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Plasticizer Effects on Physical–Mechanical Properties of Solvent Cast Soluplus® Films
Abstract and Figures
Soluplus® is a novel amphiphilic polymer that has been shown to enhance the solubility and drug dissolution rate of poorly soluble drugs. However, there still is a lack of information regarding the physical mechanical properties of Soluplus® with addition of the plasticizers. This study characterized the mechanical properties of Soluplus® with four different plasticizers. The plasticizers selected were polyethylene glycol 6, triethyl citrate, propylene glycol, and glycerin; they were studied at three different levels (15%, 20%, and 25% w/w). The effects of these plasticizers on the glass transition temperature, tensile strength, percent elongation, and Young's modulus of free films made from Soluplus® were measured and the toughness and ratio of tensile strength to Young's modulus were calculated. These results showed these four plasticizers are capable to plasticizing Soluplus® as indicated by the glass transition temperature lowering, tensile strength, and Young's modulus while increasing the percent elongation and film toughness. Among the plasticizers tested, polyethylene glycol 6 showed greatest changed in the mechanical properties studied.
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... Of the two sets of films evaluated, HB/MC/HMP/PPI/G and HB/CMC/HMP/NaCas/G had the maximum elongation at break of 131 and 139%, respectively, surpassing values reported in earlier studies, such as 13% for ethylene-vinyl alcohol (EVOH), and 64% for sugarcane bagasse [65, 78, [86][87][88][89][90]. The films developed in this work showed maximum toughness values of 8.83 and 7.56 MP, respectively. ...
... Overall, the films developed in this work exhibited a 14 to 34% increase in tensile strength and 3 to 26% in elastic modulus compared to their respective controls, demonstrating exceptional compatibility of HB with other film components because of intermolecular hydrogen bonding [82,83] as well as cross-linking potential, which was further promoted by plasticizers [86,87]. In contrast, the control films (HB/MC and HB/CMC) presented only moderate such interaction, likely due to poor adhesion between the biopolymer components without additional additives [88,89]. Figure S4 demonstrates the TGA and DTG curves for HB/ MC and HB/CMC-based films. ...
This study aims to develop biobased composite films using hemicellulose (HB), methylcellulose (MC), and carboxymethyl cellulose (CMC) combined with natural additives, including high methoxy pectin (HMP), selected proteins (whey, casein, soy, and pea), and glycerol. Results showed that integrating these components significantly improved the physical qualities, peelability, foldability, and transparency, particularly in HB/CMC-based films. Mechanical properties of the films, i.e., elongation at break, tensile stress, elastic modulus, and toughness, were also enhanced by incorporating these additives. Among the combinations studied, the HB/CMC-based films with HMP, sodium caseinate (NaCas) or pea protein isolate (PPI), and glycerol (G) films exhibited the highest elongation at a break of 139%. Supplementing additives to HB, MC, or CMC-based films improved thermal stability, supported by thermogravimetry. Combining HMP/NaCas/G to HB/CMC resulted in films with the highest peak temperature (276° C). Additionally, integrating NaCas into the films also reduced oxygen and water vapor permeabilities by up to 25% and 11%, respectively, compared to their controls. Fourier Transform Infrared spectroscopy (FTIR) revealed an additive relationship between HB and MC or CMC composite films relative to their singular spectra. SEM showed a smooth compact structure, indicating a homogeneous blending amongst all components. This work demonstrated a viable solution for developing environmentally friendly bio-packaging materials based on HB extracted from corn bran, a plentiful low-value by-product of the biofuel industry’s corn kernel dry milling process combined with other agricultural-derived biomass, such as pectin, proteins, and glycerol.
... Sacrificial microfiber templates were produced by spinning a volatile solution of Soluplus® (BASF), a polyvinyl caprolactam-polyvinyl acetatepolyethylene glycol graft copolymer, out of custom rotary chamber [40][41][42]. The polymer solution was made by combining Soluplus® at a 50% w/v ratio with a mixture of ethanol and chloroform (7:3), and allowing it to completely dissolve over 2-3 d. ...
... We began by testing multiple thermoresponsive polymers, including Pluronic F-127, poly(N-isopropylacrylamide), polyvinylcaprolactam, and Soluplus®, a polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer. Of these four, Soluplus® performed best: it produced the most mechanically robust microfibers, demonstrated negligible toxicity to cell cultures, and most importantly, showed temperature-dependent solubility in water [40][41][42]. At high concentration, Soluplus® exhibits a LCSTlike behavior at 32-37 • C: below this temperature it becomes more favorable for Soluplus® to adopt an unfolded configuration, form hydrogen bonds, and become much more soluble in water [41,48]. ...
In the body, capillary beds fulfill the metabolic needs of cells by acting as the sites of diffusive transport for vital gasses and nutrients. In artificial tissues, replicating the scale and complexity of capillaries has proved challenging, especially in a three-dimensional context. In order to better develop thick artificial tissues, it will be necessary to recreate both the form and function of capillaries. Here we demonstrate a top–down method of patterning hydrogels using sacrificial templates formed from thermoresponsive microfibers whose size and architecture approach those of natural capillaries. Within the resulting microchannels, we cultured endothelial monolayers that remain viable for over three weeks and exhibited functional barrier properties. Additionally, we cultured endothelialized microchannels within hydrogels containing fibroblasts and characterized the viability of the co-cultures to demonstrate this approach’s potential when applied to cell-laden hydrogels. This method represents a step forward in the evolution of artificial tissues and a path towards producing viable capillary-scale microvasculature for engineered organs.
... This is achieved by increasing the free volume between polymer chains which allows the chain segments to move and rotate more freely [13]. The increased movement of polymer chains with respect to each other also decreases the glass transition temperature (T g ) and melt viscosity [14][15][16][17]. Common plasticizers used for bioplastics include glycerol, sorbitol and polyethylene glycol [17]. ...
The impact of a glycerol–silicate (GS) plasticizer on the mechanical, thermal and hydrophobic properties pertaining to sodium alginate (NaAlg) and calcium alginate (CaAlg) films were investigated. Spectroscopic and physio-chemical analysis were conducted to evaluate the effects of the GS incorporation. The results determine that both NaAlg and CaAlg films exhibited poor mechanical properties which only improved by increasing the GS loading (up to 25 wt%), after which it declined. CaAlg exhibited the highest tensile strength after 25 wt% GS loading was incorporated. The elongation at break varied, with NaAlg films showing a ~10-fold increase, while the CaAlg films remained relatively unchanged. Thermal gravimetric analysis (TGA) revealed that GS reduced the onset decomposition temperature of NaAlg films, whereas CaAlg films maintained a greater onset decomposition temperature. The advancing contact angle measurements indicated a nearly linear decrease (from 54° to 39°) in hydrophobicity for the NaAlg films while the hydrophobicity for CaAlg films initially increased from 65° to 74°, and then became more hydrophilic with greater GS loading. These findings highlight the potential of GS plasticization to enhance and tailor alginate film properties, providing insights into the development of sustainable bioplastics with improved mechanical properties.
... Overall, aniline molecules have the ability to disturb the cellulose's regular arrangement, enhancing chain mobility and lowering the T g . [36] However, in the cell-PANI 10 , phase separation and PANI aggregated led to a re-arrangement of cellulose chains, causing the T g to nearly revert to its value before the addition of PANI. ...
Natural polymers offer several benefits as battery components, such as wide availability, biodegradability, non‐leakage, stability in solid form, ease of processing, electrochemical stability, and low production costs. On the contrary, conductive polymers can enhance the battery's electrochemical performance, improving factors like energy storage capacity, cycling stability, and charge/discharge rates. Thus, combining these two types of materials can yield desirable properties. In this research, thin polymer films are produced based on cellulose using the solution casting method. Polyaniline (PANI) is then mixed with cellulose in various weight ratios. The electrochemical characteristics of the prepared electrolytes are analyzed, revealing that the addition of PANI increases ionic conductivity through creating voids and benefiting from the conductive polymers’ high dielectric constant. The prepared electrolytes demonstrate impressive ionic conductivity (≈10⁻³ S cm⁻¹ upon incorporating PANI), remarkable discharge capacity, consistent cycling stability, outstanding electrochemical performance with a stability window exceeding 4.5 V, and a good Li⁺ transference number spanning from 0.44 to 0.76.
... Conversely, in the 60/40 and 50/50 blends, Young's modulus values increased, which generally occurs due to phase separation in PLA-based blends 23 . The lower Young's modulus is associated with compounds requiring less force for elastic deformation, leading to superior elastic properties and better performance 26 . The 70/30 blend exhibited the lowest Young's modulus value. ...
Blending biopolymer is a key objective in development of innovative materials and effectively enhances the characteristics of the components to achieve tailored properties. This study introduces five eco-friendly blends in different ratios, created by melt-blending polymers, incorporating Pistacia atlantica subsp. mutica gum into plasticized poly (lactic acid) with 16% acetyl tributyl citrate. To perform a comprative analysis of blends ratios, comprehensive techniques were applied, including differential scanning calorimetry, tensile testing, Fourier-transform infrared spectroscopy, scanning electron microscopy, and evaluations of water absorption behavior, chemical resistance, and biodegradability. The 70/30 (plasticized poly (lactic acid)/P. atlantica) blend was mechanically superior, exhibiting the greatest elongation at break and the lowest yield strength and Young’s modulus. FTIR analysis showed consistent spectral patterns across the 3000 to 650 cm− 1 range, with numerous absorption bands. DSC analysis identified the highest and lowest glass transition temperatures for the 90/10 and 70/30 blends, respectively. Scanning electron microscopy highlighted the development of more distinct island-sea structures as the proportion of P. atlantica gum increased. Water absorption tests differentiated the 90/10 blend as the most absorbent, while the 70/30 blend absorbed the least. Chemical resistance testing revealed all blends gained weight in HCl, but only the 90/10 blend lost weight in NaOH. All samples were confirmed to be highly biodegradable, surpassing 50% degradation after 6 months. Overall, the findings suggest that blending plasticized poly (lactic acid) and P. atlantica gum enhances the flexibility and performance of poly (lactic acid), warranting further attention.
... These results showed that DO was in a dissolved and dispersed state in DO-loaded PLGA nanoparticles. [29,[49][50][51] During the PVA and PEG blending process, a decrease in the PVA crystallinity is observed because of the between PVA and PEG H-bonding formation causing the PVA chain mobility reduction. DNPF showed a sharper Tm peak at 225.2°C due to the crystalline structure of DO [52] (Figure 5). ...
Recently developed nanoparticles and nanofibers present new brain‐specific treatment strategies, especially for Alzheimer's disease treatment. In this study, donepezil (DO)‐loaded PLGA nanoparticles (DNP) are embedded in PVA/PEG nanofibers (DNPF) produced by pressurized gyration for sublingual administration. SEM images showed produced drug‐loaded and pure nanofibers, which have sizes between 978 and 1123 nm, demonstrated beadless morphology and homogeneous distribution. FT‐IR, XRD, and DSC results proved the produced nanoparticles and fibers to consist of the DO and other polymers. The in vitro drug release test presented that the release profile of DO is completed at the end of the 18th day. It is released by the first order kinetic model. DNPF has an ultra‐fast release profile via its disintegration within 2 sec, which proved itself to be suitable for the administration sublingually. All samples presented above ≈90% cell viability via their non‐toxic natures on SH‐SY5Y human neuroblastoma cells by using Alamar blue assay. The anti‐Alzheimer effects of DO, DNP, and DNPF are evaluated on the Aβ1−42‐induced SH‐SY5Y cells at 1, 5, and 10 µM as treatment groups. The 1 µM dosage exhibited the most significant neuroprotective effects, which showed enhanced cellular uptake and superior modulation of Alzheimer's‐related proteins, including tau and Aβ.
... Liu et al., 2023), food packaging materials (Omar Anis Ainaa et al., 2021), (Chaos et al., 2019), (Dai et al., 2022), (Sanyang et al., 2015), (Harussani et al., 2021), (Tarique et al., 2021), (Syafiq et al., 2022) drug delivery (H. Lim & Hoag, 2013), air purification (Ghosh et al., 2021) and battery cells (Abdulwahid et al., 2023), (Raut et al., 2019). The researchers used tensile strength (MPa), Young's modulus (MPa) and elongation at break (%) to assess the effectiveness of the plasticizers and have consistently reported a decrease in tensile strength and Young's modulus, along with an increase in elongation at break. ...
The review article focuses on the potential of bio-based plasticizers to enhance the mechanical properties of polymer membranes, addressing the critical issues of fragility and brittleness. It highlights the environmental and health risks associated with traditional plasticizers like phthalates and also advocates for the adoption of sustainable and non-toxic bio-based alternatives. In doing so, it emphasizes the significant advancements in bio-based plasticizer research, aiming to stimulate further scientific inquiry into their application in membrane synthesis. By advocating for the adoption of green polymers, the article underscores the critical necessity for the development of environmentally benign and mechanically robust membrane technologies. These advancements hold considerable promise for a wide array of applications, notably within biomedical domains and separation processes, heralding a new era of sustainability and functionality in membrane technology.
Plasticized polymer nanocomposite electrolytes (PPNCEs) based on Poly (ethylene oxide) + NaI with dodecyl amine modified montmorillonite (DMMT) as the filler and Poly (ethylene glycol) as the plasticizer were prepared by a self-designed tape caster. The effect of plasticization on structural, microstructure, thermal and electrical properties of the PPNCEs were investigated. The changes in the structural and microstructural properties of the materials were investigated by XRD and SEM techniques. Differential scanning calorimetry (DSC) technique was used to study the thermal parameters (i.e., glass transition temperature (Tg) and crystalline melting temperature (Tm)) of the nancomposites. Complex impedance analysis was used to calculate the bulk resistance of the composites. The typical complex impedance spectrum of the samples comprises of a compressed semicircle in the high frequency region (due to the bulk properties) followed by a tail (spike) in the lower frequency region indicating the double layer response at the electrode/sample interface. The maximum conductivity of PPNCE was found to be 1.05x10 -6 for x=50% of plasticizer (at 40 0 C). The effect of plasticizer on the structural and physical properties of polymer nanocomposites was well correlated.
A large number of experimental results in the literature support and illuminate a model of behavior of chains and chain segments in the amorphous phase of semicrystalline polymers connecting the elevation of the glass transition temperature (T-g) above its normal value to several kinds of motional restrictions imposed on the chains and parts thereof: Accordingly, polymer chain, chain-segment and chain-fragment motions of all kinds comprise one or more torsions around main-chain bonds from one stable conformation to another, known as rotational isomerizations. When impediments are placed in front of thermal fluctuations and larger transversal and longitudinal motions of polymer chains, segments and shorter fragments in the amorphous phase, and the motions are thus restricted, the glass transition temperature is elevated relative amorphous phase in the bulk under the same The obstructions may prevent either the onset of rotational isomerizations or of their completion once started. The completion of the torsional isomerizations and larger motions mau be prevented by eliminating the free spaces necessary to accommodate the volumes of the interconverting chain fragments and segments even when they move in concert, or by preventing the creation of such free spaces. Another way to hinder the completion of such motions is by the introduction into the system of many rigid walls and other interfaces with strong attractive interactions with the polymer, that by geometrical constraints and attractive interactions suppress the rotational and larger motions and prevent their completion. Elimination of the necessary free volume is achievable by the application of compressive pressure, while the introduction of rigid attractive walls may be accomplished by the incorporation of crystallites, as in semicrystalline polymers, or by the addition of rigid finely comminuted foreign additives with very large surface areas or confining voids with high tortuosity. It is believed that motional restrictions imposed on the amorphous phase by the growth faces of polymer crystallites, especially in oriented semicrystalline polymers, are more effective than the restrictions imposed by the fold surfaces of these crystallites. The prevention of the onset of rotational isomerizations and larger motions may be achieved by stretching the polymer chains and chain segments in the amorphous phase and, by one means or another, pinning down the taut chains such that essentially all their rotational isomers are in the trans conformation: they cannot interconvert to the gauche conformation since it requires the chain's end-to-end distance to decrease. Parallel alignment of relatively taut chain-segments may impose additional geometrical restrictions on both the onset and completion of rotational isomeric torsions and, of course on longer-range motions. In all cases, the T-g of the motionally constrained parts of the amorphous phase, especially in semicrystalline polymers, is expected to rise. It is likely that the characteristic length associated with transversal motions and their suppression is R-c, the spatial distance between entanglements, which is of the same size scale and may be the same as the tube diameter of the reptation model. Special emphasis was placed in this work on the semicrystalline polymers poly (epsilon-caprolactam) (nylon-6) and poly (ethylene terephthalate) (PET). (C) 1998 John Wiley & Sons, Ltd.
The effects of polyethylene glycols (PEG 400, 1500 and 4000) used as plasticizer on the moisture permeability and mechanical properties of aqueous hydroxypropyl methylcellulose (HPMC) films were evaluated with free films. The free films were prepared by using a pneumatic spraying technique similar to that used in fluidized-bed coaters. There was a clear relationship between some physical film properties and the molecular weights and concentrations of the PEGs used as plasticizer. Over the range of concentrations tested, the moisture permeability of the films decreased slightly as compared to unplasticized control films with increasing molecular weight of the plasticizer. The mechanical strength of the films was shown to be more dependent on the concentration than on the molecular weight of the PEGs, while the ductility of the films was mainly dependent on the molecular weight of the PEG. The addition of PEG at a concentration of 10% resulted in relatively hard and strong films with a moderate elongation (ductility), especially when lower molecular weight plasticizers (PEG 400 or 1500) were used. As regards permeability to moisture and mechanical properties, the addition of PEG at a concentration in the range of 10–20% of the polymer weight seems to be beneficial for aqueous-based HPMC film coats.
A large number of experimental results in the literature support and illuminate a model of behavior of chains and chain segments in the amorphous phase of semicrystalline polymers connecting the elevation of the glass transition temperature (Tg) above its normal value to several kinds of motional restrictions imposed on the chains and parts thereof. Accordingly, polymer chain, chain-segment and chain-fragment motions of all kinds comprise one or more torsions around main-chain bonds from one stable conformation to another, known as rotational isomerizations. When impediments are placed in front of thermal fluctuations and larger transversal and longitudinal motions of polymer chains, segments and shorter fragments in the amorphous phase, and the motions are thus restricted, the glass transition temperature is elevated relative to that of the same amorphous phase in the bulk under normal conditions. The obstructions may prevent either the onset of rotational isomerizations or of their completion once started. The completion of the torsional isomerizations and larger motions may be prevented by eliminating the free spaces necessary to accommodate the volumes of the interconverting chain fragments and segments even when they move in concert, or by preventing the creation of such free spaces. Another way to hinder the completion of such motions is by the introduction into the system of many rigid walls and other interfaces with strong attractive interactions with the polymer, that by geometrical constraints and attractive interactions suppress the rotational and larger motions and prevent their completion. Elimination of the necessary free volume is achievable by the application of compressive pressure, while the introduction of rigid attractive walls may be accomplished by the incorporation of crystallites, as in semicrystalline polymers, or by the addition of rigid finely comminuted foreign additives with very large surface areas or confining voids with high tortuosity. It is believed that motional restrictions imposed on the amorphous phase by the growth faces of polymer crystallites, especially in oriented semicrystalline polymers, are more effective than the restrictions imposed by the fold surfaces of these crystallites. The prevention of the onset of rotational isomerizations and larger motions may be achieved by stretching the polymer chains and chain segments in the amorphous phase and, by one means or another, pinning down the taut chains such that essentially all their rotational isomers are in the trans conformation: they cannot interconvert to the gauche conformation since it requires the chain’s end-to-end distance to decrease. Parallel alignment of relatively taut chain-segments may impose additional geometrical restrictions on both the onset and completion of rotational isomeric torsions and, of course, on longer-range motions. In all cases, the Tg of the motionally constrained parts of the amorphous phase, especially in semicrystalline polymers, is expected to rise. It is likely that the characteristic length associated with transversal motions and their suppression is Rc, the spatial distance between entanglements, which is of the same size scale, and may be the same as the tube diameter of the reptation model. Special emphasis was placed in this work on the semicrystalline polymers poly (ϵ-caprolactam) (nylon-6) and poly (ethylene terephthalate) (PET). © 1998 John Wiley & Sons, Ltd.
Antiplasticization is applicable to polymers which contain rigid, polar groups and stiff chains, such as many bisphenol polycarbonates and polyesters, 2,2,4,4-tetramethyl-1,3-cyclobutanediol polycarbonates and polyesters, cellulose triacetate, and a commercial poly(sulfone ether). The stiffness, hardness, and tensile strength of these polymers are increased by antiplasticizers, and the elongation, impact strength, and heat-distortion temperature are decreased. The stiffness of antiplasticized polymers can be further increased by crystallization. A clear, hard, stiff, tough, self-extinguishing molding plastic with good electrical properties and improved resistance to stress cracking is obtained by antiplasticizing bisphenol A polycarbonate with 20% Aroclor 5460.
Currently available data on the Young's modulus of elasticity of a number of pharmaceutical materials used in tabletting are reviewed and compared with those predicted using the equation given by Marsh (1964) relating the Young's modulus of a material to its indentation hardness and yield pressure. There is very good agreement for the softer materials but anomalies exist for the harder materials.