泥岩與chitosan-pva水膠之研究swcdis.nchu.edu.tw/alldatapos/advancepos/8096042004... ·...

泥岩與chitosan-PVA水膠之研究A study on mudstone and chitosan-PVA hydrogels

指導老師：林俐玲、鄭皆達、陳鴻烈、林德貴博士研究生：江孟玲學號：89642004

中華民國九十八年五月十五日

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♦一、泥岩 mudstone♦二、水膠 hydrogels♦三、Effect of chitosan on the available

contents and vertical distribution of Cu2+ and Cd2+ in different textural soils.

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一、泥岩mudstone



泥岩（mudstone）♦台灣泥岩區域分布廣泛，涵蓋東部利吉層、西南部麓山帶與墾丁三大區域，其中以西南部泥岩丘陵之分布面積最大，涵蓋面積超過1 0 0 0 k m 2（林慧宜，2 0 0 5 ）。The area distributing mudstone in Taiwan is extensive which is characterized as three main regions, including ‘Li-Chi’ rock stratum in the Eastern, the roots area of mountains in the Southwest, and Kenting National Park. The mudstone wolds of the Southwest covering 1000 km2 in that area are dispersed widest among the above-mentioned.

♦西南部泥岩地區受八掌溪、急水溪、曾文溪、鹽水溪、二仁溪及阿公店溪上游河川作用所影響，提供沿海沖積平原充足的沉積物質（李德河， 1994）



臺灣本島泥岩之分布(Distribution of mudstone of Taiwan)



西南部泥岩層(Mudstone layer in the southwest)

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♦西南部地層包含更新世的六雙層以及上新世的古亭坑層，內含主要組成的青灰色泥岩，早期學者稱之為青灰岩，近期則有學者統稱此泥岩為南化泥岩（ Chang et al .， 1996）。由於成岩時間較短，且岩質軟弱，在自由吸水狀態容易產生回脹、崩解，對於河川、地表逕流與降雨的沖蝕作用，其抵抗力十分薄弱（林俊全，1996）。

♦ The crumbliness phenomena due to distention and contraction by aridity and moistness repeatedly result in the severe erosion and influence of this expanse by current and tectonic movement respectively.

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♦西南部岩區中乾溼分明的氣候特徵，因此泥岩區的邊坡具較高之沖蝕率，在地形表現乃為刃嶺山脊之惡地地形，一般在沉積區常見之方向性地層控制地形，反而較不明顯。

♦邊坡常發生的災害：在自然邊坡有地表沖蝕、泥流及風化土層之滑落；在人工挖方邊坡則有地表沖蝕、崩壞（落石）及風化土層滑落；在人工填方邊坡則有地表沖蝕、泥流、沉陷及管蝕（ p i p i n g）。

♦河川、水庫之泥岩邊坡亦常受到河川沖刷、水庫波浪侵蝕，以致產生崩壤或崩落，堆積於河川或水庫中，造成河川淤積、水庫儲水能量降低。

♦ The surface soil to flow away and the destruction of terrain. Moreover, that contributes low efficiency of the protection of mountainside and planting engineering.



刃嶺山脊之惡地地形

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低窪處可見白色結晶(There is white crystallization in the depression)

阿公店水庫附近



♦泥岩地區的理化性質特殊，pH值高，坋粒含量多，金屬離子含量高。The physical and chemical properties of mudstone are special, pH is high, and the content of metal ion is high.

♦由於黏土膠結不良，且孔隙水含Na量偏高，pH 值達8∼9 之間，使得黏土片間因水合Na+的吸附而失去膠結作用，造成泥岩容易流失與崩坍。因此須降低Na含量與降低pH 值著手，使泥岩之黏土能保有穩定凝聚態，即膠結作用，並建議添加膠結物來改良其性質。 The clay loses glued function because of the absorbing of hydration Na, and cause the loss of mudstone. So propose adding the glued thing to improve its property.



二、水膠 hydrogels



水膠(hydrogels)♦水膠為一親水性高分子，具有三度空間之網狀交聯(cross linking)結構，在水中可以吸水膨潤(swelling)，同時可以在膨潤狀態時，吸住並保有巨量體積的水份，吸水膨潤後產生類似果凍(jellylike)的混合物。其交聯之鍵結作用力可為共價鍵或離子鍵以及二級作用力的氫鍵或疏水基之間的相互作用力。Hydrogel is a type of hydrophilic polymer with three-dimensional structure.



水膠的吸水原理♦ 水膠最常見為聚丙烯酸鹽系列之高分子，以聚丙烯酸鈉為例，說明水膠的吸水原理：

吸水前，高分子的長鏈互相纏結、且高分子鏈為三次元網狀結構，所以整體而言為密集聚在一起之集合狀態。

吸水後，水會解離羧酸鈉官能基（－COO-－Na+）中之鈉離子（Na+），使高分子鏈上成為含有帶負電之羧酸根陰離子官能基(－COO-－），而這帶陰離子之官能基，彼此排斥而打開高分子鏈，使得水分子更加容易進入高分子網目中，直到整個高分子網目被撐開為止。

而帶陰離子之親水性官能基會將水分子緊緊抓住，故這類吸水性高分子亦同時具有保水性；另一方面，高分子水膠本身為三次元網目結構，所以不會溶於水中，藉由膨潤保持吸住水分子。

如果沒有三次元網目結構時，高分子鏈會在水中漸漸擴散，而被溶解。



水膠的結構必須具有:♦（1）水膠分子本身具有親水基或離子基。

♦（2）水膠分子鏈本身不能在水中擴散而溶解於水，須具有交聯網目等不溶於水的結構。-----(這不是完全我要的)

親水基或離子基之導入，可藉由親水基單體之直接聚合，或在高分子上接枝而獲得。另外，藉由高分子交聯方法，可得到具有不能溶解之交聯網目高分子結構。



What I need…♦ 1. 能夠吸水保水,但是適當的時機要能溶於水入滲於土壤中. It can absorb water and protect water, but also can dissolved in water and entering the soil.

♦ 2. 當材質分解後可以改善土壤的鈉金屬離子含量過高的問題. It can improve the problem that the high content of sodium ion in soil after the material is decomposed.



♦幾丁聚醣（chitosan）是由幾丁質經高濃度熱鹼處理，進行去乙醯(deacetylation)反應，去除全部或部份乙醯基形成帶有葡萄胺糖（ glucosamine）及乙醯葡萄胺糖（N-acetyglucosamine）的高分子聚合物。幾丁質的含量在自然界中僅次於纖維素，亦是地球上蘊藏量最豐富的胺基醣型式之多醣，由於幾丁聚醣是生物聚合的天然高分子，因此具有良好的生物相容性，幾乎無毒性，可被生物分解，具有生物活性，又因價格便宜、生產原料不虞匱乏等優點，使幾丁質、幾丁聚醣逐漸成為近幾年來在農業，紡織，食品加工，化工醫藥及高分子生醫材料上頗受重視的新興材料。



♦聚乙烯醇(Polyvinyl alcohol)具有良好化學穩定性、在不同的pH 值及一些有機溶劑中有良好的穩定性、薄膜性質、高親水性，黏彈性及強力接著性，然而其在水溶液中並不穩定。因此聚乙烯醇需要和其他物質交鏈或是經由化學反應改質以達到良好的機械性質

♦利用幾丁聚醣（chitosan）和聚乙烯醇（PVA）摻合（blend）形成的水膠(hydrogels) 應用於泥岩表面處理。

OH

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薄膜的製作♦ 1. 幾丁聚醣(Chitosan)溶液的配製：將幾丁聚醣

(Chitosan)溶於1%的醋酸水溶液中，配成濃度為2.5 wt%幾丁聚醣(Chitosan)溶液，置於攪拌器使其充分均勻攪拌24 小時，過濾雜質後待用。

♦ 2. 聚乙烯醇（PVA）溶液的配製：將聚乙烯醇（PVA）溶於80℃之熱水中，配製成濃度為10 wt%聚乙烯醇（PVA）溶液，置於攪拌器使其充分攪拌4 小時後待用。

♦ 3.薄膜的製備：將幾丁聚醣(Chitosan) /聚乙烯醇（PVA）按照幾丁聚醣(Chitosan)含量分別為5、10、15、20、25、30、40、50、60、70、80、90、100 wt%摻合聚乙烯醇（PVA）製成溶液。



Water absorption experiment♦ 1.將chitosan-PVA置於110℃的烘箱中24 小時，取出後置於乾燥皿冷卻精秤重量Wa至誤差範圍在0.001 克。

♦ 2.將chitosan-PVA置入蒸餾水浸泡2 小時，取出後用濾紙過濾表面多餘的水分吸除，精秤重量Wb至誤差範圍在0.001 克。

♦含水率＝(Wb-Wa)/Wa



水氣穿透試驗Water vapor permeation experiment

H2O

固定濾網

濾紙

chitosan-PVA(0.25g)

CaCl2

Water vapor permeation(g/m2/day)＝(W2－W1) ×T/πR2

未放入時W1 g放入1hr後W2 g

T=1/24

R

幾丁聚醣濃度(chitosan)含量與水氣穿透量兩者成正比關係

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計畫實驗♦ 1.樣區採取泥岩進行性質分析♦ 2.以泥岩土壤取代濾紙進行水氣穿透試驗♦ 3. chitosan-PVA降解速率研究♦ 4.應用水膠之後金屬離子的垂直梯度分佈



三、Report on a significant study



1. Introduction♦ Chitosan是由甲殼動物殼，昆蟲表皮和真菌細胞壁所分離出的chitin deacetylation所得，因為對金屬離子高的吸附能力，因此可望成為土壤中的治療劑。Chitosan, the deacetylation form of chitin which widely spreadin the crustacean shell, insect epidermis and the fungi cell walls, emerges to be a promising soil remedy additive due to its high adsorption capacity with metal ions.



♦除了利用離子交換或吸收， chitosan化合物上的OH-與NH2

-為螯合基，因此可透過錯合反應(螯合)與金屬離子結合，螯合是主要的作用，能形成穩定且不可逆的化合物。Through ion exchange, adsorption and complexation, the largely spread hydroxyl and amine groups serve as effective chelating sites for heavy metals, and complexationwas reported to be the major, the most stable, and irreversible form of chitosan.

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♦研究主要針對在不同土壤，不同劑量的chitosan對Cu2+和 Cd2+影響(吸收)的垂直的分佈。The objective of this investigationwas to study the effects of different dosages of chitosan on the available contents and vertical distribution of Cu2+ and Cd2+ in different textural soils.



2. Experimental2.1. Material

The properties of chitosan were as followings: yellowish white powder with 40 meshes, 80% degree of deacetylation and molecular weight of 6×105, industrial grade



♦實驗土壤收集自上海角湯大學(SJTU)的蔬菜田中的0–20cm犁層，放在箱子裡使用。Soils used in the box experiments were collected from the 0–20cm plow layer of the vegetable field in the experimental station, School of Agricultural and Biology in Shanghai Jiao Tong University (SJTU).

60mg/kg

0.3mg/kg

0.58 Ms/cm

1.36g /kg

1.14g/ kg

7.4

total Cu

total Cd

ECtotal Ptotal NpH

2.2. Soil characteristics

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♦以硝酸鎘和硝酸銅將實驗土壤的total Cd控制在50mg/kg、 total Cu控制在500mg/kg ，靜置21天達到平衡。The total Cu2+ and Cd2+ contents were set as 50mgCd/kgDW soil and 500mgCu/kg DW soil. Cadmium and copper were applied as Cd(NO3)2·4H2O and Cu(NO3)2·3H2O, mixed thoroughly with the soil samples, and the soil was equilibrated for 21 d before the treatments with chitosan.

♦ The soils were firstly air-dried, passed through a 2-mm sieve and mixed thoroughly, then proportioned into three textural (clay, loam and sandy) soils.



2.3. Soil treatments

♦ 1. Day/night temperature of 30/25 ℃and humidity of 65/80% were applied.

♦ 2. The air-dried soil was prepared by weighing 20 kg of soil into 0.4m×0.4m wooden boxes, respectively.

♦ 3. Two litres deionized water was then sprayed onto the soils in batches and plastic films were covered on the boxes to remain the soil moisture for 30 d.



1.050.90.750.600.450chitosan concentrationsin the soils (g /kg)

21g18g15g12g9g0gChitosan/900mL HCl

T6T5T4T3T2 T1編號

♦ Soil samplings were performed after 0 d, 7 d, 14 d, 21 d, 28 d, and 35 d. The vertical soil cylinder of 0–30cm and soil profile samples of 4–6 cm, 14–16 cm, and 24–26cm were obtained by a stainless soil sampler, respectively (only for T5). And, four replications were performed at least

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3. Results and discussion

FDBCu2+

ECACd2+

sandysoil

loam soil

clay soil

available contents

T2與T3結果相近

chitosan的濃度對Cu2+含量影響較大

前7天 , Cu2+ and Cd2+

含量減少最多

Cd2+的含量有波動

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♦如預期的, chitosan的使用量增加,三種土壤的Cu2+ and Cd2+含量都下降. With the increasing dosage of applied chitosan, the availablecontents of Cu2+ and Cd2+ in three textural soils decreased respectively.

♦ Chitosan對Cu2+選擇性比對Cd2+強,所以chitosan的濃度對Cu2+含量影響較大. Theselectivity of chitosan to Cu2+ was stronger than Cd2+, which may be the reason for the significant decrease of the available content of Cu2+ after applying chitosan in the soils.



♦但是,除了Cd2+在黏土與砂土中之外,當chitosan含量少於0.6 g/kg土壤(T3) 或大於0.9 g/kg土壤(T5) 時Cu2+ or Cd2+的含量沒有明顯不同. But no significant difference (except for Cd2+ in clay and sandy soils) was found between the dosages of chitosan on the available contents of Cu2+ or Cd2+ when less than 0.6 g chitosan /kg soil (T3) or more than 0.9 g chitosan /kg soil (T5) were applied (P > 0.05).

♦分散在chitosan的NH2這個基團透過螯合形成chitosan-Cu2+和chitosan-Cd2+的錯合物. The amino groups spread in chitosan can form chitosan-Cu2+ and chitosan-Cd2+ complexes with Cu2+ and Cd2+

through chelation.



♦最主要的效應是施用chitosan的前七天,這代表chitosa對解決重金屬的汙染物,成效在很短時間的就可看到。 The main effect of chitosan on the available contents of Cu2+ and Cd2+

occurred within the first 7 d of chitosan treatment, suggesting that chitosan application could dispose the heavy metals contaminated soils effectively in a short period.



♦ Cu2+ and Cd2+的含量在第七天後持續減少, 但是尤其是在14天之後Cd2+的含量有波動，但是Cu2+的含量曲線平滑.The available contents of Cu2+ and Cd2+ continued to decrease slightly after 7 d,furthermore, a slight fluctuation was found on the available Cd2+ content after 14 d, especially in the clay soil and loam soil, but available Cu2+ content changed smoothly.

♦這可是因為有一部分的chitosan是以離子交換形式或物理性吸附,而吸附-釋放間的動力平衡所引起.Which might result from the dynamic “adsorption–desorption” balance of complexes formed from chitosan with a small part of metal ions by ion exchange or physical adsorption.



Layers of clay (A,D), loam (B,E) and sandy (C,F) soils

5cm深的土壤含銅量最高

應用7天後,在壤土和沙土裡增加

壤土和沙土裡,趨勢接近

壤土和黏土,趨勢接近

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♦三種土壤中的Cu2+的垂直分佈都非常類似,在5cm 深的土壤中含量都很高,而15-25cm 的部份,差異很小. 原因可能是由於金屬離子的運動。The vertical distributions of available Cu2+

content changed similarly after applying chitosan into three textural soils as shown in The Cu2+ content at 5 cm surface soil layer was much higher than that at 15cm and 25cm soil layers (P < 0.05), and the Cu2+ contents between 15cm and 25cm soil layers differed little (P > 0.05), which may result from the movement of metal ions.



♦應用chitosan時的主要迅速吸收金屬離子在5cm土壤層內，並因此刺激金屬離子從更低的土壤層移動到表面土壤層。 Applied chitosan in the soils mostly adsorb metal ions rapidly in 5 cm soil layers, which resulted in a larger instantaneous concentration potential in the soil layers, hence stimulated the metal ions moving from the lower soil layers to the surface soil layers.

♦應用7天後,在5cm土壤層內,黏土中含銅量減少而在壤土和沙土裡含銅量增加。Moreover, the available Cu2+ content in the 5 cm clay soil layer decreased obviously after 7 d of chitosan application, but increased in the loam soil and sandy soil.

♦在15-25cm土壤層內,壤土和沙土含銅量趨勢相似,但粘土差異很大. The Cu2+ contents in 15 cmand 25cm soil layers presented a similar trend in the loam and sandy soils, but a greater difference was showed in the clay soil.

觀察所得



♦ 重金屬離子的移動取決於離子和土壤之間不同的物化性質所造成的相互作用,黏土粒子和有機物是兩個主要元素。 The movement of heavy metal ions in soils depends on the interaction between those ions and soils of different physicochemical properties, in which clay particles and organic matter are two main factors.

♦ 因為化學性質相近的關係,土壤中的黏粒成分越高,吸附重金屬離子的能力越強,導致離子移動越困難。意味著當時，有機物越高,越能吸附更多重金屬離子。 Under the similar chemical properties, the soils with more clay particles have stronger adsorption with heavy metal ions, thus the ions move more difficultly. Mean while, soils with higher organic matter content could adsorb more heavy metal ions.

♦ 這項研究過程中的黏粒有機物成份含量是黏土 > 壤土 > 砂土。因此，在土地裡的重金屬離子的運動速率為砂土> 壤土 > 黏土。 The contents of clay particles and organic matters of three textural soils in this study was clay soils > loam soils > sandy soils. Therefore, the movement rate of heavy metal ions in the soils should be in the order of sandy soils > loam soils > clay soils.

解釋



4. Conclusion♦在三種不同的土壤中施作Chitosan均能有效降低

Cu2+ and Cd2+含量. Chitosan application could reduce available Cu2+ and Cd2+ contents in three different textural soils.

♦ 0.9 g chitosan/kg的施作量可得最好的效率. Lower available Cu2+ and Cd2+ were detected in treatments of increasing dosage of chitosan application, and 0.9 g chitosan/kg soil was perfect for this remediation.

♦在施作後的最初7天為Cu2+ and Cd2+最主要的吸收. Moreover, chitosan mainly adsorb Cu2+ and Cd2+ in the first 7 d after applying chitosan to the soils.



Thank you for your attention

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幾丁聚醣 Chitosan

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泥岩與chitosan-pva水膠之研究swcdis.nchu.edu.tw/alldatapos/advancepos/8096042004... ·...

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