CN115369391B - 一种聚合物表面化学镀铜金属化的银胶体活化液组合物及其制备方法 - Google Patents
一种聚合物表面化学镀铜金属化的银胶体活化液组合物及其制备方法 Download PDFInfo
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- CN115369391B CN115369391B CN202210856861.4A CN202210856861A CN115369391B CN 115369391 B CN115369391 B CN 115369391B CN 202210856861 A CN202210856861 A CN 202210856861A CN 115369391 B CN115369391 B CN 115369391B
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- silver
- reducing agent
- silver colloid
- copper plating
- electroless copper
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 41
- 239000004332 silver Substances 0.000 title claims abstract description 41
- 239000000084 colloidal system Substances 0.000 title claims abstract description 40
- 238000007747 plating Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 230000003213 activating effect Effects 0.000 title claims abstract description 28
- 238000001465 metallisation Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 title claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 18
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
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- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
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- 238000001514 detection method Methods 0.000 claims description 4
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- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
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- 230000001105 regulatory effect Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 claims description 2
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- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
Abstract
本发明公开了一种聚合物表面化学镀铜金属化的银胶体活化液组合物及其制备方法,银胶体活化液组合物的pH=6‑9,其中的银胶体颗粒的粒径大小为5‑20nm,由可溶性银盐、第一还原剂、第二还原剂、稳定剂、pH调节剂和去离子水组成。本发明使用绿色环保、水溶性良好的还原剂和稳定剂,制备方法简单、成本低、对环境友好;本发明的银胶体颗粒尺寸分布窄,稳定性良好,放置半年以上仍无沉淀析出;本发明与聚合物基材之间的结合力良好,可用于催化聚合物材料表面的化学镀铜金属化工艺;聚合物经本发明活化、化学镀铜后,能够得到致密、连续、均匀、与基底结合力良好的铜镀层。
Description
技术领域
本发明属于聚合物表面金属化技术领域,具体涉及一种聚合物表面化学镀铜金属化的银胶体活化液组合物及其制备方法。
背景技术
胶体是指分散相粒径大小为1-100nm的分散体系。纳米颗粒具有量子尺寸效应、小尺寸效应、表面效应和宏观量子隧道效应等特有性质,因此,银金属纳米颗粒具有比块状金属更大的比表面积和表面结合能,更易发生吸附以及具有更高的催化活性。同时,银纳米颗粒具有优越的抗菌性能。因此,银纳米颗粒广泛应用于表面增强拉曼、抗菌织物、导电浆料、聚合物材料表面金属化、电路板通孔金属化等领域。
CN 109060762A公开了一种作为复合柔性表面增强拉曼基底的银纳米颗粒的制备方法。采用乙二醇、聚乙烯吡咯烷酮、硝酸银等制备了银胶体溶液。将银胶体溶液与PDMS预聚合的甲苯溶液混合,滴加至硬质基板上,加热固化,得到表面拉曼增强基底。所述发明中银纳米颗粒的粒径大小为70-80nm,颗粒间隙为4-7nm,增强对罗丹明(R6G)分子的拉曼检测信号。CN 111451522A公开了一种应用于防蚊、抗菌的纳米银溶液的制备方法。所述发明中,纳米银溶液组成包含β环糊精-聚甘氨酸水溶液、防蚊小分子(甲氧苄氟菊酯等)、银离子溶液、还原剂(葡萄糖、硼氢化钠、水合肼)等,通过水浴加热的方式,得到粒径大小为1-100nm的纳米银溶液。CN 113842397A公开了一种医用纳米银递送系统的制备方法。首先,采用柠檬酸还原硝酸银,再采用硼氢化钠继续还原,超滤管分离,得到粒径大小为22nm的纳米银胶体。以HS-PEG-N3作为桥联分子,cRGD修饰纳米银颗粒,形成cRGD和PEG双修饰的纳米银递送系统,具有良好的靶向能力,能有效防止血栓增大。CN 110983763A公开了一种棉织物表面的化学镀铜工艺。首先,使用聚二甲基二稀丙基氯化铵处理棉织物,随后,硼氢化钠溶液处理,干燥后,采用喷墨打印技术将银纳米粒子/乙醇混合溶液打印在棉织物表面,用于化学镀铜。CN 103619128A公开了一种柔性电路板的制备方法,采用喷墨打印技术将含有银盐、有机还原剂和润湿剂的含银墨水打印在聚酰亚胺基材上,经烧结后,产生银纳米颗粒,制备柔性电路板。
现有技术中,银纳米颗粒的制备包括物理法和化学法。其中,化学法制备银纳米颗粒具有成本低、形状可控等特点,被普遍使用。目前,化学法通常采用硼氢化钠、水合肼作为还原剂,制备流程多,操作复杂,制备的银纳米颗粒粒径分布宽,同时易发生团聚现象,稳定性较差。同时对于聚合物表面化学镀铜金属化过程中,通常采用激光照射、预浸还原剂等方式,形成银纳米颗粒,所需成本高、操作复杂。因此,发明一种简便、经济,稳定性良好、催化性能优越、可用于聚合物材料表面金属化的银胶体活化液及其制备方法至关重要。
发明内容
本发明目的在于克服现有技术缺陷,提供一种聚合物表面化学镀铜金属化的银胶体活化液组合物。
本发明的另一目的在于提供一种上述聚合物表面化学镀铜金属化的银胶体活化液组合物的制备方法。
本发明的再一目的在于提供一种聚合物表面化学镀铜金属化方法。
本发明的技术方案如下:
一种聚合物表面化学镀铜金属化的银胶体活化液组合物,pH=6-9,银胶体颗粒的粒径大小为5-20nm,由可溶性银盐、第一还原剂、第二还原剂、稳定剂、pH调节剂和去离子水组成,可溶性银盐在其中的浓度为0.1-10g/L,第一还原剂与可溶性银盐的摩尔比为1-5∶1,第二还原剂与可溶性银盐的摩尔比为1-3∶1,稳定剂在其中的浓度为10mg/L-30g/L;
第一还原剂为纤维素类化合物、羟基羧酸类化合物和氨基羧酸类化合物中的至少一种,
第二还原剂为亚硫酸钠、乙醛酸、苯酚和对苯二酚中的至少一种,
稳定剂为油酸、十八胺、多元醇类化合物、糖类物质、阴离子表面活性剂和金属无机盐中的至少一种。
在本发明的一个优选实施方案中,所述可溶性银盐为硝酸银、氯酸银和醋酸银中的至少一种。
在本发明的一个优选实施方案中,所述第一还原剂为羧甲基纤维素钠、醋酸纤维素、酒石酸、水杨酸、苹果酸、谷氨酸和胱氨酸中的至少一种。
在本发明的一个优选实施方案中,所述多元醇类化合物包括可溶性淀粉、环糊精、十八硫醇和乙二醇中的至少一种。
在本发明的一个优选实施方案中,所述糖类物质包括壳聚糖和葡萄糖中的至少一种。
在本发明的一个优选实施方案中,所述阴离子表面活性剂包括十二烷基硫酸钠和双(2-乙基己基)磺基琥珀酸钠中的至少一种。
在本发明的一个优选实施方案中,所述金属无机盐包括金属硝酸盐和金属氯酸盐中的至少一种。
在本发明的一个优选实施方案中,所述pH调节剂为5%硝酸溶液和/或25%氢氧化钠溶液。
上述银胶体活化液组合物的制备方法,包括如下步骤:
(1)向可溶性银盐水溶液中,加入稳定剂水溶液,搅拌、混合均匀;
(2)在温度为25-100℃和不断搅拌条件下,将第一还原剂加入步骤(1)所得的物料中,使用pH调节剂调节pH为6.0-9.0,反应10-120min;
(3)在温度为25-100℃和不断搅拌条件下,将第二还原剂逐渐加入步骤(2)所得的物料中,反应15-30min,使用pH调节剂调节溶液pH为6.0-9.0,然后依次经检测和定容,得到所述银胶体活化液组合物;
该检测为:使用氯化钠水溶液或铜片置换实验进行检测,以恰好不产生氯化银或铜片上无Ag置换为准。
一种聚合物表面化学镀铜金属化方法,包括:将聚合物表面除油、粗化和亲水处理后,在20-50℃的上述银胶体活化液组合物中活化0.5-10min,然后在无机酸、无机盐或有机物水溶液中解胶后进行化学镀铜。
本发明的有益效果是:
1、本发明使用绿色环保、水溶性良好的还原剂和稳定剂,制备方法简单、成本低、对环境友好。
2、本发明中的银胶体的颗粒尺寸分布窄,稳定性良好,放置半年以上仍无沉淀析出。
3、本发明与聚合物基材之间的结合力良好,可用于催化聚合物材料表面的化学镀铜金属化工艺。
4、聚合物经本发明活化、化学镀铜后,能够得到致密、连续、均匀、与基底结合力良好的铜镀层。
附图说明
图1为本发明实施例的银胶体活化液组合物的外观图。
图2为本发明实施例的银胶体活化液组合物的TEM形貌图(放大100000倍)。
图3为本发明实施例的铜镀层的SEM形貌图(放大5000倍)。
图4本发明实施例的铜镀层外观图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1至3
(1)向可溶性银盐水溶液中,加入稳定剂水溶液,搅拌、混合均匀;
(2)在温度为25-100℃和不断搅拌条件下,将第一还原剂加入步骤(1)所得的物料中,使用pH调节剂调节pH为6.0-9.0,反应10-120min;
(3)在温度为25-100℃和不断搅拌条件下,将第二还原剂逐渐加入步骤(2)所得的物料中,反应15-30min,使用pH调节剂调节溶液pH为6.0-9.0,然后依次经检测和定容,得到如图1和2所示的所述银胶体活化液组合物;
该检测为:使用氯化钠水溶液或铜片置换实验进行检测,以恰好不产生氯化银或铜片上无Ag置换为准。
应用以上银胶体活化液组合物进行聚合物表面化学镀铜金属化,具体步骤如下:
(1)在65℃条件下,对ABS除油处理10min,除去基材表面油污;
(2)除油处理后的ABS经水洗后,采用65℃的粗化液(200g/L重铬酸钠和150ml/L硫酸)粗化处理30min,增加镀层粗糙度和亲水性;
(3)粗化后的ABS经水洗后,采用20-50℃的银胶体活化液组合物活化处理0.5-10min;
(4)采用含有有机物的水溶液进行解胶处理5min,暴露出Ag催化中心;
(5)将解胶处理后的ABS经水洗后,在50℃条件下,浸于pH为12.0的乙醛酸化学镀铜液中,化学镀铜2h,得到如图3和4所述的铜镀层。
本实施例1至3所采用的银胶体活化液组合物的具体配方和效果如下表1所示:
表1银胶体活化液组合物的制备以及活化条件、银胶体活化液组合物以及镀层表征
采用本发明的银胶体活化液制备方法,能得到粒径大小为5-20nm,稳定性良好的银胶体活化液。同时,采用本发明的胶体银活化液及上述化学镀铜金属化流程,能得到致密、连续、均匀、与基底结合力良好的铜镀层。如图1所示,为银胶体活化液的外观图。如图2所示,银胶体活化液中银纳米颗粒的形貌和粒径大小由透射电子显微镜(TEM)测得,制得的银纳米颗粒为球状,平均粒径大小在20nm以下。如图3所示,铜镀层的形貌由扫描电子显微镜(SEM)测得,经银胶体活化液处理、化学镀铜后,所得铜镀层致密、连续、均匀。如图4所示,铜镀层的外观均呈现紫铜色、镀层连续、无漏镀等现象。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (3)
1.一种聚合物表面化学镀铜金属化的银胶体活化液组合物的制备方法,其特征在于:包括如下步骤:
(1)向可溶性银盐水溶液中,加入稳定剂水溶液,搅拌、混合均匀;
(2)在温度为25-100℃和不断搅拌条件下,将第一还原剂加入步骤(1)所得的物料中,使用pH调节剂调节pH为6.0-9.0,反应10-120 min;
(3)在温度为25-100℃和不断搅拌条件下,将第二还原剂逐渐加入步骤(2)所得的物料中,反应15-30 min,使用pH调节剂调节溶液pH为6.0-9.0,然后依次经检测和定容,得到所述银胶体活化液组合物;
该检测为:使用氯化钠水溶液或铜片置换实验进行检测,以恰好不产生氯化银或铜片上无Ag置换为准;
所述银胶体活化液组合物的pH=6-9,银胶体颗粒的粒径大小为5-20nm,由可溶性银盐、第一还原剂、第二还原剂、稳定剂、pH调节剂和去离子水组成,可溶性银盐在其中的浓度为0.1-10g/L,第一还原剂与可溶性银盐的摩尔比为1-5:1,第二还原剂与可溶性银盐的摩尔比为1-3:1,稳定剂在其中的浓度为10mg/L-30g/L;
可溶性银盐为硝酸银、氯酸银和醋酸银中的至少一种;
第一还原剂为羧甲基纤维素钠和醋酸纤维素中的至少一种,
第二还原剂为亚硫酸钠,
稳定剂为油酸、十八胺、多元醇类化合物、糖类物质、阴离子表面活性剂和金属无机盐中的至少一种,多元醇类化合物包括可溶性淀粉、环糊精、十八硫醇和乙二醇中的至少一种,糖类物质包括壳聚糖和葡萄糖中的至少一种,阴离子表面活性剂包括十二烷基硫酸钠和双(2-乙基己基)磺基琥珀酸钠中的至少一种,金属无机盐包括金属硝酸盐和金属氯酸盐中的至少一种。
2.如权利要求1所述的制备方法,其特征在于:所述pH调节剂为5%硝酸溶液和/或25%氢氧化钠溶液。
3.一种聚合物表面化学镀铜金属化方法,其特征在于:包括:将聚合物表面除油、粗化和亲水处理后,在20-50℃的权利要求1或2所述制备方法制得的银胶体活化液组合物中活化0.5-10 min,然后在无机酸、无机盐或有机物水溶液中解胶后进行化学镀铜。
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