CN1333842A - 可湿润和抗侵蚀/氧化的碳复合材料 - Google Patents
可湿润和抗侵蚀/氧化的碳复合材料 Download PDFInfo
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Abstract
本方法包括磨碎的定量的TiO2和B2O3(或其它金属硼化物前体)彼此混合,以生成前体混合物,然后将此前体混合物与至少一种含碳组分相混合以生成碳复合材料,当暴露于熔融铝中或经受槽的起动和运行的热的作用时,便在现场形成TiB2(或其它金属硼化物)。本发明还涉及这样生产出的碳复合材料,这类材料可以用来形成构造阴极结构用的块料(或用于这类块料的涂料)或可以用来制备嵌缝充填组分和涂料组分供铝还原槽用,或制备供与熔融金属一起使用的仪器用防护涂料。
Description
技术领域
本发明涉及碳复合材料,特别涉及用于形成电解还原槽,主要用于生产铝金属的那些电解槽的阴极或槽的内衬类材料,以及涉及这类阴极件和内衬件及有关产品。更具体而言,本发明涉及抗侵蚀/氧化的碳复合材料,且更理想是可被熔融铝湿润的碳复合材料。
背景技术
用于生产铝的电解槽阴极通常呈由炭精块等制成的内衬形式,这些炭精块沿着电解槽的底壁和侧壁安置。一种典型的电解槽10示于附图1和2上。图中熔融电解液12的表面11与槽的侧壁14相接触,阴极15往往如图示是倾斜的(这通常称为“整体倾斜式槽内衬”),以便减小由可能会引起过分的金属运动的磁流体动力(MHD)影响所造成的对电解槽的侵蚀。导电阳极(图中未示出)从上面浸入熔融电解液中,从而完解所要求的电极组合。阴极内衬是导电的并与熔融电解液12相接触,且当形成熔融金属时也与熔融金属槽17相接触。用来形成阴极电解槽内衬的块料20之间的空隙18,和底部块料20之间的和侧壁块料25之间的较宽的空隙,通常都用导电的阴极糊剂21(称为填充用粉料)来填充,当电解槽10在起动过程中受热时会发生凝固。用于这些用途的所有材料在电学上最好应该是导电的,耐熔的且还是抗侵蚀的,以便减小由于材料表面的电解液糊剂的流动所引起的物理移动,并且是耐腐蚀的(亦即是能够耐化学侵蚀的)。
在一种形式的电解槽中,位于该槽底部的阴极表面朝储器或贮罐(未表明在图中)方向稍微向下倾斜,以便使得在阳极表面和阴极表面之间形成的熔融铝能从阴极表面排出进入金属贮罐,由此将熔融铝引出电解槽。这类槽称为“排放式阴极槽”,其优点在于能够采用短的极间间距实现高的电流效率。可是,为了使这类槽正常工作,这阴极表面必须是可被熔融金属湿润,以便有一层薄金属始终覆盖在阴极表面。无烟煤和石墨块,以及通常在常规槽中用作阴极结构的其它含碳材料,都不能被熔融铝湿润。所以,已努力寻找可被铝湿润的材料,和可以用来形成阴极的材料。
根据1968年9月3日颁给R.A.刘易斯等人的US专利3,400,061,可湿润的阴极表面可由复合阴极材料构成,这种复合阴极材料包含硬质耐熔物质的混合物和至少约5%的碳。粉状硼化钛(TiB2)已是用作这类用途的优选硬质耐熔材料,虽然也可使用其它的陶瓷粉末诸如碳化硅,铝等。这碳组分经常是含煤焦油沥青的无烟煤作粘结剂。
TiB2也用于含碳组分的掺和剂中,以形成适用于所有各类槽的抗侵蚀充填糊剂。通常,只是为了改进抗侵蚀性而要求的TiB2含量,要小于为达到既抗侵蚀又表面可湿润性所要求的含量。这类糊剂经常用于充填阴极内衬的中心接缝和小的接缝,以及用来充填整体式斜面的暴露面。
虽然从性能优越的观点出发优选硼化钛,但它有一重大缺点就是非常贵。例如,目前TiB2的价格约为每公吨66,180加元(约合每吨60,000加元)。
1992年10月27日颁给汤逊特的US专利5,158,655已提出,可以给阴极结构涂以耐熔金属硼化物,而该金属硼化物则来源于直接添加在槽电解液中的或包含在阳极中的钛和硼的氧化物。可是,本发明的发明人进行的该项提议的试验已证明,用此方法难以生产出合格产品。
所以,需要有一种生产抗侵蚀和优选抗氧化的且任选可湿润的碳复合材料(例如,可用于制造电解槽的底部和侧壁的块料和充填糊剂)的方法,这种材料的价格比已知的含硼化物的材料要低廉,但有效地适用于电解槽,特别适用于排放式阴极槽。
发明内容
本发明的一个目的是要提供碳复合材料,这些材料可以加工成阴极块料,封填糊剂等,当用于电解槽时,这种材料是抗侵蚀/氧化的和优选可被熔融铝湿润的,同时是比较低廉和易于生产的。
另一个目的是降低电解槽,特别是排放式阴极槽的操作费用,而性能又无较大的牺牲。
再一个目的是要提供可以用来保护预定要浸入熔融金属中的仪器的廉价碳复合材料。
本发明是基于意外的发现,即作为制备阴极材料等的硬质耐熔物质的金属硼化物例如TiB2,可以采用下述方法在现场形成,以代替使用金属硼化物,该方法是将金属硼化物前体的的混合物作为掺合剂,连同含碳材料一起提供,它们在受到槽起动热作用时和在槽运行时,便会形成金属硼化物。
上述前体混合物通常是氧化硼(B2O3),硼酸(H3BO3)或硼砂(Na2O·2B2O3·10H2O)与一种或更多种金属氧化物的混合物。适合的金属氧化物的实例包括但不限于二氧化钛,氧化锆,氧化钒(V2O5和V2O3),二氧化铪,氧化铌,氧化钽,氧化铬和氧化钼。一旦与氧化硼,硼酸,或硼砂发生反应,这些金属氧化物便形成相应的金属硼化物。
上述金属氧化物和氧化硼(呈硼酸形态)的成本,大约是相同量的金属硼化物例如TiB2成本的三十分之一。但是,因为金属硼化物在槽运行时出现在阴极材料中,所以,与由作为原始材料的金属硼化物制备的阴极相比,在抗侵蚀/氧化和可湿润性方面基本上没有差别,或者至少其性能在工业上是可以接受的。
但是,为了使由前体现场生成金属硼化物适时完成,这些前体材料必须在它们与阴极材料的其它组分(无烟煤,沥青或焦油)相混合之前先彼此混合。如果它们分别与其它材料相混合,则不会生成满足要求的金属硼化物。
于是,根据本发明的一个方面,提供了一种生产适用于制备铝电解槽的全部或部分阴极或槽内衬,包括侧壁块料用的碳复合材料的方法,该方法包括:将定量的金属硼化物的前体彼此混合,以生产一种前体混合物,然后将上述前体混合物与至少一种含碳组分相混合,以形成所述碳复合材料;其中所述前体,在所述材料处于所述槽的起动和运行条件下时,便彼此起反应,从而在现场生成所述金属硼化物。
用来形成前体混合物的这些前体氧化物优选磨碎的。所谓术语“磨碎的”指的是,粉末具有的平均粒度小到足以使这些前体在槽起动过程中有效地起反应,以生成相应的金属硼化物。
根据本发明的另一方面,提供了利用上述方法生产的碳复合材料。
根据本发明的又一方面,提供了适合于制备铝电解槽的全部或部分的阴极或槽内衬,包括侧壁块料用的碳复合材料,所述材料包括磨碎的定量的金属硼化物的前体和至少一种含碳组分;其中所述前体,当所述材料处于所述槽的起动和运行条件下时,彼此起反应,从而在现场生成所述金属硼化物。
相比于上面所述的TiB2每公吨66,180加元(每吨60,000加元)的价格,同等量的前体氧化物混合物目前的价格每公吨在2,206加元(每吨2,000加元)左右。本发明所实现的成本节省额无疑是显著的。当本发明用于形成排放式阴极槽的可湿润阴极时,在制备铝过程中所获得的经济利益,与使用由TiB2制备的块料相比,已证实大约为每公吨金属获利66加元(每吨金属60加元)。
因为TiB2价格高,故通常已成为仅将只是呈磁砖形态的该材料或作为涂料,应用于常规碳块为的外露表面。厚度可达5cm的磁砖通过粘结化合物粘结,而涂料采用传统的等离子体喷射法被喷涂在块料表面(厚度通常小1cm)。遗憾的是,热膨胀率的差别常常引起上述磁砖和涂层裂开和与底层阴极材料分离,从而降低了槽的有效寿命。由于降低了原材料的成本,本发明的一个特有的优点在于,本发明的复合材料可以用来形成全部的阴极块料,于是显著地延长了槽的有效寿命。另外,本复合材料可以与常规材料相同的方式,但以显著低的代价用作表面涂料。
按照本发明生产的材料的一个优点在于,它不仅比石墨块料或无烟煤块料的抗侵蚀性更高,而且用作侧壁块料往往有更好的抗氧化性,于是有较长的有效寿命。
本发明的复合材普,至少在优选的形态中,通常能达到与熔融铝的接触角小于约45°,在电解槽正常使用过程中侵蚀/氧化率小于5mm/年(与常规阴极材料大于10mm/年相比)。
附图简述
图1是一张可供本发明使用的,局部切除后的常规铝电解槽透视图,为了清晰起见,该图中省略了电解液,熔融铝和阳极;和
图2是图1尺寸放大后的槽的局部横向剖面图,图中表明有熔融电解液和铝。
实施本发明的最佳模式
本发明至少包含二种主要材料,亦即供充填形成阴极(包括侧壁块料)所用元件之间的空隙用的封填化合物,和阴极元件本身,例如,构造诸如图1和图2所示槽之阴极内衬所用的阴极块料。此外,与碳相比(例如供不是自排放的常规槽用的碳),本材料基本上具有提高了的抗侵蚀/氧化性,或者是抗侵蚀/氧化二者都提高了的材料,且具有可被熔融铝湿润的表面(当烘干后)。当然,在所有这些情况下,该材料的制备首先是使金属氧化物和氧化硼(或硼酸前体,例如硼酸或硼砂)相混合,以形成氧化混合物,然后再使该氧化混合物与含碳组分相混合。
若仅为了有提高的抗侵蚀/氧化性,则通常所要求的金属硼化物前体的浓度比既要求抗侵蚀又要求可湿润性的要低。对于仅是抗侵蚀,当使用TiB2和VB2的前体时,要求至少最少5wt%的上述前体(按金属硼化物计算)。为了生产具有可湿润表面的材料,要求的最小浓度约为30wt%。
关于金属氧化物和氧化硼,优选从每种粉末具有的平均粒度约小于100微米(μm)着手。如有要求,可以采用大的颗粒,但小于30μm的颗粒有助于反应更完全和更迅速,因为能获得更均匀的前体氧化物的混合物。
前体氧化物的混合比例取决于前体的同一性,其意图是把所有的前体转化成最终的金属硼化物(亦即通常化学计量的量)。在TiO2和B2O3(或H3BO3)的情况下,优选的比例按重量计分别为40-50/50-60。为了方便起见,氧化前体可以在环境温度下彼此混合,虽然可以使用任何温度,只要前体之间的反应不过早地开始。
然后氧化混合物与适合于制备阴极组分的含碳配合剂相混合,例如无烟煤和沥青的混合物。通常,这混合步骤是在升高的温度,优选约160℃的条件下进行,以增加含碳组分的流动性,并因此使混合步骤成为可能和方便。氧化混合物与含碳配合剂的混合比,和选择的那些配合剂,取决于该材料的所预定的最终用途。可是,通常氧化混合物与常规的无烟煤/沥青混合物按重量计可分别以30-60/40-70的比值相混合。此外,在槽运作过程中,为了增加TiB2生成的动力,在混合过程中,最好是优选将具有粒度小于15μm的一定量的TiB2粉末(例如3~10wt%)添加到糊剂中。
除氧化前体和含碳材料外,本发明的材料还可按要求包含其它常规组分和配合剂。无烟煤可以部分地用石墨代替,以增加复合材料的导电性。
当该材料是用来制备阴极块料时,在压床上将该混合物制成砖块形(在压床上材料受振动而被压缩),然后该砖块在嵌入槽中之前将其预先烘干。
前体混合物处在槽的起动和运行温度下(通常为600~1100℃,更通常为700~1000℃)发生反应,从而形成相应的金属硼化物。另外,可以相信,发生在槽中的电解反应有助金属硼化物的生成,并促进前体反应的完成。事实上,这电解反应对金属硼化物的大量生成,至少当硼化物是TiB2时,可能是必需的。
以下讲述关于作为TiB2的前体的TiO2和B2O3的使用。
为了生成TiB2,优选TiO2和B2O3(H3BO3)按照化学计量比例彼此混合。这就是每1重量份B2O3约为70重量份TiO2。当然,如有要求,这些材料的相对量可以不同于化学计量量。TiO2与化学计量量的差额为±30%通常是可以接受的,不会引起性能的重大损失。
正如所指出的,前体材料均应优选呈磨碎的粉末状,以使能得到均匀的预混合料。每种粉末的平均粒度应优选不超过100微米,且这些粉末的平均粒度应最优选10~30μm。
接着,钛和硼的氧化物的前体混合物与含碳材料,通常是无烟煤(含或不含石墨)和粘结剂例如煤焦油沥青相混合。前体氧化混合物与含碳材料的比例,在某种程度上取决于最终混合物的预期用途(可湿润的阴极块料,耐熔嵌缝糊剂,等等),但此比例通常为40∶60重量份,更优选50∶50重量份。可以将一定量的粒度小于15μm的TiB2粉末(例如3%-10%)在混合过程中添加到糊剂中,以便在槽运行过程中增加TiB2生成的动力。
当最终的混合物预定作生产可湿润阴极块料用时,这混合比更优选50∶50重量份(前体氧化混合物∶含碳材料)。在彻底混合后,根据阴极构成将糊剂制成要求的尺寸和形状的块料。然后将未烧结的块料烘干到温度1000~1300℃,以便形成适用于阴极结构的承载式干燥块料。
当最终混合物预定用作充填糊剂时,该氧化前体混合物与含碳材料的混合比最优选50∶50重量份,而且这种糊剂在彻底混合后准备直接使用。这种糊剂通常以某种密封包装形式进行封装,以保证不使糊剂干燥和过分失去其粘性。这种糊剂可用作形成阴极结构的块料之间的嵌缝填料,或可以用来全部地(或者,更通常是局部地)涂覆常规阴极结构,以提供抗侵蚀性。槽内衬的整体斜侧面和中央接缝是使用本发明的糊剂进行涂覆的特定选择件,因为阴极块料之间的接缝由于电解液流动而在该处往往受到相对快的侵蚀。本发明的糊剂形成一种抗侵蚀涂层,从而延槽的有效寿命。
不管本发明的阴极材料以什么方式使用,它最终要经受在槽的起动和运行过程中电解槽的高温。这温度范围为700~1000℃。这些温度在电解条件下高得足以使氧化前体按照下面化学式基本上完成转化为二硼化钛:
3TiO2+3B2O3+10Al→3TiB2+5Al2O3
在上述反应中,铝金属的存在不是完成前体组分之间的反应所要求的,但是,铝显然将会出现在槽的某些部件中,并可能参与如上所表明的反应。但是,这种反应应最优选在还原环境中进行,例如电解槽,在这种环境中,前体氧化物被转化成它们的非氧化物形态。正如上面所指出的,如果氧化前体在添加到含碳材料中去之前没有彼此混合,形成的硼化钛不能达到要求的程度。虽然不能正确地知道其原因,但可以相信,在加热过程中,碳在每个氧化前体颗粒上形成一层涂层,从而影响了所希望的反应。
虽然对主要供形成或保护阴极内衬和侧壁块料用的本发明材料已作了叙述,事实上,本材料可以用于许多其它场合,其中有暴露于熔融金属,尤其是铝,或熔融电解液中的情况。例如,该材料可用来保护那些与熔融铝接触的仪器,例如温度传感器和探头(热电偶)等等,和用来保护通常必须浸入到铝电解槽和熔融金属槽中的仪器。该材料可以用来制成供上述仪器用的空心保护护套,或者可以将其涂覆在金属外壳上等等。
对本发明更详细的阐明请参阅下面的实例,提供这些实例仅是为了阐明的目的。
实例1底部和侧壁块料组成:
无烟煤=31wt%
TiO2=20wt%
B2O3=30wt%
沥青=19wt%制作(实验室)
混合温度:160℃
混合时间≈60分钟
振动时间:1分钟
作用在块料顶部的压力≈41.36856kPa(6 PSI)
实验室制作的块料尺寸:10mm×100mm×400mm
将TiO2和B2O3预混合,然后在温度约160℃下与无烟煤和沥青相混合达60分钟。将约3-10wt%的TiB2粉末添加到这糊剂中。混合后将热糊剂转送到固定在振动台上的模具中。振动后的块料在约1200℃下烘干5小时。
实例2:充填糊剂
作电解槽内衬用的复合糊剂的两个配方表述如下(按重量百分率计)
(A)电解槽内衬用热糊剂(糊剂温度100℃)
无烟煤=35wt%
TiO2=20wt%
B2O3=30wt%
沥青=12wt%
焦油=3wt%
先将TiO2和B2O3预混合,然后在温度约120~130℃下与无烟煤和沥青相混合达45分钟。将约3~10wt%的TiB2粉末添加到这糊剂中,并在100℃下将其用于电解槽。
(B)电解槽内衬用冷糊剂(糊剂温度30℃)
无烟煤=31wt%
TiO2=20wt%
B2O3=30wt%
沥青=12wt%
轻油=7wt%
先将TiO2和B2O3(或H3BO3)预混合,然后在温度25~35℃下与无烟煤。沥青和轻油相混合达45分钟。将大约3~10wt%的TiB2添加到这混合物中。这糊剂在25~30℃下将其用于电解槽。
当上述二种糊剂在槽运行过程中经受温度700~1000℃时,它们都转化成含有高抗粘结的TiB2的固体复合材料。
实例3
利用碳-TiO2-B2O3复合试件进行了持续约100小时的电解试验。在电解24小时之后,就观察到在复合试件上有铝层生成,这试件被极化为阴极。在这项实验过程中,可以观察到,在成形和烘干之前,在试件中使用少量的TiB2,能增加TiB2在碳试件表面上生成的动力。
电解条件:
Al2O3=6wt%
AlF3=6wt%
CaF2=6wt%
比值(AlF3/NaF)=1.25
ACD=3cm
槽温=970℃
阴极电流密度=1amp/cm2。
Claims (26)
1.一种在含有一种金属硼化物的铝电解槽中用作阴极或槽内衬的碳复合材料的生产方法,其中一种金属硼化物组分被引入一种含碳组分以形成一种碳复合材料,其特征在于将该金属硼化物组分通过混合,以金属硼化物前体混合物形态引入该含碳组分,该金属硼化物前体混合物包含多种金属硼化物前体,当它们在含碳组分中,暴露在铝电解槽的起动和运行条件下时,便生成金属硼化物。
2.权利要求1的方法,其特征在于将次要量的金属硼化物添加到所述碳复合材料中。
3.权利要求2的方法,其特征在于所述次要量为所述碳复合材料的3~10wt%。
4.权利要求1,2,或3的方法,其特征在于用来形成所述前体混合物的所述前体之一,选自氧化硼,硼酸和硼砂,而另一前体是选自钛、锆、钒、铪、铌、钽、铬和钼的一种金属的一种氧化物。
5.权利要求1,2或3的方法,其特征在于用来形成所述前体混合物的所述前体之一,选自B2O3和硼酸,而另一前体是TiO2。
6.权利要求1,2或3的方法,其特征在于用来形成所述前体混合物的所述前体之一选自B2O3和硼酸,而另一前体选自V2O5和V2O3。
7.权利要求1~6之任一项的方法,其特征在于所述前体混合按一定数量与至少一种含碳组分相混合,该量为在暴露于所述槽的起动和运行状态下之后,便能生成所述碳复合材料至少5wt%的金属硼化物。
8.权利要求1~7之任一项的方法,其特征在于所述前体混合物按数量与至少一种含碳组分相混合,该量为在暴露于所述槽的起动和运行状态下之后,便能生成一定量的所述金属硼化物,从而使所述材料的表面可被熔融铝湿润。
9.权利要求8的方法,其特征在于所述的一定量为所述碳复合材料的至少约30wt%。
10.权利要求1~4之任一项的方法,其特征在于至少所述一种含碳组分是无烟煤和沥青的混合物。
11.权利要求1~10之任一项的方法,其特征在于所述前体均呈具有的平均粒度小于100μm的粉末形态。
12.权利要求1~10之任一项的方法,其特征在于通过压制材料以形成块料,然后预烘干该块料。
13.一种适用于制备铝电解槽的全部或部分的阴极或槽内衬的碳复合材料,其特征在于所述材料已按照权利要求1~12之任一项的方法生产出来。
14.一种适用于制备铝电解槽的全部或部分的阴极或槽内衬,包括侧壁块料,的碳复合材料,所述材料包括一种金属硼化物组分和至少一种含碳组分;其特征在于所述金属硼化物组分包括多种金属硼化物前体,当所述碳复合材料暴露于铝电解槽的起动和运行状态下时,上述前体彼此反应,在现场生成金属硼化物。
15.权利要求14的材料,它进一步包含次要量的所述金属硼化物。
16.权利要求15的材料,其特征在于所述次要量为所述碳复合材料的3~10wt%。
17.权利要求14,15或16的材料,其特征在于所述前体之一选自氧化硼、硼酸或硼砂,而另一前体是选自钛、锆、钒、铪、铌、钽、铬和钼的一种金属的一种氧化物。
18.权利要求14,15或16的材料,其特征在于所述前体之一选自B2O3和硼酸,而另一前体是TiO2。
19.权利要求14,15或16的材料,其特征在于所述前体之一选自B2O3和硼酸,而另一前体选自V2O5和V2O3。
20.权利要求14-19的任一项的材料,其特征在于所述前体以一定数量存在,所述前体在暴露于电解槽的起动和运行状态条件下之后,便能生成所述复合材料的至少5wt%的金属硼化物。
21.权利要求14~19的任一项的材料,其特征在于所述前体按一定量存在,所述前体在暴露于电解槽的起动和运行状态下之后,便生成一定量的所述金属硼化物,从而使所述材料的表面可被熔融铝湿润。
22.权利要求21的材料,其特征在于所述的数量为所述复合材料的至少约30wt%。
23.权利要求14~22的任一项的材料,其特征在于所述至少一种含碳组分是无烟煤和沥青的混合物。
24.权利要求14~23的任一项的材料,其特征在于所述前体均呈具有平均粒度小于100μm的粉末形态。
25.权利要求14~24的任一项的材料,其特征在于该材料呈预烘干的槽用内衬块料形态。
26.一种适合于浸入熔融铝中的碳复合材料,所述材料包括一定量的磨碎的金属硼化物组分和至少一种含碳组分;其特征在于该金属硼化物组分以金属硼化物前体的形态存在,当所述材料暴露于熔融铝之中时,这些前体彼此反应,从而在现场生成所述金属硼化物。
Applications Claiming Priority (2)
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US10878298P | 1998-11-17 | 1998-11-17 | |
US60/108782 | 1998-11-17 |
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CN1333842A true CN1333842A (zh) | 2002-01-30 |
CN1195900C CN1195900C (zh) | 2005-04-06 |
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US (1) | US6649040B1 (zh) |
EP (1) | EP1141446B1 (zh) |
CN (1) | CN1195900C (zh) |
AU (1) | AU762779B2 (zh) |
CA (1) | CA2350814C (zh) |
IS (1) | IS2322B (zh) |
NO (1) | NO333951B1 (zh) |
NZ (1) | NZ511514A (zh) |
RU (1) | RU2232211C2 (zh) |
WO (1) | WO2000029644A1 (zh) |
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1999
- 1999-11-16 EP EP99972266A patent/EP1141446B1/en not_active Expired - Lifetime
- 1999-11-16 NZ NZ511514A patent/NZ511514A/en not_active IP Right Cessation
- 1999-11-16 US US09/831,375 patent/US6649040B1/en not_active Expired - Fee Related
- 1999-11-16 CN CNB998156027A patent/CN1195900C/zh not_active Expired - Fee Related
- 1999-11-16 CA CA002350814A patent/CA2350814C/en not_active Expired - Fee Related
- 1999-11-16 RU RU2001113450/02A patent/RU2232211C2/ru not_active IP Right Cessation
- 1999-11-16 WO PCT/CA1999/001086 patent/WO2000029644A1/en active IP Right Grant
- 1999-11-16 AU AU11445/00A patent/AU762779B2/en not_active Ceased
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2001
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101580949B (zh) * | 2009-06-24 | 2010-08-25 | 中国铝业股份有限公司 | 一种提高铝电解槽稳定性的方法 |
CN104120454A (zh) * | 2014-07-01 | 2014-10-29 | 湖南创元铝业有限公司 | 预焙阳极抗氧化性陶瓷基涂层及其涂覆方法 |
CN104120454B (zh) * | 2014-07-01 | 2016-08-17 | 湖南创元铝业有限公司 | 预焙阳极抗氧化性陶瓷基涂层及其涂覆方法 |
Also Published As
Publication number | Publication date |
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EP1141446B1 (en) | 2003-06-04 |
CN1195900C (zh) | 2005-04-06 |
NO20012391D0 (no) | 2001-05-15 |
RU2232211C2 (ru) | 2004-07-10 |
NZ511514A (en) | 2003-08-29 |
WO2000029644A1 (en) | 2000-05-25 |
NO20012391L (no) | 2001-07-16 |
EP1141446A1 (en) | 2001-10-10 |
IS2322B (is) | 2007-12-15 |
US6649040B1 (en) | 2003-11-18 |
AU762779B2 (en) | 2003-07-03 |
CA2350814A1 (en) | 2000-05-25 |
IS5937A (is) | 2001-05-09 |
AU1144500A (en) | 2000-06-05 |
NO333951B1 (no) | 2013-10-28 |
CA2350814C (en) | 2006-01-10 |
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