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Effect of Moisture on Shape Memory Polyurethane Polymers for Extrusion-Based Additive Manufacturing.

ABSTRACT: Extrusion-based additive manufacturing (EBAM) or 3D printing is used to produce customized prototyped parts. The majority of the polymers used with EBAM show moisture sensitivity. However, moisture effects become more pronounced in polymers used for critical applications, such as biomedical stents, sensors, and actuators. The effects of moisture on the manufacturing process and the long-term performance of Shape Memory Polyurethane (SMPU) have not been fully investigated in the literature. This study focuses primarily on block-copolymer SMPUs that have two different hard/soft (h/s) segment ratios. It investigates the effect of moisture on the various properties via studying: (i) the effect of moisture trapping within these polymers and the consequences when manufacturing; (ii) and the effect on end product performance of plasticization by moisture. Results indicate that higher h/s SMPU shows higher microphase separation, which leads to an increase of moisture trapping within the polymer. Understanding moisture trapping is critical for EBAM parts due to an increase in void content and a decrease in printing quality. The results also indicate a stronger plasticizing effect on polymers with lower h/s ratio but with a more forgiving printing behavior compared to the higher h/s ratio.

SUBMITTER: Garces IT

PROVIDER: S-EPMC6356422 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Effect of Moisture on Shape Memory Polyurethane Polymers for Extrusion-Based Additive Manufacturing.

Garces Irina T IT Aslanzadeh Samira S Boluk Yaman Y Ayranci Cagri C

Materials (Basel, Switzerland) 20190112 2

Extrusion-based additive manufacturing (EBAM) or 3D printing is used to produce customized prototyped parts. The majority of the polymers used with EBAM show moisture sensitivity. However, moisture effects become more pronounced in polymers used for critical applications, such as biomedical stents, sensors, and actuators. The effects of moisture on the manufacturing process and the long-term performance of Shape Memory Polyurethane (SMPU) have not been fully investigated in the literature. This ...[more]

PMID: 30642087

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Project description:Water-blown polyurethane (PU) foams are of enormous technological interest as they are widely applied in various fields, i.e., consumer goods, medicine, automotive or aerospace industries. The discovery of the one-way shape-memory effect in PU foams provided a fresh impetus for extensive investigations on porous polymeric actuators over the past decades. High expansion ratios during the shape-recovery are of special interest when big volume changes are required, for example to fill an aneurysm during micro-invasive surgery or save space during transportation. However, the need to program the foams before each operation cycle could be a drawback impeding the entry of shape-memory polymeric (SMP) foams to our daily life. Here, we showed that a reversible shape-memory effect (rSME) is achievable for polyurethane water-blown semicrystalline foams. We selected commercially available crystallizable poly(ε-caprolactone)-diols of different molecular weight for foams synthesis, followed by investigations of morphology, thermal, thermomechanical and shape-memory properties of obtained compositions. Densities of synthesized foams varied from 110 to 180 kg∙m-3, while peak melting temperatures were composition-dependent and changed from 36 to 47 °C, while the melting temperature interval was around 15 K. All semicrystalline foams exhibited excellent one-way SME with shape-fixity ratios slightly above 100% and shape-recovery ratios from the second cycle of 99%. The composition with broad distribution of molecular weights of poly(ε-caprolactone)-diols exhibited an rSME of about 12% upon cyclic heating and cooling from Tlow = 10 °C and Thigh = 47 °C. We anticipate that our experimental study opens a field of systematic investigation of rSMEs in porous polymeric materials on macro and micro scale and extend the application of water-blown polyurethane foams to, e.g., protective covers with zero thermal expansion or even cushions adjustable to a certain body shape.

Project description:Shape memory polymers (SMPs) have been found to be promising biomaterials for a variety of medical applications; however, the clinical translation of such technology is dependent on tailorable properties such as gravimetric changes in degradation environments. For SMPs synthesized from amino-alcohols, oxidation resulting in rapid mass loss may be problematic in terms of loss of material functionality as well as toxicity and cytocompatibility concerns. Control of gravimetric changes was achieved through the incorporation of small molecule antioxidants, either directly into the polymer matrix or included in microparticles to form a SMP composite material. With direct incorporation of small molecule phenolic antioxidant 2,2'-methylenebis(6- tert-butyl)-methylphenol (Methyl), SMPs displayed reduce strain recovery by more than 50% (Methyl) and increase elastic modulus from approximately 1.4 to 2.3 MPa, at the expense of the strain to failure being reduced from 45% to 32%. Importantly, such changes could not ensure retention of the antioxidants and therefore did not increase oxidative stability beyond 15 days in accelerated oxidative conditions (equivalent to approximately 800 days in porcine aneurysms) in all cases except for the inclusion of a hindered amine that capped network growth, which also resulted in shape memory reduction (only 80% recoverable strain achieved). However, the inclusion of antioxidants in microparticles was found to produce materials with similar thermomechanical ( Tg migration below 1.0 °C) and shape recovery of 100%, while increasing oxidative resistance compared to controls (oxidation onset was delayed by 3 days and material lifespan increased to approximately 20-22 days in accelerated oxidative solution or beyond 1000 days in the porcine aneurysm). The microparticle composite SMPs also act as a platform for environmental sensing, such as pH-dependent fluorescence shifts and payload release, as demonstrated by fluorescent dye studies using phloxine B and nile blue chloride and the release of antioxidants over a 3 week period. The use of polyurethane-urea microparticles in porous SMPs is demonstrated to increase biostability of the materials, by approximately 25%, and ultimately extend their lifespan for use in aneurysm occlusion as determined through calculated in vivo degradation rates corresponding to a porcine aneurysm environment.

Dataset Information

Effect of Moisture on Shape Memory Polyurethane Polymers for Extrusion-Based Additive Manufacturing.

Publications

Effect of Moisture on Shape Memory Polyurethane Polymers for Extrusion-Based Additive Manufacturing.

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