CN103619579A - 多层结构在风力发电装置中的应用 - Google Patents
多层结构在风力发电装置中的应用 Download PDFInfo
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Landscapes
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Abstract
本发明涉及多层结构在风力发电装置的转子叶片的制造中的应用,以及用于风力发电装置的转子叶片。
Description
风能正变得日益重要,因此,风力发电装置、特别是转子叶片及其制造得到了广泛的研究和进一步的发展。其中,主要关注所制造的转子叶片的质量和成本有利的制造。迄今已知的风力发电装置用转子叶片是由基于树脂作为基质材料例如聚酯树脂(UP)、乙烯基酯树脂(VE)、环氧树脂(EP)的纤维增强的塑料构成。叶片主要如此来制造,即分别以单块制造叶片的下半片和上半片。随后把这两个半片上下叠置并粘合。为了进行强化,将斜撑或弦杆一起粘合。
在制造半片叶片时首先制造必须完全固化的纤维复合材料。这种固化过程特别耗时,且不利于快速的整体制造。由上述树脂制造的风力发电装置的转子叶片通常是通过手工层压法,通过预浸料技术辅助的手工层压法,通过缠绕法或真空辅助灌注法制成。在手工层压法中,先通过将脱模剂和/或任选的胶衣施加到模具表面,来准备模具。随后,依次把单向或二轴向取向的玻璃网格布放入模具内。然后把树脂施加到网格布上并且通过辊手动压入网格布中。该步骤可以适宜地经常重复。另外还可以加入作为加固材料的弦杆以及其他部件例如避雷装置。在第一层玻璃纤维强化层上施加通常由西印度轻木、聚氯乙烯(PVC)泡沫或聚氨酯(PUR)泡沫构成的所谓的间隔层,和施加与第一层类似的第二层玻璃纤维强化层。尽管这种方法具有以下优点,即机器投资小和错误识别和修正可能性简单,然而,制造的人工成本过于高昂,因此,该方法的成本极高,并且长的制造时间还会带来更多的错误和为确保品质更大的投入。
通过预浸料技术辅助的手工层压法与简单的手工层压法类似。但是,在这里所谓的预浸料(用树脂浸渍而预先制备的玻璃纤维垫(Glasmatte))是在模具之外制造,然后定位在转子叶片模具内。尽管相对于简单手工层压而进行的用于制造预浸料的半自动化会给转子制造带来改善的品质稳定性,然而,保护作业人员不受到液态的树脂混合物所含的易挥发的化合物的危害需要不可忽视的开支(工作场所安全性等)。
在树脂主射法(也叫作“树脂传递模塑”(RTM))或“真空辅助树脂传递模塑”(VA RTM)或'SCRIMP”(Seemann复合树脂浸渍模塑工艺)中,通过施加脱模剂和可能的胶衣来准备模具。接着,按照精确的制造计划将干燥的纤维垫置在模具中。该第一插入层之后成为转子叶片的向外置放的层。随后放间隔材料,再在其上放置纤维垫,其进而形成制成的半个转子/半个转子叶片的内层。对于制造大的成型件如转子叶片而言,优选使用真空辅助灌注法进行加工。使用真空密封的薄膜把整个模具密封地包覆起来。在于不同的位置把树脂注射到模具内(薄膜与模具之间的空间)之前,从如此准备的模具中抽出纤维垫和间隔材料中的空气。这种方法-像之前所述的两种方法一样-也有缺点,即直到构件脱模所必需的固化时间极长,为多达12小时,因此大大限制了设备的生产率。
因此,本发明的目的是,提供转子叶片,其既不存在上述不足,同时也能成本有利地在更短的时间内并以更好的机械性能,例如更高的强度制成。
令人惊讶地,该目的可由此实现,即以聚氨酯替代上述树脂作为塑料来制造转子叶片,所述聚氨酯可通过多异氰酸酯与用甘油引发的聚氧化丙烯多元醇的反应获得。根据本发明,尤其是在转子叶片的外壳中使用聚氨酯作为塑料;外壳中所用的纤维层被加入这种塑料。
本发明的主题是风力发电装置的转子叶片,其具有至少部分地由具有下列层的多层结构构成的外壳:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
并且其特征在于,使用聚氨酯作为塑料,所述聚氨酯可通过下述组分的反应混合物的反应获得:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
本发明的另一主题是制造按照本发明的风力发电装置的转子叶片的方法,所述叶片具有至少部分地由具有下列层的多层结构构成的外壳:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
其特征在于,用把聚氨酯制造成塑料的反应混合物处理所述纤维层,其中所述反应混合物可得自下述组分:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
本发明的另一主题是多层结构在风力发电装置的转子叶片的制造中的应用,其中,所述层结构具有下列层:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
且其特征在于,使用聚氨酯作为塑料,所述聚氨酯可通过下述组分的反应混合物的反应获得:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
对于脱模剂层,优选使用含硅或含蜡的脱模剂。这些脱模剂由文献中已知。任选也可以使用隔离膜作为脱模剂层。
胶衣层优选是由聚氨酯树脂,环氧树脂,不饱和聚酯树脂或乙烯基树脂构成。
作为纤维层,可优选使用无规玻璃纤维层,玻璃纤维织物和玻璃纤维网格布,裁断或碾碎的玻璃纤维或矿物纤维以及基于聚合物纤维,矿物纤维,碳纤维、玄武岩纤维,钢纤维,玻璃纤维或芳纶纤维及其混合物的纤维垫,纤维非织造物与纤维针织物,特别优选使用玻璃纤维垫和玻璃纤维非织造物。在配有聚氨酯的纤维层中,纤维含量优选为40-90重量%,优选50-80重量%,且尤其优选60-75重量%。在玻璃纤维增强的部件中,纤维含量可以通过,例如,灰化来确定。作为隔离层优选使用塑料泡沫,例如PVC-泡沫、PET-泡沫或聚甲基丙烯酰亚胺-泡沫,木材,例如西印度轻木或金属。
任选使用的塑料膜f)可以在转子叶片的制造中保留下来作为外壳中的层,或者其可在半个转子叶片脱模时除去。该塑料膜尤其用于在填充液态的树脂混合物前在真空抽吸的制造工序中密封模具半壳,其中所述模具半壳已经配备有上述层。在配备有塑料的纤维层e)与塑料膜f)之间任选还可以使用助剂,例如,可剥离膜(“Peelfolien”)或流动助剂,例如,流动织物(Flieβgewebe)或纵切膜。需要时可以额外地使用它们,以实现纤维层e)的均匀浸渍。优选地,在制造多层结构之后再将它们除去,以减轻转子叶片成品中的重量。
使用聚氨酯作为塑料。聚氨酯可通过多异氰酸酯A)与具有至少两个异氰酸酯反应性氢原子的化合物B的反应获得。令人惊讶的是,通过使用甘油引发的聚氧化丙烯多元醇(丙氧基化的甘油)作为组分B可以获得在制造过程中表现出特别缓慢的黏度提高的聚氨酯,但是其可以快速固化,并且与在至今所使用的塑料用途中相比,其在制成的玻璃纤维增强的聚氨酯中表现出明显更好的机械性能。
根据本发明使用的反应混合物备注射到预先准备的已抽真空的多层结构中。
所述多元醇配制品优选包含这样的聚氧化丙烯多元醇作为用甘油引发的聚氧化丙烯多元醇,其具有250—1000毫克KOH/克的OH值,优选为300-800毫克KOH/克和特别优选为350-500毫克KOH/克。多元醇的黏度优选为≤800mPas(在25℃时),优选≤500mPas(在25℃时)。在使用多种引发剂用于制造聚氧化丙烯多元醇时,甘油在引发剂混合物中的重量份额优选为50-100重量%,优选80-100重量%。特别优选的是纯甘油引发的聚氧化丙烯多元醇。
其它常用引发剂,例如,1,1,1-三羟甲基丙烷,三乙醇胺,山梨醇,季戊四醇,乙二醇,丙二醇只能与甘油组合使用。
使用常用的脂肪族、脂环族和特别是芳香族的二异氰酸酯和/或多异氰酸酯作为多异氰酸酯组分。这样的合适的多异氰酸酯的实例是1,4-亚丁基二异氰酸酯、1,5-戊烷二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、2,2,4-和/或2,4,4-三甲基六亚甲基二异氰酸酯、双(4,4‘-异氰酸根合环己基)甲烷或其与其他异构体的混合物、1,4-亚环己基二异氰酸酯、1,4-苯二异氰酸酯、2,4-和/或2,6-甲苯二异氰酸酯(TDD)、1,5-萘二异氰酸酯、2,2‘-和/或2,4‘-和/或4,4‘-二苯基甲烷二异氰酸酯(MDI)和/或其高级同系物(pMDI)、1,3和/或1,4-双-(2-异氰酸根合丙-2-基)-苯(TMXDI)、1,3-双(异氰酸根合甲基)苯(XDI)。优选用二苯基甲烷二异氰酸酯(MDI)和特别是由二苯基甲烷二异氰酸酯与多苯基多亚甲基多异氰酸酯(pMDI)组成的混合物作为异氰酸酯。所述由二苯基甲烷二异氰酸酯与多苯基多亚甲基多异氰酸酯(pMDI)组成的混合物优选具有50至100重量%,优选60至95重量%,尤其优选70至90重量%的单体含量。所用的多异氰酸酯的NCO含量应优选超过25重量%,优选超过30重量%,尤其优选超过31.4重量%。使用的MDI优选应具有总共至少3重量%,优选为至少20重量%的2,2’-二苯基甲烷二异氰酸酯与2,4’-二苯基甲烷二异氰酸酯的含量。该异氰酸酯的粘度应优选为≤250mPas(在25℃),优选≤100mPas(在25℃),和尤其优选为≤30mPas(在25℃)。
优选除了已知的反应性组分与添加剂和添加物外,所述聚氨酯反应混合物优选还包含填料如碳纳米管、硫酸钡、二氧化钛、短玻璃纤维或者天然纤维状或薄片状矿物例如硅灰石或白云母。优选将稳定剂、消泡剂、催化剂与潜催化剂用作添加剂和添加物。还可根据需要使用其他已知的添加剂和添加物。
合适的聚氨酯体系尤其指那些透明的聚氨酯体系。因为在制造较大的成型件时,低粘度对于模具的均匀填充和纤维的润湿而言是必需的,所以尤其合适的是下述的聚氨酯体系:其具有粘度≤5000mPas(在35℃;组份混合后60分钟),优选≤4000mPas,尤其优选3500mPas,并且其在反应混合物的组分混合后立即具有30-500mPas(在35℃),优选40-150mPas(在35℃)和特别优选50-100mPas(在35℃)的粘度。优选这样来选择异氰酸酯组份和多元醇配制品之间的反应比例,使得在反应混合物中,异氰酸酯基团的数量与对异氰酸酯呈反应性的基团的数量的比为0.9至1.5,优选1.0至1.2,尤其优选1.02至1.15。
在按照DIN EN ISO527的拉伸试验中,所获得的聚氨酯优选具有大于70Mpa,优选超过80Mpa的强度,以承受转子叶片内高的机械负荷。
在一个优选实施方案中,由异氰酸酯组份与多元醇组分组成的反应混合物在20至80℃、尤其优选在25至40℃的温度下被注射。
当充填反应混合物后,可通过加热模具来加速聚氨酯的固化。在一种优选实施方案中,被注射的由异氰酸酯组份与具有至少两个对异氰酸酯呈反应性的氢原子的化合物组成的反应混合物在40至160℃、优选在60至120℃、尤其优选在70至90℃的温度下固化。
借助以下实施例意在进一步说明本发明。
实施例
为了确定基质性能,用不同的聚氨酯体系制造成型件(板材)并与标准环氧树脂-体系进行比较。在1mbar的压力下使多元醇脱气60分钟,之后加入VP.PU60RE11并且在1mbar的压力下脱气约5分钟,之后浇注在板材模具内。板材的厚度为4毫米。该板材在室内温度下浇注并且在加热到80℃的干燥箱内退火过夜。得到透明的板材。与此类似,使Larit RIM135的环氧树脂体系和固化剂Larit RIMH137脱气,浇注成板材并退火过夜。由表中可知量的数据和性能。
由所述板材制造用于按照DIN EN ISO527进行拉伸试验的试验件,并测定弹性模量和强度。
聚氨酯板材1-4在2个小时之后已经可以没有变形地脱模,在比较实施例5中,这在明显更长的时间,大约12小时之后才可行。
用实施例1和实施例2的组成,通过真空灌注法可以制造具有玻璃纤维含量超过60重量%的,透明的玻璃纤维增强聚氨酯材料。
用玻璃纤维粗纱(EC2400P207)装填直径为6毫米的特氟龙管用于通过真空灌注法制造纤维增强成型件,以至于基于之后的部件计,玻璃纤维含量达到约65重量%。聚四氟乙烯管的一侧浸入反应混合物中和该管的另一侧用油泵施加真空,从而使反应混合物被吸入管内。在该管被装填后,使其在70℃下退火10小时。分别去除特氟龙管,并得到透明的用纤维增强的成型件。
在将各种组分混合60分钟之后,在35℃恒温条件下用旋转式粘度计在60l/s的剪切速率下测定粘度。在制造较大的成型件时,在制造较大的成型件时为了均匀填充模具需要一定时长的低粘度。
起始化合物:
多元醇1:甘油引发的聚氧化丙烯多元醇,其中,官能度为3,且OH值为450毫克KOH/克和粘度为420mPas(在25℃下)。
多元醇2:甘油引发的聚氧化丙烯多元醇,其中,官能度为3,且OH值为400毫克KOH/克和粘度为370mPas(在25℃下)。
多元醇3:三羟甲基丙烷(TMP)引发的聚氧化丙烯多元醇,其中,官能度为3,且OH值为380毫克KOH/克和粘度为650mPas(在25℃下)。
多元醇4:甘油和山梨醇(重量比30:70)引发的聚氧化丙烯多元醇,其中,OH值为430毫克KOH/克和粘度为大约9000mPas(在25℃下)。
Larit RIM135(L-135i)和Larit RIMH137是Lange+Ritter公司的产品。LaritRIM135是一种基于双酚-A-表氯醇树脂和1,6-己二醇二缩水甘油醚的环氧树脂,其具有环氧当量为166-185克/当量,而RIMH137是基于IPDA(异佛尔酮二胺)和烷基醚胺的固化剂,其具有胺值为400-600毫克KOH/克。
下表中所以量的数据均以重量份给出。
表:
n.b.-未测定,因为在60分钟后粘度过高。
在2小时的短的脱模时间下,根据本发明的实施例1和实施例2表现出缓慢的粘度升高和同时非常好的机械性能(例如,强度超过70Mpa)的非常好的组合,所述缓慢的粘度升高表现为在35℃下低的初始粘度,在60分钟之后,35℃下的粘度低于5000mPas,这对于制造大的纤维增强结构部件来说是非常重要的。与此相反,比较实施例3和4显示出明显更快的粘度升高,初始粘度较高,略高的在35℃温度下的起始粘度和在60分钟之后远高于5000mPas的在35℃下的粘度,这使得制造大的纤维增强结构部件变得困难。虽然比较实施例5也显示出缓慢的粘度升高,但是同时脱模时间(约12小时)明显长于实施例1和实施例2(约2小时)。这导致生产率低。此外,机械性能差,具有低于70Mpa的强度。
Claims (8)
1.多层结构在风力发电装置用转子叶片的制造中的应用,其中所述多层结构具有下列层:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
其特征在于,使用聚氨酯作为塑料,所述聚氨酯可通过下述组分的反应混合物的反应获得:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
2.风力发电装置用转子叶片,所述叶片具有至少部分地由具有下列层的多层结构构成的外壳:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
其特征在于,使用聚氨酯作为塑料,所述聚氨酯可通过包含下述组分的反应混合物的反应获得:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
3.用于制造根据权利要求2所述的风力发电站用的转子叶片的方法,所述转子叶片具有至少部分地由具有下列层的多层结构构成的外壳:
a)脱模剂层
b)任选的胶衣层
c)经塑料处理的纤维层
d)任选的间隔层
e)配有塑料的纤维层
f)任选的塑料膜
其特征在于,用将聚氨酯制造为塑料的反应混合物处理所述纤维层,其中所述反应混合物可得自下述组分:
A)一种或多种多异氰酸酯
B)包含一种或多种用甘油引发的聚氧化丙烯多元醇的多元醇配制品
C)任选的添加剂和/或添加物
D)任选的填料。
4.根据权利要求3所述的方法,其特征在于,所述反应混合物包含具有NCO含量大于25重量%的二苯基甲烷二异氰酸酯和/或多亚苯基多亚甲基多异氰酸酯作为异氰酸酯。
5.根据权利要求3所述的方法,其特征在于,所述反应混合物含有具有OH值为300-800毫克KOH/克的化合物作为用甘油引发的聚氧化丙烯多元醇。
6.根据权利要求3所述的方法,其特征在于,在20至80℃的温度下将所述反应混合物施加到所述纤维层中。
7.根据权利要求3所述的方法,其特征在于,所述反应混合物在40℃-160℃的温度下固化。
8.根据权利要求3所述的方法,其特征在于,在35℃的恒定温度下,所述反应混合物在混合后60分钟具有≤5000mPas的粘度。
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DE102011004723.9 | 2011-02-25 | ||
DE102011004723A DE102011004723A1 (de) | 2011-02-25 | 2011-02-25 | Verwendung von Schichtaufbauten in Windkraftanlagen |
PCT/EP2012/052847 WO2012113748A1 (de) | 2011-02-25 | 2012-02-20 | Verwendung von schichtaufbauten in windkraftanlagen |
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CN (1) | CN103619579B (zh) |
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CN107771193A (zh) * | 2015-06-24 | 2018-03-06 | 科思创德国股份有限公司 | 用于风力涡轮机中的层结构的聚氨酯体系 |
CN108248170A (zh) * | 2016-12-29 | 2018-07-06 | 比亚迪股份有限公司 | 一种复合材料及其制备方法和应用 |
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DE102009058101A1 (de) * | 2009-12-12 | 2011-06-16 | Bayer Materialscience Ag | Verwendung von Schichtaufbauten in Windkraftanlagen |
DE102013217128A1 (de) * | 2013-08-28 | 2015-03-05 | Wobben Properties Gmbh | Rotorblattelement für eine Windenergieanlage, Rotorblatt, sowie ein Herstellungsverfahren dafür und Windenergieanlage mit Rotorblatt |
DE102015105336A1 (de) * | 2015-04-08 | 2016-10-13 | Peter Dolibog | Mehrschichtiger Formkörper aus Kunststoffen mit unterschiedlichen Eigenschaften und Verfahren zu seiner Herstellung |
WO2019051637A1 (en) | 2017-09-12 | 2019-03-21 | Covestro Deutschland Ag | COMPOSITE MATERIAL COMPRISING A POLYURETHANE-POLYACRYLATE RESIN MATRIX |
EP3549670A1 (en) | 2018-04-06 | 2019-10-09 | Covestro Deutschland AG | Manufacturing method for a polyurethane-poly(meth)acrylate resin |
WO2021233765A1 (en) * | 2020-05-18 | 2021-11-25 | Basf Se | A polyurethane-forming system, a composite comprising the polyurethane-forming system and a fiber-reinforced material, a process for the production of the composite, and the use of the composite |
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- 2012-02-20 WO PCT/EP2012/052847 patent/WO2012113748A1/de active Application Filing
- 2012-02-20 CN CN201280010441.9A patent/CN103619579B/zh active Active
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PL2678151T3 (pl) | 2018-01-31 |
CA2828035A1 (en) | 2012-08-30 |
EP2678151B1 (de) | 2017-08-09 |
US9085990B2 (en) | 2015-07-21 |
MX2013009565A (es) | 2013-09-06 |
EP2678151A1 (de) | 2014-01-01 |
BR112013021601A2 (pt) | 2016-11-16 |
US20130330202A1 (en) | 2013-12-12 |
ES2646391T3 (es) | 2017-12-13 |
CN103619579B (zh) | 2015-07-08 |
WO2012113748A1 (de) | 2012-08-30 |
DK2678151T3 (da) | 2017-11-20 |
AU2012219675B2 (en) | 2015-12-17 |
DE102011004723A1 (de) | 2012-08-30 |
AU2012219675A1 (en) | 2013-09-12 |
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