CN106660889A - 多孔陶瓷成型制品的成型方法和多孔陶瓷产品 - Google Patents
多孔陶瓷成型制品的成型方法和多孔陶瓷产品 Download PDFInfo
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- C04B28/188—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
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- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
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Abstract
制作多孔的、化学键合陶瓷成型制品的方法,包括:i)提供包含聚合物颗粒和陶瓷自凝固骨水泥粉末的前体粉末混合物;ii)从包含所述前体粉末混合物和含水液体的浆中制备成型制品;iii)将所述成型制品在浸泡液中浸泡大约10分钟到大约两周的一段时间以在所述浸泡液中溶解所述聚合物颗粒,从而在所述成型制品中生成孔隙,在所述浸泡液中所述聚合物颗粒是可溶的。可以通过这些方法形成具有互联孔隙、总孔隙度至少约50%和大孔隙度至少约30%的多孔的化学键合陶瓷成型制品。
Description
技术领域
本发明针对多孔陶瓷成型制品的成型方法,并且,更具体地,本申请涉及使用牺牲相(sacrifying phase)的多孔陶瓷成型制品的成型方法。在一个实施例中,本发明也针对在生物医学应用的用途中特别有益的多孔陶瓷成型制品,例如,作为在体内传递药物和细胞的支架和种植体。在某些实施例中,所述多孔陶瓷成型制品是大孔隙的,并且在某些实施例中,所述多孔成型制品具有均匀的孔隙度。
背景技术
用来填充骨空隙的合成材料已经成为令人感兴趣的研究主题很多年了,并且这些材料有很多潜在的和重要的应用,尤其包括,由于骨肉瘤和创伤的空隙填充。当今实践的黄金准则,自体骨,具有实用性有限和抵抗疼痛的风险的缺点。为了克服与自体骨使用相关的这样的缺陷,合成材料已经成为重要的替代品。磷酸钙陶瓷是在这些应用中使用的主要合成材料类别之一,并且其有利地与生物降解和生物相容性结合。所述磷酸钙陶瓷具有化学组成与骨的矿物相相似的的优点,即,离子取代的缺钙的羟磷灰石。
用于骨空隙填充应用的磷酸钙(CaP)材料以包括预制支架,颗粒,油灰和自凝固骨水泥的多种物理形式提供。通过低温的方法生成的磷酸钙,即,通过骨水泥溶解-沉淀反应,被认为是化学键合陶瓷材料和具有小晶粒的缠结网络。相比通过制备更大以及更紧凑的晶体的高温烧结法制备的支架,小尺寸的晶粒使得磷酸钙骨水泥(CPCs)更快地降解。
具有快的再吸收率、反映到同样快速形成新骨的骨空隙填充材料是令人非常期望的。可再吸收的磷酸钙种植体应该作为新骨形成的模板并在骨空隙中阻止纤维化组织的形成,而不是作为永久的骨替代品,类似于自体骨发挥作用的方式。为了增强在合成骨空隙填充物中的骨长入,已提出并且经过检测有好的结果的是引入大孔隙可能是有帮助的。两个重要的机制负责骨长入到骨空隙填充物中。第一个是破骨细胞退化,类似于骨的正常重构机制,第二个是通过溶解所述材料进行吸收。尽管磷酸钙骨水泥基底的骨空隙填充物具有高的固有孔隙度,所述孔隙尺寸主要位于1μm附近和更低。增加大孔隙的数量,即,具有大于10μm尺寸的孔隙,以及增加的孔隙的互联性,能够在材料内改善细胞定植和增加破骨细胞的降解。有研究表明,大于100μm的孔隙尺寸对于好的骨长入是必须的,为了实现增强的毛细血管和骨生成,建议达到尺寸大于300μm。见Karageorgiou等,生物材料,26:5474-91(2005)。
大孔隙骨水泥既可以被注入到骨空隙中和设置在原位,也可以在体外硬化成为所需的形状,正常的是称为颗粒形状,并且用作体外支架或者种植体。通常,可以通过几条途径将大孔隙引入骨水泥中。一种方法使用骨水泥相和牺牲相(通常为糖)的混合物,牺牲相在骨水泥凝固后溶解,从而生成空隙。另一种方法加入表面活性剂以在骨水泥混合期间捕获空气(见Sarda等,生物医用材料研究杂志A部分;65A:215-21(2003)。也使用了骨水泥浆的机械发泡(见Ginebra等,生物医用材料研究杂志A部分,80A:351-61(2007);Perut等,生物材料学报,7:1780-7(2011);Montufar等,材料科学杂志:医用材料,21:863-9(2010))。所述两大主要途径,然而,是使用牺牲相和机械发泡的。使用这些常规方法的缺陷是难以实现受控的孔隙尺寸分布和互联性,即,孔隙的互联。尽管通过严格控制的发泡步骤,发泡可以使泡沫中的孔隙可控的分布,但在骨水泥凝固期间泡沫很容易破裂和变形并且很难保证在最终产品中的孔隙的均匀分布。使用糖作为牺牲相也具有几个缺点。主要地,糖的快速溶解性经常在骨水泥凝固开始之前导致溶解,影响骨水泥凝固机制和生成不可预测的孔隙尺寸和分布。此外,糖难以成型成期望的形状,从而限制牺牲相的尺寸和形状。
因此,需要多孔陶瓷成型制品的新成型方法,并且,此外,需要避免现有技术缺陷的、适合用作种植体的、具有大孔隙的多孔陶瓷成型制品的新成型方法。
发明内容
本发明的目的是提供多孔陶瓷成型制品的新成型方法。一个相关的目的是提供多孔陶瓷成型制品。
在一个实施例中,本发明针对制作多孔的化学键合的陶瓷成型制品的方法。所述方法包括i)提供包含聚合物颗粒和陶瓷自凝固骨水泥粉末的前体粉末混合物;ii)从包含所述前体粉末混合物和含水液体的浆中制备成型制品;和iii)将所述成型制品在浸泡液中浸泡大约10分钟到大约两周的一段时间以在所述浸泡液中溶解所述聚合物颗粒,从而在所述成型制品中生成孔隙,在该浸泡液中所述聚合物颗粒是可溶的。
在另一个实施例,本申请针对具有互联孔隙的、总孔隙度至少50%的、和大孔隙度至少30%的多孔的化学键合陶瓷成型制品。
本发明的方法和成型制品在提供具有可控孔隙度以及在某些实施例中具有可控的大孔隙度的成型制品中是有优势的。鉴于这里的详细描述,这些和其他优势将会变得更充分明显。
附图说明
当与附图进行结合观察时,本申请的某些方面可能会得到更好的理解,其中
图1示出了如实例1中所述的作为前体粉末混合物中聚合物颗粒含量函数的陶瓷材料的孔隙度(总孔隙度和大孔隙度)。实心标记示出了总孔隙度并且空心标记示出了大孔隙度。
图2示出了实例2中生成颗粒的光学图像。
图3示出了实例2中生成颗粒的微型计算机断层扫描术(μCT)的图像。
图4示出了实例2中生成颗粒的孔隙体积和分布。
详细说明
本申请的方法包括i)提供包含聚合物颗粒和陶瓷自凝固骨水泥粉末的前体粉末混合物;ii)从包含前体粉末混合物和含水液体的浆中制备成型制品;和iii)将所述成型制品在浸泡液中浸泡大约10分钟到大约两周的一段时间以在所述浸泡液中溶解所述聚合物颗粒,从而在所述成型颗粒中生成孔隙,在所述浸泡液中所述聚合物颗粒是可溶的。
挑选使用的所述聚合物在所述前体粉末中是固体的并且在所述浸泡液中是可溶解的。在具体的实施例中,所述聚合物是水溶的。在另一具体实施例中,所述聚合物包含水溶的聚乙二醇,和更具体地,所述聚合物颗粒包含至少50wt%,60wt%,或70wt%水溶性的聚乙二醇。在另外的实施例中,所述聚合物颗粒基本上由水溶的聚乙二醇组成,即,仅使用了无关紧要数量的任何其他聚合物或其他材料,或者所述聚合物颗粒由水溶性的聚乙二醇组成,即,在颗粒中不包括其他聚合物或其他材料。包括在所述聚合物颗粒中的任何聚合物或其他材料不应该负面影响该颗粒的熔点,即,该颗粒的熔点应该是使得该颗粒在室温下和在任何为了提供期望尺寸的颗粒、需要固体材料的加工过程中是固体的,即,研磨,磨细,筛分等。此外,包括在所述聚合物颗粒中的任何聚合物或其他材料不应该不利地影响所述聚合物颗粒在浸泡液中的溶解超出如下讨论的参数。
在具体实施例中,所述聚合物颗粒包含具有足够高的分子量的聚乙二醇,以确保该颗粒在室温(20-25℃)下是固体的,并且,更具体地,在至少40℃的温度,或者,更具体地,50℃,使得该聚合物能够被研磨,磨碎或以其他机械加工成为在这些加工中不融化的可控的尺寸并且确保所述前体粉末混合物能够与含水液体混合以形成所述浆,并且所述制品可以在所述聚合物颗粒没有显著溶解下成形。进一步,所述聚乙二醇具有足够低的分子量以确保当所述成型制品浸泡在所述浸泡液中时所述颗粒具有足够的水溶性,以在合理的牺牲相移除时间内,在浸泡液中得到合理快速的溶解速率。在具体实施例中,所述溶解时间不少于10分钟,但是不长于10周,更具体地,少于2周,1周,或1至5天,或,更加具体地,约24小时,特别是在期望的牺牲相移除温度,即,在1至100℃的范围,或,具体地,在室温。在具体的实施例中,当所述浸泡液是水和所述浸泡是在大气压下实施时,所述聚合物在上述的牺牲相移除温度下展示出上述的溶解时间。在更具体地实施例中,所述聚乙二醇具有重均分子量,Mw,在从约900g/mol至约100,000g/mol的范围内,在从约5000g/mol至约50,000g/mol的范围内,或在从约5000g/mol至约30,000g/mol的范围内。
当前体粉末与所述含水液体混合以形成所述浆时,所述聚合物颗粒可以展示出微弱溶解度,但是所述聚合物颗粒直至成型制品成形和硬化时在所述浆中实质上是不可溶的,从而使得所述聚合物颗粒的随后溶解形成互联的孔隙结构,或,在某些实施例中,当在浸泡液中浸泡时形成的互联大孔隙结构。
选择所述聚合物颗粒或形成具体颗粒尺寸,形状和分布,以在成型制品中控制孔隙度。在具体实施例中,所述聚合物颗粒具有的平均颗粒尺寸的范围是约10μm至约1000μm,平均颗粒尺寸从约50μm至约1000μm,平均颗粒尺寸从约100μm至约800μm,平均颗粒尺寸从约300μm至约600μm,平均颗粒尺寸从约100μm至约200μm,或平均颗粒尺寸从约200μm至约300μm。在另一个实施例中,至少50%,60%,70%,80%或90%的所述聚合物颗粒具有的尺寸范围是从约10μm至约1000μm,约50μm至约1000μm,约100μm至约800μm,约300μm至约600μm,约100μm至约200μm,或约200μm至约300μm。在这些范围的聚合物颗粒将会提供具有期望大孔隙度和互联孔隙的成型制品。所述聚合物颗粒可以是通过现有技术已知的不同工艺成型和控制尺寸,包括,但不限于,成型,研磨,和/或筛分。
所述前体粉末混合物包含所述聚合物颗粒和陶瓷自凝固骨水泥粉末。陶瓷自凝固骨水泥粉末是一种形成化学键合水泥的粉末且其不需要烧结。所述自凝固骨水泥粉末可以是任何,但不限于,如下的一种或多种:磷酸钙,硫酸钙,硅酸钙(例如,CS,C2S和/或C3S(其中C=CaO和S=SiO2)),碳酸钙(例如,无定形的,霰石,方解石,球霰石),碳酸镁,和铝酸钙(例如,CA,C12A7,C3A(其中C=CaO和A=Al2O3)),或其两种或更多的混合物。在具体实施例中,该粉末包含从无水磷酸氢钙,二水磷酸氢钙,一水合磷酸一钙,磷酸八钙,α-磷酸三钙,β-磷酸三钙,无定形磷酸钙,缺钙羟磷灰石,非化学计量羟磷灰石和磷酸四钙所组成的组中挑选的一种或多种磷酸钙。可以选择所述磷酸钙粉末以形成钙磷石,三斜磷钙石,和/或羟磷灰石。在进一步的实施例中,所述磷酸钙粉末包含一水合磷酸一钙和β-磷酸三钙的混合物,例如,以大约等摩尔的量。
如本领域已知的,所述骨水泥粉末可以选择酸性的,中性的或碱性的,以促进形成期望的硬化骨水泥组合物。例如,酸性的骨水泥-成型浆将形成三斜磷钙石或钙磷石,然而,中性的或碱性的骨水泥-成型浆将形成羟磷灰石。
所述聚合物颗粒为成型制品的孔隙度,在具体的实施例中为大孔隙,起到模板的作用。大孔隙被定义为具有大于约10μm尺寸的孔隙。在具体的实施例中,所述的成型制品具有的大孔隙大于约50μm,100μm,200μm或300μm。在附加的实施例中,所述成型制品具有大孔隙的尺寸范围从约50μm至约1000μm,约100μm至约800μm,约300μm至约600μm,约100μm至约200μm,或约200μm至约300μm。可以通过使用体积和密度测量或者使用在实例中所描述的微型计算机断层扫描术计算孔隙度尺寸和分布。
所述聚合物颗粒和所述陶瓷粉末以期望的比率混合。在具体的实施例中,基于该混合物的重量,所述前体粉末混合物包含从约10至约60wt%,从约20至约50wt%,或从约20至约40wt%的所述聚合物颗粒,和平衡量的陶瓷粉末。如果所述聚合物颗粒含量太低,所述成型制品将不会具有足够的孔隙度用来负载,例如,用来诱导细胞负载,并且,如果所述聚合物含量太高,所述成型制品将不会具有足够的机械强度。
将含水液体加入前体粉末混合物中以形成骨水泥浆,在其中陶瓷骨水泥粉末的溶解-沉淀反应被引发。在具体的实施例中,所述的含水液体主要是水。在具体的实施例中,所述含水液体包含至少50wt%,至少60wt%,至少70wt%,至少80wt%,至少90wt%或100%的水。为了影响所述骨水泥的凝固时间,可以将一种或多种常规添加剂包括在所述前体粉末混合物中、用来形成浆的含水液体中或者浆自身中。
所述浆成型为期望的制品,例如,颗粒或者自定义形状。通常地,所述浆可以成型的时间相对短,几分钟至不超过1小时,这是由于含水液体导致陶瓷粉末反应和硬化,即,凝固,尽管更长的凝固时间也包含在本发明中。
在所述陶瓷凝固后,通过将所述成型制品浸泡在浸泡液中将所述聚合物颗粒移除。在具体的实施例中,所述聚合物颗粒是水溶性的并且所述浸泡液是水。所述制品在所述浸泡液中保留,直至将所有的聚合物溶解和移除。所述浸泡液优选改变一次或多次以确保移除所有聚合物。所述溶解步骤的时间被称为牺牲相移除时间并且所述溶解步骤的温度被称为牺牲相移除温度。在具体的实施例中,至少约50wt%,60wt%,70wt%,80wt%,90wt%,或所有的聚合物颗粒在室温下24小时内溶解在所述浸泡液中。
随着聚合物颗粒在所述浸泡液中溶解,在所述成型制品中产生孔隙。如这里描述尺寸的、以公开的量进行使用的聚合物颗粒,可以提供具有互联大孔隙的成型制品。从而,根据这里描述的具体实施例,所述成型制品可以直接成型成为最终具有大孔隙的几何结构。将所述聚合物颗粒的尺寸控制到窄的分布有助于形成类似均匀尺寸的大孔隙。在具体的实施例中,通过本申请中创造性方法生产的所述陶瓷成型制品具有互联孔隙,总孔隙度至少约50%,60%,或70%,并且大孔隙度至少约30%,40%或50%。因而,该创造性方法提供了生产可控的大孔隙的材料的有效方法。所述材料,以及例如颗粒尺寸的参数,以及在此描述的加工时间和温度等与加工相关的参数可以在本发明的范围内改变。
所得到的多孔成型制品可以从所述浸泡液中移除,并且可选地,为后续使用洗涤和杀菌。所述多孔成型制品适当地用作体外支架材料或生物医学种植体。对于体内传递,种植体可选地可以负载药物活性成分,细胞等。在一个实施例中,所述成型制品能够用作干细胞支架。在另一个实施例中,当所述种植体用于传递药物时,可以不选用大孔隙度,在此情况下,所述聚合物颗粒可以具有更小的尺寸,例如,小于50μm,小于10μm或小于1μm。
实例1
本实例展示了本发明方法和材料的某些实施例的各个方面。
使用Mw为20,000g/mol的聚乙二醇(PEG),其分子量足够低使得所述PEG在水中溶解的相当快,并且其分子量足够高使得PEG在室温下和稍高的温度下是固体,这就使得在不融化该聚合物(Mp=63-66℃)的情况下磨碎和研磨所述PEG成为可能。PEG薄片在100℃融化大约10分钟,冷却,手工研磨,筛分至如表1所述的期望的颗粒尺寸。
将一水合磷酸一钙(MCPM)(Scharlau,CA021 1 005P,批次14160301,西班牙)和β-TCP(Sigma-Aldrich)以45:55的摩尔比与1wt%的焦磷酸二氢二钠(SPP,Sigma-Aldrich)混合到一起。根据表1添加合适量的筛分的PEG。柠檬酸(0.5M(aq))在0.25ml/g(不包括PEG含量)的液/浆(L/P)比率下用作液相。使用Cap-震动器(Ivoclar Vivadent,列支敦斯登)在50mL的falcon管中,进行两次30秒的混合。通常将5g的CaP粉末和适量的PEG添加到50mLfalcon管的底部,并且在混合机中混合约10分钟。添加1.25mL的柠檬酸并且将所述骨水泥在Cap-振动器中混合2个周期,每个周期30秒。
所得到的浆在直径8mm×高度3mm的硅橡胶模中成型,并且在37℃下将6个样本一起放置到50mL的PBS中24h。然后将所述样本抛光(两面)并从所述磨具中拿出,并在60℃将12个样本一起放置到90mL新鲜的PBS中。当24-48h之后,更换所述PBS,再过24-48h后除去PBS。所述样本在60℃干燥24小时。
表1.组成成分
通过使用卡尺预估所述样本的表观体积和通过称量干燥后的样本重量来测定所得到的多孔样本的表观密度(ρa,p)。通过使用氦比重测定法测定骨架密度(ρs)。然后用如下等式计算总孔隙度。
根据Takagi等,材料科学杂志医学材料,12:135-9(2001),使用没有PEG样本的表观密度(ρa,np),根据如下的等式计算大孔隙度:
所述结果以表2呈现。
表2.孔隙度测量结果
该实例示出本方法可以用于有效地生产具有可控孔隙度的骨水泥。
实例2
本实例展示了本发明方法和材料的某些实施例的各个方面。
聚(乙二醇)PEG(20000g/mol,aaa,Sigma Aldrich,德国)在70℃融化,压碎和筛分为100至600μm之间。将3g筛分的PEG与0.060gβ-TCP以及1.940gα-TCP混合。在液体(0.8mL2.5%Na2HPO4(aq))加入之前,将粉末在混合机(Willy A Bachofen AG,瑞士)中混合1小时。使用Cap振动器(Ivoclar Vivadent,USA)混合浆1分钟并在直径为1.2mm,高度为1.2mm的Teflon模具中成型,并在室温(21℃)中固化48小时。然后该成型的颗粒脱模。使用100mL的水通过首先洗涤所述颗粒4次,将所述PEG从所述颗粒中移除,在此之后,添加额外的100mL并将所述颗粒在70℃储存2小时。更换水并再一次将所述颗粒在70℃下储存在100mL水中2小时。在将牺牲相(即,PEG)完全移除后,所述颗粒在70℃干燥48小时。对干颗粒进行热重量分析以确保PEG的完全移除。
所述磷酸钙颗粒所具有的直径在1.0和1.2mm之间,高度在1.2至1.6mm之间(图2和3)。所述颗粒具有的总孔隙度约为75%,大孔隙度约为45%。所述大孔隙尺寸在10和200μm之间,平均约为80μm。从μCT测量的孔隙尺寸分布在图4中示出。所述颗粒的晶体组合物是具有少于10%的β-TCP和α-TCP的缺钙羟磷灰石的混合物。
这里描述的具体的实施例和实例仅仅在本质上是示例性的,并没有意图限制由所附权利要求限定的本发明的范围。基于本说明书和本发明要求保护的范围内,进一步的实施例和实例,及其优点,将对于本领域普通技术人员是显而易见的。
Claims (17)
1.制作多孔的、化学键合陶瓷成型制品的方法,包括:
i)提供包含聚合物颗粒和陶瓷自凝固骨水泥粉末的前体粉末混合物;
ii)从包含所述前体粉末混合物和含水液体的浆中制备成型制品;
iii)将所述成型制品在浸泡液中浸泡大约10分钟到大约两周的一段时间以在所述浸泡液中溶解所述聚合物颗粒,从而在所述成型制品中生成孔隙,在所述浸泡液中所述聚合物颗粒是可溶的。
2.根据权利要求1所述的方法,其中所述聚合物颗粒包含水溶性的聚乙二醇。
3.根据权利要求1所述的方法,其中所述聚合物颗粒由水溶性的聚乙二醇组成。
4.根据权利要求2或3所述的方法,其中所述聚乙二醇具有重均分子量,Mw,的范围从约900g/mol至约100,000g/mol,范围从约5000g/mol至约50,000g/mol,或范围从约5000g/mol至约30,000g/mol。
5.根据权利要求1-4中任一项所述的方法,其中所述聚合物颗粒具有的平均颗粒尺寸是从约10μm至约1000μm,平均颗粒尺寸从约50μm至约1000μm,平均颗粒尺寸从约100μm至约800μm,平均颗粒尺寸从约300μm至约600μm,平均颗粒尺寸从约100μm至约200μm,或平均颗粒尺寸从约200μm至约300μm。
6.根据权利要求1-5中任一项所述的方法,其中所述前体粉末混合物包含从约10至约60wt%,从约20至约50wt%,或从约20至约40wt%的所述聚合物颗粒。
7.根据权利要求1-6中任一项所述的方法,其中所述陶瓷自凝固骨水泥粉末包含磷酸钙粉末,硫酸钙粉末,硅酸钙粉末,碳酸钙粉末,碳酸镁粉末,铝酸钙粉末,或其两种或更多种的混合物。
8.根据权利要求7所述的方法,其中所述陶瓷自凝固骨水泥粉末包含一水合磷酸一钙和β-磷酸三钙的混合物。
9.根据权利要求1-8中任一项所述的方法,其中所述成型制品包含颗粒。
10.根据权利要求1-9中任一项所述的方法,其中形成包含钙磷石的成型制品。
11.根据权利要求1-9中任一项所述的方法,其中形成包含三斜磷钙石的成型制品。
12.根据权利要求1-9中任一项所述的方法,其中形成包含羟磷灰石的成型制品。
13.根据权利要求1-12中任一项所述的方法,其中所述浸泡液包含水。
14.根据权利要求1-13中任一项所述的方法,其中至少约50wt%,60wt%,70wt%,80wt%,90wt%,或所有的所述聚合物颗粒在24小时内溶解在所述浸泡液中。
15.具有互联孔隙、总孔隙度至少约50%,60%,或70%和大孔隙度至少约30%,40%或50%的多孔的化学键合陶瓷成型制品。
16.根据权利要求15所述的多孔成型制品,其中用于体内传递的药学活性成分负载在其孔隙内。
17.根据权利要求15所述的多孔成型制品,其中用于体内传递的细胞负载在其孔隙内。
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