Elsevier

Progress in Polymer Science

Volume 94, July 2019, Pages 57-116
Progress in Polymer Science

Polymers for additive manufacturing and 4D-printing: Materials, methodologies, and biomedical applications

https://doi.org/10.1016/j.progpolymsci.2019.03.001Get rights and content

Abstract

Additive manufacturing (AM), also known as additive manufacturing, permits the fabrication of fully customized objects with a high level of geometrical complexity at reduced fabrication time and cost. Besides metals and ceramics, polymers have become a widely researched class of materials for applications in AM. The synthetic versatility and adaptability, as well as the wide range of properties that can be achieved using polymer materials, have rendered polymers the most widely employed class of materials for AM methodologies. In this review, the basic principles, considering the printing mechanism as well as the advantages and disadvantages, of the most relevant polymer AM technologies are described. The particular features, properties and limitations of currently employed polymer systems in the various AM technology areas are presented and analyzed. Subsequently, 4D printing, that is the fabrication of 3D printed structures that are cabable to change with time, is discussed. A brief description of the polymeric materials and technologies under development for 4D printed structures as well as the different shape changes explored are presented. Finally, based on the characteristics of the polymers employed for each technology illustrative examples of the principal applications are discussed.

Section snippets

Introduction to additive manufacturing (AM)

The ISO/ASTM standards define the term additive manufacturing (AM), colloquially known as 3D printing, as the “process of joining materials to make parts from 3D model data, usually layer upon layer, as opposed to subtractive manufacturing and formative manufacturing methodologies” [1]. It has to be clarified at this stage that there are a number of different subtypes of additive manufacturing including 3D printing, but also rapid prototyping and direct digital manufacturing (DDM). The term

Brief summary of the AM technologies

ASTM International criteria classify polymer AM technologies into seven different categories: (a) material extrusion, (b) powder bed fusion, (c) vat photopolymerization, (d) material jetting, (e) binder jetting, (f) sheet lamination, and (g) directed energy deposition [62,63]. Fig. 9 shows a diagram in which the different additive manufacturing methodologies are organized according to several parameters: state of fusion, material feedstock, material distribution, and the AM principle. While it

Fused deposition modeling (FDM)

As has been mentioned above, FDM is an AM process in which the layers are formed by extrusion of a solid plastic filament which passes through a nozzle/print head that melts and extrudes it [136]. To be used for FDM, the printing material must be able to flow, after fusion, and then solidify. Amorphous thermoplastic polymers are the ideal materials for this application due to their low thermal expansion coefficient, glass transition temperature and melting temperature, properties which can

Polymers for stereolithography (SLA)

As it has been introduced before, SLA is a manufacturing process which consists in the curing or solidification of a photosensitive liquid polymer (resin) by using a UV laser. The photosensitive resin is comprised of three major components:

(a) A photoinitiator, which absorbs the light and generates the active species.

(b) A reactive multifunctional monomer/oligomer. The backbone can vary in structure and weight and is designed to confer specific mechanical, physical or chemical properties of the

Selective laser sintering (SLS): polymer powders and composites

First of all, it is worth mentioning that the 3D printed parts fabricated using SLS can achieve similar mechanical properties as parts prepared by injection molding or similar forming techniques [168,169]. However, probably one of the major advantages of SLS is related to the “a priori” great variety of materials that could be employed, including polymers, metals, and blends (metals and ceramics/polymers) [97,169,170].

Examples of polymers that could be blended are acrylic styrene (AS), PCL or

Polymeric materials employed in 4D printing

As has been elaborated before, a general requirement for 4D printing is the use of one or more than one material with distinct physical properties which enables shape changes. Whereas a wide variety of polymeric materials are available for additive manufacturing (as has been thoroughly revised in the previous sections of this review), there still exist a lot of pending issues which must be fulfilled for the development of 4D materials. In spite of this, recent efforts to achieve complex 4D

Biomedical applications

Polymers are, without doubt, the fastest growing category among all the materials employed for biomedical applications during the last decade [263]. This remarkable growth is related to the advantages in the use of polymers for biomedical purposes in comparison to metals. Among the most important advantages, it is worth mentioning the biocompatibility of several polymers, as well as their elastic properties and bio-inertness.

The large variety of polymeric materials combined with the possibility

Conclusions and remarks

The development of a wide variety of additive manufacturing (AM) technologies offers nowadays versatile platforms for tailor-made fabrication of fully-customized products in a decentralized and cost-effective fashion. Besides its initial use limited as a tool for rapid prototyping or eventually for small-scale production of customized items, AM has become an interesting methodology to fabricate components with unusual shapes in a wide variety of applications ranging from architecture to

Acknowledgments

The authors acknowledge financial support given by FONDECYT Grant N° 1170209. M.A. Sarabia acknowledges the financial support given by CONICYT through the doctoral program Scholarship Grant. J. Rodriguez-Hernandez acknowledges financial support from the Spanish National Science Foundation (CSIC) and the Ministerio de Economia y Competitividad (MINECO) (Project MAT2016-78437-R, FONDOS FEDER). Finally, this study was funded by VRAC Grant Number L216-04 of Universidad Tecnológica Metropolitana.

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