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研究生: 葉舒
Ye, Shu
論文名稱: 矽烷成分對10-MDP基底的通用型黏著劑黏著性能探討
Effects of silane content to the bonding performance of MDP-base universal adhesives
指導教授: 莊淑芬
Chuang, Shu-Fen
共同指導: 林睿哲
Lin, Jui-Che
學位類別: 碩士
Master
系所名稱: 醫學院 - 口腔醫學研究所
Institute of Oral Medicine
論文出版年: 2021
畢業學年度: 109
語文別: 英文
論文頁數: 69
中文關鍵詞: 氧化鋯通用型黏著劑矽烷飛行式二次離子質譜儀固態核磁共振
外文關鍵詞: zirconia, universal adhesive, silane, ToF-SIMS, SSNMR
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  • 氧化鋯是一種美觀且高强度的陶瓷材料,在牙科領域中被應用於製作各式復形物。然而,其高化學穩定性卻不利於與這種材料與樹脂黏結劑的結合。爲了提高氧化鋯的黏著性能,一種名爲10-甲基丙烯酰氧基癸基二氫磷酸酯(10-MDP)的酸性單體被發展出來。其特有的磷酸基團能吸附在氧化鋯表面,而另一端的有機基團則能與樹脂發生共聚反應。這種獨特的雙官能團能和氧化鋯材料形成化學鍵結,並為其與樹脂黏著劑提供良好的鍵結。
    至今爲止,許多公司都發展出了以10-MDP為基底的牙科通用型黏著劑,並在其中加入矽烷(Silane)成分,聲稱不僅可以提高氧化鋯的黏著性能,還能同時黏著玻璃陶瓷、金屬、金屬氧化物等多種材料。然而,10-MDP和矽烷之共存可能會抑制10-MDP和氧化鋯的黏結。10-MDP的酸性會促進矽烷的聚合反應,使其失效;反之,矽烷的存在也可能阻礙氧化鋯對10-MDP的吸附。本研究的目的是探討矽烷成分在以10-MDP為基底的通用型黏著劑中的作用。本研究分爲兩個部分,第一部分是檢測商業用通用型黏著劑,第二部分是檢測10-MDP黏著劑加入矽烷後,與氧化鋯的化學鍵結與黏著性能。
    第一部分:本研究首先藉由飛行式二次離子質譜儀(ToF-SIMS)檢測兩種含矽烷之商業用通用黏著劑Scotchbond Universal (簡稱SBU)和Clearfil Universal Bond (簡稱CUB)與兩種不含矽烷通用型黏著劑Clearfil SE Bond (簡稱SE) 與All-Bond Universal (簡稱ABU),研究塗佈於氧化鋯上,矽烷與MDP在黏著層的分佈狀況,以及P-O-Zr鍵結相關離子之比例與分布;接著透過座滴法測量蒸餾水或樹脂黏著劑與氧化鋯之間的靜態接觸角;最後搭配使用兩種牙科黏著劑 (RelyX Ultimate, 3M-ESPE、Variolink II, Ivoclar/Vivadent),對黏著的樣本進行剪切强度測試,探究其黏著效果。
    第二部分:在含有10-MDP為基底的SE BOND Primer中加入不同濃度的矽烷(5wt%,10wt%),製備實驗用黏著劑(SE-5,SE-10),並如上所述,對其進行ToF-SIMS分析、接觸角測量和剪切强度測試。此外,用固態核磁共振儀 (Solid state NMR)確認實驗用黏著劑中MDP成分與氧化鋯間的鍵結方式,以及矽烷成分對該鍵結的影響。
    第一部份的ToF-SIMS的結果顯示,在商業通用型黏著劑中,不含矽烷通用型黏著劑SE與氧化鋯的界面上擁有最高的PO3-/ PO2-比值,其次是ABU。這一比值顯示可能存在磷酸鋯化合物。同時,經過兩者處理的氧化鋯,其表面與水或樹脂的親和性皆高於SBU和CUB。在剪切强度測試中,使用RelyX Ultimate黏著,SBU、CUB、ABU顯示出較高的强度;對於Variolink II,SBU和SE顯示出較高的數值。
    於第二部分研究中,ToF-SIMS在單純SE primer與氧化鋯的界面上檢測到最多的P-O-Zr相關鍵結,該鍵結的數量在SE-5,SE-10中減少。另外,隨著矽烷濃度的增加,在氧化鋯表面檢測到更多的ZrO2(OH)-離子。接觸角測試和剪切黏著强度的結果分別顯示,在氧化鋯表面塗抹含矽烷的SE-5和SE-10後,其對樹脂的親和性、以及與樹脂的黏著强度均低於單純的SE。固態核磁共振儀顯示,單純的SE有較多的P-O-Zr離子鍵以及吸附的MDP二聚體;而在SE-5和SE-10中,P-OH-Zr 氫鍵增加。
    從結論上看,通用型黏著劑中的10-MDP成分可與氧化鋯表面形成P-O-Zr離子鍵和P-OH-Zr氫鍵,增加氧化鋯的黏著性能。然而,矽烷的存在會增加氧化鋯表面(OH)基,減少10-MDP的吸附,不利於P-O-Zr 鍵結形成。

    Zirconia has been widely used in dentistry due to its excellent strength and attractive aesthetics. Unfortunately, the intrinsic chemical stability makes it difficult in bonding with resin cement. To compensate this weakness, an acidic resin monomer 10-methacryloyloxy-decyl dihydrogen phosphate (10-MDP) has been developed. The phosphate group of 10-MDP can be absorbed to zirconia, and the organic group of which can copolymerized with resin. This bifunctional group of MDP improves the chemical affinity of zirconia.
    Hitherto, 10-MDP based universal adhesives have been developed by various manufactures. Some of them contain silane monomer in order to facilitate the bonding performance between resin cement and various materials including zirconia, glass ceramics, metals, and metal oxides. However, the bonding between 10-MDP and zirconia can be compromised by the co-existence of 10-MDP and silane. The acidity caused by MDP may accelerate the polymerization process of silane, and the presence of silane may inhibit the adsorption of MDP to zirconia as well. Hereby, the purposes of this study were to investigate the presence of silane in affecting the bonding and chemical actions of MDP based universal adhesives. This study was divided into two parts: the first was the examination of commercial 10-MDP based universal adhesives, and the second was to examine the experimental silane-containing MDP primers in regards to chemical bonding and bond strengths.
    Part I: Four commercial universal adhesives/primer were examined: two silane-containing agents Scotchbond Universal (SBU) and CLEARFIL Universal Bond (CUB); and two silane-free CLEARFIL SE Bond (SE) and All-Bond Universal (ABU). These agents were applied on zirconia disks, and was investigated by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis to reveal the distribution of MDP and silane ions in the adhesive layers and the presence and distributions of P-O-Zr bond-related ions. The contact angles of water/resin adhesive on treated zirconia were measured using a sessile drop method. The bonding performance of these universal adhesives were tested in combination with two resin cements (RelyX Ultimate; 3M-ESPE, and Variolink II; Ivoclar, Vivadent).
    Part II: Experimental adhesives were formulated by adding 5wt% and 10wt% silane to MDP-based SE BOND Primer (SE-5, SE-10), which were evaluated using ToF-SIMS analysis, contact angle measurement and shear bond strength test. Additionally, the chemical states of zirconia-phosphate bonding as silane present were confirmed by a solid-state nuclear magnetic resonance (SSNMR) instrument.
    The Part I results of ToF SIMS analysis showed the highest PO3-/ PO2- ion ratio at the zirconia interface, which has been considered as an indicator of zirconia phosphate compound formation, in group SE, followed by ABU. SE and ABU also showed lower water/adhesive contact angles, implying a higher affinity to both liquids. Regarding to the shear bond strength, higher values were presented by SBU, CUB and ABU when combined with RelyX Ultimate. While with Variolink II, SBU and SE showed significantly higher strengths.
    The Part II results revealed that the treated zirconia in SE group showed the greatest amount of P-O-Zr related ions, which reduced in SE-5 and SE-10. More ZrO2(OH)- related ions were examined with more silane ions added. In regards of the contact angle measurement and shear bond strength test, SE-5 and SE-10 treated zirconia presented lower water/adhesive affinity and shear bond strength value compared to SE. In the result of SSNMR, SE showed more P-O-Zr ionic bonds and physisorbed MDP dimer, SE-5 and SE-10 showed more P-OH-Zr hydrogen bonds.
    In conclusion, the study demonstrated 10-MDP can be adsorbed onto zirconia particles by either monomer and dimer forms, via ionic bond (P-O-Zr) or hydrogen bond (P-OH-Zr), and thus the bond strength can be improved. Unfortunately, the presence of silane may increase the hydroxylation of zirconia, reduce the adsorption of MDP, and adversely affected the formation of P-O-Zr bond.

    Abstract IV Contents VIII Table contents XI Figure contents XIII Chapter1. Introduction 1 1.1 Dental all ceramics 1 1.1.1 The properties of zirconia material 1 1.1.2 Pretreatment for bonding of zirconia ceramics 4 1.2 MDP base universal adhesives 8 1.2.1 Development of universal adhesives 8 1.2.2 Bonding evidences between 10-MDP and zirconia substrate 9 1.3 Silane coupling agent 13 1.3.1 Adhesion mechanisms of silane coupling agents in ceramics 13 1.3.2 Coexistence of silane and MDP in universal adhesives 16 1.4 Motivation and aim 17 Chapter 2. Materials and Methods 18 2.1 A ToF-SIMS analysis 21 2.1.1 Analysis on the surface 23 2.1.2 Analysis at the interface 25 2.1.3 3D ion reconstructions 26 2.2 Contact angle measurement 27 2.3 Shear bond strength test 28 2.4 A ToF-SIMS analysis 31 2.5 Contact angle measurement 31 2.6 Solid state NMR analysis 32 2.7 Shear bond strength test 34 2.8 Statistically analysis 34 Chapter 3. Result 35 Part I. Examination of commercial universal adhesives 35 3.1 ToF-SIMS analysis 35 3.1.1 Analysis on the surface 35 3.1.2 Analysis at the interface 36 3.1.3 3D ion reconstructions 42 3.2 Contact angle measurement 42 3.3 Shear bond strength test 43 Part II. Effect of silane in universal adhesives 44 3.4 A ToF-SIMS analysis 44 3.4.1 Analysis on the surface 44 3.4.2 Analysis at the interface 46 3.4.3 3D ion reconstructions 51 3.5 Contact angle measurement 51 3.6 Shear bond strength test 52 3.7 Solid state NMR (SSNMR) analysis 53 Chapter 4 Discussion 56 Chapter 5 Conclusion 61 References 62 Table contents Table 1 - Adhesives/Primer and cements investigated in the present study. 20 Table 2 - The total MDP related negative ion counts and their normalized percentages to total ion counts on the top layer of adhesive. 36 Table 3 - The total silane related positive ion counts and their normalized percentages to total silane related ions on the top layer of adhesive. 36 Table 4 - The total MDP related negative ion counts and their normalized percentages to total ion counts on the top layer of adhesive. 40 Table 5 - The total PO related negative ion counts and their normalized percentages to total ion counts. 41 Table 6 - The total silane related positive ion counts and their normalized percentages to total silane related ions on the top layer of adhesive. 41 Table 7 - The value of contact angles between water/resin adhesive and zirconia surface (mean and standard deviation). 43 Table 8 - The SBS value (mean, standard deviation and standard error) of two resin cements to zirconia primed with using different universal adhesives. 43 Table 9 - The MDP related negative ion counts and their normalized percentages on the top layer of adhesive. 45 Table 10 - The total silane related positive ion counts and their normalized percentages to total silane related ions on the top layer of adhesive. 45 Table 11 - The MDP related negative ion counts and their normalized percentages on the top layer of adhesive. 49 Table 12 - The total PO related negative ion counts and their normalized percentages to total ion counts. 50 Table 13 - The total silane related positive ion counts and their normalized percentages to total silane related ions at the interface. 50 Table 14 - The value of contact angles between resin adhesive and zirconia surface (mean and standard deviation). 52 Table 15 - The results of SBS value for the tested experimental groups (mean, standard deviation and standard error). 52   Figure contents Figure 1. Schematic representation of the three polymorphs of ZrO2 and the corresponding space groups: (a) cubic, (b) tetragonal, and (c) monoclinic [6]. 3 Figure 2. Scheme of the transformation toughening mechanism [10]. 3 Figure.3 Illustration of the tribochemical silica coating process. Silica coated alumina particles are driven into the ceramic surface under high air pressure. This creates local energy which facilitates transfer of silica onto the ceramic surface. A potential problem is the creation of damage to the surface of the ceramic via the air abrasion process, which could accelerate fatigue [28]. 6 Figure 4. Amphiphilic structure of the MDP monomer. Established chemical bond between zirconia substrate and MDP has been reported, which contributing to a durable adhesion. [45, 46] 9 Figure 5. Proposed models for the surface species of various phosphate-treated zirconias. (A) terminal hydroxide group; (B) bridging hydroxide group: (C) uncoordinated Lewis acid site; (D) physisorbed phosphate group; (E) esterified phosphate group covalently bound to the surface; (F) multi-layer zirconium phosphate area resulting from partial dissolution of the zirconia matrix [53]. 12 Figure 6. Illustrations of the hypothetical interfacial zirconia–phosphate bonding, as characterized by SIMS [46]. 12 Figure 7. Schematic explaining the interactions of 10-MDP with zirconium and with the hydrated layer at the zirconia surface. (A) The 10-MDP monomer is adsorbed onto the zirconia surface via hydrogen bonding between the P= O (oxo group) and Zr-OH group. (B) The 10-MDP monomer may interact with zirconia via ionic bonding (C) in addition to ionic bonding between 10-MDP and zirconia, the adsorbed 10-MDP monomers have hydrogen-bonding interactions with zirconia via P= O (oxo group) [54]. 13 Figure 8. Monofunctional silane, γ-methacryloxypropyltrimethoxysilane (or 3-trimethoxysilylpropyl methacrylate) [55]. 14 Figure 9. Adhesion mechanism of resin bonding to silica coated substrates by an application of silane coupling agent (using 3-methacryloxypropyltrimethoxysilane as an example) [59]. 15 Figure 10. Preparation of zirconia specimens. 21 Figure 11. TOF-SIMS V, ION-TOF, German. 23 Figure 12. Scheme of ToF-SIMS analysis. 23 Figure 13. MDP related ions [46]. 24 Figure 14. Silane related ions. 25 Figure 15. Structure-specific fragments that can be traced back to zirconia phosphate compounds [46]. 26 Figure 16. Negative ions for 3D ions reconstruction. 27 Figure 17. Measurement of contact angle. 28 Figure 18. Specimen preparation for shear bond strength test. 29 Figure 19. Preparation of experimental adhesives. 31 Figure 20. Outline of this study. 31 Figure 21. Preparation of zirconia powder with SE, SE-5 and SE-10. 32 Figure 22. Specimens preparation for SSNMR analysis. 33 Figure 23. ToF-SIMS spectra (m/z = 0–200 amu) for the universal adhesives/primer groups. (A) Positive ion spectra. Zr+ (m/z 90) and ZrO+ (m/z 106) were the characteristic ion peaks of zirconia. (B) Negative ion spectra. The signals after 110 amu have been amplified by 10. Peaks of PO- related ions can by identified by PO2− (63), PO3− (79), and (PO3)2− (159). 38 Figure 24. Negative ion mass spectrum to illustrate the ZrP related structure-specific fragments in universal adhesives treated zirconia groups. Inset shows an expansion of m/z 180–360 region. Ions related to ZrP are labelled. 39 Figure 25. 3D ion reconstructions of the ion distribution in universal adhesives/primer at the interface. 42 Figure 26. ToF-SIMS spectra (m/z = 0–200 amu) for the experimental groups. (A) Positive ion spectra. Zr+ (m/z 90) and ZrO+ (m/z 106) were the characteristic ion peaks of zirconia. (B) Negative ion spectra. The signals after 110 amu have been amplified by 10. Peaks of PO- related ions can by identified by PO2− (63), PO3− (79), and (PO3)2− (159). 47 Figure 27. Negative ion mass spectrum to illustrate the ZrP related structure-specific fragments in experimental adhesives treated zirconia groups. Inset shows an expansion of m/z 180–360 region. Ions related to ZrP are labelled. 48 Figure 28. 3D ion reconstruction of the ion distribution in experimental adhesives at the interface. 51 Figure 29. Result of SSNMR analysis. 54 Figure 30. Scheme explaining interactions between MDP molecule and zirconia. [54] 55

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