生物医用形状记忆高分子材料

形状记忆聚合物作为一种智能材料,已经在生物医用领域显示出了巨大的应用前景。基于形状记忆聚合物材料的原理,组成和结构可以设计兼具生物降解性、生物相容性等多种功能的新型智能材料。本文综述了三种典型的生物降解性形状记忆聚合物材料(聚乳酸、聚己内酯、聚氨酯)的发展,从结构上对三种形状记忆聚合物进行了分类讨论,详细分析了不同种类聚合物形状记忆的机理、形状变化的固定率和回复率、回复速率等,并介绍了一些形状记忆聚合物材料在生物医学中的应用。最后对医用形状记忆聚合物未来发展进行了展望:双程形状记忆聚合物及体温转变形状记忆材料将会受到研究者的重点关注。     

A review of shape memory polymer composites and blends

Shape memory polymers (SMPs) are a kind of very important smart polymers. In order to improve the properties or obtain new functions of SMPs, SMP composites and blends are prepared. We thoroughly examine the research in SMP composites and blends achieved by numerous research groups around the world. The preparation of SMPs composites and blends is mainly for five aims: (1) to improve shape recovery stress and mechanical properties; (2) to decrease shape recovery induction time by increasing thermal conductivity; (3) to create new polymer/polymer blends with shape-memory effect (SME); (4) to tune switch temperature, mechanical properties, and biomedical properties of SMPs; (5) to fabricate shape memory materials sensitive to electricity, magnetic, light and moisture. The trend of SMP composite development is discussed. SMP composites and blends exhibit novel properties that are different from the conventional SMPs and thus can be utilized in various applications.     

Improvement of dissolution behavior of poorly water soluble drugs by biodegradable polymeric submicron carriers containing sparingly methylated β-cyclodextrin

The objective of this study was to develop submicron carriers of two drugs that are practically insoluble in water, i.e. meloxicam and aceclofenac, to improve their dissolution behavior. The phase solubility of the drugs was studied using different concentrations of sparingly methylated β-cyclodextrin, Kleptose^® Crysmeβ (Crysmeb), in the presence and absence of 0.2 % w/v water-soluble chitosan. Drug-loaded submicron particles (SMPs) were prepared using chitosan chlorhydrate and Crysmeb by the ionotropic gelation method. The SMPs were characterized in terms of powder X-ray diffraction, Fourier transforms infrared spectroscopy, size determination, process yield, drug loading, encapsulation efficiency, surface morphology and in vitro release. The drug loading in the SMPs was enhanced in the presence of Crysmeb. The in vitro drug release was found to be enhanced with SMPs prepared using higher concentrations of Crysmeb. These results indicate that SMPs formed from chitosan chlorhydrate and Crysmeb are promising submicron carriers for enhancing the dissolution of meloxicam and aceclofenac.     

形状记忆聚合物热力学本构模型研究进展

形状记忆聚合物是一种新型的智能材料,与记忆合金相比它具有密度低、高恢复率、易生产和低成本等优点。由于这些特性,它广泛应用于医疗和航天等领域,其理论研究逐渐得到人们的重视。形状记忆聚合物主要通过热致变形来实现形状记忆和恢复效应,因此热力学本构模型是其材料的形状记忆和恢复功能的关键因素。文中介绍了形状记忆聚合物热力学本构模型的一些理论研究成果,并对其中存在的一些问题作了简要地讨论。     

形状记忆高分子材料在生物医学领域的应用

形状记忆高分子材料(SMPs)作为一种新型功能材料具有生物相容性好、形变率大、形变温度可调、易于加工、可引入生物降解组分等特点,近年来,特别是在生物医药领域,SMPs已成为研究人员广泛关注的焦点之一。根据SMPs的功能及其应用研究现状,着重综述了近年来SMPs在矫形固定材料、药物缓释体系、手术缝合、微创医疗器械以及组织工程等生物医学领域的主要研究和应用,并展望了SMPs在生物医学领域未来的研究方向和前景,同时,简要介绍了SMPs的发展概况及其具有形状记忆效应的原理。     

Biomedical applications of thermally activated shape memory polymers

Shape memory polymers (SMPs) are smart materials that can remember a primary shape and can return to this primary shape from a deformed secondary shape when given an appropriate stimulus. This property allows them to be delivered in a compact form via minimally invasive surgeries in humans, and deployed to achieve complex final shapes. Here we review the various biomedical applications of SMPs and the challenges they face with respect to actuation and biocompatibility. While shape memory behavior has been demonstrated with heat, light and chemical environment, here we focus our discussion on thermally stimulated SMPs.     

Curing characteristics of shape memory polymers in 3D projection and laser stereolithography

The radical shift in 3D printing to fabricate soft active materials such as shape memory polymers (SMPs) has brought along other techniques in realising 4D printing. Stereolithography (SL) process has recently been one of the popular systems for printing SMPs. In this paper, the curing characteristics and behaviour of the SMPs fabricated via projection-type and laser-scanning-type SL process were analysed. Factors such as the UV exposure of the projection type and variation in resin compositions have significant differences in terms of energy density and curing depths when compared to the laser scanning type. Hence, theoretical calculations were made to determine the critical energy density and threshold penetration depth attainable, which enables newly developed SMP materials to be successfully printable using different types of UV-based 3D printing systems.     

Review of electro-active shape-memory polymer composite

Shape-memory polymers (SMPs) have been one of the most popular subjects under intensive investigation in recent years, due to their many novel properties and great potential. These so-called SMPs by far surpass shape-memory alloys and shape-memory ceramics in many properties, e.g., easy manufacture, programming, high shape recovery ratio and low cost, and so on. However, they have not fully reached their technological potential, largely due to that the actuation of shape recovery in thermal-responsive SMPs is normally only driven by external heat. Thus, electro-activate SMP has been figured out and its significance is increasing in years to come. This review focuses on the progress of electro-activate SMP composites. Special emphases are given on the filler types that affect the conductive properties of these composites. Then, the mechanisms of electric conduction are addressed.     

Recent advances in shape memory polymers and composites: a review

Shape memory polymers (SMPs) belong to a class of smart polymers, which have drawn considerable research interest in last few years because of their applications in microelectromechanical systems, actuators, for self healing and health monitoring purposes, and in biomedical devices. Like in other fields of applications, SMP materials have been proved to be suitable substitutes to metallic ones because of their flexibility, biocompatibility and wide scope of modifications. The shape memory properties of SMPs polymers might surpass those of shape memory metallic alloys (SMAs). In addition to block copolymers, polymers blends and interpenetrating network structured SMP systems have been developed. The present review mainly highlights the recent progress in synthesis, characterization, evaluation, and proposed applications of SMPs and related composites.     

Shape-memory surfaces for cell mechanobiology

Shape-memory polymers (SMPs) are a new class of smart materials, which have the capability to change from a temporary shape ‘A’ to a memorized permanent shape ‘B’ upon application of an external stimulus. In recent years, SMPs have attracted much attention from basic and fundamental research to industrial and practical applications due to the cheap and efficient alternative to well-known metallic shape-memory alloys. Since the shape-memory effect in SMPs is not related to a specific material property of single polymers, the control of nanoarchitecture of polymer networks is particularly important for the smart functions of SMPs. Such nanoarchitectonic approaches have enabled us to further create shape-memory surfaces (SMSs) with tunable surface topography at nano scale. The present review aims to bring together the exciting design of SMSs and the ever-expanding range of their uses as tools to control cell functions. The goal for these endeavors is to mimic the surrounding mechanical cues of extracellular environments which have been considered as critical parameters in cell fate determination. The untapped potential of SMSs makes them one of the most exciting interfaces of materials science and cell mechanobiology.     

Shape-memory surfaces for cell mechanobiology

Abstract

Shape-memory polymers (SMPs) are a new class of smart materials, which have the capability to change from a temporary shape ‘A’ to a memorized permanent shape ‘B’ upon application of an external stimulus. In recent years, SMPs have attracted much attention from basic and fundamental research to industrial and practical applications due to the cheap and efficient alternative to well-known metallic shape-memory alloys. Since the shape-memory effect in SMPs is not related to a specific material property of single polymers, the control of nanoarchitecture of polymer networks is particularly important for the smart functions of SMPs. Such nanoarchitectonic approaches have enabled us to further create shape-memory surfaces (SMSs) with tunable surface topography at nano scale. The present review aims to bring together the exciting design of SMSs and the ever-expanding range of their uses as tools to control cell functions. The goal for these endeavors is to mimic the surrounding mechanical cues of extracellular environments which have been considered as critical parameters in cell fate determination. The untapped potential of SMSs makes them one of the most exciting interfaces of materials science and cell mechanobiology.     

Improving the Bs and soft magnetic properties of Fe-based amorphous ribbons by manipulating the surface crystallization behavior

A novel amorphous structure coupling with ultra-fine nano α-Fe grains in the surface crystallization layer was fabricated successfully through composition regulation and proper quenching conditions. The microstructure of the newly formed surface crystallization layer and its effects on soft magnetic properties of FeMnCuMoCPSiB amorphous alloy were investigated systematically. The FeMnCuMoCPSiB amorphous alloy with surface α-Fe crystallization layers exhibits an excellent comprehensive performance of soft magnetic properties (SMPs) with high B_s of 1.67 T, low H_c of 1.6 A/m, and high μ_i of 9.3?×?10³ at 1 kHz. The SMPs of the amorphous alloy is considerably superior to that of widely used commercial soft magnetic materials METGLAS 2605, promising a potential engineering application. It is noteworthy that a nanoscale surface precipitation was found in the alloy, which favors SMPs of the alloy.

     

Metal-oxide-doped silica nanoparticles for the catalytic glycolysis of polyethylene terephthalate

Polyethylene terephthalate (PET) was depolymerized to monomer bis(2-hydroxyethyl) terephthalate (BHET) using excess ethylene glycol (EG) in the presence of metal oxides that were impregnated on different forms of silica support [silica nanoparticles (SNPs) or silica microparticles (SMPs)] as glycolysis catalysts. The reactions were carried out at 300 degrees C and 1.1 MPa at an EG-to-PET molar ratio of 11:1 and a catalyst-to-PET-weight ratio of 1.0% for 40-80 min. Among the four prepared catalysts (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nanocomposite had the highest monomer yield (> 90%). This high yield may be explained by the high surface area, amorphous and porous structure, and existence of numerous active sites on the nanocomposite catalyst. The BHET yield increased with time and reached the highest level where equilibrium was established between BHET and its dimer. The catalysts were characterized by their SEM, TEM, and BET surface areas, and via XRD, whereas the monomer BHET was characterized by HPLC and FT-IR. The glycolysis with the Mn3O4/SNPs nanocomposite as the glycolysis catalyst produced a maximum BHET in a short reaction time.     

A finite deformation constitutive model for shape memory polymers based on Hencky strain

In many engineering applications, shape memory polymers (SMPs) usually undergo arbitrary thermomechanical loadings at finite deformation. Thus, development of 3D constitutive models for SMPs within the finite deformation regime has attracted a great deal of interest. In this paper, based on the classical framework of thermodynamics of irreversible processes, employing the logarithmic (or Hencky) strain as a more physical measure of strain, a 3D large-strain macromechanical model is presented. In the constitutive model development, we adopt a multiplicative decomposition of the deformation gradient into elastic and stored parts. In addition, employing the averaging scheme, the logarithmic elastic strain tensor is decomposed into the rubbery and glassy parts. The evolution equations for internal variables are introduced for both cooling and heating processes. The time-discrete form of the proposed model in the implicit form is also presented. Comparing the predicted results with experimental data reported in the literature, the model is validated. Finally, using the finite element method, two boundary value problems e.g., a 3D beam and a medical stent made of SMPs are numerically simulated.     

热致形状记忆聚合物的热力学性能

形状记忆聚合物作为一类新型功能材料,具有独特优点,近年来在机理研究和工程应用方面均受到高度重视。由于其功能实现主要是通过热激励实现的,建立其热力学本构方程是开展该类功能材料变形机理研究的基础。本文首先通过单拉伸实验研究了热致形状记忆聚氨酯在预应变分别为0%、5%、10%和20%下的形状冻结和恢复性能。考虑其冻结/恢复时间延迟效应、应力松弛效应以及热变形效应的影响,对其变形过程进行了理论分析。结果证实,理论预测值与实验测试结果较为吻合。     

4D Printing-Encapsulated Polycaprolactone–Thermoplastic Polyurethane with High Shape Memory Performances

There are a few shape memory polymers (SMPs) like polylactic acid (PLA) and polyurethane (PU) that are 4D printable, and other SMPs must be synthesized with a complicated chemical lab effort. Herein, considering dual-material extrusion printing and microscopic mechanism behind shape memory effect (SME), bilayer-encapsulated polycaprolactone (PCL)–thermoplastic polyurethane (TPU) shape memory composite structures are 4D printed for the first time. The SME performance is investigated by assessing fixity, shape recovery, stress recovery, and stress relaxation under bending and compression loading modes. PCL, TPU, and melting temperature of PCL play the role of switching phase, net point, and transition temperature, respectively. Due to the destruction and dripping of molten PCL in contact with water, PCL is encapsulated by TPU. Encapsulation successfully solves the challenge of bonding/interface between printed layers, and the results show that the SME performance of the encapsulated structures is higher than bilayer PCL–TPU one's. Experiments reveal that maximum stress recovery in 4D-printed composites remains constant over time. This is a great achievement compared to the previous extrusion-based SMP structures that have great weakness in stress relaxation due to weak and low crystalline fractions and the unraveling of molecular entanglements in semicrystalline and amorphous thermoplastic SMPs, respectively.     

Fate of copper in submerged membrane bioreactors treating synthetic municipal wastewater

This paper assesses the impact of copper on the performance of two membrane bioreactors (MBR) treating municipal wastewater at a hydraulic retention time (HRT) of 4h, and solids residence times (SRT) of 20 days, at influent copper concentrations of 0.2-8 mg Cu/L. The addition of copper resulted in a significant increase in soluble microbial products (SMPs), and a predominance of >100 kDa molecular weight SMPs. The study showed that in well-buffered wastewaters, complete nitrification was achieved at total copper concentrations as high as 840 mg/L or 10% of the mixed liquor volatile suspended solids. MINTEQ simulation showed that most of the copper (99.8%) in the MBR was in the form of inorganic copper precipitates, with free Cu2+ and total soluble copper in the range of 0.0-0.11 and 0.1-0.82 mg/L, respectively.     

Unique Shape Memory Elastomer Associated with Reversible Sacrificial Hydrogen Bonds: Tough and Flexible When below Its Tg

Thermally induced shape memory polymers (SMPs) are fragile and brittle when cooling to a low temperature to generate temporary shapes. In the present study, the authors implement a new design strategy for fabricating elastomeric SMPs with low‐temperature flexibility by engineering reversible sacrificial hydrogen bonds into a chemically crosslinked network. Compatible, amorphous, hindered phenol moieties (Irganox 1010) are incorporated into epoxidized natural rubber (ENR) and the ENR composites are cured with zinc diacrylate (ZDA). Such reversible sacrificial bonds can rupture prior to the rupture of the bonds of the crosslinked network during stretching, which will dissipate energy and facilitate reorientation of the rubber chains. Based on the functional mechanisms, ENR composites exhibit unusual toughness and flexibility and can undergo large deformations even when below their T_g. Irganox 1010 can also be used to tune the glass transition temperature (T_g) and improve the chain mobility of the elastomer sample by providing sufficient intermolecular hydrogen bonding interactions. ENR composites demonstrate thermally triggered shape memory performance. Moreover, the dissociation/reformation of hydrogen bonds upon stretching/cooling can endow the elastomer sample with unique reversible plastics shape memory (RPSM) performance. These SMPs possess excellent shape fixity and recovery.

     

A 3D finite deformation constitutive model for amorphous shape memory polymers: A multi-branch modeling approach for nonequilibrium relaxation processes

Shape memory polymers (SMPs) are materials that can recover a large pre-deformed shape in response to environmental stimuli. For a thermally activated amorphous SMP, the pre-deformation and recovery of the shape require the SMP to traverse its glass transition temperature (T_g) to complete the shape memory (SM) cycle. As a result, the recovery behavior of SMPs shows strong dependency on both the pre-deforming temperature and recovery temperature. Generally, to capture the multitude of relaxation processes, multi-branch models (similar to the 1D generalized viscoelastic model or Prony series) are used to model the time-dependent behaviors of polymers. This approach often requires an arbitrary (usually numerous) number of branches to capture the material behavior, which results in a substantial number of material parameters. In this paper, a multi-branch model is developed to capture the SM effect by considering the complex thermomechanical properties of amorphous SMPs as the temperature crosses T_g. The model utilizes two sets of nonequilibrium branches for fundamentally different modes of relaxation: the glassy mode and Rouse modes. This leads to a significant reduction in the number of material parameters. Model simulation comparisons with a range of thermomechanical experiments conducted on a tert-butyl acrylate-based SMP show very good agreement. The model is further utilized to explore the intrinsic recovery behavior of an SMP and the size effects on the free recovery characteristics of a magneto-sensitive SMP composite.