CN1252752A - 涂覆多层聚合材料的金属管 - Google Patents
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Abstract
涂层金属管构造物,包含金属管(10)。第一聚合材料的内层(12)与管(10)结合以提供防腐。第一聚合材料具有高结晶性,低于0.05的阻尼因子和至少100MPa的挠曲模量。第二聚合材料的外层(14)围绕内层(12)挤压成形以吸收冲击能和消除机械振动和噪声。第二聚合物具有至少0.05的阻尼因子和低于50MPa的挠曲模量。第二聚合材料是具有至少一种玻璃化转变温度低于室温的聚合物成分的多相聚合物。
Description
发明背景
本专利申请是1995年10月10日提交的美国专利申请08/541,855的部分继续申请。
本发明涉及金属管制品,更准确地说,本发明涉及汽车工业中用作如制动系统的管路、燃油管线和输油冷却管线用途的金属管。
汽车应用中所用管路要求具有能使汽车延长使用寿命的耐腐蚀性和耐磨性。另外,所述管路按汽车遭遇的环境(即石头撞击和劈碎)必须具有耐磨性。最后,管路应能隔离和吸收机械振动和噪声。为满足这些要求,通常往用于汽车场合的金属管涂上一层或者层保护层。
用于汽车工业中的涂层一般特征在于下列中的一种或两种。首先,在钢管表面上沉积金属基质。通常这是一层消毁的层,其中基质在金属管之前被腐蚀。其次,阻挡层沉积在基质的上面以阻止腐蚀介质启动腐蚀和提供增强的耐磨性。
在汽车工业中用作基质和/或阻挡层的过去用过的材料和复合材料的例子包括:镀铅锡钢板(通常85%铅和15%锡的合金);在镀铅锡钢板上的富锌涂料;锌-铝合金(由95%锌和5%铝组成,商标为GALFAN);GALFAN涂层上的富铝涂料;电镀锌或锌-镍;电镀锌上的PVF或PVDF;热镀铝;环氧树脂和耐纶。
这些材料可以以许多组合形式用作阻挡层和/或基质层,但有许多限制它们使用的缺点。现有技术的涂层材料和方法只表现有限的抗磨性和抗来自石头的撞击劈碎和磨耗。为了提供改进的劈碎和抗磨性,经常把可以收缩的热塑性套层使用常规方法加到涂层管的周围。但是这种方法非常昂贵而且并非总是有效。例如,可收缩塑料套层仅有有限的吸收或隔离振动和噪声的能力。另外,可收缩塑料套管的使用妨碍其在终端部件或端子下使用,使管端部暴露在腐蚀作用下。
为了克服同时在汽车和流体输送管路中使用时所遇到的全部问题(即腐蚀、磨损、磨耗、劈碎、石头碰撞、机械振动、噪声),必须制定适于管涂层的具体聚合物的性能。由于没有单一的聚合材料在力争克服所有问题中是有效的,有效的产物将考虑聚合物结构和性能以及材料的加工和工程应用条件之间的关系。
由此,本发明提供了一种金属管上的极好的多层聚合物涂层,利用聚合材料的动态机械性能以达到保护用于汽车或流体输送场合下金属管的许多部件。把两层聚合物极好的动态机械性能结合起来以在耐腐蚀性和磨损、磨耗、劈碎以及石头撞击保护诸方面提供最大的效益。此外,本发明多层涂层在吸收冲击能和消除机械振动和噪声上也是有效的。
发明概述
本发明提供一种涂层金属管的构造物,第一聚合材料的内层与金属管结合以提供防止腐蚀作用。第一聚合材料的特征在于高结晶性,低阻尼因子和高挠曲模量。优选地,阻尼因子低于0.05而挠曲模量大于100MPa。
第二聚合材料的外层围绕内层以吸收冲击能和消除机械振动和噪声。第二聚合材料具有高阻尼因子和低挠曲模量。优选是,阻尼因子大于0.05的挠曲模量小于50MPa。外层材料是一种至少具有两种聚合物成分的多相聚合物。这些成分的每一种都有着截然不同的玻璃化转变温度,至少其中有一种应低于室温。
附图简述
图1是本发明部分涂层金属管构造物的截面图;和
图2是图1为便于与终端部件连结而裸露终端的管构造物截面图。
附图的详细描述
图1说明按本发明涂覆的金属管10。管10由第一聚合材料的内层12和第二聚合材料的外层14涂覆。内层12与金属管10结合而外层14围绕着内层12挤压成形。层12和14通过使用粘合剂或任何其它连结方法而不结合在一起。这样做的优点是使外层14在管10的终端上能被剥离(图2),有利于与终端部件或端子连接。
许多考虑都涉及包括层12和14的特殊聚合物材料或共混料的选择。内层聚合物必须提供化学稳定性和防止金属管10的腐蚀。外层聚合物必须能吸收冲击能并且能消除机械振动和噪声。外层聚合物还应适合于容易剥离或除去以适于端部部件或端子的连结。
为了达到这些效果必须考虑特殊聚合物的具体性能和结构特性。例如,对于具有良好化学稳定性的内层聚合物来说,必须具有高结晶性。然而,高结晶性会降低聚合物吸收冲击能。隔离机械振动和噪声的能力。这个功能由外层聚合物提供。
动态机械性能是确定外层聚合物消除机械振动和噪声能力的关键。简述这些动态机械性能如下。
聚合物的模量是测量时的温度和频率ω的函数。聚合物的阻尼因子,介质损耗角正切,tanδw,是假模是部分,GW 11,对真实模量部分,G′W(储能模量)的比值。自然频率,ω0,是能通过机械系统消除的较低噪声频率。机械系统的自然频率,ω0和可传性,T按如下被表达成聚合物动态机械性能的函数:
和
式中K是形状因数。M是系数的质量,G′0和G′W分别是在自然频率ω0和强制频率ω1下聚合物的剪切储能模量tanδw是聚合物在强制频率下阻尼的测量值,和T是机械系统的可能性。
动态模量和阻尼是温度和频率的函数。这些机械性能可通过设计聚合物的分子结构而得以控制。为达此目的,通过降低方程式中聚合物的储能模量可获得低自然频率的振动系统。另外,通过选择具有高阻尼因子的聚合物可以抑制谐振的可透性。
内层12,如上所述,由选自具有抗化学和液体的聚合材料组成。层12与底层金属管10结合而阻止腐蚀介质达到或侵蚀管10。
选择用于层12的聚合材料应特别耐腐蚀介质或通常在汽车场合下所遇到的流体,如制动液,机油和燃料。
为了达到这些目的,内层12的聚合材料必须具有高结晶性和低阻尼因子。阻尼因子是储能模量中假模量部分对真实模量部分的比值,并且就内层12而言,优选小于0.05。内层12的聚合材料还应具有至少100MPa的挠曲模量。
用于内层12合适的聚合物材料包括,但不限于聚酰胺(耐纶)、聚亚酰胺、聚酯、氟塑料(如聚氟乙烯或聚偏氟乙烯)、环氧树脂、聚苯硫化物、聚缩醛、酚醛树脂、聚酮和聚烯烃。
外层14由围绕层12挤压成形的聚合材料组成。层14与内层12未结合或弱结合。当内层12提供阻止化学品和腐蚀性液体腐蚀的保护作用时,外层14提供来自石头撞击的抗劈碎和磨损以及磨耗,这对于内层12而言是一种补充。外层14还负担吸收冲击能以及消除机械振动和噪声。热绝缘和热防护也由层14提供。
外层14的聚合材料是多相聚合物。术语“多相”表明所述材料是两种或多种聚合物的共混料或共聚物。借助于包含两种或多种聚合物成分,能设计外层聚合材料具有隔振或吸收机械振动和噪声强制频率的特定阻尼特性(自然频率和可透性)。
外层14的多相聚合物具有至少0.05的高阻尼因子。优选的是,在使用温度范围介于-50和150℃之间时,阻尼因于介于0.1和0.3。这种高阻尼因子对比内层较低的阻尼因子保证了冲击能耗散多些。外层聚合物挠曲模量应低于50MPa。较低的挠曲模量意味着聚合材料对比内层聚合物更易弯曲(易挠曲)。
外层14的壁厚大于50微米。优选壁厚在200和500微米之间。
使用至少具有两种不同聚合物成分的多相聚合物在各成分具有截然不同的玻璃化转变温度时是有利的。当温度接近聚合物的玻璃化转变温度时,聚合物具有很高的阻尼因子。因此,使多相聚合物具有多种玻璃化转变温度,会在很宽的温度范围内提供高阻尼因子,因此,会在技术维护环境下提供消除机械振动和噪声的最高能力。
优选的是,外层中至少有一种聚合物成分具有低于室温(22℃)的玻璃化转变温度且其它的聚合物成分熔点在100℃以上。另外优选一种聚合物成分是橡胶相而另一成分是热塑性相。
外层14还具有高水平的耐热性。可将热反射填料加到层14的聚合材料中以提高耐热性。
用于外层14的合适多相聚合材料包括,但不限于聚酰胺,聚酯、聚烯烃、聚氨酯和聚氯乙烯的共聚物或聚合物共混物(或合金化聚合物)。热塑性聚烯烃(TPO)是合适的聚合物共混物的具体例子。
在施加层12和14于金属管10上之前,管10用一种基质进行表面处理以进一步提高耐腐蚀性。用于表面处理管10的合适材料包括铬酸盐、磷酸盐、锌、富铝涂料、锌铝基质、锌镍基质或这些材料的混合物。这样做会进一步提高耐腐蚀性。
把层12和14极好的动态机械性能结合起来,提供了突出的性能和获得用于汽车或流体输送场合中所用的金属管多层保护。内层12能提供防止有害化学品和腐蚀性液体腐蚀的保护作用,而外层14能提供抗磨损性,磨耗性,劈碎和石头撞击、吸收冲击能和隔振或吸收机械振动和噪声。
下面的内容是按本发明具体的管涂层构造物的实例。提供这些实施例仅为了说明并非用来或被构成本发明范围的限制。
实施例1
钢管用锌铝基质表面处理。由PVF(聚氟乙烯)组成的内层与表面处理过的钢管结合。由聚酰胺与EPDM橡胶的聚合物共混物组成的外层在内层上挤压成形。在管的端部剥离外层以提供终端部件或端子的连接。
实施例2
钢管用锌铝基质表面处理,由PVF组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层的上面挤压成形,剥离掉管终端上的外层以提供终端部件或端子的连结。
实施例3
钢管用锌铝基质表面处理。由挤压耐纶组成的内层与表面处理的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形,剥离管端部的外层以提供终端部件或端子的连接。
实施例4
钢管用锌铝基质表面处理。由挤压聚酮组成的内管与表面处理过的钢管结合。由聚酰胺和EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例5
钢管用锌铝基质表面处理。由挤压聚酮组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层上挤压成形,剥离管终端上的外层以提供终端部件或端子的连接。
实施例6
钢管用锌铝基质表面处理。由PVF组成的内层与表面处理过的钢管结合。由PVC(聚氯乙烯)和丁腈橡胶的聚合物共混物组成的外层在内层上挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例7
钢管用锌铝基质表面处理。由PVF组成的内层与表面处理过的钢管结合。由PVC和丁腈橡胶的聚合物共混物组成的外层在内层上挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例8
钢管用锌铝基质表面预处理。由PVF组成的内层与表面处理过的钢管结合。由聚酯热塑性弹性体共聚物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例9
钢管用锌铝基质表面处理。由挤压耐纶组成的内层与表面处理过的钢管结合。由聚酯热塑性弹性体共聚物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例10
钢管用锌铝基质表面处理。由环氧树脂组成的内层与表面处理过的钢管结合。由聚酰胺与EPDM橡胶的聚合物共混物组成的外层在内层的上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例11
用锌铝基质表面处理钢管。由环氧树脂组成的内层与表面处理过的钢管结合。由聚烯烃与EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例12
钢管用锌镍基质表面处理。由PVF组成的内层与表面处理过的钢管结合。由聚酰胺和EPDM橡胶的聚合物共混物组成的外层在内层上挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例13
钢管用锌镍基质表面处理。由PVF组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例14
钢管用锌镍基质表面处理。由挤压耐纶组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例15
钢管用锌镍基质表面处理。由挤压聚酮组成的内层与表面处理过的钢管结合。由聚酰胺和EPDM橡胶的聚合物共混物组成的外层在内层上挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例16
钢管用锌镍基质表面处理,由挤压聚酮组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例17
钢管用锌镍基质表面处理。由PVF组成的内层与表面处理过的钢管结合。由PVC和丁腈橡胶的聚合物共混物组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例18
钢管用锌镍基质表面处理。由挤压PVF组成的内管与处理过的钢管结合。由聚酯热塑性弹性体共聚体组成的外层在内层上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
实施例19
钢管用锌镍基质表面处理。由挤压绵纶组成的内层与表面处理过的钢管结合。由聚酯热塑性弹性体共聚物组成的外层在内层上挤压成形。剥离管的终端上的外层以提供终端部件或端子的连接。
实施例20
钢管用锌镍基质表面处理。由环氧树脂组成的内层与表面处理过的钢管结合。由聚酰胺和EPDM橡胶的聚合物共混物组成的外层在内层的上面挤压成形。剥离管的终端上的外层以提供终端部件或端子的连接。
实施例21
钢管用锌镍基质表面处理。由环氧树脂组成的内层与表面处理过的钢管结合。由聚烯烃和EPDM橡胶的聚合物共混物组成的外层在内层的上面挤压成形。剥离管终端上的外层以提供终端部件或端子的连接。
参考所显示和描述过的实施例对本发明的各种特征进行了说明。然而,应当理解正如下面权利要求书所说明的不偏离本发明的精神和范围可以作出改进方案。
Claims (27)
1.涂层金属管构造物,包括:
金属管;
为提供防腐与所述管结合的第一聚合材料的内层,所述第一聚合材料具有高结晶性,低阻尼因子和高挠曲模量;和
为吸收冲击能和消除机械振动和噪声围绕所述内层的第二聚合材料的外层,所述第二聚合材料具有高阻尼因子和低挠曲模量,和所述第二聚合材料是具有至少两种聚合物成分的多相聚合物,各个所述成分具有截然不同的玻璃化转变温度。
2.根据权利要求1所述涂层金属管构造物,其中所述内层和所述外层未结合或弱结合。
3.根据权利要求1所述涂层金属管构造物,其中所述第一聚合材料具有低于0.05的阻尼因子和至少100MPa的挠曲模量。
4.根据权利要求1所述涂层金属管构造物,其中所述第二聚合材料具有至少0.05阻尼因子和低于50MPa的挠曲模量。
5.根据权利要求4所述涂层金属管构造物,其中所述第二聚合材料的所述阻尼因子在施涂温度范围在-50和150℃之间时在0.1-0.3之间。
6.根据权利要求1所述涂层金属管构造物,其中所述外层具有至少50微米的壁厚。
7.根据权利要求6所述涂层金属管构造物,其中所述壁厚在200微米和500微米之间。
8.根据权利要求1所述涂层金属管构造物,其中所述第二聚合材料的所述成分之一是橡胶相和所述成分中的另一个是热塑性相。
9.根据权利要求1所述涂层金属管构造物,其中反射热填料配置在所述第二聚合物材料中以提供高水平的耐热性。
10.根据权利要求1所述涂层金属管构造物,其中所述第一聚合材料选自于聚酰胺、聚亚酰胺、聚酯、氟塑料、环氧树脂、聚苯硫化物、聚缩醛、酚醛树脂、聚酮和聚烯烃。
11.根据权利要求1所述的涂层金属管构造物,其中所述第二聚合材料由选自聚酰胺、聚酯、聚烯烃、聚氨酯和聚氯乙烯聚合物的共聚物或聚合物共混物组成的组。
12.根据权利要求1所述涂层金属管构造物,其中所述金属管用选自铬酸盐、磷酸盐、锌、富铝涂料、锌铝、锌镍或其混合物的基质进行表面处理。
13.涂层金属管构造物,包含:
金属管;
为提供防腐与所述管结合的第一聚合材料的内层,所述第一聚合材料具有高结晶性,低于0.05的低阻尼因子和至少100MPa的高挠曲模量;和
与所述内层不结合或弱结合的第二聚合材料的外层,所述第二聚合材料是具有至少两种聚合物成分的多相聚合物,所述各个成分具有截然不同的玻璃化转变温度,所述成分中至少一种具有低于室温的玻璃化转变温度。
14.根据权利要求13所述涂层金属管构造物,其中所述第二聚合材料是具有至少两种聚合物嵌段的无定形共聚物,所述嵌段之一是具有低于室温的玻璃化转变温度的软链段嵌段,所述嵌段的另一个是熔点在100℃以上的硬链段嵌段。
15.根据权利要求13所述涂层金属管构造物,其中所述第二聚合材料的所述成分之一是橡胶相而另一所述成分是热塑性相。
16.涂层金属管构造物,包含:
金属管;
为提供防腐与所述管结合的第一聚合材料的内层,所述第一聚合材料具有高结晶性,低于0.05的低阻尼因子和至少100MPa的高挠曲模量;和
为吸收冲击能和消除机械振动和噪声与所述内层未结合或弱结合的第二聚合材料的外层,所述第二聚合材料是具有至少0.05的高阻尼因子和低于50MPa的低挠曲模量。
17.根据权利要求16所述涂层金属管构造物,其中所述第二聚合材料在施涂温度范围介于-50和150℃之间对介于0.01和0.3之间。
18.根据权利要求16所述涂层金属管构造物,其中所述外层具有大于50微米的壁厚。
19.根据权利要求18所述涂层金属管构造物,其中所述壁厚介于200微米和500微米之间。
20.根据权利要求16所述涂层金属管构造物,其中反射填料被配置在所述第二聚合材料中以提供高水平耐热性。
21.涂层金属管构造物,包含:
不锈钢管;和
与所述管不结合或弱结合的聚合材料的涂层,所述聚合材料具有至少0.05的阻尼因子和低于30MPa的挠曲模量。
22.根据权利要求21所述的涂层金属管构造物,其中所述聚合材料是选自聚酰胺、聚酯、聚烯烃、聚氨酯和聚氯乙烯聚合物的共聚物或聚合物共混物。
23.根据权利要求21所述涂层金属管构造物,其中所述阻尼因子在施涂温度范围介于-50和150℃之间时介于0.1和0.3之间。
24.涂层金属管构造物,包含:
钢管;
第一聚合材料的内层;和
与所述内层未结合或弱结合的第二聚合材料的外层,所述第二聚合材料具有至少0.05的高阻尼因子和低于30MPa的挠曲模量的。
25.根据权利要求24所述涂层金属管构造物,,其中所述第一聚合材料选自耐纶、聚氟乙烯、聚偏氟乙烯、环氧树脂或富铝涂料。
26.根据权利要求24所述涂层金属管构造物,其中所述第二聚合材料是由选自聚酰胺、聚酯、聚烯烃、聚氨酯和聚氯乙烯的聚合物的共聚物或聚合物共混物组成的。
27.涂层金属管构造物,包含:
金属管;
为防腐与所述金属管结合的第一聚合材料的内层,所述第一聚合材料具有高结晶性,低于0.05的阻尼因子和至少100MPa的挠曲模量;和
与所述内层未结合或弱结合的热塑性聚烯烃的外层。
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-
1998
- 1998-02-23 EP EP98906643A patent/EP1028844A4/en not_active Withdrawn
- 1998-02-23 JP JP53694398A patent/JP2001513171A/ja active Pending
- 1998-02-23 BR BR9807725-2A patent/BR9807725A/pt not_active IP Right Cessation
- 1998-02-23 WO PCT/US1998/003478 patent/WO1998036899A1/en not_active Application Discontinuation
- 1998-02-23 KR KR1019997007631A patent/KR20000075571A/ko not_active Application Discontinuation
- 1998-02-23 CA CA002282346A patent/CA2282346A1/en not_active Abandoned
- 1998-02-23 CN CN98804228A patent/CN1078843C/zh not_active Expired - Fee Related
- 1998-02-23 AU AU61813/98A patent/AU732160B2/en not_active Ceased
-
1999
- 1999-08-09 US US09/370,424 patent/US6589617B2/en not_active Expired - Fee Related
-
2002
- 2002-05-22 US US10/153,416 patent/US6689440B2/en not_active Expired - Lifetime
Cited By (6)
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WO2006053468A1 (fr) * | 2004-11-19 | 2006-05-26 | Kefu Chen | Dispositif de traitement de craquage magnetique de mazout a poles similaires opposes |
CN107299642A (zh) * | 2011-04-11 | 2017-10-27 | 赢创德固赛有限公司 | 用于海上建筑物的用聚酰胺包封的结构用钢管 |
CN102913693A (zh) * | 2012-07-27 | 2013-02-06 | 联塑市政管道(河北)有限公司 | 一种新型钢管及其制作方法 |
CN103244816A (zh) * | 2013-05-10 | 2013-08-14 | 苏州工业园区方圆金属制品有限公司 | 一种镀锌铁管 |
CN103775754A (zh) * | 2013-12-26 | 2014-05-07 | 孙家成 | 一种有碳纤维内涂层的输油管道及制备方法 |
CN103775754B (zh) * | 2013-12-26 | 2016-02-03 | 孙家成 | 一种有碳纤维内涂层的输油管道 |
Also Published As
Publication number | Publication date |
---|---|
EP1028844A4 (en) | 2002-02-13 |
AU732160B2 (en) | 2001-04-12 |
CN1078843C (zh) | 2002-02-06 |
AU6181398A (en) | 1998-09-09 |
KR20000075571A (ko) | 2000-12-15 |
US6589617B2 (en) | 2003-07-08 |
US20010008665A1 (en) | 2001-07-19 |
US5972450A (en) | 1999-10-26 |
JP2001513171A (ja) | 2001-08-28 |
US6689440B2 (en) | 2004-02-10 |
CA2282346A1 (en) | 1998-08-27 |
BR9807725A (pt) | 2000-02-15 |
WO1998036899A1 (en) | 1998-08-27 |
EP1028844A1 (en) | 2000-08-23 |
US20030012907A1 (en) | 2003-01-16 |
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