本研究利用連續式超臨界抗溶劑法(SAS)成功製備三種顏料微粒，抗溶劑為二氧化碳，溶劑使用二甲基亞、氯與，在適當的程序變數操控下，如噴嘴直徑、顏料溶液濃度與流率、晶析溫度與壓力，可獲得最小平均粒徑為46 nm之球形red 177顏料微粒；478 nm(長軸長度)之棒狀blue 15:6顏料微粒與40 nm之球形green 36顏料微粒。
於red 177顏料之實驗結果顯示，較小毛細管噴嘴內徑、低顏料溶液濃度、在超臨界區較低的二氧化碳+DMSO混合物密度，有利於產生較微細的顆粒。藉由實驗設計法獲得red 177顏料平均粒徑與顏料溶液濃度、流率及晶析槽內流體混合物密度之應答曲面，以及實驗條件的最適化。
適中的顏料溶液濃度與壓力，以及較高的溫度能有效降低blue 15:6顏料晶體粒徑，另由MSMPR結晶槽之顆數均衡模式擬合blue 15:6 顏料微粒粒徑分佈數據，求得晶析動力參數，結果顯示其晶析機構為二次成核，且晶體之成長屬於擴散控制。
於均相區下晶析之green 36顏料平均粒徑介於40~50 nm。以CSTR結晶槽模式計算顏料溶液噴射結束時流體混合物組成，與相圖比對發現製備之顆粒形態主要受制於溶劑與抗溶劑之相行為。當晶析過程於超臨界區域與過熱蒸汽相可製得奈米級的顆粒；而汽液共存區則得明顯聚集的微米級球狀顆粒。
一系列實驗探討將1 wt% red 177顏料分散於PGMEA溶劑中，實驗結果發現在常溫常壓下採用40 wt % Hypermer PS3分散劑，可提供較佳的分散，及穩定顏料顆粒於PGMEA溶劑中；在超臨界二氧化碳參與下，添加1 wt % 親二氧化碳分散劑(Zonyl PSO-100)可進一步促進分散效果。較高的停滯溫度與壓力，及足夠的高壓停滯時間，亦有利於改善分散效果。分散體粒徑顯示與分散槽內流體相行為相關，適當的操作條件為348.2 K與20 MPa及20 min的高壓停滯時間，此條件下所製備之分散體的平均粒徑可小至148 nm，符合產業應用(100~200 nm)要求。穿透式電子顯微鏡(TEM)照片證實超臨界二氧化碳分散法可有效分散red 177顏料於PGMEA溶劑中。

Ultra-fine particles of pigment red 177, blue 15:6, and green 36 were successfully prepared with a continuous supercritical anti-solvent (SAS) apparatus by using carbon dioxide as anti-solvent and dimethyl sulfoxide (DMSO), 1-chloronaphthalene, or quinoline as solvent. By properly manipulating the process parameters, such as diameter of the injector, concentration and flow rate of pigment solution, precipitation temperature and pressure, the minimum mean sizes of the collected samples can be as small as 46 nm for spherical red 177 particles, 478 nm (the length of major axis) for rod-like blue 15:6 particles, and 40 nm for spherical green 36 particles.
For pigment red 177, the experimental results showed that smaller inside diameters of the capillary tube, lower concentrations of the pigment solution, and lower densities (in the supercritical region of carbon dioxide + DMSO mixtures) were favorable to produce smaller particles. With the aid of experimental design method, the response surface of particle size in terms of concentration of pigment solution, flow rate of pigment solution, and density of fluid mixtures in the precipitator was obtained and the optimal processing conditions were then estimated.
It was found that moderate concentrations of pigment solution, moderate pressures, and higher temperatures could effectively reduce the particle sizes of pigment blue 15:6. The precipitation kinetic parameters were determined from the particle size distribution by using the population balance theory for a mixed-suspension, mixed-product-removal (MSMPR) precipitator. The correlated results indicated that secondary nucleation was dominant in the precipitation and diffusion controlled the particle growth.
The mean particle sizes of the prepared pigment green 36 from this study were in a range of 40 nm to 50 nm as the precipitations were conducted in a homogeneous phase region. Mapping the estimated compositions of mixtures in a continuously stirred tank reactor (CSTR) precipitator at the end of pigment solution injection onto the phase diagram showed that the morphology of prepared particles was mainly governed by the phase behavior of anti-solvent + solvent mixtures. Nano-particles were obtained as the precipitation loci were manipulated within either supercritical or superheated vapor region through the SAS process, whereas micro-metric aggregated ball-like particles were produced as the precipitation loci passed by the vapor-liquid coexistence region.
A series of experiments was also made to investigate the dispersion of 1 wt % of pigment red 177 particles in propylene glycol monomethyl ether acetate (PGMEA). It was found that 40 wt % of Hypermer PS3 dispersant could provide better dispersion and could stabilize the pigment particles in PGMEA at ambient condition. With the assistance of supercritical carbon dioxide (CO2), additional 1 wt % of CO2-philic dispersant, Zonyl FSO-100, could further enhance the dispersion. Holding the mixtures in dispersion chamber at higher temperatures and pressures for a sufficient period of time was also favorable to improve the dispersion. The size of the dispersed particles appeared to have a correlation with the phase behavior of the mixtures in the dispersion chamber. The preferable operating conditions were at 348.2 K and 20 MPa, and 20 min of holding time was long enough before rapidly releasing chamber’s pressure. Under the suggested operating conditions, the mean sizes of the dispersoids could be as small as 148 nm, which met the required range of 100 nm to 200 nm in industrial applications. The TEM images have proven that the supercritical carbon dioxide-assisted dispersion method could efficiently disperse the pigment particles in PGMEA.

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