臺灣博碩士論文加值系統

本研究先利用共沉澱法合成出鎂鋁水滑石(layered double hydroxide,LDH)及十二烷基硫酸鈉插層水滑石，並以X-ray繞射光譜(XRD)、傅利葉紅外光譜(FTIR)、穿透式電子顯微鏡(TEM)鑑定改質前後，水滑石層間距、官能基及形貌的變化，證實以該方法可成功合成出此兩種材料。
接著將有機改質及未改質之水滑石粉末以不同比例分別加入不帶電之聚乙烯吡咯烷酮(poly(N-vinylpyrrolidone),PVP)及帶負電之聚乙烯吡咯烷與丙烯酸共聚物(poly(N-vinylpyrrolidone-co-acrylicacid),PVP-co-PAA)高分子溶液中，配置成水滑石懸浮液(suspensions of LDH)。在水滑石懸浮液的黏度研究中將分為四個部分，分別為LDH/PVP、S-LDH/PVP、LDH/PVP-co-PAA及S-LDH/PVP-co-PAA。黏度數據顯示改質前後之水滑石之高分子懸浮液黏度均較原高分子溶液高。經分析後提出結論，LDH/PVP懸浮液中有消耗聚集發生、LDH/PVP-co-PAA中高分子因靜電吸引之吸附而導致架橋及電荷中和的聚集現象；而S-LDH在PVP及PVP-co-PAA系統中以疏水作用為主。

SUMMARY

The preparation and the investigation of suspensions of layered double hydroxid in poly(N-vinyl pyrrolidone) (PVP) and poly (vinyl pyrrolidone-co-acrylic acid) (PVP-co-PAA) have been studied in detail.
Mg-Al layered double hydroxides (Mg-Al LDH) and organically modified LDH using sodium dodecyl sulfate (SDS-LDH) were synthesized by co-precipitation method. The structure properties have been characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Transmission electron microscope (TEM).
The effects of interactions between LDH particles and polymers on viscous behavior were studied for suspensions of LDH particles with different concentration. For both particles (LDH and SDS-LDH), the suspensions show an increase in viscosity as compare to the polymer solutions.
The suspensions of LDH/PVP-co-PAA are flocculated by bridging and charge neutralization mechanisms, while depletion flocculation occurs in the suspensions of LDH/PVP. Furthermore, we have concluded that hydrophobic interactions dominate the increment of viscosity in both SDS-LDH/PVP and SDS-LDH/PVP-co-PAA systems.

Key words: Suspensions of LDH/polymer, viscosity.

INTRODUCTION

We live through the courtesy of plants grown on clayey soil; we eat our food from ceramic dinnerware; we live in buildings partly made of clay bricks which rest on clay-containing soils into which they sometimes tend to disappear.

Layered double hydroxides (LDHs), also known as hydrotalcite clays, are also laminar minerals with anions sandwiched between hydroxide layers. Contrary to cationic clay widely discovering in nature, LDHs can be synthesized in the laboratory; synthetic LDHs have better-defined geometry and crystal structure than their natural counterparts. LDH have the general formula [M1-x2+Mx3+(OH)2]x+[Ax/nn- • mH2O]x- , where M2+ and M3+ are di- and tri-valent metallic cations and An- represent the anions in the interlayer space.
In almost every field of clay study, one has to deal at one time or another with dispersions of clay in water or in another fluid (e.g., polymer solution).Such dispersions, which are characterized by large interfacial area between the extremely small clay particles and the surrounding liquid, are colloidal systems.
Colloid chemist looks primarily at a system on a microscopic scale.
We are well aware that the bulk properties of the dispersion of clay system depend on the concentration as well as on the type of clay (e.g., anionic clay, LDH in our research); but above of all, we are familiar with─and often puzzled by─the remarkably strong dependence of these properties on the composition of the fluid phase. Comparatively minor change in the composition of the liquid often have surprisingly large effect on the behavior of the system.
The effect of small amount of dissolved chemicals in the clay system are governed by the rules of colloid chemistry because the size of particles involved usually under micrometer or even smaller.

MATERIALS AND METHODS

Synthesis of LDH platelets

SDS-LDH particles were synthesized by co-precipitation method with DS- as the interlayer anions. SDS (3.46g) was dissolved in 20 mL boiled deionized water in a three-neck flask. Magnesium nitrate (5.28g) and aluminum nitrate (3.86g) were dissolved in 20 mL boiled deionized water. The nitrate solution was then slowly dropped into the vigorously stirred SDS solution and the pH of the reaction solution was maintained at 10 by adding 2 M NaOH solution. The reaction was proceeded about 1 day with nitrogen purging.
Preparation of suspensions for viscosity study

1%, 3%, and 5% LDH or SDS-LDH powders were add to 1%, 2%, and 3% PVP or PVP-co-PAA directly. The unit of percentage was weight percentage concentration.

RESULT and DISCUSSION

Characterization LDH and its modified forms.

The Mg-Al-LDH and SDS-LDH powders were firstly characterized by XRD. The XRD patterns are shown in Fig. 1 and Fig. 2, the basal spacing was calculated according to the Bragg diffraction law. The sharps peaks observed at 2θ=10.2° and 3.4° correspond to the d003 peak with the basal spacing of 0.87 nm and 2.6 nm respectively.
FTIR for pristine LDH and SDS-LDH were recorded for wave numbers 400-4000 cm-1. The broad band around 3500 cm-1 is due to the O-H stretching vibration of metal hydroxide layer and interlayer water molecules. The bands locate at 1220 cm-1 and 1060 cm-1 are symmetric and asymmetric S=O vibration respectly. The absorbance present around 2920 cm-1 and 2845 cm-1 are caused by stretching vibration of CH2. The FTIR result are shown in Fig. 3.

Viscosity study of LDH/polymer suspensions

Rheological measurements were carried out on Brookfield LVDV-Ⅲcone-plate rheometer. The viscos behavior were investigated by plot of apparent viscosity (cP) vs. shear rate (1/s) .we have observed conspicuous shear thinning behavior of LDH/water suspension. These results due to the breakdown of the agglomerated structure when larger shear stress was applied.
We have found that the suspensions of LDH/PVP show an increase in viscosity as compare to the PVP solutions result from depletion flocculation in Fig. 4. When PVP is added to the colloidal suspensions, because the depletion layers are impenetrable to the polymer, the polymer concentration varies from zero (around the depletion layer) to the value of the bulk polymer, there is a polymer concentration gradient resulting in unbalanced osmotic pressure which pushes the LDH plates together.
Because attractive force induce by depletion are stronger than van der waal force in LDH/water suspensions, adding PVP result in gently decrease of viscosity with increasing shear rate imply shear thinning behavior is much more unobvious.
As shown in Fig. 5, the suspensions of LDH/PVP-co-PAA show an increase in viscosity as compare to the PVP-co-PAA solutions. It’s thought to be flocculate by mechanism of bridging or charge neutralization flocculation. As adsorption of PVP-co-PAA at surface of LDH by electrostatic interaction between negative segment of polymer and positive LDH platelet, LDH particles were push together via each end of PVP-co-PAA. In addition, the adsorption of a anionic PVP-co-PAA on a positive particle would reduce the surface charge of later, and this charge neutralization could be an important factor in flocculating the particles.
In Fig. 6 and Fig. 7, we have found that elevation of viscosity in both of SDS-LDH/PVP and SDS-LDH/PVP-co-PAA suspensions and concluded that hydrophobic interactions dominate the increment of viscosity in both systems.
CONCULSION

The LDH-surfactant hybrid synthesized by co-precipitation method and characterized by XRD and FTIR. The modified Mg-Al-LDH show an increase in interlayer distance as compared to the unmodified Mg-Al-LDH.
Depletion flocculation occurs in the suspensions of LDH/PVP resulting in viscosity increment. Increase of viscosity in LDH/PVP-co-PAA systems is result from bridging and charge neutralization flocculatation.Finally, elevation of viscosity in S-LDH/PVP and S-LDH/PVP-co-PAA system are both due to hydrophobic interactions between S-LDH particles and alkyl chain of polymer. 

中文摘要 I
Abstract II
誌謝 IX
總目錄 X
表目錄 XIV
圖目錄 XV
第一章 緒論 1
第二章 文獻回顧 3
2-1水滑石的結構及基本特性 3
2-2水滑石之製備方式 7
2-2-1共沉澱法 7
2-3有機改質插層型水滑石 11
2-3-1陰離子界面活性劑插層型水滑石 11
2-3-2十二烷基硫酸鈉(Sodium dodecyl sulfate)插層水滑石 12
2-4分散系統(Dispersion) 14
2-5 Hydrophobic suspension 16
2-5-1 Hydrophobic sols之性質 17
2-5-2粒子間作用力與DLVO理論 18
2-5-3高分子致使之聚集現象(Flocculation with polymers) 20
2-6水滑石懸浮液 26
2-6-1水滑石水溶液 27
2-6-2水滑石之高分子懸浮液(LDH/polymer suspensions) 28
2-6-3陽離子型黏土懸浮液 29
第三章 實驗部分 32
3-1實驗藥品與儀器設備 32
3-1-1實驗藥品 32
3-1-2分析儀器 33
3-1-3非分析器材 34
3-2 實驗材料製備方法與步驟 35
3-2-1鎂鋁水滑石(Mg-Al-LDH)製備方法與步驟 35
3-2-2十二烷磺酸鈉(Sodium dodecyl sulfate)插層型水滑石製備 36
3-2-3 PVP-co-PAA的合成與純化 37
3-3黏度分析 38
3-3-1樣品製備 38
3-3-2實驗濃度配置 39
3-3-3流變儀操作及數據取得 40
3-4沉降實驗 40
3-5儀器分析 41
3-5-1 X-ray繞射分析(XRD) 41
3-5-2紅外線光譜分析 (FTIR) 41
3-5-3錐板式流變儀分析(Cone/Plate Rheometer) 41
3-5-4雷射光散射法粒徑及界面電位分析儀 42
3-5-5酸鹼度測量儀器 42
第四章 實驗原理 43
4-1黏度 43
4-1-1黏度的定義 43
4-1-2黏度的單位 44
4-1-3 流變學 44
4-1-4 錐板式流變儀 49
4-2沉降法 51
4-3電動勢能(electrokinetic potential) 52
4-4雷射光散射法粒徑及介面電位分析儀 54
第五章 結果與討論 58
5-1 LDH之鑑定 58
5-1-1 X-ray繞射及小角度散射圖譜 58
5-1-2 FTIR數據分析 61
5-1-3 LDH與SDS-LDH之TEM影像圖 63
5-2 熱重分析曲線 64
5-3 PVP-co-PAA組成比例鑑定 66
5-4 Agglomerate particle size 67
5-5 Zeta-potential數據分析 71
5-6沉降實驗 73
5-7黏度數據分析 78
5-7-1 LDH/PVP系統 78
5-7-2 S-LDH/PVP系統 82
5-7-3 LDH/PVP-co-PAA系統 87
5-7-4 S-LDH/PAA-co-PVP系統 93
第六章 結論 99
(一)材料部分 99
(二)水滑石/高分子懸浮液之研究 99
參考文獻 101

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