仿生贝壳珍珠质材料的制备
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摘要
自然界中,许多生物矿物具有规则的结构以及不可思议的力学性质。其中贝壳珍珠质由于其独特的光学和力学性质被人们广泛研究,它出色的强度,韧性以及硬度则很大程度上归功于珍珠质中碳酸钙和有机物交替形成的高度有序结构。因此仿生贝壳材料工作成为了一大热点并且在许多领域有很大的指导意义和应用价值。
本文基于对贝壳结构和矿化机制的研究,以及对各种晶型碳酸钙尤其是无定型碳酸钙的合成技能,制备了不同的贝壳类结构或性质材料。开始是仿生贝壳外层结构的碳酸钙复合薄膜制备,然后基于不同模板可控合成了不同晶型和形貌的碳酸钙,并进一步揭示了贝壳的矿化机理,最后实现了高力学性能有机无机复合薄膜的制备。不断深入的研究为仿生贝壳材料的制备提供了新的思路和方法,全文共分6章。
第一章主要阐述了贝壳珍珠质的结构和矿化理论研究,介绍了碳酸钙尤其是无定形碳酸钙以及其在生物矿化中的实例。又总结了目前国内外仿生贝壳材料重要的相关研究工作,并提出了我们课题的研究方向和需要解决的问题。
第二章我们仿生贝壳外层结构制备了方解石-文石的复合膜。我们首先通过无定型碳酸钙的可控转化制备了均匀的一层方解石膜,然后在镁离子的作用下又在之前的方解石膜上沉积了一层文石膜,从而用简洁的方法制备了方解石-文石复合膜,在这个过程中我们发现镁离子对方解石-文石的转化起到了非常重要的作用。这个工作通过简洁的方法实现了对贝壳最外层结构的初步模拟。
第三章我们用有机基底作为模板可控合成了不同晶型和形貌的碳酸钙晶体。我们用鸡蛋膜作为模板,在镁离子和基丙烯酸(PAA)的存在下合成了碳酸钙晶体。其中我们在钙镁比为1:1的溶液中一步沉积得到了方解石-文石的复合膜,在钙镁比为1:4的溶液中得到了致密的文石膜,我们还阐述了镁离子和PAA在这个过程中的作用。这个工作为贝壳矿化机制提供了深入的理解并且为可控合成有机-无机复合膜提供了途径。
第四章我们在贝壳模板上得到了一层致密的文石膜。我们用贝壳基底作为模板,在聚苯稀磺酸钠(PSS)的存在下沉积了文石晶体。我们发现不同次氯酸钠(NaClO)处理时间的贝壳模板可以诱导出不同形貌和取向的碳酸钙晶体,其中我们在30mmin处理时间的贝壳模板上制备了类似于贝壳取向的均—文石膜,并且我们认为贝壳中的无定型碳酸钙在这层文石膜的形成过程中起到了重要的作用。这个工作进一步揭示了贝壳的矿化机制,并为制备以碳酸钙为基础的环保功能材料提供了一条途径。
第五章我们通过无定形的先驱相制备了高强度和刚性的有机无机复合膜。首先我们在聚丙烯酸(PAA)的存在下合成了无定形碳酸钙(ACC)胶体溶液,然后又把ACC和聚乙烯醇(PVA)交替旋涂在玻璃基底上,形成有机无机的多层复合结构,再将得到的无定型复合膜在80度下结晶48h。我们发现经过热处理的膜具有高度的取向性,通过力学性质测试,结晶的复合膜在强度,硬度和弹性模量上比之前有大幅度提升,并且强度和模量接近于贝壳的最佳值,这个工作提为制备高性能复合材料提供了新的思路和方法。
第六章我们提出了仿生贝壳材料需要解决的问题,并展望了其在新材料领域的广阔发展前景。
In nature, biominerals have the ability to assemble ordered structure and remarkable mechanical properties. For example, nacre was widely studied due to its unique optical and mechanical property. Its excellent strength, toughness and hardness are largely attributed to a highly regular arrangement of organic-inorganic hybrid structure which combines polygonal calcium carbonate platelets and biological macromolecules such as chitin and proteins. Therefore, preparation of materials inspired from nacre is the vanguard of materials research with significant leading meanings and application values in many fields.
In our study, we prepare different materials inspired from nacre. Based on the study and understanding of nacre structure and its biomineralization mechanism with experiment skills in calcium carbonate especially amorphous calcium carbonate (ACC) synthesis, we do research on biomimetic preparation of different materials with nacre-like structure or mechanical property. At the beginning, we synthesized complex calcium carbonate films that mimic nacre external structure in vitro. Then calcium carbonate crystals with different polymorph and morphology were controllable deposited on different substrate. The works can lead a further understanding of nacre formation process. In the end, strong and stiff hybrid materials were achieved via amorphous precursor. In-depth study provides new methods and understanding for preparation of materials inspired from nacre. The thesis contains six chapters in total.
In chapter1, we elucidate nacre structure and its current biomineralization theory. We also introduce calcium carbonate especially amorphous calcium carbonate (ACC) and its role in biominerals formation. Then we summarize important research works related to biomimic nacre materials at present, and give our research direction and problems to be solved.
In chapter2, we fabricate calcite-aragonite complex films that duplicate nacre external structure. We first synthesize a uniform calcite film transformed from amorphous calcium carbonate. Then we deposit an aragonite film on the previous calcite film with the aid of Mg ions. A calcite-aragonite complex film was easily fabricated in vitro. In the preparation process we discuss the important role of Mg ions for the transition of calcite to aragonite crystals. This work opens a simple method to mimic nacre external structure.
In chapter3, we use organic substrate to controllably fabricate calcium carbonate crystals with different polymorph and morphology. We first use eggshell membrane as the substrate to deposit CaCO3crystals in the presence of Mg ions and PAA. We can obtain a calcite-aragonite complex film from one-step deposition in the solution of Mg/Ca ratio is1:1. While an unifrom aragonite film was obtained in the solution of Mg/Ca ratio is4:1. We also discuss the role of Mg ions and PAA in the process. This work can lead a further understanding of nacre biomineralization mechanism and provides a pathway for preparation organic-inorganic complex films.
In chapter4, we obtain a compact aragonite film on nacre substrate. Aragonite crystals were fabricated using nacre substrate in the presence of PSS. We found different NaCIO treated nacre substrate can induce different calcium carbonate crystals in morphology and polymorph. And uniform aragonite film with similar nacre orientation was obtained on30min-NaClO treated substrate. And we suggest amorphous calcium carbonate (ACC) in nacre plays key roles for this aragonite film formation. This work further reveals nacre biomineralization mechanism and provides a way to fabricate CaCO3based functional materials with environmental benignity.
In chapter5, we achieve strong and stiff hybrid films via amorphous precursor. Firstly, we synthesize uniform ACC colloid with the size around100nm in the presence of PAA. Then ACC and PVA were spin-coated on glass substrate alternatively to form a multilayered organic-inorganic hybrid film. The amorphous hybrid film was heated at80℃for48h for fully crystallization. We find crystallized hybrid film after thermal heating becomes highly oriented that is similar to nacre. After mechanical test, the hardness, stiffness and tensile strength of crystallized hybrid film increases notably. And the stiffness and tensile strength of the crystallized hybrid film is close to optimal value of nacre. This work opens an novel and simple pathway for preparation of hybrid materials with high mechanical performance.
In chapter6, we point out the problems to be solved in biomimetic materials in the future, we also highlight its broad development prospects in new materials areas.
本文基于对贝壳结构和矿化机制的研究,以及对各种晶型碳酸钙尤其是无定型碳酸钙的合成技能,制备了不同的贝壳类结构或性质材料。开始是仿生贝壳外层结构的碳酸钙复合薄膜制备,然后基于不同模板可控合成了不同晶型和形貌的碳酸钙,并进一步揭示了贝壳的矿化机理,最后实现了高力学性能有机无机复合薄膜的制备。不断深入的研究为仿生贝壳材料的制备提供了新的思路和方法,全文共分6章。
第一章主要阐述了贝壳珍珠质的结构和矿化理论研究,介绍了碳酸钙尤其是无定形碳酸钙以及其在生物矿化中的实例。又总结了目前国内外仿生贝壳材料重要的相关研究工作,并提出了我们课题的研究方向和需要解决的问题。
第二章我们仿生贝壳外层结构制备了方解石-文石的复合膜。我们首先通过无定型碳酸钙的可控转化制备了均匀的一层方解石膜,然后在镁离子的作用下又在之前的方解石膜上沉积了一层文石膜,从而用简洁的方法制备了方解石-文石复合膜,在这个过程中我们发现镁离子对方解石-文石的转化起到了非常重要的作用。这个工作通过简洁的方法实现了对贝壳最外层结构的初步模拟。
第三章我们用有机基底作为模板可控合成了不同晶型和形貌的碳酸钙晶体。我们用鸡蛋膜作为模板,在镁离子和基丙烯酸(PAA)的存在下合成了碳酸钙晶体。其中我们在钙镁比为1:1的溶液中一步沉积得到了方解石-文石的复合膜,在钙镁比为1:4的溶液中得到了致密的文石膜,我们还阐述了镁离子和PAA在这个过程中的作用。这个工作为贝壳矿化机制提供了深入的理解并且为可控合成有机-无机复合膜提供了途径。
第四章我们在贝壳模板上得到了一层致密的文石膜。我们用贝壳基底作为模板,在聚苯稀磺酸钠(PSS)的存在下沉积了文石晶体。我们发现不同次氯酸钠(NaClO)处理时间的贝壳模板可以诱导出不同形貌和取向的碳酸钙晶体,其中我们在30mmin处理时间的贝壳模板上制备了类似于贝壳取向的均—文石膜,并且我们认为贝壳中的无定型碳酸钙在这层文石膜的形成过程中起到了重要的作用。这个工作进一步揭示了贝壳的矿化机制,并为制备以碳酸钙为基础的环保功能材料提供了一条途径。
第五章我们通过无定形的先驱相制备了高强度和刚性的有机无机复合膜。首先我们在聚丙烯酸(PAA)的存在下合成了无定形碳酸钙(ACC)胶体溶液,然后又把ACC和聚乙烯醇(PVA)交替旋涂在玻璃基底上,形成有机无机的多层复合结构,再将得到的无定型复合膜在80度下结晶48h。我们发现经过热处理的膜具有高度的取向性,通过力学性质测试,结晶的复合膜在强度,硬度和弹性模量上比之前有大幅度提升,并且强度和模量接近于贝壳的最佳值,这个工作提为制备高性能复合材料提供了新的思路和方法。
第六章我们提出了仿生贝壳材料需要解决的问题,并展望了其在新材料领域的广阔发展前景。
In nature, biominerals have the ability to assemble ordered structure and remarkable mechanical properties. For example, nacre was widely studied due to its unique optical and mechanical property. Its excellent strength, toughness and hardness are largely attributed to a highly regular arrangement of organic-inorganic hybrid structure which combines polygonal calcium carbonate platelets and biological macromolecules such as chitin and proteins. Therefore, preparation of materials inspired from nacre is the vanguard of materials research with significant leading meanings and application values in many fields.
In our study, we prepare different materials inspired from nacre. Based on the study and understanding of nacre structure and its biomineralization mechanism with experiment skills in calcium carbonate especially amorphous calcium carbonate (ACC) synthesis, we do research on biomimetic preparation of different materials with nacre-like structure or mechanical property. At the beginning, we synthesized complex calcium carbonate films that mimic nacre external structure in vitro. Then calcium carbonate crystals with different polymorph and morphology were controllable deposited on different substrate. The works can lead a further understanding of nacre formation process. In the end, strong and stiff hybrid materials were achieved via amorphous precursor. In-depth study provides new methods and understanding for preparation of materials inspired from nacre. The thesis contains six chapters in total.
In chapter1, we elucidate nacre structure and its current biomineralization theory. We also introduce calcium carbonate especially amorphous calcium carbonate (ACC) and its role in biominerals formation. Then we summarize important research works related to biomimic nacre materials at present, and give our research direction and problems to be solved.
In chapter2, we fabricate calcite-aragonite complex films that duplicate nacre external structure. We first synthesize a uniform calcite film transformed from amorphous calcium carbonate. Then we deposit an aragonite film on the previous calcite film with the aid of Mg ions. A calcite-aragonite complex film was easily fabricated in vitro. In the preparation process we discuss the important role of Mg ions for the transition of calcite to aragonite crystals. This work opens a simple method to mimic nacre external structure.
In chapter3, we use organic substrate to controllably fabricate calcium carbonate crystals with different polymorph and morphology. We first use eggshell membrane as the substrate to deposit CaCO3crystals in the presence of Mg ions and PAA. We can obtain a calcite-aragonite complex film from one-step deposition in the solution of Mg/Ca ratio is1:1. While an unifrom aragonite film was obtained in the solution of Mg/Ca ratio is4:1. We also discuss the role of Mg ions and PAA in the process. This work can lead a further understanding of nacre biomineralization mechanism and provides a pathway for preparation organic-inorganic complex films.
In chapter4, we obtain a compact aragonite film on nacre substrate. Aragonite crystals were fabricated using nacre substrate in the presence of PSS. We found different NaCIO treated nacre substrate can induce different calcium carbonate crystals in morphology and polymorph. And uniform aragonite film with similar nacre orientation was obtained on30min-NaClO treated substrate. And we suggest amorphous calcium carbonate (ACC) in nacre plays key roles for this aragonite film formation. This work further reveals nacre biomineralization mechanism and provides a way to fabricate CaCO3based functional materials with environmental benignity.
In chapter5, we achieve strong and stiff hybrid films via amorphous precursor. Firstly, we synthesize uniform ACC colloid with the size around100nm in the presence of PAA. Then ACC and PVA were spin-coated on glass substrate alternatively to form a multilayered organic-inorganic hybrid film. The amorphous hybrid film was heated at80℃for48h for fully crystallization. We find crystallized hybrid film after thermal heating becomes highly oriented that is similar to nacre. After mechanical test, the hardness, stiffness and tensile strength of crystallized hybrid film increases notably. And the stiffness and tensile strength of the crystallized hybrid film is close to optimal value of nacre. This work opens an novel and simple pathway for preparation of hybrid materials with high mechanical performance.
In chapter6, we point out the problems to be solved in biomimetic materials in the future, we also highlight its broad development prospects in new materials areas.
引文
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