CN104070709B - 复合结构 - Google Patents
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Abstract
本发明描述了一种复合结构，其包含数个含热固性树脂的元件(1)和数个热塑性元件(2)和至少一个在含热固性树脂的元件(1)与热塑性元件(2)之间的界面(3)，其中含热固性树脂的元件(1)和热塑性元件(2)在界面(3)处包含在固化所述复合结构时互相键合的官能团，且所述官能团在它们的未键合状态下独立地选自胺、羧酸、酸酐、环氧乙烷类及其衍生物。另外，本发明描述了包含这种复合结构的叶片。
Description
本发明描述了基于数个热固性树脂元件的复合结构，特别是用在叶片中，例如作为风力涡轮机系统的一部分的复合结构，还涉及包含这样的复合结构的叶片。
风力涡轮机系统的叶片传统上由几个含纤维增强树脂的部件制成。通常，叶片一体浇铸或分几件浇铸，例如两个壳，然后互相胶合。制造含树脂的部件，如叶片的主要加工方法是真空树脂注入。另一加工方法是使用已含有树脂作为基质材料的机织或单向玻璃织物的预浸料坯（prepreg）模制。
为了承受大和反复的载荷，风力涡轮机叶片传统上由具有良好机械性质的热固性树脂制成。因此，典型的含树脂部件是由互相叠加并组成最终叶片结构的数个增强树脂层构成的层合材料。通常，选择叶片材料以向叶片提供高刚性以及抗扭性和抗疲劳性。由于此类叶片的机械性能，通常使用环氧树脂，尤其是如果制造大于40或50米的较长叶片。在例如汽车工业中对复合结构采用类似的工艺和树脂材料。
此类热固性元件中所用的增强树脂材料的量使所得部件比相应的未增强部件重，其中所用增强材料的量通常取决于机械要求。在专利申请US 2002/01787702 A1中，已经提出由热塑性第一层和第二热固性层的组合制成的用于汽车用途的复合部件。由热塑性材料制成的第一层提供良好表面修饰并降低整体部件重量，而由热固性树脂制成的第二层为复合部件提供良好强度和刚性。热塑性层和热固性层通过利用粘合位点（其通过作用于热塑性树脂组分的未反应的热固性树脂组分活化或通过这两种树脂机械渗透薄多孔层活化）互相粘合。使用苯乙烯基团作为这样的活性位点。
在风力涡轮机叶片领域中也考虑如汽车应用领域中所述的将一些热塑性元件并入复合结构中。为了提高加工能力或为了实现该元件在层合材料应用中的效用而做出这些考虑。
但是，在风力涡轮机叶片用途中，研究出在一定程度上（最通常不利地）影响包含热塑性和热固性树脂的层合材料的所得机械性质。这主要由热塑性材料的较差材料性质或热塑性与热固性树脂层之间的较差界面性质造成。因此，如果使用这样的复合材料，尽可能降低该复合结构中热塑性材料的量。
因此本发明的一个目的是克服包含热固性树脂元件和热塑性元件的常见复合结构的上述缺点，尤其是改进这种复合材料的机械性质。
通过根据权利要求1的复合结构和根据权利要求7的叶片实现这一目的。
根据本发明，该复合结构包含多个含热固性树脂的元件和多个热塑性元件和至少一个在含热固性树脂的元件与热塑性元件之间的界面。“数个”在本发明背景中是指在该结构中包含一个或更多个，例如至少两个、多于两个或多个相同类型的元件，即含热塑性或热固性树脂的元件。它们可以互相紧邻布置或不同类型以相继次序布置，如热塑性元件和含热固性树脂的元件的堆叠层合材料。因此，在本发明的复合结构中包含一个或多个分别在含热固性树脂的元件与热塑性元件之间的界面。
由于含热固性树脂的元件与热塑性元件在界面处的接合对该复合结构的材料性质至关重要，含热固性树脂的元件和热塑性元件在界面处包含在固化或硬化该复合结构时互相键合的官能团。通过引入热塑性材料（特别是树脂材料）或热固性树脂或这两种材料或树脂中的可以在彼此之间形成稳定键的反应性基团改进该复合材料的机械性质，例如刚性。
该官能团具体选自在制造场所对工人无害并在正确处理不同树脂材料时不提高工作相关危险的化学基团。更特别地，术语“无害”是指该官能团通常被认为很可能无害，例如如果它们以在热塑性元件中的“稀释”形式处理或在受控条件下用于制造这种元件。可引入树脂元件中的示例性的官能团在它们的未键合状态下独立地选自胺、羧酸、酸酐、环氧乙烷类及其衍生物。相应地，上述官能团与要接合的元件中的分别对应基团反应以使它们不再以它们的未键合或固化状态存在于最终产品中。在最终产品中，基本存在各自生成的反应基团，而未反应的基团仅以无关紧要的量作为副产物存在。
将上文例举的官能团并入热塑性元件和/或含热固性树脂的元件中的一个优点在于，它们很可能对工人无害或无毒或可以在没有大量安全措施的情况下处理。这些基团中的任一种可以结合到各树脂元件中的树脂组分或辅助组分上或可以选择它们以使这些官能团中的两个互相结合，由此将含热固性树脂的元件与热塑性元件接合。
在本发明的另一方面中，提供包含上文已描述的本发明的复合结构的叶片。这种叶片优于现有叶片技术，因为现在可以将热塑性元件包含到热固性树脂结构中或在叶片表面提供热塑性部件。在这两种选择中，热塑性元件都借助在至少含热固性树脂的元件中的树脂固化过程中由各自的官能团生成的共价键接合到含热固性树脂的元件上。可以在层合结构内以例如片或箔形式提供热塑性元件。因此，通过引入显著量的热塑性元件，可以以宽泛的方式调节主要由含热固性树脂的元件构成的叶片的机械性质，同时为该结构增加仅使用热固性树脂组分极难或不可能引入最终产品中的其它性质。如果在叶片表面提供热塑性元件，可以在叶片制造过程中安装用于改进叶片的空气动力学或为叶片提供额外功能的特殊元件。通常，使用根据本发明的一般概念的特定官能团提供含热固性树脂的元件与热塑性元件之间界面处的高接合强度。
通过如下列说明书中揭示的从属权利要求给出本发明的特别有利的实施方案和特征。不同权利要求类别的特征可以酌情结合以提供本文中没有明确描述但由所述优选实施方案的上下文容易推导出的另一些实施方案。
在一个优选实施方案中，该复合结构包含含热固性树脂的元件，所述含热固性树脂的元件包含由至少一种含树脂的组分和至少一种硬化剂（例如一种树脂组分与两种硬化剂一起）构成的双或三组分体系，其中该硬化剂在它们的混合物中不稳定。当使用双或三组分体系时，热塑性元件的官能团结合到树脂组分上或结合到硬化剂组分上。或者，可以调节官能团以使它们可结合到这两种组分——树脂组分和硬化剂上，以改进含热固性树脂的元件与热塑性元件之间的接合。如果在最终产品中的界面处生成每表面积较大数量的键或两种或更多种不同类型的键，该接合较强。从节省成本的角度看，如果通常在元件之一，例如热塑性元件处提供官能团并具有键合到另一树脂元件（在这种情况中是例如含热固性树脂的元件）的树脂组分或硬化剂上的功能，则更容易并且足够。这允许特别仅为一种树脂元件提供特定官能团，而另一元件在它们的一般结构中或在它们的一般结构的一部分中具有该官能团的各自对应部分。
如上所述的复合结构中所用的含树脂的组分优选包含环氧树脂作为热固性树脂材料。环氧树脂的优点在于，该单体、低聚物或聚合的部分结构，如其side changes中存在的环氧基包含可与胺、羧酸和酸酐反应的环氧基或残留环氧基。如果在热固性树脂元件中使用环氧树脂，由环氧部分和硬化剂部分构成的双组分体系是优选的。该硬化剂有利地基于胺或包含不同的胺。优选使用足以固化环氧树脂并任选为热固性树脂元件提供额外功能的量的硬化剂。此外，所用树脂材料和所用硬化剂通常在高于室温的温度下是反应性的以使热固性树脂元件在室温下容易操作并可以在升高的温度下，例如高于50°C，优选在50至120°C下固化。所用树脂和硬化剂可购自若干供应商并且是技术人员公知的。
因此，本发明的复合结构优选包括包含可与树脂组分或与硬化剂反应的官能团的热塑性元件。在环氧树脂作为含热固性树脂的元件中的热固性树脂组分的情况下，有利地为热塑性元件提供官能团，包括但不限于，胺、羧酸和酸酐。在环氧树脂混合物中，硬化剂优选基于胺。因此，与环氧硬化剂反应的官能团的优选实例包括，但不限于，环氧乙烷类、羧酸及其衍生物。
如上文例举的官能团或材料提供热塑性元件与含热固性树脂的元件之间的化学键以确保改进的界面强度。该化学键是提供这两种元件之间的最佳接合强度的共价键。该键完全避免或至少显著降低在现有技术中观察到的各元件在其界面处的层离危险。
含热固性树脂的元件和热塑性元件可带有反应性部分，优选在它们的表面处，以使反应性部分包含如上文规定的官能团。如果在元件表面提供官能团，它们容易呈递给要与其接合的元件的反应性对应部分。可以在树脂元件中，例如在树脂单体、低聚物或聚合物的侧链中或在硬化剂中固有地提供含官能团的反应性部分。或者，可以通过不同技术，例如通过形成共聚物、互穿网络、配混或表面改性在树脂元件结构中或在其表面引入它们。
根据另一优选实施方案的复合结构包含两个或更多个含热固性树脂的元件和一个或更多个热塑性元件的层合材料。层合材料在本发明背景中是指含热固性树脂的元件层和热塑性元件层彼此紧邻布置，接着紧邻热塑性元件层布置至少另外的含热固性树脂的元件层。因此，层合材料包含至少两个在含热固性树脂的元件与热塑性元件之间的界面。当然，在层合材料中可以提供多于三个树脂层以提供含热固性树脂的元件层和热塑性元件层的连续堆叠体。在这种层合材料的各界面，树脂元件中的官能团在这两种树脂元件之间生成化学键以改进界面强度和避免使用过程中的层离效应。
该热固性树脂元件有利地是由增强结构（如织物）和可能在固化前存在于该元件中（预浸料法）或可能在固化过程中浸渍（注塑法）的树脂组分构成的增强树脂元件。就本发明而言，织物是增强树脂元件的纤维层。该层包含缝合或机织纤维或包含置于一起的独立纤维。优选用于复合结构领域，尤其用于风力技术叶片的示例性纤维是玻璃纤维，如e-玻璃或高模量玻璃纤维。
在本发明的复合结构的另一实施方案中，在热固性树脂元件的表面布置热塑性元件。这一实施方案能够在热固性树脂元件的表面区域处添加主要由热塑性材料制成的结构部件。通过在未固化的复合结构中使用官能团，该结构部件可借助化学键接合到热固性树脂上以改进界面强度。由此，可以实现基于热塑性元件和含热固性树脂的元件的组合的新的层合性质，同时可以改进或确保制造场所的工人安全。这些有利的机械性质和制造简易性使本发明的复合结构可用作叶片，尤其是作为风力涡轮机系统的一部分的叶片。界面的高强度和可靠性能够制造具有更好性能，例如更好的空气动力学分布的叶片。
此外，可以制造在叶片表面具有附加元件的叶片，即使该附加元件至少部分包含热塑性材料或主要由热塑性材料制成，以例如为这种附加元件提供充足的挠性。在这种情况中，本发明的叶片优选包含热塑性元件作为这种附加元件，其中该热塑性元件是空气动力学改良元件的一部分。这样的元件是现有叶片技术中已知的，例如作为DinoShells（Siemens的商标）、DinoTails（Siemens的商标）或涡流发生器。DinoTails、DinoShells和涡流发生器是使叶片更有效的附加元件，因为它们相对于粗糙度敏感性而言使空气动力学性能和稳固性最大化。
DinoTails是单独的翼片，形状像剑龙的尾翼，它们通常靠近叶梢布置以使叶片更安静并增强起重性能。
DinoShells是从赛车中获知的翼片与普通翼片的组合。它们通常具有重叠贝壳结构。因此，它们是附加在叶片表面的后缘附近的固定控制表面以提高起重能力，尤其是在最靠近轮毂（hub）的叶片厚部上。
涡流发生器是设计成改进风力涡轮机叶片上的空气流的空气动力涡轮机。它们通常增强叶片的空气动力学性能并通常用在最靠近轮毂的叶片部分上。
当然，上述复合结构在叶片中的应用不限于上述具体实施方案，而是可用于在叶片中或叶片表面上增加附加的空气动力学元件。
从联系附图考虑的下列详述中可看出本发明的其它目的和特征。但是，要理解的是，附图仅用于图解而非规定本发明的界限。
图1显示根据图1的复合结构在组装热固性树脂元件和热塑性元件前的状态下的横截面示意图；
图2显示本发明的复合结构在组装和固化后的状态下的横截面示意图；
图3显示复合结构的横截面示意图和在固化过程中在其界面处发生的化学反应。
在图中，类似数字在各处是指类似物体。图中的物体不一定按比例绘制。
图1显示本发明的复合结构在组装含热固性树脂的元件1和热塑性元件2前的状态下的横截面示意图。该复合结构包含两个含热固性树脂的元件1，各自由以平行构造互相叠放的数个织物层构成以构造这两个热固性树脂元件。织物层可以由具有或没有热固性树脂含量的织物形成。如果织物仍含有热固性树脂含量，它们通常被称作预浸料坯。或者，可以将织物层与热塑性元件布置在一起，然后用热固性树脂浸渍。这被称作树脂注入法。当然，这两种方法可以结合。
可以在进行固化前在两个含热固性树脂的元件1之间布置热塑性元件2。这种情况显示在图1中。
图2显示根据图1的复合结构在通过预浸料法或树脂注入法组装和固化后的状态下的横截面示意图。所得复合结构在两个含热固性树脂的元件1之间包含热塑性元件2，它们此时在含热固性树脂的元件1与热塑性元件2之间的界面3处通过强键接合。由固化反应生成的键是固化前存在于含热固性树脂的元件1与热塑性元件2之间的界面3处的官能团之间的共价键。因此，这两个含热固性树脂的元件1借助它们之间的热塑性元件2牢固固定。
图3显示复合结构的横截面示意图和在固化过程中在含热固性树脂的元件1与热塑性元件2之间的界面3处发生的化学反应。在图3中，已示例性显示在其侧链上具有胺基的热塑性元件2与含热固性树脂的元件1（例如包含具有含环氧官能团的残留侧链的环氧树脂的元件）的环氧基的反应。
技术人员从上文的描述中获知可以对官能团作出各种改变。例如，可以改变该基团并容易在热固性树脂元件表面提供胺官能团，例如通过使用胺硬化剂。
尽管已经以优选实施方案及其变体形式公开了本发明，但要理解的是，可以在不背离本发明范围的情况下对其作出许多附加的修改和变化。为清楚起见，要理解的是，本申请中通篇中“一”的使用不排除复数，“包含”不排除其它步骤或元件。
Claims (9)
1.复合结构，其包含数个含热固性树脂的元件(1)和数个热塑性元件(2)和至少一个在含热固性树脂的元件(1)与热塑性元件(2)之间的界面(3)，其中含热固性树脂的元件(1)和热塑性元件(2)在界面(3)处包含在固化所述复合结构时互相键合的官能团，且所述官能团在它们的未键合状态下独立地选自胺、羧酸、酸酐、环氧乙烷类及其衍生物。
2.根据权利要1的复合结构，其中含热固性树脂的元件(1)包含由至少一种树脂组分和至少一种硬化剂构成的双或三组分体系。
3.根据权利要求2的复合结构，其中所述树脂组分包含环氧树脂。
4.根据权利要求2和3任一项的复合结构，其中热塑性元件(2)包含可与树脂组分或与硬化剂反应的官能团。
5.根据权利要求1至3任一项的复合结构，其中所述复合结构包含两个或更多个含热固性树脂的元件(1)和一个或多个热塑性元件(2)的层合材料。
6.根据权利要求1至3任一项的复合结构，其中在含热固性树脂的元件(1)的表面布置热塑性元件(2)。
7.包含根据权利要求1至6任一项的复合结构的叶片。
8.根据权利要求7的叶片，其中所述叶片是风力涡轮机系统的一部分。
9.根据权利要求7或8的叶片，其中热塑性元件(2)是空气动力学改良元件的一部分。
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| US20020187702A1 (en) * | 2001-06-07 | 2002-12-12 | Delusky Arthur K. | Composite thermoplastic-thermoset resin material |
| TWI304321B (en) * | 2002-12-27 | 2008-12-11 | Toray Industries | Layered products, electromagnetic wave shielding molded articles and method for production thereof |
| JP2005297417A (ja) * | 2004-04-14 | 2005-10-27 | Toray Ind Inc | 工業用構造部材およびその製造方法 |
| DK200401225A (da) * | 2004-08-13 | 2006-02-14 | Lm Glasfiber As | Metode til afskæring af laminatlag, eksempelvis et glasfiber- eller kulfiber-laminatlag i en vindmöllevinge |
| US8211268B1 (en) * | 2009-03-20 | 2012-07-03 | Milliken & Company | Tie layer compositions for fiber reinforced thermoplastic—thermoset structural element |
| WO2012149939A2 (en) * | 2011-05-04 | 2012-11-08 | Vestas Wind Systems A/S | Method of preparing a composite laminate |
| EP2543874A1 (en) * | 2011-07-06 | 2013-01-09 | LM Wind Power A/S | A wind turbine blade |
| DE112012003520T5 (de) | 2011-08-25 | 2014-05-08 | Bcomp Ag | Ein Verfahren zum Herstellen eines Verbundmaterials, und ein Brett hergestellt aus diesem Verbundmaterial |
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| Publication number | Publication date |
|---|---|
| CN104070709A (zh) | 2014-10-01 |
| EP2784106B1 (en) | 2018-09-05 |
| EP2784106A1 (en) | 2014-10-01 |
| DK2784106T3 (en) | 2018-12-17 |
| US10328676B2 (en) | 2019-06-25 |
| US20140295187A1 (en) | 2014-10-02 |
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