CN107880295A - 多层预浸料结构及其制造方法 - Google Patents

多层预浸料结构及其制造方法 Download PDF

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Publication number
CN107880295A
CN107880295A CN201710744548.0A CN201710744548A CN107880295A CN 107880295 A CN107880295 A CN 107880295A CN 201710744548 A CN201710744548 A CN 201710744548A CN 107880295 A CN107880295 A CN 107880295A
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China
Prior art keywords
prepreg
resin
fixed bed
multilayer
vacuum
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CN201710744548.0A
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CN107880295B (zh
Inventor
朴相润
李晓真
崔致勋
梁埈滈
尹炳哲
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Limitless Carbon Co
Hyundai Motor Co
Kia Corp
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Limitless Carbon Co
Hyundai Motor Co
Kia Motors Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C66/73—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 intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—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 intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
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Abstract

公开了一种多层预浸料结构及其制造方法。多层预浸料结构包括预浸料层，所述预浸料层通过利用第一树脂浸渍碳纤维织物形成；以及固定层，所述固定层由具有比第一树脂更高的固化速率的第二树脂形成并且提供在预浸料层的一个表面上。

Description

多层预浸料结构及其制造方法
技术领域
本发明涉及多层预浸料结构(multilayer prepreg structure)及其制造方法，并且更具体地，涉及具有改善的外观质量的多层预浸料结构及其制造方法。
背景技术
通常，由碳纤维增强塑料(CFRP)形成的部件被制造成具有预浸料结构，其中由碳纤维编织的织物利用树脂浸渍。CFRP具有低重量与强度比和期望的外观，因此可用作车辆内部材料。
然而，在常规预浸料结构中，在树脂固化过程中，树脂从碳纤维织物的表面层退出(recede)，导致预浸料结构的表面不均匀。为了平坦化不均匀的预浸料结构表面，可以重复地将涂层材料施加到预浸料结构表面。涂层材料的重复施加增加了制造时间和制造成本。
此外，残留在树脂中的气泡扩散到表面可能引起针孔(pinhole，小孔，气孔)，导致预浸料结构的外观缺陷。
图1是示出常规的预浸料结构的剖视图，以及图2是示出常规的预浸料结构的制造方法的图。
如图1和图2所示，为了制造预浸料结构10，利用树脂12浸渍碳纤维织物11，真空排气(vacuum-evacuated)，然后加热，使得树脂12在排出气泡B的同时进行热硬化。
在该过程中，气泡B从树脂12的内部排出，从而可以形成针孔。此外，树脂12可能从预浸料结构10的侧表面泄漏，从而暴露碳纤维织物11。
当透明涂层(clear coating layer)20被施加到暴露了碳纤维织物11的预浸料结构10时，透明涂层20的表面沿碳纤维织物11的形状变形。这会降低预浸料结构10的外观质量，需要施加另外的且经常重复的透明涂层，以实现预浸料结构10表面的平坦化。
因此，需要具有改进外观质量的平坦表面的新型预浸料结构和制造改进的预浸料结构的方法，该方法需要更少的透明涂层应用。
已经提供了上述描述以帮助理解本发明的背景，并且上述描述不应被解释为本领域技术人员已知的常规技术。
发明内容
本公开解决了上述问题。本公开的目的是提供具有平坦表面的改进的多层预浸料结构和制造改进的预浸料结构的方法。
在一个示例性实施方式中，改进的多层预浸料结构包括通过利用第一树脂浸渍碳纤维织物形成的预浸料层，和施加到预浸料层的一个表面的由第二树脂形成的固定层，所述第二树脂具有比第一树脂更高的固化速率(curing rate)。
在进一步的示例性实施方式中，单层预浸料层与固定层的厚度比为1:0.25～1。
在进一步的示例性实施方式中，预浸料层的厚度为0.4mm或更小。
在进一步的示例性实施方式中，第一树脂在125摄氏度的温度下具有8-30分钟的凝胶时间(gel-time)，并且第二树脂在125摄氏度的温度下具有2-10分钟的凝胶时间。
在进一步的示例性实施方式中，第一树脂是含有双氰胺类硬化剂的环氧树脂，并且第二树脂是含有脲类硬化剂的环氧树脂。
改进的多层预浸料结构还可以包括施加到固定层表面的透明涂层。
本公开还描述了制造改进的多层预浸料结构的方法的示例性实施方式，所述方法包括以下步骤：编织碳纤维织物；通过利用第一树脂浸渍碳纤维织物来制造预浸料层；将由具有比第一树脂更高固化速率的第二树脂形成的固定层施加到预浸料层的一个表面；真空包装具有施加至其的固定层的预浸料层；和在高压釜内加热真空包装的预浸料层和固定层。
在进一步的示例性实施方式中，所述方法还包括以下步骤：在施加固定层之前，层叠多个预浸料层。
在真空包装预浸料层中，将设置有施加至其的固定层的预浸料层放置在真空袋中，然后将压力降低到1巴或更小。
为了固化真空包装的预浸料结构，将真空包装的具有施加至其的固定层的预浸料层在3-7巴的压力和120-180℃的温度下固化45-90分钟。
附图说明
从以下结合附图的详细描述，将能更清楚地理解本发明的上述和其它目的、特征和其它优点，其中：
图1是常规预浸料结构的剖视图；
图2是示出用于制造常规预浸料结构的方法的图示。
图3是改进的多层预浸料结构的示例性实施方式的剖视图；
图4是示出用于制造改进的多层预浸料结构的方法的示例性实施方式的图示；
图5是示出在制造过程中处于真空包装状态的改进的多层预浸料结构的示例性实施方式的图示；以及
图6a至图6c是根据第二树脂的固化速率改变的多层预浸料结构的外观发生变化的照片。
具体实施方式
现在将详细参考本发明的优选实施方式，其实施例在附图中示出。只要可能，相同的参考标号将在整个附图中用于指代相同或相似的部件。
以下描述中使用的技术术语仅用于描述具体实施方式，但不限制本发明。除非另有说明，否则本文所用的单数形式包括复数形式。在以下对实施方式的描述中，术语“包括”是指特定属性、区域、整数、步骤、操作、元素和/或组件的具体化，而不排除存在或添加其他特定属性、区域、整数、步骤、操作、元素、组件和/或组。
除非另有说明，本文使用的包括技术或科学术语的所有术语具有与本领域技术人员通常理解的相同的含义。除非在本发明中清楚地定义，通常在词典中定义的术语应被解释为具有与相关技术中的语境含义和本文公开的含义一致的含义，而不被解释为具有理想或过于正式的含义。
本文参照附图描述改进的多层预浸料结构的示例性实施方式及其制造方法。
图3示意性地示出了改进的多层预浸料结构的示例实施方式。多层预浸料结构包括预浸料层100，所述预浸料层100包含浸渍有第一树脂120的碳纤维织物110；由第二树脂形成并且施加到预浸料层100的一个表面的固定层300，和施加到固定层300的透明涂层200。
碳纤维织物110通常用于制造CFRP部件；因此，将省略用于制造碳纤维织物或者产生特定图案的方法的详细描述。
在示例性实施方式中，第一树脂120是含有双氰胺类硬化剂的环氧树脂，并且具有比第二树脂更低的粘度和更低的固化速率。
第一树脂120具有优异的流动特性并且良好渗透碳纤维织物110，因此在制备预浸料结构中是有利的。然而，由于第一树脂120的粘度低，当在固化过程中第一树脂120中残留的气泡被释放时，第一树脂120可以从碳纤维织物110退出。当气泡从第一树脂120逸出时，可以产生薄的针孔，或者在一些区域可以减少第一树脂120的体积，暴露碳纤维织物110并产生多层预浸料结构的不平坦表面。
为了解决碳纤维织物110的暴露问题，将包含第二树脂的固定层300施加到预浸料层100的表面。
固定层300的第二树脂具有比预浸料层100的第一树脂120更高的固化速率，在固化过程中比第一树脂120更快地硬化，并且在多层预浸料结构的表面层上形成平坦膜。
在示例性实施方式中，第二树脂是含有脲类硬化剂的环氧树脂，并且具有比第一树脂120更高的粘度和更高的固化速率。
当将固定层300施加到预浸料层100的一个表面并且将多层预浸料结构固化时，固定层300首先硬化，在多层预浸料结构的表面上形成硬膜。残留在第一树脂120中的气泡B不会通过固定层300逸出，而是通过相反的未施加固定层300的预浸料层100的表面逸出预浸料层100。因此，固定层300的应用防止产生针孔。
此后，当第一树脂120硬化时，硬化的固定层300用作防止第一树脂120从碳纤维织物110退出和防止气泡B通过预浸料层100的侧表面逸出的支撑体。这最小化了空隙或不均匀预浸料层100的形成。
在示例性实施方式中，预浸料层100的厚度与固定层300的厚度之比在约1:0.25至约1:1之间。如果固定层300的厚度为预浸料层100的厚度的1/4或更小，则第一树脂120未适当固定，因此会暴露碳纤维织物110。如果固定层300的厚度大于预浸料层100的厚度，则可能由不对称堆叠结构而造成对多层预浸料结构的热损伤。
只要预浸料层100具有最小必要的强度，就不需要具体限制预浸料层100的厚度。然而，预浸料层100厚度的大幅增加需要堆叠过于大量的碳纤维织物；因此，在本文公开的示例性实施方式中，预浸料层100的厚度的上限设定为0.4mm或更小。
在另外的示例性实施方式中，在预浸料层100和固定层300固化之后施加透明涂层200。透明涂层200用于改善多层预浸料结构的整体外观并保护预浸料层100和固定层300。
与常规预浸料结构相比，本文公开的包括预浸料层100和固定层300的改进的多层预浸料结构具有优异的平整度，因此当施加透明涂层200时，需要较少的透明涂层施加。
以下参照图3至图5描述了制造改进的多层预浸料结构的方法的示例性实施方式。
首先，将碳纤维编织成碳纤维织物110。然后用第一树脂120浸渍碳纤维织物110以形成预浸料层100。在一个示例性实施方式中，第一树脂120是在固化前粘度为100-2,500cPs并且在125℃的温度下凝胶时间为8-30分钟的环氧类树脂。
尽管固定层300可以施加至单个预浸料层100，但是可以通过堆叠多个预浸料层100来改善多层预浸料结构的整体外观，特别是碳纤维织物110的图案的外观。根据一个示例性实施方式，堆叠两个预浸料层100，并且将固定层300施加到预浸料层100之一的暴露表面，以实现上述效果。
将包含具有比第一树脂120更高固化速率的第二树脂的固定层300施加到预浸料层100的一个表面。在示例性实施方式中，第二树脂是在固化前的粘度为2,500-10,000cPs并且在125℃温度下的凝胶时间为2-10分钟的环氧类树脂。
在真空包装中，将具有施加至其的固定层300的预浸料层100放置在真空袋430中，并且将真空袋430的内部抽真空以实现1巴或更小的压力，使得残留在第一树脂120中的气泡逸出。
在该方法中，将具有施加至其的固定层300的预浸料层100的表面朝下并与模具410接触。将真空袋430放置在预浸料层100的另一表面上，并且用密封剂480密封模具410和真空袋430之间的间隙，如图5所示。
织物通气器440和用于防止预浸料层100与通气器440之间粘合的分离膜450放置在真空袋430和预浸料层100之间。安装真空口470以允许从真空袋430抽空空气。
在另外的示例性实施方式中，可以在模具410和固定层300之间放置分离材料420，以允许固定层300与模具410容易地分离。还可以安装用于测量真空袋430内的温度的热电偶460。
可以通过将真空袋430和模具410放入高压釜中，然后在3-7巴的压力下加压并且在120-180℃加热45-90分钟，同时真空包装并热压真空袋装的具有施加至其的固定层300的预浸料层100。该过程热固化第一树脂120和第二树脂。
在该过程中，第二树脂首先硬化，形成用作支撑体的膜，以防止第一树脂120从预浸料层100中退出。
热压过程完成后，从真空袋430中取出硬化的预浸料层100和固定层300，然后利用透明涂层200涂覆。
图6a至图6c是显示本文描述的改进的多层预浸料结构的一个示例性实施方式的外观如何根据第二树脂的不同固化速率而变化的照片。图6a显示了使用固化速率为5-20分钟的第二树脂制备的改进的多层预浸料结构的外观。图6b显示了使用固化速率小于5分钟的第二树脂制备的改进的多层预浸料结构的外观。图6c显示了使用固化速率大于20分钟的第二树脂制备的改进的多层预浸料结构的外观。
如本文所使用的，固化速率定义为当使用差示扫描量热法(“DSC”)装置以5摄氏度/分钟的加热速率加热多层预浸料结构时，使用内部温度变化计算的树脂固化度为90％或更大的时间点。
如图6a所示，如果第二树脂的固化速率为5-20分钟，则多层预浸料结构具有光滑的表面、无针孔且透明度高。
相比之下，如图6b所示，如果第二树脂的固化速率低于5分钟，第二树脂的粘度过高，树脂不能适当地填充针孔。因此，多层预浸料结构的表面含有大量可见针孔。
如图6c所示，如果第二树脂的固化速率超过20分钟，则多层预浸料结构的表面变得不透明且不均匀。因为在这个例子中，第二树脂的固化速率与常规预浸料结构的树脂的固化速率相似，所以第二树脂的粘度较低，第二树脂可能不能适当地固定第一树脂和防止它从预浸料层中退出。
因此，在示例性实施方式中，第二树脂的固化速率设定在5-20分钟的范围内。
从上面的描述可以看出，改进的多层预浸料结构和用于制造改进的多层预浸料结构的方法表现出以下特征。
第一，将具有高固化速率的固定层施加到预浸料结构的表面层改进了预浸料结构的表面平整度。
第二，将具有高固化速率的固定层施加到预浸料结构的表面层防止了由于树脂从预浸料内部的凹入引起的针孔或空隙的产生。
第三，控制施加的固定层的厚度，导致CFRP部件外观的额外深度。
第四，将具有高固化速率的固定层施加至预浸料结构的表面层，产生了具有美学价值的CFRP部件，其具有由碳纤维织物形成的图案。
虽然为了说明的目的已经公开了本发明的优选实施方式，但是本领域技术人员将理解，在不背离所附权利要求中公开的本发明的范围和精神的情况下，可以进行各种修改、添加和替换。

Claims (10)

1.一种多层预浸料结构，包含：
预浸料层，所述预浸料层通过利用第一树脂浸渍碳纤维织物来形成；以及
固定层，所述固定层由与所述第一树脂相比具有更高固化速率的第二树脂形成并且施加到所述预浸料层的表面。
2.根据权利要求1所述的多层预浸料结构，其中所述预浸料层的厚度与所述固定层的厚度的比率在1:0.25与1:1之间。
3.根据权利要求2所述的多层预浸料结构，其中所述预浸料层的厚度为0.4mm或更小。
4.根据权利要求1所述的多层预浸料结构，其中：
所述第一树脂在125摄氏度的温度下具有8-30分钟的凝胶时间；并且
所述第二树脂在125摄氏度的温度下具有2-10分钟的凝胶时间。
5.根据权利要求1所述的多层预浸料结构，其中：
所述第一树脂是包含双氰胺类硬化剂的环氧树脂；并且
所述第二树脂是包含脲类硬化剂的环氧树脂。
6.根据权利要求1所述的多层预浸料结构，进一步包含施加至所述固定层的表面的透明涂层。
7.一种制造多层预浸料结构的方法，所述方法包括：
编织碳纤维织物；
利用第一树脂浸渍所述碳纤维织物以形成预浸料层；
向所述预浸料层的一个表面施加包含与所述第一树脂相比具有更高固化速率的第二树脂的固定层；
真空包装所述预浸料层，所述预浸料层具有施加至其的所述固定层；以及
在高压釜内热压真空包装的所述预浸料层。
8.根据权利要求7所述的方法，进一步包括在施加所述固定层之前堆叠多个预浸料层，其中所述固定层施加到堆叠的所述预浸料层的表面。
9.根据权利要求7所述的方法，其中将所述预浸料层放置在真空袋中，所述预浸料层具有施加至其的所述固定层；然后将压力降低至1巴或更小。
10.根据权利要求7所述的方法，其中在3-7巴的压力和120-180摄氏度的温度条件下，将真空包装的所述预浸料层热压45-90分钟。
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