中文版 | English


Alternative Title
Name pinyin
School number
0856 材料与化工
Subject category of dissertation
0856 材料与化工
Mentor unit
Tutor units of foreign institutions
Publication Years
Submission date
Place of Publication

4D打印作为一种新兴的制造技术,将3D打印与智能响应材料相结合,使打印的样品“活”了起来。这种“活”是指打印的样品可以在适当的外部刺激下产生自发的形变,这种外界的刺激可以是温度、光照、湿度以及电磁场等。形变的行为能够进行预先编程设计,并在打印的过程中赋予样品。4D 打印所得的样品往往具有自驱动、高能量密度、高形变能力的优势,目前已经被应用于软体机器人、生物医疗、以及航空航天等领域。




Other Abstract

As an emerging manufacturing technology, 4D printing combines 3D printing technology with smart responsive materials to make printed samples "live". This "live" means the printed sample can spontaneously deform under appropriate external stimulus, such as temperature, light, humidity, and electromagnetic fields. Altered behaviors can be pre-programmed and given to the sample during the printing technology. The samples obtained by 4D printing often have the advantages of self-actuated, high energy density and high deformability. They have been applied in soft robotics, biomedicine, aerospace and other fields.

The key to 4D printing technology is the choice of printing technology and smart response material. The printing technology largely determines the sample's accuracy, complexity and designability. While the smart response material determines the response mode to external excitation and the deformation ability.

In this study, the advantages and disadvantages of various printing technologies are compared comprehensively, and the digital light processing printing technology based on photo-aggregation printing is selected. Moreover, among the smart responsive materials that have been reported, liquid crystal elastomers with strong designability and high energy density are selected as printing materials. The magnetic field is used to align the printed liquid crystal elastomer to achieve pre-programming of the deformation effect. The printing process and alignment process can be decoupled, which further improves the designability of sample.

In the experiment, the material ratio and preparation process of liquid crystal elastomer suitable for photopolymeric printing were designed according to the requirements. Based on theoretical analysis, various parts required for liquid crystal elastomer 4D printing were designed and completed. A set of liquid crystal elastomer 4D printing system with 3D programmable magnetic field orientation function was built. Then, the built system was used to test the liquid crystal elastomer 3D printing and 4D printing, the printing accuracy of the system was evaluated, and the effect of the 4D printing of the system was preliminarily verified.

Training classes
Enrollment Year
Year of Degree Awarded
References List

[1] MOMENI F, LIU X, NI J. A review of 4D printing[J]. Materials & Design, 2017, 122: 42-79.
[2] LIU K, ZJANG Y, CAO H, et al. Programmable reversible shape transformation of hydrogels based on transient structural anisotropy[J]. Advanced Materials, 2020, 32: 2001693.
[3] BOYLE B M, FRENCH T A, PEARSON R M, et al. Structural color for additive manufacturing: 3D-printed photonic crystals from block copolymers[J]. ACS Nano, 2017, 11: 3052-3058.
[4] HU Y, WANG Z, JIN D, et al. Botanical‐inspired 4D printing of hydrogel at the microscale[J]. Advanced Functional Materials, 2020, 30: 1907377.
[5] ZHANG Y, WANG Q, YI S, et al. 4D printing of magnetoactive soft materials for on-demand magnetic actuation transformation[J]. ACS Applied Materials & Interfaces, 2021, 13: 4174-4184.
[6] AMBULO C P, FORD M J, SEARLES K, et al. 4D-Printable liquid metal–liquid crystal elastomer composites[J]. ACS Applied Materials & Interfaces, 2020, 13: 12805-12813.
[7] SONG Z, REN L, ZHAO C, et al. Biomimetic nonuniform, dual-stimuli self-morphing enabled by gradient four-dimensional printing[J]. ACS Applied Materials & Interfaces, 2020, 12: 6351-6361.
[8] VAN HOA S. Development of composite springs using 4D printing method[J]. Composite Structures, 2019, 210: 869-876.
[9] TIBBITS S. 4D printing: multi‐material shape change[J]. Architectural Design, 2014, 84: 116-121.
[10] MELLY S K, LIU L, LIU Y, et al. On 4D printing as a revolutionary fabrication technique for smart structures[J]. Smart Materials and Structures, 2020, 29: 083001.
[11] KUANG X, ROACH D J, WU J, et al. Advances in 4D printing: materials and applications[J]. Advanced Functional Materials, 2019, 29: 1805290.
[12] SHIE M Y, SHEN Y F, ASTUTI S D, et al. Review of polymeric materials in 4D printing biomedical applications[J]. Polymers, 2019, 11: 1864.
[13] ZOLFAGHARIAN A, KAYNAK A, KOUZANI A. Closed-loop 4D-printed soft robots[J]. Materials & Design, 2020, 188: 108411.
[14] GUO Y, CHEN S, SUN L, et al. Degradable and Fully Recyclable Dynamic Thermoset Elastomer for 3D‐Printed Wearable Electronics[J]. Advanced Functional Materials, 2021, 31: 2009799.
[15] BEHL M, LENDLEIN A. Shape-memory polymers[J]. Materials Today, 2007, 10: 20-28.
[16] NELSON A. Engineering interactions[J]. Nature Materials, 2008, 7(7): 523-525.
[17] YAKACKI C M, SHANDAS R, SAFRANSKI D, et al. Strong, tailored, biocompatible shape‐memory polymer networks[J]. Advanced Functional Materials, 2008, 18: 2428-2435.
[18] XIE T. Tunable polymer multi-shape memory effect[J]. Nature, 2010, 464: 267-270.
[19] YU Z, ZHANG Q, LI L, et al. Highly flexible silver nanowire electrodes for shape‐memory polymer light‐emitting diodes[J]. Advanced Materials, 2011, 23: 664-668.
[20] YU K, LIU Y, LENG J. Conductive shape memory polymer composite incorporated with hybrid fillers: electrical, mechanical, and shape memory properties[J]. Journal of Intelligent Material Systems and Structures, 2011, 22: 369-379.
[21] CHOONG Y Y C, MALEKSAEEDI S, ENG H, et al. 4D printing of high-performance shape memory polymer using stereolithography[J]. Materials & Design, 2017, 126: 219-225.
[22] YU K, LIU Y, LENG J. Conductive shape memory polymer composite incorporated with hybrid fillers: electrical, mechanical, and shape memory properties[J]. Journal of Intelligent Material Systems and Structures, 2011, 22: 369-379.
[23] ZARE M, PRABHAKARAN M P, PARVIN N, et al. Thermally-induced two-way shape memory polymers: Mechanisms, structures, and applications[J]. Chemical Engineering Journal, 2019, 374: 706-720.
[24] YANG H, LEOW W R, WANG T, et al. 3D printed photo-responsive devices based on shape memory composites[J]. Advanced Materials, 2017, 29: 1701627.
[25] O’BRYAN G, WONG B M, MCELHANON J R. Stress sensing in polycaprolactone films via an embedded photochromic compound[J]. ACS Applied Materials & Interfaces, 2010, 2: 1594-1600.
[26] ZHANG Z, DALGLEISH D G, GOFF H D. Effect of pH and ionic strength on competitive protein adsorption to air/water interfaces in aqueous foams made with mixed milk proteins[J]. Colloids and Surfaces B: Biointerfaces, 2004, 34: 113-121.
[27] QIU Y, PARK K. Environment-sensitive hydrogels for drug delivery[J]. Advanced Drug Delivery Reviews, 2001, 53: 321-339.
[28] ZHANG Y S, YUE K, ALEMAN J, et al. 3D bioprinting for tissue and organ fabrication[J]. Annals of Biomedical Engineering, 2017, 45: 148-163.
[29] PEPPAS N A, HILT J Z, KHADEMHOSSEINI A, et al. Hydrogels in biology and medicine: from molecular principles to bionanotechnology[J]. Advanced Materials, 2006, 18: 1345-1360.
[30] GUAN Y, ZHANG Y. PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies[J]. Soft Matter, 2011, 7: 6375-6384.
[31] BAKARICH S E, GORKIN III R, PANHUIS M I H, et al. 4D printing with mechanically robust, thermally actuating hydrogels[J]. Macromolecular Rapid Communications, 2015, 36: 1211-1217.
[32] TER SCHIPHORST J, COLEMAN S, STUMPEL J E, et al. Molecular design of light-responsive hydrogels, for in situ generation of fast and reversible valves for microfluidic applications[J]. Chemistry of Materials, 2015, 27: 5925-5931.
[33] DEFOREST C A, ANSETH K S. Cytocompatible click-based hydrogels with dynamically tunable properties through orthogonal photoconjugation and photocleavage reactions[J]. Nature Chemistry, 2011, 3: 925-931.
[34] MCCOY C P, STOMEO F, PLUSH S E, et al. Soft matter pH sensing: From luminescent lanthanide pH switches in solution to sensing in hydrogels[J]. Chemistry of Materials, 2006, 18: 4336-4343.
[35] MODES C, WARNER M. Shape-programmable materials[J]. Physics Today, 2016, 69: 32.
[36] DA CUNHA M P, VAN THOOR E A J, DEBIJE M G, et al. Unravelling the photothermal and photomechanical contributions to actuation of azobenzene-doped liquid crystal polymers in air and water[J]. Journal of Materials Chemistry C, 2019, 7: 13502-13509.
[37] CHEN L, DONG Y, TANG C Y, et al. Development of direct-laser-printable light-powered nanocomposites[J]. ACS Applied Materials & Interfaces, 2019, 11: 19541-19553.
[38] DEL POZO M, LIU L, PILZ DA CUNHA M, et al. Direct ink writing of a light‐responsive underwater liquid crystal actuator with atypical temperature‐dependent shape changes[J]. Advanced Functional Materials, 2020, 30: 2005560.
[39] HEBNER T S, BOWMAN C N, WHITE T J. The contribution of intermolecular forces to phototropic actuation of liquid crystalline elastomers[J]. Polymer Chemistry, 2021, 12: 1581-1587.
[40] VERPAALEN R C P, DEBIJE M G, BASTIAANSEN C W M, et al. Programmable helical twisting in oriented humidity-responsive bilayer films generated by spray-coating of a chiral nematic liquid crystal[J]. Journal of Materials Chemistry A, 2018, 6: 17724-17729.
[41] FORD M J, PALANISWAMY M, AMBULO C P, et al. Size of liquid metal particles influences actuation properties of a liquid crystal elastomer composite[J]. Soft Matter, 2020, 16: 5878-5885.
[42] AMBULO C P, FORD M J, SEARLES K, et al. 4D-Printable liquid metal–liquid crystal elastomer composites[J]. ACS Applied Materials & Interfaces, 2020, 13: 12805-12813.
[43] WARE T H, MCCONNEY M E, WIE J J, et al. Voxelated liquid crystal elastomers[J]. Science, 2015, 347: 982-984.
[44] XIA Y, CEDILLO‐SERVIN G, KAMIEN R D, et al. Guided folding of nematic liquid crystal elastomer sheets into 3D via patterned 1D microchannels[J]. Advanced Materials, 2016, 28: 9637-9643.
[45] MBOW M M, MARIN P R, POURROY F. Extruded diameter dependence on temperature and velocity in the fused deposition modeling process[J]. Progress in Additive Manufacturing, 2020, 5: 139-152.
[46] LIU Y, ZHANG W, ZHANG F, et al. Microstructural design for enhanced shape memory behavior of 4D printed composites based on carbon nanotube/polylactic acid filament[J]. Composites Science and Technology, 2019, 181: 107692.
[47] BODAGHI M, DAMANPACK A R, LIAO W H. Triple shape memory polymers by 4D printing[J]. Smart Materials and Structures, 2018, 27: 065010.
[48] YANG H, LEOW W R, WANG T, et al. 3D printed photoresponsive devices based on shape memory composites[J]. Advanced Materials, 2017, 29: 1701627.
[49] WAN X, LUO L, LIU Y, et al. Direct ink writing based 4D printing of materials and their applications[J]. Advanced Science, 2020, 7: 2001000.
[50] PRIYANKA, KUMAR A. Multistimulus-responsive supramolecular hydrogels derived by in situ coating of Ag nanoparticles on 5′-CMP-capped β-FeOOH binary nanohybrids with multifunctional features and applications[J]. ACS Omega, 2020, 5: 13672-13684.
[51] WEI H, ZHANG Q, YAO Y, et al. Direct-write fabrication of 4D active shape-changing structures based on a shape memory polymer and its nanocomposite[J]. ACS Applied Materials & Interfaces, 2017, 9: 876-883.
[52] ZHU P, YANG W, WANG R, et al. 4D printing of complex structures with a fast response time to magnetic stimulus[J]. ACS Applied Materials & Interfaces, 2018, 10: 36435-36442.
[53] WAN X, ZHANG F, LIU Y, et al. CNT-based electro-responsive shape memory functionalized 3D printed nanocomposites for liquid sensors[J]. Carbon, 2019, 155: 77-87.
[54] LOW Z X, CHUA Y T, RAY B M, et al. Perspective on 3D printing of separation membranes and comparison to related unconventional fabrication techniques[J]. Journal of Membrane Science, 2017, 523: 596-613.
[55] WU J, ZHAO Z, KUANG X, et al. Reversible shape change structures by grayscale pattern 4D printing[J]. Multifunctional Materials, 2018, 1: 015002.
[56] KIM N, BHALERAO I, HAN D, et al. Improving surface roughness of additively manufactured parts using a photopolymerization model and multi-objective particle swarm optimization[J]. Applied Sciences, 2019, 9: 151.
[57] GE Q, SAKHAEI A H, LEE H, et al. Multimaterial 4D printing with tailorable shape memory polymers[J]. Scientific Reports, 2016, 6: 1-11.
[58] LOW Z X, CHUA Y T, RAY B M, et al. Perspective on 3D printing of separation membranes and comparison to related unconventional fabrication techniques[J]. Journal of Membrane Science, 2017, 523: 596-613.
[59] WU S, SERBIN J, GU M. Two-photon polymerisation for three-dimensional micro-fabrication[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2006, 181: 1-11.
[60] LIU X, WEI M, WANG Q, et al. Capillary‐force‐driven self‐assembly of 4d‐printed microstructures[J]. Advanced Materials, 2021, 33: 2100332.
[61] HE Q, WANG Z, WANG Y, et al. Electrically controlled liquid crystal elastomer–based soft tubular actuator with multimodal actuation[J]. Science Advances, 2019, 5: eaax5746.
[62] KOTIKIAN A, MCMAHAN C, DAVIDSON E C, et al. Untethered soft robotic matter with passive control of shape morphing and propulsion[J]. Science Robotics, 2019, 4: eaax7044.
[63] ZUO B, WANG M, LIN B P, et al. Photomodulated tricolor-changing artificial flowers[J]. Chemistry of Materials, 2018, 30: 8079-8088.
[64] TASMIM S, YOUSUF Z, RAHMAN F S, et al. Liquid crystal elastomer based dynamic device for urethral support: Potential treatment for stress urinary incontinence[J]. Biomaterials, 2023, 292: 121912.
[65] KÜPFER J, FINKELMANN H. Nematic liquid single crystal elastomers[J]. Die Makromolekulare Chemie, Rapid Communications, 1991, 12: 717-726.
[66] YAKACKI C M, SAED M, NAIR D P, et al. Tailorable and programmable liquid-crystalline elastomers using a two-stage thiol–acrylate reaction[J]. Rsc Advances, 2015, 5: 18997-19001.
[67] AMBULO C P, BURROUGHS J J, BOOTHBY J M, et al. Four-dimensional printing of liquid crystal elastomers[J]. ACS Applied Materials & Interfaces, 2017, 9: 37332-37339.
[68] LI S, BAI H, LIU Z, et al. Digital light processing of liquid crystal elastomers for self-sensing artificial muscles[J]. Science Advances, 2021, 7: eabg3677.
[69] DE GENNES P G, PROST J. The physics of liquid crystals[M]. Oxford University Press, 1993.
[70] GAROFF S, MEYER R B. Electroclinic effect at the A− C phase change in a chiral smectic liquid crystal[J]. Physical Review A, 1979, 19: 338.
[71] ZHAO J, ZHANG L, HU J. Varied Alignment Methods and Versatile Actuations for Liquid Crystal Elastomers: A Review[J]. Advanced Intelligent Systems, 2022, 4: 2100065.
[72] LIN F H, HO C Y, LEE J Y. The electro-optical characteristics of liquid crystal device in multi-component liquid crystal mixture system with non-contact photo-induced vertical alignment mode[J]. Optical Materials, 2012, 34: 1181-1194.
[73] TABRIZI M, WARE T H, SHANKAR M R. Voxelated molecular patterning in three-dimensional freeforms[J]. ACS Applied Materials & Interfaces, 2019, 11: 28236-28245.
[74] YAO Y, WATERS J T, SHNEIDMAN A V, et al. Multiresponsive polymeric microstructures with encoded predetermined and self-regulated deformability[J]. Proceedings of the National Academy of Sciences, 2018, 115(51): 12950-12955.

Academic Degree Assessment Sub committee
Domestic book classification number
Data Source
Document TypeThesis
DepartmentDepartment of Electrical and Electronic Engineering
Recommended Citation
GB/T 7714
杨曦. 可编程取向液晶弹性体的4D打印[D]. 深圳. 南方科技大学,2023.
Files in This Item:
File Name/Size DocType Version Access License
12132155-杨曦-电子与电气工程系(7352KB) Restricted Access--Fulltext Requests
Related Services
Fulltext link
Recommend this item
Usage statistics
Export to Endnote
Export to Excel
Export to Csv
Altmetrics Score
Google Scholar
Similar articles in Google Scholar
[杨曦]'s Articles
Baidu Scholar
Similar articles in Baidu Scholar
[杨曦]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[杨曦]'s Articles
Terms of Use
No data!
Social Bookmark/Share
No comment.

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.