結論 - 奈米級氫氧基磷灰石-幾丁聚醣複合材料

1. 三種製程中，以製程 A(磷酸溶液與幾丁聚醣先混合，最後加入醋酸鈣溶液)之 DH 最低，可能的因素有交聯程度高、CDHA 與 CS 界面最好、粒子小且均勻分散，可由 TGA、FTIR、DMTA 來證明

2. 在製程 A 中，隨著有機/無機比例的不同，滲透係數高低依序為幾丁聚醣 50%、100%、70%、90%，隨著 CDHA 含量提高使得交鏈程度上升，導致其 DH 值降低，但是由於 CDHA 含量提高，

也會導致孔隙度的提高，影響到其滲透係數隨之上升，在兩個因素的共同影響下，幾丁聚醣含量 90%時，滲透係數最低。

3. 第二部分的實驗中，以製程 E(先合成 CDHA 再加入 PAA，最後加入幾丁聚醣)之 DH 最低，可能的因素有交鏈程度高、三種材料間的界面良好、均勻分散，可由 TGA、FTIR、DMTA 來證明

4. PAA 含量對複合材料的之影響，不管在製程 D 或 E，當 PAA 含量過少或是太多，均會降低 PAA 界面整合的功能，使得滲透係數上升。在不同製程狀況下，所需要的 PAA 含量也隨之不同。

5. PAA 分子量提高，對於擔任 CDHA 與幾丁聚醣間界面整合的角色，

似乎不是個正面的影響，應該是由於其分子量過大時，包覆的效果不良與本身的官能基過多，無法擔任界面橋樑的任務，導致滲

6. 製程中的 PO⁴^3-對交鏈程度有影響，進而影響到滲透係數。

7. in-situ 製程中，CDHA 與 CS 基材的反應，可作為成核起始點，

對於分散性有正面幫助，導致滲透係數下降，強度上升。

8. 奈米粒子與有機基材之界面反應，其對分子運動的影響，會對滲透產生重大的影響，而扮演界面橋樑的高分子電解質，含量有一定數值，過多過少都不行。

未來工作：

1. 以 NMR 深入研究 PAA 在 CDHA 上之構形(Conformation)。

2. 利用 Zeta potention 探討 PAA 含量與粒子表面電位之關係，提出更完整的證據。

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20 30 40 50 60 CDHA CDHA-CS Ca-Cs-P P-CS-Ca CS

In ten sity (a.u .)

2 θ (degree)

圖 4-1. 固定有機/無機含量比，改變添加順序之 XRD

4000 3500 3000 2500 2000 1500 1000 500 CDHA

CS 100%

CS 90%

CDHA-CS Ca-CS-P

P-CS-Ca

A bsorb an ce (a.u .)

Wave number (cm

^-1

)

圖 4-2. 固定有機/無機含量比，不同添加順序之薄膜，未經 TPP 交聯之 FTIR

4000 3500 3000 2500 2000 1500 1000 500 Before

crosslinking

After crosslinking

CS

Ab sorb an ce (a.u .)

Wave number (cm

^-1

)

圖 4-3. 幾丁聚醣薄膜經交鏈前後之 FTIR

100 200 300 400 500 600 700 800 900 20

30 40 50 60 70 80 90 100

CS 90%

We ig ht %

Temperature (

C)

P-CS-Ca Ca-CS-P CDHA-CS

圖 4-4. 固定有機/無機含量比，不同添加順序之薄膜，未經 TPP 交聯之 TGA

100 200 300 400 500 600 700 800 900 95

96 97 98 99

100

CDHA

We ig ht %

Temperature (

C)

圖 4-5. 純 CDHA 之 TGA

100 200 300 400 500 600 700 800 900 40

50 60 70 80 90

100

TPP ion-crosslinking CS 90%

We ig ht %

Temperature (

C)

P-CS-Ca Ca-CS-P CDHA-CS CS

圖 4-6. 固定有機/無機含量比，不同添加順序之薄膜，經過 TPP 交聯之 TGA

0 1 2 3 4 5 6 0.000

0.005 0.010 0.015 0.020 0.025

Conc. ( m g/ m l)

Time (hr)

P-CS-Ca CDHA-CS Ca-CS-P

圖 4-7. 固定有機/無機含量比，不同添加順序之薄膜，經過 TPP 交聯後之滲透曲線

CS P-CS-Ca CDHA-CS Ca-CS-P

0.0002 0.0003 0.0004 0.0005 0.0006 0.0007 0.0008 0.0009

DH ( cm

/h r)

PROCESS

圖 4-8. 固定有機/無機含量比，不同添加順序之薄膜，經過 TPP 交聯後之滲透係數

P-CS-Ca

Ca-CS-P

CDHA-CS

圖 4-9. 固定有機/無機含量比，不同添加順序之 TEM 100 nm

100 nm

P-CS-Ca

Ca-CS-P

CDHA-CS

圖 4-10. 固定有機/無機含量比，不同添加順序之 SEM

20μm

4μm 20μm

20μm

4μm

-100 -50 0 50 100 150 200

Temperature (

C)

P-CS-Ca

P-CS-Ca Ca-CS-P CDHA-CS CS 4000

-100 -50 0 50 100 150 200 0.00

0.02 0.04 0.06 0.08 0.10 0.12

Ta n De lt a

Temperature (

C)

P-CS-Ca Ca-CS-P CDHA-CS CS

圖 4-12. 固定有機/無機含量比，不同添加順序之薄膜，未經 TPP 交聯後之 DMTA-2

圖 4-13. 示意圖一

CDHA

CS

PO

3-NH

₃⁺

CDHA

20 30 40 50 60 10%

30%

50%

70%

P-CS-Ca, CS content

CDHA 100%

90%

in ten sity (a. u .)

2 θ (degree)

圖 4-14. 固定添加順序，不同有機/無機含量比之 XRD

4000 3500 3000 2500 2000 1500 1000 500

P-CS-Ca, CS content

100%

10%

70%

50%

30%

90%

A bso rb an ce (a .u .)

Wave number (cm

^-1

)

圖 4-15. 固定添加順序，不同有機/無機含量比之薄膜，未經 TPP 交聯之 FTIR

100 200 300 400 500 600 700 800 900

P-CS-Ca, CS content

We ig ht %

Temperature (

C)

圖 4-16. 固定添加順序，不同有機/無機含量比之薄膜，未經過 TPP 交聯之 TGA

100 200 300 400 500 600 700 800 900

100

CS content

100%

P-CS-Ca ,TPP ion-crosslinking

We ig ht %

Temperature (

C)

圖 4-17. 固定添加順序，不同有機/無機含量比之薄膜，經過 TPP 交聯之 TGA

0 1 2 3 4 5 6 0.000

0.005 0.010 0.015 0.020

P-CS-Ca, CS content

Co nc . ( m g/ ml )

TIME (hr)

50%

70%

90%

100%

圖 4-18. 固定添加順序，不同有機/無機含量比之薄膜，經過 TPP 交聯後之滲透曲線

50 60 70 80 90 100 0.0002

0.0003 0.0004 0.0005 0.0006 0.0007 0.0008

0.0009

P-CS-Ca

DH ( cm

/h r)

CS content %

圖 4-19. 固定添加順序，不同有機/無機含量比之薄膜，經過 TPP 交聯後之滲透係數

CS50%

CS70%

CS90%

圖 4-20. 固定添加順序，不同有機/無機含量比之 SEM

20μm 20μm

20μm

4μm 4μm

圖 4-21. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之 XRD

20 30 40 50 60

CDHA-CS (CDHA-PAA)-CS

(Ca-PAA-P)-CS

In ten sity (a.u .)

2 θ (degree)

4000 3500 3000 2500 2000 1500 1000 500

PAA 0.01%

CDHA-PAA-CS

CDHA-CS Ca-PAA-P-CS

CS-PAA

A bso rb an ce ( a. u .)

Wave number (cm

^-1

)

圖 4-22. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之薄膜，

未經 TPP 交聯之 FTIR

100 200 300 400 500 600 700 800 900 20

30 40 50 60 70 80 90

100

PAA 0.01%

We ig ht %

Temperature (

C)

Ca-PAA-P-CS CDHA-PAA-CS CDHA-CS CS-PAA

圖 4-23. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之薄膜，

未經 TPP 交聯之 TGA

100 200 300 400 500 600 700 800 900 40

50 60 70 80 90

100

PAA 0.01%, TPP ion-crosslinking

We ig ht %

Temperature (

C)

Ca-PAA-P-CS CDHA-PAA-CS CDHA-CS CS-PAA

圖 4-24. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之薄膜，

經過 TPP 交聯之 TGA

100 200 300 400 500 600 700 800 900 0

20 40 60 80 100

TPP

PAA

We ig ht %

Temperature (

C)

圖 4-25. PAA 與 TPP 之 TGA

0 1 2 3 4 5 6 0.000

0.005 0.010 0.015 0.020

Co nc . ( m g/ m l)

Time (hr)

Ca-PAA-P-CS CDHA-PAA-CS CDHA-CS CS-PAA

圖 4-26. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之滲透曲線

PAA-IC PAA-NI CDHA-CS CS-PAA 0.0002

0.0003 0.0004 0.0005 0.0006 0.0007

PAA-IC: Ca-PAA-P-CS PAA-NI: CDHA-PAA-CS CS : 0.000570

DH ( cm

/h r)

PROCESS

圖 4-27. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之滲透係數

-100 -50 0 50 100 150 200 0

2000 4000 6000 8000 10000 12000 14000 16000

St orage M odu lu s

Temperature (

C)

Ca-PAA-P-CS CDHA-PAA-CS CDHA-CS CS-PAA

圖 4-28. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之 DMTA-1

-100 -50 0 50 100 150 200 0.00

0.02 0.04 0.06 0.08 0.10 0.12

Ta n De lt a

Temperature (

C)

CDHA-CS (Ca-PAA-P)-CS (CDHA-PAA)-CS CS-PAA

圖 4-29. 固定 CS/CDHA/PAA 含量，不同 CDHA/PAA 製程之 DMTA-2

1800 1700 1600 1500 1400 1300 1200 1100 1000

1420-1300 and 1610-1550 R-COO

-1470-1430 -CH₃, -CH-₂ 1700-1725

R-COOH

CDHA CDHA-PAA

Ca-PAA-P PAA

Abs or ba nc e( a. u. )

Wave number (cm

^-1

)

圖 4-30. 固定 CDHA/PAA 含量，不同 CDHA/PAA 製程粉末之 FTIR

100 200 300 400 500 600 700 800 900 86

88 90 92 94 96 98 100

Ca-PAA-P

CDHA-PAA

We ig ht %

Temperature (

C)

圖 4-31. 固定 CDHA/PAA 含量，不同 CDHA/PAA 製程粉末之 TGA

CDHA

Ca-PAA-P 圖 4-32. CDHA 與 PAA 之 TEM

100 nm

圖 4-33. 示意圖二

NH

₃⁺

CS

CDHA PO

₄

3-Ca

²⁺

PAA

COO

4000 3500 3000 2500 2000 1500 1000 500

0.1%

0.05%

0.01%

0.005%

Ca-PAA-P-CS, PAA content

Wave number(cm

^-1

)

A bsorb an ce( a. u .)

( a )

4000 3500 3000 2500 2000 1500 1000 500

0.005%

0.1%

0.05%

0.01%

CDHA-PAA-CS, PAA content

A bsorb an ce ( a. u .)

Wave number(cm

^-1

)

( b )

圖 4-34. 固定製程，不同 PAA 含量之 FTIR (a)Ca-PAA-P-CS(b)CDHA-PAA-CS

( a )

( b )

圖 4-35. 固定製程，不同 PAA 含量，未經交聯之 TGA (a)Ca-PAA-P-CS(b)CDHA-PAA-CS

100 200 300 400 500 600 700 800 900 30

100 Ca-PAA-P-CS, PAA content

We ig ht %

Temperature (

C)

0.005 % 0.01 % 0.05 % 0.10 %

100 200 300 400 500 600 700 800 900 30

100 CDHA-PAA-CS, PAA content

We ig ht %

Temperature (

C)

0.005 % 0.01 % 0.05 % 0.10 %

100 200 300 400 500 600 700 800 900

Ca-PAA-P-CS, PAA content TPP ion-crosslinking

We ig ht %

Temperature (

C)

0.005 %

100 200 300 400 500 600 700 800 900 30

CDHA-PAA-CS, PAA content TPP ion-crosslinking

We ig ht %

Temperature (

C)

0.005 %

0 1 2 3 4 5 6

Ca-PAA-P-CS, PAA content

Conc. (mg/ml)

CDHA-PAA-CS, PAA content

Conc. (mg/ml)

0.005 0.01 0.05 0.1 0.0003

0.0006 0.0009 0.0012 0.0015 0.0018

DH ( cm /h r)

PAA CONTENT %

Ca-PAA-P-CS CDHA-PAA-CS CS-PAA

圖 4-38. 固定製程，不同 PAA 含量之滲透係數

4000 3500 3000 2500 2000 1500 1000 500

CDHA-PAA-CS,PAA 0.01%

Mw 450000 Mw 2000

Ab so rb an ce ( a. u .)

Wave number(cm

^-1

)

圖 4-39. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之 FTIR

100 200 300 400 500 600 700 800 900 30

40 50 60 70 80 90

100

CDHA-PAA-CS, PAA Mw different

We ig ht %

Temperature (

C)

no PAA Mw 2000 Mw 450000

圖 4-40. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之 TGA(未交鏈)

100 200 300 400 500 600 700 800 900 40

50 60 70 80 90 100

CDHA-PAA-CS, PAA Mw different TPP ion-crosslinking

We ig ht %

Temperature (

C)

no PAA Mw 2000 MW 450000

圖 4-41. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之 TGA(已交鏈)

0 1 2 3 4 5 6 0.000

0.005 0.010 0.015 0.020

Co nc . ( m g/ m l)

Time (hr)

NO PAA PAA 2000 PAA 450000

圖 4-42. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之滲透曲線

no PAA Mw2000 Mw450000 0.0000

0.0002 0.0004 0.0006 0.0008 0.0010

0.0012 CDHA-PAA-CS

DH ( cm

/h r)

PAA Mw

圖 4-43. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之滲透係數

-100 -50 0 50 100 150 200 0

2000 4000 6000 8000 10000 12000 14000 16000

St orage M odu lu s

Temperature (

C)

NO PAA PAA 2000 PAA 450000 CS+PAA

圖 4-44. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之 DMTA-1

-100 -50 0 50 100 150 200 0.00

0.02 0.04 0.06 0.08 0.10 0.12

Ta n De lt a

Temperature (

C)

CS NO PAA PAA 2000 PAA 450000 CS+PAA

圖 4-45. 固定 CDHA/CS/PAA 製程，相同 PAA 含量，不同 PAA 分子量之 DMTA-2

在文檔中奈米級氫氧基磷灰石-幾丁聚醣複合材料 (頁 62-117)