TW201602320A - 耐火製品、二氧化鋯的應用、二氧化鋯、製造耐火製品的方法以及由之製造的耐火製品 - Google Patents
耐火製品、二氧化鋯的應用、二氧化鋯、製造耐火製品的方法以及由之製造的耐火製品 Download PDFInfo
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- TW201602320A TW201602320A TW104122576A TW104122576A TW201602320A TW 201602320 A TW201602320 A TW 201602320A TW 104122576 A TW104122576 A TW 104122576A TW 104122576 A TW104122576 A TW 104122576A TW 201602320 A TW201602320 A TW 201602320A
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- zirconium dioxide
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 157
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 41
- 238000002485 combustion reaction Methods 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 230000000087 stabilizing effect Effects 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000292 calcium oxide Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011819 refractory material Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229940024548 aluminum oxide Drugs 0.000 claims 1
- 239000012071 phase Substances 0.000 description 34
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 229940091250 magnesium supplement Drugs 0.000 description 12
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 229910002078 fully stabilized zirconia Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 239000010987 cubic zirconia Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011214 refractory ceramic Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229960000869 magnesium oxide Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 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
- 230000001010 compromised effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明係有關於一種耐火製品、一種二氧化鋯的應用、一種二氧化鋯、一種製造耐火製品的方法、以及一種由所述方法所製造的耐火製品。
Description
本發明係有關於一種耐火製品、一種二氧化鋯的應用、一種二氧化鋯、一種製造耐火製品的方法、以及一種由所述方法所製造的耐火製品。
關於本發明之目的,該術語”耐火製品”特別描述具有一工作溫度超過600℃之耐火製品,及較佳地為根據DIN 51060之耐火製品,亦即,具有一示溫錐當量(pyrometric cone equivalent)>賽格測溫錐17(Seger Cone 17)之物質。該示溫錐當量可特別根據DIN EN 993-12而計算。
典型地,耐火製品係基於下列氧化物中的一者:Al2O3、MgO、Cr2O3、SiO2、CaO或ZrO2。
因良好的耐腐蝕及耐磨耗性係極為重要的,由於二氧化鋯(ZrO2)良好的耐腐蝕性,其係特別用於耐火製品。就此而言,對於包含ZrO2之耐火製品,一較佳地應用領域係連續鋼鑄件,例如其中包含ZrO2之耐火製品係用作,例
如滑動板(slide plates)、單塊阻塞器(monobloc stoppers)、浸入管(immersion pipes)或浸入式噴嘴(submerged nozzles)。在此情況下,典型地,並非整個耐火製品係基於ZrO2,而僅是那些必須被建構以特別抵抗腐蝕及磨耗之區域。特別是,這樣的區域可為,在運作時必須被置於熔渣區域中的該耐火製品之區域、或者沿著該具有相對高流速之熔融鋼材之區域。
一般而言,ZrO2已被證實係在如此之耐火製品中一耐腐蝕材料。然而,當ZrO2被用於一耐火製品中,必須考量到一已知的現象,其係根據ZrO2可出現在三種變型體之任一者。相對應地,在室溫及高達約1,173℃之一溫度,呈純相的形式的ZrO2係以一單斜晶系相存在,超過此溫度,其被轉換成正方晶系或立方晶系。超過一約2,370℃之溫度,ZrO2僅以該正方晶系變型體存在。儘管該轉換成單斜晶系低溫變型體之再轉換反應係往較低的溫度轉移、且不到約920℃之後不會發生,該等相轉換反應係可逆的。
由於該ZrO2之單斜晶系低溫相具有一大約大於該正方晶系及立方晶系高溫相之5%的體積,故每當介於該單斜晶系低溫相、及該正方晶系或立方晶系高溫相各別之溫度轉換邊界以對應的方向被跨越,該ZrO2以此量收縮或膨脹。若該耐火製品必須包含純ZrO2,此體積的變化會導致裂縫在該製品中的生成。
為了避免當溫度降至該轉換溫度以下時該ZrO2體積的暴漲,已知藉由添加特定氧化物來穩定該高溫變型
體,以致使該高溫變型體在室溫仍係維持在一介穩態。已知提供對應穩定性的氧化物為,例如MgO、CaO、Y2O3、或稀土族氧化物。例如,該立方晶系變型體藉由添加一至少16莫耳百分比的CaO、至少16莫耳百分比的MgO或至少8莫耳百分比的Y2O3至該ZrO2,在低至室溫下,可維持在一介穩態。以此方式被完全穩定之ZrO2被指為完全穩定之ZrO2(FSZ,”完全穩定之二氧化鋯”)。若ZrO2係僅以如此之百分比藉由穩定氧化物之添加而被穩定,致使該立方晶系於低至室溫下僅部分地被維持在該介穩態中,該於此形式之ZrO2被指為部分穩定之ZrO2(PSZ,”部分穩定之二氧化鋯”)。
完全穩定之ZrO2展現線性熱膨脹,而部分穩定之ZrO2僅有一較多或較少之顯著體積暴漲,其係作為一個單斜晶系ZrO2之殘餘百分比之相關性的函數,當該轉換溫度邊界以任一方向被跨越。相對應地,經完全或部分穩定之ZrO2因而適合用作為一在耐火製品中的材料。
然而,經完全及部分穩定的二氧化鋯相較於純ZrO2同有一個缺點,特別是該經完全及部分穩定的ZrO2之耐腐蝕及耐磨耗性相較於純ZrO2皆係減少的。這特別是歸因於下列事實,亦即隨著該穩定添加劑與物質結合,該耐火產品在運作過程中彼此接觸以形成具有低熔點的相。如此之物質可特別係該熔融鋼鐵或熔渣的組分,其與在CaO、MgO或Y2O3形式之穩定添加劑各自形成不同相。
就此而言,該ZrO2優異的耐腐蝕性係被穩定添加
劑所折衷。
本發明所蘊含的目的在於提供一包含ZrO2之耐火產品,特別是一耐火陶瓷產品,其中,當介於該低溫相及該高溫相間的轉換溫度邊界被以任一方向跨越時,該ZrO2展現極小的或不異常顯著的熱膨脹,但相較於由先前技藝已知之該完全或部分穩定的ZrO2,其同時具有改良的耐腐蝕性。
本發明之另一目的在於提供一用來製造如此之耐火產品的方法、及一根據如此之方法所製成的耐火產品。
為了達成該第一目的,一根據本發明之耐火產品被提供,該產品包含一在室溫下穩定、呈立方晶系變型體之二氧化鋯形式的礦物相,且其具有等同小於1重量%之鈣、鎂及釔的組份。
相較於該二氧化鋯的總質量,鈣、鎂及釔,該等元素在本發明之二氧化鋯的總質量係如所述低於1重量%。
根據本發明,被發現的是以該立方晶系變型體之二氧化鋯所形成的一礦物相,其係在室溫下穩定、且具有一不超過1重量%之鈣、鎂及釔的含量(以下亦稱為”根據本發明之二氧化鋯”),其構成一對於耐火產品而言優異的以ZrO2為主的原料,特別是耐火陶瓷產品,因為如此之二氧化鋯展現極小或無異常的熱膨脹,且同時,相較於由先前技藝所知而達成之該經部分或完全穩定之ZrO2,展現較佳的耐腐蝕性。
在室溫下穩定的、呈立方晶系變型體之二氧化鋯,其不發生或僅極少發生之異常熱膨脹係由下列事實所造成,亦即該物質在介於室溫及2,370℃之溫度區間總是以該立方晶系存在,因而該等變型體不經歷任何轉換。相較於由先前技藝所知之該部分或完全穩定的ZrO2,根據本發明之二氧化鋯具有較佳耐腐蝕性一事係藉由下列事實被解釋,亦即該在室溫下穩定的、以立方晶系變型體之二氧化鋯所包含之鈣、鎂及釔的含量係被限制在低於1重量%的分量。
為了更進一步改善根據本發明之二氧化鋯之耐腐蝕性,下列情事係根據本發明而提供,亦即,在各個情況下相對於根據本發明之二氧化鋯的總質量,該根據本發明之二氧化鋯中的鈣、鎂、及釔含量亦被限制為低於0.9重量%、0.8重量%、0.7重量%、0.6重量%、0.5重量%、或低於0.4重量%。然而,根據本發明之二氧化鋯係幾乎不可能以化學上純相的形式提供,這導致,在各個情況下相對於根據本發明之二氧化鋯的總質量,該鈣、鎂及釔可以至少0.1重量%、0.2重量%或0.3重量%的份量存在於該根據本發明之二氧化鋯中。
根據本發明概念之一成果,被提供的是,根據本發明之二氧化鋯中的外加氧化物之含量係低於1.5重量%。關於此,該術語”外加氧化物(extraneous oxides)”係用來指所有非ZrO2或HfO2之氧化物(這是由於已知天然鋯原料總是包含微量的HfO2),其亦包含以CaO、MgO、Y2O3、及由
先前技藝所知的稀土氧化物形式存在的穩定添加劑。
根據本發明,已發現若在根據本發明的下列條件下,該根據本發明之二氧化鋯之耐腐蝕性可更進一步被改善,亦即在各個情況下相對於根據本發明之二氧化鋯的總質量,該根據本發明之二氧化鋯中的該等稀土金屬氧化物的含量係低於1.5重量%,換言之,例如,限制在低於1.4重量%、1.3重量%、1.2重量%、1.1重量%、1.0重量%、0.9重量%、0.8重量%、0.7重量%、或低於0.6重量%。因為上述理由,在各個情況下相對於根據本發明之二氧化鋯的總質量,該外來氧化物之含量亦可構成例如至少0.1重量%、0.2重量%、或至少0.3重量%
根據本發明,該二氧化鋯可特別地以單晶的形式存在。就此而言,根據本發明的二氧化鋯亦可特別地以二氧化鋯晶粒的形式存在,該二氧化鋯晶粒包含以根據本發明之該二氧化鋯形式存在之該等單晶。
若二氧化鋯晶粒包含根據本發明之二氧化鋯、及非根據本發明之二氧化鋯,根據本發明,較佳地,如此之包含根據本發明之二氧化鋯之二氧化鋯晶粒係被提供在一相較於二氧化鋯晶粒總重量下至少50重量%的比例,亦即例如至少60重量%、70重量%、80重量%、90重量%或同樣地至少95重量%。
根據本發明,較佳地,亦可提供的是,若根據本發明之耐火產品包含非根據本發明之二氧化鋯及根據本發明之二氧化鋯,相對於在該產品中二氧化鋯的總質量,所
述產品包含至少50重量%之根據本發明的二氧化鋯,例如,同樣地至少60重量%、70重量%、80重量%、90重量%或甚至95重量%。較佳地,該二氧化鋯可以二氧化鋯晶粒的形式存在於根據本發明之該等產品中,特別地,該二氧化鋯晶粒可如先前所述而構成。
根據本發明,被發現的是,若根據本發明之該二氧化鋯形成具有自30至1,000μm範圍中的尺寸之單晶,特別是自40至1,000μm的範圍中,自50至1,000μm,或自60至1,000μm的範圍中,根據本發明之該二氧化鋯、或包含根據本發明之二氧化鋯之一根據本發明的產品,每一者具有特別好的耐火性質,特別是優異的耐腐蝕性。
因此,可提供的是,例如,二氧化鋯晶粒包含至少50重量%之根據本發明的以單晶形式存在之二氧化鋯,其具有自30至1,000μm範圍中、自40至1,000μm範圍中、自50至1,000μm範圍中、或自60至1,000μm範圍中的尺寸,換言之,例如同樣地,在各個情況下相對於根據本發明之二氧化鋯晶粒的總重量,具有60、70、80、90或95重量%。
根據本發明,該術語”二氧化鋯”係用來指氧化物鋯(IV)之氧化物,換言之,ZrO2。
在本文件中,該術語”非根據本發明之二氧化鋯”係被理解為,特別表示不具有根據揭露於本文件中之本發明之二氧化鋯的特徵。
根據本發明之耐火產品可特別係一經形塑的產品,較特別地為一磨耗部件、較佳特別地為一用於連續鋼
鑄件之磨耗部件。在如此之產品或磨耗部件,該根據本發明之二氧化鋯可特別存在於該產品與該熔渣接觸的區域、或存在於該產品與該快速流動的熔融鋼鑄件接觸的區域,例如,在該餵槽管路(tundish pipe)中的浸入區域、在一滑動板的流經處、在該阻塞器凸出部(stopper lug)、及在該浸入式噴嘴之流入及浸入區域。在此文中,根據本發明之產物可為一餵槽管路、一滑動板、一單塊阻塞件(monobloc plug)、一噴嘴或一浸入式噴嘴。
根據本發明之耐火產品可特別係一經由等壓壓製法形塑而成的耐火產品。
根據本發明之該產品中,該根據本發明之二氧化鋯可存在於例如一碳基質中。該碳基質可特別地以石墨的形式存在。
典型地,然而,根據本發明之該產品可為任意的耐火產品,例如,亦可為一耐火陶瓷產品,換言之,以經燒結在一起之晶粒形式存在的經燒結的一耐火產品。
由先前技藝所知之經部分或完全穩定的二氧化鋯,其對於製造根據本發明之二氧化鋯,可初始地供作該起始點。在此之後,根據本發明之二氧化鋯可在降低的大氣壓,及在一用於穩定添加劑之氣相試劑存在下,藉由燃燒如此之以穩定添加劑經部分或完全地穩定之二氧化鋯,隨後冷卻而獲得。
該以穩定添加劑而被部分或完全穩定、且供作燃燒用之基底的二氧化鋯,可特別藉由在下列至少一物質之
形式的穩定添加劑被穩定:CaO、MgO、Y2O3或稀土氧化物。
除此之外,該經部分或完全穩定之二氧化鋯可為一根據先前技藝之經部分或完全穩定的二氧化鋯。
為了製造根據本發明之二氧化鋯,該根據先前技藝之二氧化鋯係在一降低的大氣壓下、及在一用於穩定添加劑之氣相試劑的存在下於此刻被燃燒。較佳地,該降低的大氣壓可具有一低於10-6Pa之氧分壓,例如亦可具有一低於10-7或10-8Pa之氧分壓。如先前技藝所知的是,該降低的大氣壓可藉由下列方式產生,例如在碳的存在下,燃燒該經部分或完全穩定之二氧化鋯,該碳係在石墨、焦炭或煤的形式下存在,例如,較佳地,在一密閉的爐室中。為此目的,該經部分或完全穩定之二氧化鋯可被置於一由如此之碳載體所做成的床上,例如,或與如此之碳載體混合之床。
此用於製造該呈立方晶系變型體、在室溫下穩定、具有一份量之外加氧化物、在本發明範圍內之二氧化鋯之方法的一重要步驟此刻在於,該經完全或部分穩定之二氧化鋯於該降壓燃燒反應中係在一用於該穩定添加劑之一氣相試劑的同時存在下發生。由於此氣相試劑與該二氧化鋯之穩定添加劑於該二氧化鋯之降氣壓燃燒反應過程中形成化合物,這導致至少部分、且較佳為大部分的該等穩定添加劑自該二氧化鋯移除。該二氧化鋯經冷卻後,相較於在燃燒至如此程度之前的該二氧化鋯中之穩定添加劑之百分比,該仍在該二氧化鋯中的穩定添加劑之百分比因而
降低,以致使相較於其燃燒反應之前的耐腐蝕性,該二氧化鋯之耐腐蝕性係實質上增加的。同時,儘管該穩定添加劑至少部分被移除,該二氧化鋯之立方晶系高溫變型體亦於室溫下被維持在一介穩態。整體來說,透過並根據此製造方法,根據本發明之二氧化鋯被獲得,儘管有低含量之穩定添加劑,該根據本發明之二氧化鋯形成一在室溫下介穩定之立方晶系變型體的礦物相。
在該二氧化鋯之降壓燃燒反應過程中,該與穩定添加劑反應之氣相試劑典型地可為任何物質或物質混合物,該物質或物質混合物在燃燒過程中係以氣相存在於該爐內氣氛下,且該氣相試劑與至少一穩定添加劑反應,惟較佳地,與所有的穩定添加劑反應。
根據一特別有利的實施例,一包含矽及/或鋁之氣體供作一氣相試劑。為了製作一包含矽及/或鋁此等可用於該二氧化鋯之降壓燃燒反應過程的如此之氣體,金屬矽及/或金屬鋁可被導入該爐室中該二氧化鋯及該碳載體旁,以在降壓燃燒反應之過程中形成該含矽及/或含鋁之氣體。在該燃燒過程中,該含矽氣體中的矽或該含鋁氣體中的鋁特別與在該氧化鈣、氧化鎂或氧化釔形式中之穩定添加劑反應,以至於至少部分的該等穩定添加劑自該二氧化鋯移除。
擇一地或另外地,一氣相試劑可以一氧化碳存在,其可在燃燒過程中自該碳載體形成。在本文中,一氣相試劑可以下列氣相物質之至少一者之形式存在,例如
矽、鎂或一氧化碳。
較佳地,降壓燃燒反應係在一至少部分該二氧化鋯被轉換成其立方晶系變型體之範圍中的溫度下進行,換言之,較佳地在高於1,173℃之溫度。亦可提供的是,該降壓燃燒反應係在高於2,370℃之溫度進行,以至於所有的二氧化鋯被轉換成其立方晶系變型體。在後者之情況中,在其冷卻後,大多數的、並非所有的二氧化鋯可存在於一在室溫下介穩定之立方晶系變型體。燃燒反應係在低於該二氧化鋯之熔融溫度下進行,換言之,低於2,690℃。
在該降壓燃燒反應過程中,與該氣相試劑反應之穩定添加劑的量特別決定於該燃燒反應的持續時間。因此,在降壓燃燒反應過程中,該參與一與該氣相試劑反應之穩定添加劑的比例隨著燃燒進行的長度增加,直到在一特定溫度下一平衡被建立。被發現的是,根據本發明,一在約12小時之量級下的燃燒時間對於該穩定添加劑與該氣相試劑之充分的反應而言係足夠的,致使該二氧化鋯具有小於1重量%之鈣、鎂及釔含量,導致該根據本發明、具有優異耐腐蝕性之二氧化鋯被獲得。根據本發明,已發現大部分使用此方法所製得之創新的二氧化鋯主要形成具有一平均尺寸小於30μm的晶粒。如先前段落中所述,然而,當如此之創新的二氧化鋯之晶粒存在於大於30μm的尺寸時,其具有特別有利的性質,特別是大於40μm、50μm、或大於60μm。基於此理由,根據本發明,可提供的是,該使用先前所述之方法所製得之創新的二氧化鉻係暴露在一進
一步的熱負載下,在該熱負載的過程中該等晶粒一同成長以形成更大的晶粒或單晶。根據本發明,較佳地,可提供的是,該使用前述方法所製得之創新的二氧化鋯係暴露在一大於900℃溫度之熱負載下,例如特別是在一900至1,500℃之溫度範圍,致使該二氧化鋯之晶粒一同成長以形成較大之晶粒或單晶,其具有自30至1,000μm範圍中的尺寸,特別是自40μm至1,000μm之範圍中、自50μm至1,000μm、或自60μm至1,000μm的範圍中。
本發明之另一目標係在於文中所述之該創新的二氧化鋯,其係以一在立方晶系變型體之礦物相的形式存在,該立方晶系變型體於室溫下係介穩定的,且其包含小於1重量%之鈣、鎂及釔的量。
本發明之另一目標係在於一用來製造耐火產品之二氧化鋯的使用,該二氧化鋯係以一在立方晶系變型體之礦物相的形式存在,該立方晶系變型體於室溫下係介穩定的,且其包含小於1重量%之鈣、鎂及釔的量。
該所用之二氧化鋯可具有如本文所述之特徵,及其使用可如本文所述執行。
本發明之另一目標係在於一用來製備一氧化鋯的方法,該二氧化鋯係以一在立方晶系變型體之礦物相的形式存在,該立方晶系變型體於室溫下係介穩定的,且其包含小於1重量%之鈣、鎂及釔的量,如本文所述。
本發明之另一目標係在於一用來製造一耐火產品之方法,其包含下列步驟:
- 提供一於室溫下係介穩定的礦物相,其係以立方晶系變型體之二氧化鋯形式存在,該立方晶系變型體包含小於1重量%之鈣、鎂及釔的量;- 將該於室溫下係介穩定的、以該包含小於1重量%之鈣、鎂及釔的量之立方晶系變型體之二氧化鋯形式存在的礦物相與一或更多額外之耐火原料結合;- 由該二氧化鋯及該額外的耐火原料壓製成一經模製的物體;- 燃燒該經模製的物體以製造一耐火產品。
因此,在本發明之方法中,一耐火原料被提供,其對應或包含根據本發明之二氧化鋯。此原料可被單獨使用或可與一或更多額外的耐火起始材料結合,例如與基於至少下列物質之一者之耐火原料:Al2O3、MgO、SiO2、Cr2O3或碳。
該等起始材料接著被壓製以形成一經模製的物體,亦即一生坯,特別是例如藉由平均壓製法(isostatic pressing)。
該生坯可接著經歷燃燒,隨而在冷卻後一耐火產品被獲得。
如先前所述,一根據本發明之耐火產品,亦特別是如根據本發明之方法中所製造之一產物,較佳地,其包含根據本發明之二氧化鋯具有自30至1,000μm範圍中之晶粒或單晶。若經本發明方法所壓製之該經模製的物體主要包含根據本發明之二氧化鋯,該二氧化鋯係由在燃燒前較
上述小之晶粒或單晶所組成者,則根據本發明之進行一方法步驟以增加根據本發明之二氧化鋯之晶粒尺寸可被提供。如先前所述,此方法步驟可由下述組成,即令該經模製物體受到一熱負載,在此情況下,本發明之二氧化鋯之晶粒或單晶之晶體尺寸增加。特別是,該熱負載可在如此之溫度及如此之持續時間下被施加,致使該二氧化鋯生長以形成主要具有自30至1,000μm尺寸之晶粒。該熱負載可在例如自900至1,500℃範圍中之溫度及一例如約72小時之持續時間下被施加。
此以熱負載誘導晶體成長的方法步驟,可在例如該經模製物體之壓製方法及燃燒反應中間進行。例如,若一耐火陶瓷產物被製造即可為所述情況,換言之,具有一陶瓷黏結劑之耐火產品,為了晶粒之燒結,其中該陶瓷燃燒反應係在高於1,500℃之溫度進行。
擇一地,此熱負載之方法步驟,可於該經模製物體被燃燒以製造一耐火產品之同時而進行。例如,若一耐火產品係以碳黏結被製造即可為所述情況,其中該燃燒反應係在所述溫度範圍中進行以焦化該碳並產生一碳黏結基質。
本發明之另一目標係在於一使用根據本發明方法而經製成之耐火產品。
本發明另外之特徵係描述在該等請求項、所伴隨之圖式及相關註記、及示範性之實施例中。
在本發明之任何變更中,揭示於本發明中之所有
特徵可彼此結合。
根據本發明之方法、及根據本發明之一耐火產品之一實施例將被更仔細地描述於下,其中該根據本發明之一耐火產品係使用該實施例中所代表之方法而製造。
該描述於實施例中之方法係用來製造一耐火產品,該耐火產品係在一浸入式噴嘴之形式,該浸入式噴嘴係關於一連續鋼鑄件之餵槽。
為了製造該浸入式噴嘴,首先一起始材料係以一礦物相形式被提供,該礦物相在具有約0.4重量%之鈣含量的立方晶系變型體二氧化鋯之形式係於室溫下穩定的。為了製造如此之起始材料,該與約4-5重量%之氧化鈣(對應至約2.8-3.6重量%之鈣含量)一同經部分穩定之二氧化鋯,係先於一降低之大氣壓、在一含有矽及鋁之氣體的存在下被燃燒,及接著被冷卻。在特定方面,此部分穩定之二氧化鋯係與成粒狀的碳及粒狀之金屬矽及鋁混合成一粒狀物,並接著在一封閉的爐室於約1,500℃之溫度持續燃燒約8小時。在此製程中,該成粒狀的碳一降低之大氣壓,導致該爐室內之氧分壓係約10-7Pa。同時,在該燃燒反應過程中富含矽及鋁之一氣體自該粒狀矽及鋁形成,且此氣體與該部分穩定之二氧化鋯中的氧化鈣之量反應。該部分穩定之二氧化鋯中的氧化鈣百分比因而在燃燒的過程中降低至一低於0.5重量%之平均百分比。包含在該立方晶系二氧化鋯之氧化鈣係藉由燃燒反應而移除;然而,即便在大多數之氧化鈣已被移除後,該立方晶系二氧化鋯仍在一介穩態(見圖
3)。在燃燒反應後,該對應形成之二氧化鋯形成晶粒,其大多數係小於30μm(見圖1及2中的微斷面)。該對應形成之二氧化鋯接著與一在石墨形式、添加一有機黏合劑之耐火原料混合。此混合物進一步與一在氧化鋁石墨(Al2O3-C)形式之耐火原料混合,並藉由平均壓製法模製以製作一經模製之物體,該物體係呈一未經燃燒之浸入式噴嘴之形狀。在此製程中,該二氧化鋯及石墨之混合物形成該浸入式噴嘴之一部分塗層,其形成在操作過程中那些與該熔融鋼材相接觸之區域。
該對應形成之經模製物體接著在一自900至1,000℃範圍內之溫度燃燒,致使該黏著劑被焦化且形成一碳黏結或一碳基質在各情況中。同時,該熱負載在此溫度區間被施加持續一期間,該期間是長到足以確保該二氧化鋯生長成具有一主要介在50及1,000μm範圍內之尺寸的晶粒。在冷卻之後,一浸入式噴嘴形狀之耐火產品被獲得。
隨附之該等圖1及2顯示根據該歷經第一燃燒反應之實施例所產生之二氧化鋯之微斷面,如上所述,其係在1,500℃,且係在進一步加工及該於900至1,000℃之第二燃燒反應之前。
1‧‧‧二氧化鋯晶粒
2‧‧‧黑色周圍
3‧‧‧暗灰色內含物
4‧‧‧明亮的區域
5、6‧‧‧單晶晶粒
7、8‧‧‧島狀物
9‧‧‧晶粒
10‧‧‧氧化鈣島狀物
該等圖式特別顯示:圖1 二氧化鋯晶粒的一橫截面之一影像,該二氧化鋯包含根據該實施例之二氧化鋯;圖2 圖1影像之一放大影像;
圖3 根據該實施例的二氧化鋯之X-射線繞射量測之結果;及圖4 二氧化鋯晶粒的一橫截面之一影像,該二氧化鋯包含根據該實施例所製造之二氧化鋯,但為其中不同之實施例。
圖1顯示二氧化鋯1晶粒之截面積的部分影像,該二氧化鋯1幾乎全部係由根據本發明之二氧化鋯所組成,且係使用該實施例之方法所獲得。該部分影像係約為一600x450μm之面積。該於影像右下側之黑色橫條代表一100μm之長度。如該實施例中所述,晶粒1仍被嵌在其周圍之碳粒2與粒狀矽及鋁,亦即圖1中的黑色區域。在黑色周遭2中之暗灰色內含物3係碳化矽之內含物,在燃燒過程中,該碳化矽內含物係形成自矽及該碳粒中的碳。該像是環礁般圍繞晶粒1之不規則、較明亮的區域4主要由碳氮化鋯(zirconium carbonitride)所組成,其係自該二氧化鋯中的鋯、該碳粒中的碳、及燃燒過程中大氣的氧所形成。
晶粒1包含一數目大之二氧化鋯單晶晶粒。該等單晶晶粒間的邊界以在該晶粒1中薄、黑、網狀的區域顯現。晶粒1中之以白色為框架的區域係以一放大的影像顯示在圖2中。
根據圖2,晶粒1之許多單晶晶粒係清楚地以放大影像顯示。於該影像中間下側之白色橫條代表一50μm之長度。該等單晶晶粒中的其中二者,在圖2中藉由參考數值5
及6所識別,有關其等之元素組成係更進一步地被檢驗。晶粒1亦藉由X-射線繞射測定法檢驗,以決定其晶體組成。
單晶晶粒5及6的檢驗揭示下列元素組成,下列元素組成係以每一所論元素之重量%相對於該各別之單晶所表示:
單晶晶粒內部之該等黑色”島狀物”7、及圍繞各個單晶晶粒之該等薄、黑色網狀區域8亦就其等之元素組成而進一步被檢驗,被發現的是,不同於該等單晶晶粒,該等區域7、8較該等單晶晶粒包含高濃度之鈣、鋁、及矽,及較高濃度之氧,及較低濃度之鋯。因此,可提供的是,因為擴散之進行,最初存在於二氧化鋯中用作穩定化目的之氧化鈣已聚焦在該等二氧化鋯結晶內部之該等島狀物7中、及在該等二氧化鋯結晶外部之該等區域8中。更可進一步提供,由於擴散之進行,在燃燒反應的過程中該金屬鋁及矽已被氧化,且亦聚集在所述島狀物7及區域8中。
如圖3所示,根據該實施例所製成之二氧化鋯的該X-射線繞射檢定,其確定了大多數之根據該實施例所製成之二氧化鋯係在立方晶系變型體形式,且只有非常少數係在單斜晶系形式。該立方晶系二氧化鋯之主要峰值係以K為標示,及該單斜晶系二氧化鋯之主要峰值係以M為標示。
圖4顯示晶粒9之一橫截面之部分影像,該晶粒9
實質上係根據該實施例所製得之二氧化鋯,但其不同之處在於,其並非以約1,500℃之溫度持續燃燒8小時,反而係以約1,300℃之溫度持續燃燒約24小時。此清楚地顯示,在該等二氧化鋯晶粒中,相較於其他特徵,該等包含較高濃度之氧化鈣的島狀物10比起圖1及2中的二氧化鋯在數目上係較大及較小的。這是歸因於較長的燃燒期間,因為這代表更多的時間可用於該二氧化鈣之擴散。
Claims (15)
- 一種耐火產品,其包含一呈立方晶系變型體之二氧化鋯形式的礦物相,該礦物相在室溫下為介穩定,具有低於1重量%之鈣、鎂及釔含量。
- 如請求項1之產品,其中該呈立方晶系變型體之二氧化鋯包含一具有自30至1,000μm範圍內之晶粒尺寸的單晶晶粒。
- 如請求項1-2中至少任一項之產品,其中該二氧化鋯係以二氧化鋯晶粒存在,其包含至少50重量%之二氧化鋯。
- 如請求項1-3中至少任一項之產品,其為一用於連續鋼鑄件之損耗部件的形狀。
- 如請求項1-4中至少任一項之產品,其為滑動板(slide plates)、單塊阻塞器(monobloc stoppers)、噴嘴、浸入管(immersion pipes)或浸入式噴嘴(submerged nozzles)之形狀。
- 如請求項1-5中至少任一項之產品,其中該二氧化鋯存在於一碳基質中。
- 如請求項1-6中至少任一項之產品,其中該二氧化鋯在一降低之大氣壓,及一用於穩定添加劑之氣相試劑的存 在下,藉由燃燒以穩定添加劑經部分或完全穩定之二氧化鋯,隨後冷卻而獲得。
- 如請求項7之產品,其具有至少下列物質之一者之形式的穩定添加劑:氧化鈣、氧化鎂、氧化釔、或稀土族氧化物。
- 如請求項7-8中至少任一項之產品,其中該降低之大氣壓具有一低於10-6Pa之氧分壓。
- 如請求項7-9中至少任一項之產品,其具有至少下列氣相物質之一者之形式的氣相試劑:矽、鋁或一氧化碳。
- 如請求項7-10中至少任一項之產品,其中該燃燒反應係在一自1,173至2,690℃範圍內的溫度進行。
- 一種在一礦物相形式之二氧化鋯,該礦物相之立方晶系變型體於常溫下為介穩定,具有一低於1重量%之鈣、鎂及釔含量。
- 一種礦物相的用途,將該於下述情況時為介穩定的,亦即呈二氧化鋯之立方晶系變型體、常溫下、具有一低於1重量%之鈣、鎂及釔含量的礦物相,供作為用於製造耐火產品之原料。
- 一種用於製造一耐火產品的方法,其包含下列步驟: 14.1提供一在室溫下為介穩定之礦物相,其為二氧化鋯之立方晶系變型體形式、包含低於1重量%之鈣、鎂及釔含量;14.2將該二氧化鋯與額外之耐火原料相結合;14.3壓製一經模製的物體,該經模製的物體係自該二氧化鋯及該額外之耐火原料所做成;14.4燃燒該經模製的物體以製造一耐火產品。
- 一種使用如請求項14之方法所製成之耐火產品。
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