CN108950443B - 一种具有抗菌和骨诱导活性功能的医用钛合金棒材 - Google Patents
一种具有抗菌和骨诱导活性功能的医用钛合金棒材 Download PDFInfo
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Abstract
本发明提供了一种具有抗菌和骨诱导活性功能的医用钛合金棒材,包括钛合金棒材本体、离子注入层和其外部的包覆涂层,所述的钛合金棒材本体的化学成分按质量百分比计为:W 2.0%~5.0%、Zn 3%~8%、Fe 2%~6%、Mo 0.5%~1.2%、Sr 0.5%~1.0%、Se 0.5%~1.2%、Sn 0.4%~1.0%,余量为Ti;所述的离子注入层为银离子注入层;所述外部包覆涂层的组成按质量百分比计为:15%~25%的纳米β‑Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖。本发明所提供的钛合金棒材力学性能优异、具有抗菌功能、生物相容性好、骨诱导活性明显、可促进凝血和伤口愈合。
Description
技术领域
本发明属于医用新材料技术领域,特别涉及一种具有抗菌和骨诱导活性功能的医用钛合金棒材。
背景技术
金属、陶瓷和高分子材料是当今三大医用人工骨关节材料,三种材料各有其优缺点。金属和陶瓷在负载荷医疗领域已得到了广泛的应用,但是金属易磨损和腐蚀,而陶瓷则脆性大,高分子材料柔韧性好但耐磨性及硬度较差。随着现代医学与材料学的发展,金属材料以其良好的力学性能和加工性能成为目前临床应用较广泛的植入材料,钛合金以其优良的力学性能、较好的生物相容性得到了广泛的应用。
但钛合金医用新材料的应用存在以下不足:①钛合金与骨之间只是一种机械嵌连性整合,植入体在体内长期服役后,摩擦产生的磨屑会影响其生物活性,从而引发局部组织炎症,缩短其使用寿命;②有一定的生物相容性,但不具有骨诱导活性;③无抗菌性;④不具有促进凝血和伤口愈合的作用。
基于以上原因,通过采用各种表面涂层或薄膜技术在钛合金基体表面制备抗磨损生物相容涂层,用于提高人工骨关节的耐磨损性、抗腐蚀性和生物相容性,是钛合金医用新材料的研究热点。
国内专利申请号为201510508585.2公开了一种医用骨固定器件的制备方法,但没有解决耐磨性问题;申请号为201710979298.9公布了一种医用钛合金及其制备方法,耐磨性好,但不具有骨诱导活性;申请号为201510476616.0公布了一种医用钛合金棒材,申请号为201510476615.6公布了一种抗菌能力强的医用钛合金棒材,两种专利技术均是在钛合金棒外层包覆涂层,但无骨诱导活性,也没有促进凝血和伤口愈合的作用。
发明内容
为了解决上述问题,本发明提供了一种具有抗菌和骨诱导活性功能的医用钛合金棒材,具有以下优点:力学性能接近人骨,具有良好的生物相容性和骨诱导活性,且有一定的抗菌作用,并可促进凝血和伤口愈合,是一种理想的医用钛合金。
基于以上目的,本发明提供了一种具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,所述的具有骨诱导活性的医用钛合金棒材,包括钛合金棒材本体、银离子注入层和其外部的包覆涂层,所述的钛合金棒材本体的化学成分按质量百分比计为:W2.0%~5.0%、Zn 3%~8%、Fe 2%~6%、Mo 0.5%~1.2%、Sr 0.5%~1.0%、Se 0.5%~1.2%、Sn 0.4%~1.0%,余量为Ti;所述外部包覆涂层的组成按质量百分比计为:15%~25%的纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;制备工艺过程为:制备钛合金铸锭→变形加工→热处理→表面预处理→银离子注入→表面喷涂。
进一步地,所述具有抗菌和骨诱导活性功能的医用钛合金棒材由以下步骤制得:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 1.0%~4.0%、Zn 3%~8%、Fe 2%~6%、Mo 0.5%~1.2%、Sr 0.5%~1.0%、Se 0.5%~1.2%、Sn 0.4%~1.0%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径3~10mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)银离子注入:使用等离子浸没离子注入技术在钛合金表面注入银离子,本底真空度为(8.5~9.5)×10-4Pa,注入电压为18~32kV,频率为5~15Hz,脉宽为100~500μs,注入时间为3.5h;
6)表面喷涂层的制备:
①将纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1)是按总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成的复合颗粒;
②将①中制备的复合颗粒与壳聚糖混合,混合物的化学成分按质量百分计为:15%~25%纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;
③采用等离子喷涂方法,工艺参数为:电弧等离子体氢气的流量为10~22L/min,电弧等离子体氩气的流量为10~30L/min,送粉速率为3~12g/min,粉末载气(氩气)的流量为0.3~3.0L/min,电流为400~650A,喷涂距离30~40mm,喷涂厚度0.2~1.0mm。
本发明所提供的具有抗菌和骨诱导活性功能的医用钛合金棒材具有以下优点:
1)合金成分科学,Zn、Fe可降低钛合金阳极活性,提高钛合金的钝化能力;Mo可提高钛合金的热力学稳定性,进一步优化钛合金的力学性能;Zn、Fe、Sr、Se、Mo是促进骨生产元素,使钛合金具有骨诱导活性;Sn、Zn、Fe可有效降低钛合金的熔点,利于制造,W可调整钛合金的线胀系数使之接近人骨;
2)对钛合金进行变形加工和热处理,使得钛合金棒材的力学性能更加优异;
3)银离子注入后,钛合金棒材表面分布着粒径大小为8~15nm以单质形态存在的纳米银粒子,外部包覆涂层降解后,露出银离子注入层,能显著提高钛金属的抗菌能力;
4)纳米β-Ca3(PO4)2、纳米CaCO3形成复合颗粒后,由于碳酸钙的良好的可分散性,复合颗粒在喷涂粉末中能均匀分散,其降解过程中释放出的大量磷酸根离子与钙离子可原位形成类骨质磷灰石矿物的沉积,有利于钛合金棒材在人体内降解过程中骨组织的再生,生物相容性和骨诱导活性明显;壳聚糖快速降解后形成的多孔结构有利于骨组织的长入,而且具有促进凝血和伤口愈合的作用。
具体实施方式
以下结合实施例对本发明的原理和特征进行描述,所列举实例只用于解释本发明,并非限定本发明的范围。
实施例1:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 2.0%、Zn 4.0%、Fe 2%、Mo0.7%、Sr 0.5%、Se 1.2%、Sn 0.6%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径5mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)银离子注入:使用等离子浸没离子注入技术在钛合金表面注入银离子,本底真空度为8.5×10-4Pa,注入电压为20kV,频率为8Hz,脉宽为200μs,注入时间为3.5h;
6)表面喷涂层的制备:
①将纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1)是按总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成的复合颗粒;
②将①中制备的复合颗粒与壳聚糖混合,混合物的化学成分按质量百分计为:15%纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;
③采用等离子喷涂方法,工艺参数为:电弧等离子体氢气的流量为10L/min,电弧等离子体氩气的流量为15L/min,送粉速率为5g/min,粉末载气(氩气)的流量为0.5L/min,电流为480A,喷涂距离30mm,喷涂厚度0.5mm;
7)抗菌实验:将制备好的钛合金棒材截取50mm长度,经无水乙醇、去离子水超声清洗,各8min,然后放入体积分数75%酒精溶液中消毒45min。测试细菌为金黄色葡萄球菌。首先将消毒后的钛合金棒材放进培养皿中,加入50mL菌悬液,静止培养2h,以使细菌充分黏附。之后用PBS溶液冲洗掉表面疏松黏附的细菌,一共冲洗3次。将冲洗过后的钛合金棒材放进50mLPBS溶液中,超声振荡3min,将表面黏附的细菌冲洗掉。之后将含有表面黏附细菌的PBS溶液取5mL,均匀铺在培养基板上,将培养基板放进37℃的恒温培养箱中培养12h,观察、计算菌落数;
8)骨诱导活性实验:在制备好的钛合金棒材上接种新生大鼠颅骨成骨细胞,接种密度为300个/mm2,用含有体积分数为10%的新生牛血清的DMEM培养基培养,每1d换液,分别培养3d和5d,然后每孔加入MTT 0.1mL,37℃培养4h,吸弃上清液,再每孔加入DMSO0.5mL,用酶标仪于波长490nm处测定吸光度。
实施例2:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 2.2%、Zn 4.5%、Fe2.2%、Mo0.8%、Sr 0.6%、Se 1.5%、Sn 0.7%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径10mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)银离子注入:使用等离子浸没离子注入技术在钛合金表面注入银离子,本底真空度为9.0×10-4Pa,注入电压为22kV,频率为9Hz,脉宽为300μs,注入时间为3.5h;
6)表面喷涂层的制备:
①将纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1)是按总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成的复合颗粒;
②将①中制备的复合颗粒与壳聚糖混合,混合物的化学成分按质量百分计为:20%纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;
③采用等离子喷涂方法,工艺参数为:电弧等离子体氢气的流量为20L/min,电弧等离子体氩气的流量为25L/min,送粉速率为10g/min,粉末载气(氩气)的流量为2.0L/min,电流为550A,喷涂距离40mm,喷涂厚度0.6mm;
7)抗菌实验:按实施例1进行;
8)骨诱导活性实验:按实施例1进行。
实施例3:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 3.2%、Zn6%、Fe 4.8%、Mo 1.1%、Sr 0.8%、Se 0.9%、Sn 0.8%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径8mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)银离子注入:使用等离子浸没离子注入技术在钛合金表面注入银离子,本底真空度为9.0×10-4Pa,注入电压为25kV,频率为10Hz,脉宽为350μs,注入时间为3.5h;
6)表面喷涂层的制备:
①将纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1)是按总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成的复合颗粒;
②将①中制备的复合颗粒与壳聚糖混合,混合物的化学成分按质量百分计为:25%纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;
③采用等离子喷涂方法,工艺参数为:电弧等离子体氢气的流量为12L/min,电弧等离子体氩气的流量为18L/min,送粉速率为6g/min,粉末载气(氩气)的流量为0.8L/min,电流为550A,喷涂距离36mm,喷涂厚度0.6mm;
7)抗菌实验:按实施例1进行;
8)骨诱导活性实验:按实施例1进行。
对比例1:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 3.2%、Zn6%、Fe 4.8%、Mo 1.1%、Sr 0.8%、Se 0.9%、Sn 0.8%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径8mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)抗菌实验:按实施例1进行;
5)骨诱导活性实验:按实施例1进行。
对比例2:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 3.2%、Zn6%、Fe 4.8%、Mo 1.1%、Sr 0.8%、Se 0.9%、Sn 0.8%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min),将熔化过的铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径8mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)银离子注入:使用等离子浸没离子注入技术在钛合金表面注入银离子,本底真空度为9.0×10-4Pa,注入电压为25kV,频率为10Hz,脉宽为350μs,注入时间为3.5h;
6)抗菌实验:按实施例1进行;
7)骨诱导活性实验:按实施例1进行。
对比例3:
1)制备钛合金铸锭:所述的钛合金铸锭的化学成分按质量百分比计为:W 3.2%、Zn6%、Fe 4.8%、Mo 1.1%、Sr 0.8%、Se 0.9%、Sn 0.8%,余量为Ti;
将配好的原料放入非自耗电极水冷铜坩埚电弧炉中,将炉膛抽真空到8.5×10- 4Pa,通入纯度为99.99%的氩气进行3次反复洗气,通电熔炼(温度1800℃,保温时间60min)后铸造成锭,将铸锭翻转180°进行重熔5次保证成分均匀性;
2)变形加工:在铸锭表面涂覆一层六方氮化硼,防止高温加工时氧化并增加润滑,将涂有六方氮化硼的铸锭在850~1150℃保温2.5h,然后进行自由锻,终锻温度650~750℃,反复锻造5次,冷却到室温,再将初步锻造的坯料加热到880~980℃后挤压成直径8mm的棒状;
3)热处理:950℃保温2h固溶处理,然后炉冷到520℃保温6h;
4)表面预处理:将钛合金棒材进行如下处理:旋纹拉花→脱脂→热水洗→冷水洗→活化(用体积分数35%的乙酸在40℃下洗涤1min)→热水洗→冷水洗;
5)表面喷涂层的制备:
①将纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1)是按总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成的复合颗粒;
②将①中制备的复合颗粒与壳聚糖混合,混合物的化学成分按质量百分计为:15%~25%纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒(两者质量比为1∶1),余量为壳聚糖;
③采用等离子喷涂方法,工艺参数为:电弧等离子体氢气的流量为12L/min,电弧等离子体氩气的流量为18L/min,送粉速率为6g/min,粉末载气(氩气)的流量为0.8L/min,电流为550A,喷涂距离36mm,喷涂厚度0.6mm;
6)抗菌实验:按实施例1进行;
7)骨诱导活性实验:按实施例1进行;
实施例和对比例得到的结果如表1所示。
表1
上述实例表明:采用制备钛合金铸锭→变形加工→热处理工艺制造的钛合金棒材(对比例1)的力学性能好,但抗菌性差,骨诱导活性差;采用制备钛合金铸锭→变形加工→热处理→表面预处理→银离子注入工艺制造的钛合金棒材(对比例2),抗菌性好,骨诱导活性差;采用制备钛合金铸锭→变形加工→热处理→表面预处理→表面喷涂工艺制造的钛合金棒材(对比例3),抗菌性差,骨诱导活性好。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,包括钛合金棒材本体、离子注入层和其外部的包覆涂层,所述的钛合金棒材本体的化学成分按质量百分比计为:W 2.0%~5.0%、Zn 3%~8%、Fe 2%~6%、Mo 0.5%~1.2%、Sr 0.5%~1.0%、Se 0.5%~1.2%、Sn0.4%~1.0%,余量为Ti;所述的离子注入层为银离子注入层;所述外部包覆涂层的组成按质量百分比计为:15%~25%的纳米β-Ca3(PO4)2与纳米CaCO3复合颗粒,余量为壳聚糖,所述的复合颗粒中纳米β-Ca3(PO4)2与纳米CaCO3两者质量比为1∶1。
2.根据权利要求1所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,制备过程为:制备钛合金铸锭→变形加工→热处理→表面预处理→银离子注入→表面喷涂。
3.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,用非自耗电弧炉对原料熔炼,然后浇注成钛合金铸锭。
4.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,采用自由锻和热挤压进行变形加工。
5.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,热处理工艺为:950℃保温2h固溶处理,然后炉冷到520℃保温6h。
6.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,表面预处理工艺为:旋纹拉花→脱脂→热水洗→冷水洗→活化→热水洗→冷水洗,所述的活化工艺是用体积分数35%的乙酸在40℃下洗涤1min。
7.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,使用等离子浸没离子注入技术在钛合金表面注入银离子。
8.根据权利要求1所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,纳米β-Ca3(PO4)2和纳米CaCO3复合颗粒中两者的质量比为1∶1,按颗粒总质量浓度0.04~0.4g/mL加入硬脂酸钠乙醇溶液中,在40℃下搅拌2.5h,然后通过喷雾干燥形成复合颗粒。
9.根据权利要求2所述的具有抗菌和骨诱导活性功能的医用钛合金棒材,其特征在于,表面喷涂工艺为:电弧等离子体氢气的流量为10~22L/min,电弧等离子体氩气的流量为10~30L/min,送粉速率为3~12g/min,粉末载气氩气的流量为0.3~3.0L/min,电流为400~650A,喷涂距离30~40mm,喷涂厚度0.2~1.0mm。
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