CN111373061A - 冷轧退火钢板及其制造方法 - Google Patents
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Abstract
本发明涉及冷轧热处理钢板,以重量百分比计,所述冷轧热处理钢板由具有包含以下的组成的钢制成:C:0.03%至0.25%;Mn:3.5%至8%;Si:0.1%至2.0%;Al:0.03%至2.0%;Ti<0.080%;Nb≤0.080%;V<0.2%;V+Ti+Nb>0.01%;S<0.010%;P<0.020%;N<0.008%,以及任选地包含以重量百分比计的以下元素中的一者或更多者:Mo:0.1%至0.5%;Cr:0.01%至1%;B:0.0005%至0.004%,组成的剩余部分为铁和由熔炼产生的不可避免的杂质,以表面分数计,所述冷轧钢板具有由以下组成的显微组织:‑10%至30%的残余奥氏体,所述残余奥氏体作为具有至少3的长宽比的膜以及作为马氏体奥氏体岛存在,少于8%的这样的马氏体奥氏体岛具有大于0.5μm的尺寸;‑至多10%的新鲜马氏体;以及‑包含选自铌、钛和钒中的至少一种元素的析出物的回收马氏体。本发明还涉及冷轧热处理钢板的制造方法。
Description
本发明涉及具有高的延性和可成形性的高强度钢板以及涉及获得这样的钢板的方法。
为了制造各种零件例如用于机动车辆的车身结构构件和车身板件的零部件,已知使用由DP(双相)钢或TRIP(相变诱导塑性)钢制成的板。
考虑到全球环境保护,为了减轻机动车的重量以改善其燃料效率,期望拥有具有改善的屈服强度和抗拉强度的板。但是这样的板还必须具有良好的延性和良好的可成形性并且更具体地具有良好的拉伸凸缘性。
因此本发明的目的是提供这样的钢板:其达到至少700MPa的屈服强度、至少900MPa的抗拉强度、至少12%的均匀延伸率和至少20%的扩孔率。
本发明的目的通过提供根据权利要求1的钢板来实现。所述钢板还可以包括权利要求2至12中任一项的特征。另一个目的通过提供根据权利要求13的方法来实现。所述方法还可以包括权利要求14至15中任一项的特征。另一个目的通过提供根据权利要求16或17的点焊接头来实现。
现在将在不引入限制的情况下通过实例对本发明进行详细描述和举例说明。
在下文中,Ae1表示这样的平衡转变温度:低于所述平衡转变温度,奥氏体完全不稳定;Ae3表示这样的平衡转变温度:高于所述平衡转变温度,奥氏体完全稳定;Ar3表示这样的温度:直至所述温度,在冷却时显微组织保持完全奥氏体;Tθ表示这样的温度:高于所述温度,渗碳体在加热时得到溶解;以及Ms表示马氏体开始温度,即在冷却时奥氏体开始转变成马氏体的温度。
除非另外指出,否则所有的组成百分比均以重量百分比(重量%)给出。
以重量百分比计,根据本发明的钢的组成包含:
-0.03%≤C≤0.25%,以用于确保满意的强度并改善残余奥氏体的稳定性,这是获得足够的延伸率所必需的。优选地,碳含量高于或等于0.1%。如果碳含量太高,则热轧板对于冷轧而言太硬并且可焊接性不足。如果碳含量低于0.03%,则抗拉强度将无法达到目标值。
-3.5%≤Mn≤8%,以用于确保满意的强度并实现至少部分奥氏体的稳定,以获得足够的延伸率。低于3.5%,最终组织包含不足的残余奥氏体分数,以及残余奥氏体中的不足的Mn含量,因此无法实现期望的延性和强度的组合。限定最大量以避免具有对延性不利的偏析问题。优选地,锰含量高于或等于3.7%。
-0.1%≤Si≤2.0%以及0.03%≤Al≤2.0%。根据本发明,Si和Al一起发挥重要作用:在低于平衡转变温度Ae3下冷却时,硅使渗碳体的析出延迟。因此,至少0.1%的Si添加有助于使足够量的残余奥氏体稳定。Si进一步提供固溶强化并且在由于部分马氏体转变之后立即进行的再加热和保持步骤引起的碳从马氏体再分布到奥氏体期间使碳化物的形成延迟。在太高的含量下,在表面处形成硅氧化物,这损害钢的可涂覆性。因此,Si含量小于或等于2.0%。
铝是对于在加工期间使液相的钢脱氧非常有效的元素。此外,Al是提高钢的Ae1和Ae3温度的α-形成元素(alpha-former element)。因此,由于添加了至少0.03%的Al,因此临界区域(intercritical domain)(即Ae1至Ae3)为有利于Mn在奥氏体中配分的温度范围,如以下进一步详细描述的。为了避免夹杂物的出现、避免氧化问题以及确保材料的淬透性,Al含量不高于2.0%,优选地不高于1.2%。
根据本发明的钢必须以至少0.01%的最小组合含量包含选自铌、钛和钒中的至少一种元素。这样的添加将通过经由析出限制马氏体板条的生长而使回收马氏体(recoveredmartensite)强化。
-Nb≤0.080%,可以进行添加以在热轧期间精炼奥氏体晶粒并且提供析出强化。在一个优选实施方案中,添加的铌的最小量为0.010%。大于0.080%的添加下,无法确保屈服强度、延伸率和扩孔率在期望的水平。
-Ti≤0.080%,可以进行添加以提供析出强化。在一个优选实施方案中,添加的钛的最小量为0.010%。然而,当Ti的量大于或等于0.080%时,无法确保屈服强度、延伸率和扩孔率在期望的水平。
-V≤0.2%,可以进行添加以提供析出强化。在一个优选实施方案中,添加的钒的最小量为0.010%。然而,当V的量大于或等于0.2%时,无法确保屈服强度、延伸率和扩孔率在期望的水平。
钢的组成的剩余部分为铁和由熔炼产生的杂质。在这方面,至少考虑Ni、Cu、S、P和N作为剩余元素,其为不可避免的杂质。因此,其含量对于Ni小于0.05%、对于Cu小于0.03%、对于S小于0.010%、对于P小于0.020%以及对于N小于0.008%。
可以向根据本发明的钢的组成中任选地添加一些元素:
-0.1%≤Mo≤0.5%。钼提高淬透性,使残余奥氏体稳定,因此在配分期间减少奥氏体分解,以及减少可能由高的锰含量导致的并且对扩孔率不利的中心偏析。此外,Mo有助于使组织精细。考虑到之后所寻求的特性,大于0.5%,Mo的添加是昂贵且不高效的。
-0.01%≤Cr≤1%,以延迟碳化物的溶解并使残余奥氏体稳定。允许最多1%的铬,注意高于饱和效应,添加铬既无用又昂贵。
-0.0005%≤B≤0.004%,从而提高钢的可淬火性。
现在将描述根据本发明的冷轧热处理钢板的显微组织。
以表面分数计,冷轧热处理钢板具有由以下组成的组织:
-10%至30%的残余奥氏体,所述残余奥氏体作为具有至少3的长宽比的膜以及作为马氏体奥氏体岛(所谓的MA岛)存在,少于8%的这样的MA岛具有大于0.5μm的尺寸,
-至多10%的新鲜马氏体,以及
-包含选自铌、钛和钒中的至少一种元素的析出物的回收马氏体。
表面分数和长宽比通过以下方法确定:从冷轧热处理中切割试样,用本身已知的试剂进行抛光和蚀刻,以露出显微组织。此后通过耦合至电子背散射衍射(“EBSD”)装置和透射电子显微术(TEM)的放大倍率大于5000x的光学或扫描电子显微镜例如具有场发射枪的扫描电子显微镜(“FEG-SEM”)来检查该部分。
各构成要素的表面分数的确定通过本身已知的方法利用图像分析来进行。例如,残余奥氏体分数通过X射线衍射(XRD)来确定。
冷轧热处理钢板的显微组织包含至少10%的奥氏体(其在室温下为残余奥氏体)。当以至少10%的表面分数存在时,残余奥氏体有助于提高延性。大于30%下,要求的根据ISO 16630:2009的扩孔率HER的水平低于20%。
残余奥氏体作为具有至少3的长宽比的膜以及作为MA(马氏体奥氏体)岛存在,少于8%的这样的MA岛具有大于0.5μm的尺寸。
必须遵守残余奥氏体膜的长宽比的具体最小值和具有大于0.5μm的尺寸的MA岛的最大百分比,以获得所需水平的根据ISO 16630:2009的扩孔率HER。
在一个优选实施方案中,根据本发明的冷轧热处理钢板使得具有大于0.5μm的尺寸的MA岛与奥氏体膜之间的分数比低于1.0,或甚至更好地低于0.5。
在另一个优选实施方案中,根据本发明的冷轧热处理钢板使得少于5%的这样的MA岛具有大于0.5μm的尺寸。
在另一个优选实施方案中,根据本发明的冷轧热处理钢板使得具有大于3的长宽比的奥氏体膜的表面分数为至少8%。
冷轧热处理钢板的显微组织包含至多10%的新鲜马氏体。实际上,新鲜马氏体的分数高于10%将导致根据ISO 16630:2009的扩孔率HER低于20%。
在另一个优选实施方案中,根据本发明的冷轧热处理钢板使得新鲜马氏体的表面分数低于5%。
冷轧热处理钢板的显微组织包含含有选自铌、钛和钒中的至少一种元素的析出物的回收马氏体。如果不存在这样的析出物,则钢种不可以达到本发明针对的抗拉强度的最小值。
在通过扫描电子显微术(SEM)和电子背散射衍射(EBSD)观察到的经本身已知的试剂(例如Nital试剂)抛光和蚀刻的部分上,可以将回收马氏体与新鲜马氏体区分开。
根据本发明的钢板可以通过任何适当的制造方法来制造并且本领域技术人员可以限定方法。然而,优选使用根据本发明的方法,其包括以下步骤:
可以通过以下制造厚度为例如1.8mm至6mm的热轧板:铸造具有如上所述的组成的钢以获得板坯,在1150℃至1300℃的温度T再加热下对板坯进行再加热,以及对经再加热的板坯进行热轧(轧制终了温度高于Ar3)以获得热轧钢。
轧制终了温度优选地为至多1000℃,以避免奥氏体晶粒的粗化。
然后使热轧钢以例如1℃/秒至120℃/秒的冷却速率冷却,并在20℃至600℃的温度T卷取下进行卷取。
在卷取之后,可以对板进行酸洗。
然后使热轧钢板进行退火以改善热轧钢板的可冷轧性和韧性,以及以提供适用于制造具有高机械特性特别是高强度和高延性的冷轧热处理钢板的热轧退火钢板。
在一个优选实施方案中,对热轧钢板进行的退火为在500℃至680℃的温度下进行1000秒至50000秒的分批退火。
然后任选地对热轧退火钢板进行酸洗。
然后对热轧退火钢板进行冷轧以获得厚度可以为例如0.7mm至3mm,或甚至更好地在0.8mm至2mm的范围内的冷轧钢板。
冷轧压下率优选为20%至80%。低于20%,不利于在随后热处理期间的再结晶,这可能损害冷轧热处理钢板的延性。高于80%,在冷轧期间存在边缘开裂的风险。
然后在连续退火线上对冷轧钢板进行热处理。
热处理包括以下步骤:
-将冷轧钢板再加热至高于860℃的第一退火温度并将冷轧钢板在所述退火温度下保持30秒至600秒的保持时间,以在退火时获得完全奥氏体组织,
至第一退火温度的再加热速率优选为1℃/秒至200℃/秒。
-使冷轧钢板以0.5℃/秒至200℃/秒的冷却速率淬火至20℃至Ms-50℃的淬火温度,并在所述淬火温度下保持1秒至200秒的保持时间,
选择冷却速率以避免在冷却时形成珠光体。对于钢的各特定组成和各组织,本领域技术人员知晓如何通过膨胀测定法确定奥氏体的Ms起始转变点。
在该淬火步骤期间,奥氏体部分地转变成马氏体。
如果淬火温度低于20℃,则最终组织中的回收马氏体的分数太高而不能使大于10%的足够量的残余奥氏体稳定。此外,如果淬火温度高于Ms-50℃,则最终组织中的回收马氏体的分数太低而不能获得期望的扩孔率。
-任选地将淬火板在淬火温度下保持1秒至200秒,优选地3秒至7秒的保持时间,以避免在马氏体中形成ε碳化物(这将导致钢的延伸率降低)。
-将冷轧钢板再加热至Tθ至720℃的第二退火温度,并将冷轧钢板在所述退火温度下保持100秒至2000秒的时间,
在该第二退火步骤期间,渗碳体得到溶解并且碳和Mn从马氏体扩散至奥氏体,由此实现奥氏体的碳和Mn的富集并对马氏体进行回收。
-任选地在温度低于或等于480℃的浴中对所述板进行热浸涂。可以使用任何种类的涂层并且特别是锌或锌合金(例如锌-镍合金、锌-镁合金或锌-镁-铝合金)、铝或铝合金(例如铝-硅)。
-紧接在第二退火步骤之后,或紧接在热浸涂步骤(如果进行的话)之后,将冷轧钢板冷却至室温,以获得冷轧热处理钢板。冷却速率优选地高于1℃/秒,例如为2℃/秒至20℃/秒。
在该冷却步骤期间,部分奥氏体可以转变成新鲜马氏体。然而,由于奥氏体经碳和锰而稳定,因此新鲜马氏体的表面分数保持低于或等于10%。
-任选地,在冷却至室温之后,如果尚未进行热浸涂步骤,则可以通过电化学方法(例如电镀锌)或通过任何真空涂覆法(如PVD或射流气相沉积)涂覆板。可以使用任何种类的涂层并且特别是锌或锌合金,如锌-镍合金、锌-镁合金或锌-镁-铝合金。任选地,在通过电镀锌涂覆之后,可以使板经历脱气。
实施例
将组成汇总在表1中的三个钢种铸造成半成品,并且按照汇总在表2中的工艺参数加工成通过淬火和自回火获得的钢板(经历加热、受控的热轧和随后的水冷却)。
表1-组成
测试的组成汇总在下表中,其中元素含量以重量百分比表示:
钢 | C | Mn | Si | Al | Ti | Nb | V | S | P | N | Ae1 | Tθ | Ae3 |
A | O.146 | 3.86 | 1.48 | 0.03 | - | 0.059 | - | 0.001 | 0.009 | 0.004 | 645 | 660 | 780 |
B | O.126 | 5.00 | 0.51 | 1.78 | - | 0.027 | - | 0.002 | 0.009 | 0.005 | 580 | 660 | 950 |
C | 0.110 | 5.17 | 0.51 | 1.81 | - | - | - | 0.001 | 0.017 | 0.005 | 580 | 660 | 950 |
钢A和B为根据本发明的,而钢C为比较例。
对于给出的钢,本领域技术人员知晓如何通过膨胀测定法测试和金相学分析确定Ae1、Ae3和Tθ温度。
然后对所得样品进行分析并且将相应的显微组织元素和机械特性分别汇总在表3和4中。
表3-显微组织和析出物
确定所获得的钢板的显微组织的相百分比:
*:根据本发明的试验
γ:代表残余奥氏体表面分数
γ长宽比:代表奥氏体膜的长宽比
MA:代表具有大于0.5μm的尺寸的MA岛表面分数
FM:代表新鲜马氏体表面分数
RM:代表回收马氏体表面分数
RF:代表再结晶铁素体表面分数
RM中的析出物:代表在回收马氏体中存在Nb的析出物
表4-机械特性
确定测试的样品的机械特性并汇总在下表中:
试验 | YS(MPa) | TS(MPa) | UE(%) | HER(%) |
1<sup>*</sup> | 766 | 1023 | 15.1 | 24.4 |
2<sup>*</sup> | 750 | 1014 | 15.8 | 25.5 |
3<sup>*</sup> | 722 | 1046 | 16.4 | 26.4 |
4<sup>*</sup> | 774 | 985 | 15.8 | 35.3 |
5 | 796 | 1044 | <u>10.6</u> | 21 |
6 | <u>635</u> | 1181 | 14.3 | <u>17.3</u> |
7 | <u>659</u> | 1183 | 14.3 | <u>15.8</u> |
8<sup>*</sup> | 791 | 924 | 12.3 | 48.2 |
9<sup>*</sup> | 760 | 926 | 14.7 | 46.0 |
10<sup>*</sup> | 742 | 949 | 14.0 | 43.8 |
11<sup>*</sup> | 725 | 967 | 15.3 | 47.4 |
12 | 861 | 1064 | 18.5 | <u>16.2</u> |
13 | 833 | 1086 | 17,2 | <u>14.2</u> |
14 | 786 | 1110 | 15.4 | <u>11.6</u> |
15 | <u>559</u> | 936 | 13.7 | 33 |
16 | <u>560</u> | 902 | 13.2 | 35 |
17 | <u>639</u> | <u>848</u> | 13.7 | 38 |
*:根据本发明的试验
根据2009年10月公布的ISO标准ISO 6892-1测量屈服强度YS、抗拉强度TS和均匀延伸率UE。根据ISO标准16630∶2009测量扩孔率HER。由于测量方法的差异,根据ISO标准16630∶2009的扩孔率HER的值非常不同,并且与根据JFST 1001(日本钢铁联合会标准)的扩孔率λ的值没有可比性。
实施例示出根据本发明的钢板(即实施例1至4和8至11)由于其特定组成和显微组织而是仅有的显示出所有目标特性的钢板。
Claims (17)
1.一种冷轧热处理钢板,以重量百分比计,由具有包含以下的组成的钢制成:
C:0.03%至0.25%
Mn:3.5%至8%
Si:0.1%至2.0%
Al:0.03%至2.0%
Ti≤0.080%
Nb≤0.080%
V≤0.2%
V+Ti+Nb>0.01%
S≤0.010%
P≤0.020%
N≤0.008%
以及任选地包含以重量百分比计的以下元素中的一者或更多者:
Mo:0.1%至0.5%
Cr:0.01%至1%
B:0.0005%至0.004%
所述组成的剩余部分为铁和由熔炼产生的不可避免的杂质,
以表面分数计,所述冷轧钢板具有由以下组成的显微组织:
-10%至30%的残余奥氏体,所述残余奥氏体作为具有至少3的长宽比的膜以及作为马氏体奥氏体岛存在,少于8%的这样的马氏体奥氏体岛具有大于0.5μm的尺寸,
-至多10%的新鲜马氏体,以及
-包含选自铌、钛和钒中的至少一种元素的析出物的回收马氏体。
2.根据权利要求1所述的冷轧热处理钢板,其中铝含量为至多1.2%。
3.根据权利要求1或2所述的冷轧热处理钢板,其中铌含量为至少0.010%。
4.根据权利要求1至3中任一项所述的冷轧热处理钢板,其中碳含量为至少0.10%。
5.根据权利要求1至4中任一项所述的冷轧热处理钢板,其中具有大于0.5μm的尺寸的马氏体奥氏体岛与所述奥氏体膜之间的分数比低于1.0。
6.根据权利要求5所述的冷轧热处理钢板,其中具有大于0.5μm的尺寸的马氏体奥氏体岛与所述奥氏体膜之间的分数比低于0.5。
7.根据权利要求1至6中任一项所述的冷轧热处理钢板,其中新鲜马氏体的表面分数低于5%。
8.根据权利要求1至7中任一项所述的冷轧热处理钢板,其中少于5%的这样的马氏体奥氏体岛具有大于0.5μm的尺寸。
9.根据权利要求1至8中任一项所述的冷轧热处理钢板,其中具有大于3的长宽比的奥氏体膜的表面分数为至少8%。
10.根据权利要求1至9中任一项所述的冷轧热处理钢板,其中所述冷轧热处理钢板涂覆有Zn或Zn合金。
11.根据权利要求1至9中任一项所述的冷轧热处理钢板,其中所述冷轧热处理钢板涂覆有Al或Al合金。
12.根据权利要求1至11中任一项所述的冷轧热处理钢板,其中所述冷轧热处理钢板具有至少700MPa的屈服强度YS、至少900MPa的抗拉强度TS、至少12%的均匀延伸率UE、以及至少20%的扩孔率HER。
13.一种用于制造冷轧热处理钢板的方法,包括以下顺序步骤:
-铸造钢以获得板坯,所述钢具有根据权利要求1至4中任一项所述的组成,
-在1150℃至1300℃的温度T再加热下对所述板坯进行再加热,
-在高于Ar3的温度下对经再加热的板坯进行热轧以获得热轧钢板,
-在20℃至600℃的卷取温度T卷取下对所述热轧钢板进行卷取,
-对所述热轧钢板进行退火以获得热轧退火钢板,
-对所述热轧退火钢板进行冷轧以获得冷轧钢板,
-将所述冷轧钢板再加热至高于860℃的第一退火温度并将所述冷轧钢板在所述退火温度下保持30秒至600秒的保持时间,以在退火时获得完全奥氏体组织,
-使所述冷轧钢板以0.5℃/秒至200℃/秒的冷却速率淬火至20℃至Ms-50℃的淬火温度,并在所述淬火温度下保持1秒至200秒的保持时间,
-将所述冷轧钢板再加热至Tθ至720℃的第二退火温度,Tθ表示这样的温度:高于所述温度渗碳体在加热时得到溶解,并将所述冷轧钢板在所述退火温度下保持100秒至2000秒的时间,
-将所述冷轧钢板冷却至室温以获得冷轧热处理钢板。
14.根据权利要求13所述的方法,其中对所述热轧钢板进行的所述退火为在500℃至680℃的温度下进行1000秒至50000秒的分批退火。
15.根据权利要求13或14中任一项所述的方法,其中所述冷轧钢板的加热速率为1℃/秒至200℃/秒。
16.一种用于制造至少两个钢板的点焊接头的方法,包括以下步骤:
-提供根据权利要求1至12中任一项所述的冷轧热处理钢板或通过根据权利要求13至15中任一项所述的方法制造的冷轧热处理钢板,
-提供第二钢板,
-将所述冷轧热处理钢板点焊至所述第二钢板。
17.根据权利要求16所述的方法,其中所述第二钢板为根据权利要求1至12中任一项所述的冷轧热处理钢板或通过根据权利要求13至15中任一项所述的方法制造的冷轧热处理钢板。
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CN113388779A (zh) * | 2021-05-21 | 2021-09-14 | 鞍钢股份有限公司 | 1.5GPa级超高强高塑性高扩孔DH钢板及制备方法 |
CN115198165A (zh) * | 2022-06-17 | 2022-10-18 | 首钢集团有限公司 | 一种降低980MPa级冷轧高强钢的带状组织的方法 |
CN115698364A (zh) * | 2020-07-24 | 2023-02-03 | 安赛乐米塔尔公司 | 冷轧退火钢板及其制造方法 |
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WO2019111029A1 (en) * | 2017-12-05 | 2019-06-13 | Arcelormittal | Cold rolled and annealed steel sheet and method of manufacturing the same |
CN114555845B (zh) * | 2019-10-23 | 2023-04-28 | 杰富意钢铁株式会社 | 高强度钢板及其制造方法 |
KR20220068245A (ko) * | 2019-10-23 | 2022-05-25 | 제이에프이 스틸 가부시키가이샤 | 고강도 강판 및 그의 제조 방법 |
EP4029958A4 (en) * | 2019-10-23 | 2023-01-25 | JFE Steel Corporation | HIGH STRENGTH STEEL SHEET AND METHOD OF PRODUCTION THEREOF |
CN112063931B (zh) * | 2020-09-07 | 2021-11-26 | 清华大学 | 一种低碳中锰高残奥高强韧钢及其热处理方法 |
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CN113388779A (zh) * | 2021-05-21 | 2021-09-14 | 鞍钢股份有限公司 | 1.5GPa级超高强高塑性高扩孔DH钢板及制备方法 |
CN113388779B (zh) * | 2021-05-21 | 2022-07-22 | 鞍钢股份有限公司 | 1.5GPa级超高强高塑性高扩孔DH钢板及制备方法 |
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KR102383627B1 (ko) | 2022-04-08 |
JP2021505764A (ja) | 2021-02-18 |
MX2020005585A (es) | 2020-09-14 |
CA3081159C (en) | 2022-08-30 |
MA50999A (fr) | 2021-03-17 |
BR112020007989A2 (pt) | 2020-10-20 |
US11530459B2 (en) | 2022-12-20 |
JP7220714B2 (ja) | 2023-02-10 |
FI3720980T3 (fi) | 2024-05-28 |
EP3720980A1 (en) | 2020-10-14 |
WO2019111028A1 (en) | 2019-06-13 |
KR20200078617A (ko) | 2020-07-01 |
MA50999B1 (fr) | 2024-05-31 |
ZA202002387B (en) | 2021-08-25 |
UA125547C2 (uk) | 2022-04-13 |
EP3720980B1 (en) | 2024-05-15 |
US20200347471A1 (en) | 2020-11-05 |
CN111373061B (zh) | 2022-03-11 |
BR112020007989B1 (pt) | 2023-02-23 |
WO2019111083A1 (en) | 2019-06-13 |
RU2736374C1 (ru) | 2020-11-16 |
CA3081159A1 (en) | 2019-06-13 |
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