CN1016798B - 铁素体铬合金带钢连续热浸镀铝的方法 - Google Patents
铁素体铬合金带钢连续热浸镀铝的方法Info
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Abstract
本文介绍铁素体铬合金钢连续热浸镀铝的方法。在该带钢经预处理去除表面污染后,用氢气氛保护该带钢直至其通入熔融铝涂料金属中为止。该涂料金属很容易湿润该钢的表面而防止了在涂料层中无涂层区或针孔的产生。
Description
本发明涉及一种用铝连续热浸镀铁素体铬合金带钢的方法,以及一种用工业纯熔融铝增加带钢表面湿润性的方法。
热浸镀铝的钢对盐具有高的耐腐蚀性能,而且在汽车排气装置和燃烧设备方面获得了各种应用。近年来,汽车的已燃气体的温度升高了,同时腐蚀性也较严重。为此,已有必要用镀铝的铬合金钢代替镀铝低碳钢或镀铝低合金钢,来提高高温抗氧化性能和耐盐的腐蚀性。为了高温抗氧化和耐腐蚀,可在使用期间通过加热而使至少部分铝涂料层扩散到铁基中形成Fe-Al合金层。如果铝涂料层中有无镀层区存在,则会加速导致基体金属穿孔的腐蚀,而这种腐蚀可能是当Fe-Al合金没有连续地形成于铁基金属时发生的。
大家都知道可以通过使带钢进行预处理而不用助熔剂的热浸镀金属带钢,该预处理提供了无油、无尘和无氧化铁的清洁表面,这种表面很容易被涂料金属湿润。在颁发给T.赛德齐默尔(T.Sendzimir)的美国专利2,197,622和颁发给C.A.小特纳(C.A.Turner,Jr.)的美国专利3,320,085中介绍了二种型式的碳钢流水线式的预备退火处理。
制取热浸镀锌的碳钢带钢的赛德齐默尔方法包括将带钢通过一种没有气氛控制的、加热到1600°F(870℃)的氧化炉。将加热的带钢从该炉子中抽出进入空气而形成可控制的表面氧化物。然后将带钢引入含氢和氮气氛的还原炉中,带钢在炉中停留的时间足以使带钢温度至少为1350°F(732℃),而且足以还原表面的氧化物。然后,把带钢冷却到接近锌涂料熔池的温度,而且使它通过含有纯氢或氢-氮保护性气氛的进料嘴,引到涂料池的表面层下面。
普通叫做塞拉西(Selas)法,即制取热浸镀金属的碳钢带钢的特纳法包括将带钢通过一种加热到至少2200°F(1204℃)的炉子。该炉子的保护气氛没有游离的氧且至少有3%过量的可燃物。该带钢在炉中停留足够的时间以便使其温度达到至少800°F(427℃),同时保持光亮洁净的表面。然后,将带钢引入具有氢-氮保护气氛的还原炉段,在其中带钢可以进一步冷却到接近涂料金属熔池的温度,而且经过含有氢-氮气氛的进料嘴,引到涂料池的表面层下面。
颁发给C.Flinchum等人的美国专利3,925,579中介绍了一种热浸镀铝的低合金钢带钢的藉涂料金属提高湿润性的流水线予处理方法。该钢含有一种或一种以上的最高达5%铬、最高达3%铝、最高达2%硅和最高达1%钛的合金元素。在使铁氧化的气氛中,将带钢加热到1100°F(593℃)以上以形成表面的氧化物层,在能使铁的氧化物还原的条件下进一步处理带钢,从而将该表面层还原成含有均匀分布的合金元素氧化物的纯铁基体。
众所周知,浸镀的铝涂料不能像锌涂料一样很容易湿润洁净过的钢表面。颁发给皮尔逊(Pierson)等人的美国专利号4,155,235公开了使氢气远离铝涂料池进口段的重要性。本专利介绍,已洁净的钢必须在它刚要导入热浸镀铝涂料以前用氮气气氛保护,以便防止出现没有涂层的点。
关于铝涂料在铁素体不锈钢表面上无湿润性的问题也是众所皆知的。热浸镀的铝涂料对铁素体不锈钢基体金属的粘着性是很差的,而且在铝的涂层中通常有无涂层的或暴露的点。所谓较差的粘着指的是带钢在弯曲时涂层剥落或出现裂纹。为了克服粘着问题,有些人曾经提出热处理镀铝的不锈钢使涂料层粘结到基体金属上。其他一些人则提出轻度地重新轧制已涂层的不锈钢使之粘结铝涂层。最后,那些担心出现无涂层点的人一般都放弃了连续热浸镀。相反,他们采用了间歇式的热浸镀或喷
涂法。例如,不锈钢制品制造好后,将它在铝涂料池中浸渍一段很长的时间而使其产生很厚的涂料层。
没有一个人提出过一种用热浸镀铝涂料提高对铁素体铬合金钢湿润的解决办法。如果没有良好的湿润表面,则铝涂料层将不均匀,有无镀层区而且对钢基体金属粘着不牢固。我们发现了一种解决有关热浸镀铝涂料对铁素体铬合金钢的湿润问题的浸涂方法。如果使已净化的铁素体铬合金钢在进入铝涂料熔池之前,保持在保护性的氢气氛(基本上没有氮气)中,则将显著地改善湿润性。
本发明涉及一种连续热浸镀铝的、大约含至少6%(重量)铬的铁基铁素体钢。对钢表面进行预处理,以便去除油污、灰尘、氧化物等。然后,将钢加热到至少1250°F(677℃),然后在含有至少大约95%(体积)氢的气氛中对钢进行保护,同时使该钢保持于接近或略高于基本上由铝组成的涂料金属的熔点温度。该氢气氛提高了铁素体铬钢的润湿性能而基本上消除了在铝涂料层中的无涂层的或针孔的缺陷。
本发明的主要目的是用涂料金属形成具有良好湿润性的热浸镀铝的铁素体铬合金钢。
本发明的一个优点是在用铝进行热浸镀时,消除了无涂层区并提高了对铁素体铬合金基体金属的粘着力。
本发明的另一个优点是提高了高温抗氧化性能和耐盐腐蚀性能,从而提高了用于汽车排气装置中的镀铝铁素体铬合金钢的基体金属的耐穿孔性能。
根据详细介绍和附图的情况,将明显地看到本发明上述的和其他一些目的、性能以及优点。
图1是通过体现本发明的普通热浸镀铝作业线处理铁基带钢的示意图。
图2是表示进口嘴和涂料槽的图1热浸镀作业线的局部示意图。
现参阅图1,参考号数10表示具有带钢11的钢卷,带钢在进入第一炉区15的顶部以前,先通过此,然后绕过辊子12、13和14。第一炉区15可以是直接燃烧型的,在那里引入大约5%剩余的可燃物。炉子气氛温度可以大约为2300°F(1260℃)。带钢表面的污染物诸如油污等几乎立刻被燃烧和去除掉。
由号数16表示的第二炉区可以是辐射管型。可把带钢11的温度进一步加热到大约1250°F(677℃)至1750°F(954℃),而且在点18处附近达到最高温度。还原气将送入炉区16和它后面如下所述的炉区。该气体必须是作还原用的,而且最好不仅如此,除了用于碳钢的还原外,还应使基体金属中铬的氧化减到最低。
通常用号数20表示的第三炉区是冷却区。
通常,号数22表示的最后炉区是最终冷却区。带钢11从炉区22出来,经过调节辊24,通过进料嘴26进入盛有熔融铝的涂料槽28中。该带钢在该涂料槽中停留的时间很短(即2-5秒)。将含有涂料金属层的带钢11从涂料槽28垂直抽出。该涂料层凝固而且已涂层的带钢绕着导向辊32通过,同时卷成带钢卷34,供贮存或作进一步加工之用。
现参阅图2,进料嘴26因其下端或出口端26a浸没在铝涂料金属42的表面层44下面而受到保护,可免遭大气的影响。为了转动而适当地安装槽辊36和38和稳定辊40。用喷涂装置例如喷气修光刀30控制带钢从涂料槽抽出时留在带钢11上的涂料金属42的重量。带钢在进入涂料槽以前,在炉区20、22和进料嘴26时就被冷却到接近或略高于铝涂料金属的熔点温度。该温度可以低达1220°F(660℃)左右至高达1350°F(732℃)左右。
迄今介绍的方法在本技术领域内是众所周知的,而且该方法对两边的涂层采用喷气修光。正如那些擅长本技术领域的人将会了解到,可以使用变更的净化带钢表面的预处理方法,例如采用湿式净化代替直接燃
烧炉。此外,那些擅长本技术领域的人将会了解到,就本发明来说,可以采用内含无氧化气氛的密封套进行单边热浸镀或修光。
参阅图2,将详细地介绍本发明的情况。为了提高热浸镀铝涂料金属对含有至少大约6%(重量)铬的铁素体合金钢带钢的湿润性能,给这带钢以适当的预处理以去除灰尘、油膜和氧化物等。该带钢在使铁还原的气氛例如含有20%(体积)氢和80%(体积)氮中进一步加热,而且其后在它刚要进入涂料熔池以前,将这已净化的带钢通过基本上全部为氢的保护性气氛。当采用诸如上述的流水线式的退火来净化该带钢时,将该保护性气氛保持在例如密封的进料嘴26的封套中。需要时,可通过进口27引入氢气。该保护性气氛必须含有至少约95%(体积)的氢,较好含有至少97%(体积)而最好尽可能地含接近100%(体积)的氢。
控制保护性气氛中的含氧量和露点以及维持涂料槽中高的熔融金属温度也是很重要的。活性的铝涂料金属可以还原带钢表面上的薄氧化物层。铬比铁更容易被氧化,这样铬合金钢更可能是无湿润的,这是由于铬合金钢的氧化膜比碳钢的氧化物膜厚的多。因此,保护性氢气氛的露点必须不超过+40°F(4℃)左右,而且含氧量大约不大于200ppm。最好,露点应该低于+10°F(-12℃)和含氧量小于40ppm。
为了浸涂碳钢,通常把相当纯的铝涂料金属大约保持在1250°F(677℃)至1270°F(688℃)。因为铬合金钢有高的氧化倾向,所以我们必须将涂料金属保持至少这样高的温度,而且最好保持在1280°F(693℃)至1320°F(716℃)的温度范围内。这个提高的温度将增加涂料金属的活性,从而使涂料金属更容易还原铬的氧化物。由于可以产生非常厚而脆的Fe-Al合金层,因此该温度不应该超过1320°F(716℃)左右。
本发明对于汽车排气应用方面,包括催化转化器支架的金属薄片中所用的热浸涂铝的铁素体不锈钢特别有用。在属于美国系列编号USSN
741,282的1985年6月4日申请的待批专利申请中,介绍了这种金属薄片用钢,而且已将其转让给与本发明共同的受让人。一种具有热浸镀相当纯铝的大约含至少10%铬的铁素体不锈钢将具有优良的耐腐蚀性。与涂铝碳钢不同的是,我们已发现可以严格地制造用纯铝热浸镀的铁素体不锈钢而没有剥落或裂纹的涂料层。已确定可以用纯铝热浸镀409型不锈钢,这种不锈钢大约含10.0%至14.5%(重量)铬、0.1%至1.0%(重量)硅、0.2%至0.5%钛和其余为铁。此外,可以把有涂层的带钢从至少0.25毫米厚的带钢冷轧到小于0.1毫米厚的带钢而没有剥落涂料金属。因为该铝涂料层对基体金属具有极好的粘着力且不含有针孔或无涂层区,所以一种扩散热处理的金属薄片在高温下具有优良的抗氧化性能。例如,这种金属薄片可用作具有操作温度大约1500°F(800℃)~1650°F(900℃)以及“短暂偏差”温度高达2200°F(1204℃)的汽车排气中的催化剂支架。
除碳钢和低合金钢以外,含有相当数量镍的铬合金钢很容易用普通的操作进行热浸镀铝。所谓相当数量的镍是指超过大约3%(重量),例如奥氏体不锈钢。因为镍看来似乎同铝产生很牢固的结合,所以含有3%或更多镍的铬合金钢显然很容易用铝浸涂。因此,可以容易地用铝热浸镀这些高镍铬的合金钢,而不采用本发明的方法。
大部分热浸镀的铝涂料含有大约10%(重量)硅。在工业上,通常把此涂料金属定义为Ⅰ型。我们已发现这种类型的铝涂料金属不能很好地湿润铁素体的铬合金钢,甚至在采用氢保护气氛的情况下亦如此。虽然可不受理论的约束,但是应该相信,硅含量超过0.5%(重量)将降低铝涂料金属同铁素体铬合金钢基体反应所需的活性。因此,涂料金属中的硅含量必须不超过大约0.5%(重量)。
对本发明来说,最好是工业纯热浸镀的铝涂料,或者在工业上称为2型的涂料。所谓“纯”铝是指把相当数量的合金元素添加剂(例如硅)
排除在外的那些铝涂料金属。应该明白,该涂料金属可以含有残余量的杂质,特别是铁。该涂料熔池一般含有大约2%(重量)铁,这些铁主要是由穿过该熔池的带钢中的铁融化所引起的。
实例1
为了说明当采用普通保护气氛时不能防止无涂层区,在实验室的中间试验的作业线上,对3英寸(76毫米)宽的409不锈钢带钢进行流水线式的退火预处理。将炉子的直接燃烧段加热到大约2150°F(1175℃),观测到的带钢金属最高温度大约为1650°F(899℃)。把在进料嘴中刚要进入该铝涂料熔池的带钢冷却到大约1285°F(696℃)。
采用露点低于-15°F(-26℃)和氧含量小于40ppm的大约含有25%(体积)氢和剩余为氮的保护性气氛来保护炉子进料嘴部分的带钢。把涂料槽中的铝涂料金属温度保持在大约1285°F(696℃)。已浸涂的带钢含有估计约25%无涂层区,而且有时高达75%。
实例2
为了证明当采用本发明的保护性气氛时有高的湿润性能,在同样中间试验的作业线上,对3英寸(76毫米)宽的409不锈钢进行浸涂,而且给这种带钢以流水线式的退火预处理,采用的温度相似于实例1中所述的那些温度。然而,把保护性气氛调到含有大约100%(体积)氢,露点-15°F(-26℃)和氧含量小于40ppm。已浸涂的带钢外观是优良的,而且很明显没有可见的无涂层区或针孔。
实例3
在中间试验的作业线上涂敷3英寸(76毫米)宽的409不锈钢带钢。将该带钢加热到最高金属温度1600°F(871℃),而且带钢在进料嘴中刚要进入铝涂料熔池时被冷却到1280°F(693℃)。保护气氛的露点为-15°F(-26℃)和氧含量为20ppm。在进料嘴中安装气相色谱仪,以便在保护气氛中的氢数量变化时能够观测已涂覆带钢的涂层质量。当气
氛为大约92%(体积)氢和其余为氮时,涂层的质量是不合格的。在氢含量增加到大约94%(体积)时,涂层的质量可以认为勉强合格。当氢含量增加到97%(体积)时,认为观测到的涂层质量是优良的而且涂料层基本上没有无涂层区。
此外,也在生产规模的热浸镀铝作业线上进行了试验。采用下面的温度-气氛条件而且作出涂层质量的观测。
实例 DFF*温度 最高金属温度 槽温°F 露点°F氢 观测
号 °F(℃) °F(℃) (℃) (℃) %
4 1040(560) 1400(760) 1270(687) +7(-14) 0 50%无涂层
5 1040(560) 1400(760) 1270(687) +7(-14)100没有无涂层
6 1300(704) 1600(871) 1280(693)-25(-4) 100 15%无涂层
7 1300(704) 1600(871)1300(704)+30(-1) 100 没有无涂层
*在直接燃烧段中带钢的温度
实例4表示在进料嘴中采用100%(体积)氮气氛时有50%带钢是无涂层的。如实例5所示,当进料嘴中采用100%(体积)氢时在带钢上的无涂层区消失。实例6和7说明高的带钢温度和涂料金属温度的影响。炉内较高的气氛温度可以增加在带钢上所形成的铬氧化物的厚度。在有相当高的露点情况下(还原较差),必须将涂料金属的温度提高到大约1300°F(704℃)以便防止在带钢上出现无涂层区。当该炉子和/或保护性气氛还原作用不够时,可能必须增加涂料金属的温度以便还原带钢上的铬氧化物膜,保证带钢同铝涂料金属有良好的湿润,从而防止出现无涂层区。
可以在不违反本发明精神和范围的情况下,对本发明作出各种变更。例如,可以对该保护性气氛作出各种变更,只要保护气含有至少约95%(体积)氢即可。此外,可以对带钢的预处理和采用单边浸涂或无氧化喷气修光作出变更。因此,本发明的范围应该由附加的权利要求书确定。
Claims (10)
1、一种用铝连续热浸镀铁素体铬合金带钢的方法,包括以下各步骤:
净化铬合金带钢,
加热上述已净化的带钢到至少1250°F(677℃),
保持已净化带钢于含至少约95%(体积)氢的保护性气氛中,同时保持在接近或略高于涂料金属的熔点温度,所述的气氛具有不超过约+40°F(+4℃)的露点而且含有不超过大约200ppm的氧,
将所述已净化的带钢浸入涂料金属的熔池中,以便在所述带钢的至少一个面上沉积一涂料层,所述涂料金属,基本上是工业纯铝,
该带钢的基体金属含有至少约6%(重量)铬,
上述涂料层基本上没有无涂层区,而且对上述基体金属有很好的粘着力。
2、按照权利要求1所述的方法,其中所述的气氛基本上是100%(体积)氢。
3、按照权利要求1所述的方法,其中所述的气氛包括大约100%(体积)氢、露点不超过大约+10°F(-12℃)和不超过大约40ppm氧。
4、按照权利要求1所述的方法,其中所述钢的基体金属大约含有至少10%(重量)铬。
5、按照权利要求4所述的方法,其中所述钢基体金属含有10.0%至14.5%(重量)铬、0.1%至1.0%(重量)硅和0.2%至0.5%钛。
6、按照权利要求1所述的方法,其中所述的净化处理包括一种流水线式退火,在流水线式退火中将所述的钢加热到至少1040°F(560℃)。
7、按照权利要求1所述的方法,其中用喷气修光刀控制所述涂料层的重量。
8、按照权利要求7所述的方法,其中所述的喷气修光刀安装在含有对所述涂料层无氧化作用的气氛的密封套内。
9、按照权利要求1所述的方法,其中将所述的气氛保持在一个密封套内。
10、一种用铝连续热浸镀铁素体铬合金带钢的方法,包括以下各步骤:
在直接燃烧型炉的第一炉区内,用无氧化作用的气氛净化铬合金带钢,同时使带钢处于至少677℃,
在含有还原气氛的第二炉区内,进一步加热所述带钢到677-954℃,
将所述已净化的带钢冷却到接近或略高于涂料金属的熔点温度,并使所述的已净化的带钢通过密封的进料嘴,
将所述已净化的带钢保持在含至少约95%(体积)氢的保护气氛中,所述的保护性气氛具有不超过大约+40°F(+4℃)的露点并且含有不大于约200ppm氧,
将所述已净化的带钢浸入涂料金属的熔池中,以便在所述已净化带钢的至少一个面上沉积一涂料层,所述涂料金属基本上是工业纯铝,
钢的基体金属含有至少约6%(重量)铬,
所述涂料层基本上上没有无涂层区,而且对所述基体金属有很好的粘着力。
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US2082622A (en) * | 1933-02-25 | 1937-06-01 | Colin G Fink | Daluminum coated metal and process for producing the same |
US2197622A (en) * | 1937-04-22 | 1940-04-16 | American Rolling Mill Co | Process for galvanizing sheet metal |
US2570906A (en) * | 1946-07-31 | 1951-10-09 | Alferieff Michel | Process for coating metallic objects with other metals |
US3396048A (en) * | 1964-10-20 | 1968-08-06 | Olin Mathieson | Process for aluminizing metal |
US3320085A (en) * | 1965-03-19 | 1967-05-16 | Selas Corp Of America | Galvanizing |
US3378359A (en) * | 1967-01-31 | 1968-04-16 | Standard Oil Co | Method of protecting austenitic stainless steel subject to stress corrosion |
NL141933B (nl) * | 1970-04-24 | 1974-04-16 | Bekaert Sa Nv | Werkwijze voor het bekleden van een langgerekt metalen voorwerp met metaal, alsmede voorwerpen bekleed volgens deze werkwijze. |
US3779056A (en) * | 1971-12-28 | 1973-12-18 | Bethlehem Steel Corp | Method of coating steel wire with aluminum |
SE393403B (sv) * | 1972-08-09 | 1977-05-09 | Bethlehem Steel Corp | Sett att overdraga ytan av en jernstreng med en al-zn-legering |
US4053663A (en) * | 1972-08-09 | 1977-10-11 | Bethlehem Steel Corporation | Method of treating ferrous strand for coating with aluminum-zinc alloys |
US3907611A (en) * | 1972-11-10 | 1975-09-23 | Toyo Kogyo Co | Method for making ferrous metal having highly improved resistances to corrosion at elevated temperatures and to oxidization |
SE404065B (sv) * | 1972-11-30 | 1978-09-18 | Atomic Energy Authority Uk | Apparat for katalytisk rening av avgaser samt katalysator |
JPS5233579B2 (zh) * | 1972-12-25 | 1977-08-29 | ||
JPS4999982A (zh) * | 1973-01-31 | 1974-09-20 | ||
US3925579A (en) * | 1974-05-24 | 1975-12-09 | Armco Steel Corp | Method of coating low alloy steels |
JPS524491A (en) * | 1975-06-30 | 1977-01-13 | Hitachi Zosen Corp | Method of preparing catalyst for removing nox by selective catalytic r eduction with ammonia |
JPS5263123A (en) * | 1975-11-19 | 1977-05-25 | Toyo Kogyo Co | Production method of reactor material having excellent deformation resistance |
JPS5281041A (en) * | 1975-12-29 | 1977-07-07 | Komatsu Mfg Co Ltd | Device for controlling tandem torch type automatic welding machine |
JPS53130239A (en) * | 1977-04-20 | 1978-11-14 | Toyo Kogyo Co | Al diffusion osmosis method |
US4155235A (en) * | 1977-07-13 | 1979-05-22 | Armco Steel Corporation | Production of heavy pure aluminum coatings on small diameter tubing |
CA1083437A (en) * | 1977-12-28 | 1980-08-12 | Laurence B. Caldwell | Mehtod of treating ferrous strand by hot dip coating procedure |
JPS5856026B2 (ja) * | 1979-01-20 | 1983-12-13 | 日立造船株式会社 | アルミニウム被覆ステンレス鋼の製造方法 |
JPS6043476A (ja) * | 1983-08-17 | 1985-03-08 | Nippon Steel Corp | 連続溶融アルミメツキ法 |
US4535034A (en) * | 1983-12-30 | 1985-08-13 | Nippon Steel Corporation | High Al heat-resistant alloy steels having Al coating thereon |
JPS60245727A (ja) * | 1984-05-19 | 1985-12-05 | Nippon Steel Corp | 溶融アルミニウムメツキ鋼板の製造法 |
US4557953A (en) * | 1984-07-30 | 1985-12-10 | Armco Inc. | Process for controlling snout zinc vapor in a hot dip zinc based coating on a ferrous base metal strip |
-
1986
- 1986-05-20 US US06/865,238 patent/US4675214A/en not_active Expired - Lifetime
-
1987
- 1987-02-25 CA CA000530559A patent/CA1243244A/en not_active Expired
- 1987-03-19 IN IN221/CAL/87A patent/IN167354B/en unknown
- 1987-03-20 EP EP87104098A patent/EP0246418B1/en not_active Expired - Lifetime
- 1987-03-20 DE DE8787104098T patent/DE3775979D1/de not_active Expired - Fee Related
- 1987-03-20 AT AT87104098T patent/ATE71670T1/de not_active IP Right Cessation
- 1987-03-20 ES ES198787104098T patent/ES2027979T3/es not_active Expired - Lifetime
- 1987-03-23 NO NO871197A patent/NO173454C/no not_active IP Right Cessation
- 1987-04-07 YU YU618/87A patent/YU45414B/xx unknown
- 1987-04-08 JP JP62084929A patent/JPH062932B2/ja not_active Expired - Fee Related
- 1987-04-13 BR BR8701764A patent/BR8701764A/pt not_active IP Right Cessation
- 1987-04-15 ZA ZA872715A patent/ZA872715B/xx unknown
- 1987-05-14 AU AU72930/87A patent/AU592437B2/en not_active Expired
- 1987-05-18 FI FI872176A patent/FI83671C/fi not_active IP Right Cessation
- 1987-05-19 KR KR1019870004923A patent/KR910004609B1/ko not_active IP Right Cessation
- 1987-05-20 CN CN87103764A patent/CN1016798B/zh not_active Expired
Also Published As
Publication number | Publication date |
---|---|
AU7293087A (en) | 1987-11-26 |
JPS62274060A (ja) | 1987-11-28 |
EP0246418A3 (en) | 1989-02-08 |
KR870011270A (ko) | 1987-12-22 |
KR910004609B1 (ko) | 1991-07-08 |
NO871197L (no) | 1987-11-23 |
JPH062932B2 (ja) | 1994-01-12 |
NO173454B (no) | 1993-09-06 |
YU61887A (en) | 1988-12-31 |
US4675214A (en) | 1987-06-23 |
NO173454C (no) | 1993-12-15 |
CN87103764A (zh) | 1987-12-23 |
BR8701764A (pt) | 1988-02-09 |
IN167354B (zh) | 1990-10-13 |
ATE71670T1 (de) | 1992-02-15 |
DE3775979D1 (de) | 1992-02-27 |
EP0246418A2 (en) | 1987-11-25 |
ES2027979T3 (es) | 1992-07-01 |
FI872176A (fi) | 1987-11-21 |
ZA872715B (en) | 1987-12-30 |
FI872176A0 (fi) | 1987-05-18 |
CA1243244A (en) | 1988-10-18 |
NO871197D0 (no) | 1987-03-23 |
AU592437B2 (en) | 1990-01-11 |
FI83671C (fi) | 1991-08-12 |
YU45414B (en) | 1992-05-28 |
EP0246418B1 (en) | 1992-01-15 |
FI83671B (fi) | 1991-04-30 |
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