Construction of Ternary Phase Diagram of Polycaprolactone/Dimethyl Sulfoxide/Water System for Immersion Precipitation 3D Printing

GAO Ang; YIN Cun-hong; ZHANG Jun-fei; ZHOU Huan; GUO Rui; LIU Xi-xia

doi:10.14028/j.cnki.1003-3726.2025.24.398

您当前的位置：

首页 >

文章列表页 >

Construction of Ternary Phase Diagram of Polycaprolactone/Dimethyl Sulfoxide/Water System for Immersion Precipitation 3D Printing

更新时间：2025-04-29

- Construction of Ternary Phase Diagram of Polycaprolactone/Dimethyl Sulfoxide/Water System for Immersion Precipitation 3D Printing
- Polymer Bulletin Vol. 38, Issue 5, Pages: 790-800(2025)
- 作者机构：
  
  贵州大学机械工程学院，贵阳 550025
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.24.398
  CLC：
- Received：31 December 2024，
  
  Accepted：2025-01-27，
  
  Published Online：17 March 2025，
  
  Published：20 May 2025
- 稿件说明：
移动端阅览
高昂, 尹存宏, 张俊飞, 周欢, 郭蕊, 刘西霞. 面向浸没沉淀3D打印的聚己内酯/二甲基亚砜/水体系三元相图构建. 高分子通报, 2025, 38(5), 790–800.

Gao, A.; Yi, C. H.; Zhang, J. F.; Zhou, H.; Guo, R.; Liu, X. X. Construction of ternary phase diagram of polycaprolactone/ dimethyl sulfoxide/ water system for immersion precipitation 3D printing. Polym. Bull. (in Chinese), 2025, 38(5), 790–800.
高昂, 尹存宏, 张俊飞, 周欢, 郭蕊, 刘西霞. 面向浸没沉淀3D打印的聚己内酯/二甲基亚砜/水体系三元相图构建. 高分子通报, 2025, 38(5), 790–800. DOI： 10.14028/j.cnki.1003-3726.2025.24.398.

Gao, A.; Yi, C. H.; Zhang, J. F.; Zhou, H.; Guo, R.; Liu, X. X. Construction of ternary phase diagram of polycaprolactone/ dimethyl sulfoxide/ water system for immersion precipitation 3D printing. Polym. Bull. (in Chinese), 2025, 38(5), 790–800. DOI： 10.14028/j.cnki.1003-3726.2025.24.398.

摘要

浸没沉淀3D打印技术能够实现复杂多孔结构的成形，广泛应用于生物医学领域，特别是在组织工程支架的制造中。该技术尤其适用于人体植入性聚己内酯

(PCL)支架的制备。制备多孔PCL结构的关键在于构建三元相图，通过分析浸没沉淀3D打印过程中的相分离成形机理，指导多孔结构形态的调控。但是，对于聚己内酯/二甲基亚砜/水(PCL/DMSO/H

O)三元体系的相分离成形机理的研究较少。因此，本研究旨在通过理论计算及实验测定，构建该体系的三元相图。基于Flory-Huggins理论，结合二元相互作用参数计算并绘制了双节线和旋节线。通过采用浊点滴定法获得浊点数据后绘制双节线，并与上述理论计算结果进行对比，验证了三元相图的正确性。基于构建的三元相图研究了浸没沉淀3D打印过程中的相分离成形机理，分析了不同PCL浓度对打印细丝微观形态的影响。结果表明，理论计算的双节线与实验测定的双节线吻合较好，随着PCL浓度的升高，细丝横截面微观形态变得愈加致密，孔隙率越来越小。

Abstract

Immersion precipitation 3D printing technology has been widely used in the biomedical field

owing to its facilitation of porous structure formation. For example

it is used in the manufacture of biodegradable polycaprolactone (PCL) scaffolds for human implants. The construction of a ternary phase diagram is key to preparing porous PCL structures and is also used to analyze the mechanisms of phase separation during the immersion precipitation 3D printing process

thereby guiding the regulation of the porous structural morphology. However

the phase separation mechanism of the polycaprolactone/dimethyl sulfoxide/water (PCL/DMSO/H

O) ternary system has rarely been studied. Therefore

this study aimed to construct a ternary phase diagram of the PCL/DMSO/H

O system through theoretical calculations and experimental measurements. Based on the Flory-Huggins theory and combined with the binary interaction parameter

the binodal and spinodal curves of the PCL/DMSO/H

O system were calculated and plotted. In addition

the binodal curve was plotted based on the cloud point data obtained using the cloud point titration method and compared with the theoretical calculations to validate the accuracy of the ternary phase diagram. Using the constructed ternary phase diagram

the formation mechanism of phase separation during the immersion precipitation 3D printing process was investigated

and the influence of different PCL concentrations on the microscopic morphology of the printed filaments was analyzed. The results indicate that the binodal curve derived from th

e theoretical calculations closely matches that obtained experimentally. As the PCL concentration increases

the microscopic morphology of the filament cross-section becomes denser

and the porosity decreases.

关键词

Keywords

references

Dwivedi, R. ; Kumar, S. ; Pandey, R. ; Mahajan, A. ; Nandana, D. ; Katti, D. S. ; Mehrotra, D . Polycapro-lactone as biomaterial for bone scaffolds: review of literature . J. Oral Biol. Craniofac. Res. , 2020 , 10 ( 1 ), 381 – 388 .

Woodruff, M. A. ; Hutmacher, D. W . The return of a forgo-tten polymer: polycaprolactone in the 21 st century . Prog. Polym. Sci. , 2010 , 35 ( 10 ), 1217 – 1256 .

Ghaedamini, S. ; Karbasi, S. ; Hashemibeni, B. ; Honarvar, A. ; Rabiei, A . PCL/Agarose 3D-printed scaffold for tissue engineering applications: fabrication, characterization, and cellular activities . Res. Pharm. Sci. , 2023 , 18 ( 5 ), 566 – 579 .

Blázquez-Blázquez, E. ; Pérez, E. ; Lorenzo, V. ; Cerrada, M. L . Crystalline characteristics and their influen ce in the mechanical performance in poly( ε -caprolactone)/high density polyethylene blends . Polymers , 2019 , 11 ( 11 ), 1874 .

Moore, M. J. ; Tan, R. P. ; Yang, N. J. ; Rnjak-Kovacina, J. ; Wise, S. G . Bioengineering artificial blood vessels from natural materials . Trends Biotechnol. , 2022 , 40 ( 6 ), 693 – 707 .

Deng, X. X. ; Qasim, M. ; Ali, A . Engineering and polymeric composition of drug-eluting suture: a review . J. Biomed. Mater. Res. Part A , 2021 , 109 ( 10 ), 2065 – 2081 .

Mahmoud Salehi, A. O. ; Heidari Keshel, S. ; Sefat, F. ; Tayebi, L . Use of polycaprolactone in corneal tissue engineering: a review . Mater. Today Commun. , 2021 , 27 , 102402 .

Arif, U. ; Haider, S. ; Haider, A. ; Khan, N. ; Alghyamah, A. A. ; Jamila, N. ; Khan, M. I. ; Almasry, W. A. ; Kang, I. K . Biocompatible polymers and their potential biomedical applications: a review . Curr. Pharm. Des. , 2019 , 25 ( 34 ), 3608 – 3619 .

Gharibshahian, M. ; Salehi, M. ; Beheshtizadeh, N. ; Kamalabadi-Farahani, M. ; Atashi, A. ; Nourbakhsh, M. S. ; Alizadeh, M . Recent advances on 3D-printed PCL-based composite scaffolds for bone tissue engineering . Front. Bioeng. Biotechnol. , 2023 , 11 , 1168504 .

Dong, Z. Q. ; Cui, H. J. ; Zhang, H. D. ; Wang, F. ; Zhan, X. ; Mayer, F. ; Nestler, B. ; Wegener, M. ; Levkin, P. A . 3D printing of inherent ly nanoporous polymers via polymerization-induced phase separation . Nat. Commun. , 2021 , 12 ( 1 ), 247 .

Karyappa, R. ; Ohno, A. ; Hashimoto, M . Immersion precipitation 3D printing (ip3DP) . Mater. Horiz. , 2019 , 6 ( 9 ), 1834 – 1844 .

Cidonio, G. ; Costantini, M. ; Pierini, F. ; Scognamiglio, C. ; Agarwal, T. ; Barbetta, A . 3D printing of biphasic inks: beyond single-scale architectural control . J. Mater. Chem. C , 2021 , 9 ( 37 ), 12489 – 12508 .

Ju, G. N. ; Zhou, L. ; Zheng, X. F. ; Zhang, H. Q. ; Su, C. H. ; Chen, B. Y. ; Shen, H. W. ; Zhao, X. Y . Robust superhydrophobic micro-nanostructures design based on polarity-opposite amorphous polymers . Compos. Commun. , 2024 , 51 , 102032 .

Mironov, A. V. ; Mironova, O. A. ; Syachina, M. A. ; Popov, V. K . 3D printing of polylactic-co-glycolic acid fiber scaffolds using an antisolvent phase separation process . Polymer , 2019 , 182 , 121845 .

Hu, X. ; Yang, Z. ; Kang, S. ; Jiang, M. ; Zhou, Z. ; Gou, J. ; Hui, D. ; He, J . Cellulose hydrogel skeleton by extrusion 3D printing of solution . Nanotechnol. Rev. , 2020 , 9 ( 1 ), 345 – 353 .

Bobrin, V. A. ; Yao, Y. ; Shi, X. B. ; Xiu, Y. ; Zhang, J. ; Corrigan, N. ; Boyer, C . Nano- to macro-scale control of 3D printed materials via polymerization induced microphase separation . Nat. Commun. , 2022 , 13 ( 1 ), 3577 .

Zhang, R. R. ; Deng, L. L. ; Guo, J. H. ; Yang, H. Y. ; Zhang, L. N. ; Cao, X. D. ; Yu, A. X. ; Duan, B . Solvent mediating the in situ self-assembly of polysaccharides for 3D printing biomimetic tissue scaffolds . ACS Nano , 2021 , 15 ( 11 ), 17790 – 17803 .

Liu, Y. K. ; Wang, L. L. ; Liu, Y. J. ; Zhang, F. H. ; Leng, J. S . Recent progress in shape memory polymer composites: Driving modes, forming technologies, and applications . Compos. Commun. , 2024 , 51 , 102062 .

Zhang, F. Y. ; Ma, Y. ; Liao, J. S. ; Breedveld, V. ; Lively, R. P . Solution-based 3D printing of polymers of intrinsic microporosity . Macromol. Rapid Commun. , 2018 , 39 ( 13 ), 1800274 .

Ogbuoji, E. A. ; Stephens, L. ; Haycraft, A. ; Wooldridge, E. ; Escobar, I. C . Non-solvent induced phase separation (NIPS) for fabricating high filtration efficiency (FE) polymeric membranes for face mask and air filtration applications . Membranes , 2022 , 12 ( 7 ), 637 .

Sole-Gras, M. ; Ren, B. ; Ryder, B. J. ; Ge, J. Q. ; Huang, J. G. ; Chai, W. X. ; Yin, J. ; Fuchs, G. E. ; Wang, G. A. ; Jiang, X. P. ; Huang, Y . Vapor-induced phase-separation-enabled versatile direct ink writing . Nat. Commun. , 2024 , 15 ( 1 ), 3058 .

董杰 , 尹朝清 , 谭文军 , 张清华 . PI/NMP/H 2 O三元体系相行为与纤维成形研究 . 合成纤维工业 , 2014 , 37 ( 6 ), 1 – 5 .

Wang, B. ; Yao, J. Y. ; Wang, H. Y. ; Wang, M. Q . Cons-truction of a ternary system: a strategy for the rapid formation of porous poly(lactic acid) fibers . RSC Adv. , 2022 , 12 ( 11 ), 6476 – 6483 .

Luo, C. J. ; Stride, E. ; Edirisinghe, M . Mapping the influence of solubility and dielectric constant on electrospinning polycaprolactone solutions . Macromolecules , 2012 , 45 ( 11 ), 4669 – 4680 .

Dong, X. B. ; Lu, D. ; Harris, T. A. L. ; Escobar, I. C . Polymers and solvents used in membrane fabrication: a review focusing on sustainable membrane development . Membranes , 2021 , 11 ( 5 ), 309 .

Katsogiannis, K. A. G. ; Vladisavljević, G. T. ; Georgiadou, S . Porous electrospun polycaprolactone (PCL) fibres by phase separation . Eur. Polym. J. , 2015 , 69 , 284 – 295 .

Chen, Y. Y. ; Xiong, P. ; Xiao, S. S. ; Zhu, Y. Z. ; Peng, S. S. ; He, G. H . Ion conductive mechanisms and redox flow battery applications of polybenzimidazole-based membranes . Energy Storage Mater. , 2022 , 45 , 595 – 617 .

刘美惠 , 沈惠玲 , 王双双 . 聚氨酯- N , N -二甲基甲酰胺–非溶剂三元相行为研究 . 天津科技大学学报 , 2018 , 33 ( 5 ), 51 – 56 .

Xie, W. C. ; Li, T. ; Chen, C. ; Wu, H. B. ; Liang, S. M. ; Chang, H. Q. ; Liu, B. C. ; Drioli, E. ; Wang, Q. Y. ; Crittenden, J. C . Using the green solvent dimethyl sulfoxide to replace traditional solvents partly and fabricating PVC/PVC- g -PEGMA blended ultrafiltration membranes with high permeability and rejection . Ind. Eng. Chem. Res. , 2019 , 58 ( 16 ), 6413 – 6423 .

Müller, K. ; Zollfrank, C . Ionic liquid aided solution-precipitation method to prepare polymer blends from cellulose with polyesters or polyamide . Eur. Polym. J. , 2020 , 133 , 109743 .

Othman, R. ; Mun, G. K. ; Sinnathamby, N. ; Gopinanth, S. C. B. ; Ekanem, E . Compatible organic and natural solvent mixture of synthesising biodegradable polymeric nanoparticles . J. Phys.: Conf. Ser. , 2021 , 2080 ( 1 ), 012028 .

André, A. D. ; Teixeira, A. M. ; Martins, P . Influence of DMSO non-toxic solvent on the mechanical and chemical properties of a PVDF thin film . Appl. Sci. , 2024 , 14 ( 8 ), 3356 .

Denolf, R. ; Hogie, J. ; Figueira, F. L. ; Mertens, I. ; de Somer, T. ; D’Hooge, D. R. ; Hoogenboom, R. ; de Meester, S . Constructing and validating ternary phase diagrams as basis for polymer dissolution recycling . J. Mol. Liq. , 2023 , 387 , 122630 .

张银锋 , 陈世昌 , 吕汪洋 , 陈文兴 . 聚酰亚胺- N -甲基吡咯烷酮-水三元相行为研究 . 现代纺织技术 , 2013 , 21 ( 2 ), 1 – 4 .

Yeow, M. L. ; Liu, Y. T. ; Li, K . Isothermal phase diag-rams and phase-inversion behavior of poly(vinylidene fluoride)/solvents/additives/water systems . J. Appl. Polym. Sci. , 2003 , 90 ( 8 ), 2150 – 2155 .

Tan, L. J. ; Pan, D. ; Pan, N . Thermodynamic study of a water-dimethylformamide-polyacrylonitrile ternary system . J. Appl. Polym. Sci. , 2008 , 110 ( 6 ), 3439 – 3447 .

Law, S. J. ; Mukhopadhyay, S. K . The construction of a phase diagram for a ternary system used for the wet spinning of acrylic fibers based on a linearized cloudpoint curve correlation . J. Appl. Polym. Sci. , 1997 , 65 ( 11 ), 2131 – 2139 .

潘凤娇 , 周乐 , 曾少娟 , 刘雪 , 刘艳荣 , 聂毅 . 离子液体/羊毛纤维/凝固剂三元相图的构建 . 过程工程学报 , 2021 , 21 ( 2 ), 160 – 166 .

Mohsenpour, S. ; Esmaeilzadeh, F. ; Safekordi, A. ; Tavakolmoghadam, M. ; Rekabdar, F. ; Hemmati, M . The role of thermodynamic parameter on membrane morphology based on phase diagram . J. Mol. Liq. , 2016 , 224 , 776 – 785 .

Zhang, J. ; Zhang, Y. W. ; Zhao, J. X . Thermodynamic study of non-solvent/dimethyl sulfoxide/polyacrylonitrile ternary systems: effects of the non-solvent species . Polym. Bull. , 2011 , 67 ( 6 ), 1073 – 1089 .

Romay, M. ; Diban, N. ; Urtiaga, A . Thermodynamic mode-ling and validation of the temperature influence in ternary phase polymer systems . Polymers , 2021 , 13 ( 5 ), 678 .

Idris, A. ; Man, Z. ; Maulud, A. S. ; Khan, M. S . Effects of phase separation behavior on morphology and performance of polycarbonate membranes . Membranes , 2017 , 7 ( 2 ), 21 .

Boom, R. M. ; van den Boomgaard, T. ; van den Berg, J. W. A. ; Smolders, C. A . Linearized cloudpoint curve correlation for ternary systems consisting of one polymer, one solvent and one non-solvent . Polymer , 1993 , 34 ( 11 ), 2348 – 2356 .

Liu, X. X. ; Lu, X. C. ; Wang, Z. H. ; Yang, X. H. ; Dai, G. L. ; Yin, J. ; Huang, Y . Effect of bore fluid composition on poly(lactic- co -glycolic acid) hollow fiber membranes fabricated by dry-jet wet spinning . J. Membr. Sci. , 2021 , 640 , 119784 .

魏无际 , 俞强 , 崔益华 . 高分子化学与物理基础 . 第2版 . 北京 : 化学工业出版社 , 2011 .

Yilmaz, L. ; McHugh, A. J . Analysis of nonsolvent-solvent-polymer phase diagrams and their relevance to membrane formation modeling . J. Appl. Polym. Sci. , 1986 , 31 ( 4 ), 997 – 1018 .

曾小梅 . 聚丙烯腈(PAN)基碳纤维原丝凝固成形机理的研究 . 博士学位论文 , 上海 : 东华大学 , 2008 .

刘美惠 , 沈惠玲 . 聚氨酯- N , N -二甲基甲酰胺-水体系的相变行为 . 塑料 , 2018 , 47 ( 5 ), 108 – 112 .

向红兵 , 黄忠 , 诸静 , 陈蕾 , 于俊荣 , 胡祖明 . P84共聚聚酰亚胺/NMP/乙二醇体系三元相图的计算 . 东华大学学报(自然科学版) , 2011 , 37 ( 3 ), 293 – 298 .

蒋冠森 . 以1-丁基-3-甲基咪唑氯酸盐为溶剂的纤维素纤维纺丝成形研究 . 博士学位论文 , 上海 : 东华大学 , 2012 .

Shimizu, H. ; Kawakami, H. ; Nagaoka, S . Membrane formation mechanism and permeation properties of a novel porous polyimide membrane . Polym. Adv. Technol. , 2002 , 13 ( 5 ), 370 – 380 .

Views

104

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

A Derivation Method of

χ^{c}

and

ϕ^{c}

Teaching of Phase Separation of Polymer Solution by Number-shape Combination

Discussion on Mixing Free Energy-composition Curve and Phase Diagram in Polymer Physics

Phase Structure Evolution and Film Properties of PEGDA/PDMS Driven by Electric Field

Related Author

LIU Xi-xia

LU Da-wei

XU Bo-jun

GUO Fu-quan

FAN Ji-chang

QIAO Yu-hui

HU Peng-fei

LIU Ji-yan

Related Institution

College of Materials Science and Engineering, Beijing University of Chemical Technology

Department of Material Science and Engineering, Luoyang Institute of Science and Technology

Key Laboratory of Optoelectronic Chemical Materials and Devices (Ministry of Education), School of Optoelec-tronic Materials & Technology, Jianghan University

College of Ecology and Resources Engineering, Fujian Provincial Bamboo Engineering Technology Research Center, Fujian Key Laboratory of Eco-Industrial Green Technology, Wuyi University

School of Chemistry and Chemical Engineering,Hefei University of Technology

⁰