CN101563207A - 全氟聚合物组合物部件的制备方法 - Google Patents

全氟聚合物组合物部件的制备方法 Download PDF

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CN101563207A
CN101563207A CNA2007800472956A CN200780047295A CN101563207A CN 101563207 A CN101563207 A CN 101563207A CN A2007800472956 A CNA2007800472956 A CN A2007800472956A CN 200780047295 A CN200780047295 A CN 200780047295A CN 101563207 A CN101563207 A CN 101563207A
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parts
fluoropolymer
per
flat surfaces
fiber
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J·D·布泽
C·K·迪凯恩
T·P·甘尼特
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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    • Y10T428/31544—Addition polymer is perhalogenated

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

可在不打乱纤维取向的情况下，通过摩擦焊接方法例如振动焊接和超声焊接将包含平行于部件表面取向的(增强的)纤维的全氟聚合物部件接合在一起。所述部件可直接使用或切割为其他形状。此类部件可用于其中需要耐高温性和/或耐化学性以及良好物理特性例如强度和/或韧性的场合。这些类型的部件包括垫圈和密封环。

Description

全氟聚合物组合物部件的制备方法
相关申请的交叉引用
本专利申请要求2006年12月22日提交的美国临时专利申请60/876,836的优先权，该临时专利申请全文以引用方式并入本文。
发明领域
本发明涉及用于焊接包含长纤维的全氟聚合物部件的方法。本发明尤其涉及在基本上不打乱纤维取向的情况下摩擦焊接包含呈基本上平行于平面的取向的长纤维的全氟聚合物部件的方法。
发明背景
为热塑性塑料并包含呈平行于片材的主平面(所谓的x-y平面，相对于穿过片材厚度的z轴)取向的连续纤维或长纤维的全氟聚合物片材是已知的(参见如美国专利4,163,740、5,194,484、5,232,975、5,470,409、5,503,662、和5,506,052，所有专利据此以引用方式并入)。然而，现有技术并未描述在不打乱纤维取向的情况下将纤维增强的全氟聚合物材料(其中纤维在x-y平面内取向)焊接在一起的方法。
常规方法的另一个缺点在于通过常规焊接方法得到的片材厚度稍微受到了该方法的限制。例如，当期望获得厚片材时，基质聚合物的固结就可能不完全。可通过将几个片材压缩模塑在一起来获得较厚的片，例如具有大于0.05cm标称厚度的片。然而，如果需要相对厚的片材时，此类方法可能较为耗时，因为如果加热和/或冷却速率过快，则热应力可引起开裂或其他缺陷。在制备工艺中，人们通常寻求介于产品质量和生产效率之间的平衡。期望有一种用于获得此类厚部件、同时避免纤维取向发生实质性变化的更快捷方法。
发明概述
在一个方面，本发明是一种用于形成包含全氟聚合物或聚氯三氟乙烯聚合物的部件的方法，所述方法包括以下步骤：
(a)使包含全氟聚合物的第一部件的平坦表面与包含全氟聚合物或聚氯三氟乙烯聚合物的第二部件的平坦表面接触，所述第一和第二部件包含基本平行于所述平坦表面的平面取向的纤维；
(b)在相对彼此移动所述第一部件和所述第二部件的同时保持所述第一和第二部件的所述平坦表面之间的接触，以在所述第一和第二部件之间产生足量的摩擦热，从而使所述第一和第二部件的各自平坦表面熔融和/或软化；以及，
(c)在保持所述平坦表面之间接触的同时停止所述第一和第二部件的运动，并持续足够的时间以使得所述第一和第二部件的平坦表面冷却并彼此粘附。
本发明的另一方面是通过本发明的方法形成的部件。
附图简述
图1示出了已振动焊接在一起的本发明的两个全氟聚合物部件。图中标记有比例和焊接线，可以看到在焊接线处的纤维取向并未发生改变。
发明详述
在本文中使用了某些术语，其中一些定义如下：
所谓片材或平坦表面的“x-y平面”是指平行于指定表面的表面的平面。“z”方向垂直于x-y平面。
所谓“接触”是指两个(或更多个)部件实际触碰，并且它们可以使用极小的压力(力)或很大的压力接触。
所谓“片材”是指具有两个优选地彼此平行的主表面的形式，其具有边缘。片材的x-y平面平行于所述表面中的至少一个，优选地同时平行于两个表面。“z”方向穿过片材的厚度。优选地，片材厚度小于片材表面的最小线性尺寸的20％，更优选小于10％。如本文所用，本发明的片材无需为正方形或矩形形式，而是其也可以为近似于成品所需形状的“预成形件”，但其中最终制品的厚度需要大于单个片材。例如，如果制备某些类型的环，尽管两个主表面是平坦的，但片材可以为环状，并且环可具有用于获得环的片材的几个厚度。
所谓“基本平行于x-y平面取向的纤维”是指纤维的长轴平行于x-y平面取向。纤维的长轴可弯曲，但该长轴通常平行于x-y平面。
在一个实施方案中，用于本发明方法中的片材包含全氟聚合物。普通技术人员将会知道全氟聚合物是合成的有机高分子，其中基本上所有的氢原子已被氟原子取代。就本发明的目的而言，此类聚合物包含小于0.5重量％的氢，更优选小于0.2重量％且非常优选小于0.1重量％的氢。作为另外一种选择，其中至少一些但非全部氢原子被氟原子取代的氟聚合物适合以与全氟聚合物相同的方式使用。全氟聚合物是优选的。
聚合物例如热塑性塑料的摩擦焊接是熟知的，并且有几种主要的使用“类型”，所有类型均适用于本文。振动焊接仅指在给定压力下使在所要焊接处通常比较平坦的两个部件相互接触，并使两个部件以相对低的频率(例如约150Hz至约300Hz，优选约170Hz至约250Hz)相对彼此重复运动。当表面足够熔融和/或软化时，停止运动并保持部件间的接触直到热塑性塑料固化或硬化并且各部件粘结。尽管线性运动是优选的，但一个部件相对于另一个部件的运动可以为线性的(即以直线)、圆形的(即辐射线或曲线)、无规的(即非重复性运动)或它们的任何组合。
在摩擦焊接的另一种类型中，将各部件如上所述接触在一起，但运动频率要高得多，在超声波范围内，通常为15kHz至50kHz。运动也可为线性的、圆形的、无规的或运动的任何组合。
尤其对于圆形部件而言，还可使用旋转焊接。在旋转焊接中，将各部件如上所述接触在一起，但现在是相对于彼此作圆形运动，采用的速度(rpm)和压力足以熔融或软化热塑性塑料。然而，由于更靠近旋转轴的表面部分比外面部分运动更慢，因此该方法最好应用于具有平坦表面的类似环形部件。优选的焊接方法为振动焊接。
在一个优选的实施方案中，第一和第二部件的一个或两个为全氟聚合物片材。可将两个此类片材焊接在一起，随后可将所得部件焊接到第三单个片材上，并重复此操作直到制备出所需厚度的部件。普通技术人员将能够在不脱离本发明范围的情况下设计出其他组合或方法来组合片材。例如，可将两个或更多个焊接在一起的片材焊接到另一个由两个或更多个焊接在一起的片材构成的部件上。虽然可能需要多个焊接步骤来制备所需厚度的部件，但本发明的方法仍可比用于制备类似厚度的部件的常规压缩模塑方法快捷。
如本文所述，所得的此类厚部件可按原样使用，或者可被修剪和/或机器加工和/或分割从而得到所需的最终部件。由于它们由全氟聚合物制备并包含纤维，因此此类部件具有优异的化学和热稳定性，并且具有良好的强度、模量和/或韧性。它们在需要此类特性的应用中可用作例如密封件、垫圈、轴衬、管和环。
具有高模量和/或拉伸强度的纤维(通常称为增强纤维)特别有用。有用的纤维包括玻璃、碳(石墨)、芳族聚酰胺，而碳是尤其优选的，并且碳是特别优选的。纤维的典型填充量为至少约5％、更优选至少约10％、并非常优选至少约15％。纤维的最大填充量通常为65％、更优选约50％、并特别优选约30％。所有的此类百分比均为按组合物中纤维加全氟聚合物的总重量计的重量百分比。应当理解，任何优选的最小填充量可与任何优选的最大填充量组合以形成优选的填充量范围。有用的纤维“等级”包括通常用于增强热塑性塑料的那些。
优选地纤维为至少约0.3cm长、更优选地为至少约0.6cm长、非常优选地为至少约1.3cm长、并特别优选地为至少约2.5cm长。纤维长度应理解为是指实际在组合物中的纤维的长度。
通常包含在全氟聚合物组合物中的其他材料也可包含在本发明的组合物中。此类材料包括常规量的颜料。
优选地，第一和第二部件两者的全氟聚合物相同，和/或优选的全氟聚合物还可以为热塑性塑料。优选地，全氟聚合物由一种或多种包括四氟乙烯(TFE)的单体制成，更优选地此类TFE聚合物包含至少80摩尔％的衍生自TFE的重复单元。适用的具有TFE的共聚单体为全氟化烷基乙烯基醚，特别是全氟代(正丙基乙烯基醚)，以及全氟化烯烃，特别是六氟丙烯。另一种优选的全氟聚合物是聚四氟乙烯。
图1示出了在包含取向碳纤维的两个全氟聚合物片材间的振动焊接。该图片通过X射线微断层摄影术生成，这大体描述于A和D.Van Dyck的“Desktop X-Ray Microscopy and Microtomography”，“Journal ofMicroscopy”，第191卷，第151至158页(1998)中，该文献以引用方式并入本文。图中标记有焊接线，可观察到焊接线处纤维的取向无明显改变。
一般程序，实施例1至9。根据以引用方式并入的美国专利5,470,409来制备用20重量％0.64cm(0.25″)长的短切碳纤维增强的部分固结的(注-部件可为并优选为全部固结的)(95-97％)0.64cm(0.25″)厚的
Figure A20078004729500081
PFA 340(四氟乙烯和全氟代(丙基乙烯基醚)的共聚物，得自E.I.du Pontde Nemours and Company，Wilmington，DE 19898U.S.A.)片材。将这些板用带锯切成合适尺寸的正方形。将所有样本在
Figure A20078004729500082
VW-8UHL机器(Branson Ultrasonics Corp.，Danbury，CT 06813，USA)上以240Hz的频率和1.78mm(0.070″)的线性振幅进行振动焊接。在机器台板上使用防滑胶带代替夹具以防止正在焊接的样本滑动。
实施例1
将两个5.08cm的正方形(2″×2″)片材摞在一起置于焊机中。将焊机设置为供给181kg(400lbs.)的夹紧力(689kPa，100psi)并振动，直到达到1.27mm(0.050″)(焊接部件总厚度的10％)的焊接深度。在提供焊接的20秒内未达到焊接深度并产生极少的飞边。该板易于撬开并显示出仅局部区域熔融。
实施例2
将两个5.08cm的正方形(2″×2″)片材摞在一起置于焊机中。将焊机设置为供给327kg(720lbs.)的夹紧力(1.24MPa，180psi)以在20秒的振动时间内达到1.27mm(0.050″)的焊接深度。如为焊接部件总重量2.1％(相比之下，1.27mm的位移计算为约10％)的飞边所示，未达到焊接位移。然而达到了强固焊接，表现在不能使楔子通过焊缝。与单独板的约2.0相比，焊接的部件的比重为1.99。
实施例3
重复实施例2，不同的是将夹紧力提升至907kg(2000lbs.)(3.45MPa，500psi)，接着在振动停止后保持在1.72MPa(250psi)以使焊接熔体在压力下凝固。产生的飞边等于焊接的部件总重量的10.4％表明达到了完全的1.27mm。位移(即界面处熔融的开始)在振动开始后约10秒开始。获得了各侧面周围无间隙的良好焊接。焊接的部件的比重为2.01。
实施例4
使用907kg(2000lb)的夹紧力(3.45MPa，500psi)和0.64mm(0.025″)的焊接位移将两个5.08cm的正方形(2″×2″)片材焊接在一起。获得了各边缘周围无可见间隙的良好焊接。产生了大量飞边，其为基于焊接部件总重量的5.7重量％。部件比重为2.03。
实施例5
使用开始在3.45MPa(500psi)下10秒、接着在689kPa(100psi)下10秒的振动周期将两个5.08cm的正方形(2″×2″)片材焊接在一起。不控制焊接位移。产生了极少(0.3重量％)的飞边，但焊接良好，不能用手拉开。部件的比重为2.02。
实施例6
重复实施例5，不同的是将3.45MPa(500psi)下的振动时间从10秒延长至13秒。通过使楔子(冷凿和锤子)通过焊缝来测定焊接强度。对分开的板的目测表明沿着焊接界面和在其中一个板的本体材料中均失败。这表明在焊接的平面中，焊接强度相当于板的本体强度。
实施例7
通过连续焊接5个片材(4个焊缝)来构造5.08cm(2″)正方形的、3.18cm(1.25″)厚的块。焊接周期为在3.45MPa(500psi)下14秒和在689kPa(100psi)下10秒。需要的总时间为约6分钟，包括在各焊接周期后用于排尽任何聚合物烟雾的60秒。所有四个焊缝外观上看起来良好。估计的飞边为3.5重量％。
实施例8
使用2720kg(6000lb)的负荷(3.38MPa，490psi)持续24秒焊接两个8.89cm(3.5″)的正方形片材。焊缝看起来良好，但产生的飞边的量为10.2重量％。部件比重为2.02。
实施例9
重复实施例8，不同的是将焊接周期分为3.38MPa(490psi)下14秒和676kPa(98psi)下10秒。焊接线外观良好并且产生的飞边的量减至2.5重量％。该实施例表明如果振动时间/压力周期保持恒定，那么焊接时间与部件的面积大小无关。部件比重为1.97。

Claims (13)

1.用于形成包含全氟聚合物或聚氯三氟乙烯聚合物的部件的方法，所述方法包括以下步骤：
(a)使包含全氟聚合物的第一部件的平坦表面与包含全氟聚合物或聚氯三氟乙烯聚合物的第二部件的平坦表面接触，所述第一和第二部件包含呈基本上平行于所述平坦表面的平面取向的纤维；
(b)在相对彼此移动所述第一部件和所述第二部件的同时，保持所述第一和第二部件的所述平坦表面之间的接触，以在所述第一和第二部件之间产生足量的摩擦热，从而使所述第一和第二部件的各自平坦表面熔融和/或软化；以及，
(c)在保持所述平坦表面之间接触的同时，停止所述第一和第二部件的运动足够的时间，以使得所述第一和第二部件的平坦表面冷却并彼此粘附。
2.权利要求1的方法，其中所述移动是重复性运动并在约150Hz至约300Hz的频率下进行。
3.权利要求1至2中任一项的方法，其中所述运动是重复性的并在约15kHz至约50kHz的频率下完成。
4.权利要求1至3中任一项的方法，其中按所述部件中所述氟聚合物和所述纤维的总重量计，所述纤维为所述部件的约5重量％至约50重量％。
5.权利要求1至4中任一项的方法，其中所述纤维为至少约0.6cm长。
6.权利要求1至5中任一项的方法，其中所述第一部件全氟聚合物和/或所述第二部件全氟聚合物为四氟乙烯的共聚物或四氟乙烯的均聚物。
7.权利要求6的方法，其中所述共聚物包含至少80重量％的衍生自四氟乙烯的重复单元。
8.权利要求6的方法，其中所述共聚物为一种或多种包含全氟化烷基乙烯基醚或全氟化烯烃的共聚物。
9.权利要求1至8中任一项的方法，其中所述第一和第二部件具有约0.3cm或更大的最小横截面尺寸。
10.权利要求1至9中任一项的方法，其中所述纤维为玻璃、碳或芳族聚酰胺纤维中的一种或多种。
11.权利要求1至10中任一项的方法，其中所述第二部件包含全氟聚合物。
12.权利要求11的方法，其中所述第一部件全氟聚合物与所述第二部件全氟聚合物相同。
13.由权利要求1至12中任一项的方法形成的部件。
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CN105984120A (zh) * 2015-03-19 2016-10-05 丰田自动车株式会社 树脂接合体、树脂接合体的制造方法及车辆用构造体
CN114889140A (zh) * 2022-05-26 2022-08-12 成都路宝工程材料有限公司 一种基于土工格栅塑熔焊接工艺方法
CN114889140B (zh) * 2022-05-26 2023-11-24 成都路宝工程材料有限公司 一种基于土工格栅塑熔焊接工艺方法

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