CN1196696A - 用于制造挤压产品的方法和设备及挤压产品 - Google Patents

用于制造挤压产品的方法和设备及挤压产品 Download PDF

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Publication number
CN1196696A
CN1196696A CN96197091A CN96197091A CN1196696A CN 1196696 A CN1196696 A CN 1196696A CN 96197091 A CN96197091 A CN 96197091A CN 96197091 A CN96197091 A CN 96197091A CN 1196696 A CN1196696 A CN 1196696A
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China
Prior art keywords
instrument
product
thermal conductivity
fluoropolymer
extruded
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CN96197091A
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CN1061594C (zh
Inventor
于利·耶尔文基烈
泰尔霍·拉赫蒂宁
米凯尔·舍贝里
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Uponor Innovation AG
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UPONOR BV
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Priority claimed from PCT/EP1996/002801 external-priority patent/WO1997010941A1/en
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Publication of CN1196696A publication Critical patent/CN1196696A/zh
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/901—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article of hollow bodies
    • B29C48/903—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article of hollow bodies externally
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Abstract

本发明涉及通过一工具(2)挤压材料的挤压机。含氟聚合物用在挤压材料和工具(2)之间以减少材料和工具间的摩擦。至少工具(2)的接触含氟聚合物的表面是导热率大于普通工具钢的导热率的材料的。因此,所产生的摩擦热可以有效地从工具(2)和挤压材料之间的界面传向工具(2),从而可以减少含氟聚合物的磨损,从而可以改善工具(2)的耐用性。在这种情形中,挤压产品将平滑地从工具(2)滑出,因而产品表面基本是光滑的,没有以特定波长重复的横向微观条带。

Description

用于制造挤压产品的方法 和设备及挤压产品
本发明涉及用于制造挤压产品的方法，在该方法中，挤压机从其挤压部分通过一工具挤压挤压材料，含氟聚合物用在挤压材料和工具之间以减少挤压材料和工具之间的摩托。
本发明还涉及用于制造挤压产品的设备，该设备包括一个用于挤压挤压材料的挤压部分，以及一个通过其挤压挤压材料的工具，布置有含氟聚合物，作为滑动剂用在挤压材料和工具之间。
本发明也涉及用上述方法制造的产品。
在交联聚乙烯的生产中以下情况是很重要的：材料应依靠着位于挤压机螺旋后的工具的壁良好地流动，使所产生的摩擦热保持低得使交联不能太早地开始。由于分子量高，适于生产交联管的聚乙烯种类流动得很差。由于上述的低挤压热和大的粘度，挤压过程相当突然，使螺旋和缸筒的温度由于所产生的摩擦热而易于上升得太高。
在塑料工业中，挤压工具主要是用易于机加工的硬工具钢或者也可能用不锈钢制造。为了改善清洁过程所需要的耐磨性。例如，工具一般是镀铬的。EPO 507613公开了一种镀有铬聚四氟乙烯的工具。聚四氟乙烯很有效地减少了摩擦，因而塑料沿工具表面稳定地滑动，当加工具有高分子量的塑料时，在挤压过程中聚四氟乙烯会很快地从工具表面磨掉，因此，为了向工具增加新的聚四氟乙烯，必须停止挤压过程。这种再涂覆甚至必须每天进行。这种停止加工并再次开始，以及聚四氟乙烯的磨损和增加工艺显然相当高地提高了成本。由于表面质量易于受损，因而在成品中易于看到聚四氟乙烯的过度磨损。管的内表面一般可能变得粗糙，或者在那里可发现塑料变得毛糙起来。在管的外表面上不一定可以看到不良特性，但是，在显微测量中可证实不匀度。
WO 94/21441提出了一种解决上述问题的技术方案，其中不使用聚四氟乙烯，而是在挤压产品和工具之间挤压一层损耗性的热固性材料。象在大多数情形中一样，上述那层必须在挤压之后从产品的表面清除掉，该发明复杂而难于实施。
WO 92/11125公开了一种添加于塑料中的滑动剂。但是，如果滑动剂添加于具有高分子量且需要强的加工的产品中，那么，由于其滑动性，塑料会易于在熔化区与螺旋脱开，塑料将未熔化地从挤压机脱出。
本发明的目的是提供用于制造挤压产品的方法和设备，其可以避免上述缺陷。另一个目的是提供具有良好特性的挤压产品。
按照本发明的方法的特征在于：工具的至少接触挤压材料的表面是导热率大于普通工具钢的导热率的材料的，因而所产生的摩擦热可以有效地从工具和挤压材料之间的界面传向工具。
另外，按照本发明的设备的特征在于：至少工具的与含氟聚合物接触的表面，至少局部在最小横截面处是导热率大于普通工具钢的导热率的材料的。
另外，使用按照本发明所述的方法制成的产品的特征在于：产品的表面基本是光滑的，没有以特定波长重复的横向微观条带。
本发明的基本构思在于，在工具和被挤压材料之间有含氟聚合物以减少塑料和工具之间的摩擦，至少工具的接触含氟聚合物的表面是导热率大于普通工具钢的导热率的材料的，因而所产生的摩擦热可以迅速地从界面传向工具。一个推荐实施例的进一步的构思是，在工具表面有耐磨镀层，如金刚石样镀层(DLC)，它具有充满含氟化合物如聚四氟乙烯的孔。第二个推荐实施例的构思是在工具镀层和塑料之间有一个滑动剂层，其基本包括含氟化合物。中层最好至少局部地包括含氟化合物如含氟弹性体，它被送入塑料中并迁移至抵接表面。第三实施例的构思是构成滑动剂的含氟化合物主要是在工具的喷嘴前的塑料熔化区之后在塑料层和工具之间被挤压的。
本发明的优点是，当至少工具的表面是导热性良好的材料的时候，所产生的摩擦热可以有效地从被挤压的塑料和工具之间的界面传走，因而工具的温度控制很好，甚至在界面处，例如对于聚四氟乙烯来说温度也不会上升得太高。已经意外地发现，通过从界面传走热量，例如聚四氟乙烯的耐磨性已得到显著改善。在普通工具中，虽然工具的温度被例如调节至250℃，但是，即使聚四氟乙烯的熔化温度高于300℃，聚四氟乙烯也相当容易地从工具磨掉。由于摩擦，界面处的温度超过了聚四氟乙烯允许的最高温度，因而聚四氟乙烯会易于磨掉。借助按照本发明的方法，在界面处可防止温度升得太高，从而改善了工具的耐磨性。金刚石样镀层(DLC)很耐磨，当其孔充满含氟化合物时，工具和被挤压的塑料之间的摩擦将变得很小。通过在工具和塑料的抵接面之间形成一滑动剂层，材料可沿工具表面很好滑动，但是滑动剂层并不妨碍实际塑料的加工，因而塑料可以是难于加工的交联聚乙烯。通过主要在塑料熔化区后在被挤压的塑料和工具间供应滑动剂，在实际塑料熔化和加工区中也可以很有效地利用摩擦热。
现在对照以下附图详述本发明。
图1是按照本发明的一种设备的示意横剖图，
图2是按照本发明的第二种设备的示意横剖图，
图3是按照本发明的第三种设备的示意横剖图，
图4a表示从质量不满的管的表面的测量结果，
图4b表示按照图4a的测量的傅里叶分析，
图5a表示使用按照本发明的方法制成的管的表面的测量结果，
图5b表示按照图5a的测量的傅里叶分析。
为了清楚起见，在附图中只画出挤压机的挤压部分1的端部，在图中可以看到挤压部分1的螺旋部分1a的端部和圆筒形部分1b的端部。挤压机可以是本身公知的任意一种挤压机，例如，普通的螺旋挤压机。一个工具2设置在挤压部分1的端部上。工具2包括一个在挤压产品外的喷嘴和一个在挤压产品内的心轴4。工具2可以为任何普通类型，例如具有带螺旋分配器的心轴托架的工具，具有多穿支承器的所谓蓝式模头工具、具有固定在螺旋头部的心轴托架的工具或所谓十字头工具。为了清楚起见，这些细部特征已从附图中略去。挤压产品，例如管5是从喷嘴3和心轴4之间挤压的。除了管5以外，挤压产品还可以是电缆包皮、薄膜或诸如此类的产品。
工具2与被挤压塑料接触的表面涂覆含氟塑料，最好是聚四氟乙烯，以便取得尽可能好的滑动特性。在涂覆聚四氟乙烯之前，如果工具2是用工具钢制成的，那么工具的表面最好施加一种材料，这种材料的导热率优于工具2其它部分上的材料导热性。工具钢的导热率一般大约为30w/mk。工具钢易于机加工，也有足够的硬度，因而使其很耐磨。镀层例如可以是铍铜合金，其导热率大约为200w/mk或更大。借助该镀层，塑料和工具2之间的摩擦引起的摩擦热可以有效地从被挤压的塑料和工具之间的界面传向工具2。在试验中已发现，在界面处的温度最多可降至30℃。由于上述降低的温度，聚四氟乙烯不会像以前应用中那么快地磨损。由于摩擦热，即使工具在其它部分被冷却，对于聚四氟乙烯来说，界面处的温度容易较早地升得过高。试验表明，在该临界区甚至下降10℃也可减少聚四氟乙烯的磨损，从而显著提高工具的寿命。界面的温度可以使用例如导热率大于100w/mk的镀层而降低。工具2也可以是由导热率优于工具钢的材料制成的。
除了使用导热率良好的材料以外，工具可以镀有例如一层薄的铬聚四氟乙烯镀层或所谓的金刚石样镀层(DLC)，其中的孔充满含氟化合物如聚四氟乙烯。DLC非常耐磨，充满孔的含氟化合物可以减少塑料和工具2之间的摩擦。
喷嘴3具有调温装置6，该调温装置例如设有油循环。类似的调温装置6也设置在心轴4上，借助调温装置6，喷嘴3和心轴4的温度可以按照需要通过向其传热或从其散热的方式加以控制。
按照本发明的方法和设备主要适于所有需要精确调温和良好滑动特性的挤压。例如，在聚乙烯泡沫的驱动装置中，必须使用很低的温度，并且由于放热反应，热必须有效地从工艺过程中除去。例如在取向过程中，典型的熔融物流会引起在分子实际取向阶段中的紊流，因而塑料和工具之间的摩擦最好利用聚四氟乙烯来减少。特别当制造交联聚乙烯管时，高温是一个特别的问题。特别难于使用高分子量的材料来制造产品。按照本发明的方法和设备也适于使用平均分子量大于200,000g/mol的材料。
图2是按照本发明的第二种设备的示意横剖图。图2中的标号相应于图1中的标号。图2所示的挤压机生产三层的产品，其外层5b和内层5最好构成基本具有含氟塑料如聚四氟乙烯的滑动剂层。由于这些滑动剂层，挤压材料可很好地沿着工具2的表面滑动。在工具2表面上的镀层，由于良好的导热性，使多余的热量有效地从界面传走，因而不会超过所使用的含氟塑料所允许持续的最高温度、外层5b和内层5c最好至少部分地含有含氟化合物如含氟弹性体，其送入塑料中并迁移至工具的抵接表面，从而减少摩擦。也附图不同，外层5b和内层5c可显著薄于中层5a，因而它们形成管5的外表皮和内表皮。因此，滑动剂只可用作薄表皮，滑动剂的效果并不会妨碍中层5a中的材料的机加工。中层5a可以是难于机加工的交联聚乙烯。
图3是按照本发明的第三种设备的示意横剖图。图3中的标号相应于图1和2中的标号。挤压机具有第一供应通道7a和第二供应通道7b，通过这两条供应通道可以将外层5b和内层5c送至挤压材料中层5a的外、内面。供应通道7a和7b用于将含有含氟弹性体或含氟塑料的滑动剂层恰好在工具2之前送至挤压材料的外、内面。在这种情形中，当滑动剂层在塑料熔化区之后，被送至挤压机时，中层5a可高效地利用摩擦热在挤压部分1中熔化和加工。在图3中，第二供应通道7b布置在进给螺旋中，但是，它也可以用于将材料从外送过中层5a。但是，通过图3所示的技术方案可以避免形成接缝。
如果挤压材料流变化，使纯摩擦流部分地变成熔融流，那么，在产品中形成横向条带，即，在产品中可检测到以不到1毫米至若干毫米的距离规律地重复的图案。这种图案也许不一定能用肉眼看到，而在显微镜观测中却可以检测到这些横向条带。当借助傅里叶分析用数学方法处理测量结果时，已经检测到不匀度是以一定的距离出现的，该距离一般从不到1毫米至若干毫米不等。本发明的方法和设备使挤压产品平滑地在工具表面上滑动，因而在挤压产品的表面上基本看不到不平坦的现象。
图4a表示从不令人满意的管的表面的显微测量的结果。在X轴上，管的外表面是在显微光波干涉仪上，管的粗糙度是在y轴上。在图中可见的不匀度不一定用肉眼可看到，但是如在附图中所示，不匀度可清楚地在显微测量中检测到。
图4b表示图4a所示测量的傅里叶分析。在傅里叶分析中可以清楚地检测到不匀度的序列性(sequentiality)，一个序列波长为0.81mm。发现一特殊波长证明塑料流不稳定，但是纯摩擦流已部分地变成熔融流。
图5a表示按照本发明方法制成的管的显微测量。从图5a可看出，表面已相当平坦均匀。图5b所示傅里叶分析也是对图5a测量作出的，它证明不能检测到序列的不匀度。
附图及有关的说明只是想描述本发明的构思。就细节而言，本发明可以在权利要求书的范围内变化。

Claims (22)

1.一种制造挤压产品的方法，在该方法中，挤压机将挤压材料从其挤压部分(1)通过一工具(2)挤压，在挤压材料和工具(2)之间使用含氟聚合物以减少挤压材料和工具之间的摩擦，其特征在于：工具(2)的至少接触挤压材料的表面是导热率大于普通工具钢的导热率的材料的，因而所产生的摩擦热可以有效地从工具(2)和挤压材料之间的界面传向工具(2)。
2.根据权利要求1所述的方法，其特征在于：工具的温度可以按照需要由调温装置(6)调节。
3.根据权利要求1或2所述的方法，其特征在于：挤压产品是至少两层的产品，接触工具(2)的那层至少部分地包括向塑料中供应且迁移至工具(2)的抵接表面的含氟化合物。
4.根据前述任一项权利要求所述的方法，其特征在于：挤压产品是具有至少三层的塑料管(5)，它包括一外表皮和一内表皮，所述外表皮和内表皮至少部分地包括向塑料中供应且迁移至抵接表面的含氟化合物如含氟弹性体，管(5)的中层(5a)基本是不含滑动剂的材料。
5.根据前述任一项权利要求所述的方法，其特征在于：主要是在工具(2)前的塑料熔化区之后，含有含氟弹性体或含氟塑料的滑动剂在被挤压的塑料和工具(2)之间被挤压。
6.根据前述任一项权利要求所述的方法，其特征在于：至少工具(2)与含氟聚合物接触的表面的导热率大于100w/mk。
7.根据前述任一项权利要求所述的方法，其特征在于：至少工具(2)的与含氟聚合物接触的表面的导热率大于200w/mk.
8.根据权利要求7所述的方法，其特征在于：至少工具(2)的与含氟聚合物接触的表面是铍铜合金的。
9.根据前述任一项权利要求所述的方法，其特征在于：平均分子量大于200,000g/mol的塑料用作挤压材料。
10.根据前述任一项权利要求所述的方法，其特征在于：挤压产品是交联聚乙烯管(5)。
11.一种制造挤压产品的设备，该设备包括一个用于挤压挤压材料的挤压部分(1)和一个通过其挤压挤压材料的工具(2)，设置含氟聚合物，作为滑动剂用在挤压材料和工具(2)之间，其特征在于：至少工具(2)的与含氟聚合物接触的表面，至少局部在最小横截面处是导热率大于普通工具钢的导热率的材料的。
12.根据权利要求11所述的设备，其特征在于：工具(2)包括一个用于控制工具(2)的温度的调温装置(6)。
13.根据权利要求11或12所述的设备，其特征在于：至少在某些地方，工具的表面在轴向上有一铬聚四氟乙烯镀层或金刚石样镀层(DLC)，其中的孔已注满含氟化合物。
14.根据权利要求11至13中任一项所述的设备，其特征在于：所述设备已布置得制造三层的产品。
15.根据权利要求14所述的设备，其特征在于：所述设备包括主要在工具(2)前的塑料熔化区之后用于在被挤压塑料和工具(2)之间挤压含有含氟弹性体或含氟塑料的滑动剂的装置。
16.根据权利要求10至15中任一项所述的设备，其特征在于：至少工具(2)的接触含氟聚合物的表面的导热率大于100w/mk。
17.根据权利要求16所述的设备，其特征在于：至少工具(2)的接触含氟聚合物的表面是铍铜合金的，其导热率大于200w/mk。
18.使用根据权利要求1所述的方法制成的产品，其特征在于：产品的表面基本是光滑的，没有以特定波长重复的横向微观条带。
19.根据权利要求18所述的产品，其特征在于：所述产品是包括至少三层的管，至少外层和内层(5b，5c)包括含有含氟化合物的滑动剂。
20.根据权利要求19所述的产品，其特征在于：薄的表皮构成所述的外层和内层(5b，5c)。
21.根据权利要求19或20所述的产品，其特征在于：中层(5a)包括平均分子量大于200,000g/mol的材料。
22.根据权利要求21所述的产品，其特征在于：中层(5a)主要包括不含滑动剂的基本交联的聚乙烯。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104220226A (zh) * 2012-03-30 2014-12-17 住友电工超效能高分子股份有限公司 树脂剥离性治具
CN109476107A (zh) * 2016-07-29 2019-03-15 安德里茨股份公司 螺旋挤压机

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DE69624516T2 (de) 2003-07-17
CA2231860A1 (en) 1997-03-27
SE9503272L (sv) 1997-03-21
HRP960299A2 (en) 1997-10-31
AR003145A1 (es) 1998-07-08
CO4771156A1 (es) 1999-04-30
KR100439093B1 (ko) 2005-08-31
ATE226507T1 (de) 2002-11-15
US6203651B1 (en) 2001-03-20
WO1997010940A1 (en) 1997-03-27
DE69624516D1 (de) 2002-11-28
CN1061594C (zh) 2001-02-07
SE521725C2 (sv) 2003-12-02
ZA965402B (en) 1998-05-28
AU6990396A (en) 1997-04-09
EP0971812B1 (en) 2002-10-23
KR19990063608A (ko) 1999-07-26
JPH11512356A (ja) 1999-10-26
MY132142A (en) 2007-09-28
EG21194A (en) 2000-12-31
SE9503272D0 (sv) 1995-09-20
IN189245B (zh) 2003-01-18
CA2231860C (en) 2007-01-02
EP0971812A1 (en) 2000-01-19

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