CN110606762B - 一种碳纤维复合材料颅骨修补片及其制备方法 - Google Patents
一种碳纤维复合材料颅骨修补片及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种碳纤维复合材料颅骨修补片及其制备方法,颅骨修补片由至少一层碳纤维机织布和至少一层碳纤维非织造布叠加构成;碳纤维机织布和碳纤维非织造布的碳纤维间均填充有基体碳和/或碳化硅;该颅骨修补片具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、疲劳性好、可设计性强、无伪影等特点,特别适合颅骨修补使用。
Description
技术领域
本发明涉及一种颅骨修补片,具体涉及一种碳纤维复合材料颅骨修补片及其制备方法,属于生物医用材料领域。
背景技术
因创伤、感染、肿瘤、手术等造成直径大于3厘米以上的颅脑缺损,就可能产生临床症状。为保持颅腔封闭、患者外形修复、避免生理异常等,需要进行颅骨修复手术。
用于颅骨修补的材料主要有自体骨,及人工高分子、金属等材料都是颅骨修补的常用材料。相比而言,钛合金在钢性、强度、可塑性及生物相容性方面已较理想,但其存在一定缺陷:(1)机械相容性欠佳,应力分布不均匀、植入物松动或脱位,局部致骨质疏松、骨吸收、骨折、骨愈合延缓等。(2)边缘通常较锋利易损伤皮肤,造成植入物的外露;(3)导热系数高,可导致患者在温差较大下有不适感。(4)强度和硬度均低于颅骨组织,耐冲击时易产生塑性变形。(5)医学检查有伪影,会影响后期诊断与康复治疗。碳材料具有很好的生物相容性,其在生物医用的多方面得到应用,但是现有技术中还未见采用碳材料成功设计及制备颅骨修补材料的相关报道。
发明内容
针对现有技术中的颅骨修补材料存在的缺陷,本发明的第一个目的是在于提供了一种碳纤维编制和仿形相结合的碳纤维复合材料颅骨修补片,该颅骨修补片具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、疲劳性好、可设计性强、无伪影等特点,特别适合颅骨修补使用。
本发明的另一个目的是在于提供一种步骤简单、原料易得制备颅骨修补片的方法。
为了实现上述技术目的,本发明提供了一种碳纤维复合材料颅骨修补片,其由至少一层碳纤维机织布和至少一层碳纤维非织造布叠加构成;碳纤维机织布和碳纤维非织造布的碳纤维间均填充有基体碳和/或碳化硅。
优选的方案,碳纤维复合材料颅骨修补片由1~4层碳纤维机织布与1~4层碳纤维非织造布叠加构成。碳纤维复合材料颅骨修补片中的机织布由长纤维构成,碳纤维含量高,主要提供强度支持,而碳纤维非织造布为短纤维构成,其可以设置在表层,设置在表层时,利用其本身孔隙率高的特点,可为组织细胞附着提供大量表面,同时利用其短纤维穿入内层碳纤维布中,起到铆接作用,且有利于组织细胞生长至碳纤维内部,以提高颅骨修补片与组织的结合能力。碳纤维非织造布也可以设置在任意两层碳纤维机织布层间,起到填充作用,并且利用短纤维的刺穿作用起到层间铆接,且使表层碳纤维机织布表面产生孔隙,有利于为组织细胞附着提供有效表面。通过调节碳纤维机织布可以控制力学强度。
优选的方案,任意相邻两层碳纤维机织布之间层间旋转0°~45°。通过旋转一定角度可以改善复合材料的力学性能。
优选的方案,所述碳纤维复合材料颅骨修补片表面粗糙度小于0.4μm。颅骨修补片由于引入碳纤维非织造布保持一定的孔隙率可便于组织细胞长入,提高组织相容性和与组织之间的结合能力,表面粗糙度小可降低局部脱落。
优选的方案,所述基体碳包括热解碳、树脂碳、沥青碳中至少一种。
优选的方案,碳纤维机织布和碳纤维非织造布之间采用碳纤维通过逐层针刺方式或穿刺方式进行铆接,铆接点面密度为5点/cm2~25点/cm2。如果是多层碳纤维机织布和多层碳纤维非织造布不是交替叠加时,层间同样采用该铆接方法。采用碳纤维机织布和碳纤维非织造布的叠加时,可以利用碳纤维非织造布的短纤维进行铆接。通过铆接可以提高碳纤维机织布和碳纤维非织造布之间的结合强度,改善综合力学性能。
优选的方案,所述碳纤维复合材料颅骨修补片中心设有固定-引流孔,孔间距为1cm~3cm,孔径为0.1cm~0.3mm,四周设有固定孔,孔间距为0.5cm~1cm,孔径为0.1cm~0.3mm。中心设有的固定-引流孔主要是作为缝合线连接固定点和局部积液引流孔。四周的固定孔方便螺钉固定在自体骨组织上。
优选的方案,碳纤维机织布包括面密度为120g/m2~1000g/m2的平纹布、斜纹布或缎纹布。较优选为200g/m2~600g/m2。
优选的方案,所述碳纤维非织造布的面密度为10g/m2~60g/m2。较优选为20g/m2~40g/m2。
本发明还提供了一种碳纤维复合材料颅骨修补片的制备方法,该方法包括以下步骤:
1)将至少一层碳纤维机织布与至少一层碳纤维非织造布叠层(可在厚度方向进行铆接),通过模具辅助成型,得到碳纤维预制体;
2)采用化学气相渗透法和/或浸渍-裂解法和/或反应融渗法对碳纤维预制体进行增密生成基体碳和/或碳化硅后,机加工,即得。
本发明的碳纤维预制体成型模具采用的材料为现有技术常见模具材料,如铝合金、碳材料等。
本发明的方法还可以将生成基体碳和/或碳化硅后的坯体进行高温除杂处理步骤,或者不进行处理。
本发明的化学气相渗透生成基体碳工艺:将碳纤维预制体放入真空炉中,在850℃~1300℃温度下,通入的含碳气源(天然气、甲烷或丙烯等,氮气或氢气为稀释气体,碳源气体与稀释气体的流量比为1:0~2)经过裂解后,化学气相渗透在碳纤维坯料中,经过10小时~100小时,制备成碳纤维复合材料坯体。
本发明的浸渍-裂解生成基体碳工艺:碳纤维预制体经过树脂(呋喃、酚醛和糠酮等)或沥青(石墨沥青、煤沥青)真空加压浸渍、固化处理(树脂)、裂解(树脂:900℃~1050℃,常压;沥青:750℃~850℃,50MPa~200MPa)等致密化工艺。浸渍压力为1.0MPa~5.0MPa,浸渍时间为2小时~10小时;固化温度为160℃~230℃,固化时间为10小时~50小时;裂解时间为2小时~20小时。
本发明的化学气相渗透生成碳化硅基体工艺:将碳纤维预制体放入真空炉中,在900℃~1300℃温度下,通入的气源(三氯甲基硅烷,氢气为载气和稀释气体,三氯甲基硅烷与氢气的流量比为1:1~10),经过裂解后,化学气相渗透在碳纤维坯料中,经过10小时~100小时,制备成碳纤维复合材料坯体。
本发明的浸渍-裂解生成碳化硅基体工艺:碳纤维预制体经过含硅前驱体(聚碳硅烷PCS、聚甲基硅烷PMS)真空加压浸渍、固化处理、裂解等致密化工艺。浸渍压力为1.0MPa~5.0MPa,浸渍时间为2小时~10小时;固化温度为160℃~230℃,固化时间为10小时~50小时;裂解温度为800℃~1150℃,时间为2小时~20小时;陶瓷化温度为1200℃~1600℃,时间为2小时~10小时。
本发明的化学气相渗透生成碳化硅-碳基体工艺:可以先生成基体碳,再生成碳化硅,或者同时生成基体碳和碳化硅,或者先生成碳化硅,再生成碳。同时生成碳和碳化硅的工艺:将碳基体气源和三氯甲基硅烷同时通入,其他条件与生成碳的工艺条件相同。
本发明的浸渍-裂解生成碳化硅-碳基体工艺,可以先致密基体碳,再致密碳化硅,或者同时致密基体碳和碳化硅,或者先致密碳化硅,再致密基体碳。同时致密基体碳和碳化硅的工艺:将树脂/沥青和含硅前驱体同时浸渍,其他条件与致密碳的工艺条件相同,硅基陶瓷化温度为1200℃~1600℃,时间为2小时~10小时。
本发明的反应融渗法生成碳化硅基体条件为:硅粉粒度为1μm~50μm;熔渗温度为1450℃~1750℃,时间为1小时~6小时。在进行反应融渗法生成碳化硅之前最好是先生成碳基体,以减少反应融渗法生成碳化硅过程中对碳纤维反应损害强度。
本发明的高温除杂和调质处理工艺为:温度为1500℃~2300℃,保温时间为1小时~10小时。
本发明的机加工包括表面修整和打孔、抛光等处理过程。
相对现有技术,本发明的技术方案带来的有益技术效果:
本发明的碳纤维复合材料颅骨修补片具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、疲劳性好、可设计性强、无伪影等特点,特别适合颅骨修补使用。
本发明的碳纤维复合材料颅骨修补片具有多层碳纤维机织布和碳纤维非织造布叠层结构,具有较好的力学性能,且具有一定孔隙度,有利于组织细胞生长至内部,提高与组织的结合能力。
本发明的碳纤维复合材料颅骨修补片具有良好的机械性能,如弯曲强度≥200MPa,弯曲模量为10GPa~20GPa,拉伸强度为100MPa~150MPa。
本发明的碳纤维复合材料颅骨修补片是碳纤维编织和仿形相结合,可以根据实际需要,设计并制备出任意形状颅骨修补片,满足手术需要。
附图说明
图1碳纤维复合材料颅骨修补片实物图;其中,碳纤维复合材料颅骨修补片的中心均匀分布孔为固定-引流孔,四周的两排错位孔为固定孔。
具体实施方式
以下实施例旨在进一步说明本发明内容,而不是限制本发明权利要求保护范围。
实施例1
1)碳纤维预制体
将3层3k(1k表示一千根)碳纤维平纹布(面密度为200g/m2)与3层碳纤维非织造布(面密度为20g/m2)交叉叠层,三层平纹布层叠加,层间纤维排布呈30°交叉,平纹布间设置碳纤维非织造布,在叠层厚度上针刺,铆接点密度为10点/cm2,依托模具成形,层间碳纤维铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体在1100℃温度下,通入甲烷(氮气作为稀释气体,流量比为1:0.5)经过裂解后,化学气相渗透在碳纤维坯料中,经过80小时,制成所需要的碳纤维复合材料坯料。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至2000℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,碳纤维机织布抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为265MPa,弯曲模量为15GPa,拉伸强度为138MPa,存在明显孔隙,有利于组织细胞生长。
实施例2
1)碳纤维预制体
将1层6k碳纤维斜纹布(面密度为320g/m2)和1层3k碳纤维缎纹布(面密度240g/m2)与2层,厚度为0.3mm的碳纤维非织造布(面密度为30g/m2)交叉叠层,斜纹布层和缎纹布层间纤维排布呈45°交叉,在叠层厚度上针刺,铆接点密度为10点/cm2,依托模具成形,层间碳纤维铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体经过煤沥青真空加压浸渍,浸渍压力为3.0MPa,浸渍时间为5小时,裂解温度为800℃,压力为100MPa,时间为10小时使其致密化,得到坯体。
3)高温处理
将(2)所得的坯体放入高温炉中,在真空气氛条件下加热至1800℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,表面抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为226MPa,弯曲模量为18GPa,拉伸强度为143MPa,存在明显孔隙,有利于组织细胞生长实施例3
1)碳纤维预制体
将3层碳纤维机织布叠层与2层碳纤维非织造布交叉叠层,外层为1k碳纤维平纹布,面密度为140g/m2,中心夹层为3k碳纤维斜纹布,面密度为220g/m2,碳纤维机织布间设置碳纤维非织造布(厚度为0.4mm,面密度为20g/m2),在厚度方向穿刺铆接,刺密度为12点/cm2,层间纤维排布呈40°交叉,依托模具成形,层间铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体,先在1000℃温度下,通入天然气经过裂解后,化学气相渗透在碳纤维坯料中,经过40小时;再经过煤沥青真空加压浸渍,浸渍压力为2.0MPa,浸渍时间为3小时;裂解温度为850℃,压力为80MPa,时间为10小时使其致密化,得到坯体。
3)高温处理
将(2)所得的坯体放入高温炉中,在真空气氛条件下加热至1900℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,表面抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为232MPa,弯曲模量为12GPa,拉伸强度为115MPa,存在明显孔隙,有利于组织细胞生长实施例4
1)碳纤维预制体
将1层6k碳纤维平纹布(面密度为320g/m2)与1层碳纤维非织造布(面密度为30g/m2)叠层,在厚度方向穿刺铆接,铆接点密度为10点/cm2,依托模具成形,层间铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体在1200℃温度下,通入甲烷经过裂解后,化学气相渗透在碳纤维坯料中,经过90小时,制成所需要的碳纤维复合材料坯料。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至2000℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,表面抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为220MPa,弯曲模量为11GPa,拉伸强度为108MPa,存在明显孔隙,有利于组织细胞生长。
实施例5
1)碳纤维预制体
将1层24k碳纤维平纹布(面密度为600g/m2)与1层碳纤维非织造布(面密度为40g/m2)叠层,在厚度方向穿刺铆接,铆接点密度为15点/cm2,依托模具成形,层间铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体先在1200℃温度下,通入甲烷经过裂解后,化学气相渗透在碳纤维坯料中,经过40小时,再在1200℃温度下,通入的气源(三氯甲基硅烷,氢气为载气和稀释气体,三氯甲基硅烷与氢气的流量比为1:5,经过裂解后,化学气相渗透在碳纤维坯料中,经过500小时,制备成碳纤维复合材料坯体。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至1600℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,表面抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为242MPa,弯曲模量为12GPa,拉伸强度为117MPa,存在明显孔隙,有利于组织细胞生长。
实施例6
1)碳纤维预制体
将1层12k碳纤维平纹布(面密度为400g/m2)与1层碳纤维非织造布(面密度为40g/m2)叠层,在厚度方向穿刺铆接,铆接点密度为10点/cm2,依托模具成形,层间铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体经过含硅前驱体PCS真空加压浸渍、固化处理、裂解等致密化工艺。浸渍压力为3.0MPa,浸渍时间为5小时;固化温度为200℃,固化时间为20小时;裂解温度为950℃,时间10小时;其中硅基陶瓷化温度为1400℃,时间为4小时。制备成碳纤维复合材料坯体。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至1600℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,表面抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为231MPa,弯曲模量为11GPa,拉伸强度为110MPa,存在明显孔隙,有利于组织细胞生长。
对比实施例1
1)碳纤维预制体
将3层3k碳纤维平纹布(面密度为200g/m2)叠加,层间纤维排布呈30°交叉,在叠层厚度上针刺,铆接点密度为10点/cm2,依托模具成形,层间碳纤维铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体在1100℃温度下,通入甲烷(氮气作为稀释气体,流量比为1:0.5)经过裂解后,化学气相渗透在碳纤维坯料中,经过80小时,制成所需要的碳纤维复合材料坯料。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至2000℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,碳纤维机织布抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为145MPa,弯曲模量为14GPa,拉伸强度为129MPa,没有明显孔隙,不利于组织细胞生长。
对比实施例2
1)碳纤维预制体
将3层碳纤维非织造布(面密度为20g/m2)叠加,在叠层厚度上针刺,铆接点密度为10点/cm2,依托模具成形,层间碳纤维铆接而成碳纤维仿形预制体。
2)增密
将步骤(1)所得的碳纤维仿形预制体在1100℃温度下,通入甲烷(氮气作为稀释气体,流量比为1:0.5)经过裂解后,化学气相渗透在碳纤维坯料中,经过80小时,制成所需要的碳纤维复合材料坯料。
3)高温处理
将(2)所得的坯体放入高温炉中,在氩气保护气氛条件下加热至2000℃,保温时间为4小时。
4)将坯体加工,在坯体中心打固定-引流孔,孔间距为2cm,孔径为0.2mm,四周设有固定孔,孔间距为0.8cm,孔径为0.2mm,碳纤维机织布抛光至粗糙度小于0.4μm,即得碳纤维复合材料颅骨修补片。
碳纤维复合材料颅骨修补片的弯曲强度为89MPa,弯曲模量为9GPa,拉伸强度为46MPa,相对于实施例1强度大幅度下降,存在明显孔隙,有利于组织细胞生长。
Claims (6)
1. 一种碳纤维复合材料颅骨修补片,其特征在于:由1~4层碳纤维机织布与1~4层碳纤维非织造布叠加构成;且碳纤维机织布和碳纤维非织造布的碳纤维间均填充有基体碳和/或碳化硅;所述碳纤维机织布包括面密度为120g/m2~1000g/m2的平纹布、斜纹布或缎纹布;所述碳纤维非织造布的面密度为10 g/m2~60g/m2;碳纤维机织布和碳纤维非织造布之间采用碳纤维通过逐层针刺方式或穿刺方式进行铆接,铆接点面密度为5点/cm2~25点/cm2。
2.根据权利要求1所述的一种碳纤维复合材料颅骨修补片,其特征在于:任意相邻两层碳纤维机织布之间层间旋转0°~45°。
3.根据权利要求1所述的一种碳纤维复合材料颅骨修补片,其特征在于:所述碳纤维复合材料颅骨修补片表面粗糙度小于0.4μm。
4.根据权利要求1所述的一种碳纤维复合材料颅骨修补片,其特征在于:所述基体碳包括热解碳、树脂碳、沥青碳中至少一种。
5.根据权利要求1所述的一种碳纤维复合材料颅骨修补片,其特征在于:所述碳纤维复合材料颅骨修补片中心设有固定-引流孔,孔间距为1cm ~3cm,孔径为0.1cm ~0.3mm,四周设有固定孔,孔间距为0.5cm ~1cm,孔径为0.1cm ~0.3mm。
6.根据权利要求1~5任一项所述的一种碳纤维复合材料颅骨修补片的制备方法,其特征在于:包括以下步骤:
1)将至少一层碳纤维机织布与至少一层碳纤维非织造布叠层并在厚度方向采用碳纤维通过逐层针刺方式或穿刺方式进行铆接,通过模具辅助成型,得到碳纤维预制体;
2)采用化学气相渗透法和/或浸渍-裂解法和/或反应融渗法对碳纤维预制体进行增密生成基体碳和/或碳化硅后,机加工,即得。
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