CN108367512A - 用于制造纤维增强复合材料的树脂灌注方法 - Google Patents
用于制造纤维增强复合材料的树脂灌注方法 Download PDFInfo
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- CN108367512A CN108367512A CN201680073346.1A CN201680073346A CN108367512A CN 108367512 A CN108367512 A CN 108367512A CN 201680073346 A CN201680073346 A CN 201680073346A CN 108367512 A CN108367512 A CN 108367512A
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Classifications
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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
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- 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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- B29C70/40—Shaping or impregnating by compression not applied
- 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
- B29C70/48—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 and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/022—Melting the material to be shaped
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- 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
- 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
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
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- 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
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/475—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pistons, accumulators or press rams
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- 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
- 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
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/546—Measures for feeding or distributing the matrix material in the reinforcing structure
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
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Abstract
一种结合了按需熔化途径的树脂灌注方法。该方法包括:(a)提供呈冷冻树脂块(20)形式的可固化树脂组合物;(b)将该冷冻树脂块(20)联接到热的挤出机(22)的入口端口,该热的挤出机包括容纳在热的机筒(25)内的至少一个旋转螺杆(24);(c)在该入口端口处逐渐熔化该冷冻树脂块(20),并且同时将该熔化的树脂进料穿过该热的机筒(25)以产生具有适合于树脂灌注的黏度的液体树脂;(d)将从该挤出机离开的液体树脂连续地进料到包含纤维预成型件的模具中;以及(e)将该液体树脂引入该纤维预成型件中,其中该冷冻树脂块(20)提供足以灌注整个纤维预成型件的量的树脂组合物。
Description
本披露涉及通过树脂灌注方法例如树脂传递模制(RTM)制造纤维增强复合结构。
附图说明
图1示意性地示出了已知的RTM工艺,其中大量的可固化树脂被保持在环境温度或超过环境温度下。
图2示意性地示出了树脂灌注系统的实施例,该树脂灌注系统结合了用于供应树脂的按需熔化途径。
图3示意性地示出了树脂灌注系统的另一个实施例,该树脂灌注系统结合了用于供应树脂的按需熔化途径。
图4示出了根据一个实施例的用于储存冷冻树脂作为进料的可重复使用的滑动罩壳(slip case)。
图5示出了用于使用可消耗活塞的后续清洁阶段的方法。
具体实施方式
可以使用不同的方法制造三维纤维增强复合零件,这些方法之一是液体模制。树脂传递模制(RTM)和VARTM是涉及将液体树脂注入纤维预成型件中的制造工艺的实例。在RTM工艺期间,将该预成型件置于封闭的模腔中,并且将该树脂在压力下注入该腔体中。经常将具有预成型件的模具置于真空下,使得真空去除该预成型件中的所有截留空气并且加速RTM工艺。一旦液体树脂填充模腔,该树脂被固化,导致形成复合零件。VARTM类似于RTM,除了单面工具通常与真空装袋一起使用,并且真空将液体树脂拉入预成型件。该纤维预成型件是干增强纤维的组件,通常呈以堆叠布置的形式铺放的织物层形式。这些技术非常适合用于在许多情况下以合理的生产速率制造非常复杂形状的零件。
热固性树脂,特别是环氧树脂,由于其令人希望的特性例如耐热性和耐化学性、粘附性和耐磨性,已经被广泛用作此类纤维增强复合零件的基质树脂。对于RTM加工,固化剂溶解到树脂相中促进简单的“加热、注射/浸湿和固化”工艺方法,其中理解和权衡的是由于树脂和固化剂的紧密混合,树脂组合物甚至在环境温度下也显示出少许自反应性。由于此反应性,优选在树脂灌注前将树脂储存在低温条件下(例如小于-18℃)以防止反应。然而,将冷树脂加热到环境条件引起其变得极其粘性并且难以处理。进料树脂可以是呈碎屑或粒料形式,但是这些碎屑/粒料可能在室温下粘在一起并且变得难以进料到泵中,而且树脂的碎屑/粒料可能粘到进料槽或螺旋推运器(auger)的表面或沿着其拖曳。因此,对于RTM加工而言处理热固性树脂的方式是重要的考量并且已经被证明是限制因素。
当包含胺固化剂的环氧基树脂配制品储存在容器(特别是热的的容器)中时,由于树脂与固化剂之间的化学反应,安全储存时间随着储存温度的升高而减少。此外,随着储存温度提高动力学,此类反应的发热也增加。此种趋势在生产工艺中是有问题的,因为它决定了树脂在工艺周期中的特定点可具有的最大时间量或储存温度;这进而限制了使用该树脂的工艺的量和产量。如果直到在生产工艺中需要完全配制了的树脂体系的点,环氧官能团和胺官能团的相互作用可以减少,则与储存树脂相关的安全因数可以显著增加。
在RTM中经常用于克服RTM配制品的树脂储存稳定性问题的一种方法是提供两部分树脂系统,其中将环氧组分和固化剂储存在单独的罐中直到需要将它们混合在一起的点。已经示出这种方法消除反应性直到将组分混合在一起。然而,这种途径经常引入与在工艺的给定点的树脂与固化剂的比率的确定性以及混合工艺本身的彻底性有关的困难。其结果是,评估和校准重组产物的组成经常仅基于在工艺开始之前的质量或流量平衡测量。
图1示出了已知的RTM工艺,其中大量的包含固化剂的树脂被保持在环境温度或超过环境温度下。将散装树脂储存在容器11中,以便促进经由计量型装置12来泵送到热交换/脱气单元13中。最初呈颗粒形式的树脂的任何可溶性组分,例如固化剂,在单元13中溶解。然后,将热的的树脂转移到RTM模具或工具中,该模具或工具包含纤维预成型件。在停机或失常状态期间,可使树脂转向通过热交换器14以将其冷却。这种已知的工艺突出了与以上讨论的储存和处理大量反应性树脂相关的问题。
披露了结合了用于供应树脂的按需熔化(MOD)途径的替代树脂灌注方法。特别地,这种方法避免了在环境温度或超过环境温度下大量储存反应性树脂。如此,图1的部分A可以用更有效的布置代替。通常,具有MOD途径的树脂灌注方法包括:
(a)提供呈冷冻树脂块形式的可固化树脂组合物作为进料,其中该冷冻树脂块提供足以完全灌注纤维预成型件的量的树脂组合物;
(b)将该冷冻树脂块联接到热的挤出机的入口端口;
(c)在该入口端口处逐渐熔化该冷冻树脂块并且同时将该熔化的树脂进料穿过该挤出机以产生具有适合于树脂灌注的黏度的液体树脂;
(d)将该液体树脂从该挤出机连续地进料到包含纤维预成型件的模具中;以及
(e)将该液体树脂引入该纤维预成型件中。
如在此使用的术语“冷冻”是指冷却到低于树脂组合物凝固点的温度的状态。如在此使用的术语“可固化的”意指该组合物能够经受将使该组合物达到硬化或热固性状态的条件,例如加热。
图2示出了根据一个实施例的用于进行MOD树脂灌注方法的系统。在这个实施例中,将例如呈圆柱形圆材(log)形状的冷冻树脂块20包含在可重复使用的套管或“滑动罩壳”21中,该套管或“滑动罩壳”连接到挤出机22的入口端口。为了稳定和保持树脂滑动罩壳21相对于挤出机22的位置,提供引导壁23。该滑动罩壳21配置成适应该冷冻树脂块20的形状和尺寸。例如,滑动罩壳21可以具有管状形状以适应圆柱形的冷冻树脂圆材。挤出机22包括同轴地容纳在热的的圆柱形机筒25内的至少一个可旋转螺杆(或螺旋推运器)24。单螺杆或双螺杆挤出机可在此用于预期的目的。挤出机的机筒25被分成多个加热区,例如3至6个区,并且包括出口孔26。在一个实施例中,对该挤出机的这些加热区进行设置以产生从约30℃至约300℃范围内的温度梯度。挤出机具有多个单独的温度可控加热区以产生温度梯度是特别有利的。提供可移动活塞27以将冷冻树脂驱动到挤出机中。
图3示出了示例性的装配,其中使用来自热电公司(Thermo ElectronCorporation)的商业上可获得的挤出机,具有多个加热区的PRISM TSE 24TC双螺杆挤出机30,来进行在此披露的按需熔化方法。在这种情况下,单独提供导管31作为接口结构,用于将包含冷冻树脂33的滑动罩壳32联接到挤出机的入口。提供可移动活塞34以将冷冻树脂驱动到挤出机中。
在图2和图3所示装配的任一种中,当冷冻树脂块被迫使与挤出机螺杆接触时,冷冻树脂块在其下端逐渐熔化,然后该挤出机螺杆沿着热的机筒的加热区输送树脂。被机械驱动或连接到液压致动器的可移动活塞将必要的压力施加到冷冻树脂块的顶端上,以随着冷冻树脂熔化将冷冻树脂竖直地从滑动罩壳移位。优选地,驱动活塞以向树脂块施加恒定压力。挤出机的一个或多个螺杆在热的的机筒内旋转,并驱动熔化的树脂材料穿过机筒内的多个加热区。当熔化的树脂到达机筒的出口孔时,已经建立了相当大的压力,使得熔化的树脂能被迫使穿过该出口孔。离开挤出机机筒的出口孔的树脂呈液体形式,并且通过进料管线连续进料到树脂灌注模具中,该树脂灌注模具包含待注射/灌注的纤维预成型件。如此,离开挤出机出口孔的树脂具有适合于通过RTM灌注树脂的黏度。在优选的实施例中,离开挤出机的液体树脂在80℃至130℃范围内的温度下具有小于5泊的黏度。
包含纤维预成型件的模具是用于液体树脂灌注工艺、特别是RTM和VARTM的常规工具。此种模具典型地装配有一个或多个注射端口和真空机构,用于在加压条件下注射树脂。用于液体树脂灌注的模具可以是例如如美国专利号4,891,176中描述的双构件封闭模具,或者例如如美国专利号4,942,013、4,902,215、6,257,858以及8,652,371中描述的真空袋密封的单面模具。
在挤出过程期间可以改变若干条件以获得用于树脂灌注的所需的树脂特性。此类条件包括,通过举例,树脂组成、进料速度、操作温度、挤出机螺杆RPM、停留时间、加热区长度和挤出机扭矩和/或压力。优化此类条件的方法是本领域技术人员已知的。优选的是选择将在挤出过程期间使树脂组合物中的降解或固化水平的进展最小化的操作温度范围。在一些实施例中,挤出过程期间的操作温度范围可以在从约30℃至约300℃的范围内,如通过设置挤出机加热区确定的。
图4示出了在此披露的按需熔化方法前用于含有和储存冷冻树脂块的可重复使用的套管或滑动罩壳的实施例。该树脂套管具有可以是圆柱形形状的末端开放的壳体40,可以从壳体40移除的顶盖(或盖子)41和底盖(或底座)42。在使用中,将滑动罩壳40(没有盖41、42)连同其中的冷冻树脂都插入到图2所示的引导壁23或图3所示的引导管31中。可将顶盖41配置成凹入壳体中以限定要定位的活塞的接触表面。底盖42可包含安装到壳体40中的互补凹槽中的定位销42a。另外,壳体40可在下端配备有冲头止动件40a,以防止当所有树脂都被驱动到挤出机中时活塞与挤出机的一个或多个螺杆碰撞。滑动罩壳的壳体40是由低摩擦材料制成,该材料,例如聚四氟乙烯(PTFE),使得该壳体能够容易地滑入和滑出容器(例如图1所示的引导壁23),并且对冷冻树脂块具有低粘附性。此外,滑动罩壳按一定尺寸制造使得在一次使用中有足够量的树脂用于完全注射特定的预成型件。滑动罩壳保护工艺操作者免于不必要地处理树脂,由此使污染最小化。
此外,还认识到由于冷却和清洁挤出机所需的停机时间段或在“热”条件下清洁挤出机的风险,在灌注操作后清洁设备将存在困难。为了解决这个问题,在图5中提供并且示出了滑动罩壳和活塞配置的另一个实施例。在图5中,由可消耗的净化材料构成的可消耗活塞50用于将冷冻树脂块驱动到挤出机中。该净化材料是非反应性的热熔性可挤出材料,并且可以被驱动到挤出机中作为用于清洁挤出机机筒的后续清洁程序的一部分。热熔性可挤出聚合物是在标准环境温度(20℃-25℃)和压力(1atm)下足够刚性的、但在高温下能够变形或形成半液态(具有介于固体与液体之间的黏度和刚性)的聚合物。此种净化材料的实例是聚丙烯或类似的化学上不反应的材料。可消耗活塞50被配置成使含在滑动罩壳51中的校准量的树脂A完全移位,其中下盖52在另一端,使得当所有树脂块已经熔化并且进料到挤出机中时,该可消耗活塞完全填充由该树脂块占据的空间。树脂A的校准量是完全灌注和浸湿纤维预成型件所需的量。可消耗活塞50还配备有多个可断的凸耳或停止件50a,当树脂块已经完全移位时,这些凸耳或停止件起作用来阻止活塞进一步移动穿过滑动罩壳。在树脂灌注过程完成之后,将可断的凸耳50a折断并丢弃。并且可消耗活塞50经由以上参照图2和3描述的相同的机械地驱动或液压地致动的非可消耗活塞被驱动到操作挤出机中,并且将该净化材料挤出穿过该机筒的出口孔。可消耗活塞50具有突出(尖的或钝的)尖端50b,例如圆锥形尖端,其可与挤出机的旋转螺杆初始接触。然后,清洁是在挤出机冷却之后去除净化材料的再固化残余物的事件。以此方式,可以显著地降低热固性树脂在挤出机机筒中固化的风险。
含有反应性固化剂的热固性树脂配制品在储存温度下作为时间函数的稳定性是决定针对其使用的一组安全的加工条件的因素。定义安全加工条件的一种这样的方法是从加速量热法(Accelerate Rate Calorimetry)(ARC)实验导出绝热的达到最大速率的时间(Time to Maximum Rate)(TMR)。TMR定义了在达到自加速动力学开始之前组合物可保持在给定温度下的极限。据信,在此披露的MOD途径将树脂的TMR延长到用于储存的有效无穷大值,并且将树脂的加工能力保持在其环境状态或超过环境状态,由此导致在加工的树脂储存阶段期间几乎为零的放热风险。另外,连续加工意味着在升温过程中保持在超过环境温度下的树脂的体积最小,因此,相对于常规散装-树脂工艺,可以使加工期间的放热风险最小化。如果放热确实在挤出期间发生,可以将机筒清扫干净并且加工可以恢复。
纤维预成型件
将在此披露的树脂灌注方法中的纤维预成型件配置成用于通过树脂灌注或注射接收液体树脂,即,其可渗透液体树脂。预成型件由干增强纤维的组件组成,这些干增强纤维可以是呈以下形式:连续的、单向对齐(或“单向”)的纤维或纤维束,织造织物,非织造面纱或垫,多轴向织物(例如不卷曲织物或NCF),或其组合。连续纤维束由多根纤维长丝组成,例如3000-24,000根长丝。该组件可以包括以堆叠布置的形式铺放的干增强纤维的层。
这些增强纤维可由以下材料制造,这些材料选自但不限于玻璃(包括电气玻璃或E-玻璃)、碳(包括石墨)、芳族聚酰胺、聚酰胺、高模量聚乙烯(PE)、聚酯、聚苯-苯并噁唑(PBO)、硼、石英、玄武岩、陶瓷及其组合。对于制作高强度复合材料,例如用于航空航天和汽车应用的材料,特别适合的增强纤维是碳纤维。
树脂组合物
用于在此披露的树脂灌注或RTM方法的可固化树脂组合物包含一种或多种热固性树脂以及至少一种固化剂。此外,该可固化树脂组合物是可热固化的。将该树脂组合物配制成使得在小于180℃、更确切地说在约80℃至约130℃范围内的温度下黏度小于5泊。该树脂组合物还可以包含亚微米粒度的增韧颗粒,然而除非这些颗粒非常小,否则这些颗粒将被预成型件中的纤维有效地滤出,导致这些颗粒的不均匀分布,并且在一些情况下,会完全阻挡模具进一步树脂灌注。因此当存在时,这些增韧颗粒具有800nm或更小,例如在从约2nm至约800nm范围内,或在从约50nm至约200nm范围内的粒度。
热固性树脂可以选自:环氧树脂、双马来酰亚胺、苯并噁嗪、氰酸酯、乙烯基酯、聚异氰脲酸酯、双马来酰亚胺(bismalimide)、氰酸酯、酚醛树脂及其任何组合。特别适合的是具有大于1的环氧官能度的多官能环氧树脂。多官能环氧树脂包括每分子具有多于一个环氧基团的聚环氧化物化合物,这些聚环氧化物化合物可用于与胺固化剂反应。总体上,多官能树脂可以是具有环氧官能团的饱和的、不饱和的、环状或非环状的、脂肪族的、脂环族的、芳香族的或杂环的分子。多官能环氧树脂包括基于以下项的那些:苯酚和苯甲酚环氧酚醛清漆、酚醛加成物的缩水甘油醚;双脂肪族二醇的缩水甘油醚;二缩水甘油醚;二乙二醇二缩水甘油醚;芳香族环氧树脂;二脂肪族三缩水甘油醚、脂肪族多缩水甘油醚;环氧化的烯烃;溴化的树脂;芳香族缩水甘油胺;杂环缩水甘油基亚胺(imidine)和酰胺;缩水甘油醚;氟化的环氧树脂。
适合的环氧化物的实例包括通过在碱存在下表氯醇或表溴醇与多酚的反应制备的多缩水甘油醚。因此,适合的多酚是例如间苯二酚、邻苯二酚、对苯二酚、双酚A(双(4-羟基苯基)-2,2-丙烷)、双酚F(双(4-羟基苯基)甲烷)、双酚S、双(4-羟基苯基)-1,1-异丁烷、芴4,4′-二羟基二苯甲酮、双(4-羟基苯基)-1,1-乙烷、双酚Z(4,4′-亚环己基双酚)和1,5-羟基-萘。还适合的是多元醇、氨基酚或芳香族二胺的多缩水甘油醚。
附加实例包括:多价酚的多缩水甘油醚,例如邻苯二酚;间苯二酚、对苯二酚;4,4'-二羟基二苯基甲烷;4,4'-二羟基-3,3'-二甲基二苯基甲烷;4,4'-二羟基二苯基二甲基甲烷;4,4'-二羟基二苯基甲基甲烷;4,4'-二羟基二苯基环己烷;4,4'-二羟基-3,3'-二甲基二苯基丙烷;4,4’-二羟基二苯基砜;或三(4-羟基苯基)甲烷;上述二酚的氯化和溴化产物的多缩水甘油醚;酚醛清漆的多缩水甘油醚(即一元酚或多元酚与醛,特别是甲醛,在酸催化剂存在下的反应产物)。
环氧树脂的另外实例包括二烯改性的苯酚酚醛清漆的二缩水甘油醚、多官能脂环族羧酸与表氯醇的反应产物、脂环族环氧化物、脂环族环氧醚以及脂环族环氧酯等。
适合的多官能环氧树脂可以包括呈任何组合的二官能、三官能和四官能环氧树脂。双官能环氧树脂的实例包括双酚A的二缩水甘油醚(例如EponTM 828(液体环氧树脂),来自陶氏化学公司(Dow Chemical Co.)的DER 331、DER 661(固体环氧树脂),来自达因化学公司(Dyne Chemical Co.)的EJ-190,来自亨斯迈先进材料公司(Huntsman AdvancedMaterials)的Tactix 123),双酚F的二缩水甘油醚(DGEBF)(例如来自亨斯迈先进材料公司的PY306,来自迈图集团(Momentive)的EpikoteTM 158)。三官能环氧树脂的实例包括氨基酚的三缩水甘油醚,例如由亨斯迈先进材料公司供应的MY 0510、MY 0500、MY0600、MY 0610。四官能环氧树脂的实例包括亚甲基二苯胺的四缩水甘油醚(例如来自亨斯迈先进材料公司的MY 9655)、四缩水甘油基二氨基二苯基甲烷(例如由亨斯迈先进材料公司供应的MY 721、MY 720、MY 725、MY 9663、MY 9634、MY 9655)。
适合的固化剂包括一种或多种胺固化剂。此类固化剂包括每个氨基具有最高达500的分子量的化合物,例如芳香族胺或胍衍生物。特别适合的是每分子具有至少两个氨基的芳香族胺。实例包括二氨基二苯基砜,例如其中氨基位于相对于砜基的间位或对位。适用于本披露的胺固化剂的具体实例是3,3’-和4,4'-二氨基二苯基砜(DDS);4,4’-亚甲基二苯胺(MDA);双(4-氨基-3,5-二甲基苯基)-1,4-二异丙基苯;双(4-氨基苯基)-1,4-二异丙基苯;4,4’-亚甲基双-(2,6-二乙基)-苯胺(MDEA);4,4’-亚甲基双-(3-氯,2,6-二乙基)-苯胺(MCDEA);4,4’-亚甲基双-(2,6-二异丙基)-苯胺(M-DIPA);3,5-二乙基甲苯-2,4/2,6-二胺(D-ETDA80;龙沙公司(Lonza));4,4’-亚甲基双-(2-异丙基-6-甲基)-苯胺(M-MIPA);4-氯苯基-N,N-二甲基-脲;3,4-二氯苯基-N,N-二甲基脲(例如DiuronTM);二氰二胺(例如来自太平洋锚化学公司(Pacific Anchor Chemical)的AmicureTM CG 1200);和9,9双(氨基苯基)芴,如9,9双(3-氯-4-氨基苯基)芴(CAF)、9,9-双(3-甲基-4-氨基苯基)芴(OTBAF)和9,9-双(4-氨基苯基)芴。优选地,固化剂选自MCDEA、MDEA、MDA、3,3’-DDS和4,4-DDS,并且优选选自MCDEA、MDEA和MDA。
在一些实施例中,可固化树脂组合物包含多官能环氧树脂和胺固化剂的组合,其中环氧树脂和胺固化剂以足以提供固化剂中存在的胺基团:环氧组分中存在的环氧基团的以下摩尔比的量存在:从约0.5:1.0至约1.0:0.5、优选地从约0.75:1至约1:0.75、优选地从约0.9:1.0至约1.0:0.9,在一些实施例中,该比率是约1:1。
该一种或多种热固性树脂以及该一种或多种固化剂构成可固化组合物的主体,并且该可固化组合物的其余部分可以包括增韧组分,该增韧组分可以是亚微米颗粒或可溶性热塑性聚合物。
适合的增韧颗粒可以是具有800nm或更小,例如在从约50nm至约200nm范围内、优选地约50nm至约100nm范围内的粒度的核壳颗粒。核-壳颗粒包括内核部分和基本上包住内核部分的外壳部分。核部分优选是具有弹性体或橡胶特性的聚合物材料,即相对低的玻璃化转变温度(特别是相对于外壳部分的材料)、并且优选小于约0℃,例如小于约-30℃。外壳部分优选为玻璃状聚合物材料,即,具有高于环境温度(20℃)、优选高于约50℃的玻璃化转变温度的热塑性聚合物或交联的热固性聚合物。优选的核-壳颗粒包括:聚丁二烯-苯乙烯共聚物的核材料;和外壳,该外壳是任选地官能化的甲基丙烯酸甲酯的均聚物或共聚物。可商购核-壳颗粒的实例是可从钟渊公司(Kaneka Corp.)以商标Kane Ace MX,例如MX660和MX411,获得的核-壳颗粒。
还适合作为增韧剂的是选自金属盐(例如碳酸钙)和金属氧化物例如SiO2、TiO2和Al2O3的颗粒的无机颗粒。这些颗粒可以称为纳米颗粒。在一些实施例中,这些无机颗粒具有在从约2.0nm至约50nm范围内的粒度。
当存在时,增韧颗粒以基于组合物的总重量不大于5.0wt%(重量百分比)的量存在。
在此讨论的粒度可以通过动态光散射技术,例如,使用Malvern Zetasizer 2000测定。
该固化组合物可以包括少量(小于7wt%,优选地不大于5wt%)在高温下溶解于组合物中的可溶性热塑性聚合物作为增韧剂。适合的热塑性聚合物包括聚芳砜聚合物,例如聚醚砜(PES)。
Claims (17)
1.一种树脂灌注方法,该方法包括:
(a)提供呈冷冻树脂块形式的可固化树脂组合物;
(b)将该冷冻树脂块联接到热的挤出机的入口端口,该热的挤出机包括容纳在热的机筒内的至少一个旋转螺杆;
(c)在该入口端口处逐渐熔化该冷冻树脂块,并且同时将该熔化的树脂进料穿过该热的机筒以产生具有适合于树脂灌注的黏度的液体树脂;
(d)将从该挤出机离开的液体树脂连续地进料到包含纤维预成型件的模具中;以及
(e)将该液体树脂引入该纤维预成型件中,
其中,该冷冻树脂块提供足以灌注整个纤维预成型件的量的树脂组合物。
2.如权利要求1所述的方法,其中,在步骤(a)之前将该冷冻树脂块储存在可重复使用的套管中,所述套管包括管状壁、顶盖和底盖,并且
其中,在将该冷冻树脂块联接到该热的挤出机的入口端口之前将该顶盖和底盖从该管状壁移除。
3.如权利要求2所述的方法,其中,该可重复使用的套管的管状壁是由能够使该冷冻树脂块滑过的低摩擦材料制成。
4.如权利要求3所述的方法,其中,该低摩擦材料是聚四氟乙烯。
5.根据权利要求1至3中任一项所述的方法,其中,在(b)中,将该冷冻树脂块放置在容器内部,该容器机械地连接到该挤出机的入口端口使得该冷冻树脂块的一端在该挤出机的该入口端口中,并且向该冷冻树脂块的相反端施加压力以随着该冷冻树脂熔化将其从该容器移位。
6.如权利要求5所述的方法,其中,该冷冻树脂块具有圆柱形形状,并且该容器具有适应该冷冻树脂块的圆柱形形状的管状或圆柱形壁。
7.如权利要求5或6所述的方法,其中,通过被机械或液压地驱动的活塞向该冷冻树脂块的相反端施加压力。
8.根据前述权利要求中任一项所述的方法,其中,该挤出机进一步包括沿该机筒的长度的多个加热区。
9.如权利要求8所述的方法,其中,对该挤出机的这些加热区进行设置以产生在从约30℃至约300℃范围内的温度梯度。
10.根据前述权利要求中任一项所述的方法,其中,离开该挤出机的液体树脂在80℃至130℃范围内的温度下具有小于5泊的黏度。
11.根据前述权利要求中任一项所述的方法,其中,在(a)中的该可固化树脂组合物包括:一种或多种热固性树脂;以及固化剂。
12.如权利要求11所述的方法,其中,在(a)中的该可固化树脂组合物包括:一种或多种环氧树脂;以及胺固化剂。
13.根据前述权利要求中任一项所述的方法,其中,该纤维预成型件包括以堆叠布置的形式铺放的多个增强纤维层。
14.如权利要求5或6所述的方法,其中,通过可消耗活塞向该冷冻树脂块的相反端施加压力,随着该冷冻树脂熔化该可消耗活塞使该冷冻树脂从该容器移位,
其中,该可消耗活塞是由非反应性的、可挤出的聚合物制成,该聚合物可以穿过该挤出机的机筒被挤出,并且按一定尺寸制造成当所有的该冷冻树脂已经移位时填充由该冷冻树脂占据的空间。
15.如权利要求14所述的方法,其中,该可消耗活塞是由可挤出的聚合物形成,该可挤出的聚合物在环境温度20℃-25℃和压力1atm下是基本上刚性的,但是当被加热时能够变形或形成半液态。
16.如权利要求15所述的方法,其中,该可消耗活塞是由聚丙烯形成的。
17.一种用于制作复合结构的方法,该方法包括根据权利要求1至16中任一项所述的树脂灌注方法以形成经树脂灌注的预成型件,接着是:
将该经树脂灌注的预成型件固化以形成硬化的复合结构。
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CN115135700A (zh) * | 2020-02-21 | 2022-09-30 | 亨斯迈先进材料美国有限责任公司 | 增韧的热固性树脂组合物 |
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RU2686919C1 (ru) * | 2018-07-02 | 2019-05-06 | Акционерное общество "Препрег-Современные Композиционные Материалы" (АО "Препрег-СКМ") | Эпоксидное клеевое связующее, пленочный клей и клеевой препрег на его основе |
US20220118722A1 (en) * | 2019-01-11 | 2022-04-21 | Air Design, S.A. De C.V. | Carbon fiber shell having elastomer inner overmold, and method to fabricate a carbon fiber shell having elastomer inner overmold |
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BR112018012124A2 (pt) | 2018-12-04 |
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