Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Fabrication of patterned gold electrodes with spin-coated-and-fired Au(1 1 1) film by the soft lithography

We prepared high quality Au(1 1 1) film on Si wafer through the spin coating and thermal decomposition of a gold ink, spin-coated-and-fired (SCAF) Au film. The X-ray measurements, XRD and pole-figure analysis, showed that the SCAF Au film has a (1 1 1) out-of-plane orientation with a random in-plane orientation. In order to confirm the chemical activity of the SCAF Au film, we demonstrate the formation of patterned structures with the film by using soft lithography technique. The chemical activities of this physically stable SCAF Au film to the alkanethiols were at least equivalent those of physically deposited the Au films. The possibility of the mass production of micro patterned structure with the SCAF Au film was also demonstrated over the wide region on Si wafer by the microcontact lithography. These suggest that the Au film will help the easy fabrication of various nanosized devices on Si wafer and other substrates.     

Microstructure array on Si and SiOx generated by micro-contact printing, wet chemical etching and reactive ion etching

A method, combining micro-contact printing (μCP), wet chemical etching and reactive ion etching (RIE), is reported to fabricate microstructures on Si and SiOx. Positive and negative structures were generated based on different stamps used for μCP. The reproducibility of the obtained microstructures shows the methodology reported herein could be useful in Micro-Electro-Mechanical Systems (MEMS), optical and biological sensing applications.     

XPS investigations of ink‐jet printed paper

Different ink‐jet printed paper materials were investigated using X‐ray photoelectron spectroscopy (XPS) yielding the elemental composition of the near‐surface region of the papers. We found significant differences with respect to the detected elements and their atomic concentrations in the different inks studied here. Two different groups of inks could be identified by means of a lower ratio of the O and C atomic concentrations and lower concentrations in specific trace elements like Mg, Na and Si. High‐resolution spectra of C 1s and O 1s core levels allowed a detailed determination of the chemical state of the respective elements. On the basis of a detailed deconvolution of these XPS signals, significant differences between all the investigated ink‐jet printed papers were found, thereby allowing their discrimination. The applicability of the measurements and, more generally, the XPS technique for forensic investigations of paper are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

A Large-Area Patterned TiO2/SnO2 Bilayer Type Photocatalyst Prepared by Gravure Printing

Anatase TiO₂ films (thickness = 50 nm) were formed in shape of stripes (width = 1.6 mm, interval = 0.4 mm) by gravure printing on commercially available SnO₂ coated soda-lime glass substrates (dimension = 300 × 300 mm). Its photocatalytic activity was examined for the gas-phase oxidation of CH₃CHO in comparison with a simple TiO₂ photocatalyst formed on a silica glass. The patterned TiO₂/SnO₂ bilayer type photocatalyst showed a high photocatalytic activity in an H₂O bearing atmosphere. On the other hand, neither the patterning nor stacking effect was observed for the same reaction under dry conditions. These results could be explained in terms of the reducing potential of the electrons in the conduction band of the SnO₂ layer.     

植物纤维及其提取物增强聚合物的3D打印成型研究

3D打印技术作为新型成型技术,近年来受到了巨大的关注,但常见的PLA、ABS等单体打印耗材由于其自身的不同缺点,限制了其进一步的应用。本文综述了植物纤维及其提取物增强聚合物复合材料在3D打印领域的应用研究进展,重点阐述了木纤维、竹纤维,秸秆纤维等常见植物纤维用于3D打印的研究现状,还介绍了纤维素、木质素、半纤维素等植物纤维提取物增强聚合物用于3D打印的研究情况。同时对植物纤维/聚合物材料存在的一些问题及改性方法进行了分析与展望。     

油墨用聚氨酯树脂的研究

研究用于印刷油墨的单组分溶剂型聚氨酯树脂，考查聚合物多元醇和异氰酸酯对树脂微观形态、机械性能以及印刷适应性和附着性等性能的影响。结果表明：聚酯型树脂的附着性较好，4，4-二甲苯甲烷二异氰酸酯(MDI)基树脂的附着性较佳。     

Microcontact printed poly(amidoamine) dendrimer monolayers on silicon oxide surface

Patterning of silicon substrates with poly(amidoamine) generation 5 (PAMAM-G5) dendrimers using soft lithographic microcontact printing (μCP) is presented. μCP is shown to yield monolayers of dendrimers patterned with high level of definition over μm² to mm² areas. The patterns are stable over a period of weeks, which is attributed to the suppressed diffusion of partially charged G5 PAMAM on oxidized silicon. However, the dendrimers studied were shown to be relatively weakly bound to the substrate when subjected to lateral stresses. In aqueous conditions most of the dendrimers desorbed from the substrate.