CN1468293A - 用于金属材料塑性加工的水性润滑剂以及润滑薄膜的处理方法 - Google Patents
用于金属材料塑性加工的水性润滑剂以及润滑薄膜的处理方法 Download PDFInfo
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- CN1468293A CN1468293A CNA018169627A CN01816962A CN1468293A CN 1468293 A CN1468293 A CN 1468293A CN A018169627 A CNA018169627 A CN A018169627A CN 01816962 A CN01816962 A CN 01816962A CN 1468293 A CN1468293 A CN 1468293A
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- B21J3/00—Lubricating during forging or pressing
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- B21C9/005—Cold application of the lubricant
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- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
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Abstract
一种用于金属材料塑性加工的水性润滑剂,它包括:(A)水溶性无机盐,和(B)石蜡,其中这些成分是溶解或分散在水中的,(B)/(A)的固态浓度比(重量比)为0.3~1.5.一种润滑薄膜的处理方法,特征在于,通过将水性润滑剂、优选以0.5~40g/m2的干重涂覆到上面未形成任何化学薄膜的金属材料表面上,然后干燥。水性润滑剂优选还包括(C)脂肪酸的金属盐,(C)/(A)的固态浓度比为0.01~0.4。水溶性无机盐(A)优选选自硫酸盐、硅酸盐、硼酸盐、钼酸盐和钨酸盐。石蜡优选为可分散到水中、熔点为70~150℃的天然石蜡或合成石蜡。脂肪酸的金属盐(C)优选是通过让具有12~26个碳原子的饱和脂肪酸与选自以下金属的金属反应而制得的,所述金属包括锌,钙,钡,铝,镁和锂。该水性润滑剂可容易地用于为上面未形成化学薄膜的金属表面提供优良的润滑性。
Description
发明领域
本发明涉及一种用于诸如钢铁、不锈钢、钛、铝以及其它材料的金属材料塑性加工的水性润滑剂,其中的金属材料表面未经任何化学转化处理。另外,本发明还涉及该润滑剂的使用方法。
更具体而言,本发明涉及一种用于产生润滑薄膜的水性润滑油,所述润滑薄膜适合在诸如钢铁、不锈钢、钛、铝以及其他材料的金属材料的表面上进行塑性变形加工,所述塑性变形加工例如锻造、拉丝、管材拉拔和其他加工,其中金属材料表面未经任何化学转化处理。
技术背景
在对诸如钢铁、不锈钢和其他材料的金属材料实施冷塑性加工时,为了防止因金属材料与工具间的金属接触而产生的燃烧缺陷和磨损缺陷,通常要在金属材料表面上设置润滑薄膜。
考虑到要在金属表面上设置润滑薄膜,存在着使润滑剂以物理方式粘附到金属表面上的润滑薄膜,以及通过提前对金属材料进行化学转化处理、然后将润滑剂涂敷到化学转化层上从而在金属表面上形成化学转化层的其它润滑薄膜。
以物理方式粘附到金属表面上的润滑剂通常用于微减量的冷加工,这是因为它们的粘附力要弱于涂敷到化学转化层上的润滑剂的粘附力。
在利用化学转化薄膜过程中,要在金属表面上设置磷酸盐薄膜或草酸盐薄膜,这些薄膜扮演着作为其上涂敷的润滑剂的载体的角色。该类型的润滑薄膜由2层构成:载体层和润滑剂层,该润滑薄膜表现出非常优良的耐受金属材料燃烧缺陷的性能。其广泛用于诸如拉丝、管材拉拔、锻造以及其他加工的冷加工。除了用于高减量的冷加工领域之外,它还广泛用于提供磷酸盐薄膜或草酸盐薄膜,然后在这些薄膜上涂覆润滑剂。
根据用途可将化学转化层上涂覆的润滑剂分为两类。第一类包括以机械方式粘附到化学转化层上的润滑剂,第二类包括与化学转化层起反应的润滑剂。
第一类润滑剂包括:利用矿物油、植物油或合成油作为基础油而制备的那些润滑剂,所述基础油中含有极压添加剂;还包括通过将诸如石墨和二硫化钼之类的固体润滑剂与粘合剂成分一起溶解到水中而制得的另一种润滑剂。这些润滑剂要经过粘附并干燥。
由于第一类润滑剂能通过喷涂或浸涂方式方便使用,因此对于溶液处理而言,这些润滑剂具有方便使用的优点。但是,由于它们仅具有较低的润滑性,所以倾向于将它们用于需要金属材料形变量小的情况。
另一方面,在第二类润滑剂中,是将例如硬脂酸钠之类的活性皂用于需要高润滑性的冷加工。活性皂与化学转化层反应,形成高润滑性的层。
但是,因为活性皂引起了化学反应,因此处理过程中溶液的成分控制、化学反应的温度控制、以及通过从溶液中排出废物而对品质退化溶液进行再生控制等变得非常重要。
近来,为了全球的环境保护,减少工业废弃物成为一个大问题。所以,现在非常渴望不会排出废物的新型润滑剂和新型润滑处理方法。另外,还渴望一些新处理方法来简化对上述第二类中的处理方法和溶液的复杂控制。
为了解决上述问题,JP52-20967A中已经公开了一种润滑剂组合物,它包括:以水溶性聚合物或其水乳液作为基本成分,固体润滑剂和一种成膜剂。但是,没得到象利用了化学转化层的传统方法中那样具有相同程度的较好效果的组合物。
为了解决上述问题,已经披露了另一项现有技术JP10-8085A。该现有技术涉及用于金属材料塑性加工的水性润滑剂,其中(A)水溶性无机盐、(B)固体润滑剂、(C)选自矿物油、动物油、植物油和合成油的组中的至少一种油、(D)表面活性剂、以及E)水都得到很好分散并均匀乳化。但是,由于必须让油性成分保持乳化状态,而它又表现出不稳定的性质,因此依照该现有技术的润滑剂太不稳定,以致不能在工业领域使用。
引用发明JP2000-63880A作为另一项现有技术。该现有技术涉及用于金属材料塑性加工的润滑剂,该润滑剂包括(A)合成树脂、(B)水溶性无机盐和水,其中,固体状态下(B)/(A)的重量比范围为0.25/1到9/1,合成树脂在组合物中保持溶化或分散状态。但是,由于该组合物的主要成分是合成树脂,因此在缩小量大的塑性加工过程中,该组合物在展现高润滑性方面还不稳定。
所以本发明的目的是提供一种用于金属材料塑性加工的水性润滑剂以及润滑薄膜的处理方法,其中,金属材料未经任何化学转化处理,这解决了传统方法中存在的问题,也改善了全球环境保护方面的问题,可将它们涂覆到多种金属材料上。
发明内容
本发明研究了解决上述问题的方法,并发现:通过含特定比例的水溶性无机盐和石蜡的水溶液或还包含另外的脂肪酸金属盐的水溶液能获得优良的润滑性能。另外,还找到了一种在金属表面上形成润滑薄膜的处理方法,该方法可以节约处理能源和处理空间。
即,本发明是一种水性润滑剂,它包括(A)水溶性无机盐和(B)石蜡,这些成分都溶解或分散于水中,固体状态下(B)/(A)的重量比范围为0.3-1.5。另外,本发明是一种进一步包括(C)脂肪酸金属盐的水性润滑剂,其中,固体状态下(C)/(A)的重量比范围为0.01-0.4。
优选的是,上面的(A)是选自硫酸盐、硅酸盐、硼酸盐、钼酸盐以及钨酸盐的组中的一种或多种水溶性无机盐,并且优选的是,上面的(B)是熔点介于70-150℃之间的水分散性合成石蜡。
另外,优选的是,上面的(C)是通过让C12-C26的饱和脂肪酸与选自锌、钙、钡、铝、镁和锂的组中的一种或多种金属反应而得到的脂肪酸金属盐。
另外,优选的是,本发明中水性润滑剂的用量是对应于能产生0.5-40g/m2的干润滑剂层的量。此外,优选的是让金属材料表面预先经受选自喷丸处理、喷砂处理、碱洗脱脂和酸洗的组中的一项或多项清洗步骤处理,另外优选的是,在金属材料加热到60-100℃以后,再将水性润滑剂涂覆到金属材料表面上。
附图的简要说明
图1:后方冲压(rear punching)试验的示意图。
图2:成钉(spike)试验的示意图。
本发明的最佳实施方式
现在将进一步详细解释本发明。为了赋予形成的润滑薄膜一定硬度和强度,纳入了本发明的水性润滑剂中使用的水溶性无机盐(A)。为了该目的,要求该水溶性无机盐具备能均匀溶解到水溶液中、干燥后形成牢固润滑薄膜的性能。
作为具备该性能的无机盐,优选的是利用至少一种选自由硫酸盐、硅酸盐、硼酸盐、钼酸盐和钨酸盐组成的组中的盐。作为上述无机盐的例子,可给出硫酸钠、硫酸钾、硅酸钾、硼砂(四硼酸钠)、硼酸钾(四硼酸钾)、硼酸铵(四硼酸铵)、钼酸铵、钼酸钠和钨酸钠。这些盐中的任何一种既可以单独使用,也可以将2种或多种盐结合使用。
对于石蜡(B),尽管在结构和类型方面没有特别限制,但优选的是使用合成石蜡。石蜡可能因冷加工时塑性变形过程中产生的热量而融化,于是这就改善了涂膜的润滑性能。基于该原因,优选的是使用熔点在70-150℃范围内且在水性润滑剂中保持稳定的那些石蜡,以及使用那些不会降低涂膜强度、于是从塑性加工的初期阶段开始就表现出优越润滑性的石蜡。
这些石蜡的实际例子包括:微晶石蜡、聚乙烯石蜡、聚丙烯石蜡、棕榈石蜡等。这些石蜡优选与其它成分结合,将它们以水分散体或水乳液的形式被包含到本发明的水性润滑剂中。(B)/(A)、即石蜡(B)与水溶性无机盐(A)的固态重量比范围优选为0.3-1.5,更优选为0.4-1.0。当该比例小于0.3时,涂膜的滑动性会不足,当比例大于1.5时,涂膜的粘附性能变得不足。
本发明使用的脂肪酸金属盐(C)用于提供润滑性能,虽然在类型方面没有限制,但优选的是通过让C12-C26的饱和脂肪酸与选自锌、钙、钡、铝、镁和锂的组中的至少一种金属反应而得到的产品。更优选的是使用硬脂酸钙、硬脂酸锌、硬脂酸钡、硬脂酸镁和硬脂酸锂中的任意一种。本发明使用的脂肪酸金属盐以分散形式存在于水性润滑剂中,需要时可使用公知的表面活性剂。
(C)/(A)、即脂肪酸金属盐(C)与水溶性无机盐(A)的固态重量比的范围优选为0.01-0.4,更优选为0.03-0.2。当该比例低于0.01时,虽然不会进一步产生大问题,但也会发生润滑性能变得不足的情况。但是,比例大于0.4不是优选的,这是因为水性润滑剂的均匀性变得不稳定。
在形变量大的冷加工中,还可以再向本发明的水性润滑剂中加入另一种油或另一种固态润滑剂。
在为了将脂肪酸金属盐和石蜡分散到水性润滑剂中而需要表面活性剂时,可以使用非离子、阴离子、两性和阳离子型的任何表面活性剂。尽管不作限制,但非离子表面活性剂可包括:聚氧乙烯烷基醚,聚氧化烯(乙烯或丙烯)烷基苯基醚,含聚乙烯醇(或环氧乙烯)和高级脂肪酸(例如C12~C18)的聚氧化乙烯烷基酯,含山梨糖醇酐、聚乙烯醇以及高级脂肪酸(例如C12~C18)的聚氧化乙烯山梨糖醇酐烷基酯。
尽管没有任何限制,但阴离子表面活性剂包括:脂肪酸盐,硫酸酯盐,磺酸盐,磷酸酯盐,以及二硫代磷酸酯盐。尽管不作限制,但两性表面活性剂可包括:氨基酸结构或内铵盐结构的羧酸盐,硫酸酯盐,磺酸盐,磷酸酯盐。
尽管没有任何限制,阳离子表面活性剂包括脂肪酸的胺盐、季铵盐等。这些表面活性剂中的每一种都可以单独使用,或者两种或两种以上结合使用。
可将本发明的水性润滑剂涂覆到钢铁、不锈钢、铜或铜合金、铝或铝合金、钛或钛合金之类的金属材料上。对金属材料的形状不作特别限制,不仅可以使用棒材,而且还可以使用锻造产品(齿轮、轴等)。
依照本发明的润滑薄膜形成方法,可让净化过的、但未经化学转化处理的金属材料表面与前述水性润滑剂接触,然后干燥,于是在金属材料表面上形成0.5~40g/m2的润滑薄膜,因此该方法是不反应型的。可根据冷加工的形变程度调整要在金属表面上形成的润滑薄膜量。润滑薄膜量的范围更优选为2~20g/m2。当该量值低于0.5g/m2时,润滑性变得不足。当其大于40g/m2时,尽管不会出现特殊问题,但在加工过程中出现渣滓,产生的渣滓会填入工具表面上设置的凹腔。可根据金属材料的表面积和处理前后的重量差来计算润滑薄膜的量。
可以调整各成分的重量浓度以调整润滑薄膜的量。许多情况下,可通过用水稀释浓缩的水性润滑剂来获得处理溶液。对用于该稀释目的的水没有限制,但是去离子水或蒸馏水是优选的。
本发明中未进行化学转化处理的金属材料表面优选是要经过选自以下处理中的一个或多个清洁步骤的处理的表面,所述处理包括喷丸处理,喷砂处理,碱洗脱脂处理,酸洗处理。这些处理的主要目的是清除退火过程中的氧化皮或清除油或其它污染物。
近来,从环境观点出发希望减少废水的处理量。在本发明中,例如通过喷丸处理来清洁表面同时利用本发明的水性润滑剂来形成润滑薄膜可将废水减少到零。
对于将本发明的水性润滑剂涂覆到金属材料表面上的方法没有特别限制。可以采用浸渍法、流动涂覆法和其它方法。当表面被水性润滑剂充分覆盖时,涂覆就足够了,在涂覆时间方面没有任何限制。
涂覆之后,必须让水性润滑剂干燥。可通过将其保持在常温进行干燥,将其保持在60~150℃达1~30分钟也是优选的。
另外为了提高干燥效率,优选的是在将金属材料加热到60~100℃以后再涂覆水性润滑剂。此外,在将水性润滑剂加热到50~90℃以后再涂覆该润滑剂也是优选的。
这样就能大大提高干燥效率,并能大幅降低热能损耗。
举例
(后方冲压试验的试样)
从市场上获得JIS S45C的一系列钢棒试样,对它们进行球化(spherodizing)退火处理,如图1(A)所示,其直径为30mm,系列高度为18~40mm,每根棒材的高度彼此相差2mm。
(成钉试验的试样)
从市场上购买的JIS S45C的钢棒试样,对它们进行球化退火处理,其直径为25mm,高度为30mm。
(处理过程)
·过程A
(1)脱脂:使用市场上出售的脱脂剂(由Nihon Parkerizing有限公司生产的FINE CLEANERR 4360),浓度:20g/L,温度:60℃,浸渍时间:10分钟。
(2)清洗:用自来水,60℃,浸渍30秒。
(3)润滑处理:在60℃度下浸渍10秒钟。
(4)干燥:在80℃干燥3分钟。
·过程B
(1)喷丸处理:颗粒直径:0.5mm,处理5分钟。
(2)清洗:用自来水在90℃浸渍90秒。
(3)润滑处理:使其在70℃与润滑剂接触,浸渍5秒钟。
(4)干燥:在室温下吹风3分钟。
(后方冲压试验)----图1
利用图1(B)的200吨曲轴压力机对图1(A)中的一系列钢棒试样进行冷加工,制造出图1(C)所示的一系列杯形制品。每次冲压时都剩余10mm的底部,横截面积的减量为50%。检查杯子的内表面上的缺陷,将未观察到缺陷的杯子的最大深度(Zmm)作为冲压深度(mm)示于表1中。该试验中,模具材料是JIS SKDI I,冲压工具为JISHAP40,冲压直径为21.21mm,每分钟冲击30次。
(成钉试验)----图2
按照与JP5-7969A中所示方式相同的方式进行成钉试验。模具(1)的内表面为类似漏斗的形状。将棒材试样(2)置于图2(A)所示的模具(1)的顶部,然后施压,如图2(B)所示,使试样(2)底部被压迫进入模具(1)的漏斗孔。通过该过程就制出了形状与漏斗相应的长钉。将所得长钉的高度作为长钉高度示于表1中。当长钉具有很大的长钉高度时,润滑效果优良。
(实施例1)
在上述处理过程A中使用下面的水性润滑剂1(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂1
水溶性无机盐:硅酸钾
石蜡:微晶石蜡
比例(B/A):1.0
形成的薄膜量(g/m2):15
(实施例2)
在上述处理过程A中使用下面的水性润滑剂2(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂2
水溶性无机盐:四硼酸钠
石蜡:聚乙烯石蜡
脂肪酸的金属盐:硬脂酸钙
比例(B/A):0.5
比例(C/A):0.5
形成的薄膜量(g/m2):15
(实施例3)
在上述的处理过程B中使用下面的水性润滑剂3(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂3
水溶性无机盐:四硼酸钠
石蜡:聚乙烯石蜡
脂肪酸的金属盐:硬脂酸钙
比例(B/A):1.0
比例(C/A):0.2
形成的薄膜量(g/m2):15
(实施例4)
在上述的处理过程B中使用下面的水性润滑剂4(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂4
水溶性无机盐:钨酸钠和四硼酸钠(重量比为1∶2)
石蜡:硬石蜡
脂肪酸的金属盐:硬脂酸锌
比例(B/A):1.5
比例(C/A):0.4
形成的薄膜量(g/m2):15
(实施例5)
在上述的处理过程B中使用下面的水性润滑剂5(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂5
水溶性无机盐:硫酸钾
石蜡:硬石蜡
脂肪酸的金属盐:硬脂酸钙
比例(B/A):1.2
比例(C/A):0.4
形成的薄膜量(g/m2):15
(比较例1)
在上述的处理过程A中使用下面的水性润滑剂6(为了分散而含有1wt%的非离子表面活性剂)。
水性润滑剂6
水溶性无机盐:硫酸钠
石蜡:硬石蜡
比例(B/A):0.1
形成的薄膜量(g/m2):10
(比较例2)
按照下面的处理过程C进行处理。
·过程C
(1)脱脂:利用市场上的脱脂剂(由Nihon Parkerizing有限公司生产的FINE CLEANERR 4360),浓度:20g/L,温度:60℃,浸渍时间:10分钟。
(2)清洗:用自来水,室温,浸渍30秒。
(3)化学转化处理:使用从市场上购得的含有磷酸锌的化学试剂(由Nihon Parkerizing有限公司生产的PALBONDR 181X),浓度:90g/L,温度:80℃,浸渍时间:10分钟。
(4)清洗:用自来水,室温,浸渍30秒钟。
(5)皂洗处理:市场上的活性皂润滑剂(由Nihon Parkerizing有限公司生产的PALUBER 235),浓度:70g/L,温度80℃,浸渍时间:5分钟。
(6)干燥:80℃,3分钟。
(比较例3)
在处理过程A中使用下面的水性润滑剂7。
水性润滑剂7
水溶性无机盐:硼砂;10%
固体润滑剂:硬脂酸钙;10%
油组分:棕榈油;0.5%
表面活性剂:聚氧乙烯烷基醇:1%
其它:水
形成的薄膜量(g/m2):10
(比较例4)
在过程A中使用下面的水性润滑剂8(为分散而含有1wt%的非离子表面活性剂)。
水性润滑剂8
水溶性无机盐:四硼酸钠
合成树脂:尿烷树脂
脂肪酸的金属盐:硬脂酸钙
固态(水溶性无机盐/合成树脂)的比例:2/1
固态(硬脂酸钙/合成树脂)的比例:3/1
形成的薄膜量(g/m2):10
试验结果示于表1中。从表1中可以清楚看到,使用了依照本发明的金属材料塑性加工用水性润滑剂的实施例1~5展现出极好的润滑性以及简单易行的处理工艺。而比例(B)/(A)落在本发明范围之外的比较例1在润滑性方面要差一些。在利用磷酸盐层和反应皂进行处理的比较例2中,润滑性与本发明中的一样优良。但是,化学转化处理的结果会出现大量废物,处理这些废物时必须具备专用的复杂设备,保护环境的负担加重。另外还证明,在与JP10-8085A所示内容相同的比较例3的成钉试验中润滑性较差,在与JP2000-63880A所示内容相同、以合成树脂为主要成分的比较例4中润滑性也较差。发明优点
由上面的描述显而易见的是,利用本发明的水性润滑剂和本发明的润滑薄膜处理方法,经过简单易行的处理就能形成高润滑性的薄膜。另外,还降低了废物产生量,使较好的环境保护成为可能。因此,本发明具有很大的工业实用性。
表1
处理过程中的步骤数 | 处理 | 冲压深度(mm) | 长钉高度(mm) | |
实施例1 | 4 | 涂覆型 | 60 | 13.1 |
实施例2 | 4 | 涂覆型 | 60 | 13.2 |
实施例3 | 4 | 涂覆型 | 60 | 13.1 |
实施例4 | 4 | 涂覆型 | 60 | 13.1 |
实施例5 | 4 | 涂覆型 | 60 | 13.1 |
比较例1 | 4 | 涂覆型 | 40 | 11.8 |
比较例2 | 6 | 反应型/废物多 | 56 | 13.0 |
比较例3 | 4 | 涂覆型 | 56 | 12.5 |
比较例4 | 4 | 涂覆型 | 56 | 12.6 |
Claims (9)
1.一种用于金属材料塑性加工的水性润滑剂,其包括(A)水溶性无机盐和(B)石蜡,这些成分溶解或分散在水中,(B)/(A)的固态重量比范围为0.3~1.5。
2.根据权利要求1所述的用于金属材料塑性加工的水性润滑剂,其中它还包括(C)脂肪酸的金属盐,(C)/(A)的固态重量比范围为0.01~0.4。
3.根据权利要求1~2中任一项所述的用于金属材料塑性加工的水性润滑剂,其中(A)是选自硫酸盐、硅酸盐、硼酸盐、钼酸盐和钨酸盐的组中的一种或一种以上的水溶性无机盐。
4.根据权利要求1~3中任一项所述的用于金属材料塑性加工的水性润滑剂,其中(B)是熔点为70℃~150℃的水分散型合成石蜡。
5.根据权利要求2~4中任一项所述的用于金属材料塑性加工的水性润滑剂,其中(C)是通过让C12~C26的饱和脂肪酸与选自以下金属组成的组中的一种或多种金属反应而得的脂肪酸金属盐,所述金属组包括:锌,钙,钡,铝,镁,和锂。
6.润滑薄膜的处理方法,其中将根据权利要求1~5中任一项所述的用于金属材料塑性加工的水性润滑剂涂覆到金属材料表面上,所述金属材料表面先前未经过任何化学转化处理。
7.根据权利要求6所述的润滑薄膜的处理方法,其中水性润滑剂的用量是对应于能产生0.5~40g/m2的干燥润滑薄膜的量。
8.根据权利要求6~7中任一项所述的润滑薄膜的处理方法,其中金属材料的表面先前未经任何化学转化处理,它要经过选自以下处理过程组成的组中的一种或多种清洁步骤的处理,所述处理包括:喷丸处理,喷砂处理,碱洗脱脂处理,以及酸洗处理。
9.根据权利要求6~8中任一项所述的润滑薄膜的处理方法,其中是在将金属材料加热到60℃~100℃以后再将水性润滑剂涂覆到金属材料表面上。
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2001
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- 2001-04-26 CN CNB018169627A patent/CN1208441C/zh not_active Expired - Lifetime
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US20030130138A1 (en) | 2003-07-10 |
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CA2418965C (en) | 2010-10-05 |
WO2002012420A1 (fr) | 2002-02-14 |
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