CN111093922A - 将负载的浆料注入纤维织构体的方法 - Google Patents
将负载的浆料注入纤维织构体的方法 Download PDFInfo
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- CN111093922A CN111093922A CN201880059662.2A CN201880059662A CN111093922A CN 111093922 A CN111093922 A CN 111093922A CN 201880059662 A CN201880059662 A CN 201880059662A CN 111093922 A CN111093922 A CN 111093922A
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- F01D9/02—Nozzles; Nozzle boxes; Stator blades; Guide conduits, e.g. individual nozzles
- F01D9/04—Nozzles; Nozzle boxes; Stator blades; Guide conduits, e.g. individual nozzles forming ring or sector
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- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
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- B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
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Abstract
一种制造由复合材料制成的部件的方法,所述方法包括以下步骤:‑将包含悬浮在液相中的至少一种难熔陶瓷颗粒(CR)粉末的浆料(BC)注入纤维织构体(10)中,‑过滤浆料的液相并将耐火陶瓷颗粒粉末保留在所述织构体内,以获得负载有耐火陶瓷颗粒的纤维预制件,‑通过处理存在于纤维织构体中的耐火陶瓷颗粒以在所述织构体中形成耐火基质来使纤维织构体致密化。该方法还包括在压力下注入浆料(BC)的步骤之前,用载液(FP)对纤维织构体(10)进行预饱和的步骤,该步骤包括将载液注入到所述织构体中。
Description
发明背景
本发明涉及用于制造部件的方法,所述部件由热结构复合材料制得,特别是由氧化物/氧化物或陶瓷基质复合物(CMC)类型制成,即包括由耐火陶瓷材料制成的纤维形成的纤维增强件,该耐火陶瓷材料被也是由耐火陶瓷材料制成的基质致密化。本发明更特别地涉及通过液体方法由氧化物/氧化物或CMC复合材料制造部件,该方法包括以下步骤:用浆料浸渍纤维增强件,例如在氧化物/氧化物复合材料的情况中用负载有氧化铝颗粒的浆料进行浸渍,或者在CMC复合材料的情况中用负载有碳化硅颗粒(SiC)的浆料进行浸渍。
浸渍步骤是通过在纤维增强件中加压注入负载的浆料(通常为10体积%至40体积%)(“浆料传递模塑(Slurry Transfer Moulding)”,即STM)来进行的。用于注入的浆料是轻负载的,以便特别是对于在纤维增强件的体积中输送填料具有稳定的粘度。在这种情况下,必须排出或过滤浆料的液相,以获得固体填料对纤维增强件中存在的残余孔隙的最佳填充。在文献WO 2016/102839中特别描述了这种方法。
在SiC/SiC材料的情况中,对加载的浆料进行注入和过滤的步骤是在纤维坯料上进行的,该纤维坯料通过三维(3D)编织获得,并通过化学气相渗透(CVI)进行了固结或预致密化。具有固定孔隙网络的不可压缩坯料的纱间总残余孔隙率为25体积%至45体积%。然而,3D纤维坯料或由纤维层片堆叠形成的坯料具有复杂的孔隙网络,这导致难以监测负载的浆料对纤维坯料的填充。因此,将负载的悬浮液注入或过滤到纤维织构体中的步骤没有得到很好的控制,这导致在最终部件中存在孔隙。
图4示出了根据现有技术的由SiC/SiC复合材料制成的部件300的截面的两张显微照片,即此处是通过互锁编织的方式在纬纱层和经纱层之间进行3D编织而形成并且被SiC基质320致密化的SiC纤维增强件310。部件300的制造方式与上述相同,也就是说,通过从SiC纤维织构体的薄片或表面注入负载有SiC颗粒的浆料来制造,该注入在类似于众所周知的称为“RTM”(“树脂传递模塑(Resin Transfer Moulding)”)的注塑工艺的条件下进行。从图4中可以看出,部件300包括纱间孔隙330,其对应于初始存在于纤维增强件中但尚未填充SiC基质的孔隙。
在氧化物/氧化物材料的情况中,在具有双孔隙网络(即纱内孔隙网络和纱间孔隙网络)的纤维织构体中注入负载的浆料。同样,由于进入纤维织构体的整个孔隙网络的复杂性,已经观察到注入和过滤存在困难,导致在所得材料中存在孔隙或缺少基质的区域。
发明目的和概述
本发明的目的在于克服上述缺点并提出一种解决方案,该解决方案使得可以由具有复杂和/或厚的几何结构的纤维织构体,利用复合材料,特别是氧化物/氧化物或CMC类型的复合材料来制造部件,并且该制造通过对固体颗粒在纤维织构体中沉积和分布的良好监控而以可靠且可重复的方式进行,从而获得具有非常低的残余孔隙率并因此改善了性能的材料。
为此,本发明提供一种制造由复合材料制成的部件的方法,所述方法包括以下步骤:
-由耐火陶瓷纤维形成纤维织构体,
-将纤维织构体放入注塑模具的模腔中,
-将包含悬浮在液相中的至少一种难熔陶瓷颗粒粉末或难熔陶瓷前体颗粒的浆料注入纤维织构体中,
-过滤浆料的液相并将耐火陶瓷颗粒粉末或耐火陶瓷前体颗粒保留在所述织构体中,以获得负载有耐火陶瓷颗粒或耐火陶瓷前体颗粒的纤维预制件,
-通过处理存在于纤维织构体中的耐火陶瓷颗粒以在所述织构体中形成耐火基质来使纤维织构体致密化,
其特征在于,在将纤维织构体放置在注塑模具的模腔中的步骤之后,并且在压力下将浆料注入的步骤之前,该方法包括以下步骤:将纤维织构体用载液预饱和,包括将载液注入所述织构体中。
通过在将负载的浆料注入纤维织构体之前,先用载液对纤维织构体进行预饱和,建立一个瞬态状态,由此可以很好地监控织构体内的填料传递机制。因此,这允许用耐火陶瓷颗粒优化织构体的填充。预饱和步骤可以克服在将负载的浆料注入的过程中纤维织构体的润湿性问题。从注入开始就通过颗粒在已经存在于织构体中的载液中的稀释来促进存在于纤维织构体中的孔隙的填充。
根据本发明方法的特定特征,载液对应于浆料的液相。这样可以克服织构体可能存在的润湿性问题以及悬浮在浆料中的颗粒的可能的不稳定问题。
根据本发明方法的另一个特定特征,载液预饱和步骤和浆料注入步骤是连续相连的。因此,在优化由预饱和步骤建立的瞬态状态的影响的同时,缩短了部件的制造时间。
根据本发明的方法的另一特定特征,当模腔中的压力达到预定压力值时,停止预饱和步骤。因此,可以监控和验证预饱和步骤,以在最佳时间注入浆料。
根据本发明的方法的另一特定特征,在预饱和步骤期间,以第一确定流量注入载液,并且在负载的浆料注入步骤期间,以第二确定流量注入所述浆料,该第二确定流量类似于第一流量或不同于第一流量。
根据本发明方法的另一个特定特征,在纤维织构体形成步骤中,纱线以三维或多层编织的方式编织。
织构体的纱线可以是由以下一种或几种材料制成的纤维形成的纱线:氧化铝、莫来石、二氧化硅、铝硅酸盐、硼硅酸盐、碳化硅和碳。
耐火陶瓷颗粒可由选自以下的材料制成:氧化铝、莫来石、二氧化硅、铝硅酸盐、铝磷酸盐、氧化锆、碳化物、硼化物和氮化物。
在一个示例性实施方式中,所获得的由复合材料制成的部件可以构成涡轮机叶片或者甚至构成后体部分(afterbody part),燃烧室,襟翼,后燃烧臂,涡轮环,混合器,分配器等。
附图说明
本发明的其它特点和优势通过下文关于本发明具体实施方式的描述并参照附图而显而易见,所述具体实施方式以非限制示例的形式给出,附图中:
-图1是示意性截面图,示出了根据本发明的一个实施方式的用载液对纤维织构体进行预饱和的步骤,
-图2是示意性截面图,示出了将负载的浆液注入图1的纤维织构体中以及将浆料的液相排出的步骤。
-图3呈现了根据本发明方法制造的由SiC/SiC复合材料制成的部件的两张显微照片。
-图4呈现了根据现有技术制造的由SiC/SiC复合材料制成的部件的两张显微照片。
发明详述
根据本发明的用于制造由复合材料,特别是由氧化物/氧化物或CMC类型的复合材料制成的部件的方法开始于获得旨在形成部件的增强件的纤维织构体10。
纤维结构是通过已知的方式用提花型织机(Jacquard type loom)进行编织来实现的,在该提花型织机上,将一束经纱或股线以多层形式布置,经纱通过纬纱结合/粘合,反之亦可。纤维织构体可以通过堆叠以下结构来实现:由二维编织(2D)得到的层片或折叠物,或者纱线或缆线的单向片(UD),或者通过在不同方向上叠加几片UD并将这些UD片结合/粘合在一起所获得的多向片(nD),该堆叠/结合/粘合例如通过缝制、化学粘合剂或针刺来实现。
纤维织构体也可通过三维(3D)编织直接以单件形式实现。“二维编织”在这里是指传统的编织方式,通过该方式,每根纬纱从单个经纱层的纱线的一侧穿至另一侧,反之亦可。在2D纤维织构体(即通过堆叠2D层片或折叠物而获得的织构体)中注入负载的浆料的情况下,本发明特别适用于具有显著厚度的2D织构体,即厚度至少为0.5mm,优选至少1mm的2D纤维织构体。
“三维编织”或“3D编织”或者甚至“多层编织”是指一种编织模式,通过该编织模式,至少一些纬纱将几层经纱上的经纱以编织的方式结合在一起,该编织的方式对应于可以特别从以下编织中选择的编织:互锁编织(interlock)、多帆布编织(multi–canvas)、多缎纹编织(multi-satin)和多斜纹编织(multi-twill)。
“互锁编织或织物”在这里指3D编织,其中每层经纱将几层纬纱结合在一起,而同一经列的所有纱线在织物平面内的运动相同。
"多帆布编织或织物"在这里是指具有几层纬纱的3D编织,其每层的基本编织等同于常规帆布类型的编织,但编织的某些点将几层纬纱结合在一起。
"多缎纹编织或织物"在这里是指具有几层纬纱的3D编织,其每层的基本编织等同于常规的缎纹类型的编织,但是编织的某些点将几层纬纱结合在一起。
"多斜纹编织或织物"在这里是指具有几层纬纱的3D编织,其每层的基本编织等同于常规的斜纹类型的编织,但是编织的某些点将几层纬纱结合在一起。
3D织构体或通过堆叠2D层片或UD片形成的织构体具有复杂的几何结构,其中很难引入和均匀分布悬浮的固体颗粒。本发明的方法也非常适合将负载的浆料引入3D编织纤维织构体中。
用于编织旨在形成复合材料制成的部件的纤维增强件的纤维织构体的纱线可具体由纤维制成,所述纤维由以下材料中的一种制成:氧化铝、莫来石、二氧化硅、铝硅酸盐、硼硅酸盐、碳化硅、碳或这些材料中的几种的混合物。
在此处描述的示例中,纤维织构体10是通过在SiC纤维的多根纱线之间进行3D编织实现的,该织构体在编织后通过SiC的化学气相渗透而得以固结。纤维织构体10在此旨在形成由SiC/SiC复合材料制成的部件的纤维增强件(由SiC基质致密化的SiC纤维增强件)。
图1示出了根据本发明的注塑模具100,其包括外壳110和底部111,它们一起形成模腔113。过滤器120存在于外壳110的底部111上,底部111包括开口1110。外壳110的上部由盖112封闭,该盖112包括注入端口1120,该注入端口1120一方面连接到载液注入系统140,另一方面连接到负载的浆料的注入系统150,但是通过多个通向模腔113中的注入端口注入载液和负载的浆料的情况也不会背离本发明的范围。
更具体地,载液注入系统在此包括含载液FP的储器141,并且其出口导管144连接到蠕动泵142的入口。蠕动泵142的出口通过导管145和146连接到注入端口1120,在导管145和146之间插入有阀143。负载的浆料的注入系统150在此包括注入罐151,注入罐151界定了容纳负载的浆料BC的室1510,注入罐151还配备有活塞1511和与所述活塞相对的排出口1512,该排出口1512通过导管153和154连接到注入端口1120,在导管153和154之间插入有阀152。
一旦获得纤维织构体10,就将其放置在注塑模具100中,如下所述,其允许在纤维织构体中沉积耐火陶瓷颗粒或耐火陶瓷前体的颗粒。
图1示出了用根据本发明的载液FP将纤维织构体10预饱和的步骤。载液FP尤其可以选自以下液体:具有不同pH的水,醇(例如乙醇,PVA),酯(例如乙酸乙酯),酮(例如丙酮,甲乙酮),烷烃(例如十六烷),烯烃(例如甲苯),THF,聚乙烯醇(PVA),聚维酮(PVP)。载液优选具有与负载的浆料BC中存在的液相相同的性质。在这里描述的示例中,载液FP对应于pH在9和10之间的水。在该步骤中,负载的浆料注入系统150不工作,注入罐151不输送浆料BC,并且阀152关闭。在载液注入系统的一侧,载液FP通过蠕动泵142以恒定的流量输送到注入端口1120中,阀143处于打开状态。载液以介于2cm3/分钟和1500cm3/分钟之间的流量注入。在此处描述的示例中,由水组成的载液以100cm3/分钟的流量输送。所注入的载液的流量的调节可以用蠕动泵以外的其他手段来进行,例如,使用配备有活塞并且该活塞具有被监控的流量的注射器来进行。控制蠕动泵,从而至少以确定的流量值监控注入模腔113中的载液FP的流量。
当认为纤维织构体中的载液饱和完成时,即当模腔113中的压力(载液注入系统的压力损失)达到稳定阈值(例如600毫巴)时,预饱和步骤结束。在预饱和步骤结束时实现压力稳定阈值的测量可以通过压力传感器160(例如压力计)进行,该压力传感器位于注塑模具100的注入端口1120处。模腔中压力的测量也可以通过放置在模腔表面上的压力传感器(图1和2中未显示)进行。
一旦完成预饱和步骤,就如图2所示进行将负载的浆料BC注入纤维织构体10的步骤。在此处描述的示例中,浆料BC包含20%体积的SiC颗粒,其平均直径D50为0.5μm到0.9μm,并且悬浮在pH值为9到10的水中。该颗粒还可以具有微米(>10μm)或亚微米尺寸。
在该步骤期间,将负载的浆料BC在监控的压力或流量下注入模腔113。在该步骤期间,载液注入系统140不工作,蠕动泵142停止并且阀143关闭。在负载的浆料注入系统150的一侧,浆料BC由注入罐151以调节的流量输送到注入端口1120中,阀152打开,此处浆料BC以最小的流量2cm3/分钟注入。流量的调节由注入罐151的活塞1511控制,从而以低于载液注入流量的流量输送负载的浆料。在图2中,浆料BC在压力下通过注入端口1120注入。
如图2中所示,由于过滤器120,存在于浆料BC中的难熔陶瓷颗粒CR(这里是SiC颗粒)被保留在纤维织构体10中。过滤器120被校准以保留存在于浆料中的难熔氧化物颗粒,而浆料中的液体通过开口1110排出。因此,难熔氧化物颗粒通过在织构体中的沉降而逐渐沉积。过滤器120例如可以由多孔材料制成,该多孔材料例如微孔聚四氟乙烯(PTFE),例如由公司出售的“微孔PTFE”产品。例如,为了生产多孔材料的一部分,可以使用由公司销售的孔径在1μm至2μm之间的PM材料0130,由公司销售的PM材料0510,或材料。通常,能够保留注入的颗粒的任何装置,例如金属格栅或陶瓷过滤器,都可以用于该过滤步骤。与负载的浆料BC的注入结合,可以例如利用初级真空泵(图2中未示出)通过开口1110在外壳110的底部111的外侧上进行泵吸P,以改善浆料通过纤维织构体10的迁移以及浆料液相的过滤。
在进行了注入和过滤步骤后,获得了负载有耐火陶瓷颗粒(在这种情况下为SiC颗粒)的纤维预制件。然后将所获得的预制件干燥并脱模,该预制件能够在脱模后保持模腔中采用的形状。
然后通过处理预制件中存在的颗粒使预制件致密化。例如在氧化物颗粒的情况下,该处理包括例如在空气中在1000℃至1200℃之间的温度下对颗粒进行烧结热处理,以烧结颗粒并因此在纤维预制件孔隙中形成耐火陶瓷基质。在SiC颗粒的情况下,如在此描述的示例中,通过用熔融硅渗透预制件(“熔融渗透”工艺,即MI),从而使SiC颗粒被硅浸渍,由此形成SiC基质。这提供了由复合材料(这里是SiC/SiC复合材料)制成的部件,其具有由纤维预制件形成的纤维增强件,该纤维增强件具有高的基质体积比,并且耐火陶瓷基质在整个纤维增强件中均匀分布。
图3示出了根据本发明方法制造的由SiC/SiC复合材料制成的部件200的截面(纬线方向上的截面:照片的长度对应于纬线方向)的两张显微照片,本发明方法包括:
-通过以互锁编织在纬纱层和经纱层之间进行3D编织,在由此形成的SiC纤维中实现纤维织构体;
-通过SiC的化学气相渗透来使纤维织构体预致密化或固结;
-将固结的纤维织构体放置在类似于上述模具100的注塑模具中;
-用载液对纤维织构体进行预饱和,包括以100cm3/分钟的流量将pH值在9和10之间的水注入织构体中;
-以2cm3/分钟的流量将负载的浆料注入到纤维织构体中,该浆料由悬浮在pH值为9至10的水中的SiC颗粒组成;
-过滤浆料的液相,以局部地使填料在织构体中积聚,并因此增加结构中的填料比率;
-通过用熔融硅渗透以形成SiC基质来使预制件致密化。
在图3中,所得部件200包括由SiC纱线形成并由SiC基质220致密化的纤维增强件210。如图3所示,部件200没有可见的纱间孔隙或者几乎没有可见的纱间孔隙,这证明了纤维织构体预饱和步骤在随后注入负载的浆液的过程中优化织构体填充的有效性。
本发明的方法不限于注入包含悬浮在水中的SiC颗粒的浆料。更一般地,所使用的浆料可以是包含平均粒径在0.1μm至10μm之间的耐火陶瓷颗粒的悬浮液。在注入之前,浆料中的耐火陶瓷颗粒的体积含量可以在1体积%至50体积%之间,优选在20体积%至35体积%之间。耐火陶瓷颗粒可包括选自以下的材料:氧化铝,莫来石,二氧化硅,铝硅酸盐,铝磷酸盐,碳化物,硼化物,氮化物以及这些材料的混合物。根据其基本组成,耐火陶瓷颗粒还可以与以下材料的颗粒混合:氧化铝,氧化锆,铝硅酸盐,稀土氧化物,稀土硅酸盐(例如可用于环境屏障或热屏障),或任意其他可以使获得的复合材料部件具有功能的填料,例如碳黑、石墨或碳化硅。
浆料的液体介质或液相还可以例如包括具有酸性pH(即,pH小于7)的水相和/或包括例如乙醇的醇相。该浆料可以包括酸化剂,例如硝酸,并且液体介质的pH可以例如在1.5至4之间。该浆料还可以包括有机粘合剂,例如聚乙烯醇(PVA),其特别可溶于水。更一般地,浆料可以包含:
-载液,
-分散剂(例如合适的pH值),
-粘合剂(例如PVA),
-增塑剂(例如PVA),
-消泡剂,
-润湿剂。
通过用碳化硅和/或碳的纤维获得纤维织构体,并使用负载有碳化物颗粒(例如SiC、B4C或TiC)、硼化物(例如TiB2)、氮化物(例如Si3N4)或硅化物(例如TiSi2)的浆料,可以以相同的方式获得由氧化物/氧化物材料之外的CMC复合材料制成的部件。
Claims (9)
1.一种制造由复合材料制成的部件的方法,所述方法包括以下步骤:
-由耐火陶瓷纤维形成纤维织构体(10),
-将所述纤维织构体(10)放入注塑模具(100)的模腔(113)中,
-将包含悬浮在液相中的至少一种难熔陶瓷颗粒粉末或难熔陶瓷前体(CR)颗粒的浆料(BC)注入纤维织构体(10)中,
-过滤浆料的液相并将耐火陶瓷颗粒粉末或耐火陶瓷前体颗粒保留在所述织构体内,以获得负载有耐火陶瓷颗粒或耐火陶瓷前体颗粒的纤维预制件,
-通过处理存在于纤维织构体中的耐火陶瓷颗粒以在所述织构体中形成耐火基质来使纤维织构体致密化,
其特征在于,在将纤维织构体放置在注塑模具的模腔中的步骤之后,并且在压力下将浆料(BC)注入的步骤之前,所述方法包括以下步骤:将纤维织构体(10)用载液(FP)预饱和,包括将载液注入所述织构体中。
2.如权利要求1所述的方法,其中,所述载液(FB)对应于浆液(BC)的液相。
3.如权利要求1或2所述的方法,其中,载液(FP)预饱和步骤和浆液(BC)注入步骤是连续相连的。
4.如权利要求1至3中任一项所述的方法,其中,当模腔(113)中的压力达到预定压力值时,停止预饱和步骤。
5.如权利要求1至4中任一项所述的方法,其中,在预饱和步骤期间,以第一确定流量注入载液(FP),并且在浆料(BC)注入步骤期间,以第二确定流量注入所述浆料,所述第二确定流量类似于第一流量或不同于第一流量。
6.如权利要求1至5中任一项所述的方法,其中,在纤维织构体形成步骤(10)期间,纱线以三维或多层编织的方式编织。
7.如权利要求1至6中任一项所述的方法,其中,所述纤维织构体(10)的纱线由纤维形成,所述纤维由一种或几种以下材料制成:氧化铝、莫来石、二氧化硅、铝硅酸盐、硼硅酸盐、碳化硅和碳。
8.如权利要求1至7中任一项所述的方法,其中,所述耐火陶瓷颗粒由选自以下的材料制成:氧化铝、莫来石、二氧化硅、铝硅酸盐、铝磷酸盐、氧化锆、碳化物、硼化物和氮化物。
9.如权利要求1至8中任一项所述的方法,其中,所获得的由复合材料制成的部件构成涡轮机叶片、后体部分、燃烧室、襟翼、后燃烧臂、涡轮环、混合器或分配器。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1758744A FR3071245B1 (fr) | 2017-09-21 | 2017-09-21 | Procede d'injection d'une barbotine chargee dans une texture fibreuse |
FR1758744 | 2017-09-21 | ||
PCT/FR2018/052287 WO2019058054A1 (fr) | 2017-09-21 | 2018-09-19 | Procédé d'injection d'une barbotine chargée dans une texture fibreuse |
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EP (1) | EP3684575B1 (zh) |
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BR (1) | BR112020005458B1 (zh) |
CA (1) | CA3074745A1 (zh) |
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CN117545606A (zh) * | 2021-06-15 | 2024-02-09 | 赛峰航空陶瓷技术公司 | 使用在纤维预制件中就地生成的过滤器注入陶瓷粉末的方法 |
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FR3080113B1 (fr) * | 2018-04-13 | 2020-05-01 | Safran Ceramics | Procede de fabrication d'une piece en materiau composite par injection d'une barbotine chargee dans une texture fibreuse |
FR3096299B1 (fr) * | 2019-05-23 | 2023-05-12 | Safran | Procédé de fabrication d’une pièce en matériau composite par injection d’une barbotine chargée dans une texture fibreuse |
US20210355038A1 (en) * | 2020-05-12 | 2021-11-18 | Goodrich Corporation | Methods and systems for in-plane slurry infiltration of composite preforms |
CN114804905B (zh) * | 2022-05-10 | 2023-12-01 | 山东工业陶瓷研究设计院有限公司 | 一种复合材料制备方法 |
CN115008777B (zh) * | 2022-06-10 | 2023-06-30 | 安徽省国盛量子科技有限公司 | 一种温度传感宽场探头的制作方法 |
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- 2018-09-19 RU RU2020112857A patent/RU2764203C2/ru active
- 2018-09-19 EP EP18796704.7A patent/EP3684575B1/fr active Active
- 2018-09-19 US US16/649,372 patent/US11255203B2/en active Active
- 2018-09-19 WO PCT/FR2018/052287 patent/WO2019058054A1/fr unknown
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- 2018-09-19 JP JP2020516809A patent/JP6871482B2/ja active Active
- 2018-09-19 CN CN201880059662.2A patent/CN111093922B/zh active Active
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BR112020005458B1 (pt) | 2023-04-25 |
EP3684575B1 (fr) | 2021-08-18 |
US11255203B2 (en) | 2022-02-22 |
RU2020112857A3 (zh) | 2021-11-17 |
RU2020112857A (ru) | 2021-10-21 |
CA3074745A1 (fr) | 2019-03-28 |
EP3684575A1 (fr) | 2020-07-29 |
FR3071245B1 (fr) | 2019-09-20 |
JP6871482B2 (ja) | 2021-05-12 |
RU2764203C2 (ru) | 2022-01-14 |
WO2019058054A1 (fr) | 2019-03-28 |
JP2020534243A (ja) | 2020-11-26 |
CN111093922B (zh) | 2022-07-29 |
US20200269468A1 (en) | 2020-08-27 |
BR112020005458A2 (pt) | 2020-09-24 |
FR3071245A1 (fr) | 2019-03-22 |
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