下化学组成,以基于氧化物的质量百分比计且总计为100%:
33%≤ZrO2+HfO2,或“Z4”≤83.4%;
HfO2≤2%;
10.6%≤SiO2≤34.7%;
Al2O3≤50%;
0%≤Y2O3,或“Z5”;
0%≤CeO2,或“Z6”;
0.3%≤CeO2+Y2O3≤19%,条件是
(1)CeO2+3.76×Y2O3≥0.128×Z,并且
(2)CeO2+1.3×Y2O3≤0.318×Z,
其中,Z=Z4+Z5+Z6-(0.67×Z1×(Z4+Z5+Z6)/(0.67×Z1+Z2+Z3));
MgO≤5%;
CaO≤2%;
除ZrO2、HfO2、SiO2、Al2O3、MgO、CaO、CeO2和Y2O3之外的氧化物<5.0%。
2.根据权利要求1所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,Al2O3≤35%,37%≤ZrO2+HfO2,且12.6%≤SiO2;并且以基于结晶相的总量的质量百分比计,刚玉的含量为40%或更少,锆石的含量为31%或更多。
3.根据前述权利要求中任一项所述的烧结的珠粒,其中,50%≤ZrO2+HfO2和/或SiO2>14%和/或Al2O3>5%和/或MgO>0.1%和/或CaO>0.1%。
4.根据前述权利要求中任一项所述的烧结的珠粒,其中,25%>Al2O3>10%。
5.根据前述权利要求中任一项所述的烧结的珠粒,其中,1.0%>MgO>0.15%。
6.根据前述权利要求中任一项所述的烧结的珠粒,其中,1.0%>CaO>0.2%。
7.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,CeO2+Y2O3的含量大于2.2%。
8.根据紧接的前一项权利要求所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,CeO2+Y2O3的含量大于3%。
9.根据前述权利要求中任一项所述的烧结的珠粒,其中,CeO2+2.39×Y2O3≥0.212×Z。
10.根据紧接的前一项权利要求所述的烧结的珠粒,其中,CeO2+1.84×Y2O3≥0.224×Z。
11.根据紧接的前一项权利要求所述的烧结的珠粒,其中,CeO2+1.76×Y2O3≥0.229×Z。
12.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,CeO2+Y2O3的含量小于15.5%。
13.根据紧接的前一项权利要求所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,CeO2+Y2O3的含量小于11.6%。
14.根据前述权利要求中任一项所述的烧结的珠粒,其中,CeO2+1.4×Y2O3≤0.259×Z。
15.根据前述权利要求中任一项所述的烧结的珠粒,其中,CeO2的含量小于0.2%、优选小于0.1%。
16.根据前述权利要求中任一项所述的烧结的珠粒,其中,Y2O3≥3.44×Z,优选Y2O3≥5.38×Z。
17.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于氧化物的质量百分比计,除ZrO2、HfO2、SiO2、Al2O3、Y2O3、CeO2、CaO、MgO之外的氧化物的含量小于2%。
18.根据前述权利要求中任一项所述的烧结的珠粒,其中,氧化物的含量占所述珠粒的总质量的大于99%。
19.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,所述烧结的珠粒具有大于35%且小于90%的锆石含量。
20.根据前一项权利要求所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,锆石的含量小于68%。
21.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,所述烧结的珠粒具有大于10%且小于50%的稳定化的氧化锆+稳定化的二氧化铪的含量。
22.根据前一项权利要求所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,稳定化的氧化锆+稳定化的二氧化铪的含量大于27%且小于47%。
23.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,单斜氧化锆+单斜二氧化铪的含量小于35%。
24.根据前一项权利要求所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,单斜氧化锆+单斜二氧化铪的含量小于10%。
25.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,所述烧结的珠粒具有大于10%且小于25%的刚玉含量。
26.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于结晶相的总量的质量百分比计,所述烧结的珠粒具有的除锆石、稳定化的氧化锆、稳定化的二氧化铪、单斜氧化锆、单斜二氧化铪和刚玉之外的结晶相的含量小于8%。
27.根据前一项权利要求所述的烧结的珠粒,其中,莫来石的含量基本上为零。
28.根据前述权利要求中任一项所述的烧结的珠粒,其中,以基于所述珠粒的质量的质量百分比计,所述烧结的珠粒具有小于25%的非晶相的质量。
29.根据紧接的前一项权利要求所述的烧结的珠粒,其中,以氧化物表示,所述非晶相包含:
-MgO和SiO2,和/或
-Y2O3,和/或
-Al2O3,和/或
-CaO,和/或
-Na2O,和/或
-K2O,和/或
-P2O5。
30.根据紧接的前一项权利要求所述的烧结的珠粒,其中,以氧化物表示,所述非晶相包含MgO和SiO2和Y2O3和Al2O3和Na2O和K2O和P2O5。
31.根据前述权利要求中任一项所述的烧结的珠粒,其中,所述烧结的珠粒具有小于6%的总孔隙率。
32.根据前述权利要求中任一项所述的烧结的珠粒,其中,所述烧结的珠粒具有大于0.7的球形度。
33.根据紧接的前一项权利要求所述的烧结的珠粒,其中,所述烧结的珠粒具有大于0.85的球形度。
34.根据前述权利要求中任一项所述的烧结的珠粒,其中,所述烧结的珠粒具有小于10mm且大于0.005mm的尺寸。
35.一种粉末,所述粉末包含以质量百分比计大于90%的根据前述权利要求中任一项所述的珠粒。
36.一种物体,所述物体选自悬浮体、研磨机、表面处理设备和热交换器,所述物体包括根据紧接的前一项权利要求所述的珠粒粉末。
37.一种用于制造根据权利要求1至34中任一项所述的烧结的珠粒的方法,所述方法包括以下依次进行的步骤:
a)任选地,研磨一种或多种原料粉末,优选地通过共研磨来进行研磨,和
定量加入任选地研磨的所述原料粉末,
从而获得这样的颗粒状混合物:所述颗粒状混合物具有小于0.6μm的中值粒度,并且所述颗粒状混合物的组成适合于在步骤g)结束时获得具有与根据权利要求1至34中任一项所述的烧结的珠粒的组成一致的组成的烧结的珠粒,
所述颗粒状混合物包含:
-锆石颗粒和稳定化的氧化锆颗粒,和
-含有MgO和/或SiO2的玻璃颗粒、和/或含有MgO的玻璃陶瓷颗粒和/或含有MgO和SiO2的化合物颗粒,
b)任选地,干燥所述颗粒状混合物,
c)由所述颗粒状混合物制备起始进料,所述颗粒状混合物任选地被干燥过,
d)将所述起始进料成型为原始珠粒的形式,
e)任选地,洗涤所述原始珠粒,
f)任选地,干燥所述原始珠粒,所述原始珠粒任选地被洗涤过,
g)在高于1330℃且低于1450℃的烧结温度下烧结所述原始珠粒以获得烧结的珠粒,所述原始珠粒任选地被干燥过和/或被洗涤过。
38.根据紧接的前一项权利要求所述的方法,其中,在步骤c)中,除锆石ZrSiO4的粉末、稳定化的氧化锆ZrO2的粉末、任选地氧化铝Al2O3的粉末、含有MgO和/或SiO2的玻璃的粉末、和/或含有MgO的玻璃陶瓷的粉末、和/或含有MgO和SiO2的化合物的粉末之外,没有其他原料被主动地引入到所述起始进料中。
39.根据紧接的前两项权利要求中任一项所述的方法,其中,在步骤c)中,稳定化的氧化锆粉末为Y2O3稳定化的氧化锆粉末,并且基本上不含CeO2。
40.根据紧接的前三项权利要求中任一项所述的方法,其中,在步骤c)中,稳定化的氧化锆粉末以立方晶型被稳定化。
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