CN104619484A - Pmi泡沫材料的新成型方法和/或由其制备的复合组件 - Google Patents
Pmi泡沫材料的新成型方法和/或由其制备的复合组件 Download PDFInfo
- Publication number
- CN104619484A CN104619484A CN201380030574.7A CN201380030574A CN104619484A CN 104619484 A CN104619484 A CN 104619484A CN 201380030574 A CN201380030574 A CN 201380030574A CN 104619484 A CN104619484 A CN 104619484A
- Authority
- CN
- China
- Prior art keywords
- foam
- shaping
- foamed material
- instrument
- pmi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 6
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- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
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- 229920000299 Nylon 12 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C44/34—Auxiliary operations
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- B29C44/5681—Covering the foamed object with, e.g. a lining
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- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
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- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
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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
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
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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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
- B29C51/06—Combined thermoforming and prestretching, e.g. biaxial stretching using pressure difference for prestretching
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- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
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- B29K2623/00—Use of polyalkenes or derivatives thereof for preformed parts, e.g. for inserts
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Abstract
本发明涉及例如适合用于制备具有由硬质泡沫材料组成的芯的复合材料的新方法。本发明在这里具有的优点是泡沫材料和覆盖层的塑料都可自由地选择。更具体地说,采用本发明方法还可以加工其加工温度明显不同于芯材料的那些的覆盖层。本发明进一步涉及一种方法,采用该方法,在第二种实施方案中,可以将整合泡沫结构部分地压实。采用第三种实施方案,可以由至少两个泡沫材料的工件通过焊接而制备具有特别高价值的接头的中空制品。在此,这可以在有或者没有覆盖层的情况下进行。另外,采用本发明的方法特别好地可通过真空成型方法加工泡沫材料。
Description
技术领域
本发明涉及例如适合用于制备具有由硬质泡沫组成的芯的复合材料的新方法。本发明在这里具有的大的优点是泡沫材料和覆盖层都可自由地选择。更具体地说,采用本发明方法还可以加工其加工温度明显不同于芯材料的那些的覆盖层。
本发明进一步涉及一种方法,采用该方法,在第二种实施方案中,可以将整合泡沫结构部分地压实。采用第三种实施方案,可以由至少两个泡沫材料的工件通过焊接而制备具有特别高价值的接头的中空制品。在此,这可以在有或者没有覆盖层的情况下进行。
另外,采用本发明的方法特别好地可通过真空成型方法加工泡沫材料。
背景技术
在现有技术中,对于制备具有硬质泡沫材料的纤维增强塑料或成型硬质泡沫材料的各种方法进行了一般性描述。在本发明范围中,“硬质泡沫材料”是指不可以(如例如市售的PU或聚苯乙烯泡沫材料那样)采用小的力而机械变形并随后再次恢复的泡沫材料。硬质泡沫材料的实例尤其是PP、PMMA或高度交联的PU泡沫。聚(甲基)丙烯酰亚胺(PMI),如例如由Evonik公司以品名销售的那种,是可特别强负荷的硬质泡沫材料。
制备所述复合材料的一种公知的方法是成型覆盖层,然后填充入泡沫原料并最终将该泡沫原料发泡。此种方法描述在例如US 4,933,131中。这种方法的一个缺点是,发泡通常非常不均匀地进行。材料例如PMI的情况尤其如此,其最好的情况下也只能作为颗粒添加。这种方法的另一个缺点是,覆盖层必须再次被移除以成型纯的泡沫材料。在复合结构组件的情况下,覆盖层和泡沫芯之间的粘附对于被施加机械负荷的结构组件又经常是不足够的。
在Passaro等人的Polymer Composites,25(3),2004,第307页及后续页中描述了一种方法,其中在压制模具中将PP泡沫芯材料与纤维增强的塑料接合成整体,在此泡沫芯材料借助模具按目标方式仅在表面处加热,以便可以实现与覆盖材料的良好粘结。在Grefenstein等人的International SAMPE Symposium and Exhibition,35(1,Adv.Materials:Challenge Next Decade),1990,第234-44页中描述了一种相似的用于制备具有蜂窝状芯材料或PMI泡沫芯的夹芯材料的方法。然而,成型用这两种方法都是不可能的,而仅制备片材形式的夹芯材料。
WO 02/098637描述了一种方法,其中将热塑性覆盖材料作为熔体形式施加到泡沫芯材料的表面上,然后借助双片材方法与泡沫芯成型在一起而形成复合模制品,然后将该热塑性材料冷却以致所述覆盖材料在模具中凝固。然而,使用这种方法仅可以结合有限数目的材料。例如不可制备纤维增强的覆盖材料。所述方法也不能用来纯粹成型没有覆盖材料的泡沫工件。另外,泡沫材料的选择也限于可在低温下弹性成型的材料。硬质泡沫在这种方法中在泡沫材料没有被均匀加热的情况下在结构上被太大程度损坏。
EP 0 272 359中描述的方法非常相似。在此,首先将泡沫芯坯件切割成一定形状并置于模具中。然后,将热塑性材料的熔体注射到表面上。然后提高温度使泡沫所述芯坯件发泡,由此引起向所述覆盖材料的表面上挤压。这种方法虽然可提供对所述覆盖材料的更好粘附。为此,具有首先成型的附加操作步骤的该方法是更昂贵且不方便的并且总体上在可实现的形状方面是明显更大程度上受限。
在W.Pip,Kunststoffe,78(3),1988,第201-5页中描述了在压制模具中制备具有纤维增强的覆盖层和PMI泡沫芯的成型的复合材料的方法。在这种方法中,在加热的压制模具中将各个层接合在一起,在此通过在局部加热的泡沫材料中的最上层压挤在一起而进行轻微成型。同时描述了其中可以通过在模具内部的后续发泡制备型材的方法。此种方法的缺点在上面已经进行了论述。作为第三个变型,公开了一种方法,其中让材料经历弹性压实同时压挤预加热的泡沫材料。预加热在烘箱中进行。然而,这种方法的缺点是,许多泡沫材料要求非常高的温度来热弹性成型。PMI泡沫例如要求至少185℃的温度。另外,芯材料在整合材料区域必须被适当地加热以避免材料断裂。然而,在此种温度下,尤其是因为在均匀分布下它们仅在数分钟的较长时间加热的情况下才是可能的,所以许多覆盖材料例如PP将被损坏以致不能实施该方法。
在U.Breuer,Polymer Composites,1998,19(3),第275-9页中公开了用于PMI泡沫芯的得自上述Pip的第三个变型的略微改进的方法。在此,使用IR加热灯加热PMI泡沫芯和纤维增强的覆盖材料。此类IR热辐射器(它们尤其发射3-50μm的波长的光(IR-C或MIR辐射))特别好地适合用于快速地加热基材。然而,在此(希望的)能量输入是非常高的,这同时引起许多覆盖材料,例如PP的损坏。例如,在Breuer等人中也仅公开了聚酰胺12(PA 12)作为用于覆盖层的可能的基体材料。PA 12可容易地加热到大于200℃而不会损坏塑料。泡沫芯的同时成型在这种操作方法中是不可能的,因为这种IR辐射区域的热辐射不穿透入泡沫基体中并因此没有获得可热塑性成型的状态。
发明内容
问题
在所论述的现有技术的背景下,本发明的目的因此是提供一种新方法,借此硬质泡沫材料可以快速和简单地成型而没有结构损坏和/或可以与覆盖层,特别是热塑性塑料一起加工成复合材料。
本发明的目的更尤其是提供一种方法,其中在成型操作中制备这些复合材料并且同时表面材料的选择是较自由的,而这种表面材料在加工期间不会经历损坏。
该方法另外适合于可将有或者没有覆盖材料的泡沫材料部分地压实。该方法还应适合于由有或者没有覆盖层的两种或更多种泡沫材料制备中空制品。该方法另外应可改进以致它可以与真空成型工艺结合。
另外,不管作为目的提出的各个实施方案如何,采用该新方法应可实现明显小于10min的快速周期时间。
这里没有明确论述的其它目的可以在下文由现有技术、说明书、权利要求书或实施例变得明朗。
解决方案
通过成型泡沫材料的新方法达到了所述目的。这种新方法特别适合成型硬质泡沫材料,例如高度交联聚氨酯(PU),聚丙烯(PP),或聚(甲基)丙烯酰亚胺,特别是聚甲基丙烯酰亚胺(PMI)。所述方法在此包括以下步骤:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照将所述泡沫材料加热,
c)用成型工具成型,
d)将最终工件冷却和取出。
两种不同实施方案在这里是可能的。在第一种实施方案中,用于用NIR辐射加热的工具和成型工具彼此是分开的。在这种情况下该方法包括以下方法步骤:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b1)放入加热场的机器侧的作用区,
b2)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照而将所述泡沫材料加热,
c1)将泡沫材料转移到成型工具中,
c2)用所述工具成型,和
d)将最终工件冷却和取出。
在第二种实施方案中,用NIR辐射进行辐照的加热设备是成型工具的整合构成部分:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b1)放入配备有可移除加热场的成型工具,
b2)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照而将所述泡沫材料加热,
c1)从所述成型工具的操作区除去加热器,
c2)用所述工具成型,和
d)将最终工件冷却和取出。
方法步骤b1)和b2)在此应理解为上述实施方案中的方法步骤b)的分步骤。这同样适用于考虑方法步骤c)时的方法步骤c1)和c2)。
令人惊奇地发现,通过方法步骤b)(或b2))中的材料的温和加热可引起塑料的通过均匀热输入的可成型性,而同时不会发生所述材料的任何损坏。特别地,例如在烘箱中加热时观察到的硬质泡沫表面的损坏在本发明方法的恰当实施时不会发生。由于所使用的NIR谱区的热辐射穿透泡沫泡孔中的气相而未被吸收并实现泡孔壁基体的直接加热。
尤其是,根据本发明的方法的特征在于,方法步骤d)中的成型使用双片材方法在真空中或在减压下进行。所使用的双片材设备在此经配置满足它可以用作加压成型机。
双片材方法原理上特征在于,两个或更多个工件在一个方法步骤中在真空中或在减压下成型,并在此彼此焊接,而无需添加剂例如粘合剂、焊接助剂或溶剂。这种方法步骤可以高周期时间、经济地和环境友好地实施。本发明范围内惊奇地发现,通过在方法步骤b)中用具有0.78-1.40μm的波长的NIR辐射进行辐照而预加热工件的附加方法步骤,这种方法也可以用于加工根据现有技术看起来不适合于这种方法的上述硬质泡沫材料。通过用所提及的辐射可较快速实施的加热,在整个工件中达到无应力的均匀热分布。在此,辐射强度可以在所述的范围内变化,这取决于所使用的泡沫材料。当另外使用覆盖材料时,改变加热场的温度和它们的强度以致即使在不同的加工温度和成型温度下,泡沫芯和覆盖材料也共同成型并接合在一起。这样的适应性调整是本领域技术人员用很少的实验而可容易实施的。
根据本发明的方法的一个大的优点是,它可以按环境上友好的方式并以非常高的周期时间进行,同时在一个工艺中结合多个操作步骤。在此,由这种在原理上是新的方法产生各自可以用来制备完全新的产品的一系列变型:
在第一变型中,在方法步骤d)中,即在成型中,实现泡沫材料的局部压实。此种局部压实可以实现新产品。例如由具有局部压实的硬质泡沫材料形成的成型制品可用于多种方面并且整体更加稳定。此外可以实现新的形状。另外,此种产品的优点是,可以尤其在压实区域中引入增强结构、插件或螺纹连接体以便从构造周围的协调地传递力。借助此种插件或螺纹连接体,泡沫材料可随后简单地在车辆或飞机构造中进一步加工。这样的区域经常还可以更好粘接或焊接。根据本发明的方法的此种变型可以对于例如PMI泡沫用小于5min的周期时间进行。这种变型的意外之处尤其在于,根据现有技术此种结构组件不能以一步工艺制备。
在本发明方法的第二个改进型中,方法步骤d)是双片材方法。
当泡沫材料在方法步骤a)中被覆盖材料在一面或双面覆盖并且因此借助所述双片材方法提供具有单面或双面覆盖层和一个硬质泡沫芯的复合材料时,根据本发明方法的这种变型是尤其优选的。这种第二变型可以按小于6分钟的周期时间进行。
令人惊奇地,覆盖材料的选择是较自由的。它们可以是例如纯热塑性塑料,它们的机织织物或针织物或复合材料,例如所谓的有机板材,或塑料涂覆的纺织品载体幅材例如人造革。覆盖材料优选是纤维增强塑料。纤维又可以例如是芳族聚酰胺纤维、玻璃纤维、碳纤维、聚合物纤维或纺织品纤维。塑料又可以优选是PP、聚乙烯(PE)、聚碳酸酯(PC)、聚氯乙烯(PVC)、环氧树脂、异氰酸酯树脂、丙烯酸酯树脂、聚酯或聚酰胺。
在所述方法的第三个变型中,在方法步骤a)中初始加入泡沫材料的至少两个独立的块体,然后由它们在方法步骤d)的成型中成型中空制品。这种变型还可以经设计满足制备具有多于一个空腔的成型块体。这种变型的优点在于,这种类型的中空制品可在没有粘合或后续热焊接的情况下制备。这又导致,所得中空制品与现有技术中的中空制品相比较具有稳定性和重量的更好结合。另外,中空制品具有更好的外观。这可以延伸到最终产品中两个原始泡沫材料块体之间的接头不再可见或几乎不再可见。更具体地说,该方法中形成的焊接缝不可与周围材料区分开或几乎不可与周围材料区分开,并且在这种接头处还保留孔结构。这种方法还可以呈双片材方法的形式进行。在这种情况下,还可以在小于5min的周期时间中以良好的可再现性实现非常复杂的几何结构。
在本发明的与第三变型相比轻微改进的实施方案中,甚至可以借助真空支持的成型方法将硬质泡沫的单个工件在减压下成型为非常复杂的工件。这种方法特别适合用于直至10mm的泡沫厚度。优选地,在此,在方法步骤c)中将泡沫材料转移到成型工具中之前直接地或者另选在其后直接地在成型工具中进行用压缩空气的预成型。
在原理上,这些方法可以在另一个改进型中在双壳工具中进行。这导致甚至更高的几何精度。本发明的另一个大的优点是,上述三个变型还可以与彼此自由地在一个同步进行的根据本发明的方法中彼此结合。例如,可制备具有至少一个空腔的边缘压实的成型体。也可制备具有部分压实的泡沫芯和/或一个或多个空腔的复合材料。
一般而言,使用夹紧框使材料在设备中定位以避免任何滑动,而不管所述本发明实施方案如何。为此,待加工的材料例如延伸超过工具边缘数厘米并且在这一区域中通过所提及的夹紧框向下压。
可以使用本发明方法加工的硬质泡沫材料是本领域技术人员可自由选择的。在此,PMI是优选的硬质泡沫材料。此种PMI泡沫通常以两步法制备:a)制备浇铸聚合物和b)使这种浇铸聚合物发泡。
为了制备浇铸聚合物,首先制备包含(甲基)丙烯酸和(甲基)丙烯腈作为主要组分(优选按2:3-3:2的摩尔比)的单体混合物。另外可以进一步使用共聚单体,例如丙烯酸的或甲基丙烯酸的酯、苯乙烯、马来酸或衣康酸或它们的酸酐或乙烯基吡咯烷酮。然而,在此,共聚单体比例应该不超过30重量%。还可以使用少量的交联性单体,例如丙烯酸烯丙酯。然而,所述量应该优选是最高0.05重量%至2.0重量%。
用于所述共聚的混合物还包含发泡剂,所述发泡剂在大约150-250℃的温度下分解或蒸发并在此形成气相。聚合在该温度以下进行,使得浇铸聚合物含有潜伏发泡剂。聚合适宜地在两个玻璃板之间的块型模具(Blockform)中进行。
然后在第二步骤中在相应的温度下使浇铸聚合物发泡。此类PMI泡沫的制备在原理上是为本领域技术人员已知的并可以参见例如EP 1 444293、EP 1 678 244或WO 2011/138060。作为PMI泡沫尤其可以提及得自Evonik Industries AG公司的型号。在制备和加工方面,丙烯酰亚胺泡沫应认为是对于PMI泡沫而言为类似物。然而,出于毒理学原因它们相对于其它泡沫材料是明显较不优选的。
PVC泡沫是另一种可加工硬质泡沫。这种硬质泡沫材料从用于车厢构造的纤维复合技术和夹芯制备,风力***的制备和造船方面是公知的。制成的泡沫片材可以与PMI泡沫片材类似地加工。
相应地适用于PP硬质泡沫。PP泡沫尤其已知作为绝缘材料,用于运输容器和作为夹芯材料。PP泡沫可以含有填料并通常可以20-200kg/m3的密度范围商购获得。
PU硬质泡沫又不同于PU软质泡沫的特征在于更为闭合的孔结构和更高的交联度。PU硬质泡沫还可以含有较大量的无机填料。
所需要的泡沫部件可经由玻璃板的适合选择或经由借助模内发泡的制备过程制造。另选,从经发泡的泡沫片材通过切割、锯切或铣切进行制备。在此,可以优选从一个片材切割多个泡沫部件。
硬质泡沫材料的密度可较自由地选择。PMI泡沫可按例如25-220kg/m3的密度范围使用。
经锯切、切割或铣切的泡沫芯块体在此优于借助模内发泡制备的那些的优点在于,它们在表面处具有开孔。当接触树脂浸渍的纤维时,还不完全固化的树脂的一部分渗透入这些在泡沫芯表面处的开孔中。这样具有的优点是,一旦固化后就获得在泡沫芯和外壳材料之间的界面处特别强的粘附。
原则上,本发明的由硬质泡沫形成的工件具有很宽的应用领域。
通过局部压实的第一变型制备的工件也可以称为具有整合结构的泡沫材料。它们(也在附加变型中称为复合材料)特别适合用于由传递力的界面与围绕所述(复合)结构组件的材料的周边结构的接合而定的应用。这适用于任何想得到的其中由例如金属或其它合成材料制成的结构组件与所述泡沫材料和/或复合材料接合的构造。这些先决条件尤其由汽车构造、航空航天技术、船舶构造、轨道车辆构造、机械制造、医疗技术、家具工业、风力***建造或电梯构造应用领域得出。
第二变型的复合材料(甚至没有整合结构的那些)可以尤其用于批量生产,例如用于汽车工业中的车身构造或内部装饰,轨道车辆或船舶构造中的内部部件,航空航天工业,机械制造,家具构造或风力***建造中。
由硬质泡沫形成的中空制品又可以用于例如,蓄电池箱,空调设备中的通风道或用作绕线转子叶片的空气动力学组件(例如作为所谓后缘)。而且,另外,在上述工业分支中的应用也是可想得到的。
附图说明
图1:具有泡沫材料芯的纤维增强塑料的制造
A:加热阶段;B:成型
(1)成型工具的上部件
(2)成型工具的下部件
(3)顶部加热器(NIR辐射器)
(4)底部加热器(NIR辐射器)
(3a)和(4a)移到旁边的加热器
(5)泡沫芯
(6)夹紧框
(7)覆盖层
图2:制备具有泡沫材料的部分压实的整合结构
A:加热阶段;B:成型
(1)成型工具的上部件
(2)成型工具的下部件
(3)顶部加热器(NIR辐射器)
(4)底部加热器(NIR辐射器)
(3a)和(4a)移到旁边的加热器
(5)泡沫材料
(6)夹紧框
图3:中空制品的成型
A:加热阶段;B:成型
(1)成型工具的上部件
(2)成型工具的下部件
(3)顶部加热器(NIR辐射器)
(4)底部加热器(NIR辐射器)
(3a)和(4a)移到旁边的加热器
(5)泡沫材料(在这里:用于上侧面的第一工件)
(6)夹紧框
(8)泡沫材料(用于下侧面的第二工件)
图4:泡沫材料的真空成型
A:加热阶段;B:成型
(2)成型工具的下部件
(3)顶部加热器(NIR辐射器)
(4)底部加热器(NIR辐射器)
(4a)移到旁边的底部加热器
(5)泡沫材料
(6)夹紧框
(7)覆盖层
(9a)在正压力下的机器空间
(9b)在负压力(真空)下的机器空间
具体实施方式
实施例
下面显示对于本发明的一些特定的实施方案的一般性描述。在此这些还包括实施例。成功地进行了相应的试验。
实施例1:具有泡沫材料芯的纤维增强塑料(复合结构组件)的制造
在双片材成型机例如得自Geiss AG公司的T8型号上进行该方法。该机器在此按以下配置装备:
具有快速辐射器(NIR;0.78-1.40μm)的加热场
可调节工作区窗体
高度可调节的顶部加热器
压力30公吨(最小(min.)),电机驱动
可加热和可冷却成型工具
参照图1说明这一实施方案。
一般地,待选择的工艺参数取决于各个情况下使用的设备的布局。它们必须通过初步试验测定。例如,控制温度TF取决于PMI泡沫基体的Tg(S),覆盖层的成型温度,顶部加热器的高度调节Tg(S)≤TF(顶部加热器的温度)。在此适用的是,顶部加热器的温度要设置到越高,顶部加热器和泡沫基体之间的距离越大。取决于结构组件的部分区域的变形度(Ug),辐射器场强度(I)也可以变化。在靠近夹紧装置的边缘处,辐射器场强度I经选择接近于100%以确保材料的再流入和同时获得材料的夹紧状态。
覆盖层的铺层(Layups):可以将不同的覆盖材料提供于泡沫芯的一面或两面上。例如可以使用由各种纤维类型或纤维混合物制造的复合材料构成的可铺盖织物/铺层(Gelege)(所谓有机板材),它们具有热塑性相,或热塑性覆盖层例如PC、PMMA、PVC或能够与泡沫表面粘结的其它可热塑性成型的塑料。这可以任选地使用热熔粘合剂膜或纤维网作为粘合促进剂进行。在一个具体实例中,在顶部和底部使用由得自Bond Laminates公司的有机板材(Dynalite 102-RG600)形成的800μm厚度的层。另一个实例中在双面使用厚度1500μm的聚碳酸酯膜片Lexan。
操作过程:所使用的泡沫芯是得自Evonik Industries AG公司的S型PMI泡沫,其具有51kg/m3的密度和15mm的材料厚度。夹紧装置将优选在内表面上采用Al胶带或高光泽不锈钢板而具有镜面光泽度。覆盖层的规格体(Format)尺寸取决于调节的窗体尺寸并且经测量满足覆盖层在长度和宽度方面与该窗体重叠大约5cm并因此能被夹紧框卡住。待成型的泡沫芯与覆盖层一起布置在工作窗体上方并且下降夹紧框以定位。
在加热到210℃的PMI泡沫变形温度的过程中,可以观察到覆盖层开始成波浪形。在继续塑化开始时,在机器空间中设置单个压缩空气脉冲以防止下垂到底部加热器上。取决于覆盖层的要求,热辐射器的控制温度和强度可以在大约3-4min后改变以致覆盖材料塑性变形成可铺盖状态。然后将控制温度短时间地再提高大约5℃,以为材料提供更大的残留热。
当加热阶段完成后,将底部和顶部加热场移出工具半分体的工作区并尽快进行在120℃-150℃的温度下经调温的工具的闭合动作。这样,使覆盖层沿着工具几何结构的成型和铺盖以一个操作步骤中进行。在已经将工具冷却至小于80℃后,可以最后取出结构组件。在已经将工具再加热后,可以开始下一个复合结构组件的制造。
实施例2:具有局部压实的泡沫材料(整合结构)的制造
该方法例如在如实施例1所述的相同的Geiss AG公司的型号T8双片材成型机上进行。在此同样,待选择的工艺参数一般地取决于各个情况下使用的设备的布局。相应地适用于控制温度TF,如对于实施例1所述。参照图2说明这一实施方案。
操作过程:在本实施例中使用得自Evonik Industries AG公司的IG型PMI泡沫,其具有110kg/m3的密度。起始材料厚度是60mm。经由工具中突起设置的锥体达到部分压实,所述锥体使在大约25mm的直径内的材料部分地压实到34mm厚度。在结构组件的其它区域中,工具方面的几何结构也以窄半径和相当大压实度在大约6min的周期时间内再现。
夹紧装置为此将优选在内表面上采用Al胶带或高光泽不锈钢板而具有镜面光泽度。泡沫的规格体尺寸取决于设置的窗体尺寸并且经测量满足泡沫规格体在长度和宽度方面与该窗体重叠大约5cm并因此能被夹紧框卡住。待成型的泡沫规格体布置在工作窗体上方并且下降夹紧框以定位。
相应于部分压实的程度,例如在其中成型件例如插件将引入的区域中,可以适应性调节热强度。在这一具体实施例中,首先用快速辐射器(NIR;0.78-1.40μm)加热到190℃的温度。在继续塑化开始时,在机器空间中在泡沫厚度≤15mm下设置单个压缩空气脉冲以防止下垂到底部加热器上。在加热阶段后,将控制温度短时间地再提高大约5-10℃以为材料提供更大残留热。
为了成型,当完成加热阶段之后,将底部和顶部加热场移出工具半分体的工作区并尽快进行在120℃-150℃的温度下的经调温的工具的闭合动作。这样,结构组件的单个区域的成型和同时压实以一个操作步骤进行。在此,在相同操作步骤中,插件的引入可以同时地进行。
在已经将工具冷却至小于80℃的温度后,可以取出结构组件。在已经将工具再加热后,可以开始下一个纤维-塑料复合材料(FKV)结构组件的制造。
实施例3:中空制品的成型
该方法例如在如实施例1所述的相同的Geiss AG公司的型号T8的双片材成型机上进行。在此同样地,待选择的工艺参数一般性地取决于各个情况下使用的设备的布局。相应地适用于控制温度TF,如对于实施例1所述。参照图3说明这一实施方案。
操作过程:在本实施例中使用得自Evonik Industries AG公司的IG型PMI泡沫,其具有110kg/m3的密度。这两个泡沫规格体的起始材料厚度分别是15mm。
夹紧装置为此将优选在内表面上采用Al胶带或高光泽不锈钢板而具有镜面光泽度。泡沫的规格体尺寸取决于设置的窗体尺寸并且经测量而满足泡沫规格体在长度和宽度方面与该窗体重叠大约5cm并因此能被夹紧框卡住。将两个泡沫规格体放入机器的双片材框架中。待粘接形成中空制品的泡沫规格体布置在工作窗体上方并且下降夹紧框以定位。
相应于成型度,可以适应性调节热强度。在这一具体实施例中,首先用快速辐射器(NIR;0.78-1.40μm)加热到195℃的温度。在继续塑化开始时,在机器空间中在泡沫厚度≤15mm下设置单个压缩空气脉冲以防止下垂到底部加热器上。在加热阶段后,将控制温度短时间地再提高大约5-10℃以为材料提供更大残留热。
为了成型,当完成加热阶段后,将底部和顶部加热场移出工具半分体的工作区并尽快进行在120℃-150℃的温度下的经调温的工具的闭合动作。通过将塑性泡沫板块抽吸到顶部和底部工具的工具内壁上而进行成型。同时,对工具几何结构的构造测量确保泡沫规格体沿周边焊接在一起。在此,中空制品以轮廓符合方式再现工具几何结构并在周边边缘处焊接在一起以致没有产生接缝,而且再现均匀泡沫结构。
在已经将工具冷却至小于80℃的温度后,可以取出结构组件。在已经将工具再加热后,可以开始下一个纤维-塑料复合材料结构组件的制造。
实施例4:中空制品的真空成型
该方法例如在如实施例1所述的相同的Geiss AG公司的型号T8的双片材成型机上进行。在此同样地,待选择的工艺参数一般性地取决于各个情况下使用的设备的布局。相应地适用于控制温度TF,如对于实施例1所述。参照图4说明这一实施方案。
操作过程:在本实施例中使用得自Evonik Industries AG公司的ROHACELL型PMI泡沫,其具有71kg/m3的密度。泡沫规格体的起始材料厚度是5.6mm。本发明的这一实施方案中优选使用至多10mm厚度的泡沫规格体。
夹紧装置为此将优选在内表面上采用Al胶带或高光泽不锈钢板而具有镜面光泽度。泡沫的规格体尺寸取决于设置的窗体尺寸并且经测量满足泡沫规格体在长度和宽度方面与该窗体重叠大约5cm并因此能被夹紧框卡住。将两个泡沫规格体放入机器的双片材框架中。待粘结形成中空制品的泡沫规格体布置在工作窗体上方并且下降夹紧框以定位。
相应于成型度,可以适应性调节热强度。在这一具体实施例中,首先用快速辐射器(NIR;0.78-1.40μm)加热到210℃的温度。在继续塑化开始时,在机器空间中设置单个压缩空气脉冲并从而产生泡沫气泡。
为了成型,在加热阶段已经结束后仅将底部预热场移出工具半分体的工作区,并从下方在泡沫气泡下面移动成型工具。然后将工具布置在气泡下面。然后尽可能快速地排空机器空间。这样通过加载在其上的空气柱将泡沫吸引越过工具轮廓。在整个成型过程期间,顶部加热器保持在其工作位置以防止泡沫冷却。在工具已经冷却至≤80℃后,可以取出结构组件,并在重复加热工具后,可以开始下一个结构组件的制造。
如此制备的具有大约260mm的拱高的几何结构构成例如直升飞机雷达天线罩的前部区段。
Claims (10)
1.成型泡沫材料的方法,其中所述泡沫材料是高度交联的PU,是PP,或是PMI,并且所述方法包括以下方法步骤:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照而将泡沫材料加热,
c)用成型工具成型,
d)将最终工件冷却和取出。
2.根据权利要求1的方法,其中所述加热和成型在两个分开的工具中进行并且所述方法在此包括以下方法步骤:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b1)放入加热场的机器侧的作用区,
b2)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照而将泡沫材料加热,
c1)将泡沫材料转移到成型工具中,
c2)用所述工具成型,和
d)将最终工件冷却和取出。
3.根据权利要求1的方法,其中所述加热和成型在一个工具中进行并且所述方法在此包括以下方法步骤:
a)任选的采用覆盖材料和在其之间的泡沫芯的复合层构造,
b1)放入配备有可移除加热场的成型工具,
b2)通过用具有0.78-1.40μm的波长的近红外线辐射(NIR辐射)进行辐照而将泡沫材料加热,
c1)从所述成型工具的操作区除去加热器,
c2)用所述工具成型,和
d)将最终工件冷却和取出。
4.根据权利要求1-3中任一项的方法,其中方法步骤d)是真空成型方法。
5.根据权利要求1-4中任一项的方法,其中所述泡沫材料是PMI泡沫。
6.根据权利要求1-5中任一项的方法,其中采用方法步骤d)实现泡沫材料的局部压实。
7.根据权利要求1-5中任一项的方法,其中初始加入所述泡沫材料的至少两个独立的块体并在方法步骤d)中由它们成型中空制品。
8.根据权利要求4或5中任一项的方法,其中方法步骤c)之前直接地或之后直接地进行用压缩空气的预成型。
9.根据权利要求4或8中任一项的方法,其中进行方法步骤a)并将纤维增强塑料用作覆盖材料。
10.根据权利要求9的方法,其中所述塑料是PP、PE、PC、PVC、环氧树脂、异氰酸酯树脂、丙烯酸酯树脂、聚酯或者是聚酰胺,并且所述纤维材料是碳纤维、玻璃纤维、聚合物纤维或芳族聚酰胺纤维。
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