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MATERIALS LETTERS · 2019 · IF 3.019

A facile photo-polymerization method for reconfigurable shape memory polymers

Beibei Hao,Yongcheng Li,Xuan Xiao,Wei Dai,Heng Chen,Shaojun Chen

This paper reports a facile preparation of re-configurable shape memory polymer (SMP) with photo-polymerization method. A novel SMP was successfully prepared from the photo-curable resin synthesized with hexamethylenediacrylate and 1,6-Hexanedithiol. The photo-cured polymer forms semi-crystalline reversible phase and chemically cross-linked netpoints. They show good thermal-induced shape memory effect with about 92% shape fixity and about 99% shape recovery. Moreover, the photo-cured SMPs have excellent thermal-induced shape reconfiguration properties. A new permanent shape could be reconfigured easily by heat treatment at 130 °C. It is thus proposed that the photo-curable resin could be used as “printing ink” for SMP 4D printing applications.

研究领域: 材料科学 · 高分子化学
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POLYMER · 2018 · IF 3.483

Facile water-assisted permanent shape reconfiguration of zwitterionic polyurethanes

Haitao Zhuo,Hao Wen,Guanlun Liu,Heng Chen,Shaojun Chen

There have been great developments in shape memory polymers in recent years. However, the permanent shape was usually predetermined and could not be changed during the shape memory process. This work reports a facile method for permanent shape reconfiguration of shape memory polymers using a water-soaking treatment. The impact of water molecules on the structure, morphology, and properties of zwitterionic polyurethanes (ZPUs) was carefully investigated. FT-IR, DSC , TGA , and DMA analysis revealed that polymer chains of ZPU can be easily activated by absorbing water molecules and was solidified again by removal of water molecules. Direct water-soaking treatment can eliminate previous shape recovery capability and then be used to reconfigure a new permanent shape for a new thermally induced shape memory process. Thus, this work provides an alternative approach for manufacturing complicated devices at room temperature and for easily regulating the thermally induced shape memory effect.

研究领域: 材料科学 · 高分子化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 136 ·期 44 ·48177 · IF 2.188

3D printing of shape memory poly(d,l-lactide-co-trimethylene carbonate) by direct ink writing for shape-changing structures

Xue Wan,Hongqiu Wei,Fenghua Zhang,Yanju Liu,Jinsong Leng

Four-dimensional (4D) printing of shape memory materials has attracted increasing interests for personalized structures. In this study, a biocompatible poly( d , l -lactide- co -trimethylene carbonate) (PLMC) is utilized to fabricate 4D shape-changing structures with customized geometries through direct ink writing. The printed objects show shape transformations at different dimensions under thermal programming. The influence of the printing parameters on the properties including rheological, solvent evaporation, and static mechanical behavior are systematically investigated. A printing map is further depicted to achieve high-quality printing with high viscous ink flowed from micronozzle to construct various structures. The printed structures in one-dimensional, two-dimensional, and three-dimensional (3D) exhibit shape-changing behavior with fast response around body temperature. The fast responsive time shows potential in the field of surgical suture (4 s), nonwoven fabric (3 s), and self-expandable stent (35 s). The feasibility of 3D printing of PLMC opens the way for applications in shape-changing devices with small diameter. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 48177.

CAS / MDL: 75-09-2
研究领域: 生物医学工程 · 材料科学
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ADVANCED FUNCTIONAL MATERIALS · 2017 ·Vol. 27 ·期 33 ·1701962 · IF 12.124

Surface Patterning of Hydrogels for Programmable and Complex Shape Deformations by Ion Inkjet Printing

Xin Peng,Tianqi Liu,Qin Zhang,Cong Shang,Qing-Wen Bai,Huiliang Wang

Convenient patterning and precisely programmable shape deformations are crucial for the practical applications of shape deformable hydrogels. Here, a facile and versatile computer-assisted ion inkjet printing technique is described that enables the direct printing of batched, very complicated patterns, especially those with well-defined, programmable variation in cross-linking densities, on one or both surfaces of a large-sized hydrogel sample. A mechanically strong hydrogel containing poly(sodium acrylate) is first prepared, and then digital patterns are printed onto the hydrogel surfaces by using a commercial inkjet printer and an aqueous ferric solution. The complexation between the polyelectrolyte and ferric ions increases the cross-linking density of the printed regions, and hence the gel sample can undergo shape deformation upon swelling/deswelling. The deformation rates and degrees of the hydrogels can be conveniently adjusted by changing the printing times or the different/gradient grayscale distribution of designed patterns. By printing appropriate patterns on one or both surfaces of the hydrogel sheets, many complex 3D shapes are obtained from shape deformations upon swelling/deswelling, such as cylindrical shell and forsythia flower (patterns on one surface), ding (patterns on both surfaces), blooming flower (different/gradient grayscale distributive patterns on one surface), and non-Euclidean plates (different/gradient grayscale distributive patterns on both surfaces).

研究领域: 材料科学 · 生物工程
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RSC Advances · 2015 ·Vol. 5 ·期 55 ·44435-44446 · IF 3.84

A shape memory copolymer based on 2-(dimethylamino)ethyl methacrylate and methyl allyl polyethenoxy ether for potential biological applications

Yangyang Chen,Funian Mo,Shaojun Chen,Yan Yang,Shiguo Chen,Haitao Zhuo,Jianhong Liu

This study reports a novel shape memory copolymer synthesized with 2-(dimethylamino)-ethyl-methacrylate (DMAEMA) and methyl-allyl-polyethenoxy-ether (TPEG) for potential biological applications. In the DMAEMA–TPEG copolymers, TPEG segments form a semi-crystalline phase that serves as the reversible phase, while DMAEMA segments form an amorphous phase containing physical interactive networks that serve as the hard phase. As the TPEG content increases, the crystallinity and the rate of crystallization increase, and the TPEG phase changes from dispersed small spherical crystals to a continuous crystalline phase. Additionally, good crystallinity of the TPEG phase endows the copolymers with good shape fixity, whereas the shape recovery decreases as the TPEG content decreases. DMAEMA–TPEG copolymers also exhibit the multi-shape memory effect with a good triple-shape memory effect. Finally, the investigation of the water contact angle illustrates that all DMAEMA–TPEG copolymers have good hydrophilicity. Thus, it is proposed that DMAEMA–TPEG copolymers might have great potential for biological applications.

CAS / MDL: 7727-54-0 2867-47-2
研究领域: 材料科学 · 生物医学工程 · 高分子化学
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ADVANCES IN POLYMER TECHNOLOGY · 2016 ·Vol. 37 ·期 3 ·869-877 · IF 1.114

Cellulose Acetate for Shape Memory Polymer: Natural, Simple, High Performance, and Recyclable

Yongkang Bai,Yuejun Liu,Qihua Wang

In this work, a bio-shape memory polymer (SMP) with high performance is prepared by using cellulose acetate (CA) as raw material. The materials exhibit good mechanical properties with tensile strength and elongation at break over 46 MPa and 115%, respectively. With hydrogen bond interaction as physically cross-linked points, the materials also present excellent dual-shape memory properties with shape fixation and shape recovery ratio of about 99% and 96%, respectively. Moreover, the materials show good triple-shape memory effect. The recyclability of the materials is also investigated and the results show that the reclaimed samples still hold high mechanical and shape memory properties. With the intrinsic biocompatibility and biodegradation of CA, the materials could be an attractive candidate for applications in smart biomedical devices. Furthermore, the usage of CA as SMP could expand the view of preparing bio-SMP in future.

研究领域: 材料科学 · 生物医学工程
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POLYMER COMPOSITES · 2014 ·Vol. 36 ·期 3 ·439-444 · IF 1.455

Electroactive two-way shape memory polymer laminates

Shaojun Chen,Shixin Yang,Ziyu Li,Shiwei Xu,Hongming Yuan,Shiguo Chen,Zhaochuan Ge

Two-way shape changing polymers are attractive in recent years. In this short communication, carbon black (CB)/shape memory polyurethane (SMPU)-elastic polyurethane (EPU) laminated composite is prepared and electro-active two-way shape changing behavior is reported for the first time. First, the CB/SMPU composite demonstrates good electro-active shape recovery due to good electricity conduction. When the CB/SMPU composite film is elongated and form polymer laminates by combining with EPU substrate, the resulted CB/SMPU-EPU polymer laminate shows electro-active two-way shape changing behavior, e.g., bending by applying electric current, and reverse bending upon cooling without electric current. POLYM. COMPOS. 36:439–444, 2015. © 2014 Society of Plastics Engineers

CAS / MDL: 68-12-2
研究领域: 材料科学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Water-responsive shape memory PLLA via incorporating PCL-(PMVS-s-PAA)-PCL-PTMG-PCL-(PMVS-s-PAA)-PCL

Yajun Ren,ZhuanZhuan Zhang,Wenlong Xia,Qifeng Zhou,Xiaofeng Song

Poly(L-lactide) (PLLA) was one of the most well-known biodegradable polyesters. Although its thermo-responsive shape memory (SM) function has been studied by proper program, high transformation temperature is not suitable in some biomedical applications. Water-responsive SM polymer is an alternative choice and exhibits great potential because it is harmless to the cells and tissues of organisms. In the work, a novel PCL-(PMVS- s -PAA)-PCL-PTMG-PCL-(PMVS- s -PAA)-PCL copolymer was devised as an additive to endow PLLA with water-responsive SM capability. The incorporated PLLA was characterized by cross-section, water contact angle, differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Inserted PTMG segment and assisted ambient temperature were contributed to its SM behaviors. The shape fixation ratio and shape recovery ratio were 92.0% and 94.2%, respectively. The schematic diagram between internal microstructures and macroscopic properties was proposed. At the same time, the incorporated PLLA showed excellent toughness. So the obtained SM material would be promising for medical and biomimetic fields.

CAS / MDL: 502-44-3 24980-41-4
研究领域: 材料科学 · 生物医学工程 · 高分子科学
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2022 ·Vol. 33 ·期 10 ·3532-3539 · IF 3.348

Hydrophilic shape memory polymer hydrogels with virous pore structures and shape changing performance

Yang Lv,Xiaohu Chen,Peicong Zhang,Shiyi Zhou,Junfeng Li,Ruqing Bai,Li Wang

The preparation of a porous shape memory hydrogel with excellent shape changing performance is a hot research topic at present. In this paper, hydrophilic hydrogels were synthesized using polypropylene glycol (PPG) and polyethylene glycol (PEG) as raw materials and hexamethylene diisocyanate (HDI) as crosslinking agent. The pore structures were developed by gas foaming and salt leaching methods. The results showed that the hydrophilicity of hydrogel and the swelling rate in phosphate buffered saline (PBS) increased with the increase of PEG mass fraction, the shape changing performance of hydrogels varied as well with high shape recovery rate ≥90%. The recovery speed in aqueous environment was faster than in the air. After embedding hydroxyapatite (HA) particles, the materials exhibited appropriate degradable properties and good in vitro mineralization performance. Therefore, the obtained PPG/PEG system hydrogels is expected to become an ideal platform for tissue engineering and other applications in the biomedical field.

研究领域: 生物材料学 · 组织工程学
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TEXTILE RESEARCH JOURNAL · 2024 · IF 1.6

Effect of silane coupling agent modification on shape memory behavior and mechanical properties of knitting fabric reinforced composites

Ying Huang,Haipeng Ren,Wenqing Du,Weiye Li,Yiwei Ouyang,Yang Liu

Continuous glass fiber fabrics can improve the shortcomings of shape memory polymers in terms of mechanical properties. However, the mechanical properties of shape memory composites will not be optimal if the interface between the glass fibers and the matrix is poorly bonded. The purpose of this study is to explore the thermomechanical properties and shape memory behavior of shape memory epoxy resin and composites before and after the chemical modification of glass fiber. The effects of the ratios of epoxy to curing agent and whether the knitting fabrics are modified with silane coupling agent on the properties of the composites are investigated. The results show that the thermal decomposition temperature and glass transition temperature of the shape memory epoxy polymers increase with the increasing mass ratio of diaminodiphenylmethane. The shape fixing ratios and shape recovery ratios of the knitting fabric reinforced composites with different mass contents and silane coupling agent modification are above 98.0% at 18.0% tensile strain. After 10 cycles, the shape memory performance of the composites modified with KH560 is still good. Besides, the addition of silane coupling agent to the composites can reduce the shape recovery time by 17.9% and increase the recovery force with 30.0% subjected to 18.0% tensile strain. The tensile strength of the shape memory composites modified with silane coupling agent can increase 32.8% as compared with that of the composites without modification.

研究领域: 材料科学 · 聚合物复合材料 · 机械工程 · 化学改性
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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Controlled 3D Shape Transformation Activated by Room Temperature Stretching and Release of a Flat Polymer Sheet

Shuwei Wang,Guo Li,Zhaotie Liu,Zhongwen Liu,Jinqiang Jiang,Yue Zhao

Shape transformation of polymeric materials, including hydrogels, liquid crystalline, and semicrystalline polymers, can be realized by exposing the shape-changing materials to the effect of a variety of stimuli such as temperature, light, pH, and magnetic and electric fields. Herein, we demonstrate a novel and different approach that allows a flat sheet or strip of a polymer to transform into a predesigned 3D shape or structure by simply stretching the polymer at room temperature and then releasing it from the external stress, that is, a 2D-to-3D shape change is activated by mechanical deformation under ambient conditions. This particular type of stimuli-controlled shape-changing polymers is based on suppressing plastic deformation in selected regions of the flat polymer sheet prior to stretching and release. We validated the design principle by using a polymer blend composed of poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), and tannic acid (TA) whose plastic deformation can be locally inhibited by surface treatment using an aqueous solution of copper sulfate pentahydrate (Cu2+ ink) that cross-links PAA chains through a Cu2+–carboxylate coordination and, consequently, increases the material’s Young’s modulus and yield strength. After room temperature stretching and release, elastic deformation in the Cu2+ ink-treated regions leads to 3D shape transformation that is controlled by the patterned surface treatment. This facile and effective “stretch-and-release” approach widens the scope of preparation and application for shape-changing polymers.

研究领域: 材料科学 · 高分子化学
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POLYMER · 2024 · IF 4.1

Ultra-high stretchability and shape fixation rate shape memory polyurethanes based on cyclic polytetrahydrofuran molecular rings

Yu Qiao,Wenzhong Ma,You Zhang,Tiansheng Gao,Haicun Yang,Zheng Cao,Jing Zhong

Chemical cross-linking is commonly used to prevent slippage between molecular chains in shape memory polymers (SMPs) to improve shape return. However, chemical cross-linking makes SMPs less stretchable, and the disordered network structure reduces the ability of SMPs to maintain temporary shapes. To obtain ultra-high stretchability and better shape memory properties, a cyclic polymer (C-PTHF-OH) was introduced into the shape memory polyurethane (PUC X ) network, and the PUC X network topology was controlled by adjusting the content of C-PTHF-OH molecular rings. PUC 0.5 exhibited the highest shape fixation (99.9 %) and shape recovery (98.4 %), and the higher the content of the C-PTHF-OH molecular ring, the higher the elongation at break of the prepared PUC X , with a slight decrease in tensile strength. Compared to PUC 0 (2000 % elongation at break and 32 MPa tensile strength) prepared from the linear polymer, PUC 0.5 showed up to 2150 % elongation at break and 31 MPa tensile strength. This study provides new ideas for the design of network structures for SMPs and is a new paradigm introduced into the SMPs network by cyclic topological polymers.

研究领域: 材料科学 · 高分子化学
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