本文選題：珍珠層　切入點：穹頂狀板片　出處：《廣西大學》2017年博士論文　論文類型：學位論文

【摘要】：珍珠層是天然的有機-無機復合材料,具有優(yōu)越的結(jié)構(gòu)和杰出的力學性能。然而,它僅需利用環(huán)境中常見的Ca2+和C032-在常溫常壓下即可在生物體中合成。因此,珍珠層是一種環(huán)保材料,長久以來成為了生物礦化領域以及仿生合成材料領域的經(jīng)典研究對象。目前,關于珍珠層的研究積累了很多知識,但仍有很多問題存在爭議,如珍珠層的基本結(jié)構(gòu)單元-文石板片的形貌、排列、內(nèi)部結(jié)構(gòu)等。此外,幾乎所有的相關知識均基于研究成熟的平板狀板片而來,而忽略了板片的形貌和生長階段,這導致了珍珠層研究的不足。在本工作中,我們以翡翠貽貝珍珠層板片為主要研究對象,尤其是具有獨特形貌的穹頂狀板片。我們采用場發(fā)射SEM、HRTEM、XRD、DSC以及FTIR等對穹頂狀板片的形成機理進行研究,包括板片的三維形貌與排列、內(nèi)部結(jié)構(gòu)、成核與生長、結(jié)晶學關系與界面結(jié)構(gòu)、以及形成環(huán)境等,獲得以下結(jié)論:(1)穹頂狀板片和平板狀板片在翡翠貽貝中共存,前者是后者吸收外力發(fā)生形變后的產(chǎn)物;(2)板片呈梯度變化排列,包括厚度梯度和曲率梯度。自珍珠層底部到頂部,板片厚度由0.84±0.08 μm變?yōu)?.24±0.01 μm,曲率由0.77±0.12 μm-1變?yōu)? μm-1,即板片厚度和曲率之間是逐漸過渡的,沒有明顯的界限�；谟^察,我們推測厚度梯度是由于貝殼中心和貝殼邊緣的生長速率不同引起的,而曲率梯度是由于板片受到來自閉殼肌關閉貝殼和套膜回收表殼層時的壓應力梯度引起的;(3)平板狀板片和成熟的穹頂板片為單晶,未成熟穹頂狀板片為無序文石納米顆粒的集合體。其中,早期未成熟穹頂狀板片由粒徑為18-41 nm但只有部分結(jié)晶的橢圓形膠體納米顆粒組成,晚期未成熟穹頂狀板片由粒徑為20-150 nm且完全結(jié)晶的膠體納米顆粒組成。我們推測單個成熟穹頂狀板片是由ACC納米顆粒定向粘結(jié)形成的;(4)新生的板片均成核于底層板片的環(huán)表面上,呈自限生長模式生長。板片的水平生長速率不均勻,與成核時間成反比。我們推測板片的成核與水平生長速率是受到晶格不匹配誘導的應力所控制的;(5)穹頂狀板片的結(jié)晶學定向一致,其層間膜由直徑為30-50 nm的橢球形結(jié)晶蛋白質(zhì)構(gòu)成。層間膜通過厚度為10-20 nm的超晶格區(qū)域與板片相連接,繼而繼承并傳遞底層板片的結(jié)晶學定向,使得所用板片結(jié)晶學定向一致;(6)穹頂狀板片和平板狀均為天然的高能文石并伴隨著v2帶紅外頻移,其中穹頂狀板片和平板狀板片v2帶頻移分別高達8cm-1和12cm-1,這可能是由于板片的納米粒徑效應、低結(jié)晶度以及晶格畸變引起的。與平板狀板片相比,穹頂狀板片的能量相對較低,這是由于穹頂狀板片是平板狀板片通過形變實現(xiàn)應力松弛降低能量后的產(chǎn)物;(7)腹側(cè)和后端表殼層存在結(jié)構(gòu)差異性。其中,腹側(cè)表殼層內(nèi)層最薄,中層最厚,中層由直徑為43-106 nm的非晶質(zhì)納米球體組成,而后端表殼層中各結(jié)構(gòu)層厚度自外而內(nèi)遞增,中層由直徑約為178nm的纖維組成。腹側(cè)表殼層中層的納米球體由少量蛋白質(zhì)和含Ca,Mg以及CO32-的非晶質(zhì)磷酸鹽組成,這不僅能給珍珠層的形成提供原材料,還能穩(wěn)定環(huán)境的pH,促進珍珠層的礦化;(8)乳狀突起層由具有呈拋物面形狀(底部平均直徑d=2.5 μm,平均高度h=4.6 μm)的蛋白質(zhì)突起組成,它們嵌入到棱柱層中形成獨特的互鎖界面,有效防止表殼層和棱柱層之間的滑動,并替代表殼層充當了貝殼的初始礦化基底,相比于表殼層能夠給生物礦化提供約4倍大的表面積,有助于初始礦化的進行�；谟^察,我們推測乳狀突起是由于貝殼關閉時表殼層受到壓應力引起的。本工作中,我們重構(gòu)了穹頂狀板片的三維形貌并建立板片的梯度排列模型,并提出了 ACC定向粘結(jié)的非傳統(tǒng)結(jié)晶理論。此外,我們還首次在雙殼綱貝殼中直接觀察到了穹頂狀板片的界面結(jié)構(gòu),發(fā)現(xiàn)結(jié)晶的層間膜通過超晶格區(qū)域與板片相連接,繼承并傳遞底層板片的結(jié)晶學定向。這些研究結(jié)果將進一步揭示珍珠層的形成機理,有助于類珍珠層材料的合成。
[Abstract]:Nacre is organic inorganic composite material of natural, has the superior structure and mechanical properties of outstanding. However, it only uses Ca2+ and C032- common environment can be synthesized in the body under normal temperature and pressure. Therefore, the pearl layer is a kind of environmental protection material, has long been the field of biomineralization and biomimetic fields the classic synthetic materials research object. At present, the research on pearl layer accumulated a lot of knowledge, but there is still controversy many problems, such as the basic structural unit of nacre aragonite sheets - morphology, arrangement, internal structure and so on. In addition, the related knowledge of almost all the flat plate based on the mature research come, while ignoring the morphology and growth stage of the plate, which led to a shortage of nacre research. In this work, we take the pearl mussel plates as the main research object, especially with unique morphology The dome shaped plate. We use the field emission SEM, HRTEM, XRD, DSC and FTIR on the dome shaped plate forming mechanism of the internal structure of three-dimensional shape and arrangement, including plate, nucleation and growth, the relationship between crystallography and interface structure, and the formation of the environment, the following conclusions are obtained: (1) dome shaped plate and a flat plate coexist in the mussel, the former is the product of absorption force after deformation; (2) plate gradient arrangement, including thickness gradient and curvature gradient. From the bottom to the top of the nacreous layer, the thickness of the plate from 0.84 + 0.08 m to 0.24 0.01 + m, 0.77 + 0.12 M-1 by curvature is 0 M-1, which is between plate thickness and curvature gradually, no obvious boundaries. Based on the observation, we speculate that the thickness gradient is due to the growth rate of shell and shell edge center caused by different, while the curvature is due to gradient The plate from closed shell and adductor muscle film recovery case layer when the compressive stress caused by the gradient; (3) flat plate and dome plate mature for single crystal, dome shaped plate as a collection of immature disordered aragonite nanoparticles. The early immature dome shaped plate by particle size 18-41 nm but elliptical nanoparticles only partially crystalline composition, late immature dome shaped plate by the diameter of colloidal nanoparticles of 20-150 nm and fully crystallized. We speculate that single mature dome shaped plate is formed by bonding the ACC nano particle orientation; (4) the new plate surface nuclear ring on the bottom plate, a self limited growth model. In the level of growth rate is not uniform, and the nucleation time. We speculate that the plate is inversely proportional to the nucleation and growth rate is affected by the level of lattice mismatch induced stress control; (5) the dome shaped plate with crystallography orientation, the interlayer film with diameter of ellipsoidal crystal protein of 30-50 nm. The structure of the interlayer film through the thickness of the superlattice region and the plate 10-20 is connected to the nm, and then inherit and pass the bottom plate of the crystallographic orientation, the sheet crystallography orientation consistent; (6) the dome shaped plate and the plate are natural and accompanied by high-energy aragonite V2 with infrared shift, the dome shaped plate and a flat plate V2 with frequency shift were as high as 8cm-1 and 12cm-1, which may be due to the size effect of nanoparticles plate, low crystallinity and due to lattice distortion. Compared with the flat plate, dome shaped plate energy is relatively low, this is because of the dome shaped plate is a flat plate through the realization of deformation stress relaxation after the reduction product of energy; (7) there are differences in the structure of the ventral side and rear case layer. Among them, the ventral table The inner shell of the thin, middle thick, middle diameter by amorphous nano spheres composed of 43-106 nm, and each layer of layer thickness in the case is from outside to inside diameter increases, the middle is composed of 178nm fibers. The ventral case layer nano sphere by a small amount of protein and Ca containing amorphous. Mg and CO32- phosphate composition, which can not only provide the raw material for the formation of pearl layer, but also stable environment pH, promote the nacre mineralization; (8) papillae layer is composed with a parabolic shape (at the bottom of the average diameter of d=2.5 m, the average height of h=4.6 ~ m) protein consisting of protrusions, embedding them into the interlocking interface forms a unique prismatic layer, effectively prevent sliding between case and prismatic layer, and acts as a representative for the shell basal initial mineralization of shells, compared to the case for biomineralization layer can provide about 4 times as large as the surface area, help For the initial mineralization. Based on observation, we speculate that the papillae is due to closed shell case layer by compressive stress caused. In this work, we reconstructed the three-dimensional shape of the dome shaped plate and a gradient plate arrangement model, and proposes the traditional crystallization theory ACC directional bonding. In addition, we also for the first time in bivalve shells were observed directly in the interface structure of dome shaped plate, found that the crystallization of the interlayer film is connected by a superlattice region and plate, inherit and transfer plate bottom crystallography orientation. These results will further reveal the formation mechanism of nacre, contribute to the synthesis of class pearl layer material.

【學位授予單位】：廣西大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TB33

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