CN1572482A - 弹性体粘结的片材及其制造方法 - Google Patents
弹性体粘结的片材及其制造方法 Download PDFInfo
- Publication number
- CN1572482A CN1572482A CNA2004100452382A CN200410045238A CN1572482A CN 1572482 A CN1572482 A CN 1572482A CN A2004100452382 A CNA2004100452382 A CN A2004100452382A CN 200410045238 A CN200410045238 A CN 200410045238A CN 1572482 A CN1572482 A CN 1572482A
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- Prior art keywords
- elastomer
- sheet material
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- filler
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Abstract
本发明涉及弹性体粘结的片材，其包含硫化的弹性体内容物及包含至少一种粘结在其中的填料的内容物，其中所述硫化的弹性体内容物包括，基于整个弹性体内容物，大约25～70％重量，优选大约40～60％重量的至少一种硫化弹性体，该硫化弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
Description
技术领域
本发明涉及一种弹性体粘结的片材，其特别适用于密封。本发明还涉及制备这种弹性体粘结的片材的方法。
背景技术
众所周知，纤维增强的弹性体垫圈易于不可逆地老化。起先，这一问题因高达80％重量的非常高的石棉含量所掩盖，所以即使弹性体老化，该材料仍保持其稳定性。当人们认识到石棉危及健康之后，就开始尝试用其它纤维代替石棉纤维，特别是用合成纤维如对-芳族聚酰胺纤维、玻璃纤维或碳纤维代替石棉纤维。但是，这些纤维的高成本，且各自存在使用特定纤维的制造问题，这意味着它们的含量必须显著地降低，并且需要用低成本的粉状填料如高岭土、二氧化硅、石墨等替代。
其结果是，弹性体粘合剂必须承担更高比例的稳定垫圈材料的作用，虽然弹性体首先是热稳定性最低的原料，其次易于老化，这损害了纤维状与粉状填料的长期一体性。
根据常用的弹性体材料R橡胶(二烯弹性体，如NBR、SBR、NR等)的类型，以及其中共聚的三元共聚物(例如丙烯腈或苯乙烯)的量，主要用作垫圈材料的橡胶类型含有高达35％的不饱和碳双键，这使得它们容易氧化，因为这些双键可以直接与氧气反应，生成氢过氧化物。随后，所得氢过氧化物上的H原子的离去，从而形成聚合物自由基，进而使大分子断裂。这种主要依靠氧气的热老化的可测量效应包括弹性模量的显著增加及相关柔韧性的下降，即脆性的增加。后者可以导致微观裂纹，结果可能导致整个垫圈爆裂，甚至在密封法兰处的最低荷载发生变化情况下，例如因装置的启动和停止过程中管线系统的膨胀所引起的爆裂。
这里，进一步的问题是由弹性体材料主链中不饱和碳双键的后硫化(post-vulcanization)引起的。在没有消耗的交联剂(例如硫磺、硫磺给体或过氧化产生的自由基)存在下，只要主链中仍保留着未交联的二烯，该弹性体材料在硫化工艺之后就长期保持易于后交联。对垫圈，这因为上述作用同样导致材料的硬化。
发明内容
本发明的一个目的是提供一种弹性体粘结的片材，该片材具有改进的长期性能，尽管纤维状填料的含量相对较低。本发明的进一步目的是提供一种老化现象降低的弹性体粘结的片材。
本发明的另一个目的是提供一种制备弹性体粘结的片材的方法，该片材具有改进的长期性能，尽管纤维填料的含量相对较低。本发明的再一个目的是提供一种制备弹性体粘结的片材的方法，该片材具有改进的长期性能，尽管纤维填料的含量相对较低。
本发明涉及弹性体粘结的片材，该片材包含硫化的弹性体内容物及包含至少一种粘结在其中的填料的内容物，其中所述硫化的弹性体内容物包括，基于整个弹性体内容物，大约25～70％重量，优选大约40～60％重量的至少一种硫化弹性体，该硫化弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
本发明还涉及弹性体粘结的片材，该片材包含硫化的弹性体内容物及至少一种粘结于其中的填料内容物，其中至少有两层实施硫化，并因此而牢固地粘结，且该两层包括硫化的弹性体，该弹性体具有至少一种粘结于其中的填料，对于层数为至少一层且小于总层数的情形，该至少一种填料用至少一种弹性体粘结，该至少一种弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
在包含具有至少一种粘结于其中的填料的硫化弹性体的片材中，如果硫化弹性体材料，基于整个弹性体内容物，包含大约25～75％重量，优选大约40～60％重量的至少一种硫化弹性体(其主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键)，则可以显著地改进这种材料的长期性能，并使得大分子的降解进行得更缓慢。
在包含至少两层互相粘结的弹性体粘结的片材(其是通过硫化的弹性体粘结的，包含至少一种填料，并通过实施硫化而牢固地粘结)中，如果至少一层是通过硫化弹性体粘结的，该硫化弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％不饱和碳双键，特别是通过部分氢化的R橡胶或主链基本上为饱和的聚亚甲基型的M橡胶粘结的，则可以更显著地降低氧化敏感度，而且促进大分子的缓慢降解。这里，十分重要的是片材不具有均匀的结构，其是利用弹性体的混合物，如包含M橡胶和R橡胶的混合物制备的，而且如所指出的那样，包含至少两层不均匀的层，然而，两层不均匀层中至少一层是仅通过所述的弹性体粘结的，该弹性体的主链中具有≤10％的不饱和碳双键。其它层可以仅通过R橡胶或者任何所需的R橡胶和/或M橡胶的混合物进行粘结，所述R橡胶包括部分氢化的R橡胶。优选“具有与不具有碳双键”的各层交替出现。
由于在同时存在两种或多种弹性体的交联过程中出现竞争反应，所以需要这些不均匀层。例如，不同种类的二烯因为其局部电荷、空间几何学或共轭双键的差异而或者更早地交联或者更快地交联，进而夺取了所有成桥(bridge-forming)试剂。其结果是，在存在于混合物中的反应性较差的弹性体中，很少发生或不发生交联，因为交联剂不充足。如果是这样，将有弹性体以未交联或不充分交联的形式存在于片材中，而且该弹性体将不能发挥其作为粘结纤维状和粉状填料的稳定化基质的功能。
单独构建不均匀的层还允许在一种片材中使用不同交联系统。可以就pH、促进剂、活化剂配制理想的交联系统，并将其应用于每种弹性体或每种弹性体混合物，由此产生理想的交联。
本发明还涉及制备包含至少两层的弹性体粘结的片材的方法，其中每层的起始混合物是在溶剂存在下通过混合而制备的，该起始混合物包含弹性体内容物、交联剂、加工助剂和填料，并连续加工成层，得到片材，所述的层通过实施硫化而牢固地粘结，其中为了制备至少一层的起始混合物，可以专门使用包含至少一种硫化弹性体的弹性体内容物，所述硫化的弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
将在下面的说明和权利要求中说明本发明的进一步的实施方式。
附图说明
下面使用实施例和工艺说明详细解释本发明。
图1是一种弹性体粘结的垫圈用片材的一种优选实施方式的横截面图。
图2是用于制备弹性体粘结的片材的双辊压延机。
具体实施方式
适于制备平垫圈的片材的实施方式(适于图1的截面图)包含1，2两层，其填料已经通过部分氢化的双键含量＜7％的丁腈橡胶粘结。在该两层1，2之间，存在层3，其填料已经通过至少一种R橡胶粘结。层1～3已经硫化了，由此牢固地彼此粘结。层1～3的厚度为大约100μm～4mm。另外，对具体应用条件，可以存在薄的外涂层4，5，例如以粘结剂层的形式或脱模层的形式，1～3层的某些或全部也可以具有织物形式，更具体金属细网纱的增强，或膨胀金属的增强组分。
通过图2中的实施例表示的双辊压延机具有一个大的加热辊6(周长1～6m)(典型地在140～190℃)，其上有较小周长的冷却辊7(典型地在10～30℃)，它们相向旋转。通过水压力缸8，沿如箭头9所示的向加热辊6的方向，对冷却辊7加压。为了制备片材的层，将糊状或易碎的材料10送入辊隙中。双辊压延机已经在合适的容器11中调节了，以便捕获挥发的溶剂。
为制造片材，各种原材料例如弹性体材料、硫化添加剂、粉状填料、纤维材料和加工助剂与大部分有机溶剂例如石油溶剂油、甲苯和二甲苯，在高速搅拌机中混合，获得均匀的材料。如果使用多于一种弹性体，其同时在高速搅拌机中进行共混。原材料的加入顺序取决于材料的构成。搅拌机可以具有搅拌叶轮或搅拌桨叶，和如果需要，一种或多种高速刀头(knife head)。混合步骤产生糊状或易碎的材料。然后，将其在根据图2的双辊压延机上进行进一步加工，通过将糊状或易碎的材料导入辊隙，并利用滚筒6，7的相向旋转移动，典型地以同样的圆周速度旋转，将组分带入系统中而产生片材。结果是随着溶剂挥发和橡胶在加热辊6的表面早期交联，而以薄层(大约0.008～0.02mm)形式形成的片材。随着辊6的每一次进一步旋转，这些层由另外的层连续地补充。在施加到滚筒6后，每层立即干燥并在辊6的旋转过程中硫化，通过辊6，7之间施加的压力而压实。一旦要制造的每层达到了所要求的最终厚度，并且片材的所有层已经完成后，辊6，7分离并停止，将辊6周围的片材切开并从辊6上剥离。可以通过例如典型的冲压(stamp up)或切割、激光切割、使用高压水喷射切割或锯，而从得到的片材制造有用的平垫圈。
实施例1：具有唯一的的R橡胶作为基体的组合物1
在管状混炼机中混合下列原材料来制备硫化胶粉的均匀物。
13～17份R橡胶，此时为丁腈橡胶
38～45份高岭土
3～8份沉淀二氧化硅
5～9份对芳族聚酰胺纤维
25～30份玻璃纤维
2～3份硫基的硫化添加剂，包含硫磺、促进剂、活化剂、共活化剂和加工助剂。
在混合过程中，使用28～33份(基于干物质总量)的甲苯溶解NBR。
实施例2：具有R和M橡胶的共混物或部分氢化的R橡胶作为基体的组合物2
在管状混炼机中混合下列原材料来制备硫化胶粉的均匀物。
6.8～8.5份R橡胶；丁腈橡胶
6.8～8.5份M橡胶或双键含量＜7％的橡胶，此时为部分氢化的丁腈橡胶(34±1％ACN，残余双键3～5％)
38～45份高岭土
3～8份沉淀二氧化硅
5～9份对芳族聚酰胺纤维
25～30份玻璃纤维
2～3份硫基的硫化添加剂，包含硫磺、促进剂、活化剂、共活化剂和加工助剂。
在混合过程中，使用28～33份(基于干物质总量)的甲苯溶解两弹性体。
实施例3：具有唯一的M橡胶或部分氢化的R橡胶作为基体的组合物3
在管状混炼机中混合下列原材料来制备硫化胶粉的均匀物。
13～17份M橡胶或双键含量＜7％的橡胶，此时为部分氢化的丁腈橡胶(34±1％ACN，残余双键3～5％)
38～45份高岭土
3～8份沉淀二氧化硅
5～9份对芳族聚酰胺纤维
25～30份玻璃纤维
2～3份硫基的硫化添加剂，包含硫磺、促进剂、活化剂、共活化剂和加工助剂。在混合过程中，使用28～33份(基于干物质总量)的甲苯溶解HNBR。
制造样品片的实施例
使用图2的双辊垂直压延机来制造样品片。
用高压水加热辊6的表面温度至180±5℃。辊6的周长为4060mm，其宽度为1560mm。使用冷却水使冷却辊7的表面温度冷却到20±5℃。冷却辊7的周长为1585mm，其宽度为1560mm。用90±1kN的压力使冷却辊7施加到辊6上。两辊6，7同时相向运动，圆周速度(取决于片厚度及其他)为30～90米/分钟。当两辊6，7旋转时，制备的组合物10部分加入到辊隙内。选择组合物10的所有的起始重量，使得在压延加工完成后，可以得到2mm厚的垫圈片。
此时，通过压延，加工30公斤总重量的优选组合物1～3来制造2mm厚的垫圈片，如下表所示：
| 样品号 | 层的数目和厚度 | 相对粘结剂含量 | |
| 1 | 1(2mm) | 实施例1的100％NBR组合物 | |
| 2 | 1(2mm) | 实施例3的100％HNBR组合物 | |
| 3 | 1(2mm) | 实施例2的50％HNBR/50％NBR组合物 | |
| 4 | 3 | 相对含量 | 绝对含量 |
| 0.5mm | 第一层：100％HNBR | 实施例3的25％HNBR组合物 | |
| 1.0mm | 第二层：100％NBR | 实施例2的50％NBR组合物 | |
| 0.5mm | 第三层：100％HNBR | 实施例3的25％HNBR组合物 | |
| 总绝对含量：50％HNBR/50％NBR | |||
相对于样品片1～3，使用组合物1和组合物3制造样品4，得到包含3层的片。这里程序如下。首先，用滚筒加工7.5公斤的组合物3，压实并在与实施例1～3相同的加工条件下硫化。不停下滚筒，即之后直接压实15公斤组合物1并硫化到组合物3的第一层上。之后无需中间停下滚筒，再次通过滚筒直接加入另外的7.5公斤组合物3，压实并硫化。由此样品片4包含3个互相粘结的层(如图1所示)，上层和下层已经唯一地用HNBR粘结，而中间层用NBR作为基体。
这里重要的和无疑的事实是样品片3和样品片4由完全相同量的相同原料构成(除了硫化试剂)，但是弹性体分别加工意味着其在不均匀的层中存在。取决于所使用的弹性体，也有可能不同层的交联添加剂不同，以便获得理想的橡胶硫化特性。
首先为了量化使用的弹性体，其次为了量化弹性体存在的结构，对垫圈老化性能的影响，对样品片进行了高温湿蒸汽测试。该测试非常适合于测试弹性体粘结的平垫圈在极端苛刻的条件下的降解性能，因此可以对不同垫圈材料进行划分，在此测试中因为320℃的高温和120巴的湿蒸汽环境，对弹性体给予了非常大的热和氧化应力。
从样品片1～4上，冲压下直径Da＝98mm，Di＝58mm，d＝2mm的垫圈环。这些样本用44N/mm2的压力在密闭的盖板中，在测试器中夹紧。在此密闭盖板中，有10克软化水。将盖板升温至320℃。其中的一些水挥发了，并在盖板中形成湿蒸汽环境。因为盖板已经密闭，其受到蒸汽压曲线所要求的120巴的内压。使用数据阶梯(ladder)以时间的函数记录内压。
在盖板内，由蒸汽沿样本中的裂缝或破坏的连接逸出，引起的突然的压力降，指示由于弹性体降解的垫圈的破坏。
在此系统中，突然的压力降而届满的时间可以分别作为垫圈和所用的弹性体耐老化的测量值。
样品片1～4的结果分别为操作时间4、17、15和30天，因此相应的减缓了老化过程。用HNBR自身代替一半NBR，导致实质的操作时间延长，但这只是样品片4长度的一半，样品片4包含不均匀的层，并具有显著提高的耐热和耐氧化性，虽然原料和加工参数相同。因此优选包含此种层的片材。
下面纤维中的一种或多种可以任选地加入作为纤维状填料：对芳族聚酰胺纤维、碳纤维、陶瓷纤维、纤维素纤维或包含纤维素衍生物的纤维，棉花纤维、纤维状硅灰石、玻璃纤维、矿棉花纤维或聚合物纤维等。
也可以任选加入下面材料中的一种或多种作为粉状填料：煅烧的高岭土或未煅烧的高岭土、重晶石、硅灰石、粉状云母、粉状的板岩或页岩、粉状的石英、碳黑、石墨、粉状的玻璃、碳酸钙、软木、多种二氧化硅、碳化硅、氮化硅、氧化钛、氮化硼等。
当有可能和有利的，填料可以已经例如使用硅烷、钛酸盐、锡酸盐等表面处理以得到特定的性质。
也可以任选使用下列交联化学品中的一种或多种作为交联系统：硫促进剂系统、硫供体系统、过氧化物、高能辐射或二胺或磷酸盐交联系统或硫代磷酸盐交联系统。
也可以任选使用下列物质中的一种或多种作为加工助剂或添加剂：脱模剂、塑炼剂、稳定剂、抗氧剂、粘结助剂、有机或无机颜料、发泡剂、增塑剂或硫化延迟剂。
用作R橡胶的基体材料优选下列弹性体中的一种或多种：NR、NBR、SBR、BR、IR或CR(按照ISO1629的缩写)。
下列弹性体的至少一种可以作为M橡胶或主链上不饱和双键含量优选＜10％，特别＜7％的橡胶的基体材料：EPDM、EPM、HNBR、ACM、AECM、FKM或EAM。部分氢化的橡胶例如HSBR、HNR、HCR等同样可以用作基体材料。
当适合于弹性体，下列极性或非极性物质可以用作溶剂：石油溶剂油、苯、甲苯、二甲苯、乙醇、THF、水、酯、酮或二氯甲烷。
也可以通过层1～3的独立制造，接着通过硫化粘结；或通过以适应希望的应用的形式连续制造层1～3，而制造片材。
虽然已经参考优选实施方式表明并描述了本发明，对本领域技术人员，很明显可以有许多变化和改进而不脱离本发明权利要求所限定的精神和范围。
Claims (18)
1.一种弹性体粘结的片材，其包含硫化的弹性体内容物及包含至少一种粘结在其中的填料的内容物，其中该硫化弹性体内容物包括，基于整个弹性体内容物，大约25～70％重量，优选大约40～60％重量的至少一种硫化弹性体，该硫化弹性体的主链中在未硫化的状态下具有不超过10％的不饱和碳双键。
2.根据权利要求1的片材，其中至少有两层实施硫化，并因此而牢固地粘结，且包含其中粘结有至少一种填料的硫化弹性体，对于层数为至少一层且小于总层数的情形，所述至少一种填料已经被至少一种弹性体粘结，该至少一种弹性体的主链中在未硫化的状态下具有不超过10％的不饱和碳双键。
3.根据权利要求1或2的片材，其中所述弹性体的主链中包含不超过7％的不饱和碳双键。
4.根据权利要求1～3中任一项的片材，其中所述填料具有粉状、层状或纤维状，并以相应层材料的至少30％重量的比例存在。
5.根据权利要求4的片材，其中所述填料选自有机物和无机物。
6.根据权利要求1～5中任一项的片材，其中所述至少一种填料选自表面处理或非表面处理的对芳族聚酰胺纤维、玻璃纤维、矿棉花纤维、碳纤维、陶瓷纤维、纤维素纤维、纤维素衍生物纤维，棉花纤维、纤维状硅灰石、聚合物纤维、煅烧的高岭土、未煅烧的高岭土、重晶石、粉状的硅灰石、云母、板岩或页岩、石英、碳黑、石墨、粉状玻璃、碳酸钙、软木、二氧化硅、碳化硅、氮化硅。
7.根据权利要求1～6中任一项的片材，包含至少一层通过弹性体粘结的层，所述弹性体选自：NR、NBR、SBR、BR、IR、CR、EPDM、EPM、HNBR、ACM、AECM、FKM、CSM和EAM。
8.根据权利要求1～7中任一项的片材，包含至少一层通过弹性体粘结的层，所述弹性体选自：EPDM、EPM、HNBR、ACM、AECM、FKM和EAM。
9.根据权利要求2～8中任一项的片材，其中所述层的厚度为大约100μm～4mm。
10.根据权利要求2～9中任一项的片材，其中通过至少一种主链中具有不超过10％的不饱和碳双键的弹性体粘结的各层，与通过至少一种主链中具有不超过20％的不饱和碳双键的弹性体粘结的层相互交替。
11.根据权利要求2～10中任一项的片材，其中通过至少一种主链中具有不超过7％的不饱和碳双键的弹性体粘结的各层，与通过至少一种主链中具有不超过20％的不饱和碳双键的弹性体粘结的层相互交替。
12.一种弹性体粘结的片材，其包含硫化的弹性体内容物及包含至少一种粘结在其中的填料的内容物，其中至少有两层实施硫化，并因此而牢固地粘结，且包含其中粘结有至少一种填料的硫化弹性体，对于层数为至少一层且小于总层数的情形，所述至少一种填料已经被至少一种弹性体粘结，该至少一种弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
13.一种制备弹性体粘结的片材的方法，该片材包括至少两层，其中对于每一层，起始混合物是在溶剂存在下通过混合制备的，该起始混合物包含弹性体内容物、交联剂、加工助剂和填料，并连续加工成层，得到片材，对该层实施硫化，并因此而牢固地粘结，其中为了制备至少一层的起始混合物，可以专门使用包含至少一种硫化弹性体的弹性体内容物，所述硫化的弹性体的主链中在未硫化的状态下具有不超过10％，优选不超过7％的不饱和碳双键。
14.根据权利要求13的方法，其中所述起始混合物是通过具有一个加热辊和一个冷却辊的双辊压延机加工成层的。
15.根据权利要求13或14的方法，其中为制造所述至少一层的起始混合物，所使用的弹性体材料包括选自R橡胶、R橡胶的混合物、M橡胶的混合物，及R橡胶与M橡胶的混合物的弹性体。
16.包含权利要求1～11中任一项的材料的平垫圈。
17.包含权利要求12的材料的平垫圈。
18.根据权利要求16或17的平垫圈，其是通过冲压或切割步骤中的一种由所述材料制备的。
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| CN103203947A (zh) * | 2012-01-13 | 2013-07-17 | 贝尔直升机德事隆公司 | 可附接的弹性体垫 |
| CN104403210A (zh) * | 2014-11-19 | 2015-03-11 | 杭州顺豪橡胶工程有限公司 | 有色金属化学选矿设备用耐强酸橡胶辊胶料及制备方法 |
| CN111617557A (zh) * | 2010-10-06 | 2020-09-04 | 霍林斯沃思和沃斯有限公司 | 适合液压应用的过滤介质 |
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- 2004-05-12 ES ES04011228T patent/ES2397835T3/es not_active Expired - Lifetime
- 2004-05-12 EP EP20040011228 patent/EP1484360B1/de not_active Expired - Lifetime
- 2004-05-12 SI SI200431989T patent/SI1484360T1/sl unknown
- 2004-05-12 PL PL04011228T patent/PL1484360T3/pl unknown
- 2004-05-14 AU AU2004202029A patent/AU2004202029B2/en not_active Ceased
- 2004-05-27 JP JP2004158002A patent/JP2004359951A/ja active Pending
- 2004-06-03 CA CA 2469693 patent/CA2469693C/en not_active Expired - Fee Related
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- 2004-06-04 MX MXPA04005429A patent/MXPA04005429A/es active IP Right Grant
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933869A (zh) * | 2010-02-10 | 2013-02-13 | 阿尔贝托·博顶 | 配备了改进的密封组件的气弹簧 |
| CN102933869B (zh) * | 2010-02-10 | 2015-09-02 | 阿尔贝托·博顶 | 配备了改进的密封组件的气弹簧 |
| CN111617557A (zh) * | 2010-10-06 | 2020-09-04 | 霍林斯沃思和沃斯有限公司 | 适合液压应用的过滤介质 |
| CN111617557B (zh) * | 2010-10-06 | 2022-04-12 | 霍林斯沃思和沃斯有限公司 | 适合液压应用的过滤介质 |
| CN103203947A (zh) * | 2012-01-13 | 2013-07-17 | 贝尔直升机德事隆公司 | 可附接的弹性体垫 |
| US9156237B2 (en) | 2012-01-13 | 2015-10-13 | Bell Helicopter Textron Inc. | Attachable elastomeric pad |
| CN103203947B (zh) * | 2012-01-13 | 2016-06-08 | 贝尔直升机德事隆公司 | 可附接的弹性体垫 |
| CN104403210A (zh) * | 2014-11-19 | 2015-03-11 | 杭州顺豪橡胶工程有限公司 | 有色金属化学选矿设备用耐强酸橡胶辊胶料及制备方法 |
| CN104403210B (zh) * | 2014-11-19 | 2017-08-15 | 杭州顺豪橡胶工程有限公司 | 有色金属化学选矿设备用耐强酸橡胶辊胶料及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100375676C (zh) | 2008-03-19 |
| DE10325700A1 (de) | 2005-01-05 |
| US20040265559A1 (en) | 2004-12-30 |
| JP2004359951A (ja) | 2004-12-24 |
| US7217452B2 (en) | 2007-05-15 |
| PL1484360T3 (pl) | 2013-03-29 |
| CA2469693A1 (en) | 2004-12-06 |
| HK1073818A1 (en) | 2005-10-21 |
| CA2469693C (en) | 2009-08-11 |
| AU2004202029B2 (en) | 2007-08-30 |
| SI1484360T1 (sl) | 2013-02-28 |
| EP1484360A1 (de) | 2004-12-08 |
| KR20040108593A (ko) | 2004-12-24 |
| MXPA04005429A (es) | 2004-12-08 |
| BRPI0401917A (pt) | 2005-02-01 |
| ES2397835T3 (es) | 2013-03-11 |
| EP1484360B1 (de) | 2012-10-31 |
| AU2004202029A1 (en) | 2004-12-23 |
| BRPI0401917B1 (pt) | 2014-10-21 |
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