TWI555719B - 摻雜之氧化鉻產物 - Google Patents
摻雜之氧化鉻產物 Download PDFInfo
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Description
具體而言,本發明係關於自氧化鉻產生之新穎燒結產物,係關於製造該產物之方法且係關於該產物尤其在玻璃爐中之用途。
在耐火產物中,熔鑄產物可能不同於燒結產物。
與燒結產物不同,熔鑄產物通常包含高豐度粒間玻璃相,其充滿晶粒網絡。因此,燒結產物及熔鑄產物在其各別應用中所過到之問題及所採用的解決該等問題之技術方案通常不同。此外,由於製造方法間之重大差異,所研發用於製造熔鑄產物之組成根據推論不能用於製造燒結產物,反之亦然。
燒結產物係藉由以下方式獲得:將適當原料混合,然後形成呈粗坯狀態之此混合物,然後使所得粗坯部件在足以燒結此粗坯部件之溫度及時間下燃燒。
燒結產物意欲用於廣泛不同工業,此視其化學組成而定。
FR 2 647 435提出基於氧化鉻之燒結產物,其含有氧化鈦及單斜氧化鋯且對熱衝擊及熔融玻璃之腐蝕具有良好耐受性。
EP 546 432提出含有氧化鈦之基於氧化鉻之燒結產物。
WO 2010/119422提出基於氧化鉻之燒結產物,其以改良耐昇華性及耐腐蝕性之比例含有氧化鈦及氧化鋁。
自氧化鉻產生之燒結產物目前廣泛用於玻璃爐中,具體而言用於熔化意欲用於製造玻璃纖維之玻璃之爐中。特定而言,緻密氧化鉻產物展示極佳耐腐蝕性。因此,US 4 724 224闡述基於氧化鉻之燒結砌塊(block),其對熔融玻璃之腐蝕具有良好耐受性。此產物含有至少約1%二氧化矽。
然而,當在氧化氣氛中、具體而言在水分存在下將氧化鉻暴露於高於1000℃之溫度時,其對昇華特別敏感。
最後,若玻璃含有諸如鹼金屬硼酸鹽或氫氧化鈉(NaOH)等揮發性物質,則此等要素可與氧化鉻反應以形成鹼金屬鉻酸鹽,例如Na2CrO4。此等反應促使氧化鉻昇華,增加腐蝕且可導致氧化鉻及鉻酸鹽再凝結於爐之最冷區(例如用於將煙道氣(呈粉塵形式)排放至大氣之迴路中或砌塊較少暴露於熱之面(例如砌塊背面)上)。當此再凝結發生於進給砌塊或槽砌塊背面時,亦會增加富含鉻之內含物釋放至玻璃中之風險。
極高品質玻璃之現今發展提高了對玻璃爐中之耐火產物、尤其槽中所用產物之要求。因此,需要具有良好耐昇華性之新耐火產物。
本發明旨在滿足此需要。
出於此目的,本發明提出燒結產物,其以基於氧化物之重量百分比計具有如下平均化學組成:Cr2O3:80.0-99.0%
0.5%TiO2 9.0%
0.1%MgO3.0%
ZrO2 5.0%條件係TiO2/MgO莫耳比介於1.5與9.0之間且TiO2/Cr2O3莫耳比小於0.12。
出人意料地,本發明者已發現,此組成使得可達成顯著性能特徵,且具體而言極佳耐昇華性。
因此,本發明產物極適於用作槽砌塊,具體而言當其意欲與諸如增強玻璃(E-玻璃)等熔融玻璃接觸時極適合。
較佳地,本發明產物亦可具有以下可選特徵中之一或多者:- TiO2/MgO莫耳比大於2.0、大於2.5、大於3.0及/或小於8.0、小於7.5、小於7.0、小於6.0、或甚至小於5.5或小於5.0;- TiO2/Cr2O3莫耳比小於0.11、小於0.10、小於0.09或甚至小於0.08;- 氧化鉻之質量含量大於85.0%、大於87.0%、大於90.0%及/或小於98.0%、小於97.0%;- 氧化鈦TiO2之質量含量大於0.7%、較佳大於1.0%、更佳大於1.5%、或甚至大於2.0%、大於2.5%、大於3.0%及/或小於8.0%、較佳小於7.0%、或甚至小於6.0%、小於5.5%、或小於5.0%;- MgO質量含量大於0.15%、大於0.20%、大於0.24%、大於0.25%、或甚至大於0.3%及/或小於2.5%、小於2.0%、
小於1.8%、小於1.5%、小於1.2%、小於1.0%;- 在一實施例中,產物不含氧化鋯,而在另一實施例中,氧化鋯(ZrO2)質量含量大於0.2%、大於0.5%、大於1.0%、大於2.0%、及/或小於4.5%、或甚至小於4.0%;- 燒結產物中除Cr2O3、MgO、TiO2及ZrO2以外的氧化物物質的總質量含量以基於該等氧化物之重量百分比計小於3.0%、較佳小於2.0%、較佳小於1.5%、較佳小於1.0%、較佳小於0.9%、更佳小於0.7%、且仍較佳小於0.5%;- 氧化物佔產物質量之超過95%、超過98%、超過99%或甚至約100%;- 視孔隙度小於15%、較佳小於10%、較佳小於5%、較佳小於2%、較佳小於1%;- 產物具有大於4.0 g/cm3、較佳大於4.4 g/cm3、較佳大於4.5 g/cm3或甚至大於4.6 g/cm3之體密度;及- 產物呈砌塊形式,較佳具有大於5 kg、較佳大於10 kg之質量。
本發明亦係關於製造燒結產物之方法,其包含以下步驟:a)將原料混合以形成進料;b)自該進料形成粗坯部件;及c)燒結該粗坯部件以獲得該燒結產物,此方法值得注意之處在於確定進料以使該燒結產物符合本發明。
較佳地,本發明方法亦可具有以下可選特徵中之一或多者:- 包含氧化物(氧化物粉末及視情況熟料)之顆粒原料各自具有小於150 μm、較佳小於100 μm、較佳小於50 μm之中值大小;- 氧化物Cr2O3、TiO2及MgO及視情況ZrO2係以該等氧化物之微粒及視情況該等氧化物之熟料形式存於進料中,該等微粒一起形成粉末摻合物,其具有小於50 μm、較佳小於40 μm、較佳小於20 μm、較佳小於10 μm或甚至小於5 μm之中值大小;- 包含氧化物Cr2O3之全體微粒以相對於全體重量之重量百分比計較佳包含超過70%、超過80%、超過90%、超過95%、超過99%或甚至約100% Cr2O3;- 包含氧化物TiO2之全體微粒以相對於全體重量之重量百分比計較佳包含超過70%、超過80%、超過90%、超過95%、超過99%或甚至約100% TiO2;- 包含氧化物MgO之全體微粒以相對於全體重量之重量百分比計較佳包含超過70%、超過80%、超過90%、超過95%、超過99%或甚至約100% MgO;- 包含氧化物ZrO2之全體微粒以相對於全體重量之重量百分比計較佳包含超過70%、超過80%、超過90%、超過95%、超過99%或甚至約100% ZrO2;- 進料以基於進料之氧化物之重量百分比計包含至少10%及/或小於50%熟料;
- 進料中之熟料具有小於50 μm、較佳小於40 μm、較佳小於20 μm之中值大小;- 進料所包含微粒包含MgTiO3及/或Mg2TiO4及/或MgTi2O5或實質上由其組成;在一實施例中,以重量計超過50%、超過75%或甚至實質上100%之MgO係以MgTiO3形式供應;及- 藉由等壓壓製來實施成型操作。
本發明亦係關於使用本發明方法製造或能夠使用本發明方法製造之燒結產物。
最後,本發明係關於本發明燒結產物、或使用本發明方法製造或能夠使用本發明方法製造之燒結產物在玻璃爐中(具體而言在可能與熔融玻璃或與熔融玻璃所散發煙道氣接觸之爐區中,例如在煙道氣排放迴路中)之用途。
本發明亦係關於包含本發明產物之設備,該產物係置於該設備中可能與溫度高於1000℃之氧化環境或與由熔融玻璃散發之煙道氣接觸之區域中。具體而言,可將該產物置於該槽中可能與熔融玻璃,具體而言與(例如)E-玻璃、R-玻璃或S-玻璃型之增強玻璃、AR(耐鹼)玻璃或用於隔熱纖維之玻璃接觸之區域中。
在閱讀以下詳細說明後,本發明之其他特徵及優點將變得更明瞭。
術語「雜質」應理解為意指不可避免地必然由原料引入之成份或得自與此等成份之反應。雜質並非必需成份,而
僅係容許的。
術語微粒之「大小」係指其最大尺寸dM與其最小尺寸dm之平均值:(dM+dm)/2。
通常,微粒之「最大大小」對應於該等微粒可穿過之最小標準篩目。
通常,微粒摻合物之「中值大小」係指將此摻合物中之微粒劃分成數量相等之第一及第二群體之大小,此等第一及第二群體分別僅包含大小大於中值大小及大小小於中值大小的微粒。
通常,術語「熟料」係指藉由將燒結體研磨至期望粒徑而獲得之微粒粉末。燒結體可特定地製備或其可為製造廢料或用過後可由此回收之產物。
根據ASTM D 578-05標準「Standard Specification for Glass Fiber Strands」,E-玻璃以重量百分比計具有如下化學組成:
-B2O3:0-10%
-CaO:16-25%
-Al2O3:12-16%
-SiO2:52-62%
-MgO:0-5%
-鹼金屬氧化物:0-2%
-TiO2:0-1.5%
-Fe2O3:0.05-0.8%
-氟:0-1%。
除非另外提及,否則當提及燒結產物或進料時,百分比均為基於氧化物之重量百分比。
本發明產物可根據上文所述步驟a)至c)製造。
此等步驟係習用的,但在步驟a)中,以熟習此項技術者熟知之方式確定進料,以使得在步驟c)後獲得之燒結產物具有處於上文所述本發明範圍內、具體而言處於較佳範圍內之Cr2O3、TiO2、MgO及視情況ZrO2含量。
認為極小TiO2含量對於獲得有用技術效果係必須的。然而,必須限制TiO2含量以避免降低耐腐蝕性。
在一實施例中,未向進料中添加氧化鋯。然而,在另一實施例中,確定進料以使燒結產物包含氧化鋯。從而有利地改良產物之耐熱衝擊性。
亦較佳確定進料以限制燒結產物中除Cr2O3、TiO2、MgO及視情況ZrO2以外之氧化物物質(後文稱為「其他氧化物物質「)之總含量。較佳地,向進料中引入小於1重量%之並非Cr2O3、TiO2及MgO及視情況ZrO2之來源的原料。
根據定義,其他氧化物物質補足氧化物Cr2O3、TiO2及MgO及視情況ZrO2至100%之差額(balance)。藉由限制此等其他氧化物物質之總含量,可有利地增加氧化物Cr2O3、TiO2及MgO及視情況ZrO2之含量且具體而言氧化鉻含量。亦使得可限制諸如二氧化矽等有害物質之含量,其存在往往會降低耐腐蝕性。
較佳地,其他氧化物物質由雜質組成,換言之,並未出
於改變燒結產物之組成之目的向進料中引入除Cr2O3、TiO2、MgO及視情況ZrO2以外之其他物質。以基於該等氧化物之重量百分比計,在燒結產物中之含量低於3.0%時,認為雜質之影響不會實質上改變所獲得結果。較佳地,燒結產物中總雜質含量以基於該等氧化物之重量百分比計小於1.0%、更佳小於0.9%。
較佳地,燒結產物中每一雜質之含量小於0.5%、小於0.3%、或甚至小於0.1%或小於0.05%。
具體而言,雜質包含Al2O3、Fe2O3、P2O5、SiO2及鹼金屬氧化物(例如Na2O及K2O)以及鹼土金屬氧化物CaO、SrO及BaO。
較佳地,確定進料以使得在燒結產物中,發現以下基於氧化物之重量百分比:- Al2O3<1.0%,較佳地Al2O3<0.5%;及/或- Fe2O3<0.2%,較佳地Fe2O3<0.1%,更佳地Fe2O3<0.08%;及/或- P2O5<1.0%,較佳地P2O5<0.5%;及/或- SiO2<0.9%,較佳地SiO2<0.6%,較佳地SiO2<0.3%,較佳地SiO2<0.1%;及/或- Na2O<0.2%,較佳地Na2O<0.1%;及/或- K2O<0.2%,較佳地K2O<0.1%,其中較佳地Na2O+K2O<0.2%,較佳地Na2O+K2O<0.1%;- CaO<0.6%,較佳地CaO<0.5%,較佳地CaO<0.2%;及/或
- SrO<0.6%,較佳地SrO<0.5%,較佳地SrO<0.2%;及/或- BaO<0.6%,較佳地BaO<0.5%,較佳地BaO<0.2%。
限制Al2O3含量使得可避免在熔融玻璃浴中形成耐火缺陷之風險。
諸如Na2O及K2O等鹼性金屬氧化物具有揮發性且應限制其含量。此限制使得可避免形成鉻酸鹽之風險。
限制CaO及/或SrO及/或BaO之含量使得可避免形成鉻酸鹽之風險。
限制SiO2含量達成良好耐腐蝕性。
亦確定進料以使氧化物較佳佔燒結產物重量之超過99.9%,較佳佔燒結產物重量之約100%。
較佳地,在進料中,氧化物粉末各自具有小於150 μm、較佳小於100 μm、較佳小於50 μm之中值大小。更佳地,此等粉末之摻合物具有小於50 μm、較佳小於40 μm、較佳小於20 μm、較佳小於10 μm或甚至小於5 μm之中值大小。由此,有利地改良在燒結步驟期間該部件之緻密化。
進料亦較佳包括超過10%熟料。在粗坯部件形成期間,熟料微粒之結構有利地改良壓實。
可藉由燒結Cr2O3及/或TiO2及/或MgO及/或ZrO2粉末且隨後研磨來獲得熟料。具體而言,可藉由回收本發明產物得到熟料。
熟料微粒之最大大小較佳小於150 μm、較佳小於100 μm。較佳地,熟料具有小於50 μm、較佳小於20 μm之中
值大小。
進料中之熟料含量以進料之重量百分比計較佳小於50%、小於40%或甚至小於30%。
除經計量以使燒結產物具有以重量計之期望平均化學組成的原料以外,進料通常亦可包括標準黏合劑(例如有機黏合劑)及/或解凝劑。
在步驟b)中,可將步驟a)中製備之摻合物倒入模型中且然後實施成型操作,以形成粗坯部件。
較佳地,模型經定型以使得所獲得燒結產物呈重量大於5 kg、較佳大於10 kg之砌塊形式。該等砌塊非常適於預期應用。
可(例如)自等壓壓製、滑鑄、單軸壓製、凝膠澆注或振動澆注技術或自此等技術之組合實施成型。
較佳地,在高於100 Mpa之壓力下自等壓壓製技術實施成型。實際上,此技術允許更具反應性之燒結且使得能夠獲得更緻密之燒結產物。因此,燒結產物之視孔隙度可小於15%、較佳小於10%、較佳小於5%、較佳小於2%、較佳小於1%。燒結產物之體密度可大於4.0 g/cm3。
在步驟c)中,燒結粗坯部件。
較佳在介於1400℃與1700℃間之溫度下在還原或氧化氣氛中(較佳在還原氣氛中)且較佳在大氣壓力下實施燒結。
在燒結後,獲得本發明燒結產物。
有利地,根據下文所定義測試,使用以上方法製造之燒結產物具有小於7.5×10-6%.s-1、小於6.0×10-6%.s-1、小於
5.0×10-6%.s-1、或甚至小於4.0×10-6%.s-1、或小於3.5×10-6%.s-1之昇華Is。
出於闡釋本發明之目的,給出以下非限制實例。
在此等實例中,選擇以下所用原料,所給出百分比係基於氧化物之重量百分比:- Pcr:氧化鉻粉末,其含有約99.5% Cr2O3且具有2.8 μm中值大小;- Pti:氧化鈦粉末,其含有約95% TiO2且具有2.3 μm中值大小;- Pmt:粉末,其含有約99% MgOTiO2且具有約3 μm中值大小;- Pzr:粉末,其含有約99% ZrO2且具有約3.5 μm中值大小;- 自Cr2O3及TiO2粉末獲得之熟料1,其含有約91.5% Cr2O3、3.8% TiO2及3.5% ZrO2且中值大小小於50 μm;- 自Cr2O3及TiO2粉末獲得之熟料2,其含有約94.2% Cr2O3及3.8% TiO2且中值大小小於50 μm。
根據上文所述步驟a)至c)來製造燒結耐火砌塊。
在步驟b)中,藉由等壓壓製對摻合物實施成型操作,以形成尺寸為100 mm×100 mm x約150 mm高度之粗坯部件。
然後在步驟c)中,在還原氣氛中,在大氣壓力及1550℃燒結溫度下燒結粗坯部件。
密度係以相對於具有試樣之化學組成之材料之理論密度
的百分比給出。此密度對材料之機械強度及耐腐蝕性及耐昇華性具有影響(此乃因多孔性促進熔融玻璃或爐氣氛中所含侵入性物質之滲透)。出於此等原因,密度小於其理論密度之90%的材料在大多數應用中係不可接受的。
為量測耐腐蝕性,取直徑為20 mm且高度為100 mm之呈圓柱形桿形式之產物試樣並實施測試,該測試在於旋轉浸漬於加熱至1600℃之熔融E-玻璃(用於增強纖維)浴中之試樣。繞試樣夾之軸之旋轉速度係6轉/分鐘。此速度使得可極快地補充腐蝕介面且因此使測試顯著更嚴格。該測試持續180小時。在此時期結束時,將每一試樣之浸漬部分與非浸漬部分分離。對於每一部分,均測定試樣之剩餘體積,且然後藉由差值來確定測試期間之體積損失。然後自損失體積與初始體積之比率來計算損失體積之百分比。選擇對照產物(實例1)試樣之損失體積百分比作為比較基準。
將對照產物試樣因腐蝕而損失之浸漬體積百分比與整個試樣因腐蝕而損失之浸漬體積百分比之比率乘以100,得到所測試試樣之玻璃相對於對照產物之玻璃之耐腐蝕性的量度。在下表1中以及在申請專利範圍中,由此定義之腐蝕指數由「Ic」表示。
因此,腐蝕指數高於100對應於腐蝕損失低於對照產物。因此,所論述產物展示優於對照產物之對熔融玻璃之耐腐蝕性。腐蝕指數低於100對應於腐蝕損失高於對照產物。因此,所論述產物展示低於對照產物之對熔融玻璃之耐腐蝕性。
此處認為腐蝕指數Ic高於110時之耐腐蝕性特別令人滿意。
使用ATG SETARAM TG96型儀器藉由熱重分析來量測耐昇華性。為量測耐昇華性,取大小為10 mm且高度為50 mm且具有正方形基底之呈桿形式之試樣並實施測試,該測試在於將此等試樣懸置於受控氧環境中,逐漸將其加熱(以10℃/分鐘升溫)至1550℃且然後維持此溫度並保持10小時。記錄試樣之重量變化。由此,測定在10小時保持持續時間內的重量損失(保持開始時所記錄之最大重量與保持結束時所記錄之最小重量間之差值)。指數Is係每秒的重量損失(以佔試樣最大重量之百分比表示)。
此處認為當昇華指數Is比對照實例低至少20%時之耐昇華性特別令人滿意。
實例1(對照產物)係由Saint-Gobain SEFPRO出售之產物C1215。此產物目前用於玻璃熔爐之槽。
表1指示所用原料。
表2匯總所獲得之結果。
估算所測試各產物之平均化學組成(以基於氧化物之重量百分比計)。至100%之差額對應於雜質。
表2顯示,需要TiO2/MgO莫耳比大於1.5以獲得足夠緻密化,並小於9以具有足夠耐腐蝕性。
表2顯示,所測試本發明產物具有顯著改良之耐昇華性。
如實例6、7及9顯示,本發明產物之耐腐蝕性高於對照
產物之耐腐蝕性。然而,實例4顯示,若TiO2/Cr2O3莫耳比大於0.12,則儘管緻密化良好,但耐腐蝕性之改良較差。
當然,本發明不限於所闡述及所展示之實施例,此等實施例係作為說明性且非限制性之實例提供。
Claims (24)
- 一種燒結產物,其具有小於10%之視孔隙度,且以基於氧化物之重量百分比計具有如下平均化學組成:Cr2O3:80.0-99.0% 0.5%TiO2 9.0% 0.2%<MgO3.0% ZrO2<4.5%除Cr2O3、TiO2、MgO及ZrO2以外的氧化物<2.0%,條件係TiO2/MgO莫耳比介於1.5與9.0之間且TiO2/Cr2O3莫耳比小於0.12。
- 如請求項1之產物,該產物之體密度係大於4.0g/cm3。
- 如請求項1之產物,其中該等莫耳比滿足以下條件:TiO2/MgO>2.5及/或TiO2/MgO<8.0。
- 如請求項1之產物,其中該TiO2/MgO莫耳比小於7.0。
- 如請求項1至4中任一項之產物,其以基於該等氧化物之重量百分比計包含0.5%至5.0% ZrO2。
- 如請求項1至4中任一項之產物,該MgO含量以基於該等氧化物之重量百分比計係大於0.3%及/或小於1.5%。
- 如請求項1至4中任一項之產物,其包含以基於該等氧化物之重量計,小於1.5%之除Cr2O3、TiO2、MgO及ZrO2以外的氧化物。
- 如請求項7之產物,其包含以基於該等氧化物之重量計,小於1.0%之除Cr2O3、TiO2、MgO及ZrO2以外的氧化物。
- 如請求項8之產物,其包含以基於該等氧化物之重量計,小於0.5%之除Cr2O3、TiO2、MgO及ZrO2以外的氧化物。
- 如請求項1至4中任一項之產物,其係自進料製造,其中至少該等氧化物Cr2O3、MgO及TiO2係以該等氧化物之微粒及視情況該等氧化物之熟料微粒形式存在,該等微粒一起形成中值大小小於50μm之粉末摻合物。
- 如請求項10之產物,其係自進料製造,其中至少該等氧化物Cr2O3、MgO及TiO2係以該等氧化物之微粒及視情況該等氧化物之熟料微粒形式存在,該等微粒一起形成中值大小小於10μm之粉末摻合物。
- 如請求項1至4中任一項之產物,其係自進料製造,該進料以基於該等氧化物之重量百分比計包含至少10%熟料。
- 如請求項1至4中任一項之產物,其係自進料製造,其中該等氧化物粉末及視情況該熟料各自具有小於150μm之中值大小。
- 如請求項1至4中任一項之產物,其中Fe2O3<0.2%及/或P2O5<1%及/或SiO2<0.5%。
- 如請求項1至4中任一項之產物,其係呈質量大於5kg之砌塊(block)形式。
- 如請求項1至4中任一項之產物,其中CaO的含量小於0.6%。
- 如請求項1至4中任一項之產物,其中該TiO2的含量大於 1.0%。
- 如請求項17之產物,其中該TiO2的含量大於1.5%。
- 如請求項18之產物,其中該TiO2的含量大於2.5%。
- 如請求項1至4中任一項之產物,其中該MgO質量大於0.3%。
- 如請求項1至4中任一項之產物,其係藉由燒結由進料形成之粗坯部件所獲得,該進料包含含有MgTiO3及/或Mg2TiO4及/或MgTi2O5的微粒。
- 如請求項21之產物,其中以重量計超過50%之MgO係以MgTiO3形式供應。
- 一種包含如請求項1至22中任一項之產物之設備,該產物係置於該設備中可能與溫度高於1000℃之氧化環境接觸或與熔融玻璃所散發之煙道氣接觸之區域中。
- 一種包含如請求項1至22中任一項之產物之槽,該產物係置於該槽中可能與熔融玻璃接觸之區域中。
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FR1151228A FR2971504A1 (fr) | 2011-02-15 | 2011-02-15 | Produit d'oxyde de chrome dope |
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WO2014048586A1 (de) * | 2012-09-28 | 2014-04-03 | Refractory Intellectual Property Gmbh & Co. Kg | Versatz zur erstellung eines feuerfesten werkstoffs, ein feuerfester werkstoff, ein verfahren zur herstellung eines feuerfesten werkstoffes sowie eine verwendung eines stoffes als sinterhilfsmittel |
US10407990B2 (en) * | 2012-11-16 | 2019-09-10 | U.S. Well Services, LLC | Slide out pump stand for hydraulic fracturing equipment |
RU2716676C2 (ru) * | 2016-02-05 | 2020-03-13 | Сен-Гобен Серэмикс Энд Пластикс, Инк. | Огнеупорный объект из оксида хрома и способ его формования |
FR3075786B1 (fr) * | 2017-12-22 | 2024-04-19 | Saint Gobain Ct Recherches | Produit contenant de l’oxyde de chrome 3 |
JP6615276B1 (ja) * | 2018-07-02 | 2019-12-04 | 東京窯業株式会社 | クロミア質れんが |
CN108911721B (zh) * | 2018-08-31 | 2021-07-16 | 广州市石基耐火材料厂 | 骨料型氧化铬耐火材料及其制备方法 |
CN109020521B (zh) * | 2018-08-31 | 2021-09-14 | 广州市石基耐火材料厂 | 致密型氧化铬砖及其制造方法 |
CN113999044B (zh) * | 2021-11-12 | 2022-08-26 | 郑州磨料磨具磨削研究所有限公司 | 一种多孔陶瓷板及其制备方法 |
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SU1194859A1 (ru) * | 1983-09-15 | 1985-11-30 | Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им.Ленсовета | Шихта дл получени огнеупорного материала |
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DE4140417C1 (zh) | 1991-12-07 | 1993-04-29 | Dyko Industriekeramik Gmbh, 4000 Duesseldorf, De | |
JPH05279115A (ja) * | 1992-03-27 | 1993-10-26 | Shinagawa Refract Co Ltd | 緻密質酸化クロム焼結体及びその製造方法 |
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FR2944522B1 (fr) * | 2009-04-15 | 2011-09-30 | Saint Gobain Ct Recherches | Produit fritte a base d'oxyde de chrome. |
US20110033613A1 (en) * | 2009-08-04 | 2011-02-10 | Battelle Memorial Institute | Method and Composition for Protection of Refractory Materials in Aggressive Environments |
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2011
- 2011-02-15 FR FR1151228A patent/FR2971504A1/fr not_active Withdrawn
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2012
- 2012-02-09 WO PCT/IB2012/050590 patent/WO2012110923A1/fr active Application Filing
- 2012-02-09 MX MX2013009349A patent/MX352699B/es active IP Right Grant
- 2012-02-09 EP EP12705449.2A patent/EP2675769B1/fr active Active
- 2012-02-09 US US13/985,649 patent/US9242885B2/en active Active
- 2012-02-09 JP JP2013554027A patent/JP5774135B2/ja active Active
- 2012-02-09 CN CN201611259144.4A patent/CN106966710A/zh active Pending
- 2012-02-09 CN CN2012800079807A patent/CN103347837A/zh active Pending
- 2012-02-09 EA EA201391051A patent/EA201391051A1/ru unknown
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US2498622A (en) * | 1947-11-06 | 1950-02-21 | Corning Glass Works | Refractory composition |
US5106795A (en) * | 1989-05-26 | 1992-04-21 | Corhart Refractories Corporation | Chromic oxide refractories with improved thermal shock resistance |
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WO2012110923A1 (fr) | 2012-08-23 |
EA201391051A1 (ru) | 2014-01-30 |
CN103347837A (zh) | 2013-10-09 |
MX352699B (es) | 2017-12-05 |
EP2675769B1 (fr) | 2017-09-20 |
JP2014511328A (ja) | 2014-05-15 |
TW201238932A (en) | 2012-10-01 |
EP2675769A1 (fr) | 2013-12-25 |
CN106966710A (zh) | 2017-07-21 |
JP5774135B2 (ja) | 2015-09-02 |
US20140013807A1 (en) | 2014-01-16 |
MX2013009349A (es) | 2013-09-26 |
US9242885B2 (en) | 2016-01-26 |
FR2971504A1 (fr) | 2012-08-17 |
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