A review on the recent progress, opportunities, and challenges of 4D printing and bioprinting in regenerative medicine.

Four-dimensional (4 D) printing is a novel emerging technology, which can be defined as the ability of 3 D printed materials to change their form and functions. The term 'time' is added to 3 D printing as the fourth dimension, in which materials can respond to a stimulus after finishing the manufacturing process. 4 D printing provides more versatility in terms of size, shape, and structure after printing the construct. Complex material programmability, multi-material printing, and precise structure design are the essential requirements of 4 D printing systems. The utilization of stimuli-responsive polymers has increasingly taken the place of cell traction force-dependent methods and manual folding, offering a more advanced technique to affect a construct's adjusted shape transformation. The present review highlights the concept of 4 D printing and the responsive bioinks used in 4 D printing, such as water-responsive, pH-responsive, thermo-responsive, and light-responsive materials used in tissue regeneration. Cell traction force methods are described as well. Finally, this paper aims to introduce the limitations and future trends of 4 D printing in biomedical applications based on selected key references from the last decade.

Layered Double Hydroxide (MgFeAl-LDH)-Based Polypropylene (PP) Nanocomposite: Mechanical Properties and Thermal Degradation.

This work analyzes the thermal degradation and mechanical properties of iron (Fe)-containing MgAl layered double hydroxide (LDH)-based polypropylene (PP) nanocomposite. Ternary metal (MgFeAl) LDHs were prepared using the urea hydrolysis method, and Fe was used in two different concentrations (5 and 10 mol%). Nanocomposites containing MgFeAl-LDH and PP were prepared using the melt mixing method by a small-scale compounder. Three different loadings of LDHs were used in PP (2.5, 5, and 7.5 wt%). Rheological properties were determined by rheometer, and flammability was studied using the limiting oxygen index (LOI) and UL94 (V and HB). Color parameters (L*, a*, b*) and opacity of PP nanocomposites were measured with a spectrophotometer. Mechanical properties were analyzed with a universal testing machine (UTM) and Charpy impact test. The thermal behavior of MgFeAl-LDH/PP nanocomposites was studied using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The morphology of LDH/PP nanocomposites was analyzed with a scanning electron microscope (SEM). A decrease in melt viscosity and increase in burning rate were observed in the case of iron (Fe)-based PP nanocomposites. A decrease in mechanical properties interpreted as increased catalytic degradation was also observed in iron (Fe)-containing PP nanocomposites. Such types of LDH/PP nanocomposites can be useful where faster degradation or faster recycling of polymer nanocomposites is required because of environmental issues.

On the Influence of Viscoelastic Modeling in Fluid Flow Simulations of Gum Acrylonitrile Butadiene Rubber.

Computational fluid dynamics (CFD) simulation is an important tool as it enables engineers to study different design options without a time-consuming experimental workload. However, the prediction accuracy of any CFD simulation depends upon the set boundary conditions and upon the applied rheological constitutive equation. In the present study the viscoelastic nature of an unfilled gum acrylonitrile butadiene rubber (NBR) is considered by applying the integral and time-dependent Kaye-Bernstein-Kearsley-Zapas (K-BKZ) rheological model. First, exhaustive testing is carried out in the linear viscoelastic (LVE) and non-LVE deformation range including small amplitude oscillatory shear (SAOS) as well as high pressure capillary rheometer (HPCR) tests. Next, three abrupt capillary dies and one tapered orifice die are modeled in Ansys POLYFLOW. The pressure prediction accuracy of the K-BKZ/Wagner model was found to be excellent and insensitive to the applied normal force in SAOS testing as well as to the relation of first and second normal stress differences, provided that damping parameters are fitted to steady-state rheological data. Moreover, the crucial importance of viscoelastic modeling is proven for rubber materials, as two generalized Newtonian fluid (GNF) flow models severely underestimate measured pressure data, especially in contraction flow-dominated geometries.

Effect of Molar Mass on Critical Specific Work of Flow for Shear-Induced Crystal Nucleation in Poly (l-Lactic Acid).

The concept of specific work of flow has been applied for the analysis of critical shearing conditions for the formation of crystal nuclei in poly (l-lactic acid) (PLLA). Systematic variation in both time and rate of shearing the melt in a parallel-plate rheometer revealed that these parameters are interconvertible regarding the shear-induced formation of crystal nuclei; that is, low shear rate can be compensated for by increasing the shear time and vice versa. This result supports the view that critical shearing conditions can be expressed by a single quantity, providing additional options for tailoring polymer processing routes when enhanced nuclei formation is desired/unwanted. Analysis of PLLA of different mass-average molar masses of 70, 90, 120, and 576 kDa confirmed improved shear-induced crystal nucleation for materials of higher molar mass, with critical specific works of flow, above which shear-induced nuclei formation occurs, of 550, 60, 25, and 5 kPa, respectively.

The Tensile Behaviour of Highly Filled High-Density Polyethylene Quaternary Composites: Weld-Line Effects, DIC Curiosities and Shifted Deformation Mechanisms.

The interactive effects between additives and weld lines, which are frequent injection-moulding defects, were studied in high-density polyethylene (HDPE) and compared to weld-line-free reference samples. These materials were formulated around a D- and I-optimal experimental design, based on a quadratic Scheffé polynomial model, with up to 60 wt% calcium carbonate, masterbatched carbon black and a stabiliser package. Where reasonable and appropriate, the behaviours of the systems were modelled using statistical techniques, for a better understanding of the underlying trends. The characterisations were performed through the use of conventional tensile testing, digital image correlation (DIC) and scanning electron microscopy (SEM). A range of complex interactive effects were found during conventional tensile testing, with DIC used to better understand and explain these effects. SEM is used to better understand the failure mechanics of some of these systems through fractography, particularly regarding particle effects. A measure is introduced to quantify the deviation of the pre-yield deformation curve from the ideal elastic case. Novel analysis of DIC results is proposed, through the use of combined time-series plots and measures quantifying the extent and localisation of peak deformation. Through this, it could be found that strong shifts in the deformation mechanisms occur as a function of formulation and the presence/absence of weld lines. Primarily, changes are noted in the onset of continuous inter- and intralamellar slip and cavitation/fibrillation, seen through the onset of localised deformation and stress-whitening.

Effect of Filler Synergy and Cast Film Extrusion Parameters on Extrudability and Direction-Dependent Conductivity of PVDF/Carbon Nanotube/Carbon Black Composites.

In the present study, melt-mixed composites based of poly (vinylidene fluoride) (PVDF) and fillers with different aspect ratios (carbon nanotubes (CNTs), carbon black (CB)) and their mixtures in composites were investigated whereby compression-molded plates were compared with melt-extruded films. The processing-related orientation of CNTs with a high aspect ratio leads to direction-dependent electrical and mechanical properties, which can be reduced by using mixed filler systems with the low aspect ratio CB. An upscaling of melt mixing from small scale to laboratory scale was carried out. From extruded materials, films were prepared down to a thickness of 50 µm by cast film extrusion under variation of the processing parameters. By combining CB and CNTs in PVDF, especially the electrical conductivity through the film could be increased compared to PVDF/CNT composites due to additional contact points in the sample thickness. The alignment of the fillers in the two directions within the films was deduced from the differences in electrical and mechanical film properties, which showed higher values in the extrusion direction than perpendicular to it.

Constructing a Microcapacitor Network of Carbon Nanotubes in Polymer Blends via Crystallization-Induced Phase Separation Toward High Dielectric Constant and Low Loss.

Tailoring the distribution of nanoparticles and further constructing effective microcapacitors in polymer blends are important issues for developing high-performance polymer dielectric nanocomposites. The common method to control the selective localization of nanoparticles in an immiscible polymer blend is relatively difficult and it easily results in the accumulation of nanoparticles in one component, which usually leads to a dramatic increase of the dielectric loss in the nanocomposites. In this work, a novel strategy based on step-by-step crystallization has been proposed to tailor the refined distribution and dispersion of carbon nanotubes (CNTs) in a melt-miscible blend poly(butylene succinate)/poly(vinylidene fluoride) (PBS/PVDF) through the crystallization-induced phase separation and the engineered interfacial affinity between CNTs and polymer components to acquire high dielectric constant and low dielectric loss. The results reveal that PBS is excluded along the growth front of PVDF spherulites and locates in the margin areas of PVDF spherulites during the step-by-step crystallization process. Moreover, because of the higher interfacial interaction between CNTs and PBS, CNTs are located in the PBS-rich domain, resulting in a high concentration of CNTs in the interspherulites of PVDF. Thus, the dielectric constants of the nanocomposites are greatly improved by nearly 5-24 times compared with the nanocomposites achieved by quick cooling and, simultaneously, the dielectric loss of the nanocomposites is still maintained at a low level. This work shows that the step-by-step crystallization method can be used to fabricate the nanocomposites with a synergistic increase in the dielectric performance due to the formation of a refined microcapacitor assembly. To the best of our knowledge, this is the first report to show that the dielectric constant of the nanocomposites can be greatly enhanced just through the crystallization-optimized distribution and dispersion of CNTs in immiscible polymer blends, and it possibly gives a new technical route for the fabrication of advanced dielectric composites.