CN103261325A - 用于储气罐的衬里 - Google Patents
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Abstract
本发明涉及一种用于储气罐的包含聚合物组合物的衬里,其包含:i.聚酰胺A;和ii.相对于所述聚合物组合物的总量,含量为至少0.001重量%的成核剂;和iii.相对于所述聚合物组合物的总量,含量为至少1重量%的冲击改性剂。本发明还涉及一种包含含有连续的碳纤维或玻璃纤维的结构性纤维复合材料的储气罐,以及一种通过吹塑成型制造衬里的方法。
Description
本发明涉及一种用于储气罐的包含聚合物组合物的衬里,并且涉及包含该衬里的储气罐。
现有技术
储气罐是已知的,例如被称为复合包装压力容器(compositeoverwrapped pressure vessel)或真空隔热罐容器。储气罐包含薄的、通常用结构性纤维复合材料包裹的非结构性衬里,该衬里被发计用来在压力下容纳流体或气体。该衬里用于在流体或气体与复合材料之间提供屏障,以防止泄漏和结构性纤维复合材料的化学降解。在一般情况下,施加保护壳用于防止冲击损坏的防护屏。最常用的复合材料是纤维增强的聚合物。对于衬里来说,最常用的是聚乙烯,如US2002088806中所述。与尺寸相近的金属压力罐相比,这些类型的罐的优点在于其重量较低。然而,这种衬里的缺点为,从衬里渗出的气体可能使纤维变脆。US20090203845中描述了一种具有改进的阻隔性能的衬里,其包含聚酰胺树脂、共聚酰胺和抗冲击材料。该衬里的缺点为阻隔性仍然不足。
本发明的目标
本发明的目标是提供一种用于储气罐且展示出改进的阻隔性能的衬里。
发明详述
业已惊讶地发现,一种用于储气罐的包含聚合物组合物的衬里显示出改进的阻隔性能,所述衬里包含:
i.聚酰胺A;和
ii.相对于聚合物组合物的总量,含量为至少0.001重量%的成核剂;和
iii.相对于聚合物组合物的总量,含量为至少1重量%的冲击改性剂。
根据本发明的衬里具有改进的阻隔性能。该衬里使得纤维降解较少,并且与现有技术中已知储气罐相比,在储气罐中允许更薄的衬里或更少的层,这将节约材料并简化工艺。另外一个优点是,使用根据本发明的衬里,观察到更少的弯曲(buckling)。当罐中的压力低时(例如罐开口时),由于衬里和其他层之间存在渗透而存在的气体膨胀,此时发生弯曲。
本发明的衬里的另一个优点为,任选存在的真空空间(对于超隔热而存在)也能更好地被保护免于气体渗透。
术语“气体”在此理解为包括各种各样的气体,然而其在储存中可能包含液体部分。气体的例子包括生物气和天然气。具体的例子包括氢气、甲烷、丁烷、丙烷、氦气、氮气和氧气。
衬里可以存在于罐的内侧,因而与要储存的液体和/或气体接触。存在真空空间时,衬里也可以存在于罐的外侧,从而位于真空空间和罐的外侧之间。罐也可以包含衬里的组合,例如,一个在内侧,一个在外侧。
根据本发明的衬里的另一个优点是,它具有良好的阻隔性能,同时具有足够的刚度。令人惊讶的是,业已发现在衬里的制造期间,成核剂的存在几乎不影响吹塑成型性能。
聚酰胺A
含有聚合物组合物的衬里中的聚酰胺A可以是任意半结晶的聚酰胺或其混合物、以及共聚酰胺。
“半结晶的聚酰胺”在本文中被理解为包括具有结晶区和非晶区的聚酰胺。合适的聚酰胺包括脂肪族聚酰胺如PA6、PA66、PA46、PA410、PA610、PA11、PA12、PA412及其混合物,还包括半芳香族聚酰胺。合适的半芳香族聚酰胺包括基于对苯二甲酸的聚酰胺,例如PA6T、PA9T、PA4T、PA6T6I、PA10T以及PAMXD6、PAMXDT及其共聚酰胺、以及其混合物,还包括脂肪族和半芳香族聚酰胺的混合物。
优选地,聚酰胺A选自PA6、PA66及其混合物的组,因为这样做的优点是,这些聚酰胺都是易于得到的,并且具有良好的渗透水平,以及良好的延展水平或耐冲击水平。
成核剂
根据本发明的衬里以相对于聚合物组合物的总量至少0.001重量%的量包含成核剂。
术语“成核剂”是本领域技术人员已知的,指的是这样的物质,该物质当被掺入聚合物时形成用于聚合物熔体中晶体成长的核。成核剂包括例如较之聚酰胺A的熔融温度具有更高的熔融温度的聚酰胺。更高的熔融温度在本文中被理解为,优选比聚酰胺A的熔融温度高至少10℃的熔融温度,更优选比聚酰胺A的熔融温度高至少20℃的熔融温度,最优选比聚酰胺A的熔融温度高至少50℃的熔融温度。
适合作为成核剂的聚酰胺包括上面所提到的所有聚酰胺,但附加条件为熔融温度高于聚酰胺A的熔融温度。优选地,PA46、PA4T或PA410被用作成核剂。
优选地,相对于所述聚合物组合物的总量,成核剂以至少0.01wt%的量存在,更优选以至少0.02wt%的量存在,最优选以至少0.05wt%的量存在。
其他成核剂包括微滑石(micro talcum)、碳黑、二氧化硅、二氧化钛和纳米粘土。
优选地,相对于所述聚合物组合物的总量,成核剂以至多5wt%的量存在,更优选以至多4wt%的量存在,最优选以至多0.15wt%的量存在。
优选地,成核剂是微滑石。该微滑石优选具有小于1微米的中值直径,更优选小于0.7微米的中值直径,甚至更优选小于0.6微米的中值直径。
这样做的好处是,与中值直径较高的滑石颗粒相比,这种微滑石能更有效地改善阻隔性能。
微滑石可以以非常低的量存在于聚合物组合物中,例如以相对于所述聚合物组合物的总量至少0.001wt%的量,优选至少0.01wt%的量,更优选至少0.02wt%的量,甚至更优选至少0.04wt%的量。优选地,相对于所述聚合物组合物的总量,微滑石可以以至多0.8wt%的量存在于聚合物组合物中,更优选至多0.5wt%的量,甚至更优选至多0.2wt%的量。
根据本发明的微滑石的量的优点为,在-30℃至保持足够的低温冲击性。
在一个实施方式中,PA6被选作聚酰胺A,同时成核剂选自PA66、PA46、PA410和PA4T的组中。
在一个实施方式中,PA66被选作聚酰胺A,同时成核剂选自PA46和PA4T的组中。
冲击改性剂
相对于聚合物组合物的总量,根据本发明的衬里以至少1wt%的量包含冲击改性剂。冲击改性剂本身是已知的,其为不仅包含非极性单体(如烯烃)而且包含极性或反应性单体(例如丙烯酸酯和含有环氧、酸或酸酐的单体)的橡胶状聚合物。实例包括乙烯与(甲基)丙烯酸的共聚物或酸酐基团官能化的乙烯/丙烯共聚物。冲击改性剂的优点是它们不仪改善聚合物组合物的冲击强度,也有助于粘度的增加。
优选地,冲击改性剂的量为至少5wt%,更优选至少7wt%,甚至更优选至少10wt%。这样做的好处是冲击强度好。
优选地,相对于聚合物组合物的总量,冲击改性剂的量为至多60wt%,更优选至多50wt%,甚至更优选至多30wt%。最有利的是冲击改性剂的量为7-20wt%。这样做的好处是保持足够的阻隔性能同时兼具良好的刚度性能。优选地,冲击改性剂为核-壳型冲击改性剂。已表明,核-壳型冲击改性剂对阻隔性能的影响较小。
其他添加剂
根据本发明的衬里可以任选地包含其它添加剂,如填充剂、着色剂、支化剂、脱模剂和润滑剂。
合适的填料是无机填料,如粘土、云母、滑石、玻璃球。增强纤维为例如玻璃纤维或碳纤维。相对于聚合物组合物的总量,聚酰胺组合物优选地包含1-60wt%的玻璃纤维作为增强纤维,更优选包含10-45wt%的玻璃纤维作为增强纤维,最优选包含10-20wt%的玻璃纤维作为增强纤维。一般,合适的玻璃纤维的直径为5-20微米,优选8-15微米,并且用于适用于聚酰胺的涂层。含有玻璃纤维的聚合物组合物的优点为,其增大的强度和刚度,特别是在较高温度下也如此,从而允许在接近聚合物组合物中的聚合物的熔点的温度下使用。相对于聚合物组合物的总量,碳纤维可以以至多30wt%的量存在。
衬里的制造
可以通过吹塑成型或注射成型来制造衬里。注塑成型优选以双壳成型的形式进行,之后将壳焊接成衬里。通过吹塑成型制造时,衬里还优选包含支化剂以允许聚合物组合物更高的粘度。
吹塑成型在本文中被理解为包括至少下列步骤:
a.加热聚合物组合物以得到均匀的粘性液体;
b.由所述粘性液体形成型坯(parison);
c.通过加压气体使型坯膨胀并使其紧靠模具腔,直到其冷却并固化形成部件;
d.打开所述模具;
e.射出该部件。
用于制造衬里的优选的方法是吹塑成型,因为这能得到更大的衬里,并且避免使用额外的焊接工艺步骤。
储气罐
本发明还涉及一种包含结构性纤维复合材料和根据本发明的衬里的储气罐。结构性纤维复合材料通常包括连续的碳纤维或玻璃纤维。
实施例
所用材料:
对比例A和B:HDPE
实施例1:89.67wt%相对粘度为2.5的PA6,
0.5wt%支化剂,
9.75wt%冲击改性剂(马来酸酐(MAH)接枝的乙烯共聚物),
0.08wt%微滑石,作为成核剂。
实施例2:79.82wt%相对粘度为2.2的PA6,
20wt%冲击改性剂(马来酸酐(MAH)接枝的乙烯共聚物),
0.08wt%微滑石,作为成核剂。
微滑石
中值直径为0.50微米,99%的小于5微米,92%的小于2微米,并且75%的小于1微米。
测量氦气渗透性的测试方法
测试方法包括评价气体透过塑料(薄膜、片材)的稳态透过率。安装样品从而在气体透过单元的两个腔室之间形成屏障。一个腔室包含在指定的高压下的测试气体,在另一腔室中收集渗透的气体,并将该气体带入检测器。已知样品的表面,可以计算出气体透过率(gas transmission rate),即,在测试条件下单位时间内通过塑料薄膜单位表面的给定气体的数量。
氦气渗透性的测试是在40℃和25℃的温度下进行,均是在0%的相对湿度下。所有测试样品的厚度均为0.4毫米,氦气分压为6Bar。计算氦气渗透率(Helium permeability),即气体透过率与氦气分压的比值乘以膜的厚度。表示渗透率的单位是cm3mm/m2day atm。
表1:氦气渗透率的结果
*确切的组成请参见如上所述的“所用材料”;n.m.是未测定。
表1中的结果清楚地表明,与HDPE相比,根据本发明的衬里所采用的聚合物组合物显示出降低的渗透性。
还通过用于氦气的相同程序在40℃下测量了氮气的渗透性。进一步通过如ISO15105-1中所述的方法在40℃下测定甲烷的渗透性。对于根据本发明的衬里所采用的聚合物组合物来说,氮气和甲烷在40℃下的渗透率均小于1cm3mm/m2day atm。而对于作为比较的HDPE来说,氮气的渗透率为124cm3mm/m2day atm,甲烷的渗透率为341cm3mm/m2day atm。这些结果也表明,与HDPE衬里相比,根据本发明的衬里具有优异的阻隔性能。
使用毛细管流变仪(Rheograph6000)测量熔体强度。在测试过程中,使用恒定的产量,挤出聚合物组合物的线,(数据:烤箱直径12mm,Vpiston=0.1mm/sec,毛细管40/2,毛细管长度为40mm,T熔融=240℃)。在熔体强度测量期间,以恒定的加速度(1.2mm/sec2)拉长所述线材。测定不同拉伸比下的熔体强度(cN)。
令人惊讶地发现,根据本发明的衬里所用的聚合物组合物的该值为约15cN,其与不含成核剂的聚合物组合物相当。
Claims (12)
1.一种用于储气罐的包含聚合物组合物的衬里,其包含:
i.聚酰胺A;和
ii.相对于所述聚合物组合物的总量,含量为至少0.001重量%的成核剂;和
iii.相对于所述聚合物组合物的总量,含量为至少1重量%的冲击改性剂。
2.如权利要求1所述的衬里,其中,所述成核剂选自较之聚酰胺A具有更高的熔融温度的聚酰胺和微滑石的组。
3.如权利要求2所述的衬里,其中,较之聚酰胺A具有更高的熔融温度的所述聚酰胺选自PA46、PA410、PA4T的组。
4.如权利要求1所述的衬里,其中,所述聚酰胺A是PA6,并且所述成核剂选自PA66、PA46、PA410、PA4T的组。
5.如权利要求1所述的衬里,其中,所述聚酰胺A是PA66,并且所述成核剂选自PA46和PA4T的组。
6.如权利要求1所述的衬里,其中,所述成核剂是微滑石。
7.如权利要求1-6中任意一项所述的衬里,其中,相对于所述聚合物组合物的总量,所述成核剂以至少0.05wt%的量存在。
8.如上面任何一个权利要求所述的衬里,其中,相对于所述聚合物组合物的总量,所述成核剂以0.05-0.15wt%的量存在。
9.如上面任何一个权利要求所述的衬里,其中,相对于所述聚合物组合物的总量,所述冲击改性剂的含量为7-20wt%。
10.如上面任何一个权利要求所述的衬里,其中,所述冲击改性剂是核-壳型冲击改性剂。
11.储气罐,其包含如上面任何一个权利要求所述的衬里和含有连续的碳纤维或玻璃纤维的结构性纤维复合材料。
12.一种用于制备如上面任何一个权利要求所述的衬里的方法,至少包括下列步骤:
a.加热所述聚合物组合物以得到均匀的粘性液体;
b.由所述粘性液体形成型坯;
c.通过加压气体使所述型坯膨胀并使其紧靠模具腔,直到其冷却并固化形成部件;
d.打开所述模具;
e.射出所述部件。
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Cited By (4)
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US11939105B2 (en) | 2017-08-29 | 2024-03-26 | Goodrich Corporation | 3D woven conformable tank |
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EP3702765B1 (en) | 2017-10-23 | 2023-07-19 | Toray Industries, Inc. | Inspection method and manufacturing method for molded resin product as well as inspection device and manufacturing device for molded resin product |
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KR20210040285A (ko) | 2018-07-31 | 2021-04-13 | 도레이 카부시키가이샤 | 고압 수소에 접하는 압출 성형품용의 폴리아미드 수지 조성물 및 이를 이용한 압출 성형품 |
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US11841332B2 (en) | 2019-01-25 | 2023-12-12 | Toray Industries, Inc. | Inspection method and manufacturing method for structure and inspection apparatus and manufacturing apparatus for structure |
JP7404774B2 (ja) | 2019-10-29 | 2023-12-26 | Ube株式会社 | ポリアミド樹脂組成物 |
JP7196871B2 (ja) * | 2020-02-19 | 2022-12-27 | トヨタ自動車株式会社 | 高圧タンク |
KR20220094719A (ko) * | 2020-12-29 | 2022-07-06 | 코오롱플라스틱 주식회사 | 수소 탱크 라이너용 폴리아미드 수지 조성물 및 이로부터 제조된 성형품 |
FR3124516A1 (fr) * | 2021-06-28 | 2022-12-30 | Arkema France | Compositions de soufflage moulage a base de polyamides branches et leurs utilisations |
JP7235186B1 (ja) * | 2021-11-05 | 2023-03-08 | 三菱瓦斯化学株式会社 | ライナー、および、圧力容器 |
WO2023079823A1 (ja) * | 2021-11-05 | 2023-05-11 | 三菱瓦斯化学株式会社 | ライナー、および、圧力容器 |
KR20240031115A (ko) * | 2022-08-30 | 2024-03-07 | 주식회사 삼양사 | 폴리아미드 수지 조성물 |
WO2024106931A1 (ko) * | 2022-11-15 | 2024-05-23 | 코오롱플라스틱 주식회사 | 폴리아미드 수지 조성물 및 이를 이용하여 제조된 성형품 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1960842A (zh) * | 2004-06-03 | 2007-05-09 | 原子能委员会 | 制造ⅳ型贮罐的密封气囊的方法和ⅳ型贮罐 |
CN101309971A (zh) * | 2005-11-15 | 2008-11-19 | 旭化成化学株式会社 | 耐热性树脂组合物 |
US20090203845A1 (en) * | 2008-02-12 | 2009-08-13 | Ube Industries, Ltd., A Corporation Of Japan | Hydrogen tank liner material and hydrogen tank liner |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4749736A (en) | 1986-10-20 | 1988-06-07 | Allied Corporation | Nucleating system for polyamides |
GB8818622D0 (en) | 1988-08-05 | 1988-09-07 | British Petroleum Co Plc | Container for high pressure gases |
DE3904342A1 (de) | 1989-02-14 | 1990-08-16 | Hoechst Ag | Faserverstaerktes thermoplastisches verbundmaterial und daraus hergestellte formkoerper |
JPH08120099A (ja) | 1994-10-27 | 1996-05-14 | Unitika Ltd | ポリアミドフイルム及びその製造方法 |
DE19621309A1 (de) | 1996-05-28 | 1997-12-04 | Bayer Ag | Folien oder Hohlkörper enthaltend eine Polyamidschicht |
JPH101608A (ja) | 1996-06-18 | 1998-01-06 | Mitsubishi Chem Corp | ガスバリヤー性ポリアミド成形体およびその製造方法 |
BE1010777A4 (nl) | 1996-12-02 | 1999-01-05 | Dsm Nv | Werkwijze voor de produktie van polyamide vormlichamen met een verbeterd kristallisatiegedrag. |
JPH11179791A (ja) * | 1997-12-18 | 1999-07-06 | Mitsubishi Chemical Corp | 耐圧容器用の内側殻の製造方法 |
WO2000023506A1 (de) | 1998-10-16 | 2000-04-27 | Wolff Walsrode Aktiengesellschaft | Transparente polyamidfolie mit hoher festigkeit |
DE19922933A1 (de) | 1999-05-19 | 2000-11-23 | Bayer Ag | Verwendung von Polyamid und Schichtsilikat zur Herstellung von blas- und thermogeformten Gegenständen |
US20030092822A1 (en) | 2000-03-09 | 2003-05-15 | Detlev Joachimi | Highly viscous polyamide for use in extrusion blow molding |
JP2002188794A (ja) | 2000-12-21 | 2002-07-05 | Honda Motor Co Ltd | 高圧水素タンクおよび高圧水素タンクの製造方法 |
JP4359107B2 (ja) | 2003-08-27 | 2009-11-04 | 三菱エンジニアリングプラスチックス株式会社 | 自動車用樹脂製複合部品 |
JP2005272535A (ja) * | 2004-03-23 | 2005-10-06 | Mitsubishi Gas Chem Co Inc | ポリアミド複合材料用組成物およびポリアミド複合材料 |
JP4961204B2 (ja) * | 2006-12-28 | 2012-06-27 | 日本ポリエチレン株式会社 | 圧力容器及びその製造方法 |
JP5288245B2 (ja) * | 2007-05-21 | 2013-09-11 | 三菱瓦斯化学株式会社 | ガスバリア性に優れた熱可塑性樹脂組成物延伸体 |
EP2270097B1 (en) | 2008-03-28 | 2016-07-20 | Ube Industries, Ltd. | Polyamide resin composition |
JP4552159B2 (ja) * | 2008-07-09 | 2010-09-29 | トヨタ自動車株式会社 | ガスタンク及びガスタンクの製造方法 |
CN103052684B (zh) | 2010-07-26 | 2016-08-03 | 帝斯曼知识产权资产管理有限公司 | 燃料部件及用于生产燃料部件的方法 |
EP2457952A1 (de) * | 2010-11-30 | 2012-05-30 | LANXESS Deutschland GmbH | Gastank |
-
2011
- 2011-12-09 CA CA2819183A patent/CA2819183C/en active Active
- 2011-12-09 KR KR1020157021281A patent/KR20150095953A/ko not_active Application Discontinuation
- 2011-12-09 WO PCT/EP2011/072282 patent/WO2012076677A2/en active Application Filing
- 2011-12-09 CN CN201180059418.4A patent/CN103261325B/zh active Active
- 2011-12-09 KR KR1020137017781A patent/KR20130102630A/ko active Application Filing
- 2011-12-09 JP JP2013542554A patent/JP6209758B2/ja active Active
- 2011-12-09 BR BR112013014431A patent/BR112013014431A2/pt not_active Application Discontinuation
- 2011-12-09 KR KR1020187015584A patent/KR102189936B1/ko active IP Right Review Request
- 2011-12-09 PL PL11794148T patent/PL2649130T3/pl unknown
- 2011-12-09 EP EP11794148.4A patent/EP2649130B1/en not_active Revoked
- 2011-12-09 US US13/991,501 patent/US9470366B2/en active Active
- 2011-12-09 EA EA201300681A patent/EA025308B1/ru not_active IP Right Cessation
-
2017
- 2017-06-07 JP JP2017112891A patent/JP2017201213A/ja not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1960842A (zh) * | 2004-06-03 | 2007-05-09 | 原子能委员会 | 制造ⅳ型贮罐的密封气囊的方法和ⅳ型贮罐 |
CN101309971A (zh) * | 2005-11-15 | 2008-11-19 | 旭化成化学株式会社 | 耐热性树脂组合物 |
US20090203845A1 (en) * | 2008-02-12 | 2009-08-13 | Ube Industries, Ltd., A Corporation Of Japan | Hydrogen tank liner material and hydrogen tank liner |
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CN107002873A (zh) * | 2014-11-28 | 2017-08-01 | 三菱瓦斯化学株式会社 | 压力容器、衬垫和压力容器的制造方法 |
CN106255726A (zh) * | 2015-02-27 | 2016-12-21 | 东丽株式会社 | 与高压氢接触的成型品用的聚酰胺树脂组合物及使用其的成型品 |
CN106255726B (zh) * | 2015-02-27 | 2019-02-19 | 东丽株式会社 | 与高压氢接触的成型品用的聚酰胺树脂组合物及使用其的成型品 |
CN108367506A (zh) * | 2015-12-18 | 2018-08-03 | 帝斯曼知识产权资产管理有限公司 | 压力容器 |
CN112824740A (zh) * | 2019-11-20 | 2021-05-21 | 刘振国 | 一种储氢罐内胆及其制备方法 |
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JP6209758B2 (ja) | 2017-10-11 |
WO2012076677A3 (en) | 2012-09-07 |
CN103261325B (zh) | 2016-05-11 |
KR20150095953A (ko) | 2015-08-21 |
EA025308B1 (ru) | 2016-12-30 |
JP2017201213A (ja) | 2017-11-09 |
KR102189936B1 (ko) | 2020-12-14 |
KR20180063908A (ko) | 2018-06-12 |
CA2819183A1 (en) | 2012-06-14 |
CA2819183C (en) | 2018-10-30 |
US20140034654A1 (en) | 2014-02-06 |
JP2014501818A (ja) | 2014-01-23 |
EA201300681A1 (ru) | 2013-11-29 |
PL2649130T3 (pl) | 2018-01-31 |
BR112013014431A2 (pt) | 2016-09-13 |
KR20130102630A (ko) | 2013-09-17 |
EP2649130B1 (en) | 2017-08-23 |
US9470366B2 (en) | 2016-10-18 |
EP2649130A2 (en) | 2013-10-16 |
WO2012076677A2 (en) | 2012-06-14 |
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