CN109477535B - 振动阻尼系统 - Google Patents
振动阻尼系统 Download PDFInfo
- Publication number
- CN109477535B CN109477535B CN201780045496.6A CN201780045496A CN109477535B CN 109477535 B CN109477535 B CN 109477535B CN 201780045496 A CN201780045496 A CN 201780045496A CN 109477535 B CN109477535 B CN 109477535B
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- Prior art keywords
- vibration damping
- damping coating
- coating
- honeycomb body
- measured
- Prior art date
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Abstract
一种减震结构包括蜂窝体和振动阻尼涂层,该振动阻尼涂层在蜂窝体的至少一部分胞元的至少一部分内表面上。该振动阻尼涂层通过固化涂层组合物形成,所述涂层组合物包括丙烯酸类聚合物或共聚物乳液以及振动阻尼填料。所述结构可包括接合到所述蜂窝体的上表面和下表面的粘合剂以及连接到所述粘合剂的两片护套,其中一个护套位于蜂窝体的所述上表面,一个位于蜂窝体的所述下表面。
Description
技术领域
在航空航天领域,需要减少整个飞行器的振动和声音传播。对于乘客来说,振动和背景噪音是不舒服的,并且振动会在部件上形成机械应力。
背景技术
由于燃料消耗的增加与重量的增加相关,因此不希望增加飞行器的重量。另外,增加飞机的重量会增加起飞和着陆所需的距离,并降低空速。
因此,需要一种用于飞行器的改进的振动阻尼结构,其最小化由阻尼部件增加的重量。Shen等人的美国公开第2008/0182067号是已知现有技术复合板的实例。
发明内容
本发明满足了这种需求。本发明涉及包括改进的振动阻尼结构的系统及其制造方法。该结构包括具有对置表面和多个开放胞元的蜂窝结构,每个胞元具有内表面。该结构包括在一些胞元的至少一些内表面上的振动阻尼涂层,并且优选地该振动阻尼涂层在基本所有胞元的基本整个内表面上。
所述涂层通过固化涂层组合物来形成,所述涂层组合物包括含有聚合物颗粒的丙烯酸类聚合物或共聚物乳液以及振动阻尼填料。振动阻尼填料与聚合物颗粒的重量比通常为2:1至8:1。振动阻尼填料占组合物重量的至少15%。该结构包括足够多的阻尼涂层,通过以下一种或多种方式测量减少的振动传输:
a.通过ASTM E756测量的振动阻尼损耗因子比没有振动阻尼涂层的结构高至少0.05;或者
b.通过ASTM E90测量的声音穿透损耗(transmission loss)比没有振动阻尼涂层的结构高至少约5分贝,并且通常高约20分贝。
振动阻尼填料可包括云母,并且可选地可基本上由云母组成。云母可包含多个颗粒,其中不超过3重量%的颗粒直径大于300微米。
该结构通常包括用于飞行器应用的粘合剂,该粘合剂接合到蜂窝体的两个表面,还包括用于蜂窝体的两个表面的片状护套,该护套通过粘合剂连接到蜂窝体。粘合剂可包括热固性聚合物粘合剂膜。
护套可以由铝或纤维增强聚合物形成。每片护套的厚度可为约0.005英寸至约0.1英寸。
因为飞行器部件可暴露于非常低的温度,优选地,丙烯酸类聚合物或丙烯酸类共聚物的玻璃化转变温度为约-40℃至约0℃。
优选地,丙烯酸类聚合物或丙烯酸类共聚物乳液的粘度小于800厘泊,其由3号博勒飞转子(Brookfield spindle#3)在73°F和10转/分钟下测量。
振动阻尼涂层的厚度可为约0.002英寸至约0.015英寸。
该结构可以具有任何尺寸,但通常在加工到飞机地板部件的尺寸之前制成4英尺宽、8英尺或12英尺长。
附图说明
参照以下描述、所附权利要求书以及附图将更好地理解本发明的这些和其它特征、方面和优点,在附图中:
图1是具有本发明特征的结构的立体图,其中一些层被部分移除;和
图2是沿图1中的线2-2截取的图1中所示结构的剖视图。
具体实施方式
如本文所用,以下术语及其变体具有下文给出的含义,除非在使用该术语的上下文中明确意在不同的含义。
本文中更详细地描述了整个说明书中使用的化学术语的定义和一般术语的定义,但除非另有说明,否则根据元素周期表(CAS版本,化学和物理手册,第75版,内封面)认定化学元素,并且如果没有在此特别描述,特定官能团以及特定功能基团和反应性由有机化学的一般原理描述,如有机化学(第四版,L.G.Wade,Jr.,Prentice-Hall Inc.,New Jersey,1999)所描述。
术语“溶液”是指包含溶剂和溶质的组合物,并且包括纯溶液和悬浮液。溶液的实例包括溶解在液体中的固体、液体或气体以及悬浮在液体中的颗粒或胶团。
术语“乳液”是指通过表面活性剂(如皂)分散在水中的微小液滴(丙烯酸类共聚物)的精细分散体,该术语用于区别于溶液或共混物。
术语“ASTM E756”涉及具有自本申请有效提交日期起的编号的ASTM测试,该测试利用如下参数:在环境室温和环境室内湿度下,对于阻尼结构和非阻尼结构,以1,800Hz的频率测试高度为0.4英寸的ASTM测试的图2形状的试样。在环境室温和环境室内湿度下,在测试之前,材料陈化到足以用作面板。测试结果是“峰值耗损因子”。
术语“ASTM E90”涉及具有自本申请有效提交日期起的编号的ASTM测试,该测试利用如下参:对于阻尼结构和非阻尼结构,厚度或高度为0.4英寸的试样在环境室温和环境室内湿度下以1,000Hz的噪声频率进行测试。在环境室温和环境室内湿度下,测试的材料陈化到足以在测试之前用作面板。测试结果是“声音穿透损耗(STL)”。
参照图1和图2,本发明涉及包括结构100的系统,该结构100包括具有对置表面即上表面104和下表面106的蜂窝体102。该结构100包括多个开放胞元108。每个胞元108具有内表面110。在至少一部分的胞元108的至少一部分的内表面110上有振动阻尼涂层112。可选地,基本上所有胞元108的基本所有内表面110上都有振动阻尼涂层112。
蜂窝体102是柔性或刚性结构材料,其包括多个紧密堆积的几何胞元108,它们一起形成具有高比刚度、高比强度和独特能量吸收特性的轻质蜂窝状结构。这种蜂窝状结构在本领域中是公知的。如图1和图2所示,形成蜂窝体102的胞元108的几何形状可以是六边形,类似于由蜜蜂建造的天然蜂窝体102的结构。或者,堆积的胞元108的几何形状可以是非六边形。例如,胞元108可以是圆形、椭圆形、三角形、正方形、矩形、五边形和八边形或其它合适的形状,包括各种几何形状的过膨胀结构。同样合适的是加强蜂窝体和其它规则或不规则的胞元框架。通常,每个胞元108的横截面限定了最大边到边距离在约0.125英寸到约1英寸之间的区域。
蜂窝体102通常由轻质材料例如铝箔或纸制成。浸渍有酚醛树脂的芳族聚酰胺纸通常用于蜂窝体102。优选地,蜂窝体102由间位或对位芳族聚酰胺纤维纸制成,都由杜邦公司(DuPont)以商品名或销售。芳族聚酰胺纸浸渍有耐热酚醛树脂。
通常,蜂窝体102的厚度在约0.125英寸至约4英寸之间,这取决于使用蜂窝体102的结构100的应用。蜂窝体102通常还具有约24kg/m3和约200kg/m3之间的密度。
振动阻尼涂层112通过固化包含丙烯酸类聚合物或丙烯酸类共聚物乳液和振动阻尼填料的涂层组合物来形成,所述丙烯酸类聚合物或丙烯酸类共聚物乳液包含聚合物颗粒。振动阻尼涂层112可以是任何厚度,但优选地,振动阻尼涂层112具有约0.002英寸至约0.015英寸的厚度。
丙烯酸类聚合物或丙烯酸类共聚物是基于丙烯酸酯(例如,丙烯酸丁酯、丙烯酸乙基己酯、甲基丙烯酸甲酯等)的单体聚合产物,其包含一种类型的单体或多种类型。丙烯酸类聚合物或丙烯酸类共聚物在室温下是柔性的,并且可具有约-40℃至约0℃的玻璃化转变温度。丙烯酸类聚合物或丙烯酸类共聚物乳液的粘度优选小于800厘泊,由博勒飞转子(Brookfield spindle)#3在73°F和10转/分钟下测量。优选地,丙烯酸类聚合物或丙烯酸类共聚物乳液的pH大于7。例如,丙烯酸类聚合物或丙烯酸类共聚物乳液是Vinavil公司销售的4811,该公司的营业地址在Vinavil Americas,1144East Newport CenterDrive,Deerfield Beach,Florida 33442。丙烯酸类聚合物或丙烯酸类共聚物乳液可包含任何重量百分比的涂层组合物,但优选丙烯酸类聚合物或丙烯酸类共聚物的重量百分比为约15%至约40%。
振动阻尼填料可选自包括云母、陶瓷空心球、碳酸钙、硫酸钡、硅酸盐、粘土如高岭土和滑石的组。优选地,振动阻尼填料基本上包括云母。可选地,云母包含由ImerysPerformance Minerals以商品名200-HK销售的金云母,该公司的营业地址在100Mansell Court East,Suite 300,Roswell,Georgia 30076。优选地,振动阻尼填料包含涂层组合物的约20至约40的重量百分比,如在涂层组合物固化之前测量的。
通常,基本上所有云母颗粒的尺寸都小于300微米。可选地,不超过3重量%的云母颗粒的尺寸大于300微米。由于云母颗粒的形状不规则,因此术语“尺寸”是指筛眼孔径,即颗粒通过的最小筛眼。
涂层组合物中振动阻尼填料与聚合物颗粒的重量比通常为2:1至8:1,并且振动阻尼填料通常占涂层组合物重量的至少约15%。
结构100包括足够多的振动阻尼涂层112以有效地减少振动。通过本发明实现的减少可以表示为以下一个或多个:
a.通过ASTM E756测量的振动阻尼损耗因子比没有振动阻尼涂层112的结构100的振动阻尼损耗因子高至少约0.05;和/或
b.通过ASTM E90测量的声音穿透损耗比没有振动阻尼涂层112的结构100的声音穿透损耗高至少约5分贝。
除稀释剂之外,涂层组合物还可包含其它组分,例如一种或多种阻燃剂、消泡剂、增稠剂和液体混合组分。
可接受的阻燃剂的实例来自溴化有机物、磷酸盐或多磷酸盐、硼酸锌、氢氧化铝或氢氧化镁、三氧化锑或五氧化物等。优选地,该组合物包含三(1,3-二氯异丙基)磷酸酯,其由ICL以商品名FR-2销售,营业地址在Millennium Tower,23Aranha Street,TelAviv 61070 Israel;十溴二苯乙烷,其由Great Lakes Solutions以商品名2100R销售,营业地址在CT 4067,Middlebury,199Benson Road;和/或氧化锑,其由Chemtura Corporation以商品名Antimony TrioxideAO3销售,营业地址在199Benson Road,Middlebury,CT 06749。优选地,阻燃剂的总量可以为涂层组合物的约2至约7重量%。
通常,消泡剂不溶于组合物中并具有表面活性性质。消泡剂产品的基本特征是低粘度并且容易在泡沫表面上快速铺展。优选地,该组合物包含水基消泡剂,其包括矿物油或植物油和蜡,它们是长链脂肪醇、脂肪酸皂或酯。可选地,使用由Air Products andChemicals,Inc以商品名DF-37销售的乙炔基添加剂,营业地址在7201Hamilton Blvd.Allentown,PA 18195-1501。通常,消泡剂包含固化前涂层组合物的约0.1至约1的重量百分比。
增稠剂或稠化剂是可以增加液体粘度而基本上不改变其它性质的物质。增稠剂还可以改善其它成分或乳液的悬浮,这增加了产品的稳定性。可接受的增稠剂可选自化学取代的纤维素、蓖麻油衍生物、有机硅、二氧化硅微硅粉和/或粘土,例如膨润土和硅镁土。可选地,该组合物包含合成的层状硅酸盐,其掺入无机多磷酸盐胶溶剂,其由RockwoodAdditives Limited以商品名RDS销售,营业地址在Moorfield Road,Widnes,Cheshire,United Kingdom,WA8 3AA。优选地,增稠剂的重量百分比为涂层组合物的约0.1%至约2%。
可添加液体混合组分以增加成分之间的相容性,并且还可以帮助成膜和调节水蒸发速率。在组合物中优选具有中沸点的乙二醇醚或醇。可选地,使用由Ashland,Inc以商品名Glycol Ether EB销售的乙二醇单丁醚,营业地址在5200Blazer Parkway,Dublin,OH43017。优选地,液体混合组分的重量百分比为约1%至约5%。
涂层组合物还可包含稀释剂作为乳液的一部分。稀释剂是在涂层组合物固化期间最终与任何其它挥发性液体一起蒸发的液体,但添加稀释剂允许快速调节组合物中的总固体含量。优选地,稀释剂是去离子水。优选地,稀释剂的重量百分比为约10%至约65%。这允许涂层组合物的固体含量在固化前可调节约30%至约70%。
结构100可包括粘合剂114,其连接到蜂窝体102的上表面104和下表面106。通常,粘合剂114选自热熔薄膜粘合剂的组,包括热固性类型如环氧树脂、酚醛树脂、聚氨酯和双马来酰亚胺,和热塑性类型如聚酰胺、聚酯和聚酰亚胺。优选地,粘合剂114包括环氧基热固性粘合剂膜。粘合剂114用于将连接在蜂窝体102的上表面104处的第一片护套116和连接到蜂窝体102的下表面106的第二片护套118保持在适当位置。
第一片和第二片护套116、118可选自整体片材或纤维增强复合材料。整体片材可以是金属片材例如铝或钢、木质层压板、挤出塑料片材和/或陶瓷材料。纤维增强复合材料通常包括碳纤维增强聚合物、玻璃纤维增强塑料、芳族聚酰胺纤维增强聚合物和天然纤维增强塑料。优选地,护套116、118是铝片或纤维增强聚合物复合材料。第一片和第二片护套116、118优选为约0.005英寸厚至约0.1英寸厚,这取决于采用结构100的应用。
当结构100包括蜂窝体102、振动阻尼涂层112、粘合剂层114以及第一片和第二片护套116、118时,该结构100可以为约0.125英寸厚至约4英寸厚。
结构100可以制成高达约4英尺宽和12英尺长的任何尺寸。结构100的一种典型应用是切割并制造成飞飞行器地板。
结构100转化为更好的振动阻尼。峰值损耗因子是结构的振动阻尼特性的度量,通过ASTM E756测量。当在ASTM E756下测试时,在环境室温和环境室内湿度下,相比于非阻尼结构,本发明的结构100(具有足够多的振动阻尼涂层112以将蜂窝体的密度增加至少4磅/立方英尺)提供阻尼结构100的损耗因子的变化至少为0.05、优选至少0.1、最优选至少0.15。例如在安装有由阻尼/涂覆结构100制成的地板的飞行器中,这可以显著地增加乘客的舒适度。
结构100还转化为更好的隔音效果。声音穿透损耗(STL)是结构的隔音性能的度量,其通过ASTM E90测量。本发明的结构100(具有足够多的振动阻尼涂层112以将蜂窝体的密度增加至少4磅/立方英尺)提供比未涂覆的基板高至少5分贝(dB)、优选至少10dB、最优选至少25dB的STL值。
振动阻尼涂层的量通常将结构的密度增加至少4磅/立方英尺、优选至少10磅/立方英尺、最优选至少20磅/立方英尺。所使用的振动阻尼涂层的总量受到蜂窝体的胞元中可用体积以及对飞机重量的不利影响的限制。在这些优选的量下,安装有由阻尼/涂覆结构100制成的地板的客舱中的噪音水平显著降低,而没有过度的由重量带来的损失。同样,安静的客舱增加了乘坐飞机的乘客的舒适度和满意度。
一种用振动阻尼涂层涂覆蜂窝体102和胞元108的内表面110的方法包括移动所述蜂窝体102通过向下级联瀑布的步骤,其中该瀑布包括振动阻尼涂层。通过将蜂窝体102设置在轮式推车(其设置在一对对置的轨道上)上,可以实现蜂窝体102通过向下级联瀑布(cascading waterfall)的移动。振动阻尼涂层112的瀑布由进入的前体集管提供,该前体集管具有设置在轨道上方的开槽末端。过量的振动阻尼涂层被捕获在收集盘中。通常,过量的振动阻尼涂层通过压缩气体(例如压缩空气)向下吹出并离开胞元108,吹过位于进来的振动阻尼涂层集管下游的压缩气体集管的末端向下设置的喷嘴。
在用振动阻尼涂层112涂覆蜂窝体102和胞元108的内表面的替代方法中,蜂窝体102保持静止,同时向下级联瀑布通过高架起重机相对于蜂窝体102横向移动。同样安装在起重机上的是向下设置的喷嘴,其将压缩气体向下吹入蜂窝体102中以从胞元108中吹出过量的振动阻尼涂层112。可选地,过量的振动阻尼涂层112被捕获在设置在蜂窝体102下方的收集盘中,并通过再循环管线和再循环泵被再循环到进来的振动阻尼涂层。
在用振动阻尼涂层112涂覆蜂窝体102和胞元108的内表面的另一替代方法中,蜂窝体102首先完全浸没在振动阻尼涂层材料112的池中。然后将蜂窝体102以受控的速率从该池中提起。一旦蜂窝体102完全脱离池,就将其置于具有基本多孔表面的支撑物上,并且在蜂窝体102上施加类似于上述安装的起重机的吹气喷嘴,以从胞元108吹出过量的振动阻尼涂层112。可选地,过量的振动阻尼涂层112被捕获在设置于蜂窝体102下方的收集盘中并被再循环。
可选地,振动阻尼涂层112可以被喷射到蜂窝体102上。
在用振动阻尼涂层112涂覆胞元108的内表面110之后,将蜂窝体102带到干燥罩,在该干燥罩中迫使强气流通过每个蜂窝体胞元108。在该干燥步骤中,通过蒸发除去振动阻尼涂层112中的大部分载液(水、任何其它挥发性液体等),并且振动阻尼涂层112的其余部分作为固体残留物的薄层附着在胞元108的内表面110上。该残留物必须充分附着到胞元108的内表面110,以便在随后处理蜂窝体102期间不会移位。优选地,蜂窝体102进一步在延长的时间经受约250°F的热空气,使得残留在胞元108的内表面110上的振动阻尼涂层112完全干燥和固化。
通常,通过调节振动阻尼涂层112的配方来控制保留在胞元108的内表面110上的振动阻尼涂层112的量。或者,如果需要更大量的振动阻尼涂层112,则可以在同一蜂窝体102上重复上述涂覆-干燥的循环。
在第一片和第二片护套116、118包括纤维增强塑料的情况下,通常使用浸渍有半固化热固性树脂(“预浸料”)的纤维增强材料,并且该第一片和第二片护套116、118与蜂窝体102的粘合可以通过固化预浸料中的树脂或通过使用粘合剂如聚酰胺或环氧粘合剂来实现。在第一片和第二片护套116、118由铝片和/或完全固化的层压物制成的情况下,粘合剂层114通常用于将该第一片和第二片护套116、118粘合到蜂窝体102上。该粘合步骤通常包括使结构100经受至少250°F的温度和至少30psi的压力至少30分钟。
实例1
水基振动阻尼组合物112的制备是通过组合约45%的去离子水;约1%的(Rockwood Additives,United Kingdom);约20%的4811(VinavilAmericas,FL);约0.1%的DF-37(Air Products and Chemicals,Inc.,PA);约4%的乙二醇醚EB(Ashland,Inc.,OH);约2%的FR-2(ICL,Israel);约2%的2100R(Great Lakes Solutions,CT);约0.3%的BurnExTM(NyacolNanotechnologies,MA);和约27%的200-HK(Imerys Performance Minerals,GA)。该组合物的固体含量约为45%,并且博勒飞粘度约为800cP(转子#3,10RPM,73°F)。
实例2
水基振动阻尼组合物112的制备是通过组合约45%的去离子水;约1%的约20%的4811;约0.1%的DF-37;约4%的乙二醇醚EB;约4%的2100R(Great Lakes Solutions,CT);约0.8%的三氧化二锑(Chemtura Corporation,CT);和约27%的200-HK(Imerys PerformanceMinerals,GA)。该组合物的固体含量为约45%,博勒飞粘度为约900cP(转子#3,10RPM,73℉)。
实例3
首先,通过在蜂窝体102上方移动振动阻尼涂层112的向下级联瀑布来用实例1的振动阻尼涂层112涂覆蜂窝体102形成结构100。接下来,向下设置的喷嘴将压缩气体向下吹入蜂窝体102中,从胞元108中吹出过量的振动阻尼涂层112。然后通过将涂覆的蜂窝体102置于干燥罩下来干燥和固化,在干燥罩中迫使强气流通过每个蜂窝体的胞元108。接下来,使涂覆的蜂窝体102进一步在延长的时间经受约250°F的热空气,使得残留在胞元108的内表面110上的振动阻尼涂层112完全干燥并固化。
然后将粘合剂114施加到蜂窝体102的上表面104和下表面106,然后将第一片和第二片护套116、118施加到粘合剂114上。然后使组装的结构100经受至少250°F的温度和至少30psi的压力至少30分钟。
尽管已经参照某些优选实施例相当详细地描述了本发明,但其它实施例也是可能的。例如虽然已经描述了该系统用于飞行器,但其它应用也是可能的,例如船艇、轮船和陆地车辆。因此,所附权利要求书的范围不应限于本文所包含的优选实施例的描述。
Claims (6)
1.一种用作飞机地板的结构,包括:
a)具有对置表面和多个开放胞元的蜂窝体,每个胞元具有内表面;和
b)在所有所述胞元的所有所述内表面上的振动阻尼涂层,所述振动阻尼涂层的厚度为0.002英寸至0.015英寸,所述振动阻尼涂层通过固化涂层组合物形成,所述涂层组合物包括:
(i)含有聚合物颗粒的丙烯酸类共聚物乳液,所述丙烯酸类共聚物乳液的玻璃化转变温度为-40℃至0℃,所述丙烯酸类共聚物乳液的粘度小于800厘泊,由3号博勒飞转子在22.78℃和10转/分钟下测量;
(ii)阻燃剂;和
(iii)由云母组成的振动阻尼填料,
其中所述云母与聚合物颗粒的重量比为2:1至8:1,其中所述云母包含多个颗粒,并且不超过3重量%的所述颗粒的尺寸大于300微米,并且其中所述结构包括足够多的振动阻尼涂层,使得所述结构满足以下条件中的至少一个:
a)相比于没有振动阻尼涂层的结构,通过ASTM E90测量的声音穿透损耗至少为5分贝;或
b)相比于没有振动阻尼涂层的结构,通过ASTM E756测量的振动阻尼损耗因子至少为0.05;
c)接合到所述蜂窝体的两个表面的粘合剂;
d)连接到接合至所述蜂窝体的一个表面上的粘合剂的第一片护套;和
e)连接到接合至所述蜂窝体的另一个表面上的粘合剂的第二片护套。
2.根据权利要求1所述的结构,其中,所述第一片护套和所述第二片护套由选自包括铝和纤维增强聚合物的组的材料形成。
3.根据权利要求1所述的结构,其中,所述第一片护套和所述第二片护套各自包括0.005英寸至0.1英寸的厚度。
4.根据权利要求1所述的结构,包括足够多的振动阻尼涂层以使该结构的密度相比于没有振动阻尼涂层的结构增加至少4磅/立方英尺。
5.根据权利要求1所述的结构,其中所述结构包括足够多的振动阻尼涂层,使得相比于没有振动阻尼涂层的结构,通过ASTM E90测量的声音穿透损耗至少为5分贝。
6.根据权利要求1所述的结构,其中所述结构包括足够多的振动阻尼涂层,使得相比于没有振动阻尼涂层的结构,通过ASTM E756测量的振动阻尼损耗因子至少为0.05。
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ZA201900260B (en) | 2019-10-30 |
BR112019001273A2 (pt) | 2019-05-07 |
JP2019531512A (ja) | 2019-10-31 |
MY192106A (en) | 2022-07-27 |
US20180022056A1 (en) | 2018-01-25 |
GB2567571B (en) | 2022-01-05 |
KR20190031511A (ko) | 2019-03-26 |
RU2748563C2 (ru) | 2021-05-26 |
GB2567571A (en) | 2019-04-17 |
AU2017300080B2 (en) | 2022-07-28 |
AU2017300080A1 (en) | 2019-02-07 |
GB201900616D0 (en) | 2019-03-06 |
SG11201900453WA (en) | 2019-02-27 |
RU2019101465A (ru) | 2020-08-24 |
RU2019101465A3 (zh) | 2020-12-31 |
JP6952772B2 (ja) | 2021-10-20 |
NZ750059A (en) | 2024-03-22 |
PH12019500140A1 (en) | 2019-07-29 |
MX2019000901A (es) | 2019-05-15 |
WO2018017303A1 (en) | 2018-01-25 |
CN109477535A (zh) | 2019-03-15 |
EP3488120A1 (en) | 2019-05-29 |
MA44562A1 (fr) | 2019-04-30 |
BR112019001273B1 (pt) | 2023-04-04 |
US10933605B2 (en) | 2021-03-02 |
CA3031646A1 (en) | 2018-01-25 |
MA44562B1 (fr) | 2022-06-30 |
KR102422424B1 (ko) | 2022-07-20 |
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