本研究以不同分子量之聚苯乙烯硫醇化合物(thiol terminated polystyrene, PSSH)對奈米金粒子(Au) 表面進行改質，再將改質後之金粒子與團聯式共聚合物poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP)製備成奈米複合薄膜。
由TEM及TGA分析發現，改質後之粒子粒徑隨著PSSH分子量之增加而上升。在複合物中，金粒子的添加使得PS-b-P2VP之Tg上升，但是摻合高濃度且較大粒徑之粒子時，由於粒子粒徑較大，複合材料所能容納之粒子減少，此時奈米粒子產生聚集，形成巨觀相分離，對複合材料之Tg不造成影響。
在薄膜中添加低粒子濃度時，摻合大粒徑與小粒徑之粒子，皆能夠得到具有規則性之薄膜表面結構，但是摻合使用大分子量PSSH所改質的粒子，且在較短的annealing時間，薄膜表面會出現垂直層狀結構；摻合小粒子，薄膜表面形態為平行柱狀。隨著annealing時間增加，薄膜表面出現許多金粒子，此為在annealing的過程中，部份金粒子會移動至空氣/共聚物界面，增加系統的熵。在高粒子濃度時，摻合大粒徑粒子之複合薄膜，經過長時間的annealing，表面會產生粒子聚集的巨觀相分離。金粒子的濃度和表面所改質的PSSH長度改變時，除了改變薄膜表面形態，也會改變共聚物溼潤於基材的能力。結果顯示由於奈米粒子會移動至高分子/基材的界面，因此粒子濃度的提升以及PSSH長度的增加，皆能夠增加共聚物潤溼於基材的能力。
將PS-b-P2VP/PSSH-Au摻合hPS，高分子鏈的移動速率大於未添加hPS時的移動速率。摻合低濃度的小粒徑之Au粒子，薄膜表面可形成垂直柱狀的結構，這是由於PS-b-P2VP中PS區塊的體積分率增加，Au粒子的添加降低團聯式共聚物之分離程度，且共聚物/基材表面有足夠的氯仿，降低分子鏈段與界面之間的能量差距形成中性界面。增加金粒子及hPS濃度，皆無法於薄膜表面得到垂直柱狀。這是由於金粒子和hPS濃度的增加，會導致團聯式共聚合物之分離程度下降，因此無法形成有序之結構。從OM圖發現hPS的加入，與添加改質後之金粒子相同，亦有效地增加共聚物溼潤於基材的能力。

Thin films of nanocomposites composed of polystyrene-b-poly(2 vinylpyridine) (PS-b-P2VP) and different molecular weights of thiol-terminated polystyrene (PSSH) tethered Au nanoparticles were investigated. It was obtained that the particle size increases with increasing molecular weight of PSSH. The Tg of PS-b-P2VP/ PSSH-Au nanocomposites shows a strong function of particle concentration and particle size and the addition of Au particles increases the Tg of block copolymer. However when PS-b-P2VP was mixed with large particles at high loading, macrophase separation of particles from the preferred domains of PS-b-P2VP occurs, causing the nearly identical Tg of composite to the neat copolymer.
We further investigated the effect of particles on the morphology of composite thin films during neutral solvent annealing. At low particle loading with short annealing time, a well ordered structure was obtained regardless of the size of particles. For large particles, composite thin film developed to a lamellar structure perpendicular to the substrate. In contrast, composite thin film with the addition of small particles formed a parallel cylinder structure. During annealing, particles tend to move the air/ polymer interface to increase the conformational entropy of the system. At high particle loading, composite thin film with large particles formed macrophase separation. The PS-b-P2VP/particle composite thins not only affect the surface morphology but also change the wetting ability of thin films. Results showed the use of the high particle loading and the high molecular weight of PSSH significantly improves the wetting of the thin films. This behavior is due to the Au particles diffusion to the interface between poymer and substrate.
The surface morphology of PS-b-P2VP/PSSH-Au/hPS composite thin films during chloroform vapor annealing was also studied. The incorporate of hPS into the nanocomposite enhances the diffusion of the system. The composite thin film with small Au particles and low concentration exhibit a perpendicularly cylindrical structure. This structure is due to the sequestering of hPS in the PS domains, that casuses an increase in the effective volume fraction of the PS domains, resulting in the order to order transition. In addition, the addition of Au particles and hPS reduces the degree of segregation. This behavior and the chloroform vapor treatment reduce the energy difference between the polymer and subrate that induced the change in orientation of the ordered domains. The perpendicularly cylindrical structure disappeared with slightly increasing Au particle and hPS concerntration. This is attributed to the significantly decreasing the degree of segregation. OM results revealed that the wetting ability was enhances with the addition of hPS. This phenomenon is consistent with the composite manipulated with Au nanoparticles.

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